Unsaturated Aromatic Amines; a Novel Synthesis of Indoles

Hyre, John E.; Bader, Alfred R.

doi:10.1021/ja01535a048

Cited by 27 publications

(11 citation statements)

References 4 publications

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“…In 1950, Hyre et al reported the hydroamination of 1,3-butadiene with aniline in the presence of metallic sodium at 120 8C to form N-crotylaniline in 79% yield. [28] As in the case of aliphatic olefins, alkali metal amide catalysts derived in situ from Na 2 Np [29] and sec-BuLi [23] are more active than metallic sodium and are effective at much lower temperatures. For instance, piperidine and diethylamine react with 1,3-butadiene at room temperature to 50 8C in the presence of catalytic amounts of sec-BuLi or Na 2 Np forming N-2-butenylpiperidine and 1diethylaminobut-2-ene (> 80% yields).…”

Section: Hydroamination Of 13-dienesmentioning

confidence: 99%

Base‐Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

et al. 2003

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Section: Hydroamination Of 13-dienesmentioning

confidence: 99%

Base‐Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

et al. 2003

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“…Several other examples (50-60% yields) were provided, including hydroamination with primary amines, piperidine, anilines and hexamethylenediamine [197][198][199]. The special case of aziridine was reported to afford a mixture of isomers 'in a good yield' [200].…”

Section: (452)mentioning

confidence: 99%

Catalytic Hydroamination of Unsaturated Carbon‐Carbon Bonds

Brunet

Neibecker

2001

Catalytic Heterofunctionalization

139

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“…hierzu die Diskussionen in [12] [13] [19]. [28] oder Salzsaure bei 180" [14] in Anilin, Indolin-und Indolderivat eine ladungsinduzierte Umlagerung der N-Allyl-aniline einschliesst.…”

Section: *)unclassified

“…Unter den Reaktionsbedingungen wird 41 nicht in 42 uberfuhrt, d. h. der fur die Bildung von 42 notwendige Dehydrierungsschritt tritt schon bei 43 ein (vgl. hierzu [14][28]) lo).…”

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Zinkchloridkatalysierte, thermische Umlagerungen von N‐Allyl in C‐Allyl‐aniline; ladungsinduzierte, aromatische Amino‐Claisen‐Umlagerungen

Schmid

Hansen

Schmid

1973

Helvetica Chimica Acta

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N-Allyl-2-methylaniline (12) forms on heating at 140" in xylene in the presence of zinc chloride 2-allyl-6-methylaniline (19) as major compound and 4-allyl-2-methylaniline (20) as well as 2,7-dimethyl-indoline (21) as minor products. Compound 21 is also formed when 19 is heated in the presence of zinc chloride (schcme 2). That 19 arises from a chargc-induced [3 s, 3s) sigmatropic rearrangement of 12 -and 20 from two consecutive [3s, 3s]-sigmatropic transformationsfollows from the reaction of N-crotyl-2-niethylanilinc (13) in the presence of zinc chloride at 140". 2-(l'-Methylallyl)-6-methylanilinc (22) and 4-crotyl-2-mcthylaniline (23) are formed cxclusively. Small amounts of 2.3.7-trimethyl-indoline (24) and 2-(czs-and trans-1'-methylpropenyl)-6-methylaniline (cis-and tralzs-25) are observed as by-products. Compound 24 arises from 22 in the presence of zinc chloride (scheme 3 ) . Similar results are obtained when N-allyland N-(2'-methylallyl)-N-methyl-aniline (14 and 15, respectively) are heated in the presence of zinc chloride. Whercas 14 gives nearly exclusively 2-allyl-N-rncthyl-aniline (28) and only small amounts of the corresponding 1,2-dimethyl-indoline (29) and of 2-(cisand trans-propeny1)-Nmethyl-aniline (cis-and trans-27), 15 forms comparable amounts of 2-(2'-methylallyl)-N-mcthylaniline (30), 1,2,2-trimethyl-indoline (31), and 2-isobutenyl-N-methyl-aniiiline (32) (schcme 4). Compound 30, and also 32, are transformed into 31 on heating in the presence of zinc chloride.Chargc-induced aromatic amino-Claisen rearrangemcnts are also observed when N-allylated anilininm tetraphenylborates are heated a t 100-105' in hexamethyl phosphoric acid triamide. Thus, N-allyl-and N-crotyl-N, N-dimethyl-aniliniuni tetraphenylborate (16 and 17, rcspectively) yicld 2-allyl-and 2-(1'-mcthylally1)-N, N-dimethyl-aniline (33 and 34, respectively) besides small amounts of N, gives, besides appreciable amounts of N, N-dimethyl-aniline, a mixture of Z-(l'-phenylallyl)-, 2-cinnamyl-, and 4-cinnamyl-N, N-dimethyl-aniline (35, 36, and 37, respectively) in which the first two compounds predominate.Teil der geplantrn Dissertation J1. Sckmid, Universitiit Zurich. Das Ringspannung aufwcisende l-$-Bromphenyl-2-isopropenylazirldiIi wird schon bei 140 ' in hoher Ausbeutc in 7-Brom-4-methyl-2,5-diliydro-(l-benzazepin) umgcwandelt [3], z,

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Unsaturated Aromatic Amines; a Novel Synthesis of Indoles

Cited by 27 publications

References 4 publications

Base‐Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

Base‐Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

Catalytic Hydroamination of Unsaturated Carbon‐Carbon Bonds

Zinkchloridkatalysierte, thermische Umlagerungen von N‐Allyl in C‐Allyl‐aniline; ladungsinduzierte, aromatische Amino‐Claisen‐Umlagerungen

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