Synthesis of novel phosphonium betaines and bis-betaines derived from hexafluoro-1,4-naphthoquinone

Article abstract of DOI:10.1016/j.jfluchem.2017.11.010

Reactions of hexafluoro-1,4-naphthoquinone with phosphorus-centered bis-phenylphosphanes with structure Ph₂P(CH₂)_nPPh₂ (where n = 1–5) and Et₂P(CH₂)₂PEt₂ in various solvents (anhydrous C₆H₆, aq. C₆H₆, aq. dioxane, aq. DMSO, or MeOH) were investigated. It was shown that the use of aqueous dioxane and DMSO leads to target products of phosphanodefluorination (i.e., phosphorus-containing betaines and bis-betaines) with high yields. We found that the betaines upon purification by thin-layer chromatography underwent various transformations such as a ring contraction (thus yielding novel polyfluorinated indenones) or addition of an acetone molecule at the C[dbnd]O bond of the fluorinated 1,4-naphthoquinone. According to X-ray diffraction analysis, there were intermolecular F?π interactions in the crystal packing of all the obtained betaines. The interactions are characterized by short distances F?Cg from 3.151(5) to 3.831(2) ? (where Cg is a centroid of π-system).

Full text of DOI:10.1016/j.jfluchem.2017.11.010

JournalofFluorineChemistry206(2018)19–28
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis of novel phosphonium betaines and bis-betaines derived from
hexafluoro-1,4-naphthoquinone
S.I. Zhivetyevaa,⁎, E.V. Tretyakova,b, I.Yu. Bagryanskayaa,b
a
N.N. Vorozhtsov Institute of Organic Chemistry, Russian Academy of Sciences, Novosibirsk 630090, Russia
National Research University – Novosibirsk State University, Novosibirsk 630090, Russia
b
A R T I C L E I N F O
A B S T R A C T
Keywords:
Fluorinated 1,4-naphthoquinones
Bis-phosphanes
Nucleophilic substitution
Phosphonium betaines
Reactions of hexafluoro-1,4-naphthoquinone with phosphorus-centered bis-phenylphosphanes with structure
Ph2P(CH2)nPPh2 (where n = 1–5) and Et2P(CH2)2PEt2 in various solvents (anhydrous C6H6, aq. C6H6, aq. di-
oxane, aq. DMSO, or MeOH) were investigated. It was shown that the use of aqueous dioxane and DMSO leads to
target products of phosphanodefluorination (i.e., phosphorus-containing betaines and bis-betaines) with high
yields. We found that the betaines upon purification by thin-layer chromatography underwent various trans-
formations such as a ring contraction (thus yielding novel polyfluorinated indenones) or addition of an acetone
molecule at the C]O bond of the fluorinated 1,4-naphthoquinone. According to X-ray diffraction analysis, there
were intermolecular F⋯π interactions in the crystal packing of all the obtained betaines. The interactions are
characterized by short distances F⋯Cg from 3.151(5) to 3.831(2) Å (where Cg is a centroid of π-system).
1. Introduction
of the hydrocarbon chain between the two phosphorus atoms and Et2P
(CH2)2PEt2. In this regard, we performed a series of experiments to
The 1,4-naphthoquinone structure occurs frequently in numerous
synthesized and natural compounds associated with antibacterial, an-
tifungal, antiviral, antitumor, and antimalarial activities [1–3]. Re-
cently, it was shown that polyfluorinated functionalized 1,4-naphtho-
quinones can also be inhibitors of cancer cells growth [4a–f]. In our
group, it has been found that a number of polyfluorinated 1,4-naph-
thoquinone derivatives containing one phosphorus atom possess an
antitumor activity [5–7]. In addition to imparting antitumor activity to
derivatives, such 1,4-naphthoquinones can be effective antioxidants
protecting bacterial cells from H2O2-induced and spontaneous muta-
genesis [6,7].
synthesize new phosphonium betaine derivatives of hexafluoro-1,4-
naphthoquinone; these compounds hold promise as anticancer agents.
We also established a correlation between the structure of the initial
nucleophile, the solvent in which the reaction was carried out, and the
reaction product. Besides, a ring contraction of a polyfluorinated 1,4-
naphthoquinone was found to give rise to novel fluorinated indenone
betaines. Their structures were unambiguously proved by X-ray dif-
fraction (XRD) analysis.
2. Results and discussion
Lately, we reported that reactions of hexafluoro-1,4-naphthoqui-
none (1) with PPh3 or various other phosphorus-centered phenylpho-
sphanes PPh2R (Me, Ph, etc.) lead to phosphorus-containing betaines
with phosphonium structure A and B (Chart 1) [5–8]. The common
pattern of these reactions is nucleophilic substitution of the fluorine
atom at position 2 of 1,4-naphthoquinone 1 with initial formation, in
case of PPh3, of highly reactive intermediate C in dry C6H6. As it turned
out, this compound is unstable and quickly reacts with water or aniline,
thus yielding corresponding phosphobetaines A and B [7].
2.1. Reactions of hexafluoro-1,4-naphthoquinone 1 with bis-phosphanes
In our previous paper, we reported that the reaction of hexafluoro-
1,4-naphthoquinone 1 with methyldiphenylphosphane, PPh3, or var-
ious other fluorinated phenylphosphanes PPhR1R2 (R1 = Me, Ph;
R2 = 3,5-F2C6H3, 2,5-F2C6H3) in MeOH or DMSO gives phosphonium
betaines with a high yield [7,8]. As it was shown earlier, the reaction of
1,4-naphthoquinone 1 with PPh3 was carried out in thoroughly dried
C6H6 in an atmosphere of dry argon and led to highly reactive inter-
mediate C. In the latter, the presence of the > CF2 group at position 3
indicates easy further substitution. The use of bis-phosphanes Ph2P
(CH2)nPPh2 (especially with n = 2), could lead to not only the products
In light of the obtained data, it was interesting to determine how the
reaction will proceed if to expand the range of phosphorus-centered
nucleophiles to bis-phosphanes Ph2P(CH2)nPPh2 with different lengths
⁎
Corresponding author.
E-mail address: zhivietsv@nioch.nsc.ru (S.I. Zhivetyeva).
https://doi.org/10.1016/j.jfluchem.2017.11.010
Received 19 October 2017; Received in revised form 23 November 2017; Accepted 24 November 2017
Availableonline29November2017
0022-1139/©2017ElsevierB.V.Allrightsreserved.

S.I. Zhivetyeva et al.
JournalofFluorineChemistry206(2018)19–28
Chart 1. Structure A–C.
of monosubstitution but also intramolecular cyclization.
tetrafluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate (3b) (according to
31P{1H} NMR spectra, at ∼75%, isolated yield 7%), 3,3′-(ethane-1,2-
diylbis(diphenylphosphonionediyl))bis(5,6,7,8-tetrafluoro-1,4-dioxo-
1,4-dihydronaphthalen-2-olate) (4b) (NMR yield ∼5%), and 1,2-bis
(diphenylphosphoryl)ethane (NMR yield ∼15%) (Scheme 1). In all
cases, the yields of the isolated products (3a and 3b) were small; the
reason was the fact that the betaines obtained in the reaction are not
stable when isolated by thin-layer chromatography. For example, after
TLC of the reaction mixture on silica gel in an acetone–hexane mixture
and later in ethyl acetate, betaines 3-(((diphenylphosphoryl)methyl)
diphenylphosphonio)-5,6,7,8-tetrafluoro-1-hydroxy-4-oxo-1-(2-ox-
opropyl)-1,4-dihydronaphthalen-2-olate (5a) and 3-((2-(diphenylpho-
sphoryl)ethyl)diphenylphosphonio)-5,6,7,8-tetrafluoro-1-hydroxy-4-
oxo-1-(2-oxopropyl)-1,4-dihydronaphthalen-2-olate (5b) were isolated
in the form of the adduct of one molecule of acetone with 25% and 15%
isolated yields, respectively (Scheme 1).
