WO2022257957A1 - USE OF γ,δ-UNSATURATED OXIME ESTER COMPOUNDS AS PHOTOINITIATORS - Google Patents

USE OF γ,δ-UNSATURATED OXIME ESTER COMPOUNDS AS PHOTOINITIATORS Download PDF

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WO2022257957A1
WO2022257957A1 PCT/CN2022/097591 CN2022097591W WO2022257957A1 WO 2022257957 A1 WO2022257957 A1 WO 2022257957A1 CN 2022097591 W CN2022097591 W CN 2022097591W WO 2022257957 A1 WO2022257957 A1 WO 2022257957A1
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alkyl
aryl
amino
ring members
cycloalkyl
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PCT/CN2022/097591
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Chinese (zh)
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李治全
邹应全
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湖北固润科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system

Definitions

  • the invention relates to the field of photoinitiators, in particular to the use of ⁇ , ⁇ -unsaturated oxime ester compounds as photoinitiators.
  • Photocuring technology with "5E” characteristics has been widely used in traditional fields such as coatings, adhesives, and inks, as well as high-tech industries such as photoresist and 3D printing.
  • the photocuring system is mainly composed of oligomers, monomers, photoinitiators, additives, etc.
  • the photoinitiator is the core component of the photocuring system, and its function is to generate active species (free radicals, cations, etc.) after absorbing light energy. etc.), the polymerization and crosslinking of monomers and oligomers in the initiator system occurs, therefore, the activity of the photoinitiator has a decisive influence on the photocuring rate and degree of curing.
  • Oxime ester photoinitiator is a kind of high-sensitivity photoinitiator with excellent performance. After absorbing light energy, it can generate active free radicals to initiate polymerization through irreversible photodecarboxylation reaction. It is currently the most widely used commercial oxime ester photoinitiator. are OXE-1 and OXE2. It is worth noting that the photosensitivity of a photoinitiator not only depends on its absorption properties, but also its active radical quantum yield is an important determinant.
  • the active free radical quantum yields of reported oxime ester photoinitiators are lower than those of traditional I-type UV photoinitiators, such as ⁇ -dialkoxyacetophenones, ⁇ -hydroxyalkylphenones, ⁇ - Aminoalkylphenones, etc. Therefore, how to break through the active radical quantum yield limit of oxime ester photoinitiators is the key to effectively improving the sensitivity of this type of photoinitiators.
  • the present invention provides a ⁇ , ⁇ -unsaturated oxime ester used as a photoinitiator. Due to its specific molecular structure, the oxime ester initiator of the present invention has excellent initiation efficiency when used as a photoinitiator.
  • an object of the present invention is to provide a use of a ⁇ , ⁇ -unsaturated oxime ester compound as a photoinitiator, and this type of compound has excellent initiation efficiency.
  • Another object of the present invention is to provide a method for preparing the ⁇ , ⁇ -unsaturated oxime ester compound of the present invention.
  • the method is simple and easy, the conditions are mild, the raw materials are readily available and the price is low.
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, nitro, cyano, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl) amino, C 1 -C 20 alkoxy, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 10 cycloalkyl, C 4 -C 20 cycloalkylalkyl , C 4 -C 20 alkylcycloalkyl, C 3 -C 10 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 2 -C 20 alkenyl, C 6 -C 18 aryl , C 7 -C 20 aralkyl, C 7 -C 20 alkylaryl and C 6 -C 20 aryloxy;
  • R 6 represents C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 10 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 4 -C 20 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkylaryl; and
  • Ar represents aryl or heteroaryl.
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, nitro, cyano, amino, mono(C 1 -C 6 alkyl) Amino, di(C 1 -C 6 alkyl) amino, C 1 -C 12 alkoxy, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 12 cycloalkylalkyl, C 4 -C 12 alkylcycloalkyl, C 3 -C 8 cycloalkoxy, C 4 -C 12 cycloalkylalkoxy, C 2 -C 6 alkenyl, C 6 -C 10 aryl, C 7 -C 12 aralkyl, C 7 -C 12 alkylaryl and C 6 -C 10 aryloxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl) Amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 2 -C 6 alkenyl, C 6 -C 10 aryl and C 7 -C 12 alkylaryl;
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, C 1 -C 6 haloalkyl and C 1 -C 6 alkyl.
  • R 6 represents C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 12 cycloalkylalkyl , C 4 -C 12 alkyl cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkyl aryl;
  • R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkyl Cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl;
  • R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 5 -C 6 cycloalkyl, C 1 -C 6 alkane substituted by C 5 -C 6 cycloalkyl Base, phenyl or C 1 -C 6 alkyl substituted by phenyl;
  • R 6 is C 1 -C 6 alkyl.
  • Ar represents a C 6 -C 30 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl or heteroaryl group is unsubstituted Or substituted by one or more groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, hetero with 3-8 ring members Cycloalkyl, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC(O)R"' , wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl having 3-8 ring members, C 6 -C 10 aryl, heteroaryl or amino with 5-8 ring members;
  • Ar represents a C 6 -C 20 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl group or heteroaryl group is unsubstituted or replaced by one or more groups independently selected from the following group Substitution: hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5- 10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently Hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members base or amino;
  • Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein the aryl or heteroaryl group is unsubstituted or replaced by one or more groups independently selected from the group Group substitution: hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5 -Heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"' of 10 ring members, wherein R', R" and R"' are each independently is hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heterocycloalkyl with 5-8 ring members aryl or amino,
  • Ar is a heteroaryl having two or three fused rings and having 8-14, or 9-14 or 9-13 ring members, the heteroaryl having 1 or 2 N atoms as ring members , the heteroaryl is unsubstituted or substituted by one or more groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, with Heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, having 3-8 rings membered heterocycloalkyl, C 6 -C 10 aryl, heteroaryl having 5-8 ring members or amino.
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 2 -C 6 Alkenyl, C 6 -C 10 aryl and C 7 -C 12 alkylaryl;
  • R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl; and
  • Ar represents a C 6 -C 20 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : Hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino and C 1 -C 6 alkyl;
  • R 6 represents C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 6 alkyl substituted by C 5 -C 6 cycloalkyl , phenyl or C 1 - substituted by phenyl C 6 alkyl;
  • Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein the aryl group or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : Hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined in any one of items 1-7, and
  • Ar is a heteroaryl group with two or three fused rings and has 8-14, or 9-14 or 9-13 ring members, the heteroaryl group has 1 or 2 N atoms as ring members, the Heteroaryl is unsubstituted or substituted by one or more groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, with 3- Heterocycloalkyl with 8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC (O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, C having 3-8 ring members Heterocycloalkyl, C 6 -C 10 aryl, heteroaryl with 5-8 ring members
  • R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined in any one of items 1-10,
  • R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined in any one of items 1-10.
  • R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined in any one of items 1-10, and X 2 is halogen.
  • Photocurable composition comprising at least one ⁇ , ⁇ -unsaturated oxime ester compound of formula (I) according to any one of items 1-10.
  • a cured material obtainable from the photocurable composition of item 14.
  • Fig. 1 is the ultraviolet-visible light absorption spectrum of compound 2 and compound 3 in the examples of the present invention.
  • Fig. 2 is a graph of the real-time infrared conversion rate of monomers of the acrylate system containing compound 1 of Example 1 of the present invention and a reference compound respectively.
  • Fig. 3 is a digital photograph of a 3D printed structure obtained by using compound 3 of Example 3 of the present invention as a photoinitiator.
  • Figure 4 is a bar graph of monomer conversion in samples using compound 1, 2 or 3.
  • the first aspect of the present invention provides the ⁇ of formula (I), the purposes of ⁇ -unsaturated oxime ester compound as photoinitiator:
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, nitro, cyano, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl) amino, C 1 -C 20 alkoxy, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 10 cycloalkyl, C 4 -C 20 cycloalkylalkyl , C 4 -C 20 alkylcycloalkyl, C 3 -C 10 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 2 -C 20 alkenyl, C 6 -C 18 aryl , C 7 -C 20 aralkyl, C 7 -C 20 alkylaryl and C 6 -C 20 aryloxy;
  • R 6 represents C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 10 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 4 -C 20 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkylaryl; and
  • Ar represents aryl or heteroaryl.
  • the prefix "C n -C m " indicates in each case that the number of carbon atoms contained in the group is nm.
  • Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen comprises F, Cl or a combination thereof.
  • C n -C m alkyl means having nm, such as 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, especially preferably 1-4 A saturated hydrocarbon group of 2 carbon atoms, which may be branched or unbranched.
  • Examples include 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-ethyl Butyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-eth
  • C 1 -C 8 Alkyl can be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl and its isomers.
  • the C 1 -C 6 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof.
  • C 1 -C 4 Alkyl can be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl groups and their isomers.
  • C 1 -C 20 haloalkyl includes C 1 -C 12 haloalkyl, C 1 -C 8 haloalkyl, C 1 -C 6 haloalkyl, C 1 -C 4 haloalkyl.
  • Halogen and alkyl in haloalkyl are as defined herein for halogen and alkyl.
  • C 2 -C m alkenyl as used herein means having 2-m, such as 2-20, 2-12, preferably 2-6, more preferably 2-4 carbon atoms and having one or more An unsaturated open-chain hydrocarbon group with a double bond at any position, which may be branched or unbranched.
  • Examples include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4- Pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2- Methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl Alkenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl Base, 1-ethyl-2-propenyl, 1-hexen
  • C 2 -C 6 alkenyl can be vinyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, neopentenyl, 1-hex Alkenyl, 2-hexenyl, 3-hexenyl, isohexenyl, neohexenyl and isomers thereof.
  • C 2 -C 4 alkenyl can be vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl 1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl and isomers thereof.
  • C 3 -C m cycloalkyl refers to a saturated alicyclic monocyclic group having 3-m, such as 3-10, 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 means an alkyl group substituted by a cycloalkyl group and containing a total of 4-m carbon atoms, for example 4-20 carbon atoms, 4-12, preferably 4-10, 4-8 or 4-8 carbon atoms.
  • Alkyl and cycloalkyl are as defined herein, examples include cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutyl Propyl, Cyclobutylbutyl, Cyclopentylmethyl, Cyclopentylethyl, Cyclopentylpropyl, Cyclopentylbutyl, Cyclohexylmethyl, Cyclohexylethyl, Cyclohexylpropyl, Cyclohexyl Butyl, etc.
  • C 4 -C m alkylcycloalkyl means a cycloalkyl group substituted by an alkyl group and containing a total of 4-m carbon atoms, for example 4-20 carbon atoms, 4-12, preferably 4-10, 4-8 or 4-8 carbon atoms.
  • Alkyl and cycloalkyl are as defined herein, examples include methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethylcyclobutyl, propylcyclopropyl Butyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, etc.
  • C 6 -C m aryl refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group containing 6-m carbon atoms, such as 6-18, preferably 6-10 carbon atoms.
  • C 6 -C m aryl groups mention may be made of phenyl, azulenyl, cycloheptatrienyl, biphenylene, dicyclopentadienyl, fluorenyl, phenanthrenyl, triphenylene , pyrenyl, naphthacene, chrysyl, biphenyl, anthracenyl, indenyl, pentalenyl and naphthyl.
  • Aryl groups can be unsubstituted or substituted. Suitable substituents include, for example, hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, Heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"' having 5-10 ring members, wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-8 Heteroaryl or amino of ring members.
  • C 7 -C m aralkyl means an alkyl group substituted by an aryl group and contains a total of 7-m, such as 7-20 carbon atoms, 7-12, preferably 7-10 carbon atoms, more preferably 7-8 carbon atoms.
  • alkyl and aryl are as defined herein, examples include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and the like.
  • C 7 -C m alkylaryl denotes an aryl group substituted by an alkyl group and containing a total of 7-m, such as 7-20 carbon atoms, for example 7-12, preferably 7-10 carbon atoms, More preferably 7-8 carbon atoms.
  • alkyl and aryl are as defined herein, examples include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, methylnaphthalene base, ethyl naphthyl, etc.
  • C n -C m alkoxy refers to a C n -C m alkyl corresponding to any carbon atom of an open - chain C n -C m alkane bonded with an oxygen atom as a linking group.
  • C m alkyl such as C 1 -C 20 alkoxy, preferably C 1 -C 12 alkoxy, more preferably C 1 -C 8 alkoxy, especially preferably C 1 -C 6 alkoxy, especially preferably C 1 -C 4 alkoxy.
  • C 1 -C 8 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy Hexyl, hexyloxy, heptyloxy, octyloxy, isooctyloxy and their isomers.
  • C 1 -C 4 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and its isomers body.
  • C 3 -C m cycloalkoxy refers to any ring carbon atom in the C 3 -C m cycloalkane corresponding to the C 3 -C m cycloalkyl group having an oxygen atom as a linking group C 3 -C m cycloalkyl, such as C 3 -C 10 cycloalkoxy, preferably C 3 -C 8 cycloalkoxy, more preferably C 5 -C 6 cycloalkoxy, such as cyclopropyloxy, Cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy and isomers thereof.
  • C 4 -C m cycloalkylalkoxy refers to an alkoxy group substituted by a cycloalkyl group and contains a total of 4-m carbon atoms, such as 4-20, 4-12 carbon atoms, preferably 4 -8 carbon atoms.
  • examples include cyclopropylmethoxy, cyclopropylethoxy, cyclopropylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy , cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethoxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclo Hexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy and the like.
  • C 6 -C m aryloxy refers to any aromatic carbon atom in the C 6 -C m aromatic hydrocarbon corresponding to the C 6 -C m aryl group having an oxygen atom as a linking group.
  • C 6 -C m aryl such as phenoxy, tolyloxy, naphthyloxy and the like.
  • heterocycloalkyl is understood to mean comprising n-m ring members, such as 3-8, 3-7, 3-6 or 4-8, 4-7, 4-6, or 5, 6 or 7 ring members and one or more, such as 1-5, 1-3, 1 or 2 heteroatoms selected from N, O or S, as a saturated group of ring members.
  • Heteroaryl is understood to mean having 5-18 ring members, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, such as 5-16, A group of 5-14, 5-10 or 5-8, or 8-14, 9-14 or 9-13 ring members.
  • At least one ring atom of heteroaryl is a heteroatom, preferably the heteroatom is selected from N, O and S, more preferably N.
  • Heteroaryl preferably has 1 to 3, eg one or two, heteroatoms. More preferably heteroaryl is a ring system having two or three fused rings having 8-14, 9-14 or 9-13 ring members. Examples of heteroaryl groups include carbazole, pyridine, pyrrole, furan, pyrazole, imidazole and thiophene.
  • Aryl groups can be unsubstituted or substituted. Suitable substituents include, for example, hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, Heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"' having 5-10 ring members, wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-8 Heteroaryl or amino of ring members.
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, nitro, cyano, amino, mono(C 1 -C 6 alkyl)amino , Di(C 1 -C 6 alkyl)amino, C 1 -C 12 alkoxy, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 8 cycloalkyl, C 4 - C 12 cycloalkylalkyl, C 4 -C 12 alkylcycloalkyl, C 3 -C 8 cycloalkoxy, C 4 -C 12 cycloalkylalkoxy, C 2 -C 6 alkenyl, C 6 -C 10 aryl, C 7 -C 12 aralkyl, C 7 -C 12 alkylaryl and C 6 -C 10 aryloxy.
