1,4-Diaza-1,3-butadiene Diels-Alder

전체 글

(1)Journal of the Korean Chemical Society 2001, Vol. 45, No. 3 Printed in the Republic of Korea. Diels-Alder .

(2) DFT . 1,4-Diaza-1,3-butadiene. . (2001. 3. 27

(3) ) DFT Studies for the Substituent Effect on the Diels-Alder Reaction of 1,4-Diaza-1,3-butadienes Gab-Yong Lee Department of Chemistry, Catholic University of Taegu, Kyongsan 712-702, Korea Received March 27, 2001). . 1,4-Diaza-1,3-butadiene(1,4-DAB) acrolein Diels-Alder 1,4-DAB !"# $% & '()* +, '(1,4-DAB& DFT -. /01. 23 4 & -.4 FMO(Frontier Molecular Orbital) 5678 93: ;<= >?1. @, $% '(A BC% normal electron demand D EFG, H% '(A BC% inverse electron demand IJKLM7 N/O P >?1. ABSTRACT. DFT calculations have been performed on several substituted 1,4-diaza-1,3-butadienes (1,4DABs) with electron donating and withdrawing groups at the terminal two nitrogens to investigate the reactivity of Diels-Alder reaction with acrolein. The calculated FMO (Frontier Molecular Orbital) energies for the optimized 1,4-disubstituted-1,4-DABs have been used to explain both normal and inverse electron demand Diels-Alder reactions. It is shown that the electron donating and withdrawing substituents lead to the normal(HOMO diene controlled) and inverse electron demand (LUMO diene controlled) Diels-Alder reactions, respectively.. QF R: Diels-Alder S 6T QF UV U%W X YF Z[Q >% \ ]D1. D D Diels^ Alder P_N D` abc6 de3M7# Df3M7 gS / hMG, Df3 7% Be3 \], ab initio \] i DFT(Density Functional Theory) jD Z[Q >1. Froese j S klmn op Diels-Alder ab initio -. q r. 56 st0MG, uv, B3LYP/6-31G* level8 klmn uwop D Diels-Alder [4+2]. 1-3. 4-6. 7-10. 11-12. 13. x r 56 -.x y 25.0 kcal/mol D O zQ01. x{ |}7QF UV U x Diels-Alder st M7 FMO(Frontier Molecular Orbital) Df x HOMO i LUMO D ~9 ZD gD Z[Q >MG, Bachrach j S prop-2-enethial +, mn D r X '% '( FMO DfM7 st01. uv, Diels-Alder W klmn 1 4 T '(4 1,4-diaza-1,3-butadiene (1, 4-DAB) Diels-Alder S '( pyrazine& 14. 5. 207. 16.

(4) . 208. UV( A) Z+ DFT -. q DielsAlder '% '( 93: µ ¶ 01. Z4 '(% $% 7 OH, NH , CH , OCH , ·FQ H% 7 F, Cl, CN, Z01. ¢ 8 DFT-.S B3LYP NO level8 6-31G(d) basis set Z+ Gaussian 94 ¸7·¹ M7 /0MG, RS6K workstationM7 -.01. ¢ 8 ºx »¼ UV 2 3 4 0MG, 23 4 Hessian QE½ N«$¾ -.+ » ¿ ½ 6% y 7kÀ -.4 true minimaÁ ±:01. 2. 3. Scheme 1.. U $ |}7 QF. UV U M7 C [ M G, N-aryl-1,4-DAB&S D mn^ Diels-Alder V & $% M7 P_ >1. Orsini j S 1,4-DAB^, D. UV +, '( '(4 UV x FMO 56 Be3: MNDO\]M7 -.+ HOMO 56 93: D7 0M# '( D -3M7 ;<6 ¡01. ¢ 8% z 1,4-DAB^ acrolein D Diels-Alder x TS y£ i r. 56 -. D, 1,4-DAB i Scheme 1 # l¤ ¥^ ¦D 1,4-DAB $% ^ H% '()* +, '( 1,4DAB acrolein Diels-Alder 93: DFT -. q §Q x1. 17. 18. 19. 2¨ DFT(Density Functional Theory) © i st% M7 gD Z[Q >1. DFT% ªS basis set Zx HF \] i «¬x basis set Z% Post-HF \] ® ¯ 9°x £± -. ®ZD 3 ² % X³ 6Q >% \]M7 P_ >1. ¢ 8% mn7 acrolein ZQ D^ Diels-Alder ¬M´% mnM7 1,4-DAB i 1,4-DAB +, '( yU4. 20. 3. 2. 21.

