Молекулярна структура та конформаційний аналіз шестичленних дигідроциклів: Автореф. дис… д-ра хім. наук / О.В. Шишкін, Харк. держ. ун-т. — Х., 1999.

OA?E?ANUeEEE AeA?AEAAIEE OI?AA?NEOAO

OAeE 541: 548.73: 546.636

Oeoe?i Ieaa Aaea??eiae/

Iieaeoey?ia no?oeoo?a oa eiioi?iaoe?eiee aiae?c oanoe/eaiieo
aeea?ae?ioeeee?a

02.00.03- i?aai?/ia o?i?y

AAOI?AOA?AO

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy aeieoi?a o?i?/ieo iaoe

Oa?e?a — 1999

Aeena?oaoe??th ? ?oeiien

?iaioa aeeiiaia a ?inoeooo? iiiie?enoae?a Iaoe?iiaeueii? Aeaaeai?? iaoe
Oe?a?ie

Io?oe?ei? iiiiaioe /eai-ei?aniiiaeaio IAI Oe?a?ie, aeieoi? o?i?/ieo

iaoe, i?ioani? Eaiaeia Aa?aa?o Eaiiiae/,

caa?aeoaa/ a?aeae?eo O?ceei-o?i?/iiai ?inoeoooo ?i I.A. Aiaaonueeiai IAI
Oe?a?ie (i. Iaeana)

aeieoi? o?ceei-iaoaiaoe/ieo iaoe Iie?uoe A?eaae?e Iao?iae/, i?ioani?
Iaoe?iiaeueiiai oaoi?/iiai oi?aa?neoaoo “Ee?anueeee iie?oaoi?/iee
?inoeooo”

aeieoi? o?i?/ieo iaoe Eiaaeaiei Na?a?e Ieeieaeiae/, i?ioani?
Oe?a?inueei? oa?iaoeaaoe/ii? aeaaeai?? (i.Oa?e?a)

I?ia?aeia onoaiiaa ?inoeooo i?aai?/ii? o?i?? IAI Oe?a?ie, a?aeae?e
o?ceei-o?i?/ieo iaoiae?a aeine?aeaeaiiy (i. Ee?a)

Caoeno a?aeaoaeaoueny “01” aeiaoiy 1999 ?ieo i “14” aiae. ia can?aeaii?
niaoe?ae?ciaaii? a/aii? ?aaee Ae 064.051.14 o Oa?e?anueeiio aea?aeaaiiio
oi?aa?neoao? (310077, i.Oa?e?a, ie.Naiaiaee, 4, aoae. 7-80).

C aeena?oaoe??th iiaeia iciaeiieoeny o Oeaio?aeuei?e iaoeia?e
a?ae?ioaoe? Oa?e?anueeiai aea?aeaaiiai oi?aa?neoaoo (310077, Oa?e?a,
ie.Naiaiaee, 4).

Aaoi?aoa?ao ?ic?neaii “16” eeiiy 1999 ?ieo

A/aiee nae?aoa? niaoe?ae?ciaaii? a/aii? ?aaee Eia?iiaa E.I.

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue oaie Oanoe/eaii? aeea?ae?ioeeeee ? iaeieie c iaea?eueoeo
eean?a i?aai?/ieo niieoe, yeee ia? aaaeeeaa cia/aiiy ye c oai?aoe/ii?,
oae ? c i?aeoe/ii? oi/ee ci?o. Oe? niieoee aenooiathoue ?ioa?iaae?aoaie
neioaco aaaaoueio iane/aieo oa a?iiaoe/ieo nenoai. Oiio ?icoi?iiy
i?inoi?iai? aoaeiae oa eiioi?iaoe?eieo oa?aeoa?enoee oaeeo iieaeoe ae?ae
iaiao?aeii aeey iiooeo iaea?eueo ?aoe?iiaeueieo oeyo?a neioaco iiaeo
niieoe.

Oanoe/eaii? aeea?ae?ioeeeee aeeeeeathoue aaee/aciee ?ioa?an ? c
i?aeoe/ii? oi/ee ci?o. Aaaaoi i?aaenoaaiee?a oeueiai eeano i?aai?/ieo
niieoe i?iyaeythoue ??ciiiai?oio a?ieia?/io aeoeai?noue. *anoeiai
a?ae?iaai? e?eueoey i?noyoueny o neeaae? /eneaieo i?e?iaeieo niieoe,
oaeeo ye iniiae ioeea?iiaeo eeneio, noa?i?aei? ai?iiie, a?oai?ie oa ?i.
Ia iniia? aeea?ae?ioeeee?a neioaciaaii aaeeeo e?euee?noue oioi- ?
oa?iio?iiieo iaoa??ae?a, aa?aiee?a, ethi?iioi??a, iie?ia?ieo iaoa??ae?a
c? niaoe?aeueieie aeanoeainoyie. O?ceei-o?i?/i? aeanoeaino? oeeo niieoe
aaaaoi o /iio aecia/athoueny naia i?inoi?iaith aoaeiaith oa
eiioi?iaoe?eieie oa?aeoa?enoeeaie oanoe/eaiieo aeea?ae?ioeeee?a.
Noai?aiiy iiaeo iaoa??ae?a ? e?ea?nueeeo i?aia?ao?a iaiiaeeeaa aac
?icoi?iiy caeiiii??iinoae iieaeoey?ii? no?oeoo?e aeaiiai eeano
i?aai?/ieo niieoe.

Iaoa ? caaea/? aeine?aeaeaiiy Iaoith ?iaioe ? anoaiiaeaiiy iniiaieo
caeiiii??iinoae i?inoi?iai? aoaeiae ? eiioi?iaoe?eii? aeeiai?ee
oanoe/eaiieo aeea?ae?ioeeee?a oa oaeoi??a, ye? aecia/athoue noa?aio?i?th
oaeeo iieaeoe.

Iaoeiaa iiaecia iaea?aeaieo ?acoeueoao?a Anoaiiaeaii iniiai?
caeiiii??iino? i?inoi?iai? aoaeiae ? eiioi?iaoe?eii? iiaaae?iee
oanoe/eaiieo aeea?ae?ioeeee?a oa aecia/aii oaeoi?e, ye? aecia/athoue
no?oeoo?o eiaeiiai oeio /anoeiai a?ae?iaaieo e?eaoeue.

A?aee?eoi, ui an?i oeiai oanoe/eaiieo aeea?ae?ioeeee?a, iacaeaaeii a?ae
iayaiino? iane/aiiai aoiio aoaeaoeth a oeeee?, i?eoaiaiia aeniea
eiioi?iaoe?eia aio/e?noue, yea iaoiiaeaia oiieei aaeainii noa?e/ieo oa
aeaeo?iiieo aca?iiae?e, ui noaa?e?cothoue ieaia?io aai iaieineo
eiioi?iaoe?th /anoeiai a?ae?iaaiiai e?eueoey.

Iieacaii ae??oaeueio ?ieue oa?aeoa?o oeeee?/ii? noi?yaeaii? nenoaie o
eiioi?iaoe?ei?e aeeiai?oe? aeea?ae?ioeeee?a, ui ia i?noyoue iane/aieo
aoii?a aoaeaoeth a e?eueoe?.

Anoaiiaeaii iiae?ai?noue -aeaeo?iiii? no?oeoo?e o ?yaeao 1,4- oa
1,2-aeea?ae?ioeeee?a.

Aia?oa aeyaeaii aenieo eiioi?iaoe?eio aio/e?noue i??ei?aeeiiaeo oeeee?a
o iieaeoeao iniia ioeea?iiaeo eeneio, yea caa??aa?oueny i?e ooai?aii?
Oionii-E??e?anueeeo ia? iniia.

Iieacaii iiaeeea?noue aieeao eiioi?iaoe?eii? iaaei?noeino?
aeea?ae?ioeeee?a ia o?ceei-o?i?/i? aeanoeaino? niieoe, ye? i?noyoue oae?
o?aaiaioe.

Aia?oa iaea?aeaii aenia?eiaioaeuei? aeai? i?i aoaeiao iecee
aaoa?ioeeee?/ieo nenoai: eao?ii-?aaeeeae?a oaiio?aceio, iiaeo oei?a
eiiaeainiaaieo acioai?nieo aaoa?ioeeee?a, eao?ii?a iio?aeieo
1,4-aeea?ae?ii??ei?aeeio.

I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a Iaea?aeai?
aenia?eiaioaeuei? oa oai?aoe/i? aeai? i?i iieaeoey?io oa e?enoae?/io
no?oeoo?o niieoe iiaeooue aooe aeei?enoai? aeey iiooeo ?aoe?iiaeueieo
oeyo?a neioaco iiaeo i?aai?/ieo ooieoe?iiaeueieo iaoa??ae?a oa
e?ea?nueeeo cania?a c caaeaieie aeanoeainoyie. Anoaiiaeai?
caeiiii??iino? aoaeiae oanoe/eaiieo aeea?ae?ioeeee?a ? iaae?eiith
iniiaith aeey ?icoi?iiy iaoai?ci?a ae?? i?aeoe/ii aaaeeeaeo ?a/iaei, ui
aea? iiaeeea?noue noai?thaaoe a?eueo aoaeoeai? iaoa??aee oa i?aia?aoe.

Iniaenoee aianie caeiaoaa/a Iniaenoee aianie aaoi?a a iaea?aeaii?
iaoeiaeo ?acoeueoao?a ? aecia/aeueiei ia an?o aoaiao aeine?aeaeaiiy ?
iieyaa?, ia?o ca ana, a caaaeuei?e iinoaiiaoe? i?iaeaie oa iaa?oiooaaii?
caaaeaiiy, o aeai?? ia’?eo?a aeine?aeaeaiiy, ?ic?iaoe? iaoiaeeee
aeine?aeaeaiiy, aiae?c?, ?ioa?i?aoaoe?? oa ocaaaeueiaii?
aenia?eiaioaeueieo ? oai?aoe/ieo aeaieo, iaea?aeaieo naiino?eii /e
i?aaenoaaeaieo ni?aaaoi?aie ioae?eaoe?e. Aaoi?ii aeeiiaii ia?aaaaeio
a?eueo?noue ?aioaaiino?oeoo?ieo aeine?aeaeaiue ? oai?aoe/ieo
?ic?aooie?a.

Ai?iaaoe?y ?acoeueoao?a aeena?oaoe?? ?acoeueoaoe ?iaioe aeiiia?aeaeeny
ia I Ananithci?e eiioa?aioe?? c oai?aoe/ii? i?aai?/ii? o?i??
(Aieaia?aae, 1991), XII ? XIII Neiiic?oiao c i?aeiieaeoey?ii? aca?iiae??
oa eiioi?iaoe?e iieaeoe (Ioueii, 1993, Oa?e?a, 1994), XVIII ? XIX
Oe?a?inueeeo eiioa?aioe?yo c i?aai?/ii? o?i?? (Oa?e?a, 1995,
Aei?i?iiao?ianuee, 1998), XVIII Eiia?an? i?aeia?iaeii? ni?eee
e?enoaeia?ao?a (N?aoe, 1996), Oe?a?inuee?e eiioa?aioe?? c o?i??
acioai?nieo aaoa?ioeeee?a (Oa?e?a, 1997), I Iaoe?iiaeuei?e
e?enoaeia?ao?/i?e eiioa?aioe?? (*i?iiaieiaea, 1998), XVII ?a?iiaenuee?e
e?enoaeia?ao?/i?e eiioa?aioe?? (I?aaa, 1998).

Ioae?eaoe?? Iaoa??aee aeena?oaoe?? aeeeaaeaii o 36 noaooyo. Aiie
aena?oeththoue iniiaiee ci?no, ?acoeueoaoe, aeniiaee ? ?aeiiaiaeaoe??
aeena?oaoe??.

No?oeoo?a ? ianya aeena?oaoe?? Aeena?oaoe?y neeaaea?oueny ?c anooio,
iaeyaeo e?oa?aoo?e, naie ?icae?e?a, aea aeeeaaeaii iniiai? ?acoeueoaoe
?iaioe, i?iaaaeaii ?o iaaiai?aiiy oa iaaaaeaii aenia?eiaioaeueio
/anoeio, aeniiae?a, nieneo aeei?enoaieo e?oa?aoo?ieo aeaea?ae (562
iaeiaioaaiiy) oa aeiaeaoeo. Iiaiee ianya aeena?oaoe?? 473 noi??iee, o
oiio /ene? 74 ?enoiee, 98 oaaeeoeue oa 73 noi??iee aeiaeaoeo.

INIIAI? ?ACOEUeOAOE ?IAIOE OA ?O IAAIAI?AIIss

I?iaaaeaiee o e?oa?aoo?iiio iaeyae? aiae?c iieaeoey?ii? no?oeoo?e 453
niieoe, ye? i?noyoue o nai?io neeaae? oanoe/eaii? aeea?ae?ioeeeee,
iieacaa, ui aeai? i?i aoaeiao oeueiai eeano i?aai?/ieo niieoe aeoaea
iaiiai? oa ianenoaiaoe/i?. Aeey aeinyaiaiiy iaoe ?iaioe aoei aeeiiaii
?aioaaiino?oeoo?ia aeine?aeaeaiiy 54 iiaeo niieoe oa ?ic?aooiee aeecueei
500 iieaeoe (o oiio /ene? aeecueei 200 iaoiaeaie iaaii??e/ii? eaaioiai?
o?i??). Oea aeicaieeei nenoaiaoecoaaoe aeai? i?i aoaeiao oanoe/eaiieo
aeea?ae?ioeeee?a, oa anoaiiaeoe oaeoi?e, ye? aecia/athoue noa?aio?i?th
oeueiai eeano i?aai?/ieo niieoe.

1. Eiioi?iaoe?eiee aiae?c 1,4-aeea?ae?ioeeee?a

1.1 1,4-Oeeeeiaaenaaee?i oa eiai iio?aei?

