5-(2-溴-乙酰基)-2-羟基-苯甲酸甲酯 | 36256-45-8

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 烃类卤化物
• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 5-(2-溴-乙酰基)-2-羟基-苯甲酸甲酯
• 中文别名: 3-溴丙醛二甲基乙缩醛；甲基-5-2(溴乙酰基)2-羟基苯甲酸酯；2-羟基-5-(2-溴乙酰基)苯甲酸甲酯
• 英文名称: methyl 5-(bromoacetyl)salicylate
• 英文别名: methyl 5-(2-bromoacetyl)-2-hydroxybenzoate；5-bromoacetyl-2-hydroxybenzoic acid methyl ester；3-carbomethoxy-4-hydroxy-α-bromoacetophenone
• CAS: 36256-45-8
• 化学式: C₁₀H₉BrO₄
• 分子量: 273.083
• InChiKey: YRPHNSODVHXAOP-UHFFFAOYSA-N

物化性质

• 熔点：
  91-92℃
• 沸点：
  390.2±32.0 °C(Predicted)
• 密度：
  1.601±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿（少许）、甲醇（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

安全信息

• 海关编码：
  2918990090
• 包装等级：
  III
• 危险类别：
  8
• 危险性防范说明：
  P501,P260,P234,P264,P280,P390,P303+P361+P353,P301+P330+P331,P363,P304+P340+P310,P305+P351+P338+P310,P406,P405
• 危险品运输编号：
  3261
• 危险性描述：
  H314,H290
• 储存条件：
  室温且干燥

反应信息

• 作为反应物：
  描述：

  5-(2-溴-乙酰基)-2-羟基-苯甲酸甲酯 在 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 palladium 10% on activated carbon 、 三乙胺 作用下， 以 甲醇 、 乙醚 、 乙腈 为溶剂， 反应 4.67h， 生成 沙美特罗
  参考文献：
  名称：

  基于水杨苷的β2-激动剂的结构异构体：合成和反应机制的洞察

  摘要：

  沙美特罗和沙丁胺醇是众所周知的β2-腺受体激动剂，广泛用于治疗炎症性呼吸道疾病，例如支气管哮喘和慢性阻塞性肺病。在这里，我们报道了沙美特罗和沙丁胺醇结构异构体的制备，它们可以从与相应的β2-激动剂相同的起始材料中获得，具体取决于所采用的合成方法。使用一维和各种二维核磁共振测量，我们确定所制备的异构体的结构含有β-芳基-β-氨基乙醇部分，与沙美特罗和沙丁胺醇中发现的α-芳基-β-氨基乙醇部分相反。我们通过实验和计算方法研究了 β-卤代醇和胺的反应，该反应负责形成 β-芳基-β-氨基醇。具有水杨酸甲酯部分的β-卤代醇的结构决定了反应的进程。溶剂在反应方向上起着相关但模糊的作用，而碱的强度以更明显的方式影响反应产率和异构体比例。使用计算方法，我们已经表明，最有可能导致意外异构体形成的反应中间体是相应的对醌甲基化物，其可以由于水杨酸甲酯部分中存在的苯酚而形成。成功制备沙丁胺醇和沙美特罗异构体后，我

  DOI：

  10.1039/d0ob02095h
• 作为产物：
  描述：

  阿司匹林 在 三氯化铝 、 1,4-dioxane dibromide 、 硫酸 作用下， 以 1,4-二氧六环 、 乙醚 、 硝基苯 为溶剂， 反应 27.0h， 生成 5-(2-溴-乙酰基)-2-羟基-苯甲酸甲酯
  参考文献：
  名称：

  Synthesis and structure-activity relationships among .alpha.-adrenergic receptor agonists of the phenylethanolamine type

  摘要：

  Nineteen arylethanolamine derivatives related to norepinephrine were prepared and tested for alpha-adrenergic stimulant activity. In one series the analogues possess a p-hydroxy function, while the meta position is substituted by methyl, ethyl, isopropyl, chlohexyl, fluoro, chloro, iodo, carboxy, carbomethoxy, and methylsulfamido groups. The other series is meta hydroxylated with the para position substituted by the same groups. The influence of these groups upon the alpha-adrenergic activity is discussed, and the compounds are compared to octopamine, normetanephrine, norepinephrine, and norphenylephrine. It has been found that the introduction of an isopropyl, cyclohexyl, and fluoro group in the meta position of octopamine improves its affinity by three, five, and six times, respectively, whereas when these groups are introduced in the para position of norphenylephrine their effects are always detrimental. The most active compound, alpha-(aminomethyl)(4-fluoro-3-hydroxyphenyl)methanol (44), has about one-hundredth the affinity and the same intrinsic activity as norepinephrine.

