1,4-diaminoanthracene-9,10-dione

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

Procedure: In a round-bottomed flask fitted with thermometer, reflux condenser and stirrer is placed a mixture of 25 ml. glacial acetic acid and 50 ml methanol and in it is dissolved 2.38 g (0.1 mol) 1,4-diaminoanthraquinone. There is then added 4.68 g (0.2 mol) p-octyloxybenzaldehyde and the mixture is heated at 90° for one hour. The reaction mixture is cooled to about 20°-25° and poured into ice water. The precipitated product is collected and recrystallized from ethylene glycol monomethyl ether or 1:1 methanol water as small purple needles. The crystallization is repeated twice more to obtain 1,4-bis(p-octyloxybenzylidene amino)anthraquinone m.b. 280° (dec) having absorption spectra in visual and infra red ranges as shown in FIGS. 9, 10 and 11 and of sufficient purity for use in guest-host combinations. Analysis: Calculated for C44H54N2O4 ; 78.3%C, 8.06%H, 4.15%N: found 77.61%C, 7.46%H, 4.18%N. In a round-bottomed flask fitted with thermometer reflux condenser and stirrer a mixture of 25 ml the mixture is heated at 90° for one hour The reaction mixture is cooled to about 20°-25° The precipitated product is collected recrystallized from ethylene glycol monomethyl ether or 1:1 methanol water as small purple needles The crystallization

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

Procedure: In a round-bottomed flask fitted with thermometer, reflux condenser and stirrer is placed a mixture of 25 ml. glacial acetic acid and 50 ml methanol and in it is dissolved 2.38 g (0.1 mol) 1,4-diaminoanthraquinone. There is then added 4.68 g (0.2 mol) p-octyloxybenzaldehyde and the mixture is heated at 90° for one hour. The reaction mixture is cooled to about 20°-25° and poured into ice water. The precipitated product is collected and recrystallized from ethylene glycol monomethyl ether or 1:1 methanol water as small purple needles. The crystallization is repeated twice more to obtain 1,4-bis(p-octyloxybenzylidene amino)anthraquinone m.b. 280° (dec) having absorption spectra in visual and infra red ranges as shown in FIGS. 9, 10 and 11 and of sufficient purity for use in guest-host combinations. Analysis: Calculated for C44H54N2O4 ; 78.3%C, 8.06%H, 4.15%N: found 77.61%C, 7.46%H, 4.18%N. In a round-bottomed flask fitted with thermometer reflux condenser and stirrer a mixture of 25 ml the mixture is heated at 90° for one hour The reaction mixture is cooled to about 20°-25° The precipitated product is collected recrystallized from ethylene glycol monomethyl ether or 1:1 methanol water as small purple needles The crystallization

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

Procedure: In a round-bottomed flask fitted with thermometer, reflux condenser and stirrer is placed a mixture of 25 ml. glacial acetic acid and 50 ml methanol and in it is dissolved 2.38 g (0.1 mol) 1,4-diaminoanthraquinone. There is taken added 4.68 g (0.2 mol) p-octyloxybenzaldehyde and the mixture is heated at 90° for one hour. The reaction mixture is cooled to about 20°-25° and poured into ice water. The precipitated product is collected and recrystallized from ethylene glycol monomethyl ether or 1:1 methanol water as small purple needles. The crystallization is repeated twice more to obtain 1,4-bis(p-octyloxybenzylidene amino)anthraquinone m.p. 280° C. (dec) having absorption spectra in visual and infra red ranges as shown in FIGS. 9, 10, and 11 and of sufficient purity for use in guest-host combinations. In a round-bottomed flask fitted with thermometer reflux condenser and stirrer a mixture of 25 ml the mixture is heated at 90° for one hour The reaction mixture is cooled to about 20°-25° The precipitated product is collected recrystallized from ethylene glycol monomethyl ether or 1:1 methanol water as small purple needles The crystallization

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

Procedure: Following the procedure as descrilbed in Example 1, but suspending the 1-chloroanthraquinone, 1,4-diaminoanthraquinone, sodium carbonate and CuCl in 300 ml of nitrobenzene, the anthrimide is obtained in a yield corresponding to that of Example 1. When following a conventional procedure, i.e. mixing the components and heating them slowly, if such a concentrated reaction mixture is employed, the reaction can no longer be carried out in an agitator vessel.

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

Procedure: Following the procedure as descrilbed in Example 1, but suspending the 1-chloroanthraquinone, 1,4-diaminoanthraquinone, sodium carbonate and CuCl in 300 ml of nitrobenzene, the anthrimide is obtained in a yield corresponding to that of Example 1. When following a conventional procedure, i.e. mixing the components and heating them slowly, if such a concentrated reaction mixture is employed, the reaction can no longer be carried out in an agitator vessel.

