2-sulfanylidene-1,3-diazinane-4,6-dione

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

Procedure: 2-thiobarbituric acid (14.4 g) was suspended in pyridine and 4-fluorophenyl isocyanate (13.7 g) was added thereto. The reaction mixture was maintained at 90° C. for one hour, and thereafter left overnight at room temperature. The solids formed were collected, washed with pyridine, re-suspended in ethanol, and again collected and dried. A pale pink powder product was thereby obtained, mp >250° C. (dec.), NMR (DMSO) 7.0-7.7δ (multiplet, integral 4); 10.7-11.4δ (overlapping broad singlets, combined integral 4). MS, M/e 281 (Calc., 281). The solids formed were collected washed with pyridine again collected dried A pale pink powder product was thereby obtained

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

Procedure: To a solution of 5-hydroxymethyl-salicylaldehyde (5.8 g.) and 2-thiobarbituric acid (6 g.) in n-butanol (100 ml.) add methanesulfonic acid (10 ml.) and heat to reflux, with stirring, for 1 hour. Cool, filter and wash the solid with ethanol and ether to yield 7-n-butyloxymethyl-(1H,3H,5H)-(1)-benzopyrano-(2,3-d)-pyrimidine-4-one-2-thione. heat to reflux Cool filter wash the solid with ethanol and ether

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

Procedure: To n-butanol (100 ml.) add 5-cyano-salicylaldehyde (6 g.), 2-thiobarbituric acid (6 g.) and methanesulfonic acid (10 ml.) With stirring, heat the mixture to reflux for 11/2 hours. Cool, filter, and wash the solid with isopropanol and ether to yield 7-cyano-(1H,3H,5H)-(1)-benzopyrano-(2,3-d)-pyrimidine-4-one-2-thione. heat the mixture to reflux for 11/2 hours Cool filter wash the solid with isopropanol and ether

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of thiobarbituric acid (15 g) in 50% ethanol (180 ml) are added a solution of NaOH (5.1 g) in 50% ethanol (75 ml) and p-methoxybenzyl chloride (18.7 g). The mixture is heated under stirring for 60' at 60° C.; then it is cooled and the solid is filtered by suction, washed with water; then dried over CaCl2, yielding 15 g of 2-p-methoxy-benzylthio-4,6-dihydroxypyrimidine. The mixture is heated then it is cooled the solid is filtered by suction washed with water then dried over CaCl2

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of thiobarbituric acid (15 g) in 50% ethanol (180 ml) are added a solution of NaOH (5.1 g) in 50% ethanol (75 ml) and p-methoxybenzyl chloride (18.7 g). The mixture is heated under stirring for 60' at 60° C.; then it is cooled and the solid is filtered by suction, washed with water; then dried over CaCl2, yielding 15 g of 2-p-methoxy-benzylthio-4,6-dihydroxypyrimidine. The mixture is heated then it is cooled the solid is filtered by suction washed with water then dried over CaCl2

Conditions: temp:32.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Thiobarbituric acid (100 g) was added to the water (250 ml) under stirring, followed by the addition of a solution of sodium hydroxide pellets or flakes (63.13 g) in water (147.35 ml) over a period of 15 to 20 minutes at 20-25° C. The resulting mass was stirred for 40 minutes at 20-25° C., followed by the addition of water (200 ml). The reaction temperature was raised to 30-35° C., followed by addition of methanol (200 ml), propyl iodide (123.36 g) and tetrabutyl ammonium bromide (1.0 g) under stirring at 30-35° C. The resulting reaction mixture was stirred for 24 hours at 30-35° C. The reaction was monitored by thin layer chromatography. After completion of reaction, the pH of the reaction mixture was adjusted to less than 2.0 by the addition of dilute hydrochloric acid (prepared by mixing of 60 ml of concentrated hydrochloric acid with 140 ml of water). The resulting slurry was stirred for 15 hours, and the product was isolated by filtration and washed successively with water (4×200 ml) and cyclohexane (200 ml). The wet product was dried under reduced pressure at 40-45° C. to produce 85 g of 2-propylthio-pyrimidine-4,6-diol as a white powder (Yield: 65.7%; Purity by HPLC: 90.96 area-%). The resulting mass was stirred for 40 minutes at 20-25° C. under stirring at 30-35° C The resulting reaction mixture was stirred for 24 hours at 30-35° C After completion of reaction The resulting slurry was stirred for 15 hours the product was isolated by filtration washed successively with water (4×200 ml) and cyclohexane (200 ml) The wet product was dried under reduced pressure at 40-45° C.

