Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
  • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
  • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D223/08—Oxygen atoms

Definitions

• R and R are the same or different'and represent hydrogen, alkyl of one to five carbon atoms, hydroxyalkyl of one to five carbon atoms, hydroxyalkoxyalkyl of one to five carbon atoms in each alkyl residue, phenylalkyl of one to five carbon atoms in the alkyl residue, orphenylalkyl of one to five carbon atoms in the alkyl residue in which the phenyl nucleus is substituted by one or more of halogen, alkyl of one to five carbon atoms, alkoxy of one to five carbon atoms, nitro, amino, or trifluoromethyl, and R, is hydrogen, alkyl of one to five carbon atoms, phenylalkyl of one to five carbon atoms in the alkyl residue, or phenylalkyl of one to five carbon atoms in the alkyl residue in which the phenyl nucleus is
• the compounds of formula 1 are prepared by one of the following methods: I.
• the compounds of formula 1 in which R and R are both hydrogen may be prepared by reducing a compound of the general formula:
• R is as hereinbefore defined, preferably by the action of sodium in a saturated primary aliphatic alcohol of two to six carbon atoms, for example butanol, or by the action of sodium amalgam.
• R,, R, and R are as hereinbefore defined, by any method suitable for reducing a carbonamide group to a methyleneamino group.
• reducing agent it is advantageous to employ lithium aluminum hydride'and to carry out the operation in when organic solvent such as an ether, for example diethyl ether or tetr ahydrofuran.
• R is aspreviously defined and R is hydrogen, alkyl of one to fivecarbon atoms, hydroxyalkyl of one to five carbon atoms, hydroxyalkoxyalkyl of one to five carbon atoms in each alkyl residue, phenylalkyl of one to five carbon atoms in the alkyl residue, or phenylalkyl of one to five carbon atoms in the alkyl residue in which the phenyl nucleus is substituted by one or more of halogen, alkyl of one to five carbon atoms, alkoxy of one to five carbon atoms, amino, trifiuoromethyl, may be prepared by reacting a compound of the formula:
• Rr-CHO IV 2 which R, is as previously defined, and hydrogen in the presence of ahydrogenation catalyst, on a compound of the formula:
• N is of the formula N in which R is as hereinbefore defined, and R is alkyl of one to five carbon atoms, hydroxyalkyl of one to five carbon atoms, hydroxyalkoxyalkyl of one to five carbon atoms in each alkyl residue, phenylalkyl of one to five carbon atoms in the alkyl residue, or phenylalkyl of one to five carbon atoms in the alkyl residue in which the phenyl nucleus is substituted by one or more of halogen, alkyl of one to five carbon atoms, alkoxy of one to five carbon atoms, nitro, amino, or trifiuoromethyl, may be prepared by reacting a compound of the formula:
• R,-x VI in which R is as hereinbefore defined and X represents a reactive ester residue such as a halogen atom or a sulphuric or sulphonic ester residue (for example a methanesulphonyloxy or toluene-p-sulphonyloxy residue) with a compound of the formula:
• R COOH (where R is as hereinbefore defined) and to operate in an inert organic solvent such as benzene or toluene, with reflux of the solvent and in the presence or absence of a base such as a tertiary amine, for example pyridine.
• R in formula III is hydrogen
• the compounds of formula Vlllb may be obtained from compounds of the formula:
• NE V 1110 in which R, is as hereinbefore defined, by the action of cyanogen bromide, an alkyl chloroformate, an acid halide or an aliphatic or aromatic sulphonyl chloride.
• the compounds of formula I may optionally be purified by physical methods (such as distillation, crystallization or chromatography) or by chemical methods (such as formation of salts, crystallization of the latter and decomposition in alkaline medium). in these operations, the nature of the anion of the salt is immaterial, the only condition being that the salt should be well-defined and readily crystallizable.
• the compounds of formula I may be converted into acid addition salts and quaternary ammonium derivatives.
• the acid addition salts may be obtained by the action of the bases on acids in appropriate solvents.
• the organic solvents employed may be, for example, alcohols, ethers, ketones or chlorinated solvents.
