Gemini cationic surfactants with flexible perfluorinated-ether chains

Article abstract of DOI:10.1016/j.jfluchem.2020.109632

This research aims at providing alternatives for long-chain fluorosurfactants, such as perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS) and their derivatives. Gemini quaternary ammonium fluorosurfactants with perfluorinated-ether chains

Full text of DOI:10.1016/j.jfluchem.2020.109632

Journal of Fluorine Chemistry 239 (2020) 109632
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Gemini cationic surfactants with flexible perfluorinated-ether chains
,
,
,
Fangqiong Dua, Yong Guob *, Meiwei Huangb, Qingyun Chenb *, Hu Yanga *, Weidong Xiec,
Wei Caoc, Chengying Wuc, Mengying Wangc
a College of Chemical Engineering, Sichuan University of Science & Engineering, 180 Xueyuan Road, Zigong, 643000, PR China
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, PR China
c Sanming Hexafluo Chemicals Co., LTD., Fluorinated New Material Industry Park, Mingxi, Fujian, 365200, PR China
A R T I C L E I N F O
A B S T R A C T
Keywords:
This research aims at providing alternatives for long-chain fluorosurfactants, such as perfluorooctanoic acid
(PFOA), perfluorooctanesulfonic acid (PFOS) and their derivatives. Gemini quaternary ammonium fluo-
rosurfactants with perfluorinated-ether chains were synthesized and their surface tensions were measured. The
surface tensions at critical micelle concentration (γcmc) are at the range of 14.7–23.3 mN/m and among them γcmc
of four perfluorinated-chain surfactants are below 16 mN/m.We found that the flexibility of perfluorinated-ether
chains, such as CF3(OCF2)n-, contributed significantly to enhance the surface activities. We also synthesized
gemini cationic surfactants with C6F13CH2CH2- groups and their γcmc are between 15.5 to 20.1 mN/m. Good
linkage design, such as -(CH2)n- (where n is odd), -CH2CH2OCH2CH2- and 1,2-phenylenebis(methylene), helps for
lowering surface energy. The current research provides an approach for discovering non-bioaccumulative
surfactants.
Gemini cationic surfactants
Perfluorinated-ether chains
Surface tension
Environmental benignity
1. Introduction
than the normal fluorosurfactants [8]. However, this surfactant contains
two perfluorooctyl groups which are not environmental friendly. It is
Fluorinated surfactants have unique functions severing as irre-
placeable ingredients for highly-demanded applications including fire-
fighting and oil-proofing [1,2]. However, traditionally, these
applications use long-chain per/polyfluoroalkyl substances (PFASs)
which are toxic, persistent, bioaccumulative and of long-distance
transportation. The oldest and most studied examples are per-
fluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS) and
their derivatives, which are banned/restricted by Stockholm Convention
[3,4]. Although the alternative strategy using short-chain perfluoroalkyl
substances has been developed, normal short-chain fluorosurfactants
were unqualified for the application which required extremely high
surface activities. Surfactants with elegantly-designed structures are
needed to meet the requirement of high performance alongside with low
environmental risk.
generally believed that the compounds with perfluorooctyl groups will
decompose in the environment to generate bioaccumulative per-
fluorooctanoic acid or its derivatives which are harmful to human be-
ing’s health. In the same research, when using perfluorohexyl groups to
replace perfluorooctyl groups, the γcmc increases to 19.8 mN/m [8].
Shortening of perfluoroalkyl chains is unsuccessful to keep the surface
properties. The new surfactant structures with both surface activity and
environmental benignity are required. We recently discovered that some
substances with perfluorinated-ether chains are less toxic and bio-
accumulative than PFOA. For examples, salts of CF3(OCF2)2COOH and
CF3(OCF2)3COOH demonstrated almost no accumulationin the liver or
serum; whereas a salt of CF3(OCF2)4COOH was accumulated but with
weaker potential than PFOA [9]. Thus, the surfactants with
perfluorinated-ether chains are considered to desirable alternative
candidates. In this article, we report our design of gemini cationic sur-
factants with perfluorinated-ether chains and the evaluation of their
surface properties.
Gemini surfactants have attracted much attention owing to their
fascinating properties of lower critical micelle concentration (CMC) and
higher surface activity compared with monomeric surfactants [1,5,6,7].
For example, the surface tension at the critical micelle concentration
(γcmc) of a gemini surfactant 1,2-bis[dimethyl-(3-perfluorooctyl-2-hy-
droxypropyl)ammonium]ethane bromide is 13.7 mN/m, that is lower
* Corresponding authors.
E-mail addresses: yguo@sioc.ac.cn (Y. Guo), chenqy@sioc.ac.cn (Q. Chen), yanghu67@163.com (H. Yang).
https://doi.org/10.1016/j.jfluchem.2020.109632
Received 4 March 2020; Received in revised form 20 August 2020; Accepted 23 August 2020
Available online 26 August 2020
0022-1139/© 2020 Elsevier B.V. All rights reserved.

F. Du et al.
Journal of Fluorine Chemistry 239 (2020) 109632
2. Results and discussion
and 16 OC4-Bu-OC4 may allow wider coverage on the surface, and as a
result lower the surface tension. The flexibility of perfluorinated-ether
chains seems to be a predominant factor to increase surface activities
other than the length or the fluorine content of perfluorinated sub-
stituents. With this assumption, it is easily understood that the best
surface activity was found for compound 17 OC5-Bu-OC5. For com-
pound 10 C73-Bu-C73, with CF3OCF2OCF2CF2OCF(CF3) group, even
similar in length and fluorine content, is less flexible and shows a higher
surface tension than that of compound 15 OC3-Bu-OC3 to 17
OC5-Bu-OC5.
We synthesized fluorinated gemini cationic surfactants in two steps.
The reactions of 3-dimethylaminopropylamine with fluorinated esters,
carbonyl fluorides or a sulfonyl chloride gave tertiary amines with
fluorinated tails (1 - 9) (Scheme 1). The tertiary amines reacted with
bromides gave gemini cationic surfactants with perfluorinated-ether
chains (10 - 31, Scheme 2) and with perfluorohexyl groups (32 - 39,
Scheme 3). We also synthesized single-chain surfactant 40 and 41
through methylation or butylation of tertiary amine 9 with iodomethane
or 1-bromobutane (Scheme 3).
In the series of compound 10 C73-Bu-C73, 18 C73-Pr-C73 to 21
C73-ether-C73, we examined the effect of the alkyl linkage. We
observed that the surface tensions at CMC of compound 18 C73-Pr-C73
(16.5 mN/m), 19 C73-Pent-C73 (17.4 mN/m) and 21 C73-ether-C73
(15.0 mN/m) were significantly lower than those of compound 10 C73-
Bu-C73 (18.6 mN/m) and 20 C73-Hex-C73 (19.7 mN/m). CH2CH2CH2,
CH2CH2CH2CH2CH2 and CH2CH2OCH2CH2 are better linkages than
CH2CH2CH2CH2 and CH2CH2CH2CH2CH2CH2. We name the phenome-
non as the“odd number effect”. The odd number effect was also found
for the series of compound 32 C62S-Pr-C62S to 36 C62S-ether-C62S.
The surface tensions at CMC of 32 C62S-Pr-C62S (16.6 mN/m), 34
C62S-Pent-C62S (15.5 mN/m), 36 C62S-ether-C62S (16.0 mN/m) are
significantly lower than those of 33 C62S-Bu-C62S (18.2 mN/m), 35
C62S-Hex-C62S (18.9 mN/m). The alkyl chains prefer zigzag confor-
mation. The odd-number carbon chains are helpful for the orientation of
two hydrophobic fluorinated groups towards outside the water surface
and thus reduce the surface tensions.
After we obtained the gemini quaternary ammonium surfactants, the
surface tensions in gradient concentration were measured. The critical
micelle concentrations and the surface tensions at the critical micelle
concentration were calculated and depicted in Table 1.
The surface tensions at critical micelle concentration of compouds in
Table 1 are at the range of 14.7–23.3 mN/m. The γcmc of compounds 17
OC5-Bu-OC5, 21C73-ether-C73, 28 OC4-p-phenyl-OC4, 29 OC5-p-
phenyl-OC5 and 34 C62S-Pent-C62S are below 16 mN/m. To the best
of our knowledge, few gemini cationic surfactants can reach such high
surface activities like ours [8,10,11]. The critical micelle concentrations
of these five compounds are 7 ~ 8 × 10ꢀ 4 mol/L (about 1 g/L).
In the series of compound 10 C73-Bu-C73 to 17 OC5-Bu-OC5, the
surface tensions at the critical micelle concentration of compounds 17
OC5-Bu-OC5 are the lowest. The structures of compounds in this series
are same except for perfluorinated-ether substituents. The substituent of
compound 17 OC5-Bu-OC5 is CF3(OCF2)5 group, that of compound 16
OC4-Bu-OC4 is CF3(OCF2)4 group, and that of compound 15 OC3-Bu-
OC3 is CF3(OCF2)3 group. Compounds 33 C62S-Bu-C62S, a similar
compound with C6F13CH2CH2 group as the substituent is of a higher
surface tension at the critical micelle concentration (18.2 mN/m) than
compound 17 OC5-Bu-OC5 (15.7 mN/m), compound 16 OC4-Bu-OC4
(16.2 mN/m) and compound 15 OC3-Bu-OC3 (17.0 mN/m). In general,
the great surface activities of fluorosurfactants highly relate to the
extremely weak attractive intermolecular forces due to the low polar-
izability of fluorine [1,12]. A longer perfluorinated carbon chain results
a higher surface activity. Compared with compound 33 C62S-Bu-C62S,
compounds 15 OC3-Bu-OC3 and 16 OC4-Bu-OC4 are in close chain
lengths, but with lower fluorine content due to the insertion of oxygen
atoms. The flexibility of oxygen-linkage in compound 15 OC3-Bu-OC3
We also found an interesting ortho-effect when we used bis(methy-
lene)benzene groups as the linkages. For n-C6F13-substituted com-
pounds, the surface activity of ortho-substituted compound (38 C62S-o-
phenyl-C62S, 16.2 mN/m) is better than meta- (39 C62S-m-phenyl-
C62S, 19.2 mN/m) and para- (37 C62S-p-phenyl-C62S, 20.1 mN/m)
analogues. The orientation becomes an important factor while per-
fluorohexyl is rigid. We propose that the orientation is very important
structure design when the hydrophobic groups in the gemini surfac-
tantsare rigid. However, the surface activities of 30 C73-m-phenyl-C73
(meta, 17.6 mN/m) and 31 C73-o-phenyl-C73 (ortho, 17.1 mN/m) is
close. The highly flexible 27 OC3-p-phenyl-OC3 (16.1 mN/m), 28 OC4-
p-phenyl-OC4 (15.2 mN/m), and 29 OC5-p-phenyl-OC5 (14.7 mN/m),
even para-substituted, exhibit excellent surface activities. These facts
Scheme 1. Synthesis of tertiary amines with fluorinated tails.
