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Synlett 2010(1): 55-60  
DOI: 10.1055/s-0029-1218533
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Microwave-Assisted Stille Reactions as a Powerful Tool for Building Polyheteroaryl Systems Bearing a (1H)-1,2,4-Triazole Moiety

C. Cebriána, A. de Cózara, P. Prieto*a, A. Díaz-Ortiz*a, A. de la Hoza, J. R. Carrilloa, A. M. Rodrigueza, F. Montillab
a Facultad de Química, Universidad de Castilla-La Mancha, 13071, Ciudad Real, Spain
Fax: +926-295318; e-Mail: MariaPilar.Prieto@uclm.es;
b Facultad de Ciencias, Universidad de Alicante, Apdo. de Correos 99, 03080, Alicante, Spain
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Publikationsverlauf

Received 29 September 2009
Publikationsdatum:
02. Dezember 2009 (online)

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Abstract

Stille couplings and the combination of Stille/Heck cross-coupling reactions provide useful access to tricyclic systems with valuable material properties from 3,5-dibromo-1,2,4-triazoles. The reactions can all be dramatically improved under microwave irradiation.

Key words

Stille reaction - microwave - (1H)-1,2,4-triazole - 1,2,3-triazole - electropolymerization

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18

General Procedure: A mixture of 3,5-dibromo-1-methyl-1H-1,2,4-triazole (1; 200 mg, 0.83 mmol), stannyl derivative (2; 1.08 mmol), PdCl2(PPh3)2 (12 mg, 0.017 mmol) and LiCl (106 mg, 2.49 mmol) or CuI (15.8 mg, 0.083 mmol) was irradiated under argon in a Discover™ (CEM) focused microwave reactor at 110 ˚C for 15 min. The crude products 3a and 4a-g were purified by flash chromatography on silica gel (hexane-EtOAc).
5-Bromo-1-methyl-3-(thiophen-2-yl)-1 H -1,2,4-triazole (3a): Mp 54-55 ˚C; ¹H NMR (CDCl3): δ = 7.58 (dd, J = 3.7, 1.2 Hz, 1 H, H-3′), 7.28 (dd, J = 5.1, 1.2 Hz, 1 H, H-5′), 7.02 (dd, J = 5.1, 3.7 Hz, 1 H, H-4′), 3.84 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 159.0, 132.8, 129.7, 127.7, 126.8, 126.5, 36.5 (CH3).
3-Bromo-1-methyl-5-(thiophen-2-yl)-1 H -1,2,4-triazole (4a): Mp 67-68 ˚C; ¹H NMR (CDCl3): δ = 7.54-7.62 (m, 2 H, H-3′′, H-5′′), 7.19 (dd, J = 5.1, 3.7 Hz, 1 H, H-4′′), 4.06 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 151.1, 138.7, 129.4, 129.0, 128.0, 127.9, 37.4 (CH3).
3-Bromo-1-methyl-5-(1-methyl-1 H -pyrrol-2-yl)-1 H -1,2,4-triazole (4b): Mp 41-42 ˚C; ¹H NMR (CDCl3): δ = 6.74 (t, J = 1.8 Hz, 1 H, H-5′′), 6.41 (dd, J = 4.0, 1.5 Hz, 1 H, H-3′′), 6.14 (dd, J = 3.7, 2.6 Hz, 1 H, H-4′′), 4.06 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 149.9, 138.3, 126.8, 118.3, 113.1, 108.2, 37.1 (CH3), 36.0 (CH3).
5-(2,2′-Bithiophen-5-yl)-3-bromo-1-methyl-1 H -1,2,4-triazole (4c): Mp 152-154 ˚C; ¹H NMR (CDCl3): δ = 7.61 (d, J = 3.9 Hz, 1 H, H-3), 7.31 (dd, J = 5.1, 1.1 Hz, 1 H, H-3′), 7.27 (dd, J = 3.8, 1.1 Hz, 1 H, H-5′), 7.20 (d, J = 3.9 Hz, 1 H, H-4), 7.05 (dd, J = 5.1, 3.8 Hz, 1 H, H-4′); ¹³C NMR (CDCl3): δ = 150.7, 141.7, 138.7, 135.7, 129.5, 128.1, 125.9, 125.9, 125.0, 124.1, 35.5 (CH3).
3-Bromo-1-methyl-5-phenyl-1 H -1,2,4-triazole (4d): Mp 120-121 ˚C; ¹H NMR (CDCl3): δ = 7.59-7.61 (m, 2 H, o-PhH), 7.44-7.46 (m, 3 H, m-PhH, p-PhH), 3.91 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 156.6, 139.1, 130.7, 129.0, 128.7, 126.7, 37.3 (CH3).
3-Bromo-1-methyl-5-(phenylethynyl)-1 H -1,2,4-triazole (4e): Mp 119-120 ˚C; ¹H NMR (CDCl3): δ = 7.52-7.55 (m, 2 H, o-PhH), 7.28-7.94 (m, 3 H, m-PhH, p-PhH), 3.97 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 147.7, 140.3, 132.1, 132.0, 129.2, 128.7, 128.4, 121.7, 97.4, 89.5, 36.5 (CH3). 2-(3-Bromo-1-methyl-1 H -1,2,4-triazol-5-yl)pyridine (4f): Mp 78-80 ˚C; ¹H NMR (CDCl3): δ = 8.68 (dd, J = 4.8, 1.8 Hz, 1 H, H-6), 8.20 (dd, J = 7.7, 1.1 Hz, 1 H, H-3), 7.85 (td, J = 7.7, 1.8 Hz, 1 H, H-4), 7.37 (ddd, J = 7.7, 4.8, 1.1 Hz, 1 H, H-5), 4.36 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 153.4, 148.9, 146.8, 138.3, 137.1, 124.5, 124.0, 39.3 (CH3).
2-(3-Bromo-1-methyl-1 H -1,2,4-triazol-5-yl)pyrazine (4g): Mp 131-133 ˚C; ¹H NMR (CDCl3): δ = 9.45 (s, 1 H, H-3), 8.67, 8.64 (2 × s, 2 H, H-5 and H-6), 4.34 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 151.1, 145.2, 154.1, 143.1, 142.5, 138.8, 39.3 (CH3).

