CN1721402A - A kind of method of synthesizing thiocarbamate - Google Patents
A kind of method of synthesizing thiocarbamate Download PDFInfo
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- CN1721402A CN1721402A CN 200410068874 CN200410068874A CN1721402A CN 1721402 A CN1721402 A CN 1721402A CN 200410068874 CN200410068874 CN 200410068874 CN 200410068874 A CN200410068874 A CN 200410068874A CN 1721402 A CN1721402 A CN 1721402A
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Abstract
A kind of method of synthesizing thiocarbamate, in the presence of CO, selenium is as catalyzer with mercaptan or thiophenol and aromatic nitro compound, and triethylamine is a promotor, reacts in the autoclave of sealing under condition of no solvent or in the organic solvent; Wherein: the substituent R on the oil of mirbane phenyl ring
1For H or one or more are given electronics or electron-withdrawing group; R in the sulfide
2Both can be alkyl, also can be aryl with one or more donor residuess or electron withdrawing group.The molar ratio of material of mercaptan or thiophenol and aromatic nitro compound is 10: 1 to 1: 10; The mole dosage of selenium be in the reactant the less side of mole dosage 0.1～20%; The mole dosage of triethylamine be in the reactant the less side of mole dosage 10～200%; The preparation mol ratio of reactant and organic solvent is 1: 1 to 1: 50; Reaction times is 1～20 hour; Temperature of reaction is 0～200 ℃; Reaction of carbon monoxide pressure is gauge pressure 0.1～10MPa.
Description
Technical field
The present invention relates to thiocarbamates compound, relate in particular to a kind of method of catalytic reduction carbonylation reaction synthesizing thiocarbamate.
Background technology
Thiocarbamates compound is the important fine chemicals of a class, can be used as sterilant, sterilant and weedicide aspect agricultural chemicals; 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.The reaction of this class is with used isocyanate material complexity, costliness, source inconvenience, and its preparation also often relates to hypertoxic phosgene, as U.S. Pat 4066681, and J.Chem.Soc.Perkin Tras.1 1977,1069.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, US5565602.
Summary of the invention
The object of the present invention is to provide that a kind of reaction conditions gentleness, cost are low, the method for environmental friendliness, simple to operate, Atom economy good, yield the is high synthetic thiocarbamates compound of catalytic reduction carbonylation.
For achieving the above object, the technical solution used in the present invention is as follows: in the presence of CO, be starting raw material with aromatic nitro compound and mercaptan or thiophenol, selenium is catalyzer, triethylamine is a promotor, and condition of no solvent reacts in the autoclave of sealing down or in organic solvent; Reaction formula is as follows:
Wherein:
Substituent R on the nitrobenzene compounds phenyl ring
1Can be hydrogen, also can be one or more electron-donating groups or electron-withdrawing group; R in the sulfide
2Can be alkyl, also can be aryl with one or more electron-donating groups or electron-withdrawing group; The molar ratio of material of nitrobenzene compounds and mercaptan or phenyl-sulfhydrate compounds is 10: 1 to 1: 10; The mole dosage of selenium be in reactant nitrobenzene compounds and mercaptan or the phenyl-sulfhydrate compounds the less side of mole dosage 0.1～20%; The mole dosage of triethylamine be in reactant nitrobenzene compounds and mercaptan or the phenyl-sulfhydrate compounds the less side of mole dosage 10～200%; Reaction can be carried out under condition of no solvent, also can carry out in organic solvent, and the preparation mol ratio of less side of mole dosage and organic solvent is 1: 1 to 1: 50 in reactant nitrobenzene compounds and mercaptan or the phenyl-sulfhydrate compounds; Reaction times is 1～20 hour; Temperature of reaction is 0～200 ℃; Reaction of carbon monoxide pressure is 0.1～10MPa;
Be methyl, ethyl, sec.-propyl or methoxyl group etc. to electron substituent group in the wherein said reactant nitrobenzene compounds, electron-withdrawing substituent is chlorine, bromine, trifluoromethyl or trifluoromethoxy etc.; Be methyl, ethyl, sec.-propyl or methoxyl group etc. to electron substituent group in the phenyl-sulfhydrate compounds, electron-withdrawing substituent is chlorine, bromine, trifluoromethyl or trifluoromethoxy etc.; Wherein said carbon monoxide can use 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; Wherein said organic solvent is one or more polarity or nonpolar inert solvent; Described polar solvent is toluene, tetrahydrofuran (THF), chloroform, acetone or N, and dinethylformamide etc., non-polar solvent are normal hexane or benzene etc.;
The present invention has following advantage:
1. cost is low.Raw material of the present invention is simple, be easy to get, and only uses the lower nonmetal selenium of price to be catalyzer.
