Patented Oct. 28, 1941 2,260,967 UNITED STATES PATENT OFFICE COMPLEX QUATERNARY AMMONIUM SALT Herman A. Bruson, Philadelphia, Pa., assignor to The Resinous Products & Chemical Company, Philadelphia, Pa. No Drawing. Application December 10, 1938, Serial No. 244,923 14 Claims. (CI. 260-404) This invention relates to new quaternary ann plex nitrogenous condensate of the methylol monium salts derived from complex phenolic es forming phenolic body employed for the process, terbases, and is a continuation in part of copend as described above, the present invention is ap ing application Serial No. 240,009, filed on Novem plicable to any monocarboxylic or polycarboxylic ber 12, 1938 now Patent No. 2,218,739 issued Oc acid halide of the aliphatic, aromatic, allicyclic, tober 22, 1940. of heterocyclic series of the formula R(COX), According to this invention, new Substances wherein R is any organic radical, X is halogen, having useful properties are prepared by con-, and n is a small integer. densing any organic acyl halide with a com Typical acylating agents for the purpose are plex nitrogenous inter-condensation product of O acetyl chloride, chloracetyl chloride, propionyl a methylol-forming phenol, formaldehyde, and chloride, isobutyryl chloride, caproyl chloride, 2- . a strongly basic, non-aromatic secondary amine ethylhexoyl chloride, dodecanoyl chloride, oleic to form an ester hydrohalide salt, and Subse acid chloride, palmitic acid chloride, stearoyl quently reacting upon the free ester base de chloride, crotonyl chloride, acrylyl chloride, rived therefrom, with an alkylating or aralkyl 5 methacrylyl chloride, undecenoyl chloride, naph ating agent capable of converting said ester base thenic acid chloride, ricinoleic acid chloride, into a quaternary ammonium salt. phenylacetyl chloride, tetrahydrofuroyl chloride, Nitrogenous phenolic inter-condensation prod linoleic acid chloride, octyloxyacetyl chloride, ucts of a methylol-forming phenol, formaldehyde, licanic acid chloride, cinnamoyl chloride benzoyl and a strongly basic, non-aromatic Secondary 20 chloride, p-nitrobenzoyl chloride, phenoxyacetyl amine of the kind used for the present purpose chloride, campholic acid chloride, abietic acid have been in part disclosed by the applicant in chloride, ox-bromstearoyl chloride, benzoyl-o-ben U. S. Patents Nos. 2,031,557, 2,033,092, 2,036,916, Zoyl chloride, the corresponding acid bromides 2,040,039, 2040,040, and 2,045,517. These may and homologues or substitution products there be oily, Crystalline or even resinous in nature. 25 of or their obvious equivalents. The compounds obtained directly by the reac Typical complex phenolic-formaldehyde-sec tion of organic acyl halides, and these phenolic . Ondary amine condensates which may be em nitrogenous inter-condensates are hydrohalide ployed include the resinous as well as non-resin salts of phenolic esters containing aliphatically ous tertiary nitrogenous condensation products bound tertiary amine groups. From these hy 30 of methylol-forming phenolic compounds with at drohalide salts, the free nitrogenous bases are least molecular equivalents each of formaldehyde obtained by neutralization of the hydrogen halide and of strongly basic, non-aromatic, secondary radical with alkali. These free bases, in turn, amines of the aliphatic, alicyclic, or heterocyclic combine with alkylating or aralkylating agents Series, including amines having from 2 to 18 car to form quaternary ammonium salts which are 35 bon atoms and upwards. Examples of suitable useful as Wetting, cleansing, emulsifying and dis amines are dimethylamine diethylamine, dibutyl persing agents that may be used in bleaching, amine, diamylamine, diallylamine, methyl-do dyeing, mordanting, mothproofing and surface decylamine, methyl-olleyl amine, dicyclohexyl treating fibrous materials, such as cotton, cellu amine, morpholine, piperidine, piperazine, pyr lose, rayon, Wool, silk, paper, feathers, hair and 40 rolidine, diethanolamine, triethylene tetramine, leather. Particularly valuable textile assistants and the like. are obtained when either the acyl halide em The phenols which are reacted with formalde ployed or the nitrogenous phenolic inter-conden hyde and the above amines to furnish the com Sate, or both, contain an aliphatic or alicyclic plex nitrogenous condensate, which is to be con hydrocarbon group of 8 to 18 carbon atoms in 45 densed with the acyl halide, are those