Potassium Phosphate, Tribasic → HCID 66993145, compound

HRID 1801412

Reaction equation

HRID 1801412 reaction equation
Br[C:2]1[C:7]([CH3:8])=[CH:6][N+:5]([O-:9])=[CH:4][C:3]=1[CH3:10].[CH3:11][O:12][C:13]1[CH:18]=[C:17]([CH3:19])[C:16](B(O)O)=[C:15]([CH3:23])[CH:14]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C3C(C4C=CC=CC=4C=2)=CC=CC=3)CCCCC1.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:11][O:12][C:13]1[CH:18]=[C:17]([CH3:19])[C:16]([C:2]2[C:7]([CH3:8])=[CH:6][N:5]([OH:9])[CH2:4][C:3]=2[CH3:10])=[C:15]([CH3:23])[CH:14]=1

Participants

6

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 3716303(4-Methoxy-2,6-dimethylphenyl)boronic acidHCID 124930364-Bromo-3,5-dimethylpyridin-1-ium-1-olateHCID 22147288Dicyclohexyl(2-(phenanthren-9-yl)phenyl)phosphane

Product 1

HCID 66993145HCID 66993145, compoundYield 1.8%

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
120 °C

Procedure

A flame-dried sealable Schlenk tube was charged with 4-bromo-3,5-dimethyl-pyridine 1-oxide (1; 10.1 g, 50.0 mmol), 2 (18.0 g, 100 mmol), Pd2(dba)3 (0.915 g, 1.00 mmol), dicyclohexyl-(2-phenanthren-9-yl-phenyl)-phosphane (1.8 g, 4.0 mmol), and K3PO4 (31.9 g, 150 mmol). The Schlenk tube was next evacuated and backfilled with N2. Then, degassed dry toluene (100 mL) was added via syringe under N2. The Schlenk tube was sealed, and the mixture was stirred at 120° C. for 48 h. The reaction mixture was subsequently cooled to room temperature, diluted with methylene chloride (500 mL), filtered, and concentrated in vacuo. The resulting dark brown oil was allowed to stand at room temperature until the colorless crystalline product separated from the liquid. The solid was then collected by filtration and identified as the pure title compound (6.55 g). The filtrate was purified by flash chromatography eluting with 95:5 CHCl3: methanol to afford an additional 0.23 g of the title compound. The combined yield was 6.78 g (53%): mp 194-195° C.; 1H NMR (400 MHz, CD2Cl2): δ 7.990 (s, 2H), 6.705 (s, 2H), 3.798 (s, 3H), 1.892 (s, 6H), 1.842 (s, 6H); 13C NMR (125 MHz, CD2Cl2): δ 159.771, 139.578, 137.663, 137.187, 135.775, 128.289, 113.709, 55.605, 20.198, 17.087; MS (ESI): m/z 258.4 [(M+H)+,100]; Anal. Calcd. For C16H19NO2: C, 74.68; H, 7.44; N, 5.44. Found: C, 74.54; H, 7.40; N, 5.51.

Workup

  1. customThe Schlenk tube was next evacuated
  2. customThen, degassed dry toluene (100 mL)
  3. additionwas added via syringe under N2
  4. customThe Schlenk tube was sealed
  5. temperatureThe reaction mixture was subsequently cooled to room temperature
  6. additiondiluted with methylene chloride (500 mL)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto stand at room temperature until the colorless crystalline product
  10. customseparated from the liquid
  11. filtrationThe solid was then collected by filtration
  12. customThe filtrate was purified by flash chromatography
  13. washeluting with 95:5 CHCl3

Sources & evidence

ORD record
ord-6d95065f78a44f71bd6e21d805da6b4b
Source dataset
uspto-grants-2013_01
Patent number
US08349222B2

Linked notes

Loading…