the present invention relates to certain novel diazepine derivatives and oxides thereof and to the acid addition salts , particularly the pharmaceutically acceptable acid addition salts , of these azepine derivatives and oxides . more particularly the present invention relates to diazepine derivatives having the general formula i ## str1 ## wherein r 1 represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms , r 2 represents a hydroxy group , an alkoxy or an alkanoyloxy group having from 1 to 6 carbon atoms , a mono - or di - arylmethoxy group , a 2 - oxacycloalkoxy group having from 5 to 7 ring members or a fluorine atom , and a represents an alkylene group having from 1 to 3 carbon atoms and wherein each of the rings b and c may be substituted by one or more halogen atoms up to and including the atomic number 35 , trifluoromethyl groups or alkyl or alkoxy groups having from 1 to 6 carbon atoms and to their 5 - oxides as well as to the acid addition salts , particularly the pharmaceutically acceptable acid addition salts , of said diazepine derivatives and of their 5 - oxides . as alkyl group in the compounds of the general formula i , r 1 is , e . g . the methyl , ethyl or propyl group . as the alkoxy group , r 2 is , e . g . the propoxy , isopropoxy , butoxy , isobutoxy , pentyloxy , isopentyloxy , hexyloxy or isohexyloxy group , preferably , however , the methoxy or ethoxy group ; as the alkanoyl group , r 2 is , e . g . the formyloxy , acetoxy , propionoxy , butyroxy , isobutyroxy , valeroxy , isovaleroxy , pivaloyloxy , or hexanoyloxy group ; and as the monoarylmethoxy group , r 2 is , e . g . the benzyloxy , o -, m - or p - chlorobenzyloxy , o -, m - or p - methylbenzyloxy , o -, m - or p - methoxybenzyloxy or 3 , 4 , 5 - trimethoxybenzyloxy group ; as the diarylmethoxy group , r 2 is , in particular , the diphenylmethoxy group . as the 2 - oxacycloalkoxy group , r 2 is , e . g . the tetrahydrofuran - 2 - yloxy group ( 2 - oxa - cyclopentyloxy group ), the 2 - oxo - cycloheptyloxy group and , in particular , the tetrahydropyran - 2 - yloxy group . by an alkylene group a is meant any chosen bivalent , saturated aliphatic hydrocarbon radical having 1 to 3 carbon atoms , such as the methylene , ethylidene , 1 - methylethylidene , ethylene , propylene or trimethylene group ; of particular importance amongst these groups is the methylene group . halogen atoms as substituents of the rings b and c are fluorine , chlorine or bromine atoms , whilst suitable alkyl groups or alkoxy groups having 1 to 6 carbon atoms are , e . g . methyl , ethyl , propyl , isopropyl , butyl , isobutyl , tert . butyl , pentyl , isopentyl , 2 , 2 - dimethylpropyl , hexyl or isohexyl groups ; or methoxy , ethoxy , propoxy , isopropoxy , butoxy , isobutoxy , pentyloxy , isopentyloxy , 2 , 2 - dimethylpropoxy , hexyloxy or isohexyloxy groups . a substituent of the ring b is , in particular , in 8 - position , and is preferably fluorine , bromine , the trifluoromethyl group , and especially chlorine . the ring c is preferably unsubstituted , or substituted by fluorine , chlorine or bromine in any desired position , particularly , however , by fluorine or chlorine in o - position . the compounds of the general formula i , their 5 - oxides and the corresponding pharmaceutically acceptable and addition salts possess valuable pharmacological properties . they have a central depressant action , e . g . an anticonvulsive and antiagressive action ; they also inhibit somatic reflexes . the antoconvulsive effectiveness can be determined , e . g . in the electroshock test on the mouse with dosages of from ca . 2 . 0 mg / kg orally ; in the strychnine - spasm test on the mouse with dosages of from ca . 1 . 5 mg / kg orally ; and in the pentetrazole test on the mouse with dosages of from ca . 0 . 05 mg / kg orally . the antiagressive effectiveness is evident from the suppression of the fighting reaction of the mouse after oral administration of dosages of from ca . 0 . 3 mg / kg , whilst the general suppression of the central nervous system is shown , e . g . from the anaesthetic - potentiating action after oral administration to the mouse ; as well as from observation tests . the stated and also further properties , which can be assessed by selected standard tests [ cp . w . theobald and h . a . kunz , arzneimittelforsch . 13 , 122 ( 1963 ), as well as w . theobald et al ., arzneimittelforsch . 17 , 561 ( 1967 )], characterise the compounds of the general formula i and their 5 - oxides , as well as the pharmaceutically acceptable addition salts of the compounds of the general formula i and their 5 - oxides with inorganic and organic acids , as active substances for tranquillisers and for anticonvulsants , which are applicable , e . g . for the treatment of states of tension and agitation , as well as for the treatment of epilepsy . of particular importance are compounds of the general formula i having hydrogen as r 1 , the hydroxyl group as r 2 , and an alkylene group , particularly the methylene group as a ; and amongst these compounds especially those having a chlorine atom in the 8 - position , particularly 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , as well as 6 -( o - fluorophenyl )- and 6 -( o - chlorophenyl )- 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol . likewise of special pharmacological importance are compounds containing hydrogen as r 1 , fluorine as r 2 , and the methylene group as a , especially 1 -( fluoromethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine . the diazepine derivatives of the general formula i their 5 - oxides and the acid addition salts of these compounds generally are useful as intermediates in the production of pharmaceutically active products , and in particular such compounds having a mono - or diarylmethoxy group r 2 or a 2 - oxacycloalkoxy group r 2 having 5 to 7 ring members , particularly the tetrahydropyran - 2 - yloxy group , are important , apart from the fact that they are themselves pharmacologically effective , as intermediates for the preparation of corresponding compounds having an hydroxyl group as r 2 . likewise preferred , therefore , amongst these compound types are those having hydrogen as r 1 and the methylene group as a , and particularly those of them in which , at the same time , ring b is substituted in 8 - position by chlorine , whilst the ring c carries no substituent , or is substituted in o - position by fluorine or chlorine . 5 - oxides of compounds of the general formula i likewise have pharmacological activity , but their importance lies particularly in their applicability as intermediates for the production of further pharmacologically effective substances . according to the present invention there is also provided a process for the production of diazipine derivatives having the general formula i but wherein r 2 may not represent an alkanoyloxy group , which comprises condensing the corresponding compound having the general formula ii ## str2 ## wherein x represents a mercapto group , a lower alkoxy or a lower alkylthio group optionally activated by a substituent , or an optionally mono - or disubstituted amino group and r 1 has the meaning given above and the rings b and c may be substituted according to the definition given above , with a compound having the general formula iii wherein r 2 &# 39 ; has the meaning given for r 2 above with the exception that it may not represent an alkanoyloxy group and a has the meaning given above . as a lower alkylthio or alkoxy group , x is preferably the methylthio or ethylthio group , or the methoxy or ethoxy group . these groups can be activated by a substituent . such activated groups are , e . g . the o - or p - nitrobenzylthio or the o - or p - nitrobenzyloxy group . as a monosubstituted amino group , x is , in particular , a lower alkylamino group such as the methylamino group , or an aralkylamino group such as the benzylamino group . as a disubstituted amino group , x is , in particular , a lower dialkylamino group , such as the dimethylamino group . the above condensation reaction is preferably performed at a reaction temperature of ca . 80 ° to 180 ° c . in an inert solvent . suitable inert solvents are , for example , hydrocarbons such as toluene or xylene , halogenated hydrocarbons such as chlorobenzene , ethereal liquids such as diethylene glycol dimethyl ether , diethylene glycol diethyl ether or dioxane , amides , especially n , n , n &# 39 ;, n &# 39 ;, n &# 34 ;, n &# 34 ;- hexamethylphosphoric acid triamide , or n , n - dimethylacetamide , sulphoxides such as dimethylsulphoxide , and alcohols such as n - butanol . the reaction times are preferably between about one hour and 24 hours . starting materials embraced by the general formula ii are described in the literature , see , amongst others , l . h . sternbach and e . reeder , j . org . chem . 26 , 1111 ( 1961 ), s . c . bell et al ., j . med . chem . 5 , 63 ( 1962 ) and g . a . archer and l . h . sternbach , j . org . chem . 29 , 231 ( 1964 ). also described are compounds embraced by the general formula iii , such as , e . g . 2 - benzyloxyacetic acid hydrazide and glycolic acid hydrazide [ cp . th . curtius and n . schwan , j . prakt . chem . [ 2 ] 51 , 364 ( 1895 )]. further compounds of the general formulae ii and iii can be produced analogously to the known compounds . for example , further starting materials of the general formula ii having an optionally substituted amino group are obtained by reduction of the corresponding 4 - oxides described in the literature . according to a further aspect of the present invention there is provided a process for the production of diazepine derivatives having the general formula i wherein r 2 represents a hydroxy group and a represents a methylene , ethylene , trimethylene or propylene group , which comprises reducing , by means of a complex hydride in an ethereal solvent , the corresponding compound having the general formula iv ## str3 ## wherein y represents a hydrocarbon radical having at most 8 carbon atoms , r 1 has the meaning given above and the rings b and c may be substituted according to the definition given above . the complex hydride employed in this reductiom process is , e . g . lithium aluminium hydride , and the ethereal solvent , e . g . tetrahydrofuran or diethyl ether . the reduction is performed , e . g . at temperatures of between - 15 ° and + 20 ° c ., preferably around ca . 