I. Wlassics, V. Tortelli / Journal of Fluorine Chemistry 127 (2006) 240–248
247
0.9%), 260 (M2+, 1.7%), 258 (M+, 0.7%), 179 (M+, –C2F4Br,
62%), 100 (M+, –C2F4, 49.4%), 50 (M+, –CF2–, 100%).
n = 4: 19F NMR (200 MHz, CFCl3)—d ꢀ65 (s, 4F), ꢀ115 (s,
4F), ppm. MS: m/z—281 (M2+, –C4F8Br, 19.7%), 279 (M+, –
C4F8Br, 21.4%), 179 (M+, –C2F4Br, 4.9%), 129 (M+, –CF2Br,
29.6%), 100 (M+, –C2F4, 18.6%), 50 (M+, –CF2–, 100%).
n = 6: 19F NMR (200 MHz, CFCl3)—d ꢀ64 (s, 4F), ꢀ114 (s,
4F), ꢀ120 (s, 4F), ppm. Boiling point = 141–143 8C. MS: 381
(M2+, –C6F12Br, 1.87%), 379 (M+, –C6F12Br, 1.44%), 231 (M2+,
–C3F6Br, 0.52%), 179 (M+, –C2F4Br, 1.4%), 129 (M+, –CF2Br,
63.4%), 131 (M2+, –CF2Br, 100%), 50 (M+, –CF2–, 0.83%).
n = 8: 19F NMR (200 MHz, CFCl3)—d ꢀ64 (s, 4F), ꢀ114 (s,
4F), ꢀ120 (s, 4F), ꢀ123 (s, 4F), ppm. Boiling point = 150 8C
(350 mmHg). MS: 481 (M2+, –C8F16Br, 6%), 479 (M+,
–C8F16Br, 6%), 231 (M2+, –C3F6Br, 8%), 179 (M+, –C2F4Br,
11%), 131 (M2+, –CF2Br, 96%), 129 (M+, –CF2Br, 57%), 50
(M+, –CF2–, 5%).
4.4.5. Analysis of telogen (a), C2F2Cl2Br2
19F NMR (200 MHz, CFCl3): d ꢀ63.7 (s, 2F, d, l, Meso),
ppm.
GC: (3m packed, silicone column; 70 8C, 10 min, 15 8C/
min, 210 8C)—r.t. = 8.1 min.
MS: 296/294/292/290 (M6+/M4+/M2+/M+, 0.51%/1.4%/
1.5%/0.6%), 217/215/213/211 (M6+/M4+/M2+/M+, C2F2Cl2
Br–, 1.3%/47%/100%/7%), 149/147/145 (M4+/M2+/M+, –CF
ClBr, 9.5%37.7%/30.6%).
4.5. Synthesis of CH2 CH(CF2)6CH CH2 (1)
Compound (1), CH2 CH(aCF2 CF2 CF2)3CH CH2, was
synthesized in two steps (ethylation followed by dehydroha-
logenation with base) employing the same synthetic procedure
described in the literature starting from Br(CF2)nBr with n = 6
[13]. The overall isolated yield of (1) = 70 mol% (with respect
to the starting moles of Br(CF2)nBr with n = 6) after distillation
employing a Spalt-Rohr Fischer distillation apparatus with 60
theoretical plates.
b
c
4.4.3. Analysis of Br(CF2CF2)xCFClCFCl(CF2CF2)yBr
telomers
ꢁ x = 0, y = 1:
19F NMR (200 MHz, CFCl3): d ꢀ114 (s, 4F, –aCF2–), ꢀ121
MS: 313 (M2+, BrCFClCFClC2F4–, 1.4%), 311 (M+,
BrCFClCFClC2F4–, 0.6%), 277 (M1+, –BrCFCFClC2F4–,
1.9%), 181 (M2+, –C2F4Br, 26.9%), 179 (M+–C2F4Br,
24.6%), 131 (M2+, –CF2Br, 100%), 129 (M+, –CF2Br,
87.1%).
(s, 4F, –bCF2–), ꢀ124 (s, 4F, –cCF2–), ppm.
1H NMR (200 MHz, TMS): d 5.9 (m, 4H, –CH CH2), 5.5
(m, 2H, –CH CH2), ppm.
FTIR: n 1644 (–CH CH2 st), 1150 (internal –CF– st), cmꢀ1
.
ꢁ x = 1, y = 1:
Acknowledgements
MS: 413 (M2+, BrC2F4CFClCFClC2F4–, 0.2%), 411 (M+,
BrC2F4CFClCFClC2F4–, 0.12%), 247/245 (M2+/M+,
BrC2F4CFCl, 19%/14%), 181/179 (M2+/M+, –CF2Br,
19.8%/18.3%), 131/129 (M2+/M+, BrC2F4–, 88.7%/68%),
100 (M+, C2F4, 32.2%).
