butane-1,1-diol

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: 5 mmol of triethylamine are mixed with 1 mol of 1,3-butanediol. The mixture is kept on ice and stirred while 1 mol of diketene is added dropwise over 1.5 hours. Stirring is continued for 5 to 7 hours at 0° C., then for 15 hours at room temperature. The reaction is monitored occasionally by proton NMR and after 15 hours, it is complete. This procedure yields a mixture of butanediol-acetoacetate and butanediol-diacetoacetate in proportion 77:23 (assayed by gas chromatography). Butanediol-diacetoacetate can be obtained as a main product by reacting 1 mol of butanediol with 2 mol of diketene.

Conditions: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A polyethylene glycol terephtalate/polybutylene terephthalate copolymer may be synthesized from a mixture of dimethyl terephthalate, butanediol (in excess), polyethylene glycol, an antioxidant and a catalyst. The mixture is placed in a reaction vessel and heated to about 180° C., and methanol is distilled as transesterification proceeds. During the transesterification, the ester bond with methyl is replaced with an ester bond with butylene and/or the polyethylene glycol. After transesterification, the temperature is raised slowly to about 245° C., and a vacuum (finally less than 0.1 mbar) is achieved. The excess butanediol is distilled off and a prepolymer of butanediol terephthalate condenses with the polyethylene glycol to form a polyethylene/polybutylene terephthalate copolymer. A terephthalate moiety connects the polyethylene glycol units to the polybutylene terephthalate units of the copolymer and thus such a copolymer also is sometimes referred to as a polyethylene glycol terephthalate/polybutylene terephthalate copolymer (PEGT/PBT copolymer). The mixture is placed in a reaction vessel methanol is distilled as transesterification proceeds After transesterification, the temperature is raised slowly to about 245° C. The excess butanediol is distilled off

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

Procedure: A solution of 2(E)-hex-3-ene-2,5-diol (122) (0.441 g, 3.8 mmol), 5-acetoxy isophthaloyl chloride (117) (1.044 g, 4.0 mmol), a catalytic amount of 1,4-diazabicyclo[2.2.2]octane, and a catalytic amount of potassium iodide in 20 mL of pyridine was brought to 50° C. while stirring under nitrogen. After 24 hours, butanediol (0.072 g, 0.8 mmol) diluted in 10 mL of pyridine was added to the reaction mixture using a syringe pump over 8 hours. The solution was then quenched in 200 mL of cold 1N hydrochloric acid. The polymer precipitate was collected by filtration, redissolved in tetrahydrofuran, and precipitated in 100 mL of cold 1N hydrochloric acid. The polymer is then collected by filtration and dried under high vacuum. The polymer was found to have a molecular weight of ˜12,000 g/mol by GPC. was brought to 50° C. was added to the reaction mixture over 8 hours The solution was then quenched in 200 mL of cold 1N hydrochloric acid The polymer precipitate was collected by filtration redissolved in tetrahydrofuran precipitated in 100 mL of cold 1N hydrochloric acid The polymer is then collected by filtration dried under high vacuum

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

Procedure: A solution of (E)-hex-3-ene-2,5-diol (122) (0.441 g, 3.8 mmol), isophthaloyl chloride (115) (0.406 g, 2.0 mmol), 5-acetoxy isophthaloyl chloride (117) (0.522 g, 2.0 mmol), a catalytic amount of 1,4-diazabicyclo[2.2.2]octane, and a catalytic amount of potassium iodide in 20 mL of pyridine was brought to 50° C. while stirring under nitrogen. After 24 hours, butanediol (0.072 g, 0.8 mmol) diluted in 10 mL of pyridine was added to the reaction mixture using a syringe pump over 8 hours. The solution was then quenched in 200 mL of cold 1N hydrochloric acid. The polymer precipitate is collected by filtration, redissolved in tetrahydrofuran, and precipitated in 100 mL of cold 1N hydrochloric acid. The polymer is then collected by filtration and dried under high vacuum. The polymer was found to have a molecular weight of ˜12,000 g/mol by GPC. was brought to 50° C. was added to the reaction mixture over 8 hours The solution was then quenched in 200 mL of cold 1N hydrochloric acid The polymer precipitate is collected by filtration redissolved in tetrahydrofuran precipitated in 100 mL of cold 1N hydrochloric acid The polymer is then collected by filtration dried under high vacuum

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

Procedure: A solution of (E)-hex-3-ene-2,5-diol (122) (0.441 g, 3.8 mmol), isophthaloyl chloride (115) (0.812 g, 4.0 mmol), a catalytic amount of 1,4-diazabicyclo[2.2.2]octane, and a catalytic amount of potassium iodide in 20 mL of pyridine was brought to 50° C. while stirring under nitrogen. After 24 hours, butanediol (0.072 g, 0.8 mmol) diluted in 10 mL of pyridine was added to the reaction mixture using a syringe pump over 8 hours. The solution was then quenched in 200 mL of cold 1N hydrochloric acid. The polymer precipitate is collected by filtration, redissolved in tetrahydrofuran, and precipitated in cold 100 mL of cold 1N hydrochloric acid. The polymer is then collected by filtration and dried under high vacuum. The polymer was found to have a molecular weight of ˜12,000 g/mol by GPC. was brought to 50° C. was added to the reaction mixture over 8 hours The solution was then quenched in 200 mL of cold 1N hydrochloric acid The polymer precipitate is collected by filtration redissolved in tetrahydrofuran precipitated in cold 100 mL of cold 1N hydrochloric acid The polymer is then collected by filtration dried under high vacuum

