US3200130A - Derivatives of 1, 3, 4, 5-tetrahydro-benz[cd]indoles - Google Patents

Derivatives of 1, 3, 4, 5-tetrahydro-benz[cd]indoles Download PDF

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Publication number
US3200130A
US3200130A US304944A US30494463A US3200130A US 3200130 A US3200130 A US 3200130A US 304944 A US304944 A US 304944A US 30494463 A US30494463 A US 30494463A US 3200130 A US3200130 A US 3200130A
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Prior art keywords
indole
tetrahydrobenz
acid
methyl
ether
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Expired - Lifetime
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US304944A
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Szmuszkovicz Jacob
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Pharmacia and Upjohn Co
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Upjohn Co
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Priority to US304944A priority Critical patent/US3200130A/en
Priority to GB56250/64A priority patent/GB1073635A/en
Priority to GB26369/64A priority patent/GB1073634A/en
Priority to NL6409079A priority patent/NL6409079A/xx
Priority to DE19641470394 priority patent/DE1470394A1/de
Priority to CH1522467A priority patent/CH460785A/de
Priority to CH1107364A priority patent/CH460780A/de
Priority to FR1568710D priority patent/FR1568710A/fr
Priority to BE652388A priority patent/BE652388A/xx
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/90—Benzo [c, d] indoles; Hydrogenated benzo [c, d] indoles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/07—Organic amine, amide, or n-base containing

Definitions

  • the present invention relates to novel compounds and to processes for the preparation of the same. More particularly the invention relates to novel 3-(1-aminoalkyl)- 1,3,4,5-tetrahydrobenz[cd]indoles, to intermediates in the preparation thereof, to derivatives thereof, and to novel processes for the preparation of the same.
  • R represents hydrogen and lower-alkyl, e.g., methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, and the isomeric forms thereof;
  • R represents hydrogen, alkyl of from 1 to 4 carbon atoms, inclusive, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and the like, phenyl, hydroxyphenyl, e.g., p-hydroxyphenyl, m-hydroxyphenyl, 2,3-dihydroxyphenyl, 3,4-dihydroxyphenyl, 2,3,4 trihydroxyphenyl, and the like, alkoxyphenyl, wherein the alkoxy moiety is of from 1 to 4 carbon atoms, inclusive, e.g., p-methoxyphenyl, p-ethoxyphenyl, m-butoxyphenyl,
  • R represents hydrogen, benzyl and halobenzyl, e.g., chloro-, bromo-, iodo-, and fluorobenzyl which can be substituted with alkyl or alkoxy of from 1 to 4 carbon atoms, inclusive, and alkyl of from 1 to 4 carbon atoms, inclusive, e.g., methyl ethyl, propyl, butyl, isobutyl, and the like; R represents from zero to 3 members of the group consisting of hydroxy, benzyloxy, alkyl of from 1 to 4 carbon atoms, inclusive, e.g., methyl, ethyl, propyl, butyl, isobutyl, and the like, halogen, e.g., fluorine, chlorine, and bromine, and alkoxy of from 1 to 4 carbon atoms, inclusive, e.g., methoxy, ethoxy,
  • novel 3-(l-aminoalkyl)-l,3,4,5,-tetrahydrobenz- [cd]indoles of the invention exist either in the non-. protonated (free base) form or the protonated form depending upon the pH of the environment.
  • acid addition salts on neutralization with suitable acids, for example, hydrochloric, hydrobromic, sulfuric, phosphoric, nitric, perchloric, thiocyanic, fluosilicic, acetic, benzoic, salicylic, gycolic, succinic, nicotinic, tartaric, maleic, malic, lactic, methanesulfonic, cyclohexanesulfamic acids, and the like.
  • acids for example, hydrochloric, hydrobromic, sulfuric, phosphoric, nitric, perchloric, thiocyanic, fluosilicic, acetic, benzoic, salicylic, gycolic, succinic, nicotinic, tartaric, maleic, malic, lactic, methanesulfonic, cyclohexanesulfamic acids, and the like.
  • acids for example, hydrochloric, hydrobromic, sulfuric, phosphoric, nitric
  • oxides e.g., hydrogen peroxide.
  • methosulfate p-toluenesulfonate, 1 -naphthalenesulfonate, acetate, benzoate, salicylate, hydrocinnamate, succinate, lactate, or the like.
