氯化锰

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Turning now to FIG. 1, a four step synthetic route for the preparation of α,δ-bis(4-hydroxy)sexiphenylene, in accordance with an embodiment of the present invention, is presented. Thus in a first step, a first solution is prepared by adding an appropriate amount of 4-methoxyphenylacetic acid to an aqueous solution of sodium carbonate. To this first solution is added an appropriate amount of a second solution, aqueous manganese chloride, to produce a pink foamy mixture. This mixture is washed with water and filtered to yield a pink powder, now comprising sodium phenylacetate and manganese dichloride hydrate. This pink powder is distilled at 300-320° C. under vacuum to effect a thermally induced dehydrative coupling reaction to give an excellent yield (72%) of white crystals of 1,3-bis(4-methoxyphenyl)propanone, having a melting point of between approximately 75-76° C. a four step synthetic route for the preparation of α,δ-bis(4-hydroxy)sexiphenylene Thus in a first step, a first solution is prepared to produce a pink foamy mixture This mixture is washed with water filtered

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3,6,9,12,18-Pentaazabicyclo[12.3.1]octadecane prepared as in Example 38C (0.405 g, 1.59 mmol) was added to a refluxing solution of anhydrous MeOH (50 ml) containing anhydrous manganese(II) chloride (0.200 g, 1.59 mmo) under a dry nitrogen atmosphere. After refluxing for 2 h, the solution was stirred overnight at room temperature. The solution was taken to dryness. The solid was dissolved in EtOH (10 ml) and the solution was filtered through celite. Ethyl ether was added to the filtrate which induced crystallization of a white solid. The solid was collected by filtration, washed with ethyl ether and dried in vacuo to give 0.43 g (72% yield) of a white solid as product: FAB mass spectrum (NBA) m/z (relative intensity) 380 (M+, 3), 345/347 [(M-Cl)+, 100/2]; Anal. calcd for C14H31N5MnCl2 : C, 40.96; H, 7.67; N, 18.37. Found: C,40.85; H, 7.72; N, 18.32. After refluxing for 2 h the solution was filtered through celite Ethyl ether was added to the filtrate which crystallization of a white solid The solid was collected by filtration washed with ethyl ether dried in vacuo

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a methanolic solution (50 ml) at low reflux containing anhydrous manganese(II) chloride (150 mg, 1.19 mmol) was added a methanolic solution of 2-phenyl-1,4,7,10,13-pentaazacyclopentadecane prepared as in Example 31E (0.35 g, 1.2 mmol). The reaction was refluxed for 3 h under a dry nitrogen atmosphere and was then allowed to stir at room temperature overnight. The yellow solution was then filtered through celite and taken to dryness. The solid glassy oil was washed with hot ethyl ether (30 ml) and then dissolved in hot EtOH. The EtOH solution was filtered and then evaporated. The solid was recrystallized from acetone/CH3CN to give 255 mg (52% yield) of a white microcrystalline solid: FAB mass spectrum (NBA) m/z (relative intensity); 416 (M+, 2), 381/383 [(M-Cl)+, 100/32] Anal. calcd. for C16H29N5MnCl2 : C, 46.05; H, 7.01; N, 16.78. Found: C, 46.23; H, 7.04; N, 16.62. was added The reaction was refluxed for 3 h under a dry nitrogen atmosphere The yellow solution was then filtered through celite The solid glassy oil was washed with hot ethyl ether (30 ml) dissolved in hot EtOH The EtOH solution was filtered evaporated The solid was recrystallized from acetone/CH3CN to give 255 mg (52% yield) of a white microcrystalline solid

