4,5-(2,3-dibromo-1,4-dimethoxybenzo)-3,6-dihydro-1,2-oxathiin-2-oxide | 196880-73-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4,5-(2,3-dibromo-1,4-dimethoxybenzo)-3,6-dihydro-1,2-oxathiin-2-oxide
• 英文别名: 6,7-Dibromo-5,8-dimethoxy-1,4-dihydro-2,3lambda4-benzoxathiine 3-oxide；6,7-dibromo-5,8-dimethoxy-1,4-dihydro-2,3λ4-benzoxathiine 3-oxide
• CAS: 196880-73-6
• 化学式: C₁₀H₁₀Br₂O₄S
• 分子量: 386.061
• InChiKey: QNTQWGIXWCCSIX-UHFFFAOYSA-N

物化性质

• 熔点：
  136-138 °C
• 沸点：
  493.2±55.0 °C(Predicted)
• 密度：
  2.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  64
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4,5-(2,3-dibromo-1,4-dimethoxybenzo)-3,6-dihydro-1,2-oxathiin-2-oxide 在 硫酸 、 硝酸 作用下， 以 四氯化碳 为溶剂， 反应 12.0h， 生成 5-(4-nitrophenyl)-5-aza-11,12-dibromotricyclo[7.4.0.0^3,7]trideca-1(9),11-diene-4,6,10,13-tetraone
  参考文献：
  名称：

  摘要：

  A six-step synthesis was used to prepare a 5,6-dibromobenzoquinone-phenyl maleimide adduct (8). The structure of (8) and four of the intermediates are described. This dibromide is used as the starting material for the synthesis of 2-amino-1,2,3-triazoles which reacts with aldehydes and ketones to prepare materials for nonlinear optical studies. The crystal structures of five compounds were determined. (2) Pbca, a = 8.4183(7), b = 7.2479(7), c = 31.272(3) Angstrom; (3) P-1, a = 8.2023(8), b = 8.8130(8), c = 9.3555(9) Angstrom, alpha = 61.517(1), beta = 73.630(1), gamma = 86.788(2)degrees; (4) P2(1)/c, a = 11.181(1), b = 7.9157(7), c = 15.248(1) Angstrom, beta = 90.691(2)degrees; (7) Pbca, a = 10.300(1), b = 20.184(3), c = 23.469(3) Angstrom; (8) P2(1)/n, a = 6.8975(6), b = 17.877(2), c = 14.089(1) Angstrom, beta = 91.968(2)degrees.

  DOI：

  10.1023/a:1020287802834
• 作为产物：
  描述：

  5,6-Dibromo-1,4-dimethoxy-2,3-dimethyl-cyclohexa-1,3-diene 在 四丁基溴化铵 、 rongalite 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以70%的产率得到4,5-(2,3-dibromo-1,4-dimethoxybenzo)-3,6-dihydro-1,2-oxathiin-2-oxide
  参考文献：
  名称：

  Reaction of C₆₀ with Sultines:  Synthesis, Electrochemistry, and Theoretical Calculations of Organofullerene Acceptors

  摘要：

  The [4 + 2] cycloaddition reaction of o-quinodimethanes, generated in situ from 4,5-benzo-3,6-dihydro-1,2-oxathiin 2-oxides (10a,b, 13, and 19) (sultines), to [60]fullerene is described. Sultines are readily accesible from the commercially available rongalite and smoothly generate o-quinodimethanes, by extrusion of sulfur dioxide, which are efficiently trapped by the active dienophile C-60. The cycloadducts formed (21a-d) were further oxidized to the respective p-benzoquinone-containing fullerenes 23a-c. The temperature dependent H-1 NMR spectra show a dynamic process of the methylene protons. The activation free energy determined for the boat-to-boat inversion (11.3-11.6 kcal/mol) is remarkably lower than that obtained for other related carbocyclic or heterocyclic analogues. Semiempirical PM3 calculations show that the geometrical features and not the electronic properties of the organic addend in 23 are responsible for the low activation energy barriers. A linear correlation is found between the activation energy barriers and the length of the C62-C63 bond. The electrochemical properties of 23a-c have been rationalized on the basis of DFT-B3P86/3-21G calculations. The attachment of the first electron in the reduction process takes place in either the C-60 cage or the organic addend depending upon the nature of the substituents on the p-benzoquinone ring, which controls the relative energy of the LUMO of the p-benzoquinone moiety. A full agreement between the theoretical predictions and the electrochemical measurements is found.

  DOI：

  10.1021/jo9706436