Compounds of the formula IV ##STR1## wherein R is hydrogen or alkyl of 1 or 2 carbon atoms; wherein R.sub.1 is alkyl of 1 to 3 carbon atoms, inclusive; or ##STR2## is a 2-cycloalkenylene ring of 5 or 6 carbon atoms; wherein R.sub.2 is hydrogen, methyl or ethyl; wherein R.sub.3 is hydrogen, fluoro, chloro, bromo, nitro and --CF.sub.3 ; and wherein Ar is phenyl, o-chlorophenyl, o-fluorophenyl, 2,6-difluorophenyl, and 2-pyridyl, are prepared by treating a hydrazino compound of the formula: ##STR3## wherein Ar and R.sub.3 are defined as above, with a dicarbonyl compound II: ##STR4## and cyclizing the resulting compound III to give the compound IV above. Compound IV, including the pharmacologically acceptable acid addition salt of these compounds, have sedative, anxiolytic and muscle-relaxing activity and can be used for the treatment of anxieties or muscle strains of mammals, including man.

BACKGROUND OF THE INVENTION 
Field of the Invention 
This invention is directed to new organic compounds and is particularly 
concerned with as-triazinobenzodiazepines of formula IV, intermediates 
thereto of formula III, and the process therefor. 
The novel compounds and process of production therefor can be 
illustratively represented as follows: 
##STR5## 
wherein R is hydrogen or alkyl of 1 to 2 carbon atoms, inclusive; wherein 
R.sub.1 is alkyl of 1 to 3 carbon atoms, inclusive, or the group 
##STR6## 
is a 2-cycloalkylene ring of 5 or 6 carbon atoms and the group 
##STR7## 
is 2-oxocyclopentylidene or 2-oxocyclohexylidene; wherein R.sub.2 is 
hydrogen, methyl or ethyl; wherein R.sub.3 is hydrogen, fluoro, chloro, 
nitro and --CF.sub.3 ; and wherein Ar is phenyl, o-chlorophenyl, 
o-fluorophenyl, 2,6-difluorophenyl, and 2-pyridyl. 
The process of this invention comprises: treating a hydrazino compound of 
formula I with a dicarbonyl reagent of formula II to obtain the 
corresponding compound of formula III; and treating compound III with a 
cyclizing reagent to obtain the corresponding compound of formula IV. 
The invention claims the compounds of formula IV and the pharmacologically 
acceptable acid addition salts thereof, the intermediates of formula III, 
and the process to make these compounds. 
DESCRIPTION OF THE PREFERRED EMBODIMENT 
Alkyl groups of 1 to 3 carbon atoms, inclusive, are exemplifid by methyl, 
ethyl and propyl. 
The more preferred compounds of this invention are of the formulae IIIA and 
IVA: 
##STR8## 
wherein R' is hydrogen or methyl, R.sub.1 ' is methyl or ethyl; wherein 
R.sub.3 ' is fluoro, chloro, bromo, or trifluoromethyl; and wherein Ar is 
phenyl, o-chlorophenyl, o-fluorophenyl, 2,6-difluorophenyl or 2-pyridyl, 
and the pharmacologically acceptable acid addition salts of compound IVA. 
The most preferred compounds of this invention are of the formula 111B and 
IVB: 
##STR9## 
wherein R.sub.1 ' is methyl or ethyl; wherein R' is hydrogen or methyl; 
wherein R.sub.3 " is fluoro, chloro or trifluoromethyl; and wherein 
R.sub.4 is hydrogen, chloro or fluoro, and the pharmacologically 
acceptable acid addition salts of compound IVB. 
Compounds of formula IV (including IVA and IVB) are sedative, 
tranquilizing, anxiolytic, muscle-relaxing and anti-convulsive agents 
which are useful for treating anxieties, convulsions or strained muscles 
in mammals, including man. 
The sedative-tranquilizing-anxiolytic activity was evaluated in compounds 
of formula IV by the following test: 
Gamma Butyrolactone Sleep Potentiation 
Gamma-butyrolactone produces loss of righting in mice at doses higher than 
400 mg./kg. intraperitoneally. At lower doses (200 mg./kg.) the mice do 
not lose their righting reflex unless previously treated with sub-hypnotic 
doses of central nervous system depressant agents. This then provides a 
technique to study the depressant activity of potential central nervous 
system agents. Method: The test compound is injected intraperitoneally 50 
mg./kg. into a group of four mice and 30 minutes later gamma-butyrolactone 
is injected intraperitoneally, 200 mg./kg. (normally a sub-hypnotic dose). 
After 10 minutes, the mice are tested for loss of righting reflex. If more 
than two mice show a loss of righting for 1 minute or more, the compound 
is retested at multiple dose levels. 
Anti-convulsion Test: 
Protection Against Bicucullin-Induced Tonic Extensor Convulsions 
In this procedure, groups of four Carworth Farms male mice, weighing 18-22 
g. each, are injected intraperitoneally with the test agent prepared in 
0.25% methylcellulose. Thirty minutes later, bicucullin in injected 
intravenously at 1 mg./kg. Bicucullin is solubilized in 1N hydrochloric 
acid and diluted to a concentration of 1-4 mg./ml. with physiological 
saline and adjusted to a final pH of 5-6 before injection. Mice are 
observed for 5 minutes after bicucullin injection. A compound is 
considered to be active if it protects at least 2 of the four mice from 
tonic extensor convulsions during this period. Active compounds are 
retested using multiple dose levels decreasing at 0.3 or 0.5 log intervals 
and the number of mice failing to convulse is used as a quantal response 
to calculate the ED.sub.50 (Spearman and Karber: Finney, D. J., 
Statistical Method in Biological Assay, Hafner Publ. Co., N.Y., p. 524, 
1952). This procedure is a useful test for detecting compounds with minor 
tranquilizer or sedative activity. 
