Patented Apr. 15, 19% [2,2385%

UNITED STATES PATENT OFFICE‘. 2.238.826 MONACYL ETHENONES AND A PROCESS OF MAKBQG THEM John Carl Sauer, Wilmington, Del., assignor to E. I. du Pont de Nemonrs 8; Company, Wllmlng? ton, Del, a corporation of Delaware No Drawing. Application ?ctoher 13, 1938, Serial No. 234,344 11 Claims. (Cl. 260--550) This invention has as an object the provision At 0—25° C., the time required for complete re of a. process for the preparation of monacyl action varies from 1 to 16 hours, depending on ethenones. Another object is the provision of the acyl halide and amine used. Dehydrohalo a process for the preparation of novel ethenones. genation is usually complete in an hour at room A further object is the provision of intermediates U temperature when trimethylamine is employed, for the preparation of beta-ketonic esters, or in 30 minutes when the reaction is carried out amides, and other chemical compounds. Other in re?uxing benzeneor xylene with a trialkyl objects will appear hereinafter. ‘ amine such as triethylamine. Higher tempera The objects of the invention are accomplished tures promote an even more rapid reaction. The by reacting a mixture of at least two primary 10 higher substituted ethenones are conveniently monoacyl halides’ (which, except for the acid purified by fractional recrystallization, and dis halide group, are chemically unaffected by ter tillation is usually unnecessary. V ' tiary amines, acid halides, and ethenones at On the other hand, the lower acyl halides, temperatures up to 170° C.), under anhydrous such as propanoyl chloride, are very reactive conditions, with a saturated tertiary aliphatic toward tertiary aliphatic amines and are best amine free of active hydrogen and having any dehydrohalogenated under‘ a re?ux condenser by pair of nitrogens separated by a chain of at least adding the amine to a solution of the acyl halide two carbon atoms, and thereafter isolating, also . mixture (or vice versa.) just fast enough to keep under anhydrous conditions, the substituted the solvent gently re?uxing. The mixture of ethenone, or ethenones obtained. There is thus lower acyl halides is completely dehydrohalo effected an intermolecular dehydrohalogenation genated with trimethylamine within a few min of the acyl halides with formation of a mixture utes at room temperatures. ‘ of products comprising one or more new com A suitable method for determining when the pounds of the probable formula. - reaction has gone to completion'is merely to filter a small portion of the reaction mixture 1r—cm‘~co-c|:=c=o and boil a drop or two of trlalkylamine with the R’ . ?ltrate. The reaction is complete when no pre wherein R is an organic radical, preferably hy cipitate appears. drocarbon, free of groups reactive at 170° C. with The precipitated amine hydrochloride is pref tertiary amines, acid halides and ethenones, and - erably isolated by indirect ?ltration, employing R’ is di?'erent ,from R and is hydrogen or an nitrogen pressure to avoid contact with air, and organic, radical; preferably hydrocarbon, free of the ?ltrate is concentrated by distillation. 0r~ groups reactive up to 170° C. with tertiary amines, dinary direct ?ltration can be employed but re acid halides and ethenones. quires pains-taking exclusion of moisture. The When higher ‘substituted ethenones (i. e., the ' residue, consisting of a mixture of substituted ethenones derived from mixtures‘ of acyl halides ethenones, is fractionally distilled in‘ the case of each having 8 or more carbons) are desired, the the lower substituted ethenones, 'or fractionally preferred method consists in dissolving chem crystallized in the case of the higher substituted ically equivalent amounts of at least two aeyl ethenones, to separate the mixture into its in— halides in an inert solvent such as ether, adding 40 dividual components. The reaction product is a 'suilicient tertiary amine to dehydrohalogenate mixture, in varying amounts, of compounds of all the acyl halide present (or the reverse pro the probable formula R—CH2COC(R')CO, cedure can be employed, i. e., the acyl halide wherein R and R’ are hydrogen or monovalent mixture can be added to the amine), and quickly organic radicals representing invlany instance closing the reaction vessel to avoid contact with either of the acid halide residues R. and R’ of moisture. The contents of the reaction vessel the acid halides RCH2COX and R'CHzCOX. are agitated and, if necessary, cooled to oifset provided that, when R’ is ‘an organic radical, any heat of reaction. This procedure is con R is also an organic radical. R and R’ are both venient,.and the only apparatus required is a ' hydrogen only‘ when acetyl chloride is a com reaction vessel provided with agitation means. 