α-tosyloxycycloheptanone | 146040-84-8

• 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: α-tosyloxycycloheptanone
• 英文别名: 2-(tosyloxy)cycloheptanone；2-Oxocycloheptyl 4-methylbenzenesulfonate；(2-oxocycloheptyl) 4-methylbenzenesulfonate
• CAS: 146040-84-8
• 化学式: C₁₄H₁₈O₄S
• 分子量: 282.361
• InChiKey: WVZOAZUIYHADSM-UHFFFAOYSA-N

物化性质

• 沸点：
  443.6±38.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  α-tosyloxycycloheptanone 、 alkaline earth salt of/the/ methylsulfuric acid 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (cyclohepten-1-yl)diethylphosphate
  参考文献：
  名称：

  通过改进的一锅 Perkow 反应直接从酮合成烯醇磷酸酯

  摘要：

  改进的 Perkow 反应基于酮的一锅 α-甲苯磺酰氧基化，随后添加 P(iii)-试剂和 4 Å 分子筛。

  DOI：

  10.1039/d2ra02340g
• 作为产物：
  描述：

  tert-butyl methyl(tosyloxy)carbamate 在 甲烷磺酸 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 27.0h， 生成 α-tosyloxycycloheptanone
  参考文献：
  名称：

  Direct α-Oxytosylation of Carbonyl Compounds:  One-Pot Synthesis of Heterocycles

  摘要：

  N-Methyl-O-tosylhydroxylamine is an effective reagent for the direct alpha-oxytosylation of carbonyl compounds. The reactions proceed smoothly at room temperature in the presence of both moisture and air and functional group tolerance in the substrate is good. With nonsymmetrical substrates regioselectivity for primary over secondary centers is observed and complete regiospecificity for primary over tertiary centers is obtained. Addition of a bis-heteronucleophile directly to the crude reaction mixture in a one-pot process leads to the corresponding heterocyclic product.

  DOI：

  10.1021/ol701774y

文献信息

• PhI- and polymer-supported PhI-catalyzed oxidative conversion of ketones and alcohols to α-tosyloxyketones with m-chloroperbenzoic acid and p-toluenesulfonic acid
  作者：Yukiharu Yamamoto、Yuhta Kawano、Patrick H. Toy、Hideo Togo

  DOI：10.1016/j.tet.2007.03.091

  日期：2007.5

  Various ketones were converted to the corresponding α-tosyloxyketones with mCPBA and p-toluenesulfonic acid in the presence of a catalytic amount of iodobenzene. Moreover, secondary alcohols were directly converted to the corresponding α-tosyloxyketones using mCPBA and catalytic amounts of iodobenzene and potassium bromide, followed by treatment with p-toluenesulfonic acid in a one-pot manner. Poly(4-iodostyrene)

  各种酮转化成相应的α-tosyloxyketones与米CPBA和p在碘苯催化量的存在对甲苯磺酸。此外，使用m CPBA和催化量的碘代苯和溴化钾将仲醇直接转化为相应的α-甲苯磺酰氧基酮，然后以对-甲苯磺酸的一锅法处理。聚（4-碘苯乙烯）也可用作与酮相同的α-甲苯磺酰化反应的可回收催化剂
• Ultrasound promoted hypervalent iodine reactions: (α-tosyloxylation of ketones with [hydroxy(tosyloxy)iodo]benzene
  作者：Atilla Tuncay、John A. Dustman、George Fisher、Crystal I. Tuncay、Kenneth S. Suslick

  DOI：10.1016/0040-4039(93)88006-5

  日期：1992.12

  the rates of α-tosyloxylation of ketones with [hydroxy(tosyloxy)iodo] benzene and thus provides a direct, quick, and mild method of tosyloxylation of ketones without the generation of time-consuming intermediates such as trimethylsilyl enol ether derivatives and α-hydroxy ketones. The present method also provides convenient access to the tosylates of alicyclic ketones such as cyclopentanone and cycloheptanone

