methyl 2,2-dimethyl-2H-1-benzopyran-6-carboxylate | 34818-57-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: methyl 2,2-dimethyl-2H-1-benzopyran-6-carboxylate
• 英文别名: Methyl 2,2-dimethyl-2H-<1>benzopyran-6-carboxylate；2,2-dimethyl-2H-1-benzopyran-6-carboxylic acid, methyl ester；methyl 2,2-dimethyl-2H-chromene-6-carboxylate；2,2-dimethyl-6-carboxychromene methyl ester；6-methoxycarbonyl-2,2-dimethyl-2H-chromene；Methyl 2,2-dimethylchromene-6-carboxylate
• CAS: 34818-57-0
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: BVQOOKUOYKXECX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2,2-dimethyl-2H-1-benzopyran-6-carboxylate 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 4.5h， 以87%的产率得到2,2-二甲基色烯-6-羧酸
  参考文献：
  名称：

  Synthesis and Structure−Phytotoxicity Relationships of Acetylenic Phenols and Chromene Metabolites, and Their Analogues, from the Grapevine Pathogen Eutypa lata

  摘要：

  Eutypa lata, the fungus responsible for dying-arm disease in grapevines, produces a number of structurally related secondary metabolites, of which eutypine (1) has been implicated as the principal phytotoxin. However, analysis of an E. lata strain from California known to be pathogenic to grapevines showed that eutypine was not present, suggesting that other metabolites could be phytotoxic. Investigation of the relative phytotoxicities of individual metabolites has been limited by insufficient material and lack of a reliable bioassay. Metabolites of particular interest and their precursors were therefore synthesized, and a rapid, quantitative bioassay via topical application of individual compounds to disks of grape leaves and measurement of chlorophyll loss was developed to provide a relative measure of tissue damage. The recently reported metabolite eulatachromene (2) was found to have phytotoxicity greater than that of eutypine (1). The cyclization product, 5-formyl-2-methylvinyl[1]benzofuran (3), also showed significant activity, whereas the reduction product, eutypinol (4), was inactive, as was the quinol, siccayne (5). These results indicate that before strains of Eutypa are incriminated as pathogenic they must be analyzed for the presence or absence of specific constituents for which the phytotoxicity has been unequivocally established.

  DOI：

  10.1021/np020415t
• 作为产物：
  描述：

  对羟基苯甲酸甲酯 在 Lindlar's catalyst copper(l) iodide 、 polystyrene-based selenenyl bromide resin 、 氢气 、 potassium carbonate 、 potassium iodide 作用下， 以 正己烷 、 二氯甲烷 、 N,N-二甲基苯胺 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.66h， 生成 methyl 2,2-dimethyl-2H-1-benzopyran-6-carboxylate
  参考文献：
  名称：

  基于特权结构的类天然产物组合库。1. 苯并吡喃的一般原理及固相合成

  摘要：

  在此，我们报告了一种基于特权结构原理设计和构建天然和天然产物类库的新策略，该术语最初用于描述能够与各种不相关的分子靶标相互作用的结构基序。讨论了天然产物中此类特权结构的鉴定，随后选择 2,2-二甲基苯并吡喃部分作为通过该策略构建类天然产物库的初始模板。最初，采用独特的环加载策略开发了苯并吡喃基序的新型固相合成，该策略依赖于使用新的聚苯乙烯基溴化硒树脂。一旦确定了这些苯并吡喃的加载、加工和裂解，

  DOI：

  10.1021/ja002033k

文献信息

• Microwave-assisted palladium mediated decarbonylation reaction: synthesis of eulatachromene
  作者：Akanksha、Debabrata Maiti

  DOI：10.1039/c2gc35622h

  日期：——

  Microwave-assisted decarbonylation reactions were investigated using a palladium catalyst. A large number of aldehydes can be decarbonylated efficiently with lower catalyst loadings and under shorter reaction times compared to conventional heating. A successful decarbonylation led to the synthesis of natural product eulatachromene in three steps starting from easily available materials.

