US3959309_TOT

US3959309_TOT - United States Patent [191 [111 3,959,309...

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Unformatted text preview: United States Patent [191 [111 3,959,309 Mooradian @flgmmmw 0033,; [451*May 25, 1976 [54] 3-AMIDO-1,2,3,4- 3,634,420 1/1972 - Littell et al. ...................... ._ 260/315 TETRAHYDROCARBAZOLES 3,642,816 2/1972 Mooradian ........................ .. 260/3 IS [75] Inventor: Aram Mooradian, Schodack, N.Y. OTHER PUBLICATIONS [73] Assignee: Sterling Drug Inc., New York, NY. * _ . J. Pharmacol. Expt’l. Therap. 99: 450—457 (1950), [ ] Notice: The portion of the term of this Eagle et al. patent subsequent to Feb. 15, 1989, has been disclaimed. Can. J. Chem. 42: 1940—1947 (1964), Robinson et al. [22] Filed: Dec. 17, 1973 Chemical Abstracts 57: 97826 (1962), Murthy et al. [21] Appl. No.2 425,205 163] [301 [52] 151] 1581 [56] 3,592,824 Related US. Application Data Continuation-impart of Ser. No. 172,206, Aug. 16, 1971, abandoned, which is a continuation-in-part of Ser. No. 793,545, Jan. 23, l969,-abandoned, which is a continuation-in-part of Ser. No. 659,606, Aug. 10, 1967, Pat. No. 3,642,816. Foreign Application Priority Data Jan. 24, 1968 Canada ................................ .. 10686 US. Cl. ..................... .. 260/315; 260/247.5 FP; , 260/293.61; 424/267; 424/274 Int. Cl}. ..................................... .. C07D 209/88 Field of Search ................................... .. 260/315 References Cited UNITED STATES PATENTS 7/1971 Schut ................................ .. 260/315 Primary Examiner—Sherman D. Winters Attorney, Agent, or Firm—Frederik W. Stonner; B. Woodrow Wyatt [57] ABSTRACT 3-(Substituted-amino)- 1 ,2,3,4-tetrahydrocarbazoles are prepared by reacting appropriate 4-substituted- aminocyclohexanones with a phenylhydrazine, by re-"’ acting a 3-(sulfonyloxy)-1 ,2,3,4-tetrahydrocarbazole with an appropriate substituted amine, or by reduction of an appropriate 3—( acylamino )— l ,2,3 ,4- tetrahydrocarbazole. The 3—(substituted-amino)- 1,2,3,4—tetrahydrocarbazoles of this invention have an- algetic and psychotropic activities. Moreover, certain of these compounds also have antihistaminic activity. 9 Claims, No Drawings 3,959,309 1 3-AMIDO- 1 ,2,3,4-TETRAHY DROCARBAZOLES This application is a continuation-in-part of applica- . tion Ser. No. 172,206, filed Aug. 16, 1971, now aban- doned, in turn a continuation—in-part of application Ser. No. 793,545, filed Jan. 23, 1969, now abandoned, in turn a continuation-in-part of application Ser. No. 659,606, filed Aug. 10, 1967, now US. Pat. No. 3,642,816, issued Feb. 15, 1972. This invention relates to a class of chemical com— pounds known in the art of chemistry as 1,2,3,4-tet- rahydrocarbazoles, to the preparation thereof, and to intermediates therefor. In one aspect of this invention there are provided novel 3-(N=B)-9—R—1,2,3,4-tetrahydrocarbazoles hav- ing the structural formula N=B / w—z-v where N=B is NI-IR', NR’R” or NR’” —Y-NR’R", where R' and R” are lower-alkyl or Ar-lower-alkyl, or R' and R" taken together with the nitrogen form a heterocyclic ring selected from 4—morpholinyl, 4—thi— omorpholinyl, l-piperidinyl, l—pyrrolidinyl, l-piperazi— nyl, 4-lower-alkyl-l-piperazinyl and 4-Ar—1-piperazi- nyl, R'" is hydrogen or lower-alkyl and Y is lower-alky— lene; R is hydrogen, lower-alkyl, Ar—lower-alkyl, lower— alkenyl, hydroxy-lower-alkyl, lower—alkanoyloxy—low— er-alkyl, Ar-carbonyloxy—lower-alkyl, carboxy-lower- alkyl, lower—alkoxycarbonyl-lower—alkyl or Ar-lower- alkoxycarbonyl-lower-alkyl, or R is Y—NR'R”, where Y, R’ and R” have the same meaning given above; 01 is selected from the substituents of the groups desig- nated (l), (3) and (4) below; 02 is selected from the substituents of the groups designated (2), (3) and (4) below; Q3 is selected from the substituents of the groups designated (3) and (4) below; 04 is selected from the substituents of the groups designated (2) and (4) below, where the substituents of the groups desig- nated (1), (2), (3) and (4) are respectively: 1. Ar-low— er-alkyl, Ar——O, Ar, cyano, formyl, —CH20H, —CH20C—R., —(|i—O—Rl, _C—NR,R,1 ll ll 0 o o and —CH2NR2R3, where Rl is hydrogen, lower-alkyl, Ar or ——CH2Ar, and R2 and R3 are hyrogen or lower- alkyl, or R2 and R3 taken together with the nitrogen form a heterocyclic ring selected from 4-morpholinyl, 4-thi0morpholinyl, l-piperidinyl, l—pyrrolidinyl, l- piperazinyl, 4-Ar—l-piperazinyl and 4—alkyl-l-piperazi- nyl, (2) tertiary-lower-alkyl, Ar-lower-alkoxy, hydroxy, trihalomethyl, nitro, amino, lower—alkylamino, di(low- er-alkyl)amino and lower-alkanoylamino, (3) lower— alkylthio, lower-alkyl-sulfinyl and lower-alkyl—sulfonyl, and (4) hydrogen, non-tertiary-lower—alkyl, lower- 10 15 20 25 30 35 2 alkoxy and halo, provided that when Oz and Q, are selected from the substituents of the group designated ( 2) they are non-adjacent and when Q, and Oz or Q1, Q2 and 03 are substituents selected from the group designated (3) they are identical); and Ar is phenyl or phenyl substituted by from one to three of the same or different substituents selected from non—tertiary-lower- alkyl, non-adjacent tertiary-lower-alkyl, lower-alkoxy, non-adjacent trihalomethyl, non-adjacent nitro and halo; where lower-alkyl, lower-alkoxy and lower-alkan- oyl, every occurrence, have from one to six carbon atoms, lower~alkenyl has from three to six carbon atoms and lower-alkylene has from two to four carbon atoms. A preferred group of compounds of this invention are the compounds of formula I where R is hydrogen or lower—alkyl, O1 is selected from hydrogen, lower—alkyl, halo, Ar—O and Ar and 02, Q, and 04 are selected from hydrogen, lower—alkyl and halo. A more preferred group of compounds of this inven- tion are the compounds of formula I where N=B is NI-{R’ or NR’R", where R' and R” are lower—alkyl, R is hydrogen or lower~alkyl, Q1 is selected from hydro- gen, lower-alkyl, halo, Ar—O and Ar and 02, Q3 and Q4 are selected from hydrogen, lower-alkyl and halo. A more particularly preferred group of compounds of this invention are the compounds of formula I where N=B is methylamino or dimethylamino, R is hydrogen and 0,, 02, Q3 and 04 are selected from hydrogen, lower-alkyl and halo. Two especially preferred groups of compounds of this invention are the compounds of formula I where N=B is methylamino or dimethylamino, R is hydrogen, Q1 and Q2 are hydrogen and Q3 and 04 either are se- lected from hydrogen and fluoro or from hydrogen and ' methyl. 40 45 50 55 6O 65 In another aspect of this invention there is provided 3-(dimethylamino)—6-fluoro-9-(4—fluorophenyl)- l,2,3,4-tetrahydrocarbazole having the structural for— mula 3 F N\ CH3 N F IA By virtue of possessing asymetric carbon atom, that is, the carbon atom at the 3-position of the 1,2,3,4 -tetrahydrocarbazole ring, each of the compounds within the scope of formulas I and the compound of formula IA can exist as optical isomers, that is, in two 'stereoisomeric forms (enantiomers), whose molecular structure as mirror images of each other. Therefore, 3,959,309 3 within the purview of this invention are the dextrorota- tory isomers and Ievorotatory isomers, hereinafter the d- and I—isomers, and the d,l~mixtures thereof, herein— after racemic mixtures, of the compounds of formulas I and IA. The racemic mixture of any particular com- pound within the scope of formulas l and IA, obtained directly by the synthetic procedures described herein— below, is separated into the d-isomer and 1-isomer, using standard resolution procedures. Thus the racemic mixture is converted to a mixture of two diastcreomeric acid-addition salts by reaction, using standard proce- dures, with a suitable optically active acid, e.g., d-tar- taric acid, 1-malic acid, l~mandelic acid, d-camphor- lO—sulfonic acid, dibenzoyl l-tartaric acid and the like and the resulting two diastereomeric salts in the mix— ture, which are no longer identical or mirror images and therefore possess different physical properties, are separated by conventional physical procedures such as crystallization. The two separated diastereomeric salts so obtained can then be converted by standard proce— dures, e.g., by treatment with base, to the correspond— ing d-isomer and l-isomer. In a further aspect of this invention there are pro— vided novel 3-(NR”'—CO—R5) l ,2,3,4-tetrahydrocar- bazoles having the structural formula R”! l N—CO—R Q" 5 n N l H II where R5 is hydrogen, lower~alkyl or Ar; R'” is hydro- gen or lower—alkyl; Q” is fluoro; n is an integer from I to 4; and Ar is phenyl or phenyl substituted by from one to three of the same or different substituents se- lected from non-tertiary-lower-alkyl, non-adjacent ter- tiary—lower-alkyl, lower-alkoxy, non-adjacent trihalo— methyl, non-adjacent nitro and halo; where lower-alkyl and lower-alkoxy, every occurrence, have from one to six carbon atoms. In still another apsect of this invention there are provided novel 3-(OZ)-9-R4-1 ,2,3 ,4-tetrahydrocar- bazoles having the structural formula I Q 1 OZ Q'2 | Q'B III Q'4 R14 IIA where Z is hydrogen or II Ar—~C—; l0 IS 20 30 35 40 45 50 55 6O 65 4 R4 is hydrogen, lower-alkyl, Ar—lower-alky, lower-alke- nyl, carboxy-lower-alkyl or lower—alkoxycarbonyl—low— er-alkyl, or R4 is Y—NR’R", where R’ and R" are lower-alkyl or Ar-lower—alkyl, or R' and R" taken to— gether with the nitrogen form a heterocyclic ring se- lected from 4-morpholinyl, 4-thiomorpholinyl, 1- piperidinyl, l—pyrrolidinyl, l —piperazinyl, 4—lower- alkyl-l—piperazinyl and 4-Ar—l—piperazinyl and Y is lower—alkylene; Q'I is selected from the substituents of the groups designated (1), (3) and (4) below; Q’2 is selected from the substituents of the groups designated (2), (3) and (4) below; 0’3 is selected from the substit- uents of the groups designated (3) and (4) below; QC, is selected from the substituents of the groups desig— nated (2) and (4) below, where the substituents of the groups designated (1), (2), (3),and (4) are respec- tively: (1) Ar-lower—alkyl, Ar-O and Ar, (2) tertiary- lower-alkyl, Ar-lower-alkoxy, trihalomethyl, nitro, di(— lower-alkyl)arnino and lower—alkanoylamino, (3) low- er-alkylthio, lower-alkyl-sulfinyl and lower-alkyl-sulfo- nyl, and (4) hydrogen, non-tertiary-lower-alkyl, lower— alkoxy and halo, provided that when Z is hydrogen then R., cannot be lower—a1koxycarbonyl—lower—alkyl, when R4 is hydrogen or lower~alkyl at least one of 0’1, 0'2, 0’3 and 0'4 is other than hydrogen or lower—alkyl, when 0’2 and Q", are selected from the substituents of the group designated (2) they are non-adjacent and when 0’, and 0’2 or 0’1, 0’2 and Q’,; are selected from the substituents of the group designated ( 3) they are identi- cal; and Ar is phenyl or phenyl substituted by from one to three of the same or different substituents selected from non-tertiary-lower-alkyl, non-adjacent tertiary— lower—alkyl, lower-alkoxy, non-adjacent trihalomethyl, non-adjacent nitro and halo; where lower—alkyl, lower— alkoxy and lower-alkanoyl, every occurrence, have from one to six carbon atoms, lower—alkenyl as from three to six carbon atoms and lower-alkylene has from two to four carbon atoms. In yet another aspect of this invention there are pro- vided novel 3-(OZI)-9-R’4-1,2,3,4-tetrahydrocar- bazoles having the structural formula Q! Q! 1 OZ:L 2 l Q'; N Q'u liq!“ IIB where Z1 is Ar—SOz——, Ar—lower—alkyl-SOz—, or low— er-alkyl-SOg—; RC, is hydrogen, lower—alkyl, Ar-lower— alkyl, lower-alkenyl or carboxy-lower-alkyl, or RC, is Y-NR’R”, where R’ and R" are lower-alkyl or Ar-low- er-alkyl, or R’ and R” taken together with the nitrogen form a heterocyclic ring selected from 4amorpholinyl, 4-thi0morpholinyl, 1-piperidinyl, 1-pyrrolidinyl, l- piperazinyl, 4-lower-alkyl—1-piperazinyl and 4Ar-l- piperazinyl and Y is lower~alkylene; Q'1 is selected from the substituents of the groups designated (1), (3) 3,959,309 5 and (4) below; Q’2 is selected from the substituents of the groups designated (2), (3) and (4) below; Q’s is selected from the substituents of the groups designated (3) and (4) below; 0’4 is selected from the substituents _ of the groups designated (2) and (4) below, where the substituents of the groups designated ( l ), (2), (3) and (4) are respectively: (1) Ar-lower-alkyl, Ar-O and Ar, (2) tertiary—lower-alky], Ar-lower—alkoxy, trihalo- methyl, nitro, di(lower-alkyl)amino and lower- alkanoylamino, (3) lower-alkylthio, lower-alkyl—sulfi- nyl and lower-alkyl-sulfonyl, and (4) hydrogen, non— tertiary—lower-alkyl, Iower—alkoxy and halo, provided that when 0,2 and Q’4 areselected from the substitu- ents of the group designated (2) they are non-adjacent and when 0’1 and Q’2 or Q’,, Q’-2, and Q’3 are selected from the substituents of the group designated (3) they are identical; and Ar is phenyl or phenyl substituted by from one to three of the same or different substituents selected from non-tertiary—lower-alkyl, non—adjacent tertiary-lower-alkyl, lower-alkoxy, non-adjacent tribal— omethyl, non-adjacent nitro and halo; where lower- alkyl, Iower-alkoxy and lbwer-alkanoyl, every occur— rence, have from one to six carbon atoms, lower-alke— nyl has from three to six carbon atoms and lower-alky- lene has from two to four carbon atoms. The compounds of this invention having the formula I were found to be therapeutically active substances which possess useful pharmacodynamic properties as determined by test procedures more fully disclosed hereinbelow. Thus, they possess analgetic and psycho- tropic activities and are indicated for use as analgetic and psychotherapeutic agents. Moreover, certain of these compounds also possess antihistaminic activity and are indicated for use as antihistamines. The com- pound of formula IA possesses analgetic activity and is indicated for use as an analgetic agent. Compounds having the formulas [1, [IA and [IB are useful as intermediates in the preparation of the novel compounds of formula I. Here and throughout the specification it will be un— derstood that when Ar bears substituents, as defined hereinbefore, such substituents can be attached to any of the available positions of the Ar ring and when there are two or three such substituents they can be the same or different and they can be in any of the various posi— tion combinations relative to each other except as oth- erwise defined hereinbefore. Similarly it will be under- stood that substituents represented by 01, 02, ()3 and Q4 (hereinafter QM), 0’1, 0’2, 0’3 and Q’4 (hereinafter 0’14) and Q", defined hereinbefore, may be attached to any of the available positions, i.e., the 5,6,7 and 8 positions, of the 1,2,3,4-tetrahydrocarbazole ring and corresponding positions of the phenyl ring of the phen- ylhydrazine starting materials (IV and [VA below) and where there are more than one such substituents they can be in any of the various position combinations relative to each other except as otherwise defined here- inbefore. It will also be understood that as used throughout this specification, N=B, R, Ar, QM, R4, R’,, 0’”, Q”, Z and Z1 each have the meaning hereinbefore defined except where otherwise specifically defined hereinbe- low. As used throughout this specification, the term “halo” includes chloro, bromo, iodo and fluoro; and terms “lower-alkyl”, “lower-alkanoyl”, and “lower- alkoxy” mean such groups'preferably containing from one to six carbon atoms which can be arranged as 10 15 20 25 30 35 6 straight or branched chains, and, without limiting the generality of the foregoing, are illustrated by methyl, ethyl, propyl, isopropyl, butyl, sec—butyl, amyl, hexyl and the like for lower-alkyl, acetyl, propionyl, trime- thylacetyl hexanoyl and the like for lower-alkanoyl, and methoxy, ethoxy, isobutoxy, tert—butoxy, hexoxy and the like for lower—alkoxy; the term “lower-alky- lene” means a group preferably containing from two to four carbon atoms with its connecting linkages on dif— ferent carbon atoms, and without limiting the general- ity of the foregoing, is illustrated by [,2—ethylene, 1,3- propylene, 1,2-( l—methylethylene), 1,4—butylene, and the like; and the term “lower-alkenyl” means a group preferably containing from three to six carbon atoms which can be arranged in straight or branched chains, and, without limiting the generality of the foregoing, is illustrated by allyl, 2-butenyl, 3-methyl—2-butenyl, and the like. The novel l,2,3,4-tetrahydrocarbazole final products of the instant invention are the compounds of formulas I and IA and the acid-addition and quaternary ammo- nium salts thereof. The compounds of formulas I and IA, in free base form, are converted to the acid-addi- tion salt form by interaction of the base with an acid. Conversely, the free bases can be regenerated from the acid-addition salt form in a conventional manner, that is, by treating the salts with strong aqueous bases, for example alkali metal hydroxides, alkali metal carbon- ates, and alkali metal bicarbontes. The bases thus re- generated can then be interacted with the same or a different acid to give back the same or a different acid- addition salt. Thus the novel bases and all of their acid- addition salts are readily inter-convertible. It will thus be appreciated that Formula I not only represents the structural configuration of the bases of ' Formula I but is also representative of the structural 40 45 50 55 60 65 entity which is common to all of my compounds of Formula I, whether in the form of the free bases or in the form of the acid—addition salts of the bases. I have found that by virtue of this common structural entity, the bases and their acid-addition salts have inherent pharmacodynamic acitivity of a type more fully de- scribed hereinbelow. This inherent pharmacodynamic activity can be enjoyed in useful form for pharmaceuti- cal purposes by employing the free bases themselves or the acid-addition salts formed from pharmaceutically- acceptable acids, that is, acids whose anions are innoc— uous to the animal organism in effective doses of the salts so that beneficial properties inherent in the com- mon structural entity represented by the free bases are not vitiated by side-effects ascribable to the anions. In utilizing this pharmacodynamic activity of the salts of the invention, I prefer of course to use pharmaceuti- cally-acceptable salts. Although water-insolubility, high toxicity, or lack of crystalline character may make some particular salt species unsuitable or less desirable for use as such in a given pharmaceutical application, the water-insoluble or toxic salts can be converted to the corresponding pharmaceutically-acceptable bases by decomposition of the salt with aqueous base as ex- plained above, or alternatively, they can be converted to any desired pharmaceutically-acceptable acid-addi— tion salt by double decomposition reactions involving the anions, for example, by ion-exchange procedures. Moreover, apart from their usefulness in pharmaceu— tical applications, my salts are useful as characterizing or identifying derivatives of the free bases or in isola— tion or purification procedures. Like all of the acid- 3,959,309 11 potassium hydroxide. Where R4 of compound V] is lower—a1koxycarbonyl-lower-a1kyl, the corresponding compound VII, where R4 is carboxy-lower~alkyl, is obtained. 12 conveniently carried out by heating the reactants in acetic acid or in ethanolic hydrochloric acid at reflux temperature for one hour. The reaction proceeds via the corresponding 4-benzoyloxycyclohexanone phenyl~ The intermediate 5 hydrazone precursor which can be isolated, if desired, 0 if excess acid is avoided, e.g., if the amount of acid H employed is not in excess of one equivalent the amount 34 o - rC—Ar)—9-R4-l ,3}.4-tetrahydrocarhuzoles (VI ) of phenylhydrazine employed. Subsequent treatment of 10 the phenylhydrazone precursor under acidic condi— . g . tions, as described above, will effect cyclization to the are prepared by means of the Fischer indole SynthBSlS. corresponding tetrahydmcarbazole VI_ Thusa they are Obtamed by {330ng an approprlate The following reaction sequence illustrates the above phenylhydrazme (1V below) With a method of Synthesis; l5 I Q l 9. O—C-Ar I Q 2 + v N—NH Q 3 l 2 o > Q' 4 R14 IV V Q'l 0 ll Q' O-C-Ar 2 l i Q 3 N Q l I I ll R14 base VI . Q] 1 Q. 2 __/ OH 2101 (21 g H) IIB W Q! 3 N Q! I I 14 P 4 VII 0 II 4-(O—C—Ar )-cyclohexunone (V below) in an acidic medium, at elevated temperatures, for from about lxé hour to 24 hours. Acids which may be employed as cyclizing agents are inorganic acids such as hydrochloric acid or hydrobromic acid, mineral acids such as sulfuric acid or phosphoric acid, and organic acids such as acetic acid and methanesulfonic acid as well as Lewis acids such as boron trifluoride. The acidic agent should be present in at least one mole excess per mole of the phenylhydrazine. The reaction is 60 65 The cyclohexanone starting materials (V) are pre- pared from 4—hydroxy-cyclohexanone by conventional esterification procedures using known acids or their corresponding acid chlorides. The sulfonyl chlorides (Z,Cl; Zl 9e H) belong to a well known class of compounds and can be prepared by standard procedures, e.g., by treatment of the corre— sponding sulfonic acids with a suitable chlorinating agent such as thionyl chloride, phosphorus pentachlo- ride or phosphorus oxychloride. In a second process certain compounds of formula I are prepared by means of the Fischer indole synthesis, 3,959,309 13 that is, by reacting a l-R-l-(QM) phenylhydrazine (IVA) with a 4-(N=B)-cyclohexanone (VIII) and, if desired, isolating and subsequently cyclizing, the corre— sponding 4—(N=B)-cyclohexanone phenylhydrazone , precursor, using procedures similar to that described hereinbefore for the preparation of the tetrahydrocar- bazoles having formula VI. However, the phenylhydra- zines (IVA) utilized in this method, and hence com- pounds of formula I prepared by this method, cannot bear certain substituents represented by 0,, 02 and O, which interfere with, or will not survive, the‘reaction conditions of the Fischer indole synthesis and such substituents are introduced subsequent to the cycliza- tion procedure as described hereinbelow. The follow- IO ing reaction sequence illustrates the synthetic method: 15 Q1 , Q2 + Q3 N—NH2 Q. ll 0 It IVA Q1 Q3 N Q I 4 R I In either of the two above-described processes for the preparation of the compounds of formula I, when the phenylhydrazine (IV or IVA) is unsymmetrically sub- VIII stituted by one or two 0’“ or QM substituents respec- 45 tively and bears a hydrogen atom or each a-position of the phenyl ring, cyclization can occur at either of the a-positions and thus generally two isomeric tetrahy- drocarbazoles are obtained. The relative amounts of the two isomers so obtained will vary depending on the 50 degree of substitution and the nature of the substitu— ents. The isomers can be separated by means of con- ventional isolation and purification procedures. The formation of two isomers can be avoided, if desired, by utilizing in the cyclization reaction an appropriately substituted phenylhydrazine additionally bearing an a—bromo or az-chloro substituent on the phenyl ring. The corresponding 8-bromo or 8-chloro substituent of - the compound of formula I thus obtained by either of the above-described procedures is then reductiver 60 removed by catalytic hydrogenation. The hydrogena- tion can be Carried out at room temperature in a suit- able solvent, e.g., ethyl or methyl alcohol, in the pres- ence of palladium on charcoal catalyst at atmospheric or elevated’pressure. The hydrogenation can be per— formed under neutral conditions but is preferably carred out in the presence of at least an equivalent amount of an acidacceptor such as potassium hydrox- ide. 14 The compound of formula IA can be prepared by the above—described Fischer indole procedure by reaction of the known I,1—bis(4-fluorophenyl)hydrazine with 3—dimethylaminocyclohexanone. The 4—(N=B)-cyclohexanone starting materials (VIII) are prepared from 4-(p-toluenesulfonyloxy)- ‘cyclohexanone by displacement of the p-toluenesul- fonyloxy group with the amine HN=B (III), using the procedure described hereinabove, followed by conven- tional acid hydrolysis of the resulting 4-(N=B)— cyclohexanone enamine, or are prepared from 4- hydroxycyclohexanone by reaction with the amine HN=B (III), using conventional procedures, to obtain the corresponding 4—hydroxycyclohexanone enamine, catalytic reduction of the latter, e.g., over 10% palla- dium on charcoal, and finally oxidation of the resulting 4-(N=B)-cyclohexanole, using conventional oxidation procedures, e.g., with chromium trioxide in acetic acid or in acetone—sulfuric acid, to give the corresponding 4-( N=B )-cyclohexanone. The phenylhydrazine starting materials (IV and IVA) belong to a class of compounds well known in the art of . organic chemistry and can be prepared by well known 55 65 methods of Synthesis, fer example, by reaction of the corresponding (014)-NR— and (Q'H)-NR4— anilines, where 0,, Q2 and 04 cannot represent certain substitu— ents as described hereinbelow, with sodium nitrite in water in the presence of hydrochloric acid and subse- quent reduction of the diazonium chloride or N-nitroso - intermediate so obtained with an appropriate reducing agent, e.g., stannous chloride (SnClZ) or lithium alumi- num hydride. The hydrochlorides of the resulting hy- drazines are prepared by conventional methods. The HN=B (III) starting materials are well known in the art of organic chemistry and are generally available or can be prepared by conventional processes. For example, diamines represented by the formula HN=B, ‘where N=B is NR"’—Y-NR’R", can be prepared by reacting an appropriate amine, for example, a 1- phenylpiperazine, with a halo-lower-alkylnitrile, for 3,959,309 15 example, chloroacetonitrile, to give an aiminolower- alkyl-nitrile, for example, a (4-phenyl-l—piperazinyl)- acetonitrile, which can then be reduced by conven— tional methods to the corresponding diamine (R"’=H), for example, a 2-(4—phenyl-l-piperazinyl)-ethylamine. The diamines where R’” is lower—alkyl can be prepared from the corresponding diamines where R’” is hydro- gen by conventional acylation procedures, e.g., by re- action with formic acid or formamide or an appropriate lower—alkanoic acid halide, followed by conventional chemical reduction of the corresponding amides so obtained, e.g., with lithium aluminum hydride. The lower—alkanoic acid halides are known compounds or are readily prepared by conventional procedures from the known acids. In a similar manner compounds of 1 formula I where N=B is NHR’ or NR’R", where R’ and R” are lower-alkyl or Ar-lower-alkyl, or N=B is NR"A '-Y—NR’R", where R’” is lower—alkyl are prepared from the corresponding 3-(NH2)- or 3-(N=B)-1,2,3,4- tetrahydrocarbazoles where N=B is NHR’ or NH-Y- NR'R” respectively, by reaction with formamide or an appropriate carboxylic acid halide followed by chemi- cal reduction of the corresponding 3-amido-l ,2,3,4—tet- rahydrocarbazole so obtained. Where R of formula I is hydrogen, the aeylation step is preferably carried out with formamide or under aqueous conditions, that is, by reacting the appropriate amino compound with an appropriate lower—alkanoic acid halide in dilute aque- ous alkali, e.g., dilute sodium hydroxide solution, in order to avoid acylation of the unsubstituted tetrahy- drocarbazole nitrogen atom (position 9). Alternatively, the 3-amido-1,2,3,4-tetrahydrocarbazole intermediates can be obtained directly by means of the Fischer indole synthesis by employing an appropriate 4—amidocy- clohexanone. The latter can be prepared from the cor- responding 4-(NH2)- or 4-(N=B)-cyclohexanone (IX), where N=B is NHR’ or NH-Y-NR'R”, by the conven- tional N-acylation methods disclosed above. Compounds of formula I where 02 and/or Q,I are lower-alkanoylamino or lower-alkylamino can be pre- pared from the corresponding compounds where 02 and/or 0,1 are amino using the conventional N-acyla- tion and chemical reductive methods disclosed above. The compounds of formula I and formula VI when prepared by the processes described above, can be substituted at the 9-position by hydrogen (R and R4=I~I respectively) or by other substituents as hereinbefore defined for R and R4. When R and R4 are hydrogen, then appropriate substituents, if desired, can be intro- duced at the 9-position by reacting these compounds with a compound of separated and formula RX or R4X (R and R4 96 H) respectively wherein X is chlorine, bromine or iodine, in a suitable solvent at elevated temperatures and in the presence of a strong base for about one—half hour to eight hours. The reaction is preferably carried out in dimethylformamide in the presence of sodium hydride at 75°C. to 90°C. for about two hours. Where R and R.1 are carboxy-lower-alkyl or lower-alkoxycarbonyl-lower—alkyl or R is Ar-lower- alkoxycarbonyl—lower-alkyl, such substituents can also be introduced by reacting the corresponding com- pounds where R and R4 are hydrogen with acrylonitrile or an appropriate acrylic acid ester to give the corre- sponding cyanoethyl or carboxyethyl ester compounds, and in the case of the former compound, further treat- ing that compound under aqueous hydrolysis condi- tions, e.g., in aqueous ethanolic potassium hydroxide I0 5 20 25 30 35 40 45 50 55 60 65 16 under reflux for several hours, to give the correspond- ing carboxyethyl compound. The RX and R4X (R and R4 aé H) starting materials are generally well known in the art of organic chemistry and can be prepared readily by conventional processes, for example, by reaction of the corresponding alcohols in a suitable solvent with a suitable acid halide, e.g., thionyl chloride, in the presence of a base, e.g., pyri- dine. The acrylic acid esters are generally known com- pounds. Compounds of formula I, where 02 and Q4 are se- lected from amino and hydroxy substituents, or where 01 is selected from the substituents of the group desig— nated (I), defined hereinabove, excluding Ar-lower- alkyl, Ar—O, Ar and _C—o—R,. ll 0 are not prepared directly by the Fischer indole proce- dure described hereinabOve but can be prepared by the methods described as follows: The compounds of formula I where 02 and Q4 are selected from amino and hydroxy substituents can be prepared by well known catalytic hydrogenation proce- dures from the corresponding compounds where 02 and 04 are selected from nitro and benzyloxy substitu- ents, whereby said substituents are converted to amino and/or hydroxy substituents. The hydrogenation can be carried out at room temperature in an inert solvent, e.g., ethyl alcohol, under essentially neutral conditions in the presence of a suitable catalyst, e.g., Raney nickel or palladium on charcoal, at atmospheric or elevated pressures, the hydrogenation being stopped after a stoichiometric amount of hydrogen has reacted. The compounds of formula I where 01 is formyl, —CH20I-I, 0 || -CH,oc—R.. —C—OR. (R. séI-I), o 0 II fl — —NR2R3 and —'CH2NR2R3 can be prepared from the corre- sponding compound, where O1 is carboxy, by conven- tional procedures, more fully described hereinbelow, well known in the art of organic chemistry. Compounds of formula I wherein o I! Q. is —C—0R,. wherein R1 is lower-alkyl, Ar or —CH2-—-Ar, can be prepared from the corresponding compounds where Ql is carboxy by conversion of said carboxy compound to the acid choride using conventional procedures, for example, reaction in a suitable solvent with thionyl chloride, and reaction of the acid chloride so obtained with an alcohol of the formula RIOH (R, 9‘ H), both ‘ reaction steps being carried out in the presence of a suitable acid acceptor, e.g., pyridine or triethylamine. However, when a carboxyphenylhydrazine is employed in the Fischer indole synthesis and the reaction is car- ried out in an appropriate alcohol, e.g., ethyl alcohol, in the presence of excess acid, the corresponding ester, e.g., ethyl ester, is obtained directly. Compounds of formula I wherein 3,959,309 17 0 ll 0. is —C—NR._.R3 can be prepared from the corresponding acid chlorides described hereinabove by reaction with an amine hav- ing the formula RZRSNH in the presence of a suitable acid acceptor, e.g., pyridine or triethylamine. Compounds of formula I wherein Q, is —CH20H or —CH2NR2R3 can be prepared by redUCtion of the cor- responding esters or amides, i'.e., corresponding com- pounds where O1 is if ‘i l —C—0Rl (Rl # H) or -—C—NR2R,._ Ljrespectively using conventional reduction procedures. 