Processes Employing Cyclodextrin Derivative Quaternary Salts

The process of claim 23, wherein the cyclodextrin derivative salt comprises a compound, or mixture of compounds, of the Formula 1,

• wherein:
• p is 4, 5 or 6;
• Q is independently selected at each occurrence from —OH, -sulfoalkyl ether-T, -sulfated alkyl ether-T, -sulfonate-T, -sulfate-T, -carboxyalkyl ether-T, -succinylate-T, -sulfoalkylthio ether-T, -carboxylate-T, -phosphoalkyl ether-T, -phosphate-T, and -phosphonate-T, wherein at least one Q is not —OH, and optionally wherein at least one Q is selected from the group consisting of -alkyl ether and -hydroxyalkyl ether;
• and
• T is a cation independently selected at each occurrence from the group consisting of one or more cations independently selected at each occurrence from a phosphonium cation or a quaternary nitrogen-containing cation, wherein each of the above is independently substituted or unsubstituted upon each occurrence.

The process of claim 23, wherein the cyclodextrin derivative salt comprises a compound or mixture of compounds, of the formula 1:

• wherein:
• p is 4, 5 or 6;
• Q is independently selected at each occurrence from —OH and -sulfoalkyl ether-T, wherein at least one Q is not —OH, and optionally wherein at least one Q is selected from the group consisting of -alkyl ether and -hydroxyalkyl ether;
• —SAE is a —O—(C2-C6 alkylene)-SO3− group, wherein at least one SAE is independently a —O—(C2-C6 alkylene)-SO3− group, or —O—(CH2)gSO3− group, wherein g is 2 to 6;
• and
• T is a cation independently selected at each occurrence from the group consisting of one or more cations independently selected at each occurrence from a phosphonium cation or a quaternary nitrogen-containing cation, wherein each cation above is independently substituted or unsubstituted upon each occurrence.

The process of claim 23, wherein the cyclodextrin derivative salt comprises an anionic sulfoalkyl ether cyclodextrin (SAE-CD) derivative salt or mixture of derivatives salts of the formula:

• SEEx-α-CD-T, SEEx-β-CD-T, SEEx-γ-CD-T,
• SPEx-α-CD-T, SPEx-β-CD-T, SPEx-γ-CD-T,
• SBEx-α-CD-T, SBEx-β-CD-T, SBEx-γ-CD-T,
• SPtEx-α-CD-T, SPtEx-β-CD-T, SPtEx-γ-CD-T,
• SHEx-α-CD-T, SHEx-β-CD-T or SHEx-γ-CD-T,
• wherein SEE denotes sulfoethyl ether, SPE denotes sulfopropyl ether, SBE denotes sulfobutyl ether, SPtE denotes sulfopentyl ether, and SHE denotes sulfohexyl ether;
• x denotes the average degree of substitution and ranges from 1 to 18 for α-CD, β-CD, γ-CD;
• and
• T is a cation independently selected at each occurrence from the group consisting of one or more cations independently selected at each occurrence from a phosphonium cation or a quaternary nitrogen-containing cation, wherein each cation above is independently substituted or unsubstituted upon each occurrence.

The process of claim 23, wherein the cyclodextrin derivative salt comprises a sulfoalkyl ether alkyl ether cyclodextrin compound or mixture of compounds of the formula 4

• wherein:
• “v” is 4, 5 or 6;
• and
• “A” is independently selected at each occurrence from the group consisting of —OH, —(SAET)x and -AEy;
• —SAE (sulfoalkyl ether) is —O—(C2-C6 alkylene)-SO3−;
• x is the degree of substitution for the SAET moiety and ranges from 1 to 3v+5;
• T is a cation independently selected at each occurrence from the group consisting of one or more cations independently selected at each occurrence from a phosphonium cation or a quaternary nitrogen-containing cation, wherein each cation above is independently substituted or unsubstituted upon each occurrence;
• AE (alkyl ether) is —O(C1-C3 alkyl);
• and
• y is the degree of substitution for the AE moiety and ranges from 1 to 3v+5;
• provided that at least one —SAET moiety and at least one -AE moiety are present;
• and the sum of x, y and the total number of —OH groups in a cyclodextrin derivative is 3v+6.

