US3873583A - Quaternary ammonium compounds - Google Patents

Quaternary ammonium compounds Download PDF

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US3873583A
US3873583A US248714A US24871472A US3873583A US 3873583 A US3873583 A US 3873583A US 248714 A US248714 A US 248714A US 24871472 A US24871472 A US 24871472A US 3873583 A US3873583 A US 3873583A
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radical
acid
quaternary ammonium
ammonium compounds
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Klaus Walz
Klaus Gerlach
Max Schwarz
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/655—Compounds containing ammonium groups
    • D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups

Definitions

  • ABSTRACT Quaternary ammonium compounds of the formula N on R-CO-O-R1 - A 11 Claims, N0 Drawings 1 QUATERNARY AMMONIUM COMPOUNDS
  • the invention relates to quaternary ammonium compounds; more particularly it concerns quaternary ammonium compounds of the formula in which R represents a C,-,C -alkyl, C r,C- -alkenyl or opl tionally substituted cycloalkyl, aralkyl or aryl radical and R represents an alkylene radical with 2 4 carbon atoms,
  • R and R independently of one another denote a C,C,-alkyl or C,C -hydroxyalkyl group or together with the nitrogen atom form a S-membered to 7-membered heterocyclic ring which optionallyalso contains a further hetero-atom,
  • A represents a radical containing at least 2 isocyclic rings and X is an anion
  • the cyclohexyl, dimethylcyclohexyl, decahydronaphthyl and abietyl radical as aralkyl radicals, the benzyl, phenylpropyl, phenylheptadecyl, naphthylmethyl, phenoxymethyl, phenoxyethyl radical, ethylphenoxymethyl, hexylphenoxymethyl or nonylphenoxymethyl radical; as aryl radicals, the phenyl, chlorophenyl and naphthyl radical.
  • R 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2butylene and 1,4-butylene radical may be mentioned.
  • R and R may be mentioned as C -C,-alkyl and C,-C -hydroxyalkyl radicals the methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, Z-hydroxyethyl and 2-hydroxypropyl-( l) radical.
  • Possible heterocyclic rings which can be formed from R and R are especially the pyrrolidine, piperidine and morpholine ring.
  • Radicals containing at least 2 isocyclic rings which may be mentioned as examples of A are: optionally substituted naphthyl, tetrahydronaphthyl, diphenyl, cyclohexylphenyl, phenoxyphenyl, benzylphenyl, benzoylphcnyl, (benzyloxy-methyl)-phenyl and 4-[ Lphenylpropyl-(Z)l-phenyl radicals.
  • the position in which these radicals are linked to the --CH group is optional; it is preferably determined by the position at which the halogenomethyl group enters during the halogenomethylation reaction of the corresponding aromatic hydrocarbons.
  • substituents of the radical A are lower alkyl radicals, such as the methyl, ethyl, iso-propyl or tert. butyl group, also halogen atoms, such as the chlorine or bromine atom, lower C -C groups, such as the methoxy group, nitro groups or the radical of the formula R I2 -CH I ⁇ ;l-R -O-CO-R X in which R, R R and R and X have the abovementioned meaning.
  • Possible anions X are anions of both inorganic and organic acids; preferred anions are the anions of the known inorganic acids, such as hydrochloric acid, hydrobromic acid, hydriodic acid, sulphuric acid, nitric acid, phosphoric acid or perchloric acid; also the anions of organic acids, such as of the lower aliphatic carboxylic acids, for example formic acid or acetic acid, of the aromatic sulphonic acids, such as of benzenesulphonic acid and toluenesulphonic acid, and ofthe halfesters of sulphuric acid, such as methylsulphuric acid and ethylsulphuric acid.
  • the known inorganic acids such as hydrochloric acid, hydrobromic acid, hydriodic acid, sulphuric acid, nitric acid, phosphoric acid or perchloric acid
  • organic acids such as of the lower aliphatic carboxylic acids, for example formic acid or acetic acid
  • Preferred ammonium compounds of the formula (l) are those in which I R represents a C,,-C -alkyl or C -C -alkenyl radical and R represents the l,2-ethylene radical,
  • R and R denote a methyl or ethyl group or together with the nitrogen atom form a pyrrolidine, piperidine or morpholine ring and A represents an optionally substituted naphthyl, tetrahydronaphthyl, diphenyl, phenoxyphenyl, benzylphenyl or cyclohexylphenyl radical.
  • R and R represent the methyl group and A represents a naphthyl or phenoxyphenyl radical which is optionally substituted, preferably optionally substituted by the radical
  • the quaternary ammonium compounds according to the invention are preferably manufactured by reaction of basic carboxylic acid esters of the formula R-CO-O-R in which A has the abovementioned meaning and X represents chlorine or bromine and n represents The reaction is preferably carried out at temperatures of between 30 and 150C in the presence of organic solvents which are inert towards ester groups, such as acetone, diethyl ether, dioxane, tetrahydrofurane, tert.
  • quaternary ammonium compounds according to the invention are obtained, if necessary after distilling off the solvent, as watersoluble crystalline products and in some cases also as noncrystallising syrups or resins.
  • the carboxylic acid esters of the formula (II) can be manufactured in accordance with known processes from carboxylic acids or their derivatives and hydroxyalkylamines, preferably by reaction of lower alkyl esters of the carboxylic acids with hydroxyalkylamines.
  • the following esters of the formula (ll), for example, can be employed for the manufacture of the quaternary ammonium compounds according to the invention: ca-
  • prylic acid Z-dimethylaminoethyl ester 2- ethylhexanoic acid Z-dimethylaminoethyl ester, capric acid Z-diethylaminoethyl ester, lauric acid 2- dimethylaminoethyl ester, lauric acid 2-dimethylamino-isopropyl ester, lauric acid 3- dimethylamino-propyl ester, lauric acid 2- dilwtylamino-ethyl ester, myristic acid 2- dimcthylamino-ethyl ester, myristic acid 2- diethylamino-ethyl ester, myristic acid 2-( N- morpholino)-cthyl ester, palmitic acid 2- dimethylaminocthyl ester, palmitic acid Z-dimethylamino-isopropyl ester, palmitic acid 3- diethylamino-propyl ester, palm
  • halogenomethylation products of the formula (III) can be manufactured in a manner which is in itself known, for example by reaction of compounds containing at least 2 isocyclic rings with formaldehyde and hydrochloric acid or hydrobromic acid.
  • Compounds of the formula (III) which are suitable for the manufacture of the quaternary ammonium compounds according to the invention are, for example: l-chloromethylnaphthalene, 2-chloromethyl-naphthalene,
  • l-bromomethylnaphthalene bis-chloromethylnaphthalene, Z-chloro-methyl-tetrahydronaphthalene, bis-chloromethyl-tetrahydronaphthalene, lchloromethyl-4-methyl-naphthalene, l-chloro-methyl- 4-chloronaphthalene, 4-chloromethyl-diphenyl-ether, 4-bromomethyl-diphenyl-ether, 4,4'-bis-chloromethyldiphenylether, chloromethyl-ditolyl-ether, bischloromethyl-ditolylether, chloromethylchlorodiphenyl-ether, chloromethylnitrodiphenylether, chloromethyl-dibenzyl-ether, bischloromethyldibenZyl-ether, 3-chloromethyl-2,4,6-trimethylbenzophenone, chloromethyl-biphenyl, bischloromethylbiphenyl, 4-chloromethylcycl
  • the quaternary ammonium compounds according to the invention, of the formula (I), can furthermore be manufactured by esterification of amines of the formula in which R,, R R;,, A and X have the abovementioned meaning, with carboxylic acids of the formula in which R has the abovementioned meaning, or their functional derivatives capable of ester formation, such as methyl esters, phenyl esters, acid amides, acid chlorides or acid anhydrides.
