융합정보논문지 (Journal of Convergence for Information Technology)

중소기업융합학회 (Convergence Society for SMB)
권호 표지
DOI QR코드

DOI QR Code

크롬(VI)-퀴놀린 화합물에 의한 알코올류의 산화반응에 대한 반응속도론적 연구

Kinetic Study on the Oxidation Reaction of Alcohols by Cr(VI)-Quinoline Compound

  • 박영조 (강원대학교 교양교육센) ;
  • 김수종 (한라대학교 신소재화학공학과)
  • Park, Young-Cho (Center for Liberal Education, Kangwon National University) ;
  • Kim, Soo-Jong (Department of Advanced Materials & Chemical Engineering, Halla University)
  • 투고 : 2021.05.15
  • 심사 : 2021.09.20
  • 발행 : 2021.09.28
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

유기공업 화학에서 알코올류의 산화제에 대해 연구가 많이 진행 되고 있으며, 그중에서도 크롬(VI)-계열의 시약들이 산화제로 널리 이용되어 왔다. 그리고 일차알코올을 알데히드로만 산화시키는 산화제와 메카니즘 규명이 필요하게 되었다. 이러한 연구의 일환으로 본 연구에서는 퀴놀린과 chromium(VI) trioxide을 반응시켜 크롬(VI)-퀴놀린 화합물[(C9H7NH)2Cr2O7]을 합성하여, FT-IR 및 원소분석에서 구조를 확인하였다. 여러 가지 유기용매를 사용하여 크롬(VI)-퀴놀린 화합물에 의한 벤질 알코올의 산화반응은 유전상수 값이 큰 유기용매인 N,N'-dimethylformamide에서 높은 산화반응성을 보였다. N,N'-dimethylformamide 용매를 사용하여 크롬(VI)-퀴놀린 화합물은 치환 벤질 알코올류를 효율적으로 산화시켰고, Hammett 반응상수(ρ)=-0.69(303 K) 이였다. 본 실험에서 알코올의 산화반응 과정은 chromate ester 형성과정과, 속도결정단계에서 수소화 전이가 일어나는 반응경로임을 알 수 있었다. 결과적으로 크롬(VI)-퀴놀린 화합물은 벤질알코올, 알릴알코올, 일차알코올 및 이차알코올류를 알데히드나 케톤으로 전환시키는 효율적인 산화제로, 이차알코올류 존재 하에서 벤질알코올, 알릴알코올, 일차알코올의 선택적인 산화제로 사용할 수 있다.

Cr(VI)-quinoline compound[(C9H7NH)2Cr2O7] was synthesized by the reaction between of quinoline and chromium(VI) trioxide, and structure was FT-IR, elemental analysis. The oxidation ability of benzyl alcohol greatly depends upon the dielectric constant of the used organic solvent, where carbon tetrachloride was worst and N,N'-dimethylformamide was best solvent. Noticeably, in N,N'-dimethylformamide solvent, Cr(VI)-quinoline compound oxidized substituted benzyl alcohols. The Hammett reaction constant(ρ)=-0.69(303K). As a resuit, Cr(VI)-quinoline compound was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones. Cr(VI)-quinoline compound was selective oxidizing agent of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary alcohol ones.

키워드

참고문헌

  1. H. B. Davis & R. M. Sheets. (1984). High Valent Chromium Heterocyclic Complexes-ll: New Selective and Mild Oxidants. Heterocycles, 22, 2029-2035. DOI : 10.3987/R-1984-09-2029
  2. M. R. Pressprich & R, D. Willett. (1988). Peparation and Crystal Structure of Dipyrazinium Trichromate and Bond Length Correlation for Chromate Anions of the Form CrnO3n+12-. Inorg. Chem., 27, 260-264. DOI : 10.1021/jc00275a009
  3. C. S. Kim & K. S. Yoo. (2013). Preparation of Ag/TiO2 Particle for Aerobic Benzyl Alcohol Oxidation. Appl. Chem. Eng,., 24(6), 663-667. DOI : 10.14478/ace.2013.1094
  4. T. J. Cho & K. S. Yoo. (2014). Synthesis of Pd/TiO2 Catalyst for Aerobic Benzyl Alcohol Oxidation. Appl. Chem. Eng., 25(3), 281-285. DOI : 10.14478/ace.2014.1028
  5. Y. J. Choo & K. S. Yoo. (2014). Synthesis of Pd-Ag on Charcoal Catalyst for Aerobic Benzyl Alcohol Oxidation Using[Hmim][PF6]. Appl. Chem. Eng,., 25(4), 425-429. DOI : 10.14478/ace.2014.1063
  6. T. J. Cho & K. S. Yoo. (2015). Preparation of Pd/TiO2 Catalyst Using Room Temperature Ionic Liquids for Aerobic Benzyl Alcohol Oxidation. Appl. Chem. Eng., 26(3), 351-355. DOI : 10.14478/ace.2015.1044
  7. P. D. Lokhande & S. R. Waghmare. (2012). Copper Catalyzed Selective Oxidation of Benzyl Alcohol to Benzaldehyde. Journal of the Korean Chemical Society, 56(5), 539-541. DOI : 10.5012/jkcs.2012.56.5.539
  8. Y. Y. Kim & K. Y. Kwon. (2014). Synthesis of Ru Incorporated TiO2 and Application to Oxidation of Benzyl Alcohol with Molecular Oxygen. Appl. Chem. Eng,., 25(6), 645-647. DOI : 10.14478/ace.2014.1106
  9. K. W. Kim & S. M. Lee. (2014). A Study on Characterization for Catalytic Oxidation of Nitrogen Monoxide Over Mn/TiO2 Catalyst. Appl. Chem., Eng, 25, 474-480. DOI : 10.14478/ace.2014.1061
  10. J. O. Jo & Y. S. Mok. (2014). Oxidation of Isopropyl Alcohol in Air by a Catalytic Plasma Reactor System. Appl. Chem. Eng., 25(5), 531-537. DOI : 10.14478/ace.2014.1082
  11. Y. H. Lee & K. Y. Kwon. (2017). Synthesis and Oxidative Catalytic Property of Ruthenium-doped Titanate Nanosheets. Appl. Chem. Eng., 28(5), 593-596. DOI : 10.14478/ace.2017.1056
  12. S. G. Lee & S. S. Park. (2011). Solvothermal Preparation of Nanocrystalline TiO2 Using Alcohol-water Mixed Solvent. Appl. Chem. Eng., 22(6), 685-690.
  13. R. Tayebee. (2008). Simple Heteropoly Acids as Water Tolerant Catalysts in the Oxidation of Alcohols with 34% Hydrogen Peroxide, A Mechanistic Approach. J. Korean Chem. Soc., 52, 23-29. DOI : 10.5012/jkcs.2008.52.1.023
  14. Y. S. Kim & H. Choi. (2010). Kinetics and Mechanism of Nucleophilic Substittution Reaction of 4-Subsitituted-2,6-dinitrochloro- benzene with Benzylamines in MeOH-MeCN Mixtures. Bull. Korean Chem. Soc., 31, 3279-3282. DOI : 10.5012/jkcs.2008.52.1.023
  15. F. K. Behbahani & M. Farahani. (2011). Iron (III) Phosphate as a Green and Reusable Catalyst Promoted Chemo Selective Acetylation of Alcohols and Phenols with Acetic Anhydride Under Solvent Free Conditions at Room Temperature. Journal of the Korean Chemical Society, 55(4), 633-637, DOI : 10.5012/jkcs.2011.55.4.633