5-(2,3,3-trifluorocyclobuten-1-yl)spiro[1-pyrazoline-3,1'-cyclopropane] | 460744-87-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 5-(2,3,3-trifluorocyclobuten-1-yl)spiro[1-pyrazoline-3,1'-cyclopropane]
• 英文别名: 6-(2,3,3-trifluoro-1-cyclobutenyl)-4,5-diazaspiro[2.4]hept-4-ene；6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2,4]hept-4-ene；6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-4-ene；6-(2,3,3-Trifluorocyclobut-1-en-1-yl)-4,5-diazaspiro[2.4]hept-4-ene；6-(2,3,3-trifluorocyclobuten-1-yl)-4,5-diazaspiro[2.4]hept-4-ene
• CAS: 460744-87-0
• 化学式: C₉H₉F₃N₂
• 分子量: 202.179
• InChiKey: CKECSGOTVJQZJW-UHFFFAOYSA-N

物化性质

• 沸点：
  215.9±40.0 °C(Predicted)
• 密度：
  1.67±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-(2,3,3-trifluorocyclobuten-1-yl)spiro[1-pyrazoline-3,1'-cyclopropane] 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 4-acetyl-6-(3,3-difluoro-2-methoxycyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-5-ene
  参考文献：
  名称：

  含氟螺[环丙烷-1-吡唑啉]的酰化和所得加合物的脱卤化氢

  摘要：

  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。

  DOI：

  10.1007/s11172-005-0267-7
• 作为产物：
  描述：

  2-chloro-2,3,3-trifluoro-1-vinylcyclobutane 在 氢氧化钾 、 苄基三乙基氯化铵 、 potassium carbonate 作用下， 以 氢氧化钾 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 5-(2,3,3-trifluorocyclobuten-1-yl)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

• 1,3-Dipolar cycloaddition of diazomethane and diazocyclopropane to 2-fluoro-3-methylbutadiene and thermal transformations of fluorine-containing vinylpyrazolines and vinylcyclopropanes
  作者：E. V. Guseva、N. V. Volchkov、E. V. Shulishov、Yu. V. Tomilov、O. M. Nefedov

  DOI：10.1023/b:rucb.0000042293.15892.9a

  日期：2004.6

  conditions (400—600 °C), into 1-fluoro-2-methylcyclopent-1-ene and 5-fluoro-4-methylspiro[2.4]hept-4-ene (7), respectively. Spiropentane derivative 5 partially isomerizes into 1-fluoro-2-methyl-3-methylidenecyclohex-1-ene. In a similar way, thermolysis of 6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-4-ene at 400 °C gives a mixture of 1-(spiropentyl)-2,3,3-trifluorocyclobut-1-ene and 2,3,3

  2-氟-3-甲基丁-1,3-二烯与重氮甲烷在乙醚中的反应，温度为 15 °C，并与通过在 K2CO3 的 CH2Cl2 中在 –10 °C 下分解 N-环丙基-N-亚硝基脲原位生成的重氮环丙烷反应C 选择性地涉及甲基上的双键，得到 3-(1-氟乙烯基)-3-甲基吡唑啉。后者在 250 °C 下热脱重氮化产生 1-(1-fluorovinyl)-1-methylcyclopropane 和 -spiropentane 5，它们能够在更严酷的条件下 (400-600 °C) 异构化成 1-fluoro-2 -methylcyclopent-1-ene 和 5-fluoro-4-methylspiro[2.4]hept-4-ene (7)，分别。螺戊烷衍生物 5 部分异构化为 1-fluoro-2-methyl-3-methylidenecyclohex-1-ene。以类似的方式，6-(2,3,
• Formation of Cyclobutylidenepyrazolines by Methanolysis of 6-(2,3,3-Trifluorocyclobutenyl)-4,5-diazaspiro[2.4]hept-4-ene
  作者：Ekaterina V. Guseva、Nikolay V. Volchkov、Yury V. Tomilov、Boris B. Averkiev、Oleg M. Nefedov

  DOI：10.1002/ejoc.200390084

  日期：2003.2

  The reaction of 6-(2,3,3-trifluorocyclobutenyl)-4,5-diazaspiro[2.4]hept-4-ene with NaOMe in MeOH results in a mixture of isomeric (6E)- and (6Z)-6-(2-fluoro-3,3-dimethoxycyclobutylidene)-4,5-diazaspiro[2.4]hept-4-ene due to the formal substitution of methoxy groups for two geminal fluorine atoms. Both of the isomers selectively add acetyl chloride at the azo-olefin unit to give 4-acetyl-6-(1-chloro-2-fluoro-3

  6-(2,3,3-三氟环丁烯基)-4,5-二氮杂螺[2.4]庚-4-烯与NaOMe在MeOH中的反应产生异构体(6E)-和(6Z)-6-( 2-氟-3,3-二甲氧基环亚丁基)-4,5-二氮杂螺[2.4]庚-4-烯由于甲氧基对两个孪生氟原子的形式取代。两种异构体都选择性地在偶氮烯烃单元添加乙酰氯，得到 4-乙酰基-6-(1-氯-2-氟-3,3-二甲氧基环丁基)-4,5-二氮杂螺[2.4]hept-4-烯作为反式异构体，产率超过 95%。(© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2003)
• ——
  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.
• 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。