UNITED STATES PATENT Office PRODUCT and Synthesis THEREOF John Carl Sauer, Wilmington, Del, Assignor to E

Patented July 13, 1943 2,323,938 UNITED STATES PATENT office PRODUCT AND syNTHESIs THEREOF John Carl Sauer, Wilmington, Del, assignor to E. I. du Pont de Nemours & Company, Wil mington, Del, a corporation of Delaware No Drawing. Application July 25, 1940, ... ." Serial No. 34,555 10 Claims. (Cl. 260-561) This invention relates to new compositions of kyl, cycloalkyl and open chain alkyl but may matter and more particularly to amides and contain inert groups such as carbalkoxy, alkoxy, their preparation. aryloxy, aralkoxy, keto, tertiary amide, halogen This application is a continuation-in-part of attached to aromatic carbon or aliphatic hetero my copending applications Serial Nos. 234,843 cyclic groups. R' may be hydrogen but, in view and 234,844, filed October 13, 1938. of the method of preparation of the acyl ethe Amides are of use as intermediates in a num nones, is preferably a monovalent organic radi ber of chemical syntheses, and certain long chain cal With the chemical inertness of R and prefer amides are excellent intermediates for the prep ably hydrocarbon. R may be the same as R' or aration of water repellents, textile finishing may be different. An especially preferred class agents, bactericides, and the like. Long chain, of ethenones is that wherein R and R' are open high molécular weight acids or related com chain alkyl. R. and R' must total at least nine pounds from which these amides could be formed and for one of the most important fields of use are limited definitely as to number and avail fulness, the waterproofing field, preferably total ability, particularly when a high molecular weight 5 at least twenty. ' is desired. - Amides are prepared from these acyl ethe This invention has as an object the prepara nones, in the preferred practice of the inven tion of new amides. A further object is the pro tion, by adding the...basic compound containing objectsvision of will a appearnew process hereinafter. for this purpose. Other hydrogen on ammonia type nitrogen to the acyl These objects are accomplished by the follow 20 ethenone of at least thirteen carbon atoms in an ing invention wherein an alpha, acyl ethenone inert-solvent therefor. Reaction generally pro having at least thirteen carbon atoms is reacted ceeds rapidly with the generation of some heat, with a basic compound having at least one hy and generally the amide precipitates from the drogen on ammonia type nitrogen. Solution from which it is filtered and is purified ... In the preferred practice of this invention beta 25 by recrystallization from a suitable solvent. In ketocarbonamides are prepared by adding anhy Some cases the resulting amida is soluble in the drous ammonia or anhydrous amines, bearing &t Solvent in which it is prepared. In these in least one amino hydrogen atom, to a solution, in stances the solvent is removed at low tempera an inert solvent, of an alpha acyl ethenone. The ture under diminished pressure and the resulting alpha acyl ethenone may be prepared, as dis amide is recrystallized from a suitable solvent. closed in my copending applications. Serial Nos. Since the acyl ethenones are usually prepared in 234,843 and 234,844 (now U. S. Patent 2,238,826) Solutions of 5 to 10 per cent concentration, these by the reaction of a tertiary amine, e. g., tri Solutions are generally used as such in the prepa ethylamine, and at least one primary acid halide, ration of the amides. The Solutions, however, 35 can be concentrated by removing the solvent at i. e., one containing the acid halide group low temperatures under reduced preSSure, or all -CO-X attached to a carbon bearing at least the solvent can be removed in this manner be two hydrogen atoms, in an inert anhydrous sol fore reacting the acyl ethenone with an India, vent at room temperature. Removal of the ter tiary amine hydrochloride by indirect filtering Satisfactoryor a suitable as amine.when a This,solvent however, is used. is not as after the reactants have stood from 12 to 24 40 A particularly useful class of products coming hours gives a solution of the acyl ethenone. The Within the broad scope of this invention, namely acyl ethenones must be prepared under anhy that of amides containing at least- one hydrogen drous conditions and maintained in an anhy atom on the amide nitrogen may be prepared by drous environment until used. The acyl ethe the reaction of acyl ethenones on basic com. nones suitable for the purpose of this invention 45 pounds having two hydrogens on the same am have at least thirteen carbon atoms and have nonia type nitrogen and are useful intermediates the formula for the Synthesis of water repellent materials and R-CH-CO-C-CO related products. Synthesis of water repellent 50 materials, as outlined in Example I below, is ef R being a monovalent organic radical which, fected by condensing the beta-ketocarbonamide from the method of preparation, is chemically With paraformaldehyde and an anhydrous hydro inert at temperatures up to 170° C. to tertiary halogen acid in an inert solvent, and subsequently amines, acid halides and ethenones. R is pref reacting the isolated amidomethyl halide with a erably a hydrocarbon radical such as aryl, aral tertiary amine.

