Methyl hypofluorite (MeOF) reactions with various fluoroolefins

Article abstract of DOI:10.1016/S0022-1139(02)00163-X

The reaction of methyl hypofluorite (MeOF) with certain fluoroolefins, such as CF₂=CF₂, CF₂=CFCF₃, CF₂=CFOCF₃, CF₂=CFOMe, CF₂=CClF, CF₂=CHF, CF₂=CH₂, CHF=CH₂, CF₂=CFCF=CF₂, occurred in CD₃CN or in the presence of NaF. Using neat MeOF in the presence of NaF was a novel method and gave good results. We observed that when more than three fluorine atoms are bonded to the C-C double bond, the addition products were obtained in mostly good yields.

Full text of DOI:10.1016/S0022-1139(02)00163-X

Journal of Fluorine Chemistry 119 (2003) 3±8
Methyl hypo¯uorite (MeOF) reactions with
various ¯uoroole®ns
a,*
Tetsuya Suzuta , Takashi Abe , Akira Sekiya
b
b
a
Toagosei Co. Ltd., 2 Ohkubo, Tsukuba, Ibaraki 300-2611, Japan
b
National Institute ofAdvanced Industrial Science and Technology, AIST Central 5,
-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
1
Received 3 June 2002; received in revised form 5 July 2002; accepted 9 July 2002
Dedicated to Professor Tatlow on the occasion of his 80th birthday.
Abstract
The reaction of methyl hypo¯uorite (MeOF) with certain ¯uoroole®ns, such as CF2ˆCF2, CF2ˆCFCF3, CF2ˆCFOCF3, CF2ˆCFOMe,
CF2ˆCClF, CF2ˆCHF, CF2ˆCH2, CHFˆCH2, CF2ˆCFCFˆCF2, occurred in CD CN or in the presence of NaF. Using neat MeOF in the
3
presence of NaF was a novel method and gave good results. We observed that when more than three ¯uorine atoms are bonded to the C±C
double bond, the addition products were obtained in mostly good yields.
#
2002 Elsevier Science B.V. All rights reserved.
Keywords: Methyl hypo¯uorite; Fluoroole®ns; Hydro¯uoroether
1
. Introduction
2. Results and discussion
We report the reactions of methyl hypo¯uorite (MeOF)
with certain ¯uoroole®ns in CD CN or in presence of NaF.
2.1. Reaction of lf uoroole if n with MeOF in CD 3CN
3
We observed that when more than three ¯uorine atoms are
bonded to the C±C double bond, the addition products were
obtained in mostly good yields in CD CN. When MeOF
Model studies were carried out with MeOF and tetra-
¯uoroethylene 1 in CD CN. We prepared MeOF by the
3
3
reaction of 10% F /He (100 cm /min) with 3 g of methanol
3
2
reacted with ¯uoroole®ns in the absence of solvent no
addition products were obtained, but in the presence of
NaF addition products were obtained. Some of the addition
products are hydro¯uoroethers (HFE's) which have been
envisaged as alternatives to CFC's [1].
in 3 g of propionitrile solution at À40 8C for 1 h, as already
reported in the literature [2]. MeOF was carried by a stream
of nitrogen from the reactor in which it was formed to a
monel U-tube cooled by liquid nitrogen, which was linked to
a vacuum line equipped with an NMRtube containing
3
0.5 cm of CD CN. Thereafter, MeOF and 1.07 mmol of
Recent reports [2] have described the generation of
MeOF from the treatment of methanol with ¯uorine gas.
This proved to be the only source of the novel electrophilic
3
1 were carried to the NMRtube by the usual vacuum line
method. This sample was measured using H and 19F NMR
spectrometers at À45 8C. A 1.98 mmol aliquot of MeOF was
1
‡
methoxylium moiety `MeO '. MeOF can be quickly gen-
1
erated as a 0.1±0.15 mol/l solution in acetonitrile and has
been found to react with electron-rich types of C±C double
bonds [3]. On the other hand, electron-poor double bonds
such as the one present in 3-methylcyclohexanone or
methyl a-phenylcinnamate were completely resistant to
MeOF [4].
obtained as determined by the MeOF area of the H NMR
compared with the acetonitrile area which was contained in
CD CN. The sample was then cooled in a dry ice±acetone
3
bath and gradually allowed to warm to room temperature.
1
19
The reaction mixture was measured by H NMR , F NMR
and GCMS; 0.68 mmol of MeOCF CF 2 were obtained in
2
3
63% yield based on 1. Trioxane, which was a decomposition
product of MeOF was also measured. A series of ¯uoroo-
le®ns were reacted with MeOF using the same method and
the results are shown in the Table 1.
