Biphenyl Sulfonic and Disulfonic Acids with Perfluorinated Alkyl Residues

Article abstract of DOI:10.1002/ejoc.201800882

Sulfonic acids serve as interesting, yet not intensively studied alternatives to carboxylic acids as linker units in coordination polymers. In this study, we present the synthesis of hybrid sulfonic acids with polar, rigid biphenyl moieties and disordered highly fluorinated alkyl chains. Consequently, eight biphenyl sulfonic and disulfonic acids with one or two perfluoroalkyl chains were prepared. The key steps within the synthesis include two palladium catalyzed C–C bond formations: The perfluoroalkyl residue is installed by Heck reaction (up to 91 %) using 1H,1H,2H-perfluorinated alkenes (C₆ and C₈) and the biphenyl unit is established by a Suzuki coupling (up to 88 %) of boronic acids bearing one or two protected thiol groups. Finally, these thiol groups are converted into the sulfonic acids by N-chlorosuccinimide mediated oxidation followed by hydrolysis of the respective sulfonyl chloride.

Full text of DOI:10.1002/ejoc.201800882

A Journal of
Accepted Article
Title: Biphenyl Sulfonic and Disulfonic Acids with Perfluorinated Alkyl
Residues
Authors: Christoph Kahrs, Mathias Wickleder, and Jens Christoffers
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
Biphenyl Sulfonic and Disulfonic Acids with Perfluorinated Alkyl
Residues
Christoph Kahrs,[a] Mathias S. Wickleder,[b] Jens Christoffers*[a]
[a] M.Sc. C. Kahrs, Prof. Dr. J. Christoffers, Institut für Chemie, Carl von Ossietzky
Universität Oldenburg, 26111 Oldenburg, Germany. Fax: +49(0)441 798 3873. Email:
jens.christoffers@uol.de. Homepage: www.christoffers.chemie.uni-oldenburg.de
[b] Prof. Dr. M. S. Wickleder, Universität zu Köln, 50939 Köln, Germany
Graphical Abstract
Key topic: Fluorinated Biphenyl Sulfonic Acids
C6F13
C6F13
HO3S
HO3S
tBuS
B(OR)2 + TfO
t
BuS
C6F13
C6F13
Hybrid materials consisting of polar sulfonic acids, crystalline biphenyl scaffolds and
amorphous fluorinated side chains are prepared by Suzuki cross coupling.
Abstract: Sulfonic acids serve as interesting, yet not intensively studied alternatives
to carboxylic acids as linker units in coordination polymers. In this study, we present
the synthesis of hybrid sulfonic acids with polar, rigid biphenyl moieties and
disordered highly fluorinated alkyl chains. Consequently, eight biphenyl sulfonic and
disulfonic acids with one or two perfluoroalkyl chains were prepared. The key steps
within the synthesis include two palladium catalyzed C–C bond formations: The
perfluoroalkyl residue is installed by Heck reaction (up to 91%) using 1H,1H,2H-
perfluorinated alkenes (C6 and C8) and the biphenyl unit is established by a Suzuki
coupling (up to 88%) of boronic acids bearing one or two protected thiol groups.
Finally, these thiol groups are converted into the sulfonic acids by N-chlorosuccinimid
mediated oxidation followed by hydrolysis of the respective sulfonyl chloride.
Keywords: Sulfonic acids, Fluorine compounds, Biaryl compounds, Suzuki coupling,
Heck reaction, Boron compounds, Palladium catalysis, Cross coupling
1
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
Introduction
Aromatic oligocarboxylic acids are the leading structural motif for linker molecules in
metal organic frameworks and coordination polymers.[1] The key advantage of this
compound class is the flexible accessibility of various structural subtypes with diffe-
rent symmetries, which is based on a rich and well developed synthetic organic che-
mistry targeting benzene carboxylic acids. In contrast, the synthesis of aromatic sul-
fonic acids is much less developed, which is mainly due to the electronically deacti-
vating character of a sulfo group making a second sulfonation (electrophilic aromatic
substitution) very difficult. However, advantageous features of sulfonic acids com-
pared to carboxylic acids are their higher acidity and pronounced thermal stability of
their salts, making them attractive target structures for the preparation of new mate-
rials. For this reason, we have initiated a research program for the development of
aromatic sulfonic acids as linker compounds in coordination polymers.[2]
Two types of sulfonic acids have found wide spread industrial as well as consumer
applications: First, alkane and alkylbenzene sulfonates are the most common anion
tensides.[3] Secondly, perfluoroalkane sulfonic acids, so-called fluorosurfactants like
perfluorooctane sulfonic acid (PFOS),[4] represent a technologically relevant class of
materials. These compounds have found ubiquitous applications for surface treat-
ment and impregnation.[5]
Benzoic acid derivatives with perfluoroalkyl residues have been reported to exhibit
extraordinary interesting properties as crystalline as well as liquid crystalline materi-
als.[6] In extension of our efforts towards sulfonic acids as linker molecules for coordi-
nation polymers, we report herein on the development of new hybrid materials 1 con-
sisting of three entities (Scheme 1): (1) polar, hydrophilic aromatic sulfonic acids,
which might define proton conducting materials[7] in the solid state or could form
crystalline salts with various metal cations; (2) a rigid biphenyl scaffold being the
structural element for inducing crystallinity of the material; and (3) hydrophobic per-
fluorinated residues creating domains without well-defined crystalline order.[8] The
retrosynthetic approach to target compounds 1 is based on a Suzuki coupling for the
biaryl unit starting from boronic acid derivatives 2 with one or two sulfur moieties pro-
tected as tert-butyl thioethers and phenyl triflates 3[9] carrying one or two perfluori-
nated alkyl chains. An established strategy for introduction of such perfluoroalkyl
2
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
chains is the Heck reaction of an aryl halide with 1H,1H,2H-perfluoro α-olefins
followed by catalytic hydrogenation.[10]
polar
rigid scaffold
disordered
(CH2CH2RF)j
(HO3S)i
1
(CH2CH2RF)j
+ TfO
B(OR)2
( BuS)
t
i
2
3
, = 1, 2
i j
RF = (CF2)3CF3, (CF2)5CF3
Scheme 1. Target compounds of this study are biphenyl mono- and disulfonic acids 1
with one or two perfluoroalkyl residues RF. Their preparation is based on Suzuki
coupling reactions of building blocks 2 and 3.
Results and Discussion
Boronic acids 2. para-(tert-Butylthio)benzene boronic acid (2a) was literature
known[11] and prepared accordingly from the respective para-bromo thioether 4[12] by
lithium-halogen exchange, reaction with B(OMe3) and subsequent hydrolysis. Re-
spective bis(tert-butyl)benzene derivative 2b was not literature known. Therefore, we
prepared it by palladium-catalyzed borylation of bromobenzene bisthioether 5[13] with
bispinacol-diborane (B2pin2) following a literature procedure (Scheme 2).[14] Pinacol
boronate 2b was obtained with 77%.
OH
(a)
BuS
Br
BuS
t
B
t
OH
4
2a (89%)
BuS
BuS
t
t
t
t
Me
Me
O
B
O
(b)
Br
Me
Me
BuS
BuS
5
2b (77%)
Scheme 2. Preparation of boronic acid 2a and pinacol boronate 2b; reagents and
conditions: (a) 1. 1.1 equiv. nBuLi, THF, –78°C, 0.5 h; 2. 2.0 equiv. B(OMe)3, –
78°C23°C, 2 h; 3. HCl–H2O, 23°C, 5 min; (b) 1.2 equiv. B2pin2, 2.0 equiv. KOAc, 5
mol% Pd(OAc)2, 10 mol% DPPF, DMSO, 80°C, 16 h.
3
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
Fluorinated building blocks 3. For the preparation of compounds 3a and 3b with
one perfluoroalkyl residue a Heck reaction of a respective aromatic compound with
1H,1H,2H-perfluoro α-olefins was envisioned. In order to circumvent regioselectivity
problems with consecutive Heck and Suzuki reactions, we planned to install the tri-
flate leaving group after the Heck reaction by esterification of the respective phenol.
In a first exploration of this route it turned out, that a free phenol unit leads to unsatis-
factory results in the Heck reaction. Therefore, we decided to protect the hydroxyl
function as benzyl ether. Consequently, we started from para-iodo benzyl ether 6,
which was accessed according to a literature protocol,[15] and converted it with the re-
spective polyfluorinated 1-hexene and 1-octene. We started with recently published
reaction conditions [Pd(OAc)2, PPh3, NEt3, DMA, 100°C],[16] which had to be optimi-
zed for product 7a (ligands, solvents, temperature) and finally identified optimal con-
ditions [Pd(OAc)2, P(otol)3, K2CO3, DMF, 140°C; Scheme 3].[17] Compounds 7a and
7b were isolated with 91% and 80% yields, resp., after column chromatography
exclusively as (E)-isomers. Catalytic hydrogenation of the olefins also cleaved the
benzyl protective groups and gave saturated compounds 8a and 8b both in almost
quantitative yields. Introduction of the triflate leaving group (Tf2O, pyridine) pro-
ceeded smoothly and also in almost quantitative yields (97% for 3a, 95% for 3b).
(CF2)nCF3
(a)
BnO
I
BnO
6
7a ( = 3, 91%),
n
( = 5, 80%)
7b n
(b)
(CF2)nCF3
(CF2)nCF3
(c)
HO
TfO
3a ( = 3, 97%),
8a ( = 3, 97%),
n
( = 5, 95%)
8b n
n
3b ( = 5, 95%)
n
Scheme 3. Synthesis of the triflates 3a, 3b. Reagents and conditions: (a) 10 equiv.
CH2=CH(CF2)nCF3, 10 mol% Pd(OAc)2, 20 mol% P(otol)3, 5 equiv. K2CO3, DMF,
140°C, 18 h; (b) 10 mol% Pd–C, 4 bar H2, EtOAc, 70°C, 18 h; (c) 1.2 equiv. Tf2O, 2.0
equiv. pyridine, CH2Cl2, 23°C, 1.5 h.
The synthesis of congeners 3c and 3d with two fluorinated side chains started from
(dibromophenyl) ether 9, which was accessed from the respective dibromophenol as
4
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
reported in the literature (Scheme 4).[18] The same reaction conditions as for com-
pounds in Scheme 3 were chosen for all three steps, but yields are naturally a little bit
lower since all transformations had to occur twice within this scaffold. Practically, the
Heck reaction proceeded in 62% (product 10a) and 70% (product 10b). Catalytic
hydrogenations inclusive debenzylations were again quantitative (100% for 11a and
99% for 11b). The introduction of the triflate group proceeded with good yields (90%
for 3c and 81% for 3d).
(CF2)nCF3
Br
(a)
BnO
BnO
Br
9
(CF2)nCF3
( = 3, 62%),
10a n
10b ( = 5, 70%)
n
(b)
(CF2)nCF3
(CF2)nCF3
(c)
TfO
HO
(CF2)nCF3
(CF2)nCF3
11a ( = 3, 100%),
( = 3, 90%),
3c n
3d ( = 5, 81%)
n
( = 5, 99%)
11b n
n
Scheme 4. Synthesis of the triflates 3c, 3d. Reagents and conditions: (a) 10 equiv.
