Chlorotrimethylsilane → HCID 58340351, compound

HRID 2369720Notes

Reaction equation

HRID 2369720 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([C:8]2[S:9][CH:10]=[CH:11][C:12]=2[Br:13])[C:5]([Br:14])=[CH:4][C:3]=1[C:15]1[S:16][CH:17]=[CH:18][C:19]=1[Br:20].C1COCC1.C([N-]C(C)C)(C)C.[Li+].Cl[Si:35]([CH3:38])([CH3:37])[CH3:36]>O1CCCC1.CCCCCCC.C(C1C=CC=CC=1)C.O.CO>[Br:14][C:5]1[CH:4]=[C:3]([C:15]2[S:16][C:17]([Si:35]([CH3:38])([CH3:37])[CH3:36])=[CH:18][C:19]=2[Br:20])[C:2]([Br:1])=[CH:7][C:6]=1[C:8]1[S:9][C:10]([Si:35]([CH3:38])([CH3:37])[CH3:36])=[CH:11][C:12]=1[Br:13]

Participants

8

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 8028TetrahydrofuranHCID 2724682Lithium diisopropylamideHCID 58340348HCID 58340348, compound

Product 1

HCID 58340351HCID 58340351, compoundYield 74%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 22742125Tetrahydrofuran heptane ethylbenzolSolvent

Conditions

Temperature
-78 °C

Procedure

A oven dried 1000 cm3 three neck flask is charged with 2,2′-(2,5-dibromobenzene-1,4-diyl)bis(3-bromothiophene) (12.00 g, 21.51 mmol) and anhydrous THF (430 cm3). The reaction is cooled down to −78° C. using a acetone dry ice bath, and then a 2.0M solution (22.0 cm3, 44.1 mmol) of lithium diisopropylamide in tetrahydrofuran/heptane/ethylbenzene is added dropwise. After the addition completion, the reaction mixture is kept at 78° C. for a hour, and then chlorotrimethylsilane (6.00 cm3, 47.3 mmol) is added quickly. The reaction is allowed to reach 23° C. overnight, and then methanol (100 cm3) and water (400 cm3) is added. The mixture is extracted with diethyl ether (3×300 cm3). The combined organic phases are washed with diluted aqueous chlorhydric acid (3×250 cm3) and water (300 cm3), dried over magnesium sulfate, and then the solvent removed in vacuo. The crude product is recrystallized in propan-2-ol to obtain the title product. (11.12 g, Yield: 74%). NMR (1H, 300 MHz, CDCl3): δ 7.68 (s, 2H); 7.16 (s, 2H); 0.36 (s, 18H). NMR (13C, 75 MHz, CDCl3): δ 142.52; 139.96; 136.60; 136.39; 136.25; 123.11; 112.71, −0.16.

Workup

  1. dry with materialA oven dried 1000 cm3 three neck flask
  2. waitAfter the addition completion, the reaction mixture is kept at 78° C. for a hour
  3. extractionThe mixture is extracted with diethyl ether (3×300 cm3)
  4. washThe combined organic phases are washed with diluted aqueous chlorhydric acid (3×250 cm3) and water (300 cm3)
  5. dry with materialdried over magnesium sulfate
  6. customthe solvent removed in vacuo
  7. customThe crude product is recrystallized in propan-2-ol

Sources & evidence

ORD record
ord-674c4783f7224a05b9c0ad1c47aa918d
Source dataset
uspto-grants-2014_04
Patent number
US08709290B2

Reaction notes

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