1-(2-bromoethoxy)-2-[2-(2-bromoethoxy)ethoxy]ethane

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

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

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 3.08 g of 4-(4-acetyl-3-hydroxy-2-propylphenoxy)butanoic acid ethyl ester, 16.0 of 1,11-dibromo-3,6,9-trioxaundecane and 2.8 g of anhydrous potassium carbonate in 75 ml of anhydrous acetone was stirred at reflux for 5 days. During this period, 1.0 g portions of potassium carbonate were added after 18 hours and after 25 hours. The reaction mixture was filtered and the filtrate was concentrated in vacuo to an oil (20 g) which was chromatographed on 200 g of silica gel using 10% ethyl acetatetoluene to give 3.24 g (59% yield) of 4-[4-acetyl-3-[2-[2-[2-(2-bromoethoxy)ethoxy]ethoxy]ethoxy]-2-propylphenoxy]butanoic acid ethyl ester as an oil. at reflux for 5 days During this period The reaction mixture was filtered the filtrate was concentrated in vacuo to an oil (20 g) which was chromatographed on 200 g of silica gel using 10% ethyl acetatetoluene

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

Procedure: A mixture of 2.8 g (0.01 mole) of (4-acetyl-3-hydroxy-2-propylphenoxy)acetic acid ethyl ester, 11.0 g (0.034 mole) of 1,11-dibromo-3,6,9-trioxaundecane and 2.8 g (0.02 mole) of anhydrous potassium carbonate in 60 ml of anhydrous acetone and 30 ml of anhydrous dimethylformamide was stirred at reflux for 16 hours. An additional 1.4 g of potassium carbonate was added and reflux was continued for 24 hours. The solvents were removed in vacuo and the residue was chromatographed on 200 g of silica gel. Elution with 10% ethyl acetate-toluene gave 3.2 g (62% yield) of [4-acetyl-3-[2-[2-[2-(2-bromoethoxy)ethoxy]ethoxy]ethoxy]-2-propylphenoxy]acetic acid ethyl ester as an oil. at reflux for 16 hours reflux The solvents were removed in vacuo the residue was chromatographed on 200 g of silica gel Elution with 10% ethyl acetate-toluene

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

Procedure: A mixture of 2.8 g (0.01 mole) of (4-acetyl-3-hydroxy-2-propylphenoxy)acetic acid ethyl ester, 11.0 g (0.034 mole) of 1,11-dibromo-3,6,9-trioxaundecane and 2.8 g (0.02 mole) of anhydrous potassium carbonate in 60 ml of anhydrous acetone and 30 ml of anhydrous dimethylformamide was stirred at reflux for 16 hours. An additional 1.4 g of potassium carbonate was added and reflux was continued for 24 hours. The solvents were removed in vacuo and the residue was chromatographed on 200 g of silica gel. Elution with 10% ethyl acetate-toluene gave 3.2 g (62% yield) of [4-acetyl-3-[2-[2-[2-(2-bromoethoxy)ethoxy]ethoxy]ethoxy]-2-propylphenoxy]acetic acid ethyl ester as an oil. at reflux for 16 hours reflux The solvents were removed in vacuo the residue was chromatographed on 200 g of silica gel Elution with 10% ethyl acetate-toluene

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

Procedure: A mixture of 3.08 g of 4-(4-acetyl-3-hydroxy-2-propylphenoxy)butanoic acid ethyl ester, 16.0 g of 1,11-dibromo-3,6,9-trioxaundecane and 2.8 g of anhydrous potassium carbonate in 75 ml of anhydrous acetone was stirred at reflux for 5 days. During this period, 1.0 g portions of potassium carbonate were added after 18 hours and after 25 hours. The reaction mixture was filtered and the filtrate was concentrated in vacuo to an oil (20 g) which was chromatographed on 200 g of silica gel using 10% ethyl acetatetoluene to give 3.24 g (59% yield) of 4-[4-acetyl-3-[2-[2-[2-(2-bromoethoxy)ethoxy]ethoxy]ethoxy]-2-propylphenoxy]butanoic acid ethyl ester as an oil. at reflux for 5 days During this period The reaction mixture was filtered the filtrate was concentrated in vacuo to an oil (20 g) which was chromatographed on 200 g of silica gel using 10% ethyl acetatetoluene

