CH473823A - Process for the preparation of new 4H-Benzo (4,5) cyclohepta (1,2-b) thiophene derivatives - Google Patents

Process for the preparation of new 4H-Benzo (4,5) cyclohepta (1,2-b) thiophene derivatives

Info

Publication number
CH473823A
CH473823A CH806365A CH806365A CH473823A CH 473823 A CH473823 A CH 473823A CH 806365 A CH806365 A CH 806365A CH 806365 A CH806365 A CH 806365A CH 473823 A CH473823 A CH 473823A
Authority
CH
Switzerland
Prior art keywords
benzo
cyclohepta
new
preparation
hydrogen atom
Prior art date
Application number
CH806365A
Other languages
German (de)
Inventor
Ernst Dr Jucker
Anton Dr Ebnoether
Jean-Michel Dr Bastian
Erwin Dr Rissi
Andre Dr Stoll
Original Assignee
Sandoz Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from CH1046764A external-priority patent/CH444185A/en
Priority claimed from CH1046864A external-priority patent/CH444186A/en
Priority claimed from CH806465A external-priority patent/CH473139A/en
Priority to CH806365A priority Critical patent/CH473823A/en
Application filed by Sandoz Ag filed Critical Sandoz Ag
Priority to GB32955/65A priority patent/GB1112601A/en
Priority to DE1965S0098688 priority patent/DE1250449B/en
Priority to BE668053D priority patent/BE668053A/xx
Priority to NO15927765A priority patent/NO115025B/no
Priority to NO16493865A priority patent/NO115027B/no
Priority to ES0316310A priority patent/ES316310A1/en
Priority to AT734365A priority patent/AT250947B/en
Priority to NL6510328A priority patent/NL6510328A/xx
Priority to NO16493765A priority patent/NO115026B/no
Priority to SE10448/65A priority patent/SE326197B/xx
Priority to SE10449/65A priority patent/SE326454B/xx
Priority to FR27924A priority patent/FR1447527A/en
Priority to DK409765A priority patent/DK107489C/en
Priority to SE10447/65A priority patent/SE326453B/xx
Priority to OA52143A priority patent/OA01791A/en
Priority to FR37801A priority patent/FR4866M/fr
Priority to FR82203A priority patent/FR91084E/en
Priority to US642295A priority patent/US3464983A/en
Priority to US646194A priority patent/US3491103A/en
Publication of CH473823A publication Critical patent/CH473823A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • C07D333/80—Seven-membered rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

  

  



  Verfahren zur Herstellung von neuen 4H-Benzo[4,5]cyclohepta[1,2-b]thiophen-Derivaten
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von neuen 4H-B   enzo[4,Sjcyclohepta[      1.,2-b]    thiophen-Derivaten der allgemeinen Formel 1 (siehe Formelblatt) und ihren Säureadditionssalzen, worin   Rt    ein Wasserstoffatom oder die Methylgruppe, R2 ein Wasserstoffatom, R3 eine niedere Alkylgruppe bedeuten, oder R3 mit R, zusammen die Dimethylen- oder die Trimethylengruppe, bzw. mit R2 zusammen die Trimethylen- oder die Tetramethylengruppe bedeuten, wobei das andere der Symbole   Rl    und R2 für ein Wasserstoffatom steht.



   Erfindungsgemäss gelangt man zu den neuen Verbindungen der allgemeinen Formel I und ihren Säureadditionssalzen, indem man ein 4H-Benzo[4,5]cyclo-   hepta[1 ,2-b]thiophen-Derivat    der allgemeinen Formel II, worin R1, R2 und R3 obige Bedeutung besitzen, mit Jodwasserstoff und rotem Phosphor unter Erhitzen reduziert, und das Reduktionsprodukt gegebenenfalls durch Behandeln mit anorganischen oder organischen Säuren in seine Säureadditionssalze überführt.



