1,3-dimethoxybenzene-2-d | 49771-99-5

• 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: 1,3-dimethoxybenzene-2-d
• 英文别名: 1-deutero-2,6-dimethoxybenzene；2,6-dimethoxy-1-deuterobenzene；m-Dimethoxybenzol-2-d；2-deutero-1,3-dimethoxybenzene；2-deuterio-1,3-dimethoxy-benzene；2,6-dimethoxybenzene-d；2-Deuterio-1,3-dimethoxybenzene
• CAS: 49771-99-5
• 化学式: C₈H₁₀O₂
• 分子量: 139.158
• InChiKey: DPZNOMCNRMUKPS-RAMDWTOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,3-dimethoxybenzene-2-d 在 氘代硫酸 作用下， 以 乙腈 为溶剂， 生成 间苯二甲醚
  参考文献：
  名称：

  Photochemistry of dimethoxybenzenes in aqueous sulfuric acid

  摘要：

  The photochemistry of the three isomeric dimethoxybenzenes (1-3) has been studied in aqueous sulfuric acid. Two processes were found to take place: (i) photoprotonation of the ring resulting in exchange of the ring protons, which was observed for all three compounds and (ii) ipso substitution of the methoxy group by water, which was observed only for 1,2-dimethoxybenzene (3). Both of these photochemical reactions were catalyzed by acid, requiring acidities stronger than pH(D) 2 for observable reaction. Quantum yields for proton exchange and ipso substitution are reported as a function of medium acidity. The fluorescence emissions of all three compounds were quenched by acid, to give sigmoid type quenching curves, that have a complementary relationship with the corresponding plots of quantum yield of exchange vs acidity, consistent with protonation of the benzene ring in S1 as the primary photochemical step, to give cyclohexadienyl cation intermediates. Stern-Volmer analysis of fluorescence quenching by proton gave photoprotonation rates in the range 0.09-2.2 X 10(9) M-1 s-1. The results of this work demonstrate unambiguously that methoxy-substituted benzenes are much stronger bases in S1 (pK(BH)+ congruent-to 1 to -2) than in the ground state. This enhanced basicity is manifested in regioselectivity of exchange of 1 and 3 and ipso substitution chemistry of 3, processes not observed in the ground states of these compounds.

  DOI：

  10.1021/jo00061a042
• 作为产物：
  描述：

  2,6-二甲氧基苯甲酸 在 重水 、 silver(I) acetate 、 potassium carbonate 作用下， 以 N-甲基吡咯烷酮 为溶剂， 反应 16.0h， 以77%的产率得到1,3-dimethoxybenzene-2-d
  参考文献：
  名称：

  Selective Copper- or Silver-Catalyzed Decarboxylative Deuteration of Aromatic Carboxylic Acids

  摘要：

  讨论了脱羧转化在有机合成中的实际应用，并披露了作为进一步例证的（杂）芳香羧酸的脱羧氘化反应。在温和条件下，通过一步反应，从易于获得的芳香羧酸和氘水合成了多种单氘代芳烃。铜催化剂具有最广泛的适用范围，但对于某些邻位取代的苯甲酸盐，银催化剂表现更优。少数底物，例如喹啉-2-羧酸，即使在无金属催化剂的情况下也能发生脱羧反应。

  DOI：

  10.1055/s-0031-1289638

文献信息

• Selective Copper- or Silver-Catalyzed Decarboxylative Deuteration of Aromatic Carboxylic Acids
  作者：Lukas Gooßen、Martin Rudzki、Ana Alcalde-Aragonés、Wojciech Dzik、Nuria Rodríguez

  DOI：10.1055/s-0031-1289638

  日期：2012.1

  The practical utility of decarboxylative transformations in organic synthesis is discussed, and the decarboxylative deuteration of (hetero)aromatic carboxylic acids is disclosed as a further example. Various monodeuterated arenes were synthesized under mild conditions, in a single step from easily accessible aromatic carboxylic acids and deuterium oxide. Copper catalysts were found to have the widest scope, but silver catalysts are superior for some ortho-substituted benzoates. A few substrates, e.g. quinoline-2-carboxylic acid, decarboxylate even in the absence of a metal catalyst.

