Basic ionic liquids

• US 20090270248A1
• Filed: 01/04/2006
• Published: 10/29/2009
• Est. Priority Date: 01/04/2005
• Status: Active Grant

• Current Assignee: Queen's University Belfast (Queen's University)
• Original Assignee: Queen's University Belfast (Queen's University)
• Inventors: Forsyth, Stewart, Earl, Martyn John, Gunaratne, Nimal, Seddon, Kenneth Richard, Katdare, Suhas, Frohlich, Ute
• Granted Patent: US 8,609,572 B2
• Time in Patent Office: Days
• US Class Current: 502/167
• CPC Class Codes: B01J 2231/341 1,2-additions, e.g. aldol or Knoevenagel condensations
• CPC Class Codes: B01J 2231/342 Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
• CPC Class Codes: B01J 2231/346 Mannich type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues to aldimines or ketimines
• CPC Class Codes: B01J 2231/348 1,4-additions, e.g. conjugate additions
• CPC Class Codes: B01J 2231/349 1,2- or 1,4-additions in combination with further or prior reactions by the same catalyst, i.e. tandem or domino reactions, e.g. hydrogenation or further addition reactions
• CPC Class Codes: B01J 2231/4261 Heck-type, i.e. RY + C=C, in which R is aryl
• CPC Class Codes: B01J 2231/645 of C=C or C-C triple bonds
• CPC Class Codes: B01J 2231/72 Epoxidation
• CPC Class Codes: B01J 2531/824 Palladium
• CPC Class Codes: B01J 2531/90 Catalytic systems characterized by the solvent or solvent system used
• CPC Class Codes: B01J 31/0201 Oxygen-containing compounds
• CPC Class Codes: B01J 31/0204 Ethers
• CPC Class Codes: B01J 31/0225 comprising sulfonic acid groups or the corresponding salts
• CPC Class Codes: B01J 31/0234 Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
• CPC Class Codes: B01J 31/0237 Amines
• CPC Class Codes: B01J 31/0277 comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
• CPC Class Codes: B01J 31/0278 containing nitrogen as cationic centre
• CPC Class Codes: B01J 31/0282 of an aliphatic ring, e.g. morpholinium
• CPC Class Codes: B01J 31/0284 of an aromatic ring, e.g. pyridinium
• CPC Class Codes: B01J 31/0287 containing atoms other than nitrogen as cationic centre
• CPC Class Codes: B01J 31/0288 : Phosphorus
• CPC Class Codes: B01J 31/0289 : Sulfur
• CPC Class Codes: B01J 31/0291 : also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
• CPC Class Codes: B01J 31/2208 : Oxygen, e.g. acetylacetonates
• CPC Class Codes: C07B 61/00 : Other general methods
• CPC Class Codes: C07C 211/63 : having quaternised nitrogen atoms bound to acyclic carbon atoms
• CPC Class Codes: C07C 217/08 : the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
• CPC Class Codes: C07C 45/512 : the singly bound functional group being a free hydroxyl group
• CPC Class Codes: C07C 45/62 : by hydrogenation of carbon-to-carbon double or triple bonds
• CPC Class Codes: C07C 45/66 : by dehydration
• CPC Class Codes: C07C 45/67 : by isomerisation; by change of size of the carbon skeleton
• CPC Class Codes: C07C 45/72 : by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
• CPC Class Codes: C07C 45/73 : combined with hydrogenation
• CPC Class Codes: C07C 45/74 : combined with dehydration
• CPC Class Codes: C07C 47/228 : containing six-membered aromatic rings, e.g. phenylacetaldehyde
• CPC Class Codes: C07C 49/17 : containing hydroxy groups sugars C07H
• CPC Class Codes: C07C 49/203 : with only carbon-to-carbon double bonds as unsaturation
• CPC Class Codes: C07C 49/403 : of a six-membered ring
• CPC Class Codes: C07C 49/497 : a keto group being part of a six-membered ring
• CPC Class Codes: C07C 49/597 : of a five-membered ring
• CPC Class Codes: C07C 49/603 : of a six-membered ring
• CPC Class Codes: C07C 49/637 : the condensed ring system containing ten carbon atoms
• CPC Class Codes: C07C 49/647 : having unsaturation outside the ring
• CPC Class Codes: C07C 49/707 : a keto group being part of a three- to five-membered ring
• CPC Class Codes: C07D 213/73 : Unsubstituted amino or imino radicals
• 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 303/32 : by aldehydo- or ketonic radicals
• CPC Class Codes: Y02P 20/54 : using solvents, e.g. supercritical solvents or ionic liquids