The process of claim 23, wherein the cyclodextrin derivative salt comprises a sulfoalkyl ether hydroxyl alkyl ether CD (SAE-HAE-CD) compound, or mixture of compounds, of the formula 5

• wherein:
• “v” is 4, 5 or 6;
• and
• “X” is independently selected at each occurrence from the group consisting of —OH, —(SAET)x and —HAEy;
• x is the degree of substitution for the SAET moiety and is 1 to 3w+5;
• —SAE is —O—(C2-C6 alkylene)-SO3−;
• T is a cation independently selected at each occurrence from the group consisting of one or more cations independently selected at each occurrence from a phosphonium cation or a quaternary nitrogen-containing cation, wherein each cation above is independently substituted or unsubstituted upon each occurrence;
• and
• HAE (hydroxyalkyl ether) is HO(C1-C6 alkyl)-O—;
• y is the degree of substitution for the HAE moiety and is 1 to 3w+5;
• provided that at least one —SAET moiety and at least one —HAE moiety are present;
• and the sum of x, y and the total number of —OH groups in a cyclodextrin derivative is 3w+6.

The process of claim 23, wherein cation is selected from the group consisting of:

• quaternary ammonium cation with the general formula (NR1R2R3R)+;
• phosphonium cation with the general formula (PR1R2R3R)+;
• imidazolium cation with the general formula
• in which the imidazole core may be substituted with at least one group selected from C1-C6 alkyl groups, C1-C6 alkoxy groups, C1-C6 hydroxyalkyl groups, C1-C6 aminoalkyl groups, C5-C12 aryl groups or C5-C12-aryl-C1-C6 alkyl groups;
• pyridinium cation with the general formula
• in which a carbon atom of the pyridine core may be substituted with at least one group selected from C1-C6 alkyl group, C1-C6 alkoxy group, C1-C6 hydroxyalkyl groups, C1-C6 aminoalkyl group, C5-C12 aryl group or C5-C12-aryl-C1-C6 alkyl group;
• pyrazolium cation with the general formula
• in which a carbon atom of the pyrazole core may be substituted with at least one group selected from C1-C6 alkyl group, C1-C6 alkoxy group, C1-C6 hydroxyalkyl groups, C1-C6 aminoalkyl group, C5-C12 aryl group or C5-C12-aryl-C1-C6 alkyl group;
• and
• triazolium cation with the general formula
• in which a carbon atom of the triazole core may be substituted with at least one group selected from C1-C6 alkyl groups, C1-C6 alkoxy groups, C1-C6 hydroxyalkyl groups, C1-C6 aminoalkyl groups, C5-C12 aryl groups or C5-C12-aryl-C1-C6 alkyl group;
• and
• guanidinium cation with the general formula
• wherein and the radicals R1, R2, R3, R4, R5, R6 are selected independently at each occurrence from the group consisting of:
• linear or branched, saturated or unsaturated, aliphatic or alicyclic alkyl groups with 1 to 20 carbon atoms;
• heteroaryl groups, heteroaryl-C1-C6 alkyl groups with 3 to 8 carbon atoms in the heteroaryl radical and at least one heteroatom selected from N, O and S which may be substituted with at least one group selected from C1-C6 alkyl groups and/or halogen atoms;
• aryl, aryl-C1-C6 alkyl groups with 5 to 12 carbon atoms in the aryl radical, which may optionally be substituted with at least one C1-C6 alkyl group and/or a halogen atom;
• and
• the radical R is selected from the group consisting of:
• linear or branched, saturated or unsaturated, aliphatic or alicyclic alkyl groups with 1 to 20 carbon atoms;
• heteroaryl-C1-C6 alkyl groups with 3 to 8 carbon atoms in the aryl radical and at least one heteroatom selected from N, O and S, which may be substituted with at least one C1-C6 alkyl group and/or halogen atom;
• aryl-C1-C6 alkyl groups with 5 to 12 carbon atoms in the aryl radical, which may be substituted with at least one C1-C6 alkyl group and/or halogen atom;
• and
• wherein any two of R, R1, R2, R3, R4, R5, R6 can join together to form a 4- to 8-membered heterocycle including the heteroatom to which each is attached.

