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

HRID 70038

Reaktionsgleichung

Reaktionsgleichung von HRID 70038
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

Komponenten

6

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 83717Copper iodideKatalysator

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

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)+.

Aufarbeitung

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

Quellen und Nachweise

ORD-Eintrag
ord-3e82cb88d14446e2bd8f782698bad02c
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08822513B2

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