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Some Aspects of Fluorene Chemistry and Of 1_::rr:r ' .i ¿66r ãt$$E[üiEls '''.:' : i , 'goMlICg dO e{&gfn ,gO $üSfiC SSú EOfl Sü[E@IObffi SSü , ,{o tE¡ttr[ILmaà Íru&$rd uI ?gofiIs?E ðo Ã.úIsftEfÀINß gHü do EOEvEIffiã g&!r srIGIIüg güfiIcrìfÐ ,{o Ãslaoyc lr¡r& o& rîrÍ&Ifrtag " SIS$Eü T -:.'.: : : ÀIllì[E[$.c.Iï¡':s$rof I.fT ETIEÐTEE TXSüIEEOiãNÍ fftrf" EO C[f $IÍ6II$IEC gMffiOAlIt ,fO SüOSrßIf ffiOS 10 Ð8. E. E. CEÁ¡I,ESWOBS FOh EIg TãVAE'¡]Á3I,E ÂÐYI6E .å,XÐ TBFITIIEI¡T ?ÀtsIETT êT]ÐÂTCE IT tsHTS FTESÍ 9EüEEEK XTBO THE Bts,å,IT OF gEPeîr EEEiEAkGgrIHg ^AElEgR rS €IRAßFÛE| i:i', ¡¡.¡.j,:: i.,¡:!1ì.:r.rf,{, 1r'1i,,}.!j': }l :!¡J;:i":iijii.'.r.¡-,:.tffriT?Ë tri}'Ì::1t:-Ì'a¡t:ì:i:::ii.".t: Ìì1.¡.i1:/...l¡".<f¡:a?is¡ ÎABIE OF OOI{18}¡TS fltl-e page Acln:orleelgeuenù .. ... .lLL Iatroduotl.on e¡xat abstract .. ........1 tl,tenature su¡reey ......4 I' lhe ohæf.st¡ry of fluorene and fluorenone ... .. ...4 fI. Exteas Lons of the Roforuatsþ ¡reactlon ..........a3 III. Efbe¡ls of fluoreno .........,.".27 IV. Substr.ùutedl banblüurlc acl.d.s .... ........"....28 Dlgeusslon of regul.tc . ... e .. .. r . .. ' " Jl I. 8xùensLons of the Refomatsþ neactLon ,... r. ......31 A. Synthesls of ethylo(-(9-hydro¡qyfLuo:renyl) p¡ropLonatg .....rr.. .r,.'............'.....¡.J2 B. Roforæatek¡r reaotlon rf.Èh etbyl ¡'-broropooptoaate33 C. Befornatsþ reaotLot¿ wltb brononÈlonf.c ester ....35 '1. ltith e - tol.uat¿ehyde .r o... ...ç.r....:"....?5 2. Iültb cyc1ohêxanorrô rr¡ ........r?6 3r Wlth fluorenone ......r.r......e..o.r{r.............36 II. Etherg of fluorene .;.....r.......¡............"...38 III. Fniedel - Crafts reaetLons r.o.... ..,.19 1.. tsenzene - êlch1oracetLc acl.d ...... ........:9 2. DtpherryS. - dLchl-oraeetLc acLd..o..r. .......1+O 3. Bonzorx€ - illbromoaalonio eeter ......... .....¡+0 þ Olphenyf - dlib¡romomalonLc esten ... ......,.......".h1 rAtsI..E OF CONTE&SS 5. Dlphenyl - ethylld.ene eh]-onl.de oo.... .......h1 IV, Tho synthesLs of. fluorenyl bar"blturlc acLd .......hz Ex¡rerlmental .....¡...... o ù . r..........,......1¡l¡ .T¡ Befoløatsþ reactl.ons ...... ........4b Ar Synthesls of €ühyL4-(9-bfd"o¡ryfLuonerryl) . proplorrate . ù .. o . , . .......o¡+lj4 Br !