Morpholine Derivative Salts for Solubility and Stability

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Solution Overview

Problem

The free base form of Compound I exhibits poor water solubility, is prone to oxidation, and has stability issues, making it unsuitable for long-term storage and use in pharmaceutical applications.

Innovation Solution

Development of pharmaceutically acceptable salts, specifically malate and tartrate salts, including their crystal forms, which offer improved properties such as better crystallinity, increased water solubility, and enhanced stability against oxidation and light exposure.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If the free base form of Compound I is used, then the synthesis is straightforward, but the water solubility is poor and oxidation resistance is low

Engineering Contradiction:
Improvesynthesis simplicityVSAvoidoxidation resistance
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent applies parameter changes by converting the free base form of Compound I into salt forms (malate and tartrate). This chemical form transformation fundamentally alters the molecular properties, dramatically improving water solubility from negligible to approximately 100 mg/mL for malate, and enhancing oxidation resistance and stability without complicating the manufacturing process

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates composite materials by forming salts between Compound I and chiral acids (L-malic acid or L-tartaric acid). These salt forms represent composite structures that combine the pharmacologically active Compound I with counterions from the acids, resulting in a new material with superior solubility, stability, and crystalline properties while maintaining the core therapeutic function

Inventive Principle:
Principle #40Composite materials

2Ease of manufacture

If the free base form of Compound I is used, then the preparation is simple, but the water solubility is poor

Engineering Contradiction:
Improvepreparation simplicityVSAvoidwater solubility
Core Design Contradiction:
Ease of manufactureVSQuantity of substance

Solution Approach 1:

The patent transforms the chemical parameters of Compound I by converting it from free base to salt forms. This parameter change results in dramatic improvement of water solubility - the malate form achieves approximately 100 mg/mL solubility, making the substance suitable for pharmaceutical formulations requiring aqueous solubility while keeping the preparation method straightforward

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent utilizes phase transitions by forming crystalline salt structures from the free base. The malate and tartrate salts exhibit well-defined crystal forms with characteristic X-ray diffraction patterns, representing a phase transition from the amorphous or semi-solid free base to ordered crystalline structures, thereby enhancing solubility and stability

Inventive Principle:
Principle #36Phase transitions

3Ease of manufacture

If the free base form of Compound I is used, then no additional reagents are needed, but the stability under light and oxidation conditions is poor

Engineering Contradiction:
Improvereagent-free synthesisVSAvoidstability under light and oxidation
Core Design Contradiction:
Ease of manufactureVSStability of the object's composition

Solution Approach 1:

The patent changes the chemical parameters of Compound I by forming salt structures with L-malic acid or L-tartaric acid. This transformation significantly enhances stability under light and oxidation conditions, as the salt forms exhibit greater chemical inertness and resistance to degradation compared to the free base, while the synthesis remains relatively simple requiring only the addition of the chiral acid

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs readily available, inexpensive chiral acids (L-malic acid or L-tartaric acid) as reagents to form stable salt structures. These simple, easily obtainable reagents provide long-term stability benefits without requiring complex or expensive synthetic procedures, effectively protecting the pharmacologically active Compound I from degradation

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

4Reliability

If crystal forms of salts are developed, then water solubility and stability are improved, but the crystallization process becomes more complex

Engineering Contradiction:
ImprovestabilityVSAvoidcrystallization process complexity
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent utilizes phase transitions to form crystalline salt structures from the free base-compound and chiral acid mixture. By controlling the dissolution and crystallization process, well-defined crystal forms with characteristic X-ray diffraction patterns are obtained. This phase transition approach improves stability and solubility while maintaining relatively simple processing steps

Inventive Principle:
Principle #36Phase transitions

Solution Approach 2:

The patent applies parameter changes by adjusting pH, temperature, and solvent conditions to optimize the formation of crystalline salt structures. These parameter optimizations enable controlled crystallization that balances complexity with the achievement of stable, soluble crystal forms suitable for pharmaceutical applications

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 malate and tartrate salts of Compound I demonstrate improved water solubility, stability, and reduced hygroscopicity, addressing the limitations of the free base form, making them more suitable for pharmaceutical use and storage.

Implementation Method 1

The malate is a compound formed by compound I and L-malic acid in a molar ratio of 1:1... The tartrate is a compound formed by compound I and L-tartaric acid in a molar ratio of 1:1

Methodology Applied
Scientific EffectAcid-base reaction: Chemical Bonding

Implementation Method 2

characteristic peaks at 2θ of 7.767°±0.2°, 13.897°±0.2°, 14.775°±0.2°, 17.098°±0.2°, 18.999°±0.2°, 20.153±0.2°, 20.960°±0.2°, 21.423°±0.2°, 26.348°±0.2°, 27.892°±0.2° in the X-ray powder diffraction pattern

Methodology Applied
Scientific EffectX-ray diffraction: X-Ray

Implementation Method 3

measured on a Bruker D8 Advance diffractometer equipped with a θ-2θ goniometer, a Mo Monochromator and a Lynxeye detector, using K X-ray with a wavelength of 1.54 nm

Methodology Applied
Scientific EffectBragg diffraction: Bragg Diffraction

Implementation Method 4

the TGA plot shows that the malate is decomposed at about 185.8°C, and the sample loses no weight before decomposition

Methodology Applied
Scientific EffectThermogravimetric analysis: Thermolysis

Implementation Method 5

the DSC plot shows an endothermic peak (95 J/g) at about 121°C

Methodology Applied
Scientific EffectDifferential scanning calorimetry: Calorimetry

Implementation Method 6

the DVS plot shows that the weight of the morpholine derivative malate changes for about 1.2% in a range of 20%-80% humidity

Methodology Applied
Scientific EffectAdsorption: Adsorption

Data Source

PatentEP3398946B1Salt of morpholine derivative and crystalline form thereof, as well as preparation method, pharmaceutical composition and use of the same
Publication Date: 2022.05.04 SHANGHAI PHARMACEUTICALS HOLDING CO LTD
  • EP3398946B1 patent drawingFigure 1
  • EP3398946B1 patent drawingFigure 2
  • EP3398946B1 patent drawingFigure 3~4

AI summary

The present invention provides novel pharmaceutically acceptable salts of a morpholine derivative, including a malate, a tartrate, a hydrochloride, an acetate, and a naphthalene diphosphate thereof, wherein the tartrate has 3 crystal salt forms: crystal form A, crystal form B and dihydrate; the malate, the hydrochloride, and the acetate each have one crystal salt form; the naphthalene diphosphate is amorphous. When compared to the known morpholine derivative free base, the present invention has one or more improved properties, e.g., a better crystalline state, greatly improved water solubility, light stability and thermal stability, etc. The present invention further provides preparation methods for the salts of morpholine derivative and the crystal forms thereof, pharmaceutical compositions and use thereof.