3H-2,1-benzoxaselenole Se-oxide | 858524-53-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 3H-2,1-benzoxaselenole Se-oxide
• 英文别名: 3H-2,1lambda4-benzoxaselenole 1-oxide；3H-2,1λ4-benzoxaselenole 1-oxide
• CAS: 858524-53-5
• 化学式: C₇H₆O₂Se
• 分子量: 201.083
• InChiKey: JNEQAEIUMSUUCJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.34
• 重原子数：
  10
• 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：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3H-2,1-benzoxaselenole Se-oxide 、 1-戊硫醇 以 二氯甲烷 为溶剂， 反应 0.17h， 以81%的产率得到(2-Pentylsulfanylselanylphenyl)methanol
  参考文献：
  名称：

  邻羟基甲基苯基硫属元素：合成，分子内非键硫属元素···OH相互作用和谷胱甘肽过氧化物酶样活性。

  摘要：

  描述了一系列衍生自苄醇13的有机硫属元素（Se，Te）化合物的合成和表征。的关键前体二硫属化物的合成15，22，和29被实现邻-lithiation路线。通过二锂化衍生物14与Se（dtc）2的反应获得硒化物18。用H 2 O 2氧化15和22分别得到相应的环状酯衍生物17和24。硒化物的氧化18与H 2 O 2一起提供螺环化合物19。通过单晶X射线研究已经证明了二杀菌剂15和22中分子内相互作用的存在。环状化合物17和19也已经通过单晶X射线研究表征。已通过偶联生物测定法评估了GP X样硒化合物的抗氧化活性。双碲化物22在mPW1PW91级别的密度泛函理论计算已经确定了羟基氧和碲原子之间相当强的非键相互作用。通过NBO分析获得的二阶摄动能传达了n O →σ* Te - Te轨道重叠在非键相互作用中的参与。使用分子原子（AIM）方法进行波后功能分析，确定了15和22中不同的键临界点，并且还

  DOI：

  10.1021/jo051309+
• 作为产物：
  描述：

  双（2-羧基苯基）二硒化物 在 叔丁基过氧化氢 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 6.0h， 生成 3H-2,1-benzoxaselenole Se-oxide
  参考文献：
  名称：

  Aromatic Derivatives and Tellurium Analogues of Cyclic Seleninate Esters and Spirodioxyselenuranes That Act as Glutathione Peroxidase Mimetics

  摘要：

  Several novel organoselenium and tellurium compounds were prepared and evaluated as mimetics of the selenoenzyme glutathione peroxidase, which protects cells from oxidative stress by reducing harmful peroxides with the thiol glutathione. The compounds were tested for catalytic activity in a model system wherein tert-butyl hydroperoxide or hydrogen peroxide were reduced with benzyl thiol and the rate of the reaction was measured by monitoring the formation of dibenzyl disulfide. Thus, aromatic derivatives 19, 22, 24, and 25 proved to be inferior catalysts compared to the parent cyclic seleninate ester 14 and spirodioxyselenurane 16. In the case of 19 and 22, this was the result of their rapid conversion to the relatively inert selenenyl sulfides 31 and 32, respectively. In general, hydrogen peroxide was reduced faster than tert-butyl hydroperoxide in the presence of the selenium-based catalysts. The cyclic tellurinate ester 27 and spirodioxytellurane 29 proved to be superior catalysts to their selenium analogues 14 and 16, respectively, resulting in the fastest reaction rates by far of all of the compounds we have investigated to date. Oxidation of 29 with hydrogen peroxide produced the unusual and unexpected peroxide 33, in which two hypervalent octahedral tellurium moieties are joined by ether and peroxide bridges. The structure of 33 was confirmed by X-ray crystallography. Although 33 displayed strong catalytic activity when tested independently in the model system, its relatively slow formation from the oxidation of 29 rules out its intermediacy in the catalytic cycle of 29.

  DOI：

  10.1021/jo0512711
• 作为试剂：
  描述：

  3-甲基-1-环己烯 在 3H-2,1-benzoxaselenole Se-oxide 、 双氧水 、 magnesium sulfate 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 1-甲基-1,2-环氧环己烷 、 1-甲基环己烷-1,2-二醇
  参考文献：
  名称：

  环状亚硒酸酯作为催化剂，用于将硫化物氧化为亚砜，将烯烃环氧化，并将烯胺转化为α-羟基酮

  摘要：

  环状硒代酸酯用作将硫化物快速氧化为亚砜，将烯烃快速氧化为环氧化物以及将烯胺快速氧化为α-羟基酮的催化剂。发现最佳条件使产物亚砜至砜的过氧化和环氧化物至二醇的水解减至最小。在某些实例中，例如苯乙烯衍生物，观察到氧化裂解而不是环氧化。烯胺的氧化过程是通过最初形成二聚2,5-二氨基-1,4-二恶烷物质而进行的，将其原位水解为最终产物。一种这样的二聚体的结构通过X射线晶体学确认。

  DOI：

  10.1021/jo300313v

文献信息

• Optically Active Seleninate Esters:  Isolation, Absolute Configuration, Racemization Mechanism, and Transformation into Chiral Selenoxide
  作者：Yusuke Nakashima、Toshio Shimizu、Kazunori Hirabayashi、Fujiko Iwasaki、Mikio Yamasaki、Nobumasa Kamigata

  DOI：10.1021/jo050343l

  日期：2005.6.1

  Optically active seleninate esters were obtained for the first time by chromatographic resolution on an optically active column. The absolute configurations of the optically active seleninate esters were determined by comparing their chiroptical properties with those of two analogous sulfinate esters, the absolute configuration of one of which is known and that of the other was determined by X-ray

