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BBK 24.2 M30 YOK 547 Map 2x. M30 Opranuueckan xHMus. PeakiwH, MexaHHaMbl W CTpyKTypa. Yray6nennai kype Uf YHHBePCHTeTOB H XHMHYCCKHX BY3OB: B 4-x 7. T. 2. Hep. c anra.—M.: Mup, 1987.— 504 ¢., aa. Coppemenioe yieOHoe mocoSne ANA yHsepcRreToR H XUMHYECKHX By3OB, Ham CalHoe HABECTHBIM ANCPHKAHCRAM XUMHKOM IDK, Mapuem, orpaxaet Hozeflimme ocr! 2KeHH XBMME B PaSBHTHY TEOPHR HW MexaHHSKOS OpranayecKux peakgah. Uupar: ‘OxBaTA BCeX BONPOCOR B AHTePATYPM NOSBOAReT PacCMaTpHDATS STY KHUTY Kex 9) NRAOTeRAGeCKOe HATAnHe NO TeoperHieckoh OpraHAYecKoA XUMHB. Bt, 2 paccmarpasawtes pearnun aTHYeCKOTO HYKTeO@HARHOTO saMetite- HHS H PeakUMA apoMaTHYecKaro WB aAUbaTMIeCKOrO SACKTPOPHMEHOTO saeuleNEA. ot HayYWHbx paSorHexos, acnupaHron H CTYACHTOB XHMNYECKHX CHeI|HaNbHO- erefi. 1803000000—365. —— BB: 2 O41(01)-87 ToanncHoe wsRaHtne K 24. Pedakyun aureparype no xumuu MOHOrPAOHA Dxeppu Mapa OPrAHHYECKAS XHMHA B4-k romax T2 Crapuuft mayen pezantop I. |B. Oxnscra anya penaxtop H.C. Epmnsopa Xyzoxnex B. II. Kysnenos Xygomectoeianl penanrop M, H. Kyatauna nMeCKHA DeMaKTop A, 10. Dommmena Koppextop H. A. Tapa HB & 6131 Cnawo 8 waGop 10.11.86, Mlogmmcano x mesatH 17.06.87. @opwat 60x90/16. Bymai Ka. RYH, cchiKr, Tlevatb. piiconas. Tapaurypa aureparypaas, OGnew 15,76 Gym. 2. Yon. mew, x. 31,80. Yeu. xp.-orr. 31,60. Yuuon. 1, 34,70. Von. Ne 3/4880. Tapax 11000 sks. Sax. 2937. Hena 3 'p. 90 x. Hsgateaberso «Mup» 120820, ECM, Mocxea, H-110, 1-i Puxexua nep.. 2 dlenwurpaackast tHnorpabaa Mi 4 opxesa Tpyzoporo Kpacroro 3mamenn Jlennurpancxoro oGzequnenns 4 HaHMeHORaHHA yxoumuel rpynou. Ecaa yxopsitef rpymnoii apaserca Boxopor, TO ero MOXKHO He ykKa- abBaTb (Bo BCex IpHMepax cyG6crpaT sanHcaH cepa). CH,CH,Br + CH,O” —> CH,CH,—O—CH, — emzonrn-de-Sposmupoennue NO, . HO. Humpo-de -eudpupe sane © + HNO, * oO ame temipoueciees Ip HassaHHH MHoroBaJeHTHWX saMewleHHit Acnosbsyior mpe- uKch «1H» A Nepey cAOBOM «3aMetleHHe». CHCl + 2EtO- —+ CHAOED), dusmoncie-Ge-dnxnopo-duscmentenee -CH,CHO + PhyP=CH, —> CH,CH==CH, aremuren-de-onco-dersamenjenue CHCEN + 4,0 CH—C—On eudlporcie, onco-de-inimpuno-mpisamevgente oO (IIpameuanne. Harpuaorpyana — sto =N.) Hpucoedunenue. Jlaa npoctsx 1,2-npacoeaunenuh ykasusarorca o6a amelta ¢ MOCKeAy!OWHM cIOBOM empHcoenHHeHHes. Tlopagox nepeqHcAewua aazen 0B cooTsercrayer cucteme Kana — Mnroapaa — TIpexora (1. 