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C e p II R. ARTYaAbHH8 BorrpOCH XHMRqeCKOll HayKR H TeXH~OrRH n oxpaHU oKpymammett cpe~

3~eMeHTOOpraHnqeCKRe coe~eHRH

OE30PHAH l1H.MllpOHOB

3~eMeH'r repMaHHll 61>'.J1 OTKpHT B 1886 r., a qepes ron CRHTeSRpOBaHH ero rrepBue OpraHHQeCKHS COe~EHeHHR. O~aRo aKTKBHO 3TB

06ABCTb 3~eMeHToopraHRqeCKO~ XHMHH CTa~a pa3BHBBTbCR B 50-0 ro~ aaasro CTMOTMR, sorna iIORB.'leHm, pa,ll;HOs.1f6RTPOlll!1tH: BU3BaAO rrpoMHlll-AeHBoe npoasnoncreo ;'epMuHlUI R or c rI;JocToillll"I!:X B60praIDlqeCRRX coo.llHHOHID1.

B I95~ r , ""'cOpoM C5U.1J0 HB'lilTO CHCTeMaTPlT.£OCKOe HCCJlo,nOBaHRe B O,:'JIROT2I JmMJm r,?pt.alm.t:!opr,'c'HqeC'WoX coe.mrneJm1, .ltOTOpOe nponczsa;,w,;, i! c;e~qac u :;',2] .

E -co BPOMR E ():-'I'iOHll'lO"i'O.t:! XRMIl"~ :>:23MeHTOB lYE rpynml (yrJlepo,ll, RpeMHlltt, repMa!njj.~. '"JIOBO, CBl'!H8U) ID'I8ACR HaCT~ltO cymecTBeHHID\

npo08;; B qaCTll ~:~Mm JYOMatm.fl, 'fTC' H6B03MOlKHO C5wro orrpe,neJIl'lTl>, R tre;.~y OJ!IDll'6 XIlM1!f' 1'8 PM~Jl'/.~',: !\ XIDf.'AH RpeMHRH = OJIOBa.

B Haqane nCC~e~OBaHRR npeC~e~OBarrRCb qnCTO CHHTeTHqeCRHe ne~,OCOOeHHO nnR HY~ CpaBHRTe~HOfi XHMRll 8~eMeHTOB lYE rpynnH. 3aTeM OCHOBHHe YC~E 6~ HanpaBJ1eHH Ha nonCR rrYTefi nO~qeHllH bnO~OrHqeCRH aRTRBHHX COe~eHRH repMaHnH. B VoTors 6HAa cos~aHa CllCTeMa oprrrHHa~HHX nperrapaTRBHHX MeTo~oB nO~qeHHH paSHoobpasHHX ~aCCOB coe~H8Rm' repM8HllH, H3~aHH rrepBHe MOHorp~HH no XHMHH opraHllqeCRHX coe~eHHll repMaHHH [73), llX 6HO~OrnqeCROfi aRTllBHOCTH [Z29} H ilK-crreY-TpaM [147l , FJamlCaHH ocsopa no OT~eJII>RIlM pas~e~ XRMEn repMaHliff [4, 21, 84, 124, 146, 158, 163, 169,189-191, 202, 208, 214, 219, 225-228, 232, 234, 239, 250]. K 1960 r. rrOHBH~aCb BOSMOXBOCTb c~e~aTb Bno~e onpe~e~eHHoe Sa~qeHHe 00 8Ha~OrHR OpraHllqeCROfi XHMHll repMaHHH II RpeMHHH H 0 ~OBanbHO SHaqnTe~HOM ee OT~~ OT XHMHH O~OBa II CBHHUa, XOTR aTO paS~qlle R He TaRoe npRHllRllHaJII>HOe, KaK Me~ XllMHeH yr~epo~a H OCTa~bHHX a~eMeHTOB lYE rpyrrrrH [17, 23, 48].

STOT BHBO~ n03B~, KpOMe Toro, sa~MaTbCH 0 p~ repM8HRR B xa3He~eRTe~HOCTR KKBHX opraHllSMOB, TaR KaR R 8TO~~ BpeMeHll PO~D RpeMHHR K8R 6HOMHJtp03~eMsHT8 yif{e He BHShlBllJIa COMHeHnfi.

~efiCTBHTeJII>HO. BC~e~CTBHe aHa~ornn XHMHqeCRllX npeBpameHnfi coe~eHnfi KpeMERR H repMap~R MeT8bo~3M coe~HeHHfi STllX ~yx 3~eMeHTOB MOZST ORaSaB8Tb BSaHMHHe TOHKlle ~RHRR. He HCK~qeHO, qTO repMaHHfi MO~T BHcTynaTb H B po~ caMOCTORTe~bHoro dlloMnKp03~eMeHTa, ~~T B ROTOpOM, H8coMHeHHo, nCITHTHBaIDT Bce ~He opraHH3MH. CobcTBeHHhle H ~TepaTypHHe ~HHHe noc~e~llx ~eT rro~TBep~aIDT dnarOTBopHOe B03~eficTBHe MHOrHX coe~eHnn repMaHllR Ha pa3Hoodpa3Hue opraHH3MH OT BHcmmX ~o HH3mnx [169, 2291.

B HaCTOBmee BpeMR XHMHR repMaHnfiopraHnqeCKllX coe~eHllll llcrrhlTHBaeT nepllOn pacnneTa r~aBHHM odpasoM lls-sa nepcrreKTllBHOCTll nOllCxa cpezra coe,mmeHnfi repMaHI!H HOBHX wapMa:QeBTllqeCRlIX npsnaparon. Extero~o B 8TOfi ocaacra nOffJ3JIH8TCR OKO~O 400 rry6~RaIJ;llfi. a ocnoe llX Ro~qeCTBO y~e ~OCTnr~o rrpRMepHo 15000, as HllX ORO~O 5000 - OTeqeCTBeHHHe.B~bmRHCTBO 9THX ny6~Raunn paccMoTpeHo B Hamnx MOHOrpa~RX R oosopax, a Ta~e B MOHorpawnn M.]e6y , n.Masepo~ II 1Il.Ca~ "OpraHJllqecRHe COe~eHJllH repMaHRR" (M.: Map , 1974; nep. C aar,n, ).

1. XIDiMiI TPffi'AJIOI'EHI'mIAHOB

~aif{e B HaCTOamee BpeMH cnHTeShl B odnacTll OpraHVqeCKllX coe~HeHHH repMaHHR ocymeCTB~ Ha OCHOBe Tpex nORa C~HCTBeHHO ~OCTYllHhlX ero HeOpraHHqeCRRX coeAHHeHnfi: MeTa~qeCKOrO repMaHllH, ero

2

~0~C7~e H TeTpar~~OreHll~OB. IT09TOMY B Haqa~e RCC~enOBaHKH npenCTa&np~OCb. QTO ~CrrO~30BaHlle B CKHTeTHqeCRRX ue~ TpBXXOprepMa

Ed HGeC13 (HaY.6~ee npOCTO nO~qaeMOrO rnnporepMaH8) OT!poeT mHPORile H npOCTHe nyTZ nO~qeHRH OpraHHqeCKHX COenHHeH~ repM8KKH.

neaCTBKT8~HO. 9TO COB~eHHe ORasanOCb qpeSBUqaaHO ~onOT»OpHUM o&beRToM Hec~eAOBaqHn RaK B T90peTHQeCKOM. TftR H B upenapaTHEROM OTHOmeBJtIt [22. 72, 73. 84. 208, 225. 22eJ.

Bw:rCBMOC:&. qTQ He TOJI:&RO HGeC13 • HO H .lijlyrHe TpIIl'B.lOreHr9pMaau npHC09~CH no KpaTHHM CBR3RM npaRTHQeCKK Bcex Henpe~e~HHX coemrnemm [00. BMe9 roro , oaao OclHSpyJEeBO. ~TO C COIIp!DltElHHHMH ~eHaMZ pesRURH IIpOTBKaBT C~BnyDmY.M oclpaSOM:

( + HIileHa13 ----...,~ ~GeHa12 + ItHal-;»: T.e. anepBue clwro yOT8HonnBHO, qTO Tprrr~1~r9H09pMaHll B p~e peaRmrlt MoryT llBJIRTIoUli HC'j'O'UiI'IKaMH peaxnaoaaocnococnsx ,llHI'anOreKlUlOB repMSHHli TRna KapcleHOB:

..HSeHa13 _ .... Ir-[seBa131-::c:..===== GeHa12 + HHal

3TO oclCTOJiTe~b01'BO v. r'np~;flBJIR81' MHoro06pH3HB Xl!MHqeCRHX nper;p8lllelUill HGeHa13 B PEl3lmJ'!JIX ~alRe r: "',,,!illM!'! H TBMH lKa Coe,ll,l!lHeKl!lm.m. ,,-w:e oonapyxeno , QTO n]J7 E:.;.;TIl= B P';:'KI::;J!OHIIO~ opens IIpOCTHX aitJHPOD j'( awmOB. OOpiJ:]IDl'NX ;~ HG'JHa 1. I(oMIIJIeI-:'~'""'

4

1.1. HOBus rrpocTHs rryTn rrogyqeHTIa sWnpaToB n aMRHaTOB TDHralor!HrepMaHoB, a TaR~ lia0RcaHaToB GeX2

~e BHHKnep B 1886 r, odRap~, qTO repMaHRfi pearKpyeT rrp~ ~ 3000C C raaocopaaaof HCI C odpa30BaHneM HGeCI 3, MlI YJIY'mITIJlll

STOT crrocod rroJIYq8HKR HGeCI 3, rrpnMSHMB rropoDKoodpa3HyID MenD KaK KaTaJUI3aTOp, qTO CYlI\C:;TBSHHO rrOBlICllJIO BUXOn HGeCl 3 [9] , O,ll,HaKO STOT rryn OKa 3aJICR M8JIO'TpnrOneH ,lI,JI.H rrOJIYqeHRR HCJeBr 3 [50, 5IJ II COBepll1eHHO HerrpReMJleM ,lJ.'IR OllHTe3a HGe13 n HGe~3' B8pOHTHO, yYr.e He cYJlleCTByIDIqnX B CBO(iO,ll,HOM COCTOHRlfil.

C STIWOBbI:M R npyrIlMn s:pnpaMll EG-8CI 3 ,-IfGeBr) ,HGeIJ jI[ HGe~3 oopasynr YCTofi~lIe KOMrrJIeKCHlie cos~HeH~q - 3wnpaTu L47J, rrpenCTaBJIRIDIqne codott MacJIoodp83Hue ~KocTn, OKpa1l18HP~e, COOTBeTCTB8HHO, B ~eJITlIft, op8H~eBlIft, qepHUll II 3e~eHoBaTlift UBSTa [41, 51, 105, 1I4J. 3Tll sWzpaTli nOqTn He CMelllMB3IDTCR C 1136UTO~HM 3WnpoM. COCTaB 3WllpaToB He RBJIHeTCR nOCTOHHHHM II 3aBllCllT, rrO-B~ll~OMY, oT CJISnOB BJIarn, rronanarolI\efi B HllX np~ rrOJIYqeHHH. HarrpnMep, rrpn ~OdaBJleHllR B03paCTarolI\llX ROJIllqeCTB BO,ll,HOrO paCTBopa HHal SmllpaTH HGeHal 3 H3quflalOT norJIOlI\aTD sWnp R, HaKOHen, cMemnBaroTcR B HIlMll B JIIDdux COOTHomeHR.'IX, ITpn B3aIlMOnell.cTBllR HGsCl 3 I1lJIlJ: sro sWnpaTa CHBr npoaoxonnr nOJIHaR 3aMeHa BCSX aTOMOB XJIopa OpOMOM. 3TO nOKa CaMuH ynodHHH cnocod noJIYqeHIDJ: HGeBrJ[!lI, 50, 5IJ.

Haron rronHTKR nOJIYqSHRR HGe13 nporrycKaHnsM ra30odpa3Horo HI qepe3 HGeCl 3 RJIR ero ~jI[paT He YB8HqaY1nCD ycneXOM: nponyKToM peaK~ll He1l3MeHHO OKa3HBaJICR AByttonnCTllll rspMaHRll [50J.

31)RpaT HGe~3 dli.'l nOJ\YqeH HaMR rrpn pacrsopenza Ce~2 B 3WllpHOM pacTBope WTopRcToro BOnOpOna (JI[JIll npll rrponyB8HRR ~ qepea 3WllpaT HGeC13). ITPll nOdaBJIeHKll B STY peaKUllOHHyID Maccy reRcaHa npOIlCXO;II,llT paCCJIOeHlle H BaneJIR8TCR SWzpaT HGe~~ - 38JIeHOBaTaR MaCJIHHllCTaR OqeHD BR3KaR lKH,IUIOcn COCTaBa HGeFJ~Et20 [I05J. O,ll,HaRO HaM He ynaHOCb llCnOJID30BaTD STOT SWllpaT B npenapaTRBHlIX CllHTe3ax, TaK KaR H8113MeHHO rrpOT8RaJIll peaRITllll nOJIIlMepll38ITllR HerrpeneJIDHHX coennHeH~. ITOITHTRa CeJIeRTMBHOrO BOCCTaHOBJIeHllR GeX4 no HGeX3 rnnpnnaMM MeTaJIJIOB HaM He YnaJIECb [75, 89, I34J. HaRoHSn, MH odHapYmEJIH, qTO I,I,3,3-TeTpaMeTHJInHCllJIORCaH (TMnC), JIerKO nOJIyqael&ift ~oJIll30M nOCTynHoro ~eTHJIXJIOpCllJIaHa, RBJIReTCR BeCbMa s~eRTHBHHM pear8HTOM ~ npenapaTllBHOrO npnrOTOBJIeHRH s~npaToB HGeX3 ll3 TeTpara~oreHrepMaHoB, B TOM ~c~e II HenOCTyrrHoro panee 3WHpaTa TpllAonrepaana [I34}:

en CnJ JI ,

H;Ji-O-3iH+GeX, i I 4ell 'JHJ J

8:!mp8'r Tplllio,nrepM8H8 rrpe,UCT8B,'IHeT C060ll '1SpHyD TmKeJIYKl HeCT8

6~bHYID EH,llROCTb, ROTOp8H He CM8~>ffiaeT CTeKnO, Hep8CTBopRMa B SWz

pe H "BhIChlxaeT" rro.u B8RyyMOM C Bhl,ll8JIeHHeM Ge~2. )l.rr.q CeJIeRTRBHOro

BOCCraHOBJIeHHR TeTparaJIOreHH,llOB repMaHHH FpOMe TMnC 6hlJIH Hcop060B8HhI U ,npyrue r,mpOc~~aHhl, H8npHMep GH3C~D:. HSiCI , (CHJ)2SiHCl

J II (jDtO) 3SiH, 3 T3K;;;e rI1,npOCMOKC8Hhl, B qaCTHOCTH CMeClI OJm1'OMe

pOB (llliSiO) x' rrOJIy'l8allli8 rp.JlpOJlJl:;CM RHSiC1 2 (R - CR)' C~5).O.!\H8

\(0 see 9TU C08,nilHeHllH B pe8l\llIDO C GeClil B cpe.ae sq,Hpa He BcryrraJIH. IJccJIeJJ,YR X:HrWQ8CrmS CBOllCTB8 9i!mpaToB TpHrGlJIOrell1'epM8HOB, rro

JlyQeHHEU rrpn rrOMO!l11! TJ,J,L.C. MhI yCTaHOD,iJII1, 'ITO 9TH -cOe,llRHeHllR 06JIa,na

IeT TaRoll ze pearoraonuccnoooonoc-n,n, KaR H 9

MH 06Hapy~, qTO rrpH rrporrycRaHHH aMMHaRa B ~HpaT TpHXHOprepMaHa, a TaKEe rrpn RTIITHqeHRH H36HTRa 3WllpaTa C reRCaMeT~CKnasaHOM 06pa3yeTcH 6e~aH RpHCTa~qeCRaH CO~ TpHXHoprepMaHaTa aMMOHM [105J:

OpraHRqeCRXe 8MHHH rro~06HO aMMRaRy To~e crroc06HN BHTeCHHTb ~p H3 s¢HpaTa TpR~oprepMaHa. 8TH ~e ROMrr~eRCHHe coe~leHHH 06P83YDTCH H npH 06pa6oTRB HGeCl3 ~ ero 3WllpaTa CnITHHORHC~ paCTBOpaMH co~efi aMllHOB:

r~e X - CI, Br; n=1-4. 8TRM cnoc060M y~aeTcH no~y~Tb Ta~e (CH3)~GeCI3' M3 CnITHHO

Kllc~oro r~pORC~aMllHa XHOpHCTHfi BO~OPO~ BHTeCHHeTCH TaKEe ~paTOM TpRxnoprePMaHa.C~e~OBaTe~HO, HGeCl 3 II ero 3WrrpaT ~TCH 60~ee C~HHMK Kllc~oTaMR, qeM HCI, qTO OTMeqa~OCb HaMll n paRee [75J.

Bce rranyqeHHHe coe~eRM C MeT~- II 3T~aMRHaMn - 3TO 6e~e RpRCTa~qeCRRe nopoffiRR, npH rR~o~se Bo~ofi 06pasynmne Ge(OH)2' pacTBopHMHe B co~ol RRC~OTe R nOqTH He paCTBOpHMHe B opraHnqecKRX P8CTBOpHTe~.

KOMn~eRCHOe Coe~eHne (CzH5)~GeCI3' 06p8SyDmBBCH C 60HDffiRM 3RSOTepMHqeCKRM 3~eRTOM rrpH C~aHRH ~paTa HGeCl3 C TpH3~aMHHOM, rrpe~CTa~T c0601 ~e~TYD Mac~YD ~OCTD, He CMeffiHBa~DCR c ~POM R ~pyrHMR OpraHRqeCRRMR paCTBopHTe~R. 3WRpaT HGe~3 06pasyeT C TPR3T~OM RpHCTa~qecKRfi ROMD~9RC.

B 3a~qeHRe ynoMHHeM 0 CllHTese HS aMllHaTOB TpRra~oreHrepMaHOB HOBHX ROM~eRCHHX coe~HeH~ repMaHM - aMHHaTOB TpRa~ORCllrepaaaos [16r]:

R + R'oa ~ ROH 3NHGeC13

+ R3• R3N'HGe(OR')3'

TpHa~ORCKrepMaH (RO)3GeH B CB060~HOM COCTOHHHll B~e~TD He y~a~OCD, HaCTanDRO OH HeycToI~.

3TH HOBHe r~pOrePMaHH nOSB~ rro~qzTD HeRoTopHe paRee He.n.OCTyIIHH9 C09,II,HHeHHH: repxarpaa [160J, rePMMID'lpH~HH [r79]ll;IijJ. [r61, 186J. Tpl'lI'a~OreHrepMaHH HGeHal3 R HX ROMll~eRClille coe~eHM, ~P8TH H aMEHaTH c~e~eT paccMaTpRBaTb RaR pasHHe peareHTH. na~e ~ ~paToB HGeC13 C pas~qaHMH 3¢HPaMR peaKURoHHaH crroc06HoCTb cymeCTB9HHO paszasae-rca D:07].

6

3

Lanee jy~eT rrOKasaHO, qTO Haxo~eHRe rrpOCTHX rrperrapaTKBHHX nyTefi CHHTesa Tprrra~OreHrepMaHOB H ocodeHHO HX aMHHaTOB H ~pa

TOB, a Ta~e ~OKcaHaTOB ~a~oreH~OB repMaHRH OTRP~O mnpORHe rryTli CllliTesa pasHoo6paSHHX OpraHHqeCRHX CoeArrHeH~ repM8HRH.

1.2. PeaKUnH rRnPorep~poBaHHg

no 1958 r. CqHTa~OCb, qTO rrpHCOe~nHeHlle TPH~OprePMaHa (HGeC1 3) rro KpaTHUM CBHSHM Herrpe~e~HHx coe~HeHHfi MO~O ocymecTBHTb TO~RO B ~eCTKllX YC~OBHHX II llCKnIDqHTe~bHO B rrpHcyTcTBllE nepeRHcett RrrH rr~aTHHOBllX RaTa~saTo~oB. O~aKo MH o6Hapy~, qTO HGeC13 H HGeBrITpllCoe~HroTcH rrpaKTHQeCKH K ~6llM Henpe~e~bHillr, coe~HeHllRM npll KOMH8THOll TOIr.rrepaType 683 KaRllX-J]}'!60 KaT~:,aToJpOB II Hepe,lJ,KO C 3R30TepMllQeCRlli~ 3~eKTOM. B HaCTom~ee BpeMQ 8Ta ]J6aKURH cTaxa npocTefrnl~r. nyTeM CllliTe38 pa3Eoc6pasH~X repMBFHHOpraHHQeCKHX coe~emn"! [9, 15, 19, 2, 26, ;~9, 30, 50, 53, 7~, 84J.