2. the reaction conditions gentleness is simple to operate, helps large-scale industrial production.
3. the reaction process difficulty is low.
4. good economy performance.
5. catalyst recovery is easy, and can recycle.
6. the product separation and purification is easy.
7. the use of phosgene has been avoided in reaction, can carry out environmental friendliness under condition of no solvent.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 oil of mirbane (10mmol), Se (0.5mmol), propylmercaptan (10mmol), Et
3N (5mmol) rises to 0.8MPa with after the CO displacement three times with CO pressure, puts it in the oil bath pan that rises to 50 ℃ stirring reaction 10 hours, is cooled to room temperature then, opens the still venting, solid crude product.Dissolve it with tetrahydrofuran (THF), stirred 30 minutes, 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 83.5%.Also direct recrystallization in sherwood oil, colourless acicular crystal.
Embodiment 2
Mercaptan is sulfur alcohol, and consumption is 10mmol, and other experimental technique and condition are with embodiment 1, and product is a N-phenyl thioxanthamide, and is real that yield is 80.0%.
Embodiment 3
Mercaptan is isopropyl mercaptan, and consumption is 10mmol, 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 57.4%.
Embodiment 4
Mercaptan is butyl sulfhydryl, and consumption is 10mmol, and other experimental technique and condition are with embodiment 1, and product is a N-phenyl thiocarbamate butyl ester, and is real that yield is 80.2%.
Embodiment 5
Mercaptan is tert.-butyl mercaptan, and consumption is 10mmol, and other experimental technique and condition are with embodiment 1, and product is the N-phenyl thiocarbamate tert-butyl ester, and is real that yield is 7.6%.
Embodiment 6
Mercaptan is positive hexylmercaptan, and consumption is 10mmol, 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 74.6%.
Embodiment 7
Mercaptan is cyclohexylmercaptan, and consumption is 10mmol, and other experimental technique and condition are with embodiment 1, and product is a N-phenyl thiocarbamate cyclohexyl, and is real that yield is 67.1%.
Embodiment 8
Mercaptan is benzyl sulfhydrate, and consumption is 10mmol, 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 61.6%.
Embodiment 9
Thiophenol is a thiophenol, and consumption is 10mmol, 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 15.3%.
Embodiment 10
Thiophenol is a 4-chloro-thiophenol, and consumption is 10mmol, and other experimental technique and condition are with embodiment 1, and product is a N-phenyl thiocarbamate 4-chloro-phenyl ester, and is real that yield is 17.8%.
Embodiment 11
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 38.2%.
Embodiment 12
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 40.9%.
Embodiment 13
Oil of mirbane is 3-chloro-oil of mirbane, and consumption is 10mmol, and mercaptan is propylmercaptan, and consumption is 10mmol, and other experimental technique and condition are with embodiment 1, and product is N-(3-chlorine) phenyl thiocarbamate propyl ester, and is real that yield is 58.8%.
Embodiment 14
Oil of mirbane is 4-chloro-oil of mirbane, and consumption is 10mmol, and other experimental technique and condition are with embodiment 13, and product is N-(4-chlorine) phenyl thiocarbamate propyl ester, and is real that yield is 48.8%.
Embodiment 15
Oil of mirbane is 2-methyl-oil of mirbane, and consumption is 10mmol, and other experimental technique and condition are with embodiment 13, and product is N-(2-methyl) phenyl thiocarbamate propyl ester, and is real that yield is 61.2%.
Embodiment 16
Oil of mirbane is 3-methyl-oil of mirbane, and consumption is 10mmol, and other experimental technique and condition are with embodiment 13, and product is N-(3-methyl) phenyl thiocarbamate propyl ester, and is real that yield is 81.2%.
Embodiment 17
Oil of mirbane is 4-methyl-oil of mirbane, and consumption is 10mmol, and other experimental technique and condition are with embodiment 13, and product is N-(4-methyl) phenyl thiocarbamate propyl ester, and is real that yield is 58.8%.
Embodiment 18
Oil of mirbane is 2-methoxyl group-oil of mirbane, and consumption is 10mmol, and other experimental technique and condition are with embodiment 13, and product is N-(2-methoxyl group) phenyl thiocarbamate propyl ester, and is real that yield is 79.0%.
Embodiment 19
Oil of mirbane is 4-methoxyl group-oil of mirbane, and consumption is 10mmol, and other experimental technique and condition are with embodiment 13, and product is N-(4-methoxyl group) phenyl thiocarbamate propyl ester, and is real that yield is 83.9%.
Embodiment 20
The consumption of Se is 0.1mmol, and other experimental technique and condition are with embodiment 1, and product is N-phenyl thiocarbamate propyl ester (down together), and is real that yield is 40.3%.
