Cyanogen Bromide → [3-(Benzylsulfanyl)phenyl]cyanamide

HRID 556758Notes

Reaction equation

HRID 556758 reaction equation
[N:1]#[C:2]Br.[CH2:4]([S:11][C:12]1[CH:13]=[C:14]([CH:16]=[CH:17][CH:18]=1)[NH2:15])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1>C(OCC)C>[CH2:4]([S:11][C:12]1[CH:13]=[C:14]([NH:15][C:2]#[N:1])[CH:16]=[CH:17][CH:18]=1)[C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1

Participants

4

Reactant 2

HCID 10476Cyanogen BromideHCID 118443953-(Benzylsulfanyl)aniline

Product 1

HCID 59359635[3-(Benzylsulfanyl)phenyl]cyanamideYield 87.6%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

A solution of cyanogen bromide (1.42 g, 13.4 mmol) in anhydrous diethyl ether (10 ml) was added slowly to a stirred solution of 3-(benzylthio)aniline (4.6 g, 21.4 mmol) in anhydrous diethyl ether (25 ml) at 0-4° C. After the addition, the reaction mixture was stirred at room temperature for 12 hours and became a brown solution with a white precipitate. The precipitate was filtered off and the filtrate was washed with aqueous HCl (1 M, 3×40 ml) and followed by brine (40 ml). The ether solution was dried over MgSO4, filtered, and concentrated in vacuo to yield yellow oil as crude product. It was further purified by flash chromatography (SiO2, CH2Cl2/EtOAc, 0-20%) to afford 3-(benzylthio)phenylcyanamide (2.82 g, 55% yield) as a white solid: TLC: Dichloromethane/EtOAc (93:7), Rf=0.64; 1H-NMR (CDCl3) δ (ppm) 7.2-6.7 (m, 9H, Ar—H), 4.12 (s, 2H, S—CH2). IR(KBr): 3178 cm−1 (secondary N—H), 3023-3085 cm−1 (C—H aromatic stretch), 2227 cm−1 (CN).

Workup

  1. additionAfter the addition
  2. filtrationThe precipitate was filtered off
  3. washthe filtrate was washed with aqueous HCl (1 M, 3×40 ml)
  4. dry with materialThe ether solution was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto yield yellow oil as crude product
  8. customIt was further purified by flash chromatography (SiO2, CH2Cl2/EtOAc, 0-20%)

Sources & evidence

ORD record
ord-dfc6c250c6e74d20a198a94574338ad5
Source dataset
uspto-grants-2011_11
Patent number
US08058311B2

Reaction notes

Loading…