CH2=CH(CF2)nCF3, 10 mol% Pd(OAc)2, 20 mol% P(otol)3, 5.0 equiv. K2CO3, DMF,
140°C, 18 h; (b) 10 mol% Pd–C, 4 bar H2, EtOAc, 70°C, 18 h; (c) 1.2 equiv. Tf2O, 2.0
equiv. pyridine, CH2Cl2, 23°C, 1.5 h.
Suzuki coupling and elaboration of the sulfur functions. We applied previously
published conditions for a Suzuki coupling reaction {[Pd(PPh3)4] as precatalyst and
Na2CO3 as base in EtOH–toluene–water at 100°C}[19] to start off optimizations for the
conversion of boronic acid 2a with triflate 3a, which gave however only low yield of
product 12a. After variation of catalyst, base, solvent and temperature we found
[Pd2dba3] as precatalyst, SPhos [2-(dicyclohexylphosphano)-2',6'-dimethoxybiphenyl]
as ligand[20] and K2CO3 as base in toluene–water at 140°C as suitable conditions to
furnish product 12a in 76% yield (Scheme 5, Table 1). When adopting these condi-
tions to the conversions of boronic acid derivatives 2a and 2b with all four triflates
5
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European Journal of Organic Chemistry
3a–3d, biphenyl products 12a–12f were obtained in the range of 82–59% yield. Pro-
ducts 12g and 12h were isolated with significantly lower yields (43% and 36%, resp.).
The tert-butyl protective group was then oxidatively cleaved from the sulfur moiety
with a method generating chlorine in situ from NCS and HCl.[21] Sulfonyl chlorides
13a–13h were obtained with good to excellents yields (77–100%) after purification by
column chromatography. Upon heating in water, the sulfonyl chlorides 13a–13h were
hydrolyzed to sulfonic acids 1a–1h, which were obtained after evaporation to dryness
as microcrystalline materials (90–100% yields) being hardly soluble in water and or-
ganic solvents. As expected, the mono and disulfonic acids 1a–1h crystallize as the
mono or dihydrate, respectively.
[CH2CH2(CF2)nCF3]j
B(OR)2
+ TfO
( BuS)
t
i
2a-2b
3a-3d
(a)
[CH2CH2(CF2)nCF3]j
( BuS)
t
i
12a-12h
(b)
[CH2CH2(CF2)nCF3]j
(ClO2S)i
13a-13h
(c)
[CH2CH2(CF2)nCF3]j
(HO3S)i
1a-1h
Scheme 5. Suzuki coupling of boronic acid derivatives 2a (i = 1) and 2b (i = 2) with
triflates 3a, 3b (j = 1) and 3c, 3d (j = 2) and further transformation of the thioethers to
sulfonic acids. For constitution of products 1a–1h and all yields see Table 1. Rea-
gents and conditions: (a) 5 mol% [Pd2dba3], 20 mol% SPhos, 2.0 equiv. K2CO3, tolu-
ene/H2O 1:1, 140°C, 18 h; (b) 4 x i equiv. NCS, 1.1 x i equiv. HCl, MeCN, 0°C, 1 h,
23°C, 1 h; (c) H2O, 100°C, 18 h.
6
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European Journal of Organic Chemistry
Table 1. Constitutions and yields of products 1a–1h, yields for intermediate products
12a–12h and 13a–13h.
Product 1
Yield of 1
Yield of 12 Yield of 13
(CF2)nCF3
HO3S
1a (n = 3, 100%), 12a (76%), 13a (77%),
1b (n = 5, 98%),
12b (88%), 13b (80%),
HO3S
HO3S
(CF2)nCF3
1c (n = 3, 97%),
1d (n = 5, 91%),
12c (81%), 13c (85%),
12d (76%), 13d (78%),
(CF2)nCF3
HO3S
1e (n = 3, 90%),
1f (n = 5, 91%),
12e (79%), 13e (78%),
12f (82%), 13f (77%),
(CF2)nCF3
(CF2)nCF3
HO3S
HO3S
1g (n = 3, 90%),
1h (n = 5, 90%)
12g (43%), 13g (100%),
12h (36%) 13h (85%)
(CF2)nCF3
Conclusion
A series of eight biphenyl sulfonic and disulfonic acids 1a–1h with either one of two
perfluoroalkyl residues was prepared. Within the framework of our research program
on sulfonic acids as linker units in metal organic frameworks, these materials shall
serve as linker molecules for preparing coordination polymers with polar, crystalline
and disordered fluorinated domains in the solid state. Two palladium catalyzed trans-
formations were the key transformations for the formation of C–C bonds: First, the
fluorinated side chains were introduced by Heck reaction (yields 62–91%) of
1H,1H,2H-perfluoro α-olefins to the aromatic ring (followed by catalytic hydrogenation
to the saturated side chains). Secondly, the biphenyl scaffold was established by Su-
zuki coupling (yields 36–88%) of boronic acid derivatives 2a–2b holding either one or
two tert-butylthio groups with phenyl triflates carrying the perfluoro alkyl chains. In
7
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
two subsequent functional group interconversions, the tert-butylthio functions were
oxidatively transformed to the sulfonyl chlorides, which were finally hydrolyzed to the
final sulfonic acids. As a further element of diversity the lengths of the side chains
was either C6 or C8.
Experimental Section
General: Preparative column chromatography was carried out using Merck SiO2 (35–
70 µm, type 60 A) with hexanes, tert-butyl methyl ether (MTBE), and CH2Cl2 as elu-
1
19
13
ents. TLC was performed on aluminum plates coated with SiO2 F254. H, F and C
NMR spectra were recorded on a Bruker Avance DRX 300 and 500 instruments.
Multiplicities of carbon signals were determined with DEPT experiments. Due to the
high multiplicity of the carbon signals of the perfluorinated chains, we were not able
13
to identify these carbon atoms in the C NMR spectra. MS and HRMS spectra were
obtained with Thermo Scientific DFS (EI) and Waters Q-TOF Premier (ESI and APCI)
spectrometers. IR spectra were recorded on a Bruker Tensor 27 spectrometer equip-
ped with a diamond ATR unit. Elemental analyses were determined with a Euro EA-
CHNS instrument from HEKAtech. Melting points were obtained with a Gallenkamp
device; values are uncorrected. Compounds 4,[12] 5,[13] 6[15] and 9[18] were prepared
according to literature protocols. All other starting materials were commercially avai-
lable. In particular, nC4F9CH=CH2 and nC6F13CH=CH2 were purchased from Apollo.
4-(tert-Butylthio)benzeneboronic acid (2a). With exclusion of moisture and air (ni-
trogen atmosphere), n-BuLi (2 mol/L in n-hexane, 0.90 mL, 2.24 mmol, 1.1 equiv.)
was added to a solution of thioether 4 (500 mg, 2.04 mmol, 1.0 equiv.) in THF (5 mL)
at –78°C. After stirring the mixture for 30 min at –78°C, B(OMe)3 (0.46 mL, 0.43 g,
4.1 mmol, 2.0 equiv.) was added. The solution was stirred for 15 min at –78°C and
for further 1.5 h at ambient temperature. Hydrochloric acid (1 mol/L, 10 mL) was ad-
ded and the suspension was stirred for 5 min at ambient temperature. The layers
were separated and the aqueous layer was extracted with MTBE (3 x 20 mL). The
combined organic layers were dried (MgSO4) and filtered. The solvent was removed
in vacuo to furnish the title compound 2a (381 mg, 1.81 mmol, 89%) as a colorless
1
solid, which did not require further purification. H NMR (300 MHz, CDCl3): δ = 1.35
(s, 9 H), 7.66–7.69 (m, 2 H), 8.17–8.20 (m, 2 H) ppm. The protons of the boronic acid
8
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
were not observed. The data were in accordance with literature values.[11]
C10H15BO2S (210.10).
2-[3,5-Bis(tert-butylthio)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(2b).
With exclusion of moisture and air (nitrogen atmosphere), bisthioether 5 (100 mg,
0.30 mmol, 1.0 equiv.) was added to a mixture of B2pin2 (91 mg, 0.36 mmol, 1.2
equiv.), Pd(OAc)2 (3 mg, 15 µmol, 5 mol%), DPPF (17 mg, 30 µmol, 10 mol%) and
KOAc (59 mg, 0.60 mmol, 2.0 equiv.) in DMSO (3 mL). The resulting mixture was
stirred at 80°C for 16 h. MTBE (25 mL) was then added and the solution was washed
with brine (3 x 15 mL). The organic layer was dried (MgSO4) and filtered. The solvent
was removed in vacuo and the crude product purified by column chromatography
(SiO2, CH2Cl2, Rf = 0.92) to yield the title compound 2b (88 mg, 0.23 mmol, 77%) as
1
a colorless solid (mp 111°C). H NMR (300 MHz, CDCl3): δ = 1.29 (s, 18 H), 1.34 (s,
12 H), 7.82–7.83 (m, 1 H), 7.94–7.94 (m, 2 H) ppm. 13C{1H} NMR (75 MHz, CDCl3): δ
= 25.02 (4 CH3), 31.19 (6 CH3), 46.21 (2 C), 84.17 (2 C), 132.63 (2 C), 143.92 (2
CH), 148.88 (CH) ppm. Due to the quadrupole moment of the boron atom, we were
not able to identify the ipso-carbon atom. IR (ATR): nu(tilde) = 2972 (m), 2924 (w),
2862 (w), 1361 (s), 1337 (vs), 1312 (s), 1160 (s), 1141 (vs), 1124 (s), 712 (s) cm–1.
+
HRMS (ESI, pos. mode): calcd. 381.2088 (for C20H34BO2S2 ); found 381.2087 [M +
H+]. C20H33BO2S2 (380.41).
General procedure A (GPA). With exclusion of moisture and air (nitrogen atmo-
sphere), the alkene (10 equiv.) was added to a suspension of the bromo- (6) or iodo-
benzene (9) derivative (1.0 equiv.), Pd(OAc)2 (10 mol%), P(otol)3 (20 mol%) and
K2CO3 (5.0 equiv.) in anhydrous DMF (3 L/mol). The resulting mixture was heated to
140°C for 18 h. Brine (15 L/mol) was added and the mixture was extracted with
MTBE (3 x 15 L/mol). The organic layer was dried (MgSO4) and filtered. The solvent
was removed in vacuo and the crude product was purified by column chromatogra-
phy to give the alkenes 7 or 10.
