WO2020258014A1 - Long-wavelength coumarin oxime ester compound, preparation therefor, and application thereof - Google Patents

Long-wavelength coumarin oxime ester compound, preparation therefor, and application thereof Download PDF

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WO2020258014A1
WO2020258014A1 PCT/CN2019/092708 CN2019092708W WO2020258014A1 WO 2020258014 A1 WO2020258014 A1 WO 2020258014A1 CN 2019092708 W CN2019092708 W CN 2019092708W WO 2020258014 A1 WO2020258014 A1 WO 2020258014A1
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group
alkyl
thio
alkoxy
cycloalkyl
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PCT/CN2019/092708
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庞玉莲
邹应全
樊书珩
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湖北固润科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • 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

Definitions

  • the present invention relates to coumarin 3-(keto)oxime ester compounds suitable for ultraviolet-visible LED exposure light sources, and such compounds can be used as photoinitiators.
  • the invention also relates to the preparation of the coumarin 3-(keto)oxime ester compound and its application as a photoinitiator.
  • Photoinitiator also known as photosensitizer, is a type of energy that can absorb a certain wavelength of energy in the ultraviolet region (250-400nm) or visible region (400-600nm) to generate free radicals, cations, etc., thereby initiating monomer polymerization, crosslinking and curing compound of.
  • the light curing system although the content is low, it is the key component among them, which plays a decisive role in the light curing speed. It is related to whether the oligomer and diluent can be quickly cross-linked and solidified when the formula system is irradiated with light, thereby changing from liquid to solid.
  • photoinitiators must meet the needs of different light curing conditions and applications.
  • the main goals are: improve light sensitivity, improve surface curing efficiency (anti-oxidation inhibition), improve deep curing performance, improve the solubility of photoinitiators in monomers and resins, and reduce toxicity and odor , Reduce the migration of uncured initiator after curing, reduce yellowing.
  • Oxime ester photoinitiators have become a class of photoinitiators that have gradually received attention in recent years due to their excellent photosensitivity.
  • BASF's products OXE-01 and OXE-02 are two representative products of oxime esters that are common on the market. These two products have high photosensitivity, but their ultraviolet absorption wavelength is too short (250-350nm), which is not suitable for ultraviolet-visible LED light source (emission wavelength 365nm, 385nm, 395nm, 405nm, 420nm, 430nm, 450nm).
  • ultraviolet-visible LED light source emission wavelength 365nm, 385nm, 395nm, 405nm, 420nm, 430nm, 450nm.
  • CN10277552A discloses a diphenyl sulfide ketoxime ester photoinitiator and its preparation method
  • CN102492059A discloses a substituted diphenyl sulfide ketoxime ester photoinitiator. Agent and so on.
  • most initiators have UV absorption wavelengths of 250-350nm, which cannot match the increasingly developed LED light sources, which greatly limits the application of oxime ester photoinitiators.
  • LED point light sources, line light sources, and surface light sources have begun to be used in the light curing industry. Compared with traditional UV curing equipment, LED light sources have absolute advantages.
  • the service life of the mercury lamp is only 800-3000 hours, and the service life of the UV-LED ultraviolet curing system can reach 20,000-30000 hours.
  • the LED method can be lit instantaneously only when ultraviolet light is needed.
  • the traditional mercury lamp curing equipment is working, because the mercury lamp starts slowly and the opening and closing affects the life of the bulb, it must be lit all the time, which not only causes unnecessary power consumption, but also shortens the working life of the mercury lamp.
  • the traditional mercury lamp curing machine uses a mercury lamp to emit light. There is mercury in the bulb, which makes the waste disposal and transportation very troublesome, and improper handling can cause serious pollution to the environment.
  • the LED curing machine uses semiconductors to emit light and has no environmental pollution factors. Therefore, the use of LED curing machine is more environmentally friendly.
  • each illuminating head emits light independently, and the illuminating energy is not affected by the increase in the channel, and always remains at the maximum. Because of its super concentrated illuminance, compared with mercury lamps, UV-LED shortens the irradiation time of the operation and improves the production efficiency.
  • UV-LED method Low energy consumption.
  • the effective luminous efficiency of UV-LED method is more than 10 times higher than that of mercury lamp method.
  • the UV-LED method consumes power only during irradiation, and almost zero power consumption during standby.
  • UVLED surface light source and UVLED line light source both include the visible part of the UV spectrum
  • visible light curing will have less energy loss.
  • the main advantage of visible light curing is that it can pass through the UV-blocking substrate to cure the glue and can choose translucent colored materials. Improved safety is another important advantage of visible light curing equipment.
  • the output is visible light, and UV-related shading and protection can be minimized. Therefore, the development of photoinitiators suitable for UV-visible LED light sources will greatly meet the wide application needs of UV-visible LED exposure light sources in the photocuring industry.
  • CN1889960A discloses that coumarin ketoxime ester compounds can be used in pharmaceutical or cosmetic compositions to prevent and treat diseases, including immune diseases, chronic inflammation, neurological and skin diseases, tumor diseases, specific viruses (especially Is SARS) and so on. In this sense, such compounds are safe and non-toxic.
  • the inventors of the present invention have conducted extensive and in-depth research on photoinitiators suitable for radiation curing of ultraviolet-visible LED light sources (emission wavelengths of 300-500nm, especially 350-450nm). In order to find a photoinitiator that can replace OXE-01 and OXE-02 to be more suitable for UV-visible LED light source curing and has good thermal stability.
  • the modified coumarin (ketone) oxime ester compound obtained by condensing a benzo five-membered ring on the benzene ring of the coumarin (ketone) oxime ester compound has a range of 300-500nm, especially 350-450nm It has strong ultraviolet absorption in the range and has good thermal stability, so it is suitable for use as a photoinitiator for radiation curing of ultraviolet-visible LED light sources.
  • the purpose of the present invention is achieved based on the foregoing findings.
  • an object of the present invention is to provide a coumarin (ketone) oxime ester compound whose absorption wavelength is not only suitable for UV-visible LED light source radiation curing, but also has good thermal stability.
  • Another object of the present invention is to provide a method for preparing the coumarin (keto)oxime ester compound of the present invention.
  • Another object of the present invention is to provide the use of the coumarin (keto)oxime ester compound of the present invention as a photoinitiator.
  • a coumarin (keto)oxime ester compound of formula (I) comprising the following formula (I-1):
  • X is O, S, NR 1 or CR 2a R 2b , wherein R 1 , R 2a and R 2b are each independently H, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (sulfur ) Group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl group Or a C 6 -C 18 aryloxy (thio) group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the following group: halogen,
  • R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl, C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl or C 6- A C 18 aryloxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyan
  • a 1 , A 2 , A 3 , and A 4 connected to the structural part of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , wherein R 7 is H , Halogen, C 1 -C 6 alkyl group or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group may contain one or more The same or different halogen substituents;
  • R 8 is H, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and the aforementioned C 1 -C 6 alkoxy (thio) group may Contain one or more identical or different halogen substituents;
  • R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl, C 1 -C 8 alkyl, C 1 -C 8 Alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 Alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl group or C 6 -C 18 aryloxy (thio) group, wherein the foregoing except Each group other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -
  • R 10 is a C 1 -C 20 alkyl group or a C 6 -C 18 aryl group, wherein the C 1 -C 20 alkyl group and the C 6 -C 18 aryl group may contain one or more substituents independently selected from the following group : Halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group; and
  • n 0 or 1.
  • R 1 , R 2a and R 2b are each independently H, C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkyl, C 1- C 6 alkyl C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 Alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 8 cycloalkoxy (thio) group, C 6 -C 10 aryl group or C 6 -C 10 aryloxy (thio) group, wherein the foregoing
  • Each group other than H may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6
  • R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl C 1 -C 6 alkyl, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 10 aryl or C 6- C 10 aryloxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano
  • R 7 is H, fluorine, chlorine, bromine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy (sulfur) group, wherein the aforementioned C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) )
  • the group may contain one or more identical or different substituents selected from fluorine, chlorine and bromine; and/or
  • R 8 is H, fluorine, chlorine, bromine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy (sulfur) group, wherein the aforementioned C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) )
  • the group may contain one or more identical or different substituents selected from fluorine, chlorine and bromine; and/or
  • R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkyl, C 1 -C 6 alkyl C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 Alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 8 cycloalkoxy (thio) group, C 6 -C 10 aryl group or C 6 -C 10 aryloxy (thio) group, wherein the foregoing except Each group other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -
  • R 10 is a C 1 -C 6 alkyl group or a C 6 -C 10 aryl group, wherein the C 1 -C 6 alkyl group and the C 6 -C 10 aryl group may contain one or more substituents independently selected from the following group : Halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group, preferably, R 10 is C 1 -C 4 alkyl or phenyl, wherein The C 1 -C 4 alkyl group and the phenyl group may contain one or more substituents independently selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) group.
  • X is O, S, NR 1 or CR 2a R 2b , wherein R 1 is C 1 -C 8 alkyl, phenyl or naphthyl, wherein said phenyl or naphthyl may contain one or more of the same or different C 1 -C 4 alkyl substituent; and R 2a and R 2b are the same or different, and are each independently H, C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkyl Or C 1 -C 4 alkoxy C 1 -C 4 alkyl;
  • R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy (thio) or phenyl;
  • a 1 , A 2 , A 3 , and A 4 connecting the structural parts of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , wherein R 7 H or C 1 -C 4 alkyl;
  • R 8 is H or C 1 -C 4 alkyl
  • R 9 is cyano, C 1 -C 7 alkyl, halo C 1 -C 6 alkyl or C 5 -C 6 cycloalkyl C 1 -C 4 alkyl;
  • R 10 is C 1 -C 4 alkyl or phenyl.
  • a method for preparing the compound as claimed in any one of items 1-4 comprising the following steps:
  • a 1 , A 2 , A 3 , A 4 , R 8 and R 9 in formulas (II), (IIIa) and (IIIb) are as defined in any one of items 1-4;
  • the oximation reaction is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof as a catalyst; and/or, the temperature of the oximation reaction is 60-120°C; and/or,
  • the molar ratio of the compound of formula (II) to the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is 1:1.5-1.5:1, preferably 1:1.2-1.2:1; or
  • the oximation reaction is carried out in the presence of concentrated hydrochloric acid; and/or the temperature of the oximation reaction is -30 to 20°C, preferably 5-20°C; and/or, the compound of formula (II) is selected from nitrous acid and nitrite And/or the molar ratio of the alkyl nitrite compound is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
  • the alkyl nitrite is a C 1 -C 6 alkyl nitrite, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite; and/or,
  • step (2) is carried out with an esterification reagent selected from compounds of the following formulas (IVa), (IVb) and (IVc):
  • X is halogen, especially chlorine, and R 7 is as defined in any one of items 1-4.
  • a 1 , A 2 , A 3 , A 4 and R 8 in the compound of formula (V) are as defined in any one of items 1-4
  • R 9 in the compound of formula (VI) is as defined in items 1-4
  • R 11 is a C 1 -C 12 alkyl group, preferably a C 1 -C 6 alkyl group.
  • the temperature of the Novenge condensation reaction is 0-150°C, preferably 0-100°C; and/or
  • the molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
  • Figure 1 is a schematic diagram of Ugra printing test strips, where
  • a coumarin (keto)oxime ester compound of formula (I) comprising the following formula (I-1):
  • X is O, S, NR 1 or CR 2a R 2b , wherein R 1 , R 2a and R 2b are each independently H, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (sulfur ) Group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl group Or a C 6 -C 18 aryloxy (thio) group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the following group: halogen,
  • R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl, C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl or C 6- A C 18 aryloxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyan
  • a 1 , A 2 , A 3 , and A 4 connected to the structural part of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , wherein R 7 is H , Halogen, C 1 -C 6 alkyl group or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group may contain one or more The same or different halogen substituents;
  • R 8 is H, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and the aforementioned C 1 -C 6 alkoxy (thio) group may Contain one or more identical or different halogen substituents;
  • R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl, C 1 -C 8 alkyl, C 1 -C 8 Alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 Alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl group or C 6 -C 18 aryloxy (thio) group, wherein the foregoing except Each group other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -
  • R 10 is a C 1 -C 20 alkyl group or a C 6 -C 18 aryl group, wherein the C 1 -C 20 alkyl group and the C 6 -C 18 aryl group may contain one or more substituents independently selected from the following group : Halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group; and
  • n 0 or 1.
  • the compound of formula (I) contains not only the coumarin (ketone) oxime ester structural part, but also the benzo five-membered ring structure fused with it. Such a structure makes the compound have strong ultraviolet absorption in the range of 300-500nm, preferably 350-450nm. After absorbing light energy, it can quickly transfer energy, continue to initiate polymerization, and has obvious advantages in photosensitivity and pattern integrity. , It is very suitable for UV-visible LED light source and its safe and non-toxic can be used in food packaging and other fields. In addition, the compound of formula (I) also has good thermal stability.
  • C n -C m indicates 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 preferable that the halogen includes F, Cl or a combination thereof.
  • C n -C m alkyl group as used herein means having nm number, for example 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, especially preferably 1-4 Branched or unbranched saturated hydrocarbon groups with three carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3
  • C 3 -C m cycloalkyl refers to a saturated alicyclic monocyclic group having 3 to m, such as 3 to 20, preferably 3 to 8, and more preferably 5 to 6 carbon atoms. Groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
  • C 3 -C m cycloalkyl C n -C m alkyl means C n -C m alkyl substituted by C 3 -C m cycloalkyl, in which case two m may be the same or different, where C The n -C m alkyl group and the C 3 -C m cycloalkyl group apply as defined herein.
  • C 3 -C m cycloalkyl C n -C m alkyl may be C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, preferably C 3 -C 6 cycloalkyl C 1 -C 6 alkyl , More preferably C 3 -C 6 cycloalkyl C 1 -C 4 alkyl, such as cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclo Butylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl , Cyclohexylpropyl, cyclohexylbuty
  • C n -C m alkyl C 3 -C m cycloalkyl means a C 3 -C m cycloalkyl group substituted by C n -C m alkyl. In this case, two m may be the same or different, where C The n -C m alkyl group and the C 3 -C m cycloalkyl group apply as defined herein.
  • C n -C m alkyl C 3 -C m cycloalkyl can be C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, preferably C 1 -C 6 alkyl C 3 -C 6 cycloalkyl , More preferably C 1 -C 4 alkyl C 3 -C 6 cycloalkyl, such as methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethyl Cyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propyl ring Hexyl, butylcyclohexyl, etc.
  • C 6 -C m aryl group refers to a monocyclic, bicyclic or multicyclic aromatic hydrocarbon group containing 6 to m carbon atoms, such as 6 to 18, preferably 6 to 10 carbon atoms.
  • C 6 -C m aryl groups mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methyl ethyl phenyl, diethyl phenyl, Methyl ⁇ propylphenyl, naphthyl, etc.; preferably phenyl or naphthyl, especially phenyl.
  • C n -C m alkoxy (thio) group when used alone or in combination includes "C n -C m alkoxy group” and "C n -C m alkylthio group”, and refers to the C n -C m corresponding open-chain alkyl group C n -C m alkane any carbon atom bonded to an oxygen atom or a sulfur atom as a C n -C m alkyl linking group, e.g.
  • C 1 -C 20 alkoxy (thio ) Group preferably C 1 -C 12 alkoxy (thio) group, more preferably C 1 -C 8 alkoxy (thio) group, particularly preferably C 1 -C 6 alkoxy (thio) group, particularly preferably C 1 -C 4 Alkoxy (thio) group.
  • C 1 -C 8 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy Group, hexyloxy, heptyloxy, octyloxy, isooctyloxy and its isomers.
  • the C 1 -C 8 alkylthio group can be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, tert-butylthio, pentylthio, isoamylthio Group, hexylthio, heptylthio, octylthio, isooctylthio and its isomers.
  • C 3 -C m cycloalkoxy (thio) group include “C 3 -C m cycloalkoxy” and "C 3 -C m cycloalkylthio" refers to C 3 any ring carbon atom -C m cycloalkyl C 3 -C m corresponding cycloalkane is bonded to an oxygen atom or a sulfur atom as a cyclic C 3 -C m alkyl linking group, for example C 3 - C 20 cycloalkoxy (sulfur) group, preferably C 3 -C 8 cycloalkoxy (sulfur) group, more preferably C 5 -C 6 cycloalkoxy (sulfur) group, such as cyclopropyloxy, cyclobutyloxy Cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecy
  • C 3 -C m cycloalkyl C n -C m alkoxy (thio) group includes “C 3 -C m cycloalkyl C n -C m alkoxy” and "C 3 -C m cycloalkane "C n -C m alkylthio group” refers to a C n -C m alkoxy (thio) group substituted by a C 3 -C m cycloalkyl group. In this case, two m may be the same or different, where C 3- The C m cycloalkyl group and the C n -C m alkoxy (thio) group apply as defined herein.
  • C 3 -C m cycloalkyl C n -C m alkoxy (thio) group may be C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, preferably C 3 -C 6 cycloalkyl C 1 -C 6 alkoxy (thio) group, more preferably C 3 -C 6 cycloalkyl C 1 -C 4 alkoxy (thio) group, such as cyclopropylmethoxy, cyclopropylethoxy, cyclo Propylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethyl Oxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy,
  • C n -C m alkyl C 3 -C m cycloalkoxy group means a C 3 -C m cycloalkoxy group substituted by C n -C m alkyl group, in which case two m may be the same or different, Wherein C n -C m alkyl group and C 3 -C m cycloalkoxy group are defined herein.
  • C n -C m alkyl C 3 -C m cycloalkoxy may be C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy, preferably C 1 -C 6 alkyl C 3 -C 6 ring Alkoxy, more preferably C 1 -C 4 alkyl C 3 -C 6 cycloalkoxy, such as methylcyclopropoxy, ethylcyclopropoxy, propylcyclopropoxy, butylcyclopropoxy , Methylcyclobutoxy, ethylcyclobutoxy, propylcyclobutoxy, butylcyclobutoxy, methylcyclopentyloxy, ethylcyclopentyloxy, propylcyclopentyloxy, butylcyclopentyl Oxy, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, etc.
  • C 6 -C m aryloxy (thio) group includes “C 6 -C m aryloxy group” and "C 6 -C m arylthio group", which means that the C 6 -C m aryl group corresponds to the C 6 -C m on any of the aromatic carbon atoms in the aromatic hydrocarbon is bonded to an oxygen atom or a sulfur atom as a linking group C 6 -C m aryl group, e.g. phenyl group, a phenoxy group, tolyloxy , Tolylthio, naphthylthio, naphthyloxy, etc.
  • n is 0 or 1.
  • the compound of formula (I) is called a coumarin oxime ester compound; when n is 1, the compound of formula (I) is called a coumarin ketoxime ester compound.
  • coumarin (keto)oxime ester compounds are collectively referred to as coumarin (keto)oxime ester compounds.
  • X is O, S, NR 1 or CR 2a R 2b , wherein R 1 , R 2a and R 2b are each independently H, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl , C 3 -C 10 cycloalkyl, C 1 -C 8 alkyl, C 1 -C 8 alkyl, C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 Cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl or C 6 -C 18 aryloxy (sulfur) group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the following group: hal
  • R 1 , R 2a and R 2b are each independently H, C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkyl , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 alkoxy (sulfur) group, C 1 -C 6 alkyl C 3 -C 8 cycloalkoxy (sulfur) group, C 6 -C 10 aryl or C 6 -C 10 aryloxy (sulfur) Group, wherein each group other than H mentioned above may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C
  • R 1 , R 2a and R 2b are each independently H, C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkane Group, C 1 -C 4 alkyl C 5 -C 6 cycloalkyl, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy (thio) group, C 3 -C 6 cycloalkane C 1 -C 4 alkoxy (sulfur) group, C 1 -C 4 alkyl, C 5 -C 6 cycloalkoxy (sulfur) group, C 6 -C 10 aryl or C 6 -C 10 aryloxy (sulfur ) Group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 4 alkane Group
  • R 1 is C 1 -C 8 alkyl, phenyl or naphthyl, wherein the phenyl or naphthyl may contain one or more identical or different C 1 -C 4 alkyl substituents; and R 2a and R 2b are the same or different, and are each independently H, C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl C 1 -C 4 alkyl, or C 1 -C 4 alkoxy C 1- C 4 alkyl.
  • R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3- C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy ( Thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl Group or C 6 -C 18 aryloxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the group: halogen, nitro Group, amino
  • R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl C 1 -C 6 alkyl, C 1 -C 6 alkyl C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (sulfur) group, C 3 -C 8 cycloalkoxy (sulfur ) Group, C 3 -C 8 cycloalkyl C 1 -C 6 alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 10 aryl group Or a C 6 -C 10 aryloxy (thio) group, wherein each of the aforementioned groups except hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the following
  • R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 4 alkyl, C 5 -C 6 cycloalkyl, C 5- C 6 cycloalkyl C 1 -C 4 alkyl, C 1 -C 4 alkyl C 5 -C 6 cycloalkyl, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy ( Sulfur) group, C 5 -C 6 cycloalkyl C 1 -C 4 alkoxy (thio) group, C 1 -C 4 alkyl C 5 -C 6 cycloalkoxy (thio) group, phenyl or phenoxy ( Sulfur) group, wherein each of the aforementioned groups except hydrogen, halogen, nitro, cyano may contain one or more substituents independently selected from the following group: fluorine, chlorine, bromine, nitro, amino,
  • R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy (thio) or phenyl.
  • two of A 1 , A 2 , A 3 , and A 4 connected to the structural part of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 ,
  • R 7 is H, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group can be Contains one or more identical or different halogen substituents.
  • R 7 is H, fluorine, chlorine, bromine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy (thio) group, wherein the aforementioned C 1 -C 4 alkyl and C 1 -C 4
  • the alkoxy (thio) group may contain one or more identical or different substituents selected from fluorine, chlorine, and bromine.
  • R 7 is H or C 1 -C 4 alkyl.
  • R 8 is H, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and C 6 alkoxy (thio) group It may contain one or more halogen substituents that are the same or different.
  • R 8 is H, fluorine, chlorine, bromine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy (thio) group, wherein the aforementioned C 1 -C 4 alkyl group and C 1 -C 4
  • the alkoxy (thio) group may contain one or more identical or different substituents selected from fluorine, chlorine, and bromine.
  • R 8 is H.
  • R 8 is H or C 1 -C 4 alkyl.
