CN111978227A - Synthetic method of thiourea - Google Patents
Synthetic method of thiourea Download PDFInfo
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- CN111978227A CN111978227A CN202010920676.8A CN202010920676A CN111978227A CN 111978227 A CN111978227 A CN 111978227A CN 202010920676 A CN202010920676 A CN 202010920676A CN 111978227 A CN111978227 A CN 111978227A
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- amine
- thiourea
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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
- C07C335/04—Derivatives of thiourea
- C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthetic method of thiourea. The method for preparing the thiourea to generate the hydrogen sulfide is a common synthetic method under the action of tertiary amine alkali, and on one hand, the hydrogen sulfide needs to be fully absorbed by an alkali absorption system; on the other hand, hydrogen sulfide reacts with tertiary amine base to form amine salt, so a large amount of tertiary amine base catalyst needs to be added in the reaction. Aiming at the problems, the thiourea synthesis method provided by the invention adds a proper amount of inorganic base into the reaction system, on one hand, the thiourea can react with the byproduct hydrogen sulfide in time to form inorganic salt, and a subsequent alkali absorption system is not needed; on the other hand, the use amount of the catalyst tertiary amine base can be greatly reduced, and the subsequent recovery work of a large amount of tertiary amine base is also reduced.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a synthetic method of thiourea.
Background
The synthetic method of the thiourea mainly comprises the following steps: (1) synthesizing by taking thiophosgene and amine as raw materials; (2) the synthesis of isothiocyanate and amine as raw materials; (3) taking thiocyanate, acyl chloride and amine as raw materials for synthesis; (4) synthesizing by using carbon disulfide and amine as raw materials; (5) synthesizing by taking a thiocarbonyl transfer reagent and amine as raw materials. The method for preparing the thiourea to generate the byproduct hydrogen sulfide is a common synthetic method, wherein the hydrogen sulfide is fully absorbed by an alkali absorption system; on the other hand, hydrogen sulfide reacts with tertiary amine base to form amine salt, so a large amount of tertiary amine base catalyst needs to be added in the reaction.
Disclosure of Invention
Aiming at the problems, the invention provides a thiourea synthesis method, which is characterized in that a proper amount of inorganic base is added into a reaction system, so that on one hand, the thiourea can react with a byproduct hydrogen sulfide in time to form inorganic salt, and a subsequent alkali absorption system is not needed; on the other hand, the use amount of the catalyst tertiary amine base can be greatly reduced, and the subsequent recovery work of a large amount of tertiary amine base is also reduced.
The technical scheme of the invention is as follows: a method for synthesizing thiourea comprises the steps of adding a proper amount of amine, carbon disulfide, tertiary amine base, inorganic base, emulsifier and water into a reaction bottle, reacting for 0.5-2 hours at room temperature, heating to 80-95 ℃, keeping reacting for 10-20 hours, preferably heating to 85-90 ℃, reacting for 12-18 hours, more preferably for 14-18 hours, distilling back the tertiary amine base after the reaction is finished, and finally cooling and suction filtering to obtain thiourea product, wherein the reaction equation is as follows:
the mass ratio of the amine to the carbon disulfide is 1: 1.1-1.5, the amount of the tertiary amine base is 3-10% of the mass of the amine, the amount of the water is 2-3 times of the mass of the amine, the amount of the emulsifier is 2-5% of the mass of the water, and the amount of the inorganic base is the theoretical amount of the byproduct hydrogen sulfide removed by reaction.
The amine is one or a mixture of several of C1-C18 alkylamine, aniline and substituted aromatic amine.
The substituted aromatic amine is one or a mixture of more of benzidine, naphthylamine, 2-amino-4-nitrotoluene, p-chloroaniline, p-hydroxyphenylamine, p-tert-butylaniline, 2, 6-diisopropylaniline, o-toluidine, o-methoxyaniline, 2, 4-dimethylaniline, 2, 6-dimethylaniline and 2,4, 5-trimethylaniline.
The tertiary amine base is one or a mixture of several of aliphatic amine, alicyclic amine and aromatic amine.
The aliphatic amine is one or a mixture of more of triethylamine, N, N ' -dimethylhexadecylamine, dimethylbenzylamine, N, N, N ' -tetramethylmethylenediamine, N, N, N ' -tetraethylmethylenediamine, N, N, N ' -tetramethylethylenediamine, N, N, N ' -tetramethylpropylenediamine, N, N ' -tetramethylbutylenediamine, N, N, N ' -pentamethyldiethylenetriamine and bis (2-methylaminoethyl) ether.
The alicyclic amine is one or a mixture of more of triethylene diamine, N-methylmorpholine, N-ethylmorpholine, N '-dimethylpiperazine and N, N' -dimethylcyclohexylamine.
The aromatic amine is one or a mixture of pyridine and lutidine.
The tertiary amine base is one or a mixture of more of triethylamine, pyridine, N, N, N' -tetramethyl methylene diamine and triethylene diamine.
The inorganic base is one or a mixture of more of sodium carbonate, sodium bicarbonate, potassium carbonate and zinc carbonate.
The emulsifier is polyethylene glycol.
