ethyl 2-(4-formylphenoxy)acetate

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: 4-Hydroxybenzaldehyde (250 g, 2.05 M), potassium carbonate (565 g, 4.09 M), toluene (2.5 L), methanesulfonic acid (20 g, 0.21 M) and iodine (2 g, catalytic) were taken in a 5 L 4-neck round bottom flask with mechanical stirrer and a Dean-Stark condenser. Ethylbromoacetate (341 g, 2.05 M) was added and the reaction was refluxed for 6-8 hours, under azeotropic removal of water, while monitoring the reaction on TLC. After the completion of the reaction, water was added and the organic layer separated while the aq. layer was extracted with toluene (2×500 ml). The combined organic layers were washed with brine and concentrated under vacuum to yield 4-((carboethoxy)methoxy)benzaldehyde as an oily material (400 g, Y=94%, P=99%). the reaction on TLC was added the organic layer separated while the aq. layer was extracted with toluene (2×500 ml) The combined organic layers were washed with brine concentrated under vacuum

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

Procedure: 4-Hydroxybenzaldehyde (250 g, 2.05 M), potassium carbonate (565 g. 4.09 M), xylene (2.5 L), p-toluenesulfonic acid (39 g, 0.21 M) and iodine (2 g, catalytic) were taken in a 5 L 4-neck round bottom flask with mechanical stirrer and a Dean-Stark condenser. Ethylbromoacetate (341 g, 2.05 M) was added and the reaction was refluxed for 6-8 hours, under azeotropic removal of water while monitoring the reaction on TLC. After the completion of the reaction, water was added and the organic layer separated while the aq. layer was extracted with xylene (2×500 ml). The combined organic layers were washed with brine and concentrated under vacuum to yield 4-((carboethoxy)methoxy)benzaldehyde as an oily material (408 g, Y=97%, P=99%). the reaction on TLC was added the organic layer separated while the aq. layer was extracted with xylene (2×500 ml) The combined organic layers were washed with brine concentrated under vacuum

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

Procedure: 4-Hydroxybenzaldehyde (250 g, 2.05 M), potassium carbonate (565 g, 4.09 M), toluene (2.5 L), p-toluenesulfonic acid (39 g, 0.21 M) and iodine (2 g, catalytic) were taken in a 5 L 4-neck round bottom flask with mechanical stirrer and a Dean-Stark condenser. Ethylchloroacetate (251 g, 2.05 M) was added and the reaction was refluxed for 6-8 hours, under azeotropic removal of water, while monitoring the reaction on TLC. After the completion of tile reaction, water was added and the organic layer separated while the aq. layer was extracted with toluene (2×500 ml). The combined organic layers were washed with brine and concentrated wider vacuum to yield 4-((carboethoxy)methoxy)benzaldehyde as an oily material (395 g, Y=93%, P=99%). the reaction on TLC was added the organic layer separated while the aq. layer was extracted with toluene (2×500 ml) The combined organic layers were washed with brine concentrated wider vacuum

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

Procedure: 4-Hydroxybenzaldehyde (250 g, 2.05 M), potassium carbonate (565 g, 4.09 M), toluene (2.5 L), p-toluene sulphonic acid (39 g, 0.21 M) and iodine (2 g, catalytic) were taken in a 5 L 4-neck round bottom flask with mechanical stirrer and a Dean-Stark condenser. Ethylbromoacetate (341 g, 2.05 M) was added and the reaction refluxed for 6-8 hours, under azeotropic removal of water, while monitoring the reaction on TLC. After the completion of the reaction, water was added and the organic layer separated while the aq. layer was extracted with toluene (2×500 ml). The combined organic layers were washed with brine and concentrated under vacuum to yield 4-((carboethoxy)methoxy)benzaldehyde as an oily material (407 g, Y=96%, P=99%). the reaction on TLC was added the organic layer separated while the aq. layer was extracted with toluene (2×500 ml) The combined organic layers were washed with brine concentrated under vacuum

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

Procedure: Commercially available ethyl 2-(4-formylphenoxy)acetate (20.0 g, 0.1 mol) and commercially available 4′-hydroxy-3′-methylacetophenone (15.0 g, 0.1 mol) were dissolved in 200 mL of methanol and 50 mL of water. The solution was cooled with an ice-water bath, to which was added potassium hydroxide (22.0 g, 0.392 mol). The reaction mixture was stirred overnight. The resulted mixture was poured on to 600 mL of ice-water, acidified to pH=4-5 with 1 N HCl, and extracted with ethyl acetate (4×200 mL). The combined organic layers were washed with water and brine (200 mL each), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The obtained yellow oil was dried under high-vacuum, 10 g (33%) of yellowish solid was obtained. MS (EI): 313 (MH+). The solution was cooled with an ice-water bath, to which extracted with ethyl acetate (4×200 mL) The combined organic layers were washed with water and brine (200 mL each) dried over anhydrous sodium sulfate filtered concentrated in vacuo The obtained yellow oil was dried under high-vacuum

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

Procedure: Ethyl 2-(4-formylphenoxy)acetate (52) was treated in an analogous manner to compound 48 to yield the desired product (57%) as a white solid. NMR: δ 4.834 (s, 2H), 7.112 (d, J=7.2 Hz, 2H), 7.866 (d, J=7.6 Hz, 2H), 9.878 (s, 1H), 13.146 (s, 1H).

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

Procedure: In an analogous manner to compound 47, 4-hydroxy benzaldehyde (1 eq) and ethyl 2-bromoacetate (1.1 eq) were reacted to produce the desired product (52%) as a brown oil. NMR: δ 1.306 (t, J=6.8 Hz, 3H), 4.29 (q, J=7.2 Hz, 2H), 4.710 (s, 2H), 7.016 (d, J=8.8 Hz, 2H), 7.85 (d, J=8.8 Hz, 2H), 9.904 (s, 1H).

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

Procedure: Ethyl (4-formylphenoxy)acetate (104.1 g, 0.5 mole), butylamine (36.6 g, 0.5 mole) and benzene (400 ml) were united and refluxed in a flask equipped with a Dean-Stark water separator. After one hour, water ceased to separate. The heating was terminated after 6 hours and the mixture distilled. There was obtained 108.6 g of product boiling at 178°-181° C. at 0.5 mm Hg pressure. refluxed in a flask to separate The heating was terminated after 6 hours the mixture distilled