Synthesis of partially fluorinated organic compounds from perfluoro-2-methyl-2-pentene and phenol derivatives

Article abstract of DOI:10.1007/s11176-005-0238-6

The reactions of perfluoro-2-methyl-2-pentene with substituted phenols and some heterocyclic compounds containing OH group result in the substitution of the fluorine atom either exclusively at the internal multiple bond or at the terminal multiple bond of

Full text of DOI:10.1007/s11176-005-0238-6

Russian Journal of General Chemistry, Vol. 75, No. 3, 2005, pp. 394 401. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005,
pp. 430 437.
Original Russian Text Copyright
2005 by Furin, Zhuzhgov, Chi, Kim.
Synthesis of Partially Fluorinated Organic Compounds
from Perfluoro-2-methyl-2-pentene and Phenol Derivatives
G. G. Furin,* E. L. Zhuzhgov,** K.-V. Chi,*** and N.-A. Kim***
*Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division,
Russian Academy of Sciences, Novosibirsk, Russia
**Novosibirsk State University, Novosibirsk, Russia
***Ulsan University, Ulsan, Republic of Korea
Received June 7, 2003
Abstract The reactions of perfluoro-2-methyl-2-pentene with substituted phenols and some heterocyclic
compounds containing OH group result in the substitution of the fluorine atom either exclusively at the
internal multiple bond or at the terminal multiple bond of perfluoro-2-methyl-1-pentene formed by isomeriza-
tion of the starting perfluoroolefin in the course of the reaction. The reaction pathway depends on the reaction
conditions, base used, and substituents in the benzene ring. The structures of the compounds were confirmed
by 1H, 13C, and 19F NMR and IR spectroscopy.
Introduction of fluorine atoms imparts to organic
molecules new specific properties, which are widely
used in the development of modern materials [1, 2].
Perfluorinated dialkyl ethers are resistant to heat and
oxidants and have low freezing points. The viscosity
characteristics, lubricating properties, and electrophys-
ical parameters of these compounds make them valu-
able [1]. Fluorinated intermediates found wide use in
the synthesis of drugs and bioactive substances for
agriculture [3, 4].
in the synthesis of perfluorinated alkyl cyclohexyl
ethers by direct fluorination. The latter products, in
turn, show promise as high-temperature heat carriers,
dielectrics, and lubricants.
It is known that internal perfluoroolefins, when
treated with N-nucleophilic agents in the presence of
bases or without them, isomerize into terminal per-
fluoroolefins. Perfluoro-2-methyl-2-pentene I can iso-
merize into perfluoro-2-methyl-1-pentene II whose
terminal double bond contains a labile fluorine atom.
As a result, the reaction pathway can change, with
the formation of products of different structure.
A prominent place among herbicides is occupied
by fluorinated diphenyl ethers and compounds con-
taining phenoxy group. One of synthetic routes to
these compounds is based on nucleophilic substitution
of fluorine atoms in internal perfluoroolefins with
O-nucleophiles. The majority of aromatic compounds
containing OH group are effective O-nucleophiles
under the conditions of base catalysis. The reactions
of the hexafluoropropene dimer and trimer with phen-
ol in the presence of triethylamine [5, 6] (or with
sodium phenolate [7], or with p-cresol [8]), of the
hexafluoropropene dimer with N-(4-hydroxyphenyl)-
acetamide [9], of the hexafluoropropene trimer with
3-hydroxybenzodioxane [10], and of the tetrafluoro-
ethene pentamer with methyl 4-hydroxybenzoate [11]
yield products of fluorine substitution at the internal
double bond.
It was shown previously that the reaction of phenol
with I in the presence of KOH in THF yields (3,3,3-
trifluoro-1-pentafluoroethyl-2-trifluoromethylpropen-
yloxybenzene III, the product of formal substitution
of fluorine at the double bond (Scheme 1).
