CN108117488B - Benzoyl methyl cinnamate compound and preparation method and application thereof - Google Patents

Benzoyl methyl cinnamate compound and preparation method and application thereof Download PDF

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CN108117488B
CN108117488B CN201611062280.4A CN201611062280A CN108117488B CN 108117488 B CN108117488 B CN 108117488B CN 201611062280 A CN201611062280 A CN 201611062280A CN 108117488 B CN108117488 B CN 108117488B
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邹应全
庞玉莲
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HUBEI GURUN TECHNOLOGY Co Ltd
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Abstract

A benzoyl methyl cinnamate compound and a preparation method and application thereof. The invention relates to benzoylmethyl cinnamates of formula (I), wherein R is 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13And R 14The invention also relates to a method for preparing the benzoylmethyl cinnamate compounds, which comprises the step of carrying out esterification reaction on the compounds shown in the formula (II) and the compounds shown in the formula (III). The compounds can be used as photoinitiators, can absorb radiant heat within the range of 200-350nm, have good stability and yellowing resistance, and more importantly, compared with the existing α -monohydroxy ketone photoinitiators, the problems of peculiar smell and strong migration are greatly improved.
Figure DDA0001163527820000011

Description

Benzoyl methyl cinnamate compound and preparation method and application thereof
Technical Field
The invention relates to a benzoyl methyl cinnamate compound which can be used as a photoinitiator, and also relates to preparation and application of the benzoyl methyl cinnamate compound.
Background
The photoinitiator is also called photosensitizer or light curing agent, and is a compound which can absorb energy with certain wavelength in an ultraviolet region (250-400nm) or a visible light region (400-600nm) to generate free radicals, cations and the like so as to initiate the polymerization, crosslinking and curing of the monomers. In the photocuring system, the photoinitiator generally accounts for 3-5%, and the content of the photoinitiator is low but is a key component, and plays a role in determining the photocuring speed. It is related to the rapid crosslinking and curing of the oligomer and diluent upon exposure of the formulation to light, thereby changing from a liquid to a solid. At present, the photocuring technology is widely applied to the traditional fields of coatings, printing ink, microelectronics, printing and the like, and is also applied to the novel fields of laser video recording, three-dimensional elements and the like. As an important component of the photocuring system, photoinitiators must meet the needs of different photocuring conditions and applications. In the field of free radical photoinitiators, the main goals are: the method has the advantages of improving the light sensitivity, improving the surface curing efficiency (oxygen inhibition resistance), improving the deep curing performance, improving the solubility of the photoinitiator in monomers and resin, reducing the toxicity and the smell, reducing the mobility of the uncured initiator after curing and reducing the yellowing property.
α -monohydroxyketone photoinitiator is a common photoinitiator, wherein the most common photoinitiators are 1173 (2-hydroxy-2-methyl-1-phenyl acetone) and 184 (1-hydroxycyclohexyl phenyl ketone). The photoinitiator 1173 is liquid, is convenient to use, is a main initiator in various light-cured varnishes, has excellent thermal stability, good yellowing resistance and lower price, and has the defects that benzaldehyde in a photolysis product has bad smell, relatively high volatility and strong mobility, and the photoinitiator 184 is white powder and has relatively low volatility, but the photolysis product has the problems of peculiar smell and strong mobility.
Eastman-Kodak corporation produced the earliest negative photoresist, polyvinyl alcohol cinnamate based, from synthetic polymers worldwide in 1954 (US 2690966). This is the first photoresist used in electronics industry by human beings, and the principle of photopolymerization is shown in the following formula:
Figure BDA0001163527800000021
double bonds in the cinnamoyl group are opened under the action of ultraviolet light, and the double bonds on different molecules interact to form a four-membered ring to generate photodimerization crosslinking. Thus, the molecules in the exposed region are crosslinked to form a poorly soluble network structure, and the molecular properties in the unexposed region are not changed, resulting in a difference in solubility in a developer. It is this characteristic that microfabrication can be achieved.
Disclosure of Invention
The present inventors have conducted extensive and intensive studies in the field of photoinitiators in view of the above-mentioned state of the art, and have found that α -monohydroxyketone photoinitiators are improved in odor and migration properties, and have found that, if a cinnamoyl group is introduced or grafted to α -monohydroxyketone photoinitiator, the photoinitiator thus obtained improves the odor and migration properties of α -monohydroxyketone photoinitiators while retaining the advantages of α -monohydroxyketone photoinitiators, by utilizing the property of the cinnamoyl group to be polymerizable and cross-linked under ultraviolet light.
The compound can be used as a photoinitiator, can absorb radiant heat within the range of 200-350nm, has good stability and yellowing resistance, and more importantly, compared with the existing α -monohydroxy ketone photoinitiator, the compound greatly improves the problems of peculiar smell and strong mobility.
Another purpose of the invention is to provide a method for preparing the benzoyl methyl cinnamate compound.
Compared with the conventional α -monohydroxyketone photoinitiator, the benzoyl methyl cinnamate compound is used as the photoinitiator, so that the problems of peculiar smell and strong mobility are greatly improved.
The technical solution for achieving the above object of the present invention can be summarized as follows:
1. the benzoyl methyl cinnamate compound has a structure shown in a formula (I):
Figure BDA0001163527800000031
wherein
R 1、R 2、R 3、R 4And R 5Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18Aryl, wherein the aforementioned C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 6Alkyl radical, C 1-C 6Alkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenyl and C 2-C 6An alkynyl group;
R 6and R 7Same or different and selected from H, C 1-C 6Alkyl and halo C 1-C 6Alkyl, or R 6And R 7Together with the carbon atom to which they are attached form C 3-C 8A cycloalkyl group;
R 8、R 9、R 10、R 11and R 12Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18Aryl, wherein the aforementioned C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 6Alkyl radical, C 1-C 6Alkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenyl and C 2-C 6An alkynyl group; and
R 13and R 14Same or different and selected from H, C 1-C 6Alkyl and halo C 1-C 6An alkyl group.
2. A compound according to item 1, wherein R 6And R 7Same or different and selected from H, C 1-C 4Alkyl and halo C 1-C 4Alkyl, or R 6And R 7Together with the carbon atom to which they are attached form C 5-C 6A cycloalkyl group.
