benzyl 2-chloro-2-methyl-3-oxobutanoate

• 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: benzyl 2-chloro-2-methyl-3-oxobutanoate
• 化学式: C₁₂H₁₃ClO₃
• 分子量: 240.686
• InChiKey: MGEQCZPOVIIMLL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-甲基-3-氧代丁酸苄酯 在 四氯化钛 、 双氧水 作用下， 以 乙腈 、 水 为溶剂， 以96%的产率得到benzyl 2-chloro-2-methyl-3-oxobutanoate
  参考文献：
  名称：

  过氧化氢或过氧乙酸介导的1,3-二羰基化合物的自滴定α-卤化

  摘要：

  通过使用包含亚化学计量量的TiX 4（X = Cl，Br）以及环境友好的过氧化氢（H 2 O 2）或过氧乙酸的系统，可以实现1,3-二羰基化合物的有效氧化α-卤化酸（MeCO 3 H）作为氧化剂。反应的终点伴随着急剧的颜色变化。 卤化-过氧化物-钛-卤化物-亲电子

  DOI：

  10.1055/s-0030-1258367

文献信息

• Catalytic Enantioselective Chlorination and Bromination of β-Keto Esters
  作者：Lukas Hintermann、Antonio Togni

  DOI：10.1002/1522-2675(20000906)83:9<2425::aid-hlca2425>3.0.co;2-v

  日期：2000.9.6

  3-dioxolane-4,5-dimethanolato(2−)-O,O′]titanium ((R)-1b) are efficient catalysts for the electrophilic enantioselective chlorination and bromination of β-keto esters with N-chlorosuccinimide (NCS) and N-bromosuccinimide (NBS), respectively. With 5 mol-% of catalyst at room temperature an enantioselectivity of up to 88% ee could be obtained for the chlorination reaction. Under comparable conditions, bromination

  Ti(TADDOLato) 络合物二氯[(4R,5R)-2,2-二甲基-α,α,α',α'-四苯基-1,3-二氧戊环-4,5-二甲醇合(2-)-O, O']钛((R)-1a)和二氯[(4R,5R)-2,2-二甲基-α,α,α',α'-四(萘-1-基)-1,3-二氧戊环-4,5-二甲醇(2-)-O,O']钛((R)-1b)是β-酮酯与N-氯代琥珀酰亚胺(NCS)和N-溴代琥珀酰亚胺的亲电子对映选择性氯化和溴化的有效催化剂（国家统计局），分别。在室温下使用 5 mol-% 的催化剂，氯化反应可以获得高达 88% ee 的对映选择性。在可比较的条件下，溴化反应较慢且立体选择性较低。
• Hydrogen Peroxide or Peracetic Acid Mediated Self-Titrating α-Halogenation of 1,3-Dicarbonyl Compounds
  作者：Hasim Ibrahim、Ramulu Akula、Marc Galligan

  DOI：10.1055/s-0030-1258367

  日期：2011.1

  Efficient oxidative α-halogenation of 1,3-dicarbonyl compounds has been achieved by employing a system comprising of sub-stoichiometric amounts of TiX4 (X = Cl, Br) in conjunction with environmentally benign hydrogen peroxide (H2O2) or peracetic acid (MeCO3H) as the oxidants. The end point of the reaction is accompanied by a sharp colour change. halogenation - peroxides - titanium - halides - electrophilic

  通过使用包含亚化学计量量的TiX 4（X = Cl，Br）以及环境友好的过氧化氢（H 2 O 2）或过氧乙酸的系统，可以实现1,3-二羰基化合物的有效氧化α-卤化酸（MeCO 3 H）作为氧化剂。反应的终点伴随着急剧的颜色变化。 卤化-过氧化物-钛-卤化物-亲电子
• Umpolung of halide reactivity: efficient (diacetoxyiodo)benzene-mediated electrophilic α-halogenation of 1,3-dicarbonyl compounds
  作者：Ramulu Akula、Marc Galligan、Hasim Ibrahim

  DOI：10.1039/b915348a

  日期：——

  An efficient high-yielding (diacetoxyiodo)benzene-mediated α-halogenation of 1,3-dicarbonyl compounds utilising titanium tetrahalides as the halide source has been developed.

  一种利用四卤化钛作为卤素源的高效高产率（二乙酰氧碘）苯介导的1,3-二羰基化合物的α-卤化方法已得到开发。
• Congested C2-symmetric aryliodanes based on an anti-dimethanoanthracene backbone
  作者：Stephen J. Murray、Helge Müller-Bunz、Hasim Ibrahim

  DOI：10.1039/c2cc32280c

  日期：——

  A family of congested aryliodanes based on an anti-dimethanoanthracene backbone has been synthesised and two diaryliodonium salts and the iodyl derivative characterised by X-ray analysis. The latter shows a rare water coordination to the iodine(V) centre in the solid state. Applications of these reagents in functional group transfer reactions are reported.

  已经合成了基于抗-二甲基蒽蒽骨架的一系列拥挤的芳基碘化合物，并且通过X射线分析表征了两种二芳基碘鎓盐和碘衍生物。后者在固态下显示出与碘（V）中心罕见的水配位。报道了这些试剂在官能团转移反应中的应用。
• Catalytic halogenation of activated methylene and methine compounds
  申请人：——

  公开号：US20020026067A1

  公开（公告）日：2002-02-28

  A process for the halogenation of activated methylene and methine compounds with at least equimolar amounts of an electrophilic halogenation reagent, which comprises reacting said activated methylene and methine compounds in the presence of catalytic amounts of a titanium compound of the formula I or of a titanium compound of the formula II R 1 TiX 1 X 2 X 3 (I), R 2 R 3 TiX 1 X 2 (II), in which R 1 is chlorine, bromine or iodine, a substituted or unsubstituted cyclopentadienyl or indenyl, and X 1 , X 2 and X 3 are, independently of one another, chlorine, bromine or iodine, or X 1 , X 2 and X 3 are an organic sulfonate group where R 1 is a substituted or unsubstituted cyclopentadienyl or indenyl; R 2 and R 3 are a substituted or unsubstituted cyclopentadienyl or indenyl, R 2 and R 3 together are a substituted or unsubstituted and bridged or unbridged biscyclopentadienyl or bisindenyl, or R 2 and R 3 together are a substituted or unsubstituted 1,3-, 1,4- or 1,5-diolate, and X 1 , and X 2 are, independently of one another, chlorine, bromine or iodine or an organic sulfonate group. If the diolate is enantiopure, the process is enantioselective on use of racemic activated methine compounds.

  一种用至少等摩尔量的亲电卤化试剂卤代活性甲亚甲基和甲烷化合物的过程，其中在催化量的I型钛化合物或II型钛化合物的存在下，反应所述的活性甲亚甲基和甲烷化合物，其中R1为氯、溴或碘，取代或未取代的环戊二烯基或茚基，X1、X2和X3独立地为氯、溴或碘，或X1、X2和X3为有机磺酸盐基团，其中R1为取代或未取代的环戊二烯基或茚基；R2和R3为取代或未取代的环戊二烯基或茚基，R2和R3一起为取代或未取代的桥接或未桥接的双环戊二烯基或双茚基，或R2和R3一起为取代或未取代的1,3-、1,4-或1,5-二醇酸盐基团，X1和X2独立地为氯、溴或碘或有机磺酸盐基团。如果二醇酸盐是对映纯的，则在使用外消旋的活性甲烷化合物时，该过程是对映选择性的。