Preparation of first examples of RFCCIF4 molecules. A study of the fluorination of selected 1-iodoalk-1-ynes with xenon difluoride/boron trifluoride

Article abstract of DOI:10.1016/j.jfluchem.2013.01.006

First examples of alk-1-yn-1-yliodine(V) molecules, CF₃CCIF ₄ and C₆F₁₃CCIF₄, were prepared by fluorination of the corresponding 1-iodoperfluoroalk-1-ynes with XeF₂ in 1,1,1,3,3-pentafluoro

Full text of DOI:10.1016/j.jfluchem.2013.01.006

Journal of Fluorine Chemistry 146 (2013) 98–104
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Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Preparation of first examples of RFCBBCIF4 molecules. A study of the fluorination of
selected 1-iodoalk-1-ynes with xenon difluoride/boron trifluoride
Vadim V. Bardin a, Hermann-Josef Frohn b,
*
a N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, SB RAS, Acad. Lavrentjev Avenue 9, 630090 Novosibirsk, Russian Federation
b Inorganic Chemistry, University of Duisburg-Essen, Lotharstrasse 1, D-47048 Duisburg, Germany
A R T I C L E I N F O
A B S T R A C T
Article history:
First examples of alk-1-yn-1-yliodine(V) molecules, CF3CBB CIF4 and C6F13CBB CIF4, were prepared by
fluorination of the corresponding 1-iodoperfluoroalk-1-ynes with XeF2 in 1,1,1,3,3-pentafluorobutane
(PFB) in the presence of BF3. The reaction of 1-iodo-2-(4-heptafluorotolyl)ethyne, 4-CF3C6F4CBB CI, with
XeF2 (1.5 equiv) and BF3 resulted in a mixture of 4-CF3C6F4CBB CIF2 (main product), 4-CF3C6F4CBB CIF4, and
trans-(4-CF3C6F4)CF55CFI, whereas under the action of 3 equiv of XeF2/BF3 a complex mixture of
polyfluoroorganics and IF5 resulted. Non-fluorinated C4H9CBB CI reacted with XeF2/BF3 preferentially
under fluorine addition across the triple bond and gave mainly C4H9CF2CF2I. The differing reactivity of
CnF2n+1CBB CI and C4H9CBB CI is in accordance with the experimentally proved different reactivity of the
triple bond in C6F13CBB CH and C4H9CBB CH toward XeF2/BF3 in PFB. Compound C6F13CBB CH was inert
whereas C4H9CBB CH was converted into C4H9CF2CF2H (main product) under the same conditions.
ß 2013 Elsevier B.V. All rights reserved.
Received 5 December 2012
Received in revised form 6 January 2013
Accepted 8 January 2013
Available online 16 January 2013
Keywords:
Perfluoroalkynyliodine tetrafluorides
1-Iodoperfluoroalkyne
1-Iodohex-1-yne
Xenon difluoride
Fluorination
NMR spectroscopy
1. Introduction
prepared from commercially available reagents by two general
routes. A three-step process which consists in (a) the addition of 1-
In the last review on the chemistry of polyvalent perfluoro-
organo halogene compounds in 2008 the absence of perfluoroalk-
ynyliodine(V) compounds was mentioned [1]. Up to now
compounds RCBB C–IX4 are unknown in general (R represents
any organic group and X any organic or inorganic ligand). The
addition of fluorine to the iodine atom in 1-iodoalkynes seemed to
be a perspective route to alk-1-yn-1-yliodine tetrafluorides. The
perfluorinated 1-iodoalkynes, CF3CBB CI, C6F13CBB CI, 4-CF3C6F4CBB CI,
and the hydrocarbon compound, C4H9CBB CI, were chosen as
iodoalkyne starting materials and xenon difluoride was studied
as fluoro-oxidizer especially in the presence of the weak Lewis acid
boron trifluoride in the solvent PFB. The latter was shown to resist
toward strong fluoro-oxidizers like BrF3 [2], (BrF3 + Br2) [3], IF7 [4],
and XeF2 in the presence of both RFBF2 [5–7] and BF3 (Scheme 1).
iodoperfluoroalkane to trimethylsilylacetylene, (b) the elimination
of HI with t-BuOK, and (c) the iododesilylation of CnF2n+1CBB CSiMe3
with iodine [8]. An improved modification proceeds via
CnF2n+1CH55CISi(i-Pr)3 obtained from CnF2n+1I and HCBB CSi(i-Pr)3,
and the subsequent treatment of the alkenylsilane with [Bu4N]F in
THF and finally with iodine [9]. A disadvantage of this method is the
application of expensive ethynyltrialkylsilane. The second approach
is based on the transformation of 1-H-perfluoroalk-1-ynes. Initially,
alkynes CnF2n+1CBB CH were converted into CnF2n+1CX55CHI by
addition of XI, namely I2 (X = I), ICl (X = Cl), or ICN (X = CN). In a
subsequent step the 1-iodopolyfluoroalkenes were treated with
KOH in MeOH to give CnF2n+1CBB CI (yields were not reported) [10].
We performed the reaction of C6F13CBB CH with ICl in HOAc as
described[10]and obtainedC6F13CCl55CHIcontaminatedwithca. 6%
of C6F13CI55CHI. However, the treatment of thatmixturewithKOH in
MeOH resulted in
a 3-component mixture of C6F13CBB CI,
2. Results and discussion
C6F13CCl55CHI, and C6F13C(OMe)55CHI (1:2:1) (Scheme 2). Probably,
the conversion of C6F13CCl55CHI was incomplete because only the
(Z)-C6F13CCl55CHI isomer undergoes HI elimination under these
conditions (for a more detailed discussion see [9]).
An alternative route from CnF2n+1CBB CH to CnF2n+1CBB CI is based
on the intermediate formation of CnF2n+1CBB CM (M = metal) which
is finally reacted with iodine. For example, C6F13CBB CI was obtained
by the reaction of C6F13CBB CMgBr with iodine (80% yield) [11]. We
reproduced this synthesis and prepared C6F13CBB CI in 62% isolated
2.1. Preparation of the starting materials RfCBB CI
In contrast to 1-iodoalk-1-ynes, their perfluorinated analogs are
less studied. 1-Iodoperfluoroalk-1-ynes, CnF2n+1CBB CI, can be
* Corresponding author. Tel.: +49 203 379 3310; fax: +49 203 379 2231.
E-mail address: h-j.frohn@uni-due.de (H.-J. Frohn).
