Diazo-1-dicarbomethoxy-1,2-methyl-3-buten | 70557-20-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Diazo-1-dicarbomethoxy-1,2-methyl-3-buten
• 英文别名: 2-diazonio-1-methoxy-3-methoxycarbonyl-4-methylpenta-1,3-dien-1-olate
• CAS: 70557-20-9
• 化学式: C₉H₁₂N₂O₄
• 分子量: 212.205
• InChiKey: PUFQROGDASAKND-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.34
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  89.0
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  Diazo-1-dicarbomethoxy-1,2-methyl-3-buten 以 乙醚 为溶剂， 生成 1,2-dicarbomethoxy-3,3-dimethylcyclopropene
  参考文献：
  名称：

  trans-5-Palladatricyclo[4.1.0.02,4]heptanes: Complexes with monodentate, weakly coordinating ligands, formation of new derivatives and synthetic limitations

  摘要：

  The bis(acetone) complex of tetramethyl rac-3,3,7,7-tetramethyl-trans-5-palladatricyclo[4.1.0.0(2,4)]heptane-1.2,4,6-tetracarboxylate rac-1a was crystallized and investigated by X-ray structure analysis. Unlike in complexes with bidendate ligands in rac-1a.2(acetone), only a small deviation from the square planar coordination of palladium was observed. Efforts to crystallize the analogous pyridine, acetonitrile and benzonitrile complexes failed; but the labile complexes rac-1a.2([D-5]pyridine) and rac-1a. 2([D-3] acetonitrile) as well as rac-1a.2([D-6]acetone) could be characterized by H-1 and C-13 NMR spectra and a fast ligand exchange was proven by nmr. Then the ability of different 1,2-disubstituted cyclopropenes to form trans-5-pallada-tricyclo[4.1.0.0(2,4)] heptanes 1 was investigated. Only the diesters 5c-e lead to PTHs, with a diester possessing sterically demanding substituents in 3-position of the cyclopropene and with other substituents in 1- respectively 2-position of the cyclopropene either the cyclopropene-formation or the PTH-formation failed.

  DOI：

  10.1002/prac.19983400307
• 作为产物：
  描述：

  dimethyl 3,3-dimethyl-3H-pyrazole-4,5-dicarboxylate 以 乙醚 为溶剂， 生成 Diazo-1-dicarbomethoxy-1,2-methyl-3-buten
  参考文献：
  名称：

  trans-5-Palladatricyclo[4.1.0.02,4]heptanes: Complexes with monodentate, weakly coordinating ligands, formation of new derivatives and synthetic limitations

  摘要：

  The bis(acetone) complex of tetramethyl rac-3,3,7,7-tetramethyl-trans-5-palladatricyclo[4.1.0.0(2,4)]heptane-1.2,4,6-tetracarboxylate rac-1a was crystallized and investigated by X-ray structure analysis. Unlike in complexes with bidendate ligands in rac-1a.2(acetone), only a small deviation from the square planar coordination of palladium was observed. Efforts to crystallize the analogous pyridine, acetonitrile and benzonitrile complexes failed; but the labile complexes rac-1a.2([D-5]pyridine) and rac-1a. 2([D-3] acetonitrile) as well as rac-1a.2([D-6]acetone) could be characterized by H-1 and C-13 NMR spectra and a fast ligand exchange was proven by nmr. Then the ability of different 1,2-disubstituted cyclopropenes to form trans-5-pallada-tricyclo[4.1.0.0(2,4)] heptanes 1 was investigated. Only the diesters 5c-e lead to PTHs, with a diester possessing sterically demanding substituents in 3-position of the cyclopropene and with other substituents in 1- respectively 2-position of the cyclopropene either the cyclopropene-formation or the PTH-formation failed.

  DOI：

  10.1002/prac.19983400307

文献信息

• Vinylcarbenes acycliques: reactions de cycloadditions intermoleculaires
  作者：M. Franck-Neumann、C. Dietrich-Buchecker

  DOI：10.1016/0040-4020(78)88422-1

  日期：1978.1

  3-dimethyl-3H-pyrazoles in unsaturated solvents leads in good yields and often with high stereoselectivity, to vinylcarbene cycloadducts. This direct synthesis of vinylcyclopropanes, vinylcyclopropenes and divinylcyclopropanes shows that acyclic vinyl carbenes are not necessarily intramolecularly stabilized. They can actually be trapped by olefins, acetylenes or dienes, depending on the carbene substituents. Cyano

  3,3-二甲基-3H-吡唑类化合物在不饱和溶剂中的光解可产生良好的收率，并且通常具有很高的立体选择性，从而可生成乙烯基碳烯环加合物。乙烯基环丙烷，乙烯基环丙烯和二乙烯基环丙烷的这种直接合成表明，无环乙烯基卡宾不一定是分子内稳定的。实际上，取决于卡宾取代基，它们实际上可能被烯烃，乙炔或二烯捕获。到目前为止，氰基乙烯基碳烯是最有效的分子间环附加物，但是烷氧基甚至酮乙烯基碳烯都可以与二烯发生环丙烷化反应，在最后一种情况下，与沃尔夫重排的竞争很小。
• Kuznetsov; Kuchuk, Russian Journal of Organic Chemistry, 1997, vol. 33, # 11, p. 1543 - 1546
  作者：Kuznetsov、Kuchuk

  DOI：——

  日期：——