2007
DOI: 10.1021/cc700105p
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Hartwig–Buchwald Amination on Solid Supports: a Novel Access to a Diverse Set of 1H-Benzotriazoles

Abstract: Hartwig-Buchwald amination reactions of bromo- and chloroarenes were performed on solid supports with triazene-linked arenes. Immobilized 2-haloarenes were treated with diverse primary amines and anilines at 100 degrees C under palladium catalysis to yield N-substituted 2-aminoarenes. The latter were alternatively formed through reaction of bromo- and chloroarenes with immobilized primary 2-aminobenzenes. Subsequent acidic cleavage furnished 1H-benzotriazoles in high purities. The two described routes allow a … Show more

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Cited by 28 publications
(14 citation statements)
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“…The NMR data are analogous to those previously described. 41 1-(4-Fluorophenyl)-1H-benzotriazole (1b) was prepared from benzotriazole (1.2 g) and 1-fluoro-4-iodobenzene (2.7 g) using the general procedure 1, and was isolated (eluent: 4 : 1 heptane-AcOEt) in 80% yield (1.7 g) as a yellow powder: mp 119 °C; 1 H NMR (CDCl 3 , 300 MHz) 7.27-7.33 (m, 2H), 7.43 (ddd, 1H, J = 8.3, 7.0 and 1.0 Hz), 7.55 (ddd, 1H, J = 8.3, 6.9 and 1.1 Hz), 7.68 (dt, 1H, J = 8.4 and 0.9 Hz), 7.72-7.77 (m, 2H), 8.14 (ddd, 1H, J = 8.3, 1.0 and 0.9 Hz); 13 1-(4-Chlorophenyl)-1H-benzotriazole (1c) was prepared from benzotriazole (1.2 g) and 1-chloro-4-iodobenzene (2.9 g) using the general procedure 1, and was isolated (eluent: 4 : 1 heptane-AcOEt) in 78% yield (1.8 g) as a yellow powder: mp 159 °C; 1 H NMR (CDCl 3 , 300 MHz) 7.46 (ddd, 1H, J = 8.4, 6.9 and 1.0 Hz), 7.55-7.62 (m, 3H), 7.74 (ddd, 1H, J = 8.4, 1.0 and 0.9 Hz), 7.74-7.77 (m, 2H), 8.16 (ddd, 1H, J = 8.4, 1.0 and 0.9 Hz); 13 C{1H} NMR (CDCl 3 , 75 MHz) 110.2 (CH), 120.5 (CH), 124.0 (2CH), 124.7 (CH), 128.6 (CH), 130.1 (2CH), 132.2 (C), 134.5 (C), 135.6 (C), 146.6 (C). The NMR data are analogous to those previously described.…”
Section: General Methodsmentioning
confidence: 99%
“…The NMR data are analogous to those previously described. 41 1-(4-Fluorophenyl)-1H-benzotriazole (1b) was prepared from benzotriazole (1.2 g) and 1-fluoro-4-iodobenzene (2.7 g) using the general procedure 1, and was isolated (eluent: 4 : 1 heptane-AcOEt) in 80% yield (1.7 g) as a yellow powder: mp 119 °C; 1 H NMR (CDCl 3 , 300 MHz) 7.27-7.33 (m, 2H), 7.43 (ddd, 1H, J = 8.3, 7.0 and 1.0 Hz), 7.55 (ddd, 1H, J = 8.3, 6.9 and 1.1 Hz), 7.68 (dt, 1H, J = 8.4 and 0.9 Hz), 7.72-7.77 (m, 2H), 8.14 (ddd, 1H, J = 8.3, 1.0 and 0.9 Hz); 13 1-(4-Chlorophenyl)-1H-benzotriazole (1c) was prepared from benzotriazole (1.2 g) and 1-chloro-4-iodobenzene (2.9 g) using the general procedure 1, and was isolated (eluent: 4 : 1 heptane-AcOEt) in 78% yield (1.8 g) as a yellow powder: mp 159 °C; 1 H NMR (CDCl 3 , 300 MHz) 7.46 (ddd, 1H, J = 8.4, 6.9 and 1.0 Hz), 7.55-7.62 (m, 3H), 7.74 (ddd, 1H, J = 8.4, 1.0 and 0.9 Hz), 7.74-7.77 (m, 2H), 8.16 (ddd, 1H, J = 8.4, 1.0 and 0.9 Hz); 13 C{1H} NMR (CDCl 3 , 75 MHz) 110.2 (CH), 120.5 (CH), 124.0 (2CH), 124.7 (CH), 128.6 (CH), 130.1 (2CH), 132.2 (C), 134.5 (C), 135.6 (C), 146.6 (C). The NMR data are analogous to those previously described.…”
Section: General Methodsmentioning
confidence: 99%
“…Luckily, we nally succeeded in optimizing the Buchwald-Hartwig amination [20][21][22] (Table 1) with aniline using the second generation of XPhos palladium as the pre-catalyst and K 3 PO 4 as a base in the mixture of toluene/DMF at 100 C. Under these conditions the desired intermediate 4 was received in an excellent crude purity of 94% (calculated from UHPLC-UV traces). Motivated by this result we subsequently tested variously substituted anilines, benzylamines and other aliphatic amines.…”
mentioning
confidence: 99%
“…[8][9][10] A similar strategy was employed to obtain the triazoles with fused aromatic skeleton via 2,3-didehydronaphthalene intermediate. 12 Recently, Pereira et al has described the ultrasound-assisted synthesis of 1-acylbenzotriazoles from diazotization of o-phenylenediamine. 12 Recently, Pereira et al has described the ultrasound-assisted synthesis of 1-acylbenzotriazoles from diazotization of o-phenylenediamine.…”
mentioning
confidence: 99%