GB1008263A - Dibenzocycloheptene derivatives and their preparation - Google Patents
Dibenzocycloheptene derivatives and their preparationInfo
- Publication number
- GB1008263A GB1008263A GB18913/62A GB1891362A GB1008263A GB 1008263 A GB1008263 A GB 1008263A GB 18913/62 A GB18913/62 A GB 18913/62A GB 1891362 A GB1891362 A GB 1891362A GB 1008263 A GB1008263 A GB 1008263A
- Authority
- GB
- United Kingdom
- Prior art keywords
- dibenzo
- compounds
- alkyl
- cycloheptene
- dimethylaminopropyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
- C07C211/31—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring the six-membered aromatic ring being part of a condensed ring system formed by at least three rings
- C07C211/32—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring the six-membered aromatic ring being part of a condensed ring system formed by at least three rings containing dibenzocycloheptane or dibenzocycloheptene ring systems or condensed derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/30—Ortho- or ortho- and peri-condensed systems containing three rings containing seven-membered rings
- C07C2603/32—Dibenzocycloheptenes; Hydrogenated dibenzocycloheptenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Display Racks (AREA)
Abstract
Compounds of the general formula <FORM:1008263/C4-C5/1> (wherein each of X and X1 represents a hydrogen atom or a C1- 6 alkyl radical and the dotted line indicates that the compounds may be saturated or unsaturated at the 10, 11-positions) are produced by dehydrating compounds of the general formula <FORM:1008263/C4-C5/2> by means of a chemical dehydrating agent. Specification 858,188 is referred to.ALSO:The invention comprises aminopropylidene dibenzocycloheptenes and their 10,11-dihydro derivatives, of the general formula <FORM:1008263/C2/1> and the corresponding aminopropyl compounds of the general formula <FORM:1008263/C2/2> (in which formulae the dotted lines indicate that the compounds may be saturated or unsaturated at the 10,11-positions, R represents a hydrogen atom or a C1-6 alkyl radical, and each of X and X1 represents a hydrogen or halogen atom or a trifluoromethyl, C1-6 alkyl, C1-4 alkoxy, mercapto, C1-4 alkylmercapto, C1-4 alkylsulphonyl, sulphamoyl, C1- 4 alkylsulphamoyl or C2- 6 dialkylsulphamoyl radical, but excluding, in formula (I), compounds in which X and X1 are both hydrogen or one is hydrogen and the other a halogen, when R = C1-6 alkyl, and their acid addition salts, and the preparation of these compounds by processes illustrated by the following reaction schemes:-(A) (for primary amines I, R = H): <FORM:1008263/C2/3> (the first step being effected in an inert solvent with subsequent hydrolysis, the second step by the action of a chemical dehydrating agent, the third step in a low-boiling solvent, the fourth step with any cyanide salt and the fifth step with a metal hydride in the presence of a solvent); (B) (for secondary amines, R = C2-6 alkyl): <FORM:1008263/C2/4> (or analogously for the aminopropyl compounds, R here representing a C1-5 alkyl radical, the first step alternatively employing an acyl halide and the second step being effected with a metal hydride in a solvent): (C) (for primary amines II, R-H): <FORM:1008263/C2/5> (R here representing a C1-6 alkyl radical and Hal a halogen atom); (D) (for secondary amines R = C1-6 alkyl): <FORM:1008263/C2/6> (or analogously for the aminopropylidene compounds, R1 and R11 representing hydrogen atoms or alkyl radicals and together containing at most 5 carbon atoms, the initial reaction with an aldehyde or ketone R1.CO.R11 being effected in a solvent and the reduction step with a metal hydride in a solvent); (E) (for