1, pasa. 4.6), npuiem pHayane ykaablpaetca rpynna, HMelollaA MeHbUlee cTrapminncTBo. Muoropaneltuoe mpHcoenuHeHHe HasbiBaetca H T. J. 8 YACTb 2 CH,—CH=CH, + HBr — CH,—CH,—CH,—Br zudpo-Ggomo~ 7 ype UC cl +c, — Ouxhope-npucoedunenue cl CoE + HCN — HCH CN O-2udpo-G-yuano-npitcoedunenue 0 OH CH,~-C=CH + H,O — Ch C—CH, Dueudpo-orco-dunpucoeiinenue Saumunuposanue HasHRBaIoT Tak We, KaK H NpucoeanHenne, npH 9TOM BMECTO ClOBa HCNOAb3YI0T COBO eOHMHHE- . pOBaHHe», CH, —CH—CH(CHY) 2 CHCH=CICH,), aubpamo-amemumsposaonie Br sOBr -CH,CH,—CH—OH —>+ CH;CH,;CHO O- exedpo-L ~cymsponamo-amumenepoon nie $0,-Nat CH.CH,—CH—Br ME, CHYCRCH azeudpa-dudpomo-duamumumiposamie / Br B qannoh Kavre mpm onkcaHHA peaxumit 6yazyT npHBexenn Ha- 3BaHua Mo mpaButam HIOTIAK gaa MHorux mpaMBx npespalenni. Kak 6ygeT BaqHO 43 AanbHeliiero H3n0%KeHHA, AA NocrpocHna HasBabHit HeKoTOpXx peakuHi norpebyiTca Gotee pacuimpennne MpaBHla NO cpaBHeHMO c NpHBe_eHHbIMA azecn [2]. Onnako aBTop Hajleetca, 4TO, HECMOTPA Ha 9TO, Mpocrora cucTeMbl OyyeT o4e- BHHa. Eure oguo samMeuanne. Muorve npeppalienua MoxHO HasBaTb, ACHOAb3yA B KauectBe cy6ctpata Goh us peareHtos. Hanpumep, MIpeBpauleHHe, HaSBAHHOe Bbillie METHEH-7e-OKCO-ANZaMeleHHe, MOXKHO Ha3BaTb TAKKe ATHAMREH-Ne-TPHenHapocHopansAHs-qH3a- mMewenne. B jannoi KHHre GyAYT MPHBOMATHCA JHIIb HasBaHHA, Mo- CTpoenHtie Tak, uTo6u cyScrpar MOmKHO Gino paccMaTpHBaTb KaK BcTyNalollnll B peakUHIO, KOTOpad COOTBETCTBYeT HagBaHHlO TaBH, Tak, HaspaHve peakune 11-13 (ArH+RCI-ArR) 6yaer ankna-ye- THAPHpoBante, a He aPHI-fe-XAOPHpOBaHHe, XOTA BTOPoe Ha3Ba- He Take BOwHe IpHeMAeMO No mpaBHam HIOTIAK. MACTb 2 9 Ccmakn Ha Organic Syntheses B Konue onucanua Kaxpon "ponymeposa tol peakiwH nNpHBO- AHTCH cHHCOK ccbIoK Ha «Organic Syntheses» (cokpameHuo OS). 3a ucKmoqeHnem peKonopirx OUeHb pacnpocrpaHeHHHx peaKunii (42-3, 12-20, 12-22 w 12-37), stor cnHcoK comepKHT @ce CCHAKH ua OS ana KaxgoH peaxnun. B KHHTe OXBaweH MaTepHal CBOAHHIX Tomop c I no V 4 HA,MBHAyaNbHWX ToMoB or 50 go 61. Ecan B KOHUe pazqena orcytcrByir ccpinkd Ha OS, sTo osHa¥aer, YTO peakuwa He onHcalia B ykagaHioM c6opHke go Toma 61 BKaio4uH- Tembuo. [Ipupeentble cchKH MpexcTaBaaioT cBoero powa yKa3a- Teab x OS [3]. pn cocrasmennu cnuckos co6moganuch ompenener- Hble OCHOBHHIe NpaBuna. PeakwHs, B KOTOpO Be YacTH MONeKYAH B3anMOMelCTBYIOT He3aBHCHMO H OMHOBpeMeHHO, MpHBOAHTCA B pas- Aenax, Nocsallenabx o6oumM THNaM. AHaqorH4Ho, ecnH ABe peak- UHH HpOHCxXOAAT HAH MoryT MponcxogHT> Guictpo Apyr 3a Apyrom 6e3 BbIeNeHHa HHTepMeAMAaTA, ONH Take MpHBOATCA B OGOHX pasgenax. Hanpumep, peaxums, onucanuas 6 OS, IV, 266, sto 04 CUCH,),O(CH), Cl re) wagon? CKCH,) O(CH) Takoe mpeppalileiwe MoxHO paccMaTpuBaTb Kak peakuio 10-69, 3a KoTOpod cnenyet peakunsa 10-18, u mosToMy ccbInKa NpHBOANTCH pH onvcaHHu x TOM w Apyrof peakunu. Ognako HekoTapbie peax- UHH B CUHCOK He Monmasaior, Tak Kak MpencTaBasior ca6ol TpuBH- able mpHmepbt. B vacTuocTH, peakna, onucaunas BOS, III, 468 OH OH 1 . CHC} O + CH{OMe), > o NO, | NO, 9TO XAOPOMeTHMMpORAHHe HM, CNEOBATeNbHO, OHA NPHBOAMTCH HOA Homepom 11-26. Onnako B xoge peakiHH 43 alleTana o6paayerca tbopmaapgerag. Ho non HoMepom 10-7 (rupsponHs aueraseit) sta ~ peakuna He yrlomuHaercs, TaK Kak