Ammonium thiocyanate → Ethyl 2-amino-4-bromo-5-thiocyanatobenzoate

HRID 34625Notes

Reaction equation

HRID 34625 reaction equation
Cl.[NH2:2][C:3]1[CH:13]=[C:12]([Br:14])[CH:11]=[CH:10][C:4]=1[C:5]([O:7][CH2:8][CH3:9])=[O:6].[S-:15][C:16]#[N:17].[NH4+].BrBr>C(O)(=O)C>[NH2:2][C:3]1[CH:13]=[C:12]([Br:14])[C:11]([S:15][C:16]#[N:17])=[CH:10][C:4]=1[C:5]([O:7][CH2:8][CH3:9])=[O:6]

Participants

5

Reactant 3

HCID 15666Ammonium thiocyanateHCID 24408BromineHCID 14233599HCID 14233599, compound

Product 1

HCID 14233604Ethyl 2-amino-4-bromo-5-thiocyanatobenzoate

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

In a 100 ml three-neck round bottom flask equipped with an internal thermometer and magnetic stirrer, a solution of 3.26 g (0.0116 mol) of ethyl 2-amino-4-bromobenzoate hydrochloride, 2.12 g (0.0279 mol) of ammonium thiocyanate and 30 ml of acetic acid was cooled to 15° C. Bromine (1.86 g, 0.0116 mol) was then added dropwise with stirring. A precipitate formed. When the addition was complete, the solution was allowed to warm to room temperature, and to stir for an hour. The product was filtered, dried under nitrogen, and recrystallized from hexane and ethyl acetate to furnish crystalline ethyl 2-amino-4-bromo-5-thiocyanatobenzoate: yield 2.05 g (59%); m.p. 149°-150° C.; ir(KBr) 3487 cm, 3453, 3375, 3346, 2980, 2146, 1697, 1614 among others; 1H-NMR(CDCl3) 1.4 ppm (triplet, 3H, CH2CH3), 4.3 (quartet, 2H, CH2CH3), 6.0 (broad singlet), 6.9 singlet, 1H, aromatic H), 8.1 (singlet, 1H aromatic H).

Workup

  1. customIn a 100 ml three-neck round bottom flask equipped with an internal thermometer and magnetic stirrer
  2. customA precipitate formed
  3. additionWhen the addition
  4. stirringto stir for an hour
  5. filtrationThe product was filtered
  6. customdried under nitrogen
  7. customrecrystallized from hexane and ethyl acetate

Sources & evidence

ORD record
ord-daccd96df10842f4b2e90f78e1500398
Source dataset
uspto-grants-1988_08
Patent number
US04762838

Reaction notes

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