methyl 3-(bromomethyl)but-3-enoate | 911130-93-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 3-(bromomethyl)but-3-enoate
• 英文别名: Methyl 3-bromomethylbut-3-enoate
• CAS: 911130-93-3
• 化学式: C₆H₉BrO₂
• 分子量: 193.04
• InChiKey: BOTARJFFORNWNZ-UHFFFAOYSA-N

物化性质

• 沸点：
  207.7±28.0 °C(Predicted)
• 密度：
  1.387±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 3-(bromomethyl)but-3-enoate 在 sodium carbonate 、 氯化铵 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 4.0h， 生成 (6S)-6-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methyl-5,6-dihydro-2H-pyran-2-one
  参考文献：
  名称：

  Synthesis of (2S)-4-Methyl- and (2S)-4-Methyl-6-oxo-3,6-dihydro-2H-pyran-2-carbaldehydes as Precursors to C22–C27 Fragments of Fijianolides and Their Synthetic Analogs

  摘要：

  New schemes of synthesis of (2S)-4-methyl- and (2S)-4-methyl-6-oxo-3,6-dihydro-2H-pyran-2-carbaldehydes have been developed with the goal of obtaining C-22-C-27 fragments of fijianolides and their synthetic analogs on the basis of transformations of cyclopropanol intermediates. The C-22-C-27 block of fijianolides A and B has been synthesized.

  DOI：

  10.1134/s1070428018090130
• 作为产物：
  描述：

  methyl 2-(1'-mesyloxycyclopropyl)acetate 在 magnesium bromide 作用下， 以 乙醚 、 氯仿 为溶剂， 反应 8.0h， 以70%的产率得到methyl 3-(bromomethyl)but-3-enoate
  参考文献：
  名称：

  Synthesis of methyl 3-bromomethylbut-3-enoate and its reactions with aldehydes and tributylchlorostannane in the presence of zinc

  摘要：

  Methyl 3-bromomethylbut-3-enoate smoothly reacted with prenal, beta-ionylideneacetaldehyde, benzyloxyacetaldehyde, and tributylchlorostannane in the presence of zinc and aqueous ammonium chloride in tetrahydrofuran to give the corresponding delta-hydroxy-beta-methylidenecarboxylic acid esters. In the absence of ammonium chloride, satisfactory yields of the products were obtained only in the reactions with prenal and benzyloxyacetaldehyde; these reactions involved lactonization of intermediate delta-hydroxy-beta-methylidenecarboxylic acid esters, and the double carbon-carbon bond migrated to the conjugated position with the lactone carbonyl group. The condensation of beta-ionylideneacetaldehyde with methyl 3-bromomethylbut-3-enoate was successfully used to obtain isotretinoin. Initial methyl 3-bromomethylbut-3-enoate was synthesized in a good yield from readily accessible ethyl 3,3-diethoxypropionate via cyclopropanation with ethylmagnesium bromide in the presence of titanium tetra(isopropoxide), oxidation of the acetal moiety to ester, and cleavage of the cyclopropane ring in intermediate methyl (1-methylsulfonyloxycyclopropyl)acetate.

  DOI：

  10.1134/s1070428008090029

文献信息

• Allylation of (R)-2,3-O-Cyclohexylideneglyceraldehyde with Methyl 3-(Bromomethyl)but-3-enoate. Methyl 3-{(2S)-2-[(2R)-1,4-Dioxaspiro[4.5]dec-2-yl]-2-hydroxyethyl}but-3-enoate as a Convenient Universal Building Block for the Synthesis of Key Fragments of Bioactive Compounds
  作者：I. V. Mineeva

  DOI：10.1134/s1070428019080098

  日期：2019.8

  reaction with such 2-substituted functionalized allyl bromide as methyl 3-(bromomethyl)but-3-enoate under the action of various metals or metal salts. The best diastereoselectivity was observed with Zn and DMF or THF plus saturated aqueous ammonium chloride as solvents. The feasibility of the resulting homoallyl alcohol, specifically methyl 3-(2S)-2-[(2R)-1,4-dioxaspiro[4.5]dec-2-yl]-2-hydroxyethyl}but-3-enoate

