DE2301399A1 - NEW DIBENZO-TRIAZOLO-AZEPINE COMPOUNDS - Google Patents

Description

LAWYERS

DR. J ·. »*. ί> ^? 3 -CMrM. WAITER BEIL

*? A - «r ■ Φ **>'' · ■ < -si> -JiOCHSt

"Our No. 1S 384

ifhe Upjohn Company Kalamazoo, Mich .., V.St.A.

New dibenzo-trlazolo-azepine compounds.

The present invention relates to new compounds of the following formulas II and III and a method their manufacture.

The new compounds and the method of their preparation can be represented as follows:

308831/1192

II

In these J-formulas, X denotes oxygen, sulfur, the remainder, s R ₁ -

, 0, wherein R ₁ - and. Eg hydrogen atoms or alkyl

remnants .with. 1 to 3 carbon atoms, or the jtiest : / ^ E- ^ »in which S. is hydrogen, an alkyl radical according to the above Definition, one of the hests

309831/1 192

H H / \

ÜüU-1! N-0nH _o n-; HOC-CH N-CnH ₀ Ii-j

H H \ /

CnHpTi-} I A —CnH ₀ Ti- or

Gnlipn-, where η is a number from 1 to 4 and. Pure Is an alkyl radical as defined above, or one of the radicals

-0nH _o n ~ N 'or -GH ₀ OSO-CH ₀ N means, where Rr ₇ and ^d N - ^{ά ά} \'

^R 8 ^R 8

Rq hydrogen atoms or alkyl radicals as defined above

and η represent a number as defined above, or -N gives the pyrrolidino or piperidino radical.

In the above formulas, R "has the same meaning as R ₁ , while R_ and R. hydrogen, fluorine, chlorine, bromine, iodine, the amino group, alkyl radicals according to the above definition, the trifluoromethyl radical or alkoxy, alkylthio, alkylsulfinyl , Alkylsulfonyl or alkanovlamino radicals, the carbon content of which has 1 to 3 carbon atoms, or -uialkj'lainino groups with alkyl radicals as defined above.

The invention also relates to those pharmacologically acceptable acid addition salts of these compounds and the W oxides of the connections of the i? ormel III.

The method according to the invention is characterized in that daio one i'hioverbindungen of formula I with a hydrazino

309831/1192

-H-

carbonic acid alkyl ester reacts to form the triazolone compound II, which is then reacted with a compound of the formula ClR ₀ , BrR ₀ or IR ₀ , in which R _{0 has} the above meaning,

dd ad compound is alkylated to form a / of the formula III »

As examples of lower alkyl groups having 1 to 3 carbon atoms the methyl, ethyl, propyl and isopropyl radicals are named. The carbon chain of the alkoxy-, alkylsulfynyl- ^, Alkylsulfonyl and alkylthio radicals, which have 1 to 3 carbon atoms, correspond to a lower alkyl radical with 1 to 3 carbon atoms according to the above examples.

The group of the formula CnH _o n, in which η is a number from 1 to U , includes the radicals -CH ₂ -, - (CH ^ -, - (CH), -, - (CH ₂ ) ^ - and branched alkylene radicals such as e.g. -CHp-QH-CH ₀ -,

H ? CH ₃

-C-C-, -CH-CH ₀ -CH ₀ - or -CH CH ₀ -.

ti I C. d , d

CH, CH ₃ CH ₃ CH ₃

The formamido, acetamido and propionamido radicals may be mentioned as alkanoylamino groups with 1 to 3 carbon atoms.

The new compounds of the formula III, their pharmacologically acceptable acid addition salts and N-oxides have antidepressant effects and can therefore be used for treatment Depression in Mammals and Birds'.

The main function of an anti-depressant agent is to carry out the normal functions of the object to be treated restore. A careful distinction must be made here between psychological stimulants such as amphetamines, which produce over-stimulation in the normal individual.

Various methods are known for determining the anti-depressive effect. Generally they are based on that

309831/1192

Antagonism to a depressant agent such as Eeserpine or tetrabenazine or a synergistic increase in the toxicity of certain compounds (e.g. Yohimbine or 3,4-dihydroxyphenylalanine) as well as the comparison of the drug effects of the new compound with other known ones Antidepressants. kit you can do a single test alone fail to determine whether a new compound is an anti-depressant or not. That through different However, the effect profile provided by tests indicates an anti-depressive effect, if any. some suitable tests are described below.

Hypothermic tests with oxotremorine: - £ ~ 1- / ~ 4- (pyrrolidinyl) -2-butynyl7 ~ 2-pyrrolidinone7.

Oxotremorine (as well as apomorphine and tetrabenazine) cause hypothermic reactions in ivice. These are through Blocked anticholinergics and antidepressants like atropine and imipramine.

Oxotremorine produces a very pronounced hypothermia, which reaches a maximum of 60 minutes after administration.

With an administration of 0.6 mg / kg, the body temperature becomes a mouse is lowered by about 7.3 C if the mouse is kept at skin temperature. This temperature decrease is: by Antidepressants like ζ..B. Desipramine, Imipramine, Doxepin and others as seen in Table I antagonized

309831/1192

■ Table I

Effect of various compounds on oxotremorine induced hypothermia in mice.

Verb. Dose Absorp- Change in body temperature, mg / kg tion time ( ⁰ C) versus comparison with vehicle ip (min) after

15 3o '6o' .9.0 min.

Oxotremorine
(Comparison)

0.6 -3.25 -6.5 -7.4 -4.45

Desipra-

min 25. 3o -1.95-1.95 -5.3o -2, ο

Imipramine 25 3o -o, 22 -1.85 -3.15 -3.55

Iprindol 25 3o -3.5 -6.6 -7.2 -6.65

Doxepin .25 3o -1.28 -3.95 -6.15 -6.9

Amitrip

tylin 25 3o. + o, 39 -1,34 -3, ο -3, Sun

Ampheta

min 5 3o -o, S4 -2.4o -2.45 -1.22

Atropine 3 3o +0.34 -o, 34 -o, 39 '-O, 11

The present compounds were tested as follows:
4 male itice weighing 18-22 g (titamm OF = Oarworth i'rams) were given 1 mg of oxotremorine intraperitoneally
injected. The lowering of body temperature was done rectally with an electronic. Thermometer measured before and 30 minutes after administration. After administration
the mice were kept in cages at 19 ° ^. The results are summarized below :

309831/1192

i'abelle II avg. Body temperature of the mice ( ⁰ G)

Carrier (comparison) 33.5

Oxotremorine (1 mg) 28.8

Oxotremorine (1 mg) and A (loo mg) 34.1

Oxotremorine (1 mg) and B (loo mg) 32

Oxotremorine (1 mg) and O 31> 2

a = 2- / ~ 2- (dimethylaminoethyl) -2,9-dihydro-3H-dibenzo _/ / ~ c, f7-s triazolo £ ~ 4,3-a / azepin-3-one

B = 2- _/ /~2-(Oirüetnylamino)-propyl7-2,9-dita.ydro-3H-dibenzo-

C = 2- / ~ 2- (dimethylamino) propyl7-2,9 ~ dihydro-3H-dibenzo

j 3-a7azepin-3 ~ one.

Potentiation of yohimbine aggregation toxicity:

The LDp of yohimbine hydrochloride in mice is intraperitoneal administration 45 mg / kg. The administration of 3o mg / kg yohimbine hydrochloride is not fatal, becomes an anti-depressant before yohimbine hydrochloride (30 mg) administered, the lethal effect of the yohimbine hydrochloride is increased.

Jfohimbine hydrochloride in saline was administered by injection to 10 male CE mice weighing 18-22 g. 2 hours later, the LDc _{0 was} determined. Groups of 10 mice each received the anti-depressant by injection 30 minutes before the administration of the yohimbine hydrochloride (30 mg). No or at most 1 kaus is killed by 3o mg of ifohimbine hydrochloride. When yohimbine hydrochloride is administered in the presence of an anti-depressant agent, there is an increase in the

3 0 9 8 31/119 2

of yohimbine hydrochloride. The ED, - values of the 3 compounds A, B and C, which lead to death in 5 ^{o ύ} / ί> of the mice »are given in laboratory III:

Table III

ED ₅₀ mg / kg

/ ~ YCl7 (3o mg) compared no deaths

^ YCl / (3o mg) and A 7 mg (A)

/ ~ YGl7 (3o mg) and B '16 mg (B) (3o mg) and C- 4o mg (C)

YGl = yohimbine hydrochloride.
Potentiation of the rodent by apomorphine:

His group of 4 mice (male, GP, 18-22 g body weight) received the fixed compound intraperitoneally 1 hour before the subcutaneous injection of 10 mg / kg apomorphine hydrochloric. The mice are then placed in a plastic container (15.2 28 χ 12.7 cm), which is lined on the bottom with an absorbent paper with celophan underlay. The extent of the destruction of the paper after 30 minutes is rated on a scale from 0 to 4. Values 3 and 4 indicate that the compound potentiates apomorphine. All three compounds A, B and C were solid in this one at 100 mg / kg posg.it iv.

The above results therefore show that compounds of formula III and 'their pharmacologically acceptable, ... acid addi-

309831/1192

tion salts and N-oxides in mammals as .ajatidepressants can be applied.

For the compounds of formula XII, the N-oxides ^and salts thereof, pharmaceutical preparation forms for oral, parenteral and rectal use are provided, e.g. tablets, powder packets, sachets, uragees., capsules, solutions, Suspensions, sterile injectable forms, suppositories, bougias and the like. Suitable diluents such as carbohydrates, lactose, proteins, lipids, calcite phosphate, corn starch, stearic acid, methyl cellulose and the like can be used as carriers or for coating purposes Suspensions are water and oils such as coconut oil, sesame oil, saffron oil, cottonseed oil and peanut oil.

Mammals can use Jiutter premixes with starch, oatmeal, dried fish meat, fish meal, cereal meal and the like.

The compounds of the formulas II are used as antidepressants and III and their pharmacologically acceptable acid addition salts in amounts of 0.1 to 5 mg / kg in oral or injectable Preparations used to relieve depression, that occur in difficult situations. Such situations arise, for example, when i'iere their owner change or be housed in the asylum while the owner is absent.

Acid addition salts of the compounds of the formula III can can be produced, for example with fluosilicic acid, the corresponding product being usable as a moth repellent is. Salts with x'richloroacetic acid are suitable as

309831/1 192

23Q1399

- To -

Herbicides against Sorghum halepense (Johnson-öras) ,, Cynodon dactylon (Bermuda grass), yellow and red foxtail and Couch grass »

The starting materials of the process according to the invention are dihydrodibenzoazepinthiones of formula I that are either are known or simply by treating the corresponding oxo compounds with phosphorus pentasulfide can be sjäfchetislert (see. Preparations 1 to 7) ·

When the Durchfährung erfindungsgemäüen method, a l'hion the ü'ormel I with a Hydrazinokohlehsäurealkylester the i ^v Ormel

H ₂ N-NH-OOOAIk

wherein the alkyl group has 1 to 5 carbon atoms. Usually it is preferred to iithylester, but also higher allyl esters are useful (iemäii a preferred embodiment of the invention, the heated 'i'hion I with the Hydrazinokohlensäureäthylester in large shoe 1/2 to 3 hours in an oil bath at 19o to 25o ° C. The hydrazinocarbonic acid alkyl ester serves both as a heavy agent and a solvent. The product usually precipitates when the reaction mixture cools and is obtained by filtration and then purified in a conventional manner, e.g. by extraction of the impurities, chromatography or usually by recrystallization. ■ / ice die i ¹ ria ζ oil on ν inheritance '11.

The alkylation of the compound II takes place by this Product with a strong base, e.g. sodium or iCalium hydride in an organic solvent, e.g. dimethylformamide, Diet hy! "Formamid, diet hylaeet amid, I'etrahydiO-

309831/1192

furan, dioxane, benzene or the like. Using a Overshoe of the iiase converts, whereupon the so obtained Alkali metal salt with a compound Rpi-i in which X ütilor, bromine or iodine and R "denotes the above meaning owns, implements. Both! Reactions, as well as salt formation such as the reaction of the salt with RpA, are usually carried out at elevated temperatures between 50 and 125 C. The conversion of the compound II into its alkali salt usually takes 15-75 minutes. The reaction of the salt with the chloride takes longer reaction times, by inan the reaction mixture for 1 to 36 hours at increased temperature keeps. The product of formula III obtained is then isolated in a conventional manner and purified, e.g. by extraction, (chromatography, Crystallization and the like.

Preparation 1

6 (5H) -fcorphanthridinethione.

ji; in a mixture of 3o g (0.144 mol) 6 (5H) -morphanthridinone, 33.5 g (0.15S LoI) phosphorus pentasulfide and I2oo ml pyridine is refluxed for 23 hours, then the pyridine is evaporated. Methylene chloride and water are added, the organic phase is separated off (little solid present), washed with aqueous sodium carbonate solution until only traces of a pesticide are present, then washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated. When the residue is triturated with methanol, 28.8 g of 6 (5K) -morphanthridinethione with a melting point of 218-219 ° O are obtained. -üeim recrystallization from methylene chloride / methanol, the product is obtained in ΐ ^ι οπ & pale yellow rods, the melting point does not change.

309831/1192

Anal. Ber. for O ₁₄ H ₁₁ N ₂ :

O: 74.63; H: 4.92; Κι 6,22-, 3: 14,23. Found: C: 74.94; H: 5.07; N: 6.08; 3: 14.25 ·

Preparation 2

5,10-dihydro-11H-dibenzo / ~ b, £ / £ "Λ , -47diazepine-11-thione.

A mixture of 10 g (0.0476 moles) of 5,1o-dihydro-11H-dibenzo _i / ~ b, 7Z ~ ' ^I 47diazepin-11-one, 9.3 g (0.0525 moles) of phosphorus pentasulfide and 365 ml of pyridine is refluxed for 3 hours and then left to stand overnight. The pyridine is evaporated, the residue is shaken with 2 ml of water and chloroform. The resulting suspension is filtered to remove solid product. After filtration, the chloroform layer is separated from the aqueous layer, washed with water and saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated. The residue is combined with the previously obtained solid and. crystallized from methanol. The 5, io-dihydro-11H- άχΚΒηζο / ^ \ ι, (^ £ ~ '\ ₁ £ / α.ί & ζβ ^ι ρ ± η -' [Ί-ϊι \ χ1θΌ.. In two fractions, yield 9, o1 g (84 $ of theory), melting point 257-259 ° C.

Preparation 3

Dibenzo / ~ b, f7Z 1,47 ^0x azepin-11 (1H) -thione.

A mixture of 21.6 g (o.1 mole) of dibenzo ^ O ^ f ^ f ^'1, x 47 ° ^a zepin-1i (IOH) -one, 23.4 g (o, 1o5 moles) of phosphorus pentasulfide and 85o ml Pyridine is refluxed for 4 hours, then the pyridine is removed in vacuo and the residue is extracted with chloroform

309831/1192

230139S

stirred, then 500 ml of saturated aqueous sodium bicarbonate solution are added added * The resulting suspension is filtered off and the solid is discarded. The FiItrat is separated into two layers; the organic layer is washed with aqueous sodium bicarbonate solution and successively washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated. The residue is crystallized from chloroform / methanol, this gives 14.6 g of dibenzo, / ~ b, f7 ^ 1, -47oxazepine-11 (1oH) -thione in the form of pale yellow needles of ΪΡ. 194-195 ° E. At the The melting point is no longer changed when recrystallized. Anal. Ber. for C JHqNOs:

U: 68.69i H: 3.99; N: 6.16; Ss 14 * 11; Found: 68.5o; Hs 3.93; N. 6.305 Si 13 * 77.

Preparation 4

, 47thiazepine-11 (1oH) -thione.

