5-(2,2,3,3-tetrafluorocyclobutyl)spiro(1-pyrazoline-3,1'-cyclopropane) | 879213-49-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 5-(2,2,3,3-tetrafluorocyclobutyl)spiro(1-pyrazoline-3,1'-cyclopropane)
• 英文别名: 6-(2,2,3,3-tetrafluorocyclobutyl)-4,5-diazaspiro[2.4]hept-4-ene
• CAS: 879213-49-7
• 化学式: C₉H₁₀F₄N₂
• 分子量: 222.185
• InChiKey: YQJRKJVSSZFPLN-UHFFFAOYSA-N

物化性质

• 沸点：
  217.6±40.0 °C(Predicted)
• 密度：
  1.72±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• 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：
  6

反应信息

• 作为反应物：
  描述：

  5-(2,2,3,3-tetrafluorocyclobutyl)spiro(1-pyrazoline-3,1'-cyclopropane) 400.0 ℃ 、6.67 kPa 条件下， 以71%的产率得到(2,2,3,3-tetrafluorocyclobutyl)spiropentane
  参考文献：
  名称：

  摘要：

  The reactions of diazomethane and diazocyclopropane generated in situ with 1,1,2,2-tetrafluoro-3-vinylcyclobutane (1) and 2,3,3-trifluoro-1-vinylcyclobutene (2) proceeded at the double bond of the substituent as the 1,3-dipolar cycloaddition to form the corresponding 1-pyrazolines. Under the conditions of thermolysis (340-400 degreesC), the resulting cyclobutylpyrazolines 4 and 5 selectively lost the dinitrogen molecule to generate 3-cyclopropyl-1,1,2,2-tetrafluorocyclobutane (6) or 1,1, 2,2-tetrafluoro-3-spiropentylcyclobutane (7), respectively, in high yields. In the presence of Pd(acac)(2), the reactions of these fluorine-containing unsaturated compounds and 2-chloro-1,1,2-trifluoro-3-vinylcyclobutane (3) with diazomethane gave rise directly to cyclopropane derivatives 6, 11, and 12, respectively. The reactions of compounds 1 and 2 with methyl diazoacetate in the presence of Rh-2(OAc)(4) proceeded analogously to yield cis- and trans-disubstituted cyclopropanes.

  DOI：

  10.1023/a:1015049317831
• 作为产物：
  描述：

  1-环丙基-1-亚硝基脲 、 3-乙烯基-1,1,2,2-四氟环丁烷 在 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 40.0h， 以48%的产率得到5-(2,2,3,3-tetrafluorocyclobutyl)spiro(1-pyrazoline-3,1'-cyclopropane)
  参考文献：
  名称：

  摘要：

  The reactions of diazomethane and diazocyclopropane generated in situ with 1,1,2,2-tetrafluoro-3-vinylcyclobutane (1) and 2,3,3-trifluoro-1-vinylcyclobutene (2) proceeded at the double bond of the substituent as the 1,3-dipolar cycloaddition to form the corresponding 1-pyrazolines. Under the conditions of thermolysis (340-400 degreesC), the resulting cyclobutylpyrazolines 4 and 5 selectively lost the dinitrogen molecule to generate 3-cyclopropyl-1,1,2,2-tetrafluorocyclobutane (6) or 1,1, 2,2-tetrafluoro-3-spiropentylcyclobutane (7), respectively, in high yields. In the presence of Pd(acac)(2), the reactions of these fluorine-containing unsaturated compounds and 2-chloro-1,1,2-trifluoro-3-vinylcyclobutane (3) with diazomethane gave rise directly to cyclopropane derivatives 6, 11, and 12, respectively. The reactions of compounds 1 and 2 with methyl diazoacetate in the presence of Rh-2(OAc)(4) proceeded analogously to yield cis- and trans-disubstituted cyclopropanes.

  DOI：

  10.1023/a:1015049317831

文献信息

• Acylation of fluorine-containing spiro[cyclopropane-1-pyrazolines] and dehydrohalogenation of the resulting adducts
  作者：E. V. Guseva、Yu. V. Tomilov

  DOI：10.1007/s11172-005-0267-7

  日期：2005.2

  respectively. Under the same conditions, acylation of 6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-4-ene is not regioselective. The (2-chloroethyl) pyrazolines obtained undergo dehydrochlorination into vinylpyrazolines in the presence of an excess of MeONa in MeOH. The reaction of 4-acetyl-6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-5-ene with MeONa results in selective replacement

  6-(1-氟乙烯基)-6-甲基-和 6-(2,2,3,3-四氟环丁基)-4,5-二氮杂螺[2.4]庚-4-烯与乙酰氯的酰化反应作为亲电加成进行N(5) 原子并伴随着环丙烷环的打开，得到 1-乙酰基-3-(2-氯乙基)-5-(1-氟乙烯基)-5-甲基-和 1-乙酰基-3-(2 -氯乙基)-5-(2,2,3,3-四氟环丁基)-4,5-二氢吡唑分别。在相同条件下，6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-4-ene 的酰化不具有区域选择性。在过量MeONa的MeOH存在下，获得的(2-氯乙基)吡唑啉经历脱氯化氢成为乙烯基吡唑啉。4-乙酰-6-(2,3,3-三氟环丁-1-烯基)-4,5-二氮杂螺[2.4]庚-5-烯与MeONa的反应导致双键处的F原子的选择性置换由甲氧基。
• ——
  作者：Yu. V. Tomilov、E. V. Guseva、N. V. Volchkov、E. V. Shulishov

  DOI：10.1023/a:1015049317831

  日期：——

  The reactions of diazomethane and diazocyclopropane generated in situ with 1,1,2,2-tetrafluoro-3-vinylcyclobutane (1) and 2,3,3-trifluoro-1-vinylcyclobutene (2) proceeded at the double bond of the substituent as the 1,3-dipolar cycloaddition to form the corresponding 1-pyrazolines. Under the conditions of thermolysis (340-400 degreesC), the resulting cyclobutylpyrazolines 4 and 5 selectively lost the dinitrogen molecule to generate 3-cyclopropyl-1,1,2,2-tetrafluorocyclobutane (6) or 1,1, 2,2-tetrafluoro-3-spiropentylcyclobutane (7), respectively, in high yields. In the presence of Pd(acac)(2), the reactions of these fluorine-containing unsaturated compounds and 2-chloro-1,1,2-trifluoro-3-vinylcyclobutane (3) with diazomethane gave rise directly to cyclopropane derivatives 6, 11, and 12, respectively. The reactions of compounds 1 and 2 with methyl diazoacetate in the presence of Rh-2(OAc)(4) proceeded analogously to yield cis- and trans-disubstituted cyclopropanes.