[5-(hydroxymethyl)oxolan-2-yl]methanol

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

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

Procedure: 34.0 g (261 mmol) of 2,5-bis(hydroxymethyl)tetrahydrofuran are dissolved in 260 ml of dichloromethane. A solution of 99.0 g (521 mmol) of p-toluenesulfonyl chloride in 52 ml of pyridine and 130 ml of dichloromethane is added dropwise thereto. After stirring at room temperature for 24 hours, the precipitate is filtered off with suction and washed with dichloromethane. The filtrate and the washing phases are combined, washed with dilute hydrochloric acid and then with saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate and evaporated to dryness. The crude product is recrystallized from ethanol. the precipitate is filtered off with suction washed with dichloromethane washed with dilute hydrochloric acid with saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate evaporated to dryness The crude product is recrystallized from ethanol

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

Procedure: 34.0 g (261 mmol) of 2,5-bis(hydroxymethyl)tetrahydrofuran are dissolved in 260 ml of dichloromethane. A solution of 99.0 g (521 mmol) of p-toluenesulfonyl chloride in 52 ml of pyridine and 130 ml of dichloromethane is added dropwise thereto. After stirring at room temperature for 24 hours, the precipitate is filtered off with suction and washed with dichloromethane. The filtrate and the washing phases are combined, washed with dilute hydrochloric acid and then with saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate and evaporated to dryness. The crude product is recrystallized from ethanol. the precipitate is filtered off with suction washed with dichloromethane washed with dilute hydrochloric acid with saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate evaporated to dryness The crude product is recrystallized from ethanol

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

Procedure: Raney nickel [ethanol was added three times to 50% commercial aqueous Raney nickel suspension (5 mL) from Acros, and decanted] was added to a solution of (5-hydroxymethylfuran-2-yl)methanol (RK-325) (3.46 g, 27 mmol) in absolute ethanol (100 mL), and hydrogenated overnight at room temperature and at a pressure of 2 bar (hydrogen consumption 61 mmol). The reaction mixture was filtered and the filtrate was concentrated under vacuum. The reaction mixture was filtered the filtrate was concentrated under vacuum

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

Procedure: Methanesulphonyl chloride (307.8 g, 2.7 mol) is added dropwise to a solution of tetrahydrofuran-2,5-dimethanol (118.8 g, 900 mmol) and of triethylamine (454.5 g, 4500 mmol) in 1.54 L of dichloromethane at 0° C. The reaction medium is maintained at 0° C. for 1 hour, ice-cold water is then added and the organic phase is separated out and washed with 500 mL of dilute (1 M) hydrochloric acid solution. The organic phase is separated out and then washed with 500 mL of saturated aqueous NaHCO3 solution. The organic phase is finally separated out and concentrated to give 236.7 g of (tetrahydrofuran-2,5-diyl)bis(methylene) dimethanesulphonate in the form of a brown oil in a purity equal to 96% (determined by LCMS). Reaction yield: 91.0%. A solution of (tetrahydrofuran-2,5-diyl)bis(methylene) dimethanesulphonate (236.7 g, 821.7 mmol) and NaN3 (270.0 g, 4.1094 mol) in DMSO (1.350 L) is heated at 95° C. and stirred overnight. The reaction medium is added to ice-cold water and extracted with 3 times 700 mL of ethyl acetate. The extracts (phase containing ethyl acetate) are successively washed with water, saturated aqueous NaHCO3 solution and dried overnight on MgSO4 and then filtered to remove the MgSO4. The phase containing the ethyl acetate is concentrated to give 166.5 g of 2,5-bis(azidomethyl)tetrahydrofuran in the form of a brown oil. A mixture of 2,5-bis(azidomethyl)tetrahydrofuran (166.5 g) and of Pd-C (10%, 10.8 g) in methanol (2.7 L) is stirred overnight at room temperature under 1 atm of H2. The reaction medium is filtered and the filtrate is concentrated under vacuum to give 90.0 g of 2,5-bis(aminomethyl)tetrahydrofuran in the form of a yellow oil. The total yield for the 3 successive reactions is 75%. The process for synthesizing 2,5-bis(aminomethyl)tetrahydrofuran gives a 90/10 mixture of the cis/trans isomers according to 13C NMR analysis in deuterated methanol. ice-cold water is then added the organic phase is separated out and washed with 500 mL of dilute (1 M) hydrochloric acid solution The organic phase is separated out washed with 500 mL of saturated aqueous NaHCO3 solution The organic phase is finally separated out concentrated

Conditions: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 2 gal. stainless steel stirred autoclave was charged 1420.5 g. of 2,5-dihydroxymethylfuran and 113.68 g. of the cationic ruthenium zeolite and 1 gal. of methanol. The system was pressurized with H2 to 3500 psig and heated to 30° C. An exothermic gas uptake was seen and the temperature rose within a minute to 82° C. Cooling water was started to control the exothermic reaction. After 5 hours, gas uptake had essentially ceased and gas chromatographic analysis indicated no starting material was present. Distillation gave 92 percent yield of 2,5-dihydroxymethyl tetrahydrofuran and about 8 percent of a product identified as 5-methyl tetrahydrofuran-2-methanol (hydrogenolysis product). rose within a minute to 82° C the exothermic reaction Distillation

Conditions: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 300 ml stainless steel autoclave was charged 40.03 g. 2,5-bis-(hydroxymethyl)furan, 100 ml methanol and 3 g. of cationic ruthenium zeolite. After pressurizing with H2 to 1900 psig and initiating stirring, the exothermic reduction occurred increasing the temperature from 30° C. (reaction temperature) to 61° C. The reduction temperature started to decrease as the reduction slowed down. The reduction was complete in 30 minutes and workup gave 99 percent 2,5-bis-hydroxymethyl tetrahydrofuran as the sole product (verified by analysis). (reaction temperature) to 61° C

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

Procedure: 34.0 g (261 mmol) of 2,5-bis(hydroxymethyl)tetrahydrofuran are dissolved in 260 ml of dichloromethane. A solution of 99.0 g (521 mmol) of p-toluenesulfonyl chloride in 52 ml of pyridine and 130 ml of dichloromethane is added dropwise thereto. After stirring at room temperature for 24 hours, the precipitate is filtered off with suction and washed with dichloromethane. The filtrate and the washing phases are combined, washed with dilute hydrochloric acid and then with saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate and evaporated to dryness. The crude product is recrystallized from ethanol. the precipitate is filtered off with suction washed with dichloromethane washed with dilute hydrochloric acid with saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate evaporated to dryness The crude product is recrystallized from ethanol