This assumption was tested on the reaction of hexafluoro-1,4-
naphthoquinone 1 with one equivalent of bis(diphenylphosphano)me-
thane (2a) as an example in dried C6H6 in the atmosphere of dry argon
at room temperature. After 48 h, the reaction mixture was treated with
water. According to the 19F and 31P{1H} NMR spectra, the reaction
mixture contained betaine 3-(((diphenylphosphoryl)methyl)diphenyl-
phosphonio)-5,6,7,8-tetrafluoro-1,4-dioxo-1,4-dihydronaphthalen-2-
olate (3a) as the main product (according to 31P{1H} NMR, the yield
was ∼70%, and isolated yield 5%, here and hereinafter, per initial bis-
phosphane). Besides, there were signals of 3,3′-(methylenebis(diphe-
nylphosphonionediyl))bis(5,6,7,8-tetrafluoro-1,4-dioxo-1,4-dihy-
dronaphthalen-2-olate) (4a) (according to 31P{1H} NMR, the yield was
∼5%) and an oxide: bis(diphenylphosphoryl)methane (∼20% NMR
yield; Scheme 1). The structure of 3a was solved by XRD analysis (SI,
Fig. S1).
In agreement with the data obtained earlier [7,8], the formation of
betaine 3a is reasonably explained by the primarily occurring phos-
phanodefluorination of hexafluoro-1,4-naphthoquinone 1 producing
the corresponding salt with two atoms of fluorine at position 3 as in salt
C. The subsequent reaction with water leads to the observed betaine 3a,
wherein the second phosphorus atom at the end of the hydrocarbon
chain group is oxidized by oxygen of air. Nonetheless, as we can see, the
product of mono-phosphanodefluorination reacts via the PPh2 group
with another molecule of naphthoquinone 1 and yields a small amount
of the corresponding bis-betaine 4a (Scheme 1). Because the initial
reagents were present in equivalent amounts, the remaining unreacted
phosphane (usually its amount matched the bis-betaine content) is
subsequently oxidized by air oxygen. Given that the phosphane oxides
are not the products of the nucleophilic substitution of substrate 1, here
and later, we will not mention this observation in our schemes. Under
similar conditions, the reaction of hexafluoro-1,4-naphthoquinone 1
with one equivalent of 1,2-bis(diphenylphosphano)ethane (2b) pro-
duces 3-((2-(diphenylphosphoryl)ethyl)diphenylphosphonio)-5,6,7,8-
As we know from experience [7,9] the use of DMSO as a solvent
noticeably increases the phosphanodefluorination reaction rate and
consequently raises the yields of betaines. This notion is consistent with
the results of the reaction of naphthoquinone 1 with phenylphosphane
2b (1:1) in anhydrous DMSO in the atmosphere of dry argon at room
temperature. After 24 h, the reaction mixture was quenched with water
to produce betaines 3b and 4b (NMR yield ∼82% and 4%, respectively)
and oxide 1,2-bis(diphenylphosphoryl)ethane (NMR yield ∼10%;
Scheme 2). Unfortunately, the use of DMSO hindered isolation of the
monosubstitution product, betaine 3b, and lowered the yield of the
product (Scheme 2).
According to the results of the experiments, the product of in-
tramolecular cyclization in the quinone moiety of hexafluoro-1,4-
naphthoquinone 1 did not form. Because one of the goals of our work
was to obtain a variety of phosphorus-containing bis-betaines, we fo-
cused on finding the optimal conditions for the synthesis of the target
products. We chose 1,2-bis(diphenylphosphano)ethane 2b as a model
reagent because of its availability and convenience. The presence of two
Scheme 1. Reaction of
1 with bis-phosphanes Ph2P
(CH2)nPPh2, n = 1, 2, in dried C6H6 (here and below, isolated
yields are given in parentheses).
20

S.I. Zhivetyeva et al.
JournalofFluorineChemistry206(2018)19–28
Scheme 2. Reaction of 1 with bis-phosphane 2b in different solvents.
methylene groups between phosphorus atoms ruled out the influence of
steric and electrostatic factors on the course of the reactions.
(diphenylphosphoryl)pentyl)diphenylphosphonio)-5,6,7,8-tetrafluoro-
1,4-dioxo-1,4-dihydronaphthalen-2-olate (3e) were isolated with 50%
and 53% yields, respectively. In addition, we isolated bis-betaines: 3,3′-
(butane-1,4-diylbis(diphenylphosphonionediyl))bis(5,6,7,8-tetrafluoro-
1,4-dioxo-1,4-dihydronaphthalen-2-olate) (4d) and 3,3′-(pentane-1,5-
diylbis(diphenylphosphonionediyl))bis(5,6,7,8-tetrafluoro-1,4-dioxo-
1,4-dihydronaphthalen-2-olate) (4e) with 18% and 7% yields, accord-
ingly.
The interaction of naphthoquinone 1 with 1,2-bis(diphenylpho-
sphano)ethane 2b (1:1) in system C6H6–H2O (120:1) under argon gave
a solution which, according to 31P{1H} NMR data, contained betaines
3b and 4b and a small amount of 1,2-bis(diphenylphosphoryl)ethane
(yields 82%, 9%, and 9%, respectively; Scheme 2).
Reaction of 1,4-naphthoquinone 1 with bis-phenylphosphane 2b
(1:1) in methanol, along with the desired betaine 3b (NMR yield
∼45%, isolated yield 30%), produced a substantial amount of the
corresponding bis-betaine 4b (NMR ∼27%, isolated yield 21%) and
phosphane oxide (∼28%). The system dioxane–H2O (10:1) was se-
lected as the best reaction medium for preparation of betaine 3b be-
cause the NMR and isolated yields were the highest (81% and 68%,
respectively; Scheme 2). The structure of 3b was proved by XRD ana-
lysis (SI, Fig. S2).
As shown in Scheme 2, to obtain bis-betaine 4b as the main product,
we used 2 equivalents of 1,4-naphthoquinone 1. Reactions in methanol
or in the system dioxane–H2O (10:1) yielded similar results (Scheme 2).
In both cases, a significant amount of betaine 3b was detected, even
though the reaction was carried out under argon. Perhaps the con-
siderable amounts of betaine 3b are related to the fact that the initial
1,4-naphthoquinone 1 can act, in this case, as an oxidant and oxidizes
the second PPh2 group. The best result was achieved in a DMSO–water
system. The interaction of naphthoquinone 1 with 1,2-bis(diphenyl-
phosphano)ethane 2b (2:1) in system DMSO–H2O (20:1) under argon
led to a single product, betaine 4b, which precipitated from the solution
as a bright yellow powder with a quantitative yield (∼100%; Scheme
2). The structure of 4b was proved by XRD analysis (SI, Fig. S3).
