methyl 6-hydroxyhexanoate

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

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 0.786 g (5.37 mmole) of methyl-6-hydroxyhexanoate and 0.48 g (2.8 mmole) of diisopropylammonium tetrazolide in 25 ml of dichloromethane were added dropwise 1.62 g (5.37 mmole) of bis(diisopropyl amino)-2-cyanoethyoxyphosphine (Aldrich). The resulting solution was stirred at 25° C. for 2 hours and extracted with phosphate buffer at pH 7. Drying over magnesium sulfate and fast chromatography on silica gel (40% ethylacetate-hexanes, trace triethylamine) yielded the diisopropylamino-5-(carbomethoxy)pentyloxy-2-cyanoethoxy phosphine linking group as a colorless oil (1.30 g: 70%). extracted with phosphate buffer at pH 7 Drying over magnesium sulfate and fast chromatography on silica gel (40% ethylacetate-hexanes, trace triethylamine)

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 0.786 g (5.37 mmole) of methyl-6-hydroxyhexanoate and 0.48 g (2.8 mmole) of diisopropylammonium tetrazolide in 25 ml of dichloromethane were added dropwise 1.62 g (5.37 mmole) of bis(diisopropyl amino)-2-cyanoethyoxyphosphine (Aldrich). The resulting solution was stirred at 25° C. for 2 hours and extracted with phosphate buffer at pH 7. Drying over magnesium sulfate and fast chromatography on silica gel (40% ethylacetate-hexanes, trace triethylamine) yielded the diisopropylamino-5-(carbomethoxy)pentyloxy-2-cyanoethoxy phosphine linking group as a colorless oil (1.30 g: 70%). extracted with phosphate buffer at pH 7 Drying over magnesium sulfate and fast chromatography on silica gel (40% ethylacetate-hexanes, trace triethylamine)

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

Procedure: ε-Caprolactone (12.50 g, 109.51 mM) was dissolved in methanol (125 ml), and a sulfuric acid solution (1 ml, 0.01 mM) was slowly added thereto. The resulting mixture was stirred at room temperature for 2 days. After the completion of reaction, methanol was removed under reduced pressure, and then ice water was poured into the residue. The resulting mixture was extracted with ethyl ether. The organic layer was separated, washed with an aqueous saturated sodium bicarbonate solution and brine in order and concentrated under reduced pressure. The residue thus obtained was subjected to a silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/2) to obtain 10.18 g of the title compound (yield 64%). was removed under reduced pressure ice water was poured into the residue The resulting mixture was extracted with ethyl ether The organic layer was separated washed with an aqueous saturated sodium bicarbonate solution and brine in order concentrated under reduced pressure The residue thus obtained

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

Procedure: ε-Caprolactone (12.50 g, 109.51 mM) was dissolved in methanol (125 ml), and a sulfuric acid solution (1 ml, 0.01 mM) was slowly added thereto. The resulting mixture was stirred at room temperature for 2 days. After the completion of reaction, methanol was removed under reduced pressure, and then ice water was poured into the residue. The resulting mixture was extracted with ethyl ether. The organic layer was separated, washed with an aqueous saturated sodium bicarbonate solution and brine in order and concentrated under reduced pressure. The residue thus obtained was subjected to a silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/2) to obtain 10.18 g of the title compound (yield 64%). was removed under reduced pressure ice water was poured into the residue The resulting mixture was extracted with ethyl ether The organic layer was separated washed with an aqueous saturated sodium bicarbonate solution and brine in order concentrated under reduced pressure The residue thus obtained

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

Procedure: ε-Caprolactone (12.50 g, 109.51 mM) was dissolved in methanol (125 ml), and a sulfuric acid solution (1 ml, 0.01 mM) was slowly added thereto. The resulting mixture was stirred at room temperature for 2 days. After the completion of reaction, methanol was removed under reduced pressure, and then ice water was poured into the residue. The resulting mixture was extracted with ethyl ether. The organic layer was separated, washed with an aqueous saturated sodium bicarbonate solution and brine in order and concentrated under reduced pressure. The residue thus obtained was subjected to a silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/2) to obtain 10.18 g of the title compound (yield 64%). was removed under reduced pressure ice water was poured into the residue The resulting mixture was extracted with ethyl ether The organic layer was separated washed with an aqueous saturated sodium bicarbonate solution and brine in order concentrated under reduced pressure The residue thus obtained

Conditions: temp:250.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Nylon 6 (0.1 g), glycolic acid as a carboxylic acid (0.380 g) and methanol (3.0 g) were added to a 10 mL volume reactor equipped with a tube (outer diameter: ⅜ inches, inner diameter: 7.53 mm, length: 23 cm), nitrogen substitution was conducted at room temperature, and the reactor was sealed. The reactor was put into an electric furnace heated to 250° C. (pressure: 9.1 MPa), and the change over time was measured. In the measurement, the obtained reaction mixture and 1-hexanol as an internal standard substance were weighed and used as analysis samples for a gas chromatography analysis. An integral value was calculated by a gas chromatography analysis, and a table of a standard curve was prepared and the yield of methyl 6-hydroxycaproate was obtained therefrom. The result is shown in Table 6. equipped with a tube (outer diameter: ⅜ inches, inner diameter: 7.53 mm, length: 23 cm), nitrogen substitution was conducted at room temperature the reactor was sealed a table of a standard curve was prepared

