(1-ethoxy-3-methylbut-1-enoxy)-trimethylsilane

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: A 250 milliliter flask was equipped with a magnetic stirrer, reflux condenser and nitrogen inlet. The flask was dried with external heat and then charged with 19.92 grams (0.22 mol) of 3-chloro-1-butyne, 30.49 grams (0.15 mol) of 1-trimethylsilyloxy-1-ethoxy-3-methylbutene prepared in Part A, 100 milliliters of dry methylene chloride, and 0.5 grams of anhydrous zinc chloride. The reaction mixture was stirred at room temperature and monitored by infrared for 48 hours. The disappearance of the ketene acetal C=C peak at 1675 cm-1 and the appearance of an ester C=O peak at 1720 cm-1 was observed. The reaction mixture was then worked up by diluting with 150 milliliters of methylene chloride and washing five times with 100 milliliters of 5% sodium bicarbonate and twice with water. The methylene chloride was dried (MgSO4) and removed under vacuum to give a residue. The residue was vacuum distilled through a vigreux column to give 8.44 grams (0.05 mol) of ethyl 2-isopropyl-3-methyl-4-pentynoate having the appearance of a colorless oil and a boiling point of 66°-76° C. at 7 millimeters pressure. A 250 milliliter flask was equipped with a magnetic stirrer reflux condenser and nitrogen inlet The flask was dried with external heat washing five times with 100 milliliters of 5% sodium bicarbonate The methylene chloride was dried (MgSO4) removed under vacuum to give a residue distilled through a vigreux column

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2 liter flask was equipped with a mechanical stirrer, addition funnel, reflux condenser, nitrogen inlet and thermometer. The flask was dried with external heat and then charged with 563 milliliters of dry tetrahydrofuran, 75.9 grams (0.75 mol) of diisopropylamine and cooled to 0° C. Over a 30 minute period 523 milliliters of 1.6 M n-butyl lithium (0.94 mol) was added dropwise. The reaction mixture was stirred at 0° C. for 15 minutes, then cooled to -76° C. in a dry ice-acetone bath and 97.65 grams (0.75 mol) of ethyl isovalerate was added dropwise over about 30 minutes. When this addition was complete, the reaction mixture was stirred for 15 minutes at -76° C., then 205 milliliters (2.20 mol) of chlorotrimethylsilane was added dropwise. When this addition was complete, the dry ice-acetone bath was removed and the reaction mixture allowed to come to room temperature. The reaction mixture was then filtered and concentrated under reduced pressure to give a residue which was triturated with ether and filtered. The filtrate was concentrated under vacuum to give a residue and the residue was vacuum distilled through a vigreux column to give 136.44 grams (1.48 mol) of 1-trimethylsilyloxy-1-ethoxy-3-methylbutene having a boiling point of 78°-88° C. at 30 millimeters pressure. A 2 liter flask was equipped with a mechanical stirrer, addition funnel reflux condenser, nitrogen inlet The flask was dried with external heat cooled to -76° C. in a dry ice-acetone bath When this addition the reaction mixture was stirred for 15 minutes at -76° C. When this addition the dry ice-acetone bath was removed to come to room temperature The reaction mixture was then filtered concentrated under reduced pressure to give a residue which was triturated with ether filtered The filtrate was concentrated under vacuum to give a residue distilled through a vigreux column

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2 liter flask was equipped with a mechanical stirrer, addition funnel, reflux condenser, nitrogen inlet and thermometer. The flask was dried with external heat and then charged with 563 milliliters of dry tetrahydrofuran, 75.9 grams (0.75 mol) of diisopropylamine and cooled to 0° C. Over a 30 minute period 523 milliliters of 1.6 M n-butyl lithium (0.94 mol) was added dropwise. The reaction mixture was stirred at 0° C. for 15 minutes, then cooled to -76° C. in a dry ice-acetone bath and 97.65 grams (0.75 mol) of ethyl isovalerate was added dropwise over about 30 minutes. When this addition was complete, the reaction mixture was stirred for 15 minutes at -76° C., then 205 milliliters (2.20 mol) of chlorotrimethylsilane was added dropwise. When this addition was complete, the dry ice-acetone bath was removed and the reaction mixture allowed to come to room temperature. The reaction mixture was then filtered and concentrated under reduced pressure to give a residue which was triturated with ether and filtered. The filtrate was concentrated under vacuum to give a residue and the residue was vacuum distilled through a vigreux column to give 136.44 grams (1.48 mol) of 1-trimethylsilyloxy-1-ethoxy-3-methylbutene having a boiling point of 78°-88° C. at 30 millimeters pressure. A 2 liter flask was equipped with a mechanical stirrer, addition funnel reflux condenser, nitrogen inlet The flask was dried with external heat cooled to -76° C. in a dry ice-acetone bath When this addition the reaction mixture was stirred for 15 minutes at -76° C. When this addition the dry ice-acetone bath was removed to come to room temperature The reaction mixture was then filtered concentrated under reduced pressure to give a residue which was triturated with ether filtered The filtrate was concentrated under vacuum to give a residue distilled through a vigreux column