Mixture of Mbenzo ^ * "b, f7 ^ 'i, J _: 7 * h.iazepin ~ 11 (1oH) -one and phosphorus pentasulphide is refluxed in pyridine for 6 hours. Then the pyridine is removed in vacuo and the residue is as described in preparation 2, whereby the title compound is obtained with a temperature of 246 ~ 247.5 ° 0 *

309831/1192

Preparation 5 -

7-chloro-5,1o-dihydro-11H-dibenzo £ ~ b, _e // ~ "i, ^ diazepine-iithione.

A mixture of 3o _t 5 g (ο, 125 mol) 7-OtIlOi -!?, 1 ö-dl hydro-HH-dibenzo ^ bje /, / "!, 47diazepin-11-one, 2.7.8 g ( 0.13% MoX) phosphorus pentasulfide and 1 l pyridine are refluxed for 4 hours, then the pyridine is removed in vacuo. The residue is stirred for 1 hour with 1 l each of saturated aqueous sodium bicarbonate solution and ethylene chloride, then some solid product is filtered off The organic phase of the piltrate is washed successively with sodium bicarbonate solution and with saturated sodium chloride solution, dried over anhydrous magnesium sulphate and evaporated. Chlorine-5, loitH-dibenzo ^ be / ^ i ^ diazepine-ii-thione from ϊ ^1. 27 Concentration of the chloroform and methanol washing solutions gives a further 8.4 g of product with the same melting point /a.sser ^! 'wifd the analysis no received a sample in i? orm blue-yellow Efadeln from W _t 276-277 ° ö. ■

5 * 1 o-Mhydro-5-methyl-1 iH-di

A mixture of 6 _f 1 g (0.0272 mol) 5, io-Dlhydro-5-.methyl-i 1H- äiüemo / ~ h, & 7 £ "ii _f 47ü ± azeTpln-T1-Qn, 6.51 g ( 0.0286 mol) of phosphorus pentasulfide and 175 ml of pyridine is 5 5/4 hours

309831/1192

refluxed, then the pyridine is evaporated in vacuo. The residue is shaken with chloroform and saturated aqueous sodium bicarbonate solution. The resulting The suspension is filtered to give a pesticide A. The chloroform phase of the piltrate is sequentially washed with saturated aqueous sodium bicarbonate solution and saturated sodium chloride solution, over anhydrous Magnesium sulfate dried and evaporated. The residue is crystallized from methylene chloride / methanol, thereby 3.5 g of 5, 10-dihydro-5-methyl-IIH-dibenzo- / b, e7 / T, 47diazepine-II-thione are obtained from P. 217-218 ° C, which remains unchanged after further recrystallization. A second Fraction of 0.8 g melted at 214-215 ° C.

The pesticide A is shaken with methylene chloride and 10> £ sodium hydroxide and worked up as described above, a further 1.5 g of the thione from P. 216-217 C being obtained. Anal. Ber. for ^c i4 ^H i2 ^N 2 ^S:

C: 69.96; H: 5.30; N: 11.66; S: 13.34; N: 11.66; Found: C: 69.79; H 5.20; N: 11.37; S: 13.29-

Preparation 7
2-chloro-6 (5H) -morphanthridinethione.

A mixture of 10 g (0.046 mol) 2-chloro-6 (5H) -morphanthridinone, 11.2 g of phosphorus pentasulfide and 340 ml of pyridine is 3 hours. refluxed and concentrated in vacuo. The residue is saturated with 500 ml of methylene chloride and 250 ml for 2 hours aqueous sodium bicarbonate solution and filtered off, whereby a pesticide A is obtained. The organic phase of the The filtrate is washed with aqueous sodium bicarbonate solution, then with 250 ml of saturated sodium chloride solution, dried and evaporated. The residue is combined with product A. and crystallized from chloroform / methanol. 2 fractions of 2-chloro-6 (5H) -morphanthridinethione are obtained; Initially 5.6 g in Form of yellow needles from P.246-247.5 ° C, also 4.0 g from F.

309831/1192

23p 1399

245-246 ⁰ C, yield 939ε Anal. Ber. for O, H ^

O: '64.73 »H: 3.88; 011 13.65j. N: 5.39? S: 12.35 Found: C: 69.66? H: 3.83j 01: 13.89; Ni 5.38; S: 12.05

Further starting materials of the formula I according to the invention can be prepared as described in the above preparations

be, for example

3,8-dichloro-6 (5H) -morphanthridinethione, 3,8-I) ibromo-6 (5H) -morphanthridinethione, -2, 9-13ifluoro-6 (5H) -morphanthridinethione, 8-amino-6 (5H) -morphanthridinthione, 9-methyl-4- (methylthio) -6 (5H) -morphanthridinthione, 1- (ethylsulfonyl) -7-propyl-6 (5H) -morphanthridinthione, 1-diethylamino-8-sulfiny1-6 (5H) -morphanthridinthione, 9-iodo-4-isopropyl-6 (5H) -morphanthridinthione, 2,8-I) iäthoxy-6 (5H) -morphanthridinthione, 7-acetamido-3-isopropyl-6 (5H) -morphanthridinthione, 8-chloro-6 (5H) -morphanthridinethione, 7-Ii ¹ IuOr-O (SH) -morphanthridinethione, 3-amino-6 (5H) -morphanthridinethione, 7-bromo-6 (5H) -morphanthridinethione, 2,3 -Dichlor-5, lo-dihydro-HH-dibenzo / ™ b

thion, ■

2,8-dibromo-5,1o-dihydro-11H-dibenzo / ~ b,

thion,

3,7-Mfluoro-5,1o-dihydro-11H-dibenzo ^ f b

thion,

2,7-Difluoro-5,1o ~ dihydro-11H-dibenzo / ~ b

thion,

3,8-Pifluoro-5, io-dihydro-11H-d.ibenzo / ~ b

thione, 4,7-diamir »-5,1o-dihydro-1 IH-thione,

, 47 "dia.zepin-11-1,4 / diazepin-i 1-1,47diazepine-11-i , 47 <liazepin-11-, j / diazepin-i 1-

309831/1192

1301399 ~ ¹⁷ "

2,8-I) iisopropoxy-5,1o-dihydro-11H-dibenzo / ~ b, e / Z " ¹ > pin-11-thione,

5,1o-dihydro-4-formamido-8-methyl-i1H-dibenzo £ ~ "b, diazepin-11 -thion,

5,1o-dihydro-1-iodo-1iH-dibenzo _{i (} / ~ b, ^ 7Z ~ ' ¹ , 47 ^diaze P ^la - ¹ 1-thione, 5,1o-dihydro-1-methyl-7- ( propylsulfonyl) -11H-dibenzo / ~ b, e7 ~ / ~ 1, _47diazepine-11-th.ion,

1-Bromo-2- (ethylsulfinyl) -5,1o-dihydro-11H-dibenzo ^ ~ b, öj- £ ~ 1,47d.iazepine-11-tb.ion,

5,1o-l) ihydro-1- (isopropylth.io) -1 iH-dibenzo / ~ b, e7 / ~ 1, _47 ^diaze ~ pin-11-thione,

2-Diethylamino-S-fluoro-5, io-dihydro-11H-dibenzo / ~ b, ^ 7 / ~ 1.47 ~ diazepine-11-thione,

7-amino-5, io-d.ihydro-3-propoxy-i 1H-dibenzo / ~ b, pin-11 -thion. and the like

example 1

2,9-dihydro-3H-dibenzo / ~ G, f7-s-triazolo _< / f "4,3-a7azepin-3-one.

A mixture of 28.8 g (0.128 mol) 6 (5H) - morphanthridinethione and 133 g (1 * 28 mol) hydrazinocarbonic acid ethyl ether was placed in an oil bath preheated to 195-2o5 ° G using a condenser (45 ml were removed) heated. The resulting solid was mixed with methylene chloride and water and the suspension was filtered off, whereby 12.6 g of 2,9-I) ihydro-3H-dibenzo / ~ ^c »£ 7-s-triazolo / 7" 4,3-a7- azepin-3-one with a melting point of 276-279 ° 0. The filtrate was separated into two layers, the organic phase was washed with water and saturated sodium chloride solution and dried over anhydrous magnesium sulfate the solution was allowed to stand, which separated

309031/1112

2301393

2.6 g of product of melting point 288-29o ° U ab.i'erner was still a further fraction of 3.3 g of product obtained vom'Schmelzpunkt 285-288 ⁰ G. All product fractions were combined a and crystallized from methylene chloride, a yield of 14 »2 g (44 / <>) with a melting point of 289-290 ° 0, which was unchanged on recrystallization. stayed. .ν "."'·

Anal. Ber. for C ₁₅ H ₁₁ N ₃ O:

G: 72.27f H: 4.45J K: 16.86. G-ef .: O: 72.20} H: 4 »3o j N: 17.17.

Example 2

2- / ~ 2- (Dimethylamine) ethyl7-2,9-dihydro-3H-dibenzo / _> c, f7-striazolo ^ ~ 4,3-a7azepin-3-one.

0.42 g sodium hydride. (0.1 mol of a 57% dispersion in mineral oil) were added to a solution of 2.49 g (0.1 mol) of 2,9-dihyd.ro-3H-dibenzo / ~ c, f7-s-triazolo / ~ 4,3-a7azepin-3-one in 100 ml of dimethylformamide was added and the mixture was heated to 95 ° O for 30 minutes. The mixture was then cooled to 50 ° and a solution of 1.07 g (0.01 mol in 1.07 g of xylene) of dimethylaminoethyl chloride. was added. The mixture was heated 18 hours 95 ⁰ G and evaporated, the Eückstand was extracted water taken up in methylene chloride and and mit.Methylenchlorid. The extract was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated. When the residue crystallized, 2 g of 2- _/ / ~ 2- (dimethylamino) -ethyl7-2,9-dihydro-3H-dibenzo _/ / ~ c, f7-s-triazolo / ~ 4, 3-a7azepin-3-one obtained in the form of colorless prisms with a melting point of 161-162 ° O. The melting point was not changed by recrystallization. I also got a second fraction of 200 mg of product

309831/1102

2301339

from melting point 161-162 ° (J obtained.
Anal. Ber. for Ö XN.Oj

Gi 71.22; H: 6.29} N: 17.49; Found: C: 71.2oj; H: 63.4; N: 17.33

Example 3

2- ^ ~ 3- (dimethylamino) -propyl7-2,9-alhydro-3H-dibenzo / ~ c, f7-s-triazolo / ~ 4 »3-.a7azepin-3-one.

Sodium hydride (0.178 g, 4.21 millimoles of a 57 # dispersion in mineral oil) was converted into a solution of 1. o5 g (4 »21 millimoles) 2, 9-dihydro-3H-dibenzo _i / ~ c, f7- s-triazolo / ~ 4,3-a7 azepin-3-one in 50 ml of dimethylformamide, was added and the mixture was heated to 95 ° for 35 minutes. It was then cooled to 50 °, a solution of 0.51 g (4.21 millimoles in 0.51 g of xylene) of 3-dimethylaminopropyl chloride was then added, and the mixture was then heated to 95 ° for a further 21 hours. The mixture was evaporated and methylene chloride and water were added to the chopping stand. The organic phase was separated off and extracted 3 times with 10 ml of the above aqueous hydrochloric acid. The acid extract was cooled, made alkaline with 15% aqueous sodium hydroxide solution and the basic mixture was then extracted with methylene chloride. The extract was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated. When the residue was crystallized from ether, 0.975 g of 2- / ~ 3- (dimethylamino) propyl7-2,9-dihydro-3H-dibenzo _i / ~ c, f7-s-triazolo- / ~ 4,3- a7azepin-3-one of mp 130-131 ° 0 (unchanged after recrystallization).
Anal. Ber. for ^ΰ 2ο ^Η 22 ^Ν 4 ^0:

ü: 71.83} H: 6.63; Ni 16.76; Found: C: 71.91J, H: 6.63; N: 17.16.

309831/1192

2301393

2ο -

Example 4

2- / ~ 3- (4-methyl-1-piperazinyl) ~ propyl7 ~ 2, 9-dihydro-3H-dibenzo ^ f ~ c, f7-s-triazolo / f 4, 3-a7azepin-3-one and its dihydrochloride.

Sodium hydride (0.42 g, 0.1 mol of a 57% dispersion in mineral oil) was converted into a solution of 2.49 g (0.1 Iviol) 2,9-dihydro-3H-dibenzo / f "c _> f7 -s-triazolo _< / ~ 4,3-a7azepin-3-one in 100 ml of dimethylformamide was added and the mixture was heated to 95 ° for 30 minutes. It was then cooled to about 50 °, then a solution of 1 , 76 g (o, o1 mol in 1.76 g of xylene) 1- (3-chloropropyl) -4-methylpiperazine (for preparation see F.Sowinski and HLiale, J.Hed.Chem., Jj, 54 (1962)) added and the mixture was heated 21 hours at 95 ⁰ G. then to dryness was evaporated and the residue was dissolved in methylene chloride and V / ater. the organic phase was separated and extracted with 1 above aqueous hydrochloric acid. the acidic extract was cooled, diluted with "\ 5? Olger aqueous sodium hydroxide solution was made alkaline and the basic mixture was then extracted with methylene chloride. The extract was washed with saturated sodium chloride solution over anhydrous magnesium. sulfate dried and evaporated, leaving daa 2 - / "~ 3- (4-methyl-1-piperazinyl) -propyl7-2,9-d.ihydro-3H-ail3eneo- / ~ c, f7-s-triazolo / ~ The residue was dissolved in ether, treated with 100 ml of 1N hydrogen chloride in ethanol, and the resulting gum was crystallized from methanol / ether. 2.9 g of the partially hydrated 2- / ~ 3- (4-Methyl-1-piperazinyi) -propyl7-2, 9-dihydro-3H-dibenzo _(l / ~ c, f7-s-triazolo / ~ 4> 3-§7-azepin-3-one -dihydrochlorids from ^S1. 277-279 ° C. (decomposition) The üchmelzpunkt rises during recrystallization at 279-281 ⁰ G. -Anal. Ber. for C ₂₅ H ₂₇ N ₅ O

309831/1 192

Gj 59.16? H: 6.37; N: 15.00; Cl: 15.19-

Found: Ci 59.17; M: 6.45; N: 15.14; Cl: I5, o7.

The anhydrous product is obtained by drying the hydrate in

Maintained vacuum at 100 ° C for several hours.

Example 5

2,9-Mhydro-3H-dibenzo ₁ / ~ b, f7-s-triazolo _< / 4,3 3-one.

A mixture of 21 g (0.093 mol) 5,1o-dihydro-1 iH-aibenzo / ~ b, _e7- / ~ 1,47diazepine-11-thione and. 100 g of ethyl hydrazinocarbonate were heated to the stated temperature for 50 minutes in an oil bath preheated to 190-2oo ° C. using a condensation cooler. During this period, 25 ml of liquid was removed. The mixture was then cooled to 50 ° C. and 100 ml of water were added. The resulting suspension was filtered, the solid was washed with water and ether. This gave 15.4 g (66-6 yield) of 2,9-dihydro-3H-dibenzo / ~ b, f7-s-triazolo- / ~ 4,3-.d7Z ~ ¹ * i7 <iiazepin-3-one from F.- 262-263.5 ° 0. After Umkrietalliaieren of acetone and water, the melting point was 263 to 264.5 ⁰ C
Anal. Ber. for C ₁₄ H ₁₀ N ₄ O:

Ci 67.19 »Hs 4, o3j N: 22.39? Found: Ci 66.79? H: 3.96? -N: 22.43.

Example 6

2- / ~ 2 ~ (Dimethylamino) ethyl7-2,9-dihydro-3H-dibenzo ^ b, f7 ~ striazolo / ~ 4,3-d7 / ~ 1, i7diazepin-3-one.

