CN106278967B - Acyl oxime ester compound for UV curing material and synthetic method and application thereof - Google Patents

Acyl oxime ester compound for UV curing material and synthetic method and application thereof Download PDF

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CN106278967B
CN106278967B CN201510297585.2A CN201510297585A CN106278967B CN 106278967 B CN106278967 B CN 106278967B CN 201510297585 A CN201510297585 A CN 201510297585A CN 106278967 B CN106278967 B CN 106278967B
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cycloalkyl
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CN106278967A (en
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胡海军
吴进
谭玉东
黎水林
黄达
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Jiangsu Hecheng Advanced Materials Co ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/68—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with at least one of the esterifying carboxyl groups bound to a carbon atom of a six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
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    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

Abstract

The invention provides a compound with a novel acyl oxime ester structure shown in a general formula I, wherein the compound has a good ultraviolet absorption effect, has the characteristics of good solubility, high thermal stability, high photosensitive activity and low toxicity, and the application performance of the compound is obviously superior to that of similar products.
Figure DDA0000730321940000011

Description

Acyl oxime ester compound for UV curing material and synthetic method and application thereof
Technical Field
The invention relates to a photoinitiator, in particular to a photoinitiator for a UV curing material.
Background
Ultraviolet (UV) curing, abbreviated as photocuring technology, is a high-efficiency, environment-friendly, energy-saving and high-quality material surface treatment technology, is widely applied to the fields of advertisement, printing, high-grade commodity packaging, decoration, electronics, communication and the like, and the existing photocuring products mainly appear in the forms of UV coatings, UV inks, UV adhesives, photosensitive printing plates, photoresists, rapid photo-curing materials and the like.
Photocuring is a process of irradiating a liquid material with chemical activity by using ultraviolet light to initiate rapid polymerization and crosslinking of the liquid material and enable the liquid material to be cured instantly.
Compared with other curing methods such as thermal curing, photo-curing has the following advantages: 1. the speed is high, and the photocuring product can be cured within a few seconds generally, and is the fastest curing speed in various printing inks, coatings and adhesives at present; 2. the application range is wide, and the photocuring product can be suitable for various base materials, and is particularly suitable for some heat-sensitive materials such as paper, electronic components, plastics and the like: 3. the energy consumption is low, the light-cured product is rapidly cured at normal temperature, and the energy consumption is only 1/10-1/5 of heat curing; 4. the pollution is low, and the photocuring product is basically free of Volatile Organic Compounds (VOC), and is an environment-friendly product.
In daily life, light-cured products are ubiquitous and change our lives. For example, in the plate coating protection and decoration industry, the UV wood coating can improve the wear resistance, scratch resistance and resistance of the plate, can also greatly improve the decoration effect through UV three-dimensional coating, and is mainly applied to the protection and decoration of furniture and solid wood floors; in the printing industry, the use of the UV offset printing ink changes the defect that the printing ink of the prior printed matter is not dry and needs powder spraying, and has bright and saturated color and better definition, and the UV printing ink becomes the vitality of outdoor large advertisements and signboards and is also an important printing material for high-grade cigarettes, wines, health products, cosmetics and food packaging; photoresists are relatively early photocured products used in the optoelectronic, information and communications industries, particularly for the fabrication of some microelectronic products. Such as extreme ultraviolet photoresist used for manufacturing large-scale integrated circuits, the photoresist is not separated in the manufacturing of some key components in liquid crystal displays, plasma displays and organic electroluminescent displays.
The Bayer company developed the first generation of ultraviolet light curing woodware coating in 1968, and the industrialization of the light curing technology was realized firstly. With the rapid development of the light curing technology, the application field is continuously expanded, and a new industry is formed. In the last 70 and 80 years, the european and american society for radiation curing established to promote the research and development of the photo-curing technology, and in developed countries and regions such as north america, europe and japan, companies across countries such as basf, bayer and dow have joined photo-curing production, and have become industries with certain market scales. China develops the light curing technology from the 80 th of the last century, and the development is slow due to the limitation of raw materials and equipment. In the 90 s, the development of the photocuring industry in China is greatly promoted by the introduction of ultraviolet curing technology and equipment, and in the 21 st century, the photocuring industry in China is developed more rapidly, particularly, the photoinitiator has become the largest production and export country in the world, and a new high-tech industry is formed preliminarily. Nowadays, sustainable development is advocated greatly, a harmonious society is established, and environmental protection is enhanced, which provides opportunities for the development of the photocuring industry in China.
The light curing material (light curing paint, printing ink, photoresist, RGB and BM) mainly consists of unsaturated resin and monomer material thereof, and a photoinitiator or a sensitizer is needed to enable the light curing material to generate polymerization curing reaction under the irradiation of ultraviolet light, X-ray or laser. The added photoinitiator or sensitizer can generate active groups under the irradiation of ultraviolet light, X-rays or laser with certain wavelength, and the unsaturated groups in the photocuring material are excited to carry out a polymerization reaction to cause the curing of the photocuring material.
Some of the widely used conventional initiators among the photocurable materials are benzoin derivatives, benzil ketals, α -dialkoxyphenones, α -hydroxyalkylbenzones, α -aminoalkylbenzones, acylphosphine oxides, benzophenones/amines, michael ketones, thioxanthones/amines, amine accelerators, aromatic diazonium salts, arylsulfonium and sulfonium salts, ferrocene and ferrocene, hexaaryldiimidazoles, triazines and conventional oxime esters, which are more or less susceptible to the disadvantages of low sensitivity (low polymerization rate and conversion), poor solubility (low transparency and high residue lithography), large influence of oxygen on photocuring and poor storage stability, and thus their use as well as photosensitive materials is greatly limited and greatly affects the performance of photosensitive materials, in particular the manufacturing requirements for new generation of large screen L CD key parts BM and CF, the emergence of oxime ester photoinitiators, which largely solve the above-mentioned problems, the photochemical properties of oxime ester compounds appear in literature a.7, pigeon, L, german, p, german, p.
The 'reactivation' of the oxime ester photoinitiator appears in the documents R.Malliviet al, J.Photochem.Photobiol.A: Chemistry 2001,138,193 and L. L ave et aI, J.Photochem.Photobiol.A: Chemistry 2002.151,27 for the first time, because diphenyl sulfide or carbazole groups are introduced into the oxime ester compound, and the groups have larger conjugated systems and stronger intramolecular electron transfer characteristics, the stability and the photosensitive activity of the oxime ester compound are greatly improved, two representative oxime ester photoinitiators widely used at present are OXE-1 and OXE-2, and the structural formula is shown as follows:
Figure BDA0000730321920000021
the OXE-l is the most typical ketoxime ester photoinitiator, which is mainly applied to manufacturing BM and RGB of a large screen L CD display and has high price, and the structural formula of the photoinitiator is applied and protected by foreign companies, and the patent publications CN99108598 and CN02811675 have the advantages of complex synthetic method, high synthetic cost, poor application performance and poor thermal stability of products with the structure.
Now, requirements for the effects of photoinitiators and the properties of decomposition products thereof, such as toxicity, odor, migration, etc., are becoming higher and higher, and the development of macromolecular photoinitiators with good solubility, low odor or no odor and low migration, which have good properties, will become the main direction for future development. However, most of the currently commercialized macromolecular photoinitiators are expensive or have certain defects in product performance, so that products with low price and good performance are urgently needed to replace the products.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the application performance of the existing acyloxime ester photoinitiator, the invention aims to provide an acyloxime ester compound which has the advantages of good solubility, good thermal stability, high reaction activity, low production cost, low price, basically no odor, low mobility and high use safety (low toxicity).