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a refluxing solution of anhydrous manganese(II) chloride (0.18 g, 1.4 mmol) in anhydrous methanol (50 ml) was added 2-octadecy-1,4,7,10,13-pentaazacyclopentadecane prepared as in example 28I (0.65 g, 1.4 mmol). The resulting solution was refluxed under a dry nitrogen atmosphere for 2 h and then stirred at room temperature overnight. The solvent was removed in vacuo, the oily residue redissolved in hot THF (20 ml) and filtered. The solution was concentrated and hot ethyl ether was added with stirring to give 0.62 g (75% yield) of the product as a white solid: FAB mass spectrum (NBA) m/z (relative intensity) 556/558 [(M-Cl)+, 100/34]; Exact mass (M-Cl)+: calcd., 557.3996; found, 557.4058 (C28H61N5MnCl). The resulting solution was refluxed under a dry nitrogen atmosphere for 2 h The solvent was removed in vacuo the oily residue redissolved in hot THF (20 ml) filtered The solution was concentrated hot ethyl ether was added with stirring

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 2-cyclohexylmethyl-1,4,7,10,13-pentaazacyclopentadecane prepared as in Example 7A (0.43 g, 1.4 mmole) and anhydrous manganese(II) chloride (0.17 g, 1.4 mmole) in anhydrous methanol (30 ml) was refluxed under a dry nitrogen atmosphere overnight. The solution was filtered and concentrated in vacuo to a volume of 3 ml. Ethyl ether (20 ml) was added. Upon cooling to 0° C., 0.39 g (65% yield) of the product was obtained as a white solid: FAB mass spectrum (NBA) m/z (relative intensity) 401/403 [(M-Cl)+, 100/33]: Anal. Calcd. for C17H37Cl2MnN5 : C, 46.69; H, 8.53; N, 16.09. Found: C, 45.87; H, 8.40; N, 15.55. was refluxed under a dry nitrogen atmosphere overnight The solution was filtered concentrated in vacuo to a volume of 3 ml Ethyl ether (20 ml) was added

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 2-phenylmethyl-1,4,7,10,13-pentaazacyclopentadecane prepared as in Example 6D (1.5 g, 4.9 mmole) and anhydrous manganese(II) chloride (0.62 g, 4.9 mmole) in anhydrous methanol was refluxed under a dry nitrogen atmosphere overnight. The solution was filtered and the solvent removed in vacuo. The yellow gummy solid was purified by stirring vigorously in acetone to give 1.89 g (89% yield) of the product as a white solid: FAB mass spectrum (NBA) m/z (relative intensity) 395/397 [(M-Cl)+, 100/31]; Anal. calcd. for C17H31Cl2MnN5 : C, 47.34; H, 7.24; Cl, 16.44; N, 16.24. Found: C, 46.84; H, 7.51; Cl, 16.38; N, 15.86. was refluxed under a dry nitrogen atmosphere overnight The solution was filtered the solvent removed in vacuo The yellow gummy solid was purified

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 2-(2-methylpropyl)-1,4,7,10,13-pentaazacyclopentadecane prepared as in Example 5D (0.66 g, 2.4 mmole) and anhydrous manganese(II) chloride (0.31 g, 2.4 mmole) in anhydrous methanol (40 ml) was refluxed under a dry nitrogen atmosphere overnight. The solution was filtered and the solvent removed in vacuo. The resulting yellow solid was recrystallized from THF-ethyl ether to give 0.46 g (48% yield) of the product as an off-white solid: FAB mass spectrum (NBA) m/z (relative intensity) 396 (M+, 1), 361/363 [(M-Cl)+ 84/26], 272 [(M-MnCl2 +H) + 100]. Anal. Calcd. for C14H33Cl2MnN5 : C, 42.33; H, 8.37; N, 17.63. Found: C, 41.90; H, 8.22; N, 17.30. was refluxed under a dry nitrogen atmosphere overnight The solution was filtered the solvent removed in vacuo The resulting yellow solid was recrystallized from THF-ethyl ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 1,4,7,10,13-pentaazacyclopentadecane prepared as in Example 1E (2.0 g, 9.3 mmole) and anhydrous manganese(II) chloride (1.2 g, 9.3 mmole) in anhydrous methanol (50 ml) was refluxed under a dry nitrogen atmosphere for 3 h. The solution was filtered and the solvent removed in vacuo. The resulting solid was recrystallized from ethanol-ethyl ether to give 2.79 g (88% yield) of the product as an off-white crystalline solid: FAB mass spectrum (NBA) m/z (relative intensity) 340 (M+, 2), 305/307 ((M-Cl)+ 100/45)); Anal. Calcd. for C10H25Cl2MnN5 : C, 35.17; H, 7.38; Cl, 20.76; N 20.60. Found: C, 34.95; H, 7.31; Cl, 20.49; N, 20.22. was refluxed under a dry nitrogen atmosphere for 3 h The solution was filtered the solvent removed in vacuo The resulting solid was recrystallized from ethanol-ethyl ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Under argon, butyl lithium in hexane (4.1 ml, 1.6 M solution) was added to a solution of 4-picoline (0.58 ml) in THF (25 ml) at -30° C. The solution was stirred for 1 hr at room temperature then cooled to 0° C. and anhydrous manganese chloride (0.76 g) added. The reaction was then stirred at room temperature for 1 hr. then cooled to 0° C. The reaction was then stirred at room temperature for 1 hr