19

General Procedure: A mixture of 3,5-dibromo-1-methyl-1H-1,2,4-triazole (1; 200 mg, 0.83 mmol), stannyl derivative (2; 2.16 mmol, 2.6 equiv), PdCl2 (PPh3)2 (24 mg, 0.033 mmol) and LiCl (106 mg, 2.49 mmol) was irradiated under argon in a Discover™ (CEM) focused microwave reactor at 130 ˚C for the appropriate time. The crude products 5a-c were purified by flash chromatography on silica gel (hexane-EtOAc).
1-Methyl-3,5-di(thiophen-2-yl)-1 H -1,2,4-triazole (5a): Mp 107-108 ˚C; ¹H NMR (CDCl3): δ = 7.71 (dd, J = 3.7, 1.1 Hz, 1 H, H-3′), 7,54 (dd, J = 3.7, 1.1 Hz, 1 H, H-3′′), 7.53 (dd, J = 5.1, 1.1 Hz, 1 H, H-5′′), 7.34 (dd, J = 4.8, 1.1 Hz, 1 H, H-5′), 7.18 (dd, J = 5.1, 3.7 Hz, 1 H, H-4′′), 7.10 (dd, J = 5.1, 3.7 Hz, 1 H, H-4′), 4.07 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 157.3, 150.0, 133.5, 128.9, 128.7, 128.6, 127.9, 127.6, 126.3, 126.2, 37.1 (CH3).
1-Methyl-3,5-bis(1-methyl-1 H -pyrrol-2-yl)-1 H -1,2,4-triazole (5b): Mp 78-79 ˚C; ¹H NMR (CDCl3): δ = 6.74 (t, J = 2.0 Hz, 1 H, H-5′′), 6.73 (dd, J = 2.0, 1.0 Hz, 1 H, H-5′), 6.62 (t, J = 2.0 Hz, 1 H, H-3′), 6.43 (dd, J = 4.4, 2.4 Hz, 1 H, H-3′′), 6.17 (dd, J = 4.0, 2.4 Hz, 1 H, H-4′′), 6.10 (dd, J = 3.4, 2.9 Hz, 1 H, H-4′), 3.94 (s, 3 H, CH3), 3.91 (s, 3 H, CH3), 3.85 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 155.9, 148.0, 126.1, 125.0, 124.8, 119.8, 112.3, 110.3, 108.0, 107.7, 36.7 (CH3), 36.6 (CH3), 36.1 (CH3).
3,5-Di(2,2′-bithiophen-5-yl)-1-methyl-1 H -1,2,4-triazole (5c): Mp 146-148 ˚C; ¹H NMR (CDCl3): δ = 7.61 (d, J = 3.8 Hz, 1 H, H-3′′), 7.45 (d, J = 3.8 Hz, 1 H, H-3), 7.22-7.31 (m, 5 H, H-4, H-3′, H-5′, H-3′′′, H-5′′′), 7.17 (d, J = 3.8 Hz, 1 H, H-4′′), 7.07 (dd, J = 4.9, 3.8 Hz, 1 H), 7.03 (t, J = 4.3 Hz, 1 H, H-4′ and H-4′′′); ¹³C NMR (CDCl3): δ = 156.9, 149.7, 140.8, 138.2, 137.2, 136.1, 131.9, 129.0, 128.1, 127.9, 127.2, 126.9, 125.6, 124.8, 124.7, 124.2, 124.1, 124.0, 37.3 (CH3).

