Synthesis and Chemistry of CF3C6F4OC6F4 Group 14/16 Derivatives

Article abstract of DOI:10.1021/ic970528d

Reactions of 4′-CF₃C₆F₄OC₆F₄Li, generated in situ, with elements of group 16 (S, Se, Te) lead to CF₃C₆F₄OC₆F₄SH (2), (CF₃C₆F₄OC₆F₄Se) ₂ (3), and (CF₃C₆F₄OC₆F₃) ₂ (4)(CF₃C₆F₄OC₆F₃) ₂Te (4a). The phenol derivative CF₃C₆F₄OC₆F₄OH (1) is obtained by reaction of CF₃₆F₄OC₆F₄Li with B(OMe)₃/H₂O₄. The reaction of CF₃C₆F₄OC₆F₄Li with trimethylsilyl chloride or trimethyltin chloride gives CF₃C₆F₄OC₆F₄XMe ₃ (X = Si (5), Sn (6)). Oxidation of 2 in the presence of bromine results in the formation of (CF₃C₆F₄OC₆F₄-S) ₂ (7) and CF₃C₆F OC₆F₄SO₂Br (8). Mixed perfluoroaryloxo/thio ethers CF₃C₆F₄OC₆F₄R (R = NO₂ (9), CN (10), CF₃ (11)) and CF₃C₆F₄OC₆F₄SC ₅F₄N (12) are obtained upon reaction of 2 with excess C₆F₅R and pentafluoropyridine in the presence of K₂CO₃. With 4-C₆F₅OC₆F₄NO₂) a mixture of (2-CF₃C₆F₄OC₆F ₄S)(4-C₆F₅O)C₆F₃NO ₂ (13) and 9 is formed. Reaction of excess 2 with C₆F₅R gives the 2,4,6-substituted benzenes (CF₃C₆F₄OC₆F₄S) ₃C₆F₂R (R = NO₂ (14), CN (15)). The trimethylsilyl ether CF₃C₆F₄OC₆F₄OSiMe ₃ (16) is prepared from the reaction of 1 with hexamethyldisilazane. 16 is a convenient reagent for the preparation of the aryl ethers CF₃C₆F₄OC₆F₄OC ₆F₄R (R = NO₂ (17), CN (18)) and CF₃C₆F₄OC₆F₄OC ₆F₄N (19) upon reaction with C₆F₅R and C₅F₅N. The secondary alcohols CF₃C₆F₄OC₆F₄CH(C ₆H₅)OH (20) and CF₃C₆F₄OC₆F₄CH(C ₆F₅)OH (21) are synthesized by the reactions of 5 with benzaldehyde and pentafluorobenzaldehyde in the presence of tetrabutylammonium fluoride as a catalyft In the synthesis of 21 the byproduct CF₃C₆F₄OC₆F₄CH(C ₆F₅)OC₆F₄CHO (22) is also formed and isolated.

Full text of DOI:10.1021/ic970528d

5222
Inorg. Chem. 1997, 36, 5222-5230
Synthesis and Chemistry of CF3C6F4OC6F4 Group 14/16 Derivatives
Burkhard Krumm, Robert L. Kirchmeier, and Jean’ne M. Shreeve*
Department of Chemistry, University of Idaho, Moscow, Idaho 83844-2343
ReceiVed May 8, 1997X
Reactions of 4′-CF3C6F4OC6F4Li, generated in situ, with elements of group 16 (S, Se, Te) lead to CF3C6F4-
OC6F4SH (2), (CF3C6F4OC6F4Se)2 (3), and (CF3C6F4OC6F3Te)2 (4)/(CF3C6F4OC6F3)2Te (4a). The phenol
derivative CF3C6F4OC6F4OH (1) is obtained by reaction of CF3C6F4OC6F4Li with B(OMe)3/H2O2. The reaction
of CF3C6F4OC6F4Li with trimethylsilyl chloride or trimethyltin chloride gives CF3C6F4OC6F4XMe3 (X ) Si (5),
Sn (6)). Oxidation of 2 in the presence of bromine results in the formation of (CF3C6F4OC6F4S)2 (7) and CF3C6F4-
OC6F4SO2Br (8). Mixed perfluoroaryloxo/thio ethers CF3C6F4OC6F4SC6F4R (R ) NO2 (9), CN (10), CF3 (11))
and CF3C6F4OC6F4SC5F4N (12) are obtained upon reaction of 2 with excess C6F5R and pentafluoropyridine in
the presence of K2CO3. With 4-C6F5OC6F4NO2, a mixture of (2-CF3C6F4OC6F4S)(4-C6F5O)C6F3NO2 (13) and 9
is formed. Reaction of excess 2 with C6F5R gives the 2,4,6-substituted benzenes (CF3C6F4OC6F4S)3C6F2R (R )
NO2 (14), CN (15)). The trimethylsilyl ether CF3C6F4OC6F4OSiMe3 (16) is prepared from the reaction of 1 with
hexamethyldisilazane. 16 is a convenient reagent for the preparation of the aryl ethers CF3C6F4OC6F4OC6F4R
(R ) NO2 (17), CN (18)) and CF3C6F4OC6F4OC5F4N (19) upon reaction with C6F5R and C5F5N. The secondary
alcohols CF3C6F4OC6F4CH(C6H5)OH (20) and CF3C6F4OC6F4CH(C6F5)OH (21) are synthesized by the reactions
of 5 with benzaldehyde and pentafluorobenzaldehyde in the presence of tetrabutylammonium fluoride as a catalyst.
In the synthesis of 21 the byproduct CF3C6F4OC6F4CH(C6F5)OC6F4CHO (22) is also formed and isolated.
Introduction
The reaction with sulfur to give thiol 2 proceeds smoothly
just as for C6F5Li with sulfur.8 In the reaction with selenium
the selenophenol CF3C6F4OC6F4SeH that must be formed
initially is not isolable; instead, it oxidizes to form the stable
yellow diselenide 3. The reaction with tellurium is more
complex. We have spectral evidence that the initial species
formed is the ditelluride (CF3C6F4OC6F4Te)2 or the telluride
(CF3C6F4OC6F4)2Te (δ19F(o-F) ) -115.1 ppm, 125Te δ ) 299
(Perfluoroaryl)lithium reagents are widely employed as useful
intermediates for the preparation of a variety of perfluoroarylated
compounds. For example, the chemistry of (pentafluorophenyl)-
lithium is reviewed in detail.1,2 However, C6F5Li is unstable,
difficult to handle, and potentially hazardous.3,4 Recently, we
reported the synthesis of a new perfluorinated aryllithium
reagent, 4′-CF3C6F4OC6F4Li, and its reactions with ketones and
acid halides.5 During our investigations no unexpected sudden
decompositions of the reagent that is generated in situ occurred.
We believe that replacement of the fluorine atom at the para
position (relative to lithium) by the relatively bulky OC6F4CF3
group has a stabilizing effect and prevents reaction of the
(perfluoroaryl)lithium with itself. Now we report the chemistry
of CF3C6F4OC6F4Li with group 14/16 elements and other
substrates.6
3
ppm, t or p, JTe-F ) 38 Hz (CDCl3)) based on comparison
with (C6F5Te)2 (δ19F(o-F) ) -114.0 ppm, 125Te δ ) 300.2 ppm,
t, 3JTe-F ) 70.5 Hz (C6D6))9 and (C6F5)2Te (δ19F(o-F) ) -115.2
3
ppm (CH3CN)9, 125Te δ ) 298.0 ppm, p, JTe-F ) 50 Hz
(CDCl3))10 . Unfortunately, the multiplicity of the peak in the
125Te NMR spectrum for our intermediate does not clearly
distinguish between a triplet (ditelluride) or a pentet (telluride).
However, the deep red color indicates the presence of a
ditelluride. The ditellurides are in general11 deep red chro-
mophores, as is the case for (C6F5Te)2.9 It is possible that we
have a mixture of both species. The formation of a ditelluride
in the course of this reaction can be explained as in the selenium
case. In our case, the telluride anion, CF3C6F4OC6F4Te-, that
forms initially is oxidized to give a ditelluride. In contrast to
the stable diselenides, diorganoditellurides are very sensitive
to air and can eliminate tellurium, resulting in the formation of
diorganotellurides. The two possible intermediates were not
isolable and decomposed slowly into a variety of products.
Similar difficulties with the isolation of diaryl ditellurides are
reported when Grignard reagents are reacted with tellurium.12
The two decomposition products isolated in low yield from
this reaction are the telluroheterocycles (CF3C6F4OC6F3Te)2 (4)
and (CF3C6F4OC6F3)2Te (4a). Identification of 4 and 4a is
Results and Discussion
When generated in situ, CF3C6F4OC6F4Li5 reacts readily with
group 16 elements (S, Se, Te) to form CF3C6F4OC6F4SH (2),
(CF3C6F4OC6F4Se)2 (3), and (CF3C6F4OC6F3Te)2 (4)/(CF3C6F4-
OC6F3)2Te (4a). The synthesis of CF3C6F4OC6F4OH (1) is
accomplished by reacting B(OMe)3/H2O27 with CF3C6F4OC6F4-
Li. Exposure of CF3C6F4OC6F4Li to the atmosphere leads only
to hydrolysis and recovery of the precursor CF3C6F4OC6F4H5
(Scheme 1).
