methyl 2-(1-phenylethylidene)hydrazine-1-carboxylate | 91842-96-5

• 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: methyl 2-(1-phenylethylidene)hydrazine-1-carboxylate
• 英文别名: Acetophenone carbomethoxyhydrazone；methyl N-(1-phenylethylideneamino)carbamate
• CAS: 91842-96-5
• 化学式: C₁₀H₁₂N₂O₂
• 分子量: 192.217
• InChiKey: ZTHZAPSVRRTCSR-UHFFFAOYSA-N

物化性质

• 熔点：
  118-120 °C(Solv: water (7732-18-5); methanol (67-56-1))
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  50.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-(1-phenylethylidene)hydrazine-1-carboxylate 在 乙醇 、 platinum on activated charcoal 作用下， 生成 3-(alpha-甲基苄基)肼基甲酸甲酯
  参考文献：
  名称：

  DE951503

  摘要：

  公开号：
• 作为产物：
  描述：

  methyl 2-(2-(diphenylphosphoryl)-1-phenylethylidene)-hydrazine-1-carboxylate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 水 为溶剂， 以49 %的产率得到methyl 2-(1-phenylethylidene)hydrazine-1-carboxylate
  参考文献：
  名称：

  铜催化炔烃的立体选择性自由基膦酰肼化

  摘要：

  描述了一种铜催化的末端炔烃与氨基甲酸烷基酯和二芳基氧化膦的立体选择性膦酰肼化反应。该方法提供了以令人满意的收率轻松获得各种 β-肼基膦氧化物的途径。该反应在温和条件下进行，并表现出良好的官能团耐受性。提出了一种以过硫酸盐介导的氧化生成膦酰基自由基和铜辅助的水合作用为特征的机制。

  DOI：

  10.1021/acs.joc.2c01959

文献信息

• Synthesis and Crystal Structure Determination of Methyl 2-acetyl-5′-phenyl-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate and Methyl 2-acetyl-5′-(2-thienyl)-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate
  作者：Clyde R. Metz、John D. Knight、Anna C. Dawsey、William T. Pennington、Donald G. VanDerveer、Jordan B. Brown、Kevin J. Bigham、Charles F. Beam

  DOI：10.1007/s10870-009-9649-2

  日期：2010.4

  Dilithiated C(α), N-carbomethoxyhydrazones were condensed with lithiated methyl 2-(aminosulfonyl)benzoate to afford intermediates that were isolated and not characterized but cyclized with acetic anhydride, which also resulted in N-acetylation. The X-ray crystal structure determinations of methyl 2-acetyl-5′-phenyl-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate and methyl 2-acetyl-5′-(2-thienyl)-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate products were a follow up for absorption spectra, and they confirmed their structures. Mechanistic intermediates to describe the reaction may include C-acylated intermediates that cyclize to spiro(N-benzoisothiazole dioxide-pyrazole) instead of N-carbomethoxypyrazole-ortho-benzenesulfonamides. Crystals of C19H17N3O5S 7 are monoclinic, P21/c, a = 11.899(2) Å, b = 17.562(4) Å, c = 9.484(2) Å, β = 111.03(3)°, Z = 4, V = 1849.9(6) Å3, R 1 = 0.0857 and wR 2 = 0.2216 for reflections with I > 2σ(I); crystals of C17H15N3O5S2 8 are orthorhombic, Pbca, a = 16.045(3) Å, b = 10.746(2) Å, c = 20.389(4) Å, Z = 8, V = 3516(1) Å3, R 1 = 0.0841 and wR 2 = 0.2179 for all reflections with I > 2σ(I). X-ray crystal analysis was important for determining the conformation of the structure of N-acetyl-N′-carbomethoxy-spiro(benzoisothiazole–pyrazole)dioxides prepared by the condensation and twofold cyclization of dilithiated C(α), N-carbomethoxyhydrazones and methyl 2-(aminosulfonyl)benzoate.