??aiiaaaeia eiioi?iaoe?y 1,4-oeeeeiaaenaaee?io 1 aecia/a?oueny aaeainii
i?ae aeaiia a?oiaie oaeoi??a. C iaeiiai aieo, oea eooiaa iai?oaeaiiy,
yea aeeeeeaia aeaoi?iaoe??th aiaeioeeee?/ieo aaeaioieo eoo?a i?e
iane/aieo aoiiao aoaeaoeth ? iaeneiaeueia i?e ieaia?i?e aaiiao???
aeea?ae?ioeeeeo. C ?ioiai aieo — 1,2-aee?eueia iai?oaeaiiy, iaoiiaeaia
iaaaeaioieie aca?iiae?yie i?ae aoiiaie aiaeith i?e iiaea?eieo ca‘yceao
oa iaoeeaiiaeo a?oiao, ui noaa?e?co? ieineo eiioi?iaoe?th /anoeiai
a?ae?iaaiiai e?eueoey. Eaaioiaio?i?/i? ?ic?aooiee iai?aaii??e/iei
iaoiaeii AI1 iieacaee, ui aeiaeaoeiaei oaeoi?ii, yeee ni?ey? ieaia?i?e
aaiiao??? e?eueoey, ? aca?iiae?y iiaea?eieo ca‘yce?a N=N caaaeyee
ia?ae?eaaiith pz-AI ieao?iiaeo aoii?a aoaeaoeth c inaaaei—i?a?oaeyie
iaoeeaiiaeo a?oi. Aia?a?y oaeeo aca?iiae?e ?noioii ciaioo?oueny i?e
ia?aoiae? aei eiioi?iaoe?? aaiia c ?inoii oi?n?eiiai eooa N=N-N-N=.
?ic?aooiee iaoiaeii HF/6-31G iieacaee, ui ??aiiaaaeia eiioi?iaoe?y 1
ieinea. Aea iayai?noue aeaio a?oi i?eoeeaaeii ni?yiiaaieo oaeoi??a, ui
aecia/athoue eiioi?iaoe?th aeea?ae?ioeeeeo, i?ecaiaeeoue aei aeniei?
eiioi?iaoe?eii? aio/eino? /anoeiai a?ae?iaaiiai e?eueoey. Ia?ao?ae aei
eiioi?iaoe?? aaiia c oi?n?eiei eooii N=N-N-N= 20i aeeeeea? i?aeaeuaiiy
aia?a?? iieaeoee eeoa ia 1.11 eeae/iieue.

Iaaii??e/i? eaaioiaio?i?/i? ?ic?aooiee iaoiaeii HF/6-31G iieacaee, ui
aiaethaaiiy 1,4-oeeeeiaaenaaee?iiaiai e?eueoey aaicieueieie oeeeeaie ii
iiaea?eieo ca‘yceao N=N i?ecaiaeeoue aei cia/iiai iineeaiiy eooiaiai
iai?oaeaiiy a iieaeoeao 1,4-aeea?ae?iiaooae?io 2 oa
9,10-aeea?ae?iaio?aoeaio 3. Oea aeeeeea? iii?oia i?aeaeuaiiy
eiioi?iaoe?eii? aio/eino? aeea?ae?ioeeeeo, a o aeiaaeeo no?oeoo?e 3 —
iaa?oue ia?ao?ae /anoeiaiai a?ae?iaaiiai e?eueoey a eiioi?iaoe?th aaiia
c aa?‘??ii ?iaa?n?? 2,65 eeae/iieue.

Ia?cieueiaaiee oa?aeoa? iiaea?eieo ca‘yce?a o iieaeoeao 1-3 iaoiiaeth?
iii?oiee aieea aeaeo?iiieo aoaeo?a cai?niee?a ia eiioi?iaoe?ei?
oa?aeoa?enoeee aeea?ae?ioeeeeo. ?ic?aooiee iaoiaeii HF/6-31G iieacaee,
ui o ?yaeo 4-2-5 niinoa??aa?oueny aeayea cieaeaiiy eiioi?iaoe?eii?
aio/eino? aeea?ae?ioeeeeo, yea iiaea aooe iaoiiaeaii o?eueee
aeaeo?iiieie oaeoi?aie. Oea i?aeoaa?aeaeo?oueny oaeiae aiae?cii aaee/ei
ii?yaee?a ca‘yce?a oa canaeaiinoae ia?ae?eaaiiy.

Na?aae iio?aeieo niieoe 1-3 iaeieie c iaea?eueo oe?eaaeo o
eiioi?iaoe?eiiio a?aeiioaii? ? cai?uai? 9-i?o?i-9,10-aeea?ae?iaio?aoeaie
6-11, aeey yeeo iaoiaeii ssI? anoaiiaeaii aenieo eiioi?iaoe?eio
aio/e?noue aeea?ae?ioeeeeo. Iaeiae caeeoaeiny iayniei /e iaoiiaeaia oaea
iaaei?noe?noue /anoeiai a?ae?iaaiiai e?eueoey iaeith aaee/eiith aa?‘??o
eiioi?iaoe?eiiai ia?aoiaeo, /e cieiuaiith oi?iith iaeiiai i?i?ioia ia
iiaa?oi? iioaioe?eii? aia?a?? (IIA).

?ic?aooiee iaoiaeii iieaeoey?ii? iaoai?ee iieacaee, ui ia IIA iieaeoee
6 niinoa??aa?oueny o?eueee iaeei i?i?ioi, yeee a?aeiia?aea? eiioi?iaoe??
aaiia c inaaaeiaen?aeueiith (?a) i??-?ioaoe??th i?o?ia?oie. Aea oeae
i?i?ioi ia? neeueii cieiuaio oi?io, ui noai?th? iiaeeeaino? aeey
ciai?ieiueiieo eieeaaiue aeea?ae?ioeeeeo c aaeeeith aiie?ooaeith.

Iiyaa aee?eueiiai cai?nieea i?e ?ioiio iane/aiiio aoii? aoaeaoeth
(niieoee 7a-a) i?eaiaeeoue aei iiyae ia IIA i?i?ioio, yeee a?aeiia?aea?
eiioi?iaoe?? aaiia c inaaaeiaeaaoi??aeueiith (?a) i???ioaoe??th oeueiai
cai?nieea. Oea iaoiiaeaii iniaeeainoyie iaaaeaoieo aca?iiae?e i?ae
aee?eueiith a?oiith oa aoiiaie aiaeith a ia??-iieiaeaiiyo aaicieueieo
e?eaoeue. O aeiaaeeo iio?aeieo 8-11 a?aeooiaooaaiiy i?ae cai?nieeaie i?e
iane/aieo aoiiao aoaeaoeth i?ecaiaeeoue aei ?nioaaiiy eeoa
?a-eiioi?ia?o. ?acoeueoaoe ?ic?aooie?a i?aeoaa?aeaeaii oaeiae
?aioaaiino?oeoo?iei aeine?aeaeaiiyi (?NAe) niieoe 9, 12, 13.

Cai?ia aiaeioeeee?/ieo ca‘yce?a N=N ia aciiaoeiia? a?oie aeeeeea?
iii?oia iineaaeaiiy 1,2-ae?eueii? iai?oae a iieaeoe?
2,5-aeea?ae?ii??ei?aeeio 14 ii??aiyii c 1,4-oeeeeiaaenaaee?iii.

14 R1=R2=R3=H

15 R2=R3=H, a R1=Me, a R1=t-Bu, a R1=Ph

16 R1=R3=H, a R2=Me, a R2=t-Bu, a R2=Ph

17 R1=R2=H, a R3=Me, a R3=t-Bu, a R3=Ph

18 R1=H, R3=Me, a R2=Me, a R2=t-Bu, a R2=Ph

19 R1=H, R3=t-Bu, a R2=Me, a R2=t-Bu, a R2=Ph

20 R1=H, R3=Ph, a R2=Me, a R2=t-Bu, a R2=Ph

21 R2=H, a R1=R3=Me, a R1=R3=t-Bu, a R1=R3=Ph

Aiane?aeie oeueiai niioa??aa?oueny ciaioaiiy aia?a?? aeaoi?iaoe??
aeea?ae?ioeeeeo ia 0.75 eeae/iieue (ca aeaieie iaoiaeo HF/6-31G).

A?aenooi?noue A1,2 aca?iiae?? acaeiaae ca‘yce?a N-C(sp3) coiiaeth?
aeaye? iniaeeaino? eiioi?iaoe?eii? iiaaae?iee iio?aeieo
2,5-aeea?ae?ii??ei?aeeio. Oae, ca aeaieie iaoiaeo iieaeoey?ii? iaoai?ee,
iiyaa cai?niee?a R1 (niieoee 15a-a) aeeeeea?, ia a?aei?io a?ae
ea?aioeeee?/ieo aiaeia?a, ia?ao?ae aeea?ae?ioeeeeo a eiioi?iaoe?th
aaiia. I?e/iio ia IIA ?niothoue aeaa i?i?ioie, ui a?aeiia?aeathoue ye
?a, oae ? ?a-i???ioaoe?yi aee?eueii? a?oie. Iaieaia?ia eiioi?iaoe?y
aaoa?ioeeeeo ciaeaeaia ? i?e aaaaeaii? cai?niee?a aei aoii?a aoaeaoeth
iiaea?eieo ca‘yce?a (no?oeoo?e 16a-a). I?e/iio nooi?iue neeaae/aoino?
/anoeiai a?ae?iaaiiai e?eueoey a oeeo iieaeoeao aeyaey?oueny iaa?oue
a?eueoith, i?ae o 15a-a. Oea iiynith?oueny iineeaiiyi eooiai? iai?oae a
no?oeoo?ao 16a-a aiane?aeie cai?ie aaeaioieo eoo?a C(sp3)-C(sp2)-H, ye?
eaaei aeaoi?iothoueny, ia a?eueo aei?noe? N(sp3)-C(sp2)-C(sp3).
Eiioi?iaoe?ei? oa?aeoa?enoeee iio?aeieo 17a-a caeeoathoueny aeoaea
noiaeeie ia oae? aeey ea?aioeeee?/ieo aiaeia?a. Ciaeaeai?
caeiiii??iino? caa??aathoueny ? a aeecai?uaieo iio?aeieo 18-23.
?acoeueoaoe ?ic?aooie?a aeia?a ocaiaeaeothoueny c aeaieie
?aioaaiino?oeoo?ieo aeine?aeaeaiue niieoee 24.

1.2. Iio?aei? 1,4-oeeeeiaaenaaee?io c aecioeeee?/iei iiaea?eiei
ca‘yceii

Cai?ia iaei??? c iaoeeaiiaeo a?oi o iieaeoe? 1,4-oeeeeiaaenaaee?io ia
aecioeeee?/iee iiaea?eiee ca‘ycie i?ecaiaeeoue aei ciaioaiiy eooiai?
iai?oae oa iiyae noi?yaeaii? nenoaie, oiaoi aei iii?oiiai iineeaiiy
oaeoi??a, ye? noaa?e?cothoue ieineo eiioi?iaoe?th aeea?ae?ioeeeeo.

Eaaioiaio?i?/i? ?ic?aooiee iaoiaeii HF/6-31G iieacaee, ui ??aiiaaaeia
eiioi?iaoe?y aeea?ae?ioeeeeo a niieoeao 25-27 ieaia?ia. Aea iineeaiiy
cieiuoth/eo oaeoi??a cia/ii cieaeo? eiioi?iaoe?eio aio/e?noue /anoeiai
a?ae?iaaiiai e?eueoey ii??aiyii c 1,4-oeeeeiaaenaaee?iii. Ciaioaiiy
iiey?iino? aecioeeee?/iiai iiaea?eiiai ca‘yceo a ?yaeo X=O, NH, CH2
aeeeeea? i?aeaeuaiiy iaaei?noeino? aeea?ae?ioeeeeo aiane?aeie ciaioaiiy
ii?yaee?a ca‘yce?a =N-N(=O). Aiaethaaiiy 25 aaicieueieie oeeeeaie ii
iiaea?eieo ca‘yceao N=N ni?e/eiy? i?aeaeuaiiy eiioi?iaoe?eii? aio/eino?
ea?aioeeeeo, aiaeia?/ii iio?aeiei 1,4-oeeeeiaaenaaee?io. O aeiaaeeo
?i?ii oa iaoeeaiiio?aeieo 29, 30, 32, 33 a?aeooiaooaaiiy i?ae aoiiaie
aiaeith i?e aecioeeee?/iiio iiaea?eiiio ca‘yceo oa a ia??-iieiaeaiiyo
aaicieueieo e?eaoeue aeeeeea? ia?ao?ae aeea?ae?ioeeeeo a eiioi?iaoe?th
aaiia oa nooo?aa i?aeaeuaiiy eiai iaaei?noeino?.

?ic?aooiee iaoiaeii iieaeoey?ii? iaoai?ee iieacaee, ui noa?e/i? aoaeoe
cai?niee?a a iieaeoeao 34-39 i?aeoe/ii ia a?ae??ciythoueny a?ae
ciaeaeaieo ?ai?oa aeey iio?aeieo 1,4-oeeeeiaaenaaee?io.

??aiiaaaeia eiioi?iaoe?y aeea?ae?ioeeeeo caeeoa?oueny ieineith ? i?e
aaaaeaii? aeaeo?iiiaeiii?ieo oa aeoeaioi?ieo cai?niee?a aei
aiaeioeeee?/ieo iiaea?eieo ca‘yce?a N=N (niieoee 40-43). Ca aeaieie
iaoiaeo HF/6-31G eiioi?iaoe?eia aio/e?noue /anoeiai a?ae?iaaiiai
e?eueoey o oeeo iieaeoeao oaeiae i?aeoe/ii ia ci?ith?oueny. Oea
iaoiiaeaii aca?iiith eiiiainaoe??th aieeao aeaeo?iiieo oa noa?e/ieo
aoaeo?a cai?niee?a ia eiioi?iaoe?ei? oa?aeoa?enoeee ea?aioeeeeo. Oaeee
aoaeo a?aenooi?e o iieaeoeao 44-51, a yeeo cai?niee a?aeaeaeaiee a?ae
aeea?ae?ioeeeeo ? ia i?eeia? o/ano? o iaaaeaioieo aca?iiae?yo c aoiiaie
aiaeith iaoeeaiiai? a?oie oa ea?aii?eueiith a?oiith. Iaeiae ?ic?aooiee
iaoiaeii AI1 ia aeyaeee aieeao aeaeo?iiieo aoaeo?a cai?niee?a ia
eiioi?iaoe?ei? oa?aeoa?enoeee /anoeiai a?ae?iaaiiai e?eueoey.

?ic?aooiee iaoiaeii AI1 iieaeoe 52-54 oa ?aioaaiino?oeoo?ia
aeine?aeaeaiiy eae??ai? nie?

53 iieacaei, ui i?aai?/i? ai?iie a eiiieaenao Iaecaiaaia?a iathoue
aoaeiao aeoaea iiae?aio aei 9-?e?aeaiiaeo iio?aeieo
9,10-aeea?ae?iaio?aoeaio. Oea iaoiiaeaii cia/iei aeeaaeii
aoee-?aciiainii? oi?ie a no?oeoo?o i?o?ia?oie, aiane?aeie /iai ca‘ycie
N-N ia? /anoeiai iiaea?eiee oa?aeoa?.

1.3. 1,4-Aeea?ae?iaaoa?ioeeeee

Eiioi?iaoe?y aeea?ae?ioeeeeo a aaoa?ioeeee?/ieo aiaeiaao
1,4-oeeeeiaaenaaee?io 55-57 aecia/a?oueny oeie ae oaeoi?aie ui ? a
iieaeoeao 25-27. Oea coiiaeth? ieaia?io ??aiiaaaeio aaiiao??th
aaoa?ioeeee?a (ca aeaieie iaoiaeo HF/6-31G).

Aea /anoeiai a?ae?iaaia e?eueoea a no?oeoo?ao 55-57 ? cia/ii aio/e?oei,
ii??aiyii c ?e?aeaiiaeie iio?aeieie 1,4-oeeeeiaaenaaee?io, iniaeeai o
aeiaaeeo 4I-o?ii??aio 57, ui coiiaeaii iineeaiiyi eooiai? iai?oae
aiane?aeie aeaoi?iaoe?? aiaeioeeee?/iiai aaeaioiiai eooa i?e aoii?
n??ee.

