Тетразолы

µÔÒÇØË ØËÏËË 63 (10) 1994

847 杪 547.796.1

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°ÅÎÂÄÎÇÐËÇ I. II. III. IV. V. VI.

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847 847 852 854 860 860

I. £ÄÇÆÇÐËÇ

II. ®ÇÕÑÆÞ ÒÑÎÖÚÇÐËâ ÕÇÕÓÂÊÑÎÑÄ

²ÂÊÄËÕËÇ ØËÏËË ÕÇÕÓÂÊÑÎÑÄ Ä ÒÑÔÎÇÆÐÇÇ ÆÇÔâÕËÎÇÕËÇ Ä ÊÐÂÚËÕÇÎßÐÑÌ ÔÕÇÒÇÐË ÔÄâÊÂÐÑ Ô ÛËÓÑÍËÏ ÒÓËÏÇÐÇÐËÇÏ àÕËØ ÔÑÇÆËÐÇÐËÌ Ä ÏÇÆËÙËÐÇ,1 ë 12 ÃËÑØËÏËË,13 ë 17 ÔÇÎßÔÍÑÏ ØÑÊâÌÔÕÄÇ,18 ë 20 ×ÑÕÑÅÓÂ×ËË,21, 22,  ÕÂÍÉÇ Ä ÍÂÚÇÔÕÄÇ ÍÑÏÒÑÐÇÐÕÑÄ ÔËÔÕÇÏ ÓÇÅËÔÕÓÂÙËË ËÐ×ÑÓÏÂÙËË.23 ë 25 ©Â àÕË ÅÑÆÞ ÓÂÊÓÂÃÑÕÂÐÞ ÑÓËÅËÐÂÎßÐÞÇ 26 ë 29 Ë ÔÖÜÇÔÕÄÇÐÐÑ ÖÔÑÄÇÓÛÇÐÔÕÄÑÄÂÐÞ30 ë 35 ËÊÄÇÔÕÐÞÇ ÏÇÕÑÆÞ ÒÑÎÖÚÇÐËâ ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ. ¢ÎÂÅÑÆÂÓâ àÕÑÏÖ ÕÓÖÆÐÑÆÑÔÕÖÒÐÞÇ Ë Ä ÑÒÓÇÆÇÎÇÐÐÑÌ ÔÕÇÒÇÐË àÍÊÑÕËÚÇÔÍËÇ ÕÇÕÓÂÊÑÎÞ ÔÕÂÎË ÒÓÇÆÏÇÕÑÏ ÆÇÕÂÎßÐÑÅÑ ËÊÖÚÇÐËâ, Â Ä ÓâÆÇ ÔÎÖÚÂÇÄ ÃÞÎË ÓÇÍÑÏÇÐÆÑÄÂÐÞ Í ÒÓÂÍÕËÚÇÔÍÑÏÖ ÒÓËÏÇÐÇÐËá. ¢ÑÎßÛÑÌ ËÐÕÇÓÇÔ ÒÓÇÆÔÕÂÄÎâáÕ ÐÑÄÞÇ ÓÇÊÖÎßÕÂÕÞ, ÒÑÎÖÚÇÐÐÞÇ ÒÓË ËÊÖÚÇÐËË àÎÇÍÕÓÑÐÐÑÅÑ ÔÕÓÑÇÐËâ,36 ë 40 ÍËÔÎÑÕÐÑ-ÑÔÐÑÄÐÞØ ÔÄÑÌÔÕÄ,41 ë 43 ÕÂÖÕÑÏÇÓËË,44 ÓÇÂÍÙËÑÐÐÑÌ ÔÒÑÔÑÃÐÑÔÕË 45 ë 47 Ë ÕÇÓÏËÚÇÔÍÑÌ ÔÕÂÃËÎßÐÑÔÕË ÕÇÕÓÂÊÑÎÑÄ.48 ë 50 °ÓËÅËÐÂÎßÐÞÇ ÓÂÃÑÕÞ, ÑÒÖÃÎËÍÑÄÂÐÐÞÇ ÆÑ 1981 Å., ÔËÔÕÇÏÂÕËÊËÓÑÄÂÐÞ Ä ÑÃÊÑÓÂØ.46, 51 ¯ËÉÇ ÑÃÔÖÉÆÂáÕÔâ ÐÑÄÇÌÛËÇ ÆÂÐÐÞÇ ÒÑ ÏÇÕÑÆÂÏ ÒÑÎÖÚÇÐËâ, ×ËÊËÍÑ-ØËÏËÚÇÔÍËÏ ÔÄÑÌÔÕÄÂÏ Ë ÒÓÂÍÕËÚÇÔÍÑÏÖ ÒÓËÏÇÐÇÐËá ÕÇÕÓÂÊÑÎÑÄ.

1. ´ÇÕÓÂÊÑÎ ªÊÄÇÔÕÐÑ ÐÇÔÍÑÎßÍÑ ÏÇÕÑÆÑÄ ÒÑÎÖÚÇÐËâ ÕÇÕÓÂÊÑΠì ÄÊÂËÏÑÆÇÌÔÕÄËÇ ÔËÐËÎßÐÑÌ ÍËÔÎÑÕÞ Ô ÂÊÑÕËÔÕÑÄÑÆÑÓÑÆÐÑÌ, àÕËÎ×ÑÓÏËÂÕÂ Ô ÂÊËÆÑÏ ÐÂÕÓËâ Ë ØÎÑÓËÔÕÞÏ ÂÏÏÑÐËÇÏ Ä ÖÍÔÖÔÐÑÌ ÍËÔÎÑÕÇ, ÆËÂÊÑÕËÓÑÄÂÐËÇ 5-ÂÏËÐÑÕÇÕÓÂÊÑÎÂ Ä ÒÓËÔÖÕÔÕÄËË ÄÑÔÔÕÂÐÑÄËÕÇÎÇÌ, ÑÍËÔÎËÕÇÎßÐÂâ ÆÇÅÓÂÆÂÙËâ ÏÑÐÑË ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ Ë ÐÇÍÑÕÑÓÞÇ ÆÓÖÅËÇ.51 ³ÓÇÆË ÖÍÂÊÂÐÐÞØ ÏÇÕÑÆÑÄ ÔÂÏÞÏË ÓÂÔÒÓÑÔÕÓÂÐÇÐÐÞÏË âÄÎâáÕÔâ ÆËÂÊÑÕËÓÑÄÂÐËÇ 5-ÂÏËÐÑÕÇÕÓÂÊÑÎÂ Ë ÄÊÂËÏÑÆÇÌÔÕÄËÇ ÑÓÕÑàÕËÎ×ÑÓÏËÂÕÂ Ô ÂÊËÆÑÏ ÐÂÕÓËâ. £ ÒÑÔÎÇÆÐÇÏ ÔÎÖÚÂÇ ÓÇÂÍÙËâ, ÑÚÇÄËÆÐÑ, ÒÓÑÕÇÍÂÇÕ ÚÇÓÇÊ ÔÕÂÆËá ÑÃÓÂÊÑÄÂÐËâ ÅËÆÓÑØÎÑÓËÆ ËÏËÐÑà×ËÓÂ Ë ÒÑÔÎÇÆÖáÜÇÅÑ ÇÅÑ ÒÓÇÄÓÂÜÇÐËâ ÒÑÆ ÆÇÌÔÕÄËÇÏ ÂÊËÆ ÐÂÕÓËâ Ä ÕÇÕÓÂÊÑÎ.52

¥ÂÕ ÒÑÔÕÖÒÎÇÐËâ 27 ÏÂâ 1993 Å.

NaN3

OC2H5

HC NH ¤.ª.¬ÑÎÆÑÃÔÍËÌ. ¥ÑÍÕÑÓ ØËÏËÚÇÔÍËØ ÐÂÖÍ, ÒÓÑ×ÇÔÔÑÓ ÍÂ×ÇÆÓÞ ØËÏËÚÇÔÍÑÌ ÕÇØÐÑÎÑÅËË ÑÓÅÂÐËÚÇÔÍËØ ÍÓÂÔËÕÇÎÇÌ Ë ×ÑÕÑÕÓÑÒÐÞØ ÔÑÇÆËÐÇÐËÌ ³-±Ã. ÅÑÔ. ÕÇØÐÑÎ. ËÐ-ÕÂ. °ÃÎÂÔÕß ÐÂÖÚÐÞØ ËÐÕÇÓÇÔÑÄ: ÂÊÑÕÔÑÆÇÓÉÂÜËÇ ÅÇÕÇÓÑÙËÍÎÞ, ÏÇÉ×ÂÊÐÞÌ ÍÂÕÂÎËÊ Ä ÑÓÅÂÐËÚÇÔÍÑÏ ÔËÐÕÇÊÇ. ´ÇÎÇ×ÑÐ: (812)316-5349. £.¡.°ÔÕÓÑÄÔÍËÌ. ¥ÑÍÕÑÓ ØËÏËÚÇÔÍËØ ÐÂÖÍ, ÒÓÑ×ÇÔÔÑÓ ÍÂ×ÇÆÓÞ ØËÏËË Ë ÕÇØÐÑÎÑÅËË ÑÓÅÂÐËÚÇÔÍËØ ÔÑÇÆËÐÇÐËÌ ÂÊÑÕ ÕÑÅÑ ÉÇ ËÐÔÕËÕÖÕÂ. °ÃÎÂÔÕß ÐÂÖÚÐÞØ ËÐÕÇÓÇÔÑÄ: ÂÊÑÕÔÑÆÇÓÉÂÜËÇ ÅÇÕÇÓÑÙËÍÎÞ, ÍËÔÎÑÕÐÞÌ ÍÂÕÂÎËÊ ÑÓÅÂÐËÚÇÔÍËØ ÓÇÂÍÙËÌ.

HC NH . HCl

(C2H5O)3CH + NH4Cl

N3

HC N

NH N

N

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848

¤.ª.¬ÑÎÆÑÃÔÍËÌ, £.¡.°ÔÕÓÑÄÔÍËÌ

Cl3CC N

NH N

N

H2SO4

HC N

NH N

N

¯ÇÆÂÄÐÑ ÑÒËÔÂÐ ÔËÐÕÇÊ ÕÇÕÓÂÊÑÎÂ, ÔÑÆÇÓÉÂÜÇÅÑ Ä ÙËÍÎÇ ËÊÑÕÑÒ ÂÕÑÏ ÖÅÎÇÓÑÆ 13³.54

4. 5-©ÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ

2. 1-©ÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ £ÞÃÑÓ ÏÇÕÑÆÑÄ ÒÑÎÖÚÇÐËâ 1-ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÑÅÓÂÐËÚÇÐ. °ÔÐÑÄÐÞÏ ÒÑ-ÒÓÇÉÐÇÏÖ ÑÔÕÂÇÕÔâ ÒÓËÔÑÇÆËÐÇÐËÇ ÂÊÑÕËÔÕÑÄÑÆÑÓÑÆÐÑÌ ÍËÔÎÑÕÞ Í ËÊÑÐËÕÓËÎÂÏ. ¯ÂÓâÆÖ Ô àÕËÏ ÏÇÕÑÆÑÏ ËÔÒÑÎßÊÖÇÕÔâ ÕÂÍÉÇ ÓÇÂÍÙËâ ÔÑÚÇÕÂÐËâ ÔÑÎÇÌ ÆËÂÊÑÐËâ Ô ÆË×ÑÓÏËÎÅËÆÓÂÊËÐÑÏ ËÎË ÄÊÂËÏÑÆÇÌÔÕÄËÇ ËÏËÆÑËÎØÎÑÓËÆÑÄ, ÒÑÎÖÚÇÐÐÞØ ËÊ ÏÑÐÑÊÂÏÇÜÇÐÐÞØ ×ÑÓÏÂÏËÆÑÄ, Ô ÂÊÑÕËÔÕÑÄÑÆÑÓÑÆÐÑÌ ÍËÔÎÑÕÑÌ.51 ªÊ ÐÑÄÞØ ÏÇÕÑÆÑÄ ÔËÐÕÇÊ 1-ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÔÎÇÆÖÇÕ ÑÕÏÇÕËÕß ÓÇÂÍÙËá ÂÎßÆÇÅËÆÑÄ Ô ÕÓËÏÇÕËÎÔËÎËÎÂÊËÆÑÏ (´®³¡) 55 Ë ÂÏËÐÑÄ Ô àÕËÎÑÓÕÑ×ÑÓÏËÂÕÑÏ Ë ÂÊËÆÑÏ ÐÂÕÓËâ.56 ë 59 £ ÒÇÓÄÑÏ ÔÎÖÚÂÇ,55 ÒÓË ÄÊÂËÏÑÆÇÌÔÕÄËË ÂÎßÆÇÅËÆÂ Ô ´®³¡ ÔÐÂÚÂΠÑÃÓÂÊÖÇÕÔâ ÆËÂÊËÆ, ÍÑÕÑÓÞÌ Ä ÓÇÊÖÎßÕÂÕÇ ÑÕÜÇÒÎÇÐËâ ÏÑÎÇÍÖÎÞ ÂÊÑÕÂ Ë ÒÇÓÇÅÓÖÒÒËÓÑÄÍË ÒÓÇÄÓÂÜÂÇÕÔâ Ä ËÏËÆÑËÎÂÊËÆ, ÙËÍÎËÊÖáÜËÌÔâ Ä 1-ÊÂÏÇÜÇÐÐÞÌ ÕÇÕÓÂÊÑÎ. RCHO + (CH3)3SiN3