  • alkyl examples include methyl, ethyl, propyl, butyl, pentyl, hexyl', heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and isomeric forms thereof.
  • the noval compoundsof Formulea I wherein neither R is hydrogen also form N-oxides on oxidation with per-
  • the N-oxides also form stable protonates (acid addition salts) on neutralization with suitable acids, for example, hydrochloric, hydrobromic, sulfuric, phosphoric, .nitric, perchloric, thiocyanic, fluosilicic, acetic, benzoic, salicylic, glycolic, succinic, nicotinic, tartaric, maleic, malic, lactic, methanesulfonic, cyclohexanesulfamic acids, and the like.
  • acids for example, hydrochloric, hydrobromic, sulfuric, phosphoric, .nitric, perchloric, thiocyanic, fluosilicic, acetic, benzoic, salicylic, glycolic, succinic, nicotinic, tartaric, maleic, malic, lactic, methanesulfonic,
  • novelcompounds of Formula I either in the free base form, as acid addition salts wherein the acid is pharmacologically acceptable, for example, hydrochloric acid or citric acid, as lower alkyl quaternary ammonium salts, i.e., alkyl of from 1 to 8 carbon atoms, inclusive, or. as N-oxides have tranquilizing' activity in mice and rats and can be used tocalm agitated mammals, birds,
  • the fluosilicic acid addition salts and alkyl quaternary ammonium fluosilicates are useful as mothproofing agents according to US. Patents 1,915,334 and 2,075,359.
  • the .free bases of the invention also form salts with penicillins. These salts have solubility characteristics which cause them to be useful in the isolation and purification of penicillins, particularly benzyl penicillin.
  • Said Patented Aug. 10, 1965 salts like. the other salts specified above can be formed either by neutralization of the free base form of a compound of Formula I with the desired free acid, or by a metathetical exchange of the anion of a salt of a compound of Formula I, for example, the chloride ion of a hydrochloride, with the anionic form of the acid.
  • novel compounds of Formula I can be prepared by amidating an acid or an ester of the formula:
  • the amidation advantageously is effected by converting an acid of Formula II to the corresponding acyl halide, for example, by reaction with thionyl halide, carbonyl halide, or oxalyl halide, and reacting the acid halide with a compound of the formula HNRR wherein R is as given above. effected in the manner usual for such reductions of amides, for example, according to US. Patent 2,781,348.
  • novel compounds of Formula I can be prepared by reacting an acid of Formula II wherein R R and R are as given above, with an alkyl lithium to form a ketone of the formula:
  • R R R and R are as given above; and reducing the thus formed oxime with sodium and ethanol. A mixture of two diastereoisomers is obtained.
  • the mixture of isomers thus obtained can be separated.
  • a suitable process is to react the mixture Lithium aluminum hydride reduction can be of diastereoisomers with phthalic anhydride to form the corresponding isomeric phthalimides of the formula:
  • the compounds of Formula I wherein R is hydrogen can be alkylated at the 1-position by the usual procedures for alkylating indoles, e.g., they can be alkylated by reaction with an alkyl or aralkyl halide in the presence of an alkaline condensing agent such as an alkali metal amide or hydride.
  • An R hydrogen in the compounds of Formula I can be substituted by lower-alkyl by acylation followed by reduction with lithium aluminum hydride.
  • the acylation can be effected by conventional methods, such as, treatment with anhydride or acid chloride of a loweralkanoic acid, e.g., acetic anhydride or acetyl chloride, or a lower-alkyl lowcr-alkanoate, e.g., ethyl formate.
  • the lithium aluminum hydride reduction can be effected by the procedure given above. This procedure yields a secondary amine when both Rs in the compounds of Formula I are hydrogen, and a tertiary amine when only one R is hydrogen.
  • the starting compounds of Formula II are prepared by a Huang-Minlon reduction of the corresponding l,3,4,5- tetrahydro-S-oxobenz[cd]indole-3-carboxylic acid wherein R R and R are as given above, except that any hydroxy group will be acylated with alkanoyl of not more than 4 carbon atoms and R also can be alkanoyl of not more than 4 carbon atoms.
  • R R and R are as given above, except that any hydroxy group will be acylated with alkanoyl of not more than 4 carbon atoms and R also can be alkanoyl of not more than 4 carbon atoms.
