WWW.DISSERS.RU


...
    !

Pages:     | 1 || 3 |

Taa Bxo cox po p aoec aopoo c aea, eepaypa 20-25OC, pacope eo, ooe coooee peaeo 1:Coe p, oepc Aopo, Ae, RCOOCH2R Aea, RCH2OBr () RCHO () % Bxo*, %() C4H9CHO (26) 45 97 (30) C6H5CHO (27) 44 94 (31) C3H7CH2OBr (2) -ClC6H4CHO (28) 45 94 (32) -CH3OC6H4CHO (29) 47 92 (33) C3H7CHO (35) 42 98 (36) C4H9CHO (26) 42 97 (37) C5H11CH2OBr (3) C6H5CHO (27) 40 94 (38) -ClC6H4CHO (28) 39 92 (39) -CH3OC6H4CHO (29) 39 91 (40) * - xo a popeapoa ae C e ye ooceo peaoo cocooc aeo peax c -aopoa cpoe aeo a copoc opaoa cox po cooa eo oyppyx pea.

B pea c yopoo oopeeo oeac aaece apoaece ae. oyex acoce a aao yace pea, oa oepce cycpaa oo peepe, ae oocee aae copoc opaoa cooecyx cox po. Ooe e aax copoce (V0i/V01) opaoa cox po pecae a.4.

Taa Oocea peaoa cocooc aeo RiCHO pea c yopoo, eepaypa 20-25OC, pacope eo i Ri V0i/V1 C4H9 2 C6H5 0,3 -ClC6H4 0,4 -CH3OC6H4 0,5 -BrC6H4 0,6 -C2H5OC6H4 0, oyee peya oaa, o o aoc pea c yopoo ae RCHO pacoaac cey p:

C4H9 > -CH3OC6H4 > -C2H5OC6H4 > C6H5 > -ClC6H4 > -BrC6H4.

oyea acoc ooceo peaoo cocooc py eaeeoo aeex eaeo pea c yopoo (V0x/V0) o ppo aece xopoo oppepye co ae -oca aecee ocaec ypaee aea (lgV0x=lgV0 + ) (pc. 1), c ocao peaoo cep = -1,4. oyea ea ceecBr Br ye o o, o ppoa aece apoaeco oe oaae aeoe e a copoc pea.

aee, oyeoe p cceoa pea eaeo c yBr opoo o acoo ee ecoo ee, e peax c yoxopo, =-1,6 (yao P.P, 1998 .). Opaeoe aee Cl oaae o, a cyae c yoxopo, epexoo coco Br pye ca pea (op aoa oopoa o apoo py aea paaa RCH2O Br) a apoo aoe yepoa eeppyec ac ooe ap. ooy, epoooope aece oea poeae pea, o pe a epooaeope ee ae.

cxo poeex cceoa ceye, o, ecop a eoope oecee pa poea pea eaeo c opoa oxopa, eo o ocac oe cxeo.

Heoe pa aex peaox cepx c yBr Cl opoo yoxopo ca c e, o oox cyax pye ca pea apo ao oopoa opa yoce paa paaec o peaoo cocooc ao xopa poa.

Xo pa eax ee, e opx aopo eBr Cl coo oee paeo cyae yoxopa.

lg V0x/V0 0, -CH3O 0,-C2H5O 0,-0,4 -0,2 H 0,2 0,4 0,-0,2 -Cl -0,4 -Br pc. 1. acoc lg V0x/V0 o ae yox oca aecee X (e X=H, -CH3O, -C2H5O, -Cl, -Br) eaeo pea c yopoo.

Ta opao, aopo eo eo aoecy c aea c opaoae cox po. Peaoa cocooc aeo peax c aopoa cyeceo ac o x cpoe.

3. Baoece -aoaoeo c -apa eco, o ap opax ycox c ca coee. Cxoco cpoe apo c aoaoea (R-ONO, R-OX) oooc apo oepac ooecoy pacee c opaoae aocx paao oo peoo, o aoaoe oy poa paceee apo. cxo oo, ao paee yeo ooecoe paceee -aoaoeo pcyc -apo.

caoeo, o p aoec yoxopa (42) c ypo (43) p oo coooe 1:1, oao eepaype, epo aocepe (apo) opayc yo cp (34), ac ae (35), yypa (9) 1,1-yocya (44) (a. 5).

B ex e ycox p aoec yoxopa (42) c ecpo (45) ecoxopa (46) c ypo (43) oco poya pea c yo (34) eco (41) cp, ac (35) eco (47) ae, a ae coe p: yypa (9), ecypa (36), yecaoa (48) ececaoa (10) (a. 6).

p epexoe o oxopo opoa o ycaoeo, o p pox pax ycox aoece ypa (43) c ecopoo (3) ae po opaoa cooecyx cpo (34,41), aeo (35,47) cox po: yecaoaa (48), ecypaa (36), yypaa (9) ececaoaa (10) (a. 6).

oyee peya yaa a o, o ooecoe paceee -aoaoeo py pepae -apo.

