Diethyl Ether → Methyl 2-aminobenzo[d]thiazole-7-carboxylate

HRID 964765Notes

Reaction equation

HRID 964765 reaction equation
[NH:1]([C:5]1[CH:6]=[C:7]([CH:12]=[CH:13][CH:14]=1)[C:8]([O:10][CH3:11])=[O:9])[C:2]([NH2:4])=[S:3].BrBr.C(OCC)C>ClC1C=CC=CC=1>[NH2:4][C:2]1[S:3][C:6]2[C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:12][CH:13]=[CH:14][C:5]=2[N:1]=1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 24408BromineHCID 726316Methyl 3-thioureidobenzoate

Product 1

HCID 10910742Methyl 2-aminobenzo[d]thiazole-7-carboxylateYield 83%

Reagents, catalysts & solvents 1

HCID 7964ChlorobenzeneSolvent2×

Procedure

8.4 g of methyl 3-thioureido-benzoate are suspended in 120 ml of chlorobenzene, 2.2 ml of bromine in 30 ml of chlorobenzene are added at 0° C. in the course of 1 hour, while stirring as thoroughly as possible, and the mixture is then stirred to room temperature. It is then kept at 70° C. for 4 hours and subsequently cooled, a little diethyl ether is added and the precipitate is filtered off, mixed thoroughly with 70 ml of aqueous sodium bicarbonate solution, filtered off again and washed with water. 7.7 g (88%) of crude product of melting point 231°-232° C. result. HPLC analysis shows a content of more than 83% of the pure title compound, in addition to 8-18% of isomeric methyl 2-amino-benzothiazole-5-carboxylate. Suspension in and brief heating at 70° C. with ethyl acetate, cooling to 30° C. and filtration give the pure title compound of melting point >250° C. If the reaction is carried out in acetic acid (instead of in chlorobenzene), the content of the undesired isomeric methyl 2-amino-benzothiazole-5-carboxylate is only about 5%.

Workup

  1. stirringis then stirred to room temperature
  2. temperaturesubsequently cooled
  3. filtrationthe precipitate is filtered off
  4. additionmixed thoroughly with 70 ml of aqueous sodium bicarbonate solution
  5. filtrationfiltered off again
  6. washwashed with water
  7. custom7.7 g (88%) of crude product of melting point 231°-232° C. result

Sources & evidence

ORD record
ord-8ad7032d22e14afc8a1f8e90a613861e
Source dataset
uspto-grants-1998_06
Patent number
US05770758

Reaction notes

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