tetraphenyl orthocarbonate | 4513-75-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: tetraphenyl orthocarbonate
• 英文别名: tetraphenylorthocarbonate；Tetraphenylorthocarbonat；tetraphenoxymethane；Tetraphenyl-orthocarbonat；Phenyl orthocarbonat；triphenoxymethoxybenzene
• CAS: 4513-75-1
• 化学式: C₂₅H₂₀O₄
• 分子量: 384.431
• InChiKey: ZTBRXBQEWWMNBC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2909309090

反应信息

• 作为反应物：
  描述：

  tetraphenyl orthocarbonate 在 三氟乙酸 作用下， 以 乙腈 为溶剂， 生成 碳酸二苯酯 、 苯酚
  参考文献：
  名称：

  Hydrolysis of Orthocarbonates. Evidence for Charge Imbalance in the Transition State for the General Acid Catalyzed Process

  摘要：

  Catalytic constants have been measured for the hydrolysis of a range of aryl orthocarbonates, in which both the leaving group and trioxocarbenium ion moiety have been systematically varied, by neutral carboxylic acids (trichloroacetic, difluoroacetic, dichloroacetic, malonic, chloroacetic, and acetic) at 70.0 degrees C in 60% water-40% acetonitrile, I = 1.0 M (KCI). Curvature cannot be detected in Bronsted plots involving carboxylic acids only, but inclusion of the point for H3O+ suggests downward curvature (i.e. p(x) greater than or equal to 0). beta(lg), Plots are curved downward (i.e. p(y') = -partial derivative beta(lg)/partial derivative pK(lg) > 0). Substitutent effects in the tris(aryloxy)carbenium ion fragment were quantitated by use of the experimental aqueous pK(a) values of the phenol (pK(rc)), rather than Hammett sigma values, since this gave better correlations for the spontaneous reactions (Kandanarachchi, P.; Sinnott, M. L. J. Am. Chem. Sec., preceding paper in this issue). Cross coefficients are large and not constant: p(xy') (measured as partial derivative alpha/partial derivative pK(lg) rather than partial derivative beta(lg)/partial derivative pK(HA)) varies from 0.26 for (PhOC+ to 0.16 for (pMeOC(6)H(4)OC+. Likewise, p(xy) (measured as -partial derivative alpha/partial derivative pK(rc) rather than -partial derivative beta(rc)/partial derivative partial derivative pK(HA)) experiences large changes with the leaving group pK. Data to estimate p(yy') (beta(rc)/partial derivative K-lg) are more limited, but it too changes with the pK(a) of the catalyzing acid. These data indicate that a two-dimensional More O'Ferrall-Jencks diagram, with one axis representing both C-O cleavage and the ability of substituents in the tris(aryloxy)carbenium ion moiety to sense positive charge development, is inadequate to represent this reaction: separate axes are required for carbon-oxygen bond cleavage and development of carbon-oxygen double-bond character.

  DOI：

  10.1021/ja00092a010
• 作为产物：
  描述：

  碳酸二苯酯 在 五氯化磷 作用下， 以 乙醚 为溶剂， 生成 tetraphenyl orthocarbonate
  参考文献：
  名称：

  Gross,H. et al., Chemische Berichte, 1961, vol. 94, p. 544 - 550

  摘要：

  DOI：

文献信息

• Synthesis of aryl orthocarbonates
  作者：N. Narasimhamurthy、A.G. Samuelson

  DOI：10.1016/s0040-4039(00)84157-x

  日期：1986.1

  A simple and efficient method of preparing tetraaryl orthocarbonates from copper phenoxide and carbon disulfide is described.

  描述了一种由苯酚铜和二硫化碳制备原碳酸四芳基酯的简单有效的方法。
• Reaktionen der substituierten 1,3,3-Trichloro-2-aza-propene [N-(1,1-Dichloro-alkyl)-imidchloride]
  作者：K. FINDEISEN、K. WAGNER、H. HOLTSCHMIDT

  DOI：10.1055/s-1972-21944

  日期：——

  Polychloro-2-azapropenes are readily accessible via high-temperature chlorination of alkyl isocyanide dichlorides, N-alkylimidoyl chlorides, and Schiff bases1. The present review surveys the synthetically useful reactions of the lowest representative of the series, pentachloro-2-azapropene (trichloromethyl isocyanide dichloride, TMI) and shows that the ring-closure reactions of this compound can also be carried out with the higher homologous 1,3,3-trichloro-2-azapropenes 1. Reactions of Trichloromethyl Isocyanide Dichloride (TMI) involving Cleavage of the Molecule 1.1. Hydrolysis of TMI 1.2. Intramolecular Dehydration by TMI 1.3. Reaction of TMI with Alcohols 1.4. Reaction of TMI with Carboxylic Acids 1.5. Reaction of TMI with Sulfonic Acids 2. Reaction of Trichloromethyl Isocyanide Dichloride (TMI) with Carbonyl Groups 2.1. Conversion of Aldehydes into 1,1-Dichloroalkanes 2.2. Conversion of Carboxylic Acid Anhydrides into the Acid Chlorides 3. Reactions of Trichloromethyl Isocyanide Dichloride (TMI) as a Carbonic Acid Derivative (Synthesis of Orthocarbonates) 3.1. Reaction of TMI with Monofunctional Phenols and Trichloroethanol 3.2. Reaction of TMI with Polyfunctional Phenols 4. Syntheses involving Incorporation of the C-3 Atom of Trichloromethyl Isocyanide Dichloride (TMI) or Substituted 1,3,3-Trichloro-2-azapropenes into N-Heterocyclic Compounds 4.1. Synthesis of 1,3,5-Triazines 4.2. Synthesis of Pyrimidines 4.3. Synthesis of Quinazolines 4.4. Synthesis of 1,2,4-Triazoles 4.5. Synthesis of 1,2,4-Oxadiazoles