With phenols containing electron-donor substitu-
ents (2-fluorophenol, 3-methoxyphenol, 3,5-dimeth-
oxyphenol), compound I reacts similarly to give IV
VI, respectively. Some heterocyclic compounds con-
taining the OH group at the heteroring also react
similarly. The reactions of I with 2-hydroxybenzimid-
azole and 2-hydroxybenzothiazole under the same
conditions yield fluorine replacement products VII
and VIII, respectively. At the same time, the reactions
of I with 2,6-dichlorophenol and pentafluorophenol
under the same conditions yield (1,1,3,4,4,5,5,5-octa-
fluoro-2-trifluoromethylpent-2-enyloxy)-2,6-dichloro-
benzene IX and (1,1,3,3,4,4,5,5,5-nonafluoro-2-trifluo-
Our goal was to develop simple routes to partially
fluorinated alkenyl aryl ethers derived from available
perfluoro-2-methyl-2-pentene I and various phenol
derivatives. These ethers can be used as intermediates
1070-3632/05/7503-0394 2005 Pleiades Publishing, Inc.

SYNTHESIS OF PARTIALLY FLUORINATED ORGANIC COMPOUNDS
395
Scheme 1.
1
4
5
CF2CF3
CF3
KOH
THF
2 3
(CF3)2C=CFC2F5 + ArOH
6
CF3
OAr
III VIII, XI, XII
~
~
~
7
7
7
8 F
12
11
12
11
N
S
8
9
Ar = Ph (III),
(IV),
>
<
(V),
(VI),
(VIII),
9
11
OCH3
9
13
CH3O
OCH3
10
10
11
8 CH3
10
8 O1C1H3
~
~
7
7
CH3
CH3
(XI),
(XII).
9
9
romethylpentyloxy)pentafluorobenzene X, respective-
ly (Scheme 2). This can be accounted for by the re-
placement of the fluorine atom in terminal olefin II
formed by isomerization of I effected by a base.
Scheme 2.
OH
6
4
5
CF2CF3
CF3
Cl
Cl
2
3
1
F
F
F
O
7
Cl
Cl
8
9
CF3
F
F
KOH
THF
I
10
IX
CF2CF2CF3
6
CF32
II
3
4
5
H
CF2CF2CF3
F
C6F5OH
1
F
8
9
O
F
7
F
10
F
F
F
X
Such a behavior of these phenols may be due to
2,6-disubstitution of the benzene ring with the chlo-
rine and fluorine atoms and to the low reactivity of
the corresponding phenolate ions. However, the reac-
tion of I with 2,6-dimethylphenol and 2,6-dimethoxy-
phenol yields compounds XI and XII, despite consid-
erable steric shielding of the reaction center. At the
same time, our results cannot be attributed solely to
the electron-donor properties of the substituents, since
the reactions of I with 3-nitrophenol, 4-nitrophenol,
and 3-hydroxypyridine yield mixtures of fluorine re-
placement products XIII + XVI, XIV + XVII, and
XV + XVIII, respectively (Scheme 3).
Formation of XVI XVIII is apparently associated
with different rates of nucleophilic substitution of the
fluorine atom at the multiple bond in I with the phen-
oxide anion and of isomerization of I into II.
In compounds containing two nucleophilic centers,
each of them can attack the carbon atom of the multi-
ple bond, either with formation of the substitution
products or with the subsequent intramolecular cycli-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 3 2005

396
FURIN et al.
Scheme 3.
4
5
6
4
5
1
CF2CF3
CF2CF3
CF3
CF3
KOH
THF
2
3
2
3
I + ArOH
+
6
1
F
OAr
CF3
F
OAr
F
XIII XV
XVI XVIII
~
~
11
10
7
7
~
12
8
8
9
7
(XIV, XVII),
(XV, XVIII).
(XIII, XVI),
Ar = 11
9
10
NO2
9
8
NO2
N
10
zation of the heterocyclic system (Scheme 4). The
reaction of I with 2-hydroxypyridine, as expected,
yields a mixture of 2-(3,3,3-trifluoro-1-pentafluoro-
ethyl-2-trifluoromethylpropenyloxy)pyridine XIX and
1-(3,3,3-trifluoro-1-pentafluoroethyl-2-trifluorometh-
ylpropenyl)-1H-pyridin-2-one XX. This may be due
to the attack of the double bond of I with O- and
N-nucleophilic centers. The reaction of I with
2,3-dihydroxypyridine in the presence of KOH in
THF yields 2-pentafluoroethyl-2-(2,2,2-trifluoro-1-tri-
fluoromethylethyl)[1,3]dioxolo[4,5-b]pyridine
XXI.
Scheme 4.
