2-(2-hydroxyphenyl)phenol

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

Procedure: To biphenol (0.5 mole) and 200 milliliters of absolute ethanol and sodium hydroxide (1.1 millimole) at 80° C. was added dropwise a solution of 2-chloroethanol (1 mole) in 50 milliliters of absolute ethanol. The mixture was refluxed for 48 hours, and then filtered hot and washed twice with boiling ethanol (100 milliliters). Recrystallization from boiling water provided the precursor product biphenol-diethanol, 80 to 85 percent yield of colorless crystals. The melting point for this product was 210 to 211° C. The mixture was refluxed for 48 hours filtered hot washed twice with boiling ethanol (100 milliliters) Recrystallization

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

Procedure: A mixture of 74 g (0.40 moles) of biphenol and 20 g (0.50 moles) of sodium hydroxide in 600 ml of ethanol was refluxed for 1 hour. At reflux temperature 66 g (0.40 moles) of 6-bromohexane were added over a period of 1 hour. The reaction mixture was refluxed for 18 hours and cooled to room temperature, and the precipitate was filtrated. The filtrate was treated with 500 ml of water and the precipitated 4-hexyloxy-4'-hydroxybiphenyl was filtrated and washed with water. After drying 29 g of product were obtained. An additional amount of product was obtained by refluxing the precipitate collected from the reaction mixture with 45 g of potassium hydroxide in 600 ml of ethanol for 3 hours. This mixture was cooled to room temperature and the insoluble dihexyloxybiphenyl filtered off. The clear filtrate was treated with 200 ml of 6N hydrochloric acid and the precipitated 4-hexyloxy-4'-hydroxybiphenyl was filtrated, washed with water, and dried. The yield was 19 g. The total yield was 48 g (44% of theory). was refluxed for 1 hour were added over a period of 1 hour The reaction mixture was refluxed for 18 hours the precipitate was filtrated The filtrate was treated with 500 ml of water the precipitated 4-hexyloxy-4'-hydroxybiphenyl was filtrated washed with water After drying 29 g of product were obtained An additional amount of product was obtained by refluxing the precipitate collected from the reaction mixture with 45 g of potassium hydroxide in 600 ml of ethanol for 3 hours This mixture was cooled to room temperature the insoluble dihexyloxybiphenyl filtered off The clear filtrate was treated with 200 ml of 6N hydrochloric acid the precipitated 4-hexyloxy-4'-hydroxybiphenyl was filtrated washed with water dried

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

Procedure: A mixture of 74 g (0.40 moles) of biphenol and 20 g (0.50 moles) of sodium hydroxide in 600 ml of ethanol was refluxed for 1 hour. At reflux temperature 66 g (0.40 moles) of 6-bromohexane were added over a period of 1 hour. The reaction mixture was refluxed for 18 hours and cooled to room temperature, and the precipitate was filtrated. The filtrate was treated with 500 ml of water and the precipitated 4-hexyloxy-4'-hydroxybiphenyl was filtrated and washed with water. After drying 29 g of product were obtained. An additional amount of product was obtained by refluxing the precipitate collected from the reaction mixture with 45 g of potassium hydroxide in 600 ml of ethanol for 3 hours. This mixture was cooled to room temperature and the insoluble dihexyloxybiphenyl filtered off. The clear filtrate was treated with 200 ml of 6N hydrochloric acid and the precipitated 4-hexyloxy-4'-hydroxybiphenyl was filtrated, washed with water, and dried. The yield was 19 g. The total yield was 48 g (44% of theory). was refluxed for 1 hour were added over a period of 1 hour The reaction mixture was refluxed for 18 hours the precipitate was filtrated The filtrate was treated with 500 ml of water the precipitated 4-hexyloxy-4'-hydroxybiphenyl was filtrated washed with water After drying 29 g of product were obtained An additional amount of product was obtained by refluxing the precipitate collected from the reaction mixture with 45 g of potassium hydroxide in 600 ml of ethanol for 3 hours This mixture was cooled to room temperature the insoluble dihexyloxybiphenyl filtered off The clear filtrate was treated with 200 ml of 6N hydrochloric acid the precipitated 4-hexyloxy-4'-hydroxybiphenyl was filtrated washed with water dried

