1,4-双(3-氨基苯)丁二炔 | 31661-59-3

• 物质功能分类: 化学试剂 - 有机试剂 - 炔烃
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1,4-双(3-氨基苯)丁二炔
• 中文别名: 1,4-双(3-氨基苯基)丁二炔
• 英文名称: 3,3'-(buta-1,3-diyne-1,4-diyl)dibenzenamine
• 英文别名: 1,4-bis(m-aminophenyl)buta-1,3-diyne；1,4-bis(3-aminophenyl)buta-1,3-diyne；3,3'-(buta-1,3-diyne-1,4-diyl)dianiline；3-[4-(3-aminophenyl)buta-1,3-diynyl]aniline
• CAS: 31661-59-3
• 化学式: C₁₆H₁₂N₂
• 分子量: 232.285
• InChiKey: FMZHYPYMCCZVCA-UHFFFAOYSA-N

物化性质

• 熔点：
  124-125 °C
• 沸点：
  487.0±45.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)
• 稳定性/保质期：
  如果按照规格使用和储存，则不会分解，也未有已知危险反应。

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  52
• 氢给体数：
  2
• 氢受体数：
  2

安全信息

• 海关编码：
  2921590090
• 危险性防范说明：
  P261,P280,P301+P312,P302+P352,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  请将贮藏器密封，并存放在阴凉、干燥处。确保工作环境有良好的通风或排气设施。

反应信息

• 作为反应物：
  描述：

  1,4-双(3-氨基苯)丁二炔 在 sodium azide 、 硫酸 、 sodium nitrite 作用下， 生成 1,4-bis(3-azidophenyl)-1,3-butadiyne
  参考文献：
  名称：

  Magnetic interaction between the triplet centers in ethynylenebis(phenylnitrenes) and 1,3-butadiyne-1,4-diylbis(phenylnitrenes)

  摘要：

  The magnetic interaction of the two triplet phenylnitrene units linked together through an acetylene or a diacetylene linkage has been investigated by ESR spectroscopy. Two regioisomeric (meta,para' and meta,meta') diazides of 1,2-diphenylacetylene 12a and 1,4-diphenyl- 1,3-butadiyne 13a were prepared and photolyzed in a 2-methyltetrahydrofuran glass at 10 K to give the corresponding dinitrenes 12n and 13n. The m,p'-dinitrenes of 12n and 13n showed intense quintet signals which obeyed a Curie law in the temperature range 12-85 K. The m,m'-dinitrenes of 12n and 13n showed signals due to the thermally populated quintet states, the intensities of which reached a maximum at 50 and 28 K for 12n and 13n, respectively. It is concluded that the two remote phenylnitrene units in 12n and 13n interact sufficiently strongly through bonds to form quintet states that are concluded to be the ground state in the meta,para' isomers as predicted by theory. In the meta,meta' isomers, the quintet states are thermally populated from ground singlet states, the energy gaps between the two states (ca. 200 and 100 cal/mol for -C = C- and -C = C-C = C-, respectively) being dependent reasonably upon the distance between the two moieties. The results serve as good guiding principles for designing high-spin conjugated polymers with pendant radical centers.

  DOI：

  10.1021/ja00015a005
• 作为产物：
  描述：

  3-硝基苯乙炔 在 吡啶 、 copper diacetate 、 铁粉 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 4.08h， 生成 1,4-双(3-氨基苯)丁二炔
  参考文献：
  名称：

  Magnetic interaction between the triplet centers in ethynylenebis(phenylnitrenes) and 1,3-butadiyne-1,4-diylbis(phenylnitrenes)

  摘要：

  The magnetic interaction of the two triplet phenylnitrene units linked together through an acetylene or a diacetylene linkage has been investigated by ESR spectroscopy. Two regioisomeric (meta,para' and meta,meta') diazides of 1,2-diphenylacetylene 12a and 1,4-diphenyl- 1,3-butadiyne 13a were prepared and photolyzed in a 2-methyltetrahydrofuran glass at 10 K to give the corresponding dinitrenes 12n and 13n. The m,p'-dinitrenes of 12n and 13n showed intense quintet signals which obeyed a Curie law in the temperature range 12-85 K. The m,m'-dinitrenes of 12n and 13n showed signals due to the thermally populated quintet states, the intensities of which reached a maximum at 50 and 28 K for 12n and 13n, respectively. It is concluded that the two remote phenylnitrene units in 12n and 13n interact sufficiently strongly through bonds to form quintet states that are concluded to be the ground state in the meta,para' isomers as predicted by theory. In the meta,meta' isomers, the quintet states are thermally populated from ground singlet states, the energy gaps between the two states (ca. 200 and 100 cal/mol for -C = C- and -C = C-C = C-, respectively) being dependent reasonably upon the distance between the two moieties. The results serve as good guiding principles for designing high-spin conjugated polymers with pendant radical centers.

  DOI：

  10.1021/ja00015a005

文献信息

• Synthesis and structural characterization of a monomeric di-copper-substituted silicotungstate [γ-H2SiW10O36Cu2(μ-1,1-N3)2]4− and the catalysis of oxidative homocoupling of alkynes
  作者：Kazuya Yamaguchi、Keigo Kamata、Syuhei Yamaguchi、Miyuki Kotani、Noritaka Mizuno

  DOI：10.1016/j.jcat.2008.06.004

  日期：2008.8

  acetonitrile, benzonitrile, and 1,2-dichloroethane, showed that complex 1 was present as a monomer of the di-copper-substituted γ-Keggin silicotungstate. Complex 1 could act as an effective homogeneous catalyst for the oxidative homocoupling of various types of alkynes, including aromatic, aliphatic, and heteroatom-containing ones. The reaction possibly proceeds as follows: First, the ligand exchange