Special thanks go to Dr. Patrizia Dardani and Dr. Franceso
Morandi for the recording and interpretation of all the MS
spectra.
ꢁ x = 2, y = 1:
References
MS: 515/513/511 (M4+/M2+/M+, Br(C2F4)2CFClCF
ClC2F4–, 0.4%/0.8%/0.5%), 283/281/279 (M4+/M2+/M+,
Br(C2F4)2–, 0.1%/1.4%/0.8%), 181/179 (M2+/M+, –CF2Br,
24.9%/19.9%), 131/129 (M2+/M+, BrC2F4–, 100%/62.8%),
100 (M+, C2F4, 25.9%).
[1] G. Caporiccio, G. Bargigia, C. Tonelli, V. Tortelli, U.S. Patent 4,833,274,
CA 107:6762, 1989.
[2] G. Caporiccio, G. Bargigia, C. Tonelli, V. Tortelli, EP 194781, CA
106:69110, 1988.
[3] I.L. Knunjants, Izv. Akad. Nauk SSSR, Ser. Khim. 2 (1964) CA 60:11883.
[4] V. Arcella, G. Brinati, M. Albano, V. Tortelli, U.S. Patent 5,585,449, CA
123:259509, 1995.
4.4.4. Analysis of selected CxF(2xꢀ2)ClBr and other ‘‘–
ClBr’’ telomers
[5] V. Arcella, G. Brinati, M. Albano, V. Tortelli, EP 661312, CA 123:287212,
1995.
ꢁ ClCF CF(CF2CF2)nBr:
n = 1: MS—278/276 (M2+/M+, 85%/67%), 197 (M+,
C4F6Cl–, 27%), 180 (M1+, –C2F4Br, 22%), 149/147 (M2+/
M+, ClCF CFCF2–, 38.4%/100%), 131/129 (M2+/M+, –
CF2Br, 12.6%/11.2%), 100 (M+, C2F4, 61%).
n = 2: MS—380/378/376 (M4+/M2+/M+, 0.9%/4.2%/3.3%),
297 (M+, C6F10Cl–, 2.8%), 180 (M1+, –C2F4Br, 1.7%), 149/
147 (M2+/M+, ClCF CFCF2–, 35.4%/100%), 131/129 (M2+/
M+, –CF2Br, 15.7%/11.2%), 100 (M+, C2F4, 10%).
ꢁ Br(CF2CF2)nCl
[6] D. Bloor, R. Brook, M. Subhash, R. Cahn (Eds.), The Encyclopedia of
Advanced Materials, Elsevier, 1994, pp. 2767–2777.
[7] G. Baudein, B. Boutevin, R. Bertocchio, A. Lantz, C. Verge, J. Fluorine
Chem. 90 (1998) 107–115.
´
[8] B. Ameduri, B. Boutevin, Organofluorine Chemistry, Topics in Organo-
fluorine Chemistry, vol. 192, Springer, 1997, pp. 165–187.
[9] V. Tortelli, C. Tonelli, J. Fluorine Chem. 47 (1990) 199–217.
[10] I. Wlassics, V. Tortelli, M. Sala, D. Montrone, J. Fluorine Chem. 121
(2003) 65–74.
[11] T.H. Lowry, K.S. Richardson, Mechanism and Theory in Organic
Chemistry, second ed., Harper and Row Publishers, NY, 1981, p. 146.
[12] (a) C.M. Starks, Free Radical Telomerization, Academic Press, NY, 1974,
pp. 138–142;
n = 1: MS—218/216/214 (M4+/M2+/M+, 1.8%/5.3%/
3.9%), 181/179 (M2+/M+, BrCF2CF2–, 13.3%/12.2%), 137/
135 (M2+/M+, ClCF2CF2–, 31.4%/100%).
(b) C.M. Starks, Free Radical Telomerization, Academic Press, NY, 1974,
pp. 133–138.
n = 3: MS—337/335 (M2+/M+, C6F12Cl–, 2.0%/6.6%),
181/179 (M2+/M+, BrCF2CF2–, 12.3%/8.9%), 131/129 (M2+/
M+, –CF2Br, 100%/42.6%).
[13] I. Wlassics, V. Tortelli, Italian Patent MI2001A000316, 2001.
´
[14] B. Ameduri, B. Boutevin, Organofluorine Chemistry, Topics in Organo-
fluorine Chemistry, vol. 192, Springer, 1997, pp. 188–233.