Anti-convulsant, Muscular Relaxing Activity by the Pentylene-tetrazol 
(Metrazol) Test 
Metrazol Induced Convulsion Test: 
The test compound is injected intraperitoneally (50 mg./kg.) into groups of 
four mice at multiple dose levels decreasing in 0.3 log intervals. Thirty 
minutes later Metrazol is injected subcutaneously (at the nape of the 
neck), 85 mg./kg. Fifteen minutes later a set of keys is rattled over the 
cage to induce the clonic convulsions. The number of mice protected 
against convulsions and death is recorded. 
The compounds IV of this invention have positive results in these tests. 
Thus, these compounds are useful for tranquilization, sedation, treating 
anxieties, and also useful as anti-convulsants and muscle-relaxants in 
mammals and birds. 
The pharmaceutical forms contemplated by this invention include 
pharmaceutical compositions suited for oral, parenteral, and rectal use, 
e.g., tablets, powder packets, cachets, dragees, capsules, solutions, 
suspensions, sterile injectable forms, suppositories, bougies, and the 
like. Suitable diluents or carriers such as carbohydrates (lactose), 
proteins, lipids, calcium phosphate, corn starch, stearic acid, 
methylcellulose and the like may be used as carriers or for coating 
purposes. Water or oil, e.g., coconut oil, sesame oil, safflower oil, 
cottonseed oil, peanut oil may be used for preparing solutions or 
suspensions of the active drug. Sweetening, coloring and flavoring agents 
may be added. 
For mammals and birds, food premixes with starch, oatmeal, dried fishmeat, 
fishmeal, flour and the like can be prepared. 
The compounds of formulae III and IV can be used in dosages of 0.05-2 
mg./kg./day; preferably in unit dosages of 0.1-1.0 mg./kg./day in oral or 
injectable preparations as described above, to alleviate tension and 
anxiety, muscle spasm or convulsions in mammals, including man, or birds. 
The starting materials of formula I of this invention, with a 5-phenyl- or 
substituted phenyl groups, are known in the art, e.g., from Canadian Pat. 
No. 908,657. 
The compounds of formula I which have a 2-pyridyl group in the 5-position 
can be made from the corresponding 2-thiones according to U.S. Pat. No. 
3,996,230. 
In carrying out the process of this invention, a compound of formula I is 
treated with a selected vicinal dione compound II such as 2,3-butanedione, 
2,3-pentanedione, 2,3-hexanedione, or 1,2-cyclohexanedione, 
1,2-cyclopentanedione or the like, in an inert organic solvent, e.g., 
tetrahydrofuran, dioxane, diethylether, dipropylether, methanol, ethanol, 
toluene, benzene, cyclohexane, methylene chloride or the like. The 
reaction is carried out at a temperature between -10.degree. and 
100.degree. C., preferably between 0.degree. and 70.degree. C., and 
preferably in a nitrogen atmosphere. 
After the reaction is terminated, the compound III thus synthesized is 
isolated and purified by conventional procedures, e.g., evaporation, 
washings, extractions, chromatography, and the like. 
Compound III is then cyclized with a cyclizing reagent such as concentrated 
sulfuric acid, polyphosphoric acid, phosphorus pentoxide and 
methanesulfonic acid, or anhydrous liquid hydrogen fluoride, with 
anhydrous liquid hydrogen fluoride preferred. The temperature for this 
reaction depends on the reagent used, -10.degree. to 10.degree. C. for 
sulfuric acid and polyphosphoric acid, and -80.degree. to 30.degree. C., 
if anhydrous liquid hydrogen fluoride is used. In the preferred 
embodiment, a nitrogen atmosphere is used and the reaction mixture 
compound III and liquid hydrogen fluoride are allowed to warm up from 
about -80.degree. C. to room temperature in a hood overnight. 
The resulting product compound IV is recovered by neutralizing the mixture 
with aqueous sodium bicarbonate or other alkali, and extracting with an 
organic solvent, followed by conventional methods of purification, e.g., 
chromatography and crystallizations.

The following Preparation and Examples are illustrative of the process and 
the compounds of the present invention, but are not to be construed to be 
limiting. 
In the manner given in Canadian Pat. No. 908,657, U.S. Pat. No. 3,996,230 
or U.S. Pat. No. 3,734,922, 
1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazepines can be 
prepared. Representative compounds, that can be thus prepared, include: 
7-chloro-1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazepine, 
7-fluoro-1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazepine, 
7-nitro-1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazepine, 
8-bromo-1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazepine, 
8-fluoro-1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazepine, 
8-chloro-1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazepine, 
9-trifluoromethyl-1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazep 
ine, 9-bromo-1,3-dihydro-2-hydrazino-5-(pyridyl)-2H-1,4-benzodiazepine, 
8-nitro-1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazepine, 
9-nitro-1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazepine, 
7-trifluoromethyl-1,3-dihydro-2-hydrazino-5-(2-pyridyl)-2H-1,4-benzodiazep 
ine, and the like. 
EXAMPLE 1 
9-Chloro-1,5-dihydro-2-methyl-1-methylene-7-phenyl-as-triazino 4,3-a! 1,4!b 
enzodiazepine 
(A) (7-Chloro-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazone of 
2,3-butanedione 
A solution of 14.24 g. (0.05 mole) of 
7-chloro-2-hydrazino-5-phenyl-3H-1,4-benzodiazepine in 200 ml. of 
tetrahydrofuran (under nitrogen) was cooled to 0.degree. C. and a solution 
of 5.16 g. (0.06 mole) of 2,3-butanedione in 100 ml. of tetrahydrofuran 
was added with stirring. After 3 hours, the solution was evaporated in 
vacuo giving (7-chloro-5-phenyl-3H-1,4benzodiazepin-2-yl)monohydrazone of 
2,3-butanedione as a light yellow noncrystalline solid. 
