|Publication number||US2459062 A|
|Publication date||Jan 11, 1949|
|Filing date||Feb 8, 1944|
|Priority date||Feb 8, 1944|
|Publication number||US 2459062 A, US 2459062A, US-A-2459062, US2459062 A, US2459062A|
|Inventors||Cook Elmer W, Moss Philip H|
|Original Assignee||American Cyanamid Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (5), Referenced by (35), Classifications (6)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Patented Jan. 11, 1949 UNITED STATES PATENT OFFICE QUATERNARY AMMONIUM COMPOUNDS Elmer W. Cook, New York, N. Y., and Philip B. Moss, Greenwich, Conn., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application February 8, 1944,
Serial No. 521,588
The present invention is concerned with the production of new organic ammonium compounds which are adapted for various uses, more particularly as germicidal agents, wetting agents, and softening agents for textiles and the like.
These compounds are of the quaternary ammonium type which conform to the general formula The new products are in part crystalline, in-
part thickly liquid, viscous substances which in general dissolve readily in water and form stable aqueous solutions. In view of their dispersing and disinfecting properties, they exert a remarkable action as wetting and emulsifying agents and also as antiseptics. They are practically odorless and relatively non-toxic to man.
Representative compounds which fall within the scope of this invention are:
( CIHI 09H;
These quaternary ammonium salts may be prepared by treating a tertiary amine of the formulain whichR, R1 and R2 represent the molecular groups above referred to, with an alkylating agent such as an alkyl halide, dialkyl sulfate, aralkyl chloride, etc. Thus, -for example, 'ymyri'stamidopropyldimethylamine treated with benzyl chloride produces the ammonium salt, '1 myrlstamidopropyldimethylbenzylammonium chloride according to the reaction Reactions which may be involved in the preparation of the tertiary amine may be outlined as follows:
CH:=CHCN As an alternative method for step (3), the acid chloride,
Ri E-Cl may be used in place of the acid.
The invention is further illustrated by the following examples, the parts being by weight unless otherwise stated.
Example 1 Into 545 parts of a 25% aqueous solution of dimethyl amine, cooled with ice and water, there were added from a dropping funnel 170 parts of acrylonltrile. The rate of addition of the nitrile was controlled so that the temperature in the reaction vessel remained below 20 C. After the cold reaction mixture had stood for one hour, it
.vacuum distilled. 204.5 parts of N,N-dimethylpropylenediamine were collected, B. P. 134 C. at atmospheric pressure.
38 parts of myristyl chloride were added dropwise to a solution of 15.5 parts of N,N-dimethylpropylenediamine in 160 parts of benzene. After one hour of stirring, the benzene solution was washed with aqueous sodium hydroxide. The benzene layer was then washed once with water and the solvent removed by vacuum distillation. The residue was distilled at 208-215" C./1-2 mm, giving a solid distillate of y-myristamidopropyldimethylamine.
A solution of 6.2 parts of Y-myristamidopropyldimethylamine and 8.4 parts of benzyl chloride in 30 parts of benzene was refluxed during a period of four hours. The benzene was removed under vacuum, giving a light-colored, amorphous semi-solid at room temperature, which melts at about 54 C. to a clear, straw-colored liquid. This quaternary ammonium salt, 'y-myristamidopropyldimethylbenzylammonium chloride, is soluble in most organic solvents and forms a clear 25% solution in water.
This compound is an a excellent germicidal agent. It has been found effective against Staphylococcus aureus in a dilution of one part in 25,000 at 37 C. during a test of five minutes. The phenol coefficient of the compound is in the range of 277 to 333.
This product is also particularly suitable as a wetting agent for cotton fabrics.
Example II A mixture consisting of 30 parts of benzene. 8.1 parts of y-capyrylamidopropyldimethyiamine and 5 parts of benzyl chloride was heated at reflux temperature for six hours. After removing the benzene, the -caprylamidopropyldimethylbenzylammonium chloride was obtained as a viscous syrup.
Example II! Two parts of benzyl chloride were gradually added to a solution of 4.5 parts of 'y-palmitamidopropyldimethylamine dissolved in 30 parts of benzene. The resulting solution was refluxed for about four hours. The benzene was removed by vacuum distillation, leaving the quaternary ammonium salt, 1-palmitamidopropyidimethylbenzylammonium chloride, as an opaque solid, readily soluble in water. This product is an effective germicide, and also a good softening and wetting agent for textile fabrics.
