3-trimethylsilanoxybutanoic acid trimethylsilanyl ester | 55133-94-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-trimethylsilanoxybutanoic acid trimethylsilanyl ester
• 英文别名: 3-trimethylsilyloxybutyric acid trimethylsilyl ester；3-trimethylsiloxybutyric acid trimethylsilyl ester；Butanoic acid, 3-[(trimethylsilyl)oxy]-, trimethylsilyl ester；trimethylsilyl 3-trimethylsilyloxybutanoate
• CAS: 55133-94-3
• 化学式: C₁₀H₂₄O₃Si₂
• 分子量: 248.47
• InChiKey: YWRIHOYCAHATJN-UHFFFAOYSA-N

物化性质

• 沸点：
  220.5±23.0 °C(Predicted)
• 密度：
  0.902±0.06 g/cm3(Predicted)
• 保留指数：
  1160;1163;1166;1160;1164;1160;1160;1165.3

计算性质

• 辛醇/水分配系数(LogP)：
  2.99
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  频哪酮 、 3-trimethylsilanoxybutanoic acid trimethylsilanyl ester 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 以85%的产率得到2-tert-butyl-2,6-dimethyl-1,3-dioxan-4-one
  参考文献：
  名称：

  Bromination of 2,2,6-trialkyl-1,3-dioxan-4-ones. Application of the deuterium isotope effect to the synthesis of a chiral trialkyldioxinone

  摘要：

  Free-radical bromination (2 equiv of NBS) of 2-tert-butyl-2,6-dimethyl-1,3-dioxan-4-one (6a) gives the 2-bromomethyl product 7a. By contrast, bromination of 2-tert-butyl-2-methyl-1,3-dioxan-4-one (1) is reported to occur at the 6-position. Deuterium-labeling experiments established that 7a is formed by direct substitution at the 2-methyl group of 6a and not by abstraction of H-6 followed by hydrogen atom transfer from the 2-methyl group and bromination of the resultant primary radical 12. When 2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-dioxan-4-one (13) is reacted with 4 equiv of NBS, the course of the reaction is altered dramatically and the major product formed in high yield is dioxinone 16. Thus, a trideuteriomethyl group directs bromination away from the 2-methyl site to H-6. Bromination at the 6-position followed by loss of HBr, addition of Br2, and loss of a second HBr gives 16. Dioxinone 14, a valuable substrate for asymmetric induction studies, is formed in high yield by reductive debromination of 16. When (R)-3-hydroxybutyric acid is used in the preparation of 13, optically pure (-)-14 is obtained using the sequence described.

  DOI：

  10.1021/jo00048a039
• 作为产物：
  描述：

  三甲基氯硅烷 、 DL-3-羟基丁酸 以 四氢呋喃 为溶剂， 反应 12.0h， 以93%的产率得到3-trimethylsilanoxybutanoic acid trimethylsilanyl ester
  参考文献：
  名称：

  Bromination of 2,2,6-trialkyl-1,3-dioxan-4-ones. Application of the deuterium isotope effect to the synthesis of a chiral trialkyldioxinone

  摘要：

  Free-radical bromination (2 equiv of NBS) of 2-tert-butyl-2,6-dimethyl-1,3-dioxan-4-one (6a) gives the 2-bromomethyl product 7a. By contrast, bromination of 2-tert-butyl-2-methyl-1,3-dioxan-4-one (1) is reported to occur at the 6-position. Deuterium-labeling experiments established that 7a is formed by direct substitution at the 2-methyl group of 6a and not by abstraction of H-6 followed by hydrogen atom transfer from the 2-methyl group and bromination of the resultant primary radical 12. When 2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-dioxan-4-one (13) is reacted with 4 equiv of NBS, the course of the reaction is altered dramatically and the major product formed in high yield is dioxinone 16. Thus, a trideuteriomethyl group directs bromination away from the 2-methyl site to H-6. Bromination at the 6-position followed by loss of HBr, addition of Br2, and loss of a second HBr gives 16. Dioxinone 14, a valuable substrate for asymmetric induction studies, is formed in high yield by reductive debromination of 16. When (R)-3-hydroxybutyric acid is used in the preparation of 13, optically pure (-)-14 is obtained using the sequence described.

  DOI：

  10.1021/jo00048a039

文献信息

• Stereocontrolled synthesis of substituted tetrahydropyrans from 1,3-dioxan-4-ones
  作者：Nicos A. Petasis、Shao-Po Lu

  DOI：10.1016/0040-4039(95)02114-0

  日期：1996.1

  Conversion of aldehydes to 1,3-dioxan-4-ones, followed by methylenation with dimethyl titanocene gave the corresponding vinyl acetals which could undergo a stereocontrolled aluminum-mediated rearrangement to afford substituted tetrahydropyrans.

  将醛转化为1,3-二恶烷-4-酮，然后用二甲基二茂钛进行亚甲基化，得到相应的乙烯基缩醛，该缩醛可以进行立体控制的铝介导的重排，从而得到取代的四氢吡喃。
• WURTH, CLAUDINE;KUMPS, A.;MARDENS, Y., J. CHROMATOGR. BIOMED. APPL., 491,(1989) N, C. 186-192
  作者：WURTH, CLAUDINE、KUMPS, A.、MARDENS, Y.

  DOI：——

  日期：——
• DAOLIO, SERGIO;BONSEMBIANTE, MARIO;BITTANTE, GIOVANNI;RAMANZIN, MAURIZIO;+, J. AGR. AND FOOD CHEM., 37,(1989) N, C. 970-974
  作者：DAOLIO, SERGIO、BONSEMBIANTE, MARIO、BITTANTE, GIOVANNI、RAMANZIN, MAURIZIO、+

  DOI：——

  日期：——
• Bromination of 2,2,6-trialkyl-1,3-dioxan-4-ones. Application of the deuterium isotope effect to the synthesis of a chiral trialkyldioxinone
  作者：Gordon L. Lange、Michael G. Organ、Michael R. Roche

  DOI：10.1021/jo00048a039

  日期：1992.10

  Free-radical bromination (2 equiv of NBS) of 2-tert-butyl-2,6-dimethyl-1,3-dioxan-4-one (6a) gives the 2-bromomethyl product 7a. By contrast, bromination of 2-tert-butyl-2-methyl-1,3-dioxan-4-one (1) is reported to occur at the 6-position. Deuterium-labeling experiments established that 7a is formed by direct substitution at the 2-methyl group of 6a and not by abstraction of H-6 followed by hydrogen atom transfer from the 2-methyl group and bromination of the resultant primary radical 12. When 2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-dioxan-4-one (13) is reacted with 4 equiv of NBS, the course of the reaction is altered dramatically and the major product formed in high yield is dioxinone 16. Thus, a trideuteriomethyl group directs bromination away from the 2-methyl site to H-6. Bromination at the 6-position followed by loss of HBr, addition of Br2, and loss of a second HBr gives 16. Dioxinone 14, a valuable substrate for asymmetric induction studies, is formed in high yield by reductive debromination of 16. When (R)-3-hydroxybutyric acid is used in the preparation of 13, optically pure (-)-14 is obtained using the sequence described.

表征谱图