Solvolytically DMSO-promoted reactions of 1,1,1-trifluoroethyl chloride (HCFC-133a) or fluoride (HFC-134a) with nucleophiles

Article abstract of DOI:10.1016/S0040-4020(02)00257-0

Fluorinated gases HCFC-133a (CF₃CH₂Cl, bp=6°C) and HFC-134a (CF₃CH₂F, bp=-27°C) are found highly soluble in DMSO. In their DMSO solutions, oxygen-, nitrogen- and sulfur-nucleophilic reactions may occur in normal

Full text of DOI:10.1016/S0040-4020(02)00257-0

TETRAHEDRON
Pergamon
Tetrahedron 58 '2002) 4077±4084
Solvolytically DMSO-promoted reactions of 1,1,1-tri¯uoroethyl
chloride ꢀHCFC-133a)or ¯uoride ꢀHFC-134a)with nucleophiles
Kai Wu and Qing-Yun Chenp
Laboratory of Organo¯uorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road,
Shanghai 200032, People's Republic of China
Received 29 October 2001; revised 4 January 2002; accepted 16 January 2002
AbstractÐFluorinated gases HCFC-133a 'CF3CH2Cl, bpˆ68C) and HFC-134a 'CF3CH2F, bpˆ2278C) are found highly soluble in DMSO.
In their DMSO solutions, oxygen-, nitrogen- and sulfur-nucleophilic reactions may occur in normal glassware rather than in the autoclave.
q 2002 Elsevier Science Ltd. All rights reserved.
1. Introduction
be inert under normal SN2 conditions.10 In order to utilize 1
as a ¯uorine source more effectively, it would be of signi®-
cance to search for milder reaction conditions. Fortunately,
DMSO as the solvent was found to be suitable for this
purpose.11 We, herein, present the results.
The novel ¯uorous technique discovered and developed by
Horvath, Curran and their co-workers is one of the most
Á
important advances in modern organic synthesis.1 Under
¯uorous biphase conditions, many catalytic reactions, e.g.
Wilkinson's catalytic hydrogenation,2 Stille transition
metal-catalyzed cross-coupling reaction,3 copper'I)-
mediated living radical polymerization,4 etc. can proceed
with the facile separation of products from the catalyst by
leaving the catalyst in a reusable state. The key point of
2. Results and discussion
First, we examined the solubility of 1a and 1b in various
solvents and found that DMSO, DMF and NMP are good
solvents, DMSO being the best. At room temperature, a
Á
designing ¯uorous catalyst is, as pointed out by Horvath,
`the catalyst has to be catalyst phase like'.1a In other words,
¯uorous biphase catalysis, either heavy ¯uorous or light
¯uorous,5 is based on its unique solubilities 'or tempera-
ture-dependent phase miscibilities) in organic solvents.1,6
saturated solution of 1a in DMSO, 65.9% 'wCF3CH2Cl/wtotal
)
was obtained from 37.5 g 1a in 17.7 g DMSO, while of 1b
19.4% 'wCF3CH2F/wtotal) from 3.0 g 1b in 12.4 g DMSO.
Surprisingly, at atmospheric pressure, the weight loss of
1a and 1b is less than 3±5% after heating the DMSO solu-
tion at 808C for 6 h if their concentration is kept at 0.43 and
0.56N, respectively. At these concentrations, the DMSO
solution of 1a or 1b could be stored in normal glassware
for months without any loss at room temperature. So it is
unnecessary to bubble these gases from the cylinders into
DMSO, a solution of the ¯uorocarbon in DMSO can be
readily prepared simply by adding pre-cooled 1a or 1b
into DMSO.
In connection with the solubility of organo¯uorine
compounds, we very recently found that 1,1,1-tri¯uoroethyl
chloride 'HCFC-133a, CF3CH2Cl, 1a, bpˆ68C), ¯uoride
'HFC-134a, CF3CH2F, 1b, bpˆ2278C) are soluble in
aprotic solvents, such as DMSO, DMF and NMP. The
decision for choosing 1a and 1b as the substrates is that
they are produced in large scale for chloro¯uorocarbon
replacements,7 and considered to be good starting materials
for synthesizing many ¯uorine-containing compounds.8
Furthermore, our previous report demonstrated that 1a
could react with alcohols 'phenols) '2) in the presence of
aqueous KOH giving the corresponding 2,2,2-tri¯uoroethyl
'2-chloro-1,1-di¯uoroethyl) ethers in autoclave at 240±
2808C.9 The results were explained in terms of promotion
by the near-critical water 'SCW) because 1a was shown to
Using this convenient procedure, some reactions of 1a and
1b with oxygen-, nitrogen- and sulfur-nucleophiles were
carried out. The nucleophiles were readily prepared from
the corresponding alcohols, phenols '2), heterocyclic
amines '5) and thiophenols '7) in the presence of KOH.
It was found that 1a and 1b could react with phenols or
alcohols '2) in the presence of KOH in DMSO at 808C for
6 h to give a mixture of ¯uorinated ether '3) and vinyl ether
'E/Z) '4) 'Eq. '1)). The results are listed in Table 1.The pure
products 3 and 4 derived from alcohols could not be isolated
Keywords: HCFC-133a 'CF3CH2Cl); HFC-134a 'CF3CH2F); DMSO; solu-
bility.
