CN103130687A - Preparation method of methyl hydrazinocarboxylate - Google Patents
Preparation method of methyl hydrazinocarboxylate Download PDFInfo
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- CN103130687A CN103130687A CN201310087146XA CN201310087146A CN103130687A CN 103130687 A CN103130687 A CN 103130687A CN 201310087146X A CN201310087146X A CN 201310087146XA CN 201310087146 A CN201310087146 A CN 201310087146A CN 103130687 A CN103130687 A CN 103130687A
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- hydrazine hydrate
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- methylcarbonate
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- hydrazine
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Abstract
The invention discloses a method for preparing methyl hydrazinocarboxylate by reacting hydrazine hydrate and dimethyl carbonate, and particularly discloses an after treatment method for preparing methyl hydrazinocarboxylate by reacting hydrazine hydrate and dimethyl carbonate. The method comprises the following steps: by taking methanol as solvent and hydrazine hydrate and dimethyl carbonate as reaction materials, reacting for 2 hours; removing a mixture of methanol, water and residual hydrazine in vacuum of 0.06-0.08 Mpa at 80-90 DEG C; cooling the reaction system to 40 DEG C, and adding mixed solvent of dichloroethane and dimethyl carbonate; heating to 70 DEG C, and stirring for 1 hour; and then cooling to 5 DEG C or below until precipitation and crystallization, performing centrifugal filtration, and drying to obtain the methyl hydrazinocarboxylate product of which the purity is higher than 99% and the yield is higher than 90%. According to the invention, the reaction is simple in after treatment and convenient to operate; a small amount of residual hydrazine in the product can be consumed, and other impurities in the product can also be removed; the product can be separated out in the form of a crystal; and the product has the advantages of high yield, high purity and simple process.
Description
Technical field
The present invention relates to the post-treating method that the preparation method of methyl carbazate, particularly hydrazine hydrate and dimethyl carbonate prepare methyl carbazate.
Background technology
Methyl carbazate is a kind of important organic synthesis intermediate, is widely used in medicine and pesticide field.Method with hydrazine hydrate and the synthetic methyl carbazate of methylcarbonate abroad has been reported, and its building-up reactions formula is as follows:
Concrete operations are as follows:
At first add 2800g methyl alcohol in reactor, be cooled to 5 ℃, then in 10 hours, 7560g methylcarbonate and 4200g hydrazine hydrate dripped respectively simultaneously, drip process temperature and keep 5～10 ℃, finish, be warmed up to 50 ℃, insulation reaction 10 hours, then decompression is to 106mmHg, slough the mixture that 5124g contains methyl alcohol and methylcarbonate, then continue decompression to 6mmHg, be warmed up to 80 ℃ and slough the mixture that 2115g contains methyl alcohol, water and remaining hydrazine.Aftertreatment is to pass into nitrogen in reactive system, and adds 1823g toluene, then sloughs the mixture of 2561g toluene, hydrazine hydrate and methyl carbazate under 80 ℃ and 6mmHg pressure.In reactor, residue is the methyl carbazate 6583g of purity 98.2%, yield 85.5%.
The method aftertreatment is loaded down with trivial details, inconvenient operation, and yield is low, is piece sheet solids after product is cooling, is not easy to packing and uses.
Summary of the invention
hydrazine hydrate provided by the invention and dimethyl carbonate prepare the method for methyl carbazate, it is characterized in that take methyl alcohol as solvent, hydrazine hydrate and methylcarbonate are reaction raw materials, the molar ratio of hydrazine hydrate and methylcarbonate is 1 ︰ 1, the charging capacity of methyl alcohol is 1～3 times of hydrazine hydrate weight, 5～10 ℃ of feed temperatures, temperature of reaction is the solvent refluxing temperature, reaction times 2h, then slough methyl alcohol under 80～90 ℃ and 0.06～0.08Mpa vacuum, the mixture of water and remaining hydrazine, reactive system is cooled to 40 ℃ again, the mixed solvent that adds ethylene dichloride and methylcarbonate, be warming up to 70 ℃ and stir 1h, then be cooled to below 5 ℃, crystallization, centrifuging, be drying to obtain purity greater than 99%, yield is greater than 90% methyl carbazate product.
The volume ratio of mixed solvent ethylene dichloride of the present invention and methylcarbonate is 100 ︰ 0.5～1, and the charging capacity of mixed solvent is 5～10 times of hydrazine hydrate weight.
The present invention is owing to adopting ethylene dichloride and methylcarbonate mixed solvent, post-reaction treatment is simple, easy to operate, it both can consume the hydrazine that remains on a small quantity in product, can remove again other impurity in product, product with the isolated in form of crystallization out, product yield is high, purity is high, technique is simple.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment:
stirring is being housed, thermometer, in the 500ml glass reactor of reflux exchanger, add 50ml methyl alcohol, stirring is cooled to 5 ℃, then, drip simultaneously 45.4g(0.5mol) methylcarbonate and 31.3g(0.5mol) 80% hydrazine hydrate solution, drip process temperature＜10 ℃, time for adding 1h, finish, temperature rising reflux reaction 2h, slough 50ml methyl alcohol under normal temperature, then between conditioned reaction system vacuum degree to 0.05～0.08MPa, be warmed up to 80 ℃, take off most methyl alcohol under 80～90 ℃, the mixture of water and remaining hydrazine, be cooled to again 40 ℃, add 1ml methylcarbonate and 200ml ethylene dichloride, being warming up to 70 ℃ stirred 1 hour, be cooled to again below 5 ℃, separate out Powdered crystallization, filter, filter cake is under vacuum, 45 ℃ of dryings 3 hours, get white powder methyl carbazate product 41.2g, content 99.2%, yield (in hydrazine hydrate) 90.8%.