3. A compound according to item 2, wherein R 6And R 7Identical and is methyl or halomethyl, or R 6And R 7Together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl group.
4. A compound according to any one of items 1 to 3, wherein R 13And R 14Same or different and selected from H, C 1-C 4Alkyl and halo C 1-C 4Alkyl, preferably R 13And R 14Are all H.
5. The compound according to any one of items 1 to 4, wherein
R 1、R 2、R 3、R 4And R 5Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 2-C 6Alkenyloxy radical, C 2-C 6Alkynyloxy, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenylthio radical, C 2-C 6Alkynylthio, C 3-C 8Cycloalkylthio radical, C 4-C 8Cycloalkylalkylthio and C 6-C 10Aryl, wherein the aforementioned C 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 2-C 6Alkenyloxy radical, C 2-C 6Alkynyloxy, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6An alkenylthio group,C 2-C 6Alkynylthio, C 3-C 8Cycloalkylthio radical, C 4-C 8Cycloalkylalkylthio and C 6-C 10The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 4Alkyl radical, C 1-C 4Alkoxy radical, C 1-C 4Alkylthio radical, C 2-C 4Alkenyl and C 2-C 4An alkynyl group; and/or
R 8、R 9、R 10、R 11And R 12Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 2-C 6Alkenyloxy radical, C 2-C 6Alkynyloxy, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenylthio radical, C 2-C 6Alkynylthio, C 3-C 8Cycloalkylthio radical, C 4-C 8Cycloalkylalkylthio and C 6-C 10Aryl, wherein the aforementioned C 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 2-C 6Alkenyloxy radical, C 2-C 6Alkynyloxy, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenylthio radical, C 2-C 6Alkynylthio, C 3-C 8Cycloalkylthio radical, C 4-C 8Cycloalkylalkylthio and C 6-C 10The aryl radical may optionally be substituted by one orA plurality of groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 4Alkyl radical, C 1-C 4Alkoxy radical, C 1-C 4Alkylthio radical, C 2-C 4Alkenyl and C 2-C 4Alkynyl.
6. The compound according to any one of items 1 to 4, wherein
R 1、R 2、R 3、R 4And R 5Independently of one another, from hydrogen, halogen, C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4Alkylthio group wherein the foregoing C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4The alkylthio group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4An alkylthio group; and/or
R 8、R 9、R 10、R 11And R 12Independently of one another, from hydrogen, halogen, C 1-C 4Alkyl radical, C 2-C 4Alkenyl radical, C 2-C 4Alkynyl, C 1-C 4Alkoxy and C 1-C 4Alkylthio group wherein the foregoing C 1-C 4Alkyl radical, C 2-C 4Alkenyl radical, C 2-C 4Alkynyl, C 1-C 4Alkoxy and C 1-C 4The alkylthio group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4An alkylthio group.
7. The compound according to item 1, wherein the compound is selected from the group consisting of:
Figure BDA0001163527800000051
Figure BDA0001163527800000061
8. a process for the preparation of a compound of formula (I) according to any one of claims 1 to 7, comprising subjecting a compound of formula (II) to an esterification reaction with a compound of formula (III) to give a compound of formula (I),
Figure BDA0001163527800000062
wherein R is 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13And R 14As defined in any one of items 1 to 7, and X is hydroxy or halogen.
9. The process according to item 8, wherein the esterification reaction is carried out in the presence of a catalyst, preferably the catalyst is 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, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines, for example trialkylamines, such as trimethylamine and triethylamine.
10. Use of a compound according to any one of items 1 to 7 as a photoinitiator.
These and other objects, features and advantages of the present invention will become readily apparent to those skilled in the art upon consideration of the following specification in conjunction with the invention.
Brief Description of Drawings
FIG. 1 is a graph of the ultraviolet absorption spectra of compounds 1173 and 1173 CC;
FIG. 2 is a graph of the UV absorption spectra of compounds 184 and 184-CC;
FIG. 3 is a graph of the thermal decomposition rate of a compound as a function of time;
FIG. 4 is a graph of double bond conversion with time for polymerizable monomers obtained with compound 184-CC as a photoinitiator; and
FIG. 5 is a graph showing the change with time of the double bond conversion rate of a polymerizable monomer obtained by using 1173-CC as a photoinitiator.
Detailed Description
According to a first aspect of the present invention, there is provided a benzoylmethyl cinnamate compound of the formula (I):
Figure BDA0001163527800000071
wherein
R 1、R 2、R 3、R 4And R 5Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18Aryl, wherein the aforementioned C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18The aryl group may optionally be substituted with one or more substituents independently selected from the group consisting ofThe group (b) is substituted: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 6Alkyl radical, C 1-C 6Alkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenyl and C 2-C 6An alkynyl group;
R 6and R 7Same or different and selected from H, C 1-C 6Alkyl and halo C 1-C 6Alkyl, or R 6And R 7Together with the carbon atom to which they are attached form C 3-C 8A cycloalkyl group;
R 8、R 9、R 10、R 11and R 12Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18Aryl, wherein the aforementioned C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 6Alkyl radical, C 1-C 6Alkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenyl and C 2-C 6An alkynyl group; and
R 13and R 14Same or different and selected from H, C 1-C 6Alkyl and halo C 1-C 6An alkyl group.
The compound of the formula (I) retains the characteristics of α -monohydroxy ketone photoinitiator due to the existence of α -monohydroxy ketone structural part, and the cinnamoyl structural part contained in the compound enables the compound to be polymerized and crosslinked under ultraviolet radiation, so that the obtained compound of the formula (I) retains the advantages of α -monohydroxy ketone photoinitiator and improves the problems of peculiar smell and strong mobility of α -monohydroxy ketone photoinitiator.
In the present invention, the prefix "C n-C m"in each case denotes that the number of carbon atoms contained in the radical is n to m.
"halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen comprises F, Cl or a combination thereof.
The term "C" as used herein n-C mAlkyl "means a branched or unbranched saturated hydrocarbon radical having n-m, for example from 1 to 20, preferably from 1 to 12, more preferably from 1 to 8, particularly preferably from 1 to 6, particularly preferably from 1 to 4, carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and isomers thereof. C 1-C 8The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, and isomers thereof. C 1-C 6The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl and isomers thereof. C 1-C 4The alkyl group may be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, and isomers thereof.