N3

ZnCl2

R C H N3

HC

HC NR N3

N

7N2

R

NR N

NaN3

N

HC NR

HC NR

OC2H5

N3

C (CH3)2HN

(C2H5O)3CH

NHR

HC NR

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RCN + (CH3)2NH + N3H

¯ÂÒÓÂÄÎÇÐËÇ ÓÇÂÍÙËË ÊÂÄËÔËÕ ÑÕ ÔÑÑÕÐÑÛÇÐËâ ÂÎßÆÇÅËÆ : ´®³¡. ±ÓË ÕÓÇØÍÓÂÕÐÑÏ ËÊÃÞÕÍÇ ´®³¡ ÑÃÓÂÊÖáÕÔâ 1-ÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ,  ÒÓË ÔÑÑÕÐÑÛÇÐËË ÓÇÂÅÇÐÕÑÄ ÑÕ 1 : 1 ÆÑ 1 : 1.5 ì ÆËÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ. °ÆÐËÏ ËÊ ÐÂËÃÑÎÇÇ ÒÇÓÔÒÇÍÕËÄÐÞØ ÏÇÕÑÆÑÄ ÔËÐÕÇÊ 1-ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ âÄÎâÇÕÔâ ÓÇÂÍÙËâ ÂÏËÐÑÄ Ô àÕËÎÑÓÕÑ×ÑÓÏËÂÕÑÏ Ë ÂÊËÆÑÏ ÐÂÕÓËâ. ¿ÕÑÕ ÏÇÕÑÆ ÏÑÉÐÑ ÔÚËÕÂÕß ÖÐËÄÇÓÔÂÎßÐÞÏ, ÕÂÍ ÍÂÍ ÆÎâ ÒÑÎÖÚÇÐËâ ÕÇÕÓÂÊÑÎÑÄ ÏÑÅÖÕ ÃÞÕß ËÔÒÑÎßÊÑÄÂÐÞ ÂÎË×ÂÕËÚÇÔÍËÇ Ë ÂÓÑÏÂÕËÚÇÔÍËÇ ÂÏËÐÞ ÓÂÊÎËÚÐÑÅÑ ÔÕÓÑÇÐËâ. ±Ñ ÏÐÇÐËá ÂÄÕÑÓÑÄ ÓÂÃÑÕÞ,58 ÑÃÓÂÊÑÄÂÐËÇ 1-ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÒÓÑËÔØÑÆËÕ ÒÑ ÔÎÇÆÖáÜÇÌ ÔØÇÏÇ: RNH2 + (C2H5O)3CH

ÔÕÄÇÐÐÞÏ ÔÒÑÔÑÃÑÏ ÔËÐÕÇÊ 2-ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÔÎÖÉËÕ ÂÎÍËÎËÓÑÄÂÐËÇ ÕÇÕÓÂÊÑÎÂ.47, 51. £ ÕÑ ÉÇ ÄÓÇÏâ ÔÎÇÆÖÇÕ ËÏÇÕß Ä ÄËÆÖ, ÚÕÑ, ØÑÕâ ÒÓË ÂÎÍËÎËÓÑÄÂÐËË ÕÇÕÓÂÊÑΠÏÑÅÖÕ ÃÞÕß ÒÑÎÖÚÇÐÞ ÔÂÏÞÇ ÓÂÊÐÑÑÃÓÂÊÐÞÇ 2-ÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ, ÓÇÂÎËÊÂÙËâ àÕÑÅÑ ÏÇÕÑÆ ÑÃÞÚÐÑ ÔÄâÊÂÐÂ Ô ÕÓÖÆÐÑÔÕâÏË ÓÂÊÆÇÎÇÐËâ ËÊÑÏÇÓÐÞØ 1- Ë 2-ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ, ÑÃÓÂÊÖáÜËØÔâ Ä ÓÇÊÖÎßÕÂÕÇ ÓÇÂÍÙËË.

R

N

HN7 N+ N

+

C N

N (CH3)2NH2 7 N

N

£ ÕÑ ÉÇ ÄÓÇÏâ ÐÇ ËÔÍÎáÚÂÇÕÔâ ÄÑÊÏÑÉÐÑÔÕß ÑÃÓÂÊÑÄÂÐËâ 5-ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÒÑ ÆÄÖØÔÕÂÆËÌÐÑÏÖ ÏÇØÂÐËÊÏÖ. ¿ÕÑÕ ÏÇØÂÐËÊÏ, ÒÑ-ÄËÆËÏÑÏÖ, ÓÇÂÎËÊÖÇÕÔâ ÆÎâ ÔÖÃÔÕÓÂÕÑÄ, Ä ÍÑÕÑÓÞØ ÐËÕÓËÎßÐÂâ ÅÓÖÒÒ ÔÄâÊÂÐÂ Ô ÔËÎßÐÞÏ àÎÇÍÕÓÑÐÑÂÍÙÇÒÕÑÓÐÞÏ ÊÂÏÇÔÕËÕÇÎÇÏ, ÐÂÒÓËÏÇÓ ÆÎâ ÕÓË×ÕÑÓ- Ë ×ÕÑÓÆËÐËÕÓÑÂÙÇÕÑÐËÕÓËÎÑÄ,73 ë 75  ÕÂÍÉÇ ÆÎâ ÆËÐËÕÓËΠÜÂÄÇÎÇÄÑÌ ÍËÔÎÑÕÞ.76 £ àÕÑÌ ÔÄâÊË ÖÏÇÔÕÐÑ ÑÕÏÇÕËÕß, ÚÕÑ ÆËÐËÕÓËÎ ÜÂÄÇÎÇÄÑÌ ÍËÔÎÑÕÞ Ô ÄÞÔÑÍÑÌ ÔÍÑÓÑÔÕßá ÓÇÂÅËÓÖÇÕ Ô [Ph3P=N=PPh3]+Nÿ 3 . ±ÓË àÕÑÏ Ô ÄÞØÑÆÑÏ 96% ÑÃÓÂÊÖÇÕÔâ 5-ÙËÂÐÑÕÇÕÓÂÊÑÎ.76 NC CN + [Ph3P N PPh3]+ . Nÿ 3

HC N

NR N

N

1-©ÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ ÏÑÅÖÕ ÃÞÕß ÕÂÍÉÇ ÒÑÎÖÚÇÐÞ ÒÓË ÂÎÍËÎËÓÑÄÂÐËË ÕÇÕÓÂÊÑÎÂ. ¥ÇÕÂÎßÐÑ àÕ ÓÇÂÍÙËâ ÃÖÆÇÕ ÓÂÔÔÏÑÕÓÇРÒÓË ÑÃÔÖÉÆÇÐËË ØËÏËÚÇÔÍËØ ÔÄÑÌÔÕÄ ÕÇÕÓÂÊÑÎÑÄ.

3. 2-©ÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ ²ÂÊÓÂÃÑÕÍ ÒÓÑÔÕÞØ Ë à××ÇÍÕËÄÐÞØ ÔÒÑÔÑÃÑÄ ÔËÐÕÇÊ 2-ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ âÄÎâÇÕÔâ ÑÆÐÑÌ ËÊ ÐÂËÃÑÎÇÇ ÂÍÕÖÂÎßÐÞØ ÒÓÑÃÎÇÏ ØËÏËË ÕÇÕÓÂÊÑÎÑÄ. ±Ñ-ÒÓÇÉÐÇÏÖ ÇÆËÐ-

NC N

N 7 N

N

[Ph3P N PPh3]+

£ÏÇÔÕÑ ÔÑÎÇÌ Ë ÍÑÏÒÎÇÍÔÑÄ ÂÊÑÕËÔÕÑÄÑÆÑÓÑÆÐÑÌ ÍËÔÎÑÕÞ Ä ÓÇÂÍÙËË Ô ÐËÕÓËÎÂÏË ÏÑÉÐÑ ËÔÒÑÎßÊÑÄÂÕß ÕÓËÏÇÕËÎÔËÎËÎÂÊËÆ,29, 74  ÕÂÍÉÇ ÕÓËÏÇÕËÎ- Ë ÕÓËÃÖÕËÎÔÕÂÐÐËÎÂÊËÆÞ.77, 78 £ àÕËØ ÔÎÖÚÂâØ Ð ÒÇÓÄÑÌ ÔÕÂÆËË ÑÃÓÂÊÖáÕÔâ 1-ÕÓËÏÇÕËÎÔËÎËÎË 1-ÕÓËÏÇÕËÎ(ÃÖÕËÎ)ÔÕÂÐÐËÎ-5-R-ÕÇÕÓÂÊÑÎÞ, ÍÑÕÑÓÞÇ ÒÓË ÍËÔÎÑÕÐÑÏ ÅËÆÓÑÎËÊÇ ÒÓÇÄÓÂÜÂáÕÔâ Ä 5-R-ÕÇÕÓÂÊÑÎÞ.

µÔÒÇØË ØËÏËË 63 (10) 1994

849

(O2N)3CCN + (CH3)3SiN3

(O2N)3CC N

(O2N)3CC

NSi(CH3)3

N

N

RC

NH

N

N

N

7 N

N

C6H5C

N

CH3COOH NH4Cl

N

C6H5

C N

CH2 N

NH

NH N

N

 ÕÂÍÉÇ ÄÊÂËÏÑÆÇÌÔÕÄËÇ ÂÏËÐÑËÏËÐÑÏÇÕÂÐÔÖÎß×ÑÍËÔÎÑÕ Ô ÂÊËÆÑÏ ÐÂÕÓËâ Ä ÖÍÔÖÔÐÑÌ ÍËÔÎÑÕÇ.28 SOÿ 3

N

N C2H5

N3

C N

N

H2O

H N

RO

N N

N

N

N

N

N

HN

COOR

OH

HN

C

NH C

N

N

N

N

H N

N

N

N N

H2O 7CO2 , 7ROH

NH N

²ÇÂÍÙËâ ËÏËÆÑËÎØÎÑÓËÆÑÄ Ô ÂÊÑÕËÔÕÑÄÑÆÑÓÑÆÐÑÌ ÍËÔÎÑÕÑÌ ËÎË ÐÇÑÓÅÂÐËÚÇÔÍËÏË ÂÊËÆÂÏË ÒÑ-ÒÓÇÉÐÇÏÖ âÄÎâÇÕÔâ ÑÆÐËÏ ËÊ ÔÂÏÞØ ÓÂÔÒÓÑÔÕÓÂÐÇÐÐÞØ ÏÇÕÑÆÑÄ ÒÑÎÖÚÇÐËâ 1,5-ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ. ¿ÕÑÕ ÔÒÑÔÑà ËÏÇÇÕ ÖÐËÄÇÓÔÂÎßÐÞÌ ØÂÓÂÍÕÇÓ Ë ÏÑÉÇÕ ÃÞÕß ËÔÒÑÎßÊÑÄÂÐ ÆÎâ ÔËÐÕÇÊ 1,5-ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ, ÔÑÆÇÓÉÂÜËØ ÔÂÏÞÇ ÓÂÊÐÑÑÃÓÂÊÐÞÇ ×ÖÐÍÙËÑÐÂÎßÐÞÇ ÅÓÖÒÒÞ.82 ë 91 ¬ËÐÇÕËÍÂ Ë ÏÇØÂÐËÊÏ àÕÑÌ ÓÇÂÍÙËË ËÊÖÚÇÐÞ Ä ÓÂÃÑÕÂØ.92, 93 ±ÑÍÂÊÂÐÑ, ÚÕÑ ÒÓË ÄÊÂËÏÑÆÇÌÔÕÄËË ËÏËÆÑËÎØÎÑÓËÆÂ Ô ÂÊËÆÑÏ ÐÂÕÓËâ РÒÇÓÄÑÌ ÔÕÂÆËË ÑÃÓÂÊÖÇÕÔâ ÔÏÇÔß Z- Ë E-ÍÑÐ×ÑÓÏÇÓÑÄ ËÏËÆÑËÎÂÊËÆÂ, ËÊ ÍÑÕÑÓÞØ ÕÑÎßÍÑ E-ÍÑÐ×ÑÓÏÇÓ ÒÓÇÄÓÂÜÂÇÕÔâ Ä ÕÇÕÓÂÊÑÎ. R1

C N

R2

NaN3

N

¯ÇÆÂÄÐÑ ÒÑâÄËÎËÔß ÔÑÑÃÜÇÐËâ 80, 81 Ñ ÔËÐÕÇÊÇ Ô ØÑÓÑÛËÏ ÄÞØÑÆÑÏ 5-ÊÂÏÇÜÇÐÐÞØ 4,5-ÆËÅËÆÓÑÕÇÕÓÂÊÑÎÑÄ ËÊ ÏÇÕËÎ-3,3ÆËÂÊËÆÑ-2-ÙËÂÐÑÂÍÓËÎÂÕÂ Ë ÂÏÏËÂÍ ËÎË ÂÏËÐÑÄ.

R1

C

N3

R1

C

N

R2

R2

N

Z

N

N3

N

CN

NH

N

N3

C C COOCH3 N R

Cl

ªÐÕÇÓÇÔÐÞÌ ÔÒÑÔÑà ÒÑÎÖÚÇÐËâ ÆË(ÕÇÕÓÂÊÑÎ-5-ËÎ)ÂÏËРÒÓÇÆÎÑÉÇÐ Ä ÓÂÃÑÕÇ 79. ±ÓË ÐÂÅÓÇÄÂÐËË 2,4-ÆËÂÊËÆÑ-6ÂÎÍÑÍÔË-1,3,5-ÕÓËÂÊËÐÑÄ Ä ÄÑÆÇ ÒÓÑËÔØÑÆËÕ àÎËÏËÐËÓÑÄÂÐËÇ ÂÕÑÏ ÖÅÎÇÓÑÆ ÙËÍÎÂ Ë ÔÄâÊÂÐÐÑÌ Ô ÐËÏ ÂÎÍÑÍÔËÅÓÖÒÒÞ, ÚÕÑ ÒÓËÄÑÆËÕ Í ÆË(ÕÇÕÓÂÊÑÎ-5-ËÎ)ÂÏËÐÖ. N

CN

5. 1,5-¥ËÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ

C6H5

CH3COOH

+ NaN3

NH2

RO

N R

H+

R = H, Alk

7CH2N2

C2H5

N

N 7 C C COOCH3

H N

NSn(CH3)3 N

C CH2 + NaN3 N3

N C

N

H+

N3

+

CN

+

RC

RNH2

C C COOCH3

RNH3 .

