피리딘 디아조늄 염의 아릴화 반응

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

Journal of the Korean Industrial and Engineering Chemistry, Vol.15, No.8, 920-923, December, 2004

Export Citation

피리딘 디아조늄 염의 아릴화 반응

Arylation of Pyridinediazonim Salts

양일우^†, 정영진 ¹

윤군사관학교 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
¹School of Fire & Disaster Prevention, Samcheok National University, Gangwon 245-711, Korea

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초록

상이동 촉매 아릴화 반응의 해테로 방향족 화합물로의 확장 가능성 타진 연구로서 2-chloro-3-pyridinediazonium tetrafluoroborate, 2-chloro-5-pyridinediazoniumtetrafluoroborate, 그리고 3-pyridinediazonium tetrafluoroborate 등 3종의 피리딘 디아조늄 염의 상이동 촉매(phase transfer catalytic, PTC)반응을 조사하였다. 2-chloro-3-pyridinediazonium tetrafluoroborate, 2-chloro-5-pyridinediazonium tetrafluoroborate의 PTC 조건에서 초산칼륨과의 반응을 통한 아릴화는 벤젠 용매에서 수행된 두 반응에서 각각 56%, 17%의 피리딘 디아조늄 염을 얻었다. 첨가 아라인 포획 시약인 퓨란과 디아조늄염의 유사한 PTC 반응에서, 페닐피리딘과 함께 [4+2]사이클로 첨가 생성물의 생성이 확인되었다.

In order to study the possibility of the extension of the phase transfer catalytic (PTC) arylation reactions to heterocyclic compounds, three pyridinediazonium tetrafluoroborates such as 2-chloro-3-pyridinediazonium tetrafluoroborate, 2-chloro-5-pyridinediazonium tetrafluorborate, and 3-pyridinediazonium tetrafluoroborate were investigated. PTC reactions of the 2-chloro-3-pyridinediazonium tetrafluoroborate and 2-chloro-5-pyridinediazonium tetrafluoroborate with potassium acetate in benzene produced the corresponding phenylpyridines in 56% and 17% yields, respectively. In similar PTC reactions of the diazonium salts with an additional aryne trapping reagent, furan, formatiom of [4+2] cycloaddition products along with phenylpyridines were noticed.

Keywords:pyridinediazonium salts;arylation;aryne;cycloaddition;phenylpyridines

[References]

Patai S, The Chemistry of Diazonium and Diazo Groups, John Wiley & Sons, Inc., Chapter 14. New York (1978)
Carpes MJS, Correia CRD, Tetrahedron Lett., 43, 741 (2002)
Korzeniowski SH, Gokel GW, Tetrahedron Lett., 27, 2503 (1979)
Yang IW, Chung YJ, J. Korean Ind. Eng. Chem., 14(5), 641 (2003)
Pellissier H, Santelli M, Tetrahedron, 59, 2575 (2003)
Bartsch RA, Yang IW, J. Heterocycl. Chem., 21, 1063 (1984)
KcKillop A, Comprehensive Heterocyclic Chemistry 11, 5, Elsevier, Oxford (1996)
Roe A, Org. React., 5, 193 (1949)
Doyle MP, Bryker WJ, J. Org. Chem., 44, 1572 (1979)
Beadle JR, Korzeniowski SH, Rosenberg DE, Garcia-slanga BJ, Gokel GW, J. Org. Chem., 49, 1594 (1984)
Gadogan JIG, Mitchell JR, Sharp JT, Chem. Commun., 1 (1971)
Ruchard C, Tan CC, Angew. Chem. Int. Ed. Engl., 9, 522 (1970)
Fields EK, Meyerson S, Adv. Phys. Org. Chem., 6, 1 (1968)
Rapoport H, Look M, Kelly GJ, J. Am. Chem. Soc., 74, 6293 (1952)
vanderPlas HC, Accounts Chem. Res., 11, 462 (1978)

[Related Articles]

[1] Patai S, The Chemistry of Diazonium and Diazo Groups, John Wiley & Sons, Inc., Chapter 14. New York (1978)

[2] Carpes MJS, Correia CRD, Tetrahedron Lett., 43, 741 (2002)

[3] Korzeniowski SH, Gokel GW, Tetrahedron Lett., 27, 2503 (1979)

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

[5] Pellissier H, Santelli M, Tetrahedron, 59, 2575 (2003)

[6] Bartsch RA, Yang IW, J. Heterocycl. Chem., 21, 1063 (1984)

[7] KcKillop A, Comprehensive Heterocyclic Chemistry 11, 5, Elsevier, Oxford (1996)

[8] Roe A, Org. React., 5, 193 (1949)

[9] Doyle MP, Bryker WJ, J. Org. Chem., 44, 1572 (1979)

[10] Beadle JR, Korzeniowski SH, Rosenberg DE, Garcia-slanga BJ, Gokel GW, J. Org. Chem., 49, 1594 (1984)

[11] Gadogan JIG, Mitchell JR, Sharp JT, Chem. Commun., 1 (1971)

[12] Ruchard C, Tan CC, Angew. Chem. Int. Ed. Engl., 9, 522 (1970)

[13] Fields EK, Meyerson S, Adv. Phys. Org. Chem., 6, 1 (1968)

[14] Rapoport H, Look M, Kelly GJ, J. Am. Chem. Soc., 74, 6293 (1952)

[15] vanderPlas HC, Accounts Chem. Res., 11, 462 (1978)