Example IV A solution of 6.9 parts of y-lauramidopropyl.
dimethylamine and 4.5 parts of benzyl chloride in parts of benzene was refluxed during a period of four hours. After removing the solvent, the 'y-lauramidopropyldimethylbenzylammonium chloride was obtained as a colorless viscous mass, soluble in water. This product is a good germicide, and may be advantageously used for various disinfecting purposes.
Other quaternary ammonium salts can be prepared according to the procedure followed in the above examples, such as the 'y-myristamidopropyldimethyl a-naphthylmethylammonium chloride, 'y-oleamidopropyldimethylbenzylammonium chloride, -lauramidopropyldiethylmethylammonium bromide, 'y-stearamidopropyldimethylbenzylammonium chloride and 'y-myristamidopropyldimethylailyiammonium bromide.
The y-steararnidopropyldimethylbenzylammonium chloride is an excellent softening agent for rayon and cotton fibers, and acts as a permanent re-wetting agent on fabrics.
While the invention has been described with particular reference to specific embodiments, it is to be understood that it is not to be limited thereto but is to be construed broadly and restricted solely by the scope of the appended claims.
l. A germicidal composition containing as an effective germicidal agent the quaternary ammonium compound of the following formula 2. A germicidal composition containing as an eifective germicidal agent the quaternary ammonium compound of the following formula CH; CH:
3. A germicidal composition containing as an effective germicidal agent a compound of the formula OH; CH: R.CO.NH.CHQCHIOHJIf-CHIR1 CH: CH;
in wnich R. is an alkyl radical of 11-13 carbon atoms inclusive and Hal is a halogen.
5. A germicidal composition comprisinz, as an effective germicidal agent, an aqueous solution of a compound of the formula H2O CH:
11.0 O.NH.C HaQHiCHnI-C H 5 in which R is an alkyl radical of 11-13 carbon atoms.
ELMER W. COOK. PHILIP H. MOSS.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PA'I'ENTS Number" Name Date 1,860,563 Wayne May 31, 1932 1,737,458 ,Hartmann et al. Nov. 26, 1939 20 2,262,741 De Groote Nov. 11, 1941 2,345,570 Bley Apr. 4, 1944 2,362,760 Maxwell Nov. 14, 1944
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US1737458 *||Jul 19, 1928||Nov 26, 1929||Chem Ind Basel||Quaternary ammonium compound and process of making same|
|US1860563 *||May 21, 1931||May 31, 1932||Wayne Truman B||Method of resolving petroleum emulsions|
|US2262741 *||Oct 11, 1940||Nov 11, 1941||Petrolite Corp||Composition of matter and process for preventing water-in-oil type emulsions resulting from acidization of calcareous oil-bearing strata|
|US2345570 *||Oct 7, 1938||Apr 4, 1944||North American Rayon Corp||Coagulating bath containing cationactive inhibitors|
|US2362760 *||Jan 12, 1943||Nov 14, 1944||Shell Dev||Insecticidal compositions|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US2589674 *||May 24, 1947||Mar 18, 1952||American Cyanamid Co||Aliphatic amido propyl quaternary ammonium salts|
|US2644003 *||Feb 2, 1951||Jun 30, 1953||Geigy Ag J R||Quaternary ammonium compounds and their manufacture|
|US2737509 *||Nov 19, 1953||Mar 6, 1956||Jelling Murray||Carboxylic acid salts of n-dialkylaminoalkylamides|
|US2785092 *||Aug 2, 1954||Mar 12, 1957||Ciba Ltd||Condensation product and textile material softened therewith|
|US2862009 *||Feb 24, 1955||Nov 25, 1958||Ciba Ltd||New water soluble quaternary ammonium salts|
|US2950253 *||Jul 27, 1954||Aug 23, 1960||Bohme Fettchemie Gmbh||Methods of washing textile fabrics|
|US3060185 *||Apr 17, 1959||Oct 23, 1962||Ciba Geigy Corp||Hydroxamic acid esters of alkanolamines|