2

F. Du et al.
Journal of Fluorine Chemistry 239 (2020) 109632
Scheme 2. Synthesis of gemini cationic surfactants with perfluorinated-ether chains.
Scheme 3. Synthesis of cationic surfactants with perfluorohexyl group.
mean that the ortho-effect becomes less important if the hydrophobic
chains within gemini surfactants are flexible. The surface tensions
(15.5–18.9 mN/m) at CMC of gemini quaternary ammonium surfactants
32 C62S-Pr-C62S to 36 C62S-ether-C62S with C6F13CH2CH2- groups
are close to or higher than single-chain analogue 41 C62S-Bu-Br
(15.9 mN/m). The effect of counter ion was found when we compared
the γcmc of bromide 41 C62S-Bu-Br with that of iodide 40 C62S-Me-I
(22.4 mN/m).
The surface energy for single-chain carbon-based moieties are in the
following orders: CF3< CF2< CH3< CH2 [1,13]. If the compounds con-
tains more moieties with low surface energies, the compounds are more
surface active. Perfluoroalkyl surfactants possess greater surface activ-
ities over hydrocarbon analogue. The silicone surfactants achieve low
surface energy not only because of the low surface energy of methyl
groups but also because of the unique flexibility of the siloxane back-
bone [1,14]. Although compound 29 OC5-p-phenyl-OC5 with
3

F. Du et al.
Journal of Fluorine Chemistry 239 (2020) 109632
The concern is originated from the fact that these imperceptible bio-
accumlative substances will be superimposed over time and may make
the cells in the organism undergo irreversible changes leading to cancer
or other deseases eventually [15]. Hence, bioaccumulation deserves
more attention than toxicity. Hunting for alternatives with no or low
bioaccumulation, therefore, becomes an important strategy to reduce
the risk of PFASs. In the mice exposure experiment, we found that some
perfluoroether-based carboxylate were without or with low bio-
accumulation. For examples, CF3(OCF2)2CO2K and CF3(OCF2)3CO2K
demonstrated almost no accumulation in the liver or serum; whereas
CF3(OCF2)4CO2K was accumulated but with much weaker potential than
PFOA [9]. The further design of surfactants with those less bio-
accumulative perfluorinated-ether chains may provide a serial of fluo-
rinated surfactants with lower risk, although some references showed
the compounds with perfluoroether chains were still toxic to zebrafish
[16] and were still hard to decompose in simulative degragation ex-
periments [17]. In compare of some environmentally friendly short
chain perfluorinated alkyl compounds [18], perfluorinated-ether com-
pounds shows more variables and better surface properites. Research on
the development of surfactants based on perfluorinated-ether chains
should be looked as one of effective approaches to solve PFOS/PFOA
problems.
Table 1
The γcmc, CMC, Amin, and purity of fluorinated gemini quaternary ammonium
surfactants.
Compound
γcmc
(mN/
m)
CMC
Amin (nm2)
Puritya
(×10ꢀ 4mol/
L)
10
11
12
13
14
15
16
17
18
19
20
21
27
28
29
30
31
32
33
34
35
36
37
38
39
C73-Bu-C73
18.6
21.6
19.9
23.3
22.1
17.0
16.2
15.7
16.5
17.4
19.7
15.0
16.1
15.2
14.7
17.6
17.1
16.6
18.2
15.5
18.9
16.0
20.1
16.2
19.2
7.8
9.4
16
–
78 %
70 %
89 %
77 %
94 %
88 %
88 %
77 %
71 %
96 %
93 %
pure
pure
pure
pure
pure
pure
pure
pure
pure
pure
pure
pure
pure
pure
C61-Bu-C61
–
C62-Bu-C62
–
OC1-Bu-OC1
35
–
OC2-Bu-OC2
28
–
OC3-Bu-OC3
9.8
8.5
7.6
8.4
8.5
6.0
7.7
10
–
OC4-Bu-OC4
–
OC5-Bu-OC5
–
C73-Pr-C73
–
C73-Pent-C73
C73-Hex-C73
–
–
C73-ether-C73
OC3-p-phenyl-OC3
OC4-p-phenyl-OC4
OC5-p-phenyl-OC5
C73-m-phenyl-C73
C73-o-phenyl-C73
C62S-Pr-C62S
C62S-Bu-C62S
C62S-Pent-C62S
C62S-Hex-C62S
C62S-ether-C62S
C62S-p-phenyl-C62S
C62S-o-phenyl-C62S
C62S-m-phenyl-
C62S
4.4
2.2
3.6
2.8
9.7
8.3
4.3
5.5
3.6
3.2
4.9
3.7
4.2
6.0
7.3
7.7
8.9
9.7
5.8
7.7
7.9
4.9
15
3. Conclusions
4.9
3.9
4.8
Gemini cationic surfactants with perfluorinated-ether chains were
developed. The surface activities were evaluated and compared with
analogues with perfluorohexyl groups. All the surfactants can reduce
efficiently the surface tension of water. Five of them (17 OC5-Bu-OC5,
21 C73-ether-C73, 28 OC4-p-phenyl-OC4, 29 OC5-p-phenyl-OC5 and
34 C62S-Pent-C62S) achieve the γcmc below than 16 mN/m. The flexi-
bility of perfluorinated-ether chains account significantly for enhance-
ment of surface activities. The good linkages such as -(CH2)n- (where n is
odd), -CH2CH2OCH2CH2- and 1,2-phenylenebis(methylene) are also
important for increasing the surface activities. Considering some of
perfluorinated ethers functionalities have been proved to be more
environmental friendly than PFOA, the current research display a
promising future of alternatives for bioaccumulative surfactants.
40
41
C62S-Me-I
22.4
15.9
16
13
2.1
2.6
pure
pure
C62S-Bu-Br
a
The purities of compounds were determined by NMR analysis.
CF3(OCF2)5 groups and compound 37 C62S-p-phenyl-C62S with
CF3(CF2)5 groups have the same number of CF3 and CF2 groups, the
surface tension at CMC of compound 29 OC5-p-phenyl-OC5
(14.7 mN/m) is much lower than that of 37 C62S-p-phenyl-C62S
(20.1 mN/m). Compound 27 OC3-p-phenyl-OC3 (16.1 mN/m) with
CF3(OCF2)3 groups and 28 OC4-p-phenyl-OC4 (15.2 mN/m) with
CF3(OCF2)4 groups even with less number of CF2 groups are also much
better than 37 C62S-p-phenyl-C62S. Silmilar as the silicone surfactants,
the flexibility of perfluorinated-ether chains on compound 29 OC5-p--
phenyl-OC5 are one of the essential reasons for increasing surface ac-
tivities. Oxygen insertion into perfluoroalkyl chain is an effective way to
lowering surface energy.
4. Experimental
4.1. General information
Fluorinated starting materials were provided by Sanming Hexafluo
Chemicals Co., LTD. (see SI), and all other reagents were of AR grade
quality and used without further purification. Chemical shifts are
expressed in parts per million (ppm) with respect to the residual solvent
peak. Chemical shifts for 19F NMR are reported in ppm downfield from
fluorotrichloromethane (CFCl3). 13C NMR was broad-band decoupled
from hydrogen nuclei. Coupling constants are reported as hertz (Hz).
Signal shapes and splitting patterns are indicated as follows: s, singlet; d,
doublet; t, triplet; q, quartet; m, multiplet; br, broad. The resonances
corresponding the N-H protons are not included in the analysis –
possibly due to exchange broadening. HRMS (ESI) data were tested on a
Water Micromass GCT Premier. Surface tensions were obtained with
Dataphysics DCAT 21 surface tension meter.
A
min corresponds to the area per surfactant molecule at the air-water
interface at the critical micelle concentration [2]. We calculated Amin by
using the Gibbs equation
1
dγ
Γm ax = ꢀ
×
2.303 × nRT dlogc
and the equation
1014
Am in
=
NAΓm ax
The “n” was equal to 3 for gemini cationic surfactants, and the “n”
was taken as 2 for quanternary ammonium surfactants 40 and 41. Amin
were calculated and depicted in Table 1 for pure surfactants that we
synthesized. The Amin of the gemini surfactants are in the range of 2.2 to
9.7 nm2 bigger than the ones for single chain surfactant 40 and 41. The
observation consists with the fact that gemini surfactants are bigger than
single chain surfactants. The greater molecular volume of perfluoroalkyl
moieties and the larger cross section of fluorocarbon chains over hy-
drocarbon counterparts make the Amin bigger and the packing density
per unit area lower.
4.2. Typical experimental procedures
Procedure A:
To a 100 mL round-bottom flask containing a magnetic stirring bar
was added 3-dimethylaminopropylamine (20 mmol, 2.04 g, 2 eq.), tert-
butyl methyl ether (10 mL), and triethylamine (30 mmol, 3.03 g, 1.5
eq.). Stir the reaction mixture evenly. Then compound CF3OC-
F2OCF2CF2OCF(CF3)COF (10 mmol, 3.98 g, 1.0 eq.) was dropped in and
the mixture was stirred at room temperature for 2 h. After the reaction,
Some of PFASs are toxic, persistent and bioaccumulative. The bio-
accumulation are the essential property which attracts great concern.
4

F. Du et al.
Journal of Fluorine Chemistry 239 (2020) 109632
the mixture was added with water (100 mL), and the aqueous phase was
extracted with dichloromethane (3 × 50 mL). The organic layer was
dried over anhydrous sodium sulfate. After filtration, the organic extract
was concentrated by rotary evaporation under vacuum. The final com-
pound product was obtained as a light-yellow liquid (1, 4.65 g, 94 %).
Procedure B:
This compound was synthesized using procedure A and obtained as a
light-yellow liquid (4.65 g, 94 %). 1H NMR (400 MHz, CD3OD): δ 3.36 –
3.24 (m, 2 H), 2.31 (t, J =7 Hz, 2 H), 2.18 (s, 6 H), 1.74 – 1.64 (m, 2 H).
19F NMR (376 MHz, CD3OD): δ -55.3 – -55.4 (m, 2 F), -58.9 (t, J = 11 Hz,
3 F), -84.2 (s, 3 F), -86.8 (dd, J = 146, 18 Hz, 1 F), -90.2 (dd, J = 146,
8 Hz, 1 F), -91.6–-91.9 (m, 2 F),-134.0 (dd, J = 188 Hz, 1 F). 13C NMR
(100 MHz, CD3OD): δ 159.5 (d, J =26 Hz), 58.0, 45.3, 39.6, 27.2, car-
bons corresponding to the CF3OCF2OCF2CF2OCF(CF3)- group cannot be
To a 50 mL two-necked round-bottom flask containing a magnetic
stirring bar was added 3-dimethylaminopropylamine(20 mmol, 2.04 g,
1 eq.), methanol (10 mL), and triethylamine (30 mmol, 3.03 g, 1.5 eq.).