0022-1139/$ – see front matter ß 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jfluchem.2013.01.006

V.V. Bardin, H.-J. Frohn / Journal of Fluorine Chemistry 146 (2013) 98–104
PFB
99
>2 XeF2, PFB, BF3 (trace)
CF3CH2CF2CH3 + XeF2 + BF3
no reaction
CF3C CI
CF3C CIF2
24 C, 1 h
5 – 24 C
Scheme 1.
>2 XeF2, PFB, BF3 (excess)
ICl, HOAc
KOH, MeOH
22 C, 2 h
CF3C CI
CF3C CIF4
87%
C6F13C CH
C6F13CCl=CHI + C6F13CI=CHI
55 – 60 C, 4 h
24 C
C6F13C CI + C6F13CCl=CHI + C6F13C(OMe)=CHI (1:2:1)
Scheme 4.
Scheme 2.
evolved and a thick suspension was formed. After 1 h at ꢀ24 8C the
precipitate dissolved and the solution contained perfluorooct-1-
yn-1-yliodine difluoride, C6F13CBB CIF2, perfluorooct-1-yn-1-ylio-
dine tetrafluoride, C6F13CBB CIF4, (1.6:1) besides traces of the
starting material C6F13CBB CI. In a larger excess of XeF2/BF3
C6F13CBB CIF4 was obtained in 76% yield (Scheme 5).
LiC CSiMe3, ether
KOH, aq MeOH
C6F5CF3
4-CF3C6F4C CSiMe3
54%
1. BuLi, ether, hexanes
4-CF3C6F4C CH
36%
4-CF3C6F4C CI
93%
The reaction of 1-iodo-2-(4-heptafluorotolyl)ethyne with XeF2
(1.5 equiv) and BF3 in PFB at 0–24 8C resulted in a mixture of (4-
heptafluorotolyl)ethynyliodine difluoride, (4-heptafluorotolyl)-
ethynyliodine tetrafluoride, 1-iodoperfluoro-2-(4-tolyl)ethene,
and IF5 (molar ratio 64:3:15:18) besides remaining starting
material, 4-CF3C6F4CBB CI (relative molar fraction 13), and minor
amounts of not fully identified 4-CF3C6F4X compounds. Products
with X = CF2CF2I, CF2CF3, CF = CFIFn, and CF2CF2IFn (n = 2, 4) were
not detected by 19F NMR spectroscopy (Scheme 6).
2. I2
Scheme 3.
yield. Although the short-chain 1-iodoperfluoroalkynes could be
prepared similarly, their isolation from the solution in ether is
problematic. Recently we have reported two alternative syntheses
of 1-iodotrifluoropropyne: (a) by treatment of a suspension of
CF3CBB CZnCl (derived from CF3CCl55CCl2 and Zn [12]) in N,N-
dimethylacetamide (DMAc) with iodine [13,14] and (b) by
iododeboration of [Bu4N][CF3CBB CBF3] with iodine chloride in
CH2Cl2 [3]. For the current work, the last method was modified and
a solution of CF3CBB CI was prepared in 1,1,1,3,3-pentafluorobutane.
Until now the family of 1-iodo-2-perfluoroarylethynes was only
represented by C6F5CBB CI obtained from C6F5CBB CSnMe3 and I2 in
CCl4 (yield was not given) [15]. We prepared 1-iodo-2-(4-
heptafluorotolyl)ethyne, 4-CF3C6F4CBB CI, by the reaction sequence
presented in Scheme 3.
Attempts to increase the yield of 4-CF3C6F4CBB CIF4 by using an
excess of XeF2 and BF3 resulted in a complex mixture of 4-CF3C6F4X
compounds besides IF5. Neither (4-heptafluorotolyl)ethynyliodine
difluoride nor tetrafluoride were still present. The main compo-
nent in the 19F NMR spectrum was assigned to 4-CF3C6F4CF55CFIF4
but a reliable identification of the other products was not possible.
At least two compounds contained 4-CF3C6F4 and IF4 fragments
(
19F NMR). Oxidation with KMnO4 in acetone yielded mainly 4-
CF3C6F4CO2H together with not fully identified products (19
F
NMR). In the past it was found that the compounds C6F5CBB CBF2
and [C6F5CBB CXe][BF4] with an asymmetric moiety at the C–C triple
bond which includes one perfluoroaryl group and one strong
electron-withdrawing substituent are relatively unstable and are
easily transformed to not fully identified perfluoroaryl-containing
products. In contrast, their perfluoroalkynyl analogs CnF2n+1CBB CX
(X = BF2, Xe+) are significantly more stable [7,16].
Non-fluorinated 1-iodohex-1-yne did not react with XeF2 in PFB
at room temperature in the absence of BF3 and thereby it showed a
comparable property to 1-iodoperfluoroalkynes, CF3CBB CI and
C6F13CBB CI. Even in the presence of activating BF3 no products of
fluorination at iodine in C4H9CBB CI were obtained. Instead of
C4H9CBB CIF4 the reaction gave 1-iodo-1,1,2,2-tetrafluorohexane
besides several not fully identified fluoroorganic compounds.
Whether difluoroalkene, C4H9CF = CFI, nor any RIFn compound
(n = 2, 4) was observed by 19F NMR spectroscopy and iodine
pentafluoride was not present too (Scheme 7).
2.2. Reactions of RFCBB CI and RCBB CI with XeF2
The combination of XeF2 with BF3 allows the polarization of
XeF2, best represented by FXe–FÁ Á ÁBF3. The latter is a stronger
fluoro-oxidizer than XeF2 itself. Preliminary experiments had
shown that CF3CBB CI and C6F13CBB CI did not react with xenon
difluoride in PFB whether at 24 8C over 1 h nor at 45 8C over 4 h,
respectively. The reaction of XeF2 (2.5 equiv) with CF3CBB CI in PFB
at 5–24 8C in the presence of a small amount of BF3 (<0.1 equiv)
gave trifluoroprop-1-yn-1-yliodine difluoride, CF3CBB CIF2.
With XeF2 (2.5 equiv) and BF3 in excess, CF3CBB CI was converted
to trifluoroprop-1-yn-1-yliodine tetrafluoride, CF3CBB CIF4
(Scheme 4).
When the BF3 gas was bubbled into a suspension of XeF2
(2.5 equiv) in a solution of C6F13CBB CI in PFB at 0–24 8C, Xe0 gas
>1 XeF2, BF3, PFB
C6F13C CIF2 + C6F13C CIF4 C6F13C CIF4
>2 XeF2, BF3, PFB
C6F13C CI
0 – 24
C
76%
Scheme 5.