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl) amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkane Cycloalkyl, C 2 -C 6 alkenyl, C 6 -C 10 aryl and C 7 -C 12 alkylaryl.
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, C 1 -C 6 haloalkyl and C 1 -C 6 alkyl.
  • R 6 represents C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 12 cycloalkylalkyl, C 4 -C 12 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl.
  • R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl.
  • R 6 represents C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 6 alkyl substituted by C 5 -C 6 cycloalkyl , benzene or C 1 -C 6 alkyl substituted by phenyl. Most preferably R 6 is C 1 -C 6 alkyl.
  • Ar represents C 6 -C 30 aryl or heteroaryl having 5-18 ring members, wherein said aryl or heteroaryl is unsubstituted or replaced by one or more (e.g. 1-5, 1-4, 1-3, 1 or 2) are substituted with groups independently selected from the group consisting of: hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkane radical, heterocycloalkyl having 3-8 ring members, C 6 -C 10 aryl, heteroaryl having 5-8
  • Ar represents a C 6 -C 20 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl or heteroaryl group is unsubstituted or replaced by one or more (e.g.
  • Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein said aryl or heteroaryl group is unsubstituted or replaced by one or more (e.g.
  • Ar can be, for example, phenyl, naphthyl or carbazole, which can be independently selected from C 1 - C 6 alkyl, group substitution of C(O)R', where R' is hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkane with 3-8 ring members radical or C 6 -C 10 aryl.
  • each variable in the compound of formula (I) has the following definitions:
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 2 -C 6 Alkenyl, C 6 -C 10 aryl and C 7 -C 12 alkylaryl;
  • R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl; and
  • Ar represents a C 6 -C 20 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : Hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
  • each variable in the compound of formula (I) has the following definitions:
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino, C 1 -C 6 alkyl and C 1 -C 6 haloalkyl;
  • R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 5 -C 6 cycloalkyl, C 1 -C 6 alkyl substituted by C 5 -C 6 cycloalkyl , phenyl or C 1 -C 6 alkyl substituted by phenyl;
  • Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein the aryl group or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : Hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
  • each variable in the compound of formula (I) has the following definitions:
  • R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino and C 1 -C 6 alkyl;
  • R 6 represents C 1 -C 6 alkyl
  • Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein the aryl group or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members , amino, -C(O)R', wherein R' is C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 Aryl or heteroaryl having 5-8 ring members.
  • One aspect of the present invention relates to a ⁇ , ⁇ -unsaturated oxime ester compound of formula (I):
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each as defined above, and
  • Ar is a heteroaryl group with two or three fused rings and has 8-14, or 9-14 or 9-13 ring members, the heteroaryl group has 1 or 2 N atoms as ring members, the Heteroaryl is unsubstituted or substituted by one or more (such as 1-5, 1-3 or 1 or 2) groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 Alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C( O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl
  • Ar is carbazole, which is unsubstituted or substituted by one or more (such as 1-5 or 1-3) substituents as defined above, preferably by one or more (such as 1 -5, 1-4, 1-3, 1 or 2) substituted by groups independently selected from C 1 -C 6 alkyl, C(O)R', wherein R' is hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members or C 6 -C 10 aryl.
  • the compound of formula (I) is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • the second aspect of the present invention relates to a method for preparing the compound of formula (I) of the present invention, which comprises making the compound of formula (E)
  • R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined above,
  • the hydroxyl group in the oxime group is converted into an ester group, thereby obtaining the compound of formula (I).
  • the esterification agent there is no particular limitation on the esterification agent, as long as it can convert the hydroxyl group in the oxime group of the compound of formula (III) into an ester group.
  • the esterification reagent the corresponding acid halides, such as acid chlorides, the corresponding carboxylic acids, and the corresponding acid anhydrides can also be used.
  • the reaction of the compound of formula (E) and compound of formula (F) is usually carried out in the presence of a catalyst, for example, the compound of formula (E) and compound of formula (F) are dispersed in an organic solvent in the presence of a catalyst.
  • the catalyst can be any one or a mixture of two or more of triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide or sodium hydride.
  • the molar ratio of the compound of the formula (E) to the compound of the formula (F) can be 1:2-1:5; the molar ratio of the compound of the formula (E) to the catalyst can be 1:2-1:15. Said ratio is conducive to the improvement of product yield.
  • the reaction temperature can be 10-100°C, and the reaction time can be 1-8 hours, such as 1-5 hours.
  • the compound of formula (E) can be obtained by oximating the compound of formula (C) with hydroxylamine and/or hydroxylamine hydrochloride
  • R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined above.
  • the reaction of the compound of formula (C) with hydroxylamine and/or hydroxylamine hydrochloride can be carried out in the presence of a catalyst.
  • the catalyst can be, for example, sodium bicarbonate, any one of sodium carbonate or sodium acetate or a mixture of two or more.
  • the molar ratio of the compound of formula (C) to hydroxylamine and/or hydroxylamine hydrochloride may be 1:2 ⁇ 1:5.
  • the molar ratio of the compound of formula (C) to the catalyst can be 1:2-1:15.
  • the compound of formula (C) can be obtained by making the compound of formula (A)
  • R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined above, and X 2 is halogen.
  • the reaction of the compound of formula (A) with the compound of formula (B) can be carried out in the presence of a catalyst.
  • a catalyst include any one or a mixture of two or more of aluminum trichloride, aluminum tribromide, iron trichloride, boron trifluoride, and zinc dichloride.
  • the reaction described is a Friedel-Crafts acylation reaction.
  • the reaction temperature may be 50-150°C, and the reaction time may be 1-10 hours.
  • the reaction of the above-mentioned formula (A) compound and the formula (B) compound, the reaction of the formula (C) compound and hydroxylamine and/or hydroxylamine hydrochloride, the reaction of the formula (E) compound and the formula (F) compound can be carried out in the presence of an organic solvent .
  • the organic solvent can be any one or a mixture of two or more of dichloromethane, chloroform, methanol, ethanol, toluene, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide or triethylamine.
  • the compound of the formula (I) of the present invention is used as a photoinitiator in the UV-vis photocuring system, and can effectively initiate the curing reaction.
  • the compound of formula (I) of the present invention can be used as a photoinitiator in a photocuring system with a radiation wavelength of 300-550 nm, preferably 350-525 nm.
  • the compound of formula (I) of the present invention can also be used as a photoinitiator for 3D printing.
  • Another aspect of the present invention relates to a photocurable composition
  • a photocurable composition comprising at least one ⁇ , ⁇ -unsaturated oxime ester compound of formula (I) according to the invention.
  • the amount of the compound of formula (I) according to the invention is generally 0.01-10% by weight, for example 0.02% by weight, 0.05% by weight, 0.08% by weight, 0.1% by weight, 0.2% by weight, 0.5% by weight, 0.8% by weight, 1% by weight, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.5 wt% %, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, preferably 0.1-6% by weight, such as 0.2-5% by weight, based on the active ingredient amount of the photocurable composition.
  • the active ingredient refers to the ingredients in the photocurable composition except the solvent.
  • the photocurable composition contains a photocurable compound in addition to the photoinitiator of the present invention.
  • a photocurable compound refers to a monomer or oligomer containing an unsaturated carbon-carbon double bond. After the monomer or oligomer is irradiated by light, the polymerization reaction can be initiated by the photoinitiator, and then cross-linking and curing can occur.
  • a cured material obtainable from the photocurable composition of the present invention.
  • the cured material may be a photocurable coating, which includes coatings containing functional materials, coatings of color filters for UV light and/or visible light; encapsulants; photolithographic materials; holographic recording materials; 3D printing materials; lithographic printing Materials; preparation materials for optical devices and materials for improving mechanical properties, such as carbon fiber composite materials and/or inorganic nanoparticles and/or organic nanoparticles, etc.
  • the beneficial effect of ⁇ -unsaturated oxime ester compound as photoinitiator comprises:
  • the absorption wavelength of the photoinitiator can be adjusted, and it can be used as an ultraviolet photoinitiator or a visible light initiator. It can be used in conjunction with energy-saving and environmentally friendly LED light sources, and has a wide range of applications;
  • the photoinitiator of the present invention can be used for 3D printing to construct delicate three-dimensional models.
  • Embodiment 1 the preparation of compound 1:
  • Phenyl-4-penten-1-one oxime (28mg, 0.159mmol) and 5mL THF were added to a 25mL round-bottomed flask, and sodium hydride (7.5mg, 0.315mmol) was added to react for 30min while stirring in an ice bath. Then, acryloyl chloride (43.4 mg, 0.479 mmol) was added to continue the reaction for 30 min. After the reaction was completed, the reaction was quenched with deionized water. The THF was removed by rotary evaporation, and the aqueous phase was extracted three times with ethyl acetate.
  • Embodiment 2 the preparation of compound 2:
  • Embodiment 3 the preparation of compound 3:
  • N-ethylcarbazole-4-butenyl-3-(2-methylphenyl)ketone 0.563g, 1.583mmol
  • hydroxylamine hydrochloride 0.330g, 4.751mmol
  • anhydrous sodium acetate 0.89g , 4.751mmol
  • 25mL of absolute ethanol 25mL
  • N-ethylcarbazole-6-(2-methylbenzoyl)-3-methylketoxime 0.594g, 1.529mmol
  • tetrahydrofuran 20mL
  • sodium hydride 0.11g, 4.587mmol
  • acetyl chloride 0.15 g, 4.587 mmol
  • the reaction was quenched with saturated sodium bicarbonate, and the product was extracted with 20 mL ⁇ 3 dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate.
  • the properties of Compounds 2 and 3 prepared in Examples 2 and 3 were measured by UV-visible spectrophotometer at 200-600 nm.
  • the ultraviolet-visible light absorption spectra of compounds 2 and 3 are shown in Figure 1, indicating that by changing the structure and type of aromatic compounds (i.e. Ar groups), the absorption wavelength of the photoinitiator can be regulated, which can be compared with traditional high-pressure mercury lamps and energy-saving and environment-friendly lamps.
  • the LED light source is matched and has a wide range of applications.
  • Fig. 2 is the real-time curve of monomer conversion rate in the sample.
  • the results in Fig. 2 show that the photoinitiation efficiency of the ⁇ , ⁇ -unsaturated oxime ester of the present invention is significantly higher than that of the reference compound without ⁇ , ⁇ -unsaturated carbon-carbon double bonds at the end.
  • the polymerization rate and conversion rate of the initiating monomer of the ⁇ , ⁇ -unsaturated oxime ester of the present invention are higher than those of the reference compound without ⁇ , ⁇ -unsaturated carbon-carbon double bond at the end.
  • Figure 4 is a histogram of monomer conversion rates in different samples after irradiation for 600s, wherein the monomer conversion rate of the system using compound 1 is about 58%, and the monomer conversion rate of the system using compound 2 is about 69%. The monomer conversion of the system of 3 was about 81%. Result shows in Fig. 4, when using the compound of the present invention as photoinitiator, monomer good polymerization rate and conversion rate, and the polymerization rate and conversion rate of the initiation monomer of the gamma that contains carbazole group, the delta-unsaturated oxime ester The rate is higher than that of phenyl ⁇ , ⁇ -unsaturated oxime ester.

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Abstract

The present invention relates to a use of γ,δ-unsaturated oxime ester compounds of formula (I) as photoinitiators, wherein variables are as defined in the description. The present invention further relates to a preparation method for the γ,δ-unsaturated oxime ester compounds. The γ,δ-unsaturated oxime ester compounds of the present invention have excellent initiation efficiency when being used as photoinitiators.

Description

γ,δ-不饱和肟酯化合物作为光引发剂的用途Use of γ, δ-unsaturated oxime ester compounds as photoinitiators 技术领域technical field
本发明涉及光引发剂领域，具体涉及γ,δ-不饱和肟酯化合物作为光引发剂的用途。The invention relates to the field of photoinitiators, in particular to the use of γ, δ-unsaturated oxime ester compounds as photoinitiators.
背景技术Background technique
具有“5E”特点(高效、适应性广、经济、节能、环保)的光固化技术已在涂层、胶黏剂、油墨等传统领域及光刻胶、3D打印等高新技术中得到了广泛应用。光固化体系主要由低聚物、单体、光引发剂、助剂等组成，其中，光引发剂是光固化体系的核心组分，其作用是吸收光能后产生活性物种(自由基、阳离子等)，引发体系中单体和低聚物发生聚合交联，因此，光引发剂的活性对光固化速率和固化程度有决定性影响。Photocuring technology with "5E" characteristics (high efficiency, wide adaptability, economy, energy saving, and environmental protection) has been widely used in traditional fields such as coatings, adhesives, and inks, as well as high-tech industries such as photoresist and 3D printing. . The photocuring system is mainly composed of oligomers, monomers, photoinitiators, additives, etc. Among them, the photoinitiator is the core component of the photocuring system, and its function is to generate active species (free radicals, cations, etc.) after absorbing light energy. etc.), the polymerization and crosslinking of monomers and oligomers in the initiator system occurs, therefore, the activity of the photoinitiator has a decisive influence on the photocuring rate and degree of curing.
肟酯光引发剂是一类性能优良的高感光度光引发剂，其吸收光能后可通过不可逆的光致脱羧反应产生活性自由基引发聚合，目前应用最广泛的商品化肟酯光引发剂是OXE-1和OXE2。值得注意的是，光引发剂的感光性不仅取决于其吸收性能，其活性自由基量子产率也是重要的决定因素。目前已报道的肟酯光引发剂的活性自由基量子产率低于传统的I型UV光引发剂，如α-二烷氧基苯乙酮类、α-羟基烷基苯酮类、α-氨基烷基苯酮类等。因此，如何突破肟酯光引发剂的活性自由基量子产率极限是有效提升该类光引发剂感光度的关键。Oxime ester photoinitiator is a kind of high-sensitivity photoinitiator with excellent performance. After absorbing light energy, it can generate active free radicals to initiate polymerization through irreversible photodecarboxylation reaction. It is currently the most widely used commercial oxime ester photoinitiator. are OXE-1 and OXE2. It is worth noting that the photosensitivity of a photoinitiator not only depends on its absorption properties, but also its active radical quantum yield is an important determinant. The active free radical quantum yields of reported oxime ester photoinitiators are lower than those of traditional I-type UV photoinitiators, such as α-dialkoxyacetophenones, α-hydroxyalkylphenones, α- Aminoalkylphenones, etc. Therefore, how to break through the active radical quantum yield limit of oxime ester photoinitiators is the key to effectively improving the sensitivity of this type of photoinitiators.
发明内容Contents of the invention
为了解决上述问题，本发明提供了一种γ,δ-不饱和肟酯作为光引发剂用途。本发明的肟酯引发剂由于其特定的分子结构，在用作光引发剂时具有优异的引发效率。In order to solve the above problems, the present invention provides a γ, δ-unsaturated oxime ester used as a photoinitiator. Due to its specific molecular structure, the oxime ester initiator of the present invention has excellent initiation efficiency when used as a photoinitiator.
因此，本发明的一个目的是提供一种γ,δ-不饱和肟酯化合物作为光引发剂的用途，该类化合物具有优异的引发效率。Therefore, an object of the present invention is to provide a use of a γ, δ-unsaturated oxime ester compound as a photoinitiator, and this type of compound has excellent initiation efficiency.
