CN105669592A - Tebuthiuron synthesis method - Google Patents
Tebuthiuron synthesis method Download PDFInfo
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- CN105669592A CN105669592A CN201610161339.9A CN201610161339A CN105669592A CN 105669592 A CN105669592 A CN 105669592A CN 201610161339 A CN201610161339 A CN 201610161339A CN 105669592 A CN105669592 A CN 105669592A
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- synthetic method
- terbufos benzthiazuron
- terbufos
- benzthiazuron
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
- C07D285/135—Nitrogen atoms
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a tebuthiuron synthesis method. Tebuthiuron is obtained by reaction between 1,3-dimethylurea and 5-tert-butyl-1,3,4-thiadiazole derivatives under the alkaline condition. The tebuthiuron synthesis method solves the problems of safety risks caused by use of extremely toxic substances such as methyl isocyanate and N-methyl formylchloride, presence of phosgene or the like, difficulty in production operation in traditional methods.
Description
Technical field
The invention belongs to organic synthesis field, specifically, relate to the synthetic method of terbufos benzthiazuron.
Background technology
Terbufos benzthiazuron common name tebuthiuron, has another name called tebuthiuron, and chemical name is 1-(5-tertiary butyl-1,3,4-thiadiazoles-2-bases)-1,3-dimethyl urea. Tebuthiuron technical appearance white powder solid, fusing point: 162 DEG C, dissolubility 2.5g/L (25 DEG C) in water, in methanol, dissolubility is 170g/L (25 DEG C). It is the carbamide herbicides of a kind of natural disposition of going out, annual and perennial grass family and broad leaved weed are all had good preventive effect. It is mainly used in preventing and kill off the shrub in bare place weeds, pasture, the grass family in sugarcane field and broad leaved weed.
Terbufos benzthiazuron mainly has three kinds of synthetic methods according to domestic and foreign literature report.
The bibliographical informations such as 1.US4283543, DE3113328, DE3314190, GB1195672 all adopt 5-tertiary butyl-2-methylamino-1, and 3,4-thiadiazoles react with methyl isocyanate, wherein methyl isocyanate is inflammable and explosive, toxicity is very big, and boiling point is low, and the security risk in production process is high.
Disclosed in 2.CN200910100138 with 5-tertiary butyl-2-methylamino-1,3,4-thiadiazoles, Methylaminoformyl chloride are initiation material, using toluene as solvent, triethylamine as acid binding agent carry out condensation reaction prepare tebuthiuron technical. The method is because consuming a large amount of triethylamine, to its recovery also by difficult, increases cost. Methylaminoformyl chloride zest is very big, and in industrialized production, problem is a lot.
3.CN200710050307, CN201210033244 prepare tebuthiuron technical with methylamine gas or reactant aqueous solution with 5-tertiary butyl-2-methylamino-1,3,4-thiadiazoles and phosgene and derivant thereof again after raw material reaction. The phosgene toxicity used in the method is very strong, dangerous significantly high, and easily generating section impurity is difficult to remove, and affects product quality.
Therefore, the problem how solving to run in above terbufos benzthiazuron synthetic method, is the object studied of the present invention.
Summary of the invention
The problems such as the present invention is directed in prior art reaction raw materials toxicity big, security risk is high, industrial operation difficulty provide a kind of raw material low toxicity and are prone to the synthetic method of terbufos benzthiazuron of industrialized production.
The technical scheme realizing the object of the invention is:
A kind of synthetic method of terbufos benzthiazuron, it is with 1,3-dimethyl urea and 5-tertiary butyl-1, and the derivant of 3,4-thiadiazoles is reacted in the basic conditions and obtained terbufos benzthiazuron;
Wherein R is Cl, Br or first sulfo group.
Described alkali condition refers to addition alkaline matter in reaction system, preferably, described alkaline matter include in sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trimethylamine or triethylamine any one or multiple, the consumption of described alkaline matter is 1.0-1.5 times of compound 1 mole.
Further, the consumption of described alkaline matter is 1.1-1.4 times of compound 1 mole.
Preferably, the consumption of 1,3-dimethyl urea is 1.0-1.5 times of compound 1 mole.
Further, in order to take into account reaction yield and save cost, the consumption of 1,3-dimethyl urea is 1.1-1.2 times of compound 1 mole.
Preferably, the reaction dissolvent used in the synthetic method of terbufos benzthiazuron includes any one in toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, dichloromethane, chloroform, carbon tetrachloride or dichloroethanes, and its consumption is 1-10 times of the quality of compound 1.