  • the compounds according to the invention are surfaceactive products. They have proved particularly valuable as auxiliaries when dyeing, with cationic dyestuffs, fibre materials which can be dyed with cationic dyestuffs,
  • the dyeing of the fibre materials which can be dyed with cationic dyestuffs can be carried out in the customary manner, by introducing the material to be dyed into an aqueous dyeing liquor, warmed to about 50 60C, which contains the cationic dyestuff, compounds of the formula (I), added salts, such as sodium acetate or sodium sulphate, and also acids, such as acetic acid or formic acid, subsequently raising the temperature of the dyebath to about C over the course ofabout 30 minutes and then keeping the dyebath at this temperature until it is exhausted.
  • an aqueous dyeing liquor warmed to about 50 60C
  • added salts such as sodium acetate or sodium sulphate
  • acids such as acetic acid or formic acid
  • Possible cationic dyestuffs are dyestuffs of the most diverse classes of compounds, for example diphenyl- 5 methane, triphenylmethane and rhodamine dyestuffs, azo or anthraquinone dyestuffs containing onium groups, and also thiazine, oxazine, methine and azomethine dyestuffs such as are described, for example, in Ullmanns Encyclopadie der ischen Chemie (Ullmanns Encyclopedia of Industrial Chemistry), 3rd Edition, l970, Supplementary Volume, page 225.
  • the requisite amounts of the compounds of the formula (I) to be used according to the invention can be determined easily by preliminary experiments. In general, amounts of approx. 0.25 to 2.5% of these compounds, relative to the weight of the material to be dyed which has been introduced, are employed.
  • Possible fibre materials which can be dyed with cationic dyestuffs are, for example, those of anionically modified polyesters and polyamides, but especially those of'polyacrylonitrile or copolymers containing acrylonitrile.
  • Suitable copolymers containing acrylonitrile are, for example, copolymers of acrylonitrile with vinyl chloride, vinylidene chloride, vinyl acetate.
  • vinylbenzimidazole, vinylpyridine, vinylmethylpyridinc l and vinylpyrimidine provided the proportion of these co-monomers does not exceed 20 per cent by weight.
  • 0 11 -C2H4 ca CH3 CH2 0 CH -l I-CH CH -OCO-C H 15 0 x -C2H4- CH3 CH 4-Phenyl-benzy1- ca oso 16.
  • the compounds of the formula (I) display a considerably increased activity, so that it is possi- -CO-OCH CH oo C1 when dyeing with dyestuffs of high affinity, that is to say dyestuffs which are absorbed very rapidly, since in 5 that the compounds additionally impart a pleasant soft handle to the dyed materials.
  • EXAMPLE 2 65 g of palmitic acid Z-dimethylamino-ethyl ester are dissolved in 150 ml of acetone. The solution is mixed with 36 g of 2-chloromethyl-tetrahydronaphthalene and the whole is heated to the boil for 2 hours. After cooling, the reaction mixture is treated with ether and the reaction product which has precipitated is filtered off. The quaternary ammonium compound is obtained in the form of a white, water-soluble crystal powder. Melting point (after recrystallisation from methylene chloride/acetone): 160 162C.
  • EXAMPLE 3 71 g of stearic acid Z-dimethylamino-ethyl ester are dissolved in 150 ml of tetrahydrofurane. The solution is slowly mixed with 43 g of monochloromethyldiphenyl-ether and the whole is stirred for 2.5 hours at 70 to 80C. After cooling, the reaction product which has precipitated is filtered off and rinsed with acetone. The quaternary ammonium compound is obtained in the form of water-soluble, white crystals which after recrystallisation from methylene chloride/acetone sinter at 65C and meltat 152 153C.
  • EXAMPLE 4 54 g of lauric acid 2-dimethylamino-ethyl ester are .dissolved in 90 ml of tetrahydrofurane. The solution is slowly mixed with 35 g of l-chloromethy1-naphthalene and the whole is stirred for 3 hours at 70 80C. The reaction product is precipitated as a pasty mass by adding ether to the reaction mixture, and the supernatant solvent is separated off by decantation. The residue crystallises after brief standing. The crystal paste is filtered off and recrystalised from acetone. The quaternary ammonium compound is obtained in the form of a white, water-soluble powder. Melting point: 90 92C.
  • EXAMPLE 6 71 g of oleic acid 2-dimethylamino-ethyl ester are dissolved in 100 ml of tetrahydrofurane. The solution is mixed with 35 g of 1-chloromethyl-naphthalene and the whole is stirred for 3 hours at 70 80C. Thereafter the solvent is distilled off in vacuo. The reaction product is left in almost quantitative yield as a clear, watersoluble, yellowbrown resin.
  • EXAMPLE 7 Yarns of polyacrylonitrile fibres are introduced, in a liquor ratio of 1:40, into a bath warmed to C which per litre contains 0.125 g of a cationic dyestuff (Colour Index No. 51,005, Volume 3, 2nd Edition, 1956x0125 g of sodium acetate, 0.3 g of glacial acetic acid and 0.1 g of the compound of the formula )f a all CH CH OOC CH C H The bath is to 98C and kept for 60 minutes at this temperature. A uniform, brilliant blue dyeing is obtained. The dyed yarn is distinguished by a pleasant soft handle.
  • a cationic dyestuff Colour Index No. 51,005, Volume 3, 2nd Edition, 1956x0125 g of sodium acetate, 0.3 g of glacial acetic acid and 0.1 g of the compound of the formula
  • EXAMPLE 8 Yarns of polyacrylonitrile fibres are introduced, in a liquor ratio of 1:40, into a bath warmed to 80C which per litre contains 0.5 g of a cationic dyestuff of the formula (CH2)3 M011 0 gal,
  • R represents an alkylene radical with 2 to 4 carbon atoms
  • R, and R independently of one another denote a C,-C -alkyl or C,-C,-hydroxyalkyl group, or together with the nitrogen atom form a heterocyclic ring selected from the group consisting of pyrrolidine, piperidine and morpholine;
  • A represents a radical containing at least 2 isocyclic rings, selected from the group consisting of naphthyl, y-naphthyl, tetrahydronaphthyl, 'y-tetrahydronaphthyl, 4-methylnaphthyl, 4-chloronaphthyl,
  • R represents a C C ,-alky1 radical
  • R represents an alkylene radical with 2 to 4 carbon atoms
  • R, and R independently of one another denote a C,-
  • A represents a radical containing at least 2 isocyclic rings, selected from the group consisting of naphthyl, y-naphthyl, tetrahydronaphthyl, 'y-tetrahydronaphthyl, 4-methylnaphthyl, 4-chloronaphthyl, phenoxyphenyl, 4-y-phenoxyphenyl, tolyloxytolyl, y-tolyoxytolyl, chlorophenoxyphenyl, nitrophenoxyphenyl, (benzyloxy methyl)-phenyl, y-(benzyloxy-methyU-phenyl, 2,4,6-trimethyl-3- benzoylphenyl, diphenyl, y-diphenyl, cyclohexylphenyl, benzylphenyl, and 4-[2-phenyl-propyl- (2)]-phenyl, wherein y is the radical [R-COO-R- N
  • X is an anion
  • R represents the ethylene radical
  • R and R denote a methyl or ethyl group or together with the nitrogen atom form a pyrrolidine, piperidine or morpholine ring;
  • A represents a tetrahydronaphthyl, diphenyl, phenoxyphenyl, benzylphenyl or cyclohexylphenyl radical.
  • R represents a C,,-C,,,-alkyl or C,,-C, -alkenyl radical
  • R represents the ethylene radical
  • R and R represents the methyl group
  • A represents a naphthyl or phenoxyphenyl radical.
  • R represents the ethylene radical
  • R and R represent the methyl group
  • A represents a naphthyl or phenoxyphenyl radical which is substituted by the radical [R- COOCH CH N(CH,,) -CH -1X, wherein R and X are as defined above.
  • R represents a C -alkyl radical
  • R represents the ethylene radical
  • R and R represents the methyl group
  • A represents a naphthyl radical
  • A represents a naphthyl radical which is substituted by the radical [RCOOCH CH -N(CH CH X, wherein R and X are as defined above.
  • R represents the ethylene radical
  • R and R represents the methyl group
  • A represents a phenoxyphenyl radical which is substituted by the radical [R-COOCH CH N(CH -CH X, wherein R and X are as defined above.

