methyl 2,2-dimethylpropanoate

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: 116 grams (1 mole) of methyl pivalate, 60 grams (2 moles) of sodium hydride (80 weight % suspension in white oil) and 234.3 grams (2 moles) of benzyl cyanide were reacted in 750 ml of dry toluene at 60° C. until the end of the evolution of hydrogen. There were added 500 ml of water to the cooled reaction solution, the mixture stirred and the aqueous phase acidified with HCl to pH 3 after the separation and then extracted with chloroform. After concentrating the chloroform the oil residue was fractionated at 0.6 Torr. 110.6 grams (55% of theory) of 4,4-dimethyl-2-phenyl-3-oxopentanenitrile came over at 111° C. to the cooled reaction solution after the separation extracted with chloroform After concentrating the chloroform the oil residue came over at 111° C.

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

Procedure: 234.6 grams (2 moles) of methyl pivalate and 120 grams (2 moles) of sodium hydride (80 weight % suspension in white oil) were heated to 90° C. in 1500 ml of dry toluene. There were dropped in at this temperature after addition of 1 ml of methanol 233.3 grams (2 moles) of propionitrile within 2.5 hours. After the end of the development of hydrogen the suspension was extracted with a total of 1200 ml of water and after phase separation the aqueous phase was acidified with concentrated HCl to a pH of 2. The deposited oil was separated off, the water phase extracted with chloroform, the organic extracts combined, dried and concentrated. The residue was fractionated in a water jet vacuum. 2,4,4-trimethyl-3-oxopentanenitrile came over at 87° C./11 Torr in an amount of 226.1 grams (81.2% of theory). There were dropped in at this temperature After the end of the development of hydrogen the suspension was extracted with a total of 1200 ml of water after phase separation the aqueous phase The deposited oil was separated off the water phase extracted with chloroform dried concentrated came over at 87° C./11 Torr in an amount of 226.1 grams (81.2% of theory)

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 55 grams of sodium hydride (as an 80 weight % suspension in white oil) were suspended in 500 ml of dry toluene, 106 grams (0.914 mole) of methyl pivalate added and the mixture heated to 85° C. Then under vigorous stirring there were dropped in 77 grams (1.87 moles) of acetonitrile within 4 hours. Stirring was continued subsequently at 85° C. until the end of the development of hydrogen. The thickly liquid reaction mass was cooled to room temperature, treated with 700 ml of water, stirred vigorously for 30 minutes and the two phases separated in a separatory funnel. The aqueous phase was acidified with 31 weight % of hydrochloric acid at a pH 1-2 and 0° C. The precipitated pivaloylacetonitrile was filtered off with suction, washed until neutral with ice water and dried to constant weight at 25 Torr and 40° C. There were obtained 106 grams (93% of theory) of analytically pure pivaloylacetonitrile having a melting point of 65°-68° C. Stirring The thickly liquid reaction mass was cooled to room temperature stirred vigorously for 30 minutes the two phases separated in a separatory funnel was acidified with 31 weight % of hydrochloric acid at a pH 1-2 and 0° C The precipitated pivaloylacetonitrile was filtered off with suction washed until neutral with ice water dried to constant weight at 25 Torr and 40° C

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

Procedure: A suspension of 9.6 g of sodium hydride in 300 ml of tetrahydrofuran was stirred at 60° while a mixture of 23.2 g of methyl trimethylacetate and 8.2 g of acetonitrile was added in one portion. The reaction mixture was heated at reflux for five hours, and then cooled to room temperature and concentrated by evaporation of the solvent under reduced pressure. The product thus formed was dissolved in water and washed with dichloromethane. The aqueous layer was made acidic with 1N hydrochloric acid, and the acidic solution was extracted with fresh dichloromethane. The organic extracts were combined, washed with water, dried, and the solvent was removed by evaporation to give 14.0 g of cyanomethyl tert.-butyl ketone. was added in one portion The reaction mixture was heated at reflux for five hours concentrated by evaporation of the solvent under reduced pressure The product thus formed washed with dichloromethane the acidic solution was extracted with fresh dichloromethane washed with water dried the solvent was removed by evaporation

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Dimethyl methylphosphonate (13.6 g, 0.11 mol) was dissolved in anhydrous THF (100 ml) under argon atmosphere. To the solution stirred at -78° C. was added dropwise n-butyl lithium (1.61N, 68.3 ml, 0.11 mol) over 30 minutes, and then a solution of commercially available methyl pivalate (5.0 g, 0.043 mol) in anhydrous THF (10 ml) was also added dropwise over 30 minutes. The reaction mixture was warmed to room temperature. Under ice cooling, acetic acid (7 ml) and water (10 ml) were added. After concentrating, water (20 ml) was added to the resulting residue. The mixture was extracted with ethyl acetate (50 ml×2), and the ethyl acetate layers were washed with water (20 ml×1) and with brine (20 ml×1), dried over anhydrous soldium sulfate, concentrated. Distillation of the residue gave dimethyl 3,3-dimethyl-2-oxo-butylphosphonate as a colorless clear oil (6.53 g, 0.031 mol, 72.6%, b.p.=90°-93° C./0.35 mmHg). The structure was identified by the following data. The reaction mixture was warmed to room temperature After concentrating water (20 ml) was added to the resulting residue The mixture was extracted with ethyl acetate (50 ml×2) the ethyl acetate layers were washed with water (20 ml×1) and with brine (20 ml×1) dried over anhydrous soldium sulfate concentrated Distillation of the residue

