1-ethoxyprop-1-ene

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:35.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 900 g (7.4 mol) of acetaldehyde diethyl acetal (purity according to GC: 97%) and 0.85 g (0.75 ml, 6 mmol, 0.25 mol %) of boron trifluoride etherate were placed in a 2 l two-necked round flask fitted with a magnetic stirrer, a thermometer and a dropping funnel. 220 g (2.5 mol) of ethyl (1-propenyl) ether were added dropwise within about 30 minutes while cooling occasionally with ice at a temperature of about 35° C., but a maximum of 40° C. After completion of the addition the mixture was stirred at room temperature for a further 30 minutes. Then, 4 g of solid, powdered sodium carbonate were added thereto and the mixture was stirred at room temperature for 2.5 hours. Then the mixture was suction filtered and the excess acetaldehyde diethyl acetal was distilled off on a Raschig column, (30×2.5 cm) at 100 mbar. About 1 l of acetaldehyde diethyl acetal (content according to GC. 91%) was recovered in this manner at a boiling point of 40-43° C. The residue was then fractionated on the same column at a pressure of 12-13 mbar. This gave 344.5 g (66.2% yield) of 1,1,3-triethoxy-2-methyl-butane as a water-clear liquid with a boiling point of 81-84° C. and a content of 98.2% according to GC. fitted with a magnetic stirrer a maximum of 40° C After completion of the addition the mixture the mixture was stirred at room temperature for 2.5 hours filtered the excess acetaldehyde diethyl acetal was distilled off on a Raschig column, (30×2.5 cm) at 100 mbar About 1 l of acetaldehyde diethyl acetal (content according to GC. 91%) was recovered in this manner at a boiling point of 40-43° C

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 236 g of acetaldehyde diethyl acetal (abbreviation: acetal) and 1 g of aluminum chloride are added in 500 ml of four necked bottle under protection of nitrogen, the solution is freezed to −10° C., and kept at −10° C.˜−5° C., a mixture of 118 g of acetaldehyde diethyl acetal and 86 g (0.945 mol) of ethyl-(1-propenyl)-ether is slowly dropped, and continue to stir it for 10 min after finishing dropping, and the end of reaction is detected by GC. A saturated NaHCO3 solution is added in the reaction to neutralize it to pH=7, and to layer, the oil layer is dried by anhydrous sodium sulfate after being washed by water, and heated to 50° C.; most of acetaldehyde diethyl acetal is recycled, to obtain 169.6 g of 1,1,3-triethoxy-2-methyl-butane by vacuum distillation, and its content is 97.2%, and its yield is 88%. is freezed to −10° C. kept at −10° C.˜−5° C. is slowly dropped the end of reaction to layer, the oil layer is dried by anhydrous sodium sulfate after being washed by water

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

Procedure: According to the present invention, a method for synthesizing 2,7-dimethyl-2,4,6-octatriene-1,8-dialdehyde comprises the following steps: (1) adding acetaldehyde diethyl acetal (abbreviation: acetal) and ethyl-(1-propenyl)-ether under effects of a catalyst at a temperature of −10° C.˜0° C. to produce 1,1,3-triethoxy-2-methyl-butane; wherein the catalyst is ferric chloride or aluminum chloride; acetaldehyde diethyl acetal is prepared by the Chinese Patent No. ZL97115390.6 of Hoffmann-La Roche Ltd; (2) pyrolysis synthesizing 1,1,3-triethoxy-2-methyl-butane under catalytic effects of isoquinoline and p-Toluenesulfonic acid at a temperature of 180-200° C. to produce 1-methoxy-2-methyl-1,3-butadiene; but the catalyst used in the Chinese Patent ZL97115390.6 of Hoffmann-La Roche Ltd. is silicon-aluminum ball, to pyrolysis produce 1-methoxy-2-methyl-1,3-butadiene at high temperature, its conversion rate is only 41%, and its selectivity is 90%; (3) dissolving 1-methoxy-2-methyl-1,3-butadiene in anhydrous ethanol solvent for synthesis with a phase transfer catalyst and a chlorinating agent at a temperature of −5˜0° C. to generate 4,4-diethoxy-3-methyl-1-chloro-butene; wherein the phase transfer catalyst is cetyl-trimethyl ammonium bromide, the chlorinating agent is trichloroisocyanuric acid; (4) combining 4,4-diethoxy-3-methyl-1-chloro-butene with a triphenylphosphine salt at a temperature of 60˜65° C. to produce a phosphonic salt; and (5) condensing the phosphonic salt under effects of hydrogen peroxide at a temperature of 0˜5° C. in conjunction with sodium carbonate solution to generate 1,1,8,8-tetramethyl-2,7-dimethyl-2,4,6-octatriene at pH=8˜10; and then hydrolyzing under acidic conditions to synthesize 2,7-dimethyl-2,4,6-octatriene-1,8-dialdehyde.