1.5 XeF2, BF3, PFB
4-CF3C6F4C CI
4-CF3C6F4C CIF2 + 4-CF3C6F4C CIF4
5 – 24
C
+ trans-(4-CF3C6F4)CF=CFI + IF5 + 4-CF3C6F4C CI + ...
Scheme 6.

100
V.V. Bardin, H.-J. Frohn / Journal of Fluorine Chemistry 146 (2013) 98–104
2 XeF2, BF3, PFB
C4H9C CI
C4H9CF2CF2I + …
43%
2 – 24 C
Scheme 7.
2 XeF2, BF3, PFB
24 C, 1 h
C6F13C CH
C4H9C CH
no reaction
2 XeF2, BF3, PFB
2 – 24 C, 1 h
C4H9CF2CF2H + C4H9CH2CF2H + C4H9CF2CH3 +...
Scheme 8.
It is worth noting that non-functionalized hex-1-yne reacted
could be transferred to perfluoroalk-1-yn-1-yliodine tetrafluor-
ides, which were unknown up to now. In the case of the starting
materials CnF2n+1CBB CI (n = 1, 6) the triple bond withstands the
addition of fluorine so that the fluorination of I(I) to I(V) proceeds
with XeF2 and BF3 in PFB even under fluorine addition across the
triple bond forming 1,1,2,2-tetrafluorohexane (major), 1,1-difluoro-
hexane, and 2,2-difluorohexane (PFB was not the source of HF)
besides a larger number products in minor quantities. In contrast to
hex-1-yne, 1-H-perfluorooct-1-yne did not undergo an analogous
reaction (Scheme 8).
Scheme 8 underlines that the triple bond in C4H9CBB CX
undergoes more easy fluorination with respect to the perfluori-
nated analog. A comparison of the partial charges (Natural
Population Analysis Charges, RHF/LANL2DZ) of the 1-iodoalk-1-
ynes, CF3CBB CI (A) and CH3CBB CI (B), reveals (a) that the triple bond
in B is significantly more polar than in A (partial charges/eÀ in A:
C-1 À0.25, C-2 À0.16; in B: C-1 À0.40, C-2 0.03) and (b) that the
partial charge on iodine in A (0.39 eÀ) is only 0.07 eÀ more positive
than in B.
In a previous communication [17], we described the broadening
of the IF4 signal in the 19F NMR spectra of RFIF4 (RF = perfluorinated
alkyl, alkenyl, and cycloalkenyl) in the presence of BF3 and the
disappearance of the spin–spin coupling between the IF4 fluorine
nuclei and CFx fluorine nuclei of the perfluoroorgano group. A
plausible explanation of these phenomena is an acid–base
interaction between BF3 (fluoride acceptor) and RFIF4 (fluoride
donor). It is very likely, that a related acid–base interaction
between the positive iodine center (fluoride acceptor) of the IF4
group and the fluorine moiety (fluoride donor) of the IF2 group
takes place in mixtures of RFCBB CIF2 and RFCBB CIF4. The full width at
half-maximum height n1/2 of the IFx resonances in the 19F NMR
spectra of the individual compounds are 16 Hz for C6F13CBB CIF4
(CFCl2CH3, 24 8C), 9–10 Hz for CF3CBB CIF2 and CF3CBB CIF4 (PFB,
24 8C). In contrast, solutions which contained a mixture of
RFCBB CIF2 and RFCBB CIF4 showed broadened resonances of the IF2
exclusively. CnF2n+1CBB CIF4 (n = 1, 6) as prototypes with
a
perfluoroalkyl group at the CBB C fragment could be isolated in
good yields. C6F13CBB CIF4 is characterized by its significant
oxidation property. Thus the relatively inert solvent CCl2FCH3
was attacked by C6F13CBB CIF4 when a solution was stored over a
longer time (28 h). The triple bond in CnF2n+1CBB CIF2 showed a
similar trend of reactivity as it was found for CnF2n+1CBB CI. No
fluorination of CnF2n+1CBB CIF2 to CnF2n+1CF55CFIF2 or CnF2n+1CF2–
CF2IF2 was observed when CnF2n+1CBB CIF2 was treated with less
than 2 equiv of XeF2/BF3 in PFB. 4-CF3C6F4CBB CI with an aryl group
at the iodoethynyl moiety reacted preferentially at iodine and not
at the triple bond or the aromatic moiety. But perfluoro(arylethyn-
yl)iodine tetrafluoride, 4-CF3C6F4CBB CIF4, was only formed as a
minor product besides 4-CF3C6F4CBB CIF2 (main product) and trans-
4-CF3C6F4CF55CFI when XeF2/BF3 was not used in excess. With
XeF2/BF3 in excess 4-CF3C6F4CBB CIF4 was converted into several not
fully identified compounds with CF3C6F4 and IF4 fragments. Both
non-fluorinated alkynes, C4H9CBB CI and C4H9CBB CH, were trans-
formed with XeF2/BF3 into C4H9CF2CF2X (X = I and H (main
products), respectively) and demonstrate the preferential fluori-
nation of the CBB C moiety.
4. Experimental part
4.1. General
NMR spectra were recorded on the Bruker spectrometers
AVANCE 300 (300.13 MHz, 1H; 282.40 MHz, 19F), AVANCE 400
(100.61 MHz, 13C), and DRX 500 (125.76 MHz, 13C; 99.36 MHz,
29Si). The chemical shift values are referenced to TMS (1H, 13C, and
and IF4 group. IF2: RF = CF3,
2 = 1176 Hz; RF = 4-CF3C6F4,
2 = 33 Hz; RF = C6F13 1/2 = 233 Hz; RF = 4-CF3C6F4,
In the 13C NMR spectra of a mixture of RFCBB CIF2 with RFCBB CIF4
(RF = CF3, C6F13) the coupling constants 2J(C-1, IFn) and 3J(C-2, IFn)
were absent. This observation contrasts the behavior of the pure
individual compounds.
n
1/2 = 1147 Hz; RF = C6F13
1/2 = 646 Hz; IF4: RF = CF3, n1/
1/2 = 38 Hz.
, n1/
n
,
n
n
29Si) and CCl3F
(
19F, with C6F6 as secondary reference
(À162.9 ppm)), respectively. When the 1H, 19F, and 13C NMR
spectra were measured in CF3CH2CF2CH3 (PFB) the bold marked
resonances of the solvent were used as secondary reference: d
(1H)
2.70 (tq, CH2), 1.69 (t, CH3);
d(
13C) 123.7 (CF3), 119.6 (CF2), 41.1 (CH2), 22.9 (CH3). The
d
(
19F) S61.5 (tt, CF3), À86.3 (m, CF2);
3. Conclusion
substituents which are bonded at C-n of the alk-1-yne are denoted
as Hn and Fn. In case of 4-CF3C6F4CBB CX compounds the position of F
and C of the aryl moiety are presented in italic, e.g., F2,6 at C-2,6.
