1-(1-chlorovinyl)-2',4',6'-trimethylbenzene | 5312-67-4

• 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: 1-(1-chlorovinyl)-2',4',6'-trimethylbenzene
• 英文别名: 1-(2,4,6-Trimethylphenyl)vinyl chloride；α-chloro-2,4,6-trimethylstyrene；α-chloro-2,4,6-trimethyl-styrene；α-Chlor-2,4,6-trimethyl-styrol；1-chloro-1-mesitylethylene；1-Chlor-1-<2,4,6-trimethyl-phenyl>-ethylen；2-(1-Chloroethenyl)-1,3,5-trimethylbenzene
• CAS: 5312-67-4
• 化学式: C₁₁H₁₃Cl
• 分子量: 180.677
• InChiKey: BXIBDACKHDNZFI-UHFFFAOYSA-N

物化性质

• 沸点：
  122-124 °C(Press: 25 Torr)
• 密度：
  1.009±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  1-(1-chlorovinyl)-2',4',6'-trimethylbenzene 在 palladium on activated charcoal 氢气 、 sodium amide 作用下， 生成 1-Mesityl-2-(mesitylsulfonyl)-aethan
  参考文献：
  名称：

  The Stereochemistry of the Addition of Mesitylenethiol to Mesitylacetylene^1-3

  摘要：

  DOI：

  10.1021/ja01483a031
• 作为产物：
  描述：

  2′,4′,6′-三甲基苯乙酮 在 五氯化磷 作用下， 以68%的产率得到1-(1-chlorovinyl)-2',4',6'-trimethylbenzene
  参考文献：
  名称：

  阳离子结构对三唑鎓盐在二甲亚砜中酸度的影响。

  摘要：

  制备了一系列因其不同的电子和空间特性而选择的三唑鎓盐，并使用包围指示剂方法在DMSO中于25°C下测定了其p K a值。各系统的结构变化在所述三唑阳离子的酸性的效果已被认为，特别是检查系统改变电子性质，通过使用量化哈米特的效果σ参数。还报道了产生中性卡宾的偶氮盐的第一个p K a值。这些新数据允许选择适当的碱基，以使这种三唑鎓盐去质子化，并具有使p K a相关的潜力。 本文通过相应的羧苯甲酸酯的亲核性确定的值。

  DOI：

  10.1039/c9ob02258a

文献信息

• An Efficient Bismuth(III) Chloride-Catalyzed Synthesis of 1,1-Diarylalkenesvia Friedel–Crafts Reaction of Acyl Chloride or Vinyl Chloride with Arenes
  作者：Hongbin Sun、Ruimao Hua、Songjie Chen、Yingwu Yin

  DOI：10.1002/adsc.200606157

  日期：2006.9

  In the presence of catalytic amount of bismuth(III) chloride, the reactions of acyl chlorides or vinyl chlorides with arenes afforded 1,1-diarylalkenes in 25–82 % isolated yield. In the case of the reaction of acyl chlorides with arenes, the procedure includes an initial Friedel–Crafts acylation, subsequent formation of vinyl chlorides and final Friedel–Crafts-type vinylation of another arene molecule

  在催化量的氯化铋（III）的存在下，酰氯或氯乙烯与芳烃的反应可提供1,1-二芳基烯烃，分离产率为25-82％。在酰氯与芳烃反应的情况下，该程序包括最初的Friedel-Crafts酰化反应，随后形成的氯乙烯和最终的另一个芳烃分子与氯乙烯的Friedel-Crafts型乙烯基化反应。本文报道了路易斯酸催化的氯乙烯CCl键的首次裂解及其在多取代烯烃合成中的应用。
• Lifetimes and UV-visible absorption spectra of benzyl, phenethyl, and cumyl carbocations and corresponding vinyl cations. A laser flash photolysis study
  作者：Frances L Cozens、V M Kanagasabapathy、Robert A McClelland、Steen Steenken

