CN110343060A - A kind of synthetic method of thiocarbamide - Google Patents
A kind of synthetic method of thiocarbamide Download PDFInfo
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- CN110343060A CN110343060A CN201910799360.5A CN201910799360A CN110343060A CN 110343060 A CN110343060 A CN 110343060A CN 201910799360 A CN201910799360 A CN 201910799360A CN 110343060 A CN110343060 A CN 110343060A
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- thiocarbamide
- reaction
- synthetic method
- ammonia
- solvent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/02—Thiourea
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthetic method of thiocarbamide.It is passed through in solvent using carbonyl sulfur, with ammonia as raw material, synthesizes target product thiocarbamide, proper catalyst can also be added, reaction is promoted to carry out, catalyst is one of calcium chloride, molecular sieve.The invention operating procedure is simple, and low energy consumption, with short production cycle, product yield and purity is high, meets market to the quality requirement of thiocarbamide；Raw material is easy to get and price is lower；Reaction is generated without solid waste, has the very high value of environmental protection, is suitble to industrialized production.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthetic method of thiocarbamide.
Background technique
Thiocarbamide is a kind of important industrial chemicals and organic chemical industry's intermediate, and it is phonetic to can be used for producing sulfanilamide (SN) imidazoles, methyl sulphur oxygen
The drugs such as pyridine, methionine are the raw materials of piperazine citrate and contraceptive, synthesis antithyroid function resist into drug, anti-tuberculosis drugs,
It is injected intravenously anaesthetic etc.；
Thiocarbamide is equally with a wide range of applications in petrochemical industry, medication chemistry, and all there are also sulphur in many pharmaceutical molecules
The structure fragment of urea.Such as many oral hypoglycemic agents, antithyroid drug belong to Thiourea molecule currently on the market.In agricultural
On, thiocarbamide also acts as fungicide, rust remover, potato germination stimulants, domestic animal fattening agent and inhibits to nitrify fertilizer etc..Addition
Micro thiocarbamide can inhibit soil nitrification, increase the adsorptivity of soil.
Lime nitrogen method is the main technique of China's thiocarbamide production, reaction principle are as follows: (1) lime nitrogen aqueous solution absorbs vulcanization
Hydrogen, (2) calcium sulfhydrate is reacted with calcium cyanamide generates thiocarbamide.Specific process are as follows: (reflux mother liquor is washed with water by lime nitrogen
Liquid) it is uniformly mixed in synthesis reaction vessel, it is passed through hydrogen sulfide gas while stirring and carries out reaction generation thiourea solution.This solution mistake
After filter, freezing and crystallizing, crystal solution centrifuge separation, by crystal finished product obtained by drying are carried out into cooler crystallizer.The technique is in life
It produces and constantly improve highly developed in practice, production stability is relatively good, and operating technology requires low, is suitable for extensive producer
Formula, but a large amount of solid slag of by-product, every one ton of thiocarbamide of production will generate 2.7 tons of waste residue, and cause huge environmental protection pressure.
Increasingly developed with industrial or agricultural and pharmaceutical sector, the demand of thiourea process constantly increases, and thiocarbamide is raw
There is the problems such as energy consumption is high, solid slag is seriously polluted in the old technique produced.Therefore urgently development cost is low and environmentally protective
New process.
Summary of the invention
In view of the deficiencies of the prior art, it the present invention provides a kind of synthetic method of thiocarbamide, solves and gives birth in the prior art
Produce the problems such as at high cost, energy consumption is high, pollution is big.
A kind of synthetic method of thiocarbamide synthesizes target product thiocarbamide using carbonyl sulfur and ammonia as raw material, can also be added appropriate
Catalyst promotes reaction to carry out, and reaction equation is as follows:
The catalyst is one of molecular sieve, calcium chloride；
Preferably, carbonyl sulfur: the molar ratio of ammonia is 1:2.5~5；
The solvent can be methanol, toluene, tetrahydrofuran；
The range of choice of solvent is relatively broad in the present invention, other solvents such as ethyl alcohol, acetone, and methylene chloride can also be with, but
It pays the utmost attention to be easy to get safely, cheap solvent.
