Triethoxychlorosilane → 2-(Triethoxysilyl)thianthrene

HRID 716586Notes

Reaction equation

HRID 716586 reaction equation
[Mg].Cl[Si:3]([O:10][CH2:11][CH3:12])([O:7][CH2:8][CH3:9])[O:4][CH2:5][CH3:6].Br[C:14]1[C:27]2[S:26][C:25]3[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=3)[S:19][C:18]=2[CH:17]=[CH:16][CH:15]=1>C1COCC1>[CH2:5]([O:4][Si:3]([O:10][CH2:11][CH3:12])([O:7][CH2:8][CH3:9])[C:16]1[CH:15]=[CH:14][C:27]2[S:26][C:25]3[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=3)[S:19][C:18]=2[CH:17]=1)[CH3:6]

Participants

5

Reactant 3

HCID 78398TriethoxychlorosilaneHCID 5462224MagnesiumHCID 152471791-Bromothianthrene

Product 1

HCID 711166762-(Triethoxysilyl)thianthreneYield 66.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 3-neck 3 L flask was filled with magnesium turnings (35 g), THF (600 g) and chlorotriethoxysilane (278 g), and heated to reflux. Bromothianthrene solution from Example 4A was added to the flask in small portions. Grignard started instantly. The reaction was allowed to cool for 1 hour, after which magnesium salts were precipitated with heptanes (500 mL). The solution was filtered, followed by evaporation of volatiles by rotary evaporator. The material was distilled twice at <1 mbar, giving colorless 2-(triethoxysilyl)thianthrene (bp. 175 . . . 200° C., 234.2 g, 66.9% overall yield based on thianthrene, purity 99.5% by GC/MS) and bis(triethoxysilyl)thianthrene (bp. 200 . . . 225° C., 26.7 g, purity 94.6% by GC/MS, a mixture of 2,7- and 2,8-isomers, yield 5.3% by GC/MS).

Workup

  1. temperatureheated to reflux
  2. temperatureto cool for 1 hour
  3. customafter which magnesium salts were precipitated with heptanes (500 mL)
  4. filtrationThe solution was filtered
  5. customfollowed by evaporation of volatiles by rotary evaporator
  6. distillationThe material was distilled twice at <1 mbar

Sources & evidence

ORD record
ord-559757d7588846ad869d8dc20600bd95
Source dataset
uspto-grants-2015_11
Patent number
US09190616B2

Reaction notes

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