0 °. starting materials of the general formula iv can be produced analogously to the compounds of the general formula i by condensation of compounds of the general formula ii with aliphatic dicarboxylic acid ester hydrazides , e . g . with oxalic acid methyl ester hydrazide or oxalic acid ethyl ester hydrazide , instead of with compounds of the general formula iii . in addition to the foregoing diazipine derivations having the formula i wherein r 2 represents a hydroxy group may be prepared , in accordance with the present invention , by splitting the corresponding compound having the general formula i wherein r 2 represents a monoarylmethoxy , diarylmethoxy or 2 - oxacycloylkoxy group . the splitting of monoarylmethoxy or diarylmethoxy groups is preferably performed with the aid of hydrochloric acid , hydriodic acid , or especially hydrobromic acid . it is advantageous to use the hydrohalic acids in a solvent . suitable solvents are carboxylic acids such as acetic acid . the reaction temperature is ca . 20 ° to 150 ° c . the splitting of a 2 - oxacycloalkoxy group , such as , e . g . the tetrahydropyran - 2 - yloxy group , is effected likewise by the action of acids , such as , e . g . hydrohalic acids , but usually under milder conditions . splitting is performed , for example , by the action of diluted aqueous hydrochloric acid to which is added a water - miscible organic solvent , such as , e . g . methanol , at temperatures of ca . 50 ° to 100 ° c . or at the boiling temperature of the reaction mixture . the starting materials for this process may be obtained e . g . according to the first described process for the production of compounds of the formula i . finally the present invention provides a process for the production of diazepine derivatives having the general formula i wherein r 2 represents an alkanoyloxy group having from 1 to 6 carbon atoms which comprises acylating the corresponding compound having the general formula i wherein r 2 represents a hydroxy group . the starting materials wherein r 2 represents a hydroxy group may be prepared , e . g . according to any of the above described processes . the acylation can be carried out , for example , by the reaction of the free hydroxy compounds with acid halides or acid anhydrides which are derived from aliphatic carboxylic acids having 1 to 6 carbon atoms . acylation is performed preferably in an inert solvent , in the presence of a tertiary organic base such as , e . g . pyridine or triethylamine . suitable as solvents are hydrocarbons such as benzene or toluene , halogenated hydrocarbons such as carbon tetrachloride or chloroform , or excess tertiary organic bases . the reaction is carried out at ca . 0 ° to 80 ° c . the 5 - oxides of the subject diazipine derivatives are prepared by oxidation of the diazipine derivative itself . suitable oxidising agents are preferably hydrogen peroxide or peroxy acids and the oxidation is effectied e . g . at a temperature of ca . 0 ° to 70 ° c . suitable peroxy acids are , e . g . peroxyacetic acid or benzoperoxy acids such as benzoperoxy acid or , in particular , m - chlorobenzoperoxy acid . the oxidising agents are preferably used in a solvent , e . g . peroxyacetic acid in acetic acid , and benzoperoxy acid in halogenated hydrocarbons such as methylene chloride or chloroform . the compounds of the general formula i and their 5 - oxides obtained by the processes according to the invention are optionally converted , in the usual manner , into their addition salts with inorganic or organic acids . for salt formation are used , e . g . hydrochloric acid , hydrobromic acid , sulphuric acid , phosphoric acid , perchloric acid , methanesulphonic acid , ethanesulphonic acid or citric acid , preferably in the presence of a solvent such as , e . g . acetone , methanol , ethanol , ether , or mixtures thereof . the compounds of the general formula i as well as their 5 - oxides , and the corresponding pharmaceutically acceptable acid addition salts , are preferably administered orally or rectally . the daily dosages very between 0 . 01 and 2 mg / kg for warm - blooded animals . suitable dosage units , such as dragees , tablets or suppositories , preferably contain 0 . 5 - 25 mg of an active substance according to the invention , i . e . of a compound of the general formula i , of the 5 - oxide thereof , or of a pharmaceutically acceptable acid addition salt of these substances . the said dosage units are prepared by the combination of the active substance with solid pulverulent carriers such as lactose , saccharose , sorbitol , mannitol ; starches such as potato starch , maize starch or amylopectin , also laminaria powder or citrus pulp powder ; cellulose derivatives or gelatine , optionally with the addition of lubricants such as magnesium stearate or calcium stearate , or polyethylene glycols , to form tablets or dragee cores . the latter are coated e . g . with concentrated sugar solutions which may also contain , e . g . gum arabic , talcum and / or titanium dioxide , or with a lacquer dissolved in readily volatile organic solvents or solvent mixtures . dyestuffs can be added to these coatings , e . g . for identification of the various dosages of active substance . further suitable dosage units for oral administration are hard gelatine capsules , as well as soft closed capsules made from gelatine and a softener such as glycerin . the former contain the active substance preferably as a granulate in admixture with lubricants such as talcum or magnesium stearate , and , optionally , stabilisers such as sodium metabisulphite or ascorbic acid . the following directions serve to further illustrate the production of tablets , dragees and suppositories : ( a ) an amount of 50 . 