On the basis of these data, we can conclude that the most successful
conditions for the preparation of monosubstituted betaine 3b are the
system dioxane–H2O (10:1), whereas for bis-betaine 4b: DMSO–H2O
(20:1). These conditions were applied to the synthesis of bis-betaines
with different lengths of the polymethylene chain.
Equimolar amounts of naphthoquinone 1 and 1,3-bis(diphenylpho-
sphano)propane (2c) in system dioxane–H2O (10:1) were stirred under
argon at room temperature for 24 h and then in open air for 48 h.
According to 31P{1H} NMR data, the solution contained betaines 3-((3-
(diphenylphosphoryl)propyl)diphenylphosphonio)-5,6,7,8-tetrafluoro-
1,4-dioxo-1,4-dihydronaphthalen-2-olate (3c), 3,3′-(propane-1,3-diylbis
(diphenylphosphonionediyl))bis(5,6,7,8-tetrafluoro-1,4-dioxo-1,4-dihy-
dronaphthalen-2-olate) (4c) and 1,3-bis(diphenylphosphoryl)propane
oxide (yields 70%, 15%, and ∼15%, respectively). Betaines 3c and 4c
were isolated with 65% and 13% yields, respectively (Scheme 3).
Under similar conditions, target products of phosphanodefluorination,
betaines 3-((4-(diphenylphosphoryl)butyl)diphenylphosphonio)-5,6,7,8-
tetrafluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate (3d) and 3-((5-
Impressive results were obtained in the DMSO–H2O system for the
synthesis of bis-betaines 4d-e. Reactions of naphthoquinone 1 and
phosphanes 2d-e at the 2:1 initial ratio in system DMSO–H2O (20:1)
under argon led to the formation of pure bis-betaines 4d-e with quan-
titative yields. A similar reaction of naphthoquinone 1 and phosphane
2c led to bis-betaine 4c as the main product with a small amount of
betaine 3c, with isolated yields 85% and 14%, respectively (Scheme 3).
The reaction of 1,4-naphthoquinone 1 with bis(diphenylphosphano)
methane 2a (1:1) in aqueous dioxane (10:1) after 48 h produced de-
sired betaine 3a (NMR yield ∼83%, isolated yield 79%), a small
amount of betaine 4a (NMR yield ∼4%), and the corresponding
phosphane oxide (∼9%; Scheme 4). The same phosphonium betaine 3a
was formed (NMR yield ∼70%) in the reaction of bis(diphenylpho-
sphano)methane 2a with two equivalents of 1,4-naphthoquinone 1 in
system DMSO–H2O (20:1) under argon at room temperature. According
to 31P{1H} NMR data, the reaction mixture contained only 8% of de-
sired bis-betaine 4a (Scheme 4). The low yield of 4a can be explained as
follows. Initially, the reaction proceeds with formation of the inter-
mediate mono-betaine in which nucleophilicity of the PPh2 group is
decreased due to the electron-withdrawing effect of a positively
charged phosphorus atom that hinders the reaction of the mono-betaine
with the next 1,4-naphthoquinone molecule.
An increase in temperature to 120 °C in aqueous DMSO as a solvent
did not lead to significant changes in the set of products. Betaines 3a
and 4a were isolated with 70% and 12% yields, respectively (Scheme
4). It turned out that betaines are very sensitive to heating. An increase
in the temperature of the reaction mixture above 120 °C resulted in
resinous unidentified products.
The highest yield of bis-betaine 4a was achieved in the reaction of
bis(diphenylphosphano)methane 2a with two equivalents of 1,4-
naphthoquinone 1 at reflux in system dioxane–H2O (10:1). After 24 h,
according to 31P{1H} NMR data, the solution contained betaines 3a and
4a (NMR yields ∼51% and 27%), which were isolated with 43% and
21% yields, respectively (Scheme 4).
2.2. Reactions of hexafluoro-1,4-naphthoquinone 1 with bis-phosphane
Et2P(CH2)2PEt2
The reaction of hexafluoro-1,4-naphthoquinone
1 with one
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S.I. Zhivetyeva et al.
JournalofFluorineChemistry206(2018)19–28
Scheme 3. The reaction of 1 with bis-phosphanes Ph2P(CH2)nPPh2, n = 3 to 5.
equivalent of 1,2-bis(diethylphosphano)ethane (2f) was carried out in
dried C6H6 in an atmosphere of dry argon at room temperature. After
30 min, the reaction mixture was exposed to air and, according to 31P
{1H} NMR data, the solution contained betaine 3-((2-(diethylpho-
sphoryl)ethyl)diethylphosphonio)-5,6,7,8-tetrafluoro-1,4-dioxo-1,4-di-
hydronaphthalen-2-olate (3f) and 3,3′-(ethane-1,2-diylbis(diethylpho-
sphonionediyl))bis(5,6,7,8-tetrafluoro-1,4-dioxo-1,4-dihy-
bis-betaine 4f can be explained by the strong propensity of initial
bis(diethylphosphano)ethane 2f to oxidation under the action of
quinone 1.
2.3. Oxidative rearrangement of bis-betaine derivatives of hexafluoro-1,4-
naphthoquinone
dronaphthalen-2-olate) (4f) (NMR yields ∼63% and 17%, isolated
yields 48% and 12%, respectively). Additionally, there were signals of
oxide 1,2-bis(diethylphosphoryl)ethane (according to 31P{1H} NMR,
the yield was ∼17%, Scheme 5). As in the previous case, we found that
the product of cyclization did not form. Nonetheless, along with be-
taines 3f and 4f we isolated a small amount of an unexpected product –
5,6,7,8-tetrafluoro-1,4-dioxo-3-(triethylphosphonio)-1,4-dihy-
dronaphthalen-2-olate (6f) – with a 3% isolated yield (Scheme 5). Ac-
cording to 31P{1H} NMR spectra of initial 1,2-bis(diethylphosphano)
ethane 2f, the reagent was pure, without obvious traces of triethyl-
phosphane PEt3. Accordingly, the latter product 6f can be obtained only
by breaking the P − CH2 bond in the phosphonium betaine at any stage
of product formation. As we found out, such a result can be seen only in
the reaction carried out in dry C6H6. The structures of 4f and 6f were
determined by XRD analysis (SI, Figs. S4 and S5). The replacement of
dry C6H6 as a solvent with the usual system of dioxane–H2O (10:1) led
to similar results: formation of betaines 3f and 4f with isolated yields
37% and 20% yields, respectively.
The reaction of 1,4-naphthoquinone 1 with bis(diethylphosphano)
ethane 2f (2:1) in aqueous DMSO (20:1) led to strong heating and
blackening of the reaction mixture. According to 31P{1H} NMR data,
the solution consisted of only 1,4-naphthoquinone 1 and unidentified
resinous products. The use of system dioxane–H2O (10:1) gave betaines
3f and 4f (according to 31P{1H} NMR, the yields were ∼46% and 14%,
isolated yields 32% and 14%, respectively) and a small amount of the
corresponding phosphane oxide (NMR yield ∼26%). The low yields of
In the course of this work, it turned out that the resulting betaines
are not always stable when purified by chromatography on a column.
