2,2-二甲基-5-苯基-1,3-二氧杂烷-4-酮 | 6337-34-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2,2-二甲基-5-苯基-1,3-二氧杂烷-4-酮
• 英文名称: 2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one
• 英文别名: (R,S)-2,2-dimethyl-5-phenyl-1,3-dioxolane-4-one；(+/-)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one；2,2-dimethyl-5-(RS)-phenyl-1,3-dioxolan-4-one；1,3-dioxolan-2,2'-dimethyl-5-phenyl-4-one；2,2-dimethyl-5-phenyl-[1,3]dioxolan-4-one；(+/-)-2,2-dimethyl-5-phenyl-[1,3]dioxolan-4-one
• CAS: 6337-34-4
• 化学式: C₁₁H₁₂O₃
• mdl: MFCD01327620
• 分子量: 192.214
• InChiKey: JKKLKPFEVGIRGI-UHFFFAOYSA-N

物化性质

• 熔点：
  45 °C
• 沸点：
  302.9±30.0 °C(Predicted)
• 密度：
  1.131±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.363
• 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：

  2,2-二甲基-5-苯基-1,3-二氧杂烷-4-酮 在 Co(III) ortho-phenylene-bis(N'-methyloxamidate) 氢氧化钾 、 正丁基锂 、 氧气 、 特戊醛 、 二异丙胺 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 乙腈 为溶剂， 反应 14.0h， 生成 苯甲酰乙酸
  参考文献：
  名称：

  使用扁桃酸二氧戊环酮作为苯甲酰基碳负离子的合成等价物的亲核苯甲酰化。α-羟基酸的氧化脱羧

  摘要：

  报道了使用扁桃酸二氧戊环酮作为苯甲酰基碳负离子的合成等价物 (Umpolung) 合成烷基芳基酮。该方法涉及扁桃酸二氧戊环酮的烷基化、烷基化产物中二氧戊环酮部分的水解和所得α-羟基酸的氧化脱羧。最后一步是在非常温和的条件下，在新戊醛存在下，使用 Co (III) 配合物以催化有氧方式进行的。

  DOI：

  10.3390/90500365
• 作为产物：
  描述：

  (S)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one 在 三乙烯二胺 作用下， 以 二甲基亚砜 为溶剂， 生成 2,2-二甲基-5-苯基-1,3-二氧杂烷-4-酮
  参考文献：
  名称：

  Controlled racemization and asymmetric transformation of α-substituted carboxylic acids in the melt

  摘要：

  The racemization and asymmetric transformation of a series of cx substituted carboxylic acids, viz. mandelic acid, hydratropic acid, ibuprofen and naproxen, were studied. Several racemization methods for mandelic acid were studied and it was found that base-catalyzed racemization in aprotic polar solvents was the most efficient method. Moreover, a fast and mild base-catalyzed racemization reaction in the melt was developed. DBN turned out to be a very efficient racemizing base for the substrates studied. Combination of the base-catalyzed racemization in the melt with known resolution processes resulted in crystallization-induced asymmetric transformations. Treating racemic ibuprofen or hydratropic acid with 1.5-2.5 equivalents of enantiopure alpha-methylbenzylamine and a catalytic amount of DBN resulted in the isolation of enantiomerically enriched ibuprofen or hydratropic acid with ees of up to 75% and almost quantitative yields. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00387-0

文献信息

• An efficient synthetic approach towards fully functionalized tetronic acids: the use of 1,3-dioxolane-2,4-diones as novel protected-activated synthons of α-hydroxy acids
  作者：Kyriakos C. Prousis、John Markopoulos、Vickie Mckee、Olga Igglessi-Markopoulou

  DOI：10.1016/j.tet.2015.09.017

  日期：2015.11

  A new strategy for the synthesis of tetronic acids with control over the regioselective introduction of substituents at the C-5 position has been developed. The construction of the densely functionalized quaternary carbon center within these molecules is of great importance. The key element for the proposed protocol was the utilization of O-carboxyanhydrides (OCA's) of optically active α-hydroxy acids

  为的特窗酸与以上在C-5位区域选择性引入取代基的控制合成的新战略已经研制成功。这些分子中的官能密集季碳中心的建设是非常重要的。对于所提出的协议的关键因素是利用率ø -carboxyanhydrides（OCA的）的光学活性的α羟基酸，如二齿有为保护/活化前体。通过使用NMR光谱数据和X射线结构分析的新化合物的结构进行了研究。
• Organocatalytic Diastereo- and Enantioselective Michael Addition Reactions of 5-Aryl-1,3-dioxolan-4-ones
  作者：Peter S. Hynes、Daniela Stranges、Paul A. Stupple、Antonio Guarna、Darren J. Dixon

