CN101250140B - Method for synthesizing hydrazino benzyl formate - Google Patents
Method for synthesizing hydrazino benzyl formate Download PDFInfo
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- CN101250140B CN101250140B CN2008100310267A CN200810031026A CN101250140B CN 101250140 B CN101250140 B CN 101250140B CN 2008100310267 A CN2008100310267 A CN 2008100310267A CN 200810031026 A CN200810031026 A CN 200810031026A CN 101250140 B CN101250140 B CN 101250140B
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- benzyl formate
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- phenylcarbinol
- methylcarbonate
- hydrazino benzyl
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Abstract
The invention discloses a one-step method for synthesizing hydrazine benzyl formate, which is characterized in that the invention comprises processing hydrazine hydrate reaction with dimethyl carbonate to form intermediate product as hydrazine methyl formate, without separation and purification, directly adding benzyl alcohol to be reacted in the presence of catalyst to obtain the hydrazine benzyl formate. The invention has the advantages that the invention can synthesize hydrazine benzyl formate via one-step method, with simple process, high product yield and purity and low cost, and the invention can resolve the problems of prior art such as the hydrazine benzyl formate is a novel product in outer nation and imported hydrazine benzyl formate is expensive.
Description
Technical field
The present invention relates to the method for the synthetic hydrazino benzyl formate of a kind of single stage method.
Background technology
Hydrazino benzyl formate is a kind of important fine-chemical intermediate, is widely used in medicine and pesticide field, and its synthetic technology is domestic does not see the pertinent literature report so far.External pertinent literature only has three pieces:
One, on August 12nd, 1997 disclosed Japanese Patent JP9208553; Its synthetic route is: with methyl carbazate and phenylcarbinol is raw material, synthetic hydrazino benzyl formate under sodium methoxide solution catalysis.The shortcoming of this method is to raw material carbazic acid methyl esters purity requirement height, and costs an arm and a leg.
Its on May 26th, 2,1998 laid-open U.S. Patents US5756824; Its synthetic route is: with methyl carbazate and phenylcarbinol is raw material, synthetic hydrazino benzyl formate under salt of wormwood catalysis.The shortcoming of this method is that the raw material methyl carbazate requires the content height equally, cost an arm and a leg, and synthesis yield is low hydrazino benzyl formate synthesis yield (in the carbazic acid methyl esters) 54.2%.
Its on December 12nd, 3,2000 laid-open U.S. Patents US6160160; Its synthetic route and method are as follows:
(1) dimethyl benzyl is synthetic
472g (4.0mol) diethyl carbonate, 864g (8.0mol) phenylcarbinol, 8g yellow soda ash are joined in the reactor of band rectifier unit, stirring is warmed up to trim the top of column, distillates ethanol in tower top temperature below 80 ℃, when the still temperature reaches 140 ℃, trim the top of column is seldom the time, and reaction system is 10
-4MPa continues reaction 1h down, and cool to room temperature leaches yellow soda ash then, and filtrate decompression rectifying obtains the 855g dimethyl benzyl.
(2) hydrazino benzyl formate is synthetic
2556g (10.6mol) dimethyl benzyl, 575g (17.8mol) hydrazine hydrate are joined in the reactor of band rectifier unit, stirring is warmed up to trim the top of column, slowly distillates the mixture of phenylcarbinol and water, when the still temperature reaches 140 ℃, trim the top of column is seldom the time, and reaction system is 10
-4Continue to keep 1h under the MPa, cool to room temperature obtains the 1600g hydrazino benzyl formate then, yield (in dimethyl benzyl) 88.2%.
This method temperature of reaction height and vacuum tightness require to reach more than the 755mmHg, the processing condition harshness, and the operational cycle is long, product aftertreatment trouble, purity is low.
