4-ethylbenzene-1,3-diol

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

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

Procedure: In a three necked round bottom flask (equipped with a condenser, additional funnel and mechanical stirrer) was added the catalyst or combination of the catalysts. 100 ml of a mixture of 50:50 ethanol:water was added and the reaction was heated to reflux conditions. 2,4-dihydroxy acetophenone in 100 ml of water:ethanol mixture with or without acids was placed in the additional funnel and was added to the mixture (dropwise-2-4 hrs). The reaction was filtered through a milipore filter and concentrated in vacuo to give a solid. This solid was crystalized from 1,2-dichloroethane to give 4-ethyl resorcinol. The unreacted 2,4-dihydroxy acetophenone is recovered from the media and recycled. The structure of 4-ethyl resorcinol and 2,4-dihydroxy acetophenone were characterized by NMR, Gas Chromatography, IR and Mass spectroscopy In a three necked round bottom flask (equipped with a condenser, additional funnel and mechanical stirrer) was added the catalyst or combination of the catalysts the reaction was heated to reflux conditions was added to the mixture (dropwise-2-4 hrs) The reaction was filtered through a milipore filter concentrated in vacuo to give a solid This solid was crystalized from 1,2-dichloroethane

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

Procedure: In a three necked round bottom flask (equipped with a condensor, additional funnel and mechanical stirrer) was added 15.2 g of a combination of Raney Nickel and Ni supported on silica. (50:50). 100 ml of a mixture of 50:50 ethanol:water was added and the reaction was heated at reflux conditions. 15.2 g of 2,4-dihydroxy acetophenone in 100 ml of water:ethanol and 10 ml of acetic acid was placed in the additional funnel and slowly added to the mixture (dropwise). The reaction was filtered through a milipore filter to give a pale yellow solution. Concentration of this solution in vacuo gave a solid. This solid was crystalized from 1,2-dichloroethane to give 4-ethyl resorcinol in 80% isolated yield. The unreacted 2,4-dihydroxy acetophenone was recovered (−17%) form the reaction mixture and was recycled. The structure of 4-ethyl resorcinol and 2,4-dihydroxy acetophenone were characterized by NMR, Gas Chromatography, IR and Mass spectroscopy In a three necked round bottom flask (equipped with a condensor, additional funnel and mechanical stirrer) the reaction was heated at reflux conditions slowly added to the mixture (dropwise) The reaction was filtered through a milipore filter to give a pale yellow solution Concentration of this solution in vacuo gave a solid This solid was crystalized from 1,2-dichloroethane

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

Procedure: In a three necked round bottom flask (equipped with a condensor, additional funnel and mechanical stirrer) was added 15.2 g of a combination of Raney Nickel and Ni supported on silica. (50:50). 100 ml of a mixture of 50:50 ethanol:water was added and the reaction was heated at reflux conditions. 15.2 g of 2,4-dihydroxy acetophenone in 100 ml of water:ethanol and 10 ml of acetic acid was placed in the additional funnel and slowly added to the mixture (dropwise). The reaction was filtered through a milipore filter to give a pale yellow solution. Concentration of this solution in vacuo gave a solid. This solid was crystalized from 1,2-dichloroethane to give 4-ethyl resorcinol in 80% isolated yield. The unreacted 2,4-dihydroxy acetophenone was recovered (−17%) form the reaction mixture and was recycled. The structure of 4-ethyl resorcinol and 2,4-dihydroxy acetophenone were characterized by NMR, Gas Chromatography, IR and Mass spectroscopy In a three necked round bottom flask (equipped with a condensor, additional funnel and mechanical stirrer) the reaction was heated at reflux conditions slowly added to the mixture (dropwise) The reaction was filtered through a milipore filter to give a pale yellow solution Concentration of this solution in vacuo gave a solid This solid was crystalized from 1,2-dichloroethane