  DOI：10.1021/ol070532l

  日期：2007.5.1

  derivatives and hexafluoroacetone have been identified as new and effective pro-nucleophiles in highly diastereo- and enantioselective Michael addition reactions to nitro olefins catalyzed by bifunctional epi-9-amino-9-deoxy cinchona alkaloid derivatives. Diastereoselectivities up to 98% and enantioselectivities up to 89% for a range of nitro olefins and 5-aryl-1,3-dioxolan-4-ones under mild reaction conditions

  由扁桃酸衍生物和六氟丙酮衍生的5-Aryl-1,3-dioxolan-4-one杂环化合物在双官能epi-9-催化的对硝基烯烃的高度非对映和对映选择性的迈克尔加成反应中，已被确定为新的有效亲核试剂。氨基-9-脱氧金鸡纳生物碱衍生物。据报道，在温和的反应条件下，一系列硝基烯烃和5-芳基-1,3-二氧戊环-4-酮的非对映选择性高达98％，对映选择性高达89％。
• Palladium-catalyzed allylation of α-hydroxy acids
  作者：Henk Moorlag、Johannes G. de Vries、Bernard Kaptein、Hans E. Schoemaker、Johan Kamphuis、Richard M. Kellogg

  DOI：10.1002/recl.19921110304

  日期：——

  Mandelic and lactic acids are converted to the 1,3-dioxolan-4-ones by treatment with acetone dimethyl acetal. Deprotonation followed by treatment with an allyl acetate and a catalytic amount (1 mol %) of palladium catalyst afforded the allylated dioxolanones, which could be hydrolyzed to the corresponding α-allyl α-hydroxy acids. The lithium enolate of the dioxolanone of mandelic acid was also coupled

  通过用丙酮二甲基乙缩醛处理，将扁桃酸和乳酸转化为1,3-二氧戊环-4-酮。脱质子化，然后用乙酸烯丙酯和催化量（1mol％）的钯催化剂处理，得到烯丙基化的二氧戊环酮，其可以水解为相应的α-烯丙基α-羟基酸。扁桃酸二氧戊环酮的烯醇锂也与甲基烯丙基，肉桂基，香叶基和（E）-1-甲基-2-丁烯基乙酸酯偶联。乳酸二氧戊环酮的烯醇酸锌在催化反应中与乙酸烯丙酯平稳反应，而当使用烯醇酸锂时未观察到可检测到的反应。与烯酸锌相比，锂的碱性提高了，这似乎是并发症的结果。
• Synthesis of α-Hydroxycarboxamides from Acetonides of α-Hydroxycarboxylic Acids and Primary Amines
  作者：A. Khalaj、E. Nahid

  DOI：10.1055/s-1985-31460

  日期：——

  The reaction of acetonides of α-hydroxycarboxylic acids with primary amines on heating provides a useful synthetic route to N-substituted α-hydroxycarboxamides. In general, formation of the α-hydroxycarboxamides is favored by the presence of only small substituents on the acetonide, by sufficient nucleophilicity of the amine, and by high-boiling aprotic solvents.

  加热时，α-羟基羧酸的乙酰苯乙醚与初级胺反应提供了一种合成N取代的α-羟基羧酰胺的有效路线。一般而言，α-羟基羧酰胺的形成受益于乙酰苯乙醚上仅有小取代基的存在、胺的足够亲核性以及高沸点非质子溶剂。
• Behaviour of Dioxolanones as Chiral Acyl Anion Equivalents
  作者：R. Alan Aitken、Andrew W. Thomas

  DOI：10.1055/s-1998-1569

  日期：1998.1

  The 1,3-dioxolan-4-ones readily derived from α-hydroxy acids act as convenient acyl anion equivalents by deprotonation-alkylation followed by flash vacuum pyrolysis. Conjugate addition of their anions to ethyl crotonate similarly gives β-methyl-γ-oxo esters and by using chiral dioxolanones these can be obtained in up to 86% e.e.

  1,3-二恶烯-4-酮可以方便地从α-羟基酸中得到，通过去质子化-烷基化后进行快速真空热解，作为方便的酰基阴离子等效物。它们的阴离子与乙基克罗顿酸酯的共轭加成类似可得到β-甲基-γ-氧基酯，使用手性二恶烯酮可以达到最高86%的对映体过量。

表征谱图