Triethylamine → 4-{5-(3-trimethylsilyl-1-propynyl)-2-methylbenzyl}-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

HRID 2296989Notes

Reaction equation

HRID 2296989 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([CH3:18])=[C:6]([CH:17]=1)[CH2:7][N:8]1[C:12]([O:13][CH3:14])=[N:11][N:10]([CH3:15])[C:9]1=[O:16].[CH3:19][Si:20]([CH3:25])([CH3:24])[CH2:21][C:22]#[CH:23].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C>C(#N)C.COC(C)(C)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[CH3:19][Si:20]([CH3:25])([CH3:24])[CH2:21][C:22]#[C:23][C:2]1[CH:3]=[CH:4][C:5]([CH3:18])=[C:6]([CH:17]=1)[CH2:7][N:8]1[C:12]([O:13][CH3:14])=[N:11][N:10]([CH3:15])[C:9]1=[O:16]

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 83378Trimethyl-2-propynylsilaneHCID 120565184-(5-bromo-2-methylbenzyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

Product 1

HCID 183888354-{5-(3-trimethylsilyl-1-propynyl)-2-methylbenzyl}-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-oneYield 34%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 624 mg (2.0 mmol) of 4-(5-bromo-2-methylbenzyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (the compound 299 of the present invention), 700 mg (6.3 mmol) of 3-(trimethylsilyl)-1-propyne, 63 mg (0.095 mmol) of PdCl2(PPh3)2, 32 mg (0.17 mmol) of copper (I) iodide, 104 mg (0.40 mmol) of triphenylphosphine and 1.0 g of triethylamine in 6 ml of acetonitrile was stirred at 80° C. under an atmosphere of nitrogen for 9 hours. After cooling to room temperature, the reaction mixture was diluted with tert-butyl methyl ether, washed with water, dried and concentrated. The residue was subjected to silica gel column chromatography (eluted with hexane:ethyl acetate=2:1) to obtain 0.30 g (0.68 mmol) of 4-{5-(3-trimethylsilyl-1-propynyl)-2-methylbenzyl}-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (the compound 527 of the present invention).

Workup

  1. temperatureAfter cooling to room temperature
  2. washwashed with water
  3. customdried
  4. concentrationconcentrated
  5. washThe residue was subjected to silica gel column chromatography (eluted with hexane:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-abd23b6d575a4d3f888f1d6ccc704466
Source dataset
uspto-grants-2002_12
Patent number
US06489487B1

Reaction notes

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