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Table 1. Fluorocontaining alcohols dehydration in H2SO4
at zeolite presence
|
# |
Polyfluorinated alcohol (PFA) |
Zeolite |
Raw charging |
T,oC |
Time, h |
Yield,% |
Purity, % mass. |
|
PFA |
Zeolite |
H2SO4 |
g |
% |
|
f |
mole |
g |
% |
g |
mole |
|
1 |
ÍCF2CF2C(CH3)2OH |
NaX |
48 |
0.3 |
19.2 |
40 |
49 |
0.5 |
42-53 |
0.2 |
41.4 |
97.0 |
99.98 |
|
2 |
ÍCF2CF2C(CH3)2OH |
NaX |
80 |
0.5 |
0.8 |
1 |
98 |
1 |
73-98 |
0.3 |
68.7 |
96.5 |
99.81 |
|
3 |
ÍCF2CF2C(CH3)2OH |
NaX |
64 |
0.4 |
12.8 |
20 |
73.5 |
0.75 |
71-94 |
0.3 |
55.3 |
97.1 |
99.92 |
|
4 |
ÍCF2CF2C(CH3)2OH |
NaA |
48 |
0.3 |
19.2 |
40 |
49 |
0.5 |
55-69 |
0.25 |
41.1 |
96.2 |
99.85 |
|
5 |
ÍCF2CF2C(CH3)2OH |
CaA |
80 |
0.5 |
0.8 |
1 |
98 |
1 |
114-125 |
0.35 |
68.1 |
95.7 |
99.82 |
|
6 |
ÍCF2CF2C(CH3)2OH |
NaX |
48 |
0.3 |
25 |
52 |
49 |
0.5 |
43-52 |
0.3 |
41.0 |
96.0 |
99.97 |
|
7 |
ÍCF2CF2C(CH3)2OH |
NaX |
48 |
0.3 |
0.1 |
0.2 |
49 |
0.5 |
42-51 |
0.3 |
29.2 |
68.4 |
99.95 |
|
8 |
ÍCF2CF2C(CH3)2OH |
NaX |
48 |
0.3 |
19.2 |
40 |
40 |
0.4 |
45-59 |
0.25 |
40.9 |
95.8 |
96.81 |
|
9 |
ÍCF2CF2C(CH3)2OH |
NaX |
48 |
0.3 |
19.2 |
40 |
105 |
1.1 |
54-65 |
0.3 |
41.3 |
96.7 |
99.89 |
|
10 |
CF3CFHCF2C(CH3)2OH |
NaX |
84 |
0.4 |
16.0 |
19 |
73.5 |
0.75 |
61-89 |
0.3 |
74.5 |
96.9 |
99.91 |
|
11 |
CF3CFHCF2C(CH3)2OH |
NaA |
63 |
0.3 |
25.2 |
40 |
49 |
0.5 |
44-53 |
0.25 |
55.8 |
96.9 |
99.89 |
|
12 |
CF3CFHCF2C(CH3)2OH |
CaA |
105 |
0.5 |
1.5 |
1.0 |
98 |
1 |
110-118 |
0.3 |
92.1 |
96.0 |
99.90 |
Table2. NMR 1H, 13C, 19F
spectra of new partly fluorinated compounds
|
# |
NMR Spectra, d ppm. (J,
Hz) |
|
 H |
 C |
F |
|
2b
 |
5.67 (H1, t, 50);
5.43 (H4);
5.33 (H4);
1.84 (H5) |
135.3 (C3, 2JCF
22.5);
119.4 (C4, 2JCF 8.3);
115.4 (C1, 1JCF
250.2; 2JCF 24.8); 110.8 (C2,
1JCF 250.3; 2JCF
41.8); 16.6 (C5)
|
46.5 (F2, s);
28.9 (F2, d , 57.2) |
|
2d
 |
5.39 (H5, t, 1.2);
5.53 (H5, t, 0.8);
4.77 (H2, dt, 44.0; 6.4)
1.92 (H6, s) |
136.7 (C4, 1JCF
22.4);
121.4 (C1, 1JCF
281.4; 1JCF 25.9);
118.9 (C5); 116.8 (C3, 1JCF
246.6; 2JCF 23.7);
86.4 (C2, 1JCF 198.1;
2JCF 35.3); 16.4 (C6) |
89.2 (F1, s); 50.1 and 55.2 AB-system JFF
274.8 (F2);
-50.3 (F3, d, 50) |
|
3b
 |
6.19 (H1, tt, 52.4; 5.6);
3.85 (H4, t, 12.4);
1.77 (H5, s)
6.19 (H1, tt, 52.4; 5.6);
3.82 (H4, s);
1.67 (H5, s) |
115.7 (C1, 1JCF
259.3; 2JCF 24.8); 109.8 (C2, 1JCF
252.1; 2JCF 32.7); 48.4 (C5); 68.5 (C4,
2JCF 24.1); 21.9 C6)
115.9 (C1, 1JCF
259.3; 2JCF 24.8); 110 (C2, 1JCF
252.1; 2JCF 32.7); 70.1 (C4, 2JCF
23.4); 20.9 (C6); 48.4 (C5) |
41.5 and 38.6 AB-system JFF 288.1 (F1);
28.8 (F2, t, 2JCF
33.3) |
|
3d
 |
5.46 (H5, s);
5.32 (H5, s);
3.92 (H2,d, 50.0; 6.0);
1.89 (H6, s) |
