3-hydroxy-4,4,5,5-tetramethyl-3-phenyl-1,2-dioxolane | 137363-42-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-hydroxy-4,4,5,5-tetramethyl-3-phenyl-1,2-dioxolane
• 英文别名: 3-hydroxy-3-phenyl-4,4,5,5-tetramethyl-1,2-dioxolane；4,4,5,5-Tetramethyl-3-phenyldioxolan-3-ol
• CAS: 137363-42-9
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: SHNHUSLJSOIJDO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-hydroxy-4,4,5,5-tetramethyl-3-phenyl-1,2-dioxolane 在 双氧水 、 对甲苯磺酸 作用下， 以 乙腈 为溶剂， 反应 0.25h， 以93%的产率得到3-hydroperoxy-3-phenyl-4,4,5,5-tetramethyl-1,2-dioxolane
  参考文献：
  名称：

  3-氢过氧-3,4,4,5,5-五取代-1,2-二氧戊环的合成及氧原子转移反应

  摘要：

  通过与浓3-过氧化氢反应，由相应的3-羟基-1,2-二氧戊环高产率地合成了一系列3-氢过氧-3,4,4,5,5-五取代-1,2-二氧戊环2a-d以对甲苯磺酸为催化剂，在乙腈中溶解。3-氢过氧-1,2-二氧戊环是将硫代苯甲醚，三乙胺和2,3-二甲基-2-丁烯分别氧化为亚砜，N-氧化物和环氧化物的有效氧原子转移试剂。反应在温和的条件下发生，被发现总体上是二级反应。测定在氘代氯仿中2a-d氧化硫代苯甲醚的二阶速率常数（k 2）。对于2a，k还测量了N-氧化和环氧化的2个值。发现3-氢过氧-1,2-二氧戊环的反应性比结构相似的环状α-偶氮氢过氧化物低，但比简单的氢过氧化物高得多。假设氧原子转移的机理是通过底物在氢过氧化物的末端氧上的亲核攻击而发生的。氢过氧质子与二氧戊环氧的分子内氢键似乎是非质子介质中反应顺序的原因。

  DOI：

  10.1002/jhet.5570330464
• 作为产物：
  描述：

  3-Hydroperoxy-4,4,5,5-tetramethyl-3-phenylpyrazole 在 氧气 作用下， 以 苯 为溶剂， 以36%的产率得到3-hydroxy-4,4,5,5-tetramethyl-3-phenyl-1,2-dioxolane
  参考文献：
  名称：

  Synthesis of pentasubstituted 3-hydroxy-1,2-dioxolanes

  摘要：

  DOI：

  10.1021/jo00027a072

文献信息

• Synthesis and Thermolysis of Ketal Derivatives of 3-Hydroxy-1,2-dioxolanes
  作者：A. L. Baumstark、P. C. Vasquez、Y.-X. Chen