Conditions: temp:32.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Thiobarbituric acid (100 g) was added to water (250 ml) under stirring. A solution of sodium hydroxide pellets or flakes (63.13 g) in water (147.35 ml) was added to the resulting mixture over a period of 15 to 20 minutes at 20-25° C. The resulting mass was stirred for 40 minutes at 20-25° C., followed by the addition of water (200 ml). The reaction temperature was raised to 30-35° C., followed by the addition of methanol (200 ml) and propyl iodide (123.36 g) under stirring at 30-35° C. The resulting reaction mixture was stirred for 30 hours at 30-35° C. The reaction was monitored by thin layer chromatography. After completion of reaction, the pH of the reaction mixture was then adjusted to less than 2.0 by the addition of dilute hydrochloric acid (prepared by mixing of 60 ml of concentrated hydrochloric acid with 140 ml of water). The resulting slurry was stirred for 15 hours and the product was isolated by filtration and washed successively with water (4×200 ml). The wet cake was slurried in cyclohexane (500 ml) at boiling temperature for 30 minutes, followed by cooling to 25-30° C. The product was isolated by filtration and washed with cyclohexane (200 ml). The wet product was dried under reduced pressure at 40-45° C. to produce 80 g of 2-propylthio-pyrimidine-4,6-diol as a white powder (Yield: 61.9%). The resulting mass was stirred for 40 minutes at 20-25° C. under stirring at 30-35° C The resulting reaction mixture was stirred for 30 hours at 30-35° C After completion of reaction The resulting slurry was stirred for 15 hours the product was isolated by filtration washed successively with water (4×200 ml) for 30 minutes by cooling to 25-30° C The product was isolated by filtration washed with cyclohexane (200 ml) The wet product was dried under reduced pressure at 40-45° C.

Conditions: temp:32.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Thiobarbituric acid (100 g) was added to water (250 ml) under stirring. A solution of sodium hydroxide pellets or flakes (63.13 g) in water (147.35 ml) was added to the resulting mixture over a period of 15 to 20 minutes at 20-25° C. The resulting mass was stirred for 40 minutes at 20-25° C., followed by the addition of water (200 ml). The reaction temperature was raised to 30-35° C., followed by the addition of methanol (200 ml) and propyl iodide (123.36 g) under stirring at 30-35° C. The resulting reaction mixture was stirred for 30 hours at 30-35° C. The reaction was monitored by thin layer chromatography. After completion of reaction, the pH of the reaction mixture was then adjusted to less than 2.0 by the addition of dilute hydrochloric acid (prepared by mixing of 60 ml of concentrated hydrochloric acid with 140 ml of water). The resulting slurry was stirred for 15 hours and the product was isolated by filtration and washed successively with water (4×200 ml). The wet cake was slurried in cyclohexane (500 ml) at boiling temperature for 30 minutes, followed by cooling to 25-30° C. The product was isolated by filtration and washed with cyclohexane (200 ml). The wet product was dried under reduced pressure at 40-45° C. to produce 80 g of 2-propylthio-pyrimidine-4,6-diol as a white powder (Yield: 61.9%). The resulting mass was stirred for 40 minutes at 20-25° C. under stirring at 30-35° C The resulting reaction mixture was stirred for 30 hours at 30-35° C After completion of reaction The resulting slurry was stirred for 15 hours the product was isolated by filtration washed successively with water (4×200 ml) for 30 minutes by cooling to 25-30° C The product was isolated by filtration washed with cyclohexane (200 ml) The wet product was dried under reduced pressure at 40-45° C.

