US 2459088 A
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Patented Jan- 11, 1949 UNITED STATES FA ENT OFFICE ALIPHATIC A MIDE-SUB STITUTED PROPYL QUATERNARY AMMONIUM COMPOUNDS Philip H. Moss, Stamford, Conn., and Elmer W. Cook, New York, N. Y., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application May 24, 1947, Serial No. 750,368
3 Claims. 1
The present invention relates to new, organic ammonium compounds and relates more particularly to novel quaternary ammonium compounds which are suitable for useas wetting and detergent agents, germicides, fungicides, flotation agents, and the like uses.
The novel quaternary ammonium compounds of the invention are defined by the general formula:
wherein R is a member of the group consisting of aliphatic and alicyclic radicals containing at least '7 carbon atoms such as nonyl, undecyl, tridecyl, heptadecyl and the like radicals; R1 and R2 are members of the group consisting of alkyl and hydroxyalkyl radicals of 1-3 carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl, hydroxyethyl, dihydroxypropyl, and the like 1 radicals; R3 is an aralkyl radical such as benzyl,
wherein R, R1, R2, R2 and Y are substantially as defined above.
Our present invention is directed to improve.- ments in the class of compounds described in our earlier application and has for its principal object a modification therein which increases greatly the range of surface-active agents that can be prepared. We have found that a close adjustment of, the hydrophile-hydrophobe ratio can be obtained, while varying within wide limits the molecular weight of the radicals R and Rs in the above formula, by condensing eth lene oxide into the compounds in such a manne vthat the substitution occurs at the amide nitrogen atom.
By increasing the water-solubilizlng characteristics of the amido propyl-quaternary ammonium radical we are thusenabled to employ aliphatic or alicyclic radicals of substantially greater molecular weight in preparing our compounds.
The new compounds are for the most part thick liquids or amorphous solids having no definite melting points and which are soluble or dispersible in water and form stable aqueous solutions. The compounds are also readily soluble in the ordinary organic solvents such as ethanol, 7
acetone, dioxane, toluene and the like. Because of their excellent dispersing p1 operties they exert a remarkable action as wetting and emulsifying agents, and have also been found to be particularly suitable for rewetting uses, flotation agents, germicidal and fungicidal agents, and the Representative examples of the quaternary ammonium compounds embraced in the present invention are:
CH; (1) C11HIICON-C1HPNCHl 1 CHICOHI HsCHiOH Reaction product of 1 mol of gamme-stearamido ro ldlmeth lbenzylammonlum chloride and 1 mol of ethyfian zxlde y /CH: (2) Ci-IH C ON-CdI -N-CH;
- l CHICIOHI Reaction product of 1 mol of gamma-stearamido ro ldim th 1- gi iilliignaphthylmethylammonium chloride and 4 10 s h! etli yle ne CH|CH$OH (3) 0113150 ONC;Ht-N-CH:CH5OH (C1H4O):H Cl cHzct l Reaction product of 1 mol of gamma-lauramidopropyl-di(hydroxyethyl) amine and 2 mols of eth lene oxide a d net 1 mol of benzyl chloride y q naming with Reaction product oi 1 mol of amma-oaprylamido ro l-dimethl para-xylylammonium chloride and 4 mole of e thyg ne oxide The preferred method of preparing the novel quaternary ammonium salts of this invention may be expressed by the following equations and description:
( znloinu R;
where R1, R2, and n are as defined above.
(5) The.substituted amidopropylamines of (4) are then quaternarized by reaction thereof with the desired quaternarizing agents such as benzyl chloride, ethyl benzyl chloride, alpha naphthyl methyl chloride, para-methyl benzyl chloride, xylyl methyl chloride, etc.
If desired, the quaternarizing reaction may precede the ethylene oxide substitution reaction. In such cases, the amidopropylamine is reacted with the appropriate aralkyl halide, and thereafter the quaternary salt is made alkaline by adding excess sodium hydroxide or other alkali and is then reacted with 1-10 mols of ethylene oxide as in step (4) above. I
As noted above, R may be any aliphaticor alicyclic radical containing a sufficient number of carbon atoms to provide a hydrophobic radical which will produce orientation of the compounds at an oil-water interface. It is an advantage of the invention that a Wide variety of monocarboxylic acids may be used for this purpose such, for example, as caproic acid, decenoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid and other more highly unsaturated fatty acids of 14-18 carbon atoms obtained from vegetable and animal oil and fats such as soya bean oil, cottonseed oil, coconut oil, linseed oil, castor oil, dehydrated castor oil, and the like, or from other commercial sources such as talloil. Alicyclic monocarboxylic acids which may be used include abietic acid, petroleum naphthenic acid of 7-14 carbon atoms having boiling points within the range of 215-310 C., as described in Ellis, Chemistry of Petroleum Derivatives, (1934 edition) pages 1062-1085, and the like. It will be apparent that the number of carbon atoms contained by the aliphatic or alicyclic radicals is largely dependent on the purpose to which the quaternarized compound is to be put. Where compounds having good detergency and emulsifying properties are desired B may contain in excess of 20 carbon atoms. Where a high degree of wetting power is needed it is more desirable that R shall contain not more than about 19-20 carbon atoms and preferably about 11-17 carbon atoms.
