Ethyl isothiocyanatoformate → Ethyl (6-bromo-pyridin-2-ylamino)carbonothioylcarbamate

HRID 885641Notes

Reaction equation

HRID 885641 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Br:8])[N:3]=1.[CH2:9]([O:11][C:12]([N:14]=[C:15]=[S:16])=[O:13])[CH3:10]>C(Cl)Cl>[Br:8][C:4]1[N:3]=[C:2]([NH:1][C:15]([NH:14][C:12]([O:11][CH2:9][CH3:10])=[O:13])=[S:16])[CH:7]=[CH:6][CH:5]=1

Participants

4

Reactant 2

HCID 85320Ethyl isothiocyanatoformateHCID 3008092-Amino-6-bromopyridine

Product 1

HCID 57361094Ethyl (6-bromo-pyridin-2-ylamino)carbonothioylcarbamate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

To a solution of 2-amino-6-bromopyridine (1) (253.8 g, 1.467 mol) in DCM (2.5 L) cooled to 5° C. is added ethoxycarbonyl isothiocyanate (173.0 mL, 1.467 mol) dropwise over 15 min. The reaction mixture is then allowed to warm to room temp. (20° C.) and stirred for 16 h. Evaporation in vacuo gives a solid which may be collected by filtration, thoroughly washed with petrol (3×600 mL) and air-dried to afford (2). The thiourea may be used as such for the next step without any purification. 1H (400 MHz, CDCl3) δ 12.03 (1H, br s, NH), 8.81 (1H, d, J 7.8 Hz, H-3), 8.15 (1H, br s, NH), 7.60 (1H, t, J 8.0 Hz, H-4), 7.32 (1H, dd, J 7.7 and 0.6 Hz, H-5), 4.31 (2H, q, J 7.1 Hz, CH2), 1.35 (3H, t, J 7.1 Hz, CH3).

Workup

  1. customEvaporation in vacuo
  2. customgives a solid which
  3. filtrationmay be collected by filtration
  4. washthoroughly washed with petrol (3×600 mL)
  5. customair-dried

Sources & evidence

ORD record
ord-bb3d62bca17b4bee91ad6323d55e5006
Source dataset
uspto-grants-2012_08
Patent number
US08242274B2

Reaction notes

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