PL240445B1 - New diaryliodonium salts, method of preparing new diaryliodonium salts, use of new diaryliodonium salts, new stilbene derivatives, method of preparing stilbene derivatives and use of stilbene derivatives - Google Patents

Abstract

The subject of the invention are new diaryliodonium salts of general formula (1), in which - substituents R11 - R15 independently of each other represent: •H, •CN, a •CnH2n+1 group, in which n represents an integer from 1 to 12, in the form of a straight or branched alkyl such as •CH3, •C(CH3)3 •CH(CH3)2 or a •OCnH2n+1 substituent, in which n represents an integer from 1 to 12, such as •OCH3; E- represents an anion selected from the group consisting of PF6-, SbF6-, BF4-, CF3SO3-, TsO-, B(C6F5)4-, B(C6H5)4-, [Al(OC(CF3)3)4]-; - X denotes a 2-cyano•2-phenylvinylphenyl residue of general formula (2A) linked to the iodine atom via any of the carbon atoms in positions 2-6, corresponding to the position of substituents R1-R5, respectively, in which formula substituents R1-R5, provided that the carbon atom in position 2-6 corresponding to any of them does not form a bond with the iodine atom, independently of each other denote •H or a substituent •OCnH2n+1 in which n denotes an integer from 1 to 12, such as •OCH3; - substituents R6-R10 independently of each other denote •H, •CN or any two adjacent substituents from R6-R10 form an unsaturated six-membered ring, which together with the ring to which substituents R6-R10 are attached forms a naphthyl group. The subject of the invention is also a method for the preparation of new diaryliodonium salts and their use, as well as new intermediate compounds-derivatives. stlibene used for the production of new diaryliodonium salts, method of their production and use. Diaryliodonium salts according to the invention can be used as photoinitiators for cationic and free-radical photopolymerization.

Description

PL 240 445 Β1

Description of the invention

FIELD OF TECHNOLOGY

The invention relates to diaryliodonium salts, a method for producing diaryliodonium salts and the use of diaryliodonium salts. The iodonium salts of the invention can be used as photoinitiators of cationic and free-radical polymerization.

STATE OF TECHNOLOGY

The most modern technologies for producing polymer materials are currently based on photochemically initiated processes. Electromagnetic radiation ranging from ultraviolet (UV) to visible light (VIS) is used for this purpose. The synthesis of polymer materials carried out by these processes is one of the most efficient methods, which is why it is currently a very widespread and dynamically developing technique. Polymerization with light was initially used primarily in the coating industry, mainly in varnishing in the production of solvent-free paints and varnishes for the printing, furniture and automotive industries [(1) S.P. Pappas, Radiation Curing, Science and Technology, Plenum Press, New York, 1992]. Photopolymerization is also playing an increasingly important role in the design and formation of models using stereolithography, in medicine for the preparation of hydrogel polymer materials [(2) J. P. Fisher, D. Dean, P. S. Engel, A. G. Mikos, Annual Review of Materials Science 2001, 31, 171-81] and in dentistry for photocurable fillings [(3) K. D. Jandt, B. W. Sigusch, Dental Materials 2009, 2, 1001-1006]. Cationic photopolymerization is an area of science that is developing extremely dynamically and revolutionizing many areas of modern technology. Not only is there an astonishingly rapid increase in applications, but also the development of new materials that determine the pace of this development. Currently, however, the greatest hopes are associated with the development of new chemical compounds for the role of photoinitiators of cationic polymerization. The result of the conducted research is the development of a wide spectrum of chemical compounds intended for the role of cationic polymerization initiators. Despite such extensive scientific work, the number of systems commonly used in industrial practice as cationic photoinitiators is negligible and is mainly limited to diaryliodonium salts of the general formula (I), where E denotes a counterion, usually PFe', SbFs', AsFe', BF4', FSOs', CF3SO3 , CIO4 , (CsHs^B, (CsFs^B.

E and for triarylsulfonium salts.

Onium salts, which include diaryliodonium salts, are widely considered to be materials of the future due to the numerous benefits that industrial applications of these systems bring. They turn out to be the most promising solutions that will revolutionize the photochemical industry when they are improved by eliminating their existing fundamental drawbacks related to the lack of matching of absorption characteristics to the emission characteristics of industrial ultraviolet (UV) and visible (Vis) light sources. From the application point of view, the most important properties of iodonium salts used as polymerization photoinitiators (apart from solubility in monomers) are their optical properties, i.e. the range and magnitude of light absorption. Currently, almost all iodonium salts used in industry as photoinitiators exhibit similar UV absorption characteristics within the wavelength range Xmax = 220-280 nm [(4) J.V. Crivello, Advances in Polymer Science 1984, 62, 1-48] [(5) J. V. Crivello, Journal of Polymer Science: Part A: Polymer Chemistry 1999, 37, 4241-4254] (table I), i.e. the light sensitivity of commercial iodonium photoinitiators is in the short wavelength range of UV light, which is a significant technological problem in their mass applications [(6) W.A. Green, Industrial Photoinitiators A Technical Guide, Taylor & Francis Group, 2010].

PL 240 445 Β1

Table I. Known and commercially available iodonium photoinitiators commonly used in industrial practice, all listed salts absorb radiation in the range of 200-300 nm.

^PF _K σ'Ό ^PF 6- AJ Uk 0. LD Ol X Ol O ID χ ¹ Hycure-810 ChemFine λ _Μ χ = 227 ηπι Omnicat 440 1GM Ama* = 237 nm Speedcure 938 Lambson Xmax = 241 nm Deuteron UV 1240 Deuteron Ama* = 235 nm PF _e - AJ AkA SbF ₆ - kJ kAo^-yF^^ OH Έ 03 O b i ,0 b SbF ₀ - LT 1 L1 1 Irgacure 250 BASF Amax = 242 nm Sarcat CD-1012 Sartomer Amax = 240 nm Uvacure 1600 Allnex Ama» = 240 nm Sylanto'7M-S Photo HiTech & Synthos Amm = 350 nm

Graph I. Comparison of the emission characteristics of a medium-pressure mercury lamp (MPM) with the absorption characteristics of commercial iodonium photoinitiators.

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This is due to the fact that in this wavelength range there are no high-efficiency light sources that would emit light of sufficiently high power. Below 300 nm, only low-pressure mercury lamps and deuterium lamps emit, which are low-power light sources and are not used for industrial applications [(7) M. Montalti, S.L. Murov, Handbook of Photochemistry, Taylor & Francis Group, LLC, 2006]. In industry, the basic high-power UV light sources used to induce photochemical reactions, including photopolymerization reactions, are medium-pressure mercury lamps (MPM lamps), which emit the most UV energy at about 365 nm (Figure I and Table II).

Table II. Relative spectral distribution of mercury lamp radiation [(8) J. Paczkowski, Photochemistry of polymers – theory and application, Mikołaja University Publishing House, Toruń 2003].

Low-pressure mercury lamp (Hanovia SC'25 37 type) Medium-pressure mercury lamp (Hanovia A673 type, 550 W) Wavelength Intensity Inm] [u.rel.] Wavelength Intensity [nm] [J rel.J 253.7 100.00 248.2 8.6 296.7 0.20 253.7 16.6 312.9 0.60 265.3 15.3 365.4 0.54 280.4 9.3 404.7 0.39 289.4 6.0 435.8 1.00 296.7 16.6 546.1 0.88 302.3 23.9 312.9 9.9 334.2 9.3 365.4 100.0 404.7 42.2 435.8 77.5 546.1 93.0

A similar technological problem occurs in the case of using lamps equipped with LEDs (Light Emitting Diodes). LED lamps are becoming increasingly popular on the market of photo-hardened polymer coatings. Currently, a wide range of LED lamps emitting waves of different lengths is available on the market - from the visible range to ultraviolet. For photochemical processes carried out on an industrial scale, LED lamps emitting waves from the ultraviolet range with lengths of about 365, 385 or 395 nm or relatively from the visible range with a length of 405 nm are usually used. The main advantages of light emitting diodes equipped with LEDs from an industrial point of view are the fact that LEDs can be easily turned off and on in a fraction of a second. This means saving electricity and time, because the lamps do not have to warm up before starting work, as is the case with mercury lamps. In addition to low power consumption, reduced heat emission and almost unlimited service life, photochemical polymerization processes carried out using LED lamps also result from low drying temperatures. Therefore, thanks to the use of photochemical curing technology using LED light sources, it is currently possible to print substrates in printing that were impossible to use in machines with mercury lamps due to their sensitivity to heat.

PL 240 445 Β1

Graphs II and III. Comparison of the emission characteristics of UV’LED 365 nm and 395 nm light sources with the absorption characteristics of commercial iodonium photoinitiators.

This not only allows for expanding the range of media used with new, interesting materials, but also reduces costs by using cheaper, more sensitive substrates. However, the fundamental technological problem that prevents the use of LED light sources is the lack of matching the emission characteristics of LED lamps in the range from 365 nm to 405 nm with the absorption characteristics of previously commercially available photoinitiators, in particular cationic photoinitiators

PL 240 445 Β1 new. Both in the case of medium-pressure mercury lamps and in the case of lamps equipped with UV-LED diodes (365 nm, 385 nm, 395 nm) or Vis-LED diodes (e.g. 405 nm) only a small part of the energy is emitted in the absorption range of commercial iodonium photoinitiators. This causes that the cationic photoinitiators used so far based on diphenyliodonium salts have a poor fit of the absorption characteristics to the emission characteristics of industrial UV and Vis light sources such as medium-pressure lamps and UV-LED and Vis-LED diodes (Graphs II and III).

In view of the above, the development of new cationic photoinitiators that will exhibit light sensitivity in the emission range of medium-pressure mercury lamps is very important both from the cognitive and application point of view. So far, only a few iodonium salts are known, intended for the role of photoinitiators of polymerization processes, exhibiting light absorption above 300 nm. One of the first systems based on the iodonium salt skeleton coupled with a fluorenone chromophore is (9-oxy-9H-floren-2-yl)phenyliodonium hexafluoroantimonate(V) [formula (II)] published by Hartwig's group in 2001 [(9) A. Hartwig, A. Harder, A. Luhring and H. Schroder, Eur. Polym. J., 2001, 37, 1449]. The obtained photoinitiator is characterized by several absorption maxima (267 nm, 298 nm, 380 nm and 394 nm), however the most long-wave band located at 394 nm is over 100 times less intense (the molar extinction coefficient at this wavelength is only ε = 400 mol dm ³ -mol- ¹ -cnT ¹ ) than the short-wave band located at 267 nm (the molar extinction coefficient at this wavelength is ε = 42,000 mol dm ³ -mol- ¹ -cm' ¹ ). For this reason (9-oxy9H-floren-2-yl)phenyliodonium hexafluoroantimonate(V) is not used in industry.

W-1 = 367 nm ε = 42,000 [Imol^cm' ¹ ]

W-2 = 298 nm ε = 8,500 [ImorW ¹ ] ^max-3 ⁼ 380 nm ε = 430 [lmor ¹ cm' ¹ ] ^max-4 ” 394 nm ε = 400 [ImorW' ¹ ]

Another significant report on iodonium photoinitiators, showing significantly improved absorption properties, is the work of Ortyl et al. [(10 J. Ortyl and R. Popielarz, Polimery, 2012, 57, 510], in which photoinitiators based on the coumarin skeleton were presented. The most effective derivative, presented below, shows the absorption maximum at a wavelength located at 345 nm, where the molar extinction coefficient is ε = 16,300 mol dm ³ -mol- ¹ -cm ¹ , respectively. Such a high absorption coefficient allowed to achieve a high rate and conversion even when using such light sources as UV-LED diodes with a wavelength of 365 nm and Vis-LED diodes with a wavelength in the visible range during the photopolymerization process of cationic monomers [(11) H. Mokbel, J. Toufaily, T. Hamieh, F. Dumur, D. Campolo, D. Gigmes, J.P. Fouassier, J. Ortyl and J. Laleve'e, J. Appl. Polym. Sei., 2015, 132, 42759].

7 _max = 350 nm ε = 18,050 [ImorW] ^max 316 nm ε = 14,420 [ImorW ¹ ]

W = 340 nm > _lmax = 308 nm ε = 18,430 [ImorW ^-1 ] ε = 14,850 [lmor ¹ cm' ¹ ] (III)

Then, in 2016, Lalevee et al. published [(12) N. Zivic, M. Bouzrati-Zerrelli, S. Villotte, F. Morlet-Savary, C. Dietlin, F. Dumur, D. Gigmes, J. P. Fouassier and J. Laleve'e, Polym. Chem., 2016, 7, 5873] a detailed photochemical study of an iodonium photoinitiator based on a 1,8-naphthalimide(IV) skeleton. The product showed an absorption maximum at 340 nm, which allowed for efficient cationic photopolymerization of monomers using UV-LEDs. However, the initiator

PL 240 445 Β1 is still not commercially available due to the cost-effectiveness of its production. It is worth noting that in this case the chemical structure of the iodonium salt was complicated, which was expanded with the 1,8-naphthalimide chromophore. Due to the above, the molar mass of the photoinitiator also increased, and consequently the molar efficiency of generating protic acid during the photopolymerization process decreased.

pf ₆

Due to the limited number of available iodonium photoinitiators characterized by absorption in the long-wave UV spectrum (λ >300 nm), work aimed at designing and obtaining such iodonium salts is fully justified from the point of view of improving the kinetics of the photopolymerization process. Matching the absorption characteristics of initiators to the emission characteristics of medium-pressure mercury lamps and UV-LED and Vis-LED light sources will enable better energy utilization by increasing the photolysis rate of iodonium salts, and thus will affect the increase in the initiation rate.

From the patent description (13) US 4 683 317 diaryliodonium salts containing aryl ketones are known, of the formula (II)

[RR ¹ I] ⁺ X- (II) wherein R is an aromatic substituent of 6-13 carbon atoms, optionally substituted with a halogen atom or another substituent, R ¹ is a monovalent aryl ketone group attached to the iodine atom via a carbon atom of the aromatic ring, and X is a negative ion such as, for example, BFt, PFe', AsFe', SbFs', CF3SO3 , ClOt or FSOs. These salts are prepared by a metathesis reaction between a diaryliodonium tosylate precursor and a source of a negative ion, for example, a suitable halide such as KSbFs or a hydrogen-containing compound being a source of the X anion. The precursor is formed by the condensation reaction of a hydroxytosyloxyiodoarene with an aromatic ketone.

Other photoinitiators based on diaryliodonium salts are known from patent description (14) US 5 079 378. They are compounds having long-chain aliphatic ester groups attached via an aryl group to an iodine atom. These compounds are obtained by esterification of a monoaryl acid to form a monoaryl ester, which is then reacted with hydroxyltosyloxy-iodobenzene in an organic solvent and then with a suitable halide, providing anions such as BFt, PFe, AsFe or SbFs, to obtain the desired diaryliodonium salt.

Patent description (15) US 5,073,643 deals with diaryliodonium salts in which at least one aryl is substituted with a long-chain alkoxy group having a hydroxy group attached to the 2-position of the alkoxy group. These salts are prepared by reacting monoaryloxy-2-hydroxyalkanes with hydroxytosyloxy-iodobenzene in the presence of an organic solvent and a suitable reagent being a source of anions such as BFt, PFe, AsFe or SbFe.

From the American patent specification (16) US 6,632,960 diaryliodonium salts such as hexafluoroantimonates, hexafluorophosphates, triflates, tetrafluoroborates, tetra(pentafluorophenyl)borates and others are known, in which one of the aryl groups attached to the positively charged iodine atom contains a methyl substituent and the other aryl group contains an alkoxy group substituted with a hydroxy group. These compounds are prepared from hydroxytosyloxyiodoaryl salts and a suitable aromatic compound containing an alkoxy group substituted with a hydroxy group. According to example 1, included in the patent description (16) US 6,632,960, the reaction for the preparation of (4-methylphenyl)[4-(2-hydroxy-1-tetradecyloxyphenyl)]iodonium hexafluoroantimonate is carried out in dichloromethane in the presence of glacial acetic acid and p-toluenesulfonic acid, followed by adding NaSbFs in acetone. In order to obtain the desired salts with anions such as e.g. BFt, B^sFsjT, PFe, AsFe or SbFs', the reaction mixture is added

PL 240 445 Β1 a suitable reagent being a source of anions is added in a suitably selected solvent, and in order to obtain triflate, triflate is added in a suitable solvent to the reaction mixture.

From the patent description (17) EP 1 953 149 iodonium salts of formula (V) are known having in their molecule heterocyclic residues, ^{R 1} —®—R ² ' A, _(v) wherein R ²⁶ and R ²⁷ independently of each other represent an aryl group which may be substituted with a halogen atom or a (C 1 -C 6 )-alkyl group of general formula (VI) *2

O (R ³ ) ¹ (R ⁴ ) ^j (vi) wherein R ³ and R ⁴ independently of each other represent a halogen atom, an alkyl group which may be substituted with a halogen atom or an aryl group, or an aryl group which may be substituted with a (C 1 -C 6 )-alkyl group or a halogen atom; Χ 2 represents an oxygen or sulfur atom; "i" is an integer from 0 to 4 and "j" is an integer from 0 to 3; or a group of the general formula (VII)

(R ⁵ ) p (R ⁶ ) q (VII) wherein R ⁵ and R ⁶ independently of each other represent a halogen atom, an alkyl group which may be substituted with a halogen atom or an aryl group, or an aryl group which may be substituted with a (C 1 -C 6 )-alkyl group or a halogen atom; Χ 3 and Χ 4 independently of each other represent an oxygen or sulfur atom; "p" is an integer from 0 to 2 and "q" is an integer from 0 to 3;

A3 is a halogen atom or an anion derived from a strong inorganic acid, an organic acid or a compound of general formula (VIII)

HMi(R ⁷ ) ₄ (VIII) wherein Mi is a boron or gallium atom and R ⁷ is an aryl group which may be substituted with a (C 1 -C 6 )-haloalkyl group by a halogen atom, a nitro group or a cyano group; and provided that at least one of the groups R ²⁶ and R ²⁷ is a group of the general formula (VII) or (VIII) and when only one of the groups R ²⁶ and R ²⁷ is a group of the general formula (VII) or (VIII), then A 3 is an anion derived from a strong mineral acid of the general formula (IX)

HM ₃ F ₆ (IX) where M3 is a phosphorus, arsenic or antimony atom, from an organic acid or a compound with the general aurora (VIII).

In the patent description (17) EP 1 953 149 several methods of preparation of claimed compounds, which are useful as photoinitiators of cationic polymerization, are given. In one of the examples a method of preparation of phenyl-(7-coumarin) hexafluorophosphate is disclosed by reaction of a mixture of coumarin and diacetoxyiodobenzene suspended in acetic anhydride, to which concentrated sulfuric acid is added, and then ice water, dichloromethane, and then potassium hexafluorophosphate to obtain the desired product. The following scheme illustrates the course of the reaction, the yield of which is 10%.

PL 240 445 Β1

1.(CH ₃ CO) ₂ O, h ₂ s o ₄

2. HjO, CHjCIj, KPF _e

A. 0-7°C, 1h

B. room temperature, 8h

C. room temperature, 2h

diacetoxyiodobenzene coumarin

Comparative example 6 contained in patent description (17) EP 1 953 149 presents the synthesis of phenyl[2-(xanthene-9-one)]iodonium tetrafluoroborate from xanthene-9-one and diacetoxyiodobenzene in concentrated sulfuric acid with the subsequent treatment of the resulting product with potassium tetrafluoroborate.

For several claimed compounds, a graph of absorption as a function of the wavelength of light was drawn. For the above-mentioned photoinitiator - phenyl-(7-coumarin)iodonium hexafluorophosphate - the absorption maximum occurs at 309 nm, but the extinction coefficient for this wavelength is low (6376), while at 241 nm (the second maximum) the extinction coefficient is 5 times higher (31370). Based on the analysis of the graph, it can be concluded that the compounds given in the examples absorb mainly in the short-wave UV range, i.e. below 300 nm.

The invention covered by patent application (18) P.410073 relates to new derivatives (Ej-^-^-cyanophenyl]vinyl]benzene of the general formula (1),

wherein when the vinyl group is attached at position 4 of the benzene ring, the R substituent is different from Ph - H and Ph - OCH3

(E)-[2-[4-cyanophenyl]vinyl]benzene derivatives can be used as photosensitizers for photoinitiated cationic polymerization processes and as components of photoinitiating systems.

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Method for the preparation of (E)-[2-[4-cyanophenyl]vinyl]benzene derivatives of the general formula (1)

wherein R is a substituent of the vinyl group attached at position 3 or 4 of the benzene ring and is:

is characterized by the fact that:

A) 3'-bromobenzaldehyde of formula (2A)

(2A) or 4-bromobenzaldehyde of formula (2B)

is treated with 4-cyanostyrene of formula (3)

in an organic solvent, in the presence of a catalyst, in the presence of an alkaline agent, to obtain 4-[(E)-2-(3-formylphenyl)vinyl]benzonitrile of formula (4A) respectively

(4A) or 4-[(E')-2-(4-formylphenyl)vinyl]benzonitrile of formula (4B)

(4B)

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B) the compound of formula (4A) or (4B) is treated with a dimethylbenzylphosphonate derivative of general formula (5A)

(5A) wherein R' is: a hydrogen atom, a nitrile group, a methyl group, a trifluoromethyl group, a fluorine atom, a bromine atom, a methoxy group, a trifluoromethoxy group, a methylsulfinyl group, an amino group, a dimethylamino group, a nitro group, a methylamino group, a vinyl group, a carboxyl group, a hydroxyl group, or dimethyl(1-naphthyl)methylphosphonate of the formula (5B)

(5B) in an organic solvent in an alkaline medium, and the resulting product is isolated and purified.

Preferably, in step A) the reaction is carried out in an organic solvent selected from the group consisting of N,N-dimethylformamide, dimethylsulfoxide, chloroform, dichloromethane, acetonitrile, toluene, tetrahydrofuran, methanol, isopropanol, acetone, in the presence of a catalyst selected from the group consisting of palladium(II) acetate, palladium(II) chloride, tetrakis-(triphenylphosphinepalladium(0), tris(dibenzylideneacetate)dipalladium(O), bis(triphenylphosphine)palladium(II) dichloride, in the presence of an alkaline agent selected from the group consisting of potassium tert-butoxide, lithium hydroxide, sodium hydroxide, sodium hydride, potassium carbonate. Preferably, in step B) the reaction is carried out in an organic solvent selected from the group consisting of tetrahydrofuran, toluene, dimethylformamide, isopropanol, acetone, dimethyl sulfoxide, chloroform, dichloromethane, acetonitrile, methanol, in the presence of an alkaline agent selected from the group consisting of potassium fert-butoxide, lithium hydroxide, sodium hydroxide, sodium hydride.

From the publication (19) [F. Ladhar, R. El Gharbi, An International Journal for Rapid Communication of Synthetic Organic Chemistry, 21:3, 413-417, DOI: 10.1080/00397919108016764] a stilbene derivative called (Z)-3-(2-methoxyphenyl)-2-phenylprop-2-enenitrile is known. This compound was prepared by reacting phenylacetonitrile with 2-methoxybenzaldehyde at a temperature of 65°C in the presence of a basic agent K2CO3, carrying out the reaction in ethanol. After completion of the reaction, the mixture was filtered and the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography on silica gel.

