Magnesium → 2-(Triethoxygermyl)-thianthrene

HRID 716588Notes

Reaction equation

HRID 716588 reaction equation
[Mg].C(O[Ge:5]([O:12][CH2:13][CH3:14])([O:9][CH2:10][CH3:11])[O:6][CH2:7][CH3:8])C.Br[C:16]1[CH:29]=[CH:28][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>C1COCC1>[CH2:13]([O:12][Ge:5]([O:6][CH2:7][CH3:8])([O:9][CH2:10][CH3:11])[C:16]1[CH:29]=[CH:28][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)[CH3:14]

Participants

5

Reactant 3

HCID 5462224MagnesiumHCID 132131222-BromothianthreneHCID 16684444Germanium(IV) ethoxide

Product 1

HCID 892876832-(Triethoxygermyl)-thianthreneYield 30.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 3-neck 500 mL flask was filled with magnesium turnings (8 g), THF (100 g) and tetraethoxygermane (35 g), and heated to reflux. Crude 2-bromothianthrene (30 g) from Example 1 was added to the flask in small portions. Grignard started after a few minutes and kept refluxing by its own heat for ten minutes. The reaction was allowed to cool for 1 hour, after which magnesium salts were precipitated with heptanes (300 mL). The solution was filtered, followed by evaporation of volatiles by rotary evaporator. The material was distilled three times at <1 mbar, giving colorless 2-(triethoxygermyl)-thianthrene (bp. 180 . . . 210° C., 11 g, 30.5% overall yield based on 2-bromothianthrene, purity 99.5% by GC/MS). FIG. 8 shows the mass spectrum of the compound.

Workup

  1. temperatureheated to reflux
  2. waitGrignard started after a few minutes
  3. temperaturekept refluxing by its
  4. temperatureown heat for ten minutes
  5. temperatureto cool for 1 hour
  6. customafter which magnesium salts were precipitated with heptanes (300 mL)
  7. filtrationThe solution was filtered
  8. customfollowed by evaporation of volatiles by rotary evaporator
  9. distillationThe material was distilled three times at <1 mbar

Sources & evidence

ORD record
ord-863df8351ebf4d05ae633fa67c06e385
Source dataset
uspto-grants-2015_11
Patent number
US09190616B2

Reaction notes

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