1,7,7-trimethyl-3-(methylhydrazono)bicyclo[2.2.1]heptane-2,3-dione | 409321-57-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 1,7,7-trimethyl-3-(methylhydrazono)bicyclo[2.2.1]heptane-2,3-dione
• 英文别名: 1,7,7-trimethyl-3-(methylhydrazinylidene)-byciclo[2.2.1]heptan-2-one；1,7,7-trimethyl-3-(MeHN-imino)bicyclo[2.2.1]heptan-2-one；bornane-2,3-dione-3-methylhydrazone；(d-Campher)-chinon-methylhydrazon-(3)；Bornan-2,3-dion-3-methylhydrazon；1,7,7-trimethyl-3-(methylhydrazinylidene)bicyclo[2.2.1]heptan-2-one
• CAS: 409321-57-9
• 化学式: C₁₁H₁₈N₂O
• 分子量: 194.277
• InChiKey: KRRZIKOXHNDIHF-UHFFFAOYSA-N

物化性质

• 沸点：
  263.3±23.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.59
• 重原子数：
  14.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  41.46
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1,7,7-trimethyl-3-(methylhydrazono)bicyclo[2.2.1]heptane-2,3-dione 、 copper(l) chloride 以 四氢呋喃 为溶剂， 反应 18.0h， 生成
  参考文献：
  名称：

  Insight into the cytotoxicity of polynuclear Cu(I) camphor complexes

  摘要：

  Three new polynuclear Cu(I) camphor complexes, [(CuBr)(2){(p-H2NC6H4)NC10H14O}](n) (2d), [(CuCl)(4){m-C-6 H-4(NC10H14O)(2)}](n) (5f) and [(CuBr)(4){p-C6H4(NC10H14O)(2)}](n) (6e), were synthesized and their cytotoxicity, as well as that of the former reported compounds [(CuX)(2)(YNC10H14O)](n) (X = Cl : Y = NMe2 (1a), NH2 (1b), NHMe (1c), (H2NC6H4)NC10H14O (1d): X = Br; Y = NMe2 (2a)), [{Cu(Me2NNC10H14O)}(2)(mu-X)(2]) (X = Cl (3a), Br (4a)) and [(CuCl)(4){p-C6H4(NC10H14O)(2)}] (5f), were evaluated against the human colon adenocarcinoma cancer cell line HT29 using the colorimetric method (MU assay). The calculated IC50 values indicate that all the complexes have cytotoxic activity that ranges from high to moderate or low, depending on the characteristics of the camphor ligand and the halide co-ligand. The complexes [(CuCl)(4){m-C-6 H-4(NC10H14O)(2)}] (5f. IC50 = 32.0 + 1.1 mu M) and [(CuCl)(2)(H2NNC10H14O)](n) (1b, IC50 = 37.0 +/- 1.1 mu M) display the lowest IC50 values, while [(CuBr)(2){(p-H2NC6H4)NC10H14O}](n) (2d, IC50 = 119.9 +/- 1.1 mu M) displays the highest one. The IC50 value for 51 approaches that of cisplatin (26.3 + 1.1 mu M). No cytotoxic activity was detected for the camphor compounds H2NNC10H14O (b) and m-C6H4(NC10H14O)(2) (1), used as ligands. In selected cases, the copper accumulation in the cells was evaluated. No direct relationship was found between the copper uptake and the cytotoxicity of the complexes. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2014.11.020
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 盐酸 、 乙醚 作用下， 生成 1,7,7-trimethyl-3-(methylhydrazono)bicyclo[2.2.1]heptane-2,3-dione
  参考文献：
  名称：

  Forster; Cardwell, Journal of the Chemical Society, 1913, vol. 103, p. 870

  摘要：

  DOI：

文献信息

• E/Z Isomerization of 3-Hydrazonocamphor Promoted by Coordination to Palladium or Platinum
  作者：M. Fernanda N. N. Carvalho、Ana S. D. Ferreira、João L. Ferreira da Silva、Luís F. Veiros

  DOI：10.1135/cccc20070649

  日期：——

  3-Hydrazonocamphor, 3-(RR¹NN)C₁₀H₁₄O (R = Me, R¹ = H), undergoes intramolecular hydrogen bridging by coordination to platinum or palladium. This effect is evidenced by considerable decrease in the ν(C=O) frequency (compared to the free ligand) in the IR spectra of the complexes [MCl₂L₂] (M = Pd, Pt; L = 3-(RR¹NN)C₁₀H₁₄O) as well as by the magnetic non- equivalence of the two ligands, as revealed by ¹³C NMR. DFT calculations indicate that coordination of 3-(Me(H)NN)C₁₀H₁₄O promotes E/Z isomerization of the hydrazono group of the ligand, inducing formation of intramolecular hydrogen bonding and corresponding stabilization of the complex. Characterization of the complexes [MCl₂L₂] (M = Pt; L: R, R¹ = Me (1), R = Me, R¹ = H (2) and M = Pd; L: R = Me, R¹ = H (3)) was performed by analytical and spectroscopic techniques. Redox properties of the 3-hydazonocamphors and their complexes were studied by cyclic voltammetry. The structure of trans-[PtCl₂3-(Me₂NN)C₁₀H₁₄O}₂] was determined by single-crystal X-ray diffraction analysis. The complex has square-planar geometry and crystallizes in the tetragonal P4₃ space group.

