(Z)-O-methyl-4-methoxybenzohydroximoyl bromide | 140462-99-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (Z)-O-methyl-4-methoxybenzohydroximoyl bromide
• 英文别名: (Z)-N,4-dimethoxybenzenecarboximidoyl bromide；4-methoxy-O-methylbenzohydroximoyl bromide；(1Z)-N,4-dimethoxybenzenecarboximidoyl bromide
• CAS: 140462-99-3
• 化学式: C₉H₁₀BrNO₂
• 分子量: 244.088
• InChiKey: QNZVPNOLIVHOQC-LUAWRHEFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  30.82
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (Z)-O-methyl-4-methoxybenzohydroximoyl bromide 以0%的产率得到
  参考文献：
  名称：

  Sakamoto Takeshi, Kikugawa Yasuo, Synthesis, (1993) N 6, S 563-564

  摘要：

  DOI：
• 作为产物：
  描述：

  N-methoxy-4-methoxylbenzamide 在 四溴化碳 、 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 3.0h， 生成 (Z)-O-methyl-4-methoxybenzohydroximoyl bromide
  参考文献：
  名称：

  Imino 1,2-Wittig rearrangement of hydroximates and its application to synthesis of cytoxazone

  摘要：

  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.

  DOI：

  10.1016/j.tet.2004.02.048

文献信息

• Mechanism of Methoxide Ion Substitution in the <i>Z</i> and <i>E</i> Isomers of <i>O</i>-Methylbenzohydroximoyl Halides
  作者：James E. Johnson、Debra D. Dolliver、Lonchun Yu、Diana C. Canseco、Michael A. McAllister、Jeffrey E. Rowe

  DOI：10.1021/jo030299e

  日期：2004.4.1

  isomers of O-methylbenzohydroximoyl halides [1Z and 1E, ArC(X)NOCH3] with sodium methoxide in 9:1 DMSO−methanol. The reactions of methoxide ion with hydroximoyl fluorides (X = F) are stereospecific. The reaction with 1Z (X = F) gives only the Z substitution product (1Z, X OCH3). The reaction of methoxide ion with 1E (X = F) is less selective, giving ca. 85% E substitution product. The Hammett ρ-values for

  在9：1 DMSO-甲醇中，对O-甲基苯并氧肟基卤化物的Z和E异构体[ 1Z和1E，ArC（X）NOCH 3 ]与甲醇钠的反应进行了动力学和立体化学研究。甲醇离子与羟肟基氟化物（X = F）的反应是立体定向的。与1Z（X = F）的反应仅给出Z取代产物（1Z，X OCH 3）。甲醇离子与1E（X = F）的反应选择性较低，大约为。E替代品占85％。的哈米特ρ值Z和E异构体（X = F）分别为+2.94和+3.30。1Z（Ar = C 6 H 5）的元素效应为2.21（X = Br）：1.00（X = Cl）：79.7（X = F）。所述1E元件效果（AR = C 6 H ^ 5）1.00（X = Cl）的：18.3（X = F）和（AR = 4-CH 3 OC 6 H ^ 4）1.97（X = Br的）：1.00（X = Cl）：12.1（X ＝ F）。激活用于这些反应的熵是否定的（例如，Δ小号⧧
• The Preparation of Methyl (E)- and (Z)-O-Methylbenzothiohydroximates
  作者：James E. Johnson、Diana C. Canseco、Jeffrey E. Rowe

  DOI：10.1071/ch03218

  日期：——

  methyl (Z)-O-methylbenzothiohydroximates were prepared either by reaction of the corresponding (Z)-N-methoxybenzenecarboximidoyl bromides with potassium fluoride in dimethyl sulfoxide, or by reaction of N-methoxybenzamides with Lawesson’s reagent followed by alkylation. Irradiation of the Z isomers led to a photostationary equilibrium containing mixtures of approx. 40% E and 60% Z, from which the E isomers

  通过相应的 (Z)-N-甲氧基苯甲酰溴与氟化钾在二甲亚砜中的反应，或通过 N-甲氧基苯甲酰胺与劳森试剂反应然后烷基化来制备一系列甲基 (Z)-O-甲基苯并硫代羟肟酸盐。Z异构体的辐照导致含有约。40% E 和 60% Z，从中分离出 E 异构体。
• The Preparation of Imidoyl Fluorides
  作者：Jeffrey E. Rowe、Kam Lee、Debra D. Dolliver、James E. Johnson

  DOI：10.1071/ch99032

  日期：——

  The first general synthesis of imidoyl fluorides is reported here. Irradiation of the initially formed Z isomers of N-methoxybenzenecarboximidoyl fluorides led to a photoequilibrium containing both the E and Z isomers. The pure E isomers were able to be isolated from these isomeric mixtures. The n.m.r. spectra of these isomers are discussed.

  本文首次报道了酰亚胺基氟化物的一般合成方法。辐照 辐照最初形成的 N-甲氧基苯甲酰亚胺酰氟最初形成的 Z 异构体在辐照下产生了 光平衡，同时含有 E 和 Z 异构体。纯 E 异构体 从这些异构混合物中分离出了纯 E 异构体。讨论了这些异构体的 n.m.r. 光谱。 对这些异构体的 n.m.r. 光谱进行了讨论。
• 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）。
• Synthesis of<i>N</i>-alkoxybenzimidoyl azides and their reactions in electrophilic media
  作者：Debra D. Dolliver、Thomas Sommerfeld、Megan L. Lanier、Jordan A. Dinser、Richard P. Rucker、Rebecca J. Weber、Artie S. McKim

  DOI：10.1002/poc.1608

  日期：——

  (trifluoroacetic acid or acetyl chloride), these azide compounds can react by two pathways: a Schmidt‐type rearrangement to form an N‐alkoxyurea or an isomerization–cyclization reaction pathway to form an N‐alkoxytetrazole. The route of the reaction has no dependence on solvent polarity and appears to depend upon the electrophile (H+ vs. CH3CO+): reaction of the azide with trifluoroacetic acid results predominantly

  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