HaJ]}'!qne 3~eKTpOHQaKUenTOpHllx saMecTllTe~ea y yr~epo~a rrpH ~onHOll CBH3H CHll*2eT crroCOOHn0Tb Henpe~e~H~x ~oeAHHeH~ rrpHCOe~HTb Tpllra~oreHrepMaHll. TeM He M8Hee ~a~~ XJIOpHCTlltt BBH~ R ~yrRe urre~llHl1 c 3~eRTpOHOaK1J;f!j1TOPHHMll S8M8CTHTe.'lJ1MH .I\OCTBTO'lHO JIerRO npacoe,il,v,JjfllOT rpaxaoprepaaau. HaupffMSp:

:'''Z=CHCl + RG'3CL ---

\ I

~~4CllCGe!-la13 \ /'/' I

\ " "C~C\ + HGeHal

3 - HCl] -- ",C,-}, r I I llalj - ~e ~ -C - C - Go/ -, l I I \ Hal HEel Hal X

llOoTOMY MomHO 6Ufl.o O~.3Tb oGpa3cBaHllH yCToticrrrnux r6Tep~qeC

RHX COe,IUYHeHvJl B pesy.n.rare rrpnCOe,IUYHeH:IlH HGeHa13' H8rrpllMep, K COrrpmKeHHHM ,JUlBHaM BJTIil al.\BTll.1IBHY •

.llBlIcTBHTeJI'bH.o, B3amw,lJ,BlIcTBHe llUl,lJ,KorO 6YT8,lJ,lleH8 C HGeC1 3 HJIU HGBBr 3 rrpllBB~O K nO~Y'lBHKn OMBO£ nBYX COBnHH6Hnil, O~O n3 KOTOpUX oK83a~OCy, reTBpOIJ;l'lRJIOM [29, 30, 50, 56J:

/Hal

I GeC -, Hal

K o6pa30BBHKID aRa~OrllqJiUX rBTBpoUilKJIll'lBCR11X COB,JUlHBHllll OR33aJIllCy, cnocoonsaa H rOMo~orll 6yTa,lJ,HBHa [56J:

~3 CHZ=y-CH:CHZ + HGeCl 3 ~

+ CH3CH=CCHZGeCl 3 CR 3

O~aKO nUnBpHJIBH H nnR~OrreHTa,lJ,lleH B 8THX mB YCJIOBllHX B33IDMO,lJ,ellcTByIDT 11C~qnTeJI'bHO rro CX6M6 r11,lJ,pOrepMHJIllpOBaHHH [26, 3D, 33, 41];

CH=CH I .:: CHZ + HGeCl) CH=CH

06pa30BaHHB OllHcaHHHX Bume repMailH~,orreHTBHoB MO*HO 06bHCHHTY,

I ,4- ~ 1, 2-npHCOe,lJ,nHeHlIBM (c rroc.lIe,IJ,ylOlIlBlI neperpynrmpoaxoa) K COrrpmKeHHOMy ,lJ,lleHy ~a~OreHH,lJ,oB repMaHITH, 06p830BaBll11xcH H3 HGeHal~.

~ UO,lJ,TBepm,IJ,eHH~ oTcro npe,ll,UonaaeHHH MU rrpOBBJIll peaKUnID 6YTa~ ,lJ,H\3Ha 0 8eBr? H upn aTOM 06HapYllll1JIR, 'ITO o6pa3yeTcH TOT me reTeponHRJI, 'ITO H ~ HGeBr3 [50, 51]. 3TOT me reTepOllllRJI KopOlla o6p23yeTCH 11 C ,lJ,HoKcaHaToM GeBr [ZOBa]:z

____ CI-I 2CH -,

"'''"'2 ,GE;,=CIIC'I=CH2 -- GeBr 2 GH..... /

CH2

:'8 : 83 ".-':'8 b H8:ICCJI8J\OBElHHblMl'l H6rrp6):\6JII,H!I6 C06):\IDl6HIDI, CO):\6pza

'iU'!e ';YEc::·.:\Q,,:,m,TiLl8 rpyrmnpoaxx, CrrOC06Hbl6 psarapoaars rro C:B1I3JlM I)C-C~ (3 '!~CT::OC·i'l!. H8rrp8):\8JIbHble KllCJIOTbl, cnnpru, aMRHbl II np.}.

'T'2': He '''8H8e NIH 8oHaPYl¥J1.TLll, 'iTO J...Je. -Herrp6):\6JThHble KllCJIOTbl [:./IJ J1el'zn ITjlIlCOO,IT,JlEHlOT TpnraJlDr8Hr6pM3HH, 06pa3YII COOTB6TCTBj'lDme J - Tp;l)UIOprepMlt.n~,C1M8li1eHHHe ImC.JlOTU B BIl,ll6 66C\lB6THHJC KpI1CT3JI

:1!'!OCKI!X rrp0JI.,VKTOTJ (eM. 3 .n. :Ii' O"EOBO rrO.J:Y'IeHIloro rllaT8pHa~~a MOJKHO CJ\6,ila~b CJIe;n.yIrnUle BHBO

.!lH. C~..JIOHHOC':'I) lIGeJ{n13 t: peQ~J;1IjIM r!'ULpOrepMllJrnpoBaHH.fI nanaar OT

~L:\:l J ;-: =:\-~e.J:CJ M ECf"3 [:3' 1'. e. B I""Jrv~ }:\.O Harrp3BJISH1UI, B KOTOpOM B03

[1"caeT CKJIOHHOCIb hGeHal~, K reH6pal\llll G6Hal,;' 8iPllpaTH II aMllHaTH

j~G{), :5 M81lE8 CKJIOHHbI I( peaKIUlHM rv.,llporepMl'lJlllpOBaHHII, 'IeM RH):\HBll)lyaJIb'-' Hue ':e1:81,J" liepeJ!.)(o rl1)jpOrepMl1J1llpOB8HRH C HHMH Bo06m6 H6 npoac xo

znrr , c '.1bIT8CHileTCH ~8aKlUI6H ):\BotiHorc r6pMwrnpoB8H:1l.fl llJIH oopasosanxa

IlOJIl1l.:·3iJ ra , C 81PllpaTaMIl HGeEa13 B pe8KWI:JO rH,DJlor6pMwrnpoB8H¥Ifl XOpCUlO ?'~Tyna~T I TCJThKO C06)ll11l6HRfl C COrrpmK8HHliM.II Kp8THIlMll CBII3.flM¥I, OC068H

'In ::C~:;-CC .• AMIDlaTbI HGeHa13 B pe8KIJ;llIC rn,uporeDMwrnpcBaHllil aoomue :'8 IlCTYIWlO':.

AMlmaTl; :rm) :3GeH co.::ree peaKljHOHHOCrrccc6HH, 'I8M aMllIlam llalJ;eH, T'W ]("K npac: 8!J:l1HIlIOTC:; no RpaTHJB CEil8ll } -H6rrn8,I\8JThHLlX Rap6oflHJlb

i"", CC6JUlH8Hh.1 n 8KPlLlOHIlTPllJI8 [161J. OHll C ycnexoe nCCC.Jl130B3.ffilCb [;m, rn,llpOT"3pr'.'!rJII;pOB8mu" B:rlcll:'lIIlnp;a,'HoB a Bl!Hfl.i1Ir:: PPCJIl1,llCli3 [l79J:

.~./ c./ o:)c'_;,C' }{;)b:~J'; pe~~.:':c~l.rq K2I{ T~~f-j )'·::

HanpHMep, HGeC13 B OTcyTCTBHe 3~llpa pearnpyeT C aueTH~eHOM no~oOHO HSiC13, T.e. nCR~quTe~HO no cxeMe npllcoe~HeHllH:

HGeC1 CH.CH 3 ~ + C1CH2;CHGeClJ 3GeCH2CH2GeC1 3

O~aRO HarrpaB~eHlle peaRUlln pe3RO MeHHeTCH, ec~ ee rrpOBo~nTD B cpene 3~llpa, r , e , c 3cPnpaTOM HGeC1 3 [30, 41J:

AHa~orn~o pearllp~T MeT~- II n30rrporr~aueT~eH, a TaR~e ~~opOYTllli [77, 148J:

GeCl3I • ClCH2C = yCH 2Cl

GeC1 3

HGeC1 RC~CH -. Cl3 3Gey=CHGeCl 3

R

rne R = CH3• (CH3)2CH-. PeaRlU~H ,UBofiHoro repMn~poBaHnH nHorna corrpoBo~aeTc~ OO~D

HHM oOpa30BaHneM rro~~epoB:

C TpnOoprepMaHoM peaRURn ,UBOllHOrO rep~poBaHnH rrpoTeRaIDT n B orcyrcraae ~npa [50, 5rJ:

IO

~poc~e:ITllile HepSSB8TBneHHHe O~e~RHll (rrpOnnneH, 6YTnneHH R UHR

JlOreKCe,,), 3KT}:BP.O rrplWOeJlllHHJa]l:ffe TpRXJIOprepM8H no cxexe ranporsp

MRJ:rrlpOBaEll~ B OTCyTcTBHe 3~HP8, C 9~RP8TOM HGeC1 3 06paSYDT npO~RTll JlBO(IEoro repMvwrnpOB8HIIH [94]:

Cli 3CH = CH2 ------,l _ _ _ ~ HGeC13 _

CIL:,CIO",CH2 I PSSBeTBJIeHHUe OJIecj"'lL'lli (TeTpa.~eTMeH II Tjll\TllqH06YTII~9TMeH) B

O'l'.TII'!;:e 0'1' YllOMJiliYTbIX Bl1II1P, OJIe!jiMHcL' He BC:yI1a;Yr B P88KUmJ ,lUloiffio

rc repl~~pOBaHllF C U,G8C13 , KOTH MO~RO OHJlO O~MnaT~. 'ITO 9TH H8H60J:e8 3KTIDllill8 axnenrops Ktlp6eHOB OYTS' aRTiffiEO :IPZC08)llffiHTl> H R8p68

r:'JM.n GsC1 2, Vl:CTO:rHTrKOM so roporo FfL~_j{eTCFI :!Ge"..; \3. B .Il8HHOM CJlYQa8 CT8P;~'I8CKII8 rrpeITH'T'CTBliiJ., IlO-ElI,1U1MOMY• .Il8JI81lT

H8B03~OEHOn pe8I~ JlBOaHorO repMM~~poBaHflH, a rrOBHill8HH8H 9JI8RTpOHH8H n",OTHOCTl> ;'!,BOUHOn CB.fl3ll :)TEX OJJe

Oopa30BaHH8 npO,IJ,yKTOB .!lBd'lHOro r8PMilJllipOBaHlIH :,:,)~:HJ 001>HOHl:Tb

](aK peay.nsrar pfl.!lI'lKaJIEHOrO rrpouecca [41J:

O.$a](o rrpe.n:rrOQTHT8J1bH08 rrpOT81(8Hl18 3TIIX P8~11Q1IIii B 3\I'lIpHoi1: cpe

.ue (B 3qmpaTe HGeC13 ua OCHOBaHlUI cnexrpon lTI\lP OTI,18qeIl8 [JO}IHaH "pOTOH1l3aUHH aTOMa BO.!lOpO,I\a), nO-BYI,I\lIMOMY, HCKiOOqae-r raxoe 0611"C

HeH1l8. MOJKHO npe,I\nO}18JtJITb, qTO cymecTByeT 8m8 J.llIlH i"eX2Hl:m,' peOl(T:mi

.llBOllHOro repMilJllipOB8HIL8, KOTopHll m:JIJOqa8T r;Ta)],I'F) 8Dra3JB8HilH ll:1

IlGeX" rexcar-anor-ennnrepaana Hero npncoe.nnneuue no F[J8THbL\1 CBRSHM

Herrp~,I\eJlbHHX cOe,I\HHeHllli [135J.

1.4. PeaRWIH ROHneHcau,nl

ITPH rrOrrUT](e rrpllcoenHHllTb HGeC1 3 K ':5pCJ!"IlCTOMy a}!}]]l}]y BMeCTO (-OpoMnporrvwlTpllX}]oprepMaH8 oopaayerca D.l]}]]lmpllXJJopl'epMaH [l3,

:;4, 134J:

AH8}]OrllQlJO nncr pe8m,\IlH c 6POMllCTblM rU':':.T:,;~:,Ji":': Ii i1Ci,!lllCTW,1 8)]

,JIILJlOM. 0.I!H8RO (' X.lIOPllCTHM aJIJI}l}IOM peaKUll,\ n~1'\i'fJI(:WT uo c xeve npn

c:oenllHeHllH, II .JIJlIlJb C JlTnpaTOM HGeCl:J peiWI'~i' "'::Hl"B.'!neTCF B CTOpO'

uy KOH.!l8HCaUlm:

.i-> C1JG

~I'l' ,, 3" ,'u '.;:

AH8}]OrHQHO nporaxaer peaRUJ'HI }; C XJJo1,rw 'Ill' :iI.7UL'J:OM, tl 1....,

.llpyI'llMll 1> -a}]KeHJl}]ra}]OreHlwm,"l1 [4, 3:3J:

':;;::::31':') c }-x.1IOPllMI\JIOlI8HTSHOM pSaRIlliH rrpOXO,IUIT RCl\JIIlJqRTSJIl,RO lIO Cxel,~8 l\OP.,lI8HCaIl,Jm HsaaBllClWO OT H8JIR'U'!R llJlli OTCYTCTBIDi siPRpa [33, 49J:

CH2 --I CH

B OTJIil'inS 07 J -XJIOPOJIS

CJI8.ny8T OTM8TllTb, qTO B PM8 CJIyqa8B 3TY peaKID!IO KOH,U8HCaUlUl CJI8.nyeT rrpOBO~Tb He C RCH a C ilCXO~HMH RCH20H II2Cl, RCH20Si11eJ coe;!U!HeHll!1Mll, H8 TOJIbKU OOJI88 ,UocTyrrHHI,m, HO H ,llalOll1llMll JIYq]JHle BbIXO,!J,lJ [247J.

ITepBllqffbI8 il BTOpllqrlUe aJL~~1~OP~U II OPOMllnU C 3~llpaToM HGeX3 noxrrr He pear'npynr , 0.llH8KO C aJIKlUTIIOIIJ{,UaMil peaKl1}!H KOlUIeHCaIJ;IDl nporexaar C xoponnom BbIxo,UaMll [107, 134J, eme JIyqrne C aMHHaTaMfl [107J II ococeaao C sG;lJlpaTOM HGe1 3, Tax, CIlHTe3 MeTllJITpllXJlOprepMaHa rro rrOCJIe.nHeMy rryTll (BHXO.n 70%) VI,mer PM rrpellMYmeCTB nepsn "rrpm&IM" CilHTe80M 113 repMaHllR ;\ ~OPllCTOI'O ~~8TJI[Jla.

E~HCTBeHHHM He.nOCTaTKOM peaRID!ll KOH,UeHCaIJ;Rll HGeC1 3 c OpraHllqeCRRMH fio~aMll II 0pOMll.IlaMll ~eTCH qaCTllqffuH oOMeH aTOMOB XJlopa y repMallHR Ha non llJIll OpOM B pe3YJlbTaTe B3al'lMoneficTBllR C fiO~CThlM ¥Jrn OpOMllCTHM BO.nOpO.nOM, BH.Ile~~CH B rrpouecce peaKUllll [10~:

1/J RGeC1 + HI ~ 1/J RGeIJ J

r,llB R - CH 3, C~7' 3Ta o6maJI peaKUIlR, paHee oOHapyJKeHHaR rrpll rrOlI1lTKe npilcoenllHllTb

HBr R aJlJlllJII'epMaHy [aJ], MOlKeT CJIYlllliTb rrperrapaTl'lBHhlM CilOCOOOM rroJIyQellllR COOTBeTCTByromllX OPOM~OB ~~ fiO.nn.nOB [20, I04J:

+

rrte X - I IlJIll Br. B peaKUMll KOH.neHcaUllll OHJlll ll3YQeHbI Ta~e aMllHaTbI TpllraJIOreH-

Il Tplla.'lKOKCnrepMaHoB Iros , 108, 16:0. Paaaooopaaase J,-XJIOpCJI[JlaHH OQeHb JIerKO BCTyrraIOT B peaK~ KOH,UeHCauTIIl C aMllHaTaMll HGeC13 Il .n:OlK8 C ~eHGeC12' B TO BpeMR KaK C 3~IlpaTaMll HGeC13 OHll He pearnpyIOT [145J :

::SiCH2Cl + EtJN'HGeC1 -- ::SiCH2GeC1 J (fCfj,)J

CpaBHllTeJIbHOe llCCJIe.nOBaHile [108, 145, 148J B peaKUllil KOH.neHcalUll! aMJlHaTOB HGeC1 II HSiC1 rrOKa3aJIO llX cozsnoe CXO,IlCTBO.3 J

CICB2"i Cl (70%)~ 3MCH2Si

AICI ( -9a;.). M Ge. Si

R CH2CHCH;1JCI 33WHMC13

RI RlJCl (50%)3

CICH 2C=CH CI (25%)I

• 3MCH..C=CH2

Bce BCTynaID~e B peaKUHID RORUeHcaurrn opraHora~oreHRnH B peaKuaqx HYKneoP~Horo 3aMemeHllH, RaR n3BecTHo, pearnpYIDT npe~OqTllTeJI:bHO no MOHOMo.rreRyAApHoMy MexaHll3MY (SJl ) [42, 148J.

PeaKUllH ROH~eHcaUllll rrpoTeRaeT RaK pe~KllllH ~ofiHoro oOMeHa llJIll C nOHHoll WoPMOllrTPllXJIOprepMaHa J~[GeC13J-. ~JIll cera ROBaJIeHTHoll WOpMOll ~+GeC13 -:

RCI + HGeC1 ---~..... RGeCeJ + HCI3

11, aaxoaen, He~D3ff lI(;!(JIIO"lllTb Mexaml3M peaKUllz C yqaCTneM xapCeHonna GeHa1 BHe~pRIDmerOCIT rro CBR3ll C-Cl:2 ,

IIo~oCHI1e pe8Rl!}1l'l xopos;c 113BeCTHH .IV!J1 (;8' .;.OllJ12KO C G",jJrz onx, Ray. MH yCTaHOBaJIll, yJKP He rpe6yKlT I>,,;:TKIlX yU!o}ll'll1 II npOTeW3KlT npn ROMHaTHOll TeMrrepaType [lUJ:

(~Cipa30BaHn8 .r:.11.UPO!',iX)IOPI1P01~3B0rrHHX T[HG.'~C:: YK:-1SHBD8T, qT0 peaKU11:H 1~C~1,L..3i-iCElIIJn1, B03MOY.:Ur::;. TpOT8Ka8T 181-+:2 .TI.BYT'cLITOreffi:!i.TI repM8H1lH:

8RJIOHHOCTb ,:'p1IT(J.rou-':~~-Gpiv18HGD K ';·~-,a'.:;~I~~.HUIY) rOclI{'".J,ln~ xonneuca·.~.i'~i: :"03_p2C~8eT ,I: ~ ~ ":~ :.~eEbIIle·

16

1.5. 8PyrHe peaKllMH TpHra~oreHrepMaHoB

rr~oe ~ qaCTHqHOe a~~poBaHlle HGeC13 rpnHbffpOBHMR ~~l ~TnfiopraHHqeCKHMll peareHTaMn He y,naeTC.fl: oOpa3yX>TC.fl TomKO rrOJI!!Mepu. O,llHaKO Hcrrom30BaHlle n-1ff STnx us~efi TeTpa~n~pon3BO,llHilX O~OBa Kiill CBHHUa lJpllBe~O K rrpSITapaTPBHoMy cnoco6y rro~yqeHHff paHse TPY,llHO,nocTyIIHI:lX a~~oprepMaHoB [34, 4.1J:

HGeCl) + R ~ HRr.eC1 2 + R)snCl4Sn 3TH coe,llllHeHHff 6~ rro~yqeHH n rro npyrnM peaKUllHM ~02. 16?];

RGeH + snC1 ~ RGeH 2Cl + RGeHC1 23 4 TIpn rl~pO~3e swnpaTOB ~ aMllH8TOB Tpnra~oreHrepMaHOB 06pa3Y

eTCH qzCT8ff rHnPOOKnCb nBYXBa~eHTHoro repMaHn.fl (je3 Ge02 ) ;

H20 Ge(OH)2

C 6anbllillHCTBOM KHC~OP0,n- n a30Tco,nep~awnx OpraHnqeCKllX coe,nnHeHMfi Tpnra~oreHrepMaHH 06pa3yX>T KOMrr~SKCHHe coe,UllHeHn.fl.