CF3OCF2COOCH3 (20 mmol, 3.88 g, 1.0 eq.) was added to dropwise by
constant pressure funnel. The mixture was stirred at room temperature
for 20 h. After the reaction, the mixture was added with water (100 mL),
and the aqueous phase was extracted with dichloromethane
(3 × 50 mL). The organic layer was dried over anhydrous sodium sulfate.
After filtration, the organic extract was concentrated by rotary evapo-
ration under vacuum. The final compound product was obtained as a
light-yellow liquid (4, 4.44 g, 84 %).
identified due to C–F coupling. HRMS-ESI (m/z): calcd for
C
12H13F13N2O4 [M+H]+: 497.0741, found: 497.0732. IR (film) v
:
ꢀ 1
/cm
3347, 2955, 2831, 2791, 1714, 1532, 1470, 1309, 1219, 1106, 1010,
989, 963, 916, 869, 794, 765, 720, 647.
N-(3-(dimethylamino)propyl)-2,3,3,3-tetrafluoro-2-(per-
fluoropropoxy)propanamide (2):
This compound was synthesized using procedure A and obtained as a
light-yellow liquid(3.81 g, 92 %). 1H NMR (400 MHz, (CD3)2CO) δ 9.48
(s, 1 H), 3.51 – 3.40 (m, 2 H), 2.41 (t, J =6 Hz, 2 H), 2.20 (s, 6 H), 1.74
(m, 2 H).19F NMR (376 MHz, (CD3)2CO) δ -81.6 (ddq, J = 149, 19, 7 Hz,
1 F), -82.2 (t, J =7 Hz, 3 F), -83.4 (d, J =2 Hz, 3 F), -85.6 (dm, J =149 Hz,
1 F), -130.6 (s, 2 F), -133.2 (dd, J = 20, 7 Hz, 1 F). 13C NMR (100 MHz,
CD3OD): δ 159.3 (d, J =26 Hz), 58.1, 45.4, 39.6, 27.3, carbons corre-
sponding to the CF3CF2CF2OCF(CF3)-group cannot be identified due to
C–F coupling. HRMS-ESI (m/z): calcd for C11H13F11N2O2 [Mꢀ H]ꢀ :
413.0729, found: 413.0730. IR (film) vꢀ/c1m: 3341, 2955, 2831, 1716,
1533, 1470, 1343, 1232, 1163, 991, 809, 720, 629, 535, 456.
N-(3-(dimethylamino)propyl)-2,3,3,3-tetrafluoro-2-(1,1,2,2-tetra-
fluoro-2-(trifluoromethoxy)ethoxy)propanamide (3):
Procedure C:
To a 50 mL three-necked round-bottom flask containing a magnetic
stirring bar was added 3-dimethylaminopropylamine (24 mmol, 2.44 g,
1.2 eq.) and toluene (12 mL). The three-necked flask was installed with a
condenser and a constant-pressure funnel. Then, the mixture was heated
to 45 ◦C. C6F13CH2CH2SO2Cl (20 mmol, 8.92 g, 1 eq.) was added drop-
wise via the constant-pressure funnel. The solution was allowed to warm
to 75 ◦C and stirred for 24 h. After that, the solution was added with
warm aqueous solution of 4% sodium chloride (200 mL), and then the
aqueous phase was extracted with DCM (3 × 40 mL). The organic layer
was dried over anhydrous sodium sulfate. After filtration, the organic
extract was concentrated by rotary evaporation under vacuum. (Note: a
large amount of foam turned out during evaporation and the addition of
a small amount of ethanol alleviated the generation of the foam) The
crude product was yellow solid. Recrystallization using ethanol as sol-
vent gave the final product as a white solid (9, 6.96 g, 68 %).
Procedure D:
This compound was synthesized using procedure B and obtained as a
light-yellow liquid (7.75 g, 90 %). 1H NMR (400 MHz, CD3OD): δ 3.32 –
3.23 (m, 2 H), 2.32 – 2.23 (m, 2 H), 2.15 (s, 6 H), 1.70 – 1.61 (m, 2 H).
19F NMR (376 MHz, CD3OD) δ -57.1 (t, J = 9 Hz, 3 F), -84.2 (d, J =2 Hz,
3 F), -86.6 (dd, J = 147, 18 Hz, 1 F), -90.3 (dd, J = 147, 8 Hz, 1 F),-91.9 –
-92.1 (m, 2 F), -134.1 (dd, J = 18, 8 Hz, 1 F). 13C NMR (100 MHz,
CD3OD): δ 159.5 (d, J =27 Hz), 58.1, 45.4, 39.7, 27.3, carbons corre-
sponding to the CF3OCF2CF2OCF(CF3)-group cannot be identified due to
C–F coupling. HRMS-ESI (m/z): calcd for C11H13F11N2O3 [M+H]+:
431.0823, found: 431.0825. IR (film) vꢀ/c1m: 3346, 2654, 1978.17, 1711,
1537, 1469, 1222, 1075, 1041, 988, 902, 794, 764, 717, 683, 529.
N-(3-(dimethylamino)propyl)-2,2-difluoro-2-(trifluoromethoxy)
acetamide (4):
To an oven-dried Schlenk tube equipped with a magnetic stirring bar
were added 1 (4 mmol, 1998 mg, 2 eq.), BrCH2CH2CH2CH2Br (2 mmol,
432 mg, 1eq.), and CH3CN (6 mL). The mixture was stirred at 80 ℃ for
12 h. After that, the mixture was concentrated by rotary evaporation
under vacuum. The crude solid product was recrystallized with acetone
and ether and gave the final product as a white solid (10, 2222 mg, 92
%).
This compound was synthesized using procedure B and obtained as a
light-yellow liquid (5.28 g, 84 %).1H NMR (400 MHz, CD3OD): δ 3.20 (t,
J =7 Hz, 2 H), 2.24 (t, J =7 Hz, 2 H), 2.12 (s, 6 H), 1.67 – 1.57 (m, 2 H).
19F NMR (376 MHz, CD3OD): δ -56.8 (t, J = 9 Hz, 3 F), -81.7 (q, J = 9 Hz,
2 F). 13C NMR (100 MHz, CD3OD): δ 158.9 (t, J =33 Hz), 120.7 (q, J
=264 Hz), 115.0 (t, J =282 Hz), 58.0, 45.3, 39.4, 27.2. HRMS-ESI (m/z):
calcd for C8H13F5N2O2 [Mꢀ H]－: 263.0824, Found: 263.0825. IR (film)
v/cmꢀ 1: 3312, 2830, 1716, 1548, 1465, 1348, 1239, 1161, 1059, 1038,
989, 797, 668.
Procedure E:
To an oven-dried Schlenk tube equipped with a magnetic stirring bar
were added compound 4 (4 mmol, 1057 mg, 2 eq.), BrCH2CH2CH2CH2Br
(2 mmol, 432 mg, 1eq.), and CH3CN (4 mL). The mixture was stirred at
80 ℃ for 10 h. The mixture was concentrated by rotary evaporation
under vacuum. The residue was dissolved in a small amount of methanol
or acetone. The addition of ether or DCM to the solution gave a turbid
liquid layer which was separated and evaporated under vacuum. The
purification process was repeated for three times. The final product was
obtained as a light-yellow liquid (13, 1280 mg, 86 %).
2-(difluoro(trifluoromethoxy)methoxy)-N-(3-(dimethylamino)pro-
pyl)-2,2-difluoroacetamide (5):
Procedure F:
This compound was synthesized using procedure B and obtained as a
light-yellow liquid in (4.54 g, 86 %). 1H NMR (400 MHz, CD3OD): δ 3.14
(t, J =7 Hz, 2 H), 2.18 (t, J =7 Hz, 2 H), 2.05 (s, 6 H), 1.61 – 1.51 (m,
2 H). 19F NMR (376 MHz, CD3OD): δ -55.0 – -55.2 (m, 2 F), -58.6 (t,
J = 9 Hz, 3 F), -81.5 (t, J =10 Hz, 2 F). 13C NMR (100 MHz, CD3OD): δ
158.9 (t, J =33 Hz), 119.9 (q, J =264 Hz), 119.2 (t, J =269 Hz), 115.2 (t,
Into a 25 mL three-necked round-bottom flask were added 9
(2 mmol, 1025 mg, 1.0 equiv.), and t-butylmethylether (5 mL) under a
nitrogen atmosphere.The iodomethane (3 mmol, 426 mg, 1.5 equiv.)
was added dropwise through a syringe. The reaction mixture was stirred
at room temperature for 12 h. The solvent was removed by evoparation
under vacuum.The crude solid product was recrystallized with acetone
and petroleum ether (acetone / petroleum ether = 1:3 v/v). The final
product was obtained as a white solid (40, 1125 mg, 86 %).
J
=283 Hz),58.0, 45.3, 39.5, 27.2.HRMS-ESI (m/z): calcd for
C9H13F7N2O3 [Mꢀ H]－: 329.0742; found: 329.0743. IR (film) v/cmꢀ 1
:
3316, 2953, 2789, 1716, 1544, 1375, 1301, 1002, 989, 862, 765, 682.
2-((difluoro(trifluoromethoxy)methoxy)difluoromethoxy)-N-(3-
(dimethylamino)propyl)-2,2-difluoroacetamide (6):
4.3. Data for compounds
This compound was synthesized using procedure B and obtained as a
light-yellow liquid (7.13 g, 90 %). 1H NMR (400 MHz, CD3OD): δ 3.19 (t,
J =7 Hz, 2 H), 2.24 (t, J =7 Hz, 2 H), 2.11 (s, 6 H), 1.66 – 1.58 (m, 2 H).
19F NMR (376 MHz, CD3OD): δ -54.5 –-54.7 (m, 2 F), -56.8 – -57.0 (m,
2-(2-(difluoro(trifluoromethoxy)methoxy)-1,1,2,2-tetra-
fluoroethoxy)-N-(3-(dimethylamino)propyl)-2,3,3,3-tetra-
fluoropropanamide (1):
5

F. Du et al.
Journal of Fluorine Chemistry 239 (2020) 109632
2 F), -58.7 (t, J = 9 Hz, 3 F), -81.6 (t, J = 11 Hz, 2 F). 13C NMR (100 MHz,
CD3OD): δ 158.8(t, J =33 Hz), 119.8 (q, J =265 Hz), 119.3 (t, J
=270 Hz), 118.4 (t, J =270 Hz), 115.3 (t, J =284 Hz), 58.1, 45.3, 39.5,
27.3 carbons corresponding to the CF3OCF2OCF2OCF2- group cannot be
=150 Hz, 2 F), -131.1 (s, 4 F), -134.0 (dd, J = 19, 7 Hz, 2 F). 13C NMR
(100 MHz, CD3OD): 159.8 (d, J =27 Hz), 64.6, 63.2, 51.6, 32.8, 23.4,
20.7 carbons corresponding to the CF3CF2CF2OCF(CF3)- group cannot
be identifieddue to C–F coupling. HRMS-ESI (m/z): calcd for
－
–
identified due to C–F coupling. HRMS-ESI(m/z): calcd for C10H13F9N2O4
C
26H34Br2F22N4O4 [M H] : 1041.0523; found: 1041.0509. IR (film) v/
[M H] : 395.0659; found: 395.0659. IR (film) v/cmꢀ 1: 3690, 3319,
ꢀ 1: 3419, 3049, 1711, 1541, 1342, 1396, 1165, 1072, 990, 906, 809,
－
–
cm
2790, 1716, 1544, 1375, 1235, 1073, 860, 795, 764, 688.
