2-(2-methylenecyclohexyl)acetic acid | 38970-47-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-(2-methylenecyclohexyl)acetic acid
• 英文别名: 2-(2-Methylidenecyclohexyl)acetic acid
• CAS: 38970-47-7
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: YVBBLODEJNIIOW-UHFFFAOYSA-N

物化性质

• 沸点：
  139 °C(Press: 11 Torr)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(2-methylenecyclohexyl)acetic acid 在 盐酸 、 草酸氯化物 作用下， 以 乙醚 、 苯 为溶剂， 反应 1.0h， 生成 1-Chloro-3-(2-methylene-cyclohexyl)-propan-2-one
  参考文献：
  名称：

  Synthesis and evaluation of cardiotonic activity of simple butenolides II

  摘要：

  Three 3-(2-hydroxy-2-methylcyclohexylmethyl)butenolides were synthesized and checked for inotropic activity. Very weak effects were observed for all of them.

  DOI：

  10.1016/0223-5234(93)90041-c
• 作为产物：
  描述：

  2,2-二甲基环己酮 在 盐酸 、 4-二甲氨基吡啶 、 sodium hydroxide 、 正丁基锂 、 diisobutylammonium hydride 、 四甲基乙二胺 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 10.35h， 生成 2-(2-methylenecyclohexyl)acetic acid
  参考文献：
  名称：

  .beta.-Hydroxy esters: (E)- versus (Z)-enolate geometry in dianionic Claisen rearrangements

  摘要：

  DOI：

  10.1021/jo00252a037

文献信息

• Synthesis of Erythrina and Related Alkaloids. XXVIII. Studies toward Total Synthesis of Non-aromatic Erythrina Alkaloids. (1). Synthesis and Isomerization of Unsaturated Bicyclic .DELTA.-Lactones.
  作者：Yoshisuke TSUDA、Akiko ISHIURA、Saho TAKAMURA、Shinzo HOSOI、Kimiaki ISOBE、Kunihiko MOHRI

  DOI：10.1248/cpb.39.2797

  日期：——

  As a model of the C/D ring system of erythroidines, bicyclic unsaturated δ-lactones were synthesized in a regio-selective manner, and their isomerization reaction in the presence of acid, base (DBU, 1, 8-diazabicyclo[5.4.0]undec-7-ene), and NaOH were studied. In the lactone form, the 6-ene (3) was the most unstable and isomerized to the 5-ene (1) then to the 1(6)-ene (2). The latter two lactones equilibrate to give ca. 3 : 2 mixture of 1 and 2 in the presence of DBU. On the contrary, in the opened form (NaOH), the lactone 1 was the most unstable and isomerized to 2 and 3. The 1(10)-ene (4) was inert under all of the conditions examined.

  作为红细胞素C/D环系统的模型，合成了环状不饱和δ-内酯，并研究了它们在酸、碱（DBU，1, 8-二氮双环[5.4.0]十一烯）和氢氧化钠存在下的异构化反应。在内酯形式中，6-烯（3）是最不稳定的，并异构化为5-烯（1），然后再转变为1(6)-烯（2）。后两种内酯在DBU的存在下达到了大约3:2的1和2的平衡。相反，在打开状态下（氢氧化钠），内酯1是最不稳定的，异构化为2和3。1(10)-烯（4）在所有检查的条件下都表现惰性。
• Oxyamination of Unactivated Alkenes with Electron-Rich Amines and Acids via a Catalytic Triiodide Intermediate
  作者：Fan Wu、Jeewani P. Ariyarathna、Nur-E Alom、Navdeep Kaur、Wei Li

  DOI：10.1021/acs.orglett.9b04432

  日期：2020.2.7

  aerobic catalytic oxidation process is described for the olefin oxyamination using acids and primary amines as the sources of O and N. Our mechanistic findings point to the formation of triiodide as a critical catalytic intermediate to account for the tolerance of electron-rich nucleophiles. This dual iodide and copper catalytic system is suitable for a formal [5+1] annulation process to access valuable

  描述了一种使用酸和伯胺作为O和N的源的烯烃氧化胺化的好氧催化氧化方法。我们的机理发现指出，三碘化物的形成是一种关键的催化中间体，说明了富电子亲核试剂的耐受性。这种双重碘化物和铜的催化体系适用于正式的[5 + 1]环化工艺，以获取有价值的内酰胺结构，并通过药物扎米芬星的合成得到突出显示。
• Oxidative rearrangement of 1,1-disubstituted alkenes to ketones
  作者：Qiang Feng、Qian Wang、Jieping Zhu

  DOI：10.1126/science.adg3182

  日期：2023.3.31

  to the ring expansion of highly strained methylene cyclobutane derivatives. Herein, we report a solution to this synthetic challenge by designing a Pd II /Pd IV catalytic cycle incorporating a 1,2-alkyl/Pd IV dyotropic rearrangement as a key step. This reaction, compatible with a broad range of functional groups, is applicable to both linear olefins and methylene cycloalkanes, including macrocycles.

