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United States Patent Office Patented Apr. 7, 1953 2,634,292 UNITED STATES PATENT OFFICE 2,634,292 CYCLOHEXENYLETHYL AMINE AND PROC ESS FOR HE MANUFACTURE THEREOF Joseph Hellerbach, Basel, Switzerland, assignor to Hoffmann-La Roche Inc., Nutley, N.J., a cor poration of New Jersey No. Drawing. Original application May 27, 1950, Serial No. 164,849. Divided and this applica tion October 3, 1951, Serial No. 249,631. In Switzerland July 29, 1949 2 Claims. (Cl. 260-563) 1. 2 This invention relates to derivatives of mor- It has been found, according to this invention, phinane and4. salts -thereof - - - - - - if and. also to. intermes. : that morphinane and the derivatives thereof can anddiates salts used thereof, in the manufactureas well as to ofprocesses said derivatives for the be prepared according- to a process which may. be. ) manufacture of these compounds. 5 represented by the following formulae Scheme: 2,684,292 3 4 in which R, and R' are the same or different and effected. Free hydroxy groups (of the hydroxy are each a hydrogen atom or an OH, OCH3 or Or the dihydroxy-N-methyl-morphinane respec OCOCH3 group, and R'' and R'' are the same or tively) can be methylated or acetylated. different and are each a hydrogen atom or an The compounds or the Salts thereof, which are OCH3 group. obtained according to the present process, are The compounds of the general formulae I, III, effective as analgesics, IV, V, VI and VIII shown above are all new com In the following examples "parts' means pounds, Whilst the compound "parts by Weight' uniess otherwise stated. O EXAMPLE 1. N-CH CYCLOEIEXEN-(1)-YL-ETHYLAMINE (a) From cycloheacem- (1) -gl-acetamide 139 parts of cyclohexenyl-acetamide are added 5 in portions, with Stirring and ice-cooling, to a solution of 76 partS of lithium aluminium hy dride in 6000 parts of Water-free ether, the addi O CEa tion being Conducted under nitrogen. The re action mixture is allowed to Stand for 6 hours at (CH, 20 room temperature and thereafter kept boiling is new as well as compounds of the general for for 15 minutes. Afterwards the excess of lithium mula IX with the exception of N-methyl-mor aluminium hydride is decomposed slowly With phinane, 3,4-dihydroxy - N - methyl-morphinane Water and Concentrated Sodium hydroxide is and 3-methoxy-4-hydroxy-N-methyl-morphis added dropWise until the ether Solution becomes nane and it is to be understood that the present 25 Completely clear. The ethereal Solution is de invention comprises all these new compounds. Canted from the lithium and aluminium hydrox As starting material is used cyclohexen-(1)- ide and the residue is Washed twice With 150 yl-ethylamine (I) which itself may be obtained parts of ether each time. The united ether solu either from cyclohexen - (1) - yl - acetonitrile tions are dried With potaSSium carbonate and (Harding, Haworth, Perkin, J. Chem. Soc. (Lion 30 Concentrated, and the amine is distilled in the don), vol. 93, year 1908, pages 1945, 1956) or from vacuum of the Water-jet pump. (Boiling point cyclohexen- (1)-yl-acetannide (Wallach, "LiebigS 75-78° C. under a pressure of 15 mm.) Annalen der Chemie,' vol. 347, year 1906, page (b) From cycloheacem-(i)-yl-acetonitrile 328; “Liebigs Annalen der Chemie,' Vol. 353, year 1907, page 292; Darzens, Rost, Comptes RenduS, 35 121 parts of cyclohexenyl-acetonitrile dissolved vol. 153, year 1910, page 774) by reduction with in 800 parts of water-free ether are added drop lithium aluminium hydride. Wise, With Stirring, to a Solution of 42 parts of According to the present invention the amine lithium aluminium hydride in 2000 parts of (i) is reacted with phenyl-acetic acid or a Sub Water-free ether, the addition being performed stituted phenyl-acetic acid (II) to form the cor 40 at 0° C. under nitrogen; stirring is continued for responding phenyl-acetic acid (cyclohexenyl 2 hours at 0° C. ethyl)-amide (III). This latter compound is After decomposition of the excess of lithium converted under cyclization into the correspond aluminium hydride with water and addition of ing 1-benzyl-3,4,5,6,7,8 - hexahydroisoquinoline Concentrated Sodium hydroxide, the reaction (IV), this conversion being Suitably performed product is isolated according to the method de by means of condensing phosphorus compounds, 45 Scribed in part (a) of this example. such as phosphorus pentoxide or phosphorus EXAMPLE 2 halides. The methylation of IV into the N-meth ylated Octahyd'O Compound (WII) may be per N-METHYL-MORPHINANE formed in various WayS: 50 To a Solution of 125 parts of cyclohexenyl (a) By reacting a methylhalide with the hexa ethylamine in 250 parts of benzene are added hydro base (IV), the quaternary Salt (W) is ob slowly, with stirring and ice-cooling 85 parts of tained, which, upon catalytic hydrogenation, phenyl-acetic acid chloride in 170 parts of ben yields the hydrohalide of the N-methylated octa Zene. Thereafter the reaction product is allowed hydro Compound (VII). 