The term "C" as used herein 2-C mAlkenyl "means a branched or unbranched unsaturated hydrocarbon group having 2-m, e.g. 2-20, preferably 2-6, more preferably 2-4 carbon atoms and having one or more double bonds located anywhere, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 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-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 3-hexenyl, 2-hexenyl, and the like, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-2-butenyl, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2-dimethyl-3-butenyl, 2, 3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 3-dimethyl-1-butenyl, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 2, 3-dimethyl-2-butenyl, 2, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, and isomers thereof. C 2-C 6The alkenyl group may be vinyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, neopentynyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, isohexenyl, neohexenyl and isomers thereof. C 2-C 4The alkenyl group may be 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, and isomers thereof.
The term "C" as used herein 2-C mAlkynyl "means a branched or unbranched unsaturated hydrocarbon group having 2-m, e.g. 2-20, preferably 2-6, more preferably 2-4 carbon atoms and having one or more triple bonds in any position, such as ethynyl, propynyl, 1-butynyl, 2-butynyl and isomers thereof. C 2-C 6Alkynyl may be ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and isomers thereof. C 2-C 4Alkynyl may be ethynyl, propynyl, 1-butynyl, 2-butynyl and isomers thereof.
The term "C" as used herein 3-C mCycloalkyl "means a saturated alicyclic monocyclic radical having 3-m, e.g. 3-20, preferably 3-8, more preferably 5-6, ring carbon atoms, e.g. cyclopropylCyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
The term "C 4-C mCycloalkylalkyl "denotes cycloalkyl substituted by alkyl and containing a total of 4 to m carbon atoms, e.g. 4 to 20, preferably 4 to 8 carbon atoms, wherein alkyl and cycloalkyl are as defined herein.
“C n-C mAlkoxy "and" C n-C mAlkylthio "means at C n-C mC having an oxygen or sulfur atom as a linking group bonded to any valence of the alkyl group n-C mAlkyl radicals, e.g. C 1-C 20Alkoxy (or thio) radicals, preferably C 1-C 12Alkoxy (or thio) radicals, more preferably C 1-C 8Alkoxy (or thio) radicals, particularly preferably C 1-C 6Alkoxy (or thio) radicals, particularly preferably C 1-C 4Alkoxy (or thio) group. C 1-C 8The alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, isooctoxy and isomers thereof. C 1-C 4The alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and isomers thereof. C 1-C 8The alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butyl, 2-butylthio, tert-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, isooctylthio and isomers thereof. C 1-C 4The alkylthio group can be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio and isomers thereof.
“C 2-C mAlkenyloxy "and" C 2-C mAlkenylthio "is defined at C 2-C mC having an oxygen atom or a sulfur atom as a linking group bonded to any saturated valence in the alkenyl group 2-C mAlkenyl radicals, e.g. C 2-C 20Alkenyloxy (or thio) radicals, preferably C 2-C 12An alkenyloxy (or thio) group, furtherPreferably C 2-C 8Alkenyloxy (or thio) radicals, particularly preferably C 2-C 6Alkenyloxy (or thio) radicals, particularly preferably C 2-C 4An alkenyloxy (or thio) group. C 1-C 4The alkenyloxy group may be ethyleneoxy, propylenyloxy, isopropenyloxy, n-butylenyloxy, sec-butylenyloxy, iso-butylenyloxy, tert-butylenyloxy and isomers thereof. C 2-C 4The alkenylthio group may be vinylthio, propenylthio, isopropenylthio, n-butenylthio and isomers thereof.
“C 2-C mAlkynyloxy "and" C 2-C mAlkynylthio "means at C 2-C mC with an oxygen or sulfur atom as a linking group bonded to any saturated valence in the alkynyl group 2-C mAlkynyl, e.g. C 2-C 20Alkynyloxy (or thio) radicals, preferably C 2-C 12Alkynyloxy (or thio) group, more preferably C 2-C 8Alkynyloxy (or thio) radicals, particularly preferably C 2-C 6Alkynyloxy (or thio) radicals, particularly preferably C 2-C 4Alkynyloxy (or thio) group. C 1-C 4The alkynyloxy group may be ethynyloxy, propynyloxy, n-butynyloxy, sec-butynyloxy and isomers thereof. C 2-C 4The alkynylthio group may be an ethynylthio group, a propynylthio group, an n-butynylthio group, a sec-butynylthio group and isomers thereof.
“C 3-C mCycloalkoxy "and" C 3-C mCycloalkylsulfanyl "means C having an oxygen atom or a sulfur atom as a linking group bonded at any valence bond in the cycloalkyl group 3-C mCycloalkyl radicals, e.g. C 3-C 20A cycloalkoxy (or thio) group, preferably C 3-C 8A cycloalkoxy (or thio) group, more preferably C 5-C 6A cycloalkoxy (or thio) group. C 3-C 20The cycloalkoxy group may be cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy and isomers thereof. C 3-C 20The cycloalkylthio group may be cyclopropylthio, cyclobutylthio, cyclopentylthioCyclohexylthio, cycloheptylthio, cyclooctylthio, cyclodecylthio and isomers thereof.
The term "C" as used herein 6-C mAryl "means a monocyclic, bicyclic or tricyclic aromatic hydrocarbon radical containing from 6 to m carbon atoms, for example from 6 to 18, preferably from 6 to 10 carbon atoms. As C 6-C mAs examples of the aryl group, there may be mentioned phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, methylpropylphenyl, naphthyl and the like; phenyl or naphthyl is preferred, especially phenyl (also referred to as C as substituent) 6H 5)。
In the present invention, R 1、R 2、R 3、R 4And R 5Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18Aryl, wherein the aforementioned C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 6Alkyl radical, C 1-C 6Alkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenyl and C 2-C 6Alkynyl. Preferably, R is 1、R 2、R 3、R 4And R 5Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 2-C 6Alkenyloxy radical, C 2-C 6Alkynyloxy, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenylthio radical, C 2-C 6Alkynylthio, C 3-C 8Cycloalkylthio radical, C 4-C 8Cycloalkylalkylthio and C 6-C 10Aryl, wherein the aforementioned C 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 2-C 6Alkenyloxy radical, C 2-C 6Alkynyloxy, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenylthio radical, C 2-C 6Alkynylthio, C 3-C 8Cycloalkylthio radical, C 4-C 8Cycloalkylalkylthio and C 6-C 10The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfoAcid group, amino group, cyano group, C 1-C 4Alkyl radical, C 1-C 4Alkoxy radical, C 1-C 4Alkylthio radical, C 2-C 4Alkenyl and C 2-C 4Alkynyl. It is particularly preferred that R 1、R 2、R 3、R 4And R 5Independently of one another, from hydrogen, halogen, C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4Alkylthio group wherein the foregoing C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4The alkylthio group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4An alkylthio group.
