WO2019019792A1 - 香豆素肟酯类化合物及其制备和应用 - Google Patents

香豆素肟酯类化合物及其制备和应用 Download PDF

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WO2019019792A1
WO2019019792A1 PCT/CN2018/088830 CN2018088830W WO2019019792A1 WO 2019019792 A1 WO2019019792 A1 WO 2019019792A1 CN 2018088830 W CN2018088830 W CN 2018088830W WO 2019019792 A1 WO2019019792 A1 WO 2019019792A1
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alkyl
amino
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alkylthio
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French (fr)
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庞玉莲
邹应全
樊书珩
高明
辛阳阳
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Hubei Gurun Technology Co Ltd
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Hubei Gurun Technology Co Ltd
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Priority to KR1020207005324A priority Critical patent/KR102365830B1/ko
Priority to US16/633,294 priority patent/US11142511B2/en
Priority to CN201880049443.6A priority patent/CN110959006A/zh
Priority to BR112020001598-9A priority patent/BR112020001598B1/pt
Priority to JP2020504170A priority patent/JP6910533B2/ja
Priority to CA3071010A priority patent/CA3071010C/en
Priority to EP18839489.4A priority patent/EP3660008B1/en
Publication of WO2019019792A1 publication Critical patent/WO2019019792A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/12—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 3 and unsubstituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/68—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with nitrogen atoms directly attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

Definitions

  • This invention relates to coumarin 3-ketoxime ester compounds which are useful as photoinitiators.
  • the invention also relates to the preparation and use of coumarin 3-ketooxime ester compounds.
  • Photoinitiators also known as photosensitizers or photocuring agents, are a type of energy that absorbs a certain wavelength in the ultraviolet (250-400 nm) or visible (400-600 nm) regions, generating free radicals, cations, etc., thereby initiating monomers. Polymerization cross-linking cured compound. In the photocuring system, the photoinitiator generally accounts for 3-5%, and although the content is low, it is a key component thereof, which plays a decisive role in the photocuring speed. It is related to whether the oligomer and the diluent can be rapidly cross-linked and solidified in the formulation system during light irradiation, thereby changing from a liquid state to a solid state.
  • photocuring technology has been widely used in traditional fields such as coatings, inks, microelectronics, printing, etc., and is also used in the preparation of new fields such as laser recording and three-dimensional components.
  • the photoinitiator must meet the needs of different photocuring conditions and applications.
  • the main objectives are: to improve light sensitivity, improve surface curing efficiency (antioxidation inhibition), improve deep curing properties, improve the solubility of photoinitiators in monomers and resins, and reduce toxicity and odor. It reduces the migration of the uncured initiator after curing and reduces the yellowing.
  • the oxime ester photoinitiator has become a kind of photoinitiator which has been paid more and more attention in recent years because of its excellent photographic performance.
  • BASF products OXE-01 and OXE-02 are two typical oxime ester products currently on the market. These two products have high photosensitivity, but their UV absorption wavelength is short, which is not suitable for UV-LED sources (emission wavelengths 365nm, 385nm, 395nm, 405nm, 420nm).
  • UV-LED sources emission wavelengths 365nm, 385nm, 395nm, 405nm, 420nm.
  • CN102775527A discloses a diphenyl sulfide ketone oxime ester photoinitiator and a preparation method thereof
  • CN102492059A discloses a photoinitiator of substituted diphenyl sulfide ketone oxime ester. Agents and so on.
  • most of the initiators have an ultraviolet absorption wavelength of 250-350 nm, which cannot be matched with the growing LED light source, which greatly limits the application of the oxime ester photoinitiator.
  • CN104817653A discloses an oxime ester photoinitiator suitable for curing UV-LED light source, the initiator compound being a coumarin aldoxime ester compound, however, studies have shown that the thermal stability of such compounds is inferior to that of OXE-01 [Zhu Guigang] , Synthesis of Coumarin Ester Derivatives and Their Applications in LED Photocuring, Master Thesis, 2016; Dietliker K, Birbaum JL, R, et al. Photolatent catalysts [J]. CHIMIA International Journal for Chemistry, 2002, 56(5): 197-202.].
  • CN1889960A discloses that coumarin oxime ester compounds can be used in pharmaceutical compositions or cosmetic compositions for the prevention and treatment of diseases including immune diseases, chronic inflammation, neurological diseases and skin diseases, tumor diseases, specific viruses (especially It is SARS) and so on. In this sense, such compounds are safe and non-toxic, but coumarin oxime esters have not been reported in the literature as photoinitiators.
  • the inventors of the present invention conducted extensive and in-depth research on photoinitiators suitable for radiation curing of UV-LED light sources (emission wavelengths of 300-450 nm, especially 365-420 nm), with a view to A photoinitiator capable of replacing OXE-01 and OXE-02 to be more suitable for curing UV-LED sources and having good thermal stability was found.
  • the present inventors have found that the unsubstituted or substituted coumarin is linked to the oxime ester moiety directly or via a carbonyl group, and the coumarin (keto) oxime ester compound thus obtained has a very high range of from 300 to 450 nm, especially from 350 to 420 nm. Strong UV absorption, and good thermal stability, suitable for use as a photoinitiator for UV-LED source radiation curing.
  • the object of the invention is achieved based on the aforementioned findings.
  • a coumarin (keto) oxime ester compound which has an absorption wavelength which is not only suitable for radiation curing of a UV-LED source but also has excellent thermal stability.
  • Another object of the present invention is to provide a process for preparing the coumarin (keto) oxime ester compound of the present invention.
  • a further object of the invention is to provide the use of the coumarin (keto) oxime ester compounds of the invention as photoinitiators or photosensitizers.
  • n 0 or 1
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represent hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, C 1 -C 8 carboxylate, sulfonate, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkane Oxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkane a C 2 -C 20 olefinylthio group, a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group
  • R 1 and R 2 together, R 2 and R 3 together, R 3 and R 4 together or R 1 and R 2 and R 3 together with R 4 form together a total of 3-4 heteroatoms selected from C, N, O, and S And a saturated or unsaturated divalent group in which at least one of the atoms is a carbon atom;
  • R 6 and R 7 independently of each other represent a linear or branched C 1 -C 20 alkyl group, a C 3 -C 10 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group, a C 4 -C 10 alkyl group.
  • a cycloalkyl group a C 6 -C 20 aryl group, a C 7 -C 20 aralkyl group, and a C 7 -C 20 alkylaryl group, wherein the aforementioned C 1 -C 20 alkyl group, C 3 -C 10 cycloalkyl group, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkylaryl optionally
  • the ground is substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen, nitro, amino, Mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino and fluorenyl,
  • n 0, R 1 , R 2 , R 3 , R 4 and R 5 are all H, R 6 is a methyl group, and R 7 is a n-propyl group.
  • R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, thiol, carboxy, C 1 -C 6 carboxylic acid ester Base, sulfonic acid group, amino group, cyano group, C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group, C 2 -C 6 alkynyl group, C 3 -C 8 cycloalkyl group, C 4 -C 8 ring Alkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkyl Alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkylthio, C 2 -C 6 alkynylthio
  • R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, C 1 -C 4 carboxylate, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, phenoxy And phenylthio; or, R 1 together with R 2 , R 2 together with R 3 or R 3 together with R 4 form a total of 3 or 4 atoms selected from C, N, O and S and wherein at least A saturated or unsaturated divalent group in which one atom is a carbon atom, such as -O-CH 2 -O-, -S-CH 2 -S-, -N-CH 2 -N-, -O-CH 2 CH 2 -O-,
  • R 6 and R 7 independently of each other represent a linear or branched C 1 -C 8 alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 8 ring
  • An alkylalkyl group, a C 4 -C 8 alkylcycloalkyl group, a C 6 -C 10 aryl group, a C 7 -C 11 aralkyl group, and a C 7 -C 11 alkylaryl group wherein the aforementioned C 1 -C 8 Alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl
  • a C 7 -C 11 alkylaryl group is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4
  • R 6 and R 7 are independently of each other selected from a linear or branched C 1 -C 8 alkyl group, a C 5 -C 6 cycloalkyl group, a C 1 substituted by a C 5 -C 6 cycloalkyl group.
  • a -C 4 alkyl group a C 1 -C 4 alkyl group substituted with a phenyl group, and a phenyl group, wherein each of the aforementioned phenyl groups is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4- alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl) Amino group and mercapto group;
  • R 6 is a linear or branched C 1 -C 6 alkyl group, a C 5 -C 6 cycloalkyl group, a C 1 -C 2 alkyl group substituted by a C 5 -C 6 cycloalkyl group or a phenyl group, the aforementioned phenyl group being optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy , halogen, nitro, amino and thiol, and
  • R 7 is a linear or branched C 1 -C 7 alkyl or phenyl group, wherein the phenyl group is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4 alkyl Halogen, nitro, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino and fluorenyl.
  • n 0,
  • R 6 is a linear or branched C 1 -C 6 alkyl group, a halogenated C 1 -C 6 alkyl group, a C 5 -C 6 cycloalkyl group, a C 1 - substituted by a C 5 -C 6 cycloalkyl group C 2 alkyl or phenyl, the aforementioned phenyl optionally substituted by one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 alkane An oxy group, a C 1 -C 4 alkylthio group and a halogenated C 1 -C 4 alkyl group, and
  • R 7 is a linear or branched C 1 -C 7 alkyl or phenyl group, wherein the phenyl group is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4 alkyl , halogen, nitro, amino, mono(C 1 -C 4 alkyl)amino and di(C 1 -C 4 alkyl)amino, or
  • n 1,
  • R 1 , R 2 , R 3 and R 4 are independently of each other selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, mono (C 1 -C) 4 alkyl) amino, di (C 1 -C 4 alkyl) amino, phenoxy, and phenylthio; alternatively, R 1 together with R 2, R 2 and R 3 together or R 3 and R 4 together form a total a saturated or unsaturated divalent group having 3 or 4 atoms selected from C, N, O and S and at least one of which is a carbon atom, such as -O-CH 2 -O-, -S-CH 2 -S-, -N-CH 2 -N-, -O-CH 2 CH 2 -O-, -S-CH 2 CH 2 -S- or -N-CH 2 CH 2 -N;
  • R 6 is a linear or branched C 1 -C 6 alkyl group, a halogenated C 1 -C 6 alkyl group, a C 5 -C 6 cycloalkyl group or a C 1 - substituted by a C 5 -C 6 cycloalkyl group C 2 alkyl, and
  • R 7 is a linear or branched C 1 -C 6 alkyl group or a phenyl group optionally substituted by a nitro group.
  • a method of preparing a compound as claimed in any one of items 1 to 6, comprising the steps of:
  • R 1 -R 5 and R 6 in the formulae (II), (IIIa) and (IIIb) are as defined in any one of items 1 to 6;
  • the deuteration reaction is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine or a mixture thereof; and/or, the deuteration reaction is carried out in the presence of ethanol or aqueous ethanol as a solvent; and/or
  • the temperature of the deuteration reaction is 60-120 ° C; and/or, the deuteration reaction time is 0.1-20 hours, preferably 0.5-10 hours; the molar ratio of the compound of the formula (II) to a compound selected from hydroxylamine and/or hydroxylamine hydrochloride a ratio of 1:1.5-1.5:1, preferably 1:1.2-1.2:1;
  • the deuteration reaction is carried out in the presence of concentrated hydrochloric acid; and/or, the deuteration reaction is carried out in the presence of ethanol or aqueous ethanol as a solvent; and/or, the temperature of the deuteration reaction is -30 to 20 ° C Preferably, 5-20 ° C; and/or, the oximation reaction time is 0.1-20 hours, preferably 0.5-10 hours; the compound of formula (II) is selected from the group consisting of nitrous acid, nitrite and/or alkyl nitrite.
