3-methyl-1-(trimethylstannyl)but-1-yne | 22015-17-4

• 分子结构分类: 有机化合物 - 乙炔化物 - 金属乙炔化物
• 英文名称: 3-methyl-1-(trimethylstannyl)but-1-yne
• 英文别名: trimethyl(isopropylethynyl)tin；Trimethyl-<3-methyl-butin-(1)-yl>-stannan；Trimethyl-(3-methyl-butin-(1)-yl)-stannan；Trimethyl(3-methylbut-1-ynyl)stannane
• CAS: 22015-17-4
• 化学式: C₈H₁₆Sn
• 分子量: 230.925
• InChiKey: ROBYCQWFRPAGOR-UHFFFAOYSA-N

物化性质

• 沸点：
  178.0±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.52
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  3-methyl-1-(trimethylstannyl)but-1-yne 、 2,3-dibromo-5,10,15,20-tetraphenylporphyrin 在 四(三苯基膦)钯 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以67%的产率得到2,3-bis(isopropylethynyl)-5,10,15,20-tetraphenylporphyrin
  参考文献：
  名称：

  Controlling Both Ground- and Excited-State Thermal Barriers to Bergman Cyclization with Alkyne Termini Substitution

  摘要：

  The cross-coupling reaction of 2,3-dibromo-5,10,15,20-tetraphenylporphyrin with corresponding organostannanes in the presence of a Pd0 catalyst in THF at reflux temperature yields free base 2,3-dialkynylporphyrins 1a,c-e. The subsequent deprotection of trimethylsilyl group of 1a with TBAF in THF under aqueous conditions produces the 2,3-diethynyl-5,10,15,20-tetraphenylporphyrins 1b in 87% yield. Compounds 1a-d undergo zinc insertion upon treatment with Zn(OAc)2.2H2O in CHCl3/MeOH to give zinc(II) 2,3-dialkynyl-5,10,15,20-tetraphenylporphyrins (2a-d) in 70-92% yields. Thermal Bergman cyclization of 1a-e and 2a-d was studied in chlorobenzene and approximately 35-fold 1,4-cyclohexadiene at 120-210 degrees C. Compounds 1b and 2b with R = H react at lower temperature (120 degrees C) and produce cyclized products 3b and 4b in higher yields (65-70%) than their propyl, isopropyl, and phenyl analogues, with R = Ph being the most stable. Continuing in this trend, the -TMS derivatives 1a and 2a exhibit no reactivity even after heating at 190 degrees C in chlorobenzene/CHD for 24 h. Photolysis (at lambda >/= 395 nm) of 1b and 2b at 10 degrees C leads the formation of isolable picenoporphyrin products in 15 and 35% yields, respectively, in 72 h, whereas these compounds are stable in solution under same reaction conditions at 25 degrees C in the dark. Unlike thermolysis at 125 degrees C, which did not yield Bergman cyclized product for R = Ph, photolysis generated very small amounts of picenoporphyrin products (3c: 5%; 4c: 8% based on 1H NMR) as well as a mixture of reduced porphyrin products that were not separable. Thus, trends in the barrier to Bergman cyclization in the excited state exhibit the same trend as those observed in the ground state as a function of R-group. Finally, photolysis of 2b at 10 degrees C with lambda >/= 515 or 590 nm in benzene/iPrOH (4:1, 72 h) produces 4b in 15 and 6% isolated yields, indicating that conjugation of the enediyne unit into the porphyrin electronic transitions leads to sufficient distortion to generate photoproduct even with long wavelength excitation.

  DOI：

  10.1021/ja045979t
• 作为产物：
  描述：

  、 三甲基氯化锡 以 氨 为溶剂， 以80%的产率得到3-methyl-1-(trimethylstannyl)but-1-yne
  参考文献：
  名称：

  Petrov, A. A.; Mingaleva, K. S.; Zavgorodnii, V. S., Zhurnal Obshchei Khimii, 1964, vol. 34, p. 535 - 537

  摘要：

  DOI：

文献信息

• Sharanina,L.G. et al., Journal of general chemistry of the USSR, 1966, vol. 36, p. 1290 - 1297
  作者：Sharanina,L.G. et al.

  DOI：——

  日期：——
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Sn: Org.Verb.2, 1.1.2.1.10, page 108 - 120
  作者：

  DOI：——

  日期：——
• PtCl2-catalyzed benzannulation of nickel(II) 2,3-dialkynylporphyrins to form unusual phenanthroporphyrins
  作者：Mahendra Nath、Maren Pink、Jeffrey M. Zaleski

  DOI：10.1016/j.jorganchem.2011.07.008

  日期：2011.12

  Reaction of Ni(II) 2,3-dibromo-5,10,15,20-tetraphenylporphyrin with substituted stannyl alkynes generates substituted 2,3-dialkynylporphyrins in good yields. Thermolysis of these motifs with stoichiometric or even catalytic equivalents of PtCl2 yields unusual phenanthroporphyrins with only small amounts of the established picenoporphyrin or other side products. (C) 2011 Elsevier B.V. All rights reserved.
• Sharanina, L. G.; Zavgorodnii, V. S.; Petrov, A. A., Zhurnal Obshchei Khimii, 1966, vol. 36, p. 1290 - 1297
  作者：Sharanina, L. G.、Zavgorodnii, V. S.、Petrov, A. A.

  DOI：——

  日期：——
• Bunz, Uwe H. F.; Enkelmann, Volker; Räder, Joachim, Organometallics, 1993, vol. 12, # 12, p. 4745 - 4747
  作者：Bunz, Uwe H. F.、Enkelmann, Volker、Räder, Joachim

  DOI：——

  日期：——