In the present invention, R 6And R 7Same or different and selected from H, C 1-C 6Alkyl and halo C 1-C 6Alkyl, or R 6And R 7Together with the carbon atom to which they are attached form C 3-C 8A cycloalkyl group. Preferably, R is 6And R 7Same or different and selected from H, C 1-C 4Alkyl and halo C 1-C 4Alkyl, or R 6And R 7Together with the carbon atom to which they are attached form C 5-C 6A cycloalkyl group. It is particularly preferred that R 6And R 7Identical or different and is methyl or halomethyl, or R 6And R 7Together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl group.
In the present invention, R 8、R 9、R 10、R 11And R 12Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkene oxideBase, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18Aryl, wherein the aforementioned C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 2-C 20Alkenyloxy radical, C 2-C 20Alkynyloxy, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 2-C 20Alkenylthio radical, C 2-C 20Alkynylthio, C 3-C 20Cycloalkylthio radical, C 4-C 20Cycloalkylalkylthio and C 6-C 18The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 6Alkyl radical, C 1-C 6Alkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenyl and C 2-C 6Alkynyl. Preferably, R is 8、R 9、R 10、R 11And R 12Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 2-C 6Alkenyloxy radical, C 2-C 6Alkynyloxy, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenylthio radical, C 2-C 6Alkynylthio, C 3-C 8Cycloalkylthio radical, C 4-C 8Cycloalkylalkylthio and C 6-C 10Aryl, wherein the aforementioned C 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 2-C 6Alkenyloxy radical, C 2-C 6Alkynyloxy, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenylthio radical, C 2-C 6Alkynylthio, C 3-C 8Cycloalkylthio radical, C 4-C 8Cycloalkylalkylthio and C 6-C 10The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1-C 4Alkyl radical, C 1-C 4Alkoxy radical, C 1-C 4Alkylthio radical, C 2-C 4Alkenyl and C 2-C 4Alkynyl. It is particularly preferred that R 8、R 9、R 10、R 11And R 12Independently of one another, from hydrogen, halogen, C 1-C 4Alkyl radical, C 2-C 4Alkenyl radical, C 2-C 4Alkynyl, C 1-C 4Alkoxy and C 1-C 4Alkylthio group wherein the foregoing C 1-C 4Alkyl radical, C 2-C 4Alkenyl radical, C 2-C 4Alkynyl, C 1-C 4Alkoxy and C 1-C 4The alkylthio group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4An alkylthio group.
In the present invention, R 13And R 14Same or different and selected from H, C 1-C 6Alkyl and halo C 1-C 6An alkyl group. Preferably, R is 13And R 14Same or different and selected from H, C 1-C 4Alkyl and halo C 1-C 4An alkyl group. It is particularly preferred that R 13And R 14Are all H.
In a particularly preferred embodiment of the invention, the compound of formula (I) is selected from the group consisting of:
Figure BDA0001163527800000141
according to a second aspect of the present invention there is provided a process for the preparation of a compound of formula (I) according to the present invention which comprises subjecting a compound of formula (II) to esterification with a compound of formula (III) to give a compound of formula (I),
Figure BDA0001163527800000151
wherein R is 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13And R 14As defined for compounds of formula (I), and X is hydroxy or halogen.
In order to accelerate the esterification reaction, the above-mentioned esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction. As the catalyst, either an acidic catalyst or a basic catalyst may be used. As the catalyst, one or more selected from the following group may be used: sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines, for example trialkylamines, such as trimethylamine and triethylamine. The amount of catalyst used is conventional and can be determined by conventional knowledge in the art or by several routine preliminary experiments.
In order to increase the yield of the compound of formula (I), it is advantageous to remove the water of esterification during the esterification reaction. This can be done, for example, by distillative condensation.
The esterification reaction is usually carried out in a solvent, preferably an organic solvent. As the type of solvent, there is no particular limitation as long as the compounds of formula (II) and formula (III) can be dissolved and are chemically inert to the esterification reaction, i.e., do not participate in the esterification reaction. As examples of the solvent, tetrahydrofuran, benzene, toluene, N-dimethylformamide, dichloromethane, and acetone may be mentioned. The solvent may be used singly or as a mixture of two or more solvents.
The relative amounts of the compound of formula (II) and the compound of formula (III) are not particularly limited, and they are generally used in equimolar amounts.
The esterification reaction can be carried out over a very wide temperature range. Advantageously according to the invention, the esterification reaction is carried out at a temperature of from-10 ℃ to 150 ℃, preferably from 0 ℃ to 100 ℃, 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.