TIpn B3allMo,nenCTBnn TpH~oprepMaHa C HacumeHHHMn Kap6oHOBHMn KnC~OTaMll nH,nllBll,lly3AbHHe COSnnHeHll.fl BHn6~Tb He y,na~OCb. TaK, rrpn CAnBaHllll HGeC1 3 C yKcycHon KllC~OTOll rrpoTeKaeT sK30TepMllqeCKaH peaKUll.fl. o,nHaKO o6pa3y~eecH, BepoHTHo, KOMlJ~eKCHOe coe,llllHeHne pacTBOp.fleTC.fl 5 n30HTKe KnC~OTH II rRllPO~3yeTcH C 06pa30BaHneM Ge(OH)2" 3aMeHa yKCyCHOll KllC~OTl:l ee aHrn,npn,nOM rrpnBO,llllT K BHne~eHllID yCTofiQllBOrO Ha B03,nyxe KpnCT~qeCKOrO KOMrr~eKCHoro coe,nnH8HllH nByXBaJJSHTHOro repMaHnH, KOTOpOMy MOEHO npllTIllCaTb c~e,nyDmyID CTpyKTypy;

[CH)t ••] -t GeCl)' (CH 0JCO)2

CBoeo6pa3HO pearnpyfuT KaR HGeHa13' TaR n llX SwnpaTI:l C Kap6oH~bHl:lMn coennHSH¥~ln. TIpn RoHTaKTS HGeC1 3 ~n HGeBr C K8TOHaMll3 nOc~enHne rrpeTepneBaDT KpOTOHOByX> KOH,neHcalUno, n ~llib 3aTeM rrpoTe-KaeT peaKUllH rn,nporep~pOBaHnH. HarrpllMep [59, 68J:

oeH ° I ) II HGeC1 Cl)GeCCH 2CGH3 •

3 I CH)

l1Haqe pearapycr am,nerH,lll:l [b8, 99J. AusTam,nerHn rron .neficTBllsM HGeC13 ~ BGe)3r rrpeTeprreBaeT3

y~oTHeHne cBoeH Mo~eKY~, a 38TSM rrpoTeKaeT peaKUnH KOH,lleHcaunn:

XJ~eyHO-yHGeXJ~

eH] eli J

IIGeXJ

-~

.J r,e81GIllRX ';'PIU'8JIOreHrepM8HOB C Kap6oHllJICO,llepJKallWMn: cosnanem,mi;' ,,8 0'1J10 an'e'!OH':l fiH onnor-c cJlyqail B3aHMO,lletlcTBlliI HGeHa13 lIO 1\1)8TI'0;\ CBiI3H EopomHlJlb:lO;j rpynnu ( '::C",O). B TO Jlte BpeMH B lCllMlrn U:JiC1 ;1 .l\pyrllx r-azpocz.ranoa nO.D.OOHHe peaKIl,lill HaCiJIlO,llaJlliCb H80.llHO

J Kr'2\'cEO:

l!O:JTm.ly IlOJlEOll E(JO:,;;m8HWJC TbID ouno YCTaHORJI8HH8 rcro , 'ITO rrpa B~oa

I1J1C,r;dic',mm I'8:,oo6pa3Ho,'o cP0PM8jib,llel'11,ll8 C TpllJUIOprepM8HOM HJlli ero

3l('llpDTOi,l pe8K!'}lH XOTH I\ I1rOT8Ka8T rio CBH3H ~C=O, HO lIO npasmmn

8JlbHO I!Hor.!y !-i8np2.EJlOHlll0, 'l8\~ C Tll,UpOCllJIaHaMl: [80,96, 243):

H2C"O + HGeC1 J C1JGeCH20H

OOPSTHblrt nopano« rrplIcOO,llIDle'lHrr HGeCI.) K Ijx)pM8JIb,llern,n,y rrpllBeJl 06",88'JB8H1110 CBR311 Go-C. BnDOQ8M, H8JIb3R,) rrOJlHOCTblO llCRJIlO'lliTb n:

,7Ir:}'fne :~YT1f 110JIyqeHl'LQ TpHYJIO;Jrepr1,lf1J!i'.~E;~18HOjjD:

H.f,~·-.;l. +'":"..:.-:!: ·.Y ------.::.....-_._--

BMeCTO ra3006pa3HOrO WopMa~~erlma llCrrO~30BaH nOJll1-d--ORCllMeTll~eH llJil'l rpxoxcan [241, 243J:

Ha OCHOBe SToro c~aBill8ro AocTynHHM BemeCTBa ocymeCTBn8HH c~eAYIDmlle rrpeBpameHllH:

2"",mI m, ~< c'Jl':::::::~"J"cn2oc~R PC1S u~ ZnC1

2/HClC1 • OlJGeCH20H ,.JGeCH 2Cl (C1 JGeCH 2) 20

GeC1 2• 03 e" 11lIeJ Si O rne Q=N =0, -0& ° 0 C1 JGeCH 2Q. H

]ID6ollHTHoe rrpeBpameHlle I rrpOllCXOAllT rrpll ero HarpeBaHllll B cpeAe AllOKcaHa: C RO~flqeCTBeHHHM BHXOAOM 06pa3yeTcH AllOKcaHaT .!J,Byx~opllcToro repMaHHH, Tpll6pOMrePMY~eTa)r0~ MeHee CK~OHeH K STOll peaKUllll. C~OHHOCTE I K pa3~0~eHllID AO ABy~opllcToro repMaHllH, nO-BllnllMOMy, 06yc~aBJll1BaeT Tpy,lJ,HOCTE ero rrpeBpameHllH B ~ -~opMeT~TpH~oprepMaH, qTO 6HAC npeo~a~eHo nporrycKaHll8M pacTBopa I qepes c~ofi PC15•

PacRpHTR6 KO~Eua ~ -olmcefi TPll~OP- H TpH6pol.rr'epMaHoM TaKlKe npoTeKaeT C yqaCTlleM CBHSH Ge-H, a He Ge-Cl [80, 96, 99J:

CHilgCl H - CH2 + HGeX

------I,... X ,.2C 3 JGeCH2CH20H

\ / o

r'ne X - Cl IIBr. rr~yqeHHHe cnllpTH ~erKO pearnpyIDT C KeTeHOM, o6pasyH COOTBeT

cTByromvre aneraru [65, 67J. E~EillaH TepMllqeCKaH yCTofiqHBOCTE ~ -TpH6poMrepMH~saMemeHHHx

KHC~OT no cpaBHeHllID C cooTBeTcTBYIDmllMfl TpH~oprepMll~saMemeHHHMR n03Bo~a HaAeHTEcH, qTO cnHpTIl THlla BrJGe ( CH2)OH TaK~e 6YAYT BeCEMa cTa6~EHb[MH C06AIlHeHIDIMH. O,lJ,HaKO rrepBbI;i ~eH STO:L'O pana Tpll6pOMrePMKnMeTaHO~, KOTopbIfi Mil ~I1Ta~CE rro~yqHTb npllcoe~llHeHHeM HGeBr K epopMa~EAern,rr,y, BhI,Ile,rrnTE He ynaaocs. TeM He MeHee oopa

J sonanae SToro cmrpra B ~aH!lOti peaKUllll 611.JIO J\OKasaHO o6pa6oTKoil

l'8aKLilOHHOA CIll8C}: ;.;eCU'8HTOM rpliHhHpa II Bbl,II9JI8HIl8M 113B8CTHoro rpu

M8ii!JIT8PMI1.i1M8 'r3HOJIa [99J:

BrrpOq8M, rrpll llCrrOJIh30BaHllll rrOJIll- J- -OKCllM8THJI8Ha BMeCTO ra3006pa3Horo ~OpMaJIh,llerH,IIa Tpll6pOMr8pMllJIM8TaHOJI y,IIaJIOCh BU,IIeJIllTh B llH,IIll

Bll,IIyaJIhHOM COCTOHHllll [243J,

CJI8nyIOU\IDI qJI8H rOMOJIOrllQ8CKOrO PMa cS --TplllCJIOprepMHJI3aM8ru8HHblX crrrrpTOB - r -TpllXJIOpr8pM~ponaHOJI [C13G8(CH2)30HJ - MH rrblTaJIllC1 rrOJIyqnTh rrYT8M npllC08,llIlHeHVcH HGeC1 (rr.1ll 81'0 a~paTa) K aJIJIll

3 JIOBoMy (ll M8TaJIJIllJIOBOMy) crrllpTY I~TII 81'0 TP¥~8THJICHJIHJIOBOMY ~llPY

(CH ;3iOCH 2CH=CH2, OMaKO:> 060llX G;n:YQaRX 06pa30BaJIllCh llCKJIIOqn3)3 T8JIhHO r8pMaHllllCO,II8p~all~8 rrOJ1llM8pbl,KOTOpbl8 He pacru8ITJIHIOTCH Hll SOC1 Hll PC 1

5 , Hll RMgX.2•

TaKHM 06pa30M, Ha6~,IIaeTCH REHO BHpa*eQ'I08 nOHll~HH8 YCTOt!Qll

BOCTll crrllpToB C13G8(CH2)xOH C YBeJIllQ8Hll8M ~ OT ~ no 3. B c.JIYQa8 )J,jlM8THJlBllHllJIRap6llHOJl3 rrOJlUM8p1l3aIIllil yJK8 He Ha6J1l(),llaJIOCh.

3 06pa30BaHll8 H8rrp8,TI:8JThHOrO C08,l\llH8HllH cane rrpe06JIa,llalOIIlllM [96J:

CH l I

CHJ-C-G"H=CH2I 011

II8P8M8lU8H1l8 KpZTHOll eBn:,;! rrrCi130ru.JIC. B8pOHrHO, B P8:lYJ1hTaT8

',:;.Jlll.JI!>HOll neperpynrrapoaxz,

C rrpe,II8J1bHblMY ._'nHp~'3Mll (L';J![I\JlOr8l'iJ2HOJiOM, "Sil3HJlOBllM II TP8TllIffi0b:l'l'Z.,:.OBbIM) 3(~nip2S l~CeC] J pear::·PS'"8'r ~.JJlbRO nocxe .II,..JIPTRrrhHoro K~rrHqe-

r.ae R - CSH11 1 Tperr.-C(J~, (~:)15CH2. B TO JK8 BpeMP C I'i'iOM Me:!'il.~OJi8MU.uOB II ilX CHJlHJlOBblMll a~llpaMll

~ ra peaxuns npOTeFOf,T .1JenapaTUBHblMll BblXO,llaMllO [247J :

19

---

~)~ .Il.RI'r,.J·IJrf:-~~:::J~._.".~;:T r; IIA ,ILnOKC~~1131='L ..k_ ."";

~;; ~';:"~ clrnC~ Op.riJlir: CU;C E~'~X C')8.rr.Yn-i8Jl:L~

i'~DI-\ y;~:e neO,E.nOI:r::-;""~:~, ~;!::_-!::~LD~~JE)r1, ,ILlIr8JrOr8~nl,L.1:':' L8t ~

COMH8ilHO, reHCT,lr:ecJ='::' ,~;_d·- ;.~iLJ C r:"rr:l;2,i':;::J:r6Hr8J!Mr~hi:-~:,n'::

.._--......

HocoMHeEHo, qTO v c, r:~'i()Ci:,;~(' ~T;~0Bpr--l::~C;ir,~ :~epe)lXG npC1'TH--

ReFiT 'IGpe3 GeX2 • :/LL,l ))f'"F-J,~iBl~' '-', ~J :3'1'0 rIOiI.TBQ :;:..;.:' J O:'Y!llOCTb~:L peflKII1llO ,ILBy 6por-.a:c roro j'(l:-:.'~C!l ',~,',~ ~;~ DJTE::EOl'i;:

( + "GeErJ ----

Po 8KUllH ,IUITBJ10r8Hli,ITOB re It",:i:-j:I;:;: c ~~9r8H0I';:1'}Ial'edL':n8MM n::iB8C'EI8 ,UJBHO [73, 104J;

OJIH3KO llpill':18H8HHe 3TOM t:88K1T,Ul1 I', rrperHiT;2TlffiHUX C~1j-{rre~:),8X no

nOCJI8,II.HerO Bp8M8HM erie p;Y~BaJIOCb C.JlCn;Tir )C 'l'bKl [I()~,!yqeHH >.: ..n:=10HJIbI-lliX

GoCl~~ :~_ GeBr? 1~ X:'i.~,~1~qeCKo:li :TH8PTFOcc~b!l'l Ge :-~ Tpe~'OB~1B1Je}1 npOB8c

.neHUF pe3Xl~JDI B lD.IJ8.rL:iHbIX 8MIIy.:rI(j'X.

3Tnx He.D.OCTaTHOB JTI'imeJ~ :sn8pBbJ8 DO)I",j1I8HHIllI ~EJ~i1H [1'/'::: I lE:i.., I~~j, ~'99, ~:C8aJ ,JJ,1IOKC8Hr~"r .nEyOp'Jr,~~Cl'0T10 T'eI',r~;:~[n::-{ (CM. c. 5). ,jT: CYllJ,8C~BO};-· ED npeBOCXO,UUT ITO cBoea peaKII)10HBO~li \~l10COOHoc'.rn H=:meCTEu~,I "J,HOICC3HW1'

,Z,BjlXJlOpHC'J:10rO repr"1BHILF, q~O n:Y3BO,,1pe,:, rrpOBo,EHTb pe 31{LTZ;:,1 rrp:! 8i.';'.10C

Q'8pHOM uaBJIeHIrr~:

+

T','Le R - CH CH , BrGH=CH-, CH2=C;~jL..eJ' ;I-L='~~],2=CH-, 2=CHCH2

lid, BrCH Br ROOC>:::H2i;I-IZ-' :raf M np ,2-, 2CH-, ~'~CJll1 yQHTill381'1 po a:\lU:ID rE7lpore pf.:n,JliIpOBr:E;U=j I-j8nr;p,i:J ~bEL: Ie Ccr~ :~:~

l1Ci'¥;/ Tpl'ICipOMrepMaHOM [,jC:, ~)l]. il~3K:Ke ;JC,lYF:'lO ~(X1C!;'< [;;(j, tiJ]

'1'0 npenapa'nrany» ,1l0c~ynHOC'I'} r):-:~' ~T,TI'~ '~~c)rOv:::"'e ;IN;,~:H: OD ;'enFJ y }-, !-:!):T-~;:J c tI1rTa I'l, Y.Ii8B.neTBOpl'I'~e}D,;Ioj,l.

:.:C

rryTeM BBeneHI1H B 30Hy 06pa30BaHRH nRrarrOrSHRnOB rSpMaHRR RX nepeXBaT'illKOB Tllrra oyranasaa TI aueTllJIeHa [121, 136J:

CH-CH K6T IIpOTSRaT:b II qepe3 ~3GeGeX3'

2. lIPynlE i1YT:: OEPA8(JBAH1lH CBR3H Ge-C

nOB!1M rrYTeM rroJIy'rc1HlI51 OpraPH'IeClmX COenv.H8I!Ill1: repMaHJI[R C1'aJIa

peaxnzs opraHorarrOrSHHI\OB C '~8Tp2J,'aJIOreH:repMaIlaMz B IIpHCyTCTBJI[H Menl! [45, sv. IQ4]:

-"i,8 R .. )Ie, 1'1", n-BJ., .ui , .'cd, Ph, m-MePh, -llaf, -CHzol' n-Phl-Ilpu lL'YQeHll11: peax.rv- ;\1rGT~hOBI-lY. C08,OIH8HMtl repM8HM C r-anora

tlllI\aMll a,JlKlMJ1HIIH UWl' OUimpYJf.eHO, 'ITO C HllMlI 3Ta peaxrtas rrpcrexae r

3Ea'IIITe.1bHO JIeT"18, qe:i .: ,:!,WOT'~lq};;;M!1 C08P,IIH8H"lIllMH KpeMImR [37, 691:

21

22

A1Bl'" Me

3G Cl t G 2 J') () J --~ I.;e ('';';; +

x

x

O'l'M8'eIf,i, til'] Ol cJ .J0~~1E~ 0 '~O~--:E~G /'le, , no Ii: ille4·~i npoacxonnr B :JTOll pe8KWU:, e: .: R=C l;JII: It [c,s] .~ CoeJUlHeHllR C repM333H8BO:;,t CB513LIO Mory']' re D~·'mJjrl!

,1Or::L'2ic8 B03M','"',,iOCTb CeJIaKTIlBliOrO aJlKl1JllipOBaHlm tIeTHpeXXJlOpllC

ror o reiof.'i8HI\.fl 8JTIJMZHlllLrpr:1HlltIeC1UlMll COO,1J,l!HeHHHMH [34. 59. 79, 82,

'03, =CC]:

3 •MPEO'1>YHKLJlOWJI1HllE: OPI'AHHy,ECKHE CO ~lli1HEHI1H I'EPMAHllil

J6H8PYJil8HHbl8 peay.D,llll llGeX3 H 11f. KOMI1Jl8K;iiblX COe,IUlHeHlll1. ococea(, nx ,iJ,OCTYI1HblX 3(pl':paToB, OTI\pbiJffi illVpOKll8 rrYTH iJOJlYtIeHllH K8p601JYHK

UllOfi"elbHblX repM8HHilopr8HlltIecKllx coo,UllHeHlll1, B TOM tIllCJle II Herrpe.uem,

HUX COe;J)IHeHHij re pM8HllH. IT0.I1p06H8e paCCMOTpllM r:e8KJ1,J1lO rnnporePMI'Jrll POB8HYIH Herrpe.uOJlbHblX Imp6oHOBl1X [

24

CTcByDmHe TpHXROprepMRTl3aMemeHHHe RHCAOTH HaM He yna~OCb. ITPH oopa00TR6 00pa30BaBllillXCR TI~ll STOM rrO~MepOB XROpilCTHM TilOHRTlOM ~mb B

CJly'lae DpOnR0J101l0~ IUlCJlOTbl ynanocs rrOJIyq,ITJ, XJlOpaHrilJlpl\TI. J, ,J -6;IC(TpilXJIOprepMRTl)rrpOIIllOfiOBOH KIICJIOTbl [81, 238J:

Cll=CCOOll

TpllXJIOprepM8H II ero s~HpaT BSaHMOneucTByDT ~ C RHCJlOTaMH C OOJIee YJlaJIeHHHM IJo.lOJKeHHeM ,llBoJlHoll CBR3H OTHOClITeJIbHO RapOORCHJl~Hol1: rpynna (13 'laamOCTll, C BilHMJI- II aJlJlHJlYRcYCHoi1.). onaano MOHOMepH1fX npOJIYRTOB rrprrcoenllHeHllH B 3TllX CJlyqaHX BHne.1HTb He YJlaJIOCb. EOJlee 1'01'0, 00pa30BaBooIecR rrOJIHMepH rrOqTH He pearilpyIDT C XJIOPllCTllM TlIOHRnOM. JIHillb qaCTHGHO paspywaDTCR M8TIL1MarHilITXJIOpllnOM il nHTHXJlO

PllCTHM ~OC~OPOM, oopa3YH illllpoKyn raMMy npOJIYKTOB. ;CT[opanrl1,I\pl1,I\ Blilil'l.JIYKCyCHOl\. KHC,10TH JIerKO nonsepraercs rnnpore p

MRTlllpOBaHKD C OOp230BaHll8M J -TpllXJlOprepMMJIOYTllPOllJIXJlOprrna. BnpoqeM. 31'01' xnopaarnnpaa yno6H8e nOJIYtIaTh llCXOJlR U3 )'POTOHOBOI1 JmCJIOTH MJlH ee xaopaarnnpana [238J:

CH -I3CH=CHCOOH

GeC1 4CH =CHCH -+-----"----/

2 2COCl OU3iJe2H)2

YH;J:\eUfu1eHOBaR KllCJlOTa oopasyer C HGeC1 3 rrO.'lllMepHUe npOJIYKTH, KOTopHe YJlaJlOCh no OOHqaOll cxeMe np8BpaTllTb B XJlOpaHrlmpV~:

SOC12 ..