Claims (2)
1. the preparation method of a methyl carbazate, it is characterized in that take methyl alcohol as solvent, hydrazine hydrate and methylcarbonate are reaction raw materials, the molar ratio of hydrazine hydrate and methylcarbonate is 1 ︰ 1, the charging capacity of methyl alcohol is 1～3 times of hydrazine hydrate weight, 5～10 ℃ of feed temperatures, temperature of reaction is the solvent refluxing temperature, reaction times 2h, then slough methyl alcohol under 80～90 ℃ and 0.06～0.08Mpa vacuum, the mixture of water and remaining hydrazine, reactive system is cooled to 40 ℃ again, the mixed solvent that adds ethylene dichloride and methylcarbonate, be warming up to 70 ℃ and stir 1h, then be cooled to below 5 ℃, crystallization, centrifuging, be drying to obtain purity greater than 99%, yield is greater than 90% methyl carbazate product.
2. the preparation method of methyl carbazate according to claim 1, the volume ratio that it is characterized in that mixed solvent ethylene dichloride and methylcarbonate is 100 ︰ 0.5～1, the charging capacity of mixed solvent is 5～10 times of hydrazine hydrate weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310087146XA CN103130687A (en) | 2013-03-19 | 2013-03-19 | Preparation method of methyl hydrazinocarboxylate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310087146XA CN103130687A (en) | 2013-03-19 | 2013-03-19 | Preparation method of methyl hydrazinocarboxylate |
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| CN103130687A true CN103130687A (en) | 2013-06-05 |
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| CN201310087146XA Pending CN103130687A (en) | 2013-03-19 | 2013-03-19 | Preparation method of methyl hydrazinocarboxylate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980164A (en) * | 2014-04-26 | 2014-08-13 | 华北电力大学（保定） | Carbazic acid alcohol ester synthesis method |
| CN109180535A (en) * | 2018-09-27 | 2019-01-11 | 江苏师范大学 | A kind of synthetic method of 2- chloroethyl hydrazono- methyl formate |
| CN113666347A (en) * | 2021-08-26 | 2021-11-19 | 陕西大美化工科技有限公司 | Regeneration treatment method of hydrazine hydrate hydrochloride |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52108928A (en) * | 1976-03-08 | 1977-09-12 | Nippon Soda Co Ltd | Production of alkyl carbazate |
| US4401675A (en) * | 1980-10-03 | 1983-08-30 | Montedison S.P.A. | Fungicidal carbazates |
| US4596884A (en) * | 1983-11-30 | 1986-06-24 | Bristol-Myers Company | 4-(2-phenoxyethyl)-1,2,4-triazolone process intermediates |
| US6465678B1 (en) * | 1999-01-26 | 2002-10-15 | Bayer Aktiengesellschaft | Method for preparing methyl carbazate |
| CN1810808A (en) * | 2006-02-20 | 2006-08-02 | 南开大学 | New [1,2,3]-thiobiazole derivative and its synthesis and use |
| CN101823986A (en) * | 2009-12-02 | 2010-09-08 | 江苏大康实业有限公司 | Preparation method for tert-butyl carbazate |
-
2013
- 2013-03-19 CN CN201310087146XA patent/CN103130687A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52108928A (en) * | 1976-03-08 | 1977-09-12 | Nippon Soda Co Ltd | Production of alkyl carbazate |
| US4401675A (en) * | 1980-10-03 | 1983-08-30 | Montedison S.P.A. | Fungicidal carbazates |
| US4596884A (en) * | 1983-11-30 | 1986-06-24 | Bristol-Myers Company | 4-(2-phenoxyethyl)-1,2,4-triazolone process intermediates |
| US6465678B1 (en) * | 1999-01-26 | 2002-10-15 | Bayer Aktiengesellschaft | Method for preparing methyl carbazate |
| CN1810808A (en) * | 2006-02-20 | 2006-08-02 | 南开大学 | New [1,2,3]-thiobiazole derivative and its synthesis and use |
| CN101823986A (en) * | 2009-12-02 | 2010-09-08 | 江苏大康实业有限公司 | Preparation method for tert-butyl carbazate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980164A (en) * | 2014-04-26 | 2014-08-13 | 华北电力大学（保定） | Carbazic acid alcohol ester synthesis method |
| CN109180535A (en) * | 2018-09-27 | 2019-01-11 | 江苏师范大学 | A kind of synthetic method of 2- chloroethyl hydrazono- methyl formate |
| CN113666347A (en) * | 2021-08-26 | 2021-11-19 | 陕西大美化工科技有限公司 | Regeneration treatment method of hydrazine hydrate hydrochloride |
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Application publication date: 20130605 |