CN1321980C - Method of synthesizing thiocarbamate by 'one pot method' - Google Patents
Method of synthesizing thiocarbamate by 'one pot method' Download PDFInfo
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- CN1321980C CN1321980C CNB2005100621120A CN200510062112A CN1321980C CN 1321980 C CN1321980 C CN 1321980C CN B2005100621120 A CNB2005100621120 A CN B2005100621120A CN 200510062112 A CN200510062112 A CN 200510062112A CN 1321980 C CN1321980 C CN 1321980C
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Abstract
Thiocarbamate compounds are important intermediates of medicine, chemical engineering and pesticide, and have wide market prospects. The present invention relates to a method for synthesizing the thiocarbamate by reactions in one pot in an organic solvent, which uses bis(trichloromethyl)carbonate, amine compounds and substituted thiol (comprising thiophenol compounds) as raw materials. Compared with the traditional synthesizing methods, the route for synthesizing the thiocarbamate disclosed by the present invention has various advantages of conveniently stored and easily obtained raw materials, convenient and safe operation, mild reaction conditions, high reaction yield, simple post treatment, etc., and has great enforcement value and potential social and economic benefit.
Description
(1) technical field
The present invention relates to a kind of chemical synthesis process of thiocarbamate.
(2) background technology
Before the present invention made, the synthesizing thiocarbamate compounds was mainly by following route in the prior art: the 1) reaction of phosgene, amine and mercaptan; 2) reaction of urea chloride or isocyanic ester and mercaptan; 3) intramolecular rearrangement of each analog derivative reaction; 4) in the presence of catalyzer, the reaction of carbon monoxide, amine and sulphur or disulphide; 5) carbon monoxide, sulphur, amine and halid reaction; 6) reaction of trichoroacetic chloride, amine and mercaptan; 7) reaction etc. of thiocyanate and alcohol.
Mainly there is following shortcoming in above route: 1) raw material has severe toxicity or unstable; 2) raw material is not easy to obtain; 3) the catalyzer costliness of Shi Yonging reclaims difficulty; 4) the synthesis technique step is various; 5) charging capacity is too much, causes wastage of material, the aftertreatment difficulty.6) severe reaction conditions, difficult control.
(3) summary of the invention
The objective of the invention is to overcome the various shortcomings of prior art, provide that a route is simple, mild condition, raw material are easy to get, the route method of reaction yield height, " one kettle way " synthesizing thiocarbamate easy and simple to handle.
The technical solution used in the present invention is as follows:
A kind of " one kettle way " synthetic method suc as formula the thiocarbamate shown in (I), in organic solvent, to react completely suc as formula the replacement mercaptan shown in (II) and two (trichloromethyl) carbonic ethers, reaction solution is cooled to 0～5 ℃, slowly add again suc as formula the amine substance shown in (III), be warming up to reaction under the reflux temperature again, resultant gets described thiocarbamate through aftertreatment
R
3-SH
(I) (II) (III)
Wherein, the R in the formula (I)
1, R
2H, C respectively do for oneself
1～C
6Alkyl, phenyl, substituting group be the substituted-phenyl of the alkyl of C1～C6, and R
1And R
2Be not H simultaneously, or R
1With R
2The common piperidine ring of forming; R
3Be C
1～C
6Alkyl or C
1～C
6Thiazolinyl or phenyl or substituting group be C
1～C
6Alkyl or the substituted-phenyl of halogen atom, described halogen atom is F or Cl or Br or I, the amount of described raw material is than for replacing mercaptan: two (trichloromethyl) carbonic ether: amine substance is 1.0: 0.33～0.67: 1.0～1.5.
Described organic solvent is one of the following or following several combinations by arbitrary proportion arbitrarily: methylene dichloride, trichloromethane, tetracol phenixin, 1, the 2-ethylene dichloride, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, acetone, butanone, pimelinketone, ether, propyl ether, isopropyl ether, butyl ether, dithiocarbonic anhydride, Nitromethane 99Min., oil of mirbane, tetrahydrofuran (THF), benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene.Be preferably one of the following or following several combinations arbitrarily: tetrahydrofuran (THF), ethyl acetate, methylene dichloride, trichloromethane, 1,2-ethylene dichloride, benzene,toluene,xylene, chlorobenzene, dichlorobenzene by arbitrary proportion.The consumption of described organic solvent is 10～20 times of replacement mercaptan quality.
