Hydrochloric Acid → HCID 140357028, compound

HRID 1461079Notes

Reaction equation

HRID 1461079 reaction equation
C([O:4][C:5]1[CH:6]=[C:7]([S:15](Cl)(=[O:17])=[O:16])[CH:8]=[CH:9][C:10]=1[O:11]C(=O)C)(=O)C.[NH2:19][CH2:20][CH2:21][O:22]/[N:23]=[C:24](/[C:30]1[N:31]=[C:32]([NH:35]C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[S:33][CH:34]=1)\[C:25]([O:27]CC)=[O:26].[OH-].[Na+].Cl>CN(C)C1C=CN=CC=1.CN(C)C=O.O>[OH:4][C:5]1[CH:6]=[C:7]([S:15]([NH:19][CH2:20][CH2:21][O:22]/[N:23]=[C:24](/[C:30]2[N:31]=[C:32]([NH2:35])[S:33][CH:34]=2)\[C:25]([OH:27])=[O:26])(=[O:16])=[O:17])[CH:8]=[CH:9][C:10]=1[OH:11]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 190224303,4-Bis(acetyloxy)benzenesulfonyl chlorideHCID 154041583HCID 154041583, compound

Product 1

HCID 140357028HCID 140357028, compound

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
20 °C

Procedure

1.17 g of 3,4-diacetoxy-benzenesulphonyl chloride were added to a solution of 6.0 g of 2-(tritylamino)-4-thiazoleglyoxylic acid ethyl ester (Z)-O-(2-aminoethyl) oxime and 0.49 g of 4-dimethylamino-pyridine in 50 ml of N,N-dimethylformamide. The reaction solution was stirred at 20° C. for 3 hours, 10 ml of 2N sodium hydroxide solution were then added, and the solution was stirred at 20° C. for an additional hour. Then, 20 ml of water were added and the pH of the reaction mixture was lowered to 3 by the addition of 3N hydrochloric acid. The resulting precipitate was filtered off under suction, washed with a small amount of water and then heated to 50° C. for 40 minutes in 60 ml of 80% aqueous acetic acid. The mixture was cooled to 20° C. and evaporated completely in a vacuum. The residue was dissolved in 30 ml of methanol and treated in an ice bath with a total of 180 ml of diethyl ether. The precipitate was filtered off under suction, suspended in a small amount of water and brought into solution by the dropwise addition of 2N sodium hydroxide solution. The solution of pH 7.5 was applied to a MCI gel column (CHP20P) conditioned with 1% aqueous acetic acid and chromatographed according to the procedure described in the first paragraph of this Example. The product was eluted with a 9:1 (v/v) water/acetonitrile mixture. The pure fractions were concentrated completely in a vacuum and the solid residue was crystallized from methanol/diethyl ether. There was obtained 2-amino-4-thiazoleglyoxylic acid (Z)-O-[2-[(3,4-dihydroxyphenyl)sulphonamido]ethyl] oxime as white crystals of melting point 92°-94° C. (decomposition).

Workup

  1. stirringthe solution was stirred at 20° C. for an additional hour
  2. filtrationThe resulting precipitate was filtered off under suction
  3. washwashed with a small amount of water
  4. temperatureheated to 50° C. for 40 minutes in 60 ml of 80% aqueous acetic acid
  5. temperatureThe mixture was cooled to 20° C.
  6. customevaporated completely in a vacuum
  7. dissolutionThe residue was dissolved in 30 ml of methanol
  8. additiontreated in an ice bath with a total of 180 ml of diethyl ether
  9. filtrationThe precipitate was filtered off under suction
  10. additionbrought into solution by the dropwise addition of 2N sodium hydroxide solution
  11. customchromatographed
  12. washThe product was eluted with a 9:1 (v/v) water/acetonitrile mixture
  13. concentrationThe pure fractions were concentrated completely in a vacuum
  14. customthe solid residue was crystallized from methanol/diethyl ether

Sources & evidence

ORD record
ord-b54dab0c42a44f459a1e79503df6df4b
Source dataset
uspto-grants-1991_12
Patent number
US05073550

Reaction notes

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