OH
OH
O
CF2CF3
N
CH(CF3)2
O
N
KOH
THF
XXI
C2F5
I
CF3
CF3
CF3
CF3
C2F5
OH
N
+
O
N
O
N
XIX
XX
The reaction of I with phenol starts with the attack
of the O-nucleophilic center of the reagent at the
carbon atom of the double bond to give intermediate
carbanion A (Scheme 5) stabilized with two CF3
groups. Further transformations of carbanion A can
involve elimination of the fluoride ion from either CF
or CF3 group. The former pahtway is thermodynami-
cally preferable; it yields perfluoroalkenes III VIII
containing the phenoxy substituent at the double
bond. The preferential formation of perfluoroolefin II
in the reaction of I with sodium phenolate should be
accounted for by the kinetic control of the reaction.
However, we also should not rule out another reaction
pathway, involving transformation of carbanion A into
compound XXII [5] whose reaction with the phenolate
anion yields intermediate carbanion B. In this species,
stabilization of the negative charge with the phenoxy
group OAr is less efficient, and carbanion B is stabi-
lized either by elimination of the fluoride anion from
the CF group with the formation of XXIII and XXIV,
or by elimination of the phenoxide anion with the
formation of XVI XVIII. This pathway is realized
exclusively at ArO = OC6H3Cl2-2,6; the reactions
with other phenols, in particular, with those contain-
ing the NO2 group at the benzene ring, and with hy-
droxypyridine yields compounds IX and XVI XVIII.
The reaction of I with pyridazine-3,6-diol is more
complex. In the presence of KOH in THF, 1,2-bis-
(3,3,3-trifluoro-1-pentafluoroethyl-2-trifluoromethyl-
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SYNTHESIS OF PARTIALLY FLUORINATED ORGANIC COMPOUNDS
397
Scheme 5.
C2F5
CF3
CF3
F
F
OAr
C2F5
CF3
CF3
III VIII, XI, XII
I + ArO
F
OAr
C2F5
F
C2F5
CF3
CF3
CF3
F
ArO
A
F
OAr
ArO
F
F
F
F
C2F5
OAr
XXII
F
F
OAr
OAr
B
IX, XVI XVIII
F
CF2CF3
OAr
CF3
F
OAr
F
XXIII, XXIV
Ar = 2,6-C2C6H3 (IX), 3-NO2C6H4 (XII), 4-NO2C6H4 (XVII), 3-pyridyl (XVIII), C6H5 (XXIII), 2-FC6H5 (XXIV).
propenyl)-1,2-dihydropyridazine-3,6-dione
formed intead of the expected ether (Scheme 6).
XXVis
EXPERIMENTAL
The IR spectra (5% solutions in CCl4) were taken
on a Bruker IFS-66 IR Fourier spectrometer. The 19F
NMR spectra were recorded on a Bruker WP-200SY
spectrometer (188.324 MHz), and the 13C NMR spec-
tra, on a Bruker 400 spectrometer (100.614 MHz)
(internal references C6F6, TMS); the constants JCH
were not determined. The mass spectra (electron
impact, 70 eV) were recorded on a Finnigan-8200
device and on a chromatograph with a mass-selective
detector (Hewlett Packard G-1800A, GCD system).
In the latter case, we used a 30000 0.25 mm column
with HP-5 stationary phase (5% diphenyl- and 95%
dimethylsiloxane units, coating thickness 0.25 m);
Scheme 6.
CF3
OH
CF3
C2F5
C2F5
O
N
N
HO
N
I
N
CF3
CF3
KOH, THF
O
XXV
The structures of the compounds prepared were
confirmed by the mass (Table 1), H, 13C, and 19F
NMR, and IR spectra (Table 2). The IR spectra of
these compounds contain a C=C vibration band at
1647 cm . The H NMR spectra contain signals of
aromatic ring protons with the characteristic chemical
shifts. The 19F NMR spectra contain signals with the
characteristic chemical shifts and coupling constants:
J(F1F6) up to 10.7, J(F4F6) up to 23.2, and J(F5F6) up
to 4.0 Hz.
1
1
the carrier gas was He (1 ml min ), and the vaporizer
temperature, 280 C. The column temperature program
was as follows: 50 C, 2 min; heating to 280 C,
1
1
1
10 deg min ; and 280 C, 5 min. All the reactions
were monitored by 19F NMR. The reaction mixtures
were analyzed with an LKhM-72 chromatograph (15%
SE, SKTF-803 : QF-1, Chromosorb-W, 4000 4-mm
column).
