Chlorodifluoromethane → HCID 18930396, compound

HRID 129641Notes

Reaction equation

HRID 129641 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[NH:12][C:11]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:10][C:9]=2[S:18]C#N)=[CH:4][CH:3]=1.[BH4-].[Na+].[OH-].[K+].C(P(CCCC)CCCC)CCC.Cl[CH:39]([F:41])[F:40]>CC(O)C.[Cl-].[Na+].O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[NH:12][C:11]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:10][C:9]=2[S:18][CH:39]([F:41])[F:40])=[CH:6][CH:7]=1

Participants

8

Reactant 5

HCID 6372Chlorodifluoromethane2×HCID 13831Tributylphosphine2×HCID 14797Potassium HydroxideHCID 4311764Sodium borohydrideHCID 18930395HCID 18930395, compound

Product 1

HCID 18930396HCID 18930396, compound

Reagents, catalysts & solvents 2

HCID 3776IsopropanolSolvent2×HCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
70 °C

Procedure

A solution of ethyl 5-(p-chlorophenyl)-4-thiocyanatopyrrole-2-carboxylate (76.7 mg, 0.25 mmol) in 2-propanol is treated with sodium borohydride (11.0 mg, 0.29 mmol) under nitrogen, heated to 70° C. for ten minutes, cooled to room temperature, treated with a solution of potassium hydroxide (16.8 mg, 0.30 mmol) in 2-propanol, treated with tributylphosphine (81.2 mg, 0.4 mmol), heated to 65°-70° C. and treated with excess chlorodifluoromethane for one hour. Additional tributylphosphine (81.2 mg, 0.4 mmol) is added to the reaction mixture and the addition of chlorodifluoromethane is continued for 30 minutes. The mixture is then poured into brine and extracted with ethyl acetate. The combined organic extracts are washed with water, dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a liquid. Flash chromatography of the liquid using silica gel and a 1:10 ethyl acetate/hexanes solution gives the title product as a white solid (42.6 mg, mp 113°-117° C.) which is identified by 1HNMR and 13CNMR spectral analyses.

Workup

  1. temperaturecooled to room temperature
  2. temperatureheated to 65°-70° C.
  3. extractionextracted with ethyl acetate
  4. washThe combined organic extracts are washed with water
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customto obtain a liquid

Sources & evidence

ORD record
ord-ddf49d9c32a7499ba0e3cacc18e459ac
Source dataset
uspto-grants-1995_11
Patent number
US05468877

Reaction notes

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