ITPH DO~TKe nprrC08J\llHeHllR HG8C1 3 K TpllM8TllJlCllJIllJIOBHM 3~paM

Me TaKpRnOBOfi, KpOTOHOBOfi II BllH~YKCYCHOM RllCJlOT 00pa3yroTCR. B

OCHOBHOM. nOJlllMe~H II TPllM8T~xnopCl\JlaH. B nepBHX nBYX CJlY'laRX

jcl1'l,8 rrOJTI:r,'IOIIOB 3001 2 l1jJlIB8J:Zl " IJOJ\)"18HlIlO COOTB8TCTBYlOil111X

;:';::J;. 8HrH,I\jJH110B. B IJOCJl8):lH8r.i CJ1yqa8 CBOaC TBa IlOJ1llM8jJa OKa3aJlHC1

::.n8ETHQHll:,r;r CBO;lcTB8M :JOJUrM8pa. IJOJlYQ8flHOrO 113 BllEllJlyKCYCHO!1. KllC

~Bll,L,Y ror o , '170 TP1!M8T;!JrYJIOpcv..!~:m oopasye-rca Jlllll11 IJjJl1 Harp8BaelY,: ;J8aKLUIOHHOii L18CCbl CRblill8 SCOC. MO)''JlO IJp811IJOJIO;K!IT1 CJI8.rr.ylO1l1Iill L!t: Xm:;l3M 3TXX pe aKwul:

TpI'16pOfl"repM8Ii :1 81'0 :YI~Hp~~T, Tare ;&8 K3V n H~eCJ.3' JIerr:o npacoa

lilIHH8TCr, KJv, j -li8rrp8,rr8.n1Hill,'! K3n6cH05W,I KlWJlc(i'2M C 06pa30BaH1l8l! J -1' pil6po/,lr8 PMl1Jl3:JM8qeHHblx l\r;CJIOT [99J:

HGeBrJItCE:=ClL~1 )CUl)l: - .. nT3ue(~~I(H)CH(H' )COO}I

J _rlpnOpOMre.nMHJI~!;3.Mell18HI~;Je iC1CJIC :'~J - oeClm8THLI8 RpllCT8JIJrnQeCYCTOi: UYlBbi8.Kll8 B8iJPC:'B8. :'t1;JMHQ8C!\J! 'JQ8HI, OHH Bbl,n8p;:amBlOT ):lJlHT8JIb

HbEl ~~::'TIJeB rip:: :;CO_:::-;~;:.:;cC, 0C5P2:~'JBalH:8 rrQ.nHMO~JB TIIJll :JTOM H83H8tDITCJThHoe. CJle,nOB8T8JThi1'). 8B',.Clb Ge-Dr B P'O,TI,OJi'blX C08,rUlH8HllHX M8H8e

aF'='1iBE~J ITO 'JTHOLLie:ElTjO 1\ ~\8pOORc:r"JTI-:J--iG~! rpvrme , Lte!;,~ CBH31· Ge-Cl a ~Pl\6pO"Te pi.:n.D2,,':er:;OEI;UO EllC./l')i' clIOC:OClH" BCTyrraTI> B peaKIUIIl 3Te

L}:1{;)1::':2;T~1 6e~-3 :3JTfJ:::;r::BJl.:>i IlD~'L :;'-'8f',,; 0B.R3:1 Gt.:-!)r.

j~)L'l~I:.:O J."p -T,f-':;:~eJIe":=DHLlY rCfC.]J')T D J-)8aKTU01 C lIGeBr ObLlaJ '(C,nf.?;::;'OB:,~IL-l r I 'j '-ECl:aG:,I~;'~~jI1:...: -'~I:C,Tl'_Y:rL~ \I"l1'I~H,,~YKCYCH()J1). O,llH8

I;aG.Tn;_;:"jTC~'J.: DOp230Br.-JEll''l O,TI.HOrO Tc.}IbKO

~';JI,:~::C; .:~e3''\;j :-lp:aC Ct;,iLHH;-;eTC5i L': aI\'p::,",T10B()~i

~). 11e,.rdLF; D:'' ,~I':). ~._:'-*--~, 24C] Qp8JBbl l I3 :LHO ~'JrJ~)Ilb:.~ J,:e'I'C))~ l~~), ',J' [i~ J - ('rliEr'~~JICr~'fl'ET'ep,~..~~-tJI)}{l--1'pjOHOBblX VECJIOT

11 n:: IJPOl!3BOJlHtJX 6e3 c. ':'~!,U1J[1,HOrO ITOJIYQ8HllH TpllI'aJIOreHrepMaHa. 3aKJIDqafOwliiCH B Ciftelteli:M ';;,;,v, ;ij)' ',Il ,ljill i,lST8KpUOBOll KIlCJIOT" IIJlli ZX npoasBOJlHl1X c GsCl,; II ~e ,G, j·.."'h~';U';;i1JIOKCaHOM. ara CMeCI> npn KOMHaT.- -, '. :'8.",'IIep .r: '-~IP ~'r; :~-::'

o 1

CH2 =9C, + GeX 4 + (~e2HSi)20 (~100%) R X

rne R - H, Me; Y - OH, OR, Cl, NH 2"

B rrpl1cyTcTBnH C'['80?..JIH:JOTOpO :10.rmM8pn38Ullli tHHOTH83HH8 3TH pe8KUl1l1 MOlKllO rrpOBO,Il,l1':'b rrTll1 JCIITH'l8HHI1. 'lTO COKp81I18eT Bpe~jH psax

Ul111 .1\0 lIeCKOJIbKliX 'l8COB [:2:58J, .l\8JKe B C.nyQ8e 8RPI'lJIOHI'lTpI'lJIa. AMI'lH8Tbl (RO)3G81i TaKJic8 IIpI1COe,rurnJJlOTCH rro Kp8THHM CBH3HM

J-Herrpe.l\eJIbHblX KI1CJIOT IT nx rrp0I13BOnHHX. B TO BpeMH K8K 8MHH8Tbl

HGeC1 3 K 3TllM peaKlIIl.Rl,1 uecnocoonu [161. 167]. XJropaHrl1.I\pl1.I\ H 8Hr1mpl1.I\ I1T8KOHOBOll KI1CJIOTbl TElKlKe JI8rKO rrpncoe

.lUiHJJlOT 3cjiHpaT TpHXJIOprepMElHEI. B peEiKUllHX xte llTaKOHOBOIr KIICJIOTH C

3cjilIPEITOM TpHXJIOprepM8Ii8 Il ero ca.JI5IlIOKllCJIblM p8CTBOpOM oopaaye rcrr

rrOJIllMe P. c rpoenae xo roporo nonrnepxncno CJIe,IT,ylOIllllWJ XllM11'leCKIIMH rrpeBpameHI1HMI1 CoO?J:

HGeC1J'2Et 20.CH

fC1 2 GeCH2y Hc o o J2=y-COOH HGeCI/HCICH CH2COOH n2COOH

I PC1 5 f } SOC1 2HGeCl;J02Et

20 ROH/HCICH2=9-COC1 ~ C1 3GeCH 2yH-COCl CH CH 1

2COC1 2COC

~ ROH R'OH/NH 3 • (R'O)3GeCH2yH-COOR C1;JGeCH29H-COOR

CH

2COOR t CH2COOR

l ROH/HC1 CH2=?- C (0), 0 HGeC1;J02Et 20, C1 3GeCH 2yH-C(0),0

CH (0)-- CH (0) /'

2C 2C

r~e R - Me, Et; R' - Me.

MH CHHTe3a CeCKBl10KCElHC nero .l\1l1l8TpneBoil CO,'li1 6blJIll p8apa

60T8Hbl 60JI8e CJIOlKHble CXeI,11l C}!HT838:

(MeO)JGeCH2yH-COOEt CHZCOOEt

(01,5GeCHzyH-COllli2)n CHZCONHZ

3~liPHtlil KOMrr~eRC TpUXITOprepMEiHEi C BHCORI~~ BHXO~OM rH~OrepMll

28

COOTBeTCTBYlOlur:U-~ KECJIU'L'c: He ;-rDJIHE~(~H T8r:OBLJ1':~ [1[)4 1 =,,'~ J. ,,':':::;.-1 .,:

~"Tl: E'UleJK,Ilbl [23IJ. ;]O,IIp06HO BCe ,U8HHble 0 rll,UpORCaMOBhlX RilCJIOTaX. CO,IIe;)jKari(iIX 3.'18M8HTbI lYE rpynna , o606m8Hbl B ooaopax [234, 239, 250J H 1,:oClorpsq:,illl [2~,9J.

3.2. 1I8np8n8.,bHhle COeJlllli8HilH r8pMsHilH

'1e:1~e,i1eJIbHhle C08,I1l!Hellll)1 l'epMSHil.fl BnepB!18 6hlJIM nOJIYqeHhl B

1'055 r . npHMill.l CilBTe 30M [1, 2OJ:

CH2=~CIl2GeC I)

CR 3

rne X - Cl H.1ll Br.

l'e aKlu\.q KOH,IIeHCaIi,IUl (en, c. 12) TaKJK8 DPJ!BO,I1l!T K rro.ny qeHilKJ 3THX ~e COeJlllH8HHll:

CH + HG~X.j· n.> t 202"CHCH2X

--+0 CIl2=CHCH2GeX 3

()c06mlHO XO"OlliO" 'i':'!)S 11:JCJTc'ae--' C aMIDla~'a!.1ll TpID'8JIOreH

repM2HOB U45. ",If'1:

(-lOO%)

(,~ 4C%)

(~ 10%)

K re8KL('~~~ }:l·' .~,-~c~C,-lllI~-.· ·~'!\~J:-·?JInC:I: ~Iloco6EhlMn :l'1'.pyrHG ranpor-epaaHtl [;04]:

r-----·-...~ CH2"CHCH 2Ge(CzB5)) ---+------~~ (C2H5))GeCH2CH2CH~X

I

i ~ (CH 2"CHCH 3 + XGe(CzH5)3

;ieO')XlJll:~\:O(;Tb :(ud: :,':8J:~,CTBa CT;J08H;IJ'! ,I1l!repMHJI3TllJI8HOB, oopa

~5Vj()l.:U~X~:' re~;E~!'L?:;{ :u~'-:~::orr-J I'Optm"TIfpOB8H1'IH (eM. c. 9)

B1l3BaJIa H800XO,l1.RMOC'n, CMHT83a 3TIU C08,IDlH8HHM .I\PyrllMII H83am:OHMSl-·

MIl rryTHMJIl [;28, 38, 41. 52, 58, 8'7, 9rJ, B TOM

r8p~Hafi rpyrrDMpoBKa OKaSHBaeT OrrpS~eAeHHOe ~RHlle Ha

pe [' >ll.um ~erH~pClXJIapHpOBaHHR j -XJIOpBTIWTpIlXJIOprepMaHa. CpaBHll'!'SJThHOe 1:3yqeHlIe pe8KUICIT ,nerMPClXJIOpHpOBaHHH ~pyrHx CTpyKTypHO nonoo

HHX XJIapaAK~~epMaH(cHAaH)~10p~OB rrOKasarro, 'ITO ~ rspMaHOB psaK

ID!2 } -pacrr8~a B 60AbWHHCTBS c~yqaSB rrpSBaAllpyeT Ha~ psaKUHefi

1~8T:I..nPO~10pHpOBaHllH. O~aKO JlSTYOCTb OTIIlerrJleHHH HCI y repMaHJiIeBHX

"POI'3BO~HbiX 60JlbIIle, qeM y llX Kp"lMHJiIeBbiX aHaJlOrOB. Harrpznep , SCAll ::m3Tl:.naHll.mm He OTIIlenJIHeT XJIOPllCTHll rcnopon OT CI TO

JSiCH2CH2Cl, (CI 3T8 psaKUJiIH npOT8KaeT JlSrRO. OTIIlSnJleHJiIe HCI OT

JGeCH 2CH2Cl Cl ,GeOH 2CH2

CB TaK~e npOTeKaST 6biCTpee, qeM OT OlJSiCH2CH2CH2Cl,2Cl

ll~! neHCTBHH Ha HHX RaTaAllTllqeCKllX ROJlllqSCTB TIRITSpRnHHa.

rIp:! ~erll~poXJIOpHpoBaIlliH C1lHCH2GeCl,3 ':rroJlyqeHHOrO npacoenaneBYreM HGeCl3 R XJIOpHcTOMy Blffill.1JH,lleHY) B OCHOEEOM II.POHCXO~HT ,} -pac,:3):(, O~aI{[J y nanoct, Bl1,I1;e.'llll'b HeMHuro H j - X.l>OpB'mWITpUXJlOprepllBHa , ':'~o HBAAeTCfi ~()Ra3aTSJlbCTBiJM OTpyKTypH HGXO,IIHOro COS,IJ,mIeHllH:

(J'~UJ.errJIeE,:e Eel or J..,l' -MXJIoJ;:·"HJITpJifY••xoprepuaaa 6l1J1o ocy','RCTB.TI8HO K')K rrpa IlOMOI4ll Y.:IlHOJlliHa, rax I'l xaopzcvorc a~;IH. ?~I!ee r;-J,IJ06HOe OTmerrA8HI'le )w:o llCCJIe,IJ,OBaHO HaMil HO llpI

. ,~lGfjJ1fl6T } -aTor,~ xnopa r: ~10PJ!CTHfi aJl]JM!ffillit _. .L-aToM XJIO':' ~I:J [15, 38J:

( ~ 80%)

-------. ; "3HOJl\lEL "--",,, OLGeOOl=OH (~42"';\)

2

~...., 0lJBPd1 ~t J.I r ,!~\..t"'IO J:l ~ ~ ~;: ~ CG.h8.U - ~'" oI"TIJC)OrnlTI-iUMVI c.BoEcTB8M}1.: ~ -:' ':0 UB~UIHJn~;.·lYU~..no j~""~ ~>,1(~' "-:l ~,':~ neC' [\OJJ1~r:O xaccr I:' dMorrpOH3E:).}ThHO

'F',r,'-' ;PW'~'8T0H B Heap,' ,C'lEC8l'BP,JJl')8 BemeCTBO MO.10qHOrO IJ;BSTJ,

r, B Jil -XJIopmm;;J1TpI'.YJIOPT'f';WdH8. R[\K }l B ero K!lIlMHlIIeBOM eaaaore , :'1;\ l'I!TpOBaHYil'J: C',I " JaC",''-;;) 'Ji,' IIleJlO'!ll OMll.'meTCH ncero TpH aTOMa X.nor:J • :'le iipoaCXC'iIT"' J "';J8C.l.,!1 j -YJIOPBlIHllJIl1P0l1SBO~HX repMaHl'!H t~ B c..TIe.:u.yIC!~,ilx ITpGBpt:Hllr>, ".:' -E.

31

CJIe,llOBaT8JIhHC, C!UlOEHOC';'b '.;Oe,llHHeRlrn runa C13

MCH=CHC1 !\ J -o'rncn

JIe~lO, r .e , !\ rrpOTe~:E,HHlO peaKlll1ll IIO IlOJIOJKeIDllO 1-4, iIOBhllliaeTCH B CJIe,IlYlOilj8M IloPMRe ]13M8H8HHH [/1: Si < Ge -Ge > Sn ,

Ewrn II0IlblT3HbI Z ,~I;~;r;!s rrYTIl llOJIYQeHllJ1 BblCOROMOJI8RYJIHPHlllC 008W\H8HID1 re pMaHIifi [:::0, 5r];

¥e Me Me ), I I Ge(CH2) 3Si 0 Si(CH )~ I l I 2 3

,Me Me Me x

M3 lCllMUqaOKUX rrpeBpail18HID1 HeIlpe,lleJIhHlllC repMaHID10praHllqeCKllX

COe,IlIDleHID1 OJIa!l:,8T OTr.'~?I]% rrpucoaW\HaHue 1< H}lM PMa ,llUa30JIOB

[179J, THOyRCYCHCll InlCJIOTbl [19J II repMl1Jl9TwmpoBaHu8 anaaaaraaa [I70J :

ruo HtNH - 3,5-,UllMeTllJIITHpa30JI, 1:!.W.J\230JI, 2-IIUppOJlli,IlOH;

llllipORO H3yqaHll U IPU3UKO-lCllMUqeCRHe cBoiicTBa Herrpe,tieJIhHllX rep

MaHOB [7, 18, 25, 26, 31, 35, 40, 55, 63, 85, 90, II9, 120J.

3.3. Kap6ora~oreHrepMaH1l

llpH lCJIOpUpOBaHHll 3THJITpHlCJIOprepMaHa lCJIOpUCTblM cyJ!b¢yPHJIOM o6pa

syeTcH IlpHMepHO B 6-8 pas 6o~llie } -lCJIOp9THJITpUlCJIOprepMaHa, qeM

~-XJIOP3THJITpRXJIOprepMaHa. B To~e BpeMH H3BecTHO, 'ITO IlpH rro,Ilo6

32

HOM xnopnpoBaHilll aTll~TpTIxnopcn~aH3 J -llaOM8pa ojpaay8TcH BC8ro B 2,5 pasa OOJIb1ll8, '18M J., -llaOM8pa. CTP08Hll8 OeJpaaCJBaBUUlXCH J., II jl -xnopnVJJITpnxnoprepMaHOB ouno .I\OKaaaHO 11X M8TIDmpOBaHn8M

[7, 28J: CH MgC1

3 ~ (CH3)3GeCHC1CH3

CHilgC1 ~ (CH Ge + CH23)4

a TaKjK8 THTPOB3Hll8M C, I H. U\8~0%iC. iJ J. -X.}]OP8Tl'!~TpllXJIOprepMaHe OTTHTpoBblBalOTcH rpz , a B J> -X.}]OP3TllJITPH;~JlOpr8pMaH8 qeThlp8 aTOMa xnopa . OTMeQeHHhl8 npespanenan rrOJIHOCTblO COD: )J,OIOT C T3KOBblMil ,nJIH aHa~orWlHhlX C08,nlilieHID1 Kp8MHllH.);ClJl88 ML: OOHaPYjKllJIU, 'ITO ,nerl'!,UpO

xnopnpoaanne XllHOJIllHOM -fl-XJlOP8TU.}]TpUXJlOprepMaHa npasonar K rro.nyqeHHlO, rrOMllMO Cll':811T'lpyIOU\8rO dt:l)JeKTfj C13G8 - r p y m lhI npi: xnopapcaamsa.

DPil8IITUPY£G;:U;;i 3C\lJJ8KT rp .mu CI~(;8 TIpOHB.'lJl8TCH U rrpu XJIOpllpOBaHMI: M8'f);.Jl1'8PM3HX.JlOnlIZC,S fr'] _ i1pOBe~TH xnopxponanao M8TH.JIrepM3H~)jOP,~OB X.JlOpllCTll~ CY.JT~PyplWO~ H8 yua8TcH, '1'1'0,083 COMH8Hllfl,CBfl

3:'HO C 3ljx~8KTOM x.~opr8pW!.JIbEBX L']'yl1n, TOK KaJ( 8HaJIOrUqHhl8 M8TllJI

c.: '''~JlOPJl.ULl B rDy,::x: YCJlommx Y~'lr:::::;:Y'0TCfl. :,i8T}WXJIOpr8pMaHhl y,na

33

JIOCb npoxnopaponars Jllllllb npn YJIbTpaWliOJIeTOBOM OOJIyqeHliH B I1pMOOpe.

OOeCrre'IJffialOl!jeM y.I\aJl8iiile OOpaJOBaBWHXCH MOHOJUIOplinOB 01' naJIbHefune

ro B3aHMOnel'lcTBlJH C xnopox, O;L\HaKO HeCMOTpH aa HCnO.lThSOBaHMe yKUSaJlHOrO npaoopa npn X.JIOpHpOBaHHH CH3GeC13 , MOHOJUIOpl1na OdpaSOBaJIOCb acer o 18.5%. a C1 "3 .~ 43% (ocTaJThH08 npl1XCnl1JIOCb aa Bl1cll1m12CHGteCl X.JJOpM.I\ BperMl npa X.i10pMpOBaHHM B 3THX yCJIOBHHXC1 3GeCC13) . D TO ye CHJSiCI oOpa3y8TcH CiM8e oU% 1,10EOx.i10pll.I\a. TIO.I\OOHhI8 COOTH0ll18HliH

J Me;w MOHO- H rrOJllJJUIOplc.rraM;~ D1!Yili rrOJIJ"l8HbI npn JUIOpHpOBaHlHI

(CH3 ) 2GeC12 ;1 (CH ) 2SiClz. J3BecTHo. q'PS CICHZSiCl J xnopnpye-rcaJ 3Ha

TIOMUMO IJpllMOrO raJIOreHUpOBaHUJl aJIKllJIY-JIOpr8pMaHOB. J. -xnoprepeaHbI MoryT 611Th IJOJIyqeHhI qepeS ;IlIlOKCaHaTbI ,IjByr;:."OreHU,IJ,OB repMaHllJl.