J(F5F6)
The characteristics of the compounds synthesized
are given in Table 1.
J(F4F6)
Reactions of perfluoro-2-methyl-2-pentene I
with substituted phenols. a. A 10.7-g portion of I
was added dropwise with vigorous stirring at 0 C to a
suspension of 2 g of KOH in 20 ml of anhydrous
THF. Then 4 g of 2-fluorophenol was added dropwise
with stirring over a period of 15 min. The mixture
was stirred for 1 h at 0 C, 1 h at room temperature,
6
CF2CF3
3
4
CF3
>
2
5
J(F1F6)
1
OAr
CF3
The 13C and 19F NMR spectra of XVI XVIII con-
tain signals of the F and C atoms of the C=CF group.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 3 2005

398
FURIN et al.
Table 1. Yields, boiling points, and mass-spectrometric data for partially fluorinated aryl alkenyl ethers
.
bp,
(p, mm Hg)
C
Found
M
Calculated
Mass spectrum, m/z (Irel, %)
Formula
M
III
IV
70 69 71 (19) 374 [M]+ (24.64), 355 [M F]+ (2.98), 305 [M CF3]+ 374.0162 C12H5F11O
(24.38), 285 [M CF3 HF]+ (3.19), 255 [M C2F5]+
374.0165
392.0074
(0.80), 236 [M C2F5 F]+ (1.10), 186 [M CF3
C2F5]+ (10.69), 119 [C2F5]+ (2.30), 93 [C6H5O]+ (2.19),
77 [C6H5]+ (100), 69 [CF3]+ (7.06), 51 [CHF2]+ (16.42)
75 36 37 (3) 392 [M]+ (75.76), 373 [M F]+ (7.74), 353 [M
F
392.0054 C12H4F12O
HF]+ (27.14), 323 [M CF3]+ (40.56), 303 [M CF3
HF]+ (10.97), 281 [M C6H4FO]+ (0.78), 273 [M
C2F5]+ (2.07), 119 [C2F5]+ (26.77), 111 [C6H4FO]+
(31.07), 100 [CF2=CF2]+ (0.88), 95 [C6H4F]+ (100), 75
[C6H4F
HF]+ (40.14), 69 [CF3]+ (33.31)
V
71 61 62 (2) 404 [M]+ (75.36), 385 [M F]+ (16.63), 335 [M CF3]+ 404.0273 C13H7F11O2 404.0270
(95.65), 266 [M 2CF3]+ (4.76), 124 [C6H8O2]+ (2.72),
119 [C2F5]+ (2.40), 107 [C6H7O2]+ (34.26), 92 [C6H4O]+
(36.90), 69 [CF3]+ (8.72)
VI
IX
X
68 82 83 (2.5) 434 [M]+ (50.34), 415 [M F]+ (17.41), 365 [M CF3]+ 434.0371 C14H9F11O3 434.0376
(100), 315 [M C2F5]+ (0.54), 246 [M CF3 C2F5]+
(46.74), 138 [C8H9O2]+ (0.76), 119 [C2F5]+ (1.40), 107
[C7H7O]+ (8.52), 69 [CF3]+ (12.10)
75 82 84 (1) 442 [M]+ (54.87), 423 [M F]+ (12.06), 323 [M C2F5]+ 441.9402 C12H3F11Cl2O 441.9385
(78.46), 281 [M C6H3Cl2]+ (0.94), 161 [C6H3Cl2O]+
(7.67), 145 [C6H3Cl2]+ (100), 119 [C2F5]+ (4.73), 109
[C3H3Cl2]+ (35.97), 69 [CF3]+ (15.06)
40
50 51 (3) 484 [M]+ (26.15), 465 [M F]+ (22.22), 445 [M HF
F]+ (19.99), 365 [M C2F5]+ (3.45), 301 [M C6F5O]+
483.9733 C12HF17O
483.9756
(3.72), 281 [M
C6F5O HF]+ (11.01), 277 [M
C6F5 2HF]+ (5.48), 233 [C6F5OCF2]+ (66.40), 184
[C6F5OH]+ (100), 167 [C6F5]+ (69.09), 119 [C2F5]+ 93
[CF3CC]+ (7.80), 69 [CF3]+ (93.82) 51 [CHF2]+ (22.22)
XI
61 58 59 (3) 402 [M]+ (39.63), 383 [M F]+ (4.69), 333 [M CF3]+ 402.0483 C14H9F11O