Abstract

Quaternary ammonium compounds of the formula

IN WHICH R, R1, R2, R3, A and X have the meaning given in the disclosure and a process for their preparation. The quaternary ammonium compounds are excellent dyeing auxiliaries in dyeing with cationic dyestuffs fibre materials which can be dyed with cationic dyestuffs.

Description

United States Patent [191 Walz et al.
[ Mar. 25, 1975 QUATERNARY AMMONIUM COMPOUNDS [75] Inventors: Klaus Walz, Leverkusen; Klaus Gerlach, Koeln; Max Schwarz, Bergisch-Neukirchen, all of Germany [73] Assignee: Bayer Aktiengesellschaft,
Leverkusen, Germany [22] Filed: Apr. 28, 1972 [21] Appl. No.: 248,714
[30] Foreign Application Priority Data Apr. 29, I971 Germany 2121013 [52] U.S. Cl 260/404, 8/169, 260/247.2, 260/293.65, 260/293.78, 260/326.3,
[51] Int. Cl. C07c 69/00 [58] Field of Search 260/404 [56] References Cited UNITED STATES PATENTS 2,004.476 (1/1935 Barz et al 260/404 2,670,360 2/1954 Lott 260/404 Primary Examiner-Lewis Gotts Assistant Examiner-Ethel G. Love Attorney, Agent, 0" Firm-Plumley & Tyner [57] ABSTRACT Quaternary ammonium compounds of the formula N on R-CO-O-R1 -=A 11 Claims, N0 Drawings 1 QUATERNARY AMMONIUM COMPOUNDS The invention relates to quaternary ammonium compounds; more particularly it concerns quaternary ammonium compounds of the formula in which R represents a C,-,C -alkyl, C r,C- -alkenyl or opl tionally substituted cycloalkyl, aralkyl or aryl radical and R represents an alkylene radical with 2 4 carbon atoms,
R and R independently of one another denote a C,C,-alkyl or C,C -hydroxyalkyl group or together with the nitrogen atom form a S-membered to 7-membered heterocyclic ring which optionallyalso contains a further hetero-atom,
A represents a radical containing at least 2 isocyclic rings and X is an anion,
a process for their manufacture, and their use as dyeing auxiliaries in dyeing with cationic dyestuffs fibre materials which can be dyed with cationic dyestuffs.
As examples of R there may be mentioned: as C -C alkyl radicals, the n-heptyl, l-ethyl-pentyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl and nonadecyl radical; as C =,C -alkylene radicals, the decenyl, pentadecenyl and heptadecenyl radical; as cycloalkyl radicals. the cyclohexyl, dimethylcyclohexyl, decahydronaphthyl and abietyl radical; as aralkyl radicals, the benzyl, phenylpropyl, phenylheptadecyl, naphthylmethyl, phenoxymethyl, phenoxyethyl radical, ethylphenoxymethyl, hexylphenoxymethyl or nonylphenoxymethyl radical; as aryl radicals, the phenyl, chlorophenyl and naphthyl radical.
As examples of R the 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2butylene and 1,4-butylene radical may be mentioned.
For R and R may be mentioned as C -C,-alkyl and C,-C -hydroxyalkyl radicals the methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, Z-hydroxyethyl and 2-hydroxypropyl-( l) radical.
Possible heterocyclic rings which can be formed from R and R are especially the pyrrolidine, piperidine and morpholine ring.
Radicals containing at least 2 isocyclic rings which may be mentioned as examples of A are: optionally substituted naphthyl, tetrahydronaphthyl, diphenyl, cyclohexylphenyl, phenoxyphenyl, benzylphenyl, benzoylphcnyl, (benzyloxy-methyl)-phenyl and 4-[ Lphenylpropyl-(Z)l-phenyl radicals. The position in which these radicals are linked to the --CH group is optional; it is preferably determined by the position at which the halogenomethyl group enters during the halogenomethylation reaction of the corresponding aromatic hydrocarbons.
Examples of substituents of the radical A are lower alkyl radicals, such as the methyl, ethyl, iso-propyl or tert. butyl group, also halogen atoms, such as the chlorine or bromine atom, lower C -C groups, such as the methoxy group, nitro groups or the radical of the formula R I2 -CH I\;l-R -O-CO-R X in which R, R R and R and X have the abovementioned meaning.
Possible anions X are anions of both inorganic and organic acids; preferred anions are the anions of the known inorganic acids, such as hydrochloric acid, hydrobromic acid, hydriodic acid, sulphuric acid, nitric acid, phosphoric acid or perchloric acid; also the anions of organic acids, such as of the lower aliphatic carboxylic acids, for example formic acid or acetic acid, of the aromatic sulphonic acids, such as of benzenesulphonic acid and toluenesulphonic acid, and ofthe halfesters of sulphuric acid, such as methylsulphuric acid and ethylsulphuric acid.
Preferred ammonium compounds of the formula (l) are those in which I R represents a C,,-C -alkyl or C -C -alkenyl radical and R represents the l,2-ethylene radical,
R and R denote a methyl or ethyl group or together with the nitrogen atom form a pyrrolidine, piperidine or morpholine ring and A represents an optionally substituted naphthyl, tetrahydronaphthyl, diphenyl, phenoxyphenyl, benzylphenyl or cyclohexylphenyl radical.
Amongst these compounds, in turn, particularly valuable ammonium compounds have provied to be those in which R represents a C C -alkyl or C -C alkenyI radical,
R and R represent the methyl group and A represents a naphthyl or phenoxyphenyl radical which is optionally substituted, preferably optionally substituted by the radical The quaternary ammonium compounds according to the invention are preferably manufactured by reaction of basic carboxylic acid esters of the formula R-CO-O-R in which A has the abovementioned meaning and X represents chlorine or bromine and n represents The reaction is preferably carried out at temperatures of between 30 and 150C in the presence of organic solvents which are inert towards ester groups, such as acetone, diethyl ether, dioxane, tetrahydrofurane, tert. butanol, formamide, dimethylformamide, dimethylsulphoxide, hydrocarbons or halogenated hydrocarbons. The quaternary ammonium compounds according to the invention are obtained, if necessary after distilling off the solvent, as watersoluble crystalline products and in some cases also as noncrystallising syrups or resins.
