Silver-Catalyzed Tandem Ammonolysis-Cyclization of 2-Alkynylbenzenamines with Tetraalkylthiuram Disulfides to 4-Methylene-4H-benzo[d][1,3]thiazin-2-amines

Abstract

In the presence of AgBF₄, the ammonolysis-cyclization tandem reactions of various 2-alkynylbenzenamines with tetraalkyl­thiuram disulfides afforded the corresponding 4-methylene-4H-benzo[d][1,3]thiazin-2-amines in moderate to good yields.

Key words

silver - tandem reaction - 2-alkynylbenzenamine - tetra­alkylthiuram disulfide - 4-methylene-4H-benzo[d][1,3]thiazin-2-amine

References and Notes

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10

The crystal structure of compound 3 has been deposited at the Cambridge Crystallographic Data Centre and allocated the deposition number CCDC 769763.

11

General Procedure for the Silver-Catalyzed Tandem Reaction
A flame-dried Schlenk tube with a magnetic stirring bar was charged with 2-alkynylbenzenamine 1 (0.5 mmol), tetraalkylthiuram disulfide 2 (0.5 mmol), AgBF₄ (0.05 mmol), and DMSO (1 mL). The reaction mixture was stirred at 80 ˚C for 36 h. After the reaction was finished, the mixture was poured into EtOAc, washed with brine (3 × 10 mL), and extracted with EtOAc. The combined organic layers were dried by anhyd Na₂SO₄ and evaporated under vacuum. The residue was purified by flash column chromatography (hexane-EtOAc) to afford the desired product.
4-Benzylidene- N , N -dimethyl-4 H -benzo[ d ][1,3]thiazin-2-amine (3) Z/E = 90:10; pale yellow solid, mp 68.9-72.6 ˚C (uncorrected). ^¹H NMR (300 MHz, CDCl₃): δ = 7.51-7.46 (m, 3 H), 7.43-7.38 (m, 2 H), 7.29-7.25 (m, 2 H), 7.21-7.17 (m, 2 H), 7.08-7.07 (m, 2 H), 3.21 (s, 0.6 H), 3.16 (s, 5.4 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 153.3, 145.0, 136.0, 129.6, 129.4, 128.1 (2 C), 127.2, 126.0, 125.5, 124.2, 123.4, 120.0, 38.2. IR (KBr): 2924, 1560, 1187, 756 cm^-¹. LRMS (EI, 70 eV): m/z (%) = 280 (100) [M⁺], 236 (78). ESI-HRMS: m/z calcd for C₁₇H₁₇N₂S [M + H]⁺: 281.1107; found: 281.1104.
3-[2-(3,3-Dimethylbut-1-ynyl)phenyl]-1,1-dimethyl-thiourea (22) Pale yellow solid, mp 88.1-89.3 ˚C (uncorrected). ^¹H NMR (300 MHz, CDCl₃): δ = 8.34 (d, J = 8.3 Hz, 1 H), 7.77 (br, 1 H), 7.37 (d, J = 7.7 Hz, 1 H), 7.28-7.26 (m, 1 H), 7.05-7.02 (m, 1 H), 3.41 (s, 6 H), 1.34 (s, 9 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 180.3, 140.3, 131.8, 127.8, 123.5, 121.9, 115.1, 105.7, 75.0, 41.2, 31.1, 28.3. IR (KBr): 3367, 2963, 1530, 1335, 755 cm^-¹. LRMS (EI, 70 eV): m/z (%) = 260 (29) [M⁺], 245 (37), 200(18), 88 (100), 88. ESI-HRMS: m/z calcd for for C₁₅H₂₁N₂S [M + H]⁺: 261.1420; found: 261.1419.
( E )-1,1-Dimethyl-3-(2-styrylphenyl)thiourea (23) Pale yellow solid, mp 211.3-214.1 ˚C (uncorrected). ^¹H NMR (300 MHz, CDCl₃): δ = 7.52-7.49 (m, 1 H), 7.35 (d, J = 7.7 Hz, 2 H), 7.31-7.29 (m, 2 H), 7.28-7.25 (m, 4 H), 7.07-6.99 (m, 2 H), 3.30 (s, 6 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 183.3, 137.6, 137.1, 133.2, 131.5, 128.7, 128.1, 128.0, 127.3, 126.8 (2 C), 126.4, 123.7, 41.8. IR (KBr): 2924, 1524, 1332, 758 cm^-¹. LRMS (EI, 70 eV): m/z (%) = 282 (100) [M⁺], 249 (27), 237 (100), 204 (32), 88 (78). ESI-HRMS: m/z calcd for C₁₇H₁₉N₂S [M + H]⁺: 283.1263; found: 283.1260.