5-bromospiro(1-pyrazoline-3,1'-cyclopropane) | 211738-70-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 5-bromospiro(1-pyrazoline-3,1'-cyclopropane)
• 英文别名: 6-Bromo-4,5-diazaspiro[2.4]hept-4-ene
• CAS: 211738-70-4
• 化学式: C₅H₇BrN₂
• 分子量: 175.028
• InChiKey: WDOMXUHCDWZKKX-UHFFFAOYSA-N

物化性质

• 沸点：
  188.6±29.0 °C(Predicted)
• 密度：
  2.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-bromospiro(1-pyrazoline-3,1'-cyclopropane) 在 sodium azide 作用下， 以 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 3.0h， 生成 Z-N-{3-azidospiro[1-pyrazolinio-5,1'-cyclopropane]}-N-phthalimidoamide
  参考文献：
  名称：

  Different reactivities of regioisomeric azimines, adducts of phthalimidonitrene with 5-bromospiro[1-pyrazoline-3,1′-cyclopropane]

  摘要：

  The addition of the phthalimidonitrene fragment. resulting from oxidation of N-aminophthalimide by lead tetraacetate at -20 to -30 degreesC, to the N=N-bond of 5-bromospiro[1-pyrazoline-3,1'-cyclopropane] (1) affords, apart from the stable 5-bromoN-(spiro[1-pyrazolinio-3,1-cyclopropane])-N-phthalimidoamide (azimine 2), regioisomeric azimine 3, which is completely transformed into 3-acetoxy-N-(spiro[1-pyrazolinio-5,1'-cyclopropane])- N-phthalimidoamide (4) under the reaction conditions. The acetoxy group in this product easily. undergoes nucleophilic substitution on treatment with MeOH. NaN3. or the starting bromopyrazoline 1. The structures of azimines obtained were established using N M R spectra. and the structure of the product of reaction of 4 with 1 was additionally proved by X-ray difraction data.

  DOI：

  10.1007/bf02494938
• 作为产物：
  描述：

  溴乙烯 、 1-环丙基-1-亚硝基脲 在 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.17h， 生成 5-bromospiro(1-pyrazoline-3,1'-cyclopropane)
  参考文献：
  名称：

  Addition of diazocyclopropane generatedin situ to vinyl bromide and chemical transformations of the resulting 5-bromospiro(1-pyrazoline-3,1′-cyclopropane)

  摘要：

  The reaction of diazocyclopropane generated in situ with vinyl bromide occurs as regioselective 1,3-dipolar cycloaddition to give 5-bromospiro(1-pyrazoline-3,1'-cyclopropane) in similar to 60% yield. Reactions of the latter with nucleophilic reagents, which can occur both with retention and opening of the cyclopropane ring, were studied.

  DOI：

  10.1007/bf02495975

文献信息

• Reactions of spirocyclopropane-containing 1- and 2-pyrazolines with electrophilic reagents
  作者：Yu. V. Tomilov、I. V. Kostyuchenko、G. P. Okonnishnikova、E. V. Shulishov、E. A. Yagodkin、O. M. Nefedov

  DOI：10.1007/bf02494777

  日期：2000.3

  Hydrochlorination of spiro(1-pyrazoline-3,1′-cyclopropanes) proceeds regioselectively at the azocyclopropane group to form 3-(2-haloethyl)pyrazoline derivatives. If the latter contain a halogen atom in the heterocycle, they are readily converted into (2-haloethyl)pyrazole hydrohalides. Bromination of 3-cyanospiro(2-pyrazoline-5,1′-cyclopropane) withN-bromosuccinimide at 20°C proceeds with retention

  螺（1-吡唑啉-3,1'-环丙烷）的氢氯化在偶氮环丙烷基团上区域选择性地进行以形成3-（2-卤乙基）吡唑啉衍生物。如果后者在杂环中含有卤素原子，它们很容易转化为（2-卤乙基）吡唑氢卤化物。3-氰基螺（2-吡唑啉-5,1'-环丙烷）在 20°C 与 N-溴琥珀酰亚胺的溴化进行，环丙烷环保留，形成 3-溴-3-氰基螺（1-吡唑啉-5,1'-环丙烷），在 3-4 天后，在约 20°C 下以约 60% 的产率转化为（2-溴乙基）氰基吡唑。
• Formation and thermal decomposition of adducts of phthalimidonitrene with spiro(1-pyrazolinecyclopropanes)
  作者：Yu. V. Tomilov、I. V. Kostyuchenko、E. V. Shulishov、B. B. Averkiev、M. Yu. Antipin、O. M. Nefedov

  DOI：10.1007/bf02495296

  日期：1999.7

  large extent by the nature of the substituents in the pyrazoline ring. The structures of phthalimidoazimines were established based on the NMR spectra and X-ray diffraction data. Thermal conversions of the resulting adducts, which proceeded either with retention or with opening of the spiro-fused cyclopropane ring, were studied.

  在 -20°C 至 -30°C 的温度下，在螺（1-吡唑啉环丙烷）存在下用四乙酸铅氧化 N-氨基邻苯二甲酰亚胺，导致正式生成邻苯二甲酰亚胺，然后在吡唑啉环的 N=N 键上加成形成 5(3)-取代的 N-spiro[1-pyrazolinio-3(5),1'-cyclopropane]}-N-邻苯二甲酰亚胺（azimines），其区域异构组成在很大程度上取决于取代基的性质在吡唑啉环中。基于核磁共振谱和X射线衍射数据确定邻苯二甲酰亚胺的结构。对所得加合物的热转化进行了研究，该转化伴随着螺稠环丙烷环的保留或打开而进行。
• Addition of diazocyclopropane generatedin situ to vinyl bromide and chemical transformations of the resulting 5-bromospiro(1-pyrazoline-3,1′-cyclopropane)
  作者：Yu. V. Tomilov、I. V. Kostyuchenko、E. V. Shulishov、O. M. Nefedov

  DOI：10.1007/bf02495975

  日期：1998.4

  The reaction of diazocyclopropane generated in situ with vinyl bromide occurs as regioselective 1,3-dipolar cycloaddition to give 5-bromospiro(1-pyrazoline-3,1'-cyclopropane) in similar to 60% yield. Reactions of the latter with nucleophilic reagents, which can occur both with retention and opening of the cyclopropane ring, were studied.
• Different reactivities of regioisomeric azimines, adducts of phthalimidonitrene with 5-bromospiro[1-pyrazoline-3,1′-cyclopropane]
  作者：Yu. V. Tomilov、I. V. Kostyuchenko、E. V. Shulishov、B. B. Averkiev、M. Yu. Antipin

  DOI：10.1007/bf02494938

  日期：2000.11

  The addition of the phthalimidonitrene fragment. resulting from oxidation of N-aminophthalimide by lead tetraacetate at -20 to -30 degreesC, to the N=N-bond of 5-bromospiro[1-pyrazoline-3,1'-cyclopropane] (1) affords, apart from the stable 5-bromoN-(spiro[1-pyrazolinio-3,1-cyclopropane])-N-phthalimidoamide (azimine 2), regioisomeric azimine 3, which is completely transformed into 3-acetoxy-N-(spiro[1-pyrazolinio-5,1'-cyclopropane])- N-phthalimidoamide (4) under the reaction conditions. The acetoxy group in this product easily. undergoes nucleophilic substitution on treatment with MeOH. NaN3. or the starting bromopyrazoline 1. The structures of azimines obtained were established using N M R spectra. and the structure of the product of reaction of 4 with 1 was additionally proved by X-ray difraction data.

表征谱图