Ethylene Glycol → 4-[(3-Methylphenyl)thio]benzenamine

HRID 2253518Notes

Reaction equation

HRID 2253518 reaction equation
I[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.[CH3:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([SH:16])[CH:11]=1.C([O-])([O-])=O.[K+].[K+].C(O)CO>[Cu]I.CC(O)C>[C:10]1([CH3:9])[CH:15]=[CH:14][CH:13]=[C:12]([S:16][C:2]2[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=2)[CH:11]=1

Participants

7

Reactant 4

HCID 174Ethylene GlycolHCID 79303-ThiocresolHCID 108934-IodoanilineHCID 11430Potassium Carbonate

Product 1

HCID 4593754-[(3-Methylphenyl)thio]benzenamineYield 90.1%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3776IsopropanolSolvent

Procedure

The general procedure in example 39 was followed. 4-Iodoaniline (219 mg, 1.0 mmol), m-thiocresol (119 μL, 1.0 mmol), CuI (10 mg, 0.05 mmol), K2CO3 (276 mg, 2.0 mmol), ethylene glycol (111 μL, 2.0 mmol) and 2-Propanol (1.0 mL) were used to obtain the 4-(3-tolyl)sulfanylaniline (194 mg, 90% yield) as pale yellow liquid. Column chromatographic solvent (hexane/ethyl acetate=4/1). Rf=0.4 (hexane/ethyl acetate=4/1). 1H NMR (CDCl3, 300 MHz) δ 7.28 (dt, 2 H, J=7.5 Hz, 0.9 Hz), 7.08 (t, 1 H, J=7.8 Hz), 6.91 (t, 3 H, J=7.5 Hz), 3.71 (brs, 2 H), 2.26 (s, 3 H). 13C NMR (CDCl3, 75 MHz) δ 138.8, 138.1, 136.2, 128.9, 128.1, 126.4, 124.6, 117.5, 116.1, 100.0, 21.8. IR (neat, cm−1) 3460 (broad), 3377 (broad), 3211, 3051, 3027, 2919. MS (EI) m/z (relative intensity) 219 (100), 92 (80). HRMS (EI), Cald. for C13H13NS 215.0769; Found 215.0766.

Sources & evidence

ORD record
ord-438f8c113cf24a3eba9771cfc79612df
Source dataset
uspto-grants-2008_01
Patent number
US07323608B2

Reaction notes

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