  DOI：10.1139/v99-210

  日期：1999.12.5

  Benzyl (4-MeO, 4-Me, and 4-methoxy-1-naphthylmethyl), phenethyl (4-Me₂N, 4-MeO, 3,4-(MeO)₂, 4-Me, 3-Me, 4-F, 3-MeO, 2,6-Me₂, parent, and 4-methoxy-1-naphthylethyl) and cumyl (4-Me₂N, 4-MeO, 4-Me, parent) cations have been studied by laser flash photolysis (LFP) in 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). In most cases styrene or α-methylstyrene precursors were employed for the phenethyl and cumyl ions, the intermediate being obtained by solvent protonation of the excited state. Benzyl cations were generated by photoheterolysis of trimethylammonium and chloride precursors. While a 4-MeO substituent provides sufficient stabilization to permit observation of cations in TFE, cations with less stabilizing substituents usually require the less nucleophilic HFIP. Even in this solvent, the parent benzyl cation is too short-lived (lifetime <20 ns) to be observed. When generated in HFIP, phenethyl cations can be seen to react with unphotolyzed styrene, giving rise to dimer cations that are observed to grow in as the initial phenethyl cation decays. The dimer cations, in common with the oligomer cations seen in cationic styrene polymerization, have a λ_max 15-20 nm higher than the monomer and react with both solvent and styrene several orders of magnitude more slowly. This stabilization relative to the phenethyl may reflect an interaction with the aryl group present at the gamma-carbon. Cations 4-MeOC₆H₄C⁺(R)-CH₃ (R = Me, Et, i-Pr, t-Bu, cyclopropyl, C₆H₅, 4-MeOC₆H₄) were generated in TFE via the photoprotonation route. The alkyl series shows that steric effects are important in the decay reaction. The cation with R = cyclopropyl is a factor of 1.5 less reactive than the cation where R = phenyl. Several vinyl cations have also been generated by photoprotonation of phenylacetylenes. ArC⁺=CH₂ has a reactivity very similar to that of its analog ArC⁺H-CH₃, the vinyl cation being slightly (factors of 2-5) shorter-lived. For the various series of cations, including vinyl, substituents in the aryl ring have a consistent effect on the λ_max, a shift to higher wavelength relative to hydrogen of 15 nm for 4-Me, 30 nm for 4-MeO, and 50 nm for 4-Me₂N.Key words: photogenerated carbocations, carbocation lifetime, styrene, photoprotonation.

  苯甲基（4-MeO，4-Me和4-甲氧基-1-萘基甲基）、苯乙基（4-Me2N，4-MeO，3,4-(MeO)2，4-Me，3-Me，4-F，3-MeO，2,6-Me2，母体和4-甲氧基-1-萘基乙基）和叔丁基（4-Me2N，4-MeO，4-Me，母体）阳离子在2,2,2-三氟乙醇（TFE）和1,1,1,3,3,3-六氟异丙醇（HFIP）中通过激光闪光光解（LFP）进行了研究。在大多数情况下，苯乙烯或α-甲基苯乙烯前体被用于苯乙基和叔丁基离子，中间体通过溶剂质子化激发态而获得。苯甲基阳离子是通过三甲基铵和氯化物前体的光异裂生成的。虽然4-MeO取代基提供了足够的稳定性以在TFE中观察到阳离子，但具有较少稳定取代基的阳离子通常需要较不亲核的HFIP。即使在这种溶剂中，母体苯甲基阳离子也太短寿命（寿命<20 ns）而无法观察到。在HFIP中生成的苯乙基阳离子可以看到与未经光解的苯乙烯反应，导致观察到的二聚体阳离子在初始苯乙基阳离子衰减时增长。与阳离子苯乙烯聚合中观察到的寡聚体阳离子一样，二聚体阳离子的λmax比单体高15-20 nm，并且与溶剂和苯乙烯反应速度慢几个数量级。相对于苯乙基的这种稳定性可能反映了与伽马碳上存在的芳基的相互作用。在TFE中通过光质子化途径生成了4-MeOC6H4C+(R)-CH3（R = Me，Et，i-Pr，t-Bu，环丙基，C6H5，4-MeOC6H4）阳离子。烷基系列表明立体效应在衰减反应中很重要。当R = 环丙基时，其反应性比R = 苯基的阳离子少1.5倍。还通过对苯乙炔的光质子化生成了几种乙烯阳离子。ArC+=CH2的反应性与其类似物ArC+H-CH3非常相似，乙烯阳离子寿命略短（2-5倍因子）。对于包括乙烯在内的各系列阳离子，芳香环中的取代基对λmax有一致的影响，相对于氢的15 nm的4-Me，30 nm的4-MeO和50 nm的4-Me2N的波长偏移。关键词：光产生的碳正离子，碳正离子寿命，苯乙烯，光质子化。
• Chirality and conformational changes in 4,5-diaryltriphenylenes
  作者：A.H.A. Tinnemans、W.H. Laarhoven