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

Procedure: A solution of 2,5-dimethylhexane-2,5-diylbis(2-hydroxyacetate) (69) (0.997 g, 3.8 mmol), 5-acetoxy isophthaloyl chloride (117) (1.044 g, 4.0 mmol), a catalytic amount of 1,4-diazabicyclo[2.2.2]octane, and a catalytic amount of potassium iodide in 20 mL of pyridine was brought to 50° C. while stirring under nitrogen. After 24 hours, butanediol (0.072 g, 0.8 mmol) diluted in 10 mL of pyridine was added to the reaction mixture using a syringe pump over 8 hours. The solution was then quenched in 200 mL of cold 1N hydrochloric acid. The polymer precipitate is collected by filtration, redissolved in tetrahydrofuran, and precipitated in 100 mL of cold 1N hydrochloric acid. The polymer is then collected by filtration and dried under high vacuum. The polymer was found to have a molecular weight of ˜14,000 g/mol by GPC. was brought to 50° C. was added to the reaction mixture over 8 hours The solution was then quenched in 200 mL of cold 1N hydrochloric acid The polymer precipitate is collected by filtration redissolved in tetrahydrofuran precipitated in 100 mL of cold 1N hydrochloric acid The polymer is then collected by filtration dried under high vacuum

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

Procedure: A solution of 2,5-dimethylhexane-2,5-diyl bis(2-hydroxyacetate) (69) (0.997 g, 3.8 mmol), isophthaloyl chloride (115) (0.406 g, 2.0 mmol), 5-acetoxy isophthaloyl chloride (117) (0.522 g, 2.0 mmol), a catalytic amount of 1,4-diazabicyclo[2.2.2]octane, and a catalytic amount of potassium iodide in 20 mL of pyridine was brought to 50° C. while stirring under nitrogen. After 24 hours, butanediol (0.072 g, 0.8 mmol) diluted in 10 mL of pyridine was added to the reaction mixture using a syringe pump over 8 hours. The solution was then quenched in 200 mL of cold 1N hydrochloric acid. The polymer precipitate is collected by filtration, redissolved in tetrahydrofuran, and precipitated in 100 mL of cold 1N hydrochloric acid. The polymer is then collected by filtration and dried under high vacuum. The polymer was found to have a molecular weight of ˜14,000 g/mol by GPC. was brought to 50° C. was added to the reaction mixture over 8 hours The solution was then quenched in 200 mL of cold 1N hydrochloric acid The polymer precipitate is collected by filtration redissolved in tetrahydrofuran precipitated in 100 mL of cold 1N hydrochloric acid The polymer is then collected by filtration dried under high vacuum

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

Procedure: A solution of 2,5-dimethylhexane-2,5-diyl bis(2-hydroxyacetate) (69) (0.997 g, 3.8 mmol), isophthaloyl chloride (115) (0.812 g, 4.0 mmol), a catalytic amount of 1,4-diazabicyclo[2.2.2]octane, and a catalytic amount of potassium iodide in 20 mL of pyridine was brought to 50° C. while stirring under nitrogen. After 24 hours, butanediol (0.072 g, 0.8 mmol) diluted in 10 mL of pyridine was added to the reaction mixture using a syringe pump over 8 hours. The solution was then quenched in 200 mL of cold 1N hydrochloric acid. The polymer precipitate is collected by filtration, redissolved in tetrahydrofuran, and precipitated in 100 mL of cold 1N hydrochloric acid. The polymer is then collected by filtration and dried under high vacuum. The polymer was found to have a molecular weight of ˜14,000 g/mol by GPC. was brought to 50° C. was added to the reaction mixture over 8 hours The solution was then quenched in 200 mL of cold 1N hydrochloric acid The polymer precipitate is collected by filtration redissolved in tetrahydrofuran precipitated in 100 mL of cold 1N hydrochloric acid The polymer is then collected by filtration dried under high vacuum

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

Procedure: A solution of 40 mM of 6 APA and 200 mM of phenylacetic acid in 50% butanediol/50% acetate 50 mM is prepared at a pH of 6.5. The column is thermostatized at 4° C. The rest of the conditions are as in example 1. In these conditions, the degree of conversion of 6 APA to penicillin G is higher than 85%. at 4° C

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

Procedure: Butanediol (40 ml; 40.68 g; 0.452 mol) was stirred in a 100 ml round bottomed flask, and treated portionwise with potassium butoxide (17.60 g; 0.144 mol). The initial reaction was exothermic. The reaction mixture was stirred for 1.5 hours at room temperature. The resulting cloudy solution was then treated with chloromethyl styrene (20.00 g; 0.131 mol). The styrene formed an upper, pale green layer, (the colouration being due to the presence of inhibitor), whose color darkened considerably on the addition of 18-crown-6 (0.49 g; 1.86×10-3 mole). The flask was stoppered, protected from light, and stirred for 28 hours at room temperature. The mixture was then poured into water (120 ml) and extracted with dichloromethane (4×50 ml). The combined organic extracts were dried (MgSO4) and evaporated to give viscous yellow oil (932.7 g). This oil was distilled from a small amount of CuCl to give a product showing some impurities on TLC. The oil was then chromatographed on silica gel, initially eluting with dichloromethane/petrol (1:1) to remove the impurities. The product was then eluted off the column with ethyl acetate/petrol (1:1). Evaporation of the solvent gave a colourless oil, which was distilled to give the desired styrylbutyl alcohol as a colourless oil b.pt. 150°-152°/0.4 mbar. Yield 18.70 g; 69.2%. The initial reaction