Method for synthesizing spiro quartenary ammonium systems

• US 20070049750A1
• Filed: 08/28/2006
• Published: 03/01/2007
• Est. Priority Date: 08/30/2005
• Status: Active Grant

• Current Assignee: Colleen Szuch, Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Siggel, Alfred, Poss, Andrew, Demel, Sonja, Nerenz, Frank, Palanisamy, Thirumalai
• Granted Patent: US 8,426,593 B2
• Time in Patent Office: Days
• US Class Current: 540/543
• CPC Class Codes: C07D 471/10 Spiro-condensed systems
• CPC Class Codes: C07D 487/10 Spiro-condensed systems
• CPC Class Codes: H01G 9/035 Liquid electrolytes, e.g. impregnating materials H01G11/54 takes precedence

Abstract

A method for preparing a spiro quaternary ammonium system and electrolytes containing spiro quaternary ammonium cations, comprising a synthesizing step wherein a spiro ammonium system is formed in a medium that can serve as both the reaction solvent and as an electrolyte solvent.

Claims

1-48. -48. (canceled)

49. A method of preparing a spiro quaternary ammonium system comprising reacting a nitrogen-containing compound in an electrolyte solvent under conditions effective to produce a spiro quaternary ammonium system.

50. A method of making a non-aqueous electrolyte comprising:

quaternizing a cyclic amine with an alkylating agent in an organic solvent and in the presence of a base to produce a solution comprising a spiro quaternary ammonium system in said solvent; and

optionally purifying the solution by removing at least a portion of precipitate formed during said quaternization.

51. The method of claim 50 further comprising:

adding a metal tetrafluoroborate or metal bis(trifluoromethylsulfonyl)imide to said solution or purified solution to produce a spiro quaternary ammonium tetrafluoroborate or bis(trifluoromethylsulfonyl)imide electrolyte; and

optionally purifying the electrolyte by removing at least a portion of precipitate formed via said addition.

52. The method of claim 51 wherein said adding and said quaternizing are performed concurrently.

53. The method of claim 51 wherein said addition and said quaternizing are performed consecutively.

54. The method of claim 51 wherein said removal of said precipitate formed via said quaternization reaction and said removal of said precipitate formed via said addition step are preformed concurrently.

55. The method of claim 51 wherein said Spiro quaternary ammonium system comprises the structure:

wherein X′ and

X″

are independently halogen or pseudohalogenides;

n is independent an integer from about 0 to about 6;

R₁ is independently CH₂, CHF, CF₂, CH, CF;

R₂ is CF, CH₂, CR₃, CHF, CF₂, CHR₃, CR₃R₃, NH, O, S, 3-8 member cyclic or heterocyclic, or a polycyclic or polyheterocyclic wherein each ring has 3 to 8 members;

R₃ is independently

(a) H;

(b) a C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₁-C₆ alkenyl group;

or

(c) heteroalkyl groups with a chain length of about 1 to about 6;

R₄ is CF, CH₂, CR₃, CHF, CF₂, CHR₃, CR₃R₃, NH, O, S, or a quaternary ammonium Spiro junction.

56. The method of claim 55 wherein said spiro quaternary ammonium system comprises at least one of 6-azoniaspiro[5.5]undecane, 5-azoniaspiro[4.5]undecane, 5-azoniaspiro[4.4]nonane, or a derivative thereof.

57. The method of claim 51 wherein said metal tetrafluoroborate is potassium tetrafluoroborate and said metal bis(trifluoromethylsulfonyl)imide is potassium bis(trifluoromethylsulfonyl)imide.

58. The method of claim 51 wherein said alkylating agent has the formula:

wherein X′ and

X″

are independently halogen or pseudohalogenides;

n is independent an integer from about 0 to about 6;

R₁ is independently CH₂, CHF, CF₂, CH, CF;

R₃ is independently

(a) H;

(b) a C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₁-C₆ alkenyl group;

or

(c) heteroalkyl groups with a chain length of about 1 to about 6; and

R₄ is CF, CH₂, CR₃, CHF, CF₂, CHR₃, CR₃R₃, NH, O, or S.

59. The method of claim 58 wherein said alkylating agent is selected from the group consisting of 1,4-dichlorobutane, 1,5-dichloropentane, 1,4-dibromobutane, 1,5-dibromopentane, 1,4-chlorobromobutane, 1,5-chlorobromopentane, 1,4-dichloropentane, 1,4-dibromopentane, 1-Bromo-4-chlorobutane, bis(2-bromoethyl) ether, 2-bromoethyl 2-chloroethyl ether, bis(2-chloroethyl) ether;