X Abstract published in AdVance ACS Abstracts, October 1, 1997.
(1) Cohen, S. C.; Massey, A. G. In AdVances in Fluorine Chemistry;
Tatlow, J. C., Peacock, R. D., Hyman, H. H., Eds.; Butterworths &
Co.: London, 1970; Vol. 6, p 83.
(2) Burton, D. J.; Yang, Z.; Morken, P. A. Tetrahedron 1994, 50, 2993.
(3) Kinsella, E; Massey, A. G. Chem. Ind. 1971, 36, 1017B.
(4) Cohen, S. C.; Tomlinson, A. J.; Wiles, M. R.; Massey, A. G. Chem.
Ind. 1967, 21, 877.
(8) Brooke, G. M.; Abul Quasem, Md. J. Chem. Soc. C 1967, 865.
(9) Kasemann, R.; Naumann, D. J. Fluorine Chem. 1990, 48, 207.
(10) Aramini, J.; Batchelor, R. J.; Jones, C. H. W.; Einstein, F. W. B.;
Sharma, R. D. Can. J. Chem. 1987, 65, 2643.
(5) Krumm, B.; Vij, A.; Kirchmeier, R. L.; Shreeve, J. M. Inorg. Chem.
1997, 36, 366 and references therein.
(6) Krumm, B.; Kirchmeier, R. L.; Shreeve, J. M. Presented at the ACS
13th Winter Fluorine Conference, St. Petersburg, FL, 1997; Abstract
P33.
(11) Houben-Weyl, Methods of Organic Chemistry, 4th ed.; Klamann, D.,
Irgolic, K. J., Eds.; Georg Thieme Verlag: Stuttgart/New York, 1990;
Vol. E12b.
(7) Brooke, G. M.; Furniss, B. S. J. Chem. Soc. C 1967, 869.
(12) Haller, W. S.; Irgolic, K. J. J. Organomet. Chem. 1972, 38, 97.
S0020-1669(97)00528-4 CCC: $14.00 © 1997 American Chemical Society

CF3C6F4OC6F4 Group 14/16 Derivatives
Inorganic Chemistry, Vol. 36, No. 23, 1997 5223
Scheme 1
Scheme 2
based primarily on spectroscopic data. Perfluoroaryl telluro-
heterocycles with the proposed structures (Scheme 1) are to the
best of our knowledge not known. A possible mechanism for
their formation is the intermolecular attack of the strong
nucleophile CF3C6F4OC6F4Te- on a second molecule with
concomitant elimination of fluoride. We believe that the
3-position is the preferred position for attack compared to the
2-position because of the greater electron-withdrawing effect
of the vicinal oxygen. Possible structures with the sum formulas
(CF3C6F4OC6F3Te)2 (4) and (CF3C6F4OC6F3)2Te (4a) showing
the correct isotope pattern for a compound having two tellurium
atoms (4) at m/e ) 984 (130Te) and one tellurium atom (4a) at
m/e ) 854 (130Te) other than these eight- and seven-membered
rings can be ruled out. The shift ranges of the resonances as
well as the correct integrals for 4 and 4a in the 19F NMR spectra
support the structures shown. The other two possible positions
for attack to give a metallocycle product, 2′-C and 3′-C (see
Experimental Section for atom numbering of 4) on the OC6F4-
CF3-ring, can be eliminated by 19F NMR data. The resonances
of the fluorine atoms attached to 2′-C and 3′-C as well as the
integrals in the 19F NMR spectrum are identical to the
resonances seen for fluorine atoms R and â to CF3 in compounds
1-3, as well as others containing the OC6F4CF3 moiety.
Compound 4a may result from Te elimination by 4. The 125Te
resonances of 4 (δ ) 739 ppm) and 4a (δ ) 778 ppm) lie in
the range for organotellurides and can be compared to the
resonances of telluranthrene (C6H4Te)2 (125Te δ ) 888 ppm)13
and diphenyl telluride (C6H5)2Te (125Te δ ) 688 ppm).14 Due
to the limited number of reported 125Te NMR shifts, we are not
able to compare our shifts for 4 and 4a to the shifts of other
fluoroaromatic telluroheterocycles. For example, the perfluoro
analogue of telluranthrene, (C6F4Te)2, is known, but no 125Te
NMR shift is given.15 The mass spectral fragment patterns of
4 and 4a, showing the correct isotope distributions for a Te2
compound in 4 and a Te1 compound in 4a, are consistent with
those of similar Te compounds reported in the literature.16
The preparation of the trimethylsilyl and trimethyltin deriva-
tives CF3C6F4OC6F4SiMe3 (5) and CF3C6F4OC6F4SnMe3 (6) is
achieved by reaction of CF3C6F4OC6F4Li with trimethylsilyl
chloride and trimethyltin chloride (Scheme 2).
In contrast to 5, the tin derivative 6 is found to be moisture
sensitive and hydrolyzes slowly after prolonged periods (2
months). The formation of the products CF3C6F4OC6F4H and
(13) Dereu, N. L. M.; Zingaro, R. A. J. Organomet. Chem. 1981, 212,
141.
(14) McFarlane, H. C. E.; McFarlane, W. J. Chem. Soc., Dalton Trans.
1973, 2416.
(15) Rainville, D. P.; Zingaro, R. A.; Meyers, E. A. J. Fluorine Chem.
1980, 16, 245.
(16) Irgolic, K. J.; Haller, W. S. Int. J. Sulfur Chem., Part A 1972, 2, 267.

5224 Inorganic Chemistry, Vol. 36, No. 23, 1997
Krumm et al.
1
Figure 1. 119Sn{1H}and H NMR spectra of CF3C6F4OC6F4Sn(CH3)3 (6).
Scheme 3
1
a Me3SnOH/(Me3Sn)2O mixture is confirmed by 19F and H
The thiol 2 reacts readily with pentafluorobenzenes C6F5R
(R ) NO2, CN, CF3, OC6F4NO2) and pentafluoropyridine at
room temperature in the presence of K2CO3 to give the
monosubstituted (para) benzenes CF3C6F4OC6F4SC6F4R (R )
NO2 (9), CN (10), CF3 (11)) and CF3C6F4OC6F4SC5F4N (12)
(Scheme 4). When R ) NO2, the ortho-substituted product is
also formed. In the case where R ) OC6F4NO2, replacement
of the p-fluorine atom is not observed. Instead, the carbon atoms
ortho as well as para to the nitro group are activated and the
resulting products 9 (by loss of pentafluorophenolate) and (2-
CF3C6F4OC6F4S)(4-C6F5O)C6F3NO2 (13) are isolated. The
spectroscopic data for the former agree with the data for 9
isolated from the reaction of 2 with pentafluoronitrobenzene.
NMR data.
The 119Sn{1H} and 1H NMR spectra of 6 are given in Figure
1. The 119Sn nucleus shows couplings to the o- and m-fluorine
atoms, resulting in a triplet of triplets. The methyl resonances
1
in the H NMR are split by a small coupling to the o-fluorine
atoms to a triplet. The 119Sn/117Sn satellites also show the triplet
structure.
Bromine oxidizes 2 to form a mixture of the disulfide
(CF3C6F4OC6F4S)2 (7) and the sulfonyl bromide CF3C6F4OC6F4-
SO2Br (8) (Scheme 3).
The appearance of another signal in the 19F NMR spectrum
in the region of o-fluorine atoms bound to sulfur (in addition
to 2, 7, and 8) located at -127.1 ppm leads us to believe that
the sulfenyl bromide CF3C6F4OC6F4SBr is formed as a transient
intermediate. Attempts to isolate this compound failed due to
its instability, which is common for this class of compounds.
The sulfenyl bromide loses bromine to give 7 or is oxidized to
8. In a separate experiment carried out in acetic acid it was
shown that the disulfide 7 also reacts slowly with bromine to
give the resonance at -127.1 ppm attributed to the sulfenyl
bromide. But due to its instability it re-forms 7 or is oxidized
to 8.
Multiple substitution is achieved by using an excess of 2 with
pentafluoronitrobenzene and pentafluorobenzonitrile. As shown
in Scheme 5, the 2,4,6-substituted nitrobenzene (CF3C6F4-
OC6F4S)3C6F2NO2 (14) and benzonitrile (CF3C6F4OC6F4S)3C6F2-
CN (15) are obtained.
Although the reaction to give the trisubstituted products 14
and 15 proceeds at ambient temperature, further substitution of
14 or 15 with 2 does not occur even under more vigorous
conditions.

CF3C6F4OC6F4 Group 14/16 Derivatives
Inorganic Chemistry, Vol. 36, No. 23, 1997 5225
Scheme 4
Scheme 5
Scheme 6
OC6F4CH(C6F5)O- initially formed to displace the fluorine atom
in the para position of C6F5CHO.
In addition to small amounts of the hydrolysis product
CF3C6F4OC6F4H, undesirable side reactions are observed. It
appears that the reactive fluoride catalyst cleaves the aromatic
ether bond. Evidence for this cleavage is found in 19F NMR
spectra. These signals are not observed when the reaction is
carried out with benzaldehyde and C6F5SiMe3 under the same
conditions. This limits the use of 5 as an effective transfer agent
for CF3C6F4OC6F4 moieties into organic molecules. However,
the products shown in Scheme 9 were isolated and purified by
column chromatography.