2 2,828,938 The more detailed practice of the invention is The Water repelling agent (5 parts) is pasted illustrated by the following examples, wherein with ethanol (6 parts) at 40-43° C. Water (90 parts given are by Weight. There are of course parts) at 40-43 C. is added with stirring, and many forms of the invention other than these Sodium acetate (2 parts) in water (4 parts) at specific embodiments. 40-43 C. is added to produce a pH of approxi mately 5. A piece of cotton jean cloth is dipped Eacample I into the solution, squeezed through rollers, and A mixture of eicosanoic and docosanoic acids, the process repeated. The wet cloth weighs ap available commercially from the hydrogenation proximately twice its dry weight. It is then dried of fish oils, is converted to the acid chlorides O by circulating warm dry air over it, and finally which are converted to the acyl ethenones in the baked at 150° C. for 5 minutes. In examining following manner. The twice distilled Cao-2 acid the water repellent properties of the finished fab chlorides (51 parts) are dissolved in anhydrous ric by the Spray test the following results are ob benzene (880 parts) and an equivalent of tri tained: ethylamine (16.5 parts) is added. The mixture is allowed to stand for 20 hours at room tempera ture and then filtered. A total of 21 parts of tri Repellency ethylamine hydrochloride is separated by this Initial Laundered filtration. The reaction for simplicity is repre sented as follows: 20. 85 80 2RCH,COC1 + 2(CH3)N - RCHCOCscC=O -- 2(CH)N.HCl A cloth having a repellency of 100 will, when inclined at a 45° angle, completely repel 250 cc. The product is a mixture of acyl ethenones 2 5 of water at 80° F. sprayed from a height of 6 wherein the two R's are the same or different, inches directly above, and none will cling to the the R's having 18 and 20 carbon atoms. cloth. A repellency of 90 means that a few drops To a solution of 45 parts of the acyl ethenone. of Water cling to the cloth but can be completely. mixture in anhydrous benzene (7,040 parts) is removed by shaking. A repellency of 50 means added hexamethylenediamine (54 parts). After that the upper surface of the cloth is wetted the mixture has stood for several hours to insure under the experimental conditions, but the water complete reaction, an additional 100 parts of does not penetrate the cloth. hexamethylenediamine is added. The reactor The laundering treatment consists in boiling vessel is then set aside at room temperature over the sample in a 0.1% soap solution for one hour, night during, which time the reaction product rinsing thoroughly and drying. crystallizes from the solution. A yield of 45% of Eacample II the theory of purified product is obtained. The . product is represented by the formula The acid chlorides of the mixture of eicosanoic and docOSanoic acids are converted to the acyl RCHCOCHCONHCCH)NHCOCHCOCHR ethenones as illustrated in Example I. The acyl 40 ethenones are converted to the corresponding in which R, and R' contain 18 or 20 carbon atoms amides by bubbling anhydrous ammonia through . and are alike or different. The melting point of the benzene Solution of the ethenones. (Carbon the product is 88-93° C. tetrachloride solutions may also be. used.) The To the amide (205 parts) in dry benzene (1100 5 benzene solution is chilled, filtered, and the pre parts) is added paraformaldehyde (18 parts). cipitate recrystallized from aqueous ethanol. The mixture is stirred at 50 to 60° C. for 2.5 hours The melting point is 94-97° C. Analysis of the while a stream of dry hydrogen chloride is product showed 2.5% N as compared with 2.3% bubbled through the reaction mixture. After N calculated for C42H83O2N. The product has separation of the Water layer, the benzene is re 50 the general formula moved under reduced pressure - at 40 C. until RCHCOCHCONE only the chloromethyl derivative is left. Dry W pyridine in excess is added until an homogeneous solution results upon being stirred. Most of the in which R and R' contain 18 or 20 carbon atoms excess pyridine is removed under reduced pres 55 and are alike or different. sure and the last traces removed in a vacuum To these amides (170 parts) in dry benzene desiccating