For example, during chromatography on silica gel, the elution of be-
taines 3c and 4c with a dioxane–hexane mixture led to two fractions:
the first fraction contained a mixture of betaines 3c and 2-((3-(diphe-
nylphosphoryl)propyl)diphenylphosphonio)-4,5,6,7-tetrafluoro-1-oxo-
1H-inden-3-olate (7c) in the 1:1 ratio (according to 19F NMR data), the
second contained impure 2,2′-(propane-1,3-diylbis(diphenylpho-
sphonionediyl))bis(4,5,6,7-tetrafluoro-1-oxo-1H-inden-3-olate)
(8c).
Further purification by TLC gave pure compounds 7c and 8c with yields
12% and 4%, respectively (Scheme 6). Accordingly, betaine 3d was
found to transform into 2-((4-(diphenylphosphoryl)butyl)diphenyl-
phosphonio)-4,5,6,7-tetrafluoro-1-oxo-1H-inden-3-olate (7d) isolated
with a low (8%) yield. The structures of betaines 7с, 8c, and 7d were
unambiguously proved by XRD (SI, Figs. S6 and S7).
The rearrangement leading to the quinone ring contraction is typical
for the hydroxyquinone family [10a–d]. It was hypothesized that the
transformation can be induced in the presence of O2 or H2O2, by the
action of a base, halogen, or even quinone itself [10a–d]. In this work,
for the first time, a ring contraction was observed in quinone-based
phosphonium betaines. In agreement with the literature, a putative
scheme of this transformation may include oxidation of the quinone
moiety with formation of intermediate A, then its benzylic-acid-type
rearrangement and subsequent oxidative decarboxylation of inter-
mediate B (Scheme 7).
Scheme 4. The reaction of 1 with Ph2PCH2PPh2.
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S.I. Zhivetyeva et al.
JournalofFluorineChemistry206(2018)19–28
Scheme 5. Reactions of 1 with bis-phosphane Et2P(CH2)2PEt2.
3. Conclusions
The melting points were determined on an FP 900 Thermosystem mi-
croscope melting-point apparatus (Mettler-Toledo International Inc.,
Zürich, Switzerland).
We showed that bis-phosphanes Ph2P(CH2)nPPh2 (where n = 1–5)
and Et2P(CH2)2PEt2 effectively participate in the reaction with hexa-
fluoro-1,4-naphthoquinone and thus give access to a variety of new
phosphonium betaines and bis-betaines. The effect of solvents (C6H6,
aq. C6H6, aq. dioxane, MeOH, or aq. DMSO) on the observed transfor-
mations was investigated. It was demonstrated that in most cases, the
use of aqueous dioxane or aqueous DMSO leads to the highest yields
of polyfluoro-1,4-naphthoquinone-substituted phosphonium betaines
and bis-betaines, respectively. The interaction of bis-phosphanes
Ph2PCH2PPh2 and Ph2P(CH2)2PPh2 with hexafluoro-1,4-naphthoqui-
none did not lead to formation of intramolecular cyclization products. It
was revealed that upon TLC under appropriate conditions, the betaines
underwent transformations such as addition of an acetone molecule to
the C]O bond to form a stable adduct or the ring contraction affording
novel polyfluorinated indenones.
X-ray crystallographic analyses of the crystals of betaines were
carried out on a Bruker Kappa Apex II CCD diffractometer using φ,ω-
scans of narrow (0.5°) frames with Mo Kα radiation (λ = 0.71073 Å)
and a graphite monochromator. The structures were solved by direct
methods and refined by the full-matrix least-squares method against all
F2 in anisotropic approximation using the SHELX-97 software suite
[12]. The obtained crystallographic data are presented in Table S1 (SI).
The positions of hydrogen atoms were calculated using the riding
model. Absorption corrections were applied by the empirical multiscan
method in the SADABS software [13]. The resultant crystal structures
were analyzed for short contacts between nonbonded atoms in software
packages PLATON [14] and MERCURY [15]. A table listing detailed
crystallographic data, atomic positional parameters, and bond lengths
and angles can be obtained free of charge as CCDC 1578657 (3a),
1578658 (3b), 1578659 (4b), 1578660 (4f), 1578661 (6f), 1578662
(7c), 1578663 (7d), 1578664 (8c) via http://www.ccdc.cam.ac.uk/cgi-
bin/catreq.cgi, or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or e
mail: deposit@ccdc cam ac uk
4. Experimental section
4.1. Materials and methods
Benzene was dried by distillation over P2O5 and stored over mole-
cular sieves (3 Å). Hexafluoro-1,4-naphthoquinone (1) was prepared as
reported in the literature [11]. All phosphanes were purchased from
Aldrich and Acros Organics. Solvents were of reagent quality. Unless
specified otherwise, reactions of quinone 1 with phosphanes were
carried out at room temperature under argon; crude betaines were
purified by TLC on Sorbfil.
4.2. The reaction of quinone 1 with Ph2PCH2PPh2 2a in different solvents
(anhydrous C6H6, water-containing dioxane, or DMSO)
A
solution of bis(diphenylphosphano)methane (2a; 144 mg,
0.376 mmol) in anhydrous C6H6 (2.0 mL) was added to a stirred solu-
tion of quinone 1 (100 mg, 0.376 mmol) in C6H6 (6.0 mL). After mixing
at room temperature for 30 min, the reaction mixture changed color
from cherry to yellow-green. The resulting solution was stirred for 48 h,
then water (0.2 mL) was added, and the mixture was stirred for another
3 h. The solvent was distilled off, the dry residue was crystallized from
ethyl acetate and then purified by TLC to obtain betaine 3a (13 mg,
5%).
A mixture of 1 (50 mg, 0.188 mmol), 2a (72 mg, 0.188 mmol), di-
oxane (1.0 mL), and H2O (0.1 mL) was stirred for 48 h. The precipitate
was centrifuged off, and air dried to produce compound 3a (67 mg,
56%). From the mother liquid, an additional amount of 3a was isolated
by TLC; the total yield was 95 mg (79%).
The NMR spectra were recorded on Bruker AV-300 (1H:
300.13 MHz, 13C{1H}: 75.47 MHz, 19F: 282.36 MHz, 31P{1H}:
121.49 MHz), AV-400 (1H: 400.13 MHz, 13C{1H}: 100.61 MHz), and
AV-500 (13C{1H}: 125.76 MHz) spectrometers. 1H chemical shifts are
reported relative to residual protons of deuterated acetone (δH
2.07 ppm, δC 29.80 ppm), chloroform (δH 7.25 ppm, δC 77.00 ppm),
and DMSO-d6 (δH 2.50 ppm, δC 39.50 ppm) and relative to external
Me4Si (δH = 0.00 ppm). 31P{1H} chemical shifts (δP) are reported re-
lative to an unlocked, external sample of H3PO4 (δP = 0.0 ppm); 19F
chemical shifts (δF) are reported relative to external CFCl3
(δF = 0.00 ppm); and 13C{1H} chemical shifts (δC) relative to external
Me4Si (δC = 0.00 ppm). High-resolution mass spectra (HRMS) were
acquired by means of a DFS Thermo Scientific instrument (EI, 70 eV).
A mixture of two eq. of 1 (138 mg, 0.520 mmol), 2a (100 mg,
0.260 mmol), dioxane (2.0 mL), and H2O (0.2 mL) was heated for 24 h
Scheme 6. Betaines detected after TLC purification on silica gel with a dioxane–hexane eluent.
