trimethyl({3,3,6,6-tetramethyl-2-[(trimethylsilyl)oxy]cyclohex-1-en-1-yl}oxy)silane | 177263-27-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: trimethyl({3,3,6,6-tetramethyl-2-[(trimethylsilyl)oxy]cyclohex-1-en-1-yl}oxy)silane
• 英文别名: 1,2-bis(trimethylsilyloxy)-3,3,6,6-tetramethylcyclohex-1-ene；Trimethyl-(3,3,6,6-tetramethyl-2-trimethylsilyloxycyclohexen-1-yl)oxysilane
• CAS: 177263-27-3
• 化学式: C₁₆H₃₄O₂Si₂
• 分子量: 314.616
• InChiKey: MBIPVNWWPMPFLM-UHFFFAOYSA-N

物化性质

• 沸点：
  302.1±42.0 °C(Predicted)
• 密度：
  0.89±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.75
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trimethyl({3,3,6,6-tetramethyl-2-[(trimethylsilyl)oxy]cyclohex-1-en-1-yl}oxy)silane 在 3 A molecular sieve 、 溴 作用下， 以 甲醇 、 四氯化碳 为溶剂， 反应 5.0h， 生成 methyl 5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-quinoxaline carboxylate
  参考文献：
  名称：

  Synthesis and Structure−Activity Relationships of 2-Pyrazinylcarboxamido- benzoates and β-Ionylideneacetamidobenzoates with Retinoidal Activity

  摘要：

  The structure-activity relationships of two series of novel retinoids (2-pyrazinylcarboxamidobenzoates and beta-ionylideneacetamidobenzoates) have been investigated by evaluating their ability to induce differentiation in both human promyelocytic leukemia (HL60) cells and mouse embryonal carcinoma (P19) cells. The most active compound (ED50 = 8.3 x 10(-9) M) of the 2-pyrazinylcarboxamidobenzoates is 4-[2-(5,6,7,8-tetrahydro-5,5,8,8-tetramethylquinoxalyl)-carboxamido]benzoic acid (9u), while the most active analogue of the beta-ionylideneacetamidobenzoates is 4-[3-methyl-5-(2',6',6'-trimethyl-1'-cyclohexen-1'-yl)-(2E,4E)-pentadienamido]benzoic acid (10a, ED50 = 3.2 x 10(-8) M). Our studies identify an absolute requirement for the carboxylic acid moiety on the aromatic ring to be para relative to the amide linkage for activity. Benzoate substitutions in the ortho position relative to the terminal carboxylate (9d,k,r) are well-tolerated; however, a methoxy substituent meta relative to the terminal carboxylate gives rise to only weakly active analogues (9x). Conformational studies (NMR, X-ray crystallography) of the 2-pyrazinylcarboxamidobenzoates indicate that the preferred conformation exhibits a trans-amide bond and an internal hydrogen bond between the quinoxaline N1 and HN amide which locks the torsional angle between C2 and CO in the s-trans conformation. N-Methylation (9y) results in loss of activity. Studies indicate that there is now a cis-amide bond present which redirects the carboxylate toward the pharmacophoric gem-dimethyl groups. The distance between the gem-dimethyl group and the terminal carboxylate appears to be too short to activate the retinoid receptor. N-Methylation in the beta-ionylideneacetamidobenzoate series (10c) also results in the formation of a cis-amide bond and loss of activity.

  DOI：

  10.1021/jm9801354
• 作为产物：
  描述：

  2,2,5,5-四甲基己烷二酸 在 硫酸 、 sodium 作用下， 以 甲苯 、 苯 为溶剂， 反应 32.0h， 生成 trimethyl({3,3,6,6-tetramethyl-2-[(trimethylsilyl)oxy]cyclohex-1-en-1-yl}oxy)silane
  参考文献：
  名称：

  Synthesis and Structure−Activity Relationships of 2-Pyrazinylcarboxamido- benzoates and β-Ionylideneacetamidobenzoates with Retinoidal Activity

  摘要：

  The structure-activity relationships of two series of novel retinoids (2-pyrazinylcarboxamidobenzoates and beta-ionylideneacetamidobenzoates) have been investigated by evaluating their ability to induce differentiation in both human promyelocytic leukemia (HL60) cells and mouse embryonal carcinoma (P19) cells. The most active compound (ED50 = 8.3 x 10(-9) M) of the 2-pyrazinylcarboxamidobenzoates is 4-[2-(5,6,7,8-tetrahydro-5,5,8,8-tetramethylquinoxalyl)-carboxamido]benzoic acid (9u), while the most active analogue of the beta-ionylideneacetamidobenzoates is 4-[3-methyl-5-(2',6',6'-trimethyl-1'-cyclohexen-1'-yl)-(2E,4E)-pentadienamido]benzoic acid (10a, ED50 = 3.2 x 10(-8) M). Our studies identify an absolute requirement for the carboxylic acid moiety on the aromatic ring to be para relative to the amide linkage for activity. Benzoate substitutions in the ortho position relative to the terminal carboxylate (9d,k,r) are well-tolerated; however, a methoxy substituent meta relative to the terminal carboxylate gives rise to only weakly active analogues (9x). Conformational studies (NMR, X-ray crystallography) of the 2-pyrazinylcarboxamidobenzoates indicate that the preferred conformation exhibits a trans-amide bond and an internal hydrogen bond between the quinoxaline N1 and HN amide which locks the torsional angle between C2 and CO in the s-trans conformation. N-Methylation (9y) results in loss of activity. Studies indicate that there is now a cis-amide bond present which redirects the carboxylate toward the pharmacophoric gem-dimethyl groups. The distance between the gem-dimethyl group and the terminal carboxylate appears to be too short to activate the retinoid receptor. N-Methylation in the beta-ionylideneacetamidobenzoate series (10c) also results in the formation of a cis-amide bond and loss of activity.

