n-Hexyl fluoride (CAS NO.: ), which is also known as Hexane, 1-fluoro-, could be produced through the following synthetic routes.

In a thoroughly dry 500-ml. three-necked round-bottomed flask, equipped with a mercury-sealed stirrer, a 100-ml. dropping funnel and a short fractionating column, is placed a mixture of 116 g. (2.0 moles) of anhydrous finely powdered potassium fluoride and 200 g. of dry ethylene glycol (Note 4). The fractionating column carries a thermometer and is connected to a downward double-surface condenser with a filter flask as receiver. The round flask is heated at a bath temperature of 160–170°, and 165 g. (1.0 mole) of n-hexyl bromide, b.p. 154–156°, is added dropwise during 5 hours; liquid passes over intermittently at 60–90° (temperature at the top of the fractionating column). The bath temperature is allowed to fall to 110–120°, and a slow stream of air is drawn through the apparatus by attaching the side arm of the filter flask to a water pump and replacing the dropping funnel by a narrow-bore tube dipping just below the surface of the liquid; stirring is maintained during this operation. It is advisable to interpose a U-tube cooled in ice between the water pump and the receiver in order to recover any uncondensed liquid. The combined distillates are then distilled at atmospheric pressure through an efficient fractionating column; after a small fore-run (up to 10 g.) of 1-hexene, the crude n-hexyl fluoride is collected at 89–92° (46–48 g.). The crude product is purified by cooling in ice and adding 1-ml. portions of a solution containing 9.0 g. of bromine and 6.0 g. of potassium bromide in 50 ml. of water until the organic layer acquires an orange color; after each addition the mixture is shaken vigorously for a minute or so. The volume of bromine-potassium bromide solution required is usually less than 5 ml. The aqueous layer is separated, the organic layer is washed with saturated aqueous potassium bromide solution until color-less and finally with water. The liquid is dried with anhydrous magnesium sulfate and distilled through an efficient fractionating column; the n-hexyl flouride is collected at 91–92°. This procedure yields 42–47 g. (40–45% over-all yield based on the bromide employed) of a water-white product, n_D20 1.375, n_D25 1.372–1.373, d₄20 0.8011. It has been kept for 1 year without change of physical properties and therefore appears to be stable.

Notice: The 1-fluoroalkanes are the most toxic of the fluoro compounds. This fact, together with their relatively high volatility, emphasizes the need for care in handling these materials. This preparation should be carried out in a good hood and the operator should wear rubber gloves.