2-Benzoylhydrazono-3-methylbuttersaeure | 173973-79-0

• 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-Benzoylhydrazono-3-methylbuttersaeure
• CAS: 173973-79-0
• 化学式: C₁₂H₁₄N₂O₃
• 分子量: 234.255
• InChiKey: QCVUGQZXBLPNOM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.51
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  78.76
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2-Benzoylhydrazono-3-methylbuttersaeure 在 N,N'-二环己基碳二亚胺 作用下， 以 四氯化碳 、 苯 为溶剂， 反应 49.0h， 生成 4-isopropyl-1-phenyl-(4α,4aβ,5α,8α)-4,4a,5,6,7,8-hexahydro-3-oxo-5,8-methano-3H-2-benzopyran
  参考文献：
  名称：

  Cycloadditionen von 6H-1,3,4-Oxadiazin-6-onen (4,5-Diaza-?-Pyronen). 14. Nicht katalysierte und durch Trifluoressigs�ure katalysierte Reaktionen von 6H-1,3,4-Oxadiazin-6-onen mit Norbornen

  摘要：

  In 11 out of 13 non-catalysed reactions of oxadiazinones 1 with norbornene, gamma-oxoketenes 4 were observed and could be isolated in three cases (4b,d,m). Except for 4m, all gamma-oxoketenes isomerised to enollactones of type 5 on thermolysis. However, 4b furnished the cyclobutene derivative 10 as the major product. No gamma-oxoketenes were detected in the reactions of Ik and 11, which gave rise to the formation of 5k and the enollactone 19, respectively. The latter was converted into 51 on treatment with trifluoroacetic acid (TFA). Four oxadiazinones 1 were allowed to react with norbornene in the presence of TFA. Three of them (1a,b,l) afforded mixtures of enollactones of type 5 and their diastereomers 12. Heating of 4 in the presence of norbornene led to the formation of the symmetrical delta-lactones 6. This process was observed to be efficient only where the conversion 4 --> 5 is slow (4b) or inoperative (4m). In five cases, the treatment of the components with boron trifluoride etherate proved to be a useful preparative alternative (6a,d,g,h,m). On treatment of 4a with methanol, the pseudoester 7a was formed, whereas 4b gave mixtures of 7b and the esters 8b and 15. Hydrogen chloride converted 4b into the pseudochloride 14, which furnished pseudoester 7b on methanolysis. Reaction of 4b,m with formic acid gave rise to pseudoanhydrides of type 13. From 4b and TFA a mixture of the enollactones 5b and 12b was obtained. Boron trifluoride etherate transformed 4i to enollactone 12i; analogously, 12m resulted on treatment of 4m with trifluoromethanesulfonic acid.

  DOI：

  10.1002/prac.199533701140
• 作为产物：
  描述：

  2-氧代-3-甲基丁酸 、 苯甲酰肼 以 水 为溶剂， 反应 2.0h， 以70%的产率得到2-Benzoylhydrazono-3-methylbuttersaeure
  参考文献：
  名称：

  Cycloadditionen von 6H-1,3,4-Oxadiazin-6-onen (4,5-Diaza-?-Pyronen). 14. Nicht katalysierte und durch Trifluoressigs�ure katalysierte Reaktionen von 6H-1,3,4-Oxadiazin-6-onen mit Norbornen

  摘要：

  In 11 out of 13 non-catalysed reactions of oxadiazinones 1 with norbornene, gamma-oxoketenes 4 were observed and could be isolated in three cases (4b,d,m). Except for 4m, all gamma-oxoketenes isomerised to enollactones of type 5 on thermolysis. However, 4b furnished the cyclobutene derivative 10 as the major product. No gamma-oxoketenes were detected in the reactions of Ik and 11, which gave rise to the formation of 5k and the enollactone 19, respectively. The latter was converted into 51 on treatment with trifluoroacetic acid (TFA). Four oxadiazinones 1 were allowed to react with norbornene in the presence of TFA. Three of them (1a,b,l) afforded mixtures of enollactones of type 5 and their diastereomers 12. Heating of 4 in the presence of norbornene led to the formation of the symmetrical delta-lactones 6. This process was observed to be efficient only where the conversion 4 --> 5 is slow (4b) or inoperative (4m). In five cases, the treatment of the components with boron trifluoride etherate proved to be a useful preparative alternative (6a,d,g,h,m). On treatment of 4a with methanol, the pseudoester 7a was formed, whereas 4b gave mixtures of 7b and the esters 8b and 15. Hydrogen chloride converted 4b into the pseudochloride 14, which furnished pseudoester 7b on methanolysis. Reaction of 4b,m with formic acid gave rise to pseudoanhydrides of type 13. From 4b and TFA a mixture of the enollactones 5b and 12b was obtained. Boron trifluoride etherate transformed 4i to enollactone 12i; analogously, 12m resulted on treatment of 4m with trifluoromethanesulfonic acid.

  DOI：

  10.1002/prac.199533701140

文献信息

• PROCEDE D'HYDROGENATION ASYMETRIQUE D'UN COMPOSE CETONIQUE ET DERIVE
  申请人：RHODIA CHIMIE

  公开号：EP0912467A1

  公开（公告）日：1999-05-06
• PROCEDE DE PREPARATION DE DIPHOSPHINES CHIRALES
  申请人：RHODIA CHIMIE

  公开号：EP1153031A1

  公开（公告）日：2001-11-14
• POLYMERE LINEAIRE OPTIQUEMENT ACTIF UTILISABLE COMME LIGAND DANS LA PREPARATION DE COMPLEXES METALLIQUES DESTINES A LA CATALYSE ASYMETRIQUE
  申请人：RHODIA CHIMIE

  公开号：EP1161481A1

  公开（公告）日：2001-12-12
• DIPHOSPHINES CHIRALES HYDROSOLUBLES
  申请人：RHODIA CHIMIE

  公开号：EP1268496A1

  公开（公告）日：2003-01-02
• [EN] ASYMMETRIC HYDROGENATION METHOD OF A KETONIC COMPOUND AND DERIVATIVE<br/>[FR] PROCEDE D'HYDROGENATION ASYMETRIQUE D'UN COMPOSE CETONIQUE ET DERIVE
  申请人：RHODIA CHIMIE

  公开号：WO1998000375A1

  公开（公告）日：1998-01-08

  (EN) The invention discloses an asymmetric hydrogenation method of a ketonic compound and derivative. It concerns the use of optically active metal complexes as asymmetric hydrogenation catalysts of a ketonic compound and derivative. The asymmetric hydrogenation method of a ketonic compound and derivative of the invention is characterised in that an asymmetric hydrogenation of the said compound is effected in the presence of an effective amount of a metal complex comprising, as ligand, an optically active diphosphine of one of the formulae (a) or (b).(FR) La présente invention a pour objet un procédé d'hydrogénation asymétrique d'un composé cétonique et dérivé. L'invention vise l'utilisation de complexes métalliques optiquement actifs comme catalyseurs d'hydrogénation asymétrique d'un composé cétonique et dérivé. Le procédé d'hydrogénation asymétrique d'un composé cétonique et dérivé selon l'invention est caractérisé par le fait que l'on effectue l'hydrogénation asymétrique dudit composé en présence d'une quantité efficace d'un complexe métallique comprenant à titre de ligand une diphosphine optiquement active répondant à l'une des formules: (a) ou (b).