From the publication (20)[D. Lanari, M. Alonzi, F. Ferlin, S. Santora, L. Vaccaro; the ACS Publications, website at DOI: 10.1021/acs.orglett.6b01121, 2016] a stilbene derivative named (Z)-3-(2,4-dimethoxyphenyl)-2-phenylprop-2-enenitrile is known. This derivative was prepared from phenylacetonitrile and the corresponding aldehyde using Amberlyst fluoride ion exchanger and Silazane polymer.

From the publication (21) [l. Binev, E. Velcheva, I. Juchnovski; Spectrochimica Acta Part A 51, 1995, 1871-1878] stilbene derivatives are known with the names: (Z)-3-(3-methoxyphenyl)-2-phenylprop-2-enenitrile, (Z)-3-(3,5-dimethoxyphenyl)-2-phenylprop-2-enenitrile and (Z)-3-(2,6-dimethoxyphenyl)-2-phenylprop-2-enenitrile.

From the publication (22)[Ng. Ph. Buu-Hoi, Ng. Hoan, M. R. Khenessi, Macrozamin, Part II, 1951, 2307-2309] stilbene derivatives are known with the names: (Z)-3-(2-methoxyphenyl)-2-(2-naphthyl)prop-2-enenitrile and (Z)-3-(2-methoxyphenyl)-2-(1-naphthyl)prop-2-enenitrile.

These compounds were prepared by the condensation reaction of 2-methoxy-benzaldehyde and the appropriate acetonitrile derivative in the presence of alkaline agents.

From the publication of the patent description GB 1152875 (23) a derivative of stilbene called 4-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinyl]benzonitrile is known. This compound was prepared by the reaction of p-cyanophenylacetic acid nitrile with 2,4-dimethoxybenzoic aldehyde.

In none of the above publications was there any mention of the stilbene derivatives described therein being used as photoinitiators for photoinitiated cationic or free-radical polymerization.

It has surprisingly turned out that diaryliodonium salts according to the present invention can act as photoinitiators for photoinitiated cationic and free-radical polymerization processes.

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THE ESSENCE OF THE INVENTION

The subject of the invention are diaryliodonium salts of the general formula (1)

(1) in which

- substituent Rn is a hydrogen atom, a methyl group, a nitrile group; substituent R12 is a hydrogen atom, a methyl group, a nitrile group; substituent R13 is a hydrogen atom, a methyl group, a nitrile group, an isopropyl group, a methoxy group, a tert-butyl group; substituent R14 is a hydrogen atom; substituent R15 is a hydrogen atom, a methyl group, an isopropyl group, a tert-butyl group;

- E' is an anion selected from the group consisting of PFe', SbFe', BF4 , CF3SO3 , TsO', _B (CeF5)4 , B( _C6H5 )4-, [Al(OC( _CF3 ) ₃ )4]-;

- X is a 2-cyano-2-phenylvinylphenyl residue of general formula (2A)

bonded to the iodine atom via any of the carbon atoms in positions 2-6, corresponding to the position of the substituents R1-R5, respectively, in which formula - the substituent R1-R5, provided that the carbon atom in position 2-6 corresponding to any of them does not form a bond with the iodine atom, represent substituent R1 represents a hydrogen atom, a methoxy group; substituent R2 represents a hydrogen atom, a methoxy group; substituent R3 represents a hydrogen atom, a methoxy group; substituent R4 represents a hydrogen atom, a methoxy group; substituent Rs represents a methoxy group;

- the substituents Re-Rio represent: the substituent Re represents a hydrogen atom; the substituent R7 represents a hydrogen atom; the substituent Rs represents a hydrogen atom, a nitrile group; the substituent Rg represents a hydrogen atom, a nitrile group; the substituent R10 represents a hydrogen atom, a nitrile group; or any two adjacent substituents from Re-Rio form an unsaturated six-membered ring which together with the ring to which the substituents Re-Rio are attached forms a naphthyl group.

The 2-cyano-2-phenylvinylphenyl residue is covalently bonded to the iodine atom via any one of the carbon atoms in positions 2-6. When any one of the carbon atoms in positions 2-6 forms a bond with the iodine atom, no substituent is attached to it.

Preferred embodiments of the invention are iodonium salts in which the 2-cyano-2-phenylvinylphenyl residue is bonded to the iodine atom via a carbon atom in position 3 or 5 or 6.

Preferred diaryliodonium salts of the present invention are selected from the group consisting of: [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluoroantimonate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium tetrafluoroborate;

PL 240 445 B1

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium trifluoromethylsulfonate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tosylate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium pentafluorophenylborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-(1-naphthyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium hexafluoroantimonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tetrafluoroborate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tosylate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium trifluoromethylsulfonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tetra-pentafluorophenylborate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium fluorinated alkoxyaluminate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluoroantimonate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tetrafluoroborate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tosylate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium trifluoromethylsulfonate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tetra-pentafluorophenylborate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium fluorinated alkoxyaluminate; [5-[(Z)-2-cyano-2-(2-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-(3-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-methylphenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-methylphenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-cyanophenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-cyanophenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-cyanophenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-methoxyphenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluoroantimonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium tetrafluoroborate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium tosylate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium trifluoromethylsulfonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium pentafluorophenylborate; [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium fluorinated alkoxyaluminate; [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(2,4,6-triphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-(1-naphthyl)vinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate;

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[2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluoroantimonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tetrafluoroborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tosylate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium trifluoromethylsulfonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tetra-pentafluorophenylborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluoroantimonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium tetrafluoroborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]phenyliodonium tosylate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium trifluoromethylsulfonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium tetra-pentafluorophenylborate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate.

The preferred diaryliodonium salts according to the invention are listed in Table 1 below with their chemical names, structural formulae and acronyms given.

Table 1. Preferred diaryliodonium salts of the invention.

Preferred diaryliodonium salts coordinated to different cationic centers

24-087- basic system no. 1

[3-[[Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate

26-027- base system no. 2 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenylcyanoacetate hexafluorophosphate

26-026 - basic system no. 3 [2 - [(Z)-2-cyano-2-phenyl ovinyl]-4methoxyphenyl]-phenyl oiodonium hexafluorophosphate

24-151- basic system no. 4

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate

26-069- basic system no. 5

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenylcyanoic acid hexafluorophosphate

26-088- Sub-Slavic Agreement No. 6

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluorophosphate

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' , Preferred diaryliodonium salts coordinated with [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]- cation and various antho- methyl salts £ .>> £ * T ⁸ .5 About PF _and CN O* C 9 , ^o A~rw “Ί Ol. bf ₄ ^- CN 24-087- basic system no. 1 2Φ087-Α 24-087-B [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenylcyodonium hexafluoroanthimonate [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium tetrafluoroborate Π _t Tfo CM 1 JL ₊ TsC ” Chi About Έρ / ^about VJ ^ł JS — <P 1 24-087-C 24-087-D 24-087-E [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium trifluoromethylsulfonate [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenylcyodonium tosylate [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium pentafluorophenylborate Έ 9 > o o * I 24-087-F [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate ([AKOCfCFshW ^- ) ^,L - Diaryliodonium derivatives, coordinated with the centers of the methoxyphenyl and phylloiodonium compounds, formed by ficra and diacetyloxyiodo (3.-[(Z)-2-cyano-2-phenylvinyl]-4benzenniub with its derivatives cn and oo ^PFe CN li^ 28-034 28-043 28-044 [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate

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IJ ^PF ~ CN Cl - WS ¹ pf _b CN 28-036 24-087- basic system no. 1 [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(2,46-trimethylphenyl)iodonium hexafluorophosphate [3-[(Z)-2-cyano-2-phenylvinyl|-4-methoxyphenyl|-phenyliodonium hexafluorophosphate Preferred diaryliodothyl salts coordinated with cationic centers based on different chromophores Q pf ₆ ,-<y° θ c O z °Y- CN ΥΥί 26-123 23-108 26-101 [3-[(Z)-2-cyano-2-(1-naphthyl)vinyl]-4-methoxyphenyl]phenyl iodone and hexafluorophosphate [3-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-4-methoxyphenyl]phenyl iodonic 3v/y hexafluorophosphate [3-[(Z)-2-cyano-2-(2-naphthyl)vinyb]-4-methoxyphenyl]phenyliodonium hexafluorophosphate Preferred diaryliodonium salts coordinated with the cation [2-[(Z)-2-cyano-2-phenyphovinyl]-4-methoxyphenypho]- -· phenyliodonium and various anions ^0 r Y ^PFs OK, ω X:__? σ ”Ί 1 26-026 - basic system no. 3 26-026-A 26-026-B [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyl iodone and hexafluorophosphate [2-[(Z)-2-cy sno-2-phenyl tart I o| -4methoxyphenyl]phenyliodonium hexafluoroantimonate [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tetrafluoroborate - -\J~° O I Γ II ^Tf0 OT '---- ^e ĆP 1 26-026-C 26-026-D 26-026-E [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tosylate [2- [(Z) 2 cyano 2 phenyl tartaric acid Io| -4methoxyphenyl]phenyl iodonium trifluoromethyl sulfonate [2 [(Z) 2 cyano 2 phenylvinyl]-4 methoxythenyl]phenyl iodine and tetrapentafluorophenyl borate About CN Cj 26-026-F [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyl iodone and the fluorinated alkoxyaluminate ([alk(cf ₃ ) ₃ )4D

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Preferred diaryliodonium salts "coordinated with [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl-aryliodonium] cationic centers formed by reactions with diaryliodobenzene or its derivatives CN ''about ^CN A ''O CM GCCj -JkJ 27-077 27-078 26-134 [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate ^0 ^CN iii U 1* CN - ΓΥ ^PFs 26-135 26-026 - basic system no. 3 [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate Preferred diaryl iodo salts coordinated with the cation [5-[(Z)-2-cyano-2-phenylvinylphoJ-2,4-dimethoxyphenypho], 4._phenyliodomyne and various ammoniums O ff ₆ - 1 CN Ιι'Ύ' ⁰ Έρ o- /A/ “ o— 1 26-027- basic system no. 2 25-099 25-100 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluoroantimonate |5-[(Z)-2-cyano-2-phenyl]-2,4dimethoxyphenyl]phenyl iodonium tetrafluoroborate ¹ "^c; 9 ₊ \ / o b(c ₆ f ₅ >4 ^_ CM [i^ ⁰ 0^ o. 25-081 25-106 25-076 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tosylate [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium trifluoromethylsulfonate |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tetrapentaphthaldehyde

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[ί^Ί AliOCiCF^), I X 0 cn [ργ 25-090 [5-[(Z)-2-cyano-2-phenylvinyl)-2,4-dimethoxyphenyl]phenyliodonium fluorinated alkoxyaluminate ([Al(OC(CF3) ₃ )4n . Preferred diaryliodonium salts are coordinated with cation centers based on [54(Z)-2-cyano-2-' chromophores. - - ^r ..- '-Λ- - arylvinyl]-2,4-dimethoxyphenyl1phenyliodonium T ik ^pFe ikL ^PFe 'I । A o ON ON IjY And CN (ιψ ⁰ And cn 00 °x YEAH 26-114 26-102 25-080 [5-[(Z)-2-cyano-2-(2cyanophenyl)vinyl]-2,4dimethoxyphenyl o]phenyloiodonium hexafluorophosphate [5-[(Z)-2-cyano-2-(3cyanophenyl)vinyl]-2,4di methoxyphenyl]phenyl oiodonium hexafluorophosphate [5-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate .Usesofediaryphoiodonium.-coordinatedWithdeniramcationic .dimethoxyphenytoj-aryliodonium, formed in reactions with diacetoxyiodobenzene or its derivatives - ¹ » — 0 ύ ij ÆV ^F f ^CN ίΐ Ί o- । 27-047 26-104 26-103 [5-[(Z)-2-cyano-2-phenylvinyl)-2,4-dimethoxyphenyl]-(2-methylphenyl)iodonium hexafluorophosphate [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-methylphenyl)iodonium hexafluorophosphate |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate because oh ^— CN k; .X o cn ί| h 0 o — kJ 0^ 'Χ. 00 25-108 25-093 27-038 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4dimethoxyphenyl]-(2cyanophenyl)ionium hexafluorophosphate [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-cyanophenyl iodonium hexafluorophosphate |5-[(Z)-2-cyano-2-phenylvinyl]-2,4dimethoxyphenyl]-(4cyanophenyl o)iodonium hexafluorophosphate

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1 ¹ <Ρ \_____ ¹ m -o and piM ii O- -'l 27-043 26-139 26-130 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl|-(3-methoxyphenyl)iodonium hexafluorophosphate [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate ^PF6- Pi ^PF ~ ι CN 1 CN % 26-140 26-027- basic system no. 2 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-fertbutylphenyl)iodonium hexafluorophosphate [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyenyl]phenyliodonium hexafluorophosphate Preferred salts of diaryphoiodonium’, , ' dśłrwAęks; «e coordinated with the cation [2-f(Z) _; 2-cyandium-2-phenolyl]-4,6yfehyphoyphenyphoiodine is formed with various anions. / o ^0 ^x o and ^N Γί GM ^CN ιΓί Shhh °' pf ₆ Γ l| Γ T SbF ₆ - a-- 24-151- basic system no. 4 24-151-A 24-151-B [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate [2-[(Z)-2-cyano-2-phenylvinylc]-4,6-dimethoxyphenyl]phenyliodonium hexafluoroantimonium an |2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl|phenyliodonium tetrafluoroborate 0 c ^0 τ Δ CN ίΔη CM (Δη OrW ⁰ ' ^T '° L II Tto ϋ B(C ₆ F ₅ ) ₄ 24-151-C 24-151-D 24-151-E P-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium fate en [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium trifluoromethylsulfonate |2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl|phenyliodonium pentafluorophenylborate I .· __z° O Ίίό 24-151-F [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium fluorinated alkoxyaluminate ([AKOCfCFjhM ^- )

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: ^.Preferred diaryliodonium salts coordinated with 2-{(Z)-2-cyano-2-phenylvinyl]-4,6- - dimethoxyphenylaryliodonium cations - ' - - Λ - ^0 ^CN iii Οχ ⁰ ' ''o o 3 ' 25-151 25-155 25-150 [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate |2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(2,4,6-triphenyl)iodonium hexafluorophosphate about CM Γjf ^pf ~ 25-156 [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate . , Preferred diaryliodonium salts coordinated with cation centers based on ... ; o various chromophores · ' ^J . ΛΓ -- I ^0 A ? iS 'o CN [l^ COĆĆk ° ^pF6- 26-148 26-082 [2-[(Z)-2-cyano-2-(1-naphthylvinyl]-4,6dimethoxyphenyl]phenyliodonium hexafluorophosphate [2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate Preferred diaryliodonium salts coordinated with the [3-[(Z)-2-cyano-2-phenylvinylJ-2,4-dimethoxyphenyl] angle and _various ammonium I 0 FFe χΟρι,Ό o χ JO O _S J _F - ^x SbF$ bf ₄ - 26-069- basic system no. 5 26-069-A 26-069-B [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluoroantimonate |3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tefrafluoroborate

PL 240 445 Β1

ΛΑ CL /^ν ⁰ ' ο about a Pi £1 OTAL ¹ TfO ΛΑ W' Ib 1 26-069-C 26-069-D 26-069-E [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tosylate [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyl iodonium trifluoromethylsulfonate |3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tetrapentafluorophenylborate ΛΑ cl· >__1 O a w o / o ”+ and 0 26-069-F [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate ([Al(OC(CF ₃ ) ₃ )4r) Beneficial salts of diaryliodonium skin O !,- coordinated with [3-[(2)-2-cyanoenyl iodonium cation and various anions ''o I A _ SbF- MW O* ϊ /=v ^o s i- ł · · ^ 26-088- basic system no. 6 26-088-A 26-088-B [3-[(Z)-2-cyano-2-phenyl vinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluorophosphate [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluoroantimonate [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyl iodonium tetrafluoroborate ''o । HA TsO ^— Γ ITT A ^vx TfO ο'ί —° y O \—( 26-088-C 26-088-D 26-088-E [3-[(Z)-2-cyano-2-phenylvinyl o]-2,4,6trimethoxyphenyl o]-phenyl oiodonium tosylate [3-[(Zj-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium trifluoromethylsulfonate [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium tetrapentafluorophenylborate I < QI — O ⁺ c-^=< ^from O 26-088-F [3-[(Z)-2-cyano-2-phenyl aluminate]-2,4,6-trimethoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate ([Al(OC(CF ₃ ) ₃ )4j )

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The subject of the present invention is also a method for producing diaryliodonium salts. Method for producing diaryliodonium salts of general formula (1)

in which the meaning of the substituents is as defined above for the product category, characterized in that a stilbene derivative of general formula (2B) is introduced into 99.8% glacial acetic acid

(2B), wherein the substituent selected from R1-R5 attached at the corresponding 2-6 position to the carbon atom via which the 2-cyano-2-phenylvinyl-phenyl residue of the general formula (2A) is linked to the iodine atom in the produced compound of the general formula (1) is a hydrogen atom, and the remaining substituents from R1-R5 and the substituents Re-Rio in the general formula (2B) have the meanings as in the general formula (2A) as defined above for the product category, and diacetoxyiodobenzene or a derivative thereof covered by the general formula (3)

in which the meaning of the substituents from Rn to R15 is the same as in the compound of general formula (1), and an acid selected from the group consisting of p-toluenesulfenic acid, p-rtoluenesulfonic acid in the form of a monohydrate hydrate, sulfuric acid and methanesulfonic acid is added to the solution thus obtained, and the reagents are mixed at a temperature of 20°C to 100°C, monitoring the progress of the reaction, and then, after the substrates have reacted, an inorganic or organic-inorganic salt selected from the group consisting of KPFs, NaSbFs, NaBF4, CF3SO3K, TsONa, (CsH5)4BNa, (CsF5)4BNa, NaPFs, KSbFs, KBF4, CFsSOsNa, (CsHs^BK, (CsFs^BLi and [Al(OC(CF3)3)4]Li and acetic anhydride and stirring is continued for a period of 1 minute to 60 minutes, then water is added and stirring is continued for a period of 1 minute to 120 minutes, and then the precipitated product is filtered off, washed with water and an organic solvent selected from the group consisting of isopropanol, chloroform, dichloromethane, acetone, acetonitrile, diethyl ether, tetrahydrofuran, ethyl acetate, dimethylformamide, dimethyl sulfoxide, pentane, heptane, hexane, cyclohexane, benzene, toluene, xylene and dried.

Preferably, compounds of general formula (2B) are used selected from the group consisting of: (Z)-3-(2-methoxyphenyl)-2-phenylprop-2-enenitrile;

(Z)-3-(2-methoxyphenyl)-2-(4-cyanophenyl)prop-2-enenitrile;

(Z)-3-(2-methoxyphenyl)-2-(2-naphthyl)prop-2-enenitrile;

(Z)-3-(2-methoxyphenyl)-2-(1-naphthyl)prop-2-enenitrile;

(Z)-3-(3-methoxyphenyl)-2-phenylprop-2-enenitrile;

(Z)-3-(2,4-dimethoxyphenyl)-2-phenylprop-2-enenitrile;

2-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinyl]benzonitrile;

PL 240 445 B1

3-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinyl]benzonitrile;

4-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinyl]benzonitrile;

(Z)-3-(3,5-dimethoxyphenyl)-2-phenylprop-2-enenitrile;

(Z)-2-cyano-2-(1-naphthyl)vinyl]-4,6-dimethoxyphenyl;

(Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6-dimethoxyphenyl;

(Z)-3-(2,6-dimethoxyphenyl)-2-phenylprop-2-enenitrile;

(Z)-3-(2,4,6-trimethoxyphenyl)-2-phenylprop-2-enenitrile.

During the work on new diaryliodonium salts, it unexpectedly turned out that new intermediate compounds were developed - stilbene derivatives, used for the synthesis of new diaryliodonium salts. New stilbene derivatives, as well as the method of their production and use are the subject of a patent application separated from this application.

Preferably, as derivatives of diacetoxyiodobenzene of general formula (3) compounds selected from the group consisting of diacetoxyiodo-4-methylbenzene, diacetoxyiodo-2-methylbenzene, diacetoxyiodo-3-methylbenzene, diacetoxyiodo-3-methoxybenzene, diacetoxyiodo-4-cyanobenzene, diacetoxyiodo-3-cyanobenzene, diacetoxyiodo-2-cyanobenzene, 4-tert-butyl-diacetoxyiodobenzene, 4-isopropyl-diacetoxyiodobenzene, diacetoxyiodo-2,4,6-trimethylbenzene are used.

Preferably, the reaction of compounds of general formulae (2) and (3) is carried out at a molar ratio of compound (2) to compound (3) of from 1 : 1 to 1 : 2.

According to a preferred version of the method according to the invention, the reaction of the compound of general formula (2B) and the compound of general formula (3) is carried out by stirring at room temperature a solution of the reagents in glacial acetic acid to which p-toluenesulfonic acid has been added, monitoring the progress of the reaction using thin-layer chromatography, then after the reactants have reacted, the inorganic salt KPFs and acetic anhydride are added to the mixture and stirring is continued for 5 minutes, then water is added and the whole is stirred for a further 30 minutes, and then the resulting precipitate is filtered off, washed with water and diethyl ether and dried in vacuo.

According to a preferred version of the process of the invention, diaryliodonium salts selected from the group consisting of:

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluoroantimonate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tetrafluoroborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium trifluoromethylsulfonate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tosylate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium pentafluorophenylborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-(1-naphthyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium hexafluoroantimonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tetrafluoroborate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tosylate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium trifluoromethylsulfonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tetra-pentafluorophenylborate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium fluorinated alkoxyaluminate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate;

PL 240 445 B1

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluoroantimonate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tetrafluoroborate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tosylate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium trifluoromethylsulfonate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tetra-pentafluorophenylborate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium fluorinated alkoxyaluminate; [5-[(Z)-2-cyano-2-(2-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-(3-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-methylphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-methylphenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-cyanophenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-cyanophenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-cyanophenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-methoxyphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluoroantimonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium tetrafluoroborate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium tosylate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium trifluoromethylsulfonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium pentafluorophenylborate; [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium fluorinated alkoxyaluminate; [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(2,4,6-triphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-(1-naphthyl)vinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluoroantimonate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tetrafluoroborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tosylate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium trifluoromethylsulfonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tetra-pentafluorophenylborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluoroantimonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium tetrafluoroborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]phenyliodonium tosylate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium trifluoromethylsulfonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium tetra-pentafluorophenylborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate.

PL 240 445 Β1

The subject of the present invention is also the use of diaryliodonium salts of general formula (1)

(1) wherein the meanings of the substituents are as defined above for the product category as photoinitiators for photoinitiated cationic and free-radical polymerization.