  • R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl, C 1 -C 8 alkyl , C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (sulfur) group, C 1 -C 8 alkyl, C 3 -C 10 cycloalkoxy (sulfur) group, C 6 -C 18 aryl or C 6 -C 18 aryloxy (sulfur) Group, wherein each of the aforementioned groups other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino,
  • R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkyl, C 1 -C 6 alkyl C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 alkoxy (thio) group, C 1 -C 6 alkyl, C 3 -C 8 cycloalkoxy (thio) group, C 6 -C 10 aryl or C 6 -C 10 aryloxy (thio) group , Wherein each of the aforementioned groups other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano, C
  • R 9 is hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl C 1- C 4 alkyl group, C 1 -C 4 alkyl group, C 5 -C 6 cycloalkyl group, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy (thio) group, C 5 -C 6 cycloalkyl C 1 -C 4 alkoxy (thio) group, C 1 -C 4 alkyl C 5 -C 6 cycloalkoxy (thio) group, phenyl or phenoxy (thio) group, wherein the foregoing is except hydrogen
  • Each group other than fluorine, chlorine, bromine, nitro and cyano may contain one or more substituents independently selected from the following group: fluorine, chlorine, bromine, nitro, amino, cyano
  • R 9 is a cyano group, a C 1 -C 7 alkyl group, a halogenated C 1 -C 6 alkyl group or a C 5 -C 6 cycloalkyl C 1 -C 4 alkyl group.
  • R 10 is a C 1 -C 20 alkyl group or a C 6 -C 18 aryl group, wherein the C 1 -C 20 alkyl group and the C 6 -C 18 aryl group may include one or more independently selected from Substituents of the following group: halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group.
  • R 10 is C 1 -C 6 alkyl or C 6 -C 10 aryl, wherein C 1 -C 6 alkyl and C 6 -C 10 aryl may include one or more independently selected from Substituents of the group: halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group.
  • R 10 is a C 1 -C 4 alkyl group or a phenyl group, wherein the C 1 -C 4 alkyl group and the phenyl group may contain one or more substituents independently selected from the following group: fluorine, chlorine, Bromine, nitro, amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (thio) group.
  • R 10 is C 1 -C 4 alkyl or phenyl.
  • X is O, S, NR 1 or CR 2a R 2b , wherein R 1 is C 1 -C 8 alkyl, phenyl or naphthyl, wherein said phenyl or naphthyl may contain one or more of the same or different C 1 -C 4 alkyl substituent; and R 2a and R 2b are the same or different, and are each independently H, C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkyl , C 1 -C 4 alkoxy C 1 -C 4 alkyl;
  • R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy (thio) or phenyl;
  • a 1 , A 2 , A 3 , and A 4 connecting the structural parts of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , wherein R 7 H or C 1 -C 4 alkyl;
  • R 8 is H or C 1 -C 4 alkyl
  • R 9 is cyano, C 1 -C 7 alkyl, halo C 1 -C 6 alkyl or C 5 -C 6 cycloalkyl C 1 -C 4 alkyl;
  • R 10 is C 1 -C 4 alkyl or phenyl.
  • the compound of formula (I) is selected from compounds 1-64.
  • Compounds 1-64 were prepared in Examples 1-64, respectively.
  • a 1 , A 2 , A 3 , A 4 , R 8 and R 9 in formula (II), (IIIa) and (IIIb) are as defined for the compound of formula (I);
  • the oximation reaction usually starts from the carbonyl compound. For this reason, when n is 0, the compound of formula (III) is subjected to an oximation reaction with hydroxylamine, hydroxylamine hydrochloride or any combination thereof to obtain a compound of formula (IIIa):
  • a 1 , A 2 , A 3 , A 4 , R 8 and R 9 in formula (II) and (IIIa) are as defined for the compound of formula (I).
  • hydroxylamine hydrochloride NH 2 OH ⁇ HCl
  • hydroxylamine NH 2 OH
  • a mixture thereof is usually used as an oximation reagent.
  • the oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Examples of usable solvents include ethanol or water-containing ethanol.
  • a base such as sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide, or a mixture thereof.
  • pyridine, piperidine, and triethylamine can also be used as bases and/or solvents or co-solvents.
  • the temperature of the oximation reaction is generally the reflux temperature of the solvent, and the temperature range is usually 60-120°C.
  • the oximation reaction time is also not particularly limited, and it is usually carried out for 0.1-20 hours, preferably 0.5-10 hours.
  • the relative amount of the compound of formula (II) and the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is not particularly limited. Generally speaking, they are used in approximately equimolar amounts, for example, the molar ratio of the two is 1:1.5-1.5:1, Preferably it is 1:1.2-1.2:1.
  • a 1 , A 2 , A 3 , A 4 , R 8 and R 9 in formula (IIIb) are as defined for formula (I).
  • nitrous acid, nitrite, alkyl nitrite or a mixture thereof are usually used as an oximation reagent.
  • This reagent nitrosates the "active" (methylene) methyl group ( ⁇ -(methylene) methyl group, that is, the (methylene) group next to the non-cyclic carbonyl group).
  • sodium nitrite is usually used as the nitrite.
  • the alkyl nitrite may be a C 1 -C 6 alkyl nitrite, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite.
  • the oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Examples of usable solvents include tetrahydrofuran, ethanol, or water-containing ethanol. In order to promote the completion of the oximation reaction, it is generally necessary to add concentrated hydrochloric acid, the concentration of which is usually 20-40%. Concentrated hydrochloric acid can also be used as acid and/or solvent or co-solvent.
  • the temperature of the oximation reaction is a low temperature, and the temperature range is usually -30 to 20°C, preferably 5-20°C.
  • the oximation reaction time is also not particularly limited, and it is usually carried out for 0.1-20 hours, preferably 0.5-10 hours.
  • the relative amount of the compound of formula (II) and the compound selected from the group consisting of nitrous acid, nitrite and/or alkyl nitrite is not particularly limited. Generally, they are used in approximately equimolar amounts, for example, the molar ratio of the two is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
  • Each oxime ester group may have two configurations, (Z) type or (E) type.
  • the isomers can be separated by conventional methods, but it is also possible to use a mixture of isomers as the photoinitiating substance. Therefore, the present invention also relates to a mixture of each configurational isomer of the compound of formula (I).
  • the esterification of the compounds of formula (IIIa) and (IIIb) is conventional. Through this reaction, the hydroxyl group in the oxime group is converted into an ester group, thereby obtaining the compound of formula (I).
  • the esterification reagent there is no particular limitation, as long as it can convert the hydroxyl group in the oxime group of the compounds of formula (IIIa) and (IIIb) into an ester group.
  • the esterification reagent the corresponding acid halide, such as acid chloride, the corresponding carboxylic acid, and the corresponding acid anhydride can also be used. These compounds can be represented as formula (IVa), (IVb) and (IVc) respectively:
  • the above-mentioned esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction.
  • a catalyst suitable for the esterification reaction.
  • an acid catalyst or a basic catalyst may be used.
  • sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, ethanol can be used Sodium, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide, tertiary amines (e.g. trialkylamines such as trimethylamine and triethylamine) or any combination thereof.
  • the amount of catalyst used is conventional and can be determined by common sense in the field or through several routine preliminary experiments.
  • the above-mentioned esterification reaction is usually carried out in a solvent, preferably in an organic solvent.
  • a solvent preferably in an organic solvent.
  • the type of solvent there is no particular limitation on the choice of the type of solvent, as long as it can dissolve the compound of formula (IIIa) or formula (IIIb) and the esterification reagent and is chemically inert to the esterification reaction, that is, it does not participate in the esterification reaction.
  • the solvent tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone can be mentioned.
  • a single solvent may be used, or a mixture of two or more solvents may be used.
  • the relative amount of the compound of formula (IIIa) or (IIIb) and the esterification agent selected from the group of compounds (IVa), (IVb) and (IVc) is not particularly limited. Generally speaking, they are used in approximately equimolar amounts, such as two The molar ratio of these is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
  • the esterification reaction can be carried out in a very wide temperature range. According to the present invention, it is advantageous that the esterification reaction is carried out at a temperature of -10°C to 150°C, preferably 0°C to 100°C, preferably at room temperature.
  • the esterification reaction time is also not particularly limited, and it is usually carried out for 1-24 hours, preferably 1-12 hours.
  • the reaction mixture After the esterification reaction is completed, a reaction mixture containing the compound of formula (I) is obtained. Therefore, the reaction mixture needs to be post-treated to obtain a purified compound of formula (I). Generally, the reaction mixture obtained by the esterification reaction is filtered first, and the filtrate portion is taken out. Then, the filtrate is washed to remove the catalyst and unreacted raw materials.
  • the washing liquid there is no particular limitation, as long as the catalyst and unreacted raw materials can be removed.
  • dilute hydrochloric acid (aqueous solution), saturated sodium bicarbonate aqueous solution and water can be mentioned. The concentration of dilute hydrochloric acid is not particularly limited.
  • dilute hydrochloric acid with a concentration of 5-12% is used. Washing with lotion can be done once or multiple times; in the case of multiple times, a single lotion can be used, or different lotions can be used in sequence. According to the present invention, it is advantageous that the filtrate obtained by filtering the reaction mixture obtained by the esterification reaction is washed successively with dilute hydrochloric acid, a saturated sodium bicarbonate aqueous solution and water.
  • dilute hydrochloric acid a saturated sodium bicarbonate aqueous solution and water.
  • anhydrous sodium sulfate can usually be used for drying. After drying, the remaining organic solvent is removed.
  • the means for removing the organic solvent here is not particularly limited, and the organic solvent can usually be removed by distillation under reduced pressure. After removing the residual organic solvent, a crude product of the compound of formula (I) is obtained. If it is desired to further improve the purity of the compound of formula (I), the compound can be further purified, for example, by recrystallization.
  • the selection of the recrystallization solvent is conventional and not particularly limited. According to the present invention, it is advantageous to use methanol to recrystallize the crude product of the compound of formula (I).
  • the compound of general formula (II) is commercially available or can be prepared by conventional methods in the art.
  • the method further includes the step of reacting the compound of formula (V) with the compound of formula (VI) to obtain the compound of formula (II).
  • a Knoevenagel condensation reaction occurs between the compound of formula (V) and the compound of formula (VI) to obtain the compound of formula (II)
  • a 1 , A 2 , A 3 , A 4 and R 8 in the compound of formula (V) are as defined for the compound of formula (I), and R 9 in the compound of formula (VI) is as defined for the compound of formula (I) Definitions, and R 11 are C 1 -C 12 alkyl groups, preferably C 1 -C 6 alkyl groups.
  • the above-mentioned Knoevenagel condensation reaction is usually carried out in the presence of a catalyst suitable for the condensation reaction.
  • a catalyst suitable for the condensation reaction.
  • a basic catalyst can usually be selected.
  • hexahydropyridine, pyridine, piperidine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide can be used , Tertiary amines (for example, trialkylamines, such as trimethylamine and triethylamine) or any combination thereof.
  • the amount of the catalyst is conventional and can be determined by common sense in the field, or through several routine preliminary experiments.
  • the above-mentioned condensation reaction is usually carried out in a solvent, preferably in an organic solvent.
  • a solvent preferably in an organic solvent.
  • the choice of the type of solvent is not particularly limited, as long as it can dissolve the compounds of formula (V) and formula (VI) and is chemically inert to the condensation reaction, that is, it does not participate in the condensation reaction.
  • the solvent ethanol, methanol, tert-butanol, tetrahydrofuran, benzene, toluene, methylene chloride, and acetone can be mentioned.
  • a single solvent may be used, or a mixture of two or more solvents may be used.
  • the relative amount of the compound of formula (V) and the compound of formula (VI) is not particularly limited. Generally speaking, they are used in approximately equimolar amounts, for example, the molar ratio of the two is 1:1.5-1.5:1, preferably 1:1.2 -1.2:1.
  • the above condensation reaction can be carried out in a very wide temperature range. According to the present invention, it is advantageous that the condensation reaction is carried out at a temperature of 0°C to 150°C, preferably 0°C to 100°C, preferably at the reflux temperature of the solvent.
  • the condensation reaction time is also not particularly limited, and it is usually carried out for 1-24 hours, preferably 1-12 hours.
  • reaction mixture containing the compound of formula (II) is obtained. Therefore, the reaction mixture needs to be post-treated to obtain a purified compound of formula (II).
  • This post-treatment is conventional, for example, the reaction mixture obtained can be filtered first and then recrystallized.
  • the selection of the recrystallization solvent is conventional and not particularly limited. According to the present invention, it is advantageous to use methanol, ethanol or a mixture thereof to recrystallize the crude product of the compound of formula (II).
  • the compound of formula (I) of the present invention has strong absorption in the wavelength range of 300-500nm, especially 350-450nm, especially 365-450nm, so it can be applied to UV-visible LED light curing system.
  • the raw materials for the preparation of the compound of formula (I) of the present invention are all coumarin ketone compounds with less toxicity. Compared with traditional photoinitiators, the harm to the human body and the environment is reduced.
  • the use of the compound of formula (I) of the present invention as a photoinitiator is provided.
  • the compound of formula (I) of the present invention is used as a photoinitiator in a UV-visible LED light curing system, and can effectively initiate a curing reaction.
  • Particularly preferred is the use of the compound of formula (I) of the present invention as a photoinitiator in a photocuring system with a radiation wavelength of 300-500 nm, especially 350-450 nm, especially 365-450 nm.
  • the compound of formula (I) can be used as a photoinitiator or photosensitizer in coatings, inks, microelectronics, printing and other fields.
  • its dosage is conventional, or can be determined by routine preliminary tests.
  • compound 44a is synthesized.
  • the synthetic route is as follows:
  • DSC differential thermal analysis
  • COXE-15 The structure of COXE-15 is as follows:
  • the stability of the compound 1-64 in the acrylate monomer according to the present invention is significantly higher than that of the commercial products OXE-02 and COXE-15, so the compound 1-64 of the present invention has better thermal stability.
  • Ugra (Ugra) printing test strip as a mask to test the photosensitive performance of the photoinitiator.
  • the sections of the Ugra printed test strip are shown in Figure 1.
  • the test strip of Ugra printing plate is divided into 5 control sections. From left to right, they are: continuous density ladder section (1); Yin and Yang micron contour concentric circle section (2); full-step adjustment dot section (3); heavy Shadow control section (4); highlight and dark control section (5).
  • the second section Concentric circles with yin and yang micrometer contours: Concentric circles with 12 yin and yang micrometer contours, 4, 6, 8, 10, 12, 15, 20, 25, 30, 40, 55, 70, used to detect the exposure and development of the PS plate.
  • the third section Full-scale adjustment dot section: It is composed of 10%-100% and a range of 10%, and is arranged in two rows. It is used to measure the transfer of printing, proofing and printing. Measure and produce the curve graphs of film dots and printing, proofing and printing online shops.
  • the fourth section ghost control section: It is composed of thin lines with a line width of 60 lines/cm and an area rate of 60%.
  • the D block of /4 is arranged in small short lines with 90° on both sides, 45° in the middle, and 90° up and down.
  • the fifth segment highlight and dark tone control segment.
  • the fine dot segment is arranged by high light small dots and dark tone deep dots correspondingly, used to finely control the accuracy of exposure and development.
  • the photosensitive composition containing the photoinitiator is coated on the aluminum substrate, and then exposed and developed. The sensitivity is evaluated from the continuous step scale of the obtained image, and the accuracy is evaluated from the micro-line test block area to evaluate the quality of the photosensitive composition formulation .
  • the photoinitiator in the above composition is selected from the coumarin (keto)oxime ester compound represented by formula (I) of the present invention or the photoinitiator known in the prior art (for comparison).
  • Acrylic resin is a resin purchased from Shanghai Fushun International Trade Co., Ltd. under the trade name FS2600K, with a functionality of 2, and a number average molecular weight of 1400.
  • Dipentaerythritol hexaacrylate is a product purchased from Shanghai Fushun International Trade Co., Ltd. under the trade name GM66G0C.
  • Crystal violet dye is a product purchased from Shanghai Sinopharm under the trade name of hexamethyl rose aniline hydrochloride.
  • Aluminum base size 1030mm ⁇ 800mm
  • the photopolymerizable compound undergoes polymerization reaction in the presence of the initiator, and is insoluble in the developer, while the non-exposed area is soluble, so a negative image is obtained.
  • the sensitivity of the photoinitiator was evaluated from the continuous scale of the obtained image.
  • the sensitivity of the initiator system is characterized by the highest number of gray levels retained (ie, polymerized) after development. The higher the number of gray levels, the higher the sensitivity of the test system. The results are shown in Table 4.
  • OXE-01 represents 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime)
  • OXE-02 represents 1-(6-
  • the structural formulas of o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-ethanone)-1-oxime acetate are as follows:
  • the photoinitiator 1-64 of the present invention has higher gray levels at 365nm, 385nm, 395nm and 405nm and visible light 420, 436, 450nm than the commercially available photoinitiator OXE- 01 and OXE-02. That is to say, the coumarin (ketone) oxime ester photoinitiator of the present invention has better photosensitivity at 365nm, 385nm, 395nm and 405nm and visible light wavelengths of 420, 436, 450nm, and is suitable for use at 365nm, 385nm, 395nm. With LED light sources of 405 nm and visible light of 420, 436, 450 nm, the photoinitiator of the present invention has a wider application range.
  • the coumarin (ketone) oxime ester photoinitiator represented by the formula (I) of the present invention has better photosensitivity at 365nm, 385nm, 395nm and 405nm and visible light wavelengths of 420, 436, 450nm, It is superior to the currently commercially available ketoxime ester photoinitiators such as OXE-01 and OXE-02.
  • the compound disclosed in the invention has a simple production process and a high yield, which is very suitable for industrial production.
  • This kind of compound has good compatibility with 365nm, 385nm, 395nm, 405nm and visible light 420, 436, 450nm LED light sources, and can be widely used in UV-visible LED light curing fields such as coatings, inks, microelectronics, printing and other fields Used as a photoinitiator. Such substances have good market prospects.
  • the photoinitiator of the present invention can be used to promote green and environmentally friendly UV-visible LEDs.
  • the light source contributes to the wide application of UV curing industry.

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  • Plural Heterocyclic Compounds (AREA)

Abstract

Disclosed is a coumarin (ketone) oxime ester compound represented by formula (I) comprising the following formula (I-1) structural fragment, wherein X, A 1, A 2, A 3, A 4, R 3, R 4, R 5, R 6, R 8, R 9, R 10 and n are as defined in the specification. The compound has strong ultraviolet absorption in the range of 300 nm to 500 nm, can transfer energy rapidly after absorbing light energy to continuously initiate polymerization, has significant advantages on photosensitivity and pattern integrity, and is very suitable for UV-LED light source radiation curing. In addition, the compound represented by formula (I) also has excellent thermal stability. Also disclosed is a preparation method for the compound represented by formula (I) and a use of the compound. The compound is suitable for use as a photoinitiator in a UV-LED light curing system and has a radiation wavelength suitable for UV-LED light curing. (I-1), (I)

Description

长波长香豆素肟酯类化合物及其制备和应用Long-wavelength coumarin oxime ester compound and its preparation and application 技术领域Technical field
本发明涉及适用于紫外-可见LED曝光光源的香豆素3-(酮)肟酯类化合物，该类化合物可用作光引发剂。本发明还涉及所述香豆素3-(酮)肟酯类化合物的制备及其作为光引发剂的应用。The present invention relates to coumarin 3-(keto)oxime ester compounds suitable for ultraviolet-visible LED exposure light sources, and such compounds can be used as photoinitiators. The invention also relates to the preparation of the coumarin 3-(keto)oxime ester compound and its application as a photoinitiator.
背景技术Background technique
光引发剂又称光敏剂，是一类能在紫外光区(250-400nm)或可见光区(400-600nm)吸收一定波长的能量，产生自由基、阳离子等，从而引发单体聚合交联固化的化合物。在光固化体系中，含量虽低，却是其中的关键组分，对光固化速度起决定作用。它关系到配方体系在光辐照时，低聚物及稀释剂能否迅速交联固化，从而由液态转变为固态。目前，光固化技术已广泛应用在涂料、油墨、微电子、印刷等传统领域，另外还用于制备激光录像及三维元件等新型领域。作为光固化体系的重要组分，光引发剂必须满足不同光固化条件和应用的需要。在自由基光引发剂领域，主要目标是：提高光敏感度，提高表面固化效率(抗氧阻聚)，提高深层固化性能，提高光引发剂在单体及树脂中的溶解性，降低毒性和气味，降低固化后未固化引发剂的迁移性，降低黄变性。Photoinitiator, also known as photosensitizer, is a type of energy that can absorb a certain wavelength of energy in the ultraviolet region (250-400nm) or visible region (400-600nm) to generate free radicals, cations, etc., thereby initiating monomer polymerization, crosslinking and curing compound of. In the light curing system, although the content is low, it is the key component among them, which plays a decisive role in the light curing speed. It is related to whether the oligomer and diluent can be quickly cross-linked and solidified when the formula system is irradiated with light, thereby changing from liquid to solid. At present, light curing technology has been widely used in traditional fields such as coatings, inks, microelectronics, printing, etc. It is also used in the preparation of new fields such as laser video recording and three-dimensional components. As an important component of the light curing system, photoinitiators must meet the needs of different light curing conditions and applications. In the field of free radical photoinitiators, the main goals are: improve light sensitivity, improve surface curing efficiency (anti-oxidation inhibition), improve deep curing performance, improve the solubility of photoinitiators in monomers and resins, and reduce toxicity and odor , Reduce the migration of uncured initiator after curing, reduce yellowing.
肟酯类光引发剂因其具有优异的感光性能成为近年来逐渐受到重视的一类光引发剂，其中巴斯夫产品OXE-01和OXE-02是目前市场上常见的两种肟酯类代表性产品，这两种产品具有较高的光敏度，但是它们的紫外吸收波长偏短(250-350nm)，并不适用于紫外-可见LED光源(发射波长365nm、385nm、395nm、405nm、420nm、430nm、450nm)的需求。国内也有一些关于肟酯类光引发剂的专利，例如CN10277552A披露了一种二苯硫醚酮肟酯类光引发剂及其制备方法，CN102492059A公开了取代的二苯硫醚酮肟酯类光引发剂等等。但是大多数引发剂的紫外吸收波长在250-350nm，无法与日益发展的LED光源匹配，这就大大限制了肟酯类光引发剂的应用。LED点光源、线光源、面光源已开始应用于光固化行业，相对于传统UV固化设备，LED光源有着绝对的优势。Oxime ester photoinitiators have become a class of photoinitiators that have gradually received attention in recent years due to their excellent photosensitivity. Among them, BASF's products OXE-01 and OXE-02 are two representative products of oxime esters that are common on the market. These two products have high photosensitivity, but their ultraviolet absorption wavelength is too short (250-350nm), which is not suitable for ultraviolet-visible LED light source (emission wavelength 365nm, 385nm, 395nm, 405nm, 420nm, 430nm, 450nm). There are also some domestic patents on oxime ester photoinitiators. For example, CN10277552A discloses a diphenyl sulfide ketoxime ester photoinitiator and its preparation method, and CN102492059A discloses a substituted diphenyl sulfide ketoxime ester photoinitiator. Agent and so on. However, most initiators have UV absorption wavelengths of 250-350nm, which cannot match the increasingly developed LED light sources, which greatly limits the application of oxime ester photoinitiators. LED point light sources, line light sources, and surface light sources have begun to be used in the light curing industry. Compared with traditional UV curing equipment, LED light sources have absolute advantages.