  • the molar ratio of the compound is from 1:1.5 to 1.5:1, preferably from 1:1.2 to 1.2:1.
  • alkyl nitrite is a C 1 -C 6 alkyl nitrite such as methyl nitrite, ethyl nitrite, isopropyl nitrite or butyl nitrite.
  • isoamyl nitrite; and/or the esterification of step (2) is carried out using an esterification reagent selected from the group consisting of the compounds of the following formulae (IVa), (IVb) and (IVc):
  • X is a halogen, especially chlorine, and R 7 is as defined in any one of claims 1-6.
  • a compound of formula (I) as claimed in any one of items 1 to 6 as a photoinitiator, in particular as a photoinitiator in a UV-LED photocuring system, in particular at a radiation wavelength
  • a photoinitiator in photocuring systems of 300-450 nm, preferably 350-420 nm, especially 365-405 nm.
  • Figure 1 is a schematic diagram of a Ugra print strip, wherein
  • n 0 or 1
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represent hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, C 1 -C 8 carboxylate, sulfonate, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkane Oxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkane a C 2 -C 20 olefinylthio group, a C 2 -C 20 alkynylthio group, a C 3 -C 20 cycloalkylthio group
  • R 1 and R 2 together, R 2 and R 3 together, R 3 and R 4 together or R 1 and R 2 and R 3 together with R 4 form together a total of 3-4 heteroatoms selected from C, N, O, and S And a saturated or unsaturated divalent group in which at least one of the atoms is a carbon atom;
  • R 6 and R 7 independently of each other represent a linear or branched C 1 -C 20 alkyl group, a C 3 -C 10 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group, a C 4 -C 10 alkyl group.
  • a cycloalkyl group a C 6 -C 20 aryl group, a C 7 -C 20 aralkyl group, and a C 7 -C 20 alkylaryl group, wherein the aforementioned C 1 -C 20 alkyl group, C 3 -C 10 cycloalkyl group, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkylaryl optionally
  • the ground is substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, halogen, nitro, amino, Mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino and fluorenyl,
  • n 0, R 1 , R 2 , R 3 , R 4 and R 5 are all H, R 6 is a methyl group, and R 7 is a n-propyl group.
  • the compound of the formula (I) contains both a coumarin-based moiety and a (keto)oxime-ester moiety.
  • the compound has strong ultraviolet absorption in the range of 350-450 nm. It can rapidly transfer energy after absorbing light energy, and continuously initiate polymerization. It has obvious advantages in photosensitivity and pattern integrity, and is very suitable for UV-LED light source and its Safe and non-toxic can be used in food packaging and other fields. Furthermore, the compounds of formula (I) also have good thermal stability.
  • C n -C m in each case means that the number of carbon atoms contained in the group is nm.
  • Halogen means fluoro, chloro, bromo and iodo. In the present invention, it is preferred that the halogen includes F, Cl or a combination thereof.
  • C n -C m alkyl as used herein means having nm, for example 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, especially preferably 1-4 Branched or unbranched saturated hydrocarbon group of one carbon atom, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 - dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylmethylmethylbut
  • the C 1 -C 8 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl and Its isomers.
  • the C 1 -C 6 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof.
  • C 1 -C 4 alkyl may be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl Base and its isomers.
  • C 2 -C m alkenyl refers to a 2-m, for example 2-20, preferably 2-6, more preferably 2-4 carbon atoms and having one or more at any position by Branched or unbranched unsaturated open-chain hydrocarbon groups of double bonds, such as vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3- Butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl , 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl- 3-butenyl, 3-methyl-3-butenyl, 1,1
  • the C 2 -C 6 alkenyl group may be a vinyl group, a propenyl group, a 1-butenyl group, a 2-butenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a neopentenyl group, or a 1-hexyl group.
  • the C 2 -C 4 alkenyl group may be a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methylvinyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl group.
  • C 2 -C m alkynyl refers to having from 2 to m, for example from 2 to 20, preferably from 2 to 6, more preferably from 2 to 4, carbon atoms and having one or more positions at any position.
  • a branched or unbranched unsaturated open chain hydrocarbon group of an oxime bond such as an ethynyl group, a propynyl group, a 1-butynyl group, a 2-butynyl group, and isomers thereof.
  • the C 2 -C 6 alkynyl group may be ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentyne A group, a 1-hexynyl group, a 2-hexynyl group, a 3-hexynyl group, a 4-hexynyl group, a 5-hexynyl group, and isomers thereof.
  • the C 2 -C 4 alkynyl group may be ethynyl, propynyl, 1-butynyl, 2-butynyl and isomers thereof.
  • C 3 -C m cycloalkyl refers to a saturated alicyclic monocyclic group having 3 to m, for example 3 to 20, preferably 3 to 8, more preferably 5 to 6 ring carbon atoms. Groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
  • C 4 -C m cycloalkylalkyl denotes an alkyl group substituted by a cycloalkyl group and contains a total of 4 to m carbon atoms, for example 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, more preferably 4-6 carbon atoms, wherein alkyl and cycloalkyl are as defined herein, for example cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutane Ethyl ethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, Cyclohexylpropyl,
  • C 4 -C 10 alkylcycloalkyl denotes a cycloalkyl group substituted by an alkyl group and contains a total of 4 to m carbon atoms, for example 4 to 10 carbon atoms, preferably 4 to 8 carbon atoms, more preferably 4-6 carbon atoms, wherein alkyl and cycloalkyl are as defined herein, for example methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethyl Cyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl , butylcyclohexyl, buty
  • C 6 -C m aryl refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group containing 6 to m carbon atoms, for example 6 to 18, preferably 6 to 10 carbon atoms.
  • C 6 -C m aryl group examples include phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, a Phenylphenyl and naphthyl and the like; preferably phenyl or naphthyl, especially phenyl (also referred to as C 6 H 5 as a substituent).
  • C 7 -C 20 aralkyl denotes an alkyl group substituted by an aryl group and contains a total of 7 to 20 carbon atoms, for example 7 to 12, preferably 7 to 10 carbon atoms, more preferably 7 to 8 carbon atoms. Atoms wherein alkyl and aryl are as defined herein, such as benzyl, phenethyl, naphthylmethyl, naphthylethyl and the like.
  • C 7 -C 20 alkylaryl denotes an aryl group substituted by an alkyl group and contains a total of 7 to 20 carbon atoms, for example 7 to 12, preferably 7 to 10 carbon atoms, more preferably 7 to 8 a carbon atom wherein alkyl and aryl are as defined herein, for example methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, A Naphthyl, ethylnaphthyl and the like.
  • C n -C m alkoxy and "C n -C m alkylthio" refer to any carbon atom bonded to an open-chain C n -C m alkane corresponding to a C n -C m alkyl group.
  • An oxygen atom or a sulfur atom as a C n -C m alkyl group of a linking group for example a C 1 -C 20 alkoxy (or sulfur) group, preferably a C 1 -C 12 alkoxy (or sulfur) group, more preferably A C 1 -C 8 alkoxy (or thio) group, particularly preferably a C 1 -C 6 alkoxy (or thio) group, particularly preferably a C 1 -C 4 alkoxy (or thio) group.
  • the C 1 -C 8 alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy Base, hexyloxy, heptyloxy, octyloxy, isooctyloxy and isomers thereof.
  • the C 1 -C 4 alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and isomers thereof body.
  • the C 1 -C 8 alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, tert-butylthio, pentylthio, isopentylsulfide.
  • Base hexylthio, heptylthio, octylthio, isooctylthio and isomers thereof.
  • the C 1 -C 4 alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio and isomers thereof.
  • C 2 -C m alkenyl group and "C 2 -C m alkenyl group” refers to any saturated carbon atom C 2 -C m alkenyl, C 2 -C m corresponding alkene bond a C 2 -C m alkenyl group having an oxygen atom or a sulfur atom as a linking group, for example, a C 2 -C 20 olefinic oxygen (or sulfur) group, preferably a C 2 -C 12 olefinic oxygen (or sulfur) group, Preference is given to C 2 -C 8 olefinic oxygen (or thio) groups, particular preference being given to C 2 -C 6 olefinic oxygen (or sulphur) groups, particular preference being given to C 2 -C 4 olefinic oxygen (or sulphur) groups, for example ethyleneoxy groups, propylene groups Oxyl, isopropenyloxy, n-butenyloxy, sec-butenyl
  • C 2 -C m alkynyloxy and "C 2 -C m alkynylthio" refer to a bond on any saturated carbon atom in a C 2 -C m alkyne corresponding to a C 2 -C m alkynyl group.
  • a C 2 -C m alkynyl group having an oxygen atom or a sulfur atom as a linking group for example, a C 2 -C 20 alkynyloxy (or sulfur) group, preferably a C 2 -C 12 alkyne (or sulfur) group, More preferably, it is a C 2 -C 8 alkyne oxygen (or sulfur) group, particularly preferably a C 2 -C 6 alkyne oxygen (or sulfur) group, particularly preferably a C 2 -C 4 alkyne oxygen (or sulfur) group, such as an ethynyloxy group, Propynyloxy, n-butynyloxy, sec-butynyloxy and isomers thereof, acetylenethio, propynylthio, propynylthio, n-butynylthio, sec-butynylthio and their Structure.
  • C 3 -C m cycloalkoxy and "C 3 -C m cycloalkylthio" refer to any ring carbon atom in a C 3 -C m cycloalkane corresponding to a C 3 -C m cycloalkyl group.
  • a C 3 -C m cycloalkyl group having an oxygen atom or a sulfur atom as a linking group for example, a C 3 -C 20 cycloalkoxy (or thio) group, preferably a C 3 -C 8 cycloalkoxy group ( Or a thio) group, more preferably a C 5 -C 6 cycloalkoxy (or thio) group, such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy , cyclooctyloxy, cyclodecyloxy and isomers thereof, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, cyclooctyl Thio group, cyclodecylthio group and isomers thereof.
  • C 4 -C m cycloalkylalkoxy and "C 4 -C m cycloalkylalkylthio” refer to an alkoxy (thio) group substituted by a cycloalkyl group and contain a total of 4 to 4 carbons.
  • An atom for example 4 to 20 carbon atoms, preferably 4 to 8 carbon atoms, wherein the cycloalkyl and alkoxy (thio) groups are as defined herein, for example cyclopropylmethoxy, cyclopropylethoxy, ring Propylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentyl Oxyl, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy, cyclopropylmethylthio, cyclopropane Ethylthio, cyclopropylpropylthio, cyclopropylbutylthio, cyclobutyl
  • C 6 -C m aryloxy and "arylthio C 6 -C m” refers to the -C m any aromatic carbon atoms in the aromatic C 6 -C aryl group m corresponding to C 6
  • a C 6 -C m aryl group having an oxygen atom or a sulfur atom as a linking group is bonded, for example, a phenylthio group, a phenoxy group, a tolyloxy group, a tolylthio group, a naphthylthio group, a naphthyloxy group or the like.
  • n is 0 or 1.
  • the compound of the formula (I) is referred to as a coumarin oxime ester compound; when n is 1, the compound of the formula (I) is referred to as a coumarin oxime ester compound.
  • coumarin (keto) oxime ester compounds are collectively referred to as coumarin (keto) oxime ester compounds.
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of hydrogen, halogen, nitro, hydroxy, decyl, carboxyl, C 1 -C 8 carboxylate, sulfonate , amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio
  • R 1 together with R 2 , R 2 together with R 3 , R 3 together with R 4 or R 1 together with R 2 and R 3 together with R 4 form a total of 3-4 selected from C, N, The atoms of O and S and wherein at least one of the atoms is a saturated or unsaturated divalent group of carbon atoms.