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 60 parts of 1,4-diaminoanthraquinone are added to 228 parts of 25% oleum over one hour and then 20 parts of pyridine are added. The temperature of the reaction mixture is 70°-80° C. and is further raised to 120° C. The reaction mixture is stirred at this temperature for 3 hours, then cooled to 70°-80° C., and 220 parts of water are slowly added dropwise. The resultant thick suspension is filtered at room temperature and the filter cake is washed with 100 parts of 50% sulfuric acid and subsequently dispersed in water. The pH of the aqueous suspension is then adjusted to 7.5 with 35% sodium hydroxide solution, whereupon the 1,4-diaminoanthraquinone-2sulfonic acid goes into solution. The solution is then heated to 85°-90° C. and 40 parts of magnesium sulfate are added. Upon cooling the reaction solution, the 1,4-diaminoanthraquinone-2-sulfonic acid crystallises in the form of the magnesium salt, which is isolated by filtration, washed with a 5% solution of magnesium sulfate and dried, affording 72.4 parts of the magnesium salt of 1,4-diaminoanthraquinone-2-sulfonic acid, corresponding to a yield of 85%. According to chromatographic analysis, the product is homogeneous with a trace of starting material. The Rf value is 0.57, which confirms that this product is identical with that obtained in Example 1. is 70°-80° C. cooled to 70°-80° C. The resultant thick suspension is filtered at room temperature the filter cake is washed with 100 parts of 50% sulfuric acid subsequently dispersed in water The solution is then heated to 85°-90° C. 40 parts of magnesium sulfate are added Upon cooling the reaction solution the 1,4-diaminoanthraquinone-2-sulfonic acid crystallises in the form of the magnesium salt which is isolated by filtration washed with a 5% solution of magnesium sulfate dried

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 60 parts of 1,4-diaminoanthraquinone are added to 228 parts of 25% oleum over one hour and then 20 parts of pyridine are added. The temperature of the reaction mixture is 70°-80° C. and is further raised to 120° C. The reaction mixture is stirred at this temperature for 3 hours, then cooled to 70°-80° C., and 220 parts of water are slowly added dropwise. The resultant thick suspension is filtered at room temperature and the filter cake is washed with 100 parts of 50% sulfuric acid and subsequently dispersed in water. The pH of the aqueous suspension is then adjusted to 7.5 with 35% sodium hydroxide solution, whereupon the 1,4-diaminoanthraquinone-2sulfonic acid goes into solution. The solution is then heated to 85°-90° C. and 40 parts of magnesium sulfate are added. Upon cooling the reaction solution, the 1,4-diaminoanthraquinone-2-sulfonic acid crystallises in the form of the magnesium salt, which is isolated by filtration, washed with a 5% solution of magnesium sulfate and dried, affording 72.4 parts of the magnesium salt of 1,4-diaminoanthraquinone-2-sulfonic acid, corresponding to a yield of 85%. According to chromatographic analysis, the product is homogeneous with a trace of starting material. The Rf value is 0.57, which confirms that this product is identical with that obtained in Example 1. is 70°-80° C. cooled to 70°-80° C. The resultant thick suspension is filtered at room temperature the filter cake is washed with 100 parts of 50% sulfuric acid subsequently dispersed in water The solution is then heated to 85°-90° C. 40 parts of magnesium sulfate are added Upon cooling the reaction solution the 1,4-diaminoanthraquinone-2-sulfonic acid crystallises in the form of the magnesium salt which is isolated by filtration washed with a 5% solution of magnesium sulfate dried

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

Procedure: A suspension of 10 parts of 1,4-diaminoanthraquinone in 90 parts of dimethylsulfoxide is heated to 120° to 125° C., 12.5 parts of sodium cyanide is added all at once and then 5 parts of ammonium chloride is added within 15 minutes under an effective fume hood. The whole is stirred for another 3 hours at 120° to 125° C., whereupon one makes sure by a chromatogram that practically all of the starting material has been used up. The reaction mixture is allowed to cool and is diluted with 300 parts by volume of cold methanol, air is blown through under an effective fume hood for a short period, the precipitate is suction filtered and the filter cake is washed with methanol until the liquid running away is almost colorless. After drying, 9.5 parts of 1,4-diaminoanthraquinone-2,3-dinitrile is obtained. is heated to 120° to 125° C. is added within 15 minutes under an effective fume hood to cool is blown through under an effective fume hood for a short period filtered the filter cake is washed with methanol until the liquid After drying

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

Procedure: 20 parts of tetraethylammonium ethosulfate and 48 parts of 1,4-diaminoanthraquinone are introduced into 400 parts by volume of dimethylformamide and the mixture is heated to 120° to 125° C. At this temperature there is introduced in the course of thirty minutes 50 parts of sodium cyanide and then 24 parts of sodium m-nitrobenzenesulfonate is added in about twenty minutes. 6 parts of powdered sulfur is added and the whole is stirred at 120° to 125° C. until all the 1,4-diaminoanthraquinone has been used up, this being the case after from 10 to 12 hours. After the whole has cooled to about 50° to 60° C. the reaction mixture is poured into 2000 parts of water, air is passed through the mixture to oxidize leuco compound still present and finally the excess sodium cyanide is destroyed by adding 35 parts of 30% hydrogen peroxide at from 60° to 70° C. while stirring. Suction filtration is carried out while the mixture is still warm and the filter cake is washed well with water and finally washed with methanol until the liquid running away is colorless. After drying, 47 parts of 1,4-diaminoanthraquinone-2,3-dinitrile is obtained which agrees chromatographically with the product obtained according to the process of German Pat. No. 1,108,704 and which has a melting point above 350° C. Recovery of the solvent may be carried out as described in Example 2 (b). An equally good product is obtained when an equivalent amount of trimethylbenzylammonium chloride is used instead of tetraethylammonium ethosulfate. the mixture is heated to 120° to 125° C After the whole has cooled to about 50° to 60° C. the reaction mixture finally the excess sodium cyanide is destroyed by adding 35 parts of 30% hydrogen peroxide at from 60° to 70° C. Suction filtration is still warm the filter cake is washed well with water finally washed with methanol until the liquid After drying

