3,4,5,6-Tetrahydro-7-<2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro)octyloxy>-2H-azepine | 155939-25-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吖庚因类
• 英文名称: 3,4,5,6-Tetrahydro-7-<2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro)octyloxy>-2H-azepine
• 英文别名: (2-(Perfluorohexyl)ethyl)caprolactim；7-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctoxy)-3,4,5,6-tetrahydro-2H-azepine
• CAS: 155939-25-6
• 化学式: C₁₄H₁₄F₁₃NO
• 分子量: 459.25
• InChiKey: ONKOAKQSNHQKOW-UHFFFAOYSA-N

物化性质

• 沸点：
  277.8±40.0 °C(Predicted)
• 密度：
  1.47±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  3,4,5,6-Tetrahydro-7-<2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro)octyloxy>-2H-azepine 在 2-吡咯烷酮 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以44.9%的产率得到3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟-1-辛醇
  参考文献：
  名称：

  Thermal Alkylation of Ambidentate Lactams with 2-(Perfluoroalkyl)-1-iodoalkanes. The Effect of Reaction Conditions and Ring Size on the Synthesis of 2-(Perfluoroalkyl)ethanols and the Mechanism of Reaction

  摘要：

  The perfluoroalkylated long chain alcohol and their derivatives exhibit strong surface activity in solution and novel surface modification properties as adsorbed layers or films. A new, little known synthesis of 2-(perfluoroalkyl)ethanols (R(F)CH(2)CH(2)OH) employs a lactam, e.g., 2-pyrrolidinone (2), with an iodoalkane, e.g., C6F13CH2CH2I (1) Alkylation of 2 by heating with 1 gives C6F13CH2CH2OH (3) in 83% distilled yield, and treating the residual lactim ether salt (6 HI) with K2CO3 gives additional 3, up to 94% yield. Rate of alcohol formation (k(alc)) is unaffected by molar ratio of 2:1, yet rate of 1 reaction (k(iodo)) increases 2.44 times with doubling of 2:1 and side product C6F13CH=CH2 (4) decreases from 4 to 2%. For homologous lactams [(CH2)(n)NHC=O] (n = 3-5), selectivities (mel 3:4) are as follows: 5-membered ring, 18.4; 6-membered ring, 0.73; 7-membered ring, 0.13. Conversions to 3 are as follows: 6-membered ring, 19.4%; and 7-membered ring, 1.75%, Table 13. A three-step mechanism is proposed: (1) O-alkylation of the lactam by 1 gives lactim salt I; (2) N-substitution of salt I by another molecule of lactam forms a tetrahedral adduct (II); (3) breakdown of salt II gives 3 and iminolactam salt III. In model experiments, heating of 2 and lactim 6 yields 99% of 3 and iminolactam 5 and 1% of 4. By contrast, 7-membered 14 with 2 gives 45% of 3 and iminolactam 12, besides 4 and epsilon-caprolactam 10 (20%). For higher lactams, two competitive reactions can be discerned: (1) the S(N)2 displacement of alcohol by N-attack on salt II and a unimolecular, concerted fragmentation of the lactim, to lactam and alkene.

  DOI：

  10.1021/jo00112a029
• 作为产物：
  描述：

  1-氮杂-2-甲氧基-1-环庚烯 、 3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟-1-辛醇 以93.4%的产率得到3,4,5,6-Tetrahydro-7-<2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro)octyloxy>-2H-azepine
  参考文献：
  名称：

  The Effect of Ring Size on Tetrahedral Displacement Reactions of Cyclic Imidates. Synthesis of O-(Fluoroalkyl)lactim and Higher O-Alkyllactims from Lower O-Alkyllactims

  摘要：

  A recently developed synthesis of 2-(perfluoroalkyl)ethanols (R(F)CH(2)CH(2)OH) is based on heating 2-(perfluoroalkyl)-1-iodoethanes R(F)CH(2)CH(2)I with an amide, e.g., N-methylformamide or a lactam, 2-pyrrolidinone. The presumed O-[2-(perfluoroalkyl)ethyl]lactim intermediates have now been prepared in good to excellent yields (60-90%) by heating a lower molecular mass O-alkyllactim with a higher-boiling alcohol, e.g., with R(F)CH(2)CH(2)OH, to displace the lower boiling alcohol. Competitive rate experiments showed that a 7-membered O-methyllactim reacted four to five times faster than did the 5-membered O-methyllactim. This difference is attributed to increased eclipsing strain, commonly called ''I-strain''. In a ''planar'' 5-membered lactim ring, the engendered eclipsing strain appears to be greater than in the more flexible 7-membered ring. Reactant ratio and reaction conditions also affected the yield of lactim ether. Preparatively, reaction of C6F13CH2CH2OH (3) with O-ethylbutyrolactim (6) gave O-[2-(perfluorohexyl)ethyl]butyrolactim (7) in an 89.2% yield (on unrecovered 3) at 67.9% conversion. Yield was limited by dealkylation and condensation reactions that occurred during long heating times. By contrast, alcohol 3 with O-methylcaprolactim (10) gave 7-membered O-[2-(F-hexyl)ethyl]caprolactim (11) in 98% yield at 90% conversion.