(5) Frontier ~9Z% mn mn HOMO-LUMO «) 9Z% neutral Diels-Alder , mn HOMO^ mn LUMO Cw 9Z+ 6Â % normal electron demand , ·FQ mn LUMO^ mn HOMO D 9ZD Cw x inverse electron demand M7 §Ã >1. ¢ 8% acrolein mn7 Q 1,4DAB mnM7 + ÄÅ 23 )´Q 23 4 FMO 56 01. uv, 1,4-DAB 93: klmn Æ UV7 º+ ÇÈ -.0MG, '( 93: 1,4-DAB +, '( '()* UV& É) 23. )´Q 23 4 FMO 56 .01. AcroleinS 35 C Ê9Ë8 s-trans D s-cis D ® Ì 3Â gD Íb% M7 §Ã > ¢ 8% s-trans D º + -.01. ·FQ klmn, 1,4-DAB i '( 1,4-DAB&S acrolein ¬MÎ >% )Ï conformation + -.01. mn7 Z4 acrolein , klmn B3LYP/6-31G(d) level8 23 4 ¾Ð À i FMO 56 Table 1 #lÑ?1. Diels-Alder. 22. o. 23. Journal of the Korean Chemical Society.

(6) Diels-Alder

(7) DFT . 209. 1,4-Diaza-1,3-butadiene. . and bond Table 1. Optimized parameters (bond lengths in angles in degree) and FMO energies (in a.u.) for acrolein and cis-butadiene. acrolein Energy. HOMO LUMO -0.25713 -0.06505. Parameter r(C1-C2) r(C2-C3) r(C1-O) C1C2C3 OC1C2 OC1C2C3 C1C2C3C4. cis-butadiene HOMO -0.23112. 1.475 1.338 1.215 121.2 124.3 180.0. Ü Ü Ü Ü. LUMO -0.02284. Fig. 1. Frontier orbital interaction in the Diels-Alder reaction between cis-butadiene and acrolein.. 1.339 1.470 125.8. 30.1. 8 mn: acroleinS ÒÓ C 7 #lÔ1. C=C yUÕD% 1.338 ÖM7 ×3: DyU ÕD(1.34 Ö)^ ®Ø #lÔMG C-C yUÕD% 1.475 Ö7 - D ×3: ¬yU ÕD(1.54 Ö) z1 ÌÙ Ú #lÔ1. ·F Q C=O yUÕD% 1.215 ÖM7 #lÔMG, D& yUÕD% » de ½ (ÛÛ 1.335, 1.478, 1.208Ö) " ¬'01. uv, yUÛ ÜC C C % 121.2 , ÜOC C % 124.3 7 #l# É) de ½ (ÛÛ 121.0 , 124.0 ) " ¬'Ç P >1. x{ acrolein Diels-Alder ¬MÎ >% )Ï-klmnS C Ý7, ·FQ Þ D ®ßàÛS 30.1 7 23 [?1. Table 1 #l¤ FMO 56 Z+ )Ï-k lmn acrolein D Diels-Alder 8 Z % Frontier ~9Z Fig. 1 #lÑ?1. Fig. 18 mn LUMO^ mn HOMO D 56 ÙáS 0.23429 a.u.78 mn HOMO ^ mn LUMO D 56 Ùá 0.16607 a.u.z1 Ì 43 kcal/mol â ãM7 D S mn HOMO^ mn LUMO 6Â% normal electron demand M7 N/A M7 s 941. Table 1. s. 24. o. 1. o. 1. 2. o. 2. o. 2001, Vol. 45, No. 3. 2. 24. 3. o. x{ mnD )Ï-klmn8 1,4-DAB7 ¥ä 93: PuzQ, uv, '( '% 93: µ¶ Puz 1,4-DAB T +, åæ '( yU4 UV& 23 )çMG 23 4 ¾Ð À 23 4 -.4 FMO 56^ ÇÈ Table 2 Ì01. Table 2 #l¤, 1,4-DAB èÇ+ ¢ 8 ºx »¼ UVS )Ï-klmn -.y ^ «¬x C Ý7 23 [?1. Table 28 P >éD '( DAB BC N C yUÕD% '( Ð 1.272~1.287 Ö D ½M7 #lÔMG, » 1,4-DAB^ ®= ±0.02 Ö DÑ7 ê6 ëì P >1. C ^ C D yUÕD% 1.460 Ö8 1.484 ÖM7 #lÔ MG » 1,4-DAB z1 » ÌÙí Ú #lÔ1. yUÛ ÜN C C % 120.2 8 123.7 D7 #lÔ MG » 1,4-DAB ® ê zD6 ëQ >1. x{ ÒÓM7kÀ îßàÛS ï8 8ðx ¥^ ¦D )Ï-klmn BC 30.1 7 #lÔM# 1,4-DAB BC 0.0 7 " ÒÓ E6Q >1. D% 1,4-DAB BC, )Ï-klmn8 ¯ >% yU4 Þ ñ T& x òXó ô6 ë M7 Û41. ·,# ì F^ Cl i bulkyx NO '(A BC D^ ¦S õ[ D& UVD ÒÓ M7kÀ ÛÛ 27.4 , −20.8 , −23.5 7 îßF% M 7 Û41. Table 2 #l¤ FMO 56 Z+ 1,42. 1. 2. 2. o. 1. 2. o. 3. o. o. 2. o. o. o. 3.