OC06eHHO xopouio 3Ta peaRnllJl nporexaar C ,IUlO!kDfWTOM ;I\By6poMllcTOrO

1'8 pMaHllJl [179, lSI, 199J:

,------.. -100"0...O~ ( 90%)'V

x - 01, Br Jlaxoaen, H6,IJ,8BHO 6UJ1 Hafl.neH IJPOCTOll nyn, W'JLJ'q8HllJl TpUraJIOreH

l'epMllJIMeTaHOJIOB, H8 aCHOBe !:wrophIX TaKJ\\8 B03MOJK8H nperrapaTllBHblli

C;;'lTes XJ!opMeTllJITpHrdJlOrSHI'epM3aop [243J:

POI"...... He OCHODe CT3Billl1X ll,OCTYllHllMH J. --raJIOr6Ilii,ITrJE OCYJ!16c1'BJIeHhI

"HT6311 ,IJ,pyrux ~mor')'iliC,l"lJHhIX Kapory,};.\'HKI.I1'lOH8JIhm:X Coe;Il,llH6HuH rana

Me3~eOHzX, X - I, SON, -OR, -U~CR, OH, -coOR , -CH2CH~CR2ll T.~. ~:"fl, 32, 39, 93, 179J:

:'),8 ui ~m,· J. 5-.IJ,llMe Tll..GHpa :,.),,:, ':,',: ::ZMlDID. :JOJI, z-rrappOJlR,l[OH. iW ocnone J.. -y..rrC)f1MeT

4• .JII1H.Ei1Hl1E 11 lJ,l1KJIWU;cYJill ,IJJ1I'EPMKAPEOHOBElli COE.U\ffiEHl1J]

K 3TOMy xnaccy coenHHeHI!l1 OTHOCqTCH TaJ\ Ha3bIBaeMble MOCTI!KOBble

coenllHeHilH, T. e. I1Mel:J!l.(lle ,'JjparMeHT ;Ge-R-Ge~, rne MOCTIlK R qau\e Bcero MeTI1~eH. BrrepBue OHI1 ObWll rro"~qeHbI rrpHMblM cIIHTe30M. KOTOpblM

B HaCTOHmee BpeMH HEJmeTCfl enllHCTBeHHHM ~H rroEyqeHIIQ oonbillllHcTBa

113 HI1X [128, 143J.

4.1. ITpHMO}i CllHTe 3

TIpHMOl1 CMHTe3 oprarurtecknx COe,IlI1HeHl1l1 repMOHIIH. r .e , rasopaauos B3aI1MOneiicTBIIe oprmlO::-oncrelCll,I(OB CO CMeCblD rrapOWJ\OB repMaHIIH H M6)ll1. HarpeTblX na - 4CO OC, ~a Raqana Hawero lICCnenOBaHlIH Obln OCYllieCTBw'leH ncm o 118 C1M". Cl£;t, ern, II! C1Pr [1, 14JJ.

l1ccne,noBall1l8 nprmoro CIlHT83a 3EKHJwepM3HXJlOPlUlOB aa MHorllX npaMep3x M 3H3EM3 EllTepoTYPHblX .naHHblX 0 rroLyqeHMM 3TMM rryTeM opraHll

qeCKI1X coe.llllllelmii ,npyrHx 3neMeHTOB -,-Y rpynnu [143J rr03BOnI1El1 yc raIlOBIITb, qTO npz ne pe xoz;e CT Si K Ge II Sn YHllBepcanbHocTb MeTOna CHlDKaeTCH. CywecTBeHHhLM p33JliIq)ler,1 B npoTeJ\aHIIll npauor'o CI1HTe aa )lJlH YKa3aHHblx 3neMeHTOB HBAReTCH TO, qTO B cEjqae repMaHIIH il ono

aa COBepweHHO He ocpasyicrcn COe,lj,ilHelIHH, cone paamae CBH3b Ge-H Hnll Sn-H, B TC Bpe~!H J\aJ\,li,>'L'l 3i ODP030BOHlIe, HarrpMMep, coenllHeHHit rzrra RH3iC1 2 JIBAReTCH BO MHorHX CJIyqaHX naJKe rrpeoOna.nalOlllllM.

1l0MHMo XJlOllHCTblX EW.JllillS H MeTa.llJIHna [I, 20J, MbI U3yql1Jlli B peaKl\lll1 C 3neMeHTapHblM repM8Hl1eM nnrElJIOreHlUlhl rnna Cl( CH2lnCl, rns n=1-5 [42, 126J (T80Jl•.n.

T 3 0 A IT U a I

TIpHMOii CHIl1'e3 lIa OCHOBe nlfl'aJlOreHanK8HOB

Hcxonnoe coe,IIllHeHII8 ITPOnyKT peaKJlllIl Bblxon, %

CH 3GeC1J

18

C1JGeCH 2GeC1J 8,5

Cl I

(-ye-CH 2-)J Cl

9

C1JGeCH 2CH 2Cl 8

C13~eCH2CH2GeC1J 0,5 C1

JGoCH 2CH 2CH 2Cl 10

C13GeCH2ClI2CIl2GeC13 6

J6

IT p 0 ~ 0 ~ E e H B e

;:CxoMoe COe~HeHBe ITP0,TI,yl\T pe aKlum

C13Ge(CH2)4C1

CH2 - CH 2 "I »: GeC1 2 CH 2 - CH2 H2C=C(CH3)GeC13

CH 3CH(CHJ)GeCI J

Br3Ge (CH2) 5Br

9

13,5

9

9 8

Hawn Ha~e~ Ha rro~yqeHlle rrpellMy~eCTBeHHO reTepoUllR~qeCl\BX COe,!!,HHeHIDi He onpaanazacr.. oopasoaaaae reTspOI\BKJIOB HaCiJIKJ,ll;a~OCb

~D B c~qae 1.4-~xnopCiYTaHa B ~xnopMeTaHa. B noc~eAHeM c~qae o~aeMoro reTepOnaKJIa

oOHapyJKMTb He Y;:La~OCb [42, 122]. KapCiora~oreHcH~aHll. cO~epJKaruBe

B Mo~eKy~e ,ll;Be M jo~ae ~ -~opMeT~1DHlle rpyrrrrll. B YC~OBBHX rrpH

M01'O CHHTS3a c repMClHlmr,' ORa3a.rJlCb HaMBoro aKTIITlHSe CBOBX opraaa

qeCKHX anuuor-oa . HarrljllMep, BCnOJTh30BaHBe CiBC (~opMeTIlJI) WlMeTll~CH

~8Ha npuse.no K rrO~qeHllIO BOCbMll'l.7IeHHOrO re'repolIBK~a [122J:

38

B03MOJlUlOCTJ, OOp~30BamIH B YCJIOBIffiX rrpJJMOrO CllHTe~ia QSTblP8X

'LJISHHblX rSTSpOUliliJIOB H8M Y,ll3J1.OCJ, rrOR333TI> npz iICIJOJIJ,30B3Hllll npyro1'0 ,n:llcPYHRUllOH3JIJ,Hor'J K3p6or3JIOr8HCllJI3H3 [122J:

C1 C1" Ge/'Ge/Cu (CH))SiCH" "CHSi(CH)

'Ge/ 3 )

cr" 'C1

OCOOeHHO JIerRO II O~H03H3qHO IJpOTeR3eT B33llMo,n:8ncTBlle C repM3Hll

8M, RpeMHlleM II OJIOBOM I .2-611c(XJlOpMeTI~~)TeTp3MeTllJ!.I\IlCllJIORC3H3 [I 13 , 125J:

Me I WCu

0q3iCH2C1 )2 Me

r.ne M = Si, Ge, Sn.

O.I\H03H3qROCTJ, npOTsR3HllH PS3RUllll II BblCORHll BblXO,ll oop33y~srocH

rnSCTllqJISHHOru r8pM3HHllOprSHllQSCROrO UllRJI3 B 3HSQllT8JII>HOH CTSIJSHll

coxpaaazact, B PSSKT.J;ll!! C rspMsHllSM II 60JISS CJIOlKHOrO COS,IJ.llH8HIffi

OllMM.-T8Tp3RllC(XJlOPMSTllJI),n:llMSTllJI.I\llCllJIORCSHS. B aTOM cJIYqas o6pssyeTcH HOBOS llHTspSCHoe 6HUllRJIllQSCROS COe.I\llH8HllS, COCTOHmSS ll3

zrayx ROH.I\8HCllPOBSHHblX mSCTllqJIeHHblX llllRJIOB C 06li1HM pS6pOM Si-Q-Si

[125, 138J I

?R) C1CH2-.;'i-CH2C1

° C1CH2-~i-CH2C1

CR)

~O...

MHTepecHOH OC06eHHOCTbID SToro reTepOUHKna RBnHeTCH B03MOZHOCTi

rrpeBpameHRR ero B llO~S~Rq8CKOe COe~RH8Hll8 a~MaHTaHOBOI CTpyRTy

'pb! rrpa qaCTliIqHOM ranpozase [138J:

B!J:COKJiIe B!J:XO~ repNIaHdopraHJiIqeClllilX ~oe,r...lReEmi, 1I0J!YqElHHhlX

Up>! RCIIOJIl,30BaHIDi B rrpHMOM Cl'!HTeS8 M- R noza : J. -XJIOPMElTM)CIIJI8HOB. no6Y~KnR HaC liICC~e~OBaTD B aHanOrM~~UX 96a~HX IT MOH~KUROHBAL

HHe Rap6oranOreHClIJ!8HH rzna o~((,'lll) ~_nSiCH2(Jl, rna n-o-J [123J. ()Ra3a~OCb, QTO B YC.~OBllRX raao:jJa3HQI'O IIpRMoro CRHre3a YR83aHHlle

~-~OpNIeTMCMaHll o~pa3YET Jnn!e~H~8 C08r~ReHRR ~yx KA8CCOB C

rr3yMH (E) II Tpe~\ff (A) aTOMal~ ~opa y r2pMaH~H:

(i·f.;/8u Cln(CHJ)J-nSiCH2Cl --~ Cln(CHJ)J_nSiC~GeCl) +

4-1~ A

+ [eln (eH) )_nSiCH::] 2GeC1Z

50-60% l3

113M8HeHliIe lite 'IT~GJl8 'lTOMOB J':JJOp:l ::'~:peMHR.>r \D.-O-:3) npaara'J8CRliI He OTp2lK38T,';' D2 mJ.xo~e llPO.rr.yRTOB pesmntH. OCTBllllaMCIi He1ll3

',HllillO BHCORRM (57-'JZfv). ITpnporra EPyrxx 88M8CTllTeJlsfi y Kpe,mlili TaKm8 M8~O ~eT aB BH

XCJ;-d E8!iI9CTB KJlaCCOB i '" 0 [120J. 8ymecrneHBoe B..DJnU!G HS DpoTllRaHZ(' '][1HMCl'O CII[H'J'83i:i OP:T)!iBae" rrczoxeaae aTOM8 xzopa OTHOCJlTem.HO STOMa KpeMHliIS B I.lt;XO,nHOM iUlp~OrrJJIOreHClLJIBBe. TaR. BllXO,n rrpo.n:yRToB

K.;!8CCa E pasxo CHIDltae"':.:; npx nspexone OT J, - R ft - III '( -xzopazF:1"'2ITplilXJlOpClLJIaHaM. OC~l'S);r.J!·"c IiOQTliI O.n;l'lHBROBW ~ C08,lHHeHd

i(J1aCCa A [r26]:

n~1 14?'!' 52% L'~t: 10/b 37% n=3 12% 1)%

39

40

B peaKUIDO npRMOrO CHHT83a C repMaHHeM BCTyna~T H BTOpll~~e ~-~Op3aMemeHH~e CltrraHH. HanpRMep 6llC(TPllxnOPC~)xnopMeTaH

(CI3Si)2CHC1, (~-xnOP3TllJI)TPJJ.XJIOpCllJIaH CI COOTHO3SiCH(CH3)Cl.

illeHll8 npOAYKTOB npffMOrO CllHTeSa B 3TllX peaKURHX B OTJIllqne OT BCeX np8~X ll3M8HneTCfl B nOJlO3Y c08AZHeHllH C TpllXJIOprepMllJlOHO~

rpynno~, T.e. (CI3Si)2CHGeCI3 n OI3SiCH(CH3)GeCI3. B Ta6JI. 2 npKBe~eHH pe3YJI~TaTH npffMoro CHHT8sa co BceMH ll3Y

qeHHIlMH 1II0HosaM8Ill8HHHMll KapOOrallOreHCllJIallaMR.

T a 6 JI n IT a 2

ITpffMOH CHHTe3 Ha OCHOBe Kap6craJIOreHCllJI8HOB (RCI)

Baxon , % R

RGeCI

CI/;iCH2 12 52 C12CH 3SiCIl2 12 60 Cl(CH3)2SiCH2 6,5 51 (CH 3) 3

Si CH2 4 5'1 C1

3SiCH(CH3) 32 12 (CI 3Si)2CH 21 20 CI3SiCH2CH 2 10 3'1 C13Si(CH 2)3 14 13 F(CH3)2SiCH2 6 47 (CH30) (CH3)2SiCIT2 7 26 (CH3)SiOSi(CH3)2

CHZ 5 41

Pa3Hooopa3HHe COe~lleHnR TMna SiCH2GeC13,morna ynoollee noJIY'iaTb no peaRIum xoaneacanaz [I45J:

4.2. reTepO~KJIM'ieCKMe coe~HellMrr repMaHHR

flMllenH~e coe~HellHR C TpeMR O~HaKOBHMH llJIll paSHHMH aTOMaMH 3JI8MeHTOB lYE rpynn~ (KpeMHllR n repMaHllR). paS~eJIellHHMH yrJIeBO~OPOnHIlMll MocTllKaMR. HBYJIllC~ HCXOnHHMll nJIH nOJIYqeHKH HOBHX reTepOilllRJIllqeCKHX cncTeM. TaK, qaCTll'iHHll r~pOJIll3 3TllX coe~eHrrrl BJIarOll B03AYxa RJIH KOHll8HTpHpoBaHHoll COJIHHOll KnCJIOTOll npKBoAZT K npeBpaIlleHMD HX B reTepO~JIH. T.~. peaKUflH npoxo~T MCKrrDqHTeJIbHO no CBRSH Si-CI, He aarparasaa CBRSH Ge-CI [1 38J :

HZO, W [Cln (CH) )-nS1CH212 GeOl Z ----

n=1 - 90% n=2 - 47%

I n=) - 1J% Cl 01

n=2 CHZ - 'Ge - CH90% I I 2

CH)~i - ° - 3i-CH I 3

C°1 I CH)-31 - ° - S1-CH

I I)

CHz - Ge - CHz ci ' "ci

Hs06xo,11llMO OTMSTllTb, 'ITO na)KS

42

HaMIl 6HJlli H3ytIeHtl II .IJ:IJyn18 XllMlItI8CK1l8 npeapamenas rroJIYtIeHHHX rrpHMHM CllHTe30M .~ellHHX c¥~Kap6arepMaHOB. rrpllBO~B K HOBHM reTep0IJ;llKJIv.tIeCKllM CTpyKTy.paM [93, II3, 125J:

9H3 (XS1CH2) 2

GeC12

6H3

I

30C]2H,O, "'I

C1 C1

"Ge/ ,; "\

CH CH CH \ 2 \ 2CH3 CH_M,.r.l3, 31 31/ ~ CHi "0/ 'CH,

Ha OCHOBe J., -lUIOpM8Tl'LlJ,!(lIlMe=epMaHa 6bIJI CllHTB3HpOBaH Il nep~Hll npe~CTaEMTeY>D Ca!BrePMallHRY>oneHTaHOB - Ge-~e~-Si -nzMeTU-1-repM8-3-cJiU8Il;lIMOnSHT8H [sr, 92, 93J:

9H3 +

Mg ,C1~1CH=CH2 CH

3

ITo 8BanOrlltIHOH cxeMe 6an nO~qeH TaKme rrepBHll rrpe~cTaBIlTey,D cKXarePM~oreRc8HoB [8r]:

ey) CR) CH I I ) Mg+ H~eeH2el ----~C1Si(CH2»)GeCR C1 I I 2

CH~ ) CR) CR)

CHHT83 ~epMaUHRnoOYTaHOB OHn ocymecTR~eH cTla~~ nyTeM

036, 95. 97, 98, 103. 106J:

3TOT rryTb ORa:J3JICii. qm:c'0,i!,HHM ;IJ,AA rrOJIY'l8HRJI 1,1 ,3,3-TeTpaMeTM-I-repMa-3-cnTl1IIHK.i10dYT8F:J ;

ctrca ) GemL.,Gl co H ' CR' ., S' """., Me: r," I C'" } S' GU M ~Cl ) 2

MOCTIlKOBblS COS,IJ,ilHemlil rCpM8Hllli oo.nee CKJlOHHbl no cpaBH8HlllO c

KpSM!IHeBblMI! Q!Ifi.JIOraMll l( cJlS.l!YKlUleii peaKlUll1 [37, 69J (CM. c. 22):

5. IIf'UI13BOjlJillJ.. A.Ll.AMAHTAHA, COllEP~ rm!PJII.j!

HH1'ep8C K ~TOM:; ;;.r;;,ccy C08.llllHellJlli CiWl nponzxroaan 113BSCTHOii

epapMai

~ -,LHI;lln'Wlra.l0r81lI'8pMMa,IJ,aMaH TaEEI Olillli IJOJey,{8HU ,IU1J\'le TY-JlllpOBaml

81,1 ~-TpaM8TIl.JITepMMa,IJ,aMaHTaHa [AI, 18U1: onC1

4 1-Ad}~e2GeH1-AdGeMe --_.:!......,)~ 1-Adl.le2Ge Cl 3

em xo COS,IJ,1lli8HM Owm nOJl'j'lSHlJ II ,IJ,pyrllMll nYTJThl11 [ISOJ:

( B5;~)

U6IlapY;KeHO, 'ITO B yCJlOBllJIX pearoull'l ~pll,IJ,eJlH-KpaqiTca BllHltlII'epMa

HbI r8pMllJI~TYwnlPyIDT KaK caM a,IJ,aMaHTaH, TaK II 81'0 raJlOrSHrrp01l3BO,IJ,HHS

[noJ:

AID) C;iHT8~"u L- u ,.;- (w -TpllXJlOprepMllJl)QJlKllJl3J\aJllallTallOB ME npsn

:;0~~}WIl1 T8Y.;Ke npocron II Y,l\OOHHll MeTO,l\ IJPllC08;D;lilH8HlIH llG8C:3 K aenpa,IJ,eJlhHUM npOIl3BO,IJ,HlJM a,IJ,aM8HTaHa [170J:

+ HGeC1 - 1-Ad(CH2)3GeC131-AdCH2CIJ"CH 2 3 2-Ad=CH2 + HGeCl] 2-AdCH2GeCI J

IlOKasaHa B08MOMHOCTb a~~1I1pOB8HllH qieHIlJlTpllXJlDprepMaHa I-dpoM-

al\aMaHT8HOM:

1-TpllrDJlOrSHrepMIIJl II I-JlHlcleT1':JJraJlOreHrepMll.118,IJ,8Ml1llTDHLl 06J1a,l\alDT Drib! 'IHIlMll CBoJjCTBal~1I Opl'::UlI1.1rB.l0reHrepMaHOB [ib~J:

l-AdGe1ce J

t MeMgI ' n=O IROH MAlii

l-Adl.len Ge (OR) 3-n~ , -A.iJ4en GeX 3-n ---~ 1 ;t.1" _

SnG1 //

TapMllqaCKBH J: llliMlI'ISCi\3R YCTOllq};BOCTb 1-AdMe (}eOH cYlIlaCTBf:iH-

HO HIDKe. qaM y aHaJICI'l'lqHOrO COSnlflWlillil. KpeMEl'lR fl80]. IIOJIY'WHHu:I1: ITPO~RT rrpsBpalllasTCR B ~rSpMORCaH rrpM RilTIHqSHMM B I'SITT8HS r~i 08H

SOJIa. a raxse npu .ZlJIl'!T8JILHOM xpaHeHIDl:

IIspBu:I1: npa.uCTaBl'lT8JIb repMaTpaHOB, co.ue~lIlHn a.urup.aHTY~lbHHll sa

MeCTIIT8JIb. - I-a.l\UM3ETllJII'epMaTpaH, (jlIJI CIIHTSSllPOBa'1 B 1975 I'. [HIJ:

( 2J-82%)

BnOCJI8,llCTBnR bwm no.rryqeHli II npyrae rspMaTpaHbl LISS]:,

, 'CIL,-, "GH \2f /'1'" --J \ l-AdGe(OR),+N(c-rl'OCIDl:eOIl) )' : ( Oli \(CH2CIl?OH)3_--IMeGH

..J ... n - t -.......... v GF.- \ /' 2/LI. \.

