Document 8VJpZGRweY3nQedqDXDopy6Qo

VcUS niMHtOCAUHONK ANI> Utl.OROIIYI>ltOCAMK)NS SI. IV. J. Ikm-.r, J. M. /W. II, n-WfltU). X,. V- M. Il,.,'.rtl.,(CIV, MM, Dwlrty Dyw* iui.I Unlmriata, llnellnnl, York- Miinr, l!iil,<<<i|it>lwnret, IIW. . -. 24. Uni. I*i. SMl,)!.)<Jan#to, IIW'). X- Iwll and IV. C. dprent (to Imperial Ckamia*l lade*, trtvft 144.). ' 27. r.n. I*l. 1,4.17,1X1 (Oct. IS, IMS), A. (Invar (t* MrlMrem Alkali Wvriu). UAht l,.WM4ll(Jiil|f, im K. K. HUvMWk (to MaUiimM Alkali Wurka), Vi. Uar.Pkt.SM,SW<IMP)(lnailiarlwAiiilkf<Hi<ISila-VabrikA.a.). H. 8101 , Hoyden Newport Chemical Corporation CHLORINATED BIPHENYL AND RELATED COMPOUNDS j Diphenyl (diphenyl), liTjilionylr, hixlT poiyphntiylr, or mixture* of the** eom- j*.'i 'ihN rau l* clitoriiiatnl to *iv product* which liav* ouMandinx chemical and tiwrmtil MuliilitirK. Individual iromrra, which ruiRO front liquid* to htgb-meltbic ciyri.dlina aollde, are of litllo nmiinnmial Imporlanro wlirrea* the mixed chlorinated nii.-jXMieitl* have aimhleraUe OMiimerelal rixniCcanre. HrxiMen.il tr.iriinnark* for mine eonunereial Irani* of ehlorinated biphenyl* in the United Elate* are the fnlkiwing: Aroeior (Monaanto Company), Cbiorextol (MlivChalmrra Maoufaetnrinx Company), Dykanol (ComelMJul>ilier Divmion, Federal I'acifi* Klretrie Company), locrtam (Weatinxhouae Electric Corporation), Xoilnmol (Wagner Electric Corporation), Pyranol (Gcneial Elcetrie Company), ai.d llicnninoi (Monaanto Company). 8oine other regiatered trademark* or trad* name* tor cemmereial chlorinated biphenyl* found throughout the world are the following: Ctophen (1.0. Ferbeuinduetri* A.O., Germany), Fonelor (Caffaro, Italy), Kaiuicchlor (K-c*x/uehi Chemical Co., Japan), Pyralcna (Prodelee, France), and Sovol (Ruaaia), .. Commercial manufacture of the Aroeior brand of chlorinated biphenyl* wa* atartrd in 1939. The** product* vary from mobile oily liquide to white eryatailin* i'.lid* aud hard noneiyatalUne rcaiaa. Bomuae of the many form* and propertiee, il. -y Imre found application* in many diver** field*--in elaetriaal inaulation, Saw i">i tout Itani-lnuiafor and hydmuR* fluid*, hibrleant* for um at high temperature** . *) pnwMirae, aanlant and caponaion media, ami *a eouatituant* in ebmtometa, ad* lie.vvre, painta, Inequaru, rarniehca, pignumt*,'and rraaoa Pbyaical and Chemical Prapertlaa Hi* pliyuleal propertio* of indfvidoal ehtorebiphenyl iaomere vary widely a* may be aeon hi Table I. Mixed laometa a* produced in a commercial product have phyaicat property* which are cgaiHa dWcrant from thorn of the Individual Iaomere. Thi* i* particilarly true tor the aoOdlfleation point. Chlorinated biphenyl*, In general, are eonaklerod to bo inert material*, How ever, they will react with certain reagent* when treated under rather rigoroua condi tion*. For example, ehlorolilphenyl* wM raaet with aodlum hydroxtdo at elevated teniperetorea to yield phenolie matarialo (99). Mixture* of chlorinated biphenpia, ewril aa thorn bund in eommerelal product*, will not raaet with acid*, alkali**, or wmel trader normal to modaratoly rigoreoa *ondhlam09). Thay artlnooiubi* in arafor, glycerol, and too glyeela. The oil* and / / moas 076076 _____ I . 