Table 1 shows the influence of the substituent R on the 19F
NMR resonance of the o-fluorine atoms in some CF3C6F4OC6F4
derivatives. The shifts range from -163.0 ppm for R ) OH to
-115.1 ppm for R ) TenC6F4OC6F4CF3. In addition to
inductive effects, the size of the adjacent atom also plays a role;
i.e., with increasing size of the atom adjacent to the o-F atom
a downfield shift is observed. The shifts for X ) H and SH
seem to be exceptions.
The phenol 1 reacts with hexamethyldisilazane to form the
trimethylsilyl ether CF3C6F4OC6F4OSiMe3 (16) (Scheme 6).
With pentafluoronitrobenzene, 1 reacts to form CF3C6F4-
OC6F4OC6F4NO2 (17) under the same conditions employed for
the reaction with the sulfur derivative 2. In this case, however,
due to the decreased nucleophilicity of oxygen compared to
sulfur, a longer time is required for the reaction to reach
completion at 25 °C (Scheme 7).
The reaction time can be reduced by ∼50% by using the
trimethylsilyl ether 16 in place of 1. Also at higher tempera-
tures, the less reactive pentafluorobenzonitrile and pentafluo-
ropyridine form monosubstituted derivatives CF3C6F4OC6F4-
OC6F4CN (18) and CF3C6F4OC6F4OC5F4N (19) (Scheme 8).
The synthesis of the trimethylsilyl derivative 5 prompted us
to study the possibility of its use as a transfer agent for CF3C6F4-
OC6F4 groups similar to that described for CF3SiMe317 and C6F5-
SiMe3.18 Compound 5 reacts with pentafluorobenzaldehyde or
benzaldehyde in the presence of catalytic amounts of fluoride
ion to give the secondary alcohols, CF3C6F4OC6F4CH(C6H5)OH
(20) and CF3C6F4OC6F4CH(C6F5)OH (21). A byproduct
CF3C6F4OC6F4CH(C6F5)OC6F4CHO (22) was detected and
isolated from several other unidentified products in the reaction
with pentafluorobenzaldehyde (Scheme 9). Its formation can
be explained by the reaction of the alkoxide CF3C6F4-
Experimental Section
Materials. The solvents THF and diethyl ether are distilled over
sodium prior to use. Cesium fluoride is dried and maintained at 160
°C. All other chemicals are used as received (Aldrich, Fluorochem,
PCR).
General Considerations. A conventional vacuum system, consist-
ing of a Pyrex glass vacuum line fitted with Teflon needle stopcocks
and equipped with Heise Bourdon tube and Televac thermocouple
gauges, is used to handle volatile liquids. Infrared spectra are recorded
on a Perkin-Elmer 1710 FT-IR spectrometer between KBr plates as
neat liquids or solids as Nujol mulls. NMR spectra are obtained on a
Bruker AC200 or AC300 FT-NMR instrument using CDCl3 as solvent
except where otherwise indicated. Chemical shifts are reported with
(17) Prakash, G. K. S.; Krishnamurti, R.; Olah, G. A. J. Am. Chem. Soc.
1989, 111, 393.
(18) Patel, N. R.; Kirchmeier, R. L. Inorg. Chem. 1992, 31, 2537 and
references therein.

5226 Inorganic Chemistry, Vol. 36, No. 23, 1997
Krumm et al.
Scheme 7
Scheme 8
Scheme 9
respect to (CH3)4Si (1H, 13C, 29Si), CFCl3 (19F), (CH3)2Se (77Se), (CH3)4-
Sn (119Sn), and (CH3)2Te (125Te). Mass spectra are obtained with a
Varian VG 7070 HS mass spectrometer by using electron impact (EI)
techniques. Multi-isotope containing fragments refer to the isotope with
the highest abundance. Elemental analyses are performed by Beller
Mikroanalytisches Laboratorium, Go¨ttingen, Germany. All reactions
involving lithiations or silylated compounds are carried out in an
atmosphere of dry nitrogen.
Spectral data for 4-(4′-CF3C6F4O)C6F4OH (1): IR (Nujol/KBr)
3400 m vbr (νOH), 1657 m, 1531 s, 1510 s, 1500 s, 1466 m, 1428 w,
1352 s, 1310 w, 1229 m, 1188 m, 1156 s, 1090 m, 1042 w, 1012 s,
1000 s, 980 s, 880 m, 807 w, 782 w, 721 m cm-1
;
19F NMR δ -56.2
4
(4′-CF3, t, 3F, JF-F ) 21.5 Hz), -140.0 (3′-F, m, 2F), -155.3 (2′-F,
1
m, 2F), -157.5 (3-F, m, 2F), -163.0 (2-F, m, 2F); H NMR δ 5.9
(OH, br, 1H), 2.1 (H2O, br) ppm; MS (EI) [m/e (species, intensity)]
398 (M+, 62), 379 (M+ - F, 14), 351 (M+ - F - CO, 1), 329 (M+
-
CAUTION! Experiments inVolVing solutions of CF3C6F4OC6F4Li
should be handled with care, conducted at low temperatures and under
strict exclusion of oxygen and/or moisture!
CF3, 1), 301 (M+ - CF3 - CO, 1), 217 (CF3C6F4+, 8), 181 (OC6F4-
OH+, 100), 161 (OC6F3O+, 12), 148 (C6F4+, 5), 137 (C5F4H+, 8), 117
(C5F3+, 14), 105 (C4F3+, 16), 69 (CF3+, 15). Anal. Calcd for
C13H3F11O3 (monohydrate): C, 37.52; H, 0.73. Found: C, 37.42; H,
0.48.
Preparation of CF3C6F4OC6F4OH. To RFLi (RF ) CF3C6F4-
OC6F4),5 generated by lithiation of 10 mmol of CF3C6F4OC6F4H in 80
mL of ether, is added 13 mmol of trimethyl borate at -50 °C. The
mixture is warmed with stirring to -10 °C in 2 h; 30 mL of 50%
hydrogen peroxide is then added and the mixture warmed to 25 °C
and stirred for 1.5 days (under air). After phase separation, the aqueous
phase is extracted with dichloromethane. The combined organic phases
are dried over anhydrous Na2SO4. The solvents are removed under
vacuum, and the crude product is sublimed at 50 °C/0.01 Torr. The
resulting mixture, consisting of RFOH (1)/RFH in a relative ratio of
∼2:1, is extracted several times with n-hexane, where the hydroaromatic
is very soluble, but 1 is not. This purified phenol CF3C6F4OC6F4OH
(1) sublimes at 50 °C/0.01 Torr and crystallizes as a hydrate in 47%
yield (mp 74-78 °C) with a typical slightly phenolic odor.
Reaction of CF3C6F4OC6F4Li with Sulfur and Selenium. To RF-
Li,5 generated by lithiation of 10 mmol of CF3C6F4OC6F4H in 80 mL
of ether, is added 15 mmol of sulfur (selenium powder) at -50 °C.
After 1 h of stirring at that temperature, the mixture is warmed to 0 °C
in 2 h and treated with 10 mL of 10% H2SO4 and 20 mL of water.
Stirring is continued for 30 min at 25 °C, and the phases are separated
and filtered from unreacted sulfur (selenium). After extraction with
ether/water, the combined ether phases are dried over anhydrous Na2-
SO4. The solvent is removed under vacuum and the residue sublimed.
The thiol CF3C6F4OC6F4SH (2) sublimes at 40 °C/0.01 Torr to give
colorless crystals with an unpleasant odor in 82% yield (mp 55-57
°C). The yellow, odorless diselenide (CF3C6F4OC6F4Se)2 (3) sublimes

CF3C6F4OC6F4 Group 14/16 Derivatives
Inorganic Chemistry, Vol. 36, No. 23, 1997 5227
Table 1. 19F NMR (CDCl3) Resonances ortho to R in
CF3C6F4OC6F4R Derivatives
1658 m, 1603 m, 1510 s, 1466 s, 1426 s, 1344 s, 1279 w, 1263 w,
1229 m, 1191 m, 1164 m, 1146 m, 1113 m, 1066 m, 996 s, 877 m,
821 m, 801 w, 770 w, 750 w, 738 w, 718 m, 683 w, 644 w, 594 w
cm-1 19F NMR δ -56.1 (4′-CF3, t, 3F, 4JF-F ) 21.6 Hz), -102.1 (2-
;
3 4
F, dm, 1F), -107.7 (6-F, dd, 1F, JF-F ) 23.6 Hz, JF-F ) 13.2 Hz),
-139.8 (3′-F, m, 2F), -145.5 (5-F, dm, 1F), -154.6 (2′-F, m, 2F);
125Te NMR δ 739 (m) ppm; MS (EI) [m/e (130Te) (species, intensity)]
984 (M+, 100), 965 (M+ - F, 8), 854 (M+ - Te, 91), 637 (M+ - Te
- CF3C6F4, 14), 621 (M+ - Te - CF3C6F4O, 12), 609 (M+ - Te -
CF3C6F4 - CO, 23), 492 (CF3C6F4OC6F3Te+, 19), 389 (C6F3Te2+, 15),
377 (C5F3Te2+, 8), 259 (C6F3Te+, 67), 233 (CF3C6F4O+, 16). Anal.