(B) 
9-Chloro-1,5-dihydro-2-methyl-1-methylene-7-phenyl-as-triazino 4,3-a! 1,4! 
benzodiazepine 
A 5.5 g. (0.017 mole) portion of the above hydrazone was added, under 
nitrogen, to 20 ml. of liquid hydrogen fluoride at -80.degree. C. and the 
solution was allowed to warm to room temperature and evaporate overnight 
in the hood. The residue was mixed with aqueous sodium bicarbonate, 
extracted with methylene chloride, washed with water, dried over sodium 
sulfate and evaporated in vacuo. The residue was chromatographed on silica 
gel, eluting with a solution consisting of 60% hexane, 35% methylene 
chloride and 5% 2-propanol (by volume). The product was crystallized from 
ethyl acetate-hexane yielding 2.04 g. (37%) of light yellow solid of 
melting point 190.degree.-196.degree. C. (dec.). A sample for analysis was 
recrystallized from methylene chloride-ethyl acetate, to give 
9-chloro-1,5-dihydro-2-methyl-1-methylene-7-phenyl-as-triazino 4,3-a! 1,4! 
benzodiazepine of melting point 194.degree.-196.degree. C. 
Anal. Calcd. for C.sub.19 H.sub.15 ClN.sub.4 : C, 68.16; H, 4.52; Cl, 
10.59; N, 16.74. Found: C, 67.99; H, 4.71; Cl, 10.69; N, 16.78. 
EXAMPLE 2 
9-Chloro-1,5-dihydro-2-ethyl-1-methylene-7-phenyl-as-triazino 4,3-a! 1,4!be 
nzodiazepine (A) and 
9-Chloro-1,5-dihydro-1-ethylidene-2-methyl-7-phenyl-as-triazino 4,3-a! 1,4 
!benzodiazepine (B) 
In the manner given in Example 1, 2.84 g. (0.01 mole) of 
7-chloro-2-hydrazino-5-phenyl-3H-1,4-benzodiazepine was condensed with 
2,3-pentanedione in tetrahydrofuran. After evaporation, the residue was 
dissolved in methylene chloride, washed with water, dried over anhydrous 
sodium sulfate, evaporated and chromatographed on silica gel, eluting with 
hexane 70%: CH.sub.2 Cl.sub.2 25%:i-PrOH/5%. The product was an oil whose 
NMR (nuclear magnetic resonance) was consistent with that of a mixture of 
the two mono hydrazones, probably each in syn and anti forms. The yield 
was about 90%. This oil was added to liquid hydrogen fluoride at 
-80.degree. C., allowed to evaporate overnight. Chromatography yielded two 
cyclized products, A and B, which were identified by NMR. Product A 
crystallized from ethyl-hexene giving 0.44 g. (11%) of yellow crystals 
which were found by melt solvate to contain 14% solvent. It had a melting 
point 104.degree.-117.degree. C. (dec.). Recrystallization from methylene 
chloride-ether gave an unsolvated product, namely 
9-chloro-1,5-dihydro-2-ethyl-1-methylene-7-phenyl-as-triazino 4,3-a! 1,4!b 
enzodiazepine, identified by NMR (nuclear magnetic resonance spectrum) of 
melting point 155.degree.-163.degree. C. (dec.). 
Product A 
Anal. Calcd. for C.sub.20 H.sub.17 ClN.sub.4 : C, 68.86; H, 4.91; Cl, 
10.16; N, 16.06. Found: C, 68.59; H, 4.88; Cl, 10.15; N, 16.01. 
Product B from the column, 
9-chloro-1,5-dihydro-1-ethylidene-2-methyl-7-phenyl-as-triazino 4,3-a! 1,4 
!-benzodiazepine, was crystallized from ethyl acetatehexane giving 0.16 g. 
(4.6%) of yellow crystals of melting point 180.degree.-193.degree. C. 
(dec.). Identification of this product was obtained by NMR and IR 
(infrared spectrum). 
Product B 
Anal. Calcd. for C.sub.20 H.sub.17 ClN.sub.4 : C, 68.86; H, 4.91; Cl, 
10.16; N, 16.06. Found: C, 68.73; H, 4.86; Cl, 10.34; N, 16.07. 
EXAMPLE 3 
11-Chloro-1,2,3,6-tetrahydro-9phenyl 1,2,4!benzo-triazino 4,3-a! 1,4!benzod 
iazepine 
(A) (7-Chloro-5-phenyl-3H-1,4-benzodiazepin-2-yl)monohydrazone of 
1,2-cyclohexanedione 
To a solution of 6.59 g. (0.02 mole) of 
7-chloro-2-hydrazino-5-phenyl-3H-1,4-benzodiazepine in 75 ml. of 
tetrahydrofuran, under nitrogen, was slowly added with stirring 2.24 g. 
(0.02 mole) of 1,2-cyclohexanedione. After refluxing for 4 hours, the 
solution was evaporated in vacuo, dissolved in methylene chloride, washed 
with water and dried over anhydrous sodium sulfate. Filtration and 
evaporation in vacuo gave 
(7-chloro-5-phenyl-3H-1,4-benzodiazepin-2-yl)monohydrazone of 
1,2-cyclohexanedione. 
