크롬(VI)-피라진 착물을 이용한 알코올류의 산화반응과 메카니즘

박영조; 김영식; Young Cho Park; Young Sik Kim

Applied Chemistry for Engineering, Vol.27, No.1, 110-114, February, 2016

DOI10.14478/ace.2015.1118 Export Citation

크롬(VI)-피라진 착물을 이용한 알코올류의 산화반응과 메카니즘

Mechanism for the Oxidation Reaction of Alcohols Using Cr(VI)-Pyrazine Complex

박영조, 김영식 ^†

강원대학교 교양학부

Young Cho Park, and Young Sik Kim^†

The School of General Studies, Kangwon National University, 346 Joongang-ro, Samcheok, Gangwon-do 25913, Karea, Korea

E-mail:

초록

6M HCl 용매 하에서 피라진과 chromium (VI) trioxide의 반응을 통하여 PZCC (크롬 (VI)-피라진 착물)을 합성하였다. 적외선분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 여러 가지 용매 하에서 PZCC을 이용하여 벤질알코올의 산화반응을 측정한 결과, 용매의 유전상수 값이 증가함에 따라 반응수율이 증가했다. 그 순서는 N,N’-디메틸포름아미드 > 아세톤 > 클로로포름 > 시클로헥센이었다. 산(H2SO4) 촉매를 이용한 N,N’-디메틸포름아미드 용매 하에서, PZCC은 벤질알코올(H)과 그의 유도체들(p-OCH3, m-CH3, m-OCH3, m-Cl, m-NO2)을 효과적으로 산화시켰다. 전자받개 그룹들은 반응속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰고, Hammett 반응상수(ρ) 값은 -0.70 (308 K)이었다. 본 실험에서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어났다.

Cr(VI)-pyrazine complex (PZCC) was synthesized by the reaction of pyrazine with chromium (VI) trioxide in 6 M HCl. The structure was characterized using IR spectroscopy and inductively coupled plasma (ICP). The oxidation of benzyl alcohol using PZCC in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: N,N’-dimethylform- amide > acetone > chloroform > cyclohexene. In the presence of N,N’-dimethylformamide solvent with an acidic catalyst such as sulfuric acid (H2SO4 solution), PZCC oxidized benzyl alcohol (H) and its derivatives (p-OCH3, m-CH3, m-OCH3, m-Cl, m-NO2). Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (ρ) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate-determining step.

Keywords:PZCC;substituted benzyl alcohol;Hammett reaction constant (ρ);hydride ion transfer;rate-determining step

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[Related Articles]

[1] Davis HB, Sheets RM, Pandler WW, Heterocycles, 22, 2029 (1984)

[2] Pressprich MR, Willett RD, Davis HB, Inorg. Chem., 27, 260 (1988)

[3] Banerji KK, Bull. Chem. Soc. Jpn., 61, 1767 (1988)

[4] Mahanti MK, Dey D, J. Org. Chem., 55, 5848 (1990)

[5] Mahanti MK, Kuotsu B, Tiewsoh E, J. Org. Chem., 61, 8875 (1996)

[6] Mahanti MK, Bull. Chem. Soc. Jpn., 67, 2320 (1994)

[7] Yadav GD, J. Phys. Chem., 101, 36 (1997)

[8] Koo IS, Kim JS, An SK, J. Korean Chem. Soc., 43, 527 (1999)

[9] Tayebe R, J. Korean Chem. Soc., 52, 23 (2008)

[10] Kim YS, Choi H, Koo IS, Bull. Korean Chem. Soc., 31, 3279 (2010)

[11] Mahanti MK, J. Org. Chem., 58, 4925 (1993)

[12] Yadav GD, J. Phys. Chem., 101, 36 (1997)

[13] Mahanti MK, Bull. Chem. Soc. Jpn., 67, 2320 (1994)

[14] Mahanti MK, J. Org. Chem., 58, 4925 (1993)