After the esterification reaction is complete, a reaction mixture comprising the compound of formula (I) is obtained. Therefore, the reaction mixture needs to be worked up to obtain a purified compound of formula (I). In general, the reaction mixture obtained by the esterification reaction is first filtered, and a filtrate portion is taken out. Then, the filtrate was washed to remove the catalyst and unreacted raw materials. The washing liquid is not particularly limited as long as the catalyst and unreacted raw materials can be removed. As examples of the washing liquid, dilute hydrochloric acid (aqueous solution), saturated aqueous sodium bicarbonate solution and water may be mentioned. The concentration of the dilute hydrochloric acid is not particularly limited, and a dilute hydrochloric acid having a concentration of 5 to 12% is generally used. Washing with the washing liquid can be carried out once or for multiple times; in the case of multiple runs, a single wash solution may be used, or different wash solutions may be used sequentially. Advantageously according to the invention, the filtrate obtained by filtration of the reaction mixture obtained in the esterification reaction is washed successively with dilute hydrochloric acid, saturated aqueous sodium bicarbonate solution and water. Of course, after each washing with a wash liquid, it is necessary to pour off the aqueous phase and then wash the organic phase with the next wash liquid. After washing, drying is required to remove residual water. For this purpose, drying may be usually carried out using anhydrous sodium sulfate. After drying, the residual organic solvent is removed again. The means for removing the organic solvent is not particularly limited, and the organic solvent can be removed by distillation under reduced pressure. After removal of the residual organic solvent, the crude 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, for example by recrystallization. The choice of the recrystallization solvent is conventional and is not particularly limited. According to the invention, the crude product of the compound of formula (I) is advantageously recrystallized from methanol.
The compound of the formula (I) contains α -monohydroxy ketone structural part and cinnamoyl structural part, so that the compound can play a role of α -monohydroxy ketone photoinitiator, and the problems of peculiar smell and strong mobility inherent in α -monohydroxy ketone photoinitiator are solved due to the introduction of the cinnamoyl structural part.
Thus, according to a third aspect of the present invention, there is provided the use of a compound of formula (I) according to the present invention as a photoinitiator.
The compound of formula (I) can absorb electromagnetic waves of 200-350 nm. After the electromagnetic wave is absorbed, the compound of the formula (I) is changed from a ground state to an excited state, so that the acyl carbon atom in the benzoyl structure part in the compound of the formula (I) is broken with the carbon atom in the adjacent methoxyl group to form two free radicals, thereby initiating photopolymerization or photocrosslinking. In addition, as the cinnamoyl structure part of the compound in the formula (I) contains unsaturated carbon-carbon double bonds, carbon-carbon double bonds among different molecules are easy to react to form larger molecules or cross-linking structures when being irradiated by electromagnetic waves, so that the problems of peculiar smell and strong mobility caused by a photoinitiator are greatly improved, the peculiar smell is remarkably reduced, and the mobility is remarkably reduced.
The compounds of formula (I) are useful as photoinitiators in coatings, inks, microelectronics, printing and the like. When the compounds of the formula (I) are used as photoinitiators, their amounts are customary or can be determined by routine preliminary experiments.
Examples
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention.
Example 1: 3-phenyl-2-propenoic acid benzoyl isopropyl ester
16.4g (0.1mol) of 2-hydroxy-2-methyl-1-phenyl-1-propanone were placed in a 250ml three-necked flask and 100ml of methylene chloride and 10.1g (0.1mol) of triethylamine were added. After stirring uniformly, 16.6g (0.1mol) of 3-phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, 13g in total of pale yellow crystals were obtained, which were purified by filtration of the product 1The title compound was identified by H-NMR spectrum and was designated 1173-CC.
1H-NMR (spectrum) (determined in Acetone-d 6) (delta ppm): 1.80(s,6H),6.56(d,1H),7.45(m,9H),8.11(d, 2H).
Example 2: 3- (4-methoxy) phenyl-2-propenoic acid benzoyl isopropyl ester
16.4g (0.1mol) of 2-hydroxy-2-methyl-1-phenyl-1-propanone were placed in a 250ml three-necked flask and 100ml of methylene chloride and 10.1g (0.1mol) of triethylamine were added. After stirring uniformly, 18g (0.1mol) of 3- (4-methoxy) phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, a total of 18g of pale yellow crystals were obtained, which were obtained by passing the product through a column of sodium sulfate, potassium sulfate, sodium sulfate 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.60(s,6H),3.80(s,3H),6.31(d,1H),7.48(m,9H),7.97(d, 2H).
Example 3: 3-phenyl-2-propenoic acid 4-methylphenyl formyl isopropyl ester
Figure BDA0001163527800000181
17.7g (0.1mol) of 2-hydroxy-2-methyl-1- (4-methyl) phenyl-1-propanone were placed in a 250ml three-necked flask, and 100ml of methylene chloride and 10.1g (0.1mol) of triethylamine were added. After stirring uniformly, 16.6g (0.1mol) of cinnamoyl chloride was added and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, 16g in total of pale yellow crystals were obtained, which were obtained by passing the product through a filter 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.78(s,6H),2.34(s,6H),6.54(d,1H),7.35(m,9H),8.11(d, 2H).
Example 4: 3-phenyl-2-propenoic acid 4-methylthiophenylformyl isopropyl ester
Figure BDA0001163527800000182
21g (0.1mol) of 2-hydroxy-2-methyl-1- (4-methylthiophenyl) -1-propanone were placed in a 250ml three-necked flask, and 100ml of methylene chloride and 10.1g (0.1mol) of triethylamine were added. After stirring uniformly, 16.6g (0.1mol) of cinnamoyl chloride was added and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, 18g in total of yellow crystals were obtained, which was purified by filtration of the product 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.80(s,6H),2.53(s,6H),6.56(d,1H),7.45(m,9H),8.11(d, 2H).
Example 5: 3-phenyl-2-propenoic acid 1-benzoyl cyclohexyl ester
Figure BDA0001163527800000191
18.4g (0.1mol) of (1-hydroxycyclohexyl) (phenyl) methanone are placed in a 250ml three-necked flask and 100ml of dichloromethane and 10.1g (0.1mol) of triethylamine are added. After stirring uniformly, 16.6g (0.1mol) of cinnamoyl chloride was added and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, and the filtrate was washed with dilute hydrochloric acid, a saturated aqueous sodium bicarbonate solution and distilled water in this order. Then, the mixture was dried over anhydrous sodium sulfate overnight, filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, a total of 20g of yellow crystals were obtained 1The title compound was identified by H-NMR spectrum and was designated 184-CC.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.36(m,6H),1.69(m,2H),2.42(d,2H),6.59(d,1H),7.39(m,6H),7.65(m,3H),8.06(d, 2H).