  • These alkanoyls are the result of procedures used to make starting compounds, see below, but do not appear in the final products because any alkanoyl group is cleaved in the Huang-Minlon reduction.
  • the 5-oxo group of the acid is reduced with hydrazine hydrate and potassium hydroxide or other alkali metal hydroxide.
  • the reaction is carried out in an inert solvent, for example, diethylene glycol and triethylene glycol, at a temperature from about C. to about 210 C.
  • the desired l,3,4,5-tetrahydrobenz[cd]indole-3-carboxylic acid is then obtained by acidifying the reaction mixture with hydrochloric acid or other strong acid and recovered by such processes as extraction and crystallization. It can then be esterified if the ester is desired as starting compound.
  • R is other than hydrogen and can be alkanoyl (VIII) of not more than 4 carbon atoms.
  • the cyclization can be effected with aluminum chloride.
  • the reaction is advantageously effected in a Friedel-Crafts solvent, for example, ethylene dichloride, sym.-tetrachloroethane, nitrobenzene, carbon disulfide, and the like.
  • the reaction can be carried out at room temperature (about 24-30 C.), although in some cases gentle heating can be used.
  • the reagents are brought together at room temperature with or without cooling as may be desired and then heated on a steam bath until the reaction is'complete.
  • a molar excess of condensing agent for example, 3 moles of aluminum chloride for each mole of anhydride, is advantangeously used.
  • the amount of condensing agent can be varied over a wide range without afiecting the reaction other than in the matter of yield. Ordinarily it will not be necessary or desirable to use more than about 5 moles or less than about 1 mole of condensing agent for each mole of anhydride.
  • the product can be recovered from the reaction mixture and purified by recrystallization in a conventional manner.
  • the reaction mixture is cooled and treated with concentrated hydrochloric acid to insure efiective precipitation of the product.
  • Other strong acids for example, sulfuric acid and phosphoric acid can be used.
  • the 1-substituted-3-indolesuccinic anhydrides used as starting materials in the process of the invention can be prepared by reacting the corresponding l-substituted-S-indolesuccinic acid with isopropenyl lower-alkanoate, for example, isopropenyl formate, acetate, propionate, and butyrate.
  • the 1-lower-alkanoyl-3-indolesuccinic anhydrides can also be obtained by reacting the corresponding 1-substituted-3-indolesuccinic anhydrides with isopropenyl loWer-alkanoate.
  • the reaction is carried out in the presence of an inert solvent which may be an excess of the isopropenyl lower-alkanoate and in the presence of an acidic catalyst, for example, p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, sulfonic acid ionexchange resins, and the like.
  • an acidic catalyst for example, p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, sulfonic acid ionexchange resins, and the like.
  • the acetone formed in the reaction is distilled oif to complete the reaction and the product can be recovered from the solution in any suitable manner, for example, bycrystallization with or without recrystallization.
  • the l-alkanoyl group and any other alkanoyl group which may be introduced in this reaction will be cleaved in the subsequent Huang-Milon reduction.
  • the starting 3-indolesuccinic acids can be represented by the formula:
  • the aqueous solution thus obtained is acidified, e.g., with hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and the like. After standing for several hours, e.g., 2 to 12 hours, the 3-indolesuccinic acid is recovered by filtration.
  • the 3-indolesuccinic acids are prepared by the procedure of Perron et al., J. Org. Chem. 24, 1165, 1959, which involves condensing a 3-indolecarboxaldehyde with ethyl cyanoacetate or diethyl malonate, reacting the condensed product with potassium cyanide in ethanol, and hydrolyzing the resulting cyano derivativ with aqueous potassium hydroxide solution.
  • the 3-indolecarboxaldehydes can be prepared by reacting a 3-unsubstituted indole with dimethylformamide, in the presence of phosphorus oxychloride, using essentially the procedure described by Smith, J. Chem. Soc. 1954, 3842.
  • the starting indoles utilized to prepare 3-indolesuccinic acids can be prepared by the processes disclosed in US. Patent 2,825,734.
  • the benzyloxy group can be converted to hydroxy by hydrogenolysis which can be advantageously carried out in the presence of a palladium catalyst such as palladium black, palladium-barium sulfate, palladium-charcoal and the like, in the manner more fully disclosed in US. Patent 2,708, 197.