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C6H5

N3

N

RCN + (CH3)3SnN3

C6H5

N3

NH

N

N

H+

N

R1C N

N3

E

NR2 N

N

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R1

C N Cl

R2 + NaN3

(C4H9)4N Br7

R1C N

NR2 N

N

850

¤.ª.¬ÑÎÆÑÃÔÍËÌ, £.¡.°ÔÕÓÑÄÔÍËÌ

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R1

R1CNHR2 + (C6H5)3P

R2

C N

C N R2

R1C

NR2

N

N

N3

N

C N C6H5 + NaN3

CH3COOH

NR2R3

R1N

R1C N

R2

C C

R1 + NaN3

R2

NHR3

NC6H5

CH C NR3

N

N3

N

ArN C NAr

N

NR3 N

C N

R1C N

NR2 N

(C4H9)4N Cl7 C6H5CH3

ArN C NCOC6H5 N3 Ar

NCOC6H5

N Ar

HNO2

R1C

R1C N

NR2

R1

N

R2

N

N

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C6H5COCl

1,5-¥ËÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ ÏÑÅÖÕ ÃÞÕß ÒÑÎÖÚÇÐÞ ÒÓË ÑÃÓÂÃÑÕÍÇ ÅËÆÓÂÊËÆÑÄ 119, 4-ÅËÆÓÂÊËÐÑ-1,2,3-ÕÓËÂÊËÐÑÄ 120 ËÎË 3-ÅËÆÓÂÊËÐÑ-1,2,4-ÕÓËÂÊËÐÑÄ 121 ÂÊÑÕËÔÕÑÌ ÍËÔÎÑÕÑÌ. NHNH2

°ÆÐËÏ ËÊ ÆÑÔÕÂÕÑÚÐÑ ØÑÓÑÛÑ ËÊÖÚÇÐÐÞØ ÏÇÕÑÆÑÄ ÔËÐÕÇÊ 1,5-ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ âÄÎâÇÕÔâ ÓÇÂÍÙËâ ÐËÕÓËÎÑÄ Ô ÂÎË×ÂÕËÚÇÔÍËÏË Ë ÂÓÑÏÂÕËÚÇÔÍËÏË ÂÊËÆÂÏË. R1CN + N3R2

N

N

N3

ArN

N

N

ArN C NAr + NaN3

N3

C

CNHR2

+

NHR3

CH R2

N

N

N

R1

R1 R2

C C

NR2

¦ÔÎË ÓÇÂÍÙËá ÒÓÑÄÑÆËÕß Ä ÖÔÎÑÄËâØ ÏÇÉ×ÂÊÐÑÅÑ ÍÂÕÂÎËÊÂ Ä ÒÓËÔÖÕÔÕÄËË ØÎÑÓÂÐÅËÆÓËÆÑÄ ÃÇÐÊÑÌÐÞØ ÍËÔÎÑÕ, ÕÑ ÄÏÇÔÕÑ ÂÊÑÕËÔÕÑÄÑÆÑÓÑÆÐÑÌ ÍËÔÎÑÕÞ ÏÑÉÐÑ ËÔÒÑÎßÊÑÄÂÕß ÂÊËÆ ÐÂÕÓËâ.32

7

SCH3

N

R1N C NR2 + HN3

¯ÂÍÑÐÇÙ, 1,5-ÆËÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ ÏÑÅÖÕ ÃÞÕß ÒÑÎÖÚÇÐÞ ËÊ S,N-ÂÙÇÕÂÎÇÌ ÍÇÕÇРÒÓË ÐÂÅÓÇÄÂÐËË ÒÑÔÎÇÆÐËØ Ô ÂÊËÆÑÏ ÐÂÕÓËâ Ä ÆËÏÇÕËÎÔÖÎß×ÑÍÔËÆÇ.26 R1

R1 C

SnCl2

¦ÜÇ ÑÆÐËÏ ÓÂÔÒÓÑÔÕÓÂÐÇÐÐÞÏ ÏÇÕÑÆÑÏ ÔËÐÕÇÊ 1,5ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ âÄÎâÇÕÔâ ÓÇÂÍÙËâ ÍÂÓÃÑÆËËÏËÆÑÄ Ô ÂÊÑÕËÔÕÑÄÑÆÑÓÑÆÐÑÌ ÍËÔÎÑÕÑÌ.116ì118

µÆÑÃÐÞÌ ÏÇÕÑÆ ÒÑÎÖÚÇÐËâ 1,5-ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÒÓÇÆÎÑÉËÎË ÂÄÕÑÓÞ ÓÂÃÑÕÞ 102, ÍÑÕÑÓÞÇ ÐÂÛÎË, ÚÕÑ ÒÓË ÄÊÂËÏÑÆÇÌÔÕÄËË ÂÏËÆËÐÑÄ Ô ÂÊËÆÑÏ ÐÂÕÓËâ Ä ÖÍÔÖÔÐÑÌ ÍËÔÎÑÕÇ Ô ÄÞÔÑÍËÏ ÄÞØÑÆÑÏ ÑÃÓÂÊÖáÕÔâ ÔÑÑÕÄÇÕÔÕÄÖáÜËÇ ÕÇÕÓÂÊÑÎÞ. R1

R1COR2 + (CH3)3SiN3

TMCA

O P(C6H5)3 +

R1

ÐÞÏ ÑÅÓÂÐËÚÇÐËÇÏ àÕÑÅÑ ÏÇÕÑÆ ÃÞΠÐÇÑÃØÑÆËÏÑÔÕß ÒÓËÏÇÐÇÐËâ ÂÊÑÕËÔÕÑÄÑÆÑÓÑÆÐÑÌ ÍËÔÎÑÕÞ. µÍÂÊÂÐÐÞÇ ÕÓÖÆÐÑÔÕË ÖÆÂÎÑÔß ÒÓÇÑÆÑÎÇÕß, ÒÓËÏÇÐââ ÄÏÇÔÕÑ ÂÊÑÕËÔÕÑÄÑÆÑÓÑÆÐÑÌ ÍËÔÎÑÕÞ ÕÓËÏÇÕËÎÔËÎËÎÂÊËÆ Ä ÔÑÚÇÕÂÐËË Ô ØÎÑÓËÆÑÏ ÑÎÑÄ 114 ËÎË ÕÓË×ÕÑÓÖÍÔÖÔÐÑÌ ÍËÔÎÑÕÑÌ.115

NHNH2

NR2 N

HNO2

N

N

R1

N

N

R2

N

N N

N

ªÐÕÇÓÇÔÐÞÌ ÔÒÑÔÑà ÒÑÎÖÚÇÐËâ ÂÐÐÇÎËÓÑÄÂÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÄÊÂËÏÑÆÇÌÔÕÄËÇÏ 2-ÂÏËÐÑÒËÓËÆËРËÎË 2-ÂÏËÐÑØËÐÑÎËÐÂ Ô Ò-ÕÑÎÖÑÎÔÖÎß×ÑÐËÎÂÊËÆÑÏ Ä ÖÔÎÑÄËâØ ÏÇÉ×ÂÊÐÑÅÑ ÍÂÕÂÎËÊ ÃÞÎ ÒÓÇÆÎÑÉÇÐ Ä ÓÂÃÑÕÇ 122. +

R

+ p-CH3C6H4SO2N3 N

C6H5CH2N(C2H5)3 Cl7

NH2

R N

N

N

N

¯ÂÍÑÐÇÙ, ÔÎÇÆÖÇÕ ÖÍÂÊÂÕß Ð ÓâÆ ÏÇÕÑÆÑÄ ÒÑÎÖÚÇÐËâ, ÍÑÕÑÓÞÇ ÒÑÍ ËÏÇáÕ ÑÅÓÂÐËÚÇÐÐÑÇ ÓÂÔÒÓÑÔÕÓÂÐÇÐËÇ. £ ÒÇÓÄÖá ÑÚÇÓÇÆß àÕÑ ÓÇÂÍÙËâ ËÊÑÙËÂÐÂÕÑÄ Ô ÂÊËÆÑÏ ÐÂÕÓËâ 123 ËÎË

µÔÒÇØË ØËÏËË 63 (10) 1994

851

ÕÓËÏÇÕËÎÔËÎËÎÂÊËÆÑÏ,124 ÕÇÓÏËÚÇÔÍÂâ ÒÇÓÇÅÓÖÒÒËÓÑÄÍ 5-ÂÊËÆÑ-1,2,3-ÕÓËÂÊÑÎÑÄ 125, 126 Ë ÆËà×ËÓÑÄ 3,3-ÆËÂÊËÆÑÏÂÎÑÐÑÄÑÌ ÍËÔÎÑÕÞ.127 N3 CH3OOC

CH3OOCC

D

C COOCH3

N

N3

NCH3 N

³ØÇÏ 1 Br RC6H4NH N CH CH N NHC6H4R + N3

N

Br N C C N N N N N R = H, OCH3, Br, Cl

CH3CN

CH2 + IN3

NC6H4R

RC6H4N

³áÆ ÉÇ ÔÎÇÆÖÇÕ ÑÕÐÇÔÕË ÒÓËÔÑÇÆËÐÇÐËÇ ËÑÆÂÊËÆÂ Í ÐÑÓÃÑÓÐÇÐÖ 128 Ë 1-ÏÇÕËÎÇÐ-4-(ÕÓÇÕ-ÃÖÕËÎ)ÙËÍÎÑÅÇÍÔÂÐÖ 129 Ä ÂÙÇÕÑÐËÕÓËÎÇ. (CH3)3C

Br

³ØÇÏ 2 N

CH2I

(CH3)3C

N N

C N

N

C6H5N

N N

CH3

N

C NH2 O

NaNO2

N

CH3COOH

NC

NO7Na+

C N

N

N

6. 2,5-¥ËÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ ®ÇÕÑÆÞ ÔËÐÕÇÊ 2,5-ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÓÂÊÓÂÃÑÕÂÐÞ ÐÇÆÑÔÕÂÕÑÚÐÑ. ©Â ÒÑÔÎÇÆÐÇÇ ÆÇÔâÕËÎÇÕËÇ ÐÇ ÃÞÎÑ ÒÓÇÆÎÑÉÇÐÑ ÐË ÑÆÐÑÅÑ ÒÓËÐÙËÒËÂÎßÐÑ ÐÑÄÑÅÑ ÔÒÑÔÑàÒÑÎÖÚÇÐËâ ÖÍÂÊÂÐÐÞØ ÔÑÇÆËÐÇÐËÌ, ËÏÇáÜÇÅÑ ÑÃÜËÌ ØÂÓÂÍÕÇÓ. ´ÇÏ ÐÇ ÏÇÐÇÇ ÊÂÔÎÖÉËÄÂÇÕ ÖÒÑÏËÐÂÐËâ ÓÇÂÍÙËâ ËÏËÆÑËÎØÎÑÓËÆÑÄ Ô ×ÇÐËÎÅËÆÓÂÊËÐÑÏ.133 p-RC6H4C NNHSO2

N

N

N

N

NC6H5

7. ³ÑÎË ÕÇÕÓÂÊÑÎËâ ªÊÄÇÔÕÐÞ ËÊÑÏÇÓÐÞÇ 1,2,5-, 1,3,5-, 1,4,5- Ë 2,3,5-ÕÓËÊÂÏÇÜÇÐÐÞÇ ÔÑÎË ÕÇÕÓÂÊÑÎËâ. ®ÇÕÑÆÂÏ ÒÑÎÖÚÇÐËâ àÕËØ ÔÑÇÆËÐÇÐËÌ ÃÞÎ ÒÑÔÄâÜÇÐ ÑÃÊÑÓ 136. ¯ËÉÇ ÓÂÔÔÏÂÕÓËÄÂáÕÔâ ÓÂÃÑÕÞ, ÑÒÖÃÎËÍÑÄÂÐÐÞÇ ÒÑÔÎÇ 1986 Å. °ÒËÔÂÐÑ 137, 138 ÒÑÎÖÚÇÐËÇ ÔÇÓËË 1,2,5-ÕÓËÊÂÏÇÜÇÐÐÞØ ÔÑÎÇÌ ÕÇÕÓÂÊÑÎËâ ÑÍËÔÎÇÐËÇÏ 1-(2-ÒËÓËÆËÎ)-3-ÂÓËÎÕÓËÂÊÇÐÑÄ 2,4,4,6-ÕÇÕÓÂÃÓÑÏÙËÍÎÑÅÇÍÔÂ-2,5-ÆËÇÐ-1-ÑÐÑÏ. O N N NHAr

