3-Endo-(hidroxi-metil)-5-exo-biciklo[2.2.1]heptil-2-endo-amin regioszelektív szintézise és átalakítása telített vagy részlegesen telített diendo-kondenzált heterociklusokká

Translated title of the contribution: Regioselective synthesis of 3-endo-hydroxymethyl-5-exo-phenylbicyclo[2.2.1]heptane-2-endo-amine and its transformation to saturated or partially saturated diendo-fused heterocycles

Miklós Virág, G. Stájer, Angela Szabó E., G. Bernáth, P. Sohár, Reijo Sillanpää

Research output: Contribution to journalArticle

Abstract

Aluminium(III)-chloride-catalysed addition of benzene to diendo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (1) and subsequent treatment with acetic anhydride yields 5-exo-phenyl-diendo-bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (2). 3-endo-Hydroxymethyl-5-exo-phenylbicyclo[2.2.1]heptane-2-endo-amine (4) was prepared by LAH reduction of the β-amino acid 3, obtained by Hofmann degradation of the carboxamide prepared from 2. Reaction of 4 with ethyl chloroformate or with CS2/NaOH/Pb2+ furnished the methylene-bridged hexahydro-3,1-benzoxazin-2(1H)-one (5) or -benzoxazine-2(1H)-thione (6). With ethyl chloroacetate or 2-chloropropionate, 4 gave the tricyclic oxazepinones 7 and 8. The norbornane 1,3-aminoalcohol 4 was transformed with phenyl isothiocyanate to the phenylimino-1,3-oxazine 9 and -thiazine 10. The cyclizations of 4 with 2-(p-methylbenzoyl)benzoic acid or cis-2-p-chlorobenzoyl-1-cyclohexanecarboxylic acid led to the methylene-bridged isoindolo[2,1-a][3,1]benzoxazines 11 and 12. With ethyl p-chlorobenzimidate, the diendo-5,8-methano-4H-3,1-benzoxazine 13 was obtained, which was converted with dichloroacetic acid/triethylamine to the isomeric azetidinones 14 and 15, or with benzonitrile oxide to methano-1,2,4-oxadiazolo[4,5-a][3,1]-benzoxazine (16). The stereostructures of the new compounds were elucidated by NMR spectroscopy and for 13 also by X-ray diffractometry.

Original languageHungarian
JournalMagyar Kemiai Folyoirat, Kemiai Kozlemenyek
Volume103
Issue number12
Publication statusPublished - Dec 1997

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Benzoxazines
Heptanes
Amines
Norbornanes
Dichloroacetic Acid
Thiazines
Oxazines
Thiones
Aluminum chloride
Dicarboxylic Acids
Benzoic Acid
Anhydrides
Cyclization
Benzene
Oxides
X ray diffraction analysis
Nuclear magnetic resonance spectroscopy
Amino Acids
Degradation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{61f582692fb4454f9a5f7c760dabfdc1,
title = "3-Endo-(hidroxi-metil)-5-exo-biciklo[2.2.1]heptil-2-endo-amin regioszelekt{\'i}v szint{\'e}zise {\'e}s {\'a}talak{\'i}t{\'a}sa tel{\'i}tett vagy r{\'e}szlegesen tel{\'i}tett diendo-kondenz{\'a}lt heterociklusokk{\'a}",
abstract = "Aluminium(III)-chloride-catalysed addition of benzene to diendo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (1) and subsequent treatment with acetic anhydride yields 5-exo-phenyl-diendo-bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (2). 3-endo-Hydroxymethyl-5-exo-phenylbicyclo[2.2.1]heptane-2-endo-amine (4) was prepared by LAH reduction of the β-amino acid 3, obtained by Hofmann degradation of the carboxamide prepared from 2. Reaction of 4 with ethyl chloroformate or with CS2/NaOH/Pb2+ furnished the methylene-bridged hexahydro-3,1-benzoxazin-2(1H)-one (5) or -benzoxazine-2(1H)-thione (6). With ethyl chloroacetate or 2-chloropropionate, 4 gave the tricyclic oxazepinones 7 and 8. The norbornane 1,3-aminoalcohol 4 was transformed with phenyl isothiocyanate to the phenylimino-1,3-oxazine 9 and -thiazine 10. The cyclizations of 4 with 2-(p-methylbenzoyl)benzoic acid or cis-2-p-chlorobenzoyl-1-cyclohexanecarboxylic acid led to the methylene-bridged isoindolo[2,1-a][3,1]benzoxazines 11 and 12. With ethyl p-chlorobenzimidate, the diendo-5,8-methano-4H-3,1-benzoxazine 13 was obtained, which was converted with dichloroacetic acid/triethylamine to the isomeric azetidinones 14 and 15, or with benzonitrile oxide to methano-1,2,4-oxadiazolo[4,5-a][3,1]-benzoxazine (16). The stereostructures of the new compounds were elucidated by NMR spectroscopy and for 13 also by X-ray diffractometry.",
author = "Mikl{\'o}s Vir{\'a}g and G. St{\'a}jer and {Szab{\'o} E.}, Angela and G. Bern{\'a}th and P. Soh{\'a}r and Reijo Sillanp{\"a}{\"a}",
year = "1997",
month = "12",
language = "Hungarian",
volume = "103",
journal = "Magyar Kemiai Folyoirat, Kemiai Kozlemenyek",
issn = "1418-9933",
publisher = "Magyar Kemikusok Egyesulete/Hungarian Chemical Society",
number = "12",