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

Procedure: A mixture of 5-bromo-N-hydroxy-3-(methylcarbamoyl)-6-(N-methylmethylsulfonamido)benzofuran-2-carbimidoyl chloride (400 mg, 0.91 mmol), 1-ethoxyprop-1-ene (392 mg, 4.56 mmol) and NaHCO3 (153 mg, 1.82 mmol) in DMF (10 mL) was stirred at room temperature for 16 h. It was concentrated, diluted with water, extracted with EtOAc, the organic layers were washed with brine, dried over Na2SO4, and concentrated. The residue was purified by column chromatography (PE:EA=2:1) to get product 5-bromo-2-(5-ethoxy-4-methyl-4,5-dihydroisoxazol-3-yl)-N-methyl-6-(N-methylmethylsulfonamido)benzofuran-3-carboxamide (370 mg, yield: 83%). MS (M+H)+: 488/490. It was concentrated diluted with water extracted with EtOAc the organic layers were washed with brine dried over Na2SO4 concentrated The residue was purified by column chromatography (PE:EA=2:1)

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

Procedure: A mixture of 5-bromo-N-hydroxy-3-(methylcarbamoyl)-6-(N-methylmethylsulfonamido)benzofuran-2-carbimidoyl chloride (400 mg, 0.91 mmol), 1-ethoxyprop-1-ene (392 mg, 4.56 mmol) and NaHCO3 (153 mg, 1.82 mmol) in DMF (10 mL) was stirred at room temperature for 16 h. It was concentrated, diluted with water, extracted with EtOAc, the organic layers were washed with brine, dried over Na2SO4, and concentrated. The residue was purified by column chromatography (PE:EA=2:1) to get product 5-bromo-2-(5-ethoxy-4-methyl-4,5-dihydroisoxazol-3-yl)-N-methyl-6-(N-methylmethylsulfonamido)benzofuran-3-carboxamide (370 mg, yield: 83%). MS (M+H)+: 488/490. It was concentrated diluted with water extracted with EtOAc the organic layers were washed with brine dried over Na2SO4 concentrated The residue was purified by column chromatography (PE:EA=2:1)

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

Procedure: A solution of 5-iodo-6-methyl-N-[4-(methylsulfonyl)benzyl]-2-oxo-1-[3-(trifluoromethyl)phenyl]-1,2-dihydropyridine-3-carboxamide (Example 1 (d), 1500 mg, 2.5 mmol), bis[1,2-bis(diphenylphosphino)ethanelpalladium(0) (230 mg, 0.25 mmol), triethylamine (7.5 ml, 54 mmol) and ethylpropenyl ether (900 μl, 7.5 mmol) in DMP (45 ml) was heated at 100° C. overnight. After cooling, the reaction mixture was poured into water and extracted with ethyl acetate and the solvent was removed under reduced pressure. The crude product was then dissolved in DMP (25 ml) and 2M HCl (25 ml) and then stirred for 1.5 h. The reaction mixture was then poured into aqueous NaHCO3 and extracted with ethyl acetate. The extracts were separated, evaporated under reduced pressure, and the residue was chromatographed on silica using ethyl acetate/heptane (2/1, 4/1, 10/1) as eluent. Fractions containing the product were combined and evaporated to give the title compound (1.3 g, >99%). was heated at 100° C. overnight After cooling extracted with ethyl acetate the solvent was removed under reduced pressure The crude product was then dissolved in DMP (25 ml) and 2M HCl (25 ml) The reaction mixture was then poured into aqueous NaHCO3 extracted with ethyl acetate The extracts were separated evaporated under reduced pressure the residue was chromatographed on silica Fractions containing the product evaporated

