(5Z)-3,4-二甲基-5-戊亚基-2(5H)-呋喃酮 | 774-64-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 中文名称: (5Z)-3,4-二甲基-5-戊亚基-2(5H)-呋喃酮
• 中文别名: 博伏内酯2,3-二甲基-4-羟基-2,4-壬二烯酸内酯
• 英文名称: (Z)-3,4-dimethyl-5-pentylidenefuran-2(5H)-one
• 英文别名: cis-bovolide；bovolide；5-Pentyliden-3,4-dimethyl-2,5-dihydro-furan-2-on；(5Z)-3,4-dimethyl-5-pentylidenefuran-2-one
• CAS: 774-64-1
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: MTQPZHNZYWAXEH-YFHOEESVSA-N

物化性质

• 沸点：
  253.08°C (rough estimate)
• 密度：
  0.9976 (rough estimate)
• LogP：
  3.11
• 物理描述：
  Clear and colourless liquid; Spicy-herbal to mint-like aroma
• 溶解度：
  Soluble in non-polar solvents; insoluble in water
• 折光率：
  1.560-1.575

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

制备方法与用途

类别：有毒物品

可燃性危险特性：

• 热分解排出辛辣刺激烟雾

储运特性：

• 库房需通风、低温且干燥

灭火剂：

• 水、泡沫、沙土、二氧化碳、干粉

反应信息

• 作为产物：
  描述：

  2-bromomethyl-but-2-enoic acid methyl ester 在 indium 、 palladium diacetate 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 12.0h， 生成 (5Z)-3,4-二甲基-5-戊亚基-2(5H)-呋喃酮
  参考文献：
  名称：

  从Morita–Baylis–Hillman加合物轻松合成γ-亚烷基丁烯化物

  摘要：

  通过Morita–Baylis–Hillman溴化物与醛的连续铟介导的Barbier型反应与醛，内酯化和双键异构化反应，开发了一种方便的γ-亚烷基丁烯内酯的合成方法。各种合成的γ-亚烷基丁烯内酯，包括bovolide及其衍生物，均以良好的总收率合成。

  DOI：

  10.1016/j.tetlet.2011.11.001

文献信息

• Synthesis of 5-(bromomethylene)furan-2(5H)-ones and 3-(bromomethylene)isobenzofuran-1(3H)-ones as inhibitors of microbial quorum sensing
  作者：Tore Benneche、Zainab Hussain、Anne Aamdal Scheie、Jessica Lönn-Stensrud

  DOI：10.1039/b803926g

  日期：——

  (E)- and (Z)-5-(Bromomethylene)furan-2(5H)-ones and (E)- and (Z)-3-(bromomethylene)isobenzofuran-1(3H)-ones have been prepared starting from commercially available maleic anhydrides and phthalic anhydrides, respectively. A debrominative decarboxylation or a bromodecarboxylation reaction is a key step in the synthesis. The furanones were investigated for their ability to interfere with microbial communication

  制备了（E）-和（Z）-5-（溴代亚甲基）呋喃-2（5 H）-一和（E）-和（Z）-3-（溴代亚甲基）异苯并呋喃-1（3H）-一。分别从市售的马来酸酐和邻苯二甲酸酐开始。脱溴脱羧或溴脱羧反应是合成中的关键步骤。研究了呋喃酮对表皮葡萄球菌干扰微生物交流和生物膜形成的能力。
• Carboxylate-Directed Tandem Functionalisations of α,β-Dihaloalkenoic Acids with 1-Alkynes: A Straightforward Access to (Z)-Configured, α,β-Substituted γ-Alkylidenebutenolides
  作者：Samuel Inack Ngi、Khalil Cherry、Virginie Héran、Laurent Commeiras、Jean-Luc Parrain、Alain Duchêne、Mohamed Abarbri、Jérôme Thibonnet

  DOI：10.1002/chem.201102570

  日期：2011.12.2

  and stereoselectively leads to rarely described (Z)‐3‐halo‐5‐ylidene‐5H‐furan‐2‐ones. These compounds are subsequently able to undergo classical Pd‐catalysed cross‐coupling reactions, providing 3‐substituted and 3,4‐disubstituted 5‐ylidene‐5H‐furan‐2‐ones (see scheme).

