N-methyl-azaheptafulvene | 45700-20-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-methyl-azaheptafulvene
• 英文别名: 8-methylazaheptafulvene；cycloheptatrienylidene-methyl-amine；Methyl-2,4,6-cycloheptatrienyliden-imin；N-Methyliminocycloheptatrienon；N-Methyl-tropenyliden-amin；N-methylcyclohepta-2,4,6-trien-1-imine
• CAS: 45700-20-7
• 化学式: C₈H₉N
• 分子量: 119.166
• InChiKey: NUFAWAXJXMZVTJ-UHFFFAOYSA-N

物化性质

• 沸点：
  196.7±13.0 °C(Predicted)
• 密度：
  0.87±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-methyl-azaheptafulvene 以48%的产率得到
  参考文献：
  名称：

  YAMAMOTO K.; KAJIGAESHI S.; KANEMASA S., CHEM. LETT., 1977, NO 1, 91-94

  摘要：

  DOI：

文献信息

• Site specificity in cycloadditions of diphenylnitrile imine with 8-substituted-8-azaheptafulvenes and tricarbonyl (8-azaheptafulvene) iron complexes
  作者：R. Gandolfi、L. Toma

  DOI：10.1016/0040-4020(80)80045-7

  日期：1980.1

  mixture of two [8+4]-adducts in high yield. The mechanism of the reaction was investigated. The [8+4]-adducts underwent easily a reversible thermal 1,7-sigmatropic shift involving an sp3 nitrogen centre. Diphenylnitrile imine reacted also with tricarbonyl(8-azaheptafutvene)iron complexes lo give adducts to the CN double bond, the degradative oxidation of which with trimethylamine-N-oxide was investigated

  二苯基腈亚胺与8-取代的8-氮杂庚烯富烯的反应是位点和区域特异性的，并且以高收率产生两种[8 + 4]加合物的混合物。研究了反应机理。[8 + 4]加合物很容易经历一个涉及sp 3氮中心的可逆1,7-可逆热转变。二苯基腈亚胺也与三羰基（8-azaheptafutvene）铁配合物反应，生成CN双键的加合物，并研究了其被三甲胺-N-氧化物的氧化降解。在简单的扰动理论方法的基础上，简要讨论了环加成反应的特异性。
• AZAFULVENES 6. CYCLOADDITION REACTION OF 8-AZAHEPTAFULVENE TO ISOCYANATE AND ISOTHIOCYANATE
  作者：Kikuo Yamamoto、Shoji Kajigaeshi、Shuji Kanemasa

  DOI：10.1246/cl.1977.85

  日期：1977.1.5

  reacted with phenyl, methyl, benzoyl and thiobenzoyl isocyanate to give the corresponding [8+2] cycloadducts, 1,2,3,3a-tetrahydrocyclohept[d]imidazol-2-one derivatives, in good yields. The similar reactions with phenyl and methyl isothiocyanate afforded the different type of cycloadducts, 2-imino-8aH-2,3-dihydrocyclohept[d]thiazoles, which were taken to be derived from addition of the C=S bond in isothiocyanates

  8-烷基-和8-芳基-8-氮杂七富烯，原位生成或通过用碱处理8-氮杂七富维鎓氟硼酸盐而分离，与苯基、甲基、苯甲酰基和硫代苯甲酰基异氰酸酯反应得到相应的[8+2]环加合物， 1,2,3,3a-四氢环庚[d]咪唑-2-酮衍生物，收率良好。与苯基和异硫氰酸甲酯的类似反应提供了不同类型的环加合物，2-亚氨基-8aH-2,3-二氢环庚[d]噻唑，它们被认为是通过在异硫氰酸酯中通过 8π 加成 C=S 键而衍生的8-氮杂七富烯系统。另一方面，用苯甲酰异硫氰酸酯 8-氮杂七富烯得到 [8+4] 环加合物，10aH-4,5-dihydrocyclohept[f][1,3,5]oxadiazepine-4-thiones，定量产率。
• 1,3-Dipolar Cycloaddition of Nitrile Oxides to 8-Azaheptafulvenes
  作者：Remo Gandolfi、Anna Gamba、Paolo Grünanger

  DOI：10.3987/com-94-s50

  日期：——

  Azaheptafulvenes (2) reacted readily with nitrile oxides (1) to give, as a rule, only adducts derived from a reaction involving the C=N moiety of 2. The adducts consisted of a mixture of rapidly equilibrating ''spiro'' and ''condensed'' isomers, i.e. 6 reversible arrow 8, whose ratio was found to be dependent on substituents, temperature and solvent. The zwitterion (7) is an an appealing intermediate both for cycloaddition and isomerisation. Decomposition of the adducts to benzene, R(1)CN and R(2)NCO provided evidence in favor of the presence of the ''norcaradiene'' derivatives (14) (undetectable by nmr) in equilibrium with 6 and 8. Only products arising from the ''spiro'' isomer (6) were obtained in high yields in the catalytic hydrogenation of 6/8.
• Reactions between Triazolinediones and Equilibrating Forms of Cycloheptatriene Derivatives Featuring 7,7-Spiro and 1,7-Fused Heterocyclic Rings
  作者：Mauro Freccero、Remo Gandolfi、Mirko Sarzi-Amade’、Bruna Bovio

  DOI：10.1002/1099-0690(20022)2002:3<569::aid-ejoc569>3.0.co;2-w

  日期：2002.2

  Nitrile oxide-azaheptafulvene adducts consist of rapidly equilibrating mixtures of fused (1) and spiro (2) isomers, the relative stabilities of which are nicely reproduced by B3LYP/ 6-3 1 G(.) calculations. The reaction between these compounds and MTAD affords only two diastereomeric adducts [9 (dominant) and 10], both deriving from the reaction of MTAD with I even in cases in which that isomer could not be detected by NMR spectroscopy. These adducts are formal Diels-Alder adducts deriving from attacks on the two diastereotopic faces of the triene moiety of 1 and involving only the diene system adjacent to the amino substituent (N-4-C-4n=C-5-C-8=C-7). The structures of the adducts are firmly supported by spectroscopic data and X-ray analysis, and so previous incorrect assignments are revised. The mechanism of the reaction between MTAD and I is briefly discussed.
• GANDOLFI R.; TOMA L., TETRAHEDRON, 1980, 36, NO 7, 935-941
  作者：GANDOLFI R.、 TOMA L.

  DOI：——

  日期：——