Toluene → Biphenyl-3-yl(3,4,5-trimethoxyphenyl)sulfane

HRID 522567Notes

Reaction equation

HRID 522567 reaction equation
CC(C)([O-])C.[Na+].CO[C:9]1[CH:14]=[CH:13][C:12]([SH:15])=[CH:11][CH:10]=1.I[C:17]1[CH:18]=[C:19]([O:27][CH3:28])[C:20]([O:25][CH3:26])=[C:21]([O:23][CH3:24])[CH:22]=1.[C:29]1(C)[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1>[Cu](I)I>[C:14]1([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[CH:9]=[CH:10][CH:11]=[C:12]([S:15][C:17]2[CH:18]=[C:19]([O:27][CH3:28])[C:20]([O:25][CH3:26])=[C:21]([O:23][CH3:24])[CH:22]=2)[CH:13]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 127654-MethoxybenzenethiolHCID 2981335-Iodo-1,2,3-trimethoxybenzeneHCID 23676156Sodium t-butoxide

Product 1

HCID 53363791Biphenyl-3-yl(3,4,5-trimethoxyphenyl)sulfane

Reagents, catalysts & solvents 1

HCID 83717Copper iodideCatalyst

Conditions

Temperature
110 °C

Procedure

To a solution of 52a (1.1 g, crude compound) in ethanol (8 mL) was added potassium hydroxide (2.1 g, 12 mL) and heated to reflux for overnight. The solution was cooled to RT and the ethanol was evaporated under reduced pressure. The residue was dissolved in water and washed with diethyl ether (10 mL). The aqueous layer was acidified with 2 N HCl and extracted with diethyl ether (3×50 mL). The organic extracts were washed with water (50 mL), brine (50 mL), dried over MgSO4, filtered and evaporated under reduced pressure to afford 0.85 g (77.3%) of crude biphenyl-3-thiol product (overall, 3 steps). Into a round-bottomed flask, stirred magnetically, were placed 0.1 g (1.04 mmol) of sodium tert-butoxide and 83 mg of copper iodide (0.43 mmol). After the reaction vessel was sealed, 0.13 g (0.71 mmol) of 4-methoxybenzenethiol and 0.19 g (0.65 mmol) of 5-iodo-1,2,3-trimethoxybenzene in 3.0 mL of toluene were injected through the septum. The reaction mixture was heated for overnight at 110° C. Purification was performed by flash chromatography, and an amorphous solid was obtained (40% yield). 1H NMR (500 MHz, CDCl3) δ 7.54-7.52 (m, 3H), 7.44-7.41 (m, 3H), 7.37-7.33 (m, 2H), 7.23 (s, br, 1H), 6.69 (s, 2H), 3.86 (s, 3H), 3.80 (s, 6H). MS (ESI) m/z 353.2 (M+H)+.

Workup

  1. customAfter the reaction vessel was sealed
  2. customPurification
  3. customan amorphous solid was obtained (40% yield)

Sources & evidence

ORD record
ord-a0f92556e6f24f6db6b3cb9d3e2f19b9
Source dataset
uspto-grants-2016_05
Patent number
US09334242B2

Reaction notes

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