2M ('IIIAUUCAKUONH ANt> UlUHtOllYOHOCAKBONS win* am readily rehilrfe in mart of the enmroon organic relvent*, Imt meat of the hank rryatalthm aremlim are tree rehiblc than tint liquida or wider room. The chlorinated biphenyl inixturee are nohdrying even when cxpoanl to air in thin Dime. They are permanently thmnopiaatle and except Tor the tower chlorinated luemhcre are nonflammable. The raxina will adhere elrongly to amooth (urfaooe web a glean, natal, vantUiad or lacquered anrfaeaa. Moat of the eotnmon matah and alloya / TaUa I. Fhgdaal Pkapartiea f CMemMalnnrle / Ciwp--4 / lldtfaw jmfel, *C tiuiiinft jutbitp OWhjajrehy *Cimm llg) 3>rWkwwbi|itirigr1 / WhVwitijrfwiiyi / 3t3'>iirMnn4iitlMlli)rl / Ppa*re|trMnalilillllljrl / g^HirMtafliMnlirwjrl 3,4dlirMMn4iiiihm)i SeMirMnmli^iaiiirl toneliitiliiiayt 2,4,MrirM<ir*Mptonyl iMpinyl . lAt'-ufrMeniWelimrl O<rAVfO# UaiaUrexJ^Mel ur-MdiMbioei l.tJ'.t'HetnwWweWptoeirt M,3*,i'wtyiirhi>wlii|ilwm^. X>,.V-ftn*iliUa>il|>lwwyl 34i3'.4`4nrarMM<iMpl<aayl trtnwlilewhlplireyl %i,:tXA' pwuililmililfiliiiyl 3,4,ft,yt4^'4>rmfMoniliiplri>yl 2,4,0,?*,4 ,fA,4iMarMHftM(4aigrl 34 m n&,n,u . SI! 1M to 40;4two * .. 44 T0-7t 41 1441 07 M : u-n Cl in in * 108 in II M-e - in -m iii.*-n WAe.t'.aW.a'-WeHiliirnMplimet in no 207-9IM; 104 (It) 3K4-SI3 180(14) 083-324; 380-31C its-oia 100(10) in (is ire () 100-000(1/1) ' 171(10) W(M) na-nono) 346-Mn(*>) (1-0) (Ml <w> (Ml (0-1*) (Ui (I1.H) (14,1*) (II7) () (lhlO) (10) (Ml (0,111) Ml) (M) (33) (U) (11.11) . (31) (> (M) (11.14) () (Kbit) (13) Wl) l> () () / have excellent raaietanee to tha chlorinated biphenyla even at elevated temperaturea. However, copperand aotna copper alloyaare effected to a limited extent and allow pane- tration retea between 0.0014 and 0.014 la./yr. Many plaatie matariah of eonatrwtloa are attacked by chlorinated biphenyla. In addition to high waiatoneo to thermal degndation, they ahu have many intorenting electrical prepertiaa. 'Dm general prepertiea of the mere Important membara of tha Araektr bread of uUnrinatotl hiphanyl preduato are abeam In Tabio 3 and the alaatrleal prepartiaa are abewa in Table I. . .' ./ MOMS Q76b77 Vri. S TaV: I Gti^ra' frfrtiw tf S .WUi QILOKOCAUBONS AND CULOKOIlYDItOCAttOOXS MArial WttmmAmkg *C{mn) FUi Fm P*C PoKf <"C C Utraiai P**C c rlttf MHaNhA9 l.IXM.Mt 379-0)0 I4I-UI (JVU4*O AmWBtt Ait mhrt-. 1.3PM.3S UHM rXStt ia ovtt.s*o 13W-10M m-ioo MUa <svu.**C) Aimd<rttyA-g--tiild, I.A-UU MS ioo-im AmAtIOU MtM MrOR 4mwm ICA*HatjyArd,nabt.6*rim*m MvyAt*avrta*mdbM.*fe*ay, <(I1.0.S450/Sl/31t--1*Mi.55**I00S01 (UOOM/U..SMO <I.S0W/U-.15.UOI imtirBO tMiu*arjiyto Il.WOM-Cl.O)OS ois-ioo MMN W-4K <a 480-M0 Audit 4Ui tadk3M3 tefciw A--Artill ytfrfAaubfeiitrfv>nfiAy,u,mtOhjimria--miir^u^cmpiyb.tAnnwpbg.t,, Uakctka.hrM|Mig, m<(tSVf/1t11*/*...00S4*KS7*C00C0))) aavi/1t.7r*3cc4)i ((4O0W4MMm-40OIS9UOS0S)i) ((MiBc) 017 ITS pbbat 1*C 1.017-1.St* i^as-i.aa I.M7-1.M -7 l.OW-I.CSt 10 1.00-1.011 ot I.MM.M UNW.W7 tM-mr V MMO* >S90 SO-tflS.S OS-71 3l.lt*C 4I A.fC tl 44-K 70-70 00-170 (WO tfTM MO(waOOii). ICMA 'AIIMOtt. /8vMt0aM,4SnX ML *LMftm44tai hdkakn m tm pofet ^ to boflmg ln>ynitiiw. 4 ASTM" D-$7. hitetMA ewrtwlt h, Inttor Ifll wirtii-- Art 01% (Uoriw.