Calcd for C26F20O2Te2: C, 31.88; F, 38.80. Found: C, 31.88; F, 40.0.
Spectral data for [4-(4′-CF3C6F4O)C6F3]2Te (4a): IR (Nujol/KBr)
1659 m, 1622 m, 1505 s, 1462 s, 1341 s, 1278 w, 1224 m, 1193 m,
1155 m, 1113 m, 1074 w, 1058 m, 992 s, 931 w, 880 m, 831 w, 813
R
δ (ppm)
R
δ (ppm)
OH
Fa
-163.0
-161.1
-158.3
-154.9
-154.9
-154.8
-142.9
-142.7
-139.9
-137.8
-136.6
-136.2
C(CF3)2OHa
SO2Br
SSC6F4OC6F4CF3
SC6F4CF3
SC6F4NO2
SC6F4CN
-135.0
-134.4
-131.1
-131.0
-130.8
-130.8
-130.4
-127.1
-127.1
-125.0
-121.3
-115.1
OSi(CH3)3
OC6F4NO2
OC6F4CN
OC5F4N
CH(C6F5)OH
CH(C6H5)OH
C(C6F5)2OHa
Ha
w, 718 m, 612 w cm-1 19F NMR δ -56.1 (4′-CF3, t, 3F, 4JF-F ) 21.6
;
Hz), -115.0 (2-F, m, 1F), -126.0 (6-F, m, 1F), -139.8 (3′-F, m, 2F),
SC5F4N
-148.3 (5-F, m, 1F), -154.5 (2′-F, m, 2F); 125Te NMR δ 778 (s) ppm;
SBrb
MS (EI) [m/e (130Te) (species, intensity)] 854 (M+, 100), 835 (M+
F, 11), 724 (M+ - Te, 2), 637 (M+ - CF3C6F4, 6), 621 (M+
-
-
Si(CH3)3
SeSeC6F4OC6F4CF3
Sn(CH3)3
TenC6F4OC6F4CF3
CF3C6F4O, 10), 609 (M+ - CF3C6F4 - CO, 10), 404 (M+ - 2CF3C6F4
- O, 13), 388 (M+ - 2CF3C6F4O, 17), 233 (CF3C6F4O+, 18), 217
(CF3C6F4+, 8). Anal. Calcd for C26F20O2Te: C, 36.66. Found: C,
36.91.
SH
b
C(C6H5)2OHa
a Reference 5. b Not isolated, n ) 1 or 2.
Reaction of CF3C6F4OC6F4Li with Trimethylsilyl (or Trimeth-
yltin) Chloride. To RFLi, 5 generated by lithiation of 10 (or 2) mmol
of CF3C6F4OC6F4H in 80 (or 10) mL of ether, is added 14 (or 3) mmol
of trimethylsilyl (or trimethyltin) chloride at -50 °C, and the mixture
is warmed up to 25 °C and stirred for 2 h. The solvent is removed in
a slight vacuum and the residue slowly sublimed at 25-40 °C/0.01
Torr. Sublimation at 30 °C/0.01 Torr for final purification gives
at 130 °C/0.01 Torr in 80% yield (mp 103-105 °C). Thin yellow
needles are obtained upon recrystallization from ethanol or n-propanol.
Spectral data for 4-(4′-CF3C6F4O)C6F4SH (2): IR (Nujol/KBr)
2605 w (νSH), 1659 m, 1634 m, 1497 s, 1463 s, 1344 m, 1284 w, 1227
m, 1190 m, 1157 m, 1118 m, 1032 m, 1017 m, 1001 s, 980 m, 923 m,
882 m, 862 w, 799 w, 718 m, 640 w cm-1
;
19F NMR δ -56.2 (4′-CF3,
4
t, 3F, JF-F ) 21.6 Hz), -136.6 (2-F, m, 2F), -139.8 (3′-F, m, 2F),
-154.9 (2′-F, m, 2F), -155.8 (3-F, m, 2F); H NMR δ 3.70 (SH, s,
1
colorless, volatile crystals of CF3C6F4OC6F4SiMe3 (5, mp 32-34 °C)
1H) ppm; MS (EI) [m/e (species, intensity)] 414 (M+, 100), 413 (M+
- H, 16), 395 (M+ - F, 13), 367 (M+ - F - CO, 1), 249 (M+ - H
- C6F4O, 6), 217 (CF3C6F4+, 10), 197 (OC6F4SH+, 61), 181 (C6F4-
SH+, 24), 169 (C5F4SH+, 7), 165 (C6F4HO+, 12), 155 (C5F5+, 5), 149
(C5F3S+, 11), 137 (C4F3S+, 19), 131 (C5F2SH+, 6), 117 (C5F3+, 13),
93 (C3F3+, 9). Anal. Calcd for C13HF11OS: C, 37.69; H, 0.24.
Found: C, 37.57; H, 0.25.
in 77% yield [or CF3C6F4OC6F4SnMe3 (6, mp 34-36 °C) in 64% yield].
Spectral data for 4-(4′-CF3C6F4O)C6F4Si(CH3)3 (5): IR (liquid
film/KBr) 2964 m/2908 m (νCH), 1660 m, 1636 m, 1559 w, 1510 s,
1456 s, 1431 m, 1373 m, 1344 s, 1258 m, 1227 s, 1189 m, 1153 s,
1118 s, 1030 s, 1001 s, 971 s, 850 s, 817 m, 795 m, 772 m, 740 w,
730 w, 716 m, 635 m cm-1 19F NMR δ -56.1 (4′-CF3, t, 3F, 4JF-F
; )
21.6 Hz), -127.1 (2-F, m, 2F), -140.1 (3′-F, m, 2F), -154.7 (2′-F,
1
5
m, 2F), -156.3 (3-F, m, 2F); H NMR δ 0.39 (SiMe3, t, 9H, JH-F
)
Spectral data for [4-(4′-CF3C6F4O)C6F4Se]2 (3): IR (Nujol/KBr)
1660 m, 1631 m, 1505 s, 1484 s, 1431 m, 1392 m, 1343 m, 1278 w,
1229 m, 1190 m, 1155 s, 1116 m, 1028 m, 999 s, 975 s, 878 m, 824
1.5 Hz); 29Si{1H} NMR δ -0.62 (tt, 3JSi-F ) 2.9 Hz, 4JSi-F ) 1.9 Hz)
ppm; MS (EI) [m/e (species, intensity)] 454 (M+, 23), 439 (M+ - CH3,
52), 435 (M+ - F, 17), 373 (M+ - CH3SiF2, 15), 362 (M+ - (CH3)3-
SiF, 6), 343 (M+ - F - (CH3)3SiF, 10), 339 (M+ - F - (CH3)2SiF2,
17), 270 (M+ - F - (CH3)2SiF2 - CF3, 10), 242 (C9F7H+, 34), 206
w, 800 m, 718 m, 674 w, 642 w, 632 w cm-1
;
19F NMR δ -56.2
4
(4′-CF3, t, 3F, JF-F ) 21.6 Hz), -125.0 (2-F, m, 2F), -139.5 (3′-F,
m, 2F), -154.1 (2′-F, m, 2F), -154.7 (3-F, m, 2F); 77Se NMR δ 376
(t, 2Se, 3JSe-F ) 19.9 Hz) ppm; MS (EI) [m/e (80Se) (species, intensity)]
922 (M+, 20), 903 (M+ - F, 2), 842 (M+ - Se, 17), 823 (M+ - Se -
F, 2), 762 (M+ - 2Se, 6), 461 (M+/2, 100), 442 (M+/2 - F, 8), 381
(M+/2 - Se, 62), 362 (M+/2 - Se - F, 14), 297 (CF3C6F4Se+, 10),
244 (OC6F4Se+, 32), 228 (C6F4Se+, 17), 217 (CF3C6F4+, 15), 164
(C6F4O+, 14), 148 (C6F4+, 15), 117 (C5F3+, 30). Anal. Calcd for
C26F22O2Se2: C, 33.93; F, 45.43. Found: C, 34.13; F, 45.3.
(M+ - CH3 - CF3C6F4O, 20), 148 (C6F4+, 3), 117 (C5F3+, 12), 81
(CH3SiF2+, 42), 77 ((CH3)2SiF+, 100), 73 ((CH3)3Si+, 18), 69 (CF3
,
+
10). Anal. Calcd for C16H9F11OSi: C, 42.29; H, 2.00. Found: C,
42.35; H, 2.10.