20

General Procedure: A mixture of 5-monosubstituted triazole 4 (1 equiv), stannyl derivative (2; 1.3 equiv),
PdCl2 (PPh3)2 (0.02 equiv) and LiCl (3 equiv) or CuI (0.1 equiv) was irradiated at the appropriate temperature and for the appropriate time under argon in a Discover™ (CEM) focused microwave reactor. The crude products 6a-c were purified by flash chromatography on silica gel (hexane-EtOAc).
1-Methyl-3-(1-methyl-1 H -pyrrol-2-yl)-5-(thiophen-2-yl)-1 H -1,2,4-triazole (6a): Mp 88-89 ˚C; ¹H NMR (CDCl3): δ = 7.53 (dd, J = 3.7, 1.5 Hz, 1 H, H-3′′), 7.52 (dd, J = 5.1, 1.1 Hz, 1 H, H-5′′), 7.18 (dd, J = 5.1, 3.7 Hz, 1 H, H-4′′), 6.81 (dd, J = 3.7, 1.8 Hz, 1 H, H-5′), 6.70 (t, J = 2.2 Hz, 1 H, H-3′), 6.17 (dd, J = 3.7, 2.6 Hz, 1 H, H-4′), 4.08 (s, 3 H, CH3), 4.00 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 156.3, 149.1, 129.5, 128.5, 128.2, 127.8, 125.2, 124.4, 110.8, 107.8, 37.0 (CH3), 36.5 (CH3).
3-(2,2′-Bithiophen-5-yl)-1-methyl-5-(thiophen-2-yl)-1 H -1,2,4-triazole (6b): Mp 124-126 ˚C; ¹H NMR (CDCl3): δ = 7.62 (d, J = 3.8 Hz, 1 H, H-4′′), 7.57 (dd, J = 3.7, 1.1 Hz, 1 H, H-3′′′), 7.55 (dd, J = 5.1, 1.1 Hz, 1 H, H-5′′′), 7.24-7.23 (m, 2 H, H-3′, H-5′), 7.20 (dd, J = 5.1, 3.7 Hz, 1 H, H-4′′′), 7.07 (dd, J = 3.8 Hz, 1 H, H-3′′), 7.03 (dd, J = 3.8, 4.9 Hz, 1 H, H-4′), 4.09 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 156.9, 150.1, 138.2, 137.2, 131.9, 128.9, 128.8, 128.7, 127.9, 126.9, 124.7, 124.4, 124.0, 37.2 (CH3).
2-[1-Methyl-3-(thiophen-2-yl)-1 H -1,2,4-triazol-5-yl]pyrazine (6c): Mp 139-140 ˚C; ¹H NMR (CDCl3): δ = 9.55 (d, J = 1.7 Hz, 1 H, H-3 Py), 8.64-8.67 (m, 2 H, H-5, H-6 Py), 7.75 (dd, J = 3.7, 1.1 Hz, H-3 thioph), 7.37 (dd, J = 5.1, 1.1 Hz, 1 H, H-5 thioph), 7.13 (dd, J = 5.1, 3.7 Hz, 1 H, H-4 thioph), 4.37 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 157.5, 150.1, 145.4, 144.7, 143.5, 143.0, 133.5, 127.7, 126.5, 126.3.