N

R = H, CH3, OCH3, NO2

¥Îâ ÔËÐÕÇÊ ËÏËÆÑËÎØÎÑÓËÆÑÄ ÃÞÎË ËÔÒÑÎßÊÑÄÂÐÞ N-ÐÂ×ÕËÎÔÖÎß×ÑÐËÎÃÇÐÊÅËÆÓÂÊËÆÞ. °ÓËÅËÐÂÎßÐÞÌ ÏÇÕÑÆ ÒÑÎÖÚÇÐËâ 2-ÂÓËÎ-5-(2-ÂÓËÎÕÇÕÓÂÊÑÎ-5-ËÎ)ÕÇÕÓÂÊÑÎÑÄ, ÑÔÐÑÄÂÐÐÞÌ Ð ÓÇÂÍÙËË ÃËÔÂÓËÎÅËÆÓÂÊÑÐÑÄ ÅÎËÑÍÔÂÎâ Ô 2,4,6-ÕÓËÃÓÑÏÂÊËÆÑÃÇÐÊÑÎÑÏ, ÒÓÇÆÎÑÉËÎË ÂÄÕÑÓÞ ÓÂÃÑÕÞ 134 (ÔØÇÏ 1). ¯ÂÍÑÐÇÙ, ÔÎÇÆÖÇÕ ÑÕÏÇÕËÕß ËÐÕÇÓÇÔÐÞÌ ÒÓËÏÇÓ ÒÓÇÄÓÂÜÇÐËâ ÍÑÐÆÇÐÔËÓÑÄÂÐÐÑÅÑ 2-×ÇÐËÎ-4-ÂÏËÐÑ-1,2,3-ÕÓËÂÊÑÎÑ[4,5-d]-1,2,3-ÕÓËÂÊÑΠÒÑÆ ÆÇÌÔÕÄËÇÏ ÕÇÕÓÂÂÙÇÕÂÕ ÔÄËÐÙÂ Ä 2-×ÇÐËÎ-5-ÙËÂÐÑÕÇÕÓÂÊÑÎ.135 (ÔØÇÏ 2)

Br

Br Br

N 7 Br N+ N N Ar

N NC6H5

+

Br

+ C6H5NHNH2

N

N

N

N N

Cl

p-RC6H4C

N

NH2 NCC

C

N C6H5N

N

N

¯ÇÆÂÄÐÑ ÃÞÎÑ ÒÓÇÆÎÑÉÇÐÑ ÇÜÇ ÐÇÔÍÑÎßÍÑ ÏÇÕÑÆÑÄ ÒÑÎÖÚÇÐËâ 1,5-ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ: ÓÇÂÍÙËâ 1,3-ÑÍÔÂÊËÐËÇÄÞØ ÔÑÎÇÌ Ô ÂÊËÆÑÏ ÐÂÕÓËâ,130 ÃÇÐÊÑÕÓËÂÊÑÎÂ Ô ÅÎËÑÍÔÂÎÇÏ Ë ÂÊËÆÑÏ ÐÂÕÓËâ,131  ÕÂÍÉÇ ÆËÂÊÑÕËÓÑÄÂÐËÇ 3-ÂÏËÐÑ-4-ÂÊËÆÑ1,2,5-ÑÍÔÂÆËÂÊÑÎÂ.132 N3

(CH3COO)4Pb

¡ÎÍËÎËÓÑÄÂÐËÇ 1,5- Ë 2,5-ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ âÄÎâÇÕÔâ ÖÆÑÃÐÞÏ ÏÇÕÑÆÑÏ ÔËÐÕÇÊ ÔÑÎÇÌ ÕÇÕÓÂÊÑÎËâ.136 ¯ÇÆÂÄÐÑ ÒÑÍÂÊÂÐÑ,139 ÚÕÑ ÒÓË ÂÎÍËÎËÓÑÄÂÐËË 1,5-ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÆËÂÎÍËÎÔÖÎß×ÂÕÂÏË ËÎË ÂÎÍËÎËÑÆËÆÂÏË Ô ØÑÓÑÛËÏ ÄÞØÑÆÑÏ ÑÃÓÂÊÖáÕÔâ 1,4,5-ÕÓËÊÂÏÇÜÇÐÐÞÇ ÔÑÎË ÕÇÕÓÂÊÑÎËâ. µÍÂÊÂÐÐÞÇ ÔÑÎË ÕÇÕÓÂÊÑÎËâ ÃÞÎË ÕÂÍÉÇ ÒÑÎÖÚÇÐÞ ÒÓË ÒÑÔÎÇÆÑÄÂÕÇÎßÐÑÌ ÑÃÓÂÃÑÕÍÇ ÐËÕÓËÎÑÄ ÏÇÕËÎÑÄÞÏ à×ËÓÑÏ ÕÓË×ÕÑÓÏÇÕÂÐÔÖÎß×ÑÍËÔÎÑÕÞ Ë ÏÇÕËÎÂÊËÆÑÏ.140 R2HCCN

F3CSO3CH3

R2HC CH3

N CH3 + N N F3CSOÿ 3 N C

+

R2HC C N CH3 F3CSOÿ 3

CH3N3

852

°ÍËÔÎÇÐËÇ ×ÑÓÏÂÊÂÐÑÄ ÓÂÊÎËÚÐÑÅÑ ÔÕÓÑÇÐËâ ÒÇÓÏÂÐÅÂÐÂÕÑÏ ÍÂÎËâ Ä ÆÄÖØ×ÂÊÐÑÌ ÔËÔÕÇÏÇ ÑÓÅÂÐËÚÇÔÍËÌ ÓÂÔÕÄÑÓËÕÇÎß ë ÄÑÆÂ Ô ÄÞÔÑÍËÏ ÄÞØÑÆÑÏ ÒÓËÄÑÆËÕ Í ÔÑÑÕÄÇÕÔÕÄÖáÜËÏ ÔÑÎâÏ ÕÇÕÓÂÊÑÎËâ. ³ÖÜÇÔÕÄÇÐÐÑÌ ÑÔÑÃÇÐÐÑÔÕßá àÕÑÌ ÓÇÂÍÙËË âÄÎâÇÕÔâ ÕÑ, ÚÕÑ ÓÑÎß ÍÂÕÂÎËÊÂÕÑÓ ÏÇÉ×ÂÊÐÑÅÑ ÒÇÓÇÐÑÔ ÄÞÒÑÎÐâÇÕ ÅËÆÓÑÍÔËÆ ÕÇÕÓÂÊÑÎËâ, ÍÑÕÑÓÞÌ ÑÃÓÂÊÖÇÕÔâ РÒÇÓÄÑÏ àÕÂÒÇ ÓÇÂÍÙËË ì ÒÓË ÑÍËÔÎÇÐËË ×ÑÓÏÂÊÂÐÂ, ÒÓÑËÔØÑÆâÜÇÏ Ð ÅÓÂÐËÙÇ ÓÂÊÆÇΠ×ÂÊ.34, 141, 142 ±ÑÎÖÚÇÐËÇ ÏÇÊÑËÑÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÑÒËÔÂÐÑ Ä ÓÂÃÑÕÂØ 143 ë 145.

III. ¶ËÊËÍÑ-ØËÏËÚÇÔÍËÇ ÔÄÑÌÔÕÄ 1. ¿ÎÇÍÕÓÑÐÐÑÇ ÔÕÓÑÇÐËÇ ¥Îâ ËÔÔÎÇÆÑÄÂÐËâ àÎÇÍÕÓÑÐÐÑÅÑ ÔÕÓÑÇÐËâ ÕÇÕÓÂÊÑÎÑÄ Ä ÒÑÔÎÇÆÐÇÇ ÆÇÔâÕËÎÇÕËÇ ÖÔÒÇÛÐÑ ÒÓËÏÇÐâÎËÔß ÐÇàÏÒËÓËÚÇÔÍËÇ ÏÇÕÑÆÞ ÍÄÂÐÕÑÄÑÌ ØËÏËË. °ÔÐÑÄÐÑÇ ÄÐËÏÂÐËÇ ÖÆÇÎâÎÑÔß ÒÓÑÃÎÇÏÇ ÒÓÑÕÑÕÓÑÒÐÑÌ ÕÂÖÕÑÏÇÓËË, ÆÎâ ÓÇÛÇÐËâ ÍÑÕÑÓÑÌ ËÔÒÑÎßÊÑÄÂÎÔâ ÏÇÕÑÆ ab initio. £ ÃÂÊËÔÂØ 6-31G** Ë 6.311+G(2d,2p) ÄÞÚËÔÎÇРÒÑÎÐÂâ àÐÇÓÅËâ 1H- Ë 2¯-ÕÂÖÕÑÏÇÓÑÄ ÕÇÕÓÂÊÑÎÂ. ªÊ àÕËØ ÆÂÐÐÞØ ÔÎÇÆÖÇÕ, ÚÕÑ Ä ÅÂÊÑÄÑÌ ×ÂÊÇ ÃÑÎÇÇ ÖÔÕÑÌÚËÄ 2¯-ÕÂÖÕÑÏÇÓ.146, 147 £ÇÎËÚËРÄÇÓÕËÍÂÎßÐÑÅÑ ÒÑÕÇÐÙËÂΠËÑÐËÊÂÙËË 2¯-ÕÂÖÕÑÏÇÓ ÕÇÕÓÂÊÑÎÂ, ÄÞÚËÔÎÇÐÐÂâ ÍÄÂÐÕÑÄÑØËÏËÚÇÔÍËÏË ÏÇÕÑÆÂÏË, ÔÑÅÎÂÔÖÇÕÔâ Ô àÍÔÒÇÓËÏÇÐÕÂÎßÐÞÏ ÊÐÂÚÇÐËÇÏ, ÒÑÎÖÚÇÐÐÞÏ ÏÇÕÑÆÑÏ ×ÑÕÑàÎÇÍÕÓÑÐÐÑÌ ÔÒÇÍÕÓÑÔÍÑÒËË.148 ³ÎÇÆÖÇÕ ÑÕÏÇÕËÕß, ÚÕÑ Ð ÃÑÎßÛÖá ÖÔÕÑÌÚËÄÑÔÕß 2¯-ÕÂÖÕÑÏÇÓÂ Ä ÅÂÊÑÄÑÌ ×ÂÊÇ ÖÍÂÊÞÄÂáÕ ÓÇÊÖÎßÕÂÕÞ ÍÄÂÐÕÑÄÑØËÏËÚÇÔÍËØ ÓÂÔÚÇÕÑÄ ÍÂÕËÑÐÓÂÆËÍÂÎÑÄ ÆÄÖØ ÒÓÑÕÑÕÓÑÒÐÞØ ÕÂÖÕÑÏÇÓÑÄ, ÄÞÒÑÎÐÇÐÐÞØ ÒÑÎÖàÏÒËÓËÚÇÔÍËÏ ÏÇÕÑÆÑÏ CNDO/2,  ÕÂÍÉÇ ÆÂÐÐÞÇ ÏÂÔÔÔÒÇÍÕÓÑÄ.149, 150 ¯ÂÒÓÑÕËÄ, ÓÂÔÚÇÕÞ ÔÑÄÓÇÏÇÐÐÞÏ ÒÑÎÖàÏÒËÓËÚÇÔÍËÏ ÏÇÕÑÆÑÏ MNDO ÔÄËÆÇÕÇÎßÔÕÄÖáÕ Ñ ÃÑÎßÛÇÌ ÖÔÕÑÌÚËÄÑÔÕË Ä ÅÂÊÑÄÑÌ ×ÂÊÇ 1H-ÕÂÖÕÑÏÇÓÑÄ ÕÇÕÓÂÊÑÎÂ Ë 5-×ÕÑÓÕÇÕÓÂÊÑÎÂ.36, 37 °ÃÝÇÍÕËÄÐÑ ÄÞÃÑÓ ÃÂÊËÔ ÐÇ ËÅÓÂÇÕ ÒÓËÐÙËÒËÂÎßÐÑÌ ÓÑÎË ÒÓË ÂÐÂÎËÊÇ ÒÓÑÕÑÕÓÑÒÐÑÌ ÕÂÖÕÑÏÇÓËË ÕÇÕÓÂÊÑΠÐÇàÏÒËÓËÚÇÔÍËÏ ÏÇÕÑÆÑÏ. °ÆÐÂÍÑ ÔËÕÖÂÙËâ ÏÇÐâÇÕÔâ ÒÓË ÒÇÓÇØÑÆÇ Í ÒÓÑÕÑÐËÓÑÄÂÐÐÑÏÖ ÕÇÕÓÂÊÑÎÖ (ÍÂÕËÑÐÖ ÕÇÕÓÂÊÑÎËâ). ©ÆÇÔß ÔÎÇÆÖÇÕ ËÏÇÕß Ä ÄËÆÖ, ÚÕÑ ÒÓË ÓÂÔÚÇÕÇ àÐÇÓÅËË ÒÓÑÕÑÐËÓÑÄÂÐËâ ÕÇÕÓÂÊÑÎÂ Ä ÏËÐËÏÂÎßÐÑÏ ÃÂÊËÔÇ ÒÑÎÖÚÂáÕÔâ ÊÂÄÞÛÇÐÐÞÇ ÊÐÂÚÇÐËâ. ªÊ ÓÂÔÚÇÕÑÄ ÔÎÇÆÖÇÕ, ÚÕÑ ÐÂËÃÑÎÇÇ ÖÔÕÑÌÚËÄÞÏ âÄÎâÇÕÔâ ÍÂÕËÑÐ ÕÇÕÓÂÊÑÎËâ, ÔÑÆÇÓÉÂÜËÌ ÒÓÑÕÑÐÞ Ä ÒÑÎÑÉÇÐËâØ 1 Ë 4 ÅÇÕÇÓÑÙËÍÎÂ, ÒÓËÚÇÏ ÑÕÐÑÔËÕÇÎßÐÂâ ÔÕÂÃËÎßÐÑÔÕß àÕÑÅÑ ÕÂÖÕÑÏÇÓ ÖÏÇÐßÛÂÇÕÔâ Р29.3 괃 . ÏÑÎß71 ÒÓË ÒÇÓÇØÑÆÇ ÑÕ ÃÂÊËÔ STO-3G Í ÃÂÊËÔÖ 6-31G**/6-31G.38, 151 ¡ÐÂÎÑÅËÚÐÞÌ ÂÐÂÎËÊ ÒÓÑÄÇÆÇÐ ÆÎâ ÒÓÑÕÑÐËÓÑÄÂÐÐÞØ 1-ÏÇÕËÎ- Ë 2-ÏÇÕËÎÕÇÕÓÂÊÑÎÑÄ, ÆÎâ ÍÑÕÑÓÞØ, ÔÑÅÎÂÔÐÑ ÓÂÔÚÇÕÂÏ ab initio (6-31G), ÙÇÐÕÓÑÏ ÑÔÐÑÄÐÑÔÕË ÕÂÍÉÇ âÄÎâÇÕÔâ ÂÕÑÏ N(4) ÅÇÕÇÓÑÙËÍÎÂ.152 ºËÓÑÍÑÇ ÒÓËÏÇÐÇÐËÇ ÍÄÂÐÕÑÄÑØËÏËÚÇÔÍËØ ÏÇÕÑÆÑÄ ÒÑÊÄÑÎËÎÑ ÒÑÎÖÚËÕß ÙÇÐÐÖá ËÐ×ÑÓÏÂÙËá ÐÇ ÕÑÎßÍÑ Ñ ÒÓÑÕÑÕÓÑÒÐÑÌ ÕÂÖÕÑÏÇÓËË ÕÇÕÓÂÊÑÎÑÄ, ÐÑ Ë ÒÑ ÏÐÑÅËÏ ÆÓÖÅËÏ ËÐÕÇÓÇÔÐÞÏ ÄÑÒÓÑÔÂÏ. ´ÂÍ, ÏÇÕÑÆÑÏ ab initio ÒÓÑÄÇÆÇÐ ÕÑÒÑÎÑÅËÚÇÔÍËÌ ÂÐÂÎËÊ ÔÕÓÑÇÐËâ ÍÑÏÒÎÇÍÔÑÄ ÕÇÕÓÂÊÑÎÂ Ô Li+, Na+, K+ Ë Al3+. ±ÑÍÂÊÂРÄÑÊÏÑÉÐÑÔÕß ÓÂÊÎËÚÐÑÅÑ ÄÊÂËÏÐÑÅÑ ÓÂÔÒÑÎÑÉÇÐËâ Ä ÒÓÑÔÕÓÂÐÔÕÄÇ ÅÇÕÇÓÑÙËÍÎËÚÇÔÍÑÅÑ ÎËÅÂÐÆÂ Ë ËÑРÏÇÕÂÎÎÂ.40 ¥Îâ ÂÐÂÎËÊ àÎÇÍÕÓÑÐÐÑÅÑ ÔÕÓÑÇÐËâ ÕÇÕÓÂÊÑÎÂ Ë ÇÅÑ ÒÓÑËÊÄÑÆÐÞØ Ô ÖÔÒÇØÑÏ ÒÓËÄÎÇÍÂáÕÔâ Ë ÔÑÄÓÇÏÇÐÐÞÇ ÒÑÎÖàÏÒËÓËÚÇÔÍËÇ ÏÇÕÑÆÞ. ±ÑÍÂÊÂÐÑ, ÚÕÑ ÏÇÕÑÆ MNDO ÂÆÇÍÄÂÕÐÑ ÑÒËÔÞÄÂÇÕ àÎÇÍÕÓÑÐÐÖá ÔÕÓÖÍÕÖÓÖ ÕÇÕÓÂÊÑÎÑÄ, ÒÓËÚÇÏ ÒÓËÏÇÐÇÐËÇ àÕÑÅÑ ÏÇÕÑÆ ËÐÑÅÆ ÑÍÂÊÞÄÂÇÕÔâ ÃÑÎÇÇ ÒÓÇÆÒÑÚÕËÕÇÎßÐÞÏ, ÚÇÏ ËÔÒÑÎßÊÑÄÂÐËÇ ÏÇÕÑÆ ab initio Ä ÏËÐËÏÂÎßÐÑÏ ÃÂÊËÔÇ.153 £ÏÇÔÕÇ Ô ÕÇÏ ÑÕÏÇÚÂÇÕÔâ, ÚÕÑ àÕÑÕ ÏÇÕÑÆ ÆÂÇÕ ÊÂÐËÉÇÐÐÞÇ Ð 83.8 괃 . ÏÑÎß71 ÊÐÂÚÇÐËâ àÐÕÂÎßÒËË ÑÃÓÂÊÑÄÂÐËâ: 230.5 Ë 248.0 괃 . ÏÑÎß71 ÆÎâ 1H- Ë 2¯-ÕÇÕÓÂÊÑÎÑÄ ÔÑÑÕÄÇÕÔÕÄÇÐÐÑ.36