Spectral data for 4-(4′-CF3C6F4O)C6F4Sn(CH3)3 (6): IR (Nujol/
KBr) 1658 m, 1633 m, 1510 s, 1485 s, 1368 m, 1343 s, 1278 w, 1258
w, 1227 s, 1190 m, 1156 s, 1113 m, 1060 w, 1024 m, 1000 s, 964 s,
876 m, 783 m, 737 w, 717 m, 639 m, 539 s, 517 cm-1
;
19F NMR δ
Reaction of CF3C6F4OC6F4Li with Tellurium. To RFLi,5 generated
by lithiation of 5 mmol of CF3C6F4OC6F4H in 40 mL of ether, is added
5 mmol of tellurium powder at -50 °C, and the mixture is warmed to
25 °C in 1 h. The mixture is then stirred for an additional 24 h at 25
°C and treated with 5 mL of water. (Shorter reaction times result in
inseparable mixtures of (CF3C6F4OC6F4Te)2 and 4). The unreacted
tellurium is filtered off, and the remaining solution is extracted with
ether/water. After removal of all volatile materials, the residue is heated
up to 100 °C/0.01 Torr in the presence of a sublimation finger. All
condensable material is discarded. The remaining residue is washed
thoroughly with hexane. The residue, soluble in chloroform, is a
mixture of two compounds in a ratio of ∼10:1 based on the 19F NMR
spectrum. The components are separated and purified by column
chromatography using dichloromethane/hexane (1:4) as eluent on silica
gel (70-230 mesh). The compounds, based on spectroscopic data and
elemental analysis, are identified as (CF3C6F4OC6F3Te)2 (4) (mp 152
°C dec, yellow-greenish powder, major component, ∼10% yield) and
(CF3C6F4OC6F3)2Te (4a) (mp 159-161 °C, yellowish powder, minor
component, traces, shorter retention time).
4
-56.1 (4′-CF3, t, 3F, JF-F ) 21.6 Hz), -121.3 (2-F, m, 2F), -140.3
(3′-F, m, 2F), -154.9 (2′-F, m, 2F), -155.2 (3-F, m, 2F); 1H NMR δ
0.47 (SnMe3, t, 9H, 5JH-F ) 0.7 Hz, 2JH-119Sn ) 59.2 Hz (dt), 2JH-117Sn
) 56.6 Hz (dt)); 119Sn{1H} NMR δ -13.5 (tt, 3JSn-F ) 21.4 Hz, 4JSn-F
) 8.3 Hz); 13C{1H} NMR δ 148.7 (1JC-F ) 236 Hz)/144.9 (1JC-F
)
264 Hz)/140.3 (1JC-F ) 248 Hz)/139.2 (1JC-F ) 256 Hz) (CF, dm),
1
138.0/134.4 (2 CO, m), 120.7 (CF3, q, JC-F ) 275 Hz), 113.6 (CSn,
tm, 2JC-F ) 47.9 Hz), 105.7 (CCF3, m), -7.5 (CH3, t, 4JC-F ) 2.1 Hz,
1
1JC-119Sn ) 381.5 Hz (dt), JC-117Sn ) 364.4 Hz (dt)) ppm; MS (EI)
[m/e (120Sn) (species, intensity)] 531 (M+ - CH3, 100), 527 (M+ - F,
15), 501 (M+ - 3CH3, 4), 362 (M+ - (CH3)3SnF, 8), 343 (M+ - F -
(CH3)3SnF, 90), 265 (M+ - (CH3)3SnF - CF3 - CO, 13), 217
(CF3C6F4+, 6), 173 (CH3SnF2+, 15), 169 ((CH3)2SnF+, 62), 148 (C6F4
,
+
7), 139 (SnF+, 44), 135 (SnCH3+, 13), 117 (C5F3+, 26), 69 (CF3+, 10).
Anal. Calcd for C16H9F11OSn: C, 35.26; H, 1.67. Found: C, 35.38;
H, 1.75.
Reaction of 2 with Bromine. To 1 mmol of 2 in 5 mL of glacial
acetic acid is added 5 mmol of bromine at 25 °C. After 1 h of stirring,
2 has reacted completely according to 19F NMR. A mixture consisting
Spectral data for [4-(4′-CF3C6F4O)C6F3Te]2 (4): IR (Nujol/KBr)

5228 Inorganic Chemistry, Vol. 36, No. 23, 1997
Krumm et al.
of RFSBr (δ -127.1(2-F)), RFSSRF (7) (δ -131.1(2-F)), and RFSO2Br
(8) (δ -134.5(2-F)) is formed. Adding more bromine results in
increased yields of RFSBr and 8. Removal of the volatile materials
after 2 days at 25 °C leads to debromination of the intermediate RF-
SBr to give 7. The resulting mixture of 7 and 8 is separated by slow
sublimation at 60 °C/0.01 Torr. The yields based on 2 are 24% for
(CF3C6F4OC6F4S)2 (7, mp 105-107 °C, subl 90 °C/0.01 Torr) and 21%
for CF3C6F4OC6F4SO2Br (8, mp 77-79 °C, subl 50 °C/0.01 Torr).
Spectral data for [4-(4′-CF3C6F4O)C6F4S]2 (7): IR (Nujol/KBr)
1661 m, 1634 m, 1506 s, 1487 s, 1466 m, 1431 m, 1398 w, 1343 m,
1283 w, 1230 m, 1190 m, 1156 m, 1135 m, 1119 m, 1031 m, 1001 s,
m, 1330 m, 1283 w, 1262 w, 1227 m, 1189 m, 1165 s, 1117 m, 1034
w, 998 m, 977 s, 880 m, 860 w, 831 w, 718 m, 704 w, 668 w cm-1
;
4
19F NMR δ -56.2 (4′′-CF3, t, 3F, JF-F ) 21.6 Hz), -56.6 (1-CF3, t,
4
3F, JF-F ) 21.6 Hz), -131.0 (2′-F, m, 2F), -131.8 (3-F, m, 2F),
-138.7 (2-F, m, 2F), -139.3 (3′′-F, m, 2F), -154.1 (2′′-F, m, 2F),
-154.4 (3′-F, m, 2F) ppm; MS (EI) [m/e (species, intensity)] 630 (M+,
100), 611 (M+ - F, 18), 561 (M+ - CF3, 1), 413 (M+ - CF3C6F4,
35), 397 (M+ - CF3C6F4O, 3), 378 (M+ - CF3C6F4O - F, 4), 217
(CF3C6F4+, 5), 180 (C6F4S+, 4), 149 (C5F3S+, 32), 117 (C5F3+, 6), 69
(CF3+, 11). Anal. Calcd for C20F18OS: C, 38.11; F, 54.26. Found:
C, 38.20; F, 54.5.
980 m, 881 m, 857 w, 806 w, 718 m, 674 w, 651 w cm-1 19F NMR
;
Spectral data for 4-[4′-(4′′-CF3C6F4O)C6F4S]C5F4N (12): IR
(Nujol/KBr) 1660 m, 1635 m, 1510 s, 1489 s, 1465 s, 1446 m, 1408
w, 1344 m, 1289 w, 1238 m, 1226 m, 1191 m, 1160 m, 1126 w, 1036
w, 999 m, 979 m, 959 m, 891 m, 881 m, 801 w, 717 m, 699 w, 651
δ -56.1 (4′-CF3, t, 3F, 4JF-F ) 21.6 Hz), -131.1 (2-F, m, 2F), -139.4
(3′-F, m, 2F), -154.1 (2′-F, m, 2F), -154.6 (3-F, m, 2F) ppm; MS
(EI) [m/e (species, intensity)] 826 (M+, 4), 413 (M+/2, 100), 394 (M+/2
+
- F, 12), 381 (M+/2 - S, 7), 362 (M+/2 - S - F, 3), 217 (CF3C6F4
,
w, 636 w, 585 m cm-1 19F NMR δ -56.2 (4′′-CF3, t, 3F, 4JF-F ) 21.7
;
20), 196 (OC6F4S+, 48), 180 (C6F4S+, 31), 164 (C6F4O+, 11), 149
(C5F3S+, 21), 148 (C6F4+, 8), 137 (C4F3S+, 30), 117 (C5F3+, 17). Anal.
Calcd for C26F22O2S2: C, 37.79; F, 50.58. Found: C, 37.90; F, 50.3.
Spectral data for 4-(4′-CF3C6F4O)C6F4SO2Br (8): IR (Nujol/KBr)
1661 m, 1635 m, 1511 s, 1465 m, 1433 m, 1394 m (νasymSO2), 1343 m,
1296 m, 1274 w, 1222 m, 1195 m, 1176 s (νsymSO2), 1126 m, 1071 w,
1035 m, 1007 m, 994 m, 879 m, 851 m, 807 w, 734 w, 716 m, 683 w,
Hz), -88.8 (2-F, m, 2F), -130.4 (2′-F, m, 2F), -137.5 (3-F, m, 2F),
-139.2 (3′′-F, m, 2F), -153.9 (2′′-F, m, 2F), -154.4 (3′-F, m, 2F)
ppm; MS (EI) [m/e (species, intensity)] 563 (M+, 100), 544 (M+ - F,
11), 518 (M+ - FCN, 1), 494 (M+ - CF3, 2), 413 (M+ - C5F4N, 7),
346 (M+ - CF3C6F4, 29), 330 (M+ - CF3C6F4O, 6), 311 (M+
-
CF3C6F4O - F, 5), 217 (CF3C6F4+, 8), 196 (OC6F4S+, 2), 180 (C6F4S+,
4), 149 (C5F3S+, 3), 148 (C6F4+, 3), 117 (C5F3+, 4), 69 (CF3+, 3). Anal.
Calcd for C18F15NOS: C, 38.38; F, 50.60. Found: C, 38.33; F, 50.4.