Summary of the invention
The processing method that the purpose of this invention is to provide the synthetic hydrazino benzyl formate of single stage method, it is characterized in that methylcarbonate and hydrazine hydrate reaction, form intermediate product carbazic acid methyl esters and do not separate purifying, directly add one step of catalyzer and phenylcarbinol reaction to obtain hydrazino benzyl formate.Concrete operation method is that methylcarbonate is added in the reactor, ℃ following hydrazine hydrate that drips in temperature≤50, the hydrazine hydrate mole dosage is identical with the molar weight of methylcarbonate, dropping time≤1 hour, back flow reaction 3 hours, add catalyzer and phenylcarbinol again, the mole dosage of phenylcarbinol is 1～3 mole of methylcarbonate, 80～90 ℃ of temperature, reaction vacuum tightness 0.05～0.08Mpa reaction down in 2～5 hours reaction times, heats up then and takes off most low-boiling-point substance and phenylcarbinol, add water at last and carry out crystallization, filter recrystallize, filter, drying gets the hydrazino benzyl formate elaboration.Catalyzer of the present invention is any one in yellow soda ash, salt of wormwood, sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, the potassium ethylate, and catalyst consumption is 0.01～0.2 mole of methylcarbonate.
Advantage of the present invention is to adopt the processing method of the synthetic hydrazino benzyl formate of single stage method, has simple, the product yield high purity height of technology, characteristics such as production cost is low have solved the problem of raw material carbazic acid methyl esters domestic no production, foreign market monopoly price costliness.
Embodiment
The invention will be further described below in conjunction with embodiment, but do not limit the present invention.
Embodiment 1:
Stirring is being housed, thermometer, in the 500ml four-hole vial of reflux exchanger, add 54.5g (0.6mol) methylcarbonate, stirring is cooled to 10 ℃, drip the hydrazine hydrate solution of 37.5g (0.6mol) 80%, 0.5h dropwise, be warmed up to 70 ℃ then, back flow reaction is 3 hours between 70～75 ℃, add 196.4g (1.8mol) phenylcarbinol and 1.25g sodium hydroxide again, between conditioned reaction still vacuum tightness to 0.05～0.08MPa, be warmed up to 80 ℃, between 80～90 ℃, react 2h, be warmed up to 100 ℃ again and take off most low-boiling-point substance, then 110～150 ℃ of temperature, vacuum tightness 0.09MPa reclaims phenylcarbinol 119g down, adds 60g water, crystallization, filter, filter cake is dissolved in the 150ml toluene, recrystallize, filter, drying gets hydrazino benzyl formate finished product 71.5g, content 98.5%, yield (in methylcarbonate) 70.6%.
Embodiment 2:
Stirring is being housed, thermometer, in the 500ml four-hole vial of reflux exchanger, add 54.5g (0.6mol) methylcarbonate, stirring is cooled to 50 ℃, drip the hydrazine hydrate solution of 37.5g (0.6mol) 80%, 0.5h dropwise, be warmed up to 70 ℃ then, back flow reaction is 3 hours between 70～75 ℃, add 196.4g (1.8mol) phenylcarbinol and 1.25g sodium hydroxide again, between conditioned reaction still vacuum tightness to 0.05～0.08MPa, be warmed up to 80 ℃, between 80～90 ℃, react 2h, be warmed up to 100 ℃ again and take off most low-boiling-point substance, then 110～150 ℃ of temperature, vacuum tightness 0.09MPa reclaims phenylcarbinol 119g down, adds 60g water, crystallization, filter, filter cake is dissolved in the 150ml toluene, recrystallize, filter, drying gets hydrazino benzyl formate finished product 72.0g, content 96.5%, yield (in methylcarbonate) 69.8%.
Embodiment 3:
In the enamel reaction still of 2000L, add 227kg (2.5kmol) methylcarbonate, stirring is cooled to 40 ℃, drip the hydrazine hydrate solution of 156kg (2.5kmol) 80%, 0.5h dropwise, be warmed up to 70 ℃ then, back flow reaction is 3 hours between 70～75 ℃, add 818kg (7.5kmol) phenylcarbinol and 4.17kg sodium hydroxide again, between conditioned reaction still vacuum tightness to 0.05～0.08MPa, be warmed up to 80 ℃, between 80～90 ℃, react 2h, be warmed up to 100 ℃ again and take off most low-boiling-point substance, then 110～150 ℃ of temperature, vacuum tightness 0.09MPa reclaims phenylcarbinol 518kg down, adds 400kg water, crystallization, filter, filter cake is dissolved in the 800L toluene, recrystallize, filter, drying gets hydrazino benzyl formate finished product 295kg, content 98.0%, yield (in methylcarbonate) 69.6%.
Embodiment 4:
Use the sodium hydroxide among the embodiment 1 instead yellow soda ash, all the other are constant.Yield 69.8%, content 98.0%.
Embodiment 5
Use the sodium hydroxide among the embodiment 1 instead sodium methylate, all the other are constant.Yield 71.3.8%, content 98.8%.