GC–MS analysis was performed on a Hewlett-Packard 1800A
instrument with a HP-5MS column. High resolution mass spectra
were recorded on a Thermo Scientific DFS spectrometer in the EI
mode (70 eV). GC–MS as well as elemental analysis was performed
in the Collective Service Center, SB RAS (Novosibirsk).
The previously elaborated methodology to prepare perfluoro-
organyliodine tetrafluorides, RFIF4 (RF = perfluorinated alkyl, alk-
1-enyl, cycloalk-1-enyl group) [17] by fluorination of the
corresponding perfluoroorganyl iodides with the reagent combi-
nation XeF2 and BF3 (weak Lewis acid) in the weakly coordinating
solvent PFB which represents a good stability toward oxidizers

V.V. Bardin, H.-J. Frohn / Journal of Fluorine Chemistry 146 (2013) 98–104
101
1,1,1,3,3-Pentafluorobutane (PFB) (Solvay Fluor und Derivate
C-2), 117–106 (C6F13). 13C{1H} NMR (PFB):
d
87.3 (t, 3J(C-1,
GmbH) was stored over molecular sieves 3 A before use. The
F3) = 6 Hz, C-1), the signal of C-2 was too weak to be observed, 117–
106 (C6F13).
˚
solvents (C2H5)2O, CCl2FCH3, CCl4, CD2Cl2 were dried before use.
C6F5CF3 (P&M), HCBB CSiMe3 (Aldrich), 2.5 M BuLi in hexanes
(Acros), ICl (Fluka) were used as supplied. [Bu4N][CF3CBB CBF3] [3],
C4H9CBB CI [18], and BF3 [19] were prepared according to reported
procedures. The solubility of BF3 in PFB was determined to 9.9 mg
(0.146 mmol) per mL at 0 8C.
4.4. Dehydrochlorination of C6F13CCl55CHI
A round-bottom flask equipped with a magnetic stirring bar and
reflux condenser was charged with
a
mixture (1 g) of
All manipulations with xenon difluoride and RFCBB CIF4 were
performed in traps prepared from FEP tubes (block copolymer of
tetrafluoroethylene and hexafluoropropylene; o.d. = 4.1 mm,
i.d. = 3.5 mm or o.d. = 9.0 mm, i.d = 8.0 mm) or PFA tubes (block
copolymer of tetrafluoroethylene and perfluoroalkoxytrifluor-
oethylene; o.d. = 14.0 mm, i.d. = 11.7 mm) under an atmosphere
of dry argon.
C6F13CCl55CHI (94%) and C6F13CI55CHI (6%) in MeOH (1 mL). A
solution of KOH (0.123 g, 2 mmol) in MeOH (4 mL) was added. The
reaction mixture was stirred at ꢀ22 8C for 2 h, diluted with water
(1:1) and extracted with PFB (3 mL). The extract was washed with
water and dried with MgSO4. The solution contained C6F13CBB CI
(0.4 mmol), C6F13CCl55CHI (0.8 mmol), and C6F13C(OMe)55CHI
(0.4 mmol) (1H, 19F NMR, GC–MS).
C6F13CBB CH was prepared in an analogous manner to
CnF2n+1CBB CH (n = 3, 4) [20].
C6F13C(OMe)55CHI. 1H NMR (PFB): 6.95 (s, 1H, H1), 3.74 (s, 3H,
d
OCH3). 19F NMR (PFB):
d
À80.0 (m, 3F, F8), À95.8 (t, 4J(F3,
C6F13CBB CH. 1H NMR (neat):
1H NMR (PFB):
(CDCl3):
d
2.89 (t, 4J(H1, F3) = 5.5 Hz, 1H, H1).
F5) = 15 Hz, 2F, F3), À119.7 (m, CF2), À120.9 (m, CF2), À121.2 (m,
CF2), À124.7 (m, 2F, F7).
d
3.02 (t, 4J(H1, F3) = 5.5 Hz, 1H, H1) {lit. 1H NMR
3.07 (t, 4J(H1, F3) = 5.7 Hz, 1H) [21]}. 19F NMR (neat):
d
d
À80.4 (t, 4J(F8, F6) = 9 Hz, 3F, F8), À98.4 (dt, 4J(F3, H1) = 5 Hz, 4J(F3,
4.5. Preparation of C6F13CBB CI
F5) = 12 Hz, 2F, F3), À119.9 (m, CF2), À121.6 (m, 2CF2), À125.2 (m,
2F, F7). 19F NMR (PFB):
d
À80.0 (t, 4J(F8, F6) = 9 Hz, 3F, F8), À97.7 (t,
A three-necked flask equipped with a magnetic stirring bar, a
septum inlet, and a reflux condenser topped with a T-piece
connected with a bubbler and an argon inlet, was charged with
ether (12 mL) and C6F13CBB CH (3.2 g, 9.3 mmol). A solution of
BuMgBr in ether (1.6 M, 6 mL, 9.6 mmol) was added dropwise with
a syringe within 10 min. The solution was refluxed for 1 h, cooled
to ꢀ20 8C and finely grounded and dried iodine (2.56 g, 10 mmol)
was added in portions. The reaction mixture was stirred at ꢀ20 8C
for 15 h and poured into a diluted aq solution of Na2S2O3. The
organic phase was separated and the aqueous one was extracted
with ether (20 mL). The combined extracts were washed with
water and dried with MgSO4. The solvent was removed under
reduced pressure at ꢀ20 8C and the residue was distilled in vacuum
to yield C6F13CBB CI (2.72 g, 62%) (bp 72–73 8C/49 hPa) {lit. bp 48–
55 8C/20 hPa [11]}.
4J(F3, F5) = 11 Hz, 2F, F3), À119.7 (m, CF2), À121.3 (m, 2CF2), À124.9
(m, 2F, F7) {lit. 19F NMR (CDCl3):
d
À81.33 (3F), À99.76 (2F),
À121.83 (2F), À123.25 (2F), À123.39 (2F), À126.69 (2F) [21]}.
13C{19F} NMR (neat):
d 117.2 (CF3), 110.6 (CF2), 110.1 (CF2), 109.6
(CF2), 108.3 (CF2), 106.3 (d, 3J(C-3, H1) = 4 Hz, C-3), 78.9 (d, 1J(C-1,
H1) = 261 Hz, C-1), 69.2 (d, 2J(C-2, H1) = 51 Hz, C-2).
