Carbonyl olefi nation of N-substituted tetrahydroquinoline-6-carbaldehydes

Tetrahydroquinolines are important structural fragments of many biologically active compounds exhibiting antifungal, antitumor, antiviral and neurotropic properties. This paper presents methods for the synthesis of N-substituted tetrahydroquinoline-6-carbaldehydes and a study of the possibility of t...

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Main Authors: Karelina, Kristina Olegovna, Potapov, Andrey Юрьевич
Format: Article
Language:English
Published: Saratov State University 2025-06-01
Series:Известия Саратовского университета. Новая серия: Серия Химия. Биология. Экология
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Online Access:https://ichbe.sgu.ru/sites/ichbe.sgu.ru/files/text-pdf/2025/07/himiya-2025-2-128-136.pdf
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author Karelina, Kristina Olegovna
Potapov, Andrey Юрьевич
author_facet Karelina, Kristina Olegovna
Potapov, Andrey Юрьевич
author_sort Karelina, Kristina Olegovna
collection DOAJ
description Tetrahydroquinolines are important structural fragments of many biologically active compounds exhibiting antifungal, antitumor, antiviral and neurotropic properties. This paper presents methods for the synthesis of N-substituted tetrahydroquinoline-6-carbaldehydes and a study of the possibility of their olefi nation using the Wittig and Horner – Wadsworth – Emmons methods. As a result of the interaction of N-alkyl- and N-acylhydroquinolines with the Vilsmeier – Haack complex, N-substituted tetrahydroquinoline-6-carbaldehydes have been obtained in yields of 77–85%. Olefi nation of the obtained carbaldehydes by the Wittig reaction using triphenylalkylphosphonium salts has made it possible to obtain a number of N-substituted derivatives, including: (E)-3-(2,2,4-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl)acrylonitriles, (E)-1-phenyl-3-(2,2,4- trimethyl-1,2,3,4-tetrahydroquinolin-6-yl)prop-2-en-1-ones, ethyl (E)-3-(N-benzoyl-7-methoxy-2,2,4-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl) acrylate. It has been found that when this interaction is extended to N-benzyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline-6-carbaldehyde and N-benzyl-2,2,4-trimethyl-4-(4-chlorophenyl)-1,2,3,4-tetrahydroquinoline-6-carbaldehyde, diffi cult-to-separate mixtures are formed, which is explained by the presence of a methylene-active benzyl group in these compounds, which in the presence of sodium methylate can enter into condensation with the aldehyde fragment. The application of the Horner – Wadsworth – Emmons reaction for the olefi nation of N-methyl- and N-benzyl-1,2,3,4-tetrahydroquinoline-6-carbaldehydes using dimethyl (cyanomethyl) phosphonate has made it possible to synthesize (E)-3-(Nmethyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl) acrylonitrile, (E)-3-(N-benzyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl) acrylonitrile and (E)-3-(-N-benzyl-2,2,4-trimethyl-4-(4-chlorophenyl)-1,2,3,4-tetrahydroquinolin-6-yl) acrylonitrile with yields of 83–89%. Analysis of the ¹H NMR spectra has showed that all the synthesized olefi nation products are in the form of E-isomers. The obtained results demonstrate the potential of using the developed methods for the synthesis of new tetrahydroquinoline derivatives.
