(S)-1-phenyl-2-methoxypropane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-1-phenyl-2-methoxypropane
• 英文别名: [(2S)-2-methoxypropyl]benzene
• 化学式: C₁₀H₁₄O
• 分子量: 150.221
• InChiKey: RRBICPTVXCKVIL-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  氟甲烷 、 (S)-2-苯基-1-丙醇 在 氧气 、 重氧水 作用下， 以 gaseous matrix 为溶剂， 生成 2-phenyl-1-methoxypropane 、 (S)-1-phenyl-2-methoxypropane 、 <18O>-(S)-1-phenyl-2-methoxypropane
  参考文献：
  名称：

  Wagner-Meerwein Rearrangements in the Gas Phase: Anchimeric Assistance to Acid-Induced Dissociation of Optically Active Phenylpropanols

  摘要：

  The kinetics and the stereochemistry of Wagner-Meerwein rearrangements of O-protonated and O-methylated (S)-1-phenyl-2-propanol (1s(A+) A=H or Me) and (S)-2-phenyl-1-propanol (2s(A+) A=H or Me) have been investigated in the gas phase at 750 Torr and in the 25 - 140 degrees C temperature range. The 1s(A+) and 2s(A+) intermediates were generated in the gas phase by reaction of the CnH5+(n=1, 2; A=H) and (CH3)(2)F+ ions (A = Me), formed by stationary gamma radiolysis of bulk CH4 and CH3F,respectively, with the corresponding optically active alcohols. The results are consistent with unimolecular H2O loss from both 1s(H+) and 2s(H+); this is anchimerically assisted by all the groups adjacent to the leaving moiety. Anchimeric assistance appears much less efficient in both 1s(Me+). and 2 s(Me+). Analysis of the activation parameters indicates that competing neighboring-group participation in C-O bond fission in 1s(H+) and 2s(H+) respond essentially to entropic rather than enthalpic factors. The stereochemical distribution of the reaction products allowed us to discern between backside and frontside phenyl-group participation in Is,,. The counterintuitive observation of a frontside Ph participation, with an activation energy 1.3+/-0.5 kcal mol(-1) lower than that of the accompanying backside assistance, is attributed to conformational factors and to the stabilizing electrostatic interactions between the phenonium ion and the leaving H2O complex that is spatially allowed only in the frontside participation and forbidden in the backside one.

  DOI：

  10.1002/(sici)1521-3765(19990301)5:3<834::aid-chem834>3.0.co;2-g

文献信息

• COMPOUNDS
  申请人：Mciver Edward Giles

  公开号：US20100317646A1

  公开（公告）日：2010-12-16

  A compound of formula I, or a pharmaceutically acceptable salt or ester thereof, wherein R 1 is selected from: aryl; heteroaryl; —NHR 3 ; fused aryl-C 4-7 -heterocycloalkyl; —CONR 4 R 5 ; —NHCOR 6 ; —C 3-7 -cycloalkyl; —O—C 3-7 -cycloalkyl; —NR 3 R 6 ; and optionally substituted —C 1-6 alkyl; wherein said aryl, heteroaryl, fused aryl-C 4-7 -heterocycloalkyl and C 4-7 -heterocycloalkyl are each optionally substituted; R 2 is selected from hydrogen, aryl, C 1-6 -alkyl, C 2-6 -alkenyl, C 3-7 -cycloalkyl, heteroaryl, C 4-7 heterocycloalkyl and halogen, wherein said C 1-6 -alkyl, C 2-6 -alkenyl, aryl, heteroaryl and C 4-7 -heterocycloalkyl are each optionally substituted; R 3 is selected from aryl, heteroaryl, C 4-7 -heterocycloalkyl, C 3-7 -cycloalkyl, fused aryl-C 4-7 -heterocycloalkyl and C 1-6 -alkyl, each of which is optionally substituted; R 4 and R 5 are each independently hydrogen, or optionally substituted C 3-7 -cycloalkyl, aryl, heteroaryl, C 1-6 -alkyl or C 3-6 -heterocycloalkyl; or R 4 and R 5 together with the N to which they are attached form a C 3-6 -heterocycloalkyl ring; each R 6 is independently selected from C 1-6 -alkyl, C 3-7 cycloalkyl, C 4-7 -heterocycloalkyl, aryl and heteroaryl, each of which is optionally substituted each R 7 is selected from hydrogen, optionally substituted C 1-6 -alkyl and C 3-7 -cycloalkyl; each of R 8 and R 9 is independently hydrogen or optionally substituted C 1-6 -alkyl; or R 8 and R 9 together with the N to which they are attached form a C 4-6 -heterocycloalkyl; each R 10 is selected from C 3-7 -cycloalkyl and optionally substituted C 1-6 -alkyl; each R 11 is independently selected from C 1-6 -alkyl, C 3-7 -cycloalkyl, C 1-6 alkyl-C 3-7 -cycloalkyl, C 4-7 -heterocycloalkyl, aryl and heteroaryl, each of which is optionally substituted; A is selected from halogen, —NR 4 SO 2 R 5 , —CN, —OR 6 , —NR 4 R 5 , —NR 7 R 11 , hydroxyl, —CF 3 , —CONR 4 R 5 , —NR 4 COR 5 , —NR 7 (CO)NR 4 R 5 , —NO 2 , —CO 2 H, —CO 2 R 6 , —SO 2 R 6 , —SO 2 NR 4 R 5 , —NR 4 COR 5 , —NR 4 COOR 5 , C 1-6 -alkyl and —COR 6 . Further aspects relate to pharmaceutical compositions, therapeutic uses and process for preparing compounds of formula I.

