|Publication number||US3708527 A|
|Publication date||Jan 2, 1973|
|Filing date||Feb 10, 1970|
|Priority date||Feb 26, 1969|
|Also published as||DE2007428A1|
|Publication number||US 3708527 A, US 3708527A, US-A-3708527, US3708527 A, US3708527A|
|Inventors||F Casagrande, M Duennenberger, M Schellenbaum|
|Original Assignee||Ciba Geigy Ag|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (4), Classifications (26)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,708,527 QUATERNARY AMMONIUM ARYL CARBOXYLIC ACID SALTS Max Duennenberger, Frenkendorf, Max Schellenbaum Muttenz, and Fulvio Casagrande, Binningen, Switzerland, assignors to Ciba-Geigy AG, Basel, Switzerland N0 Drawing. Filed Feb. 10, 1970, Ser. No. 10,308 Claims priority, applicagog7S/v6vitzerland, Feb. 26, 1969,
Int. Cl: C07c 87/30 US. Cl. 260-50115 Claims ABSTRACT OF THE DISCLOSURE Quaternary ammonium compounds are provided which correspond to the formula in which A is an organic residue, X is a --CO-, SO or SO group, R is an aliphatic residue, R is a benzene residue, R and R each is a divalent aliphatic residue and n is 1 or 2. These compounds are used for combatting harmful micro-organisms, such as bacteria and fungi. They are especially used for the antimicrobial finishing and/or protection of organic material more particularly of textiles, againstmicro-organisms.
The subject of the invention are quaternary ammonium compounds of formula wherein A denotes an organic residue bonded to X by a carbon atom, X denotes a OO', SO or SO group, R denotes a higher molecular aliphatic residue, R denotes a monocyclic benzene residue, R and R each denote a short-chain divalent aliphatic residue and n denotes an integer-having a value of at most 2.
In particular, quaternary ammonium compounds of are of interest wherein A denotes an at most bicyclic aromatic residue, a monocyclic heterocyclic residue, a monocyclic cyloaliphatic residue, a monocyclic araliphatic residue or an aliphatic residue and R R R R X and n have the indicated significance.
Preferred quaternary ammonium compounds correspond to the formula (3) V liar-OH H: RrcHr-N lh] [GOX]] A,
3,708,527 Patented Jan. 2, 1973 are particularly suitable, wherein A denotes an optionally substituted phenyl, diphenyl, furyl or thienyl residue bonded to X by a ring carbon atom, or an optionally substituted phenylalkyl, alkyl, alkenyl, phenylpolyglycol or thiodialkyl residue, and R R R 11,, X and n have the indicated significance.
The substituents of A, A A or A can for example be halogen atoms, alkyl residues or alkoxy residues. Cycloaliphatic residues A preferably contain 3 to 5 ring members, Aliphatic residues A or A are appropriately built up from carbon chains which can also be interrupted by oxygen or sulphur atoms.
Here quaternary ammonium compounds of formula are of particular interest, wherein Y denotes a hydrogen atom, a halogen atom, an alkyl group with at most 4 carbon atoms, an alkoxy group with at most 2 carbon atoms, a hydroxyl group or a monocyclic benzene residue, Y and Y each denote a hydrogen atom, a halogen atom or an alkyl group with at most 4 carbon atoms, and X, R R R and R have the indicated significance. Where Y Y or Y represent halogen atoms, there are preferably chlorine atoms.
Possible alkyl groups for Y Y and Y are both straight-chain and branched residues, for example methyl, ethyl, n-propyl, isopropyl,n-butyl, and tert. butyl residues. Y is preferably in the para-position to X.
Amonst these quaternary ammonium compounds, those of formula Ilia-4) H [RrCHr-If m] ox- R-r-QH wherein R R R R X, Y and Y have the indicated significance, are preferred.
Other preferred quaternary ammonium compounds are derived from carboxylic acids and correspond to the formula wherein A, X, R R R R and n have the indicated significance.
Quaternary ammonium compounds of formula wherein r denotes an integer having a value of at most 3 and R R X, A and n have the indicated significance, are also of particular interest.
Quaternary ammonium compounds of formula wherein R denotes an alkyl residue containing 8 to 22, preferably 10 to 18, carbon atoms and R A, X and n have the indicated significance, are also particularly suitable.