  • R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, C 1 -C 6 carboxylate, sulfonate, Amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1- C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio
  • R 1 together with R 2 , R 2 together with R 3 or R 3 together with R 4 form a total of 3-4 atoms selected from C, N, O and S and at least one of which is a carbon atom.
  • a saturated or unsaturated divalent group
  • R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other selected from the group consisting of hydrogen, halogen, nitro, C 1 -C 4 carboxylate, C 1 -C 4 alkyl, C 2- C 4 alkenyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, benzene Oxyl and phenylthio.
  • R 6 and R 7 each independently represent a linear or branched C 1 -C 20 alkyl group, a C 3 -C 10 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group, or a C 4 group.
  • aryl group is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, C 1 -C 6 alkyl, halogen, Nitro, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl)amino and fluorenyl.
  • R 6 and R 7 independently of each other represent a linear or branched C 1 -C 8 alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 8 cycloalkylalkyl group, a C 4 - a C 8 alkylcycloalkyl group, a C 6 -C 10 aryl group, a C 7 -C 11 aralkyl group, and a C 7 -C 11 alkylaryl group, wherein the aforementioned C 1 -C 8 alkyl group, C 3 -C 8 Cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkyl
  • the aryl group is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 3
  • R 6 and R 7 are independently of each other selected from a linear or branched C 1 -C 8 alkyl group, a C 5 -C 6 cycloalkyl group, a C substituted by a C 5 -C 6 cycloalkyl group.
  • a 1- C 4 alkyl group a C 1 -C 4 alkyl group substituted by a phenyl group, and a phenyl group, wherein each of the aforementioned phenyl groups is optionally substituted by one or more groups independently selected from the group consisting of C 1 - C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkane Amino group and fluorenyl group.
  • R 6 is a linear or branched C 1 -C 6 alkyl group, a C 5 -C 6 cycloalkyl group, a C 1 -C 2 alkyl group substituted by a C 5 -C 6 cycloalkyl group or a phenyl group.
  • the aforementioned phenyl group is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, halogen, nitro, amino and fluorenyl, and R 7 is straight or branched.
  • C 1 -C 7 alkyl or phenyl wherein the phenyl group is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio C 1 -C 4 alkoxy, halogen, nitro, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino and fluorenyl.
  • R 5 is H.
  • R 6 is a linear or branched C 1 -C 6 alkyl group, a halogenated C 1 -C 6 alkyl group, a C 5 -C 6 cycloalkyl group, a C 1 - substituted by a C 5 -C 6 cycloalkyl group C 2 alkyl or phenyl, the aforementioned phenyl optionally substituted by one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 alkane An oxy group, a C 1 -C 4 alkylthio group and a halogenated C 1 -C 4 alkyl group, and
  • R 7 is a linear or branched C 1 -C 7 alkyl or phenyl group, wherein the phenyl group is optionally substituted by one or more groups independently selected from the group consisting of C 1 -C 4 alkyl , halogen, nitro, amino, mono(C 1 -C 4 alkyl)amino and di(C 1 -C 4 alkyl)amino, or
  • R 1 , R 2 , R 3 and R 4 are independently of each other selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, mono (C 1 -C) 4 alkyl) amino, di (C 1 -C 4 alkyl) amino, phenoxy, and phenylthio; alternatively, R 1 together with R 2, R 2 and R 3 together or R 3 and R 4 together form a total a saturated or unsaturated divalent group having 3 or 4 atoms selected from C, N, O and S and at least one of which is a carbon atom, such as -O-CH 2 -O-, -S-CH 2 -S-, -N-CH 2 -N-, -O-CH 2 CH 2 -O-, -S-CH 2 CH 2 -S- or -N-CH 2 CH 2 -N;
  • R 6 is a linear or branched C 1 -C 6 alkyl group, a halogenated C 1 -C 6 alkyl group, a C 5 -C 6 cycloalkyl group or a C 1 - substituted by a C 5 -C 6 cycloalkyl group C 2 alkyl, and
  • R 7 is a linear or branched C 1 -C 6 alkyl group or a phenyl group optionally substituted by a nitro group.
  • the compound of formula (I) is selected from compounds 1-50.
  • Compounds 1-50 were prepared in Examples 1-50, respectively.
  • R 1 -R 5 and R 6 in the formulae (II), (IIIa) and (IIIb) are as defined for the formula (I);
  • the deuteration reaction usually begins with a carbonyl compound.
  • n is 0, the compound of formula (II) is subjected to a oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to give a compound of formula (IIIa).
  • R 1 -R 5 and R 6 in the formulae (II) and (IIIa) are as defined for the formula (I).
  • hydroxylamine hydrochloride NH 2 OH.HCl
  • hydroxylamine NH 2 OH
  • a mixture thereof a deuteration reagent.
  • the deuteration reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Solvents which can be used are, for example, ethanol or aqueous ethanol.
  • a base such as sodium acetate, pyridine, piperidine or triethylamine.
  • pyridine, piperidine, and triethylamine can also be used as a base and/or a solvent or a co-solvent.
  • the temperature of the deuteration reaction is generally the reflux temperature of the solvent, and the temperature is usually in the range of 60 to 120 °C.
  • the deuteration reaction time is also not particularly limited and is usually carried out for 0.1 to 20 hours, preferably 0.5 to 10 hours.
  • the relative amounts of the compound of the formula (II) and the compound selected from the group consisting of hydroxylamine and/or hydroxylamine hydrochloride are not particularly limited, and generally they are used in substantially equimolar amounts, for example, a molar ratio of the two is from 1:1.5 to 1.5:1. It is preferably from 1:1.2 to 1.2:1.
  • R 1 to R 5 and R 6 in the formulae (II) and (IIIb) are as defined for the formula (I).
  • nitrous acid, nitrite and/or alkyl nitrite as a deuteration reagent.
  • This reagent nitrosates an "active" (methylene)methyl ( ⁇ -(methylene)methyl group, ie a (methylene) methyl group next to the acyclic carbonyl group).
  • sodium nitrite is usually used as the nitrite.
  • the alkyl nitrite may be a C 1 -C 6 alkyl nitrite such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite or isoamyl nitrite.
  • the deuteration reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Solvents which can be used are, for example, ethanol or aqueous ethanol. In order to promote the completion of the deuteration reaction, it is generally necessary to add concentrated hydrochloric acid. Concentrated hydrochloric acid can also be used as an acid and/or a solvent or a co-solvent.
  • the temperature of the deuteration reaction is a low temperature, and the temperature is usually in the range of -30 to 20 ° C, preferably 5 to 20 ° C.
  • the deuteration reaction time is also not particularly limited and is usually carried out for 0.1 to 20 hours, preferably 0.5 to 10 hours.
  • the relative amounts of the compound of the formula (II) and the compound selected from the group consisting of nitrous acid, nitrite and/or alkyl nitrite are not particularly limited, and generally they are used in substantially equimolar amounts, for example, the molar ratio of the two is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
  • each oxime ester group There may be two configurations for each oxime ester group, either (Z) or (E).
  • the isomers can be separated by a conventional method, but a mixture of isomers can also be used as the photoinitiating substance. Accordingly, the invention also relates to mixtures of configurational isomers of the compounds of formula (I).
  • the esterification of the compounds of the formulae (IIIa) and (IIIb) is conventional, by which the hydroxyl group in the thiol group is converted into an ester group, thereby obtaining a compound of the formula (I).
  • the esterification reagent is not particularly limited as long as the hydroxyl group in the thiol group of the compound of the formulae (IIIa) and (IIIb) can be converted into an ester group.
  • a corresponding acid halide such as an acid chloride, a corresponding carboxylic acid, or a corresponding acid anhydride can also be used.
  • These compounds can be represented by the formulae (IVa), (IVb) and (IVc), respectively:
  • X is a halogen, especially chlorine, and R 7 is as defined for formula (I).
  • the above esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction.
  • a catalyst suitable for the esterification reaction.
  • an acidic catalyst or a basic catalyst can be used.
  • the catalyst one or more selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate may be used.
  • sodium hydrogencarbonate, sodium t-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines such as trialkylamines such as trimethylamine and triethylamine.
  • the amount of catalyst used is conventional and can be determined by common knowledge in the art or by several routine preliminary experiments.
  • the above esterification reaction is usually carried out in a solvent, preferably in an organic solvent.
  • the choice of the type of the solvent is not particularly limited as long as the compound of the formula (IIIa) or the formula (IIIb) and the esterification agent can be dissolved and chemically inert to the esterification reaction, that is, the esterification reaction is not involved.
  • the solvent mention may be made of tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone.
  • the solvent may be used singly or as a mixture of two or more solvents.
  • the relative amounts of the compound of the formula (IIIa) or (Inb) and the esterification agent selected from the compounds (IVa), (IVb) and (IVc) are not particularly limited, and generally they are used in substantially equimolar amounts, for example, two.
  • the molar ratio is from 1:1.5 to 1.5:1, preferably from 1:1.2 to 1.2:1.
  • the esterification reaction can be carried out over a very wide temperature range.
  • the esterification reaction is carried out at a temperature of from -10 ° C to 150 ° C, preferably from 0 ° C to 100 ° C, preferably at ambient temperature.
  • the esterification reaction time is also not particularly limited and is usually carried out for 1 to 24 hours, preferably 1 to 12 hours.
  • reaction mixture comprising a compound of formula (I) is obtained. Therefore, the reaction mixture needs to be worked up to give a purified compound of formula (I).
  • the reaction mixture obtained by the esterification reaction is first filtered, and the filtrate fraction is taken out. The filtrate is then washed to remove the catalyst and unreacted starting materials.
  • the washing liquid is not particularly limited as long as the catalyst and the unreacted raw material can be removed.
  • dilute hydrochloric acid (aqueous solution), saturated aqueous sodium hydrogencarbonate solution and water can be mentioned.
  • the concentration of the dilute hydrochloric acid is not particularly limited, and generally, a dilute hydrochloric acid having a concentration of 5 to 12% is used.
  • the washing with the washing liquid may be carried out once or several times; in the case of multiple times, a single washing liquid may be used, or different washing liquids may be used in sequence.
  • the compound of formula (I) is obtained. If it is desired to further increase the purity of the compound of formula (I), the compound may be further purified, which may be carried out, for example, by recrystallization.
  • the selection of the recrystallization solvent is conventional and is not particularly limited. According to the invention, it is advantageous to recrystallize the crude product of the compound of formula (I) with methanol.
  • the compound of the formula (I) of the invention has a large conjugated system and a long absorption wavelength, and has strong absorption in the wavelength range of 300-450 nm, especially 350-420 nm, especially in the range of 365-405 nm, so it can be applied to UV. - LED light curing system.
  • the preparation materials of the compound of the formula (I) of the present invention are all toxic coumarin ketone compounds, and the degree of harm to the human body and the environment is reduced compared with the conventional photoinitiator.
  • a compound of formula (I) according to the invention as a photoinitiator.
  • the compound of the formula (I) of the present invention can be used as a photoinitiator in a UV-LED photocuring system to effectively initiate a curing reaction.
  • the compounds of formula (I) can be used as photoinitiators or photosensitizers in the fields of coatings, inks, microelectronics, printing, and the like.
  • the amount thereof is conventional or can be determined by routine preliminary tests.
  • Example 2 The method of Example 1 was repeated, and the reaction materials were appropriately changed to obtain the following Table 2-20 and their nuclear magnetic data, respectively.