Abstract

Use of ionic liquids as solvents in base-catalysed chemical reactions wherein the ionic liquid is composed of at least one species of cation and at least one species of anion, characterised in that a cation of the ionic liquid comprises a positively charge moiety and a basic moiety, and further wherein such ionic liquids may be used as promoters or catalysts for the chemical reactions.

Claims

1. Use of an ionic liquid as a solvent and catalyst in a base-catalysed chemical reaction, the ionic liquid being composed of at least one species of cation and at least one species of anion, characterized in that a cation of the ionic liquid comprises (i) a positively charged moiety and (ii) a basic moiety.

2. Use according to claim 1 wherein the ionic liquid is represented by the formula:

[Cat⁺-Z-Bas][X⁻

]

wherein;

Cat⁺=positively charged moiety;

Bas=basic moiety; and

Z=a covalent bond joining Cat⁺ and Bas or 1, 2 or 3 aliphatic divalent linking groups each containing 1 to 10 carbon atoms and each optionally one, two or three oxygen atoms.

X⁻

=anion; and

with the proviso that Bas is not —

OH.

3. Use according to claim 2, wherein Bas comprises at least one nitrogen, phosphorus, sulphur, oxygen or boron atom.

4. Use according to claim 3, wherein Bas comprises at least one primary, secondary or tertiary amino group.

5. Use according to claim 3, wherein Bas is selected from —

N(R₁)(R₂), and —

P(R₁)(R₂)(R₃); and

wherein R₁, R₂ and R₃ can be the same or different and are each independently selected from hydrogen, linear or branched alkyl, cycloalkyl, aryl and substituted aryl.

6. Use according to claim 5, wherein R₁, R₂ and R₃ are each selected from hydrogen, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, isobutyl, pentyl, hexyl, cyclohexyl, benzyl and phenyl.

7. Use according to claim 5, wherein Bas is selected from —

N(CH₃)₂ and —

N(CH(CH₃)₂)₂.

8. Use according to claim 2, wherein Z is selected from linear or branched C₁ to C₁₈ alkanediyl, substituted alkanediyl, dialkanylether or dialkanylketone.

9. Use according to claim 8, wherein Z is selected from —

(CH₂—

CH₂)—

, —

(CH₂—

CH₂—

CH₂)—

, —

(CH₂—

CH₂—

CH₂—

CH₂)—

, —

(CH₂—

CH₂—

CH₂—

CH₂—

CH₂)—

, —

(CH₂—

CH₂—

CH₂—

CH₂—

CH₂—

CH₂)—

, —

(CH₂—

CH₂—

O—

CH₂—

CH₂)— and

—

(CH₂—

CH₂—

O—

CH₂—

CH₂—

CH₂)—

.

10. Use according to claim 2, wherein the Cat⁺ moiety comprises or consists of a heterocyclic ring structure selected from imidazolium, pyridinium, pyrazolium, thiazolium, isothiazolinium, azathiozolium, oxothiazolium, oxazinium, oxazolium, oxaborolium, dithiazolium, triazolium, selenozolium, oxaphospholium, pyrollium, borolium, furanium, thiophenium, phospholium, pentazolium, indolium, indolinium, oxazolium, isooxazolium, isotriazolium, tetrazolium, benzofuranium, dibenzofuranium, benzothiophenium, dibenzothiophenium, thiadiazolium, pyrimidinium, pyrazinium, pyridazinium, piperazinium, piperidinium, morpholinium, pyranium, annolinium, phthalazinium, quinazolinium, quinazalinium, quinolinium, isoquinolinium, thazinium, oxazinium and azaannulenium.

