1-acetoxy-3,3-dimethylpentane-2,4-dione

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-acetoxy-3,3-dimethylpentane-2,4-dione
• 英文别名: (3,3-Dimethyl-2,4-dioxopentyl) acetate
• 化学式: C₉H₁₄O₄
• 分子量: 186.208
• InChiKey: OGEKTNQQFHDGFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-acetoxy-3,3-dimethylpentane-2,4-dione 在 肼 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 20.0h， 以90%的产率得到
  参考文献：
  名称：

  Solvent Effect on Product Distribution in Photochemical Pathways of α C−N versus β C−C Cleavage of n,π* Triplet-Excited Azoalkanes

  摘要：

  The product distribution in;the photolysis of the triplet-excited azoalkanes 1a,b depends markedly on the type of solvent used; in contrast, the azoalkanes 1c,d, which undergo efficient deazatization from the singlet-excited state, display solvent-independent photobehavior. Thus, the aziranes 3 are produced essentially exclusively in polar protic solvents, while the housanes 2 predominate in nonpolar ones. The excellent correlation (r(2) = 0.963, seven solvents) of the azirane 3b yield with Gutmann's AN solvent parameter reveals that a combination of solvent properties such as the polarity and polarizability of the medium and the hydrogen-bonding ability is decisive for the photoproduct distribution. That the observed solvent dependence derives from bulk medium effects is borne out by the similar product distribution for the hydroxy-substituted derivative 1f to that for the azoalkane 1b in benzene, i.e., the intramolecular hydroxy functionality in the azoalkane If is ineffective in influencing the photochemistry of the triplet azo chromophore. Selective formation of the aziranes 3 from the triplet-excited azoalkanes 1 in the polar protic solvents is rationalized in terms of solvent stabilization of the more polar transition state for beta cleavage (azirane 3) over that for the alpha scission (housane 2). In marked contrast to the appreciable deuterium isotope effect for quenching of the singlet-excited azoalkanes by protic solvents, the lifetimes (laser-flash photolysis) and reactivity (product analysis) of the triplet azoalkanes are not affected by deuterium substitution.

  DOI：

  10.1021/ja963948v
• 作为产物：
  描述：

  3,3-二甲基-2,4-戊二酮 在 18-冠醚-6 、 溴 作用下， 以 溶剂黄146 、 乙腈 为溶剂， 反应 30.0h， 生成 1-acetoxy-3,3-dimethylpentane-2,4-dione
  参考文献：
  名称：

  Solvent Effect on Product Distribution in Photochemical Pathways of α C−N versus β C−C Cleavage of n,π* Triplet-Excited Azoalkanes

  摘要：

  The product distribution in;the photolysis of the triplet-excited azoalkanes 1a,b depends markedly on the type of solvent used; in contrast, the azoalkanes 1c,d, which undergo efficient deazatization from the singlet-excited state, display solvent-independent photobehavior. Thus, the aziranes 3 are produced essentially exclusively in polar protic solvents, while the housanes 2 predominate in nonpolar ones. The excellent correlation (r(2) = 0.963, seven solvents) of the azirane 3b yield with Gutmann's AN solvent parameter reveals that a combination of solvent properties such as the polarity and polarizability of the medium and the hydrogen-bonding ability is decisive for the photoproduct distribution. That the observed solvent dependence derives from bulk medium effects is borne out by the similar product distribution for the hydroxy-substituted derivative 1f to that for the azoalkane 1b in benzene, i.e., the intramolecular hydroxy functionality in the azoalkane If is ineffective in influencing the photochemistry of the triplet azo chromophore. Selective formation of the aziranes 3 from the triplet-excited azoalkanes 1 in the polar protic solvents is rationalized in terms of solvent stabilization of the more polar transition state for beta cleavage (azirane 3) over that for the alpha scission (housane 2). In marked contrast to the appreciable deuterium isotope effect for quenching of the singlet-excited azoalkanes by protic solvents, the lifetimes (laser-flash photolysis) and reactivity (product analysis) of the triplet azoalkanes are not affected by deuterium substitution.

  DOI：

  10.1021/ja963948v

文献信息

• Method for Synthesis of 2,5-Dioxane-1,4-Diones
  申请人：Bourissou Didier

  公开号：US20080004453A1

  公开（公告）日：2008-01-03

  The invention relates to a novel method for the synthesis of 2,5-dioxane-1,4-diones having formula (I), comprising the oxidation of the ketone function of a cyclic compound having formula (II), wherein R 1 , R 2 , R 3 and R 4 independently represent the hydrogen atom, halo, (C 2 -C 6 ) alkenyl, (C 3 -C 7 )cycloalkyl, cyclohexenyl and a radical having formula —(CH 2 ) m —V—W.

  本发明涉及一种合成2,5-二氧杂环戊二酮（式（I））的新方法，包括氧化具有式（II）的环状化合物的酮基，其中R1、R2、R3和R4独立地表示氢原子、卤素、（C2-C6）烯基、（C3-C7）环烷基、环己烯基和具有式-（CH2）m-V-W的基团。
• Solvent Effect on Product Distribution in Photochemical Pathways of α C−N versus β C−C Cleavage of n,π* Triplet-Excited Azoalkanes
  作者：Waldemar Adam、Jarugu N. Moorthy、Werner M. Nau、J. C. Scaiano

  DOI：10.1021/ja963948v

  日期：1997.6.1

  The product distribution in;the photolysis of the triplet-excited azoalkanes 1a,b depends markedly on the type of solvent used; in contrast, the azoalkanes 1c,d, which undergo efficient deazatization from the singlet-excited state, display solvent-independent photobehavior. Thus, the aziranes 3 are produced essentially exclusively in polar protic solvents, while the housanes 2 predominate in nonpolar ones. The excellent correlation (r(2) = 0.963, seven solvents) of the azirane 3b yield with Gutmann's AN solvent parameter reveals that a combination of solvent properties such as the polarity and polarizability of the medium and the hydrogen-bonding ability is decisive for the photoproduct distribution. That the observed solvent dependence derives from bulk medium effects is borne out by the similar product distribution for the hydroxy-substituted derivative 1f to that for the azoalkane 1b in benzene, i.e., the intramolecular hydroxy functionality in the azoalkane If is ineffective in influencing the photochemistry of the triplet azo chromophore. Selective formation of the aziranes 3 from the triplet-excited azoalkanes 1 in the polar protic solvents is rationalized in terms of solvent stabilization of the more polar transition state for beta cleavage (azirane 3) over that for the alpha scission (housane 2). In marked contrast to the appreciable deuterium isotope effect for quenching of the singlet-excited azoalkanes by protic solvents, the lifetimes (laser-flash photolysis) and reactivity (product analysis) of the triplet azoalkanes are not affected by deuterium substitution.