309831/1192

Nätriumhydriä- (0/456 g, ο-, oio3'kol a 57 ^ igea dispersion in mineral oil) was added to 'a solution of 2 g 7 _f (a, o1o8 kol). -

3-one in 95 ml of dimethylformamide was added and d: aa mixture was 3o minutes at 95 ⁰ O heated. Then was cooled to 0 and a solution of 4o 1 "" 16 g (o, o1o8 mole in T, 16 g-xylene) 2-Dim.ethylaminoäthylchlorid was added. Daa mixture was' 18 laps to ^"0 O 95 and heated. evaporated .- "· Then water and methylene chloride were added and the organic phase was separated and extracted 2 each with 20 ml of 10% aqueous hydrochloric acid. The diacid extracts were washed with ether. The ether was discarded. The juice extract was cooled "Made alkaline with 15-strength aqueous sodium hydroxide solution and extracted with methylene chloride. Then it was washed with water and with saturated sodium chloride solution", dried over anhydrous magnesium sulfate and evaporated. The residue was crystallized from ether, giving 1.83 g of 2- / ~ 2- ( Dimethylamino) ethyl7-2,9-dihydro-3H-dibenzo / ~ b, fy-s-triazolo / ~ 4, 3-_d7 ₍ / ~ '' » ^{17 diaze} P ⁱⁿ ~ 5-one. In the form of small brown prisms of melting point. 143-144 "5 ° C" After recrystallization the melting point was 144-145 ⁰ O.

Anal. Ber. for G ₁ QH _1n N ₁ -Oi "

1o 19 5

C: 67.27; H: 5.96} N: /21.79; Found: C: '67.25; H: 6.1a; Ns 21.44.

Example 7

2- / ~ 3- (Whore thylamino) -pr opyl7-2,9-dihyd ro-3H-di benzo / ~ b, f7-s-

Sodium hydride (o, 456 g, o, o1o8 mol of a 57 ^ igen dispersion in Mineral oil) became a solution of 2.7 g (o, o1o8 mol)

309831/1192

2,9-Dihydro-3H-dibenzo / ~ b, f7-s-triazolo _(j / ~ 4,3-d7 _< ^ r "1,47diazepin ~ 3-one in 95 ml of dimethylformamide was added. The mixture was at room temperature Stirred for 30 minutes and then heated to 95 ° for 30 minutes. The mixture was then cooled to 40 ° C. and a solution of 1.31 g (0.0108 mol in 1.31 g of xylene) of 3-dimethylaminopropyl chloride was added, followed by the addition The mixture was heated to 95 ° O for a further 21 hours. The mixture was concentrated by distillation, water and methylene chloride were added to the concentrate. The organic phase was separated off and extracted 3 times with 20 ml of 10 ml aqueous hydrochloric acid each time. The acid extract was washed with ether ( the ether was discarded) with ^15; provided Mger aqueous sodium hydroxide solution alkaline and then extracted with methylene chloride the extract was washed with saturated ITatriumchloridlösung, dried over anhydrous magnesium sulfate and concentrated the residue was crystallized from ether to give 2.54 g of 2- / ~.. 3- (dimethylamino) propyl7-2,9-dih ydro-3H-dibenzo / b ~, F_7-s-triazolo / 4,3-d 7 ~ / ~ 1,47cliazepin-3-one, melting at 125-126 ° Ü.
Anal. Ber. for ΰ ^ Η ^ Ν, -ϋ:

Üt 68.08} H: 6.31; K: 2o, 88. Found: 0: 68.2o; Hi 6.42; N: 2o, 73

Example 8

2,9-dihydro-2- / ~ 3- (4-methyl ~ 1 ~ piperazinyl) -propyl7-3H-dibenzo / ~ b, f7-s-triazolo ₍ ^ ~ 4, 3-ύ / £ ~ Λ , 47diazepine -3-one and _i its dihydrochloride.

Hatriumhydria (o, 456 g, o, oio8 mol of a 57% dispersion in Hineralöl) became a solution of 2.7 g (o, oio8 mol) 2,9-Dihjdro-3H-dibenzo / ~ b, f7-s-triazolo / _ '~ 4, 3-Jd // "!, 47diazepin-3-one in 95 ml of dimethylformamide was added and the mixture was

309831/1192

230139g " ^u "

Heated 3o minutes at 95 ⁰ C. The mixture was then cooled to 40 ° C. and a solution of 1.9 g (0.0108 mol in 1.9 g of xylene) 1 .- (3-chloropropyl) -4-methylpiperazine was added, followed by a further 22 hours to 95 ° C heated. The mixture was evaporated, the residue was dissolved in ethylene chloride and water. The organic phase was separated off and extracted 3 times with 10 ml of 10% aqueous hydrochloric acid each time. The acid extract was washed with ether (the ether was discarded), cooled and made alkaline with 15% aqueous sodium hydroxide solution, whereupon the basic mixture was extracted with methylene chloride. The extract was washed with water and saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated to dryness. The 2, 9-dihydro-2- / f ~ 3- (4-methyl-1-piperazinyl) -propyl7-3H-dibenzo / ~ b, f7-s-triazolo / ~ 4, 3-d // ~ obtained in this way 1,47diazepin-3-one was dissolved in 3o ml of methanol and added to 1oo ml of a 1.1N ethereal hydrogen chloride solution. The gum which separated out was triturated with hot methanol, 2.4 g of 2,9-dihyd.ro-2- / ~ 3- (4-methyl-1-piperazinyl) -propyl7-3H-dibenzo / ~ b, f7 -s-triazolo / 4,3-d7Z ~ ~ ^1, j7diazepin-3-one-dihydrochloride / received from F. 288-29o ° G. After recrystallization "from methanol / methylene chloride to melt the product at 286-288 ⁰ G.
Anal. Ber. for C ₀₀ H ₀ ^ ₇ N, -0.2H01:

G: 57.02; H: 6, o9j Cl: 15, -3o; N: 18.14. Found: G: 56.99? H: 6.25} Cl: 15.08; N; 18.44.

Example 9

5- (3-Dimethylaminopropyl) -5, io-dihydro-1 iH-dibenzo / ~ b, _e7 / ~ 1 diazepine-11-thione.

A mixture of 5 g (0.17 mol) 5- (3-dimethylaminopropyl) -5,1o-dihydro-i1H-dibenzo / ~ b, e7 _z f ~ i, 47diazepin-11-one, 4.15 g

309831/1192

2301393 - 25 -

(0.0187 mol) phosphorus pentasulphide and 175 ml of pyridine were boiled for 3 hours on the reflux, then the pyridine was removed. The residue was dissolved in 150 ml of ethylene chloride and 100 ml of 5% aqueous hydrochloric acid. The organic phase was separated off and washed with water and saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated. When the residue was crystallized from kethanol, a first fraction of 4.08 g of 5- £ ~~ 3- (dimethyl 1-aminoprop, yl7-5j 10-dihydro-1iM-aiben.zo £ ~ b, e7 / ~ 'i , 4 / diazepine-11-thione from January ^1, 181-182 ° C and a second fraction of 0.257 g from J7y-18ü ° ü, yield Ö5yo.
Anal. here. for u.gH ^ -Nzu:

0: '69.41; H: 6.3o; N: 13.49? δ: 1o, 3o; Found: 0: 69.61; H; 6.63; N: 13.13; S: 1o, 33 ·

Example 1o

9- / ~ 3- (dimethylamino) propyl7-2, 9-dihydro-3H-dibenzo _/ / ~ b, f_7-striazolo / ~ 4,3-

Mn mixture of 0.5 g (1.6 milliii-oil) 5- / ~ 3- (dimethylamine) -propyl / dibenzo ^ b, £ / £ ~ Λ , 4 / diazepine-11-thione and 1.66 g ( 16 millimoles) hydrazinocarbonic acid ethyl ester was immersed for 10 minutes in an oil bath at 192 ⁰ O, then removed from it and left to stand for about 72 hours at room temperature. Water and methylene chloride were then added to the mixture and the aqueous phase was separated off and 5 times with 10 ml of ethylene chloride each time. extracted. The extract was washed 3 times with Vifasser and 1 with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and. limited. The residue was triturated with acetone and then crystallized from acetone, giving o.225 g

-2, 9-dihydro-3H-dibenzo / ~ b, f7-s-

309831/1192

triazolo ^ 4, 3-d7 / ~~ 1> 47d.iazepin-3-one in the form of irrisines with a melting point of 212-214 ° C. After recrystallization, the product melted at 213-214 ° G.
Anal. £ he. for C 'H ₂₁ N ₁ -O:

G: 68.04; H: 6.31; H: 20.88; Found: Gi 67.95; H: 6.34; N: 2o, 64.

Example 11

6, 12-dichloro-2, 9-dihydro-3H-dibenzo ^ Cji / '- s-triazolo, / 4,3-a / -a.zepin-3-one.

Following the procedure of Example 1, 3,8-dichloro-6 (5H) -morphanthridinethione is obtained and hydrazinocarbonic acid ethyl ester the title compound.

Example 12

6,12-I) chloro-2-ethyl-2,9-dihydro-3H-dibenzo £ c, f7-s-triazolo-

Following the procedure of Example 2, the 6,12-dichloro-2,9-dihydro-3ii-dibenzo ^ ~ c, f ^ -s-triazolo _i / ~ 4 ^ 3-a7azepin-3-one on treatment with sodium hydride and then with iithyl iodide the 6,12-iJichlor-2 ~ ethyl-2, 9-dihydro-3H-dibenzo-

, 3-a7azepin-3-one.

Example 13

7,11-difluoro-2, 9-dihydro-3H-dibenzo _/ / ~ c, f7-s-triazolo £ ~ 4, 3-a7-azepin-3-one.

309831/1192

According to the procedure of Example 1, 2,9-uifluor-60; 5H) -morphanthriuinthione is obtained and ethyl hydrazino carbonate the. xitel connection.

Example 14

7,11 -i) iiluor-2, y-dihydro-2- £ 3- (diprop ^ -lamino) prop ^ l7 ~ 3H-

4,3-a / azepin-3-one.

Following the procedure of Example 2, 7,11-difluoro-2,9-dihydro-3H-ciibenzo / ~ c, f7-s-triazolo / _ 4,3-a7azepin-3-one when treating with sodium hydride and then with 3-dipropylaminopropyl chloride the 7,11-Mf luor-2, 9-dihjidro-2 / ~ 3- (dipropy? .amino) -

Example 15

i2-chloro-2,9-dihydro-3H-dibenzo _/ / ~ "c, f7-s azepin-3-one.

Following the procedure of Example 1, 8-Uhlorö (£ 5H) -] norphanthriain is obtained and üydrazinokohlensäureäthylester die title connection.

Example 16

12-Uhlor-2,9-aihydro-2- £ 2- (1-p ^ rrolidinyl) -ethyl7-3H-dibenzo / ~ c, f7-s-triazolo _< / ~ 4,3-§7azepin-3-one .

Haeh. The procedure of Example 2 gives the 12-uhlor-2,9-dihjfdro-3il-dibenzo ^ f "c, f7-3 ~ triazolo ₍ / ~ 4» 3-a7azepin-3-one in

309831/1192

treat with sodium hydride and then with 1- (2-chloroethyl) -pyrrolidine the 12-chloro-2, 9-dihydro-2- / ~~ 2- (1-pyrrolidinyl) -äthyl7-3H-dibenzo _II // "c, f7-s-triazolo / ~ 4, 3-a7azepin-3-one.

Example 17

8- (ethylsulfonyl) -2,9-dihydro-13-propyl-3H-dibenzo / ~ c, f7-striazolo / f " 4,3-a7azepin-3-one.

Following the procedure of Example 1, 1- (ethylsulfonyl) -7-propyl-6 ^ 5H) -morphanthridinethione is obtained and. Propyl hydrazine carbonate the title connection.

Example 18

8- (ethylsulfonyl) -2,9-dihydro-2- (2-morpholinoethyl) -13-propyl-3H-dibenzo / ~ c, f-7-s-triazolo / ~ 4,3-a7azepin-3-one.

According to the procedure of Example 2, 8-ethylsulfonyl-2,9-dihydro-13-propyl-3H-dibenzo / ~ c, f7'-s-triazolo _/ / ~ 4,3-a7azepin-3-one is first treated with sodium hydride, and then treated with 1- (2-chloroethyl) -mprpholinj, whereby the 8- (ethylsulfonyl) -2,9-dihydro-2- (2-morpholinoethyl) -13-propyl-3H-dibenzo / ~ c, f_7 -striazolo / ~ 4,3-a7azepin-3-one receives.

Example 19

5- (diethylamino) -13- (ethylsulfynyl) -2, g-di </ ~ c, f7-s ~ triazolo / ~ 4, 3-a7azepin-3-one.

According to the procedure of Example 1, 4- (diethyl

309831/1192

amino) -7- (ethylsulfinyl) -6 (5H) -morphanthridinthione and hydrazinocarbonic acid ethyl ester the l'itel connection.

Example 2o

5- (Diä1; hylamino) -13- (ethylsulfonyl) -2,9-dihLydro-2-propyl) -3H-

According to the procedure of Example 2, 5- (diethylamino) -13- (ethylsulfonyl) -2,9-dihydro-3H-dibenzo _i / ~ c, f7-s-triazolo- ^ 4,3-8 / "Sζepin-3 -one treated with sodium hydride and then with propyl iodide, "whereby the 5-x) iäthylamino-13-ethylsulfonyl-2,9-dihydro-2-propyl-3H-dibenzo / ~ c, f7-s-triazolo _{i (} / ~ 4-, l) -a / - azepin-3-one receives.

Example 21

6, i2-dichloro-2,9-dihydro-3H-dibenzo _z / c, f7-s-triazolo-, 4 / diazepin-3-one.

Following the procedure of Example 5, 2,8-dichloro-5 is obtained io-dihydro-11-dibenzo £ ~ "b, _e7 / ~ 1,47diazepine-11-thione and Hydrazinocarbonic acid ethyl ester is the title compound.

Example 22

6ji? -Dichlor-2,9-dihydro-2- (2-morpholinoethyl) -3H-dibenzo-

, 47diazepin-3-one.

Following the procedure of Example 6, 6,12-dichloro-2,9 ~ dihydro-3H-dibenzo / ~ b, f7 * -s-triazolo / ~ 4,3-d7Zr '' ¹ »47dia ~ epin-3-one

309831/1192

treated with sodium hydride and then with 1- (2-chloroethyl) morpholine, the 6,12-x) chloro-2,9 ~ dihydro-2- (2-morpholinoethyl) -3H-dibenzo £ b, f_7 ~ s-triazolo _/ / 4 »3 - ^ // f ~ 1» .47 "diazepin-3-one receives.

Example 23

7,11-üifiuor-2,9-dihydro-3H-äibenz_o / b, F_7-s-triazolo- Λ, 47diazepin-3-one.

According to the procedure of Example 5, 3,7-difluoro-5,1o-dihydro-11H-ciibenzo ₍ / ~ b, _e7 _i / ~ '' »i / d-iazepine-i 1-thione and hydrazinocarbonic acid ethyl ester give the i 'itel connection.

Example 24

7,11-difluoro-2, g-aihydro- ^ - isopropyl- ^ H-ciibenzo, / b, f7 ~ s-

, _47diazepin-3-one.

7,11-Uifluoro-2,9-dihydro-3H-dibenzo ₎ / ~ b, f7-s-triazolo / ~ 4, 3-u // ~ ^ > _47diazepin-3-one with Sodium hydride and then treated with isopropyl chloride, the 7,11-uifluoro-2,9-dlhydro-2-isopropyl-3H-dibenzo _J / ~ b, f7-s-triazolo _i / ~ 4,3-d7Z ~ 1, 47diazepin-3-one receives.