• the salt formed precipitates after optional concentration of its solution and is separated by filtration or decantation.
• the quaternary ammonium derivatives may be obtained by the action of the bases on esters, optionally in an organic solvent, at ambient temperature or more rapidly with moderate heating.
• the compounds of formula I and their acid addition salts and quaternary ammonium derivatives have interesting pharmacodynamic properties. They are very active on the central nervous system as antidepressants and analgesics. They also have good activity as anticonvulsants and tranquillizers. They have given good results in physiological tests on animals in doses of 5 to 50 mg. per kg. of animal weight.
• the most interesting compounds are those of formula I in which R,, R and R, which are identical or different, represent hydrogen atom or alkyl of one to five carbon atoms. especially S-methyl-lO- methylaminol O, l l-dihydrodibenzo[ bflazepine.
• the new compounds may be employed either as bases or as pharmaceutically acceptable acid addition salts or quaternary ammonium derivatives, i.e. salts and derivatives which are nontoxic in the doses in which they are employed.
• pharmaceutically acceptable acid addition salts there may be mentioned salts of mineral acids (such as hydrochlorides, sulphates, nitrates and phosphates) and salts of organic acids (such as acetates, propionates, succinates, benzoates. fumarates. maleates, tartrates, theophyllineacetates, salicylates, phenolphthalinates and methylenebis-B-hydroxynaphthoates) or substitution derivatives of these acids.
• mineral acids such as hydrochlorides, sulphates, nitrates and phosphates
• organic acids such as acetates, propionates, succinates, benzoates. fumarates. maleates, tartrates, theophyllineacetates, salicylates,
• quaternary ammonium derivatives there may be mentioned derivatives of mineral or organic esters such as the methochlorides, methobromides, methiodides, ethochlorides, ethobromides. ethiodides, allylchlorides, allylbromides, allyliodides, benzyl chlorides,” benzyl-bromides, benzyliodides, the methyland ethyl-sulphates, the benzene-sulphonates and substitution derivatives of these compounds.
• the combined aqueous acid solutions are made alkaline with 100 cm. of 10 N sodium hydroxide solution and extracted three times with a total of 350 cm. of diethyl ether.
• the combined ethereal solutions are washed 3 times to neutrality with a total of 300 cm. of distilled water, dried over anhydrous sodium sulphate and evaporated.
• the residue (16.5 g.) is dissolved in 20 cm. of boiling diisopropyl ether. After cooling at 3 C. for 4 hours, the crystals which have appeared are separated, twice washed with a total of 20 cm. ice-cold diisopropyl ether and dried under reduced pressure (20 mm.Hg). 1 1.5 g.
• the starting S-methyl-l-hydroximino-10,1 1- dihydrodibenzo-[b,f]azepine may be prepared as follows. Methyl-l0-oxo-10,l 1-dihydrodibenzo[b,f]azepine (m.p. 104 C.) is prepared by the method of German Pat. No. 1,142,870. The reaction of an excess of hydroxylamine on 60 g. of 5- methyl--oxo-10,1 1-dihydrodibenzo[b,f]azepine in aqueous ethanolic medium under reflux gives 53.3 g. of 5-methyl-l0- hydroximino-10,1l-dihydrodibenzo[b,f]azepine (m.p. 196 C.).
• aqueous formaldehyde is hydrogenated in the presence of 18 g. of Raney nickel at normal temperature under a hydrogen pressure of 50 bars for 7 hours.
• the clear filtrate is evaporated under reduced pressure (l4mm.Hg).
• the residue is treated with 150 cm. of diethyl ether.
• the insoluble matter which appears is filtered off and washed with diethyl ether.
• the ethereal solution obtained is extracted four times with a total of 200 cm. of an icecold 2 N aqueous methanesulphonic acid solution, and the combined acid solutions are made alkaline in the cold with 45 cm. of 10N sodium hydroxide solution.
• dihydrodibenz0[b f]azepine are added in small portions in 2 1 minutes to a suspension of 1 1 of lithium aluminum hydride in 180 cm. of anhydrous diethyl ether, and the mixture is refluxed for 5 hours.