aromatic clusive but the new compounds are not confined hydroxy compounds which are capable of form to these substituents. ing methylol derivatives with formaldehyde. When the phenol employed contains nuclear The phenols, in a broad way, belong to the class halogen, cyano, thio, thiocyano, nitro, sulfone, of hydroxy or polyhydroxy aromatic compounds alkoxy, aryloxy, or acylamino groups, particularly 50 of either monocyclic or polycyclic structure which valuable products are obtained which are toxic to contain at least one reactive nuclear position insects and lower forms of animal life, and ortho or para to the phenolic hydroxyl group. which may be employed as insecticidal, fungicidal, The phenols which meet these conditions and and bactericidal agents. are operable in this inter-condensation are termed With due regard to the character of the com "methylol-forming" phenols, 2 2,260,967 . Typical examples of such phenols are: phenol, t The following examples illustrate this inven a- or p-naphthol, o-, m-, p-cresol, xylenol (124, O . and 13,5), the various straight or branched chain alkyl phenols, such as propyl, iso-propyl-, butyl-, Eacample 1 amyl-, hexyl-, heptyl-, octyl-, nonyl-, undecyl-, To a solution of 94 g. of phenol in 125 g. of dodecyl-, tetradecyl-, hexadecyl-, oleyl-, octa 5 aqueous 36% commercial dimethylamine solu decyl-phenois; the cycloalkyl or aralkyl phenols, tion (1 mol) there is added dropwise 100 g. of such as cyclohexyl-, bornyl-, camphyl-, benzyl-, aqueous 30% formaldehyde solution (1 mol) or phenyl-phenols, as well as nuclear alkyl, cy with stirring and the reaction mixture main cloalkyl, aryl, aralkyl, hydroxyl, nitro, acyl, acyl tained at 30° C. by cooling. The mixture is amino, halogen, thio, sulfone, aryloxy or alkoxy 10 allowed to stand 24 hours at 25-30° C. and the derivatives thereof, including guaiacol, resorcinol, lower oil layer drawn off and washed several hydroquinone, pyrocatechol, pyrogallol, p-ben times with water. It is then distilled under re zoyl phenol, p-acetyl-aminophenol, o-, m-, p duced pressure and the fraction boiling at 97 chlorphenol, o-, m-, p-bromphenol, pp'-dihy 103 C./13 mm. collected. . It is a pale reddish droxydiphenyl dimethylmethane, p-hydroxy 5 oil containing 8.9% nitrogen by analysis. stearophenone, p-dodecanoylphenol, phenolic To a solution of 45.3 g. of this oil dissolved formaldehyde resins in the 'A' stage and other in 125 cc. of methyl ethyl ketone, there is added phenolic compounds Such as p,p'-dihydroxy dropwise with stirring and cooling to about 20° C. 60 g. of cocoanut oil mixed fatty acid chlo diphenyl sulfoxide, p,p'-dihydroxydiphenyl sul 20 rides (obtained by treating mixed fatty acids of fide, p,p'-dihydroxydiphenyl sulfone, hydroxy cocoanut oil with phosphorus trichloride). The anthracenes, hydroxyphenanthrenes, and the like. clear Solution obtained is then evaporated under The reaction between the acyl halide and the reduced pressure on a steam bath to remove complex nitrogenous condensation product of the solvent. The product obtained is a waxy formaldehyde, secondary amine, and the meth 25 mass which is the hydrochloride of the nitrog ylol-forming phenol may be carried out in the enous phenolic ester of mixed cocoanut oil fatty presence or absence of an inert Organic Solvent. acids. It is mixed with water and the phenolic The chief requirement of the process is that the ester base set free at 10-15° C. by the careful acyl halide and the inter-condensation product addition of aqueous 10% sodium hydroxide solu are mixed in such a way that the reaction be 30 tion till the solution is faintly pink to phenol tween them is controlled. The permissible rate phthalein indicator. The free phenolic ester of addition of one reactant to the other Will de base separates as a pale yellow oil containing pend upon the temperature as well as on the 4.14% nitrogen by analysis. It is soluble in nature of the particular reactants. In general, dilute lactic or acetic acids to give foamy, Soapy there is a wide range of temperatures at which 35 solutions. It is converted into quaternary am the reaction may be carried out, so long as no monium Salts as follows: appreciable amount of insoluble resinous mate (a) Twenty parts of the above free base of rial results. The proportion of acyl halide re the phenolic ester is heated with 7.6 parts of quired is at least one acyl halide group for each benzyl chloride at 90-95 