B AeliCTRHTeBHOCTH He ABAAeTCH MeTOLOM Nosy4eHuA tbopMaabjerHsa. . SHTEPATYPA H NHPHMEYAHHA 1, Knaccuaxanun peaxuui no paszenam, KOHCYHO, B HeKOTOpO# crenenH npox3- Bonbna. Kaxaast peakina KHAKBHIyambHa (Hapumep, CHsCl+CN~->CHyCN u CoHsCl+CN-->C.H;CN), 4 MpH3sHakH HX rpyNNHpoBanHa BbIGHpAWTCA, Kak npazyao no OOUeNPHAATEM KpHTepHAy. B taxoy prOope HeKoTOpyo pos id YACTh 2& MOTT HTpaTh H HHAMBHAyaNbHBIe BKycL, HekoTOppe XHMHKU CouTyT, FO ypastenix CsHsNo++CuCN-+CeHsCN a CyHeNot-+CuCl+CgH,Cl saamotca Mpumepamu OOH H To Ke peaximu. [pyre oryT c sTHM HE COrnaCHTDeA, a K pagaWaHBM HAMOCTpallMAM OAHOTO Tpollecca MOryT OTHECTH cHemyMHe ypasnenua: CeHyN*+CuCl-+CgHsCl mn CyHsNo*+CuBr>CeHsBr. Aptop He yTBepalaer, TO HCNOAbsOBaHHad a HACTOAULeA KHHTe cHcTema KNaCccHbHKANMH Ayuile, ¥em mo6aa apyras. 2, Tloaupie npabuna, ony6suKkosanuble Ha Hactonmyee Bpema, cm.: Bunnett, Pure Appl. Chem., 53, 305—321 (1981). Tlonpo6nuit yxazatent K CpogHiim ToMam I— V onyGankoBan Kak 4acTb Ce- pun: Shriner, Shriner, Organic Syntheses Collective Volumes 1, I, IH, IV, V, Cumulative Indices, Wiley, New York, 1976. Ipyroi xasarene k Organic Syntheses (0 toma 45 skaowterbHO) cu.; Sugasawa, Nakai, Reaction Index of Organic Syntheses, Wiley, New York, 1967. » 10 Peakunu aindatTHyeckoro HYKJeOMHAbHOrO 3aMeljeHuA pn nykneodpibHoM saMclienHu aTakylOWlMii peareir (HyKaeo- bua) oraaet cy6crpaty cBow sNeKTPOHHYyI0 Mapy, C NOMOHIbWO Ko- Topo o6pasyeTcsx HoBaH cBasb, a YXOLAMaAd rpynna (HyKNeopyr) oTilenaderca co cBoef sxekTpoHHOH napoli: RAGE — R-Y+X B npwseqenHom ypasHenHu HuuerO He roBopuTca o 3apamax. HyK- Aeopua Y Moxer Onirb HeiTpambuWM HAH OTPHIATeIbHO 3apaxKeH- HEM, cy6ctpaT RX snGo Hefitpazen, 1160 3apaxKeH NOROKUTEABHO, MO3TOMY BO3MOXKHH B3AHMOelCTBHA YeTEIpeX THIOB, IPHMePE KO- TOpHX MpekcraBleHbl HHKe: Tani: R-1 + 0OH™ —— R-OH+T @ - Tun Wt R—-1+NMe, —— > R-NMe, +1 @ Turn (il; R—NMe, + OH” ———+ R—OH + NMe, ® Tan Vi R-NMe,+H,S ——> n—SH, +NMe, Bo pcex cayyasx Y 20MKeH HMeTb cBOGOAHYIO Napy S1eKTPOHOB, MOSsTOMy BCe HYKAeopHAN ABJsOTCA OCHOBaHHAMH JIbIonca, Ecau Y— sro pacrsoputenb, Tora peaKNWA HasBaeTCA cOADEOAUSOM. Hykaeopuabioe aamemenue z apoMaTHuecKoro aToMa yraepoaa paccmatpupaerca Br. 3, ra. 13. Hykneotpaabuoe aaMelietve y anmdaTueckoro aToMa yraeposa MpHBOAHT K GAKuAUpOBanuIO HyKAeopuna. Hanpwmep, paccmoT- peHHas Bbitle peaknHa Mexay RI u NMes mpegctasaaer co6ot Gakuauposanue TpuMeTanaMHua. AnanorH4Ho HyKeo@usbnoe 3a- MelleHwe y aTOMa yIvlepofa allHAbHoi rpynibi— sto ayuaupoBa- due HyKAeopHsa. 12 TAABA 10 MEXAHH3Mbl B peakuuax HyKleo@uabHoro saMeliieH#A B SaBHCHMOCTH OT TIpHpoaHl cy6crpara, HyKaeopHua, yxoasiveli rpyiin H oT ycroBHi peakUHH MOryT peaTH3OBBATLCA HECKOALKO PasHLIX MeXaHH3MOB. Oquako 8 KawKAOM H3 HUX aTaKyWWlH areHT HMeeT S1eKTPOHHYIO napy, HosTOMy CxXOACTBO MexKZY HHMH 6orbIe, 4em pasanite. Bua- wage OyAyT paccMOTpeHN MexaHHaMbl peakLHii, Mporekalomyx y Ha- cuittieHHoro atoma yraepona [1]. Daa rakux peakunit HaHGoulee pac- TpocrpatenHuMu ABRGIOTCA MexaHugMEl Swl 4 Sn2. 