한국산학기술학회논문지 (Journal of the Korea Academia-Industrial cooperation Society)

  • 제12권12호
  • /
  • Pages.5990-5996
  • /
  • 2011
  • /
  • 1975-4701(pISSN)
  • /
  • 2288-4688(eISSN)
한국산학기술학회 (The Korea Academia-Industrial cooperation Society)
권호 표지
DOI QR코드

DOI QR Code

6-Methylquinolinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응 속도

Kinetics of the Oxidation of Substituted Benzyl Alcohols using 6-Methylquinolinium Dichromate

  • 김영식 (강원대학교 화학공학과) ;
  • 박영조 (강원대학교 화학공학과)
  • Kim, Young-Sik (Department of Chemical Engineering, Kangwon National University) ;
  • Park, Young-Cho (Department of Chemical Engineering, Kangwon National University)
  • 투고 : 2011.09.14
  • 심사 : 2011.12.13
  • 발행 : 2011.12.31
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

$H_2O$ 용매 하에서 6-methylquinoline 과 chromium trioxide의 반응을 통하여 6-methylquinolinium dichromate [$(C_{10}H_9NH)_2Cr_2O_7$]를 합성하여, 적외선분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 여러 가지 용매 하에서 6-methylquinolinium dichromate를 이용하여 벤질 알코올의 산화반응을 측정한 결과 유전상수(${\varepsilon}$) 값이 큰 용매 순서인 시클로헥센 < 클로로포름 < 아세톤 < N,N-디메틸포름아미드 용매 하에서 높은 산화반응성을 보였다. 산촉매($H_2SO_4$)를 이용한 DMF 용매 하에서 6-methylquinolinium dichromat는 벤질 알코올과 그의 유도체들(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$)을 효과적으로 산화시켰다. 그리고 전자받개 그룹들은 반응속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰다. 또한 Hammett 반응상수(${\rho}$) 값은 -0.67(303K) 이였다. 그러므로 본 실험에서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어나는 메카니즘임을 알 수 있었다.

6-Methylquinolinium dichromate[$(C_{10}H_9NH)_2Cr_2O_7$] was synthesized by the reaction of 6-methylquinoline with chromium trioxide in $H_2O$, and characterized by IR, ICP. The oxidation of benzyl alcohol using 6-methylquinolinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene < chloroform < acetone < N,N- dimethylformamide. In the presence of hydrochloric acid($H_2SO_4$ solution), 6-methylquinolinium dichromate oxidized benzyl alcohol and its derivatives(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$) smoothly in DMF. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.67(303K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