0 g of 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol is mixed with 550 g of lactose and 292 g of potato starch ; the mixture is moistened with an alcoholic solution of 8 g of gelatine , and granulated through a sieve . after the drying of the granulate , 60 g of potato starch , 60 g of talcum , 10 g of magnesium stearate and 20 g of highly dispersed silicon dioxide are mixed in , and the obtained mixture is pressed to form 10 , 000 tablets each weighing 105 mg , and each containing 5 mg of active substance . if required , the tablets can be provided with grooves to give a more precise adjustment of the dosage amount . ( b ) an amount of 2 . 5 g of 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol is well mixed with 16 g of maize starch and 6 g of highly dispersed silicon dioxide ; the mixture is then moistened with a solution of 2 g of stearic acid , 6 g of ethylcellulose and 6 g of stearin in ca . 70 ml of isopropyl alcohol , and the whole granulated through a sieve iii ( ph . helv . v ). the granulate is dried for ca . 14 hours , and then put through sieve iii - iiia . it is afterwards mixed with 16 g of maize starch , 16 g of talcum and 2 g of magnesium stearate , and the mixture pressed to obtain 1000 dragee cores . these are coated with a concentrated syrup of 2 g of lacca , 7 . 5 g of gum arabic , 0 . 15 g of dyestuff , 2 g of highly dispersed silicon dioxide , 25 g of talcum and 53 . 35 g of sugar , and then dried . the obtained dragees each weigh 162 . 5 mg and each contain 2 . 5 mg of active substance . ( c ) 10 g of 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ]- benzodiazepine - 1 - methanol and 1990 g of finely ground suppository foundation material ( e . g . cocoa butter ) are thoroughly mixed and then melted . 1000 suppositories each weighing 2 g are poured from the melt maintained homogeneous by stirring . the suppositories each contain 10 mg of active substance . it is also possible to use as the active substance for tablets , dragees and suppositories the same amounts of 6 -( o - fluorophenyl )- 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol . in accordance with the foregoing the present invention provides in a final aspect , pharmaceutical compositions comprising a diazipine derivative , 5 - oxide or pharmaceutically acceptable acid addition salt according to the invention together with a pharmaceutically acceptable diluent or carrier therefore . the following examples further illustrate the production of the new compounds of the general formula i as well as of starting materials not hitherto known . temperatures are given in degrees centigrade . the petroleum ether employed is always one having a boiling range of 40 ° to 65 ° c . ( a ) a solution of 30 g of 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine [ cp . g . a . archer et al ., j . org . chem . 29 , 231 ( 1964 )] and 19 . 8 g of 2 - benzyloxyacetic acid hydrazide [ cp . th . curtius and n . schwan , j . prakt . chem . [ 2 ] 51 , 353 ( 1895 )] in 160 ml of hexamethylphosphoric acid triamide is heated for 8 hours at 140 °. the solvent is then distilled off in vacuo , and the residue distributed between methylene chloride and water . the organic phase is separated , washed with saturated aqueous sodium chloride solution , dried over sodium sulphate , and concentrated by evaporation . 1 -( benzyloxymethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 3 , 4 - a ][ 1 , 4 ] benzodiazepine crystallises out ; it melts at 163 °- 165 °. ( b ) in an analogous manner is obtained , with the use of 26 . 6 g of 2 -( methylthio )- 5 - phenyl - 3h - 1 , 4 - benzodiazepine : 1 -( benzyloxymethyl )- 6 - phenyl - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine , m . p . 167 °- 168 ° ( from ethyl acetate / petroleum ether ). ( a ) a solution of 7 . 8 g of 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine and 3 . 5 g of hydracrylic acid hydrazide in 70 ml of abs . hexamethylphosphoric acid triamide is heated for 9 hours at 140 ° c . the solvent is then distilled off in vacuo . the residue is taken up in methylene chloride ; the methylene chloride solution is washed with water and then with saturated sodium chloride solution , dried over sodium sulphate , and concentrated by evaporation . the residue is crystallised from methylene chloride / ethyl acetate / petroleum ether , and 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - ethanol , m . p . 227 °- 231 °, is obtained . if , instead of hydracrylic acid hydrazide , 6 . 5 g of 3 - benzyloxypropionic acid hydrazide are used , and the crude product is then purified by chromatography on aluminium oxide ( eluting agent : ethyl acetate ), and subsequent crystallisation from ethyl acetate / petroleum ether , then 1 -( 2 - benzyloxyethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine , m . p . 115 °- 117 °, is obtained . ( b ) an amount of 96 . 5 g of 3 - benzyloxypropionic acid methyl ester [ cp . j . j . bloomfield , j . org . chem . 27 , 2742 ( 1962 )] is dissolved in 1000 ml of abs . ethanol ; to the solution are then added 49 . 6 g of hydrazine hydrate , and the whole is allowed to stand for 65 hours at 25 °. the reaction mixture is then concentrated in vacuo , the residue distilled at ca . 150 °/ 0 . 005 torr , and 3 - benzyloxypropionic acid hydrazide obtained as colourless oil . an amount of 16 . 7 g of 3 - benzyloxypropionic acid hydrazide is dissolved in 200 ml of abs . ethanol ; the solution is then hydrogenated , after the addition of 2 . 0 g of palladium charcoal catalyst ( 5 % pd ), at 20 °- 25 ° and 760 torr for 61 hours . the reaction mixture is afterwards filtered through kieselguhr , and the filtrate concentrated by evaporation to ca . 