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UNITED STATES PATENT OFFICE PROCESS of PREPARING 2,2-DIPHENYL-3- TRILEMETHYL-4-Dimethylamino-BUTYRONI Earl M

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UNITED STATES PATENT OFFICE PROCESS of PREPARING 2,2-DIPHENYL-3- TRILEMETHYL-4-Dimethylamino-BUTYRONI Earl M Patented Aug. 19, 1952 2,607,794 UNITED STATES PATENT OFFICE PROCESS OF PREPARING 2,2-DIPHENYL-3- TRILEMETHYL-4-DIMETHYLAMINo-BUTYRONI Earl M. Chamberlin, Rahway, and Max Tishler, Westfield, N.J., assignors to Merck & Co., Inc., Rahway, N.J., a corporation of New Jersey No Drawing. Application April 9, 1949, Seria No. 86,596 6 Claims. (CL 260-465) . 2 This invention relates to the manufacture of dimethylamino-butyronitrile (compound 5). Compounds possessing analgesic and anesthetic These reactions may be chemically represented action. In particular, it is concerned with an as follows: improved synthetic method for preparing 2,2-di phenyl 3-methyl-4-dimethylamino - butyronia CH3CHOHCHCl + RSO: C1 - cHipHCHCI trile and With novel chemical compounds useful Öso, R. as intermediates in the preparation of this come (1) (2) (3) pound. , 2,2-diphenyl-3-methyl - 4-dimethylami (C6H5)2CHCN no-butyronitrile is itself an important interne NaNH diate in the Synthesis of isoamidone, 1-dimethyl O amino-2-methyl-3,3-diphenylhexanone - 4 and (CH3)NH SaltS thereof. ISOamidone and its salts possess (C.H.)--HCH.N(CH), --- (CH)--HCH.Cl analgesic action and may be used as substitutes CE CH: for morphine. - N N 2,2-diphenyl-3-methyl - 4 - dimethylamino 5 (5) (4) butyronitrile has been prepared previously by The organic Sulfonyl chloride employed in the reacting 1-dimethylamino-2-chloropropane with foregoing reaction can be either an aromatic diphenylacetonitrile as described by Schultz et al. Sulfonyl chloride such as p-toluene sulfonyl chlo (J. A. C. S. 69, 188-189, Jan. 1947). As pointed ride, benzene Sulfonyl chloride and the like, or out by these workers, however, when 2,2-di 20 an aliphatic Sulfonyl chloride such as methane phenyl - 3 - methyl - 4-dimethlamino-butyroni Sulfonyl chloride. - trile is prepared by this procedure, there is ob The reaction between propylene chlorohydrin tained, at the same time and mixed with this and the aromatic sulfonyl chloride is ordinarily compound, the isomeric nitrile, 2,2-diphenyl-4- carried out in the presence of pyridine, prefer methyl-4-dimethylamino-butyronitrile. The lat 25 ably at a temperature of approximately 0° C. ter nitrile isomer constitutes an unwanted by Under these conditions, the reaction is usually product since it cannot be converted to isoami complete after a reaction period of 1 to 3 days. done. The pyridine hydrochloride, formed as a by Moreover, the preparation of isoamidone direct product of this reaction, ordinarily precipitates lyi from the mixture of isomeric nitriles has not 30 and is separated from the reaction mixture by proven feasible. In order to prepare isoamidone filtration. The filtrate is then mixed with Water it has therefore previously been necessary to iso and an Organic Water-immiscible solvent such late the desired 2,2-diphenyl-3-methyl - 4 - di as ether, chloroform, benzene, toluene, xylene methylamino-butyronitrile from the mixture and and the like. The ether layer is separated and this has necessitated a complicated separation 35 Washed. With an aqueous Solution of a mineral procedure which results in a considerable loss of acid Such as hydrochloric acid, hydrobromic acid, the desired isomer. Sulfuric acid, and the like, and then with Water. It is now discovered that the desired 2,2-di The ethereal Solution is dried and eyaporated to phenyl-3-methyl - 4 - dimethylamino-butyroni dryneSS under reduced pressure to produce, in trile can be prepared by a novel process which 40 the form of an oily residue, the corresponding 1 does not produce any of the unwanted isoneric methyl-2-chloroethyl organic sulfonate, as for nitrile. This improved method thus eliminates example i s methyl-2-chloroethyl-p-toluenesul the loss due to formation of the by-product iso fonate, 1-methyl-2-chloroethyl-benzeneSulfonate, ner and at the same time avoids the need for a 1-methyl-2-chloroethyl-nethaneSulfonate, and Complicated Separation procedure with its at 45 the like. tendant losses of the desired isomer. This product is ordinarily purified by treatment This novel process is conducted as follows: With aqueous pyridine to convert the residiai Propylene chlorohydrin (compound 1 below) is Organic Sulfonyl chloride to an acid. The resulti reacted with an Organic Sulfonyl chloride (com ing mixture is teated with an Organic Water-in pound 2) to produce the corresponding 1 SO iniscible Solwent and a dueoLS hydrochloric acid methyl-2-chloroethyl -sulfonate compound 3). and the layerS are separated. The Organic Sol This compound is then treated with the reaction Went layer is Washed first With an aqueous Solt product of diphenyl acetonitrile and sodamide tion of a raineral acid and then with water; the to produce 2,2 - diphenyl-3-methyl-4-chlorobu organic layer is then further purified, if desired, tyronitrile (compound 4) which is reacted with 55 by Washing With ala aqueous alkaline Solution dimethylamine to form 2,2-diphenyl-3-methyl-4- such as aqueous sodium hydroxide, aqueous po 2,607,794 3. 