10.1. Mexannsm Sy2 Sn2 ogHayaer s@Mewmenue nyxrcopuacnoe OumoAenyaapnoe (substitution nucleophilic bimolecular), B sT0M MexanusMe araxa ocyulecTBAKeTCA C TolnoHOd CTOpoHol: Hykscopua npH6amKaetca K cyOerpaty co CTOpOHE, NpOTHBONOAOKHOA yxoasmieli rpynne. Pe- aKiMa npesetaBiaer co6oH ogHocTamHiHbl Mpouecc, T. e. B Mpo- iecce peakIHH HHTepMegHaT He BOSHAKaeT (CM., OLHAKO, pasa. 10.4). Cpaasp C—Y o6pasyerca OHOBpeMeHHo ¢ paspblBOM CBASH C—X: FTES —— Wee —- ye +X 1 Suepran, HeoOxomuMad QA paspbIBa CBASH C—X, nocrapaserca 3a CYeT CHHXpoHHoro Hponecca o6pasoBanHA CBASH C—Y. Baaxm- Hoe pachouoxKelve aTOMOB, COOTBETCTBYIOULee MAKCHMY My Ha KpuBoit CBOOOAHOR SHepraH akTHBAUHH, MOxET ObiTh H30GpaxKeHO C TOMO- wo bopmyast t. Ecrecrsenvo, peakuMfA Ha 3TOM He OCTAaHaB.H- paeTcA — 9To Mepexogiioe coctoaHHe. Kak TombKo rpynna Y BK.10- qaeTca B coeaHHenne, rpyfina X gonKHa YATH, HOCKOubKy aTOM yT- wepoma He MoxKeT HMeTb Gonee BOCbMH 94eKTPOHOB Ha BHCIHeM yposne. B mepexonHoM cocroaHHH HcxO_HaZ sp?-rHOpHausauua WeHTpaabHoro aTOMa yrnepona HaMeHaeTCA Ha Sp?-rHOpHAH3alLHio c MpHMepHO TepneHANKysapHoH p-op6uTaabw. Oava Aoas ston p- op6uTaaH TlepeKpLiBaeTcA c HyKneoHOM, a BTOpad — C yxonanleit rpynnof. Tlosromy mexaHH3m Sn2, B KOTOPOM TIpOHCXoAHIa 6u (pouraibHaa ataka, HAKorAa He Ha6awonanca. B ranoreTHieckom TepeXOAHOM CocTOAHHH ¢ pouTambHolt arakoh op6uTaqM kak HyK- neobuia, Tak H yxOAMeH rpynnbl AOWKHB NepeKpLIBaTecA C OA- Hoi H Tol Ke Aone p-op6HTann. MexaHH3M, B KOTOPOM MPOHCxO- THT ataKka C THMbHOH CTOPOHE, BKIIONAeT MAaKcHMasIbHOe TepeKpbl- BaHve op6HTasel B xote peakunu. B mepexoaNom cocToaHHH TPH HepearHpyiouive rpynnsl H YWeHTpanbHEA aToM yraepona MpAMepHo PEARIIMH AJIM@ATHYECKOLO HYKJIEOOHIbHOTO 3AMELEHHA 3 Konaanapubt. Onn Gyazyr crporo KonAaHapHel, eCHH BXOAMIat H YXOWAaa PpyNMbl OLMHAKOBET. Vimeetcs MHOXeCTBO AOKa3aTeABCTB peamHsalHH MexaHH3Ma Sn2. Paccmorpum cHayana KHHeTH¥ecKHe Aanubte, TocKombKy AH- MHTHpyioulas cragva (B aHHom caywae 9Ta Cada egMUCTBeH- Has) BkmouaeT H Hykeodun u cyGcTpaT, peakHA HOI%KHa HMeTb nepBhili NOpAgOK M0 KaxKOMy pearenty, oOmHH BIOpoH NOpAAOK H NOAYHHSTHCA CleLyOWeEMy KANCTHYeCKOMY 3aKOHY: cxopocte -= k [RX] [Y] a) OGvapyxeno, uTo sToT saKol cKopocTa cnpasegsmHB. Yxe orme- qanoch, ¥To unpa 2 B oc6osHaveHnH Sn2-mexaHHaMa yka3HIBaeT Ha GOHMoneKysApHocTb., Creqyer NOMHHTb, YTO 9TO He BCeTa TO xe, Io H BTOpoM NopagoK (7. I, pasa. 6.14). B npucyTcrena Gomb- moro H36nTKa Hykicopuna (ec1H |T0, Hallpumep, pacrRopHTesb) MeXaHii3M MO-MpexHeMy MOxKer OcTaBaTECA GHMONeKYAAPHHM, XOTH SKCHepHMeHTaAbHO onpeleseHHad KHHeTHKA peakuHu GypeT oTBe- 4aTb NepBOMy NOpsAAKy: cxopocrb = k [RX] (2) Kak yxastipanocp BT. 1, pasg. 6.14, Takaad peak HaaHBaerca peaxyued nceedonepeozo nopadKa. Kanetwveckve A0Ka3aTeJbcTBa — 3TO HeoOxoxHMoOe, HO He Jo- craTowHoe ycnOBHe, TaK KaK ROSMOKHW H ApyrHe MeXaHH3MBl, KO- Topple 6yAYT COrMaCOBHBATECA C STHMH AAHBHMH. 