Aiaethaaiiy 1,4-aeea?ae?ii??ei?aeeio ii ca‘yceo C=N (niieoee 58-61)
i?ecaiaeeoue aei i?aeaeuaiiy eiioi?iaoe?eii? aio/eino? aeea?ae?ioeeeeo.
Aea a oeeo niieoeao aeyaeaii caeaaei?noue aia?a?? aeaoi?iaoe?? e?eueoey
a?ae i?e?iaee acieueiiai oeeeeo. I?e/iio ciaeaeaia caeaaei?noue ia
ocaiaeaeo?oueny c aeaeo?iiiei oa?aeoa?ii i‘yoe/eaiiiai e?eueoey ? iiaea
aooe iiyniaia eeoa c o?aooaaiiyi ??cieoe? a aia?a?? ac?iiae?e -nenoai
acieueiiai oeeeeo oa iiaea?eiiai ca‘yceo N=N /a?ac iaoeeaiiao a?oio.

62 R2=R3=H, a R1=Me, a R1=t-Bu, a R1=Ph 65 a R=Me, a R=t-Bu, a R=Ph

63 R1=R3=H, a R2=Me, a R2=t-Bu, a R2=Ph

64 R1=R2=H, a R3=Me, a R3=t-Bu, a R3=Ph

66
67

Iineeaiiy eooiai? iai?oae i?e aaicaiaethaaii?
1,4-aeea?ae?iaaoa?ioeeee?a iaoiiaeth? a?eueo neeueiee aieea noa?e/ieo
aoaeo?a cai?niee?a ia eiioi?iaoe?ei? oa?aeoa?enoeee /anoeiai
a?ae?iaaiiai e?eueoey. Ca aeaieie iaoiaeo iieaeoey?ii? iaoai?ee nooi?iue
neeaae/aoino? aeea?ae?ioeeeeo a iieaeoeao 62-65 noooaai a?eueoa, i?ae a
iaaiaeueiaaieo aiaeiaao, a aia?a?y aeaoi?iaoe?? aaoa?ioeeeeo cia/ii
iaioa.

?aioaaiino?oeoo?ia aeine?aeaeaiiy niieoe 66,67 oa eaaioiaio?i?/i?
?ic?aooiee ?yaeo iiaeaeueieo no?oeoo? iieacaee, ui ia a?aei?io a?ae
aee?eueieo cai?niee?a, aaaaeaiiy oai?eueii? aai iaoo?eueii? a?oi aei
iane/aiiai aoiio aoaeaoeth i?ecaiaeeoue aei cieiuaiiy /anoeiai
a?ae?iaaiiai e?eueoey. I?e/eiith oeueiai ? a?aeooiaooaaiiy i?ae aoiiaie
cai?nieea oa iie?oeeee?/ii? nenoaie. I?e oeueiio niinoa??aa?oueny oaeiae
iii?oia ciaioaiiy eiioi?iaoe?eii? aio/eino? /anoeiai a?ae?iaaiiai
e?eueoey.

68 n=1, R=H 69 n=2, R=H 70 n=3, R=H

71 n=1, a R=Me, a R-t-Bu

72 n=2, a R=Me, a R=t-Bu

73 n=3, a R=Me, a R=t-Bu

Aiaethaaiiy 1,4-aeea?ae?ii??ei?aeeiiaiai e?eueoey iane/aieie
ea?aioeeeeaie ii iiaea?eiiio ca‘yceo N=N (no?oeoo?e 68-73), ca aeaieie
iaoiaeo iieaeoey?ii? iaoai?ee, i?ecaiaeeoue aei ia?aoiaeo aaoa?ioeeeeo a
eiioi?iaoe?th aaiia oa i?aeaeuaiith eiioi?iaoe?eii? aio/eino? /anoeiai
a?ae?iaaiiai e?eueoey. Oea iaoiiaeaii iaaaeaioieie aca?iiae?yie i?ae
iaoeeaiiaeie a?oiaie aaoa?ioeeeeo oa aiaethth/iai e?eueoey. ?acoeueoaoe
?ic?aooie?a i?aeoaa?aeaeaii ?NAe niieoe 74,75.

74 75 76

Oae? iaaaeaioi? aca?iiae?? iaoiiaeththoue oaeiae ? iaieaia?io
aaiiao??th aeea?ae?ii??ei?aeeiiaiai e?eueoey a ni??iiio?aeiiio 76, yea
anoaiiaeaia ?aioaaiino?oeoo?iei aeine?aeaeaiiyi.

1.4. 1,4-O?iiie

Cai?ia iaio iaoeeaiiaeo a?oi o iieaeoe? 1,4-oeeeeiaaenaaee?io ia
aecioeeee?/i? iiaea?ei? ca‘ycee ni?e/eiy? cieeiaiiy eooiai? iai?oae, yea
aeanoaa?e?co? ieaia?io eiioi?iaoe?th aeea?ae?ioeeeeo. Oiio ??aiiaaaeia
eiioi?iaoe?y e?eueoey a iieaeoeao 77-82 ieinea.

Aea iaaii??e/i? eaaioiaio?i?/i? ?ic?aooiee iaoiaeii HF/6-31G iieacaee,
ui aeea?ae?i-oeeee o oeeo no?oeoo?ao caeeoa?oueny a cia/i?e i???
eiioi?iaoe?eii iaaei?noeei. Oae o ia?a-o?iii? 77 ia?ao?ae c ieinei?
??aiiaaaeii? eiioi?iaoe?? o aaiio c oi?n?eiei eooii N=N-N(=I)-N= 20
aeeeeea? i?aeaeuaiiy aia?a?? iieaeoee iaioa i?ae ia 1.9 eeae/iieue.

Caa?aaeaiiy eiioi?iaoe?eii? aio/eino? a iieaeoeao 77-82 i?e
a?aenooiino? iane/aiiai aoiio aoaeaoeth a e?eueoe?, aeaco? ia iiyao
iiaiai oaeoi?a, yeee aeanoaa?e?co? ieaia?io aaiiao??th e?eueoey. Aiae?c
eiioi?iaoe?eieo oa?aeoa?enoee niieoe 77-82 iieacaa, ui oaeei oaeoi?ii
iiaea aooe a?aeoeeaiiy oa?aeoa?o noi?yaeaii? nenoaie a oeeee? a?ae
a?iiaoe/iiai. Cieaeaiiy iiey?iino? aecioeeee?/ieo iiaea?eieo ca‘yce?a
i?ecaiaeeoue aei ciaioaiiy eiioi?iaoe?eii? aio/eino? aeea?ae?ioeeeeo
aiane?aeie i?aeaeuaiiy aeaeo?iiii? aonoeie a 6 -aeaeo?iii?e nenoai?
oeeeeo. O aeiaaeeo iieaeoe 78, 79, 81 , ye? i?noyoue ??ci? iiaea?ei?
ca‘ycee, eiioi?iaoe?y aaiia noa? aneiao?e/iith ? aio/e?oei ? o?aaiaio
e?eueoey, c a?eueo iiey?iei ca‘ycieii. Ae??oaeueia ?ieue nooiaith
a?iiaoe/iino? noi?yaeaii? nenoaie oeeeeo i?aeoaa?aeaeo?oueny oaeiae
oi?ioith ei?aeyoe??th i?ae cia/aiiyie ?iaeaen?a a?iiaoe/iino? Auei?aea
oa Iiaea?nueeiai ? aia?a??th aeaoi?iaoe?? aeea?ae?ioeeeeo.

Aaaaeaiiy aee?eueieo a?oi a iieaeoeo ia?a-o?iiio aeeeeea? i?aeaeuaiiy
eiioi?iaoe?eii? aio/eino? aeea?ae?ioeeeeo aiane?aeie a?aeooiaooaaiiy
i?ae cai?nieeii oa aecioeeee?/iei iiaea?eiei ca‘yceii. Oa?aeoa? aieeao
cai?niee?a o iieaeoeao i?o?i oa ai?iiiio?aeieo 83, 84 iaoiiaeaiee
eiieo?aioe??th i?ae aoaeoaie noi?yaeaiiy i?ae cai?nieeii oa
ea?aii?eueieie a?oiaie c iaeiiai aieo oa iaaaeaioieie aca?iiae?yie i?ae
oeeie o?aaiaioaie c ?ioiai. Aiane?aeie oeueiai aaaaeaiiy i?o?ia?oie
i?ecaiaeeoue aei iaieaia?ii? ??aiiaaaeii? eiioi?iaoe?? aeea?ae?ioeeeeo
oa i?aeaeuaiiy eiioi?iaoe?eii? aio/eino?, o oie /an ye oa?aeoa?enoeee
iieaeoee 83 i?aeoe/ii ia a?ae??ciythoueny a?ae 77.

Aiaethaaiiy ia?a-o?iiiiaiai oeeeeo aaicieueieie e?eueoeyie ii
iiaea?eiei ca‘yceai N=N aeeeeea? i?aeaeuaiiy eiioi?iaoe?eii? aio/eino?
aeea?ae?ioeeeeo, ui iaoiiaeaii iineaaeaiiyi noi?yaeaiiy i?ae -nenoaiaie
a?iiaoe/ieo e?eaoeue oa ea?aii?eueieo a?oi. A ?i?ii oa iaoeeaiiio?aeieo
aecia/aeueio ?ieue a?ae?a?a? a?aeooiaooaaiiy i?ae aoiiaie aiaeith i?e
aecioeeee?/ieo iiaea?eieo ca‘yceao oa a ia??-iieiaeaiiyo aaicieueieo
e?eaoeue, ye? i?ecaiaeyoue, ca aeaieie iaoiaeo AI1, aei iaieaia?ii?
??aiiaaaeii? eiioi?iaoe?? oa i?aeaeuaiiy eiioi?iaoe?eii? aio/eino?
aeea?ae?ioeeeeo.

1.5. Iio?aei? 1,4-aeea?ae?iaaoa?ioeeee?a c aiaeioeeee?/iei iiaea?eiei
ca‘yceii

Cai?ia iaoeeaiiai? a?oie a 1,4-aeea?ae?iaaoa?ioeeeeao ia aecioeeee?/iee
iiaea?eiee ca‘ycie oaeiae ni?e/eiy? cieeiaiiy eooiai? iai?oae. Aea, ye ?
a ia?a-o?iiiao, oanoe/eaiia e?eueoea a iieaeoeao 85-96 caeeoa?oueny
eiioi?iaoe?eii aio/eei.

I?e/eiith iaaei?noeino? aaoa?ioeeeeo a oeeo no?oeoo?ao ? iaa?iiaoe/iee
oa?aeoa? noi?yaeaii? nenoaie a oeeee? (7 -aeaeo?ii?a). Ca?aeii c oeei,
ciaioaiiy iiey?iino? aecioeeee?/iiai iiaea?eiiai ca‘yceo aeeeeea?, ca
aeaieie iaoiaeo HF/6-31G, i?aeaeuaiiy eiioi?iaoe?eii? aio/eico?
aeea?ae?ioeeeeo.

Aieea aeaeo?iiieo aoaeo?a cai?niee?a ia iaaei?noe?noue aaoa?ioeeeeo a
iieaeoeao 94-96 iaoiiaeaia eiieo?aioe??th aeaio oaeoi??a. C iaeiiai
aieo, aeaeo?iiiiaeoeaioi?i? oa aeiii?i? a?oie, a?aeiia?aeii, ciaioothoue
aai ca?eueoothoue a?aeoeeaiiy oa?aeoa?o noi?yaeaii? nenoaie a oeeee?
a?ae a?iiaoe/iiai. Aea, c ?ioiai aieo, iayai?noue ai?iia?oie
i?ecaiaeeoue aei iii?oiiai i?aeaeuaiiy ii?yaee?a iaeeia?ieo ca‘yce?a o
aaoa?ioeeee? aiane?aeie neeueieo eii‘thaaoe?eieo aca?iiae?e c
aeaeo?iiiaeoeaioi?iith ea?aii?eueiith a?oiith, ui aeeeeea? ciaioaiiy
eiioi?iaoe?eii? aio/eino? aeea?ae?ioeeeeo. E??i oeueiai, a no?oeoo?ao
96a,a cia/io ?ieue a?ae?a?athoue iaaaeaioi? ac?iiae?? i?ae cai?nieeii oa
aecioeeee?/iei iiaea?eiei ca‘yceii.

?ic?aooiee iaoiaeii HF/6-31G iieacaee, ui noa?e/i? aoaeoe cai?niee?a o
aee?eiio?aeieo i??eaeiio-4 ia aieeaathoue ia eiioi?iaoe?ei?
oa?aeoa?enoeee aaoa?ioeeeeo.

Aaicaiaethaaiiy i??eaeiio-4 oa 4I-i??aio ii iiaea?eiei ca‘yceai N=N ia
ci?ith? ieaia?io ??a-iiaaaeio aaiiao??th aaoa?ioeeeeo. Iaeiae i?e
oeueiio niinoa??-aa?oueny iii?oia i?ae-aeuaiiy eiioi?ia-oe?eii?
aio/eino? aeea?ae?ioeeeeo aiane?aeie iineaaeaiiy noi?yaeaiiy i?ae
a?iiaoe/ieie e?eueoeyie oa ea?aii?eueieie a?oiaie.

Iaiaeiicia/i? aeai? iaea?aeaii i?i aieea aiaethaaiiy
aeea?ae?ii??ei?aeeiiaiai e?eueoey ii iaeeia?iiio ca‘yceo =C-N. ?NAe
niieoe 97, 98 iieacaei, ui a iaeiiio aeiaaeeo aeea?ae?ioeeee
ciaoiaeeoueny a eiioi?iaoe?? aaiia (97), a a ?ioiio (98) ia? ieaia?io
aaiiao??th. Eaaioiai-o?i?/i? ?ic?aooiee iaoiaeii AI1 aeaee ieineo
??aiiaaaeio aaiiao??th aeea?ae?ii??ei?aeeiiaiai e?eueoey a iieaeoeao
97-102. Aea aio/e?noue aaoa?ioeeeeo a no?oeoo?? 97 cia/ii aeua, /ei a
?ioeo. Oea iaoiiaeaii ye aiaethaaiiyi, oae ? iayai?noth cai?niee?a i?e
iiaea?eiiio ca‘yceo N=N. Oaeei /eiii, aeea?ae?ii??ei?aeeiiaa e?eueoea o
oe?e iieaeoe? ? a?eueo ni?eeiyoeeaei aei aeaoi?ioth/i? ae??
i?aeiieaeoey?ieo aca?iiae?e o e?enoae?.

1.6. Aioea?iiaoe/i? 1,4-aaoa?ioeeeee

Aecia/aeueia ?ieue oa?aeoa?o noi?yaeaii? nenoaie a oeeee? iaea?eueo
yne?aai i?iyaey?oueny a aioea?iiaoe/ieo 1,4-aaoa?ioeeeeao 103-108.

