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Kirn tit 2 of (`till mrsoii,* I mid l(ilAnc rf vM-rv uirnii- trT-fj, Tbr ulrnMy of ihr hrln-o by llr. J, Mwkfinifi l.nmii *<<) I'flirrM of Jlf, iVr Stomp* i. kiuf nl riiftpoMa) I bo tnfrurvi) fir of ]*urj:eMiiir iu:m1 o**t liCtd. Tin- niniw *f*relm Turn] Stl4iiirin<] <m<| )wr fcluff b-jf/irtoKim, NTJi* J ruinllN'im. .b'lirjod, IV. Hnlko. L. niul iip/urfr#4#i /wffri 1973 11*31. ]'. Chnnitni and //<*>** rn /'rodurto. 1^* Uhiv<TH,v id in I'rwi, Ollpll HlU tw*'.', )' ij-ri ivixt Hi'|j(ombor 2fl. 11*73. Itrtn. ru*r*/. 27 (1V73J Xu. F SHORT COMMUNICATIONS 9121 Polychlorinated Biphenyl* aa aolvenl. The fractions eluted after soma starting material and the mein product VI.* 2,3,7,8-Tctrach)orodibenco* furan, Critical Byproduct in the were investigated by maa* spectrometry for tha presence of compound* with the molecular itm 204 m.u. which corresponds Synthesis of 2,2',4,4\5.5'-Hex*chloro- to a tetrachlonlisted dilatnsofursn. .Such biphenyl by the UUmann Reaction a compound waa also found eluted with com* other byproducts, probably chlortn- ! MARIA MORON, CORAN SUNDSTROM atad terphenyla (MS) (cf. Kef. 7), The sus- . a..A CAR). AXEL TACOTMLISTER i pentad tetrachlorodibensofuran could more conveniently be isolated in a pure stato by Vrs//enbcrft*5oraiprtrt. SlvcUahu (Jiuvtruitt, UUm Frtteail, 5-/04 OS chromatography of the crude coupling product on an alumina column. The com ' Stockhtlm, Swim pound gave the expected analytical values and mats spectrum. Tlio only peaks ox- seeding 10 % of the base peak (300 m.u.) In oonnection with atructural studies of in the men spectrum was found at 24 I -- ilia component* in commercial 1*00- 243 m.u. (10 %) which uorrespniuls in loaa mixture* (polychlorinated biphenyls) we of QCO from the moleouler inn. Tin* have synthesised a number of symmetri- fragmentation wea found also by Vim el at.' rally and unsymmetncaliy substituted and could be compared with tlio loss of . chlorinated biphenyls.*.1 Ona of thaaa oom- HCO from the molecular ion of tlio parent pound*, 212',4.4'.5,5'-hc*a<!)>lcrobiphenyl, a compound, dibenxofaran.1* major component in FCLMnixturaa,**' waa Tha NMR spectrum showed singlet aynthaaiaad in larger amounta by an UU- signals at i 7,4t and t 7,05, consistent - inann coupling of 2,4,5-tnchloro)odo- only with a 2,2,7,0-letraohlorodibunxofuran lntene in order to be uaad in toxieologtoal atruoture. invert igatione. Treatment of 2,2',4,4',5,5' hexachlorobi. ' In a etudy eonceming the UUmann reae- phenyl with potaaamm hydroxide at , lion of 2-chloroiodobenrena Nilaaon ' elevated temperature* gave email amounts thuwed tliat under commonly used oondi- of the same totrachlorodibenidfumn (ULC, i ttona dibencofuran waa formed aa a by- TLC), probebly css a phenolic inter t product in the rolling raaction. Tha for mediate. > mation of minor amount* of 2,3,7,R teti%- > methoxydibenaofuran in the coupling of . t bromo-5-iodovaratroie ha* the bean re- i ported.