3HadHTeALHO Go- dee yGeqHTeNbHble LOKasaTeNbCTBA MOMMHO NOAYAHTH H3 Toro hakTa, 4To MexaHHu3M Sw2 npencKasbiBaet oGpaujenve KonpurypaunH, eCAK BaMellleHMe NpOHCXOAHT y XHpadbHoro aroma yraepoma, H 9TO He- OAHoKpatuo Ha6mogaqoch [2]. Takoe o6pamenne Kondurypaman (v. 1, pasa. 4.7) Hastpaerca eaasdenoecKum oOpawmenuem H SEIAO o6uapyxeHo 3anonro 70 Toro, Kak Xpos H Huroaby chopmyrnpo- Bald MexaHH3M Sn2 [3} 3yecb xeaTebHO BCOMHHTb O TOM, KaK B OPHTHHaAbHHIX pa- GoTax 6bi0 20Ka3aHO, ITO peakUHA 3aMellenHa MpoHcxoguT c 06- paulenHeM KoHdurypailwn, IpHtem rorya, Korma MexaHH3M peaK- -BHH ene He Obla HaBecteH. BaabAen [4] npHBer pax NpHMepos pe- ‘aki, B KOTOpHX oAHHO NPOHCXoAHTS OOpaulenue KoHpurypauyH. Hanpumep, (+)-6n0unyio KucAoTy AelicrBHeM THORMIXTOpHAa MOXKHO npeppaTHts B (-+)-xXxOpoAnTaphyw, a AeficTBHeM xJopHyAa boctbopa(V) —B (—)-xn0posurapHyro: COOH goon Goon (+)CHCI Sm Cycnon SS (-1CHEI CH,COOR CH,COOH CH,COOH 14 TJIABA 10 Onna u3 sTHx peaKUR AOAKHa HATH c OpallenueM, a apyraa— © COXpaheHiieM KOHHrypauMH, HO TOKa OcTaeTCA HeACHHIM BONDOC, Kaka H3 HHX KaK useT. 3Hak BPaWleHHA HAOCKOCTH NOMAPH3SALHA He MOMOXeT OTBETHT Ha 3TOT BOMpOc, NOcKOMbKy, Kak O6cy*KMa- noch BT. |, pasa. 4.5, HanpaBrenve Bpauienust He O6n3aTeMbHO CBA- 3aHo c KoH®urypaunel. Lpyraa o6vapykenuan Baspagenom pe- aKUAH: cooH goou Coon (cHOH ao (HICH KOH, (-)CHOH CH,COOH CH,COOH CH,COOH VM chosa Tor xe Bonpoe, B Kakoli H3 peaxunli A0.1KHO MpORCXOAHT o6pamenue Konburypauun [5]? Mono takxe sameraTs foro na- amuocTplipyerea aelicTBHeM THOHHMIxAOpHaa Ha (+)-n6n0uHyIO KHC- ROTY W Mocneayouen O6pasoTKoH npoayKra KOH], sro ontaecku AXTUBHOe COCRUHeHHe MOXKHO MpepparHTh B ero sHanTHOMep [6]. @uaaune, Kespow 1 corpyAHNKH paspaborasmM cepHio SKcIepH- MeHTOB AIM TOPO, YTOGM PelIMTL BONPOC, B KaKOM Xe ciyyae Ha caMoM fete MpoucxoguT obpaulenue xondurypanan. B 1923 r, Pua- aune nposex caexyioue peaxuun [7]: CHPh CAPA oy CHPh Me—CH—OH "+ Me—CH—OTs “ Me—CH—OBt = $33,0° a= +310 a = -19,9° K | B , CHPh CH,Ph . Me—CH—OEt Me—CH-OK Fg = 423,5° B stom uxkie peaxunit (+)-1-henna-2-nponaton npespamain B COOTBETCTBYIOUNA STHIOBL SbHP ABYMA MYTAMH: NyTb 5 upu- nogna k (—)-supy, a nyt B, !—x (+)-9bupy. dro cpngqererb- eTpoBayiO © TOM, 4TO NO Kpaiiie Mepe O“Ha 3 YeTHIpex cranuit JOUKHA HATH c O6palllenHeM KOHHTYpaHH. Upespmuafino Mavo- BepOsATHO, YTOOH HHBepCHA MpoucxonHaa wa ctaguax A, B uf, TaK Kak B STHX peaKNAX He pasphiBaerca cBasb C—O u HH B O2- HOW H3 HX HCTOWHHKOM KHCAOPOa B COe@AHHEHHA He MOKeT Cily- 2kETb pearenit, Ilostomy BecbMa BeposTHo, aro ctaguu A, B ux Cr gy c coxpasennem, a 5 —c o6pantennem konpurypaun. B mane- HeHeM NOLOGHEe WAKE HCCeEAOBATHCh HeOMNOKPATHO, HpHeM Beerqa NOAyYaNHch coriacoBalHible pesymbTaTH (cM., HallpHMep, {8])}. 