Embodiment 6
Use the sodium hydroxide among the embodiment 1 instead potassium hydroxide, all the other are constant.Yield 70.2%, content 97.0%.
Embodiment 7
Use the sodium hydroxide among the embodiment 1 instead salt of wormwood, all the other are constant.Yield 72.4%, content 96.9%.
Embodiment 8
Use the sodium hydroxide among the embodiment 1 instead potassium methylate, all the other are constant.Yield 71.2%, content 95.6%.
Embodiment 9
Use the sodium hydroxide among the embodiment 1 instead sodium ethylate, all the other are constant.Yield 68.7%, content 98.2%.
Embodiment 10
Use the sodium hydroxide among the embodiment 1 instead potassium ethylate, all the other are constant.Yield 70.6%, content 97.3%.
Claims (3)
1. the synthetic method of hydrazino benzyl formate is characterized in that methylcarbonate and hydrazine hydrate reaction are formed intermediate product carbazic acid methyl esters and do not separate purifying, directly adds one step of catalyzer and phenylcarbinol reaction to obtain hydrazino benzyl formate.
2. the synthetic method of hydrazino benzyl formate according to claim 1, it is characterized in that described catalyzer is any one in yellow soda ash, salt of wormwood, sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, the potassium ethylate, catalyst consumption is 0.01～0.2 mole of methylcarbonate molal weight.
3. the synthetic method of hydrazino benzyl formate according to claim 1 and 2, it is characterized in that the hydrazine hydrate mole dosage is identical with the molar weight of methylcarbonate, dropping temperature≤50 ℃, dropping time≤1 hour, back flow reaction 3 hours, add catalyzer and phenylcarbinol again, the mole dosage of phenylcarbinol is 1～3 mole of methylcarbonate, 2～5 hours reaction times, 80～90 ℃ of temperature of reaction, reaction vacuum tightness 0.05～0.08MPa, heat up then and take off most low-boiling-point substance and phenylcarbinol, add water at last and carry out crystallization, filter, recrystallize, filter, drying gets the hydrazino benzyl formate elaboration.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153490A (en) * | 2011-02-16 | 2011-08-17 | 东营柯林维尔化工有限公司 | Synthesis of ethyl hydrozino-formates |
| CN102241609A (en) * | 2011-04-26 | 2011-11-16 | 东营柯林维尔化工有限公司 | Synthesis of hydrazinoformate |
| CN103819366B (en) * | 2014-02-19 | 2016-08-24 | 江苏辉腾生物医药科技有限公司 | The synthetic method of hydrazino benzyl formate |
| CN103980164B (en) * | 2014-04-26 | 2015-08-19 | 华北电力大学（保定） | A kind of method of synthesizing carbazic acid alcohol ester |
| CN109020838B (en) * | 2018-09-30 | 2021-02-26 | 湖南化工研究院有限公司 | Preparation method of hydrazinoformate |
| CN109627190B (en) * | 2018-12-04 | 2021-03-09 | 新沂市永诚化工有限公司 | Synthesis method of benzyl carbazate |
| CN109748826B (en) * | 2018-12-28 | 2021-09-21 | 京博农化科技有限公司 | Synthetic method of indoxacarb intermediate hydrazinobenzyl formate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756824A (en) * | 1995-10-27 | 1998-05-26 | Bayer Aktiengesellschaft | Process for the preparation of carbazates |
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2008
- 2008-04-08 CN CN2008100310267A patent/CN101250140B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756824A (en) * | 1995-10-27 | 1998-05-26 | Bayer Aktiengesellschaft | Process for the preparation of carbazates |
Non-Patent Citations (2)
| Title |
|---|
| 石振东.碳酸二甲酯合成肼基甲酸甲酯的研究.三峡大学学报（自然科学版）24 2.2002,24(2),191-192. |
| 石振东.碳酸二甲酯合成肼基甲酸甲酯的研究.三峡大学学报(自然科学版)24 2.2002,24(2),191-192. * |
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Application publication date: 20080827 Assignee: Hunan Sipaike Material Technology Co., Ltd. Assignor: Hunan Sipaike Material Technology Co., Ltd. Contract record no.: 2015430000121 Denomination of invention: Method for synthesizing hydrazino benzyl formate Granted publication date: 20111123 License type: Exclusive License Record date: 20150728 |
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