2,2,2-trichloro-5-methylbenzo[d]-1,3,2-dioxaphosphole | 178988-65-3

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 2,2,2-trichloro-5-methylbenzo[d]-1,3,2-dioxaphosphole
• 英文别名: 5-Methyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphol；2,2,2-trichloro-5-methyl-1,3,2λ5-benzodioxaphosphole
• CAS: 178988-65-3
• 化学式: C₇H₆Cl₃O₂P
• 分子量: 259.456
• InChiKey: KGKOOYGQDBNSIE-UHFFFAOYSA-N

物化性质

• 沸点：
  95-100 °C(Press: 0.8 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2,2-trichloro-5-methylbenzo[d]-1,3,2-dioxaphosphole 在 乙酸酐 作用下， 以 1,4-二氧六环 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  Goodness of Fit in Complexes between Substrates and Ribonuclease Mimics:  Effects on Binding, Catalytic Rate Constants, and Regiochemistry

  摘要：

  The hydrolysis of 4-tert-butylcatechol cyclic phosphate and of 4-methylcatechol cyclic phosphate catalyzed by alpha-cyclodextrin-6A,6B-bisimidazolide, and by the corresponding derivatives of beta-cyclodextrin (beta CD) and gamma-cyclodextrin (gamma CD), was examined, All three catalysts were able to hydrolyze the substrate derived from 4-methylcatechol, but only the beta CD- and gamma CD-based catalysts could hydrolyze the substrate based on 4-tert-butylcatechol. Saturation kinetics were observed, from which k(cat) and K-m values were derived. The k(cat)'s showed a bell-shaped dependence on pH, indicating a bifunctional mechanism in which one imidazole acted as a base while the other, protonated, acted as an acid catalyst. The strongest binding was observed between the substrate derived from tert-butylcatechol and the beta CD-based catalyst, and this combination also had the highest k(cat), An Arrhenius plot showed that the good fit of the tert-butyl group into the beta CD cavity leads to an entropy advantage for catalysis within the complex, as well as an advantage in the binding. Furthermore, the combination with the best binding and catalytic constant also exhibited the highest regioselectivity in the substrate hydrolysis, being essentially completely selective for one mode of hydrolysis. All these effects reflect the result of a tight fit of the substrate into the catalyst binding cavity, leading to a well-defined reaction geometry.

  DOI：

  10.1021/ja954307n
• 作为产物：
  描述：

  3,4-二羟基甲苯 在 五氯化磷 作用下， 以 苯 为溶剂， 以49.6%的产率得到2,2,2-trichloro-5-methylbenzo[d]-1,3,2-dioxaphosphole
  参考文献：
  名称：

  （苯二氧基）三卤代膦酸酯与芳基乙炔的反应：VI。2,2,2-三卤-5-甲基苯并[ d ] [1,3,2]二恶唑磷与芳基乙炔反应的区域化学

  摘要：

  NMR，IR光谱和X射线衍射表明2,2,2-三氯和2,2,2-三溴-5-甲基苯并[ d ] [1,3,2]二恶唑与 对位反应 -取代的芳基乙炔继续进行区域选择性形成4-芳基-2-卤代-7-甲基-2-氧代苯并[ e ] [1,2]氧杂膦。对于三氯磷鎓，发生了对内环氧原子 对 位的亚苯基片段的选择性氯化 。与三溴磷化物一起形成6-溴和未取代的苯并[ e ] [1,2]氧杂膦作为主要产物。通过X射线衍射研究了一些所获得的氧杂膦的分子和超分子结构。

  DOI：

  10.1007/s11176-005-0108-2

文献信息

• Reaction of arylenedioxytrihalophosphoranes with acetylenes 11. Electronic effect of the substituent in arylacetylene on the reaction rate
  作者：A. V. Nemtarev、V. F. Mironov、A. S. Aniskin、D. S. Baranov、E. V. Mironova、D. B. Krivolapov、R. Z. Musin、S. F. Vasilevskii、N. O. Druzhkov、V. K. Cherkasov

  DOI：10.1007/s11172-013-0008-2

  日期：2013.1

  The reactions of 2,2,2-trichlorobenzo-1,3,2-dioxaphosphole and its benzo-substituted derivatives with arylacetylenes containing strong +M-donors and -M-acceptors afford benzo[e]-1,2-oxaphosphinine 2-oxides (phosphacoumarins) in high yields. Studies by the competitive reaction method showed that the reaction rate is sensitive to the electronic nature of the substituent in arylacetylene. Thus, the introduction

  2,2,2-三氯苯并-1,3,2-二氧杂磷及其苯并取代衍生物与含有强+M-供体和-M-受体的芳基乙炔反应生成苯并[e]-1,2-氧杂膦2-高产率的氧化物（磷香豆素）。竞争反应法研究表明，反应速率对芳基乙炔中取代基的电子性质敏感。因此，将+M-供体引入芳基乙炔的苯环导致反应速率增加，而-M-受体的引入导致反应速率显着降低。通过 X 射线衍射研究了选定的 2-羟基磷杂香豆素和取代的乙烯基膦酸酯的分子和超分子结构，它们是由 P-杂环的裂解产生的。
• Effect of electronic nature of substituents in arylacetylene on the rate of reaction with 2,2,2-trichloroareno-1,3,2-dioxaphosphols
  作者：A. S. Aniskin、A. V. Nemtarev、D. S. Baranov、V. F. Mironov、S. F. Vasilevskii