(E)-1-(Benzyloxy)-4-(1H,2H-perfluoro-1-hexenyl)benzene (7a). According to the
GPA, 1H,1H,2H-perfluoro-1-hexene (0.54 mL, 0.79 g, 3.2 mmol), 1-(benzyloxy)-4-io-
dobenzene (6) (100 mg, 0.32 mmol), Pd(OAc)2 (7 mg, 32 µmol), P(otol)3 (19 mg, 64
µmol) and K2CO3 (221 mg, 1.60 mmol) were converted to furnish compound 7a (125
9
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
mg, 0.29 mmol, 91%) after column chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf =
1
0.38) as a colorless solid (mp 52°C). H NMR (300 MHz, CDCl3): δ = 5.11 (s, 2 H),
6.05 (dt, J = 16.1 Hz, J = 12.3 Hz, 1 H), 6.98–7.01 (m, 2 H), 7.11 (dt, J = 16.1 Hz, J =
1.8 Hz, 1 H), 7.32–7.44 (m, 7 H) ppm. 13C{1H} NMR (75 MHz, CDCl3): δ = 70.24
(CH2), 111.89 (t, J = 22.8 Hz, CH), 115.39 (2 CH), 126.62 (C), 127.59 (2 CH), 128.32
(CH), 128.82 (2 CH), 129.35 (2 CH), 136.57 (C), 139.28 (t, J = 9.9 Hz, CH), 160.48
(C) ppm. 19F{1H} NMR (470 MHz, CDCl3): δ = (–125.76)–(–125.68) (m, CF2), (–
124.12)–(–124.06) (m, CF2), (–110.84)–(–110.79) (m, CF2), (–81.10)–(–81.06) (m,
CF3) ppm. IR (ATR): nu(tilde) = 2888 (w), 2857 (w), 1656 (w), 1609 (m), 1223 (vs),
1203 (vs), 1130 (vs) cm–1. HRMS (EI, 70 eV): calcd. 428.0817 (for C19H13F9O+);
found 428.0815 [M+]. C19H13F9O (428.30).
(E)-1-(Benzyloxy)-4-(1H,2H-perfluoro-1-octenyl)benzene (7b). According to the
GPA, 1H,1H,2H-perfluoro-1-octene (7.3 mL, 11.1 g, 32.2 mmol), 1-(benzyloxy)-4-io-
dobenzene (6) (1.00 g, 3.22 mmol), Pd(OAc)2 (72 mg, 0.32 mmol), P(otol)3 (196 mg,
644 µmol) and K2CO3 (2.23 g, 16.1 mmol) were converted to furnish compound 7b
(1.37 g, 2.59 mmol, 80%) after column chromatography (SiO2, hexanes/CH2Cl2 10:1,
1
Rf = 0.35) as a colorless solid (mp 60°C). H NMR (500 MHz, CDCl3): δ = 5.11 (s, 2
H), 6.08 (dt, J = 16.1 Hz, J = 12.4 Hz, 1 H), 7.00–7.02 (m, 2 H), 7.11 (dt, J = 16.1 Hz,
13
J = 1.9 Hz, 1 H), 7.35–7.46 (m, 7 H) ppm. C{1H} NMR (125 MHz, CDCl3): δ = 70.26
(CH2), 112.07 (t, J = 23.1 Hz, CH), 115.43 (2 CH), 126.70 (C), 127.60 (2 CH), 128.32
(CH), 128.83 (2 CH), 129.37 (2 CH), 136.66 (C), 139.27 (t, J = 9.5 Hz, CH), 160.55
(C) ppm. 19F{1H} NMR (470 MHz, CDCl3): δ = (–126.23)–(–126.15) (m, CF2), (–
123.25)–(–123.20) (m, CF2), (–122.94)–(–122.83) (m, CF2), (–121.67)–(–121.54) (m,
CF2), (–110.64)–(–110.56) (m, CF2), (–80.94)–(–80.90) (m, CF2) ppm. IR (ATR):
nu(tilde) = 3041 (w), 2860 (w), 1235 (s), 1191 (vs), 1141 (s), 738 (s), 714 (s), 706 (s)
cm–1. HRMS (EI, 70 eV): calcd. 528.0753 (for C21H13F13O+); found 528.0767 [M+].
C21H13F13O (528.31).
(E)-1-(Benzyloxy)-3,5-bis(1H,2H-perfluoro-1-hexenyl)benzene (10a). According to
the GPA, 1H,1H,2H-perfluoro-1-hexene (2.5 mL, 3.6 g, 15 mmol), 1-(benzyloxy)-3,5-
dibromobenzene (9) (500 mg, 1.46 mmol), Pd(OAc)2 (33 mg, 0.15 mmol), P(otol)3 (89
mg, 0.29 mmol) and K2CO3 (1.01 g, 7.30 mmol) were converted to furnish compound
10a (608 mg, 0.90 mmol, 62%) after column chromatography (SiO2, hexanes/CH2Cl2
10
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1
10:1, Rf = 0.35) as a colorless oil. H NMR (500 MHz, CDCl3): δ = 5.14 (s, 2 H), 6.22
(dt, J = 16.0 Hz, J = 12.0 Hz, 2 H), 7.11–7.17 (m, 5 H), 7.35–7.38 (m, 1 H), 7.41–7.46
(m, 4 H) ppm. 13C{1H} NMR (125 MHz, CDCl3): δ = 70.65 (CH2), 115.53 (2 CH),
116.04 (t, J = 23.0 Hz, 2 CH), 120.15 (CH), 127.66 (2 CH), 128.52 (CH), 128.92 (2
19
CH), 135.81 (2 C), 136.29 (C), 139.06 (t, J = 9.2 Hz, 2 CH), 159.80 (C) ppm. F{1H}
NMR (470 MHz, CDCl3): δ = (–125.70)–(–125.61) (m, CF2), (–124.06)–(–124.00) (m,
CF2), (–111.52)–(–111.47) (m, CF2), (–81.09)–(–81.04) (m, CF3) ppm. IR (ATR):
nu(tilde) = 3069 (w), 3039 (w), 1221 (vs), 1170 (s), 1130 (vs), 885 (s) cm–1. HRMS
(EI, 70 eV): calcd. 672.0752 (for C25H14F18O+); found 672.0744 [M+]. C25H14F18O
(672.36).
(E)-1-(Benzyloxy)-3,5-bis(1H,2H-perfluoro-1-octenyl)benzene (10b). According to
the GPA, 1H,1H,2H-perfluoro-1-octene (3.4 mL, 5.1 g, 15 mmol), 1-(benzyloxy)-3,5-
dibromobenzene (9) (500 g, 16.4 mmol), Pd(OAc)2 (33 mg, 0.15 mmol), P(otol)3 (89
mg, 0.29 mmol) and K2CO3 (1.01 g, 7.30 mmol) were converted to furnish compound
10b (889 mg, 1.02 mmol, 70%) after column chromatography (SiO2, hexanes/CH2Cl2
1
10:1, Rf = 0.39) as a yellow oil. H NMR (500 MHz, CDCl3): δ = 5.13 (s, 2 H), 6.22 (dt,
J = 16.1 Hz, J = 12.0 Hz, 2 H), 7.11–7.17 (m, 5 H), 7.35–7.37 (m, 1 H), 7.40–7.45 (m,
13
4 H) ppm. C{1H} NMR (125 MHz, CDCl3): δ = 70.66 (CH2), 115.53 (2 CH), 116.13
(t, J = 23.1 Hz, 2 CH), 120.16 (CH), 127.66 (2 CH), 128.52 (CH), 128.92 (2 CH),
19
135.81 (2 C), 136.28 (C), 139.03 (t, J = 9.6 Hz, 2 CH), 159.79 (C) ppm. F{1H} NMR
(470 MHz, CDCl3): δ = (–126.12)–(–126.04) (m, 2 CF2), (–123.14)–(–123.08) (m, 2
CF2), (–122.83)–(–122.74) (m, 2 CF2), (–121.58)–(–121.46) (m, 2 CF2), (–111.26)–(–
111.21) (m, 2 CF2), (–80.82)–(–80.78) (m, 2 CF3) ppm. IR (ATR): nu(tilde) = 3072
(w), 3039 (w), 1231 (s), 1192 (vs), 1169 (s), 1142 (vs), 1119 (s), 699 (s) cm–1. HRMS
(EI, 70 eV): calcd. 872.0624 (for C29H14F26O+); found 872.0622 [M+]. C29H14F26O
(872.39).
General procedure B (GPB). Pd–C (10 w/w%, 10 mol%) was added to a solution of
the alkene 7 or 10 (1.0 equiv.) in EtOAc (5 L/mol). The resulting suspension was stir-
red at 70°C under a H2 atmosphere (3 bar excess) for 18 h. The suspension was fil-
tered using SiO2 (MTBE). The solvent was removed in vacuo to give the phenols 8
and 11.
11
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European Journal of Organic Chemistry
4-(1H,1H,2H,2H-Perfluorohexyl)phenol (8a). According to the GPB, Pd–C (10
w/w%, 132 mg, 124 µmol) and alkene 7a (531 mg, 1.24 mmol) were converted to fur-
nish compound 8a (419 mg, 1.23 mmol, 99%) after filtration (SiO2, MTBE, Rf = 0.92)
1
as a colorless oil. H NMR (300 MHz, CDCl3): δ = 2.24–2.42 (m, 2 H), 2.82–2.88 (m,
13
2 H), 5.10 (br s, 1 H), 6.78–6.81 (m, 2 H), 7.07–7.10 (m, 2 H) ppm. C{1H} NMR (75
MHz, CDCl3): δ = 25.69 (t, J = 4.3 Hz, CH2), 33.25 (t, J = 22.2 Hz, CH2), 115.78 (2
19
CH), 129.64 (2 CH), 131.61 (C), 154.30 (C) ppm. F{1H} NMR (470 MHz, CDCl3): δ
= (–126.08)–(–126.03) (m, CF2), (–124.52)–(–124.46) (m, CF2), (–114.95)–(–114.89)
(m, CF2), (–81.08)–(–81.04) (m, CF3) ppm. IR (ATR): nu(tilde) = 3283 (w), 2970 (w),
2956 (w), 2868 (w), 1216 (vs), 1169 (s), 1131 (s) cm–1. HRMS (EI, 70 eV): calcd.
340.0504 (for C12H9F9O+); found 340.0502 [M+]. C12H9F9O (340.19).
4-(1H,1H,2H,2H-Perfluorooctyl)phenol (8b). According to the GPB, Pd–C (10
w/w%, 239 mg, 225 µmol) and alkene 7b (1.19 g, 2.25 mmol) were converted to
furnish compound 8b (963 mg, 2.19 mmol, 97%) after filtration (SiO2, MTBE, Rf =
1
0.94) as a colorless solid (mp 43°C). H NMR (500 MHz, CDCl3): δ = 2.28–2.39 (m, 2
H), 2.84–2.87 (m, 2 H), 5.12 (br s, 1 H), 6.79–6.81 (m, 2 H), 7.07–7.09 (m, 2 H) ppm.
13C{1H} NMR (125 MHz, CDCl3): δ = 25.76 (t, J = 4.0 Hz, CH2), 33.41 (t, J = 22.1 Hz,
19
CH2), 115.79 (2 CH), 129.61 (2 CH), 131.55 (C), 154.46 (C) ppm. F{1H} NMR (470
MHz, CDCl3): δ = (–126.25)–(–126.17) (m, CF2), (–123.63)–(–123.56) (m, CF2), (–
123.00)–(–122.83) (m, CF2), (–122.04)–(–121.86) (m, CF2), (–114.76)–(–114.61) (m,
CF2), (–80.95)–(–80.89) (m, CF2) ppm. IR (ATR): nu(tilde) = 3402 (w), 3029 (w), 2943
(w), 2876 (w), 1228 (s), 1204 (s), 1187 (vs), 1139 (vs), 1073 (s), 693 (s), 637 (s) cm–
1. HRMS (EI, 70 eV): calcd. 440.0440 (for C14H9F13O+); found 440.0457 [M+].
C14H9F13O (440.20).