|US3082227 *||Sep 27, 1961||Mar 19, 1963||American Cyanamid Co||Method of preparing a quaternary ammonium compound|
|US3145137 *||May 12, 1961||Aug 18, 1964||Monsanto Co||Alkanoylamidoalkyleneamines and their quaternary ammonium salts as fungicides|
|US3260671 *||Nov 23, 1962||Jul 12, 1966||Emery Industries Inc||Amide oxidation inhibitor for lubricants|
|US3270039 *||Apr 10, 1963||Aug 30, 1966||Henkel & Cie Gmbh||Addition compounds of surface active sulfuric acid semiester salts and sulfobetainesand the production thereof|
|US3390158 *||Nov 30, 1964||Jun 25, 1968||Spofa Vereinigte Pharma Werke||Aromatic quaternary ammonium salts with disinfectant activity|
|US3410880 *||Oct 30, 1963||Nov 12, 1968||Procter & Gamble||N-trialkylammonium imides of higher fatty acids|
|US3492324 *||Sep 7, 1966||Jan 27, 1970||I C I Organics Inc||Quaternary salts of tertiary amines|
|US4012398 *||Sep 16, 1975||Mar 15, 1977||Van Dyk & Company, Incorporated||Quaternary halides of mink oil amides|
|US4168302 *||Mar 30, 1978||Sep 18, 1979||The Richardson Company||Hair conditioning compositions containing a non-irritating cationic surfactant|
|US4185098 *||Apr 13, 1977||Jan 22, 1980||Hoechst Aktiengesellschaft||Disinfectant|
|US4228042 *||Jun 26, 1978||Oct 14, 1980||The Procter & Gamble Company||Biodegradable cationic surface-active agents containing ester or amide and polyalkoxy group|
|US4239660 *||Dec 13, 1978||Dec 16, 1980||The Procter & Gamble Company||Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source|
|US4965362 *||Jul 6, 1989||Oct 23, 1990||Franz Merger||Joint preparation of 3-dialkylaminopropionitriles, bis-(2-cyanoethyl) ether and, if desired, ethylene-cyanohydrin|
|US5783604 *||Dec 10, 1996||Jul 21, 1998||Garcia Nunez; Maria Rosalia||Germicidal compositions containing iodine compounds|
|US8691899 *||Oct 9, 2007||Apr 8, 2014||Ethicon, Inc.||Antimicrobial polymer compositions and the use thereof|
|US20090092648 *||Oct 9, 2007||Apr 9, 2009||Ethicon, Inc.||Antimicrobial polymer compositions and the use thereof|
|CN101100432B||Jul 4, 2006||Aug 4, 2010||中国人民解放军军事医学科学院毒物药物研究所||Method for synthesizing benzyldimethyl[3-(myristamide)propyl]ammonium chloride|
|CN101820931B||Sep 29, 2008||Apr 2, 2014||伊西康公司||Antimicrobial polymer compositions and the use thereof|
|CN102869354A *||Feb 15, 2011||Jan 9, 2013||梅根医药股份有限公司||Pharmaceutical comprising myramistin|
|CN102869354B *||Feb 15, 2011||Dec 16, 2015||梅根医药股份有限公司||包含肉豆蔻酰氨基丙基二甲基苄基氯化铵的药物制剂|
|DE1031270B *||Jul 7, 1952||Jun 4, 1958||American Cyanamid Co||Verfahren zum Antistatischmachen von Gebilden aus Vinylharzen|
|DE102008039254A1 *||Aug 20, 2008||Feb 25, 2010||Megainpharm Gmbh||Medicament, useful e.g. for treating infectious- and purulent inflammatory diseases of e.g. eyes, comprises benzyl-dimethyl-(3-(myristoylamino)-propyl)-ammonium chloride, dimethyl-(3-(myristoylamino)-propyl)-amine oxide and solvent|
|EP0327379A2 *||Feb 3, 1989||Aug 9, 1989||CRODA INTERNATIONAL plc||Humectants|
|WO1993002042A1 *||Jul 16, 1992||Feb 4, 1993||Eastman Kodak Company||Amide-containing quaternary ammonium salts|
|WO2004108125A1 *||Jun 3, 2004||Dec 16, 2004||Megainpharm Gmbh||Coronavirus inactivating agent|
|WO2007075101A1 *||Dec 28, 2005||Jul 5, 2007||Obschestvo S Organichennoi Otvetstvennostyu Naucho-Proizvodstvennaya Firma 'flobi'||Method for determining concentration of c26h47cin2o in an aqueous medium|
|WO2011100994A1||Feb 19, 2010||Aug 25, 2011||Megainpharm Gmbh||Pharmaceutical comprising myramistin|
|WO2011101113A1||Feb 15, 2011||Aug 25, 2011||Megainpharm Gmbh||Pharmaceutical comprising myramistin|
|U.S. Classification||514/625, 530/221, 554/52|