C. for three hours. hydroxyl group to be esterified. As a result of 40 The product obtained is a viscous resin which, the reaction, a product is obtained which is the when dissolved in water, is capable of forming hydrohalide salt of a phenolic tertiary amine, insoluble precipitates with direct dyestuffs con the phenolic hydroxyl of which is esterified by taining sulfonic acid groups and may be used the acyl group. These complex ester salts are therefore for fixing dyestuffs to textile fibers. usually water-soluble compounds, the higher; al 45 It may also be used to give rayon a soft, Supple kylated members of which in aqueous solution feel, and for "animalizing' cotton or rayon fibers foam when shaken and show typical soap-like so that they will take the usual silk dyestuffs. properties. Upon neutralization with a strong (b) By using 10 parts of diethyl sulfate in alkali hydroxide, the salt-forming radical is re place of the benzyl chloride as in (a) above, moved and the free acylated complex phenolic 50 the corresponding quaternary ammonium sul bases are formed. These ester bases can, in the furic ester is obtained as a pale yellow oil. It case of the lower members, be distilled under dissolves in water to give a foamy solution useful reduced pressure without decomposition. The as a flotation agent. higher members are Water-insoluble oils or res In the above example the cocoanut oil mixed inous materials. The bases react to form qua 55 fatty acid chlorides may be replaced mol for mul ternary ammonium salts with agents for alkyla by stearic acid chloride, naphthenic acid chlo tion such as dialkyl sulfates (dimethyl sulfate, ride or oleic acid chloride to yield the corre diethyl sulfate), methylene halides such as sponding stearic, naphthenic, or oleic acid esters aralkyl halides (benzyl chloride, benzyl bromide), of the complex phenolic amine. These are pale and alphatic halides (methyl iodide, ethylene, 60 yellow oils which combine with benzyl chloride, dibromide, allyl bromide, methallyl chloride, methallyl chloride, or dimethylsulfate at 80-100' B,3'-dichloro-diethyl ether, ethylene bromhy C. to give water-soluble quaternary ammonium drine), organic esters (methyl thiocyanate, di salts having capillary-active properties. methyl oxalate, methyl formate, ethyl chlor Eacample 2 acetate) etc. Those quatenary ammonium salts 65 which are water-soluble are useful as bacter To a mixture consisting of 300 g. of p-tertiary cides, mothicides, textile softening agents, flota butylphenol and 396 g. of aqueous 25% dimethyl tion agent, dyestuff fixatives, corrosion inhibi amine solution in 150 cc. of ethanol, there is tors, and mordanting, emulsifying, creaseproof added dropwise, with stirring and cooling to ing, wetting, and cleansing agents, and are also 70 30-35° C., 220 g. of 30% formaldehyde solution. useful for "animalizing' cellulosic fibers so that After stirring for four hours and allowing to they may be dyed with silk or wool dyestuffs. stand for 18 hours at room temperature, the oil The higher members are useful for breaking cer layer is separated, washed and distilled under tain types of petroleum and other emulsions. 75 overreduced at 150-160°pressure. C./12The phenolicmm... as aamine pale yellowcomes 2,260,967 3 or colorless oil which, upon redistillation, bols uct was a thick, sticky resinous mass containing at 145-150° C./5 mm. and contains 6.4% nitro 7.6% nitrogen by analysis, gen by analysis. To a solution of 68.4 g of the above resin in (a) To a solution of 62.1 g. of this oil in 150 g. 200 cc. of benzene there was added gradually 16.5 of dry benzene there is added gradually, with g. of acetyl chloride while stirring the solution stirring, 53.5 g. of n-dodecanoyl chloride, at a and keeping the temperature below 40 C. The temperature of 30-40 C. After stirring for two acetic ester hydrochloride obtained was a Waters hours, the solution is neutralized in the Cold soluble resinous material. It was removed, dis with 10% sodium hydroxide solution, and the solved in water and the cooled solution treated benzene layer separated, washed, dried and O at 10-15 C, with 10% sodium hydroxide solution filtered. After removing the benzene by evapora until faintly pink to phenolphthalein indicator. tion under reduced pressure, the free basic The oil which separated was extracted with ether, phenolic ester of dodecanoic acid is obtained as washed, dried, and freed of solvent on a