5,6-dimethyl-4,7-dihydrophthalide | 61836-17-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异苯并呋喃
• 英文名称: 5,6-dimethyl-4,7-dihydrophthalide
• 英文别名: 1(3H)-Isobenzofuranone, 4,7-dihydro-5,6-dimethyl-；5,6-dimethyl-4,7-dihydro-3H-2-benzofuran-1-one
• CAS: 61836-17-7
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: VNZVYTZXNHZUDQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5,6-dimethyl-4,7-dihydrophthalide 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲苯 为溶剂， 反应 14.0h， 生成 5,6-dimethylisobenzofuran-1(3H)-one
  参考文献：
  名称：

  (Nitroaryl)sulfinyl-substituted allenes. Novel and convenient propargyl alcohol synthons in 4 + 2 cycloaddition chemistry

  摘要：

  (Nitroaryl)sulfinyl-substituted allenes are conveniently prepared by treating propargyl alcohol or methyl 3-hydroxy-2-butynoate with a (nitroaryl)sulfenyl chloride and triethylamine. These activated allenes undergo 4 + 2 cycloaddition across the C1C2-pi-bond. The initially formed allylic sulfoxide readily undergoes a 2,3-sigmatropic rearrangement to produce a stable sulfenate ester that is easily cleaved with thiophilic reagents. The dienophilic reactivity of the (nitroary)sulfinyl-substituted allene is much greater than the corresponding propargyl alcohol, and the cycloaddition also proceeds with high regioselectivity. The Diels-Alder reaction of [(2-nitrophenyl)-sulfinyl]propadiene with Danishefsky's diene affords meta-substituted benzyl alcohols in high yield. Reaction of the more highly activated methyl 2-[(2-nitrophenyl)sulfinyl]-2,3-butadienoate with Danishefsky's diene followed by treatment of the resulting sulfenate ester with triethyl phosphite produces substituted phthalides in excellent yield. The (2,4-dinitrophenyl)sulfinyl-substituted allene was found to react smoothly with a variety of nitrones to give sulfenate esters of isoxazolidines. These allenyl sulfoxides correspond to formal equivalents of propargyl alcohol, which itself is too unreactive to undergo Diels-Alder chemistry or 1,3-dipolar cycloaddition with nitrones or nitrile oxides.

  DOI：

  10.1021/jo00013a033
• 作为产物：
  描述：

  (2-carbomethoxy-4,5-dimethyl-1,4-cyclohexadienyl)methyl 2-nitrobenzenesulfenate 在 哌啶 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以86%的产率得到5,6-dimethyl-4,7-dihydrophthalide
  参考文献：
  名称：

  (Nitroaryl)sulfinyl-substituted allenes. Novel and convenient propargyl alcohol synthons in 4 + 2 cycloaddition chemistry

  摘要：

  (Nitroaryl)sulfinyl-substituted allenes are conveniently prepared by treating propargyl alcohol or methyl 3-hydroxy-2-butynoate with a (nitroaryl)sulfenyl chloride and triethylamine. These activated allenes undergo 4 + 2 cycloaddition across the C1C2-pi-bond. The initially formed allylic sulfoxide readily undergoes a 2,3-sigmatropic rearrangement to produce a stable sulfenate ester that is easily cleaved with thiophilic reagents. The dienophilic reactivity of the (nitroary)sulfinyl-substituted allene is much greater than the corresponding propargyl alcohol, and the cycloaddition also proceeds with high regioselectivity. The Diels-Alder reaction of [(2-nitrophenyl)-sulfinyl]propadiene with Danishefsky's diene affords meta-substituted benzyl alcohols in high yield. Reaction of the more highly activated methyl 2-[(2-nitrophenyl)sulfinyl]-2,3-butadienoate with Danishefsky's diene followed by treatment of the resulting sulfenate ester with triethyl phosphite produces substituted phthalides in excellent yield. The (2,4-dinitrophenyl)sulfinyl-substituted allene was found to react smoothly with a variety of nitrones to give sulfenate esters of isoxazolidines. These allenyl sulfoxides correspond to formal equivalents of propargyl alcohol, which itself is too unreactive to undergo Diels-Alder chemistry or 1,3-dipolar cycloaddition with nitrones or nitrile oxides.

  DOI：

  10.1021/jo00013a033

文献信息

• Efficient transformation of ()-2-butene-1,4-diols to α,β-butenolides: A simple synthesis of (±)-eldanolide
  作者：T.K. Chakraborty、S. Chandrasekaran

  DOI：10.1016/s0040-4039(01)81318-6

  日期：1984.1

  ()-2-Butene-1,4-diols are efficiently converted to the corresponding α,β-butenolides using silver carbonate/celite and this methodology has been applied to the synthesis of (±)-eldanolide, the wing gland pheromone of the male African sugar cane borer, (wlk)

  使用碳酸银/硅藻土将（）-2-丁烯-1,4-二醇有效地转化为相应的α，β-丁烯化物，并且该方法已应用于合成（±）-艾丹醇化物（该物质的翼腺信息素）。非洲雄性甘蔗蛀虫，（大头）
• PADWA, ALBERT;BULLOCK, WILLIAM H.;NORMAN, BRYAN H.;PERUMATTAM, JOHN, J. ORG. CHEM., 56,(1991) N3, C. 4252-4259
  作者：PADWA, ALBERT、BULLOCK, WILLIAM H.、NORMAN, BRYAN H.、PERUMATTAM, JOHN

  DOI：——

  日期：——
• (Nitroaryl)sulfinyl-substituted allenes. Novel and convenient propargyl alcohol synthons in 4 + 2 cycloaddition chemistry
  作者：Albert Padwa、William H. Bullock、Bryan H. Norman、John Perumattam

  DOI：10.1021/jo00013a033

  日期：1991.6

  (Nitroaryl)sulfinyl-substituted allenes are conveniently prepared by treating propargyl alcohol or methyl 3-hydroxy-2-butynoate with a (nitroaryl)sulfenyl chloride and triethylamine. These activated allenes undergo 4 + 2 cycloaddition across the C1C2-pi-bond. The initially formed allylic sulfoxide readily undergoes a 2,3-sigmatropic rearrangement to produce a stable sulfenate ester that is easily cleaved with thiophilic reagents. The dienophilic reactivity of the (nitroary)sulfinyl-substituted allene is much greater than the corresponding propargyl alcohol, and the cycloaddition also proceeds with high regioselectivity. The Diels-Alder reaction of [(2-nitrophenyl)-sulfinyl]propadiene with Danishefsky's diene affords meta-substituted benzyl alcohols in high yield. Reaction of the more highly activated methyl 2-[(2-nitrophenyl)sulfinyl]-2,3-butadienoate with Danishefsky's diene followed by treatment of the resulting sulfenate ester with triethyl phosphite produces substituted phthalides in excellent yield. The (2,4-dinitrophenyl)sulfinyl-substituted allene was found to react smoothly with a variety of nitrones to give sulfenate esters of isoxazolidines. These allenyl sulfoxides correspond to formal equivalents of propargyl alcohol, which itself is too unreactive to undergo Diels-Alder chemistry or 1,3-dipolar cycloaddition with nitrones or nitrile oxides.