p-tert-butyl-α-<(chloromethyl)dimethylsilyl>toluene | 112191-50-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: p-tert-butyl-α-<(chloromethyl)dimethylsilyl>toluene
• 英文别名: p-tert-butyl-α-(chloromethyldimethylsilyl)toluene；dimethyl-4-tert-butylbenzylchloromethylsilane；(4-tert-butylphenyl)methyl-(chloromethyl)-dimethylsilane
• CAS: 112191-50-1
• 化学式: C₁₄H₂₃ClSi
• 分子量: 254.875
• InChiKey: DQNUOKJAPLJLMW-UHFFFAOYSA-N

物化性质

• 沸点：
  302.3±22.0 °C(Predicted)
• 密度：
  0.947±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.55
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  双(2-甲氧基乙基)胺 、 p-tert-butyl-α-<(chloromethyl)dimethylsilyl>toluene 生成 p-tert-butyl-α-<<methyl>dimethylsilyl>toluene
  参考文献：
  名称：

  Benzylic Lithium Compounds: The Missing Link in Carbon-Lithium Covalency. Dynamics of Ion Reorientation, Rotation around the Ring-Benzyl Bond, and Bimolecular C-Li Exchange

  摘要：

  Benzyllithium compounds, hitherto assumed from NMR data to consist of ion pairs, have been found to exhibit spin coupling between C-13 and directly bound Li-6 under conditions wherein bimolecular carbon-lithium bond exchange is too slow to average the coupling constants. These conditions involved the use of species in which lithium is internally solvated or of dilute solutions (0.005 M) of benzyllithium-C-13-Li-6 (enriched at C-alpha) at low temperature. The low values of (1)J(C-13-Li-6), 3-4 Hz, imply a small detectable degree of C-Li covalence with the arrangement around C-alpha distorted from coplanarity. The C-Li bonds in benzyllithium are concluded to lie in a continuum of C-Li covalency between the many monomeric species in which (1)J(C-13-Li-6) is 16 +/- 1 Hz and separated ion pairs. NMR line shape analysis of data for internally solvated benzyllithium 2b provides quantitative insight into the dynamics of intramolecular reorientation of coordinated lithium with respect to the benzyl plane, rotation around the ring-C-alpha bond, and bimolecular carbon-lithium bond exchange, listed in order of widely different increasing rates, the activation parameters being Delta H-double dagger (kcal/mol) and Delta S-double dagger (eu) in the same order: 14 and 6.6; 6.4 and -14; 10.8 and -21.

  DOI：

  10.1021/ja00146a018
• 作为产物：
  描述：

  氯甲基二甲基氯硅烷 、 magnesium,1-tert-butyl-4-methanidylbenzene,bromide 以 乙醚 为溶剂， 以42%的产率得到1-tert-Butyl-4-trimethylsilylmethylbenzene
  参考文献：
  名称：

  Benzylic Lithium Compounds: The Missing Link in Carbon-Lithium Covalency. Dynamics of Ion Reorientation, Rotation around the Ring-Benzyl Bond, and Bimolecular C-Li Exchange

  摘要：

  Benzyllithium compounds, hitherto assumed from NMR data to consist of ion pairs, have been found to exhibit spin coupling between C-13 and directly bound Li-6 under conditions wherein bimolecular carbon-lithium bond exchange is too slow to average the coupling constants. These conditions involved the use of species in which lithium is internally solvated or of dilute solutions (0.005 M) of benzyllithium-C-13-Li-6 (enriched at C-alpha) at low temperature. The low values of (1)J(C-13-Li-6), 3-4 Hz, imply a small detectable degree of C-Li covalence with the arrangement around C-alpha distorted from coplanarity. The C-Li bonds in benzyllithium are concluded to lie in a continuum of C-Li covalency between the many monomeric species in which (1)J(C-13-Li-6) is 16 +/- 1 Hz and separated ion pairs. NMR line shape analysis of data for internally solvated benzyllithium 2b provides quantitative insight into the dynamics of intramolecular reorientation of coordinated lithium with respect to the benzyl plane, rotation around the ring-C-alpha bond, and bimolecular carbon-lithium bond exchange, listed in order of widely different increasing rates, the activation parameters being Delta H-double dagger (kcal/mol) and Delta S-double dagger (eu) in the same order: 14 and 6.6; 6.4 and -14; 10.8 and -21.

