May 1965
FLUORENES. XIX. POTEXTIAL AKTITCIIOR COMPOUNDS
347
53 using excess dry KHBin ether solution, and the amide was reduced with LiAlH4 by the general procedure above to yield the amine hydrochloride 54. 13-(9-Triptycyl)-6-ketotridecanoicAcid (55).-The acid chloride of 8-(9-triptycyl)oct,anoicacid (52) was used to acylate the niorpholine enamine of cyclopentanone by the procedure used above. The crude p-diketone on alkaline hydrolysis afforded the ket'o acid 55. 13-(9-Triptycyl)tridecanoieAcid Amide (56).-\Volff-Kischner reduction of the ket,o acid 55 by the procedure used for 52 gave the t,ridecanoic acid, which vias converted to the amide 56 in the usual nay. Reduction of t,he amide afforded the amine hydrochloride 57. 12-(9-Triptycyl)dodecylamine Hydrochloride (58).-Hofmann degradation of the amide 56 was carried out using the procedure employed with 35. The crude carbaniate so formed was hydrolyzed by the method used for conversion 27 + 29 above.
a t 35-38" was continued for 30 min. The reaction mixt'ure was kept overnight a t room temperature, after which 25 ml. of 6 S HC1 was added. The mixt,ure was stirred a t 35-42" for 30 min. The chloroform layer was separated and washed with wat'er, and the solvent was distilled i n z~acuo. The residue %-ascrystallized from ether-petroleum ether; yield 8.5 g., m.p. 193-203". A sample vias recrystallized from ethylene dichloride-etherpetroleum ether. 5-(p-9-Triptycylpropionyl)valeric Acid (51).--4 solution of the diketone 50 (i.85g.) and 0.95 g. of NaOH i n 100 nil. of ethanol was refluxed for 4 hr. Concentrated HC1 (2.5 ml.) was added, and most of the ethanol wds distilled in w c u o . The product was filtered and washed with water; yield 7.5 g., m.p. 193-197'. il sample was recryst,allized from toluene for analysis. 8-(9-Triptycyl)octanoic Acid 152).-A mixt,urc of 7.3 g. of the keto acid 51, 1.05 g. of KOH, i . 5 ml. of 85r; hydrazine hydrate, and 20 ml. of diethylene glycol was stirred and refluxed for 6 hr. Diet,hylene glycol (20 v.1.) and 5 . 5 g. of KOH were added, and the niixture was heated for 17 hr. in an open flask in an nil bath kept a t 195". Thc reaction mixture was poured into several volumes of water. Then 12 S HC1 (20 nil.) was added. and the mixture was heated, then cooled, and the product was filtered and washed well with water; yield 6.7 g., m.p. 160-168". It vias recrystallized from met'hanol-ether. The acid chloride was prepared using oxalyl chloride according to the proredure given above for the acid chloride 34. This was converted to the amide
Acknowledgments.-The authors thank 11r. W. L. Brown and associates for the microanalyses, and Dr. H. Boaz and co-workers for physical data. The mouse behavior studies were carried out by N r . R. W. Kattau, and the antiinflammatory assays by Dr. R. Kraay and his associates. __
Derivatives of Fluorene. XIX.'' 9-o-Chlorocinnamylidenefluorene and Related Compounds T. LLOYDFLETCHER, 1\IOSES J. SAMKUSG, JOHX R. DICE,A S D SASDRAI . 76-78: ( v i p. 321.
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