1-methoxycyclohexa-1,4-diene

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2.85 g. (26 mmoles)of 1-methoxy-1, 4-cyclohexadiene and 30 ml. of absolute methanol was treated with ozone (1.25 g., 26 mmoles) at -78°C. The resulting mixture was flushed with nitrogen. The mixture was allowed to come to 0°C and 2.42 g. (39 mmoles) of dimethylsulfide were added and the mixture stirred at this temperature for 80 minutes. After cooling to -78°C, a suspension of 1.47 g/ (39 mmoles) of sodium borohydride in 20 ml. of absolute ethanol was added dropwise. The resulting mixture was allowed to come up to room temperature and then stirred for 80 minutes. The methanol was removed under vacuum to produce 3.3 g. of product (88% of theory). B.p. 60° (0.2 mm., short path distillation). A mixture of 2.85 g The resulting mixture was flushed with nitrogen to come to 0°C to come up to room temperature stirred for 80 minutes The methanol was removed under vacuum to produce 3.3 g B.p. 60° (0.2 mm., short path distillation)

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

Procedure: 11 g (0.1 mol) of 1-methoxycyclohexa-1,4-diene are heated under reflux with 0.1 g of tris(triphenylphosphine)-ruthenium dichloride and 8.8 g (0.09 mol) of maleimide in 100 ml of absolute chloroform overnight. The mixture is concentrated and the residue is recrystallized from 100 ml of toluene. The mixture is concentrated the residue is recrystallized from 100 ml of toluene

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

Procedure: 11 g (0.1 mol) of 1-methoxycyclohexa-1,4-diene are heated under reflux with 0.1 g of tris(triphenylphosphine)-ruthenium dichloride and 8.8 g (0.09 mol) of maleimide in 100 ml of absolute chloroform overnight. The mixture is concentrated and the residue is recrystallized from 100 ml of toluene. The mixture is concentrated the residue is recrystallized from 100 ml of toluene

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

Procedure: Reduction of anisole. Lithium, in small pieces, (8.75 g, 1.25 gram-atoms) was added to a solution of anisole (54 g, 0.5 mol) in n-propylamine (400 mL), ethylenediamine (105 g (1.75 mol) and t-butanol (111 g, 1.5 mol) cooled to -18°. The temperature increased to 12° and then decreased to -5°. After 2 hr all of the lithium had reacted and the reaction mixture was diluted with 800 mL of water added slowly. The mixture was extracted with ether (3×250 mL). The ether extracts were washed with water (3×200 mL) and brine (1×100 mL) and evaporated. The residue was distilled to give 27.5 g (50% of 1-methoxy-1,4-cyclohexadiene containing 10% of 1-methoxy-1,3-cyclohexadiene by glpc and nmr. cooled to -18° The temperature increased to 12° decreased to -5° added slowly The mixture was extracted with ether (3×250 mL) The ether extracts were washed with water (3×200 mL) and brine (1×100 mL) evaporated The residue was distilled

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

Procedure: 11 g (0.1 mol) of 1-methoxycyclohexa-1,4-diene are heated under reflux with 0.1 g of tris(triphenylphosphine)-ruthenium dichloride and 8.8 g (0.09 mol) of maleimide in 100 ml of absolute chloroform overnight. The mixture is concentrated and the residue is recrystallized from 100 ml of toluene. The mixture is concentrated the residue is recrystallized from 100 ml of toluene

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

Procedure: 11 g (0.1 mol) of 1-methoxycyclohexa-1,4-diene are heated under reflux with 0.1 g of tris(triphenylphosphine)-ruthenium dichloride and 8.8 g (0.09 mol) of maleimide in 100 ml of absolute chloroform overnight. The mixture is concentrated and the residue is recrystallized from 100 ml of toluene. The mixture is concentrated the residue is recrystallized from 100 ml of toluene

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

Procedure: The compounds of this invention represented by formula II are conveniently prepared by treatment of 1-methoxy-1,4-cyclohexadiene with successively ozone and methanol, dimethyl sulfide and sodium borohydride to afford methyl 6-hydroxy-(Z)-3-hexenoate. The methyl 6-hydroxy-(Z)-3-hexanoate is then converted to a protected ether, suitably either a tetrahydroxypyranyl or triethylsilyl ether. This may be achieved by reaction with 3,4-dihydropyran and pyridinium p-toluenesulfonate in methylene chloride to give methyl 6-tetrahydropyranyloxy-(Z)-3-hexenoate, which is further treated with a reducing agent such as lithium aluminum hydride to afford 6-tetrahydropyranyloxy-(Z)-3-hexen-1-ol. The latter compound is converted to the corresponding terminal iodide or bromide, 1-iodo-6-tetrahydropyranyloxy-(Z)-3-hexene is formed by reaction with p-toluenesulfonyl chloride, followed by sodium iodide. Alternately, the 6-tetrahydropyranyloxy-(Z)-3-hexen-1-ol can be converted to the corresponding bromide. Either the bromide or iodide is then reacted with triphenyl phosphine to form the 6-tetrahydropyranyloxy-(Z)-3-hexen-1-triphenylphosphonium iodide (or bromide). This iodide or bromide is then reacted with an omega hydroxy aldehyde of the formula VII ##STR1## wherein n is as hereinbefore defined, to form the intermediate of the formula VIII ##STR2## wherein n and Pr are as hereinbefore defined.