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UNITED STATES PATENT OFFICE 2,500,444 URAMIDOHOMOMEROQUINENE Robert Burns Woodward, Cambridge, Mass., and William Von Eggers Doering, New York, N

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UNITED STATES PATENT OFFICE 2,500,444 URAMIDOHOMOMEROQUINENE Robert Burns Woodward, Cambridge, Mass., and William Von Eggers Doering, New York, N Patented Mar. 14, 1950 2,500,444 UNITED STATES PATENT OFFICE 2,500,444 URAMIDOHOMOMEROQUINENE Robert Burns Woodward, Cambridge, Mass., and William von Eggers Doering, New York, N. Y., assignors to Polaroid Corporation, Cambridge, Mass., a corporation of Delaware No Drawing. Application October 10, 1944, Serial No. 558,080 Claim. (C. 260-294) 2 This invention relates to the synthesis of Which stereoisomers may be isolated as chemical quinine and cinchona-like alkaloids. individuals and then subjected to further trans The present application is a continuation-in formation. It is preferable, however, instead of part of our copending applications Serial No. 508,- isolating the stereoisoners from their mixture, to 954, filed November 4, 1943, now Patent No. 2,475,- Oxidize the latter and thus form a mixture of the 932, entitled "7-hydroxyisoquinoline derivatives Corresponding ketones, i. e., the stereoisomers of and method of preparing the same,' and Serial 2-acetyl-7-keto - 8-methyldecahydroisoquino No. 523,940, filed February 25, 1944, now Patent line, and to isolate from the latter mixture the No. 2,395,526, entitled “Isoquinoline derivatives Stereochemically homogeneous products. The and methods of preparing the same.' 10 carbocyclic ring of each stereoisomeric ketone may It is one object of the present invention to pro then be cleaved to give the corresponding N vide a novel process of synthesizing homonero acetyl - 10 - oximinodihydrohomomeroquinene quinene from isoquinoline derivatives. ethyl ester having the formula Another object is to provide novel quinine and cinchona-like alkaloids, and particularly al H. kaloids having the structural formula of quinine 5 /\H NoH and quinotoxine, derived from 1-cis-homonero CH3CON 5C-C-CE quinene and racemic-cis-homomeroquinene and O from one of the trans-homomeroquinenes. 7 8 9 Still another object is to provide novel 7-hy C2 4C-CICEICO OEt; droxyisoquinoline derivatives and Specifically the 20 N3/ N - acetyl - 10 - aminodihydrohomomeroquinene ethyl esters, the salts of Said esters, the N-acetyl 10 - trimethylammonium - dihydrohomomero The latter compound is catalytically hydrogenated quinene ethyl ester iodides and uranidohomo 25 to transform the oximino group to an amino meroquinenes. group. The hydrogenation may be carried out According to the method of the present inven without a solvent to give the corresponding amino tion, 7-hydroxyisoquinoline ester, but is preferably performed in an acidic Sol vent, such as acetic acid, whereby the correspond E. E. 30 ing amino salt, N - acetyl - 10 - aminodihydro N34in Yo1 /w w o O homomeroquinene ethyl ester acetate, having the formula, Hc & 4. 5 CH E. SH NH-HOAC is transformed to 7-hydroxy-8-methylisoquinoline 35 chicoy (-CH-CH, C C-CECCO OEt and the latter is converted to its tetrahydro deriv N/H. ative, 1,2,3,4-tetrahydro - 7 -hydroxy - 8 - meth C ylisoquinoline, from which the N-acetyl derivative, 2 - acetyl-1,2,3,4 - tetrahydro - 7 - hydroxy - 8 is formed. The amino compound is methylated, methylisoquinoline, having the formula for example with methyl iodide, to give N acetyl - 10 - trimethylammoniumdihydrohomo meroquinene ethyl esteriodidehaving the formula 45 NH N(CH)32 CaCO (-CH-CH, H. g-CH,Chicooet is obtained. The latter product is then converted C into a mixture of stereoisomers of 2 - acetyl-7- 50 EI hydroxy-8-methyldecahydroisoquinoline having which can be decomposed to homomeroquinene, the formula the latter being isolated as its uramido derivative. 55 NOC-N /SHC-CeCe. H. (-CHCH.cooH CSf 2,500, 444 3 4. The uramidohomomeroquinene is hydrolyzed to 7-hydroxyisoquinoline derivative having an N obtain the free racemic homomeroquinene Substituted-aminomethyl group, i.e., -CH2-N <, attached to the eight position of the isoquinoline C ring, the Specific amino Substituent depending B on the one of the primary and secondary annines HN/ YE-CH=CH, which is used as a reaction ingredient. The 7 H2C (-CHCH.cooH hydroxy-8-N-substituted aminomethylisoquino N/H line is thereafter reduced by reacting Said product Ea with an alkali methoxide, such as sodium methox The racemic homomeroquinene thus obtained will 10 ide or potassium methoxide, preferably in a hy have a cis Cr trans configuration, depending upon droxylic Solvent, such as methanol. The reduc the configuration of the stereoisomer of 2-acetyl tion may be carried out in an autoclave and pre 7 - keto - 8 - methyl decahydroisoquinoline from ferred temperature and time ranges therefor are Which the homomeroquinene is synthesized. between 200 and 250° C. and from six to sixteen Either of these racemic mixtures of homomero- 5 hours. The reaction products comprise the alkali quinene can be converted by esterification and Salt, e. g., the Sodium or potassium Sait, of 7-hy benzoyiation to N-benzoylhomomeroquinene ethyl droxy-8-methylisoquinoline, and Said salt is neu ester, and the latter can