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. wh BESTCOPYAVALABLE 56 ' Synthesis and Guracterization of bo-us-lee |RECEIVED December 28, 1978 || | LIoNtl ony Conducted at: CanodmmeRrickiearlLaCbhoeraaitcoarlisesD,iviIsnci.on 3St. Paul, Minnesota 55101 During: April 1979 co July, 1979 Synthesis Conducted by: FE. Behr SFpuerciitfyicDetAcetrimviintaytioanndbyR:adiochemical pasoct byt 3. D. Johnson and S. J. Gibson Z=]AC TA' ) FReEse.arcDherS,pechioadl.ist Dace Comercial chemicals Division HSCpheavcriafciitcersiAzcattiivointySeancdtioRnadiochemical SeniD.orJopkfPdtenhemsicianl sPharmY acoTlaotO egist Riker Laboratories, Inc. R~ ERa Jl.23]0c MRaCnaEgerO,berD,ughoHbe.tabolisn ate Riker Laboratories, Inc. CO2870 , on Summary Tishelsaybneltehde)s.is Tohfeasp2e0c.i0figc laocttiofvitFyC-w1a4s3-1d4eCterimsindeedscrtiobebde 0(.c3a0r7bon+yl0.0c0a5rbon uatCi/lmega.st 9R8a%diopucrhee;mictahle FpuCr-i1t4y3-14gCtewramsinaftoiunodn sshuoiwteadbletheforFCm-e1t4a3-b1o4lcismtosebuedies. Introduction wAFfaCrs-os1me4sr3yitnehsteahnedobsofidtyzeh.eexdpep"aroTnisodmseifncbathicsalirilatiictystaetborefeiizantefghdfeespecltaiennxngpeedrtihtmeoenritanstv,eescotfoigreabltoienm-it1nhaetlimaoebnetlaeobdfoliFFsCe-m-1lioi3fg-lic Figure 1 is described. . The synthetic pathway i1]ueteotod br A. Synthesis of re-143-'c I. Fractional Distillation of Cell Run, A-3265-8 cAcenolanlltyasidinrseadinbiyanbgogsuatswec1rh2er.o13dmraihteiodgghroavpbehoryiliasnnhghoywdemrdaotuetsrhieaKlFcse.lflo dThreaineirnoggse remove NE. TfFhoreractsdiiooslntisidlsl1 awteainroden.2rem(To3hv8re9e.de3 bygf)raf,citlwiteorrnaestiwocenormebtionceoyldileealcndtdedA.w3i4l(l0tabgbemisus1e)d. for the preparation of Cf Low,. 11. HFyrdornolRy-s3i2s65-a8nd Stabilization of Distilled Cell brainings eaIdqndutiiotpipaoend50w0fiutnmhlnelat,hmrececoehn-adnneeinccskaeelrd, sratoniudrnrde-trbh,eortmTtoormmuee-tdBeorrfelwaasskstwpilhraricecerhd.haastdhseenbgeieyn, macdiodxmeebddinestdoolucttehleilonfdlorafsakinNaitOnhRgrso,u(g6h8F.ra4a5c)ptiroenssasn|udrawenad-tee2qr,iuz3a(e86ld98..a34ddogif.tionwaAsfpunrnee-l ob9veethorwueres5n." m5i2An5futteeCrs. attheThae9rhmaoituxertusrurefefawicactsiioennhteattitemoed,keteotpherethpfeHl.uwxtaesm(8p5efroCan)tduroevro cb(oe2n5t7>e.n01t2s.m.l) TThahenedmi9fi6xn%taulrHeypSH0w,aswa(sc3o4o.