In the method for " one kettle way " synthesizing thiocarbamate, when described amine substance is secondary amine class material, when adding secondary amine, add catalyzer, described catalyzer is one of following: triethylamine, pyridine, N, dinethylformamide, catalyzer is 0.2～0.8: 1.0 with the amount of substance ratio that replaces mercaptan.
Above-described replacement mercaptan is preferably toluene-or thiophenol, and described amine substance is preferably aniline or piperidines.
Concrete narration, the method steps of " one kettle way " synthesizing thiocarbamate is as follows: at room temperature add in the organic solution that is dissolved with two (trichloromethyl) carbonic ethers and replace mercaptan, stirred 1～4 hour, it is complete that TLC tracks to raw material reaction, ice bath is cooled to 0-5 ℃, slowly drips primary amine solution, is warming up to normal temperature after dropwising, reflux, reacted 1～6 hour, reaction finishes and is cooled to room temperature, gets reaction solution, reaction solution gets described thiocarbamate through aftertreatment, described aftertreatment is that reaction solution is used 10%NaHCO3 respectively, H2O, the saturated common salt water washing gets water and organic phase, abandons water, with organic phase drying, recrystallization.If described amine is the secondary amine class, the method steps of then described " one kettle way " synthesizing thiocarbamate is as follows: at room temperature add in the organic solution that is dissolved with two (trichloromethyl) carbonic ethers and replace mercaptan, stirred 1～4 hour, it is complete that TLC tracks to raw material reaction, ice bath is cooled to 0-5 ℃, slowly drip the mixing solutions of secondary amine and catalyzer, described catalyzer is one of following: triethylamine, pyridine, N, dinethylformamide, catalyst consumption is warming up to normal temperature for 50% of the amount of substance that replaces mercaptan after dropwising, stirred 0.5 hour, reflux, reacted 1～3 hour, reaction finishes and is cooled to room temperature, gets reaction solution, reaction solution gets described thiocarbamate through aftertreatment, described aftertreatment is that reaction solution is used 10%NaHCO3 respectively, H2O, the saturated common salt water washing gets water and organic phase, abandons water, with organic phase drying, recrystallization.
Concrete, obtain water and organic phase in the described aftertreatment after, get an amount of anhydrous magnesium sulfate drying of organic layer, filter, concentrated thiocarbamate crude product gets described Thiourethane compound with the crude product recrystallization.
The present invention compared with prior art, its beneficial effect is embodied in: this route raw material storage conveniently is easy to get, safety simple to operate, reaction conditions gentleness, yield height, aftertreatment are simple, has bigger implementary value and potential economic results in society.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.33: 1.0, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 15 times of toluene-quality.
In thermometer, reflux condensing tube, churned mechanically 150mL four-hole boiling flask are housed, add toluene-40mmol, two (trichloromethyl) carbonic ether 13.3mmol and methylene dichloride 74.4g.Open and stir, dissolving, normal-temperature reaction 1 hour, it is complete that TLC tracks to raw material reaction, and the reaction solution ice bath is cooled to 0-5 ℃, weighing aniline 40mmol, slowly drip aniline solution, the adularescent solid occurs, and dropwises, and slowly is warming up to backflow, stir 2h, reaction is complete to be cooled to room temperature, and reaction solution is used 10%NaHCO3 respectively, H2O, the saturated common salt water washing obtains water and organic phase, abandon water, get an amount of anhydrous magnesium sulfate drying of organic layer, filter, concentrate to such an extent that white solid is S-p-methylphenyl-N-phenyl thiocarbamate crude product, get S-p-methylphenyl-N-phenyl thiocarbamate white crystal through recrystallization, yield is 75.3%, and the product fusing point is 128.3-130.3 ℃, purity 98.7%.
Embodiment 2
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.0, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 78.8%, and the product fusing point is 129.0-130.0 ℃, purity 98.5%.
Embodiment 3
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.50: 1.0, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 20 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 80.3%, and the product fusing point is 129.2-130.1 ℃, purity 98.5%.
Embodiment 4
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.67: 1.0, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 20 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 80.5%, and the product fusing point is 128.9-130.0 ℃, purity 98.6%.
Embodiment 5
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.33: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 83.6%, and the product fusing point is 129.2-130.1 ℃, purity 98.5%.
Embodiment 6
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 90.7%, and the product fusing point is 129.2-130.0 ℃, purity 98.7%.
Embodiment 7
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.50: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 20 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 89.2%, and the product fusing point is 129.0-130.0 ℃, purity 98.6%.