50 ponent of the reaction.‘ 01 these, only the 2 2,238,826 compounds in which R. and R’ are different, propanoyl chloride (73.6 parts, 0.8 mol), and come within the scope of the present invention. octanoyl chloride (129.6 parts, 0.8 mol). Tri ' The more detailed practice of the invention is ethylamine (165 parts, 1.6 mols) is added drop illustrated by the following examples, wherein wise with stirring over a period of 30 minutes. parts given are by weight. There are of course After. standing 16 hours at room‘temperature, many forms ‘of the invention other than these the theoretical amount of triethylamine hydro speci?c embodiments. chloride has precipitated and is removed by ?l EXAMPLE I tration. After distilling the solvent from the filtrate, the residue is fractionated under di ' DODECANOYLETHENONE 10 minished pressure with the results shown in In a reaction vessel equipped with a stirrer, _ Table I below: ' re?ux condenser and a device for slow intro Table I duction of liquid are added anhydrous ether (800 parts), dodecanoyl chloride (218 parts, 1.0 Fraction B. P., °C. Weight Product .Yield mol) and acetyl chloride (78 parts, 1.0 mol). Triethylamine (206 parts, 2.0 mols) is added It! m. Parts ', Pen :11! dropwise over a period of 30 minutes, with stir l ______.. 50-76/12 l2 Propanoylmethylethe- 28 , none. , ring, after which the mixture is stirred foran 2 ...... _. 124~5l14 33 Unsymmetrical etne- 26 additional two hours. The vessel is then left none, Cu 1: : standing at room temperature for 18 hours, and 3 ______. 107-42/2 31 Octanoylhexylethenone _ 3i the triethylamine hydrochloride is removed by ?ltration. The ether is next distilled from the The products of the reaction are‘character ?ltrate, and the vresidue is fractionated under ized as follows: ‘ reduced pressure. Acetylethenone (12 parts), Propanoylmethylethenone (symmetrical prod boiling at 40—-60°_C./15-50 inm., is obtained as uct).--Fraction 1 is found on analysis to con one of the symmetrical products. The next frac tain 63.9% carbon and 7.3% hydrogen, and to tion, dodecanoylethenone, distills at 130-170" have a molecular weight of 114 and an index of C./4*20 mm. and amounts to 25 parts. The refraction, residue is dodecanoyldecylethenone, which after Ni}, of 1.4280 being puri?ed by recrystallization from acetone. A compound of the formula CaHsOz has calcu melts at 41° C., and consists of 50 parts. lated carbon and hydrogen contents of 643% Of the above pure products, only dodecanoyl and 7.15%, respectively, and a calculated mo ethenone, the unsymmetrical ethenone, comes lecular weight of 112. within'the scope of the present invention. ‘The Unsymmetrical ethenOne.--Fraction 2 is found products are characterized as indicated below: 35 to have 72.2% carbon, 9.85% hydrogen, a mo Acetylethenone (symmetrical product) .--Ac lecular weight of 172, and ' ' etylethenone is characterized by reacting it with aniline. The resulting acetoacetanilide melts at N‘g, 1.4457 83-4“ 0., and a mixed melting'point determina A compound of the formula CuHraOz has calcu tion with an authentic sample of acetoacetanilide lated carbon and hydrogen contents of 72.5% shows no depression. This fraction is then the and 9.9%, respectively, and a calculated molecu compound of the probable formula lar weight of 182. Addition of excess gaseous ammonia causes ready precipitation of an amide, melting at 100-101“ C., which from its nitrogen Dodecanoylethenone (unsymmetrical prod content of 7.5% must be derived from a prod uct) .--This product is found on analysis to have uct of the formula G--CH2COC(G)CO in which 754% carbon and ‘11.7% hydrogen, whereas the the G’s are di?erent'groups representing the amounts calculated for a compound of the for acid halide residues and having together 7 car mula C14H24O2 are 75.0% and 10.8%, respectively. bon atoms. 