Hydrolysis of Alicyclic Perhalo Olefins¹

Abstract

A new free-radical initiator, azobisisobutanol diacetate, has been prepared from azobisisobutyronitrile in good yield in three steps: ( 1 ) methanolysis to convert the nitrile groups to ester functions; (2) reduction of the diester to a diol; and (3) acetylation, Thus, it is more easily synthesized than other azo compounds having similar free-radical-generating properties and may be easily tagged with Cl4 if desired. Steady production of free radicals at 167" was demonstrated.

Nucleophilic displacement of vinylic halogen in fluorinated cycloalkenes. II. Reaction with triphenylphosphine

“…These results are in accordance with earlier observations (3)(4)(5). It can be concluded that electron-donating substitue~lts favor condensation by acid catalysts and that electron-withdrawing groups favor condensation by bases.…”

Reaction of octafluorocyclopentene with various carbon nucleophiles

“…Column chromatography of the residue using hexane gave pure product, 1-(4-methoxyphenyl)-2,3,3,4,4,5,5-heptafluorocyclopentene (4m). 3,3,4,4,5, 1 H NMR (CDCl 3 ) d = 7.49-7.52 (m, 3H), 7.71-7.73 (m, 2H); 13 C NMR (CDCl 3 ) d = 110.18 (tquint.d,J = 273.8,24.9,4.8 Hz),111.08 (tq,J = 256.9,23.2 Hz),116.16 (tdt,J = 259.2,10.8,2.2 Hz),122.19 (tt,J = 25.3,6.1 Hz),123.90 (d,J = 3.7 Hz),128.77 (d,J = 5.8 Hz),129.26,131.46,J = 303.4 Hz); 19 F NMR (CDCl 3 ) d = À132.00 to À131.10 (m, 1F), À130.71 (br s, 2F), À118.86 (s, 1F), À118.68 (s, 1F), À108.40 (s, 1F), À108.26 (s, 1F); IR (neat) 3066 (w), 2927 (w), 1685 (m), 1380 (vs), 1265 (s) cm À1 ; HRMS (EI). Found: m/z 270.0277.…”

“…for C 11 H 5 F 7 : 270.0279. 3,3,4,4,5, 1 H NMR (CDCl 3 ) d = 2.43 (s, 3H), 7.31 (ABq, J = 8.0 Hz, 2H), 7.64 (ABq, J = 8.0 Hz, 2H); 13 C NMR (CDCl 3 ) d = 21.49,110.94 (tquint. d,J = 256.5,23.9,5.0 Hz),116.16 (tq,J = 237.7,28.9 Hz),120.90,122.05 (tt,J = 25.1,5.0 Hz),128.62,128.66,129.97,142.13,; 19 F NMR (CDCl 3 ) d = À133.10 to À132.10 (m, 1F), À130.74 (br s, 2F), À118.70 (s, 1F), À118.52 (s, 1F), À108.55 (s, 1F), À108.42 (s, 1F); IR (neat) 2927 (w), 2360 (m), 1685 (m), 1380 (vs), 1265 (vs), 1145 (vs) cm À1 ; HRMS (EI).…”

“…for C 12 H 7 F 7 : 284.0436. 3,3,4,4,5, 1 H NMR (CDCl 3 ) d = 5.42 (d,J = 10.5 Hz,1H),5.88 (d,J = 17.5 Hz,1H),6.74 (dd,J = 17.5,10.5 Hz,1H), 7.52 (ABq, J = 8.3 Hz, 2H), 7.70 (ABq, J = 8.3 Hz, 2H); 13 C NMR (CDCl 3 ) d = 109.98 (tquint.d,J = 272.9,23.9,6.3 Hz),110.91 (tq,J = 256.6,22.6 Hz),116.01 (tdt,J = 262.8,11.3,2.5 Hz),116.71,121.74 (tt,J = 25.2,6.3 Hz),122.88,126.90,128.96 (d,J = 6.3 Hz),135.63,140.59,150.92 4.6. Typical procedure for the synthesis of 1,2-bis(4-methoxyphenyl)-3,3,4,4,5,5-hexafluorocyclopentene (5m) by using 4-methoxyphenylmagnesium bromide A 50 mL three-necked round-bottomed flask equipped with a magnetic stirrer bar, a thermometer, a rubber septum and an inlet tube for argon was charged with a solution of 6.6 equiv.…”

“…However, very little attention has been paid to the nucleophilic substitution reactions of 2 with carbon nucleophiles thus far [4], though many studies have been made on the reaction of 2 with hetero nucleophiles, such as phenoxide [5], aryl or alkyl thiolate [6], primary or secondary amines [7], and so on [8].…”