Phosgene → Methyl 3-Isocyanatosulfonylbenzothiophene-2-carboxylate

HRID 1074370Notes

Reaction equation

HRID 1074370 reaction equation
[NH2:1][S:2]([C:5]1[C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=2[S:7][C:6]=1[C:14]([O:16][CH3:17])=[O:15])(=[O:4])=[O:3].CCC(N=[C:23]=[O:24])C.N12CCN(CC1)CC2.C(Cl)(Cl)=O.[N-]=C=O>C1(C)C(C)=CC=CC=1>[N:1]([S:2]([C:5]1[C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=2[S:7][C:6]=1[C:14]([O:16][CH3:17])=[O:15])(=[O:4])=[O:3])=[C:23]=[O:24]

Participants

7

Reactant 5

HCID 6371Phosgene3×HCID 9237DabcoHCID 105034IsocyanateHCID 5508502-IsocyanatobutaneHCID 13178321Methyl 3-sulfamoyl-1-benzothiophene-2-carboxylate

Product 1

HCID 20496347Methyl 3-Isocyanatosulfonylbenzothiophene-2-carboxylate

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent

Procedure

Methyl 3-aminosulfonylbenzothiophene-2-carboxylate (10 grams), 75 ml of xylene, 3.5 g. of 3-butyl isocyanate and 0.2 g. of 1,4-diazabicyclo[2,2,2]octane in admixture were heated to reflux under a dry ice cooled reflux condenser for 10 minutes. Phosgene gas was passed into the system until the reflux temperature dropped to 120°. The addition was discontinued until the temperature rose to 130° and then additional phosgene was added to cause the temperature to drop to 120°. The cycle was repeated until the reflux temperature remained at 120° for one half hour with no further addition of phosgene. The mixture was then cooled, filtered and the filtrate was concentrated to remove the xylene and recovered butyl isocyanate. The residue thus obtained showed absorption peaks by infrared at 2200 and 1700 cm-1 consistent for the isocyanate and carboxylate groups. This product was used for the synthesis of the herbicides of this invention without further purification. The isocyanate derivatives of Tables I-Ic can be prepared from the appropriately substituted sulfonamides by the method set forth in Examples 1 and 2.

Workup

  1. temperatureto reflux under a dry ice
  2. temperaturecooled
  3. temperaturereflux condenser for 10 minutes
  4. additiondropped to 120°
  5. additionThe addition
  6. customrose to 130°
  7. customto drop to 120°
  8. temperatureThe mixture was then cooled
  9. filtrationfiltered
  10. concentrationthe filtrate was concentrated
  11. customto remove the xylene
  12. customrecovered butyl isocyanate
  13. customThe residue thus obtained
  14. customabsorption peaks
  15. customThis product was used for the synthesis of the herbicides of this invention without further purification

Sources & evidence

ORD record
ord-fce791a3d5df46c8825f903a75311d84
Source dataset
uspto-grants-1983_07
Patent number
US04391627

Reaction notes

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