(3R)-3,7-dimethyloctanal

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

Procedure: A 3L 3-necked flask fitted with a reflux condenser, a mechanical stirrer and an argon inlet tube was charged with 161.5 g (1.033 mol) of (R)-3,7-dimethyloctanal (fractions 1-5 from Example 3, GC purity 97.3%), 413 mL of acetone and 1.24 L of 1% aq. KOH. The reaction mixture was stirred vigorously and refluxed for 48 hours. The course of the reaction was monitored by GC. The amount of starting material present was 5% after 25 hours and 3.6% after 48 hours. After cooling in an ice bath, the reaction mixture was poured into a separatory funnel containing 200 mL of brine and extracted with 3×800 mL of hexane/ether 1:1 (parts by volume). The combined organic fractions were washed with 300 mL of brine, dried over MgSO4, filtered and evaporated. Vacuum distillation of the residue through a 30 cm Vigreus column afforded (3E,6R)-6,10-dimethyl-3-undecen-2-one in the following fractions: refluxed for 48 hours after 25 hours After cooling in an ice bath the reaction mixture was poured into a separatory funnel extracted with 3×800 mL of hexane/ether 1:1 (parts by volume) The combined organic fractions were washed with 300 mL of brine dried over MgSO4 filtered evaporated Vacuum distillation of the residue through a 30 cm Vigreus column

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

Procedure: A 3 L indented flask equipped with a mechanical stirrer and a H2 inlet was charged with 205.7 g (1.333 mol) of (R)-citronellal in 7.4 L of ethyl acetate. The flask was flushed with 0.1 cu. ft. of H2 and 0.50 g (2.0 mmol) of platinum oxide were added. The reaction was stirred under a slight over-pressure of H2 at ambient temperature for 124 hours. During this time, due to relatively rapid deactivation of the catalyst, an additional 3.50 g (143. mmol) of platinum oxide had to be added in 5 portions (0.5 g at 3.5 hours., 0.5 g at 22.5 hours., 1.0 g at 96.5 hours and 0.5 g at 121 hours). The course of the hydrogenation was monitored by GC analysis. After 124 hours, GC indicated the hydrogenation to be almost complete with 1.4% of starting material remaining. A total of 1.133 cu. ft. of hydrogen (theoretically 1.166 cu. ft.) had been consumed. The catalyst was removed by filtration through a pad of Celite (diatomeaceous earth). The clear filtrate was combined with the filtrate from a previously run, analogous reduction of 10.0 g (64.8 mmol) of (R)-citronellal and concentrated on the rotovapor. Vacuum distillation of the obtained pale yellow liquid through a 30 cm Goodloe column afforded the (R)-3,7-dimethyloctanal in following fractions: equipped with a mechanical stirrer and a H2 inlet were added to be added in 5 portions (0.5 g at 3.5 hours., 0.5 g at 22.5 hours., 1.0 g at 96.5 hours and 0.5 g at 121 hours) After 124 hours A total of 1.133 cu. ft. of hydrogen (theoretically 1.166 cu. ft.) had been consumed The catalyst was removed by filtration through a pad of Celite (diatomeaceous earth) Vacuum distillation of the obtained pale yellow liquid through a 30 cm Goodloe column

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

Procedure: A 3L 3-necked flask fitted with a reflux condenser, a mechanical stirrer and an argon inlet tube was charged with 161.5 g (1.033 mol) of (R)-3,7-dimethyloctanal (fractions 1-5 from Example 3, GC purity 97.3%), 413 mL of acetone and 1.24 L of 1% aq. KOH. The reaction mixture was stirred vigorously and refluxed for 48 hours. The course of the reaction was monitored by GC. The amount of starting material present was 5% after 25 hours and 3.6% after 48 hours. After cooling in an ice bath, the reaction mixture was poured into a separatory funnel containing 200 mL of brine and extracted with 3×800 mL of hexane/ether 1:1 (parts by volume). The combined organic fractions were washed with 300 mL of brine, dried over MgSO4, filtered and evaporated. Vacuum distillation of the residue through a 30 cm Vigreus column afforded (3E,6R)-6,10-dimethyl-3-undecen-2-one in the following fractions: refluxed for 48 hours after 25 hours After cooling in an ice bath the reaction mixture was poured into a separatory funnel extracted with 3×800 mL of hexane/ether 1:1 (parts by volume) The combined organic fractions were washed with 300 mL of brine dried over MgSO4 filtered evaporated Vacuum distillation of the residue through a 30 cm Vigreus column