According to a preferred version of the application, diaryliodonium salts selected from the group consisting of:

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluoroantimonate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tetrafluoroborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium trifluoromethylsulfonate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tosylate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium pentafluorophenylborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-(1-naphthyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate; [3-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium hexafluoroantimonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tetrafluoroborate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tosylate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium trifluoromethylsulfonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium tetra-pentafluorophenylborate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium fluorinated alkoxyaluminate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluoroantimonate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tetrafluoroborate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tosylate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium trifluoromethylsulfonate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tetra-pentafluorophenylborate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium fluorinated alkoxyaluminate; [5-[(Z)-2-cyano-2-(2-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-(3-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-methylphenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-methylphenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate;

PL 240 445 Β1

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-cyanophenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-cyanophenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-cyanophenyl)iodonium hexafluorophosphate; [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-methoxyphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate;

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluoroantimonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium tetrafluoroborate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium tosylate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium trifluoromethylsulfonate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium pentafluorophenylborate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium fluorinated alkoxyaluminate; [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(2,4,6-triphenyl)iodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]-(4-tert-butylphenyl)iodonium hexafluorophosphate;

[2-[(Z)-2-cyano-2-(1-naphthyl)vinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate; [2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluoroantimonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tetrafluoroborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tosylate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium trifluoromethylsulfonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tetra-pentafluorophenylborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluoroantimonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium tetrafluoroborate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]phenyliodonium tosylate;

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium trifluoromethylsulfonate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium tetra-pentafluorophenylborate; [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium fluorinated alkoxyaluminate.

The invention is illustrated by the following examples, which do not limit the scope of its protection.

EXAMPLES

Example 1. Preparation of diaryliodonium salts according to the invention coordinated with the [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium cation and various anions.

STEP 1 - Synthesis of (Z)-3-(2-methoxyphenyl)-2-phenylprop-2-enenitrile (number 27-040) Phenylacetonitrile (0.1 mol) and 2-methoxybenzaldehyde (0.1 mol) were dissolved in methanol (100 ml), sodium methoxide (0.11 mol) was added and the reaction mixture was stirred at room temperature until the starting materials were consumed. The progress of the reaction was monitored using thin layer chromatography (TLC). Then, methanol was stripped off under reduced pressure, water (100 ml) was added to the residue and the resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. The crude product was then purified by column chromatography to obtain a yellowish oil.

PL 240 445 Β1

Spectral data:

(Z)-3-(2methoxyphenyl)-2phenylprop -2-enone11 ry 1 'HNMR (400 MHz, DMSO) δ 8.02 (s, 1H), 7.93 (dd, J = 7.7, 1.4 Hz, 1H), 7.71 (dt .J = 7.1, 1.7 Hz, 2H). 7.54-7.43 (m, 4H), 7.16 (d, J = 8.2Hz, 1H), 7.10 (t, J = 7.6 Hz, UD, 3.88 (s, 3ID)

STEP 2 - Synthesis of diaryliodonium salts with the [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium cation and with various anions.

To a solution of the stilbene derivative from the previous step (0.01 mol) and diacetoxyiodobenzene (0.01 mol) in glacial acetic acid (50 ml) was added p-toluenesulfonic acid (0.01 mol) and the mixture was stirred at room temperature until the starting materials had reacted. The progress of the reaction was monitored by thin layer chromatography (TLC). KPFe (0.01 mol) and acetic anhydride (10 ml) were then added and stirring was continued for 5 min. Water (250 ml) was added and the mixture was stirred for a further 30 min. The resulting precipitate was filtered off, washed with water and isopropanol, then dried in vacuo.

Iodonium salts with different anions were prepared according to the above described methodology. Inorganic and organic-inorganic salts used for this reaction step, depending on the obtained iodonium salt derivative with a cationic center [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium were KPFs, NaSbFs, NaBF4, CF3SO3K, TsONa, (CsHs^BNa, (CsFs^BLi, [Al(OC(CF3)3)4]Li.

Spectral data

Cl PF _S CN AJ 0^ Ή NMR (400 MHz DMSO) 6 8.70 (dd, J = 2.4, 0.8 Hz, 1H). 8.39 (dd. J = 8.9, 2.4 Hz, 1H). 8.27-8.24 (m. 2H), 7.97 <s, 1H), 7.77-7.74 (m. 2H). 7.06 (tt, J = 7.5. 1.0 Hz. 1H), 7.57-7.52 (m, 3H). 7.30 (d, J = 9.0 Hz, 1H), 3.92 (s, 3H) ¹³ CNMR(101 MHz. DMSO) δ 160.5. 139.5. 137.3. 136.1, 135.4, 133.4, 132.4, 132.1, 130.3. 129.8, 126.6, 126.4, 117.6, 117.5, 115.3, 115.0, 106.0, 57.0 = 330 nm, e _n ,ax = 15600 dm3'mol4 'cm-l IL n (Λ dA >HNMR (400 MHz DMSO) 8 8.70 (dd. 4 = 2.4, 1.0Hz, 1H). 8.35 (dd, J = 8.5. 2.2 Hz. III), 8.27-8.23 (m, 211). 7.97 (s, 1ID, 7.76 7.74 (m. 21D, 7.66 (tt, J = 7.4. 1.0Hz, 1H), 7.56-7.51 (m, 3H). 7.30 (d. J = 8.8 Hz, 1H), 3.92 (s, 3H) ¹³ CNMR(1O1 MHz.DMSO)8 160.3, 139.5 135.8, 135.4, 132.5, 130.8. 106.0, 57.4 Amex = 330nm. Emax = 1490(1 days ³ mol ¹ cm' ¹ ΉNMR (400 MHz, DMSO) 8 8.68 (dd. J = 2.5. 0.9 Hz, 1H). 8.34 (dd. J = 9.0, 2.1 Hz, 1H), 8.27-8.24 (m, 2H), 7.98(s, 1H). 7.76-7.72 (m. 2H). 7.64 (mp, 4= 7.2, 1.1 Hz. 1H), 7.56-7.52 (m, 3H), 7.28 (d, J = 8.3 Hz, 1H), 3.91 (s, 3H) ¹³ C NMR (101 MHz, DMSO) 8 160.2, 140.0, 137.0, 136.4, 135.4, 133.3, 132.0. 132.(1, 130.5, 129.9. 126.3. 126.2. 118.2. 117.6. 115.3, 115.2, 106.0, 57.3 Arna» = 330nm, = 15000 dm ³ mol' ¹ cm' ¹

a. - TfO and Λ Ή NMR (400 MHz. DMSO) 8 8.68 (dd, J = 2.3, 0.9 Hz, 1H), 8.35 (dd, J = 9.0, 2.5 Hz. 1H). 8.29-8.25 (m, 2H), 7.96 (p. 1H), 7.78'7.72 (m. 2H), 7.65 (tt, J = 6.8, 1.3 Hz. 1H), 7.56-7.52 (m, 3H), 7.29 ( d, J = 8.8 Hz, 1H), 3.90 (s, 3H) ¹³ C NMR (101 MHz. DMSO) δ 161.0, 139.2, 137.5, 136.3, 135.2, 133.1, 132.4. 132.8, 130.7, 130.0, 126.6, 126.4, 122.7, 118.1, 117.4, 115.6, 115.2, 106.2, 56.9 Ams = 325 nm, = 13800 days ³ mol ¹ cm' ¹ 1 o ó A '11 NMR (400 MHz, CDCW 6 8.44 (d, 4 = 2.2 Hz, IIP, 8.21 (d. J = 8.8. 2.1 Hz. 1H). 8.08 (d. J = 8.2 Hz. 2H), 7.72 ( s, 1H). 7.68-7.64 (m, 2H), 7.55-7.50 (m. 3H), 7.50-7.43 im, 3H), 7.37 (t, J = 7.7 Hz, 2H), 7.03 (d, J = 7.8 Hz, 2H).G.92 (d, J = 9.0 Hz. 1Hz), 3.88 (s, 3H), 2.30 (s. 3H) ^.13 C NMR (101 MHz, DMSO) H 160.4, 146.2. 139.6, 138.0, 137.3, 136.1, 135.4, 133.4.132.3. 132.1. 130.3, 129.8, 128.5, 1265 126.4. 126.0. 117.8. 117.5.115.3, 114.9. 1062, 56.9. 21.2 Ańias = 328 nm, = 15150 days ³ mol ¹ cm' ¹ 1 & J—< „ ó A A Ή NMR (400 MHz. DMSO) 8 8.65 (dd, J = 2.3, 1.1 Hz, 1H), 8.34 (dd. J = 8.8, 2.2 Hz. 1H), 8.26'8.22 (m, 2H), 7.94 (s, 1H), 7.78'7.74 (m. 2H), 7.63 (mp. J = 7.1, 1.1 Hz. III), 7.56-7.51 (m. 311), 7.30 (d,J = 9.1 Hz, III), 3.88 (s, 3ID ¹³ C NMR (101 MIL·, DMSO) δ 160.3. 149.1, 146.7, 139.7, 139.5, 137.3, 136.1 135.2, 134.3, 133.4, 132.7, 132.2, 130 0, 129.9. 126.6, 126.5, 118.0, 117.6, 115.2, 115.5. 106.1, 57.0 Am _t x = 330 nm, = 15750 dm ³ mol ¹ cm ¹ a,. CN li ⁵ ] AtOCICtJ,) a ΉNMR (400 MIIz, DMSO) δ 8.60 (dd, J = 2.3, 1.1 Hz. III), 8.34 (dd, J = 8.8, 2.2 Ilz, III), 8.28'8.22 (m. 211), 7.94 (s, 1ID , 7 78'7.74 (m, 211), 7.64 (t. J = 7.1, 1.1 Hz. 1H), 7.56-7.51 (m, 3H), 7.35 (d. 4 = 9.1 Hz, 1H), 3.85 (s, 3H) lon = 330 nm emax = 1605( 1 days ³ mol · ¹ cm' ¹

PL 240 445 Β1

Example 2. Preparation of diaryliodonium salts according to the invention, coordinated with [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-aryliodonium cationic centers, formed in reactions with various diacetoxyiodobenzene derivatives.

STEP 1 - The synthesis of (Z)-3-(2-methoxyphenyl)-2-phenylprop-2-enenitrile (number 27-040) was carried out analogously to Example 1, Step I.

STEP 2 - Synthesis of diaryliodonium salts coordinated to [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]aryliodonium cationic centers, which are formed in reactions with various diacetoxyiodobenzene derivatives.

To a solution of the stilbene derivative from the previous step (0.01 mol) and the corresponding diacetoxyiodobenzene derivative (0.01 mol) in glacial acetic acid (50 ml) was added p-toluenesulfonic acid (0.01 mol) and the mixture was stirred at room temperature until the starting materials had reacted. The progress of the reaction was monitored by thin layer chromatography (TLC). KPFs (0.01 mol) and acetic anhydride (10 ml) were then added and stirring was continued for 5 min. Water (250 ml) was added and the mixture was stirred for a further 30 min. The resulting precipitate was filtered off, washed with water and diethyl ether, then dried in vacuo.

By using various derivatives of diacetoxyiodobenzene in the above step, which were chemical compounds from the group consisting of diacetoxyiodo-4-methylbenzene, 4-tert-butyl-diacetoxyiodobenzene, 4-isopropyl-diacetoxyiodobenzene, diacetoxyiodo-2,4,6-trimethylbenzene, the compounds included in the table below with spectral data were obtained.

Spectral data:

OM with ^=/ ° \ Ή NMR (400 MHz, DMSO) 6 8.67 (d, J = 2.2 Hz, 1H), 8.35 (dd, J = 8.3,2.3 Hz, 1H), 8.13 (dt, J = 8.3, 2.1 Hz, 2H), 7.97 (s, 1H), 7.76 (dt, J = 6.9,1.8 Hz, 2H), 7.57-7.49 (m, 3H), 7.32 (d, J = 8.2 Hz, 2H), 7.29 (d, J = 9.1 Hz, 1H), 3.92 (s, 3H), 2.34 ( s, 3H) 13C NMR (101 MHz, DMSO) S 160.4, 142.8, 139.4,137.2, 136.0,135.4,133.4, 132.7,130.3,3 129.8,126.5,125.8,117.5,115.2,114.9,114.0, 56.9,21.3 λ _πΰχ = 330 nm, = 16100 dm^moH-cnr ¹ -y. - GN τ<^ι IH NMR (400 MHz, DMSO) 6 8.69 (d, J = 2.3 Hz, 1H), 8.38 (dd, J = 8.9,2.3 Hz, 1H), 8.16 (dt, j = 8.4, 2.1 Hz, 2H) , 7.97 (s, 1H), 7.78-7.74 (m, 2H), 7.57 7.47 (m, 3H), 7.39 (dt, J =8.5,2.1 Hz,2H), 7.30 (d, J = 9.0 Hz, 1H), 3.92 (s, 3H), 2.93 (quin, J = 6.9 Hz, 1H), 1.17 (d, J = 6.9 Hz, 6H] «C NMR (101 MHz, DMSO) δ 160.4, 153.3,139.5,137.2,136.1,135.5,133.4, 130.3,130.2,129.8,126.6,126.4,117.5,115.3,114.9,114.2,106.0,56.9,33.8, 23.9 =330 nm, = 17050 dm^mol· ¹ ·™· ¹ 1 ^PF ' 1 ij Ή NMR (400 MHz, DMSO) δ 8.69 (d, J = 2.1 Hz, 1H), 8.39 (dd, J = 8.9,2.3 Hz, 1H), 8.16 (dt, J = 8.6, 2.1 Hz, 2H), 7.97 (s, 1H), 7.76 (dt, J = 7.0,1.8 Hz, 2H), 7.57-7.47 (m, 5H), 7.30 (d, J = 9.1 Hz, 1H), 3.92 (s, 3H), 1.26 (s, 9H) ¹³ C NMR (101 MHz, DMSO ) S 160.4, 155.5,139.5,137.2,136.1,135.2,133.4, 130.3,129.8,129.2,126.6,126.4,117.5,115.3,115.0,114.1,106.0,56.9,35.3, 31.2 λ _η13Χ = 330 nm, Ł _milx = 15600 dm^mol-t-cm ⁴ - T 1 ^PFe CN rpy *H NMR (400 MHz, DMSO) δ 8.39 (d, )=2.3 Hz, 1H), 8.17 (dd,) = 9.0,2.3 Hz, 1H), 7.95 (s, 1H), 7.75-7.72 (m,2H ), 7.56-7.46 (m, 3H), 7.27 (d, J = 9.0 Hz, 1H),7.21 (s, 2H), 3.92 (s, 3H), 2.67 (s, 6H), 2.29 (s, 3H) « C NMR (101 MHz, DMSO) δ 160.3,143.5,141.9,139.1,136.5,134.9,133.5, 130.3,130.2,129.8, 126.5,126.4,123.6,117.5,115.4,114.5,103.9,56.9,26.9, 21.0 330 nm, = 14250 dm ³ -mol t-cm ¹

PL 240 445 Β1

Example 3. Preparation of diaryliodonium salts coordinated with cationic centers generated from different chromophores • [3-[(Z)-2-cyano-2-(1-naphthyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate

• [3-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate

• [3-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate

STEP 1 - Synthesis of intermediate products

The appropriate acetonitrile derivative (0.1 mol) and 2-methoxybenzaldehyde (0.1 mol) were dissolved in methanol (100 ml), sodium methoxide (0.11 mol) was added and the reaction mixture was stirred at room temperature until the starting materials were consumed. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, methanol was stripped off under reduced pressure, water (100 ml) was added to the residue and the resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Then, the crude product was purified by column chromatography to obtain a yellowish oil.

As a derivative of acetonitrile, (1-naphthyl)acetonitrile, (2-naphthyl)acetonitrile or 4-phenylacetonitrile were used, respectively. The intermediate products shown in the table below with spectral data were obtained.

Spectral data:

(2)-3-(2- methoxyphenyl)-2-(lnaphthyl)prop-2- enonitrile 26-123 Ή NMR (400 MHz, DMSO) δ 8.15 (d, J = 7.7 Hz, 2H), 8.08-8.05 (m, 2H), 7.73 (s, 1H), 7.69-7.59 (m, 4H), 7.57-7.53 ( m, 1H), 7.20-7.15 (m, 2H), 3.85 (s, 3H) ¹³ C NMR (101 MHz, DMSO) δ 158.0,143.8,133.8,133.3,133.0,130.5,130.2, 129.2,128.5,128.0,127.7,127.0,126.2,124.5,122.6,121.0,118.9,112.1,109.9, 56.3 (2)-3-(2- methoxyphenyl)-2-(2naphthyl)prop-2- enonitrile 26-084 Ή NMR (400 MHz, DMSO) δ 8.24 (d, J = 1.6 Hz. 1H) 8.19 (s, 1H), 8.08-8.03 (m, 2H). 8.00-7.97 (m, 2H), 7.90 (dd, J = 8.6, 2.0 Hz, 1H), 7.61-7.58 (m, 2H), 7.55-7.50 (m, 1H), 7.18 (d, J = 8.6Hz, 1H),7.13 (t, J = 7.7 Hz, 1H), 3.90 (s, 3H) ^ia CNMK(101 MHz, DMSO) 6 158.1, 139.0, 133.4, 133.3, 132.8, 131.7, 129.5, 128.9, 128.8, 128.1, 127.6, 127.5. 125.9, 123.2, 123.1. 121.0, 118.3, 112.0, 111.9, 56.3 (Z)-3-(2- methoxyphenyl)-2-(4-phenylpiOp)-2enenitrile Ή NMR (400 MHz, DMSO) δ 7.55 (d, J = 7.46 Hz, 2H), 7.35 (m. J = 7.46 Hz 2H). 3.89 (s, 2H)

PL 240 445 Β1

STEP 2 - The synthesis of diaryliodonium salts coordinated with cationic centers prepared from different chromophores was carried out in a manner analogous to that in Example 1, step 2. The spectral data of the obtained diaryliodonium salts are summarized below.

Spectral data:

PF _e iH NMR (400 MHz, DMSO) 6 8.15 (d, J = 7.7 Hz, 2H), 8.08-8.05 (m, 2H), 7.73 (s, 1H), 7.69-7.59 (m, 4H), 7.57-7.53 ( m, 1H), 7.20-7.15 (m, 2H), 3.85 (s, 3H) ¹³ C NMR (101 MHz, DMSO) δ 158.0,143.8,133.8,133.3,133.0,130.5,130.2, 129.2,128.5,128.0,127.7,127.0,126.2,124.5,122.6,121.0,118.9,112.1,109.9, 56.3 λ _ηΐ οχ= 330 nm, = 12850 dm^moK-cnr ¹ fi _pp and ιτ® CN r-|^ Ou NMR (400 MHz, DMSO) 6 8.75 (d, J = 2.2 Hz, 1H), 8.40 (dd, J = 8.8, 2.2 Hz, 1H), 8.29-8.25 (m, 3H), 8.14 (s, 1H), 8/10-8/06 (m, 2H), 8/02-7/99 (m, 1H), 7.94 (dd, J = 8.7,1.9 Hz, 1H), 7.69-7.60 (m, 3H), 7.53 (tt, J = 7.6,1.5 Hz, 2H), 7.32 (d, J = 9.0 Hz, 1H), 3.94 (s,3H) ¹³ C NMR (101 MHz, DMSO) δ 160.5,139.5,137.4,136.2,135.4,133.6,133.2, 132.4,132.1,130.9,129.6,129.0,128.2,128.0,127.7,126.7,126.4,123.1,117.6, 117.5,106.1,57.0 λη™= 335 nm, e _m , _K = 11300 dm ³ -mol' ¹ -cm- ¹ n f PFe Ή NMR (400 MHz. DMSO) 8 8.72 (d, J = 1.9 Hz, 1H), 8.42 (dd. J = 9.0, 2.3 Hz, 1H), 8.25 (dd, J = 8.3, 1.0 Hz, 2H),8.17 (s, 1H), 8/05-7/91 (dd, J= 27, 8.8 Hz. 4H), 7.66 (t. J = 7.4 Hz. 1H). 7.51 (t, J = 7.58 Hz, 2H), 7.32 (d, J = 9.1 Hz, 1H), 3.93 (s, 3H).

Example 4. Preparation of diaryliodonium salts coordinated with the [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium cation and various anions.

^x o 'o

STEP 1 - Synthesis of (Z)-3-(3-methoxyphenyl)-2-phenylprop-2-enenitrile (number 26-012)

Phenylacetonitrile (0.1 mol) and 3-methoxybenzoic aldehyde (0.1 mol) were dissolved in methanol (100 ml), sodium methoxide (0.11 mol) was added and the reaction mixture was stirred at room temperature until the starting materials were consumed. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, methanol was stripped off under reduced pressure, water (100 ml) was added to the residue and the resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Then, the crude product was purified by column chromatography to obtain a slightly yellow solid.

Spectral data:

(Z)-3-(3-methoxyHenyl)-2phenylprop -2 - enenitrile Ή NMR (400 MHz, DMSO) 5 8.04 (s, III), 7.79-7.76 (m, 211), 7.56-7.51 (m, 4H), 7.49-7.44 (m. 2H), 7.10 (ddd, J = 8.1 , 2.6, 1.0 Hz, 1H), 3.83 (s, 3H)

STEP 2 - Synthesis of diaryliodonium salts coordinated with the [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium cation and various anions.

To a solution of the stilbene derivative from the previous step, i.e. (Z)-3-(3-methoxyphenyl)-2-phenylprop-2-enenitrile (0.01 mol) and diacetoxyiodobenzene (0.01 mol) in glacial acetic acid (50 ml), p-toluenesulfonic acid (0.01 mol) was added and the mixture was stirred at room temperature until the reactants had reacted. The progress of the reaction was monitored using thin-film chromatography.

PL 240 445 Β1 tion (TLC). Then KPFs (0.01 mol) and acetic anhydride (10 ml) were added, stirring was continued for 5 min. Water (250 ml) was added and the mixture was stirred for a further 30 min. The resulting precipitate was filtered off, washed with water and isopropanol, then dried in vacuo.

Iodonium salts with different anions were prepared according to the above described methodology. Inorganic and organic-inorganic salts used for this reaction step, depending on the obtained iodonium salt derivative with the center in the form of the [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium cation, were KPFs, NaSbF4, NaBF4, CF3SO3K, TsONa, ( _CsH5 )4BNa, ( _C6F5 )4BLi, [Al(OC( _CF3 ) ₃ )4]Li.

