4-acetoxymethyl-2-methoxyphenyl acetate | 17574-14-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: 4-acetoxymethyl-2-methoxyphenyl acetate
• 英文别名: 4-acetoxy-3-methoxybenzyl acetate；1-acetoxy-4-acetoxymethyl-2-methoxy-benzene；1-Acetoxy-4-acetoxymethyl-2-methoxy-benzol；(3-Methoxy-4-acetoxy-benzyl)-acetat；Vanillylalkohol-diacetat；Vanillyl alcohol diacetate；(4-acetyloxy-3-methoxyphenyl)methyl acetate
• CAS: 17574-14-0
• 化学式: C₁₂H₁₄O₅
• 分子量: 238.24
• InChiKey: ZOQJJSKHULYOOA-UHFFFAOYSA-N

物化性质

• 沸点：
  304.2±32.0 °C(Predicted)
• 密度：
  1.168±0.06 g/cm3(Predicted)
• 保留指数：
  1747.6

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  4-acetoxymethyl-2-methoxyphenyl acetate 在 Candida rugosa lipase (CRL, Type II) 作用下， 以 异丙醚 、 正丁醇 为溶剂， 反应 288.0h， 以50%的产率得到4-acetoxymethyl-2-methoxyphenol
  参考文献：
  名称：

  Enzyme-Catalyzed Chemoselective Transesterification Reactions on Hydroxymethylated Phenolic Compounds

  摘要：

  The chemoselective capabilities of porcine pancreatic lipase (PPL) in tetrahydrofuran and Candida rugosa lipase (CRL) in diisopropyl ether have been investigated for selective acetylation and deacetylation of hydroxymethylated phenols and hydroxyaryl alkyl ketones and their peracetylated derivatives. Both PPL and CRL exhibited exclusive selectivity for the acetylation of alcoholic hydroxyl group over the phenolic hydroxyl group(s) of the hydroxymethylated phenols 1-5 and aryl alkyl ketones 6-9, and for the deacetylation of ester group involving the phenolic hydroxyl group over the ester group involving alcoholic hydroxyl of the peracetates 19-24. The preliminary results indicate that this strategy of chemoselective acetylation can also be used in the enantiomeric resolution of racemic ketones 6-9. Single crystal X-ray diffraction studies have confirmed the structures of compounds 4, 15, and 17. (C) 1999 Academic Press.

  DOI：

  10.1006/bioo.1998.1117
• 作为产物：
  描述：

  4-羟基-3-甲氧基苄醇 在 1-butyl-3-methylimidazolium tetrachloroindate 作用下， 反应 0.09h， 生成 4-acetoxymethyl-2-methoxyphenyl acetate
  参考文献：
  名称：

  [C4mim][InCl4]: An efficient catalyst-medium for alkoxymethylation of alcohols and their interconversion to acetates and TMS-ethers

  摘要：

  摘要 提出了一种简单、绿色且选择性强的方法，利用Lewis酸性室温离子液体[C4mim][InCl4]作为催化剂和反应介质，在常温、微波和超声辐射下，对一级和二级醇进行甲氧基甲基化和乙氧基甲基化。在该催化系统中，相应的MOM和EOM醚以优良的收率和短时间的反应获得。此外，该催化系统还用于在热条件及微波和超声辐射下，将这些保护醇温和高效地转化为相应的醋酸酯和三甲基硅醚。

  DOI：

  10.1016/j.crci.2010.08.006

文献信息

• Selective acylation of the phenolic hydroxyl of (hydroxyalkyl)phenols by using vinyl carboxylates as acyl donors in the presence of rubidium fluoride
  作者：Toshifumi Miyazawa、Masato Yamamoto、Hiroshi Danjo

  DOI：10.1007/s00706-013-1019-2

  日期：2013.9

  AbstractHighly selective acylation of the phenolic hydroxy group can be achieved with (hydroxyalkyl)phenols carrying both alcoholic and phenolic hydroxyls by the use of vinyl carboxylates as acyl donors in the presence of rubidium fluoride. Graphical Abstract

  摘要在氟化carrying存在下，通过使用羧酸乙烯酯作为酰基供体，可以同时携带醇羟基和酚羟基的（羟烷基）酚实现酚羟基的高度选择性酰化。 图形概要
• An efficient method for selective acetylation of alcoholic hydroxyl groups.
  作者：YOSHIMITSU NAGAO、EIICHI FUJITA、TATSUHIKO KOHNO、MASAHIRO YAGI

  DOI：10.1248/cpb.29.3202

  日期：——

  Acetylation of the C-6 hydroxyl group in oridonin (1), which is difficult by the use of acetic anhydride in pyridine, was investigated using acetic anhydride in the presence of some Lewis acids. A reagent system of acetic anhydride in the presence of a catalytic amount of boron trifluoride etherate was shown to be effective for this purpose. This reagent system was shown to be useful for selective acetylation of the alcoholic group (s) in compounds which have both alcoholic and phenolic hydroxyl groups.