Example 6 1-Benzoylcyclohexyl 3- (4-methoxyphenyl) -2-propenoate
20.4g (0.1mol) of (1-hydroxycyclohexyl) (phenyl) methanone are placed in a 250ml three-necked flask and 100ml of dichloromethane and 10.1g (0.1mol) of triethylamine are added. After stirring uniformly, 18g (0.1mol) of 3- (4-methoxy) phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, a total of 23g of yellow crystals were obtained, which was purified by filtration of the product 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.35(m,6H),1.70(m,2H),2.41(d,2H),3.75(s,3H),6.60(d,1H),7.41(m,6H),7.64(m,3H),8.05(d, 2H).
Example 7: 3-phenyl-2-propenoic acid 1- (2-methylbenzoyl) cyclohexyl ester
Figure BDA0001163527800000201
21.8g (0.1mol) of (1-hydroxycyclohexyl) (2-methylphenyl) methanone are placed in a 250ml three-necked flask and 100ml of dichloromethane and 10.1g (0.1mol) of triethylamine are added. After stirring uniformly, 16.6g (0.1mol) of cinnamoyl chloride was added and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, and the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, 21g in total of yellow crystals were obtained, which was purified by filtration of the product 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.36(m,6H),1.69(m,2H),2.42(d,2H),2.48(s,3H),6.59(d,1H),7.39(m,6H),7.65(m,3H),8.06(d, 2H).
Example 8: 3-phenyl-2-propenoic acid 1- (4-isopropylbenzoyl) cyclohexyl ester
Figure BDA0001163527800000202
24.6g (0.1mol) of (1-hydroxycyclohexyl) (4-isopropylphenyl) methanone are placed in a 250ml three-necked flask and 100ml of dichloromethane and 10.1g (0.1mol) of triethylamine are added. After stirring uniformly, 24.6g (0.1mol) of cinnamoyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, a total of 23g of yellow crystals were obtained, which was purified by filtration of the product 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.01(d,6H),1.36(m,6H),1.69(m,2H),2.42(d,2H),2.51(q,2H),6.59(d,1H),7.40(m,6H),7.64(m,3H),8.05(d, 2H).
Example 9: 3- (4-methoxy) phenyl-2-propenoic acid benzoylmethyl ester
Figure BDA0001163527800000211
13.6g (0.1mol) of 2-hydroxy-1-phenyl-1-ethanone were placed in a 250ml three-necked flask, and 100ml of dichloromethane and 10.1g (0.1mol) of triethylamine were added. After stirring uniformly, 18g (0.1mol) of 3- (4-methoxy) phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, 15.5g in total of pale yellow crystals were obtained, which were purified by filtration of the product 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (spectrum) (determined in Acetone-d 6): 3.83(s,3H),5.75(s,2H),6.54(d,1H),7.35(m,9H),8.11(d, 2H).
Example 10: 3- (4-methoxy) phenyl-2-propenoic acid (1-benzoyl-1, 1-bis (trichloromethyl)) ethyl ester
Figure BDA0001163527800000212
36.7g (0.1mol) of 2-hydroxy-2, 2-bis (trichloromethyl) -1-phenyl-1-ethanone were placed in a 250ml three-necked flask, and 100ml of dichloromethane and 10.1g (0.1mol) of triethylamine were added. After stirring uniformly, 18g (0.1mol) of 3- (4-methoxy) phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, a total of 28g of pale yellow crystals were obtained, which were obtained by passing the product through a filter 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 3.83(s,3H),6.54(d,1H),7.35(m,9H),8.11(d, 2H).
Example 11: 3- (4-methoxy) phenyl-2-propenoic acid (1-benzoyl) ethyl ester
Figure BDA0001163527800000213
15g (0.1mol) of 2-hydroxy-1-phenyl-1-propanone were placed in a 250ml three-necked flask and 100ml of methylene chloride and 10.1g (0.1mol) of triethylamine were added. After stirring uniformly, 18g (0.1mol) of 3- (4-methoxy) phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, 16g in total of pale yellow crystals were obtained, which were obtained by passing the product through a filter 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.58(d,3H),3.83(s,3H),5.64(q, 1H),6.54(d,1H),7.35(m,9H),8.11(d, 2H).
Example 12: 3-methyl-3- (4-vinyl) phenyl-2-propenoic acid 2-chlorophenylformyl isopropyl ester
Figure BDA0001163527800000221
19.8g (0.1mol) of 2-hydroxy-2-methyl-1- (2-chloro) phenyl-1-propanone were placed in a 250ml three-necked flask, and 100ml of methylene chloride and 10.1g (0.1mol) of triethylamine were added. After stirring uniformly, 20.6g (0.1mol) of 3-methyl-3- (4-vinyl) phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, a total of 19g of pale yellow crystals were obtained, which were purified by filtration of the product 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.78(s,6H),2.34(s,6H),6.54(d,1H),7.35(m,9H),8.11(d, 2H).
Example 13: 3-methyl-3- (4-ethynyl) phenyl-2-propenoic acid 2-methylphenylcarbonylisopropyl ester
Figure BDA0001163527800000222
17.7g (0.1mol) of 2-hydroxy-2-methyl-1- (2-methyl) phenyl-1-propanone were placed in a 250ml three-necked flask, and 100ml of methylene chloride and 10.1g (0.1mol) of triethylamine were added. After stirring uniformly, 16.6g (0.1mol) of 3-methyl-3- (4-ethynyl) phenyl-2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, 16g in total of pale yellow crystals were obtained, which were obtained by passing the product through a filter 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.78(s,6H),2.42(s,3H),2.48(s,3H)4.05(s, 1H),6.11(d,1H),7.35(m, 9H).
Example 14: 2-methyl-3- (4-chlorophenyl) -2-propenoic acid 1- (4-isopropylbenzoyl) cyclohexyl ester
Figure BDA0001163527800000231
29.2g of (1-hydroxycyclohexyl) (4-isopropylphenyl) methanone are placed in a 250ml three-necked flask and 100ml of dichloromethane and 10.1g (0.1mol) of triethylamine are added. After stirring uniformly, 24.6g (0.1mol) of 2-methyl-3- (4-chlorophenyl) -2-acryloyl chloride was added, and the reaction was stirred at room temperature for 3 hours. Then, the reaction solution was filtered, the filtrate was washed with dilute hydrochloric acid (5%), saturated aqueous sodium bicarbonate solution and distilled water in this order, then dried over anhydrous sodium sulfate overnight and filtered, the organic phase was distilled off under reduced pressure, and after recrystallization from methanol, 25g in total of yellow crystals were obtained, which was purified by filtration of the product 1The title compound was confirmed by H-NMR spectrum.
