WO2020118933A1 - 一种新型多环化合物 - Google Patents

一种新型多环化合物 Download PDF

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WO2020118933A1
WO2020118933A1 PCT/CN2019/077919 CN2019077919W WO2020118933A1 WO 2020118933 A1 WO2020118933 A1 WO 2020118933A1 CN 2019077919 W CN2019077919 W CN 2019077919W WO 2020118933 A1 WO2020118933 A1 WO 2020118933A1
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alkyl
branched
compound
linear
hydrogen
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French (fr)
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曾裕峰
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Eutec New Materials Technology (suzhou) Co Ltd
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Eutec New Materials Technology (suzhou) Co Ltd
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Priority to JP2021532922A priority Critical patent/JP2022511918A/ja
Priority to US17/311,987 priority patent/US12319661B2/en
Priority to CA3124463A priority patent/CA3124463A1/en
Priority to KR1020217021534A priority patent/KR20210110829A/ko
Priority to EP19896846.3A priority patent/EP3896067A4/en
Publication of WO2020118933A1 publication Critical patent/WO2020118933A1/zh
Anticipated expiration legal-status Critical
Priority to JP2023101400A priority patent/JP7674756B2/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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Definitions

  • the present invention relates to novel polycyclic compounds, their synthesis and applications.
  • the compound of the present invention includes a plurality of carbocyclic and/or heterocyclic structures, has a group emitting visible light or fluorescence, and is covalently bonded with at least one ultraviolet and/or blue light absorbing group to provide stability.
  • the compound of the present invention can be used as a light conversion agent, dye, pigment, fluorescent agent, ultraviolet light or blue light absorber, used in optical films, agricultural films, optical discs (discs), optical lenses, goggles, skin care, make-up, lighting, coatings , Adhesives, light stabilizers, or panels and other products.
  • organic compounds with light-emitting properties including dyes, pigments, or fluorescent substances, are widely used in agriculture, electronics industry, and medicine.
  • light conversion agent or optical recording medium of optical disc are widely used in agriculture, electronics industry, and medicine.
  • adding a light conversion agent to the agricultural film can convert the ultraviolet light in the sunlight or the blue light in the short wavelength band into useful light for plants.
  • red light is the most important light for the growth of crops, which can promote the increase of crop yields.
  • the red light can promote the formation of leaf cabbage, but too much blue light can inhibit it (Journal of Agricultural Machinery, Journal of Agricultural Machinery, ISSN: 1019) -0430, Vol 8(2), 1999Jun, p.63-74).
  • organic compounds are prone to degradation when they are used outdoors, such as the organic light conversion agent, RL1000. Therefore, improving stability is an important indicator for the improvement of light conversion agents.
  • optical recording media such as optical disks
  • organic dyes that irradiate a laser beam into the recording layer.
  • the laser will be converted into thermal energy, which causes the recording layer to thermally deform, for example, into a molten state.
  • the reflectance of light is recorded. Due to the local high temperature of 250°C or above during the conversion of laser into thermal energy, the melting point and thermal stability of the dye become important conditions.
  • organic compounds (B) which are used in optical recording media (JP 3876970 B2). But the melting point is lower and the stability is poor.
  • UV and/or blue light irradiation is known to be an important factor that causes degradation of organic materials, such as agricultural films or optical recording media.
  • Isolation or addition of anti-blue light and/or anti-ultraviolet agents can increase the shelf life of agricultural films or optical discs.
  • the traditional anti-blue light agent can only achieve the anti-blue light and ultraviolet long wave (UVA) functions. If you need to simultaneously prevent blue light and ultraviolet long and short waves (UVA+UVB), you must add an additional ultraviolet light absorber (UVB). This is not conducive to industrial use. Therefore, the development of compounds that absorb ultraviolet light (UVA+UVB) and blue light has become the goal of industrial efforts.
  • the design concept of the compounds of formula (1) and formula (2) of the present invention is to covalently bond the dye or the light-converting substance with the substance that absorbs ultraviolet light or/and blue light.
  • the compound of formula (1) or formula (2) designed by this brand-new concept greatly increases the stability of the original organic dye or light conversion agent, and also because of the large-scale anti-blue light and ultraviolet light (UVA+UVB), it also increases The stability of protected organic materials.
  • the covalently bonded ultraviolet light absorbing group provides stability to the light conversion agent itself at close range in the molecule.
  • ultraviolet light absorbing groups also provide stability to protected organic materials around the molecule, such as agricultural membranes. As a result of this double action, the usable time or stability of agricultural films has increased significantly.
  • Organic light conversion agent A (RL1000, BASF) currently used in agricultural film can emit orange-red light under sunlight. But its light stability is insufficient. In outdoor PE agricultural film use, RL1000 can only maintain the stability of two seasons.
  • the organic dye compound (B) applied to the optical recording medium has a melting point of 175°C. After covalent bonding with benzotriazole, the melting point of A rose to 224°C (Example 42). This is an important and unexpected improvement.
  • the organic dye of the optical disc absorbs the laser light and converts it into heat energy, it will cause local high temperature (250°C or above).
  • the compound (B) is covalently bonded with benzotriazole, not only the melting point and thermal stability are improved, but also the ultraviolet (UVA+UVB) absorption capacity provided by benzotriazole can also increase the shelf life of the optical disc.
  • the compounds of the present invention increase stability without affecting the original luminescent properties of organic dyes or light conversion agents.
  • the structure of R 1 to R 3 in the compound of formula (1) or formula (2) is designed to increase or decrease the conjugation, which can increase or decrease the original luminescent properties of the organic dye or light conversion agent.
  • the compound (19) of Example 11 has increased conjugation compared with the compound (18) on the one hand, and also increased the wavelength of absorption or emission of visible light on the one hand.
  • the application field can also be extended from dyes to other fields, such as agricultural film.
  • the highly stable compound (7) can also be applied to the red laser (640 nm) commonly used for DVD-R discs, in addition to agricultural films.
  • the compounds of the present invention can also be used as ultraviolet and/or blue light absorbers. Since the compounds of the present invention have luminescent properties, they can be used as special color ultraviolet light absorbers and/or blue light absorbers. Traditional anti-blue light absorbers can only absorb ultraviolet light (UVA) and blue light.
  • the compound of the present invention has a wide range of ultraviolet light (UVA+UVB) absorption, so without additional ultraviolet light (UVB) absorber, it can absorb ultraviolet light (UVA+UVB) and blue light at the same time, fully protect the human body, The function of polymers or other organic materials.
  • the compound provided by the present invention is a polycyclic compound having the structure represented by formula (1) or formula (2).
  • the compound of formula (1) or formula (2) of the present invention is characterized by comprising at least one visible light or fluorescence emitting group, and at least one additional ultraviolet light absorbing group;
  • R 2 -CR 3 -D or R 2 -DR 3 -C is a visible light emitting group or a fluorescent emitting group;
  • AR 1 -B is an ultraviolet light absorbing group
  • R 1 to R 3 are one bond or/and any divalent linking group; preferably, R 1 is one bond or any divalent linking group, more preferably, R 1 is both one bond and divalent Linking groups, for example, AR 1 -B is 9-hydrocarbazole or dibenzothiophene;
  • A, B, C, 5-7 membered ring which is unsubstituted or substituted by R 4 preferably, benzene ring, benzocarbocyclic ring, nitrogen-containing 5-7 membered heterocyclic ring, or benzo nitrogen-containing 5 -7-membered heterocyclic ring, nitrogen-containing heterocyclic ring does not exclude other heteroatoms, benzo nitrogen-containing 5-7-membered heterocyclic ring refers to the fused benzene ring and nitrogen-containing 5-7-membered heterocyclic ring;
  • D is an unsubstituted or substituted 5-7 membered heterocyclic ring or benzo 5-7 membered heterocyclic ring composed of carbon, nitrogen, oxygen, sulfur atoms, wherein the substituent of the ring carbon atom is selected from 1 or more H, hydroxyl, oxo, thioxo, thiol, amino, imino, C 1 ⁇ C 8 linear or branched alkyl, R 4, one or more substituents selected from H, hydroxyl, oxy (oxo), linear or branched C ring nitrogen atom 1 ⁇ C 8 alkyl group;
  • R 4 is one or more substituents (in the structural formula of the present invention, R 4 or other substituents are substituted at uncertain positions, referring to arbitrary positions on the ring, for example, when the structural formula diagram shows the bond of R 4 on the ring
  • the junction is between two atoms, which means that R 4 can be bonded at any position on the ring)
  • each is independently selected from hydrogen, halogen, hydroxyl, amino, nitro, cyano, linear, or branched C 1 ⁇ C 18 alkyl, alkenyl or alkoxy, substituted or unsubstituted phenyl, SR 5 , SO 2 R 5 , SO 3 R 5 , COOR 5 , COR 5 , OCOR 5 , C(O)NR 6 R 7 , SO 2 NR 6 R 7 , NR 6 R 7 , wherein R 5 , R 6 , and R 7 are each independently selected from hydrogen, a linear or branched C 1 -C 8 alkyl group, and R
  • R 13 to R 18 are one or more, and are each independently selected from hydrogen, halogen, hydroxy, unsubstituted or halogen-substituted linear or branched C 1 to C 6 alkyl (preferably, C 1 to C 4 alkyl), unsubstituted or phenyl substituted with halogen or C 1 -C 6 alkyl (preferably, C 1 -C 4 alkyl).
  • Ph is phenyl which is unsubstituted or substituted by halogen, OH group or by linear or branched C 1 ⁇ C 6 alkyl (preferably, C 1 ⁇ C 4 alkyl), preferably, halogen is chlorine.
  • A is selected from:
  • R 4 is one or more substituents, and each is independently selected from hydrogen, halogen, nitro, cyano, linear or branched C 1 ⁇ C 8 alkyl, alkenyl or alkoxy, SR 5 , SO 2 R 5 , COOR 5 , COR 5 , C(O)NR 6 R 7 , NR 6 R 7 , where R 5 , R 6 , R 7 are each independently selected from hydrogen, straight chain or branched chain C 1 ⁇ C 8 alkyl, preferably, R 5 , R 6 , R 7 are hydrogen or straight chain or branched chain C 1 ⁇ C 4 Alkyl, preferably halogen is chlorine.
  • Ph is unsubstituted or substituted phenyl, preferably, the substituent is halogen, hydroxy, C 1 -C 6 alkoxy (preferably, C 1 -C 4 alkoxy) or C 1 -C 6 alkyl group (preferably, C 1 ⁇ C 4 alkyl group) substituted phenyl, preferably, the halogen is chlorine.
  • R 19 to R 20 are one or more, and are each independently selected from hydrogen, linear or branched C 1 to C 6 alkyl (preferably, C 1 to C 4 alkyl), unsubstituted or
  • the substituted phenyl group is preferably a halogen or a linear or branched C 1 -C 6 alkyl group (preferably, a C 1 -C 4 alkyl group).
  • B is selected from:
  • C is selected from:
  • D is selected from:
  • R 8 to R 12 are one or more, and are each independently selected from hydrogen, a linear or branched C 1 to C 8 alkyl or alkenyl group, unsubstituted or linear or branched C 1 to C 6 alkyl (preferably, C 1 -C 4 alkyl) or halogen-substituted phenyl; D ring is unsubstituted or substituted with R 4 and through 1 to 2 double bonds or single bonds link.
  • the D ring is connected to the outside of the ring via a double bond.
  • halogen is chlorine.
  • R 13 to R 18 are one or more, and are each independently selected from H, unsubstituted or halogen-substituted linear or branched C 1 to C 6 alkyl (preferably, C 1 to C 4 alkyl), unsubstituted or halogen or C 1 ⁇ C 6 alkyl group (preferably, C 1 ⁇ C 4 alkyl group) substituted phenyl.
  • Ph is phenyl which is unsubstituted or substituted with halogen, OH group or C 1 -C 6 alkyl (preferably, C 1 -C 4 alkyl), preferably, halogen is chlorine.
  • A is selected from:
  • R 4 is one or more substituents, and each is independently selected from hydrogen, halogen, nitro, cyano, linear or branched C 1 -C 8 alkyl, alkenyl or alkoxy, SR 5 , SO 2 R 5 , COOR 5 , COR 5 , C(O)NR 6 R 7 , NR 6 R 7 , wherein R 5 , R 6 , and R 7 are each independently selected from hydrogen, straight chain, or branched chain C 1 ⁇ C 8 alkyl.
  • R 5 , R 6 , and R 7 are hydrogen or a linear or branched C 1 -C 4 alkyl group, and preferably, the halogen is chlorine.