(4.69), 283 [M C2F5]+ 214 [M CF3 C2F5]+ (1.92),
402.0477
121 [C6H3O(CH3)2]+ (2.70), 105 [C8H9]+ (100), 91
[C7H6]+ (6.28), 69 [CF3]+ (4.37)
XII
XIII
79 84 86 (2) 434 [M]+ (100), 415 [M F]+ (14.13), 315 [M C2F5]+ 434.0371 C14H9F11O3 434.0376
(1.08), 281 [M C8H9O]+ (0.75), 265 [M C8H9]+
(51.60), 153 [C8H9O3]+ (51.60), 137 [C8H9O]+ (0.84),
119 [C2F5]+ (0.83), 69 [CF3]+ (4.96)
69 91 92 (2.5) 419 [M]+ (100), 400 [M F]+ (6.01), 373 [M NO2]+ 419.0008 C12H4F11NO3 419.0015
(16.98), 350 [M CF3]+ (19.63), 330 [M CF3 HF]+
(22.44), 304 [M CF3 NO2]+ (17.78), 300 [M C2F5]+
(2.39), 235 [M 2CF3 NO2]+ (13.50), 122 [C6H5NO2]+
(14.01), 119 [C2F5]+ (15.52), 69 [CF3]+ (17.43)
XIV
55 96 97 (2.5) 419 [M]+ (100), 400 [M F]+ (3.19), 373 [M NO2]+ 418.9999 C12H4F11NO2 419.0015
(11.83), 354 [M
F
NO2]+ (17.64), 350 [M CF3]+
(4.75), 304 [M CF3 NO2]+ (10.82), 300 [M C2F5]+
(4.58), 254 [M C2F5 NO2]+ (9.86), 235 [M C2F5
NO2 F]+ (17.19), 122 [C6H4NO2]+ (12.56), 119 [C2F5]+
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SYNTHESIS OF PARTIALLY FLUORINATED ORGANIC COMPOUNDS
399
Table 1. (Contd.)
.
bp,
(p, mm Hg)
C
Found
M
Calculated
Mass spectrum, m/z (Irel, %)
Formula
M
XIV
(17.98), 76 [C6H4]+ (36.89), 69 [CF3]+ (17.38), 46
[NO2]+ (1.90), 50 [CF2]+ (19.40)
XVIII 93 46 47 (3) 391 [M]+ (27.98), 372 [M F]+ (0.60), 272 [M C2F5]+ 391.0061 C11H4F11NO2 391.0066
(100), 252 [M C2F5 HF]+ (5.77), 203 [M C2F5
CF3]+ (0.72), 119 [C2F5]+ (4.90), 109 [C5H3NO ]+
(0.83), 93 [C5H4NO]+ (28.84), 69 [CF3]+ (15.38) 265
[C5H5N]+ (22.64)
XIX
50 68 70 (2) 356 [M F]+ (5.87), 306 [M CF2]+ (58.37), 287 [M
356.0126a C11H4F10NOa 356.0133a
448.0475 C18H10F10O2 448.0521
CF3]+ (0.58), 237 [M
C2F5]+ (7.76), 206 [M
(CF3)2C]+ (3.99), 119 [C2F5]+ (0.97), 78 [C5H5N]+
(100), 69 [CF3]+ (7.16), 51 [C4H4]+ (20.13)
XXIII 33 76 77 (7) 448 [M]+ (6.63), 355 [M OC6H5]+ (32.55), 335 [M
C6H5OH F]+ (5.36), 259 [M
F
C6H5 C6H5O]+
(16.10), 119 [C2F5]+ (0.70), 94 [C6H5OH]+ (84.85), 77
[C6H5]+ (100), 69 [CF3]+ (1.23)
XXIV 25
79 80 (7) 484 [M]+ (10.20), 465 [M F]+ (0.52), 389 [M C6H4F]+ 484.0339 H18H8F12O2 484.0333
(0.47), 373 [M C6H4FO]+ (71.01), 353 [M C6H4FO
HF]+ (16.28), 161 [C6H4FOCF2]+ (1.25), 119 [C2F5]+
(1.84), 111 [C6H4FO]+ (4.21), 95 [C6H4F]+ (100), 75
[C6H4F
HF]+ (21.27), 69 [CF3]+ (9.56)
XXV
76 69 70 (1) 672 [M]+ (9.38), 653 [M F]+ (41.62), 603 [M CF3]+ 671.9769 C16H2F22N2O2 671.9765
(100), 553 [M C2F5]+ (8.06), 503 [M C2F5 CF2]+
(82.56), 391 [M C6F11]+ (0.51), 281 [C6F11]+ (2.30),
119 [C2F5]+ (11.44), 100 [CF2=CF2]+ (1.64), 80
[C4H4N2]+ (30.77), 69 [CF3]+ (36.94), 52 [C4H4]+
(12.10)
a
+
For [M
F] .
