TMP-TDI加成物

對(duì)烯烴或炔烴的加成，是合成氟代烴最直接的方法。由于F2和HF的使用不便以及反應(yīng)放熱嚴(yán)重，難以控制，限制了其在有機(jī)合成中的應(yīng)用，但在工業(yè)上應(yīng)用較多。

多種氟代試劑都能對(duì)烯烴加成，生成鄰二氟代烷烴。

而單氟代烷烴則是通過(guò)HF對(duì)烯烴的加成制備，反應(yīng)遵循Markovnikov規(guī)則。由于操作和控制不方便，一個(gè)替代方法是使用Olah試劑（HF/Pyridine）。

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

Olah試劑對(duì)炔烴的加成則生成二氟代烷烴。

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

AcOF，CF3OF，F(xiàn)OClO3，和CsSO 4F 等試劑對(duì)烯烴的加成會(huì)引入另一個(gè)官能團(tuán)，得到鄰位取代的氟化物。

NO2BF4對(duì)烯烴加成得到鄰硝基氟化物，引入一個(gè)含氮官能團(tuán)。

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

鄰鹵氟化物可以通過(guò)不同試劑對(duì)烯烴的加成制得，如環(huán)己烯，在不同的條件下生成鄰氯，鄰溴和鄰碘的氟代環(huán)己烷。

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

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

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

dAlvernhe, G; Laurent, A; Haufe, G. Synthesis.1987, 562.

eSchmidt, H; Mernert, H. Angew. Chem. 1960,72, 493.

1-Bromo-2-fluoro-2-phenylpropane. A magneticallystirred mixture of α-methylstyrene( 7.1 g ,60 mmol), triethylamine trihydrofluorideand (14.7 mL, 90 mmol)and dichloro-methane(60mL)contained in a 250 mL, single-necked, round-bottomedflaskis treated with N-bromosuccinimide( 11.8 g ,66 mmol)at 0°C .After 15 min, the bath is removed, and stirring is continued at roomtemperature 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 0.1N hydrochloric acid(2 × 150mL)and 5% sodiumhydrogen carbonatesolution (2 × 150 mL)andthen 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 ), n20D 1.5370

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

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