1H oKcnepiiMenTE! He TODKO yOeqHTeNbHO AOKA3ANH, ITO OM- PEAKUHH AJH@ATMUECKOLO HYKEOPHJIBHOTO 3AMEULEHHA 15 PexeneHHbe cTepeocneundHiecKHe peak NpPOHCXOAAT ¢ O6pa- IeHHeM KOHHrYpalHH, HO TaKKEe NOSBOMHH yCTaHOBHTb KOHOH- rypauuu Muorux coeqnHenHit. . Basbyenosckoe oGpauienne 6bn0 OGHapyxKeHO TAKxKe H y Hep- BHUNOTO aTOMa yrieposa c HCNOAL3OBAHHEM XHUpaabHoro cy6crpata, coxepKawlero jelitepHii H BOMOPOL, CBAZAHULIe ¢ ATOMOM, OT Ko- TOporo oTHIenaAKeTcA yxoamad rpynna [9]. OSpamenue Kouury- pau oGHapyxeHo uw Aa peaxunii Sn2 B rasopoi dase [10]. Upyrne AoKasatenbcTBa Sy2-MexaHu3Ma HOAyWeHLI pH HccAe- RoBavHH coeaRHeHHA, comepKAUINX TNOTeHIMAABRYIO YXOAAULYIO rpymy y aToMa yraepoga B ronope Mocra. Ecan mocryaTn Me- xahusma Sy2 sepibl, ykxasaHibe CoeqHHeHHA He MOMKHE BCTYTATD B peakuUHid MO STOMy MexaHH3My, Tak Kak HykneopHA He MOKeT Npu6ansntTbeA K peakuHOHHOMy WeHTpy ¢ THbHOM croponH. Cpean MHOFRX H3BECTHEIX MIPHMepoOB GesyciieWHHX MONHTOK BOBAeTL BO B3aNMoselicrBHe ATOM yrileposa B roAoBe MOCTa B YCOBHAX OCy- ulecTBAeHHa peakuHH Sy2 [11] o6pa6orka [2.2.2]-cnctemis 2 arH- aat-noHom [12] n gefcteve ua ([3.3.1]-cucremy 3 noanaa HaTpHA B alleroue [13], B otvx cayyaax avanora ¢ OTKPHTOM WeNbIO TerKo 0 ar Br 2 a BeTynaor B peaknuio. H naKkonell, ene OLHH NPAMeP AOKA3aTeND- _ ¢TBa peamu3zauHH Mexanisma Sw2— 9To peaKUHA MexAy ONTHUeCKH AKTHBHLM 2-OKTHAHOAHAOM H pawHOaKTHBHEIM HOAHA-HOHOM: C.HyCUMel + *I- ~— C,HyCHMe*T + 1° Syech cnenyeT OXALATE palleMAsalHH, TAK KaK CCAH MCXOAMTD 43 aucroro R-430Mepa, TO NepBoHaqaAbHO B pesyALTaTe KaxAoro aktTa o6mena AQJKeH o6pasoBbiBaTbCa S-uz0mep. OnnaKo no mMepe Ha- konsennsa S-v3z0mepa OH C&M HauHeT KOHKYPRPOBAaTh C R-w30Mepom B peakuHH o6MeHa ¢ HOAHA-ROHOM, H B HTOTe TOMYUATCA PaBHOBec- Had panwemHyeckad cmecn. IIpono_uaoch TaKxKe CpaBHewHe cKOpo- CTH HHBepCchH CO CKOPOCThIO BKAIOIeHHA B MONeKyY padHoakTHB- xoro *I~. Hafigeno [14], sro ckopocTa aTHx ABYX Mponeccos paBHbl B npemenax OWwHOKR SKCIepHMelTa: cxopocTh HHBepcnH: 2,88 + 0,03-10-* cKopocth o6meHa: 3,00 + 0,25-10-* 16 THIABA 10 Ha caMoM jene H3MepANach ckOpOcTh palleMHsaunn, KoTOpad BABOe GOMbIIe, YEM CKOPOCTh HHBEPCHH, TaK Kak Ka2KAb aKT OOpa- IleHHA KOHHUrypanHn NpHBOANT K MOABAeHMIO ABYX palleMH4ecKHX Modekya, Baxuocth 3Toro pesyaeTaTa saKalouaeTCA ellie HB TOM, 4TO OH NOKASbIBaeT, ITO KaxKAH aKT OOMeHa MpegcTaBaser Cobol aKkT HHBepcHH. Suleumosep H COTPYAHHKH Mpeactapnau yOeqHTeAbHbIe AOKAasa- TeAbCTBa TOrO, 4TO NepexoaHoe cocToAuHe B Sy2-peakHAx AoM- 4%KHO HMeTb AnHefiHyi0 reomerpwia [15]. O6pa6orKa