Corresponding author. Tel.: 186-21-641-63300; fax: 186-21-641-
66128; e-mail: chenqy@pub.sioc.ac.cn
p
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020'02)00257-0

4078
K. Wu, Q.-Y. Chen / Tetrahedron 58 12002) 4077±4084
ꢀ1†
XˆCl 'a), F 'b); RˆC6H5 'a), o-CH3C6H4 'b), p-CH3C6H4 'c), p-ClC6H4 'd), o-CH3OC6H4 'e),
'f), CH3CH2 'g), 'CH3)2CH 'h), C6H5CH2 'i), 'CH3)3C
'j)
Table 1. Reaction of 1 with phenols and alcohols '2) at 808C for 6 h
Entry
1
2
3 '%)a
4 '%)a
E/Z of 4b
314 '%)
1
2
3
4
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1b
1b
1b
1b
1b
1b
1b
2a
2b
2c
2d
2e
2f
2g
2h
2i
19 '3aa)
31 '3ab)
26 '3ac)
14 '3ad)
31 '3ae)
31 '3af)
76d '3ag)
35d '3ah)
74 '3ai)
0
10 '3ba)
35 '3bb)
23 '3bc)
34 '3bd)
32 '3bf)
64d '3bg)
21d '3bh)
72 '3bi)
0
50 '4aa)
33 '4ab)
42 '4ac)
54 '4ad)
39 '4ae)
36 '4af)
6d '4ag)
38d '4ah)
0
2.7
3.9
5.6
6.4
3.6
4.4
7.4
1.1
±
65
64
68
68
70
67
80
73
74
0
57
65
53
72
72
66
74
72
0
5
6
7c
8c
9c
10c
11
12
13
14
15
16c
17c
18c
19c
2j
0
±
2a
2b
2c
2d
2f
2g
2h
2i
47 '4ba)
30 '4bb)
30 '4bc)
38 '4bd)
40 '4bf)
2d '4bg)
53d '4bh)
0
1.0
1.1
1.2
1.3
2.9
7.9
3.1
±
2j
0
±
1:2:KOHˆ2:1:2.
a
Isolated yield based on 2.
b
c
1
E/Z ratio was determined by H NMR '3JHF
'
).3JHF
'
))12 and 19F NMR.
1:2:KOHˆ1:2:2; 24 h.
because the boiling points of 3 and 4 are very close. Their
Heterocyclic amines '5), such as imidazole '5a), 2-methyl-
imidazole '5b), indole '5c), 3-methylindole '5d), 1H-benzo-
triazole '5e) and carbazole '5f) could also react with 1a to
produce 6 in moderate yields 'Eq. '2)). Treatment of pyrrole
'5g) with 1a afforded only a non-volatile ¯uorine-contain-
ing compound, which was not identi®ed because of its
1
structures might be identi®ed by GC±MS and their H, 19F
NMR spectra 'as well as compared with the spectra of those
known compounds). Benzyl alcohols '2i) was shown to
afford 3 exclusively, while t-butyl alcohol '2j) to be inert
probably due to steric hindrance.
ꢀ2†
Table 2. Reaction 1a with 5 in DMSO
Entry
5
T '8C)
t 'h)
6 '%)a
E/Z of 6b
c
c
1
2
3
4
5
6
5a
5b
5c
5d
5e
5f
90
80
80
85
80
75
8
9
10
7
9
9
66 '6a)
45 '6b)
79 '6c)
76 '6d)
64 '6e)
84 '6f)
9.9
9.4
8.6
.10
1a:5:KOHˆ2:1:2.
a
Isolated yield based on 5.
b
c
1
E/Z ratio was determined by H NMR '3JHF
Only E isomer.
'
).3JHF
'
))12 and 19F NMR.

K. Wu, Q.-Y. Chen / Tetrahedron 58 12002) 4077±4084
4079
ꢀ3†
XˆCl 'a), F 'b); ArˆC6H5 'a), p-CH3C6H4 'b), o-CH3C6H4 'c), p-ClC6H4 'd)
Table 3. Reaction of 1 with thiophenols '7) in DMSO
Entry
1
7
1:7:KOH
T '8C)
t 'h)
8 '%)a
9 '%)a
10 '%)a
1
2
3
4
5
6
7
8
9
10
1a
1a
1a
1a
1a
1a
1a
1b
1b
1b
7a
7a
7a
7a
7b
7c
7d
7a
7b
7d
2:1:3
2:1:3
1:2:1
2:1:2
2:1:2
2:1:2
2:1:2
2:1:2
2:1:2
2:1:2
60
rt
11
11
12.5
22
24
21
22
22
10 '8a)
8 '8a)
10 '8a)
9 '8a)
8 '8b)
7 '8a)
39 '8d)
±
28 '9a)
20 '9a)
37 '9a)
21 '9a)
54 '9b)
32 '10a)
11 '10a)
12 '10a)
54 '10a)
26 '10b)
22 '10c)
56 '10d)
17 '10a)c
81 '10b)
39 '10d)
60
60
60
60
60
60
60
60
43 '9c)
b
±
±
±
24
32
±
±
a
Isolated yield based on 7.
Only trace 9d was produced.
Besides 10, bis'phenylthio)acetylene '11) 39% was also obtained.
b
c
unstability. However, no reaction occurred when 1b was
treated with heterocyclic amines '5) under the similar
reaction conditions 'Eq. '2)). Some other bases, such as
t-BuOK, K2CO3, NaH, DBU and Et3N were unable to
induce the reactions of 1b with heterocyclic amines '5).
The results are listed in Table 2.
eliminate HF from 1 presumably via the E1cB mechanism
to produce di¯uorohaloethene '12)12 'Scheme 1).
Because the 19F NMR signals showed no change before and
after a solution of 1a or 1b with or without KOH at 808C for
8 h if none of nucleophiles was added 'see Section 3.3), so
12 could not be generated from 1 and KOH alone. Since the
electron density of the carbon±carbon double bond of 12 is
reduced strongly by the electron-withdrawing ¯uorine
substituent, the nucleophilic addition reactions may occur
to give the products in which the nucleophiles attack the
di¯uoromethylene end of 12. When phenols and alcohols
'2) are used as the nucleophiles, addition of RO2 to 12
followed by protonation and by loss of ¯uoride ion gives
3 and 4, respectively. But the protonation does not take
place in case of the reactions of 1a with 5, elimination of
¯uoride ion being the dominant process with 6 as the sole
product. However, the mechanism proposed could not
explain the big difference of E/Z ratios of 4 and 6 obtained
in the reaction of 1a and 1b with either alcohols, phenols '2)
'see Table 1) or amines '5) 'see Table 2).
Treating thiophenols '7) with 1a under similar conditions
gave a mixture of ArS-substituted ethylenes 8, 9 and 10
'Eq. '3)). The regioselectivity among the products could
not be improved by changing the reactant ratios and other
conditions such as the reaction temperature and time. Thio-
phenols '7) could also react with 1b, though only to give 10
in low yields. When thiophenol '7a) was the reactant,
bis'phenylthio)acetylene '11) was also obtained besides
10. The results are listed in Table 3.
Examination of the structures of the products 3, 4, 6, 8, 9 and
10 unequivocally reveals that, different from the reaction
results of 1a with 2 in high-temperature aqueous medium9
and CF3CH2I with PhO2,13 alkoxide ion RO2 does not
attack the halogen atom of CF3CH2X '1), but readily
As for the reactions of ArS2 with 1a, 8 is ®rst formed and
further attacked by ArS2 with the elimination of a chloride
ion to produce 9. Compound 10 is generated from 9 in a
similar way. However, 8 and 9, which might be produced
also in the reaction of 1b, would be attacked by ArS2 as
soon as they were produced, so they were not isolated.
