6-bromo-3-hydroxy-2-pyrazinecarboxamide Crystal Purity Control

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Solution Overview

Problem

The production of high-purity 6-fluoro-3-hydroxy-2-pyrazinecarboxamide (compound A) is hindered by the presence of impurities, specifically 3-hydroxy-2-pyrazinecarboxamide (compound C), which is difficult to isolate due to its hydrate form and high content ratio in existing methods.

Innovation Solution

A method involving the bromination of anhydrous 3-hydroxy-2-pyrazinecarboxamide (compound C) with a controlled water content, followed by crystallization and subsequent reactions with bases and acids to produce 6-bromo-3-hydroxy-2-pyrazinecarboxamide (compound D) with reduced impurity levels, ultimately leading to high-purity compound A.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional bromination method is used to produce compound D from compound C, then compound D is obtained, but the content ratio of compound C impurity in compound D is high (300 ppm or more)

Engineering Contradiction:
Improvepurity of compound DVSAvoidcontent ratio of compound C impurity
Core Design Contradiction:
Manufacturing precisionVSObject-generated harmful factors

Solution Approach 1:

The patent changes the water content parameter in the reaction system from conventional levels to less than 5% (w/w) relative to compound C. This parameter change transforms the bromination reaction outcome, reducing compound C impurity content to less than 300 ppm while maintaining high reaction yield of compound D.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent applies local quality by using anhydrous or low-water-content compound C specifically in the bromination reaction step. This localized control of water content in the reaction environment enables selective improvement of product purity without affecting other process steps.

Inventive Principle:
Principle #3Local quality

2Productivity

If compound C is used in hydrate form for bromination, then the reaction proceeds, but the reaction yield is decreased and impurity content increases

Engineering Contradiction:
Improvereaction yield of compound DVSAvoidpurity of compound D
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The patent changes the physical state parameter of compound C from hydrate form to anhydrous form (water content less than 5% w/w). This parameter change simultaneously improves both reaction yield and product purity, resolving the contradiction between productivity and manufacturing precision.

Inventive Principle:
Principle #35Parameter changes

3Manufacturing precision

If high-purity compound D is produced through multiple crystallization steps, then impurity content decreases, but production complexity and time increase

Engineering Contradiction:
Improvepurity of compound DVSAvoidcomplexity of production process
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent performs preliminary action by controlling water content in the initial bromination reaction step. This preliminary control of reaction conditions prevents impurity formation from the outset, eliminating the need for multiple subsequent crystallization steps and reducing overall process complexity.

Inventive Principle:
Principle #10Preliminary action

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

This approach significantly reduces the content ratio of compound C in compound D and subsequently in compound A, resulting in a high-quality active pharmaceutical ingredient with improved purity and stability.

Implementation Method 1

adding bromine to the suspension obtained in step (1) wherein the content ratio of water included in the suspension obtained in step (1) is less than 5% (w/w) relative to compound C

Methodology Applied
Scientific EffectElectrophilic aromatic substitution: Chemical Bonding

Implementation Method 2

obtaining crystalline compound D (hereinafter, sometimes referred to as 'type-A crystals'), the crystal having diffraction angles of 5.5, 20.1, 23.7, 26.7, 27.5 and 28.1° in terms of 2θ in powder X-ray diffraction

Methodology Applied
Scientific EffectCrystallization: Crystallisation

Data Source

PatentEP3309149B16-bromo-3-hydroxy-2-pyrazinecarboxamide crystal and method for producing same
Publication Date: 2021.04.07 FUJIFILM TOYAMA CHEMICAL CO LTD
  • EP3309149B1 patent drawingFigure 1~2
  • EP3309149B1 patent drawingFigure 3~4
  • EP3309149B1 patent drawingFigure 5~6

AI summary

The purpose of the present invention is to provide a method for producing 6-bromo-3-hydroxy-2-pyrazinecarboxamide in which the content ratio of impurities is reduced. This production method includes a step of obtaining 6-bromo-3-hydroxy-2-pyrazinecarboxamide crystal having diffraction angles expressed in degrees 2θ of 5.5, 20.1, 23.7, 26.7, 27.5, and 28.1° and/or diffraction angles expressed in degrees 2θ of 7.1, 21.4, 25.2, 25.7, 27.1, and 28.8° in powder X-ray diffraction.