本发明的另一目的是提供制备本发明γ,δ-不饱和肟酯化合物的方法。所述方法简单易行，条件温和，原料易得，价格低廉。Another object of the present invention is to provide a method for preparing the γ, δ-unsaturated oxime ester compound of the present invention. The method is simple and easy, the conditions are mild, the raw materials are readily available and the price is low.
实现本发明上述目的的技术方案可以概括如下:The technical scheme that realizes the above-mentioned purpose of the present invention can be summarized as follows:
1.式(I)的γ,δ-不饱和肟酯化合物作为光引发剂的用途，1. the γ of formula (I), the purposes of δ-unsaturated oxime ester compound as photoinitiator,
Figure PCTCN2022097591-appb-000001
Figure PCTCN2022097591-appb-000001
其中，R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、硝基、氰基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基、C 1-C 20烷氧基、C 1-C 20烷基、C 1-C 20卤代烷基、C 3-C 10环烷基、C 4-C 20环烷基烷基、C 4-C 20烷基环烷基、C 3-C 10环烷氧基、C 4-C 20环烷基烷氧基、C 2-C 20烯基、C 6-C 18的芳基、C 7-C 20芳烷基、C 7-C 20烷基芳基和C 6-C 20芳氧基； Wherein, R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, nitro, cyano, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl) amino, C 1 -C 20 alkoxy, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 10 cycloalkyl, C 4 -C 20 cycloalkylalkyl , C 4 -C 20 alkylcycloalkyl, C 3 -C 10 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 2 -C 20 alkenyl, C 6 -C 18 aryl , C 7 -C 20 aralkyl, C 7 -C 20 alkylaryl and C 6 -C 20 aryloxy;
R 6表示C 1-C 20烷基、C 1-C 20卤代烷基、C 3-C 10环烷基、C 4-C 20环烷基烷基、C 4-C 20烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基；和 R 6 represents C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 10 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 4 -C 20 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkylaryl; and
Ar表示芳基或杂芳基。Ar represents aryl or heteroaryl.
2.根据第1项的用途，其中R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、硝基、氰基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基、C 1-C 12烷氧基、C 1-C 12烷基、C 1-C 12卤代烷基、C 3-C 8环烷基、C 4-C 12环烷基烷基、C 4-C 12烷基环烷基、C 3-C 8环烷氧基、C 4-C 12环烷基烷氧基、C 2-C 6烯基、C 6-C 10的芳基、C 7-C 12芳烷基、C 7-C 12烷基芳基和C 6-C 10芳氧基； 2. The use according to item 1, wherein R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, nitro, cyano, amino, mono(C 1 -C 6 alkyl) Amino, di(C 1 -C 6 alkyl) amino, C 1 -C 12 alkoxy, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 12 cycloalkylalkyl, C 4 -C 12 alkylcycloalkyl, C 3 -C 8 cycloalkoxy, C 4 -C 12 cycloalkylalkoxy, C 2 -C 6 alkenyl, C 6 -C 10 aryl, C 7 -C 12 aralkyl, C 7 -C 12 alkylaryl and C 6 -C 10 aryloxy;
优选的是，R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 2-C 6烯基、C 6-C 10的芳基和C 7-C 12烷基芳基； Preferably, R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl) Amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 2 -C 6 alkenyl, C 6 -C 10 aryl and C 7 -C 12 alkylaryl;
更优选R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、C 1-C 6卤代烷基和C 1-C 6烷基。 More preferably, R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, C 1 -C 6 haloalkyl and C 1 -C 6 alkyl.
3.根据第1或2项的用途，其中R 6表示C 1-C 12烷基、C 1-C 12卤代烷基、C 3-C 8环烷基、C 4-C 12环烷基烷基、C 4-C 12烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基； 3. Use according to item 1 or 2, wherein R 6 represents C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 12 cycloalkylalkyl , C 4 -C 12 alkyl cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkyl aryl;
优选的是，R 6表示C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基； Preferably, R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkyl Cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl;
更优选的是，R 6表示C 1-C 6烷基、C 1-C 6卤代烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 6烷基、苯基或者被苯基取代的C 1-C 6烷基； More preferably, R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 5 -C 6 cycloalkyl, C 1 -C 6 alkane substituted by C 5 -C 6 cycloalkyl Base, phenyl or C 1 -C 6 alkyl substituted by phenyl;
最优选R 6为C 1-C 6烷基。 Most preferably R 6 is C 1 -C 6 alkyl.
4.根据第1-3项中任一项的用途，其中Ar表示C 6-C 30芳基或具有5-18个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基； 4. Use according to any one of items 1-3, wherein Ar represents a C 6 -C 30 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl or heteroaryl group is unsubstituted Or substituted by one or more groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, hetero with 3-8 ring members Cycloalkyl, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC(O)R"' , wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl having 3-8 ring members, C 6 -C 10 aryl, heteroaryl or amino with 5-8 ring members;
优选Ar表示C 6-C 20芳基或具有5-18个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基； Preferably, Ar represents a C 6 -C 20 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl group or heteroaryl group is unsubstituted or replaced by one or more groups independently selected from the following group Substitution: hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5- 10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently Hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members base or amino;
更优选Ar表示C 6-C 14芳基或具有5-14个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂 芳基或氨基， More preferably Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein the aryl or heteroaryl group is unsubstituted or replaced by one or more groups independently selected from the group Group substitution: hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5 -Heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"' of 10 ring members, wherein R', R" and R"' are each independently is hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heterocycloalkyl with 5-8 ring members aryl or amino,
尤其是Ar为具有两个或三个稠合环的杂芳基，并且具有8-14，或9-14或9-13个环成员，该杂芳基具有1或2个N原子作为环成员，该杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 In particular Ar is a heteroaryl having two or three fused rings and having 8-14, or 9-14 or 9-13 ring members, the heteroaryl having 1 or 2 N atoms as ring members , the heteroaryl is unsubstituted or substituted by one or more groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, with Heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, having 3-8 rings membered heterocycloalkyl, C 6 -C 10 aryl, heteroaryl having 5-8 ring members or amino.
5.根据第1-4项中任一项的用途，其中式(I)化合物中的各变量具有如下定义：5. Use according to any one of items 1-4, wherein each variable in the compound of formula (I) has the following definitions:
R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 2-C 6烯基、C 6-C 10的芳基和C 7-C 12烷基芳基； R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 2 -C 6 Alkenyl, C 6 -C 10 aryl and C 7 -C 12 alkylaryl;
R 6表示C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基；和 R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl; and
Ar表示C 6-C 20芳基或具有5-18个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 Ar represents a C 6 -C 20 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : Hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
6.根据第1-5项中任一项的用途，其中式(I)化合物中的各变量具有如下定义：6. Use according to any one of items 1-5, wherein each variable in the compound of formula (I) has the following definitions:
R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和C 1-C 6烷基； R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino and C 1 -C 6 alkyl;
R 6表示C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 6烷基、苯基或者被苯基取代的C 1-C 6烷基；和 R 6 represents C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 6 alkyl substituted by C 5 -C 6 cycloalkyl , phenyl or C 1 - substituted by phenyl C 6 alkyl; and
Ar表示C 6-C 14芳基或具有5-14个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein the aryl group or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : Hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
7.根据第1-6项中任一项的用途，其中式(I)化合物选自下述化合物：7. The use according to any one of items 1-6, wherein the compound of formula (I) is selected from the following compounds:
Figure PCTCN2022097591-appb-000002
Figure PCTCN2022097591-appb-000002
8.根据第1-7项中任一项的用途，其中用于辐射波长为300-550nm、优选350-525nm的光固化体系，特别是用于3D打印。8. Use according to any one of items 1-7, for photocuring systems with radiation wavelengths of 300-550 nm, preferably 350-525 nm, especially for 3D printing.
9.一种式(I)的γ,δ-不饱和肟酯化合物：9. A γ, δ-unsaturated oxime ester compound of formula (I):
Figure PCTCN2022097591-appb-000003
Figure PCTCN2022097591-appb-000003
其中R 1、R 2、R 3、R 4、R 5和R 6如第1-7项中任一项所定义，以及 wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined in any one of items 1-7, and
Ar为具有两个或三个稠合环的杂芳基，并且具有8-14，或9-14或9- 13个环成员，该杂芳基具有1或2个N原子作为环成员，该杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 Ar is a heteroaryl group with two or three fused rings and has 8-14, or 9-14 or 9-13 ring members, the heteroaryl group has 1 or 2 N atoms as ring members, the Heteroaryl is unsubstituted or substituted by one or more groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, with 3- Heterocycloalkyl with 8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC (O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, C having 3-8 ring members Heterocycloalkyl, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
10.根据第9项的化合物，其为10. The compound according to item 9, which is
Figure PCTCN2022097591-appb-000004
Figure PCTCN2022097591-appb-000004
11.一种制备如第1-10项中任一项所定义的式(I)化合物的方法，其包括使式(E)化合物11. A method for preparing a compound of formula (I) as defined in any one of items 1-10, comprising making the compound of formula (E)
Figure PCTCN2022097591-appb-000005
Figure PCTCN2022097591-appb-000005
其中R 1、R 2、R 3、R 4、R 5和Ar如第1-10项中任一项所定义， wherein R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined in any one of items 1-10,
与式(F)化合物反应得到式(I)化合物Reaction with formula (F) compound obtains formula (I) compound
Figure PCTCN2022097591-appb-000006
Figure PCTCN2022097591-appb-000006
其中X 1为卤素、羟基或-C(＝O)-R 6，以及R 6如第1-10项中任一项所定义。 wherein X 1 is halogen, hydroxyl or -C(=O)-R 6 , and R 6 is as defined in any one of items 1-10.
12.根据第11项的方法，其包括使式(C)化合物与羟胺和/或盐酸羟胺进行肟化反应得到式(E)化合物12. The method according to item 11, which comprises making the compound of formula (C) carry out oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain the compound of formula (E)
Figure PCTCN2022097591-appb-000007
Figure PCTCN2022097591-appb-000007
其中R 1、R 2、R 3、R 4、R 5和Ar如第1-10项中任一项所定义。 wherein R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined in any one of items 1-10.
13.根据第12项的方法，其包括使式(A)化合物13. The method according to item 12, which comprises making the compound of formula (A)
Ar-HAr-H
(A)(A)
其中Ar如第1-10项中任一项所定义，where Ar is as defined in any one of items 1-10,
与式(B)化合物反应而制备式(C)化合物React with formula (B) compound and prepare formula (C) compound
Figure PCTCN2022097591-appb-000008
Figure PCTCN2022097591-appb-000008
其中R 1、R 2、R 3、R 4、R 5和Ar如第1-10项中任一项所定义，以及X 2为卤素。 wherein R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined in any one of items 1-10, and X 2 is halogen.
14.包含至少一种根据第1-10项中任一项的式(I)的γ,δ-不饱和肟酯化合物的光固化性组合物。14. Photocurable composition comprising at least one γ,δ-unsaturated oxime ester compound of formula (I) according to any one of items 1-10.
15.可由第14项的光固化性组合物得到的固化材料。15. A cured material obtainable from the photocurable composition of item 14.
附图说明Description of drawings
图1为本发明实施例中的化合物2和化合物3的紫外-可见光吸收光谱。Fig. 1 is the ultraviolet-visible light absorption spectrum of compound 2 and compound 3 in the examples of the present invention.
图2为分别包含本发明实施例1的化合物1和参比化合物的丙烯酸酯体系的单体实时红外转化率图。Fig. 2 is a graph of the real-time infrared conversion rate of monomers of the acrylate system containing compound 1 of Example 1 of the present invention and a reference compound respectively.
图3为使用本发明实施例3的化合物3作为光引发剂得到的3D打印成型结构的数码照片图。Fig. 3 is a digital photograph of a 3D printed structure obtained by using compound 3 of Example 3 of the present invention as a photoinitiator.
图4为使用化合物1、2或3的样品中单体转化率柱状图。Figure 4 is a bar graph of monomer conversion in samples using compound 1, 2 or 3.
具体实施方式Detailed ways
本发明的第一个方面提供了式(I)的γ,δ-不饱和肟酯化合物作为光引发剂的用途：The first aspect of the present invention provides the γ of formula (I), the purposes of δ-unsaturated oxime ester compound as photoinitiator:
Figure PCTCN2022097591-appb-000009
Figure PCTCN2022097591-appb-000009
其中，R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、硝基、氰基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基、C 1-C 20烷氧基、C 1-C 20烷基、C 1-C 20卤代烷基、C 3-C 10环烷基、C 4-C 20环烷基烷基、C 4-C 20烷基环烷基、C 3-C 10环烷氧基、C 4-C 20环烷基烷氧基、C 2-C 20烯基、C 6-C 18的芳基、C 7-C 20芳烷基、C 7-C 20烷基芳基和C 6-C 20芳氧基； Wherein, R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, nitro, cyano, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl) amino, C 1 -C 20 alkoxy, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 10 cycloalkyl, C 4 -C 20 cycloalkylalkyl , C 4 -C 20 alkylcycloalkyl, C 3 -C 10 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 2 -C 20 alkenyl, C 6 -C 18 aryl , C 7 -C 20 aralkyl, C 7 -C 20 alkylaryl and C 6 -C 20 aryloxy;
R 6表示C 1-C 20烷基、C 1-C 20卤代烷基、C 3-C 10环烷基、C 4-C 20环烷基烷基、C 4-C 20烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基；和 R 6 represents C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 10 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 4 -C 20 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkylaryl; and
Ar表示芳基或杂芳基。Ar represents aryl or heteroaryl.
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 " indicates 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" refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen comprises 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个碳原子的饱和烃基，其可以是支化或未支化的。实例包括甲基、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。 As used herein, the term "C n -C m alkyl" means having nm, such as 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, especially preferably 1-4 A saturated hydrocarbon group of 2 carbon atoms, which may be branched or unbranched. Examples include 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-ethyl Butyl, 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 their isomers. C 1 -C 8 Alkyl can be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl and its isomers. The C 1 -C 6 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof. C 1 -C 4 Alkyl can be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl groups and their isomers.
“C 1-C 20卤代烷基”包括C 1-C 12卤代烷基、C 1-C 8卤代烷基、C 1-C 6卤代烷基，C 1-C 4卤代烷基。卤代烷基中的卤素和烷基如本文对卤素和烷基所定义。 "C 1 -C 20 haloalkyl" includes C 1 -C 12 haloalkyl, C 1 -C 8 haloalkyl, C 1 -C 6 haloalkyl, C 1 -C 4 haloalkyl. Halogen and alkyl in haloalkyl are as defined herein for halogen and alkyl.
本文所用术语“C 2-C m烯基”是指具有2-m个，例如2-20个，2-12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不饱和开链烃基，其可以是支化或未支化的。实例包括乙烯基、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。 The term "C 2 -C m alkenyl" as used herein means having 2-m, such as 2-20, 2-12, preferably 2-6, more preferably 2-4 carbon atoms and having one or more An unsaturated open-chain hydrocarbon group with a double bond at any position, which may be branched or unbranched. Examples include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4- Pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2- Methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl Alkenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl Base, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentyl Alkenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl Base-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl Base, 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-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butene base, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl Base-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 Base-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 can be vinyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, neopentenyl, 1-hex Alkenyl, 2-hexenyl, 3-hexenyl, isohexenyl, neohexenyl and isomers thereof. C 2 -C 4 alkenyl can be vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl 1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl and isomers thereof.
