1-(diisopropoxymethyl)-4-nitrobenzene | 54149-72-3

• 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-(diisopropoxymethyl)-4-nitrobenzene
• 英文别名: p-Nitrobenzaldehyd-diisopropylacetal；1-[Di(propan-2-yloxy)methyl]-4-nitrobenzene
• CAS: 54149-72-3
• 化学式: C₁₃H₁₉NO₄
• 分子量: 253.298
• InChiKey: XIEJZONRGBUKJI-UHFFFAOYSA-N

物化性质

• 沸点：
  319.7±32.0 °C(Predicted)
• 密度：
  1.097±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(diisopropoxymethyl)-4-nitrobenzene 在 还原型辅酶II(NADPH)四钠盐 rat liver S-9 、 硫酸 、 potassium chloride 、 magnesium chloride 作用下， 以 水 、 二甲基亚砜 为溶剂， 反应 7.0h， 生成 对氨基苯甲醛
  参考文献：
  名称：

  Synthesis of the cyclic and acyclic acetal derivatives of 1-(3-C-Ethynyl-β-d-ribo-pentofuranosyl)cytosine, a potent antitumor nucleoside. Design of prodrugs to be selectively activated in tumor tissues via the bio-Reduction–Hydrolysis mechanism☆

  摘要：

  We have designed and synthesized the acetal derivatives of 1-(3-C-ethynyl-beta-D-ribo-pentofuranosyl)cytosine (ECyd, 1), the 2',3'-O-nitrobenzylidene derivatives 2 and 3 and the 5'-O-(alkoxy)(nitrophenyl)methyl derivatives 6-10 as potential prodrugs of ECyd. These prodrugs can be selectively activated in tumor tissues via a bio-reduction hydrolysis mechanism owing to the characteristic properties of tumor tissues, such as hypoxia and lower pH. Although the 2',3'-O-(4-nitrobenzylidene) derivatives 2 and 3 were converted bio-reductively into the corresponding 4-aminobenzylidene derivatives by rat S-9 mix, the reduction products, that is, the corresponding amino congeners 4 and 5, proved to be rather stable in an aqueous solution at pH 6.5 used as a pH model for acidic tumor tissues. In contrast, the 5'-O-(alkoxy)(4-nitropheny)methyl derivatives 6-8 were also reduced by rat S-9 mix to the corresponding amino congeners 11-13, which were hydrolyzed to release ECyd more effectively at pH 6.5 than at pH 7.4. Accordingly, the acyclic acetals 6-8 may be efficient prodrugs of ECyd, that are effectively reduced under physiological conditions releasing ECyd in acidic tumor tissues. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(03)00104-4
• 作为产物：
  描述：

  对硝基苯甲醛 、 异丙醇 在 1-丙基磷酸酐 作用下， 以 乙酸乙酯 为溶剂， 以91%的产率得到1-(diisopropoxymethyl)-4-nitrobenzene
  参考文献：
  名称：

  丙基膦酸酐（®T3P）在室温下催化的醛的高效化学选择性缩醛化和硫代缩醛化

  摘要：

  丙膦酸酯（®T3P），一种低毒的肽偶联剂，已被证明是在酮存在下对醛进行化学选择性缩醛化和硫代缩醛化的有效催化剂。在催化量的T3P存在下，在室温下以良好或优异的收率获得了多种醛的环状和无环缩醛。

  DOI：

  10.1016/j.tetlet.2012.07.052

文献信息

• Carbon Tetrabromide/Sodium Triphenylphosphine-m-sulfonate (TPPMS) as an Efficient and Easily Recoverable Catalyst for Acetalization and Tetrahydropyranylation Reactions
  作者：Congde Huo、Tak Hang Chan

  DOI：10.1002/adsc.200900102

  日期：——

  A solid complex, conveniently prepared from carbon tetrabromide and sodium triphenylphosphine-m-sulfonate (TPPMS), can be used as an easily recoverable catalyst for the selective acetalization of aldehydes and tetrahydropyranylation of alcohols. The catalyst can be recovered by simple precipitation with ether and can be reused at least 7 times without loss of catalytic activity.