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

Procedure: A 3L 3-necked flask fitted with a reflux condenser, a mechanical stirrer and an argon inlet tube was charged with 161.5 g (1.033 mol) of (R)-3,7-dimethyloctanal (fractions 1-5 from Example 3, GC purity 97.3%), 413 mL of acetone and 1.24 L of 1% aq. KOH. The reaction mixture was stirred vigorously and refluxed for 48 hours. The course of the reaction was monitored by GC. The amount of starting material present was 5% after 25 hours and 3.6% after 48 hours. After cooling in an ice bath, the reaction mixture was poured into a separatory funnel containing 200 mL of brine and extracted with 3×800 mL of hexane/ether 1:1 (parts by volume). The combined organic fractions were washed with 300 mL of brine, dried over MgSO4, filtered and evaporated. Vacuum distillation of the residue through a 30 cm Vigreus column afforded (3E,6R)-6,10-dimethyl-3-undecen-2-one in the following fractions: refluxed for 48 hours after 25 hours After cooling in an ice bath the reaction mixture was poured into a separatory funnel extracted with 3×800 mL of hexane/ether 1:1 (parts by volume) The combined organic fractions were washed with 300 mL of brine dried over MgSO4 filtered evaporated Vacuum distillation of the residue through a 30 cm Vigreus column

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

Procedure: A 3 L indented flask equipped with a mechanical stirrer and a H2 inlet was charged with 205.7 g (1.333 mol) of (R)-citronellal in 7.4 L of ethyl acetate. The flask was flushed with 0.1 cu. ft. of H2 and 0.50 g (2.0 mmol) of platinum oxide were added. The reaction was stirred under a slight over-pressure of H2 at ambient temperature for 124 hours. During this time, due to relatively rapid deactivation of the catalyst, an additional 3.50 g (143. mmol) of platinum oxide had to be added in 5 portions (0.5 g at 3.5 hours., 0.5 g at 22.5 hours., 1.0 g at 96.5 hours and 0.5 g at 121 hours). The course of the hydrogenation was monitored by GC analysis. After 124 hours, GC indicated the hydrogenation to be almost complete with 1.4% of starting material remaining. A total of 1.133 cu. ft. of hydrogen (theoretically 1.166 cu. ft.) had been consumed. The catalyst was removed by filtration through a pad of Celite (diatomeaceous earth). The clear filtrate was combined with the filtrate from a previously run, analogous reduction of 10.0 g (64.8 mmol) of (R)-citronellal and concentrated on the rotovapor. Vacuum distillation of the obtained pale yellow liquid through a 30 cm Goodloe column afforded the (R)-3,7-dimethyloctanal in following fractions: equipped with a mechanical stirrer and a H2 inlet were added to be added in 5 portions (0.5 g at 3.5 hours., 0.5 g at 22.5 hours., 1.0 g at 96.5 hours and 0.5 g at 121 hours) After 124 hours A total of 1.133 cu. ft. of hydrogen (theoretically 1.166 cu. ft.) had been consumed The catalyst was removed by filtration through a pad of Celite (diatomeaceous earth) Vacuum distillation of the obtained pale yellow liquid through a 30 cm Goodloe column

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

Procedure: Propynyl magnesium bromide was prepared as described earlier from ethyl bromide (77 g, 0.405 mol, freshly distilled), magnesium (10.8 g 0.4455 mol) and methyl acetylene (approximately 100 ml at -70°) in 400 ml of absolute diethyl ether. To this well stirred mixture was added dropwise 26.4 g (0.169 mol) of 3(R),7-dimethyloctanal (R-(+)-dihydrocitronellal) in 500 ml of dry ether while the reaction temperature was maintained between 0°-5° C. with external cooling. After 45 min. all aldehyde had been added and the reaction was allowed to warm to 30° and stirred at this temperature for 1.0 hr. Thin layer chromatography analysis of the reaction mixture at this point showed the disappearance of starting material. The flask was then cooled in an ice-bath and 100 g of NH4Cl in 600 ml of water was added slowly. The content was transferred to a separatory funnel and the layers separated. The aqueous phase was further extracted with ether (3×250 ml). The combined ether extract was filtered quickly through Celite and washed with saturated brine (3×500 ml) and dried over MgSO4. After filtration the solvent was evaporated to dryness in a rotary evaporator (40°/25 mmHg) to give 33.1 g (100%) of crude 6(R),10-dimethyl-undecan-2-yn-4(R,S)-ol as a clear light amber oil. was maintained between 0°-5° C. with external cooling to warm to 30° stirred at this temperature for 1.0 hr The flask was then cooled in an ice-bath The content was transferred to a separatory funnel the layers separated The aqueous phase was further extracted with ether (3×250 ml) The combined ether extract was filtered quickly through Celite washed with saturated brine (3×500 ml) dried over MgSO4 After filtration the solvent was evaporated to dryness in a rotary evaporator (40°/25 mmHg)

