4-hexylphenol

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

Procedure: 1.00 g (5.61 mM) of 4-hexylphenol was dissolved in a mixture solvent of 2.0 ml of benzene and 1.3 ml of acetic acid. To the solution, 0.62 ml (8.15 mM) of nitric acid (60%, density=1.38) was gradually added dropwise under cooling with iced water and stirring below 8° C. After the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried with anhydrous sodium sulfate and subjected to reduced-pressure distillation into a solid. The solid was purified by silica gel column chromatography (eluent: toluene/hexane=1/2) to obtain 1.16 g of oily yellow 2-nitro-4-hexylphenol (Yield: 92.6%). After the reaction extracted with ethyl acetate The organic layer was dried with anhydrous sodium sulfate subjected to reduced-pressure distillation into a solid The solid was purified by silica gel column chromatography (eluent: toluene/hexane=1/2)

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

Procedure: 1.00 g (5.61 mM) of 4-hexylphenol was dissolved in a mixture solvent of 2.0 ml of benzene and 1.3 ml of acetic acid. To the solution, 0.62 ml (8.15 mM) of nitric acid (60%, density=1.38) was gradually added dropwise under cooling with iced water and stirring below 8° C. After the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried with anhydrous sodium sulfate and subjected to reduced-pressure distillation into a solid. The solid was purified by silica gel column chromatography (eluent: toluene/hexane=1/2) to obtain 1.16 g of oily yellow 2-nitro-4-hexylphenol (Yield: 92.6%). After the reaction extracted with ethyl acetate The organic layer was dried with anhydrous sodium sulfate subjected to reduced-pressure distillation into a solid The solid was purified by silica gel column chromatography (eluent: toluene/hexane=1/2)

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

Procedure: The plasticizer 2-nitrophenyl 4-hexylphenyl ether (NPHPE) is synthesized by reacting p-hexylphenol (available from Kodak Lab. Chem., catalog No. 14,319) with 2-chloronitrobenzene (available from Aldrich Chem. Co., catalog No. C5,910-6). 1.44 g (0.06 mol) of sodium hydride is suspended in 75 ml of THF under N2. 9.01 g (0.05 mol) of p-hexylphenol are dissolved in 25 ml of THF and added dropwise to the suspension. 7.86 (0.05 mol) of 2-chloronitrobenzene are dissolved in 25 ml of THF and added dropwise to the reaction mixture; the resultant mixture is refluxed for 88 hours. Following reflux 3 ml of acetic acid are added, and the reaction is filtered through filter cel, concentrated, chromatographed twice on silical gel, and Kugelrohr distilled at 0.01 mm Hg, 140°-150° C., to yield 4.7 g (34% yield) of 2-nitrophenl 4-hexylphenyl ether as an orange oil. added dropwise to the suspension added dropwise to the reaction mixture are added the reaction is filtered through filter cel concentrated chromatographed twice on silical gel, and Kugelrohr distilled at 0.01 mm Hg, 140°-150° C.

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

Procedure: The plasticizer 2-nitrophenyl 4-hexylphenyl ether (NPHPE) is synthesized by reacting p-hexylphenol (available from Kodak Lab. Chem., catalog No. 14,319) with 2-chloronitrobenzene (available from Aldrich Chem. Co., catalog No. C5,910-6). 1.44 g (0.06 mol) of sodium hydride is suspended in 75 ml of THF under N2. 9.01 g (0.05 mol) of p-hexylphenol are dissolved in 25 ml of THF and added dropwise to the suspension. 7.86 (0.05 mol) of 2-chloronitrobenzene are dissolved in 25 ml of THF and added dropwise to the reaction mixture; the resultant mixture is refluxed for 88 hours. Following reflux 3 ml of acetic acid are added, and the reaction is filtered through filter cel, concentrated, chromatographed twice on silical gel, and Kugelrohr distilled at 0.01 mm Hg, 140°-150° C., to yield 4.7 g (34% yield) of 2-nitrophenl 4-hexylphenyl ether as an orange oil. added dropwise to the suspension added dropwise to the reaction mixture are added the reaction is filtered through filter cel concentrated chromatographed twice on silical gel, and Kugelrohr distilled at 0.01 mm Hg, 140°-150° C.

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

Procedure: A stirred suspension of 4-n-hexylphenol (972 g; 5.46 mol), 61.7 g of 5% rhodium on carbon catalyst (46.0 g of Alfa Chemical Co. lot 063081 and 17.7 g of MCB Chemicals lot A12M04), HOAc (21 ml), and MeOH (5.0 L) was hydrogenated in a 5 gallon autoclave (100 psi) at 35°-55° until 73% of theoretical H2 was consumed. A sample was withdrawn and NMR and GC tests showed that a small amount of the hexylphenol remained. Hydrogenation was continued until a total of 78% of theoretical H2 was consumed. The catalyst was filtered off, and the clear filtrate was concentrated in vacuo to a clear oil, 1065 g (106%); IR (neat) cm-1 3400, (OH) 1715 (carbonyl); NMR (CDCl3) no aromatic absorbance was observed. was hydrogenated in a 5 gallon autoclave (100 psi) at 35°-55° until 73% of theoretical H2 was consumed A sample was withdrawn was consumed The catalyst was filtered off the clear filtrate was concentrated in vacuo to a clear oil, 1065 g (106%)