  • the intermediate product 21a (6.04 g, 0.02 mol) was added to a 100 ml three-necked flask containing 30 ml of tetrahydrofuran, 15 g of concentrated hydrochloric acid (35%) was added, and after stirring for 0.5 h, the isoamyl nitrite was added dropwise at a controlled temperature of 5 ° C ( 2.36 g, 0.02 mol), after the addition was completed, the reaction was continued at 10 ° C for 3 h. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, and the organic phase was collected, and the organic phase was washed with water to neutral.
  • Example 21 The procedure of Example 21 was repeated, and the reaction materials were appropriately changed to obtain the following compounds 22-30 and their nuclear magnetic data, respectively.
  • the method of Example 1 was repeated, and the reaction materials were appropriately changed to obtain the following Table Compounds 31-50 and their nuclear magnetic data, respectively.
  • Patent Application Publication No. CN104817653A discloses the following Compound A.
  • the initial decomposition temperatures of the compound and the inventive compounds 1, 3, 21, 28, 31 and 32 are as follows:
  • the photographic properties of the photoinitiator were tested using a Ugra print strip as a mask.
  • the sections of the Ugra print test strip are shown in Figure 1.
  • the Ugra print test strip is divided into five control segments, from left to right: continuous density step (1); yin and yang micro-concentric concentric segments (2); full-order mesh points (3); Shadow control section (4); highlight, shadow control section (5).
  • the first paragraph the continuous density step section is divided into 13 gradients to control the exposure and development.
  • full-order network segment consists of 10%-100%, the difference is 10% of the evaluation network, divided into two rows, used to measure the transfer of printing, proofing and printing, and Measure the curve of film outlets and printing, proofing and printing online shop.
  • high-light, dark-control segment, fine dot segment is arranged by high-light small dots and dark-adjusted deep dots, which is used to finely control the accuracy of exposure and development.
  • the photosensitive composition containing the photoinitiator is applied onto an aluminum substrate, and then exposed and developed, the sensitivity is evaluated from the continuous adjustment ruler of the obtained image, and the precision is evaluated from the micro-line test block region, thereby evaluating the pros and cons of the photosensitive composition formulation. .
  • a photosensitive composition containing a photoinitiator is prepared according to the following composition:
  • the photoinitiator in the above composition is selected from the coumarin oxime ester compound of the formula (I) of the present invention or a photoinitiator known in the art (for comparison).
  • the acrylate resin is a resin commercially available from Shanghai Bushun International Trading Co., Ltd. under the trade name of FS2600K, having a functionality of 2 and a number average molecular weight of 1400.
  • Dipentaerythritol hexaacrylate is a product of the trade name GM66G0C purchased from Shanghai Bushun International Trading Co., Ltd.
  • the crystal violet dye is a product commercially available from Shanghai Sinopharm under the trade name of hexamethyllimanilide hydrochloride.
  • Aluminum plate base size 1030mm ⁇ 800mm
  • Aluminum plate base thickness 0.28-0.3mm
  • the rotation speed of the centrifugal coater is controlled so that the coating amount (in terms of solid content) coated on the aluminum plate base is 1.0-2.5 g/m 2 , and after preliminary drying on a centrifugal coater, the blast is transferred to 100 ° C. Drying in a dryer for 3 minutes gave a violet laser CTP original. Then, the Ugla test strip was used as a mask to test the photographic performance of the plate, and after exposure for a while, it was developed with a 1% NaOH aqueous solution.
  • the photopolymerizable compound is polymerized in the presence of an initiator, the insoluble solution is insoluble, and the non-exposed area is soluble, thus obtaining a negative image.
  • the sensitivity of the photoinitiator was evaluated from the continuous adjustment of the obtained image by exposure development.
  • the sensitivity of the initiator system is characterized by the highest gray scale number retained (i.e., polymerized) after development. The higher the gray level, the higher the sensitivity of the test system. The results are shown in Table 3.
  • OXE-01 represents 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzohydrazide)
  • OXE-02 represents 1-(6- o-Methylbenzoyl-9-ethyloxazol-3-yl)-(3-ethanone)-1-indole acetate
  • the structural formulas are as follows:
  • the photoinitiators 1-50 of the present invention have higher gray scale numbers at 365 nm, 385 nm, 395 nm, and 405 nm than the commercially available photoinitiators OXE-01 and OXE-02. That is to say, the coumarin (keto) oxime ester photoinitiator of the present invention has excellent sensitizing properties at wavelengths of 365 nm, 385 nm, 395 nm and 405 nm, and is suitable for UV-rays of 365 nm, 385 nm, 395 nm, and 405 nm. LED light source.
  • the coumarin (keto) oxime ester photoinitiator of the formula (I) of the present invention has good sensitizing properties at wavelengths of 365 nm, 385 nm, 395 nm and 405 nm, which is superior to the current stage.
  • a ketone ester photoinitiator such as OXE-01 and OXE-02.
  • the compound disclosed by the invention has simple production process and high yield, and is very suitable for industrial production.
  • UV-LED light sources of 365nm, 385nm, 395nm and 405nm
  • UV-LED photocuring such as coatings, inks, microelectronics, printing, etc.
  • Such substances have good market prospects.
  • the use of UV-LED light sources in the field of ultraviolet curing is limited to a certain extent, so the photoinitiator of the present invention can promote green environmental protection UV-LEDs.
  • Light sources contribute to the widespread use of the UV light curing industry.

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Abstract

本发明涉及一种式(I)的香豆素(酮)肟酯化合物，其中n和 R1、R2、R3、R4、R5、R6 和 R7 如说明书中所定义。该化合物在 300-450nm 范围内具有很强的紫外吸收，吸收光能后能够迅速发生能量转移，持续引发聚合，在感光性及图案完整性方面具有明显优势，非常适合于 UV-LED 光源辐射固化。此外，式 (I) 化合物还具有良好的热稳定性。本发明还涉及式 (I) 化合物的制备方法和该化合物的用途，该化合物适合在 UV-LED 光固化体系中作为光引发剂，适合 UV-LED 光固化的辐射波长。

Description

香豆素肟酯类化合物及其制备和应用 技术领域
本发明涉及香豆素3-酮肟酯类化合物，该类化合物可用作光引发剂。本发明还涉及香豆素3-酮肟酯类化合物的制备及应用。
背景技术