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

Procedure: Water (670 ml) was added to 2-thiobarbituric acid (200 g). The resulting mixture was stirred and sodium hydroxide (126.3 g) was added in portions. The mixture was stirred for 40 min. then diluted with water. 1-Methyl-2-pyrrolidinone (400 ml) and 1-iodopropane (140.9 ml) were then added. The resulting slurry was stirred at 20° C. for 22 h. The pH of the mixture was then adjusted to 6.5 by addition of 1M HCl (600 ml) over 30 min, then to pH 2.5 by the addition of 6 M HCl (180 ml) over a further 30 min. The resulting slurry was stirred for 18 h and the product was isolated by filtration and washed successively with water (4×100 ml), ethanol (200 mm) and water (2×200 ml). The product was dried under reduced pressure overnight at 50° C. to yield the title product as a white powder (185 g). The mixture was stirred for 40 min. The resulting slurry was stirred at 20° C. for 22 h The resulting slurry was stirred for 18 h the product was isolated by filtration washed successively with water (4×100 ml), ethanol (200 mm) and water (2×200 ml) The product was dried under reduced pressure overnight at 50° C.

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

Procedure: Water (670 ml) was added to 2-thiobarbituric acid (200 g). The resulting mixture was stirred and sodium hydroxide (126.3 g) was added in portions. The mixture was stirred for 40 min. then diluted with water. 1-Methyl-2-pyrrolidinone (400 ml) and 1-iodopropane (140.9 ml) were then added. The resulting slurry was stirred at 20° C. for 22 h. The pH of the mixture was then adjusted to 6.5 by addition of 1M HCl (600 ml) over 30 min, then to pH 2.5 by the addition of 6 M HCl (180 ml) over a further 30 min. The resulting slurry was stirred for 18 h and the product was isolated by filtration and washed successively with water (4×100 ml), ethanol (200 mm) and water (2×200 ml). The product was dried under reduced pressure overnight at 50° C. to yield the title product as a white powder (185 g). The mixture was stirred for 40 min. The resulting slurry was stirred at 20° C. for 22 h The resulting slurry was stirred for 18 h the product was isolated by filtration washed successively with water (4×100 ml), ethanol (200 mm) and water (2×200 ml) The product was dried under reduced pressure overnight at 50° C.

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

Procedure: Water (670 ml) was added to 2-thiobarbituric acid (200 g). The resulting mixture was stirred and sodium hydroxide (126.3 g) was added in portions. The mixture was stirred for 40 mm. then diluted with water. 1-Methyl-2-pyrrolidinone (400 ml) and 1-iodopropane (140.9 ml) were then added. The resulting slurry was stirred at 20° C. for 22 h. The pH of the mixture was then adjusted to 6.5 by addition of 1M HCl (600 ml) over 30 min, then to pH 2.5 by the addition of 6 M HCl (180 ml) over a further 30 min. The resulting slurry was stirred for 18 h and the product was isolated by filtration and washed successively with water (4×100 ml), ethanol (200 ml) and water (2×200 ml). The product was dried under reduced pressure overnight at 50° C. to yield the title product as a white powder (185 g). The mixture was stirred for 40 mm The resulting slurry was stirred at 20° C. for 22 h The resulting slurry was stirred for 18 h the product was isolated by filtration washed successively with water (4×100 ml), ethanol (200 ml) and water (2×200 ml) The product was dried under reduced pressure overnight at 50° C.

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

Procedure: The first step of synthesis of fused ring bridge, ring locked dyes according to the invention is the Birch reduction of 1,3-dimethoxybenzene, 2,7-dimethoxynaphthalene or 2,8-dimethoxyanthracene using ethanol, liquid ammonia and sodium. The reduced compounds are the starting materials for the synthesis of the dyes, as shown below. ##STR15## The Birch reduction products of 1,3-dimethoxybenzene and of 2,7-dimethoxynaphthalene each react with thiobarbituric acid to form the conjugated methoxy-thiobarbituric acid dyes as shown in FIG. 13. For this reaction, no solvent is used. The reactants were melted at 145° C. for 15 min. Methanol condensing at the walls of the flask showed successful reaction. Purification was carried out by simple filtration over a short column of SiO2 with CH2Cl2. Yields were typically around 60%. The first step of synthesis of fused ring bridge, ring for the synthesis of the dyes