(1)使用寿命长。汞灯使用寿命只有800-3000小时，采用UV-LED紫外固化系统的使用寿命达到20000-30000小时。LED方式可以仅在需要紫外线时瞬间点亮，按DUIY＝1/5(准备时间＝照射时间*5＝1)时，LED方式的使用寿命相当于汞灯方式的30-40倍。因此，LED方式减少了更换灯泡的时间，提高了生产效率，同时也非常节能。而传统汞灯方式固化设备在工作时，由于汞灯启动慢、开闭影响灯泡寿命，必须一直点亮，不仅造成不必要的电力消耗，而且缩短了汞灯工作寿命。(1) Long service life. The service life of the mercury lamp is only 800-3000 hours, and the service life of the UV-LED ultraviolet curing system can reach 20,000-30000 hours. The LED method can be lit instantaneously only when ultraviolet light is needed. When DUIY=1/5 (preparation time=irradiation time*5=1), the service life of the LED method is equivalent to 30-40 times that of the mercury lamp method. Therefore, the LED method reduces the time to replace the bulb, improves production efficiency, and is also very energy-saving. When the traditional mercury lamp curing equipment is working, because the mercury lamp starts slowly and the opening and closing affects the life of the bulb, it must be lit all the time, which not only causes unnecessary power consumption, but also shortens the working life of the mercury lamp.
(2)无热辐射。高功率发光二极管没有红外线发出。被照射的产品表面温升仅在5℃以下，而传统汞灯方式的紫外线固化机一般都会使被照射的产品表面温度升高60-90℃，这会使产品的定位发生位移，造成产品不良。(2) No heat radiation. High-power LEDs do not emit infrared light. The surface temperature rise of the irradiated product is only below 5℃, while the traditional mercury lamp method of ultraviolet curing machine generally increases the surface temperature of the irradiated product by 60-90℃, which will cause the positioning of the product to shift and cause product failure .
(3)环保无污染。传统的汞灯方式固化机采用汞灯发光方式，灯泡内有水银，废品处理、运输非常麻烦，处理不当会对环境产生严重污染。而LED式固化机采用半导体放光，没有对 环境造成污染的因素。因此使用LED式固化机更加环保。(3) Environmental protection and no pollution. The traditional mercury lamp curing machine uses a mercury lamp to emit light. There is mercury in the bulb, which makes the waste disposal and transportation very troublesome, and improper handling can cause serious pollution to the environment. The LED curing machine uses semiconductors to emit light and has no environmental pollution factors. Therefore, the use of LED curing machine is more environmentally friendly.
(4)超强照度。采用大功率LED芯片和特殊的光学设计，使紫外光达到高精度、高强度照射；紫外光输出可达到8600mW/m 2的照射强度。采用最新的光学技术和制造工艺，实现了比传统汞灯照射方式更加优化的高强度输出与均匀性，几乎是传统汞灯方式照射光度的2倍，使UV粘合剂更快固化，缩短了生产时间，大幅度提高了生产效率。传统的汞灯方式点光源固化机在增加照射通道时，通道的增加会造成单个照射通道的输出能量减少。而采用LED式的照射，各个照射头独立发光，照射能量不受通道增加的影响，始终保持在最大值。因其超强集中的光照度，与汞灯相比，UV-LED缩短了作业的照射时间，提高了生产效率。 (4) Super illuminance. High-power LED chips and special optical design are used to achieve high-precision and high-intensity irradiation of ultraviolet light; ultraviolet light output can reach 8600mW/m 2 irradiation intensity. Using the latest optical technology and manufacturing process, it has achieved a higher intensity output and uniformity that is more optimized than the traditional mercury lamp irradiation method, which is almost twice the luminosity of the traditional mercury lamp method, which makes the UV adhesive cure faster and shorten Production time has greatly improved production efficiency. When the traditional mercury lamp type point light source curing machine increases the irradiation channel, the increase of the channel will cause the output energy of a single irradiation channel to decrease. With LED-style illumination, each illuminating head emits light independently, and the illuminating energy is not affected by the increase in the channel, and always remains at the maximum. Because of its super concentrated illuminance, compared with mercury lamps, UV-LED shortens the irradiation time of the operation and improves the production efficiency.
(5)能耗低。UV-LED方式较汞灯方式有效发光效率高10倍以上。同时，汞灯方式无论是否进行有效照射，汞灯都需要连续点灯工作，电力一直处于消耗状态。而UV-LED方式只在照射时才消耗电力，而在待机时电力消耗几乎为零。可以做一个简单的计算，每台点光源固化机节省的电能：270(瓦特)*8(小时)*365(天)＝800(千瓦时)由此可见，每台每年仅耗电费用就可以省千元。不仅如此，通过节省电能，每台每年可间接减少二氧化碳的排放量1.4吨，相当于一辆轿车一年的排气量。(5) Low energy consumption. The effective luminous efficiency of UV-LED method is more than 10 times higher than that of mercury lamp method. At the same time, no matter whether the mercury lamp is irradiated effectively or not, the mercury lamp needs to be continuously lit and the power is always consumed. The UV-LED method consumes power only during irradiation, and almost zero power consumption during standby. A simple calculation can be made. The energy saved by each point light source curing machine: 270 (watts) * 8 (hours) * 365 (days) = 800 (kilowatt hours). It can be seen that only the cost of electricity consumption per year is enough Thousands of savings. Not only that, by saving electric energy, each car can indirectly reduce carbon dioxide emissions by 1.4 tons per year, which is equivalent to the annual displacement of a car.
可见光相对于紫外光固化，其固化深度更深，温度更低，在条件允许的情况下，可见光固化方式为优选方式。UVLED面光源和UVLED线光源都包含了可见光部分的UV波谱)，可见光固化会有更少的能量损耗。可见光固化的主要优势是它可以穿过阻挡紫外光的基材固化胶水并且可以选择半透明的有颜色的材料。安全性的提高是可见光固化设备的另一个重要优势。输出的是可见光，紫外光相关的遮挡和保护都可以最小化。因此，开发适用于紫外-可见LED光源的光引发剂会极大地满足紫外-可见LED曝光光源在光固化行业广泛应用的需求。Compared with UV curing, visible light has a deeper curing depth and lower temperature. When conditions permit, visible light curing is the preferred method. UVLED surface light source and UVLED line light source both include the visible part of the UV spectrum), visible light curing will have less energy loss. The main advantage of visible light curing is that it can pass through the UV-blocking substrate to cure the glue and can choose translucent colored materials. Improved safety is another important advantage of visible light curing equipment. The output is visible light, and UV-related shading and protection can be minimized. Therefore, the development of photoinitiators suitable for UV-visible LED light sources will greatly meet the wide application needs of UV-visible LED exposure light sources in the photocuring industry.
CN1889960A披露了香豆素酮肟酯类化合物可用于药物组合物或者化妆品组合物中，用以预防和治疗疾病，包括免疫性疾病、慢性炎症、神经疾病和皮肤病、肿瘤疾病、特定病毒(特别是SARS)等。从这个意义上说，此类化合物是安全无毒的。CN1889960A discloses that coumarin ketoxime ester compounds can be used in pharmaceutical or cosmetic compositions to prevent and treat diseases, including immune diseases, chronic inflammation, neurological and skin diseases, tumor diseases, specific viruses (especially Is SARS) and so on. In this sense, such compounds are safe and non-toxic.
因此，仍旧需要一种吸收波长适合UV-可见LED光源并且热稳定性良好的光引发剂。Therefore, there is still a need for a photoinitiator whose absorption wavelength is suitable for UV-visible LED light sources and has good thermal stability.
发明内容Summary of the invention
鉴于现有技术中存在的问题，本发明的发明人在适于紫外-可见LED光源(发射波长300-500nm、尤其350-450nm)辐射固化的光引发剂方面进行了广泛而又深入的研究，以期发现一种能够替代OXE-01和OXE-02以更适合UV-可见LED光源固化并且具有良好热稳定性的光引发剂。本发明人发现，在香豆素(酮)肟酯化合物的苯环上稠合上一个苯并五元环得到的改性香豆素(酮)肟酯化合物在300-500nm、尤其350-450nm范围内具有很强的紫外吸收，并且具有很好的热稳定性，从而适合用作紫外-可见LED光源辐射固化的光引发剂。本发明目的正是基于前述发现得以实现。In view of the problems in the prior art, the inventors of the present invention have conducted extensive and in-depth research on photoinitiators suitable for radiation curing of ultraviolet-visible LED light sources (emission wavelengths of 300-500nm, especially 350-450nm). In order to find a photoinitiator that can replace OXE-01 and OXE-02 to be more suitable for UV-visible LED light source curing and has good thermal stability. The present inventors found that the modified coumarin (ketone) oxime ester compound obtained by condensing a benzo five-membered ring on the benzene ring of the coumarin (ketone) oxime ester compound has a range of 300-500nm, especially 350-450nm It has strong ultraviolet absorption in the range and has good thermal stability, so it is suitable for use as a photoinitiator for radiation curing of ultraviolet-visible LED light sources. The purpose of the present invention is achieved based on the foregoing findings.
因此，本发明的一个目的是提供一种香豆素(酮)肟酯化合物，该类化合物的吸收波长不仅适用于紫外-可见LED光源辐射固化，而且还具有很好的热稳定性。Therefore, an object of the present invention is to provide a coumarin (ketone) oxime ester compound whose absorption wavelength is not only suitable for UV-visible LED light source radiation curing, but also has good thermal stability.
本发明的另一目的是提供制备本发明香豆素(酮)肟酯化合物的方法。Another object of the present invention is to provide a method for preparing the coumarin (keto)oxime ester compound of the present invention.
本发明的再一目的是提供本发明香豆素(酮)肟酯化合物作为光引发剂的用途。Another object of the present invention is to provide the use of the coumarin (keto)oxime ester compound of the present invention as a photoinitiator.
实现本发明上述目的的技术方案可以概括如下:The technical solutions for achieving the above-mentioned objects of the present invention can be summarized as follows:
1.一种包含下式(I-1)结构部分的式(I)香豆素(酮)肟酯化合物：1. A coumarin (keto)oxime ester compound of formula (I) comprising the following formula (I-1):
Figure PCTCN2019092708-appb-000001
Figure PCTCN2019092708-appb-000001
其中：among them:
X为O、S、NR 1或CR 2aR 2b，其中R 1、R 2a和R 2b各自独立地为H、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了H以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基； X is O, S, NR 1 or CR 2a R 2b , wherein R 1 , R 2a and R 2b are each independently H, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (sulfur ) Group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl group Or a C 6 -C 18 aryloxy (thio) group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group;
R 3、R 4、R 5、R 6相互独立地表示氢、卤素、硝基、氰基、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了氢、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基； R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl, C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl or C 6- A C 18 aryloxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano Group, C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group;
*和**是式(I-1)结构部分与式(I)化合物中的A 1和A 2、A 2和A 3或者A 3和A 4的连接位点； * And ** are the connection points between the structural part of formula (I-1) and A 1 and A 2 , A 2 and A 3 or A 3 and A 4 in the compound of formula (I);
A 1、A 2、A 3、A 4中连接式(I-1)结构部分的两个为碳原子，其余两个相同或不同，并且彼此独立地为CH或者CR 7，其中R 7为H、卤素、C 1-C 6烷基或C 1-C 6烷氧(硫)基，其中前述C 1-C 6烷基和C 1-C 6烷氧(硫)基可以包含一个或多个相同或不同的卤素取代基； Two of A 1 , A 2 , A 3 , and A 4 connected to the structural part of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , wherein R 7 is H , Halogen, C 1 -C 6 alkyl group or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group may contain one or more The same or different halogen substituents;
R 8是H、卤素、C 1-C 6烷基或C 1-C 6烷氧(硫)基，其中前述C 1-C 6烷基和前述C 1-C 6烷氧(硫)基可以包含一个或多个相同或不同的卤素取代基； R 8 is H, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and the aforementioned C 1 -C 6 alkoxy (thio) group may Contain one or more identical or different halogen substituents;
R 9是氢、卤素、硝基、氰基、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了H、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基； R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl, C 1 -C 8 alkyl, C 1 -C 8 Alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 Alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl group or C 6 -C 18 aryloxy (thio) group, wherein the foregoing except Each group other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (sulfur) group;
R 10是C 1-C 20烷基或C 6-C 18芳基，其中C 1-C 20烷基和C 6-C 18芳基可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基；以及 R 10 is a C 1 -C 20 alkyl group or a C 6 -C 18 aryl group, wherein the C 1 -C 20 alkyl group and the C 6 -C 18 aryl group may contain one or more substituents independently selected from the following group : Halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group; and
n为0或1。n is 0 or 1.
2.根据第1项的化合物，其中2. The compound according to item 1, wherein
R 1、R 2a和R 2b各自独立地为H、C 1-C 10烷基、C 3-C 8环烷基、C 3-C 8环烷基C 1-C 6烷基、C 1-C 6烷基C 3-C 8环烷基、C 1-C 6烷氧(硫)基、C 3-C 8环烷氧(硫)基、C 3-C 8环烷基C 1-C 6烷氧(硫)基、C 1-C 6烷基C 3-C 8环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了H以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6 烷基和C 1-C 6烷氧(硫)基，优选的是，R 1、R 2a和R 2b各自独立地为H、C 1-C 8烷基、C 5-C 6环烷基、C 5-C 6环烷基C 1-C 4烷基、C 1-C 4烷基C 5-C 6环烷基、C 1-C 4烷氧(硫)基、C 5-C 6环烷氧(硫)基、C 3-C 6环烷基C 1-C 4烷氧(硫)基、C 1-C 4烷基C 5-C 6环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了H以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基；和/或 R 1 , R 2a and R 2b are each independently H, C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkyl, C 1- C 6 alkyl C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 Alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 8 cycloalkoxy (thio) group, C 6 -C 10 aryl group or C 6 -C 10 aryloxy (thio) group, wherein the foregoing Each group other than H may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (sulfur ) Group, preferably, R 1 , R 2a and R 2b are each independently H, C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl C 1 -C 4 alkyl group, C 1 -C 4 alkyl group, C 5 -C 6 cycloalkyl group, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy (thio) group, C 3 -C 6 Cycloalkyl C 1 -C 4 alkoxy (thio) group, C 1 -C 4 alkyl C 5 -C 6 cycloalkoxy (thio) group, C 6 -C 10 aryl or C 6 -C 10 aryloxy (Thio) group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) group; and/or
R 3、R 4、R 5、R 6相互独立地表示氢、卤素、硝基、氰基、C 1-C 6烷基、C 3-C 8环烷基、C 3-C 8环烷基C 1-C 6烷基、C 1-C 6烷基C 3-C 8环烷基、C 1-C 6烷氧(硫)基、C 3-C 8环烷氧(硫)基、C 3-C 8环烷基C 1-C 6烷氧(硫)基、C 1-C 6烷基C 3-C 10环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了氢、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基，优选的是，R 3、R 4、R 5、R 6相互独立地表示氢、卤素、硝基、氰基、C 1-C 4烷基、C 5-C 6环烷基、C 5-C 6环烷基C 1-C 4烷基、C 1-C 4烷基C 5-C 6环烷基、C 1-C 4烷氧(硫)基、C 5-C 6环烷氧(硫)基、C 5-C 6环烷基C 1-C 4烷氧(硫)基、C 1-C 4烷基C 5-C 6环烷氧(硫)基、苯基或苯氧(硫)基，其中前述除了氢、卤素、硝基、氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：氟、氯、溴、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基；和/或 R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl C 1 -C 6 alkyl, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 10 aryl or C 6- C 10 aryloxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano Group, C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group, preferably, R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano , C 1 -C 4 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkyl, C 1 -C 4 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy (thio) group, C 5 -C 6 cycloalkyl C 1 -C 4 alkoxy (thio) group, C 1 -C 4 Alkyl C 5 -C 6 cycloalkoxy (thio) group, phenyl or phenoxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano group may contain one or more independently Substituents selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (thio) groups; and/or
R 7为H、氟、氯、溴、C 1-C 4烷基或C 1-C 4烷氧(硫)基，其中前述C 1-C 4烷基和C 1-C 4烷氧(硫)基可以包含一个或多个相同或不同的选自氟、氯、溴的取代基；和/或 R 7 is H, fluorine, chlorine, bromine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy (sulfur) group, wherein the aforementioned C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) ) The group may contain one or more identical or different substituents selected from fluorine, chlorine and bromine; and/or
R 8是H、氟、氯、溴、C 1-C 4烷基或C 1-C 4烷氧(硫)基，其中前述C 1-C 4烷基和C 1-C 4烷氧(硫)基可以包含一个或多个相同或不同的选自氟、氯、溴的取代基；和/或 R 8 is H, fluorine, chlorine, bromine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy (sulfur) group, wherein the aforementioned C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) ) The group may contain one or more identical or different substituents selected from fluorine, chlorine and bromine; and/or
R 9是氢、卤素、硝基、氰基、C 1-C 8烷基、C 3-C 8环烷基、C 3-C 8环烷基C 1-C 6烷基、C 1-C 6烷基C 3-C 8环烷基、C 1-C 6烷氧(硫)基、C 3-C 8环烷氧(硫)基、C 3-C 8环烷基C 1-C 6烷氧(硫)基、C 1-C 6烷基C 3-C 8环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了H、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基，优选的是，R 9是氢、氟、氯、溴、硝基、氰基、C 1-C 8烷基、C 5-C 6环烷基、C 5-C 6环烷基C 1-C 4烷基、C 1-C 4烷基C 5-C 6环烷基、C 1-C 4烷氧(硫)基、C 5-C 6环烷氧(硫)基、C 5-C 6环烷基C 1-C 4烷氧(硫)基、C 1-C 4烷基C 5-C 6环烷氧(硫)基、苯基或苯氧(硫)基，其中前述除了氢、氟、氯、溴、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：氟、氯、溴、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基；和/或 R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkyl, C 1 -C 6 alkyl C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 Alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 8 cycloalkoxy (thio) group, C 6 -C 10 aryl group or C 6 -C 10 aryloxy (thio) group, wherein the foregoing except Each group other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group, preferably, R 9 is hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl C 1 -C 4 alkyl, C 1 -C 4 alkyl C 5 -C 6 cycloalkyl, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy (Thio) group, C 5 -C 6 cycloalkyl C 1 -C 4 alkoxy (thio) group, C 1 -C 4 alkyl C 5 -C 6 cycloalkoxy (thio) group, phenyl or phenoxy (Sulfur) group, wherein each of the aforementioned groups other than hydrogen, fluorine, chlorine, bromine, nitro and cyano may contain one or more substituents independently selected from the following group: fluorine, chlorine, bromine, nitro , Amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (thio) group; and/or
R 10是C 1-C 6烷基或C 6-C 10芳基，其中C 1-C 6烷基和C 6-C 10芳基可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基，优选的是，R 10是C 1-C 4烷基或苯基，其中C 1-C 4烷基和苯基可以包含一个或多个独立地选自下组的取代基：氟、氯、溴、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基。 R 10 is a C 1 -C 6 alkyl group or a C 6 -C 10 aryl group, wherein the C 1 -C 6 alkyl group and the C 6 -C 10 aryl group may contain one or more substituents independently selected from the following group : Halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group, preferably, R 10 is C 1 -C 4 alkyl or phenyl, wherein The C 1 -C 4 alkyl group and the phenyl group may contain one or more substituents independently selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) group.
3.根据第1项的化合物，其中3. The compound according to item 1, wherein
X为O、S、NR 1或CR 2aR 2b，其中R 1为C 1-C 8烷基、苯基或萘基，其中所述苯基或萘基可以包含一个或多个相同或不同的C 1-C 4烷基取代基；以及R 2a和R 2b相同或不同，且各自独立地为H、C 1-C 6烷基、C 5-C 6环烷基C 1-C 4烷基或C 1-C 4烷氧基C 1-C 4烷基； X is O, S, NR 1 or CR 2a R 2b , wherein R 1 is C 1 -C 8 alkyl, phenyl or naphthyl, wherein said phenyl or naphthyl may contain one or more of the same or different C 1 -C 4 alkyl substituent; and R 2a and R 2b are the same or different, and are each independently H, C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkyl Or C 1 -C 4 alkoxy C 1 -C 4 alkyl;
R 3、R 4、R 5、R 6相互独立地表示氢、硝基、C 1-C 4烷基、C 1-C 4烷氧(硫)基或苯基； R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy (thio) or phenyl;
A 1、A 2、A 3、A 4中连接式(I-1)结构部分的两个为碳原子，其余两个相同或不同，并且彼此独立地为CH或者CR 7，其中R 7H或C 1-C 4烷基； Two of A 1 , A 2 , A 3 , and A 4 connecting the structural parts of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , wherein R 7 H or C 1 -C 4 alkyl;
R 8是H或C 1-C 4烷基； R 8 is H or C 1 -C 4 alkyl;
R 9是氰基、C 1-C 7烷基、卤代C 1-C 6烷基或C 5-C 6环烷基C 1-C 4烷基；以及 R 9 is cyano, C 1 -C 7 alkyl, halo C 1 -C 6 alkyl or C 5 -C 6 cycloalkyl C 1 -C 4 alkyl; and
R 10是C 1-C 4烷基或苯基。 R 10 is C 1 -C 4 alkyl or phenyl.
4.根据第1项的化合物，其中该化合物选自化合物1-64。4. The compound according to item 1, wherein the compound is selected from compounds 1-64.