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N

R1 =C2H5O, C6H5O, p-NO2C6H4O, 2-C10H7O, C6H5NH,

²ÇÂÍÙËË àÎÇÍÕÓÑ×ËÎßÐÑÅÑ ÊÂÏÇÜÇÐËâ ÒÑ ÙËÍÎËÚÇÔÍÑÏÖ ÂÕÑÏÖ ÖÅÎÇÓÑÆÂ Ä ÓâÆÖ ÕÇÕÓÂÊÑÎÑÄ ËÊÖÚÇÐÞ ÐÇÆÑÔÕÂÕÑÚÐÑ. ¯ÇÆÂÄÐÑ ÃÞÎÑ ÒÑÍÂÊÂÐÑ, ÚÕÑ 1-ÂÎÍËÎÕÇÕÓÂÊÑÎÞ ÅÎÂÆÍÑ ËÑÆËÓÖáÕÔâ ËÑÆÑÏ Ä ÓÂÔÕÄÑÓÇ ÔÇÓÐÑÌ ÍËÔÎÑÕÞ Ä ÒÓËÔÖÕÔÕÄËË ÒÇÓÏÂÐÅÂÐÂÕ ÍÂÎËâ.239 ³ÑÑÕÄÇÕÔÕÄÖáÜËÇ 1-ÂÎÍËÎ-5-ËÑÆÕÇÕÓÂÊÑÎÞ ÑÃÓÂÊÖáÕÔâ Ô ÄÞØÑÆÑÏ 55 ë 75%. µÔÕÂÐÑÄÎÇÐÑ ÕÂÍÉÇ, ÚÕÑ ÒÓË ÑÃÓÂÃÑÕÍÇ 1-ÏÇÕËÎÕÇÕÓÂÊÑΠÕÓÇÕ-ÃÖÕËÎÎËÕËÇÏ Ä ÕÇÕÓÂÅËÆÓÑ×ÖÓÂÐÇ ÄÑÆÑÓÑÆ Ö ÙËÍÎËÚÇÔÍÑÅÑ ÂÕÑÏ ÖÅÎÇÓÑÆ ÊÂÏÇÜÂÇÕÔâ РÎËÕËÌ.240 £ ÔÑÎâØ 2,3-ÆËÂÓËÎÕÇÕÓÂÊÑÎËâ ÒÑÆ ÆÇÌÔÕÄËÇÏ ÕÓÇÕ-ÃÖÕËÎÎËÕËâ Ä ÅÇÍÔÂÐÇ ÕÂÍÉÇ ÒÓÑËÔØÑÆËÕ ÊÂÏÇÜÇÐËÇ ÄÑÆÑÓÑÆÂ Ö ÂÕÑÏ ÖÅÎÇÓÑÆ ÙËÍÎÂ.241, 242 1-©ÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ Ä ÏâÅÍËØ ÖÔÎÑÄËâØ ÄÔÕÖÒÂáÕ Ä ÓÇÂÍÙËá Ô ×ÑÓÏÂÎßÆÇÅËÆÑÏ Ë ÂÏËÐÂÏË, ÆÂÄÂâ ÒÓÑÆÖÍÕÞ ÂÏËÐÑÏÇÕËÎËÓÑÄÂÐËâ.59, 243 + HCHO + R2NH

O

R2C

p-NO2C6H4NH, 2-C10H7NH,

1. ¿ÎÇÍÕÓÑ×ËÎßÐÑÇ ÊÂÏÇÜÇÐËÇ ÒÑ ÂÕÑÏÖ ÖÅÎÇÓÑÆ ÍÑÎßÙÂ

CH

N

CHR

£ 1-ÂÓËÎ-5-ÏÇÓÍÂÒÕÑÕÇÕÓÂÊÑÎÂØ ÒÓË ÜÇÎÑÚÐÑÏ ÅËÆÓÑÎËÊÇ Ä ÄÑÆÐÑÏ ÏÇÕÂÐÑÎÇ ÓÂÔÜÇÒÎâÇÕÔâ ÔÄâÊß ÏÇÉÆÖ ÂÕÑÏÂÏË ÔÇÓÞ Ë ÖÅÎÇÓÑÆÂ, ÚÕÑ ÒÓËÄÑÆËÕ Í ÑÃÓÂÊÑÄÂÐËá 1-ÂÓËÎ-5-ÕÇÕÓÂÊÑÎÑÎÑÄ.245 ´ÇÕÓÂÊÑÎßÐÞÌ ÙËÍÎ Ä 1-ÃÇÐÊÑËÎ- Ë 2-ÃÇÐÊÑËÎ-5-ÂÓËÎÕÇÕÓÂÊÑÎÂØ ÎÇÅÍÑ ÊÂÏÇÜÂÇÕÔâ ÐÖÍÎÇÑ×ËÎÂÏË ÓÂÊÎËÚÐÑÅÑ ÔÕÓÑÇÐËâ.247 N-¢ÇÐÊÑËÎÕÇÕÓÂÊÑÎÞ âÄÎâáÕÔâ ÏâÅÍËÏË ÂÙËÎËÓÖáÜËÏË ÓÇÂÅÇÐÕÂÏË, à××ÇÍÕËÄÐÞÏË Ä ÓÇÂÍÙËâØ Ô ÒÇÓÄËÚÐÞÏË Ë ÄÕÑÓËÚÐÞÏË ÂÎË×ÂÕËÚÇÔÍËÏË Ë ÂÓÑÏÂÕËÚÇÔÍËÏË ÂÏËÐÂÏË Ë ÔÒËÓÕÂÏË, ÃÇÐÊËÏËÆÂÊÑÎÑÏ Ë ÃÇÐÊÕÓËÂÊÑÎÑÏ.

IV. ²ÇÂÍÙËË ÕÇÕÓÂÊÑÎÑÄ

R1N

H2 C +

R1 N N

CCH2NR2 N

N

¯ÂÍÑÐÇÙ, ÔÎÇÆÖÇÕ ÑÕÏÇÕËÕß, ÚÕÑ Ä ÔÑÎâØ 2,3-ÆËÂÓËÎ-5-ÕÓË×ÇÐËÎ×ÑÔ×ÑÐËÌÕÇÕÓÂÊÑÎËâ ÕÓË×ÇÐËÎ×ÑÔ×ÑÐËÇÄÂâ ÅÓÖÒ-Ò ÊÂÏÇÜÂÇÕÔâ Р×ÕÑÓ ÒÑÆ ÆÇÌÔÕÄËÇÏ ×ÕÑÓËÆ ÙÇÊËâ Ä ÒÓËÔÖÕÔÕÄËË ÃÓÑÏÂ.241

N

, N

N

N

±Ñ ÔÓÂÄÐÇÐËá Ô ÛËÓÑÍÑ ÒÓËÏÇÐâÇÏÞÏË ÂÙËÎËÓÖáÜËÏË ÂÅÇÐÕÂÏË ì N-ÃÇÐÊÑËÎËÏËÆÂÊÑÎÑÏ Ë N-ÂÙËÎËÏËÆÂÊÑÎÂÏË 248 ì N-ÃÇÐÊÑËÎ-5-ÂÓËÎÕÇÕÓÂÊÑÎÞ ÑÃÎÂÆÂáÕ ÔÖÜÇÔÕÄÇÐÐÞÏË ÒÓÇËÏÖÜÇÔÕÄÂÏË. ±Ñ ÓÇÂÍÙËÑÐÐÑÌ ÔÒÑÔÑÃÐÑÔÕË N-ÃÇÐÊÑËÎÕÇÕÓÂÊÑÎÞ ÒÓÇÄÑÔØÑÆâÕ N-ÂÙËÎËÏËÆÂÊÑÎÞ,  ÕÂÍÉÇ ØÂÓÂÍÕÇÓËÊÖáÕÔâ ÄÞÔÑÍÑÌ ËÊÃËÓÂÕÇÎßÐÑÔÕßá ÒÑ ÑÕÐÑÛÇÐËá Í ÒÇÓÄËÚÐÞÏ Ë ÄÕÑÓËÚÐÞÏ ÅËÆÓÑÍÔË- Ë ÂÏËÐÑÅÓÖÒÒÂÏ.249 ±ÓËÏÇÐÇÐËÇ N-ÃÇÐÊÑËÎÕÇÕÓÂÊÑÎÑÄ ÑÔÑÃÇÐÐÑ à××ÇÍÕËÄÐÑ, ÍÑÅÆ ÓÇÂÅÇÐÕÞ Ë ÒÓÑÆÖÍÕÞ ÓÇÂÍÙËË ÚÖÄÔÕÄËÕÇÎßÐÞ Í ÍËÔÎÑÕÂÏ Ë ÜÇÎÑÚÂÏ,  ÕÂÍÉÇ ÕÇÓÏËÚÇÔÍË ÏÂÎÑÖÔÕÑÌÚËÄÞ. ´ÇÕÓÂÊÑÎßÐÞÌ ÙËÍÎ Ä 1-ÕÓË×ÇÐËÎÏÇÕËÎ-5-R-ÕÇÕÓÂÊÑÎÂØ ÎÇÅÍÑ ÊÂÏÇÜÂÇÕÔâ ÒÑÆ ÆÇÌÔÕÄËÇÏ ÕÓË×ÕÑÓÖÍÔÖÔÐÑÌ ÍËÔÎÑÕÞ Ä ÄÑÆÐÑÏ ÕÇÕÓÂÅËÆÓÑ×ÖÓÂÐÇ.78 RC N