3,5-Bis(1H,1H,2H,2H-perfluorohexyl)phenol (11a). According to the GPB, Pd–C
(10 w/w%, 15 mg, 14 µmol) and alkene 10a (96 mg, 0.14 mmol) were converted to
furnish compound compound 11a (83 mg, 0.14 mmol, 100%) after filtration (SiO2,
1
MTBE, Rf = 0.94) as a colorless solid (mp 52°C). H NMR (500 MHz, CDCl3): δ =
2.31–2.41 (m, 2 H), 2.84–2.87 (m, 2 H), 4.87 (br s, 1 H), 6.58 (s, 2 H), 6.65 (s, 1 H)
13
ppm. C{1H} NMR (125 MHz, CDCl3): δ = 26.44 (t, J = 3.9 Hz, 2 CH2), 32.88 (t, J =
19
22.1 Hz, 2 CH2), 113.84 (2 CH), 121.00 (CH), 141.74 (2 C), 156.32 (C) ppm. F{1H}
NMR (470 MHz, CDCl3): δ = (–126.07)–(–126.01) (m, 2 CF2), (–124.48)–(–124.42)
12
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(m, 2 CF2), (–114.87)–(–114.81) (m, 2 CF2), (–81.18)–(–81.13) (m, 2 CF3) ppm. IR
(ATR): nu(tilde) = 3396 (w), 2963 (w), 2893 (w), 2851 (w), 1209 (s), 1127 (s), 1097
(s), 1063 (s), 1051 (vs), 1035 (s), 1000 (s) cm–1. HRMS (EI, 70 eV): calcd. 586.0595
(for C18H12F18O+); found 586.0583 [M+]. C18H12F18O (586.26).
3,5-Bis(1H,1H,2H,2H-perfluorooctyl)phenol (11b). According to the GPB, Pd–C
(10 w/w%, 109 mg, 102 µmol) and alkene 10b (889 g, 1.02 mmol) were converted to
furnish compound 11b (798, 1.01 mmol, 99%) after filtration (SiO2, MTBE, Rf = 0.94)
1
as a colorless oil. H NMR (500 MHz, CDCl3): δ = 2.31–2.41 (m, 2 H), 2.84–2.87 (m,
2 H), 4.75 (br s, 1 H), 6.58 (s, 2 H), 6.64 (s, 1 H) ppm. 13C{1H} NMR (125 MHz,
CDCl3): δ = 26.46 (t, J = 4.7 Hz, 2 CH2), 32.97 (t, J = 21.7 Hz, 2 CH2), 113.82 (2 CH),
19
120.97 (CH), 141.70 (2 C), 156.33 (C) ppm. F{1H} NMR (470 MHz, CDCl3): δ = (–
126.12)–(–126.05) (m, 2 CF2), (–123.49)–(–123.43) (m, 2 CF2), (–122.88)–(–122.76)
(m, 2 CF2), (–121.89)–(–121.77) (m, 2 CF2), (–114.56)–(–114.49) (m, 2 CF2), (–
80.83)–(–80.79) (m, 2 CF3) ppm. IR (ATR): nu(tilde) = 3344 (w), 2948 (w), 1231 (s),
1187 (vs), 1142 (vs), 1120 (s) cm–1. HRMS (EI, 70 eV): calcd. 786.0467 (for
C22H12F26O+); found 786.0457 [M+]. C22H12F26O (786.30).
General procedure C (GPC). At 0°C, Tf2O (1.2 equiv.) was added to a solution of
pyridine (2.0 equiv.) and phenol 8 or 11 (1.0 equiv.) in anhydrous CH2Cl2 (5 L/mol). A
colorless solid precipitated immediately. The resulting suspension was stirred at am-
bient temperature for 1.5 h. MTBE (25 L/mol) and hydrochloric acid (1 mol/L, 15
L/mol) were added and the layers were separated. The organic layer was washed
with saturated aqueous NaHCO3 (15 L/mol) and brine (15 L/mol). The organic layer
was dried (MgSO4) and filtered. The solvent was removed in vacuo to give the tri-
flates 3.
4-(1H,1H,2H,2H-Perfluorohexyl)phenyl trifluoromethanesulfonate (3a). According
to the GPC, Tf2O (124 mg, 0.44 mmol), pyridine (59 mg, 0.74 mmol) and phenol 8a
(126 mg, 0.37 mmol) were converted to furnish compound 3a (171 mg, 0.36 mmol,
1
97%) as a yellow liquid. H NMR (500 MHz, CDCl3): δ = 2.33–2.43 (m, 2 H), 2.94–
13
2.98 (m, 2 H), 7.23–7.25 (m, 2 H), 7.30–7.31 (m, 2 H) ppm. C{1H} NMR (75 MHz,
CDCl3): δ = 26.05 (t, J = 4.5 Hz, CH2), 32.73 (t, J = 22.1 Hz, CH2), 118.92 (q, J =
19
320.7 Hz, C), 121.04 (2 CH), 130.28 (2 CH), 139.82 (C), 148.52 (C) ppm. F{1H}
13
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European Journal of Organic Chemistry
NMR (470 MHz, CDCl3): δ = (–126.07)–(–126.02) (m, CF2), (–124.47)–(–124.41) (m,
CF2), (–114.88)–(–114.82) (m, CF2), (–81.08)–(–81.04) (m, CF3), (–72.88) (s, CF3)
ppm. IR (ATR): nu(tilde) = 2957 (w), 2922 (w), 2858 (w), 1208 (vs), 1131 (vs), 881 (s)
cm–1. HRMS (EI, 70 eV): calcd. 471.9997 (for C13H8F12O3S+); found 471.9998 [M+].
C13H8F12O3S (472.24).
4-(1H,1H,2H,2H-Perfluorooctyl)phenyl trifluoromethanesulfonate (3b). According
to the GPC, Tf2O (0.41 mL, 0.68 g, 2.42 mmol), pyridine (0.33 mL, 0.32 g, 4.04
mmol) and phenol 8b (888 mg, 2.02 mmol) were converted to furnish compound 3b
1
(1.10 g, 1.92 mmol, 95%) as a yellow liquid. H NMR (500 MHz, CDCl3): δ = 2.33–
2.44 (m, 2 H), 2.94–2.98 (m, 2 H), 7.23–7.25 (m, 2 H), 7.30–7.31 (m, 2 H) ppm.
13C{1H} NMR (125 MHz, CDCl3): δ = 26.09 (t, J = 4.3 Hz, CH2), 32.84 (t, J = 22.2 Hz,
CH2), 118.91 (q, J = 320.7 Hz, C), 121.87 (2 CH), 130.27 (2 CH), 139.81 (C), 148.51
(C) ppm. 19F{1H} NMR (470 MHz, CDCl3): δ = (–126.18)–(–126.10) (m, CF2), (–
123.53)–(–123.42) (m, CF2), (–122.90)–(–122.80) (m, CF2), (–121.95)–(–121.82) (m,
CF2), (–114.63)–(–114.48) (m, CF2), (–80.84)–(–80.79) (m, CF2), (–72.89) (CF3) ppm.
IR (ATR): nu(tilde) = 2953 (w), 1203 (s), 1137 (vs), 886 (s) cm–1. HRMS (EI, 70 eV):
calcd. 571.9933 (for C15H8F16O3S+); found 571.9937 [M+]. C15H8F16O3S (572.26).
3,5-Bis(1H,1H,2H,2H-perfluorohexyl)phenyl trifluoromethanesulfonate (3c). Ac-
cording to the GPC, Tf2O (305 mg, 1.08 mmol), pyridine (142 mg, 1.80 mmol) and
phenol 11a (530 mg, 0.90 mmol) were converted to furnish compound 3c (583 mg,
1
0.81 mmol, 90%) as a yellow oil. H NMR (500 MHz, CDCl3): δ = 2.34–2.44 (m, 4 H),
13
2.95–2.98 (m, 4 H), 7.03 (s, 2 H), 7.11 (s, 1 H) ppm. C{1H} NMR (125 MHz, CDCl3):
δ = 26.46 (t, J = 4.5 Hz, 2 CH2), 32.56 (t, J = 22.3 Hz, 2 CH2), 118.90 (q, J = 320.5
Hz, C), 119.81 (2 CH), 128.59 (CH), 142.64 (2 C), 150.06 (C) ppm. 19F{1H} NMR (470
MHz, CDCl3): δ = (–126.00)–(–125.94) (m, 2 CF2), (–124.35)–(–124.29) (m, 2 CF2),
(–114.62)–(–114.56) (m, 2 CF2), (–81.08)–(–81.03) (m, 2 CF3), (–72.92) (s, CF3)
ppm. IR (ATR): nu(tilde) = 2960 (w), 1211 (vs), 1132 (vs), 987 (s), 884 (s), 728 (s),
611 (s) cm–1. HRMS (EI, 70 eV): calcd. 718.0088 (for C19H11F21O3S+); found
718.0079 [M+]. C19H11F21O3S (718.32).
3,5-Bis(1H,1H,2H,2H-perfluorooctyl)phenyl trifluoromethanesulfonate (3d). Ac-
cording to the GPC, Tf2O (341 mg, 1.21 mmol), pyridine (160 mg, 2.02 mmol) and
14
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phenol 11b (798 mg, 1.01 mmol) were converted to furnish compound 3d (751 mg,
1
0.82 mmol, 81%) as a yellow oil. H NMR (500 MHz, CDCl3): δ = 2.34–2.45 (m, 4 H),
13
2.95–2.98 (m, 4 H), 7.03 (s, 2 H), 7.12 (s, 1 H) ppm. C{1H} NMR (125 MHz, CDCl3):
δ = 26.45 (t, J = 4.5 Hz, 2 CH2), 32.61 (t, J = 22.7 Hz, 2 CH2), 118.87 (q, J = 321.9
Hz, C), 119.81 (2 CH), 128.62 (CH), 142.62 (2 C), 150.03 (C) ppm. 19F{1H} NMR (470
MHz, CDCl3): δ = (–126.13)–(–126.05) (m, 2 CF2), (–123.40)–(–123.34) (m, 2 CF2),
(–122.87)–(–122.77) (m, 2 CF2), (–121.89)–(–121.76) (m, 2 CF2), (–114.37)–(–
114.30) (m, 2 CF2), (–80.84)–(–80.79) (m, 2 CF3), (–72.91) (s, CF3) ppm. IR (ATR):
nu(tilde) = 2952 (w), 1235 (s), 1212 (s), 1186 (vs), 1158 (s), 1139 (vs), 1117 (s), 985
(s), 700 (s), 613 (s) cm–1. HRMS (EI, 70 eV): calcd. 917.9960 (for C23H11F29O3S+);
found 917.9956 [M+]. C23H11F29O3S (918.35).
