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 1810647Notes

Reaction equation

HRID 1810647 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-4f9618c2343b43e799ecc46b543672af
Source dataset
uspto-grants-2013_01
Patent number
US08362016B2

Reaction notes

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