  研究人员在一些路易斯酸存在的情况下，使用醋酸酐对奥里多宁（1）中的 C-6 羟基进行了乙酰化反应。结果表明，在催化量的三氟化硼醚酸存在下的醋酸酐试剂体系可以有效地实现这一目的。这种试剂体系对具有醇羟基和酚羟基的化合物中醇羟基的选择性乙酰化非常有用。
• Esterification mechanism of lignin with different catalysts based on lignin model compounds by mechanical activation-assisted solid-phase synthesis
  作者：Xiaohong Zhao、Yanjuan Zhang、Liping Wei、Huayu Hu、Zuqiang Huang、Mei Yang、Aimin Huang、Juan Wu、Zhenfei Feng

  DOI：10.1039/c7ra10482k

  日期：——

  the catalysts could enhance the esterification. Both the phenolic hydroxyl and aliphatic hydroxyl participated in the esterification and the reactivity of the basic structural units of lignin had a descending order of H, G, and S. Oxidations could happen in the presence of unsaturated groups such as aldehyde in the lignin model compounds. The catalytic mechanism of the three kinds of catalyst was different

  为了了解机械活化辅助固相合成（MASPS）技术对木质素的酯化机理，对木质素模型化合物p-羟基苯甲醛（H），香兰素和香兰醇（G）和丁香醛（S）在与乙酸酐，4-二甲基氨基吡啶（DMAP），乙酸钠和硫酸作为催化剂的反应中使用。产物的FTIR，NMR和UV / vis分析表明，所有催化剂均可增强酯化作用。酚羟基和脂肪族羟基均参与酯化反应，木质素基本结构单元的反应性依次为H，G和S。在木质素模型化合物中存在醛等不饱和基团时，氧化作用可能发生。三种催化剂的催化机理不同，其催化活性依次为DMAP，乙酸钠和硫酸。以DAMP为催化剂，酚羟基的反应活性高于脂肪族羟基，但以乙酸钠或硫酸为催化剂，脂肪族羟基的反应活性高于酚羟基。用硫酸作为催化剂，发生了一些副反应并导致苯环的环断裂或交联。一致性验证表明，使用木质素模型化合物研究木质素的酯化机理是合理可行的。
• Nature stays natural: two novel chemo-enzymatic one-pot cascades for the synthesis of fragrance and flavor aldehydes
  作者：Stefan Giparakis、Margit Winkler、Florian Rudroff

  DOI：10.1039/d3gc04191c

  日期：——

  Novel synthetic strategies for the production of high-value chemicals based on the 12 principles of green chemistry are highly desired. Herein, we present a proof of concept for two novel chemo-enzymatic one-pot cascades allowing for the production of valuable fragrance and flavor aldehydes. We utilized renewable phenylpropenes, such as eugenol from cloves or estragole from estragon, as starting materials

  人们非常需要基于绿色化学 12 项原则生产高价值化学品的新型合成策略。在本文中，我们提出了两种新型化学酶一锅法级联反应的概念验证，可用于生产有价值的香料和风味醛。我们使用可再生的苯基槐烯作为起始材料，例如丁香中的丁香酚或来自埃斯特拉贡的雌芪。对于第一种策略，进行 Pd 催化的烯丙基双键异构化和随后的酶介导的（芳香族双加氧酶，ADO）烯烃裂解以获得所需的醛。在第二条途径中，通过无铜 Wacker 氧化方案将双键氧化成相应的酮，然后进行酶促 Baeyer-Villiger 氧化（来自福氏嗜睡双歧杆菌的苯丙酮单加氧酶）、酯酶介导的（来自荧光假单胞菌的酯酶，PfeI）水解和随后的伯醇氧化（来自恶臭假单胞菌的醇脱氢酶， AlkJ） 添加到相应的醛类产物中。对八种不同的苯丙烯衍生物进行这些反应序列，允许在 4 个反应步骤后以高达 55% 的产率合成七种醛（每步为 86%）。
• H3PW12O40@[bmim][FeCl4]: A green catalytic system for alkoxymethylation of alcohols and their one-pot interconversion to acetates and TMS-ethers
  作者：I. Mohammadpoor-Baltork、M. Moghadam、S. Tangestaninejad、V. Mirkhani、A. R. Khosropour、A. Mirjafari

  DOI：10.1007/bf03249085

  日期：2011.6

  12-Tungstophosphoric acid immobilized on [bmim][FeCl4] was found to be an efficient catalyst for chemoselective methoxymethylation and ethxoymethylation of alcohols and also one-pot conversion of MOM- or EOM-ethers to their corresponding acetates and TMS-ethers under thermal conditions and microwave irradiation. These procedures were simple, rapid and the corresponding products were obtained in high yields. The catalyst exhibited remarkable reactivity and was reusable.