The carboxylic acid esters of the formula (II) can be manufactured in accordance with known processes from carboxylic acids or their derivatives and hydroxyalkylamines, preferably by reaction of lower alkyl esters of the carboxylic acids with hydroxyalkylamines. The following esters of the formula (ll), for example, can be employed for the manufacture of the quaternary ammonium compounds according to the invention: ca-
prylic acid Z-dimethylaminoethyl ester, 2- ethylhexanoic acid Z-dimethylaminoethyl ester, capric acid Z-diethylaminoethyl ester, lauric acid 2- dimethylaminoethyl ester, lauric acid 2-dimethylamino-isopropyl ester, lauric acid 3- dimethylamino-propyl ester, lauric acid 2- dilwtylamino-ethyl ester, myristic acid 2- dimcthylamino-ethyl ester, myristic acid 2- diethylamino-ethyl ester, myristic acid 2-( N- morpholino)-cthyl ester, palmitic acid 2- dimethylaminocthyl ester, palmitic acid Z-dimethylamino-isopropyl ester, palmitic acid 3- diethylamino-propyl ester, palmitic acid Z-(N- piperidyl)-ethyl ester, stearic acid Z-dimethylaminoethyl ester, stearic acid Z-diethylamino-ethyl ester, stearic acid 2-dimethylamino-isopropyl ester, stearic acid 3-dimethylamino-propyl ester, stearic acid 2- dibutylaminoethyl ester, stearic acid 2-(N- pyrrolidinyl)-ethyl ester, stearic acid Z-[bis-(B-hydroxypropyl)aminol-ethyl ester, arachidic acid 2- dimethylamino-ethyl ester, arachidic acid 2- diethylamino-ethyl ester, behenic acid 2- dimethylaminoethyl ester, undecylic acid 2- dimethylamino-ethyl ester, undecylenic acid 2- dibutylamino-ethyl ester, hexadecenoic acid 2- dimethylamino-ethyl ester, oleic acid 2- dimethylaminoethyl ester, linoleic acid Z-diethylaminoethyl ester, cyclohexanecarboxylic acid 3- diethylamino-propyl ester, dimethylcyclohexanoic acid Z-dibutylamino-ethyl ester, decahydronaphthalenecarboxylie acid 2-dimethylamino-ethyl ester, abietic acid 2-dimethylamino-ethyl ester, benzoic acid 2- dimethylamino-ethyl ester, naphthoic acid 2- dimethylaminoethyl ester, phenylacetic acid 2- dimethylamino-ethyl ester, phenoxyacetic acid 2- dibutylamino-ethyl ester and nonylphenoxyacetic acid Z-dimethylamino-ethyl ester.
The halogenomethylation products of the formula (III) can be manufactured in a manner which is in itself known, for example by reaction of compounds containing at least 2 isocyclic rings with formaldehyde and hydrochloric acid or hydrobromic acid. Compounds of the formula (III) which are suitable for the manufacture of the quaternary ammonium compounds according to the invention are, for example: l-chloromethylnaphthalene, 2-chloromethyl-naphthalene,
l-bromomethylnaphthalene, bis-chloromethylnaphthalene, Z-chloro-methyl-tetrahydronaphthalene, bis-chloromethyl-tetrahydronaphthalene, lchloromethyl-4-methyl-naphthalene, l-chloro-methyl- 4-chloronaphthalene, 4-chloromethyl-diphenyl-ether, 4-bromomethyl-diphenyl-ether, 4,4'-bis-chloromethyldiphenylether, chloromethyl-ditolyl-ether, bischloromethyl-ditolylether, chloromethylchlorodiphenyl-ether, chloromethylnitrodiphenylether, chloromethyl-dibenzyl-ether, bischloromethyldibenZyl-ether, 3-chloromethyl-2,4,6-trimethylbenzophenone, chloromethyl-biphenyl, bischloromethylbiphenyl, 4-chloromethylcyclohexylbenzene, chloromethyldiphenylmethane and chlorom'ethyl-2,2-diphenylpropane.
The quaternary ammonium compounds according to the invention, of the formula (I), can furthermore be manufactured by esterification of amines of the formula in which R,, R R;,, A and X have the abovementioned meaning, with carboxylic acids of the formula in which R has the abovementioned meaning, or their functional derivatives capable of ester formation, such as methyl esters, phenyl esters, acid amides, acid chlorides or acid anhydrides.
The compounds according to the invention are surfaceactive products. They have proved particularly valuable as auxiliaries when dyeing, with cationic dyestuffs, fibre materials which can be dyed with cationic dyestuffs,
The dyeing of the fibre materials which can be dyed with cationic dyestuffs can be carried out in the customary manner, by introducing the material to be dyed into an aqueous dyeing liquor, warmed to about 50 60C, which contains the cationic dyestuff, compounds of the formula (I), added salts, such as sodium acetate or sodium sulphate, and also acids, such as acetic acid or formic acid, subsequently raising the temperature of the dyebath to about C over the course ofabout 30 minutes and then keeping the dyebath at this temperature until it is exhausted. It is also possible to pre-treat the material to be dyed, at a temperature of 40 100C, with a liquor which contains the customary salts and acids as well as compounds of the formula (I), but as yet does not contain any dyestuff, to add the dyestuff only at this stage and to carry out the dyeing at 100C. Finally, it is also possible to introduce the material to be dyed directly into the dyebath, heated to about 100C, which contains compounds of the formula (I).
Possible cationic dyestuffs are dyestuffs of the most diverse classes of compounds, for example diphenyl- 5 methane, triphenylmethane and rhodamine dyestuffs, azo or anthraquinone dyestuffs containing onium groups, and also thiazine, oxazine, methine and azomethine dyestuffs such as are described, for example, in Ullmanns Encyclopadie der technischen Chemie (Ullmanns Encyclopedia of Industrial Chemistry), 3rd Edition, l970, Supplementary Volume, page 225.
The requisite amounts of the compounds of the formula (I) to be used according to the invention can be determined easily by preliminary experiments. In general, amounts of approx. 0.25 to 2.5% of these compounds, relative to the weight of the material to be dyed which has been introduced, are employed.
Possible fibre materials which can be dyed with cationic dyestuffs are, for example, those of anionically modified polyesters and polyamides, but especially those of'polyacrylonitrile or copolymers containing acrylonitrile.
