CN1847224A - Process of synthesizing thiocarbamate from aniline - Google Patents
Process of synthesizing thiocarbamate from aniline Download PDFInfo
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- CN1847224A CN1847224A CN 200510011565 CN200510011565A CN1847224A CN 1847224 A CN1847224 A CN 1847224A CN 200510011565 CN200510011565 CN 200510011565 CN 200510011565 A CN200510011565 A CN 200510011565A CN 1847224 A CN1847224 A CN 1847224A
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- aniline
- thiophenol
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- carbon monoxide
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Abstract
The present invention is process of synthesizing N-phenyl thiocarbamate from aniline. In the presence of selenium catalyst and organic base, aniline and mercaptan or theophenol as reactants produce oxidation and carbonylation in CO and O2 to produce N-phenyl thiocarbamate. The present invention has facile materials, low cost, less production steps, mild reaction condition, high selectivity, high yield, and other advantages, and the selenium catalyst may be separated and recovered easily for reuse.
Description
Technical field
The present invention relates to a kind of novel method by the aniline synthesizing thiocarbamate.Specifically, be under selenium catalysis, in the presence of carbon monoxide and oxygen oxidation carbonylation takes place by aniline and mercaptan or thiophenol (RSH), for the synthetic of thiocarbamate provides a kind of reaction conditions gentleness, more brief, the easy to operate novel method of step, thereby further promoted the development of thiocarbamate synthetic method.
Background technology
Thiocarbamates compound is the important fine chemicals of a class, can be used as sterilant, sterilant and weedicide aspect agricultural chemicals; Aspect biological, can be used as biological regulator and enzyme inhibitors; Pharmaceutically can be used as narcotic, sterilant and antiviral agent.In addition, it also is the important intermediate of fine chemicals.
At present, the method for synthetic this compounds mainly contains three kinds: the one, and urea chloride reacts with the mercaptan or derivatives thereof.This class is reacted the phosgene that raw materials used urea chloride more complicated, source inconvenience, preparation method are usually directed to severe toxicity, and reaction has a large amount of by products to generate, the aftertreatment difficulty, and as U.S. Pat 2913327, US 2983747, and US 3836524.The 2nd, with the same thiol reactant of isocyanic ester.Isocyanate material complexity, costliness, source inconvenience that the reaction of this class is used, and its preparation also often relates to the phosgene of severe toxicity, as U.S. Pat 4066681, and J.Chem.Soc.Perkin Tras.11977,1069.The 3rd, react with amine, carbon monoxide and sulphur earlier, and then use the halohydrocarbon alkylation, perhaps substitute carbon monoxide and sulphur with the gaseous state carbonylsulfide.This method operation steps is many, solvent load is big, and needs one or both starting raw materials excessive greatly usually, and Atom economy is low, and yield is not high usually, and as U.S. Pat 3151119, US 3167571, and US 5565602.In addition, we have reported that recently with aromatic nitro compound and mercaptan or thiophenol be starting raw material, (the Chinese patent application number: 200410068874.7) of the method for synthesizing thiocarbamate under condition of high voltage
Summary of the invention
The object of the present invention is to provide a kind of method by the synthetic N-phenyl thiocarbamate of aniline, preparation method's step of the present invention is brief, reaction conditions is gentle, cost is low, simple to operate, environmental friendliness, Atom economy is good, yield is high.
For achieving the above object, method by the synthetic N-phenyl thiocarbamate of aniline provided by the invention, with selenium is catalyzer, aniline and mercaptan or aniline and thiophenol are reactant, organic bases exists down, in carbon monoxide and oxygen oxidation carbonylation takes place, generate thiocarbamate, reaction formula is as follows:
Wherein:
R is an alkyl or with the aryl of one or more electron-donating groups or electron-withdrawing group;
The molar ratio of material of mercaptan or thiophenol and aniline is 2: 1 to 1: 2;
The mole dosage of selenium be in the reactant the less side of mole dosage 1～10%;
The mole dosage of organic bases be in the reactant the less side of mole dosage 10～400%;
Reaction times is 1～40 hour;
Temperature of reaction is room temperature～70 ℃;
The mol ratio of carbon monoxide and oxygen is 1: 1 to 20: 1;
The reaction stagnation pressure of carbon monoxide and oxygen is normal pressure-10MPa.
Described R is an alkyl, also can be the aryl with one or more electron-donating groups or electron-withdrawing group.When R is alkyl, can be straight chained alkyls such as methyl, ethyl, propyl group, butyl, also can be branched-chain alkyls such as sec.-propyl, isobutyl-, can also be cyclic alkyls such as cyclohexyl.
When described reactant is thiophenol, be methyl, ethyl, sec.-propyl or methoxyl group to electron substituent group in the thiophenol, electron-withdrawing substituent is chlorine, bromine, iodine, carbonyl, trifluoromethyl or trifluoromethoxy.
Described organic bases is triethylamine, tripropyl amine, Tributylamine or 1,8-diazabicyclo [5.4.0] 11-7-alkene (DUB).
