(Z)-N-methoxy-4-nitrobenzenecarboximidoyl bromide | 97315-84-9

• 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: (Z)-N-methoxy-4-nitrobenzenecarboximidoyl bromide
• 英文别名: (Z)-O-methyl-p-nitrobenzohydroximoyl bromide；(1Z)-N-methoxy-4-nitrobenzenecarboximidoyl bromide
• CAS: 97315-84-9
• 化学式: C₈H₇BrN₂O₃
• 分子量: 259.059
• InChiKey: HGUHLNKSLNPDIR-NTMALXAHSA-N

物化性质

• 沸点：
  327.7±44.0 °C(Predicted)
• 密度：
  1.60±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  67.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (Z)-N-methoxy-4-nitrobenzenecarboximidoyl bromide 以87%的产率得到(Z)-N-methoxy-4-nitrobenzenecarboximidoyl azide
  参考文献：
  名称：

  N-烷氧基苯甲酰亚胺基叠氮化物的合成及其在亲电介质中的反应

  摘要：

  到一个新的一般路线Ñ -alkoxybenzimidoyl叠氮化物[ARC（N 3）= NOR]从的反应Ñ -alkoxybenzimidoyl溴化物[ARC（BR）= NOR]在DMSO中的叠氮化钠进行说明。这些反应导致Z几何配置。通过差示扫描量热法评估，这些化合物显示出中等程度的热稳定性，并且在传统的1,3-偶极环加成“点击”反应中缺乏反应性。暴露于亲电子化合物（三氟乙酸或乙酰氯）后，这些叠氮化合物可以通过两种途径发生反应：施密特型重排形成N-烷氧基脲或异构化-环化反应途径形成N烷氧基四唑 反应路线与溶剂极性无关，并且似乎取决于亲电子试剂（H + 与CH 3 CO +）：叠氮化物与三氟乙酸的反应主要产生尿素；与乙酰氯的反应仅产生四唑。计算表明，尿素产物在热力学上优于四唑产物。它们还表明两种反应条件均导致起始叠氮化物和四唑之间的平衡，其中四唑是该平衡混合物中的主要成分。叠氮化物还会经历S

  DOI：

  10.1002/poc.1608
• 作为产物：
  描述：

  N-methoxy-4-nitrobenzamide 在 溴 、 三溴化磷 作用下， 以 苯 为溶剂， 生成 (Z)-N-methoxy-4-nitrobenzenecarboximidoyl bromide
  参考文献：
  名称：

  N-烷氧基亚氨基碘化物和溴化物的立体特异性铃木，Sonogashira和Negishi偶联反应

  摘要：

  描述了通过N-烷氧基酰亚胺基碘化物的Suzuki偶联合成二芳基肟醚的单一几何异构体的高产立体定向途径。该反应在完全保留酰亚胺基卤化物几何形状的情况下发生，从而给出二芳基肟醚的单一E-或Z-异构体。还已经开发了N-烷氧基酰亚胺基碘化物和溴化物与各种各样的末端炔烃的Sonogashira偶联，以提供芳基炔基肟肟醚的单一几何异构体。其中一些反应是在无铜条件下进行的。介绍了N-烷氧基亚氨基卤化物的Negishi偶联。该Ë和ž X射线晶体学证实了九种铃木偶联产物和两种Sonogashira偶联产物的构型。

  DOI：

  10.1021/jo400179u

文献信息

• Mechanism of bimolecular substitution reactions of hydroximoyl halides with amines in actonitrile solution
  作者：James E. Johnson、Susan M. Dutson、Debra D. Dolliver、Susan L. Todd、Martha Hotema

  DOI：10.1002/poc.610080505

  日期：1995.5

  ρ-value (with σ) for the reaction with pyrrolidine is +0·92. The reaction of the p-nitro compound with pyrrolidine gives a significant element effect [k(p-nitrobenzohydroximoyl bromide)/k(p)-nitrobenzohydroximoyl chloride = 10]. A Brϕonsted β-value of 0·38 was estimated from the reactions of morpholine and piperidine with the p-nitrohydroximoyl chloride. The slower reaction of (E)-O-methyl-p-nitrobenzohydroximoyl