4 tassium hydroxide, aqueous ammonium hydrox this forming the unwanted 2,2-diphenyl-4- ide, and the like, and again with Water. The (organic-sulfonyl)-valeronitrile. The forma solvent layer is then dried and evaporated to dry tion of this compound, in other than Small ness in vacuo to produce the desired 1-methyl-2- amounts, would make the reaction impractical. chloroethyl organic sulfonate as a clear light The 2,2-diphenyl-3-methyl-4-chloro-butyro yellow oil which is ready for use in the reaction nitrile is then reacted with substantially anhy with diphenyl acetonitrile. drous dimethylamine. Small amounts of Water The above procedure can be varied by using are not harmful, but larger amounts result in a considerable excess of pyridine in the reaction a heterogeneous mixture of reactants. It is between the organic sulfonyl chloride and propyl O therefore preferred to conduct the reaction under ene chlorohydrin. Under these conditions, there substantially anhydrous conditions. It is ordi is an excess of pyridine present after the pyridine narily desired to employ an excess of dimethyl hydrochloride is removed by filtration. The ad amine in the reaction. Since dimethylamine is dition of water at this point followed by a stand a gas at room temperature, it is convenient to ing period results in complete hydrolysis of Sul mix the reactants together at a temperature fonyl chloride. The step of purifying the first below about 7° C. The mixture of reactants is oily residue is eliminated since the 1-methyl-2- . then heated in a pressure vessel to a tempera chloroethyl organic sulfonate formed at this ture of approximately 100-150° C. Under these stage is of satisfactory purity for employment conditions, the reaction is ordinarily complete in the subsequent reaction step. in approximately 48 hours. The 1-methyl-2-chloroethyl organic sulfonate If desired, the reaction can be carried out in is treated with the reaction product of diphenyl the presence of a solvent for the reactants, such acetonitrile and sodamide. The diphenylaceto as ethyl alcohol, and at a temperature of about nitrile is mixed with an equivalent molar quan 100-150° C. It has been found, however, that tity of sodamide and a liquid hydrocarbon, pref the presence of an organic solvent, such as erably a liquid having a boiling point of at least ethanol, tends to lower the yield. It is ordi about 110° C., such as xylene, toluene, or liquid narily preferred, therefore, to carry out the re petrolatum. The resulting mixture is heated action utilizing dimethylamine and 2,2-diphenyl and stirred until at least about 95% of the theo 3-methyl-4-chloro-butyronitrile as the sole.com retical amount of ammonia has been liberated, ponents," and to conduct the reaction at the which Ordinarily requires between about 3 and 5 higher temperature of 150° C. employing the hours. The reaction is Ordinarily carried out longer reaction period (48 hours), since these at a temperature of about 105-110° C. under re conditions have been found to result in the flux and in the presence of a nitrogen atmos obtainment of a higher yield than that obtain phere. able when the reaction is carried out in the This reaction mixture is then cooled to be presence of a solvent. tween about 70 and 90° C. and the 1-methyl-2- A mixture. Of Water and an Organic Water chloroethyl organic sulfonate is added thereto immiscible solvent Such as...ether, chloroform, rapidly, preferably keeping the temperature be benzene, toluene, xylene, and the like, is then low about 90° C. The resulting mixture is then 40 added to the reaction mixture and the Organic heated under reflux until the reaction is sub Solvent layer is extracted With an aqueous Solu stantially complete, which ordinarily requires tion of a mineral acid such as hydrobromic acid, about 14 to 18-hours. The reaction mixture is Sulfuric acid, and the like. The aqueous acid then mixed with water, and the organic layer extracts are then neutralized with an inorganic is separated, washed with water and dried. The base such as Sodium hydroxide, potassium hy Organic layer is evaporated to dryness to pro droxide, ammonium hydroxide and the like, and duce a crude product which may be used, if de the aqueous alkaline Solution extracted with an sired, in the subsequent reaction with dimethyl Organic Water-immiscible solvent. The organic amine. The crude product can be purified by Solvent extracts are combined and evaporated to distillation in vacuo to produce substantially 50 dryness in vacuo to produce crude 2,2-diphenyl pure 2,2-diphenyl-3-methyl-4-chloro-butyro 3-methyl-4-dimethyl-amino-butyronitrile. Since nitrile (compound 4). - this material is obtained by reaction of dimethyl AS pointed out above, the nitrile product pre amine With the single isomer, 2,2-diphenyl-3- pared in this way consists only of the desired methyl-4-chloro-butyronitrile, this product is 2,2-diphenyl - 3 - methyl-4-chloro-butyronitrile 55 likewise uncontaminated with any isomeric ni uncontaminated with any isomeric product.
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