secondary amines I, R = C1-6 alkyl): <FORM:1008263/C2/7> (the hydrolysis step being alternatively performed in an alkaline medium); (F) (for secondary amines II, R = C1-6 alkyl): <FORM:1008263/C2/8> (the hydrolysis being performed in an acid or alkaline medium); (G) (for primary amines II, R = H): <FORM:1008263/C2/9> (R here representing a C1-6 alkyl radical and Hal a halogen atom); (H) (for secondary amines II, R = C1-6 alkyl): <FORM:1008263/C2/10> 5 - (3 - Dimethylaminopropyl) - 5H - dibenzo [a,d] cycloheptene and its 10,11-dihydro derivative and their 3-chloro derivatives are prepared by treating 5 - chloro - 5H - dibenzo[a,d] cycloheptene or the corresponding 10,11-dihydro compound or their 3-chloro derivatives with a solution of 3-dimethylaminopropyl magnesium chloride in tetrahydrofuran. The first compound is isolated in the form of its hydrochloride. 3 - Dimethylsulphamoyl - 5 - (3 - dimethylaminopropyl) - 5H - dibenzo[a,d]cycloheptene is prepared similarly from 5-chloro-3-dimethylsulphamoyl - 5H - dibenzo[a,d]cycloheptene, obtained by treating 3-bromo-10,11-dihydro-5H-dibenzo [a,d]cycloheptene-5-one with fluorosulphonic acid to form its 7-fluorosulphonyl derivative, reacting this with dimethylamine to form the corresponding 7-dimethylsulphamoyl compound, removing the bromine atom by catalytic hydrogenation, dehydrogenating the product at the 10,11-positions by the action of N-bromosuccinimide followed by triethylamine, reducing the 5-one to the 5-ol with potassium borohydride, and treating the product with dry hydrogen chloride in dry dioxane and absolute ether. 5 - (3 - Dimethylaminopropylidene) - 3 - methylsulphonyl - 5H - dibenzo[a,d]cycloheptene is prepared by reacting 3-bromo-5H-dibenzo[a,d] cyclohepten-5-one with cuprous methylmercaptide (prepared from cuprous chloride and methyl mercaptan in aqueous alcoholic ammonia solution) to replace the bromine atom by -SCH3, reacting the product with 3-dimethyl-aminopropyl magnesium chloride to form 5 - (3 - dimethylaminopropyl) - 5 - hydroxy - 3-methylmercapto - 5H - dibenzo[a,d]cycloheptene, oxidizing the -SCH3 group to -SO2CH3 with hydrogen peroxide in acetic acid and dehydrating the product with trifluoroacetic anhydride in trifluoroacetic acid. The final product is separated into two isomers, isolated as hydrochloride and free base respectively. These isomers may be hydrogenated in the presence of Raney nickel to give their 10,11-dihydro derivatives. 5 - (3 - Dimethylaminopropyl) - 3 - methylsulphonyl - 5H - dibenzo[a,d]cycloheptene is prepared by reducing 3-methylmercapto5H-dibenzo[a,d] cyclohepten-5-one to the 5-ol, treating the product with dry hydrogen chloride in dry dioxane to form 5-chloro-3-methylmercapto-5H-dibenzo [a,d]cycloheptene, treating this with dimethylaminopropyl magnesium chloride and finally oxidizing the -SCH3 group to -SO2CH3. Grignard compounds.-3 - Ethoxypropylmagnesium bromide is prepared by reacting 3-ethoxypropyl bromide with magnesium in ether. 3-Dimethylaminopropylmagnesium chloride is prepared from 3-dimethylaminopropyl chloride and magnesium turnings in dry tetrahydrofuran in the presence of iodine and under an atmosphere of dry nitrogen, the reaction being initiated by the addition of a small amount of previously prepared 3-dimethylaminopropyl-magnesium chloride or of ethyl bromide. Pharmaceutical preparations.-The compounds of the invention, especially the acid addition salts, may be administered as antidepressants, mood elevators and psychic energizers. Specification 858,188 is referred to.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12083561A | 1961-05-24 | 1961-05-24 | |