Eiioi?iaoe?y oaeeo iieaeoe aecia/a?oueny aaeainii i?ae ia?ae?eooyi
eiaeii? ia?e pz-AI aoii?a oeeeeo, yea iaeneiaeueia i?e ieaia?i?e
aaiiao??? e?eueoey, oa aia?aaoe/iith iaaea?aei?noth aioea?iiaoe/ii?
-nenoaie, yea aeanoaa?e?co? oaeo eiioi?iaoe?th. ?ic?aooiee iaoiaeii
HF/6-31G iieacaee ui ??aiiaaaeia aaiiao??y aaoa?ioeeeeo a iieaeoeao 103,
104, 106 ieinea. A no?oeoo?ao 105, 107, 108, ye? i?noyoue aoii n??ee,
oanoe/eaiia e?eueoea ia? eiioi?iaoe?th aaiia, ui iaoiiaeaii
aeiaeaoeiaith eooiaith iai?oaith aiane?aeie aeaoi?iaoe?? aiaeioeeee?/ieo
aaeaioieo eoo?a i?e aoii? S.

Iayai?noue aioea?iiaoe/ii? noi?yaeaii? nenoaie i?ecaiaeeoue aei a?eueo
aeniei? eiioi?iaoe?eii? aio/eino? aaoa?ioeeeeo, ii??aiyii c ?ioeie
oanoe/eaiieie aeea?ae?ioeeeeaie. O aeiaaeeo no?oeoo? 105, 107 aa?‘??
?iaa?n?? e?eueoey ia ia?aaeuo? 0.3 eeae/iieue.

Aaicaiaethaaiiy 1,4-aeea?ae?ii??aceio ia aieeaa? ia ??aiiaaaeio
eiioi?iaoe?th aaoa?ioeeeeo. Aea ciaioaiiy ia?ae?eaaiiy i?ae pz-AI
aoaeaoeth oa acioo iaoiiaeth? nooo?aa i?aeaeuaiiy aio/eino? oeeeeo.
Aiaeia?/iee aoaeo niinoa??aa?oueny ? a iio?aeieo o?aceio. I?e oeueiio
oaeiae cia/ii ca?eueoo?oueny nooi?iue ceeaae/aoino? aaoa?ioeeeeo
aiane?aeie iineeaiiy eooiai? iai?oae. Oea nie/eiy? c?inoaiiy aa?‘??o
?iaa?n?? /anoeiai a?ae?iaaiiai e?eueoey.

?ic?aooiee iaoiaeii AI1 oa ?NAe niieoe 109a-a iieacaee, ui ca?eueoaiiy
ia‘?io cai?nieea i?e aoii? acioo aeeeeea? i?aeaeuaiiy nooiaith
ceeaae/aoino? o?aceiiaiai e?eueoey aiane?aeie a?aeooiaooaaiiy i?ae
aee?eueiith a?oiith oa aoiiaie aiaeith o ia??-iieiaeaiiyo aaicieueieo
oeeee?a.

Ciaioaiiy aioea?iiaoe/iiai oa?aeoa?o noi?yaeaii? nenoaie a iiii- oa ae?
S-ieneaeao oaiio?aceio aiane?aeie iiyae iiey?ieo ca‘yce?a S=O aeeeeea?,
ca aeaieie ?NAe oa ?ic?aooie?a iaoiaeii AI1, iii?oia cieiuaiiy
aaoa?ioeeeeo.

Aiaeia?/iee aoaeo niinoa??aa?oueny ? i?e aaaaeaii?
aeaeo?iiiaeoeaioi?ieo cai?niee?a a iieaeoeao 110a-112a. A ai?iiiio?aeieo
110a-112a aaoa?ioeeee noa? iii?oii iaieaia?iei oa a?eueo eiioi?iaoe?eii
aio/eei.

Ae??oaeueio ?ieue aioea?iiaoe/iiai oa?aeoa?o noi?yaeaii? nenoaie
i?aeoaa?aeaeaii ?NAe eao?ii-?aaeeeaeo oaiio?aceio 109a. Aeaeaeaiiy
iaeiiai aeaeo?iio c -nenoaie i?ecaiaeeoue aei ??ceiai cieiuaiiy
aaoa?ioeeeeo.

2. Eiioi?iaoe?eiee aiae?c oanoe/eaiieo 1,2-aeea?ae?ioeeee?a

2.1. 1,3-Oeeeeiaaenaaee?i oa eiai acaaiaeiae

??aiiaaaeia eiioi?iaoe?y 1,3-oeeeeiaaenaaee?io 113 oa eiai aiaeia?a
114-116 oaeiae aecia/a?oueny aaeainii i?ae aeaiia a?oiaie oaeoi??a. Oea,
c iaeiiai aieo, noi?yaeaiiy i?ae iiaea?eieie ca‘yceaie, yea iaeneiaeueia
i?e ieaia?i?e aaiiao??? iieaeoee. C ?ioiai aieo, eooiaa iai?oaa, ui
aeieea? aiane?aeie aeaoi?iaoe?? aiaeioeeee?/ieo aaeaioieo eoo?a i?e
iane/aieo aoiiao aoaeaoeth, oa i?aaiaiiy aei caaaeueiiaaii? eiioi?iaoe??
acaeiaae ca‘yceo C(sp3)-C(sp3), ni?eythoue iaieaia?i?e aoaeia? /anoeiai
a?ae?iaaiiai e?eueoey. Ca aeaieie eaaioiaio?i?/ieo ?ic?aooie?a
aeea?ae?ioeeee a iieaeoeao 113-116 ia? eiioi?iaoe?th i?ii?aeio i?ae
nioith oa iai?ae??neii, ui aeaco? ia ia?aaaao ?icieiuoth/eo oaeoi??a.
Aea iayai?noue i?ioeeaaeii ni?yiiaaieo aca?iiae?e, ye? aecia/athoue
aoaeiao /anoeiai a?ae?iaaiiai e?eueoey, i?iecaiaeeoue aei iaaii?
iaaei?noeino? aeea?ae?ioeeeeo.

Eaaioiaio?i?/i? ?ic?aooiee iaoiaeii HF/6-31G** iieacaee, ui “aeieeia”
ia iiaa?oi? iioaioe?eii? aia?a?? iieaeoe 113-116, aea ciaoiaeyoueny
oi/ee i?i?ioi?a ? ia?ao?aeiiai noaio i?ioeano ?iaa?n?? e?eueoey, ia?
Z-iiae?aio oi?io. Ia?ao?ae i?ae aeaiia aeca?eaeueii-neiao?e/ieie
eiioi?ia?aie caaacia/o?oueny o?eueee iiai?ioii iaaeiei ca‘yceo
C(sp3)-C(sp3). Ci?ia ae oi?n?eiiai eooa i?ae iiaea?eieie ca‘yceaie aaaea
aei cieiuaiiy noi?yaeaiie nenoaie. I?e oeueiio eiioi?iaoe?y iane/aiiai
o?aaiaioo iieaeoee i?aeoe/ii ia ci?ith?oueny, a niinoa??aa?oueny
ce?o/oaaiiy iiaea?eieo ca‘yce?a.

Aaaaeaiiy cai?niee?a aei aoii?a aoaeaoeth a niieoeao 113-116 i?aeoe/ii
ia aieeaa? ia ??aiiaaaeio eiioi?iaoe?th aeea?ae?ioeeeeo.
Niinoa??aa?oueny o?eueee aeayea c?inoaiiy aa?‘???a ?iaa?n?? e?eueoey i?e
cia/ieo ?ici??ao aee?eueieo a?oi.

2.2. Iio?aei? 1,3-oeeeeiaaenaaee?io c aecioeeee?/iei iiaea?eiei
ca‘yceii.

Cai?ia iaei??? c iaoeeaiiaeo a?oi a 1,3-oeeeeiaaenaaee?i? ia iiaea?eiee
ca‘ycie i?ecaiaeeoue aei ??ceiai iineeaiiy oaeoi??a, ye? noaa?e?cothoue
ieaia?io eiioi?iaoe?th aeea?ae?ioeeeeo. Oiio, ca aeaieie ?ic?aooie?a
iaoiaeii HF/6-31G, ??aiiaaaeia aaiiao??y iieaeoe 117-119 ieinea.

Aea /anoeiai a?ae?iaaia e?eueoea o oeeo no?oeoo?ao ia? aenieo
eiioi?iaoe?eio aio/e?noue. Ia?ao?ae aeea?ae?ioeeeeo a iieaeoe? 117 ?c
ieaia?ii? ??aiiaaaeii? eiioi?iaoe?? a niioai?aio nioo c oi?n?eiei eooii
=N-NI2-N(=O)-N= 20 aeeeeea? i?aeaeuaiiy aia?a?? iieaeoee iaioa i?ae ia
0.6 eeae/iieue. Ciaioaiiy iiey?iino? aecioeeee?/iiai iiaea?eiiai ca‘yceo
i?ecaiaeeoue aei ca?eueoaiiy eiioi?iaoe?eii? aio/eino? oeeeeo.

?ic?aooiee iaoiaeii iieaeoey?ii? iaoai?ee iieacaee ui, noa?e/i? aoaeoe
cai?niee?a aieeaathoue ia eiioi?iaoe?ei? oa?aeoa?enoeee aeea?ae?ioeeeeo
o?eueee o ?ac? i?enooiino? cai?nieea i?e iane/aiiio aoii? aoaeaoeth. I?e
oeueiio niinoa??aa?oueny ia?ao?ae /anoeiai a?ae?iaaiiai e?eueoey o
eiioi?iaoe?th niioai?aii? nioe oa iii?oia ciaioaiiy eiai aio/eino?.

?ic?aooiee iaoiaeii HF/6-31G iieaeoe 120-123 iieacaee, ui aieea
aeaeo?iiieo aoaeo?a cai?niee?a ia eiioi?iaoe?ei? oa?aeoa?enoeee
aeea?ae?ioeeeeo iaoiiaeaii oa?aeoa?ii ?o aca?iiae?? c aecioeeee?/iei
iiaea?eiei ca‘yceii. Oae, a niieoeao 120,121 a?eueo aio/eei ? /anoeiai
a?ae?iaaia e?eueoea a ai?iiiio?aeieo, oiae? ye o iieaeoeao 122,123
niinoa??aa?oueny i?ioeeaaeiee aoaeo.

120 R2=R3=R4=H a R1=NH2, a R1=NO2

121 R1=R3=R4=H a R2=NH2, a R2=NO2

122 R1=R2=R4=H a R3=NH2, a R3=NO2

123 R1=R2=R3=H a R4=NH2, a R4=NO2

Aiaethaaiiy aeea?ae?ioeeeeo aaicieueieie e?eueoeyie ii iiaea?eieo
ca‘yceao N=N ia ci?ith? ieaia?io ??aiiaaaeio eiioi?iaoe?th iieaeoe. Aea
iiyaa a no?oeoo?? a?iiaoe/ieo oeeee?a, ye? aaaeei aeaoi?iothoueny,
iaoiiaeth? iineeaiiy eooiai? iai?oae, ui ni?e/eiy? i?aeaeuaiiy aio/eino?
/anoeiai a?ae?iaaiiai e?eueoey.

Oaeei /eiii niieoee 117-119, ca nai?ie eiioi?iaoe?eieie oa?aeoa?enoeeaie
caeiathoue i?ii?aeia iieiaeaiiy i?ae 1,4- oa 1,3-oeeeeiaaenaaee?iaie.

2.3. 1,2-Aeea?ae?iaaoa?ioeeeee

Oaeoi?e, ui aecia/athoue i?inoi?iao aoaeiao 1,2-aeea?ae?iaaoa?ioeeee?a
124,125 aiaeia?/i? ciaeaeaiei aeey iieaeoe 117-119. Aea /anoeiai
a?ae?iaaia e?eueoea a niieoeao 124,125 cia/ii a?eueo eiioi?iaoe?eii
aio/ea. Oae, ia?ao?ae aeea?ae?ioeeeeo a iieaeoe? 125 c ieaia?ii?
??aiiaaaeii? eiioi?iaoe?? aei niioai?aii? nioe c oi?n?eiei eooii
=C–C(sp3)–NH–C= 30 aeeeeea? i?aeaeuaiiy aia?a?? iieaeoee anueiai ia 0.2
eeae/iieue.

O aaicaiaeueiaaieo iio?aeieo iieaeoe 124,125 niinoa??aa?oueny cia/ia
i?aeaeuaiiy eiioi?iaoe?eii? aio/eino? aaoa?ioeeeeo aiane?aeie iineeaiiy
eooiai? iai?oae.

126 R2=R3=R4=R5=H, a R1=NH2, a R1=NO2

127 R1=R3=R4=R5=H, a R2=NH2, a R2=NO2

128 R1=R2=R4=R5=H, a R3=NH2, a R3=NO2

129 R1=R2=R3=R5=H, a R4=NH2, a R4=NO2

130 R1=R2=R3=R4=H, a R5NH2, a R5=NO2

A?eueo aeniea iaaei?noe?noue 1,2-aeea?ae?ioeeee?a ii??aiyii c?
niieoeaie 117-119 iaoiiaeth? ? i?aeaeuaio /ooeea?noue eiioi?iaoe??
aaoa?ioeeeeo aei aeaeo?iiieo aoaeo?a cai?niee?a. ?ic?aooiee iaoiaeii
HF/6-31G iieacaee, ui a iieaeoeao 127a,a, 128a ??aiiaaaeia eiioi?iaoe?y
/anoeiai a?ae?iaaiiai e?eueoey nooo?ai iaieaia?ia, a aaoa?ioeeee o an?o
iieaeoeao (ca aeeeth/aiiyi 126a, 128a) ? a?eueo aio/eei ii??aiyii c 124.

131 R2=R3=H, a R1=Me, a R1=t-Bu, a R1=Ph

132 R1=R3=H, a R2=Me, a R2=t-Bu, a R2=Ph

133 R1=R2=H, a R3=Me, a R3=t-Bu, a R3=Ph

134 R3=H, a R1=R2=Me, a R1=R2=t-Bu, a R1=R2=Ph

135 R2=H, a R1=R3=Me, a R1=R3=t-Bu, a R1=R3=Ph

136 R1=H, a R2=R3=Me, a R2=R3=t-Bu, a R2=R3=Ph

137 R2=R3=H, a R1=Me, a R1=t-Bu, a R1=Ph

138 R1=R3=H, a R2=Me, a R2=t-Bu, a R2=Ph

139 R1=R2=H, a R3=Me, a R3=t-Bu, a R3=Ph

140 R3=H, a R1=R2=Me, a R1=R2=t-Bu, a R1=R2=Ph

141 R2=H, a R1=R3=Me, a R1=R3=t-Bu, a R1=R3=Ph

142 R1=H, a R2=R3=Me, a R2=R3=t-Bu, a R2=R3=Ph

Noa?e/i? aoaeoe cai?niee?a a?ae/ooii aieeaathoue ia eiioi?iaoe?ei?
oa?aeoa?enoeee aeea?ae?ioeeeeo o?eueee i?e iayaiino? cai?nieea i?e
iane/aiiio aoii? aoaeaoeth (niieoee 131,137). I?e oeueiio
niinoa??aa?oueny ia?ao?ae aaoa?ioeeeeo aei eiioi?iaoe?? niiai?aia nioa
oa ciaioaiiy eiai aio/eino?. A ?ioeo aeiaaeeao aeayea ?icieiuaiiy
/anoeiai a?ae?iaaiiai e?eueoey oa ciaioaiiy aia?a?? eiai aeaoi?iaoe??
ciaeaeaii o?eueee i?e cia/ieo ?ici??ao aee?eueii? a?oie. ?acoeueoaoe
?ic?aooie?a i?aeoaa?aeaeaii aeaieie ?NAe niieoee 143.

