WO2020000359A1 - Method for preparing methyl benzoylcinnamate compound - Google Patents
Method for preparing methyl benzoylcinnamate compound Download PDFInfo
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- WO2020000359A1 WO2020000359A1 PCT/CN2018/093645 CN2018093645W WO2020000359A1 WO 2020000359 A1 WO2020000359 A1 WO 2020000359A1 CN 2018093645 W CN2018093645 W CN 2018093645W WO 2020000359 A1 WO2020000359 A1 WO 2020000359A1
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- 0 *C(*c1c2c(*)c(*)c(*)c1*)(C2=O)OC(C(*)=C(*)c(c(*)c1*)c(*)c(*)c1O*)=O Chemical compound *C(*c1c2c(*)c(*)c(*)c1*)(C2=O)OC(C(*)=C(*)c(c(*)c1*)c(*)c(*)c1O*)=O 0.000 description 1
- GULVRROUDTUAGO-WOJGMQOQSA-N CC(C)(C(c(cc1)ccc1Sc1ccccc1)=O)OC(/C=C/c(cc1)ccc1OC)=O Chemical compound CC(C)(C(c(cc1)ccc1Sc1ccccc1)=O)OC(/C=C/c(cc1)ccc1OC)=O GULVRROUDTUAGO-WOJGMQOQSA-N 0.000 description 1
- HCQVTVPNLKHZHL-FMIVXFBMSA-N COc1ccc(/C=C/C(OCC(c2ccccc2)=O)=O)cc1 Chemical compound COc1ccc(/C=C/C(OCC(c2ccccc2)=O)=O)cc1 HCQVTVPNLKHZHL-FMIVXFBMSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
- C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
Definitions
- the invention relates to a method for preparing benzoyl methyl cinnamate compounds.
- Light-curing materials are widely accepted and concerned as a green, environmentally friendly, and low-energy-consumption environment-friendly material because of the absence or only a small amount of solvent volatilization during the curing process.
- light curing technology has been widely used in traditional fields such as coatings, inks, microelectronics, printing, etc. In addition, it is also used to prepare new fields such as laser video and three-dimensional components.
- Photoinitiators also known as photosensitizers or light curing agents, are an indispensable part of light curing technology. It is a type that can absorb energy of a certain wavelength in the ultraviolet region (250-400nm) or visible region (400-600nm). Compounds that generate free radicals, cations, etc., thereby initiating monomer polymerization, cross-linking and curing. In the photo-curing system, the photoinitiator generally accounts for 3-5%. Although the content is low, it is the key component among them, which plays a decisive role in the photo-curing speed.
- the photoinitiator must meet the requirements of different photo-curing conditions and applications.
- the main goals are: to improve light sensitivity, improve surface curing efficiency (anti-oxidation inhibition), improve deep curing performance, improve the solubility of photoinitiators in monomers and resins, and reduce toxicity and odor , Reduce the migration of uncured initiator after curing, reduce yellowing.
- Photoinitiators 1173 (2-hydroxy-2-methyl-1-phenylacetone) and 184 (1-hydroxycyclohexylbenzene) Methylphenone).
- Photoinitiator 1173 is a liquid and easy to use. It is the main initiator in various types of photocurable varnishes. It has excellent thermal stability, good yellowing resistance, and low price. The main disadvantage is that the benzaldehyde present in the photolysis products is defective. Smell, at the same time, it is more volatile and strong in migration.
- Photoinitiator 184 is a white powder with low volatility, but it also has the problems of ambiguity and strong migration of photolysis products.
- the double bond in cinnamoyl is opened under the action of ultraviolet light, and the double bonds on different molecules interact to form a four-membered ring, resulting in photodimerization and cross-linking.
- cross-linking occurs between the molecules in the exposed areas, forming a poorly soluble body-like network structure, the molecular properties of the unexposed areas remain unchanged, and differences in solubility occur in the developing solution. It is by using this characteristic that fine machining can be achieved.
- the inventors of the present invention have conducted extensive and in-depth research in the field of cinnamate benzoyl methyl esters, with a view to discovering a new synthetic method for cinnamate benzoyl methyl esters.
- the method has the advantages of easy availability of raw materials, reduced cost and improved yield.
- the inventors have discovered that a carboxylic acid compound and an organic halide can directly react under a catalyst to form a corresponding carboxylic acid ester compound.
- the raw materials for producing such photoinitiators are changed from ⁇ -monohydroxy ketones to ⁇ -monohaloalkyl ketone compounds, so that the production cost is greatly reduced and the yield is significantly improved.
- the present invention has been achieved based on the foregoing findings.
- an object of the present invention is to provide a new method for preparing benzoyl methyl cinnamate compounds.
- this method since ⁇ -monohaloalkyl ketone compounds are used instead of ⁇ -monohydroxy ketones as raw materials, the production cost is greatly reduced, and the yield is significantly improved.
- the benzoyl methyl cinnamate compound prepared by the present invention can be used as a photoinitiator, can absorb radiant heat in the range of 200-350nm, has good stability, is resistant to yellowing, and more importantly, this type of initiator Compared with existing ⁇ -monohydroxy ketone photoinitiators such as 1173 and 184, the problem of strong odor and strong migration is greatly improved, and the ultraviolet redshift is also achieved.
- R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 Alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and
- R 6 and R 7 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, or R 6 and R 7 together with the carbon atom to which they are attached form C 3 -C 8 cycloalkyl;
- R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 Alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio,
- R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, including contacting a compound of formula (II) with a compound of formula (III) to occur Ester formation reaction to obtain a compound of formula (I),
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are as defined above, and X is halogen , Especially chlorine or bromine.
- R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 4 alkyl and halo C 1 -C 4 alkyl, Preferably, R 13 and R 14 are both H.
- R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 Alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 Alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio,
- R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 Alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 Alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and
- R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio, wherein The aforementioned C 1 -C 4 alkyl group, C 1 -C 4 alkoxy group, and C 1 -C 4 alkylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio; and / or
- R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, wherein the aforementioned C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy And C 1 -C 4 alkylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy And C 1 -C 4 alkylthio.
- ester-forming catalyst is one selected from the group consisting of Or more: sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, silver carbonate, lithium carbonate, four Silver fluoroborate, sodium tetrafluoroborate, lithium tetrafluoroborate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, lithium hydride, calcium hydride, and tertiary amines, such as trialkylamines, such as trimethylamine and triamine Ethylamine.
- R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 Alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and
- R 6 and R 7 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, or R 6 and R 7 together with the carbon atom to which they are attached form C 3 -C 8 cycloalkyl;
- R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 Alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio,
- R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, including contacting a compound of formula (II) with a compound of formula (III) to occur Ester formation reaction to obtain a compound of formula (I),
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are as defined above, and X is halogen , Especially chlorine or bromine.
- the compound of formula (I) Due to the presence of ⁇ -monohydroxy ketone structural moiety in the compound of formula (I), the compound retains the characteristics of ⁇ -monohydroxy ketone photoinitiator, and the cinnamoyl structural moiety contained therein allows the compound to be exposed to ultraviolet light. Polymerization and cross-linking can occur under irradiation.
- the compound of formula (I) thus obtained retains the advantages of ⁇ -monohydroxy ketone photoinitiators while improving the odor and strong migration of ⁇ -monohydroxy ketone photoinitiators. The problem.
- C n -C m means in each case that the number of carbon atoms contained in the group is nm.
- Halogen means fluorine, chlorine, bromine and iodine. In the present invention, it is preferable that the halogen includes F, Cl, or a combination thereof.
- C n -C m alkyl as used herein means having nm, such as 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, and particularly preferably 1-4.
- Branched or unbranched saturated open-chain hydrocarbon groups of one carbon atom such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 , 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, Hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
- C 1 -C 8 alkyl may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl and Its isomer.
- the C 1 -C 6 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a 2-butyl group, a tert-butyl group, an pentyl group, an isopentyl group, a hexyl group, and isomers thereof.
- C 1 -C 4 alkyl may be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl And its isomers.
- C 2 -C m alkenyl refers to having 2-m, such as 2-20, preferably 2-6, more preferably 2-4 carbon atoms and having one or more at any position Branched or unbranched unsaturated open-chain hydrocarbon groups of double bonds such as vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3 -Butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl , 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butene 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl -3-butenyl, 3-methyl-3-butenyl, 2-methyl -3-buten
- C 2 -C 6 alkenyl may be vinyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, neopentenyl, 1-hexyl Alkenyl, 2-hexenyl, 3-hexenyl, isohexenyl, neohexenyl and its isomers.
- C 2 -C 4 alkenyl may be vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl Methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, and isomers thereof.
- C 2 -C m alkynyl as used herein means having 2 to m, such as 2 to 20, preferably 2 to 6, and more preferably 2 to 4 carbon atoms and having one or more at any position Branched or unbranched unsaturated open-chain hydrocarbon groups of triple bonds, such as ethynyl, propynyl, 1-butynyl, 2-butynyl and its isomers.
- C 2 -C 6 alkynyl 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.
- the C 2 -C 4 alkynyl may be ethynyl, propynyl, 1-butynyl, 2-butynyl, and isomers thereof.
- C 3 -C m cycloalkyl refers to a saturated alicyclic monocyclic group having 3-m, such as 3-20, preferably 3-8, more preferably 5-6 ring carbon atoms. Groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
- C 4 -C m cycloalkylalkyl refers to an alkyl group substituted with a cycloalkyl group and contains a total of 4-m carbon atoms, such as 4-20, preferably 4-8 carbon atoms, wherein the alkyl and Cycloalkyl is as defined herein, such as cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopropyl Butylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, and the like.
- C n -C m alkoxy and “C n -C m alkylthio" mean that an oxygen atom or a sulfur atom is bonded as a linking group at any valence of a C n -C m alkyl group C n -C m alkyl, such as C 1 -C 20 alkoxy (or sulfur), preferably C 1 -C 12 alkoxy (or sulfur), more preferably C 1 -C 8 alkoxy (or sulfur)
- the group is particularly preferably a C 1 -C 6 alkoxy (or sulfur) group, and particularly preferably a C 1 -C 4 alkoxy (or sulfur) group.
- C 1 -C 8 alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, t-butoxy, pentyloxy, isopentyloxy Group, hexyloxy, heptyloxy, octyloxy, isooctyloxy and its isomers.
- C 1 -C 4 alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and its isomers body.
- C 1 -C 8 alkylthio may be methylthio, ethylthio, propylthio, isopropylthio, n-butyl, 2-butylthio, tert-butylthio, pentylthio, isopentylthio , Hexylthio, heptylthio, octylthio, isooctylthio and its isomers.
- the C 1 -C 4 alkylthio group may be a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, an n-butylthio group and an isomer thereof.
- C 2 -C m alkenyloxy and “C 2 -C m alkenylthio” refer to an oxygen atom or a sulfur atom bonded to any saturated valence bond in a C 2 -C m alkenyl group C 2 -C m alkenyl as the linking group, for example, C 2 -C 20 alkenyloxy (or sulfur) group, preferably C 2 -C 12 alkenyloxy (or sulfur) group, more preferably C 2 -C 8 alkenyloxy (or sulfur) groups, particularly preferably a C 2 -C 6 alkenyloxy (or sulfur) group, and particularly preferably a C 2 -C 4 alkenyl (or sulfur) group.
- the C 1 -C 4 alkenyloxy group may be ethyleneoxy, propyleneoxy, isopropenyloxy, n-buteneoxy, sec-buteneoxy, isobutenyloxy, tert-butenyloxy and its isomers.
- the C 2 -C 4 alkenylthio group may be ethylenethio group, propylenethio group, isopropylenethio group, n-butenethio group and isomers thereof.
- C 2 -C m alkynyloxy and “C 2 -C m alkynylthio” refer to an oxygen atom or a sulfur atom as a link at any saturated valence bond in a C 2 -C m alkynyl group
- a C 2 -C m alkynyl group such as a C 2 -C 20 alkynyloxy (or sulfur) group, preferably a C 2 -C 12 alkynyloxy (or sulfur) group, more preferably a C 2 -C 8 alkynyloxy (or A thio) group, particularly preferably a C 2 -C 6 alkynyloxy (or sulfur) group, and particularly preferably a C 2 -C 4 alkynyl (or sulfur) group.
- the C 1 -C 4 alkynyloxy group may be ethynyloxy, propynyloxy, n-butynyloxy, sec-butynyloxy, and isomers thereof.
- the C 2 -C 4 alkynylthio group may be an ethynylthio group, a propynylthio group, a propynylthio group, an n-butynylthio group, a sec-butynylthio group, and isomers thereof.
- C 3 -C m cycloalkoxy and “C 3 -C m cycloalkylthio” refer to those having an oxygen atom or a sulfur atom bonded as a linking group at any valence bond in a cycloalkyl group.
- C 3 -C m cycloalkyl such as C 3 -C 20 cycloalkoxy (or sulfur), preferably C 3 -C 8 cycloalkoxy (or sulfur), more preferably C 5 -C 6 cycloalkoxy ( Or sulfur) group.
- C 3 -C 20 cycloalkoxy may be cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy And its isomers.
- C 3 -C 20 cycloalkylthio can be cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, cyclooctylthio, cyclodecylthio And its isomers.
- C 6 -C m aryl refers to a 6-m carbon atoms, e.g. 6-18, preferably 6-10 monocyclic carbon atoms, bicyclic or tricyclic aromatic hydrocarbon group.
- C 6 -C m aryl mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, methyl Propylphenyl, naphthyl, etc .; phenyl or naphthyl is preferred, especially phenyl (also known as C 6 H 5 as a substituent).
- R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, C 4
- R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 6 Alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2- C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio,
- R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 Alkylthio, wherein the aforementioned C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio can be optionally substituted with one or more groups independently selected from the group consisting of : Halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio.
- R 6 and R 7 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, or R 6 and R 7 are connected to them The carbon atoms together form a C 3 -C 8 cycloalkyl.
- R 6 and R 7 are the same or different and are independently selected from C 1 -C 4 alkyl and halo C 1 -C 4 alkyl, or R 6 and R 7 together with the carbon atom to which they are attached C 5 -C 6 cycloalkyl is formed.
- R 6 and R 7 are the same or different and are independently selected from methyl and halomethyl, or R 6 and R 7 together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl group.
- R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylalkyl
- R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfo, amino, cyano, C 1 -C 6 Alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2- C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio,
- R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from each other from hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 Alkynyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, wherein the aforementioned C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1- C 4 alkoxy and C 1 -C 4 alkylthio.
- R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl.
- R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 4 alkyl and halo C 1 -C 4 alkyl. It is particularly preferred that both R 13 and R 14 are H.
- the compound of formula (I) is selected from the group consisting of:
- an ortho-carbonyl haloalkane compound can be contacted with a carboxylic acid compound in the presence of a conventional esterification catalyst to form an ester group, and an ester-forming reaction occurs.
