Bismuth

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

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

Conditions: temp:22.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 86.6 g quantity of 6,6-dibromo-2,2-dimethylpenam-3-carboxylic acid 1-oxide diphenylmethyl ester (Compound 1) [compound of the formula (1) wherein X═Y═Br, R=diphenylmethyl, n=1] was dissolved in 300 mL of dichloromethane. To the solution was added 36 mL of methanol with stirring and then added a suspension of 1.05 g of metal bismuth in 112 mL of 20% aqueous solution of sodium chloride. While maintaining at 20 to 25° C., to the mixture was added 10 g of aluminum powder, each 1 g, at intervals of 10 minutes, thereafter the mixture was refluxed with heating. After 23.5 hours, the reaction mixture was cooled to room temperature, an organic layer was separated and washed with diluted hydrochloric acid and 5% aqueous solution of sodium chloride. The organic layer was concentrated to give 2,2-dimethylpenam-3-carboxylic acid 1-oxide diphenylmethyl ester (Compound 2) [compound of the formula (2) wherein R=diphenylmethyl, n=1]. added each 1 g, at intervals of 10 minutes, thereafter the mixture was refluxed with heating the reaction mixture was cooled to room temperature an organic layer was separated washed with diluted hydrochloric acid and 5% aqueous solution of sodium chloride The organic layer was concentrated

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

Procedure: A palladium-bismuth catalyst is disclosed in the specification of Japanese Patent Laid-Open No. 163340/1982 which relates to a process for producing 2-keto-L-gulonic acid. In this process, a hydroxyl group of L-sorbose (ketose) is oxidized with oxygen in the presence of a catalyst containing palladium and bismuth to obtain 2-keto-L-gulonic acid in a yield of 85%. The process of the present invention is characterized in that not the hydroxyl group but an aldehydo group of glucose (aldose) is oxidized to obtain gluconic acid. The process of the present invention is different from the above-mentioned process in the functional group to be oxidized and the intended product. It has been unknown in the prior art that the palladium-bismuth catalyst selectively oxidizes only the aldehydo group of glucose as an aldose, leaving the hydroxyl group non-oxidized.

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

Procedure: A first process consists in reacting γ-resorcylic acid with a bismuth compound; the said acid is dispersed in water and the temperature of the mixture is raised to a temperature of between approximately 40° C. and approximately 60° C., preferably approximately 50° C., and then the bismuth compound is added and the temperature is raised, with stirring, to a temperature of between approximately 70° C. and approximately 90° C., preferably approximately 80° C., allowing the reaction to continue, advantageously for between 2 and 15 hours, preferably approximately 5 hours. The suspension is filtered off, washed and dried; the product obtained corresponds to a γ-resorcylate containing one atom of bismuth per molecule of acid. the temperature is raised the reaction The suspension is filtered off washed dried

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

Procedure: A hydroalcoholic mixture consisting of 600 ml of distilled water and 600 ml of ethanol is made up in the same reactor as in Example 1 and then 46.24 g of β-resorcylic acid, that is 0.3 moles are introduced into it. The mixture is heated to 50° C. with stirring. The acid dissolves completely. 69.9 g of bismuth oxide, that is 0.3 gram-atoms of bismuth, are then introduced, as according to Example 1. The suspension is heated to 80° C. and kept stirred at this temperature for approximately 5 hours, after which the suspension is treated as according to Example 1: filtration followed by vacuum-drying. are introduced into it The acid dissolves completely are then introduced The suspension is heated to 80° C. kept stirred at this temperature for approximately 5 hours after which the suspension is treated filtration by vacuum-drying

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

Procedure: A 3-liter thermostatic reactor fitted with a pneumatic stirrer, a bottom valve, temperature probes, a reflux condenser and a heating system is employed for this synthesis. 900 ml of distilled water and 15.4 g of γ-resorcylic acid, that is 0.1 mole of acid, are placed in the reactor. The heterogeneous mixture is heated to 50° C. with stirring and then 31 g of bismuth oxide, that is 0.1 gram-atom of bismuth, are added portionwise over approximately 15 minutes. The suspension thus obtained is heated to 80° C. After approximately 30 minutes approximately 1500 ml of distilled water are added to permit better stirring of the suspension and the suspension is then left stirred for approximately 5 hours at 80° C. The mixture is then filtered hot and the cake obtained is then washed with 500 ml of ethanol. The product is next vacuum-dried at 60° C. over calcium chloride. At the end of reaction 24 g of bismuth γ-resorcylate are recovered. A 3-liter thermostatic reactor fitted with a pneumatic stirrer, a bottom valve temperature probes, a reflux condenser and a heating system is employed for this synthesis are added portionwise over approximately 15 minutes The suspension thus obtained is heated to 80° C to permit better stirring of the suspension the suspension is then left stirred for approximately 5 hours at 80° C The mixture is then filtered hot the cake obtained is then washed with 500 ml of ethanol The product is next vacuum-dried at 60° C. over calcium chloride At the end of reaction 24 g of bismuth γ-resorcylate are recovered

