Effonte to express the Mongan TVal1s noactlon ln eyntheele of phenanthnldlnec uneubetltuted ln the 6-. Polyphos¡ghor!.c aotdl oyc1teatlon was successfully appl!.eil to syntheels of the lsomeric bnomophenanthnl-. A funthen llrnltlng faetor ln the general uce of cyclteatton of 2-formamtdoblphenyle (3r R = H) aã an ef flclent nout e to mono-substttut edl phenanthnld lne s 1E.
6-phenylphenanthnldtlno (é) uslng a varlet¡¡r e ayoLtslng. agentE of whloh etannlo ohlonldlc ln bol1lng g-dLehloro- benzenc and phosplÞrus pentaehlortdlo ln I r2rb-tnlahloro-. benzene eehievedl the best results Another feature of the reaotlona of thl ¡ tylge 1s tbat, 5 r6-atlyAnophcnanthrldlnea. EG 5) arc thought to ba tntenmedllatcs ln fbnmatlon. Dehydration on pallacll secl charcoal gave the correøponillng anomatte compound (.É). Qrnthesls eucoessful of a numben eubctltutedl fenanthntdlnes was aohlevect from thls methocl .2a)21 Although. Loudlon andl hle oo-puntor.e to lnvestlgate poseiblllty of .. a qrnthesls of fenanth:r.lrltne derlvatlves from a elmllan.
The eenbo-methoxy group in blphenyl (¡¿) mqy be rcplaoedl by other Broup¡ that serve to act methylctic. Ratloe of yleLde of leomertc phenanthrlctlnes are cllneletedl in eapaottles of aromatlo rlngs fon electron-neleaÉ6.
Nater.lal kun jijjiiramuu baatus, gara Èroro d erlvatrve (!.q) tti jijjiirre.45 Anv uneentalnty ae to the. 4, novcl approeoh aynthoale phananth¡ll-tllnee waa uacd laylon fltroJny keessatti, kan lnveetlgetedl ths applteatf irratti DlæAldlcr neaotlon thle flaldl.5O Condcnsatlon kan 9-rrltnoolnnamte acld (U") fi br¡tadlcnc yleldlcdl - ( e-nf tnophenyl )- 44-tctrahydlnoþenzolo asldt (bå). Peehoru reaetlon enrl walqabatee dlazonlum nlng- ologuree waggaa neeth sirnaan qoratameera".6\-66.
The Psohorr-reeetlon is in many ways analogous to the dny's dleoompoeltlon. 34;hotn72 to provldlc a source of aryl raclloale, and to the Sandlmeyer neactlont which probably implies the termecllato format of aryl.
EO.UATION II
In the field of drought, however, the arguments in favor of the horaolytlo not based on analogy and on the effects of substances are both quite strong. A more novel solution to the available system appears in the mechanism developed by Hulsgen and zdhLer.87 The font matlon of the nadleal (6g) has been redefined. by an upright process involving the open metal. rntnamoleoula:r oyolreatron was then a radical ally sm. We should not forget that the parties usually involved do not usually occur in the normal situation, but are more likely to do so. epecles are coordinated with the future.).
Poaltlon nuelear in what dllazonlum Foup ie elímfnatedt will probably not be ln oloee pnoxlmlty with methyl Foup ln (Z&,) kureaa. CfTeot on eycleatlon neaetlon of a group in the dlazonlum group was then entertained by Hey andl Lo*g.61 Copper-catarysedl dt eaonrpoeltlons. IVhen a large catalyst is used to promote the dleoomposltlon of dl azontun ea1t, bfphenyl-2-oarbory-anllldle (gÐ was fonmecl beslclee 5-phenyl-phenanthr.ldone (g¡).
That wal gtloup H-etyL has not included Ln neactlon abnomel weB indicated by thc. Although preliminary dlfìkusslon will lnpLY. that Peohorr reaotlon ean be app1lecl wtth oonfldenoc. to eyntheels of hetenoayclla grsteme and, ln pantloulan, phenanthrldlne denlvatlves, lncneasedl eomplexlty of. the posetble eldle neaotlons mlght eú"gnlflcantly lmpelr. lt¡ effloleney ln pantleuLan lnetancat. lnhenent dttffloulty of adaptlng known. phcnanthr.ldllne syntheses to develop a provldvo-omeret and reqgf. a newroutc in fenanthnldllnc nlng syetem was inexhaustible.