Spectral data:

X- ^Χ Η NMR (400 MHz. DMSO) δ 8.42 GJ.4 = «.9 Hz, III). 8.13 (p, III). H.09-8.00 (m, 211). 7.83-7.80 (m, 211), 7.65-7.57 (m. 511). 7.45 (tt, J = 7.8, 1.0 1 Is. 211), 7.20 (dd, J = 8.9, 2.9, 1 Is., III), 3.88 (s, 311) ^I3 CNMR(101 MHz, DMSO) δ 102.6, 142, 1, 139.5, 139.4, 135.2, 132.7. 132.4. 132.1, 130.9. 129.8, 126.9. 118.9. 118.4. 117.6. 118.4. 117.6, 117.3, 116.7, 108.7, 56.5 Xmox=300 mu. Emax = 18700 days ³ mul ¹ cm ¹ o-ζν-/ TO Ή NMR (400 MHz, DMSO) δ 8.41 (d.3 = 8.9 Hz, HI). 8.14 (s, HI). 8.07-8.02 (m. 2H), 7.84-7.80 (m. 211), 7.66-7.57 (in. 511), 7.43 (m. 4 = 7.6, 1.1 Hz, 2II), 7.21 (dd, J = 9.0, 2.4 , Hz. III), 3.85 (s, 311) ¹³ CNMR(K)l MHz, DMSO) δ 162.9, 142.5, 139.9. 139.4, 135.0. 132.8. 132.0. 132.3, 130.7. 129.0, 126.2, 118.4. 118.7. 117.7, 118.8, 117.7, 117.7, 116.5. 108.3, 56.9 λτηη,= 305 nm. Emm = 17800 dm ³ mu' ¹ cm' ¹ AND TO ^] H NMR (400 MHz, DMSO) δ 8.39 (d, 4 = 9.0 Hz, 111). 8.10(8, 111), 8.09-8.04 (ni, 211), 7.86-7.80 (m, 211), 7.65-7.59 (m. 511), 7.42 (mp, 4 = 7.8, 1.4 Hz, 211), 7.23 (dd. J = 8.8, 2.3, 1 Iz. 111). 3.89 (s, 311) ¹³ CNMR (101 MHz, DMSO) δ 162.7, 142.2, 139.7. 139.5, 135.2. 132.7. 132.3. 132.5, 131.1. 130.0, 126.5, 118.3, 118.2. 117.7, 118.1, 117.2, 117.8, 116.3, 108.9, 56.8 A _m ax = 300 nm, tmai - 17400 days ³ mu ¹ cm' ¹ I 0 A? U Ή NMR (400 MHz, DMSO) δ 8.43 (d,3 = 8.9 Hz. III), 8.16 (s, HI), 8.07 (d, d = 7.8 1 Iz, 2H), 7.83-7.80 (m. 211), 7.63-7.54 (m, 410. 7.49'7.41 (m. 4II), 7.18 (dd, 4 = 9.0, 3.2 1 Iz. 111). 7.10 (d, J = 7.9 11 z, 211), 3.87 (s, 311), 2.29 (s, 311) ¹³ CNMR (1O1 MHz. DMSO) δ 162.5, 146.1, 142.3, 139.6, 139.3, 138.1, 135.2, 132.7, 132.3, 132.1, 130.8, 129.8. 128.5. 126.8. 125.9. 118.8, 118.3, 117.7, 117.3, 116.7, 108.9, 56.5, 21.2 Ama* = 305 nm, Ema» = 17200 dm ³ mul' ¹ cm' ¹

'o CN Py ooO* - Γ II ^Tf0 1H NMR (400 MHz, DMSO) 6 8.38 (d, J = 8.3 Hz, 1H), 8.11 (p. 1H), 8.09-8.03 (m, 2H), 7.87-7.81 (m, 2H), 7.65-7.60 ( m, 5H), 7.42 (tt, J= 7.4, 1.5Hz.2H). 7.23 (dd, J = 8.8, 2.3, Hz. 1H), 3.87 (p. 3H) ¹³ C NMR (101 MHz. DMSO) δ 162.1. 142.3, 139.9, 139.4, 135.0. 132.8, 132.2, 132.0, 130.6, 129.9, 126.2, 122.9, 119.1, 118.5, 117.2, 118.6, 117.5, 117.3. 116.7, 109.2, 56.8 A _mo = 295 nm, Ema = 17150 dm ⁸ mol- ¹ cm' ¹ 1 .______ CQ TO Ή NMR (400 MHz. DMSO) δ 8.42 (d, J = 8.9 Hz. 1H), 8.12 (s, 1H), 8.09-8.06 (m, 2H), 7.84-7.81 (m, 2H), 7.65-7.57 ( m, 5H), 7.45 (tt, J= 7.6. 1.6Hz, 2H). 7.20 (dd, J = 8.9. 2.5, Hz. 1H), 3.88 (s, 3H) ¹³ C NMR (101 MHz. DMSO) 6 162.3, 149.2, 146.7, 142.0, 139.6, 139.5, 139.2, 135.0, 133.6. 132.7. 132.4, 132.4. 131.5, 129.6. 127.2. 118.7, 118.4, 117.6, 118.2. 117.7. 117.0, 116.7, 108.9,57.1 Amax = 300 nm, Emas = 16900 dm ³ mol · ¹ cm' ¹ 1 o o TO Ή NMR (400 MHz, DMSO) δ 8.42 (d, J = 8.9 Hz, 1H), 8.13 (s, 1H), 8.09-8.06 (m, 211), 7.84-7.80 (m, 2TI), 7.65-7.57 ( m. 5H), 7.48 (tt, J= 7.6, 1.6 Hz 2TT). 7.22 (dd, J = 8.9, 2.5, Hz, 1ΙΓ), 3.85 (s, 3H) A _has x = 303 nm, Ema» = 17500 dm ⁸ mol ¹ cm ¹

PL 240 445 Β1

Example 5. Synthesis of diaryliodonium salts coordinated with [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]aryliodonium cationic centers, which are obtained in reactions with various diacetoxyiodobenzene derivatives

STEP 1 - The synthesis of (Z)-3-(3-methoxyphenyl)-2-phenylprop-2-enenitrile (number 26-012) was carried out analogously to Example 4, step 1.

STEP 2 - Synthesis of diaryliodonium salts coordinated to [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]aryliodonium cationic centers, which are obtained in reactions with various diacetoxyiodobenzene derivatives.

To a solution of (Z)-3-(3-methoxyphenyl)-2-phenylprop-2-enenitrile from the previous step (0.01 mol) and the appropriate diacetoxyiodobenzene derivative (0.01 mol) in glacial acetic acid (50 ml) was added p-toluenesulfonic acid (0.01 mol) and the mixture was stirred at room temperature until the starting materials had reacted. The progress of the reaction was monitored by thin layer chromatography (TLC). KPFs (0.01 mol) and acetic anhydride (10 ml) were then added and stirring was continued for 5 min. Water (250 ml) was added and the mixture was stirred for a further 30 min. The resulting precipitate was filtered off, washed with water and diethyl ether, then dried in vacuo.

Chemical compounds from the group including diacetoxyiodo-4-methylbenzene, 4-tert-butyl-diacetoxyiodobenzene, 4-isopropyl-diacetoxyiodobenzene, diacetoxyiodo-2,4,6-trimethylbenzene were used as derivatives of diacetoxyiodobenzene.

Spectral data:

^s o CN LJ ^PFe iH NMR [400 MHz, DMSO) δ 8.39 (d, J = 8.8 Hz, 1H), 8.12 (s, 1H), 7.97 (dt, J = 8.4, 2.0 Hz, 2H), 7.81 (dt, J = 6.8, 1.8 Hz, 2H), 7.64-7.55 (m, 4H), 7.25 (d, J = 8.4 Hz, 2H), 7.19 (dd, J = 9.0, 3.0 Hz, 1H), 3.88 (s, 3H), 2.32 (s, 3H) ¹³ C NMR (101 MHz, DMSO ) fi 162.5,142.9,142.2,139.4,139.2,135.2,132.7, 132.6,130.8,129.8,126.8,118.8,118.4,117.2,116.7,114.1,108.9, 56.5, 21.3 Amax = 300 nm, E _max = 14350 dm^moH-cnr ¹ o Ή NMR [400 MHz, DMSO) S 8.42 (d, J = 8.9 Hz, 1H), 8.12 (s, 1H), 7.96 [dt, J = 8.4, 2.1 Hz, 2H), 7.80 [dt, J = 6.7, 1.9 Hz, 2H), 7.64-7.55 [m, 4H), 7.29 (dt, J = 8.5, 2.2 Hz, 2H), 7.21 (dd,) = 8.9, 3.0 Hz, 1H), 3.88 (s, 3H), 2.89 (quin, J = 7.0 Hz, 1H), 1.15 (d, J = 7.0 Hz, 6H) ^I3 C NMR (101 MHz, DMSO) fi 162.5,153.3,142.1,139.5,139.3,135.3,132.6, 130.8, 130.2,129.8,126.8,118.9,118.3,117.4,116.6,114.2,108.6, 56.5, 33.7, 23.9 A _max =300 nm, e _max =16100 dm^moM-cm ¹ Ή NMR [400 MHz, DMSO) 6 8.41 (d, J = 8.9 Hz, 1H), 8.11 (s, 1H), 7.93 [dt, J = 8.6, 2.3 Hz, 2H), 7.81-7.78 (m, 2H) , 7.63-7.54 (m, 4H), 7.40 (dt, J = 8.7,2.3 Hz, 2H), 7.20 (dd,) = 9.0, 3.1 Hz, 1H), 3.88 (s, 3H), 1.22 (s, 9H) ¹³ C NMR (101 MHz, DMSO) S ^I3 C NMR (101 MHz, DMSO) 6 162.5,155.4,142.0,139.5,139.3,135.0,132.6, 130.8, 129.8,129.2,128.5,126.8,125.9,118.8,118.3,117.4,116.6,114.0,108.6, 56.5,35.3,31.1 Amas =300 nm, E _max = 16800 dm^moP-cnr ¹ Ή NMR [400 MHz, DMSO) δ 8.20 (d, J = 9.0 Hz, 1H), 8.08 (s, 1H), 7.69-7.65 (m, 2H), 7.62-7.56 [m, 3H), 7.50 (d, ] = 2.9 Hz, 1H), 7.17 (dd, J = 8.9, 3.0 Hz, 1H), 6.97 (s, 2H), 3.87 (s, 3H), 2.36 (s, 6H), 2.24 (s, 3H) > ³ C NMR (101 MHz, DMSO) fi 162.4,143.2,141.7,141.5,139.7,139.6,132.5, 130.9, 130.4,129.8,129.7,126.6,126.5,122.6,118.8,118.1,117.0,116.2,105.6, 56.5,26.3,20.9 A _max = 305 nm, = 16650 dm ³ -mol ¹ -cm- ¹

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Example 6. Preparation of diaryliodonium salts coordinated with the [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium cation and various anions.

STEP 1 - Synthesis of (Z)-3-(2,4-dimethoxyphenyl)-2-phenylprop-2-enenitrile (number 25-060)

Phenylacetonitrile (0.1 mol) and 2,4-dimethoxybenzoic aldehyde (0.1 mol) were dissolved in methanol (100 ml), sodium methoxide (0.11 mol) was added and the reaction mixture was stirred at room temperature until the starting materials were consumed. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, methanol was stripped off under reduced pressure, water (100 ml) was added to the residue and the resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Then, the crude product was purified by column chromatography to obtain a slightly yellow solid.

Spectral data:

(2)-3-(2,4dimethoxyphenyl)2phenylprop-2-enonitrile Ή NMR (400 MHz, DMSO) 8 8.00 (d. J =8.5 Hz, 1H), 7.93 (s, 1H), 7.67 (dt, J = 7.8, 1.8 Hz, 2H), 7.50 (tt, J = 7.2, 1.6 Hz. 2H), 7.42 (tt, J = 7.2, 1.5 Hz, 1H), 6.736.69 (m, 2H), 3.88 (s, 3H), 3.86 (s, 3H) ¹³ C NMR (101 MHz, DMSO) 6 163.5, 159.8, 137.8, 134.8, 129.7, 129.5, 129.2, 125.9, 118.8, 115.7, 108.4, 106.2, 98.8, 56.4, 56.0

STEP 2 - Synthesis of iodonium salts coordinated with [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium cation and various anions

To a solution of the stilbene derivative from the previous step, i.e. (Z)-3-(2,4-dimethoxyphenyl)-2-phenylprop-2-enenitrile (0.01 mol) and diacetoxyiodobenzene (0.01 mol) in glacial acetic acid (50 ml), p-rtoluenesulfonic acid (0.01 mol) was added and the mixture was stirred at room temperature until the reactants had reacted. The progress of the reaction was monitored using thin layer chromatography (TLC). KPFs (0.01 mol) and acetic anhydride (10 ml) were then added and stirring was continued for 5 min. Water (250 ml) was added and the mixture was stirred for a further 30 min. The resulting precipitate was filtered off, washed with water and isopropanol, then dried in vacuo.

Iodonium salts with different anions were prepared according to the above described methodology. Inorganic and organic-inorganic salts used for this reaction step, depending on the obtained iodonium salt derivative with the center in the form of the [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium cation, were KPFs, NaSbFs, NaBF4, CF3SO3K, TsONa, ( _C6H5 ) _4BNa , ( _C6F5 )4BLi, _[ Al(OC( _CF3 ) ₃ )4]Li.

PL 240 445 Β1

Spectral data:

Γ 1 ^PF ~ CN (jY” ^{0 4} H NMR (400 MHz, DMSO) 58.79 (s, 1H), 8.16-8.13 (m, 2H), 7.90 (s, 1H), 7.757.71 (m, 2H), 7.65 [mp, J = 7.5,1.1 Hz, 1H), 7.56-7.56 [m, 5H), 6.97 [s, 1H), 4.07 (s, 3H),3.99 (s,3H) «C NMR (101 MHz, DMSO) 5163.2,160.4,137.3,136.8,135.3,133.8,132.3, 132.0,129.9,129.8,126.2,118.7,118.0,117.0,112.4, 97.6, 96.5, 58.2, 57.2 A _max = 335 nm, E _max = 19600 dms-moH-cnr ¹ fy ^sbF and p. o CN Ι|ψ Cpp ^J H NMR (400 MHz, DMSO) 5 8.79 (s, 1H), 8.15 (dt, J = 7.3,1.1 Hz, 2H), 7.90 (s, 1H), 7.73 (dt, J = 7.0,1.8 Hz, 2H ), 7.65 (tt, J = 7.5,1.1 Hz, 1H), 7.55-7.47 (m, 5H), 6.97 (s, 1H), 4.08 (s, 3H), 3.99 (s, 3H) ¹³ C NMR (101 MHz, DMSO) 5 163.2,160.3,137.3,136.8,135.3,133.8 ,132.3, 132.0,129.9,129.8,126.2,118.7,118.0,117.0,112.4, 97.6, 96.5, 58.2, 57.2 A _max = 335 nm, E _max = 18250 dm^moH-cm ⁴ ar·; .X o CN Γ|ψ ^1H NMR (400 MHz, DMSO) 5 8.78 (s, 1H), 8.14 (dt J = 7.3,1.1 Hz, 2H), 7.90 (s, 1H), 7.73 (dt, J = 7.2,1.6 Hz, 2H) , 7.65 (tt, J = 7.4,1.3 Hz, 1H), 7.55-7.45 (m, 4H), 7.11 (d, J = 7.9 Hz, 1H), 6.97 (s, 1H), 4.07 (s, 3H), 3.99 (s, 3H) ¹³ C NMR (101 MHz, DMSO) 5 163.2,160.3,138.0,137.3,136.8,135.3,133.8, 132.3,132.0,129.9,129.8,128.5,126.1,125.9,118.7,118.0,117.0,112.4, 97.6, 96.5, 58.2,57.2 A _has x= 335 nm, £ _max = 13800 dm^mol^-cm- ¹ ί| η Tso ! CN A<° Cjy^°x ^1H NMR (400 MHz, DMSO) ), 7.64 (tt, J = 7.5, 0.9 Hz, 1H), 7.55-7.45 (m, 7H), 7.11 (d, J = 7.7 Hz,2H), 6.97 [s,lH),4.07 (s, 3H), 3.99 [s,3H),2.29 (s,3H ) ¹³ C NMR (101 MHz, DMSO) δ 163.2,160.4,146.2,138.0,137.3,136.8,135.3, 133.8,132.3,132.0,129.9,129.8,128.5,126.2,125.9,118.6,118.0,117.0, 97.6, 96.6, 58.2,57.2,21.2 A _m ax = 335 nm, E _max = 10100 dmS-moH-cm · ¹ ry^π° । CN Α<° ^1H NMR (400 MHz, DMSO) δ 8.78 (s, 1H), 8.14 (d, J = 7.8 Hz, 2H), 7.90 (s, 1H), 7.73 (dt, J = 7.3,1.3 Hz, 2H), 7.65 (tt, J = 7.5,1.3 Hz, 1H), 7.55-7.45 (m, 5H), 6.97 (s, 1H), 4.07 (s, 3H), 3.99 (s, 3H) ¹³ C NMR (101 MHz, DMSO) δ 163.2,160.3,137.3,136.8,135.3,133.8 ,132.3, 132.0,129.9,129.8,128.5,126.2,125.9,118.7,118.0,117.0,112.4, 97.6,96.5, 58.2, 57.2 A _has x= 335 nm, E _max = 19300 dm^moP-cm· ¹ ZA Έρ —\ o O— Tl I Ή NMR (400 MHz, DMSO) δ 8.79 (s, 1H), 8.14 [dt, J = 7.1,1.1 Hz, 2H), 7.90 [s, 1H), 7.73 (dt, J = 7.0,1.7 Hz, 2H) , 7.64 (tt, J = 7.5,1.3 Hz, 1H), 7.54-7.44 (m, 5H), 6.98 (s, 1H), 4.07 (s, 3H), 3.99 (s, 3H) ¹³ C NMR (101 MHz, DMSO) δ 163.2,160.3,137.3,136.7, 135.3,133.8,132.3, 132.0,129.9,129.8,126.1,118.7,118.0,117.0,112.4, 97.6, 96.5, 58.2, 57.2 A _m ax= 335 nm, ε^χ = 17700 dm ³ -mol' ¹ -cm- ¹ ZA Έ p o- o o * I ^4H NMR (400 MHz, DMSO) δ 8.82 (s, 1H), 8.15 (dt, J = 7.1,1.1 Hz, 2H), 7.90 (s, 1H), 7.70 (dt, J = 7.0,1.7 Hz, 2H ), 7.64 (tt, J = 7.5,1.3 Hz, 1H), 7.54-7.40 (m, 5H), 6.92 (s, 1H), 4.05 (s, 3H), 3.97 (s, 3H) A _max = 336 nm, E _max = 19700 dm ³ -mol ⁴ ·σπ ⁴

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Example 7. Preparation of diaryliodonium salts coordinated with cationic centers based on different chromophores.

STEP 1 - Synthesis of intermediate products in the form of:

• 2-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinyl]benzonitrile (number 26-105):

• 3-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinylbenzonitrile (number 28-019):

• 4-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinyl]benzonitrile (number 25-077):

The appropriate phenylacetonitrile derivative (0.1 mol) and 2,4-dimethoxybenzoic aldehyde (0.1 mol) were dissolved in methanol (100 ml), sodium methoxide (0.11 mol) was added and the reaction mixture was stirred at room temperature until the starting materials were consumed. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, methanol was stripped off under reduced pressure, water (100 ml) was added to the residue and the resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Then, the crude product was purified by column chromatography to obtain a slightly yellow solid.

The phenylacetonitrile derivatives used in this example, depending on the intermediate obtained (stilbene derivative), were: 2'-cyano-phenylacetonitrile, 3'-cyano-phenylacetonitrile or 4'-cyano-phenylacetonitrile, respectively.

Spectral data:

2-[(Z)-1-cyano-2-(2,4dimethoxyphenyl)vinyl]benzonitrile (number 26-105) Ή NMR (400 MHz, DMSO) 6 8.11 (d, J = 8.8 Hz, 1H), 7.99 (dd, J = 7.7, 1.2 Hz, 1H), 7.84 (s, 1H), 7.83 (td, J = 7.8, 1.4 Hz, 1H), 7.73 (dd. J = 7.9, 1.2 Hz, 1H), 7.64 (td, J = 7.7, 1.3 Hz, 1H), 6.77 (dd, J = 8.8, 2.5 Hz, 1H), 6.72 (d,J = 2.4 Hz, 1H), 3.88 ( s, 3H), 3.87 (s, 3H) ¹³ CNMR (101 MHz, DMSO) δ 164.3, 160.3, 143.8, 139.0, 134.8, 134.4, 130.0, 129.9, 129.4, 118.2, 117.7, 114.8. 110.4, 106.7, 104.3.98.9, 5G.5, 56.2 3-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinyl]benzonitrile (number 28Ό19) Ή NMR (400 MHz, DMSO) δ 8.14 (t, J = 1.6 Hz, 1H), 8.07 (s, 1H), 8.02-7.97 (m, 2H), 7.88 (dt, J = 7.7, 1.1 Hz, 1H) , 7.70 (t, J = 7.8Hz, 1H), 6.75-6.70 (m, 2Π), 3.90 (β, 311), 3.87 (s, 3Π) 4-[(Z)-1-cyano-2-(2,4-dimethyloxyphenyl)vinyl benzonitrile (number 25Ό77) Ή NMR (400 MHz, DMSO) δ 8.11 (p. 1H), 8.05 (d. J = 8.6 Hz. 1H), 7.95 (d. J = 8.2 Hz, 2H), 7.86 (d, J = 8.6 Hz, 2H), 6.76-6.70 (m, 2H) i3C NMR (101 MHz, DMSO) δ 164.2, 160.3, 140.6, 139.3,133.6, 129.8, 126.6 , 119.0, 118.3, 115.3, 111.3, 106.6, 98.9, 56.5, 56.2

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STEP 2 - Synthesis of diaryl salts coordinated to different cationic centers.

In this step, the procedure used in step 2 of Example 6 was repeated. First, an iodonium salt coordinated with the [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium cation was prepared.

To a solution of (Z)-3-(2,4-dimethoxyphenyl)-2-phenylprop-2-enenitrile (0.01 mol) and diacetoxyiodobenzene (0.01 mol) in glacial acetic acid (50 ml) was added p-toluenesulfonic acid (0.01 mol) and the mixture was stirred at room temperature until the starting materials had reacted. The progress of the reaction was monitored by thin layer chromatography (TLC). KPFs (0.01 mol) and acetic anhydride (10 ml) were then added and stirring was continued for 5 min. Water (250 ml) was added and the mixture was stirred for a further 30 min. The resulting precipitate was filtered off, washed with water and diethyl ether, then dried in vacuo. Spectral data for the intermediate and the iodonium salt are given in Example 6. Iodonium salts with different cationic centers were prepared according to the above described methodology. The stilbene derivatives in this step were, in addition to (Z)-3-(2,4-dimethoxyphenyl)-2-phenylprop-2-enenitrile, the following compounds: 2-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinyl]benzonitrile (number 26-15); 3-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinyl]benzonitrile (number 28-019); and 4-[(Z)-1-cyano-2-(2,4-dimethoxyphenyl)vinyl]benzonitrile (number 25-077).

