2,2-二甲基-5-(1H-吡咯-2-基亚甲基)-1,3-二恶烷-4,6-二酮 | 23111-03-7

• 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-(1H-吡咯-2-基亚甲基)-1,3-二恶烷-4,6-二酮
• 英文名称: 5-((1H-pyrrol-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione
• 英文别名: 2,2-dimethyl-5-(1H-pyrrol-2-ylmethylidene)-1,3-dioxane-4,6-dione
• CAS: 23111-03-7
• 化学式: C₁₁H₁₁NO₄
• mdl: MFCD00075361
• 分子量: 221.213
• InChiKey: BBNAXFLKFJZVEN-UHFFFAOYSA-N

物化性质

• 熔点：
  181-182 °C
• 沸点：
  540.0±50.0 °C(Predicted)
• 密度：
  1.332±0.06 g/cm3(Predicted)
• 溶解度：
  25.4 [ug/mL]

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.272
• 拓扑面积：
  68.4
• 氢给体数：
  1
• 氢受体数：
  4

安全信息

• 海关编码：
  2934999090

反应信息

• 作为反应物：
  描述：

  2,2-二甲基-5-(1H-吡咯-2-基亚甲基)-1,3-二恶烷-4,6-二酮 600.0 ℃ 、0.13 Pa 条件下， 以88%的产率得到Pyrrolizin-3-one
  参考文献：
  名称：

  Pyrrolizin-3-one

  摘要：

  DOI：

  10.1021/jo00326a046
• 作为产物：
  描述：

  吡咯 、 5-(甲氧基甲烯基)-2,2-二甲基-1,3-二氧己环-4,6-二酮 以 乙腈 为溶剂， 以73%的产率得到2,2-二甲基-5-(1H-吡咯-2-基亚甲基)-1,3-二恶烷-4,6-二酮
  参考文献：
  名称：

  3-Hydroxypyrroles and 1H-pyrrol-3(2H)-ones. Part 13. Reactions of methoxymethylene Meldrum's acid with 3-hydroxypyrroles, with 3-methoxypyrroles and with other active substrates, and pyrolytic heterocyclisations of the products

  摘要：

  Methoxymethylene Meldrum's acid 2 in acetonitrile solution acts as a useful C-electrophile for active substrates such as pyrrole, indole or tertiary enaminones to give substitution products (e.g. 5, 6 or 12, respectively). Primary enaminones react exclusively at the nitrogen atom under these conditions. The effect of ring substituents on the regiochemistry of electrophilic substitution of 3-hydroxypyrroles and 3-methoxypyrroles was studied using methoxymethylene Meldrum's acid as the electrophile. Flash vacuum pyrolysis of the Meldrum's acid derivatives obtained in many of these reactions gave access to a range of heterocyclic systems, including the pyridone 48, quinolinedione 43, benzazepinedione 41 and fused pyrones 50, 52 and 54.

  DOI：

  10.1039/p19930002017

文献信息

• Synthesis of pyrrolizin-3-ones by flash vacuum pyrolysis of pyrrol-2-ylmethylidene Meldrum’s acid derivatives and 3-(pyrrol-2-yl)propenoic esters
  作者：Shirley E. Campbell、Murray C. Comer、Paul A. Derbyshire、Xavier L. M. Despinoy、Hamish McNab、Roderick Morrison、Craig C. Sommerville、Craig Thornley

  DOI：10.1039/a701749i

  日期：——

  Monosubstituted pyrrolizin-3-ones 1 with substituents at the 1-, 5-, 6- or 7-positions are prepared in excellent yield by flash vacuum pyrolysis (FVP) of appropriate Meldrum’s acid derivatives 2. The mechanism involves formation of the pyrrol-2-ylmethylideneketene 29, which can also be generated thermally from 3-(pyrrol-2-yl)propenoate esters (e.g. 30). This alternative route has been used to make a range of 2-substituted pyrrolizin-3-ones, again in excellent yield. The 3-oxo-3H-pyrrolizine-2-carboxylic acid 42 could not be made in this way owing to facile decarboxylation to pyrrolizinone 1, and extension to the formation of the azaazulenone 48 was again unsuccessful.

  具有1-、5-、6-或7-位取代基的单取代吡咯并吡嗪-3-酮1通过适当的美尔格酸衍生物2的闪蒸真空热解(FVP)以极佳产率制备。其机理涉及吡咯-2-亚甲基烯酮29的形成，该物质也可通过3-(吡咯-2-基)丙烯酸酯(例如30)的热解生成。这条替代路线已被用于以极佳产率制备一系列2-取代吡咯并吡嗪-3-酮。由于易于脱羧转化为吡咯并吡嗪酮1，3-氧代-3H-吡咯并吡嗪-2-羧酸42无法通过此方法制备，而扩展到制备氮杂蒽酮48的尝试再次失败。
• A readily accessible porous organic polymer facilitates high-yielding Knoevenagel condensation at room temperature both in water and under solvent-free mechanochemical conditions
  作者：Parishmita Sarma、Kashyap Kumar Sarmah、Dharittri Kakoti、Sanjeev Pran Mahanta、Nadeesh Madusanka Adassooriya、Goutam Nandi、Pranab Jyoti Das、Dejan-Krešimir Bučar、Ranjit Thakuria

  DOI：10.1016/j.catcom.2021.106304

  日期：2021.6

  Its high chemical stability, reusability and poor solubility enable the use of the porous polymer as a metal-free heterogeneous catalyst for CC bond formation at ambient temperature under environmentally benign conditions.