Preferably, catalyst quality is the 0.05%~5% of added solvent quality；
Specific synthesis step is as follows:
(1) solvent and catalyst are added in reactor；
(2) it is heated to reaction temperature, is passed through ammonia, carbonyl sulfur, reaction a period of time；
(3) cool down after the reaction was completed, crystallization obtains target product thiocarbamide.
Preferably, reaction temperature described in step (2) is 40~90 DEG C.
Under the reaction temperature, yield is higher, and reaction rate is very fast.Temperature is excessively high, will lead in reaction process along with it
The generation that he reacts, generates more impurity, influences yield and purity, while solvent loss excessively causes to waste；Temperature is too low
Then reaction speed is relatively slow even cannot sufficiently be reacted.
Preferably, the time reacted in step (2) is 0.5~5h.
If the time is too short, react insufficient, the quality of product cannot be guaranteed, if overlong time, the production cycle is too long,
Increase production cost.
Using the beneficial effects of the present invention are as follows:
(1) operating procedure is simple, and low energy consumption, with short production cycle, and product yield and purity is high, significantly larger than market is to thiocarbamide
Quality requirement；
(2) raw material is easy to get and price is lower；
(3) reaction is generated without waste, has the very high value of environmental protection.
The present invention greatly reduces production cost, improves the yield and quality of product, and the process energy consumption is low, without by-product
Object, environmental protection and energy saving are suitble to industrialized production.
A kind of synthetic method of thiocarbamide provided by the invention, relative to traditional handicraft, the process energy consumption is low, no coupling product,
It is more environmentally friendly convenient for downstream use.The reaction product only has target product thiocarbamide and water to generate, and has no other difficult to deal with solid
Useless to generate, operating procedure is simple, and raw material is easy to get and price is lower, and reaction is generated without waste, has the very high value of environmental protection.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
Using carbonyl sulfur and ammonia as raw material, target product thiocarbamide is synthesized, reaction equation is as follows:
COS+2NH3→CS(NH2)2+H2O
Specific steps are successively as follows:
(1 solvent methanol 500.14g is added in reactor；
(2) 50 DEG C are heated to, with 1L/min, ammonia is passed through in reactor with 3L/min to react 120 minutes carbonyl sulfur；
Wherein, carbonyl sulfur: the molar ratio of ammonia is 1:3 or so；
(3) decrease temperature crystalline after the reaction was completed, obtains the methanol solution of thiocarbamide solid and thiocarbamide, converts into thiocarbamide yield
91.18%, solid thiocarbamide content 99.62%.
Embodiment 2
Using carbonyl sulfur and ammonia as raw material, target product thiocarbamide, reactional equation are synthesized under the action of catalyst molecule sieve
Formula is as follows:
Specific steps are successively as follows:
(1 solvent toluene 500.26g is added in reactor；
(2) 80 DEG C are heated to, with 2L/min, ammonia is passed through in reactor with 5L/min to react 60 minutes carbonyl sulfur；
Wherein, carbonyl sulfur: the molar ratio of ammonia is 2:5 or so；
(3) decrease temperature crystalline after the reaction was completed, obtains the toluene solution of thiocarbamide solid and thiocarbamide, converts into thiocarbamide yield
94.18%, solid thiocarbamide content 99.43%.
Embodiment 3
Using carbonyl sulfur and ammonia as raw material, target product thiocarbamide, reactional equation are synthesized under the action of catalyst calcium chloride
Formula is as follows:
Specific steps are successively as follows:
(1) solvents tetrahydrofurane 500.26g is added in reactor；
(2) 40 DEG C are heated to, for carbonyl sulfur with 0.5L/min, ammonia is passed through in reactor with 2L/min reacts 180 points
Clock；Wherein, carbonyl sulfur: the molar ratio of ammonia is 0.5:2 or so；
(3) decrease temperature crystalline after the reaction was completed, obtains the tetrahydrofuran solution of thiocarbamide solid and thiocarbamide, converts into thiocarbamide yield
92.25%, solid thiocarbamide content 99.46%.