  超声大大提高了酮与[羟基（甲苯磺酰氧基）碘]苯的α-甲苯磺酰氧基化的速率，因此提供了直接，快速，温和的酮磺酰氧基化方法，而不会产生费时的中间体，例如三甲基甲硅烷基烯醇醚衍生物和α-羟基酮。本发明的方法还提供了方便获得脂环酮的甲苯磺酸盐的方法，这些脂环酮例如是环戊酮和环庚酮，否则很难获得。
• 4-MeC6H4I-Mediated Efficient α-Tosyloxylation of Ketones with Oxone® and p-Toluenesulfonic Acid in Acetonitrile
  作者：Hideo Togo、Ayumi Tanaka

  DOI：10.1055/s-0029-1218370

  日期：2009.12

  Various alkyl aryl ketones, dialkyl ketones, and cycloheptanone were efficiently converted into the corresponding α-tosyl­oxy ketones in good yields by using Oxone® and p-toluenesulfonic acid monohydrate in the presence of p-iodotoluene in acetonitrile. 4-Methoxyacetophenone and 2-acetylthiophene bearing an electron-rich aromatic group could be also converted into the corresponding α-tosyloxyketones smoothly in good yields with the present method. Here, p-iodotoluene works as catalyst and p-[(hydroxy)(tosyloxy)]iodotoluene is formed in situ as a reactive species for the α-tosyloxylation of ketones. However, one equivalent of p-iodotoluene was required to obtain α-tosyloxyketones in good yields and was recovered in 80-20% yields, depending on the reaction conditions.

  通过在乙腈中使用Oxone®和p-甲苯磺酸一水合物，并在p-碘甲苯的存在下，各种烷基芳香酮、二烷基酮和环庚酮高效地转化为相应的α-甲苯磺酰氧基酮，产率良好。带有富电子芳香基团的4-甲氧基苯乙酮和2-乙酰基噻吩也可以用当前方法顺利地转化为相应的α-甲苯磺酰氧基酮，产率良好。在这里，p-碘甲苯作为催化剂，并且原位生成p-[(羟基)(甲苯磺酰氧基)]碘甲苯作为酮的α-甲苯磺酰氧化反应的活性物质。然而，为了获得良好的α-甲苯磺酰氧基酮产率，需要等量的p-碘甲苯，并且根据反应条件的不同，其回收率为80-20%。
• A facile and regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles using click chemistry
  作者：Dalip Kumar、V. Buchi Reddy、Rajender S. Varma

  DOI：10.1016/j.tetlet.2009.02.107

  日期：2009.5

  The reaction of α-tosyloxy ketones, sodium azide, and terminal alkynes in presence of copper(I) in aqueous polyethylene glycol afforded regioselectively 1,4-disubstituted 1,2,3-triazoles in good yield at ambient temperature. The one-pot exclusive formation of 1,4-disubstituted 1,2,3-triazoles involves in situ formation of α-azido ketones, followed by cycloaddition reaction with terminal alkyne. The

  α-甲苯磺酰氧基酮，叠氮化钠和末端炔在铜（I）存在下在聚乙二醇水溶液中反应在环境温度下以良好的产率提供区域选择性的1,4-二取代的1,2,3-三唑。一锅独家形成1,4-二取代1,2,3-三唑涉及原位形成α-叠氮基酮，然后与末端炔烃进行环加成反应。通过合成一系列不同的1,4-二取代的1,2,3-三唑，证明了这种一锅法的普遍性。
• Härtung von säurehärtbaren Zusammensetzungen, enthaltend einen blockierten Härtungskatalysator, unter Verwendung von Wärme
  申请人：CIBA-GEIGY AG

  公开号：EP0132225A2

  公开（公告）日：1985-01-23

  Verbindungen der Formeln (I) oder (II) worin R', R2, R', R4 und n die in Anspruch 1 angegebene Bedeutung haben, sind latente Härtungskatalysatoren, die thermisch aktivierbar sind. Sie finden Verwendung bei der thermischen Härtung von "high-solid"-Industrielacken, Coil-Coating-, Dosen- und Holzlacken.

  式（I）或（II）的化合物 其中 R'、R2、R'、R4 和 n 的含义如权利要求 1 所述。它们可用于高固体份工业涂料、卷材涂料、罐头涂料和木器涂料的热固化。