4.2. Inertness of CF3CH2CF2CH3 toward XeF2 in the presence of BF3
Xenon difluoride (69 mg, 0.40 mmol) was dissolved in PFB
(0.8 mL) and BF3 (0.5 mmol) was bubbled slowly at 24 8C for 0.5 h.
The colorless solution was stirred for further 0.5 h before a probe
was taken under an atmosphere of dry argon. The 19F NMR
spectrum showed resonances of PFB, XeF2, and no further signals.
C6F13CBB CI. 19F NMR (PFB):
d
À80.0 (t, 4J(F8, F6) = 9 Hz, 3F, F8),
4.3. Preparation of C6F13CCl55CHI
À96.8 (t, 4J(F3, F5) = 15 Hz, 2F, F3), À119.0 (CF2), À120.1 (CF2),
À121.2 (CF2), À124.7 (m, 2F, F7) {lit. 19F NMR:
d
À97.8 (2F, F3) [11]}.
A round-bottom flask equipped with a magnetic stirring bar and
a reflux condenser was charged with ICl (7.5 g, 46 mmol) and
anhydrous HOAc (5 mL). After stirring for 10 min C6F13CBB CH
(3.2 g, 9.3 mmol) was added to the suspension. The reaction
mixture was stirred at 55–60 8C (bath) for 4 h, cooled to ꢀ22 8C,
diluted with water and treated with an aq solution of Na2SO3. The
organic phase was separated and the aqueous one was extracted
with ether (3Â 6 mL). The combined extracts were washed with
water and dried with MgSO4. The solvent was removed under
reduced pressure at 40 8C (bath) to yield a yellowish oil (3.2 g)
which consisted of C6F13CCl55CHI (94%) and C6F13CI55CHI (6%) (1H,
19F NMR, GC–MS).
13C NMR (neat): 119–108 (C5F11), 106.4 (tt, 1J(C-3, F3,3) = 243 Hz,
d
2J(C-3, F4,4) = 33 Hz, C-3), 80.7 (t, 2J(C-2, F3,3) = 37 Hz, C-2), 16.4 (t,
3J(C-1, F3,3) = 10 Hz, C-1).
4.6. Preparation of CF3CBB CI
A solution of ICl (523 mg, 3.2 mmol) in PFB (3 mL) was added
dropwise to a solution of [Bu4N][CF3CBB CBF3] (3.2 mmol) in PFB
(5.3 mL) at ꢀ20 8C and stirred for 1 h. PFB and CF3CBB CI were
distilled off in static vacuum (66–106 hPa) and collected in a trap
cooled with liquid nitrogen. The distillate was melted and the set
up was filled with dry argon and finally warmed to ꢀ20 8C. The PFB
solution contained CF3CBB CI (0.58 mmol, 18%) (19F NMR, with the
internal standard for integration C4F9Br).
C6F13CCl55CHI. 1H NMR (PFB):
d
7.31 (t, 4J(H1, F3) = 1.3 Hz, 1H,
H1) {lit. 1H NMR (CCl4):
d
7.38 [10]}. 19F NMR (PFB): À80.0 (t, 4J(F8,
F6) = 10 Hz, 3F, F8), À97.1 (t, 4J(F3, F5) = 15 Hz, 2F, F3), À117.6 (m,
CF2), À120.1 (m, CF2), À121.1 (m, CF2), À124.8 (m, 2F, F7) {lit. 19
F
4.7. Preparation of 4-CF3C6F4CBB CSiMe3
NMR (CCl4):
d
À99.3 (2F, F3) [10]}. 13C NMR (PFB):
d
132.5 (td, 3J(C-
1, F3) = 5 Hz, 1J(C-1, H1) = 202 Hz, C-1), 80.6 (t, 2J(C-2, F3) = 27 Hz,
A three-necked flask equipped as described in Section 4.5 was
charged with ether (25 mL) and HCBB CSiMe3 (1.4 g, 12.5 mmol).
The solution was cooled to 5–10 8C and BuLi in hexanes (1.25 M,
11 mL, 13 mmol) was added with a syringe. After stirring for
15 min, C6F5CF3 (2.5 g, 10.5 mmol) was added with a syringe. The
turbid solution was stirred at ꢀ20 8C for 36 h, refluxed for 3 h,
cooled to ꢀ20 8C, and poured into water. The organic phase was
washed with water and dried with MgSO4. The solvent was
removed under reduced pressure and the residue was distilled in
C-2), 117–106 (C6F13). 13C{1H} NMR (PFB):
d
132.6 (t, 3J(C-1,
F3) = 5 Hz, C-1), 80.8 (t, 2J(C-2, F3) = 27 Hz, C-2), 117–106 (C6F13).
C6F13CI55CHI. 1H NMR (PFB):
{lit. 1H NMR (CCl4):
d
8.24 (t, 4J(H1, F3) = 2.1 Hz, 1H, H1)
d
8.27 [10]}. 19F NMR (PFB):
d
À80.0 (t, 4J(F8,
F6) = 10 Hz, 3F, F8), À96.4 (t, 4J(F3, F5) = 15 Hz, 2F, F3), the signals of
4 CF2 groups overlapped with CF2 signals of C6F13CCl55CHI {lit. 19
F
NMR (CCl4):
d
À98.7 (2F, F3) [10]}. 13C NMR (PFB):
d
87.2 (td, 3J(C-1,
F3) = 6 Hz, 1J(C-1, H1) = 195 Hz, C-1), 81.8 (t, 2J(C-2, F3) = 28 Hz,

102
V.V. Bardin, H.-J. Frohn / Journal of Fluorine Chemistry 146 (2013) 98–104
vacuum (bp 45–47 8C/60–63 hPa) to yield 4-CF3C6F4CBB CSiMe3
(1.8 g, 54%), mp 34–35 8C after crystallization from MeOH.
1-Trimethylsilyl-2-(4-heptafluorotolyl)ethyne, 4-CF3C6F4C2BB
occurred (19F NMR). After the slow bubbling of BF3 for 1 h a
solution was formed which contained CF3CBB CIF4 and IF5 (83:17)
(
19F NMR). The solvent and IF5 were removed in vacuum at 24 8C to
C1SiMe3. 1H NMR (CD2Cl2):
d
0.29 (s, 9H, SiMe3). 19F NMR
give CF3CBB CIF4 (129 mg, 87%) (pale yellow solid).