1H-NMR (Spectrum) (determined in Acetone-d 6): 1.20(d,6H),1.44(s,10H),1.80(s, 3H),1.69(m,2H),2.42(d,2H),2.51(q,2H),6.59(d,1H),7.40(m,6H),7.64(m,3H),8.05(d, 2H).
Ultraviolet absorption spectrum experiment:
comparing 1173 with 1173-CC and 184 with 184-CC, finding that the ultraviolet absorption of the compounds 1173-CC and 184-CC after being inoculated with cinnamoyl has obvious red shift, thus greatly improving the utilization efficiency of the ultraviolet light source and being also used in the UV-LED exposure light source. The experimental data are shown in fig. 1 and fig. 2.
Figure BDA0001163527800000241
Thermal stability experiments:
thermogravimetric (TG) analysis of the thermal stability of each compound was performed using a thermo analyzer type zy-2P (mettler), test conditions: starting from an initial temperature of 25 ℃ the temperature was raised at a rate of 10K/min to a final temperature of 500 ℃. The weight percent of the compound as a function of time is shown in FIG. 3.
Experimental data show that when cinnamoyl is introduced into the structures of compounds 1173 and 184, the thermal stability of the resulting compounds is significantly improved. The initial thermal decomposition temperatures are shown in the following table:
name of Compound Initial decomposition temperature/. degree.C
1173 80
1173-CC 170
184 125
184-CC 175
Photoinitiation performance experiments:
the photoinitiation performance of the photoinitiator was tested by real-time infrared technology. Selecting 1173-CC and 184-CC compounds as representative initiators, and initiating polymerization of polymerizable monomer hydroxyethyl methacrylate (HEMA) under ultraviolet irradiation. 5ml of acetone is taken and added with 2g of HEMA, the mixture is stirred, after the monomer is dissolved, 0.06g of photoinitiator (1173-C or 184-CC) is added, and a 1173-CC-HEMA sample and a 184-CC-HEMA sample are respectively prepared. Coating a small amount of sample on KBr salt tablet, placing in Nicolet5700 type infrared spectrometer, irradiating sample with ultraviolet point light source (high-pressure mercury lamp), and adjusting ultraviolet light intensity of sample surface to 30mW/cm 2(light intensity was measured by a HonleUV light intensity meter). The double bond conversion rate of the monomer is acquired by near infrared in real time, and the real-time infrared parameters are set as follows: data acquisition Interval 0.3985s, 1 scan per spectrum, resolution 4cm -1. The characteristic absorption peak of the HEMA in the near infrared spectrogram of the carbon-carbon double bond is 1630cm -1Since the carbon-carbon double bond is changed to a carbon-carbon single bond as the photocuring reaction proceeds and the intensity of the absorption peak of the double bond becomes weaker as the light irradiation time increases, the degree of change in the polymerization reaction is reflected by the change in the characteristic absorption peak of the carbon-carbon double bond. Double bond conversion (DC) was calculated from omnic7.1 infrared software and origin6.1 data processing software in combination with formula (1):
DC(％)＝[1-(At/A 0)]×100％ (1)
in the formula, A 0And A is 1630cm before curing and t-time after illumination, respectively -1Area of characteristic absorption peak of hydroxyethyl methacrylate double bond.
The change with time of the double bond conversion rate of the polymerizable monomer obtained by using the compound 184-CC as the photoinitiator is shown in FIG. 4, and the change with time of the double bond conversion rate of the polymerizable monomer obtained by using the compound 1173-CC as the photoinitiator is shown in FIG. 5.
The experimental data in FIGS. 4 and 5 show that compounds 184-CC and 1173-CC have very good photoinitiating effect.
Migration resistance test:
mixing Ethyl Acrylate (EA), tripropylene glycol diacrylate (TPGDA) and trimethylolpropane triacrylate (TMPTA) according to the mass ratio of 3: 4 to obtain a mixture, respectively adding 184, 184-CC, 1173 and 1173-CC which account for 3 wt% of the total amount of the mixture, and respectively preparing four photocuring systems of a, a ', b and b'.
Under the protection of nitrogen, a 365nm light source is used for generating light with the light intensity of 100mW/cm 2The film was fully cured by exposure to light for 5min and left in a desiccator at room temperature for 24h, the cured film was crushed, weighed and the mass of each of the four photoinitiators (184, 184-CC, 1173-CC) was calculated. The solution was soaked in 50mL acetonitrile for 96h, and the resulting acetonitrile solution was filtered and the absorbance at 300nm was monitored by UV-Vis absorption Spectroscopy. The concentrations and the masses of the four photoinitiators in the acetonitrile solution can be obtained by substituting the absorbance A and the molar absorption coefficient epsilon into the formulas (2) and (3).
c＝A/(εl) (2)
m1＝M×c×10 -2×V0 (3)
R＝(m1/(W×m0))*100％ (4)
c is the concentration (mol/L) of the precipitated initiator; l is the optical path length, taken here as 1 cm; the mass M1 of the four photoinitiators extracted was calculated according to equation (3), M being the relative molecular mass of the photoinitiator and V0 being the volume of acetonitrile. R is the mobility of the photoinitiator, W is the initial addition mass fraction of the photoinitiator, m0 is the mass of the cured film, m 1Is the residual amount of the photoinitiator.
