1-(p-methylphenyl)-3,3-bis(trifluoromethyl)-3H-2,1-benzoxabismole | 143494-23-9

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1-(p-methylphenyl)-3,3-bis(trifluoromethyl)-3H-2,1-benzoxabismole
• 英文别名: 1-(4-methylphenyl)-3,3-bis(trifluromethyl)-3H-2,1-benzoxabismole
• CAS: 143494-23-9
• 化学式: C₁₆H₁₁BiF₆O
• 分子量: 542.234
• InChiKey: ODVLXGGFBDHVRP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  24.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-(p-methylphenyl)-3,3-bis(trifluoromethyl)-3H-2,1-benzoxabismole 以 乙醚 、 正己烷 为溶剂， 生成 1-(2,6-bis[(dimethylamino)methyl]-4-tert-butylphenyl)-3,3-bis-(trifluoromethyl)-3H-2,1-benzoxabismole
  参考文献：
  名称：

  Yamamoto, Yohsuke; Chen, Xiang; Kojima, Satoshi, Journal of the American Chemical Society, 1995, vol. 117, # 14, p. 3922 - 3932

  摘要：

  DOI：
• 作为产物：
  描述：

  3,3-bis(trifluoromethyl)-1,1,1-tris(p-methylphenyl)-3H-2,1-benzoxabismole 在 BuLi 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以90.3%的产率得到1-(p-methylphenyl)-3,3-bis(trifluoromethyl)-3H-2,1-benzoxabismole
  参考文献：
  名称：

  具有双齿配体（12-Bi-6）的六配位有机铋化合物的合成与结构

  摘要：

  The thermally stable 12-Bi-6 compound 3-Li+, {(o-C6H4C(CF3)20)2}Bi(p-CH3C6H4)2-Li+, was synthesized. F-19 NMR of 3-Li+ showed a pair of quartets at room temperature but showed a singlet after addition of 12-crown-4 to the solution. The result indicated an important role of the Li+ on the structure of the ate complex, and the structure of the Li salt was assigned as 3A, bearing two cis oxygens, two cis p-tolyl groups, and two trans carbons at ligation sites about the central bismuth atom. The structure of the ate complex in the presence of 12-crown-4 was assigned as 3C, bearing two cis oxygens, two trans p-tolyl groups, and two cis carbons at ligation sites. Compounds 3 were stable up to 150-degrees-C, but the pair of quartets coalesced at 70-degrees-C and the activation energy of the equilibrium between the CF3 groups was calculated to be 18 kcal mol-1 at 70-degrees-C. Bismuth-oxygen bond cleavage followed by pseudorotation was suggested for the coalescence. Compounds 3 were inert to electrophilic reagents such as p-(trifluoromethyl) benzoyl chloride. Water reacted with 3 to give an alcohol 17. The alcohol was unstable at room temperature and cyclized with elimination of toluene to afford a 10-Bi-5 (12). Intramolecularly coordinated 12-Bi-6 compounds 18, (o-C6H4C(CF3)20)BiAr2(o-C6H4CR2X) { Ar, R, X: 18a p-CH3C6H4, CF3, CH3O; 18b p-CF3C6H4, CF3, CH3O; 18c p-CH3C6H4, H, (CH3)2N; 18d p-CF3C6H4, H, (CH3)2N}, were synthesized, three of which were structurally determined by X-ray analysis. The structures were all cis geometry. The synthesis and stability of 12-Bi-6 ate complexes 5, (o-C6H4C(CF3)20)Bi(P-CH3C6H4)3R-Li+, were also described.

  DOI：

  10.1021/om00032a060

文献信息

• Synthesis, halogenolysis, and crystal structure of hypervalent organobismuth compounds (10-Bi-5)
  作者：Xiang Chen、Keisuke Ohdoi、Yohsuke Yamamoto、Kinya Akiba

  DOI：10.1021/om00029a047

  日期：1993.5

  The stable 10-Bi-5 compounds (o-C6H4C(CF3)20)BiAr2R(3(Ar,R): 3a,p-CH3CrH4,p-CH3C6H4; 3b, P-CF3C6H4, p-CF3C6H4; 3c, p-FC6H4, p-FC6H4; 3d, p-CH3C6H4, p-CF3C6H4; 3e, p-CF3C6H4, p-CH3C6H4;3f,p-CH3Cr6H4,PhC=C;3g,p-CH3C6H4,Me) were synthesized. The X-ray structures of 3a,fg showed distorted-trigonal-bipyramidal geometries, and the electronegative apical PhC=C ligand of 3f made the apical Bi-O bond (2.243(3) angstrom) shorter than the Bi-O bond of 3a,g (2.323(4) angstrom in 3a and 2.328(7) angstrom in 3g). Halogenolysis of 3 with sulfuryl chloride or pyridinium bromide perbromide gave the five-coordinate bismuth compounds (o-C6H4C(CF3)20)BiArlAr2X (6 (Ar1, Ar2, X): 6a,p-CH3C6H4,p-CH3C6H4,Cl;6b,p-CF3C6H4,p-CF3C6H4,Cl;6c,p-FC6H4, p-FC6H4, Cl; 6d, p-CH3C6H4, p-CH3C6H4, Br; 6e, p-CH3C6H4, p-CF3C6H4, Cl; 6f, p-CH3C6H4, p-CF3C6H4, Br) in good to quantitative yield with apical covalent Bi-halogen bonds which were clearly shown by the X-ray analysis of 6a,b,d,e. The reactivity order of 3 for the halogenolysis was as follows: PhC=C-Bi > Me-Bi > p-CH3CrH4-Bi > p-CF3C6H4-Bi. Direct halogenolysis of the bismuth-carbon bond was suggested. The variable-temperature F-19 NMR of unsymmetrically substituted 6e,f did not show coalescence of the CF3 groups up to 170-degrees-C in a dilute solution of toluene-d8, and the energies of inversion at the bismuth atom should be higher than 21 kcal mol-1 at 170-degrees-C.