*
Corresponding author. Tel.: ‡81-298-65-2607.
E-mail address: tetsuya_suzuta@mail.toagosei.co.jp (T. Suzuta).
0022-1139/02/$ ± see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 2 ) 0 0 1 6 3 - X

4
T. Suzuta et al. / Journal ofFluorine Chemistry 119 (2003) 3±8
Table 1
other. The substance denoted by the letter b is the reverse.
When comparing the reactions of CF OF with 3 to produce
3
Reactions of MeOF with various fluoroolefins in CD CN
MeOF in CD3CN
3
YXCˆCFZ !
CFXYCFZIMea ‡ CF2ZCXYOMeb X, Y, Z
a
3 2
À78 to R:T:
H, F, Cl, OMe, OCF
CF OCF CF CF a and CF OCF(CF ) b in the ratio of a:b
3 2
3
2
2
3
3
ˆ
3
CF
, CF=CF
ˆ
67:33, the high selectivity of this reaction was remarkable
b
c
d
Fluoroolefin
Products
Ratio (%)
Yield (%)
[
5]. Furthermore, MeOF was reacted with CF2ˆCFOCF3 5,
CF
CF
CF
CF
CF
CF
CF
2
2
2
2
2
2
2
=CF
=CFCF
=CFOCF
2
1
2
4a, 4b
±
98
100
100
100
84
72
0
63
71
22
75
61
97
10
3
CF2ˆCFOMe 7 or CF2ˆCFCl 9 to produce MeOCF C-
2
3
3
F OCF 6a, MeOCF CF OMe 8a or MeOCF CF Cl 10a,
2
2
3
2
2
2
3
5
6a
8a
respectively. In these reactions only the a series products
were obtained and the formation of the b series products
could not be seen at all. It was reported in the literature that
6a was dif®cult to obtain; it has been reported as a small
byproduct in the reaction of CF OCF CF COOH with
=CFOMe 7
=CClF 9
=CHF 11
10a
12a, 12b
14a, 14b
=CH
2
13
15
CF=CFCF
CHF=CH
CF
2
16b
±
3
2
2
3
3
17
18
±
0
HOOCCF COOCH [6].
2
3
e
17
±
±
0
In order to con®rm whether steric factors play any role in
determining the selectivity of the resulting products, the
reaction of MeOF with CF ˆCHF 11, CF ˆCH 13 or
CF
2
e
=CFCF=CF
2
±
±
0
f
18
19
±
94
a
2
2
2
If X ˆ Y ˆ F, then Z ˆ F.
b
c
d
CHFˆCH 15 were investigated. The a series were also
2
Only products from fluoroolefins.
the main products in the reactions with 11 and 13. It was
certain that the mechanism of these reactions was different
from the previously mentioned methoxylium mechanism
Percent ratio of a=ꢀa ‡ b†.
Not separated yield, standard was fluoroolefins or MeOF which was
less.
e
Solvent: propionitrile.
[3,4], because the electron density of the C±C double bond in
f
1.4 addition, cis:trans ˆ 11:89.
11 and 13 are clearly poorer than in 3-methylcyclohexanone
or methyl b-phenylcinnamate but the MeO bonds to the
more electron poor ole®n carbon to give series a. As
¯uoroole®ns were reacted with CF OF via a radical mechan-
When 0.267 mmol of MeOF were reacted with 0.31 mmol
3
of the asymmetric ole®n of CF ˆCFCF 3, the reaction was
ism [5] and MeOF decomposed via the radical mechanism
[7], we postulated that the previously mentioned series of
¯uoroole®ns reacted with MeOF via the radical mechanism
with the exception of 15. As only 15 produced series b as the
main products, we felt that the electrons in the C±C double
bonds of 15 were the richest in the series of ¯uoroole®ns,
therefore, it might react with MeOF via a methoxylium
mechanism.
2
3
1
monitored by H NMRat À45, À35 and À25 8C for 75 min,
at À15 8C for 95 min, at 0 and 20 8C for 75 min. These
results are shown in the Table 2. At À25 8C, the reaction was
very slow, and above 0 8C, the reaction was fast. Almost all
MeOF disappeared on reaction at 20 8C, and trioxane was
1
only detectable as the byproduct using H NMR .
