5-(hydroxymethyl)benzene-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: A 250 ml flask is charged with 15 g (34.5 mmol, 2.2 eq) of bromide (2) and acetone (100 ml) under an argon atmosphere. To this solution is added 3,5-dihydroxybenzyl alcohol (2.2 g, 15.7 mmol), 0.82 g (31. mmol, 0.2 eq) 18-C-6 and 4.77 g (34-5 mmol, 2.2 eq) of K2CO3 and the mixture is stirred for 48 hours whereupon a yellow suspension is formed. To the mixture is added methylene chloride (200 ml) and water (200 ml). The organic phase is separated, dried over MgSO4 and evaporated to dryness. A dark brown oil is obtained which is dissolved in toluene (40 ml) and hexane (20 ml). Upon cooling, a white powder forms which is collected by filtration to give 10.92 g (81.9% of (3A). is formed The organic phase is separated dried over MgSO4 evaporated to dryness A dark brown oil is obtained which Upon cooling a white powder forms which is collected by filtration

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 250 ml flask is charged with 15 g (34.5 mmol, 2.2 eq) of bromide (2) and acetone (100 ml) under an argon atmosphere. To this solution is added 3,5-dihydroxybenzyl alcohol (2.2 g, 15.7 mmol), 0.82 g (31. mmol, 0.2 eq) 18-C-6 and 4.77 g (34-5 mmol, 2.2 eq) of K2CO3 and the mixture is stirred for 48 hours whereupon a yellow suspension is formed. To the mixture is added methylene chloride (200 ml) and water (200 ml). The organic phase is separated, dried over MgSO4 and evaporated to dryness. A dark brown oil is obtained which is dissolved in toluene (40 ml) and hexane (20 ml). Upon cooling, a white powder forms which is collected by filtration to give 10.92 g (81.9% of (3A). is formed The organic phase is separated dried over MgSO4 evaporated to dryness A dark brown oil is obtained which Upon cooling a white powder forms which is collected by filtration

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

Procedure: A 250 ml flask is charged with 15 g (34.5 mmol, 2.2 eq) of bromide (2) and acetone (100 ml) under an argon atmosphere. To this solution is added 3,5-dihydroxybenzyl alcohol (2.2 g, 15.7 mmol), 0.82 g (31. mmol, 0.2 eq) 18-C-6 and 4.77 g (34-5 mmol, 2.2 eq) of K2CO3 and the mixture is stirred for 48 hours whereupon a yellow suspension is formed. To the mixture is added methylene chloride (200 ml) and water (200 ml). The organic phase is separated, dried over MgSO4 and evaporated to dryness. A dark brown oil is obtained which is dissolved in toluene (40 ml) and hexane (20 ml). Upon cooling, a white powder forms which is collected by filtration to give 10.92 g (81.9% of (3A). is formed The organic phase is separated dried over MgSO4 evaporated to dryness A dark brown oil is obtained which Upon cooling a white powder forms which is collected by filtration

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

Procedure: A 250 ml flask is charged with 15 g (34.5 mmol, 2.2 eq) of bromide (2) and acetone (100 ml) under an argon atmosphere. To this solution is added 3,5-dihydroxybenzyl alcohol (2.2 g, 15.7 mmol), 0.82 g (31.0 mmol, 0.2 eq) 18-C-6 and 4.77 g (34-5 mmol, 2.2 eq) of K2CO3 and the mixture is stirred for 48 hours whereupon a yellow suspension is formed. To the mixture is added methylene chloride (200 ml) and water (200 ml). The organic phase is separated, dried over MgSO4 and evaporated to dryness. A dark brown oil is obtained which is dissolved in toluene (40 ml) and hexane (20 ml). Upon cooling, a white powder forms which is collected by filtration to give 10.92 g (81.9% of (3A). is formed The organic phase is separated dried over MgSO4 evaporated to dryness A dark brown oil is obtained which Upon cooling a white powder forms which is collected by filtration

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

Procedure: A 250 ml flask is charged with 15 g (34.5 mmol, 2.2 eq) of bromide (2) and acetone (100 ml) under an argon atmosphere. To this solution is added 3,5-dihydroxybenzyl alcohol (2.2 g, 15.7 mmol), 0.82 g (31.0 mmol, 0.2 eq) 18-C-6 and 4.77 g (34-5 mmol, 2.2 eq) of K2CO3 and the mixture is stirred for 48 hours whereupon a yellow suspension is formed. To the mixture is added methylene chloride (200 ml) and water (200 ml). The organic phase is separated, dried over MgSO4 and evaporated to dryness. A dark brown oil is obtained which is dissolved in toluene (40 ml) and hexane (20 ml). Upon cooling, a white powder forms which is collected by filtration to give 10.92 g (81.9% of (3A). is formed The organic phase is separated dried over MgSO4 evaporated to dryness A dark brown oil is obtained which Upon cooling a white powder forms which is collected by filtration