<3le1dnl()tCoownag6so5Cardeddaenddpapaselrom)wi.lxytuTrtheoeotfhaecwiadFvilfeeirsekd m3tih5ex6t.ub7ro9ettwoams(f9hl1e.ua6o3treodcmahseasnticy8ai0lelCdp)hf:aosre 3w0asminsuetpeasr,atecdo.oledThetoyi6e5lCd. waned 11. T Fractional DistilrlaE etinonooffcG.hfibstoonM Tfflhaaeksek-a,opfpfaarahsetmaauldsl, cpaoancsckioesldtleedchteioaotfnedaasd5si0es0mtbimlllyl,atthi~ro7en8e-Cnceocclokulemdd, trprooauptn,d-tmbhaoegtrntmeoormmieseder, asrnatddiirorSaeucpretria-vsCeseelmfbllu(yo0,r.7ocah9n)edmiwacaasmleardc(du3er5dy6.7mtoang)ot,mheet9ed6r3i.scsiullTlfhaeutriibocansaecfcilsadtsak(n.1]2i.s0tehdenl), 02871 . BESTCO bbwaoetileloriwng4a0smpCaitreaatrtioa2rl0s0vawmcemuruevnacwruaeusmmo,vaeddjt.uhestedAdsistttiholel2ah0te0iaodmnmtwaeanmsdperctaohtneutrilenouweddrooppned aTnodwearnavlayczueudm b(y10g-a2s0 cmmh)r.omatForgarcatpihoyn.s werecol lected, weighed, rfThoeerfraapcentraicloeynnstiasteCdw7aFs)1s3CdOog,nivHee b(9ySe5ea.r0eTaabClFp)eesrCc1Oe1T)nH.t anFdractthieonass6aybhre0pogr.tedwoswas (see Table 111). 9F6r.a0c8ti%onCF3,|5C(O2,4H.)3 wge,re97c.o5%mbiC,fF1eL8d forHFu,seanidn pFrreapcatriaotnioAn o(f13F.4e-jg,is-lhc. IV. ApFnHrhaywcdatsrioounrssecNh3eHcaknewddas4afa(td3ed0re.d02u5n)htoiuwlresr.ethedTihpseHsowlsavlseudrrgyrienwaatFseCr-8f0itlhta(en9r0e8d.m,l).aTnhde sptorhleeipdaprreoadtduc6bt5yCpwauslfvoearriri1zihndogruire.tdhe iAanniartlhydesriihseodobdy.SoglaisdThceahnrdFoimndaartlyoignprgraopdhhuyeceshwoowsed sofnoollialdossws,ianyg20o.fL0n5u58;m.b8e8Lr-sUCSFBw)6e,?.eCOfS,rs0ashciytginoendaT:theedyLTC-e;ulFsdydosl,v0asHFc,-3110iN1o3-T5gi2rc5,43T:ha8e-o30, Fraction 4, 004 g. 8. Specific Activity Determination of Fe-143-''c wTie0hnrrteeo1e0 tpmhrslretepaweanirdtea1hdr0dnmbleystohwclaelunaitosgilsohniaAsnngdvdopflt1hi,Femee-1tF01rl.4ia33cs6-k1snF%elc;wa2eskr1(se1L.,-mUi2sxTB5ehs.de,38vbsyoneglesuimSneayvsmneirtwtheie1rns1egi1"sauSsjeoscrstteieotns)) TaColailqitubhorrteasetedooffmetiahccehrvoispaolilsupteciootnnttoadwirienrsrietencgtluys1e0dIunlttooalasilcqiiuqnouttoistllaasntidixont1o0cotpiuhrnetaeinnggco5bny1stixaahiia8enn0sign.5g1 o5f0 Aulquaalsioqluotswefrreomadcdaecdh. Tphreimarreymaisnoilnugtiovni,als1 mwlereofpwraetpearredandwit1h5 m31.5 mi ScotfoceuimnnmptteeeitrdhlaaltnautortwleioonatanniddnSepsea7cl.tal5rtoowmmle5edtmoeiftrno.uMteTeSqsSuTShi.eelaicbchroTauhtnweetiitshnaigmnapeltfePhfseaicckdwiaaeerrrdnkecyMbcoeodwfoeaolrsreedd33ett8tho5ee.ryrLme)iwfqnerueridegderfoartor eraecdhucesdamptloedpbym atnhde are shown in Table hti.hneteTurhCnaeil/mogvsetrwaaanlsdlarcdaavlemcreuatlghaeotde.dspefcToirhfeiecaacvhearcatvigiavelid.tydaTrbheaeseedderreoen mtehaen 36uCir/enpglicfaotuensd the overall mean. f(To1hr2eefamrceoahmnsoefacbhetthweweeeipngrhiiAmnaqgru)yaswowealisgha0in.nd5g0sN7TSw+Sas0w.ew0r1ie2thwiuinCtih/1in.ng8.