Синтез і характеристика похідних beta, beta-диметилакрилової кислоти: Автореф. дис… канд. хім. наук / Ю.І. Оглашенний, Держ. ун-т ‘Львів. політехнік

AeA?AEAAIEE OI?AA?NEOAO «EUeA?ANUeEA IIE?OAOI?EA»

Iaeaoaiiee TH??e ?aaiiae/

OAeE 547.391.4+542.951.3

NEIOAC ? OA?AEOA?ENOEEA IIO?AeIEO

(,(-AeEIAOEEAE?EEIAI? EENEIOE

02.00.03 — i?aai?/ia o?i?y

AAOI?AOA?AO

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?i?/ieo iaoe

Euea?a — 1999

Aeena?oaoe??th ? ?oeiien

?iaioa aeeiiaia o Aea?aeaaiiio oi?aa?neoao?

«Euea?anueea iie?oaoi?ea» I?i?noa?noaa ina?oe Oe?a?ie

Iaoeiaee ea??aiee: aeieoi? o?i?/ieo iaoe, i?ioani?

sso/eoei Einei Eineiiae/

AeO «Euea?anueea iie?oaoi?ea,

caa?aeoaa/ eaoaae?e aiae?oe/ii? o?i??.

Io?oe?ei? iiiiaioe: aeieoi? o?i?/ieo iaoe., i?ioani? Oaaei?iaa
Aeaaeeeaia Ieaenaiae??aia, AeO «Euea?anueea iie?oaoi?ea», i?ioani?
eaoaae?e i?aai?/ii? o?i??;

eaiaeeaeao o?i?/ieo iaoe, aeioeaio Eiaaoc Ie?ineaaa Ieaen??aia,
Euea?anueeee aea?aeaaiee oi?aa?neoao ?i. ?. O?aiea, aeioeaio
eaoaae?e o?ce/ii? o?i??.

I?ia?aeia onoaiiaa: ?inoeooo o?ceei-i?aai?/ii? o?i?? oa aoaeao?i?? ?i.
E.I.Eeoaeiaiea IAI Oe?a?ie, a?aeae?e aeine?aeaeaiiy ?aaeeeaeueieo
i?ioean?a, i. Aeiiaoeuee.

Caoeno aeena?oaoe?? a?aeaoaeaoueny «19» ea?oiy 1999 ?ieo i 15 aiae. ia
can?aeaii? niaoe?ae?ciaaii? a/aii? ?aaee Ae 35.052.01 o Aea?aeaaiiio
oi?aa?neoao? «Euea?anueea iie?oaoi?ea» ca aae?anith: 290646, i.
Euea?a-13, ie. Na. TH?a, 3/4, aoae 240.

C aeena?oaoe??th iiaeia iciaeiieoeny a a?ae?ioaoe? Aea?aeaaiiai
oi?aa?neoaoo «Euea?nueea iie?oaoi?ea» (aoe. I?ioani?nueea).

Aaoi?aoa?ao ?ic?neaiee «16» aa?aciy 1999 ?.

A/aiee nae?aoa? niaoe?ae?ciaaii??aaee,

e.o.i., aeioeaio
A.E. Nei?ioiaea

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue oaie aeena?oaoe??. Iio?aei? ae?eeiaeo eeneio ciaoiaeyoue
oe?iea canoinoaaiiy ye iiiiia?e i?e iaea?aeaii? iie?ia??a ??ciiai
i?ecia/aiiy. Iaeiae aeey oeueiai aeei?enoiaothoue, aieiaiei /eiii,
neeaaei? ao??e ae?eeiai? oa iaoae?eeiai? eeneio. Aaaaeaiiy aee?eueieo
cai?niee?a o (- /e (-iieiaeaiiy aei ea?aieneeueii?
a?oie i?eaiaeeoue aei ciaioaiiy iie?ia?ecaoe?eii? caeaoiino? iiiiia??a.

?acii c oei, i?aeoe/ia aeei?enoaiiy iio?aeieo (- oa (-aee?eae?eeiaeo
eeneio ia iaiaaeo?oueny eeoa ?aaeoe?yie iie?ia?ecaoe??. Aiie ciaeoee
canoinoaaiiy o ??cieo iaeanoyo i?aai?/ii? o?i?? ye aeo?aei? ?a/iaeie i?e
iaea?aeaii? iaeioiene/ieo ?inaeoeoeeae?a, i?ioecaiaeueieo i?aia?ao?a,
ianoeoeeae?a, (-ai?iieeneio, aioethaai?eueieo ai?iii?a, a?iiaoecoth/eo
eiiiiiaio?a o ia?othia???. Iaeiae i?aeoe/ia aeei?enoaiiy oeeo niieoe
iaiaaeo?oueny neeaaei?noth ? iaaeineiiae?noth i?ioean?a ?o iaea?aeaiiy.
Iniaeeai oea noino?oueny iio?aeieo (,(-aeeiaoeeae?eeiai? eeneioe
((,(-AeIAE). Naia oiio ?ic?iaeaiiy aeinooiieo iaoiae?a neioaco (,(-AeIAE
oa ?? iio?aeieo ? aaaeeeaei iaoeiaei ? i?aeoe/iei caaaeaiiyi aeey
?icoe?aiiy iaeanoae ?o aeei?enoaiiy.

Aeooaeuei?noue aeaii? ?iaioe i?aeoaa?aeaeo?oueny aeeth/aiiyi ?? o
i?ia?aio “?a/iaeie oa iaoa??aee o?i?/iiai ae?iaieoeoaa” (oeo? 7.3)
ca?aeii iinoaiiae AeEIO Oe?a?ie ? 12 a?ae 04.05.1992 ? a AeIOI (oeo?
“O?i?y”) ca?aeii iinoaiiae AeEIO Oe?a?ie ? 52 a?ae 22.03.1994, a oaeiae
o eii?aeeiaoe?ei? ieaie I?iina?oe Oe?a?ie c oaoiaiai iai?yieo “Iiiiia?e,
iiaa?oiaai aeoeai? ?a/iaeie, iaiiaithaa/?, iiaeeo?eaoi?e ? ia?niaeoeai?
oaoiieia?? iaea?aeaiiy iie?ia?ieo eiiiiceoe?eieo iaoa??ae?a ia ?o
iniia?”.

Iaoa ?iaioe. Aaeineiiaeaiiy iaoiae?a iaea?aeaiiy aeo?aeieo ?a/iaei —
(-iaoee-(-aooe?ieaeoiio ? (,(-AeIAE oa ?ic?iaea iaoiae?a neioaco ??
iio?aeieo (oei?aia?ae?eaeo, ao???a iaeiiaoiiieo nie?o?a oa ae?eie?a);
aea/aiiy e?iaoeee oa iaoai?cio ?aaeoe?e ?o iaea?aeaiiy; anoaiiaeaiiy
no?oeoo?e ? o?ceei-o?i?/ieo oa?aeoa?enoee iiaeo neioaciaaieo ?a/iaei oa
iiaeeeainoae ?o i?aeoe/iiai aeei?enoaiiy.

Iaoeiaa iiaecia iaea?aeaieo ?acoeueoao?a. Aeine?aeaeaii ?aaeoe?? neioaco
aeo?aeieo ?a/iaei — (-iaoee-(-aooe?ieaeoiio oa (,(-AeIAE — c aeinooiii?
ne?iaeie — aoeaoiio — c aeoiaeii iiiaae 90% oa aenieith /enoioith.
?aae?ciaaii aeaa aeueoa?iaoeai? oeyoe iaea?aeaiiy
(,(-aeeiaoeeae?eei?eoei?eaeo ((,(-AeIAO) c aeei?enoaiiyi
(-iaoee-(-aooe?ieaeoiio oa (,(-AeIAE. Aea/aii oa iienaii e?iaoeeo
?aaeoe?? aeeiaie?co (,(-AeIAO.

Aia?oa aeaoaeueii aea/aii aieea aoaeiae ? i?e?iaee nie?oo oa ?ic/eiieea,
ni?aa?aeiioaiiy ?aaaaio?a ia oaeaee?noue aeeiaie?co (,(-AeIAO. Iieacaii,
ui e?iaoe/i? caeiiii??iino? i?ioeano aaeaeaaoii iienothoueny ia’?aeiaiei
??aiyiiyi 2

Aaiiaoa-Oaooa ? Eiiiaey-Iaeueia, yea iaeii/anii a?aoiao? ye aeaeo?iii?
oae ? nieueaaoaoe?ei? ia?aiao?e nie?oo.

Anoaiiaeaii, ui aecia/aeueiee oa niia?eueithth/ee aieea ia oaeaee?noue
?aaeoe?? ia? iniiai?noue ?ic/eiieea aiane?aeie eiieo?oth/i? aca?iiae?? c
iieaeoeith oei?aia?ae?eaeo iniiaiiai ?ic/eiieea oa nie?oo i?e ooai?aii?
i?ii?aeiiai eiiieaeno. Aia?oa iieacaii, ui e?iaoeea i?ioeano aeeiaie?co
(,(-AeIAO caaeia?eueii iieno?oueny ??aiyiiyi I?oaae?na-Iaioai. Oea
i?aeoaa?aeaeo? cai?iiiiiaaiee iaoai?ci i?io?eaiiy ?aaeoe?? aeeiaie?co
oei?aia?ae?eaeo /a?ac i?ii?aeio noaae?th ooai?aiiy
aeiii?ii-aeoeaioi?iiai eiiieaeno c ia?aiinii ca?yaeo.

Anoaiiaeaii, ui ?aaeoe?y aoa?eo?eaoe?? ae?eie?a (,(-AeIAE a i?enooiino?
eeneioieo eaoae?caoi??a c acaio?iiiith a?aeaiieith aiaee i?io?ea? ca
iiiiiieaeoey?iei iaoai?ciii. Aia?oa iieacaii, ui ?aaeoe?y aoa?eo?eaoe??
ae?eie?a (,(-AeIAE i?ioiaeeoue /a?ac noaae?th aeeni?iii?oe?iioaaiiy
iiiiao??o.