5.一种制备如第1-4项中任一项所要求的化合物的方法，包括以下步骤：5. A method for preparing the compound as claimed in any one of items 1-4, comprising the following steps:
(1)肟化反应：当n为0时，使式(II)化合物与羟胺、盐酸羟胺或其任意组合进行肟化反应，得到式(IIIa)化合物(1) The oximation reaction: when n is 0, the compound of formula (II) is subjected to oximation reaction with hydroxylamine, hydroxylamine hydrochloride or any combination thereof to obtain the compound of formula (IIIa)
Figure PCTCN2019092708-appb-000002
Figure PCTCN2019092708-appb-000002
当n为1时，使式(II)化合物与亚硝酸、亚硝酸盐、亚硝酸烷基酯或其任意组合进行肟化反应，得到式(IIIb)化合物:When n is 1, the compound of formula (II) is subjected to oximation reaction with nitrous acid, nitrite, alkyl nitrite or any combination thereof to obtain a compound of formula (IIIb):
Figure PCTCN2019092708-appb-000003
Figure PCTCN2019092708-appb-000003
其中，式(II)、(IIIa)和(IIIb)中的A 1、A 2、A 3、A 4、R 8和R 9如第1-4项中任一项所定义；以及 Wherein, A 1 , A 2 , A 3 , A 4 , R 8 and R 9 in formulas (II), (IIIa) and (IIIb) are as defined in any one of items 1-4; and
(2)将式(IIIa)或(IIIb)化合物酯化，得到式(I)化合物。(2) Esterify the compound of formula (IIIa) or (IIIb) to obtain the compound of formula (I).
6.根据第5项的方法，其中6. The method according to item 5, where
当n为0时：When n is 0:
肟化反应在乙酸钠、吡啶、哌啶、三乙胺、四甲基氢氧化铵或其混合物作为催化剂存在下进行；和/或，肟化反应的温度为60-120℃；和/或，式(II)化合物与选自羟胺和/或盐酸羟胺的化合物的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1；或The oximation reaction is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof as a catalyst; and/or, the temperature of the oximation reaction is 60-120°C; and/or, The molar ratio of the compound of formula (II) to the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is 1:1.5-1.5:1, preferably 1:1.2-1.2:1; or
当n为1时，When n is 1,
肟化反应在浓盐酸存在下进行；和/或，肟化反应的温度为-30至20℃，优选5-20℃；和/或，式(II)化合物与选自亚硝酸、亚硝酸盐和/或亚硝酸烷基酯的化合物的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。The oximation reaction is carried out in the presence of concentrated hydrochloric acid; and/or the temperature of the oximation reaction is -30 to 20°C, preferably 5-20°C; and/or, the compound of formula (II) is selected from nitrous acid and nitrite And/or the molar ratio of the alkyl nitrite compound is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
7.根据第5或6项的方法，其中7. The method according to item 5 or 6, where
亚硝酸烷基酯为亚硝酸C 1-C 6烷基酯，例如亚硝酸甲酯、亚硝酸乙酯、亚硝酸异丙酯、亚硝酸丁酯、亚硝酸异戊酯；和/或， The alkyl nitrite is a C 1 -C 6 alkyl nitrite, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite; and/or,
步骤(2)的酯化采用选自下式(IVa)、(IVb)和(IVc)化合物的酯化试剂进行：The esterification of step (2) is carried out with an esterification reagent selected from compounds of the following formulas (IVa), (IVb) and (IVc):
Figure PCTCN2019092708-appb-000004
Figure PCTCN2019092708-appb-000004
其中X为卤素，尤其是氯，和R 7如第项1-4中任一项所定义。 Where X is halogen, especially chlorine, and R 7 is as defined in any one of items 1-4.
8.根据第5-7项中任一项的方法，其中酯化反应在选自下组的一种或多种催化剂存在下进行：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。8. The method according to any one of items 5-7, wherein the esterification reaction is carried out in the presence of one or more catalysts selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, Pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines, such as trialkylamines, Such as trimethylamine and triethylamine.
9.根据第7或8项的方法，其中式(IIIa)或式(IIIb)化合物与选自(IVa)、(IVb)和(IVc)化合物的酯化试剂的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。9. The method according to item 7 or 8, wherein the molar ratio of the compound of formula (IIIa) or formula (IIIb) to the esterification agent selected from the group consisting of (IVa), (IVb) and (IVc) compounds is 1:1.5-1.5 :1, preferably 1:1.2-1.2:1.
10.根据第5-9项中任一项的方法，还包括：使式(V)化合物与式(VI)化合物进行诺文葛尓缩合反应，得到式(II)化合物，10. The method according to any one of items 5-9, further comprising: subjecting the compound of formula (V) to the compound of formula (VI) to undergo a Novembert condensation reaction to obtain a compound of formula (II),
Figure PCTCN2019092708-appb-000005
Figure PCTCN2019092708-appb-000005
其中式(V)化合物中的A 1、A 2、A 3、A 4和R 8如第1-4项中任一项所定义，以及式(VI)化合物中的R 9如第1-4项中任一项所定义，和R 11为C 1-C 12烷基，优选C 1-C 6烷基。 Wherein A 1 , A 2 , A 3 , A 4 and R 8 in the compound of formula (V) are as defined in any one of items 1-4, and R 9 in the compound of formula (VI) is as defined in items 1-4 As defined in any one of the terms, and R 11 is a C 1 -C 12 alkyl group, preferably a C 1 -C 6 alkyl group.
11.根据第10项的方法，其中11. The method according to item 10, where
诺文葛尓缩合反应在六氢吡啶、吡啶、哌啶、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙、四甲基氢氧化铵、叔胺(例如三烷基胺，如三甲基胺和三乙胺)或其任意组合存在下进行；和/或，Condensation reaction of Novengrass in hexahydropyridine, pyridine, piperidine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethyl Ammonium hydroxide, tertiary amine (for example, trialkylamine, such as trimethylamine and triethylamine) or any combination thereof; and/or,
诺文葛尓缩合反应的温度为0-150℃，优选0-100℃；和/或The temperature of the Novenge condensation reaction is 0-150°C, preferably 0-100°C; and/or
式(V)化合物和式(VI)化合物的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。The molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
12.如第1-4项中任一项所要求的式(I)化合物作为光引发剂的用途，尤其是在UV-LED光固化体系中作为光引发剂的用途，特别是在辐射波长为300-500nm、特别是350-450nm、尤其是在365-450nm的光固化体系中作为光引发剂的用途。12. The use of the compound of formula (I) as required by any one of items 1 to 4 as a photoinitiator, especially the use as a photoinitiator in a UV-LED light curing system, especially at the radiation wavelength The use of 300-500nm, especially 350-450nm, especially 365-450nm light curing system as a photoinitiator.
附图说明Description of the drawings
图1是乌格拉(Ugra)晒版测试条的示意图，其中Figure 1 is a schematic diagram of Ugra printing test strips, where
1——连续密度梯尺段，1——Continuous density ladder section,
2——阴阳微米等线同心圆线圈段，2——Yin-Yang micron contour concentric circle segment,
3——全阶调网点段，3——Full-level adjustment network point segment,
4——重影控制段，和4-Ghost control segment, and
5——高光、暗调控制段。5——High light and dark tone control section.
具体实施方式Detailed ways
根据本发明的第一个方面，提供了一种包含下式(I-1)结构部分的式(I)香豆素(酮)肟酯化合物：According to the first aspect of the present invention, there is provided a coumarin (keto)oxime ester compound of formula (I) comprising the following formula (I-1):
Figure PCTCN2019092708-appb-000006
Figure PCTCN2019092708-appb-000006
其中：among them:
X为O、S、NR 1或CR 2aR 2b，其中R 1、R 2a和R 2b各自独立地为H、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了H以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基； X is O, S, NR 1 or CR 2a R 2b , wherein R 1 , R 2a and R 2b are each independently H, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (sulfur ) Group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl group Or a C 6 -C 18 aryloxy (thio) group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group;
R 3、R 4、R 5、R 6相互独立地表示氢、卤素、硝基、氰基、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了氢、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基； R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl, C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl or C 6- A C 18 aryloxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano Group, C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group;
*和**是式(I-1)结构部分与式(I)化合物中的A 1和A 2、A 2和A 3或者A 3和A 4的连接位点； * And ** are the connection points between the structural part of formula (I-1) and A 1 and A 2 , A 2 and A 3 or A 3 and A 4 in the compound of formula (I);
A 1、A 2、A 3、A 4中连接式(I-1)结构部分的两个为碳原子，其余两个相同或不同，并且彼此独立地为CH或者CR 7，其中R 7为H、卤素、C 1-C 6烷基或C 1-C 6烷氧(硫)基，其中前述C 1-C 6烷基和C 1-C 6烷氧(硫)基可以包含一个或多个相同或不同的卤素取代基； Two of A 1 , A 2 , A 3 , and A 4 connected to the structural part of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , wherein R 7 is H , Halogen, C 1 -C 6 alkyl group or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group may contain one or more The same or different halogen substituents;
R 8是H、卤素、C 1-C 6烷基或C 1-C 6烷氧(硫)基，其中前述C 1-C 6烷基和前述C 1-C 6烷氧(硫)基可以包含一个或多个相同或不同的卤素取代基； R 8 is H, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and the aforementioned C 1 -C 6 alkoxy (thio) group may Contain one or more identical or different halogen substituents;
R 9是氢、卤素、硝基、氰基、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了H、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基； R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl, C 1 -C 8 alkyl, C 1 -C 8 Alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 Alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl group or C 6 -C 18 aryloxy (thio) group, wherein the foregoing except Each group other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (sulfur) group;
R 10是C 1-C 20烷基或C 6-C 18芳基，其中C 1-C 20烷基和C 6-C 18芳基可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基；以及 R 10 is a C 1 -C 20 alkyl group or a C 6 -C 18 aryl group, wherein the C 1 -C 20 alkyl group and the C 6 -C 18 aryl group may contain one or more substituents independently selected from the following group : Halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group; and
n为0或1。n is 0 or 1.
式(I)化合物中既包含香豆素(酮)肟酯类结构部分，又包含与之稠合的苯并五元环结构。如此结构使得该化合物在300-500nm范围内、优选350-450nm范围内具有很强的紫外吸收，吸收光能后能够迅速发生能量转移，持续引发聚合，在感光性及图案完整性方面具有明显优势，非常适合于紫外-可见LED光源且其安全无毒可用于食品包装等领域。此外，式(I)化合物还具有很好的热稳定性。The compound of formula (I) contains not only the coumarin (ketone) oxime ester structural part, but also the benzo five-membered ring structure fused with it. Such a structure makes the compound have strong ultraviolet absorption in the range of 300-500nm, preferably 350-450nm. After absorbing light energy, it can quickly transfer energy, continue to initiate polymerization, and has obvious advantages in photosensitivity and pattern integrity. , It is very suitable for UV-visible LED light source and its safe and non-toxic can be used in food packaging and other fields. In addition, the compound of formula (I) also has good thermal stability.
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 "in each case indicates 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 preferable that the halogen includes F, Cl or a combination thereof.
本文所用的术语“C n-C m烷基”是指具有n-m个，例如1-20个，优选1-12个，更优选1-8个，特别优选1-6个，尤其优选1-4个碳原子的支化或未支化饱和烃基，例如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、庚基、辛基、2-乙基己基、壬基、癸基、十一烷基、十二烷基及其异构体。 The term "C n -C m alkyl group" as used herein means having nm number, for example 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, especially preferably 1-4 Branched or unbranched saturated hydrocarbon groups with three carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl -1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and isopropyl Construct.
本文所用术语“C 3-C m环烷基”是指具有3-m个，例如3-20个，优选3-8个，更优选5-6个环碳原子的饱和脂环族单环基团，例如环丙基、环丁基、环戊基、环己基、环庚基、环辛基和环癸基。 The term "C 3 -C m cycloalkyl" as used herein refers to a saturated alicyclic monocyclic group having 3 to m, such as 3 to 20, preferably 3 to 8, and more preferably 5 to 6 carbon atoms. Groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
术语“C 3-C m环烷基C n-C m烷基”表示被C 3-C m环烷基取代的C n-C m烷基，此时两个m可相同或不同，其中C n-C m烷基和C 3-C m环烷基适用本文所定义。C 3-C m环烷基C n-C m烷基可以是C 3-C 10环烷基C 1-C 8烷基，优选是C 3-C 6环烷基C 1-C 6烷基，更优选是C 3-C 6环烷基C 1-C 4烷基，例如环丙基甲基、环丙基乙基、环丙基丙基、环丙基丁基、环丁基甲基、环丁基乙基、环丁基丙基、环丁基丁基、环戊基甲基、环戊基乙基、环戊基丙基、环戊基丁基、环己基甲基、环己基乙基、环己基丙基、环己基丁基等。 The term "C 3 -C m cycloalkyl C n -C m alkyl" means C n -C m alkyl substituted by C 3 -C m cycloalkyl, in which case two m may be the same or different, where C The n -C m alkyl group and the C 3 -C m cycloalkyl group apply as defined herein. C 3 -C m cycloalkyl C n -C m alkyl may be C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, preferably C 3 -C 6 cycloalkyl C 1 -C 6 alkyl , More preferably C 3 -C 6 cycloalkyl C 1 -C 4 alkyl, such as cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclo Butylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl , Cyclohexylpropyl, cyclohexylbutyl, etc.
术语“C n-C m烷基C 3-C m环烷基”表示被C n-C m烷基取代的C 3-C m环烷基，此时两个m可相同或不同，其中C n-C m烷基和C 3-C m环烷基适用本文所定义。C n-C m烷基C 3-C m环烷基可以是C 1-C 8烷基C 3-C 10环烷基，优选是C 1-C 6烷基C 3-C 6环烷基，更优选是C 1-C 4烷基C 3-C 6环烷基，例如甲基环丙基、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 n -C m alkyl C 3 -C m cycloalkyl" means a C 3 -C m cycloalkyl group substituted by C n -C m alkyl. In this case, two m may be the same or different, where C The n -C m alkyl group and the C 3 -C m cycloalkyl group apply as defined herein. C n -C m alkyl C 3 -C m cycloalkyl can be C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, preferably C 1 -C 6 alkyl C 3 -C 6 cycloalkyl , More preferably C 1 -C 4 alkyl C 3 -C 6 cycloalkyl, such as methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethyl Cyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propyl ring Hexyl, 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、双环或更多环芳族烃基。作为C 6-C m芳基的实例，可提及苯基、甲苯基、乙苯基、丙苯基、丁苯基、二甲苯基、甲基·乙基苯基、二乙基苯基、甲基·丙基苯基和萘基等；优选苯基或萘基，尤其是苯基。 The term "C 6 -C m aryl group" as used herein refers to a monocyclic, bicyclic or multicyclic aromatic hydrocarbon group containing 6 to m carbon atoms, such as 6 to 18, preferably 6 to 10 carbon atoms. As examples of C 6 -C m aryl groups, mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methyl ethyl phenyl, diethyl phenyl, Methyl·propylphenyl, naphthyl, etc.; preferably phenyl or naphthyl, especially phenyl.
单独或联合出现的术语“C n-C m烷氧(硫)基”包括“C n-C m烷氧基”和“C n-C m烷硫基”，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或一个硫原子作为连接基团的C n-C m烷基，例如C 1-C 20烷氧(硫)基，优选C 1-C 12烷氧(硫)基，更优选C 1-C 8烷氧(硫)基，特别优选C 1-C 6烷氧(硫)基，尤其优选C 1-C 4烷氧(硫)基。C 1-C 8烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基、庚氧基、辛氧基、异辛氧基及其异构体。C 1-C 8烷硫基可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基、2-丁硫基、叔丁硫基、戊硫基、异戊硫基、己硫基、庚硫基、辛硫基、异辛硫基及其异构体。 The term "C n -C m alkoxy (thio) group" when used alone or in combination includes "C n -C m alkoxy group" and "C n -C m alkylthio group", and refers to the C n -C m corresponding open-chain alkyl group C n -C m alkane any carbon atom bonded to an oxygen atom or a sulfur atom as a C n -C m alkyl linking group, e.g. C 1 -C 20 alkoxy (thio ) Group, preferably C 1 -C 12 alkoxy (thio) group, more preferably C 1 -C 8 alkoxy (thio) group, particularly preferably C 1 -C 6 alkoxy (thio) group, particularly preferably C 1 -C 4 Alkoxy (thio) group. C 1 -C 8 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy Group, hexyloxy, heptyloxy, octyloxy, isooctyloxy and its isomers. The C 1 -C 8 alkylthio group can be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, tert-butylthio, pentylthio, isoamylthio Group, hexylthio, heptylthio, octylthio, isooctylthio and its isomers.
单独或联合出现的术语“C 3-C m环烷氧(硫)基”包括“C 3-C m环烷氧基”和“C 3-C m环烷硫基”，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或一个硫原子作为连接基团的C 3-C m环烷基，例如C 3-C 20环烷氧(硫)基，优选C 3-C 8环烷氧(硫)基，更优选C 5-C 6环烷氧(硫)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、环丙基硫基、环丁基硫基、环戊基硫基、环己基硫基、环庚基硫基、环辛基硫基、环癸基硫基及其异构体。 The term appears alone or in combination of "C 3 -C m cycloalkoxy (thio) group" include "C 3 -C m cycloalkoxy" and "C 3 -C m cycloalkylthio" refers to C 3 any ring carbon atom -C m cycloalkyl C 3 -C m corresponding cycloalkane is bonded to an oxygen atom or a sulfur atom as a cyclic C 3 -C m alkyl linking group, for example C 3 - C 20 cycloalkoxy (sulfur) group, preferably C 3 -C 8 cycloalkoxy (sulfur) group, more preferably C 5 -C 6 cycloalkoxy (sulfur) group, such as cyclopropyloxy, cyclobutyloxy Cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy and its isomers, cyclopropylthio, cyclobutylthio, cyclopentyl Cyclohexylsulfanyl, cyclohexylsulfanyl, cycloheptylsulfanyl, cyclooctylsulfanyl, cyclodecylsulfanyl and isomers thereof.
术语“C 3-C m环烷基C n-C m烷氧(硫)基”包括“C 3-C m环烷基C n-C m烷氧基”和“C 3-C m环烷基C n-C m烷硫基”，是指被C 3-C m环烷基取代的C n-C m烷氧(硫)基，此时两个m可相同或不同，其中C 3-C m环烷基和C n-C m烷氧(硫)基适用本文所定义。C 3-C m环烷基C n-C m烷氧(硫)基可以是C 3-C 10环烷基C 1-C 8烷氧(硫)基，优选C 3-C 6环烷基C 1-C 6烷氧(硫)基，更优选C 3-C 6环烷基C 1-C 4烷氧(硫)基，例如环丙基甲氧基、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、环丙基甲硫基、环丙基乙硫基、环丙基丙硫基、环丙基丁硫基、环丁基甲硫基、环丁基乙硫基、环丁基丙硫基、环丁基丁硫基、环戊基甲硫基、环戊基乙硫基、环戊基丙硫基、环戊基丁硫基、环己基甲硫基、环己基乙硫基、环己基丙硫基、环己基丁硫基等。 The term "C 3 -C m cycloalkyl C n -C m alkoxy (thio) group" includes "C 3 -C m cycloalkyl C n -C m alkoxy" and "C 3 -C m cycloalkane "C n -C m alkylthio group" refers to a C n -C m alkoxy (thio) group substituted by a C 3 -C m cycloalkyl group. In this case, two m may be the same or different, where C 3- The C m cycloalkyl group and the C n -C m alkoxy (thio) group apply as defined herein. C 3 -C m cycloalkyl C n -C m alkoxy (thio) group may be C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, preferably C 3 -C 6 cycloalkyl C 1 -C 6 alkoxy (thio) group, more preferably C 3 -C 6 cycloalkyl C 1 -C 4 alkoxy (thio) group, such as cyclopropylmethoxy, cyclopropylethoxy, cyclo Propylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethyl Oxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy, cyclopropylmethylthio, cyclopropyl Ethylethylthio, cyclopropylpropylthio, cyclopropylbutylthio, cyclobutylmethylthio, cyclobutylethylthio, cyclobutylpropylthio, cyclobutylbutylthio, cyclopentylmethylthio Cyclopentylethylthio, cyclopentylpropylthio, cyclopentylbutylthio, cyclohexylmethylthio, cyclohexylethylthio, cyclohexylpropylthio, cyclohexylbutylthio, etc.
术语“C n-C m烷基C 3-C m环烷氧基”表示被C n-C m烷基取代的C 3-C m环烷氧基，此时两个m可相同或不同，其中C n-C m烷基和C 3-C m环烷氧基适用本文所定义。C n-C m烷基C 3-C m环烷氧基可以是C 1-C 8烷基C 3-C 10环烷氧基，优选是C 1-C 6烷基C 3-C 6环烷氧基，更优选是C 1-C 4烷基C 3-C 6环烷氧基，例如甲基环丙氧基、乙基环丙氧基、丙基环丙氧基、丁基环丙氧基、甲基环丁氧基、乙基环丁氧基、丙基环丁氧基、丁基环丁氧基、甲基环戊氧基、乙基环戊氧基、丙基环戊氧基、丁基环戊氧基、甲基环己氧基、乙基环己氧基、丙基环己氧基、丁基环己氧基等。 The term "C n -C m alkyl C 3 -C m cycloalkoxy group" means a C 3 -C m cycloalkoxy group substituted by C n -C m alkyl group, in which case two m may be the same or different, Wherein C n -C m alkyl group and C 3 -C m cycloalkoxy group are defined herein. C n -C m alkyl C 3 -C m cycloalkoxy may be C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy, preferably C 1 -C 6 alkyl C 3 -C 6 ring Alkoxy, more preferably C 1 -C 4 alkyl C 3 -C 6 cycloalkoxy, such as methylcyclopropoxy, ethylcyclopropoxy, propylcyclopropoxy, butylcyclopropoxy , Methylcyclobutoxy, ethylcyclobutoxy, propylcyclobutoxy, butylcyclobutoxy, methylcyclopentyloxy, ethylcyclopentyloxy, propylcyclopentyloxy, butylcyclopentyl Oxy, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, etc.
本文所用术语“C 6-C m芳氧(硫)基”包括“C 6-C m芳氧基”和“C 6-C m芳硫基”，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或一个硫原子作为连接基团的C 6-C m芳基，例如苯硫基、苯氧基、甲苯氧基、甲苯硫基、萘硫基、萘氧基等。 As used herein, the term "C 6 -C m aryloxy (thio) group" includes "C 6 -C m aryloxy group" and "C 6 -C m arylthio group", which means that the C 6 -C m aryl group corresponds to the C 6 -C m on any of the aromatic carbon atoms in the aromatic hydrocarbon is bonded to an oxygen atom or a sulfur atom as a linking group C 6 -C m aryl group, e.g. phenyl group, a phenoxy group, tolyloxy , Tolylthio, naphthylthio, naphthyloxy, etc.
