2,2-二甲基戊-3,4-二烯醛 | 4058-51-9

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 中文名称: 2,2-二甲基戊-3,4-二烯醛
• 中文别名: 4-(3,4-二甲基苯胺基)-4-羰基丁-2-烯酸
• 英文名称: 2,2-dimethyl-3,4-pentadienal
• 英文别名: 2,2-dimethylpenta-3,4-dienal
• CAS: 4058-51-9
• 化学式: C₇H₁₀O
• 分子量: 110.156
• InChiKey: QAMJLJHOJKMLEU-UHFFFAOYSA-N

物化性质

• 熔点：
  91-98 °C
• 沸点：
  131 °C
• 密度：
  0.814±0.06 g/cm3(Predicted)
• 保留指数：
  1573

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2912190090

反应信息

• 作为反应物：
  描述：

  2,2-二甲基戊-3,4-二烯醛 在 2-双环己基膦-2',6'-二甲氧基联苯 、 (S)-联萘(3,5-二甲苯基)膦 、 palladium diacetate 、 palladium on activated charcoal 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 4-二甲氨基吡啶 、 potassium phosphate 、 三氟甲磺酸三甲基硅酯 、 氢气 、 N,N'-二环己基碳二亚胺 作用下， 以 乙醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 107.0h， 生成
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Silaboration of Allenes

  摘要：

  An enantioselective silaboration of allenes was achieved using an achiral silylborane in the presence of a palladium catalyst bearing a chiral monodentate phosphine ligand. (R)-2-Bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivities in the addition of (diphenylmethylsilyl)pinacolborane to the internal C=C bond of terminal allenes at 0 degrees C, giving the corresponding beta-borylallylsilanes in high yields with high enantiomeric excesses. The enantioselectivity depended on the bulkiness of substituents of allenes: the enantiomeric excesses were found to be 91-93% ee (R = tert- and sec-alkyl), 88-90% ee (R = aryl), and 80-82% ee (R = prim-alkyl and Me) at 0 degrees C. Perfect chirality transfer was observed in the intramolecular cyclization reactions of the functionalized allylsilanes, affording highly enantioenriched cyclic alkenylboranes, which underwent Suzuki-Miyaura coupling with aryl halides.

  DOI：

  10.1021/ja063934h
• 作为产物：
  描述：

  [NMe2(2-propynyl)(CH=C(CH3)2)][OTS] 在 [hexakis[N,N'-(naphthalene-1,5-diyl)bis(3-carbamoylbenzene-1,2-diolato)]tetragallate](III) (12-) 、 重水 、 水 作用下， 生成 2,2-二甲基戊-3,4-二烯醛
  参考文献：
  名称：

  Aza Cope Rearrangement of Propargyl Enammonium Cations Catalyzed By a Self-Assembled “Nanozyme”

  摘要：

  The tetrahedral assembly [Ga4L6](12-) [L = N,N-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) encapsulates a variety of cations, including propargyl enammonium cations capable of undergoing the aza Cope rearrangement. For propargyl enammonium substrates that are encapsulated in the [Ga4L6](12-) assembly, rate accelerations by factors of up to 184 compared with the background reaction rate were observed. After rearrangement, the product iminium ion is released into solution and hydrolyzed, allowing for catalytic turnover. The activation parameters for the catalyzed and uncatalyzed reaction were determined, revealing that a decrease in the entropy of activation is responsible for the observed rate enhancements. The catalyzed reaction exhibits saturation kinetics: the rate data obeyed the Michaelis-Menten model of enzyme kinetics, and competitive inhibition using a nonreactive guest was demonstrated.

  DOI：

  10.1021/ja8013055

文献信息

• Novel Multicomponent Domino Approach to 2,5-Bifunctionalized Five-Membered Cyclic Nitrones
  作者：Milan Potáček、Marian Buchlovič、Stanislav Man

  DOI：10.1055/s-0031-1289726

  日期：2012.3

  Multicomponent reactions of 2,2-dimethylpenta-3,4-di­enal oxime with aldehydes and primary alcohols were studied and the optimum conditions for preparing a new family of 2,5-substituted five-membered cyclic nitrones were identified. This reaction offers direct access to the target structures in a single synthetic step. The scope and limitations of the reaction were evaluated, and all products were

  研究了2,2-二甲基戊-3,4-二肟 与醛和伯醇的多组分反应，并确定了制备新的2,5-取代的五元环硝酮家族的最佳条件。该反应可在单个合成步骤中直接进入目标结构。评价了反应的范围和局限性，并对所有产物进行了分离和充分表征。 丙二烯-醇-醛-多米诺反应-多组分反应-硝酮
• Microwave-Assisted Palladium(0)-Catalyzed Alkylative Cyclization of Allenyl Aldehydes Leading to 3-Substituted 3-Cycloalken-1-ols
  作者：Hirokazu Tsukamoto、Tomotaka Matsumoto、Yoshinori Kondo

  DOI：10.1021/ja076080p

  日期：2008.1.1

  3-cyclohexenols and -cyclopentenol based on Pd0-catalyzed alkylative, arylative, alkenylative, alkynylative, and borative cyclization reaction of allene−carbonyl compounds. Microwave irradiation increases not only the reaction rate but also the product yield by suppressing formation of hydroarylation byproducts observed in the same catalytic system. Cyclization of optically active 1,3-disubstituted allene aldehyde

