Fec., IC46
STRUCTURES OF NITRATED FLUORENE DERIVATIVES
!CONTRIDUTIOS FROM THE CHEMICAL
LARORATORY OF WESTER?:
I L L I s O I S STATE
3189
TEACHERS COLLEGE]
Structures of Some Nitrated Fluorene Derivatives I3u C.l V . B E x x x r , Xi-. G. J E K S ~ ~ C K Y.\XD
J . ~ EP.
DUPUIS'
This tnvestigation was undertxken in order t o present authors after repeating this nitration clear up the structure of :L dinitro tierivati\-e of !f- several times were able t o isolate two new com2,i-dinitro-9-acetaminofluorene and acetaminofluorene reported by the srriior author pounds, of this p q x r and the Lite IY, no ye^.^ Since t',.j-dinitro-l~-acetaniinofluorene, which take the i t obviously \KLS iiot the nionoii;tro-!)-acetainino- place of the tentatively reported 1,S-dinitro-0fluorene the:,- twrt? qwking it \ws not further :~i.etatiiinofluor~iie.~ studied :tt th.it tiiiie exci:I)t for au anctlysis a11(1 Experimental the tentative suggestion that it might bp tllt 1,sPreparation of 2,7-Dinitrofluorene and 2,5-Dinitrodinitro-!I-acetaminofluoretie. I t h:is since been .-Fluorcne tvas nitrated according to the direcshown by Huntress arid Cliff that the supposed fluorene tions of Coartot and l\Ioreauxe using fuming nitric acid at 1,8-dinitrofluorenone c;f Kuhn and J:lcob4 and of room temperature. 'The 2,7-di;iitrofluoreiie, recrystallized Schmidt aud Stutzel' prepared iinder iiiore dras- froin nitrobenzeue incltetl a t 310" (uiicor.). The 2,5-dinitic conditions from n-3cetaiiiiriofluorenc, was trof-luorenc melted at 2i)7-%)So (uiicor.) after recrystallifroin glacial acctic acid. Oxidations of these isoactually a mixture of ',i-tlinitrofluorenone atid an zation mers readily yiizlticd the 2,7- and 2,s-clinitrofluorenones. unknown dinitrofluorenone, 111. 11. 2 1:I2 hatl rcj:orted 2 X - 2 5 3 ") . Goltlschrriiedt and other dinitrofluorene which he "oxidized" t o a Schraiizhofer" gave 227-228" for the 111. p. of their phenylTvliich was evidently i a p u r e . dinitrofluorenone, in. p. 2 X 0 , is evidently 2,s- hydrazone Nitration of 9-Acetaminofluorene According to dinitrofluorenone. Goldschmiedt and Schranz- Huntress and Cliff .--Fluorenone oxime prepared accordhoferY hatl obtained a mixture of 2,7-tlinitro- ing to 3 1 0 : ) ~a.id Iiuiiti-essiZwas reduced to the %aminoaccording to 11igold anti K'ilsoii's direction^'^ . fluorenonc and a more soluble, less abundant 11uoxi;e acid and ziiic dust. The crude amine was 1"'" by nitration of fluorcnone. iisirig rtcctic ccortling to Kc..-pi5 with acetic anhydride. We have ~ X I J able lo show, after repeating these of tliv 9-nci tatriitiof-luorciie, in. p . 261 was a steann-!)nth with 18 1111. of nitric acid (sp. two preparations, that the substaiicc melting at 220' of Golfcrarid that g.1 .-!?) f?r thirt.Li.n imiir5. The reaction mixture was The dried : I . I I ( ~ tlie lxi;;!it yclloiv mass filttrrcd. melting a t ?I:.; -?!-I" of Huntress ant1 Cliff'