在本发明中，n为0或1。n为0时，式(I)化合物称作香豆素肟酯化合物；当n为1时，式(I)化合物称作香豆素酮肟酯化合物。这两种化合物统称为香豆素(酮)肟酯化合物。In the present invention, n is 0 or 1. When n is 0, the compound of formula (I) is called a coumarin oxime ester compound; when n is 1, the compound of formula (I) is called a coumarin ketoxime ester compound. These two compounds are collectively referred to as coumarin (keto)oxime ester compounds.
在本发明中，X为O、S、NR 1或CR 2aR 2b，其中R 1、R 2a和R 2b各自独立地为H、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了H以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基。 In the present invention, X is O, S, NR 1 or CR 2a R 2b , wherein R 1 , R 2a and R 2b are each independently H, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl , C 3 -C 10 cycloalkyl, C 1 -C 8 alkyl, C 1 -C 8 alkyl, C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 Cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl or C 6 -C 18 aryloxy (sulfur) group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the following group: halogen, nitro, amino, Cyano groups, C 1 -C 6 alkyl groups and C 1 -C 6 alkoxy (thio) groups.
优选的是，R 1、R 2a和R 2b各自独立地为H、C 1-C 10烷基、C 3-C 8环烷基、C 3-C 8环烷基C 1-C 6烷基、C 1-C 6烷基C 3-C 8环烷基、C 1-C 6烷氧(硫)基、C 3-C 8环烷氧(硫)基、C 3-C 8环烷基C 1-C 6烷氧(硫)基、C 1-C 6烷基C 3-C 8环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了H以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基。 Preferably, R 1 , R 2a and R 2b are each independently H, C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkyl , C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 alkoxy (sulfur) group, C 1 -C 6 alkyl C 3 -C 8 cycloalkoxy (sulfur) group, C 6 -C 10 aryl or C 6 -C 10 aryloxy (sulfur) Group, wherein each group other than H mentioned above may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 Alkoxy (thio) group.
特别优选的是，R 1、R 2a和R 2b各自独立地为H、C 1-C 8烷基、C 5-C 6环烷基、C 5-C 6环烷基C 1-C 4烷基、C 1-C 4烷基C 5-C 6环烷基、C 1-C 4烷氧(硫)基、C 5-C 6环烷氧(硫)基、C 3-C 6环烷基C 1-C 4烷氧(硫)基、C 1-C 4烷基C 5-C 6环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了H以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基。 Particularly preferably, R 1 , R 2a and R 2b are each independently H, C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkane Group, C 1 -C 4 alkyl C 5 -C 6 cycloalkyl, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy (thio) group, C 3 -C 6 cycloalkane C 1 -C 4 alkoxy (sulfur) group, C 1 -C 4 alkyl, C 5 -C 6 cycloalkoxy (sulfur) group, C 6 -C 10 aryl or C 6 -C 10 aryloxy (sulfur ) Group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 Alkoxy (thio) group.
尤其是，R 1为C 1-C 8烷基、苯基或萘基，其中所述苯基或萘基可以包含一个或多个相同或不同的C 1-C 4烷基取代基；以及R 2a和R 2b相同或不同，且各自独立地为H、C 1-C 6烷基、C 5-C 6环烷基C 1-C 4烷基或C 1-C 4烷氧基C 1-C 4烷基。 In particular, R 1 is C 1 -C 8 alkyl, phenyl or naphthyl, wherein the phenyl or naphthyl may contain one or more identical or different C 1 -C 4 alkyl substituents; and R 2a and R 2b are the same or different, and are each independently H, C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl C 1 -C 4 alkyl, or C 1 -C 4 alkoxy C 1- C 4 alkyl.
在本发明中，R 3、R 4、R 5、R 6相互独立地表示氢、卤素、硝基、氰基、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了氢、卤素、硝基、氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基。 In the present invention, R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3- C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy ( Thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl Group or C 6 -C 18 aryloxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the group: halogen, nitro Group, amino group, cyano group, C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group.
优选的是，R 3、R 4、R 5、R 6相互独立地表示氢、卤素、硝基、氰基、C 1-C 6烷基、C 3-C 8环烷基、C 3-C 8环烷基C 1-C 6烷基、C 1-C 6烷基C 3-C 8环烷基、C 1-C 6烷氧(硫)基、C 3-C 8环烷氧(硫)基、C 3-C 8环烷基C 1-C 6烷氧(硫)基、C 1-C 6烷基C 3-C 10环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了氢、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基。 Preferably, R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl C 1 -C 6 alkyl, C 1 -C 6 alkyl C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (sulfur) group, C 3 -C 8 cycloalkoxy (sulfur ) Group, C 3 -C 8 cycloalkyl C 1 -C 6 alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 10 aryl group Or a C 6 -C 10 aryloxy (thio) group, wherein each of the aforementioned groups except hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro , Amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group.
特别优选的是，R 3、R 4、R 5、R 6相互独立地表示氢、卤素、硝基、氰基、C 1-C 4烷基、C 5-C 6环烷基、C 5-C 6环烷基C 1-C 4烷基、C 1-C 4烷基C 5-C 6环烷基、C 1-C 4烷氧(硫)基、C 5-C 6环烷氧(硫)基、C 5-C 6环烷基C 1-C 4烷氧(硫)基、C 1-C 4烷基C 5-C 6环烷氧(硫)基、苯基或苯氧(硫)基，其中前述除了氢、卤素、硝基、氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：氟、氯、溴、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基。 Particularly preferably, R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 4 alkyl, C 5 -C 6 cycloalkyl, C 5- C 6 cycloalkyl C 1 -C 4 alkyl, C 1 -C 4 alkyl C 5 -C 6 cycloalkyl, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy ( Sulfur) group, C 5 -C 6 cycloalkyl C 1 -C 4 alkoxy (thio) group, C 1 -C 4 alkyl C 5 -C 6 cycloalkoxy (thio) group, phenyl or phenoxy ( Sulfur) group, wherein each of the aforementioned groups except hydrogen, halogen, nitro, cyano may contain one or more substituents independently selected from the following group: fluorine, chlorine, bromine, nitro, amino, cyano , C 1 -C 4 alkyl and C 1 -C 4 alkoxy (thio) group.
尤其是，R 3、R 4、R 5、R 6相互独立地表示氢、硝基、C 1-C 4烷基、C 1-C 4烷氧(硫)基或苯基。 In particular, R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy (thio) or phenyl.
在本发明中，A 1、A 2、A 3、A 4中连接式(I-1)结构部分的两个为碳原子，其余两个相同或不同，并且彼此独立地为CH或者CR 7，其中R 7为H、卤素、C 1-C 6烷基或C 1-C 6烷氧(硫)基，其中前述C 1-C 6烷基和C 1-C 6烷氧(硫)基可以包含一个或多个相同或不同的卤素取代基。 In the present invention, two of A 1 , A 2 , A 3 , and A 4 connected to the structural part of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , Wherein R 7 is H, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group can be Contains one or more identical or different halogen substituents.
优选的是，R 7为H、氟、氯、溴、C 1-C 4烷基或C 1-C 4烷氧(硫)基，其中前述C 1-C 4烷基和C 1-C 4烷氧(硫)基可以包含一个或多个相同或不同的选自氟、氯、溴的取代基。 Preferably, R 7 is H, fluorine, chlorine, bromine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy (thio) group, wherein the aforementioned C 1 -C 4 alkyl and C 1 -C 4 The alkoxy (thio) group may contain one or more identical or different substituents selected from fluorine, chlorine, and bromine.
尤其是，R 7为H或C 1-C 4烷基。 In particular, R 7 is H or C 1 -C 4 alkyl.
在本发明中，R 8是H、卤素、C 1-C 6烷基或C 1-C 6烷氧(硫)基，其中前述C 1-C 6烷基和C 6烷氧(硫)基可以包含一个或多个相同或不同的卤素取代基。 In the present invention, R 8 is H, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and C 6 alkoxy (thio) group It may contain one or more halogen substituents that are the same or different.
优选的是，R 8是H、氟、氯、溴、C 1-C 4烷基或C 1-C 4烷氧(硫)基，其中前述C 1-C 4烷基和C 1-C 4烷氧(硫)基可以包含一个或多个相同或不同的选自氟、氯、溴的取代基。尤其是R 8是H。 Preferably, R 8 is H, fluorine, chlorine, bromine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy (thio) group, wherein the aforementioned C 1 -C 4 alkyl group and C 1 -C 4 The alkoxy (thio) group may contain one or more identical or different substituents selected from fluorine, chlorine, and bromine. Especially R 8 is H.
尤其是，R 8是H或C 1-C 4烷基。 In particular, R 8 is H or C 1 -C 4 alkyl.
在本发明中，R 9是氢、卤素、硝基、氰基、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了H、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基。 In the present invention, R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl, C 1 -C 8 alkyl , C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (sulfur) group, C 1 -C 8 alkyl, C 3 -C 10 cycloalkoxy (sulfur) group, C 6 -C 18 aryl or C 6 -C 18 aryloxy (sulfur) Group, wherein each of the aforementioned groups other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano, C 1 -C 6 Alkyl group and C 1 -C 6 alkoxy (thio) group.
优选的是，R 9是氢、卤素、硝基、氰基、C 1-C 8烷基、C 3-C 8环烷基、C 3-C 8环烷基C 1-C 6烷基、C 1-C 6烷基C 3-C 8环烷基、C 1-C 6烷氧(硫)基、C 3-C 8环烷氧(硫)基、C 3-C 8环烷基C 1-C 6烷氧(硫)基、C 1-C 6烷基C 3-C 8环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了H、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基。 Preferably, R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkyl, C 1 -C 6 alkyl C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 alkoxy (thio) group, C 1 -C 6 alkyl, C 3 -C 8 cycloalkoxy (thio) group, C 6 -C 10 aryl or C 6 -C 10 aryloxy (thio) group , Wherein each of the aforementioned groups other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano, C 1 -C 6 alkane Group and C 1 -C 6 alkoxy (thio) group.
特别优选的是，R 9是氢、氟、氯、溴、硝基、氰基、C 1-C 8烷基、C 5-C 6环烷基、C 5-C 6环烷基C 1-C 4烷基、C 1-C 4烷基C 5-C 6环烷基、C 1-C 4烷氧(硫)基、C 5-C 6环烷氧(硫)基、C 5-C 6环烷基C 1-C 4烷氧(硫)基、C 1-C 4烷基C 5-C 6环烷氧(硫)基、苯基或苯氧(硫)基，其中前述除了氢、氟、氯、溴、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：氟、氯、溴、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基。 Particularly preferably, R 9 is hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl C 1- C 4 alkyl group, C 1 -C 4 alkyl group, C 5 -C 6 cycloalkyl group, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy (thio) group, C 5 -C 6 cycloalkyl C 1 -C 4 alkoxy (thio) group, C 1 -C 4 alkyl C 5 -C 6 cycloalkoxy (thio) group, phenyl or phenoxy (thio) group, wherein the foregoing is except hydrogen Each group other than fluorine, chlorine, bromine, nitro and cyano may contain one or more substituents independently selected from the following group: fluorine, chlorine, bromine, nitro, amino, cyano, C 1- C 4 alkyl and C 1 -C 4 alkoxy (thio) groups.
尤其是，R 9是氰基、C 1-C 7烷基、卤代C 1-C 6烷基或C 5-C 6环烷基C 1-C 4烷基。 In particular, R 9 is a cyano group, a C 1 -C 7 alkyl group, a halogenated C 1 -C 6 alkyl group or a C 5 -C 6 cycloalkyl C 1 -C 4 alkyl group.
在本发明中，R 10是C 1-C 20烷基或C 6-C 18芳基，其中C 1-C 20烷基和C 6-C 18芳基可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基。 In the present invention, R 10 is a C 1 -C 20 alkyl group or a C 6 -C 18 aryl group, wherein the C 1 -C 20 alkyl group and the C 6 -C 18 aryl group may include one or more independently selected from Substituents of the following group: halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group.
优选的是，R 10是C 1-C 6烷基或C 6-C 10芳基，其中C 1-C 6烷基和C 6-C 10芳基可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基。 Preferably, R 10 is C 1 -C 6 alkyl or C 6 -C 10 aryl, wherein C 1 -C 6 alkyl and C 6 -C 10 aryl may include one or more independently selected from Substituents of the group: halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group.
特别优选的是，R 10是C 1-C 4烷基或苯基，其中C 1-C 4烷基和苯基可以包含一个或多个独立地选自下组的取代基：氟、氯、溴、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基。 It is particularly preferred that R 10 is a C 1 -C 4 alkyl group or a phenyl group, wherein the C 1 -C 4 alkyl group and the phenyl group may contain one or more substituents independently selected from the following group: fluorine, chlorine, Bromine, nitro, amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (thio) group.
尤其是，R 10是C 1-C 4烷基或苯基。 In particular, R 10 is C 1 -C 4 alkyl or phenyl.
在本发明的一些优选实施方案中，其中In some preferred embodiments of the present invention, wherein
X为O、S、NR 1或CR 2aR 2b，其中R 1为C 1-C 8烷基、苯基或萘基，其中所述苯基或萘基可以包含一个或多个相同或不同的C 1-C 4烷基取代基；以及R 2a和R 2b相同或不同，且各自独立地为H、C 1-C 6烷基、C 5-C 6环烷基C 1-C 4烷基、C 1-C 4烷氧基C 1-C 4烷基； X is O, S, NR 1 or CR 2a R 2b , wherein R 1 is C 1 -C 8 alkyl, phenyl or naphthyl, wherein said phenyl or naphthyl may contain one or more of the same or different C 1 -C 4 alkyl substituent; and R 2a and R 2b are the same or different, and are each independently H, C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkyl , C 1 -C 4 alkoxy C 1 -C 4 alkyl;
R 3、R 4、R 5、R 6相互独立地表示氢、硝基、C 1-C 4烷基、C 1-C 4烷氧(硫)基或苯基； R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy (thio) or phenyl;
A 1、A 2、A 3、A 4中连接式(I-1)结构部分的两个为碳原子，其余两个相同或不同，并且彼此独立地为CH或者CR 7，其中R 7H或C 1-C 4烷基； Two of A 1 , A 2 , A 3 , and A 4 connecting the structural parts of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , wherein R 7 H or C 1 -C 4 alkyl;
R 8是H或C 1-C 4烷基； R 8 is H or C 1 -C 4 alkyl;
R 9是氰基、C 1-C 7烷基、卤代C 1-C 6烷基或C 5-C 6环烷基C 1-C 4烷基；以及 R 9 is cyano, C 1 -C 7 alkyl, halo C 1 -C 6 alkyl or C 5 -C 6 cycloalkyl C 1 -C 4 alkyl; and
R 10是C 1-C 4烷基或苯基。 R 10 is C 1 -C 4 alkyl or phenyl.
在本发明的一些特别优选的实施方案中，式(I)化合物选自化合物1-64。化合物1-64分别在实施例1-64中制备。In some particularly preferred embodiments of the present invention, the compound of formula (I) is selected from compounds 1-64. Compounds 1-64 were prepared in Examples 1-64, respectively.
根据本发明的第二个方面，提供了一种制备本发明式(I)化合物的方法，包括以下步骤：According to the second aspect of the present invention, there is provided a method for preparing the compound of formula (I) of the present invention, which comprises the following steps:
(1)肟化反应：当n为0时，使式(II)化合物与羟胺、盐酸羟胺或其任意组合进行肟化反应，得到式(IIIa)化合物(1) The oximation reaction: when n is 0, the compound of formula (II) is subjected to oximation reaction with hydroxylamine, hydroxylamine hydrochloride or any combination thereof to obtain the compound of formula (IIIa)
Figure PCTCN2019092708-appb-000007
Figure PCTCN2019092708-appb-000007
当n为1时，使式(II)化合物与亚硝酸、亚硝酸盐、亚硝酸烷基酯或其任意组合进行肟化反应，得到式(IIIb)化合物:When n is 1, the compound of formula (II) is subjected to oximation reaction with nitrous acid, nitrite, alkyl nitrite or any combination thereof to obtain a compound of formula (IIIb):
Figure PCTCN2019092708-appb-000008
Figure PCTCN2019092708-appb-000008
其中，式(II)、(IIIa)和(IIIb)中的A 1、A 2、A 3、A 4、R 8和R 9如对式(I)化合物所定义；以及 Wherein, A 1 , A 2 , A 3 , A 4 , R 8 and R 9 in formula (II), (IIIa) and (IIIb) are as defined for the compound of formula (I); and
(2)将式(IIIa)或(IIIb)化合物酯化，得到式(I)化合物。(2) Esterify the compound of formula (IIIa) or (IIIb) to obtain the compound of formula (I).
为了制备本发明的式(I)化合物，需要先进行肟化反应，以引入肟基，然后肟基中的羟基经酯化反应转变成相应的酯基，从而获得本发明的香豆素(酮)肟酯化合物。In order to prepare the compound of formula (I) of the present invention, it is necessary to perform an oximation reaction first to introduce an oxime group, and then the hydroxyl group in the oxime group is converted into the corresponding ester group by an esterification reaction, thereby obtaining the coumarin (ketone) of the present invention ) Oxime ester compounds.
肟化反应Oximation reaction
肟化反应通常从羰基化合物开始。为此，当n为0时，使式(III)化合物与羟胺、盐酸羟胺或其任意组合进行肟化反应，得到式(IIIa)化合物：The oximation reaction usually starts from the carbonyl compound. For this reason, when n is 0, the compound of formula (III) is subjected to an oximation reaction with hydroxylamine, hydroxylamine hydrochloride or any combination thereof to obtain a compound of formula (IIIa):
Figure PCTCN2019092708-appb-000009
Figure PCTCN2019092708-appb-000009
式(II)和(IIIa)中的A 1、A 2、A 3、A 4、R 8和R 9如对式(I)化合物所定义。为了将式(II)化合物中的非环羰基转变为肟基，通常使用盐酸羟胺(NH 2OH·HCl)、羟胺(NH 2OH)或其混合物作为肟化试剂。该肟化反应通常在有机溶剂中进行，优选在有机极性溶剂中进行。可采用的溶剂例如有乙醇或含水的乙醇。为了促进肟化反应进行完全，一般需加入乙酸钠、吡啶、哌啶、三乙胺、四甲基氢氧化铵之类的碱或其混合物。这当中，吡啶、哌啶、三乙胺也可用作碱和/或溶剂或助溶剂。肟化反应的温度一般为溶剂的回流温度，温度范围通常在60-120℃。肟化反应时间也没有特别的限制，通常进行0.1-20小时，优选0.5-10小时。式(II)化合物与选自羟胺和/或盐酸羟胺的化合物的相对用量没有特别的限制，通常而言它们以大致等摩尔量使用，例如二者的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。 A 1 , A 2 , A 3 , A 4 , R 8 and R 9 in formula (II) and (IIIa) are as defined for the compound of formula (I). In order to convert the acyclic carbonyl group in the compound of formula (II) into an oxime group, hydroxylamine hydrochloride (NH 2 OH·HCl), hydroxylamine (NH 2 OH) or a mixture thereof is usually used as an oximation reagent. The oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Examples of usable solvents include ethanol or water-containing ethanol. In order to promote the completion of the oximation reaction, it is generally necessary to add a base such as sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide, or a mixture thereof. Among them, pyridine, piperidine, and triethylamine can also be used as bases and/or solvents or co-solvents. The temperature of the oximation reaction is generally the reflux temperature of the solvent, and the temperature range is usually 60-120°C. The oximation reaction time is also not particularly limited, and it is usually carried out for 0.1-20 hours, preferably 0.5-10 hours. The relative amount of the compound of formula (II) and the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is not particularly limited. Generally speaking, they are used in approximately equimolar amounts, for example, the molar ratio of the two is 1:1.5-1.5:1, Preferably it is 1:1.2-1.2:1.
当n为1时，使上述式(II)化合物与亚硝酸、亚硝酸盐、亚硝酸烷基酯或其任意组合进行肟化反应，得到式(IIIb)化合物:When n is 1, the compound of the above formula (II) is subjected to an oximation reaction with nitrous acid, nitrite, alkyl nitrite or any combination thereof to obtain a compound of formula (IIIb):
Figure PCTCN2019092708-appb-000010
Figure PCTCN2019092708-appb-000010
其中，式(IIIb)中的的A 1、A 2、A 3、A 4、R 8和R 9如对式(I)所定义。为了将式(II)化合物中的非环羰基转变为酮肟基，通常使用亚硝酸、亚硝酸盐、亚硝酸烷基酯或其混合物作为肟化试剂。该试剂将“活性”(亚)甲基(α-(亚)甲基，即紧挨着非环羰基的(亚)甲基)进行亚硝化。作为亚硝酸盐，通常使用亚硝酸钠。亚硝酸烷基酯可以是亚硝酸C 1-C 6烷基酯，例如亚硝酸甲酯、亚硝酸乙酯、亚硝酸异丙酯、亚硝酸丁酯、亚硝酸异戊酯。该肟化反应通常在有机溶剂中进行，优选在有机极性溶剂中进行。可采用的溶剂例如有四氢呋喃、乙醇或含水的乙醇。为了促进肟化反应进行完全，一般需加入浓盐酸，其浓度通常为20-40％。浓盐酸也可用作酸和/或溶剂或助溶剂。肟化反应的温度为低温，温度范围通常在-30至20℃，优选5-20℃。肟化反应时间也没有特别的限制，通常进行0.1-20小时，优选0.5-10小时。式(II)化合物与选自亚硝酸、亚硝酸盐和/或亚硝酸烷基酯的化合物的相对用量没有特别的限制，通常而言它们以大致等摩尔量使用，例如二者的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。 Wherein, A 1 , A 2 , A 3 , A 4 , R 8 and R 9 in formula (IIIb) are as defined for formula (I). In order to convert the acyclic carbonyl group in the compound of formula (II) into a ketoxime group, nitrous acid, nitrite, alkyl nitrite or a mixture thereof are usually used as an oximation reagent. This reagent nitrosates the "active" (methylene) methyl group (α-(methylene) methyl group, that is, the (methylene) group next to the non-cyclic carbonyl group). As the nitrite, sodium nitrite is usually used. The alkyl nitrite may be a C 1 -C 6 alkyl nitrite, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite. The oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Examples of usable solvents include tetrahydrofuran, ethanol, or water-containing ethanol. In order to promote the completion of the oximation reaction, it is generally necessary to add concentrated hydrochloric acid, the concentration of which is usually 20-40%. Concentrated hydrochloric acid can also be used as acid and/or solvent or co-solvent. The temperature of the oximation reaction is a low temperature, and the temperature range is usually -30 to 20°C, preferably 5-20°C. The oximation reaction time is also not particularly limited, and it is usually carried out for 0.1-20 hours, preferably 0.5-10 hours. The relative amount of the compound of formula (II) and the compound selected from the group consisting of nitrous acid, nitrite and/or alkyl nitrite is not particularly limited. Generally, they are used in approximately equimolar amounts, for example, the molar ratio of the two is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
每个肟酯基可能存在两种构型，(Z)型或(E)型。可通过常规方法分离异构体，但也可使用异构体混合物作为光引发物质。因此，本发明还涉及式(I)化合物各自的构型异构体的混合物。Each oxime ester group may have two configurations, (Z) type or (E) type. The isomers can be separated by conventional methods, but it is also possible to use a mixture of isomers as the photoinitiating substance. Therefore, the present invention also relates to a mixture of each configurational isomer of the compound of formula (I).