(B) 
11-Chloro-1,2,3,6-tetrahydro-9-phenyl 1,2,4!-benzotriazino 4,3-a! 1,4!benz 
odiazepine 
This hydrazone of Example 3A was added to 20 ml. of liquid hydrogen 
fluoride at -80.degree. C., and the solution was allowed to evaporate 
overnight in the hood. The residue was mixed with ice and sodium 
bicarbonate and extracted with methylene chloride. After evaporation in 
vacuo, the residue was chromatographed on silica gel eluting with 
chloroform containing 2% methanol. The product crystallized from ethyl 
acetate yielding 0.52 g. (7%) of yellow 
11-chloro-1,2,3,6-tetrahydro-9-phenyl 1,2,4!benzotriazino 4,3-a! 1,4!benzo 
diazepine of melting point 180.degree.-182.degree. C. (after softening at 
130.degree. C.). A sample for analysis, ecrystallized from methylene 
chloride-ethyl acetate, had the same melting point. This was shown by nmr 
to be an ethyl acetate solvate. 
Anal. Calcd. for C.sub.21 H.sub.17 ClN.sub.4.1/2 C.sub.4 H.sub.8 O.sub.2 
(ethyl acetate): C, 68.23; H, 5.23; Cl, 8.76; N, 13.84; C.sub.4 H.sub.8 
O.sub.2, 10.88. Found: C, 67.94; H, 5.15; Cl, 8.90; N, 13.86; C.sub.4 
H.sub.8 O.sub.2 (by melt solvate), 11.13. 
EXAMPLE 4 
9-Chloro-1,5-dihydro-2-methyl-1-methylene-7 
-(o-chlorophenyl)-as-triazino 4,3-a! 1,4!-benzodiazepine 
(A) 7-Chloro-5-(o-chlorophenyl)-3H-1,4-benzo-diazepin-4-yl!monohydrazone 
of 2,3-butane-dione 
In the manner given in Example 1A, 
2-hydrazino-5-(o-chlorophenyl)-3H-1,4-benzodiazepine can be reacted with 
2,3-butanedione to give 
7-chloro-5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl! monohydrazone of 
2,3-butanedione. 
(B) 
9-Chloro-1,5-dihydro-2-methyl-1-methylene-7-(o-chlorophenyl)-as-triazino 4 
,3-a! 1,4!-benzodiazepine 
In the manner given in Example 1B, 
7-chloro-5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-butanedione can be cyclized in liquid hydrogen fluoride to give 
9-chloro-1,5-dihydro-3-methyl-1-methylene-7-(o-chlorophenyl)-as-triazino 4 
,3-a! 1,4!benzodiazepine. 
EXAMPLE 5 
9-Chloro-1,5-dihydro-2-ethyl-1-methylene-7-(o-fluorophenyl)-as-triazino 4,3 
-a! 1,4!-benzodiazepine and 
9-chloro-1,5-dihydro-1-ethylidene-2-methyl-7-(o-fluorophenyl)-as-triazino 
4,3-a! 1,4!benzodiazepine 
(A) 7-Chloro-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-pentanedione 
In the manner given in Example 1A, 7-chloro-2 
-hydrazino-5-(o-fluorophenyl)-3H-1,4-benzodiazepine can be reacted with 
2,3-pentanedione to give a mixture of the isomeric 
7-chloro-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazones of 
2,3-pentanedione. 
(B) 
9-Chloro-1,5-dihydro-2-ethyl-1-methylene-7-(o-fluorophenyl)-as-triazino 4, 
3-a! 1,4!benzodiazepine and 
9-chloro-1,5-dihydro-1,ethylidene-2-methyl-7-(o-fluorophenyl)-as-triazino 
4,3-a! 1,4!benzodiazepine 
In the manner given in Example 2B, the above mixture of monohydrazones of 
2,3-pentanedione can be cyclized in liquid hydrogen fluoride to give 
9-chloro-1,5-dihydro-2-ethyl-1-methylene-7-(o-fluorophenyl)-as-triazino 4, 
3-a! 1,4!benzodiazepine and 
9-chloro-1,5-dihydro-1-ethylidene-2-methyl-7-(o-fluorophenyl)-as-triazino 
4,3-a! 1,4!benzodiazepine. 
EXAMPLE 6 
9-Bromo-1,3-dihydro-2,5-dimethyl-1-methylene-7-(2-pyridyl)-as-triazino 
4,3-a! 1,4!-benzodiazepine 
(A) 7-Bromo-3-methyl-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone 
of 2,3-butanedione 
In the manner given in Example 1A, 
7-bromo-2-hydrazino-3-methyl-5-(2-pyridyl)-3H-1,4-benzodiazepine can be 
reacted with 2,3-butanedione to give 
7-bromo-3-methyl-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-butanedione. 
(B) 
9-Bromo-1,5-dihydro-2,5-dimethyl-1-methylene-7-(2-pyridyl)-as-triazino 4,3 
-a! 1,4!benzodiazepine 
In the manner given in Example 1B, 
7-bromo-3-methyl-5-(2-pyridyl)-3H-1,4benzodiazpine-4-yl!monohydrazone of 
2,3-butanedione can be cyclized in liquid hydrogen fluoride to give 
9-bromo-1,5-dihydro-2,5-dimethyl-1-methylene-7-(2-pyridyl)-as-triazino 4,3 
-a!- 1,4!benzodiazepine 
EXAMPLE 7 
1,5-Dihydro-2-methyl-1-methylene-7-(o-chlorophenyl)-as-triazino 4,3-a! 1,4! 
-benzodiazepine 
(A) 5-(o-Chlorophenyl)-3H-1,4benzodiazepine-4-yl!monohydrazone of 
2,3-butanedione 
In the manner given in Example 1A, 
2-hydrazino-5-(o-chlorophenyl)-3H-1,4-benzodiazepine can be reacted with 
2,3-butanedione to give 
5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-butanedione. 
(B) 
1,5-Dihydro-2-methyl-1-methylene-7-(o-chlorophenyl)-as-triazino 4,3-a! 1,4 
!benzodiazepine 
In the manner given in Example 1B, 
5-(o-chlorophenyl)-3H-1,4benzodiazepin-4-yl!monohydrazone of 
2,3-butanedione can be cyclized in liquid hydrogen fluoride to give 
1,5-dihydro-2-methyl-1-methylene-7-(o-chlorophenyl)-as-triazino- 4,3-a! 1, 
4!benzodiazepine. 