3 4 Here quaternary ammonium compounds of formula (14) (10) CHZCHZOH CHzCHzOH [[R6CH2I|\I@R5 :l[ -X-]:l A Q OH L6 CH 1 z- 2 a HZCHiOH n 5 (L ll O' X A wherein R denotes a benzene residue optionally sub- HflCHZOH stituted by halogen atoms or alkyl residues with 1 to 4 wherein A, X and n have the indicated significance are carbon atoms and R A, X and n have the indicated also particularly preferred. significance are of particular interest. Quaternary ammonium compounds of formula THzCHzOH Y1 G9 Cl1zN- cHi)-cHi 0-0 0- l 11 HzCHzOH Y2 Good results are achieved with quaternary ammonium compounds of formula (11) wherein Y and Y have the indicated significance have G (CH2CH20 )rH proved particularly valuable, such as for example the H: i :l[e A3 compound of formula (JIHzCHzO-X-H n THZCHQOH 69 4: H2N-/-C rn -oni 0-0 OCH3-] l: ll H3CH20H wherein G denotes a halogen atom, a hydrogen atom or THZCHZOH CH;
69 CH2 N-/CH2)CH3 O-CO] g 11 H2CH2OH or an alkyl group with at most 4 carbon atoms and R X, A in and r have the indicated significance. The compounds of Formulae 1 to 17 are new and can I-Iere quaternary ammonium compounds of formula be manufactured according to methods which are in themwherein G denotes a methyl group or a hydrogen or selves known, by reaction of (a) a compound of formula chlorine atom and R Y Y Y and r have the in- (18) as e dicated significance should be highlighted. [Q 0X-) n A] Coin ounds of formula p v wherein A, X and n have the indicated significance and (13) Q represents a cation, with b) a compound of formula G1 CHioH20H Y4 (19) RPOH h I, e CHz-N-Ri o-co- -E 1 Z wherein R R R and R have the indicated significance are particularly interesting, wherein Y; denotes a hydro- 70 and Z denotes a halogen atomgen, chlorine or bromine atom or a hydroxyl or methyl The compouflds of Formula? 18 19 are p p group, Y denotes a hydrogen, chlorine or bro i atom ately reacted with one another in equivalent amounts, that or a hydroxyl, methyl, methoxy, butyl or phenyl residue, 15 y Where 1 mol of a compound of Formula and R5 and G1 have the indicated i nifi n 18 is reacted with 1 mol of a compound of Formula 19,
and where ru=2, 1 mol of a compound of Formula 10 is reacted with 2 mols of a compound of Formula 19.
Of the compounds of Formula 10, the quaternary am- In manufacturing the compounds of Formula 1, organic, or advantageously aqueous, solutions at 20 to 80 C. are used. The end products are as a rule colourless crystals.
The reaction medium, as well as the cation Q and the anion Z of the starting products, must in each case be so chosen that either the salt [QZ] or the quaternary ammonium compound of Formula 1 separate out from the reaction mixture as an insoluble product and that either the quaternary ammonium compound or the salt [QZ] remains in solution. As a rule, the salt [QZ] precipitates and the compound of Formula 1 remains dissolved when working in an organic solvent as the reaction medium, and in the case of an aqueous reaction medium the compound of Formula 1 precipitates and the salt [QZ] remains in solution.
Preferably, the component (a) in the form of an alkali metal salt is reacted with a halide of the component (b). Possible halogen atoms are preferably chlorine or bromine atoms and alkali salts are above all sodium or potassium salts of the organic acids.
The compounds of Formulae 2 to 17 are manufactured by reacting (a) a compound of formula (20) o oat-X 4] or of formula or of formula 2 Y 3) 1 a Q9 o-X-- Y: or of formula or of formula wherein Q, A, A A A X, Y Y Y and n have the indicated significance, with (b) a compound of Formula 19 wherein R R R and R have the indicated significance and Z represents a halogen atom.
The monocyclic benzene residue of the starting compound of Formula 19 can be both substituted and unsubstituted. Halogen atoms or alkyl residues with 1 to 4 carbon atoms as substituents are preferred. R in Formulae 1 to 9, 19 or R in Formula 10 can thus for example represent a 4-chlorophenyl, 3,4-dichlorophenyl or 4-methylphenyl residue.
The compounds of Formulae 2 to 17 are accordingly manufactured by reaction of (a) a compound of Formula 18 or of Formulae 20 to 25 with (b) a compound of formula (26) (CH2CH10),H
R -CHzN R Z memo-Ln or of formula (27) CHZCHzOH Brent-Nita Z HzOHzOH or of formula (28) CH2GH2OH sCH2N- a Ze HzCHzOH or of formula or of formula wherein the residues R R R R G, G r and Z have the indicated significance.
