Synthesen mit aliphatischen Dialdehyden, XLI. Benzylidenmalonaldehyd — Herstellung, Struktur und Reaktionen

Reichardt, Christian; Yun, Kyeong-Yeol; Massa, W.; Schmidt, Roland

doi:10.1002/jlac.198519851007

Cited by 9 publications

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“…These dialdehydes belong to a new class of cross-conjugated methylenmalonaldehydes, the chemistry of which, studied more recently (see for example [45]), has been reviewed already [46].…”

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confidence: 99%

Vilsmeier-Haack-Arnold formylations of aliphatic substrates withN-chloromethylene-N,N-dimethylammonium salts

Reichardt¹

1999

J. prakt. Chem.

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609In 1927, Anton Vilsmeier, a young thirty-three years old German chemist at the University of Erlangen [1], published with his coworker Albrecht Haack [2] a rather short paper [3], dealing with the formylation of aromatics, activated by electrondonating substituents, with phosphorus oxytrichloride (POCl 3 ) and N-methylformanilide (MFA) to give, after hydrolysis of the primary electrophilic substitution product, the corresponding aromatic aldehydes according to Scheme 1.A first, singular example of such a formylation reaction was already found by Dimroth and Zoeppritz in 1902 [4]. However, Vilsmeier and Haack discovered the general applicability of this formylation reaction to a variety of activated Abstract. The classical electrophilic substitution of activated aromatics with the Vilsmeier-Haack reagent N-chloromethylen-N,N-dimethylammonium chloride (Schemes 1 and 2) has been more recently extended to a great variety of aliphatic substrates, mainly due to the work of Arnold. In this review, a collection of representative examples for these henceforth called Vilsmeier-Haack-Arnold (VHA) formylation reaction of aliphatics is given: the reaction of polymethine cyanines, merocyanines, and other vinylogous iminium salts with the VHA reagent gives, after hydrolysis of the primary substitution products, trialdehydes such as triformylmethane (Scheme 3); VHA reaction with ene-diamines and diene-diamines yields N,N-dialkylaminomalonaldehydes and tetraalaromatic and heteroaromatic substrates [3]. The mechanistic classification of the Vilsmeier-Haack (VH) formylation reaction into the group of common electrophilic substitution reactions was later on proposed by Wizinger [5]. Nowadays,

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“…These dialdehydes belong to a new class of cross-conjugated methylenmalonaldehydes, the chemistry of which, studied more recently (see for example [45]), has been reviewed already [46].…”

mentioning

confidence: 99%

Vilsmeier-Haack-Arnold formylations of aliphatic substrates withN-chloromethylene-N,N-dimethylammonium salts

Reichardt¹

1999

J. prakt. Chem.

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“…-'H-NMR (2proz. Losung in CDCI'): Bei 290 K: 6 = 2.47 (m; 1 H, 1-H), 5.25 (dd, ' J = 5.8 und 8.9 Hz; 2H, 2,7-H), 6.25 (m; 2H, 3,6-H), 6.72 (m; 2H, 4,5-H), 8.43 (s; 2H, Aldehyd-und Enol-CH),13.84 (s, br. ; 1 H, OH; verschwindet bei D,O-Zugabe.…”

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Synthesen mit aliphatischen Dialdehyden, XL. (2,4,6‐Cycloheptatrien‐1‐yl)malonaldehyd – Herstellung, Struktur und Reaktionen

et al. 1985

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Tropylierung des Malonaldehyd-Natriumsalzes mit Cycloheptatrienylium-tetrafluoroborat ergab erstmals den enolisierten, s-trans-konfigurierten (2,4,6-Cycloheptatrien-l-yl)malonaldehyd (1). Umsetzungen von 1 rnit Anilinen fiihren zu den 3-Anilino-2-propenalen 3 und 4, rnit dem Fischerbase-Quartarsalz zum Pentamethincyanin-Farbstoff 5, mit Maleinsaureanhydrid und Tetracyanethylen zu den Cycloaddukten 6 und 7, und rnit bifunktionellen NNucleophilen zu den cycloheptatrienylsubstituierten Heterocyclen 10-12. Die Struktur von 3 und 5 wurde rontgenographisch ermittelt.Syntheses with Aliphatic Dialdehydes, XL'). -(2,4,6-Cycloheptatrien-l-yl)malonaldehyde - Synthesis, Structure, and Reactions')Tropylation of the sodium salt of malonaldehyde with cycloheptatrienylium tetrafluoroborate yielded the enolized, s-trans-configurated (2,4,6-cycloheptatrien-l-yl)malonaldehyde (1) for the first time. Reaction of 1 with anilines leads to the 3-anilino-2-propenals 3 and 4, with Fischer's base to the pentamethine cyanine dye 5, with maleic anhydride and tetracyanoethylene to the cycloadducts 6 and 7, and with bifunctional N-nucleophiles to the cycloheptatrienyl-substituted heterocycles 10-12. The structures of 3 and 5 were determined by means of X-ray analyses.Substituierte Malonaldehyde sind wertvolle bifunktionelle C,Synthesebausteine, deren Kondensationsreaktionen es gestatten, eine Vielzahl verschiedener Substituenten in offenkettige') sowie carbo-6) und heterocyclische') Zielmolekule einzufuhren, was nachtraglich oft nicht oder nur schwierig gelingt8s9).Wahrend Cycloalkylmalonaldehyde mit gesattigten Ringen (Cyclopropyl-bis Cycloheptyl-') sowie 1-und 2-Adamantylmal0naldehyd~~)) kiirzlich von uns erstmals beschrieben ~urden','~), sind Malonaldehyde rnit ungesattigten Cycloalkylsubstituenten bisher kaum bekannt geworden. Lediglich Arylmalonaldehyde") und einige heteroarylsubstituierte Malonaldehyde") sind seit langerem bekannt.Im AnschluB an die Synthese gesattigter Cycloalkylmalonaldehyde7.'0' berichten wir nun uber Herstellung, Feinstruktur und Reaktionen des (Cycloheptatrieny1)-malonaldehyds'). Dieser Malonaldehyd ist nicht nur als Synthesebaustein zur 0 VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1985

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ChemInform Abstract: Syntheses with Aliphatic Dialdehydes. Part 41. Benzylidenemalonaldehyde

Reichardt¹,

Yun²,

Massa³

et al. 1986

Chemischer Informationsdienst

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Synthesen mit aliphatischen Dialdehyden, XLI. Benzylidenmalonaldehyd — Herstellung, Struktur und Reaktionen

Cited by 9 publications

References 15 publications

Vilsmeier-Haack-Arnold formylations of aliphatic substrates withN-chloromethylene-N,N-dimethylammonium salts

Vilsmeier-Haack-Arnold formylations of aliphatic substrates withN-chloromethylene-N,N-dimethylammonium salts

Synthesen mit aliphatischen Dialdehyden, XL. (2,4,6‐Cycloheptatrien‐1‐yl)malonaldehyd – Herstellung, Struktur und Reaktionen

ChemInform Abstract: Syntheses with Aliphatic Dialdehydes. Part 41. Benzylidenemalonaldehyde

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