- the reaction is as follows:
- X is halogen, especially chlorine or bromine.
- the aforementioned esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction.
- a catalyst suitable for the esterification reaction either an acidic catalyst or a basic catalyst can be used.
- the catalyst one or more selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, and sodium carbonate can be used.
- the ester-forming reaction is performed in a stepwise manner.
- the compound of formula (III) is first contacted with the ester-forming catalyst A at -80 to 100 ° C for 0.5-20 hours, preferably at -80 to 50 ° C for 0.5-10 hours, and then the compound of formula (II) is added.
- the optional ester-forming catalyst B at -80 to 100 ° C for 0.5-10 hours, preferably at -80 to 30 ° C for 0.5-5 hours, and then hold at -10 to 50 ° C for 1-10 hours, Preferably, it is held at 0 to 30 ° C for an additional 1-4 hours so that an ester-forming reaction occurs.
- the purpose of the programmed temperature increase here is to ensure that the reaction can proceed gently.
- the purpose of contacting the compound of formula (III) with the ester-forming catalyst A is to activate the compound of formula (III), and the purpose of contacting the compound of formula (II) with the ester-forming catalyst B is also to activate the compound of formula (II) ) Compounds.
- the molar ratio of the ester-forming catalyst A to the compound of the formula (III) is usually 1: 1 to 6: 1, preferably 1: 1 to 3: 1.
- the molar ratio of the ester-forming catalyst B to the compound of the formula (II) is usually 1: 1 to 6: 1, preferably 1: 1 to 3: 1.
- the ester-forming catalyst A and the ester-forming catalyst B here may be the same or different, and the ester-forming catalyst described above is selected independently of each other.
- the above-mentioned ester-forming reaction is usually carried out in a solvent, preferably in an organic solvent.
- a solvent preferably in an organic solvent.
- the choice of the type of the solvent is not particularly limited, as long as the compounds of formula (II) and formula (III) can be dissolved and chemically inert to the ester-forming reaction, that is, they do not participate in the ester-forming reaction.
- the solvent mention may be made of tetrahydrofuran, benzene, toluene, N, N-dimethylformamide, dichloromethane and acetone.
- a single solvent may be used, or a mixture of two or more solvents may be used.
- the relative amounts of the compound of formula (II) and compound of formula (III) are not particularly limited. Generally, they are used in equal or substantially equimolar amounts. For example, the molar ratio of the compound of formula (II) to compound of formula (III) is 1.5: 1 to 1: 1.5, preferably 1.2: 1 to 1: 1.2.
- a terminator such as water is optionally added to terminate the reaction to obtain a reaction mixture comprising a compound of formula (I). Therefore, the reaction mixture needs to be worked up to obtain a purified compound of formula (I).
- the reaction mixture obtained by the ester-forming reaction is first filtered, and the filtrate portion is taken out.
- the filter residue may contain an insoluble ester-forming catalyst and the like. Part of the inorganic salt catalyst in the ester-forming catalyst is soluble in water, so it can be removed after washing with water, and the water-insoluble catalyst is removed by filtration.
- the organic base catalyst in the ester-forming catalyst it is necessary to add an appropriate amount of diluted hydrochloric acid for neutralization and then remove it by washing with water.
- the filtrate is subjected to extraction, and the extraction may be performed one or more times.
- any extractant capable of extracting the compound of the formula (I) can be used, such as dichloromethane.
- the extracted organic phase needs to be dried to remove residual water.
- anhydrous sodium sulfate can usually be used for drying. After drying, the remaining organic solvents were removed.
- the means for removing the organic solvent is not particularly limited, and the organic solvent can usually be removed by distillation under reduced pressure. After removal of the residual organic solvent, a crude product of the compound of formula (I) is obtained. If it is desired to further improve the purity of the compound of formula (I), the compound can be further purified, for example, by means of recrystallization.
- the choice of the recrystallization solvent is conventional and is not particularly limited. According to the invention, it is advantageous to recrystallize the crude product of the compound of formula (I) using methanol or ethanol.
- the compound of formula (I) prepared by the present invention contains both an ⁇ -hydroxyketone structure part and a cinnamoyl structure part, so the compound can play the role of a photoinitiator of the ⁇ -hydroxyketone type, and because the cinnamoyl structure part Introduced to improve the inherent odor and strong migration problems of ⁇ -hydroxyketone photoinitiators.
- the compound of formula (I) prepared by the present invention can absorb electromagnetic waves of 200-350 nm. After absorbing electromagnetic waves, the compound of formula (I) changes from the ground state to the excited state, so that the acyl carbon atom in the benzoyl structure part of the compound of formula (I) is broken with the carbon atom in the adjacent methoxy group, forming two free radicals. Groups, thereby initiating photopolymerization or photocrosslinking.
- the cinnamoyl structural part of the compound of formula (I) contains unsaturated carbon-carbon double bonds, the carbon-carbon double bonds between different molecules can easily react to form larger molecules or cross-linked structures when subjected to electromagnetic wave radiation, thereby greatly improving
- the problem of strong odor and migration caused by photoinitiators significantly reduces odor and significantly reduces migration.
- the compound of formula (I) prepared by the present invention can be used as a photoinitiator in the fields of coatings, inks, microelectronics, printing and the like, and in new fields such as laser video recording and three-dimensional components.
- the compound of formula (I) is used as a photoinitiator, its amount is conventional or can be determined through routine preliminary tests.
- Example 4a 4-phenyl-2-acrylic acid 4-methylthiophenylformyl isopropyl ester
- reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 25 g of yellow crystals was obtained, and the product was identified as the title compound by 1 H-NMR spectrum.
- reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry for 3 h, and then remove the organic phase by distillation under reduced pressure. A total of 18 g of pale yellow crystals were identified as the title compound by 1 H-NMR spectrum.
- Example 11a 3- (4-methoxy) phenyl-2- (1-benzoyl) ethyl acrylate
- the reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 22 g of pale yellow crystals were obtained. The product was identified by the 1 H-NMR spectrum as the title compound.
- the reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 17 g of pale yellow crystals were obtained. The product was identified as the title compound by 1 H-NMR spectrum.
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Abstract
The present invention relates to a method for preparing a methyl benzoylcinnamate compound in formula (I), comprising: making a compound as shown in formula (II) contact with a compound as shown in formula (III) to perform an ester formation reaction to obtain the compound as shown in formula (I), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and X are as defined in the description. According to the method of the present invention, the raw material for producing such photoinitiator is changed to an α-monohalogenoalkyl ketone compound from α-monohydroxyl ketone, so that production cost is lowered greatly, and the yield is increased evidently.
Description
本发明涉及一种制备肉桂酸苯甲酰基甲酯类化合物的方法。The invention relates to a method for preparing benzoyl methyl cinnamate compounds.
当今社会环境和能源问题日益突出，光固化材料由于其在固化过程中，没有或者只有少量的溶剂挥发，作为一种绿色、环保、能耗低的环境友好型材料被人们广泛接受和关注。目前，光固化技术已广泛应用在涂料、油墨、微电子、印刷等传统领域，另外还用于制备激光录像及三维元件等新型领域。Today's social environment and energy issues are becoming increasingly prominent. Light-curing materials are widely accepted and concerned as a green, environmentally friendly, and low-energy-consumption environment-friendly material because of the absence or only a small amount of solvent volatilization during the curing process. At present, light curing technology has been widely used in traditional fields such as coatings, inks, microelectronics, printing, etc. In addition, it is also used to prepare new fields such as laser video and three-dimensional components.
光引发剂又称光敏剂或光固化剂，是光固化技术中必不可少的部分，它是一类能在紫外光区(250-400nm)或可见光区(400-600nm)吸收一定波长的能量，产生自由基、阳离子等，从而引发单体聚合交联固化的化合物。在光固化体系中，光引发剂一般占3-5％，含量虽低，却是其中的关键组分，对光固化速度起决定作用。它关系到配方体系在光辐照时，低聚物及稀释剂能否迅速交联固化，从而由液态转变为固态。作为光固化体系的重要组分，光引发剂必须满足不同光固化条件和应用的需要。在自由基光引发剂领域，主要目标是：提高光敏感度，提高表面固化效率(抗氧阻聚)，提高深层固化性能，提高光引发剂在单体及树脂中的溶解性，降低毒性和气味，降低固化后未固化引发剂的迁移性，降低黄变性。Photoinitiators, also known as photosensitizers or light curing agents, are an indispensable part of light curing technology. It is a type that can absorb energy of a certain wavelength in the ultraviolet region (250-400nm) or visible region (400-600nm). Compounds that generate free radicals, cations, etc., thereby initiating monomer polymerization, cross-linking and curing. In the photo-curing system, the photoinitiator generally accounts for 3-5%. Although the content is low, it is the key component among them, which plays a decisive role in the photo-curing speed. It is related to whether the oligomer and diluent can be rapidly cross-linked and solidified when the formula system is irradiated with light, thereby changing from a liquid state to a solid state. As an important component of the photo-curing system, the photoinitiator must meet the requirements of different photo-curing conditions and applications. In the field of free radical photoinitiators, the main goals are: to improve light sensitivity, improve surface curing efficiency (anti-oxidation inhibition), improve deep curing performance, improve the solubility of photoinitiators in monomers and resins, and reduce toxicity and odor , Reduce the migration of uncured initiator after curing, reduce yellowing.
α-单羟基酮类光引发剂是常用的光引发剂，其中最常见的是光引发剂1173(2-羟基-2-甲基-1-苯基丙酮)和184(1-羟基环己基苯基甲酮)。光引发剂1173是液体，使用方便，在各类光固化清漆中是主引发剂，热稳定性优良，耐黄变性好，价格较低；缺点主要是，光解产物中存在的苯甲醛有不良气味，同时挥发性较大，迁移性强。光引发剂184是白色粉末，挥发性较低，但同样存在光解产物有异昧和迁移性强的问题。α-monohydroxy ketone photoinitiators are commonly used photoinitiators, the most common of which are photoinitiators 1173 (2-hydroxy-2-methyl-1-phenylacetone) and 184 (1-hydroxycyclohexylbenzene) Methylphenone). Photoinitiator 1173 is a liquid and easy to use. It is the main initiator in various types of photocurable varnishes. It has excellent thermal stability, good yellowing resistance, and low price. The main disadvantage is that the benzaldehyde present in the photolysis products is defective. Smell, at the same time, it is more volatile and strong in migration. Photoinitiator 184 is a white powder with low volatility, but it also has the problems of ambiguity and strong migration of photolysis products.
1954年Eastman-Kodak公司生产出了世界上最早的用合成高分子为原料的光刻胶—聚乙烯醇肉桂酸酯系负性光刻胶(US 2690966)。这是人 类最先应用在电子工业上的光刻胶，其光聚合反应的原理如下式所示：In 1954, Eastman-Kodak Company produced the world's earliest photoresist made of synthetic polymers—polyvinyl alcohol cinnamate negative photoresist (US 2690966). This is the first photoresist for humans to be used in the electronics industry. The principle of photopolymerization is shown below:
肉桂酰基中的双键在紫外光作用下打开，不同分子上的双键相互作用形成四元环，产生光二聚交联。这样，曝光区的分子间发生交联，形成难溶的体型网状结构，未曝光区的分子性质不变，在显影液中产生溶解性差异。正是利用这种特性可以实现微细加工。The double bond in cinnamoyl is opened under the action of ultraviolet light, and the double bonds on different molecules interact to form a four-membered ring, resulting in photodimerization and cross-linking. In this way, cross-linking occurs between the molecules in the exposed areas, forming a poorly soluble body-like network structure, the molecular properties of the unexposed areas remain unchanged, and differences in solubility occur in the developing solution. It is by using this characteristic that fine machining can be achieved.
基于此，本发明人发现了一种新的肉桂酸苯甲酰基甲酯类化合物(见PCT/CN2017/081258)，该化合物在保留了α-单羟基酮类光引发剂的优点的同时还改善了α-单羟基酮类光引发剂的异味和迁移性强的问题。为了合成该化合物，提出了使相应的α-单羟基酮类与相应的羧酸或酰卤化合物进行酯化反应而获得。然而，该合成工艺稍微复杂，原料为α-单羟基酮类光引发剂，相对于α-单羟基酮类光引发剂在生产成本上不占优势，因此还是需要开发一种原料易得、成本较低、产率提高的合成方法。Based on this, the present inventors have discovered a new cinnamate benzoyl methyl ester compound (see PCT / CN2017 / 081258), which retains the advantages of the α-monohydroxy ketone photoinitiator while also improving The problem of strong odor and migration of α-monohydroxy ketone photoinitiator was solved. In order to synthesize the compound, it is proposed that the corresponding α-monohydroxy ketones are obtained by esterification with the corresponding carboxylic acid or acid halide compound. However, the synthesis process is slightly complicated. The raw material is α-monohydroxy ketone photoinitiator. Compared with α-monohydroxy ketone photoinitiator, the production cost is not dominant. Therefore, it is still necessary to develop a raw material that is easy to obtain and cost. Lower, higher yield synthetic method.
发明内容Summary of the invention
鉴于现有技术的上述状况，本发明的发明人在肉桂酸苯甲酰基甲酯类化合物领域进行了广泛而又深入的研究，以期发现一种新的合成肉桂酸苯甲酰基甲酯类化合物的方法，该方法原料易得，成本降低，产率提高。本发明人发现：羧酸化合物和有机卤化物在催化剂催化下可直接发生反应，生成相应的羧酸酯化合物。通过该合成方法，生产此类光引发剂的原料由α-单羟基酮类变为α-单卤代烷基酮类化合物，从而生产成本大大降低，产率明显提高。本发明正是基于前述发现得以实现。In view of the above-mentioned conditions of the prior art, the inventors of the present invention have conducted extensive and in-depth research in the field of cinnamate benzoyl methyl esters, with a view to discovering a new synthetic method for cinnamate benzoyl methyl esters. The method has the advantages of easy availability of raw materials, reduced cost and improved yield. The inventors have discovered that a carboxylic acid compound and an organic halide can directly react under a catalyst to form a corresponding carboxylic acid ester compound. By this synthesis method, the raw materials for producing such photoinitiators are changed from α-monohydroxy ketones to α-monohaloalkyl ketone compounds, so that the production cost is greatly reduced and the yield is significantly improved. The present invention has been achieved based on the foregoing findings.
因此，本发明的一个目的是提供一种新的制备肉桂酸苯甲酰基甲酯类化合物的方法。该方法由于采用了α-单卤代烷基酮类化合物代替α-单羟基 酮类作为原料，从而使得生产成本大大降低，产率明显提高。Therefore, an object of the present invention is to provide a new method for preparing benzoyl methyl cinnamate compounds. In this method, since α-monohaloalkyl ketone compounds are used instead of α-monohydroxy ketones as raw materials, the production cost is greatly reduced, and the yield is significantly improved.