* s MONS 0 7 6 4 7 8 / A numlsv oflhe pirn rnnipnumb formed Iqr Umi chlorination of liiphmjrl, Uo phnnyl, or nsire emuplrx pulyphenyte art crystalline anlhU, mum of which have v#ry high inciting iminta (-10). llowavar, Mixturai containing a number of with eompoundn may ho either liquida or noncijfitollhio naino. Chlorination of aromatic hydro* rariiono to varhmo hnroh oat only gives ctnmrai hmamo of the mmo chlorine contoot hut aim |ivti opproeiablo portiano of the Iminera of sompoundo of higher and lower chlorine tontmlt (11,32). At any lorol of ehlorine aontont, hatch chlnriiinticn gives Um highest proportion of compounds eorraepondiug in composition to the average elilorino content, whereas single'ilego continuous chlorination gives the lowest pro portion of snrh oompminde. As the number of stones is inemened, mnltialans can* tiininus clilorinstiou gives enmpoaitisos approaching these ohtaiood by beteh chid* rinuiioa. Tho proportion of the various bomcr* and of sompoundsof higher and lower cldorine contents than tho avrregs Is alco influansod by factors sush so temperature, i|ur.utity and kind of catalyst stwplsysd, degree and typo of agitation, sod rats of luhnhthui of the chlorine. . A pmeedura for carrying out a cingisntcge Kuid-bed chlorination is described la Um potent literature for potyehlorinatisn of biphenyl (33). Continuous liquid shim ' rinotlon to a multiplestage unit can also Iw used. Batch dilorinatian has been found to 1st particularly wall suited for the manufacture of tho various products (33,34). Tho ehloriuatam may In cylindrical steel towers, 3 ft In diameter and IS It high, which am rquippad with ehkirine diatributon at tho bottom and with eoila for heating ami moling tin material undergoing maetioa. I"umps provide agitation by circulating the liquid ohwga Tho Inwar half of tho ddoriuaton it flOod with iron tamings, which have Inoa inirtnd free of oif and ambitum. In Oorwum pmetiea, tho Ohioring tom am agitated 10,000-lilcr lead-iloed vessels. and ferrie chloride fo mod as tho eotsiyet lasund of in* turning*; IWtooa kg of ferric chloride a ueod for cosh chcrgi of C000 kg (36) ef biphenyl/ . * / MCNS 076429 VoLS CHLOROCARBON8 AND CHLOKOHYDKOCABBOXS Jtt Kaw Material*. Tha raw malarial toad depend* on tlie type of chlorinated material to l pnaiucad; auhytlmu* ehlnrlna ia naed a* tin- chlorinating agent in all nan. In gnirml, it can In mM llwt hiphupyi nliHir give* ti|iikl or null, nUcky noo- rtyrtallinc product* np to a rhtnrina natml of 00%, iow-mt4ling rmiumin product* between IB ami 03% chlorine rontent, and partly cryatolliim nr cryatalline produeta - nf nuieh higher meltlap pointa at chlorine oontanU above ttt% (02). tn tire aaao at'' producta that arc aolid at onlinnry tampoiMuraa, tha higltar tha proportion of tor* phenyl* or mom mntplax pnlypitenyU In tha mixture before ehloriimtion, tlm higlwr tha aaftniing paint and the Inai tha eryatalHxlng towlency of tha chlorinated produet aftrr dirtillation. Vor thoao ptnduMa that are aolid or portly eryatallina at loom temperature, tire higher lire chlorine content, tha Maher tho aofloning point, and the greater tha tcmlroey of the nralttinl to eryrtalUao (34). Preparation af Crhde Chlerlnatad Biphenyl. For tlw manufacture of any (lean grad* of chlwhiatad hiphanyl, the chlarlnator ia charged witli tha proper m material / or mixture of rata matrrlala to give the denired product in an anuntnt Mdlieieiit to/ auveriltrealnlyal Itetl and Ur permit idmulalhm. 