Mono-or di-cinnamate photoinitiator, and preparation method and application thereof
阅读说明：本技术 单或双肉桂酸酯类光引发剂及其制备方法和应用 (Mono-or di-cinnamate photoinitiator, and preparation method and application thereof ) 是由 邹应全 庞玉莲 樊书珩 于 2018-06-06 设计创作，主要内容包括：本发明涉及式(I)的肉桂酸酯类化合物,其中式(I)化合物中的各变量如说明书中所定义。本发明还涉及一种制备本发明肉桂酸酯类化合物的方法,包括使式(II)化合物与式(III)化合物进行酯化反应。本发明的肉桂酸酯类化合物可用作光引发剂,能够吸收200-400nm范围内的辐射热、稳定性良好、耐黄变,而且更为重要的是,该类引发剂相比于现有α-羟基酮类光引发剂,大大改善了异味和迁移性强的问题,而且光引发剂紫外吸收红移至300nm-400nm左右,可适用于UV-LED光源固化中。本发明还涉及本发明肉桂酸酯类化合物作为光引发剂的用途。<Image he="525" wi="700" file="DDA0001686432470000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to cinnamate compounds of formula (I), wherein the variables in the compounds of formula (I) are as defined in the specification. Hair brushThe invention also relates to a method for preparing the cinnamate compounds of the invention, which comprises the step of carrying out esterification reaction on the compound of the formula (II) and the compound of the formula (III). The cinnamate compound can be used as a photoinitiator, can absorb radiant heat within the range of 200-400nm, has good stability and yellowing resistance, and more importantly, compared with the existing alpha-hydroxy ketone photoinitiator, the photoinitiator greatly improves the problems of peculiar smell and strong mobility, and the ultraviolet absorption red of the photoinitiator is shifted to about 300-400nm, so that the photoinitiator can be suitable for UV-LED light source curing. The invention also relates to the application of the cinnamate compounds as the photoinitiator.)
1. Mono-or bis-cinnamates of formula (I):
Wherein
R1、R2、R3And R4are the same or different from each other and are selected from H, C1-C6Alkyl, halo C1-C6Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C6Alkyl and halo C1-C6The radical of alkyl is substituted one or more times,
R5、R6、R7、R8Identical or different from each other and selected from hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18Aryl, wherein the aforementioned C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18The 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, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenyl and C2-C6An alkynyl group;
R9And R10Are the same or different from each other and are selected from H, C1-C6Alkyl and halo C1-C6Alkyl, or R9And R10together with the carbon atoms to which they are attached form a cycloalkyl group containing a total of 3 to 6 ring carbon atoms;
Y1And Y2Are identical or different from each other and are independently selected from H and a group of formula (X) provided that Y1Is not H:
Wherein
Is the site of attachment of the group of formula (X) in the compound of formula (I);
R14And R15Are the same or different from each other and are selected from H, C1-C6Alkyl and halo C1-C6An alkyl group; and
R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from the group consisting of hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18Aryl, wherein the aforementioned C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18The 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, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenyl and C2-C6alkynyl.
2. The compound of claim 1, wherein R1、R2、R3And R4Are the same or different from each other and are selected from H, C1-C4Alkyl, halo C1-C4Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C4Alkyl and halo C1-C4Alkyl groups are substituted one or more times; it is especially preferred that R1And R2One of (1) and R3And R4One of them is H, the others are the same or different from each other and are selected from C1-C4Alkyl, fluoro C1-C4Alkyl, chloro C1-C4Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C4Alkyl and halo C1-C4The alkyl group is substituted one or more times.
3. The compound of claim 1 or 2, wherein R5、R6、R7、R8Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8CycloalkanesAlkyl alkoxy, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8Cycloalkylthio radical, C4-C8Cycloalkylalkylthio and C6-C10aryl, wherein the aforementioned C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8Cycloalkylalkoxy radical, C1-C6alkylthio radical, C2-C6Alkenylthio radical, C2-C6alkynylthio, C3-C8Cycloalkylthio radical, C4-C8Cycloalkylalkylthio and C6-C10The 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, C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C2-C4Alkenyl and C2-C4An alkynyl group; preferably, R is5、R6、R7、R8Independently of one another, from hydrogen, halogen, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group.
