2,2'-(ethane-1,1-diyl)bis(3-hydroxy-5,5-dimethylcyclohex-2-en-1-one) | 7560-70-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2,2'-(ethane-1,1-diyl)bis(3-hydroxy-5,5-dimethylcyclohex-2-en-1-one)
• 英文别名: 2,2'-(ethane-1,1-diyl)bis(3-hydroxy-5,5-dimethylcyclohex-2-enone)；1,1-Bis-<2-hydroxy-4,4-dimethyl-6-oxo-cyclohexenyl>-ethan；Ethane, 1,1-bis(4,4-dimethyl-2-hydroxy-6-oxocyclohexenyl)-；3-hydroxy-2-[1-(2-hydroxy-4,4-dimethyl-6-oxocyclohexen-1-yl)ethyl]-5,5-dimethylcyclohex-2-en-1-one
• CAS: 7560-70-5
• 化学式: C₁₈H₂₆O₄
• 分子量: 306.402
• InChiKey: XVKDUYAWDLUESP-UHFFFAOYSA-N

物化性质

• 熔点：
  132-134 °C(Solv: ethanol (64-17-5))
• 沸点：
  441.8±45.0 °C(Predicted)
• 密度：
  1.163±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,2'-(ethane-1,1-diyl)bis(3-hydroxy-5,5-dimethylcyclohex-2-en-1-one) 在 manganese(III) triacetate dihydrate 作用下， 以 溶剂黄146 为溶剂， 反应 0.17h， 以60%的产率得到3,4',4',6,6-pentamethyl-3,5,6,7-tetrahydro-4H-spiro[benzofuran-2,1'-cyclohexane]-2',4,6'-trione
  参考文献：
  名称：

  使用基于锰（III）的四羰基化合物氧化选择性合成螺和双螺化合物

  摘要：

  在各种条件下研究了作为四羰基化合物的亚甲基双（环己烷二酮）和亚甲基双（哌啶二酮）的Mn（III）基氧化，根据溶剂选择性生产螺二氢呋喃和二螺环丙烷。讨论了螺二氢呋喃和双螺环丙烷的形成机理。此外，一种新型生物碱3,4,6,7,8,10-六氢-1 H-吡喃并[3,2- c：5,6- c' ]二吡啶-1,9的简单合成证明了（2 H）-二酮。

  DOI：

  10.1016/j.tet.2020.131165
• 作为产物：
  描述：

  5,5-二甲基-1,3-环己二酮 在 Candida parapsilosis ATCC 7330 whole cells 作用下， 以 乙醇 、 水 为溶剂， 以40%的产率得到2,2'-(ethane-1,1-diyl)bis(3-hydroxy-5,5-dimethylcyclohex-2-en-1-one)
  参考文献：
  名称：

  Regio- and enantioselective reduction of diketones: preparation of enantiomerically pure hydroxy ketones catalysed by Candida parapsilosis ATCC 7330

  摘要：

  Enantiomerically enriched hydroxy ketones were prepared by the reduction of the corresponding diketones with excellent enantiomeric excess (98%) and in good yields (up to 75%) using whole cells of Candida parapsilosis ATCC 7330. Cyclic diketones, such as 1,2-cyclohexanedione and 1,4-cyclohexanedione, resulted in hydroxy ketones as products. Cyclohexane-1,3-dione and 5,5-dimethylcyclohexane1,3-dione gave dimerised products, such as 2,2'-(ethane-1,1-diy1)bis(3-hydroxycyclohex-2-enone) and 2,2'-(ethane-1,1-diy1)bis(3-hydroxy-5,5-dimethylcyclohex-2-enone) with acetaldehyde generated in situ from whole cells of Candida parapsilosis ATCC 7330, which is reported here for the first time. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2015.09.001

文献信息

• Vinyl esters as effective acetaldehyde surrogates in [4 + 1] cycloaddition based multicomponent cascade
  作者：Manoj Kumar、Sourav Bagchi、Anuj Sharma

  DOI：10.1039/c5ra10073a

  日期：——

  A new multicomponent cascade has been designed by utilizing vinyl esters as effective acetaldehyde surrogate. While most of the cyclic α-ketoenols underwent a facile three component conversion to annulated furans, phenols such as naphthol and sesamol got simply acylated under the same reaction conditions. This microwave assisted method provides clean access to a wide range of functionalised furans

  通过利用乙烯基酯作为有效的乙醛替代物，设计了一种新的多组分级联反应。尽管大多数环状α-酮烯醇都容易地由三组分转化为环状呋喃，但在相同的反应条件下，酚（如萘酚和芝麻酚）却被简单地酰化了。这种微波辅助方法可在短时间内清洁范围广泛的功能化呋喃。
• Organocatalytic Sequential One-Pot Double Cascade Asymmetric Synthesis of Wieland−Miescher Ketone Analogues from a Knoevenagel/Hydrogenation/Robinson Annulation Sequence:  Scope and Applications of Organocatalytic Biomimetic Reductions
  作者：Dhevalapally B. Ramachary、Mamillapalli Kishor

