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1-Bromodecane: Applications and Synthesis Routes

Apr 23，2025

1-Bromodecane was used in the synthesis of ferrocene containing hexacatenar metallomesogen. The product's main application is as a chemical intermediate, including Grignard chemistry, in organic synthesis. 1-Bromodecane participates in alkylation of pentaerythritol and introduces two lipophilic groups in pentaerythritol. It reacts with 1,2-dimethylimidazole to yield 1-decyl-2,3-dimethylimidazolium bromide.

Synthesis from (4Z)-1-bromo-4-decene

Nickel(II) acetate (1.34 g, 0.0054 mol), zinc(II) oxide (0.44 g, 0.0054 mol), and 2-propanol (38.3 g, 0.64 mol) were placed in a reactor, heated at 50 to 55° C., and stirred for 1 hour. Next, the mixture was cooled to 40° C., subjected to addition of sodium borohydride (0.26 g, 0.0069 mol), and stirred at 35 to 45° C. for 2 hours. Subsequently, (4Z)-1-bromo-4-decene (comp. of Formula 1) (96.9 g, 0.44 mol) was added into the reactor in which the NiZn catalyst had been prepared, then the mixture was warmed to 40 to 50° C., and hydrogen gas was fed thereto for 6 hours while the progress of the reaction was observed. The resulting mixture was cooled to 40° C. or less, and the NiZn catalyst was filtered off, then water (14.6 g) was added to the filtrate for liquid separation. The organic phase was concentrated under reduced pressure, and then the residue was subjected to vacuum distillation to obtain 1-bromodecane (comp. of Formula 2) (93.4 g, 0.42 mol) at a yield of 95.5%. The yield of decane, which was a dehalogenation product, was 3.0%, so that the by-product was only slightly yielded. 1-bromodecane (comp. of Formula 2) [Nuclear magnetic resonance spectrum] 1H-NMR (500 MHz, CDCl3): δ=0.88 (3H, t, J=7.1 Hz), 1.22-1.34 (12H, m), 1.38-1.45 (2H, m), 1.85 (2H, quint-like, J=7.3 Hz), 3.40 (2H, t, J=6.9 Hz).[1]

Synthesis from hexafluoroacetylacetonate

1-Bromodecane can be obtained from hexafluoroacetylacetonate: Into an oven-dried Schlenk tube, Pd(hfacac)2 (26.0 mg, 0.05 mmol, 10 mol%; hfacac =hexafluoroacetylacetonate), L13 (17.5 mg, 0.015 mmol, 15 mol%), LiClO4 (53.4 mg, 0.5 mmol, 1.0 equiv.) and Na-NMBI (228.9 mg, 1.0 mmol, 2.0 equiv.) were weighed and dissolved in a mixture of anhydrous CH3CN/DCM (5 ml, 4:6 v/v) under argon. Then alkene substrate (0.5 mmol, 1.0 equiv.), H2O (5-10 μl), and iPr3SiH(2.0-2.2 equiv.) were added. The tube was sealed and the mixture was stirred at room temperature. After 6 h, another portion of Na-NMBI (1.0 equiv.) and iPr3SiH(1.0-1.1 equiv.) was added, and the mixture was further stirred and monitored byTLC. After the reaction was completed, solvent was removed under vacuum, and the residue was purified by column chromatography on silica gel with a gradient eluent of petroleum ether/ethyl acetate to give the desired product 1-Bromodecane.[2]

Synthesis from 1-bromononane

Into a 2 liter glass flask, 96.2 g of tri(1,2-propylene glycol), 243.3 g of 1-bromononane, 14.3 g of tetrabutylammonium bromide and 442 g of a 52% by mass aqueous solution of sodium hydroxide were placed, and the reaction was allowed to proceed at 70[deg.] C. for 8 hours under stirring. After the reaction was completed, the reaction mixture was transferred to a separatory funnel, and the aqueous phase was removed by filtration. The remaining organic phase was washed with 200 ml of water 5 times. Water was removed from the organic phase using a vacuum evaporator until the liquid became transparent. The resultant liquid was filtered by pouring into a column packed with 40 g of silica gel, and an organic substance was obtained. From the organic substance, 72 g of tri(2,3-propylene glycol) dinonyl ether was separated in accordance with the distillation under a reduced pressure. In accordance with a similar reaction using 1-bromodecane, tri(2,3-propylene glycol) didecyl ether was obtained. Into a 2 liter glass flask, 300 g of 2-hexyldecanol, 300 g of 1-bromodecane, 30 g of tetrabutylammonium bromide and 500 g of a 30% by mass aqueous solution of sodium hydroxide were placed, and the reaction was allowed to proceed at 50[deg.] C. for 20 hours under stirring. In accordance with a similar reaction using 1-bromodecane, tri(2,3-propylene glycol) didecyl ether was obtained.[3]