  通过在光学活性柱上的色谱分离，首次获得光学活性的硒酸酯。光学活性的硒酸酯的绝对构型是通过将它们的手性与两种类似的亚磺酸酯的手性进行比较而确定的，其中一种的绝对构型是已知的，另一种的绝对构型是通过X射线晶体学分析确定的。发现旋光性硒代酸酯在溶液中消旋。外消旋，与H 2 18进行氧交换反应的动力学研究O，并且理论研究澄清了旋光性硒酸酯在溶液中的消旋作用是通过与水反应形成的非手性高价亚硒酸酯中间体进行的。发现具有大取代基的旋光硒酸亚硒酸酯和亚磺酸酯与格利雅试剂的反应在保留立体化学的情况下进行，分别得到旋光亚硒酸酯和亚砜。
• WO2007/44641
  申请人：——

  公开号：——

  公开（公告）日：——
• Cyclic Seleninate Esters as Catalysts for the Oxidation of Sulfides to Sulfoxides, Epoxidation of Alkenes, and Conversion of Enamines to α-Hydroxyketones
  作者：Eric A. Mercier、Chris D. Smith、Masood Parvez、Thomas G. Back

  DOI：10.1021/jo300313v

  日期：2012.4.6

  sulfides to sulfoxides, alkenes to epoxides, and enamines to α-hydroxyketones. Optimal conditions were found that minimize the overoxidation of the product sulfoxides to sulfones and the hydrolysis of epoxides to diols. In some examples such as styrene derivatives, oxidative cleavage was observed instead of epoxidation. The enamine oxidations proceed via the initial formation of dimeric 2,5-diamino-1

  环状硒代酸酯用作将硫化物快速氧化为亚砜，将烯烃快速氧化为环氧化物以及将烯胺快速氧化为α-羟基酮的催化剂。发现最佳条件使产物亚砜至砜的过氧化和环氧化物至二醇的水解减至最小。在某些实例中，例如苯乙烯衍生物，观察到氧化裂解而不是环氧化。烯胺的氧化过程是通过最初形成二聚2,5-二氨基-1,4-二恶烷物质而进行的，将其原位水解为最终产物。一种这样的二聚体的结构通过X射线晶体学确认。
• Aromatic Derivatives and Tellurium Analogues of Cyclic Seleninate Esters and Spirodioxyselenuranes That Act as Glutathione Peroxidase Mimetics
  作者：Thomas G. Back、Dušan Kuzma、Masood Parvez

  DOI：10.1021/jo0512711

  日期：2005.11.1

  Several novel organoselenium and tellurium compounds were prepared and evaluated as mimetics of the selenoenzyme glutathione peroxidase, which protects cells from oxidative stress by reducing harmful peroxides with the thiol glutathione. The compounds were tested for catalytic activity in a model system wherein tert-butyl hydroperoxide or hydrogen peroxide were reduced with benzyl thiol and the rate of the reaction was measured by monitoring the formation of dibenzyl disulfide. Thus, aromatic derivatives 19, 22, 24, and 25 proved to be inferior catalysts compared to the parent cyclic seleninate ester 14 and spirodioxyselenurane 16. In the case of 19 and 22, this was the result of their rapid conversion to the relatively inert selenenyl sulfides 31 and 32, respectively. In general, hydrogen peroxide was reduced faster than tert-butyl hydroperoxide in the presence of the selenium-based catalysts. The cyclic tellurinate ester 27 and spirodioxytellurane 29 proved to be superior catalysts to their selenium analogues 14 and 16, respectively, resulting in the fastest reaction rates by far of all of the compounds we have investigated to date. Oxidation of 29 with hydrogen peroxide produced the unusual and unexpected peroxide 33, in which two hypervalent octahedral tellurium moieties are joined by ether and peroxide bridges. The structure of 33 was confirmed by X-ray crystallography. Although 33 displayed strong catalytic activity when tested independently in the model system, its relatively slow formation from the oxidation of 29 rules out its intermediacy in the catalytic cycle of 29.
• <i>o</i>-Hydroxylmethylphenylchalcogens: Synthesis, Intramolecular Nonbonded Chalcogen···OH Interactions, and Glutathione Peroxidase-like Activity
  作者：Santosh K. Tripathi、Upali Patel、Dipankar Roy、Raghavan B. Sunoj、Harkesh B. Singh、Gotthelf Wolmershäuser、Ray J. Butcher

  DOI：10.1021/jo051309+

  日期：2005.11.1

  The synthesis and characterization of a series of organochalcogen (Se, Te) compounds derived from benzyl alcohol 13 are described. The synthesis of the key precursor dichalcogenides 15, 22, and 29 was achieved by the ortho-lithiation route. Selenide 18 was obtained by the reaction of the dilithiated derivative 14 with Se(dtc)2. Oxidation of 15 and 22 with H2O2 afforded the corresponding cyclic ester

  描述了一系列衍生自苄醇13的有机硫属元素（Se，Te）化合物的合成和表征。的关键前体二硫属化物的合成15，22，和29被实现邻-lithiation路线。通过二锂化衍生物14与Se（dtc）2的反应获得硒化物18。用H 2 O 2氧化15和22分别得到相应的环状酯衍生物17和24。硒化物的氧化18与H 2 O 2一起提供螺环化合物19。通过单晶X射线研究已经证明了二杀菌剂15和22中分子内相互作用的存在。环状化合物17和19也已经通过单晶X射线研究表征。已通过偶联生物测定法评估了GP X样硒化合物的抗氧化活性。双碲化物22在mPW1PW91级别的密度泛函理论计算已经确定了羟基氧和碲原子之间相当强的非键相互作用。通过NBO分析获得的二阶摄动能传达了n O →σ* Te - Te轨道重叠在非键相互作用中的参与。使用分子原子（AIM）方法进行波后功能分析，确定了15和22中不同的键临界点，并且还