2-(phenylsulfonyl)-1,1,5,5-tetramethyl-1,5-diazapentadienium perchlorate | 127572-47-8

• 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: 2-(phenylsulfonyl)-1,1,5,5-tetramethyl-1,5-diazapentadienium perchlorate
• 英文别名: [(Z)-2-(benzenesulfonyl)-3-(dimethylamino)prop-2-enylidene]-dimethylazanium;perchlorate
• CAS: 127572-47-8
• 化学式: C₁₃H₁₉N₂O₂S*ClO₄
• 分子量: 366.823
• InChiKey: GQDNXVUHKLQRTR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -3.55
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  123
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-(phenylsulfonyl)-1,1,5,5-tetramethyl-1,5-diazapentadienium perchlorate 在 sodium tetrahydroborate 作用下， 以 异丙醇 为溶剂， 反应 22.0h， 生成 1,3-bis(dimethylamino)-2-(phenylsulfonyl)-1-propene
  参考文献：
  名称：

  The preparation and some reactions of 2-(arylsulfonyl)vinamidinium salts

  摘要：

  The preparation of novel 2-(arylsulfonyl)vinamidinium salts is described. The reactions of these materials with amidines, hydrazine, hydroxylamine, sodium borohydride, and Grignard reagents are presented along with an evaluation of their chemical behavior as compared to the 2-arylvinamidinium salts.

  DOI：

  10.1021/jo00003a015
• 作为产物：
  描述：

  (苯磺酰)乙酸 、 N,N-二甲基甲酰胺 在 sodium perchlorate 、 三氯氧磷 作用下， 生成 2-(phenylsulfonyl)-1,1,5,5-tetramethyl-1,5-diazapentadienium perchlorate
  参考文献：
  名称：

  The preparation and some reactions of 2-(arylsulfonyl)vinamidinium salts

  摘要：

  The preparation of novel 2-(arylsulfonyl)vinamidinium salts is described. The reactions of these materials with amidines, hydrazine, hydroxylamine, sodium borohydride, and Grignard reagents are presented along with an evaluation of their chemical behavior as compared to the 2-arylvinamidinium salts.

  DOI：

  10.1021/jo00003a015

文献信息

• The Application of Vinamidinium Salts to the Synthesis of 2-Amino-5-aryl or Formylpyridine-3-carbonitriles
  作者：Fayçel Jemmezi、Samar Chtiba、Jameleddine Khiari

  DOI：10.1002/jhet.911

  日期：2013.3

  The symmetrical vinamidinium salts were allowed to react with malononitrile in refluxing ethanol in the presence of ammonium acetate for 12 h to afford the 2‐amino‐5‐aryl or formylpyridine‐3‐carbonitriles.

  在乙酸铵存在下，使对称的vinamidinium盐与丙二腈在回流的乙醇中反应12 h，得到2-氨基-5-芳基或甲酰基吡啶-3-腈。
• Application of 2-substituted vinamidinium salts to the synthesis of 2,4-disubstituted pyrroles
  作者：John T. Gupton、Dale A. Krolikowski、Richard H. Yu、Steve W. Riesinger、James A. Sikorski

  DOI：10.1021/jo00302a047

  日期：1990.7
• A new route to 1,5-disubstituted 4-arylsulfonylpyrazoles by lithiation of 1-methyl-4-arylsulfonylpyrazoles
  作者：Michael G. Hoffmann

  DOI：10.1016/0040-4020(95)00540-o

  日期：1995.8

  The arylsulfonylvinamidinium salts 1 reacted with hydrazine in refluxing ethanol to give rise to 4-arylsulfonylpyrazoles 2 in reasonable yield. Regioselective lithiation of N-methylpyrazoles 3 with LDA followed by treatment with various electrophiles afforded the corresponding 1,5-disubstituted 4-arylsulfonylpyrazoles 5 in good yield.
• Demonstrating the Synergy of Synthetic, Mechanistic, and Computational Studies in a Regioselective Aniline Synthesis
  作者：Ian W. Davies、Jean-François Marcoux、Jeffery T. Kuethe、Michael D. Lankshear、Jeremy D. O. Taylor、Nancy Tsou、Peter G. Dormer、David L. Hughes、K. N. Houk、Vildan Guner

  DOI：10.1021/jo035677u

  日期：2004.2.1

  Tri- and tetrasubstituted anilines are formed in good to excellent yields by the addition of ketones to vinamidinium salts (up to 98%). The reaction proceeds via the formation of dienone intermediates, which react to form an enamine with the liberated amine. In the case of a nitro, or dimethylaminomethylene substituent, the enamines undergo a facile electrocyclic ring closure to form a cyclohexadiene, which goes on to form anilines with a high degree of selectivity (up to 50:1) with a minor competing pathway proceeding via the enol providing phenols. Competition experiments using isotopic substitution reveal that the rate determining step en route to dienone is enol/enolate addition to the vinamidinium salt, which is characterized by an inverse secondary isotope effect (k(H/D) 0.7-0.9). Computational studies have been used to provide a framework for understanding the reaction pathway. The original proposal for a [1,5]-H shift was ruled out on the basis of the calculations, which did not locate a thermally accessible transition state. The minimum energy conformation of the enamine is such that a facile electrocyclic ring closure is ensured, which is corroborated by the experimental studies. A framework for understanding the reaction pathway is presented.
• Efficient One-Pot Synthesis of Substituted Pyrido[2,3-d]pyrimidines from Vinamidinium and Chloropropeniminium Salts
  作者：Mohamed Adnen Hadj Ayed、Thouraya Gmiza、Jamel Eddine Khiari、Béchir Ben Hassine

  DOI：10.1080/00397911.2010.545163

  日期：2012.6.15

  A novel and efficient one-pot preparation of 6-substituted pyrido-[2,3-d]pyrimidines by cyclocondensation of 6-amino-1,3-dimethyluracil with symmetrical vinamidinium salts under basic conditions has been developed. Regioselectivity was observed with an unsymmetrical chloropropeniminium salt.