2-chloro-1,1-dimethoxyethane

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

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

Conditions: temp:27.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Benzylamine (0.927 kg), chloroacetaldehydedimethylacetal (0.909 kg), sodium hydroxide solution (0.35 kg) in 2.72 L of water were charged into the flask under stirring at 25-30° C. for 10-15 min. Reaction mass was heated to 100-102° C. under stirring for 30 hrs. After completion of reaction, reaction mass was allowed to settle for 30 min. Two layers are separated and upper product layer was collected, distilled under high vacuum. Reaction mass was heated to 100-102° C. under stirring for 30 hrs After completion of reaction, reaction mass to settle for 30 min Two layers are separated upper product layer was collected distilled under high vacuum

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

Procedure: 500 gms of chloroacetaldehyde dimethyl acetal (Aldrich catalog no C1940-6), 360 gms of 1,4-butanediol (Aldrich catalog no. 88,480 7) and 10 gms of Dowex 50 resin (Aldrich catalog No. 21,749-2) were placed in a 1000 ml, 3-neck round bottom flask equipped with a thermometer, a mechanical stirrer, a 8 inch Pen State column, and a distillation head. The mixture was heated to 115° C. under nitrogen blanket and methanol was removed continuously and the amount collected was measured by weigh up. The reaction was monitored by analyzing samples taken from the distillate in a Gas Chromatograph with a dimethyl silicon column in the temperature range of 50° C. to 250° C. The reaction was stopped when the stoichiometric amount of methanol was collected. The crude reaction mixture was filtered to remove the ion exchange resin. The product 2-chloromethyl 1,3-dioxepane was isolated from the crude mixture by fractional distillation in an Oldershaw column under partial vacuum. The fraction boiling at 105° C. at 55 mm of Hg was collected. The structure was confirmed by elemental analysis and proton NMR. Elemental analysis: C-47.2 percent (48 percent calculated), H=7.58 percent (7.33 percent calculated), 0=22.64 percent (21.34 percent calculated), C1=22.57 percent (23.3 percent calculated). Proton NMR:1.71-1.34 ppm multiplet (--OCH2CH2CH2CH2O--), 3.46-3.48 ppm doublet (--CH2Cl), 3.66-2.96 ppm 2 sets of triplets (--OCH2 ; 2 sets, 4 protons), 4.83-4.87 ppm triplet (C1CH2CH(O)2). equipped with a thermometer, a mechanical stirrer was removed continuously the amount collected taken from the distillate in a Gas Chromatograph with a dimethyl silicon column in the temperature range of 50° C. to 250° C was collected The crude reaction mixture was filtered to remove the ion exchange resin

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The monosodium salt of 3-hydroxy-5-bromophenol (0.05 mole) and dimethylformamide (75 ml) are charged under nitrogen gas into a glass reaction vessel equipped with a mechanical stirrer, thermometer and additional funnel. The mixture is stirred until dissolved, and 1-chloro-2,2-dimethoxyethane (0.05 mole) is added dropwise over a period of about 20 minutes. After the addition is completed, the reaction mixture is heated at about 90° C. with stirring for a period of about 48 hours. After this time water (200 ml) is added, and the reaction mixture is neutralized with ammonium chloride. The reaction mixture is then extracted with chloroform, and the organic phase is separated from the aqueous phase. The organic phase is then stripped of solvent, leaving an oil. This oil is distilled under reduced pressure to yield the desired product 3-(2,2-dimethoxyethoxy)-5-bromophenol. equipped with a mechanical stirrer until dissolved After the addition with stirring for a period of about 48 hours The reaction mixture is then extracted with chloroform the organic phase is separated from the aqueous phase leaving an oil This oil is distilled under reduced pressure

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

Procedure: The S-sodium salt of 3-mercaptophenol prepared in Example 7 was dissolved in dimethylformamide (25 ml) and charged under nitrogen gas into a glass reaction vessel equipped with a mechanical stirrer, thermometer and addition funnel. The solution was heated to a temperature of 45 to 50° C., and 1-chloro-2,2-dimethoxyethane (3.15 grams) was added with stirring. After the addition was completed, stirring was continued for a period of about 3 hours. After this time the reaction mixture was poured into water (150 ml), and the resulting mixture was carefully neutralized with ammonium chloride. The mixture was then extracted with chloroform and the organic phase was separated. The organic portion was washed with water and then dried with phase separation paper. The dried solution was then stripped of solvent, leaving an oil. This oil was distilled, and the fraction boiling at 138° to 144° C. at 0.04 mm of Hg pressure was collected to yield the desired product 3-(2,2-dimethoxyethylthio)phenol. charged under nitrogen gas into a glass reaction vessel equipped with a mechanical stirrer thermometer and addition funnel was added After the addition stirring The mixture was then extracted with chloroform the organic phase was separated The organic portion was washed with water dried with phase separation paper leaving an oil This oil was distilled the fraction boiling at 138° to 144° C. at 0.04 mm of Hg pressure was collected