3A preferred procedure is chemical reduction of the - 'ester or amide. Conveniently the ester or amide, in a suitable solvent, e.g., ether or tetrahydrofuran, is treated with lithium aluminum hydride (LAH) for from about one to about twenty hours and the resulting a1— coholate is decomposed with acid, e.g., dilute hydro— chloric acid. The reaction is generally carried out at temperatures ranging from about 20°C. to about 60°C. The compounds of formula I wherein O1 is o - - ll ;, —Ci-_i:o—_c,—R, can be prepared from the corresponding compounds wherein O1 is —CH20H by reaction with an acid chlor— ide having the formula i? R.C—Cl, 5-2 where Ql is Cl or Br CuCN QI=CN 18 or equivalent acid halides, by the conventional proce— dure for reacting an acid chloride and an alcohol as described hereinabove. The acid chlorides l| (RIC—Cl), 10' 15 20 25 3O 35 the amines (R2R3Nl-l) and the alcohols (RIOH, R1 96 H) used in the above—described methods of synthesis belong to well—known classes of compounds and are readily available or prepared from readily available starting materials using well-known procedures. The compounds of formula I wherein Ql is formyl 0 ll (-C—H) can be prepared from the corresponding compounds where 01 is —CH20l-l by conventional oxidation pro- cedure, i.e., by manganese dioxide (MnOz) oxidation. The reaction is conveniently carried out by treating a solution of the alcohol (Or—CH20H) in a suitable solvent, e.g., acetone, with an excess of manganese dioxide at about 20°C. to about 50°C. for from one to 20 hours. The compounds of formula I where Q] is cyano are prepared from the corresponding compounds where Ql is bromo or chloro by reaction with cuprous cyanide in a suitable solvent at elevated temperatures. The reac- tion is conveniently performed in dimethylformamide at reflux temperature for about four hours. The following reaction sequences illustrate the above-described methods of synthesis. 0 II where Ol= ~C—OH SOCI.z 0 ll Ol= —C—Cl R-anNH RICH (R.#H) O 0 ll ll Ql= —C—NR2R3 Q.= -—C—OR. LAH / LAH Qt: _CH2NR2R:i Q.= —CH20H O MnO2 || RIC—Cl 0 ll Qt: —‘C‘_H 0 || o,= --CH20—C-—-R, 3,959,309 19 Psychotropic activity of the compounds of this inven- tion was determined in the test procedures described hereinbelow. la. Reserpine Ptosis Prevention in Mice Unfasted male mice, grouped in cages of eight ani- mals each, were injected intraperitoneally (1P) with the test agent. Two hours later the mice were injected IP with 2 mg./kg. of reserpine. Three hours after the ad— ministration of reserpine the degree of eyelid ptosis was scored. 1f the test agent was significantly active, the minimal dose at which activity was noted was deter— mined. 1b. Reserpine Ptosis Reversal in Mice This test is similar to Test la described above, except the mice first received reserpine, and three hours later, when ptosis was evident, they were challenged with the test agent. Each mouse was scored one—half hour after 20 the drug injection. 2. Overt Behavioral Effects in Monkeys and Cats The animals were medicated orally (P0) with the test agent and observed for changes in behavior. The pre- test agent scored overt behavioral profile was com- pared to the post-test agent overt behavioral profile at various inte rvais. 3. Spontaneous Psychomotor Activity of Mice The effect of the test agent on the spontaneous activ— ity of mice was determined in a photocell-counter ac— tivity cage. Thirty minutes before being placed in the activity cage, groups of four mice each were medicated orally (P0) with graded doses of the test agent. Activ— ity (psychomotor stimulation or depression) was mea- sured by means of a digital counter recording the num— ber of times a beam of light impinging on a photocell was broken during a thirty-minute period. 4, Hexobarbital Potentiation Groups often male mice were medicated orally (PO) and intraperitoneally (IP) with the test agent at 100 mg./kg. and 10 mg./kg. both forty and ninety minutes prior to a subhypnotic dose of sodium hexobarbital (4O mg./kg.) injected 1?. The mice were tested for loss of righting reflex 10, 15, and 20 minutes following the sodium hexobarbital injection. The test was considered positive if the mice lost their righting reflex for 1 min— ute. 5. Maximal Electroshock Groups of ten male mice were medicated orally (PO) and intraperitoneally (1?) with the test agent at 100 mg./kg. and 10 mg./kg. both thirty and ninety minutes prior to the application of an electroshock of fifty milli- amps of AC. current for three-tenths of a second through Spiegal Corneal electrodes. The test was con- sidered positive if the mice failed to exhibit the tonic hind-leg extension phase of the seizure. 6. Pentylenetetrazol Antagonism Groups of ten male mice were medicated orally (PO) and intraperitoneally (IP) with the test agent at 100 mg./kg. and 10 mg./kg. both thirty and ninety minutes prior to a rapid intravenous injection of pentylenetetra- 15 25 35 40 45 50 55 60 65 20 201 (50 mg./kg.). The test was considered positive if the tonic hind—leg extension phase of the seizure was blocked. The antihistaminic activity of the compounds of this invention having Formula I was determined by the following test procedure: 7. Antihistamine Test Procedure The test agents, made up to appropriate concentra— tions in distilled water or as suspensions in 1% gum tragacanth, were injected subcutaneously (SC) thirty minutes prior to the intravenous administration of a challenging close of 0.57 mg./kg, (as base) of histamine diphosphate into albino guinea pigs separated into groups of three pigs each. Two groups of five pigs each served as controls and these pigs received subcutane- ous injections of l ml./kg. of 1% gum tragacanth and distilled water, respectively, thirty minutes prior to the challenging dose of the histamine. All of the control animals died. The doses at which fifty-percent of the pigs were protected by the active test agents were re— corded as the ED50: standard error. The analgetic activity of the compounds of this in— vention having Formula I was determined by the fol- lowing test procedure: 8. Analgetic Test Procedure Inhibition of Phenquuinone — Induced Writhing in Mice The test agent was administered subcutaneously prior to intraperitoneal injection of phenyl—p-quinone (PPQ). After PPQ treatment the mice are observed, and the total number of writhes for each mouse during specified intervals is recorded. More than 98% of the control mice writhe at least 3 times during the observa— tion period. Any animal writhing s 2 times is consid— ered protected. The percent of mice protected is plot- ted against dose (30 animals perdose) for determina— tion of the ED50. (ED50 is the dose at which fifty-per- cent of the mice were protected). The novel compounds of this invention having For— mula I were found to have useful analgetic activity when administered subcutaneously to mice in the dose range of 3 mg./kg. to 100 mg./kg. For purposes of comparison, the known compound, 3—amino~ 1 ,2,3 ,4«tetrahydrocarbazole hydrochloride was prepared by heating 18.8 g of 3—p-toluenesu1- fonyloxy—l,2,3,4—tetrahydrocarbazole with 300 ml. of a solution of ethyl alcohol saturated with ammonia, in a pressure reaction vessel, at 100°C. to 119°C. for 12 hours. The mixture was evaporated to dryness and the residue was treated with 10% sodium hydroxide solu— tion. The resulting free base was collected by filtration and on treatment with ethanolic hydrogen chloride was converted to 3-amino-1,2,3,4-tetrahydrocarbazole hy- drochloride which was collected by filtration and which melted at 298°—299°C. (corr.). The known 3—amino-1,2,3,4-tetrahydrocarbazole was completely inactive in the antihistamine test procedure (7). Test procedure In: active at 30 mg./kg. Test procedure 1b: active at 10 mg./kg. Test procedure 3: active at 8 mg./kg. My invention is illustrated by the following examples without, however, being limited thereto. 3,959,309 21 EXAMPLE 1 3-(Dimethylamino)-1 ,2,3,4-tetrahydrocarbazole V To .a refluxing solution of 9.2 g. of 4-dime— thylaminocyclohexanone in 23.5 g. of glacial acetic acid was added dropwise 7.1 g. of phenylhydrazine and the mixture refluxed for one hour. The solvent was removed by distillation under reduced pressure, the residue made basic with dilute sodium hydroxide solu— tion and extracted with ehterl. The ether extracts were dried and the ether evaporated to give an orange solu— tion which crystallized upon cooling. The solid was collected by filtration then recrystallized from metha- nol to give 4 g. of 3-(dimethylamino)—1,2,3,4-tetrahy- drocarbazole which melted at l38°—142 C. (corr.). Treatment of an absolute alcohol solution of the free base with alcoholic hydrochloric acid gave a white solid which was collected by filtration. There was thus ob- tained 3-(dimethylamino)-1 ,2,3,4-tetrahydrocarbazole hydrochloride which melted at 25 3°-—255°C. (uncorr.). Test procedure 1a: active at 10 mg./kg. Test procedure 1b: active at 10 mg./kg. Test procedure 2; taming in monkeys at 4 mg./kg. Test procedure 4: active at 50 mg./kg. (1P) This compound was active as an antihistamine at 0.6 i 0.1 mg./kg. in test procedure 7. I EXAMPLE 2 3-Acetamido-1 ,2 ,3 ,4-tetrahydrocarbazole Following the procedure given in Example 1 and using 30 g. of 4—acetamidocyclohexanone and excess phenylhydrazine there was obtained 3 g. of 3- acetamido-l,2,3,4-tetrahydrocarbazole which melted at 165°—167°C. (corr.). EXAMPLE 3 3-( Dimethylamino)-6-methoxy71 ,2,3,4-tetrahydrocar— bazole A mixture of 4-dimethylaminocyclohexanone hydro— chloride, prepared from 19.8 g. of 4-dimethylaminocy- clohexandne, in alcoholic hydrogen chloride and 24.6 g. of p-methoxyphenylhydrazine hydrochloride in etha- nol was warmed on a steam bath for 1 hour. The ammo— nium chloride which precipitated was removed by fil- tration and the filtrate evaporated in vacuo. The solid residue was taken up in water, made basic with dilute sodium hydroxide and extracted with ether. Evapora- tion of the ether extracts gave an oil which crystallized upon cooling. Recrystallization from ethyl acetate gave 22.4 g. of 3-(dimethylamino)—6-methoxy1,2,3,4-tet- rahydrocarbazole which melted at 126°—128°C. (corr.). Test procedure 3: active at 100 mg./kg. Test procedure 4: active at 50 rug/kg; (IP) Test procedure 7: active at 36.5 i 7.3 mg./kg. Alternatively, 37(dimethylamino)-6—methoxy- 1,2,3,4-tetrahydrocarbazole can be prepared by follow- ing the procedure given in Example 18 below and using - 3—(p—toluenesulfonyloxy )-6-methoxy- l ,2,3 ,4—tetrahy- ' drocarbazole and dimethylamine. The 3—(p—toluenesulfonyloxy)-6—methoxy—1,2,3,4—tet— rahydrocarbazole can be prepared from 3-hydroxy-6- 1‘22 methoxyl ,2,3,4—tetrahydrocarbazole and tosyl chloride by following a procedure similar to that described in Example 1.8. - 5 The 3-hydroxy—6- methoxy-l ,2 ,3 ,4-tetrahydrocar— bazole, was prepared as follows: A suspension of 25.6»g. of 3-benzoyloxy—6-methoxy— 1,2,3,4—tetrahydrocarbazole in 250 ml. ethyl alcohol was treated with 50 ml. of an aqueous solution contain— ing 6.5 g. potassum hydroxide and heated on a steam bath for one and one-half hours. The alcohol was dis— tilled under reduced pressure and the residue was treated with ethyl alcohol - water. The resulting precip- itate was collected and recrystallized from ethylene dichloride” to give 12.3 g. 3-hydroxy-6-methoxy- 1,2,3,4—tetrahydrocarbazole; m.p. 1 19°—122°C. The 3-benzoyloxy-6-methoxy-_1 ,2,3 ,4-tetrahydrocar- bazole was prepared as follows: To a suspension of 4—methoxyphenylhydrazine hy- drochloride in 200 m1. ethyl alcohol was added 21.8 g. of 4—benzolyoxycyclohexanone and the mixture was heated under reflux for one and one-half hours. The mixture was filtered and the filtrate was evaporated to dryness under reduced pressure; the residue was slur- ried in water and the resulting 3-benzoyloxy-6-methox- yl,2,3,4—tetrahydrocarbazole, m.p. l35°-141°C., was collected by filtration. By following the procedure described in Example 3, substituting for p-methoxyphenylhydrazine hydrochlo~ ride an equivalent amount of an acid-addition salt of: a. 2-ethylphenylhydrazine . b. 4-benzylphenylhydra2ine c. 5—ethoxy-2-nitrophenylhydrazine d. 4-propoxyphenylhydrazine 35 e. 4-methylthiophenylhydrazine , f. 4-methylsulfinylphenylhydrazine g. 4—methylsulfonylphenylhydralzine h. 4-chloro-2—(trifluoromethyl)—phenylhydrazine i. 4-(diethylamino)-phenylhydrazine ' 40 j. 4-acetamidophenylhydrazine k. 2—benzyloxyphenylhydrazine 1. 