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

HRID 1904133Notes

Reaction equation

HRID 1904133 reaction equation
C(=O)([O-])[O-].[K+].[K+].Cl.[C:8]([NH:27][C:28]1[S:29][CH:30]=[C:31]([C:33](=[N:39][OH:40])[C:34]([O:36][CH2:37][CH3:38])=[O:35])[N:32]=1)([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.CN(C)C=O.[Br:46][CH2:47][CH2:48]Br>C(Cl)Cl.O>[C:8]([NH:27][C:28]1[S:29][CH:30]=[C:31]([C:33](=[N:39][O:40][CH2:48][CH2:47][Br:46])[C:34]([O:36][CH2:37][CH3:38])=[O:35])[N:32]=1)([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)([C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 78391,2-DibromoethaneHCID 11430Potassium CarbonateHCID 78408569Ethyl 2-(2-tritylamino-4-thiazolyl)-2-hydroxyimino-acetate hydrochloride

Product 1

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

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

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

Workup

  1. stirringThe mixture was stirred for 30 hours
  2. customThe mixture was decanted
  3. extractionthe aqueous phase was extracted with methylene chloride
  4. customThe combined organic phases were dried
  5. filtrationvacuum filtered
  6. washThe filter was rinsed
  7. customthe filtrate was evaporated to dryness
  8. customto obtain a raw product which
  9. customwas chromatographed over silica gel
  10. washElution with benzene containing 5% of ether
  11. customyielded a first fraction which
  12. customwas crystallized from methanol
  13. dissolutionafter dissolution at 50°-60° C
  14. filtrationVacuum filtration at 0° to 5° C.

Sources & evidence

ORD record
ord-3cbbf6c321ad414e88e7adb6a1c4242d
Source dataset
uspto-grants-1984_03
Patent number
US04439433

Reaction notes

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