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United States Patent (19) 11 4,175,197 Zimmerman 45) Nov United States Patent (19) 11 4,175,197 Zimmerman 45) Nov. 20, 1979 54) 1,3,4-TRISUBSTITUTED-4-ARYL-1,4,5,6-TET. 3,125,488 3/964 Biel .................................. 260/290 H RA-HYDROPYRONES 3,716,543 2/973 Hall ...................................... 54.6/350 3,847,930 1 1/1974 Randell et al. ....................... 54.6/339 75 Inventor: Dennis M. Zimmerman, Mooresville, 4,00,414 /977 Granados et al. ............... 260/.297 R Ind. 4,028,37 6/1977 Granados et al. ............... 260/297 R 73 Assignee: Eli Lilly and Company, Indianapolis, Primary Examiner-Alan L. Rotman Ind. Attorney, Agent, or Firm-Charles W. Ashbrook; Everet 21 Appl. No.: 905,494 F. Smith 22 Filed: May 12, 1978 (57) ABSTRACT Novel 1,3,4-trisubstituted-4-arylpiperidines are pre Related U.S. Application Data pared by alkylating a 2,3-disubstituted-3-arylpyrroline to afford a 1,2,3-trisubstituted-3-aryl-1-pyrrolinium salt, (60 Division of Ser. No. 852,252, Nov. 7, 1977, Pat. No. reacting the salt with diazomethane to provide a 1,2,3- 4,115,400, which is a division of Ser. No. 690,767, May trisubstituted-3-aryl-1,2-methylene-pyrrollidinium salt, 27, 976, Pat. No. 4,081,450, which is a continuation of heating the pyrrollidinium salt to effect a ring expansion Ser. No. 503,581, Sep. 6, 1974, abandoned. to the corresponding 1,3,4-trisubstituted-4-aryl-1,4,5,6- 51) Int. C.? ................... CO7D 213/04; CO7D 213/30 tetrahydropyridinium salt, neutralizing the salt and re 52 U.S. C. .................................... 54.6/339; 54.6/348; ducing the tetrahydropyridine to provide a 1,3,4-trisub 546/350, 54.6/344 stituted-4-arylpiperidine. The piperidines so formed are 58 Field of Search ....................... 260/290 H, 297 R; useful as pharmacological agents and as intermediates in 54.6/339, 348, 350 the preparation of other piperidines of the invention. (56) References Cited The compounds provided herein are especially useful as narcotic agonists analgesics and as narcotic antagonists. U.S. PATENT DOCUMENTS 2,748,140 5/1956 Schmidle et al. .................... 54.6/348 9 Claims, No Drawings 4,175, 197 2 1,3,4-TRISUBSTITUTED-4-ARYL-1,4,5,6-TETRA- SUMMARY OF THE INVENTION HYDROPYRONES In fulfillment of the above and other objects, the This is a division of application ser. No. 852,252 filed s present invention provides compounds of the formula Nov. 17, 1977, now U.S. Pat. No. 4,115,400, issued Sept. 19, 1978, which is a division of application Ser. No. R 690,767, filed May 27, 1976, now U.S. Pat. No. 4,081,450 which is a continuation of application Ser. No. 503,581, filed Sept. 6, 1974, now abandoned. BACKGROUND OF THE INVENTION Extensive research has been focused on agents that relieve pain and on their preparation. Interest has re cently developed in compounds that display antagonis 15 N tic activity against narcotic drugs, mainly for two rea sons. First, it is desirable to have narcotic antagonist compounds which give rise to analgesia while at the The invention further provides a process for preparing same time having a greatly reduced abuse potential. 20 1,3,4-trisubstituted-4-arylpiperidines comprising treat Sally is desirable E. s ing a 2,3-disubstituted-3-aryl-1-pyrroline with an alkyl norcodeineuseful in the is treatmentprobably theof firstnarcotic specific addiction. narcotic N-allyl- antag ating agent to afford the corresponding 1,2,3-trisub onist prepared and studied. It was synthesized by J. stituted-3-arylpyrrolinium salt, reacting the salta so Pohl in 1914. Several similar compounds have been 25 formed with diazomethane to obtain the novel bicyclic synthesized in an effort to prepare a long-acting orally pyrrolidinium salt having the general formula effective antagonist. In general, all of these compounds are characterized by a relatively short duration of ac- R4' tion, low oral effectiveness, and varying degrees of agonistic effects. 30 R3 Several compounds of the piperidine class have been ye, found to display interesting analgesic activity, and some N have displayed varying degrees of antagonist activity, RCH NR as described for example by Nurimoto and Hayashi, Japan J. Pharmcol. 