NC(C6H5)3 N

N

F3CCOOH7H2O

RC (C6H5)3COH + N

NH N

N

µÔÒÇØË ØËÏËË 63 (10) 1994

855

3. ¡ÎÍËÎËÓÑÄÂÐËÇ ¡ÎÍËÎËÓÑÄÂÐËÇ ÑÕÐÑÔËÕÔâ Í ÕÇÏ ÓÇÂÍÙËâÏ ÕÇÕÓÂÊÑÎÑÄ, ÍÑÕÑÓÞÇ ËÊÖÚÇÐÞ ÐÂËÃÑÎÇÇ ÒÑÆÓÑÃÐÑ. ¡ÎÍËÎËÓÑÄÂÐËÇ ì ÒÓÑÔÕÑÌ ÒÖÕß ÔËÐÕÇÊ ÏÑÐÑ- Ë ÆËÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÓÂÊÎËÚÐÑÅÑ ÔÕÓÑÇÐËâ, ÒÑÎÖÚÇÐËÇ ÍÑÕÑÓÞØ ÆÓÖÅËÏË ÏÇÕÑÆÂÏË ÊÂÚÂÔÕÖá ÐÇÄÑÊÏÑÉÐÑ. £ ÕÇÑÓÇÕËÚÇÔÍÑÏ ÑÕÐÑÛÇÐËË àÕ ÓÇÂÍÙËâ ÒÓÇÆÔÕÂÄÎâÇÕ ÃÑÎßÛÑÌ ËÐÕÇÓÇÔ, ÕÂÍ ÍÂÍ ÏÑÉÇÕ ÔÎÖÉËÕß ÖÆÑÃÐÑÌ ÏÑÆÇÎßá ÒÓË ËÊÖÚÇÐËË ÅÇÕÇÓÑÙËÍÎËÚÇÔÍËØ ÔÖÃÔÕÓÂÕÑÄ, ÑÃÎÂÆÂáÜËØ ÆÄÑÌÔÕÄÇÐÐÑÌ ÓÇÂÍÙËÑÐÐÑÌ ÔÒÑÔÑÃÐÑÔÕßá. £ ÓÇÂÍÙËá ÂÎÍËÎËÓÑÄÂÐËâ Ä ÊÂÄËÔËÏÑÔÕË ÑÕ ÔÄÑÌÔÕÄ ÓÇÂÍÙËÑÐÐÑÌ ÔÓÇÆÞ, ÄÔÕÖÒÂáÕ ÕÇÕÓÂÊÑÎ, 5-ÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ,  ÕÂÍÉÇ ËØ ÔÑÎË. £ ÍÂÚÇÔÕÄÇ ÂÎÍËÎËÓÖáÜËØ ÂÅÇÐÕÑÄ ËÔÒÑÎßÊÖáÕ ÅÂÎÑÅÇÐÂÎÍÂÐÞ,250 ë 255 à×ËÓÞ ÔÇÓÐÑÌ Ë ÂÓÑÏÂÕËÚÇÔÍËØ ÔÖÎß×ÑÍËÔÎÑÕ,254 ÂÙÇÕÂÕÞ ÐËÕÓÑÂÏËÐÑÔÒËÓÕÑÄ,256 ÔÑÇÆËÐÇÐËâ, ÔÑÆÇÓÉÂÜËÇ ÂÍÕËÄËÓÑÄÂÐÐÞÇ ÍÓÂÕÐÞÇ ÔÄâÊË.175, 176, 257, 258 ¯ÇÆÂÄÐÑ ÑÒÖÃÎËÍÑÄÂÐÞ ÆÂÐÐÞÇ Ñ ÒÓËÏÇÐÇÐËË ÆÎâ àÕËØ ÙÇÎÇÌ ÔÒËÓÕÑÄ 259 ë 262 Ë ÐÇÒÓÇÆÇÎßÐÞØ ÔÑÇÆËÐÇÐËÌ (ÒÓÑÒËÎÇÐÂ Ë ËÊÑÃÖÕËÎÇÐÂ),263 ÐÇÍÑÕÑÓÞØ ÐËÕÓËÎËÇÄÞØ ËÑÐÑÄ 264 Ë ÒÓÑÔÕÞØ ÄËÐËÎÑÄÞØ à×ËÓÑÄ.265 °ÕÆÇÎßÐÑ ÔÎÇÆÖÇÕ ÑÕÏÇÕËÕß ÓÇÂÍÙËË 5-ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ Ô ÂÎßÆÇÅËÆÂÏË (×ÑÓÏÂÎßÆÇÅËÆÑÏ) Ë ÂÏËÐÂÏË, Ä ÓÇÊÖÎßÕÂÕÇ ÍÑÕÑÓÞØ ÑÃÓÂÊÖáÕÔâ N-ÂÏËÐÑÏÇÕËÎßÐÞÇ (N-ÑÍÔËÏÇÕËÎßÐÞÇ) ÒÓÑËÊÄÑÆÐÞÇ ÕÇÕÓÂÊÑÎÑÄ.266 ë 269 ²ÂÐÇÇ ÒÑÎÂÅÂÎË, ÚÕÑ ÒÓË ÂÎÍËÎËÓÑÄÂÐËË ÕÇÕÓÂÊÑÎÂ Ë 5-ÊÂÏÇÜÇÐÐÞØ ÕÇÕÓÂÊÑÎÑÄ ÐÇÊÂÄËÔËÏÑ ÑÕ ÒÓËÓÑÆÞ ÂÎÍËÎËÓÖáÜÇÅÑ ÂÅÇÐÕÂ Ë ÔÄÑÌÔÕÄ ÓÇÂÍÙËÑÐÐÑÌ ÔÓÇÆÞ ÄÔÇÅÆ ÑÃÓÂÊÖáÕÔâ ÔÑÑÕÄÇÕÔÕÄÖáÜËÇ 1- Ë 2-ÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ. R1C N

7 N

N Z+ N

+

R2X

R1C

NR2

N

N

N

R1C +

N

ÑÍÔÂÆËÂÊÑÎÞ ÓÂÊÎËÚÐÑÅÑ ÔÕÓÑÇÐËâ,142, 247, 270 ë 273  ÕÂÍÉÇ ÓÂÐÇÇ ÐÇÆÑÔÕÖÒÐÞÇ 3¯-1,3,4-ÃÇÐÊÑÕÓËÂÊÇÒËÐÞ.274 ë 277 ´ÂÍ, ÕÇÕÓÂÊÑÎ Ë 5-ÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ ÒÓË ÂÙËÎËÓÑÄÂÐËË ØÎÑÓÂÐÅËÆÓËÆÂÏË ÑÓÅÂÐËÚÇÔÍËØ ÍËÔÎÑÕ Ä ÒÓËÔÖÕÔÕÄËË ÑÓÅÂÐËÚÇÔÍËØ ÑÔÐÑÄÂÐËÌ ÒÓË 100 ë 1208³ Ô ÄÞÔÑÍËÏ ÄÞØÑÆÑÏ ÒÓÇÄÓÂÜÂáÕÔâ Ä ÔÑÑÕÄÇÕÔÕÄÖáÜËÇ 1,3,4-ÑÍÔÂÆËÂÊÑÎÞ. R1C

NH

N

N

N

+ R2COCl

N

C5H5N 7N2

R1C

N O

CR2

²ÂÐÇÇ ÒÑÎÂÅÂÎË, ÚÕÑ Ä àÕÑÌ ÓÇÂÍÙËË Ð ÒÇÓÄÑÌ ÔÕÂÆËË ÑÃÓÂÊÖÇÕÔâ ÐÇÖÔÕÑÌÚËÄÞÌ 2-ÂÙËÎÕÇÕÓÂÊÑÎ, ÓÂÔÜÇÒÎÇÐËÇ ÍÑÕÑÓÑÅÑ Ô ÄÞÆÇÎÇÐËÇÏ ÏÑÎÇÍÖÎÞ ÂÊÑÕ ÒÓËÄÑÆËÕ Í 1,3,4ÑÍÔÂÆËÂÊÑÎÖ.278 °ÆÐÂÍÑ Ä ÆÂÎßÐÇÌÛÇÏ, ÃÎÂÅÑÆÂÓâ ÒÓËÏÇÐÇÐËá ÏÇÉ×ÂÊÐÑÅÑ ÍÂÕÂÎËÊÂ, ÃÞÎÑ ÒÑÍÂÊÂÐÑ, ÚÕÑ ÒÓË ÂÙËÎËÓÑÄÂÐËË 5-ÂÓËÎÕÇÕÓÂÊÑÎÑÄ ØÎÑÓÂÐÅËÆÓËÆÂÏË ÊÂÏÇÜÇÐÐÞØ ÃÇÐÊÑÌÐÞØ ÍËÔÎÑÕ ÒÑÎÖÚÂáÕÔâ ÐÇ ÕÑÎßÍÑ 2-ÃÇÐÊÑËÎÕÇÕÓÂÊÑÎÞ, ÐÑ Ë ËÊÑÏÇÓÐÞÇ 1-ÃÇÐÊÑËÎÕÇÕÓÂÊÑÎÞ.247, 271 ArC

NH

N

N

N

+ R1C6H4COCl

+

1 ÏÂÔ.% (C4H9)4N Br7

ArC N

CH2Cl27ÄÑÆÐ.NaOH,

ArC

NCOC6H4R1 N

N

+

N

N N

NCOC6H4R1

N N

NR2

Z+ 7 ÍÂÕËÑÐ

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4. ¡ÙËÎËÓÑÄÂÐËÇ Ë ËÏËÆÑËÎËÓÑÄÂÐËÇ ²ÇÂÍÙËË ÕÇÕÓÂÊÑÎÑÄ Ô ÂÙËÎËÓÖáÜËÏË ÓÇÂÅÇÐÕÂÏË Ë ËÏËÆÑËÎØÎÑÓËÆÂÏË Ä ÒÑÔÎÇÆÐËÇ ÐÇÔÍÑÎßÍÑ ÎÇÕ ÒÓËÑÃÓÇÎË ÑÔÑÃÑÇ ÊÐÂÚÇÐËÇ, ÅÎÂÄÐÞÏ ÑÃÓÂÊÑÏ Ä ÔÄâÊË Ô ÕÇÏ, ÚÕÑ Ô ËØ ÒÑÏÑÜßá ÏÑÅÖÕ ÃÞÕß ÒÑÎÖÚÇÐÞ 2,5-ÆËÊÂÏÇÜÇÐÐÞÇ 1,3,4-

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NH

N

N

N

+ R2C NC6H5 Cl

CH2Cl27ÄÑÆÐ.NaOH, +

1 ÏÂÔ.% (C4H9)4N Br7

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+

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7N2

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N C NH C N R1

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NH

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N

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NH N

N

°ÃÓÂÜÂÇÕ Ð ÔÇÃâ ÄÐËÏÂÐËÇ ÕÑÕ ×ÂÍÕ, ÚÕÑ àÎÇÍÕÓÑ×ËÎßÐÑÇ ÊÂÏÇÜÇÐËÇ ÒÓÑËÔØÑÆËÕ ÕÑÎßÍÑ ÒÑ ×ÇÐËÎßÐÑÏÖ ÍÑÎßÙÖ Ë ÐÇ ÊÂÕÓÂÅËÄÂÇÕ ÕÇÕÓÂÊÑÎßÐÞÌ ÙËÍÎ. ªÐÕÇÓÇÔÐÑ, ÚÕÑ ÍÑÅÆÂ Ä ÂÐÂÎÑÅËÚÐÞØ ÖÔÎÑÄËâØ Ä ÓÇÂÍÙËá ÄÔÕÖÒÂáÕ N-ÏÇÕËÎ-5-ÂÎÍËÎÕÇÕÓÂÊÑÎÞ, àÎÇÍÕÓÑ×ËÎßÐÑÇ ÊÂÏÇÜÇÐËÇ ÒÓÑËÔØÑÆËÕ ÍÂÍ ÒÑ N-ÏÇÕËÎßÐÑÌ, ÕÂÍ Ë ÒÑ ³-ÂÎÍËÎßÐÑÌ ÅÓÖÒÒÂÏ.285

NH CHC6H4R1 CH2 N

CC6H4R2

±ÓË ÆÇÌÔÕÄËË Ð 1-ÅËÆÓÑÍÔË-5-×ÇÐËÎÕÇÕÓÂÊÑÎ ÑÍËÔÇÌ ÑÎÇ×ËÐÑÄ ÓÇÂÍÙËâ ÒÓÑËÔØÑÆËÕ ÍÂÍ ÒÑ ÅËÆÓÑÍÔËÎßÐÑÌ ÅÓÖÒÒÇ, ÕÂÍ Ë ÒÑ ÕÇÕÓÂÊÑÎßÐÑÏÖ ÙËÍÎÖ.297 £ ÕÑ ÉÇ ÄÓÇÏâ Ä ÓÇÂÍÙËË 1-ÅËÆÓÑÍÔË-5-ÏÇÕËÎÕÇÕÓÂÊÑÎÂ Ô ÏÇÕËÎÄËÐËÎÍÇÕÑÐÑÏ ÑÃÓÂÊÖáÕÔâ ÔÑÑÕÄÇÕÔÕÄÖáÜËÇ ËÊÑÏÇÓÐÞÇ N-ÑÍËÔË.298 CH3C N

O

NOH N

N

+ CH2

CH CCH3

µÔÒÇØË ØËÏËË 63 (10) 1994

CH3C N

N N

857

O

N

+

O

CH3C

O

CH3CCH2CH2

N

N N

N

±ÓË ÂÎÍËÎËÓÑÄÂÐËË ÃËÔ-(1-ÂÓËÎÕÇÕÓÂÊÑÎ-5-ËÎ)ÏÇÕÂÐÑÄ ËÑÆËÔÕÞÏ ÏÇÕËÎÑÏ 299 Ë ÂÓËÎËÓÑÄÂÐËË Ë ÂÎÍËÎËÓÑÄÂÐËË (1-×ÇÐËÎÕÇÕÓÂÊÑÎ-5-ËÎ)ÕËÑΠÔÑÑÕÄÇÕÔÕÄÇÐÐÑ 2,4-ÆËÐËÕÓÑØÎÑÓÃÇÐÊÑÎÑÏ 300 Ë ÕÓÇÕ-ÃÖÕËÎËÊÑÐËÕÓËÎÑÏ,301  ÕÂÍÉÇ ÒÓË ÄÊÂËÏÑÆÇÌÔÕÄËË ÕÇÕÓÂÊÑÎÔÑÆÇÓÉÂÜËØ ÅÎËÑÍÔËÏÑÄ Ô ÃÓÑÏÙËÂÐÑÏ 302 ÕÇÕÓÂÊÑÎßÐÑÇ ÍÑÎßÙÑ ÐÇ ÊÂÕÓÂÅËÄÂÇÕÔâ.

