CN1235874C - Chemical synthesis method of aryl isocyanate - Google Patents

Chemical synthesis method of aryl isocyanate Download PDF

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Publication number
CN1235874C
CN1235874C CN 02130077 CN02130077A CN1235874C CN 1235874 C CN1235874 C CN 1235874C CN 02130077 CN02130077 CN 02130077 CN 02130077 A CN02130077 A CN 02130077A CN 1235874 C CN1235874 C CN 1235874C
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arylamine
reaction
aryl isocyanate
trichloromethyl
yield
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CN1475480A (en
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苏为科
李永曙
蔡鸿飞
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

Aryl isocyanate is an important intermediate product for organic synthesis. In the present invention, aryl isocyanate is prepared by the catalytic reaction between bis(trichloromethyl) carbonate and arylamine in organic solvent, wherein the bis(trichloromethyl) carbonate and the arylamine are used as raw materials. In the chemical synthesis method of the present invention, potential safety hazard, waste gas sources, waste liquid sources and waste residue sources are fundamentally eliminated. Thus, the method for preparing aryl isocyanate serial products has the advantages of easy raw material obtainment, safe and reliable preparation, high reaction yield, low preparation cost, basically no waste gas, waste liquid and waste residue.

Description

The chemical synthesis process of aryl isocyanate
Technical field
The present invention relates to two (trichloromethyl) carbonic ethers of a kind of usefulness substitute phosgene or trichloromethylchloroformate directly and arylamine reaction prepare the chemical synthesis process of aryl isocyanate.Aryl isocyanate is mainly used in synthetic medicine, agricultural chemicals and macromolecular material.
Background technology
Before the present invention made, the existing main method of chemosynthesis aryl isocyanate was to be that raw material is synthesized into by arylamine photoreactive gas or trichloromethylchloroformate, for example UPS5556971, UPS3917847, UPS3763232, BP737487, FP1098303, day disclosure special permission 8052 (1983), EP147211 etc.Because phosgene (COCl 2) be the hypertoxic gas of the use of strict in the world control and limit production, no matter be laboratory work or industrial production, all there is very big potential safety hazard.Trichloromethylchloroformate is a liquid, and its security is big than phosgene, resolves into phosgene but run into gac, iron or organic amine etc., and storage and transportation etc. are also difficult, thereby still there is bigger potential safety hazard in use.
Summary of the invention
Task of the present invention is the shortcoming that overcomes prior art, provides one technology is reasonable, production safety is reliable, reaction yield is high, production cost is low, do not have substantially the aryl isocyanate series product chemical synthesis process of the three wastes.
The chemical synthesis process of aryl isocyanate, it is characterized in that with arylamine and two (trichloromethyl) carbonic ethers be raw material under the effect of catalyzer tetrabutyl urea, one of them is synthesized into as solvent to select benzene, toluene, chlorobenzene, dimethylbenzene, tetrahydrofuran (THF), tetracol phenixin and ethyl acetate; Perhaps selecting with benzene is solvent, and catalyzer is selected triethylamine, pyridine, N-methylpyrrole, and one of them is synthesized into; The molar ratio of above-mentioned reaction is an arylamine: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.34~0.8: 0.001~0.1, and solvent load is 2-8 a times of arylamine quality, and its reaction equation is:
X 1,X 2,X 3=H,CH 3,CH 2CH 3,CH 2CH 2CH 3,CH(CH 3) 2,F,Cl,Br,I
The present invention compared with prior art, the operational path advanced person, processing condition are reasonable, and used raw material is cheap and easy to get, avoided hypertoxic phosgene and trichloromethylchloroformate, safety simple to operate, the reaction yield height, generally more than 80%, production cost is low, substantially do not have the three wastes, have bigger implementary value and economic results in society.
Embodiment
Embodiment 1
In thermometer, reflux condensing tube, constant pressure funnel and churned mechanically 500ml four-hole boiling flask are housed, add two (trichloromethyl) carbonic ethers of 100g, 250ml benzene and 3g tetrabutyl urea.Open and stir, and begin to drip 93g (1mol) aniline.Finish, be warming up to 70 ℃, and react 3h down at 70-80 ℃, reaction finishes the back underpressure distillation and reclaims benzene, collects cut-product phenylcarbimide 101g of 161-163 ℃ at last, and yield is 85%.Through the gas Chromatographic Determination product purity is 99.0%.
Embodiment 2
Molar ratio is an aniline: two (trichlorotoluene zotrichloride) carbonic ether: catalyzer is 1: 0.5: 0.01, and other is operated with example 1.Yield is 88%, and the phenylcarbimide product purity is more than 99.1%.
Embodiment 3
Molar ratio is an aniline: two (trichlorotoluene zotrichloride) carbonic ether is 1: 0.75, and other is operated with example 1.Yield is 90%, and the phenylcarbimide product purity is 99.3%.