General procedure D (GPD). With exclusion of moisture and air (nitrogen atmo-
sphere), triflate 3 (1.0 equiv) was added to a suspension of boronic acid derivative 2
(1.1 equiv.), Pd2dba3 (5 mol%), SPhos (20 mol%) and K2CO3 (2.0 equiv.) in degas-
sed toluene (20 L/mol). Degassed water (20 L/mol) was added and the vial was
tightly closed. The resulting mixture was stirred at 140°C for 18 h. The layers were
separated and the aqueous layer was extracted with MTBE (2 x 40 L/mol). The com-
bined organic layers were dried (MgSO4) and filtered. The solvent was removed in
vacuo and the crude product was purified by column chromatography to give the
biphenyl derivatives 12.
4'-(1H,1H,2H,2H-Perfluorohexyl)-4-(tert-butylthio)biphenyl (12a). According to the
GPD, triflate 3a (100 mg, 0.21 mmol), boronic acid 2a (48 mg, 0.23 mmol), Pd2dba3
(10 mg, 11 µmol), SPhos (17 mg, 42 µmol) and K2CO3 (58 mg, 0.42 mmol) were con-
verted to furnish compound 12a (78 mg, 0.16 mmol, 76%) after column chromato-
1
graphy (SiO2, hexanes/CH2Cl2 10:1, Rf = 0.24) as a colorless solid (mp 87°C). H
NMR (500 MHz, CDCl3): δ = 1.33 (s, 9 H), 2.37–2.47 (m, 2 H), 2.95–2.99 (m, 2 H),
7.30–7.31 (m, 2 H), 7.53–7.55 (m, 2 H), 7.56–7.58 (m, 2 H), 7.59–7.61 (m, 2 H) ppm.
13C{1H} NMR (125 MHz, CDCl3): δ = 26.23 (t, J = 4.1 Hz, CH2), 31.14 (3 CH3), 32.96
(t, J = 22.0 Hz, CH2), 46.24 (C), 127.11 (2 CH), 127.60 (2 CH), 128.95 (2 CH),
131.90 (C), 137.99 (2 CH), 138.68 (C), 139.03 (C), 141.11 (C) ppm. 19F{1H} NMR
(470 MHz, CDCl3): δ = (–126.02)–(–125.96) (m, CF2), (–124.44)–(–124.37) (m, CF2),
(–114.86)–(–114.80) (m, CF2), (–81.01)–(–80.97) (m, CF3) ppm. IR (ATR): nu(tilde) =
15
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2971 (w), 1232 (s), 1210 (s), 1189 (s), 1167 (s), 1131 (vs), 814 (s), 712 (s) cm–1.
HRMS (EI, 70 eV): calcd. 488.1215 (for C22H21F9S+); found 488.1223 [M+]. C22H21F9S
(488.46).
4'-(1H,1H,2H,2H-Perfluorooctyl)-4-(tert-butylthio)biphenyl (12b). According to the
GPD, triflate 3b (100 mg, 0.17 mmol), boronic acid 2a (40 mg, 0.19 mmol), Pd2dba3
(8 mg, 9 µmol), SPhos (14 mg, 34 µmol) and K2CO3 (47 mg, 0.34 mmol) were con-
verted to furnish compound 12b (90 mg, 0.15 mmol, 88%) after column chromato-
1
graphy (SiO2, hexanes/CH2Cl2 10:1, Rf = 0.30) as a colorless solid (mp 83°C). H
NMR (500 MHz, CDCl3): δ = 1.33 (s, 9 H), 2.37–2.48 (m, 2 H), 2.96–2.99 (m, 2 H),
7.30–7.31 (m, 2 H), 7.54–7.55 (m, 2 H), 7.56–7.58 (m, 2 H), 7.60–7.61 (m, 2 H) ppm.
13C{1H} NMR (125 MHz, CDCl3): δ = 26.27 (t, J = 4.1 Hz, CH2), 31.14 (3 CH3), 33.08
(t, J = 22.0 Hz, CH2), 46.22 (C), 127.12 (2 CH), 127.60 (2 CH), 128.95 (2 CH),
131.96 (C), 137.99 (2 CH), 138.71 (C), 139.05 (C), 141.13 (C) ppm. 19F{1H} NMR
(470 MHz, CDCl3): δ = (–126.17)–(–126.10) (m, CF2), (–123.52)–(–123.44) (m, CF2),
(–122.92)–(–122.81) (m, CF2), (–121.93)–(–121.82) (m, CF2), (–114.64)–(–114.50)
(m, CF2), (–80.84)–(–80.80) (m, CF2) ppm. IR (ATR): nu(tilde) = 2964 (w), 2925 (w),
2865 (w), 1230 (s), 1184 (s), 1141 (vs), 698 (s) cm–1. HRMS (EI, 70 eV): calcd.
588.1151 (for C24H21F13S+); found 588.1155 [M+]. C24H21F13S (588.47).
4'-(1H,1H,2H,2H-Perfluorohexyl)-3,5-bis(tert-butylthio)biphenyl (12c). According
to the GPD, triflate 3a (100 mg, 0.21 mmol), boronic acid 2b (87 mg, 0.23 mmol),
Pd2dba3 (10 mg, 11 µmol), SPhos (17 mg, 42 µmol) and K2CO3 (58 mg, 0.42 mmol)
were converted to furnish compound 12c (96 mg, 0.17 mmol, 76%) after column
1
chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf = 0.19) as a colorless oil. H NMR
(300 MHz, CDCl3): δ = 1.35 (s, 18 H), 2.36–2.48 (m, 2 H), 2.94–3.01 (m, 2 H), 7.31–
7.34 (m, 2 H), 7.56–7.58 (m, 2 H), 7.74–7.75 (m, 1 H), 7.77–7.78 (m, 2 H) ppm.
13C{1H} NMR (125 MHz, CDCl3): δ = 26.25 (t, J = 4.0 Hz, CH2), 31.19 (6 CH3), 32.97
(t, J = 22.1 Hz, CH2), 46.46 (C), 127.68 (2 CH), 129.04 (2 CH), 133.61 (CH), 136.33
(2 CH), 138.44 (C), 138.95 (C), 141.28 (C), 144.71 (2 C) ppm. 19F{1H} NMR (470
MHz, CDCl3): δ = (–126.02)–(–125.97) (m, CF2), (–124.46)–(–124.37) (m, CF2), (–
114.84)–(–114.71) (m, CF2), (–81.06)–(–81.02) (m, CF3) ppm. IR (ATR): nu(tilde) =
2964 (w), 2924 (w), 2900 (w), 2861 (w), 1220 (s), 731 (vs) cm–1. HRMS (APCI):
+
calcd. 577.1640 (for C26H30F9S2 ); found 577.1621 [M + H+]. C26H29F9S2 (576.92).
16
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European Journal of Organic Chemistry
4'-(1H,1H,2H,2H-Perfluorooctyl)-3,5-bis(tert-butylthio)biphenyl (12d). According
to the GPD, triflate 3b (100 mg, 0.21 mmol), boronic acid 2b (72 mg, 0.19 mmol),
Pd2dba3 (8 mg, 9 µmol), SPhos (14 mg, 34 µmol) and K2CO3 (47 mg, 0.34 mmol)
were converted to furnish compound 12d (89 mg, 0.13 mmol, 76%) after column
1
chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf = 0.29) as a colorless oil. H NMR
(500 MHz, CDCl3): δ = 1.33 (s, 18 H), 2.36–2.46 (m, 2 H), 2.96–2.99 (m, 2 H), 7.31–
7.32 (m, 2 H), 7.55–7.56 (m, 2 H), 7.72–7.73 (m, 1 H), 7.75–7.76 (m, 2 H) ppm.
13C{1H} NMR (125 MHz, CDCl3): δ = 26.28 (t, J = 3.9 Hz, CH2), 31.20 (6 CH3), 33.08
(t, J = 22.1 Hz, CH2), 46.47 (C), 127.69 (2 CH), 129.05 (2 CH), 133.60 (CH), 136.35
(2 CH), 138.44 (C), 138.97 (C), 141.29 (C), 144.72 (2 C) ppm. 19F{1H} NMR (470
MHz, CDCl3): δ = (–126.14)–(–126.08) (m, CF2), (–123.53)–(–123.42) (m, CF2), (–
122.89)–(–122.80) (m, CF2), (–121.92)–(–121.79) (m, CF2), (–114.61)–(–114.48) (m,
CF2), (–80.82)–(–80.78) (m, CF2) ppm. IR (ATR): nu(tilde) = 2962 (w), 2942 (w), 2924
(w), 2864 (w), 1237 (vs), 1165 (s), 1144 (s) cm–1. HRMS (EI, 70 eV): calcd. 676.1498
(for C28H29F13S2+); found 676.1491 [M+]. C28H29F13S2 (676.64).
3',5'-Bis(1H,1H,2H,2H-perfluorohexyl)-4-(tert-butylthio)biphenyl (12e). According
to the GPD, triflate 3c (100 mg, 0.14 mmol), boronic acid 2a (32 mg, 0.15 mmol),
Pd2dba3 (6 mg, 7 µmol), SPhos (11 mg, 28 µmol) and K2CO3 (39 mg, 0.28 mmol)
were converted fo furnish compound 12e (78 mg, 0.11 mmol, 79%) after column
1
chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf = 0.29) as a colorless oil. H NMR
(500 MHz, CDCl3): δ = 1.34 (s, 9 H), 2.38–2.49 (m, 4 H), 2.97–3.00 (m, 4 H), 7.08 (s,
13
1 H), 7.33 (s, 2 H), 7.53–7.55 (m, 2 H), 7.61–7.63 (m, 2 H) ppm. C{1H} NMR (125
MHz, CDCl3): δ = 26.67 (t, J = 3.9 Hz, 2 CH2), 31.17 (3 CH3), 33.12 (t, J = 22.3 Hz, 2
CH2), 46.29 (C), 125.80 (2 CH), 127.31 (2 CH), 127.69 (CH), 132.53 (C), 138.00 (2
19
CH), 140.56 (2 C), 141.04 (C), 141.92 (C) ppm. F{1H} NMR (470 MHz, CDCl3): δ =
(–126.00)–(–125.95) (m, 2 CF2), (–124.38)–(–124.32) (m, 2 CF2), (–114.75)–(–
114.70) (m, 2 CF2), (–81.10)–(–81.05) (m, 2 CF3) ppm. IR (ATR): nu(tilde) = 2965
(w), 2900 (w), 1217 (vs), 1167 (s), 1131 (vs), 1109 (s), 880 (s) cm–1. HRMS (EI, 70
eV): calcd. 734.1306 (for C28H24F18S+); found 734.1301 [M+]. C28H24F18S (734.53).