  二锂化的C(α), N-羧甲基酰肼与甲基2-(氨基磺酰基)苯甲酸锂反应生成中间体，这些中间体被分离出来但未进行表征，但在乙酸酐的作用下环化，并导致N-乙酰化。甲基2-乙酰基-5′-苯基-2H-螺[苯并[d]异噻唑-3,3′-吡唑]-1,1-二氧化物-2′(4′H)-羧酸酯和甲基2-乙酰基-5′-(2-噻吩基)-2H-螺[苯并[d]异噻唑-3,3′-吡唑]-1,1-二氧化物-2′(4′H)-羧酸酯的X射线晶体结构测定是对吸收光谱的后续研究，并确认了它们的结构。描述反应的机制中间体可能包括环化为螺(N-苯并异噻唑二氧化物-吡唑)而不是N-羧甲基吡唑-邻苯并磺酰胺的C-酰化中间体。C19H17N3O5S 7的晶体为单斜晶系，P21/c，a = 11.899(2) Å，b = 17.562(4) Å，c = 9.484(2) Å，β = 111.03(3)°，Z = 4，V = 1849.9(6) Å3，R 1 = 0.0857，wR 2 = 0.2216（对于I > 2σ(I)的反射）；C17H15N3O5S2 8的晶体为正交晶系，Pbca，a = 16.045(3) Å，b = 10.746(2) Å，c = 20.389(4) Å，Z = 8，V = 3516(1) Å3，R 1 = 0.0841，wR 2 = 0.2179（对于所有I > 2σ(I)的反射）。X射线晶体分析对于确定由二锂化的C(α), N-羧甲基酰肼与甲基2-(氨基磺酰基)苯甲酸酯的缩合和双环化反应制备的N-乙酰-N′-羧甲基螺(苯并异噻唑-吡唑)二氧化物的结构构型非常重要。
• Carbazic Acid Esters as Carbonyl Reagents
  作者：Norman Rabjohn、H. D. Barnstorff

  DOI：10.1021/ja01105a513

  日期：1953.5
• A New Series of Proton/Charge Transfer Molecules: Synthesis and Spectral Studies of 2-(5-Aryl-1-carbomethoxy-1H-pyrazol-3-yl)phenols
  作者：Mary E. Rampey、Carrie E. Halkyard、Angela R. Williams、April J. Angel、Douglas R. Hurst、Jessica D. Townsend、Anne E. Finefrock、Charles F. Beam、Shannon L. Studer-Martinez

  DOI：10.1111/j.1751-1097.1999.tb07987.x

  日期：1999.8

  Abstract. The carbomethoxyhydrazone of 2′‐hydroxyacetophenone was trilithiated with excess lithium diisopropylamide and C‐acylated with a variety of benzoate esters followed by acid cyclization of the intermediates to 2‐(5‐aryl‐l‐car‐bomethoxy‐lHpyrazol‐3‐yl)phenols [3‐(2‐hydroxyphen‐yl)‐lH‐pyrazoles]. The products were characterized by Fourier transform‐IR, lH NMR, 13C NMR, UV‐visible absorption and fluorescence. All the derivatives in n ‐heptane have an absorption maximum at ˜304 nm and an extremely weak (φr= 10 4) fluorescence with maxima in the range of 335–460 nm. The broad range of fluorescence maxima and fluorescence quantum yields is attributed to varying contributions of charge transfer that are dependent on both the identity of the substituent and solvent polarity. A phenomenally large Stokes‐shifted fluorescence maximum at 620 nm was observed for 2‐(l‐car‐bomethoxy‐5‐[4‐dimethylaminophenyl]‐lff‐pyrazol‐3‐y1)phenol in n‐heptane and attributed to excited‐state intramolecular proton transfer. As a result, competitive excited‐state proton/charge transfer properties have been observed in the pyrazoles studied, of which the spectral properties can be fine tuned by substituent as well as solvent effects.
• Huff, Ann M.; Beam, Charles F., Journal of Heterocyclic Chemistry, 1986, vol. 23, p. 1343 - 1346
  作者：Huff, Ann M.、Beam, Charles F.

  DOI：——

  日期：——
• Duncan, Dean C.; Trumbo, Todd A.; Almquist, Catharine D., Journal of Heterocyclic Chemistry, 1987, vol. 24, p. 555 - 560
  作者：Duncan, Dean C.、Trumbo, Todd A.、Almquist, Catharine D.、Lentz, Teresa A.、Beam, Charles F.

  DOI：——

  日期：——