Example 25

5-i'ormamido-2,9-dihydro-1o-methyl-3H-dibenzo / b, f7-s-tria-

, 47diazepin-3-one.

Following the procedure of Example 5, 9-i'ormamido-5, io-

309831/1192

dihyäro-4-ynethyl-1H-dibenzo, / ~~ b, & J C ^ , 47diazepine-11-thione and hydrazinocarbonic acid eth, yl ester obtained the title compound.

Example 26

i3 ~ I ^ll orniamido-2, 9-dihydro-1o-methyl-2 _(/ ~~ 3- (1-pyrrolidinyl) -Xjropyl7-3H-äibenzo </ ~ b, f7-s-triazolo _i £ ~ 4, 5 -i

According to the description of Beiajjiel 6, S- ^ dihydro-1o-meth.yl-pii-diben2; o _i / ~ b, f7-s-triazolo / ~ "4, 3-diazepin-3-one with sodium hydride and then with 1- (3-Uhlorpropyl) -pyrrolidin treated, whereby the 5-- £ ^l orBiamido-2,9-dih.ydro-1o-iuethyl-2 - ^ '~ 3- (i-pyrrolidinyl) -propyl7-3H- dibenzo / ~ 'b, f7 - striazolo / ~ 4, 3-d7Z ~~ 1, .4y'diazepin-3-one.

Example 27

8-.ßroin-1 1- (ethylsulfynyl) -2, 9-dihydro-3H-dibenzo / ~ b, f / -s-

, 47diazepin-3-one.

Following the procedure of Example 5, 6-J3rom-2- (a ~ hylsulfinyl) -5,1o-dib.yd.ro-1 IH-dibenzo ^ / fb, e / £ ~ l , 47 <3iazepine-11 is obtained -thione and H, ydrazinocarbonic acid ethyl ester, the title compound-

Example 28

8-j3rom-2- _/ / _ 3- (dipropylamino) -propyl7-i2- (ethyl3ulfynyl) -2, 9-dihydro-3H-dibenzo / ~ b, f7-s-triazolo _/ / ~ 4, 3-7Z ~ 1,4; 7diazepin-3-one.

Each of the instructions in Example 6 is 8-bromo-i2- (ethylsulfinyl) -2,9-uihydro-3H-dibenzo / ~ b, f7-s-triazolo _/ T "4,3-d7-

309831/1192

Potassium hydride and then treated with 3-dipropyl aminopropyl chloride, whereby the S-bromo-2 - ^ / 3- (dipropylamino) propyl7-12- (ethylsulfinyl) -2,9-dihydro-3H-dibenzo _< / "~ b, f7'-s-triazolo ^ / ~ 4> 3-ä // ~ 1 , 47diazepin-3-one receives.

Example 29

7-amino-2,9-dihydro-1o-propoxy-3H-dibenzo / ~ b, f7 ~ s-triazolo-

Following the procedure of Example 5, one obtains from the 7-Amino-5,1o-d.ihydro-4-propoxy-11H-dibenzo / ~ b, e // ~ 1 11-thione and hydrazinocarbonic acid ethyl ester the l'itelverbin manure.

Example 3o

- (diethylamino) -äthyl7-2, 9-i.e. hydro-1 o-propoxy ~ 3H-dibenzo _< / ~ b, f7-8-triazolo ^ / ~ 4f 3-

Subject to the procedure of Example 6 is 7-amino-2,9-dih.ydro-1 o-propoxy-3H-dibenzo / ~ b, f_7-s-triazolo _i / ~ 4,3-jd7 / ~ 1,47diazepine 3-one with sodium hydride: and then treated with 2- (diethylamino) -1-chloroethane, the 7-amino-2- / f "2- (diethylamino) ethyl7-2,9-dihydro-10-propoxy-3H -dibenzo / ~ b, f7-striazolo _< / ~ 4, 3- ^ 7 / "O, 47diazepin-3-one.

Example 31

6,12-Oichlor-1 λ ~ [_ 3- (dimethylamino) -propyl7-2, 9-dihydro-3H-

, 37diazepin-3-one.

309831/1192

According to the procedure of Example 5, from 2,3-dichloro-3- / ~ 3- (dimethylamine) per pyl7-5 »1 o-dihydro-11-dibenzo- / ~ b, - ^ 7 / ~ 1.4 / diazepine-11-thione and hydrazinocarbonic acid ethyl ester the i ^! itel connectiono

Example 32

-2- ^ 3- (diethylamino) propyl7-11- _/ / ~ 3- (dimethylamino) -propyl7-2,9-dihydro-3H-dibenzo £ ~ b, f7-s-triazolo / ~ 4,3-d7- , _4 / ciiazepin-3-one.

According to the procedure of Example 6, 6,12-dichloro-i1- ₍ / ~ 3- (dimeth _t ylamino) propyl7-2,9-dihydro-3H-dibenzo / ~ b, f7-striazolo _i / ~ 4,3- d7Z ~ 1 »47 ^diaze P ⁱ i ^l -3-one treated with sodium hydride and then with 3- (diethylamino) propyl chloride, whereby the 6,12-dichloro-2- / ~ 3- (diet _l / lamino) - propyl7-11- / ~ 3- (dimethylamino) -propyl7-2,9-dihydro-3H-dibenzo / _ ~ b, f7-atriazolo / ~ 4,3-d7 / ~ i, 4 / diazepin-3-one .

Example 33

2- / ~ 2- (I) imethylamino) -ethyl7-2,9-dihydro-3H-dibenzo / f "c, f7-s-triazolo ^ / 4» 3- ^ ⁷ azepin-3-one hydrochloride.

A solution of 1.2 g of 2- ^ ~ 2- (dimethylamino) ethyl7-2,9-dihydro-3H-dibenzo / ~ c, f_7-s-triazolo / ~ 4,3-a7azepin-3-one in ether is treated with ethereal hydrogen chloride. When the salt thus obtained is crystallized from ethanol / ether 1.1 g of 2- / ~ 2- (dimethylamino) ethyl7-2,9-dihydro-3H: -dibenzo- / ~ c, f7-s-triazolo ^ _ 4,3-a7azepin-3-one hydrochloride vom ^.

Anal. Ber. for O

3 0 9 8 31/119 2

301399

C: 63.95> H: 5.94; Nt 15.7o; Ul: 9.93. Found: C: 63.9o; H: 5.98; IT: 15.92.

Example 34

2, .9-Lihydro-9-meth _t yl-3ii '- dibenzo _i / b, f7-s-triazolo / ~ 4, 3-d7-

in a mixture of 1 g (4.16 killimol) 5, 1o-dib.ydro-5-metb.yl-11H-dibenzo / ~ b, e7 ^ ~ 1, 47dlazepin-11-one and 4.31 g (4 , 16 miilimol) hydrazinocarbonic acid ethyl ester was placed in an oil bath for 30 minutes at 221-225 ° C! immersed, then the product was worked up as described in J3ebeispiel "Ί. Crystallization from methanol gave 0.85 g of 2,9-ihydro-9-methyl-3H-dibenzo _i / ~ b, f7-s-triazolo _i / ~ 4, J-dJT / "^, _47diazepin-3-one from i ¹ . 159 ⁰ G.

Anal. Ber. for G ₁₁ -H ₁ JST-O:

15 12 4

C: 63.17; H: 4.58; N: 21.2o; G-ef .: 0: 67.95; H: 4.66.

Example 35

2- / ~ 2- (dimuhylamino) ethyl7-2,9-dih, ydro-9-methyl-3H-dibenzo- ^ f ~ b, f7-s-triazolo _i / ~ 4,3-d7Z ~ 1> 47 ^diaze P ^lr i-3-one and its H, y hydrochloride.

0.169 g of sodium hydride (4 killimoles of a 57% dispersion in mineral oil) were added to a solution of 1.09 g (4 millimoles) of 2,9-l) ihydro-9-methyl-3H-dibenzo / ~ b, fj7-g- triazolo ^ ~ 4,3-d7 _i / ~ 1, diazepine-5-one in 35 ml of dimethylformamide was added and the mixture was heated 35 minutes at 95 ⁰ G. It was then cooled to about 40 CJ and then a solution of 0.428 g of 2-dimethylaminoethyl chloride (4 millimoles in 0.423 g

309831/1192

39

Xylene) was added, then ^{the mixture was heated to 95 °} C. for a further 18 hours, and finally the reaction mixture was concentrated to dryness in vacuo. The 2- / f ~ 2- (dimethylamino) -ethyl7 ~ 2 »9-dih.ydro-9-meth.yl-3H-dibenzo _< / ~ b, f7-s-triazolo / '~ 4,3- d7Z ~ "i» 47-diazepin-3-one. Ether and water were added to the residue thus obtained, and the organic phase was extracted 3 times with 10 ml each of the above aqueous sodium hydroxide solution

and the basic mixture was extracted with methylene chloride. The extract was washed with aqueous and saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated to dryness. The hydrochloride of the base was prepared in ether with ethereal hydrogen chloride; on crystallization from methanol, 0.518 g of 2- ^ 2- (dimethylamino) ethyl7-2,9-aihydro-9-methyl-3H-dibenzo / b was obtained , f_7-s-triazolo _i / f "4,3- ^ 7Z ~ ' ¹ , 47diazepin-3-one hydrochloride from j?. 293-294 ° G.
Anal. Ber. for O ₁₉ H ₂₁ N ₅ O-HOl:

G: 61.36} H: 5.96; 01: 9.53; N: 18.84. Found: 0: 6i, 2o; H: 5.93; oil: 9.52; N: 18.30.

Example 36

7-chloro-2,9-dihydro-3H-dibenzo / ~ ^c , f7-s-triazolo / ~ 4,3-a7-azepin-3-one.

A mixture of 2.6 g (0.1 mol) of 2-chloro-6 (5H) -morphanthrid.inthione and 10.4 g (0.1 mol) of hydrazinocarbonic acid ethyl ester was heated to this temperature for 50 minutes at 22o-227 ° G preheated oil bath immersed. During this time 4 ml of liquid were drawn off via a condenser. The product obtained was a glass-like solid that would grind and water and chloroform were added. The ü-emisch was several times with water and with saturated

309831/1192

1301399 "

Extracted sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated to dryness. When the squat was crystallized from methanol, a first fraction of 1.2 g of 7-chloro-2,9-dihydro-3H-dibenzo / ~ c, f7-striazolo / f 4, 3-a7azepin-3-one in i ^f ' orm pale yellow needles of i ¹ . 272-273 C (unchanged during recrystallization). A second product fraction from o, 45 g melting at 267-269 ⁰ C, yield 59 $.
Anal. Ber. for C ₁₅ H ClN ₅ O:

C: 63.5o; H: 3.55; Cl: 12.5o; N: 14.31. Found: C, 62.99; H: 3.49; -Cl: 12.42; N: 14.78.

Example 37

2,9-dihydro-2- / f 2- (1-methyl-2-pyrrolidinyl) -ethyl7-3M-dibenzo- / _ c, f-7-s-triazolo _z / ~ 4, 3-, a7azepin-3 ~ one .

According to the procedure of Example 2, 2,9-dihydro-311-dibenzo ₍ / ~ c, f7-s-triazolo ^ / ~ 4, 3-a7azepin-3-one with sodium hydride and then with 2- (1-kethyl -2-p, yrrolidinyl) ethyl chloride, which gave the title compound.

Example 38

7-chloro-2- _/ / 2- (dimethylamine) -ethyl7 ~ 2, 9-dihydro-3H-dibenzo-

0.188 g of sodium hydride (4.47 millimoles of a 57% dispersion in mineral oil) were added to a solution of 1.25 g (4.47 millimoles) of 7-chloro-2,9-dihydro-3H-dibenzo / ~ c, f7- s-triazolo- / ~ 4,3-a7azepin-3-one in 5o ml of dimethylformamide was added and the mixture was heated 25 minutes at 95 ⁰ C. Then became

309831/1192

cooled and a solution of 0.48 g (4.47 millirool) of 2-dimethylaminoethyl chloride in 48 g of xylene was added and the mixture was heated to 95 ° G for 16 1/2 hours. The product was then isolated according to the procedure of Example 2. Crystallization from ether gave 0.92 g of 7-uhlor-2- £ ~ 2- (dimethylamine) ethyl7-2, 9-dihydro-3H-dibenzo _i / ~ c, f7-striazolo £ ~ 4-3-a7azepine - ^ - on with a melting point of 152-153 ΰ (unchanged when recrystallized).

Anal. Ber. for ü.qH.qÜIN .Ü:

0: 64.31; H: 5.410; Cl: 9.99; N: 15.79-Found i 0: 64.17; H: 5.49; Eq: 9.99; N: 15.37.

Example 39

Dibenzo / b, f7-s-triazoio / ~ 4, 3-α7Ζ ~ Ί, J; 7oxa2epin-3- (2H) -one.

A mixture of 2.59 g (0.1 mol) of dibenzo / ~ b, f_7 / ~ 1.47oxazepine-11 (luli) -thione and 10.4 g (0.1 mol) of ethyl hydrazino carbonate was heated to 2o5 for 15 minutes -21o C preheated oil bath immersed. During this time 1 ml of liquid was collected in a condenser. The clear yellow solution was cooled to about 40 and diluted with 50 ml of water. The resulting suspension was filtered and the resulting dibenzo / ~ b, f7-s-triazolo / 7 * 4,3-d7 _l / ~ 1,47oxazepin-3 (2H) -one was washed with va3ser and crystallized from methanol, . Yield 1.6 g of the j '. 253-26o ° 0. A second fraction of ο, 24β g melted at 253-255 ° ^.
Anal. Ber. for 0 .HgW ₅ O ₂ :

ü: 66.93; H: 3.61; N: 16.73. Uef .: C: 66.7oj H: 3.53; N: 16.85.

309831/1192

2301393 -3a -

Example 40

2- / ~ 2- (Dimethylamino) ethyl7-dibenzo ^ / ~ b, f7-s-triazolo ₍ / ~ 4, 3-δ / - £ ~, -7oxaz.epin-3 (2H) -one.

0.218 g of sodium hydride (5.17 iviillimol of a 57% suspension in mineral oil) were added to a solution of 1.3g (5.17 millimoles) of dibenzo / ~~ b, f7-ö-triazolo / ~ 4, 3- d7Z ~~ 1, 47oxazepin-3 (2H) -one in 50 ml of dimethylformamide was added and the mixture was heated to 95 ° for 30 minutes. Then a solution of 0.555 g (5.17 millimoles) of 2-dimethylaminoethyl chloride in 0.555 g of xylene was added and the mixture was heated to 95 ° C. for 17 hours. The product was isolated according to the procedure of Example 2. Subsequently, it was crystallized from ether and petroleum ether (bp. 3o-6o ° ö), thereby o.65 g of 2- / ~ 2- (dimethylamine) -ethyl7-dibenzo / _ ^/ ~ b, f7-s-triazoleG / f ~ 4, 3-d7Z ~~ 1, J-7oxazepin-3 (2H) -one from ü ¹ . 1o9-111 ° 0 preserved. After recrystallization from ether, the melting point was 10-3-1o4 ° above sea level.

Example 41

o-2 - ^ * ~ 3- (1-piperidinyl) propyl7-3H-dibenzo / ~ c, f_7-s-

triazolo _/ / ~ 4, J-

According to the procedure of Example 2, 2,9-dihydro-3H-dibenzo / 3c, f7-s-triazolo / ~ 4,3-α7azepin-3-one with sodium hydride, and the resulting product was treated with 1- (3-chloropropyl) piperidine reacted, whereby the l'itelverbindungen received.

309831/1192

Example 42

2.9 ~ Dibiydro-2- ^ ~ 2- (i-meth.yl-2-pyrroliclinyl) -propyl7-3H-di-

4, .j-a / azepin-o-on.

