16-methyl-13-nitro-oxacyclohexadecan-2-one | 86911-21-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: 16-methyl-13-nitro-oxacyclohexadecan-2-one
• CAS: 86911-21-9
• 化学式: C₁₆H₂₉NO₄
• 分子量: 299.411
• InChiKey: MCZWQIFGGBILSP-UHFFFAOYSA-N

物化性质

• 沸点：
  462.8±24.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.26
• 重原子数：
  21.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  69.44
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  16-methyl-13-nitro-oxacyclohexadecan-2-one 在 Ra-Ni titanium(III) chloride 、 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 4.5h， 生成 4(1H)-蝶啶酮,2,3,7,8-四氢-2-硫代-
  参考文献：
  名称：

  合成大环内酯内酯丁香酮（±）-Phoracantholid I，（±）-Dihydrorecifeiolid und（±）-15-Hexadecanolid

  摘要：

  通过环扩大反应反应合成大环内酯。制备（±）-邻苯三甲酚I，（±）-二氢瑞吉奥奈德和（±）-15-十六烷内酯

  DOI：

  10.1002/hlca.19840670708
• 作为产物：
  描述：

  2-(3-羟基丁基)-2-硝基环十二烷-1-酮 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以98%的产率得到16-methyl-13-nitro-oxacyclohexadecan-2-one
  参考文献：
  名称：

  合成大环内酯内酯丁香酮（±）-Phoracantholid I，（±）-Dihydrorecifeiolid und（±）-15-Hexadecanolid

  摘要：

  通过环扩大反应反应合成大环内酯。制备（±）-邻苯三甲酚I，（±）-二氢瑞吉奥奈德和（±）-15-十六烷内酯

  DOI：

  10.1002/hlca.19840670708

文献信息

• An Unexpected Asymmetric Reduction of 4-(1-Nitro-2-oxocyclododecyl)butan-2-one. Determination of the absolute configuration of (-)-15-hexadecanolide
  作者：Stephan Stanchev、Manfred Hesse

  DOI：10.1002/hlca.19890720523

  日期：1989.8.9

  Reduction of the carbonyl group in the side chain of 4-(1-nitro-2-oxocyclododecyl)butan-2-one (3) with organoboron complexes are influenced by the chiral center, in 4-position with respect to the carbonyl C-atom, to which the NO2 group is attached, a rare type for an asymmetric reduction. Independent of the (R)- or (S)-configuration of the Alpine-Hydride, (+)-3 is reduced only to the (15S)-nitrolactone

  用有机硼配合物还原4-（1-硝基-2-氧代环十二烷基）丁烷-2-酮（3）的侧链中的羰基受羰基C-在4-位的手性中心的影响带有NO 2基团的原子，一种不对称还原的稀有类型。（的独立- [R ）-或（小号）中的构型高山-氢化物，（+） - 3被减小仅给（15小号）-nitrolactone（+） - 5和，随后的转化后，向（+） -（- S）-15-十六醇化物（（+）- 1），是天然存在的（-）-的对映体1。
• STANCHEV, STEPHAN;HESSE, MANFRED, HELV. CHIM. ACTA., 72,(1989) N, C. 1052-1060
  作者：STANCHEV, STEPHAN、HESSE, MANFRED

  DOI：——

  日期：——
• KOSTOVA, K.;HESSE, M., HELV. CHIM. ACTA, 1983, 66, N 3, 741-743
  作者：KOSTOVA, K.、HESSE, M.

  DOI：——

  日期：——
• Synthesen makrocyclischer Lactone durch Ringerweiterung Herstellung von (±)-Phoracantholid I, (±)-Dihydrorecifeiolid und (±)-15-Hexadecanolid
  作者：Kalina Kostava、Manfred Hesse

  DOI：10.1002/hlca.19840670708

  日期：1984.11.7

  Syntheses of Macrocyclic Lactones by Ring Enlargement Reaction Reaction. Preparation of (±)-Phoracantholide I, (±)-Dihydrorecifeiolide and (±)-15-Hexadecanolide

  通过环扩大反应反应合成大环内酯。制备（±）-邻苯三甲酚I，（±）-二氢瑞吉奥奈德和（±）-15-十六烷内酯
• Design, Synthesis, and Fungicidal Activity of Macrolactones and Macrolactams with a Sulfonamide Side Chain
  作者：Wei-Juan Zhu、Peng Wu、Xiao-Mei Liang、Yan-Hong Dong、Jian-Jun Zhang、Hui-Zu Yuan、Shu-Hua Qi、Xiang-Qing Meng、Jin-Ping Wu、Fu-Heng Chen、Dao-Quan Wang

  DOI：10.1021/jf800796z

  日期：2008.8.1

  Four series of novel macrolactones and macrolactams-12-alkylsulfonamido-1,15-pentadecanlactones (5), 12-alkylsulfonamido-15-methyl-1,15-pentadecanlactones (6), 12-alkylsulfonamido-1,15-pentadecanlactams (7), and N-(alkylsulfonamidoethyl)-l, 1 2-dodecanlactams (8)-were designed and synthesized from readily available 2-nitrocyclododecanone or cyclodoclecanone. Their structures were confirmed by 1H NIVIR, IR, and elemental analysis. The bioassay showed that these compounds displayed fair to excellent fungicidal activity against Rhizoctonia solani KOhn and have a gradual increase of fungicidal activity in the order of 6, 7, 8, and 5. Among them, compounds 5a, 5b, and 5c displayed excellent fungicidal activity against R. solani comparable with the commercial fungicide carbendazim. Above results illustrated that the rule on the relationship between the activity and hydrogen-bonding, namely the macrocyclic compounds with a hydrogen-bonding acceptor and a hydrogen-bonding donor on the ring and having a three methylenes distance between two polarizable groups have the best fungicidal activity against R. solani, has a general suitability to the macrocyclic compounds, and pesticide molecules may combine with a target enzyme by hydrogen-bonding. The facts, which compound 6 has a much lower fungicidal activity against R. solani than compound 5 but their diff erence in chemical structure is only that there is a methyl group on the C15 for compound 6 and none but hydrogen atom on the C15 for compound 5, indicated that a methyl group plays an inhibitory role to the fungicidal activity. It suggests that the existence of a methyl group with a great volume between two polarizable groups would interfere in the interaction of pesticide molecules and the target enzyme.