748, 629, 540.
N-(3-(dimethylamino)propyl)-2,2,4,4,6,6,8,8,10,10,10-undeca-
fluoro-3,5,7,9-tetraoxadecanamide (7):
N1,N1,N4,N4-tetramethyl-N1,N4-bis(3-(2,3,3,3-tetrafluoro-2-
(1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy)propanamido)propyl)
butane-1,4-diaminium bromide (12):
This compound was synthesized using procedure B and obtained as a
light-yellow liquid (7.95 g, 86 %). 1H NMR (400 MHz, CD3OD): δ 3.23 (t,
J =7 Hz, 2 H), 2.29 (t, J =7 Hz, 2 H), 2.15 (s, 6 H), 1.70 – 1.61 (m, 2 H).
19F NMR (376 MHz, CD3OD): δ -54.5 – -54.7 (m, 2 F), -56.3 – -56.5 (m,
2 F), -56.9– -57.0 (m, 2 F), -58.7– -58.8 (m, 3 F), -81.6 (t, J = 11 Hz, 2 F).
13C NMR (100 MHz, CD3OD): δ 158.8 (t, J =33 Hz), 119.9 (q, J
=265 Hz), 119.5 (t, J =270 Hz), 118.6 (t, J =269 Hz), 118.5 (t, J
=270 Hz), 115.3 (t, J =284 Hz), 58.3, 45.4, 39.8, 27.2. HRMS-ESI (m/z):
calcd for C11H13F11N2O5 [Mꢀ H]－: 461.0576; found: 461.0577.IR (film)
v/cmꢀ 1: 3649, 3327, 2870, 2790, 1717, 1544, 1465, 1235, 1065, 997,
944, 846, 796, 689.
This compound was synthesized using procedure D and obtained as a
white solid (1958 mg, 91 %). m.p.: 267.1–269.0℃. 1H NMR (400 MHz,
CD3OD): δ 3.55 (m, 4 H), 3.52 – 3.41 (m, 8 H), 3.20 (s, 12 H), 2.21 – 2.09
(m, 4 H), 2.02 – 1.90 (m, 4 H). 19F NMR (376 MHz, (CD3)2CO): δ -56.9 (t,
J = 9 Hz, 6 F), -83.8 (s, 6 F), -86.2 (dd, J = 147, 18 Hz, 2 F), -90.0 (dd,
J = 147, 8 Hz, 2 F), -91.6 – -91.8 (m, 4 F), -133.9 (dd, J = 18, 8 Hz, 2 F).
13C NMR (100 MHz, CD3OD): δ 159.9 (d, J =27 Hz), 64.6, 63.2, 51.6,
38.2, 23.4, 20.7, carbons corresponding to the CF3OCF2CF2OCF(CF3)-
group cannot be identifieddue to C–F coupling. HRMS-ESI (m/z): calcd
for C26H34Br2F22N4O6 [M – Br]+: 995.1305; found: 995.1293.IR (film) v/
N-(3-(dimethylamino)propyl)-2,2,4,4,6,6,8,8,10,10,12,12,12-tride-
cafluoro-3,5,7,9,11-pentaoxadodecanamide (8):
ꢀ 1: 3418, 3042, 2963, 2057, 1713, 1538, 1485, 1224, 1068, 985, 903,
cm
795, 720, 616.
This compound was synthesized using procedure B and obtained as a
light-yellow liquid (9.61 g, 89 %). 1H NMR (400 MHz, CD3OD): δ 3.16 (t,
J =7 Hz, 2 H), 2.23 (t, J =7 Hz, 2 H), 2.09 (s, 6 H), 1.64 – 1.53 (m, 2 H).
19F NMR (376 MHz, CD3OD): δ -54.6 – -54.7 (m, 2 F), -56.4 – -56.6 (m,
4 F), -57.0 – -57.2 (m, 2 F), -58.9 (t, J = 9 Hz, 3 F), -81.6 (t, J = 11 Hz,
2 F). 13C NMR (100 MHz, CD3OD): δ 158.9 (t, J =33 Hz), 58.2, 45.3,
39.6, 27.2 carbons corresponding to the CF3OCF2OCF2OCF2OCF2OCF2-
group cannot be identified due to C–F coupling. HRMS-ESI (m/z): calcd
for C12H13F13N2O6 [M+H]+: 529.0639; found: 529.0641. IR (film) v/
cmꢀ 1: 3317, 2955, 2870, 2791, 1717, 1465, 1054, 1004, 862, 796, 765,
687.
N1,N4-bis(3-(2,2-difluoro-2-(trifluoromethoxy)acetamido)propyl)-
N1,N1,N4,N4-tetramethylbutane-1,4-diaminium bromide (13):
This compound was synthesized using procedure E and obtained as a
light-yellow liquid (1280 mg, 86 %). 1H NMR (400 MHz, CD3OD):δ 3.58
– 3.49 (m, 4 H), 3.49 – 3.36 (m, 8 H), 3.17 (s, 12 H), 2.18 – 2.05 (m, 4 H),
1.94 (m, 4 H).19F NMR (376 MHz, CD3OD): δ -55.6 (t, J = 9 Hz, 6 F),
-80.5 (q, J = 9 Hz, 4 F).HRMS-ESI (m/z): calcd for C20H34Br2F10N4O4 [M
– Br]+: 663.1598; found: 663.1595. IR (film) v/cmꢀ 1: 3419, 3041, 2360,
1783, 1693, 1035, 956, 794, 541. 418.
N1,N4-bis(3-(2-(difluoro(trifluoromethoxy)methoxy)-2,2-difluor-
oacetamido)propyl)-N1,N1,N4,N4-tetramethylbutane-1,4-diaminium
bromide (14):
N-(3-(dimethylamino)propyl)-3,3,4,4,5,5,6,6,7,7,8,8,8-trideca-
fluorooctane-1-sulfonamide (9) [19]:
This compound was synthesized using procedure E and obtained as a
light-yellow liquid (1507 mg, 86 %). 1H NMR (400 MHz, CD3OD): δ 3.64
– 3.55 (m, 4 H), 3.54 – 3.46 (m, 8 H), 3.24 (s, 12 H), 2.25 – 2.13 (m, 4 H),
2.05 – 1.85(m, 4 H). 19F NMR (376 MHz, CD3OD): δ -54.9 – -55.0 (m,
4 F), -58.5 (t, J = 9 Hz, 6 F), -81.3 (t, J = 11 Hz, 4 F). 13C NMR (100 MHz,
CD3OD): δ 159.2 (t, J =33 Hz), 119.8 (q, J =263 Hz), 119.2 (t, J
=270 Hz), 115.0 (t, J =284 Hz), 64.4, 63.2, 51.7, 38.1, 23.4, 20.7.
HRMS-ESI (m/z): calcd for C22H34Br2F14N4O6 [M –Br]+: 795.1433;
found: 795.1426. IR (film) v/cmꢀ 1: 3418, 3065, 2066, 1550, 1236,
1141, 963, 896, 797, 683.
This compound was synthesized using procedure C and obtained as a
white solid (6.96 g, 68 %).m.p.: 81.6–82.4℃. 1H NMR (400 MHz,
(CD3)2CO): δ 3.31– 3.27 (m, 2 H), 3.13 (t, J =6 Hz, 2 H), 2.71 – 2.53 (m,
2 H), 2.34 (t, J =6 Hz, 2 H), 2.16 (s, 6 H), 1.69–1.63 (m, 2 H). 19F NMR
(376 MHz, (CD3)2CO): δ -81.5 (tt, J = 10, 2 Hz, 3 F), -113.8 – -114.0 (m,
2 F), -122.3 – -122.4 (m, 2 F), -123.1 – -123.4 (m, 2 F), -123.5 – -123.7
(m, 2 F), -126.5 – -126.7 (m, 2 F).
N1,N4-bis(1,1,1,3,3,5,5,6,6,8-decafluoro-9-oxo-8-(trifluoromethyl)-
2,4,7-trioxa-10-azatridecan-13-yl)-N1,N1,N4,N4-tetramethylbutane-1,4-
diaminium bromide (10):
N1,N1,N4,N4-tetramethyl-N1,N4-bis(1,1,1,3,3,5,5,7,7-nonafluoro-8-
oxo-2,4,6-trioxa-9-azadodecan-12-yl)butane-1,4-diaminium bromide
(15):
This compound was synthesized using procedure D. The crude solid
product was recrystallized with methanol and DCM, givng the final
product as a white solid (2222 mg, 92 %). m.p.: 143.8–144.5 ℃. 1H NMR
(400 MHz, CD3OD): δ 3.61 – 3.36 (m, 12 H), 3.17 (s, 12 H), 2.18 – 2.07
(m, 4 H), 1.94 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -55.2 – -55.4 (m,
4 F), -58.7 (t, J = 9 Hz, 6 F), -84.0 (s, 6 F), -86.6 (dd, J = 146, 18 Hz, 2 F),
-90.0 (dd, J = 146, 8 Hz, 2 F), -91.5 – -91.7 (m, 4 F), -133.9(dd, J = 18,
8 Hz, 2 F). 13C NMR (100 MHz, CD3OD): δ 159.9 (d, J =27 Hz), 64.6,
63.3, 51.6, 38.2, 23.4, 20.7, carbons corresponding to the CF3OC-
F2OCF2CF2OCF(CF3)- group cannot be identifieddue to C–F coupling.
This compound was synthesized using procedure E and obtained as a
light-yellow liquid (1501 mg, 90 %). 1H NMR (400 MHz, CD3OD): δ 3.60
– 3.51 (m, 4 H), 3.51 – 3.42 (m, 8 H), 3.20 (s, 12 H), 2.22 – 2.08 (m, 4 H),
1.97 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -54.4 – -54.6 (m, 4 F),
-56.7 – -56.9 (m, 4 F), -58.6 (t, J = 9 Hz, 6 F), -81.3 (t, J = 11 Hz, 4 F). 13C
NMR (100 MHz, CD3OD): δ 159.2 (t, J =33 Hz), 119.8 (q, J =265 Hz),
119.3 (t, J =270 Hz), 118.4 (t, J =270 Hz), 115.3 (t, J =284 Hz), 64.5,
63.2, 51.6, 38.1, 23.5, 20.7. HRMS-ESI (m/z): calcd for
－
HRMS-ESI (m/z): calcd for C28H34Br2F26N4O8 [M H] : 1205.0255;
C
24H34Br2F18N4O8 [M – Br]+: 927.1267; found: 927.1258. IR (film) v/
–
found: 1205.0248.IR (film) v/ꢀ c1m: 3418, 3049, 2960, 2055, 1712, 1632,
1538, 1485, 1196, 1026, 964, 870, 792, 721, 636.
cmꢀ 1: 3426, 3071, 2964, 2069, 1715, 1552, 1485, 1231, 1076, 985,
917, 854, 792, 684.