Spectral data:

-0 p o— ¹ Ή NMR (400 MHz, DMSO) δ 8.86 (s, 1H), 8.16 (dt. J= 7.3, 1.0 Hz, 2H), 8.03 (dd, J -7.8. 1.1 Hz, 1H) 7.87 (dt. J = 7.8 .1.4Hz.1H), 7.81 (s, 1H), 7.77 (dd. J = 7.9, 1.0 Hz, 1H). 7.68 (td, J = 7.6, 1.1 Hz, 1H). 7.66 (tt, J = 7.4, 1.1 Hz, 1H), 7.51 (tt, J = 8.0, 1.4 Hz, 2H), 6.99 <s, 1H). 4.09 (s, 3H), 3 99 fe, 3H) Amat = 340 nm, emax = 15500 dm ³ -mol' ¹ tnr ¹ [l Π ^PF ~ cn NC K0 Οχ, Ή NMR (400 MHz. DMSO) δ 8.79 (d, J = 0.8 Hz, 1H). 8.23 (t, J = 1.7 Hz, 1H), 8.16-8.13 (m, 2H), 8.07 (s, 1H), 8.05-8.02 (m. 1H), 7.94 (dt, J = 7.7, 1.2 Hz, 1H) , 7.74 (t, J= 7.8 Hz, 1H), 7.65 (tt, J = 7.4, 1.1 Hz, 1H), 7.50 (tt, J - 7.6, 1.5 Hz, 2H), 6.98 (s, 1H), 4.08 (s, 3H), 4.00 (s, 3H) ¹³ CNMR (101 MHz, DMSO) δ 163.4, 160.7, 139.2, 137.5, 135.3, 135.1, 133.2, 132.3,132.1,131.0, 130.9, 129.6, 118.7, 118.3, 117.6, 117.0, 113.0, 110.4, 97.7. 96.7, 58.2, 57.2 Amai = 340 nm, e _mas = 19300 dm ^s -mol ¹ tm ¹ A cp V/ ⁺ -o O—^| Ή NMR (400 MHz, DMSO) δ 8.83 (s, 1H), 8.16-8.12 (m. 2H), 8.09 (s, 1H), 8.00 (dt, J = 8.6, 1.8 Hz, 2H), 7.93 (dt. J = 8.6, 1.8 Hz, 2H), 7.65 (tt, J =7.4, 10 Hz, 1H), 7.50 (tt, J= 7.6, 1.5 Hz, 2H), 6.98 (s, 1H), 4.08 (s, 3H), 4.00 (s, 3H) ¹³ CNMR( 101 MHz, DMSO) δ 163.5. 160.8, 139.7, 138.3, 137.6, 135.4, 133.7, 132.3, 132.1, 127.0, 118.9, 118.2, 117.5, 117.0, 112.0, 110.7, 97.7, 96.8, 58.3, 57.3 Jl o. Amaa = 350 nm, Emax = 20500 dm ³ -mol' ¹ rm' ¹

Example 8. Synthesis of diaryliodonium salts coordinated to [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]aryliodonium cationic centers, which are obtained by reactions with various diacetoxyiodobenzene derivatives.

oh^

STEP 1 - The synthesis of (Z)-3-(2,4-dimethoxyphenyl)-2-phenylprop-2-enenitrile (number 25-060) was carried out analogously to Example 6, step 1.

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STEP 2 - Synthesis of diaryliodonium salts, coordinated with [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-aryliodonium cationic centers, formed in reactions with various diacetoxyiodobenzene derivatives.

To a solution of the stilbene derivative from the previous step, i.e. (Z)-3-(2,4-dimethoxyphenyl)-2-phenylprop-2-enenitrile (0.01 mol) and the diacetoxyiodobenzene derivative (0.01 mol) in glacial acetic acid (50 ml), p-toluenesulfonic acid (0.01 mol) was added and the mixture was stirred at room temperature until the reactants had reacted. The progress of the reaction was monitored using thin layer chromatography (TLC). KPFs (0.01 mol) and acetic anhydride (10 ml) were then added and stirring was continued for 5 min. Water (250 ml) was added and the mixture was stirred for another 30 min. The resulting precipitate was filtered off, washed with water and diethyl ether, then dried in vacuo.

Diacetoxyiodobenzene derivatives used in this example are diacetoxyiodo-4-methylbenzene, diacetoxyiodo-2-methylbenzene, diacetoxyiodo-3-methylbenzene, diacetoxyiodo-3-methoxybenzene, diacetoxyiodo-4-cyanobenzene, diacetoxyiodo-3-cyanobenzene, diacetoxyiodo-2-cyanobenzene, 4-tert-butyl-diacetoxyiodobenzene, 4-isopropyl-diacetoxyiodobenzene, diacetoxyiodo-2,4,6-trimethylbenzene.

Spectral data:

c CN I ^PF s Γ I o iH NMR (400 MHz, DMSO) S 8.77 (s, 1H), 8.30 (d, J = 8.0 Hz, 1H), 7.90 (s, 1H), 7.73 (dt, J = 7.3,1.6 Hz, 2H), 7.57 -7.51 (m, 4H), 7.47 (tt, J = 7.1,1.1 Hz, 1H), 7.277.22 (m, 1H), 6.96 (s, 1H), 4.07 (s, 3H), 3.98 (s, 3H), 2.68 (s, 3H) ¹³ C NMR (101 MHz , DMSO) δ 163.1,160.3,141.0,137.6,137.0,136.6,133.8, 133.0,131.6,129.8,129.6,126.2,122.0,118.7,118.1,112.4,97.6, 96.1,58.1, 57.2, 25.4 Amax = 335 nm, £ _nia x = 15700 dnF-moH-cm ¹ ć CN O— ^m | iH NMR (400 MHz, DMSO) 5 8.77 (s, 1H), 8.00 (s, 1H), 7.93 (d, J = 7.7 Hz, 1H), 7.90 (s, 1H), 7.73 (dt, J = 7.1, 1.4 Hz, 2H), 7.53 (tt, J = 6.9,1.4 Hz, 2H), 7.47 (tt, J = 7.3,1.7 Hz, 2H), 7.38 (t, J = 7.8 Hz, 1H), 6.97 (s, 1H), 4.08 (s, 3H), 3.99 (s, 3H ), 2.33 (p,3H) «C NMR (101 MHz, DMSO) δ 163.2,160.4,142.2,137.3,136.8,135.5,133.8, 133.0,132.5,131.7,129.9,129.8,126.2,118.6,118.1,116.8,112.4, 97.6, 96.4, 58.2,57.2,21.2 Amax = 335 nm, c _r nux = 19900 dm ³ -mol' ¹ -cm' ¹ CN 1 PF _e l ⁺ i or iR NMR (400 MHz, DMSO) δ 8.76 (s, 1H), 8.02 (dt, J = 8.3,1.9 Hz, 2H), 7.89 (s, 1H), 7.73 (dt, J = 6.9,1.6 Hz, 2H) , 7.53 (tt, J = 7.2,1.6 Hz, 2H), 7.47 (tt, J = 7.1,1.7 Hz, 1H), 7.30 (d, J = 8.3 Hz, 2H), 6.96 s, 1H), 4.07 (s, 3H), 3.98 (s, 3H), 2.34 (s, 3H) ¹³ C NMR (101 MHz, DMSO) δ 163.2, 160.3,142.7,137.2, 136.7,135.3,133.8, 132.6,129.9,129.8,126.2,118.6,118.0,113.4,112.3,97.6, 96.7, 58.2, 57.2 λ,= 335 nm, Eman = 15200 dnF-mol ¹ -cm ¹ c CN CN I ^pF 6 ^— 7 ¹ 0^ Ή NMR (400 MHz, DMSO) δ 8.84 (s, 1H), 8.54 (dd, J = 8.0,1.1 Hz, 1H), 8.15 (dd, J = 7.5,1.6 Hz, 1H), 7.91 (s, 1H) , 7.84 (td, J = 7.6,1.3 Hz, 1H], 7.78 (td, J = 7.7,1.7 Hz, 1H), 7.75-7.72 (m, 2H), 7.53 (tt, J = 7.0,1.7 Hz, 2H), 7.48 (tt, J = 7.2,1.3 Hz , 1H), 6.97 (s, 1H), 4.07 (s, 3H), 3.99 (s, 3H) ¹³ C NMR (101 MHz, DMSO) 6 163.5,160.2,137.7,136.8,136.7,136.6,135.6, 133.8,133.2,130.0,129.8,126.2,120.5,118.7,118.3,118.0,117.3,112.4,97.8, 97.6, 58.0,57.3 X _max = 335 nm, £ _m ax = 20150 dm ³ -mol' ¹ -cm· ¹

PL 240 445 Β1

CN Π pf ₆ ^_ । γιύ” >H NMR [400 MHz, DMSO) δ 8.82 (s, 1H), 8.74 (t, J = 1.7 Hz, IH), 8.47 [dq, J = 8.1, 1.0 Hz, 1H), 8.12 (dt, J = 7.9 ,1.2 Hz, IH), 7.91 (s, IH), 7.74 [dt, J = 7.1,1.7 Hz, 2H), 7.69 (t, J = 7.9 Hz, 1H), 7.53 (tt, J = 7.1,1.6 Hz, 2H), 7.47 (tt, J = 7.1,1.9 Hz, 1H), 6.98 (s, 1H), 4.08 [s, 3H), 3.99 [s, 3H) 13C NMR (101 MHz, DMSO) δ 163.4,160.3,139.9,138.6,137.4,136.9,136.0, 133.8,132.7,130.0,129.0,126.2,118.8,118.0,117.4,117.1,114.3,112.5,97.7, 96.8, 58.2, 57.3 Amax= 335 nm, e _max = 17300 dirP-moP-cnr ^{1 1} o —O Je/ 0 < o 7 ⁼ \ 00 Ή NMR (400 MHz, DMSO) δ 8.81 (s, 1H), 8.32 (d, J = 8.5 Hz, 2H), 7.96 (dt, J = 8.6, 1.7 Hz, 2H), 7.90 (s, 1H), 7.73 (dt, J = 7.2,1.7 Hz, 2H), 7.53 (t, J = 7.1,1.7 Hz, 2H), 7.48 [t, J = 7.1 Hz, 1H), 6.99 [s, 1H), 4.06 (s, 3H), 4.00 (s, 3H) ¹³ C NMR [ 101 MHz, DMSO) δ 163.4,160.4, 137.5,136.8, 136.0,135.3,133.8, 130.0,129.8,126.2,121.9,118.8,118.0,114.9,112.5, 97.7, 96.6, 58.3, 57.3 X _max = 335 nm, £ _max = 17600 dm^moH-cnr ¹ o- ”1 Ή NMR [400 MHz, DMSO) δ 8.77 [s, 1H), 8.00 [s, 1H), 7.93 [d, J = 7.7 Hz, 1H), 7.90 [s, 1H], 7.73 [dt, J = 7.1, 1.4 Hz, 2H), 7.53 [tt, J = 6.9,1.4 Hz, 2H), 7.47 (tt, J = 7.3,1.7 Hz, 2H), 7.38 (t, J = 7.8 Hz, 1H), 6.97 (s, 1H), 4.08 (s, 3H), 3.99 ( s, 3H), 2.33 (s, 3H) ¹³ C NMR [101 MHz, DMSO) δ 163.2,160.8, 160.4,137.3, 136.8,133.8,132.7, 129.9, 129.8,127.3, 126.2,120.6,118.7,118.2,118.0,116.9,112.4, 97.6, 96.5, 58.2, 57.2,56.3 A _nl - _t = 335 nm, e _max = 18400 01 J pf ₆ ¹ o cn < v Ol Ή NMR [400 MHz, DMSO) δ 8.59 (s, 1H), 7.89 [s, 1H), 7.72 (d, J = 7.4 Hz, 2H), 7.53 (mp, J = 7.8,1.8 Hz, 2H), 7.47 [tt, J = 7.1,2.1 Hz, IH), 7.18 [s, 2H), 6.97 (s, IH), 4.03 (s, 3H), 3.99 (s, 3H), 2.66 (s, 6H), 2.29 [s, 3H) «O NMR [101 MHz, DMSO) δ 163.0,160.6,143.1,142.2,136.8,136.1,133.9, 130.0,129.9,129.8,126.2,122.6,118.4,118.1,111.7, 98.0, 94.0, 57.9, 57.3, 26.6, 20.9 λητ3χ= 335 nm, c _max = 15750 dm ³ -mol^-cm ¹ iC ^PF ~ ^0* 1 CN i|Y ⁰ >H NMR [400 MHz, DMSO) δ 8.78 (s,lH), 8.05 (dt, J = 8.4,2.2 Hz, 2H), 7.89 (s, IH), 7.73 (dt, J = 7.0,1.8 Hz, 2H ), 7.53 (tt, J = 7.0,1.6 Hz, 2H), 7.47 (tt,J = 7.1,1.2 Hz, IH), 7.37 (dt,J = 8.4,2.1 Hz,2H), 6.97 (s, 1H),4.O8 (s,3H),3.99 (s,3H) ,2.93 (quin, J = 6.8 Hz, IH), 1.18 [d, J = 6.8 Hz, 6H) ^I3 C NMR (101 MHz, DMSO) δ 163.2,160.3,153.2,137.3, 136.7,135.5,133.8, 130.2,129.9,129.8,126.2,118.6,118.0,113.6,112.4, 97.6, 96.5, 58.2, 57.2, 33.7, 23.9 ληκχ= 330 nm, e _max = 17650 dm ^s -mol ¹ -cm ^{1 100p} Y Ή NMR (400 MHz, DMSO) δ 8.78 (s, 1H), 8.05 (dt J = 8.7,2.3 Hz, 2H), 7.89 (s, 1H), 7.73 (dt, J = 7.1,1.8 Hz, 2H), 7.55-7.45 (m, 5H), 6.98 (s, IH), 4.09 (s, 3H), 3.99 (s, 3H), 1.26 (s, 9H) ¹³ C NMR (101 MHz, DMSO) δ 163.2,160.4,155.4,137.3,136.7,135.1,133.8, 129.9,129.8,129.1,126.2,118.6,118.0,113.5,112.4, 97.6, 96.5, 58.2, 57.2, 35.3, 31.2 X _max = 330 nm, £ _max = 18100 dnP-moH-crrr ¹

Example 9. Preparation of diaryliodonium salts coordinated with the 2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium cation and various anions.

PL 240 445 Β1

STEP 1 - Synthesis of (Z)-3-(3,5-dimethoxyphenyl)-2-phenylprop-2-enenitrile (number 24-139)

Phenylacetonitrile (0.1 mol) and 3,5-dimethoxybenzaldehyde (0.1 mol) were dissolved in methanol (100 ml), sodium methoxide (0.11 mol) was added and the reaction mixture was stirred at room temperature until the starting materials were consumed. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, methanol was stripped off under reduced pressure, water (100 ml) was added to the residue and the resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Then, the crude product was purified by column chromatography to obtain a yellow solid.

Spectral data:

(Z)-343,5-dimethoxypheny]o)-2-phenylprop-2-enenitrile (number 24-139) >H NMR (400 MHz, DMSO) 87.99 (s, 1H), 7.78-7.75 (m, 2H), 7.53 (mp, J = 7.0, 2.1Hz,2H), 7.46 (mp, J = 7.1, 2.2 Hz, 1H), 7.16 (d, J= 2.2 Hz, 2H). 6.67 (t. J = 2.3 Hz, 1H). 3.81 (p. 6H)

STEP 2 - Synthesis of iodonium salts coordinated with 2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium cation and various anions

To a solution of the stilbene derivative from the previous step, i.e. (Z)-3-(3,5-dimethoxyphenyl)-2-phenylprop-2-enenitrile (0.01 mol) and diacetoxyiodobenzene (0.01 mol) in glacial acetic acid (50 ml), p-toluenesulfonic acid (0.01 mol) was added and the mixture was stirred at room temperature until the starting materials had reacted. The progress of the reaction was monitored using thin layer chromatography (TLC). KPFs (0.01 mol) and acetic anhydride (10 ml) were then added and stirring continued for 5 min. Water (250 ml) was added and the mixture was stirred for a further 30 min. The resulting precipitate was filtered off, washed with water and diethyl ether, then dried in vacuo.

Inorganic and organic-inorganic salts used for this reaction step, depending on the obtained iodonium salt derivative with the center in the form of the 2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium cation _, were KPFs, NaSbFs, _{NaBF 4} , CF3SO3K, TsONa, ( _C6H5 ) _4BNa , ( _C6F5 ) _4BLi , [Al(OC( _CF3 ) ₃ ) ₄ ]Li.

Spectral data:

^v o ^CN lii οΥχχ PF ₆ TJ Ή NMR (400 MHz, DMSO) δ 8.79 (s, 1H), 8.16-8.13 (m, 2H), 7.90 (s, 1H), 7.757.71 (m, 2H), 7.65 (mp, J = 7.5, 1.1 Hz, 1H), 7.56-7.56 (m, 5H), 6.97 (s, 1H), 4.07 (s, 3H), 3.99 (a, 3H) ¹³ CNMR(101 MHz, DMSO) 8 163.2, 160.4, 137.3, 136.8, 135.3, 133.8, 132.3, 132.0, 129.9, 129.8. 126.2. 118.7, 118.0, 117.0, 112.4, 97.6,96.5, 58.2, 57.2 Amax = 335 nm, Emax = 19600 dm ³ mol' ¹ cm ¹ CN and J SbF _s 1H NMR (400 MHz, DMSO) 8 8.78 (s, 1H), 8.16-8.12 (m, 2H), 7.90 (s, 1H), 7.747.70 (m. 2H), 7.64 (mp. J= 7.5, 1.1 Hz, 1H), 7.55-7.54 (m, 5H), 6.9G (s, 1H), 4.06 (s, 3H), 3.98 (s, 3H) ''o ϊ rS σ ^b ^ ^_ Ή NMR (400 MHz, DMSO) 8 8.80 (s, 1H), 8.17-8.15 (m, 2H), 7.91 (s, 1H), 7.757.71(m, 2H). 7.65 (t. J = 7.5, 1.1 Hz, 1H), 7.54-7.56(m, 5H), 6.96 (s, 1H4.05 (s. 3H), 3.97 (s, 3H) this /---- Ή NMR (400 MHz, DMSO) δ 8.79 (s, IH), 8.16-8.13 (m, 2H), 7.90 (s, 1H), 7.757.71 (m,2H), 7.65 (mp. J= 7.5, 1.1 Hz, 1H), 7.56'7.56 (m, 5H),), 7.19 (dd, J = 9.0, 3.2 Hz, 1H), 7.109 (d, J = 7.9 Hz, 2H), 6.97 (s, 1H), 4.07 (s, 3H), 3.99 (s, 3H), 2.29 (s , 3H)

PL 240 445 Β1

^CN n ΟχΓ ⁰ ' L JJ TfO Ή NMR (400 MHz, DMSO) 8 8.78 (s, 1H), 8.17-8.13 (m. 2H), 7.90 (s, 1H), 7,757.71 (m, 2H), 7.65 (mp, J = 7.5, 1.1 Hz, 1H), 7.56-7.54 (m. 5H), 6.96 (s, 1H), 4.07 (s, 3TT), 3.98 (s, 3TT) ''o ΉNMR (400 MHz, DMSO) δ 8.81 (s, ITT), 8.16-8.12(m, 2TT), 7.91 (s, ITT), 7.757.71 (m,2H), 7.64(mp. J = 7.5, 1.1 Hz. 1H), 7.56-7.55 (m. 5H). 6.97 (s, 1H), 4.07 (s. CN X °' 311), 3.99 (p. 311) Ή NMR (400 MTTz, DMSO) δ 8.81 (s, ITT), 8.16-8.10(m, 2TT), 7.91(s, ITT), 7.807.70 (m, 2H), 7.64(mp. J = 7.5 , 1.1 Hz, 1H), 7.56-7.55 (m. 5H). 6.90 (s, 1H), 4.07 (s. CN Γ T AI(OC(CF^ ₄ 311), 3.90 (p. 311)

Example 10. Preparation of diaryliodonium salts coordinated with cationic centers based on different chromophores

STEP 1 - Synthesis of intermediate products

Acetonitrile derivative (0.1 mol) and 3,5-dimethoxybenzoic aldehyde (0.1 mol) were dissolved in methanol (100 ml), sodium methoxide (0.11 mol) was added and the reaction mixture was stirred at room temperature until the starting materials were consumed. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, methanol was stripped off under reduced pressure, water (100 ml) was added to the residue and the resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Then, the crude product was purified by column chromatography to obtain a yellow solid.

(1-naphthyl)acetonitrile or (2-naphthyl)acetonitrile were used as acetonitrile derivatives, respectively.

Spectral data:

(Z)-2-cyano-2-(lnaphthyl)vinyl]-4,6dim e thoxyphenyl (26-124) Ή NMR (400 MHz, DMSO) δ 8.14 - 8.03 (τη, 2H), 7.93 - 7.86 (m, 2H), 7.67 - 7.56 (m, 4H), 6.38 (t, J = 2.3 Hz, 1H), 6.17 ( d, J = 2.2 Hz, 2H), 3.35 (s, 3H). (Z)-2-cyano-2-(2naphthyl)vinyl 1-4,6dimethoxyphenyl (number 26-077) Ή NMR (400 MHz, DMSO) 6 8.26 (d, J = 1.5 Hz, 1H), 8.15 (s, 1H), 8.078.04 (m, 2H), 8.00-7.94 (m. 2H), 7.61-7.58 ( m, 2H), 7.21 (d, J = 2.2 Hz, 2H). 6.68 (t. J = 2.2Hz, 1H). 3.83 (s, 6H)

PL 240 445 Β1

STEP 2 - Synthesis of diaryliodonium salts coordinated with cationic centers based on different chromophores

The synthesis was carried out in a similar manner to that in Example 9, step 2, but (Z)-2-cyano-2-(1-naphthyl)vinyl]-4,6-dimethoxyphenyl (number 26-124) or (Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6-dimethoxyphenyl (number 26-077) was used as the stilbene derivative.

Spectral data:

OK' -D ““W ^-0 Ή NMR (400 MHz, DMSO) δ 8.21 (dd, J = 7.9,1.1 Hz, 1H), 8.16 (d, J = 8.0 Hz, 1H), 8.11 (dd, J = 7.2,1.7 Hz, 1H), 8.04 (s, 2H), 8/03-8/02 (m, 1H), 7.77-7.63 (m, 5H), 7.50 (tt, J = 7.6,1.8 Hz, 2H), 7.45 (d, J = 2.6 Hz, 1H), 6.98 (d, J = 2.6 Hz, 1H), 4.02 (s, 3H),3.97(s, 3H) ¹³ C NMR (101 MHz, DMSO) δ 164.9,159.3,148.3,140.0,135.1,133.8,132.3, 132.1,131.9,130.9,130.4,129.8,128.5,127.8,127.3,126.2,124.9,117.6, 117.5, 116.9,109.6,100.8,98.9, 58.1, 56.9 Amax= 335 nm, E _max = 10200 drnS-moH-cm ⁴ CN COĆK Cj ^pf6 ” iH NMR (400 MHz, DMSO) δ 8.34 (s, 1H), 8.32 (d, J = 1.2 Hz, 1H), 8.18-8.11 (m, 2H), 8.08-8.03 (m, 2H), 8.01 (d, J = 7.9 Hz, 2H), 7.68-7.62 (m, 3H), 7.47 (t, J = 7.7 Hz, 2H), 7.26 (d, J = 2.4 Hz, 1H), 6.95 (d, J = 2.4 Hz, 1H), 4.01 (s, 3H), 3.93 (s, 3H) ^1S C NMR (101 MHz, DMSO) δ 164.7,159.3,142.7,140.6,135.3,133.9,133.1, 132.3,132.0,130.3,129.6,129.1,128.5,128.2,127.8,127.2,125.9,123.3, 119.1,116.9,116.8,109.6,100.6,99.0, 58.0, 56.8 315 nm, ε,η,,χ = 18200 dm ³ -mol' ¹ -cm· ¹

Example 11. Synthesis of diaryliodonium salts coordinated with 2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]aryliodonium cations obtained in reactions with various diacetoxyiodobenzene derivatives

STEP 1 - The synthesis of (Z)-3-(3,5-dimethoxyphenyl)-2-phenylprop-2-enenitrile (number 24-139) was carried out in a similar manner to example number 9, step 1.

STEP 2 - Synthesis of diaryliodonium salts coordinated with 2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]aryliodonium cations formed in reactions with various diacetoxyiodobenzene derivatives.