• the suspension, cooled to 5 C. is hydrolyzed in minutes by adding successively 1.3 cm. of distilled water, 0.95 cm. of 5 N sodium hydroxide solution and 4.3 cm. of distilled water. After stirring for 1 hour at ambient temperature, the precipitate formed is separated and washed three times with a total of 120 cm. of boiling methylene chloride The filtrate is evaporated and the residue dissolved in 250 cm. of diethyl ether.
• the ethereal solution obtained is extracted three times with a total of 150 cm. of aqueous 2 N methanesulphonic acid solution.
• the combined acid solutions are made alkaline in the cold with 40 cm. of 10N sodium hydroxide solution.
• the oil which separates out is extracted three times with a total of 300 cm? of diethyl ether.
• the starting S-methyl- 10-formamido-10, 1 ldihydrodibenzo-[b,f]a;epine is prepared as follows. 2 g. of 5- methyl-10-formarnido-l0, 1 1-dihydrodibenzo[ b,f]azepine (m.p. 142 C.) are obtained by heating 2.25 g. of 5-methy1-l0- amino-10,11dihydrodibenzo[b,f]azepine and 14.8 g. of ethyl formate in an autoclave at C. for 2 hours.
• EXAMPLE IV 205 g. of sodium amalgam containing 2.5 percent of sodium and 6.1 g. of l0-hydroximino-10,1 1-dihydrodibenzo[ b,f]azepine are brought into contact at a temperature between 30 and 40 C. in 76 cm. of percent ethanol until the sodium of the amalgam is completely consumed. in the course of this operation, the pH of the reaction medium is maintained in the neighborhood of 6 by the addition of a total of 18 cm.” of acetic acid. The reaction mixture is diluted with 760 cm. of distilled water. The mercury regenerated in the course of the reaction is eliminated by decantation. The aqueous phase is made alkaline with 25 cm.
• the starting 10-hydroximino-10,1 l-dihydrodibenzo[ b,f]azepine may be prepared as follows.
• IO-Methoxydibenzo[b,f]azepine (m.p. 125 C.) is prepared by the method of Swiss Pat. No. 375,721.
• the action of dilute hydrochloric acid on 14.0 g. of l0-methoxydibenzo[b,f] azepine gives 8.1 g. of 10-oxo-10,1 1-dihydrodibenzo-[ b,f]azepine (m.p. 141 C.).
• the aqueous acid solutions are made alkaline with 100 cm. of 10 N sodium hydroxide solution, and the oil which separates out is extracted three times with a total of 450 cm. of diethyl ether.
• the ethereal extracts are twice washed with a total of 200 cm. of distilled water, dried over anhydrous sodium sulfate, and evaporated.
• the residue obtained (7.5 g.) is dissolved in 20 cm. of boiling heptane. After cooling for 24 hours at 3 C., the crystals which have appeared are separated, washed with 10 cm. of heptane and dried under reduced pressure (20 mm.Hg).
• the product obtained (6.7 g., m.p.
• the starting 5-ethy1- 1 O-hydroximinol 0,1 1- dihydrodibenzo-[b,f]azepine may be prepared as follows. Methoxydibenzo[b,f]azepine is prepared as indicated in example IV. The reaction of sodamide and the n of ethyl iodide H in hexamethylphosphotriamide on g. of 20-methoxydibenzo[b,f]azepine give 15.4 g. of 5-ethyl-lO-methoxydibenzo[b,f]azepine (m.p. 180 C.). The action of dilute hydrochloric acid on 12.7 g.
• EXAMPLE V1 327 g. of sodium amalgam containing 2.5 percent of sodium and 1 1.6 g. of S-benzyl-lO-hydroximino-10,1 ldihydrodibenz0[b,f]azepine are brought intp ontacttug/31g in 320 cm. of 95perze iitqlianol until the sodium of the amalgam has been completely consumed.
• the pH of the reaction medium is maintained in the neighborhood of 6 by the addition of a total of 25 cm. of acetic acid.
• the mercury regenerated in the course of the reaction is eliminated by decantation.
• the aqueous ethanol phase is concentrated under reduced pressure (20 mm.Hg) to a volume of about 100 cm.