4. A compound according to any one of claims 1 to 3, wherein
R9And R10Are the same or different from each other and are selected from H, C1-C4Alkyl and halo C1-C4Alkyl, or
R9And R10Together with the carbon atoms to which they are attached, may also form cycloalkyl groups containing a total of 5 to 6 ring carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl.
5. The compound of any one of claims 1-4, wherein R14And R15Are the same or different from each other and are selected from H, C1-C4Alkyl and halo C1-C4An alkyl group; preferably, R is14And R15Are all H.
6. The compound of any one of claims 1-5, wherein R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from the group consisting of hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8Cycloalkylalkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8Cycloalkylthio radical, C4-C8Cycloalkylalkylthio and C6-C10Aryl, wherein the aforementioned C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8Cycloalkylalkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8Cycloalkylthio radical, C4-C8Cycloalkylalkylthio and C6-C10The 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, C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C2-C4alkenyl and C2-C4An alkynyl group; preferably, R is16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from hydrogen, halogen, nitro, C1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C1-C4Alkoxy radical, C1-C4Alkylthio and phenyl, wherein C is as defined above1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C1-C4Alkoxy radical, C1-C4The alkylthio and phenyl groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group; in particular, R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from hydrogen, fluorine, chlorine, bromine, nitro, C1-C4Alkyl, fluoro C1-C4Alkyl, chloro C1-C4Alkyl, bromo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio and phenyl.
7. The compound of claim 1, wherein
R1And R2One of (1) and R3And R4One of them is H, the others are the same or different from each other and are selected from C1-C4Alkyl, fluoro C1-C4Alkyl, chloro C1-C4Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C4Alkyl and halo C1-C4Alkyl groups are substituted one or more times;
R5、R6、R7、R8Independently of one another, from hydrogen, halogen, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group;
R9And R10Are the same or different from each other and are selected from H, C1-C4Alkyl and halo C1-C4An alkyl group; or, R9And R10Together with the carbon atoms to which they are attached, may also form cycloalkyl groups containing a total of 5 to 6 ring carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl;
R14And R15Are the same or different from each other and are selected from H, C1-C4Alkyl and halo C1-C4Alkyl, preferably R14And R15Are all H; and
R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from hydrogen, fluorine, chlorine, bromine, nitro, C1-C4Alkyl radical, C1-C4Fluoroalkyl, C1-C4Chloroalkyl, C1-C4bromoalkyl, C2-C4Alkenyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio and phenyl.
8. The compound of claim 1, wherein the compound of formula (I) is selected from compounds 1-17 of the group consisting of:
9. A process for the preparation of a compound of formula (I) as claimed in any one of claims 1 to 8, comprising:
a) When Y is1And Y2Are the same group of formula (X) or when Y2When the compound is H, the compound of the formula (II) and the compound of the formula (III) are subjected to esterification reaction to obtain the compound of the formula (I),
b) When Y is1And Y2When the groups are different in formula (X), the compound in formula (II) is subjected to esterification reaction with different compounds in formula (III) in sequence to obtain the compound in formula (I),
Wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R14、R15、R16、R17、R18、R19And R20As defined in any of claims 1 to 8, and Y is halogen or hydroxy, especially chlorine.
10. The method of claim 9, wherein when Y is1And Y2The molar ratio of the compound of formula (III) to the compound of formula (II) is from 5:1 to 2:1, preferably from 3:1 to 2:1, when the same radicals of formula (X) are present; when Y is2When H, the molar ratio of the compound of formula (III) to the compound of formula (II) is from 3:1 to 1:1, preferably from 1.5:1 to 1: 1; when Y is1And Y2In the case of different radicals of the formula (X), the molar ratio of each compound of the formula (III) to the compound of the formula (II) is from 3:1 to 1:1, preferably from 1.5:1 to 1: 1.