  （Z）-O-甲基苯并氢氧氯化物[ArC（Cl）NOCH 3 ]在乙腈溶液中与吗啉，吡咯烷和氮杂环丁烷反应，得到相应的（Z）-氨基肟[ArC（NR 1 R 2）NOCH 3 ]在乙腈中的反应。这些反应的速率是在拟一级条件（过量胺）下测量的。发现反应遵循总体二级动力学（在胺中一级）。与吡咯烷反应的哈米特ρ值（带有σ）为+ 0·92。对硝基化合物与吡咯烷的反应产生了显着的元素效应[ k（p-硝基苯甲氧基肟基溴化物/ k（p）-硝基苯甲氧基肟基氯＝ 10]。从吗啉和哌啶与对-硝基羟肟基氯的反应估计布朗斯通的β值为0·38 。（E）-O-甲基-对硝基苯并氧肟基氯与氮杂环丁烷的较慢反应主要产生（E）-ami胺肟（E：Z≈98：2）此反应也遵循二级动力学。将该研究中的动力学观察结果与在苯溶液中早期工作中获得的相应结果进行比较。建议在乙腈溶液中，反应通过加成消除机理进行，该速率决定氯离子的损失速率（A N
• Synthesis of O-Alkylbenzohydroximoyl Iodides and a Comparison of their Structures to other Oxime Derivatives
  作者：Debra D. Dolliver、Smitty Smith、David B. Delatte、Kavi D. Patel、Tiffany E. Thomas、Julie Chagnard、James E. Johnson、Diana C. Canseco、Frank R. Fronczek、Clinton D. Bryan、JoAnn R. Muller、Jeffrey E. Rowe、Artie S. McKim

  DOI：10.1007/s10870-007-9257-y

  日期：2007.12

  The first general synthesis of (Z)-O-alkylbenzohydroximidoyl iodides [ArC(I)=NOR] is reported. X-ray crystallographic structures of two of these compounds confirm that they are in the Z-configuration: p-NO2ArC(I)=NOCH3 crystallizes in space group Pnma with lattice constants a = 12.682(2) Å, b = 6.5217(15) Å, and c = 11.755(2) Å, and p-ClArC(I)=NOCH3 crystallizes in space group P21/n with lattice constants a = 15.670(4) Å, b = 5.742(4) Å, and c = 27.156(7) Å and beta angle 102.71(2). Their structures are compared to other O-alkylbenzohydroximoyl halides including p-NO2ArC(F)=NOCH3 which crystallizes in space group P21/c with lattice constants a = 3.8475(10) Å, b = 22.501(5) Å, and c = 10.088(2) Å and beta angle 91.130(11). The synthesis of two additional compounds containing the N-alkoxyimine moiety methyl (Z)-O-methyl-4-nitrobenzothiohydroximate [p-NO2ArC(SCH3)=NOCH3] which crystallizes in space group P21/n with lattice constants a = 11.8046(15) Å, b = 7.0774(10) Å, and c = 12.2741(15) Å and beta angle 100.401(9) and (Z)-O-methyl-4-nitrobenzohydroximoyl azide [p-NO2ArC(N3)=NOCH3] which crystallizes in space group P21/c with lattice constants a = 11.753(2) Å, b = 11.310(3) Å, and c = 7.351(2) Å and beta angle 103.805(15) are also reported. Their structures are compared to (Z)-ethyl benzohydroximate [PhC(OEt)=NOH] and (Z)-O-methyl-4-nitrobenzohydroximoyl cyanide [p-NO2ArC(CN)=NOCH3] respectively. Characterizations include spectrometric identifications employing IR, 1H-NMR, 13C-NMR and mass spectrometry. X-ray structures of several N-alkoxyimines, including the newly synthesized N-alkoxyimidoyl iodides and azide, have been performed, and these structures unambiguously show the geometric configuration (E vs. Z) of these compounds.

