ethoxycarbonylmethyl phenyl telluride | 116246-83-4

• 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: ethoxycarbonylmethyl phenyl telluride
• 英文别名: ethyl-α-phenyltelluro acetate；ethyl phenyltellurenylacetate；Ethyl phenyltelluroacetate；PhTeCH2CO2Et；Ethyl 2-phenyltellanylacetate
• CAS: 116246-83-4
• 化学式: C₁₀H₁₂O₂Te
• 分子量: 291.804
• InChiKey: NZZONPJBRXHQPE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.0
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethoxycarbonylmethyl phenyl telluride 在 lithium hydroxide 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以55%的产率得到α-phenyltelluro acetic acid
  参考文献：
  名称：

  Synthesis and¹²⁵Te NMR Spectroscopy of α-Tellurocarbonyl Compounds and Derivatives

  摘要：

  The reaction of lithium alkyl-, alkenyl-, alkynyl-, and aryl tellurolates with alpha-bromocarbonyl compounds in anhydrous tetrahydrofuran gives the title compounds in yields ranging from 55-92%. The Te-125 NMR chemical shift range for these compounds is 405-1024 ppm.

  DOI：

  10.1080/00397919108019802
• 作为产物：
  描述：

  重氮乙酸乙酯 、 联苯二碲 在 copper(II) sulfate 作用下， 以 苯 为溶剂， 反应 0.5h， 以70%的产率得到ethoxycarbonylmethyl phenyl telluride
  参考文献：
  名称：

  Synthesis of α-phenylchalcogeno acetic acids, ethyl-α-phenylchalcogeno acetates and ethyl-α-halo-α-phenylchalcogeno acetates

  摘要：

  Reaction of phenyltellurolate or phenylselenolate anion with alpha-bromoacetic acid under phase transfer conditions using a liquid-solid system affords the alpha-phenyltelluro acetic acid and the alpha-phenylseleno acetic acid in 44 and 50% yields respectively. Under similar reaction conditions, phenyl chalcogenate anions react with ethyl alpha-bromoacetate to give the corresponding ethyl-alpha-phenyltelluro acetate in 52% and ethyl-alpha-phenylseleno acetate in 47% yield.Reaction of phenylselenenyl chloride with ethyl diazoacetate in THF at 0-degrees-C yields exclusively the ethyl-alpha-chloro-alpha-phenylseleno acetate in 88% yield. Similar reactions performed by addition of phenylselenenyl bromide in THF or benzene to the ethyl diazoacetate at different temperatures result in mixtures of ethyl-alpha-bromo-alpha-phenylseleno acetate and ethyl-alpha,alpha-bis(phenylseleno) acetate in different ratios. However, when the ethyl diazoacetate was slowly added to a solution of phenylselenenyl bromide in benzene under reflux, the ethyl-alpha-bromo-alpha-phenylseleno acetate was obtained in 84% yield as the only product. Reaction of ethyl diazoacetate with phenyltellurenyl bromide in benzene at room temperature results in formation of ethyl-alpha-bromo-alpha-phenyltelluro acetate that decomposes rapidly into the corresponding tellurone.Addition of ethyl diazoacetate to a mixture of diphenyldiselenide and copper sulfate in benzene under reflux results in a mixture of ethyl-alpha-phenylseleno acetate: ethyl-alpha,alpha-bis(phenylseleno) acetate (10:1). Using an alternative route, the ethyl-alpha-phenylseleno acetate was obtained in 74% yield by esterification of alpha-phenylseleno acetic acid in benzene with ethanol/sulfuric acid. The ethyl-alpha-phenylseleno acetate was transformed into the ethyl-alpha-bromo-alpha-phenylseleno acetate in 41% yield by treatment with N-bromosuccinimide.On the other hand, the copper-catalyzed thermal reaction of ethyl diazoacetate with diphenyl ditelluride in benzene afforded the corresponding ethyl-alpha-phenyltelluro acetate as the only product.

  DOI：

  10.1016/0022-328x(93)80355-f

文献信息

• Substituent effects and stereochemistry in125Te NMR spectroscopy. Diorganyltellurium dihalides and some tellurides and ditellurides
  作者：Helmut Duddeck、Armin Biallaβ

  DOI：10.1002/mrc.1260320509

  日期：1994.4

  125Te, 19F and 13C NMR data for 33 compounds containing tellurium substituents are presented. The 125Te chemical shifts in (PhTeCl2)R compounds are between δ = 878 and 1023; in corresponding (PhTeF2)R compounds they are 220 to 360 ppm larger. Effects of substituents and conformational interconversions (dynamic 125Te NMR) are discussed. Several diastereomers were identified in (PhTeCl2)R derivatives

  提供了 33 种含有碲取代基的化合物的 125Te、19F 和 13C NMR 数据。(PhTeCl2)R 化合物中的 125Te 化学位移介于 δ = 878 和 1023 之间；在相应的 (PhTeF2)R 化合物中，它们要大 220 到 360 ppm。讨论了取代基和构象互变（动态 125 Te NMR）的影响。在 (PhTeCl2)R 衍生物中发现了几种非对映异构体，它们在室温下是稳定的，并且碲原子的构型不同（受限制的假旋转）。结果表明，125Te 是非常适合手性识别的核。
• Synthesis of α-Phenyltelluro Carbonyl Compounds
  作者：Tomoki Hiiro、Nobuaki Kambe、Akiya Ogawa、Noritaka Miyoshi、Shinji Murai、Noboru Sonoda

  DOI：10.1055/s-1987-28180

  日期：——

  Several new α-phenyltelluro carbonyl compounds have been synthesized by the reaction of benzenetellurenyl iodide with lithium enolates derived from ketones, esters, and an amide in tetrahydrofuran at -78°C.

