2-Methyl-5,6-dihydro-α-pyrano-6,6-dicarbonsaeure-diethylester | 36749-08-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 2-Methyl-5,6-dihydro-α-pyrano-6,6-dicarbonsaeure-diethylester
• 英文别名: 6-methyl-3,6-dihydro-pyran-2,2-dicarboxylic acid diethyl ester；2H-Pyran-2,2-dicarboxylic acid, 3,6-dihydro-6-methyl-, diethyl ester；diethyl 2-methyl-2,5-dihydropyran-6,6-dicarboxylate
• CAS: 36749-08-3
• 化学式: C₁₂H₁₈O₅
• 分子量: 242.272
• InChiKey: BNMASBYBVUTQBG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-Methyl-5,6-dihydro-α-pyrano-6,6-dicarbonsaeure-diethylester 在 platinum on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 生成 2,2-dicarboethoxy-6-methyltetrahydropyran
  参考文献：
  名称：

  Carbon-13 NMR spectra of saturated heterocycles: XI—Tetrahydropyrans (oxanes)

  摘要：

  AbstractThe 13C NMR spectra of 62 oxanes (tetrahydropyrans) with and without methyl substituents at various ring positions, some of them bearing in addition (or instead) ethyl, vinyl, ethynyl, carbomethoxy and methylol substituents at C‐2, have been recorded, and the 294 resulting chemical shifts have been correlated by multiple linear regression analysis. Axial and equatorial α‐, β‐, γ‐, δ‐, gem‐ and vic‐parameters for shifts caused by methyl groups at all ring positions, and similar parameters for Et,—CHCH2,—CCH, CO2Me and CH2OH groups at C‐2, are reported. Standard deviations of the parameters are, in most cases, within 0.3 ppm and the agreement of calculated and experimental shifts is excellent. This is probably the largest parameter set of this type extant. 13C NMR spectra of a number of additional substituted tetrahydropyrans, and of 3,6‐dihydro‐2H‐pyrans and 3,4‐dihydro‐2H‐pyrans, are tabulated and discussed.

  DOI：

  10.1002/omr.1270210205
• 作为产物：
  描述：

  反-1,3-戊二烯 、 酮基丙二酸二乙酯 以60%的产率得到2-Methyl-5,6-dihydro-α-pyrano-6,6-dicarbonsaeure-diethylester
  参考文献：
  名称：

  不对称狄尔斯-阿尔德反应：薄荷醇铝和镧系手性催化剂的比较

  摘要：

  通过Diels-Alder反应与手性催化剂合成的一些二氢吡喃羧酸盐显示对映体过量，对于薄荷醇铝，对映体过量高达16％，对于手性镧系元素催化剂，对映体过量高达64％。

  DOI：

  10.1039/c39870000676

文献信息

• Generation of ester enolates by reductive a-deacetoxylation
  作者：Simon N. Pardo、Subrata Ghosh、Robert G. Salomon

  DOI：10.1016/s0040-4039(01)90468-x

  日期：1981.1

  Diethyl allylmalonates or 2-arylalkanoic esters are prepared in good yield by reductive α-deoxygenation of the corresponding α-acetoxy or α-alkony esters. Since the intermediate ester enolates are generated under aprotic conditions, a one pot reductive-alkylation is also possible. One application of this procedure allows diethyl oxomalonate to serve as a conjunctive reagent for stitching together an

  烯丙基丙二酸二乙酯或2-芳基链烷酸酯可以通过相应的α-乙酰氧基或α-链烷酸酯的还原α-脱氧反应以高收率制备。由于中间体酯烯醇化物是在非质子条件下产生的，因此一锅还原烷基化也是可能的。该方法的一种应用是使恶臭丙二酸二乙酯用作结合剂，以将链烯和具有丙二酰基的卤代烷缝合在一起。
• Carbon-13 NMR spectra of saturated heterocycles: XI—Tetrahydropyrans (oxanes)
  作者：Ernest L. Eliel、Muthiah Manoharan、K. Michal Pietrusiewicz、Karl D. Hargrave

  DOI：10.1002/omr.1270210205

  日期：1983.2

  AbstractThe 13C NMR spectra of 62 oxanes (tetrahydropyrans) with and without methyl substituents at various ring positions, some of them bearing in addition (or instead) ethyl, vinyl, ethynyl, carbomethoxy and methylol substituents at C‐2, have been recorded, and the 294 resulting chemical shifts have been correlated by multiple linear regression analysis. Axial and equatorial α‐, β‐, γ‐, δ‐, gem‐ and vic‐parameters for shifts caused by methyl groups at all ring positions, and similar parameters for Et,—CHCH2,—CCH, CO2Me and CH2OH groups at C‐2, are reported. Standard deviations of the parameters are, in most cases, within 0.3 ppm and the agreement of calculated and experimental shifts is excellent. This is probably the largest parameter set of this type extant. 13C NMR spectra of a number of additional substituted tetrahydropyrans, and of 3,6‐dihydro‐2H‐pyrans and 3,4‐dihydro‐2H‐pyrans, are tabulated and discussed.
• Asymmetric Diels–Alder reaction: comparison of menthoxyaluminium and lanthanide chiral catalysts
  作者：Miguel Quimpère、Krzysztof Jankowski

  DOI：10.1039/c39870000676

  日期：——

  Some dihydropyran carboxylates synthesized via the Diels–Alder reaction with chiral catalysts display an enantiomeric excess of up to 16% for menthoxyaluminium and up to 64% for chiral lanthanide catalysts.

  通过Diels-Alder反应与手性催化剂合成的一些二氢吡喃羧酸盐显示对映体过量，对于薄荷醇铝，对映体过量高达16％，对于手性镧系元素催化剂，对映体过量高达64％。