Bromine → 2-imino-8-trifluoromethoxy-2H,4H-thiazolo[5,4,3-ij]quinolin-6-one

HRID 50600Notes

Reaction equation

HRID 50600 reaction equation
BrBr.[S-:3][C:4]#[N:5].[K+].[F:7][C:8]([F:22])([F:21])[O:9][C:10]1[CH:11]=[C:12]2[C:17](=[CH:18][CH:19]=1)[NH:16][CH2:15][CH2:14][C:13]2=[O:20]>C(O)(=O)C>[NH:5]=[C:4]1[N:16]2[C:17]3[C:12]([C:13](=[O:20])[CH2:14][CH2:15]2)=[CH:11][C:10]([O:9][C:8]([F:21])([F:7])[F:22])=[CH:19][C:18]=3[S:3]1

Participants

5

Reactant 3

HCID 24408BromineHCID 516872Potassium thiocyanateHCID 15550363HCID 15550363, compound

Product 1

HCID 155503642-imino-8-trifluoromethoxy-2H,4H-thiazolo[5,4,3-ij]quinolin-6-oneYield 6.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

The procedure is carried out as in Example 1, but starting with 2.2 g of bromine in 10 ml of acetic acid, 3.09 g of potassium thiocyanate and 3.2 g of 6-trifluoromethoxy-2,3-dihydro-(1H)-quinolin-4-one in 35 ml of acetic acid. The organic phase is extracted with 170 ml of an approximately 0.1 N aqueous hydrochloric acid solution. The aqueous hydrochloric phase is alkalinized with 4 ml of a 10 N sodium hydroxide solution and extracted with three times 100 ml of ethyl acetate. The organic extracts are combined, washed with 100 ml of distilled water, dried over magnesium sulphate and concentrated to dryness under reduced pressure (2 kPa) at 40° C. The crude product obtained is chromatographed on silica gel, eluting with a mixture of ethyl acetate and petroleum ether (80-20 by volume). The yellow solid isolated (0.3 g) is washed with a cold solution of petroleum ether and of isopropyl ether (60-40 by volume), and is then dried under reduced pressure (70 Pa) at 40° C. 0.25 g of 2-imino-8-trifluoromethoxy-2H,4H-thiazolo-[5,4,3-ij]quinolin-6-one is thus obtained in the form of a yellow powder melting at 192° C. [Analysis C11H7F3N2O2S, % calculated C: 45.84, H: 2.45, F: 19.77, N: 9.72, O: 11.1, S: 11.12, % found C: 45.5, H: 2.1, F: 19.4, N: 9.3, S: 11.1].

Workup

  1. extractionThe organic phase is extracted with 170 ml of an approximately 0.1 N aqueous hydrochloric acid solution
  2. extractionextracted with three times 100 ml of ethyl acetate
  3. washwashed with 100 ml of distilled water
  4. dry with materialdried over magnesium sulphate
  5. concentrationconcentrated to dryness under reduced pressure (2 kPa) at 40° C
  6. customThe crude product obtained
  7. customis chromatographed on silica gel
  8. washeluting with a mixture of ethyl acetate and petroleum ether (80-20 by volume)
  9. customThe yellow solid isolated (0.3 g)
  10. washis washed with a cold solution of petroleum ether and of isopropyl ether (60-40 by volume)
  11. customis then dried under reduced pressure (70 Pa) at 40° C

Sources & evidence

ORD record
ord-4696c833b3924df1b997f5d96a06e42f
Source dataset
uspto-grants-2004_03
Patent number
US06713468B2

Reaction notes

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