Aromatic Esters, Carbinols, and Derivatives Thereof with Perfluorohexyl Residues as Alternatives to Perfluoroalkanecarboxylic and -sulfonic Acids

Article abstract of DOI:10.1002/ejoc.201601298

Four perfluorohexyl carbinols have been prepared from the corresponding Grignard reagent and benzaldehyde, terephthalaldehyde, isophthalaldehyde, and trimesaldehyde. The corresponding secondary alcohols were then transformed by alkylation and acylation reactions to form a total of 14 ethers (methyl, ethyl, propyl, and n-hexyl ethers) and esters (acetyl and 2-ethylhexanoyl), respectively. Furthermore, 11 perfluoroalkyl carboxylates were prepared from aromatic, heteroaromatic, and aliphatic mono-, di-, tri-, and tetracarboxylic acids and tridecafluorooctanol. The wettability of all 29 materials was investigated by the water contact angle measurements of thin films on glass surfaces. In up to six cases, contact angles greater than 130° were observed, which indicates that the products might be suitable candidates for the impregnation of surfaces. With their relatively short perfluoroalkyl side-chains and therefore low bioaccumulativity, the target compounds might be beneficial alternatives to established products.

Full text of DOI:10.1002/ejoc.201601298

A Journal of
Accepted Article
Title: Fluorinated Alkyl Aryl Esters, Carbinols and Derivatives Thereof as Alternati-
ves to Perfluoroalkyl Carboxylic and Sulfonic Acids
Authors: Jens Christoffers; Torben Alpers; Thomas W. T. Muesmann; Oliver Temme
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Object Identifier (DOI) given below. The VoR will be published online in Early View as
soon as possible and may be different to this Accepted Article as a result of editing.
Readers should obtain the VoR from the journal website shown below when it is pu-
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201601298
Link to VoR: https://doi.org/10.1002/ejoc.201601298
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
Fluorinated Alkyl Aryl Esters, Carbinols and Derivatives Thereof as
Alternatives to Perfluoroalkyl Carboxylic and Sulfonic Acids
Torben Alpers,[a,b] Thomas W. T. Muesmann,[b] Oliver Temme,[b] Jens Christoffers*[a]
[a] MSc. T. Alpers, Prof. Dr. J. Christoffers, Institut for Chemie, Carl von Ossietzky
Universität Oldenburg, 26111 Oldenburg, Germany. Fax: +49(0)441 798 3873. Email:
jens.christoffers@uni-oldenburg.de.
oldenburg.de
Homepage:
www.christoffers.chemie.uni-
[b] MSc. T. Alpers, Dr. T. Muesmann, Dr. O. Temme, Ferdinand Eimermacher GmbH
& Co. KG, Westring 24, 48356 Nordwalde, Germany.
Graphical Abstract
Key topic: Fluorinated Compounds
Short, but still repellent. Aromatic esters and carbinols with perfluorohexyl residues
and some derivatives thereof were prepared as novel, biodegradable materials for
textile impregnation.
Abstract: Perfluorohexyl carbinols were prepared from the respective Grignard
reagent and benz-, terephthal-, isophthal- and trimesalydehyde (four products). The
corresponding secondary alcohols were further transformed by ether (methyl, ethyl,
1
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
propyl and n-hexyl) and ester formation (with acetyl chloride and 2-ethylhexanoyl
chloride) yielding 14 derivatives. Furthermore, perfluoroalkyl esters were prepared
from aromatic, heteroaromatic and aliphatic mono-, di-, tri- and tetracarboxylic acids
and tridecafluorooctanol. The wettability of all 29 materials was investigated by water
contact angle measurements of a thin film on a glass surface. In up to six cases,
contact angles >130° were observed indicating, that the products might be suitable
candidates for the impregnation of surfaces. With their relatively short perfluoroalkyl
side chains and therefore low bioaccumulativity, the target compounds might be
beneficial alternatives to established products.
Keywords: Fluorine compounds, wettability, esters, alkohols, ethers, Grignard
reagent.
Introduction
Perfluoroalkyl carboxylic and sulfonic acids with longer carbon chains (CnF2n+1CO2H
and CnF2n+1SO3H with n > 6) and derivatives thereof have found ubiquitous
applications for surface treatment of textiles, leathers, cardboard, paper, polymeric
materials, metals etc.[1] Especially so called fluorocarbon resins are widely in use as
impregnation materials for industrial as well as consumer[2] applications. The
manufacturing of impregnation materials, especially for the car industry is still based
on PFOA (C7F15CO2H) and PFOS (C8F17SO3H). While the final impregnation
products are quite harmless, their purification in the industrial scale is not thorough
enough to eliminate all of the very persistent PFOA and PFOS residues. During their
use the impregnation products pollute the environment with these residues of PFOA
and PFOS. Due to their persistency and bioaccumulativity, they are detectable
2
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
ubiquitously in the abiotic environment[3] as well as in animals and humans[4] and
have thus attracted attention as global contaminants. As a result, these compounds
were listed under Annex B (restriction of production and use) of the Stockholm
Convention in 2009.[5] PFOA is furthermore listed on the SVHC-candidates list of the
European Chemicals Agency as CMR-substance.[6] Shorter chain compounds with
C6F13 and C4F9 residues are also quite persistent, although their dwell time in
organisms is much shorter. Actually, a recent study on the cytotoxicity and
bioaccumulation of C6 to C10 perfluoroalkanoic acids showed, that compounds with
C6 to C8 are not cytotoxic in concentrations up to 200 mg/L, whereas C9 and C10
compounds are already harmful at 25 mg/L. Furthermore, the C6 compound could not
– in contrast to the longer chain compounds – be detected by mass spectrometry
inside the cells.[7] It was furthermore proposed in the literature, that compounds with
C6F13 and C4F9 residues possess improved biodegradability.[8] Therefore, several
industrial initiatives started off identifying replacements for perfluoroalkyl materials,
being e.g. shorter chain homologues or other types of fluorinated and non-fluorinated
chemicals.[9] Having the great advantages of perfluorinated compounds with their
outstanding material properties in view, we would like to contribute to this field with
new environmentally optimized compounds being readily accessible.
As a manufacturer of water repellent textile coatings, we are also aiming at identifying
new compounds with attributes fitting into on the one hand our property
characteristics and being on the other hand degradable after exposure into the
environment. We propose that both features will be addressed by compounds with a
secondary alcohol function possessing an aromatic scaffold and a perfluorohexyl
chain (nC6F13) as well as ethers and esters thereof. Furthermore, we prepared
perfluorinated alkyl esters of aromatic oligocarboxylic acids. Herein we wish to
disclose the synthesis of two small libraries of such compounds and their basic
3
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
physical properties.
Results and Discussion
Perfluorohexylcarbinols and derivatives thereof. Our first synthetic approach to
access a small library of compounds of potential interest started from perfluorohexyl
iodide and is given in Scheme 1. Aromatic aldehydes 1a–1d were converted with
perfluorohexyl Grignard reagent (nC6F13MgX) to furnish the secondary alcohols 2a–
2d. After some experimentation with activated elemental Mg, it turned out that the
Grignard reagent was conveniently prepared by magnesium-iodine exchange at low
temperature from MeMgBr-solution and nC6F13I, as recommended in the literature.[10]
Although compounds 2b and 2c possess two, and compound 2d even three
stereocenters no duplication of signal sets in the NMR spectra was observed,
presumably due to line broadening by strong association in the NMR solvent.
(a)
(b)
Ar(CHO)n
Ar[CH(OH)RF]n
Ar[CH(OR)RF]n
1a-1d
R = C F
2a (100%)
2b (88%)
2c (75%)
2d (51%)
3a-3n
n
F
6 13
CHO
CHO
CHO
CHO
CHO
OHC
CHO
CHO
1a
1b
1c
1d
Scheme 1. Synthesis of products 2a–2d and 3a–3n from aldehydes 1a–1d.
Reagents and conditions: (a) m equiv. MeMgBr, m equiv. nC6H13I, Et2O, –78°C, 8 h;
m = 1.5 for 1a, m = 4 for 1b and 1c, m = 8 for 1d; (b) For conditions, constitution of
products and yields see Table 1. Ethx = 2-ethylhexanoyl, RF = nC6F13.
4
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
Since alcohols 2 are relatively polar compounds and moreover could associate with
water by hydrogen bonding, we explored further transformations by either alkylation
or acylation. Suitable conditions were first elaborated for the simplest scaffold
represented by compound 2a (for constitutions of products, yields and conditions see
Table 1). After deprotonation with a small excess of NaH, alkylation was achieved
with a large excess of MeI, EtI, nPrBr or nHexBr in THF at 50°C. The highest yield
was achieved for product 3a (entry 1), which is not surprising since MeI is the
sterically least hindered electrophile. Surprisingly, the yields for the ethyl, propyl and
hexyl ethers do neither correlate with the leaving group (iodide vs. bromide) nor with
the lengths of the alkyl chains (range 8–42%, entires 3–5). Best results for acylations
were achieved when treating the alcohol 2a with an excess of the respective acid
chloride (AcCl or 2-ethylhexanoylchloride = EthxCl) in pyridine. Yields were satisfying
in both cases (52% and 62%, resp., entries 5 and 6). Compound 3f has two
stereocenters, thus, a doubled signal set (ratio 1 : 1) is observed in the NMR spectra.
