1-bromooctadecane

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

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

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

Procedure: A mixture of freshly distilled aniline (93 g, 1 mol), potassium carbonate (210 g, 1.5 mol), octadecyl bromide (840 g, 2.5 mol), sodium iodide (7.5 g, 0.05 mol), and 1 liter of butanol was heated at reflux for 72 hours under nitrogen with vigorous stirring. The hot solution was filtered and the filtrate was evaporated under reduced pressure. The residue was recrystallized from absolute ethanol to yield 322 g (54%) of off-white crystals mp 110°-111° C. was heated at reflux for 72 hours under nitrogen with vigorous stirring The hot solution was filtered the filtrate was evaporated under reduced pressure The residue was recrystallized from absolute ethanol

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

Procedure: Sodium (44 g, 1.92 mol) was added in small portions to 1.5 liter of absolute ethanol containing 217 g (1.75 mol) of thiocresol, with stirring, uinder nitrogen. After the addition was completed, 640 g (1.92 mol) of bromooctadecane was added, and the mixture was heated at reflux for 2 hours. The hot reaction mixture was filtered, and the ethanol was removed under reduced pressure. The residue was crystallized from heptane yielding 595 g (91%) of white crystals. mp 54°-55° C. After the addition the mixture was heated at reflux for 2 hours The hot reaction mixture was filtered the ethanol was removed under reduced pressure The residue was crystallized from heptane yielding 595 g (91%) of white crystals

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,4-dinitrophenol (85 wt %, 6.72 g, 31 mmol), octadecyl bromide (20.7 g, 62 mmol), sodium carbonate (6.57 g, 62 mmol) and dimethylformamide (31 mL) was heated to 100° C. under a nitrogen atmosphere for 22 h. The cooled mixture was diluted with water (200 mL), acidified with 10N hydrochloric acid (50 mL) and extracted with ether. The extracts were washed with water and brine, and dried over magnesium sulfate. The solvent was removed and the solid recrystallized to give 1-octadecyloxy-2,4-dinitrobenzene (10.7 g, 79%): mp 63.5°-64.0° C. extracted with ether The extracts were washed with water and brine dried over magnesium sulfate The solvent was removed the solid recrystallized

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 30.6 Grams of bromooctadecane, 10.0 g of succinimide, 13.9 g of potassium carbonate, 0.5 g of potassium iodide and 60 ml of N,N-dimethylformamide (DMF) were charged in a flask equipped with a stirrer and a condenser and stirred with heating on an oil bath of 100° C. for 2 hours. The reaction mixture was cooled to room temperature and introduced into a large amount of pure water. The precipitated crystal was filtered off under reduced pressure and washed with methanol. The crystal was recrystallized from 2-propanol to obtain 28.5 g of the desired product. m.p. 75.8° C. equipped with a stirrer and a condenser The reaction mixture was cooled to room temperature The precipitated crystal was filtered off under reduced pressure washed with methanol The crystal was recrystallized from 2-propanol

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

Procedure: Sodium metal (0.46 g, 20 mmol) was dissolved in ethanol (50 mL) and 4,4'-dihydroxybenzophenone (1.0 g, 4.67 mmol) was added followed by 1-bromooctadecane (7.8 g, 23.4 mmol) and a catalytic amount of sodium iodide (approximately 30 mg) and the reaction mixture was refluxed for 48 hours. The resulting suspension was cooled and filtered. The solid was washed with dichloromethane followed by hexane and the white solid was dried to afford compound 22 (2.85 g, 84.8% yield). 1H NMR (300 MHz, pyridine-d5) δ7.95 (d, J=8.7 Hz, 4H, aryl), 7.09 (d, J=8.7 Hz, 4H, aryl), 4.05 (t, J=6.6 Hz, 4H, 2×OCH2), 1.80 (tt, J=6.6 and 7.5 Hz, 4H), 1.48 (m, 4H), 1.33 (brS, 60H), 0.87 (t, J=6.6 Hz, 6H, 2×CH3). The resulting suspension was cooled filtered The solid was washed with dichloromethane the white solid was dried