Embodiment 21
The consumption of Se is 1mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 82.9%.
Embodiment 22
Reaction times is 2 hours, and other experimental technique and condition are with embodiment 1, and be real that yield is 37.5%.
Embodiment 23
Reaction times is 15 hours, and other experimental technique and condition are with embodiment 1, and be real that yield is 78.9%.
Embodiment 24
CO pressure is 3.0MPa, and other experimental technique and condition are with embodiment 1, and be real that yield is 83.6%.
Embodiment 25
Temperature of reaction is 30 ℃, and other experimental technique and condition are with embodiment 1, and be real that yield is 68.0%.
Embodiment 26
Temperature of reaction is 75 ℃, and other experimental technique and condition are with embodiment 1, and be real that yield is 77.3%.
Embodiment 27
Temperature of reaction is 150 ℃, and other experimental technique and condition are with embodiment 1, and be real that yield is 43.1%.
Embodiment 28
The consumption of triethylamine is 1mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 59.2%.
Embodiment 29
The consumption of triethylamine is 10mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 80.9%.
Embodiment 30
The consumption of triethylamine is 30mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 79.3%.
Embodiment 31
Solvent toluene, consumption are 10mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 79.9%.
Embodiment 32
Solvent tetrahydrofuran (THF), consumption are 10mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 81.9%.
Embodiment 33
Solvent benzene, consumption are 10mmol, and other experimental technique and condition are with embodiment 1, and be real that yield is 78.9%.
Claims (8)
1. the novel method of a synthesizing thiocarbamate in the presence of CO, is a raw material with aromatic nitro compound and mercaptan or thiophenol, is catalyzer with selenium, and triethylamine is a promotor, reacts in the autoclave of sealing, and reaction formula is as follows:
Wherein:
Substituent R on the aromatic nitro compound aromatic ring
1Be hydrogen, one or more electron-donating groups or electron-withdrawing group;
R
2For 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 aromatic nitro compound is 10: 1 to 1: 10;
The mole dosage of selenium be in reactant mercaptan or thiophenol and the aromatic nitro compound the less side of mole dosage 0.1～20%;
The mole dosage of triethylamine be in reactant mercaptan or thiophenol and the aromatic nitro compound the less side of mole dosage 10～200%;
Reaction times is 1～20 hour;
Temperature of reaction is 0～200 ℃;
Reaction of carbon monoxide pressure is 0.1～10MPa.
2. according to the method for the described synthesizing thiocarbamate of claim 1, it is characterized in that: be methyl, ethyl, sec.-propyl or methoxyl group to electron substituent group in the described reactant aromatic nitro compound, electron-withdrawing substituent is chlorine, bromine, trifluoromethyl or trifluoromethoxy.
3. according to the method for the described synthesizing thiocarbamate of claim 1, it is characterized in that: R in the described reactant sulfide
2It is alkyl.
4. according to the method for the described synthesizing thiocarbamate of claim 1, it is characterized in that: be methyl, ethyl, sec.-propyl or methoxyl group to electron substituent group in the described reactant thiophenol, electron-withdrawing substituent is chlorine, bromine, trifluoromethyl or trifluoromethoxy.
5. according to the method for the described synthesizing thiocarbamate of claim 1, it is characterized in that: wherein said carbon monoxide can use 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. according to the method for the described synthesizing thiocarbamate of claim 1, it is characterized in that: be reflected in the organic solvent and carry out.
7. according to the method for the described synthesizing thiocarbamate of claim 6, it is characterized in that: wherein said organic solvent is one or more polarity or nonpolar inert solvent.
8. according to the method for the described synthesizing thiocarbamate of claim 7, it is characterized in that: described polar solvent is toluene, tetrahydrofuran (THF), N, and dinethylformamide, acetone or chloroform, non-polar solvent are normal hexane or benzene.
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| CN 200410068874 CN1721402A (en) | 2004-07-13 | 2004-07-13 | A kind of method of synthesizing thiocarbamate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076646A (en) * | 2016-06-20 | 2016-11-09 | 曹飞 | A kind of screening technique of new copper sulfur collecting agent |
| CN106631947A (en) * | 2016-09-29 | 2017-05-10 | 广州市汇吉科技企业孵化器有限公司 | Extraction technology of thiocarbamate in moringa oleifera and application of thiocarbamate |
-
2004
- 2004-07-13 CN CN 200410068874 patent/CN1721402A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076646A (en) * | 2016-06-20 | 2016-11-09 | 曹飞 | A kind of screening technique of new copper sulfur collecting agent |
| CN106631947A (en) * | 2016-09-29 | 2017-05-10 | 广州市汇吉科技企业孵化器有限公司 | Extraction technology of thiocarbamate in moringa oleifera and application of thiocarbamate |
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