I?aeoaa?aeaeaii, ui aaaaeaiiy aeaio cai?niee?a o (-iieiaeaiiy aei
ea?aieneeueii? a?oie ae?eeiai? eeneioe i?aeoe/ii iiai?noth aaeueio?
i?ioean aiii- oa ni?aiie?ia?ecaoe?? (,(-AeIAE ? ?? iio?aeieo.
Anoaiiaeaii, ui neeaaei? ao??e oe??? eeneioe anooiathoue o ?aaeoe??
aiii- oa ni?aiie?ia?ecaoe?? o?eueee i?e iayaiino?
iie?ia?ecaoe?eiicaeaoiiai iiaea?eiiai ca`yceo a nie?oiaiio caeeoeo.

I?aeoe/ia cia/ei?noue ?iaioe. Aaeineiiaeaiiy iaoiae?a neioaco iio?aeieo
(,(-AeIAE c aeinooiii? ne?iaeie aeaei iiaeeea?noue neioacoaaoe c
e?euee?nieie aeoiaeaie 18 iiaeo ao???a, ye? iiaeooue aooe aeei?enoai? ye
?aaeoe?eiicaeaoi? niieoee aeey iaea?aeaiiy oe?iieo i?aai?/ieo
i?aia?ao?a. Iiiiao??e ae?eie?a ? (,(-AeIAE iiaeooue canoiniaoaaoenue ye
ni?aiiiiia?e o ?aaeoe?yo iie?eiiaeainaoe?? c ooai?aiiyi
aenieiiieaeoey?ieo niieoe.

Iieacaii i?aeoe/io iiaeeea?noue aeei?enoaiiy aeaio aeueoa?iaoeaieo
oeyo?a iaea?aeaiiy oei?aia?ae?eaeo (,(-AeIAE c (-iaoee-(-aooe?ieaeoiio
(aeo?ae 92%) aai c (,(-AeIAE (aeo?ae 97%) ? oei?enoiai o?ii?eo.

Iaea?aeai? ni?aiie?ia?e ae?eiaiai ao??o (,(-AeIAE ? noe?ieo
canoiniaothoueny o a?aeae?eaii? o?ceei-o?i?? ? oaoiieia?? ai?th/eo
eiiaeei ?inoeoooo o?ce/ii? o?i?? ?i. E.A.Iena?aeaanueeiai IAI Oe?a?ie
aeey aeaioiaeaiiy iai?ai?iieeieo iaia?ai c aenieith no?ee?noth aei
aaeoa??e oa a?eueoino? i?aai?/ieo ?ic/eiiee?a.

Iniaenoee aianie caeiaoaa/a iieyaa? o i?iaaaeaii? e?iaoe/ieo
aeine?aeaeaiue, neioac? iiaeo niieoe, aiae?c? oa iaoaiaoe/i?e ia?iaoe?
iaea?aeaieo ?acoeueoao?a ? ia?aa??oe? ?ic?aoiaaieo e?iaoe/ieo ??aiyiue
ia aaeaeaaoi?noue. Aeena?oaioo iaeaaeeoue ae??oaeueia ?ieue a
?ioa?i?aoaoe?? aenia?eiaioaeueieo aeaieo.

Ai?iaaoe?y ?acoeueoao?a ?iaioe. Iniiaiee ci?no aeena?oaoe?eii? ?iaioe
aeiiia?aeaany ia: XVII Oe?a?inuee?e eiioa?aioe?? c i?aai?/ii? o?i?? (i.
Oa?e?a, 1995 ?.); iaoeiai-i?aeoe/i?e eiioa?aioe?? “Euea?anuee? o?i?/i?
/eoaiiy” (i. Euea?a, 1995 ?.); iaoeiai-i?aeoe/i?e
eiioa?aioe?? “Euea?anuee? o?i?/i? /eoaiiy” (i. Euea?a, 1997 ?);
Anaoe?a?inuee?e eiioa?aioe?? c aiae?oe/ii? o?i?? (i. Oaeai?iae,
1998 ?.); Oe?a?inuee?e eiioa?aioe?? c i?aai?/ii? o?i??
(i. Aei?i?iiao?ianuee, 1998?.).

Ioae?eaoe??. ?acoeueoaoe aeena?oaoe?eii? ?iaioe iioae?eiaai? o 7 noaooyo
oa 5 oacao iaoeiaeo eiioa?aioe?e.

No?oeoo?a oa ianya ?iaioe. Aeena?oaoe?eia ?iaioa neeaaea?oueny c anooio,
oanoe ?icae?e?a, aeniiae?a, nieneo aeei?enoaii? e?oa?aoo?e ? aeiaeaoe?a.
Iaoa??aee aeena?oaoe?eii? ?iaioe, aeeeaaeai? ia 145 noi??ieao
iaoeiiieniiai oaenoo, aeeth/athoue 32 ?enoiee, 22 oaaeeoe?. Nienie
aeei?enoaii? e?oa?aoo?e ia?aoiao? 189 aeaea?ae, aeiaeaoee ?ici?uai? ia
18 noi??ieao.

INIIAIEE CI?NO ?IAIOE

O anooi? iaa?oioiaaii aeioe?euei?noue oa aeooaeuei?noue aea/aiiy
i?iaeaie neioaco iio?aeieo (,(-AeIAE, anoaiiaeaii iaoo ?iaioe, ??
iaoeiao iiaecio oa i?aeoe/io cia/ei?noue. Iaaaaeaii iniiaio ?ioi?iaoe?th
i?i ai?iaaoe?th ?iaioe oa ioae?eaoe??.

O ia?oiio ?icae?e? aeeeaaeaii iaeyae oa aiae?c e?oa?aoo?ieo aeaea?ae i?i
iaoiaee neioaco (,(-AeIAE oa ?? iio?aeieo, ia iniia? /iai c?iaeaii
ocaaaeueiaiiy ? aeniiaee i?i no/aniee noai oa ia?niaeoeae ?icaeoeo
aeine?aeaeaiue o oe?e iaeano?.

I?iaaaeaiee aiae?c aeicaieea iaa?oioiaaii aecia/eoe iniiai? iai?yiee
aenia?eiaioaeueieo aeine?aeaeaiue.

O ae?oaiio ?icae?e? aaeineiiaeaii neioac aeo?aeieo ?a/iaei —
(-iaoee-(-aooe?ieaeoiio oa (,(-AeIAE. Iienaii niiniae i/enoee ?
oa?aeoa?enoeee ?aaaaio?a, ?ic/eiiee?a oa eaoae?caoi??a, a oaeiae iniiai?
iaoiaeeee i?iaaaeaiiy o?ceei-o?i?/ieo aiae?c?a ? e?iaoe/ieo
aeine?aeaeaiue, ye? aeei?enoai? o ianooiieo ?icae?eao ?iaioe.

Iieacaii, ui iaea?eueo i?eeiyoiei c oi/ee ci?o i?aeoe/iiai aeei?enoaiiy
? iaoiae neioaco (,(-AeIAE c i?iieneiai aeinooiii? ne?iaeie — aoeaoiio —
/a?ac noaae?th iaea?aeaiiy (-iaoee-(-aooe?ieaeoiio ca?aeii noaie:

O

ti

CH3(C(CH3 (( CH2=C=O + CH4

O
CH3

[(C2H5I)2.BF3] |

4

NI3(N(NI3 + NI2=N=I ((((((( NI3 (N(NI2(N=I

( (

(O(

CH3 CH3 O

| HCl |

NI3 (N(NI2(N=I (( NI3(C=CH(C(OH

( (

(O(

A ?acoeueoao? ?ic?iaee ?iai/eo oiia neioac?a aaeaeiny i?e eiioeaio?aoe??
eaoae?caoi?a — 2,0%ian., oaiia?aoo?? 263-268 E oa iieueiiio
ni?aa?aeiioaii? eaoai:aoeaoii = 3:4 i?aeaeueoe aeo?ae eaeoiio o
ii??aiyii? c e?oa?aoo?ieie aeaieie c 75% aei 92%; a i?e oaiia?aoo??
353E, iiey?iiio ni?aa?aeiioaii? eaeoii:HCl = 1:1,5 oa aeei?enoaii?
15%-iiai ?ic/eio nieyii? eeneioe aeo?ae (,(-AeIAE c?inoa? c 72% aei 94%.

Aoaeiaa (-iaoee-(-aooe?ieaeoiio ? (,(-AeIAE i?aeoaa?aeaeaia
niaeo?ineii?/ii, a ?o o?ceei-o?i?/i? oa?aeoa?enoeee ni?aiaaeathoue c
e?oa?aoo?ieie.

O o?aoueiio ?icae?e? ?ic?iaeaii niiniae iaea?aeaiiy oei?aia?ae?eaeo
(,(-AeIAE c aeei?enoaiiyi aeoeaiiai oei?oth/iai aaaioo — oei?enoiai
o?ii?eo ye c eeneioe, oae ? aaciina?aaeiuei c (-iaoee-(-aooe?ieaeoiio.

Aeey aeinyaiaiiy caaeia?eueii? oaeaeeino? ?aaeoe?? neioac
oei?aia?ae?eaeo c (,(-AeIAE ne?ae i?iaiaeeoe i?e 313-323E c iino?eiei
aeaeaeaiiyi c ?aaeoe?eii? iane HCl i SO2 i?e iioeiaeueiiio iieueiiio
ni?aa?aeiioaii? eeneioa:SOCl2=1:1,1. A oaeeo oiiaao neioaco iia?/ia
?aaeoe?y a?ae?ioei?oaaiiy i?aeoe/ii ia i?io?ea?. (,(-AeIAO iaea?aeaii c
aeoiaeii 97% (i?ioe 65% ca?aeii e?oa?aoo?ieo aeaieo), a eiai
o?ceei-o?i?/i? oa?aeoa?enoeee a?aeiia?aeathoue e?oa?aoo?iei.