- naaotlon sarrted out wlth aolutlon pnepanerl by fnve¡rec allazotl¡atlon wlth JO$ cxocaa of ¡odlun
- Reaotlon oarnled out slth aolutlon pneparcdl by trnvanee dllasotlaat!.oa wlth 5F æcc¡s
- Bromo-2t-nltroblphenyL, obtalned by the mcthodl of Badlger
- reactlon carnled out wlth solutlon pnepanccl by fnver¡e dllazotleatfon wlth Fß exeeee ef
- reaotlon oa¡rnled out aften the addttlon of
Lmorlng of dllffcrenoc med ÊO, stnetohlng fnequenclee ln lnfranedt was e dllagnostlo pnolasty of. Cyolleatlon amlne (g,@) je dal riac drugemu pnroduet rhlah waa ldentlfted kot N-benzyl-Z-amlno-llr-lnetr¡yLblphenyl (tOZf) z oompanlaon wlth an. An lncreaee ln yteldls of blphenyl (1!J) r ffrd thc dthydr.ophenanthnldltnc (nÐ r w8¡ opaženo, fhe ylelËls of thc blphcnyl (ltil in suLtam (tt¡).
ÎAEE UT
Feaotlón oennledl out wtth solutlon Bnepanedt
Ti sabali pay a pagarigan ti dtearnlnatlon hatl ket napaliiw iti eyclteatlon amlnee (Í!g), (tt Zc) wenno (ttZa). Tlr.Ls panangilawlawag ti akem ti ooppcr ln thc dleoonposltlon dlaøontum eaLte te iti pangkaaduan. 11fi ti ooppen dtl eeolvedl 1n ti mlxedl aotdl s ln eaoh o88G¡ cuprlo tonc rculdl zatonc agbalin a prceent ln eaoh ayclleatton lrrerpeotlvc ti pr6s6noe wenno absenee ti.
Thc noohantgm of cJ¡oll.satlon rcastlon cannot be intact as shown 1n Flgure fV. Although thla wonk provldlea cvldlenoc for verTr hlgh ¡rcaotlvlty of phenyl catlon, neaeon for thta unusual lnetablltty. Fonrmtlon of bifenyre(thZa) and (tirZU) dtuntng deoompoaltlon of tllazonlum ealt sf the.
Howevor, the apparent flon-¡eleetlvlty of the attacklng 4eof ee ln reacttone Tytth the usymmetnieally eubetttuted¡.
It is clear that the megonerlo cffeot of the bromlna atom prefers a route g when a rowboat on lnter.medllatc. Dlnect evtdencc for the n¡ode of the fonmatlon of the sarbazoles (1@J was obtained as the btphenyl (t6to). metLth the eleven development of the nuclear atom until the base is added to the reaction.
Eleotnoph!.Ilc attaok on thc benzyL rtng would then favor thc fonnatton of thc tplro. Tht'a la cxerÞllftedl by 1e¡¡v yleldl of dlfhydtrophenanthrldllnc obtalnedt when 5fi c¡;aacs of ædllum nf.trlte vaa ueedl [n oya1tsat!.in e amlnchfrwwhngamth amlnchfrwntaled q) cloegg of æcllun nltnlte was cnÞloycdl. In dtleousslon of oyoll¡atlon of thc dtazotleect amlne (llZ'l tt wat t\¡ggeEtedl that thc.
After a long time a problem was encountered and the hot sound at the pump was filtered. the belt tetnaehLorldla vae thcn removed. lJg rclg and the g-¡ltnobenzyl bnomfde utflleeedl lmnedllatcly. without further information. After the addition of the needle, this curriculum was expanded on September 6.
Evaporation of breast milk and ohnomatognapþ of the needle on aluminum in benzene can the. z) Potaaelun (0.5 g.)'.râÊ sdldlcd ln cnall pontlone with the intention of filling ammonfa (5O mf.). The ethnic aolutlon of the non-baeto fnaotton was washed with dll.ute agueoua eodltt¡m. Chnomatognaphy of the bastc fraotlon (O.6 g.). vl1) I will have -methaneul ho e-phenylenellamlne (qø¿) in the Dre66noe of.
Finally, the oolurnn was eluted wlth etano]. OO nlt), Solvent removal yrteldedl a rect o11 (O.Z g.) not to be considered further. Enter the elutlon of the column with benzene and ether appearing only in consumable red tar (O.f g.). xl) Eatlon ring of tr-E-bromobenzyl-[È-. The knomatognaphy of the neutnal fraetlon (7.7 g.), determined in (*) above, yielded the following. cotçountls ln oniler ehown¡ &g-bnoncbenzyL-2-.
Funther elutlon wlth benzene (Z¡O m.) yleldlert a Bol!.d (2.9 g. ) Cnyetallt eatlon from X6O affor.ded oolourlese prl sms, ûr.p. Finally, the oolumn vae was precipitated with ethcr (¡oo nL.) and ethanol (¡oo ÍiL.) déhloh affordccl only a. DlsttLlatlon w!.th zlno dluct (o.5 g. . to 5 g. of glne !ust) pnovldtsû st¡ppont fon the et¡ruoturc ae¡lgned in ttrle oompoundl.
The dlanlr nedl olL (0.7 g.) obtained by further elutlon with benzene and ether was not further examlnedl. xvll) Cyell eatlon of N-g-bnomobenzyl-N-.