EXAMPLE 8 
9-Trifluoromethyl-1,5-dihydro-2-methyl-1-methylene-7-phenyl-as-triazino 4,3 
-a! 1,4!benzodiazepine 
(A) (7-Trifluoromethyl-5-phenyl-3H-1,4-benzodiazepine-4-yl)monohydrazone of 
2,3-butanedione 
In the manner given in Example 1A, 
7-trifluoromethyl-2-hydrazino-5-phenyl-3H-1,4-benzodiazepine can be 
reacted with 2,3-butanedione to give 
(7-trifluoromethyl-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazone of 
2,3-butanedione. 
(B) 
9-Trifluoromethyl-1,5-dihydro-2-methyl-1-methylene-7-phenyl-as-triazino 4, 
3-.alpha.! 1,4!-benzodiazepine 
In the manner given in Example 1 B, 
(7-trifluoromethyl-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazone of 
2,3-butanedione can be cyclized in liquid hydrogen fluoride to give 
9-trifluoromethyl-1,5-dilhydro-2-methyl-1-methylene-7-phenyl-as-triazino 4 
,3-a!- 1,4!benzodiazepine. 
EXAMPLE 9 
9-Nitro-1,5-dihydro-2-methyl-1-methylene-7-(o-chlorophenyl)-as-triazino 4,3 
-a!- 1,4!-benzodiazepine 
(A) 7-Nitro-5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-butanedione. 
In the manner given in Example 1A, 
9-nitro-2-hydrazino-5-(o-chlorophenyl)-3H-1,4-benzodiazepine can be 
reacted with 2,3-butanedione to give 
7-nitro-5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3- butanedine. 
(B) 
9-Nitro-1,5-dihydro-2-methyl-1-methylene-7-(o-chlorophenyl)-as-triazino 4, 
3-a! 1,4!benzodiazepine 
In the manner given in Example 1B, 
7-nitro-5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-butanedione can be cyclized in liquid hydrogen fluoride to give 
9-nitro-1,5-dihydro-2-methyl-1-methylene-7-(o-chlorophenyl)-as-triazino 4, 
3-a! 1,4!-benzodiazepine. 
EXAMPLE 10 
9-Chloro-1,5-dihydro-2-methyl-1-methylene-7-(2,6-difluorophenyl)-as-triazin 
o 4,3-a!- 1,4!benzodiazepine 
(A) 7-Chloro-5-(2,6-difluorohenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone 
of 2,3-butanedione. 
In the manner given in Example 1A, 
7-chloro-2-hydrazino-5-(2,6-difluorophenyl)-3H-1,4-benzodiazepine can be 
reacted with 2,3-butanedione to give 
7-chloro-5-(2,6-difluorophenyl)-3H1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-butanedione. 
(B) 
9-Chloro-1,5-dihydro-2-methyl-1-methylene-7-(2,6-difluorophenyl)-as-triazi 
no 4,3-a!- 1,4!benzodiazepine. 
In the manner given in Example 1B, 
7-chloro-5-(2,6-difluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone 
of 2,3-butanedione can be cyclized in liquid hydrogen fluoride to give 
9-chloro-1,5-dihydro-2-methyl-1-methylene-7-(2,6-difluorophenyl)-as-triazi 
no 4,3-a!- 1,4!benzodiazepine. 
EXAMPLE 11 
9-Chloro-1,5-dihydro-5-methyl-1-methylene-2-propyl-7-(o-chlorophenyl)-as-tr 
iazino 4,3-a! 1,4!benzodiazepine and 
9-chloro-1,5-dihydro-1,5-dimethyl-2-propylidene-7-(o-chlorophenyl)-as-tria 
zino 4,3-a! 1,4!benzodiazepine 
(A) 7-Chloro-5-(chlorophenyl)-3H-1,4-benzodiazepin-4-yl!-monohydrazone of 
2,3-hexanedione. 
In the manner given in Example 1A, 
2-hydrazino-5-(o-chlorophenyl)-3-methyl-3H-1,4-benzodiazepine can be 
reacted with 2,3-hexanedine to give a mixture of the 
7-chloro-5-(o-chlorophenyl)-3-methyl-3H-1,4-benzodiazepin-4-yl!monohydraz 
ones of 2,3-hexanedione. 
(B) 
9-Chloro-1,5-dihydro-5-methyl-1-methylene-2-propyl-7-(o-chlorophenyl)-as-t 
riazino 4,3-a! 1,4!benzodiazepine and 
9-chloro-1,5-dihydro-2,5-dimethyl-2-propylidene-7-(o-chlorophenyl)-as-tria 
zino 4,3-a! 1,4!benzodiazepine. 
In the manner given in Example 1B, the above mixture of monohydrazones of 
2,3-hexanedione can be cyclized in liquid hydrogen fluoride to give 
9-chloro-1,5-dihydro-5-methyl-1-methylene-2-propyl-7-(o-chlorophenyl)-as-t 
riazino 4,3-a! 1,4!benzodiazepine and 
9-chloro-1,5-dihydro-1,5-dimethyl-2-propylidene-7-(o-chlorophenyl)-as-tria 
zino 4,3-a! 1,4!benzodiazepine. 
EXAMPLE 12 
10-Chloro-3,6-dihydro-8-phenyl 2H!cyclopenta e! 1,2,4!triazino 4,3-a 1,4!b 
enzodiazepine 
(A) (7-Chloro-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazone of 
1,2-cyclopentanedione. 
In the manner given in Example 3A, 
7-chloro-2-hydrazino-5-phenyl-3H-1,4-benzodiazepine can be reacted with 
1,2-cyclopentanedione to give 
(7-chloro-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazone of 
1,2-cyclopentanedione. 