  • Ph is phenyl which is unsubstituted or substituted with R 4 , preferably, the substituent is hydrogen, halogen, OH group, C 1 ⁇ C 6 alkoxy (preferably, C 1 ⁇ C 4 alkoxy) or C 1 ⁇ C 6 alkyl group (preferably, C 1 ⁇ C 4 alkyl group) substituted phenyl, preferably, the halogen is chlorine;
  • B is selected from:
  • C is selected from:
  • D is selected from:
  • C S
  • C S
  • C NR 8 , C-NR 11 R 12 , N, NR 9 , C, O, S, CR 10 , CR 11 R 12 ;
  • R 8 ⁇ R 12 are one or more, and are independently selected from H, linear or Branched C 1 -C 6 alkyl (preferably, C 1 -C 4 alkyl), unsubstituted or halogenated or C 1 -C 6 alkyl (preferably, C 1 -C 4 Alkyl) substituted phenyl.
  • the D ring is unsubstituted or substituted with R 4 and is linked to the outside of the ring via 1 to 2 double bonds or single bonds. Preferably, the D ring is connected to the outside of the ring via a double bond.
  • D is selected from the following rings:
  • AR 1 -B is selected from the following groups:
  • R 4 is one or more substituents, and each is independently selected from hydrogen, halogen, hydroxy, amino, nitro, cyano, linear or branched C 1 ⁇ C 18 alkyl, alkenyl or alkoxy , Substituted or unsubstituted phenyl, SR 5 , SO 2 R 5 , SO 3 R 5 , COOR 5 , COR 5 , OCOR 5 , C(O)NR 6 R 7 , SO 2 NR 6 R 7 , NR 6 R 7 , wherein R 5 , R 6 , and R 7 are each independently selected from hydrogen, a linear or branched C 1 -C 8 alkyl group (preferably, C 1 -C 4 alkyl group), and R 4 Between adjacent R 4 or between R 4 and the adjacent ring, it may represent a fused carbocyclic ring or fused heterocyclic ring of 3-6 atoms, preferably, containing C, N, O, S A fused heterocyclic ring of 3-6
  • R 19 and R 35 to R 39 are one or more, and are each independently selected from H, a linear or branched C 1 to C 6 alkyl group (preferably, a C 1 to C 4 alkyl group), Unsubstituted or substituted with halogen or C 1 -C 6 alkyl (preferably, C 1 -C 4 alkyl) substituted phenyl; Ph is unsubstituted or substituted with halogen, OH group or C 1 -C 6 alkyl (Preferably, C 1 -C 4 alkyl) substituted phenyl, preferably, halogen is chlorine.
  • the compound of formula (1) or formula (2) includes at least one visible light or fluorescent emitting group and at least one covalently bonded ultraviolet light absorbing group, wherein the visible light or fluorescent emitting group Is R 2 -CR 3 -D or R 2 -DR 3 -C, selected from:
  • D is selected from:
  • the ultraviolet light absorbing group is AR 1 -B, selected from:
  • Benzoxazinone (Benzoxazinone):
  • Phenylformamidine (Phenylformamidine)::
  • Dibenzothiophene (Dibenzothiophene):
  • Dibenzofuran (Dibenzofuran):
  • R 4 is one or more substituents, and each is independently selected from hydrogen, halogen, hydroxy, amino, nitro, cyano, linear or branched C 1 ⁇ C 18 alkyl, alkenyl or alkoxy , Substituted or unsubstituted phenyl, SR 5 , SO 2 R 5 , SO 3 R 5 , COOR 5 , COR 5 , OCOR 5 , C(O)NR 6 R 7 , SO 2 NR 6 R 7 , NR 6 R 7 , wherein R 5 , R 6 , and R 7 are each independently selected from hydrogen, a linear or branched C 1 -C 8 alkyl group (preferably, C 1 -C 4 alkyl group), and R 4 Between adjacent R 4 , or between R
  • the method for preparing the compound of formula (1) or formula (2) is characterized by including one of the following reaction steps.
  • the preparation of the compound of formula (1) includes one of the following reaction steps:
  • the preparation of the compound of formula (2) includes one of the following reaction steps:
  • a ⁇ D ring, R 1 ⁇ R 3 as defined above;
  • D' is a precursor of D ring, selected from D'is a precursor of D ring, selected from
  • D is the precursor of the D ring
  • Z is a leaving group, including but not limited to halogen, C 1 -C 10 sulfonate group, C 1 -C 10 alkoxy group; preferably, Z is selected from halogen, p-toluenesulfonate (OTs), mesylate (OMs), C 1 ⁇ C 4 alkoxy.
  • halogen is chlorine.
  • R 50 to R 53 are the same or different and are independently selected from one bond, hydrogen, straight chain or branched C 1 ⁇ C 8 alkyl group is, preferably, alkyl is straight-chain or branched-chain C 1 ⁇ C 4 alkyl group.
  • T is the same or different, each independently selected from NH, NH 2 , OH, SH.
  • the specific preparation method 1 of the compound (1) of the present invention includes the preparation methods of Examples 1-11, 15-22, and 33.
  • the preparation method of Examples 1-4 is as follows:
  • the specific preparation method 2 of the compound (1) of the present invention includes the preparation methods of Examples 12-14 and 23-32.
  • the preparation method of Example 13 is as follows:
  • the specific preparation method 1 of the compound (2) of the present invention includes the preparation method of Example 34.
  • the method is as follows:
  • the specific preparation method 2 of the compound (2) of the present invention includes the preparation method of Example 35.
  • the method is as follows:
  • the specific preparation method 3 of the compound (2) of the present invention includes the preparation method of Example 36.
  • the method is as follows:
  • the specific preparation method 4 of the compound (2) of the present invention includes the preparation method of Example 37, and the preparation method is as follows:
  • the specific preparation method 5 of the compound (2) of the present invention includes Example 38.
  • the method is as follows:
  • the specific preparation method 6 of the compound (2) of the present invention includes the preparation method of Example 39.
  • the method is as follows:
  • the specific preparation method of traditional benzotriazole compounds usually uses 2-nitroaniline and various substituted phenols as starting materials.
  • the first step forms an azo compound
  • the second step is a reduction reaction to form a benzotriazole compound (US3773771), for example, Example 6.
  • the method is as follows:
  • the compound of the present invention can be applied to films. For example, it is used as a light conversion agent in agricultural film. It can also be used in anti-ultraviolet film or anti-blue light film to protect eyes or other tissues.
  • the compound of the present invention can be applied to general films or organic materials to protect the films or organic materials themselves.
  • the compound of the present invention can be applied to a recording layer of an optical recording medium.
  • the compounds of the present invention can also be used in combination with other compounds for different needs. The implementation of these applications can use general methods in the industry.
  • Agricultural film is usually made of resin raw materials such as polyvinyl chloride, ethylene or low density polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA), metallocene linear polyethylene (MLLDPE). Made by calendering process. Specific manufacturing methods, for example, take low-density polyethylene as the base material 1kg, metallocene linear polyethylene 200g, light conversion agent 5g, antioxidant 8g, ultraviolet absorber 5g, glyceride 9g, after mixing, through the film blowing unit According to conventional blow molding. A transparent film with a thickness of 0.03 to 2.0 mm. The amount of light conversion agent added depends on the type of crops and the thickness of the agricultural film, and the general range includes but is not limited to 0.001% to 20%, preferably, 0.2% to 5%.
  • LDPE low density polyethylene
  • EVA ethylene-vinyl acetate copolymer
  • MLLDPE metallocene linear polyethylene
  • Specific manufacturing methods for example, take low-density polyethylene
  • the light conversion or anti-blue light composition can also be coated on the base layer or the release layer and used after being hardened. Or use a transfer coating process, first coated on the release film, and then transferred to the base layer. A layer of release film is attached to the upper and lower layers of the film, which is OCA optical adhesive (Optically Clear).
  • the coating method is a conventional technique, including traditional brush coating, spray coating, curtain coating, roll coating, slit coating, air knife coating, blade coating, and metering bar coating. Drying methods include natural drying, microwave drying, ultraviolet drying, infrared drying, and hot air drying.
  • the base layer includes one or more mixtures of polyester, glass, polyethylene, polypropylene, polycarbonate, polyamide, polyacrylate, polymethacrylate, polyvinyl acetate, and polyvinyl chloride.
  • the release film includes silicon oxide type and non-silicon oxide materials.
  • Light conversion or anti-blue light composition the composition of which includes the light conversion agent, anti-ultraviolet agent, or anti-blue light agent, polymer, solvent, and/or auxiliary agent, and/or initiator, and/or monomer of the present invention .
  • the compound of the present invention is used for a recording layer of an optical recording medium.
  • the organic dye recording layer can be coated on the substrate by spin coating.
  • the substrate may be made of polycarbonate (PC) or polyacrylamine.
  • the thickness of the recording layer is usually several nanometers to tens of nanometers.
  • a reflective layer is formed on the recording layer by sputtering.
  • an adhesive layer is spin-coated, and a cover plate is adhered to the reflective layer through the adhesive layer to form an optical disc.
  • Fig. 1 UV-VIS absorption diagram of the compound (7) of the present invention (10 mg/tetrahydrofuran);
  • FIG. 4 Appearance of the agricultural film made of the light conversion agent of the present invention.
  • Table 1 is the compound of formula (1)
  • Raw material 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole is from Eutec co. (Eusorb 329, melting point: 102-106°C), or can be prepared in the following manner Get. 13.8 g of o-nitroaniline was added to 25 ml of 37% hydrochloric acid and stirred, diluted with 40 ml of water and cooled to -15°C. Add 7.5g of sodium nitrite (dissolved in water), keep the temperature at 0 ⁇ 5 °C, get the diazonium salt (Diazonium).
  • compound (20) is added with Mieic acid, ammonium acetate and acetic acid, and reacted to obtain compound (19).
  • the compound (24) was used instead of the compound (6) and separated by column chromatography to obtain the compound (22).
  • 3-indole formaldehyde is an industrial raw material and can be prepared in the following manner (Vilsmeier reaction): under an ice bath, 30 g of DMF and 16 g of POCl 3 are added dropwise within 30 minutes. Slowly add 11g of indole compound in DMF, warm to 35°C and stir for 1 hour. The obtained paste was stirred with 50 g of crushed ice, and 0.1 M NaOH was slowly added with stirring. After washing with water, recrystallize with ethanol to obtain 3-indolaldehyde, C 9 H 7 NO. Melting point: 196 ⁇ 197°C.
  • Preparation method of compound (39) the preparation method of compound (35) in Example 23, but using 4-(chloromethyl)-2-methylphenol instead of (3-(tert-butyl)-4-hydroxyl Methyl phenyl)propionate (37).
  • Preparation method of compound (43) Add 14g of 2-aminobenzoic acid (compound 44) and 11g of triethylamine to 100ml of dichloroethane, dropwise add 19g of 4-chloromethylbenzoyl chloride (compound 45) and stir, (Compound 43) is obtained.
  • Preparation method of compound (45) 4-(hydroxymethyl)benzoic acid (46) in dichloromethane, chlorinated with thionyl chloride under reflux to obtain compound (45), melting point: 28°C.
  • compound (B) Used to improve the performance of optical recording media: compound (B), after covalent bonding, compound (18) is obtained, as shown in the figure below.
  • the melting point of compound (B) is 175°C. After covalent bonding with benzotriazole compounds, the melting point is increased to 224°C (compound 18). This is an important improvement for the organic dye (B) used in optical recording media. Because the compound (18) is irradiated with the laser, the local high temperature (250 °C or above) is less likely to decompose.
  • Figure 3 illustrates the absorption range of compound (18) for ultraviolet light, covering UVA, UVB and blue light. This shows that the compound (18) dye can provide a wide range of ultraviolet light (UVA+UVB) protection for optical discs. Therefore, compound (18) is more advantageous than compound (B) in the preservation of optical discs.
  • a Compound (B) Inventive Example 10 Compound (18) Thermal properties Melting point 175°C Melting point 224°C Light absorption range UVA+visible light UVA+UVB+visible light
  • UV or blue light absorbers When the compounds of the present invention are used in ultraviolet and/or blue light absorbers, they have both ultraviolet (UVA+UVB) and blue light absorption functions. Compared with the commercially available anti-blue light agent Eusorb UV-1990 (Eutec Co.) (Table 4), it shows that the commercial product Eusorb UV-1990 has very weak absorption for UVB (wavelength 280nm). The example compounds of the present invention are superior to the currently commercially available anti-blue light agent Eusorb UV-1990 in terms of coverage and absorption of ultraviolet light.
  • TGA Thermogravimetric analyzer
  • FIG. 4 is a photograph of a PE agricultural film made of the compound (7) of Example 4 of the present invention, under a fluorescent lamp (to show color, the agricultural film is placed on a gray opaque background).
  • the agricultural film is transparent and orange-red.
  • Table 5 shows the comparison of weather resistance before and after the improvement of agricultural film compounds.
