4,4-二甲基-1-(三甲基硅烷基)戊烷-1,3-二酮 | 286854-89-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 4,4-二甲基-1-(三甲基硅烷基)戊烷-1,3-二酮
• 中文别名: 两性霉素B,N-(1-脱氧-D-果糖-1-基)-N-甲基-,甲基酯,L-天冬氨酸酯(1:1)(salt)
• 英文名称: 2,2,6,6-tetramethyl-2-sila-3,5-heptanedione
• 英文别名: 2,2,6,6-tetramethyl-2-silaheptane-3,5-dione；2,2,6,6-tetramethyl-2-silaoctane-3,5-dione；tmshdH；4,4-Dimethyl-1-(trimethylsilyl)pentane-1,3-dione；4,4-dimethyl-1-trimethylsilylpentane-1,3-dione
• CAS: 286854-89-5
• 化学式: C₁₀H₂₀O₂Si
• 分子量: 200.353
• InChiKey: XRIZYGXJDWDRKF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.44
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4-二甲基-1-(三甲基硅烷基)戊烷-1,3-二酮 在 triethylamine 作用下， 以 甲醇 、 乙醚 、 乙腈 为溶剂， 生成 silver(I) (2,2,6,6-tetramethyl-2-sila-3,5-heptanedionate)(triphenylphosphine)
  参考文献：
  名称：

  Synthesis and physical and structural characterization of Ag(I) complexes supported by non-fluorinated β-diketonate and related ancillary ligands

  摘要：

  A series of Ag(I) complexes, [Ag(X)L], where X is the anion of 2,2,6,6-tetramethyl-3,5-heptanedione (tmhdH), 2,2,7-trimethyl-3,5-octanedione (tmodH), 2-sila-2,2,6,6-tetramethyl-3,5-heptanedione (tmshdH), 5-mercapto-2,2,6,6-tetramethyl-4-hepten-3-one (S-tmhdH), 5-mercapto-2,2,7-trimethyl-4-octen-3-one (S-tmodH), or 5-amino-2,2,6,6-tetramethyl-4-hepten-3-one (N-tmhdH) and L = triphenylphosphine (PPh3) or tri-n-butylphosphine (PBu3) were prepared by treatment of silver nitrate with either the diketone derivative in the presence of a base or with the preformed sodium salt of the diketone derivative. The thermal properties of the new complexes were investigated for potential application in chemical vapor deposition (CVD) processes. Results of thermogravimetric analysis showed that the vast majority of the silver complexes have little promise for CVD, since the ligands dissociate at elevated temperatures without volatilization. The first ever reported single crystal X-ray diffraction studies of silver complexes, with simple, ancillary, non-fluorinated beta-diketonate supporting ligands, revealed [Ag(tmhd)(PPh3)] (la) to be monomeric and [Ag(S-tmhd)(PPh3)](2) (4a) to be dimeric in the solid state, respectively. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(02)00980-4
• 作为产物：
  描述：

  1-溴频哪酮 在 正丁基锂 、 mercury dichloride 、 mercury(II) oxide 作用下， 以 甲醇 、 乙醚 、 正己烷 、 水 为溶剂， 反应 3.5h， 生成 4,4-二甲基-1-(三甲基硅烷基)戊烷-1,3-二酮
  参考文献：
  名称：

  通过2-三甲基甲硅烷基-1,3-二硫烷制备sila-β-二酮的研究：双（2,2,6,6-四甲基-2-sila-3,5-庚二酮）第二多晶型物的结构表征铜（II）

  摘要：

  通过将2-三甲基甲硅烷基-1,3-二硫杂环丁烷的阴离子与1的缩合反应合成2,2,6,6-四甲基-2-silaheptane-3,5-二酮（tmshdH）的sila-β-二酮-溴-3,3-二甲基丁烷-2-酮，然后用HgO / HgCl 2掩盖潜在的羰基部分。通过X射线衍射方法对已知铜（II）配合物的单斜晶型Cu（tmshd）2进行了结晶和研究，发现其像正交晶体一样无序。尝试使用二噻吩合成二甲化的β-二酮，2,2,6,6-四甲基-2,6-二硅庚烷-3,5-二酮和单甲硅烷基化的4,4-二甲基-4-sila-3-氧代戊醛方法未成功。但是，1,3-二噻烷基前体，与杂质一起2,2 ' -双（三甲基硅烷基）-2,2 '晶体学研究了-bi-1,3-二硫杂环丁烷。对于这些分子，观察到对固态键合参数的大的立体电子和空间位阻效应。

  DOI：

  10.1016/j.jorganchem.2003.09.032

文献信息

• MOCVD precursors based on organometalloid ligands
  申请人：Research Foundation of State University of New York

  公开号：US06340768B1

  公开（公告）日：2002-01-22

  Volatile metal complexes with &agr;-sila-&bgr;-diketonate ligands containing haloalkyl, and particularly, perfluoroalkyl, substitutents are useful as metal precursors for chemical vapor deposition processes and as nanostructured materials containing fluorous domains.