Baoece aocx paao paao aoea, oax peyae pacee aoaoeo (3,42,46), c apa (43,45) po opaoa -pooocax paao, oope oooeypo pacec a ae (35,47) paa oc aoa.

..

+ RCH2O X RCH2OX 3,42,3a,42a,46a..

.

RCH2O (X ).

+ R'CHO NO R'CH2ONO R'CHONO RCH2OH (HX) 43a,45a 43,45 35,+ + R'CH2ONO H+ + R'CH2OH NO 43,45 34,O + R'CH2OH R'C HX OCH2R'..

O O O RCH2O (X ) RCH2OX 9,R'C R'C R'C.

- RCH2O (HX) RCH2OH X O H + RCH2OH R'C 35a,47a 35,- HX OCH2R 36,O + RCH2OH RC OCH2R HX..

O O O RCH2O (X ) RCH2OX 9,RC RC RC.

- RCH2O (HX) RCH2OH X H O + R'CH2OH RC 35,35a,47a - HX OCH2R' 36,3a,35a,42a,46a,47a, X poy opa e pea R = C3H7 (35), C5H11 (47); R = C3H7 (35,46), C5H11 (47,49).

X = Cl (42,46); Br (3).

Ae (35,47) pea c aoc paaa aoa aoea a ae paa, aoece oopx c aoaoea po opaoa cooecyx aaoeo. Pea ocex co cpa, oa xoe pepae cxox oaoeo apo, po opaoa cox po (9,10,36,48).

Aaoo, aeo (35,47) oyex peyae pacee aoaoeo, opayc coe p (9,10,36,48).

o-oy, opaoae 1,1-yocyaa (44) pea yoxopa (42) c ypo (43) pocxo peyae aapyeo xopc oopoo aeaa yooo cpa (34) ac aeo (35).

Taa Coca peaoo cec pea yoxopa (42) c ypo (43), eepaypa 20-25OC, pacope eo, ooe coooee peaeo 1:poy Coepae, % C4H9OH 34 C3H7CHO 35 C3H8COOCH2C3H7 6 C3H7CH(OC4H9)2 44 Taa Coca peaoo cec opayec p aoec aoaoeo c apa, eepaypa 20-25OC, pacope eo, ooe coooee peaeo 1:RCH2OX () + RCH2ONO () C3H7CH2OCl (42) C5H11CH2OCl (46) C5H11CH2OBr (3) + + + poy C5H11CH2ONO (45) C3H7CH2ONO (43) C3H7CH2ONO (43) Coepae, % () 2-3 (34) 14 (47) 4-5 (47) RCH2OH 3-4 (35) 5-6 (41) 9 (41) RCHO 19 (9) 19 (10) 13 (10) RCOOCH2R 15 (36) 16 (48) 16 (48) RCOOCH2R 17 (48) 17 (36) 22 (36) RCOOCH2R 23 (10) 22 (9) 26 (9) RCOOCH2R 15 (41) 2-3 (35) 3-4 (35) RCH2OH 3-4 (47) 2-3 (34) 3-4 (34) RCHO Ta opao, aoaoe py pepae cax opax ycox apo c opaoae pax cox po, cpo aeo.

4. ooecoe paceee oaoeo eox cpo B peyx paeax a yea oa apa ooecx pepae -aoaoeo -apo. B pooee cceoa cpoe opaecx oaoeo a x peaoy cocooc ao paee ye pea ooecoo pacee oaoeo eox cpo.

caoeo, o oxop eooo (49), o-opeooo (50) -eoceooo (51) cpo epo aocepe (apo), p 20-25 oC ececeo ocee eo oepac pacee c opaoae cooecyx cpo (52,53,54), aeo (27,55,29), exopo (56,57,58) cox po: eooo pa eoo co (59), oopeooo pa o-opeoo co (60), -eoceooo pa eoceoo co (61) (a. 7).

p epexoe eopoa ycaoeo, o aaox ycox ooecoe paceee opoa eooo cpa (62) ae po opaoa eooo aea (27), eooo cpa (52), epoa (63) eooo pa eoo co (59) (a. 7).

Aa oyex peyao ooe peoo, o pea poeae aaoo ooecoy pacee aoaoeo ( 1).

O + ArCHO ArCH2X ArCH2OH ArC + ArCH2OX + OCH2Ar 27,29,55 56-58, 49-51, 62 52-59-Ar = C6H5 (27,49,52,56,59,62,63); o-FC6H4 (50,53,55,57,60);

-CH3OC6H4 (29,51,54,58,61); X = Cl (49-51,56-58); Br (62,63).