• EXAMPLE V 14.9 g. of S-methyl-10-acetylamino-10,1 l-dihydrodibenzo- [b,f]azepine are added in small portions in 2 minutes to a suspension of 6.35 g. of lithium aluminum hydride in 700 cm. of anhydrous diethyl ether. The mixture is heated under reflux for 5 hours and the suspension is then cooled to 5 C. and hydrolyzed by the addition of 7.3 cm. of distilled water, followed by 5.45 cm. of 5 N sodium hydroxide, and finally 25 cm. of distilled water. After stirring for 1 hour at 20 C.. the precipitate formed is separated and twice washed with a total of 100 cm. of boiling methylene chloride.
• the filtrate is thrice extracted with a total of cm. of aqueous 2 N methanesulphonic acid solution.
• the aqueous acid solutions are washed with 40 cm. of diethyl ether and then made alkaline with 18 cm. of 10 N sodium hydroxide solution.
• the oil which separates out is twice extracted with a total of cm.- of diethyl ether and the ethereal extracts are washed three times with a total of cm. of distilled water, dried over potassium carbonate and evaporated.
• the residue obtained 12.4 g.) is purified by conversion into the fumarate which is crystallized from ethanol (14 g., m.p. -138 C.) and reconversion into the base.
• the purified product (7.9 g.) is dissolved in 30 cm of anhydrous diethyl ether and the solution is treated at 3 C. with 16.1 cm. of a 1.94 N methanesulphonic acid solution in ethanol. After cooling for 2 hours at 3 C., the crystals which have appeared are separated, twice washed with a total of 20 cm. of anhydrous diethyl ether, and dried under reduced pressure (20 mm.Hg). 10.2 g. of S-methyll O-ethylamino- 1 0,1 l-dihydrodibenzo- [b,f]azepine methanesulphonic, m.p. 196 C., are obtained.
• the starting S-methyl- 1 O-acetylamino- 1 0,1 1- dihydrodibenzo-[b,f]azepine may be prepared as follows. 5- Methy1-10-amin0-10,l 1dihydrodibenzo[b,f]azepine (m.p. 96 C.) is prepared as described in Example 1.
• Methyl-1o-ethylamino-l lfil-dihydrodibenakfi bfiaiepirie is prepared as described in example VII.
• EXAMPLE 1X A solution of 10 g. of 5-methyl-l0-( N-formyl-N- ethylamino)-l0,l l-dihydrodibenzo[b,f]azepine in 200 cm. of anhydrous diethyl ether is added in 10 minutes to a suspension of 4.1 g. of lithium aluminum hydride in 200 cm. of anhydrous diethyl ether at 20 C. After heating under reflux for 4 hours, the suspension is cooled to 5 C. and hydrolyzed by the addition of 4.8 cm. of distilled water, followed by 3.5 cm. 3 of 5 N sodium hydroxide, and finally 15.8 cm. of distilled water.
• the precipitate formed is separated and twice washed with a total of 200 cm. of boiling methylene chloride.
• the filtrate is twice extracted with a total of 200 cm. of aqueous 2 N methanesulphonic acid solution and three times with a total of 150 cm. of distilled water.
• the combined aqueous acid solutions are made alkaline with 70 cm. of 5 N sodium hydroxide and the oil which separates out is extracted with 100 cm. of diethyl ether.
• the aqueous alkaline phase is saturated with sodium chloride and then again twice extracted with a total of 200 cm. of diethyl ether.
• the combined ethereal solutions are dried over potassium carbonate and evaporated.
• the starting S-methyll N-formyl-N-ethylamino )-N 10,11-dihydrodibenzo[b,f]azepine may be prepared as follows. 5 -Methyl-l0-ethylamino-10,1 l-dihydrodibenzo [b,f]azepine is prepared as described in example VII. The action of an excess of formylacetic anhydride at ambient temperature on 9.1 g. of S-methyl-l0-ethylamino-l0,l ldihydrodibenzo[b,f]azepine gives g. of S-methyl-lO-(N- formyl-N-ethylamino)-10,1 1 dihydrodibenzo[b,f] azepine (as a crude oily product).