The invention also aims to provide a preparation method of the acyl oxime ester compound.
The invention further aims to provide application of the acyloxime ester compound in a UV (ultraviolet) photocuring material.
The technical scheme is as follows: in order to achieve the above object, the present invention provides an acyloxime ester compound, which has a structure represented by general formula i:
Figure BDA0000730321920000031
the R is1And R4Are the same or different and are each independently selected from
Figure BDA0000730321920000032
Figure BDA0000730321920000033
Wherein, R is3Is selected from-H, -NO2Alkyl or alkoxy of 1-8 carbon atoms, cycloalkyl of 3-8 carbon atoms, alkylene of 2-8 carbon atoms,
Figure BDA0000730321920000034
Said Y is1、Y2And Y3Identical or different, each independently selected from-H, -CH3Alkyl or alkoxy of 2-8 carbon atoms, cycloalkyl of 3-8 carbon atoms, alkylene of 2-8 carbon atoms;
said X 'and Y' are the same or different and are each independently selected from-S-, -S-S-, -O-, -CO-;
r is as defined above1And R4In selected substituents, one or more-H in the cyclic structure may be replaced by-F, -Cl, -Br, -I, -NO2、-COOR′1、-CONR′2、-OR′3、
Figure BDA0000730321920000041
Alkyl or alkoxy of 1 to 8 carbon atoms or alkenyl of 2 to 8 carbon atoms, wherein R'1And R'2Each independently selected from-H,
Figure BDA0000730321920000042
Figure BDA0000730321920000043
Alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, R'3Selected from-H, alkyl of 1-8 carbon atoms, cycloalkyl of 3-8 carbon atoms, alkenyl of 2-8 carbon atoms or carbon chain carbonyl of 1-8 carbon atoms, wherein the carbonyl in the carbon chain carbonyl of 1-8 carbon atoms is terminal and located at the connecting bond;
the R is2Selected from-H, alkyl or alkoxy of 1 to 20 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or alkenyl of 2 to 20 carbon atoms;
or R2And R1The groups shown are the same and are each,
the premise is that: the R is1And R4At least one of
Figure BDA0000730321920000044
In some preferred embodiments of the invention, R is1And R4At least one of
Figure BDA0000730321920000045
In some preferred embodiments of the invention, R is1And R4Wherein one or more-H in the cyclic structure may be-F, -NO2、-COOR′1、-CONR′2、-OR′3Alkyl or alkoxy of 1 to 8 carbon atoms, wherein R'1And R'2Each independently selected from-H,
Figure BDA0000730321920000046
Alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, R'3Selected from-H, alkyl of 1-8 carbon atoms or carbon chain carbonyl of 1-8 carbon atoms, wherein the carbonyl in the carbon chain carbonyl of 1-8 carbon atoms is terminal and located at the connecting bond.
In some preferred embodiments of the present invention, preferably, the R is1And R4Are the same or different and are each independently selected from
Figure BDA0000730321920000047
Figure BDA0000730321920000051
In some preferred embodiments of the invention, R is2Selected from-H, alkyl or alkoxy of 1-20 carbon atoms, alkylene of 2-20 carbon atoms or with R1The groups shown are the same.
In some embodiments of the invention, preferably, R is2Selected from-H, 1-20 carbonsAn alkyl or alkoxy group having 2 to 20 carbon atoms, an alkenyl group,
Figure BDA0000730321920000052
Figure BDA0000730321920000053
In some embodiments of the invention, preferably, R is2Selected from the group consisting of-H, alkyl or alkoxy of 1 to 15 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 15 carbon atoms,
Figure BDA0000730321920000054
Figure BDA0000730321920000055
In some embodiments of the invention, preferably, R is2Selected from the group consisting of-H, alkyl or alkoxy of 1 to 15 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 15 carbon atoms,
Figure BDA0000730321920000061
Figure BDA0000730321920000062
In some embodiments of the invention, preferably, R is2Selected from alkyl or alkoxy of 1-15 carbon atoms, cycloalkyl of 3-8 carbon atoms and alkylene of 2-15 carbon atoms.
In some embodiments of the invention, R is3Is selected from-H, -NO2Alkyl or alkoxy of 1-8 carbon atoms, cycloalkyl of 3-6 carbon atoms, alkylene of 2-8 carbon atoms,
Figure BDA0000730321920000063
In some embodiments of the invention, X 'and Y', which are the same or different, are each independently selected from-S-, -S-, -O-, -CO-.
Some of the present inventionIn an embodiment, the R is3Selected from-H, alkyl or alkoxy of 1-8 carbon atoms.
In some embodiments of the invention, Y is1、Y2And Y3The same or different, each independently selected from-H, alkyl or alkoxy of 1-8 carbon atoms.
In some embodiments of the invention, R is3represents-H.
In some embodiments of the invention, Y is1、Y2And Y3represents-CH3。
In some embodiments of the invention, the compound of formula I is selected from the group consisting of compounds of formulae I-1 to I-17:
Figure BDA0000730321920000064
Figure BDA0000730321920000071
Figure BDA0000730321920000081
Figure BDA0000730321920000091
Figure BDA0000730321920000092
and
Figure BDA0000730321920000093
wherein the content of the first and second substances,
the R is2Selected from-H, alkyl or alkoxy of 1-20 carbon atoms, cycloalkyl of 3-8 carbon atoms, alkylene of 2-20 carbon atoms or R1The groups shown.
The invention also provides a preparation method of the acyl oxime ester compound shown in the general formula I, which comprises the following steps:
a. synthesis of intermediates I-A: using benzene, diphenyl sulfide or thioxanthone as initial raw material and R2Acyl halide compounds of the groups are synthesized into an intermediate I-A through Friedel-crafts acylation reaction under the action of ferric trichloride, aluminum trichloride or zinc chloride and the like:
Figure BDA0000730321920000101
b. synthesis of intermediates I-B: and (3) carrying out oxidation reaction on the intermediate I and methyl nitrite, ethyl nitrite or isoamyl nitrite and the like in the presence of hydrogen chloride or hydrochloric acid to generate acyl oxime intermediates I-B:
Figure BDA0000730321920000102
c. synthesis of acyloxime ester photoinitiator: and (3) synthesizing the intermediate I-B and acyl halide or acid anhydride containing M1 structure into the compound of the general formula I in the presence of acid-binding agents such as pyridine or triethylamine and the like and taking dichloromethane, dichloroethane or dioxane and the like as solvents.
Figure BDA0000730321920000103
Wherein the content of the first and second substances,
the R is1And R4Are the same or different and are each independently selected from
Figure BDA0000730321920000104
Figure BDA0000730321920000105
Wherein, R is3Is selected from-H, -NO2Alkyl or alkoxy of 1-8 carbon atoms, cycloalkyl of 3-8 carbon atoms, alkylene of 2-8 carbon atoms,
Figure BDA0000730321920000106
Said Y is1、Y2And Y3Identical or different, each independently selected from-H, -CH3Alkyl or alkoxy of 2-8 carbon atoms, cycloalkyl of 3-8 carbon atoms, alkylene of 2-8 carbon atoms;
said X 'and Y' are the same or different and are each independently selected from-S-, -S-S-, -O-, -CO-;
r is as defined above1And R4In selected substituents, one or more H atoms in the cyclic structure may be replaced by F, Cl, Br, I, OH, NO2、
Figure BDA0000730321920000111
Alkyl or alkoxy of 1 to 8 carbon atoms or alkenyl of 2 to 8 carbon atoms,
the R is2Selected from-H, alkyl or alkoxy of 1-8 carbon atoms, cycloalkyl of 3-8 carbon atoms or alkylene of 2-8 carbon atoms
Or with R1The groups shown are the same;
the premise is that: the R is1Is composed of
Figure BDA0000730321920000112
When R is in the above-mentioned range4Is not that
Figure BDA0000730321920000113
And said R is1And R4At least one of
Figure BDA0000730321920000114
X is halogen.