  具有双-μ - 1,1-叠氮基配体的双铜取代的γ - Keggin硅钨酸盐TBA 4 [ γ- H 2 SiW 10 O 36 Cu 2（μ -1,1-N 3）2 ]（1，TBA在水性介质中合成＝（四TBA ＝四-正丁基铵）。1的阴离子部分的晶体结构是基-基末端叠氮桥联双铜取代的γ - Keggin硅钨酸盐的单体。的NMR和CSI-MS谱1在乙腈，苄腈和1,2-二氯乙烷等有机溶剂中的分析表明，配合物1作为双铜取代的γ - Keggin硅钨酸盐的单体存在。配合物1可以作为有效的均相催化剂，用于各种类型的炔烃（包括芳族，脂族和含杂原子的炔烃）的氧化均偶联。反应可能如下进行：首先，配体交换在1中的叠氮基之间进行。 和炔基通过二铜（II）-炔基中间体与还原的铜（I）物种形成相应的二炔，然后还原的物种被分子氧再氧化，氧化的物种与炔反应生成炔基中间的。
• Scope and reaction mechanism of an aerobic oxidative alkyne homocoupling catalyzed by a di-copper-substituted silicotungstate
  作者：Noritaka Mizuno、Keigo Kamata、Yoshinao Nakagawa、Takamichi Oishi、Kazuya Yamaguchi

  DOI：10.1016/j.cattod.2010.02.073

  日期：2010.11

  TBA = tetra-n-butylammonium) could act as an efficient reusable homogeneous catalyst for the aerobic oxidative alkyne homocoupling. Various kinds of structurally diverse terminal alkynes including aromatic, heteroaromatic, aliphatic, double bond-containing, silylacetylene, propargylic alcohol, and propargylic amine derivatives could selectively be converted into the corresponding diynes in the presence of I.

  二-铜-取代的γ-Keggin型硅钨TBA 4 [γ-H 2硅钨酸10 ö 36的Cu 2（μ-1,1-N 3）2 ]（我，TBA =四Ñ -butylammonium）可以充当作为有效的可重复使用的好氧氧化炔烃均相催化剂。在I的存在下，包括芳族，杂芳族，脂族，含双键，甲硅烷基乙炔，炔丙基醇和炔丙基胺衍生物在内的各种结构多样的末端炔烃可以选择性地转化为相应的二炔。I的催化活性它比单铜取代的硅钨酸盐，单体铜络合物和简单的铜盐要高得多，表明I中的双铜核在目前的炔均偶联中起着重要的作用。已经提出了反应机理，该反应机理涉及形成二铜（II）-炔基中间体，还原性消除二炔，以及被O 2再氧化还原的铜物质。
• An efficient approach to homocoupling of terminal alkynes: Solvent-free synthesis of 1,3-diynes using catalyticCu(ii) and base
  作者：Dong Wang、Jihui Li、Na Li、Tingting Gao、Sihua Hou、Baohua Chen

  DOI：10.1039/b917448f

  日期：——

  We report an environmentally friendly, efficient method for transforming terminal acetylenes into 1,3-diynes based on catalytic amounts of a Cu(II) salt and base under solvent-free conditions. The developed process conforms to the principles of ‘green’ chemistry and addresses the shortage of such methods for the synthesis of 1,3-diynes. The reaction is quite general and results in good yields. Interestingly

  我们报告了一种环保，高效的方法，可根据以下方法将末端乙炔转化为1,3-二炔 催化 金额 的Cu（II）盐和无溶剂条件下的碱。所开发的方法符合“绿色”化学原理，并解决了此类合成1,3-二炔的方法的不足。该反应是相当普遍的，并导致良好的产率。有趣的是，该系统还允许通过两个不同末端炔的交叉偶联来合成不对称的1,3-二炔。最后，催化剂 也可以回收。
• Leaf-like CuO nanosheets on rGO as an efficient heterogeneous catalyst for C-C homocoupling of terminal alkynes
  作者：Bin Wang、Lingfeng Gao、Gengxiu Zheng

  DOI：10.1016/j.catcom.2020.106260

  日期：2021.2

  CuO nanosheets/rGO were confirmed by XRD, SEM-EDS, TEM, HR-TEM, and XPS techniques. The CuO nanosheets/rGO was successfully applied as a high-performance heterogeneous catalyst in the homocoupling of 12 terminal alkynes, and the isolated yield of each product was more than 80%, except for propargyl alcohol. This catalyst could be reused five times with little activity loss. Thus, it is beneficial for

  在这项工作中，通过方便的水热法合成了在rGO上经济且定义明确的叶状CuO纳米片（CuO纳米片/ rGO）。通过XRD，SEM-EDS，TEM，HR-TEM和XPS技术确定了CuO纳米片/ rGO的形貌和化学组成。CuO纳米片/ rGO成功地用作高性能多相催化剂，用于12个末端炔的均相偶联，除炔丙醇外，每种产物的分离产率均超过80％。该催化剂可以重复使用五次而几乎没有活性损失。因此，对于有机合成化学的绿色和可持续发展是有益的。
• Silica-supported metal acetylacetonate catalysts with a robust and flexible linker constructed by using 2-butoxy-3,4-dihydropyrans as dual anchoring reagents and ligand donors
  作者：Bingbing Lai、Zhipeng Huang、Zhifang Jia、Rongxian Bai、Yanlong Gu

  DOI：10.1039/c5cy01012h

  日期：——

  2-Butoxy-3,4-dihydropyrans were used, for the first time, as dual anchoring reagents and ligand donors to prepare the immobilize homogeneous metal acetylacetonate catalysts.

  2-丁氧基-3,4-二氢吡喃首次被用作双锚定试剂和配体供体，制备固定化均相金属乙酰丙酮酸酯催化剂。

表征谱图