oct-2-ene

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

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

Procedure: 1.25 g of the mixture of 3-(1,1-methylene-5-acetoxypentyl)-6β-[3α-(2-tetrahydropyranyloxy)-5(R),9-dimethyl-1,8-decadienyl]-7α-(2-tetrahydropyranyloxy)bicyclo[3.3.0]oct-2-ene and its oct-3-ene isomer (prepared as described in Example 8) was dissolved in 30 ml of methanol. 0.25 g of anhydrous potassium carbonate was added to the mixture, and the mixture was stirred for 2.5 hours at room temperature. The reaction mixture was then diluted with 150 ml of water, and the solution was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the resulting residue was subjected to medium pressure liquid chromatography using a Lobar (trade mark) column (size C), eluted with a 1:2 by volume mixture of ethyl acetate and hexane, yielding 0.68 g of the oct-2-ene compound and 0.51 g of the oct-3-ene compound. the solution was extracted with ethyl acetate The extract was washed with water dried over anhydrous sodium sulfate The solvent was distilled off under reduced pressure eluted with a 1:2 by volume mixture of ethyl acetate and hexane

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

Procedure: 0.12 mmoles of bis-(η5-cyclopentadienyl)titanium dichloride (Cp2TiCl2; Aldrich commercial product), 20 ml of anhydrous cyclohexane, 0.03 ml of a solution of n-dibutylglima 0.45 M in anhydrous cyclohexane and 0.54 ml of 1 molar Mg(butyl)2 in n-heptane (atomic ratio Mg/Ti=4.5), are charged into a tailed test-tube equipped with a magnetic stirrer, in an atmosphere of argon. The mixture is left under stirring for 20 hours at room temperature. 18.8 ml of 1-octene (distilled and maintained on molecular sieves) are added. At this point the solution is siphoned in an autoclave previously maintained under argon and the same procedure is carried out as described in example 1 above. At the end it is cooled to room temperature. About 14 ml of octane and 4 ml of 2-octene are obtained by distillation (GC, mass GC and NMR analyses). The results and process conditions are summarized in table 1 below. equipped with a magnetic stirrer, in an atmosphere of argon The mixture is left previously maintained under argon At the end it is cooled to room temperature

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

Procedure: 0.12 mmoles of (η5-cyclopentadienyl)titanium trichloride (CpTiCl3; Aldrich commercial product), 20 ml of anhydrous cyclohexane, 0.03 ml of a solution of n-dibutylglima 0.45 M in anhydrous cyclohexane and 0.54 ml of 1 molar Mg(butyl)2 in n-heptane (atomic ratio Mg/Ti=4.5), are charged into a tailed test-tube equipped with a magnetic stirrer, in an atmosphere of argon. The mixture is left under stirring for 20 hours at room temperature (the solution takes on an extremely dark colouring). 18.8 ml of 1-octene (distilled and maintained on molecular sieves) are added. At this point the solution is siphoned in an autoclave previously maintained under argon and the same procedure is carried out as described in example 1 above. At the end it is cooled to room temperature. About 18 ml of octane and 0.4 ml of 2-octene are obtained by distillation (GC, mass GC and NMR analyses). The results and process conditions are summarized in table 1 below. equipped with a magnetic stirrer, in an atmosphere of argon The mixture is left previously maintained under argon At the end it is cooled to room temperature

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

Procedure: 0.12 mmoles of (η5-cyclopentadienyl)titanium trichloride (CpTiCl3; Aldrich commercial product), 20 ml of anhydrous cyclohexane, 0.03 ml of a solution of n-dibutylglima 0.45 M in anhydrous cyclohexane and 0.54 ml of 1 molar Mg(butyl)2 in n-heptane (atomic ratio Mg/Ti=4.5), are charged into a tailed test-tube equipped with a magnetic stirrer, in an atmosphere of argon. The mixture is left under stirring for 20 hours at room temperature (the solution takes on an extremely dark colouring). 18.8 ml of 1-octene (distilled and maintained on molecular sieves) are added. At this point the solution is siphoned in an autoclave previously maintained under argon and the same procedure is carried out as described in example 1 above. At the end it is cooled to room temperature. About 18 ml of octane and 0.4 ml of 2-octene are obtained by distillation (GC, mass GC and NMR analyses). The results and process conditions are summarized in table 1 below. equipped with a magnetic stirrer, in an atmosphere of argon The mixture is left previously maintained under argon At the end it is cooled to room temperature

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

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

Procedure: 1.25 g of the mixture of 3-(1,1-methylene-5-acetoxypentyl)-6β-[3α-(2-tetrahydropyranyloxy)-5(R),9-dimethyl-1,8-decadienyl]-7α-(2-tetrahydropyranyloxy)bicyclo[3.3.0]oct-2-ene and its oct-3-ene isomer (prepared as described in Example 8) was dissolved in 30 ml of methanol. 0.25 g of anhydrous potassium carbonate was added to the mixture, and the mixture was stirred for 2.5 hours at room temperature. The reaction mixture was then diluted with 150 ml of water, and the solution was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the resulting residue was subjected to medium pressure liquid chromatography using a Lobar (trade mark) column (size C), eluted with a 1:2 by volume mixture of ethyl acetate and hexane, yielding 0.68 g of the oct-2-ene compound and 0.51 g of the oct-3-ene compound. the solution was extracted with ethyl acetate The extract was washed with water dried over anhydrous sodium sulfate The solvent was distilled off under reduced pressure eluted with a 1:2 by volume mixture of ethyl acetate and hexane