136.6 (C4, 2JCF
22.4); 121.1 (C1, 1JCF 281.6; 2JCF
15.7); 116.7 (C3, 1JCF 270.7; 2JCF
26.7); 86.2 (C2, 1JCF 197.8; 2JCF
35.5); 48.0 (C5, c); 20.8 (C6, c) |
89.1 (F1); 55.1 and 50.0 AB-system JFF
265.8 (F2);
-46.7 (F3,multiplet) |
|
5
 |
5.97 H1, tt 53.0, 4.8),
4.72 (H6, s),
4.05 (H5, t 14.2) |
|
44,2(F4), 42.3 (F3),
36.2 (F2), 26.9 (F1, d 53.0) |
|
6
 |
5.95 (H1, tt, 3.4;49.8)
4.81 (H5, s)
4.13 (H3,tq, 7.4, 8.0)
1.33 (H4, t, 5.6)
|
115.6 (C1, 1JCF
257.8; 2JCF 6.8);
109.6 (C2, 1JCF
248.4; 2JCF 36.9)
93.4 (C4), 72.1 (C3, 2JCF
27.1)
12.3 (C4)
|
(F1) 36.0 and 32.2 (JFF
270.7); 25.9 and 22.9
(JFF 293.3)
|
|
8
 |
4.75 (H5, s)
4.13 (H4, t, 3.8)
5.03 (H2, d, 49.6) |
120.7 (C1, 1JCF
282.5; 2JCF 24.7);
116.9 (C3, 1JCF
250.2; 2JCF 24.8);
95.8 (C5); 83.9 (C2, 1JCF
191.2;2JCF 9.1); 65.7 (C4, 2JCF
27.3); 12.3 (C5)
|
(F1) 89.6; (F3) 46.9 and 42.8 (JFF
291.4);
(F2) -50.3
|
|
9
 |
4.78 (H8, s);
4.04 (H7, t, 14.2) |
117.6 (C1, 1JCF
287.6; 2JCF 33.1); 115.6 (C6, 1JCF
258.1; 2JCF 31.1); 96.3 (C8), 64.8 (C7,
2JCF 26.1) |
82.7 (F1, t, 10.2); 44.0 (F2, s); 42.3 (F3),
s); 41.6 (F4, s); 40.9 (F5, s); 37.9 (F6,
tt, 22.2; 8.09) |
|
10
 |
5.88 (H1, tt 53.0, 4.8),
4.72 (H4, s),
3.90 (H3, t 12.8) |
|
38.4 (F2, s),
24.5 (F1, d 53.3)
|
|
11
 |
5.97 (H1, tt 52; 4.8)
4.78 (H7, s);
4.05 (H8, t 4.8) |
|
44.1 (F5), 42.3 (F4), 40.9 (F2,3),
34.4 (F6), 26.5 (F1, d 52) |
|
12
 |
5.93 (H1, tt 53, 4.8),
4.78 (H9, s),
4.09 (H10, t 4.8) |
114.4 (C1, 1JCF
257.3; 2JCF 30.4); 109.5 (C2-8,
1JCF 254.0; 1JCF 31.6); 94.9 (C10);
63.3 (C9, 2JCF 25.4) |
44.2 (F7), 42.3 (F6), 40.2 (F3-5),
34.2 (F2), 26.4 (F1, d 53.0) |
Table 3. Characteristic of partly
fluorinated compounds and analytical data
|
Product |
Yield, % |
Boiling Point oC/ mm Hg |
Found, % |
Formula |
Calculated, % |
|
C |
H |
F |
C |
H |
F |
|
2a |
67 |
24-25 |
|
|
|
|
|
|
|
|
2b |
92 |
52-53 |
42.40
42.52 |
4.11
4.29 |
53.06
53.07 |
C5H6F4 |
42.25 |
4.23 |
53.52 |
|
2c |
92 |
47-48 |
|
|
|
|
|
|
|
|
2d |
97 |
69-70 |
37.78
37.57 |
2.97
3.13 |
58.75
58.45 |
C6H6F6 |
37.50 |
3.13 |
59.38 |
|
3b |
65 |
85-86 |
28.75
28.61 |
3.35
3.21 |
36.35
36.62 |
C5H6Cl2F4 |
28.17 |
2.82 |
35.68 |
|
3d |
72 |
102-103 |
43.78
43.98 |
2.70
2.68 |
43.29
43.62 |
C6H6Cl2F4 |
27.38 |
2.28 |
43.35 |
|
6 |
77 |
89-90/0.5
|
35.53
35.52 |
4.32
4.36 |
50.33
50.13 |
C9H12F8O2 |
35.53 |
3.95 |
50.00 |
|
8 |
87 |
92-93/0.5 |
35.24
35.92 |
4.25
4.08 |
50.24
50.44 |
C9H8F12O2 |
28.72 |
2.13 |
60.64 |
|
9 |
94 |
106-107/6 |
25.47
25.71 |
0.95
0/86 |
69.64
69.35 |
C15H6F26O2 |
25.28 |
0.84 |
69.38 |
|
12 |
79 |
191-194/0.4 |
25.46
25.23 |
0.99
1.22 |
69.47
69.79 |
C19H8F32O2 |
26.03 |
0.91 |
69.41 |
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