CH OCF CF CF 4a and CH OCF(CF ) 4b were obtained
3
2
2
3
3
3 2
in a yield of 71%, and the ratio of a to b was 98:2. There were
no other peaks except those due to 3, 4a or 4b detected by
F NMR. Trioxane was the only byproduct detected by H
NMR. From here on, when a starting ole®n is unsymme-
We have also investigated the reaction of MeOF with
CF3CFˆCFCF3 17 and CF2ˆCFCFˆCF2 18 in acetonitrile-
1
9
1
d , but none of these compounds was found to react with
3
MeOF under these conditions. At low temperature, two
phases were observed in all these reaction mixtures. There-
fore, in order to obtain a homogenous phase, acetonitrile-d3
was replaced with propionitrile. In spite of this change,
MeOF did not react with 17 but with 18, which resulted in
trical, the substance denoted by the letter a signi®es that a
substance has CH O attached to the most electron-poor
3
carbon (the carbon in the double bond with the greater
number of ¯uorine bonded) and ¯uorine attached to the
Table 2
1
The reaction of MeOF with 3 monitored by H NMR
a
b
b
b
c
Time
MeOF
4a ‡ 4b
Trioxane
Yields (%)
Conversion of MeOF (%)
À45 8C start
34.8
33.1
36.4
25.8
0
0.0
3.4
0.0
4.9
À35 8C, 45 min
À25 8C, 65 min
À15 8C, 95 min
1.2
1.1
5.7
Broad peak
Broad peak
Broad peak
Broad peak
10.2
3.2
16.4
25.9
95.9
d
d
0
0
2
8C, 30 min
8C, 60 min
0 8C, 30 min
2:1
33.3
57.4
d
d
0.74:1
1.41
24.6
70.7
a
The NMRtube was controlled at À45, À35 and À25 8C for 75 min, at À15 8C for 95 min, at 0 and 20 8C for 75 min.
b
c
d
3
The ratio of the peak area to the acetonitrile peak area which was contained in CD CN.
4
a ‡ 4b divided by 34.8.
1
As the H NMRspectra were indistinct, only the ratio of MeOF to 4a ‡ 4b was measured.

T. Suzuta et al. / Journal ofFluorine Chemistry 119 (2003) 3±8
5
CF CFˆCFCF OMe 19 a novel compound (cis:trans ˆ
3. Conclusion
3
2
1
1:89 (determined by cis and trans by comparison with
the 19F NMRdata of the cis and trans per¯uoro-2-penten
8])) in 94% yield. The reaction was a 1,4 addition reaction.
We investigated the reaction of MeOF with certain ¯uor-
oole®ns, such as CF2ˆCF2, CF2ˆCFCF3, CF2ˆCFOCF3,
CF2ˆCFOMe, CF2ˆCClF, CF2ˆCHF, CF2ˆCH2, CHFˆ
[
It is normal that 18 reacted via a 1,4 addition mechanism and
the trans form is the major product [9].
CH2, CF3CFˆCFCF3, CF2ˆCFCFˆCF2, in CD CN or in
3
the presence of NaF. The use of neat MeOF in the presence
of NaF method was a novel method and had good results. We
observed that when more than three ¯uorine atoms are
bonded to the C±C double bond, the addition products were
obtained in mostly good yields.
2.2. Reaction of fluoroolefin with MeOF in the presence
ofNaF
A second model study was carried out with MeOF and 7 in
the presence of NaF. It was known that MeOF was only
stable in acetonitrile or propionitrile, and the use of neat
MeOF method was a novel method. MeOF was obtained as
above and transferred to a 15 cm, 1/4 in. bore stainless steel
tube ®tted with a valve; that contained 1.3 g of NaF. The
3.1. Caution
Neat MeOF is an explosive substance. Several samples
exploded violently upon warming to dry ice temperature. In
the absence of further information, neat MeOF should be
treated as an unpredictable explosive substance.
0
.87 mmol of 7 was added to the tube. The tube was allowed
to warm in a dry ice±acetone bath using the aforementioned
method. The 0.81 mmol of MeOF was transferred to the tube
(
calculated by the weight changes minus the weight of
4. Experimental section
charged 7). The reaction products were analyzed after
separating through traps cooled to À40, À78, À98 and
À198 8C. The addition product 8a (23% yield based on
4.1. Reaction of lf uoroole if n with MeOF in CD
CN
3
Measurements: H NMRand 19F NMRspectra were
1
MeOF) was collected in the À98 8C trap and shown to be
1
9
8% pure as determined by the H NMRarea ratio.
A series of ¯uoroole®ns were reacted with MeOF using
recorded on 300 MHz spectrometer, with CD CN as solvent
3
and propionitrile and the starting material of ¯uoroole®ns as
internal standard, the peaks of which were set at the value
the same method and the results are shown in the Table 3. In
the reaction of 3 with MeOF, the separation through traps did
not work well, and 4a was obtained with 3. There was no 4b
and the yield was 7%. In the other yields were separated
measured in CDCl . GC/MS spectra were measured on a
3
spectrometer and showed: m/z (fragment), percent intensity
relative to the parent ion. All ¯uoroole®n reagents was
purchased from Daikin and used without puri®cation.