'Dint tho (low of vapnriard elilorm* I* Martial and tha eltarga ia ehaulated with the pump. Throughout tlw Hdorination, tho temperature i* kept wail aim** tha malting point of the mixturo, but below 1!S0*C, to avoid exnoahm auldintallon aud phtgging of the line tlimharging tlw hydrogen ehhrrbl* prudurod lip tlw nhlorinatian. Sample* are withdrawn for examination from lima to limn until Urn dmiml chlorine content he* been cmrhcd. At the loweroMorine content*, apndlle gravity nwaanramanbt am taken trains a hydrometer to dotamdrw < the cmnpooMioo. After the pradnet haa hacotno tea viaouua or haa roaobad tea high melting point for eeuvmieat datarminaUon at tha apeeiRe gravity at bimpetaluna latlaw |tm*C, tlw degron of chlorination hi datermiuod by nwaauring tlw held point mi tha material crystalliar*, or lry the halhandwing anfteuing-point trad (38).. Tha time required fur chlorination 1a 12 to M hr, doprading upon tlw chlorine aentontaf ' the product. The anhydmux hydrogen chloride, which is ovoivad during tha chlorine- lioue, ia atworfaad in wntar in equipment of conventional darign. DhdlUaliaa af Oudt Prodada. AHhangh tha crude produeta find coma appttew- tioa*, (or moat pntpoaaa further puriAcatioa la naaemary to remove the color, and tha Warm of hydrogen elderkiu and ferric ddbrida ()3^t,3A). The metheihi of purification - am amwahat different far the different typm of and produeta. The higlwneUing *u!U product* am difficult to dhrtUL DIMIllation uuder nduocd praaauro ia partleubirly dUliauit aa it ia dcairabio to heap tha baBing point above tha aolklifieaiion point Generally, them praduat* am diatBed In pea dead retort* nt atowaptuvU pmaaum. Tho dhttilbdo ia flaked an chilled rolli. From practical coraMerationa of quality and better overall prooowiog efficiency, tha liquid and mainoua product* am diatfllod at lower temprratum* hi own conventional equipment under reduced prcacum. The crtnlc liquid and rmhtatM produeta on held at an elevated Uxupcratum and blown `(hh dry air foraevatal hour*, after which wfaw tenth* of 1% of limeorindium hydro*, kht i* atirred with the material to moot with any remaining hydrogen ehlorklo or ferric Marti*. Thl* la hillowad by batch dkdfllatloo under reduced peamuro. Oomplct* dMHatinn and mixing af tlw libffllato ia naaamary lo order to obtain uniform material f thadevirad aampeeMan. ' .' . If iarrauad alaatrleal maitthrUy la drairad, tha malarial la atimod at aa ahvalad tomparatara pftpi af wall drlad fuller'a aartk and than Uttered' . / / / HQhS 076460 M CHLOKOCAUllONS AND CHLOROHYDROCAJUION8 Containers and Shipping ' TV h,,uid chlmin.itiil hiphrnyl* nre pnekrd mill chipped in galvaniaod-strel ur in lank ciui niiiMlmnliil of nounintiug mctnia Midi as aluminum or lin- <jaicJ ;.a! al, 'Hie icxiii'His products aw paekod ami shipprxi in open-top galvanised* .1 Ji ami tlic high-melting solid products are packed and shipped in bans. " : rail.nail shipping classification