To a solution of the stilbene derivative from the previous step, i.e. (Z)-3-(3,5-dimethoxyphenyl)-2-phenylprop-2-enenitrile (0.01 mol) and the corresponding diacetoxyiodobenzene derivative (0.01 mol) in glacial acetic acid (50 ml), p-toluenesulfonic acid (0.01 mol) was added and the mixture was stirred at room temperature until the starting materials had reacted. The progress of the reaction was monitored using thin layer chromatography (TLC). KPFs (0.01 mol) and acetic anhydride (10 ml) were then added and stirring was continued for 5 min. Water (250 ml) was added and the mixture was stirred for a further 30 min. The resulting precipitate was filtered off, washed with water and diethyl ether, then dried in vacuo.

Diacetoxyiodobenzene derivatives were chemical compounds from the group including diacetoxyiodo-4-methylbenzene, 4-tert-butyl-diacetoxyiodobenzene, 4-isopropyl-diacetoxyiodobenzene, diacetoxyiodo-2,1,6-trimethylbenzene.

PL 240 445 Β1

Spectral data:

^X Oh oh ^3H NMR (400 MHz, DMSO) δ 8.17 (s, 1H), 7.90 (dt, J = 8.3, 2.0 Hz, 2H), 7.85 (dt, J = 7.0,1.7 Hz, 2H), 7.65-7.55 (m , 3H), 7.28 (d, J = 8.4 Hz, 2H), 7.20 (d, J = 2.4 Hz, 1H), 6.92 (d, J = 2.5 Hz, 1H), 4.00 (s, 3H], 3.91 (s, 3H), 2.34 (s, 3H) ¹³ C NMR (101 MHz, DMSO] δ 164.4,159.2,142.7,142.5,140.3,135.3,132.8, 132.6,130.8,129.9,126.9,118.9,116.8,113.2,109.4,100.6,99.1,58.0, 56.7, 21.3 /.„--<=300 nm, ε _η ™ = 15550 dm^moB-cm ¹ ^0 CN [pA OAA ^3H NMR (400 MHz, DMSO) δ 8.16 (s, 1H), 7.89 (dt, J = 8.4, 2.2 Hz, 2H), 7.857.82 (m, 2H), 7.64-7.55 (m, 3H), 7.33 (dt, J = 8.4,2.2 Hz, 2H), 7.19 (d, J = 2.4 Hz, 1H], 6.94 (d, J = 2.5 Hz, 1H), 4.02 (s, 3H), 3.91 (s, 3H), 2.92 (quin, J = 6.8 Hz, 1H), 1.17 (d, J = 6.8 Hz, 6H] ¹³ C NMR (101 MHz, DMSO) 6 164.7,159.2,153.2,142.4,140.4,135.4,132.7, 130.8,130.1,129.9,126.9,119.0,116.7,113.5,109.5,100.6,99.0,58.0, 56.8, 33.7, 23 9 Amax=305 nm, £. _TE = 16250 dm ³ mol · ¹ · cm ¹ Ό □Aj' 1H NMR (400 MHz, DMSO] δ .16 (S, 1H), 7.90 (dt, J = 7.9,2.1 Hz, 2H), 7.85-7.82 (m, 2H), 7.65-7.55 (m, 3H), 7.35 (dt, J = 8.6,1.7 Hz, 2H), 7.19 (d, J = 2.4 Hz, 1H], 6.95 (d, J = 2.4 Hz, 1H], 4.02 (s, 3H), 3.91 (s, 3H), 1.26 (s, 9H) ¹³ C NMR (101 MHz) , DMSO] δ 164.9,159.2,153.2,142.3,140.4,134.9,132.3, 130.8,130.0,129.7,126.9,119.3,117.0,113.3, 109.5,100.6,99.2,58.0, 56.8, 35.3, 31 3 = 305 nm, emax= 15350 dm ³ 'mol ¹ 'Cm ¹ —Aą· ' o HI NMR (400 MHz, DMSO) δ 8.17 (s, 1H], 7.74-7.71 (m, 2H], 7.64-7.57 (m, 3H), 7.19 (d, J = 2.6 Hz, 1H), 7.06 (s, 2Η), 6.92 (d, J = 2.6 Hz, 1H), 3.91 (s, 3H], 3.90 (s, 3H), 2.39 (s, 6H), 2.27 (s,3H) , 130.2,129.9,126.6,121.8,118.8,116.4,110.0, 100.9,95.4, 57.8, 56.8,25.9, 20.8 Afnax= 305 nm, ε™ = 14850 dm^moB-cnr ¹

Example 12. Preparation of diaryliodonium salts coordinated with the [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium cation and various anions

STEP 1 - Synthesis of (Z)-3-(2,6-dimethoxyphenyl)-2-phenylprop-2-enenitrile (number 26-053)

Phenylacetonitrile (0.1 mol) and 2,6-dimethoxybenzaldehyde (0.1 mol) were dissolved in methanol (100 ml), sodium methoxide (0.11 mol) was added and the reaction mixture was stirred at room temperature until the starting materials were consumed. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, methanol was removed under reduced pressure, water (100 ml) was added to the residue and the resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Then, the crude product was purified by column chromatography to obtain a yellow solid.

Spectral data:

(Z)-3-(2,6'diine toxiphenyl)-2phenylprop-Ż-enonitrile (number 26-053) Ή NMR (400 MHz, DMSO) 6 7.73-7.70 (m, 2H). 7.51 (lt, J = 6.0. 1.9 Hz. 2H). 7.45 (dt, J = 7.0, 1.3 Hz, 1H), 7.42 (t, J = 8.5Hz, 1H), 6.78 (d, J = 8.6 Hz, 2H), 3.83 (s, 6H)

STEP 2 - Synthesis of diaryliodonium salts coordinated with [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium cation and various anions

PL 240 445 Β1

To a solution of (Z)-3-(2,6-dimethoxyphenyl)-2-phenylprop-2-enenitrile from the previous step (0.01 mol) and diacetoxyiodobenzene (0.01 mol) in glacial acetic acid (50 ml) was added p-toluenesulfonic acid (0.01 mol) and the mixture was stirred at room temperature until the starting materials had reacted. The progress of the reaction was monitored by thin layer chromatography (TLC). KPFe (0.01 mol) and acetic anhydride (10 ml) were then added and stirring was continued for 5 min. Water (250 ml) was added and the mixture was stirred for a further 30 min. The resulting precipitate was filtered off, washed with water and diethyl ether, then dried in vacuo.

The salts used for this stage of the synthesis, depending on the obtained iodonium salt derivative with the center in the form of the [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium cation, were KPFs, NaSbFs, NaBF ₄ , CF3SO3K, TsONa, (C ₆ H ₅ ) ₄ BNa, (C ₆ F ₅ ) ₄ BLi, [Al (OC(CF ₃ ) ₃ ) ₄ ]Li.

Spectral data:

□_ / U/ Ή NMR (400 MHz, DMSO) δ 8.18 (s, 1H), 8.00 (dt, J = 7.4. 1.0 Hz. 2H), 7.84 (dt, J = 7.0, 1.4 Hz, 2H). 7.66-7.57 (m. 4H), 7.47 (tt, J = 7.8, 1.4 Hz, 2H), 7.21 (d, J = 2.5 Hz, 1H), 6.94 (d. J = 2.5 Hz, 1H), 3.99 fe, 3H), 3.92 (s, 3H) ^1S C NMR (101 MHz. DMSO) δ 162.4. 157.5. 139.4, 135.1, 134.9,133.0,132.3, 132.1, 130.4. 129.8, 126.4. 118.9. 118.5. 117.2, 116.9, 110.9, 104.2, 63.5, 57.3 Amaa — 290 nm, iw, — 17300 dm^-mol' ¹ cm' ¹ \ Che SbFg Ή NMR (400 MHz, DMSO) δ 8.16 (s, 1H), 8.02 (dt, J = 7.2, 1.0 Hz. 2ID. 7.82 (dt, J = 7.1, 1.6 Hz, 2H), 7.65 7.57 (ni. 4H) .7.42 (tt, J = 7.3, 1.1 Hz, 2H). 7.23 (d, J = 2.2 Hz, 1H), 6.93 (d, J = 2.5 Hz, 1H), 4.01 (s, 3H) ^1S C NMR (101 MHz, DMSO) 5 162.2, 157.5, 139.6, 135.0, 134.8, 133 3. 132.4, 132.1, 130.4, 128.2, 126.5, 118.7, 118.5, 117.4, 116.8, 111.1, 104.5, 63.6, 57.5 λι^„, = 29ϋ nm e™ _a » = 17350 dm ⁵ mol ¹ cm ^{1 1} EF _d Ή NMR (400 MHz. DMSO) 8 8.13 (p. 1H), 8.01 (dt, J = 7.0, 1.1 Hz, 2H). 7.85 (dt, J = 7.3, 1.2 Hz, 2H), 7.66-7.57 (m, 4H), 7.43 (tt. J = 6.9, 1.0 Hz, 2H>. 7.24 (d, J = 2.0 Hz. 1H). 6.94 (d, J = 2.3 Hz. 1H), 3.99 (p. 3H) i'C NMR (101 MHz, DMSO) δ 162.3, 139.5, 135.1. 119.1. 118.7. 117.5, 116.8, 110.9, 104.3, 63.4. 57.0 .Xma _a = 295 nm ε,™» = 16900 dm^mol' ¹ cm ¹ fj 'b Ή NMR (400 MHz. DMSO) δ 8.47 (d, J = 9.1 Hz, 1ID 8.15 (dt, J = 7.2. 1.5 Hz. 2Π). 7.88 (s IIP, 7.79-7.76 (m, 2Π), 7.64 (tt , J = 7.4, 1.0 Hz, III), 7.56-7.46 (m, 7H). 7.14-7.10 (m. 3H), 3.77 (s, 3H), 2.29 (s, 3H) ^1S C NMR (101 MHz. DMSO) 5 162.3. 157.5. 138.0, 135 1.135.0. 133.0, 132.2, 132.1, 130.4. 129.8. 128.5. 126.4, 125.9, 118.9, 117 3, 116.9, 110.9, 104.3,63.5, 57.3, 21.2 Amaa— 290 nm. Εειηχ = 17000 dm ³ mol ¹ cm' ¹ ''o ,UXjO u X ^x TfO Ή NMR (400 MHz. DMSO) δ 8.17 (p. 1H), 8.00 (dt, J = 7.2, 1.2 Hz, 2H). 7.84 (dt. J = 7.3, 1.4 Hz. 2H), 7.68-7.60 (m. 4H). 7.47 (t. J = 7.7, 1.2 Hz, 2H). 7.21 (d, 4 = 2.6 Hz. 1H). 6.93 (d, J = 2.9 Hz. 1H), 3.99 fe. 3W. 3.92 (p. 3H) ^1S C NMR (101 MHz, DMSO) δ 162.2, 157.4, 139.7, 135.3, 135.1. 133.3. 132.3. 132.1,130.8, 129.3, 126.4, 122.8. 118.8, 118.8, 117.0. 117.1, 111.1, 104.5, 63.6, 57.6 λιη9κ= 290 nm Smux = 1G700 dn^-mol · ¹ cm' ¹ Ib 1 Ή NMR (400 MHz, DMSO) 8 8.18 (s, III), 8.00 (dt, J = 7.6, 1.4 Hz. 211), 7.85 (dt. J = 7.2, 1.9 Hz. 211), 7.65'7.59 (m, 4ID, 7.48 (tt, J = 7.3, 1.2 Hz. 2IP, 7.21 (d, J = 2.5 IIz. UD. 6.96 (d, J = 2.3 Hz, 11D, 3.99 fe, 3IP, 3.92 (s, 311) ¹³ C NMR (101 MIIz, DMSO) δ 162.6, 157.7, 149.2, 146.7, 139.8,139.2, 135.0, 134.9, 133.4, 133.3, 132.2, 132.1, 130.9, 129.5, 126.0. 119.2. 118.3, 117.5, 117.0. 110.8. 104.2, 63.4, 57.4 Anaa = 295 lim. 'r.. = 16350 duDuml ¹ tm ¹ 1 Q ? ⁺ - 0 / ⁰ uu ¹ b U/ ^l H NMR (400 MHz, DMSO) δ 8.25 (s, 1H), 8.05 (dt, J = 7.6, 1.4 Hz. 2H), 7.85 (dt, J = 7.2, 1.9 Hz. 2H), 7.65-7.59 (m .4H). 7.45 (t. J = 7.3, 1.2 Hz, 2H). 7.21 (d, J = 2.5 Hz, 1H). 6.96 (d, .1 = 2.3 Hz. 1H), 3.95 (p. 3H). 3.88 (p. 3H) 296 nm, em* = 16350 dm^mol ¹ cm' ¹

Example 13. Preparation of diaryliodonium salts coordinated with the [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium cation and various anions

PL 240 445 Β1

STEP 1 - Synthesis of (Z)-3-(2,4,6-trimethoxyphenyl)-2-phenylprop-2-enenitrile (number 26-051) Phenylacetonitrile (0.1 mol) and 2,4,6-trimethoxybenzaldehyde (0.1 mol) were dissolved in methanol (100 ml), sodium methoxide (0.11 mol) was added and the reaction mixture was stirred at room temperature until the starting materials were consumed. The progress of the reaction was monitored using thin layer chromatography (TLC). Then, methanol was stripped off under reduced pressure, water (100 ml) was added to the residue and the resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. The crude product was then purified by column chromatography to afford a yellow solid.

Spectral data:

(Z) 3 * (2,4.6 t rim e t o x y £e ny lo) 2 phenylprop-2-enonitrvl (number 26Ό51) Ή NMR (400 MIz, DMSO) 8 7.66 (dt, J = 7.6, 16 Hz, 2ID. 7.60 fe, III), 7.48 (mp, J = 7.8, 1.5 Hz, 2H), 7.41 (ll, J= 7.2, 1.4 Hz 1H), 6.35 (s, 2H), 3.86 (s, 3H), 3.84 fe, 6H)

STEP 2 - Synthesis of diaryliodonium salts coordinated with [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium cation and various anions

To a solution of (Z)-3-(2,4,6-trimethoxyphenyl)-2-phenylprop-2-enenitrile from the previous step (0.01 mol) and diacetoxyiodobenzene (0.01 mol) in glacial acetic acid (50 ml) was added p-toluenesulfonic acid (0.01 mol) and the mixture was stirred at room temperature until the starting materials had reacted. The progress of the reaction was monitored by thin layer chromatography (TLC). KPFe (0.01 mol) and acetic anhydride (10 ml) were then added and stirring was continued for 5 min. Water (250 ml) was added and the mixture was stirred for a further 30 min. The resulting precipitate was filtered off, washed with water and diethyl ether, then dried in vacuo.

The salts used for this stage of the synthesis, depending on the obtained iodonium salt derivative with the center in the form of the [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6 _- trimethoxyphenyl]-phenyliodonium cation, were KPFs, NaSbFe, NaBF ₄ , CF3SO3K, TsONa, ( _C6H5 ) _4BNa , ( _C6F5 ) _4BLi , _[ Al(OC( _CF3 ) ₃ ) ₄ ]Li.

Spectral data:

oh ^— ₊ oh — 1H NMR (400 MHz. DMSO) 6 8.05 (dt, J = 7.1, 1.2 Hz, 2H), 7.80 fe, 1H). 7.76 (dt, J = 6.8, 1.5 Hz. 2H). 7.64 (tt, J = 7.4, 1.0 Hz. 1H), 7.54 (tt, J = 6.8, 1.8 Hz, 2H), 7.49 (tt, J = 7.7, 1.5 Hz, 3H), 6.85 fe, 1H), 4.10 ( s, 3H), 3.98 (s, 3H). 3.81 (p. 3H) i»C NMR (101 MHz, DMSO) 8 164.0, 160.4, 158.9. 135.0, 134.8, 133.4, 132.2. 132.1, 130.2, 129.8, 126.2, 117.9, 117.2. 116.9, 110.9, 95.6, 93.8, 63.5, 58.3, 57.3 A _max = 315 nm, emns = 15800 dm ³ mor ^l -cm' ¹ 'o ¹ χυχο L JJ o. SbF ₆ “ Ή NMR (400 Ml Iz, DMSO) 8 8.06 (dt, J = 7.5, 1.3 Hz, 211), 7.80 fe, 111),7.77 (dt, J = 7.1, 1.7 Hz. 2H). 7.64 (tt, J = 7.3, 1.3 Hz. 1H), 7.55 (tt, J = 6.9, 1.4 Hz, 2H), 7.50 (tt, J = 7.6. 1.4 Hz, 3H), 6.87 (s, 1H). 4/09 fe. 3H), 3.98 Cs, 3H), 3.80 fe, 3H) ¹³ C NMR (101 MHz. DMSO) 8 164.5, 160.5, 159.0, 135.2, 134.8. 133.4, 132.8, 132.0, 130.2, 129.6, 126.3, 117.3, 117.2, 116.8, 110.8, 95.4, 93.3, 63.6, 58.5, 57.2 Amax = 315 nm, s _max = 16050 dm ³ mol ¹ -cm ¹ ΟΧ ^v bf ₄ Ή NMR (400 MHz, DMSO) 8 8.06 (dt, J = 7.0, 1.2 Hz, 2H), 7.80 fe, 1H), 7.75 (dt, J = 6.9. 1.9 Hz, 211), 7.65 (tt, J = 7.4 , 1.2 Hz, 111), 7.55 (tt, J = 7.2, 1.2 Hz, 2H), 7.49 (tt, J = 7.8, 1.3 Hz, 3H). 6.85 fe, 1H). 4/10 fe. 3H), 3.99 (s, 3H), 3.81 fe, 3H) ¹³ C NMR (101 MHz, DMSO) 8 164.2, 160.3, 158.9, 135.0, 134.5,133.3, 132.7, 132.3, 130.8, 129.7, 126.5, 117.9, 117.5, 117.2, 111.4, 95.5, 93.2, 63.4, 58.1, 57.3 A _m ax = 310 nm, Smax = 16100 dm ³ mol ¹ tm ¹

PL 240 445 Β1

t 1H NMR (400 Ml Iz, DMSO) 8 8 8.04 (d, J = 8.0 Hz, 211). 7.80 (s, 111), 7 78-7.74 (ni, 21D, 7.63 (t. J = 7.3 Hz, 111). 7.56'7.45 (m, 71D, 7.11 (d, J = 7.9 Hz, 21D, 6.84 (s , 1H). 4/09 (p, 3H). 3.97 (s, 3H), 3.80 (s, 3H) ^I3 C NMR (101 MHz, DMSO) δ 164.0, 158.9, 146.2, 135.0, 134.9, 132.1. 130.1, 129.8, 128.5, 126.2, 125.9, 117.8, 117.2, 116.9, 110.8, 95.7, 93.8, 63.5, 58.3,57.3, 21.2 310 nm, = 15850 dm ³ -mol ¹ rm ¹ T jO ^v TfO Ή NMR (400 MHz, DMSO) 6 8.07 (dt, 4 = 7.5, 1.7 Hz, 2H), 7.81 (s, 1H). 7.74 (dt, J = 8.0, 1.6 Hz, 2H), 7.63 (tt, J = 7.9, 1.4 Hz, 1H). 7.57 (tt, J = 6.6, 1.9 Hz, 2H), 7.49 (tt, J = 7.7, 1.3 Hz, 3H), 6.86 (s, 1H), 4.10 (s, 3H), 3.98 (s, 3H), 3.81 (p, 311) ¹³ CNMR(101MHz, DMSO) 8 164.0, 160.4, 159.2, 135.2, 134.9, 133.8, 132.5, 132.2, 130.2. 130.0, 126.5. 122.7. 117.8, 117.2. 116.9, 110.8. 95.4, 93.6. 63.4. 58.4. 57.3 Amax = 315 nm, Eman = 16450 dm ³ Tnol' ¹ wn' ¹ and * I HI NMR (400 MHz, DMSO) δ 8.03 (dt, J = 7.5, 1.6 Hz, 2H), 7.81 (s, 1H), 7.75 (dt. J = 6.8, 1.8 Hz, 211), 7.64 (tt, J = 7.4, 1.4 Hz, III). 7.53 (tt, J = 6.6, 1.4 Hz, 2H), 7.51 (tt, J = 7.4, 1.8 Hz, 3H). 6.86 (s, 1H), 4.11 (s, 3H), 3.98 (s, 3H), 3.82 (s, 31D ¹³ C NMR (101 MHz. DMSO) δ 164.3, 160.8, 158.7, 149.1, 146.7, 139.6, 134.8. 134.7, 133.4, 133.3, 132.2, 132.1, 130.5, 129.4, 126.6, 117.4, 117.5, 111.2, 95.9, 93.6, 63.4, 58.3, 57.3 Amax= 315 nm, and ¹ ™. - 16250 dm ⁸ mol · ¹ cm' ¹ Ł 1 ° ] o ^r i Ή NMR (400 MHz, DMSO) 8 8.13 (dt, J = 7.5, 1.6 Hz, 2H), 7.81 (s, 1H), 7.75 (dt, J = 6.8, 1.8 Hz, 2H), 7.64 (tt, J = 7.4, 1.4 Hz, 1H), 7.53 (tt, J = 6.6, 1.4 Hz, 2H), 7.58 (tt. J = 7.4, 1.8 Hz, 3H). 6.86 (s, 1H). 4.18 (p, 3H). 4.08 (p, 3H). 3.88 (s, 3H) Amax- 316 nm. ema» = 16250 dm ³ mol' ¹ cm' ¹

Example 14. Studies on the absorption characteristics of the obtained iodonium salts in order to determine their suitability as photoinitiators of polymerization processes.

Absorption studies

The absorption measurements of the tested iodonium salts were performed using a Silver Nova spectrometer from StellarNet Inc. (USA), which has a spectral range of 190-1100 nm. The measurements were performed in spectroscopically pure acetonitrile (Sigma Aldrich), using a quartz cuvette with an optical path length of 1 cm. The light source was a deuterium-halogen lamp from StellarNet Inc. (USA). All measurements were performed at room temperature.

It should be noted that stilbene derivatives, which are intermediates in the synthesis of diaryliodonium salts according to the present invention, are chromophores, however, the cationic center of the iodonium salt, in which the chromophore is incorporated, is mainly responsible for the absorption.

In order to test the effectiveness of the compounds that are the subject of the invention as photoinitiators, measurements of their molar absorption coefficients as a function of wavelength were performed. Table 2 compares the obtained values of molar absorption coefficients at the maximum of the absorption band and at wavelengths characteristic for the maximum emission of medium-pressure mercury lamps, i.e. 365 nm and UV-LED diodes 365 nm and Vis-LED 405 nm.

The values of the same parameter for commercial photoinitiators with the same or different anion are also presented.

PL 240 445 Β1

Table 2. Quantitative parameters describing the absorption properties of iodonium salts being the subject of the present invention and commercially available photoinitiators.