compartment. (970 parts) is added paraformaldehyde (22 parts) A portion of the product which comprises and a stream of dry hydrogen chloride is bub chiefly the amidomethylpyridinium chloride salt, bled into the reaction mixture with constant stir is analyzed for active ingredient content by the ring for a period of 2.5 hours. The reaction mix following method. To a weighed sample of the 60 ture is maintained at a temperature of 55-60° C. product is added ice and methanol and the cold The water layer is separated and the benzene solution is titrated with alkali immediately. This removed under reduced pressure. After removal analysis determines what portion of the chlorine of the solvent, the material is melted on the steam is present as pyridine hydrochloride. A second bath and pyridine (43 parts) is added with rapid weighed sample dissolved in methanol is heated 65 stirring and cooling. After the excess pyridine st reflux temperature from 3 to 24 hours and has been removed under reduced pressure a sam then titrated with alkali. The heating step con ple is analyzed for chlorine and found to contain verts all the quaternary annihonium salt to pyri 6.6% whereas the value calculated for dine hydrochloride and the titration with stand 70 ard alkali gives the total chlorine content. The is 5.7. difference between the total chlorine present and Analysis of "active ingredient' content shows a the chlorine present as pyridine hydrochloride value of 40 per cent. gives the “active ingredient" content. In this The amidomethylpyridinium salt (6 parts), ob- . case it is 83 per cent. m 75 tained as described above, is pasted with ethanol

2,323,988 y -- 3 (5 parts) at 40 to 43', C. Water (90 parts) at drous ammonia is bubbled into the solution of 40-43 C. is added with stirring. Sodium acetate (2 parts) in water (4 parts) at 40-43 C, is added the acyl ethenone having the formula . to give a pH of epproximately 5. This solution contains 2.4% of "active ingredient.' . The following experiment is run in duplicate: A. quantitative yield of the alpha-dodecanoyl A piece of cotton jean cloth is dipped into the dodecanamide is obtained. After three recrystal Solution and allowed to become saturated, Wrung lizations from ethanol, the product melts at 110 in a meghanical winger and the process repeated. to 111° C. The wéight of the wet cloth is twice its dry O Eacample VI weight. It is dried and baked for 5 minutes at Dodecanoyl chloride is converted to the acyl, 150° C. The results of spray tests. made on the ethenone in the same manner as outlined in Ex two samples are as follows: ample W. To an ether solution of the acyl ethenone is added aniline and the reaction mix Repellency 15 ture allowed to stand overnight, The following morning the precipitate which formedi is filtered Initial Laundered and recrystallized twice from ethanoi. The alpha-dodecanoyldodecanilide has a melting point 100 100 of 84 to 85 C. and analyzes for 78.46% carbon, 100 100 20 11.77% hydrogen and 3.18% nitrogen which com Eacample III pares with the values calculated for CoHs10 of Octadecen-9-oic acid chloride is converted to 78.72%nitrogen. carbon, 11.24% hydrogen and 3.06% the acyl ethenone by adding triethylamine (63.2 : Eacample VII parts) to octadecen-9-oyl chloride (187 parts) in dry carbon tetrachloride (2370 parts). The re 25 Octadecanoyl chloride is converted to the acyl action vessel is closed and stored at 35-40 F. for ethenone by adding triethylamine (101 parts) to three days. The triethylamine hydrochloride is a Solution of octadecanoyl chloride (76 parts) in separated by filtering. anhydrous benzene (880 parts), allowing the re- . Gaseous anhydrous ammonia is bubbled into a 30 peratureaction mixture and separating to stand for the 24 triethylamine hours at room hydro tem 6.6% solution by weight of the acyl ethenone in chloride formed by fiitering. To the filtrate is carbon tetrachloride, the Solvent removed under added 1,5-aminonaphthol (40 parts). The reac reduced pressure and the product carefully dried. . tion mixture is allowed to stand at room temper The product analyzed for 2.68% nitrogen com ature for 60 hours, and is then heated for 1 hour pared with 2.56% calculated for CashesO2N. 