CN105566201A - Green synthesis method of carbazole oxime ester photoinitiator - Google Patents
Green synthesis method of carbazole oxime ester photoinitiator Download PDFInfo
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- CN105566201A CN105566201A CN201511035286.8A CN201511035286A CN105566201A CN 105566201 A CN105566201 A CN 105566201A CN 201511035286 A CN201511035286 A CN 201511035286A CN 105566201 A CN105566201 A CN 105566201A
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- carbazole
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- ethyl carbazole
- benzene formyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
Abstract
The invention discloses a green synthesis method of a carbazole oxime ester photoinitiator. According to the method, N-ethyl carbazole is taken as the raw material; then N-ethyl carbazole carries out condensation reactions with o-toluoyl chloride and acetic anhydride/acetyl chloride in the presence of a zirconium catalyst, and finally the condensation reaction product is oximated and esterified to obtain the carbazole oxime ester photoinitiator. The synthesis method does not need high temperature and high pressure, the conditions are mild, and thus the synthesis method is very safe. During the synthesis process, a zirconium catalyst is used, no aluminum chloride or zinc wastewater is generated therefore, the generated byproducts can be recovered, moreover, no solvent that is harmful to the environment is used, and the synthesis method is environment-friendly and is suitable for industrial production.
Description
Technical field
The invention belongs to liquid crystal new material technology field, particularly relate to a kind of green synthesis method of carbazole oxime ester lightlike initiating agent.
Background technology
The chemical name of carbazole oxime ester lightlike initiating agent Oxe-02 is 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl, and the colored filter being mainly used in the Light Curing of unsaturated polyester, particularly liquid crystal is produced.Its chemical structural formula is as follows:
Prior art generally uses the catalyzer such as aluminum chloride, zinc chloride to carry out friedel-crafts acylation reaction to synthesize the 3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole of the first step, the method has following shortcoming: 1. the catalyzer such as aluminum chloride, zinc chloride facile hydrolysis releases hydrogenchloride, pollutes; 2. the catalyzer such as aluminum chloride, zinc chloride can with acyl chlorides and the complexing of product ketone, cause acyl chlorides and catalyzer usage quantity to strengthen, cause wastage of material, improve cost; 3. the catalyzer such as aluminum chloride, zinc chloride produces a large amount of acid waste water when aftertreatment, and is difficult to reclaim, and causes a large amount of pollution.
Summary of the invention
In order to solve the problem, the present invention's Zr catalyst replaces the catalyzer such as aluminum chloride, zinc chloride, provide that a kind of yield is high, cost is low, security is good, environmentally friendly, and be applicable to the preparation method of the carbazole oxime ester photoinitiator Oxe-02 of suitability for industrialized production.
In order to achieve the above object, the preparation method of carbazole oxime ester intermediate 1-provided by the invention (6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl comprises the following step carried out in order:
(1) using N-ethyl carbazole as raw material, using halohydrocarbon as solvent, condensation is carried out with o-methyl-benzene formyl chloride under the effect of Zr catalyst, then continue and Acetyl Chloride 98Min. condensation, temperature of reaction is-10 DEG C ~ 20 DEG C, add acid after reaction terminates to process, filter, drying obtains intermediate 3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole; Two step acylation reactions are combined into a step to carry out, and decreases post-processing operation, so decrease discharge of wastewater, reduces production cost;
(2) using saturated fatty alcohol roh as solvent, or saturated fatty alcohol roh and water are as solvent, under buffering salt exists, above-mentioned 3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole and oxammonium hydrochloride are reacted and make crude product at the temperature of 0 ~ 150 DEG C, finally crude product organic solvent recrystallization purifying is obtained 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime; Byproduct of reaction is water and sodium-chlor, does not produce environmentally harmful material;
(3) using halohydrocarbon as solvent; under the existence of boric acid; dewater reacting at the temperature of above-mentioned 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime and acetic acid 40 ~ 150 DEG C and make crude product, finally crude product organic solvent recrystallization purifying being obtained 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl.Byproduct of reaction is water, does not produce environmentally harmful material.
Synthetic route of the present invention is as follows:
In described step (1), solvent halohydrocarbon is at least one in methylene dichloride, chloroform, tetracol phenixin, 1,2-ethylene dichloride, chlorobenzene, and the amount ratio of halohydrocarbon and N-ethyl carbazole is 2 ~ 20ml:1g.