Method ofdetecting amount ofmolecules : We used same
yields. Compared with the reactions in CD CN, the yields
3
were low, therefore, the ratio of a:b and the ratio of cis:trans
were almost same.
Lot. No. of CD
the amount of CH
method. 0.6681 g of CD
CH
OH were put into a NMRtube and measured the 1H
NMRspectrum of the sample. The CH peak area of CH OH
was 32.61 times as large as the CH peak area of CH CN in
the CD CN. The equation is given further.
CN in all experiment. At ®rst, we measured
CN in the CD CN by the following
CN and 0.1054 g (3.29 mmol) of
3
When MeOF was reacted with 3 in the absence of NaF and
solvent, no MeOF addition product was obtained. It is
believed that the reaction works well as in the presence
of NaF because of the formation of a stable complex, MeO±
F±Na±F.
3
3
3
3
3
3
3
3
3
CH CN (mmol) in 1 g of the CD3CN ˆ 3:29 mmol/
3
3
2.61/0.6681 g.
The reaction ofMeOF with 1: The 0.9210 g of CD CN was
Table 3
3
Reactions of MeOF with various fluoroolefins in presence of NaF
put into a NMRtube. After MeOF was put into the NMRtube,
1
a
b
c
we measured the H NMRspectrum at À45 8C. The CH
Fluoroolefin
Products
Ratio (%)
Yield (%)
3
peak area of CH OF was 14.26 times as large as the CH peak
3
3
d
CF
2
CF
2
CF
2
CF
2
CF
2
CF
2
CF
2
=CFCF
3
3
4a
8a
100
100
100
90
±
7
area of CH CN in the CD CN. The equation is given further.
3
3
=CFOMe 7
=CClF 9
23
32
35
0
CH OFꢀ mmol † ˆ 0:9210 g/0:6681 g  3:29 mmol Â
10a
12a, 12b
3
=CHF 11
14:26=32:61 ˆ 1:98 mmol.
=CH
2
13
±
After this measurement, 1 was put into the NMRtube and
reacted. In this reaction, we used an unique NMRtube which
was equipped with 1/4 in. connector and was capable of
being ®tted and removed with sealing.
e
=CFCF=CF
2
18
19
±
±
19
0
f
=CFCF
3
3
±
a
Only products from fluoroolefins.
Percent ratio of a=ꢀa ‡ b†.
Separated yield.
b
c
d
e
f
4.1.1. Reaction ofCF =CF 1 with MeOF in CD CN
2
Mixed with 5 and the yield was calculated by 19F NMRarea ratio.
.4 addition, cis:trans ˆ 11:89.
In absence of NaF.
2
3
The 1.07 mmol of 1 was added to 1.98 mmol of MeOF in
0.5 ml of CD CN. After controlled warmup, 2 was obtained
1
3

6
T. Suzuta et al. / Journal ofFluorine Chemistry 119 (2003) 3±8
1
19
in 63% yield. H NMR: 3.75 (3H, s). F NMR :À86.0 (3F, s,
CF ), À92.5 (2F, s, CF ).
4.1.6. Reaction ofCF =CHF 11 with MeOF in
2
CD CN
3
3
2
The 1.40 mmol of 11 was added to 0.64 mmol of MeOF in
0.5 ml of CD CN. After controlled warmup, 12a and 12b in a
4
.1.2. Reaction ofCF =CFCF 3 with MeOF in CD CN
2
3
3
3
1
The 3.10 mmol of 3 was added to 0.81 mmol of MeOF in
.5 ml of CD CN. After controlled warmup, 4a and 4b in a
ratio of 84:16 were obtained in 97% yield. For 12a. H NMR :
0
ratio of 98:2 were obtained in 71% yield. For 4a. H NMR:
3.68 (3H, s, CH ), 5.95 (1H, t, J ˆ 53 Hz, CHF ). 19F NMR :
3
3
2
1
À93.5 (2F, s, OCF ), À136.9 (2F, d, J ˆ 53 Hz, CHF ). For
1 19
3
2
2
3
.70 (3H, s, CH ). 19F NMR: À81.7 (3F, t, J ˆ 7 Hz, CF ),
12b. H NMR: 3.60 (3H, s, CH ), 5.4 (1H, m, CHF).
