16-溴十六烷酸甲酯

反应条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 16-Bromo-hexadecanoic acid (6.0 g) was dissolved in MeOH (35 mL), toluene (100 mL) and trimethylorthoformate (20 mL), then Amberlyst 15 from Fluka (1.4 g) was added. The mixture was stirred at 55° C. for 16 h. The mixture was evaporated to dryness and dried under vacuum for 16 h to yield 7.7 g. The residue was suspended in MeOH (ca. 50 mL) and stirred for ca ½ h. The amberlyst 15 was filtered off after stirring with DCM (30 mL) for ½ h. The filtrate was concentrated to remove the DCM, and the clear solution was cooled and more MeOH (ca 20 mL, total ca 40 mL) was added. The flask was cooled and more crystals precipitated and after stirring for 30 min, the crystals were filtered off and washed with cold MeOH. The white crystals were dried under vacuum to yield 5.61 g. The mixture was evaporated to dryness dried under vacuum for 16 h to yield 7.7 g stirred for ca ½ h The amberlyst 15 was filtered off after stirring with DCM (30 mL) for ½ h The filtrate was concentrated to remove the DCM the clear solution was cooled more MeOH (ca 20 mL, total ca 40 mL) was added The flask was cooled more crystals precipitated after stirring for 30 min the crystals were filtered off washed with cold MeOH The white crystals were dried under vacuum to yield 5.61 g

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

实验步骤: A mixture of 1.37 g. of 4-aminobenzoic acid, 3.50 g. of methyl 16-bromohexadecanoate, 2.12 g. of sodium carbonate and 140 ml. of hexamethylphosphoramide is stirred at 120° C. for 18 hours, allowed to cool, and poured into dilute hydrochloric acid. The precipitate is collected by filtration, dried, and crystallized from acetonitrile to yield 4-(15-carbomethoxypentadecylamino)benzoic acid as a white solid. A mixture of 1.37 g to cool The precipitate is collected by filtration dried crystallized from acetonitrile

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

实验步骤: A solution of 12 g. of 4-aminobenzonitrile and 15 g. of methyl 16-bromohexadecanoate in 200 ml. of hexamethylphosphoramide is heated at 120° for 22 hours, allowed to cool, and diluted with water. The mixture is chilled and the precipitate which forms is collected, dried, and recystallized from etherhexane to yield 4-(15-carbomethoxypentadecylamino)benzonitrile as a white solid. to cool The mixture is chilled the precipitate which forms is collected dried

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

实验步骤: A solution of 12 g. of 4-aminobenzonitrile and 15 g. of methyl 16-bromohexadecanoate in 200 ml. of hexamethylphosphoramide is heated at 120° for 22 hours, allowed to cool, and diluted with water. The mixture is chilled and the precipitate which forms is collected, dried, and recystallized from etherhexane to yield 4-(15-carbomethoxypentadecylamino)benzonitrile as a white solid. to cool The mixture is chilled the precipitate which forms is collected dried

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

实验步骤: A solution of 21 g. of methyl 16-bromohexadecanoate and 20 g. of ethyl 4-aminobenzoate in 150 ml. of hexamethylphosphoramide is stirred at 120° C. for 20 horus, cooled, diluted with water and filtered. A methylene chloride solution of the solid is dried over anhydrous magnesium sulfate, clarified with activated charcoal, and filtered through silica gel. The filtrate is evaporated and the residue crystallized from acetonitrile to yield ethyl 4-(15-carbomethoxypentadecylamino)benzoate as a white crystalline solid. cooled filtered A methylene chloride solution of the solid is dried over anhydrous magnesium sulfate filtered through silica gel The filtrate is evaporated the residue crystallized from acetonitrile

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

实验步骤: A mixture of 22 g. of 16-bromohexadecanoic acid and 200 ml. of methanol is treated with 1.0 ml. of concentrated sulfuric acid and stirred under reflux for 24 hours. The mixture is treated with 10 g. of sodium acetate and the solvent is evaporated. The residue is partially soluble in 300 ml. of ether and the mixture is filtered. The ether solution is dried over magnesium sulfate and evaporated. The residue is crystallized from petroleum ether to yield methyl 16-bromohexadecanoate as a white solid. A mixture of 22 g under reflux for 24 hours The mixture is treated with 10 g of sodium acetate and the solvent is evaporated of ether and the mixture is filtered The ether solution is dried over magnesium sulfate evaporated The residue is crystallized from petroleum ether