In described step (1), o-methyl-benzene formyl chloride and Acetyl Chloride 98Min. consumption are 0.5-3 times of N-ethyl carbazole molar weight.
In described step (1), Zr catalyst consumption is 0.01-5 times of N-ethyl carbazole molar weight.
Acid in described step (1) is selected from least one in hydrochloric acid, sulfuric acid, nitric acid, acetic acid or butyric acid, and the consumption of acid is 2-10 times of N-ethyl carbazole molar weight.
In described step (3), halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin, 1; at least one in 2-ethylene dichloride, chlorobenzene, the amount ratio of halohydrocarbon and 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime is 2 ~ 20ml:1g.
In described step (3), recrystallization organic solvent is selected from least one in methyl alcohol, ethanol, ethyl acetate, ether, toluene, isopropyl ether and methyl tertiary butyl ether.
Further, the ingredient proportion in the present invention is optimum experimental gained, crosses that I haven't seen you for ages causes reaction not exclusively, crosses and can cause waste at most, increase cost.
The preparation method of carbazole oxime ester intermediate 1-provided by the invention (6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl is using N-ethyl carbazole as raw material, obtain 3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole with o-methyl-benzene formyl chloride and Acetyl Chloride 98Min. condensation under the effect of Zr catalyst, the latter is obtained by reacting 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime with oxammonium hydrochloride under buffering salt exists, last under the existence of boric acid with acetic acidreaction and obtain final product 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl.
Relative to prior art, the present invention has following advantage:
(1) because this preparation method adopts Zr catalyst to replace aluminum chloride class catalyzer, so do not produce aluminum chloride or zinc waste water, environmental pollution is decreased
(2) optimize operation steps, shorten the reaction times,
(3) do not relate to high-temperature high-voltage reaction, mild condition, security is good.
(4) product purity obtained is high
(5) do not use environmentally harmful solvent, the equal recoverable of the by product produced, environmentally friendly, production cost is low, is therefore suitable for suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the preparation method to carbazole oxime ester intermediate 1-provided by the invention (6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl is described in detail.
Embodiment 1:
A.3-the preparation of ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole
100.5gN-ethyl carbazole (0.51mol), 500ml chlorobenzene is added in the four-hole bottle that electric mixer and thermometer are housed, the temperature of this reaction solution is down to 15 ~ 20 DEG C, add 1mol Zr catalyst, then drip 119.0g o-methyl-benzene formyl chloride (0.77mol) and the mixing solutions of 200ml chlorobenzene, dropwise rear insulated and stirred 1 hour.Add 60.4g Acetyl Chloride 98Min. (0.77mol) and the mixing solutions of 100ml chlorobenzene afterwards, continue stirring reaction 30 minutes.After completion of the reaction, reaction solution is poured in the dilute sulphuric acid of 1500ml1mol/L, stir separatory after 1 hour, wash with water to neutrality.Decompression steams solvent, and add the making beating of 1000ml ethanol, suction filtration, drying obtains 170.1g3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole, and HPLC purity is 98.1%, and yield is 93%.
B.1-the preparation of (6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime
25.0g oxammonium hydrochloride (0.36mol), 40.3g sodium bicarbonate (0.48mol), 500ml water is added in the four-hole bottle that electric mixer and thermometer are housed; be stirred to and dissolve completely; add 1500ml methyl alcohol again; 87.6g3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole (0.24mol), reflux is to reacting complete.Poured into by reaction solution in 4500ml cold water, suction filtration, solid adds the making beating of 300ml ethanol, suction filtration, and dry, obtain 82.2g1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime, HPLC purity is 98.3%, and yield is 90%.
C.1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl
500ml chlorobenzene is added in the four-hole bottle that electric mixer, thermometer, water trap are housed; 85.4g1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime (0.23mol), 27.6g acetic acid (0.46mol) and 21.3g boric acid (0.34mol); reflux water-dividing; after completion of the reaction; successively with sodium hydrogen carbonate solution, be washed to neutrality; add anhydrous sodium sulfate drying, filter.Filtrate steams solvent, and gained semisolid adds 150ml alcohol crystal and obtains 76.0g white solid 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl, and HPLC purity is 98.7%, and yield is 80%.