'The amide is further identified (and Reaction of this unsymmetrical ethenone with with it the ethenone from which it is made) by aniline gives crude dodecanoylacetanilide melt the fact that it can be saponi?ed and decarboxyl ing at 54-7° C., and having on analysis 4.6% ated in known manner to ethylheptyl ketone nitrogen as compared to the calculated amount whose semicarbazone is _ found to melt at of 4.5% for a compound C20H21O2N. The anilide 100-101“ C. Michael (J. Am. Chem. Soc‘. 41. is further characterized by converting it into an ' 318, 1919) reports the melting point of this semi orange dye with p-nitrophenyldiazonium chlo carbazone as 101° C. ride, which dye on analysis has the calculated Octanoylhezylethenone (symmetrical prod amount of nitrogen (12.0%) for a compound of uct).--Fraction 3 is found on analysis to con the formula C26H3404N4. This fraction is thus dcdecanoylethenone of the probable formula tain 76.3% carbon and 11.2% hydrogen, and to 60 have a molecular weight of‘ 235 and an index CioH21CI-I2CO—CH=C=O. The latter series of reactions shows the compound must be do of refraction, decanoylethenone and not acetyldeeylethenone. N59, 1.4489 _ , Dodecanoyldecylketene (symmetrical prod v A compound of the formula Ciel-I280: has calcu uct).,—The residue is found on analysis to con lated carbon and hydrogen contents of 76.2% _tain'78.8% carbon and 12.2% hydrogen, and to and 11.1%, respectively, and a calculated mo have a molecular weight of 351. The calculated lecular weight of 252. , values for a compound of the formula C24H4402 are 79.1%, 12.5%, and 364, respectively. EXAMPLE IH EXAMPLE II DEHYDROHALOGENATION or PBOPANOYL CHLORIDE , HEXANOYL CHLORIDE MIXTURE DEHYDROH'ALOGENATION ' 0F PBOPANOYL CHLORIDE In an apparatus similar to that described in OCTANOYL CHLORIDE MIXTURE Example II is placed anhydrous petroleum ether In an apparatus similar to that described in (650 parts) and triethylamine (133 parts, 1.3 Example I is placed anhydrous ether (650 parts), 75 mols). A mixture of propanoyl chloride (70 2,238,826 3 parts, 0.?5 mol) and hexanoyl chloride (86 parts, choose a solvent boiling either considerably below 0.64 mol) is added dropwlse with stirring over or above the substituted ethenones, thereby facili a period of one hour and at a temperature of tating the separation of the product from the 20-25° C. After standing 24 hours at room tem solvent. Such a choice is especially bene?cial in perature, the precipitated triethylamine hydro 5 preparing and isolating the lower substituted chloride is removed by ?ltration. After distilling ethenones when distillation is used in the separa the solvent from the ?ltrate, the residue is frac tion. Speci?c suitable solvents, include ligroin, tionated under diminished pressure with the benzene, toluene, xylene, chlorobenzene, o-di results shown in Table II below: ' chlorobenzene, diethyl ether, dibutyl ether, Table II 10 chloroform, carbon tetrachloride and trichloro ethylene. The amount of solvent may be varied ' 1 Fraction B. P., °C. \Veight Product Yield within wide limits. Using 100-200 cc. solvent per 0.1 gram mol of each reactant has been found Mm. Parts Percent satisfactory. The amount of solvent used should l 70-75/30 14 Propanoylmet hylcthe :i6 15 be su?lcient to dissolve the substituted ethenones, none. 1 ll —6/30 22 Unsymmetrical ethe 44 thus facilitating the separation of the insoluble none, C;Hu0:. tertiary amine hydrochloride by ?ltration. It is 13544830 17 Hexsnoylbutylethcnone. 27 also feasible to use an excess of the amine as solvent in cases where the substituted ethenone The products of the reaction are characterized 20 can be readily separated from the amine. For as follows: those uses of ethenones in which the presence Propanoylmethylethenone (symmetrical prod of the amine hydrochloride does no harm, the uct).