对烯烃或炔烃的加成，是合成氟代烃最直接的方法。由于F2和HF的使用不便以及反应放热严重，难以控制，限制了其在有机合成中的应用，但在工业上应用较多。

多种氟代试剂都能对烯烃加成，生成邻二氟代烷烃。

而单氟代烷烃则是通过HF对烯烃的加成制备，反应遵循Markovnikov规则。由于操作和控制不方便，一个替代方法是使用Olah试剂（HF/Pyridine）。

【Olah, G, A; Welch, J,T. J. Org. Chem. 1979, 44, 3872】

Olah试剂对炔烃的加成则生成二氟代烷烃。

【Olah, G, A; Welch, J,T. J. Org. Chem. 1979, 44, 3872】

AcOF， CF3OF，FOClO3，和CsSO4F等试剂对烯烃的加成会引入另一个官能团，得到邻位取代的氟化物。

NO2BF4对烯烃加成得到邻硝基氟化物，引入一个含氮官能团。

【  Mursakulov, I, G; Talybov, A, H. Chem.Abstr, 1979,90, 38561】

邻卤氟化物可以通过不同试剂对烯烃的加成制得，如环己烯，在不同的条件下生成邻氯，邻溴和邻碘的氟代环己烷。

a    Olah, G, A; Welch, J, T. J. Org. Chem. 1979,44, 3872.

b    Rozen, S; Brand, M. J. Org. Chem, 1985,50, 3342.

c    Heasley, V. L;Gipe, R. K; Martin, J. L. J.Org. Chem. 1983, 48, 3195.

d     Alvernhe, G; Laurent, A; Haufe, G. Synthesis.1987, 562.

e    Schmidt, H; Mernert, H. Angew. Chem. 1960,72, 493.

1-Bromo-2-fluoro-2-phenylpropane. A magnetically stirred mixture of α-methylstyrene (7.1 g, 60 mmol), triethylamine trihydrofluoride and (14.7 mL, 90 mmol) and dichloro- methane  (60 mL) contained in a 250 mL, single-necked, round-bottomed flask is treated with N-bromosuccinimide (11.8 g, 66 mmol) at0°C. After 15 min, the bath is removed, and stirring is continued at room temperature for 5 hr. The reaction mixture is poured into ice water (1000 mL), made slightly basic with aqueous 28% ammonia, and extracted with dichloromethane (4 × 150 mL). The combined extracts are washed with 0.1 N hydrochloric acid (2 × 150 mL) and 5% sodium hydrogen carbonate solution (2 × 150 mL) and then dried over magnesium sulfate . After removal of the solvent by rotary evaporation, the crude product is distilled to give the product:11.6 g(89%); bp 50-52°C(0.15 mm), n20 D 1.5370

【Haufe, G; Alvernhe, G; Laurent,A. Organic Syntheses. Coll. Vol. 10, 128.】