2 g (o, oo8o5 col) 2.9 - uihydro-3-ti-dibenzo ^ ~ c, f7-3-triazolo- £ ~ 4,3-a7azepin-3-one with 194 rug sodium hydride in dimethylformamide and then with 1.13 g of 2- (3-fluoropropyl) -1-methylpyrrolidine treated, 1.7 g of the title compound obtained in the form of an amorphous solid.

Example 43

^ j 9-dihydro-3Ii-dibenzo / _ CjfJ-s-3-a / azepin-3-one and its kaleat.

According to the procedure of Example 2, 2,9-Hydro-3H-dibenzo / c, f / -s-triazolo £ 4,3-a / azepin-3-one was treated with sodium hydride and then with ethylaminoethyl chloride, whereby the title compound was obtained in ¹ orm of a yellow oil. This product was converted with maleic acid in ether into the 2- £ ~ 2- (diethylamino) ethyl7-2,9-dih ^ d.ro-3li-dibenzo / ~ c, f7-s-triazolo _{i (} / ~ 4, 3-a7-azepin-3-on-maleate from j ?. 147-148 ⁰ O transferred.

Ber. for Cp Hp.N.Ü.O.H.O .:

ü: 64.64; Hi 6, o8; Ii: 12.06.

G-ef .: 0: 64.58; H: 6, o1; IJ: 12, io.

Example 44

2, 9-Dihydro-2 - / _ 2- (1-piperidinyl) ethyl7-3H-dibenzo / ~ c, f_7-striazolo / ~ 4, ;; - a7azepin-3-one hydrochloride.

309831/1192

According to the procedure of Example 2, 2, y-iji hydro-3H-dibenzo / ~ c, f7-s-triazolo / ~ 4,3-a7azepin-3-one with sodium hydride and then with T- (2-chloroeth, yl) piperidine treated. After extraction with hydrochloric acid, the 2, 9-dihydro-2- / ~ 2- (1-piperidine ^ l) -ethyl7-5H-dibenzo _i / ~ "c," f7-s-triazolo _i / ~ 4, 3 -.§7azepin-3-one hydrochloride obtained from n \ 246.5-248 ⁰ C.

Example 45

2, 9-Dihydro-2- ^ 2- (methylamino) ethyl7-3E-dibenzo _i / ~ c, f7-striazolo _/ / ~ 4> 3-a7azepin-3-one.

Solution of 2,9-dihydro-2- _/ / ~ 2- (diir] ethylamino) ethyl7-3H-dibenzo / ~ c, f7 ~ s-triazolo / _ ~ 4> 3-a7azepin-3-one in benzene and chloroform was heated to reflux temperature for 12 hours with ethyl chloroformate, whereby the 2 - / _ '~ 2 - ^ _ ~ (ethoxycarbonyl) methylamino7äthyl7 ~ 2, Ό- _alhydro-- 3H-dibenz O - Z ^- C , f 7-striazolo ₁ / ~ 4,3-a7azepin-3-one.

This -product was heated for 3 hours on HückfIußtemperatür in potassium hydroxide containing Jrroyplenglycol to give the 2- ^ 2- (l \! Iethylamino) äthyl7-2,9-dihydro-3H-dibenzo _(/ ~ c, f7-s-triazolo / ~ 4J3-a7azepin-3-one from J ?. 125-126 ⁰ C received.

The hydrochloride of 2,9-dihydro-2- / ~ 2- (methylamino) -ethyl7-3H-dibenzo _/ / ~ c, f7-s-triazolo / ~ 4,3-a7a2epin-3-one was made by mixing the base obtained with anhydrous hydrogen chloride in Ither, melting point 257-259 ° C

Example 46

$ -Chlor-2,9-dihydro-2- _i / 2- (morpholino) ethyl7-3H-dibenzo _i / s-triazolo _i / ~ 4, 3-a7diazepin-3-one.

309831/1192

2301398

Each of the procedure of Example 2 was prepared from 6-chloro-2,9-dihydro-3ii-aibenzo / 7 ^G »f7-s-triazolo ^ ~ 4, 3-a7azepin-3-one> Sfatriuiah ^ drid and uiorpholinoethylchlorid .

Example 47

2- £ ~ (iL _i ethylpiperiäinyl-2-yl) methyl7-2,9-dihydro-3II-dibenzo-

j 3-a7azepin-3-one-h, y hydrochloride.

After the procedure of Example 2, 2, 9-Mji dibenzo ^ c,] ^ - st ■ riazolo / ~ 4,3-a7azepin-3-one, sodium hydride and i ~ kethyl-2-ehlorinethylpiperidine with subsequent extraction with Hydrochloric acid 2- / ~ (i-IvIethylpiperidinyl-2-yl) -methyl7-2,9-dihydro-3H-dibenzo / ~ c, b7-s-triazolo / ~ 4,3-a7azepin-3-one-hydrochloride from I ' ¹ . 15o- "l51 ° 0 established.

Example 43

7-0hlor-2 - / _ 2- (dimethylamino) ethyl7-3H-dibenzo / ~ b, f7s-

1,47oxazepin-3- (2H) -one.

Following the procedure of Example 2, 7-chloro-aibenzo- / ~ b, f7-s-triazolo ^ / ~ '4> 3- ^ 7Z ~ "' ⁱ > i7 ^oxaze Pii ¹ -3- (2H) -one , Sodium hydride and dimethylaminoethyl chloride, the 7-chloro-2- / 7 "2- (aimethylamino) ethyl7dibenzo _/ / ~ b, f7-s-triazolo ^ ~ 4,3-oxazepin-3- (2H) -one from i ¹ . 142-143 ⁰ O produced.

Example 49

Dibenzo ^ b, f7-s-triazolo _/ / ~ 4, 3-d7Z ~ 1, ^ 7thiazepin-3 (2H) -one

309831/1192

23013 ?! " ⁴² "

According to the formula of Example 1, dibenzo, / b, f7 / ~ "i» 47-thiazepine-11 (lOH) -thione and hydrazinocarbonic acid ethyl ester were converted to i) ibenzo / ~ b, f7-s-triazolo / ~ 4,; ^ -d [// ~ 1, i7 ' ^tlaiaze P ^{: i} - ⁿ "3 (2H) -on vom F. 3o2-3o3 ° ü.

Example 5o

2 - / _ 2- (dimethylamino) ethyi7 ⁽ 3ibenzo / b, fJZ-st £ ~ 1,47thiazepine-3 (2H) -one hydrochloride.

According to the instructions in Example 4, I) ibenzo _/ / ~ b, f7-striazolo ^ / ~ 4, 3- ^ 7 / Z ^ > ή7 ttiiazepin-JC 2H) -one was reacted first with sodium hydride and then with dimettivlaminoethyl chloride, after extraction with hydrochloric acid the 2- _/ / ~ 2- (üimethyl- am ± no) 'ethyl / ä ± beiazo £ ~' b, t / -s ~ tr ± azolo / ^ '^, 3-§ // _ -1, J / thiazepine-3 (2H) -one hydrochloride mp 292-293 ° ü received.

Example 51

6-Gh.lor-2- _< / 2- (dimethylamino) ethyl7dibenzo ₍ / b, f_7-s-triazolo-

According to the procedure of Example 2, the title compound was obtained from 6-chloro-diben_zo / ~ "b, f7-s-triazolo / ~ 4, 3-d7Z ~" i , A 3 (2H) -one, sodium hydride and. 2-dimethylaminoethyl chloride produced.

Example 52

-2- ^ 2- (dimethylamino) ethyl / -2,9-dihydro-3H-dibenzo-

1 , 47 ^dia zepin-3-one hydrochloride.

309831/1192

According to the instructions in Example 4, 7-uhlor-2,9-dihydro- ^ ji-dibenzO ₁₁ Z ^- C, f7 ~ s-triazolo ₁ / ~ "41 3-d / diazepin-3-one (prepared according to juimethylaminoathylchlorid 2 example 2 from 7 ~ ühlor-5, io-dih.ydro-11H-dibenzo ^ b, e7 / ~ 1,47diazepin-11-thione, ^i1. 289-29O ⁰ U 'and. after reaction Nixt with hydrochloric acid the x'itei compound in front of ^1. 263-264 obtained

Example 53

2 - / _ 3- (Phthalimiäo) äth _t) 'l7-2, 9-dili ^ dro-3H-dibenzo £ c, f_7-s-

0.221 g of sodium hydride (o, o1 col of a 57% uisj -sion in luineral oil) were added to a solution of 2.49 g (o, o1 col) of 2,9-dihydro-3H-dibenzo / ~ c, f7- s-triazolo £ ~ 4,3-a7azepin-3-one in 50 ml of dimethylformamide was added and the mixture was heated to 95 ° for 40 minutes. A solution of 2.54 g (0.01 col) of N- (2-bromoethyl) phthalimide in 15 ml of dimethylformamide was then added over the course of 2 minutes and the mixture was heated to 95 ° C. for 17 hours. It was then evaporated, the residue was treated with 50 parts of water and the resulting suspension was filtered. The solid was crystallized from methanol, giving 2.8 g of 2- / ~ 3- (phthalimido) ethi'l7-2,9-dihydro-3H-dibenzo ^ Cjf / '- s-triazolo ^ 4,5-a / azepin-3-on from i ¹ '. 134-185 After recrystallization, the melting point had risen to 186-187 ° C.
Anal. Ber. for O ₂₅ H ^ H.0_:

G: 71.08; H: 4.29; Ns 13.26. Found: ü: 71.105 II: 4.29; K: 13.13.

309831/1192

1301399

Example 54

/ c, f_7-s-triazolo- / ~ 4> 3-a7 ^aze Pin-3 * on and its w-naphthalenesulfuric acid salt.

In a mixture of 1.89 g (4.47 killimol) έ- £ ~ 3- (PkLthaiimido) ethyl7 2, 9-dihydro-5H-dibenzo £ ~ "c, f7-s-triazolo ₍ / ~" 4, 3- A7azepin-3-one, 9, og (o, o179 mol) hydrazine hydrate and 25 ml of ethanol were stirred for 24 hours at room temperature, and the resulting thick suspension was filtered.

The filtrate was evaporated, the chopping stand was dissolved in methylene chloride / water. The extract was washed with water, dried over anhydrous magnesium sulfate and evaporated, whereby 0.649 g of 2- ^ ~ 3- (iünino) ethyl7-2, 9-dihydro-3H-dibenzo / ~ c, f7-s-triazolo _/ / * ~ 4j 3-a7azepin-3-one received.

The 13-naphthalenesulfonic acid addition salt was prepared in methanol and recrystallized from methanol, tf. 281-, 5-283 ° above sea level

Example 55

- / f (l \ r-Benzyl-N-methylamino) ethyJ-7-2,9-dihyd.ro-3H-dibenzo / ~ c, f7-s-triazolo / "~ 4> ji-

According to the procedure of Example 2, 2,9-dihydro-3H-dibenzo _J / ~ c, f7-s-triazolo _/ / ~ 4,3-a7azepin-3-one was treated with sodium hydride and then with 2-benzylmethylaminoethyl chloride, whereby the 2- / ~ 2- (N-benzyl-W-methylamino) ethyl7-2,9-dihyd.ro-3H-dibenzo ^ ~ c, f7-s-triazolo _i / ~ 4, 3-B7azepin-3-one mp 98-99.5 received ⁰ O. When this compound is hydrogenated in a manner known per se, the compound is obtained from

309831/1192

Example 45, namely the 2,9-dihydro-2- / _> 2- (methylamino) ethyi7-3ri-üibenzo / ~ c, f7-3-triazolo / ~ 4,3-a7azepin-3-one.

Example 56

6-Ghior-2,9-dihydro-3H-dibenzo ^ C 3-on.

IIIin Geir-isch from 26.5 g (0.13 hol) 3-chloro-6- (5H) -m.orphanthridinhlon and Io7 g (1.03 col) hydrazinocarbonic acid ethyl ester was heated to 210-215 ° C for 120 minutes heated in an oil bath preheated to this temperature. During this period 45 ml of liquid was collected over a condenser. The product obtained was a solid which was ground and mixed with water and chloroform. The mixture was extracted several times with chloroform, the extracts were combined, washed with water and saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated to dryness. On crystallization from ethanol / chloroform, the residue gave 9> 5 g of 6-chloro-2, 9-dihydro-3H-dibenzo / f ~ c, f_7-s-triazolo ^ 4, 3-3-one from j * ¹ . 266-267 ⁰ C (unchanged during recrystallization). The second fraction of 3.65 g melting at 265-266 ⁰ C. Anal, itäer. for C ₁₅ H ₁₀ ClN ₅ U:

C: 63.5o; H: 3.55} Gl: 12.5o; N: 14.81. : C: 63.43; H: 3.7o; Cl: I 2.8oj N: 14.79.

Example 57

6-Chior-2- ^ f "2- (diiiiethylaniino) äthyl7-2,9-dihydro-3H-dibenzo-

309831/1192

26 U A t% SQ ε Mb

0.97 g of uranium hydride (23 Liillimol- a 57'plgen dispersion in mineral oil) were added to a solution of 6.5 β (23Jlimole) 6-chloro-2,9-dihydro-3H-c! Ibenzo / ~ c , f7-s-triazolo £ ~ 4j 3-a7 ~ azeijin-5-one in 23o rcl LiniethyIformamid was added and the (remisch was heated 40 minutes to 95 ° O. After reaction with dimethylaminomethyl chloride, the product was according to the instructions of .Example 2 Crystallization from ether gave the 6-uhlor-2- £ ~ 2 ~ (dimethylamino) ethyl7-2,9-hydro-3H-uibenzo ^ ~ c, f7-s-triazolo ^ "~ 4,3-£ 7azepin-3-one from j?. 158.5-160 ° above sea level

Anal. Lei *, for ü "H.qüll U:

.C: 64.31 ί Π: ί5.4ο; 01; 9.99; N: 15.79. G-ef .: O: 64.39} H: 5> 4oj 01; 9.35; U: I6.2o.

Example 5Ö

7-Ghlor-dibenzo ^ / bj ^ -s-triazolo ^ 4, y-äf / _ 1, _47 ^oxaze P ^{: i} - ^ri ~ 5 (2H) -on.

According to the procedure of Example 39 "7-Ohlor-d.ibenzo-1 , _47oxazepine-11 (1üE) -thione and hydrazinocarbonic acid-

äthyiester to the i ¹ it elver connection from the j ?. 313-314 ⁰ G implemented.

Example 59

7-chloro-2- / 3- (dimethylamino) propyl7dibenzo / ~ b, f7-s-triazolo- L 4 »3 ~ J7zT ~ 1» i: 7 ^{o: xaze} .Pii ^{: 1} -3 (2H) -one and its hydrochloride

According to the procedure of Example 40, 7- (chloro-dibenzo- / ~ b, f7-s-triazolo / _i ~ "4,3- ^ 7Z ~ 1» 47 ° xa2epin-3 (2H) -one with sodium hydride and then with 3-Diineth.ylaminopropylchlorid to -iitelverbindung from ^i1. 228-229 ° 0 implemented.

INSPECTED

Example 60

^ - / ~ 3- (JJiiüe u by li) ro ρ ν 1) ai'iirxo / u i ben zo £ ~ b, f_7-3-t ria 2Olo / _ "~ 4,3- £ ~ 1,4 / Ox _r zepin-3 (i-'H) -one and its hydrochloride.

In accordance with the procedure of Example 4o, dibenzo £ ~ b, f7-striazolo £ ~ 4 '; ~ & / L 1 j4 / oxazepin-i) (^ li) -one was first treated with sodium hydride and then with p-jimeth ^ laminopropyl chloride unset, v / if Eau obtained after extraction with hydrochloric acid the union of h \ 133-134 ° G as partial hydrate.

