Dichloromethane → 3-Iodo-1,5-bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-one

HRID 2097492Notes

Reaction equation

HRID 2097492 reaction equation
[CH3:1][Si:2]([CH3:26])([CH3:25])[CH2:3][CH2:4][O:5][CH2:6][N:7]1[C:11]2[CH:12]=[N:13][N:14]([CH2:17][O:18][CH2:19][CH2:20][Si:21]([CH3:24])([CH3:23])[CH3:22])[C:15](=[O:16])[C:10]=2[CH:9]=[CH:8]1.C(=O)([O-])O.[Na+].S([O-])([O-])(=O)=O.[Mg+2].ClCCl.[I:41]Cl>O.C(#N)C>[I:41][C:9]1[C:10]2[C:15](=[O:16])[N:14]([CH2:17][O:18][CH2:19][CH2:20][Si:21]([CH3:24])([CH3:23])[CH3:22])[N:13]=[CH:12][C:11]=2[N:7]([CH2:6][O:5][CH2:4][CH2:3][Si:2]([CH3:26])([CH3:25])[CH3:1])[CH:8]=1

Participants

8

Reactant 5

HCID 6344DichloromethaneHCID 24083Sulfuric acid magnesium salt (1:1)HCID 24640Iodine chlorideHCID 516892Sodium BicarbonateHCID 666029251,5-Bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-one

Product 1

HCID 666025043-Iodo-1,5-bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-oneYield 79%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

To 65 ml of acetonitrile solution containing 7.0 g (18 mmol) of 1,5-bis(2-trimethylsilylethoxymethyl)-1,5-dihydropyrrolo[2,3-d]pyridazin-4-one obtained in Reference example 18-(a) were added 6.0 g (71 mmol) of sodium hydrogencarbonate and 12.4 g (103 mmol) of anhydrous magnesium sulfate under argon atmosphere, and the mixture was stirred at room temperature for 1 hour. Then, 4.0 g (36 mmol) of s-caprolactam and 35.5 ml (35.5 mmol) of dichloromethane solution containing 1M iodine chloride were added to the mixture, and the mixture was further stirred for 3 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer after separation was washed successively with 5% aqueous sodium hydrogen sulfite solution and then a saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate, and then, concentrated under reduced pressure. The obtained residue was applied to silica gel column chromatography (Eluent; hexane:ethyl acetate=5:1 (V/V)), and the fractions containing the desired compound were concentrated under reduced pressure to obtain 7.3 g of the title compound as a brownish solid. (Yield: 79%)

Workup

  1. additionwere added to the mixture
  2. stirringthe mixture was further stirred for 3 hours
  3. additionwas added to the reaction mixture
  4. extractionthe mixture was extracted with ethyl acetate
  5. customThe organic layer after separation
  6. washwas washed successively with 5% aqueous sodium hydrogen sulfite solution
  7. dry with materiala saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. additionthe fractions containing the desired compound
  10. concentrationwere concentrated under reduced pressure

Sources & evidence

ORD record
ord-9df5871603d54189893f8516f393af6b
Source dataset
uspto-grants-2013_05
Patent number
US08450319B2

Reaction notes

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