undec-10-enal

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: Under an argon atmosphere, a stirred mixture of 101.0 grams (0.60 mole) of 10-undecenal and 251.9 grams (1.20 moles) of dibromodifluoromethane was cooled to 0° to -5° C., and a solution of 314.9 grams (1.20 moles) of triphenylphosphine in 1100 ml of N,N-dimethylacetamide was added dropwise during a five to ten minute period. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it was stirred for two hours. After this time a small portion from 70.5 grams (1.20 mole) of zinc powder was added to the reaction mixture. The reaction mixture was warmed to approximately 34° C. with an external heat source to initiate further reaction. Upon commencement of the reaction, the reaction mixture temperature rose to 44° C. The remainder of the 70.5 grams of zinc powder was added portionwise during a ten to twenty minute period. Upon completion of addition, the reaction mixture was warmed to 85°-90° C. where it stirred vigorously for two hours. After this time the reaction mixture was cooled to ambient temperature, and 400 ml of water was added. The reaction mixture was stirred for 30 minutes and then was allowed to stand for 18 hours. After this time the reaction mixture was subjected to a steam distillation using pentane as the extraction solvent. The pentane distillate was concentrated under reduced pressure to a residual oil. The residual oil was heated at 94° C. to remove any N,N-dimethylacetamide. The remaining oil was distilled under reduced pressure, yielding 24.3 grams of 1,1-difluoro-1,11-dodecadiene; b.p. 133° C./66 mm. The nmr spectrum was consistent with the proposed structure. was cooled to 0° to -5° C. Upon completion of addition The reaction mixture was warmed to approximately 34° C. with an external heat source reaction Upon commencement of the reaction rose to 44° C Upon completion of addition the reaction mixture was warmed to 85°-90° C. where it stirred vigorously for two hours After this time the reaction mixture was cooled to ambient temperature The reaction mixture was stirred for 30 minutes to stand for 18 hours After this time the reaction mixture was subjected to a steam distillation The pentane distillate was concentrated under reduced pressure to a residual oil The residual oil was heated at 94° C. to remove any N,N-dimethylacetamide The remaining oil was distilled under reduced pressure

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

Procedure: Under an argon atmosphere, a stirred mixture of 101.0 grams (0.60 mole) of 10-undecenal and 251.9 grams (1.20 moles) of dibromodifluoromethane was cooled to 0° to -5° C., and a solution of 314.9 grams (1.20 moles) of triphenylphosphine in 1100 ml of N,N-dimethylacetamide was added dropwise during a five to ten minute period. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it was stirred for two hours. After this time a small portion from 70.5 grams (1.20 mole) of zinc powder was added to the reaction mixture. The reaction mixture was warmed to approximately 34° C. with an external heat source to initiate further reaction. Upon commencement of the reaction, the reaction mixture temperature rose to 44° C. The remainder of the 70.5 grams of zinc powder was added portionwise during a ten to twenty minute period. Upon completion of addition, the reaction mixture was warmed to 85°-90° C. where it stirred vigorously for two hours. After this time the reaction mixture was cooled to ambient temperature, and 400 ml of water was added. The reaction mixture was stirred for 30 minutes and then was allowed to stand for 18 hours. After this time the reaction mixture was subjected to a steam distillation using pentane as the extraction solvent. The pentane distillate was concentrated under reduced pressure to a residual oil. The residual oil was heated at 94° C. to remove any N,N-dimethylacetamide. The remaining oil was distilled under reduced pressure, yielding 24.3 grams of 1,1-difluoro-1,11-dodecadiene; b.p. 133° C./66 mm. The nmr spectrum was consistent with the proposed structure. was cooled to 0° to -5° C. Upon completion of addition The reaction mixture was warmed to approximately 34° C. with an external heat source reaction Upon commencement of the reaction rose to 44° C Upon completion of addition the reaction mixture was warmed to 85°-90° C. where it stirred vigorously for two hours After this time the reaction mixture was cooled to ambient temperature The reaction mixture was stirred for 30 minutes to stand for 18 hours After this time the reaction mixture was subjected to a steam distillation The pentane distillate was concentrated under reduced pressure to a residual oil The residual oil was heated at 94° C. to remove any N,N-dimethylacetamide The remaining oil was distilled under reduced pressure