Alkylation of the disubstituted scaffolds 2b and 2c were performed with 5 equiv. of
NaH and 5 equiv of MeI or EtI. For the para-isomer 2b the methylation proceeded
straightforwardly and product 3g was obtained in 85% yield (entry 7). In analogy to
the ethylation of compound 3b, the yield of the ethyl ether 3h was low (9%, entry 8).
The ethylation was therefore not performed for the meta-isomer 2c. In this case, only
the methyl ether 3k was prepared (66%, entry 11). Acylation of the para- and meta-
dialcohols 2b and 2c were performed with 6 equiv. of acid chlorides yielding the
esters 3i, 3j, 3l, 3m in 29-41% yield (entries 9, 10, 12, 13). The NMR spectra of
products in entries 7–13 showed at least doubled (for Ethx-esters multiple) signal
sets due to diastereoisomers (see experimental section for details). The triple
functionalization of compound 2d turned out to be rather difficult. The triacetyl-
compound 3n (64%, entry 14) was the only derivative which could be obtained.
5
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
Table 1. Etherification and esterification of alcohols 2a–2d; RF = nC6F13.
Scaffold
Entry Product
R
Yield
Conditions
RF
OR
1
2
3
4
3a
3b
3c
3d
Me
Et
nPr
75%
21%
8%
1.5 equiv. NaH, 6.0 equiv.
MeI, EtI, nPrBr, or nHexBr,
THF, 0°C50°C, 17 h
nHex 42%
5
3e
Ac
52%
62%
1.5 equiv. AcCl, pyridine,
0°C23°C, 24 h
6
3f
Ethx
2.0 equiv. EthxCl, pyridine,
0°C23°C, 24 h
RF
OR
7
8
3g
3h
Me
Et
85%
9%
5.0 equiv. NaH, 5.0 equiv.
MeI or EtI, THF,
0°C50°C, 17 h
9
10
3i
3j
Ac
Ethx
45%
33%
6.0 equiv. RCl, pyridine,
0°C23°C, 24 h
RF
RF
OR
OR
11
3k
Me
66%
5.0 equiv. NaH, 5.0 equiv.
MeI, THF, 0°C50°C, 17 h
12
13
3l
3m
Ac
Ethx
41%
29%
6.0 equiv. RCl, pyridine,
0°C23°C, 24 h
OR
OR
RF
RF
14
3n
Ac
64%
6.0 equiv. AcCl, pyridine,
0°C23°C, 24 h
RF
OR
RO
RF
It has to be pointed out, that we were not able to obtain mass spectrometric data of
most of compounds 3, neither by using EI, CI or ESI techniques. In these cases,
matching elemental analyses were obtained from respective products in order to
have proof for the elemental compositions.
6
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
Esters of oligocarboxylic acids. As a second building block we utilized 2-
(perfluorohexyl)ethanol for the preparation of esters from several oligocarboxylic
acids. The acid chlorides were either prepared by treating the carboxylic acids with
an excess of SOCl2,[11] if they were not commercially available like PhCOCl (5a),
(COCl)2 (5i) or the solution of phosgene (5k) in toluene. The acid chlorides were then
reacted with the alcohol nC6F13CH2CH2OH in pyridine solution to yield the
corresponding esters 6a–6k after acidic workup, extraction and crystallization from
CH2Cl2.
(b)
(a)
ArEn
Ar(CO2H)n
Ar(COCl)n
-
4b-4h
5a 5k
6a-6k
E = CO2CH2CH C F
2n
6 13
E
E
E
E
E
E
E
E
E
E
E
E
E
E
(52%)
(62%)
(62%)
(43%)
E
(74%)
(98%)
6f
6a
6g
6b
6c
6d
6e
E
E
E
E OCH CH C F
2n
E E
2
6 13
E
N
E
N
(93%)
(55%)
(100%)
(67%)
(21%)
6k
6h
6i
6j
Scheme 2. Synthesis of esters and from carboxylic acids 4b–4h via the acid
chlorides 5a–5k; for products 6a, 6i and 6k acid chlorides were used directly (yield
given over one step); compound 5j was prepared from succinic anhydride and SOCl2;
in case of compound 6k a solution of phosgene (5k) in toluene was used. For
products 6b–6h and 6i the given yield is over two steps. Reagents and conditions: (a)
xs. SOCl2, 4 h, 80°C; (b) 1.5 equiv. (per COCl group) nC6F13CH2CH2OH, pyridine, 3
h, 90°C. E = CO2CH2CH2nC6F13.
7
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European Journal of Organic Chemistry
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Physical Properties. In order to obtain a first impression of water repellency of the
new products we have investigated the wettability of a thin film spread on a glass
surface by measuring the water contact angle. Figure 1 shows a representative
photograph of the droplet on the impregnated surface. Table 2 lists the average of
left and right angle together with the melting point and the fluorine content.
Obviously, no correlation can be derived from the angles and the two other pieces of
data. A great influence, however, seems to have the constitution of the compound:
As an example, the angle for the constitutional ortho, meta and para isomers
(compounds 6b, 6c, 6d) jumps from ca. 120° via 135° to 75°. These results make
clear, that predictions cannot be made, and all compounds must instead be
investigated individually, which will be our main task within the near future. Anyhow,
although we have prepared no compound with a contact angle >150°, which is
normally regarded as "super-hydrophobic",[12] with six out of 29 compounds with a
contact angle >130° we seem to be on the right way in order to obtain hydrophobic
compounds suitable for textile impregnation, which are expected to be – as a benefit
of shorter perfluoroalkyl chains – bio-degradable.
Table 2. Selected properties of fluorinated compounds: Melting points, fluorine
content (% w/w) and water contact angles (the average value between left and right
angle together with its span width is given).
Compound
contact angle
111.40.3°
126.90.2°
136.50.1°
103.80.5°
Fluorine content / % w/w
mp.
2a
2b
2c
2d
58
64
64
66
53°C
133°C
86°C
131°C
8
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European Journal of Organic Chemistry
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[a]
3a
3b
3c
3d
3e
3f
27.51.0°
56
54
53
48
53
45
62
59
58
48
62
58
48
59
58
58
58
58
58
60
57
57
63
61
65
–
[a]
64.60.8°
30.91.0°
33.31.4°
140.30.0°
118.30.4°
123.20.6°
42.10.2°
116.00.1°
130.90.2°
126.10.2°
133.00.7°
82.80.6°
119.10.1°
47.21.1°
121.10.2°
133.90.1°
74.30.2°
112.80.2°
117.80.1°
118.60.9°
117.21.0°
136.00.0°
85.32.0°
43.80.2°
–
[a]
–
[a]
–
43°C
41°C
70°C
3g
3h
3i
[a]
–
109°C
99°C
45°C
66°C
3j
3k
3l
[a]
3m
3n
6a
6b
6c
6d
6e
6f
–
[a]
–
[a]
–
161°C
47°C
36°C
73°C
114°C
127°C
132°C
43°C
6g
6h
6i
[a]
6j
–
[a]
6k
–
9
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
[a] not a solid at ambient temperature.
Figure 1. Shape of a water droplet on a glass surface coated with compound 2c;
contact angles are 136.4° and 136.5°, resp.
Summary. We have prepared 29 new compounds with up to four perfluoro-n-hexyl
moieties, which shall serve as materials for textile coatings. As a first survey of their
property profile, we have investigated their wettability by water contact angle
measurements of a thin film on a glass surface. In up to six cases, contact angles
>130° were observed indicating, that the products might be suitable candidates for
the impregnation of surfaces. Further studies are in progress in our laboratories, in
particular, studies on the biodegradability of the new compounds. The latter shall
actually be the key property of the new materials. With their relatively short
perfluoroalkyl side chains and therefore low bioaccumulativity, the target compounds
might be beneficial alternatives to established products, like PFOA (C7F15CO2H) and
PFOS (C8F17SO3H).
The compounds prepared in this study divide into two classes: Perfluorohexyl
carbinols were prepared from the respective Grignard reagent and benz-, terephthal-,
10
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
isophthal- and trimesalydehyde (four products). The corresponding secondary
alcohols were further transformed by ether (methyl, ethyl, propyl and n-hexyl) and
ester formation (with acetyl chloride and 2-ethylhexanoyl chloride) yielding 14
derivatives. As a second set of 15 compounds, we have prepared perfluoroalkyl
esters from aromatic, heteroaromatic and aliphatic mono-, di-, tri- and tetracarboxylic
acids and tridecafluorooctanol.
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 ethyl acetate
(EtOAc) as eluents. TLC was performed on Merck aluminium plates coated with SiO2
1
F254. H-, 19F- and 13C-NMR spectra were recorded on a Bruker Avance DRX 500
instrument. Multiplicities of carbon signals were determined with DEPT experiments.