Suitable copolymers containing acrylonitrile are, for example, copolymers of acrylonitrile with vinyl chloride, vinylidene chloride, vinyl acetate. vinyl chloroacetate, vinyl alcohol, acrylic and methacrylic acid, acrylic and methacrylic acid esters, allyl chloroacetate or basic vinyl compounds, such as vinylimidazole. vinylbenzimidazole, vinylpyridine, vinylmethylpyridinc l and vinylpyrimidine, provided the proportion of these co-monomers does not exceed 20 per cent by weight.
As examples of quaternary ammonium compounds suitable for the dyeing process, those compounds of the formula (I) in which R, R R R A-CH and X" have the meaning indicated in the table below may be mentioned.
. TABLE R R1 R2 R A-CH2- 7 x 1 0 11 -C2H4- ca CH5 NaphthyL-(D-methylc1 01' 2. 0 11 (1 11 CH3 CH5 n B1 5. 0 11 42 11 CH3 CH3 n I s. c a v 0 on CH3 M" I t (+)l 3 6. 0 11 -C2H4- CH3 CH -CH2- -o- ,-CH -1|i-CH CH 0-COC H C 7. 0 11 -c 1=1 CH3 CH5 Naphthyl-(l)-methylc1 8. 0 11 42 a,: CH5 CH 4-Chloronaphthyl-( 1) -methylc1 c1 9. 0 11 (12H4 C4119 C4119 Naphthyl (1) methyl Br- 10. 0 11 c 11 CH ctr l1. C H -C3H6- CH5 CH3 4-Cyclohexyl-benzyl C1 12 (1 11 --0 a CH3 CH 4-1-1 ejc h 1; hth 1-(1)-meth 1- v 01' 13. (1 11 -C2H4- CH3 CH3 4-Phenoxy-benzy1- c1 14. 0 11 -C2H4 ca CH3 CH2 0 CH -l I-CH CH -OCO-C H 15 0 x -C2H4- CH3 CH 4-Phenyl-benzy1- ca oso 16. 0 11 -c a cat on Naphthyl-(D-methyb CH-5- -so B 17 c a c 11 cn oa oa 011 03 H r 01 18. 0 11 c a CH2 (IJHOH on (II-10H CH5 CH3 I 19. 0 11 -c a{- ca cs 4-Chloronaphthy1-(l)-rnel:hylc1 20. (1 a q C2H4- CH3 CH Tetrahyd ronaphthyl-( 2 -methy1- C1 21. 0 11 -C2H4- CH.6 CH,5 4-Phenoxy-benzyl- C1 TAP LE Continued R R1 R2 R A-CH2- x (052KB 22. (2 11 -C2H4- on H3 -ca --o- -cH 1-ci1 ci1 oco-c r1 c1 23. 017F135 C2H4- CH3 CH3 4-Phenyl-benzyl C1- 24 c H -CH CH CH -cn c1 on or 5 H -I:lCH CH OCO-C H 25. 0 E -C H CH CH 4-Benzy1-benzy1- B1" on o CH 26. 0 a -C H c11 011 I 2 c1 CH 2'7. 0 x -C H CH3 CH Naphthy1-(l)-methylc1 28. C21H43 -C H CH cH 011 600 ,".wfi iimwigg ig L 3 V, .e "M GH QSO 3o. C H -C2H4- CH5 CH Naphthyl-(1)-methyl- -HSO4 31f. 0 E1 C H CH CH 4-Phenoxy-benzyl- 01 CH y 3 32. (2 L1 -C2H4- CH CH -CH -0- -CH -lT-CH CH -0-G0-C H (11 s H -CO-OCH -ca 0 H -CO-O-CH OH With the aid of the quaternary ammonium com- .pounds of the formula (1) according to the invention it is possible to dye fibre materials which in particular consist of polyacrylonitrile or copolymers containing acrylonitrile or containing such polymers or copolymers. these fibre materials being in the most diverse states of processing, for example as tows. top, flocks, filaments, yarns. woven fabrics or knitted fabrics, particularly uniformly and in deep shades.
Compared to the quaternary ammonium compounds usually employed in dyeing polyacrylonitrile with cationic dyestuffs. the compounds of the formula (I) display a considerably increased activity, so that it is possi- -CO-OCH CH oo C1 when dyeing with dyestuffs of high affinity, that is to say dyestuffs which are absorbed very rapidly, since in 5 that the compounds additionally impart a pleasant soft handle to the dyed materials.
EXAMPLE I 71 g of stearic acid Z-dimethylamino-cthyl ester, pre' pared by reacting stearic acid methyl ester with dimethylaminoethanol in the presence of titanium tetrabutylate, are dissolved in 150 ml of tetrahydrofurane. The solution is slowly mixed with 35 g of l-chloromethylnaphthalene and the whole is stirred for 2 hours at 70 80C. After cooling the reaction mixture, the precipitate is filtered off. The quaternary ammonium compound is obtained in almost quantitative yield in the form of a white, water-soluble crystal powder. After recrystallisation from methylene chloride/acetone, the compound sinters at 90C and melts at 140 142C.
EXAMPLE 2 65 g of palmitic acid Z-dimethylamino-ethyl ester are dissolved in 150 ml of acetone. The solution is mixed with 36 g of 2-chloromethyl-tetrahydronaphthalene and the whole is heated to the boil for 2 hours. After cooling, the reaction mixture is treated with ether and the reaction product which has precipitated is filtered off. The quaternary ammonium compound is obtained in the form of a white, water-soluble crystal powder. Melting point (after recrystallisation from methylene chloride/acetone): 160 162C.
EXAMPLE 3 71 g of stearic acid Z-dimethylamino-ethyl ester are dissolved in 150 ml of tetrahydrofurane. The solution is slowly mixed with 43 g of monochloromethyldiphenyl-ether and the whole is stirred for 2.5 hours at 70 to 80C. After cooling, the reaction product which has precipitated is filtered off and rinsed with acetone. The quaternary ammonium compound is obtained in the form of water-soluble, white crystals which after recrystallisation from methylene chloride/acetone sinter at 65C and meltat 152 153C.
EXAMPLE 4 EXAMPLE 5 54 g of lauric acid 2-dimethylamino-ethyl ester are .dissolved in 90 ml of tetrahydrofurane. The solution is slowly mixed with 35 g of l-chloromethy1-naphthalene and the whole is stirred for 3 hours at 70 80C. The reaction product is precipitated as a pasty mass by adding ether to the reaction mixture, and the supernatant solvent is separated off by decantation. The residue crystallises after brief standing. The crystal paste is filtered off and recrystalised from acetone. The quaternary ammonium compound is obtained in the form of a white, water-soluble powder. Melting point: 90 92C.
EXAMPLE 6 71 g of oleic acid 2-dimethylamino-ethyl ester are dissolved in 100 ml of tetrahydrofurane. The solution is mixed with 35 g of 1-chloromethyl-naphthalene and the whole is stirred for 3 hours at 70 80C. Thereafter the solvent is distilled off in vacuo. The reaction product is left in almost quantitative yield as a clear, watersoluble, yellowbrown resin.
