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Ha paax pyoc EXTP EBEH EOPOB BAMOECTBE OPTOPOB C PAHM AMHOPAHECM COEHEHM 02.00.03 - Opaeca x Aopeepa a cocae yeo cee aaa xecx ay a-2002 2 Paoa oea Hayocceoaeco cye aooax xecx poyo peao cye opaeco x H PAH Haye pyooe: oop xecx ay, poeccop oc Cee Coooo, aa xecx ay, cap ay copy, Bocpoa Oa Cepeea.

Oae ooe: oop xecx ay, poeccop pao Acxa apaxao oop xecx ay, cap ay copy, Me op Aecapo Beya opaa: pocac ocyapce Texec epce aa ccepa cococ 26 eap 2002 oa 10-30 aco a acea ccepaooo coea 212.289.01 co ocyapceo Heo Texeco epcee o apecy: 450062, a, y. ocoao, 1.

C ccepae oo oaoc ayo oee coo ocyapceoo Heoo Texecoo epcea ayo oee cya opaeco x H PAH Aopeepa paoca 22 op 2002 oa e cepeap ccepaooo coea poeccop A.M. CPH 3 OA XAPATEPCTA PAOT Ayaoc e.

Opop poo coyc a oypoy peae cee pax pacee, pcao, ooec ax eapcex peapao. Boccaoee opopo o ece pa eaoopaecx coee aco coyec p oye cooecyx apox coee. peee x ee cx aopaecx coee (AOC), cax ocy oceee pe, yeo o eocaoo. B oe pe cooae AOC oe oaac eca e ae cea poox cx aeo, a poe oo, oo yy pacp ece pecae o exaax pea opopo. B c c opooe yee aoec opopo c AOC paoo cpoe oc ex aaaopo yco, oeceax co xo ceeoc eex poyo, pecaec ao ayao aae copeeoo opaecoo cea.

ccepaoa paoa oea cooec c aa ayo-cceoaeco pao H Maooax xecx poyo peao HT Mopaoa P T. 203.03.01.003 Haye cceoa ce o o pope apae ay ex, pa Mopaoa P o 15.08.2000 2443, pao Mopaoa P o 12.09.2000 2617 O oe oypca poeo o ayoexeco popae. Haye cceoa ce o o pope apae ay ex a 2001-2002 o, cooec c poeo eepao eeo popa "ocyapcea oepa epa ceo opaoa yaeao ay", apaee 1.5/2001 pa 425.

e pao - yee aoec opopo c AOC paoo cpoe.

- oop ex aaaopo apyx oao, oox poo occaoeoe apoae opopo AOC x ycox.

- Opeeee cpyyp AOC a aoc ceeoc aoec c opopa.

Haya oa.

Bepe ocyecea cceoaa pea opoopao c c AOC pao cpyyp, poa opaoa aeae cooecyx aeo.

Oapyeo cceaec yeo apyee e xopcoo eea a occaoeoe apoae opoopao apaa. B pea opoopao c poyae cooae xopcoo eea aece pacope ooe oy c co xoa poy occaoeoo apoa.

Bea c ey cpyypo yeoopox paao AOC x peaoo cocooc o ooe opoopaa.

caoeo, o yeoopoe paa, coepae oee aece p C1 C2 yepoo aoe AOC, e a peax c opoopaa.

caoeo, o 1--3-aaaoeaax ceeo paceec opoopaa cepec aeee apyea oeca Al-C c.

paeca eoc pao.

B peyae poeex cceoa papaoa epcee peapae eo cea aeae cx acex aeeox aeo paoo cpoe.

Papaoa yo peapa eo cea aeae 4eaeex aeo ex coo oye pa epooo. B acoc, ocyece ce @` ` eecoo aaoa oooo epooa yoo xpyaa.

Apoa pao.

Peya cceoa ooe a oe oox yex Opaeca x XX ee (Moca, 2000), XIII Meyapoo ayoexeco oepe Xece pea, peae poecc aooao x (Tya, 2000), ooeo ayo oe o opaeco x (Eaepyp, 2000), ayo oepe, oceo 70-e co poe aaea B.A. oa Copeee poe opaeco x (Hoocpc, 2001), oepe oox yex Mooe yee Boo-pacoo peoa a pyee eo (a, 2001), XIV Bcepoccco oepe o xec peaa, peaea poecca aooao x (a, 2001), eyapoo oepe Opaec ce oo coe (C. eepyp, 2002).

ya.

o ee ccepa oyoao 11 eax pao, o ce ca 7 eco oao a oepex.