steam a pale yellow oil. bath. The product obtained was a viscous red (b) 34.9 g, of this ester is heated with 12.6 g. of dish oil containing 6.3% nitrogen by analysis, benzyl chloride for four hours at 90-95 C. The consisting essentially of a product having the quaternary ammonium salt obtained is a viscous formula: syrup having useful emulsifying properties. CHNCCH) (c) By using 42.2 g of benzoyl chloride in place of the dodecanoyl chloride in (a) above, 20 CH shih-ococh, the benzoic acid ester of the phenolic complex Yo amine is obtained as a crystalline product-boil ing at 179-184 C./3 mm. and melting at 89-90 C. (from petroleum ether). It combines with allyl bromide or benzyl bromide at 90° C. to give 25 11 g. of this diester ditertiary amine was mixed the corresponding quaternary ammonium bro with 6.55 g. of benzyl chloride and heated at mides as resinous masses. 70-75° C. for 6 hours. The quaternary am monium salt formed was a resinous solid which Eacample 3 was readily soluble in Water. The aqueous solu To a solution of 103 g. of p-a,c,y,-tetra 30 tion, when titrated with silver nitrate solution, methyl-butyl phenol (Jour. Amer. Chem. Soc. 55, showed ionic chloride to the extent of 10.3% in 2571 (1933)) in 100 cc. of 95% ethanol there was dicating that the essential component present added 50 g. of aqueous 30% of formaldehyde and was the di-quaternary ammonium salt having then while cooling to 30-40° C. and stirring 56 the formula: g. of aqueous 41% dimethylamine solution was 35 gradually added. The mixture was allowed to CBI-N(CH)c 9HCH, stand for 24 hours at room temperature. The lower oil layer was drawn off and allowed to crystallize in the cold. After recrystallization CHN still-o-coch, from 95% ethanol it formed colorless crystals, 40 of, cho-o-c OCH m. p. 69° C. having the formula: -NCCI) CECH (CH) C-CH-C en-K Ron The corresponding lauric acid di-ester quater CHN (CH) 45 nary ammonium salt, obtained by using lauroyl To a solution of 26.3 g. of this product in 80 chloride in place of the acetyl chloride in the cc. of benzene there is added gradually 7.8 g. of above example, is a Soapy solid useful for giving acetyl chloride while stirring and cooling to 10 cellulose a soft, Supple feel. For its preparation, C. In a short time the mixture sets to a Crystal 44 g. of lauric acid chloride is employed in place line paste of the acetyl ester hydrochloride, which 50 of the acetyl chloride. is filtered off. It dissolves in Water to give a Eacample 5 foamy, soapy solution. Such a solution, contain To a solution of 70 g. of 3-chloro-4-hydroxy ing 15 g. of the salt in 100 cc. of water, is neutral toluene, 100 cc. of methanol and 74 cc. of 30% ized in the cold with 10% sodium hydroxide Solu 55 formaldehyde Solution there is gradually added tion. The acetyl ester of the phenolic free base 148 cc. of 25% dimethylamine solution, while separates as an oil which, when shaken out with stirring and cooling to 20-25 C. After stirring ether, washed and distilled in vacuo boils at for several hours, the oil layer, is separated and 153-155° C./2 mm. It is a colorless oil. dried inder vacuum. It contains 6.98% nitrogen The quaternary ammonium salt is obtained by O by analysis corresponding to the formation of heating a mixture of 8.7 parts of this oil with 3.6 the compound: parts of benzyl chloride at 90-100° C. for several C hours. It is a colorless, hard, glassy maSS. Eacample 4. CB O 65 To a solution of 228 g. of pip'-(dihydroxy HN(CH) diphenyl)-dimethyl-methane, 400 cc. of metha A solution of 40 g. of the above phenolic base nol, and 204 cc. of aqueous 30% formaldehyde in 200 cc. of benzene is treated at 10-15 C. with solution there Was added gradually with stirring 16.5 g. of acetyl chloride. The ester hydrochlo and cooling to 25-30 C. 404 cc, of 25% aqueous 70 ride separates as a crystalline powder, m.p. i85 dimethylamine solution. Stirring was continued 191' C. A solution of 28 g. of this powder in for three hours and the mixture then allowed 200 cc. of water is neutralized in the cold with to stand for 18 hours at room temperature. The 10% sodium hydroxide solution. The free base oil layer was then separated, washed with water Separates as a reddish oil which is taken up in and dried in vacuo on the steam bath. The prod 75 ether, Washed and dried on a steam bath, 4. 