Perfluorinated Ammonium and Phosphonium Ionic Liquids

Article abstract of DOI:10.1055/s-0037-1610072

Ammonium and phosphonium ionic liquids with perfluorinated side chains were prepared as hybrid materials for surface impregnation. Melting points of the triflimide salts range up to 95 °C. The key feature of this investigation are relatively short perfluo

Full text of DOI:10.1055/s-0037-1610072

SYNTHESIS
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©
Georg Thieme Verlag Stuttgart · New York
2018, 50, A–I
paper
A
en
Synthesis
T. Alpers et al.
Paper
Perfluorinated Ammonium and Phosphonium Ionic Liquids
Torben Alpersa,b
Thomas W. T. Muesmannb
C6F13
O
Oliver Temmeb
Jens Christoffers*a
N
2
Ph P
PPh2
N
Y
N
F13C6
C6F13
F13C6
2 Y
F13C6
2 Y
C6F13
a
Institut für Chemie, Carl von Ossietzky Universität Oldenburg,
2
6111 Oldenburg, Germany
Y = I, OTf, NTf2
jens.christoffers@uol.de
b
Ferdinand Eimermacher GmbH & Co. KG, 48356 Nordwalde,
Germany
Received: 31.03.2018
Accepted after revision: 04.05.2018
Published online: 19.06.2018
tion as global contaminants. These compounds were conse-
quently listed under Annex B (restriction of production and
use) of the Stockholm Convention in 2009. Furthermore,
7
DOI: 10.1055/s-0037-1610072; Art ID: ss-2018-t0218-op
the European Chemicals Agency lists PFOA on the SVHC
Candidate List as a CMR substance (SVHC = substance of
very high concern; CMR = carcinogenic, mutagenic, or toxic
Abstract Ammonium and phosphonium ionic liquids with perfluori-
nated side chains were prepared as hybrid materials for surface impreg-
nation. Melting points of the triflimide salts range up to 95 °C. The key
feature of this investigation are relatively short perfluorohexyl residues
as the fluorinated part of the cations, making the target compounds
beneficial alternatives to established products because of their en-
hanced degradability and therefore lower bioaccumulativity. In the am-
monium series, pyrrolidinium, piperidinium, morpholinium triflimides
as well as the dication derived from DABCO were prepared. Mono-phos-
phonium triflimides were obtained from triphenyl- and diphenylphos-
phane. Diphosphonium bistriflimides were obtained from bis(diphenyl-
8
for reproduction). The chemical industry began several ini-
tiatives to identify replacements for perfluoroalkyl materi-
9
als with C8F17 chains or higher. Reasonable alternatives are
shorter chain compounds with C6F13 or C F residues, which
4
9
on the one hand could address the same outstanding mate-
rial properties, but on the other hand do not accumulate in
10
the environment due to their increased degradability.
phosphano)alkanes, Ph P(CH ) PPh with
n
=
2–5. As alkylating
2
2
n
2
As a manufacturer of water repellent textile coatings,
we are also aiming at identifying new compounds with
shorter perfluoroalkyl side chains.11 In particular fluorinat-
ed ionic liquids have come into focus as part of our re-
search. Perfluorinated solvents12 and ionic liquids are so-
called neoteric solvents, which are often associated with
reagents, n-C6F13CH CH OTf and n-C F CH CH I were applied.
2
2
6
13
2
2
Key words ionic liquids, fluorine compounds, phosphorus com-
pounds, ammonium salts, phosphonium salts, triflimide
13
14
Perfluoroalkyl carboxylic and sulfonic acids with longer
sustainable processes and green chemistry, although their
benefits are sometimes critically discussed.15 The combina-
tion of both, i.e. ionic liquids with perfluorinated side
carbon chains (CnF2n+1CO H and C F
SO H with n > 6), so-
2
n
2n+1
3
called fluorosurfactants, represent a technologically rele-
1
16
vant class of materials. These compounds have found ubiq-
chains, has been realized in a few cases. Most of them uti-
17
uitous applications for surface treatment of paper, card-
board, textiles, leathers, polymeric materials, metals, etc.2
Especially so-called fluorocarbon resins are widely used as
impregnation materials for industrial as well as consumer3
applications. The most prominent representatives for the
preparation of these materials are PFOA (C F CO H) and
lize perfluorocarboxylic acids as anions, but also perfluo-
18
rinated cations have been used. Among the perfluorinated
cations, imidazolium, triazolium,20 and quaternary am-
19
21
monium species have been reported. Fluorinated quater-
nary phosphonium salts were reported to be super-hydro-
phobic materials22 with contact angles up to 168°. Herein
we wish to disclose the synthesis of a small series of fluori-
nated ionic liquids based on cyclic ammonium, phosphoni-
um, and diphosphonium cations. As fluorinated side chains
RF, perfluorohexyl residues were applied. In the ammonium
series, pyrrolidinium 1, piperidinium 2, and morpholinium
3 cations, as well as the DABCO derivative 4, were prepared
(Figure 1). As phosphonium salts, the alkyltriphenyl 5 and
23
7
15
2
4
PFOS (C F SO H). Although PFOA and PFOS themselves are
8
17
3
quite harmless since chemically inert, they are for the same
reason persistent and they have become the focus of envi-
ronmental concerns because they pollute the environment
and are accumulated in the biosphere. Meanwhile they are
5
detectable ubiquitously in the abiotic environment as well
6
as in animals and humans and have thus attracted atten-
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

B
Synthesis
T. Alpers et al.
Paper
dialkyldiphenyl congeners 6 and the diphosphonium dica-
tions 7–10 derived from bis(diphenylphosphano)ethane
+
HN
OTf
N
N
Y
(DPPE), -propane (DPPP), -butane (DPPB), and –pentane
12
(b)
were prepared. As anions Y, iodide or triflate (OTf) originat-
ed from the synthesis, but were both exchanged to triflim-
RF
(a)
RF
RF
RF
11
13, 91%
1a, Y = OTf, 74%
ide [NTf , bis(trifluoromethanesulfonyl)imide anion].
(c)
2
1
b, Y = NTf2, 74%
RF
+
HN
RF
X
RF Ph P
OTf
N
N
Y
2
(b)
14
N
n
N
Y
(a)
N
Ph3P
Y
Ph2P
Y
PPh2
RF
RF
RF
RF
11
15, 91%
2a, Y = OTf, 77%
RF
RF
RF
2 Y
RF
RF
RF 2 Y
7, n = 1,
(c)
2
b, Y = NTf2, 99%
1
2
3
, X = CH2,
4
5
6
, X = CH2CH2,
, X = OCH2
8, n = 2,
9, n = 3,
10, n = 4
O
Y
= I, OTf, NTf2,
RF = n-C6F13
+ HN
O
O
OTf
N
N
Y
16
(b)
Figure 1 Target compounds of this study
(a)
RF
RF
RF
RF
11
17, 78%
3a, Y = OTf, 26%
3b, Y = NTf2, 55%
The iodide R CH CH I 19 (see Schemes 2 and 3) and tri-
F
2
2
(c)
flate R CH CH OTf 11 (Scheme 1) were envisioned as al-
F
2
2
kylating reagents for the introduction of the 1H,1H,2H,2H-
perfluorooctyl (R CH CH , R = n-C F ) residue into amines.