Conditions: temp:72.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,4-Dihydroxy acetophenone (76 g, 0.5 mole) was charged in a 1 liter autoclave reactor along with methanol (300 ml), acetic acid (5 ml), and Raney Nickel (15.2 g washed several times with water and water/methanol) and 750 mg of Pd/C. The pH of the system was 5.0. The autoclave was checked for leaks with nitrogen. The autoclave was pressurized to 500 psi with hydrogen and stirred at 70-75° C. up to 8 hrs. During this time 97% of the theoretical value for hydrogen was consumed. The reaction was vented and the contents were filtered through a milipore filter to give a yellow solution. Concentration of this solution in vacuo gave a solid. This solid was crystalized from 1,2-dichloroethane to give 4-ethyl resorcinol in 85% isolated yield. The unreacted 2,4-dihydroxy acetophenone was recovered (−13%) from the reaction mixture and was recycled. The structure of 4-ethyl resorcinol and 2,4-dihydroxy acetophenone were characterized by NMR (see FIG. 1), Gas Chromatography (see FIG. 2), IR (See FIG. 3) and Mass spectroscopy. The mass spectroscopy indicated that the mass was 138. During this time 97% of the theoretical value for hydrogen was consumed the contents were filtered through a milipore filter to give a yellow solution Concentration of this solution in vacuo gave a solid This solid was crystalized from 1,2-dichloroethane

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,4-dihydroxy acetophenone (76 g, 0.5 mole) was charged in a 1 liter autoclave reactor along with methanol (300 ml), and Raney Nickel (15.2 g—washed several times with water and water/methanol to a pH of 7.0) and 750 mg of Pd/C. The autoclave was checked for leaks with 100-200 psi of nitrogen. The autoclave was pressurized to 300 psi with hydrogen and stirred at 70° C. for 8 hrs. During this time 95% of the theoretical value for hydrogen was consumed. The reaction was vented and the contents were filtered through a milipore filter to give a light yellow solution. Concentration of this solution in vacuo gave a solid. This solid was crystalized from 1,2-dichloroethane to give 4-ethyl resorcinol in 70% isolated yield. The unreacted 2,4-dihydroxy acetophenone was recovered (˜27%) from the reaction mixture and was recycled. The structure of 4-ethyl resorcinol was characterized by using the NMR, Gas Chromatography, IR and Mass spectroscopy. washed several times with water and water/methanol to a pH of 7.0) and 750 mg of Pd/C During this time 95% of the theoretical value for hydrogen was consumed the contents were filtered through a milipore filter to give a light yellow solution Concentration of this solution in vacuo gave a solid This solid was crystalized from 1,2-dichloroethane

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

Procedure: A solution of tetrabutyl ammonium tribromide (15.4 g, 31.8 mmol) in CHCl3 (100 mL) was added to a stirred solution of 4-ethyl resorcinol (4 g, 29 mmol) dissolved in CHCl3 (50 mL). The reaction mixture was stirred for 2 hours and then quenched with 5% solution of sodium thiosulfate (30 mL). The biphasic mixture was stirred for 30 mins and then the layers were separated. The organic layer was washed with 1 N HCl, brine, dried over Na2SO4 and concentrated to yellow oil. The oil was dissolved in DMF (60 mL) and treated with K2CO3 (12.7 g, 92 mmol), followed by methyl iodie (2.9 mL, 46 mmol). The mixture was stirred for 15 hours and then partitioned between H2O and EtOAc. The organic layers were washed with 1 N HCl, brine, dried over Na2SO4 and concentrated to a dark red oil. Purification by flash column chromatography (0% to 10% EtOAc in hexanes) gave the product as a yellow oil (2.8 g, 39%). 1H NMR (400 MHz, CDCl3): δ 1.15 (t, J=7.6 Hz, 3 H), 2.54 (q, J=7.6 Hz, 2 H), 3.83 (s, 3 H), 3.89 (s, 3 H), 6.46 (s, 1 H), 7.26 (s, 1 H). quenched with 5% solution of sodium thiosulfate (30 mL) The biphasic mixture was stirred for 30 mins the layers were separated The organic layer was washed with 1 N HCl, brine dried over Na2SO4 concentrated to yellow oil The oil was dissolved in DMF (60 mL) The mixture was stirred for 15 hours partitioned between H2O and EtOAc The organic layers were washed with 1 N HCl, brine dried over Na2SO4 concentrated to a dark red oil Purification by flash column chromatography (0% to 10% EtOAc in hexanes)

