1,2-二溴二氟乙烯 | 359-21-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 中文名称: 1,2-二溴二氟乙烯
• 英文名称: (E/Z)-1,2-dibromo-1,2-difluoroethylene
• 英文别名: 1,2-dibromo-1,2-difluoroethene；1,2-Dibrom-1,2-difluor-aethylen；1,2-Difluor-1,2-dibrom-aethylen；1,2-Dibrom-1,2-difluor-aethen；α.β-Difluor-α.β-dibrom-aethylen
• CAS: 359-21-7
• 化学式: C₂Br₂F₂
• 分子量: 221.827
• InChiKey: HATFLOWGZBUEIE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险品标志：
  F
• 海关编码：
  2903799090

反应信息

• 作为反应物：
  描述：

  1,2-二溴二氟乙烯 、 sodium 2-ethoxyethoxide 以 乙二醇乙醚 为溶剂， 反应 1.0h， 以70%的产率得到2-ethoxyethyl bromofluoroacetate
  参考文献：
  名称：

  Nucleophilic reactions at vinylic center. 27. Vinylic substitution of 1,2-dibromo-1,2-difluoroethylene and tribromofluoroethylene. An intramolecular kBr/kF element effect and apparent inversion of configuration in SNV reactions

  摘要：

  The reactions of (E/Z)-1,2-dibromo-1,2-difluoroethylene (1) and of tribromofluoroethylene (2) with alkoxide ions and of 1 with p-toluenethiolate ion give multiplicity of products. The reaction of 1 with 1 equiv of NaOMe gives mainly a 2:1 mixture of the product of one bromine displacement, together with methyl dimethoxyacetate (3), methyl bromofluoroacetate (4), 1,1,2-trifluoro-2-bromoethyl ether (7), and 1,1-difluoro-1,2,2-trimethoxyethane (8). With 2 equiv of MeO- 3 and 4 are the main products, and at 130-degrees-C, dimethyl ether 5 is also formed. With EtOCH2CH2O- 1 gave 2-ethoxyethyl bromofluoroacetate (9), bis(2-ethoxyethyl) ether (10), and E/Z mixtures of the substitution products EtOCH2CH2OC(F)=C(F)Br (12) and EtOCH2CH2OC(Br)=C(F)Br (13). Reaction of 2 with excess RO- (R=Me, Et) gives alkyl dibromoacetates, while with 1 equiv of RO- only a bromine from the =C(F)Br carbon is displaced. Reaction of l with p-TolSNa in MeOH gives the reduction-substitution product p-TolSC(F)=CHF(18), together with (p-TolS)2(16) and p-TolSMe (17). The same reaction in DMSO gives E/Z mixtures of the product of displacement of one bromine (19) or two bromines (20). Formation of the products is rationalized by an initial nucleophilic attack on the vinylic carbon followed by leaving group expulsion, giving, e.g., 12, 13, 19, or 20. Hydrolysis of the intermediate or addition of HF to the initial substitution product gives saturated products, e.g., 3,4,7, or 8, while S(N)2 reactions on the ether oxygen give ethers 5 and 10. A bromophilic reaction gives the reduction-substitution product 18, while hydrolysis-decarboxylation leads to 17. The regiospecificity of the nucleophilic addition is due to polar and hyperconjugative effects. An intramolecular element effect k(Br)/k(F) Of >10 is reported for the first time in the reaction of 1 with EtOCH2CH2O-. This value and the absence of such effects in other reactions are consistent with a much higher nucleofugality from a -CC(F)Br system of Br- compared with F-. The E/Z compositions of 18-20 indicates an apparent inversion in their formation, but it is not known whether these compositions are thermodynamically or kinetically controlled.

  DOI：

  10.1021/jo00064a036
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 sodium ethanolate 作用下， 生成 1,2-二溴二氟乙烯
  参考文献：
  名称：

  Swarts, Chemisches Zentralblatt, 1897, vol. 68, # II, p. 1099

  摘要：

  DOI：
• 作为试剂：
  描述：

  pentacarbonyl [(N,N-dimethylamino)(2-thienyl)carbene]tungsten (0) 在 正丁基锂 、 1,2-二溴二氟乙烯 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以89%的产率得到pentacarbonyl[(N,N-dimethylamino)(5-bromo-2-thienyl)-carbene]tungsten(0)
  参考文献：
  名称：