RF
OTf
F
2
2
F
3
13
(d)
N
N
N
+
Whereas the iodo compound 19 was commercially avail-
able, the triflate had to be prepared from the alcohol
R CH CH OH (‘6:2 FTOH’) according to a literature proce-
N
RF
11
18
RF
2 Y
F
2
2
2
4
dure. An initial attempt to convert R CH CH I 19 with pyr-
4a, Y = OTf, 82%
F
2
2
(
c)
rolidine (12) resulted in a complex reaction mixture. This
4b, Y = NTf , 73%
2
observation is in accordance with a report by Honda and
Scheme 1 Preparation of pyrrolidinium 1a,b, piperidinium 2a,b, mor-
pholinium salts 3a,b and DABCO derivatives 4a,b. Reagents and condi-
tions: (a) K CO (2 equiv), EtOAc, 70 °C, 1 d; (b) 11 (1 equiv), toluene,
21a
co-workers, who observed HI elimination to the respec-
tive olefin, followed by conjugated addition of the amine,
followed again by HF elimination. With R CH CH OTf 11,
2
3
130 °C, 3 h for 1a and 3a; 150 °C, 3 h for 2a; (c) 1. column of hydroxide
F
2
2
loaded Lewatit Mono MP Plus 800, 2. HNTf (1 equiv for 1b, 2b, 3b or 2
however, these processes could be avoided and the envi-
sioned alkylated amine 13 and the ammonium salt 1a were
formed (Scheme 1). After some experimentation, it was
found that a stepwise approach is more practicable, since
the optimal conditions for the first alkylation and the sec-
ond (quaternization) were different. Thus, tertiary amines
2
equiv for 4b); (d) 11 (3 equiv), toluene, 130 °C, 17 h. R = n-C F13.
F
6
as above to furnish bistriflimide 4b in 73% after recrystalli-
zation.
In contrast to the amines, the quaternization of phos-
phanes proceeded straightforwardly when using the alkyl
25
26
1
3, 15, and 17 (78–91% yield) were obtained by conver-
sion of the amines 12, 14, and 16 with K CO as base in EtOAc
iodide 19. As a first example, Ph P was converted to furnish
2
3
3
27
at 70 °C, whereas the salts 1a, 2a, and 3a were obtained by
heating the reaction mixtures in toluene to 130–150 °C and
subsequent recrystallization from MTBE in 74% (1a), 77%
the salt 5a in 76% yield after recrystallization (Scheme 2).
This compound has been previously reported and used for
Wittig olefinations.28 The anion exchange, however, failed
when using a hydroxy-loaded resin, presumably due to
ylide formation after deprotonation. Therefore, we applied
(
2a), and 26% (3a) yields, respectively. The triflate anions
–
–
TfO were exchanged to triflimide Tf N via the hydroxide
2
23a
salts, prepared with the ion-exchange resin Lewatit Mono
MP Plus 800. Whereas compound 2b was directly obtained
analytically pure in almost quantitative yield, compounds
a protocol adapted from Ragogna and co-workers
and
stirred the iodide 5a with LiNTf in acetone. After equilibra-
2
tion, the volatiles were removed and the mixture redis-
solved in EtOAc. All water soluble components were ex-
tracted repeatedly with water until the aqueous extract was
1b (74%) and 3b (55%) required purification by recrystalli-
zation from MTBE.
For the preparation of diazonia[2.2.2]bicyclooctane de-
rivative 4a, DABCO (18) was heated with an excess of the
triflate 11; the salt 4a was obtained in 82% yield after re-
crystallization from MTBE. Anion exchange was performed
iodide-free (checked with AgNO ). Finally, the material was
3
recrystallized from MTBE to furnish triflimide 5b in 77%
yield. The respective dialkyldiphenyl salts 6a (55%) and 6b
(71%) were prepared analogously from literature known
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

C
Synthesis
T. Alpers et al.
Paper
phosphane 20,29 which we could access in 89% yield after
The signals of most carbon atoms of compounds 7a, 7b,
13
1
deprotonation of Ph PH with n-BuLi and subsequent alkyl-
8a, and 8b appear as higher-order multiplets in the C{ H}
NMR spectra, because the respective carbon atoms define
the A-part of an AXX′-system, with the two magnetically
inequivalent phosphorus atoms being the X part. In these
2
ation with compound 19.
I
Ph3P
Y
(
a)
31
31
cases (n = 1, 2) the J( P, P) is significantly larger than zero.
For n = 3, 4 (i.e., compounds 9a, 9b, 10a, and 10b) the car-
bon signals are again first order (s or d), because the cou-
RF
RF
19
5a, Y = I, 76%
(
b)
31
31
5b, Y = NTf2, 77%
pling constant J( P, P) is almost zero. Anyhow, the signals
(
c)
of aliphatic carbon atoms are hardly detectable in the 1D
RF
Y
1
1
13
spectra, but could be clearly identified by their J( H, C)
cross peaks in the 2D HMQC spectra (see experimental sec-
tion and Supporting Information).
Ph2P
(
d)
Ph2P
RF
RF
20 (89%)
All ammonium and phosphonium salts 1a,b–10a,b are
insoluble in water and sparely soluble in MTBE, CH Cl , and
6
6
a, Y = I, 55%
(
b)
2
2
b, Y = NTf2, 71%
CHCl at ambient temperature. They show limited solubility
3
in MeOH or acetone, which is however sufficient for NMR
spectroscopy. Except compound 9b, which is a wax, all
compounds are solids; their melting points are listed in Ta-
ble 2. However, only the triflimides 1b–3b and 5b–10b can
be regarded as ‘ionic liquids’ since their melting points are
below 100 °C; most of them are higher than 50 °C. The pyr-
rolidine derivative 1b has the lowest melting point with
46 °C. DABCO derivatives 4a and 4b are high-melting mate-
rials with mp >200 °C. The triflates and iodides 1a–3a and
5a–10a have a melting point between 100 °C and 175 °C
(mp 203 °C for compound 9a) and are, therefore, by defini-
tion not ionic liquids. To obtain a first impression of the wa-
ter repellency of the new materials, we investigated the
wettability of a thin film spread on a glass surface by mea-
suring the water contact angle.22 The results did not fulfill
our expectations at all, because all contact angles were be-
low 110°, most of them between 50° and 100°. The highest
value was obtained with pyrrolidinium triflate 1a (104.5°),
which is not an ionic liquid (mp 153 °C). The second highest
value (102°) was obtained for morpholinium triflimide 3b,
which melts at 82 °C.
Scheme 2 Preparation of mono-phosphonium salts 5a,b and 6a,b. Re-
agents and conditions: (a) Ph P (1.1 equiv), DMF, 105 °C, 24 h; (b) 1.
3
LiNTf (1.5 equiv), acetone, 23 °C, 2 d; 2. EtOAc–water; (c) 1. Ph PH
2
2
(
1 equiv), n-BuLi (1 equiv), 19 (2.5 equiv), THF, 23 °C, 17 h; (d) 19 (1.25
equiv), DMF, 105 °C, 17 h. R = n-C F13.
F
6
After appropriate reaction conditions had been identi-
fied for the preparation of mono-phosphonium compounds
5a and 6a, the commercially available diphosphanes DPPE
(
21), DPPP (22), DPPB (23) as well as the congener with
pentane-1,5-diyl spacer 24 were quaternized with excess
alkyl iodide 19 (Scheme 3). The salts 7a–10a were obtained
in 64–96% yield (Table 1) after recrystallization from MTBE.
