CN108017593B

CN108017593B - Simple, convenient and efficient 1-oxo-4, 5-diazepane synthesis method

Info

Publication number: CN108017593B
Application number: CN201711277522.6A
Authority: CN
Inventors: 房雷; 靳秀凤
Original assignee: Southeast University
Current assignee: Southeast University
Priority date: 2017-12-06
Filing date: 2017-12-06
Publication date: 2021-05-11
Anticipated expiration: 2037-12-06
Also published as: CN108017593A

Abstract

The invention discloses a simple and efficient new method for preparing 1-oxo-4, 5-diazepane, which comprises the steps of adding hydrazine salt and equivalent sulphonic acid ester of monoethylene glycol into a solvent, then adding equivalent alkaline medium, and carrying out condensation reaction to directly prepare 1-oxo-4, 5-diazepane; the reaction equation is shown as formula (2):

Description

Simple, convenient and efficient 1-oxo-4, 5-diazepane synthesis method

Technical Field

The invention relates to a simple and efficient method for preparing 1-oxo-4, 5-diazepane, belonging to a production method of raw materials of phenyl pyrazoline herbicides such as pinoxaden and the like.

Background

Pinoxaden is a very widely used herbicide, and 1-oxo-4, 5-diazepane is an important intermediate in its production. At present, the published synthesis method of 1-oxo-4, 5-diazepane uses di-Boc hydrazine as a raw material, carries out anhydrous reaction under the strong alkali condition of sodium hydride and the like, cyclizes with diethylene glycol disulfonate, and removes Boc protecting group to obtain 1-oxo-4, 5-diazepane, wherein the reaction equation is shown as formula (1). The method needs to use excessive sodium hydride, has strong alkalinity and higher anhydrous requirement in the reaction process, can generate a large amount of hydrogen in the reaction and the post-treatment, has the explosion risk, and is not beneficial to large-scale production; in addition, the hydrazine raw material has Boc protecting group, so that a protecting group removing step is needed after cyclization, and the route is long.

Disclosure of Invention

The technical problem is as follows: the invention aims to provide a simple and efficient method for preparing 1-oxo-4, 5-diazepane, which directly takes hydrazine salt as a raw material to carry out condensation reaction with sulfonic ester of diethylene glycol in the presence of an alkaline medium to directly prepare the 1-oxo-4, 5-diazepane. Compared with the original literature method, the method has the advantages of short steps, cheap and easily available raw materials, safe and mild reaction conditions, low production cost and the like, and is easy for large-scale production and popularization.

The technical scheme is as follows: the method for simply, conveniently and efficiently preparing the 1-oxo-4, 5-diazepane comprises the steps of adding hydrazine salt and equivalent sulfonate of monoethylene glycol into a solvent, adding equivalent alkaline medium, and carrying out condensation reaction to directly prepare the 1-oxo-4, 5-diazepane;

the reaction equation is shown as formula (2):

wherein:

the salt of hydrazine is hydrochloride, sulfate, phosphate or acetate of hydrazine.

The alkaline medium is triethylamine, pyridine, potassium carbonate, sodium hydroxide, sodium methoxide and sodium hydride.

The sulfonic ester of the monoethylene glycol is monoethylene glycol dimethyl sulfonate, monoethylene glycol diphenyl sulfonate or monoethylene glycol di-p-toluene sulfonate.

The reaction solvent is N, N-dimethylformamide, acetonitrile, ethanol, pyridine, water, ethyl acetate, toluene, chloroform or dioxane.

The condensation reaction has a reaction temperature of 0 ℃ to 90 ℃.

Has the advantages that: the new method disclosed by the invention directly takes hydrazine salt as a raw material, and the hydrazine salt and sulfonic ester of monoethylene glycol are subjected to condensation reaction in the presence of an alkaline medium to directly prepare the 1-oxo-4, 5-diazepane. Compared with the original literature method, the method has the advantages of short steps, cheap and easily available raw materials, safe and mild reaction conditions, low production cost and the like, and is easy for large-scale production and popularization.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.

Example 1.

5.2g monoethylene glycol disulfonate (20mmol) and 2.6g hydrazine sulfate (20mmol) are added to 25ml DMF, 6g triethylamine (60mmol) is added under nitrogen protection, the mixture is stirred at 50 ℃ for reaction for 1h, and the reaction is detected by TLC. After the reaction was complete, the reaction was poured into 50ml of ice water, extracted with dichloromethane (25ml x 3), the organic layers were combined, dried and concentrated to give 1.7g of product in 85% yield. ESI-MS 103.5[ M + H ]]⁺。

Example 2.

The procedure of example 1 was otherwise the same as in example 1 except that hydrazine hydrochloride was used instead of hydrazine sulfate, and the yield was 85%.

Example 3.

The procedure of example 1 was otherwise the same as that of example 1 except that hydrazine sulfate was replaced with hydrazine acetate, whereby the yield was 82%.