  • RL1000 commercial product BASF
  • BASF can only maintain the stability of two seasons in outdoor agricultural film use, and the compound (7) of the present invention exceeds 3 seasons.
  • a RL1000 The compound of the present invention (7) Weather resistance 2 seasons 3 seasons Visible light emission range Orange red (about 600-700nm) Orange red (about 600-700nm)

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Abstract

本发明提供一种新型多环化合物、合成方法及其应用。本发明化合物包括了多个碳环及/或杂环结构,其具有发射可见光或荧光的基团,且共价键结了至少一个紫外光及/或可见光(蓝光)吸收基团以提供稳定性。本发明化合物可当作转光剂、染料、颜料、荧光剂、紫外光或蓝光吸收剂,应用于光学膜、农膜、光盘(碟)、光学镜片、护目镜、护肤、彩妆、照明、涂料、粘合剂、光稳定剂、或面板等产品。

Description

一种新型多环化合物 技术领域
本发明关于新颖的多环化合物、其合成及其应用。本发明化合物包括了多个碳环及/或杂环结构,具有发射可见光或荧光的基团,且共价键结了至少一可紫外光及/或蓝光吸收基团以提供稳定性。本发明化合物可当作转光剂、染料、颜料、荧光剂、紫外光或蓝光吸收剂,应用于光学膜、农膜、光盘(碟)、光学镜片、护目镜、护肤、彩妆、照明、涂料、粘合剂、光稳定剂、或面板等产品。
背景技术
目前，具有光发射性质的有机化合物,包括染料、颜料或荧光物质,在农业、电子工业、医学或都有广泛应用。例如转光剂(Light conversion agent)或光盘的光记录媒体(Optical recording medium)。
农业上，于农膜中添加转光剂,可将太阳光中的紫外光或短波段的蓝光转变为对植物有用的光线。其中红光是农作物生长最重要的光线,可以促进农作物的增产。例如,结球白菜(Chinese Cabbage)在初期结球过程，红光有促进叶菜结球的形成，但过多的蓝光则有抑制的作用(农业机械学刊,Journal of Agricultural Machinery，ISSN:1019-0430,Vol 8(2),1999Jun,p.63-74)。此外，曾有文献揭示,用于农膜的商用有机转光剂RL1000(化合物A,BASF)，可吸收紫外光以减少蚜虫等害虫,并发出对植物有益的可见光(约635nm),然而其稳定性不足(CN 100500754 C)。
Figure PCTCN2019077919-appb-000001
普遍地,有机化合物应用在室外时,容易发生降解,例如有机的转光剂，RL1000。因此提高稳定性是转光剂改良的重要指标。
另一方面，已知的光学记录媒体,例如光盘,是将激光束照射至记录层中的有机染料。短时间内,激光会转换成热能,使记录层产生热变形,例如变成熔融状态。根据变形部分与无变形部分之间,对光的反射率的差异,进行记录信息。由于激光转换成热能的过程中,所造成局部高温达250℃或以上,因此,染料的熔点与热稳定性成为重要条件。曾有文献揭示有机化合物(B),应用于光记录媒体(JP 3876970 B2)。但熔点较低,稳定性较差。
Figure PCTCN2019077919-appb-000002
此外，已知紫外光及/或蓝光照射是造成有机材料，例如农膜或光记录媒体，降解的重要因素。隔绝或加入防蓝光及/或防紫外光剂，可以增加农膜或光盘的保存寿命。传统的防蓝光剂,仅能同时达成防蓝光及防紫外光长波(UVA)功能。如果需要同时防蓝光及紫外光长短波(UVA+UVB)，则必须添加额外的紫外光吸收剂(UVB)。这并不利于产业利用。因此，开发吸收波段涵盖紫外光(UVA+UVB)及蓝光的化 合物,成为产业努力的目标。
综合以上，增加发光记录媒体用染料或转光剂的稳定性、以及开发吸收波段涵盖紫外光(UVA+UVB)及蓝光的化合物,都是产业努力的目标。
发明内容
开发具有高稳定性的有机染料、转光剂、或开发吸收波段涵盖紫外光(UVA+UVB)及蓝光的化合物，一直是产业努力目标。为达此目的,本发明人特别设计了新颖的多环式(1)与式(2)化合物。
本发明式(1)与式(2)化合物设计的理念，在于将染料或转光物质,与吸收紫外光或/且蓝光物质，进行共价键结。这个崭新理念所设计的式(1)或式(2)化合物,大幅增加了原来有机染料或转光剂的稳定性,也因为大范围的防蓝光及紫外光(UVA+UVB)，同时增加了受保护的有机材料的稳定性。
这可能是因为共价键结的紫外光吸收基团，在分子内近距离对转光剂本身提供稳定性。进一步，紫外光吸收基团也对分子周围受保护的有机材料,例如农膜,提供稳定性。这双重作用的结果,使得农膜的可利用时间或稳定性,大幅增加。
目前应用于农膜的有机转光剂A(RL1000,BASF)，日照下可放出橘红光。但其光稳定性不足。在户外的PE农膜使用上，RL1000仅能维持两季的稳定性。
Figure PCTCN2019077919-appb-000003
经本发明人将其与苯并三唑共价键结后,得到MP259(化合物7)，则可以维持三季以上的PE农膜的户外稳定性(实例43)。
再如前述应用于光记录媒体的有机染料化合物(B)，其熔点为175℃。经与苯并三唑共价键结后，A熔点上升至224℃(实例42)。这是重要且无法预期的惊人改良。
Figure PCTCN2019077919-appb-000004
因为光盘的有机染料吸收激光后转换成热能，會造成局部高温(250℃或以上)。化合物(B)经与苯并三唑共价键结后,不仅熔点和热稳定性提高,苯并三唑所提供的紫外光(UVA+UVB)吸收能力,也可增加光盘的保存寿命。
较佳地，本发明化合物增加稳定性的同时，不影响有机染料、或转光剂原有的发光性质。
更佳地，设计式(1)或式(2)化合物中的R 1～R 3的结构，以增加或减少共轭性，则可增加或减少有机染料或转光剂原有的发光性质。例如实例11的化合物(19)，一方面较化合物(18)增加了共轭性，一方面也增加了吸收或放出可见光的波长。应用领域也可从染料扩展到其他领域，例如农膜。此外，高稳定的化合物(7)除了应用在农膜，对于 DVD-R光盘常用的红色激光(640nm)，也能适用。
再者，本发明化合物也可应用为紫外光及/或蓝光吸收剂。由于本发明化合物具有发光性质，可当作具有特殊的彩色紫外光吸收剂及/或蓝光吸收剂。传统防蓝光吸收剂，仅能吸收紫外光(UVA)及蓝光。本发明化合物则具有大范围紫外光(UVA+UVB)吸收，因此不需额外添加紫外光(UVB)吸收剂情况下，即可以同时吸收紫外光(UVA+UVB)及蓝光,充分达到保护人体、高分子或其他有机材料的功能。
本发明提供的化合物是一种多环化合物，具有式(1)或式(2)所示的结构。
A-R 1-B-R 2-C-R 3-D
(1)
A-R 1-B-R 2-D-R 3-C
(2)本发明中式(1)或式(2)所示化合物的构成片段A、B、C、D均相同，差别仅在于C环和D环的顺序不同。本发明式(1)与式(2)化合物具有单一性。
本发明式(1)或式(2)之化合物之特征在于,包括至少一个可见光或荧光发射基团，及至少一个另外的紫外光吸收基团；
其中，R 2-C-R 3-D或R 2-D-R 3-C是可见光发射基团或荧光发射基团；
A-R 1-B是紫外光吸收基团；
R 1～R 3是一键或/且任意的二价联结基团；较佳地，R 1是一键或 任意的二价联结基团,更佳地,R 1同时是一键且二价联结基团，例如，A-R 1-B是9-氢咔唑或二苯并噻吩；
A、B、C、为未取代或经R 4取代之5-7员环，较佳地,是苯环、苯并碳环、含氮的5-7员杂环、或苯并含氮5-7员杂环，含氮杂环并不排除其他杂原子，苯并含氮5-7员杂环指的是苯环与含氮5-7员杂环所稠合而成；
D为碳、氮、氧、硫原子所构成未取代之或经取代之5-7员杂环或苯并5-7员杂环,其中,环的碳原子的取代基选自1或多个H、羟基、氧基(oxo)、硫基(thioxo)、硫醇基(thiol)、胺基(amino)、亚胺基(imino)、C 1～C 8直链或支链烷基、R 4,环的氮原子的取代基选自1或多个H、羟基、氧基(oxo)、直链或支链C 1～C 8烷基；
R 4是一个或多个取代基(在本发明结构式中R 4或其他取代基的不确定位置取代,指的是在环上任意的位置,例如,当结构式图显示R 4在环上的键结是在两原子间,指的是R 4可在环上任意位置的键结),并且各自独立地选自氢、卤素、羟基、氨基、硝基、氰基、直链或支链C 1～C 18的烷基、烯基或烷氧基、取代或未经取代的苯基、SR 5、SO 2R 5、SO 3R 5、COOR 5、COR 5、OCOR 5、C(O)NR 6R 7、SO 2NR 6R 7、NR 6R 7,其中,R 5、R 6、R 7各自独立地选自氢、直链或支链C 1～C 8的烷基,且R 4与相邻的R 4之间,或R 4与相邻的环之间,可一起表示3-6原子的稠合碳环或稠合杂环,较佳地,含一或多个C、N、O、S的3-6原子的稠合杂环,较佳地,卤素为氯。
较佳地,R 1～R 3是一键,或由1-10个选自下列基团所组成的一条链: -O-、-S-、-C(＝O)-、-COO-、-C(＝S)-、-C(＝N-R 13)-、-N(R 13)-、-C(R 14)(R 15)-、-C(R 16)＝、-C≡、-C(R 17)＝C(R 18)-、-Ph-。R 13～R 18是一个或多个,并且各自独立地选自氢、卤素、羟基、未取代或经卤素取代的直链或支链C 1～C 6烷基(较佳地,C 1～C 4的烷基)、未取代或经卤素或C 1～C 6烷基(较佳地,C 1～C 4的烷基)取代的苯基。Ph是未取代或经卤素、OH基或经直链或支链C 1～C 6烷基(较佳地,C 1～C 4的烷基)所取代的苯基,较佳地,卤素为氯。
A选自:
Figure PCTCN2019077919-appb-000005
A被一个或多个R 4或Ph取代。其中,p＝0～3,较佳地,p＝0～2；R 4是一个或多个取代基,并且各自独立地选自氢、卤素、硝基、氰基、直链或支链C 1～C 8的烷基、烯基或烷氧基、SR 5、SO 2R 5、COOR 5、COR 5、C(O)NR 6R 7、NR 6R 7,其中,R 5、R 6、R 7各自独立地选自氢、直 链或支链C 1～C 8的烷基,较佳地,R 5、R 6、R 7是氢或直链或支链C 1～C 4的烷基,较佳地,卤素为氯。Ph是未取代或经取代的苯基,较佳地,取代基是卤素、羟基、C 1～C 6烷氧基(较佳地,C 1～C 4的烷氧基)或C 1～C 6烷基(较佳地,C 1～C 4的烷基)取代的苯基,较佳地,卤素为氯。R 19～R 20是一个或多个,并且各自独立地选自氢、直链或支链C 1～C 6的烷基(较佳地,C 1～C 4的烷基)、未取代或经取代苯基,较佳地,取代基是卤素或直链或支链C 1～C 6的烷基(较佳地,C 1～C 4的烷基)。
B选自:
Figure PCTCN2019077919-appb-000006
C选自:
Figure PCTCN2019077919-appb-000007
Figure PCTCN2019077919-appb-000008
D选自:
Figure PCTCN2019077919-appb-000009
其中,p＝0～3,较佳地,p＝0～2；n＝0～1；X 1～X 6,各自独立地选自 C＝O、C＝S、C＝N-R 8、N、NR 9、C、O、S、CR 10、CR 11R 12、CNR 11R 12、CR 10NR 11R 12。其中,R 8～R 12是一个或多个,并且各自独立地选自氢、直链或支链C 1～C 8的烷基或烯基、未取代或经直链或支链C 1～C 6烷基(较佳地,C 1～C 4的烷基)或卤素所取代的苯基；D环未经取代或经R 4取代且经由1～2个双键或单键与环外连结。较佳地,D环经由双键与环外连结。较佳地,卤素为氯。
更佳地,R 1～R 3是一键,或/且由1-6个选自下列基团所组成的一条链:-O-、-C(＝O)-、-COO-、-N(R 13)-、-C(R 14)(R 15)-、-C(R 16)＝、-C(R 17)＝C(R 18)-、-Ph-。其中,R 13～R 18是一个或多个,并且各自独立地选自H、未取代或经卤素取代的直链或支链C 1～C 6烷基(较佳地,C 1～C 4的烷基)、未取代或经卤素或C 1～C 6烷基(较佳地,C 1～C 4的烷基)取代的苯基。Ph是未取代或经卤素、OH基或C 1～C 6烷基(较佳地,C 1～C 4的烷基)取代的苯基,较佳地,卤素为氯。
A选自：
Figure PCTCN2019077919-appb-000010
p＝0～2；
R 4是一个或多个取代基,并且各自独立地选自氢、卤素、硝基、氰基、直链或支链C 1～C 8的烷基、烯基或烷氧基、SR 5、SO 2R 5、COOR 5、 COR 5、C(O)NR 6R 7、NR 6R 7,其中,R 5、R 6、R 7各自独立地选自氢、直链或支链C 1～C 8的烷基。较佳地,R 5、R 6、R 7是氢或直链或支链C 1～C 4的烷基,较佳地,卤素为氯。Ph是未取代或经R 4取代的苯基,较佳地,取代基是氢、卤素、OH基、C 1～C 6烷氧基(较佳地,C 1～C 4的烷氧基)或C 1～C 6烷基(较佳地,C 1～C 4的烷基)取代的苯基,较佳地,卤素为氯；