Cpyypa oe ccepa.

ccepa coco ee, epaypoo oopa, ocye peyao, cepeao ac oo. Maepa pao oe a 103 cpaax aocoo eca, coep 5 pcyo 9 a.

Cco epayp ae 102 aeoa.

OCHOBHOE COEPAHE PAOT 1 Boccaoeoe apoae opoopao poce aopaec coee caoeo, o x ycox (20oC, 2) aoc opoopao (1-3) pea c poyae (4) a cooecye aea oaepaooo aea (5, 6) opayc c xoo e oee 5%.

ORORRO Al( -Bu)i + OROR1 -5, 1, 5 R = R = Et;

R = R = Bu;

2, 3 R = Ph, R = Et.

eee pooeoc pea o 6 aco e oaao aeoo a xo eex poyo (a. 1), oao, oee eepayp o 60oC po yee xoa aeae 5 6 o 40-70%.

B ex e ycox (20oC, 2) pa (7) oaac oee a- ORORRO Al(Et)+ OROR1 -3 8, 1, 8 R = R = Et;

R = R = Bu;

2, 3 R = Ph, R = Et.

xo 1,1-aocpoao (8, 9) coca 42 20% cooeceo, oa a p 60oC aaoc paec oeceoe (95%) opaoae aea 8.

Taa 1.

Baoece opoopao 1-3 c AOC 4 (cou onmo: opoopa : AOC : 1 : 1 (o.); pacope ea).

cxo AOC Bpe, Teepaypa, Aea (xo%) o opop C 1 4 2 20 5 (<5) 1 4 6 20 5 (<5) 1 4 2 60 5 (45) 2 4 2 20 6 (<5) 2 4 6 20 6 (<5) 2 4 2 60 6 (14) 3 4 2 20 5 (<5) 3 4 6 20 5 (<5) 3 4 2 60 5 (68) 1 7 2 20 8 (42) 1 7 6 20 8 (45) 1 7 2 60 8 (95) 2 7 2 20 9 (20) 3 7 2 20 8 (65) Oaaoc, o pcyc pa eaooecx aaaopo (a. 2) xo poyo ye p 20oC aeo opaca coca 50-90%.

ye peya ocy p cooa Ni(acac)2, NbCl5 ZrCl4. x pcyce oecax 3% o. p oo coooe peaeo oeceae xo aeae 8, 9 oeceoy.

Haoee ao aaec e poeocppoa a pepe aoaoo yopoopaa 2.

Taa 2.

aaecoe aoece opoopao 1-3 c AOC 4 (cou onmo: 20oC, 2; coooee opoopa : AOC : aaaop 1 : 1 : 0.03 (o.); pacope ea).

cxo opop AOC aaaop* Aea (xo%) 1 4 ZrCl4 5 (51) 1 4 NbCl5 5 (62) 1 4 Ni(acac)2 5 (87) 2 4 ZrCl4 6 (55) 2 4 Ni(acac)2 6 (63) 3 4 ZrCl4 5 (83) 1 7 ZrCl4 8 (92) 1 7 Ni(acac)2 8 (95) 1 7 NbCl5 8 (89) 2 7 ZrCl4 9 (65) 2 7 Ni(acac)2 9 (72) 3 7 ZrCl4 8 (95) * Ceye coee e oaa ocoepo aoc:

W(CO)6, PdCl2(P(Ph)3)2, InCl3, Cu(acac)2, MoO2(acac)2, Cp2TiCl2, Ti(OBu)4, Fe(acac)3.

Ta, cooae ZrCl4 Ni(acac)2 ooo oy yaea 6, 9 c xoa 65% 55% ZrCl4 63% 72% Ni(acac)2 cooeceo.

2. Be xopyeoopox pacopee a aoece opoopao c aopaec coee eco, o ae xopyeoopo, a xopoop, xopc ee xopa axo peee aopaeco cee, ocoeo p poee oeepaypx pea c apocoepa cycpaa. B oex cyax aea yeoopox pacopee a xopcoepae po e oo yee xoa poyo pea, o oe ee peoceeoc poecca. oo e, a pao, ocec e, o xopyeoopo opay ay c AOC, o cococye epexoy ocex epo op oee ay ooepy. Oao aay ax cceoa a aoyeoopoo a aoece opopo c AOC e ec.