The specific reaction route is as follows:
Figure BDA0000730321920000115
the specific operation for synthesizing the intermediate I-A in the step a is as follows: adding a starting material (benzene, diphenyl sulfide or thiaanthracene) into an organic solvent A under the protection of nitrogenKetones, etc.), AlCl3Stirring and mixing, cooling to about-5 ℃ in ice-salt water bath, and dripping R2And (3) controlling the temperature of the mixed liquid of the acyl halide compound of the group and the organic solvent A at-5 ℃, removing the ice salt water bath after dropwise adding for about 2 hours, naturally returning to the room temperature, continuously stirring for reacting for 2-3 hours, and carrying out post-treatment to obtain a white solid intermediate I-A. Starting materials, AlCl3And R2The optimal molar ratio of the acyl halide compounds of the groups is 1: 1.1: 1.05.
the organic solvent A in the invention is dichloromethane, dichloroethane, chloroform or carbon tetrachloride.
The specific operation for synthesizing the intermediate I-B in the step B is as follows: and adding the intermediate I-A into the organic solvent B, stirring uniformly, adding hydrochloric acid or hydrogen chloride at room temperature, introducing methyl nitrite or dropwise adding isoamyl nitrite, stirring at room temperature for reacting for 3-5 h, concentrating under reduced pressure, and recrystallizing to obtain a white solid intermediate I-B.
The organic solvent B in the invention is tetrahydrofuran, isopropyl ether, methyl tert-butyl ether, diethyl ether, anisole, butyl ether, ethylene glycol diethyl ether, dioxane and the like.
The specific operation of synthesizing the acyloxime ester photoinitiator in the step c comprises the following steps: adding the intermediate I-B and pyridine or triethylamine into the organic solvent C, stirring uniformly, cooling to about 0 ℃ in an ice salt water bath, starting to dropwise add the mixed solution of the acyl halide compound of the M1 group and the organic solvent C, after dropwise adding for about 1.5h, naturally returning to room temperature, continuously stirring for reacting for about 2h, and treating to obtain light yellow oily liquid, namely the acyl oxime ester compound shown in the general formula I.
The organic solvent C in the invention is dichloromethane, dichloroethane, chloroform, carbon tetrachloride or dioxane. The molar ratio of the intermediate I-B to the acyl halide or the acid anhydride containing the M1 structure is 1: 1.1.
The invention also provides the performance of the acyl oxime ester compound shown in the general formula I and application of the acyl oxime ester compound in a UV (ultraviolet) photocuring material.
The method has the beneficial effects that under the condition that the mass concentration of the acyl oxime ester compound is the same, the ultraviolet absorption spectrogram of the acyl oxime ester compound is the same as or similar to that of OXE-1, wherein the thermal stability of the acyl oxime ester compound is obviously more stable than that of OXE-1, part of the substance structure of the acyl oxime ester compound has obvious red shift with OXE-1 in the ultraviolet absorption spectrogram, and has larger absorption at 300-365 nm, so that L ED cold light source can be used as an activation light source, and the application performance (light sensitivity, thermal stability and solubility) of the acyl oxime ester compound is better than that of the existing OXE-1.
Meanwhile, compared with the existing like products, the acyl oxime ester compound shows remarkably improved comprehensive application performance (solubility, stability, developability, surface crease resistance of a formed film and use safety) on the whole, and in addition, the acyl oxime ester compound also has very excellent storage stability and very high photocuring activity, can be crosslinked and cured under low exposure dose, has an excellent curing effect, does not generate toxic and harmful substances in the photocuring process, and has high use safety. The prepared film has smooth edge without defects, no scum, good integrity of the whole pattern and no wrinkles on the surface, and the prepared color filter has high optical transparency and no light leakage. The outstanding effects are exhibited in the odor property, storage stability, developability, surface crease resistance of a formed film, safety in use, and the like of the photosensitive composition.
Drawings
FIG. 1 is a graph showing a comparison of UV absorption of (E) -2- ((3-benzoyloxy-2, 4, 6-trimethylbenzoyloxy) imino) -1- (4- (phenylmercapto) phenyl) oct-1-one (compound I-2-1) and OXE-1, wherein A is the UV absorption of (E) -2- ((3-benzoyloxy-2, 4, 6-trimethylbenzoyloxy) imino) -1- (4- (phenylmercapto) phenyl) oct-1-one.
FIG. 2 shows nuclear magnetism of (E) -2- ((hydroxyimino) -1- (4- (benzenemercapto) phenyl) oct-1-one (Compound I-2-1-3)1HNMR spectrogram.
FIG. 3 shows nuclear magnetism of (E) -2- ((3-benzoyloxy-2, 4, 6-trimethylbenzoyloxy) imino) -1- (4- (benzenemercapto) phenyl) oct-1-one (Compound I-2-1)1HNMR spectrogram.
FIG. 4 is (E)Nuclear magnetism of 1- (3-benzoyl-2, 4, 6-trimethylphenyl) -2- (hydroxyimino) oct-1-one (Compound I-7-1-3)1HNMR spectrogram.
FIG. 5 shows nuclear magnetism of (E) -1- (3-benzoyl-2, 4, 6-trimethylphenyl) -2- ((4- (benzenemercapto) benzoyloxy) imino) oct-1-one (Compound I-7-1)1HNMR spectrogram.
FIG. 6 shows nuclear magnetism of (E) -2- (3-benzoyl-2, 4, 6-trimethylbenzoylimidoyl) -1- (3-benzoyl-2, 4, 6-trimethylphenyl) oct-1-one (Compound I-13-1)1HNMR spectrogram.
FIG. 7 is nuclear magnetism of 1-chloro-4- (2-hydroxyimino) octanoate-based thioxanthone (compound I-4-1-3)1HNMR spectrogram.
FIG. 8 shows nuclear magnetism of (E) -1-chloro- (2- (3-benzoyl-2, 4, 6-trimethylbenzoylimido ester)) -4-octanoate thioxanthone (Compound I-4-1)1HNMR spectrogram.
FIG. 9 shows a UV absorption spectrum of (E) -1- (3-benzoyl-2, 4, 6-trimethylphenyl) -2- ((4- (benzenethiol) benzoyloxy) imino) oct-1-one (Compound I-7-1).
FIG. 10 shows a UV absorption spectrum of (E) -2- (3-benzoyl-2, 4, 6-trimethylbenzoylimidoyl) -1- (3-benzoyl-2, 4, 6-trimethylphenyl) oct-1-one (compound I-13-1).
FIG. 11 shows a UV absorption spectrum of (E) -1-chloro- (2- (3-benzoyl-2, 4, 6-trimethylbenzoylimido ester)) -4-octanoate thioxanthone (compound I-4-1).
Detailed Description
The compounds of the general formula I according to the invention are preferably one or more of the following compounds:
Figure BDA0000730321920000131
Figure BDA0000730321920000132
Figure BDA0000730321920000141
Figure BDA0000730321920000151
Figure BDA0000730321920000161
Figure BDA0000730321920000171
Figure BDA0000730321920000181
Figure BDA0000730321920000191
Figure BDA0000730321920000201
Figure BDA0000730321920000211
Figure BDA0000730321920000221
Figure BDA0000730321920000231
Figure BDA0000730321920000241
Figure BDA0000730321920000251
Figure BDA0000730321920000261
example 1
Preparation of n-octanoyl chloride (I-2-1-1)
Figure BDA0000730321920000262
Adding 200ml of dichloromethane, 100g of n-octanoic acid and 2 drops of DMF into a three-neck flask, putting up a reflux condenser tube, a constant-pressure dropping funnel, a drying tube and an alkali liquor tail gas absorption device, heating to reflux, slowly dropping 165g of thionyl chloride and 30ml of dichloromethane mixed solution, after dropping for about 1h, refluxing for 2h, carrying out reduced pressure concentration, adding 100ml of fresh dichloromethane, and carrying out reduced pressure concentration again to obtain 114g of light yellow solution, namely the compound I-2-1-1.