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

Procedure: 15 drops of 85% phosphoric acid were added to a mixture, cooled to -30° C in a laboratory autoclave, of 76 g of 3-isopropenyl-1-methyl-2-methylene-cyclopentan-1-ol and 130 g of ethyl 1-propenyl ether. After gassing with nitrogen, the autoclave was brought, in an oil bath of 180° C, to an internal temperature of 150° C (this took about 15 minutes) and held at this temperature until a distinct drop in pressure occurred (about 75 minutes). The reaction mixture was then quenched, taken up in ether, washed with aqueous bicarbonate solution and water, the solution dried over anhydrous magnesium sulphate and concentrated under reduced pressure. The crude product (135 g), obtained as a yellow oil, was fractionated and yielded 64 g (67%) of pure 2-(2-formylpropyl)-3-isopropenyl-1-methyl-cyclopent-1-ene having woody, earthy, musty fragrance; boiling point 0.005 = 51° C; nD20 = 1.4825; IRfilm : νmax = 3090, 2730, 1735, 1645, 1460, 1380 and 898 cm-1. the autoclave was brought, in an oil bath of 180° C, to an internal temperature of 150° C this took about 15 minutes (about 75 minutes) The reaction mixture was then quenched washed with aqueous bicarbonate solution and water the solution dried over anhydrous magnesium sulphate concentrated under reduced pressure The crude product (135 g), obtained as a yellow oil

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

Procedure: 15 drops of 85% phosphoric acid were added to a mixture, cooled to -30° C in a laboratory autoclave, of 76 g of 3-isopropenyl-1-methyl-2-methylene-cyclopentan-1-ol and 130 g of ethyl 1-propenyl ether. After gassing with nitrogen, the autoclave was brought, in an oil bath of 180° C, to an internal temperature of 150° C (this took about 15 minutes) and held at this temperature until a distinct drop in pressure occurred (about 75 minutes). The reaction mixture was then quenched, taken up in ether, washed with aqueous bicarbonate solution and water, the solution dried over anhydrous magnesium sulphate and concentrated under reduced pressure. The crude product (135 g), obtained as a yellow oil, was fractionated and yielded 64 g (67%) of pure 2-(2-formylpropyl)-3-isopropenyl-1-methyl-cyclopent-1-ene having woody, earthy, musty fragrance; boiling point 0.005 = 51° C; nD20 = 1.4825; IRfilm : νmax = 3090, 2730, 1735, 1645, 1460, 1380 and 898 cm-1. the autoclave was brought, in an oil bath of 180° C, to an internal temperature of 150° C this took about 15 minutes (about 75 minutes) The reaction mixture was then quenched washed with aqueous bicarbonate solution and water the solution dried over anhydrous magnesium sulphate concentrated under reduced pressure The crude product (135 g), obtained as a yellow oil

Conditions: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 250 mL flask containing 37.0 g (0.31 mole) ethyl lactate and four drops 32% hydrochloric acid at 30° C. is added 71 g (0.82 mole) ethyl propenyl ether. The mixture is heated to 75° C. for thirty minutes, cooled to 25° C., then quenched with 100 g 5% sodium bicarbonate solution. The organic material was flash distilled yielding 52.3 g (90%) ethyl 2-[(1'-ethoxy)propoxy]propanoate. cooled to 25° C. quenched with 100 g 5% sodium bicarbonate solution distilled