Einwirkung von tertiären Aminen auf o‐metallierte Arylhalogenide, I Umsetzungen von tertiären Benzylaminen mit o‐metalliertem Fluorbenzol und o‐Fluor‐toluol

Hellmann, H.; Unseld, Werner

doi:10.1002/jlac.19606310108

Cited by 18 publications

(3 citation statements)

References 6 publications

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“…These rearrangements are very base and solvent dependant as well and, for benzyltrimethylammonium ion at least, almost exclusive ortho migration can be observed within the temperature range currently used.18 '8'11 The low ortho conversions ob-(9) A. R, Lepley, R. H. Becker, and A. G. Giumanini, ibid., 36, 1222 (1971). (10) C. R. Hauser, R. M. Manyik, W. R. Brasen, and P. L. Bayless, ibid., 20, 1119 (1955).…”

Section: Discussionmentioning

confidence: 99%

Quaternary benzylammonium ion rearrangements with organolithium compounds. V. Reaction of N,N-dimethyl-N-benzylanilinium halides

Lepley¹,

Giumanini²

1971

J. Org. Chem.

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A new rearrangement product, N-methyl-N-(wphenethy1)aniline (4), and a new cleavage product, N-methyl-AJ-benzylaniline (j), have been observed in reactions of N,N-dimethyl-N-beneylanilinium ion (1) with organolithium bases. N-Methyl-lV-(p-phenyl)aniline ( 5 ) was directly isolated from reaction mixtures, whereas it is destroyed by sodium amide. The Sommelet rearrangement product, N-methyl-it7-(0-xyly1)aniline ( 6 ) , was observed in very small quantities because of the benzylation of its 0-Li precursor by the starting salt, to give a dimeric product. Cleavage reactions of the quaternary benzylanilinium salt with potassium hydroxide and sodium ethoxide in refluxing ethanol also gave 3 in addition to the principal products, X,N-dimethylaniline (2) and ethyl benzyl ether. Analogous cleavage products were observed with organolithium reagents plus significant amounts of trans-stilbene (8). The effects of concentration, ether-hexane solvent mixtures, and anion of the salt on the ratios of rearrangement and cleavage products were studied for n-butyllithium reactions and are interpreted in terms of dianion and radical pair mechanisms.

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Section: Discussionmentioning

confidence: 99%

Quaternary benzylammonium ion rearrangements with organolithium compounds. V. Reaction of N,N-dimethyl-N-benzylanilinium halides

Lepley¹,

Giumanini²

1971

J. Org. Chem.

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“…Removal of the elution with chloroform afforded 80 mg (1.2%) of 7a, the spectroscopic data of which were identical with those of the authentic specimen. Evaporation of the successive elution with 5% ethanol-chloroform gave 300 mg (2.5%) of 2,4-dimethyl-1phenylpiperazine.. (9): nmr (CC14) 1.08 (3 H, d, CHCHs), 2.01-2.95 [4 H, m, -CH2N(CH3)CH2-], 2.30 (3 H, s, NCH3), (15) A. A. Morton and W. R. Salunwhite, Jr., J. Biol.…”

Section: Experimental Section13mentioning

confidence: 99%

“…In the case of the benzyne reaction of 2-benzyloxychlorobenzene with N-methylmorpholine, N-methyl-N-(2-vinyloxy ethyl) aniline (4a), and 2-[N-methyl-N-(3-methylphenyl) ] aminoethanol (8b) were obtained in addition to the desired product, 3-benzyloxy-N-methylaniline (7f). Benzyne reaction of bromobenzene with N,iV,-dimethylpiperazineaffordediV-methyl-iV'-(d-methylaminoethyl) aniline (8c) together with 7a and the Stevens type rearranged product, 2,4-dimethyl-lphenylpiperazine (9). Furthermore, piperidinobenzene was obtained on the benzyne reaction of bromobenzene with N-methylpiperidine as reported by Wittig.6 The mechanism to explain the formation of these products remained unclear but would involve the reaction of the base with the quaternary salt (2) as shown in Scheme I.…”

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confidence: 99%

Syntheses of heterocyclic compounds. CDLX. Benzyne reaction. XIII. Benzyne reaction of halogenobenzenes with N-alkylmorpholines

Kametani¹,

Kigasawa²,

Hiiragi³

et al. 1972

J. Org. Chem.

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Über das Verhalten von Dehydrobenzol gegenüber Pyrrol, N‐Benzyl‐ und N‐Phenyl‐pyrrol

Wittig

Reichel

1963

Chem. Ber.

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N-Substituierte F'yrrolderivate gehen mit Dehydrobenzol eine normale DielsAlder-Addition zu 1.4-Dihydro-naphthalin-I A-endamin-Derivaten ein. die sich mit uberschussigem Dehydrobenzol weiter umwandeln khnen. Eine Ausnahme bildet das Pyrrol selbst, das sich mit Dehydrobenzol in substituierender Addition zum a-Phenyl-pyrrol vereinigt.Nach friiheren Untersuchungen 2) reagiert Dehydrobenzol n i t N-Methyl-pyrrol, das als quasiaromatisches System wenig ausgepragte Dieneigenschaften zeigt31, in normaler Diels-Alder-Addition unter Bildung von N-Methyl-I .4-dihydro-naphfhulinlin-I .6endamin ( I ) :

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Einwirkung von tertiären Aminen auf o‐metallierte Arylhalogenide, I Umsetzungen von tertiären Benzylaminen mit o‐metalliertem Fluorbenzol und o‐Fluor‐toluol

Abstract: MERKLE, Ber. dtsch. chem. Ges. 76, 109 (1943).

Cited by 18 publications

References 6 publications

Quaternary benzylammonium ion rearrangements with organolithium compounds. V. Reaction of N,N-dimethyl-N-benzylanilinium halides

Quaternary benzylammonium ion rearrangements with organolithium compounds. V. Reaction of N,N-dimethyl-N-benzylanilinium halides

Syntheses of heterocyclic compounds. CDLX. Benzyne reaction. XIII. Benzyne reaction of halogenobenzenes with N-alkylmorpholines

Über das Verhalten von Dehydrobenzol gegenüber Pyrrol, N‐Benzyl‐ und N‐Phenyl‐pyrrol

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