8 at 40-50° C. The reaction mixture is washed The product can be converted to the amido - with water containing a small amount of sodium methylpyridinium halide by the method illus sulfite dissolved in it. The product is recrystal trated in Example. , lized from ether-petroleum ether mixture. It The amide has the formula has the formula. CHCH,Cog HCONH, 40 Ciss - &H, CissCC obic ONE Eacample IV Linseed oil acid chlorides (B. P. 180-3° C./5 m.), a mixture of the C18 multiply, unsaturated straight chain acid chlorides, are converted to the acyl ethenones by adding, during a 5 minute O period, triethylamine (25.5 parts) to a solution of the linseed oil acid chlorides (75 parts) a in . Eacample VIII anhydrous ether (720 parts). Precipitation of Alpha-octadecanoyloctadecanamide is prepared thiethylamine hydrochloride begins immediately, by adding triethylamine (233 parts) to a solution the reaction mixture is placed under an atmos of octadecanoyl chloride (694 parts) in carbon phere of nitrogen and, after 2 hours at room tetrachloride (5760 parts), allowing the reaction temperature, the reaction vessel is maintained at mixture to stand for 16 hours, separating the 35-40 F. for three days. The thiethylamine 55 aminehydrochloride by filtering, and bubbling hydrochloride is separated by filtering, and the into the filtrate an excess of anhydrous ammonia filtrate concentrated to 200 parts under reduced at room temperature whereupon the alpha-octa preSSlre. decanoyloctadecanamide crystallizes from solu tion. After recrystallization from ethanol-ace concentratedGaseous anhydrous solution ammoniaof the acylis bubbled ethenone into ina 60 tone mixture, the product, melting at 104° C., is anhydrous ether. The precipitated amide is obtained in a 95 per cent yield and contains 2.22% washed with ether, dried, and analyzed for 2.8% nitrogen, the value calculated for C36H11ON nitrogen whereas the value calculated for being 2.55%, C36H63O2N is 2.6%. The products of the present invention have the The product can be converted to the amido 65 generic formula methylpyridinium halide by the method illus (R-CO-CHR-CO-NR), R3 trated in Example II. wherein R and R have the values given above, Eacample V . are preferably both hydrocarbon and total at 70 least nine and preferably twenty carbon atoms, To triethylamine (52 parts) in anhydrous di R is hydrogen or a monovalent organic radical, ethyl ether (1050 parts) is added dodecanoyl and R is the non-amino residue of the basic con chloride (109 parts) and the reaction mixture is pound having hydrogen on ammonia type nitro allowed to stand 24 hours before the amine hydro gen, ac represents, the number of carbonamido chloride is removed by filters. Gaseous anhy 75 residues in the compound and also the number

4. 2,323,988 of hydrogen bearing ammonia type nitrogens in amines produces the most desirable products, for the parent basic compound. R may be aliphatic, when the resulting amide nitrogen is hydroger cycloaliphatic, araliphatic or aromatic and is bearing, subsequent reaction with paraformalde preferably hydrocarbon R may be all of these hyde, an anhydrous hydrohalogen acid, and a and may be monovalent or polyvalent (as in the tertiary amine produces products that are useful diamines). R and Rs may be unsubstituted, or as Water repellents and as textile treating agents. substituted as illustrated in Example VII. Amidation is effected by adding any of the amines These substituted radicals may contain dye coul described above in an anhydrous form to a solu pling nuclei as is further illustrated in Example tion of the acyl ethenone. The presence of a sol VII. In addition to the aromatic dye coupling 10 went is not necessary, however, for the amidation nuclei, both R and R can be long chain radicals reaction. The Solvent may be removed under re useful in the preparation of intermediates for duced pressure at a low temperature and the re color photography. maining acyl ethenone reacted directly with the The acyl ethanone intermediates for the prep amine in the absence of a solvent. If the amine aration of the beta-ketocarbonamides may be s is low boiling and the excess can be removed at prepared, as disclosed in my copending applica