4-Azidoformyl-4,5-dihydro-1,3-dimethyl-lH-pyrazolo [ 3,4-b]-[1,4]benzoxazepine (32). A soln of 4.56 g (0.02 mole) of 31 and 2.6 g (0.04 mole) of NaN, in 100 ml of 90% Me,CO-H,O was stirred for 12 hr. The soln was concd, and the residue was taken up in Et,O and filtered, and the filtrate was dried (MgSO,). The solid obtd upon concn was crystd from Skelly B to give 1.2 g (22%). 4-Carbamoyl and Thiocarbamoyl Derivatives of 4,s-Dihydro-1,3-dimethyI-lH-pyrazolo[ 3,4-b] [ 1,4]benzoxazepine.A soln (0.037 mole) of RNCO or RNCS and 8 g (0.037 mole) of base prepd from 30 in 250 ml of Et,O was stirred for 12 hr. The soln was concd, and the resulting solids were crystd to give yields ranging from 55 to 88%. Compds 39,42,47, and 48 were prepd in this manner. 4,5-Dihydro-l,3-dimethyl-4-formyl-lH-pyrazolo [ 3,4-b] [ 1,4]benzoxazepine (33). Compd 30 (6.4 g, 0.03 mole) was refluxed for 2 hr in 75 ml of ethyl formate. The soln was concd and the oil chilled to effect crystn. Recrystn from Skelly B gave 4.3 g (60%). S-Carbamoyl-4,S-dihydro-1,3-dimethyl-W-pyrazolo[ 3,4-b 1-[1,4]benzoxazepine (34). An aq soln of KNCO (3.3 g, 0.04 mole) was added to 10 g (0.04 mole) of 31 in 70 ml of H,O. After 1 hr the solid was collected and washed with H,O. Crystn from EtOH gave 6.3 g (61%). 4,5-Dihydro-1,3,4-trimethyl-lH-pyrazolo [ 3,4-b] [ 1,4]benzoxazepine (36). A soln of 21.5 g (0.10 mole) of base prepd from 30 in 50 ml of dioxane was added to a stirred mixt of 4.8 g (0.10 mole) of NaH in 150 ml of dioxane. The mixt was heated to 70" for 2 hr and then cooled to 20" while a soln of 14.2 g (0.10 mole) of Me1 in an equal vol of dioxane was added dropwise. The temp was then raised to 40" for 3 hr. After removal of solvent, the residue was taken up in 5% HCl and washed with Et,O. The acid soln was basified, extd with Et,O, dried, and filtered, and the filtrate was evapd to yield a solid. The solid crystd from Skelly B to give 15.6 g (67%). Compd 40 was also prepd by this method.

Aus den Dihydroxy‐benzolen (I) entstehen mit den Alkylierungsmitteln (II) die Monoäther (III), die mit Epichlorhydrin (IV) über die Glycidäther (V) durch Reaktion mit Aminen (VI) zu den Aminoalkyl‐phenolen (VII) führen.

Seventeen 2-(substituted phenoxymethyl) morpholines were synthesized by the reduction of 6-(substituted phenoxymethyl)morpholin-3-one or by the reaction of 1,2-epoxy-3-(substituted phenoxy) propane, 2-aminoethyl hydrogen sulfate and sodium hydroxide in a mixture of water and ethanol. These compounds were tested for effectiveness in preventing reserpine-induced ptosis and in prolonging the survival time of mice subjected to hypobaric hypoxia.In the reserpine ptosis test, o-benzyl, o-(3-thenyl), o-(2-pyridylmethyl) and o-(2-thenyl) substituted 2-phenoxymethylmorpholine (VIn, VIl, VIe and VIh) were effective with RD30 values of 3, 9, 10 and 12 mg/kg (p.a.), respectively.In the antihypoxia test, p-(2-thenyl), o-(5-methyl-2-thenyl) and m-(2-thenyl)substituted 2-phenoxymethylmorpholine (VIj, VIk and VIi) and VIh were effective with survival times of 515.0, 375.8, 346.7 and 406.7 s, respectively.From these results the two most promising compounds, VIh and VIn were tested for amelioration of CO2-induced amnesia. VIn but not VIn showed ameliorative activity.

239ChemInform Abstract The morpholines (VIII) mentioned in the title are synthesized from the epoxides (I) via two pathways shown in the reaction scheme. The ability of (VIII) to prevent reserpine-induced ptosis and to reduce hypobaric hypoxia in mice is investigated. (Yields given in g, IR-, 1H-NMR-, MS-data).