Nitrogen bridgehead compounds. Part 86 [1]. Synthesis and reactivity of 7,12-dihydropyrimido[1′,2′;1,2]pyrido[3,4-b]indol-4(6H)-ones. Debenzologues of rutaecarpine alkaloids

I. Hermecz, P. Forgó, Zsolt Böcskei, Miklós Fehér, J. Kökösi, G. Szász

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Abstract

A series of 7,12-dihydropyrimido[1′,2′:1,2]pyrido[3,4-b]indole-4(6H)-ones was prepared by Fischer indolization of 9-arylhydrazono-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidin-4-ones. Quantum chemical calculations (ab initio and AM1) indicate that position 3 of 7,12-dihydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indole-4(6H)-one can be involved in electrophilic substitutions, while position 2 is sensitive towards nucleophilic attack. Bromination of 6-methyl-7,12-tetrahydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indol-4(6H) -one 16 with bromine afforded 3-bromo derivative 25, which was reacted with cyclic amines to give 2-amino-7,12-dihydropyrimido[1′,2′:1,2]pyrido[3,4-b]indol-4(6H)-ones 26-30 in an addition-elimination reaction. Vielsmeier-Haack formylation of compound 16 gave 12-formyl 31 and 3,12-diformyl 32 derivatives (an N-formyl-1-deaza derivative of nauclefidine alkaloid 34) at 60° and 100°, respectively. 3,12-Diformyl compound 32 was oxidized to 3-carboxyl derivative 33 with potassium permanganate. The quaternary salt 35, obtained from compound 16 with dimethyl sulfate, suffered a ring opening on the action of aqueous sodium hydroxide. The new compounds have been characterized by elemental analyses uv, 1H nmr and in some cases by 13C ruler, CD spectra and X-ray investigations.

Original languageEnglish
Pages (from-to)799-809
Number of pages11
JournalJournal of Heterocyclic Chemistry
Volume33
Issue number3
Publication statusPublished - May 1996

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Nitrogen Compounds
Alkaloids
Derivatives
Carbolines
Potassium Permanganate
Bromine
Sodium Hydroxide
Amines
Substitution reactions
Salts
X rays
rutecarpine

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

@article{b4f9a0fdd07041a4a769e18ced999be0,
title = "Nitrogen bridgehead compounds. Part 86 [1]. Synthesis and reactivity of 7,12-dihydropyrimido[1′,2′;1,2]pyrido[3,4-b]indol-4(6H)-ones. Debenzologues of rutaecarpine alkaloids",
abstract = "A series of 7,12-dihydropyrimido[1′,2′:1,2]pyrido[3,4-b]indole-4(6H)-ones was prepared by Fischer indolization of 9-arylhydrazono-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidin-4-ones. Quantum chemical calculations (ab initio and AM1) indicate that position 3 of 7,12-dihydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indole-4(6H)-one can be involved in electrophilic substitutions, while position 2 is sensitive towards nucleophilic attack. Bromination of 6-methyl-7,12-tetrahydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indol-4(6H) -one 16 with bromine afforded 3-bromo derivative 25, which was reacted with cyclic amines to give 2-amino-7,12-dihydropyrimido[1′,2′:1,2]pyrido[3,4-b]indol-4(6H)-ones 26-30 in an addition-elimination reaction. Vielsmeier-Haack formylation of compound 16 gave 12-formyl 31 and 3,12-diformyl 32 derivatives (an N-formyl-1-deaza derivative of nauclefidine alkaloid 34) at 60° and 100°, respectively. 3,12-Diformyl compound 32 was oxidized to 3-carboxyl derivative 33 with potassium permanganate. The quaternary salt 35, obtained from compound 16 with dimethyl sulfate, suffered a ring opening on the action of aqueous sodium hydroxide. The new compounds have been characterized by elemental analyses uv, 1H nmr and in some cases by 13C ruler, CD spectra and X-ray investigations.",
author = "I. Hermecz and P. Forg{\'o} and Zsolt B{\"o}cskei and Mikl{\'o}s Feh{\'e}r and J. K{\"o}k{\"o}si and G. Sz{\'a}sz",
year = "1996",
month = "5",
language = "English",
volume = "33",
pages = "799--809",
journal = "Journal of Heterocyclic Chemistry",
issn = "0022-152X",
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TY - JOUR

T1 - Nitrogen bridgehead compounds. Part 86 [1]. Synthesis and reactivity of 7,12-dihydropyrimido[1′,2′;1,2]pyrido[3,4-b]indol-4(6H)-ones. Debenzologues of rutaecarpine alkaloids

AU - Hermecz, I.

AU - Forgó, P.

AU - Böcskei, Zsolt

AU - Fehér, Miklós

AU - Kökösi, J.

AU - Szász, G.

PY - 1996/5

Y1 - 1996/5

N2 - A series of 7,12-dihydropyrimido[1′,2′:1,2]pyrido[3,4-b]indole-4(6H)-ones was prepared by Fischer indolization of 9-arylhydrazono-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidin-4-ones. Quantum chemical calculations (ab initio and AM1) indicate that position 3 of 7,12-dihydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indole-4(6H)-one can be involved in electrophilic substitutions, while position 2 is sensitive towards nucleophilic attack. Bromination of 6-methyl-7,12-tetrahydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indol-4(6H) -one 16 with bromine afforded 3-bromo derivative 25, which was reacted with cyclic amines to give 2-amino-7,12-dihydropyrimido[1′,2′:1,2]pyrido[3,4-b]indol-4(6H)-ones 26-30 in an addition-elimination reaction. Vielsmeier-Haack formylation of compound 16 gave 12-formyl 31 and 3,12-diformyl 32 derivatives (an N-formyl-1-deaza derivative of nauclefidine alkaloid 34) at 60° and 100°, respectively. 3,12-Diformyl compound 32 was oxidized to 3-carboxyl derivative 33 with potassium permanganate. The quaternary salt 35, obtained from compound 16 with dimethyl sulfate, suffered a ring opening on the action of aqueous sodium hydroxide. The new compounds have been characterized by elemental analyses uv, 1H nmr and in some cases by 13C ruler, CD spectra and X-ray investigations.

AB - A series of 7,12-dihydropyrimido[1′,2′:1,2]pyrido[3,4-b]indole-4(6H)-ones was prepared by Fischer indolization of 9-arylhydrazono-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidin-4-ones. Quantum chemical calculations (ab initio and AM1) indicate that position 3 of 7,12-dihydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indole-4(6H)-one can be involved in electrophilic substitutions, while position 2 is sensitive towards nucleophilic attack. Bromination of 6-methyl-7,12-tetrahydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indol-4(6H) -one 16 with bromine afforded 3-bromo derivative 25, which was reacted with cyclic amines to give 2-amino-7,12-dihydropyrimido[1′,2′:1,2]pyrido[3,4-b]indol-4(6H)-ones 26-30 in an addition-elimination reaction. Vielsmeier-Haack formylation of compound 16 gave 12-formyl 31 and 3,12-diformyl 32 derivatives (an N-formyl-1-deaza derivative of nauclefidine alkaloid 34) at 60° and 100°, respectively. 3,12-Diformyl compound 32 was oxidized to 3-carboxyl derivative 33 with potassium permanganate. The quaternary salt 35, obtained from compound 16 with dimethyl sulfate, suffered a ring opening on the action of aqueous sodium hydroxide. The new compounds have been characterized by elemental analyses uv, 1H nmr and in some cases by 13C ruler, CD spectra and X-ray investigations.

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