CN1824651A - Method of synthesizing thio methyl carbamater from aniline under normal pressure - Google Patents
Method of synthesizing thio methyl carbamater from aniline under normal pressure Download PDFInfo
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- CN1824651A CN1824651A CN 200510009536 CN200510009536A CN1824651A CN 1824651 A CN1824651 A CN 1824651A CN 200510009536 CN200510009536 CN 200510009536 CN 200510009536 A CN200510009536 A CN 200510009536A CN 1824651 A CN1824651 A CN 1824651A
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Abstract
The present invention relates to a method capable of utilizing aniline to synthesize thio carbamate at normal pressure. Said method is characterized by that under the action of selenium, in the presence of organic alkali and in the presence of normal pressure CO the aniline and sulfide can be undergone the process of carbonylation reaction so as to obtain thiocarbamate, at the same time the hydrogen selenide also can be produced. After the hydrogen selenide is oxidated in air, the selenium can be again obtained. Besides, said invention also provides the concrete condition and requirements of said carbonylation reaction.
Description
Technical Field
The invention relates to a method for synthesizing thiocarbamate from aniline under normal pressure. In particular, in a system of selenium and carbon monoxide, a method with mild reaction conditions, short steps and convenient operation is provided for the synthesis of thiocarbamate through the carbonylation reaction of aniline and mercaptan or thiophenol (sulfide 1, RSH), thereby promoting the development of the synthesis method of thiocarbamate.
Background
The thiocarbamate compounds are important fine chemicals and can be used as bactericides, insecticides and herbicides in the aspect of pesticides; biologically useful as bioregulators and enzyme inhibitors; can be used as anesthetic, bactericide and antiviral agent. In addition, it is also an important intermediate for fine chemicals.
Currently, there are three main methods for synthesizing such compounds: one is the reaction of carbamoyl chloride with a thiol or derivative thereof. The raw material of the reaction, namely the carbamyl chloride, is complex, the source is inconvenient, the preparation method usually involves the virulent phosgene, a large amount of byproducts are generated in the reaction, and the post-treatment is difficult, such as U.S. Pat. Nos. 2913327, 2983747 and 3836524. Secondly, isocyanate is reacted with mercaptan. The starting isocyanates used in these reactions are complex, expensive, inconvenient to source and often involve the production of highly toxic phosgene, as described in US 4066681, j. chem. soc. perkin tras.11977, 1069. Thirdly, the reaction is carried out by amine, carbon monoxide and sulfur, and then halogenated hydrocarbon is used for alkylation, or gaseous carbonyl sulfur is used for replacing carbon monoxide and sulfur. Such processes have many operating steps, large solvent usage, and often require large excesses of one or both of the starting materials, low atom economy, and often low yields, as described in U.S. patents US 3151119, US 3167571, and US 5565602.
Disclosure of Invention
The invention aims to provide a method for synthesizing thiocarbamate from aniline under normal pressure.
The method has the advantages of short steps, mild reaction conditions, low cost, simple operation and environmental friendliness, and the organic base is triethylamine, tripropylamine, tributylamine, pyridine and the like.
Wherein the carbon monoxide can be industrial carbon monoxide tail gas containing air, nitrogen, carbon dioxide and/or water vapor, and the sum of the contents of the air, the nitrogen, the carbon dioxide and/or the water vapor is less than or equal to 10 percent of the total volume.
Wherein the organic solvent is one or more polar or non-polar inert solvents; the polar solvent is tetrahydrofuran, N-dimethylformamide, acetone, ethanol, chloroform and the like, and the nonpolar solvent is toluene, N-hexane, 1, 4-dioxane, benzene and the like.
The invention has the beneficial effects that:
1. the invention reduces the production cost by using simple and easily obtained starting raw materials.
2. The method has the advantages of very mild reaction conditions, simple operation and contribution to large-scale industrial production by metering selenium.