Example 61

7-Ghlor-dibenzo ^ b, i_7-s-triazülo / ~ 4} i-jä7 on.

According to the procedure of Example 1, 7-chloro-dibenzo

in-11- (iüH) -thione and hydrazino carbons

Acid acid ester to the title compound of the i ¹ . 293-294 ° C implemented.

Example 62

-2- £ 2- (diB'.eth ₀ lamino) ethi'i7-dibenzo / ~ b, f7-s-triazolo-

3 (^ ¹ Ii) _on.

According to the procedure of Example 4, 7-ghlor-dibenzo- / ~ b, f7-3-triözolo / ~ 4,3-d7 £ "i> 47 ^ ^a i ^a zepin-3 (2H) -one was initially carried out with Katriui: ih ^ anhydride and then reacted with 2-Oimeth ^ laminoäthylchlorid to iitelverblndung, the ¥. 121-122 C.

309831/1192

2301393 -48-

Example 63

7-chloro-2- / ~ 3- (dlmethylamino) propyl7-aibenzo / ~ b, f7-s-triazolo-, 47 "th.iazepin-3 (2H) -one.

According to the prescription of example. 4 was 7-chloro-dibenzo- _< / ~ b, f_7-s-triazolo _ii / ~ 4, 3-d_7Z ~ ^ tA / ^ h ± nze ^ ± n-3 ('dil) -oia first with sodium hydride and then with 3-dimethylaminopropyl chloride to the title compound from ü ¹ . 123-125 ° C implemented.

Example 64

9,9-dioxo-dibenzo / ~ b, f7-s-triazolo / f 4,3-3 (2H) -one.

1.3 g (o, oo5 mol) j) ibenzo / "b, f7-8-triazolo / ~ 4,3-l7Z" i »47-thiazepin-3 (2H) -one were in chlorine form / methanol (1: 1) Dissolved on a steam bath, then the G-emic was mixed up. Cooled to room temperature. Then 1.72 g (0.1 mol, 85 μQ. M-chloroperbenzoic acid were added with stirring. A precipitate forms in the course of 10-15 minutes, then the mixture is stirred overnight, giving a clear solution is poured into a separatory funnel and washed with 25 ml of saturated sodium bicarbonate solution and 5o ml of water. The organic phase is separated off and 2 χ with 25 ml of saturated sodium bicarbonate and 1 χ washed with 25 ml of saturated sodium chloride solution. The organic phase is then evaporated to dryness, 1.7 g of a white solid are obtained. Crystallization from acetic acid gives the 9,9-dioxodibenzo _z / ~ b, f7-s-triazolo / ~ 4,3-J7Z ~ ¹ ~ 17 "th- iazepin-3 (2H) -one, melting at 3o7 0 ° (wet). recrystallization from methanol / Lethylenchlorid obtained o, 763 g of the pure compound from ^i1. 3o4-3o6 ° ü.

309831/1192

Anal. Ber. for O ₁ , H ₉ N ₅ U..rf (299,3ο):

G: 56.13} H: 3.3ο; N: 14, o4j B: 1ο, 72. deep .: U: 56.22; H: -3.2ο; N: 14.26; ü: 1ο, 53 ·

Example 65

9,9-3310x0-2- ^ 2- (üiiueth.ylamino) -äthjJ-7-d.ibenzo / ~ b, f7-sbriazolo £ ~ 43d7zf "i , 4 / thiazepin-3 (2ii) -one.

1.49 g (o, oo5! Viol) 9,9-moxo-dibenzo £ ~ b, f7-s-triazolo / 4,3-j37 ~ ^ 1,4_ / thiazepine Were dissolved in diinethylformainide, then o, 12 g (0.05 LiOl) of sodium hydride were added and the mixture was heated on a steam bath for 40 minutes until a clear solution resulted, then 0.535 g of 2-dimethylamino acid chloride in aylene (1: 1, 1 , o7 g) was added and the solution was heated on the float for 17 hours. Then water and ethylene chloride were added, the organic phase was separated off and extracted 3 times with 15 ml of lo ^ iger hydrochloric acid each time. The acidic extract was cooled, made basic with 20% sodium hydroxide solution, extracted with ethylene chloride and dried over magnesium sulfate. Evaporation gave 1.6 g of solid. Crystallization from kethanol / chloroform (1: 1) gave 1.3 g of 9j9-dioxo-2- / 2- (dimethylamino) -ethyl / ^ - dibenzo ^ ~ b, f / -striazolo _/ / ~ 4,3- d7Z ~ 1,4 / thiazepin-3 (2H) -one from 1 ?. 2oo-2o1 U. Another recrystallization gave the product in jj'orm colorless rrismen (1.175 g) from Έ. 2o2-2o3 ° Co Anal. Ber. for GH ₁₃ N ₄ O ΰ (37o, 42):

Oj 58.36; H: 4.89? N: 15.13? 3: 8.660 deep, ι 0: 58.25; H: 4.92; N: 15.16; S: 8.66.

309831/1192

- 5ο -

Example 66

2,9-Dihydro-9, g-dimethi'l - '^ ii-aibenzo ^ c, fy-s-triazolo ^ / 4 »3-a / -azepin-3-one.

Ai 6-chloro-i 1,1 i-dimethylmorphanthridine.

xüa melt of 4 »72 g (0.02 LoI) 11,11-diriethyl-6 (5H) - 'morphanthridinone and. 5.8 g (o, o23 it oil) phosphorus pentachloride. was stirred under nitrogen at 130 ° for 2 hours. The phosphorus oxychloride formed was distilled off under pressure, leaving a viscous red oil (5-1 g). This was crystallized and. employed in the nactist stage without further training.

B. 11.1 i-Dimeth.j / lmorphanthridine-lM-carbethoxyhvdrazide.

5.1 g (0.02 mol) 6-chloro-11,11-uiriA-methylinorphanthridine and 1o.4 g (0.1 KoI) hydrazinocarbonate in 2oo ml absolute ethanol were refluxed in nitrogen for 21 hours Boiled and then evaporated to dryness in vacuo.

The pork stand was dissolved in 100 ml of ethylene chloride and washed with 2 ^a ß> cold sodium hydroxide solution, dtmn with water and concentrated in vacuo, where b, T g 11,11-dimethyl-morphanthridine-N-carbä.thoxy-hydrazide 'obtained. This was used in the next stage of the process without further notice.

0.2,9-dihydro-9,9-dimethyl-3ii-dibenz ^ / ~ c, f7-s-triazolo-

6 »4 g (o, o2 hol) 11,11-dimethylmorphanthridine-N-carbethoxyhydrazide in 100 ml of n-butanol were refluxed in nitrogen for 24 hours. The solvent was in vacuo removed and an oil was obtained which was dissolved in 40 ml of chloroform, with cold 5'Mger sodium hydroxide solution and with water washed and concentrated to a viscous, colorless syrup. This was crystallized using acetone,

309831/1192

1.53 g of 2, 9-iJihyäro-9,9-diiiieth _t ) l -;> Ji-dibenzo _/ / ~ c, f / '- s-triazolo _/ / ~ 4,3-a792epin-3 were obtained -on in jj'orm further needles from tf. 311-314 ° E.
Anal. Ber. for ΰ, '& ΛΐΛ) :.

O: 73.63; H: 5.45; N: 15.15. Found: O: 73.14; Hs 5.43; N: U, 3g.

Example 67

2,9-Dihydro-2 - / _ 2- (dimethylamine) ethy 17-9> 9-dimettiyl-3H-aibenzo / ~ e, fJ7-s-triazolo ^ ~ 4,3-a7azepin-3-one.

A mixture of 1.38 g (0.05 col) 2,9-dihydro-9,9-dimethyl-3H-oibenzo / ~ c, f7-3-t3? Iazolo £ ~ 4,3-a, 7azepine-3 -one ul ^T atriumhydrid in mineral oil (5o ^, 25o and 0.006 mg LoI) in 5o ml of dimethylformamide was in nitrogen atmosphere at 95 ° 4o ikinuten ^ heated. "Then, vurden added o o1 iviol Dirnethylaminoäthylchlorid in benzene, and it was still 7 iwinuten The dimethylformamide was removed in vacuo, resulting in a birup which was dissolved in 50 diol of diethyl chloride and water When the solvent was boiled off, a liquid was obtained which was crystallized from Lethvlenohlorid / Skellysolve B, v / above 6.5o mg 2, _: :) -Dihydro-2- / 2- (dimethylolino) ether ^ 17-9 "• j-dimethyl-3H-dibenzo / c ~, f7-s-triazplo · Z ~ 4,3-a7azepin-3-one from l \ 148-149 ⁰ C obtained. Anal. SSER. for U ₂₁ H ₂₄ II ₄ O:

U: 72.33; H: 6.94; N: 16, o3. Found: Gi 72.42; H: 6.97; K: 16.3-3.

309831/1192

2301393 - 52 -

Example 68

6yChlor-2- £ ~ 3- (dimethylamine) pro pyl7 ~ 2, 9-dihydro-5H-dibenzo- / ~ c, f_7-s-triazolo ^ / ~ 4> 3-a7 ^aze Pi ^I1 ~ 3-one and its üxalat «

According to the procedure of Example 2, 6-chloro-2,9-dihydro-3H-dibenzo / ~ c, f7-s-triazolo _/ / ~~ 4, 3-.a / azepin-3-one with sodium hydride and then with 3-Dimethylaminopropyl chloride to the 6-chloro- 2- / ~ 3- (dimethylamino) propyl7-2,9-dihydro-3H-dibenzo _/ / ~ "c, fy'-striazolo ₍ / '~ 4> 3- ^ 7azepine-3 -one converted, which was obtained as Cl. The oxalate was formed with oxalic acid in ether, 235-236 ⁰ G. '

Example 69

2 - / _ 2- (4-methyl-1-piperazinyl) ethyl7-3H-dibenzo / f "c, f / -striazolo ^ 4> 3-§ / azepin-3-one and its dihydrochlorides

According to the procedure of Example 2 was 2,9-dihydro-3H-dibenzo / "ο, f7 - s-triazolo / ~ 4- _3-t a7azepin-3-one with sodium hydride und'dann with 1- (2-chloroethyl treated) -4-methylpiperazine to give the title compound as an oil -B ¹ Orm would receive the Gl was dissolved in ether and treated with ethereal hydrogen chloride, besides the dihydrochloride was formed as the hydrate, mp 245 ° the O what.
can be obtained in vacuo.

F. 245 O formed. The anhydrous courtship can by i'rocir.nen

According to the instructions in the above examples, other 'ühione of the formula A can be converted into an azepine, diazepine, oxazepine or diazepine of the formula II with an alkyl hydrazinocarbonate, for example the ethyl, ethyl, propyl or isopropyl ester. Examples of compounds of formula II obtainable in this way are:

309831/1192

6, i2-I) ibroi! -2,9-clihydro-3H- (iibenz; o _i / -G, f7-s-triaz; olo / f "4, 3-a7 azepin-o-one, '· · '■

6- ^ mino-12-broffi-2, 9-dihydro-3H-dibenZO ₁ ^{Zf -} C, f7-s-triazolo- / f ~ 4,3-s / azepin-3-one, i3-l: ettiyl- 2,9-diliydro-5- (methyltb.io) -3Ji-dibenzo / ~ G, f7-striazolo, / ~ 4, 3- £ 7azepiri-3-one, 2,9-dih.ydro-5-isopropyl- 1o- ^ od-3H-dibenzo £ ~ c, f7-3-triazolo-

C, 11-Jiä azepin.-3-one, 7,12-jjiiso _iJ ropoxv-2,9-dihydro-3H-dibenzo _i / ~ c, f7-s-triazolo Z 4, ^ -a / azepin-S- on.,

ido-2, S-uihydro-6-isopropyl-3H-dibenzoZ ~ c, _i f7 ~ ^s ~ 4,3-a7azepin-3-one,

azepin-3-one.,! 5-ii ¹ luor-2,9-dib.ydro-3H-di benzoic, f7-s-triazolo _< / ~ 4,3-a7azepine-

12-Amino-2,9-dih pin-3-one, 2,9-dihydro-1i-iodo-3H-dibenzoZ ~ c, ^ ^r -a-triazolo / ~ 4 »3-a7azepin-3-one, 11 -bromo-2,9-dihydro-3H-dibenzo / ~ G, f7-s-triazolo £ -4,3-a7azepine - ^ - on, 12-j3ro «j-6-fluoro-2, 9-dib. ydro-3H-dibenzo / ~ c, f7-s-triazole-

6, i2-x>icb.lor-9,9-diiiiet; hyI-2,9-dihydro-3H-aibenzo _i / ~ c, f7-striazolo £ ~ 4 _> 3-a7 ^az spin ~ 3-one, 5 -iiraino-9,9-dietb.yl-2,9-dihydro-3fl-dibenzo / ~ c, f7-s-triazolo

pin-3-on

pin-3-ün,

309831/1192

6,12-J) ibroir; -2,9-di'aydro-3n-dIbenzo ^ / b, f / -s-triazolo ₍ / ~ 4, '$ -§ / - ^ ~ * 1, _4 / diazepine- 3-on,

6,11-diaaino-2, y-dihjdro-3H-diben2; o / ~ b, f7-s-triazulo / ~ 4,3-d7 /~1,47d.iazepin-3-on ,.

7,11-Miodo-2,9-dihydro-3H-dibenzo _i / ~ b, f7-s-triazolO £ _ ~ 4j 3-jd7 ~

5 - b'ormaiüido-2, 9-ditiydro-1§-me chi'l-3H-dibenzo _j / ~ b, f7-s - triazolo- / ~ 4,3- ^ 7 / ~ 1 ji-7diazepiri -3-on,

2,9-33i'ciydro-11-iodo-3H-diberizo /; ~ b, f7-s-triazolo / f "4,3- ^ 7Z '~' ¹ > 47 ~ diazepin-3-one,

13-i'luoro-2,9-dihydro-3H-dibenzo _i / ~ b, f7-. ^< :: - triazolo ^ ~ 4,3-d7- "/""ijj / diazepin-'i-on,

6-J3rom-2,9-dihydrO-3H-dibenzo / ~ b, f7-s-triazolo _i / ~ 4,3-d7Z ~ 1 1 $ - ~ diazepia-3-one,

i2-U-chloro-2,9-dihydro-3H-dibenzo _! / ~ b, f7-s-triazolo ₍ / ~ 4,3-d; 7zri> i / ~ diazepin-3-one,

2,9-Dihyd.ro-5-methyl-1o- (propylsulfonyl) -3H-dibeazo / ~ b, f7-striazolo / ". · Ζ _ ^ _ 7Ζ ~ 1, ^ diazepin - ^ - one, 2,9-ditiy .ro-8- (isopropylthio) -3fi-dibenzo ₍ / _ ~ "b, f7-s-triazolo-

12- (diethylaEiino) -8-fluor-2,9-dihydro-3H-dibenzo ₍ / ~ b, f7-g-triazolo £ ~ 4, 3-j ~ 7Z ~ 1,47diazepin-3-one,

2,9-Dih.ydro-11 -propoxy-o-propyl-JH-diben.zo ^ bj ^ T'-s-triazOlo- / ~ 4, 3- ^ 7Z ~ 1 »47diazepin-3-one,

7- (Ethylsulfitiyl) -2, 9-dihydro-3H-dibenzo / _ ~ b »f7 ~ ^s -i ^{; r:} i- ^azo l ^o ~

7, i3-Diättiyl-2,9-dihydro-3H-dibenzo / ~ b, f7-s-triazolo / ~ 4,3-d7 ^ / ~ 1,47diazepin-3-one,
5 - (. Dimethylamino) -2,9-ditiydro-3H-dibenzo _i /~b, f7-s-tria.zolo-

