5-二甲基甲硅烷基环戊二烯 | 83303-35-9

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 中文名称: 5-二甲基甲硅烷基环戊二烯
• 英文名称: (dimethylsilyl)cyclopentadiene
• 英文别名: 5-Dimethylsilylcyclopentadiene；cyclopentadienyldimethylsilane；Cyclopentadienyldimethylsilan；Cyclopenta-2,4-dien-1-yl(dimethyl)silane
• CAS: 83303-35-9
• 化学式: C₇H₁₂Si
• 分子量: 124.258
• InChiKey: HYJXYQBONPQCKW-UHFFFAOYSA-N

物化性质

• 沸点：
  137.7±15.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.97
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  5-二甲基甲硅烷基环戊二烯 在 叔丁基过氧化氢 、 potassium fluoride 、 bis(acetylacetonate)oxovanadium 、 双氧水 、 氯化二乙基铝 、 potassium hydrogencarbonate 、 samarium(III) trifluoromethanesulfonate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 苯 为溶剂， 生成 methyl (1S,2R,4S,5R,6R,7S,8R)-7-chloro-8-hydroxy-3-oxatricyclo[3.2.1.02,4]octane-6-carboxylate
  参考文献：
  名称：

  Yokoshima, Satoshi; Tokuyama, Hidetoshi; Fukuyama, Tohru, Angewandte Chemie - International Edition, 2000, vol. 39, # 22, p. 4073 - 4075

  摘要：

  DOI：
• 作为产物：
  描述：

  cyclopentadienyldimethylchlorosilane 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 5-二甲基甲硅烷基环戊二烯
  参考文献：
  名称：

  Barker, Philip J.; Davies, Alwyn G.; Henriquez, Roberto, Journal of the Chemical Society. Perkin transactions II, 1982, p. 745 - 750

  摘要：

  DOI：

文献信息

• Mono- and di-cyclopentadienyl zirconium derivatives containing the dimethylsilylcyclopentadienyl ligand. Agostic linear Si–H–Zr interaction in the molecular structure of [Zr{η5-C5H4(SiMe2H)}Cl3]2 †
  作者：Gemma Ciruelo、Tomás Cuenca、Rafael Gómez、Pilar Gómez-Sal‡、Avelino Martín ‡

  DOI：10.1039/b010221k

  日期：——

  Dimethylsilyl substituted mono- and di-cyclopentadienyl zirconium chlorides have been prepared and their reactions with amido and alkyl reagents studied. The silylcyclopentadienes C5H5(SiMe2H) 1, C5H4(SiMe2H)22 and C5H4(SiMe3)(SiMe2H) 3 can be prepared by reaction of Na(C5H5) with the appropriate chlorosilane reagent. The lithium salt Li[C5H4(SiMe2H)] reacts with ZrCl4 or [Zr(C5H5)Cl3] to give the metallocene complexes [Zr(C5H4R)C5H4(SiMe2H)}Cl2] (R = SiMe2H 4 or H 5) whereas the reaction of the disilylcyclopentadiene C5H4(SiMe2H)2 with ZrCl4 afforded the monocyclopentadienyl complex [ZrC5H4(SiMe2H)}Cl3] 6, which exchanges the Si–H and Zr–Cl bonds. The reaction of 6 with lithium amides produces different products depending on the basicity of the nitrogen atom and the steric demands of its amido substituents. The reaction with LiN(SiMe3)2 and LiNH(2,6-Me2C6H3) afforded the corresponding amido zirconium complexes [ZrC5H4(SiMe2H)}(NRR′)Cl2] (R = R′ = SiMe37; R = H, R′ = 2,6-Me2C6H38), but in the case of the reaction with LiNHtBu the known cyclopentadienylsilylamido derivative [Zr(η5,η1-C5H4SiMe2NtBu)Cl2] was formed. The monoamido, diamido and dialkyl dicyclopentadienyl complexes [Zr(C5H4R)C5H4(SiMe2H)}X(Y)] (R = SiMe2H 9 or H 10, X = Cl, Y = NHtBu; R = SiMe2H 11 or H 12, X = Y = NHtBu; R = SiMe2H 13 or H 14, X = Y = Me) have been synthesized by reaction of 4 and 5 with the appropriate amido or methyl reagent. Compound 9 reacts with a stoichiometric amount of water with selective hydrolysis of the Zr–amido bond to give the corresponding μ-oxo dinuclear complex [Zr[C5H4(SiMe2H)]2Cl}2(μ-O)] 15. The molecular structure of [ZrC5H4(SiMe2H)}Cl3] 6 was established by X-ray crystallography. Compound 6 is a dimer, in the solid state, in which dimerization occurs through Zr–H–Si agostic interactions and two chloride bridges.

