ethyl 3-(5-methoxy-2-nitrophenyl)pyruvate | 131761-77-8

• 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: ethyl 3-(5-methoxy-2-nitrophenyl)pyruvate
• 英文别名: ethyl 3-(5-methoxy-2-nitrophenyl)-2-oxopropanoate
• CAS: 131761-77-8
• 化学式: C₁₂H₁₃NO₆
• 分子量: 267.238
• InChiKey: ZPOUOVFBCAXACL-UHFFFAOYSA-N

物化性质

• 熔点：
  81-82 °C
• 沸点：
  419.3±35.0 °C(Predicted)
• 密度：
  1.283±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 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：
  98.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 3-(5-methoxy-2-nitrophenyl)pyruvate 在 palladium on activated charcoal sodium tetrahydroborate 作用下， 以 1,4-二氧六环 、 水 为溶剂， 以25%的产率得到1,3-dihydroxy-6-methoxy-1,2,3,4-tetrahydroquinolin-2-one
  参考文献：
  名称：

  Analogs of the cyclic hydroxamic acid 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3-one (DIMBOA): decomposition to benzoxazolinones and reaction with .beta.-mercaptoethanol

  摘要：

  Analogues of the aglucones of naturally occurring cyclic hydroxamic acids (2,4-dihydroxy-1,4-benzoxazin-3-ones) from Gramineae (Poaceae) have been synthesized by the reductive cyclization of the ring-substituted methyl alpha-(o-nitrophenoxy)-alpha-methoxyacetates, followed by demethylation of the C-2 methoxy group with BBr3 or BCl3 to reveal the 2-hydroxy group. A structure-activity series was produced by varying the substituent at C-7 on the aromatic ring [R = MeO (1), t-Bu (6), Me (7), H (8), Cl (9), F (10), CO2Me (11a)]. The pK(a) values for the hydroxamic acid and the phenol moieties were determined for each member of the C-7 series. They correlated well with sigma in a linear free energy relationship (LFER) yielding values of rho = 0.71 (with sigma-p) for pK(a1) (the hydroxamic acid) and rho = 1.6 (with sigma-m) for pK(a2) (the phenol). A LFER also existed between the rate constants for the unimolecular decomposition of these hydroxamic acids to benzoxazolinones and sigma+ (rho = 1.1). The rates of hydroxamic acid reduction to lactams by beta-mercaptoethanol were also investigated. It was found that only compounds with electron-rich aromatic rings and specifically an oxa functionality para to the hydroxamic acid nitrogen atom (compounds 1 and 3-5) had measurable rates of reduction. H-1 NMR spectra recorded during this reaction in D2O buffers (pD9), however, showed that compounds 1, 2, 6-9 (the only ones investigated) formed a hemithioacetal at C-2 even though only 1 has a measurable rate of reduction by the same thiol. The remarkable rate enhancement provided by an oxa functionality suggests that reduction occurs by direct attack of thiolate on the hydroxamic nitrogen of a resonance-stabilized ion pair.

  DOI：

  10.1021/jo00005a025
• 作为产物：
  描述：

  ethyl 2-(5-methoxy-2-nitrobenzyl)-3-oxobutanoate 在 manganese(III) triacetate dihydrate 、 溶剂黄146 、 三氟乙酸 、 cobalt(II) chloride 作用下， 反应 7.0h， 以69%的产率得到ethyl 3-(5-methoxy-2-nitrophenyl)pyruvate
  参考文献：
  名称：

  乙酰乙酸酯的串联催化氧化脱乙酰基和杂芳族环化†

  摘要：

  一锅合成呋喃，噻吩和吡咯是通过使用Mn（III）/ Co（II）催化剂进行氧化脱乙酰作用以及1,5-二羰基化合物的Paal-Knorr反应完成的，该反应是通过乙酰乙酸乙酯的共轭加成制备的α，β-不饱和羰基化合物。衍生自乙酰乙酸乙酯和邻硝基苄基溴化物的β-酮酸酯的氧化脱乙酰基和还原环化有效地产生了各种取代的吲哚。