Preparation of 1- (4- (phenylmercapto) phenyl) oct-1-one (Compound I-2-1-2)
Figure BDA0000730321920000263
123g (0.66mol) of diphenyl sulfide and 350ml of dichloromethane are added into a three-neck flask, the temperature of an ice salt water bath is reduced to-5 ℃, nitrogen is introduced, and 97.1g (0.73mol) of anhydrous A1C1 is added3Adding a drying tube, a reflux condenser tube and tail gas absorption, slowly dropping a mixed solution of 113g (0.69mol) of n-octanoyl chloride and 50ml of dichloromethane, controlling the temperature at-5 ℃, after dropping for about 2 hours, removing an ice salt water bath, naturally returning to room temperature, continuously stirring for 2-3 hours, monitoring the reaction completion by T L C, slowly pouring the reactant into 200ml of 10% ice diluted hydrochloric acid, stirring for 30 minutes, separating liquid, extracting an aqueous phase by 100ml of dichloromethane, combining organic phases, washing by 3 × 100ml of water, washing by 2% NaHCO 100ml of water, and then adding a solvent, namely sodium chloride, sodium chloride and sodium chloride into the mixture3Adjusting the solution to neutral, separating, washing with 100ml water for 1 time, and removing anhydrous MgSO4Drying, filtering, concentrating under reduced pressure, recrystallizing to obtain white solid 175g, i.e. compound I-2-1-2, with yield of 85%. MP: 31-32 ℃; MS: 312.15.
1HNMR(300MHz，CDCl3)，＝0.87(t，J＝6.8Hz，3H)，1.26～1.35(m，8H)，1.70(m，2H)，2.89(t，J＝7.4Hz，2H)，7.21(d，J＝8.3Hz，2H)，7.38～7.42(m，3H)，7.47～7.52(m，2H)，7.82(d，J＝8.3Hz，2H)
(E) Preparation of (E) -2- ((hydroxyimino) -1- (4- (benzenethiol) phenyl) oct-1-one (Compound I-2-1-3)
Figure BDA0000730321920000271
A three-necked flask was charged with 300ml of a tetrahydrofuran solution of hydrogen chloride (containing 29g of HCl) and 31.2g (0.1mol) of the compound I-2-1-2, dissolved by stirring at room temperature, 150ml of a tetrahydrofuran solution of methyl nitrite (0.12mol) was added dropwise at room temperature until the reaction was completed, and then concentrated under reduced pressure to obtain 40g of an orange-red oily liquid, and 250ml of methylene chloride, 3 × 100ml of water, anhydrous MgSO (MgSO) was added thereto, and the mixture was washed with water and dried over anhydrous magnesium sulfate (NaCl)4Drying, filtering, concentrating under reduced pressure to obtain reddish brown oily liquid 34g, adding 120ml petroleum ether, heating and dissolving completely under stirring, slowly cooling to-5 deg.C, precipitating white solid, vacuum filtering, washing filter cake with petroleum ether to obtain white solid 18.7g, which is compound I-2-1-3 with yield of 55%.
1HNMR(300MHz，CDCl3) 0.88(t, J ═ 6.6Hz, 3H), 2.73(t, J ═ 7.5Hz, 2H), 1.29 to 1.36(m, 6H), 1.50 to 1.58(m, 2H), 8.73(br, 1H), 7.18 to 7.28(d, J ═ 4.2Hz, 2H), 7.39 to 7.44(m, 3H), 7.50 to 7.53(m, 2H), 7.78 to 7.87(d, J ═ 8.7Hz, 2H), as shown in fig. 2.
Preparation of 3-benzoyl-2, 4, 6-trimethylbenzoyl chloride (Compound I-2-1-4)
Figure BDA0000730321920000272
100ml of dichloromethane, 26.8g (0.1mol) of 3-benzoyl-2, 4, 6-trimethyl benzoic acid and 2 drops of DMF are added into a three-neck flask, a reflux condenser tube, a constant pressure dropping funnel, a drying tube and an alkali liquor tail gas absorption device are arranged, the heating is carried out until the reflux is reached, 36.9g (0.3mol) of thionyl chloride and 50ml of dichloromethane mixed liquid are slowly dropped, after dropping for about 1h, the reflux is carried out for 2h, the reduced pressure concentration is carried out, 100ml of fresh dichloromethane is added, the reduced pressure concentration is carried out again, and 30g of reddish brown oily liquid is obtained, namely the compound I-2-1-4.
(E) Preparation of (E) -2- ((3-benzoyloxy-2, 4, 6-trimethylbenzoyloxy) imino) -1- (4- (phenylmercapto) phenyl) oct-1-one (compound I-2-1)
Figure BDA0000730321920000273
Adding 6.82g (0.02mol) of compound I-2-1-3 and 50ml of dichloromethane, cooling to about 0 ℃, adding 2.37g (0.03mol) of pyridine, dropwise adding 6.29g (0.022mol) of compound I-2-1-4 and 20ml of dichloromethane at controlled temperature, naturally heating to react for 3 hours after dropwise adding, and adding 30ml of H after the reaction is finished20, stirring for 30min, separating liquid, adding saturated NaHCO3Washing 100ml of the solution to pH 10, washing the solution to neutrality, adding 2% diluted hydrochloric acid to adjust the pH 4, washing 3 × 100ml of the solution to neutrality, and washing with anhydrous MgSO4Drying, filtering and concentrating under reduced pressure to obtain orange-red oily liquid 8.3g, with the yield of 70 percent, namely the compound I-2-1.
1HNMR(300MHz，CDCl3) 0.81-0.89 (t, J ═ 6.0Hz, 3H), 2.76-2.81 (t, J ═ 8.7Hz, 2H), 1.22-1.32 (m, 4H), 1.47-1.57(m, 4H), 2.13-2.15 (m, 6H), 2.36-2.42 (t, J ═ 5.8Hz, 3H), 7.03(s, J ═ 7.8Hz, 1H), 7.20-7.45 (d, J ═ 4.2Hz, 2H), 7.50-7.54 (m, 5H), 7.55-7.56 (m, 2H), 7.73(s, J ═ 5.7Hz, 1H), 7.83-7.89 (d, J ═ 8.3Hz, 2H), 7.98 (m, 2H), as shown in fig. 3H.
Example 2
Preparation of n-octanoyl chloride (I-7-1-1)
Figure BDA0000730321920000281
Adding 200ml of dichloromethane, 100g of n-octanoic acid and 2 drops of DMF into a three-neck flask, putting up a reflux condenser tube, a constant-pressure dropping funnel, a drying tube and an alkali liquor tail gas absorption device, heating to reflux, slowly dropping 165g of thionyl chloride and 30ml of dichloromethane mixed solution, after dropping for about 1h, refluxing for 2h, carrying out reduced pressure concentration, adding 100ml of fresh dichloromethane, and carrying out reduced pressure concentration again to obtain 114g of light yellow solution, namely the compound I-7-1-1.