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

Procedure: The monosodium salt of 5-methylresorcinol prepared in Example 4 and dimethyl formamide (200 ml) were charged under nitrogen gas into a glass reaction vessel equipped with a mechanical stirrer, thermometer and addition funnel. 1-Chloro-2,2-dimethoxyethane (6.25 grams) was added, and the mixture was heated at 85° to 90° C. and stirred for a period of about 221/2 hours. After this time the reaction mixture was cooled to room temperature and was added to 1200 ml of water. The resulting mixture was carefully neutralized and extracted with chloroform. The organic phase was then separated from the aqueous phase and stripped of solvent, leaving a liquid residue. The residue was distilled under reduced pressure to yield a yellow viscous liquid which solidified upon cooling to -10° C. This product was then recrystallized from a methanol-water mixture, was washed with boiling water and dried to yield the desired product 3-(2,2-dimethoxyethoxy)-5-hydroxytoluene as a white solid melting at 73° to 75° C. equipped with a mechanical stirrer thermometer and addition funnel the mixture was heated at 85° to 90° C. extracted with chloroform The organic phase was then separated from the aqueous phase leaving a liquid residue The residue was distilled under reduced pressure to yield a yellow viscous liquid which upon cooling to -10° C This product was then recrystallized from a methanol-water mixture was washed with boiling water dried

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

Procedure: The monosodium salt of hydroquinone prepared in Example 1 and dimethyl formamide (100 ml) were charged under nitrogen gas into a glass reaction vessel equipped with a mechanical stirrer, thermometer and addition funnel and were warmed to effect dissolution. The resulting solution was then allowed to warm to room temperature, and 1-chloro-2,2-dimethoxyethane was added dropwise over a period of about 20 minutes. After the addition was completed, the reaction mixture was heated at about 85° to 90° C. with stirring for a period of about 48 hours. After this time water (200 ml) was added, and the reaction mixture was neutralized with ammonium chloride. The reaction mixture was then extracted with chloroform, and the organic phase was separated from the aqueous phase. The organic phase was then stripped of solvent, leaving a red oil. This oil was distilled to yield the desired product 4-(2,2-dimethoxyethoxy)phenol as a pink oil boiling at 116° to 120° C. at 0.008 mm of Hg pressure. equipped with a mechanical stirrer thermometer and addition funnel were warmed dissolution After the addition the reaction mixture was heated at about 85° to 90° C. The reaction mixture was then extracted with chloroform the organic phase was separated from the aqueous phase leaving a red oil This oil was distilled

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Chloro-1,1-dimethoxyethane (206 mL) was treated with cyclohexanamine (575 mL) and the mixture was heated at 120° C. for 24 h under an atmosphere of nitrogen before being cooled to room temperature. A solution of sodium hydroxide (100 g) in 400 mL water was added, the mixture was stirred at room temperature for 10 min and then the layers were separated. The organic fraction was purified by distillation under reduced pressure (b.p. 105-107° C., 13 mm Hg) to give the title compound as a colourless oil (280 g). 1H NMR (400 MHz, CDCl3) δ 4.46 (t, J=5.5 Hz, 1H), 3.38 (s, 6H), 2.75 (d, J=5.6 Hz, 2H), 2.45-2.35 (m, 1H), 1.92-1.57 (m, 5H), 1.31-1.00 (m, 6H). before being cooled to room temperature the layers were separated The organic fraction was purified by distillation under reduced pressure (b.p. 105-107° C., 13 mm Hg)

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

Procedure: 10 g (55.5 mmol) of 2-hydroxy-1-(4-hydroxyphenyl)-2-methylpropan-1-one are dissolved in 50 g of methanol together with 2.22 g (55.5 mmol) of NaOH, and kept at 150° C. for 5 hours in a bomb tube with 20 g of chloroacetaldehyde dimethyl acetal. The reaction mixture is evaporated, and the residue is dissolved in ether and washed with 0.1 N NaOH. The crude product (14.8 g) is crystallized from ether/petroleum ether, giving 9.8 g (65% of theory) of a beige product of m.p. 52-53° C. The reaction mixture is evaporated the residue is dissolved in ether washed with 0.1 N NaOH The crude product (14.8 g) is crystallized from ether/petroleum ether giving 9.8 g (65% of theory) of a beige product of m.p. 52-53° C.

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

Procedure: 10 g (55.5 mmol) of 2-hydroxy-1-(4-hydroxyphenyl)-2-methylpropan-1-one are dissolved in 50 g of methanol together with 2.22 g (55.5 mmol) of NaOH, and kept at 150° C. for 5 hours in a bomb tube with 20 g of chloroacetaldehyde dimethyl acetal. The reaction mixture is evaporated, and the residue is dissolved in ether and washed with 0.1 N NaOH. The crude product (14.8 g) is crystallized from ether/petroleum ether, giving 9.8 g (65% of theory) of a beige product of m.p. 52-53° C. The reaction mixture is evaporated the residue is dissolved in ether washed with 0.1 N NaOH The crude product (14.8 g) is crystallized from ether/petroleum ether giving 9.8 g (65% of theory) of a beige product of m.p. 52-53° C.

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

Procedure: Chloroacetaldehyde dimethyl acetal (50.0 g), potassium benzoate (70.7 g), potassium iodide (6.66 g) and DMF (N,N-dimethylformamide) (250 mL) were placed in a three-neck flask, followed by refluxing. Twenty hours later, the reaction mixture was cooled to room temperature, and water (250 mL) and ethyl acetate (250 mL) were added thereto, followed by stirring. After filtration, the filtrate was extracted with ethyl acetate (500 mL). The organic layer was subjected to vacuum concentration and then to vacuum distillation at 132-135° C. and at 5 mmHg and thereby yielded the target compound (61.0 g) in a yield of 72%. by refluxing After filtration the filtrate was extracted with ethyl acetate (500 mL) The organic layer was subjected to vacuum concentration to vacuum distillation at 132-135° C.