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

Procedure: Propynyl magnesium bromide was prepared as described earlier from ethyl bromide (77 g, 0.405 mol, freshly distilled), magnesium (10.8 g 0.4455 mol) and methyl acetylene (approximately 100 ml at -70°) in 400 ml of absolute diethyl ether. To this well stirred mixture was added dropwise 26.4 g (0.169 mol) of 3(R),7-dimethyloctanal (R-(+)-dihydrocitronellal) in 500 ml of dry ether while the reaction temperature was maintained between 0°-5° C. with external cooling. After 45 min. all aldehyde had been added and the reaction was allowed to warm to 30° and stirred at this temperature for 1.0 hr. Thin layer chromatography analysis of the reaction mixture at this point showed the disappearance of starting material. The flask was then cooled in an ice-bath and 100 g of NH4Cl in 600 ml of water was added slowly. The content was transferred to a separatory funnel and the layers separated. The aqueous phase was further extracted with ether (3×250 ml). The combined ether extract was filtered quickly through Celite and washed with saturated brine (3×500 ml) and dried over MgSO4. After filtration the solvent was evaporated to dryness in a rotary evaporator (40°/25 mmHg) to give 33.1 g (100%) of crude 6(R),10-dimethyl-undecan-2-yn-4(R,S)-ol as a clear light amber oil. was maintained between 0°-5° C. with external cooling to warm to 30° stirred at this temperature for 1.0 hr The flask was then cooled in an ice-bath The content was transferred to a separatory funnel the layers separated The aqueous phase was further extracted with ether (3×250 ml) The combined ether extract was filtered quickly through Celite washed with saturated brine (3×500 ml) dried over MgSO4 After filtration the solvent was evaporated to dryness in a rotary evaporator (40°/25 mmHg)

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

Procedure: A 3 L 3-necked flask fitted with a reflux condenser, a mechanical stirrer and an argon inlet tube was charged with 161.5 g (1.033 mol) of (R)-3,7-dimethyloctanal (fractions 1-5 from Example 3, GC purity 97.3%), 413 mL of acetone and 1.24L of 1% aq. KOH. The reaction mixture was stirred vigorously and refluxed for 48 hours. The course of the reaction was monitored by GC. The amount of starting material present was 5% after 25 hours and 3.6% after 48 hours. After cooling in an ice bath, the reaction mixture was poured into a separatory funnel containing 200 mL of brine and extracted with 3 x 300 mL of hexane/ether 1:1 (parts by volume). The combined organic fractions were washed with 300 mL of brine, dried over MgSO4, filtered and evaporated. Vacuum distillation of the residue through a 30 cm Vigreux column afforded (3E,6R)-6,10-dimethyl-3-undecen- 2-one in the following fractions: A 3 L 3-necked flask fitted with a reflux condenser, a mechanical stirrer and an argon inlet tube refluxed for 48 hours after 25 hours After cooling in an ice bath the reaction mixture was poured into a separatory funnel extracted with 3 x 300 mL of hexane/ether 1:1 (parts by volume) The combined organic fractions were washed with 300 mL of brine dried over MgSO4 filtered evaporated Vacuum distillation of the residue through a 30 cm Vigreux column

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

Procedure: A 3 L indented flask equipped with a mechanical stirrer and a H2 inlet was charged with 205.7g (1.333 mol) of (R)-citronellal in 7.4L of ethyl acetate. The flask was flushed with 0.1 cu. ft. of H2 and 0.50 g (2.0 mmol) of platinum oxide were added. The reaction was stirred under a slight over-pressure of H2 at ambient temperature for 124 hours. During this time, due to relatively rapid deactivation of the catalyst, an additional 3.50 g (143.mmol) of platinum oxide had to be added in 5 portions (0.5 g at 3.5 hours., 0.5 g at 22.5 hours., 1.0 g at 96.5 hours and 0.5 g at 121 hours). The course of the hydrogenation was monitored by GC analysis. After 124 hours, GC indicated the hydrogenation to be almost complete with 1.4% of starting material remaining. A total of 1.133 cu. ft. of hydrogen (theroetically 1.166 cu. ft.) had been consumed. The catalyst was removed by filtration through a pad of Celite (diatomeaceous earth). The clear filtrate was combined with the filtrate from a previously run, analogous reduction of 10.0 g (64.8 mmol) of (R)-citronellal and concentrated on the rotovapor. Vacuum distillation of the obtained pale yellow liquid through a 30 cm Goodloe column afforded the (R)-3,7-dimethyloctanal in following fractions: equipped with a mechanical stirrer and a H2 inlet were added to be added in 5 portions (0.5 g at 3.5 hours., 0.5 g at 22.5 hours., 1.0 g at 96.5 hours and 0.5 g at 121 hours) After 124 hours A total of 1.133 cu. ft. of hydrogen (theroetically 1.166 cu. ft.) had been consumed The catalyst was removed by filtration through a pad of Celite (diatomeaceous earth) Vacuum distillation of the obtained pale yellow liquid through a 30 cm Goodloe column