655 m, 640 w, 577 m, 558 m, 547 m cm-1
;
19F NMR δ -56.2 (4′-CF3,
4
t, 3F, JF-F ) 21.6 Hz), -134.4 (2-F, m, 2F), -138.5 (3′-F, m, 2F),
-152.2 (2′-F, m, 2F), -153.7 (3-F, m, 2F) ppm; MS (EI) [m/e (79Br)
(species, intensity)] 524 (M+, 1), 505 (M+ - F, 4), 460 (M+ - SO2,
26), 445 (M+ - Br, 100), 441 (M+ - SO2 - F, 3), 429 (M+ - Br -
Reaction of 2 with 4-Nitroperfluorodiphenyl ether. To a mixture
consisting of 0.5 mmol of 2 and 0.6 mmol of C6F5OC6F4NO2 (10 in
ref 5) in 5 mL THF is added 1 mmol anhydrous K2CO3 at 25 °C. After
1 h of stirring (19F NMR monitoring), all volatile materials are removed
in vacuum, and the residue, which contains equimolar amounts of 9
and 2-[(CF3C6F4O)C6F4S](4-C6F5O)C6F3NO2 (13), is slowly sublimed
at 80 °C/0.01 Torr. The less volatile 13 sublimes at 130 °C/0.01 Torr
(26%, mp 103-105 °C).
O, 4), 397 (M+ - SO - Br, 18), 381 (M+ - SO2Br, 27), 362 (M+
-
SO2Br - F, 22), 353 (M+ - SO2Br - CO, 21), 303 (M+ - SO2Br -
CO - CF2, 14), 217 (CF3C6F4+, 28), 149 (C5F3S+, 33), 148 (C6F4
,
,
+
61), 137 (C4F3S+, 22), 117 (C5F3+, 45), 105 (C4F3+, 16), 93 (C3F3
+
19), 69 (CF3+, 29), 64 (SO2+, 87), 48 (SO+, 27). Anal. Calcd for
C13BrF11O3S: C, 29.73; F, 39.80. Found: C, 29.09; F, 38.8.
Reaction of 2 with Pentafluorobenzenes C6F5R (R ) NO2, CN,
CF3) and Pentafluoropyridine. To a mixture consisting of 0.5 mmol
of 2 and 1 mmol of pentafluoronitrobenzene, pentafluorobenzonitrile,
octafluorotoluene, or pentafluoropyridine in 5 mL of THF is added 1
mmol of anhydrous K2CO3 at 25 °C. After 1 h of stirring (19F NMR
monitoring), all volatile materials are removed in vacuum and the
residue is sublimed at 70-100 °C/0.01 Torr. The yields are 80% for
CF3C6F4OC6F4SC6F4NO2 (9, mp 125-127 °C, subl 80 °C/0.01 Torr),
82% for CF3C6F4OC6F4SC6F4CN (10, mp 108-110 °C, subl 100 °C/
0.01 Torr), 63% for CF3C6F4OC6F4SC6F4CF3 (11, mp 93-95 °C, subl
90 °C/0.01 Torr), and 71% for CF3C6F4OC6F4SC5F4N (12, mp 92-94
°C, subl 70 °C/0.01 Torr).
Spectral data for 2-[4′-(4′′-CF3C6F4O)C6F4S](4-C6F5O)C6F3NO2
(13): IR (Nujol/KBr) 1659 m, 1635 m, 1616 m, 1553 m (νasymNO2),
1518 s, 1495 s, 1464 s, 1410 w, 1368 m (νsymNO2), 1344 m, 1320 w,
1273 m, 1231 m, 1199 m, 1161 m, 1126 m, 1110 m, 1066 m, 1032 m,
990 s, 936 m, 882 m, 859 m, 809 w, 760 m, 718 m, 650 m cm-1 19F
;
NMR δ -56.2 (4′′-CF3, t, 3F, 4JF-F ) 22.2 Hz), -121.1 (3-F, m, 1F),
-131.8 (2′-F, m, 2F), -139.3 (3′′-F, m, 2F), -142.3 (6-F, m, 1F),
-143.9 (5-F, m, 1F), -153.9 (2′′-F, m, 2F), -154.7 (3′-F, m, 2F),
-156.2 (2′′′-F, m, 2F), -157.8 (4′′′-F, t, 1F, 3JF-F ) 21.9 Hz), -160.8
(3′′′-F, m, 2F) ppm; MS (EI) [m/e (species, intensity)] 771 (M+, 16),
752 (M+ - F, 7), 741 (M+ - NO, 44), 721 (M+ - CF2, 31), 706 (M+
- F - NO2, 2), 701 (M+ - CF3, 1), 687 (M+ - 2F - NO2, 2), 606
(M+ - CF3 - NO2 - CF2, 2), 574 (M+ - C6F5 - NO, 16), 554 (M+
- CF3C6F4, 11), 524 (M+ - CF3C6F4 - NO, 7), 474 (M+ - CF3C6F4
- NO - CF2, 100), 217 (CF3C6F4+, 5), 196 (OC6F4S+, 19), 149
(C5F3S+, 4), 69 (CF3+, 27). Anal. Calcd for C25F19NO4S: C, 38.93;
F, 46.80. Found: C, 39.00; F, 46.8.
Spectral data for 4-[4′-(4′′-CF3C6F4O)C6F4S]C6F4NO2 (9): IR
(Nujol/KBr) 1662 m, 1635 m, 1556 m (νasymNO2), 1509 s, 1485 s, 1404
w, 1348 m (νsymNO2), 1283 w, 1264 m, 1226 m, 1191 m, 1158 m, 1120
m, 1033 m, 1004 m, 979 m, 882 m, 860 m, 803 w, 792 w, 761 m, 718
m, 702 w, 652 w, 635 w cm-1 19F NMR δ -56.2 (4′′-CF3, t, 3F, 4JF-F
;
Reaction of Excess 2 with Pentafluorobenzenes C6F5R (R ) NO2,
CN). To a mixture consisting of 0.5 mmol of pentafluoronitrobenzene
or pentafluorobenzonitrile and 3 mmol of 2 in 10 mL of THF is added
3 mmol of anhydrous K2CO3 at 25 °C. The 19F NMR shows that,
after 1 h of stirring, no C6F5R or monosubstituted 9 or 10 is present.
After 2 days of stirring at 25 °C, the colorless precipitate (R ) NO2),
identified as the tris-substituted nitrobenzene (RFS)3C6F2NO2 14, is
filtered and washed with THF and water. When R ) CN, the solution
is filtered from the inorganic salts, and all volatile materials are removed
in vacuum. The remaining residue is washed with small portions of
ether. The yields are 20% for (CF3C6F4OC6F4S)3C6F2NO2 (14, mp
211-213 °C) and 35% for (CF3C6F4OC6F4S)3C6F2CN (15, mp 161-
163 °C, pale yellow).
) 21.6 Hz), -129.7 (3-F, m, 2F), -130.8 (2′-F, m, 2F), -139.2 (3′′-
F, m, 2F), -144.9 (2-F, m, 2F), -153.8 (2′′-F, m, 2F), -154.3 (3′-F,
m, 2F) ppm; MS (EI) [m/e (species, intensity)] 607 (M+, 4), 577 (M+
- NO, 19), 561 (M+ - NO2, 2), 413 (M+ - C6F4NO2, 1), 344 (M+
-
C6F4NO2 - CF3, 3), 217 (CF3C6F4+, 5), 196 (OC6F4S+, 19), 149
(C5F3S+, 4), 69 (CF3+, 27). Anal. Calcd for C19F15NO3S: C, 37.58;
F, 46.93. Found: C, 37.60; F, 47.1.
Spectral data for 4-[4′-(4′′-CF3C6F4O)C6F4S]C6F4CN (10): IR
(Nujol/KBr) 2242 w (νCtN), 1660 m, 1641 m, 1512 s, 1481 s, 1466 s,
1409 m, 1346 m, 1293 m, 1228 m, 1190 m, 1161 m, 1117 m, 1034 m,
997 m, 975 s, 881 m, 859 m, 843 m, 718 m, 657 w, 637 w cm-1
;
19F
4
NMR δ -56.2 (4′′-CF3, t, 3F, JF-F ) 21.6 Hz), -130.8 (2-F, 3-F,
2′-F, m, 6F), -139.2 (3′′-F, m, 2F), -153.8 (2′′-F, m, 2F), -154.4
(3′-F, m, 2F) ppm; MS (EI) [m/e (species, intensity)] 587 (M+, 100),
568 (M+ - F, 8), 518 (M+ - CF3, 1), 413 (M+ - C6F4CN, 5), 370
(M+ - CF3C6F4, 28), 354 (M+ - CF3C6F4O, 3), 217 (CF3C6F4+, 6),
196 (OC6F4S+, 1), 180 (C6F4S+, 3), 148 (C6F4+, 4), 124 (C5F2CN+, 4),
117 (C5F3+, 8), 93 (C3F3+, 4), 69 (CF3+, 4). Anal. Calcd for C20F15-
NOS: C, 40.90; F, 48.53. Found: C, 41.04; F, 48.3.
