1,1,3,3-tetraisocyanato-1,3-dimethyldisiloxane | 220289-00-9

• 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: 1,1,3,3-tetraisocyanato-1,3-dimethyldisiloxane
• 英文别名: Disiloxane, 1,1,3,3-tetraisocyanato-1,3-dimethyl-；[diisocyanato(methyl)silyl]oxy-diisocyanato-methylsilane
• CAS: 220289-00-9
• 化学式: C₆H₆N₄O₅Si₂
• 分子量: 270.308
• InChiKey: OZTHBAQGMOUPIX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.52
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  127
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  1,1,3,3-tetraisocyanato-1,3-dimethyldisiloxane 在 水 作用下， 以 1,4-二氧六环 为溶剂， 以68%的产率得到1,1,3,5,7,7-hexaisocyanato-1,3,5,7-tetramethyltetrasiloxane
  参考文献：
  名称：

  Synthesis and Structure ofcis-trans-cis-1,3,5,7-Tetraisocyanato-1,3,5,7-tetramethylcyclotetrasiloxane

  摘要：

  1,1,3,5,7,7-六异氰酸基-1,3,5,7-四甲基四硅氧烷在四氢呋喃中的受控水解得到所需的环四硅氧烷，预计其将成为具有反构型的新型梯形低聚硅氧烷的结构单元，与具有顺式构型的传统梯形低聚硅氧烷相比。

  DOI：

  10.1246/cl.2006.114
• 作为产物：
  描述：

  三异氰酸-甲基-硅烷 在 水 作用下， 以 四氢呋喃 为溶剂， 生成 1,1,3,3-tetraisocyanato-1,3-dimethyldisiloxane
  参考文献：
  名称：

  Synthesis and Structure ofsyn,anti,syn-Pentacyclic Ladder Oligomethylsilsesquioxane

  摘要：

  使用顺式，反式，顺式-[MeSi(NCO)O]4 作为结构单元合成了新型五环梯形低聚甲基倍半硅氧烷。通过再沉淀从反应混合物中分离出该化合物，收率13%。 X射线晶体学显示五环呈现顺式、反式、顺式构型，从而形成管状结构。

  DOI：

  10.1246/cl.2011.722

文献信息

• Syntheses and Properties of Isocyanatodisiloxanes and Their Alkoxy-Substituted Derivatives
  作者：Takahiro Gunji、Akira Setogawa、Kazue Asakura、Yoshimoto Abe

  DOI：10.1246/bcsj.71.2967

  日期：1998.12

  Isocyanatooligosiloxanes and their alkoxy derivatives were synthesized. The hydrolysis of triisocyanato(methyl)silane followed by distillation provided 1,1,3,3-tetraisocyanato-1,3-dimethyldisiloxane in good yield. The reaction of 1,1,3,3-tetraisocyanato-1,3-dimethyldisiloxane with ethanol, isopropyl alcohol, and t-butyl alcohol proceeded selectively to afford partially alkoxy substituted isocyanatodimethyldisiloxanes, (RO)n(NCO)4−nMe2Si2O (R = Et, n = 1—4; R = Pri, n = 1—4; and R = But, n = 1—2). On the other hand, the hydrolysis of tetraisocyanatosilane provided a mixture of isocyanatooligosiloxanes. Hexaisocyanatodisiloxane was isolated by distillation from the reaction mixture with some impurities produced by the disproportionation of hexaisocyanatodisiloxane on heating. The reaction of hexaisocyanatodisiloxane with alcohols provided partially alkoxy-substituted isocyanatodisiloxanes, [(RO)n(NCO)3−nSi]2O (R = Et, n = 2—3; R = Pri, n = 1—3; and R = But, n = 1—2), selectively and in high yield.

  合成了异氰酸酷二硅氧烷及其烷氧基衍生物。通过水解三异氰酸基（甲基）硅烷，然后进行蒸馏，得到了 1,1,3,3-四异氰酸基-1,3-二甲基二硅氧烷，收率很高。1,1,3,3-四异氰酸基-1,3-二甲基二硅氧烷与乙醇、异丙醇和叔丁醇的反应选择性地生成部分烷氧基取代的异氰酸基二甲基二硅氧烷，即 (RO)n(NCO)4-nMe2Si2O（R = Et，n = 1-4；R = Pri，n = 1-4；R = But，n = 1-2）。另一方面，四异氰酸硅烷的水解提供了异氰酸ooligosiloxanes 的混合物。通过蒸馏从反应混合物中分离出了六异氰酸基二硅氧烷，其中还含有一些杂质，这些杂质是六异氰酸基二硅氧烷在加热时发生歧化而产生的。六异氰酸基二硅氧烷与醇类反应后，可选择性地以高产率提供部分烷氧基取代的异氰酸基二硅氧烷 [(RO)n(NCO)3-nSi]2O （R = Et，n = 2-3；R = Pri，n = 1-3；R = But，n = 1-2）。
• Syntheses and Properties of Sila-Functional Oligosiloxanes—Linear and Cyclic Tetrasiloxanes with Methyl and Vinyl Groups—
  作者：Takahiro Gunji、Miho Watanabe、Koji Abe、Yoshimoto Abe