  含有卤代烷基，特别是全氟烷基取代基的α-硅-β-二酮酸配体的挥发性金属配合物可用作化学气相沉积过程中的金属前体，以及含有氟化领域的纳米结构材料。
• Facile synthesis of a novel class of organometalloid-containing ligands, the sila-β-diketones: preparation and physical and structural characterization of the copper(II) complexes, Cu[R′C(O)CHC(O)SiR3]2
  作者：Kulbinder K Banger、Silvana C Ngo、Seiichiro Higashiya、Rolf U Claessen、Kenneth S Bousman、Poay N Lim、Paul J Toscano、John T Welch

  DOI：10.1016/s0022-328x(03)00393-0

  日期：2003.7

  The substitution of a carbon atom by silicon provides an attractive, novel approach to modification of the thermal stability and volatility of metal-organic chemical vapor deposition precursors supported by beta-diketonate ancillary ligands. The low temperature reaction of the lithium enolates of acetyltrialkylsilanes with acyl chlorides affords the sila-beta-diketones, R'C(O)CH2C(O)SiR3 (R' = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu; SiR3 = SiMe3, SiEt3, SiMe2(t-Bu), SiMe2(t-hexyl), Si(i-Pr)A in good yields. Multinuclear NMR studies suggest that the sila-beta-diketones exist as the enolic tautomer with a vinylsilane isomeric structure. Homoleptic Cu(II) sila-beta-diketonate complexes were prepared in a first pass study to evaluate how precursor performance is affected by modulation of the peripheral substituents in the ligands. Thermal analyses, (TGA, DSC) show that the silylated Cu(II) precursors (SiR3 = SiMe3; R' = t-Bu or i-Bu) have greater volatility than the corresponding carbon analogues. Some of the new Cu(11) complexes exist as liquids or low melting solids, which are preferred states for industrial deposition processes. X-ray diffraction studies of selected copper complexes showed them to have typical, square planar geometry; calculations of molecular volumes suggest that packing in the solid-state is less efficient for the silicon-containing complexes than for the non-silylated analogues. (C) 2003 Elsevier Science B.V. All rights reserved.
• Synthesis and physical and structural characterization of Ag(I) complexes supported by non-fluorinated β-diketonate and related ancillary ligands
  作者：Silvana C Ngo、Kulbinder K Banger、Paul J Toscano、John T Welch

  DOI：10.1016/s0277-5387(02)00980-4

  日期：2002.6

  A series of Ag(I) complexes, [Ag(X)L], where X is the anion of 2,2,6,6-tetramethyl-3,5-heptanedione (tmhdH), 2,2,7-trimethyl-3,5-octanedione (tmodH), 2-sila-2,2,6,6-tetramethyl-3,5-heptanedione (tmshdH), 5-mercapto-2,2,6,6-tetramethyl-4-hepten-3-one (S-tmhdH), 5-mercapto-2,2,7-trimethyl-4-octen-3-one (S-tmodH), or 5-amino-2,2,6,6-tetramethyl-4-hepten-3-one (N-tmhdH) and L = triphenylphosphine (PPh3) or tri-n-butylphosphine (PBu3) were prepared by treatment of silver nitrate with either the diketone derivative in the presence of a base or with the preformed sodium salt of the diketone derivative. The thermal properties of the new complexes were investigated for potential application in chemical vapor deposition (CVD) processes. Results of thermogravimetric analysis showed that the vast majority of the silver complexes have little promise for CVD, since the ligands dissociate at elevated temperatures without volatilization. The first ever reported single crystal X-ray diffraction studies of silver complexes, with simple, ancillary, non-fluorinated beta-diketonate supporting ligands, revealed [Ag(tmhd)(PPh3)] (la) to be monomeric and [Ag(S-tmhd)(PPh3)](2) (4a) to be dimeric in the solid state, respectively. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Investigations into the preparation of sila-β-diketones via 2-trimethylsilyl-1,3-dithianes: structural characterization of a second polymorph of bis(2,2,6,6-tetramethyl-2-sila-3,5-heptanedionato)copper(II)
  作者：Rolf U Claessen、Andrei M Kornilov、Kulbinder K Banger、Silvana C Ngo、Seiichiro Higashiya、Christopher C Wells、Evgeny V Dikarev、Paul J Toscano、John T Welch

  DOI：10.1016/j.jorganchem.2003.09.032

  日期：2004.1

  condensation of the anion of 2-trimethylsilyl-1,3-dithiane with 1-bromo-3,3-dimethylbutan-2-one, followed by unmasking of the latent carbonyl moiety with HgO/HgCl2. A monoclinic polymorph of the known copper(II) complex, Cu(tmshd)2, was crystallized and studied by X-ray diffraction methods and found to be disordered like the orthorhombic one. Attempts to synthesize the disilylated β-diketone, 2,2,6,6-tetramethyl-2

  通过将2-三甲基甲硅烷基-1,3-二硫杂环丁烷的阴离子与1的缩合反应合成2,2,6,6-四甲基-2-silaheptane-3,5-二酮（tmshdH）的sila-β-二酮-溴-3,3-二甲基丁烷-2-酮，然后用HgO / HgCl 2掩盖潜在的羰基部分。通过X射线衍射方法对已知铜（II）配合物的单斜晶型Cu（tmshd）2进行了结晶和研究，发现其像正交晶体一样无序。尝试使用二噻吩合成二甲化的β-二酮，2,2,6,6-四甲基-2,6-二硅庚烷-3,5-二酮和单甲硅烷基化的4,4-二甲基-4-sila-3-氧代戊醛方法未成功。但是，1,3-二噻烷基前体，与杂质一起2,2 ' -双（三甲基硅烷基）-2,2 '晶体学研究了-bi-1,3-二硫杂环丁烷。对于这些分子，观察到对固态键合参数的大的立体电子和空间位阻效应。