If the tertiary amine base is a tertiary amine base with a low boiling point, the tertiary amine base is recovered by distillation after the reaction is finished.
The traditional method for preparing thiourea by adopting amine and carbon disulfide under the action of tertiary amine alkali is a common synthetic method, the method for preparing thiourea produces byproduct hydrogen sulfide, and on one hand, the hydrogen sulfide needs to be fully absorbed by an alkali absorption system; on the other hand, hydrogen sulfide reacts with tertiary amine base to form amine salt, so a large amount of tertiary amine base catalyst needs to be added in the reaction. According to the thiourea synthesis method provided by the invention, a proper amount of inorganic base is added into a reaction system, so that on one hand, the thiourea can react with a byproduct hydrogen sulfide in time to form inorganic salt, and a subsequent alkali absorption system is not needed; on the other hand, the use amount of the catalyst tertiary amine base can be greatly reduced, and the subsequent recovery work of a large amount of tertiary amine base is also reduced.
The prominent beneficial effects are as follows:
1. a proper amount of inorganic base is added into the reaction system, and the inorganic base can react with the byproduct hydrogen sulfide in time to form inorganic salt without a professional hydrogen sulfide absorption system, so that the environmental pollution, the equipment corrosion and the hydrogen sulfide absorption equipment investment are reduced;
2. the use of inorganic base can quickly remove the byproduct hydrogen sulfide in the system, thereby greatly reducing the use amount of tertiary amine base;
3. and a proper amount of polyethylene glycol emulsifier is added into the reaction system, so that the reaction speed can be improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described with reference to the following examples, which are only for further explanation and are not intended to limit the present invention.
Example 1
Adding 50 g of 2, 6-diisopropylaniline, 15 g of carbon disulfide, 2 g of triethylamine, 15 g of sodium carbonate, 5 g of polyethylene glycol 400 and 150 ml of water into a reaction bottle, starting stirring at room temperature for 1 hour, heating to 90 ℃, keeping reacting for 18 hours, cooling after the reaction is finished, and carrying out suction filtration after the reaction liquid is lower than 60 ℃ to obtain a light yellow crystal particle product N, N' -bis (2, 6-diisopropylphenyl) thiourea.
Example 2
Adding 60 g of 2,4, 6-triisopropylaniline, 15 g of carbon disulfide, 3 g of triethylamine, 15 g of sodium carbonate, 5 g of polyethylene glycol 400 and 150 ml of water into a reaction bottle, starting stirring at room temperature for 1 hour, heating to 90 ℃, keeping reacting for 18 hours, cooling after the reaction is finished, and performing suction filtration after the reaction solution is lower than 60 ℃ to obtain the product N, N' -bis (2, 4, 6-triisopropylphenyl) thiourea.
Example 3
Adding 30 g of o-toluidine, 15 g of carbon disulfide, 2 g of triethylamine, 15 g of sodium carbonate, 4 g of polyethylene glycol 400 and 150 ml of water into a reaction bottle, starting to stir at room temperature for 1 hour, then heating to 90 ℃ to keep reacting for 18 hours, cooling after the reaction is finished, and carrying out suction filtration after the reaction liquid is lower than 60 ℃ to obtain the product N, N' -di-o-tolyl thiourea.
Comparative example 1
Adding 50 g of 2, 6-diisopropylaniline, 15 g of carbon disulfide, 15 g of triethylamine and 150 ml of water into a reaction bottle, starting stirring at room temperature for 1 hour, heating to 90 ℃ and keeping reacting for 18 hours, cooling after the reaction is finished, and performing suction filtration after the reaction liquid is lower than 60 ℃ to obtain a yellow crystal product N, N' -bis (2, 6-diisopropylphenyl) thiourea.
Comparative example 2
Adding 50 g of 2, 6-diisopropylaniline, 15 g of carbon disulfide, 2 g of triethylamine, 15 g of sodium carbonate and 150 ml of water into a reaction bottle, starting stirring at room temperature for 1 hour, heating to 90 ℃ and keeping reacting for 18 hours, and finding that yellow large particles are generated in a reaction solution and obvious oily substances are on solid particles, which indicates that the raw material 2, 6-diisopropylaniline does not completely react and the product is not subjected to further physicochemical analysis.
The room temperature mentioned above means an indoor environment at 20-25 ℃.
The results of the examples are as follows
The above is a detailed description of the thiourea provided by the present invention, and the present invention is specifically illustrated by using specific examples, which are only used to help understanding the method and the core idea of the present invention, and the above is only a preferred example of the present invention and is not meant to limit the present invention, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A synthetic method of thiourea is characterized in that a proper amount of amine, carbon disulfide, tertiary amine alkali, inorganic alkali, emulsifier and water are added into a reaction bottle, the mixture reacts for 0.5 to 2 hours at room temperature, then the mixture is heated to 80 to 95 ℃ and kept for reaction for 10 to 20 hours, the tertiary amine alkali is distilled back after the reaction is finished, and finally the product thiourea is obtained by cooling and suction filtration, wherein the reaction equation is as follows:
2. the method for synthesizing thiourea according to claim 1, wherein the amine is one or a mixture of C1-C18 alkylamine, aniline and substituted aromatic amine.
