oxaldehyde

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:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-methylbenzene-1,2-diamine (50.0 g, 0.41 mol) in isopropanol (300 mL) was added a solution of glyoxal (40% in water, 65.3 g, 0.45 mol) at room temperature. The reaction mixture was heated at 80° C. for 2 hours and evaporated under vacuum to give 6-methylquinoxaline (55 g, 93%), which was used directly in the next step. 1H NMR (300 MHz, CDCl3) δ 8.77 (dd, J=1.5, 7.2 Hz, 2H), 7.99 (d, J=8.7 Hz, 1H), 7.87 (s, 1H), 7.60 (dd, J=1.5, 8.4 Hz, 1H), 2.59 (s, 3H). evaporated under vacuum

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

Procedure: A solution of 0.50 g (1.3 mmol) of 1-ethyl-4-(2-chloro-3-(2-hydroxyethylamino)-4-methylsulfonylbenzoyl)-5-hydroxypyrazole in 20 mL of toluene was heated to 90° C. and treated with 2 mL of 40 percent aqueous glyoxal solution with stirring. The progress of the reaction was monitored by HPLC analysis and additional aliquots of 40 percent aqueous glyoxal solution were added every few hours until the starting material was consumed. After 24 hours, the reaction was complete and the dark solution was decanted from a gummy residue. The residue was extracted with several portions of hot toluene and the organic solutions were combined. The volatiles were removed by evaporation under reduced pressure and the resulting residue was purified by adding a small amount of diethyl ether and collecting the solids present by filtration. More solids were obtained when the diethyl ether solution was concentrated by evaporation. These solids were collected by filtration as well. The solids were combined to obtain 0.39 g (71 percent of theory) of the title compound as a tan powder melting at 198°-202° C. were added every few hours until the starting material was consumed the dark solution was decanted from a gummy residue The residue was extracted with several portions of hot toluene The volatiles were removed by evaporation under reduced pressure the resulting residue was purified by adding a small amount of diethyl ether collecting the solids present by filtration More solids were obtained when the diethyl ether solution was concentrated by evaporation These solids were collected by filtration as well

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

Procedure: Approximately 53 grams (0.4 mole) tolyltriazole, 140 grams (0.4 mole) N-oleyl-1,3-diaminopropane, 100 ml ethanol, and 100 ml toluene were charged to a 1 liter flask equipped with an agitator, Dean-Stark apparatus, and dropping funnel. This mixture was stirred to a homogeneous mixture. Glyoxal (29 grams, 0.2 mole, 40% in water) was added dropwise and then stirred at room temperature for 12 hours. Water was then azeotropically removed by heating to reflux temperatures of approximately 100°-120° C. After cooling to less than 60° C., 112 grams (0.4 mole) oleic acid was added slowly. The reaction mixture was stirred at 60° C. for 1 hour. The orange product (310 grams) was isolated by filtration and removal of solvent under reduced pressure. equipped with an agitator, Dean-Stark apparatus stirred at room temperature for 12 hours Water was then azeotropically removed by heating to reflux temperatures of approximately 100°-120° C After cooling to less than 60° C. The reaction mixture was stirred at 60° C. for 1 hour

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

Procedure: Approximately 53 grams (0.4 mole) tolyltriazole, 111 grams (0.4 mole) oleyl amine, 100 ml ethanol, and 100 ml toluene were charged to a 1 liter flask equipped with an agitator, Dean-Stark apparatus, and dropping funnel. This mixture was stirred to a homogeneous mixture. Glyoxal (29 grams, 0.2 mole, 40% in water) was added dropwise and then stirred at room temperature for 12 hours. Water was then azeotropically removed by heating to reflux temperatures of approximately 100°-120° C. While maintaining a temperature of less than or equal to 60° C., 56 grams (0.2 mole) oleic acid was added slowly. The reaction mixture was stirred at 60° C. for 1 hour. The orange product (243 grams) was isolated by filtration and removal of solvent under reduced pressure. equipped with an agitator, Dean-Stark apparatus stirred at room temperature for 12 hours Water was then azeotropically removed by heating to reflux temperatures of approximately 100°-120° C was added slowly The reaction mixture was stirred at 60° C. for 1 hour