merHa-a-rosHaA- o-Tonyoucyabonata (4) ochopanvem gact o-(1-TosHAsTHaT) 6eH30A- cyabpouaT-von (6). Ponb OcHOBaHHA cOCTORT B OTulenAeHHH @-npoToua, TO NpRBOAUT K HoHYy 5. MoxHo 6E0 6H MpeanonoxKUTh, 4TO OTPHUaTeABHO 3apaxKenHE aTOM yraepoga woua 5 araxyer , C) Si SO. SO. On, ochonamce 0 | oo —_ , oh CH, oH ets cH CH, Ts Ts Ts / 4 5 6 : MeTHABHY10 Ppylny Np OcyllecTBAeHHH BHYTPHMOseKyAApHOTO Npo- wecca Sn2: SON, & ayy ort CH, Ts 5 Oawaxo ato He Tak. [epexpecrbimu skcnepHMentamn [15] (cm. omH- cane peakunu 11-32) 610 noKa3aHo, YTO OTpHUATeNbHO 3apA- WKeHMBI yriepOR aTakyeT METHAbHY1O rpyiily Apyrok MOAeKyAN, a He coceqHiolg rpynny Tol Ke MOveKYAM, T. €. peakWHA HMeeT MeXKNO- JeKYAAPHDI, 2 He BHYTPHMOMEKYAAPHEM XapakTep, HeCMOTPA Ha TO 4TO SHTpONRA MOCTeAHerO NyTH Gonee BoIroava (tT. 1, pasa. 6.4). CueqopatesbHo, BHYTPHMONeKyAApuaA aTaka He MOxeT MpousoliTH H3-34 HEBO3MOXKHOCTH AOCTHKeHHA NOAKOH AunetHOcTH, Taxaa cH- TyauRA pesKO OTMHGAeTCA OT CHyIaeB, Korza yxoANuLad rpynna He HCNITEIBaeT CTepryecKRX 3aTpyqHenHi (pasa. 10.5) a BHyTpHMOze- KyspHnit Sw2-Mexanu3m nerko peanusyercs. B wactosuee Bpema noKasaHo, ura mexani3m Sn2 BosmoxeH AAA BCX YeTbIPeX THNOB peaKuHit, nepeyMcneHHEIX B Hauase ra. 10, W Aaxke Aa peaxuwi tana TE, Korga oTpHuatenbio sapsKexHbll PEAKUHH AJIH@ATHYECKOTO HYKJEOPHIbHOrO 3AMEIMEHHA 7 HykeoHA aTakyeT NONOKUTEIDHO 3apHKeHHE cyG6cTpaT no NO- AOKeHHIO, HAHGONee YAANeHHOMy OT NOAOKUTeNBHOTO 3apaya [16], Hanpumep (R)-PhCHMe—SMeo-+- Na (S)-PhCHMe—N3-+ Me2S. B ra6a. 10.7 (pas. 10.11) mpHBegqe cnucok HeKOTOpEIX HaH- 6onee BAKHEIX peak, NpoTeKaiomlHx mo MexanHsMy Sy2. 10.2. Mexanu3m Syl Vgeanpnbiii papwauT Mexanuama Swl (samewenue nyxacoduso- Hoe mOonOMOACKYARpHOe, substitution nucleophilic unimolecular) BKAiOWaeT ABe cTaqHH (3fecb TAKKe He yKasaHH BOSMOKHNE 3a- pHabl cy6ctpata W HyKAeoduvia): medrenio Cmadas Tt R-X === Rtix Cmadun?: R*+Y “Hs py Tleppas crayun— sto Meqieniaa HOHH3aNAA Cy6cTpaTa, H HMeHHO oHa ofpegeaseT cKopocTh peaxunu. Bropan cragua — 2To Osicrpoe B3anMOevcTBHe MPOMeKYTOUHOTO KapOoKaTHOHa 4 HyKAeopusa. PactBopntenh Bcerqa OKa3HBAeT COReHCTBRE Mpoueccy HOBRH3aKHH, TaK KaK sHeprun, HeOOXOAUMAaA 1/18 Pa3pHiBa CBASH, B 3HAUHTEb- HOM cTeneHn KomMeHcupyeTca compbpaTaiuei Rt+ wa X. Hanpumep, HOHNH3auAA TpeT-6YTHIXAOpHAA Ha Tper-GyTHA-KaTHOK H XAOpHA- HOH B TasoBOH dase 6e3 pacrBoprtenn Tpe6yet 150 KKan/Monb. B.orcytcrsue pacrBoputers TaxoM Mpouecc Mpocto He Nolger unaue KaK Mp BLICOKHX TemMnepaTypax. B Boge AJA NIpoTeKaHHA AlAcco- DAanNH Heo6xo,UMO aN 20 KKan/MOnb, a pasHocTh—sToO aHep- THA CONbBATAaUHH. Torna, KOTZa PON pacTBOPHTeAA COCTOHT HCKJO- 4HTeIbHO B copeficTBHH oTIenTeHHIO yxorAMe rpymny c dpor- TaJbHOH CTOPOHH, T. €. KOPa MOJEKY/IEI pacrBOpHTeld He HMeIoT HHKaKOM BO3MOXKHOCTH YYaCTHA B aTake C Tha (Sn2), MexaHusm npercrasaser