2-tert-butylsulfanylbenzaldehyde

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: Methyl triphenylphosphonium iodide (1.57 g, 3.88 mmol) was dissolved in 25 ml ether in a 50 mL round-bottomed flask under dry nitrogen. To the mixture was added in one portion at 0° C. potassium tert-butoxide (0.47 g, 4.19 mmol) and it was stirred for 10 min at room temperature. 2-(tert-butylsulfanyl)benzenecarbaldehyde (2.77 mmol) was added in one portion at 0° C. and the reaction mixture was stirred until complete disappearance of the reactants (24 hr) at room temperature (followed by TLC). The mixture was added to 50 mL of saturated sodium bicarbonate solution, followed by extraction with 3×50 ml portions of ether. The extracts were dried with magnesium sulfate and evaporated. The crude product was further purified by chromatography on silica gel using petroleum ether 60-80 as eluent. 0.37 g, 70%, colorless oil. 1H NMR (200 MHz, CDCl3): δ 1.26 (s, 9H), 5.28 (dd, J1=11.0, J2=1.2, 1H), 5.68 (dd, J1=17.8, J2=1.2, 1H), 7.17-7.67 (m, 5H) ppm. the reaction mixture was stirred until complete disappearance of the reactants (24 hr) at room temperature (followed by TLC) followed by extraction with 3×50 ml portions of ether The extracts were dried with magnesium sulfate evaporated The crude product was further purified by chromatography on silica gel

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-fluoro-benzaldehyde (2.00 g, 16.1 mmol), potassium carbonate (2.45 g, 17.7 mmol) and 2-methyl-2-propanethiol (17.1 mmol) were dissolved in 10.0 mL DMF in a 50 mL round-bottomed flask under dry nitrogen, topped with a reflux condenser. The reaction mixture was heated to 50° C. for 4 days. After cooling, the mixture was added to 50 ml of saturated potassium carbonate solution and extracted with 3×50 mL portions of ether. The extracts were dried with magnesium sulfate and evaporated. The crude product was further purified by chromatography on silica gel using 2:1 dichloromethane/n-hexane as eluent to give a yellow oil (1.26 g, 40%). 1H NMR (200 MHz, CDCl3): δ 1.26 (s, 9H), 7.43-7.63 (m, 3H), 7.96 (dd, J1=6.9, J2=2.5, 1H), 10.76 (s, 1H) ppm. topped with a reflux condenser After cooling extracted with 3×50 mL portions of ether The extracts were dried with magnesium sulfate evaporated The crude product was further purified by chromatography on silica gel using 2:1 dichloromethane/n-hexane as eluent

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

Procedure: reacting 2-chlorobenzaldehyde with 1,1-dimethylethanethiol in the presence of a base to form 2-(1,1-dimethylethylthio)benzaldehyde;

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Powdered potassium hydroxide (21.9 g, 390 mmol) and 56 ml (497 mmol) of terbutyl mercaptan were mixed 55.5 ml of dimethylsulfoxide in a 250 ml three-neck flask. To this stirred mixture was added dropwise over a ten minute period 50 g (356 mmol) of 2-chloro-benzaldehyde. During addition of the 2-chlorobenzaldehyde, the reaction mixture warmed to 120° C. After addition was complete, the mixture was allowed to react at about 110° C. for 1.5 hours. At the end of this time, the mixture was cooled to room temperature and taken up on 600 ml of ethyl acetate and 1 liter of water. The organic layer was separated, dried and evaporated to yield 2-(1,1-dimethylethylthio)benzaldehyde, b.p. 80°-82° C. at 0.05 mm Hg, which was used without further purification in the next step of the process. After addition to react at about 110° C. for 1.5 hours At the end of this time, the mixture was cooled to room temperature The organic layer was separated dried evaporated