50 ml . after the addition of petroleum ether , hydracrylic acid hydrazide precipitates and is filtered off , m . p . 94 °- 95 °. a solution of 10 . 0 g of 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine and 4 . 85 g of 2 - methoxyacetic acid hydrazide ( cp . e . j . browne and j . b . polya , j . chem . soc . 1962 , 5149 - 5152 ) in 70 ml of abs . hexamethylphosphoric acid triamide is heaated for 11 hours at 140 °. the solvent is then distilled off in vacuo . the residue is taken up in methylene chloride ; the solution is washed with water and then with saturated sodium chloride solution , dried over sodium sulphate , and concentrated by evaporation . crystallisation of the concentration residue from ethyl acetate / petroleum ether yields 1 -( methoxymethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine , m . p . 185 °- 191 °. after chromatography of the mother liquor on 100 g of silica gel &# 34 ; merck &# 34 ;, a further amount of final product of the same melting point can be isolated . in an analogous manner is obtained , with the use of 5 . 5 g of 2 - ethoxyacetic acid hydrazide [ cp . curtius , j . prakt . chem . [ 2 ] 95 , 171 ( 1917 )]: 1 -( ethoxymethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine , m . p . 161 °- 165 ° ( from ethyl acetate / petroleum ether ). in an analogous manner is likewise obtained , by reaction , with 9 hours &# 39 ; reaction time , of 8 . 95 g of 2 -( methylthio )- 5 - phenyl - 3h - 1 , 4 - benzodiazepine and 4 . 85 g of 2 - methoxyacetic acid hydrazide : 1 -( methoxymethyl )- 6 - phenyl - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine , m . p . 153 °- 154 ° ( from ethyl acetate / petroleum ether ). ( a ) a solution of 6 . 0 g of 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine and 3 . 44 g of 3 - ethoxypropionic acid hydrazide in 60 ml of abs . hexamethylphosphoric acid triamide is heated for 5 hours at 140 °. after processing analogous to that described in example 1 and crystallisation from ethyl acetate / petroleum ether , 1 -( 2 - ethoxyethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine , m . p . 128 °- 132 °, is obtained . the 3 - ethoxypropionic acid hydrazide used as starting material is prepared as follows : ( b ) an amount of 30 g of 3 - ethoxypropionic acid methyl ester [ cp . c . e . rehberg et al ., j . am . chem . soc . 68 , 544 - 546 ( 1946 )] is dissolved in 800 ml of abs . ethanol ; to this solution are then added 22 . 7 g of hydrazinehydrate , and the whole is allowed to stand for 3 days at 25 °. the reaction mixture is concentrated in vacuo , and the residue distilled in a bulb tube at 120 °/ 10 - 3 torr . in this manner is obtained colourless 3 - ethoxypropionic acid hydrazide , m . p . 34 °. ( a ) a solution of 15 , 0 g 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine [ cf . g . a . archer et al ., j . org . chem . 29 , 231 ( 1964 )] and 11 , 5 g 2 -( p - methoxybenzyloxy )- acetic acid - hydrazide in 100 ml hexamethyl - phosphoric acid triamide is heated for 10 hours at 140 °. the reaction mixture is worked up analogously to example 1 . the crude product is crystallised from ethyl acetate - petrol ether , whereby 1 -[( p - methoxybenzyloxy )- methyl ]- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine m . p . 157 °- 159 ° is obtained . analogously is obtained on using 16 , 7 g 2 -( methylthio )- 5 -( o - chlorophenyl )- 7 - chloro - 3h - 1 , 4 - benzodiazepine , 1 -[( p - methoxybenzyloxy )- methyl ]- 6 -( o - chlorophenyl )- 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine m . p . 200 °- 203 ° from ethyl acetate ). also analogously , but with a reaction time of 14 hours , there are obtained on using 15 , 9 g 2 -( methylthio )- 5 -( o - fluorophenyl )- 7 - chloro - 3h - 1 , 4 - benzodiazepine 1 -[( p - methoxybenzyloxy ) methyl ]- 6 -( o - fluorophenyl )- 8 - chloro - 4h - s - triazole [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine m . p . 163 , 5 °- 165 ° from ethyl acetate - petrol ether ); the substituted 2 -( methylthio )- 5 - phenyl - 3h - 1 , 4 - benzodiazepines required as starting compounds for the above - named end products can be prepared from the corresponding substituted 1 , 3 - dihydro - 5 - phenyl - 2h - 1 , 4 - benzodiazepine - 2 - thiones described in j . org . chem . 29 , analogously to the preparation of 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine which is described therein . further , there are obtained analogously to the above example , with a reaction time of 14 hours , ( b ) the substituted 2 -( methylthio )- 5 - phenyl - 3h - 1 , 4 - benzodiazepines used as starting compounds are obtained from the correspondingly substituted 1 , 3 - dihydro - 5 - phenyl - 2h - 1 , 4 - benzodiazepin - 2 - ones , whereof whose compounds which contain a trifluoromethyl group are described in the u . s . pat . no . 3 , 341 , 392 and , partly also in helv . chim . acta 45 , 2226 ( 1962 ). the three other compounds are described in j . org . chem . 27 , 3788 ( 1962 ). these compounds are converted into the corresponding 2 - thiones and the latter are reacted with dimethyl sulphate in methanolic sodium hydroxic solution analogously to the process described in j . org . chem . 28 , 231 ( 1964 ). ( c ) 2 -( p - methoxybenzyloxy )- acetic acid hydrazide , used in all cases as second reaction component , is obtained by reacting 58 g 2 -( p - methoxybenzyloxy )- acetic acid ethyl ester [ cf . a . viout and h . gault , compt . rend . 