Example 4.

The procedure of example 1 was otherwise the same as that of example 1 except that monoethylene glycol disulfonate was used instead of monoethylene glycol disulfonate.

Example 5.

The procedure of example 1 was otherwise the same as that of example 1 except that diethylene glycol disulfonate was replaced with diethylene glycol ditoluene sulfonate, and the yield was 87%.

Example 6.

The procedure of example 1 was otherwise the same as that of example 1 except that pyridine was used instead of triethylamine, whereby the yield was 77%.

Example 7.

The procedure of example 1 was otherwise the same as that of example 1 except that potassium carbonate was used instead of triethylamine, whereby the yield was 80%.

Example 8.

The procedure of example 1 was otherwise the same as that of example 1 except that sodium hydroxide was used in place of triethylamine, whereby the yield was 32%.

Example 9.

The procedure of example 1 was otherwise the same as that of example 1 except that sodium methoxide was used instead of triethylamine, whereby the yield was 22%.

Example 10.

The procedure of example 1 was otherwise the same as that of example 1 except that sodium hydride was used instead of triethylamine, whereby the yield was 86%.

Example 11.

The same procedure as in example 1 was repeated except that acetonitrile was used as a solvent in place of DMF, whereby the yield was 78%.

Example 12.

The same procedure as in example 1 was repeated except that pyridine was used as a solvent in place of DMF and no other basic substance was added, whereby the yield was 60%.

Example 13.

The same procedure as in example 1 was repeated except that water was used as a solvent in place of DMF, whereby the yield was 28%.

Example 14.

The same procedure as in example 1 was repeated except that chloroform was used as a solvent in place of DMF, whereby the yield was 42%.

Example 15.

The same procedure as in example 1 was repeated except that toluene was used as a solvent in place of DMF, whereby the yield was 48%.

Example 16.

The same procedure as in example 1 was repeated except that ethyl acetate was used as a solvent in place of DMF, whereby the yield was 28%.

Example 17.

The same procedure as in example 1 was repeated except that dioxane was used as a solvent in place of DMF, and the yield was 55%.

Example 18.

5.2g monoethylene glycol disulfonate (20mmol) and 2.0g hydrazine sulfate (15mmol) are added to 25ml DMF, 6g triethylamine (60mmol) is added under nitrogen protection, the mixture is stirred at 80 ℃ for reaction for 1h, and the reaction is detected by TLC. After the reaction was complete, the reaction was poured into 50ml of ice water, extracted with dichloromethane (25ml x 3), the organic layers were combined, dried and concentrated to give 1.2g of product in 80% yield.

Example 19.

5.2g monoethylene glycol disulfonate (20mmol) and 2.6g hydrazine sulfate (20mmol) are added to 25ml DMF, 6g triethylamine (60mmol) is added under nitrogen protection, the mixture is stirred at 20 ℃ for reaction for 10h, and the reaction is detected by TLC. After the reaction was complete, the reaction was poured into 50ml of ice water, extracted with dichloromethane (25ml x 3), the organic layers were combined, dried and concentrated to give 1.1g of product in 50% yield.

Example 20.

3.9g monoethylene glycol disulfonate (15mmol) and 2.6g hydrazine sulfate (20mmol) are added into 25ml DMF, 6g triethylamine (60mmol) is added under the protection of nitrogen, the mixture is stirred and reacted for 4h at 60 ℃, and the reaction is detected by TLC. After the reaction was complete, the reaction was poured into 50ml of ice water, extracted with dichloromethane (25ml x 3), the organic layers were combined, dried and concentrated to give 1.0g of product in 65% yield.

Claims

1. A simple and efficient method for preparing 1-oxo-4, 5-diazepane is characterized by comprising the following steps: adding hydrazine salt and equivalent sulfonate of monoethylene glycol into a solvent, then adding equivalent alkaline medium, and carrying out condensation reaction to directly prepare 1-oxo-4, 5-diazepane;

the reaction equation is shown as formula (2):

the salt of hydrazine is hydrochloride, sulfate, phosphate or acetate of hydrazine;

the alkaline medium is triethylamine, pyridine, potassium carbonate, sodium hydroxide, sodium methoxide or sodium hydride.

2. The simple and efficient process for producing 1-oxo-4, 5-diazepane according to claim 1, wherein: the sulfonic ester of the monoethylene glycol is monoethylene glycol dimethyl sulfonate, monoethylene glycol diphenyl sulfonate or monoethylene glycol di-p-toluene sulfonate.

3. The simple and efficient process for producing 1-oxo-4, 5-diazepane according to claim 1, wherein: the reaction solvent is N, N-dimethylformamide, acetonitrile, ethanol, pyridine, water, ethyl acetate, toluene, chloroform or dioxane.

4. The simple and efficient process for producing 1-oxo-4, 5-diazepane according to claim 1, wherein: the condensation reaction has a reaction temperature of 0 ℃ to 90 ℃.