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of N-(diphenylmethylene)-glycine ethyl ester (67.3 g, 0.250 mol) in a 1:1 mixture of anhydrous THF (500 ml) and DMPU (500 ml) at -78° C. under a dry argon atmosphere was added a solution of lithium bis(trimethylsilyl)amide (250 ml--1.0M in THF, 0.25 mol) over a 10 min period. The resulting orange solution was stirred for 1.5 h at -78° C. While maintaining the temperature at -78° C., a solution of 1-bromooctadecane (83.4 g, 0.250 mol) in a 1:1 mixture of anhydrous THF (250 ml) and DMPU (250 ml) was added over a 10 min period and the resulting mixture was allowed to warm to room temperature. After stirring the mixture for 17 h, H2O (50 ml) and then ethyl acetate (2 l) were added. The solution was washed with H2O (4×2 l). The solution was dried over Na2CO3 -Na2SO4 and the volume was reduced in vacuo to 1 l. The product was crystallized by the addition of hexane to give 104 g (80% yield) of an off-white crystalline solid: mp 62°-5° C.; 1H NMR (CDCl3) δ 0.88 (t, J =6.6 Hz, 3 H), 1.27 (m, 35 H), 1.90 (m, 2 H), 4.03 (m, 1 H), 4.17 (m, 2 H), 7.17 (m, 2 H), 7.36 (m, 6 H), 7.64 (m, 2 H). While maintaining the temperature at -78° C. was added over a 10 min period to warm to room temperature After stirring the mixture for 17 h The solution was washed with H2O (4×2 l) The solution was dried over Na2CO3 -Na2SO4 The product was crystallized by the addition of hexane

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: After 50 ml of an N,N-dimethylformamide solution containing a mixture of 2.0 g of Compound 153a obtained in Example 119, 2 ml of octadecyl bromide and 2.0 g of potassium carbonate was stirred at 80° C. at 1.5 hours, the solvent was distilled off under reduced pressure. The aqueous phase was extracted with 200 ml of methylene chloride. The extract was washed with saturated sodium chloride aqueous solution. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The resulting residue was subjected to silica gel column chromatography (eluting solvent; hexane:ethyl acetate=15:1) to give 0.8 g of the product. the solvent was distilled off under reduced pressure The aqueous phase was extracted with 200 ml of methylene chloride The extract was washed with saturated sodium chloride aqueous solution After drying over anhydrous sodium sulfate the solvent was distilled off under reduced pressure The resulting residue was subjected to silica gel column chromatography (eluting solvent; hexane:ethyl acetate=15:1)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,4-dinitrophenol (85 wt %, 6.72 g, 31 mmol), octadecyl bromide (20.7 g, 62 mmol), sodium carbonate (6.57 g, 62 mmol) and dimethylformamide (31 mL) was heated to 100° C. under a nitrogen atmosphere for 22 h. The cooled mixture was diluted with water (200 mL), acidified with 10N hydrochloric acid (50 mL) and extracted with ether. The extracts were washed with water and brine, and dried over magnesium sulfate. The solvent was removed and the solid recrystallized to give 1-octadecyloxy-2,4-dinitrobenzene (10.7 g, 79%): mp 63.5°-64.0° C. extracted with ether The extracts were washed with water and brine dried over magnesium sulfate The solvent was removed the solid recrystallized

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,4-dinitrophenol (85 wt %, 6.72 g, 31 mmol), octadecyl bromide (20.7 g, 62 mmol), sodium carbonate (6.57 g, 62 mmol) and dimethylformamide (31 mL) was heated to 100° C. under a nitrogen atmosphere for 22 h. The cooled mixture was diluted with water (200 mL), acidified with 10N hydrochloric acid (50 ml,) and extracted with ether. The extracts were washed with water and brine, and dried over magnesium sulfate. The solvent was removed and the solid recrystallized to give 1-octadecyloxy-2,4-dinitrobenzene (10.7 g, 79%): mp 63.5°-64.0° C. extracted with ether The extracts were washed with water and brine dried over magnesium sulfate The solvent was removed the solid recrystallized

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

Procedure: Instead of octadecyl bromide, there can also be used octadecyl mercaptan which is then reacted with methyl 3-bromopropionate or added on to methyl acrylate with sodium methylate catalysis. In both cases, methyl 3-octadecylthiopropionate is obtained.