  DOI：

  10.1021/jm00181a008

文献信息

• Substituted pyrimidin-2-ones, the salts thereof, processes for their
  申请人：Glaxo Group Limited

  公开号：US04636509A1

  公开（公告）日：1987-01-13

  Compounds of the general formula: ##STR1## (wherein X represents a halogen atom or a trifluoromethyl group; R.sup.1 represents an optionally substituted C.sub.6-10 carbocyclic aromatic group; and R.sup.2 represents a hydrogen atom or a lower alkyl, C.sub.7-16 aralkyl or C.sub.6-10 aryl group or the group COR.sup.1a, in which R.sup.1a is as defined for R.sup.1, R.sup.1 and R.sup.1a being the same or different) and where an acidic or basic group is present, the salts thereof have been found to possess excellent metaphase arresting ability and are of use in combating abnormal cell proliferation. Thus a knowledge of the cell division cycles of the normal and abnormal cells enables a cytotoxic drug to be administered while the abnormal cells are in a phase susceptible to attack and while the normal cells are in a non-susceptible phase. The compounds of the invention are prepared by alkylation, deprotection of a protected keto group, oxidation or electrophilic halogenation. Pharmaceutical compositions containing the compounds of formula I, and where appropriate, the physiologically compatible salts thereof; and methods for the use of the compounds are described and claimed.

  通式为：##STR1##（其中X代表卤原子或三氟甲基基团；R.sup.1代表可选择取代的C.sub.6-10碳环芳基团；R.sup.2代表氢原子或较低的烷基、C.sub.7-16芳基烷基或C.sub.6-10芳基团或基团COR.sup.1a，其中R.sup.1a如R.sup.1所定义，R.sup.1和R.sup.1a相同或不同）并且存在酸性或碱性基团，已发现其盐具有出色的中期阻滞能力，并可用于对抗异常细胞增殖。因此，了解正常和异常细胞的细胞分裂周期使得可以在异常细胞处于易受攻击阶段而正常细胞处于不易受攻击阶段时给予细胞毒性药物。本发明的化合物通过烷基化、去保护受保护的酮基团、氧化或亲电卤代反应制备。描述和声明了含有通式I化合物的药物组合物，以及在适当情况下其生理相容盐；并描述和声明了使用这些化合物的方法。
• Surfactant-accelerated asymmetric transfer hydrogenation with recyclable water-soluble catalyst in aqueous media
  作者：Jiahong Li、Xuefeng Li、Yaping Ma、Jiashou Wu、Fei Wang、Jing Xiang、Jin Zhu、Qiwei Wang、Jingen Deng

  DOI：10.1039/c2ra22432a

  日期：——

  Water-soluble ligands (R,R)-2 were successfully prepared, in which the bis-meta-sulphonated ligand was definitely detected as the major product. The corresponding transition-metal complexes containing the ligands displayed excellent catalytic performance in asymmetric transfer hydrogenation (ATH) of aromatic ketones. Especially, the aromatic ketones with a bromine group in the α position could be smoothly

  水溶性配体（[R ，- [R ）- 2成功制备，其中，所述双元-磺化的配体肯定被检测为主要产物。含有配体的相应过渡金属络合物在芳族酮的不对称转移氢化（ATH）中表现出出色的催化性能。尤其是，在α位上具有溴基的芳族酮可以平稳地还原为预期的醇，同时保持溴基完整并具有出色的对映选择性（至多96％ee）。催化剂可以重复使用至少21次，而不会损害高转化率的对映选择性。此外，发现阳离子表面活性剂和适当的pH值对于维持高反应性是必要的。
• New 7-Methylguanine Derivatives Targeting the Influenza Polymerase PB2 Cap-Binding Domain
  作者：Stéphane Pautus、Peter Sehr、Joe Lewis、Antoine Fortuné、Andrea Wolkerstorfer、Oliver Szolar、Delphine Guilligay、Thomas Lunardi、Jean-Luc Décout、Stephen Cusack

