Diisopropylamine → HCID 86633518, compound

HRID 2428066Notes

Reaction equation

HRID 2428066 reaction equation
Br[C:2]1[CH:3]=[C:4]([S:9][C:10]2[CH:22]=[CH:21][C:13]([O:14][CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17])=[C:12]([CH3:23])[CH:11]=2)[CH:5]=[C:6]([Br:8])[CH:7]=1.[C:24]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=1)#[CH:25].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.C1CCCCC1.C(NC(C)C)(C)C>O1CCCC1.[Cu]I>[Br:8][C:6]1[CH:5]=[C:4]([S:9][C:10]2[CH:22]=[CH:21][C:13]([O:14][CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17])=[C:12]([CH3:23])[CH:11]=2)[CH:3]=[C:2]([C:25]#[C:24][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=2)[CH:7]=1

Participants

8

Reactant 5

HCID 7912DiisopropylamineHCID 8078CyclohexaneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 137268EthynylpyridineHCID 86633517HCID 86633517, compound

Product 1

HCID 86633518HCID 86633518, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
40 °C

Procedure

In nitrogen atmosphere, ethyl [4-(3,5-dibromophenylsulfanyl)-2-methylphenoxy]-acetate (460 mg, 1 mmol; prepared as described in example 1) and 2-ethynylpyridine (110 μL, 1.1 mmol) were dissolved in anhydrous tetrahydrofuran (7 mL). 0.15 M Solution of tri-tert-butylphosphine in cyclohexane (0.6 mL, 0.06 mmol) was added via syringe. Copper(I) iodide (3.8 mg, 0.02 mmol), dichloro(bisbenzonitrile)palladium (11 mg, 0.03 mmol) and diisopropylamine (155 μL, 1.1 mmol) were added. Traces of the air were removed and mixture was stirred under nitrogen at 40° C. overnight. The mixture was diluted with ethyl acetate (10 mL) and filtered through a short path of silica gel. The filtrate was concentrated and purified by column chromatography (silica gel Fluka 60, hexanes/ethyl acetate 90:10-85:15) yielding ethyl [4-[3-bromo-5-[(pyridin-2-yl)ethynyl]phenylsulfanyl]-2-methylphenoxy]acetate beside of 144 mg (30%) of unchanged starting dibromo derivative.

Workup

  1. customTraces of the air were removed
  2. additionThe mixture was diluted with ethyl acetate (10 mL)
  3. filtrationfiltered through a short path of silica gel
  4. concentrationThe filtrate was concentrated
  5. custompurified by column chromatography (silica gel Fluka 60, hexanes/ethyl acetate 90:10-85:15)

Sources & evidence

ORD record
ord-7e6dc01bd8934475b735358bd4dac3a0
Source dataset
uspto-grants-2011_06
Patent number
US07968723B2

Reaction notes

Loading…