Further, the consumption of reaction dissolvent is 2-5 times of the quality of compound 1.
Preferably, the synthetic method reaction temperature of above-mentioned terbufos benzthiazuron is between 0-110 DEG C.
Further, the synthetic method reaction temperature of terbufos benzthiazuron is between 40-80 DEG C; In order to realize high reaction yield, the synthetic method reaction temperature of terbufos benzthiazuron is between 60-80 DEG C.
Preferably, the above-mentioned response time was at 1-10 hour.
The new method of the present invention compared with the prior art, is characterized in employing 1,3-dimethyl urea and 5-tertiary butyl-1, and 3,4-thiadiazoles direct reaction generate terbufos benzthiazurons, it is to avoid use inflammable and explosive, and the great methyl isocyanate of toxicity and phosgene and derivant thereof.
Detailed description of the invention
Following example further illustrate present disclosure, but should not be construed as limitation of the present invention.
Embodiment 1:
Toluene 200g is added in reaction bulb, 5-tertiary butyl-2-chloro-1, 3, 4-thiadiazoles 100g (0.54mol), 1, 3-dimethyl urea 52.6g (0.59mol, 1.1eq), stir, it is warming up to 60 DEG C, drip 30% sodium hydrate aqueous solution 86g (0.65mol, 1.2eq), dropping Bi Jixu is incubated 5 hours, reaction is finished, layering, toluene continues washing twice mutually, precipitation, deviate from about 150g toluene, it is cooled to 0 DEG C to stand 6 hours, product precipitates out, sucking filtration obtains white solid 120g, compose through mass spectrum and hydrogen and be verified as terbufos benzthiazuron, its purity of efficient Liquid Detection is 97%, yield 94.4%.
Embodiment 2:
Chlorobenzene 300g is added in reaction bulb, 5-tertiary butyl-2-chloro-1, 3, 4-thiadiazoles 100g (0.54mol), 1, 3-dimethyl urea 55g (0.62mol, 1.15eq), potassium carbonate 90g (0.65mol, 1.2eq), stir, it is to slowly warm up to 50 DEG C, it is incubated anti-3 hours, reaction is finished, add water stirring layering, chlorobenzene continues washing twice mutually, precipitation, deviate from about 250g chlorobenzene, it is cooled to 10 DEG C to stand 4 hours, product precipitates out, sucking filtration obtains white solid 115g, compose through mass spectrum and hydrogen and be verified as terbufos benzthiazuron, its purity of efficient Liquid Detection is 96%, yield 90.0%.
Embodiment 3:
Dichloromethane 500g is added in reaction bulb, 5-tertiary butyl-2-chloro-1, 3, 4-thiadiazoles 100g (0.54mol), 1, 3-dimethyl urea 57.4g (0.64mol, 1.2eq), stir, it is to slowly warm up to 40 DEG C, dropping triethylamine 77g (0.77mol, 1.4eq), it is incubated anti-8 hours, reaction is finished, add water stirring layering, dichloromethane continues washing twice mutually, precipitation, deviate from about 450g dichloromethane, it is cooled to 20 DEG C to stand 4 hours, product precipitates out, sucking filtration obtains white solid 113g, compose through mass spectrum and hydrogen and be verified as terbufos benzthiazuron, its purity of efficient Liquid Detection is 96%, yield 88.0%.
Embodiment 4:
Toluene 300g is added in reaction bulb, 5-tertiary butyl-2-first sulfo group-1, 3, 4-thiadiazoles 100g (0.43mol), 1, 3-dimethyl urea 46.1g (0.52mol, 1.2eq), stir, it is to slowly warm up to 80 DEG C, drip 30% sodium hydrate aqueous solution 74.7g (0.56mol, 1.3eq), insulation reaction 2 hours, reaction is finished, add water stirring layering, toluene continues washing twice mutually, precipitation, deviate from about 250g toluene, it is cooled to 10 DEG C to stand 8 hours, product precipitates out, sucking filtration obtains white solid 95.4g, compose through mass spectrum and hydrogen and be verified as terbufos benzthiazuron, its purity of efficient Liquid Detection is 96%, yield 94.3%.
Claims (8)
1. the synthetic method of a terbufos benzthiazuron, it is characterised in that: with 1,3-dimethyl urea and 5-tertiary butyl-1, the derivant of 3,4-thiadiazoles, react in the basic conditions and obtain terbufos benzthiazuron;
Wherein R is Cl, Br or first sulfo group.