low temperature under reduced pressure, the re tions above identified, in anhydrous inert Solvents sulting amide can be used in any subsequent re by reaction of the corresponding acid chlorides action without further purification or can be re with tertiary amines. Removal of the tertiary Crystallized from a Suitable solvent. Amides pre anine hydrochloride gives a solution of the acyl 20 pared in solvents frequently precipitate from ethenone which can be reacted readily with an these solvents and may be used in subsequent re amine or with ammonia. Solvents suitable for action without further purification, or can be re acyl ethenone preparation are also admirably crystallized from suitable solvents. Some of the suited for the subsequent amidation reaction. amides, however, have been found to be soluble Any solvent which dissolves but is inert toward 25 in the solvents in which they were prepared. In acyl halides, tertiary amines or acyl ethenonses is these cases the solvent is removed at low tem operable. Therefore a wide variety of solvents peratures under reduced pressure, and again the including ethers, aromatic or aliphatic hydro amide can be used as isolated or can be purified carbons, aromatic and aliphatic chlorinated hy by recrystallization from a suitable solvent. drocarbons can be employed, including anhydrous Amines suitable for amidating the acyl ethenones benzene, petroleum ether, petroleum naphtha, di 30 include methylamine, ethylamine, ethanolamine, ethyl ether, di-isopropyl ether, carbon tetrachlo propylamine, butylamine, isobutylamine, cyclo ride, trichloroethylene, toluene, and other related hexylamine, pentylamine, cyclopentylamine, solvents that will not react with ammonia or hexylamine, heptylamine, octylamine, nonyl amines under the conditions required for amida amine, decylamine, hendecylamine, dodecylamine, tion. Chlorinated hydrocarbons not suitable as tridecylamine, tetradecylamine, pentadecylamine, solvents include benzyl chloride and alpha- or . . hexadecylamine, heptadecylamine, octadecyl beta-chloroethers. . amine, nonadecylamine, eicosylamine, heneicosyl The only acyl halides which can be converted amine, docosylamine, hentriacontylamine, hexa to acyl ethenones and subsequently to amides contylamine, andline, p-hydroxyaniline, naphthyl falling within the scope of this invention are amine, aminophenanthrene, aminoanthracene, those containing one (-CHCOX) group. At aminochrysene, dimethylamine, diethylamine, di tached to the -CHCOX group may be any radi butylamine, N-methylhexylamine, N-methyl cal aert towards tertiary amines, acyl halides, or cyclohexylanine, piperidine, morpholine, N acyl ethenones, such as the straight and branched methylaniline, p-methoxy-N-methylaniline, pyr chain alkyl, aryl, carbalkoxy or ether groups. role, pyrroline, pyrrollidine, 1,2,3-dioxazole, 1,3,2- The inert radicals attached to the -CH-CO-X dioxazole, 1,2,4-dioxazole, 1,3,4-dioxazole, indole, group are so chosen that they total at least nine soindole, 1,2-benzisoxazine, dipropylamine, di and preferably twenty carbons. Examples of pentylamine, di-isobutylamine, N-methylocta suchhalides are hendecanoyl chloride, dodecanoyl 50 decylamine, N-methylheptadecylamine, N-ethyl chloride, tridecanoyl chloride, tetradecanoyl chlo- . eicosylamine, N-methylheneicosylamine, N. ride, pentadecanoyl chloride, hexadecanoyl chlor methyldocosylamine, N-methylhexacosylamine, ride, heptadecanoyl chloride, octadecanoyl chlor dioctadecylamine, didodecylamine, and dipentyl ride, 4-phenoxybutanoyl chloride, cyclohexyl- . . amine, ethylenediamine, trimethylenediamine, acetyl chloride, furyldecanoyl chloride, 3-phenyl tetramethylenediamine, pentamethylenediamine, propanoyl chloride, octadecen-9-Oyl chloride, 5 hexamethylenediamine, beta-methylhexamethyl-, nonadecanoyl chloride, eicosanoyl chloride, docos enediamine, beta-phenylhexamethylenediamine, anoyl chloride and hexacosanoyl chloride. Mixir decamethylenedianine, tridecamethylenediamine, tures of acid chlorides can be used but the lower bigesimethylenedianine, dobigesimethylenedi molecular weight acid chloride should contain at amine, n-diaminobenzene, 1,5-diaminonaph least 3 carbon atoms. Any acyl ethenone of the 