Methanethiol → phenyl nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetate

HRID 442477Notes

Reaction equation

HRID 442477 reaction equation
CS[C:3]1[S:4][CH2:5][CH2:6][CH2:7][N:8]=1.[N+:9]([CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])([O-:11])=[O:10].CS.CCO[CH2:23][CH3:24].[CH:25](O)(C)[CH3:26]>[Cl-].[Zn+2].[Cl-]>[N+:9]([C:12](=[C:3]1[NH:8][CH2:7][CH2:6][CH2:5][S:4]1)[C:13]([O:15][C:16]1[CH:24]=[CH:23][CH:26]=[CH:25][CH:17]=1)=[O:14])([O-:11])=[O:10]

Participants

6

Reactant 4

HCID 878MethanethiolHCID 69379Ethyl nitroacetateHCID 27820812-(methylsulfanyl)-5,6-dihydro-4H-1,3-thiazineHCID 22147583Diethyl ether 2-propanol

Product 1

HCID 85867565phenyl nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetate

Reagents, catalysts & solvents 1

HCID 3007855ZincchlorideCatalyst3×

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. Zea, 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 further 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 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 A 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
  10. customgave A as a pale yellow solid, m.p. 105°-106°

Sources & evidence

ORD record
ord-8e869395e9454fd5a27eb6adddb4382a
Source dataset
uspto-grants-1977_08
Patent number
US04045559

Reaction notes

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