tert-butyl((12,12-dimethoxydodecyl)oxy)dimethylsilane | 920753-78-2

• 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: tert-butyl((12,12-dimethoxydodecyl)oxy)dimethylsilane
• 英文别名: Tert-butyl[(12,12-dimethoxydodecyl)oxy]dimethylsilane；tert-butyl-(12,12-dimethoxydodecoxy)-dimethylsilane
• CAS: 920753-78-2
• 化学式: C₂₀H₄₄O₃Si
• 分子量: 360.653
• InChiKey: IYGYHTROSNNHIZ-UHFFFAOYSA-N

物化性质

• 沸点：
  375.8±12.0 °C(Predicted)
• 密度：
  0.871±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.53
• 重原子数：
  24
• 可旋转键数：
  16
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl((12,12-dimethoxydodecyl)oxy)dimethylsilane 以 二氯甲烷 为溶剂， 反应 4.5h， 生成 13-(tert-butyldimethylsilyloxy)-2-methoxytridecanenitrile
  参考文献：
  名称：

  非酸性条件下乙缩醛与各种碳亲核试剂的反应：C ？通过吡啶鎓盐形成C键

  摘要：

  已经开发出乙醛与碳亲核试剂通过通过用TESOTf-2,4,6-可力丁或2,2'-联吡啶基处理乙缩醛而生成的吡啶鎓类盐进行的轻度取代反应。各种碳亲核试剂，例如有机铜酸酯，甲硅烷基烯醇醚，烯胺等，与吡啶鎓盐类反应生成高收率的相应取代产物。反应在非常温和的条件下（非酸性条件）进行，因此在反应过程中可以耐受酸敏感性官能团。此外，只有缩醛可以形成吡啶鎓盐，并在存在缩酮的情况下与亲核试剂反应。这种不寻常的选择性与在酸性条件下进行的常规方法形成对比。

  DOI：

  10.1002/asia.201100812
• 作为产物：
  描述：

  12-羟基-1-十二烷醛二甲基缩醛 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以434 mg的产率得到tert-butyl((12,12-dimethoxydodecyl)oxy)dimethylsilane
  参考文献：
  名称：

  Organic Chemistry Using Weakly Electrophilic Salts:  Efficient Formation of O,O-Mixed, O,S- and N,O-Acetals

  摘要：

  A mild and efficient method for the preparation of O,O-mixed, O,S- and N,O-acetals from symmetrical O,O-acetals has been developed. Thus, the treatment of symmetrical O,O-acetals with TESOTf and 2,4,6-collidine formed weakly electrophilic collidinium salts. The addition of nucleophiles, such as an alcohol, lithium thioxide, and sodium azide, to the salts afforded the corresponding O,O-mixed, O,S- and N,O-acetals in good yields. The reaction proceeded under weakly basic conditions. No overreaction then occurred and many acid-labile functional groups could remain intact.

  DOI：

  10.1021/jo071187g

文献信息

• Effects of Phosphorus Substituents on Reactions of α-Alkoxyphosphonium Salts with Nucleophiles
  作者：Akihiro Goto、Kazuki Otake、Ozora Kubo、Yoshinari Sawama、Tomohiro Maegawa、Hiromichi Fujioka

  DOI：10.1002/chem.201200480

  日期：2012.9.3

  The effects of phosphorus substituents on the reactivity of α‐alkoxyphosphonium salts with nucleophiles has been explored. Reactions of α‐alkoxyphosphonium salts, prepared from various acetals and tris(o‐tolyl)phosphine, with a variety of nucleophiles proceeded efficiently. These processes represent the first examples of high‐yielding nucleophilic substitution reactions of α‐alkoxyphosphonium salts

  研究了磷取代基对α-烷氧基salts盐与亲核试剂反应性的影响。由各种缩醛和三（邻甲苯基）膦制备的α-烷氧基phosph盐与各种亲核试剂的反应有效进行。这些过程代表了α-烷氧基phosph盐高亲核取代反应的第一个例子。这些盐的反应性分别取决于空间和电子因素之间的平衡，分别由锥角θ和CO拉伸频率ν（分别为空间和电子参数）表示。此外，由Ph 3衍生的α-烷氧基phosph盐的新反应观察到带有格氏试剂的P在O 2的存在下发生，以高收率得到醇。为此过程提出了一种自由基机理，该机理已获得同位素标记和自由基抑制实验的支持。
• Highly Chemoselective Alkylation of Acetals Using TESOTf-2,4,6-Collidine-Gilman Reagent Combination
  作者：Hiromichi Fujioka、Yasuyuki Kita、Takashi Okitsu、Yoshinari Sawama、Takuya Ohnaka

  DOI：10.1055/s-2006-951509

  日期：2006.11

  A new alkylation method of acetals has been developed by the reaction of the cationic intermediates, obtained by TESOTf-2,4,6-collidine treatment of acetals, followed by a Gilman reagent. The feature of the method is high chemoselectivity, which could not be attained by previously reported methods. Reaction proceeds under weakly basic conditions that acid-labile functional groups can tolerate.

  通过TESOTf-2,4,6-可力丁处理缩醛得到的阳离子中间体和吉尔曼试剂反应，开发了一种新的缩醛烷基化方法。该方法的特点是化学选择性高，这是以前报道的方法无法达到的。反应在酸不稳定官能团可以耐受的弱碱性条件下进行。
• Highly Discriminative and Chemoselective Deprotection/Transformations of Acetals with the Combination of Trialkylsilyl Triflate/2,4,6-Collidine
  作者：Reiya Ohta、Nao Matsumoto、Yoshifumi Ueyama、Yuichi Kuboki、Hiroshi Aoyama、Kenichi Murai、Mitsuhiro Arisawa、Tomohiro Maegawa、Hiromichi Fujioka

  DOI：10.1021/acs.joc.8b00675

  日期：2018.6.15

  developed a chemoselective deprotection and nucleophilic substitution of acetals from aldehydes in the presence of ketals. This article describes the highly discriminative and chemoselective transformations of acetals bearing different substitution patterns, different types of acetals, as well as mixed acetals. These reactions can achieve the transformations that cannot be attained by conventional methods,

  缩醛是羰基官能团最有用的保护基。除了保护作用外，它们还可用作羰基官能团的合成子。以前，我们开发了在缩酮存在下从醛类中缩醛的化学选择性脱保护和亲核取代。本文介绍了具有不同取代模式，不同类型的缩醛以及混合缩醛的缩醛的高判别和化学选择性转化。这些反应可以实现常规方法无法实现的转化，其结果强烈表明，R 3 SiOTf / 2,4,6-可力丁的组合可促进这种前所未有的现象。
• Organic Chemistry Using Weakly Electrophilic Salts: The Reaction with Nitrogen Nucleophiles
  作者：Hiromichi Fujioka、Yasuyuki Kita、Ozora Kubo、Kento Senami、Kazuhisa Okamoto、Takashi Okitsu

  DOI：10.3987/com-08-s(d)69

  日期：——

  The reaction of electrophilic salts, which were obtained by the treatment of acetals with TESOTf*center dot 2,4,6-collidine, with nitrogen nucleophiles was studied in detail. Treatment of the salts with potassium phthalimide afforded the corresponding N,O-acetals in good yields. The use of hydrazine in place of potassium phthalimide gave the corresponding hydrazones. The reaction is very mild and chemoselective, and acid-labile functional groups can tolerate these conditions.