MS and HRMS spectra of products were obtained with a Waters Q-TOF Premier
(ESI) spectrometer. IR spectra were recorded on a Bruker Tensor 27 spectrometer
equipped with a "GoldenGate" diamond ATR unit. Elemental analyses were
determined with a Euro EA-CHNS instrument from HEKAtech. Contact angle
measurements were performed with a Contact Angle System OCA, model 15plus
from dataphysics and a Teli ccd camera, model CS8620C1. The droplet volume was
9 μL and photograph was taken after 2 s. All starting materials were commercially
available. In particular, nC6F13I was purchased from Apollo, nC6F13CH2CH2OH from
DuPond, and MeMgBr solution from Sigma-Aldrich.
11
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European Journal of Organic Chemistry
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2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-1-phenyl-1-heptanol (2a).[13] Under an inert
atmosphere (N2) and exclusion of moisture, MeMgBr (15.0 mL, 44.7 mmol, 3 mol L–1
solution in Et2O, 1.5 equiv.) was added at –78°C (dry ice-acetone bath) to a solution
of nC6F13I (19.9 g, 44.7 mmol, 1.5 equiv.) in Et2O (60 mL) and the resulting mixture
was stirred for 2 h at the same temperature. Subsequently, freshly distilled PhCHO
(1a) (3.16 g, 29.8 mmol, 1.00 equiv.) was added at –78°C and the solution was
stirred for further 8 h at the same temperature. Saturated, aqueous NH4Cl solution
(25 mL) was added to the mixture. After warming to ambient temperature, the layers
were separated and the aqueous layer extracted with MTBE (3 x 30 mL). The
combined organic layers were washed with water (2 x 30 mL) and brine (2 x 30 mL),
dried (MgSO4) and evaporated after filtration. The residue was purified by
chromatography (SiO2, hexanes/MTBE 5 : 1, Rf = 0.45) to furnish the product 2a
(12.7 g, 29.8 mmol, 100%) as a colorless solid, mp. 53°C (lit. 47°C[13a]). 1H-NMR (500
MHz, CDCl3): δ = 2.43 (d, J = 5.1 Hz, 1H), 5.21 (dt, J = 17.8 Hz, J = 5.7 Hz, 1H),
7.39–7.51 (m, 5H) ppm. 13C{1H}-NMR (125 MHz, CDCl3): δ = 72.37–72.78 (m, CH),
128.17 (2 CH), 128.81 (2 CH), 129.89 (CH), 134.13 (C) ppm. 19F{1H}-NMR (470 MHz,
CDCl3): δ = –80.80 (tt, J = 9.6 Hz, J = 2.6 Hz), (–117.55)–(–126.84) (m) ppm. IR
(ATR): nu(tilde) = 3438 (m), 1497 (w), 1458 (s), 1365 (m), 1316 (w), 1227 (s), 1201
(s), 1141 (s), 1058 (m), 1047 (s), 1028 (m), 1004 (w), 827 (w), 776 (m), 734 (m), 717
(s), 698 (s), 662 (m), 626 (m) cm–1. MS (ESI, neg. mode): m/z (%) = 851 (25) [2 M –
H+], 471 (100), 319 (20). All spectroscopic data are in accordance with the
literature.[13] C13H7F13O (426.18): calcd. C 36.64%, H 1.66%; found C 36.32%, H
1.51%.
12
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European Journal of Organic Chemistry
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1,4-Bis(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxyheptyl)benzene
(2b).
Following the procedure given above for compound 2a, nC6F13I (26.8 g, 60.0 mmol,
4.0 equiv.), MeMgBr (20.0 mL, 60.0 mmol, 3 mol L–1 solution in Et2O, 4.0 equiv.) and
terephthalaldehyde (1b) (2.10 g, 15.0 mmol, 1.0 equiv.) were converted to give the
title compound 2b (10.3 g, 13.3 mmol, 88%) as a colorless solid (mp. 133°C) after
chromatography (SiO2, hexanes/MTBE 1 : 1, Rf = 0.61). 1H-NMR (500 MHz, acetone-
13
d6): δ = 5.46 (dd, J = 20.4 Hz, J = 5.2 Hz, 2H), 7.64 (s, 4H) ppm. C{1H}-NMR (125
MHz, acetone-d6): δ = 71.75–72.20 (m, 2 CH), 129.13 (4 CH), 137.36 (2 C) ppm.
19F{1H}-NMR (470 MHz, acetone-d6): δ = 49.86–61.06 (m), 95.72 (tt, J = 10.3 Hz, J =
2.7 Hz) ppm. IR (ATR): nu(tilde) = 3404 (m), 2925 (m), 1426 (w), 1365 (m), 1318 (m),
1230 (s), 1187 (s), 1142 (s), 1118 (s), 1066 (s), 1051 (m), 1019 (w), 942 (w), 914 (w),
863 (w), 846 (w), 813 (m), 785 (m), 764 (m), 738 (m), 717 (s), 709 (s), 691 (s), 654
(s) cm–1. HR-MS (ESI, neg. mode): calcd. 773.0031 (for C20H7F26O2), found 773.0042
[M – H+]. C20H8F26O2 (774.24).
1,3-Bis(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxyheptyl)benzene
(2c).
Following the procedure given above for compound 2a, nC6F13I (26.8 g, 60.0 mmol,
4.0 equiv.), MeMgBr (20.0 mL, 60.0 mmol, 3 mol L–1 solution in Et2O, 4.0 equiv.) and
isophthalaldehyde (1c) (2.10 g, 15.0 mmol, 1.0 equiv.) were converted to give the title
compound 2c (8.67 g, 11.2 mmol, 75%) as a colorless solid (mp. 86°C) after
chromatography (SiO2, hexanes/MTBE 1 : 1, Rf = 0.61). Due to two diastereoisomers
1
(ratio ca. 1 : 1), the 13C-NMR spectrum shows a partly doubled signal set. H-NMR
(500 MHz, acetone-d6): δ = 5.48 (dd, J = 19.8 Hz, J = 5.7 Hz, 2H), 7.50 (t, J = 7.7 Hz,
1H), 7.62 (d, J = 7.4 Hz, 2H), 7.78 (s, 1H) ppm. 13C{1H}-NMR (125 MHz, acetone-d6):
δ = 71.85–72.26 (m, 2 CH), 128.99 (CH), 129.27 (½ CH), 129.31 (½ CH), 129.95 (2
CH), 136.52 (2 C) ppm. 19F{1H}-NMR (470 MHz, acetone-d6): δ = 49.77–60.73 (m),
13
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95.66 (t, J = 10.1 Hz) ppm. IR (ATR): nu(tilde) = 3576 (w), 1366 (w), 1317 (w), 1231
(s), 1194 (s), 1138 (s), 1120 (s), 1067 (s), 907 (w), 781 (w), 756 (m), 733 (w), 719
(m), 706 (s), 662 (m), 633 (m) cm–1. HR-MS (ESI, neg. mode): calcd. 773.0031 (for
C20H7F26O2), found 773.0031 [M – H+]. C20H8F26O2 (774.24).
1,3,5-Tris(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxyheptyl)benzene
(2d).
Following the procedure given above for compound 2a, nC6F13I (22.0 g, 49.3 mmol,
8.00 equiv.), MeMgBr (16.6 mL, 49.3 mmol, 3 mol L–1 in Et2O, 8.00 equiv.) and
trialdehyde 1d (1.00 g, 6.17 mmol, 1.00 equiv.) were converted to give the title
compound 2d (3.51 g, 3.12 mmol, 51%) as a colorless solid (mp. 131°C) after
recrystallization from CH2Cl2 (50 mL). 1H-NMR (500 MHz, acetone-d6): δ = 5.55 (dt, J
= 18.9 Hz, J = 6.1 Hz, 3H), 6.03 (d, J = 6.0 Hz, 3H), 7.82 (s, 3H) ppm. 13C{1H}-NMR
(125 MHz, acetone-d6): δ = 71.84–72.30 (m, 3 CH), 129.88 (3 CH), 136.63 (3 C)
ppm. 19F{1H}-NMR (470 MHz, acetone-d6): δ = 50.07–60.57 (m), 95.73 (t, J = 10.4
Hz) ppm. IR (ATR): nu(tilde) = 3368 (w), 1367 (w), 1319 (w), 1231 (s), 1192 (s), 1174
(s), 1121 (s), 1057 (m), 903 (w), 698 (s) cm–1. C27H9F39O3 (1122.30): calcd. C
28.90%, H 0.81%; found C 29.01%, H 0.52%.