N1,N1,N4,N4-tetramethyl-N1,N4-bis(3-(2,3,3,3-tetrafluoro-2-(per-
N1,N1,N4,N4-tetramethyl-N1,N4-bis(1,1,1,3,3,5,5,7,7,9,9-undeca-
fluoro-10-oxo-2,4,6,8-tetraoxa-11-azatetradecan-14-yl)butane-1,4-dia-
minium bromide (16):
fluoropropoxy)propanamido)propyl)butane-1,4-diaminium
bromide
(11):
This compound was synthesized using procedure D and obtained as a
white solid (1838 mg, 88 %). m.p. 172.2–174.8℃. 1H NMR (400 MHz,
CD3OD): δ 3.57 – 3.41 (m, 12 H), 3.17 (s, 12 H), 2.18 – 2.08 (m, 4 H),
1.95ꢀ 1.90 (m, 4 H). 19F NMR (376 MHz, (CD3)2CO): -81.7 (ddq,
J = 149, 19, 7 Hz, 2 F), -82.9 (t, J =7 Hz, 6 F), -83.9 (s, 6 F), -86.1 (dm, J
This compound was synthesized using procedure E and obtained as a
light-yellow liquid (2007 mg, 88 %). 1H NMR (400 MHz, CD3OD): δ 3.58
– 3.49 (m, 4 H), 3.49 – 3.42 (m, 8 H), 3.18 (s, 12 H), 2.17 – 2.08(m, 4 H),
1.95 – 1.85 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -54.4– -54.5 (m,
4 F), -56.2– -56.4 (m, 4 F), -56.8 – -56.9 (m, 4 F), -58.7 (t, J = 9 Hz, 6 F),
6

F. Du et al.
Journal of Fluorine Chemistry 239 (2020) 109632
-81.3 (t, J = 11 Hz, 4 F). 13C NMR (100 MHz, CD3OD) δ 159.2 (t, J
=33 Hz), 64.5, 63.2, 51.6, 38.1, 23.5, 20.7, carbons corresponding to the
CF3OCF2OCF2OCF2OCF2- group cannot be identified due to C–F
coupling. HRMS-ESI (m/z): calcd for C26H34Br2F22N4O10 [M – Br]+:
1059.1102; found: 1059.1084. IR (film) v/ cmꢀ 1: 2849, 1714, 1557,
1488, 1255, 1219, 1111, 1064, 931, 781.
CF3OCF2OCF2CF2OCF(CF3)- group cannot be identified due to C–F
coupling. HRMS-ESI (m/z): calcd for C30H38Br2F26N4O8 [M – Br]+:
1155.1452; found: 1155.1447.IR (film) v/cmꢀ 1: 3418, 2956, 1713,
1633, 1539, 1308, 1107, 1026, 954, 869, 792.
N,N’-(oxybis(ethane-2,1-diyl))bis(1,1,1,3,3,5,5,6,6,8-decafluoro-N,
N-dimethyl-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-azatridecan-13-
aminium) bromide (21):
N1,N1,N4,N4-tetramethyl-N1,N4-bis(1,1,1,3,3,5,5,7,7,9,9,11,11-tri-
decafluoro-12-oxo-2,4,6,8,10-pentaoxa-13-azahexadecan-16-yl)butane-
1,4-diaminium bromide (17):
This compound was synthesized using procedure D. The final prod-
uct was obtained as a white solid (2326 mg, 95 %).m.p.: 169.5–171.8 ℃.
1H NMR (400 MHz, CD3OD): δ 4.11–4.00 (m, 4 H), 3.79–3.71 (m, 4 H),
3.49 – 3.31 (m, 8 H), 3.19 (s, 12 H), 2.12 – 1.98 (m, 4 H). 19F NMR
(376 MHz, CD3OD): δ -55.1 – -55.3 (m, 4 F), -58.7 (t, J = 9 Hz, 6 F), -83.9
(s, 6 F), -86.8 (dd, J = 146, 19 Hz, 2 F), -89.8 (dd, J = 146, 8 Hz, 2 F),
-91.5 – -91.7 (m, 4 F), -133.8 (m, 2 F). 13C NMR (100 MHz, CD3OD):
δ159.9 (d, J =27 Hz), 65.7, 65.1, 63.8, 52.3, 38.2, 23.6, carbons corre-
sponding to the CF3OCF2OCF2CF2OCF(CF3)- group cannot be identified
This compound was synthesized using procedure E and obtained as a
light-yellow liquid (2239 mg, 88 %).1H NMR (400 MHz, CD3OD): δ 3.59
– 3.51 (m, 4 H), 3.46 (m, 8 H), 3.20 (s, 12 H), 2.19 – 2.11 (m, 4 H), 2.03 –
1.87 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -54.4 – -54.6 (m, 4 F),
-56.2 – -56.5 (m, 8 F), -56.8 – -57.0 (m, 4 F), -58.7 (t, J = 9 Hz, 6 F), -81.3
(t, J = 11 Hz, 4 F). 13C NMR (100 MHz, CD3OD): δ 159.2 (t, J =33 Hz),
64.5, 63.2, 51.7, 38.1, 23.5, 20.7 carbons corresponding to the
CF3OCF2OCF2OCF2OCF2OCF2- group cannot be identified due to C–F
coupling. HRMS-ESI (m/z): calcd for C28H34Br2F26N4O12 [M – Br]+:
1191.0936; found: 1191.0924. IR (film) v/cmꢀ 1: 3418, 3076, 2958,
1714, 1633, 1487, 1227, 1054, 1003, 958, 683.
due to C–F coupling. HRMS-ESI (m/z): calcd for C28H34Br2F26N4O9
－
[M H] : 1221.0205; found: 1221.0205. IR (film) v/cmꢀ 1: 1706, 1653,
–
1558, 1540, 1208, 1104, 956, 869, 717, 637, 418.
N,N’-(1,4-phenylenebis(methylene))bis(1,1,1,3,3,5,5,6,6,8-decaf-
luoro-N,N-dimethyl-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-aza-
tridecan-13-aminium) bromide (22):
N1,N3-bis(1,1,1,3,3,5,5,6,6,8-decafluoro-9-oxo-8-(trifluoromethyl)-
2,4,7-trioxa-10-azatridecan-13-yl)-N1,N1,N3,N3-tetramethylpropane-
1,3-diaminium bromide (18):
This compound was synthesized using procedure D and obtained as a
white solid (2287 mg, 91 %). m.p.: 160.8–161.6 ℃. 1H NMR (400 MHz,
CD3OD): δ 7.77 (s, 4 H), 4.67 (s, 4 H), 3.52 – 3.40 (m, 8 H), 3.14 (s,
12 H), 2.23 – 2.14 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -55.1 – -55.3
(m, 4 F), -58.7 (t, J = 9 Hz, 6 F), -84.0 (d, J =1 Hz, 6 F), -86.6 (dd,
J = 146, 18 Hz, 2 F), -90.0 (dd, J = 146, 8 Hz, 2 F), -91.5 – -91.7 (m, 4 F),
-133.9 (dd, J = 18, 8 Hz, 2 F). 13C NMR (100 MHz, CD3OD): δ 159.9 (d, J
=27 Hz), 135.1, 131.4, 68.6, 63.2, 50.7, 38.2, 23.6 carbons corre-
sponding to the CF3OCF2OCF2CF2OCF(CF3)- group cannot be identified
due to C–F coupling. HRMS-ESI (m/z): calcd for C32H34Br2F26N4O8
This compound was synthesized using procedure D and obtained as a
white solid (1910 mg, 88 %).m.p.: 134.6–136.1℃. 1H NMR (400 MHz,
CD3OD): δ 3.59 – 3.39 (m, 12 H), 3.21 (s, 12 H), 2.47 – 2.34 (m, 2 H),
2.19 – 2.05 (m, 4 H).19F NMR (376 MHz, CD3OD): δ -55.1 – -55.3 (m,
4 F), -58.6 –-58.7 (m, 6 F), -84.0 (s,6 F), -86.5 – -86.8 (m, 2 F), -89.8 –
-90.3 (m, 2 F), -91.6 – -91.8 (m, 4 F), -133.9 – -134.0 (m, 2 F). 13C NMR
(100 MHz, CD3OD): δ 159.9 (d, J =27 Hz), 63.9, 61.7, 51.8, 38.2, 23.4,
18.4 carbons corresponding to the CF3OCF2OCF2CF2OCF(CF3)- group
cannot be identified due to C–F coupling. HRMS-ESI (m/z): calcd for
－
+
ꢀ 1
–
–
C27H32Br2F26N4O8 [M H] : 1191.0099; found: 1191.0095. IR (film) v/
[M H] : 1175.1139, found: 1175.1139. IR (film) v/cm: 3050, 3492,
2877, 1708, 1616, 1556, 1481, 1454, 1319, 1111, 1012, 964, 871, 834,
795, 758, 721, 703, 641, 540, 458.
ꢀ 1: 3399, 3048, 2965, 2050, 1708, 1632, 1538, 1485, 1445, 1395,
cm
1220, 1107, 1025, 956, 869, 794, 767, 719.