  DOI：10.1016/0040-4020(79)80041-1

  日期：1979.1

  Line-shape analysis of temperature dependent NMR spectra of several substituted 4,5-diphenyl-triphenylenes has been performed to determine the free energy of activation for rotation (ΔGrot*) of the phenyl groups. The rotational barrier (ΔGrot*) depends on the presence and position of substituents on the phenyl groups; it is the largest in compounds with ortho-substituents. The independent determined

  已被执行的几个取代的4,5-二苯基苯并菲依赖于温度的NMR谱的线形分析来确定的自由能激活旋转（ΔG腐*）的苯基基团。旋转阻挡（ΔG腐*）取决于在苯基基团的取代基的存在和位置; 它是具有邻位取代基的化合物中最大的。独立确定外消旋（ΔG的活化自由能外消旋*）约等于ΔG腐*在4-苯基-5-（3,5-二甲基苯基）三亚苯，但是在4,5-双- （3,5-二甲基苯基）菲ΔG RAC *比ΔG大得多腐*。可以得出结论，外消旋不是通过苯基保持平行的过程发生的，而是通过分子移动（其中苯基彼此像齿轮一样旋转）发生的。
• Absolute kinetics of mesitylmethylchlorocarbene reactions
  作者：Robert A. Moss、Dina C. Merrer

  DOI：10.1039/a607552e

  日期：——

  Absolute rate constants were determined for reactions of mesitylmethylchlorocarbene, which affords intramolecular products derived from 1,2-H migration, 1,2-mesityl migration, and C–H insertion; at -35 or -70 °C, however, the intrusion of intermolecular channels affords azine and carbene dimer, complicating interpretations of the kin-etics.

  确定反应的绝对速率常数 异丙基甲基氯卡宾，可提供衍生的分子内产物 来自 1,2-H 迁移、1,2-异丙基迁移和 C–H 插入；在 -35或-70°C，然而，分子间的侵入 通道提供吖嗪和卡宾二聚体，使解释复杂化 动力学。
• Synthesis of stable nitrile oxide compounds
  申请人：THE GOODYEAR TIRE & RUBBER COMPANY

  公开号：EP0903338A2

  公开（公告）日：1999-03-24

  Nitrile oxide compounds are extremely reactive toward multiple bonds in organic compounds and polymers. This high level of reactivity allows for dinitrile oxides to cure (crosslink) olefin-containing polymers under very mild conditions. This invention discloses a process for the synthesis of stable aryl nitrile oxides which comprises the sequential steps of (1) halomethylating a halomethyl group onto a substituted aromatic compound having at least one substituent group selected from the group consisting of alkyl groups, aryl groups, fused aryl groups, alkaryl groups, halogen atoms, alkoxy groups and nitro groups, wherein said halomethyl group is halomethylated onto a position that is ortho to at least one of the substituent groups on the substituted aromatic compound; (2) converting the ortho halomethylated-substituted aromatic compound into an ortho-substituted aromatic aldehyde by reacting the ortho halomethylated-substituted aromatic compound with a salt selected from the group consisting of sodium 2-nitropropane and potassium 2-nitropropane in a lower alcohol solvent; (3) converting the ortho-substituted aromatic aldehyde into an ortho-substituted aromatic oxime by reacting the ortho-substituted aromatic aldehyde with hydroxylamine; and (4) converting the ortho-substituted aromatic oxime into the ortho-substituted aryl nitrile oxide by reacting the ortho-substituted aromatic oxime with an aqueous sodium hypochlorite solution at a temperature which is within the range of about -5°C to about 20°C.

  氧化腈化合物对有机化合物和聚合物中的多个键具有极高的反应活性。这种高反应性使得二腈氧化物可以在非常温和的条件下固化（交联）含烯烃聚合物。本发明公开了一种用于合成稳定芳基腈氧化物的工艺，该工艺包括以下连续步骤：(1) 将一个卤甲基基团卤化到具有至少一个取代基的取代芳香族化合物上，该取代基选自由烷基、芳基、融合芳基、烷芳基、卤素原子、烷氧基和硝基组成的组，其中所述卤甲基基团卤化到取代芳香族化合物上至少一个取代基的正交位置；(2) 通过在低级醇溶剂中使正代卤代甲基化取代芳香族化合物与选自 2-硝基丙烷钠和 2-硝基丙烷钾的盐反应，将正代卤代甲基化取代芳香族化合物转化为正代取代芳香族醛；(4) 在约-5℃至约 20℃的温度范围内，通过使邻位取代的芳香族肟与次氯酸钠水溶液反应，将邻位取代的芳香族肟转化为邻位取代的芳基腈氧化物。