[4-(dimethylamino)phenyl]propargyl aldehyde | 85609-01-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [4-(dimethylamino)phenyl]propargyl aldehyde
• 英文别名: 3-[4-(N,N-dimethylamino)phenyl]prop-2-ynal；2-Propynal, 3-[4-(dimethylamino)phenyl]-；3-[4-(dimethylamino)phenyl]prop-2-ynal
• CAS: 85609-01-4
• 化学式: C₁₁H₁₁NO
• 分子量: 173.214
• InChiKey: GVLKAPCBSQMOHB-UHFFFAOYSA-N

物化性质

• 熔点：
  86-88 °C
• 沸点：
  315.6±25.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [4-(dimethylamino)phenyl]propargyl aldehyde 在 sodium selenide 、 sodium tetrahydroborate 、 正丁基锂 、 sodium ethanolate 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 2.0h， 生成 Δ-4H-2-(4-anilino)-6-(4-N,N-dimethylanilino)selenopyran-4-one
  参考文献：
  名称：

  In Vitro Photodynamic Properties of Chalcogenopyrylium Analogues of the Thiopyrylium Antitumor Agent AA1

  摘要：

  Several series of chalcogenopyrylium dyes were prepared with one or two 4-anilino substituents at the 2- and 6-positions and with phenyl, 4-N,N-dimethylanilino, or 4-(N-morphilino)phenyl substituents at 2- and/or 4-positions. The dye series are all related in structure to AA1, a thiopyrylium dye that targets mitochondria. The chalcogenopyrylium. nuclei included sulfur, selenium, and tellurium at the 1-position. Key intermediates in the dye synthesis were the corresponding Delta-4H-chalcogenopyran-4-ones. All of the dyes of this study were evaluated for dark and phototoxicity toward Colo-26 cells in vitro. There was no correlation of dark toxicity with either the reduction potential of the chalcogenopyrylium dye or the n-octanol/water partition coefficient, log P. Several of the dyes of this study (thiopyrylium dyes 1-S and 13-S, selenopyrylium dyes 1-Se, 2-Se, 3-Se, 4-Se, 13-Se, 14-Se, and 27-Se, and telluropyrylium dye 13-Te) showed added phototoxicity upon irradiation. Dyes with the highest therapeutic ratio as measured by dark toxicity/phototoxicity (15 J cm(-2) of 360-800-nm light) had values of log P of 1.0-1.2. Studies of cytochrome c oxidase activity in whole R3230AC cells suggested that dyes I-S and 3-Se, with values of log P of 2.2 and 1.7, respectively, were localized in the mitochondria. Cytocrome c oxidase activity in whole cells was inhibited by 1-S and 3-Se in the dark. Chalcogenopyrylium dyes 2-Se, 4-Se, 13-Te, and 14-Se inhibited whole-cell cytochrome c oxidase activity only following irradiation, which suggests that these dyes relocalized to mitochondria following irradiation.

  DOI：

  10.1021/jm020260m
• 作为产物：
  描述：

  3-(4-(N,N-dimethylamino)phenyl)prop-2-yn-1-ol 在 manganese(IV) oxide 作用下， 以 乙醚 为溶剂， 生成 [4-(dimethylamino)phenyl]propargyl aldehyde
  参考文献：
  名称：

  过炔基化的buta-1,2,3-三烯：积碳C = C键的旋转阻隔极低，在肽C-N键的阻隔范围内。

  摘要：

  通过相应的宝石-二溴代烯烃的二聚作用，合成了各种1,1,4,4-四氢炔基丁烯酮和1,4-二炔基丁二烯酮。（1）H和（13）C NMR光谱均表明，二和四烷基化丁二烯是顺式和反式异构体的混合物。可变温度NMR研究表明，顺式-反式容易异构化，因此可通过重力或高效液相色谱（HPLC）防止这些异构体分离。对于1,1,4,4-四炔基丁二烯，通过磁化转移测得的活化势垒deltaG（不等于）约为20 kcal mol（-1），处于绕肽键内部旋转的势垒范围内。与四炔基化的[3]枯草酮不同，1,4-二炔基丁烯酮更难异构化，在一种情况下，可以异构纯的形式获得。根据实验数据，对1,4-二炔基丁二烯的旋转势垒DeltaG（不等于）估计约为25 kcal mol（-1）。计算研究进一步支持了四个炔基取代基对这种顺反异构化的2-but-1，yne-1,4-二基单重双自由基过渡态的稳定作用的假设。

  DOI：

  10.1002/chem.200400218

文献信息

• N-Heterocyclic Carbene (NHC)-Catalyzed/Lewis Acid Mediated Conjugate Umpolung of Alkynyl Aldehydes for the Synthesis of Butenolides: A Formal [3+2] Annulation
  作者：Jing Qi、Xingang Xie、Runfeng Han、Donghui Ma、Juan Yang、Xuegong She

  DOI：10.1002/chem.201204386

  日期：2013.3.25

  Reverse to success! A new formal [3+2] annulation reaction combining alkynyl aldehydes and β,γ‐unsaturated α‐ketoesters has been disclosed by using a NHC‐catalyzed/Lewis acid mediated strategy. This cooperative catalysis strategy first allows the “allenolate” intermediate as a nucleophilic synthon at the β‐position to react with activated electrophilic reagents by an addition reaction as the key CC

