Acetyl chloride → HCID 53826813, compound

HRID 2397539Notes

Reaction equation

HRID 2397539 reaction equation
[N+:1]([C:4](=[C:8]1[NH:13][CH2:12][CH2:11][CH2:10][S:9]1)[C:5](=[O:7])[CH3:6])([O-:3])=[O:2].[H-].[Na+].[H][H].[C:18](Cl)(=[O:20])[CH3:19].C(=O)(O)[O-].[Na+]>O1CCCC1.C(OCC)(=O)C.CCOCC.C(Cl)(Cl)Cl>[C:18]([N:13]1[CH2:12][CH2:11][CH2:10][S:9][C:8]1=[C:4]([N+:1]([O-:3])=[O:2])[C:5](=[O:7])[CH3:6])(=[O:20])[CH3:19]

Participants

10

Reactant 5

HCID 6367Acetyl chlorideHCID 24758Sodium hydrideHCID 516892Sodium BicarbonateHCID 714007471-Nitro-1-(1,3-thiazinan-2-ylidene)propan-2-oneHCID 178418361HCID 178418361, compound

Product 1

HCID 53826813HCID 53826813, compound

Reagents, catalysts & solvents 4

HCID 3283Diethyl EtherSolventHCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of 20.2 g of 1-nitro-1-(tetrahydro-2H-1,3-thiazine-2-ylidene)-2-propanone (1A; Example 2, Ser. No. 547,417, now U.S. Pat. No. 3,962,225) in 200 ml of tetrahydrofuran (THF) was added dropwise to a stirred suspension of sodium hydride (4.65 g of 57% dispersion in mineral oil in 100 ml of THF), the mixture being maintained at about 0°. After the addition was complete, stirring at 0° was continued until hydrogen evolution ceased. The stirred mixture then was allowed to warm to room temperature and stirred overnight. The mixture then was cooled to 0° and a solution of 8.2 g of acetyl chloride in 50 ml of THF was added dropwise. The mixture was stirred at 0° C. for 30 minutes and then allowed to warm to room temperature gradually and stirred at room temperature for 90 hours. The reaction mixture then was poured into a mixture of chloroform and saturated sodium bicarbonate solution. The organic phase was separated, washed with water, saturated sodium chloride solution, dried (sodium sulfate) and stripped of solvent under reduced pressure to leave a dark viscous oil. The oil was dissolved in ethyl acetate, the solution was chilled and an equivalent amount of ether was added. The liquid phase was separated and stripped of solvent under reduced pressure. The resulting oil was dissolved in methylene chloride and extracted with 10% sodium hydroxide solution. The organic phase was separated, washed with water and saturated sodium chloride solution, dried (Na2SO4) and stripped of solvent under reduced pressure. The resulting liquid was triturated with ether and chilled to give 1, as a yellow solid, m.p.: 73.5°-76°.

Workup

  1. temperaturethe mixture being maintained at about 0°
  2. additionAfter the addition
  3. stirringstirred overnight
  4. temperatureThe mixture then was cooled to 0°
  5. stirringThe mixture was stirred at 0° C. for 30 minutes
  6. temperatureto warm to room temperature gradually
  7. stirringstirred at room temperature for 90 hours
  8. customThe organic phase was separated
  9. washwashed with water, saturated sodium chloride solution
  10. dry with materialdried (sodium sulfate)
  11. customto leave a dark viscous oil
  12. temperaturethe solution was chilled
  13. customThe liquid phase was separated
  14. dissolutionThe resulting oil was dissolved in methylene chloride
  15. extractionextracted with 10% sodium hydroxide solution
  16. customThe organic phase was separated
  17. washwashed with water and saturated sodium chloride solution
  18. dry with materialdried (Na2SO4)
  19. customThe resulting liquid was triturated with ether
  20. temperaturechilled
  21. customto give 1

Sources & evidence

ORD record
ord-6dda5be830964ed1a19f782913e3a8a1
Source dataset
uspto-grants-1977_05
Patent number
US04022775

Reaction notes

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