Ambrisentan Synthesis via Ammonium-Based Resolution

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Solution Overview

Problem

Current methods for producing Ambrisentan face challenges in achieving high optical purity on an industrial scale due to the expense of optically active bases and difficulties in filtering diastereomeric salts, which affect the efficiency and cost-effectiveness of the process.

Innovation Solution

A novel process for resolving racemic 2-hydroxy-3-methoxy-3,3-diphenylpropanoic acid using a suitable optically active amine as a resolving agent to form a diastereomeric salt, which is then reacted with 4,6-dimethyl-2-(methylsulfonyl)pyrimidine to produce Ambrisentan, allowing for high enantiomeric purity and scalability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If expensive optically active bases are used for resolution, then high optical purity is achieved, but production cost increases

Engineering Contradiction:
Improveoptical purityVSAvoidproduction cost
Core Design Contradiction:
Manufacturing precisionVSQuantity of substance

Solution Approach 1:

The patent replaces expensive optically active bases with cheap, readily available amines such as ammonium carbonate, ammonium bicarbonate, or ammonium fluoride. These inexpensive resolving agents form diastereomeric salts that can be easily separated, achieving high optical purity without the high costs associated with traditional optically active bases like (S)-1-(4-nitrophenyl) ethylamine

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The patent changes the chemical parameters of the resolving agent from expensive optically active bases to inexpensive inorganic or simple organic amines. This parameter change maintains the ability to form separable diastereomeric salts while dramatically reducing material costs for large-scale production

Inventive Principle:
Principle #35Parameter changes

2Manufacturing precision

If traditional resolution methods are used, then optical purity can be achieved, but filtering diastereomeric salts becomes difficult

Engineering Contradiction:
Improveoptical purityVSAvoidfiltering operation
Core Design Contradiction:
Manufacturing precisionVSEase of operation

Solution Approach 1:

The use of inexpensive ammonium-based resolving agents produces diastereomeric salts with superior filtration properties compared to traditional methods. These salts crystallize in forms that are easily separated by filtration, eliminating the need for additional washing steps and improving operational ease

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The patent utilizes controlled crystallization and phase transition of diastereomeric salts from solution to solid state. By optimizing crystallization conditions with ammonium-based agents, the salts form well-defined crystals that are easily filtered, whereas traditional methods produce oils or amorphous solids that are difficult to separate

Inventive Principle:
Principle #36Phase transitions

3Manufacturing precision

If resolution is performed on laboratory scale, then optical purity can be achieved, but scaling up to industrial production becomes problematic

Engineering Contradiction:
Improveoptical purityVSAvoidscalability
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent employs inexpensive ammonium-based resolving agents that are suitable for both laboratory and industrial scales. These agents maintain consistent performance across scale-up, providing reliable optical purity without the cost and operational challenges that plague traditional methods at larger scales

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The resolving agents ammonium carbonate, ammonium bicarbonate, and ammonium fluoride serve multiple functions: they form separable diastereomeric salts, provide easy filtration, and maintain optical purity across different scales. This universality allows the same protocol to be effectively applied from laboratory to industrial production without modification

Inventive Principle:
Principle #6Universality (Multi-functionality)

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 enables the production of Ambrisentan with high enantiomeric purity and efficiency, overcoming previous limitations by simplifying the resolution process and reducing costs associated with expensive resolving agents, thus facilitating large-scale industrial production.

Implementation Method 1

reacting the racemate compound with a suitable optically active amine and subsequently separating off the diastereomeric salt with high chiral purity

Methodology Applied
Scientific EffectDiastereomeric salt formation: Chemical Bonding

Implementation Method 2

reacting the diastereomeric salt of 2-hydroxypropanoic acids of formula (II) with 4,6-dimethyl-2-(methylsulfonyl)pyrimidine (VII), to obtain ambrisentan

Methodology Applied
Scientific EffectCondensation reaction: Chemical Bonding

Data Source

PatentEP2451786B1Improved process for the preparation of ambrisentan and novel intermediates thereof
Publication Date: 2014.01.22 ZYDUS LIFESCIENCES LTD
  • EP2451786B1 patent drawingFigure 1
  • EP2451786B1 patent drawingFigure 2
  • EP2451786B1 patent drawingFigure 3

AI summary

The invention relates to improved processes for the preparation of ambrisentan. The invention also relates to a novel intermediate useful in the preparation of ambrisentan and a process for the preparation of the intermediate. The invention also relates to new polymorphic form of ambrisentan. In particular, it relates to a polymorphic form, designated as Form I of ambrisentan and a process for the preparation of the Form I.