  DOI：10.1134/s1070363213050253

  日期：2013.5

  far a number of regularities of influence of the phosphorus center nature on a result of the reaction is known [2]. However, there is no information on the effect of the nature of substituents in arylacetylene on synthetic result as well as on the reaction rate. To estimate the effect of the electronic properties of the substituent in arylacetylene we investigated the reaction of benzodioxaphosphols

  2,2,2-trihaloareno-1,3,2-dioxaphosphols 与末端乙炔的反应是合成 benzo-1,2-oxaphosphorine-2-oxide 衍生物的简便方法 [1]。后者的形成是一个多步骤的过程。到目前为止，磷中心性质对反应结果的影响的许多规律是已知的[2]。然而，没有关于芳基乙炔中取代基的性质对合成结果以及反应速率的影响的信息。为了估计芳基乙炔中取代基的电子特性的影响，我们研究了苯并二恶磷 I、II 与芳基乙炔 III、IV 的反应，在对位含有强 +М-供体，如甲氧基，或强 М-受体如硝基。
• Regioselective chlorination of 4- and 5-methyl-2,2,2-trichlorobenzo[d]-1,3,2-dioxaphospholes
  作者：Elena N. Varaksina、Vladimir F. Mironov、Alfia A. Shtyrlina、Alexey B. Dobrynin、Igor A. Litvinov、Alexander I. Konovalov

  DOI：10.1070/mc2005v015n03abeh002069

  日期：2005.1

  The reactions of 4- and 5-methyl-2,2,2-trichlorobenzo[d]-1,3,2-dioxaphospholes with molecular chlorine in an 1:1 ratio occur selectively to give 4-methyl-2,2,2,5-tetrachloro- and 5-methyl-2,2,2,6-tetrachlorobenzo[d]-1,3,2-dioxaphospholes, which undergo hydrolysis to 4-chloro-3-methyl- and 4-chloro-5-methyl-1,2-dihydroxybenzenes, respectively.
• Chlorinations of derivatives of 2,2,2-trichlorobenzo-1,3,2-dioxaphospholes
  作者：E. N. Varaksina、V. F. Mironov、A. A. Shtyrlina、A. B. Dobrynin、K. Yu. Cherkin、A. T. Gubaidullin、I. A. Litvinov、A. I. Konovalov

  DOI：10.1134/s1070428008070087

  日期：2008.7

  By P-31, C-13, C-13-H-1}, and H-1 NMR spectroscopy the chlorination of 4- and 5-methyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphols was shown to provide in quantitative yield 4-methyl-2,2,2,5-tetrachloro- and 6-methyl-2,2,2,5-tetrachlorobenzo-1,3,2-dioxaphosphols. Their hydrolysis led to the formation of difficultly available 4-methyl-5-chloro- and 3-methyl-4-chloro-1,2-dihydroxybenzenes. The structure of the latter compound was established by XRD analysis. The 5-methyl-2-chlorobenzo-1,3,2-dioxaphosphol treated with excess chlorine was converted in succession into 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate and 5-methyl-1,2,4,4,5,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate. The hydrolysis resulted in 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-2-en-1-yl dihydrophosphate. The configuration of three chiral carbon atoms in the latter was established by XRD study. In the course of the chlorination the aromaticity of the ortho-phenylene fragment was distorted and 3,3-sigmatropic shift of the dichlorophosphoryl group occurred. The reaction with chlorine of 5-tert-butyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphol and 2,2,2-trichloro-benzo-1,3,2-dioxaphosphol was not selective: The reaction product obtained in excess chlorine transformed on hydrolysis into tetrachloropyrocatechol. Its solvates with water and dioxane were studies by XRD analysis.
• Reaction of trihalo(phenylenedioxy)phosphoranes with acetylenes: X. specific features of the reactions of substituted 2,2,2-trichloro-1,3,2λ5-benzodioxaphospholes with 3-chloro(bromo, iodo)propynes
  作者：V. F. Mironov、E. N. Varaksina、A. A. Shtyrlina、A. T. Gubaidullin、N. M. Azancheev、R. S. Musin、I. A. Litvinov、A. I. Konovalov

  DOI：10.1134/s1070363206030091

  日期：2006.3

  It was shown for the first time that 3-chloro-, 3-bromo-, and 3-iodopropynes can react with 2.2.2-trichloro-. 2.2.2-trichloro-5-methyl-, and 5,6-dibromo-2,2,2-tricliloro-1,3,2 lambda(5)-benzodioxaphosplioles to Live derivatives of 4-(haloniethyl)-2-chloro-2H-1,2 lambda(5)-benzoxaphosphinin-2-ones. The reaction involves nonselective chlorination of the phenylene substituent in different positions, and the resulting isomer ratio is temperature-dependent. In the reactions of 3-bromo- and 3-iodopropynes with 2,2,2-trichloro-1,3,2 lambda(5)-belizodioxaphosphole. a side process takes place, viz. nucleophilic substitution of bromine and iodine with chlorine. The structure of some of the prepared 4-(chloromethyl)-1,2- benzoxaphosphi nines was studied by means of X-ray diftraction.