(2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-1-methoxyheptyl)benzene (3a). NaH (14
mg, 60% w/w dispersion in mineral oil, 0.35 mmol, 1.5 equiv.) was washed with
hexanes (2 x 5 mL), dried in vacuum and then added to a solution of alcohol 2a (100
mg, 0.235 mmol, 1.0 equiv.) in THF (2 mL). The resulting mixture was stirred at 50°C
for 3 h and then cooled to 0°C. MeI (200 mg, 1.40 mmol, 6.0 equiv.) was added and
the mixture warmed to ambient temperature and stirred for 17 h. Subsequently, the
mixture was diluted with MTBE (10 mL) and washed with water (2 x 10 mL) and brine
(2 x 10 mL). The organic layer was dried (MgSO4) and evaporated after filtration to
1
yield the title compound 3a (78.0 mg, 0.177 mmol, 75%) as a colorless oil. H-NMR
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(500 MHz, CDCl3): δ = 3.35 (s, 3H), 4.66 (dd, J = 19.7 Hz, J = 4.3 Hz, 1H), 7.42–7.45
(m, 5H) ppm. 13C{1H}-NMR (125 MHz, CDCl3): δ = 57.76 (CH3), 80.56–81.12 (CH),
128.69 (2 CH), 129.05 (2 CH), 129.83 (CH), 131.72 (C) ppm. 19F{1H}-NMR (470 MHz,
CDCl3): δ = –80.78 (tt, J = 9.9 Hz, J = 2.7 Hz), (–115.51)–(–126.96) (m) ppm. IR
(ATR): nu(tilde) = 2924 (m), 2855 (m), 1716 (w), 1458 (m), 1365 (m), 1352 (m), 1237
(s), 1145 (s), 1121 (s), 1068 (m), 1030 (w), 988 (w), 860 (w), 789 (w), 776 (w), 731
(m), 716 (m), 699 (m), 664 (w), 620 (w) cm–1. C14H9F13O (440.20): calcd. C 38.20%,
H 2.06%; found C 38.58%, H 2.22%.
(1-Ethoxy-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)benzene (3b). Following the
procedure given above for product 3a, alcohol 2a (200 mg, 0.470 mmol, 1.0 equiv.)
was deprotonated with NaH (28 mg, 60% w/w dispersion in mineral oil, 0.71 mmol,
1.5 eq) and alkylated with ethyl iodide (440 mg, 2.82 mmol, 6.0 equiv.) to furnish the
title compound 3b (44 mg, 0.097 mmol, 21%) as a colorless oil after chromatography
(SiO2, hexanes/MTBE 100 : 1, Rf = 0.45). 1H-NMR (500 MHz, CDCl3): δ = 1.22 (t, J =
7.0 Hz, 3H), 3.45 (dq, J = 9.2 Hz, J = 7.2 Hz, 1H), 3.53 (dq, J = 9.2 Hz, J = 7.0 Hz,
1H), 4.77 (dd, J = 19.9 Hz, J = 4.6 Hz, 1H), 7.40–7.45 (m, 5H) ppm. 13C{1H}-NMR
(125 MHz, CDCl3): δ = 14.98 (CH3), 65.91 (CH2), 78.86–79.26 (CH), 128.60 (2 CH),
128.98 (2 CH), 129.66 (CH), 132.49 (C) ppm. 19F{1H}-NMR (470 MHz, CDCl3): δ = –
80.84 (tt, J = 10.3 Hz, J = 3.1 Hz), (–115.26)–(–127.12) (m) ppm. IR (ATR): nu(tilde)
= 2985 (w), 2888 (w), 2361 (w), 2338 (w), 1644 (w), 1497 (w), 1458 (w), 1408 (w),
1351 (w), 1315 (w), 1234 (s), 1195 (s), 1144 (s), 1106 (s), 1075 (m), 1068 (m), 1034
(m), 968 (w), 944 (w), 898 (w), 856 (w), 817 (w), 787 (w), 776 (w), 729 (m), 714 (m),
698 (s), 663 (m) cm–1. C15H11F13O (454.23): calcd. C 39.66%, H 2.44%; found C
39.26%, H 2.33%.
15
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[2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-1-(propyloxy)heptyl]benzene (3c). Follo-
wing the procedure given above for product 3a, alcohol 2a (200 mg, 0.470 mmol, 1.0
equiv.) was deprotonated with NaH (28 mg, 60% w/w dispersion in mineral oil, 0.71
mmol, 1.5 eq) and alkylated with 1-bromopropane (347 mg, 2.82 mmol, 6.0 equiv.) to
furnish the title compound 3c (18 mg, 0.038 mmol, 8%) as a colorless oil after
1
chromatography (SiO2, hexanes/MTBE 100 : 1, Rf = 0.43). H-NMR (500 MHz,
CDCl3): δ = 0.93 (t, J = 7.4 Hz, 3H), 1.57–1.65 (m, 2H), 3.33 (dt, J = 8.9 Hz, J = 6.5
Hz, 1H), 3.42 (dt, J = 8.9 Hz, J = 6.4 Hz, 1H), 4.75 (dd, J = 20.1 Hz, J = 4.6 Hz, 1H),
7.40–7.44 (m, 5H) ppm. 13C{1H}-NMR (125 MHz, CDCl3): δ = 10.56 (CH3), 22.88
(CH2), 72.08 (CH2), 79.14–79.54 (CH), 128.59 (2 CH), 129.02 (2 CH), 129.64 (CH),
132,46 (C) ppm. 19F{1H}-NMR (470 MHz, CDCl3): δ = –80.81 (tt, J = 10.1 Hz, J = 2.9
Hz), (–115.33)–(–127.03) (m) ppm. IR (ATR): nu(tilde) = 3077 (w), 2971 (w), 2885
(w), 2364 (w), 2345 (w), 1640 (m), 1459 (m), 1354 (m), 1236 (s), 1198 (s), 1146 (s),
1123 (s), 1078 (m), 1033 (m), 1003 (w), 968 (m), 913 (w), 858 (m), 818 (m), 789 (m),
778 (m), 730 (m), 700 (s), 666 (m) cm–1. C16H16F13O (468.26): calcd. C 41.04%, H
2.80%; found C 40.70%, H 2.90%.
[2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-1-(hexyloxy)heptyl]benzene (3d). Follo-
wing the procedure given above for product 3a, alcohol 2a (200 mg, 0.470 mmol, 1.0
equiv.) was deprotonated with NaH (28 mg, 60% w/w dispersion in mineral oil, 0.71
mmol, 1.5 eq) and alkylated with 1-bromohexane (465 mg, 2.82 mmol, 6.0 equiv.) to
furnish the title compound 3d (100 mg, 0.196 mmol, 42%) as a colorless oil after
1
chromatography (SiO2, hexanes/MTBE 100 : 1, Rf = 0.43). H-NMR (500 MHz,
CDCl3): δ = 0.87 (t, J = 7.0 Hz, 3H), 1.21–1.37 (m, 6H), 1.55–1.61 (m, 2H), 3.36 (dt, J
= 8.9 Hz, J = 6.5 Hz, 1H), 3.44 (dt, J = 9.0 Hz, J = 6.5 Hz, 1H), 4.74 (dd, J = 19.8 Hz,
13
J = 4.6 Hz, 1H), 7.40–7.44 (m, 5H) ppm. C{1H}-NMR (125 MHz, CDCl3): δ = 14.08
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(CH3), 22.67 (CH2), 25.63 (CH2), 29.54 (CH2), 31.59 (CH2), 70.48 (CH2), 79.15–79.56
(CH), 128.58 (2 CH), 129.02 (2 CH), 129.64 (CH), 132.47 (C) ppm. 19F{1H}-NMR
(470 MHz, CDCl3): δ = –80.81 (tt, J = 10.5 Hz, J = 2.1 Hz), (–115.31)–(–126.99) (m)
ppm. IR (ATR): nu(tilde) = 2938 (w), 2866 (w), 1459 (w), 1353 (w), 1236 (s), 1199 (s),
1146 (s), 1122 (s), 1069 (m), 700 (s) cm–1. C19H19F13O (510.34): calcd. C 44.72%, H
3.75%; found C 44.37%, H 3.49%.
(1-Acetoxy-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-phenyl)heptan (3e). AcCl (553
mg, 7.04 mmol, 1.5 equiv.) was added to ice-cooled pyridine (4 mL) and the resulting
mixture stirred for 10 min at 0°C. Subsequently, alcohol 2a (2.00 g, 4.69 mmol, 1.0
equiv.) was added and the mixture stirred for 1 d at ambient temperature. Finally,
water (20 mL) was added and the mixture acidified to pH 3 with conc. hydrochloric
acid (10 mL). After extraction with MTBE (2 x 20 mL) the combined organic layers
were dried (MgSO4) and the solvent evaporated after filtration. Chromatographic
purification of the residue (SiO2, hexanes/MTBE 50 : 1, Rf = 0.39) gave the title
compound 3e (1.14 g, 2.43 mmol, 52%) as a colorless solid, mp. 43°C. 1H-NMR (500
MHz, CDCl3): δ = 2.17 (s, 3H), 6.30 (dd, J = 17.7 Hz, J = 6.6 Hz, 1H), 7.39–7.48 (m,
5H) ppm. 13C{1H}-NMR (125 MHz, CDCl3): δ = 20.63 (CH3), 71.08–71.49 (CH),
128.78 (2 CH), 128.77 (2 CH), 130.11 (CH), 131.07 (C), 168.45 (C) ppm. 19F{1H}-
NMR (470 MHz, CDCl3): δ = –80.84 (tt, J = 9.6 Hz, J = 2.6 Hz), (–115.99)–(–126.82)
(m) ppm. IR (ATR): nu(tilde) = 3047 (w), 2971 (w), 1762 (m), 1375 (m), 1357 (m),
1216 (s), 1205 (s), 1145 (s), 1122 (m), 1091 (m), 1065 (m), 738 (m), 728 (m), 716
(m), 699 (s), 660 (m) 609 (m) cm–1. C15H9F13O2 (468.21): calcd. C 38.48%, H 1.94%;
found C 38.42%, H 1.76%.