  固体复合物，从四溴化碳和钠triphenylphosphine-方便地制备米磺酸盐（TPPMS），可以被用作醛和醇的tetrahydropyranylation的选择性缩醛化的容易恢复的催化剂。可以通过简单的乙醚沉淀法回收催化剂，并且可以重复使用至少7次而不会损失催化活性。
• Chemoselective Protection of Aldehydes in the Presence of Ketones Using RuPVP Complex as a Heterogeneous Catalyst
  作者：Siddheshwar W. Kshirsagar、Nitin R. Patil、Shriniwas D. Samant

  DOI：10.1080/00397910902985457

  日期：2010.1.14

  and trihydrated ruthenium trichloride. RuPVP catalyst was characterized by Fourier transform–infrared and diffential scanning calorimetry–thermogravimetry (TG). The catalyst was used for chemoselective protection of aldehydes in the presence of a ketonic carbonyl group.

  通过回流聚乙烯吡啶和三水合三氯化钌的甲醇溶液制备钌 (III)-聚乙烯吡啶 (RuPVP) 络合物。RuPVP催化剂通过傅里叶变换-红外和差示扫描量热-热重（TG）表征。该催化剂用于在酮羰基存在下对醛进行化学选择性保护。
• Tunable Artificial Enzyme–Cofactor Complex for Selective Hydrolysis of Acetals
  作者：Ishani Bose、Shixin Fa、Yan Zhao

  DOI：10.1021/acs.joc.0c02519

  日期：2021.1.15

  use unimpressive functional groups such as weak carboxylic acids for efficient, highly selective catalysis including hydrolysis of acetals and even amides. Much stronger acids generally have to be used for such purposes in synthetic systems. We report here a method to position an acidic group near the acetal oxygen of 2-(4-nitrophenyl)-1,3-dioxolane bound by an artificial enzyme. The hydrolytic activity

  酶经常使用不起眼的官能团（例如弱羧酸）来进行高效、高选择性的催化，包括缩醛甚至酰胺的水解。在合成系统中通常必须使用更强的酸来达到这样的目的。我们在此报告了一种将酸性基团定位在人工酶结合的 2-(4-硝基苯基)-1,3-二氧戊环的缩醛氧附近的方法。所得人工酶-辅因子复合物的水解活性通过活性位点的数量和深度以及辅因子的疏水性和酸性进行调节。复合物的选择性由活性位点的大小和形状控制，使得反应性较低的缩醛比反应性较高的缩醛能够被水解。
• New Type of Aldol Condensations Catalyzed by Metal(II) Complexes of α-Amino Acid Esters and that with Cyclodextrin System
  作者：Ken-ichi Watanabe、Yoichi Yamada、Katsuhisa Goto

  DOI：10.1246/bcsj.58.1401

  日期：1985.5

  p-nitrobenzaldehyde with acetone catalyzed by metal complexes of α-amino acid esters proceeded under mild and neutral conditions to afford an enantiomeric excess aldol-type product, 4-hydroxy-4-(4-nitrophenyl)-2-butanone, along with some dehydrated products without any by-product. The most effective catalyst system was a zinc(II) complex of the tyrosine ethyl ester, ZnII–(TyrOEt)2 in MeOH. Complexes

  α-氨基酸酯金属配合物催化对硝基苯甲醛与丙酮的羟醛缩合反应在温和和中性条件下进行，得到对映体过量的羟醛型产物 4-羟基-4-(4-硝基苯基)-2-丁酮，以及一些没有任何副产品的脱水产品。最有效的催化剂体系是酪氨酸乙酯 ZnII-(TyrOEt)2 在 MeOH 中的锌 (II) 络合物。第二排过渡金属的配合物不足以进行反应。在 30-40°C 下反应 24 小时对于不对称诱导是有利的。H2O 溶剂对于没有不对称诱导的羟醛型产物形成是最好的。环糊精（尤其是 β-CD）对 ZnII-TyrOEt 复合物的催化作用被认为是观察到的。
• Selective acetalization of aldehydes with trialkoxystibine using allyl bromide
  作者：Yi Liao、Yao-Zeng Huang、Fang-Hua Zhu

  DOI：10.1039/c39900000493

  日期：——

  Trialkoxystibine has been found to be an effective reagent for selective acetalization of aldehydes with the aid of allyl bromide.

  已经发现三烷氧基他滨是在烯丙基溴的帮助下对醛进行选择性缩醛化的有效试剂。