1,1-Dibromo-3-<(phenylmethoxy)methoxy>-1-butene | 144108-83-8

• 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: 1,1-Dibromo-3-<(phenylmethoxy)methoxy>-1-butene
• 英文别名: 4,4-Dibromobut-3-en-2-yloxymethoxymethylbenzene
• CAS: 144108-83-8
• 化学式: C₁₂H₁₄Br₂O₂
• 分子量: 350.05
• InChiKey: HFNJJHXNFPCZTD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  1,1-Dibromo-3-<(phenylmethoxy)methoxy>-1-butene 在 正丁基锂 、 1,1,2-三氯三氟乙烷（CFC-113） 、 溶剂黄146 、 zinc(II) chloride 作用下， 反应 18.0h， 生成 1-Chloro-3-<(phenylmethoxy)methoxy>-1-butene
  参考文献：
  名称：

  Reactions of 1,1-dihaloalkenes with triorganozincates: a novel method for the preparation of alkenylzinc species associated with carbon-carbon bond formation

  摘要：

  Lithium trialkylzincates react with 1,1-dibromoalkenes 1 and 1-bromo-1-chloroalkenes 2 at -85-degrees-C in THF to give 1-bromoalkenes 5 and 1-chloroalkenes 7, respectively, upon hydrolysis. The intermediate (1-haloalkenyl)zincates 4 and 6 are stable at low temperature but, when allowed to warm to 0-degrees-C, they undergo a 1,2-alkyl migration reaction to afford alkenylzinc species 10. A variety of alkylation products 11 are obtained by the hydrolysis of 10. In the presence of (Ph3P)2Pd (5 mol%), alkenylzinc species 10 react smoothly with organic halides (AcCl, EtOCOCl, CH2=CH-(Me)Br, PhBr) to yield the corresponding coupling products 13-16.

  DOI：

  10.1021/jo00070a027
• 作为产物：
  描述：

  四溴化碳 、 O-<(Benzyloxy)methyl>lactaldehyde 在 三苯基膦 作用下， 以 苯 为溶剂， 以79%的产率得到1,1-Dibromo-3-<(phenylmethoxy)methoxy>-1-butene
  参考文献：
  名称：

  Reactions of 1,1-dihaloalkenes with triorganozincates: a novel method for the preparation of alkenylzinc species associated with carbon-carbon bond formation

  摘要：

  Lithium trialkylzincates react with 1,1-dibromoalkenes 1 and 1-bromo-1-chloroalkenes 2 at -85-degrees-C in THF to give 1-bromoalkenes 5 and 1-chloroalkenes 7, respectively, upon hydrolysis. The intermediate (1-haloalkenyl)zincates 4 and 6 are stable at low temperature but, when allowed to warm to 0-degrees-C, they undergo a 1,2-alkyl migration reaction to afford alkenylzinc species 10. A variety of alkylation products 11 are obtained by the hydrolysis of 10. In the presence of (Ph3P)2Pd (5 mol%), alkenylzinc species 10 react smoothly with organic halides (AcCl, EtOCOCl, CH2=CH-(Me)Br, PhBr) to yield the corresponding coupling products 13-16.

  DOI：

  10.1021/jo00070a027

文献信息

• Stereochemistry in carbenoid formation by bromine/lithium and bromine/zinc exchange reactions of gem-dibromo compounds
  作者：Toshiro Harada、Takeshi Katsuhira、Kazuhiro Hattori、Akira Oku

  DOI：10.1016/s0040-4020(01)85284-4

  日期：——

  bromine/lithium and bromine/zinc exchange reactions take place preferentially at the sterically more hindered bromine atom of the starting gem-dibromo compounds. The observation is rationalized by an exchange mechanism involving a linear transition state of either an ate complex formation or an SN2 reaction at the more hindered bromine atom where strain relief due to the elongation of the carbon-bromine bond is

  通过宝石的溴/金属交换反应生成锂和锌酸类胡萝卜素的立体化学已经研究了分别与BuLi和三有机锌酸锂形成的二溴化合物。已证明，衍生自1，1-二溴烯烃的锂和锌酸酯类化合物在低温下是构型稳定的，而在未反应的起始二溴烯烃的存在下，锂类化合物而不是锌酸酯类化合物在类胡萝卜素碳上容易进行异构化。在起始二溴环丙烷存在下，衍生自1,1-二溴环丙烷的Zincate类胡萝卜素在类胡萝卜素碳上缓慢进行异构化。事实证明，锂和锌酸盐类胡萝卜素的异构化反应是通过涉及类胡萝卜素与起始二溴化合物之间的溴/金属交换的机理进行的。在1,1-二溴烯烃在热力学条件下的反应中观察到锂类胡萝卜素的高度立体选择性形成。在动力学控制的条件下，溴/锂和溴/锌的交换反应均优先发生在起始位点的空间受阻溴原子上宝石-二溴化合物。通过交换机制合理化该观察，该交换机制涉及在受阻溴原子处的盐配合物形成或S N 2反应的线性过渡态，在这种情况下，由于碳-溴键的延长，应力会减轻。
• Reactions of 1,1-dihaloalkenes with triorganozincates: a novel method for the preparation of alkenylzinc species associated with carbon-carbon bond formation
  作者：Toshiro Harada、Takeshi Katsuhira、Daiji Hara、Yasuo Kotani、Keiji Maejima、Ryousuke Kaji、Akira Oku

  DOI：10.1021/jo00070a027

  日期：1993.8

  Lithium trialkylzincates react with 1,1-dibromoalkenes 1 and 1-bromo-1-chloroalkenes 2 at -85-degrees-C in THF to give 1-bromoalkenes 5 and 1-chloroalkenes 7, respectively, upon hydrolysis. The intermediate (1-haloalkenyl)zincates 4 and 6 are stable at low temperature but, when allowed to warm to 0-degrees-C, they undergo a 1,2-alkyl migration reaction to afford alkenylzinc species 10. A variety of alkylation products 11 are obtained by the hydrolysis of 10. In the presence of (Ph3P)2Pd (5 mol%), alkenylzinc species 10 react smoothly with organic halides (AcCl, EtOCOCl, CH2=CH-(Me)Br, PhBr) to yield the corresponding coupling products 13-16.