1,3-Dipolar Cycloadditions of Fluorinated Allenes And Studies of Fluorinated Trimethylenemethanes

Cover 1,3-Dipolar Cycloadditions of Fluorinated Allenes And Studies of Fluorinated Trimethylenemethanes
1,3-Dipolar Cycloadditions of Fluorinated Allenes And Studies of Fluorinated Trimethylenemethanes
Burkholder, Conrad
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Through a 15 cm by 2 cm Vigreux column heated at 380 was vacuum transferred 1.3 g (13 mmoles) pyrazoline 113 over a period of 2.5 hours at a pressure of 0.6-1.0 mm. A total of 650 mg (69%) crude liquid pyrolysate was collected in a vacuum trap at dry-ice temperature.
The products were isolated by prep G-LPC (20 ft by 1/4 in 20% DNP at 50°, 60 ml/min) to give 72 mg (7.7%) of 136 ; IR(CC1 4 ) 3080, 3040, 3005, 2985, 1828(w), 1755(w), 1438, -130- 1322, 1143(b), 1110(s), 910(a), 835 cm" 1 ; 1 H NMR
...(100 MHz) 65.86(m, 1H), 5.6l(m, 1H), 4.92(d of m, 1H, J RF = 68.6 Hz, non-first-order), 1.65-1 .45(m, 2H); 19 F NMR (100 MHz) 169.6(d of m, J HF =68.0 Hz); mass spectrum gave M + 72.03732 ± 0.00107(15 ppm), calcd for C^F 72.03753 dev -0.00021(3 ppm).
There were also isolated 110 mg (11.7#) of 137: IR (CC1 4 ) 3075, 3000, 1790(a), 1435, 1326, 1125(a), 1038, 977 cm" 1 ; 1 H NMR(100 MHz) 6 6.88(d of pentet, 1H, J„-,» rir 91.5 and Jjjg-2.2 Hz), 1.27(dd, 4H, J HF »4.6 and ^=2.2 Hz), 19 F NMR(100 MHz)

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