Oeo ocoeoc ooecx pepae eoaoeo ec xo cox po (59-61) (aa 7). Bepoo, o cao c e, o aaaec a aax cax pea e ae (27,29,55) oaa ee peaoo cocooc, e aaece ae (.2). Ha o ae yaae x ae peaoo cec, oe o pacee aoaoeo, p oopo ae oapye ceox oecax.

poe oo, oe o -aoaoeo, peaoo cec oapye aex oecax exop (56), oopexop (57), -eocexop (58) epo (63). Opaoae eaoeo (56-58,63), epoo, cao c op pepae eox cpo o ece exc xoe pea xopcoo pocoo oopoa.

Taa Coca peaox cece ooecoo pacee oaoeo eox cpo, eepaypa 20-25OC, pacope eo Coepae, % () O ArC ArCH2OX () ArCHO ArCH2X ArCH2OH OCH2Ar () () () () C6H5CH2OCl (49) 43 (27) 2-3 (56) 44 (52) 11 (59) o-F-C6H4CH2OCl (50) 39 (55) 18 (57) 32 (53) 11 (60) -CH3O-C6H4CH2OCl (51) 39 (29) 6-7 (58) 44 (54) 10 (61) C6H5CH2OBr (62) 30 (27) 22 (63) 36 (52) 12 (59) B eo ceye oe, o eoaoe pacec aeo eeee, e aoaoe. o-oy, o cao c oe ycooc eoaoeo o cpae c aoaoea, a ae c ee peaoo cocooc opayxc xoe pea eaeo eocx paao.

5. ooecoe paceee oxopo opx cpo oo p cceoa cpoe opaecx oaoeo a x peaoy cocooc pao a ec yee apae ooecx pepae oaoeo opx cpo, e o ooc opaoa poeyox aeo ocycye, a ae oaoeo oo.

B ao paee ye pea ooecoo pacee oaoeo opx cpo oo.

caoeo, o ypoaoe paceee oxopo opoo oaoa-2 (64,65), 1-xop-3-po-poaoa-2 (66,67) oecaoa (68, 69) epo aocepe (apo), p eepaype 20-25OC ececeo ocee po opaoa eoo: oaoa-2 (70), 1-xop-3-popoaoa-2 (71) oecaoa (72), p o ae opayc cooecye cp (73,74,75). B cyae pacee oaoeo (68,69) apy c oecaoo oapyeo ae opaoae 2-aoeoecaoo (76,77) (a. 8).

Opaoae eoo (70,71) epoo pocxo o ceye cxee:

OX O RCHR' RCHR' X - HX 64a-67a 64-OX O OX 64a-67a ( X ) RCR' RCR' RCHR' RCHOHR' (HX) X 73,70,64b-67b 64,O O RCR' RCHR' X HX 64a-67a 70,64a-67a, 64b-67b, X poy opa e pea R=C6H13 (64,65,70); CH2Cl (66,67,71); R=CH3 (64,65,70); CH2Br-(66,67,71);

X = Cl (64,66); Br (65,67).

ooeca ccoa O-Hal c oaoeo (64-67) po opaoa aocx paao (64a-67a) aoa aoea, oope opa aoee a ao oopoa o cooecyeo oaoea (64-67) c opaoae -aoeocx paao (64b-67b). ocee oooeypo pacec o cooecyx eoo (70,71) aoo aoea. He ceo, o opaoae poyo (70,71) pocxo peyae cpoopopoa ee pacope epo paao ap, oae peyae pacee c O-Hal cxooo oaoea. Op e pea oe ocyecc peyae cpoopopoa x e paao oee pacope. Opaoae oecaoa (72), epoo, poeae o aaoo cxee.

B xoe pea poea ope pepae oecaoa (72), oopx opaec aoee a ao oopoa o eeoo py, axoec -ooe o eopy. Opayc p o 2-ocooec paa opae ao aoea o oaoea, opay cooecy 2-aoeoecao (76,77).

Taa Bxo poyo ooecoo pacee oaoeo opx cpo, eepaypa 20-25OC, pacope eo oaoe X() poy () Bxo, % Cl (64) OX O CH3(CH2)5CCHCH3(CH2)5CHCHBr (65) Cl (66) O OX ClCH2CHCH2Br ClCH2CCH2Br Br (67) O 72 OX Cl (68) O X 72 O OX Br (69) O X p ye ypoaoo pacee oxopo oo o ycaoeo, o oooxop 1,4-yaoa (78) epo aocepe (apo), p 20-25 OC ececeo ocee pepaaec 4-yao (79), 1,4-yao (80) p o eec xopc oopo. Pea poeae ypo oce eooo yooo epoa.

HO HO O + OH OCl - HCl O 78 79 (xo 53 %) oyee peya cooyoc c a o pacee aoaoeo oo peo ceyy cxey opaoa poyo pea (79,80):

Pages:     | 1 || 3 |



2011 www.dissers.ru -

, .
, , , , 1-2 .