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Ha paax pyoc CBOPHA EATEPHA CEPEEBHA OCEHE CPTOB EHOOB OCOM XOPA Ceaoc 02.00.03 "Opaeca x" ABTOPEEPAT ccepa a cocae yeo cee aaa xecx ay A - 2002 Paoa oea co ocyapceo eo execo yepcee cye opaeco x coo ayoo epa Poccco aae ay.

Haye pyooe: oop xecx ay, poeccop ae pa yao;

oop xecx ay aaoa Haa Hypyoa.

Oae ooe: oop xecx ay, poeccop oc Cee Coooo;

aa xecx ay Aaa y ayoa.

Beya opaa apc ocyapce yepce.

aa cococ 27 eap 2002 oa 1200 a acea ccepaooo coea 212.289.01 p co ocyapceo eo execo yepcee o apecy: 450062, Pecya aopoca, . a, y. ocoao, 1.

C ccepae oo oaoc oee coo ocyapceoo eoo execoo yepcea.

Aopeepa paoca 27 op 2002 oa.

e cepeap ccepaooo coea Cp A Mxao OA XAPATEPCTA PAOT Ayaoc e.

O pacpocpaex cocoo oye opaecx coee paoo cpoe ec x ocea pacopa o ece eopaecx opaecx ocee.

o oce oco, eocaea epec cceoaee, paoax oac opaeco x, ye exao ocex pepae, ocy ox, cooex ocee. C o o pe ae epec pecae oc xopa, poo pee poeoc aece oeae, a ae oooce. Oac pee opeea apaee cceoa pea ClO2. o, pee ceo, pea c oco ape eo o eoa, yeoopoa .. ox pacopax p pH=3 9 pae x oepax ocex eec (10-6 10-4 o-1). Cee o peax ClO2 opaecx pacopex paec ocycy, o opaae eo pee a oeaoo peaea. ooy cceoae pea oce opaecx coee oco xopa opaecx pacopex ec epeco ayao aae.

Paoa oea cooec c ao HP cya opaeco x H PAH o ee Ocee opaecx oey coee, coepa a copo. poy, ea exa.

( 01.9.70008865). Haye cceoa pooc p acoo oepe Pocccoo oa yaeax cceoa (poe 99-03-33195).

e pao:

yee poyo, eecx aooepoce pea oce cpo eoo oco xopa;

cceoae cpoe opaecoo coee ppo pacope a ey pea;

ycaoee exaa pea oce;

cpaee peaoo cocooc oca xopa, eocpaa xopa 2,2,6,6-epaeep-1-oca o ooe cpa.

Haya oa pao. Bepe ye poy, eece aooepoc pea oce cpo eoo oco xopa opaecx pacopex. Bepe ycaoeo e pacope cpoe eoo a ey pea oce. peoe exa pea.

paeca eoc. peoe o eo oye apox coee aeex 1,4-eoxoo ocee cpo eoo oco xopa opaecx pacopex. oyee ae o cpoe cycpaa cpe a copoc pea oo peypoa poecc oce. Peya cceoa peaoo cocooc oca xopa, xopa 2,2,6,6-epaeep-1-oca eocpaa o ooe cpa pacp oooc pee ax ocee opaeco cee.

oyee cepeae ae o oce cpo eoo peca epec aece cpaooo aepaa.

Apoa pao. Ocoe peya ccepaoo pao oaac a XIV coye "Copeea xeca a" (Tyace, 2002); o ooeo ayo oe - oepe o opaeco x (Eaepyp, 2002); oepe oox yex, acpao cyeo (a, 2002); Meyapoo oepe VI Voevodsky Conference, "Physics and Chemistry of Elementary Chemical Processes" (Novosibirsk, 2002).

ya. o ee ccepa oyoa 2 ca ec oao.

Cpyypa oe pao. ccepaoa paoa oea a cpaax aocoo eca coco ee, pex a, oo, cca epayp, coep 22 a 45 pcyo. Cco epayp ae 144 cc a ya oeecex apyex aopo.

OCHOBHOE COEPAHE PAOT Bo ee oocoaa ayaoc e ccepaoo pao, copypoa e aa pao, a ae ee oa paeca eoc.

B epo ae (oop epayp) paccope oe coca cpoee oey oca xopa. pecae eec cee o peax oca xopa c opaec coee.

Bo opo ae ocye poy, eece aooepoc oce cpo eoo. yeo e aece ppo pacope a ey pea oce. peoe exa pea.

poee cpae aa oceo cocooc eocpaa, xopa 2,2,6,6-epaeep-1-oca, oca xopa o ooe cpa.

B pee ae oca eo oc, cea aaa cxox peaeo, ea poyo pea, pecae eo poee cepeo.