(B) 
10-Chloro-3,6-dihydro-8-phenyl 2H!cyclopenta e! 1,2,4!triazino 4,3-a! 1,4! 
benzodiazepine 
In the manner given in Example 3B, 
(7-chloro-5-phenyl-3H-1,4-benzodiazepine-4-yl)monohydrazone of 
1,2-cyclopentanedione can be cyclized in liquid hydrogen fluoride to give 
10-chloro-3,6-dihydro-8-phenyl- 2H!cyclopenta e! 1,2,4!triazino 4,3-a! 1,4 
!benzodiazepine. 
Example 13 
10-Bromo-3,6-dihydro-8-(2-pyridyl) 2H!cyclopenta e! 1,2,4!triazino 4,3-a! 1 
,4!benzodiazepine 
(A) 7-Bromo-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclopentanedione. 
In the manner given in Example 3A, 
7-bromo-2-hydrazino-5-(2-pyridyl)-3H-1,4-benzodiazepine can be reacted 
with 1,2-cyclopentanedione to give 
7-bromo-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclopentanedione. 
(B) 
10-Bromo-3,6-dihydro-8-(2-pyridyl) 2H!cyclopnta e! 1,2,4!triazino 4,3-a! 1 
,4!benzodiazepine. 
In the manner given in Example 3B, 
7-bromo-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclopentanedione can be cyclized in liquid hydrogen fluoride to give 
10-bromo-3,6-dihydro-8-(2-pyridyl)- 2H!cyclopenta e! 1,2,4!triazino 4,3-a! 
1,4!benzodiazepine. 
EXAMPLE 14 
11-Bromo-1,2,3,6-tetrahydro-9-(2-pyridyl)- 1,2,4!benzotriazino 4,3-a! 1,4!b 
enzodiazepine 
(A) 7-Bromo-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclohexanedione. 
In the manner given in Example 3A, 
7-bromo-2-hydrazino-5-(2-pyridyl)-3H-1,4-benzodiazepine can be reacted 
with 1,2-cyclohexanedione to give 
7-bromo-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclohexanedione. 
(B) 
11-Bromo-1,2,3,6-tetrahydro-9-(2-pyridyl)- 1,2,4!benzotriazino 4,3-a !1,4! 
benzodiazepine. 
In the manner given in Example 3B, 
7-bromo-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclohexanedione can be cyclized in liquid hydrogen fluoride to give 
11-bromo-1,2,3,6-tetrahydro-9-(2-pyridyl)- 1,2,4!benzotriazino 4,3-a! 1,4! 
benzodiazepine. 
EXAMPLE 15 
10-Chloro-1,5-dihydro-5-ethyl-2-methyl-1-methylene-7-(o-fluorophenyl)-as-tr 
iazino- 4,3-a! 1,4!benzodiazepine 
(A) 
8-Chloro-3-ethyl-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazo 
ne of 2,3-butanedione. 
In the manner given in Example 1A, 
8-chloro-3-ethyl-2-hydrazino-5-(o-fluorophenyl)-3H-1,4-benzodiazepine can 
be reacted with 2,3-butanedione to give 
8-chloro-3-ethyl-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazo 
ne of 2,3-butanedione. 
(B) 
10-Chloro-5-ethyl-1,5-dihydro-2-methyl-1-methylene-7-(o-fluorophenyl)-as-t 
riazino 4,3-a! 1,4!-benzodiazepine. 
In the manner given in Example 1B, 
8-chloro-3-ethyl-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazo 
ne of 2,3-butanedione can be cyclized in liquid hydrogen fluoride to give 
10-chloro-1,5-dihydro-5-ethyl-2-methyl-1-methylene-7-(o-fluorophenyl)-as-t 
riazino 4,3-a! 1,4!benzodiazepine. 
EXAMPLE 16 
11-Trifluoromethyl-1,5-dihydro-2-ethyl-1-ethylidene-7-(o-fluorophenyl)-as-t 
riazino 4,3-a! 1,4!benzodiazepine 
(A) 
9-Trifluoromethyl-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydraz 
one of 3,4-hexanedione. 
In the manner given in Example 1A, 
9-trifluoromethyl-2-hydrazino-5-(o-fluorophenyl)-3H-1,4-benzodiazepine can 
be reacted with 3,4-hexanedione to give 
9-trifluoromethyl-5-(o-fluorophenyl-3H-1,4-benzodiazepin-4-yl!monohydrazo 
ne of 3,4-hexanedione. 
(B) 
11-Trifluoromethyl-1,5-dihydro-2-ethyl-1-ethylidene-7-(o-fluorophenyl)-as- 
triazino 4,3-a! 1,4!benzodiazepine. 
In the manner given in Example 1B, 
9-trifluoromethyl-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydraz 
one of 2,3-butanedione can be cyclized in liquid hydrogen fluoride to give 
11-trifluoromethyl-1,5-dihydro-2-ethyl-1-ethylidene-7-(o-fluorophenyl)-as- 
triazino 4,3-a! 1,4!benzodiazepine. 
EXAMPLE 17 
8-Nitro-1,5-dihydro-2-methyl-1-methylene-7-phenyl-as-triazino 4,3-a! 1,4!be 
nzodiazepine 
(A) (6-Nitro-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazoe of 
2,3-butanedione. 
In the manner given in Example 1A, 
6-nitro-2-hydrazino-5-phenyl-3H-1,4-benzodiazepine can be reacted with 
2,3-butanedione to give 
(6-nitro-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazone of 
2,3-butanedione. 
(B) 
8-Nitro-1,5-dihydro-2-methyl-1-metylene-7-phenyl-as-triazino 4,3-a! 1,4!be 
nzodiazepine. 