N1,N5-bis(1,1,1,3,3,5,5,6,6,8-decafluoro-9-oxo-8-(trifluoromethyl)-
2,4,7-trioxa-10-azatridecan-13-yl)-N1, N1, N5, N5-tetramethylpentane-
1,5-diaminium bromide (19):
N,N’-(1,4-phenylenebis(methylene))bis(N,N-dimethyl-3-(2,3,3,3-
tetrafluoro-2-(perfluoropropoxy)propanamido)propan-1-aminium) bro-
mide (23):
This compound was synthesized using procedure D. The crude solid
product was recrystallized with methanol and ether, giving the final
product as a white solid (2175 mg, 89 %).m.p.: 165.7–166.8℃. 1H NMR
(400 MHz, CD3OD): δ 3.43 (m, 12 H), 3.13 (s, 12 H), 2.14 – 2.03 (m,
4 H), 1.91 – 1.87 (m, 4 H), 1.49 (m, 2 H). 19F NMR (376 MHz, CD3OD): δ
-55.1 – -55.3 (m, 4 F), -58.7 (t, J = 9 Hz, 6 F), -84.0 (d, J =1 Hz, 6 F),
-86.6 (dd, J = 146, 18 Hz, 2 F), -90.1 (dd, J = 146, 8 Hz, 2 F), -91.5 –
-91.7 (m, 4 F), -133.9(dd, J = 188 Hz, 2 F). 13C NMR (100 MHz, CD3OD):
δ 159.9 (d, J =27 Hz), 65.2, 63.0, 51.6, 38.2, 24.0, 23.4, 23.1, carbons
corresponding to the CF3OCF2OCF2CF2OCF(CF3)- group cannot be
This compound was synthesized using procedure D and obtained as a
white solid (2010 mg, 92 %). m.p.: 158.6–160.4 ℃. 1H NMR (400 MHz,
CD3OD): δ 7.78 (s, 4 H), 4.69 (s, 4 H), 3.50 – 3.42 (m, 8 H), 3.16 (s,
12 H), 2.26 – 2.16(m, 4 H). 19F NMR (376 MHz, CD3OD): δ -81.7 (ddq,
J = 149, 19, 7 Hz, 2 F), -82.9 (t, J =7 Hz, 6 F), -83.9 (s, 6 F), -86.1 (dm, J
=149 Hz, 2 F), -131.1 (s, 4 F), -134.0 (dd, J = 19, 6 Hz, 2 F). 13C NMR
(100 MHz, CD3OD): δ 159.9 (d, J =27 Hz), 135.1, 131.4, 68.6, 63.2,
50.8, 38.2, 23.6, carbons corresponding to the CF3CF2CF2OCF(CF3)-
group cannot be identified due to C–F coupling. HRMS-ESI (m/z): calcd
for C30H34Br2F22N4O4 [M – Br]+: 1011.1407, found: 1011.1393. IR
(film) vꢀ/c1m: 3417, 3029, 1713, 1538, 1484, 1341, 1232, 1072, 991, 876,
748, 631, 536.
identified due to C–F coupling. HRMS-ESI (m/z): calcd for
－
–
C29H36Br2F26N4O8 [M H] : 1219.0412; found: 1219.0403. IR (film) v/
ꢀ 1: 3521, 3342, 3221, 3065, 2972, 2945, 2868, 1708, 1633, 1556,
N,N’-(1,4-phenylenebis(methylene))bis(N,N-dimethyl-3-(2,3,3,3-
tetrafluoro-2-(1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy)prop-
anamido)propan-1-aminium) (24):
cm
1497, 1449, 1319, 1212, 1108, 1014, 977, 964, 956, 906, 889, 869, 719,
701, 608.
N1,N6-bis(1,1,1,3,3,5,5,6,6,8-decafluoro-9-oxo-8-(trifluoromethyl)-
2,4,7-trioxa-10-azatridecan-13-yl)-N1,N1,N6,N6-tetramethylhexane-1,6-
diaminium bromide (20):
This compound was synthesized using procedure D and obtained as a
white solid (2024 mg, 90 %). m.p.: 159.4–160.3 ℃. 1H NMR (400 MHz,
CD3OD): δ 7.77 (s, 4 H), 4.68 (s, 4 H), 3.50 – 3.40 (m, 8 H), 3.15 (s,
12 H), 2.25 – 2.14 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -57.0 (t,
J = 9 Hz, 6 F), -83.9 (d, J =2 Hz, 6 F), -86.3 (dd, J = 147, 18 Hz, 2 F),
-90.1 (dd, J = 147, 8 Hz, 2 F), -91.7 – -91.9 (m, 4 F), -134.0 (dd, J = 18,
8 Hz, 2 F). 13C NMR (100 MHz, CD3OD): δ 159.9 (d, J =26 Hz), 135.1,
131.4, 68.6, 63.2, 50.8, 38.2, 23.6, carbons corresponding to the
This compound was synthesized using procedure D and the crude
solid product was recrystallized with methanol and ether. The final
product was obtained as a white solid (2349 mg, 95 %).m.p.:
1
188.6–189.4℃. H NMR (400 MHz, CD3OD): δ 3.49 – 3.36 (m, 12 H),
3.13 (s, 12 H), 2.12 – 2.02 (m, 4 H), 1.89ꢀ 1.79 (m, 4 H), 1.58ꢀ 1.45 (m,
4 H). 19F NMR (376 MHz, CD3OD): δ -55.1 – -55.3 (m, 4 F), -58.7 (t,
J = 9 Hz, 6 F), -84.0 (s, 6 F), -86.6 (dd, J = 146, 18 Hz, 2 F), -90.0 (dd,
J = 146, 8 Hz, 2 F), -91.5 – -91.7 (m, 4 F), -133.9 (dd, J = 188 Hz, 2 F).
13C NMR (100 MHz, CD3OD): δ 159.9 (d, J =27 Hz), 65.5, 62.8, 51.5,
CF3OCF2CF2OCF(CF3)- group cannot be identified due to C–F coupling.
－
–
HRMS-ESI (m/z): calcd for C30H34Br2F22N4O6 [M H] : 1121.0421,
found: 1121.0424. IR (film) v/ꢀ c1m: 3395, 3028, 2848, 1706, 1645, 1540,
1224, 1026, 903, 796, 720, 642.
38.2, 26.6, 23.5, 23.2, carbons corresponding
to the
N,N’-(1,4-phenylenebis(methylene))bis(3-(2,2-difluoro-2-
7

F. Du et al.
Journal of Fluorine Chemistry 239 (2020) 109632
(trifluoromethoxy)acetamido)-N,N-dimethylpropan-1-aminium) bro-
mide (25):
1713, 1636, 1550, 1484, 1224, 1053, 687.
N,N’-(1,3-phenylenebis(methylene))bis(1,1,1,3,3,5,5,6,6,8-decaf-
luoro-N,N-dimethyl-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-aza-
tridecan-13-aminium) bromide (30):
This compound was synthesized using procedure D and obtained as a
white solid (1426 mg, 90 %). m.p.: 226.1–227.2℃1H NMR (400 MHz,
CD3OD): δ 7.77 (s, 4 H), 4.69 (s, 4 H), 3.50 – 3.40 (m, 8 H), 3.15 (s,
12 H), 2.26 – 2.14 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -56.7 (t,
J = 9 Hz, 6 F), -81.6 (q, J = 9 Hz, 4 F). 13C NMR (100 MHz, CD3OD): δ
159.4 (t, J =33 Hz), 135.1, 131.5, 120.7 (q, J =264 Hz), 114.9 (t, J
=283 Hz), 68.5, 63.2, 50.8, 38.0, 23.7. HRMS-ESI (m/z): calcd for
This compound was synthesized using procedure D and obtained as a
white solid in (2337 mg, 93 %). m.p.: 218.0–219.2 ℃.1H NMR
(400 MHz, CD3OD): δ 8.04 (s, 1 H), 7.83 (t, J =8 Hz, 2 H), 7.72 (t, J
=8 Hz, 1 H), 4.76 (s, 4 H), 3.54 –3.40 (m, 8 H), 3.18 (s, 6 H), 3.17 (s,
6 H), 2.27 – 2.17 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -55.1 – -55.3
(m, 4 F), -58.7 (t, J = 9 Hz, 6 F), -83.9 (s, 6 F), -86.7 (dd, J = 146, 18 Hz,
2 F), -89.9 (ddd, J = 146, 8, 2 Hz, 2 F), -91.5–-91.7 (m, 4 F), -133.7 (dd,
J = 18, 8 Hz, 2 F). 13C NMR (100 MHz, CD3OD): δ 159.9 (d, J =27 Hz),
138.9, 136.6, 131.4, 130.0, 68.6, 63.2, 50.7, 38.2, 23.7.HRMS-ESI (m/
C
24H34Br2F10N4O4. [Mꢀ H]－: 789.0714, found: 789.0719. IR (film) v/
cmꢀ 1: 3417, 3065, 2068, 1715, 1556, 1484, 1343, 1239, 1111, 876,
638, 526.
N,N’-(1,4-phenylenebis(methylene))bis(3-(2-(difluoro(tri-
fluoromethoxy)methoxy)-2,2-difluoroacetamido)-N,N-dimethylpropan-
1-aminium) bromide (26):
z): calcd for
C
32H34Br2F26N4O8 [M
–
Br]+: 1175.1139, found:
1175.1122. IR (film) vꢀ/c1m: 3396, 3208, 3021, 2051, 1711, 1630, 1537,
1483, 1387, 1220, 1108, 1026, 956, 920, 869, 794, 718, 637.
N,N’-(1,2-phenylenebis(methylene))bis(1,1,1,3,3,5,5,6,6,8-decaf-
luoro-N,N-dimethyl-9-oxo-8-(trifluoromethyl)-2,4,7-trioxa-10-aza-
tridecan-13-aminium) bromide (31):
This compound was synthesized using procedure D and obtained as a
yellow viscous liquid (1664 mg, 90 %).1H NMR (400 MHz, CD3OD): δ
7.79 (s, 4 H), 4.71 (s, 4 H), 3.51 – 3.42 (m, 8 H), 3.17 (s, 12 H), 2.25 –
2.18 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -54.9 – -55.1 (m, 4 F),
-58.5 (t, J = 9 Hz, 6 F), -81.3 (t, J =11 Hz, 4 F). 13C NMR (100 MHz,
CD3OD): δ 159.1 (d, J =121.4 Hz), 135.1, 131.5, 68.4, 63.2 50.8, 38.0,
23.7, carbons corresponding to the CF3OCF2OCF2- group cannot be
identified due to C–F coupling. HRMS-ESI (m/z): calcd for
This compound was synthesized using procedure D and obtained as a
white solid (2337 mg, 93 %). m.p.: 106.8–108.1 ℃.1H NMR (400 MHz,
CD3OD): δ 7.86ꢀ 7.83 (m, 2 H), 7.80 – 7.75 (m, 2 H), 5.02 (s, 4 H), 3.74 –
3.56 (m, 4 H), 3.53 – 3.40 (m, 4 H), 3.16 (s, 6 H), 3.12 (s, 6 H), 2.22 –
2.09 (m, 4 H).19F NMR (376 MHz, CD3OD): δ -55.1 – -55.3 (m, 4 F), -58.7
(t, J = 9 Hz, 6 F), -83.9 (s, 6 F), -86.8 (dd, J = 146, 18 Hz, 2 F), -89.9
(ddd, J = 146, 8 Hz, 2 F), -91.5–-91.7 (m, 4 F), -133.8 (dd, J = 18, 8 Hz,
2 F). 13C NMR (100 MHz, CD3OD): δ 159.9 (d, J =27 Hz), 136.9, 132.8,
130.5, 66.1, 63.3, 50.3, 50.1, 38.2, 23.7, carbons corresponding to the
CF3OCF2OCF2CF2OCF(CF3)- group cannot be identifieddue to C–F
C
26H34Br2F14N4O6. [M – Br]+: 843.1433; found: 843.1426. IR (film) v/
cmꢀ 1: 3418, 3064, 2071, 1714, 1557, 1486, 1234, 1095, 962, 796, 680.
