3,4-Dihydro-5-<(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro)octyloxy>-2H-pyrrole | 155939-24-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 甲亚胺酸及其衍生物
• 英文名称: 3,4-Dihydro-5-<(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro)octyloxy>-2H-pyrrole
• 英文别名: O-<2-(perfluorohexyl)ethyl>butyrolactim；2-(Perfluorohexyl)ethylbutyrolactim；5-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctoxy)-3,4-dihydro-2H-pyrrole
• CAS: 155939-24-5
• 化学式: C₁₂H₁₀F₁₃NO
• 分子量: 431.197
• InChiKey: SBMQHNZMMUWUFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 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-Dihydro-5-<(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro)octyloxy>-2H-pyrrole 在 2-吡咯烷酮 作用下， 反应 3.0h， 以1%的产率得到1H,1H,2H-全氟-1-辛烯
  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：

  2-乙氧基-4,5-二氢-3H-吡咯 、 3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟-1-辛醇 反应 36.0h， 以89.22%的产率得到3,4-Dihydro-5-<(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro)octyloxy>-2H-pyrrole
  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

• 2-(Perfluoroalkyl)ethanols by Thermal Alkylation of Ambidentate Lactams with 2-(Perfluoroalkyl)-1-iodoalkanes, in the Presence of Added Water. A Change in Mechanism and Stoichiometry of the Reaction. Isolation of a Water Adduct of the Lactim Ether Intermediate
  作者：Neal O. Brace

  DOI：10.1021/jo960831g

  日期：1996.1.1

  Thermal alkylation of amides by an alkyl halide gives alcohols and esters, and the intriguing behavior of ambidentate lactams in this reaction with 2-(perfluoroalkyl)-1-iodoethanes and lactam 2 is summarized in Scheme 1. 2-(Perfluoroalkyl)ethanols (3) are the principal alkylation product, and there is obtained a range of coproducts in varying amounts. A lactim ether salt (6.HI) is the first reaction

  流程1中概述了酰胺与烷基卤的热烷基化反应生成醇和酯，歧化内酰胺在与2-（全氟烷基）-1-碘乙烷和内酰胺2的反应中表现出令人着迷的行为.2-（全氟烷基）乙醇（3 ）是主要的烷基化产物，并且获得了各种量的副产物。乳酸亚胺醚盐（6.HI）是一系列反应中的第一个反应中间体。对于δ-戊内酰胺（8）或ε-己内酰胺（11），转化为3的幅度急剧下降，R（F）CH = CH（2）（4）成为主要产品。然而，当引入水时，碘代烷1的2的烷基化速率增加，向3和4的转化率降低，并形成了新的内酰胺醚盐7.HI（6.HI的水加合物）。由于副产物2弱碱性且平衡位于碱性胺盐（7.HI）一侧，抑制了向3的转化。2-羟基-2-[[[（（（2-（全氟己基）乙基]氧基]吡咯烷）的质谱图包括母体离子和带有羟基的完整吡咯烷环的片段（m / z = 131） 。在质子溶剂中含有7.HI的产物混合物的碱性水解可得到3和2的高产率。较高的内酰
• 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.