7. ¥ÇÌÔÕÄËÇ ÐÖÍÎÇÑ×ËÎßÐÞØ ÓÇÂÅÇÐÕÑÄ Ð ÊÂÏÇÜÇÐÐÞÇ ÕÇÕÓÂÊÑÎÞ ±ÓË ÄÊÂËÏÑÆÇÌÔÕÄËË (ÕÇÕÓÂÊÑÎ-5-ËÎ)ÆËÂÊÑÐËÌØÎÑÓËÆÂ Ô ÊÂÏÇÜÇÐÐÞÏË ÂÐËÎËÐÂÏË Ô ØÑÓÑÛËÏ ÄÞØÑÆÑÏ ÑÃÓÂÊÖáÕÔâ 3-ÂÓËÎ-1-(ÕÇÕÓÂÊÑÎ-5-ËÎ)ÕÓËÂÊÇÒËÐÞ.302 °ÃÓÂÃÑÕÍÑÌ 1-ÂÎÍËÎ- Ë 2-ÂÎÍËÎ-5-ØÎÑÓàÕËÎÕÇÕÓÂÊÑÎÑÄ ÔÒËÓÕÑÄÞÏ ÓÂÔÕÄÑÓÑÏ ÅËÆÓÑÍÔËÆ ÐÂÕÓËâ ÒÑÎÖÚÇÐÞ ÔÑÑÕÄÇÕÔÕÄÖáÜËÇ 5-ÄËÐËÎÕÇÕÓÂÊÑÎÞ.303 ²ÇÂÍÙËË (1-ÂÎÍËÎ(ÂÓËÎ)ÕÇÕÓÂÊÑÎ-5-ËÎ)ÕËÑÎÑÄ Ô ÐÖÍÎÇÑ×ËÎßÐÞÏË ÓÇÂÅÇÐÕÂÏË (ÕËÑÎÂÏË, ÔÒËÓÕÂÏË) ÒÓËÄÎÇÍÂáÕ Í ÔÇÃÇ ÒÓËÔÕÂÎßÐÑÇ ÄÐËÏÂÐËÇ. ¿ÕÑ ÔÄâÊÂÐÑ Ô ÕÇÏ, ÚÕÑ Ä ÓÇÊÖÎßÕÂÕÇ ÔÑÑÕÄÇÕÔÕÄÖáÜËØ ØËÏËÚÇÔÍËØ ÒÓÇÄÓÂÜÇÐËÌ ÏÑÅÖÕ ÃÞÕß ÔËÐÕÇÊËÓÑÄÂÐÞ ÄÇÜÇÔÕÄÂ, ÑÃÎÂÆÂáÜËÇ ÃËÑÎÑÅËÚÇÔÍÑÌ ÂÍÕËÄÐÑÔÕßá.304 ´ÂÍ, ÑÃÐÂÓÖÉÇÐÑ, ÚÕÑ ÃËÔ-(1-ÏÇÕËÎÕÇÕÓÂÊÑÎ-5ËÎ)ÆËÔÖÎß×ËÆ ÒÓÑâÄÎâÇÕ ËÔÍÎáÚËÕÇÎßÐÑ ÄÞÔÑÍÖá ÓÇÂÍÙËÑÐÐÖá ÔÒÑÔÑÃÐÑÔÕß ÒÑ ÑÕÐÑÛÇÐËá Í ÕËÑÎÂÏ.305 ë 307

N

C N

S

S

N

HSC N

C N

NCH3 N

N

+ RSH

N

N

R

NC6H5 N

N

N N

R

CH3

CH3

Cl

SC N

N

Ph

+

N N

Ph

£ ÕÑ ÉÇ ÄÓÇÏâ ÔÑÎË 2,5-ÆËÏÇÕËÎ-4-×ÇÐÂÙÇÕËÎÕÇÕÓÂÊÑÎËâ ÒÑÆ ÆÇÌÔÕÄËÇÏ ÂÏÏËÂÍ ÒÓÇÄÓÂÜÂáÕÔâ Ä ÆËÅËÆÓÑ-3¯-ËÏËÆÂÊÑ[1,2-d]ÕÇÕÓÂÊÑÎÞ.315 CH3 CH3

C N CH2COPh N + N X7 N

H3 C

NH3

CH3

N

N CPh C

N

N CH2 N

8. ¥ÇÌÔÕÄËÇ ÑÍËÔÎËÕÇÎÇÌ Ë ÄÑÔÔÕÂÐÑÄËÕÇÎÇÌ ´ÇÕÓÂÊÑÎßÐÞÌ ÙËÍÎ ÖÔÕÑÌÚËÄ Í ÆÇÌÔÕÄËá ÑÍËÔÎËÕÇÎÇÌ. °ÕÏÇÚÂÇÕÔâ, ÚÕÑ ØÂÓÂÍÕÇÓ ÒÓÇÄÓÂÜÇÐËÌ, ÍÑÕÑÓÞÇ ÒÓÇÕÇÓÒÇÄÂáÕ ÕÇÕÓÂÊÑÎÞ Ä ÓÇÂÍÙËâØ Ô ÑÍËÔÎËÕÇÎâÏË, ÊÂÄËÔËÕ ÑÕ ÒÓËÓÑÆÞ Ë ÒÑÎÑÉÇÐËâ ÊÂÏÇÔÕËÕÇÎâ Ä ÅÇÕÇÓÑÙËÍÎÇ. ´ÂÍ, ÒÓË ÄÊÂËÏÑÆÇÌÔÕÄËË 2-ÃÇÐÊËÎ-5-ÄËÐËÎÕÇÕÓÂÊÑÎÂ Ô ÆËÏÇÕËÎÆËÑÍÔËÓÂÐÑÏ ÑÃÓÂÊÖÇÕÔâ ÔÑÑÕÄÇÕÔÕÄÖáÜËÌ àÒÑÍÔËÆ,316 CHC

(CH3)2C

NR

O O

NCH2C6H5

N

H2 C

CHC O

N

NR N

NCH2C6H5

 ÒÓË ÑÍËÔÎÇÐËË 5-ÂÓËÎÂÏËÐÑÕÇÕÓÂÊÑÎÑÄ ÕÓÇÕ-ÃÖÕËÎÒÇÓÑÍÔËÆÑÏ ÃÞÎË ÒÑÎÖÚÇÐÞ ÖÔÕÑÌÚËÄÞÇ ÐËÕÓÑÍÔËÎßÐÞÇ ÓÂÆËÍÂÎÞ.317 O. C6H5NH C N

+

N

Nu

+ RSSR

N

N

Nu

Ph

N

¡ÄÕÑÓÞ ÓÂÃÑÕÞ 306 ÑÕÏÇÚÂáÕ, ÚÕÑ àÕ ÓÇÂÍÙËâ âÄÎâÇÕÔâ ÖÆÑÃÐÞÏ ÏÇÕÑÆÑÏ ÔËÐÕÇÊ ÍÂÍ ÔËÏÏÇÕÓËÚÐÞØ, ÕÂÍ Ë ÐÇÔËÏÏÇÕÓËÚÐÞØ ÆËÔÖÎß×ËÆÑÄ. ´ÂÍÉÇ ÎÇÅÍÑ ÒÑÆÄÇÓÅÂáÕÔâ ÓÂÔÜÇÒÎÇÐËá S-ÅÇÕÂÓËÎßÐÞÇ ÒÓÑËÊÄÑÆÐÞÇ (1-×ÇÐËÎÕÇÕÓÂÊÑÎ-5-ËÎ)ÕËÑÎÑÄ ÒÑÆ ÆÇÌÔÕÄËÇÏ ÅËÆÓÑÍÔËÆ ÍÂÎËâ Ä ÔËÔÕÇÏÇ ÄÑÆÂìÂÙÇÕÑÐËÕÓËÎ.245 3,3-¥ËÊÂÏÇÜÇÐÐÞÇ ÙËÍÎÑÒÓÑÒÇÐÞ ÄÊÂËÏÑÆÇÌÔÕÄÖáÕ Ô (1-×ÇÐËÎÕÇÕÓÂÊÑÎ-5-ËÎ)ÔÖÎß×ÇÐËÎØÎÑÓËÆÑÏ Ä ÓÂÔÕÄÑÓÇ ØÎÑÓËÔÕÑÅÑ ÏÇÕËÎÇРÒÓË 7208³.308 ClSC

N

+

CH2

NCH3

N

Nu7

N

N + X7

CH2CH2CCH3

CH3N

N

O

NR N

N

(CH3)3COOH

C6H5N C N

NR N

N

NC6H5 N

N

£ ÏâÅÍËØ ÖÔÎÑÄËâØ, ÒÑÆ ÆÇÌÔÕÄËÇÏ ÐÇÒÓÇÆÇÎßÐÞØ ÔÒËÓÕÑÄ, Ä ÒÓËÔÖÕÔÕÄËË ÕÓÇÕËÚÐÞØ ÂÏËÐÑÄ ÒÓÑËÔØÑÆËÕ ÅËÆÓÑÎËÊ S,S0 ÃËÔ-(1-×ÇÐËÎÕÇÕÓÂÊÑÎ-5-ËÎ)ÆËÕËÑÍÂÓÃÑÐÂÕÂ.309, 310 ²ÇÂÍÕËÄÞ ¤ÓËÐßâÓ ÏÑÅÖÕ ÃÞÕß ËÔÒÑÎßÊÑÄÂÐÞ ÆÎâ ÒÑÎÖÚÇÐËâ ÓâÆ ×ÖÐÍÙËÑÐÂÎßÐÞØ ÒÓÑËÊÄÑÆÐÞØ ÕÇÕÓÂÊÑÎÂ.311 ë 313 ¯ÂÍÑÐÇÙ, ÔÎÇÆÖÇÕ ÑÕÏÇÕËÕß, ÚÕÑ ÒÓË ÆÇÌÔÕÄËË ÐÖÍÎÇÑ×ËÎßÐÞØ ÓÇÂÅÇÐÕÑÄ Ð ÔÑÎË ÕÇÕÓÂÊÑÎËÎÒËÓËÆËÐËâ ÒÓÑËÔØÑÆËÕ ÓÂÊÓÞÄ ÔÄâÊË N7C Ä ÛÇÔÕËÚÎÇÐÐÑÏ ÅÇÕÇÓÑÙËÍÎÇ.314

£ ÕÑ ÉÇ ÄÓÇÏâ ÒÓË ÆÇÌÔÕÄËË ÐÂ 1-ÂÓËÎ-3-(ÕÇÕÓÂÊÑÎ-5ËÎ)ÕÓËÂÊÇÐÞ ÕÇÕÓÂÂÙÇÕÂÕÂ ÔÄËÐÙÂ ÒÓÑËÔØÑÆËÕ ÆÇÅÓÂÆÂÙËâ ÅÇÕÇÓÑÙËÍÎÂ.318 ArNH N N C N

NH N

N

(CH3COO)4Pb

ArN N C N

£ ÓÇÂÍÙËâØ Ô ÄÑÔÔÕÂÐÑÄËÕÇÎâÏË ÕÇÕÓÂÊÑÎßÐÞÌ ÙËÍÎ ÑÃÞÚÐÑ ÐÇ ÊÂÕÓÂÅËÄÂÇÕÔâ. £ ÓÂÃÑÕÇ 288 ÒÑÍÂÊÂÐÑ, ÚÕÑ ÒÓË ÄÑÔÔÕÂÐÑÄÎÇÐËË ÕÇÕÓÂÊÑÎÑ[1,5-b]-1,2,4-ÕÓËÂÊËÐÑÄ ÄÑÆÑÓÑÆÑÏ (Pd/C) ÒÓÑËÔØÑÆËÕ ÎËÛß ÚÂÔÕËÚÐÂâ ÅËÆÓÑÅÇÐËÊÂÙËâ ÛÇÔÕËÚÎÇÐÐÑÅÑ ÙËÍÎÂ, ÕÑÅÆ ÍÂÍ ÒÓË ÄÑÔÔÕÂÐÑÄÎÇÐËË ÃÑÓÑÅËÆÓË-

858

¤.ª.¬ÑÎÆÑÃÔÍËÌ, £.¡.°ÔÕÓÑÄÔÍËÌ

ÆÑÏ ÐÂÕÓËâ Ä ÏÇÕÂÐÑÎÇ Ô ÄÞÔÑÍËÏ ÄÞØÑÆÑÏ ÑÃÓÂÊÖáÕÔâ ÔÑÑÕÄÇÕÔÕÄÖáÜËÇ 5,6,7,8-ÕÇÕÓÂÅËÆÓÑÕÇÕÓÂÊÑÎÑ[1,5-b]-1,2,4ÕÓËÂÊËÐÞ.