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

Procedure: 4-Ethylresorcinol (10 g, 73 mmol) was dissolved in acetone (250 mL), and potassium carbonate (30 g, 220 mmol) and allyl bromide (15 mL, 170 mmol) were added thereto and heated under reflux for 4 hours. The reaction mixture was cooled to room temperature, then filtered through Celite, and the filtrate was concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography (ethyl acetate/n-hexane=1/9) to obtain 2,4-bis(allyloxy)-1-ethylbenzene (15 g, 95%). heated under reflux for 4 hours filtered through Celite the filtrate was concentrated under reduced pressure The resulting residue was purified through silica gel column chromatography (ethyl acetate/n-hexane=1/9)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a tetrahydrofuran solution (10 ml) of 4-ethylresorcinol (691 mg), sodium hydride (60% dispersion in liquid paraffin) (440 mg) was added and stirred at 0° C. for 30 minutes. Then, diethyl chlorophosphate (1.73 ml) was added dropwise. After stirring at room temperature for 3 hours, water (10 ml) was added to the reaction mixture, and the extraction was carried out with ethyl acetate (30 ml). Then, the extract was washed with saturated brine (10 ml), dried with anhydrous sodium sulfate and then concentrated. The residue (2.43 g) was subjected to silica gel chromatography (silica gel 40 g, chloroform to chloroform:methanol=10:1), to give the title compound (2.05 g, yield: 100%) as a pale yellow oil. After stirring at room temperature for 3 hours the extraction Then, the extract was washed with saturated brine (10 ml) dried with anhydrous sodium sulfate concentrated

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a tetrahydrofuran solution (10 ml) of 4-ethylresorcinol (691 mg), sodium hydride (60% dispersion in liquid paraffin) (440 mg) was added and stirred at 0° C. for 30 minutes. Then, diethyl chlorophosphate (1.73 ml) was added dropwise. After stirring at room temperature for 3 hours, water (10 ml) was added to the reaction mixture, and the extraction was carried out with ethyl acetate (30 ml). Then, the extract was washed with saturated brine (10 ml), dried with anhydrous sodium sulfate and then concentrated. The residue (2.43 g) was subjected to silica gel chromatography (silica gel 40 g, chloroform to chloroform:methanol=10:1), to give the title compound (2.05 g, yield: 100%) as a pale yellow oil. After stirring at room temperature for 3 hours the extraction Then, the extract was washed with saturated brine (10 ml) dried with anhydrous sodium sulfate concentrated

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a tetrahydrofuran solution (10 ml) of 4-ethylresorcinol (423 mg), sodium hydride (60% dispersion in liquid paraffin) (269 mg) was added and stirred at 0° C. for 30 minutes. Then, dibenzyl chlorophosphate (10 w/v % solution in benzene) (20 ml) was added dropwise. After stirring at room temperature for 3 hours, water (10 ml) was added to the reaction mixture, and the extraction was carried out with ethyl acetate (30 ml). Then, the extract was washed with saturated brine (10 ml), dried with anhydrous sodium sulfate and then concentrated. The residue (2.16 g) was subjected to silica gel chromatography (silica gel 60 g, chloroform to chloroform:methanol=50:1), to give 1,3-bis(dibenzylphosphonooxy)-4-ethylbenzene (1.65 g, yield: 84%) as a yellow liquid. After stirring at room temperature for 3 hours the extraction Then, the extract was washed with saturated brine (10 ml) dried with anhydrous sodium sulfate concentrated

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

Procedure: To a mixture of 4-ethyl-benzene-1,3-diol (a, 10 mmol) and naphthalen-2-yl-acetonitrile (b, 10 mmol) in boron trifluoride etherate (20 mL) was bubbled gaseous HCl for 12 h. The solids that formed were collected by filtration and heated in 6N HCl (100 mL) and EtOH (20 mL) for 6 h. The mixture was diluted with water and extracted with CH2Cl2. The organic extract was washed with water and dried. The oil obtained on concentration of the organic layer was crystallized in EtOAc/hexanes to give 1-(5-ethyl-2,4-dihydroxy-phenyl)-2-naphthalen-2-yl-ethanone (c, 0.74 g). was bubbled gaseous HCl for 12 h The solids that formed were collected by filtration heated in 6N HCl (100 mL) The mixture was diluted with water extracted with CH2Cl2 The organic extract was washed with water dried The oil obtained on concentration of the organic layer was crystallized in EtOAc/hexanes