  我们开发了一种基于 PdO 催化的丙二烯-羰基化合物的烷基化、芳基化、烯基化、炔基化和硼酸化环化反应的 3-取代 3-环己烯醇和 -环戊烯醇的有效合成方法。微波辐射通过抑制在同一催化体系中观察到的加氢芳基化副产物的形成，不仅提高了反应速率，而且提高了产物产率。旋光性 1,3-二取代丙二烯醛的环化表明该反应不是通过碳钯化反应进行的，而是通过“反瓦克”型氧化加成反应进行的。
• Highly efficient [2 + 2] intramolecular cyclizations of allenynes under microwave irradiation: construction of fused bicyclic compounds
  作者：Chang Ho Oh、Arun Kumar Gupta、Dai In Park、Nakjoong Kim

  DOI：10.1039/b508306k

  日期：——

  A palladium [2 + 2] cycloaddition of 1,6- and 1,7-allenyne carboxylates and microwave-mediated [2 + 2] cycloaddition of various 1,n-allenynes were developed and, particularly, the microwave irradiated [2 + 2] cycloaddition of allenynes can provide a simple, general and eco-friendly synthetic method to fused bicyclo[m,2,0]alkadienes.

  1,6-和1,7-炔烃羧酸的钯[2 + 2]环加成反应以及各种1，n-炔烃的微波介导的[2 + 2]环加成反应，特别是微波照射的[2 + 2炔烃的环加成反应可提供一种简单，通用且环保的合成方法，以稠合双环[m，2,0]链二烯。
• Allenyl(vinyl)methane Photochemistry. Photochemistry of Methyl 4,4-Dimethyl-2,5,6-heptatrienoate Derivatives
  作者：Takashi Tsuno、Kunio Sugiyama

  DOI：10.1246/bcsj.72.519

  日期：1999.3

  6-heptatrienoate (3a) competitively underwent E–Z geometric isomerization and intramolecular [2+2] cycloaddition, though prolonged irradiation led to [2+2] cycloadducts as main products. For methyl (E)-4,4,7-trimethyl-2,5,6-octatrienoate (3b), the intramolecular [2+2] cycloaddition occurred under both direct and sensitized irradiation and the E–Z geometric isomerization scarcely occurred. In these allenyl(vinyl)methanes

  [2-(1,2-丙二烯基)-取代亚烷基]丙二酸酯的直接和敏化光解主要产生分子内[2+2]环加合物。另一方面，(E)-4,4-二甲基-2,5,6-庚三烯酸甲酯 (3a) 的直接辐照竞争性地经历了 E-Z 几何异构化和分子内 [2+2] 环加成，尽管长时间辐照导致以[2+2]环加合物为主要产物。对于 (E)-4,4,7-三甲基-2,5,6-辛三烯酸甲酯 (3b)，分子内 [2+2] 环加成在直接照射和敏化照射下均发生，并且几乎不发生 E-Z 几何异构化。在直接照射下的这些丙二烯基(乙烯基)甲烷中，1,2-丙二烯基取代的酯产生作为次要产物的1,2-丙二烯基环丙烷或(2-亚乙烯基环丙基)乙酸酯。当在甲苯中的硒化氢存在下照射 3b 时，形成环戊烯。环戊烯的形成表明双自由基中间体是环戊烷-1,3-二基。通过 MO...
• Allenyl(vinyl)methane Photochemistry. Photochemistry of 5-[2-(1,2-Propadienyl)-Substituted Alkylidene]-2,2-dimethyl-1,3-dioxane-4,6-diones
  作者：Takashi Tsuno、Kunio Sugiyama

  DOI：10.1246/bcsj.68.3175

  日期：1995.11

  The Photochemistry of 5-[2-(1,2-propadienyl)-substituted alkylidene]-2,2-dimethyl-1,3-dioxane-4,6-diones has been studied. These acylals formed an intramolecular charge-transfer (CT) complex between the 1,2-propadienyl and vinyl moieties in acetonitrile and in hexane, the direct photolyses of which gave (1-alkenylidene)cyclopropanes as the main products, and the intramolecular [2+2] cycloadducts, 3-alkylidene-2′

  已经研究了 5-[2-(1,2-propadienyl)-取代的亚烷基]-2,2-二甲基-1,3-二恶烷-4,6-二酮的光化学。这些酰基在乙腈和己烷中的 1,2-丙二烯基和乙烯基部分之间形成分子内电荷转移 (CT) 复合物，其直接光解得到（1-亚烯基）环丙烷作为主要产物，以及分子内 [2 +2] 环加合物，3-亚烷基-2',2',5,5-四甲基螺[双环[2.1.0]戊烷-2,5'-[1,3]二恶烷]-4',6'-二酮作为次要产品。(1-亚烯基)环丙烷是由烯醇中间体通过双自由基的优选1,5-氢转移产生的，双自由基是通过分子内CT激发态形成的。另一方面，丙酮敏化的光解主要提供分子内 [2+2] 环加合物。