Embodiment 4
Molar ratio is an aniline: two (trichlorotoluene zotrichloride) carbonic ether: catalyzer is 1: 0.35: 0.001, and other is operated with example 1.Yield is 86%, and the phenylcarbimide product purity is 99.2%.
Embodiment 5
Molar ratio is an aniline: two (trichlorotoluene zotrichloride) carbonic ether: catalyzer is 1: 0.35: 0.001, and other is operated with example 1.Yield is 87%, and the phenylcarbimide product purity is 99.1%.
Embodiment 6
The volume ratio that feeds intake is an organic solvent: aniline is 5: 1, and other is operated with example 1.Yield is 85%, and the phenylcarbimide product purity is 99.5%.
Embodiment 7
Catalyzer changes triethylamine into, and other is operated with example 1.Yield is 80%, and the phenylcarbimide product purity is more than 98.2%.
Embodiment 8
Catalyzer changes pyridine into, and other is operated with example 1.Yield is 81%, and the phenylcarbimide product purity is more than 98.0%.
Embodiment 9
Catalyzer changes the N-methylpyrrole into, and other is operated with example 1.Yield is 86%, and the phenylcarbimide product purity is 99.0%.
Embodiment 10
Organic solvent changes toluene into, and temperature of reaction is upgraded to 100-110 ℃, and other is operated with example 1.Yield is 85%, and the phenylcarbimide product purity is more than 99%.
Embodiment 11
Organic solvent changes chlorobenzene into, and temperature of reaction is upgraded to 120-130 ℃, and other is operated with example 1.Yield is 84%, and the phenylcarbimide product purity is more than 99%.
Embodiment 12
Organic solvent changes dimethylbenzene into, and temperature of reaction is upgraded to 135-145 ℃, and other is operated with example 1.Yield is 82%, and the phenylcarbimide product purity is more than 99%.
Embodiment 13
Organic solvent changes tetrahydrofuran (THF) into, and temperature of reaction is upgraded to 60-67 ℃, and other is operated with example 1.Yield is 79%, and the phenylcarbimide product purity is more than 98%.
Embodiment 14
Organic solvent changes tetracol phenixin into, and temperature of reaction is upgraded to 70-80 ℃, and other is operated with example 1.Yield is 75%, and the phenylcarbimide product purity is more than 98%.
Embodiment 15
Organic solvent changes ethyl acetate into, and temperature of reaction is upgraded to 70-80 ℃, and other is operated with example 1.Yield is 80%, and the phenylcarbimide product purity is more than 98%.
Embodiment 16
Reaction times changes 5h into, and other is operated with example 1.Yield is 86%, and the phenylcarbimide product purity is more than 99%.
Embodiment 17
Reaction times changes 8h into, and other is operated with example 1.Yield is 84%, and the phenylcarbimide product purity is more than 99%.
Embodiment 18
In thermometer, reflux condensing tube, constant pressure funnel and churned mechanically 500ml four-hole boiling flask are housed, add two (trichloromethyl) carbonic ethers of 110g, 250ml toluene and 3g tetrabutyl urea.Open and stir, and begin to drip 107g (1mol) para-totuidine.Finish, be warming up to 100 ℃, and at 100-110 ℃ of following reaction 3h, reaction finishes the back underpressure distillation and reclaims toluene, collect under the 1333pa cut-product phenylcarbimide 120g of 71-73 ℃ at last, yield is 90%.Through the gas Chromatographic Determination product purity is 99.0%.
Embodiment 19-28
In thermometer, reflux condensing tube, constant pressure funnel and churned mechanically 500ml four-hole boiling flask are housed, add two (trichloromethyl) carbonic ethers of 110g, 250ml toluene and 3g tetrabutyl urea.Open and stir, and begin to drip the 1mol arylamine, about 0.5-1h.Finish, be warming up to backflow, and under relevant temperature, (see Table 1) reaction 1-10h, reaction finishes the back vacuum distillation recovered solvent, press the vacuum tightness underpressure distillation or the air distillation of table 1 at last and collect the cut of relevant temperature, get the product phenylcarbimide, yield and purity see Table 1.
Table 1
Example 19-29 experimental result
Raw material-amine Reaction times (h) Solvent Temperature of reaction (℃) Vacuum tightness (Pa) Collection cut temperature (℃) Yield (%)
Ortho Toluidine 2 Toluene 100-110 Normal pressure 184-186 88.5
Meta-aminotoluene 2 Toluene 100-110 1600 74-76 89
O ethyl aniline 2 Toluene 100-110 399.9 54-56 86.6
2-n-propyl aniline 1.5 Toluene 100-110 6.7 49-51 82.5
4-tertiary butyl aniline 1.5 Toluene 100-110 266.6 49-51 88.8
Ortho-Chloro aniline 3 Chlorobenzene 120-130 1333 82-84 90.1
M-chloro aniline 3 Chlorobenzene 120-130 1333 76-78 87.9
P-Chlorobenzoic acid amide 3 Chlorobenzene 120-130 Normal pressure 202-204 90.5
O-bromoaniline 3.5 Chlorobenzene 120-130 66.7 62-64 85.1
M-bromoaniline 3.5 Chlorobenzene 120-130 Normal pressure 219-221 85
Para-bromoaniline 3.5 Chlorobenzene 120-130 1866.2 157-159 88
The present invention and existing chemical synthesis process relatively have safety simple to operate, and reaction time is short, and reaction yield is high, good product quality, and the advantages such as non-environmental-pollution are methods that is suitable for suitability for industrialized production.