本发明制备的肉桂酸苯甲酰基甲酯类化合物可用作光引发剂，能够吸收200-350nm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-单羟基酮类光引发剂比如1173和184，大大改善了异味和迁移性强的问题，而且紫外红移。The benzoyl methyl cinnamate compound prepared by the present invention can be used as a photoinitiator, can absorb radiant heat in the range of 200-350nm, has good stability, is resistant to yellowing, and more importantly, this type of initiator Compared with existing α-monohydroxy ketone photoinitiators such as 1173 and 184, the problem of strong odor and strong migration is greatly improved, and the ultraviolet redshift is also achieved.
实现本发明上述目的的技术方案可以概括如下：The technical solution to achieve the above-mentioned objective of the present invention can be summarized as follows:
1.一种制备式(I)的肉桂酸苯甲酰基甲酯类化合物的方法：1. A method for preparing benzoyl methyl cinnamate compounds of formula (I):
其中among them
R
1、R
2、R
3、R
4和R
5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基，其中前述C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
2-C
6链烯基和C
2-C
6炔基；
R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 Alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl, wherein the aforementioned C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl groups May be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, thiol, carboxyl, sulfonic, Group, a cyano group, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group;
R
6和R
7相同或不同且彼此独立地选自H、C
1-C
6烷基和卤代C
1-C
6烷基，或者R
6和R
7与它们所连接的碳原子一起形成C
3-C
8环烷基；
R 6 and R 7 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, or R 6 and R 7 together with the carbon atom to which they are attached form C 3 -C 8 cycloalkyl;
R
8、R
9、R
10、R
11和R
12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、 C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基，其中前述C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
2-C
6链烯基和C
2-C
6炔基；以及
R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 Alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl, wherein the aforementioned C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl groups May be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, thiol, carboxyl, sulfonic acid , Amino, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl, and C 2 -C 6 alkynyl; and
R
13和R
14相同或不同且彼此独立地选自H、C
1-C
6烷基和卤代C
1-C
6烷基，包括使式(II)化合物与式(III)化合物接触以发生成酯反应，得到式(I)化合物，
R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, including contacting a compound of formula (II) with a compound of formula (III) to occur Ester formation reaction to obtain a compound of formula (I),
其中R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12、R
13和R
14如上所定义，以及X为卤素，尤其是氯或溴。
Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are as defined above, and X is halogen , Especially chlorine or bromine.
2.根据第1项的方法，其中R
6和R
7相同或不同且彼此独立地选自C
1-C
4烷基和卤代C
1-C
4烷基，或者R
6和R
7与它们所连接的碳原子一起形成C
5-C
6环烷基。
2. The method according to item 1, wherein R 6 and R 7 are the same or different and are independently selected from C 1 -C 4 alkyl and halogenated C 1 -C 4 alkyl, or R 6 and R 7 and them The attached carbon atoms together form a C 5 -C 6 cycloalkyl.
3.根据第2项的方法，其中R
6和R
7相同或不同且彼此独立地选自甲基和卤代甲基，或者R
6和R
7与它们所连接的碳原子一起形成环戊基或环己基。
3. The method according to item 2, wherein R 6 and R 7 are the same or different and are independently selected from methyl and halomethyl, or R 6 and R 7 together with the carbon atom to which they are attached form a cyclopentyl group Or cyclohexyl.
4.根据第1-3项中任一项的方法，其中R
13和R
14相同或不同且彼此独立地选自H、C
1-C
4烷基和卤代C
1-C
4烷基，优选R
13和R
14均为H。
4. The method according to any one of items 1-3, wherein R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 4 alkyl and halo C 1 -C 4 alkyl, Preferably, R 13 and R 14 are both H.
5.根据第1-4项中任一项的方法，其中5. The method according to any one of items 1-4, wherein
R
1、R
2、R
3、R
4和R
5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧 基、磺酸基、氨基、氰基、C
1-C
6烷基、C
2-C
6链烯基、C
2-C
6炔基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
1-C
6烷氧基、C
2-C
6链烯氧基、C
2-C
6炔氧基、C
3-C
8环烷氧基、C
4-C
8环烷基烷氧基、C
1-C
6烷硫基、C
2-C
6链烯硫基、C
2-C
6炔硫基、C
3-C
8环烷硫基、C
4-C
8环烷基烷硫基和C
6-C
10芳基，其中前述C
1-C
6烷基、C
2-C
6链烯基、C
2-C
6炔基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
1-C
6烷氧基、C
2-C
6链烯氧基、C
2-C
6炔氧基、C
3-C
8环烷氧基、C
4-C
8环烷基烷氧基、C
1-C
6烷硫基、C
2-C
6链烯硫基、C
2-C
6炔硫基、C
3-C
8环烷硫基、C
4-C
8环烷基烷硫基和C
6-C
10芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基、C
2-C
4链烯基和C
2-C
4炔基；和/或
R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 Alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 Alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 aryl, wherein the aforementioned C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 aryl groups may be optionally substituted with one or more groups independently selected from the group: halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 4 alkoxy , C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl; and / or
R
8、R
9、R
10、R
11和R
12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
6烷基、C
2-C
6链烯基、C
2-C
6炔基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
1-C
6烷氧基、C
2-C
6链烯氧基、C
2-C
6炔氧基、C
3-C
8环烷氧基、C
4-C
8环烷基烷氧基、C
1-C
6烷硫基、C
2-C
6链烯硫基、C
2-C
6炔硫基、C
3-C
8环烷硫基、C
4-C
8环烷基烷硫基和C
6-C
10芳基，其中前述C
1-C
6烷基、C
2-C
6链烯基、C
2-C
6炔基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
1-C
6烷氧基、C
2-C
6链烯氧基、C
2-C
6炔氧基、C
3-C
8环烷氧基、C
4-C
8环烷基烷氧基、C
1-C
6烷硫基、C
2-C
6链烯硫基、C
2-C
6炔硫基、C
3-C
8环烷硫基、C
4-C
8环烷基烷硫基和C
6-C
10芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基、C
2-C
4链烯基和C
2-C
4炔基。
R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 Alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 Alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 aryl, wherein the aforementioned C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 aryl groups It may be optionally substituted with one or more groups independently selected from the group: halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 4 Group, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl group.
6.根据第1-4项中任一项的方法，其中6. The method according to any one of items 1-4, wherein
R
1、R
2、R
3、R
4和R
5彼此独立地选自氢、卤素、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基，其中前述C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基可任选地被一个或多个独立地选自下组的基团取代：卤素、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基；和/或
R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio, wherein The aforementioned C 1 -C 4 alkyl group, C 1 -C 4 alkoxy group, and C 1 -C 4 alkylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio; and / or
R
8、R
9、R
10、R
11和R
12彼此独立地选自氢、卤素、C
1-C
4烷基、C
2-C
4链 烯基、C
2-C
4炔基、C
1-C
4烷氧基和C
1-C
4烷硫基，其中前述C
1-C
4烷基、C
2-C
4链烯基、C
2-C
4炔基、C
1-C
4烷氧基和C
1-C
4烷硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基。
R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, wherein the aforementioned C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy And C 1 -C 4 alkylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy And C 1 -C 4 alkylthio.
7.根据第1项的方法，其中式(I)化合物选自下组：7. The method according to item 1, wherein the compound of formula (I) is selected from the group consisting of:
8.根据第1-7项中任一项的方法，其中式(II)化合物与式(II)化合物的接触在成酯催化剂存在下进行，优选该成酯催化剂为选自下组的一种或多种：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸银、碳酸锂、四氟硼酸银、四氟硼酸钠、四氟硼酸锂、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化锂、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。8. The method according to any one of items 1 to 7, wherein the contacting of the compound of the formula (II) with the compound of the formula (II) is performed in the presence of an ester-forming catalyst, preferably the ester-forming catalyst is one selected from the group consisting of Or more: sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, silver carbonate, lithium carbonate, four Silver fluoroborate, sodium tetrafluoroborate, lithium tetrafluoroborate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, lithium hydride, calcium hydride, and tertiary amines, such as trialkylamines, such as trimethylamine and triamine Ethylamine.
9.根据第1-8项中任一项的方法，其中先将式(III)化合物与成酯催化剂A在-80至100℃下接触0.5-20小时，优选在-80至50℃下接触0.5-10小时，然后加入式(II)化合物和任选的成酯催化剂B在-80至100℃下接触0.5-10小时，优选在-80至30℃下接触0.5-5小时，之后再在-10至50℃下保持1-10小时，优选再在0至30℃下保持1-4小时，以发生成酯反应，其中成酯催化剂A和成酯催化剂B相同或不同。9. The method according to any one of items 1 to 8, wherein the compound of formula (III) is first contacted with the ester-forming catalyst A at -80 to 100 ° C for 0.5-20 hours, preferably at -80 to 50 ° C. 0.5-10 hours, then add the compound of formula (II) and optional ester-forming catalyst B to contact at -80 to 100 ° C for 0.5-10 hours, preferably at -80 to 30 ° C for 0.5-5 hours, and then It is held at -10 to 50 ° C for 1-10 hours, preferably at 0 to 30 ° C for 1 to 4 hours, in order to cause an esterification reaction, wherein the esterification catalyst A and the esterification catalyst B are the same or different.
10.根据第9项的方法，其中成酯催化剂A与式(III)化合物的摩尔比为1:1至6:1，优选1:1至3:1；和/或，成酯催化剂B与式(II)化合物的摩尔比为1:1至6:1，优选1:1至3:1。10. The method according to item 9, wherein the molar ratio of the ester-forming catalyst A to the compound of formula (III) is 1: 1 to 6: 1, preferably 1: 1 to 3: 1; and / or, the ester-forming catalyst B and The molar ratio of the compound of formula (II) is 1: 1 to 6: 1, preferably 1: 1 to 3: 1.
本发明的这些和其它目的、特征和优点在结合下文考虑本发明后，将易于为普通技术人员所明白。These and other objects, features, and advantages of the present invention will be readily understood by those of ordinary skill after considering the present invention in conjunction with the following.
根据本发明，提供了一种制备下式(I)的肉桂酸苯甲酰基甲酯类化合物的方法：According to the present invention, a method for preparing a benzoyl methyl cinnamate compound of the following formula (I) is provided:
其中among them
R
1、R
2、R
3、R
4和R
5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基，其中前述C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
2-C
6链烯基和C
2-C
6炔基；
R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 Alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl, wherein the aforementioned C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl groups May be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, thiol, carboxyl, sulfonic, Group, a cyano group, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group;
R
6和R
7相同或不同且彼此独立地选自H、C
1-C
6烷基和卤代C
1-C
6烷基，或者R
6和R
7与它们所连接的碳原子一起形成C
3-C
8环烷基；
R 6 and R 7 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, or R 6 and R 7 together with the carbon atom to which they are attached form C 3 -C 8 cycloalkyl;
R
8、R
9、R
10、R
11和R
12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基，其中前述C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18 芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
2-C
6链烯基和C
2-C
6炔基；以及
R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 Alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl, wherein the aforementioned C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl groups May be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, thiol, carboxyl, sulfonic acid Amino, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group;
R
13和R
14相同或不同且彼此独立地选自H、C
1-C
6烷基和卤代C
1-C
6烷基，包括使式(II)化合物与式(III)化合物接触以发生成酯反应，得到式(I)化合物，
R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, including contacting a compound of formula (II) with a compound of formula (III) to occur Ester formation reaction to obtain a compound of formula (I),
其中R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12、R
13和R
14如上所定义，以及X为卤素，尤其是氯或溴。
Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are as defined above, and X is halogen , Especially chlorine or bromine.
式(I)化合物中由于α-单羟基酮类结构部分的存在，使得该化合物保留了α-单羟基酮类光引发剂的特性，另外其中包含的肉桂酰基结构部分使得该化合物能够在紫外光辐射下可发生聚合交联，如此得到的式(I)化合物在保留了α-单羟基酮类光引发剂的优点的同时还改善了α-单羟基酮类光引发剂的异味和迁移性强的问题。Due to the presence of α-monohydroxy ketone structural moiety in the compound of formula (I), the compound retains the characteristics of α-monohydroxy ketone photoinitiator, and the cinnamoyl structural moiety contained therein allows the compound to be exposed to ultraviolet light. Polymerization and cross-linking can occur under irradiation. The compound of formula (I) thus obtained retains the advantages of α-monohydroxy ketone photoinitiators while improving the odor and strong migration of α-monohydroxy ketone photoinitiators. The problem.
在本发明中，前缀“C
n-C
m”在每种情况下表示该基团中包含的碳原子数为n-m个。
In the present invention, the prefix "C n -C m " means in each case that the number of carbon atoms contained in the group is nm.
“卤素”是指氟、氯、溴和碘。在本发明中，优选的是，卤素包括F、Cl或其组合。"Halogen" means fluorine, chlorine, bromine and iodine. In the present invention, it is preferable that the halogen includes F, Cl, or a combination thereof.
本文所用的术语“C
n-C
m烷基”是指具有n-m个，例如1-20个，优选1-12个，更优选1-8个，特别优选1-6个，尤其优选1-4个碳原子的支化或未支化饱和开链烃基，例如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、庚基、辛基、2-乙 基己基、壬基、癸基、十一烷基、十二烷基及其异构体。C
1-C
8烷基可以是甲基、乙基、丙基、异丙基、正丁基、2-丁基、叔丁基、戊基、异戊基、己基、庚基、辛基及其异构体。C
1-C
6烷基可以是甲基、乙基、丙基、异丙基、正丁基、2-丁基、叔丁基、戊基、异戊基、己基及其异构体。C
1-C
4烷基可以是甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基及其异构体。
The term "C n -C m alkyl" as used herein means having nm, such as 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, and particularly preferably 1-4. Branched or unbranched saturated open-chain hydrocarbon groups of one carbon atom, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 , 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, Hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1- Ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and Its isomer. C 1 -C 8 alkyl may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl and Its isomer. The C 1 -C 6 alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a 2-butyl group, a tert-butyl group, an pentyl group, an isopentyl group, a hexyl group, and isomers thereof. C 1 -C 4 alkyl may be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl And its isomers.