Conditions: temp:155.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 12000 ml 4 neck resin head round bottom equipped with a temperature probe, nitrogen purge tube, an overhead stirrer and heating mantel was added 2,2′-biphenol (1415 g, 7.6 moles, 1.0 equivalents), potassium fluoride (11.8 g, 0.2 moles, 0.027 equivalents), ethylene carbonate (1415 g, 16.1 moles, 2.11 equivalents) and heated to 155° C. At 4.5 hours, GC analysis indicated 0% starting material, 0% monoethoxylated and 94% product. Cooled to 80° C., added toluene 5.4 liters, added 2.5 liters deionized water, mixed for 15 min and phase separated. Removed the water and washed again with 2.5 liters deionized water, phase separated, removed the water and distilled solution to remove residual water and approximately 1.8 liters of toluene. The solution was cooled to 50° C. and added cyclohexane 1.8 liters, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy obtained from CIBA Specialty Chemicals under the trade designation Prostab 5198, commonly referred to a 4-hydroxy TEMPO (0.52 g, 0.003 moles, 0.00044 equivalents), phenothiazine (0.52 g, 0.0026 moles, 0.00038 equivalents), acrylic acid (1089.4 g, 15.12 moles, 2.2 equivalents), methane sulfonic acid (36.3 g, 0.38 moles, 0.055 equivalents) and heated to reflux (pot temp was 92-95 C). The flask was equipped with a dean stark trap to collect water. After 18 hours GC analysis indicated 8% monoacrylate intermediate. Added an additional 8 g acrylic acid and continued refluxing for another 6 hours for a total of 24 hours. After 24 hours GC analysis indicated 3% monoacrylate intermediate. The reaction was cooled to 50° C. and treated with 2356 ml 7% sodium carbonate, stirred for 30 min, phase separated, removed aqueous, washed again with 2356 ml DI water, phase separated and removed aqueous. To the (pink-red) toluene/cyclohexane solution was added 4-hydroxy TEMPO (0.52 g, 0.003 moles, 0.00044 equivalents), phenothiazine (0.52 g, 0.0026 moles, 0.00038 equivalents), aluminum n-nitrosophenylhydroxylamine (0.52 g, 0.0012 moles, 0.00017 equivalents) and concentrated with vacuum to approximately 5000 ml solution. Filtered through a pad of celite and the filtrate was concentrated with vacuum with an air purge, at 50° C. and 12 torr vacuum for 3 hours. The resulting yellow to brown oil is further purified by distilling on a roll film evaporator. The conditions for distillation were heating the barrel at 155° C., condenser at 50° C. and 1-5 mtorr. The recovered yield was 2467 g (85% of theoretical) and purity was approximately 90% DEBPDA. purge tube, an overhead stirrer heating mantel Cooled to 80° C. added 2.5 liters mixed for 15 min phase separated Removed the water washed again with 2.5 liters separated removed the water distilled solution to remove residual water and approximately 1.8 liters of toluene The solution was cooled to 50° C. added cyclohexane 1.8 liters, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy heated to reflux (pot temp was 92-95 C) The flask was equipped with a dean stark trap to collect water After 18 hours GC analysis indicated Added an additional 8 g acrylic acid continued refluxing for another 6 hours for a total of 24 hours After 24 hours GC analysis indicated The reaction was cooled to 50° C. treated with 2356 ml 7% sodium carbonate phase separated removed aqueous washed again with 2356 ml DI water, phase separated removed aqueous concentrated with vacuum to approximately 5000 ml solution Filtered through a pad of celite the filtrate was concentrated with vacuum with an air purge, at 50° C. 12 torr vacuum for 3 hours The resulting yellow to brown oil is further purified by distilling on a roll film evaporator The conditions for distillation were heating the barrel at 155° C. at 50° C.

