Патент USA US2409700код для вставки
— Patented 0a. 22, 1946 “ ‘ ' 2,409,699 UNITED STATES PATENT OFFICE ' 2,409,699 PREPARATION OF CYANOMETHYL DIALKYL ORTHOFORM'ATES Donald J. Loder and William F. Gresham, Wil mington, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a cor poration of Delaware ‘ No Drawing. Application September '7, 1944, Serial No. 553,108 5 Claims. (Cl. 2‘60—464) This invention relates to the preparation of V charged with 28.5 parts 2(0.5 M) of formaldehyde orthoformates and more particularly cyanoalkyl a pressure of approximately 105 mm. During the dialkyl orthoformates by reacting alkyl orthofordistillation 31.6 parts of ethanol is recovered. The mates with aldehyde cyanhydrins. Yet another 10 product is then fractionated under a reduced are realized by‘su'bjecting an alkyl orthoiormate 15 . . . the process at a temperature ranging between 75 20 This exairiple illustrates the advantages de~ d Example II.—-The process of Example I is sub rated and purl?ed by fractlonatlon25 I and the cyanomethyl diethyl orthoformate ob he reaction is illustrated by the generic tained in a yield of approximately 56.2%. equation: The process illustrated in the examples may be HCXOR) 3+HORICN_>HC(OR) 2OR1CN+ROHV used for the preparation of a number of related in which R designates an alkyl and B1 an alkylene 30 produced by reacting the aldehyde cyanhydrins presence of an eizcess of the alkyl orthoformate 4r) athyl, methylpropyl, methylethylpropyl, and simi examples in which parts are by weight unless . _ otherwise indicated. general equatwn' Ervample I.—A round bottom glass ?ask is 55 HC(OR)zOR1CN+H2eHC(0R)onnmv-“?‘ 2,409,699 wherein R is an alkyl group and R1 an alkylene pressure, is obtained upon fractionation of the group. More speci?cally, valuable amines as aminoethyl diethyl orthoformate may besuch obtained in accord m . with the equation: product. Example IV.——The process of Example III is duplicated. employing 40 parts 5 substalrsltially (0.25 ) of cyanomethyl diethyl orthoformate, HC(OC2H5)2OCH2CN+2H2'> HC(OC2H5) zOCHzCHzNHz 85 parts M) catalyst of anhydrous ammonia and, parts of a (5 nickel supported on kieselguhr. The hydrogenation of the aminoethyl orthoThis reaction is conducted at a temperature be formates is preferably conducted under superattween 103 and 125° C. for approximately 4 hours mospheric pressures between 50 and 1500 utmost‘ 10“ under a hydrogen pressure of about ‘700 at Pheres and at temperatures ranging between 40 and. 150° C. Any s ‘table hydrogenation catalysts may be employed such, for example, nickel supported on kieselguhr, Raney nickel as catalysts, mospheres. Approximately an 87.5% conversion ‘ of the nitrile to the amine is realized. We 1, Aclaim; process for the preparation of a. cyano cobalt dial‘ 1 orthoformate which tocomprises like. catalysts, nickel chromite catalysts and the i5 methyl subjecting formaldehyde cyanhydrin a reac The examples which follow illustrate pi‘éfél‘i‘éd tion with an alkyl orthoformate in the presence of methods of converting the cyanoalkyl orthoiora condensation catalyst, mates to aminoalkyl orthoformates. In these 2. A process for the preparation of a cyano examples parts are by weight unless otherwise 20 methyl diethyl orthoformate which comprises indicated. subjecting formaldehyde cyanhydrin to a reac Exdmple III .-*—‘A silver-lined pressure-resisting tion with ethyl orthoiormate in the presence of autoclave is charged with 31.8 parts (0.2 M) of a condensation catalyst. cyanomethyl diethyl orthoformate, 85 parts (5 M) 3. A process for the preparation of a cyano of anhydrous ammonia and 20 parts of a nickel 25 methyl dialkyl orthoformate which comprises catalyst supported on kieselguhr. The reaction is subjecting an aldehyde cyanhydrin to a reaction conducted at a temperature between 108 and 112° C. under a hydrogen pressure of about ‘700 with a molar excess of an alkyl orthoformate at a temperature between 30 and 150° C. and in the atmospheres and for approximately 11/2 hours. presence of zinc chloride as the catalyst. Pressure is then released from the autoclave after 30 4. A cyanomethyl dialkyl orthoiormate. lowering the temperature and a ‘75.6% yield of 5. Cyanomethyl diethyl orthoformate. beta-amihoethyl diethyl orthoformate, a colorless liquid having a boiling point of 88° C. at 10 mm. DONALD J. LODER. WILLIAM F. GRESHAM.