本文所用术语“C 3-C m环烷基”是指具有3-m个，例如3-10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 3-10, 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个碳原子，4-12，优选4-10个、4-8或4-8个碳原子。烷基和环烷基适用本文所定义，实例包括环丙基甲基、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" means an alkyl group substituted by a cycloalkyl group and containing a total of 4-m carbon atoms, for example 4-20 carbon atoms, 4-12, preferably 4-10, 4-8 or 4-8 carbon atoms. Alkyl and cycloalkyl are as defined herein, examples include cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutyl Propyl, Cyclobutylbutyl, Cyclopentylmethyl, Cyclopentylethyl, Cyclopentylpropyl, Cyclopentylbutyl, Cyclohexylmethyl, Cyclohexylethyl, Cyclohexylpropyl, Cyclohexyl Butyl, etc.
术语“C 4-C m烷基环烷基”表示被烷基取代的环烷基并且总共含有4-m个碳原子，例如4-20个碳原子，4-12，优选4-10个、4-8或4-8个碳原子。烷基和环烷基适用本文所定义，实例包括甲基环丙基、乙基环丙基、丙基环丙基、丁基环丙基、甲基环丁基、乙基环丁基、丙基环丁基、丁基环丁基、甲基环戊基、乙基环戊基、丙基环戊基、丁基环戊基、甲基环己基、乙基环己基、丙基环己基、丁基环己基等。 The term "C 4 -C m alkylcycloalkyl" means a cycloalkyl group substituted by an alkyl group and containing a total of 4-m carbon atoms, for example 4-20 carbon atoms, 4-12, preferably 4-10, 4-8 or 4-8 carbon atoms. Alkyl and cycloalkyl are as defined herein, examples include methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethylcyclobutyl, propylcyclopropyl Butyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, etc.
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、薁基、并环庚三烯基、亚联苯基、二环戊二烯并苯基、芴基、菲基、三亚苯基、芘基、并四苯基、屈基、联苯基、蒽基、茚基、并环戊二烯基和萘基。芳基可以是未被取代或被取代的。合适取代基例如包括羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、 -OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 The term "C 6 -C m aryl" used herein refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group containing 6-m carbon atoms, such as 6-18, preferably 6-10 carbon atoms. As examples of C 6 -C m aryl groups, mention may be made of phenyl, azulenyl, cycloheptatrienyl, biphenylene, dicyclopentadienyl, fluorenyl, phenanthrenyl, triphenylene , pyrenyl, naphthacene, chrysyl, biphenyl, anthracenyl, indenyl, pentalenyl and naphthyl. Aryl groups can be unsubstituted or substituted. Suitable substituents include, for example, hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, Heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"' having 5-10 ring members, wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-8 Heteroaryl or amino of ring members.
术语“C 7-C m芳烷基”表示被芳基取代的烷基并且总共含有7-m个，例如7-20个碳原子，7-12个，优选7-10个碳原子，更优选7-8个碳原子。其中烷基和芳基适用本文所定义，实例包括苯甲基、苯乙基、萘甲基、萘乙基等。 The term "C 7 -C m aralkyl" means an alkyl group substituted by an aryl group and contains a total of 7-m, such as 7-20 carbon atoms, 7-12, preferably 7-10 carbon atoms, more preferably 7-8 carbon atoms. Where alkyl and aryl are as defined herein, examples include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and the like.
术语“C 7-C m烷基芳基”表示被烷基取代的芳基并且总共含有7-m个，如7-20个碳原子，例如7-12个，优选7-10个碳原子，更优选7-8个碳原子。其中烷基和芳基适用本文所定义，实例包括甲基苯基、二甲基苯基、三甲基苯基、乙基苯基、二乙基苯基、三乙基苯基、甲基萘基、乙基萘基等。 The term "C 7 -C m alkylaryl" denotes an aryl group substituted by an alkyl group and containing a total of 7-m, such as 7-20 carbon atoms, for example 7-12, preferably 7-10 carbon atoms, More preferably 7-8 carbon atoms. where alkyl and aryl are as defined herein, examples include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, methylnaphthalene base, ethyl naphthyl, etc.
术语“C n-C m烷氧基”是指在C n-C m烷基对应的开链C n-C m烷烃的任何碳原子上键合有一个氧原子作为连接基团的C n-C m烷基，例如C 1-C 20烷氧基，优选C 1-C 12烷氧基，更优选C 1-C 8烷氧基，特别优选C 1-C 6烷氧基，尤其优选C 1-C 4烷氧基。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。 The term "C n -C m alkoxy" refers to a C n -C m alkyl corresponding to any carbon atom of an open - chain C n -C m alkane bonded with an oxygen atom as a linking group. C m alkyl, such as C 1 -C 20 alkoxy, preferably C 1 -C 12 alkoxy, more preferably C 1 -C 8 alkoxy, especially preferably C 1 -C 6 alkoxy, especially preferably C 1 -C 4 alkoxy. C 1 -C 8 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy Hexyl, hexyloxy, heptyloxy, octyloxy, isooctyloxy and their isomers. C 1 -C 4 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and its isomers body.
术语“C 3-C m环烷氧基”是指在C 3-C m环烷基对应的C 3-C m环烷烃中的任何环碳原子上键合有一个氧原子作为连接基团的C 3-C m环烷基，例如C 3-C 10环烷氧基，优选C 3-C 8环烷氧基，更优选C 5-C 6环烷氧基，例如环丙基氧基、环丁基氧基、环戊基氧基、环己基氧基、环庚基氧基、环辛基氧基、环癸基氧基及其异构体。 The term "C 3 -C m cycloalkoxy" refers to any ring carbon atom in the C 3 -C m cycloalkane corresponding to the C 3 -C m cycloalkyl group having an oxygen atom as a linking group C 3 -C m cycloalkyl, such as C 3 -C 10 cycloalkoxy, preferably C 3 -C 8 cycloalkoxy, more preferably C 5 -C 6 cycloalkoxy, such as cyclopropyloxy, Cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy and isomers thereof.
术语“C 4-C m环烷基烷氧基”是指被环烷基取代的烷氧基并且总共含有4-m个碳原子，例如4-20个，4-12个碳原子，优选4-8个碳原子。其中环烷基适用本文所定义，实例包括环丙基甲氧基、环丙基乙氧基、环丙基丙氧基、环丙基丁氧基、环丁基甲氧基、环丁基乙氧基、环丁基丙氧基、环丁基丁氧基、环戊基甲氧基、环戊基乙氧基、环戊基丙氧基、环戊基丁氧基、环己基甲氧基、环己基乙氧基、环己基丙氧基、环己基丁氧基等。 The term "C 4 -C m cycloalkylalkoxy" refers to an alkoxy group substituted by a cycloalkyl group and contains a total of 4-m carbon atoms, such as 4-20, 4-12 carbon atoms, preferably 4 -8 carbon atoms. Where cycloalkyl is as defined herein, examples include cyclopropylmethoxy, cyclopropylethoxy, cyclopropylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy , cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethoxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclo Hexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy and the like.
本文所用术语“C 6-C m芳氧基”是指在C 6-C m芳基对应的C 6-C m芳烃中的任何芳族碳原子上键合有一个氧原子作为连接基团的C 6-C m芳基，例如苯氧基、甲苯氧基、萘氧基等。 The term "C 6 -C m aryloxy" as used herein refers to any aromatic carbon atom in the C 6 -C m aromatic hydrocarbon corresponding to the C 6 -C m aryl group having an oxygen atom as a linking group. C 6 -C m aryl, such as phenoxy, tolyloxy, naphthyloxy and the like.
术语杂环烷基理解为指包括n-m个环成员，如3-8，3-7，3-6或4-8，4-7，4-6，或5、6或7个环成员以及一个或多个，如1-5，1-3、1或2个选自N、O或S的杂原子作为环成员的饱和基团。The term heterocycloalkyl is understood to mean comprising n-m ring members, such as 3-8, 3-7, 3-6 or 4-8, 4-7, 4-6, or 5, 6 or 7 ring members and one or more, such as 1-5, 1-3, 1 or 2 heteroatoms selected from N, O or S, as a saturated group of ring members.
杂芳基理解为指的是具有5-18个环成员，例如5、6、7、8、9、10、11、12、13、14、15、16、17或18，如5-16、5-14、5-10或5-8，或8-14，9-14或9-13个环成员的基团。杂芳基的至少一个环原子为杂原子，优选杂原子选自N、O和S，更优选N。杂芳基优选具有1-3个，例如一个或两个杂原子。更优选杂芳基为具有两个或三个稠合环的环体系，其具有8-14，9-14或9-13个环成员。杂芳基的实例包括咔唑、吡啶、吡咯、呋喃、吡唑、咪唑和噻吩。芳基可以是未被取代或被取代的。合适取代基例如包括羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 Heteroaryl is understood to mean having 5-18 ring members, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, such as 5-16, A group of 5-14, 5-10 or 5-8, or 8-14, 9-14 or 9-13 ring members. At least one ring atom of heteroaryl is a heteroatom, preferably the heteroatom is selected from N, O and S, more preferably N. Heteroaryl preferably has 1 to 3, eg one or two, heteroatoms. More preferably heteroaryl is a ring system having two or three fused rings having 8-14, 9-14 or 9-13 ring members. Examples of heteroaryl groups include carbazole, pyridine, pyrrole, furan, pyrazole, imidazole and thiophene. Aryl groups can be unsubstituted or substituted. Suitable substituents include, for example, hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, Heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"' having 5-10 ring members, wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-8 Heteroaryl or amino of ring members.
在本发明的一个实施方案中，R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、硝基、氰基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基、C 1-C 12烷氧基、C 1-C 12烷基、C 1-C 12卤代烷基、C 3-C 8环烷基、C 4-C 12环烷基烷基、C 4-C 12烷基环烷基、C 3-C 8环烷氧基、C 4-C 12环烷基烷氧基、C 2-C 6烯基、C 6-C 10的芳基、C 7-C 12芳烷基、C 7-C 12烷基芳基和C 6-C 10芳氧基。 In one embodiment of the present invention, R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, nitro, cyano, amino, mono(C 1 -C 6 alkyl)amino , Di(C 1 -C 6 alkyl)amino, C 1 -C 12 alkoxy, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 8 cycloalkyl, C 4 - C 12 cycloalkylalkyl, C 4 -C 12 alkylcycloalkyl, C 3 -C 8 cycloalkoxy, C 4 -C 12 cycloalkylalkoxy, C 2 -C 6 alkenyl, C 6 -C 10 aryl, C 7 -C 12 aralkyl, C 7 -C 12 alkylaryl and C 6 -C 10 aryloxy.
在本发明的一个优选实施方案中，R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 2-C 6烯基、C 6-C 10的芳基和C 7-C 12烷基芳基。 In a preferred embodiment of the present invention, R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl) amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkane Cycloalkyl, C 2 -C 6 alkenyl, C 6 -C 10 aryl and C 7 -C 12 alkylaryl.
在本发明的一个优选实施方案中，R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、C 1-C 6卤 代烷基和C 1-C 6烷基。 In a preferred embodiment of the present invention, R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, C 1 -C 6 haloalkyl and C 1 -C 6 alkyl.
在本发明的一个优选实施方案中，R 6表示C 1-C 12烷基、C 1-C 12卤代烷基、C 3-C 8环烷基、C 4-C 12环烷基烷基、C 4-C 12烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基。 In a preferred embodiment of the present invention, R 6 represents C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 12 cycloalkylalkyl, C 4 -C 12 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl.
在本发明的一个优选实施方案中，R 6表示C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基。 In a preferred embodiment of the present invention, R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl.
在本发明的一个优选实施方案中，R 6表示C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 6烷基、苯基或者被苯基取代的C 1-C 6烷基。最优选R 6为C 1-C 6烷基。 In a preferred embodiment of the present invention, R 6 represents C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 6 alkyl substituted by C 5 -C 6 cycloalkyl , benzene or C 1 -C 6 alkyl substituted by phenyl. Most preferably R 6 is C 1 -C 6 alkyl.
在本发明的一个实施方案中，其中Ar表示C 6-C 30芳基或具有5-18个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个(例如1-5个，1-4个，1-3个，1或2个)独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 In one embodiment of the present invention, wherein Ar represents C 6 -C 30 aryl or heteroaryl having 5-18 ring members, wherein said aryl or heteroaryl is unsubstituted or replaced by one or more (e.g. 1-5, 1-4, 1-3, 1 or 2) are substituted with groups independently selected from the group consisting of: hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkane radical, heterocycloalkyl having 3-8 ring members, C 6 -C 10 aryl, heteroaryl having 5-8 ring members or amino.
在本发明的一个优选实施方案中，Ar表示C 6-C 20芳基或具有5-18个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个(例如1-5个，1-4个，1-3个，1或2个)独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 In a preferred embodiment of the invention, Ar represents a C 6 -C 20 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl or heteroaryl group is unsubstituted or replaced by one or more (e.g. 1-5, 1-4, 1-3, 1 or 2) are substituted with groups independently selected from the group consisting of: hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, Heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
在本发明的一个优选实施方案中，Ar表示C 6-C 14芳基或具有5-14个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个(例如1-5个，1-4个，1-3个，1或2个)独立地选自下组的基团取代：羟基、卤 素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 In a preferred embodiment of the invention, Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein said aryl or heteroaryl group is unsubstituted or replaced by one or more (e.g. 1-5, 1-4, 1-3, 1 or 2) are substituted with groups independently selected from the group consisting of: hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, Heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
Ar例如可以为苯基、萘基或咔唑，其可以被一个或多个(例如1-5个，1-4个，1-3个，1或2个)相互独立地选自C 1-C 6烷基、C(O)R’的基团取代，其中R’为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基或C 6-C 10芳基。 Ar can be, for example, phenyl, naphthyl or carbazole, which can be independently selected from C 1 - C 6 alkyl, group substitution of C(O)R', where R' is hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkane with 3-8 ring members radical or C 6 -C 10 aryl.
在本发明的一个优选实施方案中，式(I)化合物中的各变量具有如下定义：In a preferred embodiment of the invention, each variable in the compound of formula (I) has the following definitions:
R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 2-C 6烯基、C 6-C 10的芳基和C 7-C 12烷基芳基； R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 2 -C 6 Alkenyl, C 6 -C 10 aryl and C 7 -C 12 alkylaryl;
R 6表示C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基；和 R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl; and
Ar表示C 6-C 20芳基或具有5-18个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 Ar represents a C 6 -C 20 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : Hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
在本发明的一个优选实施方案中，式(I)化合物中的各变量具有如下定义：In a preferred embodiment of the invention, each variable in the compound of formula (I) has the following definitions:
R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、C 1-C 6烷基和C 1-C 6卤代烷基、； R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino, C 1 -C 6 alkyl and C 1 -C 6 haloalkyl;
R 6表示C 1-C 6烷基、C 1-C 6卤代烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 6烷基、苯基或者被苯基取代的C 1-C 6烷基；和 R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 5 -C 6 cycloalkyl, C 1 -C 6 alkyl substituted by C 5 -C 6 cycloalkyl , phenyl or C 1 -C 6 alkyl substituted by phenyl; and
Ar表示C 6-C 14芳基或具有5-14个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein the aryl group or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : Hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
在本发明的一个优选实施方案中，式(I)化合物中的各变量具有如下定义：In a preferred embodiment of the invention, each variable in the compound of formula (I) has the following definitions:
R 1、R 2、R 3、R 4和R 5相互独立地表示氢、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和C 1-C 6烷基； R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino and C 1 -C 6 alkyl;
R 6表示C 1-C 6烷基；和 R 6 represents C 1 -C 6 alkyl; and
Ar表示C 6-C 14芳基或具有5-14个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’，其中R’为C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基或具有5-8个环成员的杂芳基。 Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein the aryl group or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members , amino, -C(O)R', wherein R' is C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 Aryl or heteroaryl having 5-8 ring members.