Described carbon monoxide is the industrial carbon monoxide tail gas that contains air, nitrogen, carbonic acid gas and/or water vapour, and wherein the content sum of air, nitrogen, carbonic acid gas and/or water vapour is smaller or equal to 10% of cumulative volume.
Described reaction can also be carried out in organic solvent.When carrying out in being reflected at organic solvent, the mol ratio of less side of mole dosage and organic solvent is 1: 1 to 1: 50 in reactant mercaptan or thiophenol and the aniline.
Described organic solvent is one or more polarity or nonpolar inert solvent.
Described polar solvent is tetrahydrofuran (THF), N, and dinethylformamide, acetone, ethanol or chloroform, non-polar solvent are toluene, normal hexane, 1,4-dioxane or benzene.
The invention has the beneficial effects as follows:
The present invention by use be simple and easy to starting raw material, thereby reduced production cost.
2. the present invention makes reaction to finish in a step, thereby makes reactions steps more brief by the catalytic oxidation carbonylation of selenium, helps large-scale industrial production.
3. the present invention has improved the reactive behavior of carbon monoxide greatly by the activation of selenium to carbon monoxide, thereby has avoided the use of phosgene, has improved environment friendly.
4. reactions steps of the present invention is short, and technology difficulty is low, good economy performance.
5. selenium of the present invention reclaims easily, and can recycle.
6. product separation and purification of the present invention is easy.The present invention also has Atom economy height, advantages such as constant product quality in addition.
Embodiment
Below by embodiment in detail the present invention is described in detail; Yet, the invention is not restricted to following embodiment.
Embodiment 1
In the 100ml stainless steel autoclave, add aniline (5mmol), Se (0.15mmol), propylmercaptan (5mmol), Et
3N (10mmol) is with CO and O
2Mixed gas (mol ratio 9: 1) displacement three times after the pressure of mixed gas is risen to 1.0MPa.With its stirring reaction after 10 hours at room temperature, stopped reaction.Open the still venting, get solid crude product.To wherein add an amount of dissolution with solvents it, filter, can be recovered to Se again.Concentrated filtrate, through column chromatography purification, elutriant is a sherwood oil: chloroform (1: 2), concentrate and to remove elutriant and promptly get product, product is a N-phenyl thiocarbamate propyl ester, yield is 86.0%.Also direct recrystallization in sherwood oil, colourless acicular crystal.
Embodiment 2
Mercaptan is sulfur alcohol, and consumption is 5mmol, and other experimental technique and condition are with embodiment 1, and product is a N-phenyl thioxanthamide, and is real that yield is 83.9%.
Embodiment 3
Mercaptan is isopropyl mercaptan, and consumption is 5mmol, and other experimental technique and condition are with embodiment 1, and product is a N-phenyl thiocarbamate isopropyl ester, and is real that yield is 61.5%.
Embodiment 4
Mercaptan is pentan-thiol, and consumption is 5mmol, and other experimental technique and condition are with embodiment 1, and product is a N-phenyl thiocarbamate pentyl ester, and is real that yield is 83.3%.
Embodiment 5
Mercaptan is positive hexylmercaptan, and consumption is 5mmol, and other experimental technique and condition are with embodiment 1, and product is the just own ester of N-phenyl thiocarbamate, and is real that yield is 80.9%.
Embodiment 6
Mercaptan is cyclohexylmercaptan, and consumption is 5mmol, and other experimental technique and condition are with embodiment 1, and product is a N-phenyl thiocarbamate cyclohexyl, and is real that yield is 72.7%.
Embodiment 7
Mercaptan is benzyl sulfhydrate, and consumption is 5mmol, and other experimental technique and condition are with embodiment 1, and product is a N-phenyl thiocarbamate benzyl ester, and is real that yield is 86.3%.
Embodiment 8
Thiophenol is a thiophenol, and consumption is 5mmol, and other experimental technique and condition are with embodiment 1, and product is a N-phenyl thiocarbamate phenyl ester, and is real that yield is 34.9%.
Embodiment 9
Thiophenol is a 4-chloro-thiophenol, and consumption is 5mmol, and other adds 2ml acetone, and other experimental technique and condition are with embodiment 1, and product is N-phenyl thiocarbamate-4-chloro-phenyl ester, and is real that yield is 22.7%.
Embodiment 10
Thiophenol is 4-methyl-thiophenol, and consumption is 10mmol, and other experimental technique and condition are with embodiment 1, and product is N-phenyl thiocarbamate-4-methyl-phenyl ester, and is real that yield is 37.8%.
Embodiment 11
Thiophenol is 4-methoxyl group-thiophenol, and consumption is 10mmol, and other experimental technique and condition are with embodiment 1, and product is N-phenyl thiocarbamate-4-methoxyl group-phenyl ester, and is real that yield is 47.8%.
Embodiment 12
The consumption of triethylamine is 2.5mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 57.4%.
Embodiment 13
The consumption of triethylamine is 20mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 86.0%.
Embodiment 14
The consumption of DUB is 10mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 19.5%.
Embodiment 15
Reaction times is 1 hour, and other experimental technique and condition are with embodiment 1, and be real that yield is 21.7%.
