1,6-Dihydroxy-2,2,3,3,4,4,5,5-octafluorohexane

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

Procedure: A mixture of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (78.63 g, 0.3 mol, Aldrich Chemical Co., Milwaukee, Wis.), 1-fluoro-2,4-dinitrobenzene (18.6 g, 0.10 mmol), triethyl amine (42 mL, 0.3 mol) and acetone (100 mL) was heated to 80° C. for 1.5 hr. After aqueous workup the excess hexanediol removed by Kugelrohr distillation and the dimer by-product was removed by crystallization. The residual oil was treated with pentafluorobenzonitrile (19.3 g, 0.10 mol), triethyl amine (15.3 mL, 0.11 mol) and acetone (100 mL) and heated to reflux for 4 h. Aqueous workup followed by extraction gave 4-[6-(2,4-dinitrophenoxy)-2,2,3,3,4,4,5,5-octafluorohexyloxy]-2,3,5,6-tetrafluorobenzonitrile as an orange oil. After aqueous workup the excess hexanediol removed by Kugelrohr distillation the dimer by-product was removed by crystallization heated to reflux for 4 h Aqueous workup followed by extraction

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

Procedure: A mixture of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (78.63 g, 0.3 mol, Aldrich Chemical Co., Milwaukee, Wis.), 1-fluoro-2,4-dinitrobenzene (18.6 g, 0.10 mmol), triethyl amine (42 mL, 0.3 mol) and acetone (100 mL) was heated to 80° C. for 1.5 hr. After aqueous workup the excess hexanediol was removed by Kugelrohr distillation and the dimer by-product was removed by crystallization. The residual oil was treated with pentafluorobenzonitrile (19.3 g, 0.10 mol), triethyl amine (15.3 mL, 0.11 mol) and acetone (100 mL) and heated to reflux for 4 h. Aqueous workup followed by extraction gave 4-[6-(2,4-dinitrophenoxy)-2,2,3,3,4,4,5,5-octaflurohexyloxy]-2,3,5,6-tetrafluorobenzonitrile as an orange oil. After aqueous workup the excess hexanediol was removed by Kugelrohr distillation the dimer by-product was removed by crystallization heated to reflux for 4 h Aqueous workup followed by extraction

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

Procedure: A mixture of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (78.63 g, 0.3 mol, Aldrich Chemical Co., Milwaukee, Wis.), 1-fluoro-2,4-dinitrobenzene (18.6 g, 0.10 mmol), triethyl amine (42 mL, 0.3 mol) and acetone (100 mL) was heated to 80° C. for 1.5 hr. After aqueous workup the excess hexanediol was removed by Kugelrohr distillation and the dimer by-product was removed by crystallization. The residual oil was treated with pentafluorobenzonitrile (19.3 g, 0.10 mol), triethyl amine (15.3 mL, 0.11 mol) and acetone (100 mL) and heated to reflux for 4 h. Aqueous workup followed by extraction gave 4-[6-(2,4-dinitrophenoxy)-2,2,3,3,4,4,5,5-octaflurohexyloxy]-2,3,5,6-tetrafluorobenzonitrile as an orange oil. After aqueous workup the excess hexanediol was removed by Kugelrohr distillation the dimer by-product was removed by crystallization heated to reflux for 4 h Aqueous workup followed by extraction

Conditions: temp:97.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (7.86 g), 4-fluorobenzaldehyde (1.24 g), NMP (10 mL), and potassium carbonate (4.14 g) was heated to 95-100° C. for 48 hrs. The mixture was further processed as described in Example 1 to provide 4-(6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy)benzaldehyde.

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 15.4 g potassium hydroxide was dissolved in 200 ml of deionized water, 62 g of 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol [prepared essentially as described by I.L. Knunyants, L. Chih-yan and V. V. Shokina, Advances in Chem. (Uspekhi Khimi) 32, Original 1502, Eng. Trans. 461-476 (1963); Translation RSIC-165 (Redstone Information Center)] was added, and the mixture was heated to 90° C. Over a period of one hour, 35.7 g of ethyl iodide was added with rapid stirring to the flask via an addition funnel. The reaction mixture was then heated to reflux for two hours. The reaction mixture was cooled to room temperature, and the bottom product phase (54 g crude product) was split away from the aqueous layer. The crude product was distilled at 92°-100° C. at 5.5 mm Hg (5.5 torr) to give 29.1 g of 6-ethoxy-2,2,3,3,4,4,5,5-octafluorohexanol. Translation RSIC-165 (Redstone Information Center)] was added The reaction mixture was then heated to reflux for two hours The reaction mixture was cooled to room temperature the bottom product phase (54 g crude product) was split away from the aqueous layer The crude product was distilled at 92°-100° C. at 5.5 mm Hg (5.5 torr)

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

Procedure: A mixture of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (78.63 g, 0.3 mol, Aldrich Chemical Co., Milwaukee, Wis.), 1-fluoro-2,4-dinitrobenzene (18.6 g, 0.10 mmol), triethyl amine (42 mL, 0.3 mol) and acetone (100 mL) was heated to 80° C. for 1.5 hr. After aqueous workup the excess hexanediol removed by Kugelrohr distillation and the dimer by-product was removed by crystallization. The residual oil was treated with pentafluorobenzonitrile (19.3 g, 0.10 mol), triethyl amine (15.3 mL, 0.11 mol) and acetone (100 mL) and heated to reflux for 4 h. Aqueous workup followed by extraction gave 4-[6-(2,4-dinitrophenoxy)-2,2,3,3,4,4,5,5-octafluorohexyloxy]-2,3,5,6-tetrafluorobenzonitrile as an orange oil. After aqueous workup the excess hexanediol removed by Kugelrohr distillation the dimer by-product was removed by crystallization heated to reflux for 4 h Aqueous workup followed by extraction

Conditions: temp:97.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (7.86 g), 4-fluorobenzaldehyde (1.24 g), NMP (10 mL), and potassium carbonate (4.14 g) was heated to 95-100° C. for 48 hrs. The mixture was further processed as described in Example 1 to provide 4-(6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy)benzaldehyde.

