3-(dibutylamino)phenol

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

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

Procedure: Firstly, the starting compound N,N-dibutyl-4-amino-2-hydroxy-benzaldehyde had to be prepared by Vilsmeyer formylation of N,N-dibutyl-3-amino-phenol. The Vilsmeyer reagent was prepared by slow addition of 4.7 ml (0.0497 mol) of phosphorus oxychloride to 15 ml (0.189 mol) of N,N-dimethyl formamide with stirring for 15 minutes at room temperature. Stirring was continued for 30 more minutes before this Vilsmeyer reagent was used. 11 g (0.497 mol) N,N-dibutyl-3-amino-phenol, prepared by alkylation of 3-aminophenol after the procedure described in EP 0356173 was dissolved in 13 ml N,N-dimethyl formamide. This solution was added dropwise at room temperature to the Vilsmeyer reagent described above. The solution was stirred for 3 h, heated to 50° C. for 10 minutes. The solution was cooled to room temperature and stirred for another 2 h. Then, the reaction mixture was poured onto 70 g ice and stirred for 1 h. The aequous layer was extracted three times with 100 ml chloroform. The combined organic layers were evaporated in vacuo. The raw product was purified by column chromatography (450 g silicagel, eluent hexane/ethyl acetate 15:1, vol. ratio). 3.2 g (26%) N,N-Dibutylamino-2-hydroxy-benzaldehyde was obtained as an orange oily compound. Stirring This solution was added dropwise at room temperature to the Vilsmeyer reagent The solution was stirred for 3 h heated to 50° C. for 10 minutes The solution was cooled to room temperature stirred for another 2 h stirred for 1 h The aequous layer was extracted three times with 100 ml chloroform The combined organic layers were evaporated in vacuo The raw product was purified by column chromatography (450 g silicagel, eluent hexane/ethyl acetate 15:1, vol. ratio)

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: One part by weight of 1-amino-2-chloro-4-hydroxyanthraquinone, 10 parts by weight of 1,3-dimethyl-2-imidazolidinone, 1.0 part by weight of potassium carbonate and 1.0 part by weight of N,N-di-n-butyl-m-aminophenol were mixed at room temperature, and then heated to 140° C. While this temperature was maintained, the reaction was conducted for 3 hours. The reaction mixture was then cooled to room temperature, charged into 90 parts by weight of water, and extracted with toluene. After the solution was separated, toluene was distilled off under reduced pressure, and the residue was purified through silica gel column chromatography to obtain an anthraquinone compound as coloring matter No. 9 (yield 90%) in Table 1. While this temperature was maintained The reaction mixture was then cooled to room temperature extracted with toluene After the solution was separated toluene was distilled off under reduced pressure the residue was purified through silica gel column chromatography

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

Procedure: Firstly, the starting compound N,N-dibutyl-4-amino-2-hydroxy-benzaldehyde had to be prepared by Vilsmeyer formylation of N,N-dibutyl-3-amino-phenol. The Vilsmeyer reagent was prepared by slow addition of 4.7 ml (0.0497 mol) of phosphorus oxychloride to 15 ml (0.189 mol) of N,N-dimethyl formamide with stirring for 15 minutes at room temperature. Stirring was continued for 30 more minutes before this Vilsmeyer reagent was used. 11 g (0.497 mol) N,N-dibutyl-3-amino-phenol, prepared by alkylation of 3-aminophenol after the procedure described in EP 0356173 was dissolved in 13 ml N,N-dimethyl formamide. This solution was added dropwise at room temperature to the Vilsmeyer reagent described above. The solution was stirred for 3 h, heated to 50° C. for 10 minutes. The solution was cooled to room temperature and stirred for another 2 h. Then, the reaction mixture was poured onto 70 g ice and stirred for 1 h. The aequous layer was extracted three times with 100 ml chloroform. The combined organic layers were evaporated in vacuo. The raw product was purified by column chromatography (450 g silicagel, eluent hexane/ethyl acetate 15:1, vol. ratio). 3.2 g (26%) N,N-Dibutylamino-2-hydroxy-benzaldehyde was obtained as an orange oily compound. Stirring This solution was added dropwise at room temperature to the Vilsmeyer reagent The solution was stirred for 3 h heated to 50° C. for 10 minutes The solution was cooled to room temperature stirred for another 2 h stirred for 1 h The aequous layer was extracted three times with 100 ml chloroform The combined organic layers were evaporated in vacuo The raw product was purified by column chromatography (450 g silicagel, eluent hexane/ethyl acetate 15:1, vol. ratio)

