(Z)-but-2-en-1-ol

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

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

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen, the flask is charged with 4-iodo-2-methoxy-pyridine-3-carbaldehyde (Intermediate 1, 75.0 g, 0.29 mol), crotyl alcohol (75 mL, 0.88 mol), and triethylsilane (70 mL, 0.44 mol). To the stirred suspension at 0° C. is added trifluoroacetic acid (175 mL, 2.27 mol) dropwise via an addition funnel. The resulting solution is stirred at about 22° C. for approximately 12 hours. The reaction mixture is slowly poured into a rapidly stirring saturated sodium bicarbonate solution (2 L). The mixture is extracted with 3×500 mL of hexane. The combined organic layers are dried over sodium sulfate, filtered, and concentrated in vacuo to give an oil. Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120-130° C.) yields 3-(but-2-enyloxymethyl)-4-iodo-2-methoxypyridine as a pale yellow oil: 1H-NMR (400 MHz, CDCl3) d 7.69 (d, J=5 Hz, 1 H), 7.34 (d, J=5 Hz, 1 H), 5.71 (m, 2 H), 4.58 (s, 2 H), 4.02 (d, J=1 Hz, 2 H), 3.94 (s, 3 H), 1.72 (d, J=6 Hz, 3 H); IR (neat) 2948, 2859, 1561, 1459, 1381, 1361, 1301, 1233, 1169, 1094, 1052 cm−1; Elemental analysis: calculated for C11H14NO2I: C, 41.40; H, 4.42; N, 4.39; I, 39.76. Found: C, 41.31; H, 4.45; N, 4.37; I, 39.71. A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen The mixture is extracted with 3×500 mL of hexane The combined organic layers are dried over sodium sulfate filtered concentrated in vacuo to give an oil Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120-130° C.)

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

Procedure: A three-necked 500-mL round-bottom flask is equipped with a mechanical stirrer. Under nitrogen, the flask is charged with 6-chloro-4-iodo-2-methoxypyridine-3-carbaldehyde (53.0 g, 178 mmol) obtained as prepared in U.S. Pat. No. 5,254,690 to Comins et al. issued Oct. 19, 1993, triethylsilane (42.7 mL, 267 mmol) and crotyl alcohol (60.8 mL, 713 mmol). The slurry is cooled to 0° C. and trifluoroacetic acid (90.0 mL, 1.17 mmol) is added over 1 h. The reaction is allowed to warm to ambient temperature and stirred for 16 h. The reaction mixture is slowly poured into a rapidly stirred solution of saturated sodium bicarbonate in water (1.5 L). The mixture is extracted with methyl t-butyl ether (4×300 mL). The combined organic layers are washed with brine (700 mL) and dried over anhydrous sodium sulfate (150 g). The drying agent is removed by filtration and the solvents are removed in vacuo to afford 6-chloro-4-iodo-2-methoxy-3-(2-butenyloxymethyl)pyridine as crude product. The product can be purified by vacuum distillation to provide 6-chloro-4-iodo-2-methoxy-3-(2-butenyloxymethyl)pyridine as a light yellow oil. 1H NMR (200 MHz, CDCL3) δ1.75 (d, J=6.1 Hz, 3H), 3.92 (s, 3H), 4.00 (m, 2H), 4.59 (s, 2H), 5.74 (m, 1H) 5.75 (m, 1H), 7.39 (s, 1H). A three-necked 500-mL round-bottom flask is equipped with a mechanical stirrer obtained as prepared in U.S to warm to ambient temperature The mixture is extracted with methyl t-butyl ether (4×300 mL) The combined organic layers are washed with brine (700 mL) dried over anhydrous sodium sulfate (150 g) The drying agent is removed by filtration the solvents are removed in vacuo

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen, the flask is charged with 4-iodo-2-methoxy-pyridine-3-carbaldehyde (75.0 g, 0.29 mol) prepared as in example 1, crotyl alcohol (75 mL, 0.88 mol), and triethylsilane (70 mL, 0.44 mol). To the stirred suspension at 0° C. is added trifluoroacetic acid (175 mL, 2.27 mol) dropwise via an addition funnel. The resulting solution is stirred at about 22° C. for approximately 12 hr. The reaction mixture is slowly poured into a rapidly stirring saturated sodium bicarbonate solution (2 L). The mixture is extracted with 3×500 mL of hexane. The combined organic layers are dried over sodium sulfate, filtered, and concentrated in vacuo to give an oil. Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120°-130° C.) yields 3-(but-2-enyloxymethyl)-4-iodo-2-methoxy-pyridine as a pale yellow oil: 1H-NMR (400 MHz, CDCl3) δ7.69 (d, J=5 Hz, 1H), 7.34 (d, J=5 Hz, 1H), 5.71 (m, 2H), 4.58 (s, 2H), 4.02 (d, J=1 Hz, 2H), 3.94 (s, 3H), 1.72 (d, J=6 Hz, 3H); IR (neat) 2948, 2859, 1561, 1459, 1381, 1361, 1301, 1233, 1169, 1094, 1052 cm-1 ; Elemental analysis: calculated for C11H14NO2I: C 41.40, H 4.42, N 4.39, I 39.76; Found: C 41.31, H 4.45, N 4.37, I39.71. A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen The mixture is extracted with 3×500 mL of hexane The combined organic layers are dried over sodium sulfate filtered concentrated in vacuo to give an oil Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120°-130° C.)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In accordance with Example 1, a homogeneous solution of 6.2 grams (0.11 moles) of butadiene and 100 milliliters of a 65 volume percent aqueous sulfolane solution were reacted in the presence of a cation exchanger sold under the trademark Lewatit SPC 118 at a temperature of 100° C. After agitating at 100° C. for 6 hours, 76 percent of the mixture had reacted. A yield of 60 percent 1-butene-3-ol and a yield of 26 percent 2-butene-1-ol (crotylalcohol) was obtained.

