# US 8,785,655 B2 · Ionic liquid solvents

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- Number: US 8,785,655 B2
- Document ID: US8785655B2
- Status: Granted
- Kind: B2
- Application number: 13/203,133
- Filed: 2010-02-24
- Published: 2012-03-22
- Granted: 2014-07-22
- Earliest claimed: 2009-02-25
- Assignees: Dublin City University
- Applicants: Nicholas Gathergood; Bruce Pegot; Ian Beadham; Monika Gurbisz; Mukund D. Ghavre; Saibh Morrissey
- Inventors: Nicholas Gathergood; Bruce Pegot; Ian Beadham; Monika Gurbisz; Mukund D. Ghavre; Saibh Morrissey
- Web page: https://patentgrep.com/patent/US8785655B2

## CPC

- C07D 233/58: with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

A chiral ionic compound comprising an alkyl substituted imidazolium or pyridinium cationic core having an alkyl ester side chain (-alkyl-C(O)O—) directly linked to the core and an associated counter anion, characterized in that the —O— atom of the ester side chain is linked to an alpha, a beta or a gamma hydroxycarboxylic acid functionality via the alpha, beta or gamma hydroxy of the acid functionality and the hydroxycarboxylic acid functionality has at least one asymmetric carbon, or characterized in that an —N═ atom of the alkyl substituted imidazolium or pyridinium cationic core is substituted with an alpha, a beta or a gamma hydroxy group of a alpha, a beta or a gamma hydroxycarboxylic acid functionality and the hydroxycarboxylic acid functionality has at least one asymmetric carbon. The chiral ionic liquids (CILs) may be used as novel solvents, in particular for organic synthesis. The CILs have the potential to induce asymmetry into substrates or catalysts in a variety of organic transformations. A number of the compounds have low antimicrobial and low antifungal toxicities and are also biodegradable CILs.

## Claims

### Claim 1

A compound having general formula VII
wherein R1 is a C1-C4 alkyl;
R2 is —H or a C1-C4 alkyl;
R′ is selected from the group consisting of —H and a C1-C6 alkyl, wherein the C1-C6 alkyl group may be branched or unbranched;
R3 is a C1-C6 alkyl or a C1-C6 alkyl ether group, either the C1-C6 alkyl or the C1-C6 alkyl ether group may be branched or unbranched, and the alkyl ether group has at least one ether linkage in the alkyl chain; and
R4, R5, R6, R7, and R8 are each independently selected from the group consisting of —H, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, nitro, halo, acyl, phosphine (PR2), diarylphosphine (PAr2), phosphate, phosphite, sulfate, sulfite, phosphonamide, phosphinamide, sulfonamide, sulfonimide, sulfinamide, sulfinimide, carboxylic ester, carbonate, and carbamate, or two adjacent substitutions together form a C1-C4 alkylenedioxy ring; and
A is OctOSO3, NTf2 or N(CN)2.

### Claim 2 (depends on 1)

A compound according to claim 1 having general formula IX
wherein R1 is a C1-C4 alkyl;
R2 is —H or a C1-C4 alkyl;
R′ is selected from the group consisting of —H and a C1-C6 alkyl, wherein the C1-C6 alkyl group may be branched or unbranched;
R3 is a C1-C6 alkyl or a C1-C6 alkyl ether group, either the C1-C6 alkyl or the C1-C6 alkyl ether group may be branched or unbranched, and the alkyl ether group has at least one ether linkage in the alkyl chain; and
R4 and R5 are independently selected from the group consisting of —H, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, nitro, halo, acyl, phosphine (PR2), diarylphosphine (PAr2), phosphate, phosphite, sulfate, sulfite, phosphonamide, phosphinamide, sulfonamide, sulfonimide, sulfinamide, sulfinimide, carboxylic ester, carbonate, and carbamate, or two adjacent substitutions together form a C1-C4 alkylenedioxy ring.

### Claim 3 (depends on 1)

A compound according to claim 1 wherein R′ is —H.

### Claim 4 (depends on 2)

A compound according to claim 2 having general formula IX
wherein R1 is a C1-C4 alkyl;
R2 is —H or a C1-C4 alkyl;
R4 and R5 are independently selected from the group consisting of —H, a C1-C6 alkyl, and a C1-C6 alkoxy, or together form a methylenedioxy ring;
R3 is a C1-C6 alkyl; and
A is OctOSO3 or NTf2.

### Claim 5

A compound having general formula VII
wherein R1 is a C1-C4 alkyl;
R2 is —H or a C1-C4 alkyl;
R′ is selected from the group consisting of —H and a C1-C6 alkyl, wherein the C1-C6 alkyl group may be branched or unbranched;
R3 is a C1-C6 alkyl or a C1-C6 alkyl ether group, wherein the C1-C6 alkyl or the C1-C6 alkyl ether group may be branched or unbranched, and the alkyl ether group has at least one ether linkage in the alkyl chain; and
R4, R5, R6, R7, and R8 are each independently selected from the group consisting of —H, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, nitro, halo, acyl, phosphine (PR2), diarylphosphine (PAr2), phosphate, phosphite, sulfate, sulfite, phosphonamide, phosphinamide, sulfonamide, sulfonimide, sulfinamide, sulfinimide, carboxylic ester, carbonate, and carbamate, or two adjacent substitutions together form a C1-C4 alkylenedioxy ring; and
A is a counter anion.