When thiophenol '7a) was the reactant, 9ba could also
eliminate HF to yield bis'phenylthio)acetylene '11). The
nucleophiles generated from 5 might be too weak to
deprotonate 1b, so the corresponding addition±elimination
products were not formed.
In conclusion, it is found that HCFC-133a '1a) and HFC-
134a '1b) possess very good solubility in DMSO. In their
DMSO solutions, oxygen-, nitrogen- and sulfur-nucleo-
philic reactions may proceed in normal glassware rather
than in the autoclave. The investigation on solvent effect
of 1 and other HCFCs, HFCs in DMSO or other solvents
is in progress.
Scheme 1.

4080
K. Wu, Q.-Y. Chen / Tetrahedron 58 12002) 4077±4084
3. Experimental
618 cm21; MS m/z '%): 186 'M1, 58), 151 '9), 123 '10), 91
'100), 65 '40).
3.1. General
3.2.5. Compound 3ac.14 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 2.35 's, 3H), 4.21 't,
JHFˆ9.0 Hz, 2H), 7.13 'd, JHHˆ8.4 Hz, 2H), 7.24 'd,
JHHˆ8.4 Hz, 2H); 19F NMR 'CD3COCD3, 56.4 MHz) d:
24.8 't, JHFˆ9.0 Hz, 2F); IR 'KBr) n: 3150, 1590, 1391,
1254, 772, 618 cm21; MS m/z '%): 206 'M1, 72), 157 '13),
108 '100), 91 '18), 77 '17). Anal. calcd for C9H9ClF2O: C,
52.32; H, 4.39; F, 18.39; found: C, 52.39; H, 4.38; F, 18.56.
1
Boiling points were uncorrected. H NMR spectra were
taken on a Brucker AM-300 '300 MHz) NMR spectrometer.
19F NMR spectra were obtained on a Varian EM-360
'56.4 MHz) or a Bruker AM-300 '282 MHz) spectrometer.
Chemical shifts were reported in parts per million relative to
TMS as an internal standard 'dTMSˆ0) for 1H NMR spectra
and CF3COOH as an external standard 'dCF3COOHˆ0) for
19F NMR 'down®eld shift being designated as negative)
spectra. The solvent for NMR measurement was CDCl3 or
CD3COCD3. IR spectra were recorded on a Perkin±Elmer
Jeol 983 spectrometer. MS and HRMS spectra were
recorded on a Hewlett-Packard HP-5989A spectrometer
and a Finnigan MAT-8483 mass spectrometer. GC and
GC±MS data were obtained on a Hewlett-Packard HP-
6890 and a Finnigan MD-800 spectrometer. HPIC data
were obtained on a Dionex 500 spectrometer.
3.2.6. Compound 4ac.14 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 2.28 's, 3H) 'Z/E), 5.64 'd,
JHFˆ19.1 Hz, 1H) 'Z), 6.01 'd, JHFˆ3.8 Hz, 1H) 'E),
7.02±7.04 'm, 2H), 7.21±7.24 'm, 2H); 19F NMR
'CD3COCD3, 56.4 MHz) d: 13.1 'm, 1F) 'Z/E); IR 'KBr)
n: 3108, 3059, 1708, 1599, 1257, 960, 880, 794, 770 cm21
;
MS m/z '%): 186 'M1, 86), 151 '13), 91 '100), 77 '11), 65
'39).
3.2.7. Compound 3ad.14 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 3.90 't, JHFˆ8.4 Hz, 2H), 7.01
'd, JHHˆ7.8 Hz, 2H), 7.18 'd, JHHˆ7.8 Hz, 2H); 19F NMR
'CD3COCD3, 56.4 MHz) d: 22.9 't, JHFˆ8.4 Hz, 2F); IR
'KBr) n: 3100, 1484, 1331, 1197, 827, 618 cm21; MS m/z
'%): 226 'M1, 5), 186 '8), 124 '100), 159 '100), 128 '67),
111 '49). Anal. calcd for C8H6Cl2F2O: C, 42.32, H, 2.66;
found: C, 42.47, H, 2.64.
3.2. General procedure for the reaction of 1 with 2, 5 or 7
CF3CH2Cl '1a, 0.961 g, 8.11 mmol), which was pre-cooled
with dry ice/acetone, was added to 15 ml DMSO, then KOH
'0.454 g, 8.11 mmol) and phenol '2a, 0.382 g, 4.06 mmol)
were added to the solution. After stirring for 8 h at 808C,
water was added to the reaction mixture. The aqueous layer
was extracted three times with ether '3£10 ml). The
combined extracts were washed with brine '3£10 ml) and
dried over Na2SO4. After removal of ether, the residue was
subjected to column chromatography on silica gel
'petroleum ether) to give 3aa '0.154 g, 19%) and 4aa
'0.349 g, 50%) as colorless oil.
3.2.8. Compound 4ad. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 5.35 'd, JHFˆ18.4 Hz, 1H) 'Z),
5.64 's, 1H) 'E), 7.03±7.08 'm, 2H), 7.26±7.35 'm, 2H); 19F
NMR 'CD3COCD3, 56.4 MHz) d: 9.8 'm, 1F) 'Z/E); IR
'KBr) n: 3398, 1119, 748, 618 cm21; MS m/z '%): 206
'M1, 67), 171 '8), 111 '100), 75 '61). Anal. calcd for
C8H5Cl2FO: C, 44.41, H, 2.43, F, 9.18; found: C, 44.51,
H, 2.43, F, 9.38.
3.2.1. Compound 3aa.14 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 4.24 't, JHFˆ8.8 Hz, 2H),
7.20±7.42 'm, 5H); 19F NMR 'CD3COCD3, 282 MHz) d:
22.42 't, JHFˆ8.8 Hz, 2F); IR 'KBr) n: 3074, 1591, 1491,
1331, 1193, 859, 799, 747, 619 cm21; MS m/z '%): 192
'M1, 28), 99 '50), 94 '100), 77 '25), 66 '17), 65 '11).