11. Use of a compound of formula (I) as defined in any one of claims 1 to 8 as a photoinitiator.
Technical Field
The invention relates to a mono-or di-cinnamic acid ester compound which can be used as a photoinitiator, and also relates to a preparation method and an application of the mono-or di-cinnamic acid ester 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 -hydroxy ketone photoinitiators are commonly used photoinitiators, the most common of which are IRGACURE2959 (2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-propanone) and IRGACURE 127 (2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropanoyl) -benzyl) -phenyl) -2-methylpropan-1-one). The two photoinitiators have excellent thermal stability, good yellowing resistance and lower price; the defects are mainly as follows: benzaldehyde in the photolysis product has bad smell, and meanwhile, the benzaldehyde has high volatility and strong mobility, ultraviolet absorption is within 300nm, and the benzaldehyde is not suitable for UV-LED light source curing.
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:
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
In view of the above-mentioned state of the art, the present inventors have conducted extensive and intensive studies in the field of photoinitiators, in order to find a photoinitiator which can improve the odor and migration of α -hydroxy ketone photoinitiators, and is suitable for use in UV-LED light source curing. The inventor finds that if cinnamoyl is introduced or connected to an alpha-hydroxy ketone photoinitiator, the characteristic that cinnamoyl can be polymerized and crosslinked under ultraviolet light is utilized, the photoinitiator obtained in the way keeps the advantages of the alpha-hydroxy ketone photoinitiator and simultaneously solves the problems of peculiar smell and strong mobility of the existing alpha-hydroxy ketone photoinitiator (such as IRGACURE 2959), and simultaneously, with the increase of conjugated groups, the ultraviolet absorption red of the photoinitiator is shifted to about 300nm-400nm, so that the photoinitiator is applicable to UV-LED light source curing. The present invention has been achieved based on the foregoing findings.
Therefore, an object of the present invention is to provide a novel mono-or di-cinnamate compound. The compound can be used as a photoinitiator, can absorb the radiant heat within the range of 300-400nm, has good stability and yellowing resistance, and more importantly, compared with the existing alpha-hydroxy ketone photoinitiator (such as IRGACURE 2959), the compound greatly improves the problems of peculiar smell and strong mobility, and the ultraviolet absorption red of the photoinitiator is shifted to about 300-400nm, so that the compound can be suitable for UV-LED light source curing.
Another object of the present invention is to provide a method for preparing the mono-or di-cinnamate compounds of the present invention.
It is a further object of the present invention to provide the use of the mono-or di-cinnamates of the present invention as photoinitiators. Compared with the existing alpha-hydroxy ketone photoinitiator (such as IRGACURE 2959), the mono-or di-cinnamate compound provided by the invention is used as the photoinitiator, so that the problems of peculiar smell and strong mobility are greatly improved, and the problem that the ultraviolet absorption wavelength is short and cannot meet the requirement of a UV-LED light source is also solved.
The technical solution for achieving the above object of the present invention can be summarized as follows:
1. Mono-or bis-cinnamates of formula (I):
Wherein
R1、R2、R3And R4Are the same or different from each other and are selected from H, C1-C6Alkyl, halo C1-C6Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C6Alkyl and halo C1-C6The radical of alkyl is substituted one or more times,
R5、R6、R7、R8Identical or different from each other and selected from hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C20Alkyl radical、C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18Aryl, wherein the aforementioned C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18The 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, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenyl and C2-C6An alkynyl group;
R9And R10Are the same or different from each other and are selected from H, C1-C6Alkyl and halo C1-C6Alkyl, or R9And R10Together with the carbon atoms to which they are attached form a cycloalkyl group containing a total of 3 to 6 ring carbon atoms;
Y1And Y2Are the same or different from each other and are independently selectedFrom H and a group of formula (X) provided that Y1is not H:
Wherein
Is the site of attachment of the group of formula (X) in the compound of formula (I);
R14And R15Are the same or different from each other and are selected from H, C1-C6Alkyl and halo C1-C6An alkyl group; and
R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from the group consisting of hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18aryl, wherein the aforementioned C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18The 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, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenyl and C2-C6Alkynyl.
2. The compound of claim 1, wherein R1、R2、R3And R4Are the same or different from each other and are selected from H, C1-C4Alkyl, halo C1-C4Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C4Alkyl and halo C1-C4Alkyl groups are substituted one or more times; it is especially preferred that R1And R2One of (1) and R3And R4One of them is H, the others are the same or different from each other and are selected from C1-C4Alkyl, fluoro C1-C4Alkyl, chloro C1-C4Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C4alkyl and halo C1-C4The alkyl group is substituted one or more times.