  化合物I的公式，或其药学上可接受的盐或酯，其中R1选自：芳基；杂环芳基；—NHR3；融合的芳基-C4-7-杂环烷基；—CONR4R5；—NHCOR6；—C3-7-环烷基；—O—C3-7-环烷基；—NR3R6；和可选择取代的—C1-6烷基；其中所述的芳基，杂环芳基，融合的芳基-C4-7-杂环烷基和C4-7-杂环烷基均可选择取代；R2选自氢，芳基，C1-6-烷基，C2-6-烯基，C3-7-环烷基，杂环芳基，C4-7-杂环烷基和卤素，其中所述的C1-6-烷基，C2-6-烯基，芳基，杂环芳基和C4-7-杂环烷基均可选择取代；R3选自芳基，杂环芳基，C4-7-杂环烷基，C3-7-环烷基，融合的芳基-C4-7-杂环烷基和C1-6-烷基，每种均可选择取代；R4和R5各自独立地选自氢，或可选择取代的C3-7-环烷基，芳基，杂环芳基，C1-6-烷基或C3-6-杂环烷基；或R4和R5与它们连接的N一起形成C3-6-杂环烷基环；每个R6各自独立地选自C1-6-烷基，C3-7-环烷基，C4-7-杂环烷基，芳基和杂环芳基，每种均可选择取代；每个R7选自氢，可选择取代的C1-6-烷基和C3-7-环烷基；每个R8和R9各自独立地选自氢或可选择取代的C1-6-烷基；或R8和R9与它们连接的N一起形成C4-6-杂环烷基；每个R10选自C3-7-环烷基和可选择取代的C1-6-烷基；每个R11各自独立地选自C1-6-烷基，C3-7-环烷基，C1-6-烷基-C3-7-环烷基，C4-7-杂环烷基，芳基和杂环芳基，每种均可选择取代；A选自卤素，—NR4SO2R5，—CN，—OR6，—NR4R5，—NR7R11，羟基，—CF3，—CONR4R5，—NR4COR5，—NR7（CO）NR4R5，—NO2，—CO2H，—CO2R6，—SO2R6，—SO2NR4R5，—NR4COR5，—NR4COOR5，C1-6-烷基和—COR6。进一步方面涉及公式I化合物的制药组合物，治疗用途和制备过程。
• Wagner-Meerwein Rearrangements in the Gas Phase: Anchimeric Assistance to Acid-Induced Dissociation of Optically Active Phenylpropanols
  作者：Maurizio Speranza、Antonello Filippi

  DOI：10.1002/(sici)1521-3765(19990301)5:3<834::aid-chem834>3.0.co;2-g

  日期：1999.3.1

  The kinetics and the stereochemistry of Wagner-Meerwein rearrangements of O-protonated and O-methylated (S)-1-phenyl-2-propanol (1s(A+) A=H or Me) and (S)-2-phenyl-1-propanol (2s(A+) A=H or Me) have been investigated in the gas phase at 750 Torr and in the 25 - 140 degrees C temperature range. The 1s(A+) and 2s(A+) intermediates were generated in the gas phase by reaction of the CnH5+(n=1, 2; A=H) and (CH3)(2)F+ ions (A = Me), formed by stationary gamma radiolysis of bulk CH4 and CH3F,respectively, with the corresponding optically active alcohols. The results are consistent with unimolecular H2O loss from both 1s(H+) and 2s(H+); this is anchimerically assisted by all the groups adjacent to the leaving moiety. Anchimeric assistance appears much less efficient in both 1s(Me+). and 2 s(Me+). Analysis of the activation parameters indicates that competing neighboring-group participation in C-O bond fission in 1s(H+) and 2s(H+) respond essentially to entropic rather than enthalpic factors. The stereochemical distribution of the reaction products allowed us to discern between backside and frontside phenyl-group participation in Is,,. The counterintuitive observation of a frontside Ph participation, with an activation energy 1.3+/-0.5 kcal mol(-1) lower than that of the accompanying backside assistance, is attributed to conformational factors and to the stabilizing electrostatic interactions between the phenonium ion and the leaving H2O complex that is spatially allowed only in the frontside participation and forbidden in the backside one.