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen, the flask is charged with 4-iodo-2-methoxy-pyridine-3-carbaldehyde (Intermediate 1, 75.0 g, 0.29 mol), crotyl alcohol (75 mL, 0.88 mol), and triethylsilane (70 mL, 0.44 mol). To the stirred suspension at 0° C. is added trifluoroacetic acid (175 mL, 2.27 mol) dropwise via an addition funnel. The resulting solution is stirred at about 22° C. for approximately 12 hours. The reaction mixture is slowly poured into a rapidly stirring saturated sodium bicarbonate solution (2 L). The mixture is extracted with 3×500 mL of hexane. The combined organic layers are dried over sodium sulfate, filtered, and concentrated in vacuo to give an oil. Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120-130° C.) yields 3-(but-2-enyloxymethyl)-4-iodo-2-methoxypyridine as a pale yellow oil: 1H-NMR (400 MHz, CDCl3) d 7.69 (d, J=5 Hz, 1H), 7.34 (d, J=5 Hz, 1H), 5.71 (m, 2H), 4.58 (s, 2H), 4.02 (d, J=1 Hz, 2H), 3.94 (s, 3H), 1.72 (d, J=6 Hz, 3H); IR (neat) 2948, 2859, 1561, 1459, 1381, 1361, 1301, 1233, 1169, 1094, 1052 cm-1 ; Elemental analysis: calculated for C11H14NO2I: C 41.40, H 4.42, N 4.39, I 39.76; Found: C 41.31, H 4.45, N 4.37, I 39.71. A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen The mixture is extracted with 3×500 mL of hexane The combined organic layers are dried over sodium sulfate filtered concentrated in vacuo to give an oil Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120-130° C.)

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen, the flask is charged with 4-iodo-2-methoxy-pyridine-3-carbaldehyde (Intermediate 1, 75.0 g, 0.29 mol), crotyl alcohol (75 mL, 0.88 mol), and triethylsilane (70 mL, 0.44 mol). To the stirred suspension at 0° C. is added trifluoroacetic acid (175 mL, 2.27 mol) dropwise via an addition funnel. The resulting solution is stirred at about 22° C. for approximately 12 hours. The reaction mixture is slowly poured into a rapidly stirring saturated sodium bicarbonate solution (2 L). The mixture is extracted with 3×500 mL of hexane. The combined organic layers are dried over sodium sulfate, filtered, and concentrated in vacuo to give an oil. Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120-130° C.) yields 3-(but-2-enyloxymethyl)-4-iodo-2-methoxypyridine as a pale yellow oil: 1H-NMR (400 MHz, CDCl3) d 7.69 (d, J=5 Hz, 1H), 7.34 (d, J=5 Hz, 1H), 5.71 (m, 2H), 4.58 (s, 2H), 4.02 (d, J=1 Hz, 2H), 3.94 (s, 3H), 1.72 (d, J=6 Hz, 3H); IR (neat) 2948, 2859, 1561, 1459, 1381, 1361, 1301, 1233, 1169, 1094, 1052 cm-1 ; Elemental analysis: calculated for C11H14NO2I: C 41.40, H 4.42, N 4.39, I 39.76; Found: C 41.31, H 4.45, N 4.37, I 39.71. A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen The mixture is extracted with 3×500 mL of hexane The combined organic layers are dried over sodium sulfate filtered concentrated in vacuo to give an oil Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120-130° C.)