(CD2Cl2):
d
À57.7 (t, 4J(CF3, F3,5) = 22 Hz, 3F, CF3), À136.3 (m, 2F,
Xenon difluoride (244 mg, 1.44 mmol) was added to a solution
of CF3CBB CI (0.58 mmol) in PFB (2 mL). The suspension was stirred
at 5 8C for 10 min. A cold (5 8C) saturated solution of BF3 in PFB
(0.7 mL) was added to the suspension which was subsequently
stirred at 5 8C for 10 min and at 24 8C for 1 h. A solution resulted
which was concentrated under reduced pressure to a volume of
1 mL. The 13C and 19F NMR spectra showed resonances of
CF3CBB CIF2 and unreacted XeF2 (1:1). The solution was diluted
with PFB (2 mL) and BF3 was bubbled at 24 8C for 1 h. To destroy
the excess of XeF2, C6F6 (0.4 mmol) was added. After 30 min
the volatiles were removed under reduced pressure (27–40 hPa).
The solid residue was dissolved in PFB (0.5 mL). The 13C and 19F
NMR spectra showed signals of CF3CBB CIF2, CF3CBB CIF4, IF5
(17:56:28).
F2,6), À142.6 (m, 2F, F3,5) {lit. 19F NMR (CDCl3):
À56.8 (t, J = 21 Hz,
d
3F, CF3), À134.8 (m, 2F), À141.9 (m, 2F) [22]}. 13C{1H} and 13C{19F}
NMR (CD2Cl2): d
148.0 (dddd, 1J(C, F) = 254 Hz, 2J(C, F) = 14 Hz, 3J(C,
F) = 4 Hz, 4J(C, F) = 4 Hz, C-2,6), 144.7 (dddd, 1J(C, F) = 259 Hz, 2J(C,
F) = 16 Hz, 3J(C, F) = 4 Hz, 4J(C, F) = 4 Hz, C-3,5), 121.4 (q, 1J(CF3,
F) = 274 Hz, CF3), 113.8 (dtdecet, 1J(C-1, Si) = 75 Hz, 4J(C-1,
F2,6) = 4 Hz, 3J(C-1, H) = 3 Hz, C-1), 110.0 (tq, 2J(C-4, F3,5) = 13 Hz,
2J(C-4, CF3) = 35 Hz, C-4), 109.3 (t, 2J(C-1, F2,6) = 18 Hz, C-1), 87.5 (t,
3J(C-2, F2,6) = 3 Hz, C-2), À0.54 (dq, 1J(C, Si) = 57 Hz, 1J(C,
H) = 120 Hz, CH3). 29Si{1H} NMR (CD2Cl2):
1) = 75 Hz, 1J(Si, CH3) = 57 Hz).
d
À14.5 (dd, 1J(Si, C-
Anal. Calcd for C12H9F7Si: C, 45.9; H, 2.9; F, 42.4. Found: C, 46.0;
H, 3.0; F, 42.4.
CF3CBB CIF2. 19F NMR (PFB):
d
À51.7 (s, 3F, F3), À154.0 (s, n1/2
4.8. Preparation of 4-CF3C6F4CBB CH
= 9 Hz, IF2). 13C NMR (PFB): 113.0 (q, 1J(C-3, F3) = 261 Hz, C-3),
d
95.7 (tq, 3J(C-2, IF2) = 13 Hz, 2J(C-2, F3) = 56 Hz, C-2), 46.3 (tq, 2J(C-
1, IF2) = 23 Hz, 3J(C-1, F3) = 8 Hz, C-1).
An aqueous solution of KOH (0.1 M, 20 mL) was added to a
solution of 4-CF3C6F4CBB CSiMe3 (2.5 g, 8.0 mmol) in MeOH
(100 mL) and stirred at 24 8C for 4 h. Then the solution was
diluted with 5% aq HCl (25 mL), poured into water (150 mL), and
extracted with ether (2Â 50 mL). The combined extracts were
washed with water and dried with MgSO4. The solvent was
removed under reduced pressure at 24 8C (bath), and the residue
was distilled to yield 4-CF3C6F4CBB CH (0.74 g, 36%) (bp 148–150 8C)
{lit. bp 145–146 8C [23]}.
CF3CBB CIF4. 19F NMR (PFB):
d
11.3 (s,
n1/2 = 10 Hz, IF4), À52.4 (s,
3F, F3). 13C NMR (PFB):
d
112.6 (q, 1J(C-3, F3) = 261 Hz, C-3), 92.0 (m,
C-1), 72.5 (q, 2J(C-2, F3) = 57 Hz, C-2).
4.11. Inertness of C6F13CBB CI toward XeF2 in PFB
Xenon difluoride (200 mg, 1.20 mmol) was added to a solution
of C6F13CBB CI (1.15 mmol) in PFB (0.8 mL). The suspension was
stirred at 44–46 8C for 4 h. A probe of the mother liquor contained
C6F13CBB CI, which could be quantitatively recovered, and XeF2 in
the molar ratio 10:1 (19F NMR, with the internal standard for
integration C4F9Br).
4-CF3C6F4C2BB C1H. 1H NMR (neat): 3.79 (s, 1H). 19F NMR (neat):
d
d
À56.5 (t, 4J(CF3, F3,5) = 22 Hz, 3F, CF3), À134.7 (m, 2F, F2,6), À140.6
(m, 2F,F3,5){lit. 1H NMR (CCl4):
d
3.70(s, 1H). 19F NMR (CCl4):
d
À57.9
(t, J = 22.6 Hz, 3F, CF3), À135.3 (m, 2F), À141.6 (m, 2F) [23]}. 13C and
13C{1H} NMR (neat): 147.2 (dd, 1J(C-3,5, F-3,5) = 253 Hz, 2J(C-3,5, F-
d
2,6) = 14 Hz, C-3,5), 143.5 (dd, 1J(C-2,6, F-2,6) = 261 Hz, 2J(C-2,6, F-
3,5) = 15 Hz, C-2,6), 120.1 (q, 1J(CF3, F) = 273 Hz, CF3), 109.8 (tq, 2J(C-
4, F3,5) = 13 Hz, 2J(C-4, CF3) = 36 Hz, C-4), 106.8 (t, 2J(C-1,
F2,6) = 18 Hz, C-1), 91.6 (dt, 1J(C-1, H) = 259 Hz, 4J(C-1, F2,6) = 3 Hz,
C-1), 66.0 (dt, 2J(C-2, H) = 52 Hz, 3J(C-2, F2,6) = 3 Hz, C-2).