Ion exchange was accomplished with LiNTf as established
2
above for compounds 5b and 6b. Triflimide salts 7b–10b
were obtained in 65–88% yield (Table 1) after recrystalliza-
tion.
I
Ph Ph
(
a)
RF
P
P
RF
n
RF
PPh2
Ph Ph
2 Y
+
Ph2P
n
19
7a–10a, Y = I
2
2
2
2
1, n = 1,
2, n = 2,
3, n = 3,
4, n = 4
(b)
7
b–10b, Y = NTf2
Table 2 Melting Points of the Ammonium and Phosphonium Salts
Cation
Anion
Scheme 3 Preparation of diphosphonium salts 7a–10a, 7b–10b; for
yields see Table 1. Reagents and conditions: (a) 19 (2.5 equiv), DMF,
Triflate (a)
Iodide (a)
Triflimide (b)
1
05 °C, 24 h; (b) 1. LiNTf (3.0 equiv), acetone, 23 °C, 2 d; 2. EtOAc–
2
water. R = n-C F13.
1
2
153 °C
–
46 °C
50 °C
82 °C
206 °C
93 °C
95 °C
82 °C
54 °C
wax
F
6
139 °C
–
3
103 °C
–
Table 1 Yields of Diphosphonium Salts after Recrystallization from
MTBE
4
>250 °C
–
5
–
–
–
–
–
–
169 °C
134 °C
135 °C
165 °C
203 °C
174 °C
n
Y = I (yield)
2
Y = NTf (yield)
6
1
2
3
4
7a (96%)
8a (65%)
9a (83%)
10a (64%)
7b (88%)
8b (68%)
9b (65%)
10b (72%)
7
8
9
10
76 °C
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

D
Synthesis
T. Alpers et al.
Paper
In the course of global efforts to replace PFOA (C F CO H)
1-(1H,1H,2H,2H-Perfluorooctyl)pyrrolidine (13)
A solution of perfluorinated triflate 11 (10.0 g, 20.2 mmol, 1.0 equiv),
pyrrolidine (12; 1.44 g, 20.2 mmol, 1.0 equiv), and K CO (5.58 g, 40.3
mmol, 2.0 equiv) in EtOAc (15 mL) was stirred for 24 h at 70 °C. Water
20 mL) was added and the suspension was extracted with MTBE (2 ×
0 mL). The combined extracts were dried (MgSO ), filtered, and
7
15
2
and PFOS (C F SO H) as surface active ingredients, many
8
17
3
industrial manufacturers have begun investigations on al-
ternative resins with shorter perfluorinated alkyl chains,
hence, enhanced degradability and therefore low bioaccu-
mulativity. Our contribution to this field is the development
of novel ionic liquids with ammonium and phosphonium
2
3
(
3
4
evaporated. Product 13 (7.63 g, 18.3 mmol, 91%) was obtained as yel-
low liquid.
cations carrying perfluorinated n-hexyl residues (‘R ’),
F
IR (ATR): 2969 (w), 2790 (w), 1403 (w), 1358 (w), 1233 (s), 1190 (vs),
which were introduced by n-C F CH CH OTf (11) and n-
–1
6
13
2
2
1001 (m), 732 (m), 698 cm (m).
C F CH CH I (19) as alkylating reagents.
6
13
2
2
1
H NMR (500 MHz, CDCl ): δ = 1.70–1.89 (m, 4 H), 2.24–2.42 (m, 2 H),
3
In the ammonium series, pyrrolidine (12), piperidine
14), and morpholine (16) were first monoalkylated with
triflate 11 (78–91%) and then quaternized with the same
reagent furnishing the ammonium triflates 1a (74%), 2a
2.50–2.61 (m, 4 H), 2.72–2.82 (m, 2 H).
(
13
1
C{ H} NMR (125 MHz, CDCl ): δ = 23.64 (s, 2 CH ), 30.78–31.08 (m,
3
2
CH ), 47.31 (s, CH ), 54.28 (s, 2 CH ).
2
2
2
1
9
1
F{ H} NMR (470 MHz, CDCl ): δ = –80.80 (tt, J = 2.6 Hz, J = 10.1 Hz),
3
(
>
77%), and 3a (26%), which, as they have a melting point
–113.58 to –114.05 (m), –121.67 to –121.97 (m), –122.67 to –122.95
100 °C, are by definition not ionic liquids. However, after
(m), –123.38 to –123.67 (m), –125.97 to –126.22 (m).
HRMS (ESI): m/z [M + H]+ calcd for C12H13F13N: 418.0840; found:
418.0844.
–
–
exchange of TfO by Tf N with the aid of an anion exchange
2
resin, the triflimides 1b (74%), 2b (99%), and 3b (55%) are
obtained, which show melting points in the range of 46–
8
2 °C. Furthermore, DABCO (18) was twice quaternized
with reagent 11 furnishing the DABCOdionium bistriflate
a (82%) and after anion exchange the bistriflimide 4b
1,1-Bis(1H,1H,2H,2H-perfluorooctyl)pyrrolidinium Trifluoro-
methanesulfonate (1a)
4
A solution of perfluorinated triflate 11 (9.08 g, 18.3 mmol, 1.0 equiv)
and amine 13 (7.63 g, 18.3 mmol, 1.0 equiv) in toluene (10 mL) was
stirred in a tightly closed reaction tube for 3 h at 130 °C. After evapo-
ration of the volatiles, the residue was recrystallized (MTBE, 20 mL) to
furnish product 1a (12.4 g, 13.6 mmol, 74%) as a colorless solid; mp
(73%), which are both high-melting materials (mp >200 °C).
As phosphorus-based ionic liquids, first mono-phos-
phonium salts 5a (76%) and 6a (55%) were prepared from
Ph P or Ph PH and R CH CH I 19 with one or two R CH CH
residues. Whereas the iodides 5a and 6a are again high-
melting (mp >100 °C), ionic liquids 5b (77%, mp 93 °C) and
6
3
2
F
2
2
F
2
2
1
53 °C.
IR (ATR): 3056 (w), 3023 (w), 2975 (w), 1353 (w), 1318 (w), 1252 (s),
226 (s), 1196 (s), 1142 (s), 1125 (s), 1083 (w), 1029 (m), 961 (w), 811
1
–
b (71%, mp 95 °C) are obtained after ion exchange to Tf N ,
–1
2
(w), 726 (m), 697 (m), 640 cm (m).
which now was performed with LiNTf instead of an ion ex-
change resin. Furthermore, diphosphonium diiodides 7a–
1
2
H NMR (500 MHz, CD OD): δ = 2.21–2.38 (m, 4 H), 2.83–3.00 (m, 4
3
H), 3.66–3.77 (m, 4 H), 3.79–3.93 (m, 4 H).
1
0a (64–96%, all mp >100 °C) were prepared by twofold
13
1
C{ H} NMR (125 MHz, CD OD): δ = 22.94 (s, 2 CH ), 26.32 (t, J = 21.9
3
2
quaternization of diphosphanes Ph P(CH ) PPh (n = 2–5)
2
2
n
2
Hz, 2 CH ), 52.82 (s, 2 CH ), 65.22 (s, 2 CH ).