  广泛用于将单取代烯烃转化为相应甲基酮的 Wacker 工艺被认为是通过 Pd二/钯0涉及β-氢化物消除步骤的催化循环。这种机制场景不适用于从 1,1-二取代烯烃合成酮。目前的方法基于半-Pd 的频哪醇重排二中间体仅限于高应变亚甲基环丁烷衍生物的环扩展。在此，我们报告了通过设计 Pd 来应对这一综合挑战的解决方案二/钯四、包含 1,2-烷基/Pd 的催化循环四、促变性重排作为关键步骤。该反应与广泛的官能团相容，适用于直链烯烃和亚甲基环烷烃，包括大环化合物。区域选择性有利于更多取代碳的迁移，并且还观察到 β-羧基的强烈定向作用。
• Palladium‐Based Dyotropic Rearrangement Enables A Triple Functionalization of <i>Gem</i>‐Disubstituted Alkenes: An Unusual Fluorolactonization Reaction
  作者：Qiang Feng、Chen‐Xu Liu、Qian Wang、Jieping Zhu

  DOI：10.1002/anie.202316393

  日期：2024.1.2

  4-methylenealkanoic acid derivatives with Selectfluor provides fluorolactones via a sequence of 5-exo-trig oxypalladation, Pd oxidation, regioselective ring-enlarging 1,2-alkyl/Pd(IV) dyotropic rearrangement and C−F bond-forming reductive elimination.

  Pd 催化的 4-亚甲基链烷酸衍生物与 Selectflu 的反应通过一系列 5-exo-trig oxypalladation、Pd 氧化、区域选择性扩环 1,2-烷基/Pd(IV) 向异性重排和 C−F 键生成氟内酯形成还原消除。
• DERIVATIVES OF HYPOCRELLIN WITH PERI-POSITION AND 2-POSITION SIMULTANEOUSLY SUBSTITUTED BY AMINO GROUPS
  申请人：Technical Institute of Physics and Chemistry of the Chinese Academy of Sciences

  公开号：EP3680230A1

  公开（公告）日：2020-07-15

  The present invention discloses a hypocrellin derivative substituted both in a peri-position and in a 2-position by an amino, and a preparation method and use thereof. A general structural formula of the derivative is as represented by formulas I-a to I-d: The hypocrellin derivative substituted both in a peri-position and in a 2-position by an amino prepared in the present invention has a maximum absorption wavelength of 600-650 nm and a molar extinction coefficient reaching about 20000-40000 M-1cm-1. Compared with unmodified hypocrellin or hypocrellin having only a 2-position modified, an absorption spectrum of the derivative is significantly red-shifted and the molar extinction coefficient is greatly improved, and the derivative can efficiently produce reactive oxygen species such as singlet oxygen in a photosensitive condition. In the same condition, the hypocrellin derivative substituted both in a peri-position and in a 2-position by an amino involved in the present invention, when used as a photosensitizer, has a stronger ability to photo-dynamically inactivate tumor cells than the first and second generation commercial photosensitizers.

  本发明公开了一种在周位和 2 位均被氨基取代的次黄嘌呤衍生物及其制备方法和用途。该衍生物的一般结构式如式 I-a 至 I-d 所示： 本发明制备的在周位和 2 位被氨基取代的次黄嘌呤衍生物的最大吸收波长为 600-650 nm，摩尔消光系数约为 20000-40000 M-1cm-1。与未修饰的次黄嘌呤或仅修饰了 2 位的次黄嘌呤相比，该衍生物的吸收光谱明显红移，摩尔消光系数大大提高，在光敏条件下能有效地产生活性氧，如单线态氧。在相同的条件下，本发明中被氨基取代了周位和 2 位的次黄嘌呤衍生物在用作光敏剂时，与第一代和第二代商业光敏剂相比，具有更强的光动力灭活肿瘤细胞的能力。