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

Procedure: 20 parts of tetraethylammonium ethosulfate and 48 parts of 1,4-diaminoanthraquinone are introduced into 400 parts by volume of dimethylformamide and the mixture is heated to 120° to 125° C. At this temperature there is introduced in the course of thirty minutes 50 parts of sodium cyanide and then 24 parts of sodium m-nitrobenzenesulfonate is added in about twenty minutes. 6 parts of powdered sulfur is added and the whole is stirred at 120° to 125° C. until all the 1,4-diaminoanthraquinone has been used up, this being the case after from 10 to 12 hours. After the whole has cooled to about 50° to 60° C. the reaction mixture is poured into 2000 parts of water, air is passed through the mixture to oxidize leuco compound still present and finally the excess sodium cyanide is destroyed by adding 35 parts of 30% hydrogen peroxide at from 60° to 70° C. while stirring. Suction filtration is carried out while the mixture is still warm and the filter cake is washed well with water and finally washed with methanol until the liquid running away is colorless. After drying, 47 parts of 1,4-diaminoanthraquinone-2,3-dinitrile is obtained which agrees chromatographically with the product obtained according to the process of German Pat. No. 1,108,704 and which has a melting point above 350° C. Recovery of the solvent may be carried out as described in Example 2 (b). An equally good product is obtained when an equivalent amount of trimethylbenzylammonium chloride is used instead of tetraethylammonium ethosulfate. the mixture is heated to 120° to 125° C After the whole has cooled to about 50° to 60° C. the reaction mixture finally the excess sodium cyanide is destroyed by adding 35 parts of 30% hydrogen peroxide at from 60° to 70° C. Suction filtration is still warm the filter cake is washed well with water finally washed with methanol until the liquid After drying

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

Procedure: In a round-bottomed flask fitted with thermometer, reflux condenser and stirrer is placed a mixture of 25 ml. glacial acetic acid and 50 ml methanol and in it is dissolved 2.38 g (0.1 mol) 1,4-diaminoanthraquinone. There is then added 4.68 g (0.2 mol) p-octyloxybenzaldehyde and the mixture is heated at 90° for one hour. The reaction mixture is cooled to about 20°-25° and poured into ice water. The precipitated product is collected and recrystallized from ethylene glycol monomethyl ether or 1:1 methanol water as small purple needles. The crystallization is repeated twice more to obtain 1,4-bis(p-octyloxybenzylidene amino)anthraquinone m.b. 280° (dec) having absorption spectra in visual and infra red ranges as shown in FIGS. 9, 10 and 11 and of sufficient purity for use in guest-host combinations. Analysis: Calculated for C44H54N2O4 ; 78.3%C, 8.06%H, 4.15%N: found 77.61%C, 7.46%H, 4.18%N. In a round-bottomed flask fitted with thermometer reflux condenser and stirrer a mixture of 25 ml the mixture is heated at 90° for one hour The reaction mixture is cooled to about 20°-25° The precipitated product is collected recrystallized from ethylene glycol monomethyl ether or 1:1 methanol water as small purple needles The crystallization

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

Procedure: In a round-bottomed flask fitted with thermometer, reflux condenser and stirrer is placed a mixture of 25 ml. glacial acetic acid and 50 ml methanol and in it is dissolved 2.38 g (0.1 mol) 1,4-diaminoanthraquinone. There is taken added 4.68 g (0.2 mol) p-octyloxybenzaldehyde and the mixture is heated at 90° for one hour. The reaction mixture is cooled to about 20°-25° and poured into ice water. The precipitated product is collected and recrystallized from ethylene glycol monomethyl ether or 1:1 methanol water as small purple needles. The crystallization is repeated twice more to obtain 1,4-bis(p-octyloxybenzylidene amino)anthraquinone m.p. 280° C. (dec) having absorption spectra in visual and infra red ranges as shown in FIGS. 9, 10, and 11 and of sufficient purity for use in guest-host combinations. In a round-bottomed flask fitted with thermometer reflux condenser and stirrer a mixture of 25 ml the mixture is heated at 90° for one hour The reaction mixture is cooled to about 20°-25° The precipitated product is collected recrystallized from ethylene glycol monomethyl ether or 1:1 methanol water as small purple needles The crystallization