2 2 2
with iodide 19. Ionic liquids (mp up to 82 °C) are again ob-
19
1
F{ H} NMR (470 MHz, CD OD): δ = –80.13 (s), –82.36 to –82.53 (m),
3
tained by anion exchange with LiNTf yielding the bistri-
2
–113.80 to –114.33 (m), –122.60 to –122.84 (m), –123.53 to –124.12
(m), –126.97 to –127.49 (m).
flimides 7b–10b (65–88%).
–
HRMS (ESI): m/z [M – OTf ] calcd for C20H16F26N: 764.0868; found:
7
64.0871.
1H, 19F, 31P, and 13C NMR spectra were recorded on a Bruker Avance
DRX 500 instrument. Multiplicities of carbon signals were deter-
Exchange of Anions with HNTf ; General Procedure A (GPA)
2
13
mined with DEPT experiments. The C signals of some CH moieties
2
A column of ion-exchange resin Lewatit Mono MP Plus 800 (20 g,
Lanxess, capacity ca. 0.95 mmol/g) was regenerated prior to each use
by the following sequential washings: (1) with hydrochloric acid (10
mL, 2 mol/L) until pH 1 of the eluent, (2) with water until pH 7, (3)
with aq NaOH (10 mL, 2 mol/L) until pH 13–14 and finally (4) again
with water to pH 7.
could only be detected with 2D experiments; these are marked with
13
‘
HMQC’. C signals of CF and CF moieties (including OTf) could not
2 3
be individually distinguished due to extended overlapping. HRMS
spectra were obtained with a Waters Q-TOF Premier (ESI, all in the
+
’ve mode) spectrometer. IR spectra were recorded on a Bruker Ten-
sor 27 spectrophotometer equipped with a ‘GoldenGate’ diamond
ATR unit. Elemental analyses were determined with a Euro EA-CHNS
instrument from HEKAtech. Melting points were obtained with a Gal-
lenkamp device; values are uncorrected. Contact angle measurements
were performed with a Contact Angle System OCA, model 15plus
from dataphysics and a Teli ccd camera, model CS8620C1. The droplet
A warm (ca. 65 °C) solution of the triflate salt 1a, 2a, 3a, or 4a (1.11–
1.62 mmol) in MeOH (10 mL) was applied to the column and the hy-
droxide salt eluted with MeOH, until pH 7 of the eluent; the eluted
volume was about 100 mL each time. The hydroxide salt was not iso-
lated, but its aqueous solution was treated with HNTf (1.0 equiv per
2
nitrogen atom), the resulting mixture was evaporated and the residue
recrystallized (MTBE) to furnish the triflimide salt 1b, 2b, 3b, or 4b.
volume was
9
μL and photograph was taken after
2
s.
nC6F13CH CH OTf (11) was prepared according to the literature
2
2
24
protocol. All other starting materials were commercially available.
In particular, n-C6F13CH CH I (19) was purchased from Apollo and
2
2
n-C6F13CH CH OH from DuPont. MTBE = t-BuOMe.
2
2
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

E
Synthesis
T. Alpers et al.
Paper
1,1-Bis(1H,1H,2H,2H-perfluorooctyl)pyrrolidinium Bis(trifluoro-
1,1-Bis(1H,1H,2H,2H-perfluorooctyl)piperidinium Bis(trifluoro-
methanesulfonyl)imide (1b)
methanesulfonyl)imide (2b)
Triflate salt 1a (1.20 g, 1.31 mmol) was converted with HNTf2 (369
mg, 1.31 mmol) according to GPA to give compound 1b (1.01 g, 0.969
mmol, 74%) after recrystallization (MTBE, 20 mL) as a colorless solid;
mp 46 °C.
Triflate salt 2a (1.50 g, 1.62 mmol) was converted with HNTf2 (455
mg, 1.62 mmol) according to GPA to furnish compound 2b (1.69 g,
1.60 mmol, 99%) after evaporation of the solvent as a colorless solid;
mp 50 °C.
IR (ATR): 3153 (w), 1470 (w), 1344 (m), 1324 (m), 1185 (s), 1130 (s),
IR (ATR): 3152 (w), 2969 (w), 1350 (m), 1322 (m), 1233 (m), 1181 (s),
1126 (s), 1057 (m), 731 cm (m).
–1
–1
1059 (s), 698 cm (m).
Anal. Calcd for C22H16F32N O S : C 25.30; H, 1.54; N, 2.68; S, 6.14.
Anal. Calcd for C23H18F32N O S : C, 26.10; H, 1.71; N, 2.65; S, 6.06.
2
4
2
2
4 2
Found: C, 25.41; H, 1.85; N, 2.99; S, 5.97.
Found: C, 26.21; H, 1.83; N, 3.04; S, 6.41.
1-(1H,1H,2H,2H-Perfluorooctyl)piperidine (15)
4-(1H,1H,2H,2H-Perfluorooctyl)morpholine (17)
A solution of perfluorinated triflate 11 (10.0 g, 20.2 mmol, 1.0 equiv),
piperidine (14; 1.72 g, 20.2 mmol, 1.0 equiv), and K CO (5.58 g, 40.3
A solution of perfluorinated triflate 11 (5.46 g, 11.0 mmol, 1.1 equiv),
morpholine (16; 871 mg, 10.0 mmol, 1.0 equiv), and K CO3 (2.76 g,
2
3
2
mmol, 2.00 equiv) in EtOAc (15 mL) was stirred for 24 h at 70 °C. Wa-
ter (20 mL) was added and the suspension was extracted with MTBE
20.0 mmol, 2.00 equiv) in EtOAc (10 mL) was stirred for 24 h at 70 °C.
Water (20 mL) was added and the suspension was extracted with
(
2 × 30 mL). The combined extracts were dried (MgSO ), filtered, and
MTBE (2 × 30 mL). The combined extracts were dried (MgSO ), fil-
4
4
evaporated. Product 15 (7.88 g, 18.3 mmol, 91%) was obtained as a
colorless liquid after fractionized vacuum distillation (bp 78 °C/5.2
mbar).
tered, and evaporated. Product 17 (3.37 g, 7.78 mmol, 78%) was ob-
tained as a yellow liquid.
IR (ATR): 2965 (w), 2914 (w), 2857 (w), 2815 (w), 1452 (w), 1410 (w),
1364 (w), 1318 (w), 1234 (s), 1188 (s), 1142 (vs), 1076 (m), 1034 (w),
IR (ATR): 2939 (m), 2859 (w), 2786 (w), 1472 (w), 1446 (w), 1233 (s),
190 (s), 1143 (s), 1079 (m), 995 (m), 810 (m), 728 (m), 708 cm–1 (m).
1001 (m), 870 (m), 730 (m), 708 (m), 697 cm (m).
–1
1
1
1
H NMR (500 MHz, CDCl ): δ = 1.45 (pent, J = 5.9 Hz, 2 H), 1.60 (pent,
H NMR (500 MHz, CDCl ): δ = 2.25–2.36 (m, 2 H), 2.47–2.49 (m, 4 H),
3
3
J = 5.6 Hz, 4 H), 2.25–2.36 (m, 2 H), 2.38–2.47 (m, 4 H), 2.60–2.66 (m,
2.64–2.70 (m, 2 H), 3.71–3.73 (m, 4 H).
2
H).
1
13
1
C{ H} NMR (125 MHz, CDCl ): δ = 28.86 (s, CH ), 49.95 (s, CH ),
3
2
2
13
C{ H} NMR (125 MHz, CDCl ): δ = 24.35 (s, CH ), 26.13 (s, 2 CH ),
53.65 (s, 2 CH ), 67.01 (s, 2 CH ).
