Über die Isomerie‐Verhältnisse in der Pyrazol Reihe

Abstract

Rojahn: Isomerie-Verhdtnisse in der Pyrazol-Reihe. 607 dem Schmelzpunkt. In den meisten organischen Mitteln leicht loslich, sehr schwer dagegen in niedrigsiedendem Ligroin und Wasser. 0.0913 g Sbst.: 12.8 ccm N (14~. 740 mm). -C,H,N,Br. Ber. N 16.0. Gef. N 16.0.Das P i k r a t der Base fkillt auch aus stark verdiinnter atherischer Losung sofort aus und la& sich aus Alkohol umkrystallisieren. Griinstichig hellgelbes, krystallinisches Pulver vom Schmp. 122-122.5~.

.pi.-Equivalent heterocyclic congeners of tropone. Azatropones

“…An analytical sample was prepared by dissolving 100 mg in 0.5 ml of CH2C12, depositing this solution on top of a 70 X 5 mm Woelm neutral, activity grade I, alumina column,, and eluting with pentane. Evaporation of the pentane afforded pure 19: mp 57-58°; nmr (CCh) 6.70 (q, 1, vinyl H, J = 1 Hz), 6.13 (s, 1, vinyl ), 4.20 (q, 2, OCH2CH3, J = 7 Hz), 2.20 (s, 3, CH3), 2.08 (q, 3, CHS, J = 1 Hz), and 1.32 (t, 3, OCH2CH3, J = 7 Hz).…”

“…Thus, hydrogenation (Parr shaker, 40 psi, 12 hr) of 10 (5.0 g, 0.033 mol) in 30 ml of 95% C2H5OH over 30% Pd/C (100 g) afforded, after catalyst removal and solvent evaporation, a viscous oil which solidified upon standing. Recrystallization from CH2Cl2-pentane followed by an ether wash gave 3.8 g (73%) of 4,7-dimethylhexahydro-1Hazepine-2,5-dione (21): mp 166-168°(from CH3CN); ir 3400, 3280 (NH), 1675 (C=0), 1680 and 1670 cm"1 (NCO); nmr (DMSO-cZ6) 7.08 (mound, 1, NH), 4.62 (d, 2, =COH, / = 5 Hz), 4.00-1.42 (m, 5, ring protons plus enolic OH), 1.08 (d, 3, CH3, J = 7 Hz), and 0.78 (d, 3, CH3, J = 7 Hz); nmr (DMSO-d6-D20) absorptions at 7.08, 4.62, and 4.00-1.42 (for one proton) disappear.…”

“…An analytical sample was obtained by preparative gc and re-distilled to give 5-ethoxy-4,6,7-trimethyl-3,4-dihydro-lH-azepin-2-one (23) as an oil which could not be induced to crystallize: bp 64°( 0.1 mm); ir 1660 (C=0) and 1275 cm-1 (=COC); uv max 300 nm (e 10,000); nmr (CCl,) 4.20 (q, 2, OCH2CH3, J = 7 Hz), 1.68-2.22 (m, 3, CH and CH2), 1.97 (q, 3, CH3, J = 0.5 Hz), 1.82 (q, 3, CH3, J = 0.5 Hz), 1.27 (t, 3, OCH2CH3, J = 7 Hz), and 1.10 (d, 3, CH3, J = 7 Hz). Anal.…”

“…Upon standing at -10°c rystals formed. This procedure was repeated to give a white solid: mp 105-106°; ir 3350 cm-1 (OH); uv max 210 nm (e 36,800) and 285 (5700); nmr (CC14) 7.72-6.83 (m, 8, aromatic), 5.08 (s, 1, CH), 4.50 (m, 2, OCH2CH3) 3.29 (mound, 1, OH), and 1.47 (t, 3, OCH2CH3, J = 7 Hz).…”

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Seven azatropones, -equivalent heterocyclic congeners of tropone, have been prepared and characterized. Thus treatment of 4,4,6,and 3,4,6, with triethyloxonium fluoborate afforded respectively , 7-ethoxy-2,5-dimethyl-4ff-azepin-4-one (19), S-ethoxy-4,6,7-trimethyl-2ff-azepin-2-one (22), and 5-ethoxy-3,4,6,7-tetramethyl-2H-azepm-2-one (28). With the same reagent, lff-benz[/]azepine-2,5-dione ( 16) and 5ff-morphanthridine-6,11-dione (18) gave 2-ethoxy-5flrbenz[flazepin-5-one (34) and ll-ethoxybenz[c]cyclohexadienyl[5,6-/]-2íí-azepin-2-one (42), respectively.

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