PETAT OCEHE 1. Ocee cpo oco xopa Ocee cpo oco xopa (1) yeo a pepe poa-2oa (2), 2-epoa-1-oa (3), ya-1-oa (4), ya-2-oa (5), 3eea-1-oa (6), ea-4-oa (7), ea-2-oa (8), oecaoa (9), opeoa (10).

ooe pacxooae cpa aa p coooe cpa oca xopa 1:2 o/o. poy oce cpo paoo cpoe ClO2 pecae a. 1.

ROH C R2 H OH (2)-(9) (10) Taa poy oce cpo oco xopa (epaxopea, T = 25C) Cp poy Bxo, %2 poao 3 2-Mepoaa 2-Me-2-xoppoa-1-o 2-Me-2-xoppoaa 4 yaa 5 ya-2-o 6 3-Meeaa 3-Me-3-xopea-1-o 3-Me-3-xopeaa 7 ea-4-o 8 ea-4-o 9 oecao 10 aopa Bxo a pacxooa oce ey pea oce cpo 2-10 oco xopa ya cepoooepec o pacxooa oca xopa eae p max = 356 p yco [1]0 << [ROH]0, e [1]0 [ROH]0 - aae oepa oca xopa cpa cooeceo. cex yaax coee eece pe c co oeo oppe (0. 0.999) ocac ypaee epoo opa (pc. 1).

Pc. 1. oyoap-ece aaopo eecx px pacxooa oca -1 xopa pea co cpo 9 (ea, T= -60C, ([1]0 = 810-4 M, 1 [9]0 = 0.19 M, 2[9]0 = 0 5 10 15 20 0.39 M, 3[9]0 = 0.52 M) t 10 -2, c acoc paccax ex oca copoc epoo opa (k) o [ROH]0 ee e xapaep (pc. 2), o ceecye o ocyc accoa cpa a eo peaoy cocooc yeo epae oepa o epo ope o cpy.

Pc. 2. acoc eo oca copoc pea oce cpa oco xopa o oepa cpa p pax eepaypax (ea, 1-29, 2-42, 3-50, 0.0 0.1 0.2 0.3 0.4 0.[ 9 ]0, M 4-60C) Oceee a oc opa ec ocao epecoo pacaa oca xopa, eecoe ypaee pea ee :

d[1] - =(kd +k [ROH]) [1], e kd + k[ROH] = k ; kd - ocaa epedt coo pacaa oca xopa.

ln [ 1 ] - k 10, c cex cpo yea acoc oca copoc pea o eepayp opeee aaoe apaep (a. 2).

Taa Aaoe apaep pea oce cpo 2 10 oco xopa (T=30 C, ea, oa cepea e peae 10 %) Cp k105, M-1c-1 lgA Ea H G S, o-1 o-1K-2 5.9 5.0 53.4 50.9 98.6 -157.3 5.2 6.2 60.7 58.2 99.0 -134.4 6.4 3.0 43.5 41.0 98.5 -189.5 13.7 2.2 35.0 32.5 96.5 -211.6 6.3 3.1 42.1 39.6 98.5 -194.7 5.3 8.4 73.0 70.5 98.9 -93.8 13.6 3.7 43.7 41.2 96.6 -183.9 23.3 7.2 62.6 60.1 95.0 -115.10 63.6 4.2 42.5 40.0 92.7 -173. ax a. 2 o, o poc ep aa copooaec yeee pecoeaoo oe:

Ea = (23.0 2.3) + (5.8 0.4)lg A, (r = 0.98).

Aaoo pocxo yeee a aa c poco po aa (pc. 3):

H= (98.4 3.4) + (0.31 0.02)S, (r = 0.98).

Pc. 3. acoc H o S pea ClO2 co cpa 210, T= 30C, ea -200 -160 -120 -S, o -1 K --H, o Hae oecaooo ea ocec, o - oy, e exao oce cpo 2 - 10 oco xopa.

aaa oyex ax ceye, o yeo epae eepayp cpoee cxooo cpa cao e a ey pea.

Be pacope a pea oce cpo o yeo a pepe 2 eae (I), epaxopyepoe (II), eoe (III), 1,4-ocae (IV), xopeoe (V), aeae (VI), 1,2-xopae (VII), aeope (VIII). Bo cex pacopex eecoe ypaee pea ee d[1] - =(kd +k [ROH]) [1], e kd + k[ROH] = k ; kd - ocaa epedt coo pacaa oca xopa. yea acoc oca copoc oce poa-2-oa oco xopa o eepayp opeee aaoe apaep pea (a. 3).