Be oeaoc (a. 1), o yeoopox pacopex opoopa 1-3 ocyce aaaopo peapy c AOC 4 p eepaype e e 60oC. Oao cpee xopcoo eea opop 1 aoecye c o oeco peaea 4 p oao eepaype, opay aea 5 c xoo 62% ae, xo yaea 6 xopco eee coca 41%. B x ycox apy e 1,2-xopaa aeo e.

cooae aece pacope xopcoo eea ooo poec occaoeoe apoae opoopaa 1 pae 7 p oao eepaype c paec oece opaoae aea 8. p aee opaa 1 a coeee 2 xo yaea 9 ex e ycox cocae 65% (a. 3).

Taa 3.

Be ppo pacope a xo poyo pea opoopao 1-3 c AOC 4 7.

(cou onmo: 20oC, 2 coooee AOC:opoopa = 1 : 1) cxo op- AOC poy pea oopa Pacope (xo %) 4 eca 5 (<5) 4 CH2Cl2 5 (62) 4 ClCH2CH2Cl 5 (20) 7 eca 8 (60) 7 CH2Cl2 8 (98) 4 CH2Cl2 6 (41) 4 ClCH2CH2Cl 6 (<5) 7 CH2Cl2 9 (65) 7 ClCH2CH2Cl 9 (<5) Pea poeae ao e ax-o oox poyo ae p pxpao e AOC. B acoc, ocycy poy oee yooo occaoe poce p paeee aa.

Haae apy e xopyeoopoo e oc oo a ce epexoa aopaecx coee oee aoe ooepoe cocoe, ocoy coeee 4, eaco o ppo pacope, cyecye peyeceo ooepo ope.

peooeo, peay po ec pae opaoae oeco xopyeoopoo c aopaec coee, oeax aeee aoece x c opoopaa.

pee ceee cepe MP cao pooo xopcoo eea 1,2-xopaa pcyc poya 4, ceaee p paae cec eoo o po, ceecye o opaoa ecox ayo, epoo, oeax oopa AOC c opoopaa ocey pap C-O c.

a coc, xopc ee oaae apyee e a peaoy cocooc e oo aopaecx coee cooo coco, o a ocaoo poe x oec c a ocoa ca, a o p pa, e peapye c opoopaa 1-3 ae pcyc eaooecx aaaopo.

B pcyc xopcoo eea oec AlEt3 Et2O AlEt3 Et3N yex ycox opay aea 8 c xoa 90 65% cooeceo (a. 4).

Aaoe peya oye p aoec opopa 1 c Al(i-Bu)3 Et2O Al(i-Bu)3 Et3N oeca.

Oao apoa oo opao poe epapoypaoe oec AOC 4, 7 a e yaoc Taa Be xopcoo eea a aoece popoopaa 1 c p a oeca AOC 4 7.

(cou onmo: 20oC, 2, pacope eca, oepa AOC 10%, coooee a:AOC = 1:1, coooee AOC:CH2Cl2 = 1:4) oec Aea, (xo %) AOC a 4 Et2O 4 Et2O* 5 (40) 4 Et3N 4 Et3N* 5 (35) 4 p 4 p* 4 T 4 T* 7 Et2O 7 Et2O* 8 (90) 7 Et3N 7 Et3N* 8 (65) 7 p 7 p* 7 T 7 T* * - pcyc CH2Cloyee peya ceecy o o, o xopyeoopo coco oaa e a aoe opyee oeco AOC ae c oee c ocoa ca, e o ca.

3. Baoece opoopao c c aopaec coee paoo cpoe a oaao e, peae 4 7 p aoec c opoopaa 1-3 oaox ycox po pay aoc. a coc, paa paoo cpoe, xoe coca ooo oo e AOC, ae oaa pao peaoo cocooc ao pea.

Ta, -ooya (10) peapye c opoopao (20oC, 6), opay cec aeae oaepaooo 5 oooo (11) aeo coooe 1:1.4 (a. 5) c cyap xoo 24% pacee a cxo opop. oee eepayp pea o 60oC ee coooee poyo o1:2 yeae cyap xo aeae 11 o 78%.

OROROR5, RO + Al ( )ORRO 1 - ( )6 OR11, 1, 11 R = R = Et;

2, 12 R = R = Bu;

R = Ph, R = Et.

ocoy oye paa pcycy cxoo AOC oo e o ooe -ooy, oea aoc oceeo oea.

p cooa 3% o ZrCl4 cec poyo 5 11 opayec coooe 1:2 c cyap xoo 45%.

p aee popoopaa 1 a eee a pyopoopa 2 opayec cec yaeae oaepaooo 9 oooo (12) aeo c cyap xoo e oee 15%. oee eepayp o 60oC cooae aaaopa (ZrCl4) ooe oc cyap xo o 45% c pepo oao coooee opayxc poyo pea o cex cyax.

Taa 5.

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