4.12. Preparation of C6F13CBB CIF4
Xenon difluoride (429 mg, 2.53 mmol) was added to a solution
of C6F13CBB CI (1.00 mmol) in PFB (1.8 mL). The suspension was
cooled to 0–3 8C. A slow bubbling of BF3 effected the formation of a
white voluminous suspension which was stirred at 24 8C over a
period of 1 h under a slow bubbling of BF3 to give a pale yellow
solution which contained C6F13CBB CIF2, C6F13CBB CIF4 (1.6:1) and a
trace of C6F13CBB CI. The solution was diluted with PFB (1 mL)
before a new portion of XeF2 (190 mg, 1.12 mmol) was added.
Bubbling of BF3 led again to a voluminous suspension. Stirring at
24 8C was continued for 1.5 h. A probe of the mother liquor showed
that C6F13CBB CIFn (n = 0, 2) was vanished. The second fluorination
step was accompanied by the formation of small amounts of IF5
(C6F13CBB CIF4:IF5 = 89:11). The solvent and IF5 were removed in
vacuum at 24 8C to yield C6F13CBB CIF4 (415 mg, 0.76 mmol) (white
solid).
4.9. Preparation of 4-CF3C6F4CBB CI
A solution of 4-CF3C6F4CBB CH (571 mg, 2.36 mmol) in ether
(5 mL) was cooled to À45 8C under an atmosphere of dry argon.
BuLi in hexanes (2.5 M, 1.0 mL, 2.50 mmol) was added in portions
with a syringe. The solution was stirred at À40 8C for 30 min.
Powdered and dried iodine (597 mg, 2.35 mmol) was added in one
portion. The solution was warmed to ꢀ20 8C over a period of 1.5 h
and washed with a diluted aq solution of Na2S2O3. After drying
with MgSO4 the volatiles were removed under reduced pressure to
give 4-CF3C6F4CBB CI (810 mg, 93%).
1-Iodo-2-(4-heptafluorotolyl)ethyne, 4-CF3C6F4C2BB C1I. 19F
C6F13CBB CIF4. 19F NMR (PFB):
d
11.3 (s,
n
1/2 = 233 Hz, IF4), À80.0
NMR (neat):
d
À57.0 (t, 4J(CF3, F3,5) = 22 Hz, 3F, CF3), À135.1 (m,
(t, 4J(F8, F6) = 9 Hz, 3F, F8), À100.9 (t, 4J(F3, F5) = 12 Hz, 2F, F3),
2F, F2,6), À140.8 (m, 2F, F3,5). 13C NMR (neat):
d
147.7 (dd, 1J(C-3,5,
À119.6 (CF2), À120.7 (CF2), À121.2 (CF2), À124.8 (m, 2F, F7). 19F
F-3,5) = 257 Hz, 2J(C-3,5, F-2,6) = 13 Hz, C-3,5), 143.4 (dd, 1J(C-2,6,
F-2,6) = 261 Hz, 2J(C-2,6, F-3,5) = 15 Hz, C-2,6), 120.0 (q, 1J(CF3,
F) = 274 Hz, CF3), 109.6 (tq, 2J(C-4, F3,5) = 13 Hz, 2J(C-4, CF3) = 35 Hz,
C-4), 107.6 (t, 2J(C-1, F2,6) = 18 Hz, C-1), 76.9 (t, 3J(C-2, F2,6) = 3.7 Hz,
C-2), 24.2 (t, 4J(C-1, F2,6) = 3.6 Hz, C-1).
NMR (CCl2FCH3):
d
11.1 (s,
n
1/2 = 16 Hz, IF4), À81.3 (t, 4J(F8,
F6) = 10 Hz, 3F, F8), À101.9 (t, 4J(F3, F5) = 13 Hz, 2F, F3), À121.2
(CF2), À122.3 (CF2), À122.8 (CF2), À126.3 (m, 2F, F7). 13C NMR
(PFB): d
119–108 (C6F13), 97.0 (m, C-1), 72.4 (t, 2J(C-2, F3,3) = 39 Hz,
C-2). 13C NMR (CCl2FCH3):
d
119–107 (C6F13), 97.0 (quint, 2J(C-1,
HRMS (EI) Calcd. for C9F7I: 367.8933, found: 367.8929.
IF4) = 27 Hz, C-1), 72.5 (t, 2J(C-2, F3,3) = 39 Hz, C-2).
C6F13CBB CIF2 (in a mixture with C6F13CBB CIF4). 19F NMR (PFB):
d
4.10. Preparation of CF3CBB CIF4
À80.3 (t, 4J(F8, F6) = 10 Hz, 3F, F8), À99.6 (mt, 4J(F3, F5) = 12 Hz, 2F,
F3), À119.6 (CF2), À120.1 (CF2), À121.2 (CF2), À124.8 (m, 2F, F7),
When xenon difluoride (214 mg, 1.26 mmol) and CF3CBB CI
(0.5 mmol) were stirred at 24 8C for 1 h in PFB (2 mL) no reaction
À156.2 (s,
n d 119–108 (C6F13),
1/2 = 1176 Hz, IF2). 13C NMR (PFB):
98.5 (t, 2J(C-2, F3,3) = 39 Hz, C-2), 50.3 (t, 3J(C-1, F3,3) = 8 Hz, C-1).

V.V. Bardin, H.-J. Frohn / Journal of Fluorine Chemistry 146 (2013) 98–104
103
A freshly prepared solution of C6F13CBB CIF4 in CCl2FCH3 did not
change at 24 8C over 2–3 h. But after 28 h CClF2CH3 and IF5 were
formed besides numerous products which derived from
C6F13CBB CIF4 (ca. 90% decomposition, 19F NMR).
27 8C for 4 h. No reaction occurred (1H and 19F NMR). The
suspension was cooled to 2–5 8C and BF3 was bubbled slowly.
Within a few minutes the reaction mixture became dark and a
black precipitate was formed. Bubbling of BF3 was continued at
25 8C for 30 min and subsequently the suspension was left
overnight at 25 8C. The 1H and 19F NMR spectra of the mother
liquor showed the presence of C4H9CF2CF2I (0.28 mmol) besides
minor not fully identified products. Whether the compounds
C4H9CBB CI, C4H9CBB CH, C4H9CF = CFI, IF5, XeF2, nor any type of RIFn
(n = 2, 4) were present (19F NMR). The black precipitate was
insoluble in CH2Cl2 and did not react with aq Na2S2O3 solution.
4.13. Reactions of 4-CF3C6F4CBB CI with XeF2 and BF3 with different
stoichiometry
The 1:1.5 reaction of 4-CF3C6F4CBB CI and XeF2/BF3. Xenon
difluoride (118 mg, 0.69 mmol) was added to a solution of 4-
CF3C6F4CBB CI (171 mg, 0.46 mmol) in PFB (1.3 mL). The suspension
was stirred at 2–5 8C for 10 min. A slow stream of BF3 was passed
and within a few min a white voluminous suspension was formed.
