CN1468845A - Chemical synthesis of p-methoxyphenyl isocyanate - Google Patents

Chemical synthesis of p-methoxyphenyl isocyanate Download PDF

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CN1468845A
CN1468845A CNA03124291XA CN03124291A CN1468845A CN 1468845 A CN1468845 A CN 1468845A CN A03124291X A CNA03124291X A CN A03124291XA CN 03124291 A CN03124291 A CN 03124291A CN 1468845 A CN1468845 A CN 1468845A
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nethoxyaniline
trichloromethyl
chemical synthesis
toluene
synthesis process
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CN1228316C (en
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蔡戈冬
曹国君
王波华
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ZHEJIANG TONGFENG PHARMACEUTICAL CHEMICAL CO Ltd
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Abstract

The chemical synthesis of p-methoxyphenyl isocyanate is one process inside organic solvent with methoxyphenyl amine and di(trichloromethyl) carbonate as material and in the presence of catalyst. The process has the material molar ratio of methoxyphenyl amine to di(trichloromethyl) carbonate to catalyst being 1 to 0.34-0.8 to 0.01-0.1; organic solvent amount is 3-12 times mass of methoxyphenyl amine; the reaction temperature is 20-180 deg.c and reaction period is 4-10 hr. The organic solvent may be benzene, toluene, xylene, chlorobenzene, dichloro benzene, dichloro methane, trichloro methane, carbon tetrachloride, ethylidene dichloride, tetrafuran or hexaalkane epoxide. The said process uses no virulent phosgene and diphosgene, and is safe, reliable, high in yield, low in cost, and less corrosive and waste exhaust.