  3-肼基樟脑，3-(RR1NN)C10H14O (R = Me，R1 = H) 通过与铂或钯的配位发生分子内氢键形成。这种效应在[MCL2L2] (M = Pd，Pt; L = 3-(RR1NN) ) 的红外光谱中，与自由配体相比，ν(C=O) 频率显著降低，两个配体的磁性不等效也表明了这种效应，这可以通过13C NMR得到证实。DFT计算表明，3-(Me(H)NN) 的配位促进了配体的肼酮基团的E/Z异构化，诱导了分子内氢键的形成以及相应的配合物稳定性。通过分析和光谱技术对[MCL2L2] (M = Pt; L: R，R1 = Me (1)，R = Me，R1 = H (2) 和 M = Pd; L: R = Me，R1 = H (3)) 进行了表征。通过循环伏安法研究了3-肼基樟脑及其配合物的氧化还原性质。通过单晶X射线衍射分析确定了trans-[PtCL23-(Me2NN) }2]的结构。该配合物具有正方形平面几何结构，并结晶在四方P43空间群中。
• Tuning structure and properties of Pd and Pt camphor derived complexes
  作者：Ana S.D. Ferreira、M. Fernanda N.N. Carvalho、Adelino M. Galvão、Luís F. Veiros

  DOI：10.1016/j.ica.2012.10.036

  日期：2013.1

  Seven new camphor palladium or platinum compounds with novel metal coordination environments were obtained by convenient choice of the experimental conditions in particular the solvent. cis-[PtCl2(PhNC10 H14O)(2)]) and [Pd(MeNNC10H14O)(2)] were structurally characterized by X-ray diffraction analysis while [PtCl2(Me2NC10H13NSO2)}(2)], [PdCl2(YNC10H14O)}(2)] (Y = NMe2, NPh2) and [Pd(PhNNC10H14O)(2)] were formulated by elemental analysis and spectroscopic techniques. Relevant aspects of the IR and NMR spectra of complexes [Pd(YNC10H14O)(2)] (Y = MeN, PhN) are discussed with the help of DFT calculations. Evaluation of the properties of the new complexes as catalysts for activation of 4-pentyn-1-ol towards formation of cyclization products showed that [PdCl2(Ph2NNC10H14O)}(2)] is more efficient than [PdCl2 (Me2NNC10H14O)(2)] which is one of the more efficient camphor derived catalysts reported before. In contrast the chelate complexes [Pd(YNC10H14O)(2)] (Y = MeN, PhN) display no catalytic activity. (C)2012 Elsevier B. V. All rights reserved.
• Synthesis, characterization and study of the catalytic properties of Zn(II) camphor derived complexes
  作者：Tiago A. Fernandes、Ana M. Ferraria、Adelino M. Galvão、Ana M. Botelho do Rego、Ana C.M. Suárez、M.Fernanda N.N. Carvalho

  DOI：10.1016/j.jorganchem.2013.10.040

  日期：2014.6

  Zinc(II) complexes of general formula [ZnX2(YNC10H14O)], [ZnX2(YNC10H13NSO2)], [ZnX2(H2NNC10H14O)(2)], [ZnX2}(2)(YNC10H14O)] and [ZnX2}(2)(YNC10H13NSO2)] were obtained from zinc halides (chloride or bromide) by reaction with the suitable camphor ligands.In most of the complexes, the camphor ligands remain unchanged upon coordination, except in [Zn(MeNNC10H14O)}(2)(mu-Cl)(2)] where proton loss from MeHNNC10H14O occurs. The new complexes and camphor derivatives were characterized by IR, NMR (H-1, C-13H}, DEPT, 2D) and elemental analysis. In some cases the surface composition was studied by X-ray photoelectron spectroscopy (XPS) and imaged by Scanning Electron Microscopy (SEM). Images of [ZnCl2(Me2NNC10H14O)] and [ZnCl2(Me2NNC10H13NSO2)] obtained by SEM show the solid particles have tubular structures capped in one or both extremities. The coordination of THF in [ZnCl2(YNC10H14O) THF] was confirmed by X-ray diffraction analysis. The camphor derivatives YNC10H14NSO2 (Y = NMe2; NHMe) and p-C6H4(NC10H14O)(2) were structurally characterized by X-ray diffraction analysis.The ability of selected Zn(II) camphor complexes to catalyse the cyclization of 4-pentyn-1-ol was evaluated showing that the binuclear complex [ZnX2}(2)(YNC10H14O)] performs better than the mononuclear Zn(II) complexes. (C) 2013 Elsevier B.V. All rights reserve.