(8) . 210. Table 2. Optimized parameters (bond lengths in Å, bond angles in degree) and FMO energies (in a.u.) for 1,4-DAB and 1,4-disubstituted-1,4-DABs Substituent R OH NH2 CH3 OCH3 H F Cl CN NO2. Parameter r(N1-C2). r(C2-C3). 1.284 1.286 1.272 1.286 1.274 1.280 1.280 1.287 1.277. 1.462 1.460 1.484 1.460 1.492 1.468 1.479 1.469 1.477. (N C C ) (N C C N ) 1. 2. 122.6 123.7 123.5 122.7 122.4 120.5 120.2 121.1 120.5. 3. 1. 2. 3. 4. 0.0 −4.0− 0.0 0.0 0.0 27.40 −20.8−0 0.0 −23.5−0. Energy HOMO. LUMO. −0.23601 −0.19602 −0.25179 −0.22419 −0.26985 −0.30577 −0.28987 −0.31094 −0.32167. −0.05616 −0.03112 −0.05356 −0.05502 −0.06495 −0.09571 −0.10353 −0.16333 −0.15225. x{ Diels-Alder '% '( µ¶ Puz 1,4-DAB +, åæ '( '(4 UV FMO 56 .x y Table 28 z% ¥^ ¦D, $% '( '(A BC HOMO i LUMO 56% » » 1,4-DABz1 ÛÛ Ì 11~46 kcal/mol i 6~21 kcal/mol ÊQ, H% '(A B C% 7 » ÛÛ 13~33 kcal/mol i 19~62 kcal/mol öu÷ P >1. D,x y % Orsini j MNDO y 8 z+Æ B¶ ø ¬'x1. D^ ¦S B¶ ù â w Puz H% ^ $% 7 ©+ Fig. 3 '( 1,4-DAB^ acrolein D ~9Z # lÑ?1. 1,4-DAB $% '( O Ð úD Ê[Q, ûx Fig. 38 P >éD » 1,4-DAB ® HOMO i LUMO 56 » ÊOM7ü mn7 Z4 acrolein FMO 56^ ®¯ mn HOMO^ mn LUMO D 56 ÙáD mn LUMO^ mn HOMO D 56 Ùáz1 ýþ 36 41. Ð8 mn HOMO^ mn LUMO Ù 9ZD 93M7 Cw Z+ 6Â% normal electron demand IJKLM7 N/A M7 s941. 7 H% '(A BC% D Ê[Q, ûx HOMO i LUMO 56 » öÿM7ü mn LUMO^ mn HOMO D 56 ÙáD 93M7 u6 [ D& ~Ù 9 18. Fig. 2. Frontier orbital interaction in the Diels-Alder reaction between 1,4-DAB and acrolein.. ^ acrolein D Diels-Alder 8 Z % ~9Z Fig. 2 #lÑ?1. Table 1, 2 i Fig. 2 #l¤ ¥^ ¦D mnM 7 1,4-DAB Z= BC mn LUMO^ mn : acrolein HOMO D 56 Ùá i mn HOMO^ mn LUMO D 56 ÙáS ÛÛ 0.19218 a.u. i 0.20480 a.u. 78 Ì 7.9 kcal/mol £7 #l# Table 1 i Fig. 1 #l¤ )Ï-k lmn acrolein D (43 kcal/mol) ® C S D #l¤1. Ð8 1,4-DAB^ acrolein D Diels-Alder S )Ï-klmn op D Diels-Alder 8 ¯ >% ~ 9Z «¬ mn LUMO^ mn HOMO, ·FQ mn HOMO^ mn LUMO ÇÈ 9Z% neutral Diels-Alder IJ KLM7 N/A M7 s941. DAB. 22. Journal of the Korean Chemical Society.

(9) Diels-Alder

(10) DFT . 1,4-Diaza-1,3-butadiene. 211. Ð8 ¢ y DZ+ 1,4-DAB H% D '( '() Ê)´Q, y(electron deficient character) Ê)Î >% Lewis acid 7 Z+ kx(electron-rich) mn^ )´Ó IEDDA IJKL " +, pyrazine i quinoxaline E& U= > M 7 s941. Fig. 3. Frontier orbital interaction in the Diels-Alder reaction between acrolein and 1,4-disubstituted-1,4-DABs with electron donating (a) and withdrawing groups (b).. ZD Cw Z% inverse electron demand Diels-Alder(IEDDA) IJKLM7 N/A M7 s941. D^ ¦S y % azadiene T H% D x N-acyl i N-sulfonyl7 '( A x IEDDA ô%1% zQ ^ ø ¬'x1. uv, Boruah j D β-Formylenamide7 kÀ D N-acyl-1-aza-1,3-diene UQ, IEDDA DZ+ D UV +, enamine& ) +, åæ F E& Ux y ^ ¬'x1. 25, 26. 27. $% ^ H% '() acrolein Diels-Alder ¬MÎ '( 01. D ¢ 8 ºx »¼ UV DFT -. q 23 )´Q 23 4 FMO 56 -.01. -.4 FMO 567kÀ 1,4-DAB^ acrolein D Diels-Alder S mn i mn HOMO^ LUMO ÇÈ 9Z% neutral Diels-Alder D CwÇ PMG 1-4-DAB $% '(A BC% normal electron demand IJKLM7, 7 H% '(A B C% inverse electron demand Diels-Alder(IEDDA) IJKLM7 N/O P >?1. 1,4-DAB. 2001, Vol. 45, No. 3. ¢ % 2000

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1,4-Diaza-1,3-butadiene Diels-Alder   

1,4-Diaza-1,3-butadiene Diels-Alder