F
3
3
1
À89.1 (2F, s, CF CF ), À129.4 (2F, s, CF OMe). For 4b. H
NMR: À83.2 (3F, s, CF ), À145.0 (1F, d, J ˆ 60 Hz, CHF).
3
2
2
3
1
9
‡
‡
NMR: 3.70 (3H, s, CH ). F NMR: À81.6 (6F, s, CF ),
12a GC/MS m/z: 133 [CH OCF CF H ‡ H] (3.4), 113
3
3
3
2
2
‡
‡
À150.1 (1F, s, CF). 4a GC/MS m/z: 181 [CH OCF CF CF ]
[CH OCF CFH]
3
(8.3), 101 [CF CF H]
2
(5.1), 82
3
2
2
2
2
2
‡
‡
‡
‡
‡
‡
‡
(
1
6.3), 169 [CF CF CF ] (7.5), 147 [OCF CF CF] (6.7),
3
[CFCF ‡ H] (5.6), 81 [CFCF ] (100.0), 69 [CF ‡ F]
‡ ‡
2 2
2
2
2
2
2
2
2
‡
‡
31 [CH OCF CF ] (6.1), 119 [CF CF ] (33.5), 100
3
(10.9), 63 [CF CH] (3.7), 51 [CF H] (34.1), 47 [CFO]
2
2
2
3
‡
‡
‡
‡
‡
[
[
(
[
[
(
(
[
[
CF CF ] (8.5), 81 [CFCF ] (78.2), 69 [CF ] (53.9), 50
2
(8.2), 33 [CF ‡ 2H] (6.0), 32 [CF ‡ H] (3.2), 31 [CF]
2
2
3
‡
‡
‡
‡
‡
CF ] (4.4), 47 [OCF] (14.1), 31 [CF] (14.4), 29 [CHO]
2
(8.8). 12b GC/MS m/z: 133 [CH OCHFCF ‡ H] (8.6), 113
3
3
‡
‡
‡
‡
14.1) 4b GC/MS m/z: 219 [CH OCF(CF ) ‡F] (3.5), 181
[CH OCFHCF ] (4.5), 95 [CH OCHFCF ‡ H] (4.1), 82
3
3 2
3
2
‡
3
‡
‡
‡
CH OCF(CF ) -F] (3.1), 147 [OCF(CF ) ] (7.2), 131
[CFCF ‡ H] (5.1), 81 [CFCF ] (100.0), 69 [CF ] (20.5),
3
3 2
2 2
2
2
3
‡
‡
‡
‡
‡
‡
‡
CF(CF ) ] (56.0), 119 [CFCF ‡F] (4.9), 100 [CFCF ]
59 [COCF] (7.1), 51 [CF ‡ H] (24.5), 47 [OCF] (7.9),
2
2
3
3
2
‡
‡
‡
‡
4.9), 97 [OCFCF ] (17.7), 81 [CFCF ] (3.2), 69 [CF ]
2
31 [CH O] (7.4), 29 [CHO] (4.6).
3
2
3
‡
‡
‡
67.8), 44 [CH OC‡H] (7.5), 33 [CF‡2H] (15.2), 32
3
‡
‡
CF‡H] (14.8), 29 [CHO] (13.8), 28 [CO] (40.5), 15
4.1.7. Reaction ofCF =CH 13 with MeOF in CD CN
2
2
3
‡
CH ] (100.0).
3
The 1.24 mmol of 13 was added to 1.78 mmol of MeOF in
.5 ml of CD CN. After controlled warmup, 14a and 14b in
0
a ratio of 72:28 were obtained in 10% yield. For 14a. H
3
1
4
.1.3. Reaction ofCF =CFOCF 5 with MeOF in CD CN
2
3
3
The 1.46 mmol of 5 was added to 1.88 mmol of MeOF in
.5 ml of CD CN. After controlled warmup, 6a was
NMR: 3.59 (3H, s, CH ), 4.52 (2H, d, J ˆ 46 Hz, t,
3
1
9
0
J ˆ 9 Hz, CH F). F NMR: À86.0 (2F, d, J ˆ 16 Hz, t,
3
2
obtained in 22% yield. H NMR: 3.70 (3H, s, CH ). 19F
1
J ˆ 9 Hz, CF ), À235.5 (1F, t, J ˆ 46 Hz, t, 15 Hz, CH F).
3
2
2
1
NMR: À55.1 (3F, t, J ˆ 9 Hz, CF ), À89.7 (2F, q, J ˆ
For 14b. H NMR: 3.52 (3H, s, CH ), 3.82(2H, q, J ˆ 9 Hz,
19
2 3
3
3
1
1
[
0 Hz, CF OCF ), À92.8 (2F, s, CH OCF ). GC/MS m/z:
CH ). F NMR :À73.3 (3F, t, J ˆ 9 Hz, CF ).
