تفاعل #414353

معادلة التفاعل

3-Chloro-4-cyanobenzenamine

thiophenol potassium salt

thiophenol

potassium hydroxide

CH4

→

4-Cyano-3-phenylthiobenzenamine

المذيبات

N,N-dimethylformamide

methanol

ظروف التفاعل

المعالجة

1. 1
   أخرىprepared
2. 2
   أخرىfollowed by removal of the methanol in vacuo] and
3. 3
   غسيلwashed in with an additional 15 ml of N,N-dimethylformamide
4. 4
   workup.ADDITIONwas poured into water
5. 5
   استخلاصextracted with ethyl ether (3×150 mL)
6. 6
   أخرىthe solvent removed in vacuo
7. 7
   أخرىto yield a red oil
8. 8
   أخرىThe oil was chromatographed on silica gel
9. 9
   workup.ADDITIONThe fractions containing product (TLC-silica gel, 2% methanol/chloroform)
10. 10
    أخرىthe solvent removed
11. 11
    أخرىthe material rechromatographed
12. 12
    تركيزconcentrated to a low volume
13. 13
    workup.ADDITIONtreated with hexane
14. 14
    درجة الحرارةcooled (dry ice)
15. 15
    أخرىformed

الإجراء التجريبي

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).

المصدر