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J. Balague et al. / Journal of Fluorine Chemistry 102 (2000) 253±268
267
1-iodo-3,3,5,5,7,7,8,8,9,9,10,10,10-trideca¯uorodecane:
C4F9CH2CF2CH2CF2CH2CH2I bp: 113±1168C/20 mm Hg;
References
1
yield: 47%; H and 19F NMR: see Table 8.
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4.3.2.4. From C4F9(VDF)(HFP)I: synthesis of C4F9-
(VDF)(HFP)C2H4I by redox catalysis. From the same
experimental process, the autoclave containing 49.7 g of
C4F9(VDF)(HFP)I (0.09 mol), 0.4 g of CuCl (0.004 mol),
2.5 g of NH2C2H4OH (0.04 mol), 60 ml of tertiobutanol and
12.2 g of ethylene (0.43 mol) was heated under stirring at
1458C for 15 h.
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1-iodo-3-tri¯uoromethyl-3,4,4,5,5,7,7,8,8,9,9,10,10,10-
tetradeca¯uorodecane: C4F9CH2CF2CF2CF(CF3)CH2CH2-
I; bp: 110±1148C/18 mm Hg; yield: 85%; 1H and 19F NMR:
see Table 3.
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4.3.2.5. From i-C3F7(VDF)(HFP)I: synthesis of i-
C3F7(VDF)(HFP)C2H4I by redox end-capping. Following
the same experimental procedure, the autoclave containing
20.2% of i-C3F7(VDF)(HFP)I (0.04 mol), 0.099 of CuCl
(0.001 mol), 0.6 g of NH2C2H4OH (0.01 mol), 30 ml of
tertiobutanol and 3.4 g of ethylene (0.12 mol) was heated
under stirring at 1408C for 15 h. After distillation, the pure
fraction was characterized.
1-iodo-3,7-bis(tri¯uoromethyl)-3,4,4,5,5,7,8,8,8-nona-
¯uorooctane (pink liquid): i-C3F7CH2CF2CF2CF(CF3)CH2-
CH2I; bp: 40±438C/23 mm Hg; yield 85%; 1H and 19F
NMR: see Table 4.
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4.4. Selective reduction of iodine extremity
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Selective reductions of iodine atom of the ¯uoro cotelo-
mers (RFI) were performed under nitrogen for 30 min in an
ampoule equipped with a septum at room temperature in the
presence of tributyl stannane dropwise added (via a syringe)
into RFI saturated of argon at 2±58C with a [RFI]o/
[SnBu3H]o equimolar ratio. As soon as SnBu3H was added,
a decoloration of the ¯uorocotelomer was noted. After
reaction and decantation, the ¯uorinated lower phase was
recovered and corresponded to RFH. In case of dif®cult
separation, 5% in weight of potassium ¯uoride and 30 ml of
diethylether were added in the medium and stirred for a least
3 h at room temperature. After ®ltration of SnBu3F and
distillation of the solvent, the reduced derivative was dis-
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in Tables 3, 5 and 9.
Â
Â
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Â
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Most reduced compounds thus obtained were colorless
liquids.
Â
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Â
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Acknowledgements
submitted for publication.
[31] N. Bannai, H. Yasumi, S. Hirayama, US Patent 4,580,981 (to
Kureha), 8 April 1986.
The authors thank Dow Corning Corp. Midland (Michi-
gan), which sponsored this research and the Elf Atochem
and Hoechst Companies for the gift of linear per¯uoroalkyl
iodides and VDF, and HFP, respectively.
[32] W.S. Barnhart, US Patent 2,898,382 (to 3 M).
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(1995) 241.