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

HRID 70038

反応式

HRID 70038 の反応式
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

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 83717Copper iodide触媒

反応条件

温度
110 °C

実験手順

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)+.

後処理

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

出典と根拠

ORDレコード
ord-3e82cb88d14446e2bd8f782698bad02c
出典データセット
uspto-grants-2014_09
特許番号
US08822513B2

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