Claims (1)

1. the chemical synthesis process of aryl isocyanate, it is characterized in that with arylamine and two (trichloromethyl) carbonic ethers be raw material under the effect of catalyzer tetrabutyl urea, one of them is synthesized into as solvent to select benzene, toluene, chlorobenzene, dimethylbenzene, tetrahydrofuran (THF), tetracol phenixin and ethyl acetate; Perhaps selecting with benzene is solvent, and catalyzer is selected triethylamine, pyridine, N-methylpyrrole, and one of them is synthesized into; The molar ratio of above-mentioned reaction is an arylamine: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.34~0.8: 0.001-0.1; Its solvent load is 2-8 a times of arylamine quality; Its temperature of reaction is 15-150 ℃, and its reaction times is 1~10h.
CN 02130077 2002-08-13 2002-08-13 Chemical synthesis method of aryl isocyanate Expired - Fee Related CN1235874C (en)

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1939899B (en) * 2005-09-26 2011-12-21 杭州崇舜化学有限公司 Synthesis of 1,5-naphthalene isocyanate
CN104418773A (en) * 2013-09-02 2015-03-18 上海龙翔生物医药开发有限公司 Synthetic method of 2,4,5-trifluoro-benzene isocyanate and intermediate thereof
CN104447412A (en) * 2014-11-12 2015-03-25 上海朗亿新材料科技有限公司 Preparation method of isocyanate
CN104744306A (en) * 2015-04-10 2015-07-01 湖南利洁生物化工有限公司 P-chloroaniline isocyanate preparation method
CN110903216A (en) * 2019-12-19 2020-03-24 山东华阳农药化工集团有限公司 Preparation of diphenyl ethane diisocyanate by solid phosgene method and application thereof
CN112679388A (en) * 2020-12-28 2021-04-20 浙江丽水有邦新材料有限公司 Preparation method and preparation device of 2, 6-diisopropylbenzene isocyanate
CN113773230A (en) * 2021-09-07 2021-12-10 京博农化科技有限公司 Method for synthesizing diflubenzuron by one-pot method
CN114230489A (en) * 2021-12-31 2022-03-25 浙江丽水有邦新材料有限公司 Preparation and purification method and purification device of m-tolyl isocyanate

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