O,O-Diethyl dithiophosphate → Methyl 4-carbamothioylbenzoate

HRID 931451Notes

Reaction equation

[C:1]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=1)#[N:2].P(S)(OCC)(OCC)=[S:14]>O>[NH2:2][C:1]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=1)=[S:14]

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of methyl 4-cyanobenzoate (5.0 g, 31.0 mmol) and O,O-diethyl hydrogen dithiophosphate (10.41 g, 62 mmol) in water (100 mL) was stirred at 80° C. for 16 h under N2. The mixture was cooled to 20° C. and filtered. The precipitate was washed with water (50 mL) and dried under vacuum to give crude methyl 4-(aminocarbothioyl)benzoate (5.93 g, 98%) as a yellow powder: mp (water) 181-184° C.; 1H NMR δ 10.04 (br s, 1H, NH2), 9.65 (br s, 1H, NH2), 7.83-8.00 (m, 4H, H-2, H-3, H-5, H-6), 3.88 (s, 3H, OCH3); MS m/z 196.5 (MH+, 100%). A mixture of the crude benzoate (5.72 g, 29.2 mmol) and dichloroacetone (3.72 g, 29.3 mmol) in anhydrous DMF (50 mL) was stirred at 80° C. under N2 for 16 h. The mixture was cooled to 20° C. and poured into ice/water (400 mL) and stirred for 30 min. The precipitate was filtered, washed with water (30 mL) and dried. The residue was purified by column chromatography, eluting with a gradient (10-20%) of EtOAc/pet. ether, to give benzoate 51 (5.40 g, 69%) as a white powder: mp (EtOAc/pet. ether) 110-111° C.; 1H NMR (CDCl3) δ 8.11 (ddd, J=8.7, 2.0, 1.6 Hz, 2H, H-2, H-6), 8.02 (ddd, J=8.7, 2.0, 1.6 Hz, 2H, H-3, H-5), 7.38 (s, 1H, H-5′), 4.76 (s, 2H, CH2Cl), 3.95 (s, 3H, OCH3); MS m/z 268.6 (MH+, 100%). Anal. calcd for C12H10ClNO2S: C, 53.83; H, 3.76; N, 5.23. Found: C, 53.77; H, 3.72; N, 5.03%.

Workup

temperatureThe mixture was cooled to 20° C.
filtrationfiltered
washThe precipitate was washed with water (50 mL)
customdried under vacuum

Sources & evidence

ORD record: ord-a8e70ad17bb847eba8500c8452140630
Source dataset: uspto-grants-2016_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09296732B2

Reaction notes

Loading…