Azodicarboxylic Acid Bis(2-alkoxyethyl) Ester Solid State Purification

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Solution Overview

Problem

Conventional azodicarboxylic acid diesters are challenging to handle due to their liquid state at ordinary temperatures, instability under heat, and the difficulty in separating the insoluble 1,2-hydrazinedicarboxylic acid diester by-product in the Mitsunobu reaction, making them industrially disadvantageous.

Innovation Solution

A crystalline azodicarboxylic acid bis(2-alkoxyethyl) ester compound is developed, which can be produced without distillation and has a water-soluble by-product, allowing for easier removal, using a method involving the reaction of hydrazine with a halocarbonic acid ester followed by oxidation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional azodicarboxylic acid diesters (liquid at ordinary temperatures) are used, then the Mitsunobu reaction can be performed, but purification by distillation is required which is dangerous due to heat instability of azo compounds

Engineering Contradiction:

Improvesafety of purification processVSAvoiddifficulty of purification

Core Design Contradiction:

ReliabilityVSEase of manufacture

Solution Approach 1:

The invention changes the physical state parameter of the azodicarboxylic acid diester from liquid to solid by modifying the ester group from conventional alkyl groups to 2-alkoxyethyl groups. This phase change eliminates the need for distillation purification and allows for safe handling through filtration and washing procedures instead.

Inventive Principle:

Principle #35Parameter changes

Solution Approach 2:

The invention utilizes phase transition by designing the azodicarboxylic acid diester to be solid at ordinary temperatures while maintaining reactivity. The solid state enables simple filtration and washing for purification, avoiding the dangerous heating required for distillation of liquid azo compounds.

Inventive Principle:

Principle #36Phase transitions

2Ease of manufacture

If conventional azodicarboxylic acid diesters are used in Mitsunobu reaction, then dehydration condensation occurs, but 1,2-hydrazinedicarboxylic acid diester by-product is produced which is insoluble in water and requires many processes to remove

Engineering Contradiction:

Improveease of by-product removalVSAvoidnumber of separation processes

Core Design Contradiction:

Ease of manufactureVSDevice complexity

Solution Approach 1:

The invention changes the solubility parameter of the 1,2-hydrazinedicarboxylic acid diester by-product by modifying the ester groups to 2-alkoxyethyl groups. This structural modification makes the by-product water-soluble, enabling simple removal by washing with water instead of requiring multiple complex separation processes.

Inventive Principle:

Principle #35Parameter changes

Solution Approach 2:

The invention uses water as an intermediary solvent to remove the by-product. The modified 1,2-hydrazinedicarboxylic acid diester by-product dissolves in water, allowing for easy separation from the organic reaction mixture through simple washing operations.

Inventive Principle:

Principle #24Intermediary (Mediator)

3Reliability

If azodicarboxylic acid dimethyl ester or diethyl ester is synthesized, then the Mitsunobu reaction can be performed, but caution must be exercised due to heat instability and danger during synthesis and purification

Engineering Contradiction:

Improvesafety during synthesis and handlingVSAvoiddifficulty of handling

Core Design Contradiction:

ReliabilityVSEase of operation

Solution Approach 1:

The invention changes the temperature parameter at which the compound exists, making it solid at ordinary temperatures rather than liquid. This eliminates the need for heating during purification and allows for safe handling at room temperature, removing the caution required for conventional liquid azodicarboxylic acid esters.

Inventive Principle:

Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The azodicarboxylic acid bis(2-alkoxyethyl) ester is produced safely and efficiently, with improved reactivity and easier after-treatment, enhancing its industrial viability compared to conventional esters.

Implementation Method 1

reacting hydrazine with a halocarbonic acid (2-alkoxyethyl) ester compound represented by formula (2) to give a 1,2-hydrazinedicarboxylic acid bis(2-alkoxyethyl) ester compound

Methodology Applied

Scientific EffectChemical reaction: Chemical Bonding

Implementation Method 2

oxidizing the 1,2-hydrazinedicarboxylic acid bis(2-alkoxyethyl) ester compound represented by formula (3) to give an azodicarboxylic acid bis(2-alkoxyethyl) ester compound

Methodology Applied

Scientific EffectOxidation: Oxidation

Data Source

PatentEP2112136B1Bis(2-alkoxyethyl) azodicarboxylate ester compound and intermediate for production of the same

Publication Date: 2012.05.23 TOYOBO CO LTD

AI summary

Provided is an industrially safe and useful azodicarboxylic acid bis(2-alkoxyethyl) ester compound that is useful for the Mitsunobu reaction in which it is used in combination with a phosphorus compound to carry out a dehydration condensation reaction, and also useful as an oxidizing agent, and a starting material for various synthetic processes. Also provided are a production intermediate of the above-described compound, and methods for producing these compounds. An azodicarboxylic acid bis(2-alkoxyethyl) ester compound represented by formula (1); wherein A represents an alkyl group having 1 to 10 carbon atoms.