Embodiment 8
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.67: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 20 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 86.6%, and the product fusing point is 128.8-130.0 ℃, purity 98.9%.
Embodiment 9
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.33: 1.5, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 83.3%, and the product fusing point is 129.0-130.0 ℃, purity 98.6%.
Embodiment 10
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.5, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 90.4%, and the product fusing point is 129.6-130.5 ℃, purity 98.5%.
Embodiment 11
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.50: 1.5, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 20 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 89.6%, and the product fusing point is 129.4-130.2 ℃, purity 98.9%.
Embodiment 12
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.67: 1.5, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 20 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate product yield that makes is 89.6%, and the product fusing point is 129.2-130.2 ℃, purity 98.7%.
Embodiment 13
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a trichloromethane, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate yield that makes is 82.4%, and the product fusing point is 129.6-130.5 ℃, purity 98.2%.
Embodiment 14
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.0, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is THF, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate yield that makes is 80.3%, and the product fusing point is 129.0-130.3 ℃, purity 97.6%.
Embodiment 15
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is 1,2-ethylene dichloride, its consumption are 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate yield that makes is 78.6%, and the product fusing point is 129.1-130.0 ℃, purity 98.0%.
Embodiment 16
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is an ethyl acetate, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate yield that makes is 80.6%, and the product fusing point is 128.7-129.6 ℃, purity 98.0%.
Embodiment 17
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a toluene, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate yield that makes is 77.0%, and the product fusing point is 129.0-130.0 ℃, purity 97.0%.
Embodiment 18
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a chlorobenzene, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate yield that makes is 76.6%, and the product fusing point is 129.6-130.9 ℃, purity 97.1%.
Embodiment 19
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a benzene, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate yield that makes is 73.8%, and the product fusing point is 129.6-131.0 ℃, purity 97.0%.
Embodiment 20
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a dimethylbenzene, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate yield that makes is 70.6%, and the product fusing point is 129.0-130.5 ℃, purity 97.0%.
Embodiment 21
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a dichlorobenzene, and its consumption is 15 times of toluene-quality.
Other is with embodiment 1.The thiocarbamate yield that makes is 72.3%, and the product fusing point is 129.0-130.5 ℃, purity 97.1%.
Embodiment 22
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 15 times of toluene-quality.
When toluene-and two (trichloromethyl) carbonate reaction, reaction is heated to backflow, the reaction times is 1h, again the reaction solution ice bath is cooled to 0-5 ℃ after reacting completely, and other is with embodiment 1.The thiocarbamate yield that makes is 90.0%, and the product fusing point is 129.2-130.0 ℃, purity 98.9%.
Embodiment 23
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 15 times of toluene-quality.
After open stirring, toluene-and two (trichloromethyl) carbonic ethers at normal temperatures the reaction times be 3h, other is with embodiment 1.The thiocarbamate yield that makes is 89.9%, and the product fusing point is 129.0-129.9 ℃, purity 98.7%.
Embodiment 24
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and wherein replacing mercaptan is toluene-, and aminated compounds is an aniline, and organic solvent is a methylene dichloride, and its consumption is 15 times of toluene-quality.
Drip aniline, be warming up to backflow after, the reaction times is 6h, other is with embodiment 1.The thiocarbamate yield that makes is 90.3%, and the product fusing point is 128.9-129.9 ℃, purity 98.8%.
Embodiment 25～40
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, and the amount of substance that replaces mercaptan is 40mmol, wherein replaces the R in mercaptan and the aminated compounds molecular formula
1, R
2, R
3Be shown in Table 1, organic solvent is a methylene dichloride, and its consumption is 15 times of replacement mercaptan quality, and other is operated with embodiment 1.Experimental result sees Table 1, and reaction formula is as follows:
Table 1. example 25～40 experimental results
| The embodiment sequence number | R 1 | R 2 | R 3 | Product yield (%) | Product purity (%) |
| 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 | H H H H H H H H H H H H H H H H | p-CH 3C 6H 4 C 6H 5 C 6H 5CH 2 C 6H 5CH 2 p-CH 3C 6H 4 C 6H 5 C 6H 5CH 2 C 6H 5 p-CH 3C 6H 4 C 6H 5 C 6H 5 n-Bu t-Bu C 6H 5 p-CH 3C 6H 4 C 6H 5 | C 6H 5 C 6H 5 C 6H 5 p-CH 3C 6H 4 p-ClC 6H 4 p-ClC 6H 4 p-ClC 6H 4 C 6H 5CH 2 C 6H 5CH 2 (CH 3) 3C CH 2＝CHCH 2 n-C 6H 13 n-C 6H 13 C 2H 5 C 2H 5 CH 3CH 2ZCH 2 | 85.0 88.3 70.6 75.3 79.8 84.5 71.6 70.9 72.5 70.7 65.6 68.6 69.3 63.5 64.5 60.0 | 98.5 98.5 98.6 98.5 98.7 98.5 98.6 98.8 99.0 98.6 98.8 98.9 98.8 98.6 98.5 98.5 |
Embodiment 41
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, wherein replacing mercaptan is thiophenol, aminated compounds is a piperidines, catalyzer is a pyridine, consumption is 20% of a thiophenol amount of substance, organic solvent is a methylene dichloride, and its consumption is 15 times of thiophenol quality.