11. Use according to claim 10, wherein Cat⁺-Z-Bas is selected from:

—

wherein;

Bas and Z are as defined above; and

R^b, R^c, R^d, R^e, R^f, R^g and R^h can be the same or different, and are each independently selected from hydrogen, a C₁ to C₄₀, straight chain or branched alkyl group, a C₃ to C₈ cycloalkyl group, or a C₆ to C₁₀ aryl group, wherein said alkyl, cycloalkyl or aryl groups are unsubstituted or may be substituted by one to three groups selected from;

C₁ to C₆ alkoxy, C₆ to C₁₀ aryl, CN, OH, NO₂, C₇ to C₃₀ aralkyl and C₇ to C₃₀ alkaryl, or any two of R^b, R^c, R^d, R^e and R^f attached to adjacent carbon atoms form a methylene chain —

(CH₂)_q wherein q is from 8 to 20.

12. Use according to claim 11, wherein the Cat⁺-Z-Bas is selected from:

wherein;

Bas, Z and R^b are as defined above.

13. Use according to claim 11, wherein Cat⁺-Z-Bas is selected from:

14. Use according to claim 10, wherein Cat⁺ is obtained from alkylation, protonation and/or acylation of a precursor selected from imidazoles, pyridines, pyrazoles, thiazoles, isothiazoles, azathiozoles, oxothiazoles, oxazines, oxazolines, oxazoboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, boroles, furans, thiophenes, phospholes, pentazoles, indoles, indolines, oxazoles, isooxazoles, isotriazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophenes, dibenzothiophenes, thiadiazoles, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholenes, pyrans, annolines, phthalzines, quinazolines, quinoxalines, quinolines, isoquinolines, thazines, oxazines, and azaannulenes.

15. Use according to claim 2, wherein Cat⁺ is an acyclic organic moiety.

16. Use according to claim 15 wherein the Cat⁺ moiety comprises or consists of a group selected from amino, amidino, imino, guanidino, phosphino, arsino, stibino, alkoxyalkyl, alkylthio, alkylseleno and phosphinimino.

17. Use according to claim 16, wherein Cat⁺-Z-Bas is selected from:

[N(Z-Bas)(R^b)(R^c)(R^d)]⁺ and [P(Z-Bas)(R^b)(R^c)(R^d)]⁺

wherein;

Bas, Z, R^b, R^c, and R^d are as defined above;

with the proviso that Bas is not —

OH and —

N(Et)₂

18. Use according to claim 16 wherein Cat⁺-Z-Bas is selected from:

wherein;

Bas, Z and R^b are as defined above.

19. Use according to claim 17, wherein Cat⁺-Z-Bas is selected from:

20. Use according to claim 2, wherein Cat⁺-Z-Bas is a compound of formula:

wherein;

R^b is as defined above

21. Use according to claim 1, wherein X⁻

is an alkylated or halogenated salt of a Group IB, IIIA, IVA, VA, VIA or VIIA element.

22. Use according to claim 21 wherein X⁻

the anion is hydroxide, alkoxide, phenoxide, dicyanamide, borate, phosphate, nitrate, sulfate, triflate, halogenated copperate, antimonate, phosphite, substituted and unsubstituted metalloborane, substituted and unsubstituted carboxylate and triflate;

or mixtures thereof.

23. Use according to claim 21, wherein X⁻

is selected from BF₄, PF₆, CF₃SO₃, CF₃COO, SbF₆, CuCl₂, A₅F₆, SO4, CF₃CH₂CH₂COO, (CF₃SO₂)₃C, CF₃(CF₂)₃ SO₃, [CF₃SO₂]₂N and a metal inorganic anion.

24. Use according to claim 1, wherein, X⁻

is selected from halide, triflate, bistrifluoromethanesulfonylamide [(CF₃SO₂)₂N] and alkylsulfonate [RSO₃].

25. Use according to claim 1, wherein the ionic liquid comprises a mixture of one or more cations having a basic moiety and a positively charged moiety.

26. Use according to claim 1, wherein the ionic liquid comprises a mixture of one or more anions.

27. Use according to claim 1, wherein the ionic liquid further comprises a mixture of one or more ionic liquids composed of a cation and an anion.