式(I)化合物的具体实例可以提及：Specific examples of compounds of formula (I) may be mentioned:
Figure PCTCN2022097591-appb-000010
Figure PCTCN2022097591-appb-000010
Figure PCTCN2022097591-appb-000011
Figure PCTCN2022097591-appb-000011
本发明的一个方面涉及一种式(I)的γ,δ-不饱和肟酯化合物：One aspect of the present invention relates to a γ, δ-unsaturated oxime ester compound of formula (I):
Figure PCTCN2022097591-appb-000012
Figure PCTCN2022097591-appb-000012
其中R 1、R 2、R 3、R 4、R 5和R 6各自如上所定义，以及 wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each as defined above, and
Ar为具有两个或三个稠合环的杂芳基，并且具有8-14，或9-14或9-13个环成员，该杂芳基具有1或2个N原子作为环成员，该杂芳基未被取代或被一个或多个(如1-5、1-3或1或2个)独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 Ar is a heteroaryl group with two or three fused rings and has 8-14, or 9-14 or 9-13 ring members, the heteroaryl group has 1 or 2 N atoms as ring members, the Heteroaryl is unsubstituted or substituted by one or more (such as 1-5, 1-3 or 1 or 2) groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 Alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C( O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
在一个优选实施方案中，Ar为咔唑，其未被取代或被一个或多个(如1-5或1-3个)如上所定义的取代基取代，优选被一个或多个(例如1-5个，1-4个，1-3个，1或2个)相互独立地选自C 1-C 6烷基、C(O)R’的基团取代，其中R’为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基或C 6-C 10芳基。 In a preferred embodiment, Ar is carbazole, which is unsubstituted or substituted by one or more (such as 1-5 or 1-3) substituents as defined above, preferably by one or more (such as 1 -5, 1-4, 1-3, 1 or 2) substituted by groups independently selected from C 1 -C 6 alkyl, C(O)R', wherein R' is hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members or C 6 -C 10 aryl.
在一个实施方案中，式(I)化合物为In one embodiment, the compound of formula (I) is
Figure PCTCN2022097591-appb-000013
Figure PCTCN2022097591-appb-000013
本发明的第二方面涉及一种制备本发明的式(I)化合物的方法，其包括使式(E)化合物The second aspect of the present invention relates to a method for preparing the compound of formula (I) of the present invention, which comprises making the compound of formula (E)
Figure PCTCN2022097591-appb-000014
Figure PCTCN2022097591-appb-000014
其中R 1、R 2、R 3、R 4、R 5和Ar如上所定义， wherein R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined above,
与式(F)化合物反应得到式(I)化合物Reaction with formula (F) compound obtains formula (I) compound
Figure PCTCN2022097591-appb-000015
Figure PCTCN2022097591-appb-000015
其中X 1为卤素、羟基或-C(＝O)-R 6，以及R 6如上所定义。 wherein X 1 is halogen, hydroxyl or -C(=O)-R 6 , and R 6 is as defined above.
在式(E)化合物与式(F)化合物的反应中，肟基中的羟基转变为酯基，从而获得式(I)化合物。作为酯化试剂，没有特别的限制，只要能将式(III)化合物肟基中的羟基转变为酯基即可。作为酯化试剂，可以使用相应的酰卤，如酰氯，也可使用相应的羧酸，还可使用相应的酸酐。In the reaction of the compound of formula (E) with the compound of formula (F), the hydroxyl group in the oxime group is converted into an ester group, thereby obtaining the compound of formula (I). There is no particular limitation on the esterification agent, as long as it can convert the hydroxyl group in the oxime group of the compound of formula (III) into an ester group. As the esterification reagent, the corresponding acid halides, such as acid chlorides, the corresponding carboxylic acids, and the corresponding acid anhydrides can also be used.
所述式(E)化合物与式(F)化合物的反应通常在的催化剂存在下进行，例如将式(E)化合物与式(F)化合物在催化剂存在条件下分散在有机溶剂中。催化剂可以提及三乙胺、碳酸钠、碳酸钾、碳酸氢钠、氢氧化钠或氢化钠中任意一种或两种以上混合。所述的式(E)化合物与式(F)的化合物的摩尔 比可以为1:2-1:5；式(E)化合物与催化剂摩尔比可以为1:2-1:15。所述比例有利于产物产率的提高。在式(E)化合物与式(F)化合物的反应中，反应温度可以为10-100℃，反应时间可以为1-8小时，如1-5小时。The reaction of the compound of formula (E) and compound of formula (F) is usually carried out in the presence of a catalyst, for example, the compound of formula (E) and compound of formula (F) are dispersed in an organic solvent in the presence of a catalyst. The catalyst can be any one or a mixture of two or more of triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide or sodium hydride. The molar ratio of the compound of the formula (E) to the compound of the formula (F) can be 1:2-1:5; the molar ratio of the compound of the formula (E) to the catalyst can be 1:2-1:15. Said ratio is conducive to the improvement of product yield. In the reaction between the compound of formula (E) and the compound of formula (F), the reaction temperature can be 10-100°C, and the reaction time can be 1-8 hours, such as 1-5 hours.
根据本发明，式(E)化合物可通过使得式(C)化合物与羟胺和/或盐酸羟胺进行肟化反应得到According to the present invention, the compound of formula (E) can be obtained by oximating the compound of formula (C) with hydroxylamine and/or hydroxylamine hydrochloride
Figure PCTCN2022097591-appb-000016
Figure PCTCN2022097591-appb-000016
其中R 1、R 2、R 3、R 4、R 5和Ar如上所定义。 wherein R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined above.
式(C)化合物与羟胺和/或盐酸羟胺的反应可以在催化剂存在下进行。所述催化剂例如可以为碳酸氢钠，碳酸钠或乙酸钠中任意一种或两种以上混合。式(C)化合物与羟胺和/或盐酸羟胺的摩尔比可以为1:2～1:5。式(C)化合物与与催化剂摩尔比可以为1:2-1:15。The reaction of the compound of formula (C) with hydroxylamine and/or hydroxylamine hydrochloride can be carried out in the presence of a catalyst. The catalyst can be, for example, sodium bicarbonate, any one of sodium carbonate or sodium acetate or a mixture of two or more. The molar ratio of the compound of formula (C) to hydroxylamine and/or hydroxylamine hydrochloride may be 1:2˜1:5. The molar ratio of the compound of formula (C) to the catalyst can be 1:2-1:15.
根据本发明，式(C)化合物可通过使式(A)化合物According to the present invention, the compound of formula (C) can be obtained by making the compound of formula (A)
Ar-HAr-H
(A)(A)
其中Ar如上所定义，where Ar is as defined above,
与式(B)化合物反应而制备Prepared by reacting with a compound of formula (B)
Figure PCTCN2022097591-appb-000017
Figure PCTCN2022097591-appb-000017
其中R 1、R 2、R 3、R 4、R 5和Ar如上所定义，以及X 2为卤素。 wherein R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined above, and X 2 is halogen.
式(A)化合物与式(B)化合物的反应可以在催化剂存在下进行。催化剂的实例可以提及三氯化铝、三溴化铝、三氯化铁、三氟化硼、二氯化锌中任意一种或两种以上的混合。所述的反应是傅克酰基化反应。反应温度可以为50-150℃，反应时间可以为1-10小时。The reaction of the compound of formula (A) with the compound of formula (B) can be carried out in the presence of a catalyst. Examples of the catalyst include any one or a mixture of two or more of aluminum trichloride, aluminum tribromide, iron trichloride, boron trifluoride, and zinc dichloride. The reaction described is a Friedel-Crafts acylation reaction. The reaction temperature may be 50-150°C, and the reaction time may be 1-10 hours.
上述式(A)化合物与式(B)化合物的反应，式(C)化合物与羟胺和/或盐酸羟胺的反应，式(E)化合物与式(F)化合物的反应可以在有机溶剂存在下进行。所述的有机溶剂可以为二氯甲烷、氯仿、甲醇、乙醇、甲苯、四氢呋 喃、N,N-二甲基甲酰胺、二甲亚砜或三乙胺中任意一种或两种以上的混合。The reaction of the above-mentioned formula (A) compound and the formula (B) compound, the reaction of the formula (C) compound and hydroxylamine and/or hydroxylamine hydrochloride, the reaction of the formula (E) compound and the formula (F) compound can be carried out in the presence of an organic solvent . The organic solvent can be any one or a mixture of two or more of dichloromethane, chloroform, methanol, ethanol, toluene, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide or triethylamine.
本发明式(I)化合物在UV-vis光固化体系中作为光引发剂，可以有效地引发固化反应。本发明的式(I)化合物可以在辐射波长为300-550nm、优选350-525nm的光固化体系中作为光引发剂。本发明的式(I)化合物还可以作为光引发剂用于3D打印。The compound of the formula (I) of the present invention is used as a photoinitiator in the UV-vis photocuring system, and can effectively initiate the curing reaction. The compound of formula (I) of the present invention can be used as a photoinitiator in a photocuring system with a radiation wavelength of 300-550 nm, preferably 350-525 nm. The compound of formula (I) of the present invention can also be used as a photoinitiator for 3D printing.
本发明的另一方面涉及包含至少一种本发明的式(I)的γ,δ-不饱和肟酯化合物的光固化性组合物。Another aspect of the present invention relates to a photocurable composition comprising at least one γ,δ-unsaturated oxime ester compound of formula (I) according to the invention.
本发明式(I)化合物的量通常为0.01-10重量％，例如0.02重量％，0.05重量％，0.08重量％，0.1重量％，0.2重量％，0.5重量％，0.8重量％，1重量％，1.2重量％，1.5重量％，1.8重量％，2重量％，2.2重量％，2.5重量％，2.8重量％，3重量％，3.2重量％，3.5重量％，3.8重量％，4重量％，4.5重量％，5重量％，5.5重量％，6重量％，6.5重量％，7重量％，7.5重量％，8重量％，8.5重量％，9重量％，9.5重量％，优选0.1-6重量％，如0.2-5重量％，基于光固化性组合物的活性成分量。The amount of the compound of formula (I) according to the invention is generally 0.01-10% by weight, for example 0.02% by weight, 0.05% by weight, 0.08% by weight, 0.1% by weight, 0.2% by weight, 0.5% by weight, 0.8% by weight, 1% by weight, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.5 wt% %, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, preferably 0.1-6% by weight, such as 0.2-5% by weight, based on the active ingredient amount of the photocurable composition.
在公开的上下文中，活性成分是指光固化性组合物中除去溶剂之外的成分。In the disclosed context, the active ingredient refers to the ingredients in the photocurable composition except the solvent.
除了本发明的光引发剂之外，所述光固化性组合物还包含光固化化合物。The photocurable composition contains a photocurable compound in addition to the photoinitiator of the present invention.
在本发明中，作为光固化化合物，它指的是含有不饱和碳碳双键的单体或低聚物。该单体或低聚物经光线照射后，能由光引发剂引发聚合反应，进而发生交联固化。In the present invention, as a photocurable compound, it refers to a monomer or oligomer containing an unsaturated carbon-carbon double bond. After the monomer or oligomer is irradiated by light, the polymerization reaction can be initiated by the photoinitiator, and then cross-linking and curing can occur.
根据本发明的一个方面，提供了可由本发明光固化性组合物得到的固化材料。According to one aspect of the present invention, there is provided a cured material obtainable from the photocurable composition of the present invention.
固化材料可以是光固化涂层，这包括包含功能性材料的涂层，UV光和/或可见光的滤色器的涂层；密封剂；光刻材料；全息记录材料；3D打印材料；平版印刷材料；光学器件的制备材料及改善机械性能的材料，例如碳纤维复合材料和/或无机纳米颗粒和/或有机纳米颗粒等。The cured material may be a photocurable coating, which includes coatings containing functional materials, coatings of color filters for UV light and/or visible light; encapsulants; photolithographic materials; holographic recording materials; 3D printing materials; lithographic printing Materials; preparation materials for optical devices and materials for improving mechanical properties, such as carbon fiber composite materials and/or inorganic nanoparticles and/or organic nanoparticles, etc.
根据本发明的式(I)的γ,δ-不饱和肟酯化合物作为光引发剂的有益效果包括：According to the γ of formula (I) of the present invention, the beneficial effect of δ-unsaturated oxime ester compound as photoinitiator comprises:
(1)具有优异的引发效率；(1) have excellent initiation efficiency;
(2)通过改变芳香化合物的结构和种类，可以调控光引发剂的吸收波长，可作为紫外光引发剂，也可作为可见光引发剂，与节能环保的LED光源配合使用，应用范围较为广泛；(2) By changing the structure and type of aromatic compounds, the absorption wavelength of the photoinitiator can be adjusted, and it can be used as an ultraviolet photoinitiator or a visible light initiator. It can be used in conjunction with energy-saving and environmentally friendly LED light sources, and has a wide range of applications;
(3)本发明所述光引发剂可用于3D打印构建精致的三维模型。(3) The photoinitiator of the present invention can be used for 3D printing to construct delicate three-dimensional models.
实施例Example
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。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 in conjunction with specific examples, but they should not be construed as limiting the protection scope of the present invention. The present invention will be further described below in conjunction with specific examples, but they should not be construed as limiting the protection scope of the present invention.
实施例1：化合物1的制备：Embodiment 1: the preparation of compound 1:
(1)苯基-4-戊烯-1-酮的制备：(1) Preparation of phenyl-4-penten-1-one:
化学反应式：Chemical reaction formula:
Figure PCTCN2022097591-appb-000018
Figure PCTCN2022097591-appb-000018
冰浴条件下，在100mL的单口烧瓶中依次加入苯(20mL)、三氯化铝(0.956g，7.17mmol)后，缓慢滴加4-戊烯酰氯(0.728g，6.14mmol)，反应2小时后，将反应液倒入20mL冰水中，并用二氯甲烷萃取(20mL×3)，合并有机相，用无水硫酸钠干燥。旋蒸除去二氯甲烷，经硅胶柱层析分离得到0.55g白色固体，收率：38.7％。Under ice-bath conditions, benzene (20mL) and aluminum trichloride (0.956g, 7.17mmol) were added successively in a 100mL single-necked flask, and then 4-pentenoyl chloride (0.728g, 6.14mmol) was slowly added dropwise and reacted for 2 hours Afterwards, the reaction solution was poured into 20 mL of ice water, and extracted with dichloromethane (20 mL×3), and the organic phases were combined and dried over anhydrous sodium sulfate. The dichloromethane was removed by rotary evaporation, and 0.55 g of white solid was obtained by silica gel column chromatography, yield: 38.7%.