2-chloro-5-methoxyphcnylhydrazine m. 5-chloro-4-methyl-2-nitrophenylhydrazine There can be obtained respectively, according to this 45 invention: , ' ~3-(dimethylamino)-8-ethyl-1,2,3,4-tetrahydrocar— 10 15 20 25 30 a. bazole b. ' 3-(dimethylamino)r6-benzyl-1,2,3,4-tetrahydrocar- bazole 50 c. 3—(dirnethylamino)-5-ethoxy-8-nitro-1,2,3,4-tetrahy- drocarbazole d. 3 -( dimethylamino)—6-propoxy- 1 ,2,3 ,4-tetrahy— drocarbazole _ e. 3-( dimethylamino')-6-methylthio-1 ,2,3 ,4-tetrahy- 55 drocarbazole ' _ _ f. 3-(dimethylamino)-6-methylsulfinyl-1,2,3,4—tetrahy- drocarbazole L g. 3 -(dimethylamino)-6-methylsulfonyl-1 ,2,3 ,4-tet— rahydrocarbazole ‘ h. 3-(dimethylamino)-6-chloro-8-(trifluoromethyl)- 60 1,2,3,4-tetrahydrocarbazole i. 3—(dimethylamino)-6-(diethylamino)-1,2,3,4-tet— rahydrocarbazole . j. 3 -(dimethylamino)-6-acetamide-1 ,2,3 ,4—tetrahy— drocarbazole 65 k. 3-(dimethy1amino)-8—benzyloyl-1 ,2,3,4—tetrahy— drocarbazole 3,959,309 23 l. 3—(dimethylamino)—8-chloro-5-methoxy-1 ,2,3,4-tet— rahydrocarbazole m. 3-( dimethylamino )—5-chloro-6-methyl-8-nitro— 1 ,2,3 ,4-tetrahydrocarbazole EXAMPLE 4 3-(Dimethylamino )-6,7-dimethoxy-l ,2,3,4-tetrahy- drocarbazole Following the procedure given in Example 3 and using 14.8 g. of 4-dimethylaminocyclohexanone and 21.5 g. of 3,4-dimethoxyphenylhydrazine hydrochlo- ride there was obtained 3 g. of 3-(dimethylamino)-6,7- dimethoxy-l,2,3,4-tetrahydrocarbazole which melted at 167°—169°C. (corr.). Test procedure 3: active at 100 mg./kg. Alternatively, 3-(dimethylamino)-6,7-dimethoxy- 1,2,3,4-tetrahydrocarbazole can be prepared by follow- ing a procedure similar to that described in Example 18 below and using 3-(p-toluenesulfonyloxy)—6,7-dime- thoxy-l ,2,3 ,4-tetrahydrocarbazole and dimethylamine. The 3—(p-toluenesulfonyloxy)-6,7-dimethoxy- 1,2,3,4-tetrahydrocarbazole can be prepared from 3- hydroxy-6,7—dimethoxy- 1 ,2,3,4-tetrahydrocarbazole and tosyl chloride by following a procedure similar to that described in Example 18. The 3 -hydroxy-6,7-dimethoxy-l ,2 ,3 ,4—tetrahydrocar- bazole, m.p. 197°~199°C., was prepared from the cor- responding 3-benzoyloxy derivative by potassium hy- droxide hydrolysis following a procedure similar to that described in Example 3. The 3-benzoyloxy-6,7-dimethoxy-1 ,2,3,4-tetrahy- drocarbazole, m.p. 123°-125°C., was prepared from 102 g. of 3,4-dimethoxyphenylhydrazine and 109 g. of 4-benzoyloxycyclohexanone by following a procedure similar to that described in Example 3. EXAMPLE 5 6-(Benzyloxy)-3-(dimethy1amino)-1,2,3,4-tetrahy- drocarbazole Following the procedure given in Example 3 and using 6.7 g. of 4-dimethylaminocyclohexanone and 11.9 g. of p-benzyloxyphenylhydrazine hydrochloride there was obtained 6-(benzyloxy)-3-(dimethy|amino)- 1,2,3,4-tetrahydrocarbazole which upon treatment with alcoholic hydrochloric acid gave 8.2 g. of 6-(ben- zyloxy)-3-( dimethylamino )- 1 ,2,3 ,4-tetrahydrocar- bazole hydrochloride which melted at 209°—212°C. (corr.). Preparation of 4-benzyloxyphenylhydrazine hydro- chloride: To a stirred slurry of 12.5 g. of 4-benzylox- yaniline hydrochloride in 30 ml. concentrated hydro- chloric acid and 30 ml. of water, cooled to -5°C., was added dropwise a solution of 4 g. sodium nitrite in 5 ml. of water. With continued cooling at 0° to —5°C. there was added 35 g. of stannous chloride in 90 ml. of con- centrated hydrochloric acid and the mixture was al- lowad to stand with ice-bath cooling for 3 hours. The solid was collected, slurried in ethyl alcohol and fil- tered to give 11.9 g. of 4-benzyloxyphenylhydrazine hydrochloride; m.p. 185°—187°C. (aqueous ethyl alco- hol). IO 15 20 25 30 35 4O 45 50 55 60 65 24 EXAMPLE 6 3-(Dimethylamino)-6-hydroxy-1 ,2,3,4-tetrahydrocar- bazole The free base of Example 5, 6-(benzyloxy)-3-(dime— thylamino)-l ,2,3,4-tetrahydrocarbazole (20 g.), was hydrogenated for one hour over palladium on charcoal. The catalyst was removed by titration and the filtrate evaporated to give an off—white solid. Recrystallization from ethyl acetate gave 7.4 g. of 3(dimethylamino)-6- hydroxy-l,2,3,4-tetrahydrocarbazole which melted at 202°~204°C. (corr.). Test procedure 1a: active at 50 mg./kg. Test procedure 1b: active at 30 mg./kg. Test procedure 7: active at 4.8 i 1.8 mg./kg. EXAMPLE 7 3-( Dimethylamino)-8—methyl- l ,2,3 ,4-tetrahydrocar- ‘ bazole Following the procedure given in Example 3 and using 10 g. of 4—dimethylaminocyclohexanone and 1 1.2 g. of o-tolylhydrazine hydrochloride there was obtained 4.7 g. of 3-(dimethylamino)~8-methyl-1,2,3,4-tetrahy- drocarbazole in the form of its hydrochloride which melted at 285°-287°C. (corr.). Test procedure 7: active at 4.8 i 1.4 mg./kg. EXAMPLE 8 8-Chloro-3-( dimethylamino)- I ,2,3,4—tetrahydrocar— bazole Following the procedure given in Example 3 and using 7.05 g. of 4-dimethylaminocyclohexanone and 8.95 g. of o-chlorophenylhydrazine hydrochloride there was obtained 4.9 g. of 8-- -chloro—3-(dimethylamino )-1 ,2,3,4-tetrahydrocar- bazole which melted at 154°—157°C. (corr.). Test procedure lb: active at 50 mg./kg. Test procedure 5: active at 100 mg./kg. (1?) Test procedure 7: active at 33.5 i: 6.5 mg./kg. EXAMPLE 9 5 ,8-Dichloro-3-(dimethylamino)-1,2,3 ,4-tetrahy- ' drocarbazole Following the procedure given in Example 3 and using 7.05 g. of 4-dimethylaminocyclohexanone and 10.7 g. of 2,5-dichlorophenylhydrazine hydrochloride there was obtained 4.1 g. of 5,8-dichloro-3-(dime- thylamino)-l ,2,3,4-tetrahydrocarbazole which melted at 206°-209°C. (corr.). Test procedure 1a: active at 30 mg./kg. Test procedure 1b: active at 30 mg./kg. Test procedure 4: active at 100 mg./kg. (1P) EXAMPLE 10 3-( Dimethylamino )-6-nitro-l ,2,3,4-tetrahydrocar- bazole Following the procedure given in Example 3 and using 10 g. of 4-dimethylaminocyclohexanone and 10.8. g. of p-nitrophenylhydrazine hydrochloride there was obtained 2.2 g. of 3-(dimethylamino)-6-nitro-1,2,3,4- tetrahydrocarbazole which melted at 226°—229°C. (corr.). 3,959,309 31 ether and the mixture filtered. Evaporation of the fil- trate gave a residue which crystallized upon trituration with ether. The 3—(methylamino)—l,2,3,4-tetrahy- drocarbazole thus obtained melted at 134°—l36°C. (corr.). Test procedure 1a: active at 30 mg./kg. Test procedure lb: active at 10 mg./kg. Test procedure 2: taming in monkeys at 4 mg./kg. Test procedure 7: active at 5.2 t 0.1 mg./kg. EXAMPLE 24 3-(Ethylamino)-1,2,3,4-tctrahydrocarbazole Following the procedure given in Example 18 and using 25 g. of 3-tosyloxy-1,2,3,4- -tetrahydrocarbazole and 90 g. of ethylamine there was otained 3 g. of 31 -(ethylain0)-l,2,3,4-tetraydrocarbazole which melted at 128°—129°C. (corr.). Alternatively this compound can be prepared by reduction of 3-acetamido-l.2,3,4- tetrahydrocarbazole (Example 2) with lithium alumi- num hydride following a procedure similar to that de- scribed in Example 260 below. Test procedure 2: taming in monkeys at 4 mg./kg. Test procedure 5: active at 100 mg./kg. (PO) Test procedure 6: active at 40 mg./kg. EXAMPLE 25 3—(1-Piperidyl)-1,2,3 ,4-tetrahydrocarbazole Following the procedure given in Example 18 and using 25 g. of 3-tosyloxy-1.2,3,4-tetrahydrocarbazole and 100 g. of piperidine there was obtained 6.2 g. of 3-( l-piperidyl )—l ,2,3,4-tetrahydrocarbazole which melted at 77°—115°C. (corr.). Test procedure 3: active at 64 mg./kg. Test procedure 4: active at 100 mg./kg. (IP) Test procedure 5: active at 100 mg./kg. (1?) Test procedure 6: active at 100 mg./kg. Test procedure 7: active at 3.1 i 0.7 mg./kg. EXAMPLE 26 3-(4-Morpholinyl)-1,2,3,4—tetrahydrocarbazole Following the procedure given in Example 18 and using 34 g. of 3-tosyloxy—1,2.3,4-tetrahydrocarbazole and 200 g. of morpholine there as obtained 13 g. of 3-(4-morpholinyl)—1.2,3,4—tctrahydrocarbazole which melted at 131°—134°C. (corr.). Test procedure 3: active at 64 mg./kg. Test procedure 4: active at 100 mg./kg. (PO) Test procedure 5: active at 100 mg./kg. (1P) Test procedure 6: active at 39 mg./kg. EXAMPLE 27 3-( l—Pyrrolidinyl )- l ,2,3,4-tetrahydrocarbazole Following the procedure given in Example 18 and using 34 g. of 3—t0syloxy-1,2,3,4—tetrahydrocarbazole and 99 g. of pyrrolidine there was obtained 13 g. of 3—( l-pyrrolidiny1)- l ,2,3,4-tetrahydrocarbazole which melted at 200°—205°C. (corr.). Test procedure 3: active at 300 mg./kg. Test procedure 7: active at 0.4 i 0.1 mg./kg. EXAMPLE 28 6-Chloro-3-(dimethylamino)-1,2,3,4-tetrahydroear- bazole Following the procedue given in Example 18 and using 38 g. of 6—chloro-3-tosyloxy-I.2,3,4-tetrahy- drocarbazole and 250 ml. of dimethylamine there was 5 i0 15 20 25 30 35 40 45 50 55 60 65 32 obtained 8.6 g. of 6-chloro-3-(dmethylaino)-1,2,3,4- tetrahydrocarbazole which melted at 181°-184°C. (corr.). Test procedure 111: active at 1 mg./kg. The 6—chlor'o—3-tosyloxy—l ,2,3,4—tetrahydrocarbazole used above was prepared from 67.7 g. of 6-chloro-3- hydroxy-l,2,3,4-tetrahydrocarbazole and 59 g. of p- tosyl chloride following the procedure described in Example 18. There was thus obtained 101 g. of 6- chloro-3-tosyloxy- l ,2,3,4—tetraydrocarbazole. The 6~chloro~3-hydroxy-1 ,2,3,4-tetrahydroarbazole used above was prepared by hydrolysis of 24.2 g. of 3! -benzoyloxy-6-chloro-l ,2,3,4-tetrahydrocarbazole with 5 g. of potassium hydroxide in 50 ml. of water using the procedure given in Example 21 for the preparaton of the corresponding 6-methyl compound. There was thus obtained 15.4 g. of 6-chloro—3-hydroxy-1 ,2,3,4-tetrahy- drocarbazole which melted at 131°—133°C. The 3-benzoyloxy—6-ehloro—l ,2,3,4-tetrahydrocar- bazole used above was prepared by the reaction of 14.3 g. of p-chloropheylhydraZine and 21 g. of 4-benzoylox- ycyclohexanone using the procedure described in Ex- ample 21 for the preparation of the corresponding 6-methyl compound. There was thus obtained 18 g. of 3-benzoyloxy-6-chloro- 1 ,2,3,4—tetrahydrocarbazole which melted at 158°—160°C. EXAMPLE 29 3-(Dimethylamino)—9-methyl-1,2,3,4-tetrahydrocar- bazole Following the procedure described in Example 18 and using 36.2 g. of 9-methyl-3-tosyloxy-1,2,3,4-tet- rahydrocarbazole and 250 m1. of dimetylamine there was otained 9.5 g. of 3-(dimethylamino)-9—methyl— l,2,3,4-tetraydrocarbazole in the form of its hydrochlo- ride salt and which melted at >300°C. Test procedure la: active at 10 mg./kg. Test procedure 112: active at 10 mg./kg. Test procedure 7: active at 0.6 i 0.1 mg./kg. The 9-methyl-3-tosyloxy-1,2,3 ,4-tetrahydrocar- bazole was prepared from 49 g. of 3-hydroxy-9-methyl- 1,2,3.4-tetrahydrocarbazole and 49 g. of tosyl chloride using the procedure described in Example 21 for the preparation of 6-methyl-3-tosyloxy-1 ,2,3 ,4-tetrahy- drocarbazole. There was thus obtained 81 g. of 9-meth— y1-3-tosyloxy-1 ,2,3,4-tetrahydrocabazole which melted at 155°—157°C. The 3-hydroxy-9-methy1—1 ,2,3 ,4-tetrahydrocar- bazole was prepared by hydrolysis of 9.1 g. of 3-ben- zoyloxy-9-methyl-l ,2,3 ,4-tetrahydrocarbazole and 1.95 g. of potassium hydroxide in 100 ml. of 50% ethaol using the procedure described in Example 21 for the preparation of 3-hydroxy-6-methyl—1,2,3,4—tetrahy- drocarbazole. There was thus otained 48 g. of 31 -hy- droxy-9-methyl—1 ,2,3,4—tetrahydrocarbazole which melted at 104°—106°C. . The 3 -benzoyloxy-9 -methyl—1 ,2,3,4—tetrahydrocar- bazole was prepared by the reaction of 34.8 g. of l-phe- nyl-l-methylhydrazine and 62 g. of 4-benzoyloxycy- clohexanone using the procedure described in Example 21 for the preparation of 3-benzoyloxy-6-methyl- 1,2,3.4-tetrahydrocarbazole. There was thus obtained 71 g. of 3-benzoyloxy-9-methyl-1,2,3.4—tetrahydrocar— bazole which melted at 93°—96°C. 3,959,309 35 EXAMPLE 33 3 —( Dimethylamino )-6,7-dimethoxy—9-carboxymeth— yl-l ,2,3.4-tetrahydrocarbazole can be prepared by fol- lowing the procedure described in Example 18 but substituting for the tetrahydrocarbazole and n-butyla« mine used therein an equivalent amount of 3—(p- toluenesulfonyloxy)-6,7ddimethoxy—9-carboxymethy1- 1,2,3,4-tetrahydrocarbazole and dimethylamine re- spectively. The 3-(p-toluenesulfonyloxy)—6,7—dimethoxy-9—car- boxymethyl-1,2,3,4-tetrahydrocarbazole can be pre- pared from the correSponding 3-hydroxy derivative and a mole equivalent of tosyl chloride by following a pro- cedure similar to that in Example 18. The 3—hydroxy—6,7-dimethoxy—9-carboxymethyl- 1,2,3,4-tetrahydrocarbazole can be prepared from 3- benzoyloxy-6,7—dimethoxy—9-carbethoxymethyl- l,2,3,4—tetrahydrocarbazole by hydrolysis with at least a two mole equivalent of potassium hydroxide follow— ing a procedure similar to that described in Example 3. The 3—benzoyloxy-6,7-dimethoxy-9-carbethoxymeth— yl-1,2,3,4-tetrahydrocarbazole was prepared by follow— ing an alkylation procedure similar to that described in Example 1 l but using 17.6 g. of 3-benzoyloxy—6,7— dimethoxy—l ,2,3 ,4—tetrahydrocarbazole (see Example 4) and 2.14 g. of sodium hydride (56% in mineral oil) in 200 ml. of dimethylformamide, and 8.4 g. of ethyl bromoacetate. The crude product in ethyl acetate was filtered through alumina, the filtrate was evaporated to dryness under reduced pressure and the residue was recrystallized from ethyl acetate to give 3-benzoyloxy- 6,7-dimethoxy-9-carbethoxymethyl—l ,2,3,4-tetrahy- drocarbazole, m.p. 125°—127°C. EXAMPLE 34 3-( Dimethylamino )-6—fluoro-1 ,2,3,4—tetrahydrocar- bazole Following the procedure given in Example 3 and using 8.7 g. of 4-dimethylaminocyclohexanone and 10 g. of 4-flu0rophenylhydrazine hydrochloride there was obtained 3—(dimethylamino)-6-fluoro-1,2,3,4-tetrahy- drocarbazole which on treatment in ether with ethereal hydrogen chloride yielded 10.9 g. of the corresponding hydrochloride salt, m.p. 264°~268°C. EXAMPLE 35 3-(Dimethylamino)-6,8-dirnethyl-1,2,3,4-tetrahy- drocarbazole Following the procedure given in Example 3 and using 9 g. of 4-dimethylaminocyclohexanone and l 1 g. of 2,4—dimethylphenylhydrazine hydrochloride there was obtained, after treatment of the free base in ether with ethereal hydrogen chloride, 10.9 g. of 3-(dime- thylamino)-6,8-dimethyl-1,2,3 ,4—tetrahydrocarbazole hydrochloride; m.p. 312°—315°C. 10 15 20 25 30 35 40 45 SO 55 60 65 36 EXAMPLE 36 3-(Dimethylamino)—8-ethyl-1,2,3 ,4-tetrahydrocar- bazole Following the procedure given in Example 3 and using 9 g. of 4-dimethylaminocyclohexanone and 11 g. of 2-ethylphenylhydrazine hydrochloride there was obtained, after treatment of the free base in ether with ethereal hydrogen chloride, 6.7 . of 3-(dime- thylamino)-8-ethyl-1,2,3,4-tetrahydr0carbazole hyd ro— chloride, m.p. 282°~285°C. EXAMPLE 37 3—( Dimethylamino)-8—fluoro-1 ,2 ,3 ,4-tetrahydrocar— bazole Following the procedure given in Example 3 and using 7.8 g. of 4~dimethylaminocyclohexanone and 9 g. of 2—flu0rophenylhydrazine hydrochloride there was obtained, after treatment of the free base in ether with ethereal hydrogen chloride, 6.5 g. of 3- (dimethylamino)-8—fluoro—1,2,3,4-tetrahydrocarbazole hydrochloride, m.p. 298°~302°C. EXAMPLE 38 3-( Dimethylamino)-6-amino-1 ,2,3 ,4—tetrahydrocar— bazole is prepared by dissolving 0.1 mole of 3-(dime— thylamino)—6-nitro- I ,2,3 ,4-tetrahydrocarbazole (Ex— ample 10) in 400 ml. absolute ethyl alcohol and hydro- genating over Raney nickel at about 350 psig and at room temperature until the required amount of hydro— gen has reacted. The resulting 3~(dimethylamino)-6— amino-1,2.3,4-tetrahydrocarbazole can be isolated and purified using conventional procedures. EXAMPLE 39 3—(Dimethylamino)-8—carboxy- l ,2 ,3 ,4-tetrahydrocar— bazole A solution of 14.1 g. of 4-dimethylaminocyclohexa— none and 18.9 g. of 2-carboxyphenylhydrazine hydro— chloride in 150 ml. of absolute ethyl alcohol was heated under reflux for 6 hours, cooled, and the result— ing crystalline 4-dimethylaminocyclohexanone 2— carboxyphenylhydrazone hydrochloride was collected by filtration, washed with isopropyl alcohol and ether, suspended in 200 ml. of 2% hydrogen chloride in acetic acid and heated at reflux for eight hours. The mixture was cooled and the solids were collected by filtration, washed with isopropyl alcohol and dis— solved in 400 ml. of water. The aqueous solution was treated with alkali until neutral and allowed to stand for two hours. The resulting crystals were filtered to give. on recrystallization from water, 30.3 g. of 3-(dimethylamino)‘8-carb0xy- 1 2.3 ,4—tetrahydro— carbazole hydrate, m.p. > 300°C. (dec.) 3,959,309 37 EXAMPLE 40 3-( Dimethylamino)—6-carboxy-1 ,2,3 ,4-tetrahydrocar- bazole Following a procedure similar to thatdescribed in Example 39 and using 14.1 g. of 4—dimethylam— inocyclohexanone, 18.9 g. of 4—carboxyphenylhydra— zine hydrochloride and 150 ml. of absolute ethyl alcohol there was obtained, after recrystallization from water, 20 g. of 4-[4-(dimethylamino):cyclo— hexylidenehydrazino]benzoic acid hydrochloride (4- dimethylaminocycloheXanone 4-carboxyphenyl- hydrazone hydrochloride), m.p. 252°—254°C. Follow- ing a procedure similar to that described in Example 39 and using 24.7 g. of 4—dimethylaminocyclohexanone 4-carboxyphenylhydrazone hydrochloride in 250 ml. of 2% hydrogen chloride in acetic acid there was obtained 9.2 g. of 3—(dimethylamino)-6-carboxy- l,2,3,4—tetrahydrocarbazole, m.p. 315°C. (dec.). Following a procedure similar to that described in Example 39 but substituting for 2-carboxyphenylhydra— zine hydrochloride an equivalent amount of 3-carboxy- phenylhydrazine hydrochloride there is obtained a mix- ture of 41 . 