Synthesis and characterization of fluorous (S)- and (R)-1-phenylethylamines that effect heat facilitated resolution of (±)-2-(8-carboxy-1-naphthylsulfinyl)benzoic acid via diastereomeric salt formation and study of their circular dichroism

D. Szabó, Anikó Nemes, István Kövesdi, Viktor Farkas, M. Hollósi, J. Rábai

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7 Citations (Scopus)

Abstract

Perfluoroalkyl- or nonafluoro-tert-butoxy-alkyl-substituted enantiopure amines having the structure PhCHCH3(NR1R2) [R1 = H, CH3; R2 = (CH2)3C8F17, (CH2)2OC(CF3)3; R1 = R2 = (CH2)3C8F17, (CH2)2OC(CF3)3] are obtained in high yields, when (S)-(-)-1-phenylethylamine is reacted with readily accessible alkylating reagents or fluorous 2° amines (R1 = H; R2 = (CH2)3C8F17, (CH2)2OC(CF3)3) are methylated in a Leuckart-Wallach reaction. The solubility patterns of these novel chiral amines and their hydrochlorides are qualitatively described for a broad spectrum of solvents and the fluorous partition coefficients of the free bases are determined by GC. A novel method for the resolution of enantiomers is disclosed here, which involves the use a half-equivalent of the selected resolving agent in solvent water that displays low solubility for the crystalline diastereomeric salt(s) formed even at temperatures near to its boiling point. Compound (S)-(-)-PhCHCH3[NH(CH2)3C8F17] is found to satisfy all the latter conditions and successfully used for the heat facilitated resolution of the title racemic acid. The circular dichroism (CD) spectra of six novel fluorous (S)-(-)-1-phenylethylamine derivatives are measured in ethanol, trifluoroethanol and hexafluoropropan-2-ol and discussed in detail.

Original languageEnglish
Pages (from-to)1405-1414
Number of pages10
JournalJournal of Fluorine Chemistry
Volume127
Issue number10 SPEC. ISS.
DOIs
Publication statusPublished - Oct 2006

Fingerprint

Phenethylamines
Benzoic Acid
Benzoic acid
benzoic acid
Dichroism
Circular Dichroism
Thermal effects
dichroism
Amines
temperature effects
amines
Salts
Hot Temperature
salts
salt
Solubility
acid
solubility
synthesis
Trifluoroethanol

Keywords

  • Alkylation
  • Chiral amines
  • Circular dichroism
  • Fluorine
  • Fluorophilicity
  • Optical resolution
  • Specific rotation
  • Synthesis

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics

Cite this

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title = "Synthesis and characterization of fluorous (S)- and (R)-1-phenylethylamines that effect heat facilitated resolution of (±)-2-(8-carboxy-1-naphthylsulfinyl)benzoic acid via diastereomeric salt formation and study of their circular dichroism",
abstract = "Perfluoroalkyl- or nonafluoro-tert-butoxy-alkyl-substituted enantiopure amines having the structure PhCHCH3(NR1R2) [R1 = H, CH3; R2 = (CH2)3C8F17, (CH2)2OC(CF3)3; R1 = R2 = (CH2)3C8F17, (CH2)2OC(CF3)3] are obtained in high yields, when (S)-(-)-1-phenylethylamine is reacted with readily accessible alkylating reagents or fluorous 2° amines (R1 = H; R2 = (CH2)3C8F17, (CH2)2OC(CF3)3) are methylated in a Leuckart-Wallach reaction. The solubility patterns of these novel chiral amines and their hydrochlorides are qualitatively described for a broad spectrum of solvents and the fluorous partition coefficients of the free bases are determined by GC. A novel method for the resolution of enantiomers is disclosed here, which involves the use a half-equivalent of the selected resolving agent in solvent water that displays low solubility for the crystalline diastereomeric salt(s) formed even at temperatures near to its boiling point. Compound (S)-(-)-PhCHCH3[NH(CH2)3C8F17] is found to satisfy all the latter conditions and successfully used for the heat facilitated resolution of the title racemic acid. The circular dichroism (CD) spectra of six novel fluorous (S)-(-)-1-phenylethylamine derivatives are measured in ethanol, trifluoroethanol and hexafluoropropan-2-ol and discussed in detail.",
keywords = "Alkylation, Chiral amines, Circular dichroism, Fluorine, Fluorophilicity, Optical resolution, Specific rotation, Synthesis",
author = "D. Szab{\'o} and Anik{\'o} Nemes and Istv{\'a}n K{\"o}vesdi and Viktor Farkas and M. Holl{\'o}si and J. R{\'a}bai",
year = "2006",
month = "10",
doi = "10.1016/j.jfluchem.2006.05.011",
language = "English",
volume = "127",
pages = "1405--1414",
journal = "Journal of Fluorine Chemistry",
issn = "0022-1139",
publisher = "Elsevier BV",
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TY - JOUR