B选自:
Figure PCTCN2019077919-appb-000011
C选自:
Figure PCTCN2019077919-appb-000012
D选自:
Figure PCTCN2019077919-appb-000013
其中，当n＝0时，X 1选自C＝O、C＝S,X 2、X 3、X 4各自独立地选自C＝O、C＝S、C＝N-R 8、C-NR 11R 12、N、NR 9、C、O、S、CR 10、CR 11R 12；
当n＝1时，X 4、X 6各自独立地选自选自C＝O、C＝S，X 1、X 2、X 3各自独立地选自C＝O、C＝S、C＝N-R 8、N、NR 9、C、O、S、CR 10、CR 11R 12、C-NR 11R 12；R 8～R 12是一个或多个,并且各自独立地选自H、 直链或支链C 1～C 6的烷基(较佳地,C 1～C 4的烷基)、未取代或经卤素或C 1～C 6的烷基(较佳地,C 1～C 4的烷基)取代苯基。D环未经取代或经R 4取代且经由1～2个双键或单键与环外连结。较佳地，D环经由双键与环外连结。
更佳地，R 2是一键或-(CHR 21) qN(R 22)-,其中,R 21、R 22各自独立地选自氢、直链或支链C 1～C 8的烷基(较佳地,C 1～C 4的烷基)、未取代苯基或经C 1～C 6烷基(较佳地,C 1～C 4的烷基)取代的苯基,其中,q＝0-18,较佳地,q＝0～8,更佳地,q＝0～4,特佳地,q＝0～2,最佳地,q＝1；
D选自以下环:
Figure PCTCN2019077919-appb-000014
Figure PCTCN2019077919-appb-000015
其中，R 4是一或多个取代基,并且各自独立地选自氢、卤素、直链或支链C 1～C 8的烷基、烯基或烷氧基(较佳地,C 1～C 6或C 1～C 4的烷基、烯基或烷氧基)、SR 5、SO 2R 5、COOR 5、COR 5、C(O)NR 6R 7、NR 6R 7,其中,R 5、R 6、R 7各自独立地选自氢、直链或支链C 1～C 6的烷基(较佳 地,C 1～C 4的烷基),较佳地,卤素为氯；p＝0～2；较佳地,p＝0～1,特佳地,p＝0；R 9、R 23～R 34选自氢、直链或支链C 1～C 6的烷基(较佳地,C 1～C 4的烷基)、未取代苯基或C 1～C 6烷基(较佳地,C 1～C 4的烷基)取代的苯基。
特佳地，A-R 1-B选自以下基团：
Figure PCTCN2019077919-appb-000016
Figure PCTCN2019077919-appb-000017
R 4是一个或多个取代基，并且各自独立地选自氢、卤素、羟基、氨基、硝基、氰基、直链或支链C 1～C 18的烷基、烯基或烷氧基、取代或未经取代的苯基、SR 5、SO 2R 5、SO 3R 5、COOR 5、COR 5、OCOR 5、C(O)NR 6R 7、SO 2NR 6R 7、NR 6R 7，其中R 5、R 6、R 7各自独立地选自氢、直链或支链C 1～C 8的烷基(较佳地,C 1～C 4的烷基)，且R 4与相邻的R 4之间，或R 4与相邻的环之间，可一起表示3-6原子的稠合碳环或稠合杂环，较佳地，含C、N、O、S的3-6原子的稠合杂环，较佳地，卤素为氯；p＝0-2，较佳地，p＝0-1，更佳地，p＝0。
R 19、R 35～R 39是一个或多个，并且各自独立地选自H、直链或支链C 1～C 6的烷基(较佳地,C 1～C 4的烷基)、未取代或经卤素或C 1～C 6的烷基(较佳地,C 1～C 4的烷基)取代苯基；Ph是未取代或经卤素、OH基或C 1～C 6烷基(较佳地,C 1～C 4的烷基)取代的苯基，较佳地，卤素为氯。
非常特佳地，式(1)或式(2)化合物，包括经至少1个可见光或荧光发射基团，和至少1个共价联结的紫外光吸收基团，其中，可见光或荧光发射基团是R 2-C-R 3-D或R 2-D-R 3-C，选自：
Figure PCTCN2019077919-appb-000018
Figure PCTCN2019077919-appb-000019
D选自：
Figure PCTCN2019077919-appb-000020
Figure PCTCN2019077919-appb-000021
其中，紫外光吸收基团是A-R 1-B，选自：
苯并三唑(Benzotriazole):
Figure PCTCN2019077919-appb-000022
三嗪(Triazine):
Figure PCTCN2019077919-appb-000023
咔唑(carbazole):
Figure PCTCN2019077919-appb-000024
草酰苯胺(Oxanilide):
Figure PCTCN2019077919-appb-000025
苯并恶嗪(Benzoxazinone):
Figure PCTCN2019077919-appb-000026
喹唑啉酮(quinazolinone):
Figure PCTCN2019077919-appb-000027
二苯甲酰甲烷(Dibenzoylmethane):
Figure PCTCN2019077919-appb-000028
苯基甲脒乙酯(Phenylformamidine):：
Figure PCTCN2019077919-appb-000029
甲亚胺(Azomethine):
Figure PCTCN2019077919-appb-000030
喹唑啉(Quinazoline):
Figure PCTCN2019077919-appb-000031
苯甲酸(Benzoic acid):
Figure PCTCN2019077919-appb-000032
二苯甲酮(Benzophenone):
Figure PCTCN2019077919-appb-000033
二苯并噻吩(Dibenzothiophene):
Figure PCTCN2019077919-appb-000034
二苯并呋喃(Dibenzofuran):
Figure PCTCN2019077919-appb-000035
二苯硫醚(Diphenyl sulfide):
Figure PCTCN2019077919-appb-000036
二苯醚(Oxydibenzene):
Figure PCTCN2019077919-appb-000037
以上可见光(荧光)发射基团或紫外光吸收基团，均被(R 4) p取代基所取代，其中，p＝0～3，较佳地，p＝0～1，特佳地，p＝0。R 4是一个或多个取代基，并且各自独立地选自氢、卤素、羟基、氨基、硝基、氰基、直链或支链C 1～C 18的烷基、烯基或烷氧基、取代或未经取代的苯基、SR 5、SO 2R 5、SO 3R 5、COOR 5、COR 5、OCOR 5、C(O)NR 6R 7、 SO 2NR 6R 7、NR 6R 7，其中R 5、R 6、R 7各自独立地选自氢、直链或支链C 1～C 8的烷基(较佳地,C 1～C 4的烷基)，且R 4与相邻的R 4之间，或R 4与相邻的环之间，可一起表示3-6原子的稠合碳环或稠合杂环，较佳地，含一或多个C、N、O、S的3-6原子的稠合杂环；R 40～R 49是相同或相异各自独立选自氢、直链或支链C 1～C 8的烷基或烯基(较佳地,C 1～C 4的烷基或烯基)、未取代或经直链或支链C 1～C 6烷基(较佳地,C 1～C 4的烷基)或卤素所取代苯基；R 50选自氢、一价金属、直链或支链C 1～C 8的烷基或烯基(较佳地,C 1～C 4的烷基)、未取代或经直链或支链C 1～C 6烷基(较佳地,C 1～C 4的烷基)或卤素所取代苯基。较佳地，卤素为氯。较佳地，一价金属是锂或钠。
最佳地，式(1)或式(2)化合物如下：
Figure PCTCN2019077919-appb-000038
Figure PCTCN2019077919-appb-000039
Figure PCTCN2019077919-appb-000040
Figure PCTCN2019077919-appb-000041
式(1)或式(2)化合物的制法,其特征在于，包括以下的反应步骤之一。
式(1)化合物的制备，包括以下的反应步骤之一：
Figure PCTCN2019077919-appb-000042
其中,式(2)化合物的制备，包括以下的反应步骤之一:
Figure PCTCN2019077919-appb-000043
其中,A～D环,R 1～R 3,同前所定义；
D’为D环之前驱物,选自D’是D环之前驱物,选自
Figure PCTCN2019077919-appb-000044
Figure PCTCN2019077919-appb-000045
D”为D环之前驱物,
Figure PCTCN2019077919-appb-000046
Z是离去基,包括但不限于卤素、C 1～C 10磺酸酯基、C 1～C 10烷氧基；较佳地,Z选自、卤素、对甲苯磺酸酯(OTs)、甲磺酸酯(OMs)、C 1～C 4烷氧基。较佳地,卤素为氯。
U、V选自C＝O、C＝S、C＝N-R 51、C(R 52)(R 53)；R 50～R 53是相同或相异各自独立选自一键、氢、直链或支链C 1～C 8的烷基,较佳地,烷基是直链或支链C 1～C 4的烷基。
T为相同或相异,各自独立选自NH、NH 2、OH、SH。
本发明化合物(1)的具体制法之1,包括实施例1-11、15-22、33的制法。其中实施例1-4化合物的制法如下:
Figure PCTCN2019077919-appb-000047
本发明化合物(1)的具体制法之2,包括实施例12-14、23-32的制法。其中实施例13的制法如下:
Figure PCTCN2019077919-appb-000048
本发明化合物(2)的具体制法之1,包括实施例34的制法。制法如下:
Figure PCTCN2019077919-appb-000049
本发明化合物(2)的具体制法之2,包括实施例35的制法。制法如下:
Figure PCTCN2019077919-appb-000050
本发明化合物(2)的具体制法之3,包括实施例36的制法。制法如 下:
Figure PCTCN2019077919-appb-000051
本发明化合物(2)的具体制法之4,包括实施例37的制法,制法如下:
Figure PCTCN2019077919-appb-000052
本发明化合物(2)的具体制法之5,包括实施例38。制法如下:
Figure PCTCN2019077919-appb-000053
本发明化合物(2)的具体制法之6,包括实施例39的制法。制法如下:
Figure PCTCN2019077919-appb-000054
Figure PCTCN2019077919-appb-000055
传统苯并三唑化合物的具体制法,其合成方式通常是以2-硝基苯胺和各种取代的苯酚为起始物。第1步骤形成偶氮化合物,第2步骤是还原反应,形成苯并三唑化合物(US 3773751),例如实施例6。制法如下:
Figure PCTCN2019077919-appb-000056
本发明化合物可应用于薄膜。例如,在农膜中用为转光剂。也可用在防紫外膜或防蓝光膜,以保护眼睛或其他组织。本发明化合物可应用于一般薄膜或有机材质,以保护薄膜或有机材质本身。再如,本发明化合物可应用于光记录媒体的记录层。本发明化合物也可针对不同不同需要,组合其他化合物一起使用。这些应用的实施可使用产业上的一般方式。
农膜通常是采用聚氯乙烯、乙烯或低密度聚乙烯(LDPE)、乙烯-醋酸乙烯共聚物(EVA)、茂金属线性聚乙烯(MLLDPE)等树脂原料,添加助剂后，通过吹塑、压延工艺制成。具体制造方式,例如,取低密度聚乙烯为基料1kg，茂金属线性聚乙烯200g，转光剂5g，抗氧剂8g，紫外吸收剂5g，甘油酯9g，混匀后，经吹膜机组按常规吹塑成型。厚度为0.03～2.0mm的透明的薄膜。转光剂的添加量视农作物的种类与农膜厚度而定,通常范围包括但不限于0.001％～20％,较佳 地,0.2％～5％。
防紫外光膜或防蓝光膜,或农膜的制造,也可将转光或防蓝光组合物涂布在基底层或离型层,待硬化后使用。或采用转移涂布工艺，先涂布在离型膜上，再转移到基底层上。膜上、下层各贴合一层离型薄膜则是OCA光学胶(Optically Clear Adhesive)。涂布方式是习知技艺,包括传统刷式涂布、喷雾涂布、帘式涂布、辊式涂布、狭缝式涂布、气刀涂布、刮刀涂布、计量棒涂布。干燥方法包括自然干燥、微波干燥、紫外线干燥、红外线干燥、热空气干燥。基底层包括聚酯、玻璃、聚乙烯、聚丙烯、聚碳酸酯、聚酰胺、聚丙烯酸酯、聚甲基丙烯酸酯、聚醋酸乙烯、聚氯乙烯之一种或多种混合。离型膜包括硅氧化合物型和非硅氧化合物材质。转光或防蓝光组合物,其组成包括本发明的转光剂、防紫外光剂、或防蓝光剂、聚合体、溶剂、及/或助剂、及/或引发剂、及/或单体。
本发明化合物用于光学记录媒体的记录层。可以利用旋转涂布法,将有机染料记录层涂布于基板上。基板可以是聚碳酸酯(PC)或聚丙烯胺材质。记录层的厚度通常为数个奈米到数十个奈米。涂布后以溅镀法于记录层上形成一反射层。再旋转涂布一黏着层，并通过黏着层将一盖板黏着于反射层上,以形成光盘。
附图说明
图1本发明之化合物(7)的UV-VIS吸收图(10mg/四氢呋喃)；
图2本发明之化合物(7)的TGA(热重分析仪)图；
图3本发明之化合物(18)的UV-VIS吸收图(10mg/四氢呋喃)；
图4本发明转光剂所制成的农膜的外观。
具体实施方式
以下对本发明的具体实施方式进行说明，但本发明不限于这些实施方式。