55 to Stand for 30 minutes at room temperature (b) The hexahydro base (IV) may be reduced, and heated for additional 30 minutes on a water for instance, by catalytic hydrogenation, into the bath. The cyclohexenyl - ethyl - amine - hydro corresponding benzyl-Octahydro compound (WI), chloride is separated by filtration, the filtrate is and the latter may be reacted with formaldehyde Washed With Sodium hydrogen carbonate and and Subsequently reduced, So as to produce the 60 Water, and the solvent is distilled off; the residue desired 1-benzyl-2-methyl-Octahydro-isoquino Which Solidifies quickly is phenyl-acetic acid line (WII). - (cyclohexen-(l)-yl-ethyl)-amide. The raw ma (c) Upon treating a 1-benzyl-1,2,3,4,5,6,7,8- terial melts at 52-55. C., after recrystallization octahydroisoquinoline (WI). With ethyl formate, from a mixture of benzene and petroleum ether the formyl compound (VIII) is formed, which 65 at 69-70° C., and boils at 160° C. (temperature yields, when reduced by means of lithium alu of the oil-bath) under a pressure of 0.01 mm. minium hydride, the Corresponding 1-benzyl-2- 243 parts of phenyl acetic acid (cyclohexenyl methyl-octahydroisoquinoline (VII). ethyl)-amide are heated in an oil-bath together The l-benzyl-2-methyl-octahydroisoquinolines With 1200 parts of benzene and 730 parts of phos (VII) are converted into the N-methyl-morphi 70 phorous pentoxide at 90° C. for 45 minutes and nanes (IX) by heating with acid cyclizing agents, thereafter left standing for 2 hours at room tem Such as phosphoric acid or hydro halic acids and perature. Ice is then added with cooling to the the like. If the reaction is at the same time per reaction mixture, and the aqueous part is sep formed in a Suitable manner, a hydrolyzation of arated from the benzene. Upon addition at 0° the methoxy to free hydroxy groups may be 75 C. of Solid potassium hydroxide to the aqueous 2,634,292 5. 6 part, a base separates and is taken into ether. Solution is dried with potassium carbonate and The ether solution is dried, the solvent is driven then concentrated. off and the 1-benzyl-3,4,5,6,7,8-hexahydroiso The remaining 1-(p-methoxybenzyl)-3,4,5,6,7,8- quinoline is obtained as an oil. The same prod hexahydroisoquinoline (approximately 220 parts) uct is formed by phenyl-acetic acid (cyclohex 5 is dissolved in 5 times its quantity of methyl al enyl-ethyl)-amide being boiled for 3 hours With cohol and hydrogenated in the presence of 50 phosphorous Oxychloride in benzene. parts of Raney-nickel. After no more hydrogen The raw material is dissolved in 80 parts of is taken up, the solution is freed from the cata Water-free acetone, to this solution is added a lyst and acidified so far as just to become acid to mixture of 200 parts of methyl-bromide and 320 10 congo by means of 100 parts of 48 per cent hydro parts of water-free acetone and the whole is bromic acid. After removal of methyl alcohol, allowed to stand at room temperature for 12 the crystalline residue is recrystallized from hours. The residue, which remains after the water. The 1-(p-methoxy-benzyl)-1,2,3,4,5,6,7,8- acetone having been removed in vacuo at room octahydroisoquinoline - hydrobromide melts at temperature, is dissolved in water and extracted 5 200-201° C. with ether. The aqueous Solution of the quater A solution of 338 parts of 1-(p-methoxybenzyl)- nary salt is hydrogenated in a pressure autoclave 1,2,3,4,5,6,7,8 - octahydroisoquinoline - hydrobro for 19 hours together with a concentrated Solu mide in water is adjusted to a distinctly phenol tion of 56 parts of potassium hydroxide in meth phthalein-alkaline reaction by means of about anol in the presence of Raney-nickel, at room 20 100 parts of technical, aqueous sodium hydroxide temperature and under a preSSure of 50 atm. (about 30 per cent). The base which separates The hydrogenation product is freed from the is taken up in benzene and the benzene is dis catalyst by filtration and the methanol is Sub tilled off. The residue which is the free 1-(p- stantially removed by distillation. It is taken methoxy-benzyl)-octahydroisoquinoline-base is 2 3 dissolved in 600 parts of methanol. It is there into benzene and the benzene solution is washed after allowed to stand for 2 hours with 90 parts with Water. After distilling off the benzene, there of a formalin solution of approximately 40 per remains an oil which is 1-benzyl-2-methyl-1,2,3, cent.
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