3',5'-Bis(1H,1H,2H,2H-perfluorooctyl)-4-(tert-butylthio)biphenyl (12f). According
to the GPD, triflate 3d (100 mg, 0.11 mmol), boronic acid 2a (25 mg, 0.12 mmol),
17
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
Pd2dba3 (5 mg, 6 µmol), SPhos (9 mg, 22 µmol) and K2CO3 (30 mg, 0.22 mmol) were
converted to furnish compound 12f (80 mg, 90 μmol, 82%) after column chromato-
1
graphy (SiO2, hexanes/CH2Cl2 10:1, Rf = 0.41) as a colorless oil. H NMR (500 MHz,
CDCl3): δ = 1.33 (s, 9 H), 2.37–2.48 (m, 4 H), 2.96–3.00 (m, 4 H), 7.08 (s, 1 H), 7.33
(s, 2 H), 7.53–7.54 (m, 2 H), 7.60–7.62 (m, 2 H) ppm. 13C{1H} NMR (125 MHz,
CDCl3): δ = 26.65 (t, J = 3.2 Hz, 2 CH2), 31.13 (3 CH3), 33.16 (t, J = 22.5 Hz, 2 CH2),
46.30 (C), 125.79 (2 CH), 127.31 (2 CH), 127.71 (CH), 132.39 (C), 138.02 (2 CH),
19
140.52 (2 C), 141.01 (C), 141.85 (C) ppm. F{1H} NMR (470 MHz, CDCl3): δ = (–
126.12)–(–126.05) (m, 2 CF2), (–123.45)–(–123.36) (m, 2 CF2), (–122.85)–(–122.75)
(m, 2 CF2), (–121.87)–(–121.75) (m, 2 CF2), (–114.50)–(–114.44) (m, 2 CF2), (–
80.84)–(–80.80) (m, 2 CF3) ppm. IR (ATR): nu(tilde) = 2963 (w), 2924 (w), 1233 (s),
1189 (vs), 1142 (vs), 1120 (s) cm–1. HRMS (EI, 70 eV): calcd. 934.1178 (for
C32H24F26S+); found 934.1181 [M+]. C32H24F26S (934.56).
3',5'-Bis(1H,1H,2H,2H-perfluorohexyl)-3,5-bis(tert-butylthio)biphenyl (12g). Ac-
cording to the GPD, triflate 3c (100 mg, 0.14 mmol), boronic acid 2b (57 mg, 0.15
mmol), Pd2dba3 (6 mg, 7 µmol), SPhos (11 mg, 28 µmol) and K2CO3 (39 mg, 0.28
mmol) were converted to furnish compound 12g (50 mg, 60 μmol, 43%) after column
1
chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf = 0.21) as a colorless oil. H NMR
(500 MHz, CDCl3): δ = 1.35 (s, 18 H), 2.38–2.49 (m, 4 H), 2.97–3.00 (m, 4 H), 7.09
13
(s, 1 H), 7.30 (s, 2 H), 7.73–7.76 (m, 3 H) ppm. C{1H} NMR (125 MHz, CDCl3): δ =
26.65 (t, J = 3.7 Hz, 2 CH2), 31.23 (6 CH3), 33.07 (t, J = 22.4 Hz, 2 CH2), 46.57 (2 C),
125.88 (2 CH), 127.87 (CH), 133.82 (2 C), 136.44 (2 CH), 140.69 (2 C), 141.25 (2 C),
144.97 (CH) ppm. 19F{1H} NMR (470 MHz, CDCl3): δ = (–125.97)–(–125.92) (m, 2
CF2), (–124.34)–(–124.28) (m, 2 CF2), (–114.71)–(–114.66) (m, 2 CF2), (–81.09)–(–
81.02) (m, 2 CF3) ppm. IR (ATR): nu(tilde) = 2964 (w), 2925 (w), 2900 (w), 1217 (vs),
1166 (s), 1131 (vs), 879 (s) cm–1. HRMS (EI, 70 eV): calcd. 822.1653 (for
C32H32F18S2+); found 822.1645 [M+]. C32H32F18S2 (822.70).
3',5'-Bis(1H,1H,2H,2H-perfluorooctyl)-3,5-bis(tert-butylthio)biphenyl (12h). Ac-
cording to the GPD, triflate 3d (100 mg, 0.11 mmol), boronic acid 2b (46 mg, 0.12
mmol), Pd2dba3 (5 mg, 6 µmol), SPhos (9 mg, 22 µmol) and K2CO3 (30 mg, 0.22
mmol) were converted to furnish compound 12h (46 mg, 40 μmol, 36%) after column
1
chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf = 0.24) as a colorless oil. H NMR
18
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
(500 MHz, CDCl3): δ = 1.34 (s, 18 H), 2.38–2.49 (m, 4 H), 2.97–3.00 (m, 4 H), 7.09
13
(s, 1 H), 7.29 (s, 2 H), 7.73–7.75 (m, 3 H) ppm. C{1H} NMR (125 MHz, CDCl3): δ =
26.67 (t, J = 3.9 Hz, 2 CH2), 31.23 (6 CH3), 33.16 (t, J = 22.5 Hz, 2 CH2), 46.57 (2 C),
125.87 (2 CH), 127.88 (CH), 133.81 (2 C), 136.44 (2 CH), 140.69 (2 C), 141.23 (C),
141.25 (C), 144.96 (CH) ppm. 19F{1H} NMR (470 MHz, CDCl3): δ = (–126.11)–(–
126.04) (m, 2 CF2), (–123.40)–(–123.35) (m, 2 CF2), (–122.84)–(–122.74) (m, 2 CF2),
(–121.85)–(–121.74) (m, 2 CF2), (–114.47)–(–114.40) (m, 2 CF2), (–80.83)–(–80.78)
(m, 2 CF3) ppm. IR (ATR): nu(tilde) = 2960 (w), 2923 (w), 2864 (w), 1231 (s), 1189
(s), 1141 (vs), 1073 (s), 723 (s), 708 (s) cm–1. HRMS (EI, 70 eV): calcd. 1022.1525
(for C36H32F26S2+); found 1022.1525 [M+]. C36H32F26S2 (1022.73).
General procedure E (GPE). NCS (4.0 equiv. per thioether unit) and hydrochloric
acid (1 mol/L, 1.1 equiv. per thioether unit) were added in portions at 0°C to a solu-
tion of thioether 12 (1.0 equiv.) in CH3CN (30 L/mol). The resulting solution was stir-
red at 0°C for 1 h and at ambient temperature for 1 h. Water (30 L/mol) was added
and the mixture was extracted with CH2Cl2 (3 x 30 L/mol). The combined organic
layers were dried (MgSO4) and filtered. The solvent was removed in vacuo and the
crude product was purified by column chromatography to give the sulfonyl chlorides
13.
4'-(1H,1H,2H,2H-Perfluorohexyl)biphenyl-4-sulfonyl chloride (13a). According to
the GPE, NCS (69 mg, 0.52 mmol), hydrochloric acid (1 mol/L, 0.15 mL, 0.15 mmol)
and thioether 12a (64 mg, 0.13 mmol) were converted to furnish compound 13a (52
mg, 0.10 mmol, 77%) after column chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf =
1
0.11) as a colorless solid (mp 75°C). H NMR (500 MHz, CDCl3): δ = 2.38–2.49 (m, 2
H), 2.99–3.02 (m, 2 H), 7.36–7.38 (m, 2 H), 7.59–7.61 (m, 2 H), 7.79–7.81 (m, 2 H),
13
8.09–8.11 (m, 2 H) ppm. C{1H} NMR (125 MHz, CDCl3): δ = 26.36 (t, J = 3.8 Hz,
CH2), 32.84 (t, J = 22.2 Hz, CH2), 127.78 (2 CH), 128.02 (2 CH), 128.17 (2 CH),
19
129.37 (2 CH), 137.22 (C), 140.56 (C), 143.09 (C), 147.95 (2 C) ppm. F{1H} NMR
(470 MHz, CDCl3): δ = (–125.98)–(–125.90) (m, CF2), (–124.37)–(–124.30) (m, CF2),
(–114.68)–(–114.61) (m, CF2), (–81.05)–(–80.99) (m, CF2) ppm. IR (ATR): nu(tilde) =
2956 (w), 2928 (w), 2854 (w), 1233 (s), 1209 (vs), 1190 (s), 1165 (vs), 1127 (vs),
1085 (s), 715 (s), 581 (vs), 561 (vs) cm–1. HRMS (EI, 70 eV): calcd. 498.0097 (for
C18H12ClF9O2S+); found 498.0083 [M+]. C18H12ClF9O2S (498.79).
19
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4'-(1H,1H,2H,2H-Perfluorooctyl)biphenyl-4-sulfonyl chloride (13b). According to
the GPE, NCS (80 mg, 0.60 mmol), hydrochloric acid (1 mol/L, 0.2 mL, 0.2 mmol)
and thioether 12b (90 mg, 0.15 mmol) were converted to furnish compound 13b (72
mg, 0.12 mmol, 80%) after column chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf =
0.14) as a colorless solid (mp 90°C). 1H NMR (300 MHz, CDCl3): δ = 2.34–2.52 (m, 2
H), 2.98–3.03 (m, 2 H), 7.36–7.38 (m, 2 H), 7.58–7.61 (m, 2 H), 7.78–7.81 (m, 2 H),
13
8.09–8.12 (m, 2 H) ppm. C{1H} NMR (125 MHz, CDCl3): δ = 26.38 (t, J = 3.9 Hz,
CH2), 32.94 (t, J = 22.2 Hz, CH2), 127.78 (2 CH), 128.02 (2 CH), 128.17 (2 CH),
19
129.38 (2 CH), 137.22 (C), 140.58 (C), 143.09 (C), 147.96 (2 C) ppm. F{1H} NMR
(470 MHz, CDCl3): δ = (–126.12)–(–126.04) (m, CF2), (–123.45)–(–123.39) (m, CF2),
(–122.85)–(–122.75) (m, CF2), (–121.87)–(–121.76) (m, CF2), (–114.46)–(–114.39)
(m, CF2), (–80.84)–(–80.80) (m, CF2) ppm. IR (ATR): nu(tilde) = 2920 (w), 2850 (w),
1235 (s), 1178 (vs), 1139 (vs), 1108 (s), 696 (s), 568 (s), 556 (s) cm–1. HRMS (EI, 70
eV): calcd. 598.0033 (for C20H12ClF13O2S+); found 598.0018 [M+]. C20H12ClF13O2S
(598.80).
4'-(1H,1H,2H,2H-Perfluorohexyl)biphenyl-3,5-disulfonyl dichloride (13c). Accor-
ding to the GPE, NCS (139 mg, 1.04 mmol), hydrochloric acid (1 mol/L, 0.3 mL, 0.3
mmol) and thioether 12c (76 mg, 0.13 mmol) were converted to furnish compound
13c (66 mg, 0.11 mmol, 85%) after column chromatography (SiO2, hexanes/CH2Cl2
1
10:1, Rf = 0.03) as a colorless oil. H NMR (500 MHz, CDCl3): δ = 2.39–2.50 (m, 2
H), 3.02–3.05 (m, 2 H), 7.43–7.45 (m, 2 H), 7.64–7.66 (m, 2 H), 8.52–8.53 (m, 2 H),
13
8.60–8.61 (m, 1 H) ppm. C{1H} NMR (125 MHz, CDCl3): δ = 26.42 (t, J = 4.0 Hz,
CH2), 32.71 (t, J = 22.5 Hz, CH2), 123.55 (CH), 127.95 (2 CH), 129.90 (2 CH), 130.83
(2 CH), 134.67 (C), 141.86 (C), 145.56 (C), 146.42 (2 C) ppm. 19F{1H} NMR (470
MHz, CDCl3): δ = (–125.96)–(–125.88) (m, CF2), (–124.34)–(–124.27) (m, CF2), (–
114.58)–(–114.51) (m, CF2), (–81.03)–(–80.97) (m, CF2) ppm. IR (ATR): nu(tilde) =
3079 (w), 1211 (s), 1169 (vs), 1129 (s), 611 (vs) cm–1. HRMS (EI, 70 eV): calcd.