I?e neioac? (,(-AeIAO aaciina?aaeiuei c (-iaoee-(-aooe?ieaeoiio i?io?ea?
iia?/ia ?aaeoe?y ooai?aiiy oei?aia?ae?eaeo 3-oei?-3-iaoeeaooaiiai?
eeneioe. C iaoith i?i?i?caoe?? oeueiai i?ioeano aeioe?eueii i?e neioac?
oei?aia?ae?eaeo aeiaeaaaoe eaeoii aei oei?enoiai o?ii?eo, a ia iaaiaee,
i?e iioeiaeueiiio iiey?iiio ni?aa?aeiioaii?
(-iaoee-(-aooe?ieaeoii:SOCl2=1:1,5 a oaiia?aoo?iiio ?ioa?aae? 318-323E.
A oeeo oiiaao aeo?ae (,(-AeIAO c?inoa? c 61% (ca?aeii e?oa?aoo?ieo
aeaieo) aei 92%, aea ?icae?eeoe oe? aeaa oei?aia?ae?eaee aiane?aeie
aeecueeeo oaiia?aoo? eei?iiy iaoiaeii ?aeoeo?eaoe?? i?aeoe/ii
iaiiaeeeai. Oeae oaeo iaiaaeo? i?aeoe/ia aeei?enoaiiy aaciina?aaeiueiai
neioaco (,(-AeIAO c (-iaoee-(-aooe?ieaeoiio ? oei?enoiai o?ii?eo,
iieiath/e noaae?th iaea?aeaiiy (,(-AeIAE.

*aoaa?oee ?icae?e i?enay/aii aeine?aeaeaiith iaoai?cio ?aaeoe??
aeeiaie?co (,(-AeIAO iaeiiaoiiieie nie?oaie oa ?ic?iaoe? iaoiae?a
neioaco neeaaeieo

ao???a (,(-AeIAE. Aea/aeanue caeaaei?noue oaeaeeino? ?aaeoe?? a?ae
aoaeiae oa i?e?iaee nie?oo, ?ic/eiieea ? ni?aa?aeiioaiiy ?aaaaio?a.

Aeeiaie?c (,(-AeIAO nie?oaie ??cii? aoaeiae i?iaaaeaii a na?aaeiaeu?
ai?ioiiiiai ?ic/eiieea i?e iiey?iiio ni?aa?aeiioaii? (,(-AeIAO:ROH:C6H6
= 1:1:20 a oaiia?aoo?iiio ?ioa?aae? 293-323E (oaae.1).

Iayai?noue o aeine?aeaeoaai?e na??? ?cie?iaoe/iino? aeicaieeea
canoinoaaoe aeey e?euee?nii? ioe?iee aieeao aoaeiae nie?oo ia
oaeaee?noue aeeiaie?co (,(-AeIAO i?eioeei e?i?eiino? a?eueieo aia?a?e
oeyoii ia?aa??ee aaeaeaaoiino? c aenia?eiaioii iaeii- oa
aeaiia?aiao?iaiai ??aiyiue Aaiiaoa-Oaooa. Anoaiiaeaii, ui
iaeiiia?aiao?ia? caeaaeiino? i?ae lgk303 oa ?iaeoeoe?eiith ((*) ?
noa?e/iith (Es) eiinoaioaie ia aeathoue caaeia?eueii? ei?aeyoe??. Ni?iaa
ocaaaeueieoe aieea aeaeo?iiieo ? noa?e/ieo aoaeo?a cai?nieea ia
oaeaee?noue ?aaeoe?? aeeiaie?co (,(-AeIAO ca aeiiiiiaith
aeaiia?aiao?iaiai ??aiyiiy Aaiiaoa-Oaooa oaeiae ia aeaea caaeia?eueiiai
?acoeueoaoo:

lgk303 = (-1.84 + 0.07) — (0.58 + 0.49) (* + (0.53 + 0.12)Es
(1)

R=0.825, s=+0.179, N=14.

A?aenooi?noue aeey an?o 14-oe nie?o?a aaeaeaaoii? ei?aeyoe?eii?
caeaaeiino? i?ae lgk303, (*, oa As na?ae/eoue i?i oa, ui ia e?iaoeeo
?aaeoe?? aieeaathoue ua e aeaye? ?io? oaeoi?e.

Oaaeeoey 1.

Eiinoaioe oaeaeeino? ae?oaiai ii?yaeeo oa aeoeaaoe?ei? ia?aiao?e
?aaeoe?? aeeiaie?co (,(-AeIAO a aaicie?.

Nie?o (* Es k.103,

e/iieue.n A#,

eAeae

iieue (H#,

eAeae

iieue -(S#,

Aeae

iieue.E (G#,

eAeae

iieue

293E 303E 313E 323E

Iaoeeiaee 0 0 17.1 29.2 61.9 __ 51.8 49.2 111 83.2

Aoeeiaee -0.100 -0.27 7.0 10.6 19.6 28.5 38.2 35.7 165 85.7

i-I?ii?eiaee -0.115 -0.56 6.6 10.0 18.1 __ 38.6 36.0 173 88.4

?ci-I?ii?eiaee -0.190 -0.85 __ 4.3 7.4 12.6 43.4 40.8 156 88.0

i-Aooeeiaee -0.130 -0.59 6.0 10.0 15.0 20.8 32.6 30.1 184 85.9

?ci-Aooeeiaee -0.125 -1.13 4.9 7.9 11.8 15.4 30.6 28.1 193 86.5

o?ao-Aooeeiaee -0.300 -2.14 0.4 1.2 2.3 5.7 68.0 65.4 85 91.2

i-Ai?eiaee -0.135 -0.55 6.02 8.9 13.2 22.9 34.6 32.1 178 86.2

?ci-Ai?eiaee -1.620 -0.55 4.1 8.1 11.5 16.3 35.7 33.2 176 86.4

i-Aaeneeiaee -0.135 -0.6 6.9 8.9 13.2 22.9 31.4 28.9 189 86.2

i-Ieoeeiaee -0.125 -0.53 6.9 7.9 13.5 24.0 33.4 30.9 183 86.5

i-Aeaoeeeiaee -0.135 -0.53 6.3 7.8 14.0 21.3 33.0 30.5 184 86.5

Ae?eiaee 0.180 -0.56 5.8 7.2 9.0 11.8 18.4 15.8 234 86.7

Aaiceeiaee 0.215 0.22 5.7 6.8 8.2 12.1 17.4 14.9 238 86.9

O ca`yceo c oeei aeey aaeaeaaoiiai iieno i?ioeano canoiniaoaaeinue
ia`?aeiaia naieia?aiao?iaa ??aiyiiy, yea aeeth/a? a naaa
i`yoeia?aiao?iaa “nieueaaoaoe?eia” ??aiyiiy Eiiiaey-Iaeueia, ui a?aoiao?
caeaoi?noue nie?oo aei niaoeeo?/ii? oa ianiaoeeo?/ii? nieueaaoaoe??,
aonoeio aia?a?? eiaac??, oa aeaiia?aiao?iaa “e?iaoe/ia” ??aiyiiy
Aaiiaoa-Oaooa, yea a?aoiao? aieea aeaeo?iiieo oa noa?e/ieo oaeoi??a
cai?niee?a o iieaeoe? nie?oo. Oea ??aiyiiy aaeaeaaoii iieno? i?ioean:

n2-1
e-1

lgk303 = -18.82+(13.0+3.7) ________ — (5.9+1.8) ______ —
(0.02+0.40).10-3d2 +

n2+ 2
2e+1

+(1.8+4.1) .10-3B + (0.31+0.05)ET + (2.6+0.6)s* — (0.44+0.16)Es
(2)

R=0.984, s=+0.05, N=14.

Aeeeth/aiiy iaeicia/eieo ia?aiao??a iieaco?, ui caaeia?eueii iieno?
aieea no?oeoo?e oa i?e?iaee nie?oo ia e?iaoeeo aeeiaie?co (,(-AeIAO
/ioe?eia?aiao?iaa ??aiyiiy, yea aeeth/a? oaeoi?e ianiaoeeo?/ii?
(iiey?i?noue oa iiey?eciaai?noue) oa niaoeeo?/ii? (aeaeo?io?euei?noue)
nieueaaoaoe??, a oaeiae aieea ?iaeoeoe?eiiai aoaeoo cai?nieea:

lgk303=-9.83+(4.5+1.71)f(n2)-(4.7+1.8)f(e)+(0.17+0.01)ET-(1.5+0.3)s*
(3)

R=0.973; s=+ 0.07, N=14.

I?ioean aeeiaie?co oei?aia?ae?eae?a i?ioiaeeoue /a?ac i?ii?aeio noaae?th
ooai?aiiy ?aaaaioaie aeiii?ii-aeoeaioi?iiai eiiieaeno c ia?aiinii
ca?yaeo (EIC) (noi?. 9), yeee /a?ac aeoeaiaaiee eiiieaen
ia?aoai?th?oueny o i?iaeoeoe ?aaeoe??, ? oiio ooai?aiith EIC (a cia/eoue
? ca?eueoaiith oaeaeeino? ?aaeoe?? aeeiaie?co) ni?ey? c?inoaiiy
aeaeo?iiii? aonoeie ia aoii? eenith a?ae?ieneeo o iieaeoe? nie?oo, yea
oa?aeoa?eco?oueny ?iaeoeoe?eiith eiinoaioith (*(oaae.1).