Cnoco6nOCTb rllApOrSpMana K OrrTICaHH~ BHlliS peaKURHM r~pOrepMHF~ipOBaHllH OTKpHBaer illllPOKll8 rrYTIT rrO~qeHllfl KapdaPyHK~OHa~HliX COS)(.rneHID! C 1-AdMe2Ge -rpynnon [I87J:

)J.JJ.H: rrOJIyqSHllH repMaHllnCOnep~lllllX N-3aMS1USHHHX aMll,IlOB nJm IlMll

nOB I-anaMaHTllJIKapdoHoBoll KTICJIOTH Hapfl.llY C OdliqRHMll MSTOnaMll d~a llCrrOJIb30BaHa OdHSpY!\SHHaH HSnaBHO [177, 205J peaKUllH xoaneacanaa S¢rrpaTa TpllXJIOprepMaHa C N-(raJIOreHMeTllJI)~1.llaMll:

1-AdCOCl + EtJGe(CH2)3H(SiMe3)2 ------~#~(1-AdCO)2B{CH2)3GeEt3

HGeC13·2Et 201-AdOOJIHCH2Cl ~ 1-AdC01lHCH2GeC13 -------*"

- lI( CH 2CH2CH) J 1-AdCOJIHCH2Ge(OR)J ....---------,...." ________~. 1-AdCOJIHCH2Ge(OCH 2CH2 ) 3H

B npouecce nOllCKa dllOJIOrllqSCKll aKTKBHliX COe.llllHSHllM rSPMaHRH HaM}! caare snpoaaa PM npoaasonasx aWiHoa.uaMaHTaHa [204J:

{Me3Si);!H ~ 1-AdllHSiMe 3

)COCl

oo " "1-AdNHCCH(CH3)CH2GeMe31-AdNHC(CH2)2GeMe3

HHTepSCHO oTMeTllTh, QTO pSaKIJ;llH B3aRMOnenCTBRH XJIopaHr~p~a

2-MSTllJI-3-TpllXJIOprSpMllJIITpOITllOHOBOll KllCJIOTli C I-aMHHoauaM8HTaHOM npOTSKaST HCKJIIDqnTeJIbHO UO aToMy XJIopa rrpH Kapdo~HOH rpyurrs:

o II .JlQl!

1-~dNH2 + C1 ~ 1-AdftHCCH(CH3)CH2GeCIJ3GeCH2CH{CHJ)COCl

47

---

,l 1'0 JKe ClpeMJI ;rIl1J B3311MO)J,eHCTBlI:J1 1-8MHH08,TI/1h1iiET8H3 11Jlll ero 1'1'1:

t,le TH.7ICHJIll.>TbH01'O IlpOll3BO)J,H01'O C X.'IOpmII'V

B aaKnIDq6Hll6 yrrOMffH6M a CllHTe3e TeTparepMaa~aMaHTaHa U22]:

yH)

Ge'On) • (71) 4 CH)Ge ~ GeeH)

~b:~ )

Eo~ee no~pooH06 oooo~eHlle Bcex paOOT no XllMllll a~a~aHTaHOB~x CTpyRTyp, co~o~anulx repMaHKtl, npe~CTa~eHo B ooaopax [142, 158, 226, 227, 232].

6. I'EPMA'ITAllll 11 IIX AHAJIOn1

Hallia nepBaH nyo.TaKaURH B STOll co~aCTM OTHOCllTCH K 1965 r. ~O, 74J. CnCTeMaTnqeCKOe llcc~e~OBaHlle XllMnR repMaTpaHoB, HaqaTOe

B 1975 r , [141, 191J, Irpo~oJUtaeTcH MB HaCTo~ee BpelJir: • Jlo 1975 r. XllMYJI repMaTpaHoB npaKTnqeCKn OUAa He ncc~enoBaHa~89,191,2D6,214J. Hllxe onncaHH nyTn rrO~qeHllH 3TllX coe~HeHnn n llX XllMllqeCKlle rrpeBpaU1eHnJr.

6.1. PeaKgllH nepea~oKcn~poBaHnH

BaallMo~eilcTBne pa3Hoo6pa3HHx opraHOTpnaKRORCrrrepMaHoB C Tpll3TaHo~aMnHOM (T3A) npoTeKaeT B MRTKnx yc~oBnHx npll OTCyTCTBnR KaTa~n3aTopa II Mo~eT paccMaTpKBaTbcH KaR HalloQnee Y~OOHHrt n YHllBepca~HHfi crrocoo CllHTe3a paaHoo6pa3HHx repMaTpaHoB U5I.177,~I4,245-247,2blJ:

T3A C li::nRGe(OR'») ~ t +)R'OH o...-Ge ° I """"'0 R

r'zre R = HO-, lJeO, n-PrO, lJe, Et, CH=CH Z' CiiZCH=CHz' n., l-Ad, t-Bu, CPh3' -CHzCl, -CHzI, CH2CH2C( O)Il ':::: ,CH20H, CH2CH2CF3' CH2CE2C008t,

RC(0)HCH Cl, Br, T3A ~ N(CH2-, -CH 2CH2CONH2; 2CHzOH»). 49

3TBM MeTO~OM nanyqeHU paaHoo6paaHue ~aM6HTRnrepMaTpaHU ~41 15~, 188J:

1-AdGe(OEt).3 + N(CH (CH __2CH?OH)- n.2CHMeOH) 3-n

1-AdG~(OCH2CH2) (OCHMeCH ) ~ n 2 3-u

r~e n .. 0-3

B nocJIe,ll;HHl3 rO;:;;H na OCHOBl3 (RO) 3GeH [161. 17S] ClaMIT 6Wl paapa60TaH OpKrRHa~HHa MeTo~ cHHTeaa Rap6oPyHKUlloH~~HHX rSpM?Tp2HOB:

rns fir .. CJ', OOOSt. H, HaROHen. Ha COHOBS B~- K ~ -6DOMMl3TRr.~Pllall~ORCRrepMUnOE

6wm nO.l!Y'IeHU rSTOpOliTfHF.U;l'IORaJ.l;'RH6 T!U:'JJ!:\(HWRl'epMaR;J ~C·.·OP116 'l':~R'll8 nocJJYI!liI.lll'l OCHOBO:.\. CRFi...asa Opnr,;lB.llJ,llliI: :~lipMaTp·n.'~I' LT7

FeaJilli'liI rrepeaasoxcanapoaaxaa C IlOCJIe;r"y1lJllHM rJil,lijl0JlliI30M 6wxa RCllOJIl,30B3Ha HaMR 11 ,IJ,IT.ff rrO"1YqeHlIR I-rR,lijJoKcRrepMaTpaHa - uosoro rrpe.uCTaBHTeJL

52

6.3. ITo~yqeHlle repMaTpaHoB Ha OCHOBS TIO~OpraHorepMceCKBllOKcaHOB

ITpllCYTCTBll6 me~oqaoro KaTa~saTopa rrpll BsaRMo~ettcTBllll ceCKBll-

OKcaHOB (RGeO, ,S)x C T3A HS acsrna 06flSaTSJIbHO. YKaS3HHafl pea~fl OKas~aCb OqeHb y~o6HliM crroco60M ~eHT~llRauHll repMCSCKBllO

RcaHOB, OC06SHHO B TSX CJIyqaflX. Kor~a rrpSBpa!Ilellliil OMorc CeCRBHOKcaHa B ~pyrOH rrpOllCXO~T rro ~yHKnROH8JIbHUM rpyrrrraM B a~K7~HeH llSIIH:

1tl 40H N(CH CR OR) ~ (0, ,SGeCH 2 2 J(0, ,SGeCH 2CH2COOEt) x 2CH2C01;112) x

I 1 ~ N(CH2CH20)3GeCH2cH2CONH2

ITOJIyqeHlle rapMaTpaHoB HS ceCKBllORcaHOB MOMST CJIyMllTb T8RMS ~ORasaTS~bCTBOM 06P8S0B8lllifl HeRoTopuX opraHOTpllI'~OreHrspM8HoB. B~s~elllie KOTOpUX llS peaKQllCHHOR cpe~ 38TPYM8HO y~ HeB03MOXHO [rnJ. HanpllMep:

GeBr4 + ~ n-Br GeC6H NRR2NC 6HS 3 4 2 I -.

~ N(CH2CH20)3GeC6H4NR2

r~e R = Me, Et.

Hs~aBHO B p8aKli~V KOanSHcaUUll c ~paTaMll TpY.IT'~OreHrGpMaHOB

ycneWHo BBe~eHll (N-r~Or6HMe~)lli"~, -llMllnH II -~aRTaMll. qTO

OTRP~O rrYTll CllHT63a aosoro snacca ]'apr,:3TpaHOB [177, 2lJ5, 247J:

3TH Me repMaTpaHll nOJIyqSHl:l H ll3 COOTBeTCTBYlDIIllIX opraaorpaanxoKCllrSpMaHOB (205J.

6.4. ilo4YQeHZe repMaTpaHoB Ha OCHOBe Cll4H~OBHX 3WHpOB TpR3TaHO~MHHa

TaKOll rrYT~ rro~yqeHHH repMaTpaHOB EMeeT TO rrpeHMymeCTBO, qTO crnanaer He06xo,I\HMOCT~ rrpeBpameHHH C1 GeR B COOTBeTCTByJOlIliIe

3TpRa.JIROKCnrepMaHU [245J:

",0 CH /' ° ;R = CH r ; C(CH )C /' Ad.r.ne 2CHC -, OR 2 :3" OR

6.5. 1-f~poKcnrepMaTpffil(repMaTpaHo~).CHHTe3u Ha OCHOBe Ge02

TpR3TaHo~HH R erQ rOMo~orH ~erRO pearHpyDT He TO~KO C rro~opraHOrePMceCKBHOKCaHaMH, HO II C OKnC~ID rePMaHRH [178, 191, 197, 249J. OC068HHO HHTepecHHe pe3Y~hTaTu nO~qeHU npR llcrrO~30BaHRZ TpR3TaHO~aMHHa: peaKUllR npoTeKasT 3K30TepMRqeCRH, II C RORllqeCTBSHHUM BUXO.nOM 06pa3yeTcR MOHor~paT 1-rR.npoKcnrspMaTpasa, BHUa.naID~ ll3 BO,JJ,HOro pac rsopa B BR,I\e KpRcTaMoB [178,197]:

L tI + Ge0 2 N(CH 2CH 20) :3GeOH~H20 (~100%)N(CH 2CH20H):3

llpR BHcyrnMBaHHll 06pa3uoB repMaTpaHo~a (TeMnepaTypa rr~~eHRH 156-1570C) B BaKyyMe ~ .naEe Ha B03.nyXS Ha6~.nasTcH 3HaqnTe~HOe nOBHIDeHll8 TeMllepaTypH n.~a~eHHH BemecTBa, qrO 06~HCHH8TCH ~erKOCThID y.narrSHRH KpRcT~3auzoHHofi BO~. llpR .nRZTe~~HOM xpaHsHliZ Ha.n P205 .nOCTnraeTCH rrnnHoe 06s3Bo~aHRe COe,I\HHeHRH .no 1-rn.npoKcRrepMaTpaHa C TeMnepaTypoll pa3~OEeHl'!JI nO~qeHHOrO npo.nyKTa ~ 2900C. PaHee 1-rn.npoKcllrepMaTpaH 6~ cHHTe3RpoBaH HaMR [151, 244J rn.npo

+ I~30M 1-~oKcnrepMaHoB ROGe(OCH2CH2)3N 3KBRMO~HHM KnnRqSCTBOM BO.nu [176J. ll~qeHBOe BSmeCTBO He RMe~o onps.ne~eHHoJJ: TSMllepaTypH ~a~eHHH, TaK KaK ~OC~ CMeChID 1-rn.npoKcnrepMaTpaHa R sro M0

HOrR,I\paTa. fepMaTpffilnll R ero rn.npaT ~erKO TRTpyDTCH no ~HWepy. KaK 1-r~poKcnrepMaTpaH, TaK II ero MOHor~paT pacTBoPRDTCH B Bo.ne (30%) H MoryT 6UTh BH,I\e~eHH R3 Hee B Baue rn.npaTa nyTsM .n06a~eHRH au8TOHa ~ RcnapeHReM BO.nu. llPll KRllHqeHRH C ll36HTKOM rSKCaMeTRn

,I\HCa~a3aHa MOHor~paT rspMaTpaHo~a rro.n06Ho 6e3BO,JJ,HoMy rSPMaTpaHo~ rrpeBpamaeTcH B 1-TpRMeTRnCRnOKcHrepMaTpaH. OH TaRXS ~erRO pearRpy

eT C O-aMHHo4>eHo~OM:

§ i(Me 3Si)2XH I( ) ..

:K CH2CH20 3GeOH -I

C °;Me 3SiOGe(OCH2CH2)3· o-Irn2 6H4 H :t \ O-NH2C6H40Ge(OCH2CH2~3N

53

http:BUXO.nOM

I-~oKcnrepMaTpaH KO~qeCTBeHllO paCmennH87 CEH3h M-N ~ COOTBeTCTByJOIl!I

I1pHMe'laTeJI:bHa BhlCORaR CeJIeRTHBHOCTb H3Y'leHllhlX peaKIJ;ldl:: He3aB~CRMO OT cooraoueaaa J..-~OJ10B H ,lln3TaHOJIaMIDlOB nO'lTH ROJIH'leCTBeHHO 00pa3yeTcR HCRJIID'lHTeJI:bHO O~O coe~eHHe, a He TpH B03MOXHhlX.

B SaRJID'leHHe CJIeAYeT OTMeTHTh, 'lTO Ge02 B BOnHoi cpe~e pearHpyeT co MHOrm~H TIHP~HOBhlMll, ~ORCaMOBhlMH H aMKHORHCJIOTaMH, o~aRO 'lame Bcero 00pa3YIDTCR HepaCTBOpHMHe aMOpWHhle coe~eHHH, ~ORa3aTeJI:bCTBO CTpOOHHR ROTOphlX BCTpe'laeT Hepe~o Henpeo~~e TpYnHOCTH. TeM He MeHee, CllHTe3 repMaHanOprallli'leCKHX coe~eHE! Ha OCHOBe Ge02 ITpe~CTaBJlHeTCR BeChMB nepCITeRTKBHhlM.

6.6. CHHTe3 1-ragporepMaTpaHa Hero C-WeTHJI3aMemeHHhlX aH8!OrOB

~ rrOJIY'leIlliR ITpocTeKlliero rePMBTpaHa HGe(OCH2CH2)~ HeB03MOXHO HCnOJIb30BaTh MeTO~ nepeBJIl\ORCHJIHpOBBHRH, TaR RBR B 3TOM cAYqae

CJIe~OB8JIO Ohl HCXO,llnTb H3 HeH3BeCTHHX TpHaJIKORCnrepMBHOB (RO)3GeH, He cymecTByD~X B CBOOO~OM COCTORHHH. OnHaRO ROMnJIe~CHHi ooe,llnHeHRR TpHBJIKORCHrepMaHOB C TPH3THJIaMIDlOM B3aHMO~ejCTBY~ C TpHBJIRaHOJIaMHHaMH ITpH ROMHaTHOi TeMITepBTYpe C OOpB3aBBIllieM He~OCTYUHhlX panee 1-rH,1lJlorepMaTpBHa Hero C-MeTHJI3aMemeHHIlX rOMOJIOrOB [160, 166, 167J:

(RO)3GeH-HEt3-mROH + I(CH2yHCH30H)n(CH2CH20H)3_n

CHj= tCH6H2 , _ Mec( r ;CH2~ ° n I ° 3-nH r~e R - i-PT; n = 0-3_

3TH 1-~orepMaTpaHll - r~pOJIllTH'leCRH II TepMH'leCRll HeycToiqnBHe oe~e RpHCTaJIJIll'leCRHe BellleCTBa C TOHROBOJIORHHCTOH CTpyRTyPOll, JIerRO paCTBOpHMHe B ~eTnJICYJIbWORc~e, CJIaOO - B OeHBOJIe.

6.7. XHMn'lecRHe cBoHcTBa rePMaTpaHoB

KaR ll3BeCTHO, CBR3h Ge-O B aJIRORCnrepMaHaX RpaKRe rH,1lJlOJIHTH'leCRIl HeycTOH'lllBa (ooaee , 'leM CBR3hSi-O B aHBJIOrH'lHhlX CWUlHBX).

55

56

O~aRO repMaTpaHH aHaqzTe~HO oanee YCTOll~H R ~nrrR3Y, qeM aHallOrMqRHe CanaTpaHH, a repMaTpaHOH ~8Ee ITepeRpMCTa~aOBHBaeTCH Ma BO.!Ul.

ITPH paCTBOpeHHH I-aXKORCHrepMaTpaHOB B Bo~e aXKORcv~pyrrrra 3aMeIllaeTCH rR,l\pORCHJIOM, O,llHaRO aTpaHOBaH "MeTRa" rrOJIHOCTbKl coxpaaaeTCR. Ha OCHOBe 1-aXKORCH- H r~ORCHrepMaTpaHOB y~a~ocb paapa6oTaTb y~oOHH8 MeTO.lUl CMHTeaa ~pyrHX ~e-aaMeII1eHHHX repMaTpalloB [151, 244J, HanpKMep:

HF (Bo~HHll)

PG'e(OCH CH i2 2)

t HI" (B O~Hblll )

ITPH CIIJIaMeHHH repaarpaaoaa C aMMOHIDIl1H1Orl COJl!lMH psna 1GlC~OT ~erRO 06paayHJTCR COOTBeTCTBYKlmH8 repMaTpaHH:

N (CH 2CIJ 20) 3GeOH~H2o + NH ~ 1?.-~':f N ICH ,GeX + 'lH4X 2CH 20i o r.ne x = CI, Br, seN, F 1-1 T.,i:I.

IIo.uo6HO cBoeMy RpeMJrneBCMy- aHa~ory. I-rll.uporepMaTpaH He nplIC0e~HeTCH ITO RpaTH~ CBR3HM HeITpeAe~bHHX c08nHHeIDtil B rrpncyTcTBllll

H a300llcllao6YTHpOHllTPiIJIa _ ,le CK.'lOH8H OH H 1{ peaRIJ;1L'IMH2PtC16 ~erH.uP0Ro~eHcan>m co crm:pTaMH H q")c·;jJict,,. B TO Me Bp8M;: ycraaos~eHa BHCORaR peaKUllOHHaH crrOC06HCCTb 1-"llJ~pOI'epMaTpalla '10 OTHOliJeHIDO R ra~oreHaM II OprallHqeCRHM raJ'Ol'8llll)lHM rZ44]:

Peasnaa l-I'l'.,n:porepMaTpalla C ;lIpyr7.MVc opr-aHora.nOT'sm:;:;SMlt PH€})T oozae c~o!lHlill xapaxrep , TaR RaR HapMY C nponeccoe r3JIO,'8flllPOB8H:-;;r Ha6~.uaeTCH He CBOHCTBeHllaH I-I'~OCll.'IRTP8HY peaK!.l;llH KOHiJ8W mum, npzaonsmaa R 06paaOBaHIDll HOBoH aRaO:UID\~q€CROH csasz G8-0 [24,-1] :

ilC1:'mr~ep, npa 333nMO.ue!aCTB1UI repaarpaaa C dp0M:llcTHM aiIJIllIJIOM B opsne noaapaoro PLlCTBOPRT8JL9: (CHiN) Bbl.lJ:eJIeH I-dpOMropMaTpall, a B yCJIOBRHX ,panllRa~bHHX peaKUnn (deH3~, rrepeKRCb deH30~) - e~HCTB6HHllH MoHoMepHHll rrponyRT - I-a~JIrepMaTpaH.

TaRRM 06pa30M, npOBe.u8HHoe RCCJIe.uOBaHze BHRB&nO 3aMeTHHe pa3~'lllH lCl!Ml'l'!ecIU!X CBOHC".'B [-I'll.I\pOrepMaTpaHa ]I[ ero KpeMHKeBOrO SlHaJIOra, RoTopue ocooeHHO 'J:pRO rrpO~TCH B peaKURRX C opraHorarroreHil.IlaMR. l~o~o rrpe.unOJIO~T1, 'ITO CITeUH~R'IeCROe rrOBe.ueHne 1-rH.IlporepMaTpaHa CBR3aHO C B03MOE~OCTbID ero rrpeBpameHRH B rep~eH:

Hte(OCR2 -CH2)i - : Ge(OCH2CH2)2IfClI2CH20H =C-Hal ~ Hal, r:- i f I

- 0 - lse(OCH2CH2)2JrCH2CH2OH -::C-Ge(OCH2CH2 ) 3Jr + HHal

TIpoBe.ueHHoe KOMTIJI8KCHOe CRCTeMaTZ'IeCKOe Jl[CCJIs.uOBaHlle Ge-3aMe

~8HHUX repMaTpaHoB M YX aHSJIOrOB MeTo.uaMK liK-. HMP-crreKTpOCKOITKH, MaCc-crreKTpOCKOTI:IlJ1[, ~M3JI1KOMeTpKff II peHTrenocTpyKTypHoro aHa~3a ~50, 153, 191, 246, 251] CBaneTe~CTByeT 0 c~eCTBOBaHHH B 3T]I[X coe~HeHHRX TpaHCaHHyXffpHoro B3amMo.ueAcTB]I[H Ge~ H.