3
2
2
2
2
2
9.13 (t, J = 21.5 Hz, CH ), 50.22 (t, J = 3.9 Hz, CH ), 54.62 (s, 2 CH ).
19
1
2
2
2
F{ H} NMR (470 MHz, CDCl ): δ = –80.76 (tt, J = 2.1 Hz, J = 10.3 Hz),
3
1
9
1
F{ H} NMR (470 MHz, CDCl ): δ = –80.81 (tt, J = 2.2 Hz, J = 10.0 Hz),
–113.88 to –114.11 (m), –121.82 to –122.03 (m), –122.77 to –122.97
(m), –123.42 to –123.63 (m), –126.04 to –126.20 (m).
3
–113.95 to –114.16 (m), –121.80 to –121.96 (m), –122.72 to –122.92
(
m), –123.45 to –123.67 (m), –126.03 to –126.21 (m).
HRMS (ESI): m/z [M + H]+ calcd for C12H13F13NO: 434.0784; found:
434.0789.
HRMS (ESI): m/z [M + H]+ calcd for C13H15F13N: 432.0991; found:
432.0983.
4,4-Bis(1H,1H,2H,2H-perfluorooctyl)morpholinium Trifluoro-
1,1-Bis(1H,1H,2H,2H-perfluorooctyl)piperidinium Trifluorometh-
methanesulfonate (3a)
anesulfonate (2a)
A solution of perfluorinated triflate 11 (4.25 g, 8.56 mmol, 1.1 equiv)
and amine 17 (3.37 g, 7.78 mmol, 1.0 equiv) in toluene (5 mL) was
stirred in a tightly closed reaction tube for 3 h at 130 °C. After evapo-
ration of the volatiles, the residue was recrystallized (MTBE, 20 mL) to
furnish product 3a (1.85 g, 1.99 mmol, 26%) as a colorless solid; mp
103 °C.
A solution of perfluorinated triflate 11 (2.11 g, 4.25 mmol, 1.0 equiv)
and amine 15 (1.83 g, 4.25 mmol, 1.0 equiv) in toluene (10 mL) was
stirred in a tightly closed reaction tube for 3 h at 150 °C. After evapo-
ration of the volatiles, the residue was recrystallized (MTBE, 20 mL) to
furnish product 2a (3.04 g, 3.28 mmol, 77%) as a colorless solid; mp
1
39 °C.
IR (ATR): 3029 (w), 2996 (w), 2970 (w), 2958 (w), 1471 (w), 1319 (w),
227 (s), 1190 (s), 1142 (s), 1124 (s), 1084 (m), 1029 (s), 936 (m), 842
IR (ATR): 3033 (w), 2779 (w), 1473 (w), 1455 (w), 1425 (w), 1367 (w),
1330 (w), 1288 (m), 1224 (s), 1201 (s), 1144 (s), 1109 (m), 1091 (m),
1024 (s), 979 (m), 708 (m), 638 cm (s).
–1
1
–1
(m), 706 (m), 639 cm (s).
1
H NMR (500 MHz, CD OD): δ = 2.95–3.08 (m, 4 H), 3.77–3.83 (m, 4
3
1
H NMR (500 MHz, CD OD): δ = 1.77 (pent, J = 6.2 Hz, 2 H), 2.00 (pent,
H), 4.09–4.15 (m, 4 H), 4.15–4.21 (m, 4 H).
3
J = 6.0 Hz, 4 H), 2.83–2.96 (m, 4 H), 3.58 (t, J = 5.6 Hz, 4 H), 3.87–3.92
13
1
C{ H} NMR (125 MHz, CD OD): δ = 24.82 (t, J = 21.4 Hz, 2 CH ), 51.77
3
2
(m, 4 H).
(s, br., 2 CH ), 60.41 (s, 2 CH ), 61.17 (s, 2 CH ).
2 2 2
13
1
C{ H} NMR (125 MHz, CD OD): δ = 20.58 (s, 2 CH ), 21.79 (CH ),
19
1
3
2
2
F{ H} NMR (470 MHz, CD OD): δ = –80.15 (s), –82.38 (tt, J = 2.5 Hz,
3
2
4.81 (t, J = 21.6 Hz, 2 CH ), 49.85 (s, 2 CH ), 61.39 (s, 2 CH ).
2 2 2
J = 10.2 Hz), –114.75 to –114.89 (m), –122.75 to –122.97 (m), –123.79
to –123.97 (m), –124.04 to –124.22 (m), –127.25 to –127.40 (m).
19
1
F{ H} NMR (470 MHz, CD OD): δ = –80.16 (s), –82.32 to –82.51 (m),
3
–
114.25 to –114.39 (m), –122.73 to –122.98 (m), –123.73 to –123.95
–
HRMS (ESI): m/z [M – OTf ] calcd for C20H16F26NO: 780.0811; found:
(m), –127.22 to –127.40 (m).
780.0815.
–
HRMS (ESI): m/z [M – OTf ] calcd for C21H18F26N: 778.1024; found:
778.1027.
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

F
Synthesis
T. Alpers et al.
Paper
31
1
4,4-Bis(1H,1H,2H,2H-perfluorooctyl)morpholinium Bis(trifluoro-
P{ H} NMR (203 MHz, CD OD): δ = 24.36 (s).
3
methanesulfonyl)imide (3b)
19
1
F{ H} NMR (470 MHz, CD OD): δ = –82.40 (tt, J = 9.8 Hz, J = 2.8 Hz),
3
Triflate salt 3a (500 mg, 0.538 mmol) was converted with HNTf (151
mg, 0.538 mmol) according to GPA to furnish compound 3b (311 mg,
–114.77 to –114.96 (m), –122.58 to –122.92 (m), –123.61 to –123.84
(m), –127.15 to –127.36 (m).
2
0
.293 mmol, 55%) after evaporation of the solvent and recrystalliza-
–
HRMS (ESI): m/z [M – I ] calcd for C26H19F13P: 609.1017; found:
tion (MTBE, 10 mL) as a colorless solid; mp 82 °C.
609.1015.
IR (ATR): 1739 (w), 1463 (w), 1348 (m), 1321 (m), 1232 (m), 1181 (s),
–1
1
126 (s), 1056 (s), 905 (w), 741 (m), 618 (m), 601 cm (m).
Exchange of Anions with LiNTf ; General Procedure B (GPB)
2
Anal. Calcd for C22H16F32N O S : C, 24.92; H, 1.52; N, 2.64; S, 6.05.
Found: C, 24.83; H, 1.53; N, 2.44; S, 6.04.
2
5
2
A solution iodide salts 5a–10a (0.0484–0.50 mmol) and LiNTf2 (1.5
equiv per phosphorus atom) in acetone (30 mL/g) was stirred for 2 d
at 23 °C. The solvent was removed in vacuo and the residue redis-
solved in EtOAc (100 mL/g) and filtered. The filtrate was repeatedly
1,4-Bis(1H,1H,2H,2H-perfluorooctyl)-1,4-diazoniabicyc-
lo[2.2.2]octane Bis(trifluoromethanesulfonate) (4a)
(ca. 3 ×) extracted with H O (3 × 200 mL/g) until the aqueous extract
2
was free from iodide (monitored with a drop of aq AgNO3 solution).