Conditions: temp:155.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 12000 ml 4 neck resin head round bottom equipped with a temperature probe, nitrogen purge tube, an overhead stirrer and heating mantel was added 2,2′-biphenol (1415 g, 7.6 moles, 1.0 equivalents), potassium fluoride (11.8 g, 0.2 moles, 0.027 equivalents), ethylene carbonate (1415 g, 16.1 moles, 2.11 equivalents) and heated to 155° C. At 4.5 hours, GC analysis indicated 0% starting material, 0% monoethoxylated and 94% product. Cooled to 80° C., added toluene 5.4 liters, added 2.5 liters deionized water, mixed for 15 min and phase separated. Removed the water and washed again with 2.5 liters deionized water, phase separated, removed the water and distilled solution to remove residual water and approximately 1.8 liters of toluene. The solution was cooled to 50° C. and added cyclohexane 1.8 liters, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy obtained from CIBA Specialty Chemicals under the trade designation Prostab 5198, commonly referred to a 4-hydroxy TEMPO (0.52 g, 0.003 moles, 0.00044 equivalents), phenothiazine (0.52 g, 0.0026 moles, 0.00038 equivalents), acrylic acid (1089.4 g, 15.12 moles, 2.2 equivalents), methane sulfonic acid (36.3 g, 0.38 moles, 0.055 equivalents) and heated to reflux (pot temp was 92-95 C). The flask was equipped with a dean stark trap to collect water. After 18 hours GC analysis indicated 8% monoacrylate intermediate. Added an additional 8 g acrylic acid and continued refluxing for another 6 hours for a total of 24 hours. After 24 hours GC analysis indicated 3% monoacrylate intermediate. The reaction was cooled to 50° C. and treated with 2356 ml 7% sodium carbonate, stirred for 30 min, phase separated, removed aqueous, washed again with 2356 ml DI water, phase separated and removed aqueous. To the (pink-red) toluene/cyclohexane solution was added 4-hydroxy TEMPO (0.52 g, 0.003 moles, 0.00044 equivalents), phenothiazine (0.52 g, 0.0026 moles, 0.00038 equivalents), aluminum n-nitrosophenylhydroxylamine (0.52 g, 0.0012 moles, 0.00017 equivalents) and concentrated with vacuum to approximately 5000 ml solution. Filtered through a pad of celite and the filtrate was concentrated with vacuum with an air purge, at 50° C. and 12 torr vacuum for 3 hours. The resulting yellow to brown oil is further purified by distilling on a roll film evaporator. The conditions for distillation were heating the barrel at 155° C., condenser at 50° C. and 1-5 mtorr. The recovered yield was 2467 g (85% of theoretical) and purity was approximately 90% DEBPDA. purge tube, an overhead stirrer heating mantel Cooled to 80° C. added 2.5 liters mixed for 15 min phase separated Removed the water washed again with 2.5 liters separated removed the water distilled solution to remove residual water and approximately 1.8 liters of toluene The solution was cooled to 50° C. added cyclohexane 1.8 liters, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy heated to reflux (pot temp was 92-95 C) The flask was equipped with a dean stark trap to collect water After 18 hours GC analysis indicated Added an additional 8 g acrylic acid continued refluxing for another 6 hours for a total of 24 hours After 24 hours GC analysis indicated The reaction was cooled to 50° C. treated with 2356 ml 7% sodium carbonate phase separated removed aqueous washed again with 2356 ml DI water, phase separated removed aqueous concentrated with vacuum to approximately 5000 ml solution Filtered through a pad of celite the filtrate was concentrated with vacuum with an air purge, at 50° C. 12 torr vacuum for 3 hours The resulting yellow to brown oil is further purified by distilling on a roll film evaporator The conditions for distillation were heating the barrel at 155° C. at 50° C.

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

Procedure: To a 250 mL of three-necked bottle was added NaH (content 50%, 3.5 g, 72 mmol), anhydrous THF (60 mL) and anhydrous DMF (20 mL), after the temperature was lowered to 0° C., a solution of biphenol (5.6 g, 30 mmol) in THF (15 mL) was added, stirred at this temperature for 10 minutes. Methoxymethyl chloride (6 mL, 78 mmol) was added dropwise, and the mixture was stirred for 8 h at room temperature, quenched by adding 100 mL of water, extracted with ethyl acetate (100 mL×3), the combined organic phase was washed with brine (60 mL×2), dried over MgSO4, after filtration, the solvent was removed to give a yellow oil. Purification through chromatography give 8 g (97% yield) of the product as a light yellow oil. 1HNMR (300 MHz, CDCl3) δ (ppm) 3.39 (s, 6H), 5.12 (s, 4H), 7.13 (m, 2H), 7.30–7.37 (m, 6H). Physical data of the compound was consistent with that reported in literature. was lowered to 0° C. the mixture was stirred for 8 h at room temperature quenched by adding 100 mL of water extracted with ethyl acetate (100 mL×3) the combined organic phase was washed with brine (60 mL×2) dried over MgSO4 after filtration the solvent was removed to give a yellow oil Purification through chromatography

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

Procedure: 2′-Ethoxyl-1,1′-biphenyl-2-ol was prepared by modifying the procedure reported in J. Org. Chem. 1981, 46, 4988. In 50 mL of acetone was added 10 g of 2,2′-biphenol and 9.4 g of potassium carbonate. After stirring at room temperature for one hour, a solution of iodoethane (9.2 g in 10 mL of acetone) was added slowly dropwise. The mixture was filtered, washed with acetone, and solvent removed by rotary evaporation. The residue was flashed chromatographed to give 5.1 g of the2′-ethoxyl-1,1′-biphenyl-2-ol as a colorless oil. 1H NMR (C6D6): 7.20 (m, 3H), 7.10 (m, 1H), 7.05 (m, 1H), 6.85 (m, 2H), 6.55 (m, 1H), 3.38 (q, 2H), 0.81 (t, 3H). The mixture was filtered washed with acetone, and solvent removed by rotary evaporation The residue was flashed chromatographed