is llctin Synlhctio NOIBN, ' t Health and Safety Factors iWiiv'! exposure tv chlorinated biphenyl vapor ovulvrd at high tea um lead In synti-inic toxic clfocta. Inhalation teats on animals indicate maximum safe coiirmtiatinn of vapor is in the range of 0.S to 1.0 mu of r im.iinal' il Iiiplnuyl mixture* par eubi* nurtur of air. The thrcslHiid limi mon attonalito conccnlrntimi for an eight-hour working day) sot hy tho Ojiifi icKC of Governmental Industrial Hygienists are 1.0 mg of the lower ewontt- II I! biphenyl compounds (42% chlorine) per oubic meter of air and 0.5 nig of the inure highly chlorinated biphenyl compounds (54% ehlorlno) per euhls motor of,air. When chlorinated biphenyl compounds are uaod at elevated toinporatures, engineering ,. control* must tic applied, cither by the use of dosed systems or by effective isoal mechanical exhaust ventilation togothtr with general workroom exhaust. Although (lie chlorinated biphenyls are not normally akin Irritants, thair solvent notion aoh remove not oral protective oils aod fata, and load to drying and eraoking of tho skin. Alto, continuous or repeated ekin contact with chlorinated biphenyls should ho avoided because of the possible occutTooeo of o condition called * (28). ; '. * * * Klcetrical Applications. All of tho usee of the chlorinated biphenyls depond on their cheoiieul stability ami Uidr physical properties, whieh may lie varied to suit tho vec ific application. One very important uao it M dicloctrie madiumx in aueh appiioa- lini.s as fluids for transformersudat impregiuuitt for eapociton and eondonaars (2B, ft). Chlorinated biphenyls, used cither alono or in tdends with othrr ino- c-iii>s such as trichlorobciucno, mast the nsed for a fire-resistant diolcctrie fluid with > resistivity, s high dfcdoctrio atrength, a rdativdy high didoelris constant, and a very luw power factor. By replacing hydrocarbon oil with chlorinated biphenyls nr mixfvmn of chlorinated biphenyls with triehlorobonscna, it has been poaaibia to i , dc -lhi. equipment with n greet reduction in sise for tho seme copoeity and voltage. A t the same time, the firs hasards have boon eliminated. Baa also Dielectrics and pi.vocli'ctrirx; Insulation, ctoctrieai. / Th,, maximum dielectric eonsUat of commercial chlorinated biphonyl mixtures xt 1000 eyelet and 25*C Is approxiniatciy 0.0. In recent years, oonahierablo attantian has ticca g>vn to upgrading this property (45-40). Combinations of fractional. distillation, chlorination, and Isomoriaation can bo used to obtain dielectric constants ,f 7.0 nr slightly above. Direct qmthorie of specific trlcblorobiphonyl Isomers con I - niittrfd to obtain dielectric Constanta in the order of 10 (40). Improved onolytlool ' .i.pn s, primarily capillary gas chromatography (50), have bean of greet aid in . lying tbo complex chloroblphanyl mixtures. . HONS 076481 VW.fi ClILOKOCAUUONS AND CHUMIOIIYHHOCAIIUONS 295 Other impurtanl rlrctrirnl appHralkma for the rldnriiuilrd hiphniyk) am ae hnpivgnnnis inr mllan or ia)nlw4ilin iisniUlsni (.11), na roust'ilniiil* of asphult- laMV wmMniptvgnaling cnniponmis, ami M pbodk'ixcrs in wire-nsiting mmpumsU, particularly tlswo containing nroptrnr, rubber, or