  DOI：

  10.1039/c4ob02441a

文献信息

• Preparation of Optically Enriched 3-Hydroxy-3,4-dihydroquinolin-2(1<i>H</i>)-ones by Heterogeneous Catalytic Cascade Reaction over Supported Platinum Catalyst
  作者：György Szőllősi、Zsolt Makra、Lenke Kovács、Ferenc Fülöp、Mihály Bartók

  DOI：10.1002/adsc.201300121

  日期：2013.5.17

  The development of a novel heterogeneous catalytic asymmetric cascade reaction for the synthesis of tetrahydroquinolines from 2‐nitrophenylpyruvates is reported. Optically enriched 3‐hydroxy‐3,4‐dihydroquinolin‐2(1H)‐ones are prepared by enantioselective hydrogenation of the activated keto group over a Cinchona alkaloid‐modified Pt catalyst, reduction of the nitro group and spontaneous cyclization

  据报道，从2-硝基苯基丙酮酸合成四氢喹啉的新型非均相催化不对称级联反应的发展。通过在金鸡纳生物碱修饰的Pt催化剂上对活化的酮基进行对映选择性加氢，还原硝基和自发环化级联反应，可以制备光学富集的3-羟基-3,4-二氢喹啉-2（1 H）-酮。在金鸡纳改性的催化剂上，活性酮基的对映选择性氢化的促进生物碱确保了高的四氢喹啉酮选择性。使用十二种底物检查反应范围。产率和对映选择性都受到苯环上取代基的性质和位置的显着影响。由于邻近硝基的取代基会影响硝基的还原速率，因此大大提高了产品收率。但是，它对映选择性的作用有限。
• 아세토아세틱 에스테르 화합물을 이용한 인돌의 합성방법
  申请人：Myongji University Industry and Academia Cooperation Foundation 명지대학교 산학협력단(220050139720) BRN ▼135-82-11060

  公开号：KR101599969B1

  公开（公告）日：2016-03-04

  본 발명은 아세토아세틱 에스테르를 이용한 인돌의 합성방법에 관한 것으로 더욱 상세하게는 아세토아세틱 에스테르 화합물을 2-니트로벤질 브로마이드 화합물에 첨가시켜 얻어지는 2-니트로벤질 아세톤 화합물에 망간(III)/코발트(II) 촉매를 이용한 탈아세틸화 반응을 적용하여 2-니트로벤질 케톤 화합물을 합성한 다음, 여기에 금속 촉매를 이용한 수소화 반응을 적용하여 니트로기의 아민기로의 환원과 더불어 케톤기와의 아로마틱 고리화 반응을 유발하여 인돌을 합성하는 방법에 관한 것이다.

  本发明涉及一种利用乙酰乙酸酯合成吲哚的方法，更具体地说，涉及一种通过将乙酰乙酸酯化合物加入2-硝基苯甲溴化合物得到2-硝基苯甲酮化合物，然后应用锰（III）/钴（II）催化剂进行脱乙酰化反应合成2-硝基苯甲酮化合物，随后应用金属催化剂进行氢化反应，促使硝基基团还原为胺基并引发与酮基的芳环化反应，从而合成吲哚的方法。
• 191. The synthesis of some 3-aminohydrocarbostyrils
  作者：R. E. Bowman、P. J. Islip、I. M. Lockhart、K. E. Richards、M. Wright

  DOI：10.1039/jr9650001080

  日期：——
• Suzuki; Gyoutoku; Yokoo, Synlett, 2000, # 8, p. 1196 - 1198
  作者：Suzuki、Gyoutoku、Yokoo、Shinba、Sato、Yamada、Murakami

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• Faltis et al., Chemische Berichte, 1944, vol. 77/79, p. 686,694
  作者：Faltis et al.

  DOI：——

  日期：——