Methyl bromoacetate → HCID 54136905, compound

HRID 981430Notes

Reaction equation

HRID 981430 reaction equation
C([O-])(C)(C)C.[K+].[C:7]([NH:9][CH:10]=[N:11][CH:12]1[C:19]2[CH:18]=[CH:17][S:16][C:15]=2[CH2:14][C:13]1([CH3:21])[CH3:20])#[N:8].[CH3:22][O:23][C:24](=[O:27])[CH2:25]Br>CS(C)=O>[CH3:22][O:23][C:24]([C:25]1[N:11]([CH:12]2[C:19]3[CH:18]=[CH:17][S:16][C:15]=3[CH2:14][C:13]2([CH3:21])[CH3:20])[CH:10]=[N:9][C:7]=1[NH2:8])=[O:27]

Participants

5

Reactant 3

HCID 60984Methyl bromoacetateHCID 20069476HCID 20069476, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 54136905HCID 54136905, compound

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

3.3 g of potassium tert.-butanolate are added to a mixture of 6.2 g of N-cyano-N'-(5,6-dihydro-5,5-dimethyl-4H-cyclopenta[b]thiophen-4-yl)-formamidine and 5 ml of dimethyl sulfoxide. After the mixture has been stirred for 15 hours at room temperature, 3.1 ml of bromoacetic acid methyl ester are added dropwise thereto. After 2 hours, ice-water is added to the reaction mixture. Extraction with ether, drying of the organic phase with sodium sulfate and evaporation of the solvent yield 8.4 g of N-cyano-N'-(5,6-dihydro-5,5-dimethyl-4H-cyclopenta[b]thiophen-4-yl)-N'-methoxycarbonylmethylformamidine in the form of a yellowish-brown oil. The oil is placed in 8 ml of methanol and, after the addition of 2.6 ml of 30% methanolic sodium methanolate solution, is heated at boiling for 16 hours. After cooling, the reaction solution is poured onto an ice-water/ether mixture. The organic phase is separated off, extracted with water and dried over sodium sulfate. Filtration and evaporation yield 5.1 g of brown crystals which are purified by chromatography on silica gel (eluant: ethyl acetate/hexane 1:1). 3.7 g of 4-amino-1-(5,6-dihydro-5,5-dimethyl-4H-cyclopenta[b]thiophen-4-yl)-5-imidazolecarboxylic acid methyl ester are obtained in the form of beige crystals having a melting point of 161°-162° C.

Workup

  1. waitAfter 2 hours
  2. extractionExtraction with ether
  3. dry with materialdrying of the organic phase with sodium sulfate and evaporation of the solvent yield 8.4 g of N-cyano-N'-(5,6-dihydro-5,5-dimethyl-4H-cyclopenta[b]thiophen-4-yl)-N'-methoxycarbonylmethylformamidine in the form of a yellowish-brown oil
  4. additionafter the addition of 2.6 ml of 30% methanolic sodium methanolate solution
  5. temperatureis heated
  6. waitat boiling for 16 hours
  7. temperatureAfter cooling
  8. additionthe reaction solution is poured onto an ice-water/ether mixture
  9. customThe organic phase is separated off
  10. extractionextracted with water
  11. dry with materialdried over sodium sulfate
  12. filtrationFiltration and evaporation yield 5.1 g of brown crystals which
  13. customare purified by chromatography on silica gel (eluant: ethyl acetate/hexane 1:1)

Sources & evidence

ORD record
ord-3584d9ef12b2480cb0c631f0d5727847
Source dataset
uspto-grants-1991_02
Patent number
US04992090

Reaction notes

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