156 157

158 159

Ii??aiyiiy eiioi?iaoe?eieo oa?aeoa?enoee niieoe 144-155 iieacaei, ui
oa?aeoa? aieeao aiaethaaiiy aeea?ae?ii??ei?aeeiiaiai e?eueoey ii ca‘yceo
C-N caeaaeeoue a?ae i?e?iaee aiaethth/iai oeeeeo. Oea iaoiiaeaii
eiieo?aioe??th i?ae i?aeaeuaiiyi eooiai? iai?oae, aiane?aeie iiyae a
no?oeoo?? i‘yoe/eaiiiai e?eueoey, oa iineeaiiyi eii‘thaaoe?eieo
aca?iiae?e, ca ?aooiie ?icoe?aiiy noi?yaeaii? nenoaie iieaeoee. Ia?oee
oaeoi? ni?ey? i?aeaeuaiiy eiioi?iaoe?eii? aio/eino? aaoa?ioeeeeo a
iieaeoe? 144. A niieoeao 148,152 niinoa??aa?oueny i?ioeeaaeiee aoaeo, ui
aeaco? ia aeii?ioaaiiy aoaeo?a noi?yaeaiiy. Aiaeia?/i? caeiiii??iino?
ciaeaeaii ? aeey cai?uaieo iio?aeieo 145-147, 149-151, 153-155, cie?aia
ca aeaieie ?NAe niieoe 156,157.

?aioaaiino?oeoo?ia aeine?aeaeaiiy niieoee 158 iieacaei, ui aiaethaaiiy
2I-i??aiiaiai oeeeeo ii ca‘yceo C(sp2)-C(sp3) i?ecaiaeeoue aei aeayeiai
cieiuaiiy aaoa?ioeeeeo. Aiaeia?/iee aoaeo ciaeaeaii ? a no?oeoo?? 159.

2.4. I?oi-o?iii oa eiai iio?aei?

O iieaeoe? i?oi-o?iiio 160 cai?noue eooiai? iai?oae c‘yaey?oueny iiaee
oaeoi?, yeee aeanoaa?e?co? ieaia?io eiioi?iaoe?th aeea?ae?ioeeeeo. Oea
a?aeooiaooaaiiy i?ae iaiiae?eaieie aeaeo?iiieie ia?aie a?oeeiaeueieo
ea?aii?eueieo a?oi. Iane?aeeii oeueiai ? caa?aaeaiiy aeniei?
eiioi?iaoe?eii? aio/eino? aeea?ae?ioeeeeo ? iaa?oue cieaeaiiy aia?a??
eiai aeaoi?iaoe?? ii??aiyii c 5-ieni-1,3-oeeeeiaaenaaee?iii.

O aaicaiaeueiaaieo iio?aeieo i?oi-o?iiio niinoa??aa?oueny iiaeaeueoa
ca?eueoaiiy iaaei?noeino? i?oi-o?iiiiaiai o?aaiaioo. Oea iaoiiaeaii
iineaaeaiiyi noi?yaeaiiy ca o/anoth ea?aii?eueieo a?oi. A ?acoeueoao? o
iieaeoe? 9,10-oaiaio?ao?iiio ??aiiaaaeia eiioi?iaoe?y e?eueoey
iaieaia?ia aiane?aeie a?aeooiaooaaiiy i?ae aoiiaie aiaeith o
ia??-iieiaeaiiyo aaicieueieo oeeee?a.

161 R2=R3=R4=H, a R1=Me, a R1=Et, a R1=i-Pr, a R1=t-Bu

162 R1=R3=R4=H, a R2=Me, a R2=Et, a R2=i-Pr, a R2=t-Bu

163 R2=R3=H, a R1=R4=Me, a R1=R4=Et, a R1=R4=i-Pr,

a R1=R4=t-Bu

164 R1=R4=H, a R2=R3=Me, a R2=R3=Et, a R2=R3=i-Pr, a R2=R3=t-Bu

Noa?e/i? aoaeoe cai?niee?a nooo?ai aieeaathoue ia eiioi?iaoe?ei?
oa?aeoa?enoeee aeea?ae?ioeeeeo o?eueee a iieaeoeao 161,163. Oea
iaoiiaeaii a?aeooiaooaaiiyi i?ae aee?eueiith oa ea?aii?eueiith a?oiaie.
A niieoeao 163a-a aeayea aeaoi?iaoe?y oeeeeo niicoa??aa?oueny eeoa i?e
cia/ieo ?ici??ao cai?niee?a.

Aiaethaaiiy i?oi-o?iiiiaiai e?eueoey ea?aioeeeeii ii ca‘yceo N(2)-N(3)
ni?e/eiy? ia?ao?ae aeea?ae?ioeeeeo a eiioi?iaoe?th iai?ae??nei
aiane?aeie iiyae 1,3-ae?eueieo aca?iiae?e. O aeiaaeeo aaoa?ioeeee?/ieo
iio?aeieo 166-170 ?icoe?aiiy noi?yaeaii? nenoaie iieaeoee iaoiiaeth?
cieiuaiiy aeea?ae?ioeeeeo, ui i?aeoaa?aeaeaii ?NAe niieoe 171,172.

171 172 172a

A iieaeoe? 172 a?aeooiaooaaiiy i?ae aeaiia ia‘?iieie cai?nieeaie
ni?e/eiy? oaeiae cia/ia ii?ooaiiy ieaia?iino? aiaeioeeee?/iiai
iiaea?eiiai ca‘yeo, ui iiaea aooe iiyniaii cia/iei aeeaaeii ?aciiainii?
no?oeoo?e 172a aei caaaeueii? aoaeiae iieaeoee.

2.5. 1,2-Aeea?ae?iaaoa?ioeeeee c aecioeeee?/iei iiaea?eiei ca‘yceii

sse ? a 1,4-aeea?ae?iaiaeiaao, aaoa?ioeeee a iieaeoeao 173,174 caa??aa?
aenieo eiioi?iaoe?eio aio/e?noue iacaaaeath/e ia a?aenooi?noue eooiai?
iai?oae. Oea iaoiiaeaii iaa?iiaoe/iei oa?aeoa?ii noi?yaeaii? nenoaie a
oeeee?.

173 X=O, a Y=O, a Y=NH, a Y=CH2

174 X=NH, a Y=O, a Y=NH, a Y=CH2

Ciaioaiiy iiey?iino? aecioeeee?/iiai iiaea?eiiai ca‘yceo ni?e/eiy?
iineeaiiy iaa?iiaoe/iiai oa?aeoa?o -nenoaie ?, ye iane?aeie, i?aeaeuaiiy
eiioi?iaoe?eii? aio/eino? aaoa?ioeeeeo.

Aiaethaaiiy aeea?ae?ioeeeeo aaicieueieie e?eueoeyie ii iiaea?eieo
ca‘yceao N=N ia ci?ith? eiai ieineo ??aiiaaaeio eiioi?iaoe?th aea
cia/ii i?aeaeuo? iaaei?no?noue aaoa?ioeeeeo aiane?aeie ineaaeaiiy
aoaeo?a noi?yaeaiiy ca o/anoth ea?aii?eueii? a?oie.

175 a X=O,

a X=NH,

a X=CH2

I?ioeeaaeiee aoaeo niinoa??aa?oueny a oo?ii??ei?aeeiao 175. Oea,
?iia??ii, iaoiiaeaii aeaeo?iiiaeiii?iei oa?aeoa?ii i‘yoe/eaiiiai
aaoa?ioeeeeo.

Aieea aeaeo?iiieo aoaeo?a cai?niee?a ia eiioi?iaoe?ei? oa?aeoa?enoeee
aeea?ae?ioeeeeo a iieaeoeao 176-180 caeaaeeoue a?ae oa?aeoa?o aca?iiae??
i?ae cai?nieeii ? i?noeiaeie ea?aii?eueiith oa ?i?iia?oiaie. A iieaeoeao
176-178 aecia/aeueiei ? noi?yaeaiiy aai iaaaeaioi? aca?iiae?? cai?nieea
c aecioeeee?/iei ca‘yceii N=I. Oea ni?e/eiy? a?eueoo aio/e?noue
aaoa?ioeeeeo a i?o?iiio?aeieo ii??aiyii c ai?iicai?uaieie. A niieoeao
179,180 niinoa??aa?oueny i?ioeeaaeiee aoaeo, ui iaoiiaeaii
aeaeo?iiiaeiii?iei oa?aeoa?ii ?i?iia?oie a oeeee?.

?ic?aooiee iaoiaeii HF/6-31G iieacaee, ui noa?e/i? aoaeoe cai?niee?a o
iieaeoeao 181-185 ia aieeaathoue ia ??aiiaaaeio eiioi?iaoe?th oa
aio/e?noue aaoa?ioeeeeo. O?eueee a no?oeoo?ao 181a,a niinoa??aaeinue
iii?oia ?icieiuaiiy oa i?aeaeuaiiy iaaei?noeino? aeea?ae?ioeeeeo, ye
iane?aeie a?aeooiaooaaiiy i?ae aee?eueiith oa ea?aii?eueiith a?oiaie.
?acoeueoaoe ?ic?aooie?a aeia?a ocaiaeaeothoueny c aeaieie ?NAe ?yaeo
niieoe 186-188.

189 190 191 192

?aioaaiino?oeoo?ia aeine?aeaeaiiy niieoe 189,190 oa eaaioiaio?i?/i?
?ic?aooiee iieaeoe 191,192 iieacaee, ui aiaethaaiiy aeea?ae?ioeeeeo ii
ca‘yceo =N-N ia ci?ith? ieaia?io aaiiao??th aaoa?ioeeeeo. Aea i?e
oeueiio niinoa??aa?oueny iii?oia i?aeaeuaiiy eiioi?iaoe?eii? aio/eino?
aeea?ae?ioeeeeo.

A oe?eiio o?aaa a?aecia/eoe, ui, ca aeeeth/aiiyi 1,3-oeeeeiaaenaaee?io
oa eiai aiaeia?a, 1,2-aeea?ae?ioeeeee ? a?eueo eiioi?iaoe?eii aio/eeie
ii??aiyii c 1,4-aeea?ae?i?ciia?aie. Oea iaoiiaeaii ciaioaiiyi ?ie?
noa?e/ieo aoaeo?a (cie?aia 1,2-ae?eueii? iai?oae) oa iniaeeainoyie
noi?yaeaiiy a oeeee?.

3. Aeaeo?iiia no?oeoo?a oanoe/eaiieo aeea?ae?ioeeee?a

Aiae?c aeaeo?iiii? no?oeoo?e oanoe/eaiieo aeea?ae?ioeeee?a iieacaa, ui
1,4- oa 1,2-aeea?ae?i ?ciia?e iathoue ii 4 -II, ye? ooai?ai? ca ?aooiie
pz-AO aoii?a iiaea?eieo ca‘yce?a oa i?noeiaeo a?oi ? o?aaiaioieo
inaaaei—i?a?oaeae iaoeeaiiaeo a?oi. Cai?ia iaoeeaiiaeo a?oi ia
aecioeeee?/i? iiaea?ei? ca‘ycee /e aaoa?iaoiie ia i?eaiaeeoue aei ci?ie
caaaeueii? neiao??? oeeo II. Niinoa??aa?oueny o?eueee ia?a?iciiae?e
aeaeo?iiii? aonoeie ia eiaei?e II. Oaeei /eiii, iiaeia c?iaeoe aeniiaie
i?i i?eioeeiiao iaeiaeia?noue aoaeiae -II a ?yaeao 1,4- oa
1,2-aeea?ae?ioeeee?a. I/aaeaeii, naia oea ? iaei??th c iniiaieo i?e/ei
oiai, ui eiioi?iaoe?eia aio/e?noue ? caaaeueiith aeanoea?noth oeueiai
eeano i?aai?/ieo niieoe iacaeaaeii a?ae iayaiino? iane/aiiai aoiio
aoaeaoeth a oeeee?.

Aea/aiiy ci?i o ?iciiae?e? aeaeo?iiii? aonoeie iieacaei ui ia?ao?ae
aeea?ae?ioeeeeo c ieaia?ii? ??aiiaaaeii? eiioi?iaoe?? aei iaieinei? ia
ni?e/eiy? iii?oieo ci?i o aaee/eiao ii?yaee?a ca‘yce?a, canaeaiinoae
ia?ae?eaaiiy oa ca?yae?a ia aoiiao. Aiaeia?/iee ?acoeueoao iaea?aeaii ?
i?e aeei?enoaii? oiiieia?/ii? oai??? Aaeaea?a. Oa?aeoa?enoeee e?eoe/ieo
oi/ie ?iciiae?eo aeaeo?iiii? aonoeie (3,-1), ye? ?icoaoiaai? ia
ca‘yceao, i?aeoe/ii ia ci?iththoueny i?e ia?aoiae? aeea?ae?ioeeeeo a
?ioo eiioi?iaoe?th. Oea oaeiae ni?y? aenie?e eiioi?iaoe?ei?e aio/eino?
/anoeiai a?ae?iaaieo e?eaoeue.

5. Aieea i?aeiieaeoey?ieo aca?iiae?e a e?enoae? ia eiioi?iaoe?th
aeea?ae?ioeeee?a

Ine?eueee aia?a?y i?aeiieaeoey?ieo aca?iiae?e o e?enoae? iaaaaaoi
a?eueoa /ei aia?a?y aeaoi?iaoe?? e?eueoey a oanoe/eaiieo
aeea?ae?ioeeeeao, aoei aea/aii aieea aoaeo?a oiaeiaee iieaeoe o oaaae?e
oac? ia i?inoi?iao aoaeiao aio/eeo oeeee?a. Iniiaia ?aeay aeine?aeaeaiiy
iieyaaea o aea/aii? no?oeoo?e iieaeoe, ye? ciaoiaeyoueny o ??ciiio
e?enoae?/iiio ioi/aii?, aea iathoue iaeiaeia? aioo??oiueiiieaeoey?i?
oaeoi?e, ui aieeaathoue ia eiioi?iaoe?th /anoeiai a?ae?iaaiiai e?eueoey.
Ii??aiyiiy i?inoi?iai? aoaeiae aeea?ae?ioeeee?a o iie?ii?oieo
iiaeeo?eaoe?yo, a oaeiae o ??cieo e?enoaeinieueaaoao ?yaeo niieoe
iieacaei, ui aa??aoe?? aiaeioeeee?/ieo oi?n?eieo eoo?a i?ae aieeaii
i?aeiieaeoey?ieo aca?iiae?e o e?enoae? ia ia?aaeuothoue 5i.

