Methanethiol → Ethyl nitro(1,3-thiazinan-2-ylidene)acetate

HRID 258547Notes

Reaction equation

HRID 258547 reaction equation
[S:1]1[CH:6]=[CH:5][CH2:4][N:3]=[CH:2]1.[N+:7]([CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])([O-:9])=[O:8].CS>[Cl-].[Zn+2].[Cl-].CCOCC.C(O)(C)C>[N+:7]([C:10](=[C:2]1[NH:3][CH2:4][CH2:5][CH2:6][S:1]1)[C:11]([O:13][CH2:14][CH3:15])=[O:12])([O-:9])=[O:8]

Participants

6

Reactant 3

HCID 878MethanethiolHCID 69379Ethyl nitroacetateHCID 219899974H-1,3-Thiazine

Product 1

HCID 71443329Ethyl nitro(1,3-thiazinan-2-ylidene)acetate

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalyst3×HCID 22147583Diethyl ether 2-propanolSolvent

Procedure

To a mixture of 235 g of 5,6-dihydro-2-methylthio)-4H-1,3-thiazine (A. F. McKay et al., J. Am. Chem. Soc., 80, 3339 (1958)) and 2 g of zinc chloride at approximately 115° in a nitrogen atmosphere, 263 g of ethyl nitroacetate (S. Zen, et. al., Kogyo Kagaku Zasshi, 74, 70 (1971)) was added dropwise over a 1.5 hour period. The mixture was held at 110°-120°. When evolution of methyl mercaptan ceased after 45 minutes stirring of the heated mixture, 1 g of zinc chloride was added and the mixture was stirred at about 115° For 1.25 hours. An additional 1 g of zinc chloride then was added and stirring of the mixture at about 115° was continued for 1.5 hours. The mixture then was poured into a cooled solution of 2/1 (volume) ether/isopropyl alcohol mixture. The crystallized product was collected, washed with ether and dried under reduced pressure to leave a tan solid, m.p. 100°-102°, which on recrystallization from methanol gave ethyl nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetate (1A) as a pale yellow solid, m.p. 105°-106°.

Workup

  1. customwas held at 110°-120°
  2. additionwas added
  3. stirringstirring of the mixture at about 115°
  4. waitwas continued for 1.5 hours
  5. customThe crystallized product was collected
  6. washwashed with ether
  7. customdried under reduced pressure
  8. customto leave a tan solid, m.p. 100°-102°, which
  9. customon recrystallization from methanol

Sources & evidence

ORD record
ord-3d0f1b06a6ec404c8d8846c9e0b36f93
Source dataset
uspto-grants-1977_07
Patent number
US04033953

Reaction notes

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