A solution of perfluorinated triflate 11 (6.00 g, 12.1 mmol, 3.0 equiv)
and DABCO (18; 458 mg, 4.04 mmol, 1.0 equiv) in toluene (10 mL)
was stirred in a tightly closed reaction tube for 17 h at 130 °C. After
evaporation of the volatiles, the residue was recrystallized (MTBE, 20
mL) to furnish product 4a (3.64 g, 3.30 mmol, 82%) as a colorless sol-
id; mp >250 °C.
The organic layer was dried (MgSO ), filtered, and evaporated, and the
4
crude product recrystallized (MTBE).
(1H,1H,2H,2H-Perfluorooctyl)triphenylphosphonium Bis(trifluo-
romethanesulfonyl)imide (5b)
IR (ATR): 3033 (w), 1473 (w), 1437 (w), 1368 (w), 1323 (w), 1246 (s),
Iodide salt 5a (100 mg, 0.136 mmol, 1.0 equiv) and LiNTf (59 mg,
2
1
7
1
230 (s), 1209 (s), 1189 (s), 1145 (s), 1088 (m), 1070 (w), 1027 (s),
08 (m), 630 cm (s).
0.204 mmol, 1.5 equiv) were converted according to GPB to furnish
compound 5b (93 mg, 0.105 mmol, 77%) after recrystallization
(MTBE, 10 mL) as a colorless solid; mp 93 °C.
–1
H NMR (500 MHz, acetone-d ): δ = 3.18–3.33 (m, 4 H), 4.32–4.42 (m,
6
4
H), 4.57 (br s, 12 H).
IR (ATR): 3078 (w), 2967 (w), 2936 (w), 1443 (w), 1345 (s), 1327 (m),
1237 (m), 1197 (s), 1140 (s), 1119 (s), 1052 (s), 903 (m), 740 (m), 725
13
1
C{ H} NMR (125 MHz, acetone-d ): δ = 25.38 (t, J = 20.9 Hz, 2 CH ),
6
2
–1
(
m), 614 cm (m).
Anal. Calcd for C28
Found: C, 37.59; H, 1.79; N, 1.21; S, 7.00.
5
2.66 (s, 6 CH ), 57.67 (s, 2 CH ).
2
2
19
1
H F19NO PS : C, 37.81; H, 2.15; N, 1.57; S, 7.22.
19 4 2
F{ H} NMR (470 MHz, acetone-d ): δ = –79.46 (s), –81.96 (tt, J = 10.3
6
Hz, J = 2.7 Hz), –113.78 to –113.99 (m), –122.61 to –122.80 (m),
–
123.61 to –123.96 (m), –127.00 to –1127.21 (m).
(
1H,1H,2H,2H-Perfluorooctyl)diphenylphosphane (20)
–
HRMS (ESI): m/z [M – 2 OTf ] calcd for C22H20F26N : 403.0600; found:
2
The entire procedure including the isolation and characterization of
the product was performed under an inert atmosphere (N ). n-BuLi
403.0572.
2
(
0.94 mL, 2.4 mmol, 1.0 equiv, 2.5 mol/L solution in hexane) was add-
1
,4-Bis(1H,1H,2H,2H-perfluorooctyl)-1,4-diazoniabicyc-
ed at r.t. to a solution of Ph PH (438 mg, 2.40 mmol, 1.0 equiv) in abs
2
lo[2.2.2]octane Bis[bis(trifluoromethanesulfonyl)imide] (4b)
THF (2 mL). After stirring the mixture for 5 min at 23 °C, perfluorinat-
ed iodide 19 (1.12 g, 2.40 mmol, 1.0 equiv) was added and the mix-
ture was further stirred for 17 h at 23 °C. The mixture was then fil-
tered using a reversible frit and the resulting solution was evaporated
to furnish the product 20 (1.11 g, 2.09 mmol, 89%) as an off-white sol-
id; mp 40 °C.
Triflate salt 4a (1.23 g, 1.11 mmol) was converted with HNTf2 (626
mg, 2.23 mmol) according to GPA to furnish compound 4b (0.961 g,
0.817 mmol, 73%) after evaporation of the solvent and recrystalliza-
tion (MTBE, 30 mL) as a colorless solid; mp 206 °C.
IR (ATR): 3129 (w), 3051 (w), 1474 (w), 1443 (w), 1342 (s), 1239 (m),
–1
1187 (vs), 1119 (vs), 1055 (s), 792 (m), 742 (m), 649 (m), 571 cm (s).
IR (ATR): 3072 (w), 1482 (w), 1439 (w), 1364 (w), 1235 (m), 1182 (s),
1139 (s), 1121 (m), 1070 (m), 1028 (w), 925 (w), 847 (w), 746 (m),
735 (m), 723 (m), 693 cm (s).
Anal. Calcd for C26H20F38N O S : C, 22.85; H, 1.48; N, 4.10; S, 9.38.
Found: C, 22.47; H, 1.84; N, 4.45; S, 9.01.
4
8 4
–1
1
H NMR (300 MHz, CDCl ): δ = 2.05–2.23 (m, 2 H), 2.24–2.37 (m, 2 H),
3
(1H,1H,2H,2H-Perfluorooctyl)triphenylphosphonium Iodide (5a)
7.33–7.41 (m, 6 H), 7.42–7.51 (m, 4 H).
A solution of perfluorinated iodide 19 (1.64 g, 3.46 mmol, 1.0 equiv)
31
1
P{ H} NMR (203 MHz, CDCl ): δ = –16.05 (s).
3
and Ph P (1.00 g, 3.81 mmol, 1.1 equiv) in DMF (2 mL) was stirred in a
3
1
3
2
9
T
h
e
C
N
M
R
s
p
e
c
t
r
u
m
w
a
s
i
n
a
c
c
o
r
d
a
n
c
e
w
i
t
h
l
i
t
e
r
a
t
u
r
e
d
a
t
a
.
tightly closed reaction tube for 24 h at 105 °C. The mixture was dilut-
ed with MTBE (10 mL) and the product precipitated. It was isolated by
filtration and dried under high vacuum to furnish compound 5a (1.81
g, 2.64 mmol, 76%) as a colorless solid; mp 169 °C.
+
HRMS (ESI): m/z [M + Na] calcd for C20H14F13NaP: 555.0523; found:
555.0529.
Bis(1H,1H,2H,2H-perfluorooctyl)diphenylphosphonium Iodide
(6a)
IR (ATR): 3057 (w), 2876 (w), 1741 (w), 1438 (w), 1234 (s), 1190 (s),
–1
1115 (s), 1092 (m), 939 (m), 741 (s), 727 (s), 689 cm (s).
1
A solution of perfluorinated iodide 19 (557 mg, 1.17 mmol, 1.25
equiv) and phosphane 20 (500 mg, 0.94 mmol, 1.0 equiv) in DMF (2
mL) was stirred in a tightly closed reaction tube for 17 h at 105 °C. The
mixture was diluted with MTBE (10 mL); the crude material precipi-
H NMR (500 MHz, CD OD): δ = 2.52–2.72 (m, 2 H), 3.79–3.95 (m, 2
3
H), 7.74–7.99 (m, 15 H).
13
1
C{ H} NMR (125 MHz, CD OD): δ = 15.57 (d, J = 59.6 Hz, CH ), 25.47–
3
2
2
6.09 (m, CH ), 118.62 (d, J = 88.1 Hz, 3 C), 131.79 (d, J = 12.2 Hz, 6
2
CH), 134.98 (d, J = 10.1 Hz, 6 CH), 136.76 (d, J = 3.5 Hz, 3 CH).
