1-(3,5-dimethoxyphenyl)-2-oxo-2-phenylethyl acetate | 34904-91-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1-(3,5-dimethoxyphenyl)-2-oxo-2-phenylethyl acetate
• 英文别名: [1-(3,5-dimethoxyphenyl)-2-oxo-2-phenylethyl] acetate
• CAS: 34904-91-1
• 化学式: C₁₈H₁₈O₅
• 分子量: 314.338
• InChiKey: IVWKEMXMFCKDSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-(3,5-dimethoxyphenyl)-2-oxo-2-phenylethyl acetate 以 乙腈 为溶剂， 以80 %的产率得到2-Phenyl-5,7-dimethoxybenzofuran
  参考文献：
  名称：

  3′,5′-二甲氧基苯偶姻氟化物光环化-脱保护反应的瞬态吸收光谱研究

  摘要：

  3',5'-二甲氧基苯偶姻（DMB）体系作为一种光可去除保护基（PRPG），用于消除各种官能团，已被广泛研究，并已在许多领域得到应用。 DMB氟化物的光解导致高效的光环化-脱保护反应，在MeCN溶液中产生高产率的3',5'-二甲氧基苯并呋喃（DMBF），而在水溶液中存在竞争反应生成DMB。随着水体积比的增加，DMB的产率增加。为了了解选定的 DMB 化合物光解的溶剂效应，结合了飞秒到纳秒瞬态吸收光谱（fs-TA 和 ns-TA）、纳秒时间分辨共振拉曼光谱 (ns-TR3) 和量子化学计算采用该方法研究了DMB氟化物在不同溶液中的光物理和光化学反应机理。借助具有给电子和吸电子发色团的 DMB 氟化物的双发色团性质，可以在纯 MeCN 溶液中找到环化中间体。环状双自由基中间体的脱保护导致 DMBF 和环状阳离子物质的同时形成。另一方面，在水溶液中，fs-TA实验表明直接激发后可以观察到α-酮阳离子，它可以在8

  DOI：

  10.3390/molecules29040842
• 作为产物：
  描述：

  α-(3,5-dimethoxyphenyl)-α-(trimethylsilyloxy)acetonitrile 在 吡啶 、 盐酸 作用下， 以 二氯甲烷 为溶剂， 反应 9.0h， 生成 1-(3,5-dimethoxyphenyl)-2-oxo-2-phenylethyl acetate
  参考文献：
  名称：

  Photoremovable Protecting Groups for Phosphorylation of Chiral Alcohols. Asymmetric Synthesis of Phosphotriesters of (-)-3',5'-Dimethoxybenzoin

  摘要：

  Procedures have been developed for the preparation of dimethoxybenzoinyl (DMB) phosphate triesters that can be deprotected photochemically. These compounds can be useful in light-directed synthesis and caging. The photochemistry of a wide variety of fluorine-, oxygen-, and nitrogen-substituted benzoin acetates was examined to determine the substitution pattern in the nonacylated aromatic ring producing optimum chemical yields. Two groups, 2',3'-dimethoxybenzoin and 3',5'dimethoxybenzoin, were found to give the highest yields of the benzofuran product and were further developed for the photochemical deprotection of phosphate esters. These reactions could not be quenched, suggesting a singlet photosolvolysis mechanism. An asymmetric synthesis of 3',5'dimethoxybenzoin via the benzaldehyde cyanohydrin was developed that minimizes the number of diastereomers formed in the phosphorylation of chiral alcohols. A phosphoramidite reagent for the derivatization of alcohols was prepared and used to produce scalemic dimethoxybenzoinyl phosphate esters from pantolactone and glycerol, serine, and tyrosine derivatives. These compounds were deprotected photochemically to produce the phosphodiesters in high yield.

  DOI：

  10.1021/jo00093a021

文献信息

• Modulated photochemical reactivities of O-acetylated (3’,5’-dimethoxyphenyl)heteroaryl acyloin derivatives under direct irradiation and photo-induced electron transfer conditions
  作者：Rajesh Bisht、Saumya Singh、Kothandam Krishnamoorthy、Jayaraj Nithyanandhan

  DOI：10.1039/c8pp00082d

  日期：2018.6

  part of the O-acetylated cross-acyloin derivatives. The furan, thiophene and bithiophene derivatives led to the expected cyclized (benzofuran capped) products but the derivatives with extended conjugation decomposed under direct irradiation. However, under irradiation in the presence of an electron donor such as triethylamine, the extended acyloin derivatives afforded both cyclized and deacetoxylated