苯基-4-戊烯-1-酮的结构通过核磁共振氢谱得到确认：The structure of phenyl-4-penten-1-one was confirmed by H NMR spectroscopy:
1H NMR(400MHz,DMSO-d6)δ8.01–7.94(m,2H),7.67–7.60(m,1H),7.57–7.50(m,2H),5.88(ddt,J＝16.8,10.2,6.4Hz,1H),5.08(dq,J＝17.2,1.7Hz,1H),4.98(dq,J＝10.2,1.5Hz,1H),3.13(t,J＝7.3Hz,2H),2.43–2.34(m,2H)。 1 H NMR (400MHz, DMSO-d6) δ8.01–7.94 (m, 2H), 7.67–7.60 (m, 1H), 7.57–7.50 (m, 2H), 5.88 (ddt, J=16.8, 10.2, 6.4 Hz, 1H), 5.08(dq, J=17.2, 1.7Hz, 1H), 4.98(dq, J=10.2, 1.5Hz, 1H), 3.13(t, J=7.3Hz, 2H), 2.43–2.34(m ,2H).
(2)苯基-4-戊烯-1-酮肟的制备：(2) Preparation of phenyl-4-penten-1-one oxime:
化学反应式：Chemical reaction formula:
Figure PCTCN2022097591-appb-000019
Figure PCTCN2022097591-appb-000019
100mL圆底烧瓶中加入苯基-4-戊烯-1-酮(0.707g，4.412mmol)，盐酸羟胺(0.613g，8.825mmol)，无水乙酸钠(0.723g，8.825mmol)和30mL无水乙醇回流2小时。反应结束后冷却至室温，过滤除去固体杂质，收集液相，旋蒸除去溶剂。经硅胶柱层析(石油醚：乙酸乙酯＝10:1)得到淡黄色固体(0.494g)。产率：63.9％。In a 100mL round bottom flask, add phenyl-4-penten-1-one (0.707g, 4.412mmol), hydroxylamine hydrochloride (0.613g, 8.825mmol), anhydrous sodium acetate (0.723g, 8.825mmol) and 30mL of anhydrous Ethanol was refluxed for 2 hours. Cool to room temperature after the reaction, filter to remove solid impurities, collect the liquid phase, and remove the solvent by rotary evaporation. A light yellow solid (0.494 g) was obtained by silica gel column chromatography (petroleum ether: ethyl acetate = 10:1). Yield: 63.9%.
苯基-4-戊烯-1-酮肟的结构通过核磁共振氢谱得到确认：The structure of phenyl-4-penten-1-one oxime was confirmed by 1H NMR:
1H NMR(400MHz,DMSO-d6)δ11.19(s,1H),7.65–7.60(m,2H),7.42–7.34(m,3H),5.84(ddt,J＝16.8,10.2,6.5Hz,1H),5.04(dq,J＝17.1,1.7Hz,1H),4.96(ddt,J＝10.2,2.2,1.3Hz,1H),2.84–2.78(m,2H),2.21(dtt,J＝9.3,6.6,1.4Hz,2H)。 1 H NMR (400MHz, DMSO-d6) δ11.19 (s, 1H), 7.65–7.60 (m, 2H), 7.42–7.34 (m, 3H), 5.84 (ddt, J=16.8, 10.2, 6.5Hz, 1H), 5.04(dq, J＝17.1, 1.7Hz, 1H), 4.96(ddt, J＝10.2, 2.2, 1.3Hz, 1H), 2.84–2.78(m, 2H), 2.21(dtt, J＝9.3, 6.6, 1.4Hz, 2H).
(3)化合物1的制备：(3) Preparation of Compound 1:
化学反应式：Chemical reaction formula:
Figure PCTCN2022097591-appb-000020
Figure PCTCN2022097591-appb-000020
25mL圆底烧瓶中加入苯基-4-戊烯-1-酮肟(28mg，0.159mmol)和5mL THF冰浴搅拌下加入氢化钠(7.5mg，0.315mmol)反应30min。然后，加入丙烯酰氯(43.4mg，0.479mmol)继续反应30min。反应结束后用去离子水淬灭反应。旋蒸除去THF，并用乙酸乙酯萃取水相三次。合并有机相，并用无水硫酸钠干燥，旋蒸除去乙酸乙酯。经硅胶柱柱层析(石油醚：二氯甲烷＝1:1.5)得到黄色液体30mg。产率:82.3％。Phenyl-4-penten-1-one oxime (28mg, 0.159mmol) and 5mL THF were added to a 25mL round-bottomed flask, and sodium hydride (7.5mg, 0.315mmol) was added to react for 30min while stirring in an ice bath. Then, acryloyl chloride (43.4 mg, 0.479 mmol) was added to continue the reaction for 30 min. After the reaction was completed, the reaction was quenched with deionized water. The THF was removed by rotary evaporation, and the aqueous phase was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and ethyl acetate was removed by rotary evaporation. After silica gel column chromatography (petroleum ether:dichloromethane=1:1.5), 30 mg of yellow liquid was obtained. Yield: 82.3%.
化合物1的结构通过核磁共振氢谱得到确认。The structure of compound 1 was confirmed by H NMR spectroscopy.
1H NMR(400MHz,DMSO-d6)δ7.79–7.73(m,2H),7.57–7.47(m,3H),6.48(dd,J＝17.3,1.7Hz,1H),6.40(dd,J＝17.3,10.1Hz,1H),6.10(dd,J＝10.1,1.7Hz,1H),5.81(ddt,J＝16.9,10.1,6.7Hz,1H),5.03(dq,J＝17.1,1.6 Hz,1H),4.98(ddt,J＝10.1,2.1,1.2Hz,1H),3.00(dd,J＝8.2,7.1Hz,2H),2.26(dtt,J＝8.5,7.2,1.4Hz,2H). 1 H NMR (400MHz, DMSO-d6) δ7.79–7.73 (m, 2H), 7.57–7.47 (m, 3H), 6.48 (dd, J=17.3, 1.7Hz, 1H), 6.40 (dd, J= 17.3,10.1Hz,1H),6.10(dd,J＝10.1,1.7Hz,1H),5.81(ddt,J＝16.9,10.1,6.7Hz,1H),5.03(dq,J＝17.1,1.6Hz,1H ), 4.98(ddt, J=10.1, 2.1, 1.2Hz, 1H), 3.00(ddt, J=8.2, 7.1Hz, 2H), 2.26(dtt, J=8.5, 7.2, 1.4Hz, 2H).
实施例2：化合物2的制备：Embodiment 2: the preparation of compound 2:
(1)N-乙基咔唑-3-(4-丁烯基)酮的制备：(1) Preparation of N-ethylcarbazol-3-(4-butenyl) ketone:
化学反应式：Chemical reaction formula:
Figure PCTCN2022097591-appb-000021
Figure PCTCN2022097591-appb-000021
冰浴条件下，在50mL的单口烧瓶中依次加入二氯甲烷(20mL)、三氯化铝(0.956g，7.17mmol)和N-乙基咔唑(1.0g，5.12mmol)后，缓慢滴加4-戊烯酰氯(0.728g，6.14mmol)的二氯甲烷(10mL)溶液，反应4小时后，将反应液倒入20mL冰水中，并用二氯甲烷萃取(20mL×3)，合并有机相，用无水硫酸钠干燥。旋蒸除去二氯甲烷，经硅胶柱层析分离得到0.55g白色固体，收率：38.7％。Under ice-bath conditions, in a 50mL single-necked flask, add dichloromethane (20mL), aluminum trichloride (0.956g, 7.17mmol) and N-ethylcarbazole (1.0g, 5.12mmol) successively, and slowly drop 4-pentenoyl chloride (0.728g, 6.14mmol) in dichloromethane (10mL) solution, reacted for 4 hours, poured the reaction solution into 20mL ice water, and extracted with dichloromethane (20mL×3), combined the organic phase, Dry over anhydrous sodium sulfate. The dichloromethane was removed by rotary evaporation, and 0.55 g of white solid was obtained by silica gel column chromatography, yield: 38.7%.
N-乙基咔唑-3-(4-丁烯基)酮的结构通过核磁共振氢谱得到确认：The structure of N-ethylcarbazol-3-(4-butenyl)one was confirmed by 1H NMR:
1H NMR(400MHz,DMSO-d6)δ8.91(d,J＝1.6Hz,1H),8.32(dt,J＝7.7,1.0Hz,1H),8.10(dd,J＝8.7,1.7Hz,1H),7.72–7.64(m,2H),7.52(ddd,J＝8.3,7.1,1.2Hz,1H),7.29(ddd,J＝7.9,7.2,0.9Hz,1H),5.94(ddt,J＝16.8,10.2,6.4Hz,1H),5.17–4.96(m,2H),4.48(q,J＝7.1Hz,2H),3.25(t,J＝7.3Hz,2H),2.49–2.40(m,2H),1.32(t,J＝7.1Hz,3H)。 1 H NMR (400MHz, DMSO-d6) δ8.91 (d, J = 1.6Hz, 1H), 8.32 (dt, J = 7.7, 1.0Hz, 1H), 8.10 (dd, J = 8.7, 1.7Hz, 1H ),7.72–7.64(m,2H),7.52(ddd,J＝8.3,7.1,1.2Hz,1H),7.29(ddd,J＝7.9,7.2,0.9Hz,1H),5.94(ddt,J＝16.8 ,10.2,6.4Hz,1H),5.17–4.96(m,2H),4.48(q,J＝7.1Hz,2H),3.25(t,J＝7.3Hz,2H),2.49–2.40(m,2H) , 1.32 (t, J = 7.1 Hz, 3H).
(2)N-乙基咔唑-3-(4-丁烯基)酮肟的合成(2) Synthesis of N-ethylcarbazole-3-(4-butenyl)ketoxime
化学反应式：Chemical reaction formula:
Figure PCTCN2022097591-appb-000022
Figure PCTCN2022097591-appb-000022
将N-乙基咔唑-3-(4-正丁烯基)酮(0.55g，1.98mmol)，盐酸羟胺(0.412g，5.94mmol)，无水乙酸钠(0.487g，5.94mmol)和无水乙醇(30mL)加入到100mL圆底烧瓶中，回流2小时后，加入20mL二氯甲烷，并用去离子水洗涤(20mL×3)，无水硫酸钠干燥后，旋蒸除去二氯甲烷，经硅胶柱层析分离(石油醚：乙酸乙酯＝8：1)得到0.461g白色固体，收率：79.63％。N-ethylcarbazol-3-(4-n-butenyl) ketone (0.55g, 1.98mmol), hydroxylamine hydrochloride (0.412g, 5.94mmol), anhydrous sodium acetate (0.487g, 5.94mmol) and anhydrous Water ethanol (30mL) was added to a 100mL round-bottomed flask, and after reflux for 2 hours, 20mL of dichloromethane was added and washed with deionized water (20mL×3). After drying over anhydrous sodium sulfate, the dichloromethane was removed by rotary evaporation. Silica gel column chromatography (petroleum ether: ethyl acetate = 8: 1) gave 0.461 g of white solid, yield: 79.63%.
N-乙基咔唑-3-(4-丁烯基)酮肟的结构通过核磁共振氢谱得到确认：The structure of N-ethylcarbazole-3-(4-butenyl)ketoxime was confirmed by 1H NMR:
1H NMR(400MHz,DMSO-d6)δ10.99(s,1H),8.40(d,J＝1.6Hz,1H),8.22(d,J＝7.6Hz,1H),7.79(dd,J＝8.6,1.7Hz,1H),7.61(dd,J＝8.4,4.9Hz,2H),7.47(ddd,J＝8.3,7.1,1.2Hz,1H),7.25–7.19(m,1H),5.90(ddt,J＝16.8,10.2,6.5Hz,1H),5.11–4.94(m,2H),4.45(q,J＝7.1Hz,2H),2.98–2.92(m,2H),2.34–2.25(m,2H),1.33(t,J＝7.1Hz,3H)。 1 H NMR (400MHz, DMSO-d6) δ10.99(s, 1H), 8.40(d, J=1.6Hz, 1H), 8.22(d, J=7.6Hz, 1H), 7.79(dd, J=8.6 ,1.7Hz,1H),7.61(dd,J＝8.4,4.9Hz,2H),7.47(ddd,J＝8.3,7.1,1.2Hz,1H),7.25–7.19(m,1H),5.90(ddt, J＝16.8, 10.2, 6.5Hz, 1H), 5.11–4.94(m, 2H), 4.45(q, J＝7.1Hz, 2H), 2.98–2.92(m, 2H), 2.34–2.25(m, 2H) , 1.33 (t, J = 7.1 Hz, 3H).
(3)化合物2的合成(3) Synthesis of Compound 2
化学反应式：Chemical reaction formula:
Figure PCTCN2022097591-appb-000023
Figure PCTCN2022097591-appb-000023
冰浴条件下，将N-乙基咔唑-3-(4-丁烯基)酮肟(0.7g，2.532mmol)，氢化钠(0.181g，7.571mmol)和无水四氢呋喃(20mL)加入到100mL圆底烧瓶中，反应1小时后，将乙酰氯(0.685g，7.571mmol)加入反应体系，继续反应1小时。反应结束后，用饱和碳酸氢钠溶液猝灭反应，并 用二氯甲烷(20mL×3)萃取产物，合并有机相，用无水硫酸钠干燥。旋蒸除去溶剂，经硅胶柱层析分离(石油醚：乙酸乙酯＝15：1)得到0.753g黄色粘稠液体，收率：88.7％。Under ice-bath conditions, N-ethylcarbazole-3-(4-butenyl)ketoxime (0.7g, 2.532mmol), sodium hydride (0.181g, 7.571mmol) and anhydrous tetrahydrofuran (20mL) were added to In a 100 mL round bottom flask, after reacting for 1 hour, acetyl chloride (0.685 g, 7.571 mmol) was added to the reaction system, and the reaction was continued for 1 hour. After the reaction was completed, the reaction was quenched with saturated sodium bicarbonate solution, and the product was extracted with dichloromethane (20 mL×3), and the organic phases were combined and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation, and 0.753 g of yellow viscous liquid was obtained by silica gel column chromatography (petroleum ether: ethyl acetate = 15: 1), yield: 88.7%.
化合物2：N-乙基咔唑-3-(4-丁烯基)酮乙酰肟酯的结构通过核磁共振氢谱得到确认：Compound 2: The structure of N-ethylcarbazol-3-(4-butenyl)one acetoxime ester was confirmed by 1H NMR:
1H NMR(400MHz,DMSO-d6)δ8.58(d,J＝1.6Hz,1H),8.29–8.25(m,1H),7.88(dd,J＝8.7,1.8Hz,1H),7.65(dd,J＝14.7,8.5Hz,2H),7.50(ddd,J＝8.2,7.2,1.2Hz,1H),7.28–7.23(m,1H),5.87(ddt,J＝16.8,10.1,6.6Hz,1H),5.10–4.97(m,2H),4.46(q,J＝7.1Hz,2H),3.09(t,J＝7.7Hz,2H),2.36–2.28(m,2H),2.26(s,3H),1.32(t,J＝7.1Hz,3H)。 1 H NMR (400MHz, DMSO-d6) δ8.58 (d, J = 1.6Hz, 1H), 8.29–8.25 (m, 1H), 7.88 (dd, J = 8.7, 1.8Hz, 1H), 7.65 (dd ,J＝14.7,8.5Hz,2H),7.50(ddd,J＝8.2,7.2,1.2Hz,1H),7.28–7.23(m,1H),5.87(ddt,J＝16.8,10.1,6.6Hz,1H ),5.10–4.97(m,2H),4.46(q,J=7.1Hz,2H),3.09(t,J=7.7Hz,2H),2.36–2.28(m,2H),2.26(s,3H) , 1.32 (t, J = 7.1 Hz, 3H).
