3-n-Butyl-4-methyl-3-cyclobutene-1,2-dione 2-(ethylene acetal) | 128242-64-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-n-Butyl-4-methyl-3-cyclobutene-1,2-dione 2-(ethylene acetal)
• 英文别名: 1-Butyl-2-methyl-5,8-dioxaspiro[3.4]oct-1-en-3-one
• CAS: 128242-64-8
• 化学式: C₁₁H₁₆O₃
• 分子量: 196.246
• InChiKey: ZRVFBSSBXOMLAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-n-Butyl-4-methyl-3-cyclobutene-1,2-dione 2-(ethylene acetal) 在 盐酸 、 四氯化碳 、 二异丁基氢化铝 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 、 乙腈 为溶剂， 反应 1.92h， 生成 2-n-Butyl-4-chloro-3-methyl-2-cyclobutenone
  参考文献：
  名称：

  A general, regioselective synthesis of substituted benzocyclobutenedione monoacetals

  摘要：

  A general, regioselective synthesis of substituted benzocyclobutenedione monoacetals is reported. Palladium-catalyzed coupling of a variety of 4-chlorocyclobutenones with 3-(tri-n-butylstannyl)-3-cyclobutene-1,2-dione 2-(ethylene acetal) and heating up to 70-100-degrees-C produces substituted benzocyclobutenedione monoacetals in good to excellent yields. Thia chemistry is presumed to proceed through palladium-catalyzed formation of a 3-(1-oxo-2-cyclobuten-4-yl)-3-cyclobutene-1,2-dione-2-(ethylene acetal) followed by a thermally induced ring opening to a dienyl ketene and subsequent six-electron electrocyclic ring closure and tautomerization. 2,3-Disubstituted 4-chlorocyclobutenones afford palladium intermediates which couple exclusively at the least-substituted allylic terminus. 2,3,4-Trisubstituted 4-chlorocyclobutenones have not been studied in detail; however, preliminary results suggest that regioselective allylic cross-coupling can be achieved. The methodology described provides an expedient and efficient route to previously difficult-to-prepare benzocyclobutenedione derivatives. These function as important synthetic intermediates in a variety of reactions developed in these and other laboratories.

  DOI：

  10.1021/jo00067a029
• 作为产物：
  描述：

  3-isopropoxy-4-methyl-3-cyclobutene-1,2-dione 2-(ethylene acetal) 在 盐酸 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 0.75h， 生成 3-n-Butyl-4-methyl-3-cyclobutene-1,2-dione 2-(ethylene acetal)
  参考文献：
  名称：

  Regiospecific preparation of cyclobutenedione monoacetals

  摘要：

  DOI：

  10.1021/jo00306a011

文献信息

• A new process for the regiocontrolled synthesis of substituted catechols and other 1,2-dioxygenated aromatics: conjugate addition of vinyl-, aryl-, and heteroarylcopper reagents to cyclobutenediones followed by thermal rearrangement
  作者：Angela Gurski、Lanny S. Liebskind

  DOI：10.1021/ja00067a027

  日期：1993.7

  A general method for the synthesis of substituted catechol derivatives has been developed utilizing the 1,4-addition of vinyl-, aryl-, and heteroarylcuprates to cyclobutendiones followed by thermal rearrangement. In situ protection with (methoxyethoxy)methyl chloride of the enolate derived from addition of the cuprate yields 2-alkoxy-4-R unsat'd -2-cyclobutenones, which rearrange thermally to substituted

  已开发出一种合成取代邻苯二酚衍生物的通用方法，利用乙烯基-、芳基-和杂芳基铜酸酯与环丁二烯的 1,4-加成，然后进行热重排。用（甲氧基乙氧基）甲基氯原位保护由添加铜酸盐衍生的烯醇化物产生 2-烷氧基-4-R 不饱和 -2-环丁烯酮，其热重排为具有不同羟基的取代的儿茶酚。单取代的环丁烯二酮在未取代的碳上进行高度区域选择性的 1,4-加成；或者，可以通过添加到环丁烯二酮单缩醛中来施加区域控制
• LIEBESKIND, LANNY S.;WIRTZ, KEVIN R., J. ORG. CHEM., 55,(1990) N9, C. 5350-5358
  作者：LIEBESKIND, LANNY S.、WIRTZ, KEVIN R.

  DOI：——

  日期：——
• Regiospecific preparation of cyclobutenedione monoacetals
  作者：Lanny S. Liebeskind、Kevin R. Wirtz

  DOI：10.1021/jo00306a011

  日期：1990.9
• A general, regioselective synthesis of substituted benzocyclobutenedione monoacetals
  作者：James P. Edwards、Damian J. Krysan、Lanny S. Liebeskind

  DOI：10.1021/jo00067a029

  日期：1993.7

  A general, regioselective synthesis of substituted benzocyclobutenedione monoacetals is reported. Palladium-catalyzed coupling of a variety of 4-chlorocyclobutenones with 3-(tri-n-butylstannyl)-3-cyclobutene-1,2-dione 2-(ethylene acetal) and heating up to 70-100-degrees-C produces substituted benzocyclobutenedione monoacetals in good to excellent yields. Thia chemistry is presumed to proceed through palladium-catalyzed formation of a 3-(1-oxo-2-cyclobuten-4-yl)-3-cyclobutene-1,2-dione-2-(ethylene acetal) followed by a thermally induced ring opening to a dienyl ketene and subsequent six-electron electrocyclic ring closure and tautomerization. 2,3-Disubstituted 4-chlorocyclobutenones afford palladium intermediates which couple exclusively at the least-substituted allylic terminus. 2,3,4-Trisubstituted 4-chlorocyclobutenones have not been studied in detail; however, preliminary results suggest that regioselective allylic cross-coupling can be achieved. The methodology described provides an expedient and efficient route to previously difficult-to-prepare benzocyclobutenedione derivatives. These function as important synthetic intermediates in a variety of reactions developed in these and other laboratories.