Preparation of 1- (3-benzoyl-2, 4, 6-trimethylphenyl) oct-1-one (I-7-1-2)
Figure BDA0000730321920000282
A three-neck flask is charged with 100g (0.45mol) of 3-benzoyl-2, 4, 6-trimethylbenzene and 300ml of dichloromethane, cooled to-5 ℃ in an ice-salt water bath, purged with nitrogen, and charged with 65.3g (0.49mol) of anhydrous A1C13Adding a drying tube, a reflux condenser tube and tail gas absorption, slowly dropping a mixed solution of 76.1g (0.47mol) of n-octanoyl chloride and 50ml of dichloromethane, controlling the temperature at-5 ℃, after dropping for about 2 hours, removing an ice salt water bath, naturally returning to room temperature, continuously stirring for 2-3 hours, monitoring the reaction completion by T L C, slowly pouring the reactant into 200ml of 10% ice dilute hydrochloric acid, stirring for 30 minutes, separating liquid, extracting an aqueous phase by 100ml of dichloromethane, combining organic phases, washing by 3 × 100ml of water, washing by 2% NaHCO, adding a solvent, stirring, cooling, drying, cooling3Adjusting the solution to neutral, separating, washing with 100ml water for 1 time, and removing anhydrous MgSO4Drying, filtering, concentrating under reduced pressure, recrystallizing to obtain brown yellow solid 129g, i.e. compound I-7-1-2, with yield of 82%. MS: 350.22.
(E) Preparation of (E) -1- (3-benzoyl-2, 4, 6-trimethylphenyl) -2- (hydroxyimino) oct-1-one (I-7-1-3)
Figure BDA0000730321920000283
A three-necked flask was charged with 300ml of a tetrahydrofuran solution of hydrogen chloride (containing 29g of HCl) and 35.0g (0.1mol) of Compound I-7-1-2, dissolved by stirring at room temperature, and 150ml of a tetrahydrofuran solution of methyl nitrite (0.12mol) was added dropwise at room temperature until the reaction was completed, followed by concentration under reduced pressure to obtain 44g of an orange-red oily liquid, followed by addition of 250ml of dichloromethane, 3 × 100ml of water, washing with anhydrous MgSO 54Drying, filtering, concentrating under reduced pressure to obtain 36g of reddish brown oily liquid, adding 120ml of petroleum ether, heating and dissolving completely under stirring, slowly cooling to-5 ℃, separating out a brownish red solid, performing suction filtration, and washing a filter cake with petroleum ether to obtain 20g of brownish red solid, namely the compound I-7-1-3, wherein the yield is 53%.
1HNMR(300MHz，CDCl3) 0.86 to 0.90(t, J ═ 6.4Hz, 3H), 2.64 to 2.70(t, J ═ 8.4Hz, 2H), 1.29 to 1.37(m, 6H), 1.49 to 1.54(m, 2H), 1.89(t, J ═ 5.7Hz, 3H), 2.01 to 2.16(m, 6H), 8.99(br, 1H), 6.95(s, J ═ 7.8Hz, 1H), 7.28 to 7.45(m, 2H), 7.56 to 7.61(m, 1H), 7.82 to 7.84(d, J ═ 6.3Hz, 2H), as shown in fig. 4.
Preparation of 2-chloro-1- (4- (phenylmercapto) phenyl) ethanone (compound I-7-1-4)
Figure BDA0000730321920000291
50g (0.27mol) of diphenyl sulfide and 200ml of dichloromethane are added into a three-neck flask, the temperature of an ice salt water bath is reduced to-5 ℃, nitrogen is introduced, and 39.4g (0.30mol) of anhydrous A1C1 is added3Adding a drying tube, a reflux condenser tube and tail gas absorption, slowly dropping a mixed solution of 31.8g (0.28mol) of chloroacetyl chloride and 50ml of dichloromethane, controlling the temperature at-5 ℃, completing dropping for about 1h, removing an ice salt water bath, naturally returning to room temperature, continuing stirring for 2-3 h, monitoring the reaction completion by T L C, slowly pouring the reaction solution into 10% ice dilute hydrochloric acid, keeping the pH at 4, stirring for 30min, separating, extracting a water phase by 100ml of dichloromethane, combining organic phases, washing by 3 × 100ml of water, washing by 2% NaHCO, adding a solvent, stirring, cooling, stirring3Adjusting the solution to neutral, separating, washing with 100ml water for 1 time, and removing anhydrous MgSO4Drying, filtering, concentrating under reduced pressure, recrystallizing to obtain 45g of yellow solid, namely the compound I-7-1-4, with the yield: and 64 percent. MS: 262.7 m/z
Preparation of 4-benzenemercaptobenzoic acid (compound I-7-1-5)
Figure BDA0000730321920000292
Adding a cooled 25% NaOH solution, a NaClO solution (10%), trimethylbenzyl ammonium bromide into a three-necked flask, controlling the temperature to be 0-5 ℃, slowly dripping a mixed solution of 45g (0.17mol) of 2-chloro-1- (4- (phenylmercapto) phenyl) hexanone (a compound I-7-1-4) and 200ml of dichloromethane at the controlled temperature, removing an ice salt water bath after dripping for about 2 hours, naturally returning to the room temperature, continuously stirring for reacting for 2-3 hours,t L C monitors the reaction to be complete, sodium bisulfite is added, after stirring for 30min, 200ml of dichloromethane extraction and 10% hydrochloric acid, pH 3 are added, liquid separation is carried out, 150ml of dichloromethane is used for extracting an aqueous phase, organic phases are combined, 3 × 100ml of water is washed until the aqueous phase is neutral, liquid separation is carried out, and anhydrous MgSO (MgSO) is anhydrous4Drying, filtering, concentrating under reduced pressure, recrystallizing to obtain 30g of yellow solid, namely the compound I-7-1-5, with the yield: 76.7 percent.
Preparation of 4- (Phenylmercapto) benzoyl chloride (Compound I-7-1-6)
Figure BDA0000730321920000293
100ml of dichloromethane, 21g (0.091mol) of 4- (phenylmercapto) benzoic acid and 2 drops of DMF are added into a three-neck flask, a reflux condenser tube, a constant pressure dropping funnel, a drying tube and an alkali liquor tail gas absorption device are arranged, the mixture is heated to reflux, 11.2g (0.095mol) of thionyl chloride and 30ml of dichloromethane are slowly dropped, after dropping for about 0.5h, the mixture is refluxed for 1h, decompressed and concentrated, 100ml of fresh dichloromethane is added for decompressing and concentrating again, and 26g of brown yellow oily liquid is obtained, namely the compound I-7-1-6. (after esterification with methanol MS: m/z-244.3)
(E) Preparation of (E) -1- (3-benzoyl-2, 4, 6-trimethylphenyl) -2- ((4- (phenylmercapto) benzoyloxy) imino) oct-1-one (compound I-7-1)
Figure BDA0000730321920000301
Adding 7.58g (0.02mol) of compound I-7-1-3 and 50ml of dichloromethane, cooling to about 0 ℃, adding 2.37g (0.03mol) of pyridine, dropwise adding 5.45g (0.022mol) of compound I-7-1-6 and 20ml of dichloromethane at controlled temperature, naturally heating to react for 3 hours after dropwise adding, and adding 30ml of H after the reaction is finished20, stirring for 30min, separating liquid, adding saturated NaHCO3Washing 100ml of the solution to pH 10, washing the solution to neutrality, adding 2% diluted hydrochloric acid to adjust the pH 4, washing 3 × 100ml of the solution to neutrality, and washing with anhydrous MgSO4Drying, filtering, concentrating under reduced pressure to obtain orange yellow extremely viscous liquid (near solid), recrystallizing with ethanol to obtain 8.6g, with yield of 73%, to obtain compoundSubstance I-7-1.