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2-Ethylhexanoic acid [(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-phenyl)heptyl]-
ester (3f). According to the procedure reported above for the preparation of
compound 3e, the alcohol 2a (2.00 g, 4.69 mmol, 1.0 equiv.), 2-ethylhexanoyl
chloride (1.53 g, 9.38 mmol, 2.0 equiv.) and pyridine (5 mL) were converted to yield
the title compound 3f (1.95 g, 3.53 mmol, 62%) as a colorless solid, mp. 41°C, after
chromatography (SiO2, hexanes/MTBE 100 : 1, Rf = 0.52). The products is obtained
as a mixture of two diastereoisomers; two signal sets (ratio 1 : 1) were observed in
the NMR spectra. 1H-NMR (500 MHz, acetone-d6): δ = 0.79–0.97 (m, 6H), 1.10–1.38
(m, 4H), 1.38–1.50 (m, 4H), 2.39–2.50 (m, 1H), 6.45 (dd, J = 19.6 Hz, J = 5.9 Hz,
1H), 7.48–7.49 (m, 3H), 7.57–7.61 (m, 2H) ppm. 13C{1H}-NMR (125 MHz, acetone-
d6); isomer A: δ = 11.83 (CH3), 14.05 (CH3), 23.18 (CH2), 25.56 (CH2), 29.97 (CH2),
31.84 (CH2), 47.91 (CH), 71.63–72.05 (CH), 129.51 (2 CH), 129.65 (2 CH), 130.93
(CH), 132.13 (C), 172.39 (C) ppm; isomer B: δ = 11.84 (CH3), 14.06 (CH3), 23.21
(CH2), 25.85 (CH2), 30.05 (CH2), 32.24 (CH2), 47.96 (CH), 71.63–72.05 (CH), 129.51
19
(2 CH), 129.66 (2 CH), 130.93 (CH), 132.13 (C), 173.90 (C) ppm. F{1H}-NMR (470
MHz, acetone-d6): δ = 49.93–61.52 (m), 95.77 (tt, J = 10.1 Hz, J = 2.8 Hz) ppm. IR
(ATR): nu(tilde) = 2965 (w), 2944 (w), 2874 (w), 1743 (s), 1458 (w), 1229 (s), 1190
(s), 1148 (s), 1122 (s), 1070 (s), 699 (s) cm–1. C21H21F13O2 (552.38): calcd. C
45.66%, H 3.83%; found C 45.32%, H 4.06%.
1,4-Bis[(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-methoxy)heptyl]benzene
(3g).
Following the procedure given above for product 3a, alcohol 2b (100 mg, 0.129
mmol, 1.00 equiv.) was deprotonated with NaH (26 mg, 60% w/w dispersion in
mineral oil, 0.65 mmol, 5.0 eq) and alkylated with methyl iodide (92 mg, 0.65 mmol,
5.0 equiv.) to furnish the title compound 3g (85 mg, 0.11 mmol, 85%) as a colorless
solid, mp. 70°C, after chromatography (SiO2, hexanes/MTBE 100 : 1, Rf = 0.29). 1H-
18
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NMR (500 MHz, CDCl3): δ = 3.37 (s, 6H), 4.66 (dd, J = 19.6 Hz, J = 4.3 Hz, 2H), 7.50
(s, 4H) ppm. 13C{1H}-NMR (125 MHz, CDCl3): δ = 58.02 (2 CH3), 80.28–80.72 (2
19
CH), 129.18 (4 CH), 133.38 (2 C) ppm. F{1H}-NMR (470 MHz, CDCl3): δ = –80.86
(tt, J = 10.6 Hz, J = 2.2 Hz), (–115.45)–(–127.10) (m) ppm. IR (ATR): nu(tilde) = 2949
(w), 1451 (w), 1424 (w), 1369 (w), 1354 (w), 1318 (w), 1234 (s), 1194 (s), 1143 (s),
1097 (s), 1069 (s), 1051 (m), 1023 (w), 988 (m), 944 (w), 916 (w), 882 (w), 846 (w),
818 (w), 801 (w), 770 (w), 739 (w), 719 (m), 691 (m), 657 (s), 607 (m) cm–1. HR-MS
(ESI, pos. mode): calcd. 803.0500 (for C22H13F26O2), found 803.0500 [M + H+].
C22H12F26O2 (802.29).
1,4-Bis[(1-ethoxy-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro)heptyl]benzene
(3h).
Following the procedure given above for product 3a, alcohol 2b (200 mg, 0.258
mmol, 1.00 equiv.) was deprotonated with NaH (52 mg, 60% w/w dispersion in
mineral oil, 1.3 mmol, 5.0 eq) and alkylated with ethyl iodide (403 mg, 2.58 mmol, 10
equiv.) to furnish the title compound 3h (19 mg, 0.023 mmol, 9%) as a colorless oil
1
after chromatography (SiO2, hexanes/MTBE 100 : 1, Rf = 0.41). H-NMR (500 MHz,
acetone-d6): δ = 1.21 (t, J = 7.0 Hz, 6H), 3.56 (q, J = 7.0 Hz, 4H), 5.22 (dd, J = 20.6
Hz, J = 4.3 Hz, 2H), 7.65 (s, 4H) ppm. 13C{1H}-NMR (125 MHz, acetone-d6): δ =
15.19 (2 CH3), 66.48 (2 CH2), 78.75–78.98 (2 CH), 129.94 (4 CH), 134.89 (2 C) ppm.
19F{1H}-NMR (470 MHz, acetone-d6): δ = 49.81–64.82 (m), 95.79 (tt, J = 10.3 Hz, J =
2.3 Hz) ppm. IR (ATR): nu(tilde) = 2957 (m), 2925 (m), 2855 (m), 1715 (w), 1459 (w),
1365 (m), 1313 (w), 1231 (s), 1190 (s), 1143 (s), 1109 (s), 1081 (m), 1068 (m), 1037
(m), 1022 (m), 970 (w), 874 (w), 859 (w), 811 (w), 792 (w), 744 (m), 735 (m), 718 (m),
709 (m), 689 (m) cm–1. C24H16F26O2 (830.35): calcd. C 34.72%, H 1.94%; found C
34.85%, H 2.12%.
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1,4-Bis(1-acetoxy-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)benzene
(3i).
According to the procedure reported above for the preparation of compound 3e, the
alcohol 2b (2.00 g, 2.58 mmol, 1.0 equiv.), acetyl chloride (1.22 g, 15.5 mmol, 6.0
equiv.) and pyridine (10 mL) were converted to yield the title compound 3i (1.00 g,
1.17 mmol, 45%) as a colorless solid, mp. 109°C, after chromatography (SiO2,
hexanes/MTBE 25 : 1, Rf = 0.52). Due to two diastereoisomers (ratio ca. 1 : 1), the
1
13C-NMR spectrum shows a partly doubled signal set. H-NMR (500 MHz, CDCl3): δ
= 2.18 (s, 6H), 6.32 (dd, J = 18.3 Hz, J = 5.3 Hz, 2H), 7.51 (s, 4H) ppm. 13C{1H}-NMR
(125 MHz, CDCl3): δ = 20.60 (2 CH3), 70.56–70.97 (2 CH), 129.05 (½ x 4 CH),
129.11 (½ x 4 CH), 132.91 (C), 132.94 (C), 168.32 (2 C) ppm. 19F{1H}-NMR (470
MHz, CDCl3): δ = –80.79 (tt, J = 10.4 Hz, J = 2.7 Hz), (–115.78)–(–127.16) (m) ppm.
IR (ATR): nu(tilde) = 2975 (w), 1762 (s), 1377 (m), 1202 (s), 1184 (s), 1122 (s), 1062
(s), 1023 (m), 920 (m), 689 (s) cm–1. C24H12F26O4 (858.31): calcd. C 33.58%, H
1.41%; found C 33.84%, H 1.13%.