T1 - Synthesis and characterization of fluorous (S)- and (R)-1-phenylethylamines that effect heat facilitated resolution of (±)-2-(8-carboxy-1-naphthylsulfinyl)benzoic acid via diastereomeric salt formation and study of their circular dichroism

AU - Szabó, D.

AU - Nemes, Anikó

AU - Kövesdi, István

AU - Farkas, Viktor

AU - Hollósi, M.

AU - Rábai, J.

PY - 2006/10

Y1 - 2006/10

N2 - Perfluoroalkyl- or nonafluoro-tert-butoxy-alkyl-substituted enantiopure amines having the structure PhCHCH3(NR1R2) [R1 = H, CH3; R2 = (CH2)3C8F17, (CH2)2OC(CF3)3; R1 = R2 = (CH2)3C8F17, (CH2)2OC(CF3)3] are obtained in high yields, when (S)-(-)-1-phenylethylamine is reacted with readily accessible alkylating reagents or fluorous 2° amines (R1 = H; R2 = (CH2)3C8F17, (CH2)2OC(CF3)3) are methylated in a Leuckart-Wallach reaction. The solubility patterns of these novel chiral amines and their hydrochlorides are qualitatively described for a broad spectrum of solvents and the fluorous partition coefficients of the free bases are determined by GC. A novel method for the resolution of enantiomers is disclosed here, which involves the use a half-equivalent of the selected resolving agent in solvent water that displays low solubility for the crystalline diastereomeric salt(s) formed even at temperatures near to its boiling point. Compound (S)-(-)-PhCHCH3[NH(CH2)3C8F17] is found to satisfy all the latter conditions and successfully used for the heat facilitated resolution of the title racemic acid. The circular dichroism (CD) spectra of six novel fluorous (S)-(-)-1-phenylethylamine derivatives are measured in ethanol, trifluoroethanol and hexafluoropropan-2-ol and discussed in detail.

AB - Perfluoroalkyl- or nonafluoro-tert-butoxy-alkyl-substituted enantiopure amines having the structure PhCHCH3(NR1R2) [R1 = H, CH3; R2 = (CH2)3C8F17, (CH2)2OC(CF3)3; R1 = R2 = (CH2)3C8F17, (CH2)2OC(CF3)3] are obtained in high yields, when (S)-(-)-1-phenylethylamine is reacted with readily accessible alkylating reagents or fluorous 2° amines (R1 = H; R2 = (CH2)3C8F17, (CH2)2OC(CF3)3) are methylated in a Leuckart-Wallach reaction. The solubility patterns of these novel chiral amines and their hydrochlorides are qualitatively described for a broad spectrum of solvents and the fluorous partition coefficients of the free bases are determined by GC. A novel method for the resolution of enantiomers is disclosed here, which involves the use a half-equivalent of the selected resolving agent in solvent water that displays low solubility for the crystalline diastereomeric salt(s) formed even at temperatures near to its boiling point. Compound (S)-(-)-PhCHCH3[NH(CH2)3C8F17] is found to satisfy all the latter conditions and successfully used for the heat facilitated resolution of the title racemic acid. The circular dichroism (CD) spectra of six novel fluorous (S)-(-)-1-phenylethylamine derivatives are measured in ethanol, trifluoroethanol and hexafluoropropan-2-ol and discussed in detail.

KW - Alkylation

KW - Chiral amines

KW - Circular dichroism

KW - Fluorine

KW - Fluorophilicity

KW - Optical resolution

KW - Specific rotation

KW - Synthesis

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U2 - 10.1016/j.jfluchem.2006.05.011

DO - 10.1016/j.jfluchem.2006.05.011

M3 - Article

AN - SCOPUS:33750343706

VL - 127

SP - 1405

EP - 1414

JO - Journal of Fluorine Chemistry

JF - Journal of Fluorine Chemistry

SN - 0022-1139

IS - 10 SPEC. ISS.

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