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

Procedure: Under an argon atmosphere, a stirred solution of 82.0 grams (0.646 mole) of oxalyl chloride in 600 ml of methylene chloride was cooled to -50° to -60° C., and a solution of 100.9 grams (1.292 moles) of dimethyl sulfoxide in 120 ml of methylene chloride was added dropwise during a 10-15 minute period. The reaction mixture temperature was maintained at -50° to -60° C. during the addition. Upon completion of addition, the reaction mixture was stirred for two minutes, and then a solution of 100.0 grams (0.587 mole) of 10-undecen-1-ol in 130 ml of methylene chloride was added dropwise during a 15 minute period while maintaining the reaction mixture temperature at -50° to -60° C. Upon completion of addition, the reaction mixture was stirred for 15 minutes, and then 297.1 grams (2.936 moles) of triethylamine was added dropwise during a five minute period while still maintaining the reaction mixture temperature at -50° to -60° C. Upon completion of addition, the reaction mixture was stirred as it was allowed to warm to ambient temperature. After this time 700 ml of water was stirred with the reaction mixture. The water layer was separated and washed with two 160 ml portions of methylene chloride. The washes were combined with the organic layer, and the combination was washed with three 160 ml portions of an aqueous solution saturated with sodium chloride. The organic layer was dried with magnesium sulfate and was then filtered. The filtrate was concentrated under reduced pressure to an oil/solid residue. The residue was stirred with 400 ml of pentane, and the solid was separated by filtration. The filtrate was concentrated under reduced pressure yielding 101.4 grams of 10-undecenal as an oil. The ir spectrum was consistent with the proposed structure. The reaction mixture temperature was maintained at -50° to -60° C. during the addition Upon completion of addition while maintaining the reaction mixture temperature at -50° to -60° C Upon completion of addition the reaction mixture was stirred for 15 minutes while still maintaining the reaction mixture temperature at -50° to -60° C Upon completion of addition the reaction mixture was stirred as it The water layer was separated washed with two 160 ml portions of methylene chloride the combination was washed with three 160 ml portions of an aqueous solution saturated with sodium chloride The organic layer was dried with magnesium sulfate was then filtered The filtrate was concentrated under reduced pressure to an oil/solid residue The residue was stirred with 400 ml of pentane the solid was separated by filtration The filtrate was concentrated under reduced pressure

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

Procedure: Other primary and secondary alcohols of the present invention were also prepared from commercially available omega unsaturated alcohols by a second route. An unsaturated alcohol (I), e.g., 10-undecen-1-ol, was first oxidized to 10-undecen-1-al (V) by the Swern oxidation using oxalyl chloride, dimethyl sulfoxide, and triethylamine in methylene chloride. This aldehyde was then reacted with dibromodifluoromethane, triphenylphosphine, and powdered zinc in dimethylacetamide, producing 1,1-difluoro-1,11-dodecadiene (VI). In order to prepare a secondary alcohol from (VI), the latter was reacted with mercuric acetate in tetrahydrofuran and water and then with sodium borohydride and aqueous sodium hydroxide, producing 12,12-difluoro-11-dodecen-2-ol (VII). Oxidation of (VII) with Jones reagent in acetone yielded methyl 10,10-difluoro-9-decenyl ketone (VIII) which could in turn be reacted with a Grignard reagent, e.g., methylmagnesium bromide, to produce 2-methyl-12,12-difluoro-11-dodecen-2-ol (IX), a tertiary alcohol. Synthesis of primary alcohols was accomplished by reacting (VI) with borane tetrahydrofuran complex and then with sodium hydroxide and hydrogen peroxide, yielding 12,12-difluoro-11-dodecen-1-ol (X). Examples 3, 4, and 5 detail the methods employing this route.

