Methane → HCID 10585340, compound

HRID 327171Notes

Reaction equation

HRID 327171 reaction equation
Cl[C:2]1[CH:3]=[C:4]([NH2:10])[CH:5]=[CH:6][C:7]=1[C:8]#[N:9].[K].[C:12]1([SH:18])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C1(S)C=CC=CC=1.[OH-].[K+].C>CO.CN(C)C=O>[C:8]([C:7]1[CH:6]=[CH:5][C:4]([NH2:10])=[CH:3][C:2]=1[S:18][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)#[N:9]

Participants

8

Reactant 5

HCID 297MethaneHCID 7969ThiophenolHCID 14797Potassium HydroxideHCID 887284-Amino-2-chlorobenzonitrileHCID 686835543111-52-2

Product 1

HCID 10585340HCID 10585340, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
140 °C

Procedure

3-Chloro-4-cyanobenzenamine (20.0 g, 13.1 mmol) was added to a N,N-dimethylformamide (115 mL) solution of thiophenol potassium salt [prepared by adding thiophenol (13.5 mL, 13.1 mmol) to a solution of potassium hydroxide (7.35 g, 13.1 mmol) in methanol followed by removal of the methanol in vacuo] and washed in with an additional 15 ml of N,N-dimethylformamide. After stirring at 140° C. for 16 hours the mixture was poured into water, extracted with ethyl ether (3×150 mL) and the solvent removed in vacuo to yield a red oil. The oil was chromatographed on silica gel using methylene chloride as eluent. The fractions containing product (TLC-silica gel, 2% methanol/chloroform) were combined, the solvent removed and the material rechromatographed using 2:1 methylene chloride/hexane as eluent. The proper fractions were combined, concentrated to a low volume, treated with hexane and cooled (dry ice) and scratched as crystals formed. The white solid weighed 8.29 g (30%); mp 69°--71° C. 1H--NMR (250 MHz, CDCl3): 4.07 (s, 2H, NH2), 6.29 (d,1H, J=2.2 Hz, aromatic), 6.46 (dd 1H, J=2.2 Hz, aromatic), 7.36-7.50 (m, 6H, aromatic). MS (CI, CH4): 227(M+1).

Workup

  1. customprepared
  2. customfollowed by removal of the methanol in vacuo] and
  3. washwashed in with an additional 15 ml of N,N-dimethylformamide
  4. additionwas poured into water
  5. extractionextracted with ethyl ether (3×150 mL)
  6. customthe solvent removed in vacuo
  7. customto yield a red oil
  8. customThe oil was chromatographed on silica gel
  9. additionThe fractions containing product (TLC-silica gel, 2% methanol/chloroform)
  10. customthe solvent removed
  11. customthe material rechromatographed
  12. concentrationconcentrated to a low volume
  13. additiontreated with hexane
  14. temperaturecooled (dry ice)
  15. customformed

Sources & evidence

ORD record
ord-bf8203e248984f0790e2c90de2c3c287
Source dataset
uspto-grants-1993_12
Patent number
US05272163

Reaction notes

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