29. Use according to claim 1 wherein the chemical reaction is selected from the Heck Reaction, Suzuki Coupling, nucleophilic displacement reactions, hydrolysis, esterification, transesterification aldol reactions, epoxidation, hydrogenation, condensation, oxidation reduction, hydration, dehydration, substitution, aromatic substitution, addition (including to carbonyl groups), elimination, polymerisation, depolymerisation, oligomerisation, dimersiation, coupling, electrocyclic, isomerisation, carbene formation, epimerisation, inversion, rearrangement, photochemical, microwave assisted, thermal, sonochemical and disproportionation reactions.

31. Use according to claim 1, wherein X⁻

is represented by the formula;

[X—

R-Bas]⁻

Wherein;

X and Bas are as defined above; and

R is a covalent bond joining X and Bas, or a linking group comprising 1 to 10 carbon atoms and optionally one, two or three oxygen atoms.

28. (canceled)

30. (canceled)

32. A basic ionic liquid of formula:

[Cat⁺-Z-Bas][X]

wherein;

Cat⁺=is a positively charged moiety comprising or consisting of a heterocyclic ring structure selected from pyridinium, pyrazolium, thiazolium, isothiazolinium, azathiozolium, oxothiazolium, oxazinium, oxazolium, oxaborolium, dithiazolium, triazolium, selenozolium, oxaphospholium, pyrollium, borolium, furanium, thiophenium, phospholium, pentazolium, indolium, indolinium, oxazolium, isooxazolium, isotriazolium, tetrazolium, benzofuranium, dibenzofuranium, benzothiophenium, dibenzothiophenium, thiadiazolium, pyrimidinium, pyrazinium, pyridazinium, piperazinium, piperidinium, morpholinium, pyranium, annolinium, phthalazinium, quinazolinium, quinazalinium, quinolinium, isoquinolinium, thazinium, oxazinium and azaannulenium;

Z=a covalent bond joining Cat⁺ and Bas or 1, 2 or 3 aliphatic divalent linking groups each containing 1 to 10 carbon atoms and each optionally one, two or three oxygen atoms;

X⁻

=is selected from alkoxide, phenoxide, dicyanamide, borate, nitrate, sulfate, triflate, halogenated copperate, antimonate, phosphite, substituted and unsubstituted metalloborane, substituted and unsubstituted carboxylate and triflate, or mixtures thereof, and

Bas=a hindered basic moiety.

33. A basic ionic liquid according to claim 32 selected from a compound of formula:

wherein;

Bas, Z, R^b, R^c, R^d, R^e, R^f, R^g, R^h and X⁻

are as defined above.

34. A basic ionic liquid according to claim 33, selected from:

wherein;

Bas, Z, X⁻

and R^b are as defined above.

35. A basic ionic liquid according to claim 33, selected from:

36. A basic ionic liquid represented by the formula:

[Cat⁺-Z-Bas][X⁻

]

wherein;

Cat⁺=acyclic positively charged moiety;

Z=a covalent bond joining Cat⁺ and Bas or 1, 2 or 3 aliphatic divalent linking groups each c containing 1 to 10 carbon atoms and each optionally one, two or three oxygen atoms;

X⁻

=anion;

Bas=a hindered basic moiety selected from —

N(R₁)(R₂), —

P(R₁)(R₂)(R₃), —

PO(OR₁), PO(OR₁)(OR₂), —

S(R₁), —

SO₂(OR₁), and boron containing groups, wherein R₁, R₂ and R₃ can be the same or different and are each independently selected from hydrogen, linear or branched alkyl, cycloalkyl, aryl and substituted aryl;

with the proviso that Bas is not —

NH₂, —

NHMe, N(Et)₂, or boratrane; and

with the proviso that where Cat⁺ comprises an amino group, the anion X⁻

is selected from dicyanamide, borate, phosphate, nitrate, sulfate, triflate, halogenated copperate, antimonate, phosphite, substituted and unsubstituted metalloborane and mixtures thereof.

37. A basic ionic liquid according to claim 36, selected from a compound of formula:

wherein;

Bas and Z are as defined above.

38. A basic ionic liquid according to claim 36, selected from a compound of formula:

wherein;

X⁻

is as defined above.