Conditions: temp:97.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (7.86 g), 4-fluorobenzaldehyde (1.24 g), NMP (10 mL), and potassium carbonate (4.14 g) was heated to 95-100° C. for 48 hrs. The mixture was further processed as described in Example 1 to provide 4-(6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy)benzaldehyde.

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

Procedure: A mixture of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (7.86 g) was treated with pentafluoronitrobenzene (2.13 g) and triethylamine (1.39 mL) in NMP (15 mL) at room temperature for 1 hr. The mixture was diluted with water, acidified with acetic acid, and extracted with ethyl ether. The extract was washed with water and brine; dried (MgSO4) and concentrated. Excess diol was removed by distillation and the residual oil purified by chromatography to give 4-(6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy)tetrafluoronitrobenzene (3.06 g). extracted with ethyl ether The extract was washed with water and brine dried (MgSO4) concentrated Excess diol was removed by distillation the residual oil purified by chromatography

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

Procedure: A mixture of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (7.86 g) was treated with pentafluoronitrobenzene (2.13 g) and triethylamine (1.39 mL) in NMP (15 mL) at room temperature for 1 hr. The mixture was diluted with water, acidified with acetic acid, and extracted with ethyl ether. The extract was washed with water and brine; dried (MgSO4) and concentrated. Excess diol was removed by distillation and the residual oil purified by chromatography to give 4-(6-hydroxy-2,2,3,3,4,4,5,5-octafluorohexyloxy)tetrafluoronitrobenzene (3.06 g). extracted with ethyl ether The extract was washed with water and brine dried (MgSO4) concentrated Excess diol was removed by distillation the residual oil purified by chromatography

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

Procedure: To 1-[11-(2-ethylhexyl)-5-(4-fluoro-benzoyl)-11H-benzo[a]carbazol-8-yl]-3,5,5-trimethyl-hexan-1-one (1.18 g; 2.00 mmol) in pyridine (5 mL) are added 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (0.24 g; 0.90 mmol) and sodium hydroxide (0.16 g; 4 mmol) at 80° C., and the mixture is stirred at 100° C. for 43 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and poured into ice water. The crude product is extracted with ethyl acetate, and the combined organic layer is washed with water and brine, dried over MgSO4, and concentrated to give a yellow resin. The crude is purified by column chromatography on silica gel eluting with a mixed solvent of CH2Cl2 and n-hexane (1:1) to give a yellow solid (0.40 g; 32%). The structure is confirmed by 1H-NMR spectrum (CDCl3). δ [ppm]: 0.81-0.92 (m), 1.03 (d), 1.18-1.46 (m), 2.27-2.35 (m), 2.89-2.96 (m), 3.02-3.08 (m), 4.60 (t), 4.74 (m), 7.06 (d), 7.58 (m), 7.66 (t), 7.99 (m), 8.14 (dd), 8.33 (s), 8.43 (d), 8.61 (d), 8.68 (d); 19F-NMR spectrum (CDCl3). δ [ppm]: −123.32, −119.45. the reaction mixture is cooled to room temperature The crude product is extracted with ethyl acetate the combined organic layer is washed with water and brine dried over MgSO4 concentrated to give a yellow resin The crude is purified by column chromatography on silica gel eluting with a mixed solvent of CH2Cl2 and n-hexane (1:1) to give a yellow solid (0.40 g; 32%)

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

Procedure: To 1-[11-(2-ethylhexyl)-5-(4-fluoro-benzoyl)-11H-benzo[a]carbazol-8-yl]-3,5,5-trimethyl-hexan-1-one (1.18 g; 2.00 mmol) in pyridine (5 mL) are added 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (0.24 g; 0.90 mmol) and sodium hydroxide (0.16 g; 4 mmol) at 80° C., and the mixture is stirred at 100° C. for 43 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and poured into ice water. The crude product is extracted with ethyl acetate, and the combined organic layer is washed with water and brine, dried over MgSO4, and concentrated to give a yellow resin. The crude is purified by column chromatography on silica gel eluting with a mixed solvent of CH2Cl2 and n-hexane (1:1) to give a yellow solid (0.40 g; 32%). The structure is confirmed by 1H-NMR spectrum (CDCl3). δ [ppm]: 0.81-0.92 (m), 1.03 (d), 1.18-1.46 (m), 2.27-2.35 (m), 2.89-2.96 (m), 3.02-3.08 (m), 4.60 (t), 4.74 (m), 7.06 (d), 7.58 (m), 7.66 (t), 7.99 (m), 8.14 (dd), 8.33 (s), 8.43 (d), 8.61 (d), 8.68 (d); 19F-NMR spectrum (CDCl3). δ [ppm]: −123.32, −119.45. the reaction mixture is cooled to room temperature The crude product is extracted with ethyl acetate the combined organic layer is washed with water and brine dried over MgSO4 concentrated to give a yellow resin The crude is purified by column chromatography on silica gel eluting with a mixed solvent of CH2Cl2 and n-hexane (1:1) to give a yellow solid (0.40 g; 32%)