酯化反应Esterification reaction
式(IIIa)和(IIIb)化合物的酯化是常规的，通过该反应，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(IIIa)和(IIIb)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。这些化合物可分别表示为式(IVa)、(IVb)和(IVc):The esterification of the compounds of formula (IIIa) and (IIIb) is conventional. Through this reaction, the hydroxyl group in the oxime group is converted into an ester group, thereby obtaining the compound of formula (I). As the esterification reagent, there is no particular limitation, as long as it can convert the hydroxyl group in the oxime group of the compounds of formula (IIIa) and (IIIb) into an ester group. As the esterification reagent, the corresponding acid halide, such as acid chloride, the corresponding carboxylic acid, and the corresponding acid anhydride can also be used. These compounds can be represented as formula (IVa), (IVb) and (IVc) respectively:
Figure PCTCN2019092708-appb-000011
Figure PCTCN2019092708-appb-000011
其中X为卤素，尤其是氯，和R 10如对式(I)化合物所定义。 Where X is halogen, especially chlorine, and R 10 is as defined for the compound of formula (I).
为了加速酯化反应，上述酯化反应通常在适于酯化反应的催化剂存在下进行。作为催化剂，既可以使用酸性催化剂，也可以使用碱性催化剂。作为催化剂，可以使用硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙、四甲基氢氧化铵、叔胺(例如三烷基胺，如三甲基胺和三乙胺)或其任意组合。催化剂的用量是常规的，可以通过本领域的常识确定，或者通过几个例行的预备实验来确定。In order to accelerate the esterification reaction, the above-mentioned esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction. As the catalyst, either an acid catalyst or a basic catalyst may be used. As a catalyst, sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, ethanol can be used Sodium, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide, tertiary amines (e.g. trialkylamines such as trimethylamine and triethylamine) or any combination thereof. The amount of catalyst used is conventional and can be determined by common sense in the field or through several routine preliminary experiments.
为了提高式(I)化合物的产率，有利的是，在酯化反应过程中移除酯化反应产生的水。这例如可以通过蒸馏冷凝来进行。In order to increase the yield of the compound of formula (I), it is advantageous to remove water produced by the esterification reaction during the esterification reaction. This can be done, for example, by distillation and condensation.
上述酯化反应通常在溶剂中，优选在有机溶剂中进行。作为溶剂的类型的选择，没有特 别的限制，只要能够将式(IIIa)或式(IIIb)化合物和酯化试剂溶解并且对酯化反应呈化学惰性即可，即不参与该酯化反应即可。作为溶剂的实例，可以提及四氢呋喃、苯、甲苯、N,N-二甲基甲酰胺、二氯甲烷和丙酮。溶剂可以使用单一种，也可以使用两种或更多种溶剂的混合物。The above-mentioned esterification reaction is usually carried out in a solvent, preferably in an organic solvent. There is no particular limitation on the choice of the type of solvent, as long as it can dissolve the compound of formula (IIIa) or formula (IIIb) and the esterification reagent and is chemically inert to the esterification reaction, that is, it does not participate in the esterification reaction. . As examples of the solvent, tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone can be mentioned. A single solvent may be used, or a mixture of two or more solvents may be used.
式(IIIa)或式(IIIb)化合物与选自(IVa)、(IVb)和(IVc)化合物的酯化试剂的相对用量没有特别的限制，通常而言它们以大致等摩尔量使用，例如二者的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。The relative amount of the compound of formula (IIIa) or (IIIb) and the esterification agent selected from the group of compounds (IVa), (IVb) and (IVc) is not particularly limited. Generally speaking, they are used in approximately equimolar amounts, such as two The molar ratio of these is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
酯化反应可以在非常宽的温度范围内进行。根据本发明有利的是，酯化反应在-10℃至150℃，优选0℃至100℃的温度下进行，优选常温下进行。酯化反应时间也没有特别的限制，通常进行1-24小时，优选1-12小时。The esterification reaction can be carried out in a very wide temperature range. According to the present invention, it is advantageous that the esterification reaction is carried out at a temperature of -10°C to 150°C, preferably 0°C to 100°C, preferably at room temperature. The esterification reaction time is also not particularly limited, and it is usually carried out for 1-24 hours, preferably 1-12 hours.
在酯化反应完成之后，获得包含式(I)化合物的反应混合物。因此，需要对该反应混合物进行后处理，以得到提纯的式(I)化合物。通常而言，首先过滤酯化反应得到的反应混合物，取出滤液部分。然后，将滤液进行洗涤，以除去催化剂和未反应的原料。作为洗液，没有特别的限制，只要能除去催化剂和未反应的原料即可。作为洗液的实例，可以提及稀盐酸(水溶液)、饱和碳酸氢钠水溶液和水。稀盐酸的浓度没有特别的限制，通常而言使用浓度为5-12％的稀盐酸。用洗液洗涤可以进行一次，也可进行多次；在进行多次的情况下，可使用单一种洗液，也可依次使用不同的洗液。根据本发明有利的是，将对酯化反应得到的反应混合物过滤得到的滤液依次用稀盐酸、饱和碳酸氢钠水溶液和水进行洗涤。当然，每一次用洗液洗涤后，都需要倒掉水相之后再用下一种洗液对有机相进行洗涤。洗涤之后，需要干燥以除去残留的水。为此，通常可使用无水硫酸钠进行干燥。干燥之后，再除去残留的有机溶剂。作为这里除去有机溶剂的手段，没有特别的限制，通常可通过减压蒸馏来除去有机溶剂。除去残留有机溶剂之后，得到了式(I)化合物的粗产物。如果想要进一步提高式(I)化合物的纯度，还可对该化合物进行进一步提纯，这例如可通过重结晶的方式来进行。重结晶溶剂的选择是常规的，没有特别的限制。根据本发明，有利的是，采用甲醇对式(I)化合物的粗产物进行重结晶。After the esterification reaction is completed, a reaction mixture containing the compound of formula (I) is obtained. Therefore, the reaction mixture needs to be post-treated to obtain a purified compound of formula (I). Generally, the reaction mixture obtained by the esterification reaction is filtered first, and the filtrate portion is taken out. Then, the filtrate is washed to remove the catalyst and unreacted raw materials. As the washing liquid, there is no particular limitation, as long as the catalyst and unreacted raw materials can be removed. As examples of the washing liquid, dilute hydrochloric acid (aqueous solution), saturated sodium bicarbonate aqueous solution and water can be mentioned. The concentration of dilute hydrochloric acid is not particularly limited. Generally, dilute hydrochloric acid with a concentration of 5-12% is used. Washing with lotion can be done once or multiple times; in the case of multiple times, a single lotion can be used, or different lotions can be used in sequence. According to the present invention, it is advantageous that the filtrate obtained by filtering the reaction mixture obtained by the esterification reaction is washed successively with dilute hydrochloric acid, a saturated sodium bicarbonate aqueous solution and water. Of course, after each washing with a lotion, you need to pour off the water phase and then use the next lotion to wash the organic phase. After washing, it needs to be dried to remove residual water. For this reason, anhydrous sodium sulfate can usually be used for drying. After drying, the remaining organic solvent is removed. The means for removing the organic solvent here is not particularly limited, and the organic solvent can usually be removed by distillation under reduced pressure. After removing the residual organic solvent, a crude product of the compound of formula (I) is obtained. If it is desired to further improve the purity of the compound of formula (I), the compound can be further purified, for example, by recrystallization. The selection of the recrystallization solvent is conventional and not particularly limited. According to the present invention, it is advantageous to use methanol to recrystallize the crude product of the compound of formula (I).
通式(II)化合物可市购，也可用本领域的常规方法制备。在本发明方法的一些优选实施方案中，还包括步骤：使式(V)化合物与式(VI)化合物反应，得到式(II)化合物。式(V)化合物与式(VI)化合物之间发生诺文葛尓(Knoevenagel)缩合反应，得到式(II)化合物The compound of general formula (II) is commercially available or can be prepared by conventional methods in the art. In some preferred embodiments of the method of the present invention, the method further includes the step of reacting the compound of formula (V) with the compound of formula (VI) to obtain the compound of formula (II). A Knoevenagel condensation reaction occurs between the compound of formula (V) and the compound of formula (VI) to obtain the compound of formula (II)
Figure PCTCN2019092708-appb-000012
Figure PCTCN2019092708-appb-000012
其中式(V)化合物中的A 1、A 2、A 3、A 4和R 8如对式(I)化合物所定义，以及式(VI)化合物中的R 9如对式(I)化合物所定义，和R 11为C 1-C 12烷基，优选C 1-C 6烷基。 Wherein A 1 , A 2 , A 3 , A 4 and R 8 in the compound of formula (V) are as defined for the compound of formula (I), and R 9 in the compound of formula (VI) is as defined for the compound of formula (I) Definitions, and R 11 are C 1 -C 12 alkyl groups, preferably C 1 -C 6 alkyl groups.
上述诺文葛尓(Knoevenagel)缩合反应通常在适于该缩合反应的催化剂存在下进行。作为催化剂，通常可以选用碱性催化剂。例如可以使用六氢吡啶、吡啶、哌啶、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙、四甲基氢氧化铵、叔胺(例如三烷基胺，如三甲基胺和三乙胺)或其任意组合。该催化剂的用量是常规的，可以通 过本领域的常识确定，或者通过几个例行的预备实验来确定。The above-mentioned Knoevenagel condensation reaction is usually carried out in the presence of a catalyst suitable for the condensation reaction. As the catalyst, a basic catalyst can usually be selected. For example, hexahydropyridine, pyridine, piperidine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide can be used , Tertiary amines (for example, trialkylamines, such as trimethylamine and triethylamine) or any combination thereof. The amount of the catalyst is conventional and can be determined by common sense in the field, or through several routine preliminary experiments.
上述缩合反应通常在溶剂中，优选在有机溶剂中进行。作为溶剂的类型的选择，没有特别的限制，只要能够将式(V)和式(VI)化合物溶解并且对该缩合反应呈化学惰性即可，即不参与该缩合反应即可。作为溶剂的实例，可以提及乙醇、甲醇、叔丁醇、四氢呋喃、苯、甲苯、二氯甲烷和丙酮。溶剂可以使用单一种，也可以使用两种或更多种溶剂的混合物。The above-mentioned condensation reaction is usually carried out in a solvent, preferably in an organic solvent. The choice of the type of solvent is not particularly limited, as long as it can dissolve the compounds of formula (V) and formula (VI) and is chemically inert to the condensation reaction, that is, it does not participate in the condensation reaction. As examples of the solvent, ethanol, methanol, tert-butanol, tetrahydrofuran, benzene, toluene, methylene chloride, and acetone can be mentioned. A single solvent may be used, or a mixture of two or more solvents may be used.
式(V)化合物和式(VI)化合物的相对用量没有特别的限制，通常而言它们以大致等摩尔量使用，例如二者的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。The relative amount of the compound of formula (V) and the compound of formula (VI) is not particularly limited. Generally speaking, they are used in approximately equimolar amounts, for example, the molar ratio of the two is 1:1.5-1.5:1, preferably 1:1.2 -1.2:1.
上述缩合反应可以在非常宽的温度范围内进行。根据本发明有利的是，所述缩合反应在0℃至150℃，优选0℃至100℃的温度下进行，优选溶剂的回流温度下进行。缩合反应时间也没有特别的限制，通常进行1-24小时，优选1-12小时。The above condensation reaction can be carried out in a very wide temperature range. According to the present invention, it is advantageous that the condensation reaction is carried out at a temperature of 0°C to 150°C, preferably 0°C to 100°C, preferably at the reflux temperature of the solvent. The condensation reaction time is also not particularly limited, and it is usually carried out for 1-24 hours, preferably 1-12 hours.
在缩合反应完成之后，获得包含式(II)化合物的反应混合物。因此，需要对该反应混合物进行后处理，以得到提纯的式(II)化合物。该后处理使常规的，例如可以首先过滤得到的反应混合物，然后重结晶。重结晶溶剂的选择是常规的，没有特别的限制。根据本发明，有利的是，采用甲醇、乙醇或其混合物对式(II)化合物的粗产物进行重结晶。After the condensation reaction is completed, a reaction mixture containing the compound of formula (II) is obtained. Therefore, the reaction mixture needs to be post-treated to obtain a purified compound of formula (II). This post-treatment is conventional, for example, the reaction mixture obtained can be filtered first and then recrystallized. The selection of the recrystallization solvent is conventional and not particularly limited. According to the present invention, it is advantageous to use methanol, ethanol or a mixture thereof to recrystallize the crude product of the compound of formula (II).
本发明式(I)化合物在300-500nm、特别是350-450nm、尤其是在365-450nm的波长范围内有很强吸收，故可应用于UV-可见LED光固化体系中。本发明式(I)化合物的制备原料都是毒性较小的香豆素酮类化合物，相比传统的光引发剂，对人体和环境的危害程度降低。The compound of formula (I) of the present invention has strong absorption in the wavelength range of 300-500nm, especially 350-450nm, especially 365-450nm, so it can be applied to UV-visible LED light curing system. The raw materials for the preparation of the compound of formula (I) of the present invention are all coumarin ketone compounds with less toxicity. Compared with traditional photoinitiators, the harm to the human body and the environment is reduced.
因此，根据本发明的第三个方面，提供了本发明式(I)化合物作为光引发剂的用途。本发明式(I)化合物在紫外-可见LED光固化体系中作为光引发剂，可以有效地引发固化反应。特别优选的是，本发明式(I)化合物在辐射波长为300-500nm、特别是350-450nm、尤其是在365-450nm的光固化体系中作为光引发剂的用途。式(I)化合物可在涂料、油墨、微电子、印刷等领域用作光引发剂或光敏剂。当式(I)化合物用作光引发剂时，其用量是常规的，或者通过例行的预备试验即可确定。Therefore, according to the third aspect of the present invention, the use of the compound of formula (I) of the present invention as a photoinitiator is provided. The compound of formula (I) of the present invention is used as a photoinitiator in a UV-visible LED light curing system, and can effectively initiate a curing reaction. Particularly preferred is the use of the compound of formula (I) of the present invention as a photoinitiator in a photocuring system with a radiation wavelength of 300-500 nm, especially 350-450 nm, especially 365-450 nm. The compound of formula (I) can be used as a photoinitiator or photosensitizer in coatings, inks, microelectronics, printing and other fields. When the compound of formula (I) is used as a photoinitiator, its dosage is conventional, or can be determined by routine preliminary tests.
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。The present invention will be further described below in conjunction with specific examples, but it should not be understood as a limitation on the protection scope of the present invention.
实施例1：化合物1的制备Example 1: Preparation of Compound 1
Figure PCTCN2019092708-appb-000013
Figure PCTCN2019092708-appb-000013
化合物1的合成路线如下：The synthetic route of compound 1 is as follows:
Figure PCTCN2019092708-appb-000014
Figure PCTCN2019092708-appb-000014
中间化合物1a的合成Synthesis of Intermediate Compound 1a
将3,9-二甲基-9H-咔唑基-1-羟基-2-甲醛(0.05mol，11.95g)加入盛有50mL乙醇的250mL三口圆底烧瓶中，搅拌均匀后，将混合液加热至35℃使反应物全部溶于乙醇中。然后加入六氢吡啶(0.01mol，1mL)和乙酰乙酸乙酯(0.06mol，7.8g)，再将反应混合物加热至回流，搅拌反应1h。待反应完全后，将混合物冷却至室温，过滤得黄色固体，然后用乙醇重结晶，得13g产品，产率90％，经鉴定为化合物1a。1H-NMR(400MHz,CDCl 3)δ2.27(s，3H)，3.48(s，3H)，3.82(s，3H)，7.02(s，1H)，7.30(d，1H)，7.42-7.45(m，2H)，8.17(d，1H)，8.45(s,1H)。 Add 3,9-dimethyl-9H-carbazolyl-1-hydroxy-2-carbaldehyde (0.05mol, 11.95g) into a 250mL three-neck round bottom flask containing 50mL of ethanol, and after stirring, heat the mixture Dissolve all the reactants in ethanol at 35°C. Then hexahydropyridine (0.01 mol, 1 mL) and ethyl acetoacetate (0.06 mol, 7.8 g) were added, and the reaction mixture was heated to reflux, and the reaction was stirred for 1 h. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a yellow solid, and then recrystallized with ethanol to obtain 13 g of product with a yield of 90%, which was identified as compound 1a. 1H-NMR (400MHz, CDCl 3 ) δ 2.27 (s, 3H), 3.48 (s, 3H), 3.82 (s, 3H), 7.02 (s, 1H), 7.30 (d, 1H), 7.42 to 7.45 ( m, 2H), 8.17 (d, 1H), 8.45 (s, 1H).
中间化合物1b的合成Synthesis of intermediate compound 1b
将中间化合物1a(11.64g，0.04mol)和50mL乙醇和水的混合溶液(V 乙醇：V 水＝2:1)倒入100mL三口圆底烧瓶中，再加入盐酸羟胺(2.76g，0.04mol)和醋酸钠(3.28g，0.04mol)。70℃下搅拌反应0.5h后，过滤反应液，然后将滤液真空旋蒸后得淡黄色固体，乙醇重结晶，得11.2g产品，产率为92％，经鉴定为化合物1b。1H-NMR(400MHz,CDCl 3)δ2.27(s，3H)，3.48(s，3H)，3.82(s，3H)，7.02(s，1H)，7.30(d，1H)，7.42-7.45(m，2H)，8.17(d，1H)，8.45(s,1H)，8.45(s,1H)，8.70(s,1H)。 Pour intermediate compound 1a (11.64g, 0.04mol) and 50mL ethanol and water mixed solution (V ethanol : V water = 2:1) into a 100mL three-necked round bottom flask, and then add hydroxylamine hydrochloride (2.76g, 0.04mol) And sodium acetate (3.28g, 0.04mol). After stirring and reacting at 70°C for 0.5 h, the reaction solution was filtered, and then the filtrate was vacuum-rotated to obtain a light yellow solid, which was recrystallized from ethanol to obtain 11.2 g of product with a yield of 92%. It was identified as compound 1b. 1H-NMR (400MHz, CDCl 3 ) δ 2.27 (s, 3H), 3.48 (s, 3H), 3.82 (s, 3H), 7.02 (s, 1H), 7.30 (d, 1H), 7.42 to 7.45 ( m, 2H), 8.17 (d, 1H), 8.45 (s, 1H), 8.45 (s, 1H), 8.70 (s, 1H).
目标产物1的合成Synthesis of target product 1
将上述中间化合物1b(9.18g，0.03mol)和30ml四氢呋喃加入到100mL三口圆底烧瓶中，然后加入乙酰氯(2.81g，0.036mol)和三乙胺(4.67g，0.045mol)，常温搅拌反应1h。终止反应，将反应液过滤后，滤液倒入水中，用乙酸乙酯萃取，收集有机相后依次用稀盐酸溶液、饱和碳酸钠水溶液和蒸馏水洗涤，然后收集有机相，并用MgSO 4干燥过夜。过滤后减压蒸馏蒸掉有机相后，得黄色粉末状固体9.4g，产率90.0％，经鉴定为化合物1。1H-NMR(400MHz,CDCl 3)δ2.20(s，3H)，2.48(s，3H)，3.11(s，3H)，3.82(s，3H)，7.26(s，1H)，7.33(t，1H)，7.44(t，1H)，7.54(s，1H)，7.59(d，1H)，8.17(d，1H) Add the above-mentioned intermediate compound 1b (9.18g, 0.03mol) and 30ml of tetrahydrofuran into a 100mL three-necked round bottom flask, then add acetyl chloride (2.81g, 0.036mol) and triethylamine (4.67g, 0.045mol), stir and react at room temperature 1h. The reaction was terminated, the reaction solution was filtered, the filtrate was poured into water, extracted with ethyl acetate, the organic phase was collected and washed with dilute hydrochloric acid solution, saturated sodium carbonate aqueous solution and distilled water successively, then the organic phase was collected and dried with MgSO 4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 9.4 g of a yellow powdery solid with a yield of 90.0%, which was identified as compound 1. 1H-NMR (400MHz, CDCl 3 ) δ 2.20 (s, 3H), 2.48 ( s, 3H), 3.11(s, 3H), 3.82(s, 3H), 7.26(s, 1H), 7.33(t, 1H), 7.44(t, 1H), 7.54(s, 1H), 7.59(d , 1H), 8.17(d, 1H)
实施例2-43：化合物2-43的制备Example 2-43: Preparation of Compound 2-43
重复实施例1的方法，适当改变反应原料，分别获得下表1所示的化合物2-43及其核磁数据。Repeat the method of Example 1 and appropriately change the reaction materials to obtain the compounds 2-43 and its nuclear magnetic data shown in Table 1 below.