mnnhhislinm a( pnlyvhiyl chloride, elhyirrUulorr, and polyvinyl bulyrnl (MrSS). Abo, chlorinated biphenyU are em ployed es ending medium* (or dretrieal insulators and aa impretpiaata for carlmn rsskuoe* lo reduce the influenen of moiatura. rustic*, 1-vequers, Paints, and Varnishes. Chlorinated biplionyla are compatible with mod ot the common plaatio materials and teaim, and am eoiuhlo in paint and varnish oils (30). In conddnalkm with asphalt, othylerituliioo, ehlorinatod robber, llfcdile (styrene-butadiene copolymer), or other pkwlie materials, they an waal *- tinmvdy in protective nailing* for wmal, nwlnl, aud mnwreto (:I8,'WI,II7). In com- hinaliun with dwclyl plitliukile, they am eupUsUciism for polyvinyl chloridecompo- sitiuns CIMr'Ih). the also Omliitios imliwtrial; Paint. In pninia ami vamisbn* the lutitl resinous ddnrinalrd Uplienyb am uacil to impart Incrtwcd liardnew to llm films, and the softer rnalii* are used to give Ihrxi- bility. Tire role of them material* i* similar lo that of tlie oil, except that they do not osMiie and lose flexibility on egoing. In nitrocellulose lacquers, chlorinated M- phenyls am employed either stone or Isa combination with otlwr plasticiser* and main* to impart increased weather resistance, luster, adhesion, and deereaaed burning rata (J7 40). The hard, while, crystalUno chlorinated biphenyls of high mailing point an useful s > pigments with various plasties (61). Adhoaires (qv). The resinous produets are used in synthetic adhesive come positions in combination with aueh baa* materials a* polyvinyl acetate, ethyleellulciae, ehlerinaltd rubber, polyviuyl butyral, isepwne styrene copolymer, and polyiso- butyUrc. Chlorinated biphenyU ate used bt the preparation of Boatings of pressure nipturshlr cnpeules for adhesive tap* (OS). / ImbrUanU (qv). Chloriiiahd biphenyU ind applieation as lubricants rntder extrema lun lilion* aueh a* highly oxidising osodiliuns, high temperatures, extreme pcrwsirr.<, nr submerged location*. Mixturv* with other oil* to form heavier-than- waler liil'ricnnl* are used in submerged location*, *uel> a* bridge rollers. / Lubricant* for extreme pressures arc mad* by adding up to 1#% of the chlnrin*ud biphenyls to petroleum hydroeartxm oils, ' Ilcsl-l russfer Media (qv). Chlorinated biplraiyls hnvs hesn want for some time in indirect beating applications (bit). Hoeontly, product! of tide type sold by Mon- sacto i.'ompuiiy under Die registered undomaek Tbcnuinol hove boso iotnalueed, whieii ora opoeiAesily directed to use sa haoMmnefcr media (fit). These fluids art particularly wed suilad for efficient and snfe operation in applieation* Involving flaumiiiU.i i.ialwriab where uniform temperatures are rutpiiiud amid for high-Umporo- turn (liulk temperatures of IM)*P) indirect beating. Hpecifieally doeigned unite for curb appHotkme are rei|iiirad to prevent local overheating! MiserlUnootm A*pUcallous. Carnauha wax may bo extended by Mending with ithUrinsirri hiplumyl in combination with Sereda and paraffin (20,1111). HatUfaetoiy waxes and i/.linlms am prepared without lb* ua* of earnaubawax by blending ourleury (liruri) wsx with ehktrinnied Ididienyl, oereain, and paraffin. Chlorinated Idphenyb