6.8. I-OpraHllJI-2-Rap6arepMaToaHH

BrrepBue TIO~'IeHH 1-oprsHRJI-2-KapdarepM3TpaHH - coe~HeHllH, B MOJIeKYJIe KOTOpUX O~H aTOM KRCJIOpo.ua B rrOJIOXeHKH 2 3aMeHeH MeTRieHOBoH rpynITOH [159. 162J.

B Ka'IeCTBe RCXO.uHUX coe.uRHeHRH RCrrOJI130BaHH 3-~oprrpOrrRJIrepMaHu:

RC12Ge(CH2)JC1 ~to1Ge(CH2)3Cl+HN(CH2CH20H)2+Et3N EtOH

CH~~ .-eH

c(C7--"-~-i----· 2-. CH

\ CH2 t I 2 \ ~ /~qe ---- CH2

rne R ~ Me, Et, Ph. ° R 2-KapdarepMaTpaHU OOJIa.uaIDT rrOBHilleHHOM paCTBOpRMOCT1D B OpraHH

'IeCRHX paCTBOpllTeJIHX M 60JI1rneH rH.IlpO~3yeMOCT1D, 'IeM aHaJIOrR

6.9. Kap6oHMCOlleplltanm8 aHaJ.lOI'R rspMaTpaHoB (rSlJM8Th;i21!li)

He1l311ecTHHe panee KapOOHMCOllSPl!taIT(l'I8 aaaxorz repaarpaaos (rep

MaTpaHOHH) nanyqeHH B3aRMOlle~cTBReM TpF.a~OKC!/[repMaHoB :II aMilHoyK

CyCHHX KRC~OT [155, 172]: RGe(OR).,

~ 1.(~H2COOH) n (CH2CH20~) )-n' n~ 1-3 Hjr-C-~-C-H--\-If----' H \ C!l2 (-:;\

2C/" 2 H:,. ()(j,J:~'i.Ua ..;;,~ c: KaK :l'I3BeCTHO. DmpOIUIM ;J,[;°RTPOM \papMaF::·~.,;.l:·{eC!:CIO ,l\eE,;",'~ LI:0~.

229J:

58

AE3JIOrll'IllHM 06pa30M 6wm nOJIy'!81W CIDlPOI:(1'lltllllQBCKJlB repMOW!HH, npoasnonase ,IQyrl'IX TpnS.;maHOJIaMl1lHOB, ,ltI'!STBHOJIaMl1lHOB :it ,ltI'!::lTaHOJII'Dmma [186, 233):

(HOCR 'HCR2) 2NR

(HOOCCHRCH2Ge01, S) x ~ r- 0~~-0-4e(OCHR 'CH2)2k (HCCH2CH2)2NCH2COOH CHR-CH2

CTP08HH8 repMommOE YCTaHOBJISHO MSTOnOM pSHTrBHOCTPYRTYPHoro aaaaasa [I65J, MSTOnmm .8M? (If{. I3C) 11 MaCC-CIIBKTPOM9T£HH. IIp.II IlCCJI8nOBaH~ T8MrrspaTypHOn 3aBHCllMOCT.II CIISRTpOB BMP (IH, 3C) o6HapyJKeHO TaYToMspHoe rrpespanenaa HS1l3BeCTHoro paaes TEa, IIpl'IBollJmlee R o6pa30BaHllID I-(2-Kap6oRCll::lTKn)rspMaTpaHB [165, 186J:

(;:::'0 /'0 _ ~"""O

RaI( M8!t,lJy lGIMH6ll YI'JI8po,na II OCTaJThHlllt SJI8M8HTOD lYE rp"JI-re-l" ~y.28 48J Ha J ~u • '. -,),

, • OCHoBaHHZ IIsYQ8HlIR OTHOCHT8JIDHOll p8aKUHOH~OCJIO~~~HOCTII aHaJIOrK'UlIiX J., -Kap60!IJyHKIJ,lIoHaJIl,HhlX COS,n,nHsHID!: KpSMHI'IiI L P3JlM8HIlH

C,I(8AaH BYBO,ll, 'ITO B STIIX COS,JUlli8HIU1X rspMaHlrJ! 60..168 9JIeKTpOOTpm::a

T8.JISH, '18M Ep8MHHll, HaJIpRM6p [32J:

~e4Ge + MeMe JSiCH 2HgCH2GeMe J JSiCH 2HgCl

PaCJIaJIaraR 60JIDrerrM RO~'lSCTBOM rSpM8Hnll- II Kp8MHIlROpraHIl'lSC

RRX coe,l\H1I8HHli, COCl'aBJLr r -UOJ)o].{eHJlli (n = 2). ii."!ilJ!OrlrtlliO 113~j"l!fl)].;'1Cb h':"'UI!GC

,J;",::oc"" rrr.:,,10Cll nOrJlCEi8HllR S,'!' M B 1rr~-Cn8K1'paX, T. 8. Cn8KTpaJlhHbl8 X';l13KT8 ,;lIOTHKlI 8TllX B8l118CTB HSM8fUilOTC5I Cn:.103THO C IIX p8aKIUWHHoit

~710L:OOHOCTDl0.

i;CCJI8~OBaHll8 BaKY~~~HHX YJlhTpaWllOJI8TOBHX Cn8K1'pOB oOHapy~o

08TOXPOMH08 CM8l118Hll8 8JI8KTpOfJHOn 1l0JlOCH rrOrJlOlil,8HllR B aJl.IDlJII'8pMaHax,

;W1'Op08 H8 H30JllO,lla8TCFc JlJ1i1 JJ,pyr;lx 1.J18HOB rOMOJlOl'llq8CKOrO pzna,

CnOKl'pbl 3Jl8KTpOIIHoro nap8MaI'}l;ITHOrO p8S0H3Hca (3TIP) TaKJK8 noxasann

1'iCK.'IKJ'IllT8JlhHOCTD 3J'w1Y.JlCll"'I:JHOB, IIX CllI'H8Jl no c(JOpM8 OTJillQaJICR OT

CllI'H8Jla BHHllJI- H r -OY1'eHMJlC?w18HOB, B TO BpeMfl KaK ,llJlfl nOCJle,llHHX CO8,llllH8Hlli\ cn8KTpH 3I~ TIOJ'~OCThro COBna,ll3roT. CpaBH9H1I8 BblqjfCJl8HHOM

I' H311u8HHOM MOJl8KyJ1flpHOH pee!JpaKlum (I,m) ,llM C08,llHH8HIID PM8

R3M( CH2) n CH=CH noxa SHB88T flBHyro 8KSaJlb1'aumo (+C!,:2) )lM anzancn2 JiaHoB (n = 1) II 8e O1'CyTCTBII8 ,I\Jlfl C08,mmeHHM, rne n = 0, 2-4 un] .

H3J1wm8 B a.rLilliJlC,1Jl8HaX II -r8pMaHaX IICKJlIOqjfT8JThHHX no cpasueHlllO C ,llpyrHMil 'W8HaMH rOMOJlOrHQ8CKOrO pana cpllSllQ8CKllX OC008HHOC

Teli, nO-BllX~MOMY, CTaHOBHTCH BOSMO~HM B CIWy r80M8TpllQ8CKOrO

CO.TIlJK8HMH BTOM8 r8pMaHlIH II KOH8QHOrO aTOMa yr.nepona KpaTHOM CBHSH,

KOTOp08 00Jl81'Qa8TCH, B8pOHTHO, B p8aKUlloHHOM KOMnJl8KC8 n8peXO,llHO

1'0 COCTOHEllH. BOSMOmBOCTh cymecTBoBaHllfl aJl.illlJlCIWaHOB II -r8pMaHOB

B IlO,llOOHOI'O pO,ll8 rrpOCTpaHCTB8HHOll KOHCPOPMaullH

('" CHo: /' 2 0+ R CH

31'1. ". ~ ~

Ha1'.TlFJ\HO o6HapyJKHBaeTCH lIS MO,ll8.~fIX CTroapTa-EpllrJl86a. O~aKO 1'80

M8TpMQeC!W8 cOmm8m18 elTOMa 1'8pMaHllfl II KpSTH01I CBflSH, OQ8BM,llHO,

E8 HBJlfl8TCP. CTpOrQ H806XO,llIlMHM YCJIOBll8M 6"',11 -conpaxenas , TaK KaK B ft -illlKJIOrr8HT8HllJIT8pMBllax OHO H8BOSMOlKHO, O,llHaKO 8Tll C08,llllH8HIIH rrpORBnHIDT B cn8K1'pax YO Il KP BC8 npllSHaKIl tI) 11 -conpH~8HHHX CHC1'8M [33, 5SJ.

HaHOOJl88 flpK08 npoflB~8Hll8 BJIllflHllfl npHpO,llH 8Jl8M8HT8 IY 1'pynnH

y,ll8AOCh oOHapyJKHTh B P88KU¥~X npHc08~H8HHH p0,ll8Ha no KpaTHoll

CBRSH K C08,llllH8HHmA Tlllla RMCH~CH2' 1',ll8 R - CH3,

C2H5, aM - C,

Si, Ge, Sn [7, II, IS, 39J. OKaSaJlOCh, QTO CKOpOCTL npIlc08~H8HHfl pO,llaHa K 8TllM C08~H8Hll.F!M P8SKO YB8AllQllB8TCfl npll n8p8XO,ll8

OT y1'Jl8p0,lla K OJlOBy. KaK M CA8,llOBaJlO o~aTh, P88~HoHHaH cnocoo

HOCTh 3TllX C08,llllH8Hllll. HO B pa~KaJIbHHX p8aKUHRx (nO.illlMepilSaUMH),

H8XO~TCR B ocparnoit saBIlcllMoCTH, T.8. nanae r OT Si K Sn [S].

IIPil ranpaposaann Rj,1CH~CH2 II Ri,\CH

62

;oaIJ;IDl ~i:> Ge:> C :> Sn ). B T8ROM lEe nopanxs 1I3M8fiRe'?Gc cxc; 'CO'!:" npnCOe,lJ;llHernW HSiC1 x COe,lJ;llHeHlUlM rnna B ,IiCH=CH J 3 2,

MSy'leHHe cnexrpon y~, KP. l1K l\ TIMP Herrpe,nemH!1X coe,mmeHllI' RpeMHRR, rspMaHHR II OJIOBa noxaaano , 'iTO 3.JI.ml.ITbH8R rpynna , npncor)lllliSHHaR: R aTOMY si , Ge n Sn, OCiJI21la8T COBORynHOCTblO xapas-1'8pHCTI'I'l8CXnX qaCTOT. lIHT8HClIBHOCTb XOTOpHX C pOCTOM L1-:CJI8 EJJ1JlliJT't,

HIlX rpyrm B03pac'raeT annarasao [18. 40, 43. 54, 120, It,7, 15,;. ITPII nepexo,ne 01' Si R Sn odmall xapaRTep 28MeHSBliR cneRTpa COG~CllT

B TOM. 'ITO peSRO sospacraar I'IHT8HCllBHOCT:b JIDHV,ll, CBH38HHllX C ),0."8' daHHJ'lMR. B ROTOpllX l1pHHHMaST yqaCTl18 aTOM M [I29J. I1BT8HCLBHOCTb JIRHHfi, COOTBeTcTByromux RpaTHofi CBR:Sll. Ta~8 B03paCTaeT ITpllMe~HO B

rSOMSTplFleCKO? nporpeccza (I:2: 4; 8). B TO B;l6MR 1"2 r: ;1:::, OCTa.'lJ:,t;ilX JII'IHllfi rrOqTI'I HS 1I3MSHJJ1OTCR HlI qaCTOTa, HI'I IDITeHC}'fj,ll')CTb [IE]. ,,'w cmmsTsJU>cTByeT ad yCI'IJISHI'II'I BSal';MO.I\slkTBI'IH f3TOMa M GJ CBR~oh][) C"C B .p -rrOJIOJKeHI'!I'I K HSMy no Mepe 3aMeHll aroaa si na Ge x: ,h [25, 31J. :'GOClSHHO qeTKO arc rrpOflBJlJ18TCH B BaRYYMHflX Ycj}-CITe~:'1'p"X nOrJIOlI\Slffi5i ;rJ)lH COe,lJ;llHeHRll (CH3)3M(CH2)nCH=C12' r,Ua daT0XDCC.1lmfi C.I\Bl1I' nOJIOCH norJ!o~~e!U1Jl B BH,l\HMYJD OCiJDC'J'b pos!

·.Joe;;;\EOmm 3JIe:,leHTOB tWTBepTOi\ r'pynrru rana Cl:f~CH2CH2Cl. R i>OTOpWf lIIJHlla,IJJI9JKUT G1 Si CH CH .TI.IIH M - Ge, Sn, Pb noJ 2 2G1, aacTo;rrneli pa6o~!1 6wm HeU3BeCTH!1. D czrysae OJIOBa II CBIIHl,f! 3TOT 'rIm COe,lJ,ID18HID1, BSpOHTHO, He 6bLJI lIO.r.Y'i8H lIa-aa Kpafulef! IIX H8CTOH

EOCTII. Ol\HaKO HaM y,n3J10C:b rro.nyqUTIo C13GeCH2CH2Cl [28J. CpaBHHTeJII>Hoe 113y'leHHe ero X1IMH'leCRllX rrpSBpaU18HIDI noxaaaao , 'ITO 3TO COS,IUl

HeHue 60JIee CKJIOHHO l\ ~ -pacrra,ny, 'ISM ero KpsMllueBH:li anazor , T.e. ~Tc6!1 3alIOJIllUT:b lIpo6eJI B p~ coe~ellKnC1JSiCH2CH2C1. 3JIeMSHTOB lYE rpymnr TillIa C1~~CH=CHCl, M1I cllHTeallpoBamI cosnaH6HRH c M - Si U Ge,noKa3aJIll UX TpallcKoHWurypauuro (~OJIDH!1S MOMeHTu) II UCCJISnOBaJIll XHMU'lSCKHS CBollcTBa [15, 28J. ITo aHaJIOrllH c c1:lbCH=CHC1 JlJlII 1I0TOpli1l non ne~cTB»:eM pasHoo6palIWIC1J3nCH=CHC1, peareHToB pacnanaDTcH C B!1,ne~eHlleM aueT~ella, MOXHO 6uxo o~aTb. qTO MeTil~poBaHue ~ CIJCeCH=CHCl lIPB nOMO~ CHJWgXC13SiCH=CHC1 ocymecTBHTh He y~aeTCH. O,nHaIlO Z MeTHAHpoBaKKlI.B o6pa6oTila meAOQhD. a TaR~e llClIOJIL30BaHlle lIOJIyqellllHX (CHJ)JSiCH=CHC1 H (CHJ)JGeCH=CHC1 B paaJIll'lllliX CKHTeaax lIpOXO,nuT 6ea RaROrO-Jlll60 p-OTmelIJIellZR, COlIpOBo~aIDrnerOCH Bu,neJIeHllSM auSTllJIeHa. CJIenOBaTe~HO, B COs,nuHeHUHX TllIla CIJ~CH2CH2Cl u Cl3MCH=CH2Cl, rne M - Si, Ge, Sn H Pb, CTelIeHb COlIP~IlJJ:H BoapaCTasT OT Si K Ge,Sn II Pb,lIpUqeM ,IJJIH

C13SnCH2CH2C1 II 3TO BaaHMOneHCTBHe llaCTOJIbKOC1JPbCH2CH2C1 BeJlllKO, 'ITO coe,nuHellHH 3Toro THlIa, BepOHTHO, na~e He MoryT cymecTBOBaTD CKOJIhRO-Hll6YnD lIpO~O~TeJIDHOe BpeMH [28]. repMaHHll, OJIOBO II CBHlleu eme B 6o~mell CTelIeHll, qeM KpeMHHll, CRJIOHHH obpaaoBHBaTh llOHH TUlIa (MHa1 6) 2-. ~ repMaHHH raJIOreH B 8TllX HOHax MOEBT 6HTD y~e XJIOpOM. 3 ,IJJIH CBllHUa II OJIOBa ~a~ bpOMOM II HOnOM. nr~ Sn U Pb

llaB8CTHH COe~qeHHH TllIla K4(M~P8)' CJIenOBaTSJIbHO, C rrepeXOAOM OT Si R Pb aospac raar B03MOlKHOCTb y'iaCTRH BaRaHTH!1X a-opoar 3TllX 3JIeMeHTOB B 06pa30BaHllU nOlIOJIllllTe~HliX cBH3ell C } -aTOMOM raJIOrella, 'ITO II B8~eT K Bce'BoapacT8~mell CKJIOHHOCTll j -XJIopRap6oaaMemeHHliX coe~eHllfi 3THX 3JIeMeHTOB K fi -pacnany , ococeaao HarJIMHO 3Ta saxoaoze paoc'rs lIpoHBAAeTcH B cJIe,IIylDmell peazmra [28J:

C1JGeyH - yHSiC1 XIUiOJIKH 3

C1 C1

ECTeCTBeHHO, 'iTO cymecTBoBaHUe yKaaaHHoro lIpOCTpaHcTBeHHoro COCTORHHH } -RpeMHSraJIOreHJJ:,na aaBHCHT OT MHOrllX ~e o6cy~eHHlix ~aRTopOB, rJIaBHliM ua ROTOpliX RBJIHeTCH lIpHpOna aTaRYIDU1ero peareHTa, OlIpe~eJIRIDmero reOMeTpllID MOJIeRyJIll B peaKQllOHHOM KOMTIJIeKC8.

Ha OCHOBaHHH BlillielIpHBe~eHHoro MaTepHaJIa MH npllillJIH R BHBOny, 'iTO CTeneHD b, 0- II 6",1' -conpsxeaaa B PH.IIY } --¢YHKW'lOHaJIDHHX 3JIe

63

MeHTOOprallll'feCKllX COe)U'lHSlIllll IY rjJyrri1,l B03paC,,:,aST B CJIeiJ,yKJilLeM PH,Ily: S.i "- Ge < Sn < Pb [28. 54. 76. 85. 90. 9IJ.

Ec.IDl COOTHoru8Hl:le B peaRIl1l0HIlOit cnococnocrn cpaBH;maeMbIx

HSiCIJ II HCeCl3 B nx paaxuaax C lIerrpene.:IMIbIMll GOe.illlHeHl'lIJMll He

Bbl311BaeT KaKllX-Jlll60 cOMIleHltii [9J, TO no coornoureuae ,Il..:1H: .n,pyrllx r~pllJ(OB KPSMIITIH II repMaHHH lie CTO~b OqeB3~H0. Ma Tpex rl~p~CB ~~05;~) ~~~ ~all6o..'lbliletl peaKT\110IlHOCrrOC00rrOCTl>1O 06JJ8,1\3ST

OTMS'fSHHOS pa3Jlll'flle B psaKIIllOHHcLi cnoc06HOCT:; llcc~e.uyeMliX T}lex

I'H,llpll'uOB (C2''15) d,m 00068HHO 'feTRO npOIJBl'JIOCb rrpz 113y'feIllG1 nx asanMO,USnCTBliH C IC%-HOH crrllpTOBOn KGH. rM,I1pH,ll repMaHllH rrpil 3TOM

coaepmenno He Bbl,llSJLnIT8J;I :JO,,~Rfi.J~~

.3i-Cl He 3aBylC~IJVjO OT B8JHl tB1Hhl n [132J ~ Cl>~,LJ:nf--~=~Ji. T ~;'~lTa ;,1c:, ".L!JC""~' rraCCUBHee ~ tI8M Me d'.10P no ClTHOm8HIU) R :~'ocreny ~! pf~cn0.,1Ia::(-Llyrc;:; ;-' ;'1-

ny OTIIOCliTBJIEHO:a 3f\TIHF{OCT:: [127, I3~}J: Sn :'''l- Ge ~ .i , :,,1 1 EEH':():-F~~~'" CBJI3E (;e-CI ::...:}wrnIT8~ThtL) YCTD~:q~:Bee vr :-::nrpTSBO:M: :ue

8. EJ10JIOIWiECKAH AKTl1BHOCTh I'EI'MAIDllioprAHJ11lECKID:. CoE,1ll1HEHl1tl

Eaxe B HaCTORmee BpeMH MllpOBOe npoRSBO~PTBO repMaRHH ~OCTEraeT npli~epHo Bcero 150 T B ro~. ilo3ToMY B CaMOM Haqarre Moero ncC$e~OB8HRH dune O'IeB~O, 'ITO npHKnaAHoe RcrrO~SOBaHRe CpraHHqeCKliX coe~eHllll repMaHHH paSYMHee Bcero HCKaTh B o~aCTn Me~HH >Will ~1E $erHpOB3HHH, T.e. MO~WHK8uaR CBolCTB, KpeMHKfiopraaa'IecKHX MaTepnarrOB rryTeM BBe~eHRH Hedo~llioro KO~'IeCTBa repMOKcaHOBHX SBeHbeB B CKrrOKC8HOBY~ uenb. OnHaKO 3TH llcc~enOB8HRH ynaBS~OCb ocymeCTBnRTb T~KO 3nHSO~'IeCKH. B 1968 r. HITOHC~ llcc~encsarexs K.Acm: odeapyJKJ1.lI , 'ITO 2-RapdoKC},[ST~epMMcecKBHoKc8H [WI ,5GeCH2CH2C -: OR) xJ, CHHTes xoroporo dun pasea paapaooran B MoeR ~dOP3TOPHH [81, 238J, Od~anaeT lliHpCKZM cneKTpoM dROAOrU'IeCKOrO nelicTBHH, B TOM qnc~e U npoTllBoonyx~eB~ 8KTllBHOCTDD. IIp$ccop K.Acal1 opraHH3osaJI "HHCTHTyT H3YQeHRH repM8HRH" }'[ "KJIilHllKY repM8HuH", nne ycnsnao ~etraT TRlKeJIod~HlIX JllQIJ.eR R B HaCTORmee BpeMH.