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

Procedure: A 250 ml R.B. flask was equipped with a magnetic stirrer, reflux condenser, and N2 inlet tube. The glassware was dried thoroughly then charged with 23.91 g (0.15 mol) of 1,1,3-trichloro-1-butene, 30.36 g (0.15 mol) of 1-trimethylsilyloxy-1-ethoxy-3-methyl-1-butene, 100 ml of methylene chloride, and ~0.50 g of anhydrous zinc chloride. The reaction mixture was stirred at room temperature and monitored by infrared. The gradual disappearance of the ketene acetal C=C peak at 1675 cm-1 and the appearance of an ester C=O peak at 1720 cm-1 was observed. The reaction mixture after 67 hours showed only a c=O peak at 1720 cm-1 and no 1675 cm-1, and was diluted with 150 ml of methylene chloride, washed with 5×100 ml of 5% sodium bicarbonate solution, then 2×with 50 ml of water. The methylene chloride was dried (MgSO4), stripped, and the residue vacuum distilled through a vigreux column to give 23.41 g (62% yield) of the desired product, b.p. 64°-68° C./0.30 mm. flask was equipped with a magnetic stirrer reflux condenser, and N2 inlet tube The glassware was dried thoroughly washed with 5×100 ml of 5% sodium bicarbonate solution The methylene chloride was dried (MgSO4) the residue vacuum distilled through a vigreux column

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 1 liter flask was equipped with a mechanical stirrer, a reflux condenser, an addition funnel, nitrogen inlet, and thermometer. The glassware was dried carefully and charged with 225 ml of tetrahydrofuran, 30.36 g (0.300 mol) of diisopropylamine, and cooled to 0° C. Over a 30 minute period, 190 ml (0.300 mol) of 1.6 M n-butyl lithium in hexane was added. The reaction mixture was stirred at 0° C. for 15 min., then cooled to -76° C. and 39.06 g (0.300 mol) of ethyl isovalerate added dropwise over ~15 min. When addition was complete, the reaction mixture was stirred for 15 min. at -76° C., then 82 ml (0.88 mol) of chlorotrimethylsilane added dropwise. When addition was complete, the Dry Ice-acetone bath was removed and the reaction mixture stirred for 11/2 hrs. while coming up to room temperature. A 1 liter flask was equipped with a mechanical stirrer, a reflux condenser, an addition funnel, nitrogen inlet The glassware was dried carefully cooled to -76° C. When addition the reaction mixture was stirred for 15 min. at -76° C. When addition the Dry Ice-acetone bath was removed the reaction mixture stirred for 11/2 hrs coming up to room temperature

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

Procedure: A 250 milliliter flask was equipped with a magnetic stirrer, reflux condenser and nitrogen inlet. The flask was dried with external heat and then charged with 19.92 grams (0.22 mol) of 3-chloro-1-butyne, 30.49 grams (0.15 mol) of 1-trimethylsilyloxy-1-ethoxy-3-methylbutene prepared in Part A, 100 milliliters of dry methylene chloride, and 0.5 grams of anhydrous zinc chloride. The reaction mixture was stirred at room temperature and monitored by infrared for 48 hours. The disappearance of the ketene acetal C=C peak at 1675 cm-1 and the appearance of an ester C=O peak at 1720 cm-1 was observed. The reaction mixture was then worked up by diluting with 150 milliliters of methylene chloride and washing five times with 100 milliliters of 5% sodium bicarbonate and twice with water. The methylene chloride was dried (MgSO4) and removed under vacuum to give a residue. The residue was vacuum distilled through a vigreux column to give 8.44 grams (0.05 mol) of ethyl 2-isopropyl-3-methyl-4-pentynoate having the appearance of a colorless oil and a boiling point of 66°-76° C. at 7 millimeters pressure. A 250 milliliter flask was equipped with a magnetic stirrer reflux condenser and nitrogen inlet The flask was dried with external heat washing five times with 100 milliliters of 5% sodium bicarbonate The methylene chloride was dried (MgSO4) removed under vacuum to give a residue distilled through a vigreux column

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2 liter flask was equipped with a mechanical stirrer, addition funnel, reflux condenser, nitrogen inlet and thermometer. The flask was dried with external heat and then charged with 563 milliliters of dry tetrahydrofuran, 75.9 grams (0.75 mol) of diisopropylamine and cooled to 0° C. Over a 30 minute period 523 milliliters of 1.6 M n-butyl lithium (0.94 mol) was added dropwise. The reaction mixture was stirred at 0° C. for 15 minutes, then cooled to -76° C. in a dry ice-acetone bath and 97.65 grams (0.75 mol) of ethyl isovalerate was added dropwise over about 30 minutes. When this addition was complete, the reaction mixture was stirred for 15 minutes at -76° C., then 205 milliliters (2.20 mol) of chlorotrimethylsilane was added dropwise. When this addition was complete, the dry ice-acetone bath was removed and the reaction mixture allowed to come to room temperature. The reaction mixture was then filtered and concentrated under reduced pressure to give a residue which was triturated with ether and filtered. The filtrate was concentrated under vacuum to give a residue and the residue was vacuum distilled through a vigreux column to give 136.44 grams (1.48 mol) of 1-trimethylsilyloxy-1-ethoxy-3-methylbutene having a boiling point of 78°-88° C. at 30 millimeters pressure. A 2 liter flask was equipped with a mechanical stirrer, addition funnel reflux condenser, nitrogen inlet The flask was dried with external heat cooled to -76° C. in a dry ice-acetone bath When this addition the reaction mixture was stirred for 15 minutes at -76° C. When this addition the dry ice-acetone bath was removed to come to room temperature The reaction mixture was then filtered concentrated under reduced pressure to give a residue which was triturated with ether filtered The filtrate was concentrated under vacuum to give a residue distilled through a vigreux column