Aniline → 2-[(Diphenylmethyl)sulfanyl]aniline

HRID 258863Notes

Reaction equation

HRID 258863 reaction equation
N[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:8]([S:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.C(OCl)(C)(C)C.C[O-].[Na+].C(#[N:33])C>CO.C(Cl)Cl>[NH2:33][C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][C:16]=1[S:15][CH:8]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

8

Reactant 5

HCID 6115AnilineHCID 6342AcetonitrileHCID 13255Benzyl phenyl sulphideHCID 521297Tert-Butyl hypochloriteHCID 10942334Sodium Methoxide

Product 1

HCID 713914592-[(Diphenylmethyl)sulfanyl]anilineYield 72%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-40 °C

Procedure

To a rapidly stirred solution of 2.3 g. (0.025 mole) of aniline and 10.0 g (0.050 mole) of benzylphenylsulfide in 300 ml. of dry acetonitrile and 100 ml. of methylene chloride under nitrogen at -40° C., was added dropwise 3.5 g. (0.032 mole, 28% excess) of tert-butylhypochlorite in 25 ml. of methylene chloride at -78° C. in diffuse light. The reaction mixture was stirred 4 hours at -40° C. then allowed to warm slowly to -20° C. over 3 hours. Sodium methoxide (7.0 g., 0.13 mole) in 50 ml. of dry methanol (at 25° ) was added quickly. The reaction mixture was stirred for 1 hour as it warmed to room temperature. The solution was concentrated in vacuo, 100 ml. of water was added, and extracted with 5 × 100 ml. of chloroform. The combined organic phases were washed with 50 ml of 5% aqueous sodium hydroxide, 100 ml. of saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and filtered. Solvent was removed in vacuo giving a dark brown oil which was chromatographed on 300 g. of Fisher basic alumina (Act I) using etherpentane as eluant. Recovered was 5.2 g. (72% yield based on starting aniline) of 2-aminodiphenylthiophenoxymethane. Recrystallizaton from ethanol-water gave light yellow crystals, m.p. 64°-65.50°; ir (cm-1) (CCl4) 3480, 3380, 3090, 1620, 1580, 1490, 1450, 1310, 1270, 1160, 1080, 1070, 1025, 690; NMR (CCl4) τ: 2.4-3.7 (14H, m), 4.51 (1H, s), 6.0-6.4 (2H, br s).

Workup

  1. customat -78° C.
  2. temperatureto warm slowly to -20° C. over 3 hours
  3. stirringThe reaction mixture was stirred for 1 hour as it
  4. temperaturewarmed to room temperature
  5. concentrationThe solution was concentrated in vacuo, 100 ml
  6. additionof water was added
  7. extractionextracted with 5 × 100 ml
  8. washThe combined organic phases were washed with 50 ml of 5% aqueous sodium hydroxide, 100 ml
  9. dry with materialof saturated sodium chloride solution, dried over anhydrous magnesium sulfate
  10. filtrationfiltered
  11. customSolvent was removed in vacuo
  12. customgiving a dark brown oil which
  13. customwas chromatographed on 300 g
  14. customRecovered

Sources & evidence

ORD record
ord-73c17dc63fa54eb0ad69706174cbe291
Source dataset
uspto-grants-1977_07
Patent number
US04035375

Reaction notes

Loading…