2,2,5,5-tetramethyl-3,6-di(cyanomethylene)1,4-dioxane | 87215-69-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: 2,2,5,5-tetramethyl-3,6-di(cyanomethylene)1,4-dioxane
• 英文别名: 2,5-di(cyanomethylidene)-3,3,6,6-tetramethyl-1,4-dioxane；2,5-di(cyanomethylidene)-1,4-dioxane；2,2'-(3,3,6,6-Tetramethyl-1,4-dioxane-2,5-diylidene)diacetonitrile；2-[5-(cyanomethylidene)-3,3,6,6-tetramethyl-1,4-dioxan-2-ylidene]acetonitrile
• CAS: 87215-69-8
• 化学式: C₁₂H₁₄N₂O₂
• 分子量: 218.255
• InChiKey: YULSURVLKGXFAI-UHFFFAOYSA-N

物化性质

• 熔点：
  213 °C(Solv: benzene (71-43-2))
• 沸点：
  337.5±42.0 °C(Predicted)
• 密度：
  1.169±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  66
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3-hydroxy-3-methyl-1-cyano-1-butyne 在 potassium carbonate 、 胞苷 作用下， 以 neat (no solvent) 为溶剂， 反应 24.0h， 以31%的产率得到2,2,5,5-tetramethyl-3,6-di(cyanomethylene)1,4-dioxane
  参考文献：
  名称：

  胞嘧啶与氰基炔丙醇的反应：官能化胞苷环缩酮的合成

  摘要：

  摘要 胞苷通过核糖部分的羟基在温和的条件下（K 2 CO 3，DMF，20–25°C，10–48 h）与一个或两个氰基炔丙醇分子反应，以提供两个新的胞苷家族的代表环状缩酮。第一个（53-76％的收率）仅在两个邻羟基（2'，3'-顺式位置）参与下形成。第二个（7-21％的收率）代表胞苷与两个涉及所有三个羟基的氰基炔丙醇分子的加合物。 胞苷通过核糖部分的羟基在温和的条件下（K 2 CO 3，DMF，20–25°C，10–48 h）与一个或两个氰基炔丙醇分子反应，以提供两个新的胞苷家族的代表环状缩酮。第一个（53-76％的收率）仅在两个邻羟基（2'，3'-顺式位置）参与下形成。第二个（7-21％的收率）代表胞苷与两个涉及所有三个羟基的氰基炔丙醇分子的加合物。

  DOI：

  10.1055/s-0033-1338539

文献信息

• Skvortsov, Yu. M.; Mal'kina, A. G.; Trofimov, B. A., Journal of Organic Chemistry USSR (English Translation), 1984, vol. 20, # 5, p. 1008 - 1014
  作者：Skvortsov, Yu. M.、Mal'kina, A. G.、Trofimov, B. A.、Kositsina, E. I.、Voronov, V. K.、Baikalova, L. V.

  DOI：——

  日期：——
• Modification of guanosine with cyanopropargylic alcohols
  作者：Valentina V. Nosyreva、Anastasiya G. Mal’kina、Alexander I. Albanov、Boris A. Trofimov

  DOI：10.1016/j.tetlet.2014.08.012

  日期：2014.10

  Guanosine has been modified with tertiary cyanopropargylic alcohols under mild conditions (1:1.1-2 molar ratio, K2CO3, DMF, 20-25 degrees C, 19-50 h) to simultaneously give two modifications. The first product (1:1 adduct) is formed by the stereoselective addition of the amide function of the purine ring to the triple bond (38-43% yields), and the second product is the 1:2 adduct, with a second molecule of cyanopropargylic alcohol having reacted with the two vicinal hydroxy groups of the ribose moiety to give a functionalized 1,3-dioxolane ring (29-50% yields). (C) 2014 Elsevier Ltd. All rights reserved.
• Chemo-, regio- and stereospecific addition of adenine and 8-azaadenine to α,β-acetylenic γ-hydroxy nitriles: a short-cut to novel acyclic adenosine analogues
  作者：Boris A. Trofimov、Anastasiya G. Mal'kina、Valentina V. Nosyreva、Olesya A. Shemyakina、Angela P. Borisova、Lyudmila I. Larina、Olga N. Kazheva、Grigorii G. Alexandrov、Oleg A. Dyachenko

  DOI：10.1016/j.tet.2010.01.015

  日期：2010.2

  Adenine (9H-purin-6-amine) adds readily to available alpha,beta-acetylenic gamma-hydroxy nitriles under mild conditions (molar ratio 1 1, K2CO3, DMF, rt, 10 min) to afford chemo-, regio- and stereospecifically (Z)-3-(6-amino-9H-purin-9-yl)-4-hydroxy-4-alkyl-2-alkenenitriles novel functionalized acyclic nucleoside analogues (95-98% yield) Under similar conditions (K2CO3, DMF, rt, 1 h), 8-azaadenine (3H-[1,2,3]triazolo[4,5-d]pyrimidin-7-amine) reacts with 4-hydroxy-4-methyl-2-pentynenitrile nonselectively at the 7-, 8- and 9-positions to give the corresponding adducts in a 1 10 5 9 ratio, the total yield being 81% Chemo-, regio- and stereospecific addiction of 8-azaadenine to the above alpha,beta,-acetylenic gamma-hydroxy nitriles leading to (Z)-3-(7-amino-2H-[1,2,3]triazolo[4,5-d]pyrimidin-2-yl)-4-hydroxy-4-alkyl-2-alkenenitriles in 44-90% yield is attained when the reaction is carried Out without solvent in the presence Of Et3N (30 mol%), the molar ratio of 8-azaadenine alpha,beta-acetylenic nitriles being 1 2 0 (rt, 12-38 h) (C) 2010 Elsevier Ltd All rights reserved
• Сhemo- and regioselective modification of adenosine with tertiary cyanopropargylic alcohols
  作者：Boris A. Trofimov、Valentina V. Nosyreva、Olesya A. Shemyakina、Anastasiya G. Mal’kina、Alexander I. Albanov

  DOI：10.1016/j.tetlet.2012.08.064

  日期：2012.10

  Adenosine reacts with tertiary cyanopropargylic alcohols under mild conditions (K2CO3. DMF, 20-25 degrees C, 4-30 h) with 100% chemo- and regioselectivity by the way of two vicinal hydroxy groups of the ribose moiety to afford (in 52-72% yield) a novel family of adenosine cyclic ketals possessing cyano and hydroxyalkyl functions. (C) 2012 Elsevier Ltd. All rights reserved.
• Bis(cyanomethylidene)-1,4-dioxanes
  作者：Yu. M. Skvortsov、A. G. Mal'kina、B. A. Trofimov

  DOI：10.1007/bf00506117

  日期：1983.7