Description

A kind of chemical synthesis process of p-Methoxyphenyl isocyanate
Technical field
The present invention relates to synthetic medicine, agricultural chemicals and dye field, mainly is a kind of chemical synthesis process of p-Methoxyphenyl isocyanate.
Background technology
P-Methoxyphenyl isocyanate is important medicine, agricultural chemicals and macromolecular material intermediate.The chemical synthesis process of prior art p-Methoxyphenyl isocyanate is to be that raw material reaction makes with phosgene and P-nethoxyaniline.The shortcoming of this technology is to use in the world the hypertoxic raw material phosgene that restriction is used, and potential safety hazard is big, and reaction time is long, and equipment corrosion is serious, and what bother most is that quantity of three wastes is big, and difficult treatment, expense height.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of technology is reasonable, production safety is reliable, reaction yield is high, production cost is low, does not have the p-Methoxyphenyl isocyanate chemical synthesis process of the three wastes substantially.
The technical solution adopted for the present invention to solve the technical problems.The chemical synthesis process of this p-Methoxyphenyl isocyanate, is that raw material is synthesized in the organic solvent in the presence of catalyzer with P-nethoxyaniline with two (trichloromethyl) carbonic ethers, and its molar ratio is a P-nethoxyaniline: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.34~0.8: 0.01-0.1; Its consumption of organic solvent is 3-12 a times of P-nethoxyaniline quality; Its temperature of reaction is 20-180 ℃; Its reaction times is 4~10h.
Its reaction equation is:
The technical solution adopted for the present invention to solve the technical problems can also be further perfect.Described organic solvent can be benzene or toluene or dimethylbenzene or chlorobenzene or dichlorobenzene or methylene dichloride or trichloromethane or tetracol phenixin or ethylene dichloride or tetrahydrofuran (THF) or epoxy six alkane.
Described catalyzer can be 1,3-dimethyl-2-imidazolidone or 1,3-diethyl-2-imidazolidone or other 1,3-dialkyl group-2-imidazolidone or triethylamine or pyridine or 3-picoline or N-methylpyrrole or N-methyl Pyrrolidine or tetrabutyl urea.
It is P-nethoxyaniline that molar ratio can be preferably its molar ratio: two (trichloromethyl) carbonic ether: toluene: 1, and 3-dimethyl-2-imidazolidone=1: 0.35: 0.02 (mol ratio), the charging capacity of toluene are 8 times of P-nethoxyaniline quality.At first with P-nethoxyaniline, 1,3-dimethyl-2-imidazolidone and toluene are added in the reactor, after stirring, at room temperature drip the toluene solution of two (trichloromethyl) carbonic ethers in the 30min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, then temperature rising reflux reaction 4h, reaction is finished, toluene is reclaimed in elder generation's air distillation, and 106-108 ℃ cut is collected in vacuum distilling then under 2KPa.
Or molar ratio is a P-nethoxyaniline: two (trichloromethyl) carbonic ether: tetrabutyl urea=1: 0.35: 0.01 (mol ratio), solvent chlorobenzene.At first with P-nethoxyaniline, tetrabutyl urea and chlorobenzene are added in the reactor, after stirring, at room temperature drip the chlorobenzene solution of two (trichloromethyl) carbonic ethers in the 45min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, temperature rising reflux reacts 4h then, and solvent is reclaimed in first air distillation, 106-108 ℃ cut is collected in vacuum distilling then under 2KPa.
Or its molar ratio is a P-nethoxyaniline: two (trichloromethyl) carbonic ether: tetrabutyl urea=1: 0.35: 0.02 (mol ratio), the charging capacity of benzene are 10 times of P-nethoxyaniline quality.At first with P-nethoxyaniline, tetrabutyl urea and benzene are added in the reactor, after stirring, at room temperature drip the benzole soln of two (trichloromethyl) carbonic ethers in the 45min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, temperature rising reflux reacts 5h then, and solvent is reclaimed in first air distillation, 106-108 ℃ cut is collected in vacuum distilling then under 2KPa.
The effect that the present invention is useful is: the present invention compared with prior art, the operational path advanced person, processing condition are reasonable, and used raw material has been avoided hypertoxic phosgene and trichloromethylchloroformate, and production safety is reliable, the reaction yield height, generally more than 93%, production cost is lower, and equipment corrosion is little, few and the easy processing of the three wastes has bigger implementary value and economic results in society.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
P-nethoxyaniline: two (trichloromethyl) carbonic ether: toluene: 1,3-dimethyl-2-imidazolidone=1: 0.35: 0.02 (mol ratio), the charging capacity of toluene are 8 times of P-nethoxyaniline quality.
P-nethoxyaniline, 1,3-dimethyl-2-imidazolidone and toluene are added in the reactor, after stirring, at room temperature drip the toluene solution of two (trichloromethyl) carbonic ethers in the 30min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, temperature rising reflux reaction 4h reacts and finishes then, and toluene is reclaimed in first air distillation, vacuum distilling then, under 2KPa, collect 106-108 ℃ cut, yield 95.6%, content (GC) 99.4%.
Embodiment 2
P-nethoxyaniline: two (trichloromethyl) carbonic ether: 1,3-dimethyl-2-imidazolidone=1: 0.35: 0.01 (mol ratio), the charging capacity that reclaims toluene is 8 times of P-nethoxyaniline quality.
P-nethoxyaniline, 1,3-dimethyl-2-imidazolidone and recovery toluene are added in the reactor, after stirring, at room temperature drip the toluene solution of two (trichloromethyl) carbonic ethers in the 30min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, temperature rising reflux reaction 4h reacts and finishes then, and toluene is reclaimed in first air distillation, vacuum distilling then, under 2KPa, collect 106-108 ℃ cut, yield 96.3%, content (GC) 99.3%.
Embodiment 3
P-nethoxyaniline: two (trichloromethyl) carbonic ether: 1,3-dimethyl-2-imidazolidone=1: 0.50: 0.02 (mol ratio), the charging capacity of toluene are 8 times of P-nethoxyaniline quality.
By embodiment 1 reaction that feeds intake, the last cut of under 2 KPa, collecting 106-108 ℃, yield 97.0%, content (GC) 99.0%.
Embodiment 4
P-nethoxyaniline: two (trichloromethyl) carbonic ether: 1,3-dimethyl-2-imidazolidone=1: 0.80: 0.02 (mol ratio), the charging capacity of toluene are 8 times of P-nethoxyaniline quality.
By embodiment 1 reaction that feeds intake, the last cut of under 2 KPa, collecting 106-108 ℃, yield 96.1%, content (GC) 98.8%.
Embodiment 5
P-nethoxyaniline: two (trichloromethyl) carbonic ether: tetrabutyl urea=1: 0.35: 0.02 (mol ratio), the charging capacity of benzene are 10 times of P-nethoxyaniline quality.
P-nethoxyaniline, tetrabutyl urea and benzene are added in the reactor, after stirring, at room temperature drip the benzole soln of two (trichloromethyl) carbonic ethers in the 45min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, temperature rising reflux reacts 5h then, solvent is reclaimed in elder generation's air distillation, and 106-108 ℃ cut is collected in vacuum distilling then under 2KPa, yield 93.6%, content (GC) 99.8%.
Embodiment 6
P-nethoxyaniline: two (trichloromethyl) carbonic ether: tetrabutyl urea=1: 0.35: 0.01 (mol ratio), solvent chlorobenzene.
P-nethoxyaniline, tetrabutyl urea and chlorobenzene are added in the reactor, after stirring, at room temperature drip the chlorobenzene solution of two (trichloromethyl) carbonic ethers in the 45min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, temperature rising reflux reaction 4h reacts and finishes then, and other is with embodiment 5.Yield 93.8%, content (GC) 99.7%.
Embodiment 7
P-nethoxyaniline: two (trichloromethyl) carbonic ether: pyridine=1: 0.35: 0.2 (mol ratio), solvent toluene.
P-nethoxyaniline, pyridine and toluene are added in the reactor, after stirring, at room temperature drip the toluene solution of two (trichloromethyl) carbonic ethers in the 45min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, then temperature rising reflux reaction 4h, reaction is finished, and other is with embodiment 5.Yield 93.1%, content (GC) 99.5%.

