테트라플루오로보론산 3-클로로벤젠다이아조늄으로부터 아라인 첨가생성물 생성 반응 조건 연구(I)

양일우; 정영진; Il-Woo Yang; Yeong-jin Chung

Journal of the Korean Industrial and Engineering Chemistry, Vol.14, No.5, 641-644, August, 2003

Export Citation

테트라플루오로보론산 3-클로로벤젠다이아조늄으로부터 아라인 첨가생성물 생성 반응 조건 연구(I)

Optimization of an Aryne Adduct Generated from 3-Chlorobenzenediazonium Tetrafluoroborate (I)

양일우^†, 정영진 ¹

육군사관학교 화학과, 서울 139-799
¹삼척대학교 소방방재학부, Gangwon 245-711

Il-Woo Yang^†, and Yeong-jin Chung¹

Department of Chemistry, Korea Miitary Arcademy, Seoul 139-799, Korea
¹Department of Fire & Disaster Prevention Engineering, Samcheok National University, Gangwon 245-711, Korea

E-mail:

초록

테트라플루오로보론산 3-클로로벤젠다이아조늄과 초산 칼륨염의 반응을 벤젠 용매에서 18-크라운-6와 테트라페닐사이클로펜타다이인온(TPCP)존재하에 실시하여 아라인 첨가 생성물인 5-클로로-1,2,3,4-테트라페닐나프탈린을 얻었으며 반응의 수득율은 반응 조건에 따라 달라짐을 확인하였다. 본 연구에서 18-크라운-6는 이온성 고체 반응물들인 테트라플루오로보론산 3-클로로벤젠다이아조늄과 유기산의 칼륨염을 비극성 유기 용매층으로 이동시키는 상이동 촉매로 사용된 것이며, TPCP는 효과적인 아라인 포획물질로서 [4+2] 사이클로 첨가반응 메카니즘을 따라 아라인의 첨가생성물을 형성케하였다. 본 실험을 통하여 조사된 반응 조건들은 반응 온도 그리고 반응물간의 몰비 관계를 조사하였다. 3-클로로벤젠다이아조늄염과 초산 칼륨의 상이동 촉매반응을 환류조건에서 실시하면 동일한 반응을 실온에서 수행했을 때 보다 아라인 첨가 생성물의 수득율이 28% 증가된 73%로 얻었다. 다이아조늄염:초산칼륨염:TPCP:18-크라운-6 간의 최적 몰수비가 1:1:0.5:0.03 이었을 때 가장 높은 첨가 생성물의 수득율을 나타내었다.

Reactions of 3-chlorobenzenediazonium tetrafluoroborate with potassium acetate in the presence of 18-crown-6 and tetraphenylcyclo-pentadienone (TPCP) were investigated and found the formation of aryne adduct, 5-chloro-1,2,3,4-tetraphenylnaphtha-lene in poor to reasonable yield according to reaction conditions employed. In these reactions, 18-crown-6 was used as a phase transfer catalyst (PTC) for transfering solid ionic reactants into nonpolar solvent layer, and TPCP was used as an effective aryne scavenger to form an adduct by thermal [4+2] cycloaddition. The reaction was studied on the various temperature and molar ratio of reactants. When the reaction run in higher temperature, the yield increased up to 28%. It was found that the optimum molar ratio of reactants, diazonium salts:potassium acetate:TPCP:18-crown-6 should be 1:1:0.5:0.03 for the maximum yield 73% of aryne adduct.

Keywords:Aryne Adduct;tetraphenylcyclopentadienone (TPCP);phase transfer catalyst (PTC);potassium acetate;diazonium salts

[References]

Battiste MA, Duan JX, Zhai YA, Ghiviriga I, Abboud KA, Roitberg A, Shelton GR, Doliber WR, Tetrahedron Lett., 43, 7047 (2002)
Raymo F, Kohnke FH, Cardullo F, Girreser U, Stoddart JF, Tetrahedron, 48, 6827 (1992)
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[Referenced By]

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[1] Battiste MA, Duan JX, Zhai YA, Ghiviriga I, Abboud KA, Roitberg A, Shelton GR, Doliber WR, Tetrahedron Lett., 43, 7047 (2002)

[2] Raymo F, Kohnke FH, Cardullo F, Girreser U, Stoddart JF, Tetrahedron, 48, 6827 (1992)

[3] Gribble GW, Keavy DJ, Branzt SE, Kelly WJ, Pals MA, Tetrahedron Lett., 29, 6227 (1988)

[4] Ruchard C, Tan CC, Chem. Int. Eng., 9, 522 (1970)

[5] Cadogan JIG, Chem. Soc. Spec. Publ., 24, 71 (1970)

[6] Brennan J, Cadogan JIG, Sharp JT, J. Chem. Res., 1156 (1977)

[7] Baigrie B, Cadogan JIG, Mitchell JR, Robertson AK, Sharp JT, J. Chem. Soc.-Perkin Trans. 1, 2563 (1972)

[8] Brydon DL, Cadogan JIG, Cook J, Harge MJP, Sharp JT, Chem. Soc., 1996 (1971)

[9] Cadogan JI, Murray CD, Sharp JT, J. Chem. Soc.-Perkin Trans. 2, 546 (1975)

[10] Bartsch RA, Yang IW, Tetrahedron Lett.(20), 2503 (1979)

[11] Bartsch RA, Yang IW, J. Hetero. Chem., 21, 1063 (1984)

[12] Roe A, Graham JR, J. Am. Chem. Soc., 74, 6297 (1952)

[13] Broxton TJ, Bunnett JF, Nouveau J. Chem., 3, 133 (1979)

[14] Korzeniowski SH, Gokel GW, Tetrahedron Lett.(19), 1633 (1977)