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

Procedure: A mixture of 1a (1.50 g, 11.0 mmol) and 10-undecenal (2.80 g, 16.5 mmol) in ethanol (28 ml) was heated under reflux for 2 h. After cooling to room temperature, the product was concentrated, washed with hexane and dried under vacuum (0.20 mbar) to give 2.78 g (88%) of a white solid. was heated under reflux for 2 h the product was concentrated washed with hexane dried under vacuum (0.20 mbar)

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

Procedure: Undec-10-enal (84 g, 0.5 mol.), heptane (84 g, 100 wt. %, technical grade), and (ethylenediamine)[1,2-bis(diphenylphosphino)ethane]ruthenium[bis((adamantane-1-carboxylate)] (45.9 mg, 0.05 mmol, 0.01 mol.%) were loaded altogether in a 300 ml autoclave equipped with a mechanical stirring device. Sealed autoclave was then purged under stirring with nitrogen (3 times 5 bars) and hydrogen (3 times 5 bars) before being pressurized to 10 bars hydrogen. It was then heated to 70° C. and hydrogen pressure was maintained to 10 bars during all the reaction to afford desired product with 90% selectivity. After complete reaction conversion (checked by both hydrogen consumption and GC), autoclave was cooled down to 25° C. It was then depressurized and purged with nitrogen (3 times 5 bars) and reaction mixture was then transferred to a round-bottomed flask and solvent was removed under vacuum. After initial flash distillation and further fractional distillation, undec-10-en-1-ol was obtained in 85% yield. equipped with a mechanical stirring device Sealed autoclave was then purged hydrogen pressure was maintained to 10 bars during all the reaction

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

Procedure: To a solution of 16.8 g 10-undecenal in 25 ml methylene chloride, crystals of di-μ-chlorodichlorobis(ethylene)-diplatinum (II) were added and the solution heated to 40°-45° C. A solution of 16.4 g triethoxysilane in 25 ml methylene chloride was added dropwise over a period of 90 minutes. After reagent addition was completed, the rection mixture was heated for an additional 30 minutes. The mixture was fractionated and the product, 11-triethoxysilylundecanal (I) was obtained at 65° C. at 0.2 mm Hg at a 30% yield. the solution heated to 40°-45° C After reagent addition the rection mixture was heated for an additional 30 minutes

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

Procedure: Under an argon atmosphere, a stirred mixture of 101.0 grams (0.60 mole) of 10-undecenal and 251.9 grams (1.20 moles) of dibromodifluoromethane was cooled to 0° to -5° C., and a solution of 314.9 grams (1.20 moles) of triphenylphosphine in 1100 ml of N,N-dimethylacetamide was added dropwise during a five to ten minute period. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it was stirred for two hours. After this time a small portion from 70.5 grams (1.20 mole) of zinc powder was added to the reaction mixture. The reaction mixture was warmed to approximately 34° C. with an external heat source to initiate further reaction. Upon commencement of the reaction, the reaction mixture temperature rose to 44° C. The remainder of the 70.5 grams of zinc powder was added portionwise during a ten to twenty minute period. Upon completion of addition, the reaction mixture was warmed to 85°-90° C. where it stirred vigorously for two hours. After this time the reaction mixture was cooled to ambient temperature, and 400 ml of water was added. The reaction mixture was stirred for 30 minutes and then was allowed to stand for 18 hours. After this time the reaction mixture was subjected to a steam distillation using pentane as the extraction solvent. The pentane distillate was concentrated under reduced pressure to a residual oil. The residual oil was heated at 94° C. to remove any N,N-dimethylacetamide. The remaining oil was distilled under reduced pressure, yielding 24.3 grams of 1,1-difluoro-1,11-dodecadiene; b.p. 133° C./66 mm. The nmr spectrum was consistent with the proposed structure. was cooled to 0° to -5° C. Upon completion of addition The reaction mixture was warmed to approximately 34° C. with an external heat source reaction Upon commencement of the reaction rose to 44° C Upon completion of addition the reaction mixture was warmed to 85°-90° C. where it stirred vigorously for two hours After this time the reaction mixture was cooled to ambient temperature The reaction mixture was stirred for 30 minutes to stand for 18 hours After this time the reaction mixture was subjected to a steam distillation The pentane distillate was concentrated under reduced pressure to a residual oil The residual oil was heated at 94° C. to remove any N,N-dimethylacetamide The remaining oil was distilled under reduced pressure