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen, the flask is charged with 4-iodo-2-methoxy-pyridine-3-carbaldehyde (Intermediate 1, 75.0 g, 0.29 mol), crotyl alcohol (75 mL, 0.88 mol), and triethylsilane (70 mL, 0.44 mol). To the stirred suspension at 0° C. is added trifluoroacetic acid (175 mL, 2.27 mol) dropwise via an addition funnel. The resulting solution is stirred at about 22° C. for approximately 12 hours. The reaction mixture is slowly poured into a rapidly stirring saturated sodium bicarbonate solution (2 L). The mixture is extracted with 3×500 mL of hexane. The combined organic layers are dried over sodium sulfate, filtered, and concentrated in vacuo to give an oil. Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120-130° C.) yields 3-(but-2-enyloxymethyl)-4-iodo-2-methoxypyridine as a pale yellow oil: 1 H-NMR (400 MHz, CDCl3d 7.69 (d, J=5 Hz, 1 H), 7.34 (d, J=5 Hz, 1 H), 5.71 (m, 2 H), 4.58 (s, 2 H), 4.02 (d, J=1 Hz, 2 H), 3.94 (s, 3 H), 1.72 (d, J=6 Hz, 3 H); IR (neat) 2948, 2859, 1561, 1459, 1381, 1361, 1301, 1233, 1169, 1094, 1052 cm−1; Elemental analysis: calculated for C11H14NO2I: C 41.40, H 4.42, N 4.39, I 39.76; Found: C 41.31, H 4.45, N 4.37, I 39.71. A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen The mixture is extracted with 3×500 mL of hexane The combined organic layers are dried over sodium sulfate filtered concentrated in vacuo to give an oil Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120-130° C.)

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen, the flask is charged with 4-iodo-2-methoxy-pyridine-3-carbaldehyde (Intermediate 1, 75.0 g, 0.29 mol), crotyl alcohol (75 mL, 0.88 mol), and triethylsilane (70 mL, 0.44 mol). To the stirred suspension at 0° C. is added trifluoroacetic acid (175 mL, 2.27 mol) dropwise via an addition funnel. The resulting solution is stirred at about 22° C. for approximately 12 hours. The reaction mixture is slowly poured into a rapidly stirring saturated sodium bicarbonate solution (2 L). The mixture is extracted with 3×500 mL of hexane. The combined organic layers are dried over sodium sulfate, filtered, and concentrated in vacuo to give an oil. Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120-130° C.) yields 3-(but-2-enyloxymethyl)-4-iodo-2-methoxypyridine as a pale yellow oil: 1 H-NMR (400 MHz, CDCl3d 7.69 (d, J=5 Hz, 1 H), 7.34 (d, J=5 Hz, 1 H), 5.71 (m, 2 H), 4.58 (s, 2 H), 4.02 (d, J=1 Hz, 2 H), 3.94 (s, 3 H), 1.72 (d, J=6 Hz, 3 H); IR (neat) 2948, 2859, 1561, 1459, 1381, 1361, 1301, 1233, 1169, 1094, 1052 cm−1; Elemental analysis: calculated for C11H14NO2I: C 41.40, H 4.42, N 4.39, I 39.76; Found: C 41.31, H 4.45, N 4.37, I 39.71. A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen The mixture is extracted with 3×500 mL of hexane The combined organic layers are dried over sodium sulfate filtered concentrated in vacuo to give an oil Purification of this oil by vacuum distillation (about 0.4 mm Hg, about 120-130° C.)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A stirred mixture of 36.06 g of crotyl alcohol, 162.2 g of triethyl orthoacetate and 2.22 g of propionic acid was slowly heated to 100° C. (1.25 hours), stirred and heated at 100°-115° C. for 1 hour, at 115°-145° C. for 2.5 hours, then at 145°-155° C. for 6 hours. The mixture was cooled in an ice bath and treated with 50 ml of glacial acetic acid and 50 ml of water. The mixture was stirred at room temperature for 45 minutes, diluted with ether, extracted with saturated sodium bicarbonate solution, then with brine and dried (MgSO4). The solvent was evaporated under reduced pressure and the residue was distilled under reduced pressure to give ethyl 3-methyl-4-pentenoate (3A), as a colorless liquid, b.p.: 88°-91° C. (60 Torr.). heated at 100°-115° C. for 1 hour, at 115°-145° C. for 2.5 hours The mixture was cooled in an ice bath The mixture was stirred at room temperature for 45 minutes extracted with saturated sodium bicarbonate solution with brine and dried (MgSO4) The solvent was evaporated under reduced pressure the residue was distilled under reduced pressure

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A stirred mixture of 36.06 g of crotyl alcohol, 162.2 g of triethyl orthoacetate and 2.22 g of propionic acid was slowly heated to 100° C. (1.25 hours), stirred and heated at 100°-115° C. for 1 hour, at 115°-145° C. for 2.5 hours, then at 145°-155° C. for 6 hours. The mixture was cooled in an ice bath and treated with 50 ml of glacial acetic acid and 50 ml of water. The mixture was stirred at room temperature for 45 minutes, diluted with ether, extracted with saturated sodium bicarbonate solution, then with brine and dried (MgSO4). The solvent was evaporated under reduced pressure and the residue was distilled under reduced pressure to give ethyl 3-methyl-4-pentenoate (3A), as a colorless liquid, b.p.: 88°-91° C. (60 Torr.). heated at 100°-115° C. for 1 hour, at 115°-145° C. for 2.5 hours The mixture was cooled in an ice bath The mixture was stirred at room temperature for 45 minutes extracted with saturated sodium bicarbonate solution with brine and dried (MgSO4) The solvent was evaporated under reduced pressure the residue was distilled under reduced pressure