3.2.9. Compound 3ae. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 3.86 's, 3H), 3.97 't,
JHFˆ9.2 Hz, 2H), 6.90±7.28 'm, 4H); 19F NMR
'CD3COCD3, 56.4 MHz) d: 2.65 't, JHFˆ9.2 Hz, 2F); IR
'KBr) n: 2974, 1602, 1498, 1331, 1061, 862, 752,
618 cm21; MS m/z '%): 222 'M1, 43), 186 '16), 124
'100), 109 '58), 99 '24), 77 '35). Anal. calcd for
C9H9ClF2O: C, 48.56, H, 4.07; found: C, 48.46, H, 4.08.
3.2.2. Compound 4aa.14 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 5.29 'd, JHFˆ18.2 Hz, 1H) 'Z),
5.64 's, 1H) 'E), 7.08±7.41 '5H, m); 19F NMR 'CD3COCD3,
56.4 MHz) d: 12.1 'm, 1F) 'Z/E); IR 'KBr) n: 3110, 1698,
1591, 1295, 865, 749, 688 cm21; MS m/z '%): 172 'M1, 38),
137 '11), 96 '19), 77 '100), 51 '24).
3.2.10. Compound 4ae. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 3.89 's, 3H) 'Z/E), 5.09 'd,
JHFˆ18.7 Hz, 1H) 'Z), 5.51 's, 1H) 'E), 6.91±7.27 'm,
4H); 19F NMR 'CD3COCD3, 56.4 MHz) d: 14.0 'm, 1F)
'Z/E); IR 'KBr) n: 3103, 1710, 1391, 1299, 1122, 960,
793, 618 cm21; MS m/z '%): 202 'M1, 91), 124 '43), 92
'50), 77 '100). Anal. calcd for C9H8ClFO: C, 53.35, H, 3.98;
found: C, 53.11, H, 3.97.
3.2.3. Compound 3ab.14 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 2.31 's, 3H), 4.17 't,
JHFˆ8.8 Hz, 2H), 7.18±7.24 'm, 4H); 19F NMR
'CD3COCD3, 56.4 MHz) d: 23.0 't, JHFˆ8.8 Hz, 2F); IR
'KBr) n: 3100, 1598, 1391, 1328, 772, 618; MS m/z '%):
206 'M1, 17), 157 '9), 108 '100), 91 '21). Anal. calcd for
C9H9ClF2O: C, 52.32; H, 4.39; F, 18.39; found: C, 52.20; H,
4.46; F, 18.49.
3.2.11. Compound 3af.14 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 4.45 't, JHFˆ8.9 Hz, 2H),
7.47±8.26 'm, 7H); 19F NMR 'CD3COCD3, 56.4 MHz) d:
22.5 't, JHFˆ8.9 Hz, 2F); IR 'KBr) n: 3100, 1598, 1391,
1105, 772, 618 cm21; MS m/z '%): 242 'M1, 68), 144 '100),
127 '31), 115 '59).
3.2.4. Compound 4ab.14 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 2.38 's, 3H) 'Z), 2.35 's, 3H)
'E), 5.23 'd, JHFˆ18.5 Hz, 1H) 'Z), 5.61 's, 1H) 'E), 6.99±
7.04 'm, 2H), 7.16±7.26 'm, 2H); 19F NMR 'CD3COCD3,
56.4 MHz) d: 11.9 'm, 1F) 'Z/E); IR 'KBr) n: 3100, 1120,

K. Wu, Q.-Y. Chen / Tetrahedron 58 12002) 4077±4084
4081
3.2.12. Compound 4af.14 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 5.83 'd, JHFˆ19.1 Hz, 1H) 'Z),
6.20 's, 1H) 'E), 7.27±8.26 'm, 7H); 19F NMR 'CD3COCD3,
56.4 MHz) d: 14.2 'm, 1F) 'Z/E); IR 'KBr) n: 3108, 1709,
1596, 1390, 1226, 1051, 960, 880, 793, 618 cm21; MS m/z
'%): 222 'M1, 41), 187 '37), 186 '15), 127 '100). Anal.
calcd for C12H8ClFO: C, 64.74, H, 3.62, F, 8.53; found: C,
64.74, H, 3.74, F, 8.78.
3.2.19. Compound 4bb. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 2.30 's, 3H), 5.94 'dd,
JHFˆ8.7, 44.6 Hz, 1H) 'Z), 6.19 'd, JHFˆ72.2 Hz, 1H) 'E),
7.36±7.22 'm, 4H); 19F NMR 'CD3COCD3, 56.4 MHz) d:
38.2 'm, 1F) 'Z), 52.4 'm, 1F) 'E), 112.1 'm, 1F) 'Z), 108.7
'm, 1F) 'E); IR 'KBr) n: 3100, 1747, 1491, 1247, 1113, 919,
750, 618 cm21; MS m/z '%): 170 'M1, 55), 137 '14), 123
'6), 91 '100), 65 '44). HRMS calcd for C9H8F2O:
170.05432; found: 170.05240.
1
3.2.13. Compounds 3ag15 and 4ag.16 Colorless oil; H
NMR 'CDCl3, 300 MHz) 'mixture of 3ag and 4ag) d:
1.18±1.39 'm, ±CH3), 3.68 't, JHFˆ8.2 Hz, CF2CH2Cl),
4.10±4.17 'm, ±CH2±), 4.73 'CvCH) 'Z), 5.18 'CvCH),
'E); 19F NMR 'CDCl3, 56.4 MHz) 'mixture of 3ag and 4ag)
d: 22.1 't, JHFˆ8.2 Hz, CF2CH2Cl), 15.5 'm, CvCF) 'Z/E);
GC±MS, 144 for 3ag and 124 for 4ag '3ag require 144 and
4ag require 124).
3.2.20. Compound 3bc. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 2.33 's, 3H), 4.90 'dt,
JHFˆ8.8, 47.8 Hz, 2H), 7.13 'd, JHHˆ8.5 Hz, 2H), 7.25 'd,
JHHˆ8.5 Hz, 2H); 19F NMR 'CD3COCD3, 56.4 MHz) d:
16.1 'm, 2F), 157.7 'm, 1F); IR 'KBr) n: 3100, 1491,
1122, 619 cm21; MS m/z '%): 190 'M1, 82), 108 '100),
107 '69), 91 '35), 77 '50), 51 '22). HRMS calcd for
C9H9F3O: 190.06055; found: 190.06017.
