5-{(hydroxy)[(3-chlorophenyl)amino]methylidene}-2,2-dimethyl-1,3-dioxane-4,6-dione | 917107-40-5

• 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: 5-{(hydroxy)[(3-chlorophenyl)amino]methylidene}-2,2-dimethyl-1,3-dioxane-4,6-dione
• 英文别名: 5-{[(3-chlorophenyl)amino](hydroxy)methylene}-2,2-dimethyl-1,3-dioxane-4,6-dione；5-[hydroxy((3-chlorophenyl)amino)-methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione；5-[hydroxy((3-chlorophenyl)amino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione；5-{[hydroxy(3-chlorophenylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione}；5-[[(3-chlorophenyl)amino](hydroxy)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione
• CAS: 917107-40-5
• 化学式: C₁₃H₁₂ClNO₅
• 分子量: 297.695
• InChiKey: SZFZRSLBOHGBBS-UHFFFAOYSA-N

物化性质

• 熔点：
  116-118 °C(Solv: ethyl acetate (141-78-6); hexane (110-54-3))
• 沸点：
  481.1±45.0 °C(Predicted)
• 密度：
  1.472±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.36
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  84.86
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  5-{(hydroxy)[(3-chlorophenyl)amino]methylidene}-2,2-dimethyl-1,3-dioxane-4,6-dione 在 叔丁基亚甲基胺 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以71%的产率得到5-[difluoroboroxy(3-chlorophenylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione
  参考文献：
  名称：

  Boron difluoride complexes of carbamoyl Meldrum's acids

  摘要：

  5-[Hydroxy(aryl/alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones react with BF3 center dot Et2O in mild conditions leading to the formation of boron difluoride complexes of carbamoyl Meldrum's acids. The X-ray structure has been obtained for one representative complex. The obtained new compounds are air and moisture stable at standard ambient conditions and easily isolable. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2012.07.004
• 作为产物：
  描述：

  丙二酸环(亚)异丙酯 、 间氯苯异氰酸酯 在 三乙胺 、 盐酸 作用下， 以 N,N-二甲基甲酰胺 、 水 为溶剂， 反应 1.4h， 以63%的产率得到5-{(hydroxy)[(3-chlorophenyl)amino]methylidene}-2,2-dimethyl-1,3-dioxane-4,6-dione
  参考文献：
  名称：

  One-Step Synthesis of β-Lactams with Retro-Amide Side Chain

  摘要：

  开发了一种一步法合成1,4-二取代2-氧代氮杂环丁-3-羧酰胺的方法。5-[(N-取代氨基)(羟基)亚甲基]梅尔德伦酸作为烯酮源，与沸腾甲苯中的亚胺反应，得到具有逆转酰胺侧链的β-内酰胺。

  DOI：

  10.1055/s-0030-1258966

文献信息

• A new approach to the stereoselective synthesis of trans-3-carbamoyl-β-lactam moieties
  作者：Anna Zakaszewska、Ewelina Najda-Mocarska、Sławomir Makowiec

  DOI：10.1039/c7nj00445a

  日期：——

  One-pot synthesis of optically active 1,4-disubstituted-3-carbamoyl-azetidinones from 5-[(N-arylamino)(hydroxyl)methylene]-2,2-dimethyl-1,3-dioxa-4,6-diones and chiral aldimines is achieved via thermal generation of carbamoyl ketenes and subsequent [2+2] cycloaddition. Three possible chiral induction approaches were tested and (R)-(+)-1-phenylethylamine was confirmed as the best chiral auxiliary. Among

  由5-[（N-芳基氨基）（羟基）亚甲基] -2,2-二甲基-1,3-二氧杂-4,6-二酮一锅法合成旋光的1,4-二取代-3-氨基甲酰基-氮杂环丁酮通过氨基甲酰基烯酮的热生成和随后的[2 + 2]环加成反应可得到手性醛亚胺。测试了三种可能的手性诱导方法，并证实（R）-（+）-1-苯基乙胺是最佳手性助剂。在四种可能的非对映异构体中，仅形成了两种，其中一种明显过量。
• Evidence for an umpolung type of [2+2] cycloaddition of 2-carbamoyl ketenes
  作者：Anna Zakaszewska、Ewelina Najda-Mocarska、Sławomir Makowiec

  DOI：10.1039/c7nj00830a

  日期：——

  Ketenes generated during the thermal decomposition of 5-[(N-aryl/alkylamino)(hydroxyl)methylene]-2,2-dimethyl-1,3-dioxa-4,6-diones react with highly electrophilic iminium ions. The initial [2+2] cycloaddition product rearranges to 2-arylidene malonamide. Mechanistic aspects of the process are presented.