Embodiment 4
Using carbonyl sulfur and ammonia as raw material, target product thiocarbamide is synthesized, reaction equation is as follows:
COS+2NH3→CS(NH2)2+H2O
Specific steps are successively as follows:
(1 solvent toluene 500.14g is added in reactor；
(2) 90 DEG C are heated to, with 1L/min, ammonia is passed through in reactor with 3L/min to react 90 minutes carbonyl sulfur；
Wherein, carbonyl sulfur: the molar ratio of ammonia is 1:3 or so；
(3) decrease temperature crystalline after the reaction was completed, obtains the toluene solution of thiocarbamide solid and thiocarbamide, converts into thiocarbamide yield
90.11%, solid thiocarbamide content 99.35%.
Embodiment 5
Using carbonyl sulfur and ammonia as raw material, target product thiocarbamide is synthesized, reaction equation is as follows:
COS+2NH3→CS(NH2)2+H2O
Specific steps are successively as follows:
(1 solvent methanol 500.26g is added in reactor；
(2) 40 DEG C are heated to, for carbonyl sulfur with 1L/min, ammonia is passed through in reactor with 2.5L/min reacts 240 points
Clock；Wherein, carbonyl sulfur: the molar ratio of ammonia is 1:2.5 or so；
(3) decrease temperature crystalline after the reaction was completed, obtains the methanol solution of thiocarbamide solid and thiocarbamide, converts into thiocarbamide yield
92.27%, solid thiocarbamide content 99.21%.
Claims (9)
1. a kind of synthetic method of thiocarbamide, which is characterized in that this method is using carbonyl sulfur and ammonia as raw material, reaction equation are as follows:
2. a kind of synthetic method of thiocarbamide according to claim 1, which is characterized in that catalyst is molecular sieve, calcium chloride
One of.
3. a kind of synthetic method of thiocarbamide according to claim 1, which is characterized in that carbonyl sulfur and the molar ratio of ammonia are
1:2.5~5.
4. a kind of synthetic method of thiocarbamide according to claim 1, which is characterized in that the solvent be methanol, toluene,
Tetrahydrofuran, ethyl alcohol, acetone, any one in methylene chloride.
5. a kind of synthetic method of thiocarbamide according to claim 4, which is characterized in that the solvent be methanol, toluene,
Any one in tetrahydrofuran.
6. a kind of synthetic method of thiocarbamide according to claim 1, which is characterized in that catalyst quality is solvent quality
0.05%~5%.
7. a kind of synthetic method of thiocarbamide according to claim 1, which is characterized in that specifically synthesis step includes:
(1) solvent and catalyst are added in reactor；
(2) it is heated to reaction temperature, is passed through ammonia, carbonyl sulfur, reaction a period of time；
(3) cool down after the reaction was completed, crystallization obtains target product thiocarbamide.
8. a kind of synthetic method of thiocarbamide according to claim 7, which is characterized in that reaction temperature described in step (2)
Degree is 40~90 DEG C.
9. a kind of synthetic method of thiocarbamide according to claim 7, which is characterized in that the time of reaction is in step (2)
0.5~5h.
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Citations (1)
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| CN110003068A (en) * | 2019-05-21 | 2019-07-12 | 嘉应学院 | A kind of method that one-step method prepares thiocarbamide |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003068A (en) * | 2019-05-21 | 2019-07-12 | 嘉应学院 | A kind of method that one-step method prepares thiocarbamide |
Non-Patent Citations (3)
| Title |
|---|
| 化学工业部人事教育司等: "《合成氨净化》", 31 August 1997 * |
| 化工百科全书编辑部编: "《化工百科全书》", 30 April 1996, 化学工业出版社 * |
| 宁平等编: "《含CO工业废气中有机硫深度净化关键技术》", 31 January 2014, 冶金工业出版社 * |
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