3. The method for synthesizing thiourea according to claim 2, wherein the substituted aromatic amine is one or a mixture of benzidine, naphthylamine, 2-amino-4-nitrotoluene, p-chloroaniline, p-hydroxyphenylamine, p-tert-butylaniline, 2, 6-diisopropylaniline, o-toluidine, o-methoxyaniline, 2, 4-dimethylaniline, 2, 6-dimethylaniline and 2,4, 5-trimethylaniline.
4. The method for synthesizing thiourea according to claim 1, wherein the tertiary amine base is one or a mixture of aliphatic amine, alicyclic amine and aromatic amine.
5. The method for synthesizing thiourea according to claim 4, wherein the aromatic amine is one or a mixture of pyridine and lutidine.
6. The method for synthesizing thiourea according to claim 1, wherein the tertiary amine base is one or a mixture of triethylamine, pyridine, N, N, N' -tetramethylmethylenediamine and triethylenediamine.
7. The method for synthesizing thiourea according to claim 1, wherein the inorganic base is one or a mixture of sodium carbonate, sodium bicarbonate, potassium carbonate and zinc carbonate.
8. The method for synthesizing thiourea according to claim 1, wherein the emulsifier is polyethylene glycol.
9. A process for the synthesis of thiourea according to claim 1, wherein the heating is carried out at 85-90 ℃ for 12-18 hours, more preferably 14-18 hours.
10. The method for synthesizing thiourea according to claim 1, wherein the reaction ratio of the amine to the carbon disulfide is 1: 1.1-1.5 (molar ratio), the amount of the tertiary amine base is 3-10% of the mass of the amine, the amount of the water is 2-3 times of the mass of the amine, the amount of the emulsifier is 2-5% of the mass of the water, and the amount of the inorganic base is calculated according to the theoretical amount of the byproduct hydrogen sulfide, so that the inorganic base can exactly neutralize the generated hydrogen sulfide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200866A (en) * | 2021-03-29 | 2021-08-03 | 龙曦宁（上海）医药科技有限公司 | Synthetic method of diafenthiuron impurity D |
| CN114150335A (en) * | 2021-08-20 | 2022-03-08 | 韶关学院 | Electrochemical method for preparing thiourea compound by using tertiary amine |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04312568A (en) * | 1991-04-10 | 1992-11-04 | Kawaguchi Kagaku Kogyo Kk | Production of n,n'-bis(2,6-dialkylphenyl)thiourea |
| CN1911911A (en) * | 2005-08-09 | 2007-02-14 | 沈阳化工研究院 | Method for preparing 1-tert butyl-3-(2,6-diisopropyl-4-phenyl cxypheny) thiourea |
| CN1962629A (en) * | 2006-11-21 | 2007-05-16 | 浙江大学 | N, N'-diisopropyl thiourea synthesis method |
| CN102731357A (en) * | 2012-07-04 | 2012-10-17 | 山东汇海医药化工有限公司 | Preparation method of high purity N,N'-dicyclohexylthiourea |
| CN103288681A (en) * | 2013-07-04 | 2013-09-11 | 山西省化工研究所 | Process for producing N, N'-diisopropylbenzene carbodiimide by thiourea method |
| CN106316906A (en) * | 2016-08-23 | 2017-01-11 | 山东阳谷华泰化工股份有限公司 | Method for synthesizing accelerator DPTU |
-
2020
- 2020-09-04 CN CN202010920676.8A patent/CN111978227A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04312568A (en) * | 1991-04-10 | 1992-11-04 | Kawaguchi Kagaku Kogyo Kk | Production of n,n'-bis(2,6-dialkylphenyl)thiourea |
| CN1911911A (en) * | 2005-08-09 | 2007-02-14 | 沈阳化工研究院 | Method for preparing 1-tert butyl-3-(2,6-diisopropyl-4-phenyl cxypheny) thiourea |
| CN1962629A (en) * | 2006-11-21 | 2007-05-16 | 浙江大学 | N, N'-diisopropyl thiourea synthesis method |
| CN102731357A (en) * | 2012-07-04 | 2012-10-17 | 山东汇海医药化工有限公司 | Preparation method of high purity N,N'-dicyclohexylthiourea |
| CN103288681A (en) * | 2013-07-04 | 2013-09-11 | 山西省化工研究所 | Process for producing N, N'-diisopropylbenzene carbodiimide by thiourea method |
| CN106316906A (en) * | 2016-08-23 | 2017-01-11 | 山东阳谷华泰化工股份有限公司 | Method for synthesizing accelerator DPTU |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200866A (en) * | 2021-03-29 | 2021-08-03 | 龙曦宁（上海）医药科技有限公司 | Synthetic method of diafenthiuron impurity D |
| CN114150335A (en) * | 2021-08-20 | 2022-03-08 | 韶关学院 | Electrochemical method for preparing thiourea compound by using tertiary amine |
| CN114150335B (en) * | 2021-08-20 | 2022-12-06 | 韶关学院 | Electrochemical method for preparing thiourea compound by using tertiary amine |
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