23

S.I. Zhivetyeva et al.
JournalofFluorineChemistry206(2018)19–28
Scheme 7. Oxidative rearrangement of betaine 3c.
at 101 °C. The solvent was distilled off, the residue was purified by TLC
to prepare betaines 3a (72 mg, 43%) and 4a (47 mg, 21%).
A mixture of 1 (100 mg, 0.376 mmol), 2a (72 mg, 0.188 mmol),
DMSO (1.0 mL), and H2O (0.05 mL) was sealed in an NMR ampoule and
heated for 1 h at 120 °C. After addition of water (200 mL), the pre-
cipitate was centrifuged off, washed with water (3 × 5 mL), and air
dried. The aqueous fraction was extracted with chloroform (3 × 50 mL)
and ethyl acetate (1 × 20 mL). The combined extracts were dried over
MgSO4, filtered, and evaporated. The combined crude product was
purified by TLC to isolate betaines 3a (85 mg, 70%) and 4a (20 mg,
12%).
powder, Rf = 0.5 (acetone–hexane, 1:1), m.p. 92.0 °C followed by de-
composition. 1H NMR (CDCl3): δ = 7.83–7.90 (m, 2H, C6H5),
7.72–7.80 (m, 2H, C6H5), 7.54–7.64 (m, 4H, C6H5), 7.22–7.52 (m, 12H,
C6H5), 4.80 (br. s, 1H, OH), 4.14–4.45 (m, 2H, CH2), 3.02–3.34 (m, 2H,
CH2C(O)), 2.21 (s, 3H, CH3) ppm. 13C{1H} NMR (CDCl3): δ = 206.4 (s,
2
2
C]O), 191.8 [d, JCP = 4.1 Hz, C2], 178.7 [dm, JCP = 6.7 Hz, C4],
146.7 [ddm, 1JCF ∼ 264 Hz, 2JCF ∼ 10 Hz, C6or7], 145.2 [ddm,
1JCF = 264 Hz, 2JCF ∼ 10 Hz, C6or7], 142.7 [dm, 1JCF ∼ 280 Hz, C5or8],
4
140.7 [dm, 1JCF ∼ 255 Hz, C5or8], 133.5 [d, JCP = 3.4 Hz, C6H5],
132.5 [d, 4JCP = 3.4 Hz, C6H5], 133.1 [d, 2JCP = 11.4 Hz, C6H5], 132.9
2
4
[d, JCP = 11.5 Hz, C6H5], 132.8 [d, JCP = 3.2 Hz, C6H5], 131.9 [d,
3
For TLC, the use of the 1:1 acetone–hexane mixture instead of
diethyl ether as the eluent led to conversion of 3a into 5a.
4JCP = 2.3 Hz, C6H5], 131.9 [d, JCP = 10.7 Hz, C6H5], 131.8 [d,
3JCP = 10.7 Hz, C6H5], 130.5 [d, JCP = 10.0 Hz, C6H5], 130.3 [d,
3
2
3-(((Diphenylphosphoryl)methyl)diphenylphosphonio)-5,6,7,8-tetra-
fluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate (3a): bright yellow crys-
tals, Rf = 0.8 (Sorbfil, diethyl ether), m.p. 136.8 °C followed by de-
composition. 1H NMR (CDCl3): δ = 7.74–7.85 (m, 4H, C6H5),
7.49–7.60 (m, 4H, C6H5), 7.38–7.49 (m, 4H, C6H5), 7.28–7.38 (m, 8H,
3JCP = 9.7 Hz, C6H5], 128.8 [d, JCP = 13.4 Hz, C6H5], 128.7 [d,
2JCP = 12.3 Hz, C6H5], 128.6 [d, JCP = 12.6 Hz, C6H5], 125.4 [ddd,
2
2JCF = 9.6 Hz, JCF = 4.2 Hz, JCP = 1.5 Hz, C10F4O2], 121.8 [dd,
3
3
1JCP = 91.1 Hz, JCP = 1.5 Hz, C6H5], 121.2 [dd, JCP = 93.1 Hz,
3JCP = 1.3 Hz, C6H5], 116.3 [dm, 2JCF ∼ 9 Hz, C10F4O2], 83.5 [dd,
1JCP = 104.9 Hz, 3JCP = 1.6 Hz, C3], 73.5 [dm, 3JCF ∼ 10 Hz, C1], 55.5
3
1
2
2
C6H5), 4.43 [dd, JHP = 16.4 Hz, JHP = 11.4 Hz, 2H, CH2] ppm. 19F
1
NMR (CDCl3): δ = −139.4, −142.7, −151.9, −156.7 [ddd, 1F,
(br. s, CH2C(O)), 31.8 (br. s, C(O)CH3), 25.9 [dd, JCP = 60.0 Hz,
ortho
para
J
20.0÷21.0 Hz metaJFF 3.7÷8.5 Hz,
J
13.0÷13.2 Hz]
1JCP = 52.0 Hz, CH2] ppm. 19F NMR (CDCl3): δ = −139.4, −142.7,
FF
FF
ppm.31P{1H} (CDCl3): δ = 23.50 [d, 1P, 2JPP = 13.9 Hz], 13,13 [d, 1P,
2JPP = 13.9 Hz] ppm. IR (neat): 3504 w, 3444 m, 3059 w, 3030 vw,
2991 vw, 2960 w, 2908 w, 1701 m, 1618 m, 1579 vs, 1504 m, 1485 w,
1470 w, 1439 m, 1371 s, 1336 m, 1277 m, 1200 m, 1165 m, 1115 m,
1074 w, 1045 w, 999 w, 953 w, 893 w, 822 w, 795 w, 769 m, 742 m,
692 m, 663 vw, 602 vw, 550 w, 501 m cm−1. HRMS: calcd. for
С35H22F4O4P2 [M] 644.0924; found 644.0923; Anal. calcd. for
С35H22F4O4P2*2C3H6O (acetone): C, 64.74; H, 4.51; found: C, 64.37; H,
4.15. Crystals suitable for XRD analysis were grown in acetone–heptane
(1:1) in a refrigerator in an open flask at −5 °C.
−151.8, −156.7 [ddd, 1F,
J
19.8÷21.2 Hz metaJFF 3.7÷8.5 Hz,
FF
ortho
para
J
13.1÷13.2 Hz] ppm.31P{1H} (CDCl3): δ = 23.6 [d, 1P,
FF
2JPP = 14.0 Hz], 13.1 [d, 1P, JPP = 14.0 Hz] ppm. IR (neat): 3356 w,
3253 w, 3059 w, 3030 w, 3012 w, 2993 w, 2962 w, 2926 w, 2902 w,
2858 w, 1782 vw, 1709 m, 1618 m, 1566 vs, 1508 s, 1485 m, 1473 m,
1466 m, 1439 s, 1398 m, 1365 s, 1338 s, 1275 m, 1184 s, 1107 s,
1072 w, 1055 m, 1028 w, 999 w, 976 w, 933 m, 876 w, 787 m, 777 m,
2
744 s, 692 s, 661w, 617 vw, 550 w, 527 w, 500 m, 478 w, 419 w cm−1
.