本文所用术语“C
2-C
m链烯基”是指具有2-m个，例如2-20个，优选2-6个，更优选2-4个碳原子并且具有一个或多个位于任何位置的双键的支化或未支化不饱和开链烃基，如乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-甲基-1-丁烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、1-甲基-2-丁烯基、2-甲基-2-丁烯基、3-甲基-2-丁烯基、1-甲基-3-丁烯基、2-甲基-3-丁烯基、3-甲基-3-丁烯基、1,1-二甲基-2-丙烯基、1,2-二甲基-1-丙烯基、1,2-二甲基-2-丙烯基、1-乙基-1-丙烯基、1-乙基-2-丙烯基、1-己烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、1-甲基-1-戊烯基、2-甲基-1-戊烯基、3-甲基-1-戊烯基、4-甲基-1-戊烯基、1-甲基-2-戊烯基、2-甲基-2-戊烯基、3-甲基-2-戊烯基、4-甲基-2-戊烯基、1-甲基-3-戊烯基、2-甲基-3-戊烯基、3-甲基-3-戊烯基、4-甲基-3-戊烯基、1-甲基-4-戊烯基、2-甲基-4-戊烯基、3-甲基-4-戊烯基、4-甲基-4-戊烯基、1,1-二甲基-2-丁烯基、1,1-二甲基-3-丁烯基、1,2-二甲基-1-丁烯基、1,2-二甲基-2-丁烯基、1,2-二甲基-3-丁烯基、1,3-二甲基-1-丁烯基、1,3-二甲基-2-丁烯基、1,3-二甲基-3-丁烯基、2,2-二甲基-3-丁烯基、2,3-二甲基-1-丁烯基、2,3-二甲基-2-丁烯基、2,3-二甲基-3-丁烯基、3,3-二甲基-1-丁烯基、3,3-二甲基-2-丁烯基、1-乙基-1-丁烯基、1-乙基-2-丁烯基、1-乙基-3-丁烯基、2-乙基-1-丁烯基、2-乙基-2-丁烯基、2-乙基-3-丁烯基、1,1,2-三甲基-2-丙烯基、1-乙基-1-甲基-2-丙烯基、1-乙基-2-甲基-1-丙烯基、1-乙基-2-甲基-2-丙烯基及其异构体。C
2-C
6烯基可以是乙烯基、丙烯基、1-丁烯基、2-丁烯基、异丁烯基、1-戊烯基、2-戊烯基、新戊烯基、1-己烯基、2-己烯基、3-己烯基、异己烯基、新己烯基及其异构体。 C
2-C
4烯基可以是乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基及其异构体。
As used herein, the term "C 2 -C m alkenyl" refers to having 2-m, such as 2-20, preferably 2-6, more preferably 2-4 carbon atoms and having one or more at any position Branched or unbranched unsaturated open-chain hydrocarbon groups of double bonds such as vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3 -Butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl , 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butene 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl -3-butenyl, 3-methyl-3-butenyl, 1,1-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, 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, 1,1-dimethyl-3-butenyl, 1,2-dimethyl Methyl-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, 2,2-dimethyl-3-butenyl, 2,3-dimethyl- 1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3, 3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl- 1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-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 6 alkenyl may be vinyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, neopentenyl, 1-hexyl Alkenyl, 2-hexenyl, 3-hexenyl, isohexenyl, neohexenyl and its isomers. C 2 -C 4 alkenyl may be vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl Methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, and isomers thereof.
本文所用术语“C
2-C
m炔基”是指具有2-m个，例如2-20个，优选2-6个，更优选2-4个碳原子并且具有一个或多个位于任何位置的叁键的支化或未支化不饱和开链烃基，如乙炔基、丙炔基、1-丁炔基、2-丁炔基及其异构体。C
2-C
6炔基可以是乙炔基、丙炔基、1-丁炔基、2-丁炔基、1-戊炔基、2-戊炔基、3-戊炔基、4-戊炔基、1-己炔基、2-己炔基、3-己炔基、4-己炔基、5-己炔基及其异构体。C
2-C
4炔基可以是乙炔基、丙炔基、1-丁炔基、2-丁炔基及其异构体。
The term "C 2 -C m alkynyl" as used herein means having 2 to m, such as 2 to 20, preferably 2 to 6, and more preferably 2 to 4 carbon atoms and having one or more at any position Branched or unbranched unsaturated open-chain hydrocarbon groups of triple bonds, such as ethynyl, propynyl, 1-butynyl, 2-butynyl and its isomers. C 2 -C 6 alkynyl 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. The C 2 -C 4 alkynyl may be ethynyl, propynyl, 1-butynyl, 2-butynyl, and isomers thereof.
本文所用术语“C
3-C
m环烷基”是指具有3-m个，例如3-20个，优选3-8个，更优选5-6个环碳原子的饱和脂环族单环基团，例如环丙基、环丁基、环戊基、环己基、环庚基、环辛基和环癸基。
The term "C 3 -C m cycloalkyl" as used herein refers to a saturated alicyclic monocyclic group having 3-m, such as 3-20, preferably 3-8, more preferably 5-6 ring carbon atoms. Groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
术语“C
4-C
m环烷基烷基”表示被环烷基取代的烷基并且总共含有4-m个碳原子，例如4-20个，优选4-8个碳原子，其中烷基和环烷基适用本文所定义，例如环丙基甲基、环丙基乙基、环丙基丙基、环丙基丁基、环丁基甲基、环丁基乙基、环丁基丙基、环丁基丁基、环戊基甲基、环戊基乙基、环戊基丙基、环戊基丁基、环己基甲基、环己基乙基、环己基丙基、环己基丁基等。
The term "C 4 -C m cycloalkylalkyl" refers to an alkyl group substituted with a cycloalkyl group and contains a total of 4-m carbon atoms, such as 4-20, preferably 4-8 carbon atoms, wherein the alkyl and Cycloalkyl is as defined herein, such as cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopropyl Butylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, and the like.
“C
n-C
m烷氧基”和“C
n-C
m烷硫基”是指在C
n-C
m烷基的任何价键处键合有一个氧原子或一个硫原子作为连接基团的C
n-C
m烷基，例如C
1-C
20烷氧(或硫)基，优选C
1-C
12烷氧(或硫)基，更优选C
1-C
8烷氧(或硫)基，特别优选C
1-C
6烷氧(或硫)基，尤其优选C
1-C
4烷氧(或硫)基。C
1-C
8烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基、庚氧基、辛氧基、异辛氧基及其异构体。C
1-C
4烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基及其异构体。C
1-C
8烷硫基可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁基、2-丁硫基、叔丁硫基、戊硫基、异戊硫基、己硫基、庚硫基、辛硫基、异辛硫基及其异构体。C
1-C
4烷硫基 可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基及其异构体。
"C n -C m alkoxy" and "C n -C m alkylthio" mean that an oxygen atom or a sulfur atom is bonded as a linking group at any valence of a C n -C m alkyl group C n -C m alkyl, such as C 1 -C 20 alkoxy (or sulfur), preferably C 1 -C 12 alkoxy (or sulfur), more preferably C 1 -C 8 alkoxy (or sulfur) The group is particularly preferably a C 1 -C 6 alkoxy (or sulfur) group, and particularly preferably a C 1 -C 4 alkoxy (or sulfur) group. C 1 -C 8 alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, t-butoxy, pentyloxy, isopentyloxy Group, hexyloxy, heptyloxy, octyloxy, isooctyloxy and its isomers. C 1 -C 4 alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and its isomers body. C 1 -C 8 alkylthio may be methylthio, ethylthio, propylthio, isopropylthio, n-butyl, 2-butylthio, tert-butylthio, pentylthio, isopentylthio , Hexylthio, heptylthio, octylthio, isooctylthio and its isomers. The C 1 -C 4 alkylthio group may be a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, an n-butylthio group and an isomer thereof.
“C
2-C
m链烯氧基”和“C
2-C
m链烯硫基”是指在C
2-C
m烯基中的任何饱和价键处键合有一个氧原子或一个硫原子作为连接基团的C
2-C
m链烯基，例如C
2-C
20链烯氧(或硫)基，优选C
2-C
12链烯氧(或硫)基，更优选C
2-C
8链烯氧(或硫)基，特别优选C
2-C
6链烯氧(或硫)基，尤其优选C
2-C
4链烯氧(或硫)基。C
1-C
4链烯氧基可以是乙烯氧基、丙烯氧基、异丙烯氧基、正丁烯氧基、仲丁烯氧基、异丁烯氧基、叔丁烯氧基及其异构体。C
2-C
4链烯硫基可以是乙烯硫基、丙烯硫基、异丙烯硫基、正丁烯硫基及其异构体。
"C 2 -C m alkenyloxy" and "C 2 -C m alkenylthio" refer to an oxygen atom or a sulfur atom bonded to any saturated valence bond in a C 2 -C m alkenyl group C 2 -C m alkenyl as the linking group, for example, C 2 -C 20 alkenyloxy (or sulfur) group, preferably C 2 -C 12 alkenyloxy (or sulfur) group, more preferably C 2 -C 8 alkenyloxy (or sulfur) groups, particularly preferably a C 2 -C 6 alkenyloxy (or sulfur) group, and particularly preferably a C 2 -C 4 alkenyl (or sulfur) group. The C 1 -C 4 alkenyloxy group may be ethyleneoxy, propyleneoxy, isopropenyloxy, n-buteneoxy, sec-buteneoxy, isobutenyloxy, tert-butenyloxy and its isomers. . The C 2 -C 4 alkenylthio group may be ethylenethio group, propylenethio group, isopropylenethio group, n-butenethio group and isomers thereof.
“C
2-C
m炔氧基”和“C
2-C
m炔硫基”是指在C
2-C
m炔基中的任何饱和价键处键合有一个氧原子或一个硫原子作为连接基团的C
2-C
m炔基，例如C
2-C
20炔氧(或硫)基，优选C
2-C
12炔氧(或硫)基，更优选C
2-C
8炔氧(或硫)基，特别优选C
2-C
6炔氧(或硫)基，尤其优选C
2-C
4炔氧(或硫)基。C
1-C
4炔氧基可以是乙炔氧基、丙炔氧基、正丁炔氧基、仲丁炔氧基及其异构体。C
2-C
4炔硫基可以是乙炔硫基、丙炔硫基、丙炔硫基、正丁炔硫基、仲丁炔硫基及其异构体。
"C 2 -C m alkynyloxy" and "C 2 -C m alkynylthio" refer to an oxygen atom or a sulfur atom as a link at any saturated valence bond in a C 2 -C m alkynyl group A C 2 -C m alkynyl group, such as a C 2 -C 20 alkynyloxy (or sulfur) group, preferably a C 2 -C 12 alkynyloxy (or sulfur) group, more preferably a C 2 -C 8 alkynyloxy (or A thio) group, particularly preferably a C 2 -C 6 alkynyloxy (or sulfur) group, and particularly preferably a C 2 -C 4 alkynyl (or sulfur) group. The C 1 -C 4 alkynyloxy group may be ethynyloxy, propynyloxy, n-butynyloxy, sec-butynyloxy, and isomers thereof. The C 2 -C 4 alkynylthio group may be an ethynylthio group, a propynylthio group, a propynylthio group, an n-butynylthio group, a sec-butynylthio group, and isomers thereof.
“C
3-C
m环烷氧基”和“C
3-C
m环烷硫基”是指在环烷基中的任何价键处键合有一个氧原子或一个硫原子作为连接基团的C
3-C
m环烷基，例如C
3-C
20环烷氧(或硫)基，优选C
3-C
8环烷氧(或硫)基，更优选C
5-C
6环烷氧(或硫)基。C
3-C
20环烷氧基可以是环丙基氧基、环丁基氧基、环戊基氧基、环己基氧基、环庚基氧基、环辛基氧基、环癸基氧基及其异构体。C
3-C
20环烷硫基可以是环丙基硫基、环丁基硫基、环戊基硫基、环己基硫基、环庚基硫基、环辛基硫基、环癸基硫基及其异构体。
"C 3 -C m cycloalkoxy" and "C 3 -C m cycloalkylthio" refer to those having an oxygen atom or a sulfur atom bonded as a linking group at any valence bond in a cycloalkyl group. C 3 -C m cycloalkyl, such as C 3 -C 20 cycloalkoxy (or sulfur), preferably C 3 -C 8 cycloalkoxy (or sulfur), more preferably C 5 -C 6 cycloalkoxy ( Or sulfur) group. C 3 -C 20 cycloalkoxy may be cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy And its isomers. C 3 -C 20 cycloalkylthio can be cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, cyclooctylthio, cyclodecylthio And its isomers.
本文所用术语“C
6-C
m芳基”是指含有6-m个碳原子，例如6-18个，优选6-10个碳原子的单环、双环或三环芳族烃基。作为C
6-C
m芳基的实例，可提及苯基、甲苯基、乙苯基、丙苯基、丁苯基、二甲苯基、甲基乙基苯基、二乙基苯基、甲基丙基苯基和萘基等；优选苯基或萘基，尤其是苯基(作为取代基也称为C
6H
5)。
As used herein, the term "C 6 -C m aryl" refers to a 6-m carbon atoms, e.g. 6-18, preferably 6-10 monocyclic carbon atoms, bicyclic or tricyclic aromatic hydrocarbon group. As examples of C 6 -C m aryl, mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, methyl Propylphenyl, naphthyl, etc .; phenyl or naphthyl is preferred, especially phenyl (also known as C 6 H 5 as a substituent).
在本发明中，R
1、R
2、R
3、R
4和R
5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
20烷基、C
2-C
20链烯基、 C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基，其中前述C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
2-C
6链烯基和C
2-C
6炔基。优选的是，R
1、R
2、R
3、R
4和R
5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
6烷基、C
2-C
6链烯基、C
2-C
6炔基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
1-C
6烷氧基、C
2-C
6链烯氧基、C
2-C
6炔氧基、C
3-C
8环烷氧基、C
4-C
8环烷基烷氧基、C
1-C
6烷硫基、C
2-C
6链烯硫基、C
2-C
6炔硫基、C
3-C
8环烷硫基、C
4-C
8环烷基烷硫基和C
6-C
10芳基，其中前述C
1-C
6烷基、C
2-C
6链烯基、C
2-C
6炔基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
1-C
6烷氧基、C
2-C
6链烯氧基、C
2-C
6炔氧基、C
3-C
8环烷氧基、C
4-C
8环烷基烷氧基、C
1-C
6烷硫基、C
2-C
6链烯硫基、C
2-C
6炔硫基、C
3-C
8环烷硫基、C
4-C
8环烷基烷硫基和C
6-C
10芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基、C
2-C
4链烯基和C
2-C
4炔基。特别优选的是，R
1、R
2、R
3、R
4和R
5彼此独立地选自氢、卤素、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基，其中前述C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基可任选地被一个或多个独立地选自下组的基团取代：卤素、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4烷硫基。
In the present invention, R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl, where The aforementioned C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C The 18 aryl group can be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, thiol, carboxyl Sulfo, sulfo, amino, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group. Preferably, R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 6 Alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2- C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 aryl, wherein C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 Alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 Alkylthio, C 2 -C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl group. It is particularly preferred that R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 Alkylthio, wherein the aforementioned C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio can be optionally substituted with one or more groups independently selected from the group consisting of : Halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio.
