1471784 Fused dibenzo[c,f]azepines and dibenzo[b,f][1,4] - diazepines - oxazines and -thiazepines AKZO NV 24 April 1974 [26 April 1973] 17985/74 Heading C2C Novel compounds IV and salts thereof in which R 1 , R 2 , R 3  and R 4  are hydrogen, hydroxy, halogen, C 1-6  alkyl, C 1-6  alkoxy, C 1-6  alkylthio or trifluoromethyl, X is >O, >S, >NR 7  or >CR 8 R 9  (where R 7  is hydrogen or C 1-4  alkyl and R 8  and R 9  are each hydrogen or methyl) A is the group (where R 5  and R 6  are hydrogen, C 1-6  alkyl, C 7-10  aralkyl or NR 5 R 6  represents a 5- or 6-membered heterocyclic ring and n is 0 to 3 with the (CH 2 ) n -NR 5 R 6  moiety being either # or γ to the N atom) are prepared by standard methods from compounds II Compounds IV in which A is are prepared from compounds II by (1) reaction with ethylformate and sodium methoxide to give followed by tosylation, reduction and animation to give the group -CH 2 -NR 5 R 6 , (2) bromination and amination to give A= (3) Mannich reaction to give A= (4) reaction with isoamyl nitrate and potassium t-butoxide followed by reduction to give A = (5) reaction with sodamide and to give (6) reaction with hydroxylamine and tosyl chloride followed by the Nelser rearrangement to give A is Compounds IV in which A is are prepared by Wolff-Kishner reduction of the corresponding keta compounds. Compounds IV in which A is are also prepared by (1) reaction of a compound V in which Y is halogen or a sulphonyloxy group with an amine HNR 5 R 6 , (2) reduction of a compound VII in which R is -(CH 2 ) p CN or -(CH 2 ) n -N 3  (where p is 0 to 2 and n is as above) to form compounds in which R 5  and R 6  are hydrogen (3) reacting a compound II with an amine HNR 5 R 6  in the presence of a reducing agent to form compounds in which n is 0, (4) reduction of the oxime of compounds II to form compounds in which A is (5) reduction of a compound IX or X in which n is 0 to 2 to give compounds in which n#1, (6) reaction of a compound II with acetonitrile in the presence of sodium ethoxide followed by reduction to give compounds in which n = and R 5  and R 6  are hydrogen. Compounds IV in which R 5  and R 6  are hydrogen are methylated by reaction with formaldehyde. Compounds IV form isomers in which the substituent (CH 2 ) n -NR 5 R 6  may be in the equatorial or axial position. Compounds II are prepared by condensation of vinyl methyl ketone with the appropriately substituted derivative of morphanthridine, dibenzoxazepine, dibenzothiazepine or dibenzodiazepineto give the 2-oxo compound which may be converted to the 3-oxo derivative by reaction with isoamyl nitrate and potassium t-butoxide after which the 2-oxo group of the 2-oxo-3-oximino compound is reduced and the oximino moiety saponified. Compounds V are prepared by reduction of the ketone group of compounds II to hydroxy and esterifying or halogenating and for compounds V in which n is 1 to 3 extending the alkyl chain length by the standard homologation procedure. Compounds VII in which R is -(CH 2 ) n N 3  are prepared by treating a compound V with sodium azide; those in which R is -(CH 2 ) p -CN are prepared by (i) reacting a compound V (n is only 0, 1 or 2) with sodium cyanide or (ii) by reacting a compound II with HCN, eliminating the hydroxyl group and reducing the double bond. Compounds IX are prepared by hydrolysis of the cyano compounds of Formula VII to form the acid followed by conventional amidation. Compounds X are prepared by a Wittig reaction on compounds II. Compounds IV are CNS depressants and form with a carrier a pharmaceutical composition which may be administered orally or parenterally.