3,3-dimethyl-1-buten-2-yl acetate | 3814-40-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3,3-dimethyl-1-buten-2-yl acetate
• 英文别名: 3-methyl-2-acetoxy-1-butene；2-Acetoxy-3-methyl-1-buten；2-Acetoxy-3-methyl-buten-1；3-Methylbut-1-en-2-yl acetate
• CAS: 3814-40-2
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: GGFZWCZYTMEWNP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2915390090

反应信息

• 作为反应物：
  描述：

  1-溴-2-甲基-1-丙烯 、 3,3-dimethyl-1-buten-2-yl acetate 在 二氯双(三邻甲苯膦)合钯(II) 三正丁基甲氧基锡 作用下， 以 甲苯 为溶剂， 反应 0.5h， 以74%的产率得到2,6-dimethyl-5-hepten-3-one
  参考文献：
  名称：

  酮的α-位的1-烯基化：钯催化的烯醇化锡和1-溴-1-烯烃的反应

  摘要：

  发现由甲醇三丁基锡和烯醇乙酸酯原位制备的三丁基锡烯醇化物与 1-溴-1-烯烃在催化量的 PdCl2(o-tolyl3P)2 存在下反应得到良好的烯丙基酮衍生物产量。

  DOI：

  10.1246/cl.1983.839
• 作为产物：
  描述：

  3-甲基-2-丁酮 、 乙烯酮 在 硫酸 作用下， 以34%的产率得到3,3-dimethyl-1-buten-2-yl acetate
  参考文献：
  名称：

  Kosugi, Masanori; Hagiwara, Isao; Sumiya, Takao, Bulletin of the Chemical Society of Japan, 1984, vol. 57, # 1, p. 241 - 246

  摘要：

  DOI：

文献信息

• Hydrocarbonylation of Enol Esters Catalyzed by a Palladium(II) Complex
  作者：Kiyoshi Kudo、Yuji Oida、Koichi Mitsuhashi、Sadayuki Mori、Koichi Komatsu、Nobuyuki Sugita

  DOI：10.1246/bcsj.69.1337

  日期：1996.5

  The palladium(II)-catalyzed carbonylation of various enol esters in the presence of methanol under pressurized carbon monoxide was investigated. As typical results, the carbonylation of isopropenyl acetate afforded a cyclocarbonylation product, 2-methoxy-2,5,5-trimethyl-1,3-dioxolan-4-one, in 46% yield under carbon monoxide of 150 atm at 100 °C, whereas vinyl acetate selectively gave an α-hydroesterification product, methyl 2-acetoxypropionate, in 56% yield under 250 atm at 100 °C. On the contrary, the reaction of 3,3-dimethyl-1-buten-2-yl acetate gave exclusively a β-hydroesterification product, methyl 3-acetoxy-4,4-dimethylpentanoate, in 64% yield. The yields of these products show a maximum as a function of the base/palladium ratio and of the carbon monoxide pressure. The effects of the reaction variables, such as the MeOH/substrate ratio, the structure of the base, the base/Pd ratio, the CO pressure, and the reaction temperature, were examined for optimizing the process. The mechanisms for the unique cyclocarbonylation and highly regioselective hydrocarbonylation of enol esters involving hydridopalladium(II) intermediate are discussed.

  研究了在加压一氧化碳和甲醇存在下，钯(II)催化的各种烯醇酯的羰基化反应。作为典型结果，在150大气压、100°C的条件下，异丙烯基乙酸酯的羰基化反应得到了环状羰基化产物，2-甲氧基-2,5,5-三甲基-1,3-二氧杂环己烷-4-酮，产率为46%；而乙烯基乙酸酯在250大气压、100°C的条件下，选择性地得到了α-羟基酯化产物，乙酸甲酯-2-乙酰氧基丙酸酯，产率为56%。相反，3,3-二甲基-1-丁烯-2-基乙酸酯反应得到了唯一的β-羟基酯化产物，乙酸甲酯-3-乙酰氧基-4,4-二甲基戊酸酯，产率为64%。这些产物的产率作为碱/钯比的函数和一氧化碳压力的函数达到最大值。为了优化过程，考察了反应变量，如甲醇/底物比、碱的结构、碱/钯比、一氧化碳压力和反应温度等的影响。讨论了含氢钯(II)中间体参与的烯醇酯独特环羰基化和高度区域选择性羟基羰基化的机理。
• α-Phenylation of ketones via tin enolates catalysed by a palladium complex
  作者：Masanori Kosugi、Isao Hagiwara、Takashi Sumiya、Toshihiko Migita