cobol npedeaoxorl caysad npoyecca Swl. Cymect- BYIOT KHNeTHYCCKHE H ANIC AOKa3aTeNbcTBa [17] Toro, yo MpH OT- puse X or RX Ape MONeKyIH MpOTOHHOrO pacTBopHtena Ob6pasyior cna6he Boopomtisie cBasH c X: -H—O—R “HOR TIpn novcKkax xokasaTenbcTBa ocyulecTaieHud Mexanisma Syl B MepBylo Oveperb cHeayeT OXKUAATH, YTO peakiunA GyzeT HMeTb Hepsei NopaxAOK HW TOAYHHATCA ceLyouleMy ypaBHeHHto: exopocrs = & [RX] 8) 18 TAABA 10 Tlockonbxy Me/VieHHan CTaXHA BKUOUaCT AHILb cy6ctpar, cKOpoctTb npowecca AosDKHa 3aBHCeTbh TOAbKO OT ero KOHICHTpalnn. Xora B Mpouecce HOKH3allun Heo6x02HMO coneficrBue PacTBOpHTess, OH Re BXOZHT B BLIPAaKeHHe CKOPOCTH, TAK Kak MPHCyYTCTBYeT B 60nb- WOM H36bITKe. OguaKO NpOcToH KHHeTUKe, ONACHBaeMOM ypaBHe- nnem (3), yaonneTBopaioT He Bce nannNe, Bo MHorHx cayaaax NeicTBHTeAbHO COOMIOMAIOTCA 3AKOHOMEPHOCTH AA peakuni nep- Boro MOpsaKa, HO H3BeCTHO Gouploe HCHO ApyrHx NpAMepos, Korga KHHeETHKAa OOsee COxKHA. ITO MOKHO OODACHHTD, IPHHHMAA BO BHRMaHHe O6paTHMOcTb NepBoli craguu. O6pasyomasicn Ha STO cragqnu yacTuua X MOxer KOHKypapoBaTb c HyKAeo@uiom Y npy BSaHMOefcTBHH C KATHOHOM, TOrAa ypaBHelwe CKOpOcTR peakuHA HeO6XOMHMO MOMMPHUAPOBATh CAeLyIOMUM O6pasom (cM. ra. 6): 4, RX == R*+X as Ri+yY —t> rv oh Ak ARXIY] OS = HR] + AY) B wauane peaxunn, Korga KoHWeHTpauua X ouetb Mana, Npou3- penenne &. [X} npexe6pexumo Mao m0 cpaBHeHwio c A, [Y] H KH- HeTH4ecKOe ypaBietiile peakKUHA MpHHHMaeT BHA, MpeacTaBnenuplll ypasHesnem (3). H B aelicrsnreabiocru peaknun Syl o6naHo HMeIOT MpOcTyi0 KHHETHKy MepBoro Topsaka B HadatbHEh nepHod. Kuterayeckne uccnegopaiina peakuuit Syl mpoBoaHAHch B OCHOB- HOM Ha IpHMepe peakuHA combBonnsa, TAK KaK SombmHCTBO Swl- peakuniit npHHansexut UMeHHO atom KaTeropuu. Ha Gonee n0sAHHX CTAAMAX MpOWeccOB COABBOMHZa KONUEHTpauA X Bospactaer H, Co- raacHo ypasHermio (4), cKopocth qomxKHa cumKaTaca. OOuapy- 2KeHO, ITO 8TO cipaBesMBO AH AHapHIMeTHArArOrenHAB [18], HO He In Tper-6yTHATaNOTeHHAOB, peakUHA KOTOPHIX Oo BceMy XOAY nogunusetcn ypapnenmo (3) [19]. Taxoe paasnnave oOpacHAeTCA TeM, 4TO Tper-GyTHA-KAaTHOHH MeHee CeACKTHBHEI, YeM GoTee cTa- Oudbibe KaTHOHE! AHapuaMeTHabHOro Tana (rT. 1, pasa. 5.2). Xora TanoreHu{-HOH — 3HauHTebHO Gozee crabib HyKneodua, eM BONA, NOCHeAHAR NIPHCyTCTByeT B 3HAUTeABHO GoAbUeM KONHUECTBE, NOckOJIbKy sBseTcA pacrBopuTerem [20]. Bonee cenekTuBHo B3aH- MOfeficTBYIONINA ANeHHAMeTHA-KATHOH BLIAepAUBACT MHOTO CTOMK- HOBeHHM © paCTBOPHTevieM Mpexse, eM COeAHHUTCA C Sone peak- WHOHHOCHOCOOHEIM TaJOreHHAOM, a MeHee CeAeKTHBHO pearupylo- WHA Tper-GyTHA-KaTHOH He MOxXeT 3KMATb CTOAKHOBEHUA C GOsee AKTHBHEIM, HO OTHOCHTeIbHO pee BCTpeyaloUlHMcA rasoreHHa- HOHOM H COeAHHAeTCA ¢ pacTBopuTemeM. : Ecan o6pasyiouanca B pe3ysLTaTe peakuan yacTiua X Moet CHYWKAT eC CKOPOCTh, TO HO KpaitHeH Mepe B HEKOTOpbIX cayyanx