Dichloromethane → HCID 86734073, compound

HRID 1287817Notes

Reaction equation

HRID 1287817 reaction equation
[CH3:1][C:2]1[N:3]=[C:4]([C:8]([OH:10])=[O:9])[S:5][C:6]=1[CH3:7].C(Cl)Cl.C(Cl)(=O)C(Cl)=O.[CH:20]1([NH:26][CH:27]2[CH2:32][CH2:31][CH2:30][CH2:29][CH2:28]2)[CH2:25][CH2:24][CH2:23][CH2:22][CH2:21]1>C(O)C.O>[CH3:1][C:2]1[N:3]=[CH:4][S:5][C:6]=1[CH3:7].[CH:27]1([NH:26][CH:20]2[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25]2)[CH2:28][CH2:29][CH2:30][CH2:31][CH2:32]1.[S:5]1[CH:6]=[CH:2][CH:1]=[C:4]1[C:8]([OH:10])=[O:9]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 7582DicyclohexylamineHCID 65578Oxalyl chlorideHCID 215055104,5-Dimethyl-1,3-thiazole-2-carboxylic acid

Product 1

HCID 86734073HCID 86734073, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 962WaterSolvent

Procedure

To a slurry of 19.0 g. (0.121 mole) of 4,5-dimethylthiazole-2-carboxylic acid in 250 ml. of dry methylene chloride was added over 1 hour 10.3 ml. (0.121 mole) of oxalyl chloride. The reaction mixture was stirred at room temperature for 1 hour and was refluxed for 2 hours. The small amount of insoluble material was removed by filtration and the filtrate was concentrated under reduced pressure to a yellow oil. Infrared spectrum indicated this to be the desired acid chloride. This was added dropwise to a stirred and cooled solution of 26.4 g. (0.24 mole) of hydrated sodium sulfhydrate in 275 ml. of ethanol and 30 ml. of water at such a rate as to keep the temperature of the mixture at 10°-15°. After the addition was completed, the reaction mixture was stirred for 40 minutes at 5°-10°. Then most of the ethanol was removed under reduced pressure and the residue was dissolved in 150 ml. of water. The pH of the solution was lowered to 2.5 with 6N hydrochloric acid and was maintained there, while the mixture was extracted with 5 × 100 ml. of ethyl acetate. The extracts were combined, washed with ice water, dried over magnesium sulfate, filtered and evaporated to dryness to give 10.6 g. of a reddish solid. It was dissolved in 200 ml. of hot ethanol and 7.5 ml. of dicyclohexylamine were added. Bright yellow crystals resulted. The mixture was cooled at 5° for 1 hour. Then the precipitate was removed by filtration, washed with ether and dried under high vacuum to give 11.75 g. (27%) of a yellow solid. NMR spectrum was consistent with the desired material.

Workup

  1. temperaturewas refluxed for 2 hours
  2. customThe small amount of insoluble material was removed by filtration
  3. concentrationthe filtrate was concentrated under reduced pressure to a yellow oil
  4. additionThis was added dropwise to
  5. stirringa stirred
  6. temperaturecooled solution of 26.4 g
  7. customat 10°-15°
  8. additionAfter the addition
  9. stirringthe reaction mixture was stirred for 40 minutes at 5°-10°
  10. customThen most of the ethanol was removed under reduced pressure
  11. dissolutionthe residue was dissolved in 150 ml
  12. temperaturewas maintained there, while the mixture
  13. extractionwas extracted with 5 × 100 ml
  14. washwashed with ice water
  15. dry with materialdried over magnesium sulfate
  16. filtrationfiltered
  17. customevaporated to dryness
  18. customto give 10.6 g
  19. dissolutionIt was dissolved in 200 ml
  20. customBright yellow crystals resulted
  21. temperatureThe mixture was cooled at 5° for 1 hour
  22. customThen the precipitate was removed by filtration
  23. washwashed with ether
  24. customdried under high vacuum
  25. customto give 11.75 g

Sources & evidence

ORD record
ord-4e24903f42344906b8e20dbecac6644d
Source dataset
uspto-grants-1976_10
Patent number
US03985740

Reaction notes

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