2-allyloxy-3-hydroxybenzaldehyde | 108059-04-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-allyloxy-3-hydroxybenzaldehyde
• 英文别名: 3-hydroxy-2-prop-2-enoxybenzaldehyde
• CAS: 108059-04-7
• 化学式: C₁₀H₁₀O₃
• 分子量: 178.188
• InChiKey: ZBEKCPLSINCHPN-UHFFFAOYSA-N

物化性质

• 熔点：
  80-81 °C
• 沸点：
  315.5±27.0 °C(Predicted)
• 密度：
  1.175±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-allyloxy-3-hydroxybenzaldehyde 在 对甲苯磺酸 sodium sulfide 、 selenium(IV) oxide 、 potassium carbonate 、 溶剂黄146 作用下， 以 1,4-二氧六环 、 甲醇 、 甲苯 、 乙腈 为溶剂， 反应 61.0h， 生成 3,3'-bis(2-hydroxybenzaldehyde)
  参考文献：
  名称：

  Macrocyclic trinucleating ligands for the cocomplexation of two "soft" (Cu2+, Ni2+, or Zn2+) metal centers and one "hard" (Ba2+ or Cs+) metal center

  摘要：

  Macrocyclic heterotrinucleating ligands that have one compartment for complexation of alkaline or alkaline earth cations and two compartments for transition-metal cations have been synthesized. The Ba2+-templated (2 + 2) macrocyclization of the dialdehydes 3a and 3b with the diamine 8 yielded the barium complexes (9b, 9e) in high yield. The Cs+-templated (2 + 2) macrocyclization of the dialdehyde 3a and the diamine 8 gave the cesium complex 9c. The mononuclear complexes were converted into the heterotrinuclear complexes 10a-h by reaction with 2 equiv of copper, nickel, or zinc acetate. The barium complex 9b, the dicopper/barium complex 10a, and the dinickel/barium complex 10b have been analyzed by X-ray crystallography. In all three crystal structures the O10 cavity is folded around the barium cation. The copper-copper distance in the dicopper/barium complex 10a is 3.50 angstrom and the nickel-nickel distance in the dinickel/barium complex 10b is 3.42 angstrom. The electrochemistry of the copper-containing heterotrinuclear complexes 10a, 10d, and 10g and the nickel-containing heterotrinuclear complexes 10b, 10e, and 10h has been studied by polarography, cyclic voltammetry, and coulometry in DMSO. The dinickel/barium complex 10b was also studied by Kalousek polarography. The dicopper/metal complexes 10a, 10d, and 10g all show a copper-copper interaction, which is the strongest for the dicopper/barium complex 10a. Coulometry revealed that the complexes 10a, 10d, and 10g undergo a reduction with two electrons, and cyclic voltammetry showed that the reduction/oxidation processes of 10a, 10d, and 10g are chemically reversible. The reduction/oxidation processes of the nickel-containing heterotrinuclear complexes 10b, 10e, and 10h are complicated by adsorption phenomena. Frozen EPR spectra of 10a and 10g exhibit typical triplet spectra with a zero-field splitting of about 0.04 cm-1. This behavior is typical for Cu(II) dimers and confirms that both Cu(II) cations are also exchange coupled in solution. A Cu-Cu distance in solution of 3.6 angstrom agrees best with the spectra. Attempts to add exogenous bridging ligands like F- and imidazolate were unsuccessful.

  DOI：

  10.1021/jo00001a043
• 作为产物：
  描述：

  2,3-二羟基苯甲醛 、 3-溴丙烯 在 sodium hydride 作用下， 以 二甲基亚砜 为溶剂， 以50%的产率得到2-allyloxy-3-hydroxybenzaldehyde
  参考文献：
  名称：

  Electroorganic reactions. Part 55.† Quinodimethane chemistry. Part 3. Transition metal complexes as inter- and intra-molecular redox catalysts for the electrosynthesis of poly(p-xylylene) (PPX) polymers and oligomers‡