1
3.2.14. Compounds 3ah15 and 4ah.16 Colorless oil; H
NMR 'CDCl3, 300 MHz) 'mixture of 3ah and 4ah) d:
1.05±1.35 'm, CH3), 3.64 't, JHFˆ8.6 Hz, CF2CH2Cl),
3.99 'm, 'CH3)2C±H), 4.51 'm, 'CH3)2C±H), 4.86
'CvCH) 'Z), 5.19 'CvCH) 'E); 19F NMR 'CDCl3,
56.4 MHz) 'mixture of 3ah and 4ah) d: 22.7 't,
JHFˆ8.6 Hz, CF2CH2Cl), 16.5 'm, CvCF) 'Z/E); GC-MS,
158 for 3ah and 138 for 4ah '3ah require 158 and 4ah
require 138).
3.2.21. Compound 4bc. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 2.30 's, 3H) 'Z), 2.32 's, 3H)
'E), 6.93 'dd, JHFˆ13.1, 73.0 Hz, 1H) 'Z), 7.09 'dd,
JHFˆ73.0, 3.6 Hz, 1H) 'E), 6.99±7.26 'm, 4H); 19F NMR
'CD3COCD3, 282 MHz) d: 21.63 't, JFFˆJHFˆ13.1 Hz, 1F)
'Z), 47.28 'dd, JHFˆ3.6 Hz, JFFˆ121.9 Hz, 1F) 'E), 105.45
'dd, JHFˆ73.0 Hz, JFFˆ13.1 Hz, 1F) 'Z), 112.14 'dd,
JFFˆ121.9 Hz, JHFˆ73.0 Hz, 1F) 'E); MS m/z '%): 170
'M1, 58), 127 '14), 91 '100), 65 '44). HRMS calcd for
C9H8F2O: 170.05432; found: 170.05356.
3.2.15. Compound 3ai. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 3.89 't, JHFˆ9.0 Hz, 2H), 5.00
's, 2H), 7.24±7.44 'm, 5H); 19F NMR 'CD3COCD3,
56.4 MHz) d: 0.5 't, JHFˆ9.0 Hz, 2F); MS m/z '%):
206 'M1, 36), 205 '16), 110 '11), 91 '100), 79 '24), 65
'14). HRMS calcd for C9H9F2ClO: 206.03100; found:
206.02602.
3.2.22. Compound 3bd. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 4.54 'dt, JHFˆ8.3, 45.8 Hz,
2H), 6.91 'd, JHHˆ8.2 Hz, 2H), 7.21 'd, JHHˆ8.2 Hz, 2H);
19F NMR 'CD3COCD3, 282 MHz) d: 21.82 'dt,
JHFˆ19.2 Hz, JFFˆ8.2 Hz, 2F), 155.43 'tt, JHFˆ45.8 Hz,
JFFˆ19.2 Hz, 1F); MS m/z '%): 210 '67), 190 '26), 128
'100), 111 '65), 75 '35). HRMS calcd for C8H6F3ClO:
210.00593; found: 210.00476.
3.2.16. Compound 3ba.17 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 4.66 'dt, JHFˆ8.5, 45.8 Hz,
2H), 7.21±7.41 'm, 5H); 19F NMR 'CD3COCD3,
282 MHz) d: 3.81 'dt, JHFˆ8.5 Hz, JFFˆ91.0 Hz, 2F),
161.11 'tt, JHFˆ45.8 Hz, JFFˆ91.0 Hz, 1F); IR 'KBr) n:
3100, 1591, 1491, 1296, 1108, 935, 750, 619 cm21; MS
m/z '%): 176 'M1, 68), 94 '100), 77 '38), 65 '17).
3.2.23. Compound 4bd. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 6.99 'dd, JHFˆ13.4, 71.9 Hz,
1H) 'Z), 7.29 'dd, JHFˆ74.1, 121.2 Hz, 1H) 'E), 7.22±
7.25 'm, 2H), 7.46±7.51 'm, 2H); 19F NMR 'CD3COCD3,
282 MHz) d: 22.42 't, JHFˆJFFˆ13.4 Hz, 1F) 'Z), 47.82 'dd,
JHFˆ41.2 Hz, JFFˆ121.2 Hz, 1F) 'E), 104.11 'dd,
JHFˆ71.9 Hz, JFFˆ72.9 Hz, 1F) 'Z), 110.67 'dd,
JHFˆ41.2 Hz, JFFˆ121.2 Hz, 1F) 'E); MS m/z '%): 190
'M1, 62), 155 '15), 143 '29), 111 '100), 75 '82). HRMS
calcd for C8H5F2ClO: 189.99970; found: 190.00069.
3.2.17. Compound 4ba.17 Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 6.61 'dd, JHFˆ72.5, 13.2 Hz,
1H) 'Z), 6.81 'd, JHHˆ73.3 Hz, 1H) 'E), 7.05±7.40 'm,
5H); 19F NMR 'CD3COCD3, 58.4 MHz) d: 24.4 't,
JHFˆJFFˆ13.2 Hz, 1F) 'Z), 50.2 'd, JHFˆ0 Hz, JFFˆ
122.0 Hz, 1F) 'E), 109.2 'dd, JHFˆ72.5 Hz, JFFˆ13.2 Hz,
1F) 'Z), 115.4 'dd, JHFˆ73.3 Hz, JFFˆ122.0 Hz, 1F) 'E); IR
'KBr) n: 3105, 1503, 1334, 1251, 619, 1123 cm21; MS m/z
'%): 156 'M1, 47), 109 '9), 77 '100), 51 '38).
3.2.24. Compound 3bf. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 5.07 'dt, JHFˆ8.8, 45.7 Hz,
2H), 7.48±8.18 'm, 7H); 19F NMR 'CD3COCD3,
282 MHz) d: 1.31 'dt, JHFˆ8.8 Hz, JFFˆ17.3 Hz, 2F),
154.44 'tt, JHFˆ45.7 Hz, JFFˆ17.3 Hz, 1F); MS m/z '%):
226 'M1, 97), 144 '79), 127 '16), 115 '100), 89 '12), 63
'15). HRMS calcd for C12H9F3O: 226.06055; found:
226.05822.