1-bromometyl 2-chloroethyl ether, 2-bromoethyl 1-chloromethyl ether, 1,4-ditosylbutane, 1,5-ditosylpentane, 1,4-ditosylbutane, 1,5-ditosylpentane, 1,4-bromotosylbutane, 1,5-tosylbromopentane, 1,4-ditosylpentane, 1,4-ditosylpentane, 1-bromo-4-tosylbutane, 1,4-dimesylbutane, 1,5-dimesylpentane, 1,4-dimesylbutane, 1,5-dimesylpentane, 1,4-bromomesylbutane, 1,5-mesylbromopentane, 1,4-dimesylpentane, 1,4-dimesylpentane, 1-bromo-4-mesylbutane, 1,4-ditriflylbutane, 1,5-ditriflylpentane, 1,4-ditriflylbutane, 1,5-ditriflylpentane, 1,4-bromotriflylbutane, 1,5-triflylbromopentane, 1,4-ditriflylpentane, 1,4-ditriflylpentane, and 1-bromo-4-triflylbutane.

60. The method of claim 51 wherein said cyclic amine comprises cyclic secondary amine moiety having the formula:

wherein n is independent an integer from about 0 to about 6;

R₁ is independently CH₂, CHF, CF₂, CH, CF;

R₂ is CF, CH₂, CR₃, CHF, CF₂, CHR₃, CR₃R₃, NH, O, S, 3 to 8 member cyclic or heterocyclic, or a polycyclic or polyheterocyclic wherein each ring has 3 to 8 members; and

R₃ is independently

(a) H;

(b) a C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₁-C₆ alkenyl group;

or

(c) heteroalkyl groups with a chain length of about 1 to about 6.

61. The method of claim 60 wherein said cyclic secondary amine is selected from the group consisting of pyrrolidine, morpholine, thiomorpholine, and piperidine, piperazine, imidazolidine, piperazine, imidazoline, oxadiazol, and pyrazolidine.

62. The method of claim 51 wherein said organic solvent is selected from the group consisting of nitriles, organic carbonates, lactones, sulfolanes, ketones, N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, and mixtures thereof.

63. The method of claim 62 wherein said nitrile is selected from the group consisting of acetonitrile, succinonitrile, glutaronitrile, propionitrile, phyenylacetonitrile, isobutylronitrile, benzonitrile, acrylonitrile, and mixtures thereof;

said organic carbonate is selected from the group consisting of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl 2,2,2-trifluoroethyl carbonate, and mixtures thereof;

said lactone is gamma-butryolactone; and

said ketone is selected from the group consisting of methylpropylketone and methylisobutylketone.

64. The method of claim 51 wherein said base is selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal hydrides and alkaline earth metal hydrides, alkali metal amides, alkali metal carbonates and alkaline earth metal carbonates, alkali metal hydrogen carbonates, basic metal oxidhydroxides, organometallic compounds, alkylmagnesium halides, and alkali metal alcoholates and alkaline earth metal alcoholates.

65. The method of claim 51 wherein said base has a formula selected from the group consisting of M_a(CO₃)_c, M_aH_b(CO₃)_c, M_a(PO₄)_c, M_aH_b(PO₄)_c, and M(OH)_c,

wherein M is an alkali or alkaline-earth metal,

a is an integer from about 1 to about 2,

b and c are independently an integer from 0 to about 2.

66. The method of claim 51 wherein said spiro quaternary ammonium system comprises the structure:

wherein X′ and

X″

are independently halogen or pseudohalogenides;

n is independent an integer from about 0 to about 6;

R₁ is independently CH₂, CHF, CF₂, CH, CF;

R₂ is CF, CH₂, CR₃, CHF, CF₂, CHR₃, CR₃R₃, NH, O, S, 3-8 member cyclic or heterocyclic, or a polycyclic or polyheterocyclic wherein each ring has 3 to 8 members;

R₃ is independently

(d) H;

(e) a C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₁-C₆ alkenyl group;

or

(f) heteroalkyl groups with a chain length of about 1 to about 6;

R₄ is CF, CH₂, CR₃, CHF, CF₂, CHR₃, CR₃R₃, NH, O, or S; and

Y is an anion selected from the group consisting of tetrafluoroborate and bis(trifluoromethylsulfonyl)imide.

67. The method of claim 66 wherein

X′

and X″

are independently chlorine or bromine;

n is independent an integer from about 1 to about 2;

R₁ is CH₂;

R₂ is CH₂ or O;

R₃ is H; and

R₄ is CH₂.

68. The method of claim 51 wherein said electrolyte comprises a Spiro quaternary ammonium compound selected from the group consisting of 6-azoniaspiro[5.5]undecane tetrafluoroborate, 5-azoniaspiro[4.5]undecane tetrafluoroborate, 5-azoniaspiro[4.4]nonane tetrafluoroborate, 6-azoniaspiro[5.5]undecane bis(trifluoromethylsulfonyl)imide, 5-azoniaspiro[4.5]undecane bis(trifluoromethylsulfonyl)imide, and 5-azoniaspiro[4.4]nonane bis(trifluoromethylsulfonyl)imide.