Diisopropylamine → HCID 86633520, compound

HRID 2428069Notes

Reaction equation

HRID 2428069 reaction equation
Cl[C:2]1[CH:7]=C[C:5]([C:8]#[C:9][C:10]2[CH:15]=[C:14]([S:16][C:17]3[CH:27]=[CH:26][C:20]([O:21][CH2:22][C:23]([OH:25])=[O:24])=[C:19]([CH3:28])[CH:18]=3)[CH:13]=[C:12]([C:29]#[C:30][C:31]3[CH:36]=[CH:35][C:34](Cl)=CC=3)[N:11]=2)=[CH:4][CH:3]=1.C(C1C=CC=[CH:42][N:41]=1)#C.C(P([C:55]([CH3:58])(C)C)C(C)(C)C)(C)(C)C.C1CCCCC1.C([NH:68]C(C)C)(C)C>O1CCCC1.[Cu]I>[N:68]1[CH:7]=[CH:2][CH:3]=[CH:4][C:5]=1[C:8]#[C:9][C:10]1[CH:15]=[C:14]([S:16][C:17]2[CH:27]=[CH:26][C:20]([O:21][CH2:22][C:23]([O:25][CH2:55][CH3:58])=[O:24])=[C:19]([CH3:28])[CH:18]=2)[CH:13]=[C:12]([C:29]#[C:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:42][N:41]=2)[N:11]=1

Participants

8

Reactant 5

HCID 7912DiisopropylamineHCID 8078CyclohexaneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 137268EthynylpyridineHCID 57826288HCID 57826288, compound

Product 1

HCID 86633520HCID 86633520, compound

Reagents, catalysts & solvents 2

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

Procedure

In nitrogen atmosphere, ethyl [4-(2,6-dibromopyridine-4-ylsulfanyl)-2-methylphenoxy]acetate (110 mg, 0.239 mmol; prepared as described in example 6) and 2-ethynylpyridine (74 mg, 0.717 mmol) were dissolved in degassed anhydrous tetrahydrofuran (2 mL). A 0.15 M Solution of tri-tert-butylphosphine in cyclohexane (0.191 mL, 0.029 mmol) was added via syringe. Copper(I) iodide (1.9 mg, 0.010 mmol), dichloro(bisbenzonitrile)palladium (5.5 mg, 0.014 mmol) and diisopropylamine (80 μL, 0.574 mmol) were subsequently added. The traces of air were removed and the mixture was stirred under nitrogen at ambient temperature 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 9:1-1:9) yielding ethyl [4-[2,6-bis[(2-pyridyl)ethynyl]pyridine-4-ylsulfanyl]-2-methylphenoxy]acetate as a brown oil beside of a by-product-mono substituted derivative, ethyl [4-[6-bromo-2-[(2-pyridyl)ethynyl]pyridine-4-ylsulfanyl]-2-methylphenoxy]acetate (50 mg, 22% yield).

Workup

  1. customThe traces of 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 9:1-1:9)

Sources & evidence

ORD record
ord-f6875951f5414659ba131f8f4c15aee9
Source dataset
uspto-grants-2011_06
Patent number
US07968723B2

Reaction notes

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