3-(Dimethylamino)-5-carboxy-1,2,3 ,4-tetrahy— drocarbazole and 42. 3-(Dimethylamino)-7-carboxy-1,2,3,4-tetrahy- drocarbazole ' which are separated and purified by standard recrystal- lization procedures. EXAMPLE 43 3-( Dimethylamino)-6-ethoxycarbonyl-1 ,2,3 ,4-tetrahy— drocarbazole A solution of 15.5 g. of 4—dimethylaminocyclohexa— none and 15.2 g. of 4-carboxyphenylhydrazine in 200 ml. of 5—N hydrogen chloride in ethyl alcohol was re- fluxed for 24 hours and the reaction mixture was evap- orated to dryness under reduced pressure. The residue was dissolved in water, the aQueous solution was made alkaline with dilute sodium hydroxide and extracted with methylene dichloride and the extract was evapo— rated to dryness under reduced pressure to give, after recrystallization from isopropyl alcohol, 17.8 g. of (3- (dimethylamino)—6-ethoxycarbonyl-1 ,2,3,4-tetrahy- drocarbazole, m.p. 188°—-190°C. EXAMPLE 44 3—( Dimethylamino)-8-ethoxycarbonyl-1 ,2,3,4—tetrahy— drocarbazole A solution of 4.5 g. of 3-(dimethylamino)-8_—carboxy- l,2,3,4—tetrahydrocarbazole (Example 39) in 150 ml. of S-N hydrogen chloride in ethyl alcohol was heated under reflux for thirty hours. The solution was evapo- rated to dryness. under reduced pressure and therresi- due was recrystallized from ethanol to give 3 ,g. of 33- (dimethylamino)-8-ethoxycarbonyl-1,2,3,4—tetrahy- drocarbazole hydrochloride, m.p. 263°5264°C. 5 10 15 25 30 35 40" 45 50 55 60 65 38 EXAMPLE 45 , . (A) 3—( Dimethylamino )-5-'ethoxycarbony1-1 ,2 ,3 ,4-tetrahy- , drocarbazole and (B) 3-( Dimethylami no )-7—ethoxycarbonyl— 1 ,2,3 ,4—tetrahy— - drocarbazole - Following a procedure similar to that described in Example 43 and using 15.5 g. of 4—dimethylaminocy- clohexanone and 13.2 g. of 3-carboxyphenylhydrazine in 200 m1. of 5-N hydrogen chloride in ethyl alcohol there was obtained, on evaporation to dryness of the methylene‘dichloride extract, a crude mixture which was dissolved in ether and treated with ethereal hydro— genchloride. Isopropyl alcohol was added to the mix- ture. and the ether was evaporated to give a clear solu- tionwhich on refrigeration and filtration gave 9.8 g. of 3-(dimethylamino)—7—ethoxycarbonyl-1 ,2,3 ,4-tetrah y- drocarbazole hydrochloride, m.p. 243°—245°C. This salt was treated with dilute sodium hydroxide and the resulting free base was extracted into methylene di- chloride, dried, and evaporated to dryness to give 8.1 g. of 3—(dimethylamino )-7-ethoxycarbonyl-1 ,2,3 ,4-tet— rahydrocarbazole, m.p. l44°—l46°C. The isopropyl alcohol filtrate from above was concentrated under reduced pressure, cooled and filtered, and the filtrate was filtered again to yield a total of 12.8 g. of crystals which were recrystallized from ethyl alcohol and then from water to give a solid, m.p. 22l°—223°C. A solution of this solid in water was made alkaline with dilute sodium hydroxide and extracted with methylene di- chloride, dried, and evaporated to dryness under re- duced pressure to give' 8.9 g. of 3~(dimethylamino)-5- ethoxycarbonyl-l ,2,3 ,4-tetrahydrocarbazole, m .p. 114°-116°C. Other compounds which are encompassed by this invention and which are prepared by the conventional procedures descried hereinbefore are listed below: By reaction of the carboxylic acid chlorides, pre- pared by conventional procedures (see Example 250 below) from the appropriate compounds of Examples 39 to 42 above, with the apprdpriate alcohols there are obtained: 46. 3-(Dimethylamino)-8—benzyloxycarbonyl- l ,2,3 ,4-tetrahydrocarbazole 4 47. 3-(Dimethylamino)—5-hexyloxycarbonyl-l,2,3,4- tetrahydrocarbazole 48. 3-( Di methylamino )-6-isopropyloxycarbonyl— l ,2,3 ,4etetrahydrocarbazole 49. 3-( Dimethylamino)—6-(4-trifluoromethylben- zyloxy)carbonyl-1 ,2,3 ,4-tetrahydrocarbazole 50. 3-(Dimethylamino)—8—(4-nitrobenzyloxy)carbo- nyl- 1 ,2,3 ,4-tetrahydrocarbazole 5 l. 3-(Dimethylamino)-8-(4-fluorobenzyloxy)carbo- nyl-l ,2,3 ,4-tetrahydrocarbazole 52. 3-(Dimethylamino)-8—(3,4,5—trimethoxyben— zyloxy )carbonyl-l ,2,3 ,4—tetrahydrocarbazole 53. 3-(Dimethylamino)-7-(4-methylbenzyloxy)car- bonyl-l ,2,3 ,4-tetrahydrocarbazole 54. 3-(Dimethylamino)-8~(2—chloro-4-methoxyben- zyloxy)carbonyl-1 ,2,3 ,4—tetrahydrocarbazole. EXAMPLE 55 3-(Dimethylamino)—6—hydroxymethyl—l ,2,3 ,4-tetrahy- drocarbazole A solution'of 12.8 g. of 3-(dimethylamino)-6—ethox- ycarbonyl-l,2,3,4-tetrahydrocarbazole (Example 43) 3,959,309 39 in 350 ml. of dry tetrahydrofuran was added dropwise to a refluxing solution of 3.5 g. of lithium aluminum hydride in 100 ml. of dry tetrahydrofuran and refluxing was continued for one hour after completion of the addition._ Ethyl acetate was added followed by water, the mixture was filtered, and the filtrate was evapo- rated to dryness to give, after recrystallization from ethyl alcohol, 6.4- g. of 3-(dimethylamino)-6-hydrox- ymethzyl—1,2,3 ,4-tetrahydrocarbaZole, m.p. 195°—197°C. ' ' . EXAMPLE 56 3-(Dimethylamino)-8-hydroxymethyl-1,2,3 ,4-tetrahy- drocarbazole Following a' procedure similar to that, described in Example 55 and using 2.4 g. of 3-(dimethylamino)-8- ethoxycarbonyl— l ,2,3,4rtetrahydrocarbazole (Example 44), 1.6 g. of lithium. aluminum hydride and 150 ml. of dry tetrahydrofuran there was obtained, after succes— sive recrystallizations from isopropyl alcohol and ethyl alcohol, 0.56 g. of 3-(dimethylamino)—8-hydroxymeth- yl-l ,2,3,4-tetrahydrocarbazole, m.p. 227°—230°C. EXAMPLE 57 3-( Dimethylamino )-5-hydroxymethyl— l ,2,3 ,4-tetrahy— ‘ . drocarbazole A solution of 3.4‘ g. of 3-(dimethylamino)-5—ethox- ycarbonyl-l ,2,3,4—tetrahydrocarbazole (Example 45A) in 40 ml. of benzene was added to 1 14 ml. of a refluxing solution 'of' sodium bis(2-methoxyethoxy) aluminum hydride, prepared by diluting 14 ml. of a 70% benzene solution ‘of sodium bis(2-methoxyethoxy) aluminum hydride with 100 m1. of benzene, and refluxing was continued for three hours. The reaction mixture, was Cooled; water was added and the resulting white solid was collected by filtration and slurried in Water. The slurry was adjusted to pH 4 by addition of l-N sulfuric add and filtered. The filtrate was made alkaline with dilute ‘sOdium hydroxide and the resulting solid was collected by filtration‘to give, after crystallization‘from ethyl alcohol, 2.26 g. of 3-(dimethylamino)—5-hydrox- yrnethyl-l,2,3,4-tetrahydrocarbazole, ‘ m.p. 245°~248°C. ‘ , By conventional esterification procedures using the appropriate carboxylic acid chlorides and hydroxy- methyl compounds'of Examples 55 and 56 there are obtained: ' , 58._ 3-( Dimethylamino )-6-acetoxymethyl-l ,2,3,4—tet- rahydrocarbazole . 59. 3-(Dimethylamino)—8-hexanoyloxymethyl— 1 ,2,3 ,4-tetrahydrocarbazole _ _ 60. 3-(Dimethylamino)—8-benzoyloxymethyl-1,2,3,4— tetrahydrocarbazole 61. 3-( Dimethylamino )~6-isopropanoyloxymethyl- 1 ,2,3 ,4-tetrahydrocarbazole 62. 3-( Dimethylamino )—8-( 4-trifluoromethylben- zoyloxy)methy1- l ,2,3,‘4-tetrahydrocarbazole - . 63. 3 -( Dimethylamino )-6-( 3 ,4 ,5 -trimethoxyben- zoyloxy )methyl- l ,2,3,4-tetrahydrocarbazole 64. 3-(Dimethylamino)-6-(2—chloro—4-methoxyben- zoyloxy )methyl- 1 ,2,3,4—tetrahydrOCarbazole 65. 3-( Dimethylamino )—8-( 4-methylbenzoyloxy )- methyl-1 ,2,3 ,4-tetrahydrocarbazole. By a conventional oxidation procedure, e.g., oxida- tion with manganese dioxide .there are obtained respec- tively from the compounds of Examples 55 and 56: 10 15 20 25 30 35 40 40 66. 3-(Dimethylamino)«6-formyl-1,2,3,4-tetrahy- drocarbazole ' - 67. 3—(Dimethylamino)—8-formyl-1,2,3,4-tetrahy- drocarbazole. I. By reaction of the appropriate carboxylic acid chlo— rides, prepared by conventional procedures from com- pounds 39 »and >40 ab0ve, with the» appropriate amines there are obtained: _ s r 68. 3—(Dimethylamino)-8-dimethylaminocarbonyl- 1 ,2,3,4—tetrahydrocarbazole . 69. 3:( Dimethylamino )-6-dihexylaminocarbonyl- 1,2,3,4-tetrahydrocarbazole ' . ' 70. 3-( Dimethylamino)-8v(4-morpholinyl)carbonyl- 1 ,2,3 ,4rtetrahydrocarbazole I 71 . 3-(Dimethylamino)-6-( l-pyrrolidinyl )carbonyl— l,2,3,4-tetrahydrocarbazole ; ~ . , 72. _ 3-( Dimethylamino)-8'-( l—piperazinyl)carbonyl~ 1,2,3,4—tetrahydrocarba201e ' I ‘ 73. 3-( Dimethylamino)-6-( 4—me‘thyl- l -piperazinyl )- carbonyl— 1 ,2,3 ,44tetrahydrocarbazole 74. 3-(Dime‘thyl‘amino)-6-(4-thiomorpholinyl)carbo— nyl-l ,2,3 ,4-tetrahydrocarbazole v 75. 3-(Dimethylamino)-8-( l-piperidinyl)carbonyl- 1 ,2,3‘,4—tetrahydrocarbazole 76. 3-(Dimethylamino)-8-(4-phenyl-1-piperazinyl)- carbonyl- 1 ,2 ,3 ,4-tetrah ydrocarbazole 77. 3-( Dimethylamino)—.6—[4-( 4-trifluoromethyl— phenyl)—1-piperazinyl]carbonyl-1 ,2,3,4—tetrahydrocar- bazole ,. 78. 3'—( Dimethylamino)—8-[4-( 2-chloro-4-methoxy- phenyl)—1-piperazinyl]carbonyl-1 ,2,3 ,4-tetrahydrocar- bazole ' ' ' ‘ ' 79. 3-( Dimethylamino )-6-[4-(4-tolyl )— 1 — piperazinyl ] carbonyl-1 ,2,3 ,4—tetrahydrocarbazole. By using conventional reduction procedures there are obtained from compounds 68 to 79 inclusive: 80. 3-( Dimethylamino )-8-dimethylaminomethyl- l ,2,3 ,4-tetrahydrocarbazole 8 l . 3—( Dimethylamino)-6-dihexylaminomethyl- 1,2,3,4-tetrahydrocarbazole , . 82. ‘ 3-(Dimethylamino)-8-(4-morpholinyl)methyl- 1 ,2,3 ,4-tetrahydrocarbazole. ’83 . 3-( Dimethylamino )—6—( l-pyrrolidinyl )methyl- . 1,2,3,4—tetrahydrocarbazole 45 50 55 60 65 84. 3-(DimethylaminO)-8-( l¥piperazinyl)methyl- l ,2,3 ,4-tetrahydrocarba‘zole - I 85. 3-( Dimethylamino)-6-( 4-methylél -piperazinyl )- methyl—1,2,3,4-tetrahydrocarbazole ‘ - v ' 86. 3-( Dimethylamino )-6—( 4—thi0morpholinyl )meth— yl—l ,2,3,4-tetrahydrocarbazole . , 87. 3-( Dimethylamino )-8-( l-piperidinyl )methyl- 1 ,2,3,4-tetrahydrocarbazole 88. 3—(Dimethylamino)-8-(4—phenyl-1-piperazinyl)- methyl-1 ,2,3 ,4-tetrahydrocarbazole 89. 3-( Dimethylaminoj-6-[4'-( 4-trifluoromethyl- phenyl)-1 -piperazinyl }methy1,— 11,2,3 ,4-tetrahydrocar- bazole 90. 3-(Dimethylamino)-8-[4—(2-chloro-4—methoxy— phenyl)-1 -piperazinyl]methyl-1 ,2,3,4-tetrahydrocar- bazole ' ‘ 91. ' 3-(Dimethylamino)—6-[4-(4-tolyl)—l- piperazinvyl ] methyl— 1 ,2,3 ,4-tetrahydrocarbazole. / By following a procedure similar to that described in Example 3 and substitutingfor p-methoxyphenylhydra— zine hydrochloride an equivalent amount of the hydro- chlorides of: , .4-hydrazino-4 ’-methoxybiphenyl 2-hydrazino-4’-fl uorobiphenyl 3,959,309 41 2-hydrazino-4’-methylbiphenyl 2-hydrazino-3 ’-trif1uoromethylbiphenyl (2-phenoxyphenyl )hydrazine [4-(4-chlor0phenoxy)phenyl ]hydrazine . [2—(3-trifluoromethylphenoxy)phenyl]hydrazine [4-(4-tolyloxy)phenyl]hydrazine There are obtained respectively: 92. 3—(Dimethylamino)-6-(4-methoxyphenyl)- 1,2,3 ,4-tetrahydrocarbazole 93. 3-(Dimethylamino)—8-(4-fluorophenyl)—1,2,3,4— tetrahydrocarbazole 94. 3—( Dimethylamino )-8-(4—tolyl)— l ,2,3,4-tetrahy- drocarbazole 95. 3—(Dimethylamino)-8—(3-trifluoromethylphenyl)— l,2,3,4-tetrahydrocarbazole 96. 3-(Dimethylamino)-8— phenoxy- 1 ,2,3 ,4-tetrahydrocarbazole 97. 3-( Dimethylamino )-6-( 4-chlorophenoxy )- 1 ,2 ,3 ,4-tetrahydrocarbazole 98. 3—(Dimethylamino)-8-(3-trifluoromethylphenox- y)—1 ,2,3 ,4-tetrahydrocarbazole 99. 3—(Dimethylamino)-6—(4-tolyloxy)-1,2,3,4-tet— rahydrocarbazole Following a procedure similar to that given in Exam- ple 21 and substituting for 4-benzoyloxycyclohexanone an equivalent amount of the following 4-benzoyloxycy- clohexanones (prepared in a conventional manner from 4-hydroxycyclohexanone and the appropriate benzoyl chlorides): 4—(4—methoxybenzoyloxy)cy— clohexanone , '4-( 3 ,4,5 -trimethoxybenz_oyloxy )cy— clohexanone, 4-(4—methylbenzoyloxy)cyclohexanone, 4-( 2~chloroj4-nitrobenzoyloxy )-cyc10hexanone, 4-( 3- trifluoromethylbenzoyloxy)cyclohexanone, 4-(4-hexyl- benzoyloxy)cyclohexanone, 4-(4-isopropylbenzoylox- y )-cyclohexanone, 4-( 2-fluorobenzoyloxy)cyclohexa— none, " 4-(2-ethoxybenzoyloxy)cyclohexanone, _ 4—(2- n itro -4—methoxybenzoyloxy )cyclohexanone, 4-( 4- iodobenzoyloxy)cyclohexanone, 4-(4—bromoben- zoyloxy)cyclohexanone and 4-(4-pentyloxybenzoylox-, y)cyclohexanone; and substituting for p-tolylhydrazine 10 15 20 25 30 35 40 an equivalent amount of 2—ethylphenylhydrazine, _4- . benzylhydrazine, 5-ethoxy—2-nitrophenylhydrazine, 4-prop0xyphenylhydrazine, 4-methylthiophenylhydra— zine, 4-methylsulfinylphenylhydrazine, 4-methylsul- fonylphenylhydrazine, 4-chloro-2-(trifluoromethyl)- phenylhydrazine, 4-(diethylamino)phenylhydrazine, 4-acetamidophenylhydrazine, 2-benzyloxyphenylhy- drazine, 2—chloro-S-methoxyphenylhydrazine, and 5- chloro-4-methyl-2-nitrophenylhydrazine, there are ob— tained respectively: 100. 3—(4-Methoxybenzoyloxy)-8-ethyl—1,2,3,4—tet— rahydrocarb azole . 101, 3 -( 3 ,4,5-Trimethoxybenzoyloxy)-6-benzyl:_ l ,2,3 ,4-tetrahydrocarbazole 102. 3-(4-Methylbenzoyloxy )-5 -ethoxy-8-nitro- l ,2,3,4-tetrahydrocarbazole 103 . 3 ( 2—Chloro-4—nitrobenzoyloxy )-6-propoxy- 1 ,2,3 ,4—tetrahydrocarbazole r 104. 3-( 3-Trifluoromethylbenzoyloxy )-6-methylthio- 1 ,2,3 ,4-tetrahydrocarbazole 105 . 3-(4-Hexylbenzoyloxy )-6-methylsulfinyl- 1,2,3,4-tetrahydrocarbazole 106. 3-(4-Isopropylbenzoyloxy)-6-methylsulfonyl- 1 ,2,3,4-tetrahydrocarbazole 107. 3-( 2-Flu0robenzoyloxy)-6-chloro-8—(tri- fluoromethyl)-1,2,3 ,4-tetrahydr0c'arbazole 108. 3-(2-Ethoxybenzoyloxy )-6-(diethylamino )- 1,2,3 ,4-tetrahydrocarbazole 45 50 55 60 65 42 109. 3-( 2-Nitro-4-methoxybenzoyloxy ) -6- acetamido-l ,2 ,3 ,4-tetrahydrocarbazole 1 10. 3-(4-lodobenzoyloxy)-8-benzyloxy- l ,2,3,4-tet- rahydrocarbazole 1 l 1. 3—(4—Bromobenzoyloxy)-8-chloro-5-methoxy- l ,2,3,4—tetrahydrocarbazole 1 12. 3-(4-Pentyloxybenzoyloxy)—5-Ch10ro-6-methyl- 8-nitro-1,2,3,4-tetrahydrocarbazole. Following a procedure similar to that given in Exam- ple 21, using 4-benzoyloxycyclohexanone and substi- tuting for p-tolylhydrazine an equivalent amount of: 2-hydrazinobiphenyl, 4-hydrazino—4’-methoxybiphe- nyl, 2-hydrazino-4’-fluorobiphenyl, 2-hydrazino-4’- methylbiphenyl, 2-hydrazino-3’-trifluoromethy1biphe- nyl , (2—phenoxyphenyl )-hydrazine, [4—( 4-chloro- phenoxy )phenyl ]hydrazine, [2-( 3—trifluoromethyl— phenoxy)phenyl]hydrazine and [4—(4-tolyloxy) —phe- nyllhydrazine there are obtained respectively: 1 l3. 3-( Benzoyloxy)-8—phenyl-l ,2,3,4-tctrahy- drocarbazoie 1 l4. 