When manufacturing compounds of Formula 1 one is thus always dealing with reactions of a quaternary ammonium salt With a salt of an acid. -In the case of the acids one is dealing with sulphonic acids, acid sulphuric acid esters or preferably carboxylic acids. Here both monobasic and dibasic acids can be used such as for example: acetic acid, chloracetic acid, trichloracetic acid, bromacetic acid, propionic acid, 2-chloropropionic acid, 3-chloropropionic acid, 2,2-dichloropropionic acid, 2,2-dimethylpropionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, heptylic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, acrylic acid, crotonic acid, vinylacetic acid, sorbic acid, undecylenic acid, oleic acid, linoleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, glycollic acid, thioglycollic acid, thiodiglycollic acid, methoxyacetic acid, malic acid, tartaric acid, pyruvic acid, 3,3'-thiodipropionic acid, cyanacetic acid, chlorocyanacetic acid, dichlorocyanacetic acid, lactic acid, cyclopropanecarboxylic acid, naphthenic acid, benzoic acid, 2-chlorobenzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, 3,4-dichlorobenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 4-tert.butylbenzoic acid, diphenyl-4-carboxylic acid, salicylic acid, 5'-chlorosalicylic acid, S-bromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, B-methylsalicylic acid, S-methylsalicylic acid, 4-methoxybenzoic acid, 2,4- dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, phenylacetic acid, cinnamic acid, mandelic acid, phenoxyacetic acid, 4-chlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, phthalic acid, isophthalic acid, terephthalic acid, diphenyl-4,4-dicarboxylic acid, thiophene-Z-carboxylic acid, furane-Z-carboxylic acid, nicotinic acid, thiophene-2,5-dicarboxylic acid, furane-2,5-dicarboxylic acid, benzenesulphonic acid, 0- or p-toluenesulphonic acid and sulphuric acid half-esters of alkoxyphenylpolyglycols.
A particularly surprising feature of the compounds of Formula 1 is the broad antibacterial range of action, which in some of these compounds extends both to gram-positive and also gram-negative bacteria. Here the absence of odour and of colour of the compound of Formula 1 is of particular value as regards technical use aspects.
The present invention also comprises the use of the compounds of Formula 1 in combating pests quite generally. The use of the antimicrobial compounds is possible on a very broad basis, especially for the protection of organic substrates against attack by destructive and pathogenic (also phytopathogenic) micro-organisms. The antimicrobial agents mentioned are accordingly suitable both for use as preservatives and for use as disinfectants for technical products of all kinds, in plant protection, in agriculture, in veterinary medicine and in cosmetics.
Amongst the non-textile technical products which can be preserved with the aid of the compounds of Formula 1, the following may be selected as examples: glues, adhesives, paints, textile aids or finishing agents, colour pastes and printing pastes and similar preparations based on organic and inorganic dyestuffs and pigments, including also those which contain casein or other organic compounds as admixtures. Wall paints and ceiling paints, for example those containing an albuminous colour binder, are also protected against attack by pests through an addition of the new compounds. The use for the protection of timber is also possible.
The compounds of Formula 1 can also be employed as preservatives in the cellulose and paper industry, inter alia for prevention of the known slime formation, caused by microorganisms, in equipment used for producing paper.
Further, detergents and cleaning agents having an excellent antibacterial or anti-mycotic action are obtained by combining the compounds of Formula 1 with surfaceactive substances especially with detergent substances. The compounds of Formula 1 can for example be incorporated into soaps or be combined with soap-free, detergent or otherwise surface-active substances, especially also non-ionic or cationic detergents, or can be combined together with mixtures of soaps and soap-free detergent substances, with their antimicrobial activity remaining fully preserved in these combinations. Using aqueous preparations of such detergent and cleansing agents which contain compounds of Formula 1 it is for example possible to impart an antimicrobial finish to textile materials on washing, since the active substance can be substantively absorbed on the textile material.
Cleansing agents which contain the compounds of the above-mentioned formula can also be employed in industry and in households, as well as in the foodstuff trade, for example dairies, breweries and abattoirs. The present compounds can also be used as a component of preparations which serve for the purpose of cleansing or disinfection.