  通过使用钯催化剂，对微波辅助脱羰反应进行了研究。与传统加热方式相比，许多醛类可以在较低的催化剂用量和较短的反应时间内高效地进行脱羰反应。成功的脱羰反应使得从易得原料出发，通过三个步骤合成了天然产物eulatachromene。
• Thieme Chemistry Journal Awardees - Where Are They Now? Microwave-Assisted Rhodium-Catalyzed Decarbonylation of Functionalized 3-Formyl-2<i>H</i>-chromenes: A Sequence for Functionalized Chromenes like Deoxycordiachromene
  作者：Stefan Bräse、Manuel Bröhmer、Nicole Volz

  DOI：10.1055/s-0029-1217179

  日期：——

  3-Formyl-2H-chromenes which are readily accessible through an oxa-Michael reaction of salicylaldehydes and α,β-unsaturated aldehydes undergo a smooth decarbonylation reaction upon treatment with rhodium catalysts. With our method, a great variety of functionalized chromenes is accessible in a two-step sequence from salicylaldehydes.

  3-甲酰基-2H-色烯可通过水合物迈克尔反应，由水杨醛和α，β-不饱和醛轻易制得。这些化合物在铑催化剂作用下会顺利进行脱羰反应。运用我们的方法，可通过水杨醛的两步反应，大量制备功能化色烯。
• A Concise Approach to Benzoic Acid Derivatives Bearing an α,β-Unsaturated Ketone Substituent: Synthesis of Methyl Taboganate
  作者：Theodora Calogeropoulou、Anastasia Detsi、Vassilios Roussis、Andrew Tsotinis、Christos Roussakis

  DOI：10.1055/s-2005-921933

  日期：——

  concise route to benzoic acid derivatives bearing an α,β-unsaturated ketone moiety and its application to the synthesis of the natural product methyl taboganate (1) is described. The methodology is based on the additionof a Grignard reagent to an appropriately substituted salicylaldehyde followed by oxidation of the resulting allylic alcohol to the corresponding α,β-unsaturated ketone. The new compounds

  描述了带有 α,β-不饱和酮部分的苯甲酸衍生物的简明路线及其在合成天然产物塔博加酸甲酯 (1) 中的应用。该方法基于将格氏试剂添加到适当取代的水杨醛中，然后将所得烯丙醇氧化成相应的 α,β-不饱和酮。测试了新化合物的细胞毒活性。
• Asymmetric Epoxidation of Olefins with Hydrogen Peroxide by an in Situ-Formed Manganese Complex
  作者：Wen Dai、Sensen Shang、Bo Chen、Guosong Li、Lianyue Wang、Lanhui Ren、Shuang Gao

  DOI：10.1021/jo501178k

  日期：2014.7.18

  Asymmetric epoxidation of a variety of cis, trans, terminal, and trisubstituted olefins in excellent yields (up to 94%) and enantioselectivities (>99% ee) by an in situ-formed manganese complex using H2O2 has been developed. A relationship between the hydrophobicity of the catalyst imposed by ligand and the catalytic activity has been observed. The influence of the amount and identity of the acid additive

  已经开发出了使用H 2 O 2原位形成的锰配合物，可以以优异的收率（高达94％）和对映选择性（> 99％ee）对各种顺式，反式，端基和三取代的烯烃进行不对称环氧化。已经观察到配体施加的催化剂的疏水性与催化活性之间的关系。检查了酸添加剂的量和特性的影响，并且通过使用催化量的羧酸添加剂实现了改进的对映选择性。
• A Novel Method for the Preparation of Acid-Sensitive Epoxides from Olefins with the Combined Use of Molecular Oxygen and Aldoacetal Catalyzed by a Cobalt(II) Complex
  作者：Kiyotaka Yorozu、Toshihiro Takai、Tohru Yamada、Teruaki Mukaiyama

  DOI：10.1246/bcsj.67.2195

  日期：1994.8

  An efficient synthesis of acid-sensitive epoxides, such as chromene oxide or epoxide of γ,δ-unsaturated alcohol, was successfully achieved by the oxygenation of corresponding olefins with the combined use of an atmospheric pressure of molecular oxygen and aldoacetal catalyzed by a cobalt(II) complex coordinated with the 1,3-diketone ligand. The reactions proceeded under mild and neutral conditions

  通过在常压下分子氧和醛缩醛的协同作用，将相应的烯烃氧化，并在钴催化下，成功地合成了酸敏感环氧化物，如色烯氧化物或γ,δ-不饱和醇的环氧化物（ II) 与 1,3-二酮配体配位的复合物。反应在温和且中性的条件下进行，并以良好的收率获得所需的环氧化物。在本反应条件下，既没有观察到过氧化也没有观察到形成的环氧化物分解。此外，各种甲硅烷基烯醇醚和甲硅烷基烯酮缩醛，酸敏感化合物，也分别顺利地单氧化成相应的 α-羟基酮和 α-羟基羧酸酯。