D. Lahiouhel et al. / Journal of Fluorine Chemistry 107 (2001) 81±88
87
4.3.1. Radical bis(monoaddition) of 1,6-diiodoperfluoro-
hexane (5) to allyl alcohol (2)
support and for the gift of 1,6-diiodoper¯uorohexane, the Elf
Atochem Company for the gift of 1-iodoper¯uorohexane
and 1H,1H,2H,2H-per¯uorooctanol, Akzo for Perkadox
16 and La Chalonnaise des Peroxydes for t-butyl peroxy-
pivalate.
A similar experiment as that starting from 1 was per-
formed in a two-necked round-bottom ¯ask using 50.05 g
(0.09 mol) of 5, 11.12 g (0.19 mol) of 2 and 0.697 g
(43 mmol) of AIBN magnetically stirred. The same amounts
of AIBN and of 2 were added every 4 h while the reaction
was monitored by gas chromatography (GC). After 10 h, the
conversion of 5 was quantitative. After evaporation of excess
of 2 until constant weight, 49.2 g (73 mmol, 81% yield) of
an orange wax was obtained showing the formation of the
a,o-diiodohydrin 7 by GC.
References
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4.3.1.1. 2,11-Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodecafluoro-
1,12-dodecanediol (7). 1H NMR ((D3C)2CO) d:
4.4(m,CHI,2H); 3.8(m, down field shifted with Cl3CNCO,
CH2OH,4H); 2.8(m,CH2CHI,4H); 2.2(broad singlet shifted
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123.1(m,CF2±(CF2)2±CH2CHI,4F).
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4.3.2. Reduction of 7 into 8
Similarly to the reduction of 3, 61 ml (0.227 mol) of
tributylstannane were added dropwise into 48.32 g
(71.9 mmol) of 7 saturated with argon, and cooled in an
ice bath.
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After total addition, the mixture was left stirring and
progressively heated up to room temperature for 8 h.
145 mg of potassium ¯uoride and 150 ml of diethyl ether
were added into the mixture and stirred at room temperature
for 3 h. A complex of KF and SnBu3X (X I, H) precipi-
tated and was ®ltered off. After almost total evaporation of
Et2O, diol 8 was precipitated from water, and then recrys-
tallised from ClCF2CFCl2. 22.1 g (53 mmol) of yellow
crystals were obtained in 73% yield. Tm: 718C
(ClCF2CFCl2).
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dodecanediol (8). 1H NMR ((D3C)2CO) d: 3.9(broad signal,
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3
2.4(m,C6F12CH2,4H); 1.8(q, JHH 6:9 Hz, CH2CH2C6-
F12,4H).
19F NMR ((D3C)2CO) same spectrum as that of 7, except
a more simple system centred at 113.5 ppm for CH2CF2
groups.
13C NMR ((D3C)2CO) d: 110 125(m,C6F12,6C);
61.2(s,CH2OH,2C); 30.3(t, 2JCF 22:1 Hz, CH2C6F12,2C);
24.8(s,CH2CH2OH,2C).
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 Â
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Acknowledgements
Caporiccio, J. Fluorine Chem. 73 (1995) 151.
 Â
[31] A. Manseri, D. Boulahia, B. Ameduri, B. Boutevin, G. Caporiccio, J.
The authors would like to thank the Daikin Industries,
Ltd. (Drs Shimizu, Morita and Yamamoto) for its ®nancial
Fluorine Chem. 81 (1997) 103.
[32] A.R. Li, Q.Y. Chen, Synthesis (1997) 1481.