Aiaeia?/iee ?acoeueoao aoei iaea?aeaii i?e ii??aiyii? aaiiao???
aeea?ae?ii??ei?aeeiiaiai e?eueoey a no?oeoo?ao 156,193, ye?
a?ae??ciythoueny cai?nieeii o ia?eoa??ei?e /anoei? iieaeoee.

?noioi? a?aei?iiino? o eiioi?iaoe?? aeea?ae?ioeeeeo ciaeaeaii i?e
ii??aiyii? aoaeiae aea/aii? iaie niieoee 194 c e?oa?aoo?ieie aeaieie
aeey 195. ?aioaaiino?oeoo?ia aeine?aeaeaiiy 194 iieacaei, ui
aeea?ae?ii??ei?aeeiiaa e?eueoea a oe?e iieaeoe? cia/ii cieiuaia
ii??aiyii c 195 (ia?aiao?e ceeaae/aoino?: 194 S=0.11, =73.1, =7.9; 195
S=0.25, =71.9, =1.7). I?e/eiith oeueiai ? ??cieoey a aia?a??
i?aeiieaeoey?ieo aiaeiaaeo ca‘yce?a o e?enoaeao oeeo niieoe. Ooai?aiiy
a?eueo neeueieo aiaeiaaeo ca‘yce?a ni?e/eiy? cieiuaiiy aeea?ae?ioeeeeo a
iieaeoe? 194.

156 R=Br 194 R=H 196

193 R=F 195 R=Me

I?e a?aenooiino? iane/aiiai aoiio aoaeaoeth a e?eueoe? aeea?ae?ioeeee ?
iii?oii iaio /ooeeaei aei aieeao i?aeiieaeoey?ieo ac?iiae?e o e?enoae?.
O?eueee o aeiaaeeo niieoee 196 aoei ciaeaeaii, ui eiioi?iaoe?y aeaio
iieaeoe, ye? ?icoaoiaai? o neiao?e/ii iacaeaaei?e /anoei? aeaiaioa?ii?
eii??ee, iii?oii a?ae??ciy?oueny. Oea iaoiiaeaii iayai?noth cei?i/aiiai
i?aeiieaeoey?iiai eiioaeoo N…H o?eueee o iaei??? iieaeoee.

Oaeei /eiii, i?aeiieaeoey?i? aca?iiae?? o e?enoae? iiaeooue nooo?ai
aieeaaoe ea ??aiiaaaeio eiioi?iaoe?th aio/eeo oanoe/eaiieo
aeea?ae?ioeeee?a. Oiio i?e aeei?enoaii? ?acoeueoao?a ?NAe niieoe, ye?
i?noyoue o nai?io neeaae? oae? o?aaiaioe, iaiao?aeii aeaoaeueii
aiae?coaaoe e?enoae?/io no?oeoo?e aeey oiai, uia aecia/eoe iayai?noue
cia/ii? aeaoi?iaoe?? iieaeoey?ii? no?oeoo?e i?ae ae??th oiaeiai/ieo
aoaeo?a.

6. Eiioi?iaoe?eia aio/e?noue oanoe/eaiieo aeea?ae?ioeeee?a o a?ieia?/ii
aeoeaieo niieoeao

6.1. Aaii?noe oa aioaaii?noe eaeueoe??aeo eaiae?a ee?oei.

Aeniea eiioi?iaoe?eia aio/e?noue oanoe/eaiieo aeea?ae?ioeeee?a iiaea
noooaai aieeaaoe ia o?ceei-o?i?/i? aeanoeaino? niieoe, iniaeeai i?e
o/ano? iieaeoe o aca?iiae?yo oeio “a?noue-ainiiaea?”, iai?eeeaae o
a?ieia?/ieo nenoaiao. Oae? aoaeoe iaoiiaeththoue, cie?aia, a?ieia?/io
ae?th aaii?no?a oa aioaaii?no?a eaeueoe??aeo eaiae?a ee?oei — iio?aeieo
1,4-aeea?ae?ii??ei?aeeio. I?iaaaeai? i?ioyaii aaaaoueio ?ie?a
aeine?aeaeaiiy caeaaeiino? “no?oeoo?a-aeoeai?noue” i?eaaee aei
anoaiiaeaiiy ei?aeyoe?? i?ae nooiaiai ceeaae/aoino?
aeea?ae?ii??eaeeiiaiai e?eueoey ? o?c?ieia?/iith ae??th.

Aea ?ic?aooiee iaoiaeii iieaeoey?ii? iaoai?ee iieaeoe 197-205 iieacaee,
ui /anoeiai a?ae?iaaia e?eueoea a oeeo iieaeoeao ia? aenieo
eiioi?iaoe?eio aio/e?noue. ?ioa?aae ci?ie oi?n?eiiai eooa C=C-C(sp3)-C=
o yeiio aia?a?y iieaeoee i?aeaeuo?oueny iaioa i?ae ia 1 eeae/iieue
neeaaea? aeecueei 40i. Iaa?oue i?eeiath/e aei oaaae iaaeineiiae?noue
iaoiaeo ?ic?aooieo oey aaee/eia caeeoa?oueny aeinoaoiuei aaeeeith ?
iiai?noth ia?ae?eaa? iaeanoue o ye?e aoei ciaeaeaii ei?aeyoe?th. Oaeei
/eiii aeea?ae?ii??eaeeiiaee oeeee iiaea eaaei i?eeiaoe iaeaea?aei?oo
aeey ac?iiae?? c a?ieia?/iei ?aoeaioi?ii eiioi?iaoe?th aac nooo?aeo
cao?ao aia?a??. Oiio ciaeaeaia ?ai?oa ei?aeyoe?y i?ae ceeaae/aoino?
aeea?ae?ii??eaeeiiaiai e?eueoey ? o?c?ieia?/iith ae??th ? cia/iith
i??ith aeiaaeeiaa.

6.2. Iniiae ioeea?iiaeo eeneio

?ic?aooiee iaoiaeaie HF/6-31G**, B3LYP/6-31G** ? MP2/6-31G** iieacaee,
ui i??ei?aeeiia? e?eueoey, ye? i?noyoueny o neeaae? iniia ioeea?iiaeo
eeneio — o?aoeeeo (206), oei?io (207), oeeoiceio (208), ?cioeeoiceio
(209) oa aoai?io (210) — oaeiae ? eiioi?iaoe?eii iaaei?noeeie. Iaea?eueo
aio/eei ? aaoa?ioeeee a o?aoeee? ? oei?i?, ye? iathoue aioea?iiaoe/io
noi?yaeaio nenoaio, a iaea?eueo aei?noeei — o ?cioeeoicei? oa aoai?i?
(oaae.1).

206 R=H 208 209 210

207 R=Me

Oaaeeoey 1.

Ci?ia aia?a?? (eeae/iieue) i?e aeaei? i??ei?aeeiiaiai oeeeeo a
iieaeoeao 206-210 oa Oionii-E??e?anueeeo ia?ao iniia AO oa GC ca aeaiei
eaaioiaio?i?/ieo ?ic?aooie?a.

Niie.Oi?n?e-IaoiaeAaee/eia oi?n?eiiai eooa, a?aae.iee
eoo0102030206N-C-N-CMP2/6-31G**00.170.711.75207N-C-N-CMP2/6-31G**00.170.
731.80208C-N-C-NMP2/6-31G**00.150.721.78209C-N-C-CMP2/6-31G**00.311.202.
84210C-N-C-CMP2/6-31G**00.271.132.76
AON-C-N-CMP2/6-31G**00.230.952.30GCC-N-C-N MP2/6-31G**00.612.435.78

Iaaei?noe?noue i??ei?aeeiiaiai e?eueoey a niieoeao 207,208,210
caa??aa?oueny ? i?e ooai?aii? aiaeiaai ca‘ycaieo Oionii-E??e?anueeeo ia?
iniia (oaae. 1). I?e oeueiio ciai?ieiueii? eieeaaiiy aeea?ae?ioeeee?a o
ia?? aoai?i-oeeoicei i?aeoe/ii ia caeaaeaoue iaeei a?ae iaeiiai.

7. Aieea eiioi?iaoe?eii? aio/eino? aeea?ae?ioeeee?a ia o?ceei-o?i?/i?
aeanoeaino? niieoe

7.1. Aieea eiioi?iaoe?eii? aio/eino? e?eueoey ia a?aeiinio
noaa?euei?noue ?ciia?ieo oeeeeiaaenaaee?i?a.

Aeniea eiioi?iaoe?eia aio/e?noue oanoe/eaiieo aeea?ae?ioeeee?a icia/a?
iayai?noue o eieeaaeueiiio niaeo?? oaeeo niieoe iecueei/anoioieo
eieeaaiue, ye? a?ae?ia?aeathoue aeaoi?iaoe?? /anoeiai a?ae?iaaiiai
e?eueoey. ??cia eiioi?iaoe?eia aio/e?noue aeea?ae?ioeeee?a
a?aeaeaa?oueny ia aaee/eiao /anoio oaeeo eieeaaiue. Oiaoi
iecueei/anoioi? eieeaaiiy iieaeoe, ye? ii??aiththoueny, aoaeooue aiineoe
??ciee aeeaae aei eieeaaeueii? /anoeie aio?ii??. Oaeei /eiii, ??cieoey o
eiioi?iaoe?ei?e aio/eino? /anoeiai a?ae?iaaieo e?eaoeue iiaea nooo?ai
aieeaaoe ia aaee/eio aio?ii?? ?, ye iane?aeie, ia a?aeiinio
noaa?euei?noue ?ciia??a oa oaooiia??a.

Oaaeeoey 2

A?aeiinia noaa?euei?noue ?ciia?ieo oeeeeiaaenaaee?i?a ca aeaiei
iaaii??e/ieo eaaioiaio?i?/ieo ?ic?aooie?a.

IaoiaeNiaae.EDFT (EMP2), eeae/iieueG0K, eeae/iieue Gt, (0298K)
eeae/iieue G298K,
eeae/iieueMP2/6-31G(d,p)CHD13000.610CHD141.471.2900.68MP2/6-311++G(d,p)C
HD13001.040CHD142.001.5900.55

Iaaii??e/i? eaaioiaio?i?/i? ?ic?aooiee oa?iiaeeiai?/ieo oa?aeoa?enoee
?ciia?ieo oeeeeiaaenaaee?i?a iieacaee (oaae.1), ui NHD13 i?e 0 E ? ia
1.3-1.6 eeae/iieue a?eueo noaa?eueiei. I?aeaeuaiiy oaiia?aoo?e aei 298 E
ni?e/eiy? nooo?ao aeanoaa?e?caoe?th oeueiai ?ciia?o (G=0.6 eeae/iieue).
Oea iaoiiaeaii ??cieoeath o eieeaaeueieo aeeaaeao o aio?ii?th aiane?aeie
cia/ii a?eueoi? eiioi?iaoe?eii? aio/eino? aeea?ae?ioeeeeo o CHD14.

7.2. Aieea eiioi?iaoe?eii? aio/eino? /anoeiai a?ae?iaaiiai e?eueoey ia
o?ceei-o?i?/i? aeanoeaino? aei?noeieaioethaiaeo aaoa?ioeeee?/ieo
iie?ia??a.

Eiioi?iaoe?eia aio/e?noue /anoeiai a?ae?iaaieo e?eaoeue iiaea nooo?ai
aieeaaoe ? ia ?io? o?ceei-o?i?/i? aeanoeaino? ?a/iaei, iai?eeeaae,
aei?noeieaioethaiaeo aaoa?ioeeee?/ieo iie?ia??a ia iniia? iaoo?e?i?aeo,
ye? ? iniiaith aeey noai?aiiy iaaei?oeieo iaoa??aae?a c? niaoe?aeueieie
aeanoeainoyie. Iniiaiith oa?aeoa?enoeeith oaeeo iie?ia??a ? aeiaaeeia
i?yiiai a?ae??cea iae?iiieaeoee (aaee/eia naaiaioo Eoia). O aeiaaeeo
iie?ia??a, ye? ia i?noyoue iane/aieo aoii?a aoaeaoeth, oey aaee/eia
iiaeiia aooe aeoaea aaeeeith, iaaeeaeath/enue o a?aieoe? aei
aace?ia/iino?. Aea aenia?eiaioaeuei? aeine?aeaeaiiy iieacaee, ui naaiaio
Eoia a oaeeo iae?iiieaeoeao cia/ii ei?iooee a?ae ia?aaeaa/oaaiiai.
Iiynieoe oea i?ioyaii aeiaaiai /ano ia aaeaaaeiny.

?ic?aooiee iaoiaeii AI1 ?yaeo iiaeaeueieo niieoe 210-213 iieacaee, ui
?i?aeiee oa aia?ae?eaeiee oeeeee a oeeo iieaeoeao iathoue aenieo
eiioi?iaoe?eio aio/e?noue. Ia?ao?ae c ieinei? ??aiiaaaeii? eiioi?iaoe??
aei eiioi?iaoe?? nioa c a?aeiia?aeiei oi?n?eiei eooii 20 aeeeeea?
i?aeaeuaiiy aia?a?? iieaeoe iaioa i?ae ia 1.2 eeae/iieue. Oea aeicaiey?
i?eionoeoe iiaeeea?noue ?nioaaiiy nooo?ai iaieaia?ieo /anoeiai
a?ae?iaaieo e?eaoeue o iae?iiieaeoeao, ye? i?noyoue oae? o?aaiaioe.
Aiane?aeie oeueiai iiaea a?aeaoaaoeny cia/ia aeaoi?iaoe?y
iaee/eiiiae?aiiai iie?ia?o, ui ni?e/eiy? ciaioaiiy naaiaioo Eoia.

Iiaeaethaaiiy aoaeiae iie?iaoo?e?i?ae?a iaoiaeii Iiioa-Ea?ei, yea
aeeiiaii ?.I.?iiiaith (?IAIN ?AI) iiai?noth i?aeoaa?aeeei oea
i?eiouaiiy. O?aooaaiiy iaieaia?ii? aaiiao??? ?i?aeieo oeeee?a anueiai a
10-15% aeaiaioa?ieo eaiie aeicaiey? iaea?aeaoe aaee/eie naaiaioo Eoia
aeecuee? aei aenia?eiaioaeueieo aeaieo.

Aeniiaee

1. Ia iniia? iaea?aeaieo aenia?eiaioaeueieo ? oai?aoe/ieo aeaieo i?i
aoaeiao oanoe/eaiieo aeea?ae?ioeeee?a anoaiiaeaii:

n noa?e/i? aoaeoe cai?niee?a nooo?ai aieeaathoue ia eiioi?iaoe?ei?
oa?aeoa?enoeee aeea?ae?ioeeeeo o aeiaaeeo iayaiino? cai?niee?a i?e
iane/aieo aoiiao aoaeaoeth, iai?eeeaae o 1,4- oa
1,2-aeea?ae?iaaoa?ioeeeeao;

n aieea aeaeo?iiieo aoaeo?a cai?niee?a iaoiiaeaiee, o ia?oo /a?ao,
oa?aeoa?ii oa aoaeoeai?noth ?o eii‘thaaoe?eieo aca?iiae?e c i?noeiaeie
a?oiaie;

n aiaethaaiiy aeea?ae?ioeeee?a a?iiaoe/ieie e?eueoeyie ii iiaea?eiei
ca‘yceai ni?e/eiy? i?aeaeuaiiy eiioi?iaoe?eii? iaaei?noeino? /anoeiai
a?ae?iaaiiai e?eueoey aiane?aeie iineeaiiy eooiai? iai?oae ? ineaaeaiiy
eii‘thaaoe?eieo aca?iiae?e ca o/anoth i?noeiaeo a?oi.

