Gas phase rearrangement reactions of 2-(arylamino)phenylaminyl radicals

Cadogan, J. I. G.; Hutchison, H. S.; McNab, Hamish

doi:10.1039/p19870001407

Cited by 12 publications

(5 citation statements)

References 6 publications

(8 reference statements)

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“…The crude pyrolysate from the FVP of N-[2-(benzyloxy)phenyl]pyrrole 5aa (0.553 g, 2 mmol), (T f 750 • C, T i 140-160 • C, P 0.005 Torr, t 10 min) was worked up as described for 5a and the products were separated by dry-flash chromatography to give N-(2-hydroxyphenyl)pyrrole 4a (0.040 g, 11%), 2-(2hydroxyphenyl)pyrrole 24 8 (0.071 g, 20%), bp 150-155 • C (0.1 Torr) (Found: M + 159.0686. C 10 H 9 NO requires M 159.0684), 1 H NMR and mass spectra compatible with those reported above; and 3-(2-hydroxyphenyl)pyrrole 9 (0.035 g, 10%), 24…”

Section: Fvp Of N-[2-(benzyloxy)phenyl]pyrrole 5aasupporting

confidence: 79%

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Reactions of 2-(pyrrol-1-yl)benzyl radicals and related species under flash vacuum pyrolysis conditions

et al. 2009

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2-(Pyrrol-1-yl)phenoxyl, aminyl, thiophenoxyl and benzyl radicals 2a-2d, respectively, were generated in the gas-phase under flash vacuum pyrolysis conditions. In all cases except the phenoxyl, cyclisation took place providing acceptable synthetic routes to the fused heterocycles 11, 14 and 15, respectively. Only sigmatropic rearrangement products were isolated, in low yields, from the phenoxyl 2a. The pyrrolo[1,2-a]benzimidazole 11 adopts the 1H-tautomer exclusively in chloroform solution. Electrophilic substitution reactions of pyrrolo[2,1-b]benzothiophene 14 were studied, including protonation, deuterium exchange, Vilsmeier formylation and reaction with dimethyl acetylenedicarboxylate. 2-(2,5-Diarylpyrrol-1-yl)thiophenoxyl, phenoxyl and aminyl radicals 23a-f, were also generated in the gas-phase under similar conditions. The thiophenoxyls 23a/b gave extremely complex pyrolysate mixtures in which primary cyclisation products were formed by attack of the radical at the pyrrrole ring and attack at the ipso-, ortho- and meta- positions of the aryl ring. Secondary pyrolysis products were obtained by specific sigmatropic shifts of the N-aryl group. The 2,5-di(thien-2-yl)thiophenoxyl radical 23c gave the pyrrolobenzothiazole 31c as the only cyclisation product in low yield. FVP of the phenoxyl and aminyl radical generators 26d and 26f, respectively, gave 3-arylpyrrolo[1,2-f]phenanthridines 46d and 46f, respectively, by a hydrogen transfer-cyclisation mechanism.

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Section: Fvp Of N-[2-(benzyloxy)phenyl]pyrrole 5aasupporting

confidence: 79%

“…1 X, Y = O, NH, S, CH 2 ). [1][2][3][4] The radicals were generated in the gas-phase by flash vacuum pyrolysis (FVP). Reactions of soft radicals 1 (X = CH 2 or S) are dominated by ipso-attack to provide a 5-membered ring intermediate, leading to rearranged cyclised products.…”

Section: Introductionmentioning

confidence: 99%

Reactions of 2-(pyrrol-1-yl)benzyl radicals and related species under flash vacuum pyrolysis conditions

et al. 2009

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“…When 2-aminodiphenylamine 5d was reacted at 450-6 0 0°C, phenazine 1 2 was obtained in good yields (51-77%) (Entry 13-16). The yield is better compared to flash vaccum pyrolysis (57%) of 2-aminodiphenylamine [20] and reaction (46%) of 2-nitrodiphenylamine with iron [1a]. In contrast, reaction of 2-aminodiphenyl ether 5e at 450°C gave only 2-hydroxydiphenylamine 13 in 25% yield and phenazine was not obtained (Entry [17][18][19].…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Carbazole, Acridine, Phenazine, 4H‐Benzo[def]carbazole and Their Derivatives by Thermal Cyclization Reaction of Aromatic Amines.

et al. 2004

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Ring closure reactions Ring closure reactions O 0130Synthesis of Carbazole, Acridine, Phenazine, 4H-Benzo[def]carbazole and Their Derivatives by Thermal Cyclization Reaction of Aromatic Amines. -An intramolecular cyclization reaction of aromatic amines yields nitrogen-containing fiveand six-membered heterocycles by passing vapors of the amines over calcium oxide at 450-650°C under nitrogen carrier gas. The reactions are carried out with 2-amino--2'-substituted biphenyls as well as with amines having a carbon-, nitrogen-, or oxygen--containing linker group between two benzene rings. Additionally, the intramolecular cyclization behavior of aminophenanthrene (XIV) is investigated. At present, the reaction mechanism is not yet clear. -(HORAGUCHI*, T.; OYANAGI, T.; CREENCIA, E. C.; TANEMURA, K.; SUZUKI, T.; J. Heterocycl. Chem. 41 (2004) 1, 1-6; Dep. Chem., Fac. Sci., Niigata Univ., Ikarashi, Niigata 950-21, Japan; Eng.) -H. Hoennerscheid 26-036

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“…C,,Hl,NO requires C, 81.0; H, 6.35; N, 5.9"/,,): 6" 8.75 (1 H, br s), 7.25-7.69 (7 H, m), 6.44-6.82 (2 H, m), 5.99 ( 1 H, m), 5.13-5.48 (2 H, m) and 3.95 (2 H, m); 6c 199.14 (q), 151.42 (q), 140.32 (q), 135.25, 134.69, 134.09, 130.53, 128.78, 127.80, 117.23 (q), 116.02, 113.76, 11 1.68 and 44.97; mi-237 (M', 100"4J), 236 (36), 167 (18), 132 (36), 105 (30), 91 (15) and 77 (45). 3.85 (2 H, m) and 2.39 (3 H, s); 6c 155.04 (q), 143.41 (q), 139.95 (q), 135.17, 132.04 (q), 129.98, 124. 33, 118.51, 117.34, 116.57, 115.83, 111.70, 45.87 and 20.43; m / z 239 (M+, loo%), 183 (29), 132 (16), 131 (33), 130 (23), 120 (39, 105 (25) This material was not further purified, but was dissolved in methanol (20 cm3), and reduced to the N-benzyl compound by treatment with solid sodium borohydride l o (1.0 g, 25 mmol).…”

Section: -Allylaminodiphenylmethane and Relatedmentioning

confidence: 99%

Gas-phase rearrangement and cyclisation reactions of 2-benzylphenylaminyl radicals and related 2-hetero-analogues

Cadogan¹,

Hickson²,

Hutchison³

et al. 1991

J. Chem. Soc., Perkin Trans. 1

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Gas phase rearrangement reactions of 2-(arylamino)phenylaminyl radicals

Cited by 12 publications

References 6 publications

Reactions of 2-(pyrrol-1-yl)benzyl radicals and related species under flash vacuum pyrolysis conditions

Reactions of 2-(pyrrol-1-yl)benzyl radicals and related species under flash vacuum pyrolysis conditions

Synthesis of Carbazole, Acridine, Phenazine, 4H‐Benzo[def]carbazole and Their Derivatives by Thermal Cyclization Reaction of Aromatic Amines.

Gas-phase rearrangement and cyclisation reactions of 2-benzylphenylaminyl radicals and related 2-hetero-analogues

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