Journal of the Korean Industrial and Engineering Chemistry, Vol.5, No.5, 871-877, October, 1994
4-비닐시클로헥센을 이용한 방향족 니트로 화합물의 환원반응
Catalytic Hydrogen Transfer Reduction of Aromatic Nitro Compounds with 4-Vinylcyclohexene
초록
부타디엔의 고분자반응 또는 운반 및 보관과정에서 이량화되어 생성되는 4-비닐시클로헥센(VCH)을 이용하여 방향족 니트로화합물을 Pd/C 촉매하에서 촉매 전달 수소화반응시켜 높은 수율의 아닐린유도체로 합성하였다. 니트로벤젠고리에 치환기가 치환된 오르토-니트로톨루엔, 오르토-니트로페놀, 오르토-니트로아니졸의 경우는 파라-디트로톨루엔, 파라-니트로페놀, 파라-니트로아니졸의 반응보다 반응 소요시간이 길었다. 4-비닐시클로헥센-에탄올-Pd/C계에서 오르토, 메타, 파라-클로로니트로벤젠, 파라-니트로벤즈알데히드, 파라-니트로벤질알코올, 파라-니트로벤질 아세테이트 등의 화합물에서는 환원반응뿐만 아니라 가수소 분해반응도 진행되어 파라-톨루이딘이 생성되었다.
Most of the aromatic nitro compounds were reduced to amines in high yield by transfer of hydrogen from 4-vinyl cyclohexene to the substrate via palladium catalyst. The usefulness of the method is not affected by the presence of a variety of other functional groups such as -OH, -OCH3, -CH3, -CO2H, and -Cl, except for halogen which is removed during hydrogenation. The reduction of ortho-substituted nitrobenzene such as o-nitrotoluene, o-nitrophenol, o-nitroanisole was slower than the para isomer. Typically, the nitro compound is refluxed in ethanol with a large exess of 4-vinylcyclohexene in the presence of Pd-C catalyst. Under the above conditions, p-nitrobenzaldehyde, p-nitrobenzyl alcohol, and p-nitrobenzyl acetate were reduced to p-toluidine.
- Larock RC, "Comprehensive Organic Transformation," 6, VCH, New York (1989)
- House HO, "Modern Synthetic Reactions," 1-34, Benjamin, Menlo Park (1972)
- Johnstone RAW, Wilby AH, Chem. Rev., 85, 129 (1985)
- Brieger G, Nestrick TJ, Chem. Rev., 74, 567 (1974)
- Entwistle ID, Johnstone RAW, Povall TJ, J. Chem. Soc.-Perkin Trans. 1, 1300 (1975)
- Braude EA, Linstead RP, Wooldridge KRH, J. Chem. Soc., 3585 (1954)
- Coutts RT, Edwards JB, Can. J. Chem., 44, 2009 (1966)
- Braude EA, Linstead RP, Jackman LM, Mitchell PWD, Wooldridge KRH, Nature, 169, 100 (1952)
- Eschinazi HE, Bergmann ED, J. Am. Chem. Soc., 72, 5651 (1950)
- Braude EA, Linstead RP, Wooldridge KRH, Mitchell PWD, J. Chem. Soc., 3595 (1954)
- Kinder K, Luhrs K, Justus Liebigs Ann. Chem., 685, 36 (1965)
- Braude EA, Linstead RP, Mitchell PWD, J. Chem. Soc., 3578 (1954)
- Kleiderer EC, Kornfeld EC, J. Org. Chem., 13, 455 (1948)
- Sasson Y, Blum J, Tetrahedron Lett., 2617 (1971)
- Volpin ME, Kukolev VP, Chernyshev VO, Kolomnikov IS, Tetrahedron Lett., 4435 (1971)
- Perrin DD, Armarego WLF, "Purification of Laboratory Chemicals," 3rd Ed., Pergamon Press, New York (1988)
- Crabtree RH, Chem. Rev., 85, 245 (1985)
- Entwistle ID, Jackson AE, Johnstane RAW, Telford RP, J. Chem. Soc.-Perkin Trans. 1, 443 (1977)