An extractions process for the separation of enantiomers or diastereomers, the process comprising:

• a. exposing a solid or liquid containing at least one compound to be extracted to an extraction phase containing a cyclodextrin derivative salt comprising one or more anionic cyclodextrin derivatives and one or more cations independently selected at each occurrence from a phosphonium cation or a quaternary nitrogen-containing cation, wherein the at least one compound is a mixture of Isomer-1 and Isomer-2 of enantiomers or diastereomers, and the salt comprises an anionic cyclodextrin derivative and a quaternary nitrogen-containing cation;
• b. mixing the solid or liquid with the extraction phase for a period of time sufficient to specifically or selectively extract a first portion of Isomer-1 into the extraction phase;
• and
• c. separating the extraction phase from the solid or liquid;
• and
• d. separating the extracted first portion of Isomer-1 from the extraction phase to provide an enantiomerically enriched, enantiomerically pure, diastereomerically-enriched or diastereomerically-pure Isomer-1 of the compound.

A supercritical fluid extraction process for the separation of one or more target compounds from a mass comprising the one or more target compounds, the process comprising:

• a. providing a solid or liquid mass comprising one or more target compounds;
• b. treating the mass with a cyclodextrin derivative salt comprising one or more anionic cyclodextrin derivatives and one or more cations independently selected at each occurrence from a phosphonium cation or a quaternary nitrogen-containing cation and with a supercritical fluid to form an ionic liquid phase and a supercritical fluid phase;
• c. separating the supercritical fluid phase from the phase containing the cyclodextrin derivative salt;
• and
• d. isolating the one or more target compounds from the supercritical fluid phase by removal of the supercritical fluid, e.g. evaporation thereof;
• and/or
• e. isolating the one or more target compounds from the phase containing the cyclodextrin derivative salt by treating the ionic liquid with an aqueous or organic phase into which the one or more compounds is extracted.

A method of separating one or more compounds from a mixture of structurally related compounds, the method comprising:

• a. exposing a solid or liquid containing a mixture of structurally related compounds to an extraction phase containing a cyclodextrin derivative salt, wherein the salt comprises an anionic cyclodextrin derivative and a quaternary nitrogen-containing cation;
• b. mixing the solid or liquid with the extraction phase for a period of time sufficient to specifically or selectively extract one or more compounds from the mixture of structurally related compounds into the extraction phase;
• and
• c. separating the extraction phase from the solid or liquid;
• and
• d. separating the extracted one or more compounds from the extraction phase to provide an enriched or pure one or more compounds.

An extraction process for the separation of a first compound from a mixture of first and second compounds comprising:

• a. exposing a solid or liquid containing at least a first compound and a second compound to an extraction phase containing a cyclodextrin derivative salt, wherein the salt comprises an anionic cyclodextrin derivative and a quaternary nitrogen-containing cation;
• b. mixing the solid or liquid with the extraction phase for a period of time sufficient to specifically or selectively extract a first portion of first compound into the extraction phase;
• c. separating the extraction phase from the solid or liquid;
• and
• d. separating the extracted first portion of first compound from the extraction phase to provide an enriched or pure first compound.

A chemical process comprising:

• a. providing a cyclodextrin derivative salt as a reaction medium, one or more starting materials and optionally one or more catalysts, wherein the salt comprises an anionic cyclodextrin derivative and a quaternary nitrogen-containing cation;
• b. mixing the salt, one or more starting materials and optionally one or more catalysts, whereby the one or more starting materials complexes with the salt in situ, to form a reaction milieu, optionally while heating the reaction milieu, cooling the reaction milieu and/or exposing the reaction milieu to radiation, and causing a chemical reaction to form at least one enantiomerically-enriched, enantiomerically-pure, diastereomerically-pure or diastereomerically-enriched reaction product;
• and
• c. isolating the reaction product.