HRMS: calcd. for С38H28F4O5P2 [M] 702.1343; found 702.1336; Anal.
calcd. for С38H28F4O5P2: C, 64.96; H, 4.02; found: C, 64.93; H, 4.18.
3,3′-(Methylenebis(diphenylphosphonionediyl))bis(5,6,7,8-tetrafluoro-
1,4-dioxo-1,4-dihydronaphthalen-2-olate) (4a): yellow powder, Rf = 0.5
(ethyl acetate), decomposes without melting. 1H NMR (CDCl3):
δ = 7.63–7.73 (m, 8H, C6H5), 7.48–7.56 (m, 4H, C6H5), 7.36–7.45 (m,
4.3. The reaction of quinone 1 with Ph2P(CH2)2PPh2 2b in different
solvents (anhydrous C6H6 or DMSO; water-containing C6H6, dioxane or
DMSO, and MeOH)
2
8H, C6H5), 5.86 [t, JHP = 17.0 Hz, 2H, CH2) ppm. 13C{1H} NMR
(CDCl3): δ = 178.1 (m, C1or4), 177.7 (m, C1or4), 174.1 (m, C2), 147.3
A mixture of quinone 1 (100 mg, 0.376 mmol), phosphane 2b
(150 mg, 0.376 mmol), and anhydrous C6H6 (6.0 mL) was stirred for
48 h at room temperature. The solvent was distilled off, and the residue
was purified by TLC to isolate betaine 3b (17 mg, 7%).
[ddm,
1JCF ∼ 273 Hz,
2JCF ∼ 11 Hz,
C6or7],
146.4
[ddm,
1JCF ∼ 270 Hz, 2JCF ∼ 10 Hz, C6or7], 144.8 [ddd, 1JCF ∼ 220 Hz,
2JCF ∼ 10 Hz, 3JCF ∼ 5 Hz, C5or8], 142.9 [ddd, 1JCF ∼ 263 Hz,
2JCF ∼ 17 Hz, 3JCF ∼ 12 Hz, C5or8], 133.6 (br. s, C6H5), 133.1 [m,
A
solution of 2b (150 mg, 0.376 mmol) in anhydrous DMSO
3JCP = 11.3 Hz, C6H5], 129.0 [m, JCP = 13.5 Hz, C6H5], 120.9 [d,
2
(1.5 mL) was added to a stirred solution of 1 (100 mg, 0.376 mmol) in
anhydrous DMSO (1.5 mL). The resulting solution was stirred for 24 h.
After addition of water (100 mL), the precipitate was separated by
centrifugation, washed with water (4 × 5 mL), and air dried. The
product was purified by TLC to obtain betaines 3b (62 mg, 25%) and 4b
(7 mg, 2%).
A solution of 1 (50 mg, 0.188 mmol) in C6H6 (2.0 mL) and H2O
(0.1 mL) was added to a stirred solution of 2b (75 mg, 0.188 mmol) in
C6H6 (10.0 mL). The reaction mixture was stirred for 24 h at room
temperature. The solvent was distilled off, the crude product was pur-
ified by column chromatography to isolate betaine 3b with yield 82 mg
(66%).
1JCP = 95.7 Hz, C6H5], 118.8 (m, C10F4O2), 116.0 (m, C10F4O2), 88.3
1
3
1
[dd, JCP = 99.9 Hz, JCP = 3.0 Hz, C3], 18.4 [t, JCP = 52.6 Hz, CH2]
ppm. 19F NMR (CDCl3): δ = −138.2, −140.7, −144.6, −149.2 [ddd,
ortho
para
1F,
J
19.5÷20.1 Hz metaJFF 9.3÷11.3 Hz,
J
13.5÷13.6 Hz]
FF
FF
ppm.31P{1H} (CDCl3): δ = 12.04 (s) ppm. IR (neat): 3427 w, 3061 w,
2956 w, 2929 w, 2872 w, 2857 w, 1704 m, 1618 s, 1580 vs, 1570 vs,
1506 s, 1485 m, 1472 m, 1439 m, 1371 s, 1335 m, 1274 s, 1166 m,
1106 m, 1046 m, 1029 w, 999 w, 954 m, 935 w, 894 w, 821 w, 798 w,
769 m, 742 m, 723 w, 689 m, 647 vw, 602 w, 549 vw, 527 w, 497 w,
473 w cm−1. HRMS: calcd. for С45H22F8O6P2 [M] 872.0758; found
872.0774; Anal. calcd. for С45H22F8O6P2*C4H8O2 (ethyl acetate): C,
61.26; H, 3.15; found: C, 61.30; H, 2.99.
A solution of 1 (100 mg, 0.376 mmol) in dioxane (10.0 mL) and
H2O (1.0 mL) was added slowly to a stirred solution of 2b (150 mg,
0.376 mmol) in dioxane (4.0 mL) and H2O (0.4 mL). After stirring for
3-(((Diphenylphosphoryl)methyl)diphenylphosphonio)-5,6,7,8-tetrafluoro-
1-hydroxy-4-oxo-1-(2-oxopropyl)-1,4-dihydronaphthalen-2-olate (5a): white
24

S.I. Zhivetyeva et al.
JournalofFluorineChemistry206(2018)19–28
24 h, the solvent was distilled off, and the crude product was purified
by TLC to obtain betaines 3b (168 mg, 68%) and 4b (20 mg, 6%).
A mixture of 1 (30 mg, 0.113 mmol), 2b (45 mg, 0.113 mmol), and
MeOH (1.0 mL) was stirred for 4 h at room temperature. A precipitate
was centrifuged off, and purified by TLC to isolate betaine 4b with a
yield of 21 mg (21%). The mother liquid was evaporated, and the re-
sidue was purified by TLC (Sorbfil, acetone) to isolate betaine 3b
(22 mg, 30%).
A mixture of two eq. of quinone 1 (100 mg, 0.376 mmol), 2b
(75 mg, 0.188 mmol), DMSO (2.0 mL), and H2O (0.1 mL) was stirred
for 1 h at room temperature. A precipitate was centrifuged off, washed
with water (4 × 5 mL), and air dried to obtain compound 4b (166 mg,
100%).
A mixture of 1 (50 mg, 0.188 mmol), 2b (37 mg, 0.094 mmol), and
methanol (1.0 mL) was stirred for 5 h at room temperature. A pre-
cipitate was centrifuged off and crystallized from methanol (1 mL) to
isolate betaine 4b (10 mg, 12%). The mother liquid was evaporated, the
residue was purified by TLC to obtain 4b (33 mg, 40%) and an addi-
tional amount of 3b (22 mg, 35%). The total yield of betaine 4b was
43 mg (52%).
A mixture of 1 (50 mg, 0.188 mmol), 2b (37 mg, 0.094 mmol), di-
oxane (1.0 mL), and H2O (0.1 mL) was stirred for 24 h at room tem-
perature. Water (∼4 mL) was added; the precipitate was centrifuged
off, washed with water (3 × 5 mL), and air dried to obtain compound
4b (50 mg, 60%). The aqueous fraction was extracted with chloroform
(4 × 20 mL). The extract was dried over MgSO4 and evaporated to
obtain a residue, which was purified by TLC. The yield of betaine 3b
was 21 mg (34%).
