3-butenal dibenzylacetal | 223906-12-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-butenal dibenzylacetal
• 英文别名: 1-Phenylmethoxybut-3-enoxymethylbenzene；1-phenylmethoxybut-3-enoxymethylbenzene
• CAS: 223906-12-5
• 化学式: C₁₈H₂₀O₂
• 分子量: 268.356
• InChiKey: QYXYKSIXOXMMBI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-butenal dibenzylacetal 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以55%的产率得到2-(2,2-Bis-benzyloxy-ethyl)-oxirane
  参考文献：
  名称：

  Pentacoordinate Organoaluminum Chemistry:  Catalytic Efficiency of Me₃Al in the Epoxide Cleavage with Alkynyllithiums

  摘要：

  A new and highly effective catalytic method for epoxide alkynylations has been developed that involves the chelation-controlled alkylation of heterosubstituted epoxides with Me3Al via pentacoordinate organoalluminum complexes by taking advantage of the exceedingly high affinity of aluminum to oxygen. For example, reaction of epoxy ether, (l-benzyloxy)-3-butene oxide (1), in toluene with PhC=CLi under the influence of catalytic Me3Al (10 mol%) proceeded smoothly at O degrees C for 5 h to furnish the alkynylation product, l-(benzyloxy)-6-phenylhex-5-yn-3-ol, in 76% yield [cf. 3% without Me3Al catalyst; 78% with stoichiometric Me3Al under similar conditions]. This represents the first catalytic procedure for the amphiphilic alkylation of epoxides. The participation of pentacoordinate Me3Al complexes of epoxy ethers of type 1 is emphasized by comparing the reactivity with the corresponding simple epoxide, 5-phenyl-l-pentene oxide, which was not susceptible to nucleophile attack of PhC=CLi with catalytic Me3A1 under similar conditions. The pentacoordinate complex formation of Me3Al with epoxy ether 1 is characterized by low-temperature C-13 and Al-27 NMR spectroscopy. This approach is also applicable to the selective alkynylation of tosyl aziridines with adjacent ether functionality, which provides a promising method for amino alcohol synthesis.

  DOI：

  10.1021/ja9842464
• 作为产物：
  描述：

  4,4-二乙氧基-1-丁烯 、 苯甲醇 在 4-甲基苯磺酸吡啶 作用下， 以 苯 为溶剂， 反应 4.5h， 以70%的产率得到3-butenal dibenzylacetal
  参考文献：
  名称：

  Pentacoordinate Organoaluminum Chemistry:  Catalytic Efficiency of Me₃Al in the Epoxide Cleavage with Alkynyllithiums

  摘要：

  A new and highly effective catalytic method for epoxide alkynylations has been developed that involves the chelation-controlled alkylation of heterosubstituted epoxides with Me3Al via pentacoordinate organoalluminum complexes by taking advantage of the exceedingly high affinity of aluminum to oxygen. For example, reaction of epoxy ether, (l-benzyloxy)-3-butene oxide (1), in toluene with PhC=CLi under the influence of catalytic Me3Al (10 mol%) proceeded smoothly at O degrees C for 5 h to furnish the alkynylation product, l-(benzyloxy)-6-phenylhex-5-yn-3-ol, in 76% yield [cf. 3% without Me3Al catalyst; 78% with stoichiometric Me3Al under similar conditions]. This represents the first catalytic procedure for the amphiphilic alkylation of epoxides. The participation of pentacoordinate Me3Al complexes of epoxy ethers of type 1 is emphasized by comparing the reactivity with the corresponding simple epoxide, 5-phenyl-l-pentene oxide, which was not susceptible to nucleophile attack of PhC=CLi with catalytic Me3A1 under similar conditions. The pentacoordinate complex formation of Me3Al with epoxy ether 1 is characterized by low-temperature C-13 and Al-27 NMR spectroscopy. This approach is also applicable to the selective alkynylation of tosyl aziridines with adjacent ether functionality, which provides a promising method for amino alcohol synthesis.

  DOI：

  10.1021/ja9842464

文献信息

• [EN] POLY (ETHYLENE GLYCOL) CONTAINING CHEMICALLY DISPARATE ENDGROUPS<br/>[FR] POLY(ÉTHYLÈNE GLYCOL) CONTENANT DES ENDOGROUPES CHIMIQUEMENT DISPARATES
  申请人：INTEZYNE TECHNOLOGIES INC

  公开号：WO2007127473A2

  公开（公告）日：2007-11-08

  [EN] The present invention provides bifunctional polymers, methods of preparing the same, and intermediates thereto. These compounds are useful in a variety of applications including the PEGylation of biologically active molecules. The invention also provides methods of using said compounds and compositions thereof.
  [FR] L'invention concerne des polymères bifonctionnels, leurs méthodes d'obtention et des intermédiaires de ces polymères.Ces composés conviennent pour diverses applications, dont la PEGylation de molécules biologiquement actives. L'invention concerne également des méthodes d'utilisation de ces composés et des compositions obtenues à partir de ces composés.
• Pentacoordinate Organoaluminum Chemistry:  Catalytic Efficiency of Me₃Al in the Epoxide Cleavage with Alkynyllithiums
  作者：Takashi Ooi、Naoko Kagoshima、Hayato Ichikawa、Keiji Maruoka

  DOI：10.1021/ja9842464

  日期：1999.4.1

  A new and highly effective catalytic method for epoxide alkynylations has been developed that involves the chelation-controlled alkylation of heterosubstituted epoxides with Me3Al via pentacoordinate organoalluminum complexes by taking advantage of the exceedingly high affinity of aluminum to oxygen. For example, reaction of epoxy ether, (l-benzyloxy)-3-butene oxide (1), in toluene with PhC=CLi under the influence of catalytic Me3Al (10 mol%) proceeded smoothly at O degrees C for 5 h to furnish the alkynylation product, l-(benzyloxy)-6-phenylhex-5-yn-3-ol, in 76% yield [cf. 3% without Me3Al catalyst; 78% with stoichiometric Me3Al under similar conditions]. This represents the first catalytic procedure for the amphiphilic alkylation of epoxides. The participation of pentacoordinate Me3Al complexes of epoxy ethers of type 1 is emphasized by comparing the reactivity with the corresponding simple epoxide, 5-phenyl-l-pentene oxide, which was not susceptible to nucleophile attack of PhC=CLi with catalytic Me3A1 under similar conditions. The pentacoordinate complex formation of Me3Al with epoxy ether 1 is characterized by low-temperature C-13 and Al-27 NMR spectroscopy. This approach is also applicable to the selective alkynylation of tosyl aziridines with adjacent ether functionality, which provides a promising method for amino alcohol synthesis.