Triphenylphosphine → 6-bromo-4-methyl-2-(2-thiophen-2-yl-ethyl)-2H-[1,2,4]triazine-3,5-dione

HRID 1917088Notes

Reaction equation

HRID 1917088 reaction equation
[Br:1][C:2]1[C:3](=[O:10])[N:4]([CH3:9])[C:5](=[O:8])[NH:6][N:7]=1.[S:11]1[CH:15]=[CH:14][CH:13]=[C:12]1[CH2:16][CH2:17]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O>C1COCC1.C1(C)C=CC=CC=1>[Br:1][C:2]1[C:3](=[O:10])[N:4]([CH3:9])[C:5](=[O:8])[N:6]([CH2:17][CH2:16][C:12]2[S:11][CH:15]=[CH:14][CH:13]=2)[N:7]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 794002-ThiopheneethanolHCID 2605646-bromo-4-methyl-1,2,4-triazine-3,5(2h,4h)-dioneHCID 5462977Diethyl azodicarboxylate

Product 1

HCID 582698036-bromo-4-methyl-2-(2-thiophen-2-yl-ethyl)-2H-[1,2,4]triazine-3,5-dioneYield 79%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

0.4 g (1.94 mmol) of intermediate 2a are placed in the presence of 0.24 mL (2.14 mmol) of 2-thiophen-2-yl-ethanol, 0.61 g (2.33 mmol) of triphenylphosphine in 4 mL of THF. At 0° C., 0.54 mL (2.33 mmol) of DEAD in solution in toluene are added dropwise. The reaction medium is heated for 7 h at 70° C. After concentration, the obtained residue is taken up with ethyl acetate and washed with water. After drying on MgSO4, the organic phase is dry concentrated. The obtained residue is purified by flash chromatography on silica (CH2Cl2/MeOH, gradient 100/0 to 97/3 over 30 min). 0.48 g of crystals corresponding to the compound 4k are obtained (yield: 79%).

Workup

  1. concentrationAfter concentration
  2. washwashed with water
  3. customAfter drying on MgSO4
  4. customthe organic phase is dry
  5. concentrationconcentrated
  6. customThe obtained residue is purified by flash chromatography on silica (CH2Cl2/MeOH, gradient 100/0 to 97/3 over 30 min)

Sources & evidence

ORD record
ord-d8930fc73b854711bb04d529f1351cbd
Source dataset
uspto-grants-2013_12
Patent number
US08618287B2

Reaction notes

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