* Tlte ooeurrenoe of chlorinated di- ` benaofurana as contaminant* in ehtorobi- ' phenyl aampla* prepared for toxieoloRteel experiments ooutd be serious in view of the high toxicity of them compounds, raoantly . delected by Vee tt at.1 aa contaminants in ; antne eommerr-ial PCB-mixturea. W# liava ; therefore studied the byproducts in the ' above coupling reaction with apeeiel at tention to chlorinated dihensofurane. _ T1 coupling reaction waa performed ` wilji commercial 2.4,0-teich)oroidobeniena which *-aa thoroughly purifted. The copper ' broil*# was of tha asm* quality as tha ona used hy Nilsson' end contained a small amount of fatty aoida. The use of very pure electnilytic ooppar did not signifi cantly change the nalura or yield of by. pnxturt*. No precautions were taken to exclude air from tlio reaction mixture. The crude coupling product was frac- The reaulte presented here show tlint any prcparstion of polychlorinntod bi phenyl* ayntheeiaed via tlio UUmann reac tion using iodo-eompounds u-itli chlorino atom* in the ortAo-positione must ho thoroughly analysed for the presence of chlorinated dibenr-cfurans. A comparison of the toxicity of 2,2',4,4',5,5' hexncliloro. biphenyl, aynthseisod by tho Uthnomi method, and a commercial PCU-mixture (Aroclor 12541 wea recently piibliah.-d.11 No details of tho purification of the pmdurt were given. However, our crudo biphenyl contained oa, 3 % tetrachlorodibenrofursn and trace amounts of tins compound wore detected (QLC1 even after repeated ciyi nl- lisHtious from hexene, ethanol or acetic arid, 1 itmubvl on a silica gel column witii haxone Siperimtnlal. Tho melting point * were de 1'art V, m Itaf. 1, termined on a Kufior micro l>n tpi. Mu* Actm CAem, Scond. 27 (1473) No, I HONS 207296 3 SHOUT COMMUNICATIONS *1 rft wnff* on im J.KH 0000 l<crtroinoinr. T)io NMK apeclrtmi wa# ol- tiHiM'i] on a Vhiiwj IIVKHiI) m^trumont uiili l. lmintjiJiy)i]aiMi an inltirnnl aLamlnnl. (Ju tUrantuttHjTnjihy. Tim products wcro Uy 01.0 lifting a Duulrtt- J^ii'kurit 7tJ2tlA >:(ruiliunf filled with an KC (ftilreior- (I'lfeM rr'ltninid (0.20k If1(> ctv) con fining ? % (w/w) Apieznn I. on (liromowrb IV AfW DMC'S (Jon - r_*n mHii t 210* w-nm numl. The gna flow (Hrgi'n rntflhnn' 6:1) was abmtl- 2ft ml/mm- Coupling Miction. 2.41ft-Tricililniv>iodol>enr.ene (Koch-hight, recryshdliwd from ethanol or ptiri/ird on a *ihcn pel Column wil.fi litxnne hi xuivrnt. 10 g) wa* thnrc.ighjy mixed with copjmr-brtmz* (tithngHiplue bronxe, tf. Kef. 7; 1*.:i p| nml the mixture wxj heated from 1B0* to 230* during onn hour with occasional *t(rr>.ig. Extraction of the roaction mixtun in * So*|ikat npparatu-i vriUi hexane and vapora tion nf solvent g*v* ft.7 g of cruel# product. Itolatum of 2,?M,tf1T5,5''AazacAjoro6t* pftmyl.' **1* 2.ft g of tho above product wot Added to a column (ft.ftx 62 cm) of silica gal (Merck, <0.063 mm) which was eluted with liuxon#. After ooriiu starting material 2,1Z\4,4\W haxnchJorobjphenyl wan obtained One from byproduct.* (OLC), 2.05 g. rap. 103.ft-104.6* (KtOH), (EtOH) 261 tun (c 2u40), 2l>0 nm (i iKftO). After ilia major product the Ulruhlorcdi- benr.oftiran eluted together with sums other 1-vfnLMl'-ct*, must jtrobebly terphsnyl* (8 Cl) 0* nhoivn by MS. fiolutiM of !i,7,f-frlrdrUprorfibue/iiras, When 2.ft g of the crude product was chro* malopApbcd oti neutral alumina (Merck, activity grade 2. 1.2* 72 cm) with hexane as Mulveht the biphenyl end the tuspooled tar* phenyls eluted together. The column wee further eluted wrth hexene-ether (8:1). Finally elution with other gevo a fraction of 2,17.1- (otreohlorodibenxofuren (0.08 g) which crystal* IimhI from hexani. The compound recryttah IunhI on the hot plate from os. 160* to give needle*, m.p. 223--226* (subl. from oa. 210*). c(Found: 47.0; H 1.3. M+ 904 m.u. (4 Cl). C,,n.t140 (906.0) requires C 47.); U U).] (NMH (CDCM J 7-49 (*) and 3 7.86 (). ^ (KvOH) 222.6 nm (eh) ft 46 600}, 229.6 Am (c 50 200), 240 am (*h> U 26 C00). 