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

Procedure: Under an argon atmosphere, a stirred solution of 82.0 grams (0.646 mole) of oxalyl chloride in 600 ml of methylene chloride was cooled to -50° to -60° C., and a solution of 100.9 grams (1.292 moles) of dimethyl sulfoxide in 120 ml of methylene chloride was added dropwise during a 10-15 minute period. The reaction mixture temperature was maintained at -50° to -60° C. during the addition. Upon completion of addition, the reaction mixture was stirred for two minutes, and then a solution of 100.0 grams (0.587 mole) of 10-undecen-1-ol in 130 ml of methylene chloride was added dropwise during a 15 minute period while maintaining the reaction mixture temperature at -50° to -60° C. Upon completion of addition, the reaction mixture was stirred for 15 minutes, and then 297.1 grams (2.936 moles) of triethylamine was added dropwise during a five minute period while still maintaining the reaction mixture temperature at -50° to -60° C. Upon completion of addition, the reaction mixture was stirred as it was allowed to warm to ambient temperature. After this time 700 ml of water was stirred with the reaction mixture. The water layer was separated and washed with two 160 ml portions of methylene chloride. The washes were combined with the organic layer, and the combination was washed with three 160 ml portions of an aqueous solution saturated with sodium chloride. The organic layer was dried with magnesium sulfate and was then filtered. The filtrate was concentrated under reduced pressure to an oil/solid residue. The residue was stirred with 400 ml of pentane, and the solid was separated by filtration. The filtrate was concentrated under reduced pressure yielding 101.4 grams of 10-undecenal as an oil. The ir spectrum was consistent with the proposed structure. The reaction mixture temperature was maintained at -50° to -60° C. during the addition Upon completion of addition while maintaining the reaction mixture temperature at -50° to -60° C Upon completion of addition the reaction mixture was stirred for 15 minutes while still maintaining the reaction mixture temperature at -50° to -60° C Upon completion of addition the reaction mixture was stirred as it The water layer was separated washed with two 160 ml portions of methylene chloride the combination was washed with three 160 ml portions of an aqueous solution saturated with sodium chloride The organic layer was dried with magnesium sulfate was then filtered The filtrate was concentrated under reduced pressure to an oil/solid residue The residue was stirred with 400 ml of pentane the solid was separated by filtration The filtrate was concentrated under reduced pressure

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

Procedure: Other primary and secondary alcohols of the present invention were also prepared from commercially available omega unsaturated alcohols by a second route. An unsaturated alcohol (I), e.g., 10-undecen-1-ol, was first oxidized to 10-undecen-1-al (V) by the Swern oxidation using oxalyl chloride, dimethyl sulfoxide, and triethylamine in methylene chloride. This aldehyde was then reacted with dibromodifluoromethane, triphenylphosphine, and powdered zinc in dimethylacetamide, producing 1,1-difluoro-1,11-dodecadiene (VI). In order to prepare a secondary alcohol from (VI), the latter was reacted with mercuric acetate in tetrahydrofuran and water and then with sodium borohydride and aqueous sodium hydroxide, producing 12,12-difluoro-11-dodecen-2-ol (VII). Oxidation of (VII) with Jones reagent in acetone yielded methyl 10,10-difluoro-9-decenyl ketone (VIII) which could in turn be reacted with a Grignard reagent, e.g., methylmagnesium bromide, to produce 2-methyl-12,12-difluoro-11-dodecen-2-ol (IX), a tertiary alcohol. Synthesis of primary alcohols was accomplished by reacting (VI) with borane tetrahydrofuran complex and then with sodium hydroxide and hydrogen peroxide, yielding 12,12-difluoro-11-dodecen-1-ol (X). Examples 3, 4, and 5 detail the methods employing this route.