光引发剂又称光敏剂或光固化剂，是一类能在紫外光区(250-400nm)或可见光区(400-600nm)吸收一定波长的能量，产生自由基、阳离子等，从而引发单体聚合交联固化的化合物。在光固化体系中，光引发剂一般占3-5％，含量虽低，却是其中的关键组分，对光固化速度起决定作用。它关系到配方体系在光辐照时，低聚物及稀释剂能否迅速交联固化，从而由液态转变为固态。目前，光固化技术已广泛应用在涂料、油墨、微电子、印刷等传统领域，另外还用于制备激光录像及三维元件等新型领域。作为光固化体系的重要组分，光引发剂必须满足不同光固化条件和应用的需要。在自由基光引发剂领域，主要目标是：提高光敏感度，提高表面固化效率(抗氧阻聚)，提高深层固化性能，提高光引发剂在单体及树脂中的溶解性，降低毒性和气味，降低固化后未固化引发剂的迁移性，降低黄变性。
肟酯类光引发剂因其具有优异的感光性能成为近年来逐渐受到重视的一类光引发剂，其中巴斯夫产品OXE-01和OXE-02是目前市场上常见的两种肟酯类代表性产品，这两种产品具有较高的光敏度，但是它们的紫外吸收波长偏短，并不适用于UV-LED光源(发射波长365nm、385nm、395nm、405nm、420nm)的需求。国内也有一些关于肟酯类光引发剂的专利，例如CN102775527A披露了一种二苯硫醚酮肟酯类光引发剂及其制备方法，CN102492059A公开了取代的二苯硫醚酮肟酯类光引发剂等等。但是大多数引发剂的紫外吸收波长在250-350nm，无法与日益发展的LED光源匹配，这就大大限制了肟酯类光引发剂的应用。
CN104817653A披露了一种适用于UV-LED光源固化的肟酯类光引发剂，该引发剂化合物为香豆素醛肟酯类化合物，然而研究表明此类化合物的热稳定性不及OXE-01[朱桂刚，香豆素肟酯衍生物的合成及其在LED光固化中的应用，硕士论文，2016；Dietliker K，Birbaum J L，
Figure PCTCN2018088830-appb-000001
R，et al.Photolatent catalysts[J].CHIMIA International Journal for Chemistry，2002，56(5)： 197-202.]。
CN1889960A披露了香豆素酮肟酯类化合物可用于药物组合物或者化妆品组合物中，用以预防和治疗疾病，包括免疫性疾病、慢性炎症、神经疾病和皮肤病、肿瘤疾病、特定病毒(特别是SARS)等。从这个意义上说，此类化合物是安全无毒的，但并未有文献报道将香豆素酮肟酯类化合物用作光引发剂。
因此，仍旧需要一种吸收波长适合UV-LED光源(发射波长300-450nm、尤其365-420nm)并且热稳定性良好的光引发剂。
发明内容
鉴于现有技术中存在的问题，本发明的发明人在适于UV-LED光源(发射波长300-450nm、尤其365-420nm)辐射固化的光引发剂方面进行了广泛而又深入的研究，以期找到一种能够替代OXE-01和OXE-02以更适合UV-LED光源固化并且具有良好热稳定性的光引发剂。本发明人发现，将未取代或取代的香豆素直接或经由羰基连接上肟酯结构部分，如此获得的香豆素(酮)肟酯化合物在300-450nm、尤其350-420nm范围内具有很强的紫外吸收，并且具有良好的热稳定性，从而适合用作UV-LED光源辐射固化的光引发剂。本发明目的正是基于前述发现得以实现。
因此，本发明的一个目的是提供一种香豆素(酮)肟酯化合物，该类化合物的吸收波长不仅适合UV-LED光源辐射固化，而且还具有很好的热稳定性。
本发明的另一目的是提供制备本发明香豆素(酮)肟酯化合物的方法。
本发明的再一目的是提供本发明香豆素(酮)肟酯化合物作为光引发剂或光敏剂的用途。
实现本发明上述目的的技术方案可以概括如下：
1.式(I)的香豆素(酮)肟酯化合物：
Figure PCTCN2018088830-appb-000002
其中：
n为0或1；
R 1、R 2、R 3、R 4、R 5相互独立地表示氢、卤素、硝基、羟基、巯基、羧基、C 1-C 8羧酸酯基、磺酸基、氨基、氰基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基，其中前述氨基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 2-C 6烯基和C 2-C 6炔基，或者
R 1与R 2一起、R 2与R 3一起、R 3与R 4一起或者R 1与R 2一起且R 3与R 4一起形成总共具有3-4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和的二价基团；以及
R 6、R 7相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基，其中前述C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷氧基、卤素、硝基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基和巯基，
其中满足如下定义的化合物除外：n为0，R 1、R 2、R 3、R 4和R 5均为H，R 6为甲基，并且R 7为正丙基。
2.根据第1项的化合物，其中R 1、R 2、R 3、R 4和R 5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、C 1-C 6羧酸酯基、磺酸基、氨基、氰基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基，其中前述氨基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯 氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、C 2-C 4烯基和C 2-C 4炔基；或者，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3-4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和的二价基团，
优选的是，R 1、R 2、R 3、R 4和R 5彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 4烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；或者，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3个或4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和二价基团，例如-O-CH 2-O-、-S-CH 2-S-、-N-CH 2-N-、-O-CH 2CH 2-O-、-S-CH 2CH 2-S-、-N-CH 2CH 2-N-或-CH＝CH-CN＝CH-。
3.根据第1或2项的化合物，其中R 6、R 7相互独立地表示直链或支化的C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基，其中前述C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基，
优选的是，R 6、R 7彼此独立地选自直链或支化的C 1-C 8烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 4烷基、被苯基取代的C 1-C 4烷基和苯基，其中前述苯基各自任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基；
更优选的是，R 6为直链或支化的C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基和巯基，以及
R 7为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。
4.根据第1-3项中任一项的化合物，其中R 5为H。
5.根据第1或4项的化合物，其中
n为0，
R 1、R 2、R 3和R 4彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 6烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；或者，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3个或4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和二价基团，例如-CH＝CH-CN＝CH-；
R 6为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：氟、氯、溴、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基和卤代C 1-C 4烷基，以及
R 7为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基和二(C 1-C 4烷基)氨基，或者
n为1，
R 1、R 2、R 3和R 4彼此独立地选自氢、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；或者，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3个或4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和二价基团，例如-O-CH 2-O-、-S-CH 2-S-、-N-CH 2-N-、-O-CH 2CH 2-O-、-S-CH 2CH 2-S-或-N-CH 2CH 2-N；
R 6为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基或被C 5-C 6环烷基取代的C 1-C 2烷基，以及
R 7为直链或支化的C 1-C 6烷基或任选被硝基取代的苯基。
6.根据第1项的化合物，其中式(I)化合物选自化合物1-50。
7.一种制备如第1-6项中任一项所要求的化合物的方法，包括以下步骤：
(1)肟化反应：当n为0时，使式(II)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(IIIa)化合物
Figure PCTCN2018088830-appb-000003
当n为1时，使式(II)化合物与选自亚硝酸、亚硝酸盐和亚硝酸烷基酯中的试剂进行肟化反应，得到式(IIIb)化合物：
Figure PCTCN2018088830-appb-000004
其中，式(II)、(IIIa)和(IIIb)中的R 1-R 5和R 6如第1-6项中任一项所定义；以及
(2)将式(IIIa)或(IIIb)化合物酯化，得到式(I)化合物。
8.根据第7项的方法，其中
当n为0时：肟化反应在乙酸钠、吡啶、哌啶、三乙胺或其混合物存在下进行；和/或，肟化反应在乙醇或含水的乙醇作为溶剂存在下进行；和/或，肟化反应的温度为60-120℃；和/或，肟化反应时间为0.1-20小时，优选0.5-10小时；式(II)化合物与选自羟胺和/或盐酸羟胺的化合物的摩尔比为1∶1.5-1.5∶1，优选为1∶1.2-1.2∶1；
当n为1时，肟化反应在浓盐酸存在下进行；和/或，肟化反应在乙醇或含水的乙醇作为溶剂存在下进行；和/或，肟化反应的温度为-30至20℃，优选5-20℃；和/或，肟化反应时间为0.1-20小时，优选0.5-10小时；式(II)化合物与选自亚硝酸、亚硝酸盐和/或亚硝酸烷基酯的化合物的摩尔比为1∶1.5-1.5∶1，优选为1∶1.2-1.2∶1。
9.根据第7或8项的方法，其中亚硝酸烷基酯为亚硝酸C 1-C 6烷基酯，例如亚硝酸甲酯、亚硝酸乙酯、亚硝酸异丙酯、亚硝酸丁酯、亚硝酸异戊酯；和/或，步骤(2)的酯化采用选自下式(IVa)、(IVb)和(IVc)化合物的酯化试剂进行：
Figure PCTCN2018088830-appb-000005
其中X为卤素，尤其是氯，和R 7如权利要求1-6中任一项所定义。
10.根据第7-9项中任一项的方法，其中酯化反应在选自下组的一种或多种催化剂存在下进行：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。
11.根据第7-10项中任一项的方法，其中酯化反应在选自四氢呋喃、苯、甲苯、N，N-二甲基甲酰胺、二氯甲烷和丙酮的溶剂中进行；和/或，式(IIIa)或式(IIIb)化合物与选自(IVa)、(IVb)和(IVc)化合物的酯化试剂的摩尔比为1∶1.5-1.5∶1，优选为1∶1.2-1.2∶1。
12.如第1-6项中任一项所要求的式(I)化合物作为光引发剂的用途，尤其是在UV-LED光固化体系中作为光引发剂的用途，特别是在辐射波长为300-450nm、优选350-420nm、尤其365-405nm的光固化体系中作为光引发剂的用途。
附图说明
图1是乌格拉(Ugra)晒版测试条的示意图，其中
1——连续密度梯尺段，
2——阴阳微米等线同心圆线圈段，
3——全阶调网点段，
4——重影控制段，和
5——高光、暗调控制段。
具体实施方式
根据本发明的第一个方面，提供了一种下(I)的香豆素(酮)肟酯化合物：
Figure PCTCN2018088830-appb-000006
其中：
n为0或1；
R 1、R 2、R 3、R 4、R 5相互独立地表示氢、卤素、硝基、羟基、巯基、羧基、C 1-C 8羧酸酯基、磺酸基、氨基、氰基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基，其中前述氨基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 2-C 6烯基和C 2-C 6炔基，或者
R 1与R 2一起、R 2与R 3一起、R 3与R 4一起或者R 1与R 2一起且R 3与R 4一起形成总共具有3-4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和的二价基团；以及
R 6、R 7相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基，其中前述C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷氧基、卤素、硝基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基和巯基，
其中满足如下定义的化合物除外：n为0，R 1、R 2、R 3、R 4和R 5均为H，R 6 为甲基，并且R 7为正丙基。
式(I)化合物中既包含香豆素基结构部分，又包含(酮)肟酯类结构部分。该化合物在350-450nm范围内具有很强的紫外吸收，吸收光能后能够迅速发生能量转移，持续引发聚合，在感光性及图案完整性方面具有明显优势，非常适合于UV-LED光源且其安全无毒可被用于食品包装等领域。此外，式(I)化合物还具有良好的热稳定性。
在本发明中，前缀“C n-C m”在每种情况下表示该基团中包含的碳原子数为n-m个。
“卤素”是指氟、氯、溴和碘。在本发明中，优选的是，卤素包括F、Cl或其组合。