After stopping the stream of BF3, the suspension was stirred at 2–
5 8C for 30 min and at 24 8C for 1 h. The volatile compounds were
removed at 24 8C in vacuum to get a white solid (208 mg). A
solution in CH2Cl2 (1 mL) contained 4-CF3C6F4CBB CIF2, 4-
CF3C6F4CBB CIF4, trans-(4-CF3C6F4)CF55CFI [24], IF5 (relative molar
ratio 64:3:15:18), and still unreacted 4-CF3C6F4CBB CI (relative
molar ratio 13) (19F NMR). The 19F NMR spectrum showed also
signals of minor not fully identified products with a 4-CF3C6F4
moiety {triplets of 22 Hz at À57 ppm (CF3) and multiplets at À133
to À138 ppm}.
C4H9CF2CF2I. 1H NMR (CH2Cl2 + PFB):
d
2.00 (tt, 3J(H3,
H4) = 9 Hz, 3J(H3, F2) = 18.4 Hz, 2H, H3), 1.47 (m, CH2), 1.32 (m,
CH2), 0.86 (t, 3J(H6, H5) = 7 Hz, 3H, H6). 19F NMR (PFB):
d
À58.0 (t,
3J(F1, F2) = 5 Hz, 2F, F1), À106.8 (tt, 3J(F2, F1) = 5 Hz, 3J(F2,
H3) = 18 Hz, 2F, F2) {cf. 19F NMR spectrum of C2H5CF2CF2I (CDCl3):
d
À59.9 (t, 3J(F1, F2) = 4.9 Hz, 2F, F1), À110.0 (tt, 3J(F2, F1) = 4.6 Hz,
3J(F2, H3) = 17.1 Hz, 2F, F2) [26]}.
4.15. Reaction of C4H9CBB CH with XeF2 and BF3
A slow stream of boron trifluoride was bubbled into the stirred
suspension of xenon difluoride (154 mg, 0.91 mmol) in a solution
of C4H9CBB CH (37 mg, 0.45 mmol) in PFB (1.3 mL) at 2–4 8C for
ꢁ5 min. Immediately, a dark brown solution was formed. It was
stirred at 2–4 8C for 30 min, at 24 8C for 30 min, before being
washed in sequence with water, an aq solution of Na2SO3, and
water. After drying the solution with MgSO4 the 1H and 19F NMR
spectra showed signals of C4H9CF2CF2H [26] (0.23 mmol),
C4H9CH2CF2H [26] (0.02 mmol), and C4H9CF2CH3 [26] (0.02 mmol)
besides minor amounts of not fully identified products. Resonances
of C4H9CF2CH2F, C4H9CHFCH2F, C4H9CHFCHF2, C4H9CF55CHF,
C4H9CF55CH2, C4H9CH55CF2, and C4H9CH55CHF were not detected
(1H, 19F NMR).
4-CF3C6F4CBB CIF2 (in the reaction mixture). 19F NMR (CH2Cl2):
d
À57.1 (t, 4J(CF3, F3,5) = 22 Hz, 3F, CF3), À131.7 (m, 2F, F2,6), À139.4
(m, 2F, F3,5), À150.1 (s,
n1/2 = 646 Hz, IF2).
4-CF3C6F4CBB CIF4 (in the reaction mixture). 19F NMR (CH2Cl2):
d
7.8 (s,
n
1/2 = 38 Hz, IF4), À57.2 (t, 4J(CF3, F3,5) = 22 Hz, 3F, CF3),
À130.7 (m, 2F, F2,6), À140.2 (m, 2F, F3,5).
The 1:2.9 reaction of 4-CF3C6F4CBB CI and XeF2/BF3. Xenon
difluoride (231 mg, 1.36 mmol) and 4-CF3C6F4CBB CI (175 mg,
0.47 mmol) in PFB (1.5 mL) were stirred at 2–5 8C. The slow
bubbling of BF3 caused the formation of a voluminous suspension
which after 5–10 min changed to a pale brown solution. The
solution was stirred at 24 8C over a period of 30 min without BF3
bubbling. Following the volatile compounds were removed in
vacuum (60–90 hPa). The resulting yellow oil was dissolved in PFB
(0.7 mL). The 19F NMR spectrum showed resonances of IF5, signals
4.16. Attempted reaction of C6F13CBB CH with XeF2 and BF3
Boron trifluoride was bubbled into the stirred suspension of
xenon difluoride (116 mg, 0.68 mmol) in a solution of C6F13CBB CH
(136 mg, 0.39 mmol) in PFB (1.5 mL) at 24 8C for 1 h. No reaction
occurred (1H and 19F NMR).
at À14.6 (s,
n
1/2 = 72 Hz, IF4), À55.9 (t, 4J(CF3, F3,5) = 22 Hz, 3F, CF3),
À135.9 (m, 2F, F2,6), À137.3 (m, 2F, F3,5), À131.2 (d, J = 122 Hz, 1F),
À138.1
(d,
J = 122 Hz,
1F)
{presumably,
trans-(4-
CF3C6F4)CF = CFIF4}, À17.0 (s,
n
1/2 = 58 Hz, IF4), À55.8 (t, 4J(CF3,
F3,5) = 22 Hz, 3F, CF3), À131.7 (m, 2F, F2,6), À138.9 (m, 2F, F3,5) {4-
Acknowledgement
CF3C6F4CꢀCIF4}, À15.6 (s,
n
1/2 = 61 Hz, IF4), À55.9 (t, 4J(CF3,
F3,5) = 22 Hz, 3F, CF3), À133.5 (m, 2F, F2,6), À138.4 (m, 2F, F3,5
)
We gratefully acknowledge financial support by the Fonds der
Chemischen Industrie.
{4-CF3C6F4CꢀCIF4} (ratio 50:36:14), and a number of weak signals
in the ranges from À57 to À59, from À88 to À122, and from À129
to À140 ppm. The notation ‘‘CꢀC’’ means that the substituents at
the C55C or C–C moiety deriving from CBB C are unknown. The
solution was washed with an aq solution of Na2SO3 and water, and
finally dried with MgSO4 and evaporated under reduced pressure.
The resulting oil was dissolved in acetone (1.5 mL) and KMnO4
(64 mg) was added. A suspension was formed which was stirred for
2 h, diluted with water (1 mL), treated with an aq solution of
Na2SO3, acidified, and filtered. Acetone was removed on an
evaporator. The aqueous phase was extracted with ether (2Â
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