2,2-dibromo-1-(4-methylphenyl)-1-propanone | 850010-87-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-dibromo-1-(4-methylphenyl)-1-propanone
• 英文别名: 2,2-Dibromo-1-(4-methylphenyl)propan-1-one
• CAS: 850010-87-6
• 化学式: C₁₀H₁₀Br₂O
• 分子量: 305.997
• InChiKey: RRAGXGQYOQVFDC-UHFFFAOYSA-N

物化性质

• 沸点：
  299.7±25.0 °C(Predicted)
• 密度：
  1.698±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2-dibromo-1-(4-methylphenyl)-1-propanone 在 锌 作用下， 以 乙醚 、 乙酸乙酯 为溶剂， 反应 1.5h， 生成 9c-methyl-3,4-dioxo-1-(p-tolyl)-9b,9c-dihydro-2,5-dioxacyclopenta[2,3]cyclopropa[1,2-a]naphthalen-1-yl acetate
  参考文献：
  名称：

  Cyclopropanation of N-substituted 3-aryl-2-cyanoprop-2-enamides and derivatives of 5,5-Dimethyl-2-oxo-2,5-dihydrofuran-3-carboxylic acid and 2-oxochromene-3-carboxylic acid with bromine-containing zinc enolates

  摘要：

  Zinc enolates derived from 1-aryl-2,2-dibromoalkanones react with N-substituted 3-aryl-2-cyanoprop-2-enamides and 5,5-dimethyl-2-oxo-2,5-dihydrofuran-3-carboxylic and 2-oxochromene-3-carboxylic acid derivatives to give, respectively, N-substituted 2-alkyl-3-aryt-2-aroyl-1-cyanocyclopropane-1-carboxamides, 6-(4-bromobenzoyi)-4,4,6-trimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane-1-carboxylic acid ethyl ester and morpholide, and 1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-1a-carboxylic acids as a single geometric isomer. Treatment of 1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-la-carboxylic acids with carboxylic acid anhydrides leads to the formation of the corresponding 9c-alkyl-1-aryl-3,4-dioxo-9b,9c-dihydro-2,5-dioxacyclopenta[2,3]cyclopropa[1,2-a]naphthalen-1-yl carboxylates.

  DOI：

  10.1134/s1070428006070086

文献信息

• 一种由α,α-二溴代酮一锅法制备α-砜基酮类化合物的合成方法
  申请人：温州大学

  公开号：CN110305048A

  公开（公告）日：2019-10-08

  本发明公开了一种以α,α‑二溴代酮类化合物为原料，一锅法合成具有高附加值的α‑砜基酮类化合物的方法。本方法从简单易得的α,α‑二溴代酮出发，不需要分离α‑溴代酮中间体，一锅法合成α‑砜基酮衍生物，减少了中间产物的分离过程，缩短了步骤，符合绿色环保要求；此外，本方法步骤简单易于操作，无需添加过渡金属试剂，直接使用经济廉价、污染小的亚磺酸盐同时作为α,α‑二溴代酮还原脱溴的促进剂和砜化试剂，节约了成本，增加了反应的经济效益。本发明发展出的一锅法制备α‑砜基酮类衍生物的体系为该类化合物的制备提供了全新的合成方法，具有良好的工业化前景和潜在的应用价值。
• Reactions of zinc enolates derived from 1-aryl-2,2-di-bromoalkanones with 2-acyl-3H-benzo[f]chromen-3-ones, 6-bromo-2-oxochromene-3-carboxamides, and 3-oxo-3H-benzo-[f]chromene-2-carboxamides
  作者：V. V. Shchepin、M. M. Kalyuzhnyi、P. S. Silaichev、N. Yu. Russkikh、R. V. Shchepin、M. A. Ezhikova、M. I. Kodess