US14022361A | 1961-09-25 | 1961-09-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1008263A true GB1008263A (en) | 1965-10-27 |
Family
ID=26818813
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB18913/62A Expired GB1008263A (en) | 1961-05-24 | 1962-05-16 | Dibenzocycloheptene derivatives and their preparation |
Country Status (13)
Country | Link |
---|---|
BE (1) | BE617967A (en) |
BR (1) | BR6239240D0 (en) |
CH (7) | CH464893A (en) |
CY (1) | CY354A (en) |
DE (2) | DE1593098A1 (en) |
DK (6) | DK110035C (en) |
FI (3) | FI41391B (en) |
FR (1) | FR2516M (en) |
GB (1) | GB1008263A (en) |
GT (1) | GT197016875A (en) |
MY (1) | MY6700003A (en) |
NO (1) | NO121833B (en) |
SE (8) | SE317369B (en) |
-
1962
- 1962-05-16 GB GB18913/62A patent/GB1008263A/en not_active Expired
- 1962-05-18 FI FI1007/62A patent/FI41391B/fi active
- 1962-05-21 DE DE19621593098 patent/DE1593098A1/en active Pending
- 1962-05-21 DE DE19621468212 patent/DE1468212A1/en active Pending
- 1962-05-22 BR BR139240/62A patent/BR6239240D0/en unknown
- 1962-05-22 BE BE617967A patent/BE617967A/en unknown
- 1962-05-23 DK DK232162AA patent/DK110035C/en active
- 1962-05-23 NO NO144482A patent/NO121833B/no unknown
- 1962-05-23 DK DK106164AA patent/DK107420C/en active
- 1962-05-23 DK DK106264AA patent/DK106278C/en active
- 1962-05-23 DK DK166663AA patent/DK106326C/en active
- 1962-05-23 DK DK106064AA patent/DK108151C/en active
- 1962-05-24 CH CH628562A patent/CH464893A/en unknown
- 1962-05-24 SE SE5885/62A patent/SE317369B/xx unknown
- 1962-05-24 CH CH1531868A patent/CH467744A/en unknown
- 1962-05-24 CH CH1532168A patent/CH465599A/en unknown
- 1962-05-24 CH CH1531968A patent/CH467238A/en unknown
- 1962-05-24 CH CH1104067A patent/CH464900A/en unknown
- 1962-05-24 CH CH1532268A patent/CH467743A/en unknown
- 1962-05-24 CH CH1532068A patent/CH464903A/en unknown
- 1962-05-24 SE SE13207/65A patent/SE325269B/xx unknown
- 1962-08-22 FR FR907533A patent/FR2516M/en active Active
-
1964
- 1964-02-27 DK DK97064AA patent/DK111679B/en unknown
-
1965
- 1965-05-14 SE SE635365A patent/SE318869B/xx unknown
- 1965-10-12 SE SE13209/65A patent/SE326441B/xx unknown
- 1965-10-12 SE SE13211/65A patent/SE326442B/xx unknown
- 1965-10-12 SE SE13204/65A patent/SE323364B/xx unknown
- 1965-10-12 SE SE13205/65A patent/SE326440B/xx unknown
- 1965-10-12 SE SE13210/65A patent/SE325874B/xx unknown
-
1966
- 1966-10-03 FI FI2587/66A patent/FI41646B/fi active
- 1966-10-03 FI FI2588/66A patent/FI41647B/fi active
- 1966-10-14 CY CY35466A patent/CY354A/en unknown
-
1967
- 1967-12-31 MY MY19673A patent/MY6700003A/en unknown
-
1970
- 1970-05-11 GT GT197016875A patent/GT197016875A/en unknown
Also Published As
Publication number | Publication date |
---|---|
CH465599A (en) | 1968-11-30 |
SE317369B (en) | 1969-11-17 |
CH464900A (en) | 1968-11-15 |
GT197016875A (en) | 1971-11-02 |
CH467238A (en) | 1969-01-15 |
NO121833B (en) | 1971-04-19 |
SE325269B (en) | 1970-06-29 |
MY6700003A (en) | 1967-12-31 |
CH464903A (en) | 1968-11-15 |
DE1468212A1 (en) | 1969-01-02 |
DE1593098A1 (en) | 1969-10-16 |
FI41391B (en) | 1969-07-31 |
DK106326C (en) | 1967-01-23 |
CH464893A (en) | 1968-11-15 |
BE617967A (en) | 1962-11-22 |
SE318869B (en) | 1969-12-22 |
DK106278C (en) | 1967-01-16 |
DK111679B (en) | 1968-09-30 |
SE326440B (en) | 1970-07-27 |
CH467744A (en) | 1969-01-31 |
BR6239240D0 (en) | 1973-05-24 |
DK108151C (en) | 1967-09-25 |
SE326442B (en) | 1970-07-27 |
SE323364B (en) | 1970-05-04 |
CH467743A (en) | 1969-01-31 |
CY354A (en) | 1966-10-14 |
SE326441B (en) | 1970-07-27 |
DK110035C (en) | 1968-09-02 |
FR2516M (en) | 1964-05-11 |
SE325874B (en) | 1970-07-13 |
FI41646B (en) | 1969-09-30 |
DK107420C (en) | 1967-05-29 |
FI41647B (en) | 1969-09-30 |
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