  DOI：10.1021/jo070277i

  日期：2007.7.1

  practical and novel organocatalytic chemo- and enantioselective process for the cascade synthesis of highly substituted 2-alkyl-cyclohexane-1,3-diones and Wieland−Miescher (W−M) ketone analogs is presented via reductive alkylation as a key step. First time, we developed the one-step alkylation of dimedone and 1,3-cyclohexanedione with aldehydes and Hantzsch ester through an organocatalytic reductive alkylation

  通过还原烷基化，提出了一种实用且新颖的有机催化化学和对映选择性工艺，用于级联合成高度取代的2-烷基-环己烷-1,3-二酮和Wieland-Miescher（WM）酮类似物，这是关键步骤。首次，我们通过有机催化还原烷基化策略开发了二醛和1,3-环己二酮与醛和Hantzsch酯的一步烷基化。l的直接组合CH酸（二甲酮和1,3-环己烷二酮），醛，汉茨sch酯和甲基乙烯基酮的脯氨酸催化的级联Knoevenagel /加氢和级联的Robinson环氧化反应提供了高官能度的W-M酮类似物，并具有良好的收率。优异的对映选择性。许多还原性烷基化产物直接显示在药物化学中。
• Cyclic Diacylcarbene Generated from Iodonium Ylides and Diazodiketones
  作者：Yosio Hayasi、Taiiti Okada、Mituyosi Kawanisi

  DOI：10.1246/bcsj.43.2506

  日期：1970.8

  iodosobenzene in the presence of acetic anhydride. Thermal and Cu-catalyzed decomposition of iodonium ylides can be differentiated and both are explained in terms of diacylcarbene intermediate with different multiplicity. For the sake of comparison diazodimedone and related compounds are also decomposed by Cu-catalysis as well as by photochemical reaction. Carbene is also found to be a highly probable

  碘鎓叶立德的制备方法 Ph–\overset⊕I–\overset\ominusC(COR)(COR') 通过活性亚甲基化合物 H2C(COR)(COR') 与碘苯在醋酸酐。碘鎓叶立德的热和铜催化分解可以区分，两者都可以用具有不同多样性的二酰基卡宾中间体来解释。为了比较，重氮二甲酮和相关化合物也可通过铜催化和光化学反应分解。还发现卡宾是一种很有可能的中间体。在这些研究中，卡宾的自旋多重性是在产物分布的基础上讨论的。值得注意的是，在乙醇中存在均相 Cu 催化剂的情况下，重氮二甲酮会产生 O-H 键的插入产物，2-乙氧基-3-羟基-5，5-二甲基-2-环己烯酮（XVII），而碘鎓叶立德不产生这种化合物。XVII的形成通过假设酮卡宾-Cu-螯合物来解释。
• Generation and Reactivity of Electron-Rich Carbenes on the Surface of Catalytic Gold Nanoparticles
  作者：Judit Oliver-Meseguer、Mercedes Boronat、Alejandro Vidal-Moya、Patricia Concepción、Miguel Ángel Rivero-Crespo、Antonio Leyva-Pérez、Avelino Corma

  DOI：10.1021/jacs.7b13696

  日期：2018.3.7

  receiving additional electron density from a metal. Here, it is shown that Au nanoparticles (NPs) generate an electron-rich carbene on surface after transferring electron density to the carbonyl group of an in situ activated diazoacetate, as assessed by Fourier transformed infrared (FT-IR) spectroscopy, magic angle spinning nuclear magnetic resonance (MAS NMR), and Raman spectroscopy. Density functional

  通过从金属接收额外的电子密度，可以调节并最终逆转卡宾的反应性。在这里，通过傅立叶变换红外 (FT-IR) 光谱法、魔角旋转法评估，金纳米粒子 (NPs) 在将电子密度转移到原位活化的重氮乙酸酯的羰基后，在表面产生富电子卡宾核磁共振（MAS NMR）和拉曼光谱。密度泛函理论 (DFT) 计算支持观察到的实验值，并揭示了至少三个不同的 Au 原子在卡宾稳定过程中的参与。表面稳定的卡宾对亲核试剂显示出非凡的稳定性，并与亲电试剂反应生成新产品。
• A synthetic entry into fused pyran derivatives through carbon transfer reactions of 1,3-oxazinanes and oxazolidines with carbon nucleophiles
  作者：Kamaljit Singh、Jasbir Singh、Harjit Singh

  DOI：10.1016/0040-4020(96)00879-4

  日期：1996.11

  of various 2 substituted 1,3-oxazinanes 3 and 1,3-oxazolidines 4 with cyclic carbon nucleophiles viz. 5,5-dimethyl-1,3-cyclohexanedione and 1,3-cyclohexanedione furnish xanthene derivatives, whereas a Knoevenagel reaction proceeds with acyclic nucleophiles. In case of 4b and 4c, a unique synthesis of functionalised α-tetralones has emerged. Reactions of mixtures of cyclic and acyclic carbon nucleophiles

  各种2个取代的1,3-恶嗪并3和1,3-恶唑烷4与环状碳亲核试剂的酸催化缩合。5,5-二甲基-1,3-环己二酮和1,3-环己二酮提供了x吨衍生物，而Knoevenagel反应则与无环亲核试剂一起进行。在4b和4c的情况下，出现了功能化的α-四氢萘酮的独特合成。环状和无环碳亲核试剂与3的混合物的反应提供了一些官能化的且部分还原的苯并吡喃衍生物。