are tnqnxbvnta of many flre-rasletaat compceltioiis. Klre-ratanllng palate usually eeataln antimony oxids or barium suVata in addition to the chlorinated biphenyl. In making fireproof fibarboaid, emulsified chlorinated biphenyl hr added to the fiber - / / 7 MQNS 076482 2M CHLOKOCAHUONK AND ClILOUOIlYUltOCAlUIOKB Mark (iW). MndifyinK wan* an alM In rliluriimtaTlMiibmiyt iu llw praparaikm at trxtilr-rmMinK innlrriala. In mklil Inn U* llw uarn limnd nlniro, ahbiriiuUrd liiplMujrb ora inKreUirnU *d "who araling mmpmiiid* fur hot with wood nr ranvan l *ivn pmunlitm mmiwt nadatare, rniUmr, or attarka u( orpuiwin*. They are nlan uarel in funmilatlng ralkinn cowpounda, pnirdcrai matal pnln, mH aoU-pobon and woud-preaorviim eompaaitioiia, paper traneparauliaore, and palatine Inina Carhonlcaa reproducing paper ia made by an anrapaalatioa preeadnra wldeh mm ohiorlnated blphooyt aa part of the formula tion (07) (bn EacapaulaUon). feibliefraphj ' "CW-ainalnl IMtdaMyta" malar "Cklarhai CXaapanaiH Orpmtf' la KT lat ad, Vak a, pp. no-aph by 0. Y. Unulli. MananalaClmialral Oaapaay. : i. k. ino. j. r*>. Aw. in. ina oeii). *. Hranoiaa. 4aa. ttna. UdM* IN, Mb 14* 0*77), X K. If. Maw aad H. A. ybindi, S./ad. Cbm. Pat. tf, *7 (1044). 4. M. Oaailirfa iu.1 W. B. Hmbaman. J. Am. l*a Aaa. 44. *143 (1*34). .v rm., aa.no ooitx e. U. Mahi, ,laa. rVm. lirMpa IT4. *e* (11741. 7. K. dawlaauar. /hr. Pud. Vhm. Gat. 4S4 (MM). X i. J. Dobbin 1. A Faa, mat A. J. H. Gaaaa A Cbm. Pan M, 1010 (toll), X I.Mammil.P.Paul.K.Jana.ot4T.Iaaarial,Caw ah.Mlt,IIHI>(W HLlllLmM,7.aiia.fcM,W(HN). II. i.aCala,/.rtaa.M.H.7<nMX 13. 7. nbaaaa. .laa. nWm. UrMyr MX 34~M(IUMX 1X7. K. Iliakal and U. H. Hay, J. Claa. Pm. Ill, I7ao-I7*a <line). 14. II. A. Sradaaaaab and W. A. WaW%/. fbna. Pa*. 130,03-04(1047). IX T. Craa, *. Trm. OMm. *4, 7*3(1*41). IX W.abaaadH.XPmlbinaa^b/.Cfcaaa.ne.nd7(tlW). IT. W. ZfTWeefc aad C. PddMa, dan. dtaar. M.adw(IMS). ia. CnNdaa>IV.IMMdla,eaH:nUbi.fW.4,3M(ieM). I'l. Y. X Wkiad aad Id. V. Hdibaaa, J.Om. 17km. HUM (Payf. TVmwtf X Iblb(1*30), 3H. II. Ilamlalli wdb H. Palau. Brr. ItnL .Han. taa. ax 743 (IW7). / 31. Y. DedavKa, Cam. rMn./bd.0XtM(lfe4). / 33. L-MototHH. IX CaUI,and X1 anon Caia Clin,, lad. 4X444 (IMal ax T U W. V Mummdm, dm. IVm CUa. H. ua (1KHX / S4. yr.vhktar aad M. Adba, JM* CMn. data . affUMaX / XX It. Mnyar aad A. Ilaftaaaa, ifaaahX Chan. 3X 144 (1017). .* 3X If. Maakh and O. Madia, daa. OaaL UWya M7.340(limi). . 37. I. W. PkiMI, H. IX Wallar, aad II. Fraani, A Anl. CTba*. pm. 44,3304(1*30). **. Bril. PM. 773,331 (My 17, iaa7)(lafraadx 3b. rkt daadar CaaiOTaaria, baaklat. ttaaaMda Co. Kx laala, Ma. an. r.M.IJmXTbmia WnOm*ia.dbaaX4X-TI (IM4X/ .11. 1(. U. tlaaKaMa, rtna. day. rraya. 44 (3X IKt-lM^iaax IX IIJI. rabk tJMJHI aad IJMIMI (Uaa. 17, IWh It. I. Jaakiaa (la Haaaa Haaaarah; la- t 3X tlJLIbil.XddtMl(AprilM) MM)!MwiThanaatandlaalmlaParei(InbaadUd'ldaalaa- fhlada H'Wratwmrudliirala at dm AdWaa Maairbiaaa d'l/jlaaX . 