5-Bromopyridine-2-carbonitrile → 5-(Methylsulfonyl)pyridine-2-carbonitrile

HRID 1517472Notes

Reaction equation

Br[C:2]1[CH:3]=[CH:4][C:5]([C:8]#[N:9])=[N:6][CH:7]=1.[CH3:10][S:11]([O-:13])=[O:12].[Na+]>CS(C)=O>[CH3:10][S:11]([C:2]1[CH:3]=[CH:4][C:5]([C:8]#[N:9])=[N:6][CH:7]=1)(=[O:13])=[O:12]

Participants

Conditions

Temperature: 100 °C

Procedure

To 5-Bromo-2-cyanopyridine (17.5 kg, 1 mol eq, limiting reagent) and DMSO (103.6 L, 6 rel vol) was charged sodium methanesulfinate (13.7 kg, 1.4 mol eq) and the reaction heated to 100° C. for 24 hours. The reaction mixture was cooled to 50° C. and the product precipitated by addition of water (163 L, 9.3 rel vol). The mixture was then cooled to 25° C. and stirred for at least 9 hours. The solid was collected by filtration, washed twice with water (40 L, 2.3 rel vol) and dried to constant weight yielding the title compound (10.9 kg, 5.9 mol, 60%; 1H NMR (CDCl3): 9.24 (dd, 1H, J 0.8, 2.3 Hz); 8.41 (dd, 1H, J 2.3, 8.2 Hz); 7.93 (dd, 1H, J 0.8, 8.2 Hz); 3.17 (s, 3H) ppm.

Workup

temperatureThe reaction mixture was cooled to 50° C.
customthe product precipitated by addition of water (163 L, 9.3 rel vol)
temperatureThe mixture was then cooled to 25° C.
filtrationThe solid was collected by filtration
washwashed twice with water (40 L, 2.3 rel vol)
customdried to constant weight

Sources & evidence

ORD record: ord-3ee09d722a674346b3df77e29cfe5d35
Source dataset: uspto-grants-2012_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08232296B2

Reaction notes

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