Phosphonoethylthio Cyclodextrins for Drug Solubilization and Chiral Separation

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Solution Overview

Problem

Existing cyclodextrin derivatives like Sualphadex, Subetadex, and Sugammadex lack improved properties suitable for specific applications such as reversal of neuromuscular blockade, chiral selectors, and solubilizing agents for anticancer drugs.

Innovation Solution

Synthesis of α-, β-, and γ-cyclodextrin derivatives with 2-mercaptoethylphosphonic acid residues by iodination, replacement with (2-diethoxyphosphoryl)ethylthio branches, and hydrolysis to form (2-phosphonoethyl)thio branches at all C-6 positions.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Adaptability or versatility

If cyclodextrin derivatives are functionalized with (2-carboxyethyl)thio branches (Sualphadex, Subetadex, Sugammadex), then specific applications are enabled, but improved properties for specific applications such as reversal of neuromuscular blockade, chiral selectors, and solubilizing agents for anticancer drugs are not achieved

Engineering Contradiction:
Improveapplicability for specific usesVSAvoidperformance in specific applications
Core Design Contradiction:
Adaptability or versatilityVSReliability

Solution Approach 1:

The patent changes the chemical parameter of the functional branch from (2-carboxyethyl)thio to (2-phosphonoethyl)thio, specifically replacing the carboxylic acid group with a phosphonic acid group. This parameter change enables new applications including reversal of neuromuscular blockade, chiral selection in HPLC, and solubilization of anticancer drugs, while maintaining the cyclodextrin core structure that provides encapsulation capability

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite structure combining the cyclodextrin cyclic oligosaccharide core with (2-phosphonoethyl)thio functional branches at the C-6 positions. This composite material integrates the host-guest encapsulation property of cyclodextrins with the specific binding and solubilization properties of phosphonic acid groups, enabling multiple specialized applications

Inventive Principle:
Principle #40Composite materials

2Reliability

If the C-6 positions of cyclodextrin are decorated with (2-carboxyethyl)thio branches, then characteristic properties are obtained, but enhanced properties for medical and analytical applications are not achieved

Engineering Contradiction:
Improvecharacteristic propertiesVSAvoidsuitability for medical and analytical applications
Core Design Contradiction:
ReliabilityVSAdaptability or versatility

Solution Approach 1:

The patent modifies the functional group parameter from carboxylic acid to phosphonic acid at the C-6 positions. This change enhances affinity for specific medical targets (neuromuscular blockers) and analytical applications (chiral recognition in HPLC, capillary electrophoresis) while preserving the characteristic cyclodextrin encapsulation properties

Inventive Principle:
Principle #35Parameter changes

3Adaptability or versatility

If cyclodextrin derivatives are synthesized with modified functional groups, then new properties are obtained, but synthesis complexity increases

Engineering Contradiction:
Improvenew properties for applicationsVSAvoidsynthesis procedure
Core Design Contradiction:
Adaptability or versatilityVSDevice complexity

Solution Approach 1:

The patent employs preliminary iodination of the C-6 positions of cyclodextrin to create reactive iodine-substituted intermediates. This preliminary action enables subsequent straightforward nucleophilic substitution with phosphonic acid-containing reagents, streamlining the overall synthesis of the final functionalized derivatives

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent uses iodine as an intermediary group at the C-6 positions, which is introduced first and then replaced by the desired (2-phosphonoethyl)thio branches. This intermediary approach simplifies the synthesis by providing a reactive handle that facilitates the introduction of the final functional groups

Inventive Principle:
Principle #24Intermediary (Mediator)

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

Enhances the properties of cyclodextrin derivatives for applications like reversal of neuromuscular blockade, chiral selectors, and solubilizing agents for anticancer drugs, with potential uses in medicine, HPLC columns, and capillary electrophoresis.

Implementation Method 1

The synthetic procedure consists of the steps of (i) iodination of all C-6 positions of the native cyclodextrins, replacing the OH groups at those positions with iodine atoms

Methodology Applied
Scientific EffectIodination: Chemical Bonding

Implementation Method 2

replacement of the iodine atoms with (2-diethoxyphosphoryl)ethylthio branches

Methodology Applied
Scientific EffectNucleophilic substitution: Chemical Bonding

Implementation Method 3

hydrolysis of the diethyl esters to give free phosphonic acid groups

Methodology Applied
Scientific EffectHydrolysis: Hydrolysis

Implementation Method 4

These properties allow their use in a wide variety of applications. In addition, cyclodextrins can undergo structural modifications leading to changes in their properties, particularly referring to their solubility and their ability to form inclusion complexes

Methodology Applied
Scientific EffectInclusion complexation: Absorption (physical)

Data Source

PatentEP4656660A1Alfa-, beta-, and gamma- cyclodextrin derivatives decorated with (2-mercaptoethyl)phosphonic acid branches, synthesis and applications
Publication Date: 2025.12.03 UNIV DE ALMERI12A
  • EP4656660A1 patent drawingFigure 1(A)~1(C)
  • EP4656660A1 patent drawingFigure 2(A)~2(D)
  • EP4656660A1 patent drawingFigure 3(A)~3(C)

AI summary

The present invention refers to α-, β-, or γ-cyclodextrin derivatives wherein the hydroxyl groups at all C-6 positions of the α-, β-, or γ-cyclodextrin are replaced with 2-mercaptoethylphosphonic acid as (2-phosphonoethyl)thio branches. The invention further describes a method for obtaining α-, β-, or γ-cyclodextrin derivatives in accordance with the invention, wherein the method comprises: (a) preparing α-, β-, or γ-cyclodextrin derivatives where the hydroxyl groups at all C-6 positions of the α-, β-, or γ-cyclodextrin are replaced with iodine atoms; (b) replacing the iodine atoms at all C-6 positions of the α-, β-, or γ-cyclodextrin with [2-(diethoxyphosphoryl)ethyl]thio branches by using the isothiouronium salt of diethyl 2-mercaptoethylphosphonate; and (c) hydrolysing the diethyl esters of the [2-(diethoxyphosphoryl)ethyl]thio branches to give phosphonic acids as (2-phosphonoethyl)thio branches (-S-CH2-CH2-PO(OH)2). Finally, the invention describes several uses of the α-, β-, or γ-cyclodextrin derivatives obtained in accordance with the invention.