3. The compound according to item 1 or 2, wherein R5、R6、R7、R8Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8Cycloalkylalkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8cycloalkylthio radical, C4-C8Cycloalkylalkylthio and C6-C10Aryl, wherein the aforementioned C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8Cycloalkylalkoxy radical, C1-C6alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8Cycloalkylthio radical, C4-C8cycloalkylalkylthio and C6-C10The 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, C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C2-C4Alkenyl and C2-C4An alkynyl group; preferably, R is5、R6、R7、R8Independently of one another, from hydrogen, halogen, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group.
4. the compound according to any one of items 1 to 3, wherein
R9And R10Are the same or different from each other and are selected from H, C1-C4Alkyl and halo C1-C4Alkyl, or
R9And R10together with the carbon atoms to which they are attached, may also form cycloalkyl groups containing a total of 5 to 6 ring carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl.
5. The compound of any one of claims 1-4, wherein R14And R15Are the same or different from each other and are selected from H, C1-C4Alkyl and halo C1-C4an alkyl group; preferably, R is14And R15Are all H.
6. the compound of any one of claims 1-5, wherein R16、R17、R18、R19And R20are identical or different from each other if R16、R17、R18、R19And R20when there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from the group consisting of hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8Cycloalkylalkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8Cycloalkylthio radical, C4-C8Cycloalkylalkylthio and C6-C10Aryl, wherein the aforementioned C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8cycloalkylalkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8Cycloalkylthio radical、C4-C8Cycloalkylalkylthio and C6-C10The 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, C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C2-C4Alkenyl and C2-C4An alkynyl group; preferably, R is16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17two R18Two R19and two R20Are also identical or different from each other and are selected from hydrogen, halogen, nitro, C1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C1-C4Alkoxy radical, C1-C4Alkylthio and phenyl, wherein C is as defined above1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C1-C4Alkoxy radical, C1-C4The alkylthio and phenyl groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group; in particular, R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from hydrogen, fluorine, chlorine, bromine, nitro, C1-C4Alkyl, fluoro C1-C4Alkyl, chloro C1-C4Alkyl, bromo C1-C4Alkyl radical, C2-C4An alkenyl group,C1-C4Alkoxy radical, C1-C4Alkylthio and phenyl.
7. The compound according to item 1, wherein
R1And R2One of (1) and R3And R4One of them is H, the others are the same or different from each other and are selected from C1-C4Alkyl, fluoro C1-C4alkyl, chloro C1-C4Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C4Alkyl and halo C1-C4Alkyl groups are substituted one or more times;
R5、R6、R7、R8Independently of one another, from hydrogen, halogen, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group;
R9And R10Are the same or different from each other and are selected from H, C1-C4Alkyl and halo C1-C4An alkyl group; or, R9And R10Together with the carbon atoms to which they are attached, may also form cycloalkyl groups containing a total of 5 to 6 ring carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl;
R14And R15Are the same or different from each other and are selected from H, C1-C4Alkyl and halo C1-C4Alkyl, preferably R14And R15Are all H; and
R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from hydrogen, fluorine, chlorine, bromine, nitro, C1-C4Alkyl radical, C1-C4Fluoroalkyl, C1-C4Chloroalkyl, C1-C4Bromoalkyl, C2-C4Alkenyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio and phenyl.
8. The compound according to item 1, wherein the compound of formula (I) is selected from compounds 1 to 17 of the present invention.
9. A process for the preparation of a compound of formula (I) as described in any one of claims 1 to 8, comprising:
a) When Y is1And Y2Are the same group of formula (X) or when Y2When the compound is H, the compound of the formula (II) and the compound of the formula (III) are subjected to esterification reaction to obtain the compound of the formula (I),
b) When Y is1And Y2When the groups are different in formula (X), the compound in formula (II) is subjected to esterification reaction with different compounds in formula (III) in sequence to obtain the compound in formula (I),
Wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R14、R15、R16、R17、R18、R19And R20As defined in any one of items 1 to 8, and Y is halogen or hydroxy, especially chlorine.
