1-bromo-3,7,11,15-tetramethylhexadecane

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

Procedure: Magnesium bromide etherate (17 g, 55 mmol) and a stir bar were added to a 500 mL round bottom flask. The flask was sealed and flushed with nitrogen and anhydrous diethyl ether (200 mL) added via cannula. A solution of phytanyl mesylate (23) (10.9 g, 28.9 mmol (FW=377)) in anhydrous ether (50 mL) was also added via canulla, and the suspension stirred overnight. The following morning a precipitate had formed on the side of the flask. Chilled water (200 mL) was added (ppte dissolved) and the mixture transferred to a 1000-mL separating funnel. After shaking, the organic phase was separated. The aqueous phase was then extracted with ether (2×150 mL) and all ether phases combined. The ether phase was washed with water (2×150 mL), brine (150 mL) and dried over anhydrous Mg2SO4. The solution was filtered, concentrated, and purified by flash chromatography. Final yield 9.5 g (26.3 mmol, 91.1%). The flask was sealed flushed with nitrogen and anhydrous diethyl ether (200 mL) added via cannula The following morning a precipitate had formed on the side of the flask (ppte dissolved) separating funnel After shaking the organic phase was separated The aqueous phase was then extracted with ether (2×150 mL) The ether phase was washed with water (2×150 mL), brine (150 mL) dried over anhydrous Mg2SO4 The solution was filtered concentrated purified by flash chromatography

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

Procedure: Magnesium bromide etherate (17 g, 55 mmol) and a stir bar were added to a 500 mL round bottom flask. The flask was sealed and flushed with nitrogen and anhydrous diethyl ether (200 mL) added via cannula. A solution of phytanyl mesylate (10.9 g, 28.9 mmol (FW=377)) in anhydrous ether (50 mL) was also added via canulla, and the suspension stirred overnight. The following morning a precipitate had formed on the side of the flask. Chilled water (200 mL) was added (ppte dissolved) and the mixture transferred to a 1000-mL separating funnel. After shaking, the organic phase was separated. The aqueous phase was then extracted with ether (2×150 mL) and all ether phases combined. The ether phase was washed with water (2×150 mL), brine (150 mL) and dried over anhydrous Mg2SO4. The solution was filtered, concentrated, and purified by flash chromatography. Final yield 9.5 g (26.3 mmol, 91.1%). The flask was sealed flushed with nitrogen and anhydrous diethyl ether (200 mL) added via cannula The following morning a precipitate had formed on the side of the flask (ppte dissolved) separating funnel After shaking the organic phase was separated The aqueous phase was then extracted with ether (2×150 mL) The ether phase was washed with water (2×150 mL), brine (150 mL) dried over anhydrous Mg2SO4 The solution was filtered concentrated purified by flash chromatography

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

Procedure: To a suspension of magnesium bromide diethyl etherate (25.9 g, 100.3 mmol) in anhydrous diethyl ether (250 mL) under nitrogen at room temperature was added a solution of phytanyl mesylate (18.9 g, 50.2 mmol) in anhydrous diethyl ether (200 mL) dropwise over 15 minutes. The resulting slurry was stirred for 72 hours at room temperature. Upon completion, the reaction mixture was cooled to 0° C. and ice cold water was added dropwise until all solid dissolved and bubbling stopped. Diethyl ether (300 mL) was added, and the organic and aqueous layers separated. The aqueous layer was back-extracted with diethyl ether (200 mL). The combined diethyl ether extracts were dried on MgSO4, filtered, and concentrated. The resulting oil was purified by column chromatography (column 10″L×2″W; eluted with 100% hexanes) to afford the product as a pale yellow oil (16.3 g, 90%). Upon completion, the reaction mixture was cooled to 0° C. ice cold water was added dropwise until all solid dissolved bubbling Diethyl ether (300 mL) was added the organic and aqueous layers separated The aqueous layer was back-extracted with diethyl ether (200 mL) The combined diethyl ether extracts were dried on MgSO4 filtered concentrated The resulting oil was purified by column chromatography (column 10″L×2″W; eluted with 100% hexanes)

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 21.69 g (60 mmol) of 1-bromo-3,7,11,15-tetramethylhexadecane and 25 g (150 mmol) of triethyl phosphite was heated at 150° C. After 18 h, an additional 20 g (120 mmol) of triethyl phosphite was added, and heating was continued for 24 h. Diethyl ethylphosphonate and other volatiles were distilled, bp 30-50° C. at 0.05 mm Hg, and bulb-to-bulb distillation of the concentrate provided 23.51 g (94%) of 1-(diethylphosphono)-3,7,11,15-tetramethylhexadecane as a clear, colorless liquid, bp 190-230° C. at 0.05 mm Hg. heating was continued for 24 h Diethyl ethylphosphonate and other volatiles were distilled bp 30-50° C. at 0.05 mm Hg, and bulb-to-bulb distillation of the concentrate