1HNMR(300MHz，CDCl3) 0.85 to 0.89(t, J ═ 6.6Hz, 3H), 2.82 to 2.87(t, J ═ 8.7Hz, 2H), 1.30 to 1.32(m, 4H), 1.45(m, 2H), 1.60 to 1.65(m, 2H), 1.97(m, 3H), 2.12(m, 3H), 2.24(t, J ═ 5.8Hz, 3H), 6.99(s, J ═ 7.8Hz, 1H), 7.21 to 7.28(d, J ═ 8.9Hz, 2H), 7.43 to 7.62(m, 8H), 7.90 to 7.93(m, 4H), as shown in fig. 5.
Example 3
Preparation of n-octanoyl chloride (I-13-1-1)
Figure BDA0000730321920000302
Adding 200ml of dichloromethane, 100g of n-octanoic acid and 2 drops of DMF into a three-neck flask, putting up a reflux condenser tube, a constant-pressure dropping funnel, a drying tube and an alkali liquor tail gas absorption device, heating to reflux, slowly dropping 165g of thionyl chloride and 30ml of dichloromethane mixed solution, after dropping for about 1h, refluxing for 2h, carrying out reduced pressure concentration, adding 100ml of fresh dichloromethane, and carrying out reduced pressure concentration again to obtain 114g of light yellow solution, namely the compound I-13-1-1.
Preparation of 1- (3-benzoyl-2, 4, 6-trimethylphenyl) oct-1-one (I-13-1-2)
Figure BDA0000730321920000303
A three-neck flask is charged with 100g (0.45mol) of 3-benzoyl-2, 4, 6-trimethylbenzene and 300ml of dichloromethane, cooled to-5 ℃ in an ice-salt water bath, purged with nitrogen, and charged with 65.3g (0.49mol) of anhydrous A1C13Adding a drying tube, a reflux condenser tube and tail gas absorption, slowly dropping a mixed solution of 76.1g (0.47mol) of n-octanoyl chloride and 50ml of dichloromethane, controlling the temperature at-5 ℃, after dropping for about 2 hours, removing an ice salt water bath, naturally returning to room temperature, continuously stirring for 2-3 hours, monitoring the reaction completion by T L C, slowly pouring the reactant into 200ml of 10% ice dilute hydrochloric acid, stirring for 30 minutes, separating liquid, extracting an aqueous phase by 100ml of dichloromethane, combining organic phases, washing by 3 × 100ml of water, washing by 2% NaHCO, adding a solvent, stirring, cooling, drying, cooling3Adjusting the solution to neutral, separating100ml of water 1 time, anhydrous MgSO4Drying, filtering, concentrating under reduced pressure, recrystallizing to obtain brown yellow solid 129g, i.e. compound I-13-1-2, with yield of 82%. MS: 350.22.
(E) Preparation of (E) -1- (3-benzoyl-2, 4, 6-trimethylphenyl) -2- (hydroxyimino) oct-1-one (I-13-1-3)
Figure BDA0000730321920000311
A three-necked flask was charged with 300ml of a tetrahydrofuran solution of hydrogen chloride (containing 29g of HCl) and 35.0g (0.1mol) of the compound I-13-1-2, dissolved by stirring at room temperature, and 150ml of a tetrahydrofuran solution of methyl nitrite (0.12mol) was added dropwise at room temperature until the reaction was completed, followed by concentration under reduced pressure to obtain 44g of an orange-red oily liquid, followed by addition of 250ml of methylene chloride, washing with 3 × 100ml of water, and anhydrous MgSO4Drying, filtering, concentrating under reduced pressure to obtain 36g of reddish brown oily liquid, adding 120ml of petroleum ether, heating and dissolving completely under stirring, slowly cooling to-5 ℃, separating out a brownish red solid, performing suction filtration, and washing a filter cake with petroleum ether to obtain 20g of brownish red solid, namely the compound I-13-1-3, wherein the yield is 53%.
1HNMR(300MHz，CDCl3)，0.86～0.90(t，J＝6.4Hz，3H)，2.64～2.70(t，J＝8.4Hz，2H)，1.29～1.37(m，6H)，1.49～1.54(m，2H)，1.89(t，J＝5.7Hz，3H)，2.01～2.16(m，6H)，8.99(br，1H)，6.95(s，J＝7.8Hz，1H)，7.28～7.45(m，2H)，7.56～7.61(m，1H)，7.82～7.84(d，J＝6.3Hz，2H)。
Preparation of 3-benzoyl-2, 4, 6-trimethylbenzoyl chloride (Compound I-13-1-4)
Figure BDA0000730321920000312
100ml of dichloromethane, 26.8g (0.1mol) of 3-benzoyl-2, 4, 6-trimethyl benzoic acid and 2 drops of DMF are added into a three-neck flask, a reflux condenser tube, a constant pressure dropping funnel, a drying tube and an alkali liquor tail gas absorption device are arranged, the mixture is heated to reflux, 36.9g (0.3mol) of thionyl chloride and 50ml of dichloromethane are slowly dropped into the mixture, after dropping for about 1h, the mixture is refluxed for 2h, decompressed and concentrated, 100ml of fresh dichloromethane is added into the mixture and decompressed and concentrated again, and 30g of reddish brown oily liquid is obtained, namely the compound I-13-1-4.
(E) Preparation of (E) -2- (3-benzoyl-2, 4, 6-trimethylbenzoylimidoyl) -1- (3-benzoyl-2, 4, 6-trimethylphenyl) oct-1-one (Compound I-13-1)
Figure BDA0000730321920000313
Adding 7.8g (0.02mol) of compound I-13-1-3 and 50ml of dichloromethane, cooling to about 0 ℃, adding 2.37g (0.03mol) of pyridine, dropwise adding 6.29g (0.022mol) of compound I-13-1-4 and 20ml of dichloromethane at controlled temperature, naturally heating to react for 3 hours after dropwise adding, and adding 30ml of H after the reaction is finished20, stirring for 30min, separating liquid, adding saturated NaHCO3Washing 100ml of the solution to pH 10, washing the solution to neutrality, adding 2% diluted hydrochloric acid to adjust the pH 4, washing 3 × 100ml of the solution to neutrality, and washing with anhydrous MgSO4Drying, filtering, concentrating under reduced pressure to obtain pale yellow slightly viscous solid, and recrystallizing with ethanol to obtain 9.8g with yield of 78% to obtain compound I-13-1.
1HNMR(300MHz，CDCl3) 0.83 to 0.87(t, J ═ 6.6Hz, 3H), 2.72 to 2.77(t, J ═ 8.7Hz, 2H), 1.26 to 1.37(m, 4H), 1.50 to 1.63(m, 4H), 1.92 to 2.05(m, 3H), 2.12 to 2.16(t, J ═ 12.4Hz, 3H), 2.30(m, 6H), 2.72 to 2.77(m, 6H), 6.95 to 6.97(d, J ═ 8.1Hz, 2H), 7.45 to 7.57(m, 4H), 7.60 to 7.64(m, 2H), 7.80 to 7.88(m, 4H), as shown in fig. 6.
Example 4
Preparation of n-octanoyl chloride (Compound I-4-1-1)
Figure BDA0000730321920000321
Adding 200ml of dichloromethane, 100g of n-octanoic acid and 2 drops of DMF into a three-neck flask, putting up a reflux condenser tube, a constant-pressure dropping funnel, a drying tube and an alkali liquor tail gas absorption device, heating to reflux, slowly dropping 165g of thionyl chloride and 30ml of dichloromethane mixed solution, after dropping for about 1h, refluxing for 2h, carrying out reduced pressure concentration, adding 100ml of fresh dichloromethane, and carrying out reduced pressure concentration again to obtain 114g of light yellow solution, namely the compound I-4-1-1.