本文所用的术语“C n-C m烷基”是指具有n-m个，例如1-20个，优选1-12个，更优选1-8个，特别优选1-6个，尤其优选1-4个碳原子的支化或未支化饱和烃基，例如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1，1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2，2-二甲基丙基、1-乙基丙基、己基、1，1-二甲基丙基、1，2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1，1-二甲基丁基、1，2-二甲基丁基、1，3-二甲基丁基、2，2-二甲基丁基、2，3-二甲基丁基、3，3-二甲基丁基、1-乙基丁基、2-乙基丁基、1，1，2-三甲基丙基、1，2，2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、庚基、辛基、2-乙基己基、壬基、癸基、十一烷基、十二烷基及其异构体。C 1-C 8烷基可以是甲基、乙基、丙基、异丙基、正丁基、2-丁基、叔丁基、戊基、异戊基、己基、庚基、辛基及其异构体。C 1-C 6烷基可以是甲基、乙基、丙基、异丙基、正丁基、2-丁基、叔丁基、戊基、异戊基、己基及其异构体。C 1-C 4烷基可以是甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1，1-二甲基乙基及其异构体。
本文所用术语“C 2-C m烯基”是指具有2-m个，例如2-20个，优选2-6个，更优选2-4个碳原子并且具有一个或多个位于任何位置的双键的支化或未支化不饱和开链烃基，如乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-甲基-1-丁烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、1-甲基-2-丁烯基、2-甲基-2-丁烯基、3-甲基-2-丁烯基、1-甲基-3-丁烯基、2-甲基-3-丁烯基、3-甲基-3-丁烯基、1，1-二甲基 -2-丙烯基、1，2-二甲基-1-丙烯基、1，2-二甲基-2-丙烯基、1-乙基-1-丙烯基、1-乙基-2-丙烯基、1-己烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、1-甲基-1-戊烯基、2-甲基-1-戊烯基、3-甲基-1-戊烯基、4-甲基-1-戊烯基、1-甲基-2-戊烯基、2-甲基-2-戊烯基、3-甲基-2-戊烯基、4-甲基-2-戊烯基、1-甲基-3-戊烯基、2-甲基-3-戊烯基、3-甲基-3-戊烯基、4-甲基-3-戊烯基、1-甲基-4-戊烯基、2-甲基-4-戊烯基、3-甲基-4-戊烯基、4-甲基-4-戊烯基、1，1-二甲基-2-丁烯基、1，1-二甲基-3-丁烯基、1，2-二甲基-1-丁烯基、1，2-二甲基-2-丁烯基、1，2-二甲基-3-丁烯基、1，3-二甲基-1-丁烯基、1，3-二甲基-2-丁烯基、1，3-二甲基-3-丁烯基、2，2-二甲基-3-丁烯基、2，3-二甲基-1-丁烯基、2，3-二甲基-2-丁烯基、2，3-二甲基-3-丁烯基、3，3-二甲基-1-丁烯基、3，3-二甲基-2-丁烯基、1-乙基-1-丁烯基、1-乙基-2-丁烯基、1-乙基-3-丁烯基、2-乙基-1-丁烯基、2-乙基-2-丁烯基、2-乙基-3-丁烯基、1，1，2-三甲基-2-丙烯基、1-乙基-1-甲基-2-丙烯基、1-乙基-2-甲基-1-丙烯基、1-乙基-2-甲基-2-丙烯基及其异构体。C 2-C 6烯基可以是乙烯基、丙烯基、1-丁烯基、2-丁烯基、异丁烯基、1-戊烯基、2-戊烯基、新戊烯基、1-己烯基、2-己烯基、3-己烯基、异己烯基、新己烯基及其异构体。C 2-C 4烯基可以是乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基及其异构体。
本文所用术语“C 2-C m炔基”是指具有2-m个，例如2-20个，优选2-6个，更优选2-4个碳原子并且具有一个或多个位于任何位置的叁键的支化或未支化不饱和开链烃基，如乙炔基、丙炔基、1-丁炔基、2-丁炔基及其异构体。C 2-C 6炔基可以是乙炔基、丙炔基、1-丁炔基、2-丁炔基、1-戊炔基、2-戊炔基、3-戊炔基、4-戊炔基、1-己炔基、2-己炔基、3-己炔基、4-己炔基、5-己炔基及其异构体。C 2-C 4炔基可以是乙炔基、丙炔基、1-丁炔基、2-丁炔基及其异构体。
本文所用术语“C 3-C m环烷基”是指具有3-m个，例如3-20个，优选3-8个，更优选5-6个环碳原子的饱和脂环族单环基团，例如环丙基、环丁基、环戊基、环己基、环庚基、环辛基和环癸基。
术语“C 4-C m环烷基烷基”表示被环烷基取代的烷基并且总共含有4-m个碳原子，例如4-20个碳原子，优选4-10个碳原子，更优选4-6个碳原子，其中烷基和环烷基适用本文所定义，例如环丙基甲基、环丙基乙基、环丙基丙基、环丙基丁基、环丁基甲基、环丁基乙基、环丁基丙基、环丁基丁基、环戊基甲基、环戊基乙基、环戊基丙基、环戊基丁基、环己基甲基、环己基乙基、环己基丙基、 环己基丁基等。
术语“C 4-C 10烷基环烷基”表示被烷基取代的环烷基并且总共含有4-m个碳原子，例如4-10个碳原子，优选4-8个碳原子，更优选4-6个碳原子，其中烷基和环烷基适用本文所定义，例如甲基环丙基、乙基环丙基、丙基环丙基、丁基环丙基、甲基环丁基、乙基环丁基、丙基环丁基、丁基环丁基、甲基环戊基、乙基环戊基、丙基环戊基、丁基环戊基、甲基环己基、乙基环己基、丙基环己基、丁基环己基等。
本文所用术语“C 6-C m芳基”是指含有6-m个碳原子，例如6-18个，优选6-10个碳原子的单环、双环或三环芳族烃基。作为C 6-C m芳基的实例，可提及苯基、甲苯基、乙苯基、丙苯基、丁苯基、二甲苯基、甲基乙基苯基、二乙基苯基、甲基.丙基苯基和萘基等；优选苯基或萘基，尤其是苯基(作为取代基也表示为C 6H 5)。
术语“C 7-C 20芳烷基”表示被芳基取代的烷基并且总共含有7-20个碳原子，例如7-12个，优选7-10个碳原子，更优选7-8个碳原子，其中烷基和芳基适用本文所定义，例如苯甲基、苯乙基、萘甲基、萘乙基等。
术语“C 7-C 20烷基芳基”表示被烷基取代的芳基并且总共含有7-20个碳原子，例如7-12个，优选7-10个碳原子，更优选7-8个碳原子，其中烷基和芳基适用本文所定义，例如甲基苯基、二甲基苯基、三甲基苯基、乙基苯基、二乙基苯基、三乙基苯基、甲基萘基、乙基萘基等。
术语“C n-C m烷氧基”和“C n-C m烷硫基”是指在C n-C m烷基对应的开链C n-C m烷烃的任何碳原子上键合有一个氧原子或一个硫原子作为连接基团的C n-C m烷基，例如C 1-C 20烷氧(或硫)基，优选C 1-C 12烷氧(或硫)基，更优选C 1-C 8烷氧(或硫)基，特别优选C 1-C 6烷氧(或硫)基，尤其优选C 1-C 4烷氧(或硫)基。C 1-C 8烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基、庚氧基、辛氧基、异辛氧基及其异构体。C 1-C 4烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基及其异构体。C 1-C 8烷硫基可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基、2-丁硫基、叔丁硫基、戊硫基、异戊硫基、己硫基、庚硫基、辛硫基、异辛硫基及其异构体。C 1-C 4烷硫基可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基及其异构体。
术语“C 2-C m烯氧基”和“C 2-C m烯硫基”是指在C 2-C m烯基对应的C 2-C m链烯 烃中的任何饱和碳原子上键合有一个氧原子或一个硫原子作为连接基团的C 2-C m烯基，例如C 2-C 20烯氧(或硫)基，优选C 2-C 12烯氧(或硫)基，更优选C 2-C 8烯氧(或硫)基，特别优选C 2-C 6烯氧(或硫)基，尤其优选C 2-C 4烯氧(或硫)基，例如乙烯氧基、丙烯氧基、异丙烯氧基、正丁烯氧基、仲丁烯氧基、异丁烯氧基、叔丁烯氧基及其异构体、乙烯硫基、丙烯硫基、异丙烯硫基、正丁烯硫基及其异构体。
术语“C 2-C m炔氧基”和“C 2-C m炔硫基”是指在C 2-C m炔基对应的C 2-C m链炔烃中的任何饱和碳原子上键合有一个氧原子或一个硫原子作为连接基团的C 2-C m炔基，例如C 2-C 20炔氧(或硫)基，优选C 2-C 12炔氧(或硫)基，更优选C 2-C 8炔氧(或硫)基，特别优选C 2-C 6炔氧(或硫)基，尤其优选C 2-C 4炔氧(或硫)基，例如乙炔氧基、丙炔氧基、正丁炔氧基、仲丁炔氧基及其异构体、乙炔硫基、丙炔硫基、丙炔硫基、正丁炔硫基、仲丁炔硫基及其异构体。
术语“C 3-C m环烷氧基”和“C 3-C m环烷硫基”是指在C 3-C m环烷基对应的C 3-C m环烷烃中的任何环碳原子上键合有一个氧原子或一个硫原子作为连接基团的C 3-C m环烷基，例如C 3-C 20环烷氧(或硫)基，优选C 3-C 8环烷氧(或硫)基，更优选C 5-C 6环烷氧(或硫)基，例如环丙基氧基、环丁基氧基、环戊基氧基、环己基氧基、环庚基氧基、环辛基氧基、环癸基氧基及其异构体、环丙基硫基、环丁基硫基、环戊基硫基、环己基硫基、环庚基硫基、环辛基硫基、环癸基硫基及其异构体。
术语“C 4-C m环烷基烷氧基”和“C 4-C m环烷基烷硫基”是指被环烷基取代的烷氧(硫)基并且总共含有4-m个碳原子，例如4-20个碳原子，优选4-8个碳原子，其中环烷基和烷氧(硫)基适用本文所定义，例如环丙基甲氧基、环丙基乙氧基、环丙基丙氧基、环丙基丁氧基、环丁基甲氧基、环丁基乙氧基、环丁基丙氧基、环丁基丁氧基、环戊基甲氧基、环戊基乙氧基、环戊基丙氧基、环戊基丁氧基、环己基甲氧基、环己基乙氧基、环己基丙氧基、环己基丁氧基、环丙基甲硫基、环丙基乙硫基、环丙基丙硫基、环丙基丁硫基、环丁基甲硫基、环丁基乙硫基、环丁基丙硫基、环丁基丁硫基、环戊基甲硫基、环戊基乙硫基、环戊基丙硫基、环戊基丁硫基、环己基甲硫基、环己基乙硫基、环己基丙硫基、环己基丁硫基等。
本文所用术语“C 6-C m芳氧基”和“C 6-C m芳硫基”是指在C 6-C m芳基对应的C 6-C m芳烃中的任何芳族碳原子上键合有一个氧原子或一个硫原子作为连接基 团的C 6-C m芳基，例如苯硫基、苯氧基、甲苯氧基、甲苯硫基、萘硫基、萘氧基等。
在本发明中，n为0或1。n为0时，式(I)化合物称作香豆素肟酯化合物；当n为1时，式(I)化合物称作香豆素酮肟酯化合物。这两种化合物统称为香豆素(酮)肟酯化合物。
在本发明中，R 1、R 2、R 3、R 4和R 5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、C 1-C 8羧酸酯基、磺酸基、氨基、氰基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基，其中前述氨基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 2-C 6烯基和C 2-C 6炔基。作为选择，R 1与R 2一起、R 2与R 3一起、R 3与R 4一起或者R 1与R 2一起且R 3与R 4一起形成总共具有3-4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和的二价基团。
优选的是，R 1、R 2、R 3、R 4和R 5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、C 1-C 6羧酸酯基、磺酸基、氨基、氰基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基，其中前述氨基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4 烷硫基、C 2-C 4烯基和C 2-C 4炔基。作为选择，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3-4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和的二价基团。
特别优选的是，R 1、R 2、R 3、R 4和R 5彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 4烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基。作为选择，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3个或4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和二价基团，例如-O-CH 2-O-、-S-CH 2-S-、-N-CH 2-N-、-O-CH 2CH 2-O-、-S-CH 2CH 2-S-、-N-CH 2CH 2-N-或-CH＝CH-CN＝CH-。
在本发明中，R 6、R 7相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基，其中前述C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 6烷硫基、C 1-C 6烷氧基、C 1-C 6烷基、卤素、硝基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基和巯基。
优选的是，R 6、R 7相互独立地表示直链或支化的C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基，其中前述C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。
特别优选的是，R 6、R 7彼此独立地选自直链或支化的C 1-C 8烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 4烷基、被苯基取代的C 1-C 4烷基和苯基，其中前述苯基各自任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。尤其是，R 6为直链或支化的C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基和巯基，以及R 7为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单 (C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。
还优选的是，R 5为H。
尤其优选的是，当n为0时，
R 1、R 2、R 3和R 4彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 6烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；或者，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3个或4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和二价基团，例如-CH＝CH-CN＝CH-；