Uiaei aieeao oaeoi??a ianiaoeeo?/ii? nieueaaoaoe??, oi c ?inoii
iiey?iino? na?aaeiaeua aoaea c?inoaoe noaa?euei?noue eiiieaeno, ui
oo?oaeithaaoeia eiai ianooiia ia?aa?oioaaiiy o i?iaeoeoe. Iaeaaaii?oei ?
aieea ia oaeaee?noue aeeiaie?co (,(-AeIAO caeaoiino? nie?o?a aei
aeaeo?io?eueii? nieueaaoaoe?? AO (eeneioi?noue), yea oa?aeoa?eco? ?o
caeaoi?noue aei ooai?aiiy eiiieaen?a c aiaeiaaei ca`yceii ? na?ae/eoue
i?i ooai?aiiy ia ia?aeii?e noaae?? ?aaeoe?? ca`yceo I…I i?ae i?ioiiii
aiaeith nie?oo ? ea?aii?eueiei eeniai oei?aia?ae?eaeo.

I?iaaaeaiee aiae?c aeicaiey? noaa?aeaeoaaoe, ui ia ?aaeoe?th aeeiaie?co
(,(-AeIAO aieeaathoue ia o?eueee aeaeo?iii?, a e nieueaaoaoe?ei?
ia?aiao?e nie?oo iaa?oue i?e aea?iiey?iiio ni?aa?aeiioaii? ?aaaaio?a,
aiane?aeie /iai aieea eiai aoaeiae ? o?ceei-o?i?/ieo aeanoeainoae ia
oaeaee?noue aeine?aeaeoaaii? ?aaeoe?? ? noia?iei ?acoeueoaoii an?o
i?ioean?a, ye? a?aeaoaathoueny a nenoai?.

C iaoith a?eueo aeaoaeueiiai anoaiiaeaiiy iaoai?cio ?aaeoe?? aea/aii
oaeaee?noue ?aaeoe?? iaoaiie?co (,(-AeIAO a na?aaeiaeu? ?yaeo
?ic/eiiee?a c??ciith caeaoi?noth aei nieueaaoaoe?? i?e 293-323E,
iiey?iieo ni?aa?aeiioaii? (,(-AeIAO:iaoaiie:?ic/eiiee = 1:1:20 (oaae.
2).

Anoaiiaeaii, ui aeiaeai c ia?aiao??a ?ic/eiiee?a nai ii nia?
caaeia?eueii ia oa?aeoa?eco? aieea na?aaeiaeua ia oaeaee?noue ?aaeoe??,
oi/a inoaiiy neiaaoii ciaioo?oueny c ?inoii iniiaiino? (A) oa iiey?iino?
((-1/2(+1) na?aaeiaeua.

E?euee?nia ioe?iea aieeao i?e?iaee ?ic/eiieea ia oaeaee?noue iaoaiie?co
(,(-AeIAO aeicaiey? iaea?aeaoe /ioe?eia?aiao?iaa ??aiyiiy, yea
caaeia?eueii iieno? aeine?aeaeoaaiee i?ioean ? a?aoiao? oaeoi?e
ianiaoeeo?/ii? nieueaaoaoe??, iniiai?noue ?ic/eiieea oa aonoeio aia?a??
eiaac??:

lgk30=-2.57+(4.7+1.5)f(n2)-(4.6+0.8)f(()+(3.3+0.6).10-3(2-(3.2+0.5).10-3
B (4)

R=0.952, s=+0.189, N=20.

Oaaeeoey 2.

Aenia?eiaioaeuei? cia/aiiy eiinoaio oaeaeeino? ?aaeoe?? iaoaiie?co
(,(-AeIAO a ??cieo ?ic/eiieeao i?e 303E oa ?o oa?aeoa?enoeee.

?ic/eiiee k.103,

e/iieue.n n2+1

n2+2 (-1

2(+1 (2,

eAeae/iieue A,

ni-1 AO

Aaicie 29.2 0.2931 0.2306 349.7 48 34.3

Oei?ioi?i 8.9 0.2653 0.3584 353.1 14 39.1

Aoeaoii 1.1 0.2200 0.4655 397.2 193 42.2

Oao?aoei?iaoai 63.6 0.2770 0.2263 311.2 0 32.4

Aeeiaoeeoi?iai?ae 1.8 0.2586 0.4803 613.6 294 43.8

Aaenai 37.8 0.2288 0.1862 222.0 0 31.0

Aeeiaoeenoeueoieneae 4.8 0.2826 0.4848 634.9 362 45.1

Aoeaoii?o?ee 5.3 0.2120 0.4803 590.5 178 45.6

Oeeeeiaaenaiii 1.9 0.2692 0.4601 431.2 242 39.8

1,2-Aeeoei?aoai 15.9 0.2660 0.4328 396.4 40 41.9

Oei?aaicie 21.4 0.3064 0.3788 381.0 38 37.5

Ai?cie 18.1 0.3030 0.3473 380.0 155 37.1

Aeeaooeeiaee yo?? 1.8 0.2420 0.2907 250.4 285 33.0

Iaoeeaoeeeaoii 0.7 0.2308 0.4605 361.7 209 41.3

Aoeaoioaiii 8.0 0.3124 0.4581 464.3 202 40.6

Aeeiaoeeaoeaoai?ae 0.9 0.2621 0.481 479.1 343 43.7

I?o?iaaicie 8.4 0.3198 0.4793 479.4 67 41.2

Oao?aa?ae?ioo?ai 0.6 0.2465 0.4072 363.8 305 37.4

i-Ai?eaoeaoao 1.1 0.2440 0.3582 298.1 190 38.0

Aaicii?o?ee 6.7 0.3080 0.4708 515.0 155 42.0

Ca?eueoaiiy iniiaiino? ?ic/eiieea a?ae/ooii iiieaeo? oaeaee?noue
?aaeoe??, ui na?ae/eoue i?i iayai?noue eiieo?aioe?? i?e ooai?aii? EIC
i?ae iieaeoeith iniiaiiai ?ic/eiieea oa nie?oo ca iieaeoeo
oei?aia?ae?eaeo. Aiaeia?/iee aoaeo noai?th? ca?eueoaiiy iiey?iino?
?ic/eiieea, yea ni?ey? ia?aiino aeaeo?ii?a a ooai?thaaiiio EIC i?ae
oei?aia?ae?eaeii oa i?aai?/iith iniiaith.

?acii c oei, c?inoaiiy aia?a?? eiaac?? na?aaeiaeua i?eoaeaeoo? i?ioean,
ine?eueee ?ic/eiieee c aenieith aia?a??th eiaac?? ni?eythoue ooai?aiith
i?ii?aeiiai EIC, noai?thth/e iaaeiei iueiai nai???aeio iaieiieo, yea
iieaaoo? ia?aoai?aiiy EIC a aeoeaiaaiee eiiieaen oa i?iaeoeoe ?aaeoe??.

Aeey ?aaeoe?e, ye? i?io?eathoue /a?ac ia?aeiio noaae?th ooai?aiiy
i?ii?aeiiai eiiieaeno:

K??ai k?ici

[A:B] (( i?iaeoeoe

aoaeoeaia eiinoaioa oaeaeeino? ae?oaiai ii?yaeeo i?e ci?i?
ni?aa?aeiioaiiy ?aaaaio?a ia ? iino?eiith, a e?iaoeea i?ioeano
iieno?oueny ??aiyiiyi I?oaae?na-Iaioai:

(5)

aea kao — aenia?eiaioaeueii aecia/aia aeey aeaiiai ni?aa?aeiioaiiy
eiinoaioa oaeaeeino? ae?oaiai ii?yaeeo e/iieue.n; K??ai — eiinoaioa
??aiiaaae ooai?aiiy EIC aeo?aeieie ?a/iaeiaie, e/iieue; k?ici —
eiinoaioa oaeaeeino? iiiiiieaeoey?iiai ?iciaaeo ooai?aiiai EIC a
i?iaeoeoe ?aaeoe??, n-1, NA- iiey?ia eiioeaio?aoe?y ?aaaoth/i? ?a/iaeie,
acyoi? o iaaeeeoeo, iieue/e.

Anoaiiaeaii, ui ci?ia aoaeoeaieo eiinoaio oaeaeeino? iaoaiie?co
(,(-AeIAO a caeaaeiino? a?ae iaaeeeoeo oei?aia?ae?eaeo caaeia?eueii
iieno?oueny ?aiyiiyi I?oaae?na-Iaioai (?en. 1). C oaiaaina eooa iaoeeo
iaea?aeaieo i?yieo iaea?aeaii cia/aiiy k?ici, a aaee/eie a?ae??ce?a ia
in? i?aeeiao, ye? a?aeoeiathoueny oeeie i?yieie, aeicaieythoue aecia/eoe
aaee/eie E??ai (oaae. 3).

Oaaeeoey 3.

Cia/aiiy eiinoaio ??aiiaaae (E??ai) ? oa?iiaeeiai?/ieo ia?aiao??a
ooai?aiiy EIC, eiinoaio oaeaeeino? (k?ici) oa aeoeaaoe?eieo ia?aiao??a
ia?aoai?aiiy EIC a i?iaeoeoe ?aaeoe?? i?e 303E.