Spectral data for 2,4,6-[4′-(4′′-CF3C6F4O)C6F4S]3C6F2NO2 (14):
IR (Nujol/KBr) 1659 m, 1635 m, 1505 s, 1485 s, 1465 m, 1398 m,
1352 m (νsymNO2), 1344 m, 1282 w, 1230 s, 1189 m, 1154 m, 1122 m,
1035 w, 1000 m, 980 m, 881 m, 860 w, 848 w, 800 w, 719 m, 634 w
cm-1 19F NMR (C6D6) δ -56.1 (4′′-CF3, t, 9F, 4JF-F ) 21.6 Hz), -95.8
;
(3-F, m, 2F), -134.2 (2′-F, m, 6F), -140.3 (3′′-F, m, 6F), -155.4
(2′′-F, m, 6F), -155.8 (3′-F, m, 6F) ppm; MS (EI) [m/e (species,
intensity)] 1366 (M+ - NO, 100), 1347 (M+ - NO - F, 11), 1328
(M+ - NO - 2F, 4), 1327 (M+ - CF3, 4), 1114 (M+ - CF3C6F4O -
Spectral data for 4-[4′-(4′′-CF3C6F4O)C6F4S]C6F4CF3 (11): IR
(Nujol/KBr) 1658 m, 1647 m, 1512 m, 1500 s, 1482 s, 1430 m, 1344

CF3C6F4OC6F4 Group 14/16 Derivatives
Inorganic Chemistry, Vol. 36, No. 23, 1997 5229
NO - F, 5), 881 (M+ - 2CF3C6F4O - NO - F, 53). Anal. Calcd
for C45F35NO5S3: C, 38.72; F, 47.65. Found: C, 38.95; F, 47.4.
Spectral data for 2,4,6-[4′-(4′′-CF3C6F4O)C6F4S]3C6F2CN (15):
IR (Nujol/KBr) 2243 vw (νCtN), 1660 m, 1635 m, 1510 s, 1495 s,
1465 m, 1432 m, 1407 m, 1350 m, 1299 w, 1284 w, 1231 m, 1191 m,
1162 m, 1122 m, 1034 m, 1000 m, 982 m, 882 m, 859 m, 803 w, 718
(species, intensity)] 571 (M+, 100), 552 (M+ - F, 10), 397 (M+
-
C6F4CN, 15), 354 (M+ - CF3C6F4, 15), 217 (CF3C6F4+, 17), 174 (C6F4-
+
CN+, 13), 148 (C6F4+, 9), 124 (C5F2CN+, 7), 117 (C5F3+, 7), 93 (C3F3
,
4), 69 (CF3+, 7). Anal. Calcd for C20F15NO2: C, 42.05; F, 49.89.
Found: C, 40.64; F, 49.2.
Spectral data for 4-[4′-(4′′-CF3C6F4O)C6F4O]C5F4N (19): IR
(Nujol/KBr) 1650 m, 1644 m, 1515 s, 1466 s, 1429 m, 1354 m, 1311
m, 1276 m, 1231 m, 1194 m, 1169 m, 1158 m, 1115 m, 1104 m, 1043
m, 667 w, 655 w, 635 w cm-1
;
19F NMR δ -56.2 (4′′(2,6)-CF3, t, 6F,
4
4JF-F ) 21.6 Hz), -56.3 (4’’(4)-CF3, t, 3F, JF-F ) 21.6 Hz), -97.8
dp/-98.5 dt (3/5-F, 1F/1F, 4JF-F ) 15.3 Hz, 6JF-F ) 4.0 Hz), -131.5
(2’(4)-F, m, 2F), -131.7/-132.4 (2′(2/6)-F, m, 4F), -139.4 (3′′-F, m,
6F), -153.9 to -154.9 (2′′/3′-F, m, 12F) ppm; MS (EI) [m/e (species,
intensity)] 1375 (M+, 100), 1356 (M+ - F, 8), 1158 (M+ - CF3C6F4,
2), 1142 (M+ - CF3C6F4O, 2), 981 (M+ - CF2C6F4OC6F4 - S, 37),
962 (M+ - CF3C6F4OC6F4S, 28), 943 (M+ - CF3C6F4OC6F4S - F,
4). Anal. Calcd for C46F35NO3S3: C, 40.16; F, 48.34. Found: C,
40.11; F, 48.1.
m, 992 s, 972 s, 960 m, 880 m, 790 w, 734 w, 722 m, 707 w, 670 w,
4
644 w, 630 w cm-1
;
19F NMR δ -56.2 (4′′-CF3, t, 3F, JF-F ) 21.7
Hz), -87.1 (2-F, m, 2F), -139.3 (3′′-F, m, 2F), -154.8 (2′/3′/2′′-F,
m, 6F), -157.4 (3-F, m, 2F) ppm; MS (EI) [m/e (species, intensity)]
547 (M+, 100), 528 (M+ - F, 9), 478 (M+ - CF3, 1), 397 (M+
-
C5F4N, 16), 330 (M+ - CF3C6F4, 22), 295 (M+ - CF3C6F4O - F, 4),
217 (CF3C6F4+, 33), 150 (C5F4N+, 26), 117 (C5F3+, 14), 69 (CF3+, 14).
Anal. Calcd for C18F15NO2: C, 39.51; F, 52.08. Found: C, 39.15; F,
51.6.
Preparation of CF3C6F4OC6F4OSiMe3. A mixture consisting of
2.5 mmol of 1 and 10 mmol of hexamethyldisilazane is stirred at 100-
120 °C for 17 h after having been stirred for 1 h at 25 °C. The excess
hexamethyldisilazane is removed in vacuum at 25 °C, and the residue
is distilled at 64 °C/0.01 Torr. The liquid solidifies to colorless,
hydrolyzable crystals in 93% yield (16, mp 29-31 °C).
Spectral data for 4-(4′-CF3C6F4O)C6F4OSiMe3 (16): IR (liquid
film/KBr) 2967 w (νCH), 1660 m, 1509 s, 1431 m, 1344 m, 1314 m,
1260 m, 1228 m, 1192 m, 1155 m, 1092 m, 1053 w, 1009 m, 992 m,
Reaction of 5 with Benzaldehyde. To a mixture consisting of 2
mmol of 5 and 6 mmol of benzaldehyde in 3 mL of THF, cooled to 0
°C, is added 1 drop of n-Bu4N+F- (1 M in THF), and the mixture is
stirred for 1 h. The 19F NMR of the mixture shows complete reaction
of 5. All volatile materials are removed in vacuum, and the residue is
treated with 3 mL of concentrated HCl and stirred for 5 h. After
extraction with ether/water, the combined ether phases are dried over
anhydrous Na2SO4 and all volatile materials are removed in vacuum.
The crude product is purified by column chromatography twice using
dichloromethane/hexane (1:2) as the eluent on silica gel (70-230 mesh).
The secondary alcohol CF3C6F4OC6F4CH(C6H5)OH (20) is obtained
as a viscous liquid in 36% yield.
876 m, 854 m, 761 w, 717 m, 634 w cm-1
;
19F NMR δ -56.1 (4′-CF3,
4
t, 3F, JF-F ) 21.6 Hz), -140.2 (3′-F, m, 2F), -155.2 (2′-F, m, 2F),
-157.8 (3-F, m, 2F), -158.3 (2-F, m, 2F); 1H NMR δ 0.29 (SiMe3, s,
9H) ppm; MS (EI) [m/e (species, intensity)] 470 (M+, 31), 455 (M+
-
CH3, 1), 451 (M+ - F, 4), 377 (C14H3F10O+, 3), 359 (M+ - F - (CH3)3-
SiF, 1), 222 (C6F4OSiMe2+, 23), 203 (C6F3OSiMe2+, 1), 133 (C5F3O+,
1), 117 (C5F3+, 2), 81 (CH3SiF2+, 5), 77 ((CH3)2SiF+, 32), 73 ((CH3)3-
Si+, 100). Anal. Calcd for C16H9F11O2Si: C, 40.86; H, 1.93. Found:
C, 40.74; H, 1.86.
Spectral data for 4-(4′-CF3C6F4O)C6F4CH(C6H5)OH (20): IR
(liquid film/KBr) 3610 m, 3353 s br (νOH), 3093 w, 3067 w, 3035 m
(νCH(Ar)), 2925 m (νCH), 1646 m, 1605 s, 1505 s, 1454 m, 1432 m,
1344 s, 1296 m, 1229 s, 1191 s, 1153 s, 1087 m, 1063 m, 1041 m, 992
s, 942 m, 910 m, 876 m, 844 m, 801 w, 778 m, 738 m, 717 m, 700 m,
668 m, 647 m, 616 m cm-1 19F NMR δ -56.3 (4′-CF3, t, 3F, 4JF-F
; )
Reaction of 16 with Pentafluorobenzenes C6F5X (X ) NO2, CN)
and Pentafluoropyridine. To a mixture consisting of 0.5 mmol of
16 and 1 mmol pentafluoronitrobenzene, pentafluorobenzonitrile, or
pentafluoropyridine in 5 mL of THF is added a catalytic amount of
CsF at 25 °C. After stirring (26 h/25 °C for C6F5NO2; 9 h/75 °C for
C6F5CN; 12 h/75 °C for C5F5N) (19F NMR monitoring), all volatile
materials are removed in vacuum and the residue is sublimed at 80
°C/0.01 Torr. When R ) NO2, considerable amounts (∼5-10%) of
the ortho isomer are formed and can be removed by slow sublimation
at 60 °C/0.01 Torr. The yields are 80% for CF3C6F4OC6F4OC6F4NO2
(17, mp 92-94 °C), 71% for CF3C6F4OC6F4OC6F4CN (18, mp 85-87
°C), and 75% for CF3C6F4OC6F4OC5F4N (19, mp 71-73 °C).