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

Procedure: A 3 L 3-necked flask fitted with a reflux condenser, a mechanical stirrer and an argon inlet tube was charged with 161.5 g (1.033 mol) of (R)-3,7-dimethyloctanal (fractions 1-5 from Example 3, GC purity 97.3%), 413 mL of acetone and 1.24 L of 1% aq. KOH. The reaction mixture was stirred vigorously and refluxed for 48 hours. The course of the reaction was monitored by GC. The amount of starting material present was 5% after 25 hours and 3.6% after 48 hours. After cooling in an ice bath, the reaction mixture was poured into a separatory funnel containing 200 mL of brine and extracted with a 3×800 mL of hexane/ether 1:1 (parts by volume). The combined organic fractions were washed with 300 mL of brine, dried over MgSO4, filtered and evaporated. Vacuum distillation of the residue through a 30 cm Vigreux column afforded (3E,6R)-6,10-dimethyl-3-undecen-2 -one in the following fractions: A 3 L 3-necked flask fitted with a reflux condenser, a mechanical stirrer and an argon inlet tube refluxed for 48 hours after 25 hours After cooling in an ice bath the reaction mixture was poured into a separatory funnel extracted with a 3×800 mL of hexane/ether 1:1 (parts by volume) The combined organic fractions were washed with 300 mL of brine dried over MgSO4 filtered evaporated Vacuum distillation of the residue through a 30 cm Vigreux column

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

Procedure: A 3 L indented flask equipped with a mechanical stirrer and a H2 inlet was charged with 205.7 g (1.333 mol) of (R)-citronellal in 7.4 L of ethyl acetate. The flask was flushed with 0.1 cu. ft. of H2 and 0.50 g (2.0 mmol) of platinum oxide were added. The reaction was stirred under a slight over-pressure of H2 at ambient temperature for 124 hours. During this time, due to relatively rapid deactivation of the catalyst, an additional 3.50 g (143. mmol) of platinum oxide had to be added in 5 portions (0.5 g at 3.5 hours., 0.5 g at 22.5 hours., 1.0 g at 96.5 hours and 0.5 g at 121 hours). The course of the hydrogenation was monitored by GC analysis. After 124 hours, GC indicated the hydrogenation to be almost complete with 1.4% of starting material remaining. A total of 1.333 cu. ft. of hydrogen (theoretically 1.166 cu. ft.) had been consumed. The catalyst was removed by filtration through a pad of Celite (diatomeaceous earth). The clear filtrate was combined with the filtrate from a previous run, analogous reduction of 10.0 g (64.8 mmol) of (R)-citronellal and concentrated on the rotovapor. Vacuum distillation of the obtained pale yellow liquid through a 30 cm Goodloe column afforded the (R)-3,7-dimethyloctanal in following fractions: equipped with a mechanical stirrer and a H2 inlet were added to be added in 5 portions (0.5 g at 3.5 hours., 0.5 g at 22.5 hours., 1.0 g at 96.5 hours and 0.5 g at 121 hours) After 124 hours A total of 1.333 cu. ft. of hydrogen (theoretically 1.166 cu. ft.) had been consumed The catalyst was removed by filtration through a pad of Celite (diatomeaceous earth) concentrated on the rotovapor Vacuum distillation of the obtained pale yellow liquid through a 30 cm Goodloe column

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

Procedure: A 3 L 3-necked flask fitted with a reflux condenser, a mechanical stirrer and an argon inlet tube was charged with 161.5 g (1.033 mol) of (R)-3,7-dimethyloctanal (fractions 1-5 from Example 3, GC purity 97.3%). 413 mL of acetone and 1.24L of 1% ag. KOH. The reaction mixture was stirred vigorously and refluxed for 48 hours. The course of the reaction was monitored by GC. The amount of starting material present was 5% after 25 hours and 3.6% after 48 hours. After cooling in an ice bath, the reaction mixture was poured into a separatory funnel containing 200 mL of brine and extracted with 3×800 mL of hexane/ether 1:1 (parts by volume). The combined organic fractions were washed with 300 mL of brine, dried over MgSO4, filtered and evaporated. Vacuum distillation of the residue through a 30 cm Vigreux column afforded (3E,6R)-6,10-dimethyl-3-undecen-2-one in the following fractions: A 3 L 3-necked flask fitted with a reflux condenser, a mechanical stirrer and an argon inlet tube refluxed for 48 hours after 25 hours After cooling in an ice bath the reaction mixture was poured into a separatory funnel extracted with 3×800 mL of hexane/ether 1:1 (parts by volume) The combined organic fractions were washed with 300 mL of brine dried over MgSO4 filtered evaporated Vacuum distillation of the residue through a 30 cm Vigreux column