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

Procedure: Firstly, the starting compound N,N-dibutyl-4-amino-2-hydroxy-benzaldehyde had to be prepared by Vilsmeyer formylation of N,N-dibutyl-3-amino-phenol. The Vilsmeyer reagent was prepared by slow addition of 4.7 ml (0.0497 mol) of phosphorus oxychloride to 15 ml (0.189 mol) of N,N-dimethyl formamide with stirring for 15 minutes at room temperature. Stirring was continued for 30 more minutes before this Vilsmeyer reagent was used. 11 g (0.497 mol) N,N-dibutyl-3-amino-phenol, prepared by alkylation of 3-aminophenol after the procedure described in EP 0356173 was dissolved in 13 ml N,N-dimethyl formamide. This solution was added dropwise at room temperature to the Vilsmeyer reagent described above. The solution was stirred for 3 h, heated to 50° C. for 10 minutes. The solution was cooled to room temperature and stirred for another 2 h. Then, the reaction mixture was poured onto 70 g ice and stirred for 1 h. The aequous layer was extracted three times with 100 ml chloroform. The combined organic layers were evaporated in vacuo. The raw product was purified by column chromatography (450 g silicagel, eluent hexane/ethyl acetate 15:1, vol. ratio). 3.2 g (26%) N,N-Dibutylamino-2-hydroxy-benzaldehyde was obtained as an orange oily compound. Stirring This solution was added dropwise at room temperature to the Vilsmeyer reagent The solution was stirred for 3 h heated to 50° C. for 10 minutes The solution was cooled to room temperature stirred for another 2 h stirred for 1 h The aequous layer was extracted three times with 100 ml chloroform The combined organic layers were evaporated in vacuo The raw product was purified by column chromatography (450 g silicagel, eluent hexane/ethyl acetate 15:1, vol. ratio)

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: One part by weight of 1-amino-2-chloro-4-hydroxyanthraquinone, 10 parts by weight of 1,3-dimethyl-2-imidazolidinone, 1.0 part by weight of potassium carbonate and 1.0 part by weight of N,N-di-n-butyl-m-aminophenol were mixed at room temperature, and then heated to 140° C. While this temperature was maintained, the reaction was conducted for 3 hours. The reaction mixture was then cooled to room temperature, charged into 90 parts by weight of water, and extracted with toluene. After the solution was separated, toluene was distilled off under reduced pressure, and the residue was purified through silica gel column chromatography to obtain an anthraquinone compound as coloring matter No. 9 (yield 90%) in Table 1. While this temperature was maintained The reaction mixture was then cooled to room temperature extracted with toluene After the solution was separated toluene was distilled off under reduced pressure the residue was purified through silica gel column chromatography

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

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

Procedure: In 70 ml of 1-methyl-2-pyrrolidone were dissolved 10.0 g (45.18 mmol) of 3-(dibutylamino)phenol and 12.8 g (90.18 mmol) of methyl iodide. To this mixture was added 18.7 g (135.3 mmol) of anhydrous potassium carbonate and the mixture was stirred with heating at 60° C. for 6 hours. After the reaction mixture was poured into 350 ml of water, extraction with ethyl acetate, washing with a saturated saline solution, drying over anhydrous sodium sulfate, and concentration were performed. The residue was purified by silica gel column chromatography to give 5.2 g of a colorless oily matter (yield: 48.7%). washing with a saturated saline solution drying over anhydrous sodium sulfate, and concentration The residue was purified by silica gel column chromatography to give 5.2 g of a colorless oily matter (yield: 48.7%)