  DOI：10.1007/s11178-005-0019-z

  日期：2004.9

  Zinc enolates derived from substituted 1-aryl-2,2-dibromoalkanones reacted with 2-acyl-3H-benzo-[f]chromen-3-ones to give 1-alkyl-1-aroyl-1a-acyl-1a, 9c-dihydro-1H-3-oxacyclopropa[c]phenanthren-2-ones which were formed as a single stereoisomer. Reactions of the same zinc enolates with 6-bromo-2-oxo-chromene-3-carboxamides (piperidides and morpholides) afforded 1-aroyl-6-bromo-1-alkyl-1a-piperidino-(morpholino)carbonyl-1a,7b-dihydrocyclopropa[c]chromen-2-ones with high stereoselectivity. Likewise, 1-benzoyl-1-methyl-1a-morpholinocarbonyl-1a, 9c-dihydro-1H-3-oxacyclopropa[c]phenanthren-2-one was obtained by reac-tion with 3-oxo-3H-benzo[f]chromene-2-carboxylic acid morpholide.

  由取代的1-芳基-2,2-二溴烷酮衍生的锌醇盐与2-酰基-3H-苯并[f]色烯-3-酮反应，生成1-烷基-1-酰基-1a-酰基-1a, 9c-二氢-1H-3-氧杂环丙烷[c]菲-2-酮，以单一立体异构体的形式形成。相同的锌醇盐与6-溴-2-氧-色烯-3-氨基酸酯（哌啶类和吗啉类）反应，得到1-酰基-6-溴-1-烷基-1a-哌啶（吗啉）羰基-1a, 7b-二氢环丙烷[c]色烯-2-酮，具有高立体选择性。同样，1-苯甲酰-1-甲基-1a-吗啉羰基-1a, 9c-二氢-1H-3-氧杂环丙烷[c]菲-2-酮是通过与3-氧-3H-苯并[f]色烯-2-羧酸吗啉的反应获得的。
• Cyclopropanation of N-Substituted 2-Oxochromene- and 6-Bromo-2-oxochromene-3-carboxamides with Zinc Enolates Derived from 1-Aryl-2,2-dibromoalkanones
  作者：V. V. Shchepin、P. S. Silaichev、R. V. Shchepin、M. A. Ezhikova、M. I. Kodess

  DOI：10.1007/s11178-005-0199-6

  日期：2005.4

  Zinc enolates derived from 1-aryl-2,2-dibromoalkanones react with N-cyclohexyl-2-oxochromene-3-carboxamides to give N-cyclohexyl-1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-1a-carboxamides mainly as cis isomers with respect to the substituents in positions 1 and 1a. Reactions of the same zinc enolates with N-benzyl-2-oxochromene-3-carboxamide and N-benzyl-6-bromo-2-oxochromene-3-carboxamide lead to formation of 1-aryl-2-benzyl- and 1-aryl-2-benzyl-6-bromo-1-hydroxy-9c-alkyl-1,2,9b,9c-tetrahydro-5-oxa-2-azacyclopenta[2,3]cyclopropa[1,2-a]naphthalene-3,4-diones. The reaction of zinc enolates with N-aryl-2-oxochromene-3-carboxamides in a weakly polar solvent (diethyl ether or ethyl acetate) affords mixtures of cis-N-aryl-1-aroyl-1-alkyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-1a-carboxamides and their cyclic isomers, 9c-alkyl-1,2-diaryl-1-hydroxy-1,2,9b,9c-tetrahydro-5-oxa-2-azacyclopenta[2,3]cyclopropa[1,2-a]naphthalene-3,4-diones, the latter prevailing. N-Substituted 1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-1a-carboxamides in which the aroyl group on C1 and the carboxamide group on C1a are arranged trans are formed by reactions of zinc enolates with the corresponding 2-oxochromene-3-carboxamides in the presence of hexamethylphosphoric triamide.