EXAMPLE 7 Yarns of polyacrylonitrile fibres are introduced, in a liquor ratio of 1:40, into a bath warmed to C which per litre contains 0.125 g of a cationic dyestuff (Colour Index No. 51,005, Volume 3, 2nd Edition, 1956x0125 g of sodium acetate, 0.3 g of glacial acetic acid and 0.1 g of the compound of the formula )f a all CH CH OOC CH C H The bath is to 98C and kept for 60 minutes at this temperature. A uniform, brilliant blue dyeing is obtained. The dyed yarn is distinguished by a pleasant soft handle.
An equally uniform blue dyeing was obtained if instead of the abovementioned compound an equal amount of one of the compounds mentioned in the table under numbers 6,8,10,12,14,24, 27, 28, 21 and 22 was used.
EXAMPLE 8 Yarns of polyacrylonitrile fibres are introduced, in a liquor ratio of 1:40, into a bath warmed to 80C which per litre contains 0.5 g of a cationic dyestuff of the formula (CH2)3 M011 0 gal,
0.25 g of sodium acetate, 0.3 g of glacial acetic acid and 0.125 g of the compound of the formula 011 1 m it ca cn -ooc-c The temperature of the bath is brought to 98C and the yarns are treated at this temperature for 60 minutes. A blue dyeing of outstanding uniformity is obtained. The handle of the dyed yarn is pleasantly soft.
An equally level blue dyeing was obtained if instead of the compound mentioned the same amount of one of the compounds mentioned in the table under numbers 4,5, 11, 13,14, 15,18, 20, 23, 26, 31 and 32, or the compound was used.
EXAMPLE 9 Yarns of polyacrylonitrile fibres are introduced, in a liquor ratio of 1:40, into a bath warmed to 98C which per litre contains 0.2 g of a cationic dyestuff of the for- EXAMPLE 1O Yarns of polyacrylonitrile fibres are introduced, in a liquor ratio of 1:40, into a bath warmed to 80C which per litre contains 0.1 g of the cationic dyestuff described in Example 8 of British Patent Specification 973,259, 0.25 g of sodium acetate, 0.3 g of glacial acetic acid and 0.35 g of the compound of the formula i 3 11 co O-CH2CH2 If CH2 The bath is heated to 98C and kept at this temperature for 60 minutes. A uniform blue dyeing is obtained.
We claim: 1. Quaternary ammonium compound of the formula R co 0 R 2 Ill CH 3 in which R represents a C,-,-C ,-alky1 or -alkenyl radical;
R, represents an alkylene radical with 2 to 4 carbon atoms;
R, and R independently of one another denote a C,-C -alkyl or C,-C,-hydroxyalkyl group, or together with the nitrogen atom form a heterocyclic ring selected from the group consisting of pyrrolidine, piperidine and morpholine;
A represents a radical containing at least 2 isocyclic rings, selected from the group consisting of naphthyl, y-naphthyl, tetrahydronaphthyl, 'y-tetrahydronaphthyl, 4-methylnaphthyl, 4-chloronaphthyl,
phenoxyphenyl, 4-y-phenoxyphenyl, tolyloxytolyl;
chlorophenoxyphenyl, nitrophenoxyphenyl, (benzyloxymethyl)-phenyl, y-(benzyloxy-methyl)-phenyl, 2,4,6-trimethyl-3- benzoylphenyl, diphenyl, 'y-diphenyl, cyclohexylphenyl, benzylphenyl, and 4-[2-phenyl-propyl- (Zllphenyl, wherein y is the radical [R-COO-R- N(R (R )-CH ]X', wherein the Rs are as defined above; and X is an anion. 2. Quaternary ammonium compound of claim I having the formula y-tolyloxytolyl,
in which R represents a C C ,-alky1 radical;
R, represents an alkylene radical with 2 to 4 carbon atoms;
R, and R independently of one another denote a C,-
C,-a1kyl or C,-C,-hydroxyalkyl group, or together with the nitrogen atom form a heterocyclic ring selected from the group consistting of pyrrolidine, piperidine and morpholine;
A represents a radical containing at least 2 isocyclic rings, selected from the group consisting of naphthyl, y-naphthyl, tetrahydronaphthyl, 'y-tetrahydronaphthyl, 4-methylnaphthyl, 4-chloronaphthyl, phenoxyphenyl, 4-y-phenoxyphenyl, tolyloxytolyl, y-tolyoxytolyl, chlorophenoxyphenyl, nitrophenoxyphenyl, (benzyloxy methyl)-phenyl, y-(benzyloxy-methyU-phenyl, 2,4,6-trimethyl-3- benzoylphenyl, diphenyl, y-diphenyl, cyclohexylphenyl, benzylphenyl, and 4-[2-phenyl-propyl- (2)]-phenyl, wherein y is the radical [R-COO-R- N-(R (R )-CH -]X, wherein the Rs are as defined above; and
X is an anion.
3. Quaternary ammonium compounds according to claim 1, wherein R represents a C C ,-alkyl or C C ,-alkenyl radical;
R, represents the ethylene radical;
R and R denote a methyl or ethyl group or together with the nitrogen atom form a pyrrolidine, piperidine or morpholine ring; and
A represents a tetrahydronaphthyl, diphenyl, phenoxyphenyl, benzylphenyl or cyclohexylphenyl radical.
4. Quaternary ammonium compounds according to claim 1, wherein R represents a C,,-C,,,-alkyl or C,,-C, -alkenyl radical;
R, represents the ethylene radical;
R and R represents the methyl group; and
A represents a naphthyl or phenoxyphenyl radical.
5. Quaternary ammonium compounds according to claim 1, wherein R represents a C,,C, -a|kyl or C,,-C, -alkenyl radical;
R, represents the ethylene radical;
R and R represent the methyl group; and
A represents a naphthyl or phenoxyphenyl radical which is substituted by the radical [R- COOCH CH N(CH,,) -CH -1X, wherein R and X are as defined above.
6. Quaternary ammonium compounds according to claim 5, wherein A represents a naphthyl radical which is substituted by the radical [R-COO-CH CH N(CH -CH -]X', wherein R and X are as defined above.
7. Quaternary ammonium compounds according to claim 5, wherein A represents a phenoxyphenyl radical which is substituted by the radical [RCOO-CH CH N(CH;,
) CH X, wherein R and X are as defined above.
8. Compound according to claim 1 wherein R represents a C -alkyl radical; R represents the ethylene radical; R and R represents the methyl group; and A represents a naphthyl radical.
9. Compounds according to claim 8 wherein A represents a naphthyl radical which is substituted by the radical [RCOOCH CH -N(CH CH X, wherein R and X are as defined above.
10. Compounds according to claim 1 wherein R represents a C -alkyl radical;
R represents the ethylene radical;
R and R represents the methyl group; and
A represents a phenoxyphenyl radical which is substituted by the radical [R-COOCH CH N(CH -CH X, wherein R and X are as defined above.
11. Compound according to claim 1 having the for-