N,N’-(1,4-phenylenebis(methylene))bis(1,1,1,3,3,5,5,7,7-non-
afluoro-N,N-dimethyl-8-oxo-2,4,6-trioxa-9-azadodecan-12-aminium)
bromide (27):
This compound was synthesized using procedure D and obtained as a
white solid (1923 mg, 91 %). m.p.: 210.1–212.6 ℃. 1H NMR (400 MHz,
CD3OD): δ 7.77 (s, 4 H), 4.68 (s, 4 H), 3.49 – 3.40 (m, 8 H), 3.15 (s,
12 H), 2.24 – 2.15 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -54.4 – -54.6
(m, 4 F), -56.7 – -56.9 (m, 4 F), -58.6 (t, J = 9 Hz, 6 F), -81.3 (t, J = 11 Hz,
4 F). 13C NMR (100 MHz, CD3OD): δ 159.4 (d, J=33 Hz), 135.1, 131.5,
68.4, 63.2, 50.7, 38.0, 23.7, carbons corresponding to the CF3OC-
F2OCF2OCF2- group cannot be identified due to C–F coupling. HRMS-ESI
－
–
coupling. HRMS-ESI (m/z): calcd for C32H34Br2F26N4O8 [M H] :
1253.0255, found: 1253.0255. IR (film) vꢀ/c1m: 3443, 3041, 1714, 1539,
1487, 1311, 1223, 1106, 654, 868, 788, 651.
N1,N1,N3,N3-tetramethyl-N1,N3-bis(3-((3,3,4,4,5,5,6,6,7,7,8,8,8-tri-
decafluorooctyl)sulfonamido)propyl)propane-1,3-diaminium bromide
(32):
This compound was synthesized using procedure D. The crude solid
product was recrystallized with ethanol, giving the final product as a
white solid (1202 mg, 98 %).m.p.: 272.6–273.2℃, 1H NMR (400 MHz,
CD3OD): δ 3.59 – 3.47 (m, 8 H), 3.45 – 3.38 (m, 4 H), 3.27– 3.23 (m,
16 H), 2.77 – 2.60 (m, 4 H), 2.44 – 2.32 (m, 2 H), 2.15 – 2.05 (m, 4 H).
19F NMR (376 MHz, CD3OD): δ -82.5 (t, J =10 Hz, 6 F), -114.7 – -115.0
(m, 4 F), -122.9 – -123.1 (m, 4 F), -123.9–-124.1 (m, 4 F), -124.2 – -124.4
(m, 4 F), -127.4 – -127.6 (m, 4 F). 13C NMR (100 MHz, CD3OD) δ 62.9,
61.2, 52.4, 44.0, 40.7, 27.2 (t, J =22 Hz), 24.9, 18.5, carbons corre-
sponding to the CF3CF2CF2CF2CF2CF2- group cannot be identified due to
C–F coupling. HRMS-ESI (m/z): calcd for C29H40Br2F26N4O4S2 [M –
(m/z): calcd for
C
28H34Br2F18N4O8 [M –Br]+:975.1267; found:
975.1257.IR (film) v/cmꢀ 1: 3427, 3056, 2073, 1713, 1557, 1481, 1223,
1003, 960, 834, 689, 457.
N,N’-(1,4-phenylenebis(methylene))bis(1,1,1,3,3,5,5,7,7,9,9-unde-
cafluoro-N,N-dimethyl-10-oxo-2,4,6,8-tetraoxa-11-azatetradecan-14-
aminium) bromide (28):
This compound was synthesized using procedure D and obtained as a
white solid (2187 mg, 92 %). m.p.: 210.2–211.4 ℃.1H NMR (400 MHz,
CD3OD): δ 7.77 (s, 4 H), 4.68 (s, 4 H), 3.49–3.39 (m, 8 H), 3.15 (s, 12 H),
2.25 – 2.15 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -54.4 – -54.5 (m,
4 F), -56.2 – -56.4 (m, 4 F), -56.8 – -56.9 (m, 4 F), -58.6 (t, J = 9 Hz, 6 F),
-81.3 (t, J = 11 Hz, 4 F). 13C NMR (100 MHz, CD3OD): δ 159.2 (t, J
=33 Hz), 135.1, 131.5, 68.4, 63.2, 50.8, 38.0, 23.7, carbons corre-
sponding to the CF3OCF2OCF2OCF2OCF2- group cannot be identified
Br]+:1145.1254; found: 1145.1251. IR (film) v : 3419, 2924, 1638,
ꢀ 1
/cm
1305, 1233, 1145, 1092, 964, 913, 515.
N1,N1,N4,N4-tetramethyl-N1,N4-bis(3-((3,3,4,4,5,5,6,6,7,7,8,8,8-tri-
decafluorooctyl)sulfonamido)propyl)butane-1,4-diaminiumbromide
(33):
due to C–F coupling. HRMS-ESI (m/z): calcd for C30H34Br2F22N4O10
－
[M H] : 1185.0218, found: 1185.0222. IR (film) v/cmꢀ 1: 3486, 3069,
This compound was synthesized using procedure D and obtained as a
white solid (2283 mg, 92 %). m.p.: 259.8–260.9℃, 1H NMR (400 MHz,
CD3OD): δ 3.53 – 3.40 (m, 12 H), 3.26 (t, J =6 Hz, 4 H), 3.17 (s, 12 H),
2.79 – 2.62 (m, 4 H), 2.13 – 2.04 (m, 4 H), 1.97–1.88 (m, 4 H). 19F NMR
(376 MHz, CD3OD): δ -82.5 (m, 6 F), -114.7 – -114.9 (m, 4 F), -122.8 –
-123.0 (m, 4 F), -123.8 – -124.0 (m, 4 F), -124.2 – -124.3 (m, 4 F),
-127.3–-127.4 (m, 4 F).13C NMR (100 MHz, CD3OD): δ 64.0, 62.7, 52.0,
44.0, 40.8, 27.2 (t, J =23 Hz), 24.8, 20.7, carbons corresponding to the
–
2361, 1702, 1633, 1566,1454, 1231,1064, 997,940,834, 641, 458.
N,N’-(1,4-phenylenebis(methylene))bis(1,1,1,3,3,5,5,7,7,9,9,11,11-
tridecafluoro-N,N-dimethyl-12-oxo-2,4,6,8,10-pentaoxa-13-azahex-
adecan-16-aminium) bromide (29):
This compound was synthesized using procedure D and obtained as a
white solid (2337 mg, 93 %). m.p.: 220.4–221.4 ℃.1H NMR (400 MHz,
CD3OD): δ 7.78 (s, 4 H), 4.70 (s, 4 H), 3.50 – 3.42 (m, 8 H), 3.17 (s,
12 H), 2.28 – 2.18 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -54.4 – -54.6
(m, 4 F), -56.2 – -56.4 (m, 8 F), -56.8 – -57.0 (m, 4 F), -58.7 (t, J = 9 Hz,
6 F), -81.3 (t, J = 11 Hz, 4 F). 13C NMR (100 MHz, CD3OD): δ 159.2 (t, J
=33 Hz), 135.1, 131.5, 68.5, 63.2, 50.8, 38.0, 23.7, carbons corre-
sponding to the CF3OCF2OCF2OCF2OCF2OCF2- group cannot be identi-
CF3CF2CF2CF2CF2CF2- group cannot be identified due to C–F coupling.
－
–
HRMS-ESI (m/z): calcd for C30H42Br2F26N4O4S2 [M H] : 1237.0526;
found: 1237.0512. IR (film) v/ꢀ c1m:3418, 3103, 2859, 1632, 1487, 1305,
1207, 1144, 1093, 964, 848, 747, 708, 652, 518.
N1,N1,N5,N5-tetramethyl-N1,N5-bis(3-((3,3,4,4,5,5,6,6,7,7,8,8,8-tri-
decafluorooctyl)sulfonamido)propyl)pentane-1,5-diaminium bromide
(34):
fied due to C–F coupling. HRMS-ESI (m/z): calcd for C32H34Br2F26N4O12
－
[M H] : 1317.0052; found: 1317.0056. IR (film) v/cmꢀ 1: 3418, 3073,
–
8

F. Du et al.
Journal of Fluorine Chemistry 239 (2020) 109632
This compound was synthesized using procedure D and obtained as a
m.p.: 237.8–239.8 ℃,1H NMR (400 MHz, CD3OD): δ 7.89 – 7.82 (m,
2 H), 7.80 – 7.74 (m, 2 H), 4.95 (s, 4 H), 3.65 – 3.57 (m, 4 H), 3.43 – 3.38
(m, 4 H), 3.27 (t, J =6.0 Hz, 4 H), 3.13 (s, 12 H), 2.79– 2.60 (m, 4 H),
2.17– 2.05 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -82.4 – -82.5 (m,
6 F), -114.7 – -114.9 (m, 4 F), -122.8 – -123.1 (m, 4 F), -123.8 – -124.1
(m, 4 F), -124.2 – -124.5 (m, 4 F), -127.3 – -127.5 (m, 4 F). 13C NMR
(100 MHz, CD3OD): δ 136.9, 132.8, 130.5, 66.5, 63.5, 50.4, 44.3, 40.8,
white solid (2359 mg, 94 %).m.p.: 261.8–262.5 ℃. 1H NMR (400 MHz,
CD3OD): δ 3.50 – 3.39 (m, 12 H), 3.25 (t, J =6 Hz, 4 H), 3.15 (s, 12 H),
2.77 – 2.60 (m, 4 H), 2.10 – 2.00 (m, 4 H), 1.99 – 1.87 (m, 4 H), 1.58 –
1.46 (m, 2 H). 19F NMR (376 MHz, CD3OD): δ -82.5 (t, J =10 Hz, 6 F),
-114.7 – -114.9 (m, 4 F), -122.9 – -123.0 (m, 4 F), -123.7 – -124.1 (m,
4 F), -124.2 – -124.3 (m, 4 F), -127.3 – -124.5 (m, 4 F).13C NMR
(100 MHz, CD3OD):δ 64.5, 62.3, 51.0, 44.0, 40.8, 27.2 (t, J =22 Hz),
25.0, 23.8, 23.0, carbons corresponding to the CF3CF2CF2CF2CF2CF2-
group cannot be identified due to C–F coupling. HRMS-ESI (m/z): calcd
27.2 (t,
J
=22 Hz), 24.9, carbons corresponding to the
CF3CF2CF2CF2CF2CF2- group cannot be identified due to C–F coupling.
HRMS-ESI (m/z): calcd for C34H42Br2F26N4O4S2 [M -Br]+:1207.1410,
found: 1207.1405.IR (film) v/cmꢀ 1: 3426, 3105, 2850, 2032, 1630,
1482, 1305, 1143, 1092, 963, 779, 738, 652, 517.
－
–
for C31H44Br2F26N4O4S2 [M H] :1251.0683; found: 1251.0699. IR
(film) vꢀ/c1m: 3418, 3104, 2920, 2850, 2064, 1632, 1486, 1445, 1305,
1144, 1092, 963, 847, 776, 708, 652, 517.