6,12-I) ichlor-9- (dimethylamino) ynethyl-2,9-ditiydro.-3H-dibenzo- ^ ~ b, f7-s-triazolo ^ / "~ 4,3-d ^ 7zr"'' » j47diazepin-3-one, 9- _/ / ~ 3-Cl) iäthylaiT! ino) propyl7 ~ 1 i-fluoro-2, 9-di ^ dro-3H-dibenzo-

, 47diazepin-3-one,

309831/1192

2,9-i) ihydro-3-methyl-9- (2-1110rpholinoethyl) -3H-dibenzo / _ b, s-triazolo ^ ~ 4,3-d // ~ 1,4 / diazepin-3-one,

6, i2-Di ~ 77 "7Z ~

(2H) -one,

7-chloro-dibenzo _/ / ~ b, f7-e-triazolo _j / ~ 4, 3-

4,;) - α7Ζ ~ ¹ »47oxazepin-3 (2H) -one, j ^ -s-triazolo / ~ 4» '■} -§ / £ ~ Λ , 4 / oxazepin-3 (2fi) -one, 5 -sroin-12- (aiprop ^ iaraino) dibenzo / ~ b, f7-Q-tr-iazolO £ ~ 4j3-d7Z 1 j 4 / oxazepin-3 (2 ^.) -one,

oxazepin-3 (2H) -one,

10-k'etb.yl-dibenzo _/ / ~ b, f7-s-triazoloZ ~ 4, 3-c [7z

6,12-I) i.lor-dibenzo / ~ "b, ^ 7 ~ s-triazolo _i / ~ 4j 5 ~ üJ £ ~ ^ , _47thiazepin-3 (2H) -one, 7,11-dinitro-dibenzoZ ~ b, f7-s- "fcriazoloZ ~ 4, 3-d7 / ~ 1> 47 5 (2H) -one, 7- (ethyl sulfone3 ⁷ i) rjibenzo / ~ b, f7-s-triazoloZ ~ 4, 3-d / ^? / ~ 1,4 / -t hia zepin - ':> (2ii) -on,

3 (2H) -one,

ΐhiazepin-3 (2H) -one, 6,7-I) ifluor-oibenzo _{/ L} ~ b, f7-3-triazolo _i / ~ 4, 3 (2H) -one,

3 (2Hj-on,

309831/1192

301399 -56-

5-iodo-dibenzo / ~ b, f7-s-triazolo _i / ~ 4,3-d / '/ ~ 1,4 on,

13- ^(r Diättii lamino) -5-ethoxy-dibenzo _j / ~ b, f7-s-triazolo _/ / ~ 4j _47thiazepin.-3 (2H) -one, and the like. like

If these compounds of the formula II are treated with a strong base, for example sodium hydride, potassium hydride, sodium butoxide or potassium isopropoxide, and then with a halogen compound of the formula RpX, in which Rp has the above meaning and X denotes chlorine, bromine or iodine, the corresponding ones are obtained 'Compounds of formula III. Examples of such "compounds are:

6,12-dibromo-2- / ~ 3- (diethylamino) propyl7-2,9-dihydro-3H-dibenzo / ~ c, f7-s-triazolo £ ~ 4, 3-ja7azepin-3-one, 6-amino -12-bromo2- (2-morpholinoethyl) -2,9-dihydro-3H-dibenzenes, fy'-s-triazolo / ~ 4,3-a7azepin-3-one, 2- / ~ 3- (dimethylamino) propyl7- 2,9-dihyd.ro-13-methyl-5- (methylthio) -3E-dibenzo / ~ c, f_7-s-triazolo ₁ / "- 4, 3-a7azepin-5-one, 2- / ~ 3- (Dipropylamino) propyl7-2,9-dihydro-5-isopropyl-1o-3od-3H-dib-enzo / ~ "c, f7-s-triazolo / ~ 4, 3-a7azepin-3-one, 6.11 - Diethoxy-2- _i / "~ 3- (diethylamino) propyl7-2, 9-dih; / - dro-3H-aibenzo _i / ~ c, f7-s-triazolo / ~ 4, 3-a7azepin-3-one,

7,12-diisopropoxy-2- £ 2- (dimethylamino) ethyl7-2, 9-dihydro-3II-dibenzo _i / -c, f7-s-triazolo _i / ~ 4, 3-α7azepin-3-one, 13 -Acetamido-2- / ~ 2- (diethylamino) ethyl7-2,9-dihydro-6-isopropyl-3H-dibenzo _i / ~ c, f7-s-triazolo / ~ 4, 3-a7azepin-3-one, 12 -Formamido-2,9-dihydro-2- / ~ 3- (1-pyrrolidinyl) propyi7-3H-dibenzo / -c _f f7-s-triazolo / ~ 4,3-a7azepin-3-one, 5-i " ¹ luoro-2,9-dihydro-2- / ~ 2- (i-piperidinyl) ethyl7-3H-dibenzo- -triazolo / -4j 3-a7azepin-3-one, '

-2- ^ 2- (4-methyl-1-piperazinyl) ethyl7-2,9-dihydro-3H-dibenzo _/ / ~~ c, f7-s-triazolo / ~ "4, 3-a7azepin-3-one, 2,9-dihydro-11-ood-2- / ~ 2- / ~ 2- (i-methyl-2-piperidinylJ.7-eth3rl7-3H-dibenzo _i / ~ c, f7-s-triazolo / ~ 4, 3- ^ 7

309831/1192

2301393

2,9-i) ih; / ciro-11-bro] ü-2- ₍ /~3-(2-(i-ethanol )-piperazino)propyl.7-3H-dibenso£~c,f7-s- triazolo / f ~ 4, -ja / azepxn ^ -on, 12-bromo-bf luor-2, 9-dihydro-2- (2-morpholinoätlayl) -3H-dibenzo £ ~ "c, f7-8-triazolo ^ ~ 4j 3-a7azepin-3-one, 6.1 £ -I) I.lor-2- £ ~~ 3- (diet h ". Lamino) -propyl7 ~ 9,9-dlmethyl-2 :, 9-

5-iiiaino-9, y-dietli _t / l-2- / ~ 2- (diineth _t> -lamino) eth. _< yl7-2, 9-ciihydro-3ii-uibenzo _/ / ~ c, f7 ~ ^s - " ⁱ ' ^r iy ^so l ^o Z. 4» 3-a7azepine ~ 3-oa, 6,12-iJibroni ~ 2- £ . ~ 3- (dimeth / Iaiiiiao) propyl7- _c:, 9-dib ydrü _t-3H-aibenzo / ~ b, f7 - ^ - "b ^r" ia2olü ^ ~ 4,3-d7Z ~ '', Ά / αί & ζερίΏ .- 'ί-ΟΏ., 6,1 i-jjiamino-2, 9-dihydro-2- (3-morptiolinopropyl) -3H-aibenzo-

7,11-jji3od-2,9-dahydro-2- / ~ 3- (1-piperidinyl) piopyl7-3H-

s-triazolo £ ~ "4,3-d7 / ~ 1,47diazepin-3-one, ^ · lamino) ätihjl7-5 ~ forfflainido-2,9-dihydro-1o-ine thy 1;) ii-üibenzo / ~" b, f7-s-triazolo £ ~ 4, '') - <$ / ^r £ Ί, 47d.iazepin- ^ 3-one, 2-ethyl-2,9-dihydro-11-3od-3HT

13-i'luor-ii, 9-dih.ydro-2-meth.yl-3H-dibenzo / ~ b, f7-3-triazolo- ^ £ "4,3-d7ZT ¹ » i; 7diazepine-3-un ,
6-bromo-2- / ~ 2- (dimeth.ylaD) ino) ethyl. 7 ~ 2, 9-dih.ydro-3H-dibenzo-

12- (Jhlor-2- _i /~2-(diäthylan!.ino)äth.yl7-2,9-dih.ydro-3H-dibenzo-

2,9-.L) ih.ydro-5-methyl-2-propyl-1 o- (prop ^ ri sulfonyl) -3H-dibenzo- ^ b, f / -s-triazolo _i! £ ~ 4,3-d7Z ~ 1 »47dlazepin-3-one, 2,9-ditiydro-8- (isopropyltb.io) -2- (2-morph.olinoättiyl) -3H-aibenzo _/ / ~ b, f7- s-triazolo _/ / ~ 4> ~ i ~ Ö7 £ ~ ^ »^ diazepin - ^ - on, 12- (xiiättiylaiaino) -8-fluoro-2,9-dib.ydro-2-morph.olinomethyl-5xi-" ibenzo ^ ~ b, f7-s-triazolo / ~ 4,3- ^ 7Z " ¹ » 47diazepin-3-one, 2,9-liihydro-11-propoxy-2,6-dipropyl-3H-dibenzo / ~ b, f7-s-triazolo-Z ~ 4, 3-d / ^r / ~ 1, 47diazepin-3-one,

7- _(ii.th; laulfinyl) -2,9-dihydro-2 / ~ 3- (i-piperiditiyl) propi'l7-3H-dibenzo / b ~, f7-s-triazolo / ~ 4> 3- d7 / ~ 1, ^ d

309831/1192

7,13-Uiätb. / L-2, 9-ditivdro-2- £ 2- (1-κ rrolIdinyl) ethyl7-3H-dibenzo / ~ b, f7-s-triazoloZ ~ 4, S-

1 ».47diazepin-3-one,
6 ,. 12-l) chloro-2,9-bis / ~ (diir ^! Eth.ylaniino) methyl7 - ^> 9-dihydro-3H-dibenzo _i / ~ b, f7-s-triazolo / f ~ 4, 3-d7Z ~ 1 "J: 7i3iazepin-3-one, 5-Βγοβι-9- / ~ 2- (diethj 'laraino) ät hyl7-2- _< / ~'; j« (dipropylamirio) -p-ropyl / -2,9- dihydro-3H-dibenzo / ~ b, f7-s-triazolo / ~ 4,3- ^ 7 / ~ 1> i7aiazepin-3-one,

6,12-jjichlor-2- ^ ~ 3- (dimethylamirio) propyl7dibenzo _i / ~ b, f7-striazolo / ~ 4, 3- ^ 7Z "" ¹ jj7 ^{o ;;} "azepia-3 (2H) -one, 6-chloro-2- / ~ 2- (4-methyl-1-piuera ^ inyl) ethy _i l7c3ibeazo _i / ~ b, f7-striazolo / ~ 4, 3- ^ 7Z ~ 1 »j47 ^ox a2epin-3 (2H) -one, 7-chloro-2-Z ~ 4- (diäth.ylarüino) -2-butin-1-yl7aibenzo ^ ~ b, f7-a-

_} j7oxazepin-3 (2H) -one,

-3- (2-pyridinyl) propyl7dibenzo , 47 ° xazepin - 3 (2H) -one,

5-bromo-12-dipropyiamino-2-dibenzo ^ ~ "b, f7-s-triazoloZ ~ Z ~ 1.47oxaKepin-3 (2H) -one,

8-jungino-13-isopropyl-2-dibeazoZ ~ b, f7-s-triazoloZ ~ 4, 3- aoxazepin-3 (2H) -one,
11-Cyan-2-Z 3-Z ~ 4 - (2-hydroxyätiayl) piperazinyl7propyl7dibenzo-Z ^- b, f7-a-triazolo / "4, 3-J7Z""» i7 ^0X aζepin-3 (2H) - on, 1o-methyl-2-Z ~ ^ -crotyl-1- (piperidinylJ _> 7dibenzoZ ~ b, f7-s-tria-

2-Z ~ 3- (Dii) iethylamino) -2-meth3 ^ 1propyl7-i2-äth.oxy-dibenzo-Z ~ b, f7-s-triazoloZ 4,3 ~ ^ ~ 7Z ^1, 47oxazepin-3 (2H ) -oa,

6,12-Diclilor-2-Z ~ 2- (iriorpholino) ethyl7dibenzoZ ~ byf7i! -S-triazolo-Ζ ~ 4,3- ^ 7ζ. 1.47 "btiiazepin-3 (2H) -one,

7 »11-Oinitro-2-Z ~ 4- (1-iithyl-3-pyrrolidinyl) butyl7dibenzo-

309831/1192

- (1-propyl-4-piperidinjl) prop2 / l7 - "'+' ^ ~ ^ 7Z ~ 1 ι Af ^ hiazeirin -"? (2ti) -one,

-1; j-roeth7lthio-dibonzo £ ~ b, f7-s-triazolo _i / "" 4, 3-d // ~ 1,47-thiazepin-3 (2H) -one,

t hiazepin-3 (2x1) -on,

b, 7-i) i ± "luor-2- _i / ~ 4- (din eth, / lamino) croΐ ^ i7-Qxbenzo / ~ b, f Js ■ fcriszolo / ~ 4,5-7Z ~ 7 ()

, 4 / thiazepin-3 (2H) -one,
7-Ohlor-2- / ~ 2- (4-methyl-1-piperazinyl) eth ^ l7-2,9-dihydro c, f7 ~ s-triaZoIo _- / 4,;> - a7

ⁱ ^ -lamino); propyl7-2,

zo £ _ c, f7-s-triazolo ₍ / ~ 4, 3-a
6-0hlor-2- _/ / "~ 3- (4-ni.et hy 1-1 -pipe razinyl) per pyl / -3H- ^ i benzoic, f7-s-triazolo / ~ 45 3-a7 ^{aze pin-} 3-one, 6-chloro-2- / ~ 2- (dimeter,! Amino) ethyl7-9,9-dinethyl-3H-dibenzo / ~ c, f7-s-triazolo / _ "~ 4> 3-a7ozepine- '3-on,

H,; ! amino) ethyl7 ~ 2, 9-dihydro-3H-dibenzo / ~ b, f7-s-

and the like

the compounds of the -e'ornieln II and III are treated with a pharmacologically permissible acid such as hydrochloric acid, jjromvvasaersιοί acid, phosphoric acid, sulfuric acid, acetic acid, propionic acid, ioluenesulphonic acid, u-haphthalenesulphonic acid, kethanesulphonic acid, << monoic acid, citric acid , lactic acid, malic acid, calic acid or cyclohexanesulfamic acid, the pharmacologically acceptable values of these compounds are obtained. JJiese can x'ür the same Z v ^ tvie the free na be used sen "

309831/1192

- 6ο -

The salt formation takes place in a conventional manner by reacting the "compounds of Formula III" with an excess of the respective acid in a suitable medium such as water, alkanols, ether or acetone and then by evaporating the solvent, preferably in vacuo.
isolated.