  DOI：10.1246/bcsj.76.341

  日期：2003.2

  The syntheses of the titled oligosiloxanes by controlled hydrolysis of the corresponding isocyanatosilanes under vapor phase or in THF (or THF/ether) were investigated. The vapor phase hydrolysis of RSi(NCO)3 (R = Me, Vinyl) with a water–1,4-dioxane vapor gave the disiloxanes [R(OCN)2Si]2O in yields of 85% (R = Me) and 90% (R = Vinyl). Further vapor phase hydrolysis of the disiloxanes provided the linear tetrasiloxanes NCO[SiR(NCO)O]3SiR(NCO)2 in yields of 71% (R = Me) and 69% (R = Vinyl). The cyclotetrasiloxanes [R(OCN)SiO]4 were synthesized in yields of 12% (R = Me) and 33% (R = Vinyl) or 24% (R = Me) and 58% (R = Vinyl) by hydrolysis of the disiloxanes or of the linear tetrasiloxanes in THF, respectively. On the other hand, the linear tetrasiloxanes OCN[SiR(OPri)O]3SiR(OPri)(NCO) were obtained in yields of 50% (R = Me) and 56% (R = Vinyl) by hydrolysis of [R(OCN)(PriO)Si]2O prepared from RSi(OPri)(NCO)2 under mild conditions in THF/ether, while the cyclic tetrasiloxanes [R(PriO)SiO]4 were afforded in the yield of 61–62% by hydrolysis of the disiloxanes under more severe conditions in THF.

  研究人员通过在气相或 THF（或 THF/乙醚）中控制相应异氰酸硅烷的水解，合成了标题低硅氧烷。RSi(NCO)3（R = Me，Vinyl）与水-1,4-二氧六环蒸汽的气相水解得到了二硅氧烷[R(OCN)2Si]2O，产率分别为 85%（R = Me）和 90%（R = Vinyl）。进一步对二硅氧烷进行气相水解，可得到线性四硅氧烷 NCO[SiR(NCO)O]3SiR(NCO)2 ，产率分别为 71%（R = Me）和 69%（R = Vinyl）。通过在 THF 中水解二硅氧烷或线型四硅氧烷，合成了环四硅氧烷 [R(OCN)SiO]4，产率分别为 12%（R = Me）和 33%（R = 乙烯基），或 24%（R = Me）和 58%（R = 乙烯基）。另一方面，由 RSi(OPri)(NCO)2制备的[R(OCN)(PriO)Si]2O在 THF/乙醚中的温和条件下水解得到线性四硅氧烷 OCN[SiR(OPri)O]3SiR(OPri)(NCO)，产率分别为 50%（R = Me）和 56%（R = Vinyl）、而环状四硅氧烷[R(PriO)SiO]4 则是在 THF 中以更苛刻的条件水解二硅氧烷得到的，产率为 61-62%。
• Syntheses and Properties of Sila-functional Oligosiloxanes: A Simple and Practical Method for the Synthesis of 1,1,3,3-Tetra-isocyanato-1,3-disubstituted Disiloxane
  作者：Yoshimoto Abe、Koji Abe、Miho Watanabe、Takahiro Gunji

  DOI：10.1246/cl.1999.259

  日期：1999.3

  The titled disiloxanes with the substituents of methyl, vinyl, phenyl, and isocyanato group were synthesized in excellent yields by a vapor phase hydrolysis of the corresponding isocyanatosilanes using a simple reaction apparatus. The process would provide a practical method for the syntheses of not only the sila-functional disiloxanes but also the other oligosiloxanes with various functional groups.

  通过使用简单的反应装置对相应的异氰酸硅烷进行气相水解，合成了具有甲基、乙烯基、苯基和异氰酸基取代基的标题二硅氧烷，并获得了极高的产率。该工艺不仅为合成硅烷官能团二硅氧烷，还为合成其他具有不同官能团的低聚硅氧烷提供了一种实用方法。
• Synthesis and crystal structure of disiloxane-1,3-diols and disiloxane-1,1,3,3-tetraol
  作者：Ken-ichi Suyama、Takanori Nakatsuka、Takahiro Gunji、Yoshimoto Abe

  DOI：10.1016/j.jorganchem.2007.01.016

  日期：2007.4

  1,3-Dimethyl- or 1,3-divinyl-1,3-di-t-butoxydisiloxane-1,3-diol and 1,3-diphenyldisiloxane-1,1,3,3-tetraol were synthesized by hydrolysis of the corresponding diisocyanatodisiloxanes and tetrachlorodisiloxane. The disiloxanediols were soluble in common organic solvents and thermally very stable, therefore, they could be sublimed without decomposition. X-ray crystallography showed that the disiloxane-1,3-diols in the crystal feature a 1.21 nm diameter columnar array with intermolecular hydrogen bonding. The disiloxane1,1,3,3,-tetraol, on the other hand, revealed molecules with a gauche- and anti-conformation depending on crystallization method which formed a columnar array and a sheet-like array, respectively. It was confirmed that these silanols can be potential building blocks for ladder oligosilsesquioxanes. (c) 2007 Elsevier B.V. All rights reserved.
• Synthesis and Structure of<i>syn</i>,<i>anti</i>,<i>syn</i>-Pentacyclic Ladder Oligomethylsilsesquioxane
  作者：Hiroyasu Seki、Noritaka Abe、Yoshimoto Abe、Takahiro Gunji

  DOI：10.1246/cl.2011.722

  日期：2011.7.5

  Novel pentacyclic ladder oligomethylsilsesquioxane was synthesized using cis,trans,cis-[MeSi(NCO)O]4 as a building block. This compound was isolated in 13% yield by reprecipitation from the reaction mixture. X-ray crystallography revealed that pentacyclic rings assume a syn,anti,syn-configuration, resulting in the tube-like structure.

  使用顺式，反式，顺式-[MeSi(NCO)O]4 作为结构单元合成了新型五环梯形低聚甲基倍半硅氧烷。通过再沉淀从反应混合物中分离出该化合物，收率13%。 X射线晶体学显示五环呈现顺式、反式、顺式构型，从而形成管状结构。