  多氯-2-氮丙烯可通过高温氯化烷基异氰二氯化物、N-烷基亚胺基氯和席夫碱1来容易地获得。目前的综述调查了该系列中最低代表物五氯-2-氮丙烯（三氯甲基异氰二氯化物，TMI）的合成上有用的反应，并表明通过较高同系物的1,3,3-三氯-2-氮丙烯也可以进行环闭合反应。 1. 三氯甲基异氰二氯化物（TMI）的分子断裂反应 1.1. TMI的水解 1.2. TMI的分子内脱水 1.3. TMI与醇的反应 1.4. TMI与羧酸的反应 1.5. TMI与磺酸的反应 2. 三氯甲基异氰二氯化物（TMI）与羰基的反应 2.1. 醛转化为1,1-二氯烷烃 2.2. 羧酸酐转化为酰氯 3. 三氯甲基异氰二氯化物（TMI）作为碳酸衍生物的反应（正碳酸盐的合成） 3.1. TMI与单功能酚和三氯乙醇的反应 3.2. TMI与多功能酚的反应 4. 合成涉及将三氯甲基异氰二氯化物（TMI）或取代的1,3,3-三氯-2-氮丙烯的C-3原子并入N-杂环化合物 4.1. 1,3,5-三嗪的合成 4.2. 嘧啶的合成 4.3. 喹唑啉的合成 4.4. 1,2,4-三唑的合成 4.5. 1,2,4-噁二唑的合成
• Chemistry of phenoxo complexes. VI. Reactions of phenoxocopper(I) complexes with carbon tetrachloride
  作者：John F. Harrod、Patrick Van Gheluwe

  DOI：10.1139/v79-147

  日期：1979.4.15

  The reactions of several substituted cuprous phenoxides with CCl4 in acetonitrile were examined. Phenoxides without ortho-substituents usually gave high yields of tetraarylorthocarbonates. It is sh...

  研究了几种取代的苯氧基亚铜与四氯化碳在乙腈中的反应。不含邻位取代基的酚盐通常会产生高产率的原碳酸四芳基酯。它是...
• Preparation of Tris(spiroorthocarbonate) Cyclophanes as Back to Back Ditopic Hosts
  作者：Hiroshi Danjo、Kazuhisa Iwaso、Masatoshi Kawahata、Kazuaki Ohara、Toshifumi Miyazawa、Kentaro Yamaguchi

  DOI：10.1021/ol4006882

  日期：2013.5.3

  tris(spiroorthocarbonate) cyclophanes were designed and prepared as ditopic hosts for electrically neutral or electron-rich guests. Preparation of the desired cyclophanes was achieved by cyclotrimerization of 2,2′,3,3′-tetrahydroxy-1,1′-binaphthyl (THB) via the transesterification of tetraphenyl orthocarbonate or dichlorodiphenoxymethane. In those reactions, bis(spiroorthocarbonate) cyclophane containing two

  设计并制备了双碗形的tris（spiroorthocarbonate）环烷作为双位宿主，用于电中性或电子富集的客体。通过原碳酸四苯酯或二氯二苯氧基甲烷的酯交换反应，将2，2'，3，3'-四羟基-1，1'-联萘基（THB）进行环三聚，从而制备所需的环烷。在那些反应中，还形成了含有两个THB单元的双（原碳酸正碳酸酯）环烷作为动力学上有利的产物。螺原碳酸盐双碗在结晶状态下对富勒烯C 60表现出对位分子识别。
• Method for making diaryl carbonate
  申请人：General Electric Company

  公开号：US05504238A1

  公开（公告）日：1996-04-02

  Diaryl carbonate is prepared by hydrolysis of a tetraaryl orthocarbonate in the presence of an acid catalyst. The tetraaryl orthocarbonate is synthesized by a reaction between carbon disulfide and a cuprous phenate; the cuprous phenate can be made from cuprous chloride and the corresponding alkali metal phenate. The process may be integrated with recycle of by-products.

  二苯基碳酸酯是在酸性催化剂存在下，通过四苯基正碳酸酯的水解制备而成。四苯基正碳酸酯是由碳二硫化物和铜酚盐反应合成的；铜酚盐可以由铜氯和相应的碱金属酚盐制备。该过程可以与副产物的回收集成。