Íltb É-bronopnopionate ...r.. ......U5 1o Wlth flÌ¡orenorlê ¡r....... ...,115 &¡ Prepanatlon of f -bnonopropLoïric acid .......,...46 b" PreparatLon of etþyL É-b"oropoopfonate ........,þ6 oe OxLdLatlon of f1uorene to fluorenohê .¡r ¡ .. .. ..".42 d. Frepa:ratlon of activatêd 31nc 2¿ üIlttrr acetophenone ...,¡...,.....,...................51 3. WlËh benzophênorlê ¡¡e¡e..... ...... ......,..52 ¿!. WLth acetonê o e e ¡¡ .. .. .._...52 Cr Wtth ethyL bromomalonate . ... ., . " . ..53 1r flll th eyclohexånon€ .. r.... ...... ... ....52 . 2. Tfltb' m - tolualdehyd.e .... .,..¡r..........51t år Synthes ls of ra-tolyl. earbfr¡ol ....... .."...55 ?, Wlth fluoreftort€ ¡ . ¡ . .. .r . , . ,56 â.o Synthesls of the p-nf.trobenzoate fLuo of nerol ".52 b. Synthes ls of èhe 3r5 dtnttrobenzoate of fluorono l ..r... G¡ Synthesls of th6 pheny]. u::ethan of fluorenol .,.58 i-.'{i,s ",:., ?AtsIE OF-CONTENES A. Synthesls of tb.ed-naphthyl urethan of fllrorenol . o............ ........5g II. Ether"s of fluorene . ..... ,....5g 1. Methyl ethen . .. .. .. .. ..,.59 2. Et?r¡r1 ethen 2. Propy1 ether ....... .........ó0 ¡+., Cyelohexyl ether ...¡........r. ...... r..r..62 '5, N-buty1 ethen....... o . 63 . " . 6. Benzyl othor ¡¡.............,...........r......t6? fII^" Frloitel - Craafte ::eaetlons . r . ¡ ¡ í o ¡ r . ...6? i. Benzene. - ¿llchlo"acetLc acld......¡ ,......61 2, Dtphenyl - d.lchlonacetic acid ......611 . 3. Benzene - d.Lb:eonromal-onl c ester .,.... .....66 4. Dlphercfl - dLb:rouomal.onL c esten r . r r. .66 5.. Dlphenyl - ethyLlcleno ehLorÍdê oo.r. ......68 XV. Subetituted. barbíturlc acLd ... .....68 1. S¡rnthosls of fluorenyl malonLe ester . .. .. .ó8 2. Synthes f.s of Rono fluorenyt barbitunLc acl.d c..t.6Ç SûütnaIT of Regul.ts ....... ........ ...... c.........¡¡........?1 Bf,bllognaphy ... r. ¡...... r . ¡ . .....73 i:ì'¡i i-* r :. 1.: (1) IITBODÛCTIOT AFD .â,BSTB¡,GT Íhc pnesenÈ fnvosËigatl.ôn was ontgtaal.ly lntendeå to bc a eontiauatloa a¡d corrolnsfon of Ëhe ro¡îk bêggn f,n tbose laboratorles by E. torl.Ëc (Ç) fn 1950r üorlta hedt sta¡tedl a.a fnvestf.gatLoa Lnto the ertEnsl.on of t¡be Eof,oraatsþ :reactLon to the uge of etb¡rl ; f -þronop¡loBLsnate¡ Ee ras pantleralar:t¡r. lntor.ssted. tn LÈs uac tn the ¡rroparatfoa, of :, fluonose de¡rLvatLveg b¡r eoadeaalng 1t rtt"h !-f,luøreaoae (X) tn tbfs ¡rcactLon . iì,-r': c,,.- c<:rr i: ;>r:,i Ès- e J-1.