在本发明中，R
6和R
7相同或不同且彼此独立地选自H、C
1-C
6烷基和卤代C
1-C
6烷基，或者R
6和R
7与它们所连接的碳原子一起形成C
3-C
8环烷基。优选的是，R
6和R
7相同或不同且彼此独立地选自C
1-C
4烷基和卤代C
1-C
4烷基，或者R
6和R
7与它们所连接的碳原子一起形成C
5-C
6环烷基。 特别优选的是，R
6和R
7相同或不同且彼此独立地选自甲基和卤代甲基，或者R
6和R
7与它们所连接的碳原子一起形成环戊基或环己基。
In the present invention, R 6 and R 7 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, or R 6 and R 7 are connected to them The carbon atoms together form a C 3 -C 8 cycloalkyl. Preferably, R 6 and R 7 are the same or different and are independently selected from C 1 -C 4 alkyl and halo C 1 -C 4 alkyl, or R 6 and R 7 together with the carbon atom to which they are attached C 5 -C 6 cycloalkyl is formed. It is particularly preferred that R 6 and R 7 are the same or different and are independently selected from methyl and halomethyl, or R 6 and R 7 together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl group.
在本发明中，R
8、R
9、R
10、R
11和R
12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基，其中前述C
1-C
20烷基、C
2-C
20链烯基、C
2-C
20炔基、C
3-C
20环烷基、C
4-C
20环烷基烷基、C
1-C
20烷氧基、C
2-C
20链烯氧基、C
2-C
20炔氧基、C
3-C
20环烷氧基、C
4-C
20环烷基烷氧基、C
1-C
20烷硫基、C
2-C
20链烯硫基、C
2-C
20炔硫基、C
3-C
20环烷硫基、C
4-C
20环烷基烷硫基和C
6-C
18芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
6烷基、C
1-C
6烷氧基、C
1-C
6烷硫基、C
2-C
6链烯基和C
2-C
6炔基。优选的是，R
8、R
9、R
10、R
11和R
12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
6烷基、C
2-C
6链烯基、C
2-C
6炔基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
1-C
6烷氧基、C
2-C
6链烯氧基、C
2-C
6炔氧基、C
3-C
8环烷氧基、C
4-C
8环烷基烷氧基、C
1-C
6烷硫基、C
2-C
6链烯硫基、C
2-C
6炔硫基、C
3-C
8环烷硫基、C
4-C
8环烷基烷硫基和C
6-C
10芳基，其中前述C
1-C
6烷基、C
2-C
6链烯基、C
2-C
6炔基、C
3-C
8环烷基、C
4-C
8环烷基烷基、C
1-C
6烷氧基、C
2-C
6链烯氧基、C
2-C
6炔氧基、C
3-C
8环烷氧基、C
4-C
8环烷基烷氧基、C
1-C
6烷硫基、C
2-C
6链烯硫基、C
2-C
6炔硫基、C
3-C
8环烷硫基、C
4-C
8环烷基烷硫基和C
6-C
10芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C
1-C
4烷基、C
1-C
4烷氧基、C
1-C
4烷硫基、C
2-C
4链烯基和C
2-C
4炔基。特别优选的是，R
8、R
9、R
10、R
11和R
12彼此独立地选自氢、卤素、C
1-C
4烷基、C
2-C
4链烯基、C
2-C
4炔基、C
1-C
4烷氧基和C
1-C
4烷硫基，其中前述C
1-C
4烷基、C
2-C
4链烯基、C
2-C
4炔基、C
1-C
4烷氧基和C
1-C
4烷硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、C
1-C
4烷基、C
1-C
4烷氧基和C
1-C
4 烷硫基。
In the present invention, R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl, where The aforementioned C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl group may be optionally substituted with one or more groups independently selected from the group: halogen, nitro, hydroxy, mercapto, Group, a sulfonic acid group, an amino group, a cyano group, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group. Preferably, R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfo, amino, cyano, C 1 -C 6 Alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2- C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 aryl, wherein C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 Alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 Alkylthio, C 2 -C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 The aryl group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano , C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl group. It is particularly preferred that R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from each other from hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 Alkynyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, wherein the aforementioned C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1- C 4 alkoxy and C 1 -C 4 alkylthio.
在本发明中，R
13和R
14相同或不同且彼此独立地选自H、C
1-C
6烷基和卤代C
1-C
6烷基。优选的是，R
13和R
14相同或不同且彼此独立地选自H、C
1-C
4烷基和卤代C
1-C
4烷基。特别优选的是，R
13和R
14均为H。
In the present invention, R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl. Preferably, R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 4 alkyl and halo C 1 -C 4 alkyl. It is particularly preferred that both R 13 and R 14 are H.
在本发明的一个特别优选的实施方案中，式(I)化合物选自下组：In a particularly preferred embodiment of the invention, the compound of formula (I) is selected from the group consisting of:
本发明人发现，邻羰基卤代烷化合物可以与羧酸化合物在常规酯化催化剂存在下接触形成酯基，发生成酯反应，该反应如下：The inventors have discovered that an ortho-carbonyl haloalkane compound can be contacted with a carboxylic acid compound in the presence of a conventional esterification catalyst to form an ester group, and an ester-forming reaction occurs. The reaction is as follows:
其中X为卤素，尤其是氯或溴。Where X is halogen, especially chlorine or bromine.
为了加速成酯反应，上述成酯反应通常在适于酯化反应的催化剂存在下进行。作为成酯催化剂，既可以使用酸性催化剂，也可以使用碱性催化剂。作为催化剂，可以使用选自下组的一种或多种：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸银、碳酸锂、四氟硼酸银、四氟硼酸钠、四氟硼酸锂、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化锂、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。In order to accelerate the esterification reaction, the aforementioned esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction. As the ester-forming catalyst, either an acidic catalyst or a basic catalyst can be used. As the catalyst, one or more selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, and sodium carbonate can be used. , Sodium bicarbonate, silver carbonate, lithium carbonate, silver tetrafluoroborate, sodium tetrafluoroborate, lithium tetrafluoroborate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, lithium hydride, calcium hydride, and tertiary amines, such as Trialkylamines, such as trimethylamine and triethylamine.
在本发明中，成酯反应以分步加料的方式进行。通常而言，先将式(III)化合物与成酯催化剂A在-80至100℃下接触0.5-20小时，优选在-80至50℃下接触0.5-10小时，然后加入式(II)化合物和任选的成酯催化剂B在-80至100℃下接触0.5-10小时，优选在-80至30℃下接触0.5-5小时，之后再在-10至50℃下保持1-10小时，优选再在0至30℃下保持1-4小时，以发生成酯反应。此处程序升温的目的是确保反应能够温和地进行。在发生成酯反应之前，将式(III)化合物与成酯催化剂A接触的目的是为了活化式(III)化合物，将式(II)化合物与成酯催化剂B接触的目的也是为了活化式(II)化合物。成酯催化剂A与式(III)化合物的摩尔比通常为1:1至6:1，优选1:1至3:1。成酯催化剂B与式(II)化合物与的摩尔比通常为1:1至6:1，优选1:1至3:1。这里的成酯催化剂A和成酯催化剂B可以相同或不同， 其彼此独立地选择上文所述的成酯催化剂。In the present invention, the ester-forming reaction is performed in a stepwise manner. Generally, the compound of formula (III) is first contacted with the ester-forming catalyst A at -80 to 100 ° C for 0.5-20 hours, preferably at -80 to 50 ° C for 0.5-10 hours, and then the compound of formula (II) is added. Contact with the optional ester-forming catalyst B at -80 to 100 ° C for 0.5-10 hours, preferably at -80 to 30 ° C for 0.5-5 hours, and then hold at -10 to 50 ° C for 1-10 hours, Preferably, it is held at 0 to 30 ° C for an additional 1-4 hours so that an ester-forming reaction occurs. The purpose of the programmed temperature increase here is to ensure that the reaction can proceed gently. Before the esterification reaction occurs, the purpose of contacting the compound of formula (III) with the ester-forming catalyst A is to activate the compound of formula (III), and the purpose of contacting the compound of formula (II) with the ester-forming catalyst B is also to activate the compound of formula (II) ) Compounds. The molar ratio of the ester-forming catalyst A to the compound of the formula (III) is usually 1: 1 to 6: 1, preferably 1: 1 to 3: 1. The molar ratio of the ester-forming catalyst B to the compound of the formula (II) is usually 1: 1 to 6: 1, preferably 1: 1 to 3: 1. The ester-forming catalyst A and the ester-forming catalyst B here may be the same or different, and the ester-forming catalyst described above is selected independently of each other.
上述成酯反应通常在溶剂中，优选在有机溶剂中进行。作为溶剂的类型的选择，没有特别的限制，只要能够将式(II)和式(III)化合物溶解并且对成酯反应呈化学惰性即可，即不参与该成酯反应即可。作为溶剂的实例，可以提及四氢呋喃、苯、甲苯、N,N-二甲基甲酰胺、二氯甲烷和丙酮。溶剂可以使用单一种，也可以使用两种或更多种溶剂的混合物。The above-mentioned ester-forming reaction is usually carried out in a solvent, preferably in an organic solvent. The choice of the type of the solvent is not particularly limited, as long as the compounds of formula (II) and formula (III) can be dissolved and chemically inert to the ester-forming reaction, that is, they do not participate in the ester-forming reaction. As examples of the solvent, mention may be made of tetrahydrofuran, benzene, toluene, N, N-dimethylformamide, dichloromethane and acetone. A single solvent may be used, or a mixture of two or more solvents may be used.
式(II)化合物与式(III)化合物的相对用量没有特别的限制，通常而言它们以等摩尔量或基本等摩尔量使用，例如式(II)化合物与式(III)化合物的摩尔比为1.5:1至1:1.5，优选1.2:1至1:1.2。The relative amounts of the compound of formula (II) and compound of formula (III) are not particularly limited. Generally, they are used in equal or substantially equimolar amounts. For example, the molar ratio of the compound of formula (II) to compound of formula (III) is 1.5: 1 to 1: 1.5, preferably 1.2: 1 to 1: 1.2.
在成酯反应完成之后，任选地加入终止剂比如水终止反应，获得包含式(I)化合物的反应混合物。因此，需要对该反应混合物进行后处理，以得到提纯的式(I)化合物。After the esterification reaction is completed, a terminator such as water is optionally added to terminate the reaction to obtain a reaction mixture comprising a compound of formula (I). Therefore, the reaction mixture needs to be worked up to obtain a purified compound of formula (I).
通常而言，首先过滤成酯反应得到的反应混合物，取出滤液部分，滤渣可包含不溶的成酯催化剂等。对于成酯催化剂中的无机盐类催化剂，一部分溶于水，因而可经水洗后除去，不溶于水的催化剂则通过滤除去。对于成酯催化剂中的有机碱类催化剂，则需要加入适量稀盐酸中和后经水洗除去。Generally speaking, the reaction mixture obtained by the ester-forming reaction is first filtered, and the filtrate portion is taken out. The filter residue may contain an insoluble ester-forming catalyst and the like. Part of the inorganic salt catalyst in the ester-forming catalyst is soluble in water, so it can be removed after washing with water, and the water-insoluble catalyst is removed by filtration. For the organic base catalyst in the ester-forming catalyst, it is necessary to add an appropriate amount of diluted hydrochloric acid for neutralization and then remove it by washing with water.
然后，将滤液进行萃取，萃取可进行一次或多次。作为这里的萃取剂，可采用任何能将式(I)化合物萃取出来的萃取剂，例如二氯甲烷。萃取得到的有机相需要干燥以除去残留的水。为此，通常可使用无水硫酸钠进行干燥。干燥之后，再除去残留的有机溶剂。作为这里除去有机溶剂的手段，没有特别的限制，通常可通过减压蒸馏来除去有机溶剂。除去残留有机溶剂之后，得到了式(I)化合物的粗产物。如果想要进一步提高式(I)化合物的纯度，还可对该化合物进行进一步提纯，这例如可通过重结晶的方式来进行。重结晶溶剂的选择是常规的，没有特别的限制。根据本发明，有利的是，采用甲醇或乙醇对式(I)化合物的粗产物进行重结晶。Then, the filtrate is subjected to extraction, and the extraction may be performed one or more times. As the extractant herein, any extractant capable of extracting the compound of the formula (I) can be used, such as dichloromethane. The extracted organic phase needs to be dried to remove residual water. For this purpose, anhydrous sodium sulfate can usually be used for drying. After drying, the remaining organic solvents were removed. The means for removing the organic solvent is not particularly limited, and the organic solvent can usually be removed by distillation under reduced pressure. After removal of the residual organic solvent, a crude product of the compound of formula (I) is obtained. If it is desired to further improve the purity of the compound of formula (I), the compound can be further purified, for example, by means of recrystallization. The choice of the recrystallization solvent is conventional and is not particularly limited. According to the invention, it is advantageous to recrystallize the crude product of the compound of formula (I) using methanol or ethanol.
本发明制备的式(I)化合物中既包含α-羟基酮类结构部分，又包含肉桂酰基结构部分，因此该化合物即可发挥α-羟基酮类的光引发剂作用，又因为肉桂酰基结构部分的引入而改善α-羟基酮类光引发剂固有存在的异味 和迁移性强的问题。The compound of formula (I) prepared by the present invention contains both an α-hydroxyketone structure part and a cinnamoyl structure part, so the compound can play the role of a photoinitiator of the α-hydroxyketone type, and because the cinnamoyl structure part Introduced to improve the inherent odor and strong migration problems of α-hydroxyketone photoinitiators.
本发明制备的式(I)化合物可吸收200-350nm的电磁波。在吸收电磁波后，式(I)化合物由基态变为激发态，使得式(I)化合物中苯甲酰结构部分中的酰基碳原子与相邻甲氧基中的碳原子断裂，形成两个自由基，从而引发光聚合或光交联。另外，由于式(I)化合物的肉桂酰基结构部分含有不饱和的碳碳双键，因此不同分子间碳碳双键在受到电磁波辐射时容易反应形成更大的分子或交联结构，从而大大改善光引发剂导致的异味和迁移性强的问题，显著减少了异味和显著降低了迁移性。The compound of formula (I) prepared by the present invention can absorb electromagnetic waves of 200-350 nm. After absorbing electromagnetic waves, the compound of formula (I) changes from the ground state to the excited state, so that the acyl carbon atom in the benzoyl structure part of the compound of formula (I) is broken with the carbon atom in the adjacent methoxy group, forming two free radicals. Groups, thereby initiating photopolymerization or photocrosslinking. In addition, because the cinnamoyl structural part of the compound of formula (I) contains unsaturated carbon-carbon double bonds, the carbon-carbon double bonds between different molecules can easily react to form larger molecules or cross-linked structures when subjected to electromagnetic wave radiation, thereby greatly improving The problem of strong odor and migration caused by photoinitiators significantly reduces odor and significantly reduces migration.
本发明制备的式(I)化合物可在涂料、油墨、微电子、印刷等领域以及制备激光录像及三维元件等新型领域用作光引发剂。当式(I)化合物用作光引发剂时，其用量是常规的，或者通过例行的预备试验即可确定。The compound of formula (I) prepared by the present invention can be used as a photoinitiator in the fields of coatings, inks, microelectronics, printing and the like, and in new fields such as laser video recording and three-dimensional components. When the compound of formula (I) is used as a photoinitiator, its amount is conventional or can be determined through routine preliminary tests.