10. The method of claim 9, wherein when Y is1And Y2the molar ratio of the compound of formula (III) to the compound of formula (II) is from 5:1 to 2:1, preferably from 3:1 to 2:1, when the same radicals of formula (X) are present; when Y is2When H, the molar ratio of the compound of formula (III) to the compound of formula (II) is from 3:1 to 1:1, preferably from 1.5:1 to 1: 1; when Y is1And Y2in the case of different radicals of the formula (X), the molar ratio of each compound of the formula (III) to the compound of the formula (II) is from 3:1 to 1:1, preferably from 1.5:1 to 1: 1.
11. Use of a compound of formula (I) as described in any one of items 1 to 8 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.
Drawings
FIG. 1 is a schematic representation of a Ugra (Ugra) printing test strip, wherein
1-a continuous density ladder section,
2-concentric circle coil segment with equal line of yin and yang micron,
3-a full tone dot segment,
4-ghost control segment, and
5-highlight, dark tone control section.
Detailed Description
According to a first aspect of the present invention there is provided a mono-or di-cinnamic ester of formula (I):
wherein
R1、R2、R3And R4Are the same or different from each other and are selected from H, C1-C6Alkyl, halo C1-C6Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C6Alkyl and halo C1-C6The radical of alkyl is substituted one or more times,
R5、R6、R7、R8Identical or different from each other and selected from hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18Aryl, wherein the aforementioned C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18The 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, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenyl and C2-C6An alkynyl group;
R9And R10Are the same or different from each other and are selected from H, C1-C6Alkyl and halo C1-C6Alkyl, or R9And R10Together with the carbon atoms to which they are attached form a cycloalkyl group containing a total of 3 to 6 ring carbon atoms;
Y1And Y2Are identical or different from each other and are independently selected from H and a group of formula (X) provided that Y1Is not H:
Wherein
Is the site of attachment of the group of formula (X) in the compound of formula (I);
R14And R15Are the same or different from each other and are selected from H, C1-C6Alkyl and halo C1-C6An alkyl group; and R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20are also identical or different from each other and are selected from the group consisting of hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C20Alkyl radical, C2-C20alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18Aryl, wherein the aforementioned C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18The 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, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenyl and C2-C6Alkynyl.
The compound of the formula (I) retains the characteristics of the alpha-hydroxyketone photoinitiator due to the existence of the alpha-hydroxyketone structural part (hydroxyl is already esterified or is not esterified), and the compound can be polymerized and crosslinked under ultraviolet radiation due to the cinnamoyl structural part contained in the compound, so that the obtained compound of the formula (I) retains the advantages of the alpha-hydroxyketone photoinitiator and simultaneously improves the problems of strong odor and mobility and short ultraviolet absorption wavelength of the alpha-hydroxyketone photoinitiator, and the compound can be red-shifted to about 300-400nm, preferably to 350-400 nm.
In the present invention, the prefix "Cn-Cm"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 hereinn-CmAlkyl "means a branched or unbranched saturated open-chain 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-dimethylpropyl, 1-methylpropyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-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. C1-C8The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butylPentyl, isopentyl, hexyl, heptyl, octyl and isomers thereof. C1-C6The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl and isomers thereof. C1-C4The alkyl group may be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, and isomers thereof.
The term "C" as used herein2-CmAlkenyl "means a branched or unbranched unsaturated open-chain hydrocarbon group having 2 to m, for example 2 to 20, preferably 2 to 6, more preferably 2 to 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, C-methyl-1-propenyl, C-methyl, 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-butene.A phenyl group, 3-dimethyl-2-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1, 2-trimethyl-2-propenyl group, 1-ethyl-1-methyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group and isomers thereof. C2-C6The 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. C2-C4The 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 herein2-CmAlkynyl "means a branched or unbranched unsaturated open-chain hydrocarbon group having 2 to m, for example 2 to 20, preferably 2 to 6, more preferably 2 to 4 carbon atoms and having one or more triple bonds in any position, such as ethynyl, propynyl, 1-butynyl, 2-butynyl and isomers thereof. C2-C6Alkynyl 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. C2-C4Alkynyl may be ethynyl, propynyl, 1-butynyl, 2-butynyl and isomers thereof.