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

Procedure: To a mixture of 40.0 g (134 mmol) of 3,7,11,15-tetramethyl-1-hexadecanol and 400 mL of 48% hydrobromic acid was slowly added 40 mL of concentrated sulfuric acid. The reaction mixture was heated at 100° C. for 24 h and poured into 1.2 L of water. The mixture was extracted with hexanes, and the combined organic phases were washed with saturated aqueous NaHCO3 and dried over MgSO4. The solution was concentrated to a dark liquid, which was eluted through 3 inches (7.6 cm) of silica with hexanes. Concentration of the eluent yielded a light amber liquid, and bulb-to-bulb distillation gave 40.8 g (84%) of 1-bromo-3,7,11,15-tetramethylhexadecane as a clear, colorless liquid, bp 160-180° C. at 0.06 mm Hg. The mixture was extracted with hexanes the combined organic phases were washed with saturated aqueous NaHCO3 dried over MgSO4 The solution was concentrated to a dark liquid, which was eluted through 3 inches (7.6 cm) of silica with hexanes Concentration of the eluent yielded a light amber liquid, and bulb-to-bulb distillation

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

Procedure: Phytanyl bromide (12.34 g), potassium phthalimide (6.95 g) and DMF (50 ml) were heated at 120-130° C. for 4 hours. Most of the DMF was removed under reduced pressure and the crude product was dissolved in dichloromethane (100 ml), washed with water (2×50 ml), dried (MgSO4). The light yellow crude product was chromatographed on flash silica (dichloromethane/hexane as eluant) to yield pure N-phytanyl phthalimide in 11.89 g (80.9%) 1H-n.m.r. (CDCl3) δ0.82-1.8 (m, 39H), 3.73 (t, 2H, CH2N), 7.73 (m, 2H, ArH), 7.88 (m, 2H, ArH); m/z 431 (M+). Most of the DMF was removed under reduced pressure the crude product was dissolved in dichloromethane (100 ml) washed with water (2×50 ml) dried (MgSO4) The light yellow crude product was chromatographed on flash silica (dichloromethane/hexane as eluant)

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

Procedure: Phytanyl bromide (12.34 g), potassium phthalimide (6.95 g) and DMF (50 ml) were heated at 120-130° C. for 4 hours. Most of the DMF was removed under reduced pressure and the crude product was dissolved in dichloromethane (100 ml), washed with water (2×50 ml), dried (MgSO4). The light yellow crude product was chromatographed on flash silica (dichloromethane/hexane as eluant) to yield pure N-phytanyl phthalimide in 11.89 g (80.9%) 1H-n.m.r. (CDCl3) δ0.82-1.8 (m, 39H), 3.73 (t, 2H, CH2N), 7.73 (m, 2H, ArH), 7.88 (m, 2H, ArH); m/z 431 (M+). Most of the DMF was removed under reduced pressure the crude product was dissolved in dichloromethane (100 ml) washed with water (2×50 ml) dried (MgSO4) The light yellow crude product was chromatographed on flash silica (dichloromethane/hexane as eluant)

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

Procedure: To a suspension of magnesium bromide diethyl etherate (25.9 g, 100.3 mmol) in anhydrous diethyl ether (250 mL) under nitrogen at room temperature was added a solution of phytanyl mesylate (18.9 g, 50.2 mmol) in anhydrous diethyl ether (200 mL) dropwise over 15 minutes. The resulting slurry was stirred for 72 hours at room temperature. Upon completion, the reaction mixture was cooled to 0° C. and ice cold water was added dropwise until all solid dissolved and bubbling stopped. Diethyl ether (300 mL) was added, and the organic and aqueous layers separated. The aqueous layer was back-extracted with diethyl ether (200 mL). The combined diethyl ether extracts were dried on MgSO4, filtered, and concentrated. The resulting oil was purified by column chromatography (column 10″L×2″W; eluted with 100% hexanes) to afford the product as a pale yellow oil (16.3 g, 90%). Upon completion, the reaction mixture was cooled to 0° C. ice cold water was added dropwise until all solid dissolved bubbling Diethyl ether (300 mL) was added the organic and aqueous layers separated The aqueous layer was back-extracted with diethyl ether (200 mL) The combined diethyl ether extracts were dried on MgSO4 filtered concentrated The resulting oil was purified by column chromatography (column 10″L×2″W; eluted with 100% hexanes)