Claims (9)

1, a kind of chemical synthesis process of p-Methoxyphenyl isocyanate, it is characterized in that: is that raw material is synthesized in the organic solvent in the presence of catalyzer with P-nethoxyaniline with two (trichloromethyl) carbonic ethers, and its molar ratio is a P-nethoxyaniline: two (trichloromethyl) carbonic ether: catalyzer is 1: 0.34~0.8: 0.01-0.1; Its consumption of organic solvent is 3-12 a times of P-nethoxyaniline quality; Its temperature of reaction is 20-180 ℃; Its reaction times is 4~10h.
2, the chemical synthesis process of p-Methoxyphenyl isocyanate according to claim 1 is characterized in that: described organic solvent can be benzene or toluene or dimethylbenzene or chlorobenzene or dichlorobenzene or methylene dichloride or trichloromethane or tetracol phenixin or ethylene dichloride or tetrahydrofuran (THF) or epoxy six alkane.
3, the chemical synthesis process of p-Methoxyphenyl isocyanate according to claim 1, it is characterized in that: described catalyzer can be 1,3-dimethyl-2-imidazolidone or 1,3-diethyl-2-imidazolidone or other 1,3-dialkyl group-2-imidazolidone or triethylamine or pyridine or 3-picoline or N-methylpyrrole or N-methyl Pyrrolidine or tetrabutyl urea.
4, according to the chemical synthesis process of claim 1 or 2 or 3 described p-Methoxyphenyl isocyanates, it is characterized in that: its molar ratio is a P-nethoxyaniline: two (trichloromethyl) carbonic ether: toluene: 1,3-dimethyl-2-imidazolidone=1: 0.35: 0.02 (mol ratio), the charging capacity of toluene are 8 times of P-nethoxyaniline quality.
5, according to the chemical synthesis process of claim 1 or 2 or 3 described p-Methoxyphenyl isocyanates, it is characterized in that: its molar ratio P-nethoxyaniline: two (trichloromethyl) carbonic ether: tetrabutyl urea=1: 0.35: 0.02 (mol ratio), the charging capacity of benzene are 10 times of P-nethoxyaniline quality.
6, according to the chemical synthesis process of claim 1 or 2 or 3 described p-Methoxyphenyl isocyanates, it is characterized in that: its molar ratio is a P-nethoxyaniline: two (trichloromethyl) carbonic ether: tetrabutyl urea=1: 0.35: 0.01 (mol ratio), solvent chlorobenzene.
7, the chemical synthesis process of p-Methoxyphenyl isocyanate according to claim 4, it is characterized in that: at first with P-nethoxyaniline, 1,3-dimethyl-2-imidazolidone and toluene are added in the reactor, after stirring, at room temperature drip the toluene solution of two (trichloromethyl) carbonic ethers in the 30min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, temperature rising reflux reacts 4h then, reaction is finished, toluene is reclaimed in elder generation's air distillation, 106-108 ℃ cut is collected in vacuum distilling then under 2KPa.
8, the chemical synthesis process of p-Methoxyphenyl isocyanate according to claim 5, it is characterized in that: at first with P-nethoxyaniline, tetrabutyl urea and benzene are added in the reactor, after stirring, at room temperature drip the benzole soln of two (trichloromethyl) carbonic ethers in the 45min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, temperature rising reflux reacts 5h then, solvent is reclaimed in elder generation's air distillation, and 106-108 ℃ cut is collected in vacuum distilling then under 2KPa.
9, the chemical synthesis process of p-Methoxyphenyl isocyanate according to claim 6, it is characterized in that: at first with P-nethoxyaniline, tetrabutyl urea and chlorobenzene are added in the reactor, after stirring, at room temperature drip the chlorobenzene solution of two (trichloromethyl) carbonic ethers in the 45min, open the absorption system of byproduct hydrogen chloride system technical hydrochloric acid simultaneously, temperature rising reflux reacts 4h then, solvent is reclaimed in elder generation's air distillation, and 106-108 ℃ cut is collected in vacuum distilling then under 2KPa.
CN 03124291 2003-05-08 2003-05-08 Chemical synthesis of p-methoxyphenyl isocyanate Expired - Lifetime CN1228316C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101318913B (en) * 2008-07-21 2011-04-27 国家农药创制工程技术研究中心 Method for preparing parachlorobenzyl isocyanic ester
CN1939899B (en) * 2005-09-26 2011-12-21 杭州崇舜化学有限公司 Synthesis of 1,5-naphthalene isocyanate
CN102617401A (en) * 2012-03-08 2012-08-01 象山志华新材料有限公司 Synthesis method for co-producing p-chloroaniline and p-chlorophenol isocyanate

Cited By (3)

* 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
CN101318913B (en) * 2008-07-21 2011-04-27 国家农药创制工程技术研究中心 Method for preparing parachlorobenzyl isocyanic ester
CN102617401A (en) * 2012-03-08 2012-08-01 象山志华新材料有限公司 Synthesis method for co-producing p-chloroaniline and p-chlorophenol isocyanate

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