共軛不飽和酮　第十五報　9-Phenyl-1, 2, 3, 4, 5, 6, 7, 8-octahyfroacridine之合成

Conjugated Unsaturated Ketones. XV. Synthesis of 9-Phenyl-1, 2, 3, 4, 5, 6, 7, 8-octahydroacridine

楊緒煫(Shü-Shu Yang) ； 黃維鏞(Wei-Yong Huang) ； 陳淑敏(Shu-Min Chen)

《化學》 51年2期 (1962/06) Pp. 65-68

https://doi.org/10.6623/chem.1962012

摘要

2-苯亞甲基環己酮與環己酮經硫酸處理，即得樹脂狀物。萃取水溶性之oxonium 鹽(IV)，並以氨水處理，得微量鹼性物質。經柱層色析法精製後，製成苦味酸鹽，確認所鹼性物為9-phenyl-1, 2, 3, 4, 5, 6, 7, 8-octahydroacridine (V)。

並列摘要

Recently, Wizinger et al, synthesized 2, 4, 6-triphenylpyrylium perchlorate (II) by heating 1 hr. a mixture of benzaldehyde and acetophenone in coned. sulfuric acid, followed by adding perchloric acid t o the reaction product. When II was treated with ammon triphenylpyridine (III) was obtained. In the present work, attempts were made to synthesize 9-phenyl-1, 2, 3, 4, 5, 6, 7, 8-octahyfroacridine(V) by the similar reaction. The condensation of □ cyclohexanone, in the presence of coned. sulfuric acid followed by adding perchloric acid at room temperature did not yield any crystalline product. Condensation of 2-benzyli-denecyclohexanone with cyclohexanone under similar condition was also failed. Finally we synthesized V as follows: 2-Benzylidenecyc1ohexanone (0.01 mole) and cyclohexanone (0.03 mole) were condensed in the presence of 3 g. 98% sulfuric acid at room temperature to give a highly viscous blood-red product (probably IV). After standing overnight, the product was extd. with cold water until the ext. became colorless. The brown solid could not be purified by recrystn. nor by alumina chromatography. The aq. exts. were combined and it was neutralized with NaOH to give yellow-brown viscous resinous matter, which could not be purified. This resinous matter was again dissolved in dill. sulfuric acid and neutralized with ammonia to give white ppt., the color of which first turned to yellow, then to orange. The ppt. was filtered, dissolved in benzene and chromatographed on alumina to give 50 mg. pale yellow crude V, m. 167-171° (recrystd. from benzene), which showed positive Mayer 's test for alkaloids. This was dissolved in 2 ml. 2% Hel, filtered, and mixed with satd. aq. soln. of picric acid to give 42 mg. pale yellow picrate (needles), m. 175-6°. The picrate was dissolved in 2 ml. ethanol and decompd. with 5 ml. 2% ammonia to give 10 mg. colorless needles, V, m. 176-177°. After the completion of the present work, we found that Tilichenko et al. B had prepared V (m. 177-8°, picrate m. 175-5.5°) from 2-phenyl-3,4-tetramethylenebicyclo (3, 3,1) nonane-9-one--4-o1 (VI), ammonia and AcOH by heating 2 hrs. at 133-7°. When V was heated with Pd-C at 240-313°, 9-phenylacridine (VII) was obtained.