Conditions: temp:270.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Nylon 6 (0.1 g), glycolic acid as a carboxylic acid (0.380 g) and methanol (3.0 g) were added to a 10 mL volume reactor equipped with a tube (outer diameter: ⅜ inches, inner diameter: 7.53 mm, length: 23 cm), nitrogen substitution was conducted at room temperature, and the reactor was sealed. The reactor was put into an electric furnace heated to 270° C. (pressure: 11.8 MPa), and the change over time was measured. In the measurement, the obtained reaction mixture and 1-hexanol as an internal standard substance were weighed and used as analysis samples for a gas chromatography analysis. An integral value was calculated by a gas chromatography analysis, and a table of a standard curve was prepared and the yield of methyl 6-hydroxycaproate was obtained therefrom. The result is shown in Table 5. equipped with a tube (outer diameter: ⅜ inches, inner diameter: 7.53 mm, length: 23 cm), nitrogen substitution was conducted at room temperature the reactor was sealed a table of a standard curve was prepared

Conditions: temp:300.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Nylon 6 (0.1 g), methoxyacetic acid as a carboxylic acid (0.45 g) and methanol (3.0 g) were added to a 10 mL volume reactor equipped with a tube (outer diameter: ⅜ inches, inner diameter: 7.53 mm, length: 23 cm), nitrogen substitution was conducted at room temperature, and the reactor was sealed. The reactor was put into an electric furnace heated to 300° C. (pressure: 16.3 MPa), and the change over time was measured. In the measurement, the obtained reaction mixture and 1-hexanol as an internal standard substance were weighed and used as analysis samples for a gas chromatography analysis. An integral value was calculated by a gas chromatography analysis, and a table of a standard curve was prepared and the yield of methyl 6-hydroxycaproate was obtained therefrom. The result is shown in Table 3. equipped with a tube (outer diameter: ⅜ inches, inner diameter: 7.53 mm, length: 23 cm), nitrogen substitution was conducted at room temperature the reactor was sealed a table of a standard curve was prepared

Conditions: temp:300.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Nylon 6 (0.1 g), methoxyacetic acid as a carboxylic acid (0.45 g) and methanol (3.0 g) were added to a 10 mL volume reactor equipped with a tube (outer diameter: ⅜ inches, inner diameter: 7.53 mm, length: 23 cm), nitrogen substitution was conducted at room temperature, and the reactor was sealed. The reactor was put into an electric furnace heated to 300° C. (pressure: 16.3 MPa), and the change over time was measured. In the measurement, the obtained reaction mixture and 1-hexanol as an internal standard substance were weighed and used as analysis samples for a gas chromatography analysis. An integral value was calculated by a gas chromatography analysis, and a table of a standard curve was prepared and the yield of methyl 6-hydroxycaproate was obtained therefrom. The result is shown in Table 3. equipped with a tube (outer diameter: ⅜ inches, inner diameter: 7.53 mm, length: 23 cm), nitrogen substitution was conducted at room temperature the reactor was sealed a table of a standard curve was prepared

Conditions: temp:300.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Nylon 6 (0.1 g), glycolic acid as a carboxylic acid (0.380 g) and methanol (3.0 g) were added to a 10 mL volume reactor equipped with a tube (outer diameter: ⅜ inches, inner diameter: 7.53 mm, length: 23 cm), nitrogen substitution was conducted at room temperature, and the reactor was sealed. The reactor was put into an electric furnace heated to 300° C. (pressure: 16.1 MPa), and the change over time was measured. In the measurement, the obtained reaction mixture and 1-hexanol as an internal standard substance were weighed and used as analysis samples for a gas chromatography analysis. An integral value was calculated by a gas chromatography analysis, and a table of a standard curve was prepared and the yield of methyl 6-hydroxycaproate was obtained therefrom. The result is shown in Table 2. equipped with a tube (outer diameter: ⅜ inches, inner diameter: 7.53 mm, length: 23 cm), nitrogen substitution was conducted at room temperature the reactor was sealed a table of a standard curve was prepared

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

Procedure: Trityl chloride (18.8 g, 67.4 mmol) was added to an ice cold (0° C.) stirring solution of 14a (9.9 g, 67.4 mmol) in 80 mL of pyridine. The reaction mixture was warmed to room temperature and stirred under argon for 2 days, during which time a white byproduct formed. The solvent was removed under reduced pressure, and the resulting material was redissolved in ice cold THF. The insoluble byproduct was removed by filtration, and the filtrate was dried under reduced pressure to obtain 22.6 g (86%) of an orange oil 15a. 1H-NMR (400 MHz, CDCl3, δH ppm): 7.43 (6H, m, p-Ar), 7.29 (6, m, m-Ar), 7.22 (3H, m, o-Ar), 3.65 (3H, s, CO2CH3), 3.05 (2H, t, 3JH—H=6.6 Hz, HO—CH2), 2.29 (2H, t, 3JH—H=7.5 Hz, CH2CO2), 1.54-1.71 (4H, m, 2CH2), 1.33-1.45 (m, 2H, CH2). HRMS (EI): m/z calcd 388.2038 (C26H28O3), found 388.2039 [M]+. formed The solvent was removed under reduced pressure the resulting material was redissolved in ice cold THF The insoluble byproduct was removed by filtration the filtrate was dried under reduced pressure