实施例Examples
以下将结合具体实施例对本发明作进一步说明，但不应将其理解为对本发明保护范围的限制。The present invention will be further described below with reference to specific embodiments, but it should not be construed as limiting the scope of protection of the present invention.
实施例1：3-苯基-2-丙烯酸苯甲酰基异丙酯Example 1: Benzoyl isopropyl 3-phenyl-2-acrylate
将14.8g(0.1mol)肉桂酸置于250ml三口瓶中，加入100ml二氯甲烷和27.6g(0.1mol)碳酸银，置于-70℃下搅拌2h，然后向反应瓶中加入18.2g(0.1mol)2-氯-2-甲基-1-苯基-1-丙酮和19.5g(0.1mol)四氟硼酸银。然后在-70℃下持续搅拌1h后升温至-10℃再搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取，然后合并有机相，用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得到淡黄色晶体，共15g，该产物经
1H-NMR谱确认为标题化合物，称作1173-CC。
Put 14.8g (0.1mol) of cinnamic acid in a 250ml three-necked flask, add 100ml of dichloromethane and 27.6g (0.1mol) of silver carbonate, stir at -70 ° C for 2h, and then add 18.2g (0.1 mol) 2-chloro-2-methyl-1-phenyl-1-acetone and 19.5 g (0.1 mol) of silver tetrafluoroborate. Then, the mixture was continuously stirred at -70 ° C for 1 hour, and then heated to -10 ° C and stirred for 2 hours to 3 hours. TLC detected that the reaction was complete. Then, 50 ml of water was added to the reaction solution to stop the reaction, the silver salt was removed by filtration, and then extracted with 2 * 100 ml of dichloromethane, and the organic phases were combined, dried with MgSO 4 for 3 h, and then the organic phase was distilled off under reduced pressure, and then recrystallized from ethanol. A total of 15 g of pale yellow crystals were obtained. The product was identified by the 1 H-NMR spectrum as the title compound, which was named 1173-CC.
1H-NMR(谱)(在Acetone-d6中测定)(δppm)：1.80(s,6H),6.56(d,1H),7.45(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6) (δ ppm): 1.80 (s, 6H), 6.56 (d, 1H), 7.45 (m, 9H), 8.11 (d, 2H).
实施例1a：3-苯基-2-丙烯酸苯甲酰基异丙酯Example 1a: Benzoyl isopropyl 3-phenyl-2-acrylate
将14.8g(0.1mol)肉桂酸置于250ml三口瓶中，加入100ml二氯甲烷和39.1g(0.12mol)碳酸铯，置于-60℃下搅拌1h，然后向反应瓶中加入22.7g(0.1mol)2-溴-2-甲基-1-苯基-1-丙酮和19.5g(0.1mol)四氟硼酸银。然后在-50℃下持续搅拌2h后升温至-5℃再搅拌反应4h-5h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取，然后合并有机相，用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得到淡黄色晶体，共15g，该产物经
1H-NMR谱确认为标题化合物，称作1173-CC。
Place 14.8 g (0.1 mol) of cinnamic acid in a 250 ml three-necked flask, add 100 ml of dichloromethane and 39.1 g (0.12 mol) of cesium carbonate, stir at -60 ° C for 1 h, and then add 22.7 g (0.1 mol) 2-bromo-2-methyl-1-phenyl-1-acetone and 19.5 g (0.1 mol) of silver tetrafluoroborate. Then, the mixture was continuously stirred at -50 ° C for 2 hours, and then heated to -5 ° C and stirred for 4 hours to 5 hours. TLC detected that the reaction was complete. Then, 50 ml of water was added to the reaction solution to stop the reaction, the silver salt was removed by filtration, and then extracted with 2 * 100 ml of dichloromethane, and the organic phases were combined, dried with MgSO 4 for 3 h, and then the organic phase was distilled off under reduced pressure, and then recrystallized from ethanol. A total of 15 g of pale yellow crystals were obtained. The product was identified by the 1 H-NMR spectrum as the title compound, which was named 1173-CC.
1H-NMR(谱)(在Acetone-d6中测定)(δppm)：1.80(s,6H),6.56(d,1H),7.45(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6) (δ ppm): 1.80 (s, 6H), 6.56 (d, 1H), 7.45 (m, 9H), 8.11 (d, 2H).
实施例2：3-(4-甲氧基)苯基-2-丙烯酸苯甲酰基异丙酯Example 2: 3- (4-methoxy) phenyl-2-acrylic acid benzoyl isopropyl
将17.8g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和55.2g(0.2mol)碳酸银，置于-40℃下搅拌40min，然后向反应瓶中加入18.2g(0.1mol)2-氯-2-甲基-1-苯基-1-丙酮和19.5g(0.1mol)四氟硼酸银。然后在-50℃持续搅拌1h后升温至0℃再搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得淡黄色晶体，共20g，该产物经
1H-NMR谱确认为标题化合物。
Place 17.8 g (0.1 mol) of 3- (4-methoxy) phenyl-2-acrylic acid in a 250 ml three-necked flask, add 100 ml of dichloromethane and 55.2 g (0.2 mol) of silver carbonate, and place at -40 ° C After stirring for 40 min, 18.2 g (0.1 mol) of 2-chloro-2-methyl-1-phenyl-1-acetone and 19.5 g (0.1 mol) of silver tetrafluoroborate were added to the reaction flask. Then, the mixture was continuously stirred at -50 ° C for 1 hour, and then heated to 0 ° C and stirred for 2 hours to 3 hours. The reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. 20 g of pale yellow crystals were obtained, and the product was confirmed to be the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.60(s,6H),3.80(s,3H),6.31(d,1H),7.48(m,9H),7.97(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 1.60 (s, 6H), 3.80 (s, 3H), 6.31 (d, 1H), 7.48 (m, 9H), 7.97 (d, 2H) .
实施例3：3-苯基-2-丙烯酸4-甲基苯基甲酰基异丙酯Example 3: 3-phenyl-2-acrylic acid 4-methylphenylformyl isopropyl
将14.8g(0.1mol)3-苯基-2-丙烯酸置于250ml三口瓶中，加入100ml四氢呋喃和15.9g(0.15mol)碳酸钠，置于-60℃下搅拌3h，然后向反应瓶中加入19.6g(0.1mol)2-氯-2-甲基-1-(4-甲基)苯基-1-丙酮和19.5g(0.2mol)四氟硼酸银。然后在-70℃持续搅拌3h后升温至0℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐和未溶解的碳酸钠，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得淡黄色晶体，共19g，该产物经
1H-NMR谱确认为标题化合物。
Put 14.8g (0.1mol) of 3-phenyl-2-acrylic acid in a 250ml three-necked flask, add 100ml of tetrahydrofuran and 15.9g (0.15mol) of sodium carbonate, stir at -60 ° C for 3h, and then add to the reaction flask 19.6 g (0.1 mol) of 2-chloro-2-methyl-1- (4-methyl) phenyl-1-acetone and 19.5 g (0.2 mol) of silver tetrafluoroborate. Then, the mixture was continuously stirred at -70 ° C for 3h, and then heated to 0 ° C to stir the reaction for 2h-3h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt and undissolved sodium carbonate by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, and then remove the organic by distillation under reduced pressure. The phase was then recrystallized from ethanol to give pale yellow crystals, a total of 19 g, which was confirmed to be the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.78(s,6H),2.34(s,6H),6.54(d,1H),7.35(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 1.78 (s, 6H), 2.34 (s, 6H), 6.54 (d, 1H), 7.35 (m, 9H), 8.11 (d, 2H) .
实施例4：3-苯基-2-丙烯酸4-甲硫基苯基甲酰基异丙酯Example 4: 4-Phenyl-2-acrylic acid 4-methylthiophenylformyl isopropyl ester
将14.8g(0.1mol)3-苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和22.2g(0.3mol)碳酸锂，置于-60℃下搅拌2h，然后向反应瓶中加入22.8g(0.1mol)2-氯-2-甲基-1-(4-甲硫基)苯基-1-丙酮和29.25g(0.15mol)四氟硼酸银。然后在-70℃持续搅拌4h后升温至20℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐和未溶解的碳酸锂，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得黄色晶体，共20g，该产物经
1H-NMR谱确认为标题化合物。
14.8g (0.1mol) of 3-phenyl-2-acrylic acid was placed in a 250ml three-necked flask, 100ml of dichloromethane and 22.2g (0.3mol) of lithium carbonate were added, and the mixture was stirred at -60 ° C for 2h, and then added to the reaction flask. 22.8 g (0.1 mol) of 2-chloro-2-methyl-1- (4-methylthio) phenyl-1-acetone and 29.25 g (0.15 mol) of silver tetrafluoroborate were added. Then, the mixture was continuously stirred at -70 ° C for 4h, and then heated to 20 ° C to stir the reaction for 2h-3h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, filter to remove the silver salt and undissolved lithium carbonate, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic by distillation under reduced pressure. The phase was then recrystallized from ethanol to obtain yellow crystals, a total of 20 g, which was confirmed to be the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.80(s,6H),2.53(s,6H),6.56(d,1H),7.45(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 1.80 (s, 6H), 2.53 (s, 6H), 6.56 (d, 1H), 7.45 (m, 9H), 8.11 (d, 2H) .
实施例4a：3-苯基-2-丙烯酸4-甲硫基苯基甲酰基异丙酯Example 4a: 4-phenyl-2-acrylic acid 4-methylthiophenylformyl isopropyl ester
将14.8g(0.1mol)3-苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和1.11g(0.15mol)碳酸锂，置于-60℃下搅拌4h，然后向反应瓶中加入27.3g(0.1mol)2-溴-2-甲基-1-(4-甲硫基)苯基-1-丙酮和22.2g(0.3mol)碳酸锂。然后在-60℃持续搅拌3h后升温至0℃搅拌反应3h-4h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去锂盐和钾盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得黄色晶体，共21g，该产物经
1H-NMR谱确认为标题化合物。
14.8g (0.1mol) of 3-phenyl-2-acrylic acid was placed in a 250ml three-necked flask, 100ml of dichloromethane and 1.11g (0.15mol) of lithium carbonate were added, and the mixture was stirred at -60 ° C for 4h, and then added to the reaction flask. 27.3 g (0.1 mol) of 2-bromo-2-methyl-1- (4-methylthio) phenyl-1-acetone and 22.2 g (0.3 mol) of lithium carbonate were added. Then, the mixture was continuously stirred at -60 ° C for 3h, and then heated to 0 ° C, and the reaction was stirred for 3h-4h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, remove the lithium salt and potassium salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, and then remove the organic phase by distillation under reduced pressure. Recrystallization from ethanol gave yellow crystals, a total of 21 g, which was confirmed to be the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.80(s,6H),2.53(s,6H),6.56(d,1H),7.45(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 1.80 (s, 6H), 2.53 (s, 6H), 6.56 (d, 1H), 7.45 (m, 9H), 8.11 (d, 2H) .
实施例5：3-苯基-2-丙烯酸1-苯甲酰基环己基酯Example 5: 3-phenyl-2-acrylic acid 1-benzoylcyclohexyl ester
将14.8g(0.1mol)3-苯基-2-丙烯酸置于250ml三口瓶中，加入100ml甲苯和44.16g(0.16mol)碳酸银，置于-60℃下搅拌2.5h，然后向反应瓶中加入22.2g(0.1mol)(1-氯环己基)(苯基)甲酮和39g(0.2mol)四氟硼酸银。然后在-40℃持续搅拌1h后升温至20℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得黄色晶体，共24g，该产物经
1H-NMR谱确认为标题化合物，称作184-CC。
14.8g (0.1mol) of 3-phenyl-2-acrylic acid was placed in a 250ml three-necked flask, 100ml of toluene and 44.16g (0.16mol) of silver carbonate were added, and the mixture was stirred at -60 ° C for 2.5h, and then added to the reaction flask 22.2 g (0.1 mol) of (1-chlorocyclohexyl) (phenyl) methanone and 39 g (0.2 mol) of silver tetrafluoroborate were added. Then, the mixture was continuously stirred at -40 ° C for 1 hour, and then heated to 20 ° C to stir the reaction for 2h-3h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 24 g of yellow crystals were obtained. The product was identified by the 1 H-NMR spectrum as the title compound, which is called 184-CC.
1H-NMR(谱)(在Acetone-d6中测定)：1.36(m,6H),1.69(m,2H),
1 H-NMR (spectrum) (determined in Acetone-d6): 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)。2.42 (d, 2H), 6.59 (d, 1H), 7.39 (m, 6H), 7.65 (m, 3H), 8.06 (d, 2H).
实施例5a：3-苯基-2-丙烯酸1-苯甲酰基环己基酯Example 5a: 3-phenyl-2-acrylic acid 1-benzoylcyclohexyl ester
将14.8g(0.1mol)3-苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和32.5g(0.1mol)碳酸铯，置于-40℃下搅拌2h，然后向反应瓶中加入22.2g(0.1mol)(1-溴环己基)(苯基)甲酮和19.5g(0.1mol)四氟硼酸银。然后在-40℃持续搅拌1h后升温至50℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得黄色晶体，共25g，该产物经
1H-NMR谱确认为标题化合物，称作184-CC。
14.8g (0.1mol) of 3-phenyl-2-acrylic acid was placed in a 250ml three-necked flask, 100ml of dichloromethane and 32.5g (0.1mol) of cesium carbonate were added, and the mixture was stirred at -40 ° C for 2h, and then added to the reaction flask. 22.2 g (0.1 mol) of (1-bromocyclohexyl) (phenyl) methanone and 19.5 g (0.1 mol) of silver tetrafluoroborate were added. Then, stirring was continued at -40 ° C for 1 hour, and then the temperature was raised to 50 ° C, and the reaction was stirred for 2h-3h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 25 g of yellow crystals were obtained. The product was identified by the 1 H-NMR spectrum as the title compound, which is called 184-CC.
1H-NMR(谱)(在Acetone-d6中测定)：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)
1 H-NMR (spectrum) (determined in Acetone-d6): 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)
实施例5b：3-苯基-2-丙烯酸1-苯甲酰基环己基酯Example 5b: 3-phenyl-2-acrylic acid 1-benzoylcyclohexyl ester
将14.8g(0.1mol)3-苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和10.1g(0.1mol)三乙胺，置于-20℃下搅拌30min，然后向反应瓶中加入22.2g(0.1mol)(1-氯环己基)(苯基)甲酮和19.5g(0.1mol)四氟硼酸银。然后在-20℃持续搅拌1h后升温至25℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机 相，然后乙醇重结晶，得黄色晶体，共21g，该产物经
1H-NMR谱确认为标题化合物，称作184-CC。
14.8g (0.1mol) of 3-phenyl-2-acrylic acid was placed in a 250ml three-necked flask, 100ml of dichloromethane and 10.1g (0.1mol) of triethylamine were added, and the mixture was stirred at -20 ° C for 30min, and then reacted to the reaction. 22.2 g (0.1 mol) of (1-chlorocyclohexyl) (phenyl) methanone and 19.5 g (0.1 mol) of silver tetrafluoroborate were added to the bottle. Then, the mixture was stirred continuously at -20 ° C for 1h, and then heated to 25 ° C to stir the reaction for 2h-3h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 21 g of yellow crystals were obtained. The product was identified by the 1 H-NMR spectrum as the title compound, which is called 184-CC.