Embodiment 2:
A.3-the preparation of ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole
100.5gN-ethyl carbazole (0.51mol), 300ml chloroform is added in the 2L four-hole bottle that electric mixer and thermometer are housed, the temperature of this reaction solution is down to 0 ~ 5 DEG C, add 2mol Zr catalyst, then drip 78.8g o-methyl-benzene formyl chloride (0.51mol) and the mixing solutions of 200ml chloroform, dropwise rear insulated and stirred 1 hour.Add 40.0g Acetyl Chloride 98Min. (0.51mol) and the mixing solutions of 100ml chloroform afterwards, continue stirring reaction 30 minutes.After completion of the reaction, reaction solution is poured in the dilute hydrochloric acid of 1200ml1mol/L, stir separatory after 1 hour, wash with water to neutrality.Decompression steams solvent, and add the making beating of 1000ml ethanol, suction filtration, drying obtains 155.5g3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole, and HPLC purity is 97.9%, and yield is 85%.
B.1-the preparation of (6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime
33.4g oxammonium hydrochloride (0.48mol), 65.3g potassium primary phosphate (0.48mol), 300ml water is added in the four-hole bottle that electric mixer and thermometer are housed; be stirred to and dissolve completely; add 900ml propyl alcohol again; 87.6g3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole (0.24mol), reflux is to reacting complete.Poured into by reaction solution in 3000ml cold water, suction filtration, solid adds the making beating of 300ml propyl alcohol, suction filtration, and dry, obtain 84.9g1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime, HPLC purity is 98.5%, and yield is 93%.
C.1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl
500ml chloroform is added in the four-hole bottle that electric mixer, thermometer, water trap are housed; 85.4g1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime (0.23mol), 41.4g acetic acid (0.69mol) and 21.3g boric acid (0.34mol); reflux water-dividing; after completion of the reaction; successively with sodium hydrogen carbonate solution, be washed to neutrality; add anhydrous sodium sulfate drying, filter.Filtrate steams solvent, and gained semisolid adds 150ml alcohol crystal and obtains 71.2g white solid 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl, and HPLC purity is 98.5%, and yield is 75%.
Embodiment 3:
A.3-the preparation of ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole
100.5gN-ethyl carbazole (0.51mol), 300ml methylene dichloride is added in the four-hole bottle that electric mixer and thermometer are housed, the temperature of this reaction solution is down to-10 ~ 0 DEG C, add 1mol Zr catalyst, then drip 102.0g o-methyl-benzene formyl chloride (0.66mol) and the mixing solutions of 100ml methylene dichloride, dropwise rear insulated and stirred 1 hour.Add 51.8g Acetyl Chloride 98Min. (0.66mol) and the mixing solutions of 50ml methylene dichloride afterwards, continue stirring reaction 30 minutes.After completion of the reaction, reaction solution is poured in the dilute hydrochloric acid of 1500ml1mol/L, stir separatory after 1 hour, wash with water to neutrality.Decompression steams solvent, and add the making beating of 1000ml ethanol, suction filtration, drying obtains 151.8g3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole, and HPLC purity is 98.0%, and yield is 83%.
B.1-the preparation of (6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime
25.0g oxammonium hydrochloride (0.36mol), 47.1g Potassium ethanoate (0.48mol), 300ml water is added in the four-hole bottle that electric mixer and thermometer are housed; be stirred to and dissolve completely; add 1200ml ethanol again; 87.6g3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole (0.24mol), reflux is to reacting complete.Poured into by reaction solution in 4000ml cold water, suction filtration, solid adds the making beating of 300ml ethanol, suction filtration, and dry, obtain 82.1g1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime, HPLC purity is 98.2%, and yield is 90%.
C.1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl
300ml methylene dichloride is added in the four-hole bottle that electric mixer, thermometer, water trap are housed; 85.4g1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime (0.23mol), 27.6g acetic acid (0.46mol) and 21.3g boric acid (0.34mol); reflux water-dividing; after completion of the reaction; successively with sodium hydrogen carbonate solution, be washed to neutrality; add anhydrous sodium sulfate drying, filter.Filtrate steams solvent, and gained semisolid adds the crystallization of 150ml ethyl acetate and obtains 67.4g white solid 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl, and HPLC purity is 98.6%, and yield is 71%.