3.2.18. Compound 3bb. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 2.06 's, 3H), 4.92 'dt, JHFˆ
8.7, 45.8 Hz, 2H), 7.02±7.33 'm, 4H); 19F NMR
'CD3COCD3, 282 MHz) d: 21.72 'dt, JHFˆ8.7 Hz, JFFˆ
9.5 Hz, 2F), 166.13 'tt, JHFˆ45.8 Hz, JFFˆ9.5 Hz, 1F); IR
'KBr) n: 3197, 1666, 1491, 1291, 1164, 975, 750,
618 cm21; MS m/z '%): 190 'M1, 69), 108 '100), 91 '29),
77 '34). HRMS calcd for C9H9F3O: 190.06055; found:
190.05991.
3.2.25. Compound 4bf. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 5.84 'dd, JHFˆ12.7, 71.2 Hz,
1H) 'Z), 6.02 'd, JHFˆ71.2 Hz, 1H) 'E), 7.28±8.23 'm,
7H); 19F NMR 'CD3COCD3, 56.4 MHz) d: 23.4 'm, 1F)

4082
K. Wu, Q.-Y. Chen / Tetrahedron 58 12002) 4077±4084
'Z), 46.8 'm, 1F) 'E), 106.1 'm, 1F) 'Z), 113.7 'm, 1F) 'E);
MS m/z '%): 206 'M1, 54), 186 '16), 159 '13), 127 '100), 77
'13). HRMS calcd for C12H8F2O: 206.05432; found:
206.05100.
N, 6.71, F, 9.11; found: C, 63.37, H, 4.08, N, 6.90, F,
9.19.
3.2.33. Compound 6e. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 6.88 'd, JHFˆ19.6 Hz, 1H) 'Z),
7.20 's, 1H) 'E), 7.59±8.23 'm, 4H); 19F NMR 'CD3COCD3,
58.4 MHz) d: 16.1 'm, 1F) 'Z/E); MS m/z '%): 197 'M1,
28), 171 '33), 169 '100), 136 '38), 107 '83). HRMS calcd
for C8H5N3FCl: 197.01560; found: 197.01433.
1
3.2.26. Compounds 3bg18 and 4bg.19 Colorless oil; H
NMR 'CDCl3, 300 MHz) 'mixture of 3bg and 4bg) d:
1.18±1.26 'm, CH3), 2.12±2.35 'm, MeCH2), 4.43 'dt,
JHFˆ46.2, 8.5 Hz, CF2CH2F), 4.91 'm, CvCH) 'Z), 4.96
'm, CvCH) 'E); 19F NMR 'CDCl3, 56.4 MHz) 'mixture
of 3bg and 4bg) d: 5.2 'm, ±CF2), 27.1 'm, CvF) 'Z),
51.2 'm, CvCF) 'E), 117.4 'm, CvCF) 'Z), 121 'm,
CvCF) 'E), 158.0 'm, CH2F); GC-MS, 128 for 3bg and
108 for 4bg '3bg require 128 and 4bg require 108).
3.2.34. Compound 6f. Mpˆ79±808C; 1H NMR
'CD3COCD3, 300 MHz) d: 7.03 's, 1H) 'E), 7.36±7.61
'm, 8H); 19F NMR 'CD3COCD3, 58.4 MHz) d: 13.4 's,
1F) 'E); MS m/z '%): 245 'M1, 100), 210 '81), 209 '52),
190 '12). HRMS calcd for C14H9NFCl: 245.04076; found:
245.03621.
1
3.2.27. Compounds 3bh18 and 4bh.19 Colorless oil; H
NMR 'CDCl3, 300 MHz) 'mixture of 3bh and 4bh) d:
1.17±1.34 'm, CH3), 4.01 'm, 'CH3)2C±H), 4.39 'dt,
JHFˆ45.0, 9.0 Hz, CF2CH2F), 4.61 'm, 'CH3)2C±H), 6.51
'm, CvCH) 'Z), 6.69 'm, CvCH) 'E); 19F NMR 'CDCl3,
56.4 MHz) 'mixture of 3bh and 4bh) d: 5.7 'm, CF2), 27.9
'm, CvF) 'Z), 54.2 'm, CvCF) 'E), 119.8 'm, CvCF) 'Z),
122.3 'm, CvCF) 'E), 156.5 'm, CH2F); GC-MS, 142 for
3bh and 122 for 4bh '3bh require 142 and 4bh require 122).
1
3.2.35. Compound 8a.20 Colorless oil; H NMR 'CDCl3,
300 MHz) d: 5.32 'd, JHFˆ22.7 Hz, 1H) 'Z), 5.95 'd,
JHFˆ8.9 Hz, 1H) 'E), 7.21±7.48 'm, 5H); 19F NMR
'CDCl3, 282 MHz) d: 12.77 'd, JHFˆ22.7 Hz, 1H) 'Z),
22.09 'd, JHFˆ8.9 Hz, 1H) 'E); MS m/z '%): 188 'M1,
86), 153 '100), 109 '86), 77 '35), 51 '36).
1
3.2.36. Compound 9a. Colorless oil; H NMR 'CDCl3,
3.2.28. Compound 3bi. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 5.21 'dt, JHFˆ8.8, 45.8 Hz,
2H), 5.56 's, 2H), 7.83±7.95 'm, 5H); 19F NMR
'CD3COCD3, 282 MHz) d: 22.08 'dt, JHFˆ8.8 Hz,
JFFˆ15.3 Hz, 2F), 155.12 'tt, JHFˆ45.8 Hz, JFFˆ15.3 Hz,
1F); MS m/z '%): 190 'M1, 59), 107 '17), 91 '100), 79
'44), 77 '27), 65 '21). HRMS calcd for C9H9F3O:
190.06055; found: 190.06040.
300 MHz) d: 6.34 'd, JHFˆ28.2 Hz, 1H) 'E), 6.48 'd,
JHFˆ9.9 Hz, 1H) 'Z), 7.29±7.53 'm, 10H); 19F NMR
'CDCl3, 282 MHz) d: 4.11 'd, JHFˆ28.2 Hz, 1F) 'E), 8.91
'd, JHFˆ9.9 Hz, 1F) 'Z); MS m/z '%): 262 'M1, 98), 153
'100), 152 '91), 109 '86), 77 '19). HRMS calcd for
C14H11FS2 262.02862; found: 262.02754.