2
3
3
2
‡
‡
‡
31 [CF CF OCH3] (7.9), 119 [CF CF ‡F] (6.7), 97
2
2
2
2
‡
‡
CF CFO] (6.5), 81 [CF O] (100.0), 69 [CF ] (56.0), 47
3
4.1.8. Reaction ofCHF=CH 2 15 with MeOF in
CD CN
2
3
‡
[
CFO] (12.1).
3
The 0.78 mmol of 15 was added to 0.91 mmol of MeOF in
0.5 ml of CD CN. After controlled warmup, 16b was
4
.1.4. Reaction ofCF =CFOCH 7 with MeOF in CD CN
3
2
3
3
The 1.00 mmol of 7 was added to 0.11 mmol of MeOF in
.5 ml of CD CN. After controlled warmup, 8a was obtained
obtained in 3% yield. 19F NMR :À126.5 (1F, d, J ˆ
0
44 Hz, t J ˆ 14 Hz, CHF ). GC/MS m/z 96 [CH OCH -
3
2
3
2
1
19
‡ ‡
CHF ] (74.7), 95 [CH OCH CHF -H] (10.2), 94 [CH -
2 3 2 2 3
in 75% yield. H NMR: 3.63 (3H, s, CH ). F NMR: À93.5
3
‡
‡ ‡
OCH CHF -2H] (79.3), 93 [CH OCH CHF -3H] (14.5),
2 2 3 2 2
(
4F, s, CF ) 8a GC/MS m/z: 143 [CH OCF CFOCH ] (1.6),
2
2
3
3
‡
‡
‡ ‡
81 [OCH CHF ] (12.9), 77 [CH OCH CHF] (12.1), 47
2 2 3 2
1
12 [CH OCF CF] (1.1), 109 [CH OCF CO] (2.3), 100
3
2
3
2
‡
‡
‡
‡
‡
[
CF CF ] (2.0), 97 [CF CO ‡ F] (1.3), 93 [CH OCF C]
[CH CHF ‡ H] (41.8), 31 [OCH ] (85.9).
2
2
2
3
2
2
3
‡
‡
(
5.1), 82 [CH3OCF2 ‡ H] (2.7), 81 [CFCF ] (100.0),
2
‡
‡
‡
7
8 [COCF ] (1.3), 69 [CF2 ‡ F] (3.2), 62 [CFOCH ]
4.1.9. Reaction ofCF CF=CFCF 17 with MeOF in
3 3
CD CN
3
2
3
‡
‡
(
4
1.5), 47 [OCF] (9.1), 45 [CH OCH ‡ H] (1.8),
3
3 [CH OC] (4.2), 33 [CF ‡ 2H]‡ (1.4), 31 [CH O]
‡
‡
The 1.61 mmol of 17 was added to 1.68 mmol of MeOF in
0.5 ml of CD CN. After controlled warmup, only 17 was
3
3
(
3.1).
3
recovered. When attempted in CH CH CN (17:0.57 mmol,
3
2
4
0
.1.5. Reaction ofCF =CClF 9 with MeOF in CD CN
3
MeOF: 0.79 mmol), no reaction was found.
2
The 1.20 mmol of 9 was added to 1.65 mmol of MeOF in
.5 ml of CD CN. After controlled warmup, 10a was
4.1.10. Reaction ofCF =CFCF=CF 18 with MeOF in
2
3
2
obtained in 61% yield. H NMR: 3.73 (3H, s, CH ). 19F
1
CD CN
3
3
NMR: À71.5 (1F, s, CClF), À90.8 (3F, s, CF ). GC/MS m/z:
The 1.07 mmol of 18 was added to 0.54 mmol of MeOF in
0.5 ml of CD CN. After controlled warmup, only 18 was
3
‡
‡
1
35 [ClCF CF ] (4.4), 131 [CH OCF CF ] (8.4), 100
2
2
3
2
2
3
‡
‡
‡
[
8
(
(
CF CF ] (4.5), 97 [OCF CF] (10.1), 87 [ClCF ] (6.3),
recovered. When reacted in CH CH CN (18:0.31 mmol,
2
2
2
2
2
3
‡
‡
‡
‡
5 [ClCF ] (19.2), 81 [CF OCH ] (100.0) 69 [CF ‡F]
MeOF: 0.13 mmol), 19 cis and trans in a ratio of 11:89
was obtained in 94% yield. GC/MS m/z 212 [CH -
2
2
3
2
‡
‡
14.5), 50 [CF ] (5.4), 47 [CFO] (12.6), 31 [CH O]
2
3
3
‡
‡
11.3).
