Cr(VI)-6-Methylquinoline을 이용한 치환 벤질 알코올류의 산화반응과 속도론에 관한 연구

박영조; 김영식; Young Cho Park; Young Sik Kim

Applied Chemistry for Engineering, Vol.26, No.3, 372-376, June, 2015

DOI10.14478/ace.2015.1021 Export Citation

Cr(VI)-6-Methylquinoline을 이용한 치환 벤질 알코올류의 산화반응과 속도론에 관한 연구

A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using Cr(VI)-6-Methylquinoline

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 245-711, Karea, Korea

E-mail:

초록

6M HCl 용매 하에서 6-메틸퀴놀린과 chromium(VI) trioxide의 반응을 통하여 6-MQCC(크롬(VI)-6-메틸퀴놀린) 착물을 합성하였다. 적외선분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 여러 가지 용매 하에서 6-MQCC을 이용하여 벤질 알코올의 산화반응을 측정한 결과, 용매의 유전상수 값이 증가함에 따라 반응수율이 증가했다. 그 순서는 DMF > 아세톤 > 클로로포름 > 시클로헥센이었다. 산(H2SO4) 촉매를 이용한 DMF 용매 하에서, 6-MQCC은 벤질 알코올 (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 -0.69 (308 K)이었다. 본 실험에 서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어났다.

6-MQCC (Cr(VI)-6-methylquinoline) complex was synthesized by the reaction of 6-methylquinoline with chromium(VI) trioxide in 6 M HCl. The structure was characterized using IR (Infrared Spectroscopy) and ICP (Inductively Coupled Plasma) analysis. The oxidation of benzyl alcohol using 6-MQCC in various solvents showed that the reactivity increased with the increase of the dielectric constant, in descending order of DMF > acetone > chloroform > cyclohexene. In the presence of DMF solvent with acidic catalyst such as sulfuric acid (H2SO4 solution), 6-MQCC oxidized benzyl alcohol (H) and its derivatives (p-OCH3, m-CH3, m-OCH3, m-Cl, m-NO2) were effectively oxidized. Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (ρ) was -0.69 (308 K). The observed experimental data was used to rationalize the fact that the hydride ion transfer occurred at the rate-determining step.

Keywords:6-MQCC;substituted benzyl alcohol;Hammett reaction constant (ρ);hydride ion transfer;rate-determining step

[References]

Bae SK, Selective Oxidation of Alcohols with Compounds of Chromium(VI) and Heterocyclic Bases, D. Sc. Thesis, Yonsei University (1986).
Davis HB, Sheets RM, Pandler WW, Heterocycles, 22, 2029 (1984)
Pressprich MR, Willett RD, Davis HB, Inorg. Chem., 27, 260 (1988)
Banerji KK, Bull. Chem. Soc. Jpn., 61, 1767 (1988)
Mahanti MK, Dey D, J. Org. Chem., 55, 5848 (1990)
Mahanti MK, Kuotsu B, Tiewsoh E, J. Org. Chem., 61, 8875 (1996)
Mahanti MK, Bull. Chem. Soc. Jpn., 67, 2320 (1994)
Yadav GD, J. Phys. Chem., 101, 36 (1997)
Koo IS, Kim JS, An SK, J. Korean Chem. Soc., 43, 527 (1999)
Tayebee R, J. Korean Chem. Soc., 52, 23 (2008)
Kim YS, Choi H, Koo IS, Bull. Korean Chem. Soc., 31, 3279 (2010)
Mahanti MK, J. Org. Chem., 58, 4925 (1993)
Yadav GD, J. Phys. Chem., 101, 36 (1997)
Mahanti MK, Bull. Chem. Soc. Jpn., 67, 2320 (1994)
Mahanti MK, J. Org. Chem., 58, 4925 (1993)
Gilliom RD, Introduction to Physical Organic Chemistry, 169-250, Addison-Wesley Educational Publishers Inc, USA (1970).

[Related Articles]

[1] Bae SK, Selective Oxidation of Alcohols with Compounds of Chromium(VI) and Heterocyclic Bases, D. Sc. Thesis, Yonsei University (1986).

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

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

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

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

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

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

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

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

[10] Tayebee R, J. Korean Chem. Soc., 52, 23 (2008)

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

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

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

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

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

[16] Gilliom RD, Introduction to Physical Organic Chemistry, 169-250, Addison-Wesley Educational Publishers Inc, USA (1970).