   Die neuen Verbindungen der Formel 1 besitzen wertvolle pharmakodynamische Eigenschaften. So zeichnen sie sich durch starke, für Antidepressiva typische Wirkungen aus, die sich am Tier u. a. in einer Hemmung der durch Reserpin oder Tetrabenazin hervorgerufenen vegetativen und motorischen Symptome äussern. Die Verbindungen potenzieren die Noradrenalinwirkung und besitzen vorwiegend zentral gerichtete anticholinergische Effekte. Die sedativ/neuroleptischen Eigenschaften sind bei den Substanzen nur mässig entwickelt. Die antidepressive Wirkung ist also insofern spezifisch, als die dämpfenden Eigenschaften bei den Verbindungen eher zurücktreten. Die Toxizität der Verfahrensprodukte ist verhältnismässig gering.



   Die neuen Verbindungen sollen zur Behandlung neurotischer und psychotischer Störungen, vor allem des depressiven Formenkreises Verwendung finden, ebenso können sie zur Therapie psychosomatischer Störungen verwendet werden. Sie werden vorzugsweise in Form ihrer physiologisch verträglichen, wasserlöslichen Salze verabreicht.



   In den nachfolgenden Beispielen, die die Ausführung des Verfahrens erläutern, den Umfang der Erfindung aber in keiner Weise einschränken sollen, erfolgen alle Temperaturangaben in Celsiusgraden und sind nicht korrigiert.
EMI1.1     




   Beispiel 4-[2-(2-Piperidyl)-äthyl]-9,10-dihydro-4H-benzo[4,5]    cyclohepta[1,2-bjthiophen   
Das Gemisch von   1,0    g   4-[2-(2-Piperidyl)-äthyliden]-      9,10    - dihydro -   4H-benzo[4,5]cydohepta1,2-    b]thiophen, 1,0 g rotem Phosphor, 5,6 ccm 56-proz. Jodwasserstoffsäure und 20 ccm Eisessig wird 10 Minuten zum Sieden erhitzt. Das Reaktionsgemisch wird wie in Beispiel 1 beschrieben aufgearbeitet. Die erhaltene Base wird im Hochvakuum destilliert, wobei das Isomerengemisch bei 165 bis   170     unter einem Druck von 0,08 mm Hg als gelbliches   öl    übergeht.



   Hydrochlorid: Eine acetonische Lösung der destillierten Base versetzt man mit der berechneten Menge acetonischer Salzsäure. Nach mehreren Stunden filtriert man das ausgefallene Hydrochlorid ab und kristallisiert es aus Aceton um. Smp. 164 bis   169C    (Zers.) (Isomerengemisch).



   Das als Ausgangssubstanz verwendete   4-[2-(2-Piper-      idyl) - äthylidenj - 9, 10-dihydro-4H -benzo[4,5]cyclohepta      [1,2-bithiophen    wird wie folgt hergestellt: a) Eine Lösung von 2,6 g Chlorameisensäureäthylester in 15 ccm abs. Benzol versetzt man mit der Lösung von 2,5 g   4-[2-(1-Methyl-2-piperidyl)-äthyliden]-9    10-dihydro-4H-benzo[4,5]cyclohepta[1,2-b]thiophen in 15 ccm abs. Benzol und lässt die erhaltene Lösung 24 Stunden bei Raumtemperatur stehen. Die Lösung wird anschliessend dreimal mit 1-n. Salzsäure, dann noch dreimal mit Wasser gewaschen, und über Natriumsulfat getrocknet.

   Nach Verdampfen des Lösungsmittels erhält man das reine 4-[2-(1-Äthoxycarbonyl-2-piperidyl)-   äthyliden]-9,1 O-dihydro-4H-benzo[4,5lcyclohepta[l ,2-b]    thiophen.   n2D      1,5772.    b) Die Lösung von 2,0 g   4-[2-(1-Äthoxycarbonyl-2-      piperidyl)-äthyliden1 -9,10-dihydro-4H-benzo[4,5lcyclo-      hepta[1,2-b]thiophen    und 25 ccm 48prozentiger Bromwasserstoffsäure in 50 ccm Eisessig wird in einer Stickstoffatmosphäre 20 Minuten zum Sieden erhitzt. Nach dem Abkühlen giesst man die Reaktionslösung in 250 ccm Eiswasser, stellt die Lösung mit Natronlauge stark alkalisch und schüttelt sie dreimal mit Methylenchlorid aus.

