Ionic Liquids Based on Imidazolium Salts Incorporating a Nitrile Functionality

• US 20090143597A1
• Filed: 08/25/2004
• Published: 06/04/2009
• Est. Priority Date: 08/26/2003
• Status: Active Grant

• Current Assignee: Ecole polytechnique fãdãrale de lausanne epfl (Schweizerische Eidgenossenschaft)
• Original Assignee: Ecole polytechnique fãdãrale de lausanne epfl (Schweizerische Eidgenossenschaft)
• Inventors: Fei, Zhaofu, Zhao, Dongbin, Dyson, Paul
• Granted Patent: US 8,101,777 B2
• Time in Patent Office: Days
• US Class Current: 548/109
• CPC Class Codes: B01J 2231/4211 Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
• CPC Class Codes: B01J 2231/645 of C=C or C-C triple bonds
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 2531/824 Palladium
• CPC Class Codes: B01J 2531/828 Platinum
• CPC Class Codes: B01J 31/0218 Sulfides
• CPC Class Codes: B01J 31/0284 of an aromatic ring, e.g. pyridinium
• CPC Class Codes: B01J 31/0285 also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
• CPC Class Codes: B01J 31/1805 the ligands containing nitrogen
• CPC Class Codes: B01J 31/30 Halides
• CPC Class Codes: B01J 31/4038 containing noble metals
• CPC Class Codes: C07D 233/54 having two double bonds between ring members or between ring members and non-ring members
• CPC Class Codes: C07D 233/56 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• CPC Class Codes: C07F 5/022 without C-boron linkages
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

Novel chemical compounds of the general formula

K⁺A⁻,

in which K⁺is a 5- or 6-membered heterocyclic ring having 1-3 hetereo atoms, which can be independently N, S, or O;

with the proviso that at least one of the hetereo atoms must be a quaternized nitrogen atom having a —R′CN substituent, wherein R′ is alkyl (C₁ to C₁₂);

the heterocyclic ring having up to 4 or 5 substituents independently chosen from the moieties:

(i) H;

(ii) halogen or

(iii) alkyl (C₁ to C₁₂), which is unsubstituted or partially or fully substituted by further groups, preferably F, Cl, N(C_nF_(2n+1−x)H_x)₂, O(C_nF_(2n+1−x)H_x), SO₂(C_nF_(2n+1−x)H_x)₂ or C_nF_(2n+1−x)H_x where 1<n<6 and 0<x<13; and

(iv) a phenyl ring which is unsubstituted or partially or fully substituted by further groups, preferably F, Cl, N(C_nF_(2n+1−x)H_x)₂, O(C_nF_{(2n+1−X)Hx)}, SO₂(C_nF_(2n+1−x)H_x)₂ or C_nF_(2n+1−x)H_x where 1<n<6 and 0<x≦13; and

A⁻ is any anion that provides a salt with a low melting point, below about 100° C.; A can be halide, BF₄−, PF₆⁻, NO₃⁻, CH₃CO₂⁻, CF₃SO₃⁻, (CF₃SO₂)₂N⁻, (CF₃SO₂)₃C⁻, CF₃CO₂⁻ or N(CN)₂₋ or [BF₃RCN]

These compounds can be used as industrial solvents, especially as ligands for efficient catalyst recycling.

Claims

1. Chemical compounds of the general formula,

K⁺A⁻

,

in which K^{+ is a} 5- or 6-membered heterocyclic ring having 1-3 hetero atoms, which can be independently N, S, or 0;

with the proviso that at least one of the hetero atoms must be a quaternized nitrogen atom having a —

R′

CN substituent, wherein R′

is alkyl (C₁ to C₁₂);

the heterocyclic ring having up to 4 or 5 substituents independently chosen from the moieties;

(i) H;

(ii) halogen or

(iii) alkyl (C₁ to C₁₂), which is unsubstituted or partially or fully substituted by further groups, preferably F, Cl, N(C_nF<sub>(2n+1−

x)</sub>H_x)₂, O(C_nF<sub>(2n+1−

x)</sub>H_x), SO₂(C_nF<sub>(2n+1−

x)</sub>H_x)₂ or C_nF<sub>(2n+1−

x)</sub>H_x where 1<

n<

6 and0<

x≦

13; and

(iv) a phenyl ring which is unsubstituted or partially or fully substituted by further groups, preferably F, Cl, N(C_nF<sub>(2n+1−

x)</sub>H_x)₂, O(C_nF<sub>(2n+1−

0)</sub>H_x), SO₂(C_nF<sub>(2n+1−

x)</sub>H_x)₂ or C_nF<sub>(2n+1−

x)</sub>H_x where 1<

n<

6 and 0<

x≦

13; and

A⁻

is halide, such as chloride, bromide, fluoride and the like;

BF₄⁻

, PF6−

−

, NO₃⁻

, CH₃CO₂⁻

, CF₃SO₃⁻

, (CF₃SO₂)₂⁻

, (CF₃SO₂)₃C⁻

, CF₃CO₂⁻

or N(CN)₂⁻

.

2. The compound of claim 1 in which the heterocyclic ring is the pyrrolium, pyrazolium, pyridinium, pyrazinium, pyrimidinium, pyrazinium, imidazolium, thiazolium, oxazolium, or triazolium.

3. The compound of claim 2 in which the heterocyclic ring is the pyridinium or imidazolium.

4. The compound of claim 1 in which the anion is chloride.

5. The compound of claim 1 in which the anion is BF₄ or PF₆.

6. The compound of claim 1 in which the anion is BF₄.

9. The use of the compounds of claim 1 in the immobilization of metal catalysts, by mixing the compounds of claim 1 with the desired amounts of lanthanide and actinide series and transition metal catalyst compounds, such as palladium and platinum chlorides PdCl₂, PtCl₂, RuCl₃, RhCl₃, or [Ru(arene)Cl₂]₂.

10. The compound of claim 1 complexed with PdCl₂, PtCl₂, RuCl₃, RhCl₃, or [Ru(arene)Cl₂]₂.

7. The chemical compounds of the general formula,

K⁺A⁻

,

in which K⁺ is a 5- or 6-membered heterocyclic ring having 1-3 hetero atoms, which can be independently N, S, or O;

with the proviso that at least one of the hetero atoms must be a quaternized nitrogen atom having a —

R′

CN substituent, wherein R′

is alkyl (C₁ to C₁₂);

the heterocyclic ring having up to 4 or 5 substituents independently chosen from the moieties;

(i) H;

(ii) halogen or

(iii) alkyl (C₁ to C₁₂), which is unsubstituted or partially or fully substituted by further groups, preferably F, Cl, N(C_nF<sub>(2n+1−

x)</sub>H_x)₂, O(C_NF<sub>(2n+1−

x)</sub>H_x), SO₂(C_nF<sub>(2N+1−

x)</sub>H_x)₂ or C_nF<sub>(2n+1−

x)</sub>H_x where 1<

n<

6 and 0<

x<

13; and

(iv) a phenyl ring which is unsubstituted or partially or fully substituted by further groups, preferably F, Cl, N(C_nF<sub>(2n+1−

x)</sub>H_x)₂, O(C_nF<sub>(2n+1−

x)</sub>H_x), SO₂(C_nF<sub>(2n+1−

x)</sub>H_x)₂ or C_NF<sub>(2n+1−

x)Hx</sub> where 1<

n<

6 and 0<

x≦

13; and

A⁻

is [BF₃RCN]⁻

wherein R′

is alkyl (C₁ to C₁₂).

8. The chemical compounds according to claim 7 wherein A⁻

is [BF₃CHCH₃CH₂CN]⁻

.