3-( Benzoyloxy )-6-(4-methoxyphenyl)-l ,2,3,4— tetrahydrocarbazole 1 15. 3-(Benzoyloxy)-8-(4-fluorophenyl)-1,2,3,4-tet- rahydrocarbazole l 16. 3.—( Benzoyloxy)-8-(4-tolyl )- l ,2,3 ,4—tetrahy- drocarbazole 1 17. 3-( Benzoyloxy )—8-( 3-trifl uoromethylphenyl )- 1 ,2,3,4-tetrahydrocarbazole l 18. 3-(Benzoyloxy)—8-phenoxy-l ,2,3,4-tetrahy— drocarbazole ' 1'19. 3—( Benzoyloxy )-6-( 4-chlorophenoxy )«l ,2,3 ,4- tetrahydrocarbazole 120. 3 -( Benzoyloxy)-8-( 3-trifluoromethylphenoxy)- > l,2,3,4-tetrahydrocarbazole 121. 3-( Benzoyloxy)-6-( 4-tolyloxy )-l ,2,3,4-tetrahy~ drocarbazole ' By following a procedure similar to that described in Example 11, substituting for 3-benzoyloxy—1,2,3,4-tet- rahydrocarbazole an equivalent amount of compounds 7100 to 115 inclusive, and for p-chlorobenzyl chlorides an equivalent amount of n-hexyl chloride, 2-phenethyl chloride, 3,3-dimethylallyl bromide, 2-dimethylamino- propyl chloride, 2-(4-morpholinyl)ethyl chloride, 2—(4- thiomorpholinyl)ethyl chloride, 2-( l-piperidinyl )ethyl chldride, 2-(1—pyrrolidinyl)ethyl chloride, 2—( 1- piperazinyl)ethyl chloride, 2-(4-methyl-l-piperazinyl- )ethyl chloride, 24(4-phenyl-l~piperazinyl)ethyl chlor- ide, 3,4-difluorobenzyl chloride, 2,6-dichlorobenzyl bromide, 1-bromo—3-(3-methoxyphenyl)propane, 4— methylbenzyl bromide, and 2,5—dimethylbenzyl chlor- ide, there are obtained respectively: 122. 3-(4—Methoxybenzoyloxy)-8-ethyl-9-(n-hexyl)- 1 ,2,3 ,4-tetrahydrocarbazole 123. 3-( 3,4,5-Trimethoxybenzoyloxy )-6-ben2yl-9- (2-phenethyl )-1 ,2,3 ,4-tetrahydrocarbazole , 124. 3-(4-Methylbenzoyloxy )-5-ethoxy-8-nitro-9- (3 ,3-dimethylallyl)—l ,2,3,4-tetrahydrocarbazole 1 25. 3-,( 2-Chloro-4-nitrobenzoyloxy)-6-propoxy-9- ( 2-dimethylaminopropy1)-l ,2,3 ,4—tetrahydrocarbazole 126. 3—( 3—Trifluoromethylbenzoyloxy )-6-methylthio- 9-[2-(4-morpholinyl)ethyl]-1,2,3,4-tetrahydrocar- bazole 127. 3-(4-Hexylbenzoyloxy)—6-methylsulfinyl-9-[2- ( 4-thiomo rpholiny)ethyl ]-l ,2,3 ,4-tetrahydrocarbazole ' 128. 3—(4-Isopropylbenzoyloxy)-6—methylsulfonyl-9- [2-( l-piperidinyl )ethyl ] -l ,2,3 ,4-tetrahydrocarbazole 3,959,309 43 129. 3-( 2—Fluorobenzoyloxy)-6-chloro-8-(tri— fluoromethyl)-9—[2—( 1-pyrrolidinyl)ethyl]-1,2,3 ,4—tet- rahydrocarbazole 130. 3—(2-Ethoxybenzoyloxy)—6-(diethy1amino)—9- 12-( 1-piperazinyl)ethy1]—1,2,3,4-tetrahydrocarbazole 131. 3-( Z-Nitro-4-methoxybenzoyloxy)-6— acetamido-9—[2-(4-methy1-1—piperazinyl)ethyl]— 1,2,3 ,4-tetrahydrocarbazole 132. 3-( 4-lodobenzoyloxy)—8-benzyloxy—9-[ 2—( 4- phenyl- 1 -piperazinyl )ethyll- 1 ,2,3 ,4—tetrahydrocar~ bazole 133. 3-(4—Bromobenzoyloxy)-8-chloro—5-methoxy-9—(3,4—- -difluorobenzyl )- 1 ,2,3 ,4—tetrah ydrocarbazole 134. 3—(4—Pentyloxybenzoyloxy)-5-chloro-6-methy1- 8—nitro—9—(2,6-dichlorobenzyl)—1,2,3,4—tetrahydrocar— bazole 135. 3-(Benzoyloxy)-8-pheny1—9—[3—(3-methoxy— phenyl)—l-propyl]-1,2,3 ,4-tetrahydrocarbazole 136. 3 -( Benzoyloxy)-6—(4—methoxyphenyl )—9—( 4— methylbenzyl )-1 ,2,3,4-tetrahydrocarbazolc 137. 3-( Benzoyloxy)—8—(4-f1uorophenyl)-9-(2,5- dimethylbenzyl)-1,2,3 ,4vtetrahydrocarbazole By using conventional ester hydrolysis procedures described hereinbefore there are obtained from com- pounds 1 16 to 137 inclusive above the following: 138. 3-(Hydroxy)-8-(4-tolyl)-1,2,3,4—tctrahydrocar— bazole 139. 3—(Hydr0xy)—8-( 3-trifluoromethylpheny1 )— 1 ,2,3,4—tetrahydrocarbazole 140. 3-( Hydroxy)-8-phenoxy- l ,2,3,4—tetrahydrocar- bazole 141 . 3-(Hydroxy)-6-(4—chlorophenoxy)—1,2,3,4-tet— rahydrocarbazolc 142. 3-( Hydroxy)-8-( 3-trifluoromethylphenoxy )~ 1,2,3,4-tetrahydrocarbazole 143. 3-(Hydroxy)—6-(4—tolyloxy)-1,2,3,4—tetrahy- drocarbazole ‘ 144. 3-(Hydroxy)-8-ethyl-9—(n-hexyl)—1,2,3,4—tet- rah ydrocarbazole 145. 3-( Hydroxy )—6‘benzyl-9-( 2—phenethyl )-1 ,2,3 ,4— tctrahydrocarbazole 146. 3-( Hydroxy )-5—ethoxy-8-nitro-9—( 3,3—dime— thylallyl)-1,2,3,4-tetrahydrocarbazolc 147. 3-( Hydroxy)—6-propoxy-9—( 2-dimethylamino- propy1)— 1 ,2,3,4—tetrahydrocarbazole 148. 3-(Hydroxy)-6-methy1thio-9-[2-(4-mor- pholiny1)ethyl]-1 ,2,3 ,4-tetrahydrocarbazole 149. 3-(Hydroxy )-6-.methylsu1finy1-9—[ 2-(4-thiomor— pholinyl )—ethyl]—l ,2,3 ,4-tetrahydrocarbazole 150. 3-(Hydroxy)—6-methylsulfonyl-9-[ 2—( l— piperidinyl )ethyl ]— 1 ,2,3 ,4-tetrahydrocarbazole 151. 3-(Hydroxy)—6-chloro-8-(trifluoromethyl )«9-[2— ( l—pyrrolidinyl )ethyl]- l ,2,3,4-tetrahydrocarbazole 152. 3-( Hydroxy)-6 -(diethylamino)-9-[2—( 1- piperazinyl)ethyl]—1,2,3,4-tetrahydrocarbazole 15 3. 3-(Hydroxy)-6-acetamido-9-[2-(4-methyl-1- piperazinyl)-ethyl]-1,2,3,4-tetrahydrocarbazole 154. 3-( Hydroxy )-8-benzyloxy—9~[ 2-( 4-phenyl- 1 - piperazinyl—ethyl ]—1 ,2 ,3 ,4—tetrahydrocarbazole 155. 3-( Hydroxy)-8—chloro-5-methoxy-9-( 3,4- difluorobenzyl)-1,2,3,4-tetrahydrocarbazole 15 6. 3—( Hydroxy)-5-chloro-6-methyl-8-nitro-9-( 2,6- dichlorobenzyl)-1,2,3 ,4-tetrahydrocarbazole 157. 3-(Hydroxy)-8—phenyl-9-[3-(3-methoxy— phenyl )- 1 —propyl ]- l ,2,3 ,4-tetrahydrocarbazole 158. 3-(Hydroxy)-6 -(4—methoxyphenyl)—9—(4— methylbenzyl)—1,2,3,4-tetrahydrocarbazole 5 10 15 20 25 3O 35 4O 45 50 55 60 65 44 159. 3-(Hydroxy)-8-(4-fluorophenyl)-9-(2,5-dime- thylbenzy1)—1,2,3 ,4-tetrahydrocarbazole Following the conventional procedure given herein— before for preparing 3-su1fonyloxy—1,2,3,4—tetrahy- drocarbazoles from the corresponding 3-hydroxy com- pounds there are obtained from compounds 138 to 150 inclusive on reaction with benzenesulfonyl chloride, methylsulfonyl chloride, hexanesulfonyl chloride, ben- zylsulfonyl chloride, 4-methoxybenzylsulfony1 chlor- ide, 4-fluorobenzylsulfonyl chloride, 4-nitrobenzylsul- fonyl chloride, 3,4,5-trimethoxybenzenesulfonyl chlor- ide, 3—(trifluoromethyl)benzenesulfonyl chloride, 4- chlorobenzenesulfonyl chloride, 4-nitrobenzenesulf0— nyl chloride, 2-chlorobenzenesulfonyl chloride and 2-bromo—4—nitrobenzenesulfonyl chloride and from compounds 151 to 159 inclusive on reaction with 4— toluenesulfonyl chloride respectively the following: 160. 3—(Benzenesulfonyloxy)-8—(4—tolyl)-1,2,3,4—tet— rahydrocarbazole 161. 3—( Methylsulfonyloxy )-8—( 3—trifluoromethy1— phenyl)—1,2,3 ,4-tetrahydrocarbazole 162. 3-(Hexanesulfonyloxy)—8—phenoxy-1,2,3,4-tet- rahydrocarbazole 163. 3-( Benzylsulfonyloxy )-6—( 4-chlorophenoxy)- 1 ,2 ,3 ,4—tetrahydrocarbazole 164. 3-(4-Methoxybenzylsulfonyloxy )-8—( 3-tri— fluoromethylphenoxy)- 1 ,2,3,4-tetrahydrocarbazole 165. 3-(4—Fluorobenzylsulfonyloxy)—6-(4—tolyloxy)- 1,2,3 ,4—tetrahydrocarbazole 166. 3-(4—Nitrobenzylsulfonyloxy)—8—ethy1—9-(n-hex— yl)-1,2,3,4- tetrahydrocarbazole 167. 3-( 3,4,5-Trimethoxybenzenesulfonyloxy )—6- benzyl-9-( 2—phenethyl )-1 ,2,3 ,4-tetrahydrocarbazole 168. 3-[3-(Trifluoromethyl)benzenesulfonyloxy]—5- ethoxy—8-nitro-9-(3,3—dimethylallyl)-1,2,3,4-tetrahy- drocarbazole 169. 3—( 4-Chlorobenzenesulfonyloxy)—6-propoxy—9- (2-dimethy1aminopropy1)-1,2,3 ,4-tetrahydrocarbazole 170. 3-(4—Nitrobenzenesulfonyloxy)-6-methy1thio—9- [2-(4—morpholiny1)ethy1]-1 ,2,3,4—tetrahydrocarbazole 171. 3-( 2—Chlorobenzenesulfonyloxy )-6-methylsulfi— nyl-9—[2-(4-thiomorpholiny1)ethyl]—1,2,3,4-tetrahy— drocarbazole 172.' 3-( Z-Bromo-4-nitr0benzenesulfonyloxy )-6- methylsulfonyl-Q-[2-(1—piperidiny1)ethy1]-1,2,3,4-tet— rahydrocarbazole 173. 3-(4—Toluenesulfonyloxy)—6—chloro—8—(tri— fluoromethyl)—9—[2-(1-pyrrolidiny1)ethyl]-1,2,3,4—tet—‘ rahydrocarbazole 1'74. 3-(4—Toluenesulfonyloxy)-6-(diethylamino)-9- [2—(1-piperazinyl)ethy1]-1,2,3,4-tetrahydrocarbazole 175. 3‘(4—T01uenesu1fonyloxy)-6—acetamido—9—[2—(4~ methyl- 1 -piperazinyl )ethyl ]- 1 ,2,3 ,4-tetrahydrocar- bazole 176. 3-(4-Toluenesulfonyloxy)-8—benzyloxy-9-12-(4— phenyl-l-piperazinyl)ethy1]-1 ,2,3,4-tetrahydrocar- bazole 177. 3-(4-Toluenesu1fonyloxy)—8-chloro-5-methoxy- 9-(3,4-difluorobenzyl)—1,2,3 ,4-tetrahydrocarbazole 178. 3-(4-Toluenesulfonyloxy)-5-ch10ro-6-methyl-8- ‘ nitro—9—(2,6-dichlorobenzy1)1,2,3,4-tetrahydrocar- bazole 179. 3-(4-Toluenesulfonyloxy)-8-phenyl-9—[3-(3- methoxypheny1)-1-propyl]—1,2,3,4—tetrahydrocar- bazole 180. 3-(4—Toluenesu1fonyloxy )—6-( 4—methoxy- phenyl)-9-(4-methy1benzyl)-1,2,3,4—tetrahydrocar- bazole 3,959,309 47 phenoxyphenylhydrazine hydrochloride and the mix- ture was heated at reflux for 6 hours. The mixture was filtered, the filtrate was made alkaline with 10% potas- sium hydroxide and extracted with chloroform, and the chloroform extract was washed with water and evapo- rated to dryness under reduced pressure to give 3- (dimethylamino)-6-phenoxy- 1 ,2,3,4-tetrahydrocar— bazole. The free base was taken up in ether and ethereal hydrogen chloride was added and the resulting solid was filtered to give, on recrystallization from isopropyl alcohol, 25 g. of 3-(dimethylamino)—6-phenoxy- 1 ,2,3,4tetrahydrocarbazole hydrochloride, m.p. 235°—240°C. EXAMPLE 206-233 By following the manipulative procedure described above in Example 205, substituting for the 4-phenoxy- phenylhydrazine hydrochloride used therein equivalent amounts of the phenylhydrazines listed in Table ll be- low, the respective 3-( N=B)-9—R-l ,2,3,4-tetrahy- drocarbazoles of formula I (where N=B is dimethyl- amino and R is hydrogen) listed be10w in Table l were prepared. Table l 3-( Dimcthylamino)-Q._,- l ,2 ,3 ,4-tetruhydmcarbazolc 0H (other than Example hydrogen) Salt M .P.( °C.) 206 7,8-dimethyl HCI 318—322 207 6,7—difluoro HCI 257—260 208 5.8—dimcthyl —- 138—148 209 6,8—dichloro -— 192—1935 210 7,8-dichloro — 181—182 211 {8-bromo - 136—137 HCl 273—275 212 8-(trifluorumethyl) ~ 77— 80 213 S-chlnro-s-mcthoxy HCI 304—307 214 8-methoxy -— l94—i95 215 8-methylthio -— 136—139 216 8-methylsulfonyl HCI 274—275 217 8-iodo HCI 265—266 218 S-chloro-S-mcthyl — 167—169 219 8—bromo-S-fluoro — 162—163 220 8-brorno-5-chloro ~ 175—181 221 5,7-dimcthyl — 124—128 222 5,8-difluoro HCI >260 223 5.6.7.8—tctrafluoro — 219—222 224 B-fiuoro—S—methyl HCl 182—184 225 8-Chloro-5«(trifluoro- methyl) HCI 291—293 226 7,8-difluoro — 200—202 227 8-chloro-7-methyl HCI 280—282 228 5-fluoro-8-t 4-fluoro- phenyl) — 163—166 229 8-phenyl — 131—134 230 6-acetamido HCI 304—306 231 8—(henzyloxy) HCI 252—253 232 8-pr0pyl HCl 242—244 233 S—bromo-S-methyl — 149—150 The phenylhydrazines of formula lVA (where R is hydrogen), listed in Table [1 below, used in the prepara- tion of the compounds of Examples 206—233 above were prepared from the corresponding anilines using a procedure similar to that described in Example 5. The phenylhydrazines were isolated either in the free base form or as the hydrochloride salts. In some cases the products were used directly in the next step without recrystallization. Table ll (014)-Phenylhydrazine 0.-., (other than hydrogen) Salt M.P.(°C.) 2,3—dimethyl HCI 218—220 3,4-difluoro HCI 5 10 15 20 25 30 35 4O 45 50 55 60 65 48 Table Il-continued . (Q,_,)»Phenylhydrazine O H (other than hydrogen) Salt M.P.(°C.) 2,5—dimethyl HCl 2.4—dichlom — 91— 94 2.3-dichloro — 111—1 14 2—bromo HCI 197—198 2-(triflu0romethyl) — 61— 63 2-methoxy—S -chlorn HCI 2—methoxy HCI 2-methylthio HCI 142-144 Z—methylsulfonyl HCI 2>iod0 HCl 175 (dec.) 2»chloro»5»methyl HCl 2~bromo-5—fluoro HCI 174—175 2-hromo-5-chloro HCl 3,5-dimethyl HCl 155—157 2,5-diflu0ro HCI 2.3.4.5.tetrafluoro HCI 207 (dec.) 2-fluor0»5-methyl HCl 195—197 2-chloro-5-( trifiuoro- methyl) ~— 2.3-difluoro HCI 81— 84 2-chloro—3-methyl — 217 (dec.) 5-fluoro-2-(4-fluoro— phenyl) -— 105—1 15 2-phenyl HCl 4-acetamido HCI I73 (dee) 2-benzyloxy HCI 153—155 2-propyl HCI 2-bromo’5-mcthyl HCI 188—190 EXAMPLE 234 3-(Dimethy1amino)-5-(trifluoromethyl)-1,2,3,4—tet- rahydrocarbazole To a solution of 4 g. of 3—(dimethylamino)-8-chloro- 5-( trifluoromethyl )-1 ,2,3,4-tetrahydrocarbazole (Ex- ample 225) in 200 ml. ofethyl alcohol was added 1.4 g. of potassium hydroxide and 1 g. of 10% palladium on charcoal and the mixture was subjected to a hydrogen atmosphere at room temperature and 50 psig. When approximately an equimolar amount of hydrogen had reacted the mixture was acidified with 10% hydrochlo- ric acid, diluted with 50 m1. of water, filtered, made alkaline with 10% sodium hydroxide and concentrated to a small volume under reduced pressure. The result- ing precipitate was collected by filtration and washed with water to give 3.6 g. of 3-(dimethylamino)—5-(tri- fiuoromethyl )—l ,2,3,4-tetrahydrocarbazole, m .p. 222°-225°C. EXAMPLE 235 3-(Dimethylamino)-5-fluoro-1,2,3,4-tetrahydrocar- bazole Following a procedure similar to that described in Example 234 but using 2 g. of 3-(dimethylamino)-8- bromo~5-fluoro-l ,2,3,4-tetrahydrocarbazole (Example 219), in 100 ml. of methyl alcohol, 1 g. of 10% palla- dium on charcoal and 1 g. of potassium hydroxide in 2 ml. of water there was obtained, after recrystallization from benzene, 1.3 g. of 3-(dimethylamino)-5-fluoro- l,2,3,4—tetrahydrocarbazole, m.p. 166°~l68°C. EXAMPLE 236 3-( Dimethylamino )-5 ~chloro- l ,2,3 ,4-tetrahydrocar- bazole To a solution of 14.8 g. of 3—(dimethylamino)-8- bromo-S-chloro~ 1 ,2,3,4-tetrahydrocarbazole (Example 220) in 200 m1. of methyl alcohol was added a slurry of 2 g. of 10% palladium on charcoal in 100 m1. of ethyl alcohol. The mixture was subjected to a hydrogen at- 3,959,309 49 mosphere at about 60 psig at room temperature. When an equimolar amount of hydrogen had reacted (about ten minutes), the uptake of hydrogen ceased. The mix- ture was filtered, the filtrate was evaporated to dryness, ' the residue was dissolved in water and the resulting solution was made alkaline with dilute sodium hydrox- ide. The resulting solids were collected by filtration and recrystallized from ethyl alcohol to give 6.2 g. of 3- ( dimethylamino )-5 -chloro-1 ,2,3 ,4-tetrahydrocar- bazole, m.p. 21 2°—2 14°C. When 4 g. of 3-(dimethylamino)-8-bromo-5-fluoro- 1,2,3,4—tetrahydrocarbazole was subjected to a proce- dure similar to that described in Example 234, that is, in the presence of 1 g. of potassium hydroxide, there was obtained 3-(dimethylamino)-1,2,3,4-tetrahy— drocarbazole (Example 1) which was converted to 1.2 g. of the hydrochloride salt. EXAMPLE 237 3-( Dimethylamino)—8-chloro-5-ethoxycarbonyl- 1 ,2,3 ,4-tetrahydrocarbazole Following a procedure similar to that described in Example 43 and using 14.2 g. of 4-dimethylaminocy- clohexanone hydrochloride and 13.6 g. of 2-chloro—5- carboxyphenylhydrazine [m.p. 198°C. (dec.)] in 250 m1. of 4—N hydrogen chloride in ethyl alcohol there was obtained on evaporation of the reaction mixture to dryness, followed by recrystallization of the residue from ethyl alcohol, 6.1 g. of 3-(dimethylamino )—8— chloro-S-ethoxycarbonyl— 1 ,2,3 ,4—tetrahydrocarbazole hydrochloride, m.p. 236°—237°C. EXAMPLE 238 3-(Dimethylamino)-7-fluoro-1,2,3,4-tetrahydrocar- bazole A solution of 35.5 g. of dimethylaminocyclohexa- none hydrochloride and 34.5 g. of 3-fluorophenylhy- drazine hydrochloride in 500 ml. of absolute ethyl alco- hol was heated at reflux for 20 hours and'then cooled in an ice bath. The resulting crystals were collected by filtration, suspended in chloroform, and treated with dilute potassium hydroxide. The chloroform layer was separated and evaporated to dryness under reduced pressure to give, after recrystallizaton from isopropyl .alcohol, 31.5 g. of 3-(dimethylamino)-7-fluoro—1,2,3,4— tetrahydrocarbazole, m.p. l74°—176°C. EXAMPLE 239 3-( Dimethylamino )-7-( benzyloxy)-l ,2,3 ,4-tetrahy- drocarbazole A solution of 15.8 g. of 4-dimethylaminocyclohexa— none hydrochloride and 20.3 g. of 