Eiinoaioe 283E 293E 303E 313E A#?ici,

eAeae

iieue (I#?ici

((I),

eAeae

iieue (S#?ici

((S),

Aeae

iieue E (G#?ici

((G),

eAeae

iieue

Kp?ai.102, e/iieue 18,90 20,65 25,13 28,01 ( — 10.09 — 21 — 3.73

k?ici.102, .n-1 4.94 7.47 10.08 19.60 32.73 30.21 -164 -79,90

A?ae’?ii? cia/aiiy (H??ai oa (S??ai aeacothoue ia aia?aaoe/io
aea?aei?noue ooai?aiiy EIC ? na?ae/aoue i?i ooai?aiiy iiaeo ca’yce?a, ui
i?aeoaa?aeaeo? ?nioaaiiy EIC. Cia/aiiy (G??ai<0 na?ae/eoue i?i naiia?euei?noue i?ioiaeaeaiiy ?aaeoe?? eiiieaeniooai?aiiy. Cia/aiiy aia?a?? aeoeaaoe?? ?iciaaeo eiiieaeno o i?iaeoeoe (A#?ici=30,21 eAeae/iieue) nooo?ai iaioa, i?ae aia?a?y aeoeaaoe?? a?oooi 9 i?ioeano (A#aeo=43,1eAeae/iieue), a oea icia/a?, ui ?iciaae EIC o i?iaeoeoe ?aaeoe?? ia ? e?i?ooth/ith noaae??th i?ioeano. Oaeei /eiii iieacaii, ui aeeiaie?c (,(-AeIAO i?io?ea? /a?ac i?ii?aeio ??aiiaaaeio noaae?th ooai?aiiy EIC, yeee, i?ney ia?aa?oioaaiiy a aeoeaiaaiee eiiieaen (AE), ?iciaaea?oueny o i?iaeoeoe ?aaeoe??. A?aeiinii iecuee? cia/aiiy eiinoaio ??aiiaaae oa iaaaeeea a?ae’?iia cia/aiiy (G??ai=-3.73 eAeae/iieue aeacothoue ia oa, ui e?i?ooth/ith noaae??th i?ioeano aeeiaie?co (,(-AeIAO ? ooai?aiiy EIC: NI3 O NI3 O(- R | K??ai | / CH3(C=NI(N(+ (--- :O(- (( | \ Cl H (EIC) CH3 I R NI3 O | / k?ici | (( CH3(C=NI(N...I (( CH3(C=NI(N(OR + HNl Cl...H (AE) ?en. 1. Caeaaei?noue aoaeoeaii? eiinoaioe oaeaeeino? iaoaiie?co (,(-AeIAO a?ae ii/aoeiai? eiioeaio?aoe?? oei?aia?ae?eaeo a oaiia?aoo?iiio ?ioa?aae? 283-313E (i?e iino?ei?e eiioeaio?aoe?? nie?oo 0.5 iieue/e). Aeineoue aenie? cia/aiiy e?iaoe/ieo oa aeoeaaoe?eieo ia?aiao??a i?ioeano i?aeoaa?aeaeothoue aeioe?euei?noue aeai?o i?aia?aoeaiiai iaoiaeo neioaco ao???a (,(-AeIAE aeeiaie?cii ?? oei?aia?ae?eaeo. Aeey aeinyaiaiiy caaeia?eueii? oaeaeeino? ?aaeoe?? (oaae. 1) neioac ao???a ne?ae i?iaiaeeoe i?e 303-323E ? iiey?iiio ni?aa?aeiioaii? (,(-AeIAO:nie?o=1:1,1. Iacia/iee iaaeeeoie nie?oo acyoi c a?aooaaiiyi eiia??iino? oaoiieia?/ieo ao?ao. A oaeeo oiiaao ?aaeoe?y a?ae?ioei?oaaiiy iiaea?eiiai ca’yceo i?aeoe/ii ia i?io?ea?. Iaea?aeai? ao??e ? i?ici?eie ??aeeiaie c oa?aeoa?iei caiaoii, ?o aoaeiaa i?aeoaa?aeaeaia niaeo?ineii?/ii, a aeoiaee oa o?ceei-o?i?/i? oa?aeoa?enoeee iaaaaeaii o oaae.4. Oaaeeoey 4. O?ceei-o?i?/i? oa?aeoa?enoeee ao???a (,(-AeIAE CH3-C(CH3)=CH-C(O)OR R Oeei., E(EIa) nD20 d420, a/ni3 Iieaeoey?ia ?ao?aeoe?y Iieaeoey?ia iana Ai?no iniiaii? ?a/iaeie Aeo?ae, % ciaeae. ia/ene ciaeae ia/ene % ian. CH3* 401(101) 1.4372 0.9668 30.904 31.218 114 115 96.7 91 C2H5** 354(9.12) 1.4398 0.9457 35.660 35.866 128 129 98.8 95 C3H7 348(1.31) 1.4470 0.9401 40.358 40.514 142 145 98.6 95 ?ci-C3H7 356(1.31) 1.4458 0.9412 40.217 40.514 142 144 98.1 93 C4H9 335(0.65) 1.4496 0.9329 44.904 45.162 156 159 98.3 94 ?ci-C4H9 349(0.69) 1.4478 0.9466 44.951 45.162 156 159 98.5 94 o?ao-C4H9 372(0.65) 1.4476 0.9336 44.983 45.162 156 157 96.9 92 C5H11 348(0.53) 1.4530 0.9194 49.977 49.810 170 172 97.2 95 ?ci-C5H11 362(0.55) 1.4502 0.9228 49.527 49.810 170 173 98.7. 93 C6H13 367(0.43) 1.4530 0.9102 54.640 54.458 184 187 98.1 94 C8H18 375(0.35) 1.4548 0.9054 63.505 63.754 212 215 98.3 92 C10H21 387(0.33) 1.4578 0.9053 72.909 73.050 240 242 97.9 92 NI2=NI-NI2 337(0.30) 1.4560 0.9477 40.158 40.036 140 144 97.5 90 C6H5NI2 352(0.40) 1.4610 0.9427 55.305 55.346 190 194 96.3 88 * nD20=1.4361, Oeei.,=405 E(101.3 EIa). ** nD20=1.4380, Oeei.,=362 K (11 KIa) (ca?aeii e?oa?aoo?ieo aeaieo). *enoioo iaea?aeaieo ao???a eiio?iethaaee o?i?/ieie iaoiaeaie (aiae?c ia iaiane/ai?noue oa ao??ia /enei) oa o?iiaoia?ao?/ii. Aoaeiaa ao???a i?aeoaa?aeaeaia ?*-niaeo?ineii?/ii. I’yoee ?icae?e i?enay/aiee neioaco ?ai?oa ia iienaieo o e?oa?aoo?? ao???a, ooai?aieo (,(-AeIAE oa ae?eieyie, iaoiaeii i?yii? aoa?eo?eaoe?? o ia??aiiaaaeieo oiiaao c acaio?iiiith a?aeaiieith aiaee. Aea/aii aieea iniiaieo ia?aiao??a neioaco ia aeo?ae iiii- ? aeeao???a ae?eie?a. Aenia?eiaioaeueii anoaiiaeaii, ui iioeiaeueia ni?aa?aeiioaiiy (,(-AeIAE:ae?eieue noaiiaeoue 2,2:1 o aeiaaeeo neioaco aeeao???a, oa 1,2:1 i?e neioac? iiiicai?uaieo ao???a. Iaeneiaeueiee aeo?ae aeinyaa?oueny i?e aeei?enoaii? ?ic/eiieea aaicieo (ni?aa?aeiioaiiy (,(-AeIAE:aaicie=1:3,5-4). Anoaiiaeaii, ui iaeneiaeueiee aeo?ae ao???a aeinyaa?oueny i?e aeei?enoaii? eaoae?caoi?a i-oieoienoeueoieeneioe (i-ONE) i?e iioeiaeuei?e ?? eiioeaio?aoe?? 0.3 iieue/e (oaae.5, ?en.2). A oeeo oiiaao neioaciaaii iiii- ? aeeao??e (,(-AeIAE oa ae?eie?a, ?o aoaeiaa i?aeoaa?aeaeo?oueny ?*-niaeo?ineii?/ii, a o?ceei-o?i?/i? oa?aeoa?enoeee iaaaaeaii a oaae.6. I?yiie?i?eia caeaaei?noue i?ae lg(N0een/Neen) ? /anii i?iaaaeaiiy i?ioeano na?ae/eoue i?i oa, ui oaeaee?noue aeo?aoe (,(-AeIAE caaeia?eueii iieno?oueny e?iaoe/iei ??aiyiiyi ia?oiai ii?yaeeo. Cia/aiiy eiinoaio oaeaeeino? ?aaeoe?? ia?oiai ii?yaeeo e?i?eii caeaaeaoue a?ae eiioeaio?aoe?? eaoae?caoi?a aei cia/aiiy inoaiiuei? 0.3 iieue/e (?en. 2). ?acii c oei, oaeaee?noue ?aaeoe?? aoa?eo?eaoe?? ia caeaaeeoue a?ae eiioeaio?aoe?? ? aoaeiae ae?eieth, oiaoi aeo?aoa (,(-AeIAE ia? ioeueiaee ii?yaeie ii nie?oo. Oaaeeoey 5. Aeoiaee aee-(,(-aeeiaoeeae?eeaoo oao?aiaoeeaiae?eieth (OIA) ? cia/aiiy eiinoaio oaeaeeino? ?aaeoe?? ia?oiai (k) ? ae?oaiai ii?yaeeo (kaeni) aoa?eo?eaoe?? (,(-AeIAE OIA a aaicie? a i?enooiino? ??cieo eaoae?caoi??a (eiioeaio?aoe?y eaoae?caoi?a 0.3 iieue/e) Eaoae?caoi? EO-2/8 I3?I4, n-ONE H2SO4 Aeo?ae, % 82.7 77.3 93.9 85.2 k.105, n-1 1.40 2.37 6.61 8.34 kaeni.105, e/iieue.n 4.67 7.9 22.03 27.8 Oaaeeoey 6. O?ceei-o?i?