The term "C" as used herein3-CmCycloalkyl "means a saturated alicyclic monocyclic group having 3 to m, such as 3 to 20, preferably 3 to 8, more preferably 5 to 6, ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
The term "C4-CmCycloalkylalkyl "denotes alkyl substituted by cycloalkyl and containing a total of 4 to m carbon atoms, e.g. 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, more preferably 4 to 6 carbon atoms, where alkyl and cycloalkyl applyAs defined herein, e.g., cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, and the like.
The term "C" as used hereinn-CmAlkoxy "and" Cn-CmAlkylthio "means at Cn-CmC having an oxygen or sulfur atom as a linking group bonded to any valence of the alkyl groupn-CmAlkyl radicals, e.g. C1-C20Alkoxy (or thio) radicals, preferably C1-C12Alkoxy (or thio) radicals, more preferably C1-C8Alkoxy (or thio) radicals, particularly preferably C1-C6Alkoxy (or thio) radicals, particularly preferably C1-C4Alkoxy (or thio) group. C1-C8The alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, isooctoxy and isomers thereof. C1-C4The alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and isomers thereof. C1-C8The alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butyl, 2-butylthio, tert-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, isooctylthio and isomers thereof. C1-C4The alkylthio group can be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio and isomers thereof.
The term "C" as used herein2-CmAlkenyloxy "and" C2-CmAlkenylthio "means in C2-CmC having an oxygen atom or a sulfur atom as a linking group bonded to any valence in the alkenyl group2-CmAlkenyl radicals, e.g. C2-C20Alkenoxy (or thio) radicals, preferably C2-C12Alkenyloxy (or thio) radicals, more preferably C2-C8Alkenoxy (or thio) radicals, particularly preferably C2-C6Alkenoxy (or thio) radicals, particularly preferably C2-C4Alkenyloxy (or thio) radicals. C2-C4The alkenyloxy group may be ethyleneoxy, propyleneoxy, isopropenyloxy, n-butyleneoxy, sec-butyleneoxy, iso-butyleneoxy, tert-butyleneoxy and isomers thereof. C2-C4The alkenylthio group may be vinylthio, propenylthio, isopropenylthio, n-butenylthio and isomers thereof.
The term "C" as used herein2-CmAlkynyloxy "and" C2-CmAlkynylthio "means at C2-CmC with one oxygen or one sulfur atom as a linking group bonded to any valence bond in the alkynyl group2-CmAlkynyl, e.g. C2-C20alkynyloxy (or thio) radicals, preferably C2-C12Alkynyloxy (or thio) group, more preferably C2-C8Alkynyloxy (or thio) radicals, particularly preferably C2-C6Alkynyloxy (or thio) radicals, particularly preferably C2-C4Alkynyloxy (or thio) group. C2-C4The alkynyloxy group may be ethynyloxy, propynyloxy, n-butynyloxy, sec-butynyloxy and isomers thereof. C2-C4The alkynylthio group may be an ethynylthio group, a propynylthio group, an n-butynylthio group, a sec-butynylthio group and isomers thereof.
The term "C" as used herein3-CmCycloalkoxy "and" C3-CmCycloalkylthio "means C having an oxygen atom or a sulfur atom as a linking group bonded to any ring atom in the cycloalkyl group3-CmCycloalkyl radicals, e.g. C3-C20A cycloalkoxy (or thio) group, preferably C3-C8A cycloalkoxy (or thio) group, more preferably C5-C6A cycloalkoxy (or thio) group. C3-C20the cycloalkoxy group may be cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy and isomers thereof. C3-C20The cycloalkylthio group may be cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, cyclooctylthio, cyclodecylthio and isomers thereof.
The term "C" as used herein4-CmCycloalkylalkoxy "and" C4-CmCycloalkylalkylthio "means at C4-CmThe alkyl group of the cycloalkylalkyl group containing the group having an oxygen atom or a sulfur atom as a linking group bonded at any valence bond, e.g. C4-C8Cycloalkyl alkoxy (or thio) radicals, e.g. C3-C8Cycloalkyl radical C1-C8Alkoxy (or thio) radicals, C3-C8Cycloalkyl radical C1-C4alkyl oxy (or thio) radical, C5-C6Cycloalkyl radical C1-C8Alkoxy (or thio) radicals, C5-C6Cycloalkyl radical C1-C4An alkyloxy (or thio) group.