  • the reaction with isopropenyl lower-alkanoate will acylate the nitrogen with a 'loWer-alk-anoyl group.
  • the same or a difierent acyl group can be present in the starting 3-indolesuccinic acids.
  • These acyl groups can, when desired, be removed from the -1,3,4,5-tetrahydro-S-oxobenz[cdJindole-3-carboxylic acid by simple hydrolysis or they can be carried on in further processing of the compound and removed when and if desired by simple hydrolysis.
  • EXAMPLE 1 A. 2-methyl-1,3,4,5-ietrahydr0benz [cd] indol'e-3-carbonyl chloride c 0 OH 6 0 01 (C 0 Cl) 3 N CH3 ⁇ N/ CH: L I LE I 7 B. Z-methyZ-I ,3,4,5-tetrahydrbenz [cd] ind0le-3- carboxamide I C 0 01 C-NH2 ⁇ N/-CH3 CH3 Fifty ml. of aqueous ammonium hydroxide (29%) was added to one-half of the oily acid chloride of Part A (cooled in ice). An oily product separated which was broken up to give a precipitate.
  • the first figure is the wave length in millim-icrons and the second in parentheses is the molar absorptivity; the letter f stands for (flex; and unless otherwise specified, the solvent was 95% ethanol.
  • UV. 227 (62,800); f 274 (6,750); 280 (6,950); f 290 (5,100).
  • U.V. 227 (32,150); f 274 (6,900); 280 (6,950); f 290 (5,100).
  • U.V. 222 (71,850); f 242 (11,400); 275 (9,150); 279 (9,250); 290 (7,250).
  • dimethylamine in the amidation reaction there can be substituted other alkylamines, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, diethyl- 5 amine, ethylmethylamine, dipropylamine, dibutylamine,
  • R is selected from the group consisting of hy-' drogen and loweralkyl;
  • R is selected from the group consisting of hydrogen, alkyl of from 1 to 4 carbon atoms, inclusive, phenyl, hydroxyphenyl, alkoxyphenyl wherein alkoxy is of not more than 4 carbon atoms, and halophenyl;
  • R is selected from the group consisting of hydrogen, benzyl and halobenzyl which can be substituted with alkyl or alkoxy of from 1 to 4 carbon atoms, inclusive, and alkyl of from 1 to 4 carbon atoms, inclusive;
  • R is selected from zero to three members of the group consisting of hydroxy, benzyloxy, alkyl of not more than 4 carbon atoms, halogen, and alkoxy of not more than 4 carbon atoms; and
  • R is selected from the group consisting of hydrogen and alkyl of not more than 4 carbon atoms.
  • R (IV) wherein R is alkyl of not more than 4 carbon atoms and R R and R are as given in claim 1.
  • alkanoyl-2-methyl-1,3,4,5-tetrahydrobenz[cd]indole wherein the alkanoyl is from 2 to 5 carbon atoms, inclusive.
  • R is alkyl of not more than 4 carbon atoms, and R R and R are as given in claim 1.
  • alkanoyl-Z-methyl-l,3,4,5-tetrahydrobenz[cd]indole oxime wherein alkanoyl is from 2 to 5 carbon atoms, inclusive.