  容易和温和的铜（I）催化的易获得的（E）-2,3-二卤代丙酸衍生物的区域选择性和立体选择性内酯化导致很少描述的（Z）-3-卤代-5-亚烷基-5 H-呋喃- 2个 这些化合物随后能够进行经典的Pd催化的交叉偶联反应，提供3-取代的和3,4-二取代的5-亚烷基-5 H-呋喃-2-（参见方案）。
• Reactions of cobalt carbene complexes with alkynes. .eta.4-Vinylketene-complexed intermediates and a novel synthesis of bovolide
  作者：William D. Wulff、Scott R. Gilbertson、James P. Springer

  DOI：10.1021/ja00263a035

  日期：1986.2

  conclusively that, for Rh2(02CCH3)4(PPh3)2, v(RhRh) is a t 289.3 cm-I. Since the RhRh bond length in this complex is 2.4505 (2) A," longer than in the analogous AsPh3 (2.427 (1) A),'2 SbPh, (2.421 (4) A),'* and H20 (2.3855 (5) A)I6 complexes, the implication is that v(RhRh) in these complexes must all lie above 289.3 cm-I, as indeed is found to be the case for the AsPh3 and SbPh, derivatives (vide

  因此，共振拉曼和同位素工作的结合最终证明，对于 Rh2(02CCH3)4(PPh3)2，v(RhRh) 为 289.3 cm-I。由于该复合物中的 RhRh 键长为 2.4505 (2) A，比类似的 AsPh3 (2.427 (1) A)、'2 SbPh、(2.421 (4) A)、'* 和 H2O (2.3855 (5) ) A)I6 复合物，这意味着这些复合物中的 v(RhRh) 必须都高于 289.3 cm-I，正如发现 AsPh3 和 SbPh 衍生物的情况确实如此（见上文）。 v(RhRh) 被认为是由四个螯合乙酸酯基团（主要通过四个 OCO 弯曲坐标，它们仅以二阶耦合到 RhRh 拉伸坐标）带来的对 RhRh 恢复力的显着贡献而产生的。详细信息这些和相关的研究将在别处发表。
• A Copper(I)-Catalyzed Addition/Annulation Sequence for the Two-Component Synthesis of γ-Ylidenebutenolides
  作者：Sangwon Seo、Michael C. Willis

  DOI：10.1021/acs.orglett.7b02151

  日期：2017.9.1

  A highly efficient Cu(I)-catalyzed addition/annulation sequence has been developed for the synthesis of (Z)-ylidenebutenolides employing readily available alpha-ketoacids and alkynes as substrates. The reactions employ a simple commercially available Cu(I)-catalyst, display good substrate scope, and deliver products with high stereoselectivity. The synthetic utility of the method is demonstrated by the straightforward derivatization of the ylidenebutenolides into a diverse range of heterocycles, and also by the preparation of the natural product bovolide, and analogs thereof.
• Acylpalladation of Internal Alkynes and Palladium-Catalyzed Carbonylation of (Z)-.beta.-Iodoenones and Related Derivatives Producing .gamma.-Lactones and .gamma.-Lactams
  作者：Christophe Coperet、Takumichi Sugihara、Guangzhong Wu、Izumi Shimoyama、Ei-ichi Negishi

  DOI：10.1021/ja00117a011

  日期：1995.3

  The reaction of either an internal alkyne-organic halide mixture or (Z)-beta-iodoenones with CO in the presence of a Pd-phosphine catalyst, e.g., Cl2Pd(PPh(3))2, can give one of the three discrete types of compounds as the major products depending on the substrate structure and the reaction conditions. Those substrates which are convertible to (Z)-gamma-oxo-alpha,beta-unsaturated acylpalladium derivatives lacking delta-H atoms are converted to the corresponding 2-butenolides (13) in the presence of water, which serves as a H donor. Carbon monoxide most likely is the source of two electrons. Either in the absence of water (or any other suitable H source) or in the presence of some factors disfavoring the butenolide formation, the same reaction gives the corresponding dimeric product (16). Even in cases where there is an alpha-H atom in the alpha-substitutent, 1,4-elimination products (11), reported to be the major products in a related Pd-catalyzed reaction of terminal alkyne-aryl iodide mixtures with CO, were not detected. In sharp contrast, those substrates which can give rise to (Z)-gamma-oxo-alpha, beta-unsaturated acylpalladium derivatives containing delta-H atoms give, under comparable reaction conditions, enol lactones (12), i.e., (Z)-3-alkylidene-2-butenolides, contaminated with only very minor amounts of 22 even in cases where an excess (4 equiv) of water was present. The required (Z)-beta-iodoenones can be readily prepared in one pot via ZrCp(2)-promoted cyclization of alkynes with nitriles. The ready availability of the starting compounds and the high Z stereoselectivity make the overall sequence an attractive synthetic route to 12. The courses of the Pd-catalyzed carbonylation reactions of (Z)-beta-iodo-alpha,beta-unsaturated imines 23 closely parallel the reactions of enones and produce the corresponding lactams, i.e., 24 and 25.