  DOI：

  10.1021/jo00092a028

文献信息

• Brace Neal O., Davidson Barbara C., Shellhamer Dale F., Daniels Mirna, J. Org. Chem, 59 (1994) N 13, S 3670-3675
  作者：Brace Neal O., Davidson Barbara C., Shellhamer Dale F., Daniels Mirna

  DOI：——

  日期：——
• The Effect of Ring Size on Tetrahedral Displacement Reactions of Cyclic Imidates. Synthesis of O-(Fluoroalkyl)lactim and Higher O-Alkyllactims from Lower O-Alkyllactims
  作者：Neal O. Brace、Barbara C. Davidson、Dale F. Shellhamer、Mirna Daniels

  DOI：10.1021/jo00092a028

  日期：1994.7

  A recently developed synthesis of 2-(perfluoroalkyl)ethanols (R(F)CH(2)CH(2)OH) is based on heating 2-(perfluoroalkyl)-1-iodoethanes R(F)CH(2)CH(2)I with an amide, e.g., N-methylformamide or a lactam, 2-pyrrolidinone. The presumed O-[2-(perfluoroalkyl)ethyl]lactim intermediates have now been prepared in good to excellent yields (60-90%) by heating a lower molecular mass O-alkyllactim with a higher-boiling alcohol, e.g., with R(F)CH(2)CH(2)OH, to displace the lower boiling alcohol. Competitive rate experiments showed that a 7-membered O-methyllactim reacted four to five times faster than did the 5-membered O-methyllactim. This difference is attributed to increased eclipsing strain, commonly called ''I-strain''. In a ''planar'' 5-membered lactim ring, the engendered eclipsing strain appears to be greater than in the more flexible 7-membered ring. Reactant ratio and reaction conditions also affected the yield of lactim ether. Preparatively, reaction of C6F13CH2CH2OH (3) with O-ethylbutyrolactim (6) gave O-[2-(perfluorohexyl)ethyl]butyrolactim (7) in an 89.2% yield (on unrecovered 3) at 67.9% conversion. Yield was limited by dealkylation and condensation reactions that occurred during long heating times. By contrast, alcohol 3 with O-methylcaprolactim (10) gave 7-membered O-[2-(F-hexyl)ethyl]caprolactim (11) in 98% yield at 90% conversion.
• Thermal Alkylation of Ambidentate Lactams with 2-(Perfluoroalkyl)-1-iodoalkanes. The Effect of Reaction Conditions and Ring Size on the Synthesis of 2-(Perfluoroalkyl)ethanols and the Mechanism of Reaction
  作者：Neal O. Brace

  DOI：10.1021/jo00112a029

  日期：1995.4

  The perfluoroalkylated long chain alcohol and their derivatives exhibit strong surface activity in solution and novel surface modification properties as adsorbed layers or films. A new, little known synthesis of 2-(perfluoroalkyl)ethanols (R(F)CH(2)CH(2)OH) employs a lactam, e.g., 2-pyrrolidinone (2), with an iodoalkane, e.g., C6F13CH2CH2I (1) Alkylation of 2 by heating with 1 gives C6F13CH2CH2OH (3) in 83% distilled yield, and treating the residual lactim ether salt (6 HI) with K2CO3 gives additional 3, up to 94% yield. Rate of alcohol formation (k(alc)) is unaffected by molar ratio of 2:1, yet rate of 1 reaction (k(iodo)) increases 2.44 times with doubling of 2:1 and side product C6F13CH=CH2 (4) decreases from 4 to 2%. For homologous lactams [(CH2)(n)NHC=O] (n = 3-5), selectivities (mel 3:4) are as follows: 5-membered ring, 18.4; 6-membered ring, 0.73; 7-membered ring, 0.13. Conversions to 3 are as follows: 6-membered ring, 19.4%; and 7-membered ring, 1.75%, Table 13. A three-step mechanism is proposed: (1) O-alkylation of the lactam by 1 gives lactim salt I; (2) N-substitution of salt I by another molecule of lactam forms a tetrahedral adduct (II); (3) breakdown of salt II gives 3 and iminolactam salt III. In model experiments, heating of 2 and lactim 6 yields 99% of 3 and iminolactam 5 and 1% of 4. By contrast, 7-membered 14 with 2 gives 45% of 3 and iminolactam 12, besides 4 and epsilon-caprolactam 10 (20%). For higher lactams, two competitive reactions can be discerned: (1) the S(N)2 displacement of alcohol by N-attack on salt II and a unimolecular, concerted fragmentation of the lactim, to lactam and alkene.