Water → Ethyl 2-(bromoethoxyimino)-2-(2-tritylamino-4-thiazolyl)-acetate

HRID 1904130Notes

Reaction equation

HRID 1904130 reaction equation
Cl.[OH:2][N:3]=[C:4]([C:10]1[N:11]=[C:12]([NH:15][C:16]([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[S:13][CH:14]=1)[C:5]([O:7][CH2:8][CH3:9])=[O:6].C(=O)([O-])[O-].[K+].[K+].[Br:41][CH2:42][CH2:43]Br.O>CN(C)C=O.C(Cl)Cl>[Br:41][CH2:42][CH2:43][O:2][N:3]=[C:4]([C:10]1[N:11]=[C:12]([NH:15][C:16]([C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)([C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[S:13][CH:14]=1)[C:5]([O:7][CH2:8][CH3:9])=[O:6]

Participants

7

Reactant 4

HCID 962WaterHCID 78391,2-DibromoethaneHCID 11430Potassium CarbonateHCID 78408569HCID 78408569, compound

Product 1

HCID 53679114Ethyl 2-(bromoethoxyimino)-2-(2-tritylamino-4-thiazolyl)-acetate

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

A mixture of 4.94 g of the syn isomer of ethyl 2-hydroxyimino-2-(2-tritylamino-4-thiazolyl)-acetate hydrochloride in 10 ml of dimethylformamide was admixed under an inert atmosphere at room temperature over 3 minutes with 4.14 g of potassium carbonate and the mixture was stirred at 20° C. for 20 minutes. 8.65 ml of 1,2-dibromoethane were added thereto and the mixture was stirred for 30 hours and was then poured into a mixture of 100 ml of distilled water and 20 ml of methylene chloride. The decanted aqueous phase was extracted with methylene chloride and the combined organic phases were rinsed with distilled water. The wash water was reextracted with methylene chloride and the combined organic solution were dried and vacuum filtered. The filter was rinsed with methylene chloride and the filtrate was evaporated to dryness. The residue was chromatographed over silica gel and was eluted with benzene containing 5% ether. The first fraction was crystallized from methanol after dissolution at 50°-60° C. and was vacuum filtered at 0° to 5° C. to obtain 1.16 g of of the syn isomer of ethyl 2-(bromoethoxyimino)-2-(2-tritylamino-4-thiazolyl)-acetate in the form of a white cream product melting at 117° C. and a second homogeneous fraction of 1.258 of product was also obtained.

Workup

  1. stirringthe mixture was stirred for 30 hours
  2. extractionThe decanted aqueous phase was extracted with methylene chloride
  3. washthe combined organic phases were rinsed with distilled water
  4. customthe combined organic solution were dried
  5. filtrationvacuum filtered
  6. washThe filter was rinsed with methylene chloride
  7. customthe filtrate was evaporated to dryness
  8. customThe residue was chromatographed over silica gel
  9. washwas eluted with benzene containing 5% ether
  10. customThe first fraction was crystallized from methanol
  11. dissolutionafter dissolution at 50°-60° C.
  12. filtrationfiltered at 0° to 5° C.

Sources & evidence

ORD record
ord-37335fc4b09747848894e751ed13b11e
Source dataset
uspto-grants-1984_03
Patent number
US04439433

Reaction notes

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