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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 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]三氟化硼乙醚的存在下,它和2-叠氮基乙醇二氯甲烷中反应,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). 
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  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). 
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  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). 
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