The term "C" as used herein6-CmAryl "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 C6-CmAs 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)6H5)。
In the present invention, R1、R2、R3And R4Are the same or different from each other and are selected from H, C1-C6Alkyl, halo C1-C6Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C6Alkyl and halo C1-C6The alkyl group is substituted one or more times. Preferably, R is1、R2、R3And R4Are the same or different from each other and are selected from H, C1-C4Alkyl, halo C1-C4Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C4Alkyl and halo C1-C4The alkyl group is substituted one or more times. It is especially preferred that R1And R2One of (1) and R3And R4One of them is H, the others are the same or different from each other and are selected from C1-C4Alkyl, fluoro C1-C4Alkyl, chloro C1-C4Alkyl and phenyl, the phenyl being optionally substituted by one or more substituents selected from halogen, C1-C4Alkyl and halo C1-C4The alkyl group is substituted one or more times.
In the present invention, R5、R6、R7、R8Identical or different from each other and selected from hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C20Alkyl radical, C2-C20alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18Aryl, wherein the aforementioned C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18The 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, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenyl and C2-C6Alkynyl. Preferably, R is5、R6、R7、R8Independently of one another, from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8Cycloalkylalkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8Cycloalkylthio radical, C4-C8Cycloalkylalkylthio and C6-C10Aryl, wherein the aforementioned C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8Cycloalkylalkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8Cycloalkylthio radical, C4-C8Cycloalkylalkylthio and C6-C10The 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, C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C2-C4Alkenyl and C2-C4Alkynyl. It is particularly preferred that R5、R6、R7、R8Independently of one another, from hydrogen, halogen, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group.
In the present invention, R9And R10Are the same or different from each other and are selected from H, C1-C6Alkyl and halo C1-C6An alkyl group. Preferably, R is9And R10Are the same or different from each other and are selected from H, C1-C4Alkyl and halo C1-C4Alkyl (e.g. chloro C)1-C4Alkyl, bromo C1-C4Alkyl groups).
Alternatively, R9And R10Together with the carbon atoms to which they are attached, may also form cycloalkyl groups containing a total of from 3 to 6 ring carbon atoms, preferably 5 to 6 ring carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl.
In the present invention, Y1And Y2Are identical or different from each other and are independently selected from H and a group of formula (X) provided that Y1Is not H:
Wherein is the site of attachment of the group of formula (X) in the compound of formula (I).
In the present invention, R14And R15Are the same or different from each other and are selected from H, C1-C6Alkyl and halo C1-C6An alkyl group. Preferably, R is14And R15Are the same or different from each other and are selected from H, C1-C4Alkyl and halo C1-C4alkyl (e.g. chloro C)1-C4Alkyl, bromo C1-C4Alkyl groups). It is particularly preferred that R14And R15Are all H.
In the present invention, R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17two R18Two R19and two R20Are also identical or different from each other and are selected from the group consisting of hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20Alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18Aryl, wherein the aforementioned C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C1-C20Alkoxy radical, C2-C20Alkenoxy group, C2-C20alkynyloxy, C3-C20Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C1-C20Alkylthio radical, C2-C20Alkenylthio radical, C2-C20Alkynylthio, C3-C20Cycloalkylthio radical, C4-C20Cycloalkylalkylthio and C6-C18The 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, C1-C6Alkyl radical, C1-C6alkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenyl and C2-C6Alkynyl. Preferably, R is16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from the group consisting of hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, amino, cyano, C1-C6alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8Cycloalkylalkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8Cycloalkylthio radical, C4-C8Cycloalkylalkylthio and C6-C10Aryl, wherein the aforementioned C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C1-C6alkoxy radical, C2-C6Alkenoxy group, C2-C6Alkynyloxy, C3-C8Cycloalkoxy, C4-C8Cycloalkylalkoxy radical, C1-C6Alkylthio radical, C2-C6Alkenylthio radical, C2-C6Alkynylthio, C3-C8Cycloalkylthio radical, C4-C8Cycloalkylalkylthio and C6-C10The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino,Cyano radicals, C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C2-C4Alkenyl and C2-C4Alkynyl. It is particularly preferred that R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from hydrogen, halogen, nitro, C1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C1-C4Alkoxy radical, C1-C4Alkylthio and phenyl, wherein C is as defined above1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C1-C4Alkoxy radical, C1-C4The alkylthio and phenyl groups may be optionally substituted with one or more groups independently selected from the group consisting of: halogen, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group. In particular, R16、R17、R18、R19And R20Are identical or different from each other if R16、R17、R18、R19And R20When there are two each, then two R16Two R17Two R18Two R19And two R20Are also identical or different from each other and are selected from hydrogen, halogen (e.g. fluorine, chlorine, bromine), nitro, C1-C4Alkyl radical, C1-C4Haloalkyl (e.g. chloro C)1-C4Alkyl, bromo C1-C4Alkyl group), C2-C4Alkenyl radical, C1-C4alkoxy radical, C1-C4Alkylthio and phenyl.