   Die organischen Extrakte werden mit Wasser gewaschen, über Natriumsulfat getrocknet und das Lösungsmittel unter vermindertem Druck verdampft.



   Hydrochlorid: Die Lösung des Rückstandes in Isopropanol wird mit der berechneten Menge isopropanolischer Salzsäure versetzt. Das ausgefallene Salz wird abfiltriert und aus Isopropanol umkristallisiert. Das 4 [2-(2-Piperidyl)-äthyliden]-9,10-dihydro-4H-benzo[4,5]   cyclohepta[1,2-b]thiophen-hydrochlorid    schmilzt bei 244 bis   247O    (Zers.) (Isomerengemisch).



  



  Process for the preparation of new 4H-benzo [4,5] cyclohepta [1,2-b] thiophene derivatives
The present invention relates to a process for the preparation of new 4H-B enzo [4, Sjcyclohepta [1., 2-b] thiophene derivatives of the general formula 1 (see formula sheet) and their acid addition salts, in which Rt is a hydrogen atom or the methyl group, R2 a hydrogen atom, R3 a lower alkyl group, or R3 with R, together the dimethylene or trimethylene group, or with R2 together the trimethylene or the tetramethylene group, the other of the symbols R1 and R2 being a hydrogen atom.



   According to the invention, the new compounds of the general formula I and their acid addition salts are obtained by adding a 4H-benzo [4,5] cyclohepta [1,2-b] thiophene derivative of the general formula II, in which R1, R2 and R3 Have the above meaning, reduced with hydrogen iodide and red phosphorus with heating, and the reduction product optionally converted into its acid addition salts by treatment with inorganic or organic acids.



   The new compounds of formula 1 have valuable pharmacodynamic properties. They are characterized by strong effects typical of antidepressants, which can be seen in animals and the like. a. manifest themselves in an inhibition of the vegetative and motor symptoms caused by reserpine or tetrabenazine. The compounds potentiate the norepinephrine effect and have mainly centrally directed anticholinergic effects. The sedative / neuroleptic properties of the substances are only moderately developed. The antidepressant effect is specific in that the depressant properties of the compounds tend to recede. The toxicity of the process products is relatively low.



   The new compounds are to be used for the treatment of neurotic and psychotic disorders, especially of the depressive type, and they can also be used for the therapy of psychosomatic disorders. They are preferably administered in the form of their physiologically compatible, water-soluble salts.



   In the following examples, which explain the implementation of the process but are not intended to restrict the scope of the invention in any way, all temperatures are given in degrees Celsius and are not corrected.
EMI1.1




   Example 4- [2- (2-piperidyl) ethyl] -9,10-dihydro-4H-benzo [4,5] cyclohepta [1,2-bjthiophene
The mixture of 1.0 g of 4- [2- (2-piperidyl) ethylidene] - 9.10 - dihydro - 4H-benzo [4.5] cydohepta1,2-b] thiophene, 1.0 g of red phosphorus, 5.6 cc 56 percent Hydroiodic acid and 20 cc of glacial acetic acid are heated to the boil for 10 minutes. The reaction mixture is worked up as described in Example 1. The base obtained is distilled in a high vacuum, the isomer mixture passing over as a yellowish oil at 165 to 170 under a pressure of 0.08 mm Hg.



   Hydrochloride: An acetone solution of the distilled base is mixed with the calculated amount of acetone hydrochloric acid. After several hours, the precipitated hydrochloride is filtered off and recrystallized from acetone. M.p. 164 to 169C (decomp.) (Mixture of isomers).



   The 4- [2- (2-piperidyl) -ethylidenj-9, 10-dihydro-4H-benzo [4,5] cyclohepta [1,2-bithiophene] used as starting substance is prepared as follows: a) A solution of 2.6 g of ethyl chloroformate in 15 ccm abs. Benzene is mixed with a solution of 2.5 g of 4- [2- (1-methyl-2-piperidyl) ethylidene] -9 10-dihydro-4H-benzo [4,5] cyclohepta [1,2-b] thiophene in 15 ccm abs. Benzene and the resulting solution is left to stand at room temperature for 24 hours. The solution is then three times with 1-n. Hydrochloric acid, then washed three times with water and dried over sodium sulfate.

