5-[Bis(tert-butylamino)methylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione | 131297-21-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-[Bis(tert-butylamino)methylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione
• CAS: 131297-21-7
• 化学式: C₁₅H₂₆N₂O₄
• 分子量: 298.382
• InChiKey: PIKSHCMCNASZRO-UHFFFAOYSA-N

物化性质

• 熔点：
  151 °C
• 沸点：
  428.4±45.0 °C(Predicted)
• 密度：
  1.070±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  76.7
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-[Bis(tert-butylamino)methylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione 600.0 ℃ 、133.32 Pa 条件下， 以58%的产率得到N-(叔丁基)-2-氰乙酰胺
  参考文献：
  名称：

  Synthesis of .alpha.-cyano carbonyl compounds by flash vacuum thermolysis of (alkylamino)methylene derivatives of Meldrum's acid. Evidence for facile 1,3-shifts of alkylamino and alkylthio groups in imidoylketene intermediates

  摘要：

  The syntheses and flash vacuum thermolyses of 5-[(alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones (Meldrum's acid derivatives) 13a-i are described. Thermolysis of 13a as well as of ethyl 3-(tert-butylamino)acrylate (22) gives a tautomeric mixture of cyanoacetaldehyde (14) and 3-hydroxypropenenitrile (15). Thermolysis of 13b gives iminoacrolein 26 and not cyanoacetone (29). Thermolysis of 13c,d gives S-methyl cyanothioacetate (30), and 13f-h give cyanoacetamides 31 in high yields. 2-Cyanopent-4-enoic acid derivatives 32 are obtained from Meldrum's acids 13e,i. The results are discussed in terms of facile 1,3-shifts of methylthio and alkylamino groups in imidoylketenes, interconverting imidoylketenes and acylketene imines.

  DOI：

  10.1021/jo00003a014
• 作为产物：
  描述：

  丙二酸环(亚)异丙酯 在 二硫化碳 、 三乙胺 作用下， 以 乙醇 为溶剂， 反应 63.0h， 生成 5-[Bis(tert-butylamino)methylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione
  参考文献：
  名称：

  Synthesis of .alpha.-cyano carbonyl compounds by flash vacuum thermolysis of (alkylamino)methylene derivatives of Meldrum's acid. Evidence for facile 1,3-shifts of alkylamino and alkylthio groups in imidoylketene intermediates

  摘要：

  The syntheses and flash vacuum thermolyses of 5-[(alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones (Meldrum's acid derivatives) 13a-i are described. Thermolysis of 13a as well as of ethyl 3-(tert-butylamino)acrylate (22) gives a tautomeric mixture of cyanoacetaldehyde (14) and 3-hydroxypropenenitrile (15). Thermolysis of 13b gives iminoacrolein 26 and not cyanoacetone (29). Thermolysis of 13c,d gives S-methyl cyanothioacetate (30), and 13f-h give cyanoacetamides 31 in high yields. 2-Cyanopent-4-enoic acid derivatives 32 are obtained from Meldrum's acids 13e,i. The results are discussed in terms of facile 1,3-shifts of methylthio and alkylamino groups in imidoylketenes, interconverting imidoylketenes and acylketene imines.

  DOI：

  10.1021/jo00003a014

文献信息

• Cyanoketene and Iminopropadienones
  作者：Daniel W. J. Moloney、Ming Wah Wong、Robert Flammang、Curt Wentrup

  DOI：10.1021/jo9701288

  日期：1997.6.1

  Cyanoketene (8) is generated in high yields on flash vacuum thermolysis (FVT) of suitably substituted Meldrum's acid derivatives (5-[(alkylamino)(methylthio or alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones) (3e-j), and also on FVT of cyanoacetic acid derivatives 9e,f,g,j,k,m. The major reaction pathway from 3 proceeds via ketenimines 6 and (alkylimino)propadienones 7, the latter undergoing

  氰基乙烯酮（8）通过闪蒸真空热解（FVT）适当取代的麦德鲁姆酸衍生物（5-[（（烷基氨基）（甲硫基或烷基氨基）亚甲基] -2,2-二甲基-1,3-二恶烷-4）高产率生成，6-二酮）（3e-j），以及氰基乙酸衍生物9e，f，g，j，k，m的FVT。3的主要反应途径是通过烯酮亚胺6和（烷基亚氨基）丙二烯酮7进行的，后者进行逆烯反应至8。次要途径是通过亚氨基酮烯4e，h和氧烯酮5e，h，它们进行逆烯反应。 9.所有中间体均通过Ar矩阵FTIR和串联质谱（碰撞活化MS）进行表征。还报道了用亲核试剂捕获4、5和8。1,3-X的优先级会超过1，酰亚胺基乙烯酮12（X = SMe或NMe（2））中的5-H位移已通过计算得出的激活势垒得到证实。纯的氰基烯酮具有很高的反应活性，在80 K或更低的温度下会发生反应，这归因于低洼的烯酮LUMO的可用性。氰基烯（Ar，14 K）的IR光谱主要受2163（s; C =
• CHEIKH, ABDELHAMID;BEN;CHUCHE, JOSSELIN;MANISSE, NOEL;POMMELET, JEAN CLAU+, J. ORG. CHEM., 56,(1991) N, C. 970-975
  作者：CHEIKH, ABDELHAMID、BEN、CHUCHE, JOSSELIN、MANISSE, NOEL、POMMELET, JEAN CLAU+

  DOI：——

  日期：——
• Synthesis of .alpha.-cyano carbonyl compounds by flash vacuum thermolysis of (alkylamino)methylene derivatives of Meldrum's acid. Evidence for facile 1,3-shifts of alkylamino and alkylthio groups in imidoylketene intermediates
  作者：Abdelhamid Ben Cheikh、Josselin Chuche、Noel Manisse、Jean Claude Pommelet、Klaus Peter Netsch、Primoz Lorencak、Curt Wentrup

  DOI：10.1021/jo00003a014

  日期：1991.2

  The syntheses and flash vacuum thermolyses of 5-[(alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones (Meldrum's acid derivatives) 13a-i are described. Thermolysis of 13a as well as of ethyl 3-(tert-butylamino)acrylate (22) gives a tautomeric mixture of cyanoacetaldehyde (14) and 3-hydroxypropenenitrile (15). Thermolysis of 13b gives iminoacrolein 26 and not cyanoacetone (29). Thermolysis of 13c,d gives S-methyl cyanothioacetate (30), and 13f-h give cyanoacetamides 31 in high yields. 2-Cyanopent-4-enoic acid derivatives 32 are obtained from Meldrum's acids 13e,i. The results are discussed in terms of facile 1,3-shifts of methylthio and alkylamino groups in imidoylketenes, interconverting imidoylketenes and acylketene imines.