2,260,967 10 g. of the above oil is mixed with 5.6 g. of reacting benzyl chloride and the lauric acid ester benzyl chloride and warmed at 70-75 C. for 8 of the complex nitrogenous condensation product hours. The product is a brown, brittle resin of phenol with at least one molecular equivalent which dissolves in Water. each of formaldehyde and dimethylamine. Eacample 6 5 8. A quaternary ammonium salt obtained by reacting benzyl chloride and the oleic acid ester To a solution of 26 g. of di- (morpholinoneth of the complex nitrogenous condensation product yl)-resorcinol (U. S. Patent No. 2,040,040) in 250 of phenol with at least one molecular equivalent cc. of methyl ethyl ketone there is added grad each of formaldehyde and dimethylamine. ually at 80° C. 11 g. of 2-ethyl butyryl chloride. O 9. A quaternary ammonium salt obtained by The whole precipitate is filtered off, washed with reacting an alkylating agent and a tertiary amine dry acetone and dried. It is dissolved in Water which is an Organic carboxylic acid ester of the and exactly neutralized with dilute Sodium hy Condensation product of a phenol with at least droxide. The crystalline ester base which sepa one molecular equivalent each of formaldehyde rates is removed and dried. Upon heating 5.5 g. 5 and a strongly basic, non-aromatic Secondary of this ester base with 3.5 g. of benzyl chloride amine. 0. for 10 hours at 70-75 C., a crumbly reddish solid 10. A quaternary ammonium salt obtained by is obtained which is moderately soluble in Water. reacting a methylene halide and a tertiary amine I claim: which is an organic carboxylic acid ester of the 1. Aquaternary ammonium salt of an organic 20 condensation product of a phenol with at least carboxylic acid ester of a nitrogenous phenolic one molecular equivalent each of formaldehyde condensation product obtained from a methylol and a strongly basic, non-aromatic secondary forming phenol With at least One molecular amine. equivalent each of formaldehyde and a strongly li. A quaternary ammonium salt obtained by basic, non-aromatic secondary amine. reacting an alkylating agent and a tertiary a 2. A quaternary ammonium salt of a fatty acid mine which is an organic carboxylic acid ester ester of a nitrogenous phenolic condensation of the condensation product of a phenol with at product obtained from a methylol-forming phen least one molecular equivalent each of formal ol with at least one molecular equivalent each dehyde and a strongly basic-non-aromatic sec of formaldehyde and a strongly basic, non-aro 30 Ondary amine. matic Secondary amine. 12. A process for producing a quaternary am 3. A quaternary ammonium salt of an organic monium Salt which comprises reacting an alkyl carboxylic acid ester of a complex nitrogenous ating agent and a tertiary amine which is an or condensation product obtained from a methylol ganic carboxylic acid ester of the condensation forming phenol with at least one molecular 35 product obtained from a phenol with at least equivalent each of formaldehyde and dimethyl one molecular equivalent each of formaldehyde anine. and a strongly basic, non-aromatic secondary 4. A quaternary ammonium salt of a fatty acid amine. ester of a complex nitrogenous condensation 13. A process for producing a quaternary am product obtained from a methylol-forming phen 40 monium Salt which comprises reacting a methyl ol with at least one molecular equivalent each of ene halide and a tertiary amine which is an or formaldehyde and dimethylamine. ganic carboxylic acid ester of the condensation 5. A quaternary ammonium salt of a higher product obtained from a phenol with at least one fatty acid ester of a complex nitrogenous con molecular equivalent of each formaldehyde and densation product obtained by reacting p,p'-(di a strongly basic, non-aromatic secondary amine. hydroxy diphenyl)-dimethyl methane with at 14. A process for producing a quaternary am least one molecular equivalent each of formalde monium salt which comprises reacting an alkyl hyde and dimethylamine. ating agent and a tertiary amine which is an 6. A quaternary ammonium salt of the lauric Organic carboxylic acid ester of the condensa acid ester of the complex nitrogenous condensa 50 tion product obtained from a phenol with at least tion product obtained by reacting phenol with at . One molecular equivalent of each formaldehyde least one molecular equivalent each of formaldie and a strongly basic, non-aromatic secondary hyde and dimethylamine. amine. 7. A quaternary ammonium salt obtained by HERMAN A. BRUSSN.