595.9327 (for C18H11Cl2F9O4S2+); found 595.9345 [M+]. C18H11Cl2F9O4S2 (597.29).
4'-(1H,1H,2H,2H-Perfluorooctyl)biphenyl-3,5-disulfonyl dichloride (13d). Accor-
ding to the GPE, NCS (96 mg, 0.72 mmol), hydrochloric acid (1 mol/L, 92 mg, 90
μmol) and thioether 12d (64 mg, 90 μmol) were converted to furnish compound 13d
20
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
(50 mg, 70 μmol, 78%) after column chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf
1
= 0.05) as a colorless solid (dec. 112°C). H NMR (300 MHz, CDCl3): δ = 2.35–2.53
(m, 2 H), 3.01–3.06 (m, 2 H), 7.42–7.45 (m, 2 H), 7.64–7.66 (m, 2 H), 8.52–8.53 (m,
13
2 H), 8.60–8.61 (m, 1 H) ppm. C{1H} NMR (125 MHz, CDCl3): δ = 26.44 (t, J = 4.2
Hz, CH2), 32.80 (t, J = 22.4 Hz, CH2), 123.55 (CH), 127.95 (2 CH), 129.90 (2 CH),
19
130.83 (2 CH), 134.67 (C), 141.87 (C), 145.56 (C), 146.42 (2 C) ppm. F{1H} NMR
(470 MHz, CDCl3): δ = (–126.10)–(–126.02) (m, CF2), (–123.42)–(–123.32) (m, CF2),
(–122.85)–(–122.73) (m, CF2), (–121.87)–(–121.74) (m, CF2), (–114.35)–(–114.29)
(m, CF2), (–80.80)–(–80.76) (m, CF2) ppm. IR (ATR): nu(tilde) = 3079 (w), 2921 (w),
2851 (w), 1245 (s), 1215 (s), 1173 (vs), 1136 (vs), 1118 (s), 603 (vs), 563 (s) cm–1.
+
HRMS (EI, 70 eV): calcd. 695.9263 (for C20H11Cl2F13O4S2 ); found 695.9263 [M+].
C20H11Cl2F13O4S2 (697.30).
3',5'-Bis(1H,1H,2H,2H-perfluorohexyl)biphenyl-4-sulfonyl chloride (13e). Accor-
ding to the GPE, NCS (48 mg, 0.36 mmol), hydrochloric acid (1 mol/L, 0.10 mL, 0.10
mmol) and thioether 12e (63 mg, 90 μmol) were converted to furnish compound 13e
(51 mg, 70 μmol, 78%) after column chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf
1
= 0.13) as a colorless oil. H NMR (300 MHz, CDCl3): δ = 2.34–2.52 (m, 4 H), 2.98–
3.04 (m, 4 H), 7.18 (s, 1 H), 7.35 (s, 2 H), 7.78–7.81 (m, 2 H), 8.10–8.13 (m, 2 H)
13
ppm. C{1H} NMR (125 MHz, CDCl3): δ = 26.65 (t, J = 4.2 Hz, 2 CH2), 32.99 (t, J =
22.2 Hz, 2 CH2), 126.18 (2 CH), 127.78 (2 CH), 128.47 (2 CH), 129.23 (CH), 140.08
19
(C), 141.11 (2 C), 143.45 (C), 147.84 (C) ppm. F{1H} NMR (470 MHz, CDCl3): δ =
(–125.97)–(–124.91) (m, 2 CF2), (–124.34)–(–124.28) (m, 2 CF2), (–114.66)–(–
114.61) (m, 2 CF2), (–81.06)–(–81.01) (m, 2 CF3) ppm. IR (ATR): nu(tilde) = 2957
(w), 2926 (w), 2852 (w), 1216 (vs), 1192 (s), 1170 (s), 1126 (vs), 569 (vs) cm–1.
HRMS (EI, 70 eV): calcd. 744.0188 (for C24H15ClF18O2S+); found 744.0183 [M+].
C24H15ClF18O2S (744.86).
3',5'-Bis(1H,1H,2H,2H-perfluorooctyl)biphenyl-4-sulfonyl chloride (13f). Accor-
ding to the GPE, NCS (17 mg, 0.13 mmol), hydrochloric acid (1 mol/L, 41 mg, 40
μmol) and thioether 12f (31 mg, 33 μmol) were converted to furnish compound 13f
(24 mg, 25 μmol, 76%) after column chromatography (SiO2, hexanes/CH2Cl2 10:1, Rf
1
= 0.22) as a colorless oil. H NMR (500 MHz, CDCl3): δ = 2.39–2.49 (m, 4 H), 3.00–
3.03 (m, 4 H), 7.18 (s, 1 H), 7.34 (s, 2 H), 7.78–7.80 (m, 2 H), 8.11–8.13 (m, 2 H)
21
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13
ppm. C{1H} NMR (125 MHz, CDCl3): δ = 26.66 (t, J = 3.0 Hz, 2 CH2), 33.00 (t, J =
22.4 Hz, 2 CH2), 126.19 (2 CH), 127.79 (2 CH), 128.48 (2 CH), 129.24 (CH), 140.09
19
(C), 141.12 (2 C), 143.46 (C), 147.85 (C) ppm. F{1H} NMR (470 MHz, CDCl3): δ =
(–126.10)–(–126.03) (m, 2 CF2), (–123.39)–(–123.33) (m, 2 CF2), (–122.84)–(–
122.72) (m, 2 CF2), (–121.83)–(–121.72) (m, 2 CF2), (–114.41)–(–114.34) (m, 2 CF2),
(–80.81)–(–80.76) (m, 2 CF3) ppm. IR (ATR): nu(tilde) = 2962 (w), 2928 (w), 1233 (s),
1191 (vs), 1178 (vs), 1142 (vs), 1122 (s), 707 (s), 568 (vs), 560 (s) cm–1. HRMS (EI,
70 eV): calcd. 944.0061 (for C28H15ClF26O2S+); found 944.0062 [M+]. C28H15ClF26O2S
(944.89).
3',5'-Bis(1H,1H,2H,2H-perfluorohexyl)biphenyl-3,5-disulfonyl dichloride (13g).
According to the GPE, NCS (43 mg, 320 μmol) hydrochloric acid (1 mol/L, 92 mg, 90
μmol) and thioether 12g (37 mg, 40 μmol, 1.0 equiv.) were converted to furnish com-
pound 13g (37 mg, 40 μmol, 100%) after column chromatography (SiO2,
1
hexanes/CH2Cl2 10:1, Rf = 0.07) as a colorless oil. H NMR (300 MHz, CDCl3): δ =
2.36–2.55 (m, 4 H), 3.02–3.08 (m, 4 H), 7.27 (s, 1 H), 7.38 (s, 2 H), 8.51–8.51 (m, 2
13
H), 8.63–8.65 (m, 1 H) ppm. C{1H} NMR (125 MHz, CDCl3): δ = 26.67 (t, J = 3.7 Hz,
2 CH2), 32.94 (t, J = 22.3 Hz, 2 CH2), 123.95 (CH), 126.16 (2 CH), 130.31 (CH),
19
131.09 (2 CH), 137.49 (C), 141.87 (2 C), 145.47 (C), 146.47 (2 C) ppm. F{1H} NMR
(470 MHz, CDCl3): δ = (–125.96)–(–125.90) (m, 2 CF2), (–124.32)–(–124.22) (m, 2
CF2), (–114.78)–(–114.53) (m, 2 CF2), (–81.08)–(–81.00) (m, 2 CF3) ppm. IR (ATR):
nu(tilde) = 2950 (w), 2922 (w), 2854 (w), 1218 (vs), 1178 (s), 1132 (vs) cm–1. HRMS
(EI, 70 eV): calcd. 841.9418 (for C24H14Cl2F18O4S2+); found 841.9416 [M+].
C24H14Cl2F18O4S2 (843.36).
3',5'-Bis(1H,1H,2H,2H-perfluorooctyl)biphenyl-3,5-disulfonyl dichloride (13h).
According to the GPE, NCS (29 mg, 0.22 mmol), hydrochloric acid (1 mol/L, 61 mg,
60 μmol) and thioether 12h (29 mg, 28 μmol) were converted to furnish compound
13h (23 mg, 22 μmol, 79%) after column chromatography (SiO2, hexanes/CH2Cl2
1
10:1, Rf = 0.05) as a colorless oil. H NMR (500 MHz, CDCl3): δ = 2.41–2.51 (m, 4
H), 3.04–3.07 (m, 4 H), 7.27 (s, 1 H), 7.38 (s, 2 H), 8.51–8.51 (m, 2 H), 8.64–8.64 (m,
13
1 H) ppm. C{1H} NMR (125 MHz, CDCl3): δ = 26.67 (t, J = 3.7 Hz, 2 CH2), 32.94 (t,
J = 22.3 Hz, 2 CH2), 123.95 (CH), 126.16 (2 CH), 130.31 (CH), 131.09 (2 CH),
137.49 (C), 141.87 (2 C), 145.47 (C), 146.47 (2 C) ppm. 19F{1H} NMR (470 MHz,
22
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European Journal of Organic Chemistry
CDCl3): δ = (–126.09)–(–126.02) (m, 2 CF2), (–123.33)–(–123.27) (m, 2 CF2), (–
122.85)–(–122.72) (m, 2 CF2), (–121.82)–(–121.72) (m, 2 CF2), (–114.32)–(–114.26)
(m, 2 CF2), (–80.80)–(–80.76) (m, 2 CF3) ppm. IR (ATR): nu(tilde) = 2961 (w), 2923
(w), 2854 (w), 1235 (s), 1184 (vs), 1143 (s) cm–1. HRMS (EI, 70 eV): calcd.
+
1041.9290 (for C28H14Cl2F26O4S2 ); found 1041.9292 [M+]. C28H14Cl2F26O4S2
(1043.39).
General procedure F (GPF). A suspension of sulfonyl chloride 13 (1.0 equiv.) in wa-
ter (20 L/mol) was heated to reflux for 18 h. The solvent was removed in vacuo to fur-
nish the sulfonic acids 1.