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

G
Synthesis
T. Alpers et al.
Paper
tated and was collected by filtration. The residue was recrystallized
MTBE, 10 mL) to furnish product 6a (521 mg, 0.517 mmol, 55%) as a
pound 7b (108 mg, 65.3 μmol, 88%) after recrystallization (MTBE, 10
mL) as a colorless solid; mp 82 °C.
(
colorless solid; mp 134 °C.
IR (ATR): 3071 (w), 2964 (w), 2928 (w), 1440 (w), 1350 (m), 1333 (m),
1231 (m), 1182 (s), 1142 (s), 1127 (s), 1092 (m), 1051 (m), 738 (m),
649 (m), 610 cm (m).
IR (ATR): 2890 (w), 2875 (w), 1140 (w), 1405 (w), 1231 (s), 1187 (s),
–1
–1
1120 (s), 1071 (m), 808 (m), 737 (m), 688 cm (m).
1
H NMR (500 MHz, CD OD): δ = 2.37–2.62 (m, 4 H), 3.51–3.69 (m, 4
Anal. Calcd for C46H32F38N O P S : calcd.: C, 33.43; H, 1.95; N, 1.69; S,
3
2
8 2 4
H), 7.74–7.89 (m, 4 H), 7.89–8.12 (m, 6 H).
7.76. Found: C, 33.10; H, 1.83; N, 1.51; S, 7.57.
13
1
C{ H} NMR (125 MHz, CD OD): δ = 12.25–15.26 (m, 2 CH ; HMQC),
3
2
2
2.77–27.04 (m, 2 CH ; HMQC), 116.81 (d, J = 85.3 Hz, 2 C), 131.86 (d,
1,3-Bis[(1H,1H,2H,2H-perfluorooctyl)diphenylphosphonio]pro-
2
J = 14.5 Hz, 4 CH), 134.47 (d, J = 11.8 Hz, 4 CH), 137.10 (d, J = 3.3 Hz, 2
pane Diiodide (8a)
CH).
A solution of perfluorinated iodide 19 (1.44 g, 3.03 mmol, 2.5 equiv)
and DPPP (22; 500 mg, 1.21 mmol, 1.0 equiv) in DMF (5 mL) was
stirred in a tightly closed reaction tube for 24 h at 105 °C. The mixture
was diluted with MTBE (20 mL); the crude product precipitated and
was collected by filtration. The residue was recrystallized (MTBE, 50
mL) to furnish product 8a (1.07 g, 0.786 mmol, 65%) as a colorless sol-
id; mp 165 °C.
31
1
P{ H} NMR (203 MHz, CD OD): δ = 29.20 (s).
3
19
1
F{ H} NMR (470 MHz, CD OD): δ = –82.35 to –82.47 (m), –114.77 to
3
–
–
115.08 (m), –122.65 to –122.92 (m), –123.65 to –123.97 (m),
127.15 to –127.39 (m).
–
HRMS (ESI): m/z [M – I ] calcd for C28H18F26P: 879.0731; found:
879.0718.
IR (ATR): 2911 (w), 2875 (w), 1739 (w), 1438 (w), 1228 (s), 1189 (s),
–1
1
143 (s), 1116 (s), 737 (m), 689 cm (m).
Bis(1H,1H,2H,2H-perfluorooctyl)diphenylphosphonium Bis(tri-
fluoromethanesulfonyl)amide (6b)
1
H NMR (500 MHz, CD OD): δ = 1.65–1.82 (m, 2 H), 2.34–2.60 (m, 4
3
H), 3.42–3.57 (m, 4 H), 3.58–3.73 (m, 4 H), 7.65–7.83 (m, 8 H), 7.83–
Iodide salt 6a (500 mg, 0.50 mmol, 1.0 equiv) and LiNTf (72 mg, 0.75
mmol, 1.5 equiv) were converted according to GPB to furnish com-
pound 6b (410 mg, 0.354 mmol, 71%) after recrystallization (MTBE,
2
7.98 (m, 12 H).
13
1
C{ H} NMR (125 MHz, CD OD): δ = 12.61–15.32 (m, 2 CH ; HMQC),
3
2
1
4.14–18.85 (m, CH ; HMQC), 19.56–24.98 (m, 2 CH ; HMQC), 25.10
20 mL) as a colorless solid; mp 95 °C.
2
2
(
t, J = 22.3 Hz, 2 CH ), 116.87–117.56 (m, 4 C), 131.67–131.77 (m, 8
2
IR (ATR): 2962 (w), 2931 (w), 1440 (w), 1345 (m), 1329 (m), 1179 (s),
CH), 134.42–134.49 (m, 8 CH), 136.73–136.84 (m, 4 CH).
–
1
1129 (s), 1062 (m), 950 (m), 922 (m), 692 (m), 609 cm (m).
31
1
P{ H} NMR (203 MHz, CD OD): δ = 27.69 (s).
3
Anal. Calcd for C30H18F32NO PS : C, 31.08; H, 1.56; N, 1.21; S, 5.53.
Found: C, 31.18; H, 1.64; N, 0.84; S, 5.17.
4
2
19
1
F{ H} NMR (470 MHz, CD OD): δ = –82.42 (tt, J = 10.4 Hz, J = 2.6 Hz),
3
–114.79 to –115.17 (m), –122.66 to –123.04 (m), –123.49 to –123.76
(
m), –123.76 to –124.08 (m), –127.18 to –127.42 (m).
1
,2-Bis[(1H,1H,2H,2H-perfluorooctyl)diphenylphosphonio]eth-
–
HRMS (ESI): m/z [M – 2 I ] calcd for C43H34F P2: 553.0855; found:
5
ane Diiodide (7a)
26
53.0842.
A solution of perfluorinated iodide 19 (11.9 g, 25.0 mmol, 2.6 equiv)
and DPPE (21; 3.88 g, 9.70 mmol, 1.00 equiv) in DMF (10 mL) was
stirred in a tightly closed reaction tube for 24 h at 105 °C. The mixture
was diluted with MTBE (50 mL); the crude product precipitated and
was collected by filtration. The residue was recrystallized (MTBE, 100
mL) to furnish product 7a (12.5 g, 9.29 mmol, 96%) as a colorless sol-
id; mp 135 °C.
1
,3-Bis[(1H,1H,2H,2H-perfluorooctyl)diphenylphosphonio]pro-
pane Bis[bis(trifluoromethanesulfonyl)imide] (8b)
Iodide salt 8a (100 mg, 73.5 μmol, 1.0 equiv) and LiNTf (63 mg, 0.22
2
mmol, 3.0 equiv) were converted according to GPB to furnish com-
pound 8b (83 mg, 50 μmol, 68%) after recrystallization (MTBE, 5 mL)
as a colorless solid; mp 54 °C.
IR (ATR): 2867 (w), 1437 (w), 1339 (w), 1198 (s), 1142 (s), 1122 (m),
–1
736 (m), 685 cm (m).
IR (ATR): 3071 (w), 2998 (w), 2959 (w), 2928 (w), 1441 (w), 1347 (m),
1328 (m), 1228 (m), 1181 (s), 1133 (s), 1054 (s), 1054 (s), 738 (m),
1
H NMR (500 MHz, CD OD): δ = 2.36–2.50 (m, 4 H), 3.54–3.62 (m, 4
3
–1
614 (m), 601 cm (m).