1H-NMR(谱)(在Acetone-d6中测定)：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)。
1 H-NMR (spectrum) (determined in Acetone-d6): 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).
实施例6:3-(4-甲氧基苯基)-2-丙烯酸1-苯甲酰基环己基酯Example 6: 3- (4-methoxyphenyl) -2-benzoylcyclohexyl acrylate
将17.8g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酸置于250ml三口瓶中，加入100mlN,N-二甲基甲酰胺和12g(0.3mol)氢氧化钠，置于-80℃下搅拌1h，然后向反应瓶中加入22.2g(0.1mol)(1-氯环己基)(苯基)甲酮和58.5g(0.3mol)四氟硼酸银。然后在-70℃持续搅拌1h后升温至30℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得黄色晶体，共25g，该产物经
1H-NMR谱确认为标题化合物。
Place 17.8 g (0.1 mol) of 3- (4-methoxy) phenyl-2-acrylic acid in a 250 ml three-necked flask, add 100 ml of N, N-dimethylformamide and 12 g (0.3 mol) of sodium hydroxide. After stirring at -80 ° C for 1 h, 22.2 g (0.1 mol) of (1-chlorocyclohexyl) (phenyl) methanone and 58.5 g (0.3 mol) of silver tetrafluoroborate were added to the reaction flask. Then, the mixture was continuously stirred at -70 ° C for 1 hour, and then heated to 30 ° C to stir the reaction for 2h-3h. The reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 25 g of yellow crystals was obtained, and the product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：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)。
1 H-NMR (spectrum) (determined in Acetone-d6): 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).
实施例7：3-苯基-2-丙烯酸1-(2-甲基苯甲酰基)环己基酯Example 7: 3-phenyl-2-acrylic acid 1- (2-methylbenzoyl) cyclohexyl ester
将14.8g(0.1mol)3-苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和9.6g(0.1mol)叔丁醇钠，置于-60℃下搅拌3h，然后向反应瓶中加入23.6g(0.1mol)(1-氯环己基)(2-甲基苯基)甲酮和19.2g(0.2mol)叔丁醇钠。然后在-70℃持续搅拌3h后升温至0℃搅拌反应2h-3h，TLC检测至反应完全。然 后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得黄色晶体，共24g，该产物经
1H-NMR谱确认为标题化合物。
14.8g (0.1mol) of 3-phenyl-2-acrylic acid was placed in a 250ml three-necked flask, 100ml of dichloromethane and 9.6g (0.1mol) of sodium tert-butoxide were added, and the mixture was stirred at -60 ° C for 3h, and then 23.6 g (0.1 mol) of (1-chlorocyclohexyl) (2-methylphenyl) methanone and 19.2 g (0.2 mol) of sodium tert-butoxide were added to the reaction flask. Then, the mixture was continuously stirred at -70 ° C for 3h, and then heated to 0 ° C to stir the reaction for 2h-3h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 24 g of yellow crystals were obtained. The product was confirmed to be the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：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)。
1 H-NMR (spectrum) (determined in Acetone-d6): 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).
实施例8：3-苯基-2-丙烯酸1-(4-异丙基苯甲酰基)环己基酯Example 8: 3-phenyl-2-acrylic acid 1- (4-isopropylbenzoyl) cyclohexyl ester
将14.8g(0.1mol)3-苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和27.6g(0.1mol)碳酸银，置于-60℃下搅拌30min，然后向反应瓶中加入26.4g(0.1mol)(1-氯环己基)(4-异丙基苯基)甲酮和19.5g(0.1mol)四氟硼酸银。然后在-70℃持续搅拌1h后升温至0℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得黄色晶体，共25g，该产物经
1H-NMR谱确认为标题化合物。
14.8 g (0.1 mol) of 3-phenyl-2-acrylic acid was placed in a 250 ml three-necked flask, 100 ml of dichloromethane and 27.6 g (0.1 mol) of silver carbonate were added, and the mixture was stirred at -60 ° C for 30 min. 26.4 g (0.1 mol) of (1-chlorocyclohexyl) (4-isopropylphenyl) methanone and 19.5 g (0.1 mol) of silver tetrafluoroborate were added. Then, the mixture was continuously stirred at -70 ° C for 1 hour, and then heated to 0 ° C, and the reaction was stirred for 2h-3h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 25 g of yellow crystals was obtained, and the product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：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)。
1 H-NMR (spectrum) (determined in Acetone-d6): 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).
实施例9：3-(4-甲氧基)苯基-2-丙烯酸4-甲氧基苯甲酰基异丙酯Example 9: 3- (4-methoxy) phenyl-2-acrylic acid 4-methoxybenzoyl isopropyl
将17.8g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和11g(0.1mol)四氟硼酸钠，置于-20℃下搅拌30min，然后 向反应瓶中加入21.2g(0.1mol)2-氯-2-甲基-1-(4-甲氧基)苯基-1-丙酮和22g(0.2mol)四氟硼酸钠。然后在-70℃持续搅拌6h后升温至0℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得淡黄色晶体，共17g，该产物经
1H-NMR谱确认为标题化合物。
Place 17.8 g (0.1 mol) of 3- (4-methoxy) phenyl-2-acrylic acid in a 250 ml three-necked flask, add 100 ml of dichloromethane and 11 g (0.1 mol) of sodium tetrafluoroborate, and place at -20 ° C After stirring for 30 min, 21.2 g (0.1 mol) of 2-chloro-2-methyl-1- (4-methoxy) phenyl-1-acetone and 22 g (0.2 mol) of sodium tetrafluoroborate were added to the reaction flask. . Then, the mixture was continuously stirred at -70 ° C for 6h, and then heated to 0 ° C, and the reaction was stirred for 2h-3h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 17 g of pale yellow crystals were obtained. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定):1.50(s,6H),3.83(s,6H),5.75(s,2H),6.54(d,1H),7.35(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 1.50 (s, 6H), 3.83 (s, 6H), 5.75 (s, 2H), 6.54 (d, 1H), 7.35 (m, 9H) 8.11 (d, 2H).
实施例9a：3-(4-甲氧基)苯基-2-丙烯酸苯甲酰基甲酯Example 9a: 3- (4-methoxy) phenyl-2-acrylic acid benzoyl methyl ester
将17.8g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和27.6g(0.1mol)碳酸银，置于-60℃下搅拌30min，然后向反应瓶中加入15.4g(0.1mol)2-氯-1-苯基-1-乙酮和6.8g(0.1mol)乙醇钠。然后在-70℃持续搅拌1h后升温至0℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得淡黄色晶体，共18g，该产物经
1H-NMR谱确认为标题化合物。
Place 17.8 g (0.1 mol) of 3- (4-methoxy) phenyl-2-acrylic acid in a 250 ml three-necked flask, add 100 ml of dichloromethane and 27.6 g (0.1 mol) of silver carbonate, and place at -60 ° C After stirring for 30 min, 15.4 g (0.1 mol) of 2-chloro-1-phenyl-1-ethanone and 6.8 g (0.1 mol) of sodium ethoxide were added to the reaction flask. Then, the mixture was continuously stirred at -70 ° C for 1 hour, and then heated to 0 ° C, and the reaction was stirred for 2h-3h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 18 g of pale yellow crystals were obtained. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定):3.83(s,3H),5.75(s,2H),6.54(d,1H),7.35(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 3.83 (s, 3H), 5.75 (s, 2H), 6.54 (d, 1H), 7.35 (m, 9H), 8.11 (d, 2H) .
实施例9b：3-(4-甲氧基)苯基-2-丙烯酸苯甲酰基甲酯Example 9b: 3- (4-methoxy) phenyl-2-acrylic acid methyl ester
将17.8g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和10.6g(0.1mol)碳酸钠，置于-50℃下搅拌30min，然后向反应瓶中加入15.4g(0.1mol)2-氯-1-苯基-1-乙酮和11g(0.1mol)四氟硼酸钠。然后在0℃持续搅拌反应1h后升温至10℃搅拌反应2h-4h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去剩余未溶于水的钠盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得淡黄色晶体，共17g，该产物经
1H-NMR谱确认为标题化合物。
Place 17.8 g (0.1 mol) of 3- (4-methoxy) phenyl-2-acrylic acid in a 250 ml three-necked flask, add 100 ml of dichloromethane and 10.6 g (0.1 mol) of sodium carbonate, and place at -50 ° C After stirring for 30 min, 15.4 g (0.1 mol) of 2-chloro-1-phenyl-1-ethanone and 11 g (0.1 mol) of sodium tetrafluoroborate were added to the reaction flask. Then, the reaction was continuously stirred at 0 ° C for 1h, and then heated to 10 ° C for 2h-4h, and the reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, filter to remove the remaining insoluble sodium salt, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, and then remove the organic by distillation under reduced pressure. The phase was then recrystallized from ethanol to give a pale yellow crystal, a total of 17 g, which was confirmed to be the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定):3.83(s,3H),5.75(s,2H),6.54(d,1H),7.35(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 3.83 (s, 3H), 5.75 (s, 2H), 6.54 (d, 1H), 7.35 (m, 9H), 8.11 (d, 2H) .
实施例10：3-(4-甲氧基)苯基-2-丙烯酸(1-苯甲酰基-1,1-双(三氯甲基))甲酯Example 10: 3- (4-methoxy) phenyl-2-acrylic acid (1-benzoyl-1,1-bis (trichloromethyl)) methyl ester
将17.8g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酸置于250ml三口瓶中，加入100ml和27.6g(0.1mol)四氟硼酸银，置于-30℃下搅拌30min，然后向反应瓶中加入38.5g(0.1mol)2-氯-2,2-双(三氯甲基)-1-苯基-1-乙酮和19.5g(0.1mol)氢化钠。然后在-70℃持续搅拌5h后升温至0℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得淡黄色晶体，共30g，该产物经
1H-NMR谱确认为标题化合物。
Put 17.8g (0.1mol) of 3- (4-methoxy) phenyl-2-acrylic acid in a 250ml three-necked flask, add 100ml and 27.6g (0.1mol) of silver tetrafluoroborate, and stir at -30 ° C After 30 min, 38.5 g (0.1 mol) of 2-chloro-2,2-bis (trichloromethyl) -1-phenyl-1-ethanone and 19.5 g (0.1 mol) of sodium hydride were added to the reaction flask. Then, the mixture was continuously stirred at -70 ° C for 5h, and then heated to 0 ° C to stir the reaction for 2h-3h. TLC detected that the reaction was complete. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry for 3 h, and then remove the organic phase by distillation under reduced pressure. A total of 30 g of pale yellow crystals were confirmed by 1 H-NMR spectrum as the title compound.
1H-NMR(谱)(在Acetone-d6中测定)：3.83(s,3H),6.54(d,1H),7.35(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 3.83 (s, 3H), 6.54 (d, 1H), 7.35 (m, 9H), 8.11 (d, 2H).
实施例11：3-(4-甲氧基)苯基-2-丙烯酸4-苯硫基苯基甲酰基异丙酯Example 11: 3- (4-methoxy) phenyl-2-acrylic acid 4-phenylthiophenylformyl isopropyl ester
将17.8g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酸置于250ml三口瓶中，加入100ml甲苯和27.6g(0.1mol)碳酸银，置于-30℃下搅拌30min，然后向反应瓶中加入29.1g(0.1mol)2-氯-2-甲基-1-(4-苯硫基苯基)-1-丙酮和19.5g(0.1mol)四氟硼酸银。然后在-20℃持续搅拌1h后升温至0℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得淡黄色晶体，共18g，该产物经
1H-NMR谱确认为标题化合物。
Put 17.8g (0.1mol) of 3- (4-methoxy) phenyl-2-acrylic acid in a 250ml three-necked flask, add 100ml of toluene and 27.6g (0.1mol) of silver carbonate, and stir at -30 ° C for 30min Then, 29.1 g (0.1 mol) of 2-chloro-2-methyl-1- (4-phenylthiophenyl) -1-acetone and 19.5 g (0.1 mol) of silver tetrafluoroborate were added to the reaction flask. Then, the mixture was stirred continuously at -20 ° C for 1 hour, and then heated to 0 ° C, and stirred for 2 hours to 3 hours. The reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry for 3 h, and then remove the organic phase by distillation under reduced pressure. A total of 18 g of pale yellow crystals were identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.58(d,6H),3.83(s,3H),5.64(q，1H),6.54(d,1H),7.35(m,13H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 1.58 (d, 6H), 3.83 (s, 3H), 5.64 (q, 1H), 6.54 (d, 1H), 7.35 (m, 13H) 8.11 (d, 2H).
实施例11a：3-(4-甲氧基)苯基-2-丙烯酸(1-苯甲酰基)乙酯Example 11a: 3- (4-methoxy) phenyl-2- (1-benzoyl) ethyl acrylate
将17.8g(0.1mol)3-(4-甲氧基)苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和27.6g(0.1mol)碳酸银，置于-60℃下搅拌30min，然后向反应瓶中加入16.8g(0.1mol)2-氯-1-苯基-1-丙酮和58.5g(0.3mol)四氟硼酸银。然后在-70℃持续搅拌10h后升温至0℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得淡黄色晶体，共18g，该产物经
1H-NMR谱确认为标题化合物。
Place 17.8 g (0.1 mol) of 3- (4-methoxy) phenyl-2-acrylic acid in a 250 ml three-necked flask, add 100 ml of dichloromethane and 27.6 g (0.1 mol) of silver carbonate, and place at -60 ° C After stirring for 30 min, 16.8 g (0.1 mol) of 2-chloro-1-phenyl-1-acetone and 58.5 g (0.3 mol) of silver tetrafluoroborate were added to the reaction flask. Then, the mixture was stirred continuously at -70 ° C for 10 hours, and then heated to 0 ° C, and the reaction was stirred for 2 hours-3 hours. The reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol A total of 18 g of pale yellow crystals were obtained. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.58(d,3H),3.83(s,3H),5.64(q，1H),6.54(d,1H),7.35(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 1.58 (d, 3H), 3.83 (s, 3H), 5.64 (q, 1H), 6.54 (d, 1H), 7.35 (m, 9H) 8.11 (d, 2H).