%0o.f1T2h%e, and the means between 10 ul and 50 ul aliquots were within 2.0%. 2 Riker Isotope Number 453. bWaeliagnhciengwshiwcehrehaadccobmeepnlisrheecdentolnyaca5l-iplbarcaetedMetbytle3rh MHehtroelloegcyt.ronic L/1 Hicropipettor, Lab Industries, Berkeley, CA. 2 New England Nuclear, Boston, Mass. Modified T55:25.2 5 1.01 g Dimethyl POPOP and 3.8 liters toluene. COR872 C. Radiochenical Purity Analysis of Fe-iz-'ic + Thin-Layer Chromatoaraphy Systems and Carbon-14 Analysis TooaffaSktehcgniinay-lolyraeeyiesrrooufstyisrnteeedlmiysachdueesnviienclgaolpSeGdFpur2ini50ty1m0iwcasrxonc1a24rprrexiesdocroorutethdinUweintijhpasleaatevsar.iety CTItuana2.sn%0tk5:o%5smmcwFaneidrtewetieddtaeelmlwpoislwteaghetmdeegnlttaoasns.dsdevleTihldeospascn1rd5apc|ininngaendwdawsiwetrahec.csoasctmruparrpaoetndieodnracopeairdsss!h.iVy TgLoool)lSxheaeccttemldeytihn0a.n5soc,licnmt7wi.il5dltamhti.ioonfsThvhMaieIraSplsSescnrewcadaopsensdttaaisininillniegcsas2.gs5etlemeilseogsfmpeanmtteucslhsawmogerrsee.und sbgcaorcuaknpoteredodunfadrnodnustbiheneglocwaountsthuseitoaprbeilrgeimnbilnoaunntketh((ecupsapmudl)adaletwldeye.rbetewTiochnoe0r.rs5eactcmenednsefoucrnoenmts SSipcmh wesreeamennotl plate: wcaosrreecxtperdessfeodr aesffipceirecnecnyt. ofThteoctaalrbgcoaanrsbs1osany|ce-bodn)eteentcthreoe.f TncopFm ocnp_soegnnenets x 100 = % carbon-14 content i; nsegnent. sSThphegomweipnnetgrcentnuhntebercr.aadribooanThc-it1si4vipctroyonvtpieednaetkdsofacoterahrciehns-plsoaenygdenirenngt component wraasdiopclhortetnesdtovpeernssus fo sepmcasey s in the material applied to the plote. !1- SoR slouluta tiioondUsUsei eddffooorr c Radih ocheemicaml PPui urrittyc yAnAa naallyysl sis ph3jla9oac0oci,io72n1ng1u0t3.i00o.n39mlumsgecldaosftsoFACs-tv1ro4el3au-km1e4tthrei(ctRihkFielnra-slkaI,y3eoartdojppuelsattIiennsgv.ewnatsotrhyprNveupomarbreeesrd by 459) eOaFchthipslatsweoi.ltuhtimoenthawansol,appalnidedmixiinnag nbayrrhoanwdfobuyr ionnverrtoinngg.str`obnitreLoLoyo 111. RResueltssaanndudDiDlsisccutussssison TYbShnyieanscSbreyeenlstteuhhdleetssiFcshCoe-fm1ai1nc3dtahlewgaassidcneohntrtoicmtoay-tcoohgfrroatmphahetyoFgC(r-sae1pe4h3es-de1c4wtCiitoihns Aw.ellthiessrteasbglries)h,e the Feo1hg The) gTpoppaeren3t aonnd orems did nPiolntatFeirgeNsuourrlenavsbdeeir2o-tc6h2h.iesm(iFcAiaglusrmeaplul3r)i.taymoTuahnntealoyotsfhiesirmaprfueoruirtsytsoa(w+lv3ie5ns) was