2. Iieacaii, ui an? oeie oanoe/eaiieo 1,2- oa 1,4-aeea?ae?ioeeee?a, o
oiio /ene? ? o?, ye? ia i?noyoue iane/aieo aoii?a aoaeaoeth a e?eueoe?,
iathoue aenieo eiioi?iaoe?eio aio/e?noue, iaoiiaeaio oiieei aaeainii
noa?e/ieo ? aeaeo?iiieo aca?iiae?e, noaa?e?coth/eo ieaia?io aai iaieineo
eiioi?iaoe?th /anoeiai a?ae?iaaiiai e?eueoey.

3. Anoaiiaeaii aecia/aeueiee aieea nooiaith a?iiaoe/iino? oeeee?/ii?
noi?yaeaii? nenoaie ia eiioi?iaoe?eio aio/e?noue aeea?ae?ioeeee?a o
o?iiiao oa iio?aeieo aeea?ae?iaaoa?ioeeee?a c aecioeeee?/iei iiaea?eiei
ca‘yceii.

4. Ca aeiiiiiaith iaaii??e/ieo eaaioiai-o?i?/ieo ?ic?aooie?a iieacaii
i?eioeeiiao iiae?ai?noue -aeaeo?iiii? no?oeoo?e /anoeiai a?ae?iaaieo
e?eaoeue o ?yaeo 1,4- ? 1,2-aeea?ae?ioeeee?a. Anoaiiaeaii, ui ci?ia
eiioi?iaoe?? /anoeiai a?ae?iaaiiai e?eueoey ianooo?ai aieeaa? ia
?iciiae?e aeaeo?iiii? aonoeie oa aaee/eie ii?yaee?a ca‘yce?a ? ca?yae?a
ia aoiiao.

5. Ia iniia? c?noaaeaiiy ?acoeueoao?a ?ic?aooie?a aaiiao??? iieaeoe ?
aeaieo ?aioaaiino?oeoo?ieo aeine?aeaeaiue iieacaii, ui aoaeoe oiaeiaee
iieaeoe o e?enoae? iii?oii aeaoi?iothoue eiioi?iaoe?th oanoe/eaiieo
aeea?ae?ioeeee?a o?eueee i?e iayaiino? neeueieo niaoeeo?/ieo
i?aeiieaeoey?ieo aca?iiae?e oaeeo, ye i?aeiieaeoey?i? aiaeiaa? ca‘ycee.

6. Anoaiiaeaii, ui ei?aeoia iiaoaeiaa caeaaeiinoae
“no?oeoo?a-aeoeai?noue” o ?yaeo aaii?no?a oa aioaaii?no?a eaeueoe??aeo
eaiae?a ee?oei, iio?aeieo 1,4-aeea?ae?ii??eaeeio, iiaeeeaa o?eueee c
o?aooaaiiyi eiioi?iaoe?eii? aeeiai?ee aeea?ae?ii??eaeeiiaiai e?eueoey.

7. Aia?oa ciaeaeaii aenieo eiioi?iaoe?eio aio/e?noue i??ei?aeeiiaeo
e?eaoeue a iniiaao ioeea?iiaeo eeneio, yea caa??aa?oueny i?e ooai?aii?
Oionii-E??e?anueeeo ia? iniia, ? iiaea nooo?ai aieeaaoe ia no?oeoo?o oa
ooieoe?? AeIE.

8. Iieacaii, ui a?aei?ii?noue a aia?a?? aeaoi?iaoe?? aeea?ae?ioeeeeo
nooo?ai aieeaa? ia a?aeiinio noaa?euei?noue ?ciia?ieo oeeeeiaaenaaee?i?a
aaea i?e e?iiaoi?e oaiia?aoo??.

9. Ia iniia? aiae?co eiioi?iaoe?eii? aeeiai?ee oanoe/eaiieo /anoeiai
a?ae?iaaieo e?eaoeue, ye? aoiaeyoue aei neeaaeo iiiiia?ii? eaiee
aei?noeieaioethaiaeo aaoa?ioeeee?/ieo iie?ia??a, aia?oa iiyniaii
aenia?eiaioaeueii ciaeaeai? aaee/eie naaiaioo Eoia o oaeeo
iae?iiieaeoeao.

Iniiai? ?acoeueoaoe ?iaioe aeeeaaeai? a oaeeo ioae?eaoe?yo:

1. Oeoeei I.A. Eiioi?iaoeeiiiay aeaeinoue oanoe/eaiiuo aeeaeae?ioeeeeia
(iaci?)//Eca.AI. Na?.oei.-1997.-?12.-N.2095-2105.

2. Aeeyiea caianoeoaeae i?e iaianuuaiiuo aoiiao oaea?iaea ia
eiioi?iaoeeth 1,3-oeeeeiaaenaaeeaiiaiai eieueoea / I.A.Oeoeei,
A.A.Ca?oei, N.I.Aeanaiei, A.Ae.I?eia, O.A.Oeiioaaaa, N.A.Eeiaeaiai,
TH.O.No?o/eia // Oai?. e yenia?.oeiey.-1992.-?4.-N.334-337.

3. Eiaa?ney oeeeea a 1,3-oeeeeiaaenaaeeaia e aai 5-aeeeei?iecaiaeiuo
/I.A.Oeoeei, A.A.Ca?oei, O.A.Oeiioaaaa, N.I.Aeanaiei, A.Ae.I?eia,
N.A.Eeiaeaiai, TH.O.No?o/eia //Eca. AI. Na?. oei.-1993.-?6.-N.1120-1122.

4. Aeeyiea acieueiiai oeeeea ia eiioi?iaoeeiiioth aeaeinoue
aeeaeae?iie?eieaeeiiaiai eieueoea a
4,7-aeeaeae?iaciei[1,5-a]ie?eieaeeiao ii aeaiiui iaoiaea MNDO /
I.A.Oeoeei, N.I.Aeanaiei, A.Ae.I?eia, N.A.Eeiaeaiai, TH.O.No?o/eia,
A.N.Iieyeiaa, A.E.Ieoaaeueeeia //Eca. AI.
Na?.oei.-1994.-?8.-N.1418-1420.

5. Conformational flexibility of 1,4-dihydroazines / O.V.Shishkin,
A.S.Polyakova, S.M.Desenko, Yu.T.Struchkov // Mendeleev
Commun.-1994.-?5.-?.182-183.

6. Aeeyiea yeaeo?iiiuo acaeiiaeaenoaee iaaeaeo aeaieiuie naycyie ia
eiioi?iaoeeiiioth aeaeinoue 1,4-oeeeeiaaenaaeeaia / I.A.Oeoeei,
A.N.Iieyeiaa, N.I.Aeanaiei, I.A.I?aaeaei, A.Ae.I?eia, TH.O.No?o/eia //
Eca. AI. Na?. oei.-1994.-?9.-N.1676-1677.

7. Oeoeei I.A., No?o/eia TH.O. Eiioi?iaoeeiiiay aeaeinoue oanoe/eaiiiai
oeeeea a 5-ieni-1,3-oeeeeiaaenaaeeaia e aai i?iecaiaeiuo//Eca.AI.
Na?.oei.-1995.-?5.-N.849-854.

8. The novel thermal rearrangement in the pyrido[1,2-a]pyrimidine
series: the transformation of
3-acetyl-4-phenylaminopyrido[1,2-a]pyrimidine-4-on/ V.S.Bogdanov,
K.L.Cherkasova, V.A.Dorokhov, O.V.Shishkin, Yu.T.Struchkov// Mendeleev
Commun.-1995.-?3.-P.106-107.

9. I no?iaiee i?iaeoeoia acaeiiaeaenoaey
5,6-aeeaieii-1,3-aeeiaoeeo?aoeeea n
1,3-aeea?ee-2,3-aeeaaeiaaii?iiaiiiaie/ I.I.Eiein, I.A.Oeoeei,
A.Ae.I?eia, TH.O.No?o/eia// Oeiey aaoa?ioeeee.
niaaeei.-1995.-?4.-N.551-557.

10. Shishkin O.V. Conformational flexibility of dihydropyrimidinone and
tetrahydropyrimidin-2,4-dione rings in DNA bases.//
J.Chem.Soc.Chem.Commun.-1995.-?8.-P.1539.

11. Shishkin O.V. Conformational flexibility of 1,4-dihydroazine
carbonyl derivatives. // Monatsch. Chem.-1996.-V.127.-?8-9.-P.883-886.

12. Neioac e no?iaiea i?iecaiaeiuo
3,7-aeeaeae?i-2I-1,2,4-o?eaciei[1’,5’-a’]ie?eieaei[4,5-d]aaici[b]ie?aia
/ N.I.Aeanaiei, A.Ae.I?eia, I.A.Aaoiaineee, N.A.Eiiuoia, A.A.Iaiiiia,
A.TH.Eiaaeaaneee, I.A.Oeoeei, TH.O.No?o/eia // Oeiey aaoa?ioeeee.
niaaeei.-1996.-?2.-N.240-246.

13. Neioac iaeioi?uo na?oniaea?aeaueo ie?eaei[1,2-a]ie?eieaeeiia /
E.E.*a?eaniaa, A.A.Aiaaeaiia, A.A.Aei?ioia, I.A.Oeoeei, TH.O.No?o/eia //
Eca.AI. Na?.oei.-1996.-?6.-N.1508-1510.

14. Shishkin O.V. Conformational flexibility of the 1,4-dihydropyridine
ring in calcium channel agonists and antagonists molecules. //
J.Mol.Struct.-1996.-V.385.-?3.-P.209-214.

15. Oeoeei I.A., Iieyeiaa A.N. Yeaeo?iiiay no?oeoo?a e eiioi?iaoeeiiiay
aeaeinoue 1,4-aeeaeae?iaceiia e eo 4-eeeaeiuo i?iecaiaeiuo // Eca.AI.
Na?. oei.-1996.-?8.-N.1938-1941.

16. Ia?aciaaiea aaicioo?aiiaie e 2I-ie?aiiaie no?oeoo? a ?acoeueoaoa
iaeiie ?aaeoeee. Iiaue neioac i?iecaiaeiuo 2I-o?iiaia / E.TH.Ooei,
AE.E.I?eiaa, I.A.Oeoeei, TH.O.No?o/eia // Eca.AI.
Na?.oei.-1996.-?5.-N.1222-1228.

17. Oeoeei I.A. Eiioi?iaoeeiiiay aeaeinoue oanoe/eaiiuo
1,2-aeeaeae?ioeeeeia ii aeaiiui iaoiaea AI1. // Eca.AI.
Na?.oei.-1996.-?11.-N.2650-2652.

18. Neioac i?iecaiaeiuo 5I-oeaciei[3,2-a]ie?eieaeeia ec
6-iaoee-2-oeio?aoeeea, 1-aoeee-2-a?iiaoeaoeeaiia. ?aioaaiino?oeoo?iia
enneaaeiaaiea 3-aaiciee-7-iaoee-5I-oeaciei[3,2-a]-ie?eieaeei-5-iia /
A.I.Aeioeia, A.N.Iaoiaiiae/, C.A.Noaiaiiaa, A.A.Eiiu?aa, I.A.Aaiieeiaa,
TH.O.No?o/eia, I.A.Oeoeei // Eca.AI. Na?.oei.-1996.-?9.-N.2306-2308.

19. Neioac i?iecaiaeiuo 5I-oeaciei[2,3-c][1,2,4]o?eaceia e caiauaiiuo
3-aoeeeaeieeoei-1,2,4-o?eacei-5-iiia ec
6-iaoee-3-oeieni-1,2,4-o?eacai-5-iia, 1-aoeaoee-2-aeiee-a?iiaoeaoeeaiia
e 2-aoeaoeeaiiauo eaoiiia. ?aioaaiino?oeoo?iia enneaaeiaaiea
3-aaiciee-5I-oeaciei[2,3-c][1,2,4]o?eacei-5-iia / A.I.Aeioeia,
A.N.Iaoiaiiae/, O.I.Eiia?iaa, ?.A.Ea?iaooiaa, I.A.Aaiieeiaa,
A.A.Eiiu?aa, TH.O.No?o/eia, I.A.Oeoeei, E.A.Iioaoei // Eca.AI.
Na?.oei.-1996.-?12.-N.2971-2974.

20. Oeoeei I.A. Yeaeo?iiiay no?oeoo?a e eiioi?iaoeeiiiay aeaeinoue
1,6-aeeaeae?iie?eaeeia, 1,2-, 1,6-aeeaeae?iie?eieaeeiia e eo eeeaeiuo
i?iecaiaeiuo // Eca.AI. Na?.oei.-1996.-?8.-N.1934-1937.

21. Shishkin O.V., Antonov D.M. Molecular, electronic structure and
conformational flexibility of the 1,6-dihydropyrimidine,
4,5-dihydrofuro[2,3-d]pyrimidine and their oxo, imino and methylene
derivatives // J.Mol.Struct.-1996.-V.385.-?1.-P.55-63.

22. Shishkin O.V. Molecular structure and conformational flexibility of
the 1,3-cyclohexadiene carbonyl derivatives //
J.Mol.Struct.-1997.-V.403.-?2.-P.167-170.

23. Oeoeei I.A., Eiein I.I., I?eia A.Ae. Iieaeoey?iay e e?enoaeee/aneay
no?oeoo?a N,N’-aeeiaoee-5,6-aeeaieiio?aoeeea //
E?enoaeeia?aoey.-1997.-O.42.-?2.-N.293-295.

24. Shishkin O.V. Conformational flexibility of six-membered
1,4-dihydrocycles // J. Mol.Struct.-1997.-V.412.-?3.-P.115-120.

25. Ooei E.TH., Oeoeei I.A. Neioac
2-aeae?iene-5-ieo?ioaieeaee[1-(2-aeae?ieneiaooee)]iaoaia e
12-[1-(2-aeae?ieneiaooee)]-10-ieo?i-12I-aaici-[a]enaioaia ec
i?iecaiaeiuo 5-ieo?inaeeoeeeiaiai aeueaeaaeaea e -iaooiea // Eca. AI.
Na?.oei.-1997.-?7.-N.1336-1339.

26. ?iiiaa E.A., Iiiiia?aa E.E., Oeoeei I.A. Oniaaiiinoe
eiioi?iaoeeiiiiai iiaaaeaiey noa?aeiaia?aciuo iieeiaooieeaieieaeia //
Aunieiiie. niaaeei.-1997.-O.A39.-?10.-N.1666-1669.