实施例12：3-甲基-3-(4-乙烯基)苯基-2-丙烯酸2-氯苯基甲酰基异丙酯Example 12: 3-methyl-3- (4-vinyl) phenyl-2-acrylic acid 2-chlorophenylformyl isopropyl
将18.8g(0.1mol)3-甲基-3-(4-乙烯基)苯基-2-丙烯酸置于250ml三口瓶中，加入100ml丙酮和27.6g(0.1mol)氢化钙，置于-60℃下搅拌8h，然后向反应瓶中加入21.6g(0.1mol)2-氯-2-甲基-1-(2-氯)苯基-1-丙酮和19.5g(0.1mol)四氟硼酸银。然后在-10℃持续搅拌1h后升温至0℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得淡黄色晶体，共22g，该产物经
1H-NMR谱确认为标题化合物。
Place 18.8g (0.1mol) of 3-methyl-3- (4-vinyl) phenyl-2-acrylic acid in a 250ml three-necked flask, add 100ml of acetone and 27.6g (0.1mol) of calcium hydride, and place at -60 After stirring at ℃ for 8 hours, 21.6 g (0.1 mol) of 2-chloro-2-methyl-1- (2-chloro) phenyl-1-acetone and 19.5 g (0.1 mol) of silver tetrafluoroborate were added to the reaction flask. . Then, the mixture was continuously stirred at -10 ° C for 1 hour, and then heated to 0 ° C and stirred for 2 hours to 3 hours. The reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 22 g of pale yellow crystals were obtained. The product was identified by the 1 H-NMR spectrum as the title compound.
1H-NMR(谱)(在Acetone-d6中测定)：1.78(s,6H),2.34(s,6H),6.54(d,1H),7.35(m,9H),8.11(d,2H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 1.78 (s, 6H), 2.34 (s, 6H), 6.54 (d, 1H), 7.35 (m, 9H), 8.11 (d, 2H) .
实施例13：3-甲基-3-(4-乙炔基)苯基-2-丙烯酸2-甲基苯基甲酰基异丙酯Example 13: 3-methyl-3- (4-ethynyl) phenyl-2-acrylic acid 2-methylphenylformyl isopropyl
将18.6g(0.1mol)3-甲基-3-(4-乙炔基)苯基-2-丙烯酸置于250ml三口瓶中，加入100ml二氯甲烷和27.6g(0.1mol)碳酸银，置于-60℃下搅拌30min，然后向反应瓶中加入24g(0.1mol)2-溴-2-甲基-1-(2-甲基)苯基-1-丙酮和19.5g(0.1mol)四氟硼酸银。然后在-70℃持续搅拌8h后升温至0℃搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得淡黄色晶体，共17g，该产物经
1H-NMR谱确认为标题化合物。
Put 18.6g (0.1mol) of 3-methyl-3- (4-ethynyl) phenyl-2-acrylic acid in a 250ml three-necked flask, add 100ml of dichloromethane and 27.6g (0.1mol) of silver carbonate, and place After stirring at -60 ° C for 30 min, 24 g (0.1 mol) of 2-bromo-2-methyl-1- (2-methyl) phenyl-1-acetone and 19.5 g (0.1 mol) of tetrafluoro were added to the reaction flask. Silver borate. Then, the mixture was continuously stirred at -70 ° C for 8 hours, and then heated to 0 ° C, and the reaction was stirred for 2 hours to 3 hours. The reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 17 g of pale yellow crystals were obtained. The product was identified as the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：1.78(s,6H),2.42(s,3H),2.48(s,3H)4.05(s，1H),6.11(d,1H),7.35(m,9H)。
1 H-NMR (spectrum) (determined in Acetone-d6): 1.78 (s, 6H), 2.42 (s, 3H), 2.48 (s, 3H) 4.05 (s, 1H), 6.11 (d, 1H), 7.35 (m, 9H).
实施例14：2-甲基-3-(4-氯苯基)-2-丙烯酸1-(4-异丙基苯甲酰基)环己基酯Example 14: 2-methyl-3- (4-chlorophenyl) -2-acrylic acid 1- (4-isopropylbenzoyl) cyclohexyl ester
将19.6g(0.1mol)2-甲基-3-(4-氯)苯基-2-丙烯酸置于250ml三口瓶中，加入100ml甲苯和27.6g(0.1mol)碳酸银，置于50℃下搅拌30min，降温至20℃，然后向反应瓶中加入26.4g(0.1mol)(1-氯环己基)(4-异丙基苯基)甲酮和11.0g(0.1mol)四氟硼酸钠。然后保持在20℃下持续搅拌反应2h-3h，TLC检测至反应完全。然后向反应液中加入50ml水终止反应，过滤除去银盐，然后用2*100ml二氯甲烷萃取有机相，合并有机相后用MgSO
4干燥3h后，减压蒸馏除去有机相，然后乙醇重结晶，得黄色晶体，共28g，该产物经
1H-NMR谱确认为标题化合物。
Put 19.6g (0.1mol) of 2-methyl-3- (4-chloro) phenyl-2-acrylic acid in a 250ml three-necked flask, add 100ml of toluene and 27.6g (0.1mol) of silver carbonate, and place at 50 ° C After stirring for 30 min, the temperature was lowered to 20 ° C, and then 26.4 g (0.1 mol) of (1-chlorocyclohexyl) (4-isopropylphenyl) methanone and 11.0 g (0.1 mol) of sodium tetrafluoroborate were added to the reaction flask. Then, the reaction was kept stirring at 2 ° C for 2h-3h, and the reaction was detected to be complete by TLC. Then add 50 ml of water to the reaction solution to stop the reaction, remove the silver salt by filtration, then extract the organic phase with 2 * 100 ml of dichloromethane, combine the organic phases and dry with MgSO 4 for 3 h, then remove the organic phase by distillation under reduced pressure, and then recrystallize from ethanol. A total of 28 g of yellow crystals were obtained. The product was confirmed to be the title compound by 1 H-NMR spectrum.
1H-NMR(谱)(在Acetone-d6中测定)：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)。
1 H-NMR (spectrum) (determined in Acetone-d6): 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).
由上述实施例可见，本申请各实施例的得到的产率无一例外地明显高于WO2018/094960中对应各实施例和对比例公开的相应产率。It can be seen from the above examples that the yields obtained by the examples of this application are, without exception, significantly higher than the corresponding yields disclosed in the corresponding examples and comparative examples in WO2018 / 094960.
Claims (10)
- 一种制备式(I)的肉桂酸苯甲酰基甲酯类化合物的方法：Method for preparing benzoyl methyl cinnamate compounds of formula (I):
其中among themR 1、R 2、R 3、R 4和R 5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 20烷基、C 2-C 20链烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20链烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20链烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基和C 6-C 18芳基，其中前述C 1-C 20烷基、C 2-C 20链烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20链烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20链烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基和C 6-C 18芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 2-C 6链烯基和C 2-C 6炔基； R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 Alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl, wherein the aforementioned C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl groups May be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, thiol, carboxyl, sulfonic, Group, a cyano group, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group;R 6和R 7相同或不同且彼此独立地选自H、C 1-C 6烷基和卤代C 1-C 6烷基，或者R 6和R 7与它们所连接的碳原子一起形成C 3-C 8环烷基； R 6 and R 7 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, or R 6 and R 7 together with the carbon atom to which they are attached form C 3 -C 8 cycloalkyl;R 8、R 9、R 10、R 11和R 12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 20烷基、C 2-C 20链烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20链烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20链烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基 和C 6-C 18芳基，其中前述C 1-C 20烷基、C 2-C 20链烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20链烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20链烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基和C 6-C 18芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 2-C 6链烯基和C 2-C 6炔基；以及 R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 Alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 Alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl, wherein the aforementioned C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -C 20 cycloalkylthio, C 4 -C 20 cycloalkylalkylthio, and C 6 -C 18 aryl groups Can be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, thiol, carboxyl, sulfonic Amino, cyano, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl group;R 13和R 14相同或不同且彼此独立地选自H、C 1-C 6烷基和卤代C 1-C 6烷基，包括使式(II)化合物与式(III)化合物接触以发生成酯反应，得到式(I)化合物， R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 6 alkyl and halo C 1 -C 6 alkyl, including contacting a compound of formula (II) with a compound of formula (III) to occur Ester formation reaction to obtain a compound of formula (I),
其中R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13和R 14如上所定义，以及X为卤素，尤其是氯或溴。 Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are as defined above, and X is halogen , Especially chlorine or bromine. - 根据权利要求1的方法，其中R 6和R 7相同或不同且彼此独立地选自C 1-C 4烷基和卤代C 1-C 4烷基，或者R 6和R 7与它们所连接的碳原子一起形成C 5-C 6环烷基。 A method according to claim 1, wherein R 6 and R 7 are the same or different and are independently selected from C 1 -C 4 alkyl and halo C 1 -C 4 alkyl, or R 6 and R 7 are attached to them The carbon atoms together form a C 5 -C 6 cycloalkyl.
- 根据权利要求2的方法，其中R 6和R 7相同或不同且彼此独立地选自甲基和卤代甲基，或者R 6和R 7与它们所连接的碳原子一起形成环戊基或环己基。 A method according to claim 2, wherein R 6 and R 7 are the same or different and are independently selected from methyl and halomethyl, or R 6 and R 7 form a cyclopentyl or ring together with the carbon atom to which they are attached Jiji.
- 根据权利要求1-3中任一项的方法，其中R 13和R 14相同或不同且彼此独立地选自H、C 1-C 4烷基和卤代C 1-C 4烷基，优选R 13和R 14均为H。 Process according to any one of claims 1 to 3, wherein R 13 and R 14 are the same or different and are independently selected from H, C 1 -C 4 alkyl and halo C 1 -C 4 alkyl, preferably R 13 and R 14 are both H.
- 根据权利要求1-4中任一项的方法，其中A method according to any one of claims 1-4, whereinR 1、R 2、R 3、R 4和R 5彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 2-C 6链烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6链烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6链烯硫 基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基和C 6-C 10芳基，其中前述C 1-C 6烷基、C 2-C 6链烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6链烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6链烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基和C 6-C 10芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、C 2-C 4链烯基和C 2-C 4炔基；和/或 R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 Alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 Alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 aryl, wherein the aforementioned C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 aryl groups may be optionally substituted with one or more groups independently selected from the group: halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 4 alkoxy , C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl; and / orR 8、R 9、R 10、R 11和R 12彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 2-C 6链烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6链烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6链烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基和C 6-C 10芳基，其中前述C 1-C 6烷基、C 2-C 6链烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6链烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6链烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基和C 6-C 10芳基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、C 2-C 4链烯基和C 2-C 4炔基。 R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 Alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 Alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 aryl, wherein the aforementioned C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -C 8 cycloalkylthio, C 4 -C 8 cycloalkylalkylthio, and C 6 -C 10 aryl groups It may be optionally substituted with one or more groups independently selected from the group: halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic, amino, cyano, C 1 -C 4 Group, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl group.
- 根据权利要求1-4中任一项的方法，其中A method according to any one of claims 1-4, whereinR 1、R 2、R 3、R 4和R 5彼此独立地选自氢、卤素、C 1-C 4烷基、C 1-C 4烷氧基和C 1-C 4烷硫基，其中前述C 1-C 4烷基、C 1-C 4烷氧基和C 1-C 4烷硫基可任选地被一个或多个独立地选自下组的基团取代：卤素、C 1-C 4烷基、C 1-C 4烷氧基和C 1-C 4烷硫基；和/或 R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio, wherein The aforementioned C 1 -C 4 alkyl group, C 1 -C 4 alkoxy group, and C 1 -C 4 alkylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and C 1 -C 4 alkylthio; and / orR 8、R 9、R 10、R 11和R 12彼此独立地选自氢、卤素、C 1-C 4烷基、C 2-C 4链烯基、C 2-C 4炔基、C 1-C 4烷氧基和C 1-C 4烷硫基，其中前述C 1-C 4烷基、C 2-C 4链烯基、C 2-C 4炔基、C 1-C 4烷氧基和C 1-C 4烷硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、C 1-C 4烷基、C 1-C 4烷氧 基和C 1-C 4烷硫基。 R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, wherein the aforementioned C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy And C 1 -C 4 alkylthio groups may be optionally substituted with one or more groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy And C 1 -C 4 alkylthio.
- 根据权利要求1的方法，其中式(I)化合物选自下组：The method according to claim 1, wherein the compound of formula (I) is selected from the group consisting of:
- 根据权利要求1-7中任一项的方法，其中式(II)化合物与式(II)化合 物的接触在成酯催化剂存在下进行，优选该成酯催化剂为选自下组的一种或多种：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸银、碳酸锂、四氟硼酸银、四氟硼酸钠、四氟硼酸锂、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化锂、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。The method according to any one of claims 1 to 7, wherein the contacting of the compound of formula (II) with the compound of formula (II) is performed in the presence of an ester-forming catalyst, preferably the ester-forming catalyst is one or more selected from the group consisting of Species: sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, silver carbonate, lithium carbonate, tetrafluoroborate Silver, sodium tetrafluoroborate, lithium tetrafluoroborate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, lithium hydride, calcium hydride, and tertiary amines, such as trialkylamines, such as trimethylamine and triethylamine .
- 根据权利要求1-8中任一项的方法，其中先将式(III)化合物与成酯催化剂A在-80至100℃下接触0.5-20小时，优选在-80至50℃下接触0.5-10小时，然后加入式(II)化合物和任选的成酯催化剂B在-80至100℃下接触0.5-10小时，优选在-80至30℃下接触0.5-5小时，之后再在-10至50℃下保持1-10小时，优选再在0至30℃下保持1-4小时，以发生成酯反应，其中成酯催化剂A和成酯催化剂B相同或不同。The method according to any one of claims 1 to 8, wherein the compound of formula (III) is first contacted with the ester-forming catalyst A at -80 to 100 ° C for 0.5-20 hours, preferably at -80 to 50 ° C for 0.5- 10 hours, then add the compound of formula (II) and optional ester-forming catalyst B to contact at -80 to 100 ° C for 0.5-10 hours, preferably at -80 to 30 ° C for 0.5-5 hours, and then at -10 It is held at 50 ° C for 1-10 hours, preferably at 0-30 ° C for 1 to 4 hours, in order to cause an esterification reaction, wherein the esterification catalyst A and the esterification catalyst B are the same or different.
- 根据权利要求9的方法，其中成酯催化剂A与式(III)化合物的摩尔比为1:1至6:1，优选1:1至3:1；和/或，成酯催化剂B与式(II)化合物的摩尔比为1:1至6:1，优选1:1至3:1。The method according to claim 9, wherein the molar ratio of the ester-forming catalyst A to the compound of formula (III) is 1: 1 to 6: 1, preferably 1: 1 to 3: 1; and / or, the ester-forming catalyst B and formula ( II) The molar ratio of the compound is 1: 1 to 6: 1, preferably 1: 1 to 3: 1.
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