--Fraction 1 is found on analysis to con dehydrohalogenation can be carried out in the tain 63.9% carbon and 7.3% hydrogen, and to absence of a solvent. have a molecular weight of 114 and an index of 25 A wide temperature ‘range for the reaction is refraction, also permissible, the process having been ap N295, of 1.4280 plied successfully at temperatures ranging from 0° C. to 140° C. The higher temperatures pro A compound of the formula CsHaOa has calcu~ lated carbon and hydrogen contents of 64.3% mote a more rapid reaction. The process is ordi 30 narlly carried out at atmospheric pressure (about and ‘7.15%, respectively, and a calculated mo-, lecular weight of 112. , 760 mm.), but operation at pressures above or Unsymmetrical ethenone.--Fraction 2 is found below atmospheric is feasible. to have 69.3% carbon, 9.8% hydrogen, a molecular The process of the present invention is gen weight of 144, and an index of refraction, erically applicable to a mixture of at 35 least two different primary monoacyl halides \ Nii, of 1.4417 R’-CHzCO'-—X, where X is any halogen and R’ ' A compound of the formula C9H‘14O2 has calcu ‘ is hydrogen or a monovalent organic radical lated carbon and hydrogen contents of 69.6% which is chemically inert at temperatures up to and 9.7%, respectively, and a calculated molec 40 170° C. to tertiary amines, acid halides and ular weight of 154. Addition of excess gaseous ethenones. R’ is preferably a hydrocarbon radi ammonia causes ready precipitation of an amide, cal such as aryl, aralkyl, cycloalkyl, and open melting at 102-103° C., which, from its nitrogen chain alkyl (especially alkyl) but may contain content of 8.3%, must be derived from a product inert groups such as carbalkoxy, alkoxy, araloxy, aralkoxy, keto, tertiary amide, halogen attached of the formula G—CH2COC(G) CO, in which the 45 G’s are different groups representing the' acid to aromatic carbon, or aliphatic heterocyclic halide residues and having together ?ve carbons. groups. By the latter is meant heterocyclic radi The amide formed from this unsymmetrical cals not having benzene-type unsaturation, which ethenone has a theoretical nitrogen content of is commonly represented by three or more alter , 8.2%. nating double bonds in a ring structure. The '00 Heranoylbutylethenone (symmetrical prod? heterocyclic radical may thus be saturated or un uct) .—'Fraction 3 is found on analysis to have a saturated. Types of radicals which should not molecular weight of 198 and an index of refrac be present are aromatic heterocyclic radicals, tion, amide groups having amido hydrogen, and an M acyloxy groups. Suitable speci?c halides include N33", of 1/1478 the following: n-dodecancyl, n-decanoyl, n-non A compound of the formula C12H20O2 has ‘a calcu anoyl, n-octanoyl, n-hexanoyl, 9,10~octadecenoyl lated molecular weight of 196. (oleyl), linoleyl, n-heptanoyl, 3-methylbutanoyl, A most important condition of the present’ n-butanoyl, propanoyl, acetyl, 4-phenoxybuta process is that it must be carried out in toto 60 noyl, 5-(2,3,5-trichlorophenoxy) p e n t a n o y l , (both reaction and isolation of products) under 5-ketooctanoyl, furyldecanoyl, delta-carbmeth anhydrous conditions. ' ‘ oxypentanoyl, delta-methoxypentanoyl, 3 - Any solvent which dissolves and is inert, under phenylpropanoyl, octadecanoyl, hexadecanoyl, the conditions of the process, towards acyl tetradecanoyl, and cyclohexylacetyl chlorides. halides, tertiary amines, and ethenones may be (i5 The corresponding bromides, iodides, and ?uo used. Thus a wide variety of solvents, includ rides are also suitable for the reaction. Mixtures ing ethers, aromatic or aliphatic hydrocarbons, of fatty acid halides derived from the mixture aromatic or aliphatic chlorinated hydrocarbons of fatty acids obtained by saponi?cation of fatty containing inactive halogen atoms, such as tri . oils provide a convenient source of mixed halides. chloroethylene, tetrachloroethylene, or carbon‘ 70 The amine component of the reaction may be tetrachloride, is suitable. Chlorinated hydrocar any tertiary, saturated, mono- or polyamine free bons not suitable as solvents include benzyl from active hydrogen (i. e., hydrogen which is chloride and alpha- or beta-chloroethers. In joined to an inorganic element, e. g., O,S,Se, those cases where the substituted ethenones are Te,N,P,As) in which all the radicals attached to isolated by distillation, it is most convenient to 75 the amino nitrogen or nitrogens are aliphatic in 4 . 