In the manner given in Example 1B, 
(6-nitro-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazone of 
2,3-butanedione can be cyclized in liquid hydrogen fluoride to give 
8-nitro-1,5-dihydro-2-methyl-1-methylene-7-phenyl-as-triazino 4,3-a! 1,4!b 
enzodiazepine. 
EXAMPLE 18 
1,5-Dihydro-2-ethyl-1-methylene-7-(o-fluorophenyl)-as-triazino 4,3-a! 1,4!b 
enzodiazepine and 
1,5-dihydro-1-ethylidene-2-methyl-7-(o-fluorophenyl)-as-triazino 4,3-a! 1, 
4!benzodiazepine 
In the manner given in Example 2, 
2-hydrazino-5-(o-fluorophenyl)-3H-1,4-benzodiazepine can be reacted with 
2,3-pentanedione to give a mixture of the 
5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazones of 
2,3-pentanedione. 
This mixture of monohydrazones of 2,3-pentanedione can be cyclized in 
liquid hyrogen fluoride to give 
1,5-dihydro-2-ethyl-1-methylene-7-(o-fluorophenyl)-as-triazino 4,3-a! 1,4! 
benzodiazepine and 
1,5-dihydro-1-ethylidene-2-methyl-7-(o-fluorophenyl)-as-triazino- 4,3-a! 1 
,4!benzodiazepine. 
EXAMPLE 19 
9-Fluoro-1,5-dihydro-1-methylene-2-propyl-7-(o-fluorophenyl)-as-triazino 4, 
3-a! 1,4!benzodiazepine and 
9-fluoro-1,5-dihydro-1-methyl-2-propylidene-7-(o-fluorophenyl)-as-triazino 
4,3-a! 1,4!benzodiazepine 
In the manner given in Example 2, 
7-fluoro-2-hydrazino-5-(o-fluorophenyl)-3H-1,4-benzodiazepine can be 
reacted with 2,3-hexanedione to give a mixture of the 
7-fluoro-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazones of 
2,3-hexanedione. 
This mixture of monohydrazones of 2,3-hexanedione can be cyclized in liquid 
hydrogen fluoride to give 
9-fluoro-1,5-dihydro-1-methylene-2-propyl-7-(o-fluorophenyl)-as-triazino 4 
,3-a! 1,4!benzodiazepine and 
9-fluoro-1,5-dihydro-1-methyl-2-propylidene-7-(o-fluorophenyl)-as-triazino 
4,3-a! 1,4!benzodiazepine. 
EXAMPLE 20 
10-Chloro-3,6-dihydro-8-(o-chlorophenyl)- 2H!-cyclopenta e! 1,2,4!triazino 
4,3-a!- 1,4!benzodiazepine 
(A) 7-Chloro-5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclopentanedione. 
In the manner given in Example 3A, 
7-chloro-2-hydrazino-5-(o-chlorophenyl)-3H-1,4-benzodiazepine can be 
reacted with 1,2-cyclopentanedione to give 
7-chloro-5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclopentanedione. 
(B) 
10-Chloro-3,6-dihyro-8-(o-chlorophenyl)- 2H!-cyclopenta e! 1,2,4!triazino 
4,3-a! 1,4!benzodiazepine. 
In the manner given in Example 3B, 
7-chloro-5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclopentanedione can be cyclized in liquid hydrogen fluoride to give 
10-chloro-3,6-dihydro-8-(o-chlorophenyl)- 2H!cyclopenta e! 1,2,4!triazino- 
4,3-a! 1,4!benzodiazepine. 
In the manner given in Example 1A, other 
2-hydrazino-5-phenyl-3H-1,4-benzodiazepines can be reacted with vicinal 
alkane or cycloalkane diones of formula II to give the corresponding 
(2-hydrazino-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazones of the 
diones of formula II. 
Representative diones that can be thus obtained include: 
(7-chloro-5-phenyl-3H-1,4-benzodiazepin-4-yl)-monohydrazone of 
1,2-cyclopentanedione; 
7-nitro-3-ethyl-5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazon 
e of 1,2-cyclopentanedione; 
!7-trifluoromethyl-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydraz 
one of 1,2-cyclopentanedione; 
(9-trifluoromethyl-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazone of 
1,2-cyclopentanedione; 
(9-nitro-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazone of 
1,2-cyclopentanedione; 
8-bromo-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclohexanedione; 
8-nitro-3-methyl-5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazo 
ne of 1,2-cyclohexanedione; 
6-chloro-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,2-cyclohexanedione; 
7-chloro-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
1,3-cyclohexanedione; 
9-fluoro-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!-monohydrazone of 
1,2-cyclohexanedione; 
(7-nitro-5-phenyl-3H-1,4-benzodiazepin-4-yl)monohydrazone of 
2,3-hexanedione; 8-nitro- 
5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-hexanedione; 
5-(o-chlorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-hexanedione; 
5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-hexanedione; 
8-bromo-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-hexanedione; 
7-bromo-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-hexanedione; 
9-fluoro-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-pentanedione; 
9-nitro-3-methyl-5-(2-pyridyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-pentanedione; 
6-chloro-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-pentanedione; 
7-fluoro-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydrazone of 
2,3-butanedione; 
7-trifluoromethyl-5-(o-fluorophenyl)-3H-1,4-benzodiazepin-4-yl!monohydraz 
one of 2,3-butanedione; and the like. 