H2 (Pd/C)

R1

N

R2

N

N N

R1 H N

H

N N N

R2 N

N

R1 H N

H

NaBH4

N

H R2

N

N N N H

N

N

9. ²ÇÂÍÙËË ÙËÍÎÑÒÓËÔÑÇÆËÐÇÐËâ £ ÔÄâÊË Ô ÂÍÕËÄÐÞÏË ÒÑËÔÍÂÏË ÏÇÕÑÆÑÄ ÔËÐÕÇÊ ÐÑÄÞØ ÅÇÕÇÓÑÙËÍÎËÚÇÔÍËØ ÔËÔÕÇÏ ÊÂÏÇÕÐÑ ÄÑÊÓÑÔ ËÐÕÇÓÇÔ Í ÓÇÂÍÙËâÏ ÙËÍÎÑÒÓËÔÑÇÆËÐÇÐËâ Ô ÖÚÂÔÕËÇÏ ÕÇÕÓÂÊÑÎÑÄ ÍÂÍ ÆËÒÑÎâÓÑ×ËÎÑÄ.321 ±ÑÍÂÊÂÐÑ, ÚÕÑ ÒÓË ÄÊÂËÏÑÆÇÌÔÕÄËË 6-ØÎÑÓÕÇÕÓÂÊÑÎÑ[1,5-b]ÒËÓËÆÂÊËÐÂ Ô ÆËÂÊÑÂÎÍÂÐÂÏË ÑÃÓÂÊÖáÕÔâ ÔÑÑÕÄÇÕÔÕÄÖáÜËÇ ÙËÍÎÑÂÆÆÖÍÕÞ. £ÊÂËÏÑÆÇÌÔÕÄËÇ ÒÑÔÎÇÆÐËØ Ô ÂÙÇÕÑÐÑÏ ÒÓËÄÑÆËÕ Í ÖÔÕÑÌÚËÄÞÏ ÂÊÑÏÇÕËÐËÏËÐÂÏ, ÍÑÕÑÓÞÇ ÒÓË ÐÂÅÓÇÄÂÐËË Ä ÍÔËÎÑÎÇ ÒÓÇÄÓÂÜÂáÕÔâ Ä ÕÇÕÓÂÊÑÎÔÑÆÇÓÉÂÜËÇ 1,2-ÆËÂÊÇÒËÐÞ.322 H3C CH3 N

N N

N

(CH3)2CN2

N

N

HN

N

HN

N

Cl

N

(CH3)2CO

Cl H3C CH3 N H3C H3 C

+

N

C N

N

N

N

7

N

N

H3C H3C

N N

N N H

C

H3C N

N

NCH3 + CH3N3

N

N

H2C

N CH3 C

H3C N

N HC

N CH3 N

N

N C

NCH3 + CH3N3

NHCH3

°ÃÓÂÊÑÄÂÐËÇ ÖÔÕÑÌÚËÄÑÅÑ ÒÓÑÆÖÍÕ ÙËÍÎÑÒÓËÔÑÇÆËÐÇÐËâ ÖÆÂÇÕÔâ ÊÂ×ËÍÔËÓÑÄÂÕß ÒÓË ÒÓÑÄÇÆÇÐËË ÓÇÂÍÙËË ×ÇÐËÎÂÊËÆÂ Ô 4,5-ÆËÅËÆÓÑ-1-ÏÇÕËÎ-4-×ÇÐËÎ-5-(1-ÏÇÕËÎàÕËÎËÆÇÐ)ÕÇÕÓÂÊÑÎÑÏ Ä ÙËÍÎÑÅÇÍÔÂÐÇ.

10. ±ÑÎËÏÇÓËÊÂÙËâ ÄËÐËÎÕÇÕÓÂÊÑÎÑÄ £ËÐËÎÕÇÕÓÂÊÑÎÞ ÆÑÔÕÂÕÑÚÐÑ ÎÇÅÍÑ ÒÑÎËÏÇÓËÊÖáÕÔâ Ä ÓÂÔÕÄÑÓÇ ËÎË Ä ÏÂÔÔÇ Ä ÒÓËÔÖÕÔÕÄËË ÍÂÕÂÎËÊÂÕÑÓÑÄ ÓÂÆËÍÂÎßÐÑÅÑ ÕËÒÂ, ÐÂÒÓËÏÇÓ ÂÊÑÃËÔËÊÑÃÖÕËÓÑÐËÕÓËÎÂ. £ÂÉÐÞÇ ÆÂÐÐÞÇ ÆÎâ ÒÑÐËÏÂÐËâ ÏÇØÂÐËÊÏ ÒÑÎËÏÇÓËÊÂÙËË ÄËÐËÎÕÇÕÓÂÊÑÎÑÄ Ë ÒÓÑÅÐÑÊËÓÑÄÂÐËâ ÔÄÑÌÔÕÄ ÑÃÓÂÊÖáÜËØÔâ ÒÑÎËÏÇÓÑÄ ÒÑÎÖÚÇÐÞ ÒÓË ËÔÔÎÇÆÑÄÂÐËË ÒÑÎËÏÇÓËÊÂÙËË 1-ÄËÐËÎ-, 1-ÄËÐËÎ-5-ÏÇÕËÎ- Ë 2-ÏÇÕËÎ-5-ÄËÐËÎÕÇÕÓÂÊÑÎÑÄ Ä ÄÑÆÐÞØ ÓÂÔÕÄÑÓÂØ ÓÑÆÂÐËÆ ÐÂÕÓËâ.323 ±ÑÍÂÊÂÐÑ, ÚÕÑ ÒÑÎËÏÇÓËÊÂÙËâ àÕËØ ÔÑÇÆËÐÇÐËÌ ÄÑ ÏÐÑÅÑÏ ÒÑÆÑÃРÒÑÎËÏÇÓËÊÂÙËË ÂÍÓËÎÑÐËÕÓËÎÂ Ä ÂÐÂÎÑÅËÚÐÞØ ÖÔÎÑÄËâØ Ë ËÏÇÇÕ, ÒÑ-ÄËÆËÏÑÏÖ, ÍÑÏÒÎÇÍÔÐÑ-ÓÂÆËÍÂÎßÐÞÌ ØÂÓÂÍÕÇÓ. ªÔÒÑÎßÊÑÄÂÐËÇ ÓÂÔÕÄÑÓÑÄ ÓÑÆÂÐËÆ ÐÂÕÓËâ Ä ÍÂÚÇÔÕÄÇ ÓÇÂÍÙËÑÐÐÑÌ ÔÓÇÆÞ ÒÑÊÄÑÎâÇÕ ÒÑÎÖÚÂÕß ÕÇÕÓÂÊÑÎÔÑÆÇÓÉÂÜËÇ ÒÑÎËÏÇÓÞ Ô ÃÑÎßÛÑÌ ÏÑÎÇÍÖÎâÓÐÑÌ ÏÂÔÔÑÌ, ÒÓËÚÇÏ ÒÓÑÙÇÔÔ ÒÑÎËÏÇÓËÊÂÙËË ÒÓÑÕÇÍÂÇÕ ÅÑÓÂÊÆÑ ÃÞÔÕÓÇÇ, ÚÇÏ Ä ÑÓÅÂÐËÚÇÔÍËØ ÓÂÔÕÄÑÓËÕÇÎâØ. ¯ÂÓâÆÖ Ô ÅÑÏÑÒÑÎËÏÇÓËÊÂÙËÇÌ ËÔÔÎÇÆÑÄÂРÔÑÒÑÎËÏÇÓËÊÂÙËâ 1-ÄËÐËÎ- Ë 2-ÏÇÕËÎ-5-ÄËÐËÎÕÇÕÓÂÊÑÎÑÄ Ô ÂÍÓËÎÑÄÑÌ Ë ÏÇÕÂÍÓËÎÑÄÑÌ ÍËÔÎÑÕÂÏË, ËØ ÒÓÑËÊÄÑÆÐÞÏË,  ÕÂÍÉÇ ÔÑ ÔÕËÓÑÎÑÏ.324 ë 326 µÔÕÂÐÑÄÎÇÐÑ, ÚÕÑ ÒÓË ÔÑÒÑÎËÏÇÓËÊÂÙËË 2-ÏÇÕËÎ-5-ÄËÐËÎÕÇÕÓÂÊÑÎÂ Ô ÂÍÓËÎÑÐËÕÓËÎÑÏ Ä ÏÂÍÓÑÙÇÒË ÔÑÒÑÎËÏÇÓ ÏÑÅÖÕ ÑÃÓÂÊÑÄÞÄÂÕßÔâ ÃÎÑÍË ÊÄÇÐßÇÄ ÅÑÏÑÒÑÎËÏÇÓ ÊÐÂÚËÕÇÎßÐÑÌ ÆÎËÐÞ, ÚÕÑ ÔÄËÆÇÕÇÎßÔÕÄÖÇÕ Ñ ÔÍÎÑÐÐÑÔÕË ÄËÐËÎÕÇÕÓÂÊÑÎÂ Í ÅÑÏÑÒÑÎËÏÇÓËÊÂÙËË. £ ÕÑ ÉÇ ÄÓÇÏâ ÒÓË ÔÑÒÑÎËÏÇÓËÊÂÙËË 2-ÏÇÕËÎ-5-ÏÇÕËÎÇÐÕÇÕÓÂÊÑÎÂ Ô ÏÇÕÂÍÓËÎÑÄÑÌ ÍËÔÎÑÕÑÌ Ë ÇÇ à×ËÓÂÏË ÄÇÓÑâÕÐÑÔÕß ÑÃÓÂÊÑÄÂÐËâ ÃÎÑÍÔÑÒÑÎËÏÇÓ ÄÞÛÇ.

11. ¶ÑÕÑØËÏËÚÇÔÍËÇ ÒÓÇÄÓÂÜÇÐËâ D

Cl CH3

N H2C

·ÑÓÑÛËÇ ÓÇÊÖÎßÕÂÕÞ ÃÞÎË ÒÑÎÖÚÇÐÞ ÒÓË ÍÂÕÂÎËÕËÚÇÔÍÑÏ (Pd) ÄÑÔÔÕÂÐÑÄÎÇÐËË 5-(2-ÐÂ×ÕÑÍÔË)-1-×ÇÐËÎÕÇÕÓÂÊÑΠÅËÒÑ×ÑÔ×ËÕÑÏ ÕÇÕÓÂÃÖÕËÎÂÏÏÑÐËâ Ä ÆÄÖØ×ÂÊÐÑÌ ÔËÔÕÇÏÇ ÃÇÐÊÑÎìÄÑÆÂ.319 £ ÒÑÔÎÇÆÐËÇ ÅÑÆÞ ÑÒÖÃÎËÍÑÄÂÐÑ ÐÇÊÐÂÚËÕÇÎßÐÑÇ ÍÑÎËÚÇÔÕÄÑ ÓÂÃÑÕ, ÒÑÔÄâÜÇÐÐÞØ àÎÇÍÕÓÑØËÏËÚÇÔÍÑÏÖ ÄÑÔÔÕÂÐÑÄÎÇÐËá ÕÇÕÓÂÊÑÎÑÄ. ¯ÂÌÆÇÐÑ, ÚÕÑ àÎÇÍÕÓÑØËÏËÚÇÔÍÑÇ ÄÑÔÔÕÂÐÑÄÎÇÐËÇ 1-ÄËÐËÎ- Ë 5-ÄËÐËÎÕÇÕÓÂÊÑÎÑÄ Ä ÂÙÇÕÑÐËÕÓËÎÇ ÒÓÑËÔØÑÆËÕ Ô ÒÇÓÇÐÑÔÑÏ ÑÆÐÑÅÑ àÎÇÍÕÓÑÐÂ.320 ¿ÎÇÍÕÓÑØËÏËÚÇÔÍÑÇ ÄÑÔÔÕÂÐÑÄÎÇÐËÇ 5-ÕÓËØÎÑÓÏÇÕËÎÕÇÕÓÂÊÑΠÒÓËÄÑÆËÕ Í ÑÃÓÂÊÑÄÂÐËá ÕÇÕÓÂÊÑÎÂ, 5-ØÎÑÓÏÇÕËÎ- Ë 5-ÆËØÎÑÓÏÇÕËÎÕÇÕÓÂÊÑÎÑÄ Ô ÄÞØÑÆÑÏ 16; 5 Ë 28% ÔÑÑÕÄÇÕÔÕÄÇÐÐÑ.53

N

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N

N

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Cl

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F

N N

N

N F

N H

Cl

hn 7N2

µÔÒÇØË ØËÏËË 63 (10) 1994

859

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N N

H N

hn

N R

O

N R

N

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F3C N

N

N

N

N

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N3

CF3

F3C N

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N

N

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R2 R2

H3C N N

C

N CH3

hn 7N2

N

R1

NCH3 N CH3

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N

N + N N

e7 7e7

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. N

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C

N

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TETRAZOLES G.I.Koldobskii, V.A.Ostrovskii St.Petersburg State Institute of Technology, 26, Moskovskii Prosp., 198013 St.Petersburg, Russian Federation, Fax +7(812)110-6285 In the review new data on preparation, physicochemical properties and practical application of tetrazoles have been systematised. Results of recent researches of elecronic structure, base-acid properties, tautomerism, reactivity as well as thermal stability of tetrazoles have been discussed. Bibliography ì 369 references. Received 27th May 1993