4'-(1H,1H,2H,2H-Perfluorohexyl)biphenyl-4-sulfonic acid monohydrate (1a). Ac-
cording to the the GPF, sulfonyl chloride 13a (39 mg, 78 μmol) was converted to fur-
1
nish compound 1a (39 mg, 78 μmol, 100%) as a colorless solid (dec. 165°C). H
NMR (500 MHz, acetone-d6): δ = 2.55–2.66 (m, 2 H), 3.01–3.05 (m, 2 H), 7.47–7.49
13
(m, 2 H), 7.68–7.70 (m, 2 H), 7.81–7.82 (m, 2 H), 7.93–7.95 (m, 2 H) ppm. C{1H}
NMR (125 MHz, acetone-d6): δ = 26.54 (t, J = 3.9 Hz, CH2), 32.84 (t, J = 21.8 Hz,
CH2), 127.88 (2 CH), 127.92 (2 CH), 128.27 (2 CH), 130.06 (2 CH), 138.64 (C),
19
140.49 (C), 141.45 (C), 144.91 (C) ppm. F{1H} NMR (470 MHz, acetone-d6): δ = (–
126.64)–(–126.58) (m, CF2), (–124.88)–(–124.82) (m, CF2), (–114.98)–(–114.92) (m,
CF2), (–81.95)–(–81.90) (m, CF2) ppm. IR (ATR): nu(tilde) = 2954 (w), 2922 (w), 2853
(w), 1210 (vs), 1194 (s), 1130 (vs), 805 (s), 710 (s) cm–1. HRMS (ESI, pos. mode):
calcd. 481.0514 (for C18H14F9O3S+); found 481.0527 [M – OH]+. C18H13F9O3S ∙ H2O
(498.36).
4'-(1H,1H,2H,2H-Perfluorooctyl)biphenyl-4-sulfonic acid monohydrate (1b). Ac-
cording to the GPF, sulfonyl chloride 13b (49 mg, 82 μmol) was converted to furnish
1
compound 1b (48 mg, 80 μmol, 98%) as a colorless solid (dec. 91°C). H NMR (500
MHz, acetone-d6): δ = 2.56–2.67 (m, 2 H), 3.02–3.05 (m, 2 H), 7.48–7.49 (m, 2 H),
13
7.69–7.70 (m, 2 H), 7.82–7.84 (m, 2 H), 7.94–7.96 (m, 2 H) ppm. C{1H} NMR (125
MHz, acetone-d6): δ = 26.64 (t, J = 3.9 Hz, CH2), 33.02 (t, J = 21.7 Hz, CH2), 127.98
(2 CH), 128.04 (2 CH), 128.32 (2 CH), 130.09 (2 CH), 138.62 (C), 140.62 (C), 141.00
19
(C), 145.25 (C) ppm. F{1H} NMR (470 MHz, acetone-d6): δ = (–126.74)–(–126.66)
(m, CF2), (–123.92)–(–123.87) (m, CF2), (–123.41)–(–123.29) (m, CF2), (–122.42)–(–
23
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
122.31) (m, CF2), (–114.74)–(–114.67) (m, CF2), (–81.71)–(–81.66) (m, CF2) ppm. IR
(ATR): nu(tilde) = 3032 (w), 2950 (w), 1229 (s), 1181 (s), 1140 (vs), 1124 (vs), 1073
(s), 1036 (s), 594 (s), 562 (s) cm–1. HRMS (ESI, neg. mode): calcd. 579.0305 (for
C20H12F13O3S–); found 579.0280 [M – H3O+]. C20H13F13O3S ∙ H2O (598.38): calcd. C
40.15, H 2.53, S 5.36; found C 40.31, H. 2.60, S 5.10.
4'-(1H,1H,2H,2H-Perfluorohexyl)biphenyl-3,5-disulfonic acid dihydrate (1c). Ac-
cording to the GPF, sulfonyl chloride 13c (15 mg, 22 μmol) was converted to furnish
1
compound 1c (20 mg, 34 μmol, 97%) as a yellow solid (dec. 138°C). H NMR (500
MHz, acetone-d6): δ = 2.59–2.70 (m, 2 H), 3.08–3.11 (m, 2 H), 7.61–7.63 (m, 2 H),
13
7.97–7.98 (m, 2 H), 8.64–8.65 (m, 1 H), 8.81–8.82 (m, 2 H) ppm. C{1H} NMR (125
MHz, acetone-d6): δ = 26.62 (t, J = 4.3 Hz, CH2), 32.65 (t, J = 21.1 Hz, CH2), 124.12
(CH), 128.90 (2 CH), 130.56 (2 CH), 132.05 (2 CH), 135.28 (C), 142.56 (C), 146.48
19
(C), 146.65 (2 C) ppm. F{1H} NMR (470 MHz, acetone-d6): δ = (–126.63)–(–126.57)
(m, CF2), (–124.87)–(–124.81) (m, CF2), (–114.91)–(–114.85) (m, CF2), (–81.94)–(–
81.89) (m, CF2) ppm. IR (ATR): nu(tilde) = 3404 (w), 2927 (w), 1714 (m), 1217 (s),
1130 (vs), 1030 (s) cm–1. HRMS (ESI, neg. mode): calcd. 558.9937 (for
–
C18H12F9O6S2 ); found 558.9938 [M – 2 H2O – H+]. C18H13F9O6S2 ∙ 2 H2O (596.43).
4'-(1H,1H,2H,2H-Perfluorooctyl)biphenyl-3,5-disulfonic acid dihydrate (1d). Ac-
cording to the GPF, sulfonyl chloride 13d (15 mg, 22 μmol) was converted to furnish
compound 1d (14 mg, 20 μmol, 91%) as a colorless solid (dec. 125°C). 1H NMR (500
MHz, acetone-d6): δ = 2.61–2.71 (m, 2 H), 3.08–3.12 (m, 2 H), 7.61–7.62 (m, 2 H),
13
7.96–7.97 (m, 2 H), 8.64–8.65 (m, 1 H), 8.81–8.81 (m, 2 H) ppm. C{1H} NMR (125
MHz, acetone-d6): δ = 26.72 (t, J = 4.4 Hz, CH2), 32.84 (t, J = 21.5 Hz, CH2), 124.15
(CH), 128.94 (2 x CH), 130.60 (2 CH), 132.07 (2 CH), 134.35 (C), 142.63 (C), 146.57
19
(C), 146.76 (2 C) ppm. F{1H} NMR (470 MHz, acetone-d6): δ = (–126.73)–(–126.65)
(m, CF2), (–123.92)–(–123.87) (m, CF2), (–123.42)–(–123.31) (m, CF2), (–122.39)–(–
122.31) (m, CF2), (–114.74)–(–114.61) (m, CF2), (–81.70)–(–81.65) (m, CF2) ppm. IR
(ATR): nu(tilde) = 3343 (w), 3079 (w), 2945 (w), 1215 (s), 1172 (vs), 1135 (vs), 1118
(s), 610 (vs), 602 (vs) cm–1. HRMS (ESI, neg. mode): calcd. 328.9900 (for
2–
C20H11F13O6S2 ); found 328.9881 [M – 2 H3O+]. C20H13F13O6S2 ∙ 2 H2O (696.45):
calcd. C 34.49, H 2.46, S 9.21; found C 34.84, H 2.30, S 9.35.
24
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European Journal of Organic Chemistry
3',5'-Bis(1H,1H,2H,2H-perfluorohexyl)biphenyl-4-sulfonic
acid monohydrate
(1e). According to the GPF, sulfonyl chloride 13e (22 mg, 30 μmol) was converted to
1
furnish compound 1e (20 mg, 27 μmol, 90%) as a colorless solid (dec. 101°C). H
NMR (500 MHz, acetone-d6): δ = 2.61–2.72 (m, 4 H), 3.07–3.10 (m, 4 H), 7.52 (s, 1
13
H), 7.73 (s, 2 H), 8.11–8.13 (m, 2 H), 8.19–8.20 (m, 2 H) ppm. C{1H} NMR (125
MHz, acetone-d6): δ = 26.94 (t, J = 3.7 Hz, 2 CH2), 32.99 (t, J = 21.9 Hz, 2 CH2),
127.04 (2 CH), 128.48 (2 CH), 129.51 (2 CH), 130.59 (CH), 139.96 (C), 141.85 (2 C),
19
143.71 (C), 149.04 (C) ppm. F{1H} NMR (470 MHz, acetone-d6): δ = (–126.66)–(–
126.59) (m, 2 CF2), (–124.86)–(–124.79) (m, 2 CF2), (–115.00)–(–114.95) (m, 2 CF2),
(–81.97)–(–81.93) (m, 2 CF3) ppm. IR (ATR): nu(tilde) = 3426 (w), 2957 (w), 2932
(w), 1216 (vs), 1192 (s), 1176 (s), 1126 (vs), 568 (vs) cm–1. HRMS (ESI, neg. mode):
calcd. 726.0460 (for C24H15F18O3S–); found 726.0453 [M – H3O+]. C24H16F18O3S ∙
H2O (744.44): calcd. C 38.72, H 2.44, S 4.31; found C 39.11, H 2.44, S 4.50.
3',5'-Bis(1H,1H,2H,2H-perfluorooctyl)biphenyl-4-sulfonic acid monohydrate (1f).
According to the GPF, sulfonyl chloride 13f (10 mg, 11 μmol) was converted to fur-
nish compound 1f (9 mg, 10 μmol, 91%) as a colorless solid (dec. 91°C). Due to no
solubility in any solvent, we were not able to obtain NMR spectra. IR (ATR): nu(tilde)
= 3417 (w), 2954 (w), 1186 (vs), 1142 (s), 1122 (s), 630 (s) cm–1. HRMS (ESI, neg.
mode): calcd. 925.0332 (for C28H15F26O3S–); found 925.0317 [M – H3O+].
C28H16F26O3S ∙ H2O (944.47).
3',5'-Bis(1H,1H,2H,2H-perfluorohexyl)biphenyl-3,5-disulfonic
acid
dihydrate
(1g). According to the GPF, sulfonyl chloride 13g (22 mg, 30 μmol) was converted to
furnish compound 1g (23 mg, 27 μmol, 90%) as a colorless solid (dec. 107°C). Due
to no solubility in any solvent, we were not able to obtain NMR spectra. IR (ATR):
nu(tilde) = 2936 (w), 1625 (s), 1396 (s), 1372 (s), 1006 (s), 979 (s), 831 (vs), 703 (vs)
cm–1. HRMS (ESI, neg. mode): calcd. 401.9978 (for C24H14F18O6S22–); found
401.9966 [M – 2 H3O+]. C24H16F18O6S2 ∙ 2 H2O (842.51).
3',5'-Bis(1H,1H,2H,2H-perfluorooctyl)biphenyl-3,5-disulfonic acid dihydrate (1h).
According to the GPF, sulfonyl chloride 13h (10 mg, 10 μmol) was converted to fur-
nish compound 1h (9 mg, 9 μmol, 90%) as a colorless solid (dec. 93°C). Due to no
solubility in any solvent, we were not able to obtain NMR spectra. IR (ATR): nu(tilde)
25
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10.1002/ejoc.201800882
European Journal of Organic Chemistry
= 3458 (w), 2924 (w), 1233 (s), 1189 (vs), 1143 (s) cm–1. HRMS (ESI, neg. mode):
calcd. 501.9914 (for C28H14F26O6S22–); found 501.9893 [M – 2 H3O+]. C28H16F26O6S2 ∙
2 H2O (1042.54).
Acknowledgement
Financial support from the Deutsche Forschungsgemeinschaft is gratefully acknow-
ledged. MTBE was obtained as a generous gift from Evonik Industries, Marl, Ger-
many.
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