34. IM, Pai. IAM.4W (llaa. IT, IIMX X. U Jaakiaa aad J. X MbanU (la taiaaa Itaaaarab; amalyaad la Miaaaala Claaalral Oa.X / XX J. Vf.J. f> mal 3. IL HaHianK "lwyiaaiiola llaatlln fiiaaaia PaiiarOu'adliaVQPat TW*. Max I'll Ht/A. raaap(IM7)| mot(OrdWI/aadiymr. ObpoAaa datamaOba) rmtUaLmt. IX ".VaamataXa MalatW AtTU Bd. MmW, l^flll-A (ID43X 37. U4krM.na*4>M(MaraklXIIMh/-*LOkrk(laaOTldatoalrtaOa.X MCNS 076483 / Vl. 3 niMlKOCAKUONX AND CIlLOttOllYDKOC'AMIONil jMwIttr TWi. Mw*. Xh. I'UV^MmiMhIu (V, Ht. IawIi, Mik, IHt. IU I* II. numlttH *iMl H. T. ^IjNixIrr, Ikn. Kkr. Ut% ILZIUCRI (ItKW); 40. K. M. Hitrt, M. Kmf. firm. 15. IRM-nVIlKf). 41. W. .1 ISO. IW-IOO (I1U.U' 43. A. II. WWl# ml 0. o. ybwm*. j- /*. SIS. Ctt-044 < t*m). 40. I*A r4.l,Mri,l*>(llrr. I.\ IMU. a & MrCd0MihmmI It U Unkkm(U>OwMM I rn--IkwH l<t Chmiinl Ch>X / 4k I'A Ml, l.mljn.ml l,ll,t(nit. I?, IHHX r. M. Ctok (toUcnrml tArelri* Co.). l. V 4'X PM. , IMX K. I. WrhcwiM (to M.imnto CtwmtrM Co.). 40. I*#. I*al. (Iter. 11, iwttX 11.1. WWngnrtm (U Mwmiila ChcndMl On.). 4T. If. I. ttVMft#*, J.0rf.rfcr* M.O4J-0**0IX / III /W, XT, `*fl (lOM). ' / 411. l`XPM.S.l7JII0(MMHiSlt IflOIXU.I. Vjlmpirtm(M>Mmimmlo6wuldQu.), * U U. I. WrWn(4ri. W. U. Rim, J. M. ScWMr.MidC.WMrr, Jr., An*. Ckim. At* SI. *M- *4(imsx / II. t'.H. Pm. l,KMkH7(JMM 14, nnsx j. H. YmuikOa ll. H. IMutrih.*. Or.). - M. rAI'M.S,inn<(HN|>l.0,IH3SXILW.TNlMMMW.C.\v;UM(VtlViKylM>llvwliirttX .*4. 1/X I'm. a.IPUOMHrf*. 13,I#**). P. M. (Snrk mmI J. II. Kwrni* (l (Ml C*). *. rx ivl i,ut.tim(ivr. *7, iw*x w. c. iim <t im i&vwi c*>. a i'A pm. tiawi (Mr io i*x j. a m Mid a r. iiui <* woi)mm m m Mmitdiif'iurWitf GkX / 34 ArvUr Hr*mn md CMmM Sdlr(> Tcrk. Hull. PUSH, Maftauit* Ok*. Hi. Mn., April l!*W. / ST. .Irvrfar >7r frtoaftnf I'UMirimr* **d J/WOfcfli/hrXjMrf Amm, Twk 1WU. (XU, MhiicmiIm <%., Hi l.noi., ,\V, K.M. . it. w. Hmwmm, /w rw. t. *n? <u#rx M. II. A. linlMf w.1 O. <). Kw-td, Mat MX M te^r JkUA. Cto. M. M, tai-UM(i<m). M ItI. JmkiM wM R. X. Ktor. (W. A* Ctow. U. < nalX U. rx Pw. Vn7.7a(Apiim WWX KHWall* It I.*. IWd.XnanaiiACto, InaJ. . l'APkktMN,Atl(JM*ltlMIXK.I.MMl(I.XMlMMlCMlilU^MwOtX at W.J.I)*M.m4P.tl. Bantam* Cfcn.A*.Pn-.-(IWX to. TVnotoM Ftt PIMA tf<to toMdM, KmmI. C*. *k ImH m. o.wwM.v/,.rvA(i(na-w4<iaaaj. Ct lOt. PM. *,HRM(IMk II, IMMX H.'0.4XM(tohtoraMliml hpwCtoX r. VA PM. t^MAH (April lWI)B.J(.OtMI wlH. W.MMtol(to!Mi.MlCM!.Hc*btof CkV ' 11. L. liUMtAM. ' . Momauto CompMjr CUI.OIUNATKD NAPltTilALXNK^ Unrrul, in INXt, otv.Tvt.1 lliat waiUltn nwlarMi retultod (nun ranetion at Utlutiiw with imylilhainM in tin ptwanaa <rf eorUin anlnlynU. That elilorlnUiM piwlnrto mm fuiUwr Mnrfinl tty Kinahar in 1171. (t vm timra Uuut twenty yawn lator, Imnnyer, liwt Aytownrtli ilinmniail tlwir tnliininnintl potonlkUtiM (1). _ Owmimtty and yitynintily, tint aMmrlna dartvative. of napliUnlana proacntad ' iuveMianUini wath a miieh nnne aninplai problnin than tin rlitombmiaenra. VUtraring KrlennwyerV iwUltlMinmil of tint fnnad-rinK ntniahira of noplitindana in MOO, many yntrn ttopatti Mini uauty of lint tlmmttiaally |ma4Mn ahlorinalkm darirativaa of the ernniMuw! wiwi Inulatoti ami .khmtilled; ayan today tlm ptwitinun of tha aubatltuaM eitlnciim atonat in nil ianlatotl totnalilmw- and pentipdilomnuphthalonn^nnia not bean allnaatod with eartaioty (ni Taltla I), l*hyailwlly, tlm dillietdty of iaolatiny iaoumra ' nn^mi ni tialnraa praduaad by ehlariItalian at aapiiUialmm la auah that indiraat MOMS 076484 /