1279 s, 1194 w, 1161 m, 1107 m, 1074 w, 1043 m, 999 w, 953 m,
887 w, 820 vw, 768 m, 741 m, 731 m, 714 w, 692 m, 667 w, 602 w,
517 m, 501 w, 486 w cm−1. Anal. calcd. for С46H24F8O6P2: C, 62.31; H,
2.73; F 17.14; found: C, 62.30; H, 2.58; F 17.14. Crystals suitable for
XRD analysis were grown from acetone.
3-((2-(Diphenylphosphoryl)ethyl)diphenylphosphonio)-5,6,7,8-tetra-
fluoro-1-hydroxy-4-oxo-1-(2-oxopropyl)-1,4-dihydronaphthalen-2-olate
(5b), white powder, m.p. 207.4 °C followed by decomposition. 1H NMR
(CDCl3): δ = 7.55–7.81 (m, 10H, C6H5), 7.40–7.55 (m, 10H,
C6H5), 4.45 [d, 1H, J = 2.6 Hz, OH), 2.90–3.30 (m, 4H, 2CH2),
2.32–2.62 (m, 2H, CH2C(O)), 2.12 (s, 3H, CH3) ppm. 13C{1H}
2
NMR (CDCl3): δ = 205.6 (s, C]O), 191.6 [d, JCP = 4.2 Hz, C2or4],
2
1
179.5 [d, JCP = 6.1 Hz, C2or4], 146.8 [ddm, JCF = 266.3 Hz,
2JCF ∼ 10 Hz, C6or7], 145.4 [ddd, JCF = 254.0 Hz, JCF = 10.7 Hz,
1
2
3JCF = 4.0 Hz, C6or7], 142.7 [ddd, JCF = 257.0 Hz, 2JCF ∼ 14 Hz,
1
3JCF ∼ 3.0 Hz, C5or8], 140.8 [ddd, 1JCF = 255.0 Hz, 2JCF
=
13.4 Hz, JCF = 3.0 Hz, C5or8], 133.1 [d, JCP = 1.7 Hz, C6H5],
3
4
3
3
132.3 [d, JCP = 9.4 Hz, C6H5], 132.2 [d, JCP = 9.5 Hz, C6H5],
4
4
132.1 [d, JCP = 3.0 Hz, C6H5], 132.1 [d, JCP = 2.9 Hz, C6H5],
3
3
130.9 [d, JCP = 9.5 Hz, C6H5], 130.9 [d, JCP = 9.6 Hz, C6H5],
2
2
129.5 [d, JCP = 13.0 Hz, C6H5], 129.4 [d, JCP = 12.9 Hz, C6H5],
2
2
128.8 [d, JCP = 11.9 Hz, C6H5], 128.7 [d, JCP = 11.9 Hz, C6H5],
125.2 [dd, 2JCF = 8.9 Hz, 3JCF = 3.2 Hz, C10F4O2], 122.5 [d,
1JCP = 89.6 Hz, C6H5], 122.2 [d, JCP = 91.3 Hz, C6H5], 116.5 [dd,
1
2JCF = 8.6 Hz, JCF = 2.7 Hz, C10F4O2], 81.4 [d, JCP = 100.8 Hz, C3],
73.2 [d, 3JCF ∼ 10 Hz, C1], 55.5 (br. s, CH2C(O)), 31.9 (s, C(O)CH3),
22.8 [dd, 1JCP = 68.2 Hz, 2JCP = 4.0 Hz, CH2], 19.5 [d,
3
1
1JCP = 56.4 Hz, CH2] ppm. 19F NMR (CDCl3): δ = −139.3, −142.7,
ortho
For TLC, the use of the 1:1 acetone–hexane mixture instead of ethyl
acetate as the eluent led to conversion of 3b into 5b.
−151.6, −156.3 [ddd, 1F,
J
20.0÷21.0 Hz metaJFF 3.0÷8.6 Hz,
FF
para
J
13.0÷13.1 Hz] ppm.31P{1H} (CDCl3): δ = 32.70 [d, 1P,
FF
3
3-((2-(Diphenylphosphoryl)ethyl)diphenylphosphonio)-5,6,7,8-tetra-
fluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate (3b): orange powder,
Rf = 0.4 (Sorbfil, ethyl acetate), m.p. 293.2 °C followed by decom-
position. 1H NMR (acetone-d6): δ = 7.83–7.94 (m, 4H, C6H5),
7.67–7.77 (m, 6H, C6H5), 7.57–7.66 (m, 4H, C6H5), 7.44–7.57 (m, 6H,
3JPP = 57.0 Hz], 19,30 [d, 1P, JPP = 57.0 Hz] ppm. IR (neat): 3392
vw, 3203 w, 3080 w, 3059 w, 3030 vw, 3012 vw, 2974 w, 2960 w,
2914 w, 2891 vw, 2858 vw, 1709 m, 1618 m, 1570 vs, 1508 m,
1483 w, 1462 m, 1437 m, 1417 w, 1394 w, 1362 s, 1325 m, 1302 w,
1273 m, 1200 m, 1173 m, 1138 w, 1120 m, 1107 m, 1059 w, 1024 w,
999 w, 978 w, 931 w, 891 w, 854 vw, 802 w, 787 vw, 739 m, 694 m,
C6H5), 3.15–3.32 (m, 2H, CH2), 2.42–2.56 (m, 2H, CH2) ppm. 19F NMR
ortho
(acetone-d6): δ = −140.3, −140.8, −146.8, −151.4 [ddd, 1F,
J
677 w, 544 m, 519 m, 498 w, 482 w cm−1
. HRMS: calcd. for
FF
18.7÷19.4 Hz metaJFF 8.2÷9.8 Hz,
J
FF
13.7 Hz] ppm.31P{1H}
С39H30F4O5P2 [M] 716.1500; found 716.1493; Anal. calcd. for
С39H30F4O5P2: C, 65.37; H, 4.22; F, 10.60; found: C, 65.83; H, 4.22; F,
10.61.
para
3
(acetone-d6): δ = 29.86 [d, 1P, JPP = 55.9 Hz], 20,76 [d, 1P,
3JPP = 55.9 Hz] ppm. IR (neat): 3442 w, 3054 w, 3025 vw, 2984 vw,
1698 m, 1617 m, 1592 s, 1581 vs, 1503 m, 1485 w, 1462 w, 1438 m,
1410 w, 1364 s, 1351 m, 1332 m, 1278 s, 1262 m, 1195 m, 1164 m,
1120 m, 1110 m, 1047 w, 998 w, 948 w, 892 w, 822 vw, 790 vw,
769 m, 755 m, 741 s, 732 s, 708 w, 692 m, 671 w, 600 w, 537 w,
527 m, 511 w, 500 m, 488 w, 480 w, 462 vw cm−1. HRMS: calcd. for
С36H24F4O4P2 [M] 658.1081; found 658.1091; Anal. calcd. for
С36H24F4O4P2: C, 65.66; H, 3.67; F, 11.54; found: C, 65.96; H, 3.35; F,
11.54. Crystals suitable for XRD analysis were grown in acet-
one–heptane (1:1) in a refrigerator in an open flask at −5 °C.
4.4. The reaction of quinone 1 with Ph2P(CH2)3PPh2 2c in water-
containing dioxane or DMSO
A solution of quinone 1 (100 mg, 0.376 mmol) in dioxane (10.0 mL)
and H2O (1.0 mL) was added slowly to a stirred solution of phosphane
2c (155 mg, 0.376 mmol) in dioxane (4.0 mL) and H2O (0.4 mL).