1,4-Bis[1-(2-ethylhexanoyloxy)(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)]ben-
zene (3j). According to the procedure reported above for the preparation of
compound 3e, the alcohol 2b (2.00 g, 2.58 mmol, 1.0 equiv.), 2-ethylhexanoyl
chloride (2.52 g, 15.5 mmol, 6.0 equiv.) and pyridine (5 mL) were converted to yield
the title compound 3j (867 mg, 0.845 mmol, 33%) as a colorless solid, mp. 99°C,
after chromatography (SiO2, hexanes/MTBE 100 : 1, Rf = 0.17). The product is
obtained as a mixture of several diastereoisomers; two signal sets (ratio 1.2 : 1) were
1
observed in the NMR spectra. H-NMR (500 MHz, CDCl3): δ = 0.75–0.85 (m, 12H),
1.07–1.34 (m, 8H), 1.45–1.70 (m, 8H), 2.39 (tt, J = 5.4 Hz, J = 8.8 Hz, 2H), 6.32 (dd,
J = 5.6 Hz, J = 17.4 Hz, 2H), 7.50 (s, 4H) ppm. 13C{1H}-NMR (125 MHz, CDCl3);
isomer A: δ = 11.58 (2 CH3), 13.78 (2 CH3), 22.58 (2 CH2), 25.27 (2 CH2), 29.44 (2
20
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CH2), 31.54 (2 CH2), 47.28 (2 CH), 70.05–71.14 (2 CH), 129.04 (4 CH), 133.13 (2 C),
173.77 (2 C) ppm; isomer B: δ = 11.62 (2 CH3), 13.80 (2 CH3), 22.63 (2 CH2), 25.48
(2 CH2), 29.44 (2 CH2), 31.73 (2 CH2), 47.28 (2 CH), 70.05–71.14 (2 CH), 129.04 (4
CH), 133.13 (2 C), 173.78 (2 C) ppm. 19F{1H}-NMR (470 MHz, CDCl3): δ = –80.83 (tt,
J = 9.7 Hz, J = 2.8 Hz), (–115.87)–(–127.17) (m) ppm. IR (ATR): nu(tilde) = 2968 (w),
2943 (w), 2869 (w), 1746 (s), 1461 (w), 1384 (w), 1366 (w), 1317 (w), 1281 (w), 1230
(s), 1188 (vs), 1173 (s), 1150 (vs), 1132 (s), 1086 (m), 1070 (s), 1020 (w), 954 (w),
690 (s), 646 (s) cm–1. C36H36F26O4 (1026.64): calcd. C 42.12%, H 3.53%; found C
42.41%, H 3.60%.
1,3-Bis[(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-methoxy)heptyl]benzene
(3k).
Following the procedure given above for product 3a, alcohol 2c (2.00 g, 2.58 mmol,
1.0 equiv.) was deprotonated with NaH (516 mg, 60% w/w dispersion in mineral oil,
12.9 mmol, 5.0 equiv.) and alkylated with methyl iodide (1.83 g, 12.9 mmol, 5.00
equiv.) to furnish the title compound 3k (1.36 mg, 1.69 mmol, 66%) as a brownish
solid after chromatography (SiO2, hexanes/MTBE 100 : 1, Rf = 0.55), mp. 45°C. Due
1
to two diastereoisomers (ratio ca. 1 : 1), the H-and 13C-NMR spectra show partly
1
doubled signal sets. H-NMR (500 MHz, CDCl3): δ = 3.36 (s, ½ x 6H), 3.37 (s, ½ x
6H), 4.71 (dd, J = 19.1 Hz, J = 4.9 Hz, 2H), 7.49–7.53 (m, 4H) ppm. 13C{1H}-NMR
(125 MHz, CDCl3): δ = 57.89 (2 CH3), 80.41–80.84 (2 CH), 128.95 (½ CH), 129.01
129.31 129.47 (½ CH), 130.27 (½ x 2 CH), 130.34 (½ x 2 CH), 132.32 (½ x 2 C),
132.36 (½ x 2 C) ppm. 19F{1H}-NMR (470 MHz, CDCl3): δ = –80.88 (tt, J = 9.8 Hz, J =
2.5 Hz), (–115.77)–(–126.97) (m) ppm. IR (ATR): nu(tilde) = 2256 (w), 1243 (m),
1209 (m), 1150 (w), 905 (s), 726 (s), 652 (m), 586 (w) cm–1. HR-MS (ESI, pos.
mode): calcd. 825.0320 (for C22H12F26NaO2), found 825.0320 [M + Na+]. C22H12F26O2
(830.35).
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1,3-Bis(1-acetoxy-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)benzene
(3l).
According to the procedure reported above for the preparation of compound 3e, the
alcohol 2c (2.00 g, 2.58 mmol, 1.00 equiv.), acetyl chloride (1.22 g, 15.5 mmol, 6.00
equiv.) and pyridine (10 mL) were converted to yield the title compound 3l (910 mg,
1.06 mmol, 41%) as a colorless solid, mp. 66°C, after chromatography (SiO2,
hexanes/MTBE 50 : 1, Rf = 0.43). Due to two diastereoisomers (ratio ca. 1 : 1), the
1H-NMR spectrum shows a partly doubled signal set. 1H-NMR (500 MHz, CDCl3): δ =
2.17 (s, ½ x 6H), 2.18 (s, ½ x 6H), 6.34 (dt, J = 5.8 Hz, J = 17.1 Hz, 2H), 7.45–7.49
13
(m, 1H), 7.52–7.56 (m, 3H) ppm. C{1H}-NMR (125 MHz, CDCl3): δ = 20.54 (CH3),
20.60 (CH3), 70.61–71.04 (2 CH), 128.84 (CH), 129.14 (CH), 130.47 (2 CH), 131.78
(2 C), 168.27 (C), 168.39 (C) ppm. 19F{1H}-NMR (470 MHz, CDCl3): δ = –80.85 (tt, J
= 9.7 Hz, J = 2.1 Hz), (–116.65)–(–126.99) (m) ppm. IR (ATR): nu(tilde) = 3020 (w),
2980 (w), 2974 (w), 1770 (s), 1761 (s), 1434 (w), 1371 (m), 1314 (w), 1231 (s), 1190
(vs), 1140 (vs), 1122 (s), 1066 (s), 1039 (m), 919 (m), 707 (s) cm–1. C24H12F26O4
(858.31): calcd. C 33.58%, H 1.41%; found C 33.61%, H 1.29%.
1,3-Bis[1-(2-ethylhexanoyloxy)(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)]ben-
zene (3m). According to the procedure reported above for the preparation of
compound 3e, the alcohol 2c (2.00 g, 2.58 mmol, 1.00 equiv.), 2-ethylhexanoyl
chloride (2.52 g, 15.5 mmol, 6.00 equiv.) and pyridine (5 mL) were converted to yield
the title compound 3m (772 mg, 0.752 mmol, 29%) as a colorless oil after
chromatography (SiO2, hexanes/MTBE 100 : 1, Rf = 0.17). Three signal sets (ratio 5 :
4 : 1) were observed in the NMR spectra due to the six possible diastereoisomers of
1
this compound. H-NMR (500 MHz, CDCl3): δ = 0.68–0.91 (m, 12H), 1.02–1.28 (m,
8H), 1.37–1.67 (m, 8H), 2.26–2.37(m, 2H), 6.23–6.30 (m, 2H), 7.34–7.47 (m, 3H),
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13
7.53 (s, 1H) ppm. C{1H}-NMR (125 MHz, CDCl3); signal set A: δ = 11.58 (2 CH3),
13.74 (2 CH3), 22.55 (CH2), 22.58 (CH2), 25.00 (2 CH2), 29.41 (2 CH2), 31.21 (2
CH2), 47.18 (2 CH), 70.36–71.08 (2 CH), 128.54 (CH), 128.89 (CH), 130.70 (2 CH),
131.85 (2 C), 173.70 (2 C) ppm; signal set B: δ = 11.63 (2 CH3), 13.84 (2 CH3), 22.60
(CH2), 22.62 (CH2), 25.23 (2 CH2), 29.44 (2 CH2), 31.48 (2 CH2), 47.40 (2 CH),
70.36–71.08 (2 CH), 128.54 (CH), 130.16 (CH), 130.70 (2 CH), 131.85 (2 C), 173.78
(2 C) ppm; signal set C: δ = 11.77 (2 CH3), 14.01 (2 CH3), 22.76 (CH2), 22.77 (CH2),
25.45 (2 CH2), 29.51 (2 CH2), 31.62 (2 CH2), 48.38 (2 CH), 70.36–71.08 (2 CH),
128.54 (CH), 129.05 (CH), 130.70 (2 CH) 131.85 (2 C), 173.85 (2 C) ppm. 19F{1H}-
NMR (470 MHz, CDCl3): δ = –80.88 (tt, J = 10.0 Hz, J = 2.6 Hz), (–116.39)–(–126.73)
(m) ppm. IR (ATR): nu(tilde) = 2964 (m), 2937 (m), 2866 (w), 1812 (w), 1756 (m),
1463 (m), 1235 (s), 1195 (s), 1156 (s), 1069 (m), 1040 (m), 1026 (m), 703 (m) cm–1.
C36H36F26O4 (1026.64): calcd. C 42.12%, H 3.53%; found C 41.88%, H 1.57%.
1,3,5-Tris(1-acetoxy-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)benzene
(3n).