   After evaporation of the solvent, the pure 4- [2- (1-ethoxycarbonyl-2-piperidyl) ethylidene] -9,1 O-dihydro-4H-benzo [4,5lcyclohepta [1,2-b] thiophene is obtained. n2D 1.5772. b) The solution of 2.0 g of 4- [2- (1-ethoxycarbonyl-2-piperidyl) -äthyliden1 -9,10-dihydro-4H-benzo [4,5lcyclo- hepta [1,2-b] thiophene and 25 cc of 48 percent hydrobromic acid in 50 cc of glacial acetic acid is heated to boiling for 20 minutes in a nitrogen atmosphere. After cooling, the reaction solution is poured into 250 cc of ice water, the solution is made strongly alkaline with sodium hydroxide solution and shaken out three times with methylene chloride.

   The organic extracts are washed with water, dried over sodium sulfate and the solvent is evaporated off under reduced pressure.



   Hydrochloride: The solution of the residue in isopropanol is mixed with the calculated amount of isopropanolic hydrochloric acid. The precipitated salt is filtered off and recrystallized from isopropanol. The 4 [2- (2-piperidyl) ethylidene] -9,10-dihydro-4H-benzo [4,5] cyclohepta [1,2-b] thiophene hydrochloride melts at 244 to 247O (decomp.) (Mixture of isomers ).

Claims (1)

PATENTANSPRUCH Verfahren zur Herstellung von neuen 4H-Benzo[4,5] cyclohepta[1,2-b]thiophen-Derivaten der allgemeinen Formel I und ihren Säureadditionssalzen, worin R1 ein Wasserstoffatom oder die Methylgruppe, R2 ein Wasserstoffatom, R3 eine niedere Alkylgruppe bedeuten oder R8 mit R1 zusammen die Dimethylen- oder die Trimethylengruppe, bzw. PATENT CLAIM Process for the preparation of new 4H-benzo [4,5] cyclohepta [1,2-b] thiophene derivatives of the general formula I and their acid addition salts, in which R1 is a hydrogen atom or the methyl group, R2 is a hydrogen atom, R3 is a lower alkyl group or R8 and R1 together represent the dimethylene or trimethylene group, or mit R2 zusammen die Trimethylen- oder die Tetramethylengruppe bedeuten, wobei das andere der Symbole R1 und R2 für eine Wasserstoffatom steht, dadurch gekennzeichnet, dass man ein 4H Benzo[4,5]cyclohepta[1,2-b]thiophen-Derivat der allgemeinen Formel II, worin R,, R2 und R3 obige Bedeutung besitzen, mit Iodwasserstoff und rotem Phosphor unter Erhitzen reduziert, und das Reduktionsprodukt gegebenenfalls durch Behandeln mit anorganischen oder organischen Säuren in seine Säureadditionssalze überführt. with R2 together denote the trimethylene or the tetramethylene group, the other of the symbols R1 and R2 being a hydrogen atom, characterized in that a 4H benzo [4,5] cyclohepta [1,2-b] thiophene derivative of the general Formula II, in which R 1, R 2 and R 3 have the above meanings, reduced with hydrogen iodide and red phosphorus with heating, and the reduction product optionally converted into its acid addition salts by treatment with inorganic or organic acids.
CH806365A 1963-12-19 1965-06-09 Process for the preparation of new 4H-Benzo (4,5) cyclohepta (1,2-b) thiophene derivatives CH473823A (en)

Priority Applications (20)