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Dimethyl methylphosphonate (13.6 g, 0.11 mol) was dissolved in anhydrous THF (100 ml) under argon atmosphere. To the solution stirred at -78° C. was added dropwise n-butyl lithium (1.61N, 68.3 ml, 0.11 mol) over 30 minutes, and then a solution of commercially available methyl pivalate (5.0 g, 0.043 mol) in anhydrous THF (10 ml) was also added dropwise over 30 minutes. The reaction mixture was warmed to room temperature. Under ice cooling, acetic acid (7 ml) and water (10 ml) were added. After concentrating, water (20 ml) was added to the resulting residue. The mixture was extracted with ethyl acetate (50 ml×2), and the ethyl acetate layers were washed with water (20 ml×1) and with brine (20 ml×1), dried over anhydrous soldium sulfate, concentrated. Distillation of the residue gave dimethyl 3,3-dimethyl-2-oxo-butylphosphonate as a colorless clear oil (6.53 g, 0.031 mol, 72.6%, b.p.=90°-93° C./0.35 mmHg). The structure was identified by the following data. The reaction mixture was warmed to room temperature After concentrating water (20 ml) was added to the resulting residue The mixture was extracted with ethyl acetate (50 ml×2) the ethyl acetate layers were washed with water (20 ml×1) and with brine (20 ml×1) dried over anhydrous soldium sulfate concentrated Distillation of the residue

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

Procedure: 116 grams (1 mole) of methyl pivalate, 60 grams (2 moles) of sodium hydride (80 weight % suspension in white oil) and 234.3 grams (2 moles) of benzyl cyanide were reacted in 750 ml of dry toluene at 60° C. until the end of the evolution of hydrogen. There were added 500 ml of water to the cooled reaction solution, the mixture stirred and the aqueous phase acidified with HCl to pH 3 after the separation and then extracted with chloroform. After concentrating the chloroform the oil residue was fractionated at 0.6 Torr. 110.6 grams (55% of theory) of 4,4-dimethyl-2-phenyl-3-oxopentanenitrile came over at 111° C. to the cooled reaction solution after the separation extracted with chloroform After concentrating the chloroform the oil residue came over at 111° C.

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

Procedure: 234.6 grams (2 moles) of methyl pivalate and 120 grams (2 moles) of sodium hydride (80 weight % suspension in white oil) were heated to 90° C. in 1500 ml of dry toluene. There were dropped in at this temperature after addition of 1 ml of methanol 233.3 grams (2 moles) of propionitrile within 2.5 hours. After the end of the development of hydrogen the suspension was extracted with a total of 1200 ml of water and after phase separation the aqueous phase was acidified with concentrated HCl to a pH of 2. The deposited oil was separated off, the water phase extracted with chloroform, the organic extracts combined, dried and concentrated. The residue was fractionated in a water jet vacuum. 2,4,4-trimethyl-3-oxopentanenitrile came over at 87° C./11 Torr in an amount of 226.1 grams (81.2% of theory). There were dropped in at this temperature After the end of the development of hydrogen the suspension was extracted with a total of 1200 ml of water after phase separation the aqueous phase The deposited oil was separated off the water phase extracted with chloroform dried concentrated came over at 87° C./11 Torr in an amount of 226.1 grams (81.2% of theory)

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 55 grams of sodium hydride (as an 80 weight % suspension in white oil) were suspended in 500 ml of dry toluene, 106 grams (0.914 mole) of methyl pivalate added and the mixture heated to 85° C. Then under vigorous stirring there was dropped in 77 grams (1.87 moles) of acetonitrile within 4 hours. Stirring was continued subsequently at 85° C. until the end of the development of hydrogen. The thickly liquid reaction mass was cooled to room temperature, treated with 700 ml of water, stirred vigorously for 30 minutes and the two phases separated in a separatory funnel. The aqueous phase was acidified with 31 weight % of hydrochloric acid at a pH 1-2 and 0° C. The precipitated pivaloylacetonitrile was filtered off with suction, washed until neutral with ice water and dried to constant weight at 25 Torr and 40° C. There were obtained 106 grams (93% of theory) of analytically pure pivaloylacetonitrile having a melting point of 65°-68° C. Stirring The thickly liquid reaction mass was cooled to room temperature stirred vigorously for 30 minutes the two phases separated in a separatory funnel was acidified with 31 weight % of hydrochloric acid at a pH 1-2 and 0° C The precipitated pivaloylacetonitrile was filtered off with suction washed until neutral with ice water dried to constant weight at 25 Torr and 40° C