Embodiment 16
Reaction times is 40 hours, and other experimental technique and condition are with embodiment 1, and be real that yield is 86.0%.
Embodiment 17
Temperature of reaction is 30 ℃, and other experimental technique and condition are with embodiment 1, and be real that yield is 65.5%.
Embodiment 18
Temperature of reaction is 50 ℃, and other experimental technique and condition are with embodiment 1, and be real that yield is 47.1%.
Embodiment 19
Temperature of reaction is 70 ℃, and other experimental technique and condition are with embodiment 1, and be real that yield is 27.7%.
Embodiment 20
Solvent toluene, consumption are 2ml, and other experimental technique and condition are with embodiment 1, and be real that yield is 83.0%.
Embodiment 21
Solvent tetrahydrofuran (THF), consumption are 2ml, and other experimental technique and condition are with embodiment 1, and be real that yield is 84.0%.
Embodiment 22
Solvent ethanol, consumption are 2ml, and other experimental technique and condition are with embodiment 1, and be real that yield is 85.0%.
Embodiment 23
Solvent N, dinethylformamide, consumption are 2ml, other experimental technique and condition are with embodiment 1, and be real that yield is 85.0%.
Embodiment 24
Solvent acetone, consumption are 2ml, and other experimental technique and condition are with embodiment 1, and be real that yield is 86.0%.
Embodiment 25
The propylmercaptan consumption is 6mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 85.0%.
Embodiment 26
The propylmercaptan consumption is 10mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 86.0%.
Embodiment 27
The consumption of selenium is 0.05mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 62.5%.
Embodiment 28
The consumption of selenium is 0.50mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 60.4%.
Embodiment 29
The consumption of propylmercaptan is 10mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 86.0%.
Embodiment 30
The mol ratio of carbon monoxide and oxygen is 1: 1, and other experimental technique and condition are with embodiment 1, and be real that yield is 21.5%.
Embodiment 31
The total pressure of carbon monoxide and oxygen is a normal pressure, and other experimental technique and condition are with embodiment 1, and be real that yield is 14.3%.
Claims (9)
1, a kind of method by the synthetic N-phenyl thiocarbamate of aniline, selenium is catalyzer, aniline and mercaptan or aniline and thiophenol are reactant, organic bases exists down, in carbon monoxide and oxygen oxidation carbonylation takes place, generate thiocarbamate, reaction formula is as follows:
Wherein:
R is an alkyl or with the aryl of one or more electron-donating groups or electron-withdrawing group;
The molar ratio of material of mercaptan or thiophenol and aniline is 2: 1 to 1: 2;
The mole dosage of selenium be in the reactant the less side of mole dosage 1～10%;
The mole dosage of organic bases be in the reactant the less side of mole dosage 10～400%;
Reaction times is 1～40 hour;
Temperature of reaction is room temperature～70 ℃;
The mol ratio of carbon monoxide and oxygen is 1: 1 to 20: 1;
The reaction stagnation pressure of carbon monoxide and oxygen is normal pressure-10MPa.
2, in accordance with the method for claim 1, it is characterized in that R is methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-or cyclohexyl.
3, in accordance with the method for claim 1, its feature also is, when reactant is thiophenol, is methyl, ethyl, sec.-propyl or methoxyl group to electron substituent group in the thiophenol, and electron-withdrawing substituent is chlorine, bromine, iodine, carbonyl, trifluoromethyl or trifluoromethoxy.
4, in accordance with the method for claim 1, it is characterized in that wherein said organic bases is triethylamine, tripropyl amine, Tributylamine or 1,8-diazabicyclo [5.4.0] 11-7-alkene.
5, in accordance with the method for claim 1, it is characterized in that, carbon monoxide is the industrial carbon monoxide tail gas that contains air, nitrogen, carbonic acid gas and/or water vapour, and wherein the content sum of air, nitrogen, carbonic acid gas and/or water vapour is smaller or equal to 10% of cumulative volume.
6, in accordance with the method for claim 1, it is characterized in that, be reflected in the organic solvent and carry out.
7. in accordance with the method for claim 6, it is characterized in that be reflected at when carrying out in the organic solvent, the mol ratio of less side of mole dosage and organic solvent is 1: 1 to 1: 50 in reactant mercaptan or thiophenol and the aniline.
According to claim 6 or 7 described methods, it is characterized in that 8, wherein said organic solvent is one or more polarity or nonpolar inert solvent.
9, in accordance with the method for claim 8, it is characterized in that described polar solvent is tetrahydrofuran (THF), N, dinethylformamide, acetone, ethanol or chloroform, non-polar solvent are toluene, normal hexane, 1,4-dioxane or benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510011565 CN1847224A (en) | 2005-04-14 | 2005-04-14 | Process of synthesizing thiocarbamate from aniline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510011565 CN1847224A (en) | 2005-04-14 | 2005-04-14 | Process of synthesizing thiocarbamate from aniline |
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| CN1847224A true CN1847224A (en) | 2006-10-18 |
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| CN 200510011565 Pending CN1847224A (en) | 2005-04-14 | 2005-04-14 | Process of synthesizing thiocarbamate from aniline |
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