  DOI：10.1021/jo00101a030

  日期：1994.11

  3-[(Trimethylsilyl)oxy]-3,4,4,5-tetramethyl-5-phenyl-1,2-dioxolane (2), 3-methoxy-3,4,4,5-tetra-methyl-5-phenyl-1,2-dioxolane (3), and 3-acetoxy-3,4,4,5-tetramethyl-5-phenyl-1 (4) were synthesized from the corresponding 3-hydroxy-1,2-dioxolane (1a) under basic conditions. 3-Acetoxy-4,4-dimethyl-3,5,5-triphenyl-1,2-dioxolane (5) was also synthesized via this approach. Under acidic conditions, 3-hydroxy-1,2-dioxolane la underwent quantitative decomposition to phenol and 3,3-dimethyl-2,4-pentanedione. This competing degradation was dependent on the nature of the substituents at position-5. Methyl groups at position-5 slowed the degradative rearrangement whereas phenyl groups favored it. 3-Methoxy- and 3-(allyloxy)-4,4,5,5-tetramethyl-3-pheny dioxolanes (6, 7) were synthesized under acidic conditions from the appropriate 1,2-dioxolane precursors and the corresponding alcohols. At 60 degrees C, derivatized 1,2-dioxolanes 2-7 were found to be more stable than the corresponding 3-hydroxy-1, 2-dioxolanes. The first order rate constants for the thermolysis of 1,2-dioxolanes 2-7 were determined. Product studies showed that thermolysis of 2-5 yielded pairs of ketones and derivatized carboxylic acids. In addition to R-group migration products, an acetoxy migration product was observed for the thermolysis of 4. Thermolysis of 6 at 60 degrees C in benzene yielded methyl benzoate and pinacolone, quantitatively. Thermolysis of 7 yielded products analogous to those for 6. No evidence for internal trapping of radicals by the carbon-carbon double bond of the allyloxy group in 7 was found. The thermolyis appeared to proceed with peroxy bond homolysis as the rate-determining step. Subsequent beta-scissions of the intermediate 1,5-oxygen diradical with interesting rearrangements that show a high preference for alkyl vs phenyl migration account for the observed product distributions. The results suggest that the beta-scission/ rearrangement mechanism may not be concerted but rather stepwise to yield 1,3-diradical and carbonyl fragments.
• Baumstark, A. L.; Vasquez, Pedro C., Journal of Heterocyclic Chemistry, 1992, vol. 29, # 7, p. 1781 - 1783
  作者：Baumstark, A. L.、Vasquez, Pedro C.

  DOI：——

  日期：——
• Baumstark A. L., Vasquez P. C., Chen Y.-X., J. Org. Chem, 59 (1994) N 22, S 6692-6696
  作者：Baumstark A. L., Vasquez P. C., Chen Y.-X.

  DOI：——

  日期：——
• Synthesis of pentasubstituted 3-hydroxy-1,2-dioxolanes
  作者：Alfons L. Baumstark、Pedro C. Vasquez

  DOI：10.1021/jo00027a072

  日期：1992.1
• Synthesis and oxygen-atom transfer reactions of 3-hydroperoxy-3,4,4,5,5-pentasubstituted-1,2-dioxolanes
  作者：A. Baumstark、Y.-X. Chen、A. Rodriguez

  DOI：10.1002/jhet.5570330464

  日期：1996.7

  A series of 3-hydroperoxy-3,4,4,5,5-pentasubstituted-1,2-dioxolanes 2a-d were synthesized in good yield from the corresponding 3-hydroxy-1,2-dioxolanes by reaction with concentrated hydrogen peroxide in acetonitrile with p-toluenesulfonic acid as catalyst. The 3-hydroperoxy-1,2-dioxolanes were effective oxygen-atom transfer reagents for the oxidation of thioanisole, triethylamine and 2,3-dimethyl-2-butene

  通过与浓3-过氧化氢反应，由相应的3-羟基-1,2-二氧戊环高产率地合成了一系列3-氢过氧-3,4,4,5,5-五取代-1,2-二氧戊环2a-d以对甲苯磺酸为催化剂，在乙腈中溶解。3-氢过氧-1,2-二氧戊环是将硫代苯甲醚，三乙胺和2,3-二甲基-2-丁烯分别氧化为亚砜，N-氧化物和环氧化物的有效氧原子转移试剂。反应在温和的条件下发生，被发现总体上是二级反应。测定在氘代氯仿中2a-d氧化硫代苯甲醚的二阶速率常数（k 2）。对于2a，k还测量了N-氧化和环氧化的2个值。发现3-氢过氧-1,2-二氧戊环的反应性比结构相似的环状α-偶氮氢过氧化物低，但比简单的氢过氧化物高得多。假设氧原子转移的机理是通过底物在氢过氧化物的末端氧上的亲核攻击而发生的。氢过氧质子与二氧戊环氧的分子内氢键似乎是非质子介质中反应顺序的原因。