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

Procedure: Magnesium bromide etherate (17 g, 55 mmol) and a stir bar were added to a 500 mL round bottom flask. The flask was sealed and flushed with nitrogen and anhydrous diethyl ether (200 mL) added via cannula. A solution of phytanyl mesylate (23) (10.9 g, 28.9 mmol (FW=377)) in anhydrous ether (50 mL) was also added via canulla, and the suspension stirred overnight. The following morning a precipitate had formed on the side of the flask. Chilled water (200 mL) was added (ppte dissolved) and the mixture transferred to a 1000-mL separating funnel. After shaking, the organic phase was separated. The aqueous phase was then extracted with ether (2×150 mL) and all ether phases combined. The ether phase was washed with water (2×150 mL), brine (150 mL) and dried over anhydrous Mg2SO4. The solution was filtered, concentrated, and purified by flash chromatography. Final yield 9.5 g (26.3 mmol, 91.1%). The flask was sealed flushed with nitrogen and anhydrous diethyl ether (200 mL) added via cannula The following morning a precipitate had formed on the side of the flask (ppte dissolved) separating funnel After shaking the organic phase was separated The aqueous phase was then extracted with ether (2×150 mL) The ether phase was washed with water (2×150 mL), brine (150 mL) dried over anhydrous Mg2SO4 The solution was filtered concentrated purified by flash chromatography

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

Procedure: To a suspension of magnesium bromide diethyl etherate (25.9 g, 100.3 mmol) in anhydrous diethyl ether (250 mL) under nitrogen at room temperature was added a solution of phytanyl mesylate (18.9 g, 50.2 mmol) in anhydrous diethyl ether (200 mL) dropwise over 15 minutes. The resulting slurry was stirred for 72 hours at room temperature. Upon completion, the reaction mixture was cooled to 0° C. and ice cold water was added dropwise until all solid dissolved and bubbling stopped. Diethyl ether (300 mL) was added, and the organic and aqueous layers separated. The aqueous layer was back-extracted with diethyl ether (200 mL). The combined diethyl ether extracts were dried on MgSO4, filtered, and concentrated. The resulting oil was purified by column chromatography (column 10″L×2″W; eluted with 100% hexanes) to afford the product as a pale yellow oil (16.3 g, 90%). Upon completion, the reaction mixture was cooled to 0° C. ice cold water was added dropwise until all solid dissolved bubbling Diethyl ether (300 mL) was added the organic and aqueous layers separated The aqueous layer was back-extracted with diethyl ether (200 mL) The combined diethyl ether extracts were dried on MgSO4 filtered concentrated The resulting oil was purified by column chromatography (column 10″L×2″W; eluted with 100% hexanes)

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

Procedure: Magnesium bromide etherate (17 g, 55 mmol) and a stir bar were added to a 500 mL round bottom flask. The flask was sealed and flushed with nitrogen and anhydrous diethyl ether (200 mL) added via cannula. A solution of phytanyl mesylate (23) (10.9 g, 28.9 mmol (FW=377)) in anhydrous ether (50 mL) was also added via canulla, and the suspension stirred overnight. The following morning a precipitate had formed on the side of the flask. Chilled water (200 mL) was added (ppte dissolved) and the mixture transferred to a 1000-mL separating funnel. After shaking, the organic phase was separated. The aqueous phase was then extracted with ether (2×150 mL) and all ether phases combined. The ether phase was washed with water (2×150 mL), brine (150 mL) and dried over anhydrous Mg2SO4. The solution was filtered, concentrated, and purified by flash chromatography. Final yield 9.5 g (26.3 mmol, 91.1%). The flask was sealed flushed with nitrogen and anhydrous diethyl ether (200 mL) added via cannula The following morning a precipitate had formed on the side of the flask (ppte dissolved) separating funnel After shaking the organic phase was separated The aqueous phase was then extracted with ether (2×150 mL) The ether phase was washed with water (2×150 mL), brine (150 mL) dried over anhydrous Mg2SO4 The solution was filtered concentrated purified by flash chromatography

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

Procedure: Magnesium bromide etherate (17 g, 55 mmol) and a stir bar were added to a 500 mL round bottom flask. The flask was sealed and flushed with nitrogen and anhydrous diethyl ether (200 mL) added via cannula. A solution of phytanyl mesylate (10.9 g, 28.9 mmol (FW=377)) in anhydrous ether (50 mL) was also added via canulla, and the suspension stirred overnight. The following morning a precipitate had formed on the side of the flask. Chilled water (200 mL) was added (ppte dissolved) and the mixture transferred to a 1000-mL separating funnel. After shaking, the organic phase was separated. The aqueous phase was then extracted with ether (2×150 mL) and all ether phases combined. The ether phase was washed with water (2×150 mL), brine (150 mL) and dried over anhydrous Mg2SO4. The solution was filtered, concentrated, and purified by flash chromatography. Final yield 9.5 g (26.3 mmol, 91.1%). The flask was sealed flushed with nitrogen and anhydrous diethyl ether (200 mL) added via cannula The following morning a precipitate had formed on the side of the flask (ppte dissolved) separating funnel After shaking the organic phase was separated The aqueous phase was then extracted with ether (2×150 mL) The ether phase was washed with water (2×150 mL), brine (150 mL) dried over anhydrous Mg2SO4 The solution was filtered concentrated purified by flash chromatography