Preparation of 1-chloro-4-octanoate-based thioxanthone (Compound I-4-1-2)
Figure BDA0000730321920000322
Adding 5.24g (0.02mol) of compound 1-chloro-4-hydroxythioxanthone and 50ml of dichloromethane, cooling to about 0 ℃, adding 2.37g (0.03mol) of pyridine, dropwise adding 3.56g (0.022mol) of compound I-4-1-1 and 20ml of dichloromethane at controlled temperature, naturally heating to react for 3 hours after dropwise adding, tracking by a T L C plate until the reaction is finished, adding 30ml of H 20, stirring for 30min, separating liquid, adding saturated NaHCO3Washing 100ml of the solution to pH 10, washing the solution to neutrality, adding 2% diluted hydrochloric acid to adjust the pH 4, washing 3 × 100ml of the solution to neutrality, and washing with anhydrous MgSO4Drying, filtering, concentrating under reduced pressure to obtain brown yellow solid, recrystallizing with ethanol to obtain 6.5g, with yield of 84%, to obtain compound I-4-1-2.
Preparation of 1-chloro-4- (2-hydroxyimino) caprylate thioxanthone (I-4-1-3)
Figure BDA0000730321920000323
A three-necked flask was charged with 300ml of a tetrahydrofuran solution of hydrogen chloride (containing 29g of HCl) and 38.9g (0.1mol) of the compound I-4-1-2, dissolved by stirring at room temperature, and 150ml of a tetrahydrofuran solution of methyl nitrite (0.12mol) was added dropwise at room temperature until the reaction was completed, followed by concentration under reduced pressure to obtain 49g of an orange-red oily liquid, followed by addition of 250ml of methylene chloride, washing with 3 × 100ml of water, and anhydrous MgSO4Drying, filtering, concentrating under reduced pressure to obtain 41g of reddish brown oily liquid, adding 120ml of petroleum ether, heating and completely dissolving under stirring, slowly cooling to-5 ℃, separating out brown solid, performing suction filtration, and washing a filter cake with petroleum ether to obtain 26.7g of brown solid, namely the compound I-4-1-3, wherein the yield is 64%.
1HNMR(300MHz，CDCl3) 0.85 to 0.88(t, J ═ 7.3Hz, 3H), 2.71 to 2.75(t, J ═ 9.4Hz, 2H), 1.30 to 1.36(m, 6H), 1.50 to 1.57(m, 2H), 11.24(br, 1H), 7.21(s, J ═ 7.2Hz, 1H), 7.26 to 7.31(s, J ═ 7.2Hz, 1H), 7.46(s, J ═ 8.1Hz, 1H), 7.54 to 7.57(d, J ═ 8.9Hz, 2H), 8.24 to 8.26(s, J ═ 7.2Hz, 1H), as shown in fig. 7.
Preparation of 3-benzoyl-2, 4, 6-trimethylbenzoyl chloride (Compound I-4-1-4)
Figure BDA0000730321920000331
100ml of dichloromethane, 26.8g (0.1mol) of 3-benzoyl-2, 4, 6-trimethyl benzoic acid and 2 drops of DMF are added into a three-neck flask, a reflux condenser tube, a constant pressure dropping funnel, a drying tube and an alkali liquor tail gas absorption device are arranged, the heating is carried out until the reflux is reached, 36.9g (0.3mol) of thionyl chloride and 50ml of dichloromethane mixed liquid are slowly dropped, after dropping for about 1h, the reflux is carried out for 2h, the reduced pressure concentration is carried out, 100ml of fresh dichloromethane is added, the reduced pressure concentration is carried out again, and 30g of reddish brown oily liquid is obtained, namely the compound I-4-1-4.
(E) Preparation of (E) -1-chloro- (2- (3-benzoyl-2, 4, 6-trimethylbenzoylimido ester)) -4-octanoate thioxanthone (Compound I-13-1)
Figure BDA0000730321920000332
Adding 8.36g (0.02mol) of compound I-4-1-3 and 50ml of dichloromethane, cooling to about 0 ℃, adding 2.37g (0.03mol) of pyridine, dropwise adding 6.29g (0.022mol) of compound I-4-1-4 and 20ml of dichloromethane at controlled temperature, naturally heating to react for 3 hours after dropwise adding, and adding 30ml of H after the reaction is finished20, stirring for 30min, separating liquid, adding saturated NaHCO3Washing 100ml of the solution to pH 10, washing the solution to neutrality, adding 2% diluted hydrochloric acid to adjust the pH 4, washing 3 × 100ml of the solution to neutrality, and washing with anhydrous MgSO4Drying, filtering, concentrating under reduced pressure to obtain solid of earthy yellow, recrystallizing with ethanol to obtain 11.3g, with yield of 85%, to obtain compound I-4-1. MP: 140.76 deg.C.
1HNMR(300MHz，CDCl3) 0.81 to 0.83(t, J ═ 6.5Hz, 3H), 2.76 to 2.78(t, J ═ 8.5Hz, 2H), 1.21 to 1.26(m, 4H), 1.47 to 1.52(m, 4H), 2.13 to 2.15(m, 6H), 2.42(m, 3H), 7.23(s, J ═ 7.4Hz, 1H), 7.48 to 7.56(m, 8H), 7.85 to 7.88(m, 2H), 8.73 to 8.46(s, J ═ 8.4Hz, 1H), as shown in fig. 8.
Application example 1
The solubility of the compounds I-2-1, I-7-1, I-13-1 and I-4-1 in a common organic solvent, such as ethyl acetate, ethylene glycol monoethyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate, is detected, four equal parts of the compounds I-2-1, I-7-1, I-13-1 and I-4-1 are respectively placed in four sample bottles, are respectively dissolved by ethylene glycol monoethyl ether and propylene glycol methyl ether acetate, and the stability of the photoinitiator in the solution is detected by T L C.
Application example 2
The pyrolysis performance of the compounds I-2-1, I-7-1, I-13-1 and I-4-1 is measured by a differential thermal-thermogravimetric analyzer. Temperature rise rate: 10 ℃/min. The initial decomposition temperatures of the compounds I-2-1, I-7-1, I-13-1 and I-4-1 are all detected to be above 150 ℃, and the thermal stability is good.
Application example 3
Dissolving compound compounds I-2-1, I-7-1, I-13-1 and I-4-1 in acetonitrile, respectively preparing solutions with certain molar concentrations, and comparing by measuring an ultraviolet absorption spectrum by using an ultraviolet-visible spectrophotometer. The detection spectrogram shows that the synthesized compounds have wide ultraviolet absorption bands and have large absorption bands at 300-365 nm, as shown in figure 1, figure 9, figure 10 and figure 11.
Application example 4
The conversion of double bonds of the compounds I-2-1, I-7-1, I-13-1 and I-4-1 of the examples to initiate polymerization of hydroxyethyl methacrylate was compared using real-time infrared measurements. Acetone is used as solvent to prepare compounds I-2-1 and I-7-1Samples with the concentration of 3 percent of the monomer concentration, I-13-1 and I-4-1 are coated on a KBr salt plate, then the KBr salt plate is put into Nico-let5700, an ultraviolet point light source is used for irradiating the sample, and the ultraviolet light intensity on the surface of the sample is adjusted to be 30mW/cm2. The conversion rate of double bonds of the monomers is collected in real time by near infrared, the real-time infrared parameters are set as data collection intervals of 0.3985s, each spectrum is scanned for 1 time, and the resolution is 4cm-1. The characteristic absorption peak of the carbon-carbon double bond of the hydroxyethyl methacrylate in a near infrared spectrogram is 1630cm-1Since the carbon-carbon double bond is changed to a carbon-carbon single bond as the photocuring reaction proceeds and the intensity of the absorption peak of the double bond becomes weaker as the light irradiation time increases, the degree of change in the polymerization reaction is reflected by the change in the characteristic absorption peak of the carbon-carbon double bond. Double bond conversion (DC) was calculated by data processing software in conjunction with the following formula.