Table 2. 1H, 13C, and 19F NMR spectra of partially fluorinated alkyl alkenyl ethers
.
19F NMR spectrum, F, ppm
F1 F3 F4 F5 F6
1H NMR
spectrum,
, ppm
13C NMR spectrum, C, ppm (JCF, Hz)
1
2
2
IV
7.00
109.9 (C4, JCF 264.8, JCF 40.1), 117.4 (C9, JCF 18.2), 118.1 106.6 30.2a 50.2 81.6 103.3
(C5, JCF = JCF 35.2), 118.2 (C10), 120.3 (C1, 1JCF 275.4), 120.7
1
(C6, JCF 276.2), 121.2 (C2, JCF 25.8), 124.4 (C11), 124.8 (C12)
1
2
144.4 (C7, 2JCF 10.8), 151.9 (C8, 1JCF 248.9), 153.7 (C3, 2JCF 30)
V
7.06, 6.54, 110.3 (C4, 1JCF 264.9, 2JCF 40.1), 118.4 (C5, 1JCF 287.7, 2JCF 35.1), 106.9
51.5 82.1 103.6
51.5 82.6 103.6
6.45, 3.55, 20.3 (C6, 1JCF 274.8), 120.5 (C1, 1JCF 277), 121.5 (C2, 2JCF 33.8),
2
6.58
153 (C3, JCF 28.9)
VI
6.19,6.16, 54.8 (C11), 94.6 (C8), 96.5 (C10), 110.2 (C4, 1JCF 265.2, 2JCF 39.7), 107
2
3.58
118.3 (C5, 1JCF 287.6, JCF 34.9), 120.2 (C6, 1JCF2 275), 120.4 (C1,
1JCF 277.7), 121.6 (C3, JCF 29.5), 152.8 (C2, JCF 28.3), 158.7
2
(C7), 162 (C9)
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FURIN et al.
Table 2. (Contd.)
.
19F NMR spectrum, F, ppm
F1 F3 F4 F5 F6
1H NMR
spectrum,
, ppm
13C NMR spectrum, C, ppm (JCF, Hz)
IX
X
7.27 (H9),
7.26(H10)
4.17
102.5 39.1 53.1 83.4 108
1
a
128.6 (C8), 128.9 (C9), 142.5 (C10), 148.3 (C7), 160.4 (C1, JCF
37.6 55.6 82.4 102.8
2
1
2
b
309.4) 52.0 (C2, JCF 15.4), 109.0 (C4, JCF 268.3, JCF 38.2),
109.5 (C1, JCF 287.5), 113.4 (C3, JCF 266.9, JCF 33.8), 118.2
1
1
2
(C5, JCF 287.4, JCF 30.2), 120.9 (C6, JCF 287.5), 124.5 (C7),
1
2
1
1
2
1
2
138.7 (C9, JCF 266.4, JCF 5.6), 141.4 (C10, JCF 245.9, JCF
1
2
13.1), 143.2 (C8, JCF 256.1, JCF 8.9)
XI
6.85, 2.13 16.4 (C11), 109.2 (C2, 2JCF 35.5), 110.6 (C4, 1JCF 265, 2JCF 38.5), 108.1
118.8 (C5, 1JCF 288, 2JCF 35.2), 120.6 (C6, 1JCF 275.1), 121.3 (C1,
1JCF 253.7), 126.3 (C8), 127.9 (C10), 129.9 (C9), 153.1 (C7), 157
50.6 83.1 104.6
49.5 81.8 103.4
51.8 82.4 103.7
(C3, JCF 36)
2
XII 7.02, 6.54, 53.1 (C11), 55.6 (C11), 104.8 (C9), 109.9 (C4, JCF 263.4, JCF 107
1
2
1
2
1
3.74
39.1), 118.2 (C5, JCF 287.8, JCF 35.3), 120.5 (C6, JCF 274.7),
