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环丙基甲醛

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环丙基甲醛
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  checkY
PubChem 123114
SMILES
 
  • C1CC1C=O
InChI
 
  • 1S/C4H6O/c5-3-4-1-2-4/h3-4H,1-2H2
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

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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（德语：Trans-Crotonaldehyd）巴豆醛：[13]

反应

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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-4,5-二氢噁唑。[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

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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（德语：Profluralin）：[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

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  1. ^ 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）. 
  2. ^ 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）. 
  3. ^ 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）. 
  4. ^ CHA, J. S.; LEE, K. D.; KWON, O. O.; KIM, J. M.; LEE, H. S. ChemInform Abstract: Systematic Study on Bis(dialkylamino)aluminum Hydride: Reexamination of the Reagents for Reduction of Carboxylic Acids to Aldehydes.. ChemInform (Wiley). 2010-08-16, 26 (51). ISSN 0931-7597. doi:10.1002/chin.199551071 （英语）. 
  5. ^ Cha, Jin Soon; Kim, Jin Euog; Oh, Se Yeon; Lee, Jae Cheol; Lee, Kwang Woo. Direct conversion of saturated and unsaturated carboxylic acids into aldehydes by thexylbromoborane-dimethyl sulfide. Tetrahedron Letters (Elsevier BV). 1987, 28 (21): 2389–2392. ISSN 0040-4039. doi:10.1016/s0040-4039(00)96132-x （英语）. 
  6. ^ 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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  8. ^ 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）. 
  9. ^ 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）. 
  10. ^ 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）. 
  11. ^ 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）. 
  12. ^ Cyclopropanecarboxaldehyde. Organic Syntheses (Organic Syntheses). 1981, 60: 25. ISSN 0078-6209. doi:10.15227/orgsyn.060.0025 （英语）. 
  13. ^ 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）. 
  14. ^ Kleemiss, Wolfgang; Feld, Marcel. Hydrogenation process and catalysts for the preparation of (hydroxymethyl)cyclopropane from formylcyclopropane. EP 794166 A2. 1997 （德语）. 
  15. ^ Zhao, Junfeng; Mück-Lichtenfeld, Christian; Studer, Armido. Cooperative N-Heterocyclic Carbene (NHC) and Ruthenium Redox Catalysis: Oxidative Esterification of Aldehydes with Air as the Terminal Oxidant. Advanced Synthesis & Catalysis (Wiley). 2013-04-08, 355 (6): 1098–1106. ISSN 1615-4150. doi:10.1002/adsc.201300034 （英语）. 
  16. ^ Huang, Huawen; Ji, Xiaochen; Wu, Wanqing; Jiang, Huanfeng. A cascade approach to fused indolizinones through Lewis acid–copper(i) relay catalysis. Chemical Communications (Royal Society of Chemistry (RSC)). 2013, 49 (32): 3351. ISSN 1359-7345. doi:10.1039/c3cc40643a （英语）. 
  17. ^ Wei, Yahui; Zhao, Cong; Xuan, Qingqing; Song, Qiuling. An expedient and novel strategy for reductive amination by employing H2O as both a hydrogen source and solventviaB2(OH)4/H2O systems. Organic Chemistry Frontiers (Royal Society of Chemistry (RSC)). 2017, 4 (12): 2291–2295. ISSN 2052-4129. doi:10.1039/c7qo00769h （英语）. 
  18. ^ Porter, David W.; Bradley, Michelle; Brown, Zarin; Charlton, Steven J.; Cox, Brian; Hunt, Peter; Janus, Diana; Lewis, Sarah; Oakley, Paul; O’Connor, Des; Reilly, John; Smith, Nichola; Press, Neil J. The discovery of potent, orally bioavailable pyrimidine-5-carbonitrile-6-alkyl CXCR2 receptor antagonists. Bioorganic & Medicinal Chemistry Letters (Elsevier BV). 2014, 24 (15): 3285–3290. ISSN 0960-894X. doi:10.1016/j.bmcl.2014.06.011 （英语）. 
  19. ^ Dong, Kuiyong; Humeidi, Ahmad; Griffith, Wendell; Arman, Hadi; Xu, Xinfang; Doyle, Michael P. Ag I ‐Catalyzed Reaction of Enol Diazoacetates and Imino Ethers: Synthesis of Highly Functionalized Pyrroles. Angewandte Chemie International Edition (Wiley). 2021-05-06, 60 (24): 13394–13400. ISSN 1433-7851. doi:10.1002/anie.202101641 （英语）. 
  20. ^ Hatano, Manabu; Mizuno, Tomokazu; Ishihara, Kazuaki. Catalytic enantioselective synthesis of sterically demanding alcohols using di(2°-alkyl)zinc prepared by the refined Charette's method. Chemical Communications (Royal Society of Chemistry (RSC)). 2010, 46 (30): 5443. ISSN 1359-7345. doi:10.1039/c0cc01301c （英语）. 
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  22. ^ Wang, Zhe; Campagna, Silvio; Yang, Kaihong; Xu, Guoyou; Pierce, Michael E.; Fortunak, Joseph. M.; Confalone, Pat. N. A Practical Preparation of Terminal Alkynes from Aldehydes. The Journal of Organic Chemistry (American Chemical Society (ACS)). 2000-03-01, 65 (6): 1889–1891. ISSN 0022-3263. doi:10.1021/jo9916582 （英语）. 
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