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

Procedure: To 5 ml of dioxane and 200 mg of a suspension of 55% w/w sodium hydride in mineral oil was added 1 ml of diethyl carbonate, and the mixture was heated, with stirring, at an external temperature of 90° C. To the mixture was then added dropwise a solution of 150 ml of 3-(5-benzyloxypentyl)-7-oxo-cis-bicyclo[3,3,0]oct-2-ene (prepared as described in Preparation 5) in 3 ml of dioxane. During this addition, a catalytic amount of ethanol was also added. The mixture was stirred for 1 hour at 0° C., after which it was poured into ice-water, acidified with acetic acid and then extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. The solvent was evaporated off under reduced pressure, and the resulting residue was purified by silica gel column chromatography. 72 mg of the oct-2-ene isomer of the title compound and 57 mg of the oct-3-ene isomer were obtained from the fractions eluted with hexane containing 3% by volume of ethyl acetate and 5% by volume of ethyl acetate, respectively. the mixture was heated During this addition The mixture was stirred for 1 hour at 0° C. extracted with ethyl acetate The extract was washed with a saturated aqueous solution of sodium chloride dried over anhydrous sodium sulfate The solvent was evaporated off under reduced pressure the resulting residue was purified by silica gel column chromatography

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

Procedure: To 5 ml of dioxane and 200 mg of a suspension of 55% w/w sodium hydride in mineral oil was added 1 ml of diethyl carbonate, and the mixture was heated, with stirring, at an external temperature of 90° C. To the mixture was then added dropwise a solution of 150 ml of 3-(5-benzyloxypentyl)-7-oxo-cis-bicyclo[3,3,0]oct-2-ene (prepared as described in Preparation 5) in 3 ml of dioxane. During this addition, a catalytic amount of ethanol was also added. The mixture was stirred for 1 hour at 0° C., after which it was poured into ice-water, acidified with acetic acid and then extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. The solvent was evaporated off under reduced pressure, and the resulting residue was purified by silica gel column chromatography. 72 mg of the oct-2-ene isomer of the title compound and 57 mg of the oct-3-ene isomer were obtained from the fractions eluted with hexane containing 3% by volume of ethyl acetate and 5% by volume of ethyl acetate, respectively. the mixture was heated During this addition The mixture was stirred for 1 hour at 0° C. extracted with ethyl acetate The extract was washed with a saturated aqueous solution of sodium chloride dried over anhydrous sodium sulfate The solvent was evaporated off under reduced pressure the resulting residue was purified by silica gel column chromatography

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

Procedure: Under a nitrogen atmosphere, 2-(allyl carboxylate)-3-(monofluoroacetyl)-7-(R,S)-(t-butoxycarbonylamino)-8-oxo-1,5-diazabicyclo 3.3.0]octa-2-ene (190 mg, 0.5 mmol) was combined with a glacial acetic acid solution that was 3N in anhydrous hydrogen chloride (10 ml). The solution was stirred at room temperature for 10 minutes then concentrated in vacuo. The remaining volatiles on the concentrate were removed by azeotropic distillation with methylene chloride (2 x) to give 2-(allyl carboxylate)-3-(monofluoroacetyl)-7-(R,S)-amino-8-oxo-1,5-diazabicyclo 3.3.0]octa-2-ene hydrochloride. then concentrated in vacuo The remaining volatiles on the concentrate were removed by azeotropic distillation with methylene chloride (2 x)

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2 mmol of 2-octene (a mixture of cis- and trans-isomers), 10 mmol of tetralin, 0.2 mmol of N-hydroxyphthalimide, 0.1 mmol of molybdenum hexacarbonyl, 0.002 mmol of cobalt (II) acetate, and 2 ml of acetonitrile was stirred at 70° C. under an oxygen atmosphere (1 atm) for 5 hours. Gas chromatographic analysis of products in a reaction mixture revealed that 2-octene was converted, at a rate of 56%, into 2,3-epoxyoctane in yield of 49%. In this connection, tetralin was found to be converted, at a rate of 23%, into α-tetralol (yield: 7.7%) and α-tetralone (yield: 10%).

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2 mmol of 2-octene (a mixture of cis-isomer and trans-isomer), 10 mmol of tetralin, 0.2 mmol of N-hydroxyphthalimide, 0.1 mmol of molybdenum hexacarbonyl, 0.002 mmol of manganese (II) acetate, and 2 ml of benzonitrile was stirred at 70° C. under an oxygen atmosphere (1 atm) for 5 hours. Gas chromatographic analysis of products in a reaction mixture revealed that 2-octene was converted, at a rate of 67%, into 2,3-epoxyoctane in yield of 53%. In this connection, tetralin was found to be converted, at a rate of 20%, into α-tetralol (yield: 8.2%) and α-tetralone (yield: 8.3%).