251 am (e 17 400), 230.5 nm {t 2ft 100). 208.6nm (*h) <e 24 000), 304 nm (e 26 200), end 3U nm (e 23 300). Hniention time* on GbC, conditions ah He. scribed above, for 2,2'.4.4`,5i,'V.h*xacblorobi. phrnyl and 2,3.7.8-tetmclderodibentofuran were 11.6 end 14.8 mm, respectively, lion time* for the terphenyki were several hour, undo. llivw oomhtioria. On TLC (ailica golhex.n.) the tatraoliloro. dilxancnfuran hu en BP valua of 0.30 ud th. heiactjurobiphaay) 0.41. ^deniMfin.itli. Wo thank I>r. Rotf AndorMon, Agrioultwal College. Uppoaia. for running the NItUI ipectruio. Thin work m financially .uppertod by tha BumtcA Com. onil*. o/ IA. National Siooditk XnnnmeuM frMeom Board. 1. Sundatrfim, Q. Bull. Environ. Cwlini. Toxicol. In prut. 1. Sundstrfira, C. Jteta CA.ua. Scond. 27 (1(73) 000. 3. Sund>tr6n>, G. To Ac jnMiakod. 1. SiMou, D. and Walt.) D. J. CAnwnalegr. CO (1071) IS. 5. Webb. R. O. end McCall. A. C. J. Aoo. Ojf. Anal. Chmlmt 55 (1972) 740. 6. Tae, A. C. and daVea, R. H. Eminm. Seitnco TuJtnol. 5 (1971) 1310. 7. KiUwn. H. Acta CKtm. Seaml. 12 (1950) 537. t. Baker, W.. Barton, J. W,, McOmi., J. T. W.. Pannak, R. J, and Watta. M. L. J, CAcm. Sot. 1901 3900. 9. VTM, J. Q., Koaman, J, H., van dor Maaa, 1. L., tan Nuavar da Brauw, M. C. and deVoe, R. H. Food Coomotieo Toxicol. 9 (197U) 025. 10. Prinj, B. and StjarnelrOm, N. E, Ada CAem. A'oand, 22 (1900) 549. 11, Voa, J, Q, and Notanboom. Kao,, E. 7'asieot. Appl. PAormOcsI. 22 (I012) S03. II. Safa, 8. and Hutlinger, O. J. CAcm, Boo. Perkin Tran*. 1 If72 M. Raoaivad Ootobar 1, 1972. Aaot CAem, Stood. 17 (1*73) Na. * * II <> l: T * Diffttrcnii;i(<nn liflwpnn t-GItHani) ] ;Clnii I'tplides, mill ot- A n>itm.u \ Acids liy J'MU Spri t nMt>| m KlIlKTtNniA 3nd 1'fcDKR OI.ESK.N |. VH"KN llcparlmcnt of Or~nnir Chmuitn'- /t F*if biary and Agrirultumt ( iif OA*IWI CopeniiQgtn, Ovnmark Nummeueiarnaun^ dy glulamyl fh?rh ammn dreer mIiv*w *f i:-itnruJI-. ImUkxIc fur tho uner|inv*ir-n| sin determination of thcet' therefore of unporUince. \\Jirmu t and methods enn be to c-*tnhu* cquence of di|>optide* eoritiiuun^ acid tJie differentiation bviueou a y-glutiunyl donvativcH a problem. The only three rclmble cFk solutions to this problem are iynt qutntitative dscarboxylatioti with hydrin.* and dearrumttiun wMii n acid.1 The latter two m struct've an rl demand cunaidt-mbi" iun of material. Tlio higi-.er p/x. vulu- ghitfiinyl e-omino sct<U ili<r> f glutiunyl e*vnini acids dth-rinMif dutiou behaviour on itmri^ly exchange resins tu the aretnte t <r plutemyl peptides bomg cluii il lhrl arctic acta. Iliffnrentiatiori y-glutcunyi peptidea hoe brrr cruitlr nmino acia analyser, win r * y p-l.r peptides am ehrtod before hi,it a ^hii peptides after the second mmix* hgmI a strongly teidte inn-exclmirj.1 n^on citrate buffer.1 Vanuus m*lh"*ts on paper cliromntogmpiiy. Wcrrn'ph< or acid labtltty for Uistinctiou Iwnvee two isomer pneaibihties rtqnm* isomers for mlrnhta results Tits 4*vahja for tliu pmtim u glutamic acid moiety is larpur f< glutamyl ntnmo acids than fur y ^hit amino acids in aqueous solution, und difference hot been proposed as a m for differentiation between - sue glutaroyl derivatives.4 However, tlr value for the *proton in 7 duimn> tamiti acid (3.82 ppm) is higher than upper limit of 9.00 ppm given for tl proton in rglutorayl derivative?*.4 similar to the shift fur the * pratr gliiiaraic aetd m v-glutaioylpheci^iul. Actm Ch*m, Stand. 27 0973) Nig 9