The action of the compounds of Formula 1 can also be utilised in preservative and disinfectant finishes of plastics. When using plasticisers it is advantageous to add the antimicrobial additive, dissolved or dispersed in the plasticiser, to the plastic. It is desirable to ensure as uniform as possible a distribution in the plastic. The plastics with antimocrobial properties can be used for utensils of all kinds in which an activity against the most diverse germs, such as for example bacteria and fungi, is desired, as for example in doormats, bathroom curtains, lavatory seats, foot grids in swimming baths, wall coverings and the like. Floor and furniture polishes with a disinfectant action are obtained by incorporation into appropriate wax and polishing compositions.
The compounds of Formula 1 can furthermore be used for the preservative and disinfectant finishing of fibres and textiles, it being possible to apply them to natural and synthetic fibres, where they develop a long-lasting action against harmful (including pathogenic) micro-organisms, for example fungi and bacteria. Here the compounds can be added before, simultaneously with, or after a treatment of these textiles with other substances, for example dyestuffs or printing pastes, flameproofing agents, agents for softening the handle, and other finishes and the like.
Textiles treated in this way also show protection against the occurrence of perspiration odour, as is caused by microorganisms.
The antimicrobial active substances can be applied in the most diverse manner to the textile materials to be protected, for example by impregnation or spraying with solutions or suspensions which contain the abovementioned compounds as the active substance, or by successive impregnation r spraying with solutions of the starting compounds required for the manufacture of the active substances, with the active substance only being formed in situ on the material to be protected. Depending on the end use, the active substance content can be between 1 and 30 g. of active substance per litre of treatment liquid.
In most cases, textile materials of both synthetic or natural origin are adequately protected against fungal and bacterial attack by a content of 0.1 to 3% of active substance. The active substances mentioned can be employed together with other textile auxiliaries such as finishing agents, creaseproof finishes and the like.
The use forms of the active substances according to the invention can correspond to the usual formulations of pesticides; for example, agents which contain the said active substances can optionally also contain additives such as solvents, dispersing agents, Wetting agents or adhesives and the like, as well as other pesticides. In particular, the agents can however also contain a solid or liquid diluent or a solid or liquid carrier in addition to the active substance of Formula 1.
The parts indicated in the examples which follow are parts by weight, and the percentages are percentages by weight.
EXAMPLE 1 40 parts of benzyl-bis-(Z-hydroxyethyl)-dodecyl-ammonium chloride are dissolved in 70 parts of Water and added at 55 to 60 C. to a solution of 13.6 parts of ptoluic acid, 4 parts of sodium hydroxide and 50 parts of water. The mixture is stirred for a further hour at the same temperature and cooled to 10 C., whereupon the product of Formula 101 according to Table I precipitates in the form of colourless crystals. After recrystallising once from methanol-water, the product for analysis melts at 74 to 75 C.
EXAMPLE 2 A solution of 13.8 parts of salicylic acid in 50 parts by volume of methanol is mixed at 25 C., whilst stirring, firstly with 8.4 parts of sodium bicarbonate and then with 40.0 parts of benzyl-bis-(Z-hydroxyethyl)-dodecyl-ammonium chloride, after which the reaction mixture is boiled for minutes under refiux. The sodium chloride which has precipitated is filtered off and the filtrate evaporated in vacuo (12 mm. Hg).
The product of Formula 102 according to Table I is left as a viscous oil which crystallises on standing. The yield is about 46 parts. The product which has been purified by recrystallisation from ether or acetonitrile shows a melting point of 73 to 75 C.
EXAMPLE 3 A solution of 12.0 parts of 3-chlorobenzyl-di-(2-hydroxyethyl)-dodecyl-ammonium bromide in 25 parts of Water is added to 5.0 parts of diphenyl-4carboxylic acid and 1.4 parts of potassium hydroxide in 75 parts of water at C. over the course of 10 minutes. The reaction mixture is cooled to 5 C. and the product of Formula 130' according to Table II is filtered off, washed with water and dried. The yield is 14 parts; melting point to 108 C. The product which has been purified by recrystallisation from acetic acid ethyl ester melts at 110 to 111 C.
The compounds of Formula 103 to 142, Which correspond to the general formulae of Tables "I and II respectively are manufactured according to one of Examples 1 to 3.
