Acetic acid 4-methoxy-5,8-dioxo-7-propyl-5,8-dihydro-naphthalen-2-yl ester | 137396-04-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: Acetic acid 4-methoxy-5,8-dioxo-7-propyl-5,8-dihydro-naphthalen-2-yl ester
• CAS: 137396-04-4
• 化学式: C₁₆H₁₆O₅
• 分子量: 288.3
• InChiKey: DJDZIQAOLRNVAT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.73
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  69.67
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  氟磺酸甲酯 、 1-戊炔 、 乙酸酐 、 (4-bromo-3-methoxyphenoxy)(tert-butyl)dimethylsilane 、 alkaline earth salt of/the/ methylsulfuric acid 在 吡啶 、 4-二甲氨基吡啶 、 正丁基锂 、 Ce(NH₄)6(NO₂)2 、 硝酸 、 sodium methylate 作用下， 生成 Acetic acid 4-methoxy-5,8-dioxo-7-propyl-5,8-dihydro-naphthalen-2-yl ester 、 2-[2-(4-Acetoxy-2-methoxy-phenyl)-2-oxo-eth-(Z)-ylidene]-pentanoic acid methyl ester
  参考文献：
  名称：

  Substrate regulation of product distribution in the reactions of arylchromium carbene complexes with alkynes

  摘要：

  The reactions of arylcarbene complexes with alkynes were examined for six of the nine possible substitution patterns for mono- and dioxygenated aryl substituents of the carbene carbon. The product distributions were found to be highly dependent on a number of factors, including solvent, temperature, concentration of alkyne, and the nature of the aryl substituent. The product distributions were determined in nearly all cases for phenol and indene products and in some cases for furans, cyclobutenones, and cyclopentenediones, which were minor products in these reactions. The product distribution for the reaction of each arylcarbene complex was determined as a function of both temperature and alkyne concentration, since the combined product distribution profiles provided a much more sensitive measure of the relative influences of the aryl substituents on the reaction outcome. Furthermore, this distribution profile was determined for the reactions with 3-hexyne and I-pentyne for each carbene complex. A series of monosubstituted arylcarbene complexes were examined to identify the effects of oxygen substituents at various positions on the aryl ring. The m-methoxy group has no effect on the product distribution, whereas the o-methoxy group influences the distribution by its ability to chelate to the metal center and the p-methoxy group influences the distribution by its ability to donate electrons by resonance. The product distributions from the reactions of the 2,3-, 2,4-, and 2,5-dimethoxy complexes followed the profile expected from the simple sum of the profiles of the monomethoxyl complexes. In all cases where an effect was observed, higher concentrations of alkyne led to a higher selectivity for phenol over indene products. The dependence of the product distribution on the concentration of the alkyne substrate is suggested to be due to a process in which a second molecule of alkyne coordinates to the metal center and determines the chemical outcome of an intermediate that has covalently incorporated the first alkyne. It is further suggested that the special ability of an alkyne to display this effect is related to the ability of an alkyne to readily switch from a 2 to a 4 e- donor. This phenomenon of substrate regulation of product distribution is termed the allochemical effect, and a mechanistic explanation is developed that features this proposed process and that is refined to accommodate the observed effects of solvent, temperature, chelation, and steric and electronic effects that have been observed for the reaction of carbene complexes and alkynes.

  DOI：

  10.1021/ja00024a040

文献信息

• Substrate regulation of product distribution in the reactions of arylchromium carbene complexes with alkynes
  作者：Mary Ellen Bos、William D. Wulff、Ross A. Miller、Steven Chamberlin、Timothy A. Brandvold

  DOI：10.1021/ja00024a040

  日期：1991.11

  The reactions of arylcarbene complexes with alkynes were examined for six of the nine possible substitution patterns for mono- and dioxygenated aryl substituents of the carbene carbon. The product distributions were found to be highly dependent on a number of factors, including solvent, temperature, concentration of alkyne, and the nature of the aryl substituent. The product distributions were determined in nearly all cases for phenol and indene products and in some cases for furans, cyclobutenones, and cyclopentenediones, which were minor products in these reactions. The product distribution for the reaction of each arylcarbene complex was determined as a function of both temperature and alkyne concentration, since the combined product distribution profiles provided a much more sensitive measure of the relative influences of the aryl substituents on the reaction outcome. Furthermore, this distribution profile was determined for the reactions with 3-hexyne and I-pentyne for each carbene complex. A series of monosubstituted arylcarbene complexes were examined to identify the effects of oxygen substituents at various positions on the aryl ring. The m-methoxy group has no effect on the product distribution, whereas the o-methoxy group influences the distribution by its ability to chelate to the metal center and the p-methoxy group influences the distribution by its ability to donate electrons by resonance. The product distributions from the reactions of the 2,3-, 2,4-, and 2,5-dimethoxy complexes followed the profile expected from the simple sum of the profiles of the monomethoxyl complexes. In all cases where an effect was observed, higher concentrations of alkyne led to a higher selectivity for phenol over indene products. The dependence of the product distribution on the concentration of the alkyne substrate is suggested to be due to a process in which a second molecule of alkyne coordinates to the metal center and determines the chemical outcome of an intermediate that has covalently incorporated the first alkyne. It is further suggested that the special ability of an alkyne to display this effect is related to the ability of an alkyne to readily switch from a 2 to a 4 e- donor. This phenomenon of substrate regulation of product distribution is termed the allochemical effect, and a mechanistic explanation is developed that features this proposed process and that is refined to accommodate the observed effects of solvent, temperature, chelation, and steric and electronic effects that have been observed for the reaction of carbene complexes and alkynes.