Ethyl Acetoacetate → Ethyl 3-(3-methylphenyl)-3-oxopropanoate
Reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[OH-].[Na+].[C:12]1([CH3:21])[CH:17]=C[CH:15]=[C:14](C(Cl)=O)[CH:13]=1.[Na].C1(C)C=CC=C(C(CC(=O)CC(OCC)=O)=O)C=1.[Cl-].[NH4+]>O.C1C=CC=CC=1>[C:12]1([CH3:21])[CH:13]=[CH:14][CH:15]=[C:5]([C:3]([CH2:2][C:1]([O:7][CH2:8][CH3:9])=[O:6])=[O:4])[CH:17]=1Participants
Reactant 6
Product 1
Reagents, catalysts & solvents 2
Procedure
To a cold (5° C.) mixture of 137.5 g (1.05 mole) of ethyl acetoacetate, 175 ml. of benzene, 325 ml. of water, and 45.8 ml. of 33% sodium hydroxide was added simultaneously 221.05 g (1.430 mole) of m-toluoyl chloride and 190 ml. of 33% sodium hydroxide as described in Example 4. The aqueous solution of sodium salt of ethyl m-toluoylacetoacetate was stirred with 56.3 g of ammonium chloride overnight and worked up as described in Example 4 to give 38.0 g (17%) of crude ethyl m-toluoylacetate after a Kugelrohr distillation (95°-98° C.) at 0.05 mm Hg). A mixture of 20.6 g (0.1 mole) of crude ethyl m-toluoylacetate, 13.6 g (0.105 mole) of sulfuryl chloride, and 30 ml. of chloroform was held at reflux for 6 hours and worked up as described in Example 4 to give 25.0 g of ethyl 2-chloro-m-toluoylacetate, which was used directly as described below. A mixture of 22.5 g (0.1 mole) of ethyl 2-chloro-m-toluoylacetate, 7.6 g (0.11 mole) of thiourea and 100 ml. of ethanol was held at reflux for 2 hours and worked up as described in Example 4 to give 23.0 g of solid, which was recrystallized from ethanol to give 11.6 g (44%) of ethyl 2-amino-4-(m-tolyl)-5-thiazolecarboxylate, m.p. 185°-187° C.
Sources & evidence
- ORD record
- ord-4f556aac8b6a4b0e97fda98207e806b8
- Source dataset
- uspto-grants-1981_12
- Patent number
- US04308391
Reaction notes
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