Claims (11)

1. QUATERNARY AMMONIUM COMPOUND OF THE FORMULA
2. Quaternary ammonium compound of claim 1 having the formula
3. Quaternary ammonium compounds according to claim 1, wherein R represents a C9-C21-alkyl or C9-C21-alkenyl radical; R1 represents the ethylene radical; R2 and R3 denote a methyl or ethyl group or together with the nitrogen atom form a pyrrolidine, piperidine or morpholine ring; and A represents a tetrahydronaphthyl, diphenyl, phenoxyphenyl, benzylphenyl or cyclohexylphenyl radical.
4. Quaternary ammonium compounds according to claim 1, wherein R represents a C11-C19-alkyl or C11-C19-alkenyl radical; R1 represents the ethylene radical; R2 and R3 represents the methyl group; and A represents a naphthyl or phenoxyphenyl radical.
5. Quaternary ammonium compounds according to claim 1, wherein R represents a C11-C19-alkyl or C11-C19-alkenyl radical; R1 represents the ethylene radical; R2 and R3 represent the methyl group; and A represents a naphthyl or phenoxyphenyl radical which is substituted by the radical (R-COO-CH2CH2-N(CH3)2-CH2-)X , wherein R and X are as defined above.
6. Quaternary ammonium compounds according to claim 5, wherein A represents a naphthyl radical which is substituted by the radical (R-COO-CH2CH2-N(CH3)2-CH2-)X , wherein R and X are as defined above.
7. Quaternary ammonium compounds according to claim 5, wherein A represents a phenoxyphenyl radical which is substituted by the radical (R-COO-CH2CH2-N(CH3)2-CH2-) X , wherein R and X are as defined above.
8. Compound according to claim 1 wherein R represents a C17-alkyl radical; R1 represents the ethylene radical; R2 and R3 represents the methyl group; and A represents a naphthyl radical.
9. Compounds according to claim 8 wherein A represents a naphthyl radical which is substituted by the radical (R-COO-CH2CH2-N(CH3)2-CH2-) X , wherein R and X are as defined above.
10. Compounds according to claim 1 wherein R represents a C17-alkyl radical; R1 represents the ethylene radical; R2 and R3 represents the methyl group; and A represents a phenoxyphenyl radical which is substituted by the radical (R-COO-CH2CH2-N(CH3)2-CH2-) X , wherein R and X are as defined above.
11. Compound according to claim 1 having the formula
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US4128485A (en) * 1976-08-16 1978-12-05 Colgate-Palmolive Company Fabric softening compounds
US4313889A (en) * 1975-09-22 1982-02-02 Merck & Co., Inc. Soft quaternary surface active agents
WO1983000086A1 (en) * 1981-07-06 1983-01-20 Univ Georgia Res Found Use of calmodulin binding drugs in uterus to prevent pregnancy
US4470995A (en) * 1982-07-14 1984-09-11 University Of Georgia Research Foundation, Inc. Use of 9-anthroylcholine as a vaginal contraceptive
US4497717A (en) * 1981-04-01 1985-02-05 The British Petroleum Company P.L.C. Compositions for use in oil recovery and method of use
US4727151A (en) * 1974-06-24 1988-02-23 Interx Research Corporation Labile quaternary ammonium salts as prodrugs
WO1988007569A1 (en) * 1987-03-25 1988-10-06 The Gillette Company Triglyceride quaternary ammonium compounds, their preparation anduse
US4797489A (en) * 1987-12-02 1989-01-10 American Home Products Corp. Adamantyl- and fluorenyl-arylpiperazines and -arylpiperidines
US4923642A (en) * 1986-11-14 1990-05-08 Henkel Kommanditgesellschaft Auf Aktien Quaternary ammonium compounds, their production and use in fabric aftertreatment preparations
US5110977A (en) * 1990-02-14 1992-05-05 Eastman Kodak Company Ester-containing quaternary ammonium salts as adhesion improving toner charge agents
US5741437A (en) * 1995-06-07 1998-04-21 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5792218A (en) * 1995-06-07 1998-08-11 The Clorox Company N-alkyl ammonium acetonitrile activators in dense gas cleaning and method
US5814242A (en) * 1995-06-07 1998-09-29 The Clorox Company Mixed peroxygen activator compositions
US5888419A (en) * 1995-06-07 1999-03-30 The Clorox Company Granular N-alkyl ammonium acetontrile compositions
US6046150A (en) * 1995-06-07 2000-04-04 The Clorox Company Liquid compositions containing N-alkyl ammonium acetonitrile salts
US6183665B1 (en) 1995-06-07 2001-02-06 The Clorox Company Granular N-alkyl ammonium acetonitrile compositions
US6235218B1 (en) 1995-06-07 2001-05-22 The Clorox Company Process for preparing N-alkyl ammonium acetonitrile compounds
US6764613B2 (en) 1995-06-07 2004-07-20 Mid-America Commercialization Corporation N-alkyl ammonium acetonitrile salts, methods therefor and compositions therewith