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

Procedure: 1.8 g (8.1 mmol) of 3-di-n-butylamino-phenol are dissolved in 20 ml of dry chloroform with exclusion of moisture. 0.7 ml (8.8 mmol) of chloroacetyl chloride is added dropwise with vigorous stirring. Silica gel (about 10 g in total) is then allowed to trickle in until a large proportion of the reaction solution has been absorbed, and the mixture is boiled under reflux for 15 hours. Finally, the solid is filtered off and washed with chloroform until the wash solution remains virtually colourless. The organic phases are combined. After the solvent has been stripped off on a rotary evaporator, 1.4 g of a dark brown, highly viscous crude product are obtained. Working up of the crude product by column chromatography over silica gel using chloroform as the solvent gives the oxindigo colorant as a red-violet fraction in the first runnings. After the chloroform has been stripped off, the resulting colorant is dried under an oil pump vacuum at 75° C. for 5 hours. has been absorbed under reflux for 15 hours Finally, the solid is filtered off washed with chloroform until the wash solution After the solvent has been stripped off on a rotary evaporator, 1.4 g of a dark brown, highly viscous crude product are obtained gives the oxindigo colorant as a red-violet fraction in the first runnings the resulting colorant is dried under an oil pump vacuum at 75° C. for 5 hours

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

Procedure: Firstly, the starting compound N,N-dibutyl-4-amino-2-hydroxy-benzaldehyde had to be prepared by Vilsmeyer formylation of N,N-dibutyl-3-amino-phenol. The Vilsmeyer reagent was prepared by slow addition of 4.7 ml (0.0497 mol) of phosphorus oxychloride to 15 ml (0.189 mol) of N,N-dimethyl formamide with stirring for 15 minutes at room temperature. Stirring was continued for 30 more minutes before this Vilsmeyer reagent was used. 11 g (0.497 mol) N,N-dibutyl-3-amino-phenol, prepared by alkylation of 3-aminophenol after the procedure described in EP 0356173 was dissolved in 13 ml N,N-dimethyl formamide. This solution was added dropwise at room temperature to the Vilsmeyer reagent described above. The solution was stirred for 3 h, heated to 50° C. for 10 minutes. The solution was cooled to room temperature and stirred for another 2 h. Then, the reaction mixture was poured onto 70 g ice and stirred for 1 h. The aequous layer was extracted three times with 100 ml chloroform. The combined organic layers were evaporated in vacuo. The raw product was purified by column chromatography (450 g silicagel, eluent hexane/ethyl acetate 15:1, vol. ratio). 3.2 g (26%) N,N-Dibutylamino-2-hydroxy-benzaldehyde was obtained as an orange oily compound. Stirring This solution was added dropwise at room temperature to the Vilsmeyer reagent The solution was stirred for 3 h heated to 50° C. for 10 minutes The solution was cooled to room temperature stirred for another 2 h stirred for 1 h The aequous layer was extracted three times with 100 ml chloroform The combined organic layers were evaporated in vacuo The raw product was purified by column chromatography (450 g silicagel, eluent hexane/ethyl acetate 15:1, vol. ratio)

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: One part by weight of 1-amino-2-chloro-4-hydroxyanthraquinone, 10 parts by weight of 1,3-dimethyl-2-imidazolidinone, 1.0 part by weight of potassium carbonate and 1.0 part by weight of N,N-di-n-butyl-m-aminophenol were mixed at room temperature, and then heated to 140° C. While this temperature was maintained, the reaction was conducted for 3 hours. The reaction mixture was then cooled to room temperature, charged into 90 parts by weight of water, and extracted with toluene. After the solution was separated, toluene was distilled off under reduced pressure, and the residue was purified through silica gel column chromatography to obtain an anthraquinone compound as coloring matter No. 9 (yield 90%) in Table 1. While this temperature was maintained The reaction mixture was then cooled to room temperature extracted with toluene After the solution was separated toluene was distilled off under reduced pressure the residue was purified through silica gel column chromatography