  一种简便方法官能Aminocarbene配合：铬和钨Aminocarbene配合物的锂化

  摘要：

  噻吩和呋喃衍生aminocarbene络合物区域选择性由丁基锂在5位锂化，同时含吡咯基或苯基锂化aminocarbenes可以通过使用丁基锂溴锂交换反应来获得。这样制得的锂化aminocarbene络合物与烷基卤化物，醛，酮，酰基氯反应，DMF，赋予官能aminocarbene络合物通过其他方式难以进入的产量高。

  DOI：

  10.1021/om500182p

文献信息

• Swarts, Chemisches Zentralblatt, 1899, vol. 70, # I, p. 588
  作者：Swarts

  DOI：——

  日期：——
• Building block synthesis of predominantly (E) symmetrical and unsymmetrical 1,2-difluorostilbenes from 1,2-dibromo-1,2-difluoroethene
  作者：Said Eddarir、Mohammed Kajjout、Christian Rolando

  DOI：10.1016/j.tet.2013.10.067

  日期：2013.12

  An efficient synthesis of predominantly (E) symmetrical or unsymmetrical 1,2-difluorostilbenes based on the Suzuki-Miyaura palladium-catalyzed cross-coupling reaction of arylboronic acids with predominantly (E)-1,2-dibromo-1,2-difluoroethene in the presence of Cs2CO3 in toluene is described. The reaction preserved the stereochemistry of the building block and performed in good yield independently of the electron-withdrawing or electron-donating character of the substituents. (C) 2013 Elsevier Ltd. All rights reserved.
• Swarts, Chemisches Zentralblatt, 1899, vol. 70, # II, p. 281
  作者：Swarts

  DOI：——

  日期：——
• Nucleophilic reactions at vinylic center. 27. Vinylic substitution of 1,2-dibromo-1,2-difluoroethylene and tribromofluoroethylene. An intramolecular kBr/kF element effect and apparent inversion of configuration in SNV reactions
  作者：Bagrat A. Shainyan、Zvi Rappoport

  DOI：10.1021/jo00064a036

  日期：1993.6

  The reactions of (E/Z)-1,2-dibromo-1,2-difluoroethylene (1) and of tribromofluoroethylene (2) with alkoxide ions and of 1 with p-toluenethiolate ion give multiplicity of products. The reaction of 1 with 1 equiv of NaOMe gives mainly a 2:1 mixture of the product of one bromine displacement, together with methyl dimethoxyacetate (3), methyl bromofluoroacetate (4), 1,1,2-trifluoro-2-bromoethyl ether (7), and 1,1-difluoro-1,2,2-trimethoxyethane (8). With 2 equiv of MeO- 3 and 4 are the main products, and at 130-degrees-C, dimethyl ether 5 is also formed. With EtOCH2CH2O- 1 gave 2-ethoxyethyl bromofluoroacetate (9), bis(2-ethoxyethyl) ether (10), and E/Z mixtures of the substitution products EtOCH2CH2OC(F)=C(F)Br (12) and EtOCH2CH2OC(Br)=C(F)Br (13). Reaction of 2 with excess RO- (R=Me, Et) gives alkyl dibromoacetates, while with 1 equiv of RO- only a bromine from the =C(F)Br carbon is displaced. Reaction of l with p-TolSNa in MeOH gives the reduction-substitution product p-TolSC(F)=CHF(18), together with (p-TolS)2(16) and p-TolSMe (17). The same reaction in DMSO gives E/Z mixtures of the product of displacement of one bromine (19) or two bromines (20). Formation of the products is rationalized by an initial nucleophilic attack on the vinylic carbon followed by leaving group expulsion, giving, e.g., 12, 13, 19, or 20. Hydrolysis of the intermediate or addition of HF to the initial substitution product gives saturated products, e.g., 3,4,7, or 8, while S(N)2 reactions on the ether oxygen give ethers 5 and 10. A bromophilic reaction gives the reduction-substitution product 18, while hydrolysis-decarboxylation leads to 17. The regiospecificity of the nucleophilic addition is due to polar and hyperconjugative effects. An intramolecular element effect k(Br)/k(F) Of >10 is reported for the first time in the reaction of 1 with EtOCH2CH2O-. This value and the absence of such effects in other reactions are consistent with a much higher nucleofugality from a -CC(F)Br system of Br- compared with F-. The E/Z compositions of 18-20 indicates an apparent inversion in their formation, but it is not known whether these compositions are thermodynamically or kinetically controlled.
• Swarts, Chemisches Zentralblatt, 1897, vol. 68, # II, p. 1099
  作者：Swarts

  DOI：——

  日期：——