Thiophosgene → HCID 131719367, compound

HRID 1720190Notes

Reaction equation

HRID 1720190 reaction equation
[NH2:1][C:2]1[CH:17]=[CH:16][C:5]([S:6]/[C:7](=[C:11](\[OH:15])/[C:12]([OH:14])=[O:13])/[C:8]([OH:10])=[O:9])=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].[C:24](Cl)(Cl)=[S:25]>C1COCC1>[N:1]([C:2]1[CH:3]=[CH:4][C:5]([S:6]/[C:7](=[C:11](\[OH:15])/[C:12]([OH:14])=[O:13])/[C:8]([OH:10])=[O:9])=[CH:16][CH:17]=1)=[C:24]=[S:25]

Participants

5

Reactant 3

HCID 10040ThiophosgeneHCID 11430Potassium CarbonateHCID 131719366HCID 131719366, compound

Product 1

HCID 131719367HCID 131719367, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a slurry of 2-[4'-(amino)thiophenoxy]-3-hydroxymaleic acid (0.370 g, 1.438 mmol) and freshly powdered, freshly dried K2CO3 (1.217 g, 8.806 mmol in THF (30 mL) under nitrogen was added thiophosgene (0.33 mL, 0.498 g, 4.33 mmol). The reaction mixture was stirred vigorously at room temperature for 1 hour, then at reflux for 30 minutes. Upon cooling to room temperature, the reaction mixture was filtered and the solvent evaporated off to afford crude 2-[4'-(isothiocyanato)-thiophenoxy]-3-hydroxymaleic acid as an orange oil; (This material was used directly in the next step but could be crystallized from CHCl3) MP 156°-158° C. with decomposition; 1H NMR (acetone-d6, d) 10.2 (2H, br), 7.58 (2H, d, J=8.8 Hz), 7.32 (2H, d, J=8.8 Hz), 4.99 (1H, br s), 4.79 (1H, d, J=4.8 Hz), 4.26 (1H, d, J=4.8 Hz); 13C NMR (acetone-d6, d) 172.7, 171.0, 135.7, 133.7, 130.9, 127.1, 127.0, 71.7, 55.7; IR (Nujol mull, cm-1) 3390 (br, m), 2040 (s), 1730 (s), 1695 (s); mass spectrum, m/e 299, 263, 191, 166, 108, 57 (base).

Workup

  1. temperatureat reflux for 30 minutes
  2. temperatureUpon cooling to room temperature
  3. filtrationthe reaction mixture was filtered
  4. customthe solvent evaporated off

Sources & evidence

ORD record
ord-a64038a38fa04a269ba5d9b69434a12a
Source dataset
uspto-grants-1996_04
Patent number
US05505931

Reaction notes

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