OCF CFCFCF ]
2
(10.5), 193 [CH OCF CFCFCF ]
3
3
2
2

T. Suzuta et al. / Journal ofFluorine Chemistry 119 (2003) 3±8
7
‡
‡
‡
(
(
(
8
13.6), 181 [CF CFCFCF ] (30.1), 159 [OCF CFCFCF]
2
4.2.4. Reaction ofCF =CClF 9 with MeOF in the presence
2
ofNaF
3
2
‡
46.4), 143 [CH OCF CFCF] (17.3), 131 [CFCFCF ]
3
2
3
‡
‡
77.6), 109 [OCFCFCF] (16.3), 93 [CFCFCF] (23.1),
‡
The 1.05 mmol of 9 was reacted with 0.39 mmol of MeOF
in the presence of 1.0 g of NaF as above. The reaction
mixture was separated via trap to trap. 10a was collected in
‡
‡
1 [CFCF3] (80.5), 69 [CF ] (39.0), 62 [CH OCF]
3
3
‡
‡
1
(
47.4), 47 [OCF] (15.5), 31 [CH O] (33.0). For cis. H
3
1
9
1
NMR: 3.70 (3H, s, CH3). F NMR :À65.8 (3F, m, CF ),
the À98 8C trap. The purity was 75% as detected by the H
3
À74.8 (2F, m, CF ), À139.5 (1F, m, CFCF ), À147.1 (1F, m,
NMRarea ratio. The yield which was calculated by pressure
1
2
3
1
19
MeOCF CF). For trans. H NMR: 3.70 (3H, s, CH ).
2
F
was 32% based on MeOF. For 10a, H NMR: 3.73 (3H, s,
CH3). 19F NMR :À73.1 (1F, s, CClF), À93.0 (3F, s, CF ). IR:
3
NMR: À68.9 (3F, d, 21 Hz d,10 Hz, CF ), À76.5 (2F, d,
3
3
2
1 Hz d,10 Hz, CF ), À157.1 (1F, d, 138 Hz, CFCF ),
775 (w), 914 (w), 947(s), 1016 (s), 1051(m), 1130 (vs), 1180
(vs), 1251(s), 1352 (m), 1460 (s), 1743 (sh, m), 1755 (m),
2
3
À162.8 (1F, d, 138 Hz, MeOCF CF).
2
2974 (w).
4.2. Reaction of fluoroolefin with MeOF in the presence
ofNaF
4.2.5. Reaction ofCF =CHF 11 with MeOF in the
2
presence ofNaF
Measurements: 1H NMRand 19F NMRspectra were
The 0.98 mmol of 11 was reacted with 0.36 mmol of
MeOF in the presence of 1.3 g of NaF as above. The reaction
mixture was separated via trap to trap. 12a and 12b were
collected in the À98 8C trap. The purity was 98% as detected
recorded on an NMRspectrometer (282.238 MHz for 19F
1
and 299.95 MHz for H, respectively) with CDCl as solvent
3
and TMS and CFC-11 as internal standards. The gas phase
samples of IRspectra were measured with a usual FTIR
spectrometer.
1
by the H NMRarea ratio. The yield which was calculated
by pressure was 35% based on MeOF. The ratio of 12a and
1
1
2b was 90:10 detected by 19F NMR. For 12a, H NMR :
4
presence ofNaF
.2.1. Reaction ofCF =CFCF 3 with MeOF in the
3
3.68 (3H, s, CH ). 5.69 (1H, t, J ˆ 53 Hz t, J ˆ 3 Hz, CHF )
2
3
2
19
F NMR: À94.8 s, À137.3 (2F, t, J ˆ 53, t, J ˆ 3 Hz,
1
The 2.98 mmol of 3 was added to MeOF in the presence of
.2 g of NaF. The stainless steel tube weighed 219.211 g
CHF ) 12b, H NMR: 3.65 (3H, s, CH ). 5.28 (1H, d,
2
3
1
9
0
after NaF was charged, and it weighed 219.675 g after
MeOF and 3 were charged. The 2.98 mmol of 5 weighed
J ˆ 59 Hz q, J ˆ 3 Hz, CHF) F NMR: À84.1 (3F, s,
CF ), À146.1 (1F, d, J ˆ 59 Hz, q, J ˆ 3 Hz, CHF). IR
3
(12a ‡ 12b(90:10)): 744(w), 840(w), 1001(w), 1045(m),
1109(sh, m), 1139 (vs), 1238 (sh, m), 1288 (s), 1327 (m),
1462 (w), 2974 (w).
