Sodium hydride → nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetic acid

HRID 442096Notes

Reaction equation

HRID 442096 reaction equation
CSCCO.[H-].[Na+].[N+:8]([C:11](=[C:16]1[NH:21][CH2:20][CH2:19][CH2:18][S:17]1)[C:12]([O:14]C)=[O:13])([O-:10])=[O:9]>O1CCCC1>[N+:8]([C:11](=[C:16]1[NH:21][CH2:20][CH2:19][CH2:18][S:17]1)[C:12]([OH:14])=[O:13])([O-:10])=[O:9]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 789252-(Methylthio)ethanolHCID 71400745Methyl nitro(1,3-thiazinan-2-ylidene)acetate

Product 1

HCID 73791479nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetic acid

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 100 g of 2-(methylthio)ethanol in dry tetrahydrofuran was added slowly to a solution of 6.0 g of sodium hydride (57% in mineral oil) in dry tetrahydrofuran at 0°. The mixture was then allowed to warm to room temperature and 13.1 g of methyl nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetate (1A), prepared as described in U.S. Pat. No. 3,962,234, was added, and the mixture was allowed to stand overnight at room temperature. The solvent then was evaporated under reduced pressure, the residue was poured into water and the mixture was extracted with ether. The separated aqueous phase was acidified with acetic acid, and the product was extracted with methylene chloride. The extract was dried (MgSO4), decolorized, and the solvent was evaporated under reduced pressure. The residue was washed with pentane, then crystallized from ether and recrystallized from isopropyl alcohol to give the 2-(methylthio)ethyl ester of nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetic acid (1B), as a pale yellow solid, m.p.: 72°-73°.

Workup

  1. addition3,962,234, was added
  2. customThe solvent then was evaporated under reduced pressure
  3. additionthe residue was poured into water
  4. extractionthe mixture was extracted with ether
  5. extractionthe product was extracted with methylene chloride
  6. dry with materialThe extract was dried (MgSO4)
  7. customthe solvent was evaporated under reduced pressure
  8. washThe residue was washed with pentane
  9. customcrystallized from ether
  10. customrecrystallized from isopropyl alcohol

Sources & evidence

ORD record
ord-6431fce8dd0b4e228a05307ee3b40253
Source dataset
uspto-grants-1977_08
Patent number
US04044128

Reaction notes

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