### Claim 6 (depends on 2)

A compound according to claim 2 wherein R′ is —H.

### Claim 7 (depends on 5)

A compound according to claim 5 selected from the group consisting of:
KG 86 RS-3-methyl-1-[1-(methoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 87 R-3-methyl-1-[1-(methoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 88 S-3-methyl-1-[1-(methoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 89 RS-3-methyl-1-[1-(methoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 90 R-3-methyl-1-[1-(methoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 91 S-3-methyl-1-[1-(methoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 92 RS-3-methyl-1-[1-(methoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 93 R-3-methyl-1-[1-(methoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 94 S-3-methyl-1-[1-(methoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 300 S-3-methyl-1-[1-(ethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 301 R-3-methyl-1-[1-(ethoxyethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 302 S-3-methyl-1-[1-(pentoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 303 R-3-methyl-1-[1-(pentoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 304 RS-3-methyl-1-[1-(pentoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 305 S-3-methyl-1-[1-(ethoxyethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 306 S-3-methyl-1-[1-(butoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 307 RS-3-methyl-1-[1-(ethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 308 RS-3-methyl-1-[1-(butoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 400 RS-3-methyl-1-[1-(ethoxyethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 401 R-3-methyl-1-[1-(ethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 812 RS-3-methyl-1-[1-(ethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 813 RS-3-methyl-1-[1-(ethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 814 RS-3-methyl-1-[1-(butoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 815 RS-3-methyl-1-[1-(butoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 816 RS-3-methyl-1-[1-(pentoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 817 RS-3-methyl-1-[1-(pentoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 818 RS-3-methyl-1-[1-(ethoxyethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 819 RS-3-methyl-1-[1-(ethoxyethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 820 S-3-methyl-1-[1-(ethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 821 S-3-methyl-1-[1-(ethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 822 S-3-methyl-1-[1-(butoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 823 S-3-methyl-1-[1-(butoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 824 S-3-methyl-1-[1-(pentoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 825 S-3-methyl-1-[1-(pentoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 826 S-3-methyl-1-[1-(ethoxyethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 827 S-3-methyl-1-[1-(ethoxyethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 828 R-3-methyl-1-[1-(ethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 829 R-3-methyl-1-[1-(ethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 830 R-3-methyl-1-[1-(butoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 831 R-3-methyl-1-[1-(butoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 832 R-3-methyl-1-[1-(butoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium octyl sulphate
KG 833 R-3-methyl-1-[1-(pentoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 834 R-3-methyl-1-[1-(pentoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 835 R-3-methyl-1-[1-(ethoxyethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bromide
KG 836 R-3-methyl-1-[1-(ethoxyethoxycarbonyl)-1-phenylmethoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 1022 RS-3-methyl-1-[1-(butoxycarbonyl)-1-(3,4-methylenedioxyphenyl)methoxycarbonylmethyl]imidazolium bromide
KG 1026 RS-3-methyl-1-[1-(butoxycarbonyl)-1-(3,4-methylenedioxyphenyl)methoxycarbonylmethyl]imidazolium octyl sulphate
KG 1027 RS-3-butyl-1-[1-(butoxycarbonyl)-1-(3,4-methylenedioxyphenyl)methoxycarbonylmethyl]imidazolium bromide
KG 1029 RS-3-methyl-1-[1-(butoxycarbonyl)-1-(3,4-methylenedioxyphenyl)methoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 1034 RS-3-methyl-1-[1-(methoxycarbonyl)-1-(4-bromophenyl)methoxycarbonylmethyl]imidazolium bromide
KG 1035 RS-3-methyl-1-[1-(methoxycarbonyl)-1-(4-trifluoromethylphenyl)methoxycarbonylmethyl]imidazolium bromide
KG 1036 RS-3-methyl-1-[1-(methoxycarbonyl)-1-(4-methoxyphenyl)methoxycarbonylmethyl]imidazolium bromide
KG 1037 RS-3-butyl-1-[1-(butoxycarbonyl)-1-(3,4-methylenedioxyphenyl)methoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 1038 RS-3-butyl-1-[1-(butoxycarbonyl)-1-(3,4-methylenedioxyphenyl)methoxycarbonylmethyl]imidazolium octyl sulphate
KG 1039 RS-3-methyl-1-[1-(methoxycarbonyl)-1-(4-methoxyphenyl)methoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 1040 RS-3-methyl-1-[1-(methoxycarbonyl)-1-(4-trifluoromethylphenyl)methoxycarbonylmethyl]imidazolium bis(trifluoromethanesulphonyl)imide
KG 1044 RS-3-methyl-1-[1-(methoxycarbonyl)-1-(4-methoxyphenyl)methoxycarbonylmethyl]imidazolium octyl sulphate
KG 1047 RS-3-methyl-1-[1-(methoxycarbonyl)-1-(4-trifluoromethylphenyl)methoxycarbonylmethyl]imidazolium octyl sulphate and
KG 2011 RS-3-methyl-1-[1-(methoxycarbonyl)-1-(3,4-methylenedioxyphenyl)methoxycarbonylmethyl]imidazolium chloride.