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publishDate 2025-06-01
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series Известия Саратовского университета. Новая серия: Серия Химия. Биология. Экология
spelling doaj-art-4eea58132e06490ea1a6856cedd92c8c2025-08-24T15:04:29ZengSaratov State UniversityИзвестия Саратовского университета. Новая серия: Серия Химия. Биология. Экология1816-97752541-89712025-06-0125212813610.18500/1816-9775-2025-25-2-128-136Carbonyl olefi nation of N-substituted tetrahydroquinoline-6-carbaldehydesKarelina, Kristina Olegovna0Potapov, Andrey Юрьевич1Voronezh State University, Universitetskaya sq., 1, Voronezh, Voronezh region, 394036Voronezh State University, Universitetskaya sq., 1, Voronezh, Voronezh region, 394036Tetrahydroquinolines are important structural fragments of many biologically active compounds exhibiting antifungal, antitumor, antiviral and neurotropic properties. This paper presents methods for the synthesis of N-substituted tetrahydroquinoline-6-carbaldehydes and a study of the possibility of their olefi nation using the Wittig and Horner – Wadsworth – Emmons methods. As a result of the interaction of N-alkyl- and N-acylhydroquinolines with the Vilsmeier – Haack complex, N-substituted tetrahydroquinoline-6-carbaldehydes have been obtained in yields of 77–85%. Olefi nation of the obtained carbaldehydes by the Wittig reaction using triphenylalkylphosphonium salts has made it possible to obtain a number of N-substituted derivatives, including: (E)-3-(2,2,4-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl)acrylonitriles, (E)-1-phenyl-3-(2,2,4- trimethyl-1,2,3,4-tetrahydroquinolin-6-yl)prop-2-en-1-ones, ethyl (E)-3-(N-benzoyl-7-methoxy-2,2,4-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl) acrylate. It has been found that when this interaction is extended to N-benzyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline-6-carbaldehyde and N-benzyl-2,2,4-trimethyl-4-(4-chlorophenyl)-1,2,3,4-tetrahydroquinoline-6-carbaldehyde, diffi cult-to-separate mixtures are formed, which is explained by the presence of a methylene-active benzyl group in these compounds, which in the presence of sodium methylate can enter into condensation with the aldehyde fragment. The application of the Horner – Wadsworth – Emmons reaction for the olefi nation of N-methyl- and N-benzyl-1,2,3,4-tetrahydroquinoline-6-carbaldehydes using dimethyl (cyanomethyl) phosphonate has made it possible to synthesize (E)-3-(Nmethyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl) acrylonitrile, (E)-3-(N-benzyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinolin-6-yl) acrylonitrile and (E)-3-(-N-benzyl-2,2,4-trimethyl-4-(4-chlorophenyl)-1,2,3,4-tetrahydroquinolin-6-yl) acrylonitrile with yields of 83–89%. Analysis of the ¹H NMR spectra has showed that all the synthesized olefi nation products are in the form of E-isomers. The obtained results demonstrate the potential of using the developed methods for the synthesis of new tetrahydroquinoline derivatives.https://ichbe.sgu.ru/sites/ichbe.sgu.ru/files/text-pdf/2025/07/himiya-2025-2-128-136.pdf1234-tetrahydroquinolinevilsmeier – haack reactionolefi nationwittig reactionhorner – wadsworth – emmons reaction
spellingShingle Karelina, Kristina Olegovna
Potapov, Andrey Юрьевич
Carbonyl olefi nation of N-substituted tetrahydroquinoline-6-carbaldehydes
Известия Саратовского университета. Новая серия: Серия Химия. Биология. Экология
1
2
3
4-tetrahydroquinoline
vilsmeier – haack reaction
olefi nation
wittig reaction
horner – wadsworth – emmons reaction
title Carbonyl olefi nation of N-substituted tetrahydroquinoline-6-carbaldehydes
title_full Carbonyl olefi nation of N-substituted tetrahydroquinoline-6-carbaldehydes
title_fullStr Carbonyl olefi nation of N-substituted tetrahydroquinoline-6-carbaldehydes
title_full_unstemmed Carbonyl olefi nation of N-substituted tetrahydroquinoline-6-carbaldehydes
title_short Carbonyl olefi nation of N-substituted tetrahydroquinoline-6-carbaldehydes
title_sort carbonyl olefi nation of n substituted tetrahydroquinoline 6 carbaldehydes
topic 1
2
3
4-tetrahydroquinoline
vilsmeier – haack reaction
olefi nation
wittig reaction
horner – wadsworth – emmons reaction
url https://ichbe.sgu.ru/sites/ichbe.sgu.ru/files/text-pdf/2025/07/himiya-2025-2-128-136.pdf
work_keys_str_mv AT karelinakristinaolegovna carbonylolefinationofnsubstitutedtetrahydroquinoline6carbaldehydes
AT potapovandreyûrʹevič carbonylolefinationofnsubstitutedtetrahydroquinoline6carbaldehydes