In a particularly preferred embodiment of the present invention, the compounds of formula (I) are selected from compounds 1 to 17 of the following group:
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 invention which comprises:
a) When Y is1And Y2Are the same group of formula (X) or when Y2when the compound is H, the compound of the formula (II) and the compound of the formula (III) are subjected to esterification reaction to obtain the compound of the formula (I),
b) When Y is1And Y2When the groups are different in formula (X), the compound in formula (II) is subjected to esterification reaction with different compounds in formula (III) in sequence to obtain the compound in formula (I),
Wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R14、R15、R16、R17、R18、R19And R20As defined for compounds of formula (I), and Y is halogen or hydroxy, especially chloro.
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.
When Y is hydroxy, in order to increase the yield of the compound of formula (I), it is advantageous to remove the water produced by the esterification reaction 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.
Y1And Y2Wherein both are the same group of formula (X) or when Y is2In the case of H, the preparation of the compound can be realized by controlling the raw material feeding ratio. Y is1And Y2In the case of different radicals of the formula (X), it is possible to react the compounds of the formula (II) successively with different compounds of the formula (III).
The present inventors have found that the compounds of formula (II) have different reactivity of the two hydroxyl groups, wherein the left hydroxyl group (i.e., to which R is attached)1And R2The hydroxyl group on the carbon) is more reactive than the hydroxyl group on the right side (i.e., attached with R)9And R10The hydroxyl group on carbon) of the compound of the present invention can be obtained by the order and the ratio of the compounds of the formula (III). The inventors have also found that when the molar ratio of compound of formula (II) to compound of formula (III) is from 2:1 to 1:1, preferably from 1.5:1 to 1:1, the ester formation reaction occurs predominantly with the attachment of R1And R2On a hydroxyl group on carbon.
When Y is1And Y2the molar ratio of compound of the formula (III) to compound of the formula (II) is generally 5:1-2:1, preferably 3:1 to 2: 1. When Y is2In the case of H, the molar ratio of the compound of the formula (III) to the compound of the formula (II) is generally from 3:1 to 1:1, preferably from 1.5:1 to 1: 1. When Y is1And Y2In the case of different radicals of the formula (X), the molar ratio of each compound of the formula (III) to the compound of the formula (II) is generally from 3:1 to 1:1, preferably from 1.5:1 to 1:1, and the target compound is obtained by controlling the order of addition, i.e. initially charging the compound to be bound with R1And R2after the compound of formula (III) is added to be reacted with the hydroxyl group on the carbon to which R is attached9And R10A hydroxyl group on the carbon of (III).
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 formula (I) of the invention comprises both an alpha-hydroxy ketone structural part (hydroxyl is already formed into ester or is not formed into ester) and a cinnamoyl structural part, so that the compound can play a role of a photoinitiator of alpha-hydroxy ketone, and the problems of peculiar smell, strong mobility and short ultraviolet absorption wavelength inherent in the alpha-hydroxy ketone photoinitiator are improved due to the introduction of the cinnamoyl structural part, so that the compound can be red-shifted to about 300-400nm, and preferably red-shifted to 350-400 nm.
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 300-400nm, especially 350-400 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.
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