2,238,826 character; or, more simply, saturated tertiary The unsymmetrical products are the subject of aliphatic amines free of active hydrogen. In the the present invention. , case 01’ polyamine any pair of nitrogens must be The dehydrohalogenation 01' more than two separated by a chain of at least two carbon atoms. primary acyl halides theoretically gives additional Saturated tertiary acyclic amines free of active symmetrical and unsymmetrical ethenones. The hydrogen are preferred. Speci?c suitable amines following table shows the number of symmetrical includes trimethylamine, triethylamine, tri-n and unsymmetrical products theoretically pos propylamine, methyldiethylamine, benzyl-N,N sible when a mixture of n-acyl halides is ‘dehy dimethylamine, ethylmethylpropylamine, l-ethyl drohalogenated. piperdine, l-isopropylpiperidine, l-methylhexa hydroazepine, l-methylpyrrolidine, N,N,N’,N' Bym- Unsym- ‘ tetramethylethylenediamine, N-m'ethylmorpho Acyl halides metrical metrical Total . line, N-ethylthiomorp'holine, ,cyclohexyl-NN-di products products ‘ethylamine, 1,6-bis(dimethy1amino)hexane, 1,3 2 I 2 4 di(1-piperidyl)-propane,' and 1,4-bis(diethyl 3 6 9 amino)butane. Pyridine, di-l-piperdylmethane, 4 12 16 bis(dimethylamino)methane, and dimethylaniline - 1| n(n~1) 1|I do not dehydrohalogenate the above described acyl halides under the conditions used. These substituted ethenones may be used in the Usually chemically equivalent amounts of tri preparation of unsymmetrical ketones, substitut alkylamine and acyl halide are used. An excess ed beta-ketoamides, aniiides, and esters. Certain of amine or of acyl halide may be employed, but of these ethenones, as well as their derivatives, this may introduce some diiilculty in isolating have proved useful as dye intermediates. The the products. The acyl halides can be present higher molecular weight substituted ethenones in any molar ratio to each other. are particularly useful for imparting desirable properties to fibrous materials, as is disclosed and On the basis of the reactions they undergo, claimed in copending application Serial No. 234, the products of the present invention are con , 842 ?led October 13, 1938, by W. E. Hanford. sidered to be substituted ethenones and to have Thus, substituted ethenones prepared from mix the following probable formula. in which R and tures containing octanoyl and higher molecular B.’ have the values hereinbefore given: 30 weight acyl halides impart both waterproo?ng and softening effects to such materials. With Two mechanisms which may account for the substituted ethenones of lower carbon content, production of substituted ethenones by the reac the outstanding change in properties is a favor able alteration of dyeing characteristics. tion of a primary acid chloride and a tertiary 35 amine are given in the following series of equa In the speci?cation and claims the term “pri mary monoacyl halide" is used to designate a tions: - s monoacyl halide in which the halide group is primary, i. e., attached to a methylene radical, thus, —CH2»—CO—X. The expression “hydro‘ 40 carbon primary monoacyl halide" indicates that the —CH2-—CO—X group is attached to a hydro carbon radical. The term “aliphatic carbon” is used to designate a non-aromatic carbon atom, i. e., a carbon which is not a part of an aromatic 45 (including an aromatic heterocyclic) ring. It is thus used to designate a carbon which may be an open chain carbon, an alicyc'lic carbon, or an all The exact course of the reaction cannot be phatic heterocyclic carbon. As already explained, predicted on the basis of known facts. In view the term “active hydrogen” is used to indicate of this, the products for absolutev accuracy must 50 hydrogen Joined to an inorganic element. at present be de?ned as the intermolecular de The term unsymmetrical ethenone is used to hydrohalogenation products of at leasttwo pri designate the intermolecular dehydrohalogena- mary monoacyl halides of the type hereinbefore tion products obtained from one mol of a primary given. monoacyl halide and one mol of a di?'erent pri When a mixture of acyl halides is dehydrohalo 55 mary monoacyl halide. The symmetrical