环丙基甲醛
外观
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环丙基甲醛 | |
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IUPAC名 cyclopropanecarbaldehyde | |
英文名 | Cyclopropanecarboxaldehyde |
别名 | 环丙甲醛 甲酰基环丙烷 |
识别 | |
CAS号 | 1489-69-6 ![]() |
PubChem | 123114 |
SMILES |
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InChI |
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InChIKey | JMYVMOUINOAAPA-UHFFFAOYSA-N |
性质 | |
化学式 | C4H6O |
摩尔质量 | 70.09 g·mol−1 |
外观 | 无色液体 |
密度 | 0.938 g·cm−3[1] |
沸点 | 98—101 °C(371—374 K)[2] |
溶解性(水) | 可溶 |
危险性 | |
GHS提示词 | 危险 |
H-术语 | H225, H314 |
P-术语 | P210, P233, P240, P241, P242, P243, P260, P264, P280, P301+330+331, P303+361+353, P304+340, P305+351+338, P310 |
相关物质 | |
相关化学品 | 环丁基甲醛 环戊基甲醛 环己基甲醛 |
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。 |
环丙基甲醛是一种有机化合物,化学式为C4H6O,是环丙烷的一个氢被甲酰基取代的产物。它是无色至黄色的液体,可溶于水及一些有机溶剂。
合成
[编辑]环丙基甲醛可由9-硼杂双环[3.3.1]壬烷[3]、二(二乙氨基)氢化铝[4]、1,1,2-三甲基丙基溴代甲硼烷二甲基硫醚配合物[5]等还原剂还原环丙基甲酸制得。高碘酸[6]、重铬酸钠[7]、3-亚碘酰苯甲酸[8]、硝酸铈铵[9]、氧气[10]等氧化剂氧化环丙基甲醇也能得到环丙基甲醛。
丁二酸二乙酯的酮醇缩合反应可以得到2-羟基环丁酮[11],它可以被氢化铝锂还原为1,2-环丁二醇,再在三氟化硼二丁醚缩环,可以得到环丙基甲醛:[12]
2,3-二氢呋喃在加热、加压下经氧化铝催化下发生重排反应,也能得到环丙基甲醛,副产物是反式巴豆醛:[13]
反应
[编辑]环丙基甲醛可以发生醛的特征反应,如加氢还原为环丙基甲醇[14]或氧化为环丙基甲酸[15];它和苄胺在对甲苯磺酸的催化下缩合,得到N-(环丙基亚甲基)苄胺[16],在该体系中,加入二硼酸可以将亚胺加氢为胺[17];和氰乙酸乙酯发生Knoevenagel缩合反应,生成2-氰基-3-环丙基-2-丙烯酸乙酯。[18]在三氟化硼乙醚的存在下,它和2-叠氮基乙醇于二氯甲烷中反应,可以得到2-环丙基-4,5-二氢𫫇唑。[19]
它和二环戊基锌反应,可以得到α-环丙基环戊基甲醇。[20]
应用
[编辑]环丙基甲醛和正丙胺缩合后氢化,得到N-(环丙基甲基)丙胺,它再与4-氯-3,5-二硝基三氟甲苯反应,可以得到除草剂环丙氟灵:[21]
以环丙基甲醛为原料可以合成环丙基乙炔。它首先和三氯乙酸反应,得到α-三氯甲基环丙基甲醇,经对甲基苯基磺酰氯(TsCl)转化为对甲苯磺酸酯,所得的酯再与甲基锂反应,水解后生成环丙基乙炔。[22]
参考文献
[编辑]- ^ Haynes, William. CRC handbook of chemistry and physics : a ready-reference book of chemical and physical data. Boca Raton, Florida: CRC Press. 2017: 3-138. ISBN 978-1-4987-5429-3. OCLC 957751024 (英语).
- ^ Venus-Danilova, E. D.; Kazimirova, V. F. Aldehydes and hydroxyaldehydes of the polymethylene series. IX. Isomeric changes of cyclopropylformaldehyde. Zhurnal Obshchei Khimii. 1938, 8: 1438-1436. ISSN 0044-460X (俄语).
- ^ Cha, Jin Soon; Kim, Jin Euog; Oh, Se Yeon; Kim, Jong Dae. One-pot conversion of carboxylic acids to aldehydes through treatment of acyloxy-9-borabicyclo[3.3.1]nonanes with lithium 9-boratabicyclo[3.3.1]nonane. Tetrahedron Letters (Elsevier BV). 1987, 28 (39): 4575–4578. ISSN 0040-4039. doi:10.1016/s0040-4039(00)96568-7 (英语).
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- ^ Ganesamoorthy, S.; Shanmugasundaram, K.; Karvembu, R. Mild oxidation of alcohols with periodic acid catalyzed by [Ru(acac)2(CH3CN)2]PF6 in water. Catalysis Communications (Elsevier BV). 2009, 10 (14): 1835–1838. ISSN 1566-7367. doi:10.1016/j.catcom.2009.06.010 (英语).
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- ^ Yusubov, Mekhman S.; Gilmkhanova, Marina P.; Zhdankin, Viktor V.; Kirschning, Andreas. m-Iodosylbenzoic Acid as a Convenient Recyclable Reagent for Highly Efficient RuCl3-Catalyzed Oxidation of Alcohols to Carbonyl Compounds.. ChemInform (Wiley). 2007-07-10, 38 (28). ISSN 0931-7597. doi:10.1002/chin.200728043 (英语).
- ^ Young, Lewis Brewster; Trahanovsky, Walter S. Cerium(IV) oxidation of organic compounds. III. Preparation of cyclopropanecarboxaldehyde from cyclopropanemethanol. The Journal of Organic Chemistry (American Chemical Society (ACS)). 1967, 32 (7): 2349–2350. ISSN 0022-3263. doi:10.1021/jo01282a058 (英语).
- ^ Wang, Xinliang; Liu, Renhua; Jin, Yu; Liang, Xinmiao. TEMPO/HCl/NaNO2 Catalyst: A Transition-Metal-Free Approach to Efficient Aerobic Oxidation of Alcohols to Aldehydes and Ketones Under Mild Conditions. Chemistry - A European Journal (Wiley). 2008-03-17, 14 (9): 2679–2685. ISSN 0947-6539. doi:10.1002/chem.200701818 (英语).
- ^ Gatling, Sterling C.; Jackson, James E. Reactivity Control via Dihydrogen Bonding: Diastereoselection in Borohydride Reductions of α-Hydroxyketones. Journal of the American Chemical Society (American Chemical Society (ACS)). 1999, 121 (37): 8655–8656. ISSN 0002-7863. doi:10.1021/ja991784n (英语).
- ^ Cyclopropanecarboxaldehyde. Organic Syntheses (Organic Syntheses). 1981, 60: 25. ISSN 0078-6209. doi:10.15227/orgsyn.060.0025 (英语).
- ^ Liang, Shaowo; Price, Timothy W. Process for the conversion of 2,3-dihydrofuran to cyclopropanecarboxaldehyde. US5633410A. 1997-05-27 [2021-08-29]. (原始内容存档于2021-08-29) (英语).
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