  摘要：

  金属配合物在聚对苯二甲基酚（PPXs）的电合成中作为氧化还原介质的作用得到了研究，目的是设计出既能作为介质又能作为金属含聚合物的起始材料的金属含前体。一些过渡金属配合物[Cr(III)、Ni(II)和Co(II)]是生产 quinodimethanes 及因此 PPXs 的有效氧化还原催化剂。在使用基于邻氨基苯酸和水杨醛配体的介质进行实验后取得了令人鼓舞的结果，设计并成功合成了一种宏环化合物，该合成采用了汇聚方法，其中包含了 1,4-双(氯甲基芳烃)作为 quinodimethane 的前体和 Ni(II) salen 单元作为分子内氧化还原催化剂。该宏环成功通过阴极还原得到了一种与 Ni(II) 结合的 PPX 聚合物。提供了分子内氧化还原催化（同调介导）作用的证据。

  DOI：

  10.1039/b103274g

文献信息

• 5-lipoxygenase inhibitory thiazoles
  申请人：ICI Pharma

  公开号：US05089513A1

  公开（公告）日：1992-02-18

  The invention concerns a thiazole of the formula I, ##STR1## wherein Ar.sup.1 is optionally substituted aryl of up to 10 carbon atoms; A is a direct link to X, or is (1-6C)alkylene, (3-6C)alkenylene, (3-6C)alkynylene or cyclo(3-6C)alkylene; X is oxy, thio, sulphinyl, sulphonyl or imino; Ar.sup.2 is optionally substituted phenylene, or a 6-membered heterocyclene moiety containing up to three nitrogen atoms; R.sup.1 is hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl or substituted (1-4C)alkyl; R.sup.2 is hydrogen, (1-6C)alkyl, (3-6C)alkenyl, (3-6C)alkynyl, substituted (1-4C)alkyl or (2-6C)alkanoyl; Q is optionally substituted thiazolyl; or a pharmaceutically-acceptable salt thereof. The invention also concerns processes for the manufacture of a thiazole of the formula I, or a pharmaceutically-acceptable salt thereof, and pharmaceutical compositions containing said thiazole.

  该发明涉及一种式I的噻唑化合物，其中Ar.sup.1是最多含有10个碳原子的可选择取代的芳基；A是直接连接到X，或者是(1-6C)烷基，(3-6C)烯基，(3-6C)炔基或环(3-6C)烷基；X是氧，硫，亚硫基，磺酰基或亚胺基；Ar.sup.2是可选择取代的苯基，或者含有最多三个氮原子的6元杂环基；R.sup.1是氢，(1-6C)烷基，(2-6C)烯基，(2-6C)炔基或取代的(1-4C)烷基；R.sup.2是氢，(1-6C)烷基，(3-6C)烯基，(3-6C)炔基，取代的(1-4C)烷基或(2-6C)烷酰基；Q是可选择取代的噻唑基；或其药学上可接受的盐。该发明还涉及制备式I的噻唑化合物或其药学上可接受的盐的方法，以及含有该噻唑化合物的药物组合物。
• Functionalized UO2 Salenes: Neutral Receptors for Anions
  作者：Dmitry M. Rudkevich、Willem Verboom、Zbigniew Brzozka、Marcin J. Palys、Walter P. R. V. Stauthamer、Gerrit J. van Hummel、Sybille M. Franken、Sybolt Harkema、Johan F. J. Engbersen、David N. Reinhoudt

  DOI：10.1021/ja00089a023

  日期：1994.5

  unique combination of an immobilized Lewis acidic binding site (UO[sub 2][sup 2+]) and additional amide C(O)NH groups, which can form a favorable H-bond with a coordinated anion guest, has been developed. The unique combination of a Lewis acidic UO[sub 2] center and amide C(O)NH groups in one receptor leads to highly specific H[sub 2]PO[sub 4[sup [minus]] anion recognition. The anion complexation has been

  一类新型的阴离子中性受体，包含固定的路易斯酸性结合位点 (UO[sub 2][sup 2+]) 和额外的酰胺 C(O)NH 基团的独特组合，可形成有利的 H 键与一个协调的阴离子客体，已经开发。路易斯酸性 UO[sub 2] 中心和酰胺 C(O)NH 基团在一个受体中的独特组合导致高度特异性的 H[sub 2]PO[sub 4[sup [minus]] 阴离子识别。阴离子络合已通过 X 射线分析、电导测定法、循环伏安法、[sup 1] H 和 [sup 31] P NMR 光谱以及 FAB 质谱法得到证实。在三个预先组织的配体的情况下，强（K[sub ass] > 10[sup 5] M[minus]1] in MeCN-DMSO，99:1）和 H[sub 2]PO[sub 4]NO[sub 2][sup [minus]] 分别获得了一个受体。[开引号] 裸 [闭引号] UO[sub 2]
• Functionalized binaphthyl salophen crown ethers as models for the enzyme urease
  作者：Arjen M. Reichwein、Willem Verboom、David N. Reinhoudt