  已经制备了二甲基硅烷取代的单环戊二烯基和二环戊二烯基锆氯化物，并研究了它们与氨基和烷基试剂的反应。通过Na(C5H5)与适当的氯硅烷试剂反应，可以制备硅基环戊二烯C5H5(SiMe2H) 1、C5H4(SiMe2H)22和C5H4(SiMe3)(SiMe2H) 3。锂盐Li[C5H4(SiMe2H)]与ZrCl4或[Zr(C5H5)Cl3]反应，得到金属茂配合物[Zr(C5H4R)C5H4(SiMe2H)}Cl2]（R = SiMe2H 4或H 5），而二硅基环戊二烯C5H4(SiMe2H)2与ZrCl4反应得到单环戊二烯基配合物[ZrC5H4(SiMe2H)}Cl3] 6，该配合物交换了Si–H和Zr–Cl键。6与锂胺反应，根据氮原子的碱性和其氨基取代基的立体要求，产生不同的产物。与LiN(SiMe3)2和LiNH(2,6-Me2C6H3)反应得到相应的氨基锆配合物[ZrC5H4(SiMe2H)}(NRR')Cl2]（R = R' = SiMe37；R = H，R' = 2,6-Me2C6H38），但在与LiNHtBu反应的情况下，形成了已知的环戊二烯基硅基氨基衍生物[Zr(η5,η1-C5H4SiMe2NtBu)Cl2]。通过4和5与适当的氨基或甲基试剂反应，合成了单氨基、二氨基和二烷基二环戊二烯基配合物[Zr(C5H4R)C5H4(SiMe2H)}X(Y)]（R = SiMe2H 9或H 10，X = Cl，Y = NHtBu；R = SiMe2H 11或H 12，X = Y = NHtBu；R = SiMe2H 13或H 14，X = Y = Me）。化合物9与化学计量水反应，选择性水解Zr–氨基键，得到相应的μ-氧二核配合物[Zr[C5H4(SiMe2H)]2Cl}2(μ-O)] 15。通过X射线晶体学确定了[ZrC5H4(SiMe2H)}Cl3] 6的分子结构。化合物6在固态下是二聚体，二聚化通过Zr–H–Si暂稳相互作用和两个氯桥实现。
• Convenient Route to Both Enantiomerically Pure Forms of<i>trans</i>-4,5-Dihydroxy-2-cyclopenten-1-one: Efficient Synthesis of the Neocarzinostatin Chromophore Core
  作者：Koji Toyama、Satoru Iguchi、Hayato Sakazaki、Tohru Oishi、Masahiro Hirama

  DOI：10.1246/bcsj.74.997

  日期：2001.6

  An enantioselective synthesis of an epoxybicyclo[7.3.0]dodecenediyne core system of the neocarzinostatin chromophore has been achieved via intramolecular acetylide addition and palladium-mediated coupling of iodocyclopentene 5 with alkyne 6. The key cyclopentene moiety, trans-4,5-dihydroxy-2-cyclopenten-1-one 7, was conveniently prepared in both enantiomerically pure forms via enzymatic desymmetrization

  通过分子内乙炔加成和钯介导的碘环戊烯 5 与炔烃 6 偶联，实现了新制癌素发色团的环氧双环 [7.3.0] 十二烯二炔核心系统的对映选择性合成。 关键的环戊烯部分，反式-4,5-二羟基-通过内消旋-3,4,5-反式，反式-三羟基环戊烯衍生物的酶促去对称化，可以方便地以两种对映体纯形式制备2-cyclopenten-1-one 7。
• Silicon- and Zirconium-containing compositions for vapor deposition of Zirconium-containing films
  申请人：L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude

  公开号：US09663547B2

  公开（公告）日：2017-05-30

  Disclosed are Silicon- and Zirconium-containing precursors having one of the following formulae: wherein each R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 is independently selected from H; a C1-C5 linear, branched, or cyclic alkyl group; or a C1-C5 linear, branched, or cyclic fluoroalkyl group. Also disclosed are methods of synthesizing the disclosed precursors and using the same to deposit Zirconium-containing thin films on substrates via vapor deposition processes.

  披露了具有以下公式之一的含硅和含锆前体物质：其中每个R1、R2、R3、R4、R5、R6、R7、R8、R9和R10分别独立地选择自H；C1-C5线性、支链或环烷基；或C1-C5线性、支链或环氟烷基。还披露了合成所述前体物质的方法，并利用它们通过蒸发沉积工艺在基底上沉积含锆薄膜。
• [2.2.1]-Bicyclic systems relevant to synthetic studies on CP-225,917—use of a new silylated cyclopentadiene
  作者：Derrick L.J Clive、Hua Cheng、Pulak Gangopadhyay、Xiaojun Huang、Bodhuri Prabhudas

  DOI：10.1016/j.tet.2004.03.042

  日期：2004.5

  The [2.2.1]-bicyclic ketone 6, a potential synthetic precursor to CP-225,917, was prepared by a sequence beginning with Diels–Alder reaction between dimethyl fumarate and the silylated cyclopentadiene 38. The adduct 40 was subjected to Tamao–Fleming oxidation, which converted it into alcohol 21. During the oxidation BF3·Et2O–AcOH was used instead of the more expensive BF3·2AcOH complex. Alcohol 21

  [2.2.1]-双环酮6是CP-225,917的潜在合成前体，其制备顺序是从富马酸二甲酯与甲硅烷基化的环戊二烯38之间的Diels-Alder反应开始的。加合物40经过Tamao-Fleming氧化，将其转化为酒精21。在氧化过程中，使用了BF 3 ·Et 2 O-AcOH代替了较昂贵的BF 3 ·2AcOH络合物。将醇21精制为6，它带有CP-225,917的侧链之一，以及其他适合进一步精制的取代基。
• Yokoshima, Satoshi; Tokuyama, Hidetoshi; Fukuyama, Tohru, Angewandte Chemie - International Edition, 2000, vol. 39, # 22, p. 4073 - 4075
  作者：Yokoshima, Satoshi、Tokuyama, Hidetoshi、Fukuyama, Tohru

  DOI：——

  日期：——