27. ?aaeoeee a?iiaoe/aneeo ieo?iniaaeeiaiee. LXXI. Acaeiiaeaenoaea
aieiiiiuo -eiiieaenia 9-ieo?iaio?aoeaia n ia?ieneaeii aiaei?iaea
/E.A.Aeioei, TH.I.Ao?iuaiei, I.A.Oeoeei, N.N. Aeoen, A.I.Aeeoaiiaa,
I.E.Aeioeia, A.ss.Eaieineee, TH.Ae.A?oaeoeui, E.A.Oaoeaeueaeyi // AE.
I?a. Oei.-1997.-O.33.-?9.-N.1363-1367.

28. Structure of
6a,7-dihydro-2,6-dimethyl-7-phenyl-6H-chromeno[4,3-d][1,2,4]triazolo-[1,
5-a]pyrimidine-6a-ol. / A.Yu.Kovalevsky, V.A.Chebanov, S.M.Desenko,
S.A.Komykhov, V.D.Orlov, O.V.Shishkin, H.Meier // Acta
Cryst.-1997.-V.C53.-?9.-P.1356-1357.

29. The unusual transformation of 2-hydroxy-1-naphtalaldehyde in case
of reactions with morpholine / L.Yu.Ukhin, Z.S.Morkovnik,
O.S.Philipenko, S.M.Aldoshin, O.V.Shishkin // Mendeleev
Commun.-1997.-?4.-P.153-154.

30. Oeoeei I.A., Iiiiia?aa E.E. Eiioi?iaoeeiiiay aeaeinoue /anoe/ii
aeae?e?iaaiiuo oeeeeia a yeaiaioa?iuo caaiueyo aeanoeioeaiiuo
aaoa?ioeeeee/aneeo iieeia?ia // Eca. AI. Na?. oei.-1997.-?1.-N.64-66.

31. Iieaeoey?iay e e?enoaeee/aneay no?oeoo?a
11-oaiee-4,9,10,11-oao?aaeae?i-1,2,4-o?eaciei[5,1-b]iaooi[1,2-d]ie?eieae
eia. I?e?iaea ?acoii?yaei/aiiinoe aeeaeae?iiaooaeeiiaiai o?aaiaioa /
I.A.Oeoeei, I.I.Aaaeoiia, N.I.Aeanaiei, I.A.Aaoiaineee, A.Ae.I?eia //
E?enoaeeia?aoey-1998.-O.43.-?1.-N.39-46.

32. Borbulevych O.Y., Shishkin O.V. Conformational flexibility of 1,4
heterocyclic analogues of 1,4-cyclohexadiene //
J.Mol.Struct.-1998.-V.446.-?1-2.-P.11-14.

33. Iieaeoey?iay, yeaeo?iiiay no?oeoo?a e eiioi?iaoeeiiiue aiaeec
aieiiiuo -eiiieaenia i?iecaiaeiuo 9-ieo?iaio?aoeaia / I.A.Oeoeei,
I.ss.Ai?aoeaae/, E.A.Aeioei, TH.I.Ao?iuaiei, N.N.Aeoen // Eca. AI. Na?.
oei.-1998.-?3.-N.438-443

34. Eiaaeaaneee A.TH., Oeoeei I.A., Aeaeai?eeaae/ I.I. Aeeyiea
aaicaiiaee?iaaiey ia eiioi?iaoeeiiioth aeaeinoue oeeeea a ieni, eieii e
iaoeeaii?iecaiaeiuo 1,4-oeeeeiaaenaaeeaia // Eca.
AI.Na?.oei.-1998.-?3.-N.388-390.

35. Shishkin O.V. Conformational flexibility of six-membered
1,2-dihydrocycles and substituent electronic effects // J.
Mol.Struct.-1998.-V.447.-?3.-P.217-222.

36. Shishkin O.V. Conformational flexibility of di- and
tetrahydropyrimidine rings in nucleic acid bases. An ab initio
HF/6-31G** study // J.Mol.Struct.-1998.-V.447.-?1.-P.1-5.

AIIOAOe?ss

Oeoe?i I.A. Iieaeoey?ia no?oeoo?a oa eiioi?iaoe?eiee aiae?c
oanoe/eaiieo aeea?ae?ioeeee?a.-?oeiien.

Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy aeieoi?a o?i?/ieo iaoe ca
niaoe?aeuei?noth 02.00.03 — i?aai?/ia o?i?y. Oa?e?anueeee aea?aeaaiee
oi?aa?neoao, Oa?e?a, 1999.

Anoaiiaeaii iniiai? caeiiii??iino? i?inoi?iai? aoaeiae oanoe/eaiieo
aeea?ae?ioeeee?a. Iieacaii, ui an? oeie oeeee?a iathoue aaeeeo
eiioi?iaoe?eio aio/e?noue. Aeine?aeaeaii aieea aeaeo?iiieo oa noa?e/ieo
aoaeo?a cai?niee?a ? aiaethaaiiy e?eueoeyie ??ciiai oeio ia
eiioi?iaoe?ei? oa?aeoa?enoeee /anoeiai a?ae?iaaieo oeeee?a. Aea/aii
aieea i?aeiieaeoey?ieo aca?iiae?e o e?enoae? ia eiioi?iaoe?th aio/eeo
oeeee?a. Iieacaii, ui aeniea eiioi?iaoe?eia aio/e?noue oanoe/eaiieo
aeea?ae?ioeeee?a iiaea iii?oii aieeaaoe ia o?ceei-o?i?/i? aeanoeaino?
niieoe, iniaeeai o a?ieia?/ieo nenoaiao.

Eeth/ia? neiaa: oanoe/eaii? aeea?ae?ioeeeee, iieaeoey?ia no?oeoo?a,
eiioi?iaoe?eiee aiae?c, eiioi?iaoe?eia aio/e?noue.

AIIIOAOeEss

Oeoeei I.A. Iieaeoey?iay no?oeoo?a e eiioi?iaoeeiiiue aiaeec
oanoe/eaiiuo aeeaeae?ioeeeeia.- ?oeiienue.

Aeenna?oaoeey ia nieneaiea o/aiie noaiaie aeieoi?a oeie/aneeo iaoe ii
niaoeeaeueiinoe 02.00.03 — i?aaie/aneay oeiey. Oa?ueeianeee
ainoaea?noaaiiue oieaa?neoao, Oa?ueeia, 1999.

Aeenna?oaoeey iinayuaia enneaaeiaaiey i?ino?ainoaaiiiai no?iaiey e
eiioi?iaoeeiiiuo oa?aeoa?enoee oanoe/eaiiiuo 1,4- e
1,2-aeeaeae?ioeeeeia.N iiiiuueth ni/aoaiey aeaiiuo ?aioaaiino?oeoo?iiai
enneaaeiaaiey e ?an/aoia iaoiaeaie iieaeoey?iie iaoaieee e eaaioiaie
oeiee ?yaeia niaaeeiaiee onoaiiaeaii, /oi iieaeoey?iay no?oeoo?a
/anoe/ii aeae?e?iaaiiuo eieaoe ii?aaeaeyaony oiieei aaeainii
acaeiiaeaenoaee, iaeie ec eioi?uo (1,2-aeeeeueiia iai?yaeaiea,
nii?yaeaiea, acaeiiaeaenoaey /a?ac aaeaioioth naycue) noaaeeece?otho
ieaia?ioth eiioi?iaoeeth oeeeea, a ae?oaea (oaeiaia iai?yaeaiea,
noa?e/aneia iooaeeeaaiea iaaeaeo caianoeoaeyie, ioeeiiaiea oa?aeoa?a
nii?yaeaiiie nenoaiu a oeeeea io a?iiaoe/aneiai) aeaaii?eyonoaotho
iaieineiio no?iaiea eieueoea.Iieacaii, /oi ana oeiu aeeaeae?ioeeeeia,
iacaaeneii io iaee/ey eee ionoonoaey ianuuaiiuo aoiiia oaea?iaea a
eieueoea, iaeaaeatho aunieie eiioi?iaoeeiiiie aeaeinoueth.

Noa?e/aneea yooaeou caianoeoaeae ea?atho iaeaieaa nouanoaaiioth ?ieue
i?e iaee/ee a oeeeea ianuuaiiuo aoiiia oaea?iaea. Aaaaeaiea aeeeeueiuo
a?oii e yiaeioeeeee/aneei aeaieiui naycyi i?aeoe/anee ia eciaiyao
eiioi?iaoeeiiiua oa?aeoa?enoeee /anoe/ii aeae?e?iaaiiiai eieueoea. A
neo/aa iiyaeaiey oaeeo caianoeoaeae i?e aoiia N(sp3) i?ienoiaeeo
?acoieiuaiea aeeaeae?ioeeeea e caiaoiia nieaeaiea aai eiioi?iaoeeiiiie
aeaeinoe.

Aeeyiea yeaeo?iiiuo yooaeoia caianoeoaeae ii?aaeaeyaony oa?aeoa?ii
acaeiiaeaenoaey yoeo a?oii n iinoeeiauie o?aaiaioaie, a oaeaea i?e?iaeie
nii?yaeaiiie nenoaiu eieueoea. Oae, a aioea?iiaoe/aneeo
1,4-aeeaaoa?ioeeeeao ana aeoeaioi?iua caianoeoaee aucuaatho oieiuaiea
oeeeea e cia/eoaeueiia iiauoaiea aai eiioi?iaoeeiiiie aeanoeinoe.

Aiiaee?iaaiea aeeaeae?ioeeeeia aaicieueiuie eieueoeaie i?eaiaeeo e
nouanoaaiiiio iiauoaieth aeaeinoe /anoe/ii aeae?e?iaaiiiai eieueoea, a a
iaeioi?uo neo/ayo e aai ?acoieiuaieth. Yoi iaoneiaeaii oneeaieai
oaeiaiai iai?yaeaiey (i?e iaee/ee a oeeeea ianuuaiiuo aoiiia oaea?iaea)
e ineaaeaieai nii?yaeaiey iaaeaeo -nenoaiaie a?iiaoe/aneeo eieaoe e
iinoeeiauo a?oii (a inoaeueiuo neo/ayo).

Aiaeec -aeaeo?iiiie no?oeoo?u oanoe/eaiiuo aeeaeae?ioeeeeia iieacae,
/oi iauay neiiao?ey -II a ?yaeao 1,4- e 1,2-aeeaeae?ioeeeeia
nio?aiyaony, iacaaeneii io i?enoonoaey a no?oeoo?a ianuuaiiuo aoiiia
oaea?iaea, aaoa?iaoiiia eee yecioeeeee/aneeo aeaieiuo naycae. Eciaiaiee
eiioi?iaoeee aeeaeae?ioeeeeia ia ieacuaaao caiaoiiai aeeyiey ia
aaee/eiu ii?yaeeia naycae, ca?yaeia ia aoiiao a oaeaea oa?aeoa?enoeee
?ani?aaeaeaiey yeaeo?iiiie ieioiinoe a iieaeoea.

Yooaeou oiaeiaee iieaeoe a e?enoaeea ieacuaatho nouanoaaiiia aeeyiea ia
?aaiiaanioth aaiiao?eth aeeaeae?ioeeeeia oieueei a neo/aa ionoonoaey a
e?enoaeee/aneie no?oeoo?a enneaaeoaiiai ?yaea niaaeeiaiee niaoeeoe/aneeo
iaaeiieaeoey?iuo acaeiiaeaenoaee (iai?eia?, aiaei?iaeiuo naycae) n
neeueii ioee/athueieny oa?aeoa?enoeeaie.

Oanoe/eaiiua aeeaeae?ioeeeeu i?iyaeytho aunieoth eiioi?iaoeeiiioth
aeaeinoue e a aeieiae/anee aeoeaiuo niaaeeiaieyo. Enneaaeiaaiey
eiioi?iaoeeiiiie aeeiaieee 1,4-aeeaeae?iie?eaeeiiaiai eieueoea a
aaiienoao e aioaaiienoao eaeueoeeaauo eaiaeia eeaoie iieacaee, /oi
iao/ao aeeiaie/aneeo naienoa /anoe/ii aeae?e?iaaiiiai eieueoea iiaeao
i?eaiaeeoue e ioeai/iui auaiaeai i ei??aeyoeee “no?oeoo?a-aeoeaiinoue”.

Aia?aua onoaiiaeaia aunieay aeaeinoue ie?eieaeeiiauo eieaoe a
iniiaaieyo ioeeaeiiauo eeneio, eioi?ay nio?aiyaony e i?e ia?aciaaiee
aiaei?iaeii-naycaiiuo Oionii-E?eeianeeo ia? iniiaaiee.

Iieacaii, /oi iaaeanoeinoue oanoe/eaiiuo aeeaeae?ioeeeeia iiaeao
ieacuaaoue nouanoaaiiia aeeyiea ia oeceei-oeie/aneea oa?aeoa?enoeee
niaaeeiaiee, niaea?aeaueo oaeea o?aaiaiou. Oae, ?acee/ey a
eiioi?iaoeeiiiie aeaeinoe /anoe/ii aeae?e?iaaiiuo eieaoe a eciia?iuo
oeeeeiaaenaaeeaiao i?eaiaeeo e nouanoaaiiie aeanoaaeeecaoeee 1,3-eciia?a
i?e eiiiaoiie oaiia?aoo?a ca n/ao iaiueoae aaee/eiu eieaaaoaeueiiai
aeeaaea a yio?iieth.

Onoaiiaeaii, /oi oai?aoe/aneia iauyniaiea yenia?eiaioaeueii
iaaethaeaaiuo aaee/ei naaiaioa Eoia a aeanoeioeaiiuo aaoa?ioeeeee/aneeo
iieeia?ao, iieo/aiiuo ia iniiaa iaooeeaeeeieaea, iaaiciiaeii aac o/aoa
eiioi?iaoeeiiiie aeeiaieee eieaeiiai eieueoea, aoiaeyuaai a ninoaa
iiiiia?iiai caaia iae?iiieaeoeu.

Eeth/aaua neiaa: oanoe/eaiiua aeeaeae?ioeeeeu, iieaeoey?iay no?oeoo?a,
eiioi?iaoeeiiiue aiaeec, eiioi?iaoeeiiiay aeaeinoue.

SUMMARY

Shishkin O.V. Molecular structure and conformational analysis of
six-membered dihydrocycles.- Manuscript.

Thesis for a doctor’s degree by speciality 02.00.03 — organic
chemistry.- Kharkiv State University, Kharkiv, 1999.

The main rules of molecular structure of six-membered dihydrocycles
have been established. It was demonstrated that all types of rings
possess high conformational flexibility. An influence of electronic and
steric substituent effects and anneletaion by various rings on
conformational characteristics of partially hydrogenated rings have been
studied. Intermolecular interaction effects in the crystal phase and
their influence on conformation of flexible rings have been
investigated. It was shown that high conformational flexibility of
six-membered dihydrocycles may essentially change physico-chemical
properties of compounds especially in biological systems.

Key words: six-membered dihydrocycles, molecular structure,
conformational analysis, conformational flexibility

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