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Approximately 66.6 grams (0.5 mole) tolyltriazole, 175 grams (0.5 mole) N-oleyl-1,3-diaminopropane (Armak Chemical Co.), 100 ml ethanol, and 100 ml toluene were charged to a 1 liter flask equipped with an agitator, Dean-Stark apparatus, and dropping funnel. This mixture was stirred to a homogeneous mixture. Glyoxal (36.3 grams, 0.25 mole, 40% in water) was added dropwise and then stirred at room temperature for 12 hours. Water was then azeotropically removed by heating to 150° C. The orange product (237 grams) was isolated by filtration and removal of solvent under reduced pressure. equipped with an agitator, Dean-Stark apparatus stirred at room temperature for 12 hours Water was then azeotropically removed

Conditions: temp:115.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Approximately 80 grams (0.6 mole) tolyltriazole (Sherwin Williams Co.), 167 grams (0.6 mole) oleyl amine (Armak-O, Armak Chemical Co.), 100 ml ethanol, and 100 ml toluene were charged to a 1 liter flask equipped with an agitator, Dean-Stark apparatus and dropping funnel. This mixture was stirred to a homogeneous mixture. Glyoxal (43.5 grams, 0.3 mole, 40% in water) was added dropwise and then stirred at room temperature for 12 hours. Water was then azeotropically removed by heating to 115° C. The dark brown product (261 grams) was isolated by filtration and removal of solvent under reduced pressure. equipped with an agitator, Dean-Stark apparatus stirred at room temperature for 12 hours Water was then azeotropically removed

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

Procedure: A solution of 87.2 g of 1,10-diamino-4,7-diazadecane in 500 ml of toluene was admixed with 72.3 g of a 40% aqueous glyoxal solution, and the mixture was refluxed, with a water separator fitted, for 3 hours. When the solution was cooled, a solid precipitated out which was filtered off with suction, washed three times with 50 ml of toluene each time and dried under reduced pressure. This gave 34.9 g of pale yellow needles. separator fitted, for 3 hours When the solution was cooled a solid precipitated out which was filtered off with suction washed three times with 50 ml of toluene each time dried under reduced pressure

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

Procedure: 1,4,7,10-tetraazadodecane (1.1.4) trihydrobromide in acetonitrile with potassium carbonate was reacted with glyoxal to form 1,4,7,10-tetraazatetracyclo-[5,5,2,04,13,010,14 ] tetradecane (1.1.23). Following separation the pure product was obtained by low pressure distillation. This was dissolved in acetonitrile and benzylbromide was added to form 1,7-dibenzylonium-1,4,7,10-tetraazatetracyclo[5,5,2,04,13,010,14 ] tetradecane (1.1.24). Following recrystallization from ethanol this was reacted with sodium borohydride. HCl was added, followed by water and NaOH, and the product extracted with chloroform. Following evaporation of solvent the solids were dissolved in methanol and HBr was added to obtain 1,7-dibenzyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane (1.1.25) as the hydrobromide salt. This was dissolved in water and reduced using H2 and a Pd-C catalyst to remove the benzyl groups. Purification of the title compound was by crystallization of the hydrobromide salt. The base form was obtained by low pressure distillation following addition of base. ##STR9## 1.1.26 1,4,7,10,13-Pentaazabicyclo [8.5.2]heptadecane.

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of N-(2-hydroxyethyl)laurylimidazoline (5 g, 18.7 mmol) and sodium hydroxide pellets (40 mg) in water (1.06 g) is heated at 80° C. for 1 hour. A mixture of glyoxal at a concentration of 40% in water (2.7 g, 18.7 mmol) and 1-propanol (5 g) is then added and the residual solution is heated for 6 hours at 80° C. An assay by capillary electrophoresis indicates a yield of 85% of N-lauroyl-N'-(2-hydroxyethyl)-N'-(carboxymethyl)ethylene-diamine.