0
2
.447 g, so that a calculation of MeOF was follows
19:675-219:211-0:447 ˆ 0:0172 g: 0.34 mmol.
After tube was allowed to warm up in a dry ice/acetone
bath, the reaction mixture was separated through traps
cooled À40, À78, À98 and À198 8C on 30 torr. 4a was
seen in the À98 8C trap with 3, the purity was 19% detected
4.2.6. Reaction ofCF =CH 13 with MeOF in the presence
2
ofNaF
2
The 0.94 mmol of 13 was reacted with 0.37 mmol of
MeOF in the presence of 1.2 g of NaF as above. The reaction
mixture was separated via trap to trap. Neither 14a and 14b
were found.
1
9
by the F NMRarea ratio, the yield which was calculated by
1
pressure was 7% based on MeOF. For 4a, H NMR: 3.74 s.
9
1
F NMR: À82.1 (3F, t, J ˆ 7 Hz CF ), À90.0 (2F, s,
3
CF CF ), À130.0 (2F, s, CF OMe).
3
2
2
4.2.7. Reaction ofCF =CFCF=CF 18 with MeOF in the
presence ofNaF
2 2
4
.2.2. Reaction ofCF =CFCF 3 with just MeOF
2
3
The 1.73 mmol of 3 was reacted with 1.21 mmol of MeOF
The 1.08 mmol of 18 was reacted with 1.94 mmol of
MeOF in the presence of 1.3 g of NaF as above. The reaction
mixture was separated via trap to trap. 19 was collected in
without NaF by the same method as in the presence of NaF,
and the reaction mixture was separated via trap to trap. 4a
was not found.
1
the À78 8C trap. The purity was 93% as detected by the H
NMRarea ratio. The yield which was calculated by pressure
was 19% based on 18. The ratio of cis and trans was 90:10
4.2.3. Reaction ofCF =CFOMe 7 with MeOF in the
2
presence ofNaF
1
9
1
detected by F NMR . Forcis H NMR: 3.70 (3H, s, CH ).
3
1
9
The 0.87 mmol of 7 was reacted with 0.81 mmol of MeOF
in the presence of 1.3 g of NaF as above, and the reaction
mixture was separated via trap to trap. 8a was collected in
F NMR: À66.3 (3F, m, CF ), À75.5 (2F, m, CF ), À139.4
1
3 2
3
2
(1F, m, CFCF ), À147.1 (1F, m, MeOCF CF). For trans: H
1
9
NMR: 3.70 (3H, s, CH ). F NMR: À69.1 (3F, d, 20 Hz d,
3
1
the À98 8C trap, the purity was 98% detected by the H
10 Hz, CF ), À77.3(2F, d, 20 Hz, d, 10 Hz, CF ), À157.2
3
2
NMRarea ratio, the yield which was calculated by pressure
1
(1F, d, 138 Hz, CFCF ), À162.7 (1F, d, 138 Hz,
3
was 23% based on MeOF. For 8a, H NMR: 3.68 (3H, s,
MeOCF CF). IR(19 ( cis:trans ˆ 10:90)): 698 (s), 860
2
CH3). 19F NMR :À94.0 (4F, s, CF ). IR: 754(m), 1049 (m),
(m), 923 (w), 1002 (s), 1074 (sh, w), 1101(s), 1182 (vs),
1234 (vs), 1296 (vs), 1350 (m), 1460 (m), 1728 (w), 1786
(w), 2871 (w), 2974 (m).
2
1
3
115 (vs), 1184 (vs), 1230 (vs), 1461(s), 2874 (m), 2972 (s),
012 (m).

8
T. Suzuta et al. / Journal ofFluorine Chemistry 119 (2003) 3±8
[
3] (a) S. Rozen, E. Mishani, M. Kol, J. Am. Chem. Soc. 114 (1992)
643±7645;
Acknowledgements
7
(
(
(
b) S. Rozen, M. Kol, J. Org. Chem. 58 (1993) 1593±1595;
c) S. Rozen, Chem. Rev. 96 (1996) 1717±1736;
d) S. Rozen, Acc. Chem. Res. 29 (1996) 243±248.
This research was supported by the Research Institute of
Innovative Technology for the Earth (RITE).
[
[
4] S. Rozen, E. Mishani, M. Kol, I. Ben-David, J. Org. Chem. 59 (1994)
281±4284.
5] (a) K.K. Johri, D.D. DesMarteau, J. Org. Chem. 48 (1983) 242±250;
b) A. Sekiya, K. Ueda, Chem. Soc. Jpn. Lett. (1990) 609-612.
4
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(
7