Claims (7)
1. a green synthesis method for carbazole oxime ester lightlike initiating agent, is characterized in that: described preparation method comprises the following step carried out in order:
(1) using N-ethyl carbazole as raw material, using halohydrocarbon as solvent, condensation is carried out with o-methyl-benzene formyl chloride under the effect of Zr catalyst, then continue and Acetyl Chloride 98Min. condensation, temperature of reaction is-10 DEG C ~ 20 DEG C, add acid after reaction terminates to process, filter, drying obtains intermediate 3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole;
(2) using saturated fatty alcohol roh as solvent, or saturated fatty alcohol roh and water are as solvent, under buffering salt exists, above-mentioned 3-ethanoyl-6-o-methyl-benzene formyl radical-N-ethyl carbazole and oxammonium hydrochloride are reacted and make crude product at the temperature of 0 ~ 150 DEG C, finally crude product organic solvent recrystallization purifying is obtained 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime;
(3) using halohydrocarbon as solvent; under the existence of boric acid; dewater reacting at the temperature of above-mentioned 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime and acetic acid 40 ~ 150 DEG C and make crude product, finally crude product organic solvent recrystallization purifying being obtained 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime-O-acetyl.
2. the green synthesis method of a kind of carbazole oxime ester lightlike initiating agent according to claim 1, it is characterized in that: in described step (1), solvent halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin, 1, at least one in 2-ethylene dichloride, chlorobenzene, the amount ratio of halohydrocarbon and N-ethyl carbazole is 2 ~ 20ml:1g.
3. the green synthesis method of a kind of carbazole oxime ester lightlike initiating agent according to claim 1, is characterized in that: in described step (1), o-methyl-benzene formyl chloride and Acetyl Chloride 98Min. consumption are 0.5-3 times of N-ethyl carbazole molar weight.
4. the green synthesis method of a kind of carbazole oxime ester lightlike initiating agent according to claim 1, it is characterized in that: in described step (1), Zr catalyst is selected from least one in zirconium white or the zirconium white of load on the carriers such as aluminum oxide, kaolin, diatomite, Zr catalyst consumption is 0.01-5 times of N-ethyl carbazole molar weight.
5. the green synthesis method of a kind of carbazole oxime ester lightlike initiating agent according to claim 1, it is characterized in that: the acid in described step (1) is selected from least one in hydrochloric acid, sulfuric acid, nitric acid, acetic acid or butyric acid, the consumption of acid is 2-10 times of N-ethyl carbazole molar weight.
6. the green synthesis method of a kind of carbazole oxime ester lightlike initiating agent according to claim 1; it is characterized in that: in described step (3), halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin, 1; at least one in 2-ethylene dichloride, chlorobenzene, the amount ratio of halohydrocarbon and 1-(6-o-methyl-benzene formyl radical-N-ethyl carbazole-3-base)-acetophenone oxime is 2 ~ 20ml:1g.
7. the green synthesis method of a kind of carbazole oxime ester lightlike initiating agent according to claim 1, is characterized in that: in described step (3), recrystallization organic solvent is selected from least one in methyl alcohol, ethanol, ethyl acetate, ether, toluene, isopropyl ether and methyl tertiary butyl ether.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100059A (en) * | 2018-10-28 | 2020-05-05 | 北京艾德旺科技发展有限公司 | Structural design and synthesis of novel carbazole oxime ester photoinitiator |
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| CN101723875A (en) * | 2009-11-25 | 2010-06-09 | 优缔精细化工（苏州）有限公司 | Light trigger |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101723875A (en) * | 2009-11-25 | 2010-06-09 | 优缔精细化工（苏州）有限公司 | Light trigger |
Non-Patent Citations (3)
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| 宋国强等: "肟酯类光引发剂OXE-2的合成", 《精细化工》 * |
| 王春芳等: "硼酸催化合成水杨酸异丙酯的研究", 《河北化工》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111100059A (en) * | 2018-10-28 | 2020-05-05 | 北京艾德旺科技发展有限公司 | Structural design and synthesis of novel carbazole oxime ester photoinitiator |
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