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 1039471Notes

Reaction equation

HRID 1039471 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-e7c8956d74e440a182bd4da5e3d43ab6
Source dataset
uspto-grants-2013_10
Patent number
US08551993B2

Reaction notes

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