methyl 4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate | 106342-09-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate
• 英文别名: Benzoic acid, 4-[(tetrahydro-2H-pyran-2-yl)oxy]-, methyl ester；methyl 4-(oxan-2-yloxy)benzoate
• CAS: 106342-09-0
• 化学式: C₁₃H₁₆O₄
• 分子量: 236.268
• InChiKey: KDMICHPWNLJREW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate 在 aluminium(III) iodide 、 N,N-二甲基甲酰胺二甲基缩醛 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以85%的产率得到对羟基苯甲酸甲酯
  参考文献：
  名称：

  三碘化铝和N，N-二甲基甲酰胺二甲基乙缩醛对酸不稳定的芳烷基醚的手性辅助选择性裂解。

  摘要：

  N，N-二甲基甲酰胺二甲基乙缩醛（DMF-DMA）利用三碘化铝通过相邻基团的参与选择性裂解醚。包括羧酸盐，烯丙基，叔丁基二甲基甲硅烷基（TBS）和叔丁氧羰基（Boc）在内的各种酸不稳定官能团均完好无损。该方法为裂解邻苯二酚单烷基醚和从乙缩醛型保护基（如甲氧基甲基（MOM），甲氧基乙氧基甲基（MEM）和四氢吡喃基（THP））上化学选择性解吸酚提供了一种有效的方法。

  DOI：

  10.1021/acs.joc.0c00290
• 作为产物：
  描述：

  sodium methylparaben 、 2-氯-四氢-2H-吡喃 在 盐酸 作用下， 生成 methyl 4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate
  参考文献：
  名称：

  Intramolecular general-acid and electrostatic catalysis in acetal hydrolysis. Hydrolysis of 2-(substituted phenoxy)-6-carboxytetrahydropyrans and 2-alkoxy-6-carboxytetrahydropyrans

  摘要：

  Rate constants have been determined for hydrolysis of a series of trans-2-(substituted phenoxy)-6-carboxytetrahydropyrans (e,a) in H2O and 50% dioxane-H2O. The second-order rate constant (k2) for the apparent hydronium ion catalyzed reaction of the anionic species of the p-nitro derivative in 50% dioxane-H2O (50-degrees-C) is 620-fold larger than the second-order rate constant for hydrolysis of 2-(p-nitrophenoxy)tetrahydropyran. The slope (rho) of the Hammett plot of log k2 vs sigma is approximately 0, which supports a mechanism involving intramolecular general-acid catalysis by the un-ionized carboxyl group with proton transfer to the leaving group oxygen. Sizable catalytic effects can therefore be obtained in an intramolecular general-acid-catalyzed reaction when the leaving group is sufficiently good, even though the steric fit is poor and proton transfer may necessarily occur via an intervening water molecule. Intramolecular general-acid-catalyzed ring opening is not a favorable process in the hydrolysis of tetrahydropyranyl acetals; such a mechanism does not occur in the hydrolysis of 2-alkoxy-6-carboxytetrahydropyrans. In the pH-independent decomposition of 2-(p-nitrophenoxy)-6-carboxytetrahydropyran at pH > 6, the neighboring carboxylate anion participates electrostatically in 50% dioxane-H2O and gives a 10-fold rate enhancement. The plot of log k(obsd) vs pH for hydrolysis of 2-(o-carboxyphenoxy)-6-carboxytetrahydropyran is bell shaped, which indicates that the monoanionic species is maximally reactive. The rate enhancement in that reaction in comparison with the hydrolysis of 2-(p-carboxyphenoxy)-6-carboxytetrahydropyran or 2-(p-carboxyphenoxy)tetrahydropyran is a factor of (2-4) x 10(3) in H2O but is 10(4)-10(5) in 50% dioxane-H2O. The o-carboxyl group acts as an intramolecular general acid. However, bifunctional catalysis does not take place in this system. The lack of efficient electrostatic facilitation of these reactions by a neighboring carboxylate anion is most likely due to the energy expenditure required for the 6-carboxylate group to approach the developing oxocarbonium ion closely. There is no chemical support for proposed mechanisms of lysozyme-catalyzed reactions that involve intracomplex general-acid-catalyzed opening of an unstrained hexose ring or large electrostatic stabilization effects by Asp-52.

  DOI：

  10.1021/ja00020a028

文献信息

• Method Of Preparing Fused Ring Indeno Compounds
  申请人：Transitions Optical, Inc.

  公开号：US20150141662A1

  公开（公告）日：2015-05-21

  The present invention relates to methods of preparing fused ring indeno compounds that involves reacting together a dienophile and a lactone compound, in the presence of a catalyst, and a carboxylic acid anhydride. With some embodiments, the fused ring indeno compound is represented by the following Formula (I-A), the dienophile is represented by the following Formula (II-A), and the lactone compound is represented by the following Formula (III-A):

  本发明涉及一种制备融合环吲哚化合物的方法，涉及将双亲受体和内酯化合物在催化剂和羧酸酐的存在下反应在一起。在某些实施例中，融合环吲哚化合物由以下式(I-A)表示，双亲受体由以下式(II-A)表示，内酯化合物由以下式(III-A)表示：
• Photochromic Indeno-Fused Ring Pyran Compounds
  申请人：Transitions Optical, Inc.