23743 (1973). Many 1,2,3-trialkyl-3- 35 arylpiperidines have been prepared and evaluated as heating the bicyclic pyrrolidinium salt to a temperature analgesic drugs; see for example U.S. Pat. Nos. sufficient to effect a ring expansion to produce a 1,3,4- 3,043,845 and 2,892,842. Very interesting antagonistic trisubstituted-4-aryl-1,4,5,6-tetrahydropyridinium salt, properties have been displayed by a group of 1,4-disub- 40 neutralizing the salt and reducing the tetrahydropyri stituted-4-arylpiperidines, as described by Langbein, et dine to the corresponding 1,3,4-trisubstituted-4-aryl al., Narcotic Antagonists, Advances in Biochemical Psy- piperidine. The piperidine so formed can be converted chopharmacology, Vol. 8, Raven Press, New York, 1974, to other piperidines of the invention by standard proce pp. 157-165. Several 1-methyl-4-alkyl-4-(3-hydroxy- dures phenyl)piperidineshenvl)piperidi were prepared and evaluated as an-- 454 In the foregoing formulae, R is hydrogen, C1-C8 algesics by McElvain, U.S. Pat. No. 2,892,842. Very little work has been directed to the preparation alkyl, C4-C8 (cycloalkyl)alkyl, benzyl, C3-C8 alkenyl, of 1,3,4-trisubstituted-4-arylpiperidines, presumably C3-C8 alkynyl, or substituted alkyl, because of the difficulty of their preparation. McElvain R1' is a subgroup of R which includes C-C8 alkyl, et al. reported the preparation of 1,3,4-trimethyl-4-(2-0 C4-C8(cycloalkyl)alkyl, and benzyl; methoxyphenyl)piperidine as a bi-product in the syn- R2 is hydrogen, C1-C4 alkyl, or C2-C6 alkenyl; thesis of a 1,4-dialkyl-4-arylpiperidine; J. Am. Chem. R3 is C1-C4 alkyl, or C-C6 alkenyl; Soc. 80, 3918 (1958). It was reported, however, that an ortho- or para-methoxyl group on the phenyl substitu R4 is hydrogen, hydroxy, C1-C3 alkoxy, or acyloxy; ent rendered such compounds almost totally inactive as 55 R4 is a subgroup of R4 consisting of hydrogen, hy analgesics. Similarly, Janssen prepared several l-aroyl droxy, and C1-C3 alkoxy; and 3,4-dialkyl-4-arylpiperidine derivatives which are useful Ye is a non-nucleophilic anion. as central nervous system depressants, U.S. Pat. No. Also included within the scope of this invention are 3,080,372. 60 the pharmaceutically acceptable acid addition salts and forIt preparing is an object 4-arylpiperidines of this invention substituted to Provide in a theProcess 1,3, quaternary ammonium salts of the piperidines provided and 4-positions with alkyl or alkenyl groups. It is a herein. further object to provide such piperidines which dis- DETALED DESCRIPTION OF THE play useful analgesic activity and which, in some cases, 65 INVENTION are potent narcotic antagonists. An additional object of the invention is to provide novel intermediates useful The compounds provided by this invention include for preparing new piperidines. those having the general structural formula 4, 175, 197 4. phenylaminopropyl, 2-(3-methylthiophenyl)ethyl, 3-(4- nitrophenyl)propyl, (3-aminophenyl)methyl, (4-tri fluoromethylphenyl)methyl, 2-(3-hydroxyphenyl)ethyl, (3,4-dimethylphenyl)methyl, (3,4-dimethoxyphenyl)- methyl, (3,4-dichlorophenoxy)methyl, 2-(3-nitro-4- chlorophenyl)ethyl, N-(3,4-dichlorophenyl)-N-acetyl laminomethyl, (2-thiophene)methyl, 2-(3-thi opene)ethyl, 2-(2-thiophene)-2-oxo-ethyl, 2-(2-furyl)-2- RCH2 hydroxyethyl, 3-2-(5-methylthiophene)-2-propenyl, N O and the like. R2 in the above formula is hydrogen, C1-C4 alkyl, or R C2-C6 alkenyl. Examples of C1-C4 alkyl include methyl, ethyl, isobutyl, and n-butyl. Typical C2-C6 alkenyl and the pharmaceutically acceptable salts thereof. groups include vinyl, allyl, 4-methyl-3-pentenyl, 5 R in the above formula is hydrogen, C3-C8 alkenyl, 15 C3-C8 alkynyl, substituted alkyl, C1-Cs alkyl, C4-C8 hexenyl, and the like. (cycloalkyl)alkyl, or benzyl. R4 in Formula I is hydrogen, hydroxy, C1-C3 alkoxy, The term "C1-Cs alkyl" refers to straight or branched or acyloxy. The term "C1-C3 alkoxy' includes me carbon chains having no more than eight carbons. Ex thoxy, ethoxy, propoxy, and isopropoxy. The term amples of C1-C8 alkyl groups include methyl, ethyl, "acyloxy' refers to C1-Cl2 alkanoyloxy groups such as isopropyl, isobutyl, pentyl, 3-methylheptyl, octyl, and 20 acetoxy, butyroxy, pentanoyloxy, isohexanoyloxy, 4 the like. "C3-C8 alkenyl' refers to groups having the butyloctanoyloxy, lauroyloxy, and the like. The term formula CH2A, wherein A is C2-C7 alkenyl. Examples "acyloxy" also refers to groups of the formulae of C3-C8 alkenyl groups include allyl, 3-butenyl, 3 methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 5-octenyl, and the like. Similarly, "C3-C8 alkynyl' refers to groups 25 having the formula CH2B, wherein B is C-C7 alkynyl. Examples of such C3-C8 alkynyl groups include 2-pro pynyl, 3-butynyl, 4-hexynyl, 4-methyl-5-hexynyl, 6 (O), octynyl, and the like. Typical examples of C4-C8 (cy 30 cloalkyl)alkyl groups include cyclopropylmethyl, 1 in which m is 0 or 1. cyclopropylethyl, 2-cyclopropylethyl, cyclobutyl While most of the piperidines of this invention are methyl, 2-cyclobutylpropyl, (2-methylcyclobutyl)- conveniently prepared by the process described herein methyl, 2-cyclohexylethyl, and the like. The term "sub below, a preferred aspect of the invention comprises stituted alkyl' refers to groups having the formula 35 carrying out the process with pyrrolines bearing substit uents which are not modified by any subsequent step of the reaction sequence and which can be easily manipu Rs lated to provide either compounds of the invention or -(CH2)-(X) intermediates therefore.
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