3.2.37. Compound 10a.21 Mpˆ53±548C; 1H NMR 'CDCl3,
300 MHz) d: 5.74 's, 1H), 7.18±7.44 'm, 15H); MS m/z
'%): 352 'M1, 70), 243 '14), 165 '57), 134 '100), 109
'39), 77 '22); IR 'KBr) n: 3102, 1576, 1475, 1021, 902,
800, 744, 735, 688.
1
3.2.29. Compound 6a. Colorless oil; H NMR 'CDCl3,
300 MHz) d: 6.06 'd, JHFˆ3.7 Hz, 1H), 7.18 'd,
JHHˆ3.1 Hz, 1H), 7.93 'd, JHHˆ3.1 Hz, 1H), 7.94 's, 1H);
19F NMR 'CDCCl3, 56.4 MHz) d: 20.0 'd, JHFˆ3.7 Hz, 1F);
MS m/z '%): 146 'M1, 95), 111 '100), 84 '26), 79 '21), 57
'22). HRMS calcd for C5H4N2FCl: 146.00470; found:
146.00711.
1
3.2.38. Compound 8b.20 Colorless oil; H NMR 'CDCl3,
300 MHz) d: 2.31±2.32 'm, 3H) 'Z/E), 5.40 'd,
JHFˆ23.1 Hz, 1H) 'E), 5.95 'd, JHFˆ11.3 Hz, 1H) 'Z),
7.18±7.37 'm, 6H); 19F NMR 'CDCl3, 282 MHz) d: 13.67
'd, JHFˆ11.3 Hz, 1H) 'Z), 26.78 'd, JHFˆ23.1 Hz, 1H) 'E);
MS m/z '%): 202 'M1, 71), 167 '78), 152 '33), 133 '21), 91
'28).
3.2.30. Compound 6b. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 2.39 's, 3H), 6.83 'd,
JHHˆ1.5 Hz, 1H), 6.98 's, 1H), 7.29 'd, JHHˆ1.5 Hz, 1H);
19F NMR 'CD3COCD3, 58.4 MHz) d: 10.8 's, 1F); MS m/z
'%): 160 'M1, 99), 125 '100), 84 '22), 79 '23), 74 '18), 42
'23). HRMS calcd for C6H6N2FCl: 160.02035; found:
160.01744.
1
3.2.39. Compound 9b.20b Colorless oil; H NMR 'CDCl3,
300 MHz) d: 2.33±2.34 'm, 6H) 'Z/E), 6.21 'd,
JHFˆ26.8 Hz, 1H) 'E), 6.28 'd, JHFˆ11.9 Hz, 1H) 'Z),
7.11±7.39 'm, 8H); 19F NMR 'CDCl3, 282 MHz) d: 3.81
'd, JHFˆ11.9 Hz, 1F) 'Z), 7.45 'd, JHFˆ26.8 Hz, 1F) 'E);
MS m/z '%): 290 'M1, 31), 167 '100), 152 '75), 123 '61),
91 '32), 77 '23). Anal. calcd for C16H15FS2: C, 66.17, H,
5.21; found: C, 66.27, H, 5.31.
3.2.31. Compound 6c. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 6.31 'd, JHFˆ19.8 Hz, 1H) 'Z),
6.70 's, 1H) 'E), 7.22±7.66 'm, 6H); 19F NMR 'CD3COCD3,
58.4 MHz) d: 11.6 'm, 1F) 'Z/E); MS m/z '%): 195 'M1,
100), 160 '89), 133 '69), 117 '40), 77 '28). HRMS calcd for
C10H7NFCl: 195.02511; found: 195.02626.
3.2.40. Compound 10b.21 Mpˆ58±598C; 1H NMR 'CDCl3,
300 MHz) d: 2.39±2.41 'm, 9H), 6.38 '3, 1H), 7.11±7.40
'm, 12H); MS m/z '%): 394 'M1, 77), 271 '18), 148 '100),
147 '90), 123 '55), 91 '35).
3.2.32. Compound 6d. Colorless oil; 1H NMR
'CD3COCD3, 300 MHz) d: 2.30±2.31 's, 3H) 'Z/E), 6.15
'd, JHFˆ21.0 Hz, 1H) 'Z), 6.59 's, 1H) 'E), 7.18±7.61 'm,
5H); 19F NMR 'CD3COCD3, 58.4 MHz) d: 17.3 'm, 1F)
'Z/E); MS m/z '%): 209 'M1, 100), 174 '11), 154 '10),
128 '43). Anal. calcd for C11H9NFCl: C, 63.32, H, 3.86,
1
3.2.41. Compound 8c. Colorless oil; H NMR 'CDCl3,
300 MHz) d: 2.14±2.16 'm, 3H) 'Z/E), 5.94 'd,
JHFˆ22.8 Hz, 1H) 'E), 6.15 'd, JHFˆ9.3 Hz, 1H) 'Z),

K. Wu, Q.-Y. Chen / Tetrahedron 58 12002) 4077±4084
4083
Table 4. 19F NMR signals of 1 in DMSO in the absence or in the presence of KOH before and after heating at 808C for 8 h
At 258C 'ppm)
Absence of KOH
After heating 'ppm)
Absence of KOH
KOH
KOH
1a
1b
27.37
22.09 'CF3)
161.85 'CH2F)
27.95
22.09 'CF3)
161.92 'CH2F)
27.37
22.09 'CF3)
161.86 'CH2F)
27.96
2.27 'CF3)
161.68 'CH2F)
7.18±7.38 'm, 4H); 19F NMR 'CDCl3, 282 MHz) d: 13.56
'd, JHFˆ9.3 Hz, 1F) 'Z), 17.98 'd, JHFˆ22.8 Hz, 1F) 'E);
MS m/z '%): 202 'M1, 50), 167 '81), 152 '39), 133 '11),
91 '28). HRMS calcd for C9H8ClFS: 202.00193; found:
202.02361.
'40.11 ppm) and HPIC. Therefore, the following reaction
seems to occur.