3 0 9 8 3 1/119 2

Claims (1)

Claims l'riazolo-azepine of the formula III III wherein ^ oxygen, sulfur reads in which K _n . and S1 denotes hydrogen or alkyl radicals with 1 to 3 carbon atoms, or denotes the nest ^ NH ₁ , in which It denotes hydrogen, an alkyl radical as defined above, one of the radicals H-UnHn-; HOuH ₉ -CH ₉ -N N-OnH n-; 0 N ι H Gnli ₂ n-; N-OnH ₀ : CnH ₂ n- or • 41— OnH, -, η— 3 0 9 8 31/119 in which η is a number from 1 to 4 and R is an alkyl radical according to of the above definition, or one of the residues or -CH ₂ C = CH-N.
8 ' ^R 8 represents in which R ₇ and Rg are hydrogen or alkyl radicals as defined above and η is a number as defined above or / ^ 7 ^R 8 gives a pyrrolidino or piperidino radical, R has the same meaning as R ₁ and R and Ru hydrogen, fluorine, chlorine, bromine, iodine, the amino, nitro or cyano group, an alkyl radical as defined above, trifluoromethyl, an alkoxy, Alkylthio, alkylsulfinyl, alkylsulfonyl or alkanoylamino, the carbon content of which has 1 to 3 carbon atoms, or dialkylamino with alkyl groups as defined above, and their pharmacologically acceptable acid addition salts. 2. 2,9-Dihydro-3H-dibenzo / ^ b, f7-s-triazolo_ / ¥, 3-a7azepin-3-one the formula 3098 31/1192 wherein R ^ and R, - hydrogen atoms or alkyl radicals with 1 to 3 carbon atoms, R _? Hydrogen, an alkyl radical as defined above, one of the radicals CH ₅ -N, N-CnH ₂ n-; HOCH ₂ -CH ₂ -N N-CnH "n-j JnELn-: f - | CnH _o n- CnH ₂ n- in which η is a number from 1 to 4 and R is an Al "..-! remainder according to of the above definition, or one of the residues R ^ - .. 7 R or -CH ₂ = C-CH ₂ N ^{8 R} 8 represents in which R ₇ and Rn are hydrogen or alkyl radicals as defined above and η is a number as defined above, or s ^ n -H gives a pyrrolidino or piperidino radical, and R, and R ^ Hydrogen, fluorine ^ chlorine, bromine, iodine, the amino, nitro or cyano group, an alkyl radical as defined above, trifluoromethyl, an alkoxy, alkylthio, alkylsulfinyl, Alkylsulfonyl or alkanoylamino, its carbon content Has 1 to 3 carbon atoms, or a dialkylamino radical represent with alkyl groups as defined above. 309831/1192 3.2,9 - Dihydro-3H-dlbenzo ₍ / ~ o, f7-s-triazolo / 4, 3-.§ one. 4. 2- / ~ 2- (DimethylaminO) ethyl7-2, 9-difcLydro-3H-ciibenzo / c, f "J / ^, 3-a7azepin-3-one. 5. Hydrochloride of the compound according to iuiopruch 6. 2- / ~ 3- (jjimeii "h ^ lamino) propyl7-2, 9-üih ^ dro-'j $ H-dibenzo /" ~ c , s-triazolo / ~ 4> j-a7 7. 2,9-iJil: iyd.ro-2- / ~ 3 - (4-ineth.yl-1-piperazin _l yl) propyl7-3H-dibenzo / c ^ Zs-triazolo / 4 »3- 7th 8. Dihydrochloride. the connection according to the claim 9 · 7-chloro-2, 9 ~ dihydro-3H-dibenzo / c, f7-s-triazolo / 4 » '3- azepin-3-one. 1o. 7-chloro-2- / ~ 2- (dimethylamino) ether 7-2,9-dihydro-3H-dibenzo / ~ c ^ 7-s-triazolo / ~ "4j3-a / azepin-3-one. 1'1. 2- / ~ 2- (diethylamino) ethyl7-2, 9-dih ^ dro-3Il-Qibenzo / ~ c s-triazolo / 4 »5 ~ £ 7 ^aze Pin ~ 3-one. 12. Llaleat of the connection according to claim 11. 13- 9,9-Din] ethyl-2- / ~ 2- (dimethylaiGino) ethyl 7-2,9-dihj - d.ro-3H dibenzo / c, f7-s-triazolo / ~ 4,3- ^ a ze pin-3-one. 14. 2,9-Dihydro-2- / ~ 2- (i-piperidinyl) ethyl7-3H-dibenzo- / ~ c, f / -s-triazolo / ~ 4,3-a7azepin-3-one hyarochloride 15. ^, 9-Tue
dibenzo / ~ c, f7-s-triazolo / ~ 4,3-a7azepin-3-one hydrochloride. 309831/1192 16. 2, yL>ih; ydro-2- ₍ / _ 2- > 3-a7azepin-3-one. "c, f7- 17 · Hydro chloride of the compound according to claim 16. 18. 6-Chloro-2,9-dihydro-3H-dibenzo / ~ c, f7-s-triazolo ^ ~ 4,3-a azepin-3-one. 19. 6-chloro-2- / ~ 2- (dimethylamino) ethy3-7-2,9-dihydro-3H-di- 20. 2- / ~ 2- (iiinino) ethyl7-2,9-dihydro-3H-dibenzo ^ ~ c, f7-striazolo ₍ / ~ 4,3-a7azepin-13-naphthalenic acid salt. 21 2- / 2- ~ (3enzylmethylamino) ä "thy_l7-2,9-dih _ydro-1 3H-dibenzo 4 »3- ^ 7azepin-3-one hydrochloride. 22. 6-chloro-2,9-aihydro-2- ^ f "3- (dimethylamino) propyl7-3H-aibenzo ^ c, f7-s-triazolo ₍ / ~ 4,3-a7azepin-3-one oxalate. 23. 2,9-2iiaydro-2- / ~ 2- (4-methyl-1-piperazinyl) ethyl7-3H-aibenzo ^ c, f7 ~ s-triazolo ^ / ~ 4, 3-a7azepin-3-one dihydrochloride. 24 · 2,9-l3ih diazepin-3-one of Jj'omel 309831/1192 230 $ 139., wherein R _{1 is} hydrogen, an alkyl radical as defined above, one of the radicals CH ₃ -N. , N-CnHgn-; N-CnH η-; j -L-CnHpn-; j 4 — CnH ₂ n- or t I R R CnH ~ n- in which η is a number from 1 to 4 and R is an alkyl radical according to of the above definition, or one of the residues ^R 7 / - ^R 7 -CnH _o nN or -CH ₀ C = CH ₀ N 2 \ 2 2 ^R 8 ^R 8 represents, wherein RyUnd Rg is hydrogen or alkyl radicals according to above definition and η denote a number as defined above, or R -N- gives a pyrrolidino or piperidino radical, R the 2 has the same meaning as R> and R, and R ₁ , hydrogen, fluorine, chlorine, bromine, iodine, the amino, nitro or cyano group, an alkyl radical as defined above, trifluoromethyl, an alkoxy, alkylthio, alkylsulfinyl , Alkylsulfpny} - or alkanoylamino radical, the carbon content of which has 1 to 3 carbon atoms, or dialkylamino radical with alkyl groups as defined above. 25. 2,9-Dihydro-3H-dibenzo _j / F, f7-s-triazolo _: / ⁱ r, 3-d_7 / ^ T, £ 7-diazepin-3-one. 3Q9831 / 1192 26. 2 - / _ 2- (Dimeth ^ lamino) ethyl7-2,9-dihydro-31i-dibenzo _/ / 27.2 / 3 28. 7-Chior-2- £ 2- (aimeth7lainino) eth _t yl / -2, 9-dihydro-3H-dibenzo- 29 2, 9-3jih 4-met h7l-1 -piperazineI) propyl / -5H- 3o. Hydrochloride of the compound according to claim 29 31. 9- / ~ 3- ~ ² »9 ~ dihydro-5ti-diüenzo- 32.2, 9-Mhy £ ~ 1.47 "diazepin-3-one ι 4 / * diazepin-3-one. 34 · Hjrdrochiorid the connection Gewäia claim 33 · , _47oxazepine-3 (2ü) - 35 · Ui £ ont of the formula 309831/1192 where FL hydrogen, an alkyl radical as defined above, one of the leftovers N-CnH η; HOC-CN N-CnH ^ n-; ^d HH \ / ^{d ΓΛ} N-CnH "~ .1 H-CnHn- ί ^ Χ- CnH ^ n- or T t R R in which η is a number from 1 to 4 and R is an alkyl radical according to of the above definition, or one of the residues . . or -CH ₀ C = C-CH ₀ N ^ R ₈ ^R 8 represents in which R "and R _{ft are} hydrogen or alkyl radicals as defined above and η is a number as defined above, or ^R 8 gives a pyrrolidino or piperidino radical, and R, and R ₁ hydrogen, fluorine, chlorine, bromine, iodine, the amino, nitro or cyano group, an alkyl radical as defined above, trifluoromethyl, an alkoxy, alkylthio, alkylsulfinyl, Alkylsulfonyl or alkanoylamino, the carbon content of which is 1 to 3 carbon atoms on v / e, or dialkylamino with alkyl groups as defined above. 36. 6-chloro-dibenzo_ / F, £ 7-s-triazolo_ / T, 3 ~ d7 / T, 47oxazepin-3 (2H) -one. 309831/1192 37 "Dibenzo / b, f7-s ^ triazolo / ~ 4j 3-.d7 / ~ * 1 ₅ 47o ^x azepine -;> (2H) -one 33.. H- / ~ 2 - (]) i7
¹ , 47oxazepine ~ .5 (2ii) -one. 39. 6-chloro-2- / ~ 2- (dimethylamirio) ethyl7-dibenzo / ~ ^b > f7-s , 4 / oxazepin-3 (2H) -one. 4o. 7-chloro-2- £ ~ 2- (dimethylamino) ethyl7-aibenzo ₍ / ~ b, f7-s triazolo _i / ~ "4, i ~ ^ 41.7-0 4,3-d7 £ ~ 1.47 " ^ox azepin-3 (2K) -on-h.ydrocb.lorid. 42. 2- _/ / ~ 3- (dimethylamino) prop / 17dibenzo / ~ b, f7-s-triazolo / ^ ~ 4,3-d7 / ""i> 47 oxazepin-3 (2H) -one hydrochloride . 43. jJibenzo _i / ~ b, f7-s - t; riazolo / _ "~ 4-> 3- ^ 7Z" i, 47thiazepin-3 (2H) -one of the formula where R ^ hydrogen, an alkyl radical as defined above, one of the iieste 309831/1192 H H .-N N-CnH η-; HOC-CN N-CnH _o n-; 0 ^JK ' ^ά HH' ^ Cx- . . CnH _p n- or I 44, CnH ^ n- B ^R in which η is a number from 1 to 4 and R is an alkyl radical is according to the above definition, or one of the residues -CnH ₂ nN or -CH ₂ -C = C-CH ₅ - ^ ^R 8 ^XR 8 represents in which R ₇ and Rg are hydrogen or alkyl radicals according to the above definition and η is a 2 & hl according to the above definition or H R ₈ gives a pyrrolidino or piperidino radical, and R_ and Rj. Hydrogen, fluorine, chlorine, bromine, iodine, the amino, nitro or cyano group, an alkyl radical as defined above, Trifluoromethyl, an alkoxy, alkylthio, alkylsulfinyl, Alkylsulfonyl or alkanoylamino, its carbon content Has 1 to 3 carbon atoms, or dialkylamino radical with alkyl groups as defined above, and their pharmacologically acceptable acid addition salts. kh, dibenzo / b, f7s-triazolo / _ ¥, 3-d7 / T, ^ 7thiazepin-3 (2H) -one. 45, 2 - / _ '2- (dimethylamino) ethyl7- ^d i ^b enzo / _b, f7-s-triazolo - / _ ¥, 3-d7yT, _47thiazepin-3- (2H) -one hydrochloride. 6.7-Chloro-2-_ / '2- (dimethylamino) ethyl7dibenzo £ F _i f7 "' S-triazolo - / _ ?, 3-d7 / T, J [7thiazepin-3 (2H) -one. 3 Q 9 8 3 1/1 1 9 2 kj . 7-chloro-2- ^ 3 ^ (dimethylamino) propyl / dibenzo / b, f _ / - stria2olo / T ₉ 3-d7 / T, i | 7thiazepin-3 (2H) -one. k8. Dibenzo / F, f7-s-triazoloA, 3-d7 / T, 47-thiazepine-3 (2H) -one-9,9-dioxide of the formula where R _? Hydrogen, an alkyl radical as defined above, one of the radicals CH ₃ - N-CnH ₂ n-; -CnH ₂ n; CnH ₂ n- or CnH ₂ n- in which η is a number from 1 to 4 and R is an alkyl radical according to of the above definition, or one of the residues ^l 7 / ^R 7 -CnH ₂ nN or -CH ₂ -C = C- represents in which R ₇ and R «are hydrogen or alkyl radicals as defined above and η is a number as defined above mean or s " 7 -N 309831/1192 301399 gives a pyrrolidino or piperidino radical, and IL, and H, Hydrogen, fluorine, chlorine, bromine, iodine, the amino, nitro or cyano group, an alic group according to the above definition, 'jjrifluormethyl, an alkoxy-, alkylthio-, a1 ± q isulfynyl-, Alkylsulfonyl or alkanovlamino, its carbon content Has 1 to 3 carbon atoms, or a liialkylamino radical represent with alkyl groups as defined above, and their pharmacologically permissible oleic acid addition salts. 49 · 9, 9-dioxo-2 _/ / ~ 2- (dimethylamino) eth ^ l7-dibenzo / b ~, f7-s- '4' 3-.d 5o. Process for the preparation of I'riazoloazepinen der Formula III where X is oxygen, sulfur, which reads ^ ^u - ^. ./ XLg in which it, - and Rr denote hydrogen or alkyl radicals with 1 to carbon atoms, or the xtest ¹ ^ ¹ H-Ii ₁ denotes in which. E _{1 is} hydrogen, an alkyl radical as defined above, one of the radicals r ~ \ N-GoH ₉ QJ HOC-C-NH ^d HH I. IN THE l · I ~ ^mL 2 ⁿ >
N I. I. E. R. 309831/1192 or j fj CnH ₂ n- in which η is a number from 1 to H and R is an alkyl radical as defined above, or one of the radicals R. or -CH ₂ -C = C-CH ₂ N ^l 8 represents in which R ₇ and R «are hydrogen or alkyl radicals as defined above and η is a number as defined above, or _R -n gives a pyrrolidino or piperidino radical, R_ the same Has meaning like R. and R and R ^ hydrogen, fluorine, Chlorine, bromine, iodine, the amino, nitro or cyano group, an alkyl radical according to the other definition, trifluoromethyl or a Alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or alkanoylamino, the carbon content of which is 1 to 3 carbon atoms or represent dialkylamino radicals with alkyl groups according to the above definition, characterized in that that a compound of the formula I 309831/1192 in .welcher X, H ₇ and K have the above meaning, with a Hydrazlnokohl "nsäurealkylester the jj'orrael whose alkyl radical has 1 to 3 carbon atoms, converts to form the corresponding compound of Ji ¹ and. the compound II in the presence of a base with an alkylating agent of the formula HpCl, R _? Br or R "J, where Rp has the above meaning, treated to form a compound of formula III. 51. The method according to claim 5o, characterized in that the hydrazinokohlensäureäth, yl ester is used. 52. The method according to claim 5o, characterized in that the starting material used is I 6 (5H) -liorphanthridinethione and the 2,9-dihydro-3H-dibenzo _i / ~ c, f7-s-triazolo ^ 4 as the product of the first otufe , 3-a7azepin-3-one receives. 309831/1192 53 · Method according to claim 5o, characterized in that one the product 2,; - Dih ^ dro-'JH-dibenzo ^ / fcjfJ-s-triazolo- ^ ~ 4 »3-a7azepin-3-one in 'cregenv.art of a base with 2- (dim ethyl-LBiino) ethyl chloride, 3- (Die-thylamino) propyl chloride or 1- (3-Ohlornropvl) -4-üethwlpiperazin treated. 54 · The method according to claim 5o, characterized in that The starting material is 5,1o ~ hydro-11Ii-dibenzo / f ~ b, e7Z ~ 1,47 "-diazepine-11-thione used and correspondingly in the first step the 2, y-; dihydro-5H-dibenzo / _ * ~ b, f7-s-triazolo / ~ 4,3-d7- / ~ 1,47 <3iazei) in-3- on receives. 55 · The method according to claim 5o, characterized in that the product 2, b ⁾ -Dih.ydro-3ii-dibenzo / ~ b, f7-s-tri ^: *, olo ^ f ~ 4, 3 ~ d / - £ ~ - \ , 4 / 'diazepin-3-one treated in the presence of a base with 2- ^ dimethylamino) -eth; yl chloride, 3- (diethylamino) propyl chloride or 1- (3-fluoropropyl) -4-methpiperazine. For: ihe Upjohn (Jompany Kalamazoo, kich., V'.öt.A. Lawyer 309831/1192