No abstract

No abstract

A plan of approach to novel 8‐azasteroids was tested with suitable model compounds to determine its feasibility. The results of these experiments are described.

VOL. 28 2950 M%YERS AND RALHAN 0.45 g. of platinum oxide was reduced under a pressure of 45 lb. a t 25". The absorption of 0.036 mole of hydrogen was complete in 1 hr. The catalyst was removed and the solution neutralized with sodium hydroxide and extracted with ether. Distillation of the ether residue gave 2.8 g. of a colorless oil, b.p. 67-68'(1.5 mm.); n% 1.4710. A sample injected into the gas chromatograph exhibited one strong peak (987,) and a small fore peak (2%). The mixture upon elemental analyses gave the following results.Anal. Calcd. for CllHzlN: C, 79.04; H, 12.57; N, 8.38. Found: C, 78.99; H, 12.48; N, 8.37.A Zerewitinoff determination of active hydrogen gave 0.55y0 H (calcd., 0.61%).The hydrochloride of the mixture, after a single recrystallization from methanol-ethyl acetate, melted sharply a t 289' (sublimed a t 240" at 1 atm.).Anal. Calcd. for CIIHnNCI: C, 64.86; H, 10.81; C1, 17.44. Found: C, 65.10; H, 11.20; C1, 17.80. Hydrogenation of XIX to the Mixture XXIa and XX1b.-A solution of 6.0 g. of the tetrahydropyridine in 60 nil. of acetic acid and 1.5 g. of platinum oxide was hydrogenated a t 60 Ib. a t 25" for 48 hr. After this period of time the theoretical uptake of hydrogen was complete. Removal of the catalyst, neutralization of the solution, and extraction with ether gave 5.8 g. of a colorless oil, b.p. 74-77" ( 3 mm.); n a o D 1.4703; the analytical results were in accord with the c h h l a t e d values. Gas chrornatographic examination indicated that the sample was composed of two peaks in the ratio of 49.17, to 50.9%. Injection of the acetic acid reduction produrt of I under identical instrument conditions revealed that it was the same as one of the two reduction products of T'. An attempt to separate the hydrochlorides of XXIa and XXIb was successful insofar as obtaining one of the isomers in a pure state, m.p. 289". The other isomer could not be obtained without contamination, m.p. 235-260". N-2,6,6-Tetramethyl-3,4-cyclopentanopiperdine.-~4 solution of 4.0 g. of 2,6,6-trimethyl-3,4-cyclopentanopiperdine (XXIa) in 50 ml. of 98% formic acid and 30 ml. of 37% formalin solution was heated overnight on a steam bath. Upon cooling the solution was poured into 200 ml. of 257, sodium hydroxide and the resulting mixture extracted with ether. Tlistillation of the ethereal residue gave a colorless oil, b.p. 79' (1 mm.); n 3 3~ 1.4796. The methiodide recrystallized from methanol-carbon tetrachloride, melted a t 253". A study dcaigned to obtain azasteroids by their total synthesis via a novel route has led to three new tricyclic bases, 2,2-dimethylryclopenteno[d]-l-azabicyclo[4.2.O]octane (I), 2,2-dimethylcyclopenteno[d]-l-azabicyclo-[4.3.0]nonane (11), and 2,2-dimethylcyclopenteno[d]-l-azabicyclo[4.4.O]de~ane (111). These systems were prepared from a single synthetic operation involving the appropriate chloroalkyl nitrile and a-(2-hydroxycyclopentyl)-t-butyl alcohol. The mechanism for the formation of these ring systems is consistent with previous studies which have led to related compounds.The plan...

Thiazolo[2,3-c][1,2,4]triazepines have been synthesized by the condensation of thiazol-2-ylhydrazines with requisite 1,3-diketones and a β-keto ester.