Dimethylformamide → 2-Difluoromethoxy-6-propylsulfanylbenzonitrile

HRID 1983984Notes

Reaction equation

[F:1][CH:2]([F:13])[O:3][C:4]1[CH:11]=[CH:10][CH:9]=[C:8](F)[C:5]=1[C:6]#[N:7].CN(C)C=O.[CH2:19]([SH:22])[CH2:20][CH3:21].[OH-].[K+]>O>[F:1][CH:2]([F:13])[O:3][C:4]1[CH:11]=[CH:10][CH:9]=[C:8]([S:22][CH2:19][CH2:20][CH3:21])[C:5]=1[C:6]#[N:7]

Participants

Conditions

Temperature: 0 °C

Procedure

180 g (0.96 mol) 2-difluoromethoxy-6-fluorobenzonitrile were introduced into 1.5 l of dimethylformamide at room temperature. 73.2 g (0.96 mol) of propanethiol were added dropwise and, after cooling to 0° C., 70 g (1.25 mol) of potassium hydroxide pellets, dissolved in 600 ml of water, were added dropwise at 0° C. The mixture was stirred for one hour and then warmed to room temperature. The reaction mixture was stirred into 3.5 l of ice-water and extracted three times with 500 ml of methyl tert.-butyl ether. The combined organic phases were washed twice with 500 ml of 1N hydrochloric acid and dried over sodium sulfate. Then, the solvent was distilled off in vacuo. The oil obtained was distilled in vacuo (b.p.: 180-185° C./0.5 mbar). Yield: 76% of theory. 1H NMR (in CDCl3): δ=1.1 ppm (t, 3H, CH3), 1.75 ppm (m, 2H, CH2CH3), 3.0 ppm (t, 2H, SCH2), 6.5-6.85 ppm (t, 1H, OCF2H), 7.05 ppm (d, 1H, arom. H), 7.2 ppm (d, 1H, arom. H), 7.5 ppm (t, 1H, arom. H).

Workup

additionwere added dropwise at 0° C
temperaturewarmed to room temperature
extractionextracted three times with 500 ml of methyl tert.-butyl ether
washThe combined organic phases were washed twice with 500 ml of 1N hydrochloric acid
dry with materialdried over sodium sulfate
distillationThen, the solvent was distilled off in vacuo
customThe oil obtained
distillationwas distilled in vacuo (b.p.: 180-185° C./0.5 mbar)

Sources & evidence

ORD record: ord-85c6807445fc4885b4d3b72aa0833232
Source dataset: uspto-grants-2009_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07544637B2

Reaction notes

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