  DOI：

  10.1021/jm9801354

文献信息

• [EN] SYNTHESIS OF LIGANDS FOR USE IN ACTINIDE EXTRACTION<br/>[FR] SYNTHÈSE DE LIGANDS UTILISABLES POUR L'EXTRACTION D'ACTINIDES
  申请人：UNIV READING

  公开号：WO2011077081A1

  公开（公告）日：2011-06-30

  The invention discloses an improved process for the preparation of 2,2,5,5-tetrasubstituted hexane-1,6-dicarbonyl compounds, and in particular diethyl 2,2,5,5-tetramethylhexanedioate and dimethyl 2,2,5,5-tetramethylhexanedioate, by the alkylation of 1,2-difunctional ethane compounds with enolates of carbonyl compounds. The process provides higher yields and greater synthetic brevity than existing processes.

  该发明披露了一种改进的工艺，用于制备2,2,5,5-四取代己烷-1,6-二酮化合物，特别是通过将1,2-二官能乙烷化合物与羰基化合物的烯醇酸盐进行烷基化来制备二乙酯-2,2,5,5-四甲基己二酸和二甲酯-2,2,5,5-四甲基己二酸。该工艺提供了比现有工艺更高的收率和更大的合成简洁性。
• Influence of Electronic Modulation of Phenanthroline-Derived Ligands on Separation of Lanthanides and Actinides
  作者：Ming-Ming Li、Xiao-Juan Liu、Qi Yang、Yue-Kun Liu、Jiang Nie、Shu-Ming Yang、Ya-Ya Yang、Fu-Yan Lou、Song-Tao Xiao、Ying-Gen Ouyang、Guo-An Ye

  DOI：10.3390/molecules27061786

  日期：——

  stability constants of various ligands with Eu(lll) were obtained by fitting titration curve. Additionally, the basicity of various ligands was determined to be 3.1 ± 0.1, 2.3 ± 0.2, 0.9 ± 0.2, 0.5 ± 0.1 by NMR in the media of CD3OD with the addition of DClO4. The basicity of ligands follows the order of L1 > L2 > L3 > L4, indicating the tendency of protonation decreases with the electron-withdrawing

  四齿N-供体2,9-双(5,5,8,8-四甲基-5,6,7,8-四氢-1,2,4-苯并三嗪-3-)的溶剂萃取、络合能力和碱度yl)-1,10-phenanthroline (CyMe4-BT-Phen)及其被Br、羟苯基、硝基功能化的衍生物进行了讨论和比较。已证明四种 BTPhen 配体能够选择性地提取 Am(III) 而不是 Eu(III)。值得注意的是，5-硝基-CyMe4-BTPhen 对 Eu(lll) 的分配比被抑制在 0.02 以下，与 CyMe4-BTPhen 的 DEu(lll) = 1 相比要低得多。通过紫外/可见光和荧光光谱滴定分析取代基对镧系元素亲和力的影响。通过拟合滴定曲线得到各种配体与Eu(III)的稳定常数。此外，在添加 DClO4 的 CD3OD 介质中通过 NMR 测定各种配体的碱度为 3.1 ± 0.1、2.3 ± 0.2、0.9 ± 0.2、0.5 ± 0
• WO2020183173A5
  申请人：——

  公开号：WO2020183173A5

  公开（公告）日：2023-02-14
• Gleiter, Rolf; Doerner, Thomas; Irngartinger, Hermann, Liebigs Annalen, 1996, # 3, p. 381 - 391
  作者：Gleiter, Rolf、Doerner, Thomas、Irngartinger, Hermann

  DOI：——

  日期：——
• Highly Efficient Separation of Actinides from Lanthanides by a Phenanthroline-Derived Bis-triazine Ligand
  作者：Frank W. Lewis、Laurence M. Harwood、Michael J. Hudson、Michael G. B. Drew、Jean F. Desreux、Geoffrey Vidick、Nouri Bouslimani、Giuseppe Modolo、Andreas Wilden、Michal Sypula、Trong-Hung Vu、Jean-Pierre Simonin

  DOI：10.1021/ja203378m

  日期：2011.8.24

  The synthesis, lanthanide complexation, and solvent extraction of actinide(III) and lanthanide(III) radiotracers from nitric acid solutions by a phenanthroline-derived quadridentate bis-triazine ligand are described. The ligand separates Am(III) and Cm(III) from the lanthanides with remarkably high efficiency, high selectivity, and fast extraction kinetics compared to its 2,2'-bipyridine counterpart. Structures of the 1:2 bis-complexes of the ligand with Eu(III) and Yb(III) were elucidated by X-ray crystallography and force field calculations, respectively. The Eu(III) bis-complex is the first 1:2 bis-complex of a quadridentate bis-triazine ligand to be characterized by crystallography. The faster rates of extraction were verified by kinetics measurements using the rotating membrane cell technique in several diluents. The improved kinetics of metal ion extraction are related to the higher surface activity of the ligand at the phase interface. The improvement in the ligand's properties on replacing the bipyridine unit with a phenanthroline unit far exceeds what was anticipated based on ligand design alone.