Esterification method for preparing hydrogenated dialkyl azodicarbonic acid

A technology for dialkyl hydroazodicarboxylate and dimethyl hydroazodicarboxylate, which is applied in the field of dialkyl hydroazodicarboxylate represented by the formula ROOCNHHNCOOR, can solve the problem of non-compliance, environment and operators Harm, production equipment corrosion and other problems, to achieve the effect of low production cost, short process route, mild reaction conditions

Active Publication Date: 2013-07-10
SHANDONG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The biggest problem in preparing dialkyl hydroazodicarboxylate with alkyl chloroformate is: the main raw material alkyl chloroformate is produced by phosgene, and phosgene is a highly toxic substance, which is harmful to the environment and operation. Both of them bring huge harm and do not meet the requirements of modern green chemistry; and the reaction of phosgene and alcohol to prepare alkyl chloroformate will produce hydrogen chloride, which will corrode the production equipment

Method used

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  • Esterification method for preparing hydrogenated dialkyl azodicarbonic acid

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Experimental program
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Effect test

Embodiment 1

[0027] The preparation of embodiment 1 dipropyl hydroazodicarboxylate

[0028] In a 250mL three-necked round-bottomed flask equipped with a mechanical stirrer, a condensing reflux device and a thermometer, add 100mL of n-propanol, and under nitrogen protection, add 0.14g (0.006mol) of sodium metal. After the sodium metal is completely dissolved, add dropwise 14.80 g of dimethyl hydroazodicarboxylate was reacted for 18 hours under reflux in an oil bath, and the reaction was stopped. The pH of the reaction solution was adjusted to 6 with 10% hydrochloric acid (mass fraction, the same below), and the organic phase was extracted three times with dichloromethane, combined and dried with anhydrous sodium sulfate overnight (10h), and the unreacted normal Propanol was recovered, and recrystallized with ethyl acetate-petroleum ether mixture (the volume ratio of the two was 1:8) to obtain 17.41 g of dipropyl hydroazodicarboxylate as a white solid, with a yield of 85.3%.

[0029] 1 HNM...

Embodiment 2

[0032] The preparation of embodiment 2 diisobutyl hydroazodicarboxylate

[0033] In a 250mL three-necked round-bottomed flask equipped with a mechanical stirrer, a condensing reflux device and a thermometer, add 100mL of isobutanol, and under nitrogen protection, add 0.14g (0.006mol) of sodium metal. After the sodium metal is completely dissolved, add dropwise 14.80 g of dimethyl hydroazodicarboxylate was reacted for 16 hours under reflux in an oil bath, and the reaction was stopped. The pH value of the reaction solution was adjusted to 5 with 10% hydrochloric acid solution, the organic phase was extracted three times with dichloromethane, the organic phase was combined, and dried with anhydrous sodium sulfate overnight (10h), the unreacted isobutanol was evaporated to recover, and the acetic acid Ethyl ester-petroleum ether mixture (the volume ratio of the two is 1:12) was recrystallized to obtain 20.60 g of diisobutyl hydroazodicarboxylate as a white solid, with a yield of 8...

Embodiment 3

[0037] The preparation of embodiment 3 dipentyl hydroazodicarboxylates

[0038] In a 250mL three-necked round-bottomed flask equipped with a mechanical stirrer, a condensing reflux device and a thermometer, add 100mL of isoamyl alcohol, and under nitrogen protection, add 0.14g (0.006mol) of sodium metal. After the sodium metal is completely dissolved, add 14.80 g dimethyl hydroazodicarboxylate, reacted for 12 hours under reflux in an oil bath, and stopped the reaction. The pH of the reaction solution was adjusted to 5 with 10% hydrochloric acid solution, the organic phase was extracted three times with dichloromethane, the organic phase was combined, and dried overnight (8h) with anhydrous sodium sulfate, the unreacted isoamyl alcohol was evaporated to recover, and the acetic acid Ethyl ester-petroleum ether mixture (the volume ratio of the two is 1:10) was recrystallized to obtain 23.72 g of dipentyl hydroazodicarboxylate as a white solid, with a yield of 91.2%.

[0039] 1 ...

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Abstract

The invention discloses a method for preparing hydrogenated dialkyl azodicarbonic acid. The method comprises the steps of: mixing hydrogenated dimethyl azodicarbonic acid with sodium alkoxide solution, heating and reacting for 1-24h, and producing transesterification reaction between the dimethyl azodicarbonic acid and alcohol under the catalytic action of sodium alkoxide; after the reaction is completed, regulating the pH value of the solution to 3-8, extracting an organic phase for 2-3 times with dichloromethane, combining the organic phases, drying for 8-12h with anhydrous sodium sulfate, and then performing recrystallization to obtain the hydrogenated dialkyl azodicarbonic acid ROOCNHHNCOOR, wherein R is alkyl containing 2-16 carbon atoms. According to the method, the hydrogenated dimethyl azodicarbonic acid is used as raw material, and is green and environment-friendly, and easily available; the production cost is low, and the economy is good; the synthetic process of chloroformate ester in the traditional process can be ensured to be clean and environment-friendly, thereby meeting the green and chemical requirements; and the method for preparing the hydrogenated dialkyl azodicarbonic acid through esterification is simple to operate, short in process route, mild in reaction conditions, and high in yield, as well as suitable for industrialized development.

Description

technical field [0001] The present invention relates to a method for preparing dialkyl hydroazodicarboxylates represented by the formula ROOCNHHNCOOR. Background technique [0002] Hydrogenated dialkyl azodicarboxylate is an important organic intermediate for the preparation of dialkyl azodicarboxylate (Mitsunobu reagent). Dialkyl azodicarboxylate is an azo compound with both azo and ester functional groups. Because of its unique electronic and structural properties, it has been widely used as a multifunctional reagent in the field of organic synthesis. It is mainly manifested in the Mitsunobu reaction, ammoniation reaction, ring formation reaction, and synthesis of heterocyclic compounds. In addition, because the azo group is usually electron-deficient, it can often be used as an electrophile to hydrazine with a nucleophile It can be used as an oxidizing agent for the dehydrogenation of alcohols and amines. Common dialkyl azodicarboxylates include dimethyl azodicarboxyla...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C281/02
Inventor 张志德王重斌吕硕满成娜
Owner SHANDONG NORMAL UNIV
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