TABLE II Significance of the symbols in Formula 33 Melting pom. U1 U3 Us in 7 in C:
H 01 H 12 1 110-111 01 H H 12 1 ins-122.5 0 H H 01 12 1 122.5-123 9 H H CH3 12 1 s3-s5 o H H H s 1 118-119 H H H 12 2 on H H H 12 3 on H H H 18 1 118-11 0 H H H s 1 87-88 & H H H 12 2 on 0 H H H 12 3 on H H H 13 1 94.5-96
EXAMPLE 4 TABLEContinued Determination of the minimum inhibitory concentration Minimuminmbitow (MIC) against bacteria and fungi in the gradient plate Bacteriostasis Fungistasis 1 2 test Formula Staphylococcus Escherichia Aspergillus Trichophyton The compounds of Formula 1 1n the sultable formula- No. harm coli 'aigcr mentagrophytcs tions (for example as solutions in dimethylsulphoxide) of 3 1O 100 10 a certain concentration are mixed with warm brain heart 10 10 10 10 infusion agar (bacteria) and mycophil-agar (fungi) re- -2 i8 18 i8 spectively. The liquid mixtures are cast onto a solidified 4 10 1o 10 wedge-shaped base agar layer and are also allowed to 5 i3 38 $8 solidify. 2. 5 10 so 10 The test organisms are now applied in a line at right ,3 3?, 8 angles to the gradient by means of a Pasteur pipette. 2 i 10 g After an incubation of 24 hours at 37 C. (bacteria) or g 3 38 1 72 hours at C. (fungi) respectively, the length of 2 2. g 5 g the germs which have grown on the inoculation smear are 6 60 20 10 measured and expressed in p.p.m. of active substance. 1 )0 198 fig 4.5 30 20 10 1 W. Szybaiski et 211., Science 116, 26 (1952). 1 100 100 10 Nuesch and Knfisel, Sideromycins, in the book by Gott- 2 5 20 6 lieb and Shaw, Antibiotics, Mechanism of Action, v01. 1
(1967), Springer Verlag. EXAMPLE 5 Minimum inhibitory concentration in p.p.m.
Samples of 100 g. of cotton cretonne are impregnated on a paddcr with a 1% strength solution of compounds Bacteriostasis Fungistasis of Formula 1 in isopropanol at 20 C. and subsequently Formula Staphylococcus Escherichia Aspergillus Trichophyton squeezed out to leave 100% liquor uptake. h mmmgmphyt Samples of 100 g. of wool cheviot are also treated in 3 i2 8 28 the same manner. 10 30 10 The fabrics dried at 30 to 40 C. contain 1% of active 2 i 6 g substance relative to their own weight. 25 25 6 50 To test the action against bacteria, 10 mm. diameter 5 5g 2 discs of the impregnated fabrics are placed, unsoaked and 3 15 10 8 after soaking for 24 hours at 29 C., on brain heart infug 32 2g 1g sion agar plates which are inoculated beforehand with 3 30 I 7 Staphylococcus aureus and Escherichia coli respectively. g-g i 2 55 The plates are thereafter incubated for 18 hours at 37 C. 1 20 5 6 The inhibitory zone (HZ in mm.) occurring around -3 i8 388 g8 the discs, On the one hand, and the microscopically detec- 4 10 10 able growth (W in percent) under and on the fabric on 4 10 the other, are assessed.
Substrate Unsoaked Soaked (with 1% of active Active HZ, HZ, W Microorganisms substance) substance mm. percent mm. percent 101 s 0 4 0 i8? a 2 s Staphylococcus ameas g g g 8 i8? 2 s 2 g 121 c o 1 o 101 6 o 0 0 i3? 2 s 2 s Escherichia coli g g 3 i8? 2 s s a 121 2 o 0 0 1 5 EXAMPLE 6 Fabric samples of 3 kg. each of cotton poplin and cotton frott are treated in a domestic washing machine, using a liquor ratio of 1:8, according to the following programme:
Containing 7% of a mixture of dioctadecyl dimethylammonium chloride and dihexadecyldimetllylammonium chloride.
Drying is carried out in a fully automatic drier at 80 C. for 90 minutes for cotton poplin and 60 minutes for cotton frott, respectively.
In order to test the finished fabrics for their action against bacteria, mm. diameter discs are placed on brain heart infusion agar plates which are inoculated beforehand with Staphylococcus aureus. The plates are thereafter incubated for 18 hours at 37 C.
The inhibition zone (HZ in mm.) arising around the discs, on the one hand, and the microscopically detectable growth (W in percent) under and on the fabric, on the other, are assessed.