21

General Procedure: A mixture of 1-phenyl-4-(tributyl-stannyl)-1H-1,2,3-triazole (11; 100 mg, 0.23 mmol), halogenated derivative 12 (0.25 mmol), PdCl2(PPh3)2 (3 mg, 0.004 mmol) and LiCl (29.3 mg, 0.69 mmol) was irradiated at the appropriate temperature and for the appropriate time under argon in a Discover™ (CEM) focused microwave reactor. The crude products 13a-g were purified by flash chromatography (hexane-EtOAc).
4-(3,5-Dimethylphenyl)-1-phenyl-1 H -1,2,3-triazole (13a): Mp 115-116 ˚C; ¹H NMR (CDCl3): δ = 8.1 (s, 1 H, H-5), 7.8 (d, J = 7.3 Hz, 2 H, o-PhH), 7.5 (m, 4 H, Ph′H), 7.4 (t, J = 7.3 Hz, 1 H, p-Ph′H), 7.0 (s, 1 H, p-PhH), 2.2 (s, 6 H, 2 × CH3); ¹³C NMR (CDCl3): δ = 148.6, 138.5, 137.1, 130.1, 129.9, 128.7, 123.6, 120.5, 117.5, 21.3 (CH3).
4-(2,6-Dimethylphenyl)-1-phenyl-1 H -1,2,3-triazole (13b): Colorless oil; ¹H NMR (CDCl3): δ = 7.9 (s, 1 H, H-5), 7.8 (d, J = 7.1 Hz, 2 H, o-PhH), 7.5 (t, J = 6.9 Hz, 2 H,
m-PhH), 7.4 (t, J = 7.3 Hz, 1 H, p-PhH), 7.2-7.1 (m, 3 H, PhH′), 2.3 (s, 6 H, 2 × CH3); ¹³C NMR (CDCl3): δ = 146.2, 137.9, 137.1, 129.8, 129.6, 123.6, 120.3, 117.5, 20.8 (CH3).
4-(3-Bromophenyl)-1-phenyl-1 H -1,2,3-triazole (13c): Yellow oil; ¹H NMR (CDCl3): δ = 8.2 (s, 1 H), 8.0 (m, 1 H), 7.8-7.7 (m, 3 H), 7.6-7.5 (m, 4 H), 7.3 (t, J = 7.3 Hz, 1 H, p-PhH); ¹³C NMR (CDCl3): δ = 147.0, 136.9, 132.3, 131.3, 130.5, 129.8, 128.9, 128.8, 124.4, 123.0, 120.6, 117.9.
4-(Naphthalen-1-yl)-1-phenyl-1 H -1,2,3-triazole (13d): Mp 106-107 ˚C; ¹H NMR (CDCl3): δ = 8.5-8.4 (m, 1 H, H-Naph), 8.2 (s, 1 H, H-5), 7.9-7.8 (m, 5 H), 7.6-7.4 (m, 6 H); ¹³C NMR (CDCl3): δ = 147.6, 137.1, 133.9, 131.2, 129.9, 129.8, 129.2, 128.8, 128.5, 127.7, 127.4, 126.7, 126.1, 125.4, 120.6.
2-(1-Phenyl-1 H -1,2,3-triazol-4-yl)pyrazine (13e): Colorless oil; ¹H NMR (CDCl3): δ = 9.5 (s, 1 H, H-Py), 8.6 (s, 1 H, H-5), 8.6-8.5 (m, 2 H, H-Py), 7.8 (d, J = 7.3 Hz, 2 H, o-PhH), 7.5 (t, J = 7.3 Hz, 2 H, m-PhH), 7.4 (t, J = 7.3 Hz, 1 H, p-PhH); ¹³C NMR (CDCl3): δ = 146.6, 145.7, 144.1, 143.9, 142.3, 136.7, 129.9, 129.2, 120.9, 120.6.
1,1′-Diphenyl-1 H ,1′ H -4,4′-bi(1,2,3-triazole) (13f): Mp 118-119 ˚C; ¹H NMR (CDCl3): δ = 8.6 (s, 1 H), 8.0 (s, 1 H), 7.7 (d, J = 7.3 Hz, 4 H, o-PhH), 7.5 (t, J = 7.3 Hz, 4 H,
m-PhH), 7.4 (d, J = 7.3 Hz, 2 H, p-PhH). ¹³C NMR (CDCl3): δ = 137.0, 134.4, 129.7, 128.7, 121.6, 120.6.
4-(3-Bromo-1-methyl-1 H -1,2,4-triazol-5-yl)-1-phenyl-1 H -1,2,3-triazole (13g): Mp 104-105 ˚C; ¹H NMR (CDCl3): δ = 8.5 (s, 1 H, H-5), 7.7 (d, J = 7.3 Hz, 2 H, o-PhH), 7.5 (t, J = 8 Hz, 2 H, m-PhH), 7.4 (d, J = 7.1 Hz, 1 H, p-PhH), 4.3 (s, 3 H, CH3); ¹³C NMR (CDCl3): δ = 147.5, 138.9, 137.7, 136.3, 130.1, 129.6, 122.6, 120.6, 38.3 (CH3).