A-R 1-B-R 2-C-R 3-D
(1)
表1 为式(1)化合物
Figure PCTCN2019077919-appb-000057
Figure PCTCN2019077919-appb-000058
Figure PCTCN2019077919-appb-000059
Figure PCTCN2019077919-appb-000060
A-R 1-B-R 2-D-R 3-C
(2)
表2 为式(2)化合物
Figure PCTCN2019077919-appb-000061
Figure PCTCN2019077919-appb-000062
实施例1
2-(2-羟基-3-(氯甲基)-5-甲基)苯并三氮唑(化合物3)的制备
Figure PCTCN2019077919-appb-000063
在5000ml反应瓶加入2-(2-羟基-5-甲基)苯并三氮唑(UV-P,化合物3)350g、多聚甲醛55g、乙酸2000克、35％盐酸300克，升温到60℃保温反应10个小时，取样监控反应。降温、水洗、烘干得白色粉末(氯甲基UV-P,化合物4)，收率96％。C 14H 12ClN 3O,熔点:163-164℃。
实施例2
2-(2-羟基-3-(N,N-二甲基苯胺)-5-甲基)苯并三氮唑(化合物5)的制备
Figure PCTCN2019077919-appb-000064
投入甲苯180ml、碳酸钾17g、N-甲基苯胺13.9g、相催化剂0.2g、化合物(4)33.3g，升温到90-100℃反应5小时，取样监控反应。降温到30℃,水洗并回收甲苯。加入180g甲醇搅拌,过滤、烘干得到固体(化合物5)。纯度98.3％，收率为84％。C 21H 20N 4O,熔点:98-100℃。
实施例3
2-(2-羟基-3-(4-甲酰基-N,N-二甲基胺基苯)-5-甲基)苯并三氮唑(化合物6)的制备
Figure PCTCN2019077919-appb-000065
投入化合物(5)35g、DMF 8.7g，保持20-25℃下滴加三氯氧磷18.4g，约2小时加完。升温到90℃反应2小时，取样监控反应(Vilsmeier-Haack formylation)。将反应物料慢慢加到30℃以下的300g水中水解，加完再用30％液碱中和,调整pH到8，滤出固体。用甲苯溶解,水洗,降温到15℃,固体析出，烘干得黄色固体31.8g(化合物6)。C 21H 19N 4O 2,熔点:111-113℃。
实施例4
5-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(甲基)氨基)亚苄基)嘧啶-2,4-，6(1H，3H，5H)三酮(化合物7)的制备
Figure PCTCN2019077919-appb-000066
化合物(6)50g和巴比妥酸17.1克溶于甲苯，加入5g乙酸铵和10g乙酸，保持80-90℃,反应1小时。再升温至回流反应反应8小时，取样监控反应，反应完成后,降温，滤出固体，用甲苯洗涤，再用二氯乙烷洗涤，过滤、水洗、烘干,得化合物(7)固体。收率：约80％。C 26H 22N 6O 4，熔点:262-270℃。
实施例5
5-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(乙基)氨基)亚苄基)嘧啶-2,4-，6(1H，3H，5H)三酮(化合物8)的制备。
Figure PCTCN2019077919-appb-000067
根据实施例1-4方法,但以N-乙基苯胺代替N-甲基苯胺,得到化合物(8)。C 27H 24N 6O 4,熔点:263-267℃。
实施例6
5-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-(2-甲基庚-2-基)苄基)(乙基)氨基)亚苄基)嘧啶-2,4,6(1H，3H，5H)-三酮(化合物9)的制备。
Figure PCTCN2019077919-appb-000068
原料2-(2-羟基-5-叔辛基苯基)-2H-苯并三唑(化合物10)来自Eutec co.(Eusorb 329,熔点:102-106℃),或可以下所述方式制得。13.8克邻硝基苯胺加入25毫升37％盐酸搅拌,用40ml水稀释并冷却至-15℃。加入7.5g亚硝酸钠(溶于水中),保持温度在0～5℃,得到重氮盐(Diazonium)。混合5.2g的4-对叔辛基苯酚(4-tert-Octylphenol)、20ml的石油醚、5ml的水和2.5g的氢氧化钙，取样监控反应。反映完成 后,加入20g冰,并升温至0℃。加入前述的重氮盐,搅拌2小时。加入浓盐酸中和,干燥后得到2-((2-硝基苯基)二氮烯基)-4-(2,4,4-三甲基戊-2-基)苯酚(化合物11)。C 20H 25N 3O 3,熔点:114-115℃。
取35.7g化合物(11)溶于100ml石油醚,加入17.2g锌和100ml的水。50℃下4小时内加入41.6g的NaOH溶液(25％),并留置1小时。加入100ml浓盐酸留置2小时，取样监控反应，有机层用水洗涤,去除溶剂得到化合物(10)。C 20H 25N 3O,熔点:102-106℃。
Figure PCTCN2019077919-appb-000069
根据实施例1-5方法,但以2-(2-羟基-5-叔辛基苯基)-2H-苯并三唑(Eusorb 329,化合物10)代替UV-P(化合物3)当作起始物,得到化合物(9)。C 34H 38N 6O 4,m/z:594.3[M] +。
实施例7
5-(4-((3-(5-氯-2H-苯并[d][1,2,3]三唑-2-基)-2-羟基苄基)(乙基)氨基)亚苄基)嘧啶-2,4-，6(1H，3H，5H)三酮(化合物12)的制备。
Figure PCTCN2019077919-appb-000070
根据实施例6方法,以4-氯-2-硝基苯胺代替邻硝基苯胺为起始物,得到2-(2'-羟基-苯基)-5-氯-苯并三唑(化合物13),C 12H 8ClN 3O,熔点:139-140℃。根据实施例1-5方法,但以2-(2'-羟基-苯基)-5-氯- 苯并三唑(化合物13)代替UV-P(化合物3)当作起始物,得到化合物(12)。C 26H 21ClN 6O 4,m/z:516.1[M] +。
实施例8
5-(4-((3-(5-甲氧基-2H-苯并[d][1,2,3]三唑-2-基)-2-羟基苄基)(乙基)氨基)亚苄基)嘧啶-2,4-，6(1H，3H，5H)三酮(化合物14)的制备。
Figure PCTCN2019077919-appb-000071
根据实施例6方法,以4-甲氧基-2-硝基苯胺代替邻硝基苯胺为起始物,得到2-(2'-羟基-苯基)-5-氯-苯并三唑(化合物15)。C 14H 13N 3O 2,熔点:126-127℃。根据实施例1-5方法,但以2-(2'-羟基-苯基)-5-甲氧基-苯并三唑(化合物15)代替UV-P(化合物3)当作起始物,得到化合物(14)。C 28H 26N 6O 5,m/z:526.2[M] +。
实施例9
3-(2H-苯并[d][1,2,3]三唑-2-基)-5-((乙基(4-((2,4,6-三氧代四氢嘧啶-5(2H)-亚基)甲基)苯基)氨基)甲基)-4-羟基苯甲酸甲酯(化合物16)的制备。
Figure PCTCN2019077919-appb-000072
根据实施例6方法,以4-羟基苯甲酸取代4-对叔辛基苯酚,得到3-(2H-苯并[d][1,2,3]三唑-2-基)-4-羟基苯甲酸。加入氯化亚砜,升温至回流2小时后,蒸干氯化亚砜,加入正己醇回流，取样监控反应。得到3-(2H-苯并[d][1,2,3]三唑-2-基)-4-羟基苯甲酸己酯(化合物17)。C 19H 21N 3O 3,熔点:83-84℃。
Figure PCTCN2019077919-appb-000073
根据实施例1-5方法,但以3-(2H-苯并[d][1,2,3]三唑-2-基)-4-羟基苯甲酸己酯(化合物17)代替UV-P(化合物3)当作起始物,得到化合物(16)。C 33H 34N 6O 6,m/z:610.3[M] +。
实施例10
5-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(乙基)氨基)亚苄基)-2,2-二甲基-1,3-二恶烷-4,6-二酮(化合物18)的制备
Figure PCTCN2019077919-appb-000074
20g的化合物(6)和8.2g米氏酸(Meldrum's acid)在甲苯中，加入4.1g乙酸铵和10g乙酸。回流脱水反应4小时，取样监控反应，反应完成后,滤出固体，用二氯乙烷升温溶解，水洗，蒸馏出二氯乙烷，加入甲苯重结晶，得化合物(18)。C 29H 28N 4O 5,熔点:220-224℃。
实施例11
5-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(乙基)氨基)亚苄基)-2,2-二甲基-1,3-二恶烷-4,6-二酮(化合物19)制备
Figure PCTCN2019077919-appb-000075
12g化合物(6)加入1％氢氧化钠、15％乙醇的溶液200ml中。滴加5g的30％乙醛水溶液。反应过夜，加入l5g的NaCl搅拌，并用稀盐酸调节pH成为中性。然后用乙酸乙酯萃取、干燥后得到3-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(乙基)氨基)苯基)丙烯醛(20)。
Figure PCTCN2019077919-appb-000076
再根据实施例10方法,化合物(20)加入米氏酸、乙酸铵和乙酸,进行反应,得到化合物(19)。C 31H 30N 4O 5,m/z:538.2[M] +。
实施例12
5-(4-(甲基氨基)亚苄基)嘧啶-2,4,6(1H，3H，5H)-三酮(化合物21)的制备
Figure PCTCN2019077919-appb-000077
将20g巴比妥酸及13.6g的4-甲基胺基苯甲醛,溶解于二氯甲烷。加入分子筛除水并装置氯化钙管以防水。加入1ml呱啶和0.6ml醋酸，并加热回流,反应2小时，反应期间补充新鲜分子筛，取样监控反应。反应完成后除去溶剂,酸洗、干燥后得到化合物(21)。C 12H 11N 3O 3,m/z:245.1[M] +。
实施例13
5-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(甲基)氨基)亚苄基)嘧啶-2,4-，6(1H，3H，5H)三酮(化合物7)的制备
Figure PCTCN2019077919-appb-000078
根据实施例2方法,但以化合物(21)代替N-甲基苯胺,得到化合物(7)。原料化合物(4)之H1-NMR中化学位移4.6消失(-C H 2 Cl),且化学位移5.0新生(化合物7,- CH 2 N),代表反应完成。熔点范围与实例4方法所制备的化合物(7)相同。
实施例14
3-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(甲 基)氨基)苯基)-2-氰基-3-苯基丙烯酸乙酯(化合物22)的制备
Figure PCTCN2019077919-appb-000079
根据实施例2方法,但以4-甲基胺基二苯甲酮(化合物23)代替化合物N-甲基苯胺,得到化合物(24)。
Figure PCTCN2019077919-appb-000080
再根据实施例4方法,以化合物(24)代替化合物(6),经管柱层析分离,得到化合物(22)。C 32H 26N 6O 4,m/z:558.2[M] +。
实施例15
5-((1-(3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)-1H-吲哚-3-基)亚甲基)嘧啶-2,4,6-(1H，3H，5H)-三酮(化合物25)的制备
Figure PCTCN2019077919-appb-000081
根据实施例3方法,以3-吲哚甲醛代替N-甲基苯胺,经管柱层析 分离,得到化合物(26)。再根据实施例4方法,以化合物(26)取代化合物(6),经管柱层析分离,得到化合物(25),C 27H 20N 6O 4。m/z:492.2[M] +。
其中3-吲哚甲醛为工业原料,可以以下方式制得(Vilsmeier反应):冰浴下，30g DMF，30分钟内滴入16g的POCl 3。缓慢加入11g吲哚化合物的DMF溶液,升温至35℃搅拌反应1小时。得到的糊状物加入50g碎冰搅拌,搅拌下将0.1M的NaOH慢慢加入。水洗后，用乙醇重结晶，得到3-吲哚甲醛,C 9H 7NO。熔点：196～197℃。
实施例16
5-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(甲基)氨基)亚苄基)-4-硫代噻唑-2-酮(化合物27)的制备
Figure PCTCN2019077919-appb-000082
根据实施例4方法,以化合物4-硫代噻唑-2-酮(CAS RN.4303-29-1)取代巴比妥酸化合物,得到化合物(27)。C 25H 21N 5O 4,m/z:455.2[M] +。
实施例17
5-((6-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(甲基)氨基)萘-2-基)亚甲基)嘧啶-2,4,6(1H，3H，5H)-三酮(化合物28)的制备
Figure PCTCN2019077919-appb-000083