  扭转成功！通过使用NHC催化/路易斯酸介导的策略，已公开了一种新的正式的[3 + 2]环化反应，该反应将炔醛与β，γ-不饱和α-酮酸酯结合在一起。这种协同催化策略首先允许“烯丙酸酯”中间体作为亲核合成子在β-位通过加成反应作为关键的CC键形成步骤与活化的亲电子试剂反应。
• Convenient Methods for the Preparation of<i>p</i>-Dialkylaminophenylacetylenes
  作者：Shuzo Akiyama、Shin’ichi Nakatsuji、Keiko Yoshida、Kenichiro Nakashima、Toshimitsu Hagiwara、Haruki Tsuruta、Toshio Yoshida

  DOI：10.1246/bcsj.56.361

  日期：1983.1

  Two convenient methods for the preparation of p-dialkylaminophenylacetylenes are reported: a) Dehydrobromination of the brominated compounds obtained easily from the dialkylamino substituted cinnamic acids in acetic acid instead of chloroform; b) dehydrochlorination of the 2-chlorostyrene derivative obtained from the reaction of p-dimethylaminobenzaldehyde with chloromethylenetriphenylphosphorane.

  报道了两种制备对二烷基氨基苯乙炔的简便方法： a) 将二烷基氨基取代的肉桂酸在乙酸中而不是氯仿中容易地获得的溴化化合物脱溴化氢；b) 由对二甲氨基苯甲醛与氯亚甲基三苯基正膦反应得到的 2-氯苯乙烯衍生物的脱氯化氢。
• Synthesis of 1,4-Diethynyl- and 1,1,4,4-Tetraethynylbutatrienes
  作者：Audrey Auffrant、Fran�ois Diederich、Corinne Boudon、Jean-Paul Gisselbrecht、Maurice Gross

  DOI：10.1002/hlca.200490277

  日期：2004.12

  In this paper, we report the synthesis and opto-electronic properties of differentially substituted 1,4-diethynyl- and 1,1,4,4-tetraethynylbuta-1,2,3-trienes. These novel chromophores greatly extend the series of building modules for oxidative coupling, which includes 1,2-diethynyl- and 1,1,2,2-tetraethynylethenes and 1,3-diethynylallenes (Fig. 1). A general synthesis of 1,1,4,4-tetraethynylbutatrienes

  在本文中，我们报告了差异取代的1,4-二乙炔基-和1,1,4,4-四乙炔基丁-1,2,3-三烯的合成和光电性能。这些新颖的生色团极大地扩展了用于氧化偶联的建筑模块系列，其中包括1,2-二乙炔基-和1,1,2,2-四乙炔基乙稀和1,3-二乙炔基丙二烯（图1）。1,1,4,4-四乙炔基丁二烯的一般合成可以耐受大量的周边取代基，其起始原料是戊二炔醇，它们被氧化成相应的二乙炔基酮，然后进行Corey-Fuchs二溴代烯烃化反应，以及过渡金属介导的二聚化作用（方案2和3）。包括炔丙醛的氧化，二溴代烯烃化和二聚化在内的类似方案产生的稳定性较差的1,4-二乙炔二丁基三烯（方案4）。迄今为止，制备具有四个末端电子供体取代的芳基的1,1,4,4-四乙炔基丁烯的尝试失败，这主要是由于二溴代烯烃化步骤的困难（方案6）。差异取代的1,1,4,4-四乙炔基丁烯酮的顺反异构化非常容易，旋转障碍在肽键异构化的范围内（ΔG
• N,N′-Dibutylbarbituric acid as an acceptor moiety in push–pull chromophores
  作者：Milan Klikar、Filip Bureš、Oldřich Pytela、Tomáš Mikysek、Zdeňka Padělková、Alberto Barsella、Kokou Dorkenoo、Sylvain Achelle

  DOI：10.1039/c3nj00683b

  日期：——

  Twelve novel D–π–A chromophores with the N,N′-dibutylbarbituric acid acceptor, the N,N-dimethylamino donor and a systematically extended π-linker were synthesized. The extent of intramolecular charge-transfer, structure–property relationships and nonlinear optical properties were further investigated by X-ray analysis, electrochemistry, UV/Vis absorption spectra, calculations and EFISH experiments.

  合成了具有N，N'-二丁基巴比妥酸受体、N，N-二甲基氨基供体和系统性延长的π连接体的十二种新型D-π-A型色团。通过X射线分析、电化学、紫外/可见吸收光谱、计算和EFISH实验进一步研究了分子内电荷转移程度、结构-性质关系和非线性光学性质。
• From Linear to T-Shaped Indan-1,3-dione Push-Pull Molecules: A Comparative Study
  作者：Parmeshwar Solanke、Aleš Růžička、Tomáš Mikysek、Oldřich Pytela、Filip Bureš、Milan Klikar

  DOI：10.1002/hlca.201800090

  日期：2018.8

  A series of indan‐1,3‐dione‐based linear, quadrupolar and T‐shaped push–pull chromophores have been designed and synthesized by the Knoevenagel condensation and Pd‐catalyzed Suzuki–Miyaura or Sonogashira cross‐coupling reactions. The number and position of the peripheral donor branches attached to the central withdrawing indan‐1,3‐dione moiety have been varied jointly with the type of π‐linker used

  通过Knoevenagel缩合和Pd催化的Suzuki-Miyaura或Sonogashira交叉偶联反应，设计和合成了一系列基于indan-1,3-dione的线性，四极和T形推挽生色团。连接到中心提取茚满-1,3-二酮部分的外围供体分支的数量和位置已随π的类型而变化用于调制基本光电特性的链接器。X射线分析证实了两种生色团的分子结构。通过差示扫描量热法，电化学，UV / Vis吸收光谱和DFT计算进一步研究了热和光电性质。在这些实验和理论数据的基础上，进一步评估了彻底的结构-性质关系，并讨论了特定结构修饰对生色团性质的影响。