The experimental results are as follows:
name of substance Mobility (%)
184 0.123
184-CC 0.0075
1173 0.104
1173-CC 0.024

Claims (16)

1. The benzoyl methyl cinnamate compound has a structure shown in a formula (I):
Figure FDA0002287019730000011
wherein
R 1、R 2、R 3、R 4And R 5Independently of one another, from hydrogen, halogen, hydroxyl, mercapto, C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 3-C 20Cycloalkylthio radicals and C 4-C 20Cycloalkylalkylthio radical, wherein C is as defined above 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 3-C 20Cycloalkylthio radicals and C 4-C 20The cycloalkylalkylthio group may optionally be substituted withSubstituted with one or more groups independently selected from the group consisting of: halogen, hydroxy, mercapto, C 1-C 6Alkyl radical, C 1-C 6Alkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenyl and C 2-C 6An alkynyl group;
R 6and R 7Are the same or different and are selected from C 1-C 6Alkyl and halo C 1-C 6Alkyl, or R 6And R 7Together with the carbon atom to which they are attached form C 3-C 8A cycloalkyl group;
R 8、R 9、R 10、R 11and R 12Independently of one another, from hydrogen, halogen, hydroxyl, mercapto, C 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 3-C 20Cycloalkylthio radicals and C 4-C 20Cycloalkylalkylthio radical, wherein C is as defined above 1-C 20Alkyl radical, C 2-C 20Alkenyl radical, C 2-C 20Alkynyl, C 3-C 20Cycloalkyl radical, C 4-C 20Cycloalkylalkyl radical, C 1-C 20Alkoxy radical, C 3-C 20Cycloalkoxy, C 4-C 20Cycloalkylalkoxy radical, C 1-C 20Alkylthio radical, C 3-C 20Cycloalkylthio radicals and C 4-C 20The cycloalkylalkylthio group may be optionally substituted with one or more groups independently selected from: halogen, hydroxy, mercapto, C 1-C 6Alkyl radical, C 1-C 6Alkoxy radical, C 1-C 6Alkylthio radical, C 2-C 6Alkenyl and C 2-C 6An alkynyl group; and
R 13and R 14Same or different and selected from H, C 1-C 6Alkyl and halo C 1-C 6An alkyl group.
2. A compound according to claim 1, wherein R 6And R 7Are the same or different and are selected from C 1-C 4Alkyl and halo C 1-C 4Alkyl, or R 6And R 7Together with the carbon atom to which they are attached form C 5-C 6A cycloalkyl group.
3. A compound according to claim 2, wherein R 6And R 7Identical and is methyl or halomethyl, or R 6And R 7Together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl group.
4. A compound according to claim 1, wherein R 13And R 14Same or different and selected from H, C 1-C 4Alkyl and halo C 1-C 4An alkyl group.
5. A compound according to claim 2, wherein R 13And R 14Same or different and selected from H, C 1-C 4Alkyl and halo C 1-C 4An alkyl group.
6. A compound according to claim 3, wherein R 13And R 14Same or different and selected from H, C 1-C 4Alkyl and halo C 1-C 4An alkyl group.
7. A compound according to claim 4, wherein R 13And R 14Are all H.
8. A compound according to any one of claims 1 to 7, wherein
R 1、R 2、R 3、R 4And R 5Independently of one another, from hydrogen, halogen, hydroxyl, mercapto, C 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 2-C 6Alkenyloxy radical, C 2-C 6Alkynyloxy, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 3-C 8Cycloalkylthio radicals and C 4-C 8Cycloalkylalkylthio radical, wherein C is as defined above 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 3-C 8Cycloalkylthio radicals and C 4-C 8The cycloalkylalkylthio group may be optionally substituted with one or more groups independently selected from: halogen, hydroxy, mercapto, C 1-C 4Alkyl radical, C 1-C 4Alkoxy radical, C 1-C 4Alkylthio radical, C 2-C 4Alkenyl and C 2-C 4An alkynyl group; and/or
R 8、R 9、R 10、R 11And R 12Independently of one another, from hydrogen, halogen, hydroxyl, mercapto, C 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 3-C 8Cycloalkylthio radicals and C 4-C 8Cycloalkylalkylthio radical, wherein C is as defined above 1-C 6Alkyl radical, C 2-C 6Alkenyl radical, C 2-C 6Alkynyl, C 3-C 8Cycloalkyl radical, C 4-C 8Cycloalkylalkyl radical, C 1-C 6Alkoxy radical, C 3-C 8Cycloalkoxy, C 4-C 8Cycloalkylalkoxy radical, C 1-C 6Alkylthio radical, C 3-C 8Cycloalkylthio radicals and C 4-C 8The cycloalkylalkylthio group may be optionally substituted with one or more groups independently selected from: halogen, hydroxy, mercapto, C 1-C 4Alkyl radical, C 1-C 4Alkoxy radical, C 1-C 4Alkylthio radical, C 2-C 4Alkenyl and C 2-C 4Alkynyl.
9. A compound according to any one of claims 1 to 7, wherein
R 1、R 2、R 3、R 4And R 5Independently of one another, from hydrogen, halogen, C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4Alkylthio group wherein the foregoing C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4The alkylthio group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4An alkylthio group; and/or
R 8、R 9、R 10、R 11And R 12Independently of one another, from hydrogen, halogen, C 1-C 4Alkyl radical, C 2-C 4Alkenyl radical, C 2-C 4Alkynyl, C 1-C 4Alkoxy and C 1-C 4Alkylthio group wherein the foregoing C 1-C 4Alkyl radical, C 2-C 4Alkenyl radical, C 2-C 4Alkynyl, C 1-C 4Alkoxy and C 1-C 4The alkylthio group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, C 1-C 4Alkyl radical, C 1-C 4Alkoxy and C 1-C 4An alkylthio group.
10. The compound according to claim 1, wherein the compound is selected from the group consisting of:
Figure FDA0002287019730000031
Figure FDA0002287019730000041
11. a process for the preparation of a compound of formula (I) according to any one of claims 1 to 10, comprising subjecting a compound of formula (II) to an esterification reaction with a compound of formula (III) to give a compound of formula (I),
Figure FDA0002287019730000042
wherein R is 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13And R 14As defined in any one of claims 1 to 10, and X is hydroxy or halogen.
12. The process according to claim 11, wherein the esterification reaction is carried out in the presence of a catalyst.
13. The process according to claim 12, wherein the catalyst is one or more selected from the group consisting of: sulfuric acid, perchloric acid, zinc chloride, ferric trichloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines.
14. The process according to claim 13, wherein the tertiary amine is a trialkylamine.
15. The method of claim 14, wherein the trialkylamines are trimethylamine and triethylamine.
16. Use of a compound according to any one of claims 1 to 10 as a photoinitiator.
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