根据实施例15方法,以6-(甲基氨基)-2-萘甲醛取代3-吲哚甲醛,得到化合物(28)。C 30H 24N 6O 4,m/z:532.2[M] +。
实施例18
5-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(甲基)氨基)亚苄基)恶唑烷-2,4-二酮(化合物29)的制备
Figure PCTCN2019077919-appb-000084
根据实施例4方法,以化合物恶唑烷-2,4-二酮(CAS RN.2346-26-1),取代巴比妥酸化合物,得到化合物(29)。C 25H 21N 5O 4,m/z:455.2[M] +。
实施例19
2-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(甲基)氨基)亚苄基)环戊-4-烯-1,3-二酮(化合物30)的制备
Figure PCTCN2019077919-appb-000085
根据实施例4方法,以4-环戊烯-1,3-二酮化合物取代巴比妥酸化 合物,得到化合物(30)。C 26H 19N 4O 3,m/z:435.2[M] +
实施例20
2-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(甲基)氨基)亚苄基)-1H-茚-1,3(2H)-二酮(化合物31)的制备
Figure PCTCN2019077919-appb-000086
根据实施例4方法,以化合物1H-茚-1,3(2H)-二酮,取代巴比妥酸化合物,得到化合物(31)。C 31H 24N 4O 3,m/z:500.2[M] +。
实施例21
5-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(甲基)氨基)亚苄基)-3,5-二氢-4H-咪唑-4-酮(化合物32)的制备
Figure PCTCN2019077919-appb-000087
根据实施例4方法,但以化合物1,4-二氢咪唑-5-酮(CAS RN.1968-28-1),取代巴比妥酸化合物,得到化合物(32)。C 25H 22N 6O 2,m/z:438.2[M] +。
实施例22
4-(4-((3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)(甲基)氨基)亚苄基)恶唑-5-(4H)-酮(化合物33)的制备
Figure PCTCN2019077919-appb-000088
根据实施4方法,以化合物4H-5-氧代-恶唑(CAS RN.497-24-5),取代巴比妥酸化合物，得到化合物(33)。C 25H 21N 5O 3,m/z:439.2[M] +。
实施例23
3-(3-(4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-(叔丁基)-4-羟基苯基)-N-(4-((2,4,6-三氧代四氢嘧啶-5(2H)-亚基)甲基)苯基)丙酰胺(化合物34)的制备
Figure PCTCN2019077919-appb-000089
取3-(3-(4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-(叔丁基)-4-羟基苯基)丙酸甲酯(化合物35)5.2g,溶于甲苯中,在配置冷凝分水器的烧瓶中,加热回流。向甲苯溶液中加入化合物(21),取样监控反应。反应完成后,真空蒸馏。经层析分离,得到化合物(34)，C 44H 44N 6O 5。m/z:736.3[M] +。
Figure PCTCN2019077919-appb-000090
化合物(35)制备方法(根据CN201710949552.0):简要地,将16g的2-氯-4,6-二(2′,4′二甲基-苯基)-1,3,5-三嗪(化合物36)和15g的(3-叔丁基-4-羟基苯基)丙酸甲酯(化合物37)溶于150ml氯苯中,加入10g无水三氯化铝,加热搅拌溶解。升温至90℃,取样监控反应。反应完成后,减压蒸馏,经层析分离后,得到化合物(35)。
Figure PCTCN2019077919-appb-000091
实施例24
5-(4-((3-(4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-(叔丁基)-4-羟基苄基)氨基)亚苄基)嘧啶-2,4,6(1H，3H，5H)-三酮(化合物38)的制备
Figure PCTCN2019077919-appb-000092
如实施例13方法,但以2-(4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-6-(叔丁基)-4-(氯甲基)苯酚(化合物39)代替化合物(4),产物经层析分离,得到化合物(38)。C 39H 36N 6O 4。m/z:652.3[M] +。
Figure PCTCN2019077919-appb-000093
化合物(39)的制法:如实施例23的化合物(35)的制法,但以4-(氯甲基)-2-甲基苯酚,代替(3-(叔丁基)-4-羟基苯基)丙酸甲酯(37)。
实施例25
5-(4-((5-苯甲酰基-4-羟基-2-(辛氧基)苄基)(甲基)氨基)亚苄基)嘧啶-2,4,6(1H，3H，5H)-三酮(化合物40)的制备
Figure PCTCN2019077919-appb-000094
如实施例13方法,但以(5-(氯甲基)-2-羟基-4-(辛氧基)苯基)(苯基)甲酮(化合物41)代替化合物(4)。经层析分离,得到化合物(40),C 34H 37N 3O 6。m/z:583.3[M] +。
Figure PCTCN2019077919-appb-000095
化合物(41)的制备:如实施例1方法,但以(2-羟基-4-(辛氧基)苯基)(苯基)甲酮(Eutec co.,Eusorb UV-531)代替UV-P(化合物3),得到化合物(41)。
实施例26
5-(4-(甲基(4-(4-氧代-4H-苯并[d][1,3]嗪-2-基)苄基)氨基)亚苄基)嘧啶-2,4,6(1H，3H，5H)三酮(化合物42)的制备
Figure PCTCN2019077919-appb-000096
如实施例13方法,但以2-(氯甲基)-4H-苯并[d][1,3]恶嗪-4-酮(化合物43)代替化合物(4)。经层析分离,得到化合物(42),C 27H 20N 4O 5。m/z:480.1[M] +。
Figure PCTCN2019077919-appb-000097
化合物(43)的制法:100ml二氯乙烷中加入14g的2-氨基苯甲酸(化合物44)、11g三乙胺,滴入19g的4-氯甲基苯甲酰氯(化合物45)搅拌,得到(化合物43)。化合物(45)的制法:4-(羟甲基)苯甲酸(46)在二氯甲烷中,以氯化亚砜回流氯化,得到化合物(45),熔点:28℃。
Figure PCTCN2019077919-appb-000098
实施例27
5-(4-((4-(((2,4-二羟基-喹啉-3-基)亚甲基)氨基)苄基)(甲基)氨基)亚苄基)嘧啶-2,4,6(1H，3H，5H)-三酮(化合物47)的制备
Figure PCTCN2019077919-appb-000099
如实施例13方法,但以3-(((4-(氯甲基)苯基)亚氨基)甲基)喹啉-2,4-二醇(化合物48)代替化合物(4),得到化合物(47),C 29H 23N 5O 5。m/z:521.2[M] +。
Figure PCTCN2019077919-appb-000100
3-(((4-(氯甲基)苯基)亚氨基)甲基)喹啉-2,4-二醇(48)的制法:如实施例1方法,但以3-((苯基亚氨基)甲基)喹啉-2,4-二醇(UA-3701,熔点194℃)代替UV-P(化合物3)。
实施例28
4-(((甲基(4-((甲基(4-((2,4,6-三氧代四氢嘧啶-5(2H)-亚基)甲基)苯基)氨基)甲基)苯基)氨基)亚甲基基)氨基)苯甲酸乙酯(化合物49)的制备
Figure PCTCN2019077919-appb-000101
如实施例13方法,但以4-((((4-(氯甲基)苯基)(甲基)氨基)亚甲基)氨基)苯甲酸乙酯(化合物50)代替代替化合物(4),经纯化,得到化合物(49),C 30H 29N 5O 5。m/z:539.2[M] +。
Figure PCTCN2019077919-appb-000102
化合物(50)制法:如实施例1方法,但以4-(((甲基(苯基)氨基)亚甲基)氨基)苯甲酸乙酯(UV-1,熔点137℃)代替UV-P(化合物3)。
实施例29
N1-(2-乙氧基-4-((甲基(4-((2,4,6-三氧代四氢嘧啶-5(2H)-亚基)甲基)苯基)氨基)甲基)苯基)-N2-(2-乙基苯基)草酰胺(化合物51)的制备
Figure PCTCN2019077919-appb-000103
如实施例13方法,但以N1-(4-(氯甲基)-2-乙氧基苯基)-N2-(2-乙基苯基)草酰胺(化合物52)代替化合物(4),得到化合物(51),C 31H 31N 5O 6。m/z:569.2[M] +。
Figure PCTCN2019077919-appb-000104
N1-(4-(氯甲基)-2-乙氧基苯基)-N2-(2-乙基苯基)草酰胺(化合物52)的制法:如实施例1方法,但以N-(2-乙氧基苯基)-N'-(4-乙基苯基)-乙二酰胺(Eutec co.,UV-312,熔点120℃)代替UV-P(化合物3)。
实施例30
5-(4-(((9H-咔唑-3-基)甲基)(甲基)氨基)亚苄基)嘧啶-2,4,6(1H，3H，5H)-三酮(化合物53)的制备
Figure PCTCN2019077919-appb-000105
如实施例13方法,但以3-(氯甲基)-9H-咔唑(化合物54)代替化合物(4),得到化合物(53),C 25H 20N 4O 3。m/z:424.2[M] +。
Figure PCTCN2019077919-appb-000106
3-(氯甲基)-9H-咔唑(化合物44)的制法:如实施例1方法,但以9H-咔唑代替UV-P(化合物3)。
实施例31
5-(4-(((9H-咔唑-1-基)甲基)(甲基)氨基)亚苄基)嘧啶-2,4,6(1H，3H，5H)-三酮(化合物55)的制备
Figure PCTCN2019077919-appb-000107
如实施例13法,但以9H-咔唑-3-羧酸甲酯(化合物56)代替化合物(4),得到化合物(55),C 25H 18N 4O 4。m/z:438.1[M] +。
Figure PCTCN2019077919-appb-000108
9H-咔唑-1-羧酸甲酯的制法:9H-咔唑-1-羧酸(AKOS BC-1282),以 浓硫酸为催化剂,于过量甲醇中回流获得化合物(56)。
实施例32
5-(4-((二苯并[b，d]噻吩-2-基甲基)(甲基)氨基)亚苄基)嘧啶-2,4,6(1H，3H，5H)-三酮(化合物57)的制备
Figure PCTCN2019077919-appb-000109
如实施例13方法,但以2-(氯甲基)二苯并[b，d]噻吩(化合物58)代替化合物(4),得到化合物(57)。C 25H 19N 3O 3S。m/z:441.1[M] +。
Figure PCTCN2019077919-appb-000110
2-(氯甲基)二苯并[b，d]噻吩(化合物58)的制法:如实施例1方法,但以二苯并[b，d]噻吩代替UV-P(化合物3)。
实施例33
2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯(Eutec co.,Eusorb UV-120)和5-(4-(甲基氨基)亚苄基)嘧啶-2,4,6(1H，3H，5H)-三酮(化合物21)的反应混合物(59)的制备
如实施例2方法,但以2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯(Eutec co.,Eusorb UV-120,熔点149℃)代替UV-P(化合物3)。水洗、烘干后直接与在二氯甲烷中与(化合物21)反应回流,得到产物(59)混合物。
实施例34
1-(3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)-5-(4-(二甲基氨基)亚苄基)嘧啶-2,4-，6(1H，3H，5H)三酮(化合物60)的制备
Figure PCTCN2019077919-appb-000111
将15g的4-(二甲基胺基)苯甲醛、13.2g丙二酸二甲酯、15ml吡啶,溶于甲苯中，并加热回流。取样监控反应，除去溶剂,层析后得到二甲基2-(4-(二甲基氨基)亚苄基)丙二酸二甲酯化合物(化合物61)。C 14H 17NO 4,熔点86-88℃。
Figure PCTCN2019077919-appb-000112
取26.3g二甲基2-(4-(二甲基氨基)亚苄基)丙二酸二甲酯化合物(化合物61)及4.6g二胺基甲烷,在乙醇中回流3小时。蒸干溶剂得到闭环化合物。混合14.6g闭环化合物化合物、21g三氧化铬、和100ml的水。滴入45ml浓硫酸。滴完浓硫酸后,再滴加三氧化铬(21g/50ml水),并加热回流，取样监控反应。冷却至室温后，将反应混合物倒入等体积的水中,并在冰浴中冷却至10℃。分离出沉淀物，用水洗涤。将沉淀物分散于30毫升的水,加入50ml饱和碳酸钠溶液搅拌。过滤得到化合物(60)。C 27H 24N 6O 4,MS:m/z＝496.2[M] +。
实施例35