In thermometer, reflux condensing tube, churned mechanically 150mL four-hole boiling flask are housed, add thiophenol 40mmol, two (trichloromethyl) carbonic ether 16mmol and methylene dichloride 66.0g.Open and stir, dissolving, normal-temperature reaction 1h, it is complete that TLC tracks to raw material reaction, weighing piperidines 48mmol, pyridine 8mmol, reaction solution ice bath are cooled to 0-5 ℃, slowly drip piperidines and pyridine mixing solutions, dropwise, slowly be warming up to backflow, stir 2h, reaction is complete to be cooled to room temperature, and reaction solution is used 10%NaHCO respectively
3, water, saturated common salt water washing, get water and organic phase, abandon water, get an amount of anhydrous magnesium sulfate drying of organic layer, filter, concentrate to such an extent that yellow semisolid is S-phenyl-N-piperidyl thiocarbamate crude product, get faint yellow S-phenyl-N-piperidyl thiocarbamate solid through recrystallization, yield is 64.3%, and the product fusing point is 50.5-51.5 ℃, purity 98.0%
Embodiment 42
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, wherein replacing mercaptan is thiophenol, aminated compounds is a piperidines, catalyzer is a triethylamine, consumption is 20% of a thiophenol amount of substance, organic solvent is a methylene dichloride, and its consumption is 15 times of thiophenol quality.
Other is with embodiment 41.The thiocarbamate yield that makes is 53.1%, and the product fusing point is 51.3-52.6 ℃, purity 97.3%.
Embodiment 43
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, wherein replacing mercaptan is thiophenol, aminated compounds is a piperidines, catalyzer is N, dinethylformamide, consumption is 20% of a thiophenol amount of substance, and organic solvent is a methylene dichloride, and its consumption is 15 times of thiophenol quality.
Other is with embodiment 41.The thiocarbamate yield that makes is 60.1%, and the product fusing point is 50.8-52.3 ℃, purity 98.0%.
Embodiment 44
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, wherein replacing mercaptan is thiophenol, aminated compounds is a piperidines, catalyzer is a pyridine, consumption is 50% of a thiophenol amount of substance, organic solvent is a methylene dichloride, and its consumption is 15 times of thiophenol quality.
Other is with embodiment 41.The thiocarbamate yield that makes is 65.1%, and the product fusing point is 50.3-51.0 ℃, purity 98.0%.
Embodiment 45
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, wherein replacing mercaptan is thiophenol, aminated compounds is a piperidines, catalyzer is a pyridine, consumption is 80% of a thiophenol amount of substance, organic solvent is a methylene dichloride, and its consumption is 15 times of thiophenol quality.
Other is with embodiment 41.The thiocarbamate yield that makes is 58.1%, and the product fusing point is 50.3-51.6 ℃, purity 97.5%.
Embodiment 46
The amount of substance that feeds intake is than being replacement mercaptan: two (trichloromethyl) carbonic ether: amine is 1.0: 0.40: 1.2, wherein replacing mercaptan is thiophenol, aminated compounds is a diethylamine, catalyzer is a pyridine, consumption is 50% of a thiophenol amount of substance, organic solvent is a methylene dichloride, and its consumption is 15 times of thiophenol quality.
Other is with embodiment 41.The thiocarbamate yield that makes is 57.1%, and product is a yellow oil, purity 97.0%.