  （- [R）-2,3- ö -Cyclohexylideneglyceraldehyde参与与Barbier的烯丙基化反应，例如2-取代的各种金属或金属盐的作用下官能化的烯丙基溴甲基-3-（溴甲基）丁-3-烯酸甲酯。用Zn和DMF或THF加饱和氯化铵水溶液作为溶剂，观察到最佳非对映选择性。生成的高烯丙基醇，特别是3-（2 S）-2-[（2 R）-1,4-dioxaspiro [4.5] dec-2-yl] -2-羟乙基} but-3- enoate甲酯的可行性，作为大环抗癌剂（例如laulimalides）及其合成类似物的组成部分。
• Functionalized 2-Substituted Allyl Bromides in the Barbier Allylation of (R)-2,3-O-Isopropylideneglyceraldehyde. Synthesis of the C8–C17, C8–C18, and C5–C17 Building Blocks of Laulimalides and Their Synthetic Analogs
  作者：I. V. Mineyeva

  DOI：10.1134/s1070428019040195

  日期：2019.4

  Several new 2-substituted allyl bromides were synthesized through cyclopropanol intermediates and were then involved in the Barbier allylation of (R)-2,3-O-isopropylideneglyceraldehyde in the presence of zinc in a mixture of tetrahydrofuran and saturated aqueous ammonium chloride to obtain the corresponding homoallylic alcohols with high diastereoselectivity. The possibility of using the latter as

  通过环丙醇中间体合成了几种新的2-取代的烯丙基溴，然后在四氢呋喃和饱和氯化铵水溶液的混合物中，在锌的存在下，参与（R）-2,3- O-异亚丙基甘油醛的Barbier烯丙基化反应。具有高非对映选择性的相应的均烯丙基醇。证明了将后者用作大环抗肿瘤剂（月桂酰亚胺）及其合成类似物的基础。
• α,β-Unsaturated β-Methyl-δ-lactones in Nitrile Oxide Cycloaddition Reactions. Synthesis of Saturated Lactones and Lactams
  作者：I. V. Mineyeva

  DOI：10.1134/s1070428022060033

  日期：2022.6

  Abstract New isoxazoline derivatives have been synthesized in high yields by cycloaddition of acetonitrile oxide to α,β-unsaturated β-methyl-δ-lactones. These unsaturated lactones have been used to obtain β-methyl branched saturated lactones and lactams, as well as lactones with an inversed configuration of hydroxy group, following the divergent approach.

  摘要 通过将氧化乙腈环加成到 α,β-不饱和 β-甲基-δ-内酯上，以高收率合成了新的异恶唑啉衍生物。这些不饱和内酯已被用于获得β-甲基支链饱和内酯和内酰胺，以及具有反相羟基构型的内酯，遵循发散的方法。
• Allylation of Ketones with Methyl 3-(Bromomethyl)but-3-enoate. Synthesis of Bioactive Unsaturated Lactones Based on Benzo[f]coumarin and Its Derivatives
  作者：Yu. P. Lamekina、T. A. Kulahava、V. A. Shumski、I. V. Mineyeva

  DOI：10.1134/s1070428022060021

  日期：2022.6

  developed for the allylation of structurally diverse ketones with methyl 3-(bromomethyl)but-3-enoates, and the possibility of using the allylation products in the target-oriented synthesis of new heterocyclic compounds has been demonstrated. Modification of benzo[f]coumarin derivatives at the keto group via Barbier allylation with methyl 3-(bromomethyl)but-3-enoate has been performed for the first time with

  摘要 已经开发出有效的方法来用 3-(溴甲基)丁-3-烯酸甲酯对结构多样的酮进行烯丙基化，并且已经证明了在新杂环化合物的靶向合成中使用烯丙基化产物的可能性。首次使用 3-(溴甲基)丁-3-烯酸甲酯通过 Barbier 烯丙基化对酮基上的苯并[ f ]香豆素衍生物进行修饰，目标是随后形成内酯片段。合成的苯并[ f ]香豆素衍生物已通过光谱方法表征，并估计了它们穿透磷脂双层的能力。已发现这些化合物既不影响 C6 大鼠神经胶质瘤细胞的活力也不影响增殖。得到的苯并[ f]香豆素衍生物在基于过氧化氢和次氯酸钠的模型系统中表现出抗氧化特性。
• 2-Substituted Allyl Bromides as Electrophilic and Nucleophilic Building Blocks for 1,3-Dicarbonyl Compounds and Their Use in the Synthesis of Heterocycles
  作者：I. V. Mineyeva

  DOI：10.1134/s1070428022090032

  日期：2022.9

  Abstract An efficient procedure has been developed for the synthesis of new heterocyclic compounds from 2-substituted functionalized allyl bromides as precursors to electrophilic and nucleophilic building blocks for 1,3-dicarbonyl compounds.

  摘要 已经开发了一种有效的方法，用于从 2-取代官能化烯丙基溴作为 1,3-二羰基化合物的亲电和亲核结构单元的前体合成新的杂环化合物。