2. the synthetic method of a kind of terbufos benzthiazuron described in claim 1, it is characterized in that described alkali condition refers to addition alkaline matter in reaction system, described alkaline matter include in sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trimethylamine or triethylamine any one or multiple, the consumption of described alkaline matter is 1.0-1.5 times of compound 1 mole.
3. the synthetic method of a kind of terbufos benzthiazuron described in claim 1, it is characterised in that the consumption of described 1,3-dimethyl urea is 1.0-1.5 times of compound 1 mole.
4. the synthetic method of a kind of terbufos benzthiazuron described in claim 1, being characterised by that the reaction dissolvent used in the synthetic method of described terbufos benzthiazuron includes: any one in toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, dichloromethane, chloroform, carbon tetrachloride or dichloroethanes, its consumption is 1-10 times of the quality of compound 1.
5. the synthetic method of a kind of terbufos benzthiazuron described in claim 4, is characterised by 2-5 times of the quality that consumption is compound 1 of described reaction dissolvent.
6. the synthetic method of a kind of terbufos benzthiazuron described in claim 1, is characterised by that the synthetic method reaction temperature of described terbufos benzthiazuron is between 0-110 DEG C.
7. the synthetic method of a kind of terbufos benzthiazuron described in claim 6, is characterised by that the synthetic method reaction temperature of described terbufos benzthiazuron is between 40-80 DEG C.
8. the synthetic method of a kind of terbufos benzthiazuron described in claim 1, wherein the response time was at 1-10 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794427A (en) * | 2018-07-13 | 2018-11-13 | 江苏快达农化股份有限公司 | A kind of synthetic method of 1,3,4- thiadiazoles derivatives |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283543A (en) * | 1979-10-19 | 1981-08-11 | Morton-Norwich Products, Inc. | Process for preparing the compound 5-t-butyl-2-methylamino-1,3,4-triadiazole |
| CN101597269A (en) * | 2009-06-24 | 2009-12-09 | 浙江一帆化工有限公司 | A kind of method for synthesizing tebuthiuron technical |
| CN102603672A (en) * | 2012-02-15 | 2012-07-25 | 江苏快达农化股份有限公司 | Method for synthesizing tebuthiuron technical material |
| CN103288777A (en) * | 2013-05-28 | 2013-09-11 | 浙江禾田化工有限公司 | Synthesis method of key intermediate of tebuthiuron, namely 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole |
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2016
- 2016-03-21 CN CN201610161339.9A patent/CN105669592B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283543A (en) * | 1979-10-19 | 1981-08-11 | Morton-Norwich Products, Inc. | Process for preparing the compound 5-t-butyl-2-methylamino-1,3,4-triadiazole |
| CN101597269A (en) * | 2009-06-24 | 2009-12-09 | 浙江一帆化工有限公司 | A kind of method for synthesizing tebuthiuron technical |
| CN102603672A (en) * | 2012-02-15 | 2012-07-25 | 江苏快达农化股份有限公司 | Method for synthesizing tebuthiuron technical material |
| CN103288777A (en) * | 2013-05-28 | 2013-09-11 | 浙江禾田化工有限公司 | Synthesis method of key intermediate of tebuthiuron, namely 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole |
Non-Patent Citations (2)
| Title |
|---|
| 20070203: ""Mono- and di-substituted urea derivatives of cyclodiphosphazane: [ClP(μ-NtBu)2PN(Me)CON(H)Me] and [Me(H)NCON(Me)P(μ-NtBu)]2"", 《TETRAHEDRON LETTERS》 * |
| 凌岗 等: ""丁噻隆的合成"", 《农药》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794427A (en) * | 2018-07-13 | 2018-11-13 | 江苏快达农化股份有限公司 | A kind of synthetic method of 1,3,4- thiadiazoles derivatives |
| CN108794427B (en) * | 2018-07-13 | 2022-07-29 | 江苏快达农化股份有限公司 | Synthetic method of 1,3, 4-thiadiazole derivative |
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Effective date of registration: 20210730 Address after: 225400 No. 8, tuanjiehe Road, Taixing Economic Development Zone, Taizhou City, Jiangsu Province Patentee after: JIANGSU CHANGLONG CHEMICALS Co.,Ltd. Address before: 224600 shadang village, Chenjiagang Town, Xiangshui County, Yancheng City, Jiangsu Province (Chengang chemical concentration area) Patentee before: YANCHENG SOUTH CHEMICALS Co.,Ltd. |