ô t¡o l' ll*- -o [ )a= qF -cHr-cí¿q.]t- ¿. t1,! Ee also lalt!,ateð aa LnveøtlgatLoa lato tho ap¡¡X.f.eabl,11ty of tho Þloêel - GrAfù¡ regetl,on to the s¡ratbesle s.f fluoranc - 9r9 - dtlea¡rborryllo eater (II) from ittpheayl andl eÈhyl dlbromo- [alonatc. fi.,i,"i;î:*b &.ï.:ï lbe êl,ceovef5r of bi.ologlcsJ. eetivtüy fa lrårty flt¡orcr¡o coqlounêa, suob as Z-acoÈy1a:nlne fluo:re¡re, (fl1) rrhtcb ls bXgLly earelaogea!.e, leð MorlÈa t'o atÈæ¡rù Èho pncpanatf'oa illl -co-cra (TTI ) of sonê ot'hê¡t olsss of flüg¡lGrrê eoqrouado rhf.eh elgþt al'so Þe biologloal.l.y Êctlve, as fl€sronyJ. bårblturfe aelcl (W). "tåh il*-c,'(""-1þ' (rr) Þree ts Xeck of Èfuer torLta ras snåb1e ùo eartgttbeoe iaveø tlgettons ta oenpleùloa. &e probl,æ !,4 thls nescareh ras to fc-êrsûlqê ad colpl.âte $onl,tels ¡orkr to ltlsattfy êErÈafll ntlrrlê¡ra Plreduetg e¡ild tô clart fþ Ëhe ¡oaotLoas by rhlcb Èheeo lcrc obta!'nsdl' flre BcfslneÈsbilr ls¡êùLoa eqrto¡riag et&yl -l - brr@æItroptonatc rao atteqrteê noË oaly wltb. fl¡¡orcaøae (I), Þttt alee çltb a rinsbe¡l of otbor kctones as rel.l¡ A fLuoreae êonlnat!.ve r fluo¡reac -9- oa¡rborylte aotd (Y) m.e s¡nrtlrcolreê by neaae of e Þtredle1 ." Graftg conêe¡rsaùf'oa $ eryLoylng blpberyl and dlchloracif,to aoldo cc Ég. l" u*)"u-too' (v) 8"rt'**-iteþ An attqrt ras [adc to pnepare sevena]. ethe¡:s sf flno¡oae b¡r ooadeas lng 9-brerof,lüorcae (lI) rlth t¡he sod!.r¡! aalts of ya¡rLoug aleobola (fil,ltanssn nethoil) r .t't" B - redl.oals . æ¡r3.oycdl : a noñr ll:y-å" i:þo-åo\G E* è-Hut -' 1vr) slaoe oaly fos¡ eÈhcfc of fluo¡ronc arc ¡recorôeô Ln t, fho 1lte¡ratuner. , Slaee oaly tro dlcrlvatlvês of fluoreoo3. (YII) r by rhlcb. lt utght be elasslfiedl , fêlo 3.Lstcd, lt ¡ls 1,,. eôrûslåêreô¿ of sose Latêrcst Èo s¡æüheetze aevc:ral of th.c .i. '..'.: ag:r€ €o@rì dtø¡dvaÈLves, aueh as thc rLt¡robcszoete, etc. (WII). ' i:tì i.i¡,r, ii:*'L-c¿1,¡-,úo¿ (wr) (vrrr) i,:..¿ I+FERATüBE snRYtr T. : Irr 1867 tarccl].ln Bertbolet (8) feolateil Èon the 3OO - 3fgo botl.tag f¡racÈlon of orrud.e e¡¡Èhraecae a fluoneseent bryrdÞooarbon aelttrg at Xl3o. Beoeuso lt fluoreseoê hc n¡ne4 It rl¡luo¡.caet. Itg I t¡fl¡otûre has bcea dcte:nfaeð tbrougb thc LavoetlgaÈ!.ons of FdtÈLg eadl Oato¡u.Eyer (22)r a¿r$ter (6)' aad, l,s sbor& t¡c ùbc prø¡laraüLoa of tbe ooultsüEd &on btpheryrl eud dl.etrlorglcth¿ac (1). l)''" Ê'c'|' G-- +¿Flcl 8* ry &e Eùm.eture of Flso¡tênc f.c Íeêleêtêat by (IX). Cr. Èlr €!': [*u]* (Ix) Fluorcae possesses aa aotlye uetÞylene grory fn the p poo!.!loa, løcatoð rt6ar tro ¡ratrrs of doubXy l.lakodl earbon atons. lhl.s aetLvity lae been c:pl'el,neù by tbø æðera eLcet:ronl.e thce¡t of, Gosg añat Ingolgat {251 aa çc1L ag by tbc oldler lhl'clc ir:: theort of tbe eÈb¡rl'crll.e boado flrls aetLve netsleac gr:.on¡r la (5) cv!.dleat Þy tts f,oraêtioa of â ôed.flÐ dcrlvatlvc rlttr ¡¡cÈaIl!.e soilù¡s ag reLl as rlt¡r ¡ocla¡¡lðe r lbc øyaÈihes!.s of f,lEô¡9cae dlc¡lvatf'veg bg,g bêêE aêeo$pl'tshc.l È,¡r tl1¡reet sêbsttttltloa La the noleoul-e f'tgelf or Lnd'íneefþ th¡rougb sonc LstcrEeålete o@ror¡aèc Dtneot nrolsar sEbõÈlËEfLôt¡ la thc boa¡cao rtngs e¡rpcarc to fol&pr ¿ êeffalte roulee. chì.ollac¡ bloalue ¡ af,t¡rle a¡rit astpbul.io aot ile rôaet f.a fJae 2 poaltl.o¡ eadl c¡têaåô{t sabet!'taÈf'ens lcad ùo tùe 2r7 osqrcuadls¡ lfhlg parÈLouf'tr reaeùlvlË¡r of tho 2r? Poslütoag I'g oLataedl to ba O¡¡c to tAo rupellon äl¡reeÈf.ve lt¡toPolttiles of thc pþryL gttoglt (p9). IÈ ls of süe ùrto¡rcgt th¡t substltuêaüa [u ùþô 2 poaltloa gfcatll¡ aotlvató tiho nsth¡r1eae g¡ory Ln Gbs $ poeLtl'or¡ ag notprtcdt by SohsLaslol. aEd Elð¡oit (56). pfnon (l#) f¡E postulateê übat, übta Lac¡reaaed aotlvtþ lalr aecour¡t f,or tbe oarclnogcnl,c AettvltÍ of ccrtata 2 substl.Èuücå f,luo¡rcaes. &e e¡|,åattoa pnød'uot af, f,tr¡ø"orla¡ fluorenoao (I)r l. l '''.:.::.:.. Cc [1.., ,'¡..':,'i;,. | '\q --r',-o cct Il(. /- (x) ii:ji:':..+i- ts a ogæn staFtLag naùcnL¡X f,on Ëhc prcparatfoa of ¡eay of, i;t;:''::'': tbc alnc cubstl'ttlËc¿l f,lus¡Eeaggr trta p e¡4,raüloa hag bcc¡l t&p iJìJ{"_1il1:5¿:i-ï*Ë:.ffrn^r.¡_1:i*-t{.":Í 9)i1:1r.r;iti}:-r.:i.í-iQì:i;; -,lji"'--:ia¡:r'.+ t'-r:;:::.Y".r't¡::e"}¿r (6) obJcet of stüdIr fo¡r Eå.qr reseå¡ch lo:rEcra o fbe siø¡l1esü arad uosË gaùicfaototTr of Ëtre Dånür varledt uethoda ls the oxldatloa sf flLuore¡rc by sodtlnao dìlebro¡aate ta rsüüla eoið (A9). $to advantage of thls uetbod Ll.eE ln the facù tbgt tcchntoel fluonene (98É) ca¡r be uaedl¡ the luryuntt!,es havLng uo cffeot otl the flnal ytelfu Wltle poteo al.rnr perraaaga¡ete solutlon ea the orf.df.ztng ageat, ütre yteX.d, ís le¡rorted to be aLnsEt quaatf,üettvc (L5).
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