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

양일우; 정영진; Il Woo Yang; Yeong Jin Chung

Journal of the Korean Industrial and Engineering Chemistry, Vol.14, No.7, 1003-1006, November, 2003

Export Citation

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

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

양일우^†, 정영진 ¹

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

Il Woo Yang^†, and Yeong Jin Chung¹

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

E-mail:

초록

테트라플루오로보론산 3-클로로벤젠다이아조늄과 유기산 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 실험을 통하여 조사된 반응 조건들은 유기산 염의 종류 그리고 용매의 영향 등을 조사하였다. 3-클로로벤젠다이아조늄 이온의 아라인 경로를 통한 분해와 아라인 첨가 생성물 형성반응에서 조사된 7종의 유기산염 종류를 수득율이 높은 순서로 열거하면 PhCO₂K > CH₃(CH₂)₆CO₂K > CH₃CH₂CO₂K > CH₃CO₂K > ClCH₂CO₂K > K₂CO₃ > KOH 순서로 나타났다. 이 순서는 수용액에서 측정된 각 산의 pka와는 무관하며 유기산의 짝지움이 18-크라운-6와 착물을 형성 K⁺와의 이온쌍 형태로 비극성 용매인 벤젠이 이동되는 효율과 관계가 있을 것으로 판단된다. 조사된 3종류의 유기 용매(벤젠, 클로로폼, 1,2-디클로로에탄)중에서는 벤젠에서 가장 높은 수득율의 아라인 첨가생성물이 얻어졌다.

Reactions of 3-chlorobenzenediazonium tetrafluoroborate with potassium salts of carboxylic acids in the presence of 18-crown-6 and tetraphenylclopentadienone (TPCP) were investigated and an aryne adduct, 5-chloro-1,2,3,4-tetraphenylnaphthalene was isolated in poor to reasonable yield depending on the reaction conditions. The reaction was studied on the effects of salts of carboxylic acids and the solvents. Reactivity of 7 carboxylic acids fowards the research for the decomposition of 3-chlorobenzenediazonium cation via aryne pathway was found to be in the order of PhCO₂K > CH₃(CH₂)₆CO₂K > CH₃CH₂CO₂K > CH₃CO₂K > ClCH₂CO₂K > K₂CO₃ > KOH. This order seems to reflect the effectiveness of transferring solid acid salts into nonpolar benzene ne layer as an ion pair with 18-crown-6 complexed K⁺ cation. Benzene was the best nonpolar solvent for aryne adduct generation among 3 solvents (benzene, chloroform, and 1,2-dichloroethane) investigated in this research.

Keywords:aryne adduct;tetraphenylcyclopentadienone (TPCP);potassium salts;carboxylic acids;diazonium salts

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[Related Articles]

[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, Angew. Chem.-Int. Edit., 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., 27, 2503 (1979)

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

[12] Yang IW, Chung YJ, J. Korean Ind. Eng. Chem., 14(5), 641 (2003)

[13] Steigman J, Sussman D, J. Am. Chem. Soc., 89, 6400 (1967)

[14] Kolthoff JM, Sandell EB, Meehan EJ, Bruckenstein S, Quantitative Chemical Analysis, 4th ed., 1144, Cooier-Macmillan, London (1969)

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

[16] Weber WP, Gokel GW, Phase Transfer Catalysis in Organic Synthesis, 9, Spring-Verlag, New York (1977)