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US2670360A (en) * 1951-11-30 1954-02-23 Olin Mathieson Quaternary ammonium salts of basic derivatives of substituted cinnamic acids and methods of producing same

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Cited By (23)

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Publication number Priority date Publication date Assignee Title
US4727151A (en) * 1974-06-24 1988-02-23 Interx Research Corporation Labile quaternary ammonium salts as prodrugs
US4313889A (en) * 1975-09-22 1982-02-02 Merck & Co., Inc. Soft quaternary surface active agents
US4128485A (en) * 1976-08-16 1978-12-05 Colgate-Palmolive Company Fabric softening compounds
US4497717A (en) * 1981-04-01 1985-02-05 The British Petroleum Company P.L.C. Compositions for use in oil recovery and method of use
WO1983000086A1 (en) * 1981-07-06 1983-01-20 Univ Georgia Res Found Use of calmodulin binding drugs in uterus to prevent pregnancy
US4470995A (en) * 1982-07-14 1984-09-11 University Of Georgia Research Foundation, Inc. Use of 9-anthroylcholine as a vaginal contraceptive
US4923642A (en) * 1986-11-14 1990-05-08 Henkel Kommanditgesellschaft Auf Aktien Quaternary ammonium compounds, their production and use in fabric aftertreatment preparations
WO1988007569A1 (en) * 1987-03-25 1988-10-06 The Gillette Company Triglyceride quaternary ammonium compounds, their preparation anduse
US4857310A (en) * 1987-03-25 1989-08-15 The Gillette Company Triglyceride quaternary ammonium compounds, their preparation and use
US4797489A (en) * 1987-12-02 1989-01-10 American Home Products Corp. Adamantyl- and fluorenyl-arylpiperazines and -arylpiperidines
US5110977A (en) * 1990-02-14 1992-05-05 Eastman Kodak Company Ester-containing quaternary ammonium salts as adhesion improving toner charge agents
US5741437A (en) * 1995-06-07 1998-04-21 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5792218A (en) * 1995-06-07 1998-08-11 The Clorox Company N-alkyl ammonium acetonitrile activators in dense gas cleaning and method
US5814242A (en) * 1995-06-07 1998-09-29 The Clorox Company Mixed peroxygen activator compositions
US5877315A (en) * 1995-06-07 1999-03-02 The Clorox Company Dimeric N-Alkyl ammonium acetonitrile bleach activators
US5888419A (en) * 1995-06-07 1999-03-30 The Clorox Company Granular N-alkyl ammonium acetontrile compositions
US5959104A (en) * 1995-06-07 1999-09-28 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5958289A (en) * 1995-06-07 1999-09-28 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US6017464A (en) * 1995-06-07 2000-01-25 The Clorox Company Dimeric N-alkyl ammonium acetonitrile bleach activators
US6046150A (en) * 1995-06-07 2000-04-04 The Clorox Company Liquid compositions containing N-alkyl ammonium acetonitrile salts
US6183665B1 (en) 1995-06-07 2001-02-06 The Clorox Company Granular N-alkyl ammonium acetonitrile compositions
US6235218B1 (en) 1995-06-07 2001-05-22 The Clorox Company Process for preparing N-alkyl ammonium acetonitrile compounds
US6764613B2 (en) 1995-06-07 2004-07-20 Mid-America Commercialization Corporation N-alkyl ammonium acetonitrile salts, methods therefor and compositions therewith

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