N,N-Dimethylpropargylamine → methyl (E)-[2-methyl-4-[3-(2-methylbenzo[b]furan-5-yl)-3-[4-[3-(dimethylamino)propynyl]phenyl]-allyloxy]phenoxy]acetate

HRID 549855Notes

Reaction equation

HRID 549855 reaction equation
[CH3:1][N:2]([CH2:4][C:5]#[CH:6])[CH3:3].I[C:8]1[CH:13]=[CH:12][C:11](/[C:14](/[C:31]2[CH:40]=[CH:39][C:34]3[O:35][C:36]([CH3:38])=[CH:37][C:33]=3[CH:32]=2)=[CH:15]/[CH2:16][O:17][C:18]2[CH:29]=[CH:28][C:21]([O:22][CH2:23][C:24]([O:26][CH3:27])=[O:25])=[C:20]([CH3:30])[CH:19]=2)=[CH:10][CH:9]=1>O1CCCC1.C(N(CC)CC)C.C1C=CC=CC=1.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.[Cu]I>[CH3:30][C:20]1[CH:19]=[C:18]([O:17][CH2:16]/[CH:15]=[C:14](/[C:31]2[CH:40]=[CH:39][C:34]3[O:35][C:36]([CH3:38])=[CH:37][C:33]=3[CH:32]=2)\[C:11]2[CH:12]=[CH:13][C:8]([C:6]#[C:5][CH2:4][N:2]([CH3:3])[CH3:1])=[CH:9][CH:10]=2)[CH:29]=[CH:28][C:21]=1[O:22][CH2:23][C:24]([O:26][CH3:27])=[O:25]

Participants

8

Reactant 2

HCID 81643N,N-DimethylpropargylamineHCID 86629296methyl (Z)-[4-[3-(4-iodophenyl)-3-(2-methylbenzo[b]furan-5-yl)allyloxy]-2-methylphenoxy]acetate

Product 1

HCID 86629297methyl (E)-[2-methyl-4-[3-(2-methylbenzo[b]furan-5-yl)-3-[4-[3-(dimethylamino)propynyl]phenyl]-allyloxy]phenoxy]acetate

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 241BenzeneSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
0 °C

Procedure

Under nitrogen atmosphere, 3-(N,N-dimethylamino)propyne (250 mg, 3.00 mmol) was added to a degassed solution of methyl (Z)-[4-[3-(4-iodophenyl)-3-(2-methylbenzo[b]-furan-5-yl)allyloxy]-2-methylphenoxy]acetate (370 mg, 0.63 mmol; prepared as described in example 25) in a mixture of tetrahydrofuran (6 mL) and triethylamine (6 mL) The solution was cooled to 0° C., tetrakis(triphenylphosphine)palladium (71 mg, 0.06 mmol) and copper(I) iodide (21 mg, 0.11 mmol) were added. The reaction mixture was stirred at ambient temperature for 72 h, diluted with benzene (100 mL), decanted and evaporated in vacuo. The residue was purified by column chromatography (silica gel Fluka 60, benzene/ethyl acetate 1:0-0:1) yielding methyl (E)-[2-methyl-4-[3-(2-methylbenzo[b]furan-5-yl)-3-[4-[3-(dimethylamino)propynyl]phenyl]-allyloxy]phenoxy]acetate.

Workup

  1. customdecanted
  2. customevaporated in vacuo
  3. customThe residue was purified by column chromatography (silica gel Fluka 60, benzene/ethyl acetate 1:0-0:1)

Sources & evidence

ORD record
ord-d6ddcbe2854640fbaf9434cb715f0660
Source dataset
uspto-grants-2011_05
Patent number
US07943613B2

Reaction notes

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