Anal. Calcd for C47H F N O P S : C, 33.87; H, 2.06; N, 1.68; S, 7.68.
34 38 2 8 2 4
H), 3.64–3.72 (m, 4 H), 7.74–7.83 (m, 8 H), 7.89–7.99 (m, 12 H).
13
1
C{ H} NMR (125 MHz, CD OD): δ = 14.82–15.40 (m, 2 CH ), 16.89 (t,
3
2
Found: C, 33.58; H, 2.42; N, 1.57; S, 7.42.
J = 25.1 Hz, 2 CH ), 25.28 (t, J = 22.8 Hz, 2 CH ), 115.26–116.35 (m, 4
2
2
C), 131.83–132.14 (m, 8 CH), 134.99–135.32 (m, 8 CH), 137.23 (s, 4
CH).
1,4-Bis[(1H,1H,2H,2H-perfluorooctyl)diphenylphosphonio]bu-
tane Diiodide (9a)
31
1
P{ H} NMR (203 MHz, CD OD): δ = 31.25 (s).
3
A solution of perfluorinated iodide 19 (1.39 g, 2.93 mmol, 2.5 equiv)
and DPPB (23; 500 mg, 1.17 mmol, 1.0 equiv) in DMF (5 mL) was
stirred in a tightly closed reaction tube for 24 h at 105 °C. The mixture
was diluted with MTBE (20 mL); the crude material precipitated and
was collected by filtration. The residue was recrystallized (MTBE, 50
mL) to furnish product 9a (1.33 g, 0.968 mmol, 83%) as a colorless sol-
id; mp 203 °C.
1
9
1
F{ H} NMR (470 MHz, CD OD): δ = –82.40 (tt, J = 9.9 Hz, J = 2.6 Hz),
3
–
114.40 to –114.67 (m), –122.69 to –122.87 (m), –123.49 to –123.69
(m), –123.69 to –123.91 (m), –127.19 to –127.35 (m).
–
HRMS (ESI): m/z [M – 2 I ] calcd for C 2H32F P2: 546.0782; found:
5
4
26
46.0763.
1
,2-Bis[(1H,1H,2H,2H-perfluorooctyl)diphenylphosphonio]eth-
IR (ATR): 2876 (w), 1438 (m), 1230 (s), 1189 (s), 1142 (s), 1116 (s),
ane Bis[bis(trifluoromethanesulfonyl)imide] (7b)
–1
1087 (m), 736 (s), 687 cm (s).
Iodide salt 7a (100 mg, 74.3 μmol, 1.0 equiv) and LiNTf (64 mg, 0.223
2
mmol, 3.0 equiv) were converted according to GPB to furnish com-
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

H
Synthesis
T. Alpers et al.
Paper
1
H NMR (500 MHz, CD OD): δ = 1.84–1.97 (m, 4 H), 2.49–2.64 (m, 4
IR (ATR): 3071 (w), 2950 (w), 2931 (w), 1441 (w), 1343 (m), 1328 (m),
1230 (m), 1184 (s), 1138 (s), 1057 (s), 739 (m), 611 cm (m).
3
–1
H), 3.43–3.48 (m, 4 H), 3.50–3.60 (m, 4 H), 7.82–7.91 (m, 8 H), 7.96–
8
.11 (m, 12 H).
Anal. Calcd for C49H38F38N O P S : C, 34.72; H, 2.26; N, 1.65; S, 7.58.
Found: C, 34.33; H, 2.66; N, 1.42; S, 7.88.
2
8 2 4
13
1
C{ H} NMR (125 MHz, CD OD): δ = 14.45 (d, J = 55.0 Hz, 2 CH ),
3
2
2
1.18 (d, J = 50.2 Hz, 2 CH ), 23.61 (d, J = 18.9 Hz, 2 CH ), 25.31 (t, J =
2
2
2
3.0 Hz, 2 CH ), 117.85 (d, J = 84.9 Hz, 4 C), 131.66 (d, J = 12.7 Hz, 8
2
CH), 134.55 (d, J = 9.8 Hz, 8 CH), 136.59 (d, J = 2.2 Hz, 4 CH).
Acknowledgement
31
1
P{ H} NMR (203 MHz, CD OD): δ = 28.43 (s).
3
This work was funded by the ‘Zentrales Innovationsprogramm Mittel-
stand (ZIM)’ of the ‘Bundesministerium für Wirtschaft und Energie
1
9
1
F{ H} NMR (470 MHz, CD OD): δ = –82.41 (tt, J = 10.9 Hz, J = 3.3 Hz),
3
–
114.72 to –115.09 (m), –122.53 to –122.91 (m), –123.49 to –123.71
(BMWi)’ (Germany). MTBE was obtained as a generous gift from
(m), –123.71 to –124.09 (m), –126.99 to –127.42 (m).
Evonik Industries, Marl, Germany.
–
HRMS (ESI): m/z [M – 2 I ] calcd for C44H36F26P2: 560.0939; found:
560.0923.
Supporting Information
1
,4-Bis[(1H,1H,2H,2H-perfluorooctyl)diphenylphosphonio]bu-
Supporting information for this article is available online at
https://doi.org/10.1055/s-0037-1610072.
tane Bis[bis(trifluoromethanesulfonyl)imide] (9b)
S
u
p
p
o
nrtogI
i
f
rm oaitn
S
u
p
p
ortioIgnfmr oaitn
Iodide salt 9a (100 mg, 72.8 μmol, 1.0 equiv) and LiNTf (63 mg, 0.22
2
mmol, 3.0 equiv) were converted according to GPB to furnish com-
pound 9b (79 mg, 47 μmol, 65%) after recrystallization (MTBE, 5 mL)
as a colorless wax.
References
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1182 (s), 1133 (s), 1055 (s), 738 (m), 614 (m), 600 cm (m).
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1
072 (m), 737 (s), 688 (s), 648 cm (m).
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H NMR (500 MHz, CD OD): δ = 1.54–1.65 (m, 4 H), 1.73–1.81 (m, 2
3
(
(
(
6) (a) Kubwabo, C.; Vais, N.; Benoit, F. M. J. Environ. Monit. 2004, 6,
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13
1
C{ H} NMR (125 MHz, CD OD): δ = 14.35 (d, J = 54.4 Hz, 2 CH ),
3
2
2
1.30 (d, J = 49.7 Hz, 2 CH ), 22.36–22.43 (m, 2 CH ), 25.25 (t, J = 22.9
2
2
Hz, 2 CH ), 31.97–32.25 (m, CH ), 118.11 (d, J = 84.7 Hz, 4 C), 131.61
2
2
(d, J = 12.6 Hz, 8 CH), 134.47 (d, J = 9.9 Hz, 8 CH), 136.51 (d, J = 3.0 Hz,
4
CH).
31
1
P{ H} NMR (203 MHz, CD OD): δ = 28.34 (s).
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19
1
F{ H} NMR (470 MHz, CD OD): δ = –82.40 (tt, J = 10.3 Hz, J = 3.1 Hz),
3
–114.59 to –115.25 (m), –122.53 to –123.02 (m), –123.36 to –124.30
(
(m), –126.88 to –127.69 (m).
–
HRMS (ESI): m/z [M – 2 I ] calcd for C45H38F26P2: 567.1011; found:
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©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I