According to the procedure reported above for the preparation of compound 3e, the
alcohol 2d (1.00 g, 0.891 mmol, 1.00 equiv.), acetyl chloride (0.57 mL, 8.0 mmol, 9.0
equiv.) and pyridine (3 mL) were converted to yield the title compound 3n (711 mg,
0.570 mmol, 64%) as a colorless oil after chromatography (SiO2, hexanes/MTBE 20 :
1, Rf = 0.34). Three signal sets (ratio 2 : 3 : 4) were observed in the NMR spectra due
to the two possible diastereoisomers of this compound; the major diastereoisomer
possesses furthermore two diastereotopic side chains in the ratio 1 : 2. 1H-NMR (500
MHz, CDCl3): δ = 2.18–2.21 (m, 9H), 6.37 (dd, J = 8.3 Hz, J = 15.6 Hz, 3H), 7.61–
7.63 (m, 3H) ppm. 13C{1H}-NMR (125 MHz, CDCl3); signal set A: δ = 20.46 (CH3),
69.82–70.45 (m, 3 CH), 130.42 (3 CH), 132.46 (3 C), 168.11 (C) ppm; signal set B: δ
= 20.52 (CH3), 69.82–70.45 (m, 3 CH), 130.49 (3 CH), 132.50 (3 C), 168.21 (C) ppm;
23
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
signal set C: δ = 20.58 (CH3), 69.82–70.45 (m, 3 CH), 130.53 (3 CH), 132.55 (3 C),
168.35 (C) ppm. 19F{1H}-NMR (470 MHz, CDCl3): δ = (–80.86)–(–80.94) (m), (–
117.17)–(–127.16) (m) ppm. IR (ATR): nu(tilde) = 2976 (w), 1768 (s), 1374 (m), 1192
(vs), 1144 (vs), 1122 (s), 1066 (s), 896 (m), 735 (m), 708 (m) cm–1. C33H15F39O6
(1248.41): calcd. C 31.75%, H 1.21%; found C 31.64%, H 1.33%.
(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctyl)
benzoate
(6a).
The
alcohol
nC6F13CH2CH2OH (1.16 mL, 5.34 mmol, 1.50 eq.) was added to an ice-cooled
solution of PhCOCl (5a) (500 mg, 3.56 mmol, 1.00 eq.) in pyridine (5 mL) and the
mixture was subsequently stirred for 96 h at ambient temperature. It was then diluted
with water (30 mL) and acidified with conc. hydrochloric acid (7 mL) until pH 3. The
mixture was extracted with MTBE (2 x 30 mL) and the combined organic extracts
dried (MgSO4) and evaporated after filtration. The oily residue was treated with
CH2Cl2 (5 mL) in order to extract impurities. The oily layer was separated and dried to
1
furnish the title compound 6a (879 mg, 1.88 mmol, 52%) as a colorless oil. H-NMR
(500 MHz, CDCl3): δ = 2.62 (tt, J = 18.1 Hz, J = 6.3 Hz, 2H), 4.64 (t, J = 6.4 Hz, 2H),
7.46 (t, J = 7.8 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H), 8.04 (d, J = 6.9 Hz, 2H) ppm.
13C{1H}-NMR (125 MHz, CDCl3): δ = 30.09 (CH2), 56.97 (CH2),128.63 (2 CH), 129.70
(C), 129.84 (2 CH), 133.48 (CH), 166.29 (C) ppm. 19F{1H}-NMR (470 MHz, CDCl3): δ
= –80.79 (tt, J = 2.7 Hz, J = 10.1 Hz), (–113.37)–(–113.46) (m), (–121.75)–(–121.92)
(m), (–122.72)–(–122.93) (m), (–123.39)–(–123.59) (m), (–125.98)–(–126.20) (m)
ppm. IR (ATR): nu(tilde) = 3066 (w), 2978 (w), 1726 (s), 1274 (s), 1233 (vs), 1190
(vs), 1117 (s), 708 (s) cm–1. HR-MS (ESI, pos. mode): calcd. 491.0293 (for
C15H9F13NaO2), found 491.0284 [M + Na+]. C15H9F13O2 (468.21).
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European Journal of Organic Chemistry
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Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)terephthalate (6b). A mixture of
terephthalic acid (4b) (5.00 g, 30.1 mmol, 1.00 eq.) and SOCl2 (10.7 g, 90.2 mmol,
3.00 eq.) was stirred for 4 h at 80°C. Excess of SOCl2 was then removed by
distillation and the residue dried in high vacuum to yield the acid chloride 5b (5.55 g,
27.4 mmol, 91%) as colorless solid. A portion of compound 5b (2.00 g, 9.85 mmol,
1.00 eq.) was dissolved in pyridine (5 mL) and nC6F13CH2CH2OH (7.89 g, 21.7 mmol,
2.2 eq.) was added to this mixture while cooling with an ice-water bath. After stirring
the mixture for 3 h at 90°C, it was diluted with water (50 mL) and acidified with conc.
hydrochloric acid (14 mL) until pH 3. The mixture was extracted with MTBE (2 x 50
mL) and the combined organic extracts dried (MgSO4) and evaporated after filtration.
Product 6b (5.71 g, 6.66 mmol, 68%) was obtained as a colorless solid, mp. 161°C,
after recrystallization from CH2Cl2 (50 mL). 1H-NMR (500 MHz, CDCl3): δ = 2.63 (tt, J
13
= 18.1 Hz, J = 6.4 Hz, 4H), 4.67 (t, J = 6.4 Hz, 4H), 8.11 (s, 4H) ppm. C{1H}-NMR
(125 MHz, CDCl3): δ = 30.83 (2 CH2), 57.41 (2 CH2), 129.91 (4 CH), 133.78 (2 C),
19
165.37 (2 C) ppm. F{1H}-NMR (470 MHz, CDCl3): δ = –80.77 (tt, J = 10.2 Hz, J =
2.3 Hz), (–113.32)–(–113.48) (m), (–121.63)–(–121.92) (m), (–122.66)–(–122.87)
(m), (–123.42)–(–123.58) (m), (–126.00)–(–126.19) (m) ppm. IR (ATR): nu(tilde) =
2975 (w), 2842 (w), 1718 (s), 1686 (m), 1280 (s), 1233 (s), 1182 (s), 1139 (vs), 1120
(vs), 1078 (s), 728 (s), 695 (s), 649 (s) cm–1. HR-MS (ESI, pos. mode): calcd.
881.0218 (for C24H12F26NaO4), found 881.0228 [M + Na+]. C24H12F26O4 (858.31).
Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) isophthalate (6c). Following the
procedure given above for compound 6b, isophthalic acid (4c) (5.00 g, 30.1 mmol,
1.00 eq.) and SOCl2 (6.6 mL, 90 mmol, 3.0 eq.) were converted to give compound 5c
(6.11 g, 30.1 mmol, 100%). A portion of the acid chloride 5c (500 mg, 2.46 mmol,
25
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
1.00 eq.) and nC6F13CH2CH2OH (1.60 mL, 7.39 mmol, 3.00 eq.) were converted to
give the title compound 6c (1.30 g, 1.52 mmol, 62%) as a colorless solid, mp. 47°C,
after recrystallization from CH2Cl2 (20 mL). 1H-NMR (500 MHz, CDCl3): δ = 2.63 (tt, J
= 18.2 Hz, J = 6.4 Hz, 4H), 4.67 (t, J = 6.4 Hz, 4H), 7.57 (t, J = 7.8 Hz, 1H), 8.25 (dd,
J = 7.8 Hz, J = 1.7 Hz, 2H), 8.67 (t, J = 1.7 Hz, 1H) ppm. 13C{1H}-NMR (125 MHz,
CDCl3): δ = 30.82 (2 CH2), 57.37 (2 CH2), 129.06 (CH), 130.29 (2 C), 131.01 (CH),
134.41 (2 CH), 165.30 (2 C) ppm. 19F{1H}-NMR (470 MHz, CDCl3): δ = –80.87 (tt, J =
2.4 Hz, J = 9.5 Hz), (–113.40)–(–113.59) (m), (–121.75)–(–121.99) (m), (–122.76)–(–
122.95) (m), (–123.48)–(–123.63) (m), (–126.07)–(–126.23) (m) ppm. IR (ATR):
nu(tilde) = 2975 (w), 2836 (w), 1717 (s), 1679 (m), 1283 (m), 1232 (s), 1184 (s), 1139
(vs), 1077 (s), 727 (s), 696 (s) cm–1. HR-MS (ESI, pos. mode): calcd. 859.0399 (for
C24H13F26O4), found 859.0356 [M + H+]. C24H12F26O4 (858.31).
Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) phthalate (6d). Following the
procedure given above for compound 6b, phthalic anhydride 4d (5.00 g, 33.8 mmol,
1.00 eq.) and SOCl2 (7.4 mL, 100 mmol, 3.0 eq.) were converted to give compound
5d (4.03 g, 21.2 mmol, 63%). A portion of the acid chloride 5d (500 mg, 2.46 mmol,
1.00 eq.) and nC6F13CH2CH2OH (1.17 mL, 5.41 mmol, 2.20 eq.) were converted to
give the title compound 6d (1.46 g, 1.70 mmol, 69%) as a colorless solid, mp. 36°C,
after recrystallization from CH2Cl2 (20 mL). 1H-NMR (500 MHz, CDCl3): δ = 2.63 (tt, J
= 18.1 Hz, J = 6.3 Hz, 4H), 4.65 (t, J = 6.5 Hz, 4H), 7.55–7.61 (m, 2H), 7.68–7.76 (m,
2H) ppm. 13C{1H}-NMR (125 MHz, CDCl3): δ = 30.57 (2 CH2), 57.54 (2 CH2), 129.17
(2 CH), 131.66 (2 C), 131.67 (2 CH), 167.00 (2 C) ppm. 19F{1H}-NMR (470 MHz,
CDCl3): δ = –80.87 (tt, J = 2.4 Hz, J = 10.4 Hz), (–113.54)–(–113.73) (m), (–121.79)–
(–121.97) (m), (–122.73)–(–123.06) (m), (–123.49)–(–123.73) (m), (–125.97)–(–
126.44) (m) ppm. IR (ATR): nu(tilde) = 2978 (w), 1732 (m), 1232 (s), 1189 (vs), 1141
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
(vs), 1079 (s), 842 (m), 809 (m), 733 (m), 697 (s) cm–1. HR-MS (ESI, pos. mode):
calcd. 881.0218 (for C24H12F26NaO4), found 881.0205 [M + Na+]. C24H12F26O4
(858.31).
Tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)trimesate (6e). Following the
procedure given above for compound 6b, trimesic acid 4e (3.00 g, 14.3 mmol, 1.00
eq.) and SOCl2 (4.7 mL, 64 mmol, 4.5 eq.) were converted to give compound 5e
(3.78 g, 14.3 mmol, 100%). A portion of the acid chloride 5e (500 mg, 1.88 mmol,
1.00 eq.) and nC6F13CH2CH2OH (1.35 mL, 6.20 mmol, 3.30 eq.) were converted to
give the title compound 6e (1.73 g, 1.39 mmol, 74%) as a colorless solid, mp. 73°C,
after recrystallization from CH2Cl2 (20 mL). 1H-NMR (500 MHz, CDCl3): δ = 2.65 (tt, J
13
= 18.2 Hz, J = 6.4 Hz, 6H), 4.70 (t, J = 6.3 Hz, 6H), 8.87 (s, 3H) ppm. C{1H}-NMR
(125 MHz, CDCl3): δ = 30.76 (3 CH2), 57.76 (3 CH2), 131.07 (3 CH), 135.15 (3 C),
164.36 (3 C) ppm. 19F{1H}-NMR (470 MHz, CDCl3): δ = –80.87 (tt, J = 2.6 Hz, J = 9.8
Hz), (–113.45)–(–113.55) (m), (–121.76)–(–121.94) (m), (–122.74)–(–122.97) (m), (–
123.47)–(–123.67) (m), (–126.09)–(–126.23) (m) ppm. IR (ATR): nu(tilde) = 3069 (w),
2969 (w), 1748 (m), 1729 (s), 1320 (m), 1229 (s), 1193 (vs), 1139 (vs), 1122 (s),
1079 (s), 1006 (m), 708 (s), 696 (s) cm–1. HR-MS (ESI, pos. mode): calcd. 1271.0144
(for C24H12F26NaO4), found 1271.0126 [M + Na+]. C33H15F39O6 (1248.41).
Pyromellitic acid tetrakis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoroctyl) ester (6f). A
solution of pyromellitic acid (4f) (1.00 g, 3.93 mmol, 1.00 eq.) in SOCl2 (20 mL, 280
mmol) and catalytic amounts of DMF (38 mg) was stirred under exclusion of moisture
(N2 atmosphere) for 16 h at 90°C. Subsequently, all volatiles were removed by
distillation and the alcohol nC6F13CH2CH2OH (8.59 g, 23.6 mmol, 6.00 eq.) was
added to the residue. The mixture was stirred for further 96 h at 90°C and
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European Journal of Organic Chemistry
10.1002/ejoc.201601298
subsequently diluted with water (100 mL), at which most of the crude product
precipitated. The suspension was extracted with MTBE (2 x 100 mL) and the solid
material separated by filtration and washed with H2O (30 mL) and MTBE (30 mL).
The combined organic layers were dried (MgSO4) and evaporated after filtration. The
combined solid products were recrystallized from CH2Cl2 (60 mL) to furnish product
6f (6.31 g, 3.85 mmol, 98%) as a colorless solid, mp. 114°C. Due to poor solubility in
acetone or CDCl3, no well resolved 1D-13C-NMR spectrum was obtained. The 13C-
1
3
signals were therefore assigned by J(1H,13C) and J(1H,13C) correlations out of the
HMQC and HMBC spectra. 1H-NMR (500 MHz, CDCl3): δ = 2.60 (tt, J = 18.2 Hz, J =
6.5 Hz, 8H), 4.66 (t, J = 6.4 Hz, 8H), 8.06 (s, 2H), ppm. 13C{1H}-NMR (125 MHz,
CDCl3): δ = 29.55 (4 CH2), 57.60 (4 CH2), 128.96 (2 CH), 134.01 (4 C), 165.10 (4 C)
13
1
2
3
ppm; the C resonances were indentified by J, J and J(1H,13C) correlations out of
19
the HMQC and HMBC spectra (see supporting information). F{1H}-NMR (470 MHz,
CDCl3): δ = –80.88 (tt, J = 2.5 Hz, J = 10.7 Hz), –113.65 (tq, J = 13.9 Hz, J = 5.4 Hz),
(–121.80)–(–122.00) (m), (–122.81)–(–122.96), (–123.52)–(–123.64) (m), (–126.12)–
(–126.25) (m) ppm. IR (ATR): nu(tilde) = 3082 (w), 2982 (w), 1744 (m), 1723 (s),
1291 (m), 1234 (s), 1183 (s), 1139 (vs), 1108 (s), 1073 (m), 1006 (m), 697 (s) cm–1.
HR-MS (ESI, pos. mode): calcd. 1661.0069 (for C42H18F52NaO8), found 1661.0063 [M
+ Na+]. C42H18F52O8 (1638.52).
Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) pyridine-2,6-dicarboxylate (6g).
Following the procedure given above for compound 6f, 2,6-pyridinedicarboxylic acid
4g (500 mg, 2.99 mmol, 1.00 eq.), SOCl2 (2.2 mL, 29.9 mmol, 10.0 eq.), DMF (16
mg) and nC6F13CH2CH2OH (1.43 mL, 6.58 mmol, 2.2 eq.) were converted to give the
title compound 6g (1.41 g, 1.64 mmol, 55%) as a colorless solid, mp. 127°C, after
1
recrystallization from CH2Cl2 (20 mL). H-NMR (500 MHz, CDCl3): δ = 2.70 (tt, J =
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European Journal of Organic Chemistry
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18.2 Hz, J = 6.8 Hz, 4H), 4.73 (t, J = 6.7 Hz, 4H), 8.04 (t, J = 7.8 Hz, 1H), 8.30 (d, J =
7.8 Hz, 2H) ppm. 13C{1H}-NMR (125 MHz, CDCl3): δ = 30.70 (2 CH2), 58.13 (2 CH2),
128.42 (2 CH), 138.62 (CH), 148.08 (2 C), 164.17 (2 C) ppm. 19F{1H}-NMR (470
MHz, CDCl3): δ = –80.82 (tt, J = 2.5 Hz, J = 10.1 Hz), (–112.40)–(–114.40) (m), (–
121.35)–(–124.08) (m), (–125.85)–(–126.54) (m) ppm. IR (ATR): nu(tilde) = 3064 (w),
1741 (s), 1235 (s), 1200 (s), 1178 (s), 1079 (s), 1079 (s), 999 (m), 867 (m), 768 (m),
693 (s) cm–1. HR-MS (ESI, pos. mode): calcd. 860.0351 (for C23H12F26NO4), found
860.0328 [M + H+]. C23H11F26NO4 (859.30).
Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) pyridine-3,5-dicarboxylate (6h).
Following the procedure given above for compound 6f, 3,5-pyridine dicarboxylic acid
4h (4.00 g, 23.9 mmol, 1.00 eq.), SOCl2 (17.6 mL, 240 mmol, 10.0 eq.), DMF (ca. 38
mg) and nC6F13CH2CH2OH (11.4 mL, 52.8 mmol, 2.2 eq.) were converted to give the
title compound 6h (19.09 g, 22.2 mmol, 93%) as a colorless solid, mp. 132°C, after
1
recrystallization from CH2Cl2 (50 mL). H-NMR (500 MHz, CDCl3): δ = 2.66 (tt, J =
18.2 Hz, J = 6.4 Hz, 4H), 4.73 (t, J = 6.3 Hz, 4H), 8.93 (t, J = 1.9 Hz, 1H), 9.41 (d, J =
2.0 Hz, 2H) ppm. 13C{1H}-NMR (135 MHz, CDCl3): δ = 30.71 (2 CH2), 58.10 (2 CH2),
126.46 (2 CH), 139.57 (CH), 153.13 (2 C), 163.36 (2 C) ppm. 19F{1H}-NMR (470
MHz, CDCl3): δ = –80.80 (tt, J = 2.6 Hz, J = 10.2 Hz), –113.42 (ddt, J = 4.9 Hz, J =
15.0 Hz, J = 19.9 Hz), (–121.33)–(–122.07) (m), (–122.37)–(–123.04) (m), (–123.28)–
(–123.84) (m), (–125.73)–(–126.55) (m) ppm. IR (ATR): nu(tilde) = 3057 (w), 3008
(w), 2937 (w), 2860 (w), 1738 (s), 1343 (m), 1307 (m), 1284 (m), 1232 (s), 1194 (s),
1140 (s), 1122 (s), 1090 (s), 999 (m), 651 (s) cm–1. HR-MS (ESI, pos. mode): calcd.
860.0351 (for C23H12F26NO4), found 860.0331 [M + H+]. C23H11F26NO4 (859.30).
29
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