2-(trimethylstannyl)-1,3-xylyl-18-crown-5 | 114563-83-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 2-(trimethylstannyl)-1,3-xylyl-18-crown-5
• 英文别名: trimethyl(3,6,9,12,15-pentaoxabicyclo[15.3.1]henicosa-1(21),17,19-trien-21-yl)stannane
• CAS: 114563-83-6
• 化学式: C₁₉H₃₂O₅Sn
• 分子量: 459.17
• InChiKey: PWKNQWUWVLNFEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.33
• 重原子数：
  25.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  (2-(bromomagnesio)-1,3-xylylene)-18-crown-5 、 三甲基氯化锡 以 四氢呋喃 为溶剂， 生成 2-(trimethylstannyl)-1,3-xylyl-18-crown-5
  参考文献：
  名称：

  Intra-annular reactions of the (1,3-xylylene)-18-crown-5 system: synthesis and crystal structure of [2-(bromomagnesio)-1,3-xylylene]-18-crown-5, [2-(bromomercurio)-1,3-xylylene]-18-crown-5 and bis[(1,3-xylylene-18-crown-5)-2-yl]mercury

  摘要：

  The Grignard compound [2-(bromomagnesio)-1,3-xylylene]-18-crown-5 (4) was prepared from the aryllithium compound (2-lithio-1,3-xylylene)-18-crown-5 (9) and magnesium bromide. The crystal structure of 4 shows that it crystallizes without solvent and is coordinatively saturated (distorted octahedral) by complexation of the magnesium with four of the five crown ether oxygens.The 1:1 reaction of 9 with HgBr2 yielded the corresponding organomercury compound [2-(bromomercurio)-1,3-xylylene]-18-crown-5 (10), which crystallizes without solvent. Its crystal structure reveals that intramolecular Hg-O coordination occurs with two of the five oxygens, and only weak interaction with a third crown ether oxygen. Reaction of 10 with metallic magnesium lead to the symmetric compound bis[(1,3-xylylene-18-crown-5)-2-yl]mercury (11). The centrosymmetric crystal structure of 11 shows that the mercury is intramolecularly coordinated with only four of the ten oxygens; the mercury atom is completely shielded by the crown ether rings. This shielding is probably the reason for the failure to bring about reaction of 11 with magnesium to give the corresponding diarylmagnesium compound.The crown ether Grignard 4 was treated with deuterium oxide, chlorotrimethylstannane, iodine and benzophenone to give the products (2-D-1,3-xylylene)-18-crown-5 (14a), (2-trimethylstannyl-1,3-xylylene)-18-crown-5) (15), (2-iodo-1,3-xylylene)-18-crown-5 (16) and 2-(diphenylhydroxy)methyl-1,3-xylylene)-18-crown-5 (17) (the latter being converted into its methyl ether (2-(1,1-diphenyl-2-oxapropyl)-1,3-xylylene)-18-crown-5 (17a) for identification), respectively. The lithium compound 9 was treated with benzophenone, chlorotrimethylgermane, chlorodiphenyrphosphine and 4,4'-dimethoxybenzophenone to give intra-annularly substituted crown ether derivatives 17, (2-trimethylgermyl-1,3-xylylene)-18-crown-5 (18), (2-diphenylphosphinyl-1,3-xylylene)-18-crown-5 (19) (the latter undergoing slow oxidation to (2-oxodiphenylphosphinyl-1,3-xylylene)-18-crown-5 (20)) and (2-(4,4'-dimethoxy-diphenylhydroxymethyl)-1,3-xylylene)-18-crown-5 (21) (which was converted under acidic conditions to (2-[(4-methoxyphenyl)(4'oxo-2',5'-cyclohexylidene)methyl]-1,3-xylylene)-18-crown-5 (22)), respectively.

  DOI：

  10.1016/0022-328x(93)83392-9

文献信息

• Crown ether Grignard reagents; x-ray structure of 2-(bromomagnesio)-1,3-xylyl-15-crown-4
  作者：Peter R. Markies、Otto S. Akkerman、Friedrich. Bickelhaupt、Wilberth J. J. Smeets、Anthony L. Spek

  DOI：10.1021/ja00221a030

  日期：1988.6
• Unusual metalation and halogen-metal exchange reactions between 1,3-xylyl crown ethers and organomagnesium reagents. X-ray structure of 2-[(p-tert-butylphenyl)magnesio]-1,3-xylylene-18-crown-5
  作者：Peter R. Markies、Tateo Nomoto、Gerrit Schat、Otto S. Akkerman、Friedrich Bickelhaupt、Wilberth J. J. Smeets、Anthony L. Spek

  DOI：10.1021/om00057a011

  日期：1991.11

  The scope of the surprising exchange reactions between 1,3-xylyl crown ethers and organomagnesium reagents was investigated. Halogen-metal exchange was found for both 2-bromo-1,3-xylylene-15-crown-4 (4) and 2-bromo-1,3-xylylene-18-crown-5 (14) as substrates, while metalation occurred with 1,3-xylylene-15-crown-4 (1). Attempts with other substrates failed, which demonstrates the highly specific structural requirements of these reactions. They are proposed to proceed after initial formation of a 1:1 complex of crown ether and organometallic reagent. Support was obtained by the metalation of 5-bromo-1,3-xylylene-15-crown-4 (17) at the intraannular 2-position. Product formation was investigated by H-1 NMR spectroscopy and by derivatization. An X-ray structure determination of the metalation product 2-[(p-tert-butylphenyl)magnesio]-1,3-xylylene-18-crown-5 (25) was carried out: space group P1BAR (triclinic), a = 10.297 (1) angstrom, b = 10.825 (1) angstrom, c = 12.476 (2) angstrom, alpha = 109.27 (1)-degrees, beta = 94.43 (1)-degrees, gamma = 106.74 (1)-degrees, V = 1234.0 (3) angstrom 3, Z = 2, R = 0.052. Reactions of 2-(phenylmagnesio)-1,3-xylylene-15-crown-4 (2) with 9-phenylfluorene or with diphenylzinc suggest the formation of a stable organomagnesium cation of the type RMg+ (32, 33, 34; R = 1,3-xylylene-15-crown-4-2-yl). Metal-halogen exchange is not restricted to organomagnesiums as illustrated by the reaction of diphenylcalcium with 14, which gave 2-(phenylcalcio)-1,3-xylylene-18-crown-5 (35).
• MARKIES, PETER R.;AKKERMAN, OTTO S.;BICKELHAUPT, FRIEDRICH;SMEETS, WILBER+, J. AMER. CHEM. SOC., 110,(1988) N 13, 4268-4292
  作者：MARKIES, PETER R.、AKKERMAN, OTTO S.、BICKELHAUPT, FRIEDRICH、SMEETS, WILBER+

  DOI：——

  日期：——