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

Procedure: In this process the β-resorcylic acid is dissolved in the hydroalcoholic medium with an increase in the temperature to a temperature of between approximately 40° C. and approximately 60° C., preferably approximately 50° C., and then a bismuth compound is added with stirring; the temperature is raised to a temperature of between approximately 70° C. and approximately 90° C., preferably approximately 80° C., allowing the reaction to continue, advantageously for between 2 and 15 hours, preferably approximately 5 hours. The suspension is filtered off, washed and dried. The product obtained corresponds to a bismuth β-resorcylate containing two bismuth atoms per molecule of acid. the temperature is raised to a temperature of between approximately 70° C. and approximately 90° C., preferably approximately 80° C. the reaction The suspension is filtered off washed dried

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

Procedure: 4.6 g of 2-n-butyl-5-hydroxymethylimidazole, 4.6 g of dodecane as internal GC standard, 0.6 g of 5 percent platinum and 5 percent bismuth on activated carbon (comprising 61.3 percent water), 42 g of isobutyl methyl ketone and 7.5 g of 1.6 percent strength NaOH solution were heated to about 80° C. with stirring. At 80° C., 3.6 liters (STP) of air/hour was introduced into the solution until the absorption of oxygen was complete (350 min!). The reaction mixture was filtered. The filtrate was transferred to a separating funnel, the H2O phase was separated off, the organic phase was concentrated and cooled, and the product crystallized out and was filtered off. The reaction was monitored using GC analysis (internal standard). The reaction yield was 90.0 percent (0.3 percent of starting material). (350 min!) The reaction mixture was filtered The filtrate was transferred to a separating funnel the H2O phase was separated off the organic phase was concentrated cooled the product crystallized out was filtered off The reaction yield was 90.0 percent (0.3 percent of starting material)

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

Procedure: 4.4 g of 2-n-butyl-5-hydroxymethylimidazole (crude starting material, 90.4 percent), 0.6 g of 5 percent platinum and 5 percent bismuth on activated carbon (comprising 61.3 percent water), 25.6 ml of 1N NaOH solution and 5 ml of methanol were heated to about 60° C. with stirring. At 60° to 64° C., 6.8 g of 15 percent strength aqueous H2O2 solution was added dropwise over the course of 45 min. The reaction mixture was then allowed to react for 15 min and then filtered. The pH of the filtrate was adjusted from 13.0 to 9.0 using 20 percent H2SO4, as a result of which a yellow suspension formed. This was cooled, and the crude product was able to be filtered off and/or extracted with methylene chloride. The reaction was monitored by GC analysis. The reaction yield was 94.5 percent (3.5 percent of starting material). to react for 15 min filtered as a result of which a yellow suspension formed This was cooled to be filtered off extracted with methylene chloride The reaction yield was 94.5 percent (3.5 percent of starting material)

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

Procedure: 4.0 g of 2-n-butyl-5-hydroxymethylimidazole, 0.6 g of 5 percent platinum and 5 percent bismuth on activated carbon (comprising 61.3 percent water), and 25.6 ml of 1N NaOH solution were heated to about 60° C. with stirring. At 60° to 64° C., 6.8 g of 15 percent strength aqueous H2O2 solution was added dropwise over the course of 45 min. The reaction mixture was then allowed to react for 15 min and then filtered off. The pH of the filtrate was adjusted from 13.2 to 9.0 using 20 percent H2SO4, as a result of which a yellow suspension formed. This was cooled, and the crude product was able to be filtered off and/or extracted with methylene chloride. The reaction was monitored by GC analysis. The reaction yield was 98.2 percent (1.8 percent of starting material). to react for 15 min filtered off as a result of which a yellow suspension formed This was cooled to be filtered off extracted with methylene chloride The reaction yield was 98.2 percent (1.8 percent of starting material)

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

Procedure: 2.0 g of 2-n-butyl-5-hydroxymethylimidazole, 0.3 g of 5 percent platinum and 5 percent bismuth on activated carbon (comprising 61.3 percent water), 13 ml of 1 N NaOH solution and 7 g of H2O were heated to about 60° C. with stirring. At 60° to 64° C., 3.4 g of 15 percent strength aqueous H2O2 solution was added dropwise over the course of 45 min. The reaction mixture was then allowed to react for 15 min and then filtered. The pH of the filtrate was adjusted from 13.4 to 9.0 using 20 percent H2SO4, as a result of which a pale yellow suspension formed. This was cooled, and the crude product was able to be filtered off and/or extracted with methylene chloride. The reaction was monitored by GC analysis. The reaction yield was 100 percent (0 percent of starting material). to react for 15 min filtered as a result of which a pale yellow suspension formed This was cooled to be filtered off extracted with methylene chloride The reaction yield was 100 percent (0 percent of starting material)