  使用微波辅助方法合成了一种新型的富氮无定形多孔有机聚合物。它的高化学稳定性，可重复使用性和较差的溶解度使该多孔聚合物可用作无金属的非均相催化剂，可在环境温度良好的环境条件下形成C C键。
• Structure and electronics in 1H-pyrrol-2-ylmethylene compounds
  作者：Briana R. Schrage、Victor N. Nemykin、Christopher J. Ziegler

  DOI：10.1016/j.tet.2020.131149

  日期：2020.5

  between pyrrole aldehydes and several organic CH acids. New compounds were characterized by a variety of spectroscopic methods, electrochemistry as well as X-ray crystallography. DFT calculations on these compounds indicates an appreciable amount of electronic delocalization between the pyrrole and acid-derived alkene units. The compounds display a single intense π→π* transitions in the UV–visible

  在这份报告中，我们介绍了1H-吡咯-2-基亚甲基的合成和表征，它是由吡咯醛醛与几种有机CH酸之间的Knoevenagel缩合制备的。通过多种光谱方法，电化学以及X射线晶体学对新化合物进行了表征。这些化合物的DFT计算表明，在吡咯和酸衍生的烯烃单元之间有相当数量的电子离域。这些化合物在紫外可见区域内显示出单个强烈的π→π*跃迁。从头算和半经验计算表明，HOMO到LUMO单电子激发是新发色团吸收最强的原因。
• Enantioselective Ammonium Ylide Mediated One‐Pot Synthesis of Highly Substituted <i>γ</i> ‐Butyrolactones
  作者：Till Drennhaus、Laura Öhler、Saveh Djalali、Svenja Höfmann、Clemens Müller、Jörg Pietruszka、Dennis Worgull

  DOI：10.1002/adsc.202000039

  日期：2020.6.15

  diastereoselectivities (>95:5) via a DABCO‐mediated [2+1] annulation. Utilization of enantiomerically pure cinchona alkaloid derivatives enables the first asymmetric ammonium ylide mediated method to provide (3R , 4R )‐β,γ ‐disubstituted and (2R , 3R, 4R )‐α,β,γ ‐trisubstituted γ ‐butyrolactones in moderate to good yields with up to very good enantiomeric ratios (97:3). The scalability of the transformation

  对铵内盐介导的接入反式β，γ双取代的，全反式- α，β，γ三取代，和α，α，β，γ -tetrasubstituted γ丁内酯轴承各种各样的功能开发。从广为人知的亚苄基Meldrum酸衍生物和α-溴代羰基化合物开始，通过DABCO介导的[2 + 1]环化法获得的γ-丁内酯的收率在32-99％之间，具有极好的非对映选择性（> 95：5）。对映体纯金鸡纳生物碱衍生物的使用使第一个不对称的叶立铵铵介导的方法能够提供（3 R，4R）-β，γ-二取代和（2 R，3 R， 4 R）-α，β，γ-三取代γ-丁内酯，产率中等至良好，对映体比例非常高（97：3）。在确定绝对配置时，证明了转换的可伸缩性。
• Synthesis of Bis-spiro Cyclopropanes Based on Meldrum’s Acid by Milling
  作者：Elmira Kashani、Nader Noroozi Pesyan、Tuncay Tunç、Ertan Sahin

  DOI：10.1002/jccs.201400320

  日期：2015.3

  Reaction of 2,2‐dimethyl‐1,3‐dioxane‐4,6‐dione (Meldrum’s acid) with various solid aldehydes in the presence of cyanogen bromide and solid sodium ethoxide (EtONa) leads to the selective and efficient formation of bis‐spiro cyclopropanes based on Meldrum’s acid at the range of 0 °C to room temperature. The products were obtained in good to excellent yields. Structure elucidation is carried out by 1H

  在溴化氰和乙醇钠（EtONa）存在下，2,2-二甲基-1,3-二恶烷-4,6-二酮（麦德鲁姆酸）与各种固体醛的反应导致选择性和有效地形成双-基于Meldrum酸的螺环丙烷，温度范围为0°C至室温。获得的产物具有良好至优异的产率。通过1 H NMR，13 C NMR，FT-IR光谱，质量分析和X射线晶体学技术进行结构阐明。还讨论了在无溶剂条件下形成产品的可能机理。