Ammonium Chloride → HCID 58669199, compound

HRID 1444997Notes

Reaction equation

HRID 1444997 reaction equation
Br[C:2]1[S:6][C:5]([CH:7]=[O:8])=[C:4]([CH3:9])[C:3]=1[CH:10]1[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]1.B([O-])[O-].[Cl-].[NH4+]>[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:7]([C:5]1[S:6][CH:2]=[C:3]([CH:10]2[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]2)[C:4]=1[CH3:9])=[O:8]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 58669189HCID 58669189, compoundHCID 178514824HCID 178514824, compound

Product 1

HCID 58669199HCID 58669199, compound

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 178418397HCID 178418397, compoundCatalyst2×

Procedure

5-bromo-3-methyl-4-cyclohexyl-2-formylthiophene (1.5 g, 5.2 mmol), 3-methyl-4-cyclohexylthiophene-2-boryl pinacolate (1.9 g, 6.24 mmol) and Bu4NBr (33 mg, 0.1 mmol) were added to a 100 ml flask. The mixture of solids was evacuated for 2 hours, then dissolved in dry toluene (30 ml) under argon with stirring. Tetrakis(triphenylphosphine)palladium (100 mg, 0.09 mmol) was added and the solution was heated to 95° for 16 hours. Afterwards, an additional aliquot of boronate (0.5 g) and tetrakis(triphenylphosphine)palladium (50 mg) were added. The reaction was checked, after stirring an additional 20 hours, and found to be complete. The mixture was poured into a saturated solution of ammonium chloride, and extracted with toluene (3×20 mL). The combined organic layers were washed with brine and dried over anhydrous Na2SO4. After the solvent was removed by rotary evaporation. The remaining oil was purified by column chromatography (CH2Cl2:petroleum ether, 2:3) to afford the product 2-formyl-3-methyl-4-cyclohexylthiophene dimer as a yellow solid (1.5 g, 75%). 1H NMR (CDCl3) δ 10.08 (s, 1, CHO), 7.01 (s, 1,thienyl-H), 2.67 (m,1,cyclohexyl methane), 2.65 (s, 3,CH3), 2.52 (m,1,cyclohexyl methane), 2.07 (s, 3,CH3), 1.78 and 1.31 (m, 20, cyclohexyl). 13C NMR (CDCl3) δ 182.5, 148.3, 147.9, 146.5, 140.4, 138.2, 136.7, 128.6, 119.4, 39.7, 38.8, 33.8, 31.3, 27.1, 26.9, 26.3, 25.9, 14.01, 13.3.

Workup

  1. additionwere added to a 100 ml flask
  2. additionThe mixture of solids
  3. customwas evacuated for 2 hours
  4. dissolutiondissolved in dry toluene (30 ml) under argon
  5. temperaturethe solution was heated to 95° for 16 hours
  6. stirringafter stirring an additional 20 hours
  7. extractionextracted with toluene (3×20 mL)
  8. washThe combined organic layers were washed with brine
  9. dry with materialdried over anhydrous Na2SO4
  10. customAfter the solvent was removed by rotary evaporation
  11. customThe remaining oil was purified by column chromatography (CH2Cl2:petroleum ether, 2:3)

Sources & evidence

ORD record
ord-79414850e41147258aeb598f01aadebd
Source dataset
uspto-grants-2010_02
Patent number
US07663301B2

Reaction notes

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