Compound 17 can be prepared in 67% yield in a manner similar to
that described for the sulfur derivative 9, using the phenol 1 and
anhydrous K2CO3. The reaction time is significantly longer (60 h/25
°C), as is the case for the trimethylsilyl ether 16.
21.6 Hz), -139.9 (3′-F, m, 2F), -142.7 (2-F, m, 2F), -154.7 (2′-F,
m, 2F), -156.2 (3-F, m, 2F); 1H NMR δ 7.5-7.3 (C6H5, m, 5H), 6.26
(CH, d, 1H, 3JH-H ) 7.4 Hz), 2.64 (OH, d) ppm; MS (EI) [m/e (species,
intensity)] 488 (M+, 49), 471 (M+ - OH, 4), 469 (M+ - F, 7), 411
(M+ - C6H5, 13), 409 (CF3C6F4OC6F4CO+, 20), 237 (M+ - CF3C6F4O
- H2O, 7), 217 (CF3C6F4+, 3), 176 (C6F4CO+, 6), 148 (C6F4+, 7), 117
+
(C5F3+, 3), 107 (C6H5CHOH+, 28), 105 (C6H5CO+, 20), 79 (C6H7
,
100), 78 (C6H6+, 26), 77 (C6H5+, 27), 69 (CF3+, 4). Anal. Calcd for
C20H7F11O2: C, 49.19; H, 1.45. Found: C, 48.23; H, 1.44.
Reaction of 5 with Pentafluorobenzaldehyde. The experiment is
carried out analogously to the reaction with benzaldehyde, but a more
complex product mixture is obtained, on the basis of 19F NMR (two
main components), requiring repeated column chromatography using
dichloromethane/hexane mixtures as eluents. The desired secondary
alcohol CF3C6F4OC6F4CH(C6F5)OH (21) exhibits a longer retention time
than CF3C6F4OC6F4CH(C6F5)OC6F4CHO (22) derived from reaction
of the alkoxide with the p-fluorine atom of pentafluorobenzaldehyde.
The yields are ∼10% for 21 (mp 95-97 °C) and ∼10% for 22 (viscous
liquid).
Spectral data for 4-[4′-(4′′-CF3C6F4O)C6F4O]C6F4NO2 (17): IR
(Nujol/KBr) 1661 m, 1650 m, 1562 m (νasymNO2), 1505 s, 1463 s, 1409
w, 1360 m (νsymNO2), 1344 m, 1311 w, 1290 m, 1269 w, 1228 m, 1187
m, 1171 m, 1160 m, 1113 m, 1015 s, 990 s, 928 w, 877 m, 826 w, 806
w, 786 w, 768 m, 738 w, 717 m, 664 w, 640 w cm-1
;
19F NMR δ
Spectral data for 4-(4′-CF3C6F4O)C6F4CH(C6F5)OH (21): IR
(Nujol/KBr) 3625 m, 3616 m, 3387 m br (νOH), 1651 m, 1505 s, 1464
s, 1342 m, 1309 m, 1278 m, 1225 m, 1199 m, 1170 m, 1124 m, 1079
m, 1051 m, 1002 m, 904 m, 874 m, 809 m, 791 w, 779 w, 752 m, 737
-56.2 (4′′-CF3, t, 3F, 4JF-F ) 21.6 Hz), -139.3 (3′′-F, m, 2F), -145.1
(2-F, m, 2F), -153.2 (3-F, m, 2F), -154.7 (2′′-F, m, 2F), -154.9 (2′/
3′-F, m, 4F) ppm; MS (EI) [m/e (species, intensity)] 591 (M+, 100),
575 (M+ - O, 2), 572 (M+ - F, 11), 561 (M+ - NO, 38), 545 (M+
- NO2, 18), 526 (M+ - NO2 - F, 2), 517 (M+ - NO2 - CO, 2), 397
(M+ - C6F4NO2, 82), 381 (M+ - OC6F4NO2, 3), 374 (M+ - CF3C6F4,
3), 362 (M+ - OC6F4NO2 - F, 4), 353 (M+ - OC6F4NO2 - CO, 7),
217 (CF3C6F4+, 46), 198 (CF2C6F4+, 10), 180 (OC6F4O+, 46), 148
(C6F4+, 40), 117 (C5F3+, 25), 69 (CF3+, 18). Anal. Calcd for C19F15-
NO4: C, 38.60; F, 48.21. Found: C, 38.67; F, 48.4.
m, 716 m, 673 m, 633 m, 596 w, 577 w cm-1
;
19F NMR δ -56.2
4
(4′-CF3, t, 3F, JF-F ) 21.5 Hz), -139.5 (3′-F, m, 2F), -142.9 (2-F,
3
m, 2F), -143.4 (2′′-F, m, 2F), -152.6 (4′′-F, tt, 1F, JF-F ) 21.0 Hz,
4JF-F ) 2.5 Hz), -154.4 (2′-F, m, 2F), -155.4 (3-F, m, 2F), -160.8
1
3
(3′′-F, m, 2F); H NMR δ 6.50 (CH, d, 1H, JH-H ) 10.0 Hz), 3.30
(OH, dp, 1H, 5JH-F ) 2.0 Hz) ppm; MS (EI) [m/e (species, intensity)]
578 (M+, 26), 561 (M+ - OH, 7), 559 (M+ - F, 10), 411 (M+
-
C6F5, 67), 409 (CF3C6F4OC6F4CO+, 18), 391 (M+ - C6F5 - HF, 9),
363 (M+ - C6F5 - HF - CO, 5), 217 (CF3C6F4+, 3), 197 (C6F5CHOH+,
Spectral data for 4-[4′-(4′′-CF3C6F4O)C6F4O]C6F4CN (18): IR
(Nujol/KBr) 2256 vw (νCtN), 1651 m, 1505 s, 1466 m, 1428 w, 1411
w, 1398 w, 1353 m, 1322 w, 1306 w, 1265 w, 1232 m, 1187 m, 1153
100), 195 (C6F5CO+, 52), 177 (C6F4COH+, 13), 167 (C6F5+, 14), 148
(C6F4+, 18), 137 (C5F4H+, 12), 117 (C5F3+, 27), 93 (C3F3+, 9), 69 (CF3
,
+
m, 1126 m, 1066 w, 1008 s, 990 s, 931 w, 879 m, 797 w, 722 m, 655
4
w, 637 w cm-1
;
19F NMR δ -56.1 (4′′-CF3, t, 3F, JF-F ) 21.6 Hz),
16). Anal. Calcd for C20H2F16O2: C, 41.54; H, 0.35. Found: C, 41.60;
H, 0.39.
Spectral data for 4-(4′-CF3C6F4O)C6F4CH(C6F5)OC6F4CHO
-131.0 (2-F, m, 2F), -139.3 (3′′-F, m, 2F), -153.4 (3-F, m, 2F),
-154.7 (2′′-F, m, 2F), -154.9 (2′/3′-F, m, 4F) ppm; MS (EI) [m/e

5230 Inorganic Chemistry, Vol. 36, No. 23, 1997
Krumm et al.
(22): IR (Nujol/KBr) 2727 m (νCH(dO)), 1717 m (νCdO), 1647 m, 1511
CHO - HF - F, 12), 256 (M+ - CF3C6F4OC6F4 - C5F3, 10), 217
(CF3C6F4+, 3), 193 (OC6F4CHO+, 8), 167 (C6F5+, 2), 137 (C5F4H+,
9), 117 (C5F3+, 11). Anal. Calcd for C27H2F20O3: C, 42.99; H, 0.27.
Found: C, 41.67; H, 0.34.
s, 1465 m, 1344 m, 1309 m, 1226 m, 1158 s, 1070 m, 1004 m, 973 m,
920 m, 875 m, 816 m, 736 w, 719 m, 672 w, 629 w, 577 w cm-1 19F
;
NMR δ -56.2 (4′-CF3, t, 3F, 4JF-F ) 22.2 Hz), -139.4 (3′-F, m, 2F),
-140.1 (2-F, m, 2F), -140.5 (2′′-F, m, 2F), -144.4 (2′′′-F, m, 2F),
-149.8 (4′′-F, tt, 1F, 3JF-F ) 21.0 Hz, 4JF-F ) 3.6 Hz), -154.4 (2′-F,
m, 2F), -154.7 (3-F, m, 2F), -155.2 (3′′′-F, m, 2F), -159.9 (3′′-F, m,
2F); 1H NMR δ 10.21 (CHO, m, 1H), 7.11 (CH, s, 1H) ppm; MS (EI)
[m/e (species, intensity)] 734 (M+ - HF, 1), 561 (M+ - OC6F4CHO,
100), 542 (M+ - OC6F4CHO - F, 1), 332 (M+ - CF3C6F4 - C6F5 -
Acknowledgment. We are grateful for the support of British
Nuclear Fuels plc and for generous gifts of chemicals by
Fluorochem Ltd. We thank Dr. Gary Knerr for obtaining the
mass spectral data.
2F, 17), 315 (M+ - CF3C6F4O - C6F5 - HF - F, 21), 305 (M+
CF3C6F4 - OC6F4CHO - HF - F, 6), 289 (M+ - CF3C6F4O - OC6F4-
-
IC970528D