Union No. Structure Amax [nm] Cmax [dm ⁵ mol ¹ cm '] eaes [dm ⁵ mol ¹ cm 4 £405 [dm ⁵ mol ¹ cm 4 .And atOTyhandiowe £ * Ql.Pl.0i©· HIP References 228 14600 0 0 Rhodosil 2074 237 17470 0 0 Speedcure 938 pbcp 242 16503 0 0 Omnicat440 PFe 00 ¹ Ό 241 13830 0 0 Irgacure 250 ΧΤ'Ό. 242.1 14522 0 0 cation according to invention Kku 2 diff. the ones pLŁdłiiii [3-|(Z)-2-cyano-2phenylvinyl]-4-methoxyphenyl|phenyliodonium hexafluorophosphate 24-087 u ó 0 00 321 14000 4300 325 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl|phenyliodine hexafluorophosphate 26-027 K 9 O - 0^1 336 20000 13700 560 [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl|phenyliodonium hexafluorophosphate 26-026 0Tb 00 294 18800 980 45 [2-|(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate 24-151 ^PF ~ 302 17000 1440 245 [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl|phenyliodonium hexafluorophosphate 26-069 00 Z°y7 b’ 286 17400 260 120 [3-|(Z)-2-cyano-2phenylvinyl]-2,4,6-trimethoxyphenyl]phenyl iodonium hexafluorophosphate 26-088 1 1 O O λ. Γ ΤΎ iTti 313 16000 2700 305

PL 240 445 Β1

Iodonium salts based on l3-[(Z^2-cyanó-2-ą^ cationic centers Stem. . . .. BASIC SYSTEM No. 1: |3-[(Z)-2-cyano-2phenyvinyl]-4methoxyphenyl]phenyliodonium hexafluorophosphate 24-087 Ol FF _e 321 14000 4300 325 [3-[(Z)-2-cyano-2-{2-naphthyl)vinyl]4-methoxyphenyl|phenyliodonium hexafluorophosphate 26-101 O. ^PFr COo 335 11300 7500 770 (lojodsnK coordinatedżceh based on the 2 ((Ζ) 2 cyano 2 iodine system Basic system no. 3: |2-[(Z)-2-cyano-2- phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate 24-151 '9 dr 302 17000 1440 245 [2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate 26-082 coPP ^PF * 315 18200 7500 650 Benefits ocphonium coordinated with the cation [5-[(Z)-2-cyano-2-phenylovnyl]-2,4-dfrinet< and phenyphoiodomic acid and various anions ¹ xyphenyfo]- |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl|phenyliodonium hexafluorophosphate 26-027 H ^PR si CN 336 20000 13700 560 |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluoroantimonate 25-099 Έρ /° W “ 8 ο- 336 18300 10600 610 |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tetrafluoroborate 25-100 ¹ m'-- 6 Ρ 336 13800 8000 425 |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium tosylate 25-081 ΛΛ Έρ /Όκ ⁺ g ο— 1 336 10100 6000 385 |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium trifluoromethylsulfonate 25-106 ιΓί ^πο 1 Κ ο ^CN ΙιΔ οΡΡ 336 19300 11200 425

PL 240 445 Β1

|5-[(Z)-2-cyano-2- phenylvinyl]-2,4- dimethoxyphenyl|- phenyliodonium tetrapentafluorophenylborate Preferred Sofa diar 25-076 yiojodontc AND CN coordinated with the price of arylyl]-2,4-dimethox 336 rafnikationt yfehylojfeny 17800 > based on iodonium 10800 jklad [5-1(3-24 . - 1- 775 ;yjano-2- Basic system no. 2: |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl|phenyliodonium hexafluorophosphate 26-027 a, ^pFr 336 20000 13700 560 [5-[(Z)-2-cyano-2-(2cyanophenyl)vinyl]2,4-dimethoxyphenyl]phenyliodine hexafluorophosphate 26-114 CN CN ÓY 339 15500 9600 545 [5-[(Z)-2-cyano-2-(3-cyanophenyl)vinyl]· 2,4-dimethoxyphenyl]phenyliodine hexafluorophosphate 26-102 Oh, ^pFs ~ r rY 342 19300 13400 760 [5-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]· 2,4-dimethoxyphenyl]phenyliodine hexafluorophosphate 25-080 । o —o O < u 352 20500 18000 2400 * Preferred diaryliodonium salts, coordinated with p>'[(Z)-2-cyj dimethoxyphenyl-aryliodonium cationic centers, formed by reactions with various di ano-i-phenylvinylDj-Ż, 4-icetoxyiodobenzetiu. |5-[(Z)-2-cyano-2- phenylvinyl]-2,4-dimethoxyphenyl]-(4-cyanophenyl)iodonium hexafluorophosphate 27-038 La — at 3Y 333 17600 9900 430 |5-[(Z)-2-cyano-2- phenylvinyl]-2,4-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate 26-103 /° o— । 337 15200 9350 300 |5-[(Z)-2-cyano-2- phenylvinyl]-2,4-dimethoxyphenyl]-(3-methoxyphenyl)iodonium hexafluorophosphate 27-048 ''''i i A. .o CN f| 335 18400 10500 560

PL 240 445 Β1

30000

25000

20000 cc f j o 15000 o 7=

O. what £ E S S

10000 oh oh

5000

24-087

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate

26-027

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4di methoxyphenyl]-phenyliodonium hexafluorophosphate

26-026

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate

24-151

[2- [(Z)-2-cyano-2-phenyl vinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate

26-069

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyl iodonium hexafluorophosphate

26-088

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6trimethoxyphenyl]-phenyliodonium hexafluorophosphate

Graph 1. Graph of the extinction versus wavelength dependence of the iodonium salts of the invention coordinated to different cationic centers.

PL 240 445 Β1

Wavelength [nm]

24-087 [3-[(Z)-2-cyano-2-phenylvinyl|-4-methoxyphenyl]phenyliodonium hexafluorophosphate

[3-[(Z)-2-cyano-2-(2-naphthyl)vinyl]4-methoxyphenyl]phenyliodonium hexafluorophosphate

Graph 2. Graph of the extinction dependence on wavelength for diaryliodonium salts coordinated with cationic centers based on [3 Lfe) 2 c^ano 2 arylmyl] 4-methoxyphenylphenyliodonium chromophores.

24-151

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate

26-082 |2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate

Wavelength [nm]

Graph 3. Graph of the extinction dependence on wavelength for diaryliodonium salts coordinated with cation centers based on 2-[(Z)-2-eyjano'2-arylvinyl]4,6-dimethoxyphenyl]phenyliodonium chromophores.

PL 240 445 Β1

Wavelength [nm]

26-027

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate

25-099

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyl-1-cyanoacetate

25-100

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tetrafluoroborate

25-081

[5-[(Z)-2-cya n ο-2-pheny nyl]-2,4dimethoxyphenylj-phenyliodonium tosylate

25-106

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium trifluoromethylsulfonate

25-076

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium tetrapentafluorophenylborate

Graph 4. Graph of the extinction dependence on wavelength for diaryliodonium salts coordinated with the [S-łCZl-Ź-cyano-Ź-phenylmyl-Ź^^dimethoxy^phenyl]· phenyl oj odonium cation and various anions.

PL 240 445 Β1

Wavelength [nm]

26-027

26-114

[5-[(Z)-2-cyano-24-enylvinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate

[5-[(Z)-2-cyano-2-(2-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate

26-102

[5-[(Z)-2-cyano-2-(3-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate

25-080

[5-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-2 _> 4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate

Graph 5. Graph of extinction versus wavelength for diaryliodonium salts coordinated to cationic centers based on [5'f(Z)'2-cyano'2'arylvinyl] 2,4-dimethoxyphenylphenyliodonium chromophores.

PL 240 445 Β1

Wavelength [nm]

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-cyanophenyl)iodonium hexafluorophosphate

26-103

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate

27-048

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-methoxyphenyl)iodonium hexafluorophosphate

Graph 6. Graph of the extinction versus wavelength dependence of diaryliodonium salts coordinated with [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]aryliodonium cationic centers, formed in reactions with various diactyl iodine derivatives.

PL 240 445 Β1

26-101

[3-[(Z)-2-cyano-2-(2naphthyl)vinyl]4methoxyphenyl]phenyliodonium hexafluorophosphate

26-082

[2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate

Figure 7. Extinction versus wavelength graph for diaryliodonium salts coordinated to cationic centers containing naphthylvinyl groups.

Example 15. Study of the kinetics of cationic photopolymerization using the real-time FT-IR method to determine the suitability of the developed iodonium salts as photoinitiators of photopolymerization processes.

For the real-time FT-IR photopolymerization process studies, a Jasco FT/IR-4700 FTIR spectrophotometer equipped with a horizontal attachment was used. A 365 nm UV-LED diode with a nominal power of 190 mW emitting light perpendicularly to the sample surface at a wavelength of Xmax = 365 nm was used as a light source. Measurements were performed for up to 800 seconds, and the obtained data were saved in the SPECTRA MENAGER program, dedicated to the processing of FT-IR spectra. The data were recorded in a darkened room, in which only lamps emitting red light were used as lighting.

Preparation of samples for monitoring the photopolymerization process using the real-time FT-IR method

Compositions for real-time FT-IR studies were prepared in vials made of dark amber glass in a darkened room. Each composition contained 2% by weight of iodonium initiator in relation to the total composition, which was an epoxy monomer in the form of a cycloaliphatic epoxy resin with the acronym CADE manufactured by Lambson. A drop of the prepared measuring composition was applied using a glass pipette to a pellet made of barium fluoride with a diameter of φ = 25 ± 0.2 mm x 5 ± 0.1 mm in the case of monitoring cationic photopolymerization processes. After this operation, the pellet was placed on a metal holder and placed in the horizontal attachment of the spectrometer. Measurements were performed maintaining the same thickness of the applied composition layer, which was 25 µm, respectively. After 10 seconds from starting the MENAGER SPECTRA software, which records the IR spectrum, the UV-LED emitting light at a wavelength of Xmax = 365 nm was turned on. All compositions were tested in a room with limited access to daylight. Thanks to the combination of recording the infrared spectrum of individual compositions over time, while simultaneously exposing the sample to a given light source, it is possible to observe the photopolymerization reaction in real time. Change in peak intensity at appropriate wave numbers:

PL 240 445 Β1 • For cationic photopolymerization of epoxy monomer CADE (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate manufactured by Lambson) at 790 cm' ¹ and 1080 cm' ¹ • For cationic photopolymerization of vinyl monomer TEGDVE (triethylene glycol divinyl ether manufactured by Sigma Aldrich) at a band length of 1630 cm' ¹ • For free-radical photopolymerization of acrylic monomer TMPTA (trimethylolpropane triacrylate manufactured by Sigma Aldrich) at a band length of 1635 cm 1 indicates an efficient course of photopolymerization process. The conversion of functional groups can be calculated from the following formula:

K=(1-(A/A _O ))*100% where:

K - conversion

A - value of the band surface area monitored during the photopolymerization process as a function of time

Ao - initial value of the band area at the monitored wavenumber • Cationic photopolymerization of the epoxy monomer CADE (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) at a wavelength of 365 nm.

Table 3. Data collected during measurements of the ring-opening photopolymerization process of epoxy monomer at a wavelength of 365 nm and a power of 700 mA using the FT-IR technique in compositions containing iodonium salts of the present invention or commercial photoinitiators.

and - that's it * ^{4 1} - - STrukhW» ' ¹ KwwwjyH - Monnmoir epoxy ΓΛΗΕ , - ¹ Handlom, diarylhydric acid salts ΠΙΡ 0 Rhodosil 2074 F F 0 Speedcure 938 FFs 0 Omnicat 440 PF _e 0

PL 240 445 Β1

Irgacure 250 PFj 0 Preferred diaryliodont salts < ' coordinated with different cationic centers [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate 24-087 About P W 68 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-methoxyphenyl]-phenyliodonium hexafluorophosphate 26-027 Έρ O - 87 [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate 26-026 ^v o CT ^PFe 87 [2-[(Z)-2-cyano-2-phenylvinyl]-4,6dimethoxyphenyl]phenyl iodine hexafluorophosphate 24-151 X iS pf ₅ ν j 80 [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-188 1 1 _Λ χΧΧ O κι- ₆ 35 . ’ jgw and various cationic centers iBeS [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate 24-087 Ol - ^A|* PF _e CN 68 [3-|(Z)-2-cyano-2-(2-naphthyl)vinyl)4-methoxyphenyl]phenyliodonium hexafluorophosphate 26-101 Cl J* ^p F _s CN li^ 87 [2-[(Z)-2-cyano-2-phenylvinyl]-4,6dimethoxyphenyl]phenyl iodonium hexafluorophosphate 24-151 Oh, 80 [2-[(Z)-2-cyano-2-(2-naffyl)vinyl]-4,6dimethoxyphenyl]phenyl iodonium hexafluorophosphate 26-082 ^x o CN ^PF S 66

PL 240 445 Β1

ĄKorzy&iiosotedfar^kijodotyaw^ cationic systems based on the P l(Z)-2 cyan system with aiylifflnylcj^i-dimetokś^ [5-[(Z)-2-cyano-2-(2-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-114 cn cn ri^r' ⁰ XX 83 [5-[(Z)-2-cyano-2-(3-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-102 Ol . ^pf ' ^{_ NC} >*^xJ%JAJ 89 [5-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate 25-080 Ol ^ρρ ' ^_ I CN 78 according to ..l^gi^fitnejatela^iodpniomikodfdyhoi^ « ^ł &fihet<^syf^ were formed in the reaction of rifflni later on dhymi diacetoxyiodobentenO' [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate 26-103 । m —o 0 < Z / \ 88 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-cyanophenyl)iodonium hexafluorophosphate 27-038 Ti ^pF <> I CN jiy ⁰ 79 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-methoxyphenyl)iodonium hexafluorophosphate 27-048 A JlS° AJ a 86 - / The preferred diaryliodonium salts^coordinated dlmptokeyphenylolaiyliodonium^ will be vanez centrummikatio nowe I^fŻFfccyjaitb^^ C ale In reactions with various derivatives of diacetoxyiodidene, [2-[(Z)-2-cyano-2-phenylvinyl]-4,6dimethoxyphene Io]phenes I oidonium hexafluorophosphate 24-151 ^x o ^CN A OOlA ΡΡ ₀ Γ J 76.6 [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl](isopropylphenyl)iodine hexafluorophosphate 25-155 ^0 CN 80 [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl](trimethylphenyl)iodonium hexafluorophosphate 25-150 'X _Ο ΧΥ*ΑΛ / \=/ £ 5 J W 76.5

PL 240 445 Β1

T' Preferably a diaryl|odontium salt, coordinated with cation centers [2-[(Z)-2*cyai, c* ^^tdrst^ylol-ary^ are formed in the reaction with various derivatives of diacfe io-2-phenyWinyfó]-4- ΐ j olśyjodpBiiltt^^ [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate 26-026 ^X Q OCC> Or ^pFs 75 [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl](4-isopropylphenyl)iodonium hexafluorophosphate 27-078 ''Oh 66 [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl](2,4,6-trimethylphenyl)iodonium hexafluorophosphate 26-135 CN I ^{ł ρρ} Γ 73 Preferably, diaryliodonium salts coordinated with [[3-((Z)-2-cyano-2-phenylmethyl]-4-methoxyphenyl]aryliodonium cationic centers are formed by reactions with various diaceioxyiodonenzene derivatives [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate 24-087 A - pf ₆ CN rj^Yi 74 [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl](4-isopropylphenyl)iodonium hexafluorophosphate 28-043 iTLl ^PF s CN 73.8 [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl](2,4,6-trimethylphenyl)iodonium hexafluorophosphate 28-036 ΎΥ Ιχ ^PF6 CN 71.5

PL 240 445 Β1

24-087 [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate

26-027

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate

26-026

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate

24-151

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate

26-069 - no polymerization [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate

26-088 [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluorophosphate

Graph 8. Comparison of the kinetics of the cationic photopolymerization process of epoxy monomer during irradiation with light of wavelength of 365 nm and power of 700 mA for diaryliodonium salts coordinated with different cationic centers.

PL 240 445 Β1

100

100 200 300 400 500 600 700 800 900

Time [s]

24-087

[3-[(Z)-2-cyan ο-2-pheny wrapped | 4-methoxyphenyl]phenyl oiodonium hexafluorophosphate

24-151

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyl26-101 26-082 iodonium hexafluorophosphate

[3-[(Z)-2-cyano-2-(2-naphthyl)vinyl]4-methoxyphenyl]phenyliodonium hexafluorophosphate

[2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate 26-082

Figure 9. Comparison of the kinetics of the cationic photopolymerization process of epoxy monomer during irradiation with light of wavelength 365 nm and power of 700 mA for diaryliodonium salts coordinated to different cationic centers.

PL 240 445 Β1

[3-[(Z)-2-cyaηο-2-phenyl]-4methoxyphenyl]-phenyliodonium hexafluorophosphate

26-027

[5-[(Z)-2-cyan ο-2-phenyl]-2,4dimethoxyphenyl]-phenyliodonium hexafluorophosphate

26-101

[3-[(Z)-2-cyano-2-(2-naphthyl)vinyl]4-methoxyphenyl]phenyliodonium hexafluorophosphate

Figure 10. Comparison of the kinetics of the cationic photopolymerization process of epoxy monomer during irradiation with light of wavelength 365 nm and power of 700 mA for diaryliodonium salts coordinated to different cationic centers.

PL 240 445 Β1

24-151

[2-[(Z)-2-cyano-2-phenynyl]-4,6dimethoxyphenyl]phenyl iodonium hexafluorophosphate

26-026

[2- [(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate

26-082

[2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6 dimethoxyphenyl]phenyl iodonium hexafluorophosphate

Figure 11. Comparison of the kinetics of the cationic photopolymerization process of epoxy monomer during irradiation with light of wavelength 365 nm and power of 700 mA for diaryliodonium salts coordinated to different cationic centers.

PL 240 445 Β1

100

100 200 300 400 500 600 700 800 900

Time [s]

[5-[(Z)-2-cyano-2-(2-cyanophenyl)yl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate

[5-[(Z)-2-cyano-2-(4-cyanophenyl)vinyl]-2,4 dimethoxyphenyl]phenyliodonium hexafluorophosphate

[5-[(Z)-2-cyano-2-(3-[5-[(Z)-2-cyano-2-cyanophenyl)vinyl]-2,4-phenylvinyl|-2,4-dimethoxyphenyl]-dimethoxyphenyl]phenyliodonium phenyliodonium hexafluorophosphate hexafluorophosphate

25-080 26-102 26-027

Graph 12. Comparison of the kinetics of the cationic photopolymerization process of the epoxy monomer during irradiation with light of wavelength 365 nm and power of 700 mA for diaryliodonium salts coordinated with cationic centers based on [5-[(Z)-2-cyano'2-arylvinyl]-2,4-dimethoxyphenyl]phenyliodonium chromophores

PL 240 445 Β1

100 200 300 400 500 600 700 800 900

Time [s]

[5-[(Z)-2-cyano-2-phenylvinyl]2,4-dimethoxyphenyl]-(3methoxyphenyl)iodonium hexafluorophosphate

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-cyanophenyl)iodonium hexafluorophosphate

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]phenyliodonium hexafluorophosphate

27-038 26-103 26-027

Graph 13. Comparison of the kinetics of the cationic photopolymerization process of epoxy monomer during irradiation with light of wavelength 365 nm and power of 700 mA for diaryliodonium salts coordinated with [5-[(Z)-2-cyano-2-phenylvinyl]-2,4'-dimethoxyphenyl]-aryliodonium cationic centers, formed in the reaction with various di- and di-alkylbenzene derivatives.

PL 240 445 Β1

100

PHT25-150_CADE_365nm_0p7A

Eh?

<D

PHT24-151_CADE_365nm_0p7A

PHT25-155

PHT25-155_CADE_365nm_0p7A

PHT25-15O

PHT24-151

200

400

Time [s]

600

800

24-151

25-155

25-150

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6- [2-[(Z)-2-cyano-2-phenylvinyl]-4,6- [2-[(Z)-2-cyano-2-phenylvinyl]-4,6- dimethoxyphenyl]phenyliodonium dimethoxyphenyl](isopropylphenyl)iodonium dimethoxyphenyl](trimethylphenyl)iodonium hexafluorophosphate i hexafluorophosphate i hexafluorophosphate

Graph 14. Comparison of the kinetics of the cationic photopolymerization process of epoxy monomer during irradiation with light of wavelength 365 nm and power of 700 mA for diaryliodonium salts coordinated with [[2-1(Z)-2-cyano-2-phenylvinyl] 4,6-dimethoxyphenylaryliodonium cationic centers, formed in reactions with various diaethoxy iodobenzene derivatives.

PL 240 445 Β1

about

''ABOUT

26-026

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenylthiodonium hexafluorophosphate

27-078

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate

26-135

[2-|(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-( _2,1,4,6 -trimethylphenyl)iodonium hexafluorophosphate

Graph 15. Comparison of the kinetics of the cationic photopolymerization process of epoxy monomer during irradiation with light of wavelength 365 nm and power of 700 mA for diaryliodonium salts coordinated with [2-[(Z)-2-cyano’2-phenylvinyl]-4-methoxyphenyl]-aryliodonium cationic centers, formed in reactions with various diacetoxyiodobenzene derivatives.

PL 240 445 Β1

Time [s]

28-036 [3-(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate

28-043

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(2 _J 4,6-trimethylphenyl)iodonium hexafluorophosphate

Graph 16. Comparison of the kinetics of the cationic photopolymerization process of an epoxy monomer during irradiation with light of a wavelength of 365 nm and a power of 700 mA for diaryliodonium salts coordinated with [13-](Z)-2-cyano-2-phenylvinyl]4-methoxyphenyl]aryliodonium cationic centers formed in reactions with various diacetoxyiodobenzene derivatives.

PL 240 445 Β1 • Cationic photopolymerization of the epoxy monomer CADE (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) at a wavelength of 405 nm.

Table 4. Data collected during measurements of the ring-opening photopolymerization process of epoxy monomer at a wavelength of 405 nm and a power of 1000 mA using the FT-IR technique in compositions containing iodonium salts of the present invention.

No. lured *“ in», Structure , Il IX 1' J ·Κ· and II 1Λ3 nm, Monomw ¹ _in 1 jeDuksidwyC.MJE ' [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate 24-087 _PF6CN 12 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-027 ί X ^PF ~ 1 CN 53 [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate 26-026 u 0 [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate 24-151 ^CMPF5 57 [3-[(Z)-2-cyano-2-phenyl inyl]-2,4,6trimethoxyphenes I o]-phenes Ipiodone and new hexafluorophosphate 26-188 1 1 o o -o- ^Xęc,.c uC,, 0 [3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-069 ę^° ^from V0 0 PA wii-ιπ- μιΙκΧ' jl ' i· y * j bil on [5 (,7,-/ *.J« Z* uk Λ łlu] _Ł ' arylojphocfontowy -dwnaloxyfetyl)-(2- [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-methylphenyl)iodonium hexafluorophosphate 27-047 ¹ in -o vJ 37

PL 240 445 Β1

- [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-cyanophenyl iodonium hexafluorophosphate) 25-108 FOR KP O “(\ /)--4- ^O 0 — 51 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-cyanophenyl)iodonium Hexafluorophosphate 25-093 ZA —X O— 50 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4dimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-027 'ii? — o o P O 53

Figure 17. Comparison of the kinetics of the cationic epoxy photopolymerization process during irradiation with light of wavelength 405 nm and power of 1 A for diaryliodonium salts coordinated to different cationic centers.

PL 240 445 Β1

27-047

[5-[(Z)-2-cya η ο-2-phenylaminyl|2,4-dimethoxyphenyl]-(2-methylphenyl)iodonium hexafluorophosphate

25-108

- [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-cyanophenyl)iodonium hexafluorophosphate

25-093 26-027

[5-[(Z)-2-cyano-2-[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-phenyvinyl]-2,4 dimethoxyphenyl]-(3-dimethoxyphenyl [cyanophenyl iodonium phenyl iodonium hexaph I uorophosphate hexafluorophosphate

Graph 18. Comparison of the kinetics of the cationic photopolymerization process of epoxy monomer during irradiation with light of wavelength 405 nm and power of 1 A for diaryliodonium salts coordinated with aryliodonium [5'[(Z)-2-cyano'2-phenylvinyl]ol'2 ₎ 4'dimethyloxyphenyl]ol' cationic centers, formed in reactions with various diacetoxyiodobenzene derivatives.