R 6为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：氟、氯、溴、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基和卤代C 1-C 4烷基，以及
R 7为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基和二(C 1-C 4烷基)氨基，或者
当n为1时，
R 1、R 2、R 3和R 4彼此独立地选自氢、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；或者，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3个或4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和二价基团，例如-O-CH 2-O-、-S-CH 2-S-、-N-CH 2-N-、-O-CH 2CH 2-O-、-S-CH 2CH 2-S-或-N-CH 2CH 2-N；
R 6为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基或被C 5-C 6环烷基取代的C 1-C 2烷基，以及
R 7为直链或支化的C 1-C 6烷基或任选被硝基取代的苯基。
在本发明的一个特别优选的实施方案中，式(I)化合物选自化合物1-50。化合物1-50分别在实施例1-50中制备。
根据本发明的第二个方面，提供了一种制备本发明式(I)化合物的方法，包括以下步骤：
(1)肟化反应：当n为0时，使式(II)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(IIIa)化合物
Figure PCTCN2018088830-appb-000007
当n为1时，使式(II)化合物与选自亚硝酸、亚硝酸盐和亚硝酸烷基酯中的试剂进行肟化反应，得到式(IIIb)化合物：
Figure PCTCN2018088830-appb-000008
其中，式(II)、(IIIa)和(IIIb)中的R 1-R 5和R 6如对式(I)所定义；以及
(2)将式(IIIa)或(IIIb)化合物酯化，得到式(I)化合物。
为了制备本发明的式(I)化合物，需要先进行肟化反应，以引入肟基，然后肟基中的羟基经酯化反应转变成相应的酯基，从而获得本发明的香豆素(酮)肟酯化合物。
肟化反应
肟化反应通常从羰基化合物开始。为此，当n为0时，使式(II)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(IIIa)化合物
Figure PCTCN2018088830-appb-000009
式(II)和(IIIa)中的R 1-R 5和R 6如对式(I)所定义。为了将式(II)中的非环羰基转变为肟基，通常需要使用盐酸羟胺(NH 2OH.HCl)、羟胺(NH 2OH)或其混合物作为肟化试剂。该肟化反应通常在有机溶剂中进行，优选在有机极性溶剂中进行。可采用的溶剂例如有乙醇或含水的乙醇。为了促进肟化反应进行完全，一般需 加入乙酸钠、吡啶、哌啶、三乙胺之类的碱。这当中，吡啶、哌啶、三乙胺也可用作碱和/或溶剂或助溶剂。肟化反应的温度一般为溶剂的回流温度，温度范围通常在60-120℃。肟化反应时间也没有特别的限制，通常进行0.1-20小时，优选0.5-10小时。式(II)化合物与选自羟胺和/或盐酸羟胺的化合物的相对用量没有特别的限制，通常而言它们以大致等摩尔量使用，例如二者的摩尔比为1∶1.5-1.5∶1，优选为1∶1.2-1.2∶1。
当n为1时，使式(II)化合物与亚硝酸、亚硝酸盐和/或亚硝酸烷基酯进行肟化反应，得到式(IIIb)化合物：
Figure PCTCN2018088830-appb-000010
其中，式(II)和(IIIb)中的R 1-R 5和R 6如对式(I)所定义。为了将式(II)中的非环羰基转变为酮肟基，通常需要使用亚硝酸、亚硝酸盐和/或亚硝酸烷基酯作为肟化试剂。该试剂将“活性”(亚)甲基(α-(亚)甲基，即紧挨着非环羰基的(亚)甲基)进行亚硝化。作为亚硝酸盐，通常使用亚硝酸钠。亚硝酸烷基酯可以是亚硝酸C 1-C 6烷基酯，例如亚硝酸甲酯、亚硝酸乙酯、亚硝酸异丙酯、亚硝酸丁酯、亚硝酸异戊酯。该肟化反应通常在有机溶剂中进行，优选在有机极性溶剂中进行。可采用的溶剂例如有乙醇或含水的乙醇。为了促进肟化反应进行完全，一般需加入浓盐酸。浓盐酸也可用作酸和/或溶剂或助溶剂。肟化反应的温度为低温，温度范围通常在-30至20℃，优选5-20℃。肟化反应时间也没有特别的限制，通常进行0.1-20小时，优选0.5-10小时。式(II)化合物与选自亚硝酸、亚硝酸盐和/或亚硝酸烷基酯的化合物的相对用量没有特别的限制，通常而言它们以大致等摩尔量使用，例如二者的摩尔比为1∶1.5-1.5∶1，优选为1∶1.2-1.2∶1。
每个肟酯基可能存在两种构型，(Z)型或(E)型。可通过常规方法分离异构体，但也可使用异构体混合物作为光引发物质。因此，本发明还涉及式(I)化合物的构型异构体的混合物。
酯化反应
式(IIIa)和(IIIb)化合物的酯化是常规的，通过该反应，肟基中的羟基转变 为酯基，从而获得式(I)化合物。作为酯化试剂，没有特别的限制，只要能将式(IIIa)和(IIIb)化合物肟基中的羟基转变为酯基即可。作为酯化试剂，可以使用相应的酰卤，如酰氯，也可使用相应的羧酸，还可使用相应的酸酐。这些化合物可分别表示为式(IVa)、(IVb)和(IVc)：
Figure PCTCN2018088830-appb-000011
其中X为卤素，尤其是氯，和R 7如对式(I)所定义。
为了加速酯化反应，上述酯化反应通常在适于酯化反应的催化剂存在下进行。作为催化剂，既可以使用酸性催化剂，也可以使用碱性催化剂。作为催化剂，可以使用选自下组的一种或多种：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。催化剂的用量是常规的，可以通过本领域的常识确定，或者通过几个例行的预备实验来确定。
为了提高式(I)化合物的产率，有利的是，在酯化反应过程中移除酯化反应产生的水。这例如可以通过蒸馏冷凝来进行。
上述酯化反应通常在溶剂中，优选在有机溶剂中进行。作为溶剂的类型的选择，没有特别的限制，只要能够将式(IIIa)或式(IIIb)化合物和酯化试剂溶解并且对酯化反应呈化学惰性即可，即不参与该酯化反应即可。作为溶剂的实例，可以提及四氢呋喃、苯、甲苯、N，N-二甲基甲酰胺、二氯甲烷和丙酮。溶剂可以使用单一种，也可以使用两种或更多种溶剂的混合物。
式(IIIa)或式(Inb)化合物与选自(IVa)、(IVb)和(IVc)化合物的酯化试剂的相对用量没有特别的限制，通常而言它们以大致等摩尔量使用，例如二者的摩尔比为1∶1.5-1.5∶1，优选为1∶1.2-1.2∶1。
酯化反应可以在非常宽的温度范围内进行。根据本发明有利的是，酯化反应在-10℃至150℃，优选0℃至100℃的温度下进行，优选常温下进行。酯化反应时间也没有特别的限制，通常进行1-24小时，优选1-12小时。
在酯化反应完成之后，获得包含式(I)化合物的反应混合物。因此，需要对该反应混合物进行后处理，以得到提纯的式(I)化合物。通常而言，首先过滤酯 化反应得到的反应混合物，取出滤液部分。然后，将滤液进行洗涤，以除去催化剂和未反应的原料。作为洗液，没有特别的限制，只要能除去催化剂和未反应的原料即可。作为洗液的实例，可以提及稀盐酸(水溶液)、饱和碳酸氢钠水溶液和水。稀盐酸的浓度没有特别的限制，通常而言使用浓度为5-12％的稀盐酸。用洗液洗涤可以进行一次，也可进行多次；在进行多次的情况下，可使用单一种洗液，也可依次使用不同的洗液。根据本发明有利的是，将对酯化反应得到的反应混合物过滤得到的滤液依次用稀盐酸、饱和碳酸氢钠水溶液和水进行洗涤。当然，每一次用洗液洗涤后，都需要倒掉水相之后再用下一种洗液对有机相进行洗涤。洗涤之后，需要干燥以除去残留的水。为此，通常可使用无水硫酸钠进行干燥。干燥之后，再除去残留的有机溶剂。作为这里除去有机溶剂的手段，没有特别的限制，通常可通过减压蒸馏来除去有机溶剂。除去残留有机溶剂之后，得到了式(I)化合物的粗产物。如果想要进一步提高式(I)化合物的纯度，还可对该化合物进行进一步提纯，这例如可通过重结晶的方式来进行。重结晶溶剂的选择是常规的，没有特别的限制。根据本发明，有利的是，采用甲醇对式(I)化合物的粗产物进行重结晶。
本发明式(I)化合物的共轭体系较大，吸收波长较长，在300-450nm、特别是350-420nm、尤其是在365-405nm的波长范围内有较强吸收，故可应用于UV-LED光固化体系中。本发明式(I)化合物的制备原料都是毒性较小的香豆素酮类化合物，相比传统的光引发剂，对人体和环境的危害程度降低。
因此，根据本发明的第三个方面，提供了本发明式(I)化合物作为光引发剂的用途。本发明式(I)化合物在UV-LED光固化体系中作为光引发剂，可以有效地引发固化反应。
式(I)化合物可在涂料、油墨、微电子、印刷等领域用作光引发剂或光敏剂。当式(I)化合物用作光引发剂或光敏剂时，其用量是常规的，或者通过例行的预备试验即可确定。
实施例
以下将结合具体实施例对本发明作进一步说明，但不应将其理解为对本发明保护范围的限制。
实施例1：化合物1的制备
Figure PCTCN2018088830-appb-000012
化合物1的合成路线如下：
Figure PCTCN2018088830-appb-000013
中间产物1a的合成
将4-甲氧基水杨醛(0.0293mol，4.45g)加入盛有15mL乙醇的50mL三口圆底烧瓶中，搅拌均匀后，将混合液加热至35℃使反应物全部溶于乙醇中。然后加入六氢吡啶(0.01mol，1mL)和乙酰乙酸乙酯(0.036mol，4.68g)，再将反应混合物加热至回流，搅拌反应1h。待反应完全后，将混合物冷却至室温，过滤得黄色固体，然后用乙醇重结晶，得6.2g产品，产率97％，经鉴定为化合物1a。1H-NMR(400MHz，CDCl 3)δ2.70(s，3H)，3.91(s，3H)，6.82(d，1H)，6.88(d，1H)，7.55(d，1H)，8.48(s，1H)。
中间产物1b的合成
将中间产物1a(4.66g，0.021mol)和50mL乙醇和水的混合溶液(V 乙醇∶V 水＝2∶1)倒入100mL三口圆底烧瓶中，再加入盐酸羟胺(1.45g，0.021mol)和醋酸钠(1.72g，0.021mol)。70℃下搅拌反应0.5h后，过滤反应液，然后将滤液真空旋蒸后得淡黄色固体，乙醇重结晶，得4.47g产品，产率为90％，经鉴定为化合物1b。1H-NMR(400MHz，DMSO-D6)δ2.05(s，3H)，3.86(s，3H)，6.95(d，1H)，7.01(d，1H)，7.70(d，1H)，8.03(s，1H)，11.30(s，1H)。
目标产物1的合成
将上述中间产物1b(2.08g，0.009mol)和30ml四氢呋喃加入到100mL三口圆底烧瓶中，然后加入乙酰氯(0.78g，0.01mol)和三乙胺(1.35g，0.013mol)，常温搅拌反应1h。终止反应，将反应液过滤后，滤液倒入水中，用乙酸乙酯萃取，收集有机相后依次用稀盐酸溶液、饱和碳酸钠溶液、蒸馏水洗涤，然后收 集有机相，并用MgSO 4干燥过夜。过滤后减压蒸馏蒸掉有机相后得白色固体2.37g，产率97.0％，经鉴定为化合物1。1H-NMR(400MHz，CDCl 3)δ2.25(s，3H)，2.40(s，3H)，3.89(s，3H)，6.82(d，1H)，6.87(d，1H)，7.44(d，1H)，8.04(s，1H)。
实施例2-20
重复实施例1的方法，适当改变反应原料，分别获得下表化合物2-20及其核磁数据。
Figure PCTCN2018088830-appb-000014
Figure PCTCN2018088830-appb-000015
Figure PCTCN2018088830-appb-000016
实施例21：化合物21的制备
Figure PCTCN2018088830-appb-000017
化合物21的合成路线如下：
Figure PCTCN2018088830-appb-000018
中间产物21a的合成
将4-甲氧基水杨醛(0.0293mol，4.45g)加入盛有15mL乙醇的50mL三口圆底烧瓶中，搅拌均匀后，将混合液加热至35℃使反应物全部溶于乙醇中。然后加入六氢吡啶(0.01mol，1mL)，辛酰乙酸乙酯(0.029mol，6.21g)，再将反应混合物加热至回流，搅拌反应1h。待反应完全后，将混合物冷却至室温，过滤得黄色固体，然后用乙醇重结晶，得6.3g产品，产率90％，经鉴定为化合物21a。1H-NMR(400MHz，CDCl 3)δ0.88(t，3H)，1.30(m，10H)，2.94(t，2H)，3.91(s，3H)，6.88(d，2H)，7.55(d，1H)，8.48(s，1H)。
中间产物21b的合成
将中间产物21a(6.04g，0.02mol)加入盛有30ml四氢呋喃的100ml三口瓶中，加入15g浓盐酸(35％)，搅拌0.5h后，控制温度在5℃下滴加亚硝酸异戊酯(2.36g，0.02mol)，滴加完毕后继续在10℃下反应3h。反应完毕后，将反应液倒入水中，乙酸乙酯萃取，收集有机相，水洗有机相至中性。干燥有机相，旋蒸除去有机溶剂，用10g石油醚重结晶，低温下抽滤，得白色固体3.31g，产率50％，经鉴定为化合物21b。1H-NMR(400MHz，CDCl 3)δ0.88(t，3H)，1.30(m，8H)，2.94(t，2H)，3.91(s，3H)，6.88(d，2H)，7.55(d，1H)，8.48(s，1H)，11.31(s，1H)
终产物21的合成
将上述中间产物21b(3.31g，0.01mol)和30ml四氢呋喃加入到100mL三口圆底烧瓶中，然后加入乙酰氯(0.78g，0.01mol)和三乙胺(1.35g，0.013mol)，常温搅拌反应1h。终止反应，将反应液过滤后，滤液倒入水中，用乙酸乙酯萃取，收集有机相后依次用稀盐酸、饱和碳酸钠溶液、蒸馏水洗涤，然后收集有机相，并用MgSO 4干燥过夜。过滤后减压蒸馏蒸掉有机相后得白色固体3.58g，产率96.0％，经鉴定为化合物21。1H-NMR(400MHz，CDCl 3)δ0.88(t，3H)， 1.30(m，8H)，2.94(t，2H)，2.23(s，3H)，2.39(s，3H)，6.88(d，2H)，7.55(d，1H)，8.48(s，1H)。
实施例22-30
重复实施例21的方法，适当改变反应原料，分别获得下表化合物22-30及其核磁数据。重复实施例1的方法，适当改变反应原料，分别获得下表化合物31-50及其核磁数据。
Figure PCTCN2018088830-appb-000019
Figure PCTCN2018088830-appb-000020
Figure PCTCN2018088830-appb-000021
Figure PCTCN2018088830-appb-000022
Figure PCTCN2018088830-appb-000023
热稳定性测试：
专利申请公开CN104817653A披露了如下化合物A。该化合物和本发明化合物1、3、21、28、31和32的初始分解温度见下表：
Figure PCTCN2018088830-appb-000024
化合物 初始分解温度(℃) 化合物 初始分解温度(℃)
化合物1 187 化合物31 170
