4-羟基-2,4-二甲基戊-1-烯-3-酮 | 15185-08-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 4-羟基-2,4-二甲基戊-1-烯-3-酮
• 英文名称: 4-hydroxy-2,4-dimethylpent-1-en-3-one
• 英文别名: 4-hydroxy-2,4-dimethyl-pent-1-en-3-one
• CAS: 15185-08-7
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: TXLFTINZKIKDIC-UHFFFAOYSA-N

物化性质

• 沸点：
  187.4±23.0 °C(Predicted)
• 密度：
  0.958±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  4-羟基-2,4-二甲基戊-1-烯-3-酮 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 2,4-二甲基-3-己酮
  参考文献：
  名称：

  Functional group hybrids. Reactivity of .alpha.'-nucleofuge .alpha.,.beta.-unsaturated ketones. 1. Reactions with organocopper reagents

  摘要：

  A series of alpha-nucleofuge alpha',beta'-unsaturated ketones encompassing a variety of structural types and nucleofuges was prepared. Treatment of these compounds with lithium dimethylcuprate or methylcopper leads primarily to either reductive cleavage of the alpha-nucleofuge or conjugate addition. Good alpha-nucleofuges favored the reduction pathway while poorer nucleofuges favored conjugate addition.

  DOI：

  10.1021/jo00024a014
• 作为产物：
  描述：

  2,4-二甲基-2,3-戊二烯 在 盐酸 作用下， 以 乙醚 、 氯仿 为溶剂， 生成 4-羟基-2,4-二甲基戊-1-烯-3-酮
  参考文献：
  名称：

  Reaction of nitrosobenzene with tetramethylallene

  摘要：

  DOI：

  10.1021/jo01271a052

文献信息

• Photooxygenation of tetramethylallene competing (2+2) cycloaddition and ene-reactions with singlet oxygen
  作者：Klaus Gollnick、Albert Schnatterer

  DOI：10.1016/s0040-4039(01)80844-3

  日期：1985.1

  TPP-sensitized photooxygenation of tetramethylallene (4) in carbon tetrachloride yields acetone (5), 2,4-dimethyl-4-hydroxy-1-penten-3-one (8) and 2,4-dimethyl-1,4-pentadien-3-one (9) in a ratio of 35:20:45, besides minor amounts of resinous products and carbon dioxide. Isomerization of 4 to 2,4-dimethyl-1,3-pentadiene (6) does not occur under the reaction conditions. DABCO quenches the photooxygenation

  在四氯化碳中TPP致敏的四甲基丙烯烯（4）的光氧合反应可生成丙酮（5），2,4-二甲基-4-羟基-1-戊烯-3-酮（8）和2,4-二甲基-1,4-戊二烯-3-一（9）的比例为35:20:45，除了少量的树脂产品和二氧化碳。在反应条件下不会发生4至2,4-二甲基-1,3-戊二烯（6）的异构化。DABCO可以终止光氧合，而2,4,6-三叔丁基苯酚（10）可以提高耗氧率，但5：8：9的比例不变。这些结果表明4被单线态氧氧化。提出了一种机理，根据该机理，通过（2 + 2）环加成反应生成丙酮，而通过4和单线态氧之间的烯反应形成8和9。
• Asymmetric Assembly of All-Carbon Tertiary/Quaternary Nonadjacent Stereocenters through Organocatalytic Conjugate Addition of α-Cyanoacetates to a Methacrylate Equivalent
  作者：Igor Iriarte、Silvia Vera、Eider Badiola、Antonia Mielgo、Mikel Oiarbide、Jesús M. García、José M. Odriozola、Claudio Palomo

  DOI：10.1002/chem.201603082

  日期：2016.9.12

  An efficient, highly diastereo‐ and enantioselective assembly of acyclic carbonyl fragments possessing nonadjacent all‐carbon tertiary/quaternary stereoarrays is reported based on a Brønsted base catalyzed Michael addition/α‐protonation sequence involving α‐cyanoacetates and 2,4‐dimethyl‐4‐hydroxypenten‐3‐one as novel methacrylate equivalent.

  基于布朗斯台德碱催化的迈克尔加成/α-质子化序列，涉及α-氰基乙酸酯和2,4-二甲基-4-基羟基戊烯-3-一作为新的甲基丙烯酸酯等同物。
• Regioselective Carbon–Carbon Bond Cleavage in the Oxidation of Cyclopropenylcarbinols
  作者：Ahmad Basheer、Masaaki Mishima、Ilan Marek

  DOI：10.1021/ol201581c

  日期：2011.8.5

  The strained double bond of cyclopropenylcarbinols undergoes a facile oxidation reaction to lead to unsaturated carbonyl derivatives. The distribution of the formed products depends on the relative stability of carbon-centered radical species, and the Sharpless kinetic resolution leads to enantiomerically pure Baylis–Hillman enal adducts.

  环丙烯基甲醇的应变双键容易发生氧化反应，从而生成不饱和羰基衍生物。成型产物的分布取决于以碳为中心的自由基种类的相对稳定性，而Sharpless动力学拆分导致对映体纯的Baylis-Hillman烯醛加合物。
• Peracid oxidation of tetramethylallene
  作者：Jack K. Crandall、Warren H. Machleder

  DOI：10.1021/ja01028a021

  日期：1968.12
• 1,4-Dioxaspiro[2.2]pentanes. Synthesis, spectroscopic properties, and reactions with nucleophiles
  作者：Jack K. Crandall、David J. Batal、David P. Sebesta、Feng Lin

  DOI：10.1021/jo00003a044

  日期：1991.2

  A number of simple allenes have been converted cleanly to the corresponding 1,4-dioxaspiro[2.2]pentanes in good yields by oxidation with dimethyldioxirane. Mono- and trisubstituted allenes give the anti diastereomers with good stereoselectivity, whereas 1,3-disubstituted allenes show only a slight preference for the anti,anti isomers, unless steric effects are extreme. Stereochemical assignments are based on steric considerations and a consistent set of NMR characteristics that permit structural attributions. The addition of a range of nucleophiles (water, alcohols, amines, thiophenol, acetate, chloride, and fluoride) to these intermediates proceeded smoothly under buffered conditions to give highly functionalized products of general type 5. These reactions were shown to take place with the appropriate selectivities for S(N)2 substitutions in instances where these features were observable, namely, regioselective attack at the less-substituted epoxide carbon and inversion of configuration at the site of substitution. Under acidic conditions dioxaspiropentanes gave mixtures of other types of products, which appear to arise from carbocationic processes.