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Under argon, butyl lithium in hexane (4.1 ml, 1.6 M solution) was added to a solution of 4-picoline (0.58 ml) in THF (25 ml) at -30° C. The solution was stirred for 1 hr at room temperature then cooled to 0° C. and anhydrous manganese chloride (0.76 g) added. The reaction was then stirred at room temperature for 1 hr. then cooled to 0° C. The reaction was then stirred at room temperature for 1 hr

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3,6,9,12,18-Pentaazabicyclo[12.3.1]octadecane prepared as in Example 38C (0.405 g, 1.59 mmol) was added to a refluxing solution of anhydrous MeOH (50 ml) containing anhydrous manganese(II) chloride (0.200 g, 1.59 mmo) under a dry nitrogen atmosphere. After refluxing for 2 h, the solution was stirred overnight at room temperature. The solution was taken to dryness. The solid was dissolved in EtOH (10 ml) and the solution was filtered through celite. Ethyl ether was added to the filtrate which induced crystallization of a white solid. The solid was collected by filtration, washed with ethyl ether and dried in vacuo to give 0.43 g (72% yield) of a white solid as product: FAB mass spectrum (NBA) m/z (relative intensity) 380 (M+, 3), 345/347 [(M-Cl)+, 100/2]; Anal. calcd for C14H31N5MnCl2 : C, 40.96; H, 7.67; N, 18.37. Found: C,40.85; H, 7.72; N, 18.32. After refluxing for 2 h the solution was filtered through celite Ethyl ether was added to the filtrate which crystallization of a white solid The solid was collected by filtration washed with ethyl ether dried in vacuo

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3,6,9,12,18-Pentaazabicyclo[12.3.1]octadecane prepared as in Example 38C (0.405 g, 1.59 mmol) was added to a refluxing solution of anhydrous MeOH (50 ml) containing anhydrous manganese(II) chloride (0.200 g, 1.59 mmo) under a dry nitrogen atmosphere. After refluxing for 2 h, the solution was stirred overnight at room temperature. The solution was taken to dryness. The solid was dissolved in EtOH (10 ml) and the solution was filtered through celite. Ethyl ether was added to the filtrate which induced crystallization of a white solid. The solid was collected by filtration, washed with ethyl ether and dried in vacuo to give 0.43 g (72% yield) of a white solid as product: FAB mass spectrum (NBA) m/z (relative intensity) 380 (M+, 3), 345/347 [(M-Cl)+, 100/2]; Anal. calcd for C14H31N5MnCl2 : C, 40.96; H, 7.67; N, 18.37. Found: C,40.85; H, 7.72; N, 18.32. After refluxing for 2 h the solution was filtered through celite Ethyl ether was added to the filtrate which crystallization of a white solid The solid was collected by filtration washed with ethyl ether dried in vacuo