/i? oa?aeoa?enoeee oa aeoiaee iaea?aeaieo iiii- oa aeeao???a, ooai?aieo (,(-AeIAE oa ae?eieyie. Ae?eieue nD20 d420, a/ni3 Iieaeoey?ia ?ao?aeoe?y, MR Ai?no iniiaii? ?a/iaeie, Aeo?ae, % ciaeae. ia/ene. % IIIIAO??E Oao?aiaoeeaiae?eieue 1.4620 1.0171 46.49 46.67 97.9 90.8 Aeeaoeeaiae?eieue 1.4629 1.0789 47.99 48.45 97.5 89.3 O?eaoeeaiae?eieue 1.4656 1.0865 59.10 59.53 97.4 88.0 AeEAO??E Oao?aiaoeeaiae?eieue 1.4684 1.0295 69.34 69.68 98.7 93.9 Aeeaoeeaiae?eieue 1.4798 1.0793 71.04 71.46 98.4 92.5 O?eaoeeaiae?eieue 1.4804 1.0869 82.13 82.54 98.3 90.9 Oaeei /eiii, oaeaee?noue aeo?aoe (,(-AeIAE a aaicie? c acaio?iiiith a?aeaiieith aiaee i?e eiioeaio?aoe?? eaoae?caoi?a aei 0.3 iieue/e iiaeia iienaoe ianooiiei ??aiyiiyi: W=-kaeni[(,(-AeIAE][i-ONE] (6), aea kaeni - aenia?eiaioaeueia eiinoaioa oaeaeeino? ?aaeoe??, e/iieue.n. Iaea?aeai? ?acoeueoaoe iiaeia ?ioa?i?aooaaoe c oi/ee ci?o iiiiiieaeoey?iiai iaoai?cio ?aaeoe?? aoa?eo?eaoe?? aeaiaoiiieo nie?o?a (,(-AeIAE c ?ic?eaii ca’yceo aoeee - eenaiue: E? (NI3)2N=NINII+I2 (?) k2 (NI3)2N=NINII+I2 (( (NI3)2N=NINI+ + I2I (??) k3 (NI3)2N=NINI++ IIRII (( (NI3)2N=NINIIRII + I+ (???) k4 (NI3)2N=NINI+ + (NI3)2N=NINIIRII (( (( (NI3)2N=NINIIRIINNIN=(NI3)2 + I+ (?V) ?en. 2. Caeaaei?noue aenia?eiaioaeueii? eiinoaioe oaeaeeino? ia?oiai ii?yaeeo ?aaeoe?? aoa?eo?eaoe?? OIA (,(-AeIAE a?ae eiioeaio?aoe?? eaoae?caoi?a i-ONE a aaicie?, ni?aa?aeiioaiiy aaicie:OIA: (,(-AeIAE=4:1:2.2. Ca?aeii oe??? noaie aeeiai?ea iaa?iiaaeaeaiiy iiii- (IAeIA) ? aee-(,(-aeeiaoeeae?eeaoo (AeAeIA) OIA iieno?oueny e?iaoe/ieie ia?aiao?aie aeo?aoe (,(-AeIAE oa a?aeiioaiiyi eiinoaio oaeaeeinoae aca?iiae?? ?iio aoeee?th c aeaiaoiiiei nie?oii oa IAeIA oeueiai nie?oo. Eiinoaioa kA= k3 / k4 aei??aith? a?aeiioaiith iaeneiaeueii? eiioeaio?aoe?? IAeIA OIA aei eiioeaio?aoe?? OIA, yea a?aeiia?aea? oe?e iaeneiaeuei?e eiioeaio?aoe??. ?ic?aooiee aeathoue aaee/eio kA=1.02. Oea icia/a?, ui eiinoaioa oaeaeeino? ?aaeoe?? ?iio aoeee?th c ae?eieai i?eaeecii aei??aith? eiinoaio? oaeaeeino? eiai aca?iiae?? c iiiiao??ii. Iaeiae oea iaeieiia??ii, ine?eueee ae?eieue ia? aea? ooieoe?iiaeuei? a?oie, a iiiiao?? - iaeio, ? eiinoaioa oaeaeeino? ?aaeoe?? ?iio aoeee?th c ae?eieai iiaeiia aooe oi/a a o aeaa ?ace a?eueoa, i?ae c iiiiao??ii. E??i oeueiai, ?ic?aooiie aeeiai?ee iaa?iiaaeaeaiiy i?iaeoeo?a ?aaeoe?? c aeei?enoaiiyi cia/aiue k ? kA aeaco? ia oa, ui nii/aoeo ?ic?aooieiaa eiioeaio?aoe?y iiiiao??o cia/ii iaioa, i?ae aenia?eiaioaeueia, a iio?i aaea nooo?ai ia?aaaaea? ??. Oea na?ae/eoue i?i ?nioaaiiy aeiaeaoeiaiai oeyoo ooai?aiiy aeeao??o c iiiiao??o e??i eiai aca?iiae?? c ?iiii aoeee?th. A?aeiii, ui iiiiao?? iiaea aeeni?iii?oe?iioaaoe ia aeeao?? ? ae?eieue (AE): kae 2(NI3)2N=NINIIRII (( (NI3)2N=NINIIRIINNI=N(NI3)2+IIRII Anoaiiaeaii, ui ocaiaeaeaiiy aenia?eiaioaeueieo aeaieo c ?acoeueoaoaie ?ic?aooie?a a?aeaoaa?oueny oiae?, yeui i?eionoeoe ia?aa?a ?aaeoe?? aeeni?iii?oe?iioaaiiy /a?ac i?ii?aeia ooai?aiiy aaeoeoo iiiiao??o c aeeao??ii ca a?oooi ?aaeoe??th: 2kae (NI3)2N=NINIIRII + (NI3)2N=NINIIRIINNI=N(NI3)2 (( 3 1 (( ( (NI3)2N=NINIIRIINNI=N(NI3)2 + ( IIRII (V) 2 2 Iaea?aeaia noaia iieno?oueny nenoaiith ??aiyiue: W((,(-AeIAE)= (ke[(,(-AeIAE] (7) kA[AE] W(AE)= ke[(,(-AeIAE][i-ONE] (((((((( + kae[IAeIA][AeIA] (8) kA[AE]+[IAeIA] kA[AE]([IAeIA] W(IAeIA)=ke[(,(-AeIAE][i-ONE] ((((((( -2 kae[AeAeIA][IAeIA] (9) kA[AE]+[IAeIA] [IAeIA] W(AeAeIA)=ke[(,(-AeIAE][i-ONE]((((((( +kae[AeAeIA][IAeIA] (10) kA[AE]+[IAeIA] c ianooiieie cia/aiiyie eiinoaio oaeaeeino? ke= 0.000069 n-1, ui i?eaeecii aei??aith? aenia?eiaioaeueiiio cia/aiith k=0.0000661 n-1 (oaae.5); kA= 2.19; kae= 0.00032 e/iieue.n i?e [i-ONE] ( 0.3 iieue/e. E?iaoe/i? e?ea? ?aaeoe?? aoa?eo?eaoe??, ?ic?aoiaai? ca iaea?aeaieie ??aiyiiyie, a?aeiia?aeathoue aenia?eiaioaeueiei cia/aiiyi (?en.3). ?en. 3. ?ic?aoiaai? e?iaoe/i? e?ea? aeo?aoe (,(-AeIAE, OIA oa iaa?iiaaeaeaiiy ao???a aeey ?aaeoe?? aoa?eo?eaoe?? i?e iaea?aeaii? oao?aiaoeeai-aee-(,(-aeeiaoeeae?eeaoo. Oi/eaie iicia/aii aenia?eiaioaeuei? cia/aiiy.1- aeo?aoa (,(-AeIAE; 2 - aeo?aoa OIA; 3 - iaa?iiaaeaeaiiy oao?aiaoeeai-iiii-(,(-aeeiaoeeae?eeaoo; 4 - iaa?iiaaeaeaiiy oao?aiaoeeai-aee-(,(-aeeiaoeeae?eeaoo. O oinoiio ?icae?e? aeine?aeaeaii caeaoi?noue ao???a (,(-AeIAE aei ?aaeeeaeueii? aiii- oa ni?aiie?ia?ecaoe?? Iaoiaeii OOO, a oaeiae ia iniia? niaeo??a II? anoaiiaeaii, ui iaoeeiaee ao?? (,(-AeIAE aiiiiie?ia?o ia ooai?th?, a ae?eiaee ao?? iie?ia?eco?oueny aeeeth/ii ii iiaea?eiiio ca’yceo nie?oiai? a?oie. Iaoiaeii II? anoaiiaeaii, ui iaoeeiaee ao?? o ?aaeoe?th ni?aiie?ia?ecaoe?? c noe?ieii ia anooia?, a ae?eiaee ao?? ooai?th? ni?aiie?ia? ii iiaea?eiiio ca’yceo nie?oiai? a?oie, caeeoath/e a?eueiei iiaea?eiee ca’ycie eeneioii? a?oie. Aeineoue aenie? cia/aiiy iieaeoey?ieo ian (~ 3.105) ni?aiie?ia??a na?ae/aoue i?i oa, ui a i?ioean? iie?ia?ecaoe?? ia niinoa??aa?oueny a?ae/ooia ia?aaea/a eaioethaa ia (-aoaeaoeaaee aoii ae?eiai? a?oie. Eiinoaioe ni?aiie?ia?ecaoe?? aecia/aeenue a?ao?/iei ?ica’ycaiiyi ??aiyiiy Oaeiiaia-?inna i?e eiiaa?n?yo iiiiia??a, ye? iaio?, i?ae 10%. Iaea?aeaii ianooii? cia/aiiy rnoe?ieo=5.445 ? rae.ao.=0.121, ui na?ae/eoue i?i oa, ui i?e an?o ni?aa?aeiioaiiyo iiiiia??a iaea?aeaiee ni?aiie?ia? caaaa/aiee noe?ieii. Cia/aiiy Qao=0.11, aao=-0.15 noaie Aeo?ay-I?aena aeey ae?eiaiai ao??o (,(-AeIAE aeacothoue ia oa, ui aeeaae ?aciiainii? neeaaeiai? aeaeo?iiiiai aieeao cai?nieea o iieaeoe? ao??o iacia/iee. A?eueo aaaiiei ? aieea ?iaeoeoe?eii? neeaaeiai?. Oaeei /eiii, aeiaaaeaii, ui iiaea?eiee ca`ycie eeneioiiai oa?oioaaiiy a iio?aeieo (,(-AeIAE ia noeeueiee aei iie?ia?ecaoe?? ? neeaaei? ao??e oe??? eeneioe anooiathoue o ?aaeoe?? aiii- oa ni?aiie?ia?ecaoe?? o?eueee i?e iayaiino? iiaea?eiiai ca`yceo a nie?oiaiio caeeoeo. Oea aea? iiaeeea?noue iiaeeo?eoaaoe ni?aiie?ia?e, aeei?enoiaoth/e a?eueiee iiaea?eiee ca’ycie o eeneioi?e a?oi?. Io?eiaii iiceoeai? ?acoeueoaoe i?e aeei?enoaii? ao???a (,(-AeIAE ye ni?aiiiiia??a o neeaae? oioiiie?ia?ieo eiiiiceoe?e c ie?aio?aoaiae?eeaoii, ye? canoiniaothoueny aeey iaea?aeaiiy iie?ia?ieo iaia?ai c aenieith naeaeoeai?noth, no?ee?noth aei aaeoa??e oa i?aai?/ieo ?ic/eiiee?a. AENIIAEE 1. Aaeineiiaeaii iaoiaee neioaco aeo?aeieo ?a/iaei - (-iaoee- (-aooe?ieaeoiio oa (,(-AeIAE, aeoiaey/e c i?iieneiai aeinooiii? ne?iaeie - aoeaoiio, a ?acoeueoao? /iai i?aeaeuaii aeo?ae eaeoiio c 75% aei 92%, a eeneioe c 72% aei 94%. 2. Aia?oa neioaciaaii 18 iiaeo ao???a (,(-AeIAE, aecia/aii ?o o?ceei-o?i?