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

Procedure: Synthesis of monomers was achieved from 3,5-dihydroxybenzoic acid or 3,5-dihydroxybenzyl alcohol as shown in above scheme. Commercially available 3,5-dihydroxybenzoic acid 1 was dissolved in ethanol along with catalytic amount of concentrated sulfuric acid and refluxed for 12 h to obtain ethyl-3,5-dihydroxybenzoate 1a. The ester 1a was then treated with one equivalent of alkyl halide to afford the mono alkylated ester 3 and 4. The yield of this reaction was rather low, because of the disubstituted byproduct obtained in the reaction along with the product as a statistical mixture. Compounds 3 and 4 were then reduced using LiAlH4 in dry THF under ambient temperature to give the monoalkylated phenols 3a and 4a. Compounds 2a and 5a were prepared by the reaction of 3,5-dihydroxybenzyl alcohol with 1 equivalent of alkyl halide under alkylation conditions. The phenols 2a-5a were then treated with tert-butylbromoacetate and sodium iodide to give compounds 2b-5b, which upon oxidation by PCC afforded the corresponding aldehydes 2c-5c. Treatment of aldehydes with methyl triphenylphosphonium bromide and potassium tert-butoxide under THF afforded the monomers 2d-5d. Polymers 2e-5e (n>1) was synthesized by nitroxide mediated living polymerization, using unimolecular intiator. The polymers were then hydrolyzed using potassium hydroxide as the base to afford carboxylic acid polymers 2f-5f. Synthesis of monomers refluxed for 12 h

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

Procedure: Synthesis of monomers was achieved from 3,5-dihydroxybenzoic acid or 3,5-dihydroxybenzyl alcohol as shown in above scheme. Commercially available 3,5-dihydroxybenzoic acid 1 was dissolved in ethanol along with catalytic amount of concentrated sulfuric acid and refluxed for 12 h to obtain ethyl-3,5-dihydroxybenzoate 1a. The ester 1a was then treated with one equivalent of alkyl halide to afford the mono alkylated ester 3 and 4. The yield of this reaction was rather low, because of the disubstituted byproduct obtained in the reaction along with the product as a statistical mixture. Compounds 3 and 4 were then reduced using LiAlH4 in dry THF under ambient temperature to give the monoalkylated phenols 3a and 4a. Compounds 2a and 5a were prepared by the reaction of 3,5-dihydroxybenzyl alcohol with 1 equivalent of alkyl halide under alkylation conditions. The phenols 2a-5a were then treated with tert-butylbromoacetate and sodium iodide to give compounds 2b-5b, which upon oxidation by PCC afforded the corresponding aldehydes 2c-5c. Treatment of aldehydes with methyl triphenylphosphonium bromide and potassium tert-butoxide under THF afforded the monomers 2d-5d. Polymers 2e-5e (n>1) was synthesized by nitroxide mediated living polymerization, using unimolecular intiator. The polymers were then hydrolyzed using potassium hydroxide as the base to afford carboxylic acid polymers 2f-5f. Synthesis of monomers refluxed for 12 h

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

Procedure: Synthesis of monomers was achieved from 3,5-dihydroxybenzoic acid or 3,5-dihydroxybenzyl alcohol as shown in above scheme. Commercially available 3,5-dihydroxybenzoic acid 1 was dissolved in ethanol along with catalytic amount of concentrated sulfuric acid and refluxed for 12 h to obtain ethyl-3,5-dihydroxybenzoate 1a. The ester 1a was then treated with one equivalent of alkyl halide to afford the mono alkylated ester 3 and 4. The yield of this reaction was rather low, because of the disubstituted byproduct obtained in the reaction along with the product as a statistical mixture. Compounds 3 and 4 were then reduced using LiAlH4 in dry THF under ambient temperature to give the monoalkylated phenols 3a and 4a. Compounds 2a and 5a were prepared by the reaction of 3,5-dihydroxybenzyl alcohol with 1 equivalent of alkyl halide under alkylation conditions. The phenols 2a-5a were then treated with tert-butylbromoacetate and sodium iodide to give compounds 2b-5b, which upon oxidation by PCC afforded the corresponding aldehydes 2c-5c. Treatment of aldehydes with methyl triphenylphosphonium bromide and potassium tert-butoxide under THF afforded the monomers 2d-5d. Polymers 2e-5e (n>1) was synthesized by nitroxide mediated living polymerization, using unimolecular intiator. The polymers were then hydrolyzed using potassium hydroxide as the base to afford carboxylic acid polymers 2f-5f. Synthesis of monomers refluxed for 12 h

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

Procedure: Finely powdered K2CO3 (14 g, 0.10 mol), and KI (17 g, 0.10 mol) were stirred in acetone (200 mL) under a nitrogen atmosphere. 3,5-Dihydroxybenzyl alcohol (4.2 g, 0.030 mol), and propargyl chloride (5.3 g, 0.071 mol) were added and mixture was allowed to reflux overnight. After the solution was filtered, and evaporated down to dryness, the residue was diluted with DCM, worked up and the solvents were removed in vacuo leaving a yellow oil, which solidified upon standing to give 6.3 g in 97% yield. to reflux overnight After the solution was filtered evaporated down to dryness the residue was diluted with DCM the solvents were removed in vacuo leaving a yellow oil, which to give 6.3 g in 97% yield