In the manner shown in Example 1B, treating the above hydrazones of formula 
II with liquid hydrogen fluoride produces the corresponding 
as-triazino 4,3-a! 1,4!benzodiazepines of formula IV. Representative 
compounds thus obtained include: 
10-chloro-3,6-dihydro-8-phenyl- 2H!cyclopenta e! 1,2,4!triazino 4,3-a! 1,4 
!benzodiazepine; 
10-nitro-6methyl-3,6-dihydro-8-(o-chlorophenyl)- 2H!cyclopenta e! 1,2,4!tr 
iazino 4,3-a! 1,4!benzodiazepine; 
10-trifluoromethyl-3,6-dihydro-8-(o-fluorophenyl)- 2H!cyclopenta e! 1,2,4! 
triazino 4,3-a! 1,4!benzodiazepine; 
12-trifluoromethyl-3,6-dihydro-8-phenyl- 2H!cyclopenta e! 1,2,4!triazino 4 
,3-a! 1,4!benzodiazepine; 
12-nitro-3,6-dihydro-8-phenyl- 2H!cylcopenta e! 1,2,4!triazino 4,3-a! 1,4! 
benzodiazepine; 
12-bromo-1,2,3,6-tetrahydro-9-(o-fluorophenyl) 1,2,4!benzotriazino 4,3-a! 
1,4!benzodiazepine; 
12-nitro-1,2,3,6-tetrahydro-9-(o-chlorophenyl)-7-methyl- 1,2,4!-benzotriaz 
ino 4,3-a! 1,4!benzodiazepine; 
10-chloro-1,2,3,6-tetrahydro-9-(o-fluorophenyl) 1,2,4!benzotriazeino 4,3-a 
! 1,4!benzodiazepine; 
11-chloro-1,2,3,6-tetrahydro-9-(2-pyridyl)- 1,2,4!benzotriazino 4,3-a! 1,4 
!benzodiazepine; 
13-fluoro-1,2,3,6-tetrahydro-9-(2-pyridyl) 1,2,4!benzotriazino 4,3-a! 1,4! 
benzodiazepine; 
9-nitro-1,5-dihydro-1-methylene-2-propyl-7-phenyl-as-triazino- 4,3-a! 1,4! 
benzodiazepine; 
9-nitro-1,5-dihydro-2-methyl-1-propylidene-7-phenyl-as-triazino 4,3-a! 1,4 
!benzodiazepine; 
10-nitro-1,5-dihydro-1-methylene-2-propyl-7-(o-chlorophenyl)-as-triazino 4 
,3-a! 1,4!benzodiazepine; 
10-nitro-1,5-dihydro-2-methyl-1-propylidene-7-(o-chlorophenyl)-as-triazino 
4,3-a! 1,4!benzodiazepine; 
1,5-dihydro-1-methylene-2-propyl-7-(o-chlorophenyl)-as-triazino 4,3-a! 1,4 
!benzodiazepine; 
1,5-dihydro-2-methyl-1-propyliene-7-(o-chlorophenyl)-as-triazino 4,3-a! 1, 
4!benzodiazepine; 
1,5-dihydro-1-methylene-2-propyl-7-(o-fluorophenyl)-as-triazino 4,3-a! 1,4 
!benzodiazepine; 
1,5-dihydro-2-methyl-1-propylidene-7-(o-fluorophenyl)-as-triazino 4,3-a! 1 
,4!benzodiazepine; 
10-bromo-1,5-dihydro-1-metylene-2-propyl-7-(o-fluorophenyl)-as-triazino 4, 
3-a! 1,4!benzodiazepine; 
10-bromo-1,5-dihydro-2-methyl-1-propyliene-7-(o-fluorophenyl)-as-triazino- 
4,3 -a! 1,4!benzodiazepine; 
9-bromo-1,5-dihydro-1-methylene-2-propyl-7-(2-pyridyl)-as-triazino 4,3-a! 
1,4benzodiazepine; 
9-bromo-1,5-dihydro-2-methyl-1-propyliene-7-(2-pyridyl)-as-triazino 4,3-a! 
1,4!benzodiazepine; 
11-fluoro-1,5-dihydro-2-ethyl-1-methylene-7-(2-pyridyl)-as-triazino 4,3-a! 
1,4!benzodiazepine; 
11-fluoro-1,5-dihydro-1-ethylidene-2-methyl-7-(2-pyridyl)-as-triazino 4,3- 
a! 1,4!benzodiazepine; 
11-nitro-1,5-dihydro-2-ethyl-5-methyl-1-methylene-7-(2-pyridyl)-as-triazin 
o 4,3-a 1,4!benzodiazepine; 
11-nitro-1,5-dihydro-1-ethylidene-2,5-dimethyl-7-(2-pyridyl)-as-triazino 4 
,3-a! 1,4!benzodiazepine; 
8-chloro-1,5-dihydro-2-ethyl-1-methylene-7-(o-fluorophenyl)-as-triazino 4, 
3-a! 1,4!benzodiazepine; 
8-chloro-1,5-dihydro-1-ethylidene-2-methyl-7-(o-fluorophenyl)-as-triazino 
4,3-a! 1,4!benzodiazepine; 
9-fluoro-1,5-dihydro-2-methyl-1-methylene-7-(o-fluorophenyl)-as-triazino 4 
,3-a! 1,4!benzodiazepine; 
9-trifluoromethyl-1,5-dihydro-2-methyl-1-methylene-7-(o-fluorophenyl)-as-t 
riazino 4,3-a! 1,4!benzodiazepine; and the like. 
Treating the compounds of formula IV with pharamacologically acceptable 
acids such as hydrochloric, hydrobromic, phosphoric, sulfuric, acetic, 
propionic, toluenesulfonic, methanesulfonic, tartaric, citric, lactic, 
malic, maleic, and cyclohexanesulfamic acids produces the 
pharmacologically acceptable stals of these compounds of formula IV which 
can be used like the free base compounds of formula IV. Salt formation is 
achieved in conventional manner by reacting the compounds of Formula IV 
with excess of a selected acid in a suitable medium, e.g., water, a lower 
alkanol, ether, or acetone and recovering the salt by evaporating the 
solvent, preferably in vacuo.