DC(％)＝[1-(At/Ao)]×100％
In which Ao and At1630cm before curing and t-time after illumination, respectively-1Area of characteristic absorption peak of hydroxyethyl methacrylate double bond. The detection result shows that the compounds I-2-1, I-7-1, I-13-1 and I-4-1 can initiate the polymerization of hydroxyethyl methacrylate, and the conversion rate of acrylic double bonds can reach more than 60% after illumination for l0 min.
Application example 5
Preparing a film resin from polyvinylpyrrolidone (MW 40000) and polymethacrylate resin (Mn 50000), using 2-hydroxybutyl acrylate as a polymerization monomer, adding compounds I-2-1, I-7-1, I-13-1 and I-4-1 respectively, adding a proper amount of chain transfer agent and dye, using propylene glycol methyl ether as a solvent to prepare free radical synthesis imaging photosensitive glue solutions 1,2, 3 and 4, and performing performance test on the glue solutions according to the following method2. Controlling the rotation speed of the centrifugal coating machine to ensure that the coating weight (based on solid content) coated on the aluminum plate base is 0.5-2.5 g/m2And after primary drying on a centrifugal coating machine, transferring the plate to a blast drier at 100 ℃ for drying for 3min to obtain the purple laser CTP original plate. And exposing the original plate by using a purple laser, and testing the photosensitive performance of the plate material by using a Ugra test strip as a mask. After exposure, development was carried out with 1% aqueous NaOH solution. In the exposed areas, the photopolymerizable compound is polymerized in the presence of an initiator and is insoluble in the developer, while the unexposed areas are soluble, thus giving a negative image. Sensitivity was evaluated from the continuous scale of the obtained image by exposure and development, and accuracy was evaluated from the area of the microwire test block, thereby evaluating the quality of the photosensitive property of the photosensitive composition. The experimental results show that under the condition that the exposure time is 40s, the plates of the compounds I-2-1, I-7-1, I-13-1 and I-4-1 can display more than 3 sections of a continuous gradient ruler with the precision of more than 6 mu. Therefore, the compounds I-2-1, I-7-1, I-13-1 and I-4-1 can achieve better imaging effect under certain exposure time and exposure amount, and can be suitable for a purple laser imaging system.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (6)

1. An acyloxime ester compound, wherein the acyloxime ester compound has a structure shown in a general formula I:
Figure FDF0000005422680000011
wherein the content of the first and second substances,
the R is1And R4The same or different, each independently selectedFrom
Figure FDF0000005422680000012
Figure FDF0000005422680000013
Said X 'and Y' are the same or different and are each independently selected from-S-, -S-S-, -O-, -CO-;
r is as defined above1And R4In selected substituents, one or more-H in the cyclic structure may be replaced by-F, -Cl, -Br, -I, -NO2、-COOR'1、-CONR'2、-OR'3、
Figure FDF0000005422680000014
Alkyl or alkoxy of 1 to 8 carbon atoms or alkenyl of 2 to 8 carbon atoms, wherein R'1And R'2Each independently selected from-H,
Figure FDF0000005422680000015
Figure FDF0000005422680000016
Alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, R'3Selected from-H, alkyl of 1-8 carbon atoms, cycloalkyl of 3-8 carbon atoms, alkenyl of 2-8 carbon atoms or carbon chain carbonyl of 1-8 carbon atoms, wherein the carbonyl in the carbon chain carbonyl of 1-8 carbon atoms is terminal and located at the connecting bond;
the R is2Selected from-H, alkyl or alkoxy of 1 to 20 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or alkenyl of 2 to 20 carbon atoms;
or R2And R1The groups shown are the same;
the premise is that: r is as defined above1And R4At least one of which is
Figure FDF0000005422680000017
2. The acyloxime ester compound as claimed in claim 1 wherein R is1And R4Are the same or different and are each independently selected from
Figure FDF0000005422680000021
Figure FDF0000005422680000022
3. The acyloxime ester compound as claimed in claim 1 wherein R is2Selected from-H, alkyl of 1-8 carbon atoms, alkoxy or alkenyl of 2-8 carbon atoms or with R1The groups shown are the same.
4. The acyloxime ester compound as claimed in claim 1 or claim 2 wherein the compound of the general formula i is selected from the group consisting of compounds of the general formulae i-1 to i-17:
Figure FDF0000005422680000023
Figure FDF0000005422680000031
Figure FDF0000005422680000041
Figure FDF0000005422680000051
wherein the content of the first and second substances,
the R is2Selected from-H, alkyl or alkoxy of 1-20 carbon atoms, cycloalkyl of 3-8 carbon atoms, alkylene of 2-20 carbon atoms or R1The groups shown.
5. A method for preparing acyloxime ester compounds described by general formula I comprises the following steps:
a. synthesis of intermediates I-A: using benzene, diphenyl sulfide or thioxanthone as starting material and a compound containing R2Acyl halide compound of the group is synthesized into an intermediate I-A through Friedel-crafts acylation reaction under the action of ferric trichloride, aluminum trichloride or zinc chloride:
Figure FDF0000005422680000052
b. synthesis of intermediates I-B: and (3) carrying out oxidation reaction on the intermediate I-A and methyl nitrite, ethyl nitrite or isoamyl nitrite in the presence of hydrogen chloride or hydrochloric acid to generate an acyl oxime intermediate I-B:
Figure FDF0000005422680000053
c. synthesis of acyloxime ester photoinitiator: intermediates I-B and compounds containing R4Synthesizing a compound with a general formula I by using acyl halide or acid anhydride with a structure in the presence of a pyridine or triethylamine acid-binding agent and in a dichloromethane, dichloroethane or dioxane solvent:
Figure FDF0000005422680000061
wherein the content of the first and second substances,
the R is1And R4Are the same or different and are each independently selected from
Figure FDF0000005422680000062
Figure FDF0000005422680000063
Figure FDF0000005422680000064
Said X'and Y', which are the same or different, are each independently selected from the group consisting of-S-, -S-S-, -O-, -CO-;
r is as defined above1And R4In selected substituents, one or more-H in the cyclic structure may be replaced by-F, -Cl, -Br, -I, -NO2、-COOR'1、-CONR'2、-OR'3、
Figure FDF0000005422680000065
Alkyl or alkoxy of 1 to 8 carbon atoms or alkenyl of 2 to 8 carbon atoms, wherein R'1And R'2Each independently selected from-H,
Figure FDF0000005422680000066
Figure FDF0000005422680000067
Alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, R'3Selected from-H, alkyl of 1-8 carbon atoms, cycloalkyl of 3-8 carbon atoms, alkenyl of 2-8 carbon atoms or carbon chain carbonyl of 1-8 carbon atoms, wherein the carbonyl in the carbon chain carbonyl of 1-8 carbon atoms is terminal and located at the connecting bond;
the R is2Selected from-H, alkyl or alkoxy of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or alkenyl of 2 to 8 carbon atoms;
or R2And R1The groups shown are the same;
the premise is that: the R is1And R4At least one of
Figure FDF0000005422680000068
6. Use of the acyloxime ester compounds according to any one of claims 1 to 4 in UV-light-curable materials.
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