Methyl 3-aminocrotonate → 3-imino-2-methoxycarbonyl-N-phenoxycarbonylthiobutyramide

HRID 437721Notes

Reaction equation

HRID 437721 reaction equation
[NH2:1]/[C:2](/[CH3:8])=[CH:3]\[C:4]([O:6][CH3:7])=[O:5].[O:9]([C:16]([N:18]=[C:19]=[S:20])=[O:17])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1>C1(C)C=CC=CC=1>[NH:1]=[C:2]([CH3:8])[CH:3]([C:4]([O:6][CH3:7])=[O:5])[C:19]([NH:18][C:16]([O:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:17])=[S:20]

Participants

4

Reactant 2

HCID 643918Methyl 3-aminocrotonateHCID 12212046Phenoxycarbonyl isothiocyanate

Product 1

HCID 78265373-imino-2-methoxycarbonyl-N-phenoxycarbonylthiobutyramide

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

A warm solution of methyl 3-aminocrotonate (prepared according to the method of Conrad and Epstein, Chemische Berichte, 1887, 20, 3054, 10.4 g.) in toluene (20 ml.) was added with stirring to a solution of phenoxycarbonylisothiocyanate (16 g.) in toluene (50 ml.). The temperature of the mixture rose from 20° C. to 35° C. The mixture was then stirred for 11/2 hours at ambient temperature, filtered and the solid residue washed with light petroleum (b.p. 40°-60° C.) to give 3-imino-2-methoxycarbonyl-N-phenoxycarbonylthiobutyramide (8.6 g.) in the form of an orange solid, which was then dissolved in ethyl acetate (100 ml.). To this solution, a solution of bromine (1.67 ml.) in ethyl acetate (5 ml.) was added over 15 minutes at 2°-5° C. The mixture was stirred at ambient temperature for 11/2 hours and the solid product filtered off to give 4-methoxycarbonyl-3-methyl-5-phenoxycarbonylaminoisothiazole hydrobromide (9.6 g.) m.p. 170°- 173° C. A solution of methylamine in ethanol (30% w/v; 20 ml.) was added to 4-methoxycarbonyl-3-methyl-5-phenoxycarbonylaminoisothiazole hydrobromide (9.0 g.). The mixture was heated under reflux for 15 minutes, diluted with water (30 ml.), filtered and the solid residue dried at 100° C., to give 1-(4-methoxycarbonyl-3-methylisothiazol-5-yl)-3-methylurea (4.1 g.), m.p. 236°-237° C.

Workup

  1. customrose from 20° C. to 35° C
  2. filtrationfiltered
  3. washthe solid residue washed with light petroleum (b.p. 40°-60° C.)

Sources & evidence

ORD record
ord-040bc73c70ed4840a1cfb2a58deb6750
Source dataset
uspto-grants-1977_06
Patent number
US04032323

Reaction notes

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