1
3.2.42. Compound 9c. Colorless oil; H NMR 'CDCl3,
300 MHz) d: 2.35±2.41 'm, 6H) 'Z/E), 6.21 'd,
JHFˆ29.1 Hz, 1H) 'E), 6.35 'd, JHFˆ10.2 Hz, 1H) 'Z),
7.13±7.40 'm, 8H); 19F NMR 'CDCl3, 282 MHz) d: 3.66
'd, JHFˆ10.2 Hz, 1F) 'Z), 7.58 'd, JHFˆ29.1 Hz, 1F) 'E);
MS m/z '%): 290 'M1, 100), 167 '83), 152 '41), 123 '29),
91 '22). Anal. calcd for C16H15FS2: C, 66.17, H, 5.21; found:
C, 66.11, H, 5.23.
Acknowledgements
We thank the Chinese National Natural Science Foundation
for their ®nancial support.
3.2.43. Compound 10c.21 Mpˆ62±638C; 1H NMR 'CDCl3,
300 MHz) d: 2.29±2.30 'm, 9H), 6.45 's, 1H), 7.16±7.77
'm, 12H); MS m/z '%): 394 'M1, 65), 271 '12), 239 '10),
179 '81), 148 '100), 123 '49).
References
1
3.2.44. Compound 8d. Colorless oil; H NMR 'CDCl3,
Á
1. 'a) Horvath, I. T. Acc. Chem. Res. 1998, 31, 641±650.
300 MHz) d: 6.15 'd, JHFˆ18.6 Hz, 1H) 'E), 6.41 'd,
JHFˆ6.0 Hz, 1H) 'Z), 7.25±7.41 'm, 4H); 19F NMR
'CDCl3, 282 MHz) d: 13.91 'd, JHFˆ18.6 Hz, 1H) 'E),
19.09 'd, JHFˆ6.0 Hz, 1H) 'Z); MS m/z '%): 222 'M1,
50), 187 '40), 159 '15), 143 '15), 108 '20), 75 '18).
HRMS calcd for C8H5ClFS2: 221.94731; found: 222.02156.
'b) Dewolf, E.; Vankoten, G.; Deelman, B. J. Chem. Soc.
Rev. 1999, 28, 37±41.
2. Richter, B.; Spek, A. L.; Koten, G. V.; Deelman, B. J. J. Am.
Chem. Soc. 2000, 122, 3945±3951.
3. 'a) Schneider, S.; Bannwarth, W. Angew. Chem., Int. Ed. Engl.
2000, 39, 4142±4145. 'b) Curran, D. P.; Hoshino, M. J. Org.
Chem. 1996, 61, 6480±6481.
1
3.2.45. Compound 10d. Bpˆ83±858C; H NMR 'CDCl3,
4. Haddletan, D.; Jackson, S. G.; Bon, S. A. F. J. Am. Chem. Soc.
2000, 122, 1542±1543.
300 MHz) d: 6.58 'm, 1H), 7.10±7.36 'm, 12H); MS m/z
'%): 456 'M1, 24), 313 '4), 267 '12), 235 '26), 199 '57),
168 '100), 143 '45); IR 'KBr) n: 3011, 475, 1388, 1089,
1011, 817, 799, 741. Anal. calcd for C20H13Cl3S2: C, 52.70,
H, 2.87, S, 21.10; found: C, 52.82, H, 2.92, S, 20.69.
5. Curran, D. P.; Luo, Z. J. Am. Chem. Soc. 1999, 121, 9049±
9072.
6. 'a) Rocaboy, C.; Rutherford, D.; Bennett, B. L.; Gladysz, J. A.
J. Phys. Org. Chem. 2000, 13, 596±603. 'b) Wende, M.;
Meier, R.; Gladysz, J. A. J. Am. Chem. Soc. 2001, 123,
11490±11491.
1
3.2.46. Compound 11.22 Mpˆ40±418C; H NMR 'CDCl3,
300 MHz) d: 7.30±7.55 'm, 10H); MS m/z '%): 242 'M1,
100), 165 '31), 133 '6), 109 '5), 77 '35).
7. Powell, R. L. Refrigerants, Propellants and Foaming-blowing
Agents. In Chemistry of Organic Fluorine Compounds II;
Hudlicky, M., Pavlath, A. E., Eds.; ACS Monograph 187;
American Chemical Society, Washington, DC, 1995;
pp 1087±1098.
3.3. An attempt to obtain 12 from 1
A solution of CF3CH2X '1a, 1.113 g, 0.00939 mol; 1b,
1.048 g, 0.0103 mol) in 12 ml DMSO was obtained as
described as above. Their 19F NMR spectra were measured
at 258C or after heating at 808C for 8 h. After adding KOH
'0.789 g, 0.0141 mol) to the solution of 1a, and KOH
'0.863 g, 0.0154 mol) to the solution of 1b, the correspond-
ing 19F NMR spectra were also measured 'see Table 4).
8. 'a) Drakesmith, F. G.; Richardson, R. D.; Stewart, O. J.;
Tarrant, P. J. Org. Chem. 1968, 33, 286±291. 'b) Burdon,
J.; Coe, P. L.; Haslock, I. B.; Powell, R. L. J. Chem. Soc.,
Chem. Comm. 1996, 49±50. 'c) Burdon, J.; Coe, P. L.;
Haslock, I. B.; Powell, R. L. J. Fluorine Chem. 1997, 85,
151±153. 'd) Coe, P. L. J. Fluorine Chem. 1999, 100, 45±52.
9. Wu, K.; Chen, Q. Y. J. Fluorine Chem. 2002, 113, 79±83.
10. Fuchigami, T.; Yamamoto, K.; Nakagaw, Y. J. Org. Chem.
1991, 56, 137±142 and references cited therein.
11. A preliminary note see: Wu, K.; Chen, Q. Y. Chin. J. Chem.
2001, 19, 1273±1279.
All the data showed that 12 could not be obtained from 1. At
the same time, a part of 1a could be recovered from the
mixture of 1a/KOH/DMSO by distillation. The 19F NMR
signal of 1a was disappeared after treating 1a/KOH/DMSO
with H2O, and the ¯uoride ion was observed by 19F NMR
12. Nakai, T.; Tanaka, K.; Ishikawa, N. J. Fluorine Chem. 1977,
9, 89±93.

4084
K. Wu, Q.-Y. Chen / Tetrahedron 58 12002) 4077±4084
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