Chlorosulfonic acid → HCID 178514331, compound

HRID 965325Notes

Reaction equation

HRID 965325 reaction equation
[N+:1](=[C:3]1[C:12](=[O:13])[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[O:5][C:4]1=[O:14])=[N-:2].[Cl:15][S:16](O)(=[O:18])=[O:17]>C(O)C>[Cl:15][S:16]([C:9]1[CH:10]=[C:11]2[C:6](=[CH:7][CH:8]=1)[O:5][C:4](=[O:14])[C:3](=[N+:1]=[N-:2])[C:12]2=[O:13])(=[O:18])=[O:17]

Participants

4

Reactant 2

HCID 24638Chlorosulfonic acidHCID 178514330HCID 178514330, compound

Product 1

HCID 178514331HCID 178514331, compoundYield 81.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
50 °C

Procedure

A 250 mL three-necked round-bottom flask equipped with a magnetic stirrer, water bath, nitrogen inlet and bubbler, thermometer and temperature controller was charged with 3-diazo-4-oxo-3,4-dihydrocoumarin (10.1 g, 53.7 mmol) prepared in accordance with Example 1 and chlorosulfonic acid (75.1 g). The reaction mixture was then heated to 50° C. and maintained at 50° C. for 42 hours, during which time HPLC analysis showed 99% conversion. The reaction was allowed to cool and was poured slowly, in portions, with stirring, into 420 g ice cold ethanol (the temperature of the ethanol slurry was kept below 10° C. throughout the addition). The ethanolic slurry was filtered, and dried in an oven overnight under vacuum at 58° C. to yield 12.5 g of pure 6-chlorosulfonyl-3-diazo-4-oxo-3,4-dihydrocoumarin (81% yield). The product was characterized by 13C NMR, DSC and UV-Vis. The results are as follows: the vacuum dried sample melted at 184.7° C. 13C-NMR in THF-d8 solvent, showed 9 singlet lines at the following chemical shifts, in ppm: 172.693, 1158.932, 157.050, 141.502, 134.467, 126.202, 121.104, 121.091, 77.983. The UV absorption spectrum of the product in THF solvent was determined at a dilution factor, DF=109,182.05 yielding, λ1 max=232 nm, ε1 max=29,532.1 liters/mole cm; and λ2max=288 nm, ε2 max=9,472.8 liters/mole cm.

Workup

  1. customA 250 mL three-necked round-bottom flask equipped with a magnetic stirrer, water bath, nitrogen inlet
  2. temperaturemaintained at 50° C. for 42 hours, during which time HPLC analysis
  3. temperatureto cool
  4. additionwas poured slowly, in portions
  5. additionwas kept below 10° C. throughout the addition)
  6. filtrationThe ethanolic slurry was filtered
  7. customdried in an oven overnight under vacuum at 58° C.

Sources & evidence

ORD record
ord-1b3a947f77434c4c9540333c1ff3d760
Source dataset
uspto-grants-1998_06
Patent number
US05773591

Reaction notes

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