The invention will be further illustrated by the Example 1 Into 545 gm. of a 25% aqueous solution of dimethylamine, cooled with ice and water, were added 170 gm. of acrylonltrile, the rate of addition of the nitrile being controlled so that the temperature in the reaction vessel remained below 20 C. After the cooled reaction mixture had stood for one hour, it was poured into 350 cc. of 10% aqueous sodium hydroxide solution, the oily layer collected and the aqueous layer extracted with ether. The extract and the oily layer were dried over sodium sulfate and distilled. 218 gm. of beta-dimethylaminopropionitrile were collected at 73-74 C. at 22 mm.
207 gm. of beta-dimethylaminoproprionitrile were hydrogenated in an autoclave under a pressure of about atmospheres at C. in the presence of 72.4 gm. of anhydrous ammonia, using Raney nickel as the catalyst. The product was dried over solid potassium hydroxide and vacuum distilled. There were collected 204.5 gm. of gamma-dimethylaminopropylamine having a boiling point of 134 C. at atmospheric pressure.
49 gm. of stearyl chloride were added drop-wise to a solution of 15.5 gm. of gamma-dimethylaminopropylamine in gm. of benzene. After one hour of stirring, the benzene solution was washed with 10% aqueous sodium hydroxide. The benzene layer was then washed with water and the solvent was removed by vacuum distillation. The residue was distilled at 208-2l5 C. at 1 to 2 mm. giving a solid distillate of gammastearamidopropyldimethylamine.
0.4 mol of gamma-stearamidopropyldimethylamine was reacted with ethylene oxide in the presence of 0.93 gm. of sodium hydroxide in tbutanol at a temperature of about 65 C. Following this operation, the alkali was neutralized by the addition of 1.9 cc. of 38% hydrochloric acid. The N-(hydroxy ethyl) stearamidopropyldimethylamine was quaternarized by reaction with 51 gm. (0.4 mol) of benzyl chloride at about 75 C. for 2 hours. The solution was then filtered and the solvent removed by vacuum distillation. The product:
O :CHaOH was a crystalline solid at room temperature having no odor of benzyl chloride. It was soluble in water or carbonate solution indicating that quaternarization was essentially complete.
Example 2 filtered and the solvent removed by vacuum distillation. The product:
/OHI 011E350 N-O|H|NCH;
was a brown solid at room temperature, and was soluble in warm water, ethanol, toluene. acetone, and the like organic solvents.
Example 3 A mixture consisting of 30 parts of benzene, 8.1 parts of gamma-caprylamidopropyldimethylamine, and 5 parts of benzyl chloride was heated at reflux temperature for. 6 hours. After removing the benzene, the gamma-caprylamidopropyldimethyl benzyl-ammonium chloride was obtained as a viscous syrup. This material was thereafter dissolved in t-butanol containing about 2 parts of sodium hydroxide, and ethylene oxide was passed into the solution under reflux conditions. The reaction was carried out for 2.5 hours at a temperature of 70-80 0., after which the solvent was removed by vacuum distillation. Analyses indicated that 4 mols of ethylene oxide had reacted with each mol of the quaternary ammonium and that the product had the formula This product was readily soluble in water and had excellent wetting properties.
Example 4 Two parts of benzyl chloride were gradually added to a solution of 4.5 parts of gamma-palmitamidopropyldimethylamine dissolved in parts of benzene. The resulting solution was refluxed for about 4 hours. Thereafter the solution was adjusted to about 8.5-9 pH by the addition of sodium hydroxide. The quaternary ammonium salt was then reacted with ethylene oxide in an amount equal to 10 mols of ethylene oxide for each mol of the salt, at a temperature of 70-80 C. for 3 hours. Upon neutralization, filtering and removal of the solvent a product was obtained having the formula CHI This product was a brown solid at room temperature; it was soluble in warm water and the ordinary organic solvents, and had very good detergent and wetting properties, and was quite satisfactory as a germicidal agent.
Example 5 A solution of 6.9 parts of gamma-lauramidopropyldimethylamine and 4.5 parts of benzyl chloride in '75 parts of benzene was refluxed during a period of 4 hours. Thereafter the solvent was removed, the residue was dissolved in 100 parts of t-butanol containing 2 parts of NaOH. Ethylene oxide was passed into the solution over a period of 0.5 hour, and the reaction was continued for 2.5 hours at -75 C. The product OuHuOON-Olfle- OH| c omoa was a light tan solid, soluble in water, and had good germicidal properties.
Example 6 perature was maintained for about 6' hours.
After filtering. and removing the solvent, a product was obtained .having the formula The material was a brown solid which was readily soluble in water and had very good wetting and detergent properties.
What we' claim is: g
l. The quaternary ammonium compound having the formula ./OH: C17HuC ON-CgHo-N-o H3 1 CHCOHI C IOHlOH 2. The quaternary ammonium compound having the formula I 01 CH:
0 H81 0 0 N C rHc-N-O HI iH0)ioH. OHSCOHB 3. A quaternary ammonium compound having the general formula R1 R--C ON--C;He-NRg I IH40)1|H wherein R. is a member of the group consisting of aliphatic and alicyclic radicals containing from 7 to 17 carbon atoms. R1 and R2 are alkyl radicals of 1-3 carbon atoms. Re is an aralkyl radical, n is an integer of 140, and Y is halogen.
PHILIP H. MOSS. ELMER W. COOK.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,303,366 Katzman Dec. 1, 1942 2,329,406 Mauerberger Sept. 14. 1943 2,345,570 Bley Apr; 4, 1944 7 2,409,275 Harris Oct. 15, 1946