3. The invention greatly improves the reaction activity of the carbon monoxide by activating the carbon monoxide by selenium, thereby avoiding the use of phosgene and improving the environmental friendliness.
4. The method has the advantages of short reaction steps, low process difficulty and good economy.
5. The selenium is easy to recover and can be recycled.
6. The product of the invention is easy to separate and purify. In addition, the method also has the advantages of high atom economy, stable product quality andthe like.
Detailed Description
The present invention is described in detail below by way of examples; however, the present invention is not limited to the following examples.
Example 1
A500 mL round-bottom three-necked flask was charged with aniline (5mmol), Se (5mmol), propanethiol (5mmol), Et3N (10mmol), the flask was evacuated and then charged with CO and connected to atmospheric CO; stirring the mixture at room temperature for reaction for 10 hours, and stopping the reaction; stirring in air for 30 min, filtering and recovering Se. Concentrating the filtrate, purifying by column chromatography to obtain eluent of petroleum ether and chloroform 1: 2(v/v), and concentrating to remove the eluent to obtain the product, wherein the product is N-phenyl propyl thiocarbamate, and the yield is 86.0%. Or directly recrystallizing in petroleum ether to obtain colorless needle crystal.
Example 2
A500 mL round-bottom three-necked flask was charged with aniline (5mmol), Se (5mmol), propanethiol (5mmol), Et3N (10mmol), the flask was evacuated and then charged with CO and allowed to react with atmospheric pressureGood economical efficiency and high yield.
The technical scheme of the invention is as follows:
under the action of stoichiometric selenium and in the presence of organic alkali, aniline and mercaptan or thiophenol are carbonylated in the presence of CO at normal pressure to obtain thiocarbamate and hydrogen selenide. The hydrogen selenide is oxidized in the air to obtain the selenium again, and the activity of the hydrogen selenide is kept unchanged, so the selenium can be recycled. The reaction can be carried out under the condition of no solvent or under the condition of polar or non-polar organic solvent; the reaction formula is as follows:
wherein:
r in the sulfide (thiol or thiophenol, RSH represented by the number 1 in the reaction formula) may be an alkyl group, or an aryl group with one or more electron donating or withdrawing groups.
The molar ratio of aniline to mercaptan or thiophenol compound is 10: 1 to 1: 10.
The molar amount of selenium is equal to the smaller molar amount of the reactant mercaptan or thiophenol and aniline.
The molar amount of the organic base is 1-400% of the smaller molar amount of the reactant aniline and thiol or thiophenol compound.
The reaction can be carried out under the condition of no solvent or in an organic solvent. When an organic solvent is used, the amount of the solvent to be added is not particularly limited, and generally, the molar ratio of the organic solvent to the reactant thiol or thiophenol in a smaller molar amount to the aniline is 1: 1 to 1: 50.
The reaction time is 1-40 hours.
The reaction temperature is 0-100 ℃.
The carbon monoxide reaction pressure is normal pressure.
The alkyl group in the reactant sulfide may be a straight-chain alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, a branched-chain alkyl group such as an isopropyl group or an isobutyl group, or a cyclic alkyl group such as a cyclohexyl group. The thiophenol compound may have no substituent or substituent on the benzene ring, wherein the electron donating substituent is methyl, ethyl, isopropyl or methoxy, etc., and the electron withdrawingsubstituent is chlorine, bromine, iodine, trifluoromethyl or trifluoromethoxy, etc.
Connecting with CO; stirring the mixture at room temperature for reaction for 10 hours, and stopping the reaction; adding a proper amount of solvent 1, 4-dioxane (the amount of the solvent added in the invention is not strictly limited, generally, the molar ratio of the smaller molar amount of mercaptan or thiophenol and aniline to the organic solvent is 1: 1 to 1: 50), stirring the reaction mixture in air for 30 minutes, and filtering to recover Se. Other experimental methods and conditions were the same as in example 1. The yield thereof was found to be 85.6%.