  讨论了脱羧转化在有机合成中的实际应用，并披露了作为进一步例证的（杂）芳香羧酸的脱羧氘化反应。在温和条件下，通过一步反应，从易于获得的芳香羧酸和氘水合成了多种单氘代芳烃。铜催化剂具有最广泛的适用范围，但对于某些邻位取代的苯甲酸盐，银催化剂表现更优。少数底物，例如喹啉-2-羧酸，即使在无金属催化剂的情况下也能发生脱羧反应。
• Microwave Enhanced Decarboxylations of Aromatic Carboxylic Acids: Improved Deuteriation/Tritiation Potential
  作者：Lottie B. Frederiksen、Thomas H. Grobosch、John R. Jones、Shui-Yu Lu、Chao-Cheng Zhao

  DOI：10.3184/030823400103165644

  日期：2000.1

  Decarboxylation of aromatic carboxylic acids under microwave enhanced conditions is an increasingly attractive method of preparing deuterium/tritium labelled compounds.

  在微波增强条件下芳族羧酸的脱羧是一种越来越有吸引力的制备氘/氚标记化合物的方法。
• Sodium Diisopropylamide in Tetrahydrofuran: Selectivities, Rates, and Mechanisms of Arene Metalations
  作者：Russell F. Algera、Yun Ma、David B. Collum

  DOI：10.1021/jacs.7b08734

  日期：2017.10.25

  Sodium diisopropylamide (NaDA)-mediated metalations of arenes in tetrahydrofuran (THF)/hexane or THF/Me2NEt solutions are described. A survey of >40 benzenoid- and pyridine-based arenes with a range of substituents demonstrates the efficacy and regioselectivity of metalation. Metalations of activated disubstituted arenes and selected monosubstituted arenes are rapid at −78 °C. Rate studies of 1,3-dimethoxybenzene

  描述了在四氢呋喃（THF）/己烷或THF / Me 2 NEt溶液中，二异丙基氨基钠（NaDA）介导的芳烃金属化。对超过40种具有一系列取代基的基于苯并吡啶和吡啶的芳烃的研究表明，其金属化的功效和区域选择性都很高。活化的二取代的芳烃和选定的单取代的芳烃在-78°C时快速金属化。1,3-二甲氧基苯和相关甲氧基化芳烃的速率研究表明，基于单体的原金属具有两个或三个配位的THF配体。苯和具有弱活化基团的单取代芳烃的同位素交换速率研究表明，类似的二溶剂化和三溶剂化的单体基金属化反应。讨论了协同的诱导，消旋，空间和螯合作用。
• Halogen–deuterium exchange reaction mediated by tributyltin hydride using THF-d8 as the deuterium source
  作者：Tomonobu Mutsumi、Hiroki Iwata、Kazuo Maruhashi、Yasunari Monguchi、Hironao Sajiki

  DOI：10.1016/j.tet.2010.12.007

  日期：2011.2

  A regioselective deuteration method for a wide variety of aromatic compounds using the halogen–deuterium exchange reaction initiated by Bu3SnH using THF-d8 as the deuterium source was developed.

  开发了一种区域选择性氘化方法，该方法通过使用THF- d 8作为氘源，通过Bu 3 SnH引发的卤素-氘交换反应，对多种芳香族化合物进行区域选择性氘化。
• Stable arylsilver compounds containing dimethylamino, (dimethylamino)methyl or methoxy groups at the aryl nucleus
  作者：A.J. Leusink、G. Van Koten、J.G. Noltes

  DOI：10.1016/s0022-328x(00)89991-x

  日期：1973.8

  The following organosilver compounds have been prepared from the corresponding lithium compounds and silver bromide : 2-[(dimethylamino)methyl]phenyl}silver, 2-[(dimethylamino)methyl]phenyl}silver·silver bromide, bis[2-(dimethylamino)phenyl]silver} · silver bromide, (2,6-dimethoxyphenyl)silver and (2,4,6-trimethoxyphenyl)silver. These substituted phenylsilvers, which have been characterized by elemental

  由相应的锂化合物和溴化银制备了以下有机银化合物：2-[（（二甲基氨基）甲基]苯基}银，2-[（（二甲基氨基）甲基]苯基}银·溴化银，双[2- （二甲基氨基）苯基]银}·溴化银，（2,6-二甲氧基苯基）银和（2,4,6-三甲氧基苯基）银。这些取代的苯基银，已通过元素分析表征，mol。重量 红外光谱和PMR光谱以及降解反应的测定显示出比苯基银更高的热，氧化和水解稳定性。通常，这些化合物在100°至200°之间分解，并与氧气和水缓慢反应。