/i? oa?aeoa?enoeee oa iiaeeeaino? i?aeoe/iiai canoinoaaiiy. ?ic?iaeai? iaoiaee neioaco oa?aeoa?ecothoueny aenieeie (iiiaae 90%) aeoiaeaie oa /enoioith oe?eueiaeo i?iaeoeo?a. Anoaiiaeaii oeyoe i?aeoe/iiai canoinoaaiiy neioaciaaieo ao???a. 3. Aea/aiiy e?iaoe/ieo caeiiii??iinoae ?aaeoe?? aeeiaie?co (,(-AeIAO nie?oaie ??cii? aoaeiae aeicaieeei anoaiiaeoe, ui ia oaeaee?noue i?ioeano aieeaathoue ia o?eueee aeaeo?iii?, a e nieueaaoaoe?ei? ia?aiao?e nie?oo iaa?oue i?e aea?iiey?iiio ni?aa?aeiioaii? ?aaaaio?a. 4. Anoaiiaeaii, ui ia oaeaee?noue aeeiaie?co (,(-AeIAO aecia/aeueiee ? niia?eueithth/ee aieea ia? iniiai?noue ?ic/eiieea aiane?aeie eiieo?oth/i? aca?iiae?? c iieaeoeith oei?aia?ae?eaeo iniiaiiai ?ic/eiieea oa nie?oo i?e ooai?aii? i?ii?aeiiai eiiieaeno c ia?aiinii ca?yaeo. 5. Aia?oa iieacaii, ui e?iaoeea i?ioeano aeeiaie?co (,(-AeIAO caaeia?eueii iieno?oueny ??aiyiiyi I?oaae?na-Iaioai. Oea i?aeoaa?aeaeo? cai?iiiiiaaiee iaoai?ci i?io?eaiiy ?aaeoe?? aeeiaie?co oei?aia?ae?eaeo /a?ac i?ii?aeio noaae?th ooai?aiiy aeiii?ii-aeoeaioi?iiai eiiieaeno c ia?aiinii ca?yaeo. 6. Anoaiiaeaii, ui ?aaeoe?y aoa?eo?eaoe?? ae?eie?a (,(-AeIAE a i?enooiino? eeneioieo eaoae?caoi??a c acaio?iiiith a?aeaiieith aiaee i?io?ea? ca iiiiiieaeoey?iei iaoai?ciii. Cai?iiiiiaaii iinoaae?eio noaio i?io?eaiiy ?aaeoe??. Nenoaia e?iaoe/ieo ??aiyiue, neeaaeaieo ia iniia? cai?iiiiiaaii? noaie aaeaeaaoii iieno? aenia?eiaioaeuei? aeai?. Aia?oa iieacaii, ui ?aaeoe?y aoa?eo?eaoe?? ae?eie?a (,(-AeIAE i?io?ea? /a?ac noaae?th aeeni?iii?oe?iioaaiiy iiiiao??o. 7. I?aeoaa?aeaeaii, ui aaaaeaiiy aeaio cai?niee?a o (-iieiaeaiiy aei ea?aieneeueii? a?oie ae?eeiai? eeneioe i?aeoe/ii iiai?noth i?aaeth? caeaoi?noue iio?aeieo (,(-AeIAE aei aiii- oa ni?aiie?ia?ecaoe??. Neeaaei? ao??e oe??? eeneioe anooiathoue o ?aaeoe?? aiii- oa ni?aiie?ia?ecaoe?? o?eueee i?e iayaiino? iie?ia?ecaoe?eiicaeaoiiai iiaea?eiiai ca`yceo a nie?oiaiio caeeoeo. Iiiiao??e ae?eie?a ? (,(-AeIAE iiaeia aeei?enoiaoaaoe ye ni?aiiiiia?e o ?aaeoe?yo iie?eiiaeainaoe?? c ooai?aiiyi aenieiiieaeoey?ieo niieoe. Iniiaiee ci?no aeena?oaoe?? iioae?eiaaiee o ?iaioao: 1. Ia?oaeie A.A., Iaeaoaiiue TH.E., Iaeeo?a ?.A., Ie?ea ss.I., sso/eoei E.E. Iniaaiiinoe eeiaoeee aeeiaieeca oei?aiaeae?eaea (,(-aeeiaoeeae?eeiaie eeneiou.// AEo?iae i?aaie/aneie oeiee.- 1998.- O. 34.Aui. 10.- N. 1471-1480. 2. Iaeaoaiiee TH.?., Ia?oaeie A.I., Iae?o?a ?.A., sso/eoei E.E. Aoaeoe nieueaaoaoe?? i?e aca?iiae?? (,(-aeeiaoeeae?eei?eoei?eaeo c? nie?oaie.// Aeiiia?ae? IAI Oe?a?ie.- 1998.- ? 11.- N. 145-149. 3. Iaeaoaiiee TH.?., Ia?oaeie A.A., sso/eoei E.E., Iaeaeueiiia A.I., Eieaiaei A.TH. Neioac e iieeia?ecaoeey yoe?ia (,(-aeeiaoeeae?eeiaie eeneiou.// Oe?a?inueeee o?i?/iee aeo?iae.- O. 64.- ? 9-10.- 1998.- N. 131-134. 4. Iaeaoaiiee TH.?., Ia?oaeie A.I., sso/eoei E.E., Eiaaeuenueeee ss.I. Aecia/aiiy (,(-aeeiaoeeae?eeiai? oa nieyii? eeneio i?e ?o noi?ni?e i?enooiino?// A?niee AeO "Euea?anueea iie?oaoi?ea". O?i?y, oaoiieia?y ?a/iaei oa ?o canoinoaaiiy.- 1996.- ? 298.- C.37-38. 5. Eioiae/ O.C., Ia?oaeie A.I., Iaeaoaiiee TH.?., sso/eoei E.E. Neioac oei?aia?ae?eaeo (,(-aeeiaoeeae?eeiai? eeneioe// A?niee AeO "Euea?anueea iie?oaoi?ea". O?i?y, oaoiieia?y ?a/iaei oa ?o canoinoaaiiy. 1997.- ? 316.- C.27-29. 6. Iaeaoaiiee TH.?., Ia?oaeie A.I., sso/eoei E.E., Iaeaeueiiia A.I. Aeine?aeaeaiiy ni?aiie?ia?ecaoe?eii? caeaoiino? ao???a (,(-aeeiaoeeae?eeiai? eeneioe.// A?niee AeO "Euea?anueea iie?oaoi?ea". O?i?y, oaoiieia?y ?a/iaei oa ?o canoinoaaiiy.(tha?eaeiee).- 1997.- ? 332.- C.91-94. 7. Naiaithe ?.A., Oethiei O.?., Iaeaoaiiee TH.?. Aiae?oe/iee eiio?ieue a i?ioean? iaea?aeaiiy ae?eeiaeo iiiiia??a.// A?niee AeO "Euea?anueea iie?oaoi?ea". O?i?y, oaoiieia?y ?a/iaei oa ?o canoinoaaiiy.- 1997.- ? 316.- C.26. 8. Iaeaoaiiee TH.?., Ia?oaeie A.I., sso/eoei E.E., Eiaaeuenueeee ss.I. Aieea no?oeoo?e nie?oo ia oaeaee?oue aeeiaie?co (,(-aeeiaoeeae?eeiai? eeneioe.// Oace XVII Oe?a?inueei? eiioa?aioe?? c i?aai?/ii? o?i??. Oa?e?a, 3-6.10.1995.- O.2.- N. 443. 9. sso/eoei E.E., Iaeaoaiiee TH.?., Ia?oaeie A.I., Eiaaeuenueeee ss.I. Noi?nia aecia/aiiy (,(-aeeiaoeeae?eeiai? oa nieyii? eeneio// Oace V iaoeiai-i?aeoe/ii? eiioa?aioe?? «Euea?anuee? o?i?/i? /eoaiiy». 25-27.05.1995.- N. 135. 10. Iaeaoaiiee TH.?., Ia?oaeie A.I., Iae?o?a ?.A., Ie??a ss.I. E?iaoe/i? caeaaeiino? oa iaoai?ci aeeiaie?co (,(-aeeiaoeeae?eei?eoei?eaeo.// Oace VI iaoeiai-i?aeoe/ii? eiioa?aioe?? «Euea?anuee? o?i?/i? /eoaiiy». 29-30.05.1997.- N. 47. 11. Naiaithe ?.A., Iaeaoaiiee TH.?., Ia?oaeie A.I., sso/eoei E.E. Aacio?iiaoia?ao?/iee iaoiae aiae?co (,(-aeeiaoeeae?eeiaeo ao???a.// Oace Anaoe?a?inueei? eiioa?aioe?? c aiae?oe/ii? o?i?? Oaeai?iae, 15-17. 09.1998.- N.96. 12. Iaeaoaiiee TH.?., Ia?oaeie A.I., sso/eoei E.E., Naiaithe ?.A. Oai?aoe/i? ? i?aeoe/i? iniiae neioaco (,(-aeeiaoeeae?eeao?a.// Oace XVIII Oe?a?inueei? eiioa?aioe?? c i?aai?/ii? o?i??. Aei?i?iiao?ianuee. 6-9.10.1998.- N. 146. Iaeaoaiiee TH.?. Neioac ? oa?aeoa?enoeea iio?aeieo (,(-aeeiaoeeae?eeiai? eeneioe.- ?oeiien. Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa o?i?/ieo iaoe ca niaoe?aeuei?noth 02.00.03 - i?aai?/ia o?i?y.- Aea?aeaaiee oi?aa?neoao «Euea?anueea iie?oaoi?ea», Euea?a, 1999. Aeena?oaoe?y i?enay/aia aeine?aeaeaiith iaoiae?a neioaco oa aeanoeainoae iio?aeieo (,(-aeeiaoeeae?eeiai? eeneioe. Aea/aii o?ceei-o?i?/i? oa?aeoa?enoeee oa i?aeoaa?aeaeaii aoaeiao 18-oe neioaciaaieo iiaeo niieoe - ao???a (,(-aeeiaoeeae?eeiai? eeneioe. Aaeineiiaeaii iaoiaee neioaco aeo?aeieo ?a/iaei - (-iaoee-(-aooe?ieaeoiio ? (,(-aeeiaoeeae?eeiai? eeneioe a ?acoeueoao? /iai i?aeaeuaii aeo?ae eaeoiio c 75% aei 92%, a eeneioe c 72% aei 94%.Aea/aii aieea aoaeiae ? i?e?iaee nie?o?a oa ?ic/eiiee?a ia oaeaee?noue ?aaeoe?? aeeiaie?co oei?aia?ae?eaeo (,(-aeeiaoeeae?eeiai? eeneioe iaeiiaoiiieie nie?oaie. Anoaiiaeaii iaoai?ci oe??? ?aaeoe??. Aeine?aeaeaii aieea ??cieo oaeoi??a ia e?iaoeeo ?aaeoe?? aoa?eo?eaoe?? (,(-aeeiaoeeae?eeiai? eeneioe ae?eieyie o ia??aiiaaaeieo oiiaao c acaio?iiiith a?aeaiieith aiaee oa cai?iiiiiaaii iinoaae?eiee iaoai?ci oe??? ?aaeoe??. Aeine?aeaeaii iie?ia?ecaoe?eio caeaoi?noue iio?aeieo (,(-aeeiaoeeae?eeiai? eeneioe ? aecia/aii iiaeeeaino? ?o i?aeoe/iiai canoinoaaiiy. Eeth/ia? neiaa: (-iaoee-(-aooe?ieaeoii, (,(-aeeiaoeeae?eeiaa eeneioa, (,(-aeeiaoeeae?eei?eoei?eae, ao??e (,(-aeeiaoeeae?eeiai? eeneioe, neioac, aeeiaie?c, aoa?eo?eaoe?y, ei?aeyoe?eiee aiae?c. Iaeaoaiiue TH.E. Neioac e oa?aeoa?enoeea i?iecaiaeiuo (,(-aeeiaoeeae?eeiaie eeneiou.