Example 3
The mercaptan was ethanethiol in an amount of 0.5mmol, the other experimental procedures and conditions were the same as in example 2, and the product was N-phenylthiourethane, yielding 86.1%.
Example 4
The mercaptan was isopropylmercaptan in an amount of 5mmol, and other experimental procedures and conditions were the same as in example 2, and the product was isopropyl N-phenylthiocarbamate, which was obtained in a yield of 63.5%.
Example 5
The mercaptan was butylmercaptan in an amount of 5mmol, and other experimental methods and conditions were the same as in example 2, and the product was N-phenylthiocarbamate, which was obtained in a yield of 83.1%.
Example 6
The mercaptan was pentanethiol in an amount of 5mmol, other experimental procedures and conditions were the same as in example 2, and the product was pentyl N-phenylthiocarbamate, giving a yield of 83.3%.
Example 7
The mercaptan was N-hexylmercaptan in an amount of 5mmol, the other experimental procedures and conditions were the same as in example 2, and the product was N-hexylN-phenylthiocarbamate, which was obtained in 83.4% yield.
Example 8
The mercaptan was cyclohexylmercaptan in an amount of 5mmol, the product was cyclohexyl N-phenylthiocarbamate in the same experimental procedure and conditions as in example 2, and the yield was 73.9%.
Example 9
The mercaptan was benzyl mercaptan in an amount of 10mmol, as in example 2, and the product was benzyl N-phenylthiocarbamate in 90.4% yield.
Example 10
The thiophenol was thiophenol in an amount of 10mmol, and other experimental methods and conditions were the same as in example 1, and the product was phenyl N-phenylthiocarbamate, and the yield was found to be 30.5%.
Example 11
The thiophenol was 4-chloro-thiophenol in an amount of 50mmol, and 2ml of acetone was additionally added, and other experimental methods and conditions were the same as in example 2, and the product was 4-chloro-phenyl N-phenylthiocarbamate, and the yield was 22.0%.
Example 12
The thiophenol was 4-methyl-thiophenol in an amount of 10mmol, and other experimental methods and conditions were the same as in example 2, and the product was 4-methyl-phenyl N-phenylthiocarbamate, giving a yield of 39.5%.
Example 13
The thiophenol was 4-methoxy-thiophenol in an amount of 10mmol, and the product was 4-methoxy-phenyl N-phenylthiocarbamate in the same experimental method and conditions as in example 2, giving a yield of 53.2%.
Example 14
The amount of tripropylamine used is 0.05mmol, and other experimental methods and conditions are the same as in example 2, whereby the yield is 66.6%.
Example 15
The amount of tributylamine used was 5mmol, and the other experimental methods and conditions were the same as in example 2, yielding 79.9%.
Example 16
The amount of pyridine used was 20mmol, and the other experimental methods and conditions were the same as in example 2, whereby the yield was 85.0%.
Example 17
The reaction time was 40 hours, and other experimental methods and conditions were the same as in example 2, to obtain a yield of 61.5%.
Example 18
The reaction time was 1 hour, and other experimental methods and conditions were the same as in example 2, yielding 81.9%.
Example 19
The reaction temperature was 0 ℃ and the other experimental methods and conditions were the same as in example 2, giving a yield of 76.8%.
Example 20
The reaction temperature was 50 ℃ and the other experimental methods and conditions were the same as in example 2, giving a yield of 54.3%.
Example 21
The reaction temperature was 100 ℃ and the other experimental methods and conditions were the same as in example 2, giving a yield of 35.8%.
Example 22
The solvent used was toluene in an amount of 2ml, and other experimental methods and conditions were the same as in example 2, whereby the yield was 80.9%.
Example 23
Tetrahydrofuran was used as a solvent in an amount of 2ml, and other experimental methods and conditions were the same as in example 2, whereby the yield was 85.0%.