  DOI：10.1021/jm401369y

  日期：2013.11.14

  directly inhibit viral replication. Docking studies using the structure of the PB2 cap-binding domain suggested that 7-alkylguanine derivatives substituted at position N-9 and N-2 could be good candidates. Four series of 7,9-di- and 2,7,9-trialkyl guanine derivatives were synthesized and evaluated by an AlphaScreen assay in competition with a biotinylated cap analogue. Three synthesized compounds display

  异三聚体流感病毒聚合酶在感染细胞的核内执行病毒RNA的复制和转录。通过“帽捕捉”进行转录需要宿主细胞前mRNA通过其5'帽与PB2亚基结合。因此，PB2帽结合位点可能是直接抑制病毒复制的新抗病毒药物的良好靶标。使用PB2帽结合结构域的结构的对接研究表明，在N -9和N -2位置取代的7-烷基鸟嘌呤衍生物可能是不错的选择。合成了四个系列的7,9-二-和2,7,9-三烷基鸟嘌呤衍生物，并通过AlphaScreen分析与生物素化帽类似物竞争进行了评估。三种合成的化合物具有IC 50的强大体外活性值低于10μM。与H5N1 PB2帽结合结构域复合的三种抑制剂的高分辨率X射线结构证实了结合模式，并为进一步的化合物优化提供了详细信息。
• <i>p</i>-Hydroxyphenacyl photoremovable protecting groups — Robust photochemistry despite substituent diversity
  作者：Richard S. Givens、Kenneth Stensrud、Peter G. Conrad、Abraham L. Yousef、Chamani Perera、Sanjeewa N. Senadheera、Dominik Heger、Jakob Wirz

  DOI：10.1139/v10-143

  日期：2011.2

  A broadly based investigation of the effects of a diverse array of substituents on the photochemical rearrangement of p-hydroxyphenacyl esters has demonstrated that common substituents such as F, MeO, CN, CO₂R, CONH₂, and CH₃have little effect on the rate and quantum efficiencies for the photo-Favorskii rearrangement and the release of the acid leaving group or on the lifetimes of the reactive triplet state. A decrease in the quantum yields across all substituents was observed for the release and rearrangement when the photolyses were carried out in buffered aqueous media at pHs that exceeded the ground-state pK_aof the chromophore where the conjugate base is the predominant form. Otherwise, substituents have only a very modest effect on the photoreaction of these robust chromophores.

  一项关于各种取代基对对羟基苯乙酯光化学重排影响的广泛研究表明，常见取代基（如 F、MeO、CN、CO2R、CONH2 和 CH3）对光-Favorskii 重排和酸离去基团释放的速率和量子效率影响很小，对反应三重态的寿命影响也很小。当光解在缓冲水介质中进行时，pH 值超过发色团的基态 pKao（其中共轭碱是主要形式），则释放和重排的量子产率在所有取代基中都会降低。否则，取代基对这些坚固发色团的光反应影响很小。
• A Multi-Functional Tool - Cyclopentadienyl Re and 99mTc Complex Synthesis on Highly Functionalised Arenes
  作者：Raphael Lengacher、Sandro Ott、Olivier Blacque、Henrik Braband、Roger Alberto

  DOI：10.1016/j.jorganchem.2022.122281

  日期：2022.3

  pyrene units were functionalized with a cyclopentadiene unit. The Re and 99mTc complexes of the latter two were synthesized and fully characterized. During crystallization of the ligands, [2+2] and [6+6] cycloadditions were observed for the cyclopentadiene modified coumarin. A light-induced mechanism, supported by DFT calculations, is proposed for these reactions. The fluorescent properties of the coumarin

  生物学相关的芳烃水杨酸乙酯和水杨酰胺以及荧光香豆素和芘单元用环戊二烯单元官能化。后两者的 Re 和99m Tc 配合物被合成并充分表征。在配体结晶过程中，观察到环戊二烯改性香豆素的 [2+2] 和 [6+6] 环加成反应。为这些反应提出了一种由 DFT 计算支持的光诱导机制。研究了香豆素和芘基环戊二烯及其相应的铼配合物的荧光性质。