实施例3：化合物3的制备：Embodiment 3: the preparation of compound 3:
(1)N-乙基咔唑-4-丁烯基-3-(2-甲基苯基)酮的制备：(1) Preparation of N-ethylcarbazole-4-butenyl-3-(2-methylphenyl)ketone:
化学反应式：Chemical reaction formula:
Figure PCTCN2022097591-appb-000024
Figure PCTCN2022097591-appb-000024
冰浴条件下，将二氯甲烷(20mL)，三氯化铝(0.835g，6.266mmol)和N-乙基咔唑-3-(2-甲基苯基)酮(0.469g，1.566mmol)加入到100mL圆底烧瓶中，并将4-戊烯酰氯(0.247g，1.878mmol)的二氯甲烷溶液(10mL)缓慢滴加至反应体系，反应4小时。反应结束后，将反应液倒入20mL冰水中。用20mL×3二氯甲烷萃取产物，合并有机相，用无水硫酸钠干燥。旋蒸除去二氯甲烷，经硅胶柱层析分离(石油醚：乙酸乙酯＝5：1)得到0.53g淡黄色固体，收率：95.2％。Under ice-bath conditions, dichloromethane (20mL), aluminum chloride (0.835g, 6.266mmol) and N-ethylcarbazole-3-(2-methylphenyl) ketone (0.469g, 1.566mmol) It was added to a 100 mL round bottom flask, and a dichloromethane solution (10 mL) of 4-pentenoyl chloride (0.247 g, 1.878 mmol) was slowly added dropwise to the reaction system and reacted for 4 hours. After the reaction, the reaction solution was poured into 20 mL of ice water. The product was extracted with 20 mL×3 dichloromethane, and the organic phases were combined and dried over anhydrous sodium sulfate. Dichloromethane was removed by rotary evaporation, and 0.53 g of light yellow solid was obtained by silica gel column chromatography (petroleum ether: ethyl acetate = 5: 1), yield: 95.2%.
N-乙基咔唑-4-丁烯基-3-(2-甲基苯基)酮的结构通过核磁共振氢谱得到确认：The structure of N-ethylcarbazol-4-butenyl-3-(2-methylphenyl)one was confirmed by 1H NMR:
1H NMR(400MHz,DMSO-d6)δ8.87(d,J＝1.6Hz,1H),8.62(d,J＝1.5 Hz,1H),8.11(dd,J＝8.6,1.7Hz,1H),7.88(dd,J＝8.6,1.7Hz,1H),7.80(dd,J＝8.7,6.4Hz,2H),7.59(ddd,J＝8.4,5.9,2.9Hz,1H),7.43–7.35(m,3H),5.88(ddt,J＝16.8,10.2,6.4Hz,1H),5.08(dq,J＝17.2,1.7Hz,1H),4.88(dq,J＝10.2,1.5Hz,1H),4.53(q,J＝7.1Hz,2H),3.11(t,J＝7.3Hz,2H),2.59(s,3H),2.43–2.34(m,2H),1.32(t,J＝7.1Hz,3H)。 1 H NMR (400MHz, DMSO-d6) δ8.87(d, J=1.6Hz, 1H), 8.62(d, J=1.5 Hz, 1H), 8.11(dd, J=8.6, 1.7Hz, 1H), 7.88(dd, J=8.6,1.7Hz,1H),7.80(dd,J=8.7,6.4Hz,2H),7.59(ddd,J=8.4,5.9,2.9Hz,1H),7.43–7.35(m, 3H), 5.88(ddt, J＝16.8, 10.2, 6.4Hz, 1H), 5.08(dq, J＝17.2, 1.7Hz, 1H), 4.88(dq, J＝10.2, 1.5Hz, 1H), 4.53(q , J=7.1Hz, 2H), 3.11(t, J=7.3Hz, 2H), 2.59(s, 3H), 2.43–2.34(m, 2H), 1.32(t, J=7.1Hz, 3H).
(2)N-乙基咔唑-6-(2-甲基苯甲酰基)-4-丁烯基酮肟的合成(2) Synthesis of N-ethylcarbazole-6-(2-methylbenzoyl)-4-butenyl ketoxime
化学反应式：Chemical reaction formula:
Figure PCTCN2022097591-appb-000025
Figure PCTCN2022097591-appb-000025
将N-乙基咔唑-4-丁烯基-3-(2-甲基苯基)酮(0.563g，1.583mmol)，盐酸羟胺(0.330g，4.751mmol)，无水乙酸钠(0.389g，4.751mmol)和25mL无水乙醇加入到100mL圆底烧瓶中，回流3小时。反应结束后，过滤收集液相，旋蒸除去溶剂得到粗产物，并将其溶解于20mL二氯甲烷中，并用20×3mL去离子水洗涤，并用无水硫酸钠干燥，旋蒸除去二氯甲烷，经硅胶柱层析分离(石油醚：二氯甲烷＝1：3)得到0.594g淡黄色固体，收率：96.6％。N-ethylcarbazole-4-butenyl-3-(2-methylphenyl)ketone (0.563g, 1.583mmol), hydroxylamine hydrochloride (0.330g, 4.751mmol), anhydrous sodium acetate (0.389g , 4.751mmol) and 25mL of absolute ethanol were added into a 100mL round bottom flask, and refluxed for 3 hours. After the reaction, the liquid phase was collected by filtration, and the solvent was removed by rotary evaporation to obtain the crude product, which was dissolved in 20 mL of dichloromethane, washed with 20×3 mL of deionized water, dried with anhydrous sodium sulfate, and the dichloromethane was removed by rotary evaporation , separated by silica gel column chromatography (petroleum ether: dichloromethane = 1:3) to obtain 0.594 g of light yellow solid, yield: 96.6%.
N-乙基咔唑-6-(2-甲基苯甲酰基)-4-丁烯基酮肟的结构通过核磁共振氢谱得到确认：The structure of N-ethylcarbazole-6-(2-methylbenzoyl)-4-butenyl ketoxime was confirmed by 1H NMR:
1H NMR(400MHz,DMSO-d6)δ11.02(s,1H),8.52(d,J＝1.7Hz,1H),8.37(d,J＝1.7Hz,1H),7.72(dd,J＝8.7,1.7Hz,1H),7.64(dd,J＝8.7,1.7Hz,1H),7.51(dd,J＝18.4,8.7Hz,2H),7.49–7.45(m,1H),7.42–7.34(m,3H),5.68(ddt,J＝16.8,10.2,6.4Hz,1H),5.06(dq,J＝17.2,1.7Hz,1H),4.88(dq,J＝10.2,1.5Hz,1H),4.45(q,J＝7.1Hz,2H)，3.11(t,J＝7.3Hz,2H),2.69(s,3H),2.43–2.34(m,2H),1.26(t,J＝7.1Hz,3H)。 1 H NMR (400MHz, DMSO-d6) δ11.02(s, 1H), 8.52(d, J=1.7Hz, 1H), 8.37(d, J=1.7Hz, 1H), 7.72(dd, J=8.7 ,1.7Hz,1H),7.64(dd,J＝8.7,1.7Hz,1H),7.51(dd,J＝18.4,8.7Hz,2H),7.49–7.45(m,1H),7.42–7.34(m, 3H), 5.68(ddt, J=16.8, 10.2, 6.4Hz, 1H), 5.06(dq, J=17.2, 1.7Hz, 1H), 4.88(dq, J=10.2, 1.5Hz, 1H), 4.45(q , J=7.1Hz, 2H), 3.11(t, J=7.3Hz, 2H), 2.69(s, 3H), 2.43–2.34(m, 2H), 1.26(t, J=7.1Hz, 3H).
(3)化合物3的合成(3) Synthesis of compound 3
化学反应式：Chemical reaction formula:
Figure PCTCN2022097591-appb-000026
Figure PCTCN2022097591-appb-000026
冰浴条件下，将N-乙基咔唑-6-(2-甲基苯甲酰基)-3-甲基酮肟(0.594g，1.529mmol)，四氢呋喃(20mL)和氢化钠(0.11g，4.587mmol)加入到100mL圆底烧瓶，反应1小时。然后，将乙酰氯(0.415g，4.587mmol)滴加至反应体系继续反应1小时。反应结束后用饱和碳酸氢钠猝灭反应，并用20mL×3二氯甲烷萃取产物，合并有机相，并用无水硫酸钠干燥。旋蒸除去溶剂，经硅胶柱层析分离(石油醚：二氯甲烷＝1：3)得到0.57g淡黄色液体，收率：90％。Under ice bath conditions, N-ethylcarbazole-6-(2-methylbenzoyl)-3-methylketoxime (0.594g, 1.529mmol), tetrahydrofuran (20mL) and sodium hydride (0.11g, 4.587mmol) was added to a 100mL round bottom flask and reacted for 1 hour. Then, acetyl chloride (0.415 g, 4.587 mmol) was added dropwise to the reaction system to continue the reaction for 1 hour. After the reaction was completed, the reaction was quenched with saturated sodium bicarbonate, and the product was extracted with 20 mL×3 dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate. The solvent was removed by rotary evaporation, and 0.57 g of light yellow liquid was obtained by silica gel column chromatography (petroleum ether:dichloromethane=1:3), yield: 90%.
化合物3的结构通过核磁共振氢谱得到确认：The structure of compound 3 was confirmed by H NMR spectroscopy:
1H NMR(400MHz,DMSO-d6)8.62(d,J＝1.7Hz,1H),8.47(d,J＝1.7Hz,1H),7.92(dd,J＝8.7,1.7Hz,1H),7.84(dd,J＝8.7,1.7Hz,1H),7.71(dd,J＝18.4,8.7Hz,2H),7.51–7.45(m,1H),7.42–7.34(m,3H),5.88(ddt,J＝16.8,10.2,6.4Hz,1H),5.08(dq,J＝17.2,1.7Hz,1H),4.98(dq,J＝10.2,1.5Hz,1H),4.55(q,J＝7.1Hz,2H)，3.13(t,J＝7.3Hz,2H),2.43–2.34(m,2H),2.69(s,3H),2.31(s,3H),1.36(t,J＝7.1Hz,3H)。 1 H NMR (400MHz, DMSO-d6) 8.62 (d, J = 1.7Hz, 1H), 8.47 (d, J = 1.7Hz, 1H), 7.92 (dd, J = 8.7, 1.7Hz, 1H), 7.84 ( dd,J=8.7,1.7Hz,1H),7.71(dd,J=18.4,8.7Hz,2H),7.51–7.45(m,1H),7.42–7.34(m,3H),5.88(ddt,J= 16.8,10.2,6.4Hz,1H),5.08(dq,J=17.2,1.7Hz,1H),4.98(dq,J=10.2,1.5Hz,1H),4.55(q,J=7.1Hz,2H), 3.13 (t, J = 7.3Hz, 2H), 2.43–2.34 (m, 2H), 2.69 (s, 3H), 2.31 (s, 3H), 1.36 (t, J = 7.1Hz, 3H).
实施例4Example 4
本发明γ,δ-不饱和肟酯化合物的吸收性能测定Determination of Absorption Properties of γ, δ-Unsaturated Oxime Ester Compounds of the Present Invention
对实施例2和3制备的化合物2和3分别进行性能测定，通过紫外-可见光分光光度计在200-600nm下测量。化合物2和3的紫外-可见光吸收光谱见图1，说明通过改变芳香化合物(即Ar基团)的结构和种类，可以调控光引发剂的吸收波长，能与传统的高压汞灯及节能环保的LED光源 相匹配，应用范围广。The properties of Compounds 2 and 3 prepared in Examples 2 and 3 were measured by UV-visible spectrophotometer at 200-600 nm. The ultraviolet-visible light absorption spectra of compounds 2 and 3 are shown in Figure 1, indicating that by changing the structure and type of aromatic compounds (i.e. Ar groups), the absorption wavelength of the photoinitiator can be regulated, which can be compared with traditional high-pressure mercury lamps and energy-saving and environment-friendly lamps. The LED light source is matched and has a wide range of applications.
实施例5Example 5
本发明γ,δ-不饱和肟酯的光引发效率Photoinitiation Efficiency of γ, δ-Unsaturated Oxime Esters of the Invention
避光条件下，将10mg实施例1的化合物1加入到1g三羟甲基丙烷三丙烯酸酯单体中，溶解完全得到聚合样品。按照同样的方法制备了参比化合物的聚合样品，其中参比化合物的结构如下：Under light-shielded conditions, 10 mg of compound 1 of Example 1 was added to 1 g of trimethylolpropane triacrylate monomer, and dissolved completely to obtain a polymerized sample. A polymeric sample of the reference compound was prepared in the same manner, wherein the structure of the reference compound is as follows:
Figure PCTCN2022097591-appb-000027
Figure PCTCN2022097591-appb-000027
在广谱高压汞灯辐照(100mW/cm 2，250-1000nm,主发射波长365nm)下，通过实时红外光谱仪测试单体的转化率。图2为样品中单体转化率实时曲线。图2中结果表明，本发明的γ,δ-不饱和肟酯光的引发效率明显高于末端不含γ,δ-不饱和碳碳双键的参比化合物。本发明γ,δ-不饱和肟酯的引发单体的聚合速率和转化率高于末端不含γ,δ-不饱和碳碳双键的参比化合物。 Under the irradiation of a broad-spectrum high-pressure mercury lamp (100mW/cm 2 , 250-1000nm, the main emission wavelength is 365nm), the conversion rate of the monomer was tested by a real-time infrared spectrometer. Fig. 2 is the real-time curve of monomer conversion rate in the sample. The results in Fig. 2 show that the photoinitiation efficiency of the γ, δ-unsaturated oxime ester of the present invention is significantly higher than that of the reference compound without γ, δ-unsaturated carbon-carbon double bonds at the end. The polymerization rate and conversion rate of the initiating monomer of the γ, δ-unsaturated oxime ester of the present invention are higher than those of the reference compound without γ, δ-unsaturated carbon-carbon double bond at the end.
实施例6Example 6
本发明γ,δ-不饱和肟酯光引发剂在3D打印中的应用Application of γ, δ-unsaturated oxime ester photoinitiator of the present invention in 3D printing
避光条件下，在装有搅拌子的玻璃容器中加入800mg化合物3，80g三羟甲基丙烷三丙烯酸酯，搅拌振荡24h，使化合物3溶解完全，即可得到用于3D打印的光固化材料，将其倒入打印机(无锡金谷3D科技有限公司，mini-fab DLP)树脂槽，打印机所用光源波长为405nm，调出所要打印的3D模型，打印机自动打印出立体结构，如图3。Under the condition of avoiding light, add 800mg of compound 3 and 80g of trimethylolpropane triacrylate into a glass container equipped with a stirring bar, stir and shake for 24 hours, so that compound 3 is completely dissolved, and then the photocurable material for 3D printing can be obtained , pour it into the resin tank of the printer (Wuxi Jingu 3D Technology Co., Ltd., mini-fab DLP). The wavelength of the light source used by the printer is 405nm. Call out the 3D model to be printed, and the printer will automatically print out the three-dimensional structure, as shown in Figure 3.