  3′，5′-二甲氧基苯偶姻酯是重要的可光除去的保护基，其在光释放时形成2-苯基苯并呋喃衍生物。我们利用相似的概念来测试通过直接光照射和光诱导的电子转移反应使O-乙酰化的（3'，5'-二甲基苯基）杂芳基酰基蛋氨酸衍生物经受将苯并呋喃部分安装到共轭骨架上的光化学方法。对这些光化学方法进行了探索，以发现附着在O酮部分上的各种杂芳族底物-乙酰化的交叉酰基辅酶衍生物。呋喃，噻吩和联噻吩衍生物可产生预期的环化（苯并呋喃封端）产品，但在直接辐射下具有扩展共轭作用的衍生物会分解。然而，在电子给体例如三乙胺存在下的辐射下，扩展的酰基辅酶衍生物既提供环化的产物又提供脱乙酰氧基化的产物。对于溶液处理的有机场效应晶体管，还探索并测试了扩展的环化产物的半导体性质，该晶体管的最大空穴迁移率为1.3×10 -6 cm 2 V -1 s -1。
• Photoacylation of Alcohols in Neutral Medium
  作者：Jean-Luc Débieux、Anne Cosandey、Céline Helgen、Christian G. Bochet

  DOI：10.1002/ejoc.200600790

  日期：2007.5

  We report here conditions which allow the photoacylation of primary, secondary and tertiary alcohols with N-acetyl-5,7-dinitroindoline under exceptionally mild conditions, at wavelengths harmless to most functional groups, including otherwise photosensitive ones. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  我们在这里报告了允许伯醇、仲醇和叔醇与 N-乙酰基-5,7-二硝基二氢吲哚在异常温和的条件下，在对大多数官能团无害的波长下光酰化的条件，包括其他光敏的。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Mechanistic Studies on the Photochemical Deprotection of 3′,5′‐Dimethoxybenzoin Esters
  作者：Michael C. Pirrung、Tong Ye、Zheng Zhou、John D. Simon

  DOI：10.1562/2006-02-07-ra-798

  日期：2006.9

  theoretical evidence suggest the mechanism is heterolysis of the singlet excited state to form a carboxylate and the alpha-ketocation. The alpha-ketocation has been observed by transient spectroscopy. We propose the alpha-ketocation undergoes electrocyclization to an intermediate with extended conjugation, whose deprotonation gives the observed benzofuran product. A Bronsted study of the rates of benzofuran

  提出了几种用于二甲氧基苯偶姻酯的光化学脱保护的机制替代方案。实验和理论证据均表明其机理是单线激发态杂化形成羧酸盐和α-酮基阳离子。通过瞬态光谱法已经观察到α-酮化。我们建议对α-酮阳离子进行电环化，使其具有扩展的共轭中间体，该中间体的去质子化作用可观察到苯并呋喃产物。对衍生自不同pKa酸的二甲氧基安息香酯与苯并呋喃形成速率的布朗斯台德研究表明，该速率与离去基团的碱性无关。在该多步反应中，通过最终去质子化形成的苯并呋喃比α-酮化反应的生成要慢。
• Improved polyaromatic benzoin photoremovable protecting groups
  作者：Laura J. McKay、Carl-Johan Carling、Neil R. Branda

  DOI：10.1016/j.jphotochem.2021.113530

  日期：2021.12

  Two novel photoremovable protecting groups in the benzoin class have been prepared and their photochemistry investigated. These polyaromatic benzoin photoremovable protecting groups have significantly improved molar extinction coefficients with absorptions that extend further towards the visible region of the spectrum and should not be hindered by a ‘inner filter’ effects, making them appealing for

  已经制备了安息香类中的两种新型光可去除保护基团并研究了它们的光化学。这些聚芳族安息香可光去除保护基团具有显着改善的摩尔消光系数，其吸收进一步扩展到光谱的可见区域，不应受到“内部过滤”效应的阻碍，使它们对敏感环境中的应用具有吸引力。我们的结果表明，这些特征并不总是可转化为光响应功效。
• Mechanism of 3‘,5‘-Dimethoxybenzoin Ester Photochemistry:  Heterolytic Cleavage Intramolecularly Assisted by the Dimethoxybenzene Ring Is the Primary Photochemical Step
  作者：Yijian Shi、John E. T. Corrie、Peter Wan

  DOI：10.1021/jo971121t

  日期：1997.11.1