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

Procedure: A stirred suspension of 4-n-hexylphenol (972 g; 5.46 mol), 61.7 g of 5% rhodium on carbon catalyst (46.0 g of Alfa Chemical Co. lot 063081 and 17.7 g of MCB Chemicals lot A12M04), HOAc (21 ml), and MeOH (5.0 L) was hydrogenated in a 5 gallon autoclave (100 psi) at 35°-55° until 73% of theoretical H2 was consumed. A sample was withdrawn and NMR and GC tests showed that a small amount of the hexylphenol remained. Hydrogenation was continued until a total of 78% of theoretical H2 was consumed. The catalyst was filtered off, and the clear filtrate was concentrated in vacuo to a clear oil, 1065 g (106%); IR (neat) cm-1 3400, (OH) 1715 (carbonyl); NMR (CDCl3) no aromatic absorbance was observed. was hydrogenated in a 5 gallon autoclave (100 psi) at 35°-55° until 73% of theoretical H2 was consumed A sample was withdrawn was consumed The catalyst was filtered off the clear filtrate was concentrated in vacuo to a clear oil, 1065 g (106%)

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

Procedure: A stirred suspension of 4-n-hexylphenol (972 g; 5.46 mol), 61.7 g of 5% rhodium on carbon catalyst (46.0 g of Alfa Chemical Co. lot 063081 and 17.7 g of MCB Chemicals lot A12M04), HOAc (21 ml), and MeOH (5.0 L) was hydrogenated in a 5 gallon autoclave (100 psi) at 35°-55° until 73% of theoretical H2 was consumed. A sample was withdrawn and NMR and GC tests showed that a small amount of the hexylphenol remained. Hydrogenation was continued until a total of 78% of theoretical H2 was consumed. The catalyst was filtered off, and the clear filtrate was concentrated in vacuo to a clear oil, 1065 g (106%); IR (neat) cm-1 3400, (OH) 1715 (carbonyl); NMR (CDCl3) no aromatic absorbance was observed. was hydrogenated in a 5 gallon autoclave (100 psi) at 35°-55° until 73% of theoretical H2 was consumed A sample was withdrawn was consumed The catalyst was filtered off the clear filtrate was concentrated in vacuo to a clear oil, 1065 g (106%)

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

Procedure: To a solution of sodium hydride (60 wt % in mineral oil, 202 mg, 5.05 mmol) in N,N-dimethylformamide (1.0 ml) was added 4-hexylphenol (899 mg, 5.04 mmol) at room temperature, and stirred for one hour. 2-Chloro-1-methyl-1H-[4,4′]bipyrimidinyl-6-one (935 mg, 4.20 mmol) was added to the solution. The mixture was stirred at room temperature overnight. The mixture was poured into water, and extracted with dichloromethane. The organic layer was washed with water (three times), dried over sodium sulfate, and concentrated in vacuo. The residue was purified by silica gel column chromatography (eluent; hexane/ethyl acetate=50/50) to afford 2-(4-hexylphenoxy)-1-methyl-1H-[4,4′]bipyrimidinyl-6-one as a colorless solid (1.14 g, 3.13 mmol, 75%). The mixture was stirred at room temperature overnight extracted with dichloromethane The organic layer was washed with water (three times) dried over sodium sulfate concentrated in vacuo The residue was purified by silica gel column chromatography (eluent; hexane/ethyl acetate=50/50)

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

Procedure: 1.00 g (5.61 mM) of 4-hexylphenol was dissolved in a mixture solvent of 2.0 ml of benzene and 1.3 ml of acetic acid. To the solution, 0.62 ml (8.15 mM) of nitric acid (60%, density=1.38) was gradually added dropwise under cooling with iced water and stirring below 8° C. After the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried with anhydrous sodium sulfate and subjected to reduced-pressure distillation into a solid. The solid was purified by silica gel column chromatography (eluent: toluene/hexane=1/2) to obtain 1.16 g of oily yellow 2-nitro-4-hexylphenol (Yield: 92.6%). After the reaction extracted with ethyl acetate The organic layer was dried with anhydrous sodium sulfate subjected to reduced-pressure distillation into a solid The solid was purified by silica gel column chromatography (eluent: toluene/hexane=1/2)

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

Procedure: The plasticizer 2-nitrophenyl 4-hexylphenyl ether (NPHPE) is synthesized by reacting p-hexylphenol (available from Kodak Lab. Chem., catalog No. 14,319) with 2-chloronitrobenzene (available from Aldrich Chem. Co., catalog No. C5,910-6). 1.44 g (0.06 mol) of sodium hydride is suspended in 75 ml of THF under N2. 9.01 g (0.05 mol) of p-hexylphenol are dissolved in 25 ml of THF and added dropwise to the suspension. 7.86 (0.05 mol) of 2-chloronitrobenzene are dissolved in 25 ml of THF and added dropwise to the reaction mixture; the resultant mixture is refluxed for 88 hours. Following reflux 3 ml of acetic acid are added, and the reaction is filtered through filter cel, concentrated, chromatographed twice on silical gel, and Kugelrohr distilled at 0.01 mm Hg, 140°-150° C., to yield 4.7 g (34% yield) of 2-nitrophenl 4-hexylphenyl ether as an orange oil. added dropwise to the suspension added dropwise to the reaction mixture are added the reaction is filtered through filter cel concentrated chromatographed twice on silical gel, and Kugelrohr distilled at 0.01 mm Hg, 140°-150° C.