V.A. Petrov et al. / Journal of Fluorine Chemistry 109 12001) 25±31
31
Table 1 .Continued )
No.
Compound bp .8C)
Pressure
Yield
IR .C=C,
cmÀ1
19F NMR
1H NMR
Anal. .MS):
.mmHg)
.%)
)
.d, ppm; J, Hz)
.d, ppm; J, Hz)
found .calcd.)
11
34ac
79±80
75
1677
À74.71 .3F, m)
1.10 .3H, t; 8)
2.12 .2H)
C, 41.74 .40.79)
H, 4.12 .3.91)
F, 54.64 .55.30)
À108.00 .1F, dm; 272)
À113.11 .1F, dm; 272)
À210.27 .1F, dm; 50)
4.80 .1H, d; 50)
5.28 .1H, s)
5.49 .1H, br, s)
34bc
79±80
75
1677
À74.88 .3F, m)
1.75 .6H, m)
4.80 .1H, d; 50)
6.00 .1H, m)
À108.25 .1F, dm; 256)
À113.15 .1F, dm; 256)
À210.27 .1F, dm; 50)
a Ratio 23:77.
b Isolated after attempt to isolate 18 by distillation at atmospheric pressure.
c Ratio 25:75.
Alcohols 11, 13, 15, 17, 27, 29 and 33 were made by
radical addition of hydrocarbon alcohol to the corresponding
¯uoro-ole®n .tetra¯uoroethylene, hexa¯uoropropylene or
per¯uorobutylethylene) at 120±1408C using t-butylperoxide
as initiator. Other starting materials and solvents are com-
mercial. Compound 1 .made by the reaction of dimethyla-
mine and tetra¯uoroethylene, see below) was stored at room
temperatureinproperlyclosed polyethyleneofTe¯on1 bottle
and handled in a fume hood. Since material of high purity
.>96%) can be easily prepared using this procedure, for the
most of ¯uorination reaction crude, nondistilled 1 was used.
Compounds 2, 5, 7a, 10, 10a,b, 12, 12a,b, 26, 36, 36a, 38,
38a, 40, 40a, 42 and 42a, 50, 53a, 54a were identi®ed by
comparison to authentic samples .GC, NMR). Fluorides 8a,
24a,b, 42, 50 [9], 3-b-¯uorocholest-5-ene [5], 52a [12], 8d
[13], 45a [14], 45b [15,16], 46a [17] and 47a [18] by
comparison of NMR data gave the reported values.
Reaction mixture is brought to ambient temperature,
stirred for 1 or 2 h poured on ice, organic layer is
separated, washed twicewith 10% HCl, dried over MgSO4
and distilled. Data for new materials are given in Table 1.
2. Alcohol .primary or polyfluorinated) is added dropwise
to 1 in Teflon1 or polyethylene reactor to keep
temperature below 308C. Reaction mixture is refluxed
for 1±6 h at 70±1008C and worked up as it is described
above. Reaction of compounds 19, 20, 25, 49 and 1 were
carried out in Hastelloy shaker tube. Some data for new
materials can be found in Table 1.
References
[1] G.A. Olah, X.-Y. Li, in: G.A. Olah, R.D. Chambers, G.K.S. Prakash
.Eds.), Synthetic Fluorine Chemistry, Wiley, New York, 1992, p. 163.
[2] A.I. Burmakov, B.V. Kunshenko, L.A. Alekseeva, L.M. Yagupolskii,
in: L.S. German, S. Zemskov .Eds.), New Fluorinating Agents in
Organic Synthesis, Springer, New York, 1989, p. 197.
[3] L.N. Markovskii, V.E. Pashinnik, in: L.S. German, S. Zemskov
.Eds.), New Fluorinating Agents in Organic Synthesis, Springer, New
York, 1989, p. 254.
Caution: Compound 1 in the presence of water or moist-
ure is a powerful source of hydrogen ¯uoride, which can
cause severe chemical burns. Compound 1 has to be handled
with great caution and by a trained personnel. Compound 1
reacts violently with water.
[4] W. Dmowski, in: M. Hudlicky, A.E. Pavlath .Eds.), Chemistry of
Organic Fluorine Compounds. II. A Critical Review, American
Chemical Society, Washington, DC, 1995, p. 263.
4.1. Preparation of 1
[5] A. Takao, H. Iwakiri,N. Ishikawa, Bull. Chem. Soc.Jpn. 52 .1979)3377.
[6] W. Dmowskii, M. Kamienski, J. Fluorine Chem. 23 .1983) 219.
[7] N.N. Yarovenko, M.A. Raksha, Z. Obsh. Khim. 29 .1959) 158.
[8] D. England, L. Melby, M. Dietrich, R. Lindsey, J. Am. Chem. Soc. 82
.1960) 3377.
A 400 ml Hastelloy reactor was charged with 22 g
.0.49 mol) of dimethylamine and 50 g .0.5 mol) of tetra-
¯uoroethylene. The reactor was kept with agitation for 12 h
at ambient temperature and unloaded. Crude product iso-
lated in four runs was combined and distilled at reduced
pressure to give 278.5 g .96%) of 1, bp 35±368C/150 mmHg
.328C/127 mmHg). NMR data of 1 are given in Table 1.
[9] W. Middleton, J. Org. Chem. 40 .1975) 574.
[10] V. Dedek, F. Liska, Collection Czechoslov. Chem. Commun. 32
.1967) 4297.
[11] F. Liska, V. Dedek, Z. Chvatal, L. Cvak, Czechoslov. Chem.
Commun. 40 .1975) 1441.
[12] V.I. Stepanov, A.I. Burmakov, B.V. Kunshenko, L.A. Alekseeva,
L.M. Yagupol'skii, Z. Org. Khim. 19 .1983) 273.
4.2. Typical procedures for reaction of 1 with alcohols
[13] L. Eliane, M. Bernard, T. Robert, Tetrahedron 45 .1989) 4431.
[14] W. Offerman, A. Annschreck, Org. Magn. Res. 22 .1984) 355.
[15] J. San Filippo, L.J. Louis, J. Org. Chem. 40 .1975) 782.
[16] E.L. Elier, R.J.L. Martin, J. Am. Chem. Soc. 90 .1968) 682.
[17] G.A. Olah, J.G. Shih, V.V. Krishnamurty, B.P. Singh, J. Am. Chem.
Soc. 106 .1984) 4492.
1. Solution of secondary, tertiary or cyclic alcohol .0.01±
0.05 mol in 10±15 ml of inert solvent) is slowly added to a
solution of 1 .solution in 10±15 ml of the same solvent, 5±
10 mol% excess) in Teflon1 or polyethylene reactor with
agitation, keeping temperature between 0 and 108C.
[18] F.J. Weigert, J. Org. Chem. 45 .1980) 3476.