Ethanol → HCID 90092917, compound

HRID 1774555Notes

Reaction equation

HRID 1774555 reaction equation
Br[C:2]1[C:3]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[N:4][N:5]([CH3:9])[C:6]=1[CH:7]=[O:8].C(=O)([O-])[O-].[Na+].[Na+].B1([C:31]2[CH2:36][CH2:35][C:34]([CH3:38])([CH3:37])[CH2:33][CH:32]=2)OC(C)(C)C(C)(C)O1.C(O)C>C1(C)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].O>[CH3:37][C:34]1([CH3:38])[CH2:35][CH2:36][C:31]([C:2]2[C:3]([C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=3)=[N:4][N:5]([CH3:9])[C:6]=2[CH:7]=[O:8])=[CH:32][CH2:33]1

Participants

8

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 231420132-(4,4-Dimethylcyclohex-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 83913406HCID 83913406, compound

Product 1

HCID 90092917HCID 90092917, compoundYield 81%

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
95 °C

Procedure

A solution of 4-bromo-1-methyl-3-phenyl-1H-pyrazole-5-carbaldehyde (1c) (150 mg, 0.57 mmol), sodium carbonate (240 mg, 2.26 mmol), and 4,4-(dimethylcyclohexene-1-yl)boronic acid pinacol ester (174 mg, 0.74 mmol) in a mixture of toluene (0.8 mL), ethanol (0.3 mL) and water (0.3 mL) was bubbled with nitrogen for 5 minutes. Palladium tetrakis(triphenylphosphine) (32.7 mg, 0.028 mmol) was added and the reaction mixture was heated at 95° C. overnight. The solution was concentrated in vacuo. Water (3 mL) was added to the residue. The aqueous layer was extracted with ethyl acetate (2×5 mL) and the organic layer was dried over sodium sulfate and concentrated in vacuo. The crude was purified by preparative TLC (cyclohexane/ethyl acetate 80/20) to provide 4-(4,4-dimethylcyclohex-1-en-1-yl)-1-methyl-3-phenyl-1H-pyrazole-5-carbaldehyde (1d) (135 mg, 0.46 mmol, 81%).

Workup

  1. customwas bubbled with nitrogen for 5 minutes
  2. concentrationThe solution was concentrated in vacuo
  3. additionWater (3 mL) was added to the residue
  4. extractionThe aqueous layer was extracted with ethyl acetate (2×5 mL)
  5. dry with materialthe organic layer was dried over sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe crude was purified by preparative TLC (cyclohexane/ethyl acetate 80/20)

Sources & evidence

ORD record
ord-b8ee913cab3145d19970bbb491aed2a4
Source dataset
uspto-grants-2016_02
Patent number
US09260395B2

Reaction notes

Loading…