  DOI：10.1002/recl.19931121106

  日期：——

  Functionalized binaphthyl salophen crown ethers 2 and 3 containing a Lewis-acidic uranyl cation were prepared by the Ba2+-templated cyclization of dialdehydes 15 and 22, for which two convenient synthetic routes were developed, with diamines 23 and 24. Intramolecular complexation of the amide groups in metallomacrocycles 2 and 3 was demonstrated by the isolation of two different forms of 2a, which

  通过对二醛15和22进行Ba 2+模板化的环化反应，制备了含路易斯酸酸性铀酰阳离子的功能化联萘二酚冠醚2和3，并用二胺23和24开发了两种便捷的合成途径。金属大环化合物2和3中酰胺基的分子内络合通过两种不同形式的2a的分离证明，通过1 H-NMR和IR光谱以及通过电化学测量，观察到它们相互转化。使用二胺24在环化过程中，导致单官能化的金属大环3a-d形成了两种不同的立体异构体，并且导致了双官能化的金属大环3e和3f的“偏侧性” 。分离了尿素与2c和2d的固体配合物，但在尿烷在二恶烷/水中的水解过程中，未观察到2a的催化活性。
• Binaphthyl metallomacrocycles for complexation of neutral molecules
  作者：Arjen M. Reichwein、Willem Verboom、David N. Reinhoudt

  DOI：10.1002/recl.19931120609

  日期：——

  Binaphthyl salophen crown ethers 1 and 2, containing an immobilized electrophilic uranyl cation, were synthesized by cyclization of dialdehyde 10 with 1,2-benzenediamine (14) or cis-1,2-cyclohexanediamine (15), respectively, in the presence of Ba2+ as a template ion and subsequent transmetallation with UO22+. Solid complexes of urea and 1 and 2 were isolated. Molecular-mechanics calculations show that

  通过在Ba的存在下分别用1,2-苯二胺（14）或顺式-1,2-环己二胺（15）对二醛10进行环化反应，合成了含有固定的亲电子性铀酰阳离子的双萘酚盐二酚冠醚1和2。2+作为模板离子，随后与UO 2 2+进行金属转移。分离出尿素与1和2的固体复合物。分子力学计算表明1和2的几何 适用于在金属大环的腔附近引入官能团。
• Novel chiral (salen)Mn(<scp>iii</scp>) complexes containing a calix[4]arene unit in 1,3-alternate conformation as catalysts for enantioselective epoxidation reactions of (Z)-aryl alkenes
  作者：Carmela Bonaccorso、Giovanna Brancatelli、Francesco P. Ballistreri、Silvano Geremia、Andrea Pappalardo、Gaetano A. Tomaselli、Rosa M. Toscano、Domenico Sciotto

  DOI：10.1039/c3dt52550c

  日期：——

  Two new chiral calix[4]arene-salen ligands 1a,b, based on calix[4]arene platforms in 1,3-alternate conformation, have been prepared by a new general synthetic pathway. Their Mn(III) complexes, 3a,b, have shown fairly good efficiency in the asymmetric epoxidation of styrene and substituted styrenes, whereas excellent catalytic activity and selectivity were observed with rigid bicyclic alkenes, namely

  通过新的一般合成途径，制备了基于1,3-交替构象的杯[4]亚芳基平台的两个新的手性杯[4]亚芳-salen配体1a，b。它们的Mn（III）配合物3a，b在苯乙烯和取代的苯乙烯的不对称环氧化中显示出相当好的效率，而在刚性双环烯烃（即1,2-二氢萘和取代的2）上观察到优异的催化活性和选择性。 ，2'-二甲基色烯。3a的较高催化性能可能归因于结构相似的UO 2络合物2a，b的分子建模，NMR光谱和X射线数据证明，具有更高的刚性和固有的手性结构。