1-(3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)-5-(4-(二甲基氨基)亚苄基)-3-甲基咪唑烷-2,4-二酮(化合物62)的制备
Figure PCTCN2019077919-appb-000113
如实施例2方法,取27.5g化合物(4)加入甘氨酸甲酯10g反应,得到(3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)甘氨酸甲酯(化合物63)。
Figure PCTCN2019077919-appb-000114
取16.3g的化合物(63)和5.1g的2-异氰酸基-2-甲基丙烷,在二氯乙烷中加热回流过夜,减压蒸馏除去未反应2-异氰酸基-2-甲基丙烷和二氯乙烷后,经层析分离,得到1-(3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)-3-(叔-丁基)咪唑烷-2,4-二酮(化合物64)。
Figure PCTCN2019077919-appb-000115
如实施例4方法,取4g的化合物(65),1.5g的4-(二甲基氨基)苯甲醛,反应后得到1-(3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)-3-(叔-丁基)咪唑烷-2,4-二酮(化合物62)。C 30H 32N 6O 3,m/z:524.3[M] +。
Figure PCTCN2019077919-appb-000116
实施例36
5-(3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苄基)-2-(4-(二乙基氨基)苯基)-2-甲基-1,3-二恶烷-4,6-二酮(化合物67)和5-(3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基亚苄基)-2-(4-(二乙基氨基)苯基)-2-甲基-1,3-二恶烷-4,6-二酮(化合物90)的制备
Figure PCTCN2019077919-appb-000117
Figure PCTCN2019077919-appb-000118
取5.2g丙二酸(68)溶于6ml乙酸酐中，在冰水冷却搅拌下加入0.15ml浓硫酸，水浴中加热溶解，加入4-(二乙基氨基)苯乙酮(69),室温下搅拌过夜。水洗，再用乙酸乙酯萃取，得到2-(4-(二乙基氨基)苯基)-2-甲基-1,3-二恶烷-4,6-二酮(化合物70)。
Figure PCTCN2019077919-appb-000119
取2.75g化合物(4)加入2.34g化合物(70),在乙醇钠的乙醇溶液回流反应过夜,抽去溶剂并用HCl中和后,经层析分离,得到化合物(67)。C 29H 30N 4O 5,m/z:514.2[M] +。
Figure PCTCN2019077919-appb-000120
如实施例3方法,但由代替化合物(3)代替化合物(5),得到3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基苯甲醛(化合物89)。如实施例4方法,但以化合物(70)代替巴比妥酸,化合物(89)代替化合物(6),反应后得到5-(3-(2H-苯并[d][1,2,3]三唑-2-基)-2-羟基-5-甲基亚苄基)-2-(4-(二乙基氨基)苯基)-2-甲基-1,3-二恶烷-4,6-二酮(化合物 90)。C 29H 28N 4O 5,m/z:512.2[M] +。
Figure PCTCN2019077919-appb-000121
实施例37
5-(9H-咔唑-3-基)-3-(4-(二甲基氨基)苯基)恶唑烷-2,4-二酮(化合物71)的制备
Figure PCTCN2019077919-appb-000122
冰水浴下，取34克9H咔唑溶于400毫升干燥的二氯甲烷中，缓慢加入30克无水AlCl 3并继续搅拌10分钟，此后缓慢滴加31克2-氯-2-氧代乙酸甲酯(化合物72)。滴加完毕后，室温下继续搅拌。反应完毕后,取样监控，将反应物倒入盐酸-冰水浴中，以二氯甲烷萃取，干燥后得到2-(9H-咔唑-3-基)-2-氧代乙酸甲酯(化合物73)。
Figure PCTCN2019077919-appb-000123
取18g化合物(73)加入150mL无水乙醇,室温下搅拌。加入2.6g硼氢化钠，并将反应混合物在室温搅拌50分钟。反应完毕后,取样监 控，将反应物倒入盐酸-冰水浴中。使用乙酸乙酯萃取，干燥后得到2-(9H-咔唑-3-基)-2-氧代乙酸甲酯(化合物74)。
Figure PCTCN2019077919-appb-000124
取2.5g化合物(74)溶于20ml二氯甲烷,加入1.5ml的三乙胺搅拌。滴加1.6g的4-异氰酸根-N，N-二甲基苯胺(75)的二氯甲烷溶液(10％)。滴加完毕在二氯甲烷中回流,监控反应。反应完成后,用HCl中和。水洗,抽去溶剂后,经层析分离,得到化合物(71)。C 23H 19N 3O 3,m/z:385.1[M] +。
Figure PCTCN2019077919-appb-000125
实施例38
5-((9H-咔唑-3-基)氯甲基)-3-(4-(二甲基氨基)苯基)恶唑烷-2,4-二酮(化合物76)和5-((9H-咔唑-3-基)亚甲基)-3-(4-(二甲基氨基)苯基)恶唑烷-2,4-二酮(化合物88)的制备
Figure PCTCN2019077919-appb-000126
Figure PCTCN2019077919-appb-000127
如实施例3方法,由9H-咔唑代替化合物(5),得到9H-咔唑-3-甲醛(化合物77),熔点158℃。
Figure PCTCN2019077919-appb-000128
在4℃下，5g的9H-咔唑-3-甲醛(化合物77)和2.5ml的2,2-二氯乙酸甲酯的无水乙醚(30ml)溶液，在氩气下分批加入1.95g甲醇钠，保持低温下搅拌1小时，然后加热回流。取样监控,反应完成后，加水并分离有机层。经干燥、浓缩及层析分离，得到3-(9H-咔唑-3-基)-3-氯-2-氧代丙酸甲酯(79)。
如实施例37方法,以化合物(79)代替化合物(73),得到3-(9H-咔唑-3-基)-3-氯-2-羟基丙酸甲酯(80)。
Figure PCTCN2019077919-appb-000129
如实施例37方法,以化合物(80)代替化合物(74),得到3-(9H-咔唑-3-基)-3-氯-2-羟基丙酸甲酯(76)。C 24H 20ClN 3O 3,m/z:433.1[M] +。
Figure PCTCN2019077919-appb-000130
4.3g化合物(76)溶于吡啶中，加热至80℃。加入加1.5ml的DBU(1，8－二氮杂二环十一碳－7－烯)，进行反应。反应完成后(取样监控)，减压蒸馏。经层析分离,得到化合物(88)。C 24H 19N 3O 3,m/z:397.1[M] +。
Figure PCTCN2019077919-appb-000131
实施例39
2-(1-(9H-咔唑-3-基)乙基)-5-(4-(二甲基氨基)亚苄基)-1,3-二恶烷-4,6-二酮(化合物81)的制备
Figure PCTCN2019077919-appb-000132
在冰水浴下，取34g的9H-咔唑溶于二氯甲烷中，然后缓慢加入30克无水AlCl 3并继续搅拌10分钟，此后缓慢滴加20ml乙酰氯。待滴加完毕后，在室温下继续搅拌。反应完毕后，将反应液缓慢倒入盐酸-冰水浴中，二氯甲烷萃取，经浓缩、层析分离,得到主产物3-乙酰基咔唑(82),熔点167℃。
Figure PCTCN2019077919-appb-000133
水浴中加热5.2g丙二酸、15.3g醋酸酐、和0.2ml浓硫酸。冷却至室温，滴加8.4g的3-乙酰基咔唑(82)，反应1小时，然后在冰箱中放置过夜。水洗后用乙酸乙酯萃取，经层析分离，得到2-(1-(9H-咔唑-3-基)乙基)-1,3-二恶烷-4,6-二酮(83)。
Figure PCTCN2019077919-appb-000134
如实施例35方法,但以化合物(83)代替化合物(65),得到化合物(81)。C 27H 24N 2O 4,m/z:440.2[M] +。
Figure PCTCN2019077919-appb-000135
实施例40
5-(((4-(二甲基氨基)苯基)亚氨基)甲基)喹啉-7-基3-(3-(2H-苯并[d][1,2,3]三唑-2-基)叔丁基)-4-羟基苯基)丙酸酯(化合物84)的制备
Figure PCTCN2019077919-appb-000136
3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)丙酸甲酯(Eutec co.,BZTME,化合物85),在KOH/MeOH水解后,加酸中和。以二氯甲烷萃取,得到3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)丙二酸(86)。充分干燥后,加入过量二氯亚砜,加热回流进行反应,反应完成后(取样确认)抽去未反应的二氯亚砜,得到化合物3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)丙酰氯,备用。
Figure PCTCN2019077919-appb-000137
称取1.75g的8-羟基喹啉-5-甲醛(NSC 122131,化合物87),溶于20ml二氯甲烷中，并加入2g三乙胺搅拌。滴加3.6g前述的3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)丙酰氯化合物(86)的二氯甲烷溶液(20ml)。室温下搅拌过夜。产物倒入冰水中,用二氯甲烷萃取，再用1％稀盐酸和盐水洗涤。干燥后得到化合物5-甲酰基喹啉-8-基3-(3-(2H-苯并[d][1,2,3]三唑-2-基)-5-(叔丁基)-4-羟基苯基)丙酸酯(91)。
称取5g化合物(91)和1.4g对-(二甲基氨基)苯胺,溶于40ml无水乙醇，除水加热回流4小时。取样监控，反应结束后，除去溶剂，得到化合物(84)。C 37H 36N 6O 3,m/z:612.3[M] +。
Figure PCTCN2019077919-appb-000138
实施例41
用于光学记录媒体的性能改良：化合物(B),经共价键结后,得到化合物(18),如下图所示。
Figure PCTCN2019077919-appb-000139
化合物(B)的熔点为175℃,经过与苯并三唑类化合物共价键结后,熔点提升到224℃(化合物18)。这对用于光学记录媒体的有机染料(B)而言,是重要的改良。因为化合物(18)在激光照射光盘,局部所产生高温(250℃或以上)下,较不易分解。
附图3说明化合物(18)对紫外光的吸收范围,涵盖了UVA、UVB和蓝光。这说明化合物(18)染料可对光盘提供较广的紫外光(UVA+UVB)保护。因此,在光盘保存上,相对于化合物(B),化合物(18)是较有利的。
表3 化合物(B)和本发明化合物(18)的性质比较
  化合物(B) 本发明实例10化合物(18)
热性质 熔点175℃ 熔点224℃
光吸收范围 UVA+可见光 UVA+UVB+可见光
实施例42
用于紫外光或蓝光吸收剂的优点：本发明化合物用于紫外光及/或蓝光吸收剂时,兼具紫外光(UVA+UVB)及蓝光吸收功能。与市售抗蓝光剂Eusorb UV-1990(Eutec co.)比较(表4),显示市售品Eusorb UV-1990对于UVB(波长280nm)吸收非常弱。本发明的实例化合物,对紫外光的涵盖范围以及吸收度,均优于目前市售抗蓝光剂Eusorb UV-1990。
表4.本发明实例的标题化合物和市售Eusorb UV-1990防蓝光剂比较
Figure PCTCN2019077919-appb-000140
实施例43
用于转光剂的稳定性与耐候性：使用热重分析仪(TGA),测量实例化合物的热稳定性。重量损失愈大代表稳定性愈差。附图2结果显示TGA结果:升温到220℃,实例4化合物(7)重量损失小于1％。升温高 达312℃,重量损失仅约5％。这说明,化合物(7)具有非常高度的热稳定性。
附图4是本发明实例4化合物(7)所制成的PE农膜,在日光灯下照片(为显示呈色,农膜置于灰色不透明背景)。农膜为透明且呈现橘红色。
表5显示农膜化合物改良前后之耐候性比较。RL1000商品(BASF)在户外农膜使用上,仅能维持两季的稳定性,本发明化合物(7)则超过3个季节。
Figure PCTCN2019077919-appb-000141
表5.农膜化合物改良前后之耐候性比较
  RL1000 本发明化合物(7)
耐候性 2个季 3个季
可见光发射范围 橘红色(约600-700nm) 橘红色(约600-700nm)
以上已以较佳实施例公布了本发明，然其并非用以限制本发明，凡采取等同替换或等效变换的方案所获得的技术方案，均落在本发明的保护范围内。

Claims (12)

  1. 一种新型多环化合物，其特征在于：具有式(1)或式(2)所示的结构式
    A-R 1-B-R 2-C-R 3-D
    (1)
    A-R 1-B-R 2-D-R 3-C
    (2)；