237 , 1162 ( 1953 )] with 22 , 7 g hydrazine hydrate analogously to example 4b ). a solution of 1 , 5 g 2 -( methylamino )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine [ cf . l . h . sternbach et al . j . org . chem . 26 , 1111 ( 1961 )] and 2 g of 2 - benzyloxy - acetic acid hydrazide in 10 ml abs . hexamethyl - phosphoric acid triamide is heated 24 hours at 160 ° and a further 4 hours at 170 °. then , the reaction mixture is evaporated in vacuo and the residue is distributed between ethyl acetate and water . the organic phase is separated , washed with saturated aqueous sodium chloride solution dried over sodium sulphate and evaporated . chromatography of the residue on silica gel , using ethyl acetate - isopropanol ( 7 : 1 ) as eluent and crystallisation from ethyl acetate - ether - petrol ether yields 1 -( benzyloxymethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazine , m . p . 163 °- 165 °. analogously , the same product is obtained on using the following starting compounds instead of 2 -( methylamino )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine : 1 , 44 g 2 - amino - 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine [ cf . s . c . bell et al ., j . med . chem . 5 , 63 ( 1962 )] or 1 , 90 g 2 -( benzylamino )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine [ obtainable according to british patent specification 1 , 023 , 793 or from the 4 - oxide described by s . c . bell et al ., loc . cit . analogously to the method of l . h . sternbach et al ., loc . cit ] or also in an analogous manner are obtained on using 1 , 60 g 2 - amino - 5 - phenyl - 7 -( trifluoromethyl )- 3h - 1 , 4 - benzodiazepine 1 -( benzyloxymethyl )- 6 - phenyl - 8 -( trifluoromethyl )- 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine , on using 1 , 42 g 2 - amino - 5 - phenyl - 7 - methoxy - 3h - 1 , 4 - benzodiazepine 1 -( benzyloxymethyl )- 6 - phenyl - 8 - methoxy - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine , and on using 1 , 34 g 2 - amino - 5 - phenyl - 7 - methyl - 3h - 1 , 4 - benzodiazepine 1 -( benzyloxymethyl )- 6 - phenyl - 8 - methyl - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine . the three starting compounds mentioned above are obtained e . g . according to the process of deutsche offenlegungsschrift 1 . 933 . 986 , chemical abstracts 72 , 100772 h ( 1970 ), or analogously to the 2 - amino - compound named before . a solution of 8 . 0 g of 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine and 1 . 4 g of 3 - hydroxybutyric acid hydrazide [ cp . j . biol . chem . 60 , 180 ( 1924 )] in 70 ml of abs . hexamethylphosphoric acid triamide is heated for 9 hours at 140 °. after processing analogous to that described in example 1 and crystallisation from ethyl acetate / ether , α - methyl - 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - ethanol , m . p . 182 °- 184 °, is obtained . with application of 4 . 1 g of 2 - methyllactic acid hydrazide [ cp . r . metze and w . kort , chem . ber . 91 , 417 ( 1958 )] is obtained , after a reaction time of 23 hours with otherwise the same procedure , α , α - dimethyl - 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , m . p . 234 °- 236 ° ( from ethyl acetate / petroleum ether ). crude 1 -[( diphenylmethoxy )- methyl ]- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine is obtained , analogously to example 1 , starting with 15 . 0 g of 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine and 14 . 1 g of 2 -( diphenylmethoxy )- acetic acid hydrazide in 100 ml of hexamethylphosphoric acid triamide , the reaction time being 12 hours . the crude product is purified by chromatography on silica gel with employment of benzyene / ethyl acetate ( 1 : 1 ) as the eluting agent , and crystallisation of the homogeneous fractions from ethyl acetate / petroleum ether . the pure substance melts at 202 °- 203 °. the hydrazide required as starting material is obtained from 2 -( diphenylmethoxy )- acetic acid methyl ester [ cp . c . djerassi and c . r . scholz , j . org . chem . 13 , 830 ( 1948 )] and hydrazine hydrate , analogously to example 4b ), as oil . from 15 . 0 g of 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine and 9 . 6 g of 2 -( tetrahydropyran - 2 - yloxy )- acetic acid hydrazide in 80 ml of hexamethylphosphoric acid triamide is obtained analogously to example 1 , but with a reaction duration of 24 hours , crude 1 -[( tetrahydropyran - 2 - yloxy )- methyl ]- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine . this is purified by chromatography on silica gel with the use of benzene / isopropanol ( 95 : 5 ) as the eluting agent , and subsequent crystallisation of the homogeneous fractions from ethyl acetate / petroleum ether . the pure substance melts at 159 °- 161 °. ( a ) 84 g of 3 , 4 - dihydro - 2h - pyran and 132 g of glycolic acid butyl ester are dissolved at room temperature . to this solution are added 0 . 5 ml of concentrated hydrochloric acid , whereupon the temperature immediately rises to 90 °. the solution is cooled to room temperature and stirred for 2 hours . after the addition of 1 g of sodium bicarbonate , the crude product is distilled under 17 torr to obtain 2 -( tetrahydropyran - 2 - yloxy )- acetic acid butyl ester , b . p . 127 °/ 17 torr . ( b ) 10 . 81 g of the above ester and 5 g of hydrazine hydrate are dissolved in 50 ml of abs . ethanol , the solution being then stirred for 20 hours at 60 °. the solution is concentrated in vacuo , and the residue distilled in a ball tube . 