1,1-二甲基-4-硅杂环己酮 | 18276-42-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1,1-二甲基-4-硅杂环己酮
• 英文名称: 1,1-dimethyl-1-silacyclohexan-4-one
• 英文别名: dimethyl-4,4 sila-4 cyclohexanone；4,4-dimethyl-4-silacyclohexanone；1,1-dimethylsilinan-4-one；dimethylsilacyclohexanone；1,1-dimethylsilinane-4-one；1,1-dimethyl-silinan-4-one
• CAS: 18276-42-1
• 化学式: C₇H₁₄OSi
• 分子量: 142.273
• InChiKey: YJWAMCPLZPXFCB-UHFFFAOYSA-N

物化性质

• 沸点：
  118-120 °C(Press: 59 Torr)
• 密度：
  0.89±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.06
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2914190090

反应信息

• 作为反应物：
  描述：

  1,1-二甲基-4-硅杂环己酮 在 乙酸铵 、 溶剂黄146 作用下， 以 乙醇 、 水 、 甲苯 为溶剂， 反应 5.0h， 生成 Cyano-(4-cyano-1,1-dimethyl-silinan-4-yl)-acetic acid ethyl ester
  参考文献：
  名称：

  Antiarthritic and supressor cell inducing activity of azaspiranes: structure-function relationships of a novel class of immunomodulatory agents

  摘要：

  Spirogermanium (1; 8,8-diethyl-N,N-dimethyl-2-aza-8- germaspiro[4.5]decane-2-propanamine dihydrochloride) is a potent cytotoxic agent in vitro which has demonstrated limited activity in experimental animal tumor models. Subsequently, it has been reported that spirogermanium has antiarthritic and suppressor cell-inducing activity. We have synthesized a series of substituted 8-hetero-2-azaspiro[4.5]decane and 9-hetero-3-azaspiro[5.5]undecane analogues of spirogermanium to identify the heteroatom requirements for in vivo antiarthritic and suppressor cell-inducing activity. This structure-activity relationship study has identified that appropriately substituted silicon and carbon analogues of spirogermanium retain both antiarthritic and immunosuppressive activity, with the 8,8-dipropyl (carbon) analogue being among the most active. Following the identification of N,N-dimethyl-8,8-dipropyl-2-azaspiro[4.5]decane-2-propanamine++ + dihydrochloride (9) as a more active analogue than spirogermanium, a series of 8,8-dipropyl analogues with various amine substituents were synthesized. A number of these analogues had activity similar to that of 9. A correlation between activity in the adjuvant arthritic rat and the ability to induce suppressor cells (r = 0.894, p less than 0.001) suggests an association between the two pharmacologic effects. While the precise biochemical mechanism(s) for the pharmacological activity is unclear, these data suggest that compounds within this series, e.g., N,N-dimethyl-8,8-dipropyl-2-azaspiro[4.5]decane-2-propanamine++ + dihydrochloride, may provide effective therapy in diseases of autoimmune origin and/or the prevention of rejection in tissue transplantation.

  DOI：

  10.1021/jm00173a010
• 作为产物：
  描述：

  3,3'-(dimethylsilanediyl)dipropan-1-ol 在 sodium hydroxide 、 potassium permanganate 、 硫酸 、 potassium tert-butylate 作用下， 以 苯 为溶剂， 生成 1,1-二甲基-4-硅杂环己酮
  参考文献：
  名称：

  Spirans XXI。silaazaspiro [4.5]癸烷的合成

  摘要：

  N-（2-二甲基氨基丙基）-8,8-二甲基-8-sila-2-azaspiro [4.5]癸烷（1）和N-（3-二甲基氨基丙基）-9,9-二甲基-9-sila-3由4，4-二甲基-4-硅环己酮（5）合成了-azaspiro [5.5]十一烷（2）。对1和2的生物学评估表明，它对组织培养中生长的人类癌细胞具有细胞毒作用。

  DOI：

  10.1002/jhet.5570100510

文献信息

• Synthesis of Silacyclohexanones from Divinylsilanes and Allylamines by a Rh-Catalyzed Cyclization
  作者：Jiawei Guo、Song Liu、Qinjiao Pang、Hongyun Zhang、Lu Gao、Li Chen、Zhenlei Song

  DOI：10.1021/acs.orglett.1c04183

  日期：2022.1.21

  An efficient synthesis of silacyclohexanones bearing a variety of silyl substituents has been developed by a [Rh(coe)2Cl]2/PCy3-catalyzed cyclization of divinylsilanes with Jun’s allylamine. The silacyclohexanones can be oxidized with DDQ to give the corresponding silacyclohexadienones, which are further transformed into silicon analog of 2-deoxystreptamine or exo-alkylidenesilacyclohexadienes.