The fabric finished by means of the combined treatment with laundry softening rinse agent and antimicrobial agent shows a good soft handle.
EXAMPLE 7 350 g. of 80% strength 3-(dimethylphosphono)-propionic acid methylolamide in 300 ml. of water, 80 g. of 60% strength pentamethylol-melamine-dimethyl-ether in 65 ml. of water and 20 g. of a 20% strength polyethylene emulsion in 40 ml. of water are mixed together.
Thereafter an aqueous Solution containing 30 g. of 85% strength phosphoric acid and 12.5 g. of the compound of Formula 101 is added to this bath. Finally, the entire solution is diluted with water to a volume of 1000 ml. A cotton fabric is padded in this bath on a Z-roll padder at 20 to C. to a liquor uptake of 80%. The
'fabric subsequently dried for minutes at 80 C. and
cured for 5 minutes at 160 C., then given a preliminary rinse with hot water and washed for 5 minutes with a solution of 1 g. of anhydrous sodium carbonate in one litre of water at 95 C., and then rinsed with water until free of alkali and dried.
In order to test the action against bacteria, 10 mm. diameter discs of the impregnated fabrics are laid on brain heart infusion agar plates which are beforehand inoculated with Staphylococcus aureus and Escherichia coli respectively. The plates are thereafter incubated for 18 hours at 37 C.
The assessment is carried out as indicated in Examples 5 and 6.
The fabric finished by the combined treatment with fiameproofing agent and antimicrobial agent shows very good fiameproof behaviour. The antimicrobial agent and the flameproofing agent do not mutually impair each others action.
Instead of the compound of Formula 101 it is also possible to use a compound of Formulae 102 to 142, whereby similar antimicrobial effects are achieved.
What is claimed is:
1. A quaternary ammonium compound of the formula a o-ooin which G is C -C alkyl, chloro or hydrogen,
R is alkyl containing 8 to 22 carbon atoms,
r is l, 2 or 3,
Y, is hydrogen or hydroXy,
Y is hydrogen, chloro, bromo, and
Y is alkyl of l to 4 carbon atoms, chloro, phenyl,
bromo, hydrogen, methoxy or ethoxy.
2. A quaternary ammonium compound according to claim 1 of the formula in which G is methyl, hydrogen or chloro,
R is alkyl containing 8 to 22 carbon atoms,
ris l, 2 or 3, and
Y Y and Y independently are hydrogen or alkyl with at most 4 carbon atoms.
3. A quaternary ammonium compound according to claim 1 in which r is one, G is hydrogen, and R is dodecanyl.
4. A quaternary ammonium compound according to claim 1 of the formula OH OHzOH HzCHzOH 5. A quaternary ammonium compound according to claim 1 of the formula H2CH2OH 1 CH3 -CHz-N CH CH3 9 HzCHzOH References Cited UNITED STATES PATENTS 1/1968 Wakeman et a1. 260-50115 8/1956 Chiddix et a1. 260-501.15
18 FOREIGN PATENTS 566,930 12/1958 Canada 260-567.6 M
BERNARD HELFIN, Primary Examiner M. W. GLYNN, Assistant Examiner Pw UNITED STATES PATENT OFFICE 569 CERTIFICATE OF CORRECTION Patent No. 3,7 ,5 7 Dated January 2, 973 inventor) MAX DUENNENBERGER ET AL I It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
7 Column 16, line 65, delete "G and insert G Signed arid sealed this Lth day of June 19714..
. EDWARD nmmwcimnmn. c. MARSHALL mm:
Attesting Officer v v Conmisaioner of Patents I
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|US20040167195 *||Jan 22, 2002||Aug 26, 2004||Rainer Muller||Microbicidal agent and composition for cosmetic treatment containing it|
|US20050136015 *||Dec 17, 2003||Jun 23, 2005||McKie Derrick B.||Topical use of halosalicylic acid derivatives|
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|U.S. Classification||562/493, 562/472, 510/518, 562/468, 562/474, 549/484, 562/475, 546/322, 562/506, 562/602, 562/473, 549/71, 558/27, 554/109, 562/469, 562/492|
|International Classification||C07C211/63, C07D307/68, A01N33/12, C07D333/38|
|Cooperative Classification||A01N33/12, C07D333/38, C07D307/68|
|European Classification||C07D333/38, A01N33/12, C07D307/68|