  几种新的α-苯基碲羰基化合物是通过苯碲基碘化物与由酮、酯和酰胺衍生的烯醇锂在四氢呋喃中在-78°C 下反应合成的。
• Free radical addition of α-telluroesters to alkenes
  作者：Nobuaki Kambe、Li-Biao Han、Shin-ichi Fujiwara、Noboru Sonoda

  DOI：10.1002/hc.20716

  日期：——

  α-(Phenyltelluro)esters 2 reacted with electron-rich alkenes 3 in the presence of a catalytic amount of azobisisobutyronitrile (AIBN) as an initiator to give the corresponding addition products 4. This carbotelluration of alkenes proceeded via a radical chain mechanism involving the bimolecular homolytic substitution (SH2) reaction on tellurium as the key step, wherein tellurium plays an important role in a kinetic

  在催化量的偶氮二异丁腈 (AIBN) 作为引发剂的存在下，α-（苯基碲）酯 2 与富电子烯烃 3 反应，得到相应的加成产物 4。烯烃的这种碳化反应是通过涉及双分子的自由基链机制进行的碲上的均裂取代（SH2）反应是关键步骤，其中碲在动力学方式中起着重要作用，以实现快速的基团转移过程，从而抑制竞争性烯烃聚合。© 2011 Wiley Periodicals, Inc. 杂原子化学 22:518–522, 2011; 在 wileyonlinelibrary.com 上在线查看这篇文章。DOI 10.1002/hc.20716
• Synthetic and Theoretical Studies on Group-Transfer Imidoylation of Organotellurium Compounds. Remarkable Reactivity of Isonitriles in Comparison with Carbon Monoxide in Radical-Mediated Reactions
  作者：Shigeru Yamago、Hiroshi Miyazoe、Ryuta Goto、Masahiro Hashidume、Takashi Sawazaki、Jun-ichi Yoshida

  DOI：10.1021/ja003879r

  日期：2001.4.1

  Imidoylation of organotellurium compounds with isonitriles has been investigated in conjunction with the radical-mediated C1 homologation reaction by using CO and isonitriles. Carbon-centered radicals generated photochemically or thermally from organotellurium compounds react with isonitriles in a group-transfer manner to give the corresponding imidoylated products. Organotellurium compounds have been found to serve as effective precursors of a wide variety of stabilized radicals, namely benzyl, alpha -alkoxy, alpha -amino, and acyl radicals, which take part in the imidoylation with high efficiency. The reactions are compatible with various functional groups, and can be carried out in various solvents including environmentally benign water. The reactivity of isonitriles has been compared with that of CO through competition experiments, and the results indicate that isonitriles are superior to CO as radical accepters in reactions with stabilized radicals. The origin of the differences has been addressed in theoretical studies with density functional theory calculations using the B3LYP hybrid functional. The calculations suggest that both carbonylation and imidoylation proceed with low activation energies, and that there an virtually no differences in the kinetic sense, instead, it indicates that thermodynamic effects, namely differences in the stability of the acyl and the imidoyl radicals, control the overall course of the reactions.
• Rate constants for chalcogen group transfers in bimolecular substitution reactions with primary alkyl radicals
  作者：Dennis P. Curran、Amanda A. Martin-Esker、Sung Bo Ko、Martin Newcomb

  DOI：10.1021/jo00069a036

  日期：1993.8

  Rate constants for group transfers of the MeS, PhS, PhSe, and PhTe groups from chalcogen-substituted acetate, acetonitrile, malonate, and malononitrile compounds, from N-(phenylthio) phthalimide and from Me2S2 and Ph2S2 to primary alkyl radicals, have been determined by competition kinetics using PTOC esters as the radical precursors and competing trapping agents. Thio group transfers from malononitrile derivatives are marginally faster than the corresponding group transfer from the symmetrical disulfide, and the rate constant for PhSe group transfer from PhSeSePh is greater than those from the derivatives studied here. Substituent effects suggest that the chalcogen transfer reactions may be concerted. For three cases in which direct comparisons can be made, the rate constants for reactions of phenylchalcogenides are approximately equal to those for halogen atom transfer when the chalcogen and halide are in the same row of the periodic table and the radical resulting from displacement is the same. The rate constants reported in this work will be useful for the rational design of synthetic schemes based on homolytic group transfer chemistry.