1,4,10,13-tetraoxa-7,16-diazacyclooctadecane

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

Procedure: In a manner similar to that described in Example 5, treat the cyclic diamine obtained in Example 4 and triethylamine in anhydrous benzene with a solution of n-decanoyl chloride (capryl chloride) in anhydrous benzene. Isolate and purify the resultant product in a manner similar to that described to obtain 4,13-di-(n-decanoyl)-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane. Isolate purify the resultant product in a manner similar to

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

Procedure: In a manner similar to that described in Example 5, treat the cyclic diamine obtained in Example 4 and triethylamine in anhydrous benzene with a solution of n-decanoyl chloride (capryl chloride) in anhydrous benzene. Isolate and purify the resultant product in a manner similar to that described to obtain 4,13-di-(n-decanoyl)-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane. Isolate purify the resultant product in a manner similar to

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

Procedure: In a manner similar to that described in Example 5, treat the cyclic diamine obtained in Example 4 and triethylamine in anhydrous benzene with a solution of n-decanoyl chloride (capryl chloride) in anhydrous benzene. Isolate and purify the resultant product in a manner similar to that described to obtain 4,13-di-(n-decanoyl)-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane. Isolate purify the resultant product in a manner similar to

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

Procedure: To 50 ml of methylene chloride were dissolved 0.9 g/4 mmol of 3,5-dimethyl-4-acetoxybenzoyl chloride and 0.5 g/1.9 mmol of 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane, and to this solution was added 2.2 ml of triethylamine and a catalytic amount (40 mg/0.3 mmol) of diethylaminopyridine in an ice bath. The reaction mixture was refluxed under heat for 4 hours, and allowed to cool to room temperature. The reaction solution was washed with 1N hydrochloric acid, distilled water, saturated aqueous solution of sodium hydrogencarbonate, and saturated aqueous solution of sodium chloride, in this order. The organic layer was dried with anhydrous sodium sulfate, and after removing the drying agent, the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using methylene chloride-methanol for the eluting solution to obtain 1.1 g of the desired 1,10-bis(3',5'-dimethyl-4'-acetoxyphenylcarbonyl)-1,10-diaza-4,7,13,16-tetraoxacyclooctadecane. MS: 642 (M+), 451, 191. 1H-NMR (CDCl3): δ2.15 (6H, s), 2.34 (12H, s), 3.6 (16H, br), 3.8 (8H, br), 7.05 (4H, s). The reaction mixture was refluxed under heat for 4 hours The reaction solution was washed with 1N hydrochloric acid distilled water, saturated aqueous solution of sodium hydrogencarbonate, and saturated aqueous solution of sodium chloride The organic layer was dried with anhydrous sodium sulfate after removing the drying agent the solvent was evaporated under reduced pressure The residue was purified by silica gel column chromatography

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

Procedure: To 50 ml of methylene chloride were dissolved 0.9 g/4 mmol of 3,5-dimethyl-4-acetoxybenzoyl chloride and 0.5 g/1.9 mmol of 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane, and to this solution was added 2.2 ml of triethylamine and a catalytic amount (40 mg/0.3 mmol) of diethylaminopyridine in an ice bath. The reaction mixture was refluxed under heat for 4 hours, and allowed to cool to room temperature. The reaction solution was washed with 1N hydrochloric acid, distilled water, saturated aqueous solution of sodium hydrogencarbonate, and saturated aqueous solution of sodium chloride, in this order. The organic layer was dried with anhydrous sodium sulfate, and after removing the drying agent, the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using methylene chloride-methanol for the eluting solution to obtain 1.1 g of the desired 1,10-bis(3',5'-dimethyl-4'-acetoxyphenylcarbonyl)-1,10-diaza-4,7,13,16-tetraoxacyclooctadecane. MS: 642 (M+), 451, 191. 1H-NMR (CDCl3): δ2.15 (6H, s), 2.34 (12H, s), 3.6 (16H, br), 3.8 (8H, br), 7.05 (4H, s). The reaction mixture was refluxed under heat for 4 hours The reaction solution was washed with 1N hydrochloric acid distilled water, saturated aqueous solution of sodium hydrogencarbonate, and saturated aqueous solution of sodium chloride The organic layer was dried with anhydrous sodium sulfate after removing the drying agent the solvent was evaporated under reduced pressure The residue was purified by silica gel column chromatography

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

Procedure: Analogously to Example 2 from 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane and 3,3-dimethylbutyryl chloride.

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

Procedure: Analogously to Example 2 from 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane and 2,2-dimethylbutyryl chloride.

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

Procedure: Analogously to Example 2 from 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane and 1-adamantylcarbonyl chloride.

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

Procedure: Analogously to Example 2 from 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane and pivalyl chloride.

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

Procedure: After neutralizing 1.743 g (9.53 mmol) of 2-bromomalonic acid in 2.0 ml of water by adding calcium hydroxide in portions in the presence of phenolphthalein indicator, 1.000 g (3.81 mmol) of 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane is added. The reaction mixture is heated at 40°, 45° and finally at 50° C. for a total of 72 hours, then the reaction mixture is heated at 60° C. for 24 hours while portionwise adding 0.85 g (11.47 mmol) of calcium hydroxide under vigorous stirring. Then, the precipitate (the major part of which is calcium hydroxymalonate) is filtered off and washed with 4 to 5 ml of water in 3 portions. The combined filtrate is evaporated under reduced pressure and then 2×35 ml of methylene chloride are distilled off from the evaporation residue to obtain a solid product which is dried at 75° to 85° under reduced pressure. In this way the title product is obtained in a yield of 2.710 g (89.7%) with a calcium bromide content of 31.5% by weight. is added the reaction mixture is heated at 60° C. for 24 hours is filtered off washed with 4 to 5 ml of water in 3 portions The combined filtrate is evaporated under reduced pressure 2×35 ml of methylene chloride are distilled off from the evaporation residue to obtain a solid product which is dried at 75° to 85° under reduced pressure

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

Procedure: In a manner similar to that described in Example 5, treat the cyclic diamine obtained in Example 4 and triethylamine in anhydrous benzene with a solution of n-decanoyl chloride (capryl chloride) in anhydrous benzene. Isolate and purify the resultant product in a manner similar to that described to obtain 4,13-di-(n-decanoyl)-1,7,10,16-tetraoxa-4,13-diazacyclooctadecane. Isolate purify the resultant product in a manner similar to

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

Procedure: A solution of 18.5 g. of the diamide obtained in Example 3 in 450 ml. anhydrous tetrahydrofurane is slowly added to a mixture of 150 ml. anhydrous tetrahydrofurane and 12 g. LiAlH4 while stirring and heating at the reflux temperature. After the addition is completed, the mixture is stirred under reflux and under a nitrogen atmosphere for 24 hours. After cooling to room temperature the excess reagent is destroyed by adding a mixture of water and THF (1:2). The mixture is filtered and the filtrate is evaporated to dryness. The residue is dissolved in benzene and the solution is passed through a column of Al2O3 with benzene as eluant. The solution is evaporated to dryness and after recrystallization from benzene/petrol ether 13.5 g. of the desired product is obtained. m.p. = 115°C-116°C. heating at the reflux temperature After the addition under reflux and under a nitrogen atmosphere for 24 hours is destroyed by adding a mixture of water and THF (1:2) The mixture is filtered the filtrate is evaporated to dryness The residue is dissolved in benzene The solution is evaporated to dryness after recrystallization from benzene/petrol ether 13.5 g