}

TY - JOUR

T1 - 3-Endo-(hidroxi-metil)-5-exo-biciklo[2.2.1]heptil-2-endo-amin regioszelektív szintézise és átalakítása telített vagy részlegesen telített diendo-kondenzált heterociklusokká

AU - Virág, Miklós

AU - Stájer, G.

AU - Szabó E., Angela

AU - Bernáth, G.

AU - Sohár, P.

AU - Sillanpää, Reijo

PY - 1997/12

Y1 - 1997/12

N2 - Aluminium(III)-chloride-catalysed addition of benzene to diendo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (1) and subsequent treatment with acetic anhydride yields 5-exo-phenyl-diendo-bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (2). 3-endo-Hydroxymethyl-5-exo-phenylbicyclo[2.2.1]heptane-2-endo-amine (4) was prepared by LAH reduction of the β-amino acid 3, obtained by Hofmann degradation of the carboxamide prepared from 2. Reaction of 4 with ethyl chloroformate or with CS2/NaOH/Pb2+ furnished the methylene-bridged hexahydro-3,1-benzoxazin-2(1H)-one (5) or -benzoxazine-2(1H)-thione (6). With ethyl chloroacetate or 2-chloropropionate, 4 gave the tricyclic oxazepinones 7 and 8. The norbornane 1,3-aminoalcohol 4 was transformed with phenyl isothiocyanate to the phenylimino-1,3-oxazine 9 and -thiazine 10. The cyclizations of 4 with 2-(p-methylbenzoyl)benzoic acid or cis-2-p-chlorobenzoyl-1-cyclohexanecarboxylic acid led to the methylene-bridged isoindolo[2,1-a][3,1]benzoxazines 11 and 12. With ethyl p-chlorobenzimidate, the diendo-5,8-methano-4H-3,1-benzoxazine 13 was obtained, which was converted with dichloroacetic acid/triethylamine to the isomeric azetidinones 14 and 15, or with benzonitrile oxide to methano-1,2,4-oxadiazolo[4,5-a][3,1]-benzoxazine (16). The stereostructures of the new compounds were elucidated by NMR spectroscopy and for 13 also by X-ray diffractometry.

AB - Aluminium(III)-chloride-catalysed addition of benzene to diendo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (1) and subsequent treatment with acetic anhydride yields 5-exo-phenyl-diendo-bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (2). 3-endo-Hydroxymethyl-5-exo-phenylbicyclo[2.2.1]heptane-2-endo-amine (4) was prepared by LAH reduction of the β-amino acid 3, obtained by Hofmann degradation of the carboxamide prepared from 2. Reaction of 4 with ethyl chloroformate or with CS2/NaOH/Pb2+ furnished the methylene-bridged hexahydro-3,1-benzoxazin-2(1H)-one (5) or -benzoxazine-2(1H)-thione (6). With ethyl chloroacetate or 2-chloropropionate, 4 gave the tricyclic oxazepinones 7 and 8. The norbornane 1,3-aminoalcohol 4 was transformed with phenyl isothiocyanate to the phenylimino-1,3-oxazine 9 and -thiazine 10. The cyclizations of 4 with 2-(p-methylbenzoyl)benzoic acid or cis-2-p-chlorobenzoyl-1-cyclohexanecarboxylic acid led to the methylene-bridged isoindolo[2,1-a][3,1]benzoxazines 11 and 12. With ethyl p-chlorobenzimidate, the diendo-5,8-methano-4H-3,1-benzoxazine 13 was obtained, which was converted with dichloroacetic acid/triethylamine to the isomeric azetidinones 14 and 15, or with benzonitrile oxide to methano-1,2,4-oxadiazolo[4,5-a][3,1]-benzoxazine (16). The stereostructures of the new compounds were elucidated by NMR spectroscopy and for 13 also by X-ray diffractometry.

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