eth genated, the formation of four different substi enone is similarly the intermolecular dehydro tuted ethenones is theoretically possible. The halogenation product of two molecules of the > formation of these four products may be ex same primary monoacyl halide. , plained on the basis of either of the two mecha ‘The above description and examples are in nisms proposed above. Using the ?rst of the 60 tended to be illustrative only. ’ Any modification above mechanisms, the reactions involved when of or variation therefrom which conforms to the a mixture of two primary acyl halides is dehy spirit of the invention is intended to be included drohalogenated may be as follows: . within the scope of the claims. 1 I claim: . 65 1. Process which comprises reacting, in an 2A->RCH:COC(R)CO (symmetrical product) anhydrous solvent, under anhydrous conditions, 2B-,+R'CH2COC(R') CO (symmetrical product) a mixture of. at least two primary monoacyl hal A+B—>RCH:COC(R') CO (unsymmetrical ides, each of which is free from groups reactive product, “C”) > under the conditions of the dehydrohalogenation 70 other than the one acyl halide group, with a satu product, “D”) ‘ rated tertiary aliphatic amine free from active hydrogen and selected from the ‘class consisting The symmetrical products are‘ disclosed in of monoamines and polyamines having any pair greater detail and ‘claimed in my application of nitrogens separated by a chain of at least two Serial No. 234,183, ?led of even date herewith. 75 carbon atoms, and isolating, also under anhy 2,238,826 drous conditions, an intermolecular dehydrohalo ing substantially identical with that obtained by genation product of two different acyl halides. reacting, under anhydrous conditions, a mix 2. Process which comprises reacting, in an an . ture of ‘ at least two primary monoacyl h'alides, hydrous solvent, a mixture of at least two hydro each of which is free from groups reactive under carbon primary monoacyl halides under anhy-‘ the conditions of dehydrohalogenation other than drous conditions with a saturated tertiary acyclic the one acyl halide group, with a saturated‘ ter monoamine free of active hydrogen, and isolat tiary ‘aliphatic monoamine, and isolating, also ing, also under anhydrous conditions, an unsym under anhydrous conditions, the ethenone. metrical ethenone. _ 8. An acyl ethenone of the probable formula 3. Process which comprises reacting, in an an 10 RCH2—-CO-C(>R')=CO wherein R and R’ are hydrous ,solvent, a mixture of primary fatty acid different monovalent organic radicals free of halides under anhydrous conditions with a satu groups reactive under the conditions of the de rated tertiary acyclic monoamine free of active hydrohalogenation, said ethenone being substan hydrogen, and isolating, also under anhydrous tially identical with that obtained by reacting, " conditions, an unsymmetrical ethenone. under anhydrous conditions, a mixture of at least ‘ 4. An intermolecular dehydrohalogenation two primary monoacyl halides each of which is product of two diiferent primary monoacyl hal free from groups, other than the one acyl halide ides. I group, reactive with acyl halides, ethenones, and 5. An intermolecular dehydrohalogenation tertiary amines and isolating, also under anhy product of two different primary hydrocarbon 20 drous conditions, the ethenone. " monoacyl halides. ‘ 9. The intermolecular dehydrohalogenation B. An intermolecular dehydrohalogenation product of dodecanoyl chlorideand acetyl chlo product of two different primary fatty acid hal ride. ‘ ' ides. 10. The, intermolecular dehydrohalogenation 7. An acyl ethenone of the probable formula product of propanoyl chloride and octanoyl chlo RCH2—~CO——C(R') :00 wherein R isv an organic ride. radical free of groups reactive under the condi 11. An intermolecular dehydrohalogenation tions of the dehydrohalogenation, and R’ is dif product of the mixture of fatty acid halides de ferent from R and- is chosen from the class con , rived from the mixture of fatty acids obtained by sisting of hydrogen and organic radicals free of 30 saponi?cation of a fatty oil. groups reactive at 170° C. with acyl halides, ethenones and tertiary amine, said ethenone be JOHN CARL SAUER.