3-benzyloxyphenyl- hydrazine hydrochloride (m.p. l65°—-168°C.) in 225 m1. of absolute ethyl alcohol was heated under reflux for three hours, cooled to room temperature and diluted with 50 ml. of water. After standing for three hours the resulting crystals were collected by filtration and washed with ethyl alcohol to give, after recrystallizaton from ethyl alcohol, 6.1 g. of 3-(dimethylamino)-7- (benzyloxy)-1 ,2,3,4-tetrahydrocarbazole hydro— chloried, m.p. 237°—239°C. 10 15 20 25 30 35 ' 50 EXAMPLE'24O 3-( Dimethylamino )-7—methoxy-l ,2,3 ,4-tetrahydrocar— bazole A solution of 7 g. of dimethylaminocyclohexanone and 8.4 g. of 3-methy0xyphenylhydrazine hydrochlo- ride in 40 ml. of absolute ethyl alcohol and 12 ml. of 4-N hydrogen cthride in ethyl alcohol was heated under reflux for 2 hours. The reaction mixture was allowed to stand for sixteen hours, filtered, and the filtrate was evaporated to dryness under reduced pres- sure. The residue was taken up in water, made alkaline with dilute sodium hydroxide and extracted with ether. The ether extract was washed with water, dried, ethe- real hydrogen. chloride was added, and the resulting oily precipitate was collected by decantation, recrystal- lized twice from isopropyl alcohol, suspended in chlo— roform and treated with dilute sodium hydroxide. The chloroform extract was evaporated to dryness under reduced pressure to -' give 3-(‘dimethylamino)-7— methoxy— 1 ,2,3,4-tetrahydrocarbazole, m.p. 100°—105°C. ’ ' EXAMPLE 241 3-(Dimethylamino)-5 -ethyl-1,2,3,4-tetrahydrocar- bazole - A solution of 21.2 g. of 4-dimethylaminocyclohexa- none hydrochloride and 20.7 g. of 3—ethylphenylhydra— zine hydrochloride (m.p. 205°—207°C-.) in 200 ml. of absolute ethyl alcohol was heated under reflux for 2 hours, filtered, and evaporated to dryness. The residual oil was taken up in ether, filtered, and the filtrate was - treated with dilute sodium hydroxide, separated, dried, 40 45 50 55 60 65 ‘dimeth’yl- l ,2,3,4-tetrahydrocarbazole, allowed to stand for 16 hours, and the resulting crystals were collected by filtration. The ether filtrate was ex- tracted six times with ‘warm cyclohexane. The cyclo- hexane was evaporated to dryness and the residue re- crystallized from ether-hexane. The resulting crystals were collected by filtration, combined with the crystals previously obtained above and recrystallized from cy— clohexane to give 4.1‘ g. of .3-(dimethylamino)-5-ethyl- 1,2,3-,4-tetrahydrocarbazole, m.p. 157°—161°C. EXAMPLE 242 ' 3—(Dimethy1amino)-6 ,7—dimethyl-1 ,2,3 ,4-tetrahy- drocarbazole A solution of 11.5 g. of 4-dimethylaminocyclohexa— none hydrochloride and 1 1 g. of 3,4—dimethylphenylhy- drazine hydroChloride in 200 ml. of absolute ethyl alco- hol was heated under reflux for 6 hours, cooled, fil- tered, and the filtrate was diluted with ether. The oily precipitate, which was collected by decantation and solidified On standing, was suspended in boiling isopro— pyl alcohol, filtered and dissolved in methyl alcohol. This solution was diluted with isopropyl alcohol and the methyl alcohol was removed by distillation. The cooled mixture was filtered to give 9.2 g. of a solid whichwas suspended in ether and treated with dilute potassium hydroxide. The ether extract was evaporated to dryness and the residue was suspended and boiled in hexane and filtered to give 3.2 g. of 3-(dimethylamin0)-6,7- m.p. 183°—187°C. ‘ - 3,959,309 55 lization from benzene, 6.9 g. of 3-(dimethylamino)-8- cyano-l ,2,3,4-tetrahydrocarbazole, m.p. l77°—179°C. EXAMPLE 252 3-( 1-Pyrrolidinyl)-8—methyl—l ,2,3 ,4-tetrahydrocar— bazole To a solution of 87.3 g. of 4-benzoyloxycyclohexa- none in 350 ml. of acetic acid was added 63.4 g. of 2-tolylhydrazine hydrochloride and the solution was heated under reflux for one hour, cooled, and filtered. The resulting solids were treated with 1.5 liters of boil- ing methyl alcohol and the undissolved solids were collected by filtration and recrystallized from 1 liter of methyl alcohol to give 32.5 g. of crystals, m.p. 159°—163°C. The first methyl alcohol filtrate on cooling yielded 29.1 g. of crystals, m.p. 159°~169°C. The first crop was recrystallized from 300ml. of acetic acid, the second crop was slurried in water and filtered, and the resulting solids were combined to yield 54 g. of 3-( ben- zoyloxy)-8-methyl-1,2 ,3 ,4-tetrahydrocarbazole , m.p. 159°—163°C. The 3-(benzoyloxy)—8-methyl—l,2,3,4-tet- rahydrocarbazole (62 g.) was converted to 23.9 g. of 3-( hydroxy)-8-methyl-l ,2,3 ,4—tetrahydrocarbazole, m.p. 201°—204°C., following a procedure similar to that described in Example 3 for the preparation of 3-(hy- droxy)-6-methoxy-1,2,3,4-tetrahydrocarbazole, 21.9 g. of which was converted to 32.6 g. of 3-(p—toluenesul- fonyloxy)—8—methyl-l ,2,3 ,4-tetrahydrocarbazole, m.p. 130°-—132°C., by following a procedure similar to that described in Example 18 for the preparation of 3-(p- toluenesulfonyloxy)-1,2,3,4-tetrahydrocarbazole. A mixture of 26.9 g. of 3-p-toluenesulfonyloxy)-8-meth- yl-i,2,3,4-tetrahydrocarbazole and 75 ml. of pyrrol- idine was heated under reflux for 11/2 hours in a nitro- gen atmosphere and the solution was evaporated to dryness under reduced pressure. The residue was re- crystallized from isopropyl alcohol and the resulting 8.5 g. of crystals were dissolved in ether and treated with hydrogen chloride in ethyl alcohol to give, after recrystallization from methyl alcohol, 6.8 g. of 3-(1- pyrrolidinyl )-8-methyl- l ,2,3,4—tetrahydrocarbazole, m.p. >300°C. - EXAMPLE 253 3-(Dimethylamino)-5,9-dimethyl—1,2,3,4-tetrahy— drocarbazole To a slurry of 1 g. of sodium hydride in 20 ml. of dimethylformamide was added 9.5 g. of 3-(dime— thylamino )-5-methyl- l ,2,3 ,4-tetrahydrocarbazole (Ex- ample 245A) in 100 ml. of dimethylformamide. The mixture was stirred for one hour, 5.9 g. of methyl io- dide was added to the resulting clear solution in one portion, and the solution was heated for 2 hours on a steam bath, stirred at room temperature for 1 hour, diluted in 300 ml. of water and left stand for 18 hours. The resulting solids were filtered, the filtrate was ex— tracted with ether, the ether extract was washed with water and dried over magnesium sulfate and evapo- rated to dryness. The residue was combined with the solids, dissolved in ether and, treated with hydrogen chloride in ethyl alcohol to give, on recrystallization from water, 3.5 g. of 3-(dimethylamino)-5,9-dimethyl- 1 ,2,3 ,4—tetrahydrocarbazole hydrochloride, m.p. 318°—320°C. 10 IS 20 25 30 35 40 45 50 55 60 65 56 EXAMPLE 254 3—( Dimethylamino )-5 ,7,9—trimethyl-1 ,2, 3 ,4-tetrahy- drocarbazole Following a procedure similar to that described in Example 253 and using 10.3 of 3~(dimethylamino)-5,7— dimethyl—1,2,3,4—tetrahydrocarbazole (Example 221 ), 7.02 g. of sodium hydride, 6.65 g. of methyl iodide, and 70 ml. of dimethylformamide there was obtained 5.4 g. of 3-(dimethylamino)-5,7,9—trimethyl-1,2,3,4—tetrahy- drocarbazole hydrochloride, m.p. 320°—322°C. EXAMPLE 255 3—(Dimethylamino )-9—carboxymethyl-l ,2,3,4-tetrahy- drocarbazole A mixture of 9.9 g. of 9-carbethoxymethyl—3-(dime- thylamino )-l ,2,3,4-tetrahydrocarbazole hydrochloride (Example 14) in 50 ml. of 6—N hydrochloric acid was heated on a steam bath' for one and one-half hours, cooled, and the resulting solids were collected by filtra- tion to give, after recrystallization from ethyl alcohol— water, 6.26 g. of 3-(dimethylamino)-9-carboxymethyl- 1 ,2,3 ,4-tetrahydrocarbazole hydrochloride, m.p. 316°—319°C. EXAMPLE 256 3-( Dimethylamino)-l ,2 ,3 ,4-tetrahydrocarbazole-9- propionic acid To a solution of 17.1 g. of 3-(dimethylamino)- 1,2,3,4-tetrahydrocarbazole in 150 ml. of benzene was added 10.6 g. of acrylonitrile followed by 1 ml. of 35% benzyltrimethylammonium hydroxide in methyl alco- hol. The solution was heated under reflux for one hour and fifteen minutes, cooled to room temperature, fil- tered, and evaporated to dryness. The residue was treated with hot hexane and then hot heptane (total volume 3.3 liters), both solutions being decanted from insoluble gum. The combined hexane-heptane solution was cooled and filtered to give a solid which, on recrys- tallization from hexane, yielded 8.6 g. of 3-(dime- thylamino )-9-(2-cyanoethyl )-1 ,2,3 ,4-tetrahydrocar- bazole, m.p. 106°-108°C. A solution of 13 g. of 3- (dimethylamino)-9-(2-Cyanoethyl)-1,2,3,4-tetrahy- drocarbazole in 125 ml. of ethyl alcohol and 150 ml. of 10% potassium hydroxide solution was heated under reflux for three hours, cooled, and the ethyl alcohol was removed under reduced pressure. The resulting aqueous solution was extracted with benzene, and the aqueous layer was separated and treated with acid to pH 7, cooled, and filtered to give 5.6 g. of solid mate- rial. The filtrate waas acidified to pH 6 and the result- ing crystals were collected by filtration. The filtrate was V evaporated to dryness under reduced pressure and the solid residue was slurried in water and collected by filtration. The above three crops of solids were com- bined, dissolved in ethyl alcohol and treated with hy- drogen chloride in ethyl alochol to give, on filtration and recrystallization from ethyl alcohol, 11.4 g. of 3- (dimethylamino )-l ,2,3,4-tetrahydrocarbazole-9-pro- pionic acid hydrochloride, m.p. 304°—305°C. 3,959,309 57 EXAMPLE 257 Ethyl 3-(dimethylamino)-l ,2,3,4-tetrahydrocarbazole-Q-pro— pionate Following a procedure similar to that described in Example 256 and using 20 g. of 3-(dimethylamino)— 1,2,3,4—tetrahydrocarbazole, 20 g. of ethyl acrylate, 1 ml. of 35% benzyltrimethylammonium hydroxide in methyl alcohol and 150 ml. of benzene and increasing the reflux time to three hours, there was obtained, on the evaporation of the reaction mixture to dryness, on oil, a solution of which in ethyl alcohol was treated with hydrogen chloride in ethyl alcohol. The resulting solids were filtered to give, after recrystallization from aque- ous ethyl alcohol, 20.5 g. of ethyl 3-(dimethylamino)- 1 ,2,3 ,4—tetrahydrocarbazole-9—propionate hydrochlo— ride, m.p. 259°—261°C. EXAMPLE 258 3-( Dimethylamino)—8—hydroxy—1 ,2,3 ,4—tetrahydrocar- bazole To a solution of 14 g. of 3—(dimethylamino)-8—ben- zyloxy-l ,2,3,4—tetrahydrocarbazole hydrochloride (Ex- ample 231 ) in aqueous ethyl alcohol (121) was added 1 g. of 10% palladium on charcoal and the mixture was subjected to a hydrogen atmosphere at about 60 psig until hydrogen uptake ceased. The mixture was filtered and the filtrate was evaporated to dryness to give 9.7 g. of 3-(dimethylamino)-8—hydroxy-1,2,3 ,4—tetrahy- drocarbazole hydrochloride, m.p. 315°—318°C. EXAMPLE 259 3-(Dimethylamino)-7-hydroxy-1 ,2,3 ,4-tetrahydrocar— - bazole Following a procedure similar to that described in Example 258 and using 12 g. of 3-(dimethylamino)-7- benzyloxy-l ,2,3 ,4-tetrahydrocarbazole hydrochloride (Example 239) in 200 ml. of aqueous ethyl alcohol (1:1) and 2 g. of 10% palladium on charcoal, there was obtained 10 g. of 3-(dimethylamino)-7-hydroxy- 1,2,3 ,4-tetrahydrocarbazole hydrochloride, m.p. 286°—288°C. EXAMPLE 260 3-(Benzylmethylamino)-6,8—difluoro-1,2,3,4-tetrahy- drocarbazole 4-(N-methylbenzamido)-cyclohexanol — A stirred solution of 12.9 g. of 4—methylaminocyclohexanol in 100 ml. of water and 50 ml. of 10% sodium hydroxide solution was cooled in an ice bath and 15.5 g. of ben- 20yl chloride was added dropwise and stirring was con- tinued for 30 minutes. The resulting precipitate was collected by filtration and washed with water to give 18.2 g. of 4-(N-methylbenzamido)-cyclohexanol, m.p. 159°—164°C. 4-(N-methylbenzamide)-cyclohexanone — A solu— tion of 17 g. of 4(-N-methylbenzamido)-cyclohexanol in 500 ml. of aqueous acetone (1:1) was heated under reflux and a solution of S-N chromium trioxide in aque- _ous sulfuric acid (prepared by adding 26.7 g. of chro- mium trioxide to 40 ml. of water followed by the addi— tion of 23 ml. of concentrated sulfuric acid and dilution to 100 ml.) was added dropwise until no starting mate— rial remained (as determined by thin layer chromatog- raphy). The mixture was cooled, made neutral by the 10 15 20 25 30 35 40 45 50 55 60 65 '58 addition of solid sodium bicarbonate, and the acetone was evaporated under reduced pressure. The mixture was filtered and the solids were washed several times with chloroform. The chloroform washes were used to extract the aqueous filtrate, dried, and evaporated to dryness to give 7 g. of 4-(N-methylbenzamido)- cyclohexanone, m.p. 126°—128°C. 3—( N-methylbenzamido—6,8-difluoro-1 ,2,3,4-tetrahy- drocarbazole — A solution of 16.2 g. of 4-(N—methyl~ benzamido)-cyclohexanone, 9.6 g. of 2,4—difluoro- phenylhydrazine, amd 13.4 g. of methanesulfonic acid in 200 ml. of absolute ethyl alcohol was heated under reflux for 2 hours, cooled, and filtered. The resulting solid was taken up in chloroform, filtered from undis— solved solids and evaporated to dryness to give, after recrystallization from isdpropyl alcohol, 9 g. of 3-(N- methylbenzamido)-6,8—difluoro-1,2,3 ,4—tetrahydrocar— bazole, m.p. 212°—214°C. To a slurry of 1.2 g. of lithium aluminum hydride in 60 ml. of dry tetrahydrofuran was added dropwise a solution of 4.6 g. of 3-(N—methylbenzamido-6,8— difluoro-l,2,3,4—tetrahydrocarbazole in 60 ml. of dry tetrahydrofuran and when addition was complete, the mixture was refluxed for forty minutes. Ethyl acetate (15 ml.) was added, followed by 10 ml. of wet ether and, finally 5 ml. of water. The mixture Was filtered and the filtrate was evaporated to dryness to give, after recrystallizations from cyclohexane and then isopropyl alcohol, 2.9 g. of 3-(benzylmethylamino)-6,8—difluoro- 1,2,3,4—tetrahydrocarbazole, m.p. 137°—139°C. A solu- tion of 0.85 g. of this free base was treated in acetonit- rile with 0.1 1 ml. of methyl iodide, and the solution was warmed on a steam bath for 15 minutes, cooled, and the resulting crystals were collected by filtration to give 0.65 g. of 3-(benzylmethyl-amino)-6,8-difluoro- 1 ,2,3',4-tetrahydrocarbazole methiodide, m .p, 235°—236°C. EXAMPLE 261 3 - [( 4-Fluorobenzyl )methylamino]-8—fluoro-1 ,2 ,3 ,4-tet— rahydrocarbazole Following procedures similar to those described in Example 260 there was obtained from 64.6 g. of 4- methyl-aminocyclohexanol, on reaction with 87.2 g. of 4-fluorobenzoyl chloride, 100.6 g. of 4-(N-methyl-4— fluorobenzamido)-cyciohexanol, m.p. 120°—130°C., 25.1 g. of which were oxidized to give 22.3 g. of 4-(N- methyl-4-fluorobenzamido)—cyclohexanone, m.p. 132°—136°C. 3-(N-methyl-4-fluorobenzamide)-8-fluor0-1,2,3,4- ’ tetrahydrocarbazole — A solution of 21.8 g. of 4-(N- methyl-4—fluorobenzamido)-cyclohexanone and 10.1 g. of 2-fluorophenyl—hydrazine in 200 ml. of absolute ethyl alcohol and 80 ml. of 5—N hydrogen chloride in absolute ethyl alcohol was heated under reflux for three and one-half hours, cooled, and filtered. The solids were slurried in water, filtered, and recrystallized from dimethylformamide to give 9.1 g. of 3-(N-methyl- 4-fluorobenzamido)-8-fluoro-i ,2 ,3 ,4—tetrahydrocar- bazole, m.p. 276°—278°C. By following a procedure similar to that described in Example 260 and using 6 g. of 3-(N-methyl-4- fluorobenzamido)—8-fluoro-1 ,2,3 ,4—tetrahydrocar— bazole in 500 ml. of dry tetrahydrofuran and 3 g. of 'lithium aluminum hydride in 60 ml. of dry tetrahydro- furan, there was obtained crude base as a yellow