Example 24
The solvent used was 2ml of ethanol, and other experimental methods and conditions were the same as in example 2, whereby the yield was 83.0%.
Example 25
The solvent was N, N-dimethylformamide in an amount of 2ml, and other experimental methods and conditions were the same as in example 2, whereby the yield was 86.0%
Example 26
The amount of acetone used was 2ml, and the other experimental methods and conditions were the same as in example 2, yielding 87.1%.
Example 27
The amount of propanethiol used was 6mmol, and the other experimental procedures and conditions were the same as in example 2, giving a yield of 84.0%.
Example 28
The amount of propanethiol used was 10mmol, and the other experimental procedures and conditions were the same as in example 2, giving a yield of 83.0%.
Claims (9)
1. A process for synthesizing thiocarbamate from phenylamine under ordinary pressure has the following reaction formula
In the formula:
RSH is sulfide, wherein substituent R is alkyl or aryl with one or more electron donating groups or electron withdrawing groups;
the method mainly comprises the following steps:
a) adding aniline, selenium, sulfide and organic base into carbon monoxide atmosphere, and reacting for 1-40 hours at 0-100 ℃;
b) stirring the reactant in the air for 10-60 minutes, filtering, concentrating the filtrate, purifying by column chromatography, and eluting the eluent according to the volume ratio of 1: 2 of petroleum ether to chloroform; concentrating to remove the eluent to obtain a target product;
the sulfide is mercaptan or thiophenol, and the molar ratio of the sulfide to the aniline is 10: 1 to 1: 10;
the molar dosage of selenium is the same as that of the less sulfide and aniline;
the molar consumption of the organic base is 1-400% of the less molar consumption of the sulfide and the aniline;
the carbon monoxide reaction pressure is normal pressure.
2. The process according to claim 1, wherein step b is carried out after addition of the organic solvent to the reactants of step a, the molar ratio of the less molar amount of sulfide to aniline to organic solvent being from 1: 1 to 1: 50.
3. The process according to claim 2, characterized in that the organic solvent is one or more polar or non-polar inert solvents.
4. A process according to claim 3, characterized in that the polar solvent is tetrahydrofuran, N-dimethylformamide, acetone, ethanol or chloroform and the nonpolar solvent is toluene, N-hexane, 1, 4-dioxane or benzene.
5. The process as claimed in claim 1, characterized in that the sulfide is ethanethiol, propanethiol, isopropylmercaptan, butanethiol, pentanethiol, n-hexanethiol, cyclohexanethiol, benzylmercaptan, thiophenol, 4-chloro-thiophenol or 4-methoxy-thiophenol.
6. The process according to claim 1, wherein the alkyl group represented by R in the sulfide is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a cyclohexyl group.
7. The process of claim 1, further characterized in that the electron donating substituent represented by R in the thiophenol is methyl, ethyl, isopropyl, or methoxy; the electron-withdrawing substituent is chlorine, bromine, iodine, carbonyl, trifluoromethyl or trifluoromethoxy.
8. The process according to claim 1, characterized in that the carbon monoxide is an industrial carbon monoxide off-gas comprising air, nitrogen, carbon dioxide and/or water vapour, the sum of the contents of air, nitrogen, carbon dioxide and/or water vapour being less than or equal to 10% of the total volume.
9. A process according to claim 1, characterized in that the organic base is triethylamine, tripropylamine, tributylamine or pyridine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200510009536 CN1824651A (en) | 2005-02-21 | 2005-02-21 | Method of synthesizing thio methyl carbamater from aniline under normal pressure |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510009536 CN1824651A (en) | 2005-02-21 | 2005-02-21 | Method of synthesizing thio methyl carbamater from aniline under normal pressure |
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| CN1824651A true CN1824651A (en) | 2006-08-30 |
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| CN 200510009536 Pending CN1824651A (en) | 2005-02-21 | 2005-02-21 | Method of synthesizing thio methyl carbamater from aniline under normal pressure |
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