  通过[Rh(coe) 2 Cl] 2 /PCy 3催化的二乙烯基硅烷与Jun's烯丙胺的环化，开发了一种有效合成具有多种甲硅烷基取代基的硅环己酮。硅杂环己酮可以用 DDQ 氧化得到相应的硅环己二烯酮，其进一步转化为 2-脱氧链霉胺或外亚烷基硅环己二烯的硅类似物。
• Acetolysis of 4,4-disubstituted 4-silacyclohexyl tosylates: effect of remote silicon substitution on organic reactivity
  作者：Stephen S. Washburne、Ram R. Chawla

  DOI：10.1016/s0022-328x(00)98112-9

  日期：1977.6

  and phenyl-methyl-substituted 4-silacyclohexyl tosylates (IcId) were compared with isosteric 4,4-disubstituted cyclohexyl tosylates. The rates of acetolysis of the silatosylates were three to five times greater than those of the carbocyclic analogs. With the exception of Ia, which largely fragmented to di-4-pentenyltetramethyldisiloxane, the acetolysis products of compounds I were acetates and olefins

  比较了4，4-二甲基-（Ia），4，4-二苯基-（Ib）和苯基-甲基取代的4-硅烷基环己基甲苯磺酸酯（IcId）与等排性4,4-二取代环己基甲苯磺酸酯。硅藻土酸酯的乙酰分解速率是碳环类似物的三到五倍。除了Ia，其大部分片段化为二-4-戊烯基四甲基二硅氧烷外，化合物I的乙酰分解产物是乙酸酯和烯烃，其比例与环己基甲苯磺酸酯的比例相似。结论是，γ-甲硅烷基取代基对甲苯磺酸酯的动力学和产物确定作用很小，尽管在通过重排可以形成稳定的β-甲硅烷基碳离子的情况下，如Ia，碎裂产物将占主导地位。
• Silacycles as templates for acyclic diastereoselection
  作者：John A. Soderquist、Alvin Negron

  DOI：10.1016/s0040-4039(98)02200-x

  日期：1998.12

  The 4-substituted silacyclohex-3-enes (3) prepared from the vinyl triflate (9) derived from 1,1-dimethyl-1-silacyclohexan-4-one (1) and higher-order organocuprates provides a versatile template for the construction of non-racemic 3-methyl-4-penten-1-ol (6). Through asymmetric hydroboration, 3 affords the requisite β-hydroxysilane (4) with the ideal geometry to undergo elimination to the chiral acyclic

  由衍生自1,1-二甲基-1-silacyclohexan-4-one（1）的三氟甲磺酸乙烯酯（9）和高阶有机铜酸酯制备的4-取代的silacyclohex-3-enes（3）提供了通用的结构模板非外消旋的3-甲基-4-戊烯-1-醇（6）。通过不对称氢硼化，3可获得具有理想几何结构的必需β-羟基硅烷（4），以消除被氧化转化为6的手性无环硅烷（5）。
• Spirans XXI. Synthesis of silaazaspiro[4.5]decanes and silaazaspiro[5.5]undecanes
  作者：Leonard M. Rice、Bhagvandas S. Sheth、James W. Wheeler

  DOI：10.1002/jhet.5570100510

  日期：1973.10

  N-(2-Dimethylaminopropyl)-8,8-dimethyl-8-sila-2-azaspiro[4.5]decane (1) and N-(3-dimethyl-aminopropyl)-9,9-dimethyl-9-sila-3-azaspiro[5.5]undecane (2) have been synthesized from 4,4-dimethyl-4-silacyclohexanone (5). Biological evaluation of 1 and 2 indicated cytotoxic action against human cancer cells grown in tissue culture.

  N-（2-二甲基氨基丙基）-8,8-二甲基-8-sila-2-azaspiro [4.5]癸烷（1）和N-（3-二甲基氨基丙基）-9,9-二甲基-9-sila-3由4，4-二甲基-4-硅环己酮（5）合成了-azaspiro [5.5]十一烷（2）。对1和2的生物学评估表明，它对组织培养中生长的人类癌细胞具有细胞毒作用。
• Polymer, resist composition and patterning process
  申请人：——

  公开号：US20010003772A1

  公开（公告）日：2001-06-14

  A polymer bearing specific cyclic silicon-containing groups is novel. A resist composition comprising the polymer as a base resin is sensitive to high-energy radiation and has excellent sensitivity and resolution at a wavelength of less than 300 nm, and high resistance to oxygen plasma etching. The resist composition lends itself to micropatterning for the fabrication of VLSIs.

  一种具有特定环状含硅基团的高分子轴承是新颖的。以该高分子为基础树脂的抗蚀剂组合物对高能辐射敏感，在小于300纳米的波长下具有良好的敏感性和分辨率，并具有高抗氧等离子体刻蚀性能。该抗蚀剂组合物适用于微细图案制造，用于制造超大规模集成电路。