5-(methoxymethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,2-Dimethyl-1,3-dioxane-4,6-dione (100 g) was heated in trimethylorthoformate (500 ml) at 100° C. for 2 h. The solution was evaporated under reduced pressure to give an oil. The oil was triturated with 1:1 isohexane/diethyl ether (400 ml) and the solid was filtrated and dried in vacuo to give the sub-title compound (99.8 g). The solution was evaporated under reduced pressure to give an oil The oil was triturated with 1:1 isohexane/diethyl ether (400 ml) the solid was filtrated dried in vacuo

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3-Methoxy-4-methoxycarbonylaniline (14.15 g, 78 mmol) was suspended in isopropanol and heated at 50° C. 2,2-Dimethyl-5-methoxymethylene-1,3-dioxane-4,6-dione (14.8 g, 80 mmol), (Montatsh. Chem. 1967, 98, 564), was then added in portions over 10 minutes and the mixture was heated at reflux for 30 minutes. The mixture was left to cool to ambient temperature overnight. The precipitate formed was collected by filtration, washed with isopropanol and dried under vacuum to give 5-((3-methoxy-4-methoxycarbonylanilino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (25.2 g, 96%). the mixture was heated at reflux for 30 minutes The mixture was left to cool to ambient temperature overnight The precipitate formed was collected by filtration washed with isopropanol dried under vacuum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2-acetamido-6-aminopyridine (2.9 g, 19 mmol), (Angew. chem. 1995, 107, 2589), and 2,2-dimethyl-5-methoxymethylene-1,3-dioxane-4,6-dione (4.28 g, 23 mmol), (Montatsh. Chem. 1967, 98, 564), in ethanol (75 ml) was stirred and heated at reflux for 5 hours. The mixture was allowed to cool and the precipitated product was collected by filtration and dried to give 5-((6-acetamido-2-pyridylamino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (1.3 g, 22%) as a yellow solid. heated at reflux for 5 hours to cool the precipitated product was collected by filtration dried

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Cyano-3-(3-morpholinopropoxy)aniline (2.5 g, 9.6 mmol) and 2,2-dimethyl-5-methoxymethylene-1,3-dioxane-4,6-dione (2.4 g, 13 mmol), (Montatsh. Chem. 1967, 98, 564), in ethanol (40 ml) was heated at reflux for 2 hours. The mixture was allowed to cool and the solid was collected by filtration to give 5-((4-cyano-3-(3-morpholinopropoxy)anilino)methylene)-2,2-dimethyl-1,3-dioxane-4.6-dione (2.96 g, 74%). at reflux for 2 hours to cool the solid was collected by filtration

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Cyano-3-(2-methoxyethoxy)aniline (760 mg, 4 mmol) and 2,2-dimethyl-5-methoxymethylene-1,3-dioxane-4,6-dione (1.0 g, 5.4 mmol), (Montatsh. Chem. 1967, 98, 564), in ethanol (20 ml) was heated at reflux for 1 hour. The mixture was allowed to cool and the solid collected by filtration to give 5-((4-cyano-3-(2-methoxyethoxy)anilino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (840 mg, 61%) as an orange solid. at reflux for 1 hour to cool the solid collected by filtration

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 10g of meldrum acid were dissolved in 39 ml of trimethylorthoformate and the mixture refluxed at 90° C. under nitrogen atmosphere for 3 hours. After cooling at room temperature, pale yellow solid was collected by filtration. washed with a small amount of trimethylorthoformate, petroleum ether, then dried to yield 7.8 g product. After cooling at room temperature pale yellow solid was collected by filtration washed with a small amount of trimethylorthoformate, petroleum ether dried

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,2-dimethyl-1,3-dioxane-4,6-dione (D-2) (10.0 g, 70 mmol, 1.0 eq) in trimethyl orthoformate (100 mL, 365 mmol, 5.0 eq) is stirred at reflux for 3 h. The resulting mixture is cooled to RT and concentrated in vacuo. The residue is triturated with diethyl ether and then filtered. The filter cake is washed with cooled diethyl ether and dried in vacuo to afford the product, 5-(methoxymethylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (D-3). at reflux for 3 h concentrated in vacuo The residue is triturated with diethyl ether filtered The filter cake is washed with cooled diethyl ether dried in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The mixture of 6-chloropyridin-3-amine (5.0 g, 38.8 mmol) and 5-(methoxymethylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (7.2 g, 38.8 mmol) in i-PrOH (60 mL) was stirred at reflux for 2 h, and the solvent was removed to afford 5-((6-chloropyridin-3-ylamino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione as a solid in 91% yield (10.0 g). m/z 283 (M+H)+ at reflux for 2 h the solvent was removed

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The mixture of 6-chloropyridin-3-amine (5.0 g, 38.8 mmol) and 5-(methoxymethylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (7.2 g, 38.8 mmol) in i-PrOH (60 mL) was stirred at reflux for 2 h, and the solvent was removed to afford 5-((6-chloropyridin-3-ylamino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione as a solid in 91% yield (10.0 g). m/z 283 (M+H)+ at reflux for 2 h the solvent was removed