实施例44：化合物44的制备Example 44: Preparation of Compound 44
首先合成化合物44a，合成路线如下：First, compound 44a is synthesized. The synthetic route is as follows:
Figure PCTCN2019092708-appb-000015
Figure PCTCN2019092708-appb-000015
中间化合物44a的合成Synthesis of intermediate compound 44a
将4-甲基-6-羟基-7-甲基羰基二苯并呋喃(0.05mol，12g)加入盛有50mL乙醇的250mL三口圆底烧瓶中，搅拌均匀后，将混合液加热至35℃使反应物全部溶于乙醇中。然后加入六氢吡啶(0.01mol，1mL)和乙酰乙酸乙酯(0.06mol，7.8g)，再将反应混合物加热至回流，搅拌反应1h。待反应完全后，将混合物冷却至室温，过滤得黄色固体，然后用乙醇重结晶，得12.5g产品，产率81.6％，经鉴定为化合物44a。1H-NMR(400MHz,CDCl 3)δ2.27(s，3H)，3.48(s，3H)，3.82(s，3H)，7.02(d，1H)，7.30(d，1H)，7.38(d，2H)，7.45(m，1H)。 Add 4-methyl-6-hydroxy-7-methylcarbonyl dibenzofuran (0.05mol, 12g) into a 250mL three-necked round bottom flask containing 50mL of ethanol. After stirring, heat the mixture to 35°C. The reactants are all dissolved in ethanol. Then hexahydropyridine (0.01 mol, 1 mL) and ethyl acetoacetate (0.06 mol, 7.8 g) were added, and the reaction mixture was heated to reflux, and the reaction was stirred for 1 h. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a yellow solid, and then recrystallized with ethanol to obtain 12.5 g of product with a yield of 81.6%, which was identified as compound 44a. 1H-NMR (400MHz, CDCl 3 ) δ 2.27 (s, 3H), 3.48 (s, 3H), 3.82 (s, 3H), 7.02 (d, 1H), 7.30 (d, 1H), 7.38 (d, 2H), 7.45 (m, 1H).
其他步骤与化合物1类似，其中用化合物44a代替化合物1a，最终得到化合物44，其核磁数据如下表1中所示。The other steps are similar to those of compound 1, in which compound 44a is used instead of compound 1a to finally obtain compound 44. The nuclear magnetic data is shown in Table 1 below.
化合物45-51的制备Preparation of compound 45-51
重复实施例1的方法，适当改变反应原料，分别获得下表1所示的化合物45-51及其核磁数据。Repeat the method of Example 1 and appropriately change the reaction materials to obtain compounds 45-51 and their nuclear magnetic data shown in Table 1 below.
表1Table 1
Figure PCTCN2019092708-appb-000016
Figure PCTCN2019092708-appb-000016
Figure PCTCN2019092708-appb-000017
Figure PCTCN2019092708-appb-000017
Figure PCTCN2019092708-appb-000018
Figure PCTCN2019092708-appb-000018
Figure PCTCN2019092708-appb-000019
Figure PCTCN2019092708-appb-000019
Figure PCTCN2019092708-appb-000020
Figure PCTCN2019092708-appb-000020
Figure PCTCN2019092708-appb-000021
Figure PCTCN2019092708-appb-000021
实施例52:化合物52的制备Example 52: Preparation of Compound 52
Figure PCTCN2019092708-appb-000022
Figure PCTCN2019092708-appb-000022
化合物52的合成路线如下：The synthetic route of compound 52 is as follows:
Figure PCTCN2019092708-appb-000023
Figure PCTCN2019092708-appb-000023
中间化合物52a的合成Synthesis of intermediate compound 52a
将1-羟基-3-甲基-9-乙基-9H-咔唑基-2-甲醛(0.05mol，11.95g)加入盛有50mL乙醇的250mL三口圆底烧瓶中，搅拌均匀后，将混合液加热至35℃使反应物全部溶于乙醇中。然后加入六氢吡啶(0.01mol，1mL)和辛酰乙酸乙酯(0.06mol，12.84g)，再将反应混合物加热至回流，搅拌反应1h。待反应完全后，将混合物冷却至室温，过滤得黄色固体，然后用乙醇重结晶，得20.7g产品，产率92％，经鉴定为化合物52a。1H-NMR(400MHz,CDCl 3)δ0.88(t，3H)，1.31-1.36(m，10H)，1.29(t，3H)，2.48(s，3H)，2.94(t，2H)，4.53(q，2H)，7.02(s，1H)，7.42(m，2H)，7.59(d，1H)，8.17(d，1H)，8.45(s，1H)。 Add 1-hydroxy-3-methyl-9-ethyl-9H-carbazolyl-2-carbaldehyde (0.05mol, 11.95g) into a 250mL three-neck round bottom flask containing 50mL of ethanol, stir well, then mix The solution was heated to 35°C to dissolve all the reactants in ethanol. Then hexahydropyridine (0.01mol, 1mL) and ethyl octanoylacetate (0.06mol, 12.84g) were added, and the reaction mixture was heated to reflux, and the reaction was stirred for 1h. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a yellow solid, and then recrystallized with ethanol to obtain 20.7 g of product with a yield of 92%, which was identified as compound 52a. 1H-NMR (400MHz, CDCl 3 ) δ 0.88 (t, 3H), 1.31-1.36 (m, 10H), 1.29 (t, 3H), 2.48 (s, 3H), 2.94 (t, 2H), 4.53 ( q, 2H), 7.02 (s, 1H), 7.42 (m, 2H), 7.59 (d, 1H), 8.17 (d, 1H), 8.45 (s, 1H).
中间化合物52b的合成Synthesis of intermediate compound 52b
将中间化合物52a(7.51g，0.02mol)加入盛有30ml四氢呋喃的100ml三口瓶中，加入15g浓盐酸(35％)，搅拌0.5h后，控制温度在5℃下滴加亚硝酸异戊酯(2.36g，0.02mol)，滴加完毕后继续在10℃下反应3h。反应完毕后，将反应液倒入水中，乙酸乙酯萃取，收集有机相，水洗有机相至中性。干燥有机相，旋蒸除去有机溶剂，用10g石油醚重结晶，低温下抽滤，得白色固体5.3g，产率63％，经鉴定为化合物52b。1H-NMR(400MHz,CDCl 3)δ0.88(t，3H)，1.31-1.36(m，8H)，1.44(t，2H)，1.29(t，3H)，2.48(s，3H)，4.53(q，2H)，7.02(s，1H)，7.42(m，2H)，7.59(d，1H)，8.17(d，1H)，8.45(s，1H)，8.70(s，1H)。 Intermediate compound 52a (7.51g, 0.02mol) was added to a 100ml three-necked flask containing 30ml of tetrahydrofuran, 15g of concentrated hydrochloric acid (35%) was added, and after stirring for 0.5h, the temperature was controlled at 5°C and isoamyl nitrite was added dropwise ( 2.36g, 0.02mol), continue to react at 10°C for 3h after the addition is complete. After the completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the organic phase was collected, and the organic phase was washed with water until it became neutral. The organic phase was dried, the organic solvent was removed by rotary evaporation, recrystallized with 10 g of petroleum ether, and suction filtered at low temperature to obtain 5.3 g of white solid, with a yield of 63%, which was identified as compound 52b. 1H-NMR (400MHz, CDCl 3 ) δ 0.88 (t, 3H), 1.31-1.36 (m, 8H), 1.44 (t, 2H), 1.29 (t, 3H), 2.48 (s, 3H), 4.53 ( q, 2H), 7.02 (s, 1H), 7.42 (m, 2H), 7.59 (d, 1H), 8.17 (d, 1H), 8.45 (s, 1H), 8.70 (s, 1H).
终产物52的合成Synthesis of end product 52
将上述中间化合物52b(4.19g，0.01mol)和30ml四氢呋喃加入到100mL三口圆底烧瓶中，然后加入乙酰氯(0.78g，0.01mol)和三乙胺(1.35g，0.013mol)，常温搅拌反应1h。终止反应，将反应液过滤后，滤液倒入水中，用乙酸乙酯萃取，收集有机相后依次用稀盐酸、饱和碳酸钠水溶液和蒸馏水洗涤，然后收集有机相，并用MgSO 4干燥过夜。过滤后减压蒸馏蒸掉有机相后，得白色固体4.42g，产率95.0％，经鉴定为化合物52。 Add the above intermediate compound 52b (4.19g, 0.01mol) and 30ml of tetrahydrofuran to a 100mL three-necked round bottom flask, then add acetyl chloride (0.78g, 0.01mol) and triethylamine (1.35g, 0.013mol), stir and react at room temperature 1h. The reaction was terminated, the reaction solution was filtered, the filtrate was poured into water, extracted with ethyl acetate, the organic phase was collected and washed with dilute hydrochloric acid, saturated sodium carbonate aqueous solution and distilled water successively, and then the organic phase was collected and dried with MgSO 4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 4.42 g of a white solid with a yield of 95.0%, which was identified as compound 52.
1H-NMR(400MHz,CDCl 3)δ0.88(t，3H)，1.31-1.36(m，8H)，1.44(t，2H)，1.29(t，3H)，2.28(s，3H),2.48(s，3H)，4.53(q，2H)，7.02(s，1H)，7.42(m，2H)，7.59(d，1H)，8.17(d，1H)，8.45(s，1H)。 1H-NMR (400MHz, CDCl 3 ) δ 0.88 (t, 3H), 1.31-1.36 (m, 8H), 1.44 (t, 2H), 1.29 (t, 3H), 2.28 (s, 3H), 2.48 ( s, 3H), 4.53 (q, 2H), 7.02 (s, 1H), 7.42 (m, 2H), 7.59 (d, 1H), 8.17 (d, 1H), 8.45 (s, 1H).
实施例53-64：化合物53-64的制备Example 53-64: Preparation of compound 53-64
重复实施例52的方法，适当改变反应原料，分别获得下表2所示的化合物53-64及其核磁数据。Repeat the method of Example 52 and appropriately change the reaction materials to obtain the compounds 53-64 and their nuclear magnetic data shown in Table 2 below.
表2Table 2
Figure PCTCN2019092708-appb-000024
Figure PCTCN2019092708-appb-000024
Figure PCTCN2019092708-appb-000025
Figure PCTCN2019092708-appb-000025
热稳定性测试Thermal stability test
利用差热分析(DSC)法测试光引发剂引发可聚合单体聚合的初始温度是衡量光引发剂热稳定性有效的方法。利用此方法，选用二缩三丙二醇二丙烯酸酯(TPGDA)作为单体，测试了化合物1、3、17、55与市售肟酯光引发剂OXE-02及CN201710620077.2专利中披露的香豆素肟酯化合物COXE-15各自引发TPGDA聚合的初始温度。差热分析测试结果见表3。Using differential thermal analysis (DSC) to test the initial temperature of the photoinitiator to initiate polymerization of the polymerizable monomer is an effective method to measure the thermal stability of the photoinitiator. Using this method, using tripropylene glycol diacrylate (TPGDA) as the monomer, the compounds 1, 3, 17, 55 and the commercially available oxime ester photoinitiator OXE-02 and the coumarone disclosed in the CN201710620077.2 patent were tested. The initial temperature at which the prime oxime ester compound COXE-15 initiates the polymerization of TPGDA. The test results of differential thermal analysis are shown in Table 3.
表3table 3
化合物名称Compound name TPGDA初始聚合温度(℃)TPGDA initial polymerization temperature (℃)
11 120120
33 130130
1717 125125
5555 127127
OXE-02OXE-02 100100
COXE-15COXE-15 9898
由表3可见，化合物1、3、17、55各自引发TPGDA聚合的初始温度均高于OXE-02(其结构见下文)和COXE-15(其结构见下文)各自引发TPGDA聚合的初始温度。It can be seen from Table 3 that the initial temperatures of compounds 1, 3, 17, and 55 each initiating TPGDA polymerization are higher than the initial temperatures of OXE-02 (see below for its structure) and COXE-15 (see below for its structure).
COXE-15结构见下:The structure of COXE-15 is as follows:
Figure PCTCN2019092708-appb-000026
Figure PCTCN2019092708-appb-000026
另外，采用化合物2、4-16、18-54和56-64中的每一个重复上述热稳定性实验。结果显示，化合物2、4-16、18-54和56-64各自引发TPGDA聚合的初始温度均高于120℃。In addition, the above thermal stability experiment was repeated using each of Compounds 2, 4-16, 18-54, and 56-64. The results showed that the initial temperature of each of Compounds 2, 4-16, 18-54 and 56-64 to initiate TPGDA polymerization was higher than 120°C.
因此，根据本发明的化合物1-64在丙烯酸酯单体中的稳定性显著地高于市售商品OXE-02和COXE-15，因而本发明的化合物1-64具有更佳的热稳定性。Therefore, the stability of the compound 1-64 in the acrylate monomer according to the present invention is significantly higher than that of the commercial products OXE-02 and COXE-15, so the compound 1-64 of the present invention has better thermal stability.
应用实施例：感光性能测试：Application Example: Photosensitive performance test:
采用乌格拉(Ugra)晒版测试条作掩膜来测试光引发剂的感光性能。乌格拉晒版测试条的各段见图1。乌格拉晒版测试条分为5个控制段，从左到右分别是：连续密度梯尺段(1)；阴阳微米等线同心圆段(2)；全阶调网点段(3)；重影控制段(4)；高光、暗调控制段(5)。第一段：连续密度梯尺段共分为13个梯度用来控制曝光量和显影。第二段：阴阳微米等线同心圆段：由12个阴阳微米等线组成的同心圆线图，分别为4、6、8、10、12、15、20、25、30、40、55、70，用于检测晒PS版时的曝光和显影情况。第三段：全阶调网点段：由10％-100％、极差为10％的评网组成，分为上下两行排列，用于测量晒版、打样和印刷的网点转移情况，并可测制出胶片网点与晒版、打样和印刷网店变化曲线图。第四段：重影控制段：由线宽60线/厘米、面积率为60％的细线条组成，它分为4小块，0°、45°、90°三个角度排列线条和有1/4的D小块中以两边90°、中间小方块45°、上下90°的小短线排列。第五段：高光、暗调控制段，精细网点段由高光小网点与暗调深网点对应排列，用于精细控制晒版曝光和显影的准确性。将包含光引发剂的感光组合物涂敷于铝基板上，然后曝光显影，从得到的图像的连续调梯尺评价感度，从微线条测试块区域评价精度，从而评价感光组合物配方的优劣。Ugra (Ugra) printing test strip as a mask to test the photosensitive performance of the photoinitiator. The sections of the Ugra printed test strip are shown in Figure 1. The test strip of Ugra printing plate is divided into 5 control sections. From left to right, they are: continuous density ladder section (1); Yin and Yang micron contour concentric circle section (2); full-step adjustment dot section (3); heavy Shadow control section (4); highlight and dark control section (5). The first section: The continuous density ladder section is divided into 13 gradients to control exposure and development. The second section: Concentric circles with yin and yang micrometer contours: Concentric circles with 12 yin and yang micrometer contours, 4, 6, 8, 10, 12, 15, 20, 25, 30, 40, 55, 70, used to detect the exposure and development of the PS plate. The third section: Full-scale adjustment dot section: It is composed of 10%-100% and a range of 10%, and is arranged in two rows. It is used to measure the transfer of printing, proofing and printing. Measure and produce the curve graphs of film dots and printing, proofing and printing online shops. The fourth section: Ghost control section: It is composed of thin lines with a line width of 60 lines/cm and an area rate of 60%. It is divided into 4 small blocks, with lines arranged at three angles of 0°, 45°, and 90°, and there is 1 The D block of /4 is arranged in small short lines with 90° on both sides, 45° in the middle, and 90° up and down. The fifth segment: highlight and dark tone control segment. The fine dot segment is arranged by high light small dots and dark tone deep dots correspondingly, used to finely control the accuracy of exposure and development. The photosensitive composition containing the photoinitiator is coated on the aluminum substrate, and then exposed and developed. The sensitivity is evaluated from the continuous step scale of the obtained image, and the accuracy is evaluated from the micro-line test block area to evaluate the quality of the photosensitive composition formulation .
具体地，按照以下步骤对式(I)化合物的感光性能进行测试。Specifically, the photosensitivity properties of the compound of formula (I) were tested according to the following steps.
(1)按照如下组成配制含有光引发剂的感光性组合物：(1) Prepare a photosensitive composition containing a photoinitiator according to the following composition:
Figure PCTCN2019092708-appb-000027
Figure PCTCN2019092708-appb-000027
上述组合物中光引发剂选自本发明的式(I)所示的香豆素(酮)肟酯类化合物或现有技术已知的光引发剂(作对比)。丙烯酸酯树脂为从上海釜顺国际贸易有限公司购买的商品名为FS2600K的树脂，官能度为2，数均分子量1400。二季戊四醇六丙烯酸酯为从上海釜顺国际 贸易有限公司购买的商品名为GM66G0C的产品。结晶紫染料为从上海国药购买的商品名为六甲基玫苯胺盐酸盐的产品。The photoinitiator in the above composition is selected from the coumarin (keto)oxime ester compound represented by formula (I) of the present invention or the photoinitiator known in the prior art (for comparison). Acrylic resin is a resin purchased from Shanghai Fushun International Trade Co., Ltd. under the trade name FS2600K, with a functionality of 2, and a number average molecular weight of 1400. Dipentaerythritol hexaacrylate is a product purchased from Shanghai Fushun International Trade Co., Ltd. under the trade name GM66G0C. Crystal violet dye is a product purchased from Shanghai Sinopharm under the trade name of hexamethyl rose aniline hydrochloride.
感光性能测试Photographic performance test
(2)将上述各组合物在黄光下搅拌混合均匀，利用离心机旋涂在预先处理好的并满足下列条件的PS铝版基上：(2) Stir and mix the above-mentioned compositions uniformly under yellow light, and spin-coating on the PS aluminum plate substrate that has been pre-treated and meets the following conditions by using a centrifuge:
铝板基尺寸：1030mm×800mmAluminum base size: 1030mm×800mm
铝板基厚度：0.28-0.3mmAluminum base thickness: 0.28-0.3mm
砂目规格：Ra＝0.5-0.6μmSand mesh specifications: Ra＝0.5-0.6μm
Rh＝0.3-0.35μmRh＝0.3-0.35μm
阳极氧化膜重量：3-3.5g/m 2 Anodized film weight: 3-3.5g/m 2
控制离心涂布机的转速，使涂在铝版基上的涂布量(以固含量计)为1.0-2.5g/m 2，在离心涂布机上初步干燥后，转移到100℃的鼓风干燥机中干燥3分钟，得紫激光CTP原版。然后，用Ugra测试条做掩膜测试版材的感光性能，曝光一段时间后用1％NaOH水溶液显影。 Control the rotating speed of the centrifugal coater so that the coating amount (in terms of solid content) coated on the aluminum plate base is 1.0-2.5g/m 2 , after preliminary drying on the centrifugal coater, transfer to a blast at 100°C Dry in the dryer for 3 minutes to get the original CTP of the violet laser. Then, use the Ugra test strip as a mask to test the photosensitive performance of the plate, and develop it with 1% NaOH aqueous solution after a period of exposure.
在曝光区，可光聚合化合物在引发剂存在下发生聚合反应，显影液中不溶，而非曝光区是可溶的，于是得到阴图。通过曝光显影，从得到的图像的连续调梯尺评价光引发剂的感度。引发剂体系感光度特征为显影后保留了(即聚合的)最高灰阶数。灰阶数越高，表明测试体系灵敏度越高。结果示于表4中。In the exposed area, the photopolymerizable compound undergoes polymerization reaction in the presence of the initiator, and is insoluble in the developer, while the non-exposed area is soluble, so a negative image is obtained. By exposure and development, the sensitivity of the photoinitiator was evaluated from the continuous scale of the obtained image. The sensitivity of the initiator system is characterized by the highest number of gray levels retained (ie, polymerized) after development. The higher the number of gray levels, the higher the sensitivity of the test system. The results are shown in Table 4.
表4Table 4
Figure PCTCN2019092708-appb-000028
Figure PCTCN2019092708-appb-000028
Figure PCTCN2019092708-appb-000029
Figure PCTCN2019092708-appb-000029
表4中，OXE-01表示1-[4-(苯硫基)苯基]-1,2-辛烷二酮2-(O-苯甲酰肟)，OXE-02表示1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-乙酮)-1-肟乙酸酯，结构式分别如下：In Table 4, OXE-01 represents 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), and OXE-02 represents 1-(6- The structural formulas of o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-ethanone)-1-oxime acetate are as follows:
Figure PCTCN2019092708-appb-000030
Figure PCTCN2019092708-appb-000030
由表4中的实验结果可以明显看出，本发明光引发剂1-64在365nm、385nm、395nm和405nm以及可见光420、436、450nm处灰阶数均高于商购的光引发剂OXE-01和OXE-02。也就是说，本发明的香豆素(酮)肟酯类光引发剂在365nm、385nm、395nm和405nm以及可见光420、436、450nm波长处感光性能更为优异，适合用于365nm、385nm、395nm、405nm以及可见光420，436，450nm的LED光源，本发明的光引发剂应用范围更广泛。It can be clearly seen from the experimental results in Table 4 that the photoinitiator 1-64 of the present invention has higher gray levels at 365nm, 385nm, 395nm and 405nm and visible light 420, 436, 450nm than the commercially available photoinitiator OXE- 01 and OXE-02. That is to say, the coumarin (ketone) oxime ester photoinitiator of the present invention has better photosensitivity at 365nm, 385nm, 395nm and 405nm and visible light wavelengths of 420, 436, 450nm, and is suitable for use at 365nm, 385nm, 395nm. With LED light sources of 405 nm and visible light of 420, 436, 450 nm, the photoinitiator of the present invention has a wider application range.
综上所述，本发明式(I)所示的香豆素(酮)肟酯类光引发剂在365nm、385nm、395nm和405nm以及可见光420、436、450nm波长处具有较好的感光性能，优于现阶段可商购的OXE-01和OXE-02等酮肟酯类光引发剂。另外本发明公开的化合物生产工艺简单，产率高，非常适合于工业生产。此类化合物与365nm、385nm、395nm、405nm以及可见光420、436、450nm的LED光源匹配性良好，且可广泛应用于紫外可见LED光固化所涉及的领域例如涂料、油墨、微电子、印刷等领域用作光引发剂。此类物质具有很好的市场前景。鉴于目前可应用于紫外可见LED的光引发剂品种较少，从一定程度上限制了紫外可见LED光源在紫外光固化领域的推广应用，故本发明光引发剂可为推动绿色环保的紫外可见LED光源在UV光固化行业的广泛应用做出贡献。In summary, the coumarin (ketone) oxime ester photoinitiator represented by the formula (I) of the present invention has better photosensitivity at 365nm, 385nm, 395nm and 405nm and visible light wavelengths of 420, 436, 450nm, It is superior to the currently commercially available ketoxime ester photoinitiators such as OXE-01 and OXE-02. In addition, the compound disclosed in the invention has a simple production process and a high yield, which is very suitable for industrial production. This kind of compound has good compatibility with 365nm, 385nm, 395nm, 405nm and visible light 420, 436, 450nm LED light sources, and can be widely used in UV-visible LED light curing fields such as coatings, inks, microelectronics, printing and other fields Used as a photoinitiator. Such substances have good market prospects. In view of the fact that there are few types of photoinitiators that can be applied to UV-visible LEDs, which limits the promotion and application of UV-visible LED light sources in the field of ultraviolet light curing to a certain extent, the photoinitiator of the present invention can be used to promote green and environmentally friendly UV-visible LEDs. The light source contributes to the wide application of UV curing industry.