  DOI：10.1039/c39830000344

  日期：——

  The reaction of tributyltin enolates, prepared from tributyltin methoxide and enol acetates in situ, with bromobenzene in the presence of a catalytic amount of PdCl2(o-tolyl3P)2 was found to give α-phenyl ketones in good yields with essentially complete retetion of the acetate regiochemistry.

  发现在催化量的PdCl 2（o- tolyl 3 P）2存在下，由甲醇三丁基锡和乙酸烯醇酯原位制备的烯丙基三丁基锡与溴苯的反应可得到高收率的α-苯基酮，基本完全完成醋酸盐区域化学的检测。
• COMPOSITIONS AND METHODS FOR PRODUCING ISOPRENE FREE OF C5 HYDROCARBONS UNDER DECOUPLING CONDITIONS AND/OR SAFE OPERATING RANGES
  申请人：CALABRIA Anthony R.

  公开号：US20100048964A1

  公开（公告）日：2010-02-25

  The invention features methods for producing isoprene from cultured cells wherein the cells in the stationary phase. The invention also provides compositions that include these cultured cells and/or increased amount of isoprene. The invention also provides for systems that include a non-flammable concentration of isoprene in the gas phase. Additionally, the invention provides isoprene compositions, such as compositions with increased amount of isoprene or increased purity.

  这项发明涉及从培养细胞中生产异戊二烯的方法，其中细胞处于静止阶段。该发明还提供包括这些培养细胞和/或增加的异戊二烯量的组合物。该发明还提供包括气相中非易燃浓度的异戊二烯的系统。此外，该发明提供异戊二烯组合物，例如含有增加的异戊二烯量或增加纯度的组合物。
• METHODS FOR PRODUCING ISOPRENE FREE OF C5 HYDROCARBONS UNDER DECOUPLING CONDITIONS AND/OR SAFE OPERATING RANGES
  申请人：Danisco US Inc.

  公开号：EP3406722A1

  公开（公告）日：2018-11-28

  The invention features methods for producing isoprene from cultured cells wherein the cells in the stationary phase. The invention also provides compositions that include these cultured cells and/or increased amount of isoprene. The invention also provides for systems that include a non-flammable concentration of isoprene in the gas phase. Additionally, the invention provides isoprene compositions, such as compositions with increased amount of isoprene or increased purity.

  本发明的特点是利用处于静止期的培养细胞生产异戊二烯的方法。本发明还提供了包括这些培养细胞和/或增加的异戊二烯量的组合物。本发明还提供了包括气相中不易燃浓度的异戊二烯的系统。此外，本发明还提供异戊二烯组合物，如增加异戊二烯用量或提高纯度的组合物。
• Compositions and methods for producing isoprene free of c5 hydrocarbons under decoupling conditions and/or safe operating ranges
  申请人：Danisco US Inc.

  公开号：US10774345B2

  公开（公告）日：2020-09-15

  The invention features methods for producing isoprene from cultured cells wherein the cells in the stationary phase. The invention also provides compositions that include these cultured cells and/or increased amount of isoprene. The invention also provides for systems that include a non-flammable concentration of isoprene in the gas phase. Additionally, the invention provides isoprene compositions, such as compositions with increased amount of isoprene or increased purity.

  本发明的特点是利用处于静止期的培养细胞生产异戊二烯的方法。本发明还提供了包括这些培养细胞和/或增加的异戊二烯量的组合物。本发明还提供了包括气相中不易燃浓度的异戊二烯的系统。此外，本发明还提供异戊二烯组合物，如增加异戊二烯用量或提高纯度的组合物。