120.7 (C1, JCF 74.7), 125.4 (C10), 127.3 (C3, JCF 17.2), 134.9
1
1
2
(C7), 149.6 (C8), 156.4 (C3, JCF 27.4)
XIII 8.98, 7.95, 109.9 (C4, JCF 265.2, JCF 40.2), 111.2 (C11), 117.9 (C5, JCF 106.8
1
2
1
7.67, 7.47 287.9, JCF 35), 119.6 (C6, JCF 270.2), 119.9 (C1, JCF 278.3),
2
1
1
120 (C8), 120.7 (C10), 124 (C2, 2JCF 30.8), 130.5 (C12), 149 (C9),
2
151.4 (C3, JCF 28.4), 156 (C7)
XIV 9.33 9.28, 109.7 (C4, 1JCF 265.5, 2JCF 40.1), 115.3 (C8), 117.6 (C5, 1JCF 288, 106.6
51.5 81.6 103.4
51.9 82.3 103.7
7.19 7.14 JCF 35.1), 119.3 (C6, JCF 276.1), 119.7 (C1, JCF 277.4), 125.4
2
1
1
(C9), 126 (C2, 2JCF 17.6), 144.2 (C7), (C3, 2JCF 29.6), 160.3 (C10)
2
2
XV
8.51, 8.41, 109.6 (C4, 1JCF 265.2, JCF 39.8), 117.6 (C5, 1JCF 287.9, JCF2 36), 107.2
7.39, 7.23 119.3 (C6, JCF 286.7), 119.9 (C1, JCF 286.7), 121.6 (C2, JCF
24.6), 122.3 (C10), 122.5 (C11), 137.9 (C9), 145.9 (C8), 151.8 (C3,
2JCF 34.2), 153 (C7)
1
1
XVI 8.59, 8.46,
108.5 51.1 38.9 83.8 107.5
7.28, 7.28
XVII 7.41, 8.28
106.9 50.8 38.4 83.6 107.0
c
XVIII 7.83, 7.31, 51.6 (C7, 2JCF 37.9), 106.7 (C6, 2JCF 28.8), 109.4 (C7, 1JCF 265.2,
7.01, 4.83 JCF 36.3), 116.1 (C5), 117.9 (C8, JCF 287.1, JCF 39),
2
1
2
118.4 (C11,12, 1JCF 285.1), 119.2 (C6), 137.3 (C3), 141 (C4), 155.4
(C2)
XIX 8.02, 7.60, 110.2 (C4, JCF 264.3, JCF 39.6), 110.5 (C10), 118.5 (C5, JCF 106.6 51.5
82.5 103.2
1
2
1
6.95, 6.88 287.9, JCF 35.3), 120 (C6, JCF 243), 120.4 (C1, JCF 235.2),
2
1
1
2
120.6 (C9), 121.9 (C11), 122.8 (C2, JCF 35), (C8), 162.4 (C7)
XXIII 7.11, 6.95,
108.8
38.8 83.7 107.6
6.45
XXIV 6.93
108.6 32.6d 39.0 83.9 107.7
XXV 7.46, 7.26 109.3 (C4, JCF 264.8, JCF 39.5), 116.1 (C2, JCF 28.2), 117.7 106.3
55.0 82.7 103.1
1
2
2
(C5, 1JCF 288.2, JCF 31.5), 118.9 (C6, 1JCF 275.4), 119 (C5, 1JCF
2
259.2, 2JCF 30.3), 119.5 (C1, 1JCF 277.1), 126.3 (C12), 127.3 (C12),
133.6 (C11), 134.6 (C11), 151.5 (C7,10), 158 (C2, 2JCF 28.5), 158.1
(C3, JCF 18.9)
2
a
1
b
8
10
9
c
98.5 and 97.8 ppm (F ), AB system, J 145.4 Hz. 12.6 (F ), 7.3 (F ), 0.9 ppm (F ) (F atoms in the benzene ring). 102.5
(F
FF
11, 12
8
9
d
), 39.1 (F ), 84.2 ppm (F ).