2 -( tetrahydropyran - 2 - yloxy )- acetic acid hydrazide passes over under 0 . 08 torr at ca . 150 ° and is in the form of a colourless oil , which soon crystallises , m . p . 55 °- 78 °. a solution of 8 g of 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine and 3 . 68 g of 2 - fluoroacetic acid hydrazide [ cp . m . a . phillips , agr . vet . chem . 2 , 86 - 87 ( 1961 ), c . a . 57 , 12314 ( 1962 )] in 80 ml of hexamethylphosphoric acid triamide is heated for 8 hours at 140 ° the solvent is then distilled off in vacuo , and the residue distributed between methylene chloride and water . the organic phase is separated , washed with saturated aqueous sodium chloride solution , dried over magnesium sulphate , and concentrated by evaporation . the residue is recrystallized from ethyl acetate / petroleum ether to obtain 1 -( fluoromethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine , m . p . 153 °- 154 °. ( a ) an amount of 25 g of 1 -( benzyloxymethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine is dissolved in 200 ml of glacial acetic acid ; to this solution are then added 170 ml of 48 % aqueous hydrobromic acid . the mixture is heated for 90 minutes at 80 °, and afterwards cooled to 5 °; the ph - value of the mixture is adjusted with concentrated sodium hydroxide solution to 6 , whilst stirring is maintained , and water and also methylene chloride are then added . the organic phase is separated , washed with saturated aqueous sodium chloride solution , dried over sodium sulphate , and concentrated by evaporation . the residue is dissolved in ethyl acetate / methanol ( 9 : 1 ), the solution filtered through a column of 150 g of silica gel ( merck ®, particle size 0 . 05 - 0 . 2 mm ), and the column eluted with ethyl acetate / methanol ( 9 : 1 ) to ( 7 : 3 ). the eluate is concentrated by evaporation and the residue crystallised from ethyl acetate / ether . in this manner is obtained 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , m . p . 210 °- 211 °. ( b ) in an analogous manner is obtained , starting with 5 g of 1 -( benzyloxymethyl )- 6 - phenyl - 4h - s - triazolo [ 4 , 3 - a ] [ 1 , 4 ] benzodiazepine in 40 ml of glacial acetic acid and 35 ml of 48 % aqueous hydrobromic acid with a reaction time of 105 minutes : 6 - phenyl - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , m . p . 205 °- 206 ° ( from ethyl acetate / petroleum ether ). in a likewise analogous manner is obtained , with application of the acid amounts stated in the second paragraph and with a reaction time of 120 minutes , from 5 g of 1 -( benzyloxymethyl )- 6 - phenyl - 8 -( trifluoromethyl )- 3h - 1 , 4 - benzodiazepine :- 6 - phenyl - 8 -( trifluoromethyl )- 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol ; from 5 g of 1 -( benzyloxymethyl )- 6 - phenyl - 8 - methoxy - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine :- 6 - phenyl - 8 - methoxy - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol ; and from 5 g of 1 -( benzyloxymethyl )- 6 - phenyl - 8 - methyl - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine :- 6 - phenyl - 8 - methyl - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol . to a solution of 3 , 0 g 1 -[( p - methoxybenzyloxy )- methyl ]- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine in 30 ml of glacial acetic acid is added at 25 ° 24 ml 48 % aqueous hydrobromic acid . the reaction mixture is stirred for 20 minutes , neutralised with 30 % sodium hydroxide solution and extracted with methylenechloride . the organic phase is separated , washed with water , dried over sodium sulphate and evaporated to dryness . the crystallisation of the residue from acetate - ether - petrol ether yields 6 - phenyl - 8 - chloro - 4 - h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , m . p . 209 °- 211 °. analogously are obtained from 3 , 23 g 1 -[( p - methoxybenzyloxy ) methyl ]- 6 -( o - chlorophenyl )- 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine at a reaction temperature of 20 ° and 55 minutes reaction time 6 -( o - chlorophenyl )- 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , m . p . 235 °- 237 ° ( from ethyl acetate - petrol ether ); from 3 , 12 g 1 -[( p - methoxybenzyloxy )- methyl ]- 6 -( o - fluorophenyl )- 8 - chloro - 4h - s - triazole [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine at a reaction temperature of 20 ° and a reaction time of 15 minutes 6 -( o - fluorophenyl )- 8 - chloro - 4h - s - triazolo [ 4 , 3a ][ 1 , 4 ] benzodiazepine - 1 - methanol m . p . 195 °- 197 ° ( from ethyl acetate - petrol ether ). also analogously are obtained at 20 ° with a reaction of 75 minutes a solution of 100 mg of 1 -[( diphenylmethoxy )- methyl ]- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine in 10 ml of glacial acetic acid and 8 ml of 48 % hydrobromic acid is stirred for 45 minutes at 25 °. the reaction mixture is then neutralised with 30 % aqueous sodium hydroxide solution , and extracted with ethyl acetate . the organic phase is washed with saturated sodium chloride solution , dried over sodium sulphate , and concentrated by evaporation . crystallisation of the residue from ethyl acetate / ether / petroleum ether yields : 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , m . p . 