C SToro MOMeHTa HRTepec K dUOJIOrU'IeCKOll 8KTllBHOCTH coe~eHllli repM3HllH peSKO BOSpOC BO BceM Mllpe. EOCTaTO~O CK8S3Tb, 'ITO K Ha'Ia~ 1992 r. 'IllC~O rry6nllR8URll no dlloaKTllBHocTH repMaHllR nOCTllrBeT rrpZMepHo 1000 H8HMeBOBaHllll. HecKonKo Coe,l\llHeHRll repMaHI1H yJKe BOlliJIO B cPapMaKorroH Hr!OBI1H, ClIlA :I'l ,lijJyrl1x cTpaH.

J1HTeHcllBHo CTa~o pa3BllB8TbCH :I'l Moe COTpYnHU'IeCTBO C aKaneM:I'lKOM JIaTBuH S.H.JlyKeBHll, non pyKOBonCTBOM KOToporo CTaJIll CHCTeMaTUQeCKI1 rrpOBO;U1TbCH lliupOKlle dnOHCITHTaHHH pa3Hoo6paSIlHX repMaH~OpraHlltrecKllX coe~eHilH, CllHTeSllpOB8RIlHX B MoeH ~60paTopllH. DRnR 06HapYJKeHlI HOBHe COe~eRRH R KRaCCR coe~eHRfi repMaHRH, odJIanaDmue MHoroo6e~~eR cPapMaueBTRQeCKOH neHHOCTDD, H8npZMep, rnnpOKcaMOBHe KllCJIOT1l [231, 234, 239, 250J, repMllJlMeTHJlBMn,IUl [195, 205, 2Il, 247J, repMllJIanaMaHTHH1I [ZI0, 226J II ocooenao repM8TpaHH R ax ananor-n [176, 2IIJ, cpenz KOTOpllX repaarpaaon [N(CH2CH;P)3GeoHJ [178, 197, 214J B~eRReTCH rrpocToTOM CBoero rrO~qeHHff, B~anme!CH wnPOTOll dl10neficTBllH, P8CTBOPHMOCTb~ B Bo~e z nOqTR rrOAHHM oTcyTcTBlleM TOKCZtrHOCTH. HeBOSMO~O rrpe~cTaBHTb cede KaROe-JIHdo npyroe opraHlltrecKoe coe~HeHlle repMaHllH, KOTopoe 6llJIO 611 nellieBJIe repMaTp8Ho~ II Mor~o dHTb rrpome rrO~'IeHo.

O~llM ll3 caMHX SaMeqaTe~HHX CBOllCTB MHOTllX repMaHHROpraHllqeCRllX coe;u1HeHllH HBJIHeTCH llHTep~pOHllHnYnHPYD~8H II ilMMYHOMonyJIllPYID~8H crroco6HoCTb. 3TO rr03BOJIITeT lIaneHTbCff Ha nO~qeHHe HOBHX npenapaToB rrpoTllB PH3JIHtrHlIX BnpycH1Iy' 3a60~eBaHHJ1, BKJIDQaH C~OM rrpHodpeTeHHoro uMMyHlloro nei!mmT8 (Cmm).

65

56

ria MHorllX npl1MSpaX 6hlJIO o6Hapy1tSHO, 'ITO Tnv.'1ll~oCl'D COc,w.'"H8

mill rSpMaHI1.f.l DO cpaBHSHIDO C aHaJIOrf;~llI!Jlf COS,lJ,lLc8HIlf:!·n: !'iPSMlci1.f.l HSl13MSHHO 11 CymSCTBSHHO MSH:bms. GTOT pesymrar noxa TpYTJJlO .norllqSCKll 06~flCHHT:b, B TO BpSMfl KaR y~nTS~:bHOe 6~arOTBopHoe

~sliCTBns pa3Hoo6paSHSllrul1X coe~HSH~ repMaHV~ rrpaKTaqSCKR Ba

BCS ~ue opraH1l3MH 06~HCHflSTCH TSI1, 'ITO OHll llCrrtlTHBaIDT B BsM

HS~OCTaTOK BCJIS~CTBllS aeocparaaoro llCQS3HOBSHIlH (J';';'IHB'JlUliJ) 1'8p

.MaHllH 113 3SMHOll KOpH B npoueccs rSOXllMllqeCKOll 3BOA~nR. TIOMIIMO np1l3HaHllH rspMaHllH 6ll0MllKP03JI8MSHTOM cxonCTBO ero Xll

Mllll C XllMll8fi KpeMHIiH Il03BOJIHST rrps~o~araT1, QTO B ~HX opraH1l3

Max re pMaHllli. KpOM8 roro , MOlKST BR,moqaTDCH II B M8T:J6OJYi.3M Coe,!l.1Fa

HnR KpSMHll.f.l - 3J1SMSHTa ylK8 rrp1l3HaHHoro OAOMllRp03JIeM8HTOM.

COOCTBSHHHS llCC~S~OBaHllH no 6noaKTllBHOCTll rspMaHrffiopraHll4SC

xax c08~eHlllt II JIllTepaTypHHe ~aHHHe llcqSprrlIDalOUlS paCCMOTpeHl> HaMll B 6pOWDpe [169J, a 3aTeM paCillllpSHH B HS~BHO Bllills~ell MOHOrpaWIDI [229J. TIOMllMO 6ll0JIOrllqeCKoit aKTlffillOCTll (;cc:;:;rnsmdt rSpMallliH B 3TOll MOHorpaWllll npOaHaJIll3llpOBaHH ~aHHHS 0 co~erlKaHIDI repM8HllH

}J paCTy.T8jIbHHX y. )!tY.EOTHbiX opraaasxax.

1

.JlliTEPATYFA

Ilerpoa A..ll., Ml1pm-ICB 13 .-~., ,UOJII'IDt H.E. CllliT83 H8II.pB.zr.8JI1HHX repMaHIDiopraHll~BCIGIX coe,nIDlemlli//J1SB. AH CCCP. OXH. 1956. J~ 9. C. 1146-1148.

2. Kopniax B.B., IIOJIHIWBG A.r~., IIeTpoB A.n., MUPOIIOB B.'I>. IIO.7.!llM8plISaUHB: Henpe.ll8JIhHhlX re'pr~mmnOpraHHtIeCllliX COe,llIDl8Hni1//.uORJI. AH CCCP. 1957. T. 112. ~ 3. C. 436-435.

3. IIeTpoB A.n., MUpOHOB B.O. MarHni1opraHlltIecKni1 CIDlTes BIDIllJIIIPOUS

BO~HX RpeMHllB:, rapMaHMB: MOJIOBa//VisB. AH CCCP. OXH. 1957. ~ 12. C. 1491-1493.

4. :IIMpOHoB B.O., IIoHoMapBHRo B.A., Bssaxoaa r.R., 'uOJInm M.E., Ilerpoa A.n. CllWi'eS MMSY"leillle OTHOCllTeJIhHol1 pBaRUIlOHHOfi cnococHOCTM lIeKoTopIIX OpraHMqeCRIlX cOe.llllHeHrrll 3JIeMeHTOB lY rpYIIIIH//XIlMl![lf MrrpaKTMq. npVJf,eHBHlle RpeMHni10praHlltIeCKUX COe.llllHBHrrfi: Te3. .llOKJI. ~ •• 1958. T. I, C. 189.

5. IIeTpoB A.n., i~llPOIIOB s.e.. Iloaoaapeaxo B.A., CanHx-3a.ll8 C.M., ~epHHDleB E.A. CilliTes HOBHX Bll.llOB KpeMHllllCOnepxamnx MOHOMepOB// HaD. All CCCP. OXll. 1958. !0 8. C. 954-963.

6. Kcpuiax B.B., !10JIHKOBa ;,.1.1., MllPOHOB B.O., IIeTpoB A.,ll. IIO.7.!llMepllSaUl!H BllHllJI- II a~poll3BO~HX 3JIeMeHTOB lY rpYIIIIH//Vi3B. AIl CCCP. oxn, 1959. "~, 1. C. 178-180.

7. MrrpOHOB B.m., EropoB ID.II., IIeTpoB A.n. OTHOCllTBJIhHaH peaKUlloHHaR cnoco6HoCTh HeKoTopHX RpeMHe-, repMaHrrll- II OJIOBOOpraHlltIeCRllX COB.llllHBHlru II llX cn8KTpH KOMc5ID1auMoHHoro paCCBRHllfl/A1sB. AH CCCP. OXH. 1959. ~ 8. C. 1400-1407.

a. MMpOHOB B.m., IIeTpoB A.,U., MaRCllMOBa H.r. MarHnllopraHllQBcKni1 CllHTBS ~- II j -TPllMBTllJICRJIllJIaKpllJIOBHX llliCJIOT II BIDlllJIIIPOMSBO.llHIIX KpBMHllfl, rBpMaHllB: II OJIOBa//VisB. AH CCCP. OXH. 1959. MII. C. 1954-196C.

9. II8TPOB A.n .• MrrpOHoB B.m., ~YPIDIcKaR H.r. IIPIlCOB.llllHBHllfl TpllXJIOprBpMaHa K auBT1VlBHY, OJI8~MHaM MMX npOllSBO,llHHM B OTCYTCTBllB KaTaJIllSaTopoB//,UOKJI. AH CCCP. 1959. T. 128. Je 2. C. 302-304.

IO.KopillaK B.B., IIoJIRKoBa A.M., B,ll.OBIDIa B.M., Mapoaoa B.m., IIBTpoB A.n. o BSallMOnBllCTBllll TBTpaaJIK~nrll.llpll.ll.llllCllJIOKCaHOB C .llllWYHKUlloHaJIhHHMll HBHacHmBHHHMll COB.llllHBHllflMil//,llOKJI. AH CCCP. 1959. T. 128, ~ 5. C. 960-963.

II.EyropKoBa A.A., MMpOHOB B.O., IIBTpoB A.,ll. MccJI8.lloBaHllB OTHOCllTBJIhHOM pBaKUllOHHofi cnoco6HOCTll KpaTH0fi CBHSll B MBTa~OOpraHllQBCKllX coeAHHBHHflX lY rpynnH MBTO.llOM p0.llaHOBHX 'lllCBJI//Vi3B. AH CCCP. OXH. 1960. ~ 3. C. 474-479.

67

12. Kapl(eB LH., CHpRIlH H.K., MnpoHoB B.eD. ,I[,llno;ll., -ue MC,>1":'TH HeROTOpUX OpraHlPl:6CKRX coe,lUmeHIlli :r'epMaHI1JI//Y13B. AH rx(;p. GZH. 1960. ~ 5. C. 948, 949.

13. MHpoHoB B.~, ~pRHCRaJI H.r., lleTpoB A.A. B3al1MOneficTBlle a~~ranoreHllnOB C TpHxnoprepMaHoM//H3B. Ali CCCP. OXH. 1960. ~ II. C. aJ66.

14. ~pe~ ~.X., XyRoBa Y1.~ .• MRPOllOB B.~. Y1cc~enoBaHlle CKOpOCTll r~pHpoBaHnJI BnH~HHX n ~HUX cOenHHeHlltt yr~8pona, KpetmV~, repMaHllH n ~OBa Ha CRe~eTHOM HnRs~eBOM RaTa~3aTope// M3E. Ali CCCP OXH. 1960. ),\ 12. C. 2258-22 so,

15. Ml1pOHOB B .~., .!DKypnHCRaJI 'Lr., Ilerpos A•.II, IIpl1coemmeHl!e HGeC1 3 R ra~oreH3aMemeHHIDl 3THJI8IiaM//.IIOK..'l. All CCCP. 1960. T. 131, ~ I, C. 98-100.

16. lIeTpoB A•.rr., MnpOHoB B.!Ji., Byrcpzoaa A.A. Dber die relative Reakt ions - fahigkeit del' Doppelbindungen in e Ln.i.gen organi.achen

5ili.cium- und )4etall-Verbindungen gegenuber Rhodan/v'Pe t t e ,

Seifen, Anstl'ichmittel. 1960. n 12. S. 1101-1109. 17. IISTpOB A.n., MnpOHOB B.~., !1oHoMspeHRo B.A., TjepHHlIl8B E.A. Cl!H-'

Teg RpeMHMOpraRl'!'leCRllX MOHoMepoB. ;,1.: AB CCCP, 1961. 18. Eropos lO.II., j~ettTec J1.A., MnpOHOlJ B.!Ii. Cp8BHll1'e.'ThHOe 113YQeHlle

cneRTpoB ROM6nH~noHHoro paCCeJIHllH 8~~cn~HOB, -repM8HoB II -cT8HHaHoB//lK. CTpyRTypH. 7..nMIDl. EJ5I. T. 2, I~ S. C. 562-5['3.

19. J].lKYpllHcRaJI H.I'., r,lIlpoHoB R.!Ji., ITe '~lJOB A . .II. ITpl1COe,IDlHeHlle rspaaH~P~OB K Henpene~RUM coe~eHllm~//nOR~~ ltH CCCP. IS61. T. 138, ),\ S. C. 1107-1110.

20. MnpOHOB B.~., )~pRHCKaH H.r•• ITeTpoB ! .~. B32~o~eficTB£e a~eH>Wl- n aY~~R.~epMaHY~OpllnOB C 6~OMY.CTIDlBO~OPO~OM//M3B. Ali CCCP. OXH. 1961. ~ II. C. 2095-3..198.

21. IIeTpoB A•.Il•• ImpoHoB B.!Ji. 3y;.•cllf,,,e und Reaktio;"',l von siliciwn-; germanium-, und Zi.nn·-organiachen V"J'bindlU'.gen//Ange... Ch

.,LlpOHOB b.~., rap T.K., JIeltTec JI..A. CV.HTe3 n Cl!eKTpbl oprana

qeCKMX coe~8Hilfi rspMaHMH, CO~~P~mRX pa~Ka~: URK~onBHTa

.:r:JCIIM.~. !JYlK.~orreHTeHV..JI M C:llK~Ol!SHTM//lbB. AH CCCP. OXH. 196~. ;., I,. C. 1387-1392.

Eropos KUI., I\Mpsj~ r.J:'., JIeitT8c JI.A., Ml'lpOHOB B.~., IIBTpoB A.n. ITOJLH:PHI18 SCWl8KTbl E IDIIPpal,pacHblx crrexrpax OpraIDlQSClGlX COB,l1l'IHB

HID! 3J18MSHTOB IY rpYIIlIU//viSB. AH CCCP. OXH. 1962. !f> IO. C. 1880-1882. MrrpoHoB B.1; •• ~yplUICK8il 1I.r. 3CWJSRT COrrpRlKSHJi.f! B r8pM8HIDtop

:'afIl1QeCKI'lX coe,llllHeHI'lHx//llaB. AH CCCP. OXH. 1963. }f> 1. C. 75-82. :,hfPOHOB B .1Ji •• I'ap T.K. B3aHMo.n;ei1:cTBl'Is Tpl'IXJIOprePMaIia C 6YT3AI'!eHOM}/v13B. AH CCCP. OXH. 1963 •.'f> 3. C. 578. MrrpoHoB B.~., fap T.K. UaaHMo.n;ettcTBl'Ie Tpl'I~OprepMaHa C COrrpRlKBHHllMl:l ,lllleHaMM//J],oKJI. AH CCCP. 1963. T. 152. ~ 5. C. IIII-lII4. Er-opoa 1O.r., JIeilTec !l.A., KpaBIJ;OBa M.n.• MHpOHOB B .ill. BJII'lRHns r:PllPO.n;u CllJIllJI1H0i1 ,1 repMM.~1110A rpyrrrr aa crraxrpa ROMOI'IH3D;l'JOHHO

1'0 pacceanaa aJIJlllJICMaHOB II aJIJll'lJJrSpMaIlOB//l13B. AH CCCP. OXH. 1963. ~ 6. C. 1114-1117. :AlfPOHOB 3 .1Ji B cnexrpax .J' -aJlKeH:mrepMaHoB B 3aEJ.!CilMOCTll OT rrpocrpaaCTBSHIIIJX qiaKTopOB//.llOKJI. Ali CCCP. 1964. T. 158. JI, 2. C. 400-403. [,IUpOlICB B.'ll., KprmqeHKC A.!I. Homill: MSTO.n; rro.rryQaHllil 8JIKIDl,ll11XJ10PrOpI!aEOD if a,'lKMJITPIfx.Jiorrepr1aHoB//nOKJI. Mi CCC? 1964. T. 158, J 3. C. G5G-C59. Kaprroa r.ii., CUPRlIH iLl(. , ]{paBqSIUW A.JI •• Ml:lPOHOB B. 4. C. biJ-b45. V!rrpoHoE B .;J.• Kpaassuxc fl.J: .• IIeTpoB A.n. CRHT83 Kap601JYllKWlo

H33bm,nc coemmeHPIl repM8HH.rr ua OCHOBe ~OPMSTMTplIMeTMr8PMa

,!;i:lB. AH eee? Csp. XlfIl • .iSlGt. .'t 'I. C. 1209-1215.

70

40. Eropo'lliJIH A.H., XH,IlR8JTh u.a., Pa3yBa8B f.A., M:Z:DOH~B ~-~., KpaBQ8HRo A.Jl. Crr8RTpH npcronnorc MarHllTHoro p83CHaHGa H8KO-

TOpHX

55. .uOpJIM8H a.r.. JIerreH,lUIHa O.Jr., ~I'lHKSJIl,mTeHH E.IlI., J.J.YprapilJUI c.r., MllpOHOB B.cr>. B3aIDJo,IleHcTIllle MSlI!.IlY aTOMaMll

69. MHpoHoB B.~., COdOJISB E.C., A!lTarrmr Jl.M. 0 H8KOTOJ,b[X npsBI,b'1l8HRflX rSKCaa~ITepMa3aHoB II -AHrCpMOKcaHoB//i. oOm. X~~AE. 1967. T. 37, ~ 12. C. 2573-2576.

70. A.B. 190897 CCCP. cnocoo nOJIyqeHllH opraiULil(2,2', 2"-aMlIEOTpll;J

TOKcH)rspMaHoB!BopoHKoB M.r., 3eJIqaH r.M., WilipOHOB B.~.

71. A. c. 213873 CCCP. cnocoo nOJIyqeHllH C-rspMaHlU13aMeU;SHHJ1X sapoopaaon/ CBJJl.lllH P.A., braq A.~., AHTllnRH JI.M., COd0JI8B E.C., MHpOHOB B.~.

72. MllpOHOB B.~., fap T.K. XID!JID! TpI'lXJIOprSpMalia//Mslli,ll,yHap. Gl1I.,no3llyM no 3JISM8HToopraHI'lQecKoil XllMllll: Ts3. ,n:OJ(.l]. MKlHXSH, I907.

C. 214. 73. MJIlpOHOB B.~., I'ap T.K. OpraHl'lqeCKlle coe.romeHlln: repMaHlln:. Iii.:

HayKa, 1967.

74. BOpOHKOB M.r., 3SJIQaH r .11., MllpOHOB D.l>., EJIsll,us"1I1c H.H •• KeMMB A.A. Arpanu , XIY. I-OpraHllJIrSpMaTpaHll//Xl'!MllJI re re pomuci. coenHHSH. 1968. ~ 2. e. 227-229.

75. AHTllllllH n.M., COdOJISB E.C., MllpOHOB 0.11. 0 jJeaKUl'lll qeTllpeXX-lJOpllC"

Toro repMaHKJI C rnnpRnOdopaT~Mll KaJIllH llJTII HaTpllH//l.. HeopraH.

XllMllli. 1968. T. 13.

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