α-(pivaloyl)-α-(ethoxycarbonyl)methylenetriphenylphosphorane | 143706-82-5

• 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-(pivaloyl)-α-(ethoxycarbonyl)methylenetriphenylphosphorane
• 英文别名: ethyl 2-(triphenylphosphoranylidene)-4,4-dimethyl-3-oxovalerate；Ethyl 4,4-dimethyl-3-oxo-2-(triphenyl-lambda5-phosphanylidene)pentanoate；ethyl 4,4-dimethyl-3-oxo-2-(triphenyl-λ5-phosphanylidene)pentanoate
• CAS: 143706-82-5
• 化学式: C₂₇H₂₉O₃P
• 分子量: 432.499
• InChiKey: PSHATOHCYFHHIK-UHFFFAOYSA-N

物化性质

• 熔点：
  154 °C
• 沸点：
  553.7±33.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  α-(pivaloyl)-α-(ethoxycarbonyl)methylenetriphenylphosphorane 150.0~220.0 ℃ 、1.33 kPa 条件下， 以64%的产率得到ethyl 4,4-dimethylpent-2-ynoate
  参考文献：
  名称：

  Cyclocondensation of alkylhydrazines and .beta.-substituted acetylenic esters: synthesis of 3-hydroxypyrazoles

  摘要：

  Addition of monosubstituted alkylhydrazines to acetylenic esters with either electron-withdrawing or sterically bulky beta-substituents afforded 1-alkyl-3-hydroxy-5-substituted-pyrazoles 1 as the major regioisomeric product. By comparison, the classical cyclocondensation of alkylhydrazines with beta-keto esters gives the regioisomeric pyrazol-5-ones 2. The reaction solvent employed in these cyclocondensations can have a profound effect on regioisomeric product ratios. Addition of methylhydrazine to 5g in methylene chloride gave regiospecific formation of pyrazolinone 2o, whereas addition in water-methanol mixtures afforded hydroxypyrazole 1o as the major product. Structural assignment of regioisomers 1 and 2 are based on C-13 NMR chemical shifts, long-range heteronuclear coupling constants, and comparisons with regiochemically known hydroxypyrazoles and/or pyrazolinones. Additions of acetylene 5b to 1,1-dimethylhydrazine afforded either acyclic enehydrazone 12 or pyrazolium betaine 13 depending on the reaction conditions.

  DOI：

  10.1021/jo00047a021
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 三乙胺 作用下， 以41%的产率得到α-(pivaloyl)-α-(ethoxycarbonyl)methylenetriphenylphosphorane
  参考文献：
  名称：

  Cyclocondensation of alkylhydrazines and .beta.-substituted acetylenic esters: synthesis of 3-hydroxypyrazoles

  摘要：

  Addition of monosubstituted alkylhydrazines to acetylenic esters with either electron-withdrawing or sterically bulky beta-substituents afforded 1-alkyl-3-hydroxy-5-substituted-pyrazoles 1 as the major regioisomeric product. By comparison, the classical cyclocondensation of alkylhydrazines with beta-keto esters gives the regioisomeric pyrazol-5-ones 2. The reaction solvent employed in these cyclocondensations can have a profound effect on regioisomeric product ratios. Addition of methylhydrazine to 5g in methylene chloride gave regiospecific formation of pyrazolinone 2o, whereas addition in water-methanol mixtures afforded hydroxypyrazole 1o as the major product. Structural assignment of regioisomers 1 and 2 are based on C-13 NMR chemical shifts, long-range heteronuclear coupling constants, and comparisons with regiochemically known hydroxypyrazoles and/or pyrazolinones. Additions of acetylene 5b to 1,1-dimethylhydrazine afforded either acyclic enehydrazone 12 or pyrazolium betaine 13 depending on the reaction conditions.

  DOI：

  10.1021/jo00047a021

文献信息

• Infrared spectroscopy and ab initio computation in conformer determination of keto ester and diketo triphenylphosphonium ylides
  作者：Clifford A. Bunton、Fernando Castañeda

  DOI：10.1016/j.molstruc.2009.07.028

  日期：2009.11

  fits for both keto ester and diketo ylides. For both methods agreement between observed and predicted frequencies is lowest for the syn – anti di- t -butyl keto ester ylide, although, unlike the situation for diester ylides, one bulky alkyl group does not significantly degrade the fits. Comparison of predicted and observed acyl stretching frequencies is useful in establishing conformations of these stabilized

  摘要对于稳定的三苯基鏻酮酯叶立德，来自 HF/6-31G(d) 计算的抗酯基团的酰基拉伸频率与比例因子 SF = 0.866 拟合实验值，如早先估计的二酯叶立德，但比例因子 = 0.834 具有用于拟合合成酮组和合成 - 反二酮叶立德的数据。DFT 泛函 BLYP/6-31G(d)，文献中的比例因子 = 0.9945，通常对酮酯和二酮叶立德都有很好的拟合。对于这两种方法，观察到的和预测的频率之间的一致性对于顺 - 抗二叔丁基酮酯叶立德是最低的，尽管与二酯叶立德的情况不同，一个庞大的烷基不会显着降低拟合度。
• Demonic axe-like conjugated alkynes in combating microbes
  作者：Jayaram Reddy Komsani、Satish Koppireddi、Sreenivas Avula、Pranay Kumar Koochana、Rambabu Yadla

  DOI：10.1016/j.ejmech.2013.07.013

  日期：2013.10

  A new series of disubstituted alkynes was obtained by microwave induced internal splitting of the corresponding beta-oxo-alkylidenetriphenylphosphoranes. The antimicrobial potential of these conjugated alkynes and phosphoranes was assayed in vitro against three Gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis, Staphylococcus epidermidis), three Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae) and five fungal strains (Aspergillus niger, Candida albicans, Aspergillus flavus, Candida rugosa, Saccharomyces cerevisiae). The 3-pyridylalkyne derivatives viz., 3-(6-chloropyridin-3-yl)propynenitrile (6a), 3-(2-chloropyridin-3-yl)propynenitrile (6b), ethyl 3-(6-chloropyridin-3-yl)propiolate (6c), iso-propyl 3-(6-chloropyridin-3-yl)propiolate (6d) and 3-(2,6-dichloro-5-fluoropyridin-3-yl) propynenitrile (6e) were found to be highly potent towards all tested microorganisms except E. coli. (C) 2013 Elsevier Masson SAS. All rights reserved.
• Zinc promoted facile method for the acylation of ylides at α-carbon
  作者：H.M. Meshram、Gondi Sudershan Reddy、M. Muralidhar Reddy、J.S. Yadav

  DOI：10.1016/s0040-4039(98)00667-4

  日期：1998.6

  Stabilised triphenylphosphonium ylides are acylated at the alpha-carbon with different acyl groups using zinc. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.