反应条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 16-Bromo-hexadecanoic acid (6.0 g) was dissolved in MeOH (35 mL), toluene (100 mL) and trimethylorthoformate (20 mL), then Amberlyst 15 from Fluka (1.4 g) was added. The mixture was stirred at 55° C. for 16 h. The mixture was evaporated to dryness and dried under vacuum for 16 h to yield 7.7 g. The residue was suspended in MeOH (ca. 50 mL) and stirred for ca ½ h. The amberlyst 15 was filtered off after stirring with DCM (30 mL) for ½ h. The filtrate was concentrated to remove the DCM, and the clear solution was cooled and more MeOH (ca 20 mL, total ca 40 mL) was added. The flask was cooled and more crystals precipitated and after stirring for 30 min, the crystals were filtered off and washed with cold MeOH. The white crystals were dried under vacuum to yield 5.61 g. The mixture was evaporated to dryness dried under vacuum for 16 h to yield 7.7 g stirred for ca ½ h The amberlyst 15 was filtered off after stirring with DCM (30 mL) for ½ h The filtrate was concentrated to remove the DCM the clear solution was cooled more MeOH (ca 20 mL, total ca 40 mL) was added The flask was cooled more crystals precipitated after stirring for 30 min the crystals were filtered off washed with cold MeOH The white crystals were dried under vacuum to yield 5.61 g

反应条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 16-bromohexadecanoic acid methyl ester (1.40 g, 4.0 mmol) in MeCN (20 ml) were added malonodinitrile (1.01 g, 15.3 mmol) and K2CO3 (0.92 g, 6.64 mmol). The mixture was stirred at 80° C. for 18.5 h. Water (50 ml) and 1N HCl (50 ml) were added, and the product was extracted with AcOEt. The combined extracts were washed with brine, dried over MgSO4, and concentrated under reduced pressure. 1.87 g (100%) of an oil was obtained which crystallized completely after some hours. the product was extracted with AcOEt The combined extracts were washed with brine dried over MgSO4 concentrated under reduced pressure

反应条件: temp:82.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 16-bromohexadecanoic acid methyl ester (4.86 g, 13.9 mmol), MeCN (20 ml), 4-cyano-4′-hydroxybiphenyl (3.16 g, 16.2 mmol), and K2CO3 (2.45 g, 17.7 mmol) was stirred at 82° C. After 17 h satd aqueous NaHCO3 (150 ml) was added, and the product was filtered, washed with water, and recrystallized from boiling MeCN (approx 80 ml). Filtration and drying under reduced pressure yielded 5.40 g (84%) of (4′-cyanobiphenyl-4-yloxy)hexadecanoic acid methyl ester colorless needles. the product was filtered washed with water recrystallized Filtration drying under reduced pressure

反应条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 16-bromohexadecanoic acid (15.5 g, 46.2 mmol), MeOH (100 ml), PhMe (30 ml), trimethylorthoformate (30 ml), and polystyrene-bound benzenesulfonic acid (3.6 g) was stirred at 55° C. After 69 h the mixture was filtered through celite and the filtrate was concentrated to yield 16.85 g of an oil (100% yield). After 69 h the mixture was filtered through celite the filtrate was concentrated

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

实验步骤: 16-bromohexadecanoic acid methyl ester is reacted with sodium azide in acetonitrile for four days at reflux temperature to give the corresponding azide (Zinic et al., Positionally Isomeric Organic Gelators: Structure-Gelation Study, Racemic versus Enantiomeric Gelators, and Solvation Effects, Chem. Eur. J. 2010; 16:3066-82). at reflux temperature

反应条件: temp:27.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Solutions of sodium sulfite (327 g, 2.60 mol) in water (1.26 L) and 16-bromo-hexadecanoic acid methyl ester (728 g, 2.00 mol, 96% purity) in 1-propanol (945 mL) and methanol (420 mL) were heated to reflux in 6 L reactor equipped with mechanical stirrer for 48 hours. The reaction mixture was cooled to 27° C. and diluted with tetrahydrofuran (2 L). Reaction mixture was filtered and solid material was washed with tetrahydrofuran (3×700 mL). Filtrate was cooled to 0° C. and another portion of material was precipitated. This precipitate was filtered and washed with tetrahydrofuran (2×200 mL). Solids were combined and mixed with water (8.4 L) in 20 L pot. Solution of sodium hydroxide (120 g, 3.00 mol) was added. The mixture was heated to boiling for about 5 hours. Solution of sulfuric acid (430 mL, 8.00 mol) in water (500 mL) was slowly added into the reaction mixture (sulfur dioxide is formed). Reaction mixture was heated to boiling for 10 minutes and then let to cool to 15° C. (ice bath). The mixture was filtered on Büchner funnel through filter paper Seitz (several layers filter) applying vacuo. This procedure was very slow and took two days. Solid material was several times washed with distilled water until pH of filtrate was between 2 and 3. This procedure took about three days. Muddy white material was dried in oven at 80° C. giving desired product. to reflux in 6 L reactor equipped with mechanical stirrer for 48 hours Reaction mixture was filtered solid material was washed with tetrahydrofuran (3×700 mL) Filtrate was cooled to 0° C. another portion of material was precipitated This precipitate was filtered washed with tetrahydrofuran (2×200 mL) mixed with water (8.4 L) in 20 L pot The mixture was heated Reaction mixture was heated to boiling for 10 minutes to cool to 15° C. (ice bath) The mixture was filtered on Büchner funnel through filter paper Seitz (several layers filter) took two days washed with distilled water until pH of filtrate This procedure took about three days Muddy white material was dried in oven at 80° C.