  公开号：US20150141661A1

  公开（公告）日：2015-05-21

  The present invention relates to photochromic indeno-fused ring pyran compounds represented by the following Formula (I-A): The present invention also relates to photochromic dichroic compounds, such as represented by Formula (I-A), in which (i) Z 2 is a group N—R 13 in which R 13 is a group L, and (ii) optionally at least one R 1 independently for each n is selected from a group L, in which the group L independently in each case is a lengthening group that provides the photochromic compound with dichroic properties, in accordance with some embodiments. The present invention also relates to photochromic articles, such as photochromic ophthalmic articles, that include one or more photochromic compounds according to the present invention, such as represented by Formula (I-A).

  本发明涉及由以下式（I-A）表示的光致变色吲哚融合环吡喃化合物。本发明还涉及光致二向色化合物，例如由式（I-A）表示，其中（i）Z2是一个N—R13基团，其中R13是一个L基团，以及（ii）对于每个n，可选地至少选择一个R1，每种情况下独立选择自L基团，其中每种情况下L基团是一个提供光致化合物二向色性能的延伸基团，符合某些实施例。本发明还涉及光致物品，例如光致眼科物品，包括根据本发明的一个或多个光致化合物，例如由式（I-A）表示。
• Construction of C–O bond via cross-dehydrogenative coupling of sp [ ] C–H bond with phenols catalyzed by copper porphyrin
  作者：Shuang Yang、Ming-Feng Xiong、Wan-Qun Tian、Hao Zhang、Xin-Yan Xiao、Hai-Yang Liu、Chi-Kwong Chang

  DOI：10.1016/j.tet.2020.131569

  日期：2020.11

  Copper porphyrin-catalyzed construction of ether bond by cross-dehydrogenative coupling of sp [3] C–H bond with phenols bearing electron-withdrawing groups (EWG) was described for the first time. A broad range of substrates afforded different acetals in moderate to excellent yields with good functional group tolerance. The developed method is not only suitable for phenol substrates with ortho-directing

  首次描述了铜卟啉催化的sp [3] C–H键与带有吸电子基团（EWG）的酚的交叉脱氢偶联形成醚键。各种各样的底物以中等至优异的产率提供了不同的缩醛，并且具有良好的官能团耐受性。所开发的方法不仅适用于具有邻位导向基团的苯酚底物，而且还适用于不具有邻位导向基团的苯酚。显着地，在克级测试中达到了高达7300的高周转率（TON）。
• 一种选择性的芳基烷基醚的醚键断裂方法
  申请人：荆楚理工学院

  公开号：CN111620764B

  公开（公告）日：2023-05-05

  本发明公开了一种选择性的芳基烷基醚裂解方法，该方法是：芳基烷基醚与碘化铝和一种添加剂在有机溶剂中，在‑20℃至回流的温度下发生选择性的醚键断裂反应，生成苯酚及其衍生物。该方法条件温和，操作简便，适用于含有邻羟基、邻羰基的芳基烷基醚以及缩醛类的醚的裂解，也可以用于脱除三苯甲基、叔丁基等叔碳类的位阻较大的羟基保护基。
• The construction of C(sp³)–O bond via copper porphyrin catalyzed cross-dehydrogenative coupling reaction: Substituent and electronic effect of the catalysts
  作者：Feng-Hua Wang、Zheng-Yan Liu、Shuang Yang、Lei Shi、Dong-Zi Lin、Hai-Yang Liu、Gao-Qing Yuan

  DOI：10.1080/00397911.2021.1919900

  日期：——

  effect of copper porphyrin catalysts on the cross-dehydrogenative coupling (CDC) reaction between the hydroxyl group of phenol substrates and C(sp3)-H bond have been investigated. Results showed that copper porphyrin bearing electron-withdrawing, bulky steric hindrance or heteroatom of pyridyl groups could increase the catalytic activity in the reaction. 5,10,15,20-(tetrakis(4-pyridyl)porphyrin)copper

  摘要 已经研究了铜卟啉催化剂对苯酚底物的羟基与 C(sp 3 )-H 键之间的交叉脱氢偶联 (CDC) 反应的推挽电子和空间效应。结果表明，带有吸电子、大体积位阻或吡啶基杂原子的铜卟啉可以提高反应的催化活性。5,10,15,20-(四(4-吡啶基)卟啉)铜(CuTPyP)在所有测试的催化剂中被发现是最好的。带有各种官能团的苯酚底物提供了中等至极好的产率（99%）。值得注意的是，与其他测试的铜卟啉相比，CuTPyP 不仅表现出显着更高的活性，而且可以将反应时间从 12 小时缩短到 6 小时。