Radiation-chemical alkylation of olefines with adamantane

Free radical chemistry. Part 10. Addition of acyclic and cyclic alkanes to hexafluoropropene

“…C 13 H 16 F 6 requires C, 54.5; H, 5.6%); δ H (250 MHz; CDCl 3 ; Me 4 Si) 1.76 (12 H, m, CH 2 ), 2.07 (3 H, s, CH), 4.93 (1 H, ddq, 2 J HF 44, 3 J HF 20, 3 J HF 6.4, CFH); δ F (235 MHz; CDCl 3 ; CFCl 3 ) Ϫ74.3 (3 F, br s, CF 3 ), Ϫ122.6 and Ϫ130.0 (2 F, AB, J AB 274, CF 2 ), Ϫ206.9 (1 F, d, 2 J HF 41, CFH); δ C (100 MHz; CDCl 3 ; Me 4 Si) 27.5 (s, CH), 34.6 (q, 5 J CF 3.4, CH 2 ), 36.4 (s, CH 2 ), 40.0 (t, 2 J CF 21, CCF 2 ), 83.6 (ddqd, 1 J CF 197, 2 J CF 41, 2 J CF 33, 2 J CF 26, CFH), 119.5 (ddd, 1 J CF 261, 1 J CF 247, 2 J CF 22, CF 2 ), 121.3 (qd, 1 J CF 283, 2 J CF 26, CF 3 ); m/z (EI ϩ ) 151 (1%), 135 (100), 79 (43), 41 (35); MS and NMR data are consistent with those contained in the literature; 8 and the second fraction was identified as 1,3-bis-(1,1,2,3,3,3-hexafluoropropyl)adamantane 32 (7.9 g, 19%), bp 9 124-126 ЊC (Found: C, 43.7; H, 3.8. C 16 H 16 F 12 requires C, 44.0; H, 3.7%); δ H (250 MHz; CDCl 3 ; Me 4 Si) 1.80 (12 H, m, CH ϩ CH 2 ), 2.28 (2 H, br s, CH 2 ), 4.93 (2 H, ddq, 2 J HF 44, 3 J HF 20, 3 J HF 6.4, CFH); δ F (235 MHz; CDCl 3 ; CFCl 3 ) Ϫ74.3 (6 F, br s, CF 3 ), Ϫ121.7 and Ϫ129.4 (4 F, AB, J AB 275, CF 2 ), Ϫ207.1 (2 F, d, 2 J HF 37, CFH); δ C (100 MHz; CDCl 3 ; Me 4 Si) 27.0 (s, CH), 31.8 (br s, CH 2 ), 33.8 (s, CH 2 ), 35.3 (s, CH 2 ), 40.6 (t, 2 J CF 21, CCF 2 ), 83.8 (ddqd, 1 J CF 197, 2 J CF 42, 2 J CF 34, 2 J CF 26, CFH), 119.1 (ddd, 1 J CF 261, 1 J CF 247, 2 J CF 23, CF 2 ), 121.1 (qd, 1 J CF 283, 2 J CF 26, CF 3 ); m/z (EI ϩ ) 397 (1%), 285 (100), 243(11), 229(12), 55(16); MS and NMR data are consistent with those contained in the literature 21.…”

“…trans-1,4-Bis(1,1,2,3,3,3-hexafluoropropyl)cyclohexane 20a (2.4 g, 6 mmol) was passed through the cobalt trifluoride reactor, at 400 ЊC, to give a colourless liquid (2.9 g). Preparative scale GC gave a mixture of cis-and trans-isomers of perfluoro-1,4-dipropylcyclohexane 52 (1.9 g, 65%); cis-perfluoro-1,4dipropylcyclohexane δ F (235 MHz; CDCl 3 ; CFCl 3 ) Ϫ81.0 (6 F, s, CF 3 ), Ϫ113.4 (4 F, s, CF 2 ), Ϫ119.4 (4 F, s, CF 2 ), Ϫ124.8 (8 F, br s, CF 2 ), Ϫ183.0 (2 F, br s, CF); m/z (EI ϩ ) 481 (4%), 331 (20), 181 (21), 169 (100), 131 (27), 119 (37), 69 (46); trans-perfluoro-1,4-dipropylcyclohexane mp 80-81 ЊC (from CFCl 3 ); δ F (235 MHz; CDCl 3 ; CFCl 3 ) Ϫ81.2 (6 F, br s, CF 3 ), Ϫ117.7 and Ϫ126.7 (8 F, AB, J AB 297, CF 2 ), Ϫ119.4 (4 F, s, CF 2 ), Ϫ126.7 (4 F, s, CF 2 ), Ϫ186.7 (2 F, s, CF); m/z (EI ϩ ) 481 (4%), 331 (16), 181 (21), 169 (100), 131 (21), 119 (26), 69 (69).…”