  DOI：

  10.1021/ja00146a018

文献信息

• Stereochemistry of Solvation of Benzylic Lithium Compounds:  Structure and Dynamic Behavior
  作者：Gideon Fraenkel、Joseph H. Duncan、Kevin Martin、Jinhai Wang

  DOI：10.1021/ja990485v

  日期：1999.11.1

  been prepared. Ring 13C NMR shifts indicate that 12−15 have partially delocalized structures. Externally solvated allylic lithium compounds are found to be delocalized, and only some internally coordinated species are partially delocalized. Compound 15 exists as >95% of one stereoisomer of the two invertomers at Cα. This is in accord with a published ee of >98% in products of the reactions of 15 with

  几种仲苄基锂化合物，均外部配位，[α-（三甲基甲硅烷基）苄基]锂·PMDTA（12）和对叔丁基-α-（二甲基乙基甲硅烷基）苄基锂·TMEDA（13），以及内部配位，[α-（三甲基甲硅烷基）苄基]锂·PMDTA（12）和对叔丁基-α-（二甲基乙基甲硅烷基）苄基锂·TMEDA（13） -[[[[cis-2,5-双(甲氧基甲基)-1-吡咯烷基]甲基]二甲基甲硅烷基]-对叔丁基苄基]锂(14)和[α-[[[(S)-2-(甲氧基甲基) -1-吡咯烷基]甲基]二甲基甲硅烷基]苄基]锂（15）。环 13C NMR 位移表明 12-15 具有部分离域结构。发现外部溶剂化的烯丙基锂化合物是离域的，只有一些内部配位的物种部分离域。化合物 15 以超过 95% 的两种转化异构体的一种立体异构体形式存在于 Cα。这与公开的 15 与醛反应产物中的 ee 大于 98% 是一致的。所有四种化合物都显示出单键 13C-6Li
• Microbicides
  申请人：Ciba-Geigy Corporation

  公开号：US04762826A1

  公开（公告）日：1988-08-09

  The invention relates to novel heterocyclic organosilyl compounds of the general formula I ##STR1## wherein R.sub.1 is hydrogen, C.sub.1 -C.sub.10 alkyl, C.sub.3 -C.sub.7 cycloalkyl, phenyl or trimethylsilyl, R.sub.2 is hydrogen or C.sub.1 -C.sub.4 alkyl, or R.sub.1 and R.sub.2 together form a saturated or unsaturated ring containing 6 carbon atoms; R.sub.3 and R.sub.4 are each independently of the other hydrogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy, and R.sub.4 may also be C.sub.3 -C.sub.7 cycloalkyl; R.sub.5 to R.sub.12 are each independently hydrogen or C.sub.1 -C.sub.4 alkyl, and R.sub.8 and R.sub.9 together may also form a saturated or unsaturated ring containing 6 carbon atoms; X is CH.sub.2, oxygen or sulfur, and n and Z are each independently of the other 0 or 1, and, if Z is 0, to the acid addition salts thereof. The novel compounds have microbicidal properties and are suitable in particular for controlling phytopathogenic microorganisms.

  本发明涉及新颖的杂环有机硅化合物，其一般式为I 其中，R1是氢、C1-C10烷基、C3-C7环烷基、苯基或三甲基硅基，R2是氢或C1-C4烷基，或R1和R2一起形成一个含有6个碳原子的饱和或不饱和环；R3和R4分别独立地是氢、C1-C4烷基或C1-C4烷氧基，而R4还可以是C3-C7环烷基；R5至R12各自独立地是氢或C1-C4烷基，而R8和R9也可以一起形成一个含有6个碳原子的饱和或不饱和环；X是CH2、氧或硫，n和Z各自独立地为0或1，如果Z为0，则是其酸加成盐。这些新型化合物具有杀菌性能，特别适用于控制植物病原微生物。
• Benzylic Lithium Compounds: The Missing Link in Carbon-Lithium Covalency. Dynamics of Ion Reorientation, Rotation around the Ring-Benzyl Bond, and Bimolecular C-Li Exchange
  作者：Gideon Fraenkel、Kevin Martin

  DOI：10.1021/ja00146a018

  日期：1995.10

  Benzyllithium compounds, hitherto assumed from NMR data to consist of ion pairs, have been found to exhibit spin coupling between C-13 and directly bound Li-6 under conditions wherein bimolecular carbon-lithium bond exchange is too slow to average the coupling constants. These conditions involved the use of species in which lithium is internally solvated or of dilute solutions (0.005 M) of benzyllithium-C-13-Li-6 (enriched at C-alpha) at low temperature. The low values of (1)J(C-13-Li-6), 3-4 Hz, imply a small detectable degree of C-Li covalence with the arrangement around C-alpha distorted from coplanarity. The C-Li bonds in benzyllithium are concluded to lie in a continuum of C-Li covalency between the many monomeric species in which (1)J(C-13-Li-6) is 16 +/- 1 Hz and separated ion pairs. NMR line shape analysis of data for internally solvated benzyllithium 2b provides quantitative insight into the dynamics of intramolecular reorientation of coordinated lithium with respect to the benzyl plane, rotation around the ring-C-alpha bond, and bimolecular carbon-lithium bond exchange, listed in order of widely different increasing rates, the activation parameters being Delta H-double dagger (kcal/mol) and Delta S-double dagger (eu) in the same order: 14 and 6.6; 6.4 and -14; 10.8 and -21.