N,N’-(1,3-phenylenebis(methylene))bis(N,N-dimethyl-3-
N1,N1,N6,N6-tetramethyl-N1,N6-bis(3-((3,3,4,4,5,5,6,6,7,7,8,8,8-tri-
decafluorooctyl)sulfonamido)propyl)hexane-1,6-diaminium bromide
(35):
((3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfonamido)propan-1-
aminium) bromide (39):
This compound was synthesized using procedure D. The crude solid
product was recrystallized with acetone and ether. The final product was
obtained as a white solid (2345 mg, 91 %). m.p.: 247.8–248.4℃, 1H
NMR (400 MHz, CD3OD): δ 7.92 (s, 1 H), 7.82 (d,J =8 Hz, 2 H), 7.72 (t, J
=8 Hz, 1 H), 4.73 (s, 4 H), 3.54 – 3.38 (m, 8 H), 3.28 (t, J =6 Hz, 4 H),
3.16 (s, 12 H), 2.78 – 2.62 (m, 4 H), 2.25 – 2.14 (m, 4 H). 19F NMR
(376 MHz, CD3OD): δ -82.5 (t, J =10 Hz, 6 F), -114.6 – -114.9 (m, 4 F),
-122.6– -123.1 (m, 4 F), -123.8 – -124.1 (m, 4 F), -124.1– -124.4 (m, 4 F),
-127.2 – -127.5(m, 4 F). 13C NMR (100 MHz, CD3OD): δ 138.5, 136.7,
131.4, 130.1, 68.1, 62.8, 51.1, 44.0, 40.8, 27.2 (t, J =22 Hz), 25.0,
carbons corresponding to the CF3CF2CF2CF2CF2CF2- group cannot be
identified due to C–F coupling. HRMS-ESI (m/z): calcd for
This compound was synthesized using procedure D and obtained as a
white solid (2385 mg, 94 %).m.p.: 270.6–271.1 ℃. 1H NMR (400 MHz,
CD3OD): δ 3.52 – 3.37 (m, 12 H), 3.25 (t, J =6 Hz, 4 H), 3.15 (s, 12 H),
2.78 – 2.60(m, 4 H), 2.11 – 2.00 (m, 4 H), 1.94 – 1.82 (m, 4 H), 1.58 –
1.48 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -82.5 (t, J =10 Hz, 6 F),
-114.7 – -114.9 (m, 4 F), -122.8–-123.1 (m, 4 F), -123.8–-124.1 (m, 4 F),
-124.1–-124.4 (m, 4 F), -127.3 – -127.5 (m, 4 F). 13C NMR (100 MHz,
CD3OD): δ 65.1, 62.2, 51.9, 44.0, 40.8, 27.2 (t, J =22 Hz),26.5, 24.9,
23.0, carbons corresponding to the CF3CF2CF2CF2CF2CF2- group cannot
be identified due to C–F coupling. HRMS-ESI (m/z): calcd for
C
32H46Br2F26N4O4S2 [M – Br]+: 1187.1723; found: 1187.1713.IR (film)
vꢀ/c1m: 3417, 2952, 2866, 2057, 1639, 1487, 1446, 1327, 1145, 1093.
N,N’-(oxybis(ethane-2,1-diyl))bis(N,N-dimethyl-3-
C
34H42Br2F26N4O4S2 [M – Br]+: 1207.1410; found: 1207.1400. IR (film)
vꢀ/c1m: 3414, 3108, 2850, 1633, 1448, 1304, 1194, 1144, 1092, 962, 747,
655, 518.
((3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfonamido)propan-1-
aminium) bromide (36):
N,N,N-trimethyl-3-((3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sul-
fonamido)propan-1-aminium iodide (40):
This compound was synthesized using procedure D and obtained as a
white solid (2287 mg, 91 %).m.p.: 268.3–269.5℃. 1H NMR (400 MHz,
CD3OD): δ 4.09 – 4.02 (m, 4 H), 3.79 – 3.72 (m, 4 H), 3.64 – 3.56 (m,
4 H), 3.46 – 3.38 (m, 4 H), 3.28 (t, J =6 Hz, 4 H), 3.22 (s, 12 H), 2.79 –
2.60 (m, 4 H), 2.14 – 2.01 (m, 4 H). 19F NMR (376 MHz, CD3OD): δ -82.5
(t, J =10 Hz, 6 F), -114.7 – -114.9 (m, 4 F), -122.8 – -123.1 (m, 4 F),-
123.8 – -124.1 (m, 4 F), -124.1 – -124.4 (m, 4 F), -127.3 – -127.5 (m, 4 F).
13C NMR (100 MHz, CD3OD): δ 65.8, 65.6, 64.1, 52.3, 44.1, 41.0, 27.2 (t,
J =23 Hz), 24.9 carbons corresponding to the CF3CF2CF2CF2CF2CF2-
This compound was synthesized using procedure F and obtained as a
white solid (1125 mg, 86 %). m.p.: 264.4–265.2℃.1H NMR (400 MHz,
CD3OD) δ 3.53 – 3.47 (m, 2 H), 3.44 – 3.39 (m, 2 H), 3.26 (t, J =8 Hz,
2 H), 3.20 (s, 9 H), 2.78 – 2.61 (m, 2 H), 2.08 (m, 2 H).19F NMR
(376 MHz, CD3OD) δ -82.5 (tt, J = 10, 2 Hz, 3 F), -114.7 – -115.0 (m,
2 F), -122.8 – -123.1 (m, 2 F), -123.8 – -124.1 (m, 2 F), -124.2 – -124.5
(m, 2 F), -127.2 – -127.5 (m, 2 F). 13C NMR (100 MHz, CD3OD) δ 65.5,
53.9, 44.1, 40.8, 27.2 (t, J =23 Hz), 25.2, carbons corresponding to the
group cannot be identified due to C–F coupling. HRMS-ESI (m/z): calcd
CF3CF2CF2CF2CF2CF2- group cannot be identified due to C–F coupling.
－
+
–
–
for C30H42Br2F26N4O5S2 [M H] : 1253.0475; found: 1253.0469. IR
HRMS – ESI (m/z): Calculated for C14H20IF13N2O2S [M I] :527.1032.
(film) vꢀ/c1m: 3452, 3067, 2867, 1481, 1444, 1366, 1308, 1123, 1074,
1020, 912, 849, 778, 709, 603, 564, 519.
Found: 527.1025. R (film) vꢀ/c1m: 3605, 3434, 3105, 3013, 2881, 1628,
1482, 1444, 1368, 1234, 1145, 1091, 1029, 965, 887, 781, 747, 712,
N,N’-(1,4-phenylenebis(methylene))bis(N,N-dimethyl-3-
((3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfonamido)propan-1-
aminium) bromide (37):
651, 560, 522, 459 cmꢀ 1
.
N,N-dimethyl-N-butyl-3-((3,3,4,4,5,5,6,6,7,7,8,8,8-trideca-
fluorooctyl)sulfonamido)propan-1-aminium bromide (41):
This compound was synthesized using procedure D and obtained as a
white solid (2423 mg, 94 %). m.p.: 264.9–265.2℃. 1H NMR (400 MHz,
D6-DMSO): δ 7.69 (s, 4 H), 7.61 (t, J =6.0 Hz, 2 H), 4.63 (s, 4 H), 3.42 –
3.34(m, 8 H), 3.09 – 3.05 (m, 4 H), 3.01 (s, 12 H), 2.73 – 2.57 (m, 4 H),
2.06 – 1.98 (m, 4 H). 19F NMR (376 MHz, D6-DMSO): δ -82.4 – -82.5 (m,
6 F), -114.7 – -114.9 (m, 4 F), -122.9 – -123.1 (m, 4 F), -123.8 – -124.1
(m, 4 F), -124.2 – -124.4 (m, 4 F), -127.3 – -127.5 (m, 4 F). 13C NMR
(100 MHz, D6-DMSO) δ 133.4, 130.0, 65.7, 61.1, 49.4, 42.1, 25.4(t, J
=22 Hz), 23.1, carbons corresponding to the CF3CF2CF2CF2CF2CF2-
group cannot be identified due to C–F coupling. HRMS-ESI (m/z): calcd
for C34H42Br2F26N4O4S2 [M – Br]+: 1207.1410; found: 1207.1400. IR
(film) vꢀ/c1m: 3278, 3050, 1488, 1308, 1144, 1075, 998, 778, 711, 746,
695, 560, 521, 497.
This compound was synthesized using procedure F and obtained as a
white solid (1245 mg, 89 %). m.p.: 184.9–185.6℃.1H NMR (400 MHz,
CD3OD) δ 3.50 – 3.29 (m, 6 H), 3.24 (t, J =6 Hz, 2 H), 3.13 (s,
6 H),2.74ꢀ 2.62 (m, 2 H), 2.09 – 1.98 (m, 2 H), 1.85 – 1.72 (m, 2 H), 1.50
– 1.39 (m, 2 H), 1.04 (t, J =8 Hz, 3 H).19F NMR (376 MHz, CD3OD) δ
-82.5 (t, J =7 Hz, 3 F), -114.7 – -114.9 (m, 2 F), -122.8 – -123.1 (m, 2 F),
-123.8 – -124.1 (m, 2 F), -124.2 – -124.5 (m, 2 F), -127.2 – -127.5 (m,
2 F).13C NMR (100 MHz, CD3OD)δ 65.4, 62.8, 51.6 (t, J =4 Hz), 44.1,
40.9, 27.2 (t, J =22 Hz), 25.5, 24.8, 20.7, 13.9, carbons corresponding to
the CF3CF2CF2CF2CF2CF2- group cannot be identified due to C–F
coupling. HRMS
–
ESI (m/z): Calculated for C17H26BrF13N2O2S
ꢀ
-1
–
[M H] :647.0618. Found:647.0620. R (film) v/cm:3046, 2849, 1481,
1333, 1144, 1094, 1035, 989, 808, 778, 739, 696, 652, 558, 519, 470.
N,N’-(1,2-phenylenebis(methylene))bis(N,N-dimethyl-3-
((3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfonamido)propan-1-
aminium) bromide (38):
Declaration of Competing Interest
This compound was synthesized using procedure D. The crude solid
product was recrystallized with methanol and ethyl ether. The final
product was obtained as a white solid (2320 mg, 90 %).
The authors report no declarations of interest.
9

F. Du et al.
Journal of Fluorine Chemistry 239 (2020) 109632
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Acknowledgements
The support of our work by the National Natural Science Foundation
of China (Nos. 21737004, 21672239, and 21421002), STS Program of
Chinese Academy of Science (KF-STS-QYZX-068), and the Sanming
Institute of Fluorochemical Industry (Nos. FCIT201704GR,
FCIT201705GR, FCIT201701BR) is gratefully acknowledged.
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10