210 °- 211 °. an amount of 10 ml of 1 - n hydrochloric acid is added to a solution of 200 mg of 1 -[( tetrahydrofuran - 2 - yloxy ) methyl ]- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ]- benzodiazepine in 3 ml of methanol ; the whole is then stirred for 11 / 2 hours at 70 °- 80 °. the reaction mixture is diluted with ethyl acetate , and extracted with aqueous sodium bicarbonate solution . the organic phase is washed with water and saturated sodium chloride solution , dried over sodium sulphate , and concentrated by evaporation . crystallisation of the residue from ethyl acetate / ethyl / petroleum ether yields : 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , m . p . 210 °- 211 °. an amount of 7 . 0 g of 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol is dissolved in 50 ml of absolute pyridine ; to the solution are added 2 . 4 ml of acetic anhydride , and the whole is then allowed to stand for 17 hours at 25 °. the reaction mixture is afterwards concentrated in vacuo . the residue is dissolved in methylene chloride , and the solution washed with water and saturated sodium chloride solution , dried over sodium sulphate , and concentrated by evaporation . after crystallisation of the residue from ethyl / acetate is obtained 1 -( acetoxymethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine , m . p . 210 °- 212 °. a solution of 3 . 11 g of m - chloroperoxybenzoic acid in 40 ml of methylene chloride is added dropwise at 0 °- 5 ° in the course of 10 minutes , with stirring , to a solution of 3 . 0 g of 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol in 80 ml of methylene chloride . the reaction mixture is stirred , in a melting ice bath , for a further 16 hours . it is then concentrated in vacuo , and to it are added ether and petroleum ether . the precipitated crystals are filtered off under suction , and recrystallised twice from methanol / ethyl acetate / ether . the obtained 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol - 5 - oxide melts at 267 °- 269 °. starting with 3 . 13 g of 1 -( methoxymethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine is obtained : 1 -( methoxymethyl )- 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 5 - oxide , m . p . 244 °- 248 ° ( from dioxane ); ( a ) a solution of 0 . 37 g of 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - carboxylic acid ethyl ester in 5 ml of absolute tetrahydrofuran is added dropwise in the course of 15 minutes , with ice cooling and with stirring , to a suspension of 0 . 078 g of lithium aluminium hydride in 5 ml of absolute tetrahydrofuran . after a further 45 minutes of stirring at 0 °- 5 °, 0 . 40 ml of 1 - n sodium hydroxide solution are added dropwise . the inorganic salts are filtered off , the filtrate is concentrated in vacuo , and the residue dissolved in 10 ml of chloroform . the solution is washed with 1 - n sodium hydroxide solution and then with water , dried over sodium sulphate , and concentrated by evaporation . the residue is recrystallised from ethyl acetate / petroleum ether to obtain 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4benzodiazepine - 1 - methanol , m . p . 210 °- 211 °. from 0 . 33 g of 6 - phenyl - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - carboxylic acid ethyl ester is obtained : 6 - phenyl - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , m . p . 205 °- 206 ° ( from ethyl acetate / petroleum ether ); from 0 . 38 g of 6 -( o - fluorophenyl )- 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - carboxylic acid ethyl ester is obtained : 6 -( o - fluorophenyl )- 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , m . p . 195 °- 197 ° ( from ethyl acetate / petroleum ether ); and pg , 44 from 0 . 40 g of 6 -( o - chlorophenyl )- 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - carboxylic acid ethyl ester is obtained : 6 -( o - chlorphenyl )- 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol , m . p . 235 °- 237 ° ( from ethyl acetate / petroleum ether ). the ethyl ester required as starting material for the first mentioned reduction is produced as follows : ( b ) a solution of 3 . 0 g of 2 -( methylthio )- 5 - phenyl - 7 - chloro - 3h - 1 , 4 - benzodiazepine [ cp . g . a . archer et al ., j . org . chem . 29 , 231 ( 1964 )] and 4 . 0 g of oxalic acid monoethyl ester hydrazide in 100 ml of n - butanol is refluxed for 8 hours . the solvent is then evaporated off in vacuo , and the residue distributed between methylene chloride and water . the organic phase is separated , washed with saturated aqueous sodium chloride solution , dried with anhydrous potassium carbonate solution , and concentrated by evaporation . the residue is chromatographed on 300 g of silica gel with the use of a mixture of ethyl acetate and hexane ( 3 : 2 ) as solvent and eluting agent . the fractions are concentrated by evaporation , the homogeneous residues combined and recrystallised from ethyl acetate / hexane to thus obtain 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - carboxylic acid ethyl ester , m . p . 233 °- 235 °. the further ethyl esters employed as starting materials are obtained in an analogous manner . an amount of 0 . 13 ml of 70 % perchloric acid is added at 25 ° to a solution of 0 . 5 g of 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol in 1 ml of methanol and 1 ml of acetone . the mixture is allowed to stand for 16 hours at 0 °; the precipitated crystals are filtered off under suction , and recrystallised from methanol / acetone . the obtained 6 - phenyl - 8 - chloro - 4h - s - triazolo [ 4 , 3 - a ][ 1 , 4 ] benzodiazepine - 1 - methanol - perchlorate melts at 247 °- 250 °. the crystals contain an equimolar amount of acetone .