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

Procedure: A mixture of 2.8 g (0.01 mole) of (4-acetyl-3-hydroxy-2-propylphenoxy)acetic acid ethyl ester, 11.0 g (0.034 mole) of 1,11-dibromo-3,6,9-trioxaundecane and 2.8 g (0.02 mole) of anhydrous potassium carbonate in 60 ml of anhydrous acetone and 30 ml of anhydrous dimethylformamide was stirred at reflux for 16 hours. An additional 1.4 g of potassium carbonate was added and reflux was continued for 24 hours. The solvents were removed in vacuo and the residue was chromatographed on 200 g of silica gel. Elution with 10% ethyl acetate-toluene gave 3.2 g (62% yield) of [4-acetyl-3-[2-[2-[2-(2-bromoethoxy)ethoxy]ethoxy]ethoxy]-2-propylphenoxy]acetic acid ethyl ester as an oil. at reflux for 16 hours reflux The solvents were removed in vacuo the residue was chromatographed on 200 g of silica gel Elution with 10% ethyl acetate-toluene

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

Procedure: Under an argon atmosphere, 2 g of [(8-acetyl-7-hydroxy-2-naphthalenyl)oxy]acetic acid methyl ester was added to a suspension of 0.32 g of 60% sodium hydride in 30 ml of anhydrous dimethylformamide. The mixture was stirred at room temperature for 40 minutes and then 11.6 g of bis[2-[2-bromoethoxy)ethyl]ether was added and the mixture was stirred at room temperature for 20 hours. The resulting dark mixture was concentrated in vacuo to an oil which was dissolved in methylene chloride, washed with water and concentrated to give an oil. Purification by high pressure liquid chromatography (35% ethyl acetate-toluene) gave 3.0 g (80%) of [[8-acetyl-7-[2-[2-[2-(2-bromoethoxy)ethoxy]ethoxy]ethoxy]-2-naphthalenyl]oxy]acetic acid methyl ester as an oil. the mixture was stirred at room temperature for 20 hours The resulting dark mixture was concentrated in vacuo to an oil which was dissolved in methylene chloride washed with water concentrated to give an oil Purification by high pressure liquid chromatography (35% ethyl acetate-toluene)

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

Procedure: To a solution of 5-hydroxy-4-(2-methoxyethoxy)-2-nitrobenzonitrile (0.4 g) in DMF (8 mL) was added 1-bromo-2-(2-(2-(2-bromoethoxy)ethoxy)ethoxy)ethane (1.0 g) and K2CO3 (0.5 g). The resulting mixture was heated at 80° C. overnight under N2 atmospheres. After reaction finished, the mixture was diluted with water (50 mL) and exacted with EA (3×50 mL). The combined organic layer was dried over Na2SO4, concentrated under reduced pressure, and purification by silica chromatography to give 0.2 g of 5-(2-(2-(2-(2-bromoethoxy)ethoxy)ethoxy)ethoxy)-4-(2-methoxyethoxy)-2-nitrobenzonitrile. 1H-NMR (400 MHz, CDCl3): δ: 7.85 (s, 1H), 7.33 (s, 1H), 4.33-4.28 (m, 4H), 3.95-3.92 (m, 2H), 3.83-3.79 (m, 4H), 3.74-3.72 (m, 2H), 3.69-3.66 (m, 6H), 3.49-3.47 (m, 2H), 3.45 (s, 3H). After reaction The combined organic layer was dried over Na2SO4 concentrated under reduced pressure, and purification by silica chromatography

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

Procedure: To a solution of 5-hydroxy-4-(2-methoxyethoxy)-2-nitrobenzonitrile (0.42 g) in DMF (5 mL) was added 1-bromo-2-(2-(2-(2-bromoethoxy)ethoxy)ethoxy)ethane (0.26 g) and K2CO3 (0.5 g). The resulting mixture was heated at 80° C. overnight under N2 atmospheres. After reaction finished, the mixture was diluted with water (50 mL) and exacted with EA (3×50 mL). The combined organic layer was dried over Na2SO4, concentrated under reduced pressure, and purification by silica chromatography to give 0.25 g of 5,5′-((((oxybis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl))-bis(oxy))bis(4-(2-methoxyethoxy)-2-nitrobenzonitrile). 1H-NMR (400 MHz, CDCl3): δ: 7.84 (s, 2H), 7.35 (s, 2H), 4.33-4.28 (m, 8H), 3.92-3.90 (m, 4H), 3.83-3.81 (m, 4H), 3.73-3.70 (m, 4H), 3.68-3.65 (m, 4H), 3.45 (s, 6H). After reaction The combined organic layer was dried over Na2SO4 concentrated under reduced pressure, and purification by silica chromatography