Synthesis method of diisopropyl azodiformate

A technology of diisopropyl azodicarboxylate and diisopropyl hydrazine dicarboxylate, which is applied in the field of organic chemical synthesis, can solve the problems of serious environmental pollution, large discharge of three wastes, large energy consumption, etc., and achieve high product purity , The effect of low oxidant cost and low energy consumption

Inactive Publication Date: 2012-05-23
CHANGZHOU HIGH TECH RES INST OF NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Using concentrated nitric acid as oxidant, oxidation reaction at 0°C, yellow smoke is released, this method is highly corrosive, consumes a lot of energy, has low yield, and seriously pollutes the environment
British patent GB1012264A uses chlorine gas to oxidize diisopropyl hydrazine dicarboxylate under alkaline conditions, extracts with organic solvent, and then removes the solvent to obtain the product. The highest yield is 92% and the purity is 97.5%. This method produces a large amount of sodium hypochlorite. The discharge of three wastes is large and the environment is seriously polluted

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] In a 500ml three-necked flask equipped with a thermometer, dropping funnel and agitator, add 10g of diisopropyl hydrazine dicarboxylate and 100ml of water, add 20ml of 50% concentrated sulfuric acid while stirring, and then add 0.05g of 40% hydrobromic acid 13g of 10% hydrogen peroxide was added dropwise at -15°C, the dropwise addition was completed in 0.5h, then stirred for 1h, left standing after the reaction was completed, the oil phase was separated, and the 2 Cl 2 Extract the water phase, combine the oil phase with the extract, wash with water until neutral, and wash with anhydrous MgSO 4 After drying and distilling off the solvent, 9.4 g of diisopropyl azodicarboxylate (93% yield, 99.5% purity) was obtained, and its H NMR and IR spectra were consistent with those of the standard sample.

Embodiment 2

[0017] In a 500ml three-necked flask equipped with a thermometer, a dropping funnel, and a stirrer, add 10g of diisopropyl hydrazine dicarboxylate, 100ml of water, add 20ml of 40% sulfuric acid under stirring, and then add 0.05g of 40% hydrobromic acid, Add 13g of 10% hydrogen peroxide dropwise at 0°C for 0.5h, then stir for 6h, let stand after the reaction is complete, separate the oil phase, and use CH 2 Cl 2 Extract the water phase, combine the oil phase with the extract, wash with water until neutral, and wash with anhydrous MgSO 4 After drying and distilling off the solvent, 9.6 g of diisopropyl azodicarboxylate (95% yield, 99.4% purity) was obtained, and its H NMR and IR spectra were consistent with those of the standard sample.

Embodiment 3

[0019] In a 500ml three-necked flask equipped with a thermometer, a dropping funnel, and a stirrer, add 10g of diisopropyl hydrazine dicarboxylate, 100ml of water, add 20ml of 30% sulfuric acid under stirring, and then add 0.2g of 40% hydrobromic acid, Add 13g of 10% hydrogen peroxide dropwise at 0°C for 0.5h, then stir for 6h, let stand after the reaction is complete, separate the oil phase, and use CH 2 Cl 2 Extract the water phase, combine the oil phase with the extract, wash with water until neutral, and wash with anhydrous MgSO 4 After drying and distilling off the solvent, 9.6 g of diisopropyl azodicarboxylate (95% yield, 99.5% purity) was obtained, and its H NMR and IR spectra were consistent with those of the standard sample.

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PUM

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Abstract

The invention relates to a synthesis method of diisopropyl azodiformate, comprising the following steps of: adding diamine diisopropyl dicarboxylic acid and water in sequence under the temperature of 15 DEG C below zero to 40 DEG C, slowly adding 10 to 70 percent sulfuric acid solution, adding bromide as catalyst, and slowing dripping hydrogen peroxide, wherein the mol ratio between the hydrogen peroxide and the diamine diisopropyl dicarboxylic acid is 1.0 to 2.5: 1; controlling the dripping speed and dripping off within 0.5 to 2 hours, preserving the temperature for 1 to 10 hours after the dripping is over, extracting reaction mixture by solvent, drying after oil-phase washing, and distilling to eliminate the solvent to prepare the claret diisopropyl azodiformate. The invention has the advantages that: mild oxidant hydrogen peroxide is selected as oxidant, the oxidant cost is low, no residual impurities exist after reaction, and the product purity is high. The invention has the advantages of simple operation, clean operation environment, recycled extracting solution, wide reaction temperature range and stable reaction; and the prepared product is unnecessary to further refine so that low energy consumption and high production ratio are ensured.

Description

technical field [0001] The invention relates to a preparation process of diisopropyl azodicarboxylate, belonging to the technical field of organic chemical synthesis. Background technique [0002] Azodicarboxylate diesters are a class of Mitsunobu cyclization reagents and important intermediates. They can be used as cyclization reagents for Mitsunobu reactions to synthesize some important heterocyclic compounds. Diisopropyl azodicarboxylate (DIAD for short) ), is the main member of this class of cyclization reagents, and can also be used in the synthesis of photosensitizers, polymerization catalysts, bactericides and other products; diisopropyl azodicarboxylate can also be used as a liquid foaming agent, and its compatibility with plastics Well, the decomposition product is colorless, pollution-free, odorless, and has broad application prospects. [0003] The currently disclosed synthesis method of diisopropyl azodicarboxylate mainly uses diisopropyl hydrazine dicarboxylate...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C245/04
Inventor 张秀芹陆荣青陈强崔源席海涛孙小强
Owner CHANGZHOU HIGH TECH RES INST OF NANJING UNIV
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