Claims (8)
1. one kind " one kettle way " synthesizes the method suc as formula the thiocarbamate shown in (I), it is characterized in that described method is to react completely in organic solvent suc as formula the replacement mercaptan shown in (II) and two (trichloromethyl) carbonic ethers, reaction solution is cooled to 0～5 ℃, slowly add again suc as formula the amine substance shown in (III), be warming up to reaction under the reflux temperature again, resultant gets described thiocarbamate through aftertreatment
Wherein, the R in the formula (I)
1, R
2H, C respectively do for oneself
1～C
6Alkyl, phenyl, substituting group be C
1～C
6The substituted-phenyl of alkyl, and R
1And R
2Be not H simultaneously, or R
1With R
2The common piperidine ring of forming; R
3Be C
1～C
6Alkyl or C
1～C
6Thiazolinyl or phenyl or substituting group be C
1～C
6Alkyl or the substituted-phenyl of halogen atom, described halogen atom is F, Cl, Br or I, the amount of described raw material is than for replacing mercaptan: two (trichloromethyl) carbonic ether: amine substance is 1.0: 0.33～0.67: 1.0～1.5.
2. the method for " one kettle way " as claimed in claim 1 synthesizing thiocarbamate, it is characterized in that described organic solvent is one of the following or following several combinations by arbitrary proportion arbitrarily: methylene dichloride, trichloromethane, tetracol phenixin, 1, the 2-ethylene dichloride, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, acetone, butanone, pimelinketone, ether, propyl ether, isopropyl ether, butyl ether, dithiocarbonic anhydride, Nitromethane 99Min., oil of mirbane, tetrahydrofuran (THF), benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene.
3. the method for " one kettle way " as claimed in claim 2 synthesizing thiocarbamate, it is characterized in that described organic solvent is one of the following or following several combinations by arbitrary proportion arbitrarily: tetrahydrofuran (THF), ethyl acetate, methylene dichloride, trichloromethane, 1,2 one ethylene dichloride, benzene,toluene,xylene, chlorobenzene, dichlorobenzene.
4. the method for " one kettle way " as claimed in claim 1 synthesizing thiocarbamate, the consumption that it is characterized in that described organic solvent are 10～20 times of replacement mercaptan quality.
5. the method for " one kettle way " as claimed in claim 1 synthesizing thiocarbamate, when it is characterized in that described amine substance is secondary amine class material, when adding secondary amine, add catalyzer, described catalyzer is one of following: triethylamine, pyridine, N, dinethylformamide, catalyzer is 0.2～0.8: 1.0 with the amount of substance ratio that replaces mercaptan.
6. as the method for one of claim 1～5 described " one kettle way " synthesizing thiocarbamate, it is characterized in that described replacement mercaptan is toluene-or thiophenol, described amine substance is aniline or piperidines.
7. the method for " one kettle way " as claimed in claim 1 synthesizing thiocarbamate, it is characterized in that described method steps is as follows: at room temperature in the organic solution that is dissolved with two (trichloromethyl) carbonic ethers, add and replace mercaptan, stirred 1～4 hour, it is complete that TLC tracks to raw material reaction, ice bath is cooled to 0-5 ℃, slowly drip primary amine solution, be warming up to normal temperature after dropwising, reflux, reacted 1～6 hour, reaction finishes and is cooled to room temperature, gets reaction solution, reaction solution gets described thiocarbamate through aftertreatment, and described aftertreatment is that reaction solution is used 10%NaHCO respectively
3, H
2O, saturated common salt water washing get water and organic phase, abandon water, with organic phase drying, recrystallization.
8. the method for " one kettle way " as claimed in claim 1 synthesizing thiocarbamate, it is characterized in that described method steps is as follows: at room temperature in the organic solution that is dissolved with two (trichloromethyl) carbonic ethers, add and replace mercaptan, stirred 1～4 hour, it is complete that TLC tracks to raw material reaction, ice bath is cooled to 0-5 ℃, slowly drip the mixing solutions of secondary amine and catalyzer pyridine, the consumption of pyridine is for replacing 50% of mercaptan amount of substance, slowly be warming up to backflow after dropwising, reacted 1～3 hour, reaction finishes and is cooled to room temperature, get reaction solution, reaction solution gets described thiocarbamate through aftertreatment, and described aftertreatment is that reaction solution is used 10%NaHCO respectively
3, H
2O, saturated common salt water washing get water and organic phase, abandon water, with organic phase drying, recrystallization.
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| 浙江工业大学硕士论文 蔡鸿飞，23 2004 * |
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