• the united ethereal solutions are extracted twice with a total of 60 cm. of aqueous N methanesulphonic acid.
• the aqueous acid solutions are united and made alkaline with 10 cm. of 10 N sodium hydroxide solution, and the alkaline mixture is extracted three 3 times with a total of 120 cm. of diethyl ether.
• the etherealsolutions are united, dried over potassium carbonate, and evaporated.
• the residue 1.6 g.) is converted into the hydrochloride in ethanol, and then reconverted into the base which is recrystallized from aqueous ethanol to give 0.9 g. of S-methyl-l0-dimethylamino-10,l l-dihydrodibenzo[ b,f] azepine, m.p. 65-66 C.
• EXAMPLE Xlll A solution of 0.53 g. of 5-methyl-l0-(N-formyl-N- methylamino)-l0,ll-dihydrodibenzo(b,f]azepine in 10 cm. of n-butanol is heated under reflux for 8 hours in the presence of 0.66 g. of potassium hydroxide. After cooling, 100 cm. of distilled water are added, and the mixture is extracted twice with a total of 100 cm. of diethyl ether. The united ethereal extracts are washed with 25 cm. of distilled water, and then extracted twice with a total of 100 cm. of ice-cold aqueous N methanesulphonic acid solution.
• the united aqueous acid solutions are made alkaline with 25 cm. of 10 N sodium hydroxide solution, and extracted three times with a total of 120 cm. of diethyl ether.
• the united ethereal extracts are washed with 30 cm. of distilled water, dried over anhydrous magnesium sulphate, and evaporated.
• the residue obtained (0.39 g.) is converted in isopropanol into the hydrochloride of 5-methyll O-methylamino- 1 0,1 l-dihydrodibenzo[b,f]azepine (0.39 g.), m.p. 237-240C.
• S-methyl- 1 0-(N-formyl-N-methylamino)- l 0,1 ldihydrodibenzo-[b.flazepine used as starting material can be prepared as follows.
• S-Methyll O-formamidol 0,1 1- dihydrodibenz0[b,f]azepine is prepared the manner des'cibedin'examplelll.
• sodium hydride, followed by dimethyl sulphate at ambient temperature in anhydrous tetrahydrofuran, on 2.5 g. of 5-methyl-l0-formamido-l0,1 l-dihydrodibenzo-[b,f]azepine, 1.8 g. of 5- methyl-10-(N-formyl-N-methylamino)-10, l ldihydrodibenzo[b,f]azepine, m.p. 95 C., are obtained.
• EXAMPLE XIV 0.58 g. of sodium is added in portions over 8 minutes to a suspension of 0.98 of 5-methyl-l0-(N-methyl-N- tosylamino)-l0,l l-dihydrodibenzo[b,f]azepine in 15 cm. of n-butanol at 100 C. The reaction mixture is then heated under reflux for 30 minutes until the sodium has completely disappeared. After cooling, 100 cm. of distilled water are added, and the mixture is extracted twice with a total of 100 cm. of diethyl ether. The united ethereal extracts are extracted twice with a total of 80 cm. of ice-cold aqueous N methanesulphonic acid solution.
• the united aqueous acid solutions are made alkaline with 20 cm. of 10 N sodium hydroxide solution, and extracted twice with a total of 120 cm. of diethyl ether.
• the united ethereal extracts are dried over potassium carbonate and evaporated.
• the reside (0.56 g.) is dissolved in a mixture of 3 cm. of isopropanol and 3 cm. of diethyl ether.
• 0.6 cm. of a 4 N anhydrous solution of hydrogen chloride in diethyl ether is added, and after cooling for 1 hour at 3 C., the crystals formed are separated, washed with 2 cm. of a mixture of isopropanol and diethyl ether (1:1), then twice with a total of 4 cm.
• the suspension is then cooled to 5 C. and hydrolyzed in 1 hour by the successive addition of 1.45 cm. of distilled water, 1.1 cm. of 5 N sodium hydroxide solution, and 4.9 cm. of distilled water.
• the precipitate formed is filtered off and washed four times with a total of 200 cm. of diethyl ether.
• the filtrate is extracted twice with a total of 100 cm. of ice-cold aqueous 2 N methanesulphonic acid, and then with 50 cm? of distilled water.