  源自1-芳基-2,2-二溴代烷基酮的锌烯醇盐与N-环己基-2-氧代色烯-3-羧酰胺反应，主要生成顺式异构体，相对于位置1和1a的取代基，形式为N-环己基-1-烷基-1-芳酰基-2-氧代-1a,7b-二氢环丙[c]色烯-1a-羧酰胺。同样的锌烯醇盐与N-苄基-2-氧代色烯-3-羧酰胺和N-苄基-6-溴-2-氧代色烯-3-羧酰胺反应，生成1-芳基-2-苄基和1-芳基-2-苄基-6-溴-1-羟基-9c-烷基-1,2,9b,9c-四氢-5-氧-2-氮杂环戊[2,3]环丙[1,2-a]萘-3,4-二酮。锌烯醇盐与N-芳基-2-氧代色烯-3-羧酰胺在弱极性溶剂（乙醚或乙酸乙酯）中反应，得到顺式N-芳基-1-芳酰基-1-烷基-2-氧代-1a,7b-二氢环丙[c]色烯-1a-羧酰胺及其环状异构体，即9c-烷基-1,2-二芳基-1-羟基-1,2,9b,9c-四氢-5-氧-2-氮杂环戊[2,3]环丙[1,2-a]萘-3,4-二酮，后者占优势。在六甲基磷酸三胺存在下，锌烯醇盐与相应的2-氧代色烯-3-羧酰胺反应，生成N-取代的1-烷基-1-芳酰基-2-氧代-1a,7b-二氢环丙[c]色烯-1a-羧酰胺，其中C1上的芳酰基和C1a上的羧酰胺基团以反式排列。
• Reaction of Zinc Enolates Formed from 1-Aryl-2,2-dibromoalkanones and Zinc, with Aryl Esters and Chloride of 2-Oxo-2H-chromene-3-carboxylic Acid
  作者：V. V. Shchepin、M. M. Kalyuzhnyi、N. Yu. Russkikh

  DOI：10.1007/s11176-005-0444-2

  日期：2005.9

  Zinc enolates formed from 1-aryl-2,2-dibromoalkanones and zinc react with 2-oxo-2H-chromene-3-carboxylates to give aryl 1-alkyl-1-aroyl-2-oxo-1a,7b-dihydro-1H-cyclopropa[c]chromene-1a-carboxylates as a single geometric isomer. The reaction of the same zinc enolates with 2-oxo-2H-chromene-3-carboxyl chloride to form 2-bromo-1-arylalkenyl 1-alkyl-1-aroyl-2-oxo-1,7b-dihydro-1H-cyclopropa[c]chromene-1a-carboxylates.

  锌烯醇盐由1-芳基-2,2-二溴烷酮和锌反应形成，并与2-氧代-2H-香豆烯-3-羧酸酯反应，生成单一几何异构体的芳基1-烷基-1-芳酰基-2-氧代-1a,7b-二氢-1H-环丙 [c] 香豆烯-1a-羧酸酯。相同的锌烯醇盐与2-氧代-2H-香豆烯-3-羧酸氯反应，形成2-溴-1-芳基烯基1-烷基-1-芳酰基-2-氧代-1,7b-二氢-1H-环丙 [c] 香豆烯-1a-羧酸酯。
• Cyclopropanation of 3-(2-Oxo-2H-chromen-3-yl-carbonyl)-2H-chromen-2-one with Zinc Enolates Derived from 1-Aryl-2,2-dibromoalkanones
  作者：V. V. Shchepin、N. Yu. Russkikh、D. V. Uzun、P. S. Silaichev

  DOI：10.1007/s11178-005-0135-9

  日期：2005.1

  Zinc enolates derived from 1-aryl-2,2-dibromoalkanones react with 3-(2-oxo-2H-chromen-3-ylcarbonyl)-2H-chromen-2-one to give 1-alkyl-1-aroyl-1a-(2-oxo-2H-chromen-3-ylcarbonyl)-1a, 7b-dihydrocyclopropa[c]-chromen-2(1H)-ones as a single stereoisomer.

  衍生自 1-芳基-2,2-二溴烷酮的烯醇锌与 3-(2-氧代-2H-苯并吡喃-3-基羰基)-2H-苯并吡喃-2-酮反应，得到 1-烷基-1-芳酰基-1a- (2-氧代-2H-苯并-3-基羰基)-1a, 7b-二氢环丙[c]-苯并-2(1H)-酮作为单一立体异构体。