Methanethiol → Ethyl nitro(1,3-thiazinan-2-ylidene)acetate
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>[Cl-].[Zn+2].[Cl-].CCOCC.C(O)(C)C>[N+:9]([C:12](=[C:3]1[NH:8][CH2:7][CH2:6][CH2:5][S:4]1)[C:13]([O:15][CH2:16][CH3:17])=[O:14])([O-:11])=[O:10]Participants
Procedure
To a mixture of 235 g of 5,6-dihydro-2-(methylthio)-4H-1,3-thiazine and 2 g of zinc chloride at approximately 115° in a nitrogen atmosphere, 263 g of ethyl nitroacetate was added dropwise over a 1.5 hour period. The mixture was held at 110°-120° and the nitrogen atmosphere was maintained during the addition. Evolution of methyl mercaptan ceased after 45 minutes further stirring of the heated mixture when 1 g of zinc chloride was added to the stirred mixture at ca. 115°. After 1.25 hours an additional 1 g of zinc chloride was added and stirring of the mixture at ca. 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 which on recrystallization from methanol gave 2a as a pale yellow solid, m.p.: 105°-106°.
Workup
- additionwas added dropwise over a 1.5 hour period
- customwas held at 110°-120°
- temperaturethe nitrogen atmosphere was maintained during the addition
- additionwas added to the stirred mixture at ca. 115°
- customThe crystallized product was collected
- washwashed with ether
- customdried under reduced pressure
- customto leave a tan solid which
- customon recrystallization from methanol
Sources & evidence
- ORD record
- ord-2ef918d0b0634a019882b993f5e407ab
- Source dataset
- uspto-grants-1976_06
- Patent number
- US03962225
Reaction notes
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