Claims (12)

  1. 一种包含下式(I-1)结构部分的式(I)香豆素(酮)肟酯化合物：A coumarin (keto)oxime ester compound of formula (I) containing the following formula (I-1):
    Figure PCTCN2019092708-appb-100001
    Figure PCTCN2019092708-appb-100001
    其中：among them:
    X为O、S、NR 1或CR 2aR 2b，其中R 1、R 2a和R 2b各自独立地为H、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了H以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基； X is O, S, NR 1 or CR 2a R 2b , wherein R 1 , R 2a and R 2b are each independently H, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (sulfur ) Group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl group Or a C 6 -C 18 aryloxy (thio) group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group;
    R 3、R 4、R 5、R 6相互独立地表示氢、卤素、硝基、氰基、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了氢、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基； R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl C 1 -C 8 alkyl, C 1 -C 8 alkyl, C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl or C 6- A C 18 aryloxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano Group, C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group;
    *和**是式(I-1)结构部分与式(I)化合物中的A 1和A 2、A 2和A 3或者A 3和A 4的连接位点； * And ** are the connection points between the structural part of formula (I-1) and A 1 and A 2 , A 2 and A 3 or A 3 and A 4 in the compound of formula (I);
    A 1、A 2、A 3、A 4中连接式(I-1)结构部分的两个为碳原子，其余两个相同或不同，并且彼此独立地为CH或者CR 7，其中R 7为H、卤素、C 1-C 6烷基或C 1-C 6烷氧(硫)基，其中前述C 1-C 6烷基和C 1-C 6烷氧(硫)基可以包含一个或多个相同或不同的卤素取代基； Two of A 1 , A 2 , A 3 , and A 4 connected to the structural part of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , wherein R 7 is H , Halogen, C 1 -C 6 alkyl group or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group may contain one or more The same or different halogen substituents;
    R 8是H、卤素、C 1-C 6烷基或C 1-C 6烷氧(硫)基，其中前述C 1-C 6烷基和前述C 1-C 6烷氧(硫)基可以包含一个或多个相同或不同的卤素取代基； R 8 is H, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (thio) group, wherein the aforementioned C 1 -C 6 alkyl group and the aforementioned C 1 -C 6 alkoxy (thio) group may Contain one or more identical or different halogen substituents;
    R 9是氢、卤素、硝基、氰基、C 1-C 20烷基、C 3-C 10环烷基、C 3-C 10环烷基C 1-C 8烷基、C 1-C 8烷基C 3-C 10环烷基、C 1-C 20烷氧(硫)基、C 3-C 10环烷氧(硫)基、C 3-C 10环烷基C 1-C 8烷氧(硫)基、C 1-C 8烷基C 3-C 10环烷氧(硫)基、C 6-C 18芳基或C 6-C 18芳氧(硫)基，其中前述除了H、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基； R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl, C 1 -C 8 alkyl, C 1 -C 8 Alkyl C 3 -C 10 cycloalkyl, C 1 -C 20 alkoxy (thio) group, C 3 -C 10 cycloalkoxy (thio) group, C 3 -C 10 cycloalkyl C 1 -C 8 Alkoxy (thio) group, C 1 -C 8 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 18 aryl group or C 6 -C 18 aryloxy (thio) group, wherein the foregoing except Each group other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (sulfur) group;
    R 10是C 1-C 20烷基或C 6-C 18芳基，其中C 1-C 20烷基和C 6-C 18芳基可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基；以及 R 10 is a C 1 -C 20 alkyl group or a C 6 -C 18 aryl group, wherein the C 1 -C 20 alkyl group and the C 6 -C 18 aryl group may contain one or more substituents independently selected from the following group : Halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group; and
    n为0或1。n is 0 or 1.
  2. 根据权利要求1的化合物，其中The compound according to claim 1, wherein
    R 1、R 2a和R 2b各自独立地为H、C 1-C 10烷基、C 3-C 8环烷基、C 3-C 8环烷基C 1-C 6烷基、C 1-C 6烷基C 3-C 8环烷基、C 1-C 6烷氧(硫)基、C 3-C 8环烷氧(硫)基、C 3-C 8环烷基C 1-C 6烷氧(硫) 基、C 1-C 6烷基C 3-C 8环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了H以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基，优选的是，R 1、R 2a和R 2b各自独立地为H、C 1-C 8烷基、C 5-C 6环烷基、C 5-C 6环烷基C 1-C 4烷基、C 1-C 4烷基C 5-C 6环烷基、C 1-C 4烷氧(硫)基、C 5-C 6环烷氧(硫)基、C 3-C 6环烷基C 1-C 4烷氧(硫)基、C 1-C 4烷基C 5-C 6环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了H以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基；和/或 R 1 , R 2a and R 2b are each independently H, C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkyl, C 1- C 6 alkyl C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 Alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 8 cycloalkoxy (thio) group, C 6 -C 10 aryl group or C 6 -C 10 aryloxy (thio) group, wherein the foregoing Each group other than H may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (sulfur ) Group, preferably, R 1 , R 2a and R 2b are each independently H, C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl C 1 -C 4 alkyl group, C 1 -C 4 alkyl group, C 5 -C 6 cycloalkyl group, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy (thio) group, C 3 -C 6 Cycloalkyl C 1 -C 4 alkoxy (thio) group, C 1 -C 4 alkyl C 5 -C 6 cycloalkoxy (thio) group, C 6 -C 10 aryl or C 6 -C 10 aryloxy (Thio) group, wherein each of the aforementioned groups other than H may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) group; and/or
    R 3、R 4、R 5、R 6相互独立地表示氢、卤素、硝基、氰基、C 1-C 6烷基、C 3-C 8环烷基、C 3-C 8环烷基C 1-C 6烷基、C 1-C 6烷基C 3-C 8环烷基、C 1-C 6烷氧(硫)基、C 3-C 8环烷氧(硫)基、C 3-C 8环烷基C 1-C 6烷氧(硫)基、C 1-C 6烷基C 3-C 10环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了氢、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基，优选的是，R 3、R 4、R 5、R 6相互独立地表示氢、卤素、硝基、氰基、C 1-C 4烷基、C 5-C 6环烷基、C 5-C 6环烷基C 1-C 4烷基、C 1-C 4烷基C 5-C 6环烷基、C 1-C 4烷氧(硫)基、C 5-C 6环烷氧(硫)基、C 5-C 6环烷基C 1-C 4烷氧(硫)基、C 1-C 4烷基C 5-C 6环烷氧(硫)基、苯基或苯氧(硫)基，其中前述除了氢、卤素、硝基、氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：氟、氯、溴、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基；和/或 R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl C 1 -C 6 alkyl, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 10 cycloalkoxy (thio) group, C 6 -C 10 aryl or C 6- C 10 aryloxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano may contain one or more substituents independently selected from the following group: halogen, nitro, amino, cyano Group, C 1 -C 6 alkyl group and C 1 -C 6 alkoxy (thio) group, preferably, R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, halogen, nitro, cyano , C 1 -C 4 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkyl, C 1 -C 4 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy (thio) group, C 5 -C 6 cycloalkyl C 1 -C 4 alkoxy (thio) group, C 1 -C 4 Alkyl C 5 -C 6 cycloalkoxy (thio) group, phenyl or phenoxy (thio) group, wherein each group other than hydrogen, halogen, nitro and cyano group may contain one or more independently Substituents selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (thio) groups; and/or
    R 7为H、氟、氯、溴、C 1-C 4烷基或C 1-C 4烷氧(硫)基，其中前述C 1-C 4烷基和C 1-C 4烷氧(硫)基可以包含一个或多个相同或不同的选自氟、氯、溴的取代基；和/或 R 7 is H, fluorine, chlorine, bromine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy (sulfur) group, wherein the aforementioned C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) ) The group may contain one or more identical or different substituents selected from fluorine, chlorine and bromine; and/or
    R 8是H、氟、氯、溴、C 1-C 4烷基或C 1-C 4烷氧(硫)基，其中前述C 1-C 4烷基和C 1-C 4烷氧(硫)基可以包含一个或多个相同或不同的选自氟、氯、溴的取代基；和/或 R 8 is H, fluorine, chlorine, bromine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy (sulfur) group, wherein the aforementioned C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) ) The group may contain one or more identical or different substituents selected from fluorine, chlorine and bromine; and/or
    R 9是氢、卤素、硝基、氰基、C 1-C 8烷基、C 3-C 8环烷基、C 3-C 8环烷基C 1-C 6烷基、C 1-C 6烷基C 3-C 8环烷基、C 1-C 6烷氧(硫)基、C 3-C 8环烷氧(硫)基、C 3-C 8环烷基C 1-C 6烷氧(硫)基、C 1-C 6烷基C 3-C 8环烷氧(硫)基、C 6-C 10芳基或C 6-C 10芳氧(硫)基，其中前述除了H、卤素、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基，优选的是，R 9是氢、氟、氯、溴、硝基、氰基、C 1-C 8烷基、C 5-C 6环烷基、C 5-C 6环烷基C 1-C 4烷基、C 1-C 4烷基C 5-C 6环烷基、C 1-C 4烷氧(硫)基、C 5-C 6环烷氧(硫)基、C 5-C 6环烷基C 1-C 4烷氧(硫)基、C 1-C 4烷基C 5-C 6环烷氧(硫)基、苯基或苯氧(硫)基，其中前述除了氢、氟、氯、溴、硝基和氰基以外的各个基团可以包含一个或多个独立地选自下组的取代基：氟、氯、溴、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基；和/或 R 9 is hydrogen, halogen, nitro, cyano, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 alkyl, C 1 -C 6 alkyl C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy (thio) group, C 3 -C 8 cycloalkoxy (thio) group, C 3 -C 8 cycloalkyl C 1 -C 6 Alkoxy (thio) group, C 1 -C 6 alkyl C 3 -C 8 cycloalkoxy (thio) group, C 6 -C 10 aryl group or C 6 -C 10 aryloxy (thio) group, wherein the foregoing except Each group other than H, halogen, nitro and cyano may contain one or more substituents independently selected from the group consisting of halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group, preferably, R 9 is hydrogen, fluorine, chlorine, bromine, nitro, cyano, C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl C 1 -C 4 alkyl, C 1 -C 4 alkyl C 5 -C 6 cycloalkyl, C 1 -C 4 alkoxy (thio) group, C 5 -C 6 cycloalkoxy (Thio) group, C 5 -C 6 cycloalkyl C 1 -C 4 alkoxy (thio) group, C 1 -C 4 alkyl C 5 -C 6 cycloalkoxy (thio) group, phenyl or phenoxy (Sulfur) group, wherein each of the aforementioned groups other than hydrogen, fluorine, chlorine, bromine, nitro and cyano may contain one or more substituents independently selected from the following group: fluorine, chlorine, bromine, nitro , Amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (thio) group; and/or
    R 10是C 1-C 6烷基或C 6-C 10芳基，其中C 1-C 6烷基和C 6-C 10芳基可以包含一个或多个独立地选自下组的取代基：卤素、硝基、氨基、氰基、C 1-C 6烷基和C 1-C 6烷氧(硫)基，优选的是，R 10是C 1-C 4烷基或苯基，其中C 1-C 4烷基和苯基可以包含一个或多个独立地选自下组的取代基：氟、氯、溴、硝基、氨基、氰基、C 1-C 4烷基和C 1-C 4烷氧(硫)基。 R 10 is a C 1 -C 6 alkyl group or a C 6 -C 10 aryl group, wherein the C 1 -C 6 alkyl group and the C 6 -C 10 aryl group may contain one or more substituents independently selected from the following group : Halogen, nitro, amino, cyano, C 1 -C 6 alkyl and C 1 -C 6 alkoxy (thio) group, preferably, R 10 is C 1 -C 4 alkyl or phenyl, wherein The C 1 -C 4 alkyl group and the phenyl group may contain one or more substituents independently selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C 1 -C 4 alkyl and C 1 -C 4 alkoxy (sulfur) group.
  3. 根据权利要求1的化合物，其中The compound according to claim 1, wherein
    X为O、S、NR 1或CR 2aR 2b，其中R 1为C 1-C 8烷基、苯基或萘基，其中所述苯基或萘基 可以包含一个或多个相同或不同的C 1-C 4烷基取代基；以及R 2a和R 2b相同或不同，且各自独立地为H、C 1-C 6烷基、C 5-C 6环烷基C 1-C 4烷基或C 1-C 4烷氧基C 1-C 4烷基； X is O, S, NR 1 or CR 2a R 2b , wherein R 1 is C 1 -C 8 alkyl, phenyl or naphthyl, wherein said phenyl or naphthyl may contain one or more of the same or different C 1 -C 4 alkyl substituent; and R 2a and R 2b are the same or different, and are each independently H, C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 4 alkyl Or C 1 -C 4 alkoxy C 1 -C 4 alkyl;
    R 3、R 4、R 5、R 6相互独立地表示氢、硝基、C 1-C 4烷基、C 1-C 4烷氧(硫)基或苯基； R 3 , R 4 , R 5 , and R 6 independently represent hydrogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy (thio) or phenyl;
    A 1、A 2、A 3、A 4中连接式(I-1)结构部分的两个为碳原子，其余两个相同或不同，并且彼此独立地为CH或者CR 7，其中R 7H或C 1-C 4烷基； Two of A 1 , A 2 , A 3 , and A 4 connecting the structural parts of formula (I-1) are carbon atoms, and the remaining two are the same or different, and independently of each other are CH or CR 7 , wherein R 7 H or C 1 -C 4 alkyl;
    R 8是H或C 1-C 4烷基； R 8 is H or C 1 -C 4 alkyl;
    R 9是氰基、C 1-C 7烷基、卤代C 1-C 6烷基或C 5-C 6环烷基C 1-C 4烷基；以及 R 9 is cyano, C 1 -C 7 alkyl, halo C 1 -C 6 alkyl or C 5 -C 6 cycloalkyl C 1 -C 4 alkyl; and
    R 10是C 1-C 4烷基或苯基。 R 10 is C 1 -C 4 alkyl or phenyl.
  4. 根据权利要求1的化合物，其中该化合物选自下组：The compound according to claim 1, wherein the compound is selected from the group consisting of:
    Figure PCTCN2019092708-appb-100002
    Figure PCTCN2019092708-appb-100002
    Figure PCTCN2019092708-appb-100003
    Figure PCTCN2019092708-appb-100003
    Figure PCTCN2019092708-appb-100004
    Figure PCTCN2019092708-appb-100004
    Figure PCTCN2019092708-appb-100005
    Figure PCTCN2019092708-appb-100005
  5. 一种制备如权利要求1-4中任一项所要求的化合物的方法，包括以下步骤：A method for preparing a compound as claimed in any one of claims 1-4, comprising the following steps:
    (1)肟化反应：当n为0时，使式(II)化合物与羟胺、盐酸羟胺或其任意组合进行肟化反应，得到式(IIIa)化合物(1) The oximation reaction: when n is 0, the compound of formula (II) is subjected to oximation reaction with hydroxylamine, hydroxylamine hydrochloride or any combination thereof to obtain the compound of formula (IIIa)
    Figure PCTCN2019092708-appb-100006
    Figure PCTCN2019092708-appb-100006
    当n为1时，使式(II)化合物与亚硝酸、亚硝酸盐、亚硝酸烷基酯或其任意组合进行肟化反应，得到式(IIIb)化合物:When n is 1, the compound of formula (II) is subjected to oximation reaction with nitrous acid, nitrite, alkyl nitrite or any combination thereof to obtain a compound of formula (IIIb):
    Figure PCTCN2019092708-appb-100007
    Figure PCTCN2019092708-appb-100007
    其中，式(II)、(IIIa)和(IIIb)中的A 1、A 2、A 3、A 4、R 8和R 9如权利要求1-4中任一项所定义；以及 Wherein, A 1 , A 2 , A 3 , A 4 , R 8 and R 9 in formulas (II), (IIIa) and (IIIb) are as defined in any one of claims 1-4; and
    (2)将式(IIIa)或(IIIb)化合物酯化，得到式(I)化合物。(2) Esterify the compound of formula (IIIa) or (IIIb) to obtain the compound of formula (I).
  6. 根据权利要求5的方法，其中The method according to claim 5, wherein
    当n为0时：When n is 0:
    肟化反应在乙酸钠、吡啶、哌啶、三乙胺、四甲基氢氧化铵或其混合物作为催化剂存在下进行；和/或，肟化反应的温度为60-120℃；和/或，式(II)化合物与选自羟胺和/或盐酸羟胺的化合物的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1；或The oximation reaction is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof as a catalyst; and/or, the temperature of the oximation reaction is 60-120°C; and/or, The molar ratio of the compound of formula (II) to the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is 1:1.5-1.5:1, preferably 1:1.2-1.2:1; or
    当n为1时，When n is 1,
    肟化反应在浓盐酸存在下进行；和/或，肟化反应的温度为-30至20℃，优选5-20℃；和/或，式(II)化合物与选自亚硝酸、亚硝酸盐和/或亚硝酸烷基酯的化合物的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。The oximation reaction is carried out in the presence of concentrated hydrochloric acid; and/or the temperature of the oximation reaction is -30 to 20°C, preferably 5-20°C; and/or, the compound of formula (II) is selected from nitrous acid and nitrite And/or the molar ratio of the alkyl nitrite compound is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
  7. 根据权利要求5或6的方法，其中The method according to claim 5 or 6, wherein
    亚硝酸烷基酯为亚硝酸C 1-C 6烷基酯，例如亚硝酸甲酯、亚硝酸乙酯、亚硝酸异丙酯、亚硝酸丁酯、亚硝酸异戊酯；和/或， The alkyl nitrite is a C 1 -C 6 alkyl nitrite, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite; and/or,
    步骤(2)的酯化采用选自下式(IVa)、(IVb)和(IVc)化合物的酯化试剂进行：The esterification of step (2) is carried out with an esterification reagent selected from compounds of the following formulas (IVa), (IVb) and (IVc):
    Figure PCTCN2019092708-appb-100008
    Figure PCTCN2019092708-appb-100008
    其中X为卤素，尤其是氯，和R 7如权利要求1-4中任一项所定义。 Wherein X is halogen, especially chlorine, and R 7 is as defined in any one of claims 1-4.
  8. 根据权利要求5-7中任一项的方法，其中酯化反应在选自下组的一种或多种催化剂存在下进行：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙和叔胺，例如三烷基胺，如三甲基胺和三乙胺。The method according to any one of claims 5-7, wherein the esterification reaction is carried out in the presence of one or more catalysts selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, P-toluene sulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines, such as trialkylamines, such as Methylamine and triethylamine.
  9. 根据权利要求7或8的方法，其中式(IIIa)或式(IIIb)化合物与选自(IVa)、(IVb)和(IVc)化合物的酯化试剂的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。The method according to claim 7 or 8, wherein the molar ratio of the compound of formula (IIIa) or formula (IIIb) to the esterification agent selected from the group consisting of compounds (IVa), (IVb) and (IVc) is 1:1.5-1.5:1 , Preferably 1:1.2-1.2:1.
  10. 根据权利要求5-9中任一项的方法，还包括：使式(V)化合物与式(VI)化合物进行诺文葛尓缩合反应，得到式(II)化合物，The method according to any one of claims 5-9, further comprising: subjecting the compound of formula (V) to the compound of formula (VI) to carry out a Novengal condensation reaction to obtain a compound of formula (II),
    Figure PCTCN2019092708-appb-100009
    Figure PCTCN2019092708-appb-100009
    其中式(V)化合物中的A 1、A 2、A 3、A 4和R 8如权利要求1-4中任一项所定义，以及式(VI)化合物中的R 9如权利要求1-4中任一项所定义，和R 11为C 1-C 12烷基，优选C 1-C 6烷基。 Wherein A 1 , A 2 , A 3 , A 4 and R 8 in the compound of formula (V) are as defined in any one of claims 1-4, and R 9 in the compound of formula (VI) is as defined in claim 1- As defined in any one of 4, and R 11 is C 1 -C 12 alkyl, preferably C 1 -C 6 alkyl.
  11. 根据权利要求10的方法，其中The method according to claim 10, wherein
    诺文葛尓缩合反应在六氢吡啶、吡啶、哌啶、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙、四甲基氢氧化铵、叔胺(例如三烷基胺，如三甲基胺和三乙胺)或其任意组合存在下进行；和/或，Condensation reaction of Novengrass in hexahydropyridine, pyridine, piperidine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethyl Ammonium hydroxide, tertiary amine (for example, trialkylamine, such as trimethylamine and triethylamine) or any combination thereof; and/or,
    诺文葛尓缩合反应的温度为0-150℃，优选0-100℃；和/或The temperature of the Novenge condensation reaction is 0-150°C, preferably 0-100°C; and/or
    式(V)化合物和式(VI)化合物的摩尔比为1:1.5-1.5:1，优选为1:1.2-1.2:1。The molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1.5-1.5:1, preferably 1:1.2-1.2:1.
  12. 如权利要求1-4中任一项所要求的式(I)化合物作为光引发剂的用途，尤其是在UV-LED光固化体系中作为光引发剂的用途，特别是在辐射波长为300-500nm、特别是350-450nm、尤其是在365-450nm的光固化体系中作为光引发剂的用途。The use of the compound of formula (I) as claimed in any one of claims 1 to 4 as a photoinitiator, especially as a photoinitiator in a UV-LED light curing system, especially at a radiation wavelength of 300- Use of 500nm, especially 350-450nm, especially 365-450nm as a photoinitiator in the photocuring system.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101370772A (en) * 2006-01-13 2009-02-18 东洋油墨制造株式会社 Diketooxime ester compound and use thereof
CN104817653A (en) * 2015-04-22 2015-08-05 江南大学 Coumarin oxime ester photoinitiator and preparation method thereof
CN109305951A (en) * 2017-07-26 2019-02-05 湖北固润科技股份有限公司 Cumarin oxime ester compound and its preparation and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101370772A (en) * 2006-01-13 2009-02-18 东洋油墨制造株式会社 Diketooxime ester compound and use thereof
CN104817653A (en) * 2015-04-22 2015-08-05 江南大学 Coumarin oxime ester photoinitiator and preparation method thereof
CN109305951A (en) * 2017-07-26 2019-02-05 湖北固润科技股份有限公司 Cumarin oxime ester compound and its preparation and application

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