4-methyl-3-furaldehyde | 107658-19-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methyl-3-furaldehyde
• 英文别名: 4-methyl-furan-3-carbaldehyde；4-Methyl-furan-3-carbaldehyd；4-Methylfuran-3-carbaldehyde
• CAS: 107658-19-5
• 化学式: C₆H₆O₂
• 分子量: 110.112
• InChiKey: XVLTWSMCDADDAL-UHFFFAOYSA-N

物化性质

• 沸点：
  55 °C(Press: 11 Torr)
• 密度：
  1.099±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  30.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-methyl-3-furaldehyde 在 lithium hydroxide 、 4 A molecular sieve 、 pH 7 aq. phosphate buffer 、 Raney nickel (W-4) 、 三氟甲磺酸二丁硼 、 双氧水 、 氧气 、 rose bengal 、 氟化氢吡啶 、 三乙胺 、 N,N-二异丙基乙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 10.58h， 生成 trimethyl (Z,3R)-3-hydroxy-1-methylbut-1-ene-1,2,4-tricarboxylate
  参考文献：
  名称：

  Synthetic studies on tautomycin

  摘要：

  The 2,3-disubstituted maleic anhydride segment of tautomycin has been synthesized in optically active form. Oxidation of 3,4-disubsrituted furan employing singlet oxygen completes the construction of the maleic anhydride moiety. Esterification of the maleic anhydride segment without protecting anhydride moiety resulted in the successful coupling reaction with fragment derived from tautomycin.

  DOI：

  10.1016/s0040-4020(01)85365-5
• 作为产物：
  描述：

  4-甲基-呋喃-2,3-二羧酸 在 Pd-BaSO₄ 、 氯化亚砜 、 xylene 作用下， 生成 4-methyl-3-furaldehyde
  参考文献：
  名称：

  2,3-和3,4-二甲基呋喃的合成

  摘要：

  DOI：

  10.1002/hlca.19330160107

文献信息

• Regioselective Preparation of 2,4-, 3,4-, and 2,3,4-Substituted Furan Rings. 2.¹ Regioselective Lithiation of 2-Silylated-3-substituted Furan Rings
  作者：Edward Bures、James A. Nieman、Shuyuan Yu、Patrick G. Spinazzé、Jean-Louis J. Bontront、Ian R. Hunt、Arvi Rauk、Brian A. Keay

  DOI：10.1021/jo971098b

  日期：1997.12.1

  A new method for the preparation of 3,4- and 2,5-disubstituted furan rings is described. A variety of 2-silylated-3-(hydroxymethyl)furans and 2-silylated-3-furoic acids lithiate exclusively at C-4 when treated with 2.2 equivs of BuLi. The resulting dianions were quenched with a variety of electrophiles to provide 2-silylated-3-(hydroxymethyl)-substituted furans and 2-silylated-4-substituted 3-furoic acids in good to excellent yields. Removal of the silyl group (n-Bu4NF) provided a variety of 4-substituted-3-(hydroxymethyl)furans and methyl 4-substituted-3-furoates, respectively. The latter esters were prepared due to difficulties encountered in isolating 4-substituted-3-furoic acids. The site of lithiation was altered by protecting the 3-hydroxyl group with a triethylsilane. Lithiation of 2-silylated-3-(((triethylsilyl)oxy)methyl)furan with 1.2 equivs of BuLi followed by the addition of electrophiles provided 2-silylated-3-(((triethylsilyl)oxy)methyl)-5-substituted furan rings. Subsequent removal of both silyl groups provided 2,4-disubstituted furan rings in moderate to good yields. A rationale is provided to explain why protection of the hydroxyl group at C-3 leads to a change in lithiation from the C-4 to the C-5 position of the furan ring. In addition, an explanation for the observed effect of adding HMPA or LiCl to the solution during the lithiation of 2-(tert-butyldimethylsilyl)-3-(hydroxymethyl)furan is provided.
• A general approach to 5-substitution of 3-furaldehydes
  作者：Gary C. M. Lee、Judy M. Holmes、Dale A. Harcourt、Michael E. Garst

  DOI：10.1021/jo00037a032

  日期：1992.5

  Herein we report the details of the conversion of 3-furaldehyde into 2-substituted 4-furaldehydes and the transformations of 2-substituted 4-furaldehydes and 4-substituted 3-furaldehydes into tri- and tetrasubstituted furans. We have developed a new disubstituted furan synthesis by applying metalation to the direct conversion of 3-substituted furans into 2,4-disubstituted furans. In situ protection of 3-furaldehyde with lithium morpholide followed by metalation at the C-5 position and quenching with several electrophiles affords 2-substituted 4-furaldehydes in 30-70% yield. The electrophiles include chlorosilanes, chlorostannanes, aldehydes, ketones, and primary iodides. This work provides a general route to a previously relatively inaccessible furan substitution pattern and is the first example of selective metalation at the C-5 position of 3-substituted furans. Other bulky a-alkoxy substituents at C-3 direct remote metalation to C-5 of furan. We examined other 3-furaldehyde metalations. The amino alkoxide intermediate derived from lithio N,N,N'-trimethylethylenediamine and 3-furaldehyde, when treated with BuLi and electrophiles, provided a product mixture which included metalation at the C-4 position of 3-furaldehyde. Several approaches to enhance this unusual C-4 metalation were unsuccessful. Using this amino alkoxide-metalation chemistry, 4-alkyl- or 4-phenyl-3-furaldehyde could be substituted at C-2 or C-5 selectively. Finally we converted trisubstituted furans into tetrasubstituted furans with metalation/electrophilic trapping.
• An Enantioselective Approach to Furanoeremophilanes: (+)-9-Oxoeuryopsin
  作者：Ana L. Silva、Rubén A. Toscano、Luis A. Maldonado

  DOI：10.1021/jo400399q

  日期：2013.6.7

  An enantioselective total synthesis of the furanoeremophilane sesquiterpene (+)-9-oxoeuryopsin 1 is reported. The synthesis involves as a key step a copper(II) triflate catalyzed tandem asymmetric conjugate addition of AlMe3 to 2-methyl-2-cyclohexen-1-one with the Feringa (S,R,R)-phosphoramidite binaphthol ligand, followed by aldol condensation of the resulting aluminum enolate with 4-methyl-3-furaldehyde 4. This tandem transformation has not been previously reported with a 2-substituted-2-cyclohexen-1-one. Conventional functional group manipulations completed the synthesis.
• Preparation of 3-substituted 4-methylfurans: 3-iodo-4-methyl- and 3-formyl-4-methylfuran
  作者：Hans J. Reich、Richard E. Olson

  DOI：10.1021/jo00387a043

  日期：1987.5
• REICH H. J.; OLSON R. E., J. ORG. CHEM., 52,(1987) N 11, 2315-2317
  作者：REICH H. J.、 OLSON R. E.

  DOI：——

  日期：——