6. thalene, 3,6-dioxa-1,8-diamino-octane, hepta formula methylenediamine, nonamethylenediamine, octa R-CH-CO-CR'-CO methylenediamine, hendecamethylenediamine, wherein R and R' are as above may be used. dodecamethylenedianine, tetradecannethylenedi In the preparation of the amides, any basic 65 amine, pentadecamethylenediamine, hexadeca. compound having hydrogen on ammonia type methylenedianine, heptadecamethylenediamine, nitrogen may be employed including annonia, octadecamethylenediamine, nona decamethylene hydrazine, hydroxylamine, and amines having at . diamine, N,N-dimethylhexamethylenediamine, least one hydrogen on the amino nitrogen. While N,N' - didodecamethylenedobigesimethylenedi amines, etc. having other groups reactive with amine, piperazine, N,N-dimethyl-1,3-diamino the acyl ethenones may be employed, it is pre benzene, N,N'-diethylethylenediamine, N,N'-di ferred that the basic ammonia type compound methylpropylenediamine, N,N-dimethylbutylene have only the =NH grouping reactive with acyl diamine, N,N'-dimethylpentamethylenedianine, ethenOnes. N,N'-dimethylheptamethylenediamine, N,N'-di Amidation with ammonia and with primary 75 methyloctamethylenedianine, N,N'-dimethyl

d 2,823,988 :S nonamethylenediamine, N,N' - dimethyldeca-. 3. Process which comprises reacting an acyl methylenediamine, N,N' - dimethyloctadeca- ethenone of the formula methylenedianine, N-methyl-1,4-diaminoben Zene, N-methylhexamethylenediamine, N-methyl R-CH-CO-CRECO ethylenedianine, 4-aminopiperidine, N-methyl s wherein R and R are monovalent aliphatic hy propylenedianine, N-ethylbutylenediamine, N drocarbon radicals totalling at least nine carbon heptyltetradecamethylenediamine, N-propylde atoms with a basic compound having a hydrogen camethylenediamine, N-methyloctadecamethyl bearing ammonia type nitrogen of the class con enediamine, and N-methyloctamethylenediamine. sisting of ammonia, and aliphatic hydrocarbon The term "aliphatic hydrocarbon monamine hav O monoamines having hydrogen on amino nitrogen, ing hydrogen on amino nitrogen" is used to desig 4. A beta-ketocarbonamide of the formula rate a monoamine which, apart from the amino nitrogen and hydrogen attached thereto, is ali R-CH-CO-CHRA CO-NH phatic hydrocarbon. where R and R are monovalent aliphatic hydro The products of this invention are useful inter 5 carbon radicals totalling at least twenty carbon mediates in the synthesis of water repellents, tex atoms. tile treating agents, and other products of com 5. Process of claim 3 wherein the basic com mercial importance. pound is ammonia. The above description and examples are in 6. Process of claim 3 wherein the basic com tended to be illustrative only. Any modification 20 pound is an amine. of or variation therefron which conforms to the 7. Process of claim 3 wherein the acyl ethenone spirit of the invention is intended to be included is one obtained from at least one fatty acid chlo within the scope of the claims. ride. What is claimed is: 8. Process of claim 3 wherein the acyl ethenone 1. A beta-ketocarbonamide of the formula 25 is obtained from a mixture of fatty acid halides. R-CH-CO-CHR. CO-NHR 9. A beta-ketocarbonamide of the formula wherein R, R and R2 are monovalent aliphatic R-CH-CO-CHR-CO-NHR hydrocarbon radicals and R and R total at least wherein R and Rare monovalent aliphatic hy nine carbon atoms. drocarbon radicals totalling at least nine carbon 2. A beta-ketocarbonamide of the formula, 30 atoms and R is a member of the class consisting of hydrogen and monovalent aliphatic hydro R-CH-CO-CHR-CO-NHR carbon radicals. where R and R are alkyl radicals totalling at 10. Alpha-octadecanoyloctadecanamide. least nine carbon atoms. JOHN CAR SAUER. CERTIFICATE OF CORRECTION . . . Patent No. 2,525,938. . July 13, 1943. JOHN CARL SAUER. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows : Page 5, first column, line 52, claim 2, for that portion of the formula reading st NHR2n read --NH2--; and that the said Letters Patent should be read with this . correction there in that the same may conform to the record of the case in the Patent Office. Signed and sealed this 7th day of September, A. D. 1943.

w Henry Van Arsdale, (Seal) Acting Commissioner of Patents.