    包括至少一个可见光或荧光发射基团，及至少一个另外的紫外光吸收基团，其中，可见光或荧光发射基团是：R 2-C-R 3-D或R 2-D-R 3-C；紫外光吸收基团是:A-R 1-B；R 1～R 3是一键或/且任意的二价联结基团；A、B、C、是未经取代或经R 4取代之苯环、苯并碳环、含氮的5-7员杂环、或苯并含氮的5-7员杂环；D是由碳、氮、氧、硫原子所构成的未经取代或经取代的5-7员杂环或苯并5-7员杂环；其中,环碳原子的取代基选自1个或多个氢、羟基、氧基、硫基、硫醇基、胺基、亚胺基、C 1～C 8直链或支链烷基或烯基、R 4；环氮原子的取代基选自1个或多个氢、羟基、氧基、直链或支链C 1～C 8烷基；R 4是一个或多个取代基，并且若为多个取代基时，各自独立地选自氢、卤素、羟基、氨基、硝基、氰基、直链或支链C 1～C 18的烷基、烯基或烷氧基、未取代或经取代的苯基、SR 5、SO 2R 5、SO 3R 5、COOR 5、COR 5、OCOR 5、C(O)NR 6R 7、SO 2NR 6R 7、NR 6R 7,其中R 5、R 6、R 7各自独立地选自氢、直链或支链C 1～C 8的烷基,且R 4与相邻 的R 4之间，或R 4与相邻的环之间，一起表示成3-6原子的稠合碳环或稠合杂环。
  2. 根据权利要求1所述的化合物，其特征在于，D选自：
    Figure PCTCN2019077919-appb-100001
    其中，n＝0～1；X 1～X 6各自独立地选自C＝O、C＝S、C＝N-R 8、N、NR 9、C、O、S、CR 10、CR 11R 12、CNR 11R 12、CR 10NR 11R 12，其中,R 8～R 12各自独立地选自氢、直链或支链C 1～C 8的烷基或烯基、未经取代或经一个或多个直链或支链C 1～C 6烷基或卤素所取代的苯基；R 4为取代基,并且各自独立地选自氢、卤素、硝基、氰基、直链或支链C 1～C 8烷基、烯基或烷氧基、SR 5、SO 2R 5、COOR 5、COR 5、C(O)NR 6R 7、NR 6R 7,其中,R 5、R 6、R 7各自独立地为氢、直链或支链C 1～C 8的烷基；p＝0～3。
  3. 根据权利要求2所述的化合物，其特征在于，D选自：
    Figure PCTCN2019077919-appb-100002
    其中,n＝0～1；X 1～X 6各自独立地选自C＝O、C＝S、C＝N-R 8、N、NR 9、C、O、S、CR 10、CR 11R 12,R 9～R 12各自独立地选自氢、直链 或支链C 1～C 6的烷基或烯基；R 4是取代基,并且各自独立地选自氢、卤素、硝基、氰基、直链或支链C 1～C 8的烷基、烯基或烷氧基、SR 5、SO 2R 5、COOR 5、COR 5、C(O)NR 6R 7、NR 6R 7,其中,R 5、R 6、R 7各自独立地为氢、直链或支链C 1～C 6的烷基；p＝0～2。
  4. 根据权利要求2或3所述的化合物，其特征在于：R 1～R 3是一键、或由1-10个选自下列基团所组成的一条链：-O-、-S-、-C(＝O)-、-COO-、-C(＝S)-、-C(＝N-R 13)-、-N(R 13)-、-C(R 14)(R 15)-、-C(R 16)＝、-C≡、-C(R 17)＝C(R 18)-、-Ph-，其中,R 13～R 18各自独立地选自氢、卤素、羟基、未取代或经卤素取代的直链或支链的C 1～C 6烷基或烯基、未取代或经1或2个卤素或直链或支链的C 1～C 6烷基取代苯基；Ph是未经取代或经1或多个卤素、羟基、C 1～C 6烷氧基、或直链或支链C 1～C 6烷基取代的苯基。
  5. 根据权利要求4所述的化合物，其特征在于：
    A选自：
    Figure PCTCN2019077919-appb-100003
    Figure PCTCN2019077919-appb-100004
    Figure PCTCN2019077919-appb-100005
    B选自：
    Figure PCTCN2019077919-appb-100006
    C选自：
    Figure PCTCN2019077919-appb-100007
    Figure PCTCN2019077919-appb-100008
    其中，R 19～R 20各自独立地选自氢、直链或支链C 1～C 6的烷基、未取代或经一或多个卤素或直链或支链C 1～C 6的烷基所取代的苯基；Ph是未取代或经一或多个卤素、羟基、C 1～C 6烷氧基、或直链或支链C 1～C 6烷基取代的苯基。
  6. 根据权利要求5所述的化合物，其特征在于：
    A选自：
    Figure PCTCN2019077919-appb-100009
    Figure PCTCN2019077919-appb-100010
    B选自：
    Figure PCTCN2019077919-appb-100011
    C选自：
    Figure PCTCN2019077919-appb-100012
    D选自：
    Figure PCTCN2019077919-appb-100013
    Figure PCTCN2019077919-appb-100014
    其中，当n＝0时，X 1选自C＝O、C＝S,X 2、X 3、X 4各自独立地选自C＝O、C＝S、C＝N-R 8、N、NR 9、C、O、S、CR 10、CR 11R 12、CNR 11R 12；
    当n＝1时，X 4、X 6各自独立地选自选自C＝O、C＝S,X 1、X 2、X 3各自独立地选自C＝O、C＝S、C＝N-R 8、N、NR 9、C、O、S、CR 10、CR 11R 12；R 1～R 3是一键,或/且由1-6个选自下列基团所组成的一条链:-O-、-C(＝O)-、-COO-、-N(R 13)-、-C(R 14)(R 15)-、-C(R 16)＝、-C(R 17)＝C(R 18)-；
    R 4是取代基,并且各自独立地选自氢、卤素、硝基、氰基、直链或支链C 1～C 8的烷基、烯基或烷氧基、COOR 5、COR 5、NR 6R 7；
    p＝0～2；
    R 5～R 7各自独立地选自氢、直链或支链C 1～C 6的烷基；
    R 8～R 12各自独立地选自氢、直链或支链C 1～C 6烷基、未取代或经1或2个卤素或C 1～C 6烷基取代的苯基；
    R 13～R 18是各自独立地选自氢、卤素、直链或支链C 1～C 6烷基、未取代或经1或2个卤素或C 1～C 6烷基取代的苯基；
    R 19选自氢、直链或支链C 1～C 6烷基、未取代或经1或2个卤素或C 1～C 6烷基取代的苯基；
    Ph是未取代或经1或2个卤素、羟基、C 1～C 6烷氧基、或直链或支链C 1～C 6烷基取代的苯基。
  7. 根据权利要求6所述的化合物，其特征在于：R 2是一键或-(CHR 21) q N(R 22)-,R 21、R 22各自独立地选自氢、直链或支链C 1～C 6的烷基,q＝0～6；
    D选自以下环：
    Figure PCTCN2019077919-appb-100015
    Figure PCTCN2019077919-appb-100016
    R 4是取代基，并且各自独立地选自氢、卤素、直链或支链C 1～C 8的烷基或烷氧基、COOR 5、COR 5、NR 6R 7，其中,R 5、R 6、R 7各自独立地选自氢、直链或支链C 1～C 6的烷基；p＝0～2；R 9、R 23～R 34选自氢、直链或支链C 1～C 6的烷基、未取代或经1或2个直链或支链C 1～C 6烷基取代的苯基。
  8. 根据权利要求1或5所述的化合物，其特征在于，A-R 1-B选自以下基团：
    Figure PCTCN2019077919-appb-100017
    R 4各自独立地选自氢、卤素、直链或支链C 1～C 8的烷基、烯基或烷氧基、SR 5、SO 2R 5、COOR 5、COR 5、C(O)NR 6R 7、NR 6R 7，其中，R 5、R 6、R 7各自独立地选自氢、直链或支链C 1～C 6的烷基；p＝0～2； R 19、R 35～R 39各自独立地选自氢、直链或支链C 1～C 6的烷基、未取代或经1或2个卤素或C 1～C 6烷基取代的苯基；Ph是未取代或经1或2个卤素、OH基、C 1～C 6烷氧基、或直链或支链C 1～C 6烷基取代的苯基。
  9. 根据权利要求1所述的化合物,其特征在于：
    R 2-C-R 3-D选自：
    Figure PCTCN2019077919-appb-100018
    R 2-D-R 3-C选自：
    Figure PCTCN2019077919-appb-100019
    D选自：
    Figure PCTCN2019077919-appb-100020
    Figure PCTCN2019077919-appb-100021
    Figure PCTCN2019077919-appb-100022
    A-R 1-B选自：
    苯并三唑:
    Figure PCTCN2019077919-appb-100023
    三嗪:
    Figure PCTCN2019077919-appb-100024
    咔唑:
    Figure PCTCN2019077919-appb-100025
    草酰苯胺:
    Figure PCTCN2019077919-appb-100026
    苯并恶嗪酮:
    Figure PCTCN2019077919-appb-100027
    喹唑啉酮:
    Figure PCTCN2019077919-appb-100028
    二苯甲酰甲烷：
    Figure PCTCN2019077919-appb-100029
    苯基甲脒乙酯：
    Figure PCTCN2019077919-appb-100030
    甲亚胺：
    Figure PCTCN2019077919-appb-100031
    喹唑啉:
    Figure PCTCN2019077919-appb-100032
    苯甲酸:
    Figure PCTCN2019077919-appb-100033
    二苯甲酮:
    Figure PCTCN2019077919-appb-100034
    二苯并噻吩:
    Figure PCTCN2019077919-appb-100035
    二苯并呋喃:
    Figure PCTCN2019077919-appb-100036
    二苯硫醚:
    Figure PCTCN2019077919-appb-100037
    二苯醚:
    Figure PCTCN2019077919-appb-100038
    以上可见光发射基团或紫外光吸收基团，均被(R 4)p取代基所取代，其中，p＝0～3，R 4是取代基,并且各自独立地选自氢、卤素、羟基、氨基、硝基、氰基、直链或支链C 1～C 18的烷基、烯基或烷氧基、未取代或经一或多个直链或支链C 1～C 6烷基或卤素所取代苯基、SR 5、SO 2R 5、SO 3R 5、COOR 5、COR 5、OCOR 5、C(O)NR 6R 7、SO 2NR 6R 7、NR 6R 7，其中，R 5、R 6、R 7各自独立地选自氢、直链或支链C 1～C 8的烷基，且R 4与相邻的R 4之间，或R 4与相邻的环之间，可一起表示3-6原子的稠合碳环或稠合杂环；R 40～R 49是相同或相异各自独立选自氢、直链或支链C 1～C 8的烷基或烯基、未取代或经直链或支链C 1～C 6烷基或卤素所取代苯基；R 50选自氢、一价金属、直链或支链C 1～C 8的烷基或烯基、未取代或经一或多个直链或支链C 1～C 6烷基或卤素所取代苯基。
  10. 根据权利要求1～9项中任一项所述的化合物，其特征在于为以下结构式：
    Figure PCTCN2019077919-appb-100039
    Figure PCTCN2019077919-appb-100040
    Figure PCTCN2019077919-appb-100041
    Figure PCTCN2019077919-appb-100042
  11. 一种制备权利要求1中所述式(1)或式(2)化合物的方法，特征在于，包括以下的反应步骤之一：
    Figure PCTCN2019077919-appb-100043
    Figure PCTCN2019077919-appb-100044
    Figure PCTCN2019077919-appb-100045
    Figure PCTCN2019077919-appb-100046
    Figure PCTCN2019077919-appb-100047
    其中，A～D环，R 1～R 3同权利要求1中所定义；
    D’是D环之前驱物,选自
    Figure PCTCN2019077919-appb-100048
    D”是D环之前驱物,结构式为
    Figure PCTCN2019077919-appb-100049
    Z是离去基,包括卤素、或C 1～C 6烷氧基；
    T为相同或相异,各自独立选自NH、NH 2、OH、SH；
    U、V选自C＝O、C＝S、C＝N-R 51、C(R 52)(R 53)；
    R 50～R 53是相同或相异各自独立选自一键、氢、直链或支链C 1～C 6的烷基。
  12. 一种膜，其用于转光剂、染料、颜料、荧光剂、紫外光或/且蓝光吸收剂,特征在于：包括权利要求1～10任一项的式(1)或式(2)化合物。
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