PL 240 445 Β1 • Cationic photopolymerization of the vinyl monomer TEGDVE (triethylene glycol divinyl ether) at a wavelength of 365 nm and a visible range of 405 nm.

Table 5. Data collected during measurements of the photopolymerization process of the vinyl monomer TEGDVE at a wavelength of 405 nm (at a power of 1000 mA) and also for studies at a wavelength of 365 nm (at a power of 1000 mA) using the FT-IR technique in compositions containing iodonium salts being the subject of the present invention.

Ni ’ ab •Tj j p- i ^i^rj j,u· lwiiw^n<ja tK) In MnAoittcr _t vinyl .......TFGłO _m Convoy ^j.ł ।Kj A'!'-·! H > 4111 um Munniticr in my luft and [3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate 24-087 pf ₆ 88 62 |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyl iodone hexafluorophosphate 26-027 A 9 ° m , o — 89 94 [2-[(Z)-2-cyano-2-phenyl ovinyl]-4methoxyphenyl]-phenyl iodonium hexafluorophosphate 26-026 ^x o CN <^1 - 3 ^PFe 87 14 [2-[(Z)-2-cyano-2-phenylvinyl]-4,6di methoxyphenyl]phenyl oiodonium hexafluorophosphate 24-151 ¢2 >=x / 93 91 [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-118 1 1 O λ. O a. ΓΥΎ /9 65 41 |3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-069 1 _ _JĆCT£i ęr 22 12 PhFfWWWnifł nŁlarttł HTtarłanAr 1 Jf* -Ł ΐΜΛν [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-027 clay ^ρ Ά CN 89 94

PL 240 445 Β1

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-methylphenyl)iodonium hexafluorophosphate 27-047 f J pf ₆ ¹ b 80 92 - [5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(2-cyanophenyl)iodonium hexafluorophosphate 25-108 0 - 87 92 |5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-(3-cyanophenyl)iodonium Hexafluorophosphate 25-093 U —o W 88 94 [5-[(Z)-2-cyano-2-phenylvinyl]-2,4di methoxyphenyl]-phenyliodonium hexafluorophosphor n 26-027 Cl ^pf ^1' and CN ί|Υ° Ci I 89 94 ftdra^ani&dlaLikiadćiwopariychó cation.[2-[(Z)^^^ [2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6-dimethoxyphenyl]-(4-methylphenyl)iodonium hexafluorophosphate 25-151 ^0 ^CN iii OÓĆP aj 59 86 [2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6-dimethoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate 25-155 ° t ° b / \ ^z \=/ 89 S2 [2-[(Z)-2-cyano-2-(2-naphthyl o)vinyl]-4.6 dmethoxyphenyl|-(2,4,6 triphenyl iiodonium hexafluorophosphate 25-150 b3 \ o 80 50 |2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyl-jcdonium hexafluorophosphate 24-151 ^0 r iS Ci ςΧ PF _e jTj 93 91

PL 240 445 Β1

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6d methoxyphenyl]phenyliodonium hexafluorophosphate

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluorophosphate

Figure 19. Comparison of the kinetics of the cationic photopolymerization process of the vinyl monomer TEGDVE during irradiation with light of a wavelength of 365 nm for diaryliodonium salts coordinated to different cationic centers.

[2- [(Z)-2-cyano-2-phenes I cw i nyl]-4,6dimethoxyphenyl phenyl iodonium hexafluorophosphate -24-151

|2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl](isopropylphenyl)iodonium hexafluorophosphate 25-155

|2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl](trimethylphenyl)hydrogen hexafluorophosphate -25-150

Graph 20. Comparison of the kinetics of the cationic photopolymerization process of the vinyl monomer TEGDYE during irradiation with light of a wavelength of 365 nm for diaryliodonium salts coordinated with [2-[(Z)-2-cyano'2-phenylvinyl] ^_4,6 -dimethoxyphenyl]-aryliodonium and [2-[(Z)-2-cyano'2-phenylvinyl]-4,6-dimethoxyphenyl]-4-methyl-2-carboxylic acid cationic centers.

PL 240 445 Β1

|2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl|-phenyliodonium hexafluorophosphate -26-026

|2-[(Z)-2-cyano-2-phenyl inyl|-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate -27-078

|2-[(Z)-2-cyano-2-phenyl inyl|-4-methoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate -26-135

Graph 21. Comparison of the kinetics of the cationic photopolymerization process of the vinyl monomer TEGDYE during irradiation with light of a wavelength of 365 nm for diaryliodonium salts coordinated with [2-[(Z)-2-cyano-2-phenylvinyl] ^_ 4-methoxyphenyl] aryliodonium cationic centers.

|3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyl iodonium hexafluorophosphate 24-087

|3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-(4-isopropylphenyl)iodonium hexafluorophosphate -28-043

|3-[(Z)-2-cyano-2-phenylvinyl|-4-methoxyphenyl]-(2,4,6-trimethylphenyl)iodonium hexafluorophosphate -28-036

Graph 22. Comparison of the kinetics of the cationic photopolymerization process of TEGDYE vinyl monomer during irradiation with light of a wavelength of 365 nm for diaryliodonium salts coordinated with [3-[(Z)'2-cyano-2-phenylvinyl]-4-methoxyphenyl]aryliodonium cationic centers.

PL 240 445 Β1

PHT24-087_TEGDVE_405nm_1A PHT24-151 _TEGDVE_405nm_1 A PHT26-026_TEGDVE_405nm_1A PHT26-069_TEGDVE_405nm_1A PHT26-027_TEGDVE_405nm_1A PHT26-118_TEGDVE_405nm_1A

24-087

[3-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate

[5-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate

[2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]phenyliodonium hexafluorophosphate

24-151

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]phenyliodonium hexafluorophosphate

26-069

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate

26-188

[3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6-trimethoxyphenyl]-phenyliodonium hexafluorophosphate

Figure 23. Comparison of the kinetics of the cationic photopolymerization process of the vinyl monomer TEGDWR during irradiation with light of a wavelength of 405 nm for diaryliodonium salts coordinated to different cationic centers.

PL 240 445 Β1

[2-[(Z)-2-cyano-2-phenylvinyl]-4 _J 6-dimethoxy/enyl]phenyl iodonic acid hexafluorophosphate -24-151

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6di methoxyphenyl](isopropylphenyl)onium hexafluorophosphate 25-155

[2-[(Z)-2-cyano-2-phenylvinyl]-4,6dimethoxyphenyl](trimethylphenyl)iodonium hexafluorophosphate -25-150

Figure 24. Comparison of the kinetics of the cationic photopolymerization process of the vinyl monomer TEGDVE during irradiation with light of a wavelength of 405 nm for diaryliodonium salts coordinated to [2-[(Z)-2-cyano-2-phenylvinyl]-4,6-dimethoxyphenyl]aryliodonium cationic centers.

PL 240 445 Β1 • Radical photopolymerization of the acrylic monomer TMPTA (trimethylolpropane triacrylate) at a wavelength of 365 nm and in the visible range of 405 nm.

Table 6. Data collected during measurements of the free-radical photopolymerization process of the acrylic monomer TMPTA at a wavelength of 405 nm and also for studies at a wavelength of 365 nm using the FT-IR technique in compositions containing iodonium salts being the subject of the present invention.

' Nrzwwku W * Loss no. ¹ ' ’ KojtweiMaTh) ~ _ Motif „ Jtrjfotw TMPTA hunw-r-ia background 'i-I 1« łii nm Monomer 11 rt I«<ó [3-[(Z)-2-cyano-2-phenylvinylc]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate 24-087 PF ₅ CN li^ 17 No polymerization [5-[(Z)-2-cyano-2-phenylvinyl-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-027 Ol ^pFr I CN Γιψ ⁰ No polymerization No polymerization [2-[(Z)-2-cyano-2-phenylvinyl]-4-methoxyphenyl]-phenyliodonium hexafluorophosphate 26-026 oD Cr ^pFr 22 No polymerization [2-[(Z)-2-cyano-2-phenylvinyl|-4,6di methoxyphenes]phenes and oiodonium hexafluorophosphate 24-151 oDr ^pFr XJ 36 22 [3-[(Z)-2-cyano-2-phenylvinyl]-2,4,6trimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-118 II O .— O ΧΧΧ,Ό PF ₀ No polymerization No polymerization [3-[(Z)-2-cyano-2-phenylvinyl|-2,4-dimethoxyphenyl]-phenyliodonium hexafluorophosphate 26-069 ΑΥώ No polymerization No polymerization [2-[(Z)-2-cyano-2-(2-naphthyl)vinyl]-4,6dimethoxyphenyl]phenyl iodonium hexafluorophosphate 26-082 oh* oh, , Ό ⁰ o 33 No polymerization

PL 240 445 Β1

26-118_TMPTA_365nm_0p7A no polymerization

ST

PHT24-151 • 26-082_TMPTA_365nm_0p7A • 24-151_TMPTA_365nm_0p7A or 24-087_TMPTA_365nm_0p7A * 26-026_TMPTA 365nm_0p7A * 26-027_TMPTA_365nm_0p7A no polymerization

PHT26-0B2

PHT26-026

PHT24-087

100

200

Time [s]

300

400

Figure 25. Comparison of the kinetics of the free-radical photopolymerization process of the acrylic monomer TMPTA during irradiation with light of a wavelength of 365 nm for diaryliodonium salts coordinated with different cationic centers.

Figure 26. Comparison of the kinetics of the free-radical photopolymerization process of the acrylic monomer TMPTA during irradiation with light of a wavelength of 405 nm for diaryliodonium salts coordinated with different cationic centers.

Claims (11)

PL 240 445 Β1 Patent claims 1. New diaryliodonium salts of general formula (1) in which - Rn represents a hydrogen atom, a methyl group, a nitrile group; R12 represents a hydrogen atom, a methyl group, a nitrile group; R13 represents a hydrogen atom, a methyl group, a nitrile group, an isopropyl group, a methoxy group, a tert-butyl group; R14 is hydrogen; R15 represents a hydrogen atom, a methyl group, an isopropyl group, a tert-butyl group; - E ~ is an anion selected from the group consisting of PFe ", SbFe", BF4 ", CF ₃ SO ₃ ~, TsO ~, B (CeF5) 4", B (C ₆ H ₅ ) 4-, [AI (OC (CF ₃ ) ₃ ) ₄ ] “; - X represents a 2-cyano-2-phenylvinylphenyl residue of general formula (2A) bonded to iodine through any of the carbon atoms in positions 2-6 corresponding to the position of R1 - Rs, respectively, in which formula - R1 - Rs, as long as the carbon atom corresponding to any of the 2-6 position does not form a bond with iodine, are: R1 is hydrogen, methoxy; R2 represents a hydrogen atom, a methoxy group; R ₃ is hydrogen, methoxy; R4 represents a hydrogen atom, a methoxy group; Rs represents methoxy; - Re - R10 are: Re is a hydrogen atom; R7 is hydrogen; Rs represents a hydrogen atom, a nitrile group; Rg represents a hydrogen atom, a nitrile group; R10 represents a hydrogen atom, a nitrile group; or any two adjacent substituents of Re - R10 form an unsaturated six membered ring which together with the ring to which Re - R10 is attached to form a naphthyl group. 2. The diaryliodonium salt according to claim 1 The compound of claim 1, wherein the 2-cyano-2-phenylvinylphenyl residue is bonded to the iodine atom via a carbon atom in the 3- or 5- or 6-position. 3. The diaryliodonium salt according to claim 1 2 selected from the group consisting of: [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium hexafluoroantimonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium tetrafluoroborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium trifluoromethyl sulfonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium tosylate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium pentafluorophenylborate; PL 240 445 B1 [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium fluorinated alkoxyaluminate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2- (1-naphthyl) vinyl] -4-methoxyphenyl] phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2- (4-cyanophenyl) vinyl] -4-methoxyphenyl] phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2- (2-naphthyl) vinyl] -4-methoxyphenyl] phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium hexafluoroantimonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium tetrafluoroborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium tosylate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium trifluoromethyl sulfonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium tetra-pentafluorophenylborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium fluorinated alkoxyaluminate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium tosylate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium trifluoromethylsulfonate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium tetra-pentafluorophenylborate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium fluorinated alkoxyaluminate; [5 - [(Z) -2-cyano-2- (2-cyanophenyl) vinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2- (3-cyanophenyl) vinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2- (4-cyanophenyl) vinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (3-methylphenyl) iodonium phosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-methylphenyl) iodonium phosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (2-cyanophenyl) iodonium phosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (3-cyanophenyl) iodonium phosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-cyanophenyl) iodonium phosphate; hexafluorohexafluorophoshexafluorophoshexafluorophoshexafluorophos [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (3-methoxyphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (2,4,6-trimethoxyphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; PL 240 445 Β1 [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium tosylate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium trifluoromethyl sulfonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium pentafluorophenylborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium fluorinated alkoxyaluminate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (2,4,6-triphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2- (1-naphthyl) vinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2- (2-naphthyl) vinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium hexafluoroantimonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium tetrafluoroborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium tosylate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium trifluoromethyl sulfonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium tetra-pentafluorophenylborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium fluorinated alkoxyaluminate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium hexafluoroantimonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium tetrafluoroborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium tosylate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium trifluoromethyl sulfonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium tetra-pentafluorophenylborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium fluorinated alkoxyaluminate. 4. The method of producing diaryliodonium salts of general formula (1) (1) wherein the meaning of the substituents is defined in claim 1 A process according to claim 1, characterized in that a stilbene derivative of the general formula (2B) is introduced into glacial acetic acid with a concentration of 99.8% (2B), PL 240 445 Β1 wherein the substituent selected from Ri - Rs attached to the corresponding 2-6 position to the carbon atom through which a 2-cyano-2-phenylvinyl-phenyl residue of general formula (2A) is bonded to the compound of general formula (2A) to be produced (1) with an iodine atom is a hydrogen atom, and the remaining substituents of Ri - Rs and Re - Rio in general formula (2B) are as defined in claim 1. 1 for general formula (2A) and diacetoxyiodo-benzene or a derivative thereof covered by general formula (3) in which the meaning of Rn to R15 is as in a compound of general formula (1) as defined in claim 1 and an acid selected from the group consisting of p-toluenesulfonic acid, p-toluenesulfonic acid in the form of a hydrate monohydrate, sulfuric acid and methanesulfonic acid is added to the solution thus obtained, and the reactants are stirred at a temperature of 20 ° C to 100 ° C, monitoring the progress of the reaction, and then, after reacting the reactants, an inorganic or organic-inorganic salt selected from the group consisting of KPFs, NaSbFs, NaBF ₄ , CF3SO3K, TsONa, (C ₆ H ₅ ) ₄ BNa, (C ₆ F ₅ ) is added to the reaction mixture ₄ BNa, NaPF ₆ , KSbFs, KBF ₄ , CF ₃ SO ₃ Na, (C ₆ H ₅ ) ₄ BK, (CsFs ^ BLi and [AI (OC (CF3) 3) ₄ ] Li and acetic anhydride and continued mixing for 1 minute to 60 minutes, then water is added and stirring is continued for 1 minute to 120 minutes, then the precipitate is filtered off, washed with water and an organic solvent selected from the group consisting of isopropanol, chloroform , dichloromethane, acetone, acetonitrile, diethyl ether, tetrahydrofuran, ethyl acetate lu, dimethylformamide, dimethylsulfoxide, pentane, heptane, hexane, cyclohexane, benzene, toluene, xylene and dried. 5. The method according to p. A process according to claim 4, characterized in that the compounds of general formula (2B) are compounds selected from the group consisting of: (Z) -3- (2-methoxyphenyl) -2-phenylprop-2-enenitrile; (Z) -3- (2-methoxyphenyl) -2- (4-cyophenylprop) -2-enenitrile; (Z) -3- (2-methoxyphenyl) -2- (2-naphthyl) prop-2-enenitrile; (Z) -3- (2-methoxyphenyl) -2- (1-naphthyl) prop-2-enenitrile; (Z) -3- (3-methoxyphenyl) -2-phenylprop-2-enenitrile; (Z) -3- (2,4-dimethoxyphenyl) -2-phenylprop-2-enenitrile; 2 - [(Z) -1-cyano-2- (2,4-dimethoxyphenyl) vinyl] benzonitrile; 3 - [(Z) -1-cyano-2- (2,4-dimethoxyphenyl) vinyl] benzonitrile; 4 - [(Z) -1-cyano-2- (2,4-dimethoxyphenyl) vinyl] benzonitrile; (Z) -3- (3,5-dimethoxyphenyl) -2-phenylprop-2-enenitrile; (Z) -2-cyano-2- (1-naphthyl) vinyl] -4,6-dimethoxyphenyl; (Z) -2-cyano-2- (2-naphthyl) vinyl] -4,6-dimethoxyphenyl; (Z) -3- (2,6-dimethoxyphenyl) -2-phenylprop-2-enenitrile; (Z) -3- (2,4,6-trimethoxyphenyl) -2-phenylprop-2-enenitrile. 6. The method according to p. 4. The process as claimed in claim 4, characterized in that the diacetoxyiodobenzene derivatives of the general formula (3) are compounds selected from the group consisting of: diacetoxyiodo-4-methylbenzene, diacetoxyodo-2-methylbenzene, diacetoxyodo-3-methylbenzene, diacetoxyiodo-3-methoxybenzene, diacetoxyiodo-4-cyanobenzene, diacetoxyiodo-3-cyanobenzene-4-butylbenzene, diacetoxy-2-cyanobenzene-4-butylbenzene - isopropyl diacetoxy iodobenzene, diacetoxy iodo-2,4,6-trimethylbenzene. 7. The method according to p. 4. The process of claim 4, wherein the reaction of the compounds of general formulas (2B) and (3) is carried out with a molar ratio of the compound (2B) to the compound (3) ranging from 1: 1 to 1: 2. 8. The method according to p. 4 or 5, 6 or 7, characterized in that the reaction of the compound of general formula (2B) and the compound of general formula (3) is carried out by stirring at room temperature a solution of the reactants in glacial acetic acid to which p-tolu acid has been added After the reactants have reacted, the inorganic KPFs salt and acetic anhydride are added to the mixture and stirring is continued for 5 minutes, then water is added and the mixture is stirred for a further 30 minutes. min., and then the resulting precipitate is filtered off, washed with water and diethyl ether and dried in vacuo. 9. The method according to p. A process according to claim 4 or 8, characterized in that diaryliodonium salts are prepared selected from the group consisting of: [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium hexafluoroantimonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium tetrafluoroborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium trifluoromethyl sulfonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium lot] an; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium pentafluorophenylborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium fluorinated alkoxyaluminate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2- (1-naphthyl) vinyl] -4-methoxyphenyl] phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2- (4-cyanophenyl) vinyl] -4-methoxyphenyl] phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2- (2-naphthyl) vinyl] -4-methoxyphenyl] phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium hexafluoroantimonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium tetrafluoroborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium tosylate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium trifluoromethyl sulfonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium tetra-pentafluorophenylborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium fluorinated alkoxyaluminate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium tosylate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium trifluoromethylsulfonate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium tetra-pentafluorophenylborate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium fluorinated alkoxyaluminate; [5 - [(Z) -2-cyano-2- (3-cyanophenyl) vinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2- (4-cyanophenyl) vinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate; PL 240 445 B1 5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-methylphenyl) iodonium phosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (2-cyanophenyl) iodonium phosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (3-cyanophenyl) iodonium phosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-cyanophenyl) iodonium phosphate; hexafluorophoshexafluorophoshexafluorophoshexafluorophos [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (3-methoxyphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium tosylate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium trifluoromethyl sulfonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium pentafluorophenylborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium fluorinated alkoxyaluminate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (2,4,6-triphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2- (1-naphthyl) vinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2- (2-naphthyl) vinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium hexafluoroantimonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium tetrafluoroborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium tosylate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium trifluoromethyl sulfonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium tetra-pentafluorophenylborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium fluorinated alkoxyaluminate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium hexafluoroantimonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium tetrafluoroborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium tosylate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium trifluoromethyl sulfonate; 3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium tetra-pentafluorophenylborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium fluorinated alkoxyaluminate. PL 240 445 Β1 10. The use of diaryliodonium salts of general formula (1) wherein the meaning of the substituents is defined in claim 1 1 as photoinitiators for photoinitiated cationic and radical polymerization. 11. Use according to claim 1 The process of claim 10, wherein the photoinitiators are diaryliodonium salts selected from the group consisting of: [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] -phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium hexafluorophosphate; 3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium hexafluoroantimonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium tetrafluoroborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium trifluoromethyl sulfonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium tosylate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium pentafluorophenylborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] -phenyliodonium fluorinated alkoxyaluminate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2- (1-naphthyl) vinyl] -4-methoxyphenyl] phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2- (4-cyanophenyl) vinyl] -4-methoxyphenyl] phenyliodonium hexafluorophosphate; 3 - [(Z) -2-cyano-2- (2-naphthyl) vinyl] -4-methoxyphenyl] phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium hexafluoroantimonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium tetrafluoroborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium tosylate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium trifluoromethyl sulfonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium tetra-pentafluorophenylborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] phenyliodonium fluorinated alkoxyaluminate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4-methoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium tosylate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium trifluoromethylsulfonate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium tetra-pentafluorophenylborate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] phenyliodonium fluorinated alkoxyaluminate; PL 240 445 B1 [5 - [(Z) -2-cyano-2- (2-cyanophenyl) vinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2- (3-cyanophenyl) vinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2- (4-cyanophenyl) vinyl] -2,4-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate; 5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-methylphenyl) iodonium phosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (2-cyanophenyl) iodonium phosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (3-cyanophenyl) iodonium phosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-cyanophenyl) iodonium phosphate; hexafluorophos- hexafluorophos- hexafluorophos- hexafluorophos- [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (3-methoxyphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [5 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; 2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium tosylate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium trifluoromethyl sulfonate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium pentafluorophenylborate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] phenyliodonium fluorinated alkoxyaluminate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (2,4,6-triphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2-phenylvinyl] -4,6-dimethoxyphenyl] - (4-tert-butylphenyl) iodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2- (1-naphthyl) vinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2 - [(Z) -2-cyano-2- (2-naphthyl) vinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium hexafluoroantimonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium tetrafluoroborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium tosylate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium trifluoromethyl sulfonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium tetra-pentafluorophenylborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4-dimethoxyphenyl] -phenyliodonium fluorinated alkoxyaluminate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium hexafluoroantimonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium tetrafluoroborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium tosylate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium trifluoromethyl sulfonate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium tetra-pentafluorophenylborate; [3 - [(Z) -2-cyano-2-phenylvinyl] -2,4,6-trimethoxyphenyl] -phenyliodonium fluorinated alkoxyaluminate.