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。Having described various embodiments of the present invention, the foregoing description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and alterations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
实施例7Example 7
避光条件下，将10mg实施例1的化合物1加入到1g三羟甲基丙烷三丙烯酸酯单体中，溶解完全得到聚合样品。按照同样的方法分别制备了含化合物2和化合物3的聚合样品。广谱高压汞灯辐照(100mW/cm 2，250-1000nm,主发射波长365nm)下，通过实时红外光谱仪测试单体的转化率。图4为辐照600s之后不同样品中单体转化率柱状图，其中使用化合物1的体系的单体转化率为约58％，使用化合物2的体系的单体转化率为约69％，使用化合物3的体系的单体转化率为约81％。图4中结果表明，使用本发明化合物作为光引发剂时，单体良好的聚合速率和转化率，而且含咔唑基团的γ,δ-不饱和肟酯的引发单体的聚合速率和转化率高于苯基γ,δ-不饱和肟酯。 Under light-shielded conditions, 10 mg of compound 1 of Example 1 was added to 1 g of trimethylolpropane triacrylate monomer, and dissolved completely to obtain a polymerized sample. Polymerized samples containing compound 2 and compound 3 were prepared in the same way. Under the irradiation of a broad-spectrum high-pressure mercury lamp (100mW/cm 2 , 250-1000nm, the main emission wavelength is 365nm), the conversion rate of the monomer was tested by a real-time infrared spectrometer. Figure 4 is a histogram of monomer conversion rates in different samples after irradiation for 600s, wherein the monomer conversion rate of the system using compound 1 is about 58%, and the monomer conversion rate of the system using compound 2 is about 69%. The monomer conversion of the system of 3 was about 81%. Result shows in Fig. 4, when using the compound of the present invention as photoinitiator, monomer good polymerization rate and conversion rate, and the polymerization rate and conversion rate of the initiation monomer of the gamma that contains carbazole group, the delta-unsaturated oxime ester The rate is higher than that of phenyl γ, δ-unsaturated oxime ester.

Claims (15)

  1. 式(I)的γ,δ-不饱和肟酯化合物作为光引发剂的用途，The gamma of formula (I), the purposes of the delta-unsaturated oxime ester compound as photoinitiator,
    Figure PCTCN2022097591-appb-100001
    Figure PCTCN2022097591-appb-100001
    其中，R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、硝基、氰基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基、C 1-C 20烷氧基、C 1-C 20烷基、C 1-C 20卤代烷基、C 3-C 10环烷基、C 4-C 20环烷基烷基、C 4-C 20烷基环烷基、C 3-C 10环烷氧基、C 4-C 20环烷基烷氧基、C 2-C 20烯基、C 6-C 18的芳基、C 7-C 20芳烷基、C 7-C 20烷基芳基和C 6-C 20芳氧基； Wherein, R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, nitro, cyano, amino, mono(C 1 -C 6 alkyl)amino, di(C 1 -C 6 alkyl) amino, C 1 -C 20 alkoxy, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 10 cycloalkyl, C 4 -C 20 cycloalkylalkyl , C 4 -C 20 alkylcycloalkyl, C 3 -C 10 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 2 -C 20 alkenyl, C 6 -C 18 aryl , C 7 -C 20 aralkyl, C 7 -C 20 alkylaryl and C 6 -C 20 aryloxy;
    R 6表示C 1-C 20烷基、C 1-C 20卤代烷基、C 3-C 10环烷基、C 4-C 20环烷基烷基、C 4-C 20烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基；和 R 6 represents C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 10 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 4 -C 20 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkylaryl; and
    Ar表示芳基或杂芳基。Ar represents aryl or heteroaryl.
  2. 根据权利要求1的用途，其中R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、硝基、氰基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基、C 1-C 12烷氧基、C 1-C 12烷基、C 1-C 12卤代烷基、C 3-C 8环烷基、C 4-C 12环烷基烷基、C 4-C 12烷基环烷基、C 3-C 8环烷氧基、C 4-C 12环烷基烷氧基、C 2-C 6烯基、C 6-C 10的芳基、C 7-C 12芳烷基、C 7-C 12烷基芳基和C 6-C 10芳氧基； The use according to claim 1, wherein R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, nitro, cyano, amino, mono(C 1 -C 6 alkyl)amino, Di(C 1 -C 6 alkyl)amino, C 1 -C 12 alkoxy, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 12 cycloalkylalkyl, C 4 -C 12 alkylcycloalkyl, C 3 -C 8 cycloalkoxy, C 4 -C 12 cycloalkylalkoxy, C 2 -C 6 alkenyl, C 6 -C 10 aryl, C 7 -C 12 aralkyl, C 7 -C 12 alkylaryl and C 6 -C 10 aryloxy;
    优选的是，R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 2-C 6烯基、C 6-C 10的芳基和C 7-C 12烷基芳基； Preferably, R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl) Amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 2 -C 6 alkenyl, C 6 -C 10 aryl and C 7 -C 12 alkylaryl;
    更优选R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、C 1-C 6卤代烷基和C 1-C 6烷基。 More preferably, R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, C 1 -C 6 haloalkyl and C 1 -C 6 alkyl.
  3. 根据权利要求1或2的用途，其中R 6表示C 1-C 12烷基、C 1-C 12卤代烷基、C 3-C 8环烷基、C 4-C 12环烷基烷基、C 4-C 12烷基环烷基、C 6-C 10芳 基、C 7-C 11芳烷基和C 7-C 11烷基芳基； Use according to claim 1 or 2, wherein R 6 represents C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 12 cycloalkylalkyl, C 4 -C 12 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl;
    优选的是，R 6表示C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基； Preferably, R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkyl Cycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl;
    更优选的是，R 6表示C 1-C 6烷基、C 1-C 6卤代烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 6烷基、苯基或者被苯基取代的C 1-C 6烷基； More preferably, R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 5 -C 6 cycloalkyl, C 1 -C 6 alkane substituted by C 5 -C 6 cycloalkyl Base, phenyl or C 1 -C 6 alkyl substituted by phenyl;
    最优选R 6为C 1-C 6烷基。 Most preferably R 6 is C 1 -C 6 alkyl.
  4. 根据权利要求1-3中任一项的用途，其中Ar表示C 6-C 30芳基或具有5-18个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基； Use according to any one of claims 1-3, wherein Ar represents a C 6 -C 30 aryl group or a heteroaryl group with 5-18 ring members, wherein the aryl or heteroaryl group is unsubstituted or replaced by Substituted by one or more groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkane with 3-8 ring members radical, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl having 3-8 ring members, C 6 - C 10 aryl, heteroaryl or amino with 5-8 ring members;
    优选Ar表示C 6-C 20芳基或具有5-18个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基； Preferably, Ar represents a C 6 -C 20 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl group or heteroaryl group is unsubstituted or replaced by one or more groups independently selected from the following group Substitution: hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5- 10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently Hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members base or amino;
    更优选Ar表示C 6-C 14芳基或具有5-14个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基， More preferably Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein the aryl or heteroaryl group is unsubstituted or replaced by one or more groups independently selected from the group Group substitution: hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5 -Heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"' of 10 ring members, wherein R', R" and R"' are each independently is hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heterocycloalkyl with 5-8 ring members aryl or amino,
    尤其是Ar为具有两个或三个稠合环的杂芳基，并且具有8-14，或9- 14或9-13个环成员，该杂芳基具有1或2个N原子作为环成员，该杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 In particular Ar is a heteroaryl having two or three fused rings and having 8-14, or 9-14 or 9-13 ring members, the heteroaryl having 1 or 2 N atoms as ring members , the heteroaryl is unsubstituted or substituted by one or more groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, with Heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, having 3-8 rings membered heterocycloalkyl, C 6 -C 10 aryl, heteroaryl having 5-8 ring members or amino.
  5. 根据权利要求1-4中任一项的用途，其中式(I)化合物中的各变量具有如下定义：Use according to any one of claims 1-4, wherein each variable in the compound of formula (I) has the following definitions:
    R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 2-C 6烯基、C 6-C 10的芳基和C 7-C 12烷基芳基； R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 2 -C 6 Alkenyl, C 6 -C 10 aryl and C 7 -C 12 alkylaryl;
    R 6表示C 1-C 6烷基、C 1-C 6卤代烷基、C 3-C 6环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基；和 R 6 represents C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl; and
    Ar表示C 6-C 20芳基或具有5-18个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 Ar represents a C 6 -C 20 aryl group or a heteroaryl group having 5-18 ring members, wherein the aryl or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : Hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
  6. 根据权利要求1-5中任一项的用途，其中式(I)化合物中的各变量具有如下定义：Use according to any one of claims 1-5, wherein each variable in the compound of formula (I) has the following definitions:
    R 1、R 2、R 3、R 4和R 5相互独立地表示氢、卤素、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和C 1-C 6烷基； R 1 , R 2 , R 3 , R 4 and R 5 independently represent hydrogen, halogen, amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino and C 1 -C 6 alkyl;
    R 6表示C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 6烷基、苯基或者被苯基取代的C 1-C 6烷基；和 R 6 represents C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 6 alkyl substituted by C 5 -C 6 cycloalkyl , phenyl or C 1 - substituted by phenyl C 6 alkyl; and
    Ar表示C 6-C 14芳基或具有5-14个环成员的杂芳基，其中所述芳基或杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、 氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 Ar represents a C 6 -C 14 aryl group or a heteroaryl group having 5-14 ring members, wherein the aryl group or heteroaryl group is unsubstituted or substituted by one or more groups independently selected from the following group : Hydroxy, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, with 5-10 ring member heteroaryl, amino, -C(O)R', -C(O)OR", -OC(O)R"', wherein R', R" and R"' are each independently hydrogen , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heterocycloalkyl with 3-8 ring members, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
  7. 根据权利要求1-6中任一项的用途，其中式(I)化合物选自下述化合物：Use according to any one of claims 1-6, wherein the compound of formula (I) is selected from the following compounds:
    Figure PCTCN2022097591-appb-100002
    Figure PCTCN2022097591-appb-100002
  8. 根据权利要求1-7中任一项的用途，其中用于辐射波长为300-550nm、优选350-525nm的光固化体系，特别是用于3D打印。Use according to any one of claims 1-7, wherein it is used in photocuring systems with a radiation wavelength of 300-550 nm, preferably 350-525 nm, in particular for 3D printing.
  9. 一种式(I)的γ,δ-不饱和肟酯化合物：A γ, δ-unsaturated oxime ester compound of formula (I):
    Figure PCTCN2022097591-appb-100003
    Figure PCTCN2022097591-appb-100003
    其中R 1、R 2、R 3、R 4、R 5和R 6如权利要求1-7中任一项所定义，以及 wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined in any one of claims 1-7, and
    Ar为具有两个或三个稠合环的杂芳基，并且具有8-14，或9-14或9- 13个环成员，该杂芳基具有1或2个N原子作为环成员，该杂芳基未被取代或被一个或多个独立地选自下组的基团取代：羟基、卤素、氰基、C 1-C 6烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-10个环成员的杂芳基、氨基、-C(O)R’、-C(O)OR”、-OC(O)R”’，其中R’、R”和R”’各自独立地为氢、C 1-C 6烷基烷基、C 3-C 8环烷基、具有3-8个环成员的杂环烷基、C 6-C 10芳基、具有5-8个环成员的杂芳基或氨基。 Ar is a heteroaryl group with two or three fused rings and has 8-14, or 9-14 or 9-13 ring members, the heteroaryl group has 1 or 2 N atoms as ring members, the Heteroaryl is unsubstituted or substituted by one or more groups independently selected from the group consisting of hydroxyl, halogen, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, with 3- Heterocycloalkyl with 8 ring members, C 6 -C 10 aryl, heteroaryl with 5-10 ring members, amino, -C(O)R', -C(O)OR", -OC (O)R"', wherein R', R" and R"' are each independently hydrogen, C 1 -C 6 alkylalkyl, C 3 -C 8 cycloalkyl, C having 3-8 ring members Heterocycloalkyl, C 6 -C 10 aryl, heteroaryl with 5-8 ring members or amino.
  10. 根据权利要求9的化合物，其为A compound according to claim 9 which is
    Figure PCTCN2022097591-appb-100004
    Figure PCTCN2022097591-appb-100004
  11. 一种制备如权利要求1-10中任一项所定义的式(I)化合物的方法，其包括使式(E)化合物A method for preparing a compound of formula (I) as defined in any one of claims 1-10, comprising making the compound of formula (E)
    Figure PCTCN2022097591-appb-100005
    Figure PCTCN2022097591-appb-100005
    其中R 1、R 2、R 3、R 4、R 5和Ar如权利要求1-10中任一项所定义，与式(F)化合物反应得到式(I)化合物 wherein R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined in any one of claims 1-10, reacting with the compound of formula (F) to obtain the compound of formula (I)
    Figure PCTCN2022097591-appb-100006
    Figure PCTCN2022097591-appb-100006
    其中X 1为卤素、羟基或-C(＝O)-R 6，以及R 6如权利要求1-10中任一项所 定义。 wherein X 1 is halogen, hydroxyl or -C(=O)-R 6 , and R 6 is as defined in any one of claims 1-10.
  12. 根据权利要求11的方法，其包括使式(C)化合物与羟胺和/或盐酸羟胺进行肟化反应得到式(E)化合物The method according to claim 11, which comprises making the compound of formula (C) carry out oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain the compound of formula (E)
    Figure PCTCN2022097591-appb-100007
    Figure PCTCN2022097591-appb-100007
    其中R 1、R 2、R 3、R 4、R 5和Ar如权利要求1-10中任一项所定义。 wherein R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined in any one of claims 1-10.
  13. 根据权利要求12的方法，其包括使式(A)化合物according to the method for claim 12, it comprises making formula (A) compound
    Ar-HAr-H
    (A)(A)
    其中Ar如权利要求1-10中任一项所定义，wherein Ar is as defined in any one of claims 1-10,
    与式(B)化合物反应而制备式(C)化合物React with formula (B) compound and prepare formula (C) compound
    Figure PCTCN2022097591-appb-100008
    Figure PCTCN2022097591-appb-100008
    其中R 1、R 2、R 3、R 4、R 5和Ar如权利要求1-10中任一项所定义，以及X 2为卤素。 wherein R 1 , R 2 , R 3 , R 4 , R 5 and Ar are as defined in any one of claims 1-10, and X 2 is halogen.
  14. 包含至少一种根据权利要求1-10中任一项的式(I)的γ,δ-不饱和肟酯化合物的光固化性组合物。Photocurable composition comprising at least one γ,δ-unsaturated oxime ester compound of formula (I) according to any one of claims 1-10.
  15. 可由权利要求14的光固化性组合物得到的固化材料。Cured material obtainable from the photocurable composition of claim 14.
PCT/CN2022/097591 2021-06-11 2022-06-08 USE OF γ,δ-UNSATURATED OXIME ESTER COMPOUNDS AS PHOTOINITIATORS WO2022257957A1 (en)

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