Application Number Priority Date Filing Date Title
CH806365A CH473823A (en) 1964-08-11 1965-06-09 Process for the preparation of new 4H-Benzo (4,5) cyclohepta (1,2-b) thiophene derivatives
GB32955/65A GB1112601A (en) 1964-08-11 1965-08-02 9,10-dihydro-4h-benzo[4,5] cyclohepta [1,2-b] thiophene derivatives and their production
DE1965S0098688 DE1250449B (en) 1964-08-11 1965-08-06 Process for the preparation of 9, 10-Dihydro-4H-benzo [4, 5] cyclohepta- [1, 2-b] thiophenes
NO16493765A NO115026B (en) 1964-08-11 1965-08-09
NL6510328A NL6510328A (en) 1964-08-11 1965-08-09
BE668053D BE668053A (en) 1964-08-11 1965-08-09
AT734365A AT250947B (en) 1964-08-11 1965-08-09 Process for the preparation of new 9, 10-dihydro-4H-benzo [4, 5] cyclohepta [1, 2-b] thiophene derivatives
NO15927765A NO115025B (en) 1964-08-11 1965-08-09
NO16493865A NO115027B (en) 1964-08-11 1965-08-09
ES0316310A ES316310A1 (en) 1964-08-11 1965-08-09 A procedure for the obtaining of derivatives of 9,10-dihydro-4h-benzo (4,5) ciclohepta (1,2-b) thiophene. (Machine-translation by Google Translate, not legally binding)
OA52143A OA01791A (en) 1964-08-11 1965-08-10 New benzo-cyclohepta-thiophenes and their preparation.
SE10448/65A SE326197B (en) 1964-08-11 1965-08-10
SE10447/65A SE326453B (en) 1964-08-11 1965-08-10
DK409765A DK107489C (en) 1964-08-11 1965-08-10 Process for the preparation of 9,10-dihydro-4H-benzo [4,5] cyclohepta [1,2-b] thiophene derivatives or acid addition salts thereof.
SE10449/65A SE326454B (en) 1964-08-11 1965-08-10
FR27924A FR1447527A (en) 1964-08-11 1965-08-10 New benzo-cyclohepta-thiophenes and their preparation
FR37801A FR4866M (en) 1964-08-11 1965-11-09
FR82203A FR91084E (en) 1964-08-11 1966-11-02 New benzo-cyclohepta-thiophenes and their preparation
US642295A US3464983A (en) 1964-02-04 1967-05-31 4h-benzo(4,5)cyclohepta(1,2-b)thiophenes
US646194A US3491103A (en) 1963-12-19 1967-06-15 Certain 4h-benzo(4,5)cyclohepta-(1,2-b) thiophenes

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CH1046864A CH444186A (en) 1964-08-11 1964-08-11 Process for the preparation of new thiophene derivatives
CH1046764A CH444185A (en) 1964-08-11 1964-08-11 Process for the preparation of new thiophene derivatives
CH806465A CH473139A (en) 1965-06-09 1965-06-09 Process for the preparation of new 9,10-dihydro-4H-benzo (4,5) cyclohepta (1,2-b) thiophene derivatives
CH806365A CH473823A (en) 1964-08-11 1965-06-09 Process for the preparation of new 4H-Benzo (4,5) cyclohepta (1,2-b) thiophene derivatives
CH806265 1965-06-09
CH1519265 1965-11-03

Publications (1)

Publication Number Publication Date
CH473823A true CH473823A (en) 1969-06-15

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ID=27543810

Family Applications (1)

Application Number Title Priority Date Filing Date
CH806365A CH473823A (en) 1963-12-19 1965-06-09 Process for the preparation of new 4H-Benzo (4,5) cyclohepta (1,2-b) thiophene derivatives

Country Status (8)

Country Link
BE (1) BE668053A (en)
CH (1) CH473823A (en)
DE (1) DE1250449B (en)
FR (1) FR4866M (en)
GB (1) GB1112601A (en)
NL (1) NL6510328A (en)
NO (3) NO115025B (en)
SE (3) SE326453B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8530245D0 (en) * 1985-12-09 1986-01-22 Sandoz Ltd Organic compounds

Also Published As

Publication number Publication date
NO115026B (en) 1968-07-08
NO115027B (en) 1968-07-08
GB1112601A (en) 1968-05-08
NO115025B (en) 1968-07-08
BE668053A (en) 1966-02-09
FR4866M (en) 1967-02-27
DE1250449B (en) 1967-09-21
SE326454B (en) 1970-07-27
SE326197B (en) 1970-07-20
NL6510328A (en) 1966-02-14
SE326453B (en) 1970-07-27

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