SbdhadyseoinmstaitofofygrgtaahpsehycI,hmrpotuhmr.aittoyrgardfaiopouchnhydemo(insicemaPcplltuiaroptinutery.iAu.tmybtNeohofrisart2e.tpemopbrtet)ewraasanldsaedteehintne-o.elayer 98%. The FC-143-c is suitable formetabol Ffoomtisso.udicUes.is me Teale 2 2 Analtech, 75 Supelco Inc. Blue Hen Dri Bellefonte, ve, Newark,Delaware. Fennsylvania. 02873 Acknowledgenent dTtohhneeeacuabtyrhbooMrrn.s-14TgordaldtaebMfealuteldhliysceealnclkonfdorwalCioenmdimgneegrscti,haelfrgCaashcetmiciohcnraaoltmseadtDoiagvcriiasdpi,hoinac.ndanTaFhlCey-s1ai4us3t-h1oo4frcs gHeraadtreifcukllyduraicnkgnowtlheedgeelectthreocahsesmiisctaalnceFlouforJionhantioCn. oHfansleanbeiaendd CLoar3ry00G.. COR874 - List of sable and rigures Table 1 Data from One Plate Distillation of Cell Fun R-3265-5. NB 50942 p. 53 . Sable 2: DB ata frome Fractional Distiliasion of Cytlog. Taste 3: Date for Refractionasion of G6, 30. NB 52343 p..8 Tig Table 4: Seon Specific pan: Activity Determination of FC-143-1%c. Table 5: Thin-layer Chromatography Systems for FC-143- %c. NB 51807 p. 35. Figure 1: Pathway for Synthesis of rc-143-Yc. NB 52343 p.4, 5, 6, 8, 9. Figuse 2: Thine-iearye.s fadiochromatogran, Plate i. Figure 3: TSoin7-tay5er Raadioc3h5:rosatosran, Plate 2. Figuce 4: TaaiSnieaayyes.taTdshoc:hzomatogran, Plate 3. Figuze 5: ThinE-ieaye.r Radiochzonatosran, Place 4. Figuce 6: Tphin-r iayesatadiochromacogran, Plate 5. COR87S -- Tate 1 Data trom One Plate Distillation of Cell Run, K-3265-3 Assay Gic (area Percent) m--_--_o-- m we wers! 8 T oon.ece m? Tcoeme"r TmeTse 1 es ase ss mer ses 10.20 0 2 sos ama a2 ees 25.50 0 soso oma - nan 00.87 17.6 soteons 2a Hostly High Boilers ---------------------------------------------- # 15's Hlonbotlers -- unidentified bue wich retention tines < GF, Ci: Cg cylic other = various perfluorsbucyltecrahydrofuraus and isomers. a's inacerials boiling higher than CF, (COF. C02876 "he Table 2 Daca from Fractional Distillation of C,F, Co Bx bpo2C WI(g) FE ETa 2 35-40 103.6 3 2647 om) 2.4 4 ss-101 2.1 5 101-103 1.2 6 06-109 (7mm) dio Inerts 99.98 2.18 597 -- -- [3ZAFas1vs1aCey0o7n CgF13C0pH -9.41 13.19 15.85 5.19 F750150! -87.9 79.8 78.8 90.3 GLC analysis of FR #6 showed about 3.9% high boiling materials . CORE77? E --_-- e) 1 en 0) 2 nas 3 ne "oe Ww -- rable 3 Data for Refractionasion of CF,Lou YiTeldT(8)F 1s 3.7 2%.3 13.4 "2.9 (1 Assay (Area 3) OC7sFy5o00,H3 89.03 97.26 97.5 96.08 Assay for input