pentane-2,4-diol

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:

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

Procedure: With 4-nitrobenzylphosphonic acid and 2,4-pentanediol, the same procedure as in Reference Example 11 was followed, to yield 4,6-dimethyl-2-(4-nitrobenzyl)-1,3,2-dioxaphosphorinane-2-oxide, which was then recrystallized from ethanol-hexane to yield colorless needles having a melting point of 152° to 153° C.

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

Procedure: With 4-nitrobenzylphosphonic acid and 2,4-pentanediol, the same procedure as in Reference Example 11 was followed, to yield 4,6-dimethyl-2-(4-nitrobenzyl)-1,3,2-dioxaphosphorinane-2-oxide, which was then recrystallized from ethanol-hexane to yield colorless needles having a melting point of 152° to 153° C.

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

Procedure: Reaction of N-Acetyl-2-methoxypyrrolidine (E) with 2,4-Pentandiol. One g of N-acetyl-2-methoxypyrrolidine (largely E plus lesser an amounts of B, C and D), 0.9 g of 2,4-pentandiol and 240 mg of N-methyl-2-pyrrolidone internal standard were heated at 50°-55° C. in 1 mL of H2O. A separate sample was heated in 1 mL of EtOAc. Results in both samples were similar: rapid initial formation of a small peak at 8.02 min (cyclic hemiamidal of the diol?), followed by growth of major product peaks at 8.35 and 8.73 min, the epimeric cyclic acetals. Small quantities of dehydrated product G (r.t.=4.75 min), and, in the aqueous sample, N-acetyl-2-hydroxypyrrolidine, F (before A at ~5.6 min) were also produced. One of the diols appeared to react faster and to a greater extent than the other. Measurements at 3-4 hr were close to the overnight values: ~87% conversion of A, 60-70% of B and essentially quantitative conversion of C and D. Results in both samples followed by growth of major product peaks at 8.35 and 8.73 min

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

Procedure: Reaction of N-Acetyl-2-methoxypyrrolidine (E) with 2,4-Pentandiol. One g of N-acetyl-2-methoxypyrrolidine (largely E plus lesser an amounts of B, C and D), 0.9 g of 2,4-pentandiol and 240 mg of N-methyl-2-pyrrolidone internal standard were heated at 50°-55° C. in 1 mL of H2O. A separate sample was heated in 1 mL of EtOAc. Results in both samples were similar: rapid initial formation of a small peak at 8.02 min (cyclic hemiamidal of the diol?), followed by growth of major product peaks at 8.35 and 8.73 min, the epimeric cyclic acetals. Small quantities of dehydrated product G (r.t.=4.75 min), and, in the aqueous sample, N-acetyl-2-hydroxypyrrolidine, F (before A at ~5.6 min) were also produced. One of the diols appeared to react faster and to a greater extent than the other. Measurements at 3-4 hr were close to the overnight values: ~87% conversion of A, 60-70% of B and essentially quantitative conversion of C and D. Results in both samples followed by growth of major product peaks at 8.35 and 8.73 min

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

Procedure: 4-Nitrobenzylphosphonic acid and 2,4-pentanediol were treated in the same manner as in Reference Example 20 to yield 4,6-dimethyl-2-(4-nitrobenzyl)-1,3,2-dioxaphosphorinan-2-oxide, which was then recrystallized from ethanol-hexane to yield colorless needles having a melting point of 152°-153° C.

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A three-neck round bottom flask is vacuum dried, fitted with a stir bar, thermometer, and drying tube and maintained under nitrogen. About 500 milliliters (ml) of anhydrous xylene is cannulated into the flask. Two ml of 3,4-dimethoxy thiophene 1 (DMOT) (0.0166 mol), 4.85 ml of 2,4-pentanediol 2 (0.0332), and 0.61 ml of catalyst dodecylbenzene sulfonic acid (DBSA) (0.0025 mol) are added to the flask sequentially with previously degassed disposable syringes through the rubber septa fitted on one of the necks of the flask. The molar proportion between DMOT:diol:DBSA is 1.00:2.00:0.15. The reaction is set to run for five days under stirring at a temperature of around 100° C. The reaction is monitored on a daily basis by gas chromatography-mass spectrometry (GC-MS). After five days, the reaction is cooled to ambient temperature and filtered to remove any solid particulates. The xylene is stripped using a rotary evaporator to result in a green oil. The oil is taken up in a small amount of chloroform and extracted with water three times using sodium chloride to break any emulsion. The chloroform is stripped leaving a green oil. The crude mixture is purified by column chromatography using 70:30 toluene:n-hexane as the eluting solvent. The first fractions contain the product 2,4-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine 3 (aDM-ProDOT) and subsequent fractions contain DMOT 1 starting material. The aDM-ProDOT 3 is isolated as a white solid that is dried under vacuum. The final product was confirmed by GC-MS and 1H-NMR. A three-neck round bottom flask is vacuum dried fitted with a stir bar thermometer, and drying tube maintained under nitrogen fitted on one of the necks of the flask After five days the reaction is cooled to ambient temperature filtered to remove any solid particulates a rotary evaporator to result in a green oil extracted with water three times The chloroform is stripped leaving a green oil The crude mixture is purified by column chromatography

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A three-neck round bottom flask is vacuum dried, fitted with a stir bar, thermometer, and drying tube and maintained under nitrogen. About 500 milliliters (ml) of anhydrous xylene is cannulated into the flask. Two ml of 3,4-dimethoxy thiophene 1 (DMOT) (0.0166 mol), 4.85 ml of 2,4-pentanediol 2 (0.0332), and 0.61 ml of catalyst dodecylbenzene sulfonic acid (DBSA) (0.0025 mol) are added to the flask sequentially with previously degassed disposable syringes through the rubber septa fitted on one of the necks of the flask. The molar proportion between DMOT:diol:DBSA is 1.00:2.00:0.15. The reaction is set to run for five days under stirring at a temperature of around 100° C. The reaction is monitored on a daily basis by gas chromatography-mass spectrometry (GC-MS). After five days, the reaction is cooled to ambient temperature and filtered to remove any solid particulates. The xylene is stripped using a rotary evaporator to result in a green oil. The oil is taken up in a small amount of chloroform and extracted with water three times using sodium chloride to break any emulsion. The chloroform is stripped leaving a green oil. The crude mixture is purified by column chromatography using 70:30 toluene:n-hexane as the eluting solvent. The first fractions contain the product 2,4-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine 3 (aDM-ProDOT) and subsequent fractions contain DMOT 1 starting material. The aDM-ProDOT 3 is isolated as a white solid that is dried under vacuum. The final product was confirmed by GC-MS and 1H-NMR. A three-neck round bottom flask is vacuum dried fitted with a stir bar thermometer, and drying tube maintained under nitrogen fitted on one of the necks of the flask After five days the reaction is cooled to ambient temperature filtered to remove any solid particulates a rotary evaporator to result in a green oil extracted with water three times The chloroform is stripped leaving a green oil The crude mixture is purified by column chromatography