• the united aqueous acid solutions are made alkaline with cm. of 10 N sodium hydroxide solution and then extracted three times with a total of 240 cm. of diethyl ether.
• the ethereal solutions are united and washed with cm.
• S-methyl-10-(N-ethoxycarbonyl-N-methylamino)- l0,l l-dihydrodibenzo[b,f]azepine used as starting material can be prepared as follows: S-Methyl-10-methy1amino-l0,l ldihydrodibenzo[b,f]azepine is prepared by the method of ex-z ample Ill. The action of ethyl chlorofiarmatein benzene in the presence of triethylamine on 13.9 g. of S-methyl-lO- methyIamino-l0,l l-dihydrodibenzo[b,f]azepine, gives 10.1 g.
• compositions comprising, in association with a pharmaceutically acceptable carrier or coating, at least one 10,1 1- dihydrodibenzo[b,f]eazepine derivative of formula 1 or a nontoxic acid addition salt or quaternary ammonium derivative thereof.
• compositions may be in a form suitable for oral, parenteral, or rectal administration.
• Solid compositions for oral administration include tablets, pills, powders, or granules.
• the active compound is mixed with one or more inert diluents such as sucrose, lactose or starch.
• These compositions may also comprise, as is normal practice, substances other than diluents, e.g. lubricants such as magnesium stearate.
• Liquid compositions for oral administration include pharmaceutically acceptable emulsions, solutions, suspensions, syrups and elixers containing inert diluents such as water or paraffin oil. These compositions may also comprise substances other than diluents, for example wetting agents, sweetening agents, perfumes and preservatives.
• compositions according to the invention for parenteral administration may be aqueous or nonaqueous sterile solutions, suspensions or emulsions.
• solvent or vehicle there may be employed propylene glycol, polyethylene glycol, vegetable oils, more particularly olive oil, and injectable organic esters, for example ethyl oleate.
• These compositions may also contain adjuvants, more particularly wetting agents, emulsifiers and dispersing agents.
• the sterilization may be effected in various ways, for example with the aid of a bacteriological filter, by incorporating sterilizing agents in the composition, by irradiation or by heating.
• the compositions may also be prepared in the fonn of sterile solid compositions which may be dissolved at the time of use in sterile water or any other sterile injectable medium.
• compositions for rectal administration are suppositories which contain, in addition to the active compound, excipients such as cacao butter or suppository wax.
• the dose employed depends upon the desired therapeutic effect, the route of administration and the duration of treatment.
• When orally administered generally between 10 and 250 mg. per day of active product is administered to an adult.
• EXAMPLE B Tablets having the following composition are prepared by the usual technique:
• R and R are the same or different and each represent hydrogen or alkyl of one to five carbon atoms, and R, is hydrogen, alkyl of one to five carbon atoms, or benzyl.
• a derivative as claimed in claim I which is lO-aminol0,l l-dihydrodibenzo[b,f]azepine or a pharrnaceutically acceptable acid addition salt.
• a derivative as claimed in claim I which is S-ethyl-lO- amino-10,1l-dihydrodibenzo[b,f]azepine or 'a pharmaceutically acceptable acid addition salt.
• a derivative as claimed in claim 1 which is S-benzyl-lO- amino-10,1l-dihydrodibenzo[b,f]azepine or a pharmaceutically acceptable acid addition salt.
• a derivative as claimed in claim 1 which is 5-methyl-l0- ethylamino-lO,l l-dihydrodibenzo[b,f]azepine or a pharrnaceutically acceptable acid addition salt.
• a derivative as claimed in claim 1 which is S-methyl- IO-diethylamino- 10,1 l-dihydrodibenzo[b,f]azepine or a pharrnaceutically acceptable acid addition salt.
• a derivative as claimed in claim I which is S-methyll0-methylethylamino-l0,l l-dihydrodibenzo[b,f]azepine or a pharrnaceutically acceptable acid addition salt.

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• 1967
  • 1967-01-18 FR FR91646A patent/FR1532301A/fr not_active Expired
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• 1968
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• 1971
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• 1972
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