  5-[（N-芳基/烷基氨基）（羟基）亚甲基] -2,2-二甲基-1,3-二氧杂-4,6-二酮热分解过程中产生的酮与高亲电性亚胺离子反应。初始的[2 + 2]环加成产物重排为2-亚芳基丙二酰胺。介绍了过程的机械方面。
• Preparation of bicyclic <b>β</b>-lactam and bicyclic 1,3-oxazinone scaffolds using combined cycloaddition and metathesis processes
  作者：Anna Zakaszewska、Ewelina Najda-Mocarska、Sławomir Makowiec

  DOI：10.1080/00397911.2018.1465980

  日期：2018.7.18

  Abstract A simple, efficient two-step method for the preparation of heterobicyclic compounds was developed. Starting from 5-acyl or 5-carbamoyl-2,2-dimethyl-1,3-dioxa-4,5-dione bicyclic scaffolds of 1-azabicyclo[5.2.0]non-3-en-9-one, 6,9,10,10a-tetrahydro-4H-[1,3]oxazino[3,2-a]azepin-4-one, and 6,9,10,10a-tetrahydro-2H-[1,3]oxazino[3,2-a]azepine-2,4(3H)-dione were prepared using cycloaddition of thermally

  摘要 开发了一种简单、高效的两步法制备杂双环化合物。从1-氮杂双环[5.2.0]non-3-en-9-one的5-酰基或5-氨基甲酰基-2,2-二甲基-1,3-二氧杂-4,5-二酮双环支架开始，6， 9,10,10a-四氢-4H-[1,3]恶嗪并[3,2-a]氮杂-4-one和6,9,10,10a-四氢-2H-[1,3]恶嗪[3] ,2-a]氮杂-2,4(3H)-二酮是通过将热生成的烯酮环加成到具有不饱和侧链的醛亚胺，然后进行复分解来制备的。该方法应用于不同杂环底物的闭环复分解（RCM）以证明其多功能性。图形概要
• One-Step Formation of N-Alkenyl-malonamides and N-Alkenyl-thiomalonamides from Carbamoyl Meldrum's Acids
  作者：Paweł Punda、Sławomir Makowiec

  DOI：10.1080/00397911.2011.634082

  日期：2013.5.15

  Abstract A one-pot synthesis for the preparation of N-alkenyl-malonamides and N-alkenyl-thiomalonamides was developed. 5-[Hydroxy/mercapto(aryl/alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-dione act as a source of ketenes that react with the tautomeric form of alkyl-(2-phenyl-propylidene)-amines. A possible [2 + 2] or [4 + 2] cycloaddition product of ketene to imines was not observed. GRAPHICAL

  摘要 开发了一种用于制备N-烯基-丙二酰胺和N-烯基-硫代丙二酰胺的一锅法合成方法。5-[羟基/巯基(芳基/烷基氨基)亚甲基]-2,2-二甲基-1,3-二恶烷-4,6-二酮作为烯酮的来源，与烷基-(2-苯基)的互变异构形式反应-亚丙基)-胺。未观察到乙烯酮与亚胺的可能的[2+2]或[4+2]环加成产物。图形概要
• Synthesis of 3-Carbamoyl<i>β</i>-Lactams<i>via</i>Manganese(III)-Promoted Cyclization of<i>N</i>-Alkenylmalonamides
  作者：Paweł Punda、Łukasz Ponikiewski、Sławomir Makowiec

  DOI：10.1002/hlca.201200646

  日期：2013.11

  Manganese(III)‐promoted cyclization of N‐alkenylmalonamides (=N‐alkenylpropanediamides) gave 3‐(aryl/(alkylamino)carbonyl) β‐lactams as well as 3‐(aryl/(alkylamino)thiocarbonyl) β‐lactams. The relative configuration of the obtained products was unambiguously determined by X‐ray crystallography. The proposed method is very useful for the one‐pot synthesis of a number of 3‐(aryl/(alkylamino)carbonyl)

  锰（III）促进的N-链烯基丙二酰胺（= N-链烯基丙烷二酰胺）的环化反应生成3-（芳基/（烷基氨基）羰基）β-内酰胺以及3-（芳基/（烷基氨基）硫羰基）β-内酰胺。所得产物的相对构型是由X射线晶体学确定的。所提出的方法对于一锅合成许多3-（芳基/（烷基氨基）羰基）β-内酰胺非常有用，尤其是那些含有氨基（硫羰基）部分的内酰胺，而其他方法无法选择性地获得这些内酰胺。