Taa eece apaep oce poa-2-oa oco xopa pax pacopex (T = 30C, oa epe e peae 10 %) Paco- k104, H G S, Ea, lg A pe o-1-M-1c-o-I 0.59 53.2 50.7 98.5 -157.6 II 0.74 79.6 77.1 97.6 -67.8 9.III 0.86 61.6 59.1 98.2 -129 6.IV 0.38 48.5 45.7 100.4 -180.6 3.V 0.41 90.5 88.0 99.3 -37.2 11.VI 0.2 51.1 48.6 101.6 -174.8 4.VII 0.41 70.8 68.3 99.8 -104.1 7.VIII 0.27 52.0 49.4 100.7 -169 4.IX* 0.26 53.2 50.7 100.8 -165.3 4.* Boa, epaype ae.

ax a. 3 o, o poc ep aa copooaec yeee pecoeaoo oe:

Ea= (27.1 1.7) + (5.5 0.2)lg A, (r = 0.99).

Aaoo pocxo yeee a aa c poco po aa (pc. 4):

H= (97.6 1.1) + (0.29 0.01)S, (r = 0.99).

Pc. 4. acV oc H o S II pea oce poa-2-oa oVII co xopa yex pacopeIII IX VI I x, T=30 C VIII IV -160 -120 -80 -S, o-1 K -Hae oecaooo ea ocec, o - oy, e exao oce poa-2-oa oco xopa yex pacopex.

Heaeoe e pacope a ey pea ceecye o o, o epexooe cocoe ao opo.

opao - eece aooepoc (ep opo o cpy o oce) oo cea o o o, o pye ca yacye oa oeya oca xopa; oe aee po aa (S = -211.2-93.7 o-1K-1) peoaae cooyopoeoe epexooe cocoe; ocyce pacope a ey pea ceecye o o, o epexooe cocoe aoopo; ooe pacxooae cpa aaec p coooe peaeo cp : ClO2 = 1 : 2 o/o. Coaco epayp a aoee xapaep oca xopa c pea epeoca epoa.

oyee peya coacyc co cey exao pea:

-H, o OH RR1 OH R1 OH ClO2 C O C C + ClO- HClO2 RO R2 H R2 Cl # R1 H O RO C HClO2 + C O RCl R2 O Opaoae xoppoax poyo ao, o ce oc, peae oey cpa c xopoaco coo HClO, oopa opayec peyae pea cpoopopoa xop oo:

2ClO2- + H+ HClO + ClO3-.

2. Ocee eoo oco xopa yee aoec oca xopa c eoa poo a pepe eoa (11), 3-eeoa (12), 4-eeoa (13), 4-mpemyeoa (14), 2-oeceoa (15), 2,6--mpem-y-4eeoa (16), 2,4-xopeoa (17).

OH OH OH OH CHCHCH3 CHCH11 12 OH OH OH CHCHCl CH3 CHCHCHCH3 Cl caoeo, o oa oepc cxooo eoa pocxo p coooe eo : ClO2 = 1 : 2 o/o. Ocoe poy pea oca xopa c eoa pee a. 4.

Taa poy oce eoo oco xopa eo poy Bxo1, % 11 1,4-eoxo 2-Xop-1,4-eoxo eoxo 12 3-Me-1,4-eoxo 3-Me-6-xop-1,4-eoxo 13 1,4-eoxo 14 1,4-eoxo 15 2-oec-1,4-eoxo 2-oec-5-xop-1,4-eoxo 16 2,6--mpem-y-1,4-eoxo Bxo a pacxooa oce ey pea oce eoo 11-17 ya cepoooepec eoo o pacxooa oca xopa p = 400 cpee aeopa. p o e o ao ooe eoa oex poyo oecy ooc oo peepe. eoo 11 - 17 ey pea ya p yco [1]0<<[PhOH]0, e [1]0 [PhOH]0 - aae oepa oca xopa eoa cooeceo.

cex yex eoo eece pe c co oeo oppe (0.9900.999) ocac ypaee epoo opa (pc. 5).

oyoapecx aaopo eecx px pacca ee oca copoc epoo opa k = k[PhOH]n, (k ocaa copoc opoo opa), oope e ac o oepa 1.

Haaec ea acoc k o [PhOH]0 (pc. 6), eecoe ypaee pea ee :

d [1] - =k[1][ PhOH].

dt Pc. 5. oyo-7.apece aaopo eecx px pacxooa oca xopa -8. pea c eoo 11 (aeop, T= 40C, 1-[PhOH]-8. = 0.05 M, 2[PhOH]0 = 0.17 M) t 10 -2, c Pc. 6. acoc eo oca copoc pea oce eoa 11 oco xopa o oepa eoa p pax eepaypax (ae048 12 op, 1-20, 2[PhOH]0 10 2, M 30, 3-40, 4-50C) acoc oca copoc oce eoo oco xopa o eepayp opeee aaoe apaep (a. 5).

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