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

Procedure: A solution of 2,2′-biphenol (28.1 g, 0.151 mol) in 49 mL phosphorus trichloride was heated at reflux for 2 hours. The excess PCl3 was removed by distillation. The residue was purified by vacuum distillation (140-143° C. at 0.5 mm Hg) to give 30.70 g (81% yield) 1,1′-biphenyl-2,2′-diyl phosphorochloridite (as a clear viscous oil which solidified to a white solid upon standing at room temperature in an inert atmosphere for an extended period of time). 31P{1H}NMR (121.4 MHz, d8-toluene): δ 180.1 (s), 85% H3PO4 external reference. To a solution containing 1.018 g (2.84 mmoles) of 2,2′-dihydroxy-3,3′-di-t-butyl-5,5′-dimethoxy-1,1′-biphenyl and 0.575 g (5.68 mmoles) of NEt3 in 15 ml of tetrahydrofuran (THF) was added 1.412 g (5.68 mmoles) of 1,1′-biphenyl-2,2′-diyl phosphorochloridite in 5 ml of THF. The mixture was stirred overnight at room temperature. The mixture was filtered through celite, washed with THF and solvent removed to give 2.2 g of white solid. 31P{1H} nmr (121.4 MHz, C6D6): 145.15 s and 138.5 s. 1H nmr (300 MHz, C6D6): singlet at 3.15 and 1.3 along with aromatic resonances. at reflux for 2 hours The excess PCl3 was removed by distillation The residue was purified by vacuum distillation (140-143° C. at 0.5 mm Hg)

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

Procedure: A solution of 2,2′-biphenol (28.1 g, 0.151 mol) in 49 mL phosphorus trichloride was heated at reflux for 2 hours. The excess PCl3 was removed by distillation. The residue was purified by vacuum distillation (140-143° C. at 0.5 mm Hg) to give 30.70 g (81% yield) 1,1′-biphenyl-2,2′-diyl phosphorochloridite (as a clear viscous oil which solidified to a white solid upon standing at room temperature in an inert atmosphere for an extended period of time). 31P{1H}NMR (121.4 MHz, d8-toluene): δ 180.1 (s), 85% H3PO4 external reference. To a solution containing 1.018 g (2.84 mmoles) of 2,2′-dihydroxy-3,3′-di-t-butyl-5,5′-dimethoxy-1,1′-biphenyl and 0.575 g (5.68 mmoles) of NEt3 in 15 ml of tetrahydrofuran (THF) was added 1.412 g (5.68 mmoles) of 1,1′-biphenyl-2,2′-diyl phosphorochloridite in 5 ml of THF. The mixture was stirred overnight at room temperature. The mixture was filtered through celite, washed with THF and solvent removed to give 2.2 g of white solid. 31P{1H} nmr (121.4 MHz, C6D6): 145.15 s and 138.5 s. 1H nmr (300 MHz, C6D6): singlet at 3.15 and 1.3 along with aromatic resonances. at reflux for 2 hours The excess PCl3 was removed by distillation The residue was purified by vacuum distillation (140-143° C. at 0.5 mm Hg)

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

Procedure: To a round-bottom flask is charged biphenyl-2,2′-diol (7.45 g, 40 mmol) and pyridine (50 mL). The flask is immersed in an ice-water bath and ethyl chloroformate (9.48 mL, 100 mmol) is added dropwise. After gradually warming to room temperature, the mixture is stirred overnight. The volatiles are removed in vacuo, and the residue is suspended in 100 mL of ethyl acetate. After filtration, the filtrate is concentrated and purified by flash chromatography. The product is obtained as a colorless oil. Yield: 5.0 g; 1H NMR (500 MHz, CDCl3, ppm) δ 7.23-7.44 (m, 8H), 4.13 (q, 4H), 1.19 (t, 6H). The flask is immersed in an ice-water bath The volatiles are removed in vacuo After filtration the filtrate is concentrated purified by flash chromatography The product is obtained as a colorless oil

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

Procedure: To biphenol (0.5 mole) and 200 milliliters of absolute ethanol and sodium hydroxide (1.1 millimole) at 80° C. was added dropwise a solution of 2-chloroethanol (1 mole) in 50 milliliters of absolute ethanol. The mixture was refluxed for 48 hours, and then filtered hot and washed twice with boiling ethanol (100 milliliters). Recrystallization from boiling water provided the precursor product biphenol-diethanol, 80 to 85 percent yield of colorless crystals. The melting point for this product was 210 to 211° C. The mixture was refluxed for 48 hours filtered hot washed twice with boiling ethanol (100 milliliters) Recrystallization

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

Procedure: To biphenol (0.5 mole) and 200 milliliters of absolute ethanol and sodium hydroxide (1.1 millimole) at 80° C. was added dropwise a solution of 2-chloroethanol (1 mole) in 50 milliliters of absolute ethanol. The mixture was refluxed for 48 hours, and then filtered hot and washed twice with boiling ethanol (100 milliliters). Recrystallization from boiling water provided the precursor product biphenol-diethanol, 80 to 85 percent yield of colorless crystals. The melting point for this product was 210 to 211° C. The mixture was refluxed for 48 hours filtered hot washed twice with boiling ethanol (100 milliliters) Recrystallization