Stannous Chloride → HCID 58995239, compound

HRID 1445964Notes

Reaction equation

HRID 1445964 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].C([Li])C[CH2:9][CH3:10].[Br:12][C:13]1[CH:26]=[CH:25][C:24]2[C:23](=O)[C:22]3[C:17](=[CH:18][CH:19]=[C:20]([Br:28])[CH:21]=3)[C:16](=O)[C:15]=2[CH:14]=1.[Sn](Cl)Cl>C1COCC1.Cl.O.CCCCCC>[Br:12][C:13]1[CH:26]=[CH:25][C:24]2[C:15](=[C:16]([C:10]#[C:9][Si:2]([CH3:4])([CH3:3])[CH3:1])[C:17]3[C:22]([C:23]=2[C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])=[CH:21][C:20]([Br:28])=[CH:19][CH:18]=3)[CH:14]=1

Participants

9

Reactant 4

HCID 24479Stannous ChlorideHCID 66111TrimethylsilylacetyleneHCID 109594842,6-DibromoanthraquinoneHCID 178418339Butyllithium

Product 1

HCID 58995239HCID 58995239, compoundYield 84%

Reagents, catalysts & solvents 4

HCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

Trimethylsilylacetylene (13.51 g, 137.5 mmol) and dry hexane (300 mL) were charged to an oven-dried round bottom flask (1 L) under dry nitrogen. Butyl lithium (2.7 M in hexane, 46.3 mL, 125.1 mmol) was added dropwise under dry nitrogen through a syringe with water bath cooling. A white precipitate appeared immediately. The mixture was stirred at room temperature for 2 hours. It was then added to a suspension of 2,6-dibromoanthraquinone (18.30 g, 50.0 mmol) in dry THF (600 mL) under dry nitrogen. All of the solids dissolved after the addition and a dark red solution was obtained. A precipitate appeared after about 1 hour. The reaction mixture was stirred at room temperature for 16 hours. DI water (10.0 mL) was added and a white precipitate appeared. Tin (II) chloride (22.8 g, 120 mmol) in HCl (50 mL, 6 M) aqueous solution was then added. The mixture was heated to 70° C. for 2 hours and then cooled to room temperature. The solvent was removed by rotary evaporation. The residue washed with water and then extracted with warm CHCl3 (300 mL). After removal of the CHCl3 solvent, the residue was recrystallized from CHCl3. An orange solid (22.1 g, yield 84%) was obtained as the product. 1H NMR (400 MHz, CDCl3). δ ppm 9.061-9.100 (d, 2H, J=2.4 Hz), 8.757-8.812 (d, 2H, J=9.2 Hz), 8.030-8.091 (dd, 2H, J=9.2 Hz, J=2.0 Hz), 0.851 (s, 18H).

Workup

  1. temperaturecooling
  2. dissolutionAll of the solids dissolved
  3. additionafter the addition
  4. customa dark red solution was obtained
  5. waitA precipitate appeared after about 1 hour
  6. stirringThe reaction mixture was stirred at room temperature for 16 hours
  7. temperatureThe mixture was heated to 70° C. for 2 hours
  8. temperaturecooled to room temperature
  9. customThe solvent was removed by rotary evaporation
  10. washThe residue washed with water
  11. extractionextracted with warm CHCl3 (300 mL)
  12. customAfter removal of the CHCl3 solvent
  13. customthe residue was recrystallized from CHCl3

Sources & evidence

ORD record
ord-d3154f4a392c405b8ca83c1d24ef20b5
Source dataset
uspto-grants-2010_02
Patent number
US07666968B2

Reaction notes

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