- ?oeiienue. Aeenna?oaoeey ia nieneaiea iao/iie noaiaie eaiaeeaeaoa oeie/aneeo iaoe ii niaoeeaeueiinoe 02.00.03 - i?aaie/aneay oeiey.- Ainoaea?noaaiiue oieaa?neoao «Eueaeanueea iieeoaoieea», Eueaia, 1999. Aeenna?oaoeey iinayuaia enneaaeiaaieth iaoiaeia neioaca e naienoa i?iecaiaeiuo (,(-aeeiaoeeae?eeiaie eeneiou. Eco/aiu oeceei-oeie/aneea oa?aeoa?enoeee e iiaeoaa?aeaeaii no?iaiea 18-oe neioace?iaaiiuo iiauo niaaeeiaiee - yoe?ia (,(-aeeiaoeeae?eeiaie eeneiou. Oniaa?oainoaiaaiu iaoiaeu neioaca enoiaeiuo niaaeeiaiee - (-iaoee-(-aooe?ieaeoiia e (,(-aeeiaoeeae?eeiaie eeneiou a ?acoeueoaoa /aai iiauoai auoiae eaeoiia n 75% aei 92%, a eeneiou n 72% aei 92%. Eco/aii aeeyiea no?iaiey e i?e?iaeu nie?oia e ?anoai?eoaeae ia nei?inoue ?aaeoeee aeeiaieeca oei?aiaeae?eaea (,(-aeeiaoeeae?eeiaie eeneiou iaeiiaoiiiuie nie?oaie. Onoaiiaeai iaoaieci ?aaeoeee. Enneaaeiaaii aeeyiea ?acee/iuo oaeoi?ia ia eeiaoeeo ?aaeoeee yoa?eoeeaoeee (,(-aeeiaoeeae?eeiaie eeneiou aeeeieyie a ia?aaiiaaniuo oneiaeyo n acaio?iiiie ioaiieie aiaeu e i?aaeeiaeai iinoaaeeeiue iaoaieci yoie ?aaeoeee. Enneaaeiaaia iieeia?ecaoeeiiiay niiniaiinoue i?iecaiaeiuo (,(-aeeiaoeeae?eeiaie eeneiou e ii?aaeaeaiu aiciiaeiinoe eo i?aeoe/aneiai eniieueciaaiey. Eeth/aaua neiaa: (-iaoee-(-aooe?ieaeoii, (,(-aeeiaoeeae?eeiaay eeneioa, (,(-aeeiaoeeae?eeieeoei?eae, yoe?u (,(-aeeiaoeeae?eeiaie eeneiou, neioac, aeeiaieec, yoa?eoeeaoeey, ei??aeyoeeiiiue aiaeec. Oglashennyi Y.I. Synthesis and characteristic of (,(-dimethylacrylic acid derivatives.- Manuscript. The dissertation for a Candidate degree in Chemical Sciences in speciality 02.00.03 - Organic Chemistry, State University «Lvivska Polytechnika», Lviv, 1999. The derivatives of (,(-dimethylacrylic acid can be applied as initial compounds for preparation of useful substances - untoxic insecticides, anti-inflammatory preparations, pesticides, (-aminoacids, anti-juvenile hormones, aromatic parfumer components. However, the practical using of the above mentioned derivatives is limited for lack of simple and available methods of their obtaining. Therefore the presented dissertation is dedicate to improvement of synthesis methods of the initial compounds - (-methyl-(-butyrolactone and (,(-dimethylacrylic acid, working out preparation methods of the acid derivatives (such as chloride, esters of monoatomic alcoholos and glycols), investigation of kinetic regularity and mechanism of derivatives obtaining process, determination of structure and physico-chemical characteristics of the compounds, as well as ways of their practical using. The methods of initial substances ((-methyl-(-butyrolactone, (,(-dimethylacrylic acid) synthesis from available raw material (acetone) are improved. The yields raise from 75% to 92% for lactone and from 72% to 94% for (,(-dimethylacrylic acid. There are two alternative ways of chloride of (,(-dimethylacrylic acid realized. (,(-Dimethylacrylic acid chloride can be obtained by interaction of thionyl chloride with (,(-dimethylacrylic acid or (-methyl-(,(-butyrolactone. The (,(-dimethylacrylic acid chloride alcoholysis reaction has been investigated and its kinetic has been described. The reagent ratio, structure and nature of alcohols and solvents influence on the alcoholysis rate have been studied in details for the first time. It is shown that kinetic regularity of the process can be adequately described by using of combined of Hammet-Taft and Koppel-Palm equation only. Such using allows to take into account simultaneously electronic and solvatation alcohols parameters. The investigation of solvent nature influence on the alcoholysis process rate allows to reveal the most essential decelerating effect of solvent basicity as a result of competitive interaction of basic solvents with a chloride molecule during intermediate complex formation. The satisfactory description of alcoholysis reaction by Michaelis-Menten equation is determined for the first time. This dependence confirms proposed mechanism of the chloride alcoholysis reaction proceeding by intermediate stage of donor-acceptor charge transfer complex formation. The proceeding of glycols esterification by (,(-dimethylacrylic acid in the presence of acidic catalysts with azeotropic drying according to monomolecular mechanism have been determined. The proposed esterification process scheme is adequately described in stage by the system of kinetic equation. The obtained experimental data correspond to calculated kinetic curves. The monoester disproportionation is proved as one of esterification stages in the first time. The presence of two methyl substituents on (-position according to carboxyl group of acrylic acid inhibits ability of (,(-dimethylacrylic acid derivatives for homo- and copolymerization completely. The esters of (,(-dimethylacrylic acid can be homo- and copolymerized in the presence of polymerizanble double bond in the residue only. Such copolymers have vacant functional group - acrylic double bond. Obtained copolymer of (,(-dimethylacrylic acid allyl ester and styrene is applied for preparation of semipercolate membranes, which are characterized be high steadiness to bacterium and organic solvents. Monoesters of glycols and (,(-dimethylacrylic ester can be used as comonomers for copolymers synthesis by polycondensation reaction. Key words: (-methyl-(-butyrolactone, (,(-dimethylacrylic acid, (,(-dimethylacrylic acid chloride, esters of (,(-dimethylacrylic acid, synthesis, alcoholysis, esterification, correlation analysis. PAGE

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