  报道了 (Z)-O-烷基苯并羟基肟酰碘 [ArC(I)=NOR] 的第一个一般合成。其中两种化合物的 X 射线晶体结构证实它们处于 Z 构型：p-NO2ArC(I)=NOCH3 在空间群 Pnma 中结晶，晶格常数 a = 12.682(2) Å，b = 6.5217(15) Å，c = 11.755(2) Å，p-ClArC(I)=NOCH3 在空间群 P21/n 中结晶，晶格常数 a = 15.670(4) Å，b = 5.742(4) Å，c = 27.156 (7) Å 和 β 角 102.71(2)。它们的结构与其他 O-烷基苯并羟基肟酰卤化物进行了比较，包括 p-NO2ArC(F)=NOCH3，其在空间群 P21/c 中结晶，晶格常数 a = 3.8475(10) Å、b = 22.501(5) Å 和 c = 10.088 (2) Å 和 β 角 91.130(11)。合成另外两种含有 N-烷氧基亚胺部分的化合物甲基 (Z)-O-甲基-4-硝基苯并硫代肟酸酯 [p-NO2ArC(SCH3)=NOCH3]，其在空间群 P21/n 中结晶，晶格常数 a = 11.8046( 15) Å，b = 7.0774(10) Å，c = 12.2741(15) Å 和 β 角 100.401(9) 和 (Z)-O-甲基-4-硝基苯并羟基肟酰叠氮化物 [p-NO2ArC(N3)=NOCH3]其在空间群 P21/c 中结晶，晶格常数 a = 11.753(2) Å、b = 11.310(3) Å、c = 7.351(2) Å 和 β 角 103.805(15)。将它们的结构分别与(Z)-苯并羟肟酸乙酯[PhC(OEt)=NOH]和(Z)-O-甲基-4-硝基苯并羟肟酰氰化物[p-NO2ArC(CN)=NOCH3]进行比较。表征包括采用 IR、1H-NMR、13C-NMR 和质谱的光谱鉴定。已经对几种 N-烷氧基亚胺（包括新合成的 N-烷氧基亚胺酰碘化物和叠氮化物）进行了 X 射线结构分析，这些结构明确地显示了这些化合物的几何构型（E 与 Z）。
• Imino 1,2-Wittig rearrangement of hydroximates and its application to synthesis of cytoxazone
  作者：Okiko Miyata、Tomoko Koizumi、Hiroshi Asai、Ryuichi Iba、Takeaki Naito

  DOI：10.1016/j.tet.2004.02.048

  日期：2004.4

  The imino 1,2-Wittig rearrangement of hydroximates provides a novel method for the construction of 2-hydroxyoxime ethers. Upon treatment with LDA, Z-hydroximates smoothly underwent stereoselective rearrangement to give Z-2-hydroxyoxime ethers in good yield, which were converted into amino alcohols. On the other hand, the rearrangement of E-hydroximates gave a mixture of E- and Z-2-hydroxyoxime ethers. This method was successfully applied to a practical synthesis of cytoxazone. (C) 2004 Elsevier Ltd. All rights reserved.
• Mechanism of amine and amide ion substitution reactions at the carbon-nitrogen double bond
  作者：James Elver Johnson、Abdolkarim Ghafouripour、Mohammad Arfan、Susan L. Todd、Deborah A. Sitz

  DOI：10.1021/jo00218a021

  日期：1985.9
• Mechanisms and stereochemistry of amine substitution reactions at the carbon-nitrogen double bond
  作者：James Elver Johnson、Susan L. Todd、Susan M. Dutson、Abdolkarim Ghafouripour、Reidun M. Alderman、Martha R. Hotema

  DOI：10.1021/jo00043a022

  日期：1992.8

  The reaction of (Z)-O-methyl-p-nitrobenzohydroximoyl chloride [4-NO2C6H4C(Cl)=NOCH3] with morpholine, piperidine, pyrrolidine, and azetidine gives the corresponding (Z)-amidoximes [4-NO2C6H4C(NR1R2)=NOCH3]. The rate equations for these reactions in benzene solution contain both first-order and second-order terms in amine. The rates of these reactions increase with increasing basicity [k(pyrrolidine > k(morpholine)] and d size of the amine [k(azetidine) > k(pyrrolidine) > k(piperidine)]. The approximate Hammett rho-values for the reaction of (Z)-hydroximoyl chlorides with azetidine are +1.0 for the amine-catalyzed process and 0 for the uncatalyzed pathway. The element effect, k(p-nitrobenzohydroximoyl bromide)/k(p-nitrobenzohydroximoyl chloride), is 11.9 for the amine-catalyzed reaction and 8.16 for the uncatalyzed reaction. These results suggest that the reactions proceed by an addition-elimination mechanism (A(N) + D(N)) in which the amine is deprotonating the zwitterionic tetrahedral intermediate in the amine-catalyzed process. The slow reaction of azetidine in benzene solution with (E)-O-methyl-p-nitrobenzohydroximoyl chloride gives a mixture of the (Z)- and (E)-amidoxime with the E isomer predominating (E/Z is-approximately-equal-to 98:2). The rate equation for this reaction contains first-order and third-order terms in azetidine. It is suggested that the amine-catalyzed route involves nucleophilic attack by an amine monomer to form a tetrahedral intermediate which breaks down with the assistance of an amine dimer (or the homoconjugate acid of the amine). The difference in the observed rate equations for (Z)- and (E)-hydroximoyl chlorides with azetidine is attributed to stereoelectronic effects.