oil, a 3,959,309 59 solution of which in ethyl alcohol was treated with 10 ml. of S—N hydrogen chloride in ethyl alcohol to give, on filtration of the resulting solid, 5.1 g. of 3-[(4— fluorobenzyl )methylamin01-8-fluoro-l ,2,3,4-tetrahy- drocarbazole hydrochloride, m.p. 262°—264°C. EXAMPLE 262 3-( Ethylamino)—8—fluoro-l ,2,3,4—tetrahydrocarbazole 3—Acetamido—8—fiuoro-1,2,3,4—tetrahydrocarbazole — A solution of 7.8 g. of 4-acetamidocyclohexanone and 8.1 g. of 2-fluorophenylhydrazine hydrochloride in 75 ml. of absolute ethyl alcohol and 25 ml. of S-N hydrogen chloride in absolute ethyl alcohol was heated under reflux for two hours, cooled, filtered, and the filtrate was evaporated to dryness. The residue was dissolved in chloroform and adsorbed on a column of aluminum oxide. Dilution with ether yielded first a small amount of side—product followed by the desired product which was recrystallized by dissolving in methyl alcohol, adding toluene, and evaporation of the methyl alcohol, to give 10.5 g. of 3-acetamido—8—fluoro- l,2,3,4-tetrahydrocarbazole, m.p. 202°—204°C. Following a reductive procedure similar to that de- scribed in Example 260 but substituting for 3-(N— methylbenzamido-6,8-difluoro-1 ,2 ,3 ,4-tetrahydrocar- bazole an equivalent amount of 3-acetamido-8-fluoro— 1,2,3,4-tetrahydrocarbazole there can be obtained 3- (ethylamino )-8-fluoro- l ,2,3,4-tetrahydrocarbazole. EXAMPLE 263 3-(Isobutylamino)—6,8-difluoro-1,2,3 ,4-tetrahydrocar— bazole 3 -( Acetamido )-6,8-difluoro- l ,2 ,3 ,4-tetrahydrocar- bazole — A solution of 15.5 g. of 4-acetamidocy— clohexanone, 18 g. of 2,4-difluorophenylhydrazine hydrochloride and 10 g. of methanesulfonic acid in 200 ml. of absolute ethyl alcohol was heated under reflux for 2 hours, cooled, filtered, and the filtrate was evapo— rated to dryness under reduced pressure. The residual oil was triturated with water and the resulting solid was collected by filtration, triturated with ether, and recrys- tallized by dissolving in methanol, adding toluene, and evaporating the methanol to give 8.5 g. of 3- (acetamido)-6,8-difluoro-1 ,2,3,4-tetrahydrocarbazole, m.p. 179°—l83°C. 3-Amino-6,8vdifluoro-1 ,2,3 ,4-tetrahydrocarbazole — A suspension of 6 g. of 3-(acetamido)-6,8-difluoro- l,2,3,4 w tetrahydrocarbazole in 200 ml. of 20% aque- ous sulfuric acid was heated under reflux for forty hours and the resulting solution was cooled, filtered, made alkaline with dilute potassium hydroxide, and extracted with ether. The ether extract was washed with water, dried and ethereal hydrogen chloride was added to give on filtration 4.9 g. of 3-amino-6,8- difluoro- I ,2,3,4-tetrahydrocarbazole hydrochloride, m.p. > 300°C. This compound was found to have psy- chotrophic activity when tested in mice and is indicated for use as an antianxiety and antipsychotic agent. Following the acylation procedure similar to that described in Example 260 for the preparation of N— methylbenzamidocyclohexanol, there is obtained from 3-amino-6,8-difluoro-1,2,3 ,4-tetrahydrocarbazole and isobutyryl chloride, 3-isobutyramido-6,8-difluoro- 1,2,3,4-tetrahydrocarbazole, which by following the lithium aluminum hydride reductive procedure de- scribed in Example 260, can be converted to 3- 10 15 20 25 30 35 40 45 50 55 60 65 60 (isobutylamino)-6,8—difluor0-l ,2,3,4-tetrahydr0car- bazole. ‘ By following the lithium aluminum hydride reductive procedure described in Example 260 but using 3- ( acetamido )-6,8-difluoro-l ,2,3 ,4-tetrahydrocarbazole there is obtained 264. 3-(Ethylamino)-6,8-difluoro- 1 ,2,3,4-tetrahydrocarbazole. EXAMPLE 265 3-( Dimethylamino)-6-fluoro-9-(4-fluorophenyl )- 1 ,2,3 ,4-tetrahydrocarbazole A solution of 7.8 g. of 4-dimethylaminocyclohexa— none and 11 g. of l,l-bis(4-fluor0phenyl)hydrazine in 350 ml. of absolute ethyl alcohol and 90 ml. of 5—N hydrogen chloride in absolute ethyl alcohol was heated under reflux for five hours, cooled, and filtered. The solids were suspended in ether and treated with dilute sodium hydroxide solution and the ether extract was separated, dried and evaporated to dryness. The result- ing oil was dissolved in ethyl alcohol, treated with hy- drogen chloride in ethyl alcohol and the solution was concentrated and cooled. The resulting solids were collected by filtration to give, after recrystallization from ethyl alcohol, 5.6 g. of 3-(dimethylamino)-6- fluoro-9-( 4-fluorophenyl )—1 ,2 ,3 ,4-tetrahydrocarbazole hydrochloride, m.p. 283°~285°C. EXAMPLES 266—27 1 By following an acylation procedure similar to that described in Example 260 for the preparation of 4-(N- methylbenzamido)-cyclohexanol but substituting for 4-methylaminocyclohexanol an equivalent amount of 3-( methylamino )-5,6,7,8-tetrafluoro-l ,2,3,4-tetrahy- drocarbazole, 3-(dimethylamino)—6-amino-1,2,3 ,4-tetrahydrocar— bazole (Example 38), or 3-[2~(diethylamino)ethylamino]-1,2,3,4—tetrahy- drocarbazole (Example 31) and, in each case, for benzoyl chloride an equivalent amount of isobutyryl chloride or hexanoyl chloride there are obtained, respectively, 3 -( N—methylisobutyramido )-5 ,6,7 ,8-tetrafluoro- 1 ,2,3 ,4-tetrahydrocarbazole, 3-(N-methylhexanamido)—5,6,7,8-tetrafluoro- 1 ,2,3,4-te trahydrocarbazole, 3—(dimethylamino )-6—isobutyramido— l ,2,3 ,4-tetrahy- drocarbazole, 3—(dimethylamino )-6-hexanamido-1 ,2,3,4-tetrahy- drocarbazole, 3- N-[ 2-( diethylamino )ethyl ] isobutyramido — 1 ,2,3 ,4-te trahydrocarbazole, and 3- N-[2-(diethylamino)ethyl]hexanamido -1,2,3,4— tetrahydrocarbazole. By following a lithim aluminum hydride reduction pro- cedure similar to that described in Example 260 there are obtained from the above amides, respectively, 266. 3-(Methylisobutylamino)-5,6,7,8-tetrafluoro» l ,2,3,4-te trahydrocarbazole, 267. 3-(Methylhexylamino)-5,6,7,8-tetraf1uoro- 1 ,2,3,4-tetrahydrocarbazole, 268. 3-(Dimethylamino)—6-isobutylamino-1,2,3,4- tetrahydrocarbazole, 269. 3-(Dimethylamino)—6-hexylamino-l,2,3,4-tet- rahydrocarbazole, 270. 3-{lsobutyl-[2-(diethylamino)ethyllamino}- l,2,3,4—tetrahydrocarbazole, and 3,959,309 6 l 271. 3- Hexyl-[2-(diethylamino)ethyl]amino}- 1 ,2,3 ,4-tetrahy rocarbazole. The 3—(methylamino)-5 ,6,7,8—tetrafluoro-1 ,2,3,4-tet— rahydrocarbazole above can be prepared by following a . procedure similar to that described in Example 205 but substituting for 4-phenoxyphenylhydrazine hydrochlo— ride and 4-dimethy1aminocyclohexanone equivalent amounts of 2,3,4,5-tetrafluorophenylhydrazine hydro— chloride and 4-methylaminocyclohexanone respec- tively. EXAMPLES 272—273 By heating a solution of 3-(dimethylamino)-6-amino- 1,2,3,4-tetrahydrocarbazole or 3-[2—(diethylamino)e- thylamino]-l,2,3,4-tetrahydrocarbazole in formamide for several hours there can be obtained, after isolation by standard procedures, respectively, , 3-(dimethylamino)-6-formamido—l ,2,3,4—tetrahy- drocarbazole and 3- N-[2-(diethylamino)ethyl]formamido}-1,2,3,4- tetra ydrocarbazole, - which can be reduced with lithium aluminum hydride, following a procedure similar to that described in Ex- ample 260, to give, respectively, 272. 3-( Dimethylamino )-6-methylamino-1 ,2,3,4-tet- rahydrocarbazole and 273. 3-{ Methyl-[2-(diethylamino)ethyl ] amino} - l ,2,3 ,4-tetrahydrocarbazole. EXAMPLES 274—281 By following an acylation procedure similar to that described in Example 260 for the preparation of 4-N- (methylbenzamido)-cyclohexanol but substituting for 4—methylaminocyclohexanol an equivalent amount of 3-(methylamino)—6,8—difluoro— l ,2,3,4-tetrahydrocar- bazole (Example 249) and for benzoyl chloride an equivalent amount of the benzoyl chlorides substituted as follows: 3,4,5-trimethoxy, 4-methyl, 2-chloro-4— nitro, 3-trifluoromethyl, 4-hexyl, 4-isopropyl, 4-fluoro and 4-pentyloxy, there are obtained, respectively, 3 -( N—methyl-3 ,4,5-trimethoxybenzamido )-6,8- difluoro- l ,2,3 ,4-tetrahydrocarbazole, . 3-(N-methyl-4—methylbenzamido)-6,8—difluoro- 1 ,2,3 ,4-tetrahydrocarbazole, 3-(N-methyl-2—chloro-4—nitrobenzamido)-6,8- difluoro-l ,2 ,3 ,4-tetrahydrocarbazole, 3-[N-methyl-3-(trifluoromethyl)benzamido]-6,8- difluoro-l ,2 ,3 ,4—tetrahydrocarbazole, 3-( N-methyl—4—hexylbenzamido )-6 ,8-difluoro- . 1,2,3,4-tetrahdrocarbazole, 3~(N-methyl-4-isopropylbenzamido)-6,8-difluoro- l ,2,3 ,4-tetrahydrocarbazole, 3-(N-methyl~4-fluorobenzamido)-6,8-difluoro- 1,2,3,4-tetrahydrocarbazole, and 3-( N-meth yl-4-pentyloxybenzamido )-6, 8-difluoro- - 1,2,3,4-tetrahydrocarbazole, .By following a lithium aluminum hydride reducton procedure similar to that described in Example 260 there are obtained from the above benzamides, respec- tively, 274. 3-[( 3,4,5-Trimethoxybenzyl)methylamino]—6,8- difluoro-l ,2,3 ,4—tetrahydrocarbazole, ' 275. 3-[(4-Methylbenzyl)methylamino]-6,8- difluoro-l ,2,3,4-tetrahydrocarbazole, 276. 3- [ ( 2-Chloro-4—nitrobenzyl )methylamino]-6,8- difluoro-l ,2, 3 ,4—tetrahydrocarbazole, 277. 3-{[3-(Trifluoromethyl)benzyl]methylamino}- 6,8-difluoro-l ,2,3 ,4-tetrahydrocarbazole, 10 15 20 25 30 35 - 62 278. 3—[(4-Hexylbenzyl)methylamino]-6,8—difluoro- 1,2,3 ,4-tetrahydrocarbazole, 279. 3-[(4‘lsopropylbenzyl)methylamino]—6,8- difluoro-l ,2,3 ,4-tetrahydrocarbazole, 280. 3-[(4-Fluor0benzyl)methylamino]—6,8-difluoro- 1,2,3,4-tetrahydrocarbazole, and 281. 3-[(4-Pentyloxybenzyl )methylamino]~6,8- difluoro-l ,2 ,3 ,4-tetrahydrocarbazole. The following. compounds’(Example numbers given in parenthesis) were found to have antihistaminic activ- ity when tested according to test procedure 7, de- scribed hereinbefore, in the dose range of 1 to 30 mg./kg. (as base): 3-(dimethylamino)-8-fluoro- l ,2,3,4-tetrahydrocar- bazole (37), 3-( dimethylamino )-6,8-difluoro-l ,2 ,3 ,4-tetrahy- drocarbazole (204), 3-(dimethylamino)-5,8—difluoro-l ,2,3 ,4-tetrahy- drocarbazole (222), and 3-(dimethylamino)-8—fluoro-5-methyl-1 ,2,3,4-tet— rahydrocarbazole (224). By following the conventional procedures described hereinbefore for the preparation of acid-addition salts by reaction of the corresponding free bases with the appropriate acid there were obtained from the title compounds of Examples 37, 239 and 240 respectively the following: 37A. 3—(dimethylamino)-8-fluoro-1,2,3,4—tetrahy- drocarbazole methane sulfonate'; m.p. l74°—176°C.- (acetone); 239A. 3-(dimethylamino)-7-(benzyloxy)—1,2,3,4—tet- rahydrocarbazole methane sulfonate; m.p. 190°—l 93°C.(acetone-ether); and 240A. 3-(dimethylamino )-7-methoxy-1 ,2,3,4—tet— rahydrocarbazole hydrochloride; m.p. 250°—255°C- ' .(ethyl alcohol). 40 45 50 55 60 65 EXAMPLE 209A A mixture of racemic 3-(dimethylamino)-6,8- dichloro— l ,2,3 ,4-tetrahydrocarbazole (Example 209)(52g) and (-)-2,3:4,‘6-di-O-isopropylidene—Z— keto-L-gulonic acid hydrate (L-diacetone-Z-keto-L- gulonic acid hydrate) (53.8g.) in 550 ml. of water was stirred and warmed to 45°C. The resulting solution was filtered and allowed to stand at room temperature for 65 hours. The resulting crystals were filtered (filtrate A), washed with water, dried (yield 38g.) and recrystal- lized from ethyl alcohol (67ml)-water(136ml) and dried to give 35.5g. of d-3-(dimethylamino)-6,8— dichloro- 1 ,2,3 ,4—tetrahydrocarbazole L-diacetone-Z- keto-L—gulonate; m.p. 140°-150°C., which was con- verted to the free base (26g.) on treatment with aque- ous sodium hydroxide and extraction with chloroform. The free base was recrystallized from benzene to give 16g. of d-3—(dimethylamino)—6,8-dichloro-l,2,3,4-tet— rahydrocarbazole, m.p. 164°—166°C., [04025 = +89.6° ( 1% in CHCla), of which 14.7g. was treated with 4.3 ml. of concentrated hydrochloric acid in 300ml. isopropyl alcohol to give the corresponding hydrochloride salt, m.p. 297°—299°C.(dec.), [a],,25=-+7l.7°( 1% in H20). Filtrate A (above) was treated with sodium hydroxide until alkaline and extracted with chloroform and the extract was evaporated to dryness. The resulting resi— due was slurried in 200ml. of boiling isopropyl acetate and the mixture was cooled and filtered to give 15.5g. of the racemic base starting material. The isopropyl acetate filtrate was evaporated to dryness and the resi- due was triturated in boiling hexane and filtered to give 3,959,309 65 284A. 3-(ethylamino)-5,7-dichloro- l ,2,3,4-tetrahy- drocarbazole, and 3-(ethylamino)—6,8-dichloro- l,2,3,4—tetrahydroearbazole (Example 288). Following procedures similar to those described in ' Example 252 there are obtained starting from 3-(ben- zoyloxy )-6,8-dichloro- l ,2,3,4—tetrahydrocarbazole (Example 292) the following: 292A. 3~hydroxy-6,8-dichloro-l ,2,3 ,4—tetrahy- drocarbazole, m.p. 153°—156°C., 292B. 3-(p-tolueneslfonyloxy)-6,8-dichloro-l ,2,3,4- tetrahyrocarbazole, and 292C. 3-(l-pyrrolidinyl)-6,8-dichloro-1 ,2,3,4—tet- rahydrocarbazole. Following a hydrogenation procedure similar to that described in Example 258 there was obtained from the hydrochloride salts of the compounds of Examples 239B, 282A, 2828 and 291 respectively: 293. 3—( Dimethylamino)-5 -hydroxy- l ,2,3 ,4—tetrahy— drocarbazole hydrochloride, m.p.>300°C., 294. 3-(Dimethylamino)-57hydroxy—9-methyl- 1 ,2 ,3 ,4-tetrahyrocarbazole hydrochloride , m.p. 255°—258°C.(dec.), 295. 3-( Dimethylamino )-7-hydroxy—9 -methyl— 1 ,2,3 ,4-tetrahydrocarbazole hydrochloride, m.p. 295°C. ( dec. ), methane sulfonate salt, m.p. 227°—230°C., and 296. 3—(Dimethylamino)-7-hydroxy-6-methyl- 1 ,2,3 ,4—tetrahydrocarbazole hydrochloride, m.p. 299—301°C., methane sulfonate salt, m.p. 259°—261°C. EXAMPLE 297 3-( Dimethylamino )-5 -methoxy-1 ,2,3 ,4-tetrahydrocar- bazole Following a procedure similar to that described in Example 234 there was obtained from 12.1 g. of 3- (dimethylamino )-5-methoxy-8-chioro- l ,2,3 ,4-tetrahy- drocarbazole (Example 286), 8.7g. of the title com- pound, m.p. 185°—189°C. I claim: 1. A 3-(NR”’-CO-R5)-l,2,3,4-tetrahydrocarbazole having the formula Q [In 10 l5 20 25 30 35 40 45 50 55 60 65 66 where R5 is hydrogen, lower-alkyl or Ar; R’” is hydrogen or lower-alkyl; Q” is fluoro; n is an integer from 1 to 4; and Ar is phenyl or phenyl substituted by from one to three of the same or different substituents selected from non-tertiary-lower—alkyl, non-adjacent terti- ary-lower-alkyl, lower-alkoxy, non—adjacent trihal- omethyl, non-adjacent nitro and halo; where lower-alkyl and lower—alkoxy, every occurrence, have from one to six carbon atoms. 2. A compound according to claim 1 selected from: a. 3-( N-methylbenzamido—6,8-difluoro-l ,2,3,4-tet- rahydrocarbazole , 3-(N—methyl-4-fluorobenzamido)-8-fluoro- 1,2,3 ,4-tetrahydrocarbazole, and . 3 —acetamido—8 -fluoro-1 ,2 ,3 ,4-tetrahydrocar- bazole. 3. A 3-(NH-CO-R6)-l,2,3,4-tetrahydrocarbazole having the formula b. C Q' N NH—CO—R6 392 where R6 is hydrogen or lower—alkyl containing from one to six carbon atoms; 0'” is halo or lower-alkoxy containing from one to six carbon atoms; and p is the integer 2. 4. A compound according to claim 3 where R6 is methyl. ' 5. A compound according to claim 4 where Q’” is lower-alkoxy. 6. A compound according to claim 4 where Q’” is halo. ' 7. 3-Acetamido-6,7-dimethoxy-l ,2,3 ,4-tetrahy- drocarbazole according to claim 5. 8. ' 3-Acetamido-6,8-dichloro«l ,2,3,4-tetrahyrocar- bazole according to claim 6. 9. 3-Acetamido-5,7-dichloro- l ,2,3,4-tetrahydrocar- bazole according to claim 6. ' a: * * * * ...
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US3959309_TOT - United States Patent [191 [111 3,959,309...

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