Phosgene → HCID 15572339, compound

HRID 2412947Notes

Reaction equation

HRID 2412947 reaction equation
[F:1][C:2]1[CH:21]=[CH:20][C:5]([C:6]([NH:8][CH2:9][C:10]([CH3:19])=[CH:11][C:12]2[CH:17]=[CH:16][C:15]([F:18])=[CH:14][CH:13]=2)=O)=[CH:4][CH:3]=1.C(Cl)(Cl)=O.CC(C)([O-])C.[K+]>C1(C)C=CC=CC=1.C1COCC1.CS(C)=O>[F:1][C:2]1[CH:21]=[CH:20][C:5]([C:6]2[NH:8][CH:9]=[C:10]([CH3:19])[C:11]=2[C:12]2[CH:17]=[CH:16][C:15]([F:18])=[CH:14][CH:13]=2)=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 6371PhosgeneHCID 23665647Potassium tert-butoxideHCID 53909840HCID 53909840, compound

Product 1

HCID 15572339HCID 15572339, compound

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

Using the general procedure of N. Engel and W. Steglich, Angew. Chem. Int. Ed. Engl., 17, 676 (1978), to a slurry at room temperature of 28.7 g (0.1 mole) of 4-fluoro-N-[3-(4-fluorophenyl)-2-methyl-2-propenyl]benzamide in 100 ml toluene containing 1 ml DMF, stirred under nitrogen, with a dry ice condenser attached, was added dropwise a solution of 39.6 g (28.3 ml, 0.4 mole) of phosgene in 100 ml toluene. The mixture was warmed slightly with a heat gun, then stirred at room temperature overnight. The solution was concentrated by rotary evaporation to give a yellow oil. This was dissolved in 100 ml dry THF (small amount of insoluble solid removed by decanting the solution) and the solution was added dropwise to a cool (15°) solution of 33.5 g (0.3 mole) of potassium t-butoxide in 150 ml DMSO. The dark purple solution was stirred at ~20° C. for 1 hour, then was poured into 1 liter ice water. This was extracted with ether and the ether layers backwashed with water. The ether layer was dried and concentrated and the residue was chromatographed on 900 g of silica gel, eluting with hexane containing 10-40% toluene, to give, after recrystallization from methyl cyclohexane, 10.8 g (40%) of white product, m.p. 126°-7° C.

Workup

  1. temperatureThe mixture was warmed slightly with a heat gun
  2. concentrationThe solution was concentrated by rotary evaporation
  3. customto give a yellow oil
  4. customremoved
  5. customby decanting the solution) and the solution
  6. additionwas added dropwise to
  7. stirringThe dark purple solution was stirred at ~20° C. for 1 hour
  8. extractionThis was extracted with ether
  9. dry with materialThe ether layer was dried
  10. concentrationconcentrated
  11. customthe residue was chromatographed on 900 g of silica gel
  12. washeluting with hexane containing 10-40% toluene
  13. customto give
  14. customafter recrystallization from methyl cyclohexane, 10.8 g (40%) of white product, m.p. 126°-7° C.

Sources & evidence

ORD record
ord-c06b295b7fb94aeaa27068901fe5d010
Source dataset
uspto-grants-1985_01
Patent number
US04495196

Reaction notes

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