Co refractionation was 94.35% CF)CON analyzed as CF) sCO,CH | -_-- CO2878 _ BEST COPY AVA Specific Activity betermination of FC-1643-19 Solution 1 10.5S6em3/10.0m1 G00.:i458s837 0G0.35i00s6%t1 ooi:iseiAa 0p0:5e:3i30]78 :35850.0124 Solution 11 25.2T808h/10.081 000:.:54239959 030..333005006687 H003:e53%3 o00::3331116600 3i65.0.0110 Sotucton 111 f20.0t6m5o/10.m081 oo0i.ii4d5ed6s6 0G6:r35i00e08s7 GP0:ie5s1t io03i0es% 3:3858:0.0056 Comparison of Scintillation Solvents ar Aquaso1 0o0::.3440s808n7 00033:1133270s 0G0:r:5i3n93s eo0:ee35 O00irsiiose%ass ao0i.ii30i61 0.50740.0137 MwIiSrS a0oi.si5os0t6r1 0o0:3e:%0s53 000.3:3300600)6 00053:1330960 o:0.3e5o0r80e 005.e05s80t88 0.5068+0.0093 Goparisen of 1041 and 50u1 Aliquots i 10ul o5G..4i3a08s%7 o0o.ls3is0st8y1 000.333239605s78 300:::33030868 O0Filiisenzas eoGiiiires 0.502120.0109 vm 50u1 oo0.i5s1s2 S00i3.d03e75s60 F00::e33 Fo0e:ee3s1 o0Gl:si3de0e 00G..4i5500s35 0.512120.0101 Overall average = 0.5071:0.01154Ci/mg . 02879 To Thin-Layer Chromatography Systems forre-143-Y4 nn ee TE + 100 acetone 0.03 2 acetic acids 5 ammonium hydroxideS - nn 2 Solvents were prepared volume:volume; a 100 ml aliquot of solvent mixture t 1s of major (-:98%) pesk on the chin-layer chromatography place. Acetic acid and ammonium hydroxide were concentrated. COZ830 v Figure 1 BESTTCCODPY Ava 4p. Pathway for Synthesis of FC-143-Yc ny to:ct BErE. PPraetphafriendderby Laboratories rd C7F15COF one-rlate Distillation T+ Noon BPulge;ss 1 FractLions al IT + Ny Fe e-80 ns cp,so2 r 3256-3 2 C7F11 5COF C7F115020,1 Refractionation wm b+o,cor, Fo-143-14cd >CyoFsyszto 1m Assay #-Denotes position of Carbon-1 * re-143-Y, Amoniun perfluorooctancate COR881 ,. 90 os 0 7 0 es 6 Loss EI Eu fw FEE ix a 0 15 10 5 o LE i Figure 2 BESTCOPY AVA ABLE Te top mseerin of SG Uniplaces 190 chlorarurn Total CP on Place = 99,892 EE Distance from origin (@ COR882 " " Zw iow Ew 0 . - Fe-143-14c, Plate No. 2 BEST COAVAPBYLE see, scm ori (cM) COR883 6 " = 40 3 ow FEY . . Fe-143-14, Plate No. 3 BEST COPY Aishuii. (a) COR884 sigu5r BESTCOPY A4ii hate Thinlayer adiochronatopean of #C-143-14, plate No. 4 " SOF Uniplate: 13300 cmehtlhoornootrars 5 Semonim bydronide 0 Total Ch on Place = 105,567 Fr Zw & HE 0 o 1 * 3 {3 7353 TLE LTD biscance trom Origen (an CO2885 paus6e P[E restr -- ea-- ts w so SGF Uniplate: 10f0s mCoholmoersonftorhmparonia i. otal can on Pl=a10c7.1e20 iw : & 20 " . C1: 3 4 567 53mm omen sistance@teem origin COR886