Water → 5-[3-Trimethylsilyl-ethynyl-4,5-dimethoxy-benzyl]-pyrimidine-2,4-diamine

HRID 963391Notes

Reaction equation

HRID 963391 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:15]=[C:16](I)[C:17]=1[O:18][CH3:19])[CH2:6][C:7]1[C:8]([NH2:14])=[N:9][C:10]([NH2:13])=[N:11][CH:12]=1.C([Si:23]([CH3:26])([CH3:25])[CH3:24])#C.O.[CH2:28](N(CC)CC)[CH3:29]>CN(C)C=O.[Cu]I>[CH3:24][Si:23]([CH3:26])([CH3:25])[C:16]1[CH:15]=[C:5]([CH:4]=[C:3]([O:2][CH3:1])[C:17]=1[O:18][CH3:19])[CH:6]([C:28]#[CH:29])[C:7]1[C:8]([NH2:14])=[N:9][C:10]([NH2:13])=[N:11][CH:12]=1

Participants

7

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 111010945-(3,4-Dimethoxy-5-iodo-benzyl)pyrimidine-2,4-diamine

Product 1

HCID 190815445-[3-Trimethylsilyl-ethynyl-4,5-dimethoxy-benzyl]-pyrimidine-2,4-diamineYield 59%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Procedure

A mixture of 8.7 g of 5-(3,4-dimethoxy-5-iodobenzyl)-pyrimidine-2,4-diamine, 6.2 ml of ethynyltrimethylsilane, 80 mg of bis-trimethylphosphine-palladium dichloride and 1 mg of copper(I) iodide in 25 ml of triethylamine and 25 ml of dimethylformamide is stirred at 60° for 16 hrs. After cooling to room temperature the reaction mixture is treated with 400 ml of water and extracted three times with 200 ml of methylene chloride each time. The combined organic phases are washed twice with 250 ml of water, once with 250 ml of a saturated sodium chloride solution and dried over magnesium sulphate. The crude product is chromatographed on silica gel with methylene chloride/methanol 9:1. 4.73 g (59%) of 5-[3-trimethylsilyl-ethynyl-4,5-dimethoxy-benzyl]-pyrimidine-2,4-diamine are obtained as beige crystals. M.p. 189°-190°.

Workup

  1. extractionextracted three times with 200 ml of methylene chloride each time
  2. washThe combined organic phases are washed twice with 250 ml of water, once with 250 ml of a saturated sodium chloride solution
  3. dry with materialdried over magnesium sulphate
  4. customThe crude product is chromatographed on silica gel with methylene chloride/methanol 9:1

Sources & evidence

ORD record
ord-796060440b9c4307b5154120d4c9930d
Source dataset
uspto-grants-1998_06
Patent number
US05763450

Reaction notes

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