化合物3 190 化合物32 200
化合物21 165 化合物A 150
化合物28 175    
由上表可见，根据本发明的化合物1、3、21、28、31和32的初始分解温度显著地高于化合物A，因此具有更佳的热稳定性。感光性能测试：
采用乌格拉(Ugra)晒版测试条作掩膜来测试光引发剂的感光性能。乌格拉晒版测试条的各段见图1。乌格拉晒版测试条分为5个控制段，从左到右分别是：连续密度梯尺段(1)；阴阳微米等线同心圆段(2)；全阶调网点段(3)；重影控制段(4)；高光、暗调控制段(5)。第一段：连续密度梯尺段共分为13个梯度用来控制曝光量和显影。第二段：阴阳微米等线同心圆段：由12个阴阳微米等线组成的同心圆线图，分别为4、6、8、10、12、15、20、25、30、40、55、70，用于检测晒PS版时的曝光和显影情况。第三段：全阶调网点段：由10％-100％、极差为10％的评网组成，分为上下两行排列，用于测量晒版、打样和印刷的网点转移情况，并可测制出胶片网点与晒版、打样和印刷网店变化曲线图。第四段：重影控制段：由线宽60线/厘米、面积率为60％的细线条组成，它分为4小块，0°、45°、90°三个角度排列线条和有1/4的D小块中以两边90°、中间小方块45°、 上下90°的小短线排列。第五段：高光、暗调控制段，精细网点段由高光小网点与暗调深网点对应排列，用于精细控制晒版曝光和显影的准确性。将包含光引发剂的感光组合物涂敷于铝基板上，然后曝光显影，从得到的图像的连续调梯尺评价感度，从微线条测试块区域评价精度，从而评价感光组合物配方的优劣。
具体地，按照以下步骤对式(I)化合物的感光性能进行测试。
(1)按照如下组成配制含有光引发剂的感光性组合物：
Figure PCTCN2018088830-appb-000025
上述组合物中光引发剂选自本发明的式(I)所示的香豆素酮肟酯类化合物或现有技术已知的光引发剂(作对比)。丙烯酸酯树脂为从上海釜顺国际贸易有限公司购买的商品名为FS2600K的树脂，官能度为2，数均分子量1400。二季戊四醇六丙烯酸酯为从上海釜顺国际贸易有限公司购买的商品名为GM66G0C的产品。结晶紫染料为从上海国药购买的商品名为六甲基玫苯胺盐酸盐的产品。
感光性能测试
(2)将上述各组合物在黄光下搅拌混合均匀，利用离心机旋涂在预先处理好的并满足下列条件的PS铝版基上：
铝板基尺寸：1030mm×800mm
铝板基厚度：0.28-0.3mm
砂目规格：Ra＝0.5-0.6μm
Rh＝0.3-0.35μm
阳极氧化膜重量：3-3.5g/m 2
控制离心涂布机的转速，使涂在铝版基上的涂布量(以固含量计)为1.0-2.5g/m 2，在离心涂布机上初步干燥后，转移到100℃的鼓风干燥机中干燥3分钟，得紫激光CTP原版。然后，用Ugra测试条做掩膜测试版材的感光性能，曝光一段时间后用1％NaOH水溶液显影。
在曝光区，可光聚合化合物在引发剂存在下发生聚合反应，显影液中不溶，而非曝光区是可溶的，于是得到阴图。通过曝光显影，从得到的图像的连续调梯尺评价光引发剂的感度。引发剂体系感光度特征为显影后保留了(即聚合的) 最高灰阶数。灰阶数越高，表明测试体系灵敏度越高。结果示于表3中。
表3
Figure PCTCN2018088830-appb-000026
Figure PCTCN2018088830-appb-000027
表3中，OXE-01表示1-[4-(苯硫基)苯基]-1，2-辛烷二酮2-(O-苯甲酰肟)，OXE-02表示1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-乙酮)-1-肟乙酸酯，结构式分别如下：
Figure PCTCN2018088830-appb-000028
由表3中的实验结果可以明显看出，本发明光引发剂1-50在365nm、385nm、395nm和405nm处灰阶数均高于商购的光引发剂OXE-01和OXE-02。也就是说，本发明的香豆素(酮)肟酯类光引发剂，其在365nm、385nm、395nm和405nm波长处感光性能更为优异，适合用于365nm、385nm、395nm、405nm的UV-LED光源。
综上所述，本发明式(I)所示的香豆素(酮)肟酯类光引发剂在365nm、385nm、395nm和405nm波长处具有较好的感光性能，优于现阶段可商购的OXE-01和 OXE-02等酮肟酯类光引发剂。另外本发明公开的化合物生产工艺简单，产率高，非常适合于工业生产。此类化合物与365nm、385nm、395nm、405nm的UV-LED光源匹配性良好，且可广泛应用于UV-LED光固化所涉及的领域例如涂料、油墨、微电子、印刷等领域用作光引发剂。此类物质具有很好的市场前景。鉴于目前可应用于UV-LED的光引发剂品种较少，从一定程度上限制了UV-LED光源在紫外光固化领域的推广应用，故本发明光引发剂可为推动绿色环保的UV-LED光源在UV光固化行业的广泛应用做出贡献。

Claims (12)

  1. 式(I)的香豆素(酮)肟酯化合物：
    Figure PCTCN2018088830-appb-100001
    其中：
    n为0或1；
    R 1、R 2、R 3、R 4、R 5相互独立地表示氢、卤素、硝基、羟基、巯基、羧基、C 1-C 8羧酸酯基、磺酸基、氨基、氰基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基，其中前述氨基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 2-C 6烯基和C 2-C 6炔基，或者
    R 1与R 2一起、R 2与R 3一起、R 3与R 4一起或者R 1与R 2一起且R 3与R 4一起形成总共具有3-4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和的二价基团；以及
    R 6、R 7相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基，其中前述C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基任选地被一个或多个独立 地选自下组的基团取代：C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷氧基、卤素、硝基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基和巯基，
    其中满足如下定义的化合物除外：n为0，R 1、R 2、R 3、R 4和R 5均为H，R 6为甲基，并且R 7为正丙基。
  2. 根据权利要求1的化合物，其中R 1、R 2、R 3、R 4和R 5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、C 1-C 6羧酸酯基、磺酸基、氨基、氰基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基，其中前述氨基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、C 2-C 4烯基和C 2-C 4炔基；或者，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3-4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和的二价基团，
    优选的是，R 1、R 2、R 3、R 4和R 5彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 4烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；或者，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3个或4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和二价基团，例如-O-CH 2-O-、-S-CH 2-S-、-N-CH 2-N-、-O-CH 2CH 2-O-、-S-CH 2CH 2-S-、-N-CH 2CH 2-N-或-CH＝CH-CN＝CH-。
  3. 根据权利要求1或2的化合物，其中R 6、R 7相互独立地表示直链或支化的C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基，其中前述C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷 基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基，
    优选的是，R 6、R 7彼此独立地选自直链或支化的C 1-C 8烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 4烷基、被苯基取代的C 1-C 4烷基和苯基，其中前述苯基各自任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基；
    更优选的是，R 6为直链或支化的C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基和巯基，以及R 7为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。
  4. 根据权利要求1-3中任一项的化合物，其中R 5为H。
  5. 根据权利要求1或4的化合物，其中
    n为0，
    R 1、R 2、R 3和R 4彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 6烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；或者，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3个或4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和二价基团，例如-CH＝CH-CN＝CH-；
    R 6为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：氟、氯、溴、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基和卤代C 1-C 4烷基，以及
    R 7为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基和二(C 1-C 4烷基)氨基，或者
    n为1，
    R 1、R 2、R 3和R 4彼此独立地选自氢、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；或者，R 1与R 2一起、R 2与R 3一起或者R 3与R 4一起形成总共具有3个或4个选自C、N、O和S的原子并且其中至少一个原子为碳原子的饱和或不饱和二价基团，例如-O-CH 2-O-、-S-CH 2-S-、-N-CH 2-N-、-O-CH 2CH 2-O-、-S-CH 2CH 2-S-或-N-CH 2CH 2-N；
    R 6为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基或被C 5-C 6环烷基取代的C 1-C 2烷基，以及
    R 7为直链或支化的C 1-C 6烷基或任选被硝基取代的苯基。
  6. 根据权利要求1的化合物，其中式(I)化合物选自下组：
    Figure PCTCN2018088830-appb-100002
    Figure PCTCN2018088830-appb-100003
    Figure PCTCN2018088830-appb-100004
    Figure PCTCN2018088830-appb-100005
    Figure PCTCN2018088830-appb-100006
  7. 一种制备如权利要求1-6中任一项所要求的化合物的方法，包括以下步骤：
    (1)肟化反应：当n为0时，使式(II)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(IIIa)化合物
    Figure PCTCN2018088830-appb-100007
    当n为1时，使式(II)化合物与选自亚硝酸、亚硝酸盐和亚硝酸烷基酯中的试剂进行肟化反应，得到式(IIIb)化合物：
    Figure PCTCN2018088830-appb-100008
    其中，式(II)、(IIIa)和(IIIb)中的R 1-R 5和R 6如权利要求1-6中任一项所定义；以及
    (2)将式(IIIa)或(IIIb)化合物酯化，得到式(I)化合物。
  8. 根据权利要求7的方法，其中
    当n为0时：肟化反应在乙酸钠、吡啶、哌啶、三乙胺或其混合物存在下进行；和/或，肟化反应在乙醇或含水的乙醇作为溶剂存在下进行；和/或，肟化反应的温度为60-120℃；和/或，肟化反应时间为0.1-20小时，优选0.5-10小时；式(II)化合物与选自羟胺和/或盐酸羟胺的化合物的摩尔比为1∶1.5-1.5∶1，优选为1∶1.2-1.2∶1；
    当n为1时，肟化反应在浓盐酸存在下进行；和/或，肟化反应在乙醇或含水的乙醇作为溶剂存在下进行；和/或，肟化反应的温度为-30至20℃，优选5-20℃；和/或，肟化反应时间为0.1-20小时，优选0.5-10小时；式(II)化合物与选自亚硝酸、亚硝酸盐和/或亚硝酸烷基酯的化合物的摩尔比为1∶1.5-1.5∶1，优选为1∶1.2-1.2∶1。
  9. 根据权利要求7或8的方法，其中亚硝酸烷基酯为亚硝酸C 1-C 6烷基酯，例如亚硝酸甲酯、亚硝酸乙酯、亚硝酸异丙酯、亚硝酸丁酯、亚硝酸异戊酯；和/或，步骤(2)的酯化采用选自下式(IVa)、(IVb)和(IVc)化合物的酯化试剂进行：
    Figure PCTCN2018088830-appb-100009
    其中X为卤素，尤其是氯，和R 7如权利要求1-6中任一项所定义。
  10. 根据权利要求7-9中任一项的方法，其中酯化反应在选自下组的一种或多种催化剂存在下进行：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。
  11. 根据权利要求7-10中任一项的方法，其中酯化反应在选自四氢呋喃、苯、甲苯、N，N-二甲基甲酰胺、二氯甲烷和丙酮的溶剂中进行；和/或，式(IIIa)或式(IIIb)化合物与选自(IVa)、(IVb)和(IVc)化合物的酯化试剂的摩尔比为1∶1.5-1.5∶1，优选为1∶1.2-1.2∶1。
  12. 如权利要求1-6中任一项所要求的式(I)化合物作为光引发剂的用途，尤其是在UV-LED光固化体系中作为光引发剂的用途，优选在辐射波长为300-450nm、特别350-420nm、尤其是365-405nm的光固化体系中作为光引发剂或光敏剂的用途。
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