키워드

참고문헌

  1. K. K. Banerji, "Kinetic Study of the Oxidation of Substituted Benzyl Alcohols by Ethyl Chloro-chromate", Bull. Chem. Soc. Japan, 61, 5, pp.1767-1771, 1988. https://doi.org/10.1246/bcsj.61.1767
  2. J. F. Kuo, "Chromium(VI) Complexation with Triisooctylamine in Organic Solvents", Bull. Chem. Soc. Japan, 64, 10, pp. 3059-3062, 1991. https://doi.org/10.1246/bcsj.64.3059
  3. M. K. Mahanti, D. Dey, "Kinetics of Oxid-ation of Substituted Benzyl Alcohols by Quin-olinium Dichromate", J. Org. Chem., 55, 23, pp.5848-5850, 1990. https://doi.org/10.1021/jo00310a015
  4. M. K. Mahanti, "Kinetics of Oxidation of Nitro-toluenes by Acidic Hexacyanoferrate(III)", Bull. Korean Chem. Soc., 4, 3, pp. 120-123, 1983.
  5. G. P. Panigrahi, "Michaelis-Menten Behaviour in the Oxidation of Benzaldehydes by Pyridinium Chlorochromate", Bull. Korean Chem. Soc., 13, 5, pp. 547-550, 1992.
  6. M. K. Mahanti, B. Kuotsu, E. Tiewsoh, "Quino-linium Dichromate Oxidation of Diols: A Kineti-cs Study", J. Org. Chem., 61, 25, pp. 8875-8877, 1996. https://doi.org/10.1021/jo961079m
  7. H. B. Davis, R. M. Sheets, W.W. Pandler, "High Valent Chromium Heterocyclic Complexes-ll: New Selective and Mild Oxidants", Heterocyc-les, 22, 9, pp. 2029-2035, 1984. https://doi.org/10.3987/R-1984-09-2029
  8. M. R. Pressprich, R, D. Willett, H. B. Davis, "Peparation and Crystal Structure of Dipyrazin-ium Trichromate and Bond Length Correlation for Chromate Anions of the Form $Cr_nO_{3n+1}\;^{2-}$, Inorg. Chem., 27, 2, pp. 260-264, 1988. https://doi.org/10.1021/ic00275a009
  9. M. H. Cho, J. H. Kim, H. B. Park, "Kinetic St-udy of Macrocyclic Ligand-Metal Ion Compl-exes", J. Korean Chem. Soc., 33, 4, pp. 366-370, 1989.
  10. G. D. Yadav, "Mechanistic and Kinetic Investi-gation of Liquid-Liquid Phase Transfer Catalyz-ed Oxidation of Benzyl Chloride to Benzald-ehyde", J. Phys Chem., 101, 1, pp. 36-48, 1997. https://doi.org/10.1021/jp961678x
  11. M. K. Mahanti, "Kinetics and Mechanism of the Oxidative Cleavage of Unsaturated Acids by Quinolinium Dichromate", Bull. Chem. Soc. Japan, 67, 8, pp. 2320-2322, 1994. https://doi.org/10.1246/bcsj.67.2320
  12. M. K. Mahanti, "Quinolinium Dichromate Oxida-tions Kinetics and Mechanism of the Oxidative Cleavage of Styrenes", J. Org. Chem., 58, 18, pp. 4925-4928, 1993. https://doi.org/10.1021/jo00070a031
  13. I. S. Koo, J. S. Kim, S. K. An, "Kinetic Studies on Solvolyses of Subsitituted Cinnamoyl Chlorides in Alcohol-Water Mixture", J. Korean Chem. Soc., 43, 5, pp. 527-534, 1999.
  14. R. Tayebee, "Simple Heteropoly Acids as Water Tolerant Catalysts in the Oxidation of Alcohols with 34% Hydrogen Peroxide, A Mechanistic Approach", J. Korean Chem. Soc., 52, 1, pp. 23-29, 2008. https://doi.org/10.5012/jkcs.2008.52.1.023
  15. R. Y. Sung, H. Choi, I. S. Koo, "Kinetic Studies on the Nucleophilic Substittution Reaction of 4-X-Subsitituted-2, 6-dinitrochlorobenzene with Pyridines in MeOH-MeCN Mixtures", Bull. Korean Chem. Soc., 30, 7, pp. 1579-1582, 1988 https://doi.org/10.5012/bkcs.2009.30.7.1579
  16. Y. S. Kim, H. Choi, I. S. Koo, "Kinetics and Mechanism of Nucleophilic Substittution Rea-ction of 4-Subsitituted-2,6-dinitrochlorobenzene with Benzylamines in MeOH-MeCN Mixtures", Bull. Korean Chem. Soc., 31, 11, pp. 3279-3282, https://doi.org/10.5012/bkcs.2010.31.11.3279
  17. M. H. Cho, J. H. Kim, and H. B. Park, "Kine-tic Study of Macrocyclic Ligand-Metal Ion Complexes", J. Korean Chem. Soc., 33, pp.366-371, 1989.
  18. G. D. Yadav, "Mechanistic and Kinetic Investi-gation of Liquid-Liquid Phase Transfer Cata-lyzed Oxidation of Benzyl Chloride to Benz-aldehyde", J. Phys. Chem., 101, pp. 36-40, 1997. https://doi.org/10.1021/jp961678x
  19. M. K. Mahanti, "Kinetics and Mechanism of the Oxidative Cleavage of Unsaturated Acids by Qu-inolinium Dichromate", Bull. Chem. Soc. Japan., 67, pp. 2320-2324, 1994. https://doi.org/10.1246/bcsj.67.2320
  20. D. Richard and Gilliom, Physical OrganicChemi-stry", pp. 169-180, 1992.
  21. M. K. Mahanti, "Quinolinium Dichromate Oxid-ations Kinetics and Mechanism of the Oxidative Cleavage of Styrenes", J. Org. Chem., 58, pp.4925-4928, 1993. https://doi.org/10.1021/jo00070a031