2,6-dimethylbenzenethiol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using the method of Example 3, Step A, 2,6-dimethylbenzenethiol (0.872 g, 6.31 mmol), 60% sodium hydride in mineral oil (252 mg, 6.31 mmol), and 2-chloro-4-nitropyridine (1.00 g, 6.31 mmol) were reacted to provide 2-chloro-4-(2,6-dimethylphenylthio)pyridine (1.35 g, 86% yield) as a white solid. 1H NMR (CDCl3) δ 8.07 (d, 1H), 7.22-7.34 (m, 3H), 6.75 (s, 1H), 6.71 (d, 1H), 2.40 (s, 6H). were reacted

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using the method of Example 3, Step A, 2,6-dimethylbenzenethiol (0.872 g, 6.31 mmol), 60% sodium hydride in mineral oil (252 mg, 6.31 mmol), and 2-chloro-4-nitropyridine (1.00 g, 6.31 mmol) were reacted to provide 2-chloro-4-(2,6-dimethylphenylthio)pyridine (1.35 g, 86% yield) as a white solid. 1H NMR (CDCl3) δ 8.07 (d, 1H), 7.22-7.34 (m, 3H), 6.75 (s, 1H), 6.71 (d, 1H), 2.40 (s, 6H). were reacted

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-benzyl-2-(4-bromo-phenyl)-morpholine (2.00 g; 6.02 mmol) and 2,6-dimethylthiophenol (0.88 mL; 6.62 mmol) in DMF (15 mL) was added CuBr (0.43 g; 3.01 mmol), 1,2,3,4-tetrahydro-quinolin-8-ol (0.45 g; 3.01 mmol) and Cs2CO3 (2.45 g; 7.52 mmol; 1.25 eq.). The resulting mixture was heated, in a closed vessel, at 130° C., for 2 days. After cooling to RT, water was added and the mixture extracted with Et2O. The combined organic layers were washed with water, dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (Et2O/hexanes 1:1) to afford 4-benzyl-2-[4-(2,6-dimethyl-phenylsulfanyl)-phenyl]-morpholine (1.60 g). After cooling to RT the mixture extracted with Et2O The combined organic layers were washed with water dried (Na2SO4) filtered concentrated in vacuo The residue was purified by column chromatography (Et2O/hexanes 1:1)

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-benzyl-2-(4-bromo-phenyl)-morpholine (2.00 g; 6.02 mmol) and 2,6-dimethylthiophenol (0.88 mL; 6.62 mmol) in DMF (15 mL) was added CuBr (0.43 g; 3.01 mmol), 1,2,3,4-tetrahydro-quinolin-8-ol (0.45 g; 3.01 mmol) and Cs2CO3 (2.45 g; 7.52 mmol; 1.25 eq.). The resulting mixture was heated, in a closed vessel, at 130° C., for 2 days. After cooling to RT, water was added and the mixture extracted with Et2O. The combined organic layers were washed with water, dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (Et2O/hexanes 1:1) to afford 4-benzyl-2-[4-(2,6-dimethyl-phenylsulfanyl)-phenyl]-morpholine (1.60 g). After cooling to RT the mixture extracted with Et2O The combined organic layers were washed with water dried (Na2SO4) filtered concentrated in vacuo The residue was purified by column chromatography (Et2O/hexanes 1:1)

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The general procedure was used to convert iodobenzene and 2,6-dimethylthiophenol to the title product. Purification by flash chromatography (hexane as the eluent) gave the analytically pure product as a clear oil (409 mg, 95% yield). 1H NMR (300 MHz, CDCl3) δ 7.1–6.98 (m, 5H; Hc, Hc, Hd, Hd′, He), 6.93–6.86 (m, 1H; Hb), 6.77 (d, J=7.16, 2H; Ha, Ha′) 2.34 (s, 6H; methyl protons). 13C NMR (75 MHz, CDCl3) δ 143.86 (C2, C6), 137.98 (C9), 130.43 (C1), 129.22 (C4), 128.86 (C10, C14), 128.40 (C1, C13), 125.59 (C3, C5), 124.57 (C12), 21.82 (C7, C8). Anal. Calcd. for C14H14S: C, 78.45; H, 6.58; S, 14.96; Found C, 78.58; H, 6.71; S, 14.98.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The general procedure was used to convert iodobenzene and 2,6-dimethylthiophenol to the title product. Purification by flash chromatography (hexane as the eluent) gave the analytically pure product as a clear oil (409 mg, 95% yield). 1H NMR (300 MHz, CDCl3) δ 7.1–6.98 (m, 5H; Hc, Hc, Hd, Hd′, He), 6.93–6.86 (m, 1H; Hb), 6.77 (d, J=7.16, 2H; Ha, Ha′) 2.34 (s, 6H; methyl protons). 13C NMR (75 MHz, CDCl3) δ 143.86 (C2, C6), 137.98 (C9), 130.43 (C1), 129.22 (C4), 128.86 (C10, C14), 128.40 (C1, C13), 125.59 (C3, C5), 124.57 (C12), 21.82 (C7, C8). Anal. Calcd. for C14H14S: C, 78.45; H, 6.58; S, 14.96; Found C, 78.58; H, 6.71; S, 14.98.