be condensed with ethyl tralized by acidification to free the 7-hydroxy-8- quininate, as by following the general methods methylisoquinoline, the latter compound being of Rabe disclosed in Berichte der Chemischen ( thereafter isolated from the reaction products, Gesellschaft 51, 1360 (1918); ibid., 52, 1842 (1919), preferably by Sublimation and crystallization. and of Prostenik and Prelog disclosed in Helvetica The 7-hydroxy-8-methylisoquinoline Inay be Chemica Acta, 26, 1965 (1943), to form the cor purified, for example, by forming the oxalate of responding racemic mixtures having the struc said co:npound, crystallizing Said oxalate and tural formula of quinotoxine. The l- and d 2: then liberating the pure 7-hydroxy-8-methyliso isomers of these quinotoxine-like compounds may quinoline. be resolived, as for example, by means of diben The 7-hydroxy-8-methylisoquinoline is hydro ZOyl-d-tartaric acid, d-quinotoxine-dibenzoyl-d- genafed over a suitable catalyst, as for example tartrate being less soluble in water than 1-quino platinum, being thus smoothly and quantitatively toxine-di-dibenzoyl-d-tartrate. From any of 30 converted to the tetrahydro-derivative, 1,2,3,4- these isomers, or either of the racemic mixtures tetrahydro-7-hydroxy-8-methylisoquinoline. It thereof, the corresponding cinchona-like alkaloids is to be expressly understood that while platinum having the Structural formula of quinine, includ is the preferred catalyst for this purpose, other. ing the novel racemic quinine and d-quinine, may hydrogenation catalysts, Such as nickel, may be be obtained, for example, by means of the con S 5 enployed. The tetrahydro-derivative is there version reported by Rabe in Berichte der Chem after converted into the corresponding N-acetyl ischen Gesellschaft, 51, 466 (1918). To make d derivative, 2-acetyl-1,2,3,4-tetrahydro-7-hydroxy quinine the starting material is liquinotoxine 8-methylisoquinoline, by reaction With acetic an Which is converted to a mixture of stereo-isomeric hydride in ethanol and this N-acetyl-derivative is quinines according to the method described by 40 hydrogenated, as for example, over Raney nickel Rabe and analogous to the method described to give a practically quantitative yield of a rix herein, followed by resolution of the optical ture of stereoisoners of 2-acetyl-7-hydroxy-8- isomers to give d-quinine. The l-quinotoxine is methyldecahydroisoquinoline. A certain propor employed to make d-quinine. tion of each of the stereoisomers in this reaction. The method of the present invention is pref 4. mixture can be isolated as a chemical individual erably carried out with 7-hydroxyisoquinoline as and when so isolated may thereafter be subjected the Starting material and the latter is reacted to the following transformation in the pure form. With formaldehyde and a compound from the However, it is preferable to oxidize the crude inix class consisting of primary and secondary amines, ture of the stereoisomers to produce the cor these ingredients being preferably mixed in a ii responding stereoisomeric ketones, since this proc hydroxylic Solvent, such as ethanol, methanol and ess reduces by one the number of asymmetric Water, or in a mixture of said solvents, as for centers in the molecule. From the mixture of . example, aqueous ethanol and aqueous methanol. ketones thus obtained the crystalline site:eochein The formaldehyde may be obtained from any ically homogeneous cis ketone may be isolated as suitable Source and may be conveniently intro- 55 a hydrate. This form of stereochemical indi duced into the reaction mixture in aqueous solu vidual has the same configuration as the cor tion. The primary or secondary amine may, for responding atoms of the quinine molecule. example, be any one of the following: piperidine, The stereoisoner of 2-acetyl-7-keto-3-innethyl morpholine, aniline and its homologues, and the decahydroisoquinoline thus obtained is cleaved alkyl and dialkyl amines, such as methylamine, 80 between the 7- and 8-positions of its carbocyclic ethylamine, dimethylamine, diethylamine, neth ring to give the N-acetyl-10-oximinodihydro yethylaxine, propylamine, dipropylamine, homomeroquinene ethyl ester. The cleavage is methylpropylamine, ethylpropylamine, ethyl accomplished by reacting the ketone with ethyl butylamine, isopropylbutylamine, as Well as aryl nitrite and Sodium methoxide, best results being Substituted derivatives of said alkyl and of said 65 obtained during this step of the giocess by ex dialkylamines. The completely aromatic second cluding moisture from the reaction. To accorn alry amines, as for exaltaple diphenylanine, and plish this all of the materials are preferably puri the aromatic heterocyclic amines such as indole fied just prior to use and are handled in vessels and thiazole, are less preferred than the non equipped, for example, with calcium chloride aromatic heterocyclic secondary amines, such as 70 tubes in order to obtain a complete exclusion of morpholine and piperidine and the noia-cyclic moisture. A rigid exclusion of moisture is also amines having, at least one alkyl group attached effected during the reaction. to the nitrogen, such as the alkyl and dialkyl The N-acetyl- 10 - OXininodihydrohonomero amines.
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