F atoms in the benzene ring.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 3 2005

SYNTHESIS OF PARTIALLY FLUORINATED ORGANIC COMPOUNDS
and 2 h at 45 C. Then the mixture was poured into
401
ACKNOWLEDGMENTS
water (100 ml) and neutralized with dilute HCl; the
reaction products were extracted with CH2Cl2 (3
30 ml), and the extract was dried over MgSO4. The
solvent was distilled off, and the residue was distilled
in a vacuum to obtain 2-trifluoromethyl-3-o-fluoro-
phenoxy-1,1,1,4,4,5,5,5-octafluoropent-2-ene III.
The study was performed within the Universities of
Russia program of the Ministry of Education of the
Russian Federation (project no. UR.05.01.023).
REFERENCES
b. A 3.33-mmol portion of 2-hydroxybenzimida-
zole or 2-hydroxybenzothiazole was added with vigor-
ous stirring at 0 C to a solution of 1 g of I and 1.01 g
of triethylamine in 30 ml of acetonitrile. The mixture
was stirred for 1 h at 0 C, 1 h at 25 C, and 2 h at
40 C. Then the mixture was poured into water, the
products were extracted with CH2Cl2 (3 30 ml), and
the extract was dried over CaCl2. The solvent was
distilled off, and the residue was dried in a vacuum
and recrystallized from CH2Cl2.
1. Novoe v tekhnologii soedinenii ftora (Fluorine Com-
pounds. Modern Techonology and Application),
Ishikawa, N., Ed., Moscow: Mir, 1984.
2. Organofluorine Chemistry, Principles and Commer-
cial Applications, Banks, R.E., Smart, B.E., and
Tatlow, J.C., Eds., New York: Plenum, 1994.
3. Organofluorine Compounds in Medicinal Chemistry
and Biomedical Applications, Filler, R., Kobaya-
shi, Y., and Yagupolskii, L.M., Eds., Amsterdam:
Elsevier, 1993.
4. Welch, J.T. and Eswarakrishnan, S., Fluorine in Bio-
organic Chemistry, New York: Wiley, 1991.
5. Maruta, M. and Ishikawa, N., J. Fluorine Chem.,
1979, vol. 13, no. 5, p. 421.
6. Ishikawa, N. and Nagashima, A., Bull. Chem. Soc.
Jpn., 1976, vol. 49, no. 2, p. 502.
7. Makarov, K.N., Gervits, L.L., Cheburkov, Yu.A., and
Knunyants, I.L., J. Fluorine Chem., 1977, vol. 10,
no. 4, p. 323.
8. Sereda, S.V., Antipin, M.Yu., Gervits, L.L., and
Struchkov, Yu.T., Izv. Akad. Nauk SSSR, Ser. Khim.,
1989, no. 11, p. 1549.
9. JPN Patent 62-178551, 1987, Chem. Abstr., 1988,
vol. 108, 55648w.
10. JPN Patent 0841045, 1996, Chem. Abstr., 1996,
vol. 124, 343275v.
11. UK Patent 1366691, 1974, Ref. Zh. Khim., 1975,
18N197P.
2-(3,3,3-Trifluoro-1-pentafluoroethyl-2-trifluoro-
methylpropenyloxy)-1H-benzimidazole VII. Yield
56%, yellow crystals, mp 57 58 C. IR spectrum, ,
1
1
cm : 3040, 1762, 1487, 1201, 1033. H NMR spec-
trum (CDCl3), , ppm: 7.00 7.06 m (2H), 7.28 d.d
(2H, J 3.6, 5.8 Hz). 19F NMR spectrum (CDCl3),
,
F
ppm: 51.0 m (2F), 81.3 d (3F, J 9.7 Hz), 100.2 q (3F,
J 10.4 Hz), 104.6 m (3F). Mass spectrum, m/z (Irel):
419 (80) [M]+, 373 (16), 350 (23), 304 (30).
2-(3,3,3-Trifluoro-1-pentafluoroethyl-2-trifluoro-
methylpropenyloxy)benzothiazole VIII. Yield 76%,
1
yellow crystals, mp 48 50 C. IR spectrum, , cm :
1
3095, 1698, 1474, 1193. H NMR spectrum (CDCl3),
, ppm: 7.27 7.48 m (4H). 19F NMR spectrum
(CDCl3), F, ppm: 52.0 m (2F), 82.1 q (3F, J 9.5 Hz),
100.2 q (3F, J 10.6 Hz), 104.6 m (3F). Mass spec-
trum, m/z (Irel, %): 431 (76) [M]+, 362 (99).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 3 2005