  • R is alkyl of not more than :4 carbon atoms and R R and R are as given in claim 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Indole Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
US304944A 1963-08-27 1963-08-27 Derivatives of 1, 3, 4, 5-tetrahydro-benz[cd]indoles Expired - Lifetime US3200130A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US304944A US3200130A (en) 1963-08-27 1963-08-27 Derivatives of 1, 3, 4, 5-tetrahydro-benz[cd]indoles
GB56250/64A GB1073635A (en) 1963-08-27 1964-06-25 Improvements in or relating to tetrahydrobenzo[cd]indoles and the manufacture thereof
GB26369/64A GB1073634A (en) 1963-08-27 1964-06-25 Improvements in or relating to tetrahydrobenz[cd]indoles and the manufacture thereof
NL6409079A NL6409079A (de) 1963-08-27 1964-08-07
DE19641470394 DE1470394A1 (de) 1963-08-27 1964-08-20 3-(1-Aminoalkyl)-1,3,4,5-tetrahydrobenz[cd]indole und Verfahren zu deren Herstellung
CH1522467A CH460785A (de) 1963-08-27 1964-08-24 Verfahren zur Herstellung von 3-(1-Aminoalkyl)-1,3,4,5-tetrahydrobenz(cd)indolen
CH1107364A CH460780A (de) 1963-08-27 1964-08-24 Verfahren zur Herstellung von 3-Amino-methyl-1,3,4,5-tetrahydrobenz(cd)indolen
FR1568710D FR1568710A (de) 1963-08-27 1964-08-26
BE652388A BE652388A (de) 1963-08-27 1964-08-27

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BE (1) BE652388A (de)
CH (2) CH460785A (de)
DE (1) DE1470394A1 (de)
FR (1) FR1568710A (de)
GB (2) GB1073634A (de)
NL (1) NL6409079A (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3386998A (en) * 1964-05-19 1968-06-04 Rohm & Haas Nu-alkenoyloxy-2-morpholinones and their corresponding hydrolysis products
US4110339A (en) * 1977-11-25 1978-08-29 Eli Lilly And Company 4-(Di-n-propyl)amino-1,3,4,5-tetrahydrobenz[cd]indole
US4282240A (en) * 1979-11-23 1981-08-04 Merck & Co., Inc. Amino substituted tetrahydrobenzindoles
US4501900A (en) * 1979-11-23 1985-02-26 Merck & Co., Inc. Amino substituted tetrahydrobenzindoles
US4576959A (en) * 1984-02-06 1986-03-18 Eli Lilly And Company 6-Substituted-4-dialkylaminotetrahydrobenz[c,d]indoles
US4983622A (en) * 1984-02-06 1991-01-08 Eli Lilly And Company 6-substituted-4-dialkylaminotetrahydrobenz(c,d)indoles
US5026869A (en) * 1984-02-06 1991-06-25 Eli Lilly And Company 6-substituted-4-dialkylaminotetrahydrobenz(c,d)indoles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2846382A (en) * 1955-07-25 1958-08-05 Ciba Pharmacentical Products I New process for the preparation of amines
US2890223A (en) * 1956-03-22 1959-06-09 Research Corp 1-benzyl, 2-methyl, 5-methoxy tryptamine
US2921941A (en) * 1958-02-21 1960-01-19 Du Pont Production of indolylmethyl-hydantoin
US2951090A (en) * 1958-04-17 1960-08-30 Ogilvie Flour Mills Co Ltd Preparation of dl-glutamine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2846382A (en) * 1955-07-25 1958-08-05 Ciba Pharmacentical Products I New process for the preparation of amines
US2890223A (en) * 1956-03-22 1959-06-09 Research Corp 1-benzyl, 2-methyl, 5-methoxy tryptamine
US2921941A (en) * 1958-02-21 1960-01-19 Du Pont Production of indolylmethyl-hydantoin
US2951090A (en) * 1958-04-17 1960-08-30 Ogilvie Flour Mills Co Ltd Preparation of dl-glutamine

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3386998A (en) * 1964-05-19 1968-06-04 Rohm & Haas Nu-alkenoyloxy-2-morpholinones and their corresponding hydrolysis products
US4110339A (en) * 1977-11-25 1978-08-29 Eli Lilly And Company 4-(Di-n-propyl)amino-1,3,4,5-tetrahydrobenz[cd]indole
US4282240A (en) * 1979-11-23 1981-08-04 Merck & Co., Inc. Amino substituted tetrahydrobenzindoles
US4501900A (en) * 1979-11-23 1985-02-26 Merck & Co., Inc. Amino substituted tetrahydrobenzindoles
US4576959A (en) * 1984-02-06 1986-03-18 Eli Lilly And Company 6-Substituted-4-dialkylaminotetrahydrobenz[c,d]indoles
US4983622A (en) * 1984-02-06 1991-01-08 Eli Lilly And Company 6-substituted-4-dialkylaminotetrahydrobenz(c,d)indoles
US5026869A (en) * 1984-02-06 1991-06-25 Eli Lilly And Company 6-substituted-4-dialkylaminotetrahydrobenz(c,d)indoles

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DE1470394A1 (de) 1970-01-02
GB1073635A (en) 1967-06-28
BE652388A (de) 1965-03-01
CH460785A (de) 1968-08-15
CH460780A (de) 1968-08-15
FR1568710A (de) 1969-05-30
NL6409079A (de) 1965-03-01
GB1073634A (en) 1967-06-28

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