Sodium Carbonate → 4-Methylbenzothiazole

HRID 974806Notes

Reaction equation

HRID 974806 reaction equation
[CH3:1][C:2]1[C:7]2[N:8]=[C:9](N)[S:10][C:6]=2[CH:5]=[CH:4][CH:3]=1.N([O-])=O.[Na+].OP=O.C(=O)([O-])[O-].[Na+].[Na+]>P(=O)(O)(O)O>[CH3:1][C:2]1[C:7]2[N:8]=[CH:9][S:10][C:6]=2[CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 10340Sodium CarbonateHCID 151322-Amino-4-methylbenzothiazoleHCID 22497phosphenous acidHCID 23668193Sodium Nitrite

Product 1

HCID 182724-Methylbenzothiazole

Reagents, catalysts & solvents 1

HCID 1004Phosphoric AcidSolvent

Procedure

4-Methyl-2-amino-1,3-benzothiazole (4.93 g, 30 mmol) was dissolved in phosphoric acid (85%, 200 ml) with warming and vigerous stirring. The solution was cooled (-10°) and aqueous sodium nitrite (12.42 g in 35 ml water) added with stirring and cooling to maintain the temperature below -4°. The resulting solution was added dropwise, with vigerous stirring, to a cooled solution of hypophosphorus acid (50% by weight, 75 ml) at 0°. The reaction mixture was allowed to warm to ambient temperature and when evolution of gas was complete the mixture was diluted with ice-water, neutralised with sodium carbonate and extracted with dichloromethane (about 2.5 litres). Evaporation of the organic extracts, after drying over magnesium sulphate, gave an orange oil that was purified by chromatography on silica (dichloromethane as eluant). The product with adequate purity for further reaction was obtained as a dark orange oil.

Workup

  1. temperaturewith warming
  2. additionadded
  3. temperaturecooling
  4. temperatureto maintain the temperature below -4°
  5. extractionextracted with dichloromethane (about 2.5 litres)
  6. customEvaporation of the organic extracts
  7. dry with materialafter drying over magnesium sulphate
  8. customgave an orange oil that
  9. customwas purified by chromatography on silica (dichloromethane as eluant)
  10. customThe product with adequate purity for further reaction
  11. customwas obtained as a dark orange oil

Sources & evidence

ORD record
ord-783506b107f043f982e287d68ea40004
Source dataset
uspto-grants-1997_03
Patent number
US05607929

Reaction notes

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