Within 2 h, the reaction mixture changed its color from yellow to or-
ange. The solvents were evaporated, and the residue was purified by
TLC to isolate betaines 3c (164 mg, 65%) and 4c (44 mg, 13%).
A mixture of 1 (200 mg, 0.752 mmol), 2c (155 mg, 0.376 mmol),
DMSO (2.0 mL), and H2O (0.1 mL) was stirred for 1 h. Addition of
water (∼8 mL) gave a precipitate, which was centrifuged off, washed
with water (4 × 5 mL), and dried. The aqueous fraction was extracted
with chloroform (3 × 15 mL). The extracts were dried over MgSO4,
filtered, and evaporated. The residue was purified by TLC to give be-
taines 3c (35 mg, 14%) and 4c (287 mg, 85%).
For TLC, the use of the 1:1 dioxane–hexane mixture instead of ethyl
acetate as the eluent led to conversion of 3c and 4c into 7c and 8c,
respectively.
3-((3-(Diphenylphosphoryl)propyl)diphenylphosphonio)-5,6,7,8-tetra-
fluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate (3c): orange powder,
Rf = 0.1 (ethyl acetate), m.p. 74.1 °C followed by decomposition. 1H
NMR (CDCl3): δ = 7.44–7.64 (m, 10H, C6H5), 7.27–7.42 (m, 10H,
C6H5), 3.06–3.19 (m, 2H, CH2), 2.30–2.42 (m, 2H, CH2), 1.58–1.74 (m,
2H, CH2) ppm. 13C{1H} NMR (CDCl3): δ = 178.2 (br. s, C1or4), 178.1
3,3′-(Ethane-1,2-diylbis(diphenylphosphonionediyl))bis(5,6,7,8-tetra-
fluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate) (4b): bright yellow
powder, Rf = 0.9 (Sorbfil, ethyl acetate); decomp. before melting. 1H
NMR (DMSO-d6): δ = 7.66–7.77 (m, 12H, C6H5), 7.54–7.62 (m, 8H,
C6H5), 3.10–3.16 (m, 4H, 2CH2) ppm. 13C{1H} NMR (DMSO-d6):
δ = 178.0 (m, C1or4), 177.7 (m, C1or4), 173.6 (m, C2), 146.4 [ddm,
1JCF = 265.2 Hz, 2JCF = 10.8 Hz, C6or7], 145.6 [ddm, 1JCF = 263.7 Hz,
1
2JCF = 10.2 Hz, C6or7], 144.1 [ddd, JCF = 258.0 Hz, 2JCF ∼ 19 Hz,
3JCF ∼ 13 Hz, C5or8], 141.9 [ddd, 1JCF ∼ 257 Hz, 2JCF ∼ 17 Hz,
3JCF ∼ 11 Hz,
C5or8],
133.2
(br.
s,
C6H5),
132.2
[m,
2
3JCP = 10.5 Hz, C6H5], 129.3 [m, JCP = 12.7 Hz, C6H5], 121.7 [m,
1JCP = 90.2 Hz, C6H5], 119.2 (m, C10F4O2), 117.0 (m, C10F4O2), 87.6
[m, 1JCP = 97.1 Hz, C3], 18.9 [m, 1JCP = 53.1 Hz, CH2] ppm. 19F NMR
ortho
(CDCl3): δ = −151.6, −154.2, −158.2, −162.9 [ddd, 1F,
J
FF
19.4÷20.1 Hz metaJFF 9.1÷11.5 Hz,
J
13.2÷13.6 Hz] ppm.31
P
FF
para
{1H} (CDCl3): δ = 20.36 (s) ppm. IR (neat): 3435 w, 2931 vw, 1703 m,
1618 s, 1579 vs, 1506 s, 1485 w, 1466 m, 1439 m, 1373 s, 1333 s,
25

S.I. Zhivetyeva et al.
JournalofFluorineChemistry206(2018)19–28
(br. s, C1or4), 173.6 [d, 2JCP = 3.7 Hz, C2], 147.0 [ddm,
1JCF = 270.3 Hz, 2JCF = 10.1 Hz, C6or7], 146.1 [ddm, 1JCF = 268.6 Hz,
2JCF = 11.1 Hz, C6or7], 144.8 [dm, 1JCF ∼ 238 Hz, 2JCF ∼ 12 Hz,
C5or8], 142.2 [dm, 1JCF ∼ 235 Hz, 2JCF ∼ 11 Hz, C5or8], 132.8 [d,
4JCP = 2.9 Hz, C6H5], 132,5 (s, C6H5), 131.8 [d, 3JCP = 10.2 Hz, C6H5],
4.37; F, 11.79. Crystals suitable for XRD analysis were grown from
acetone–heptane (1:1) in the refrigerator in an open flask at −5 °C.
2,2′-(Propane-1,3-diylbis(diphenylphosphonionediyl))bis(4,5,6,7-tetra-
fluoro-1-oxo-1H-inden-3-olate) (8c): yellow crystals, Rf = 0.8 (dioxane-
hexane, 1:1), m.p. 240.8 °C followed by decomposition. 13C{1H} NMR
(CDCl3): δ = 186.4 (m, C1,3), 143.0 [dm, 1JCF ∼ 259 Hz, C4,7or5,6],
4
4
131.6 [d, JCP = 2.5 Hz, C6H5], 131.5 [d, JCP = 2.8 Hz, C6H5], 130.3
3
2
4
[d, JCP = 9.4 Hz, C6H5], 129.0 [d, JCP = 12.8 Hz, C6H5], 128.4 [d,
141.3 [dm, 1JCF ∼ 265 Hz, C4,7or5,6], 133.4 [m, JCP = 3.0 Hz, C6H5],
2JCP = 11.7 Hz, C6H5], 121.6 [d, JCP = 90.2 Hz, C6H5], 119.0 [dm,
132.4 [m, JCP = 10.7 Hz, C6H5], 129.4 [m, JCP = 12.8 Hz, C6H5],
1
3
2
2JCF = 9.7 Hz, C10F4O2], 116.2 (br. s, C10F4O2), 88.9 [d,
122.1 [d, JCP = 91.1 Hz, C6H5], 120.7 (m, C10F4O2), 73.4 [d,
1
1JCP = 94.2 Hz, C3], 29.9 [dd, JCP = 70.9 Hz, JCP = 16.5 Hz, CH2],
26.1 [dd, 1JCP = 53.9 Hz, 3JCP = 12.3 Hz, CH2], 15.9 [t, 2JCP = 2.5 Hz,
CH2] ppm. 19F NMR (CDCl3): δ = –138.7, −141.2, −145.1, −150.0
1JCP = 112.6 Hz, C2], 22.7 [dd, JCP = 57.3 Hz, JCP = 17.5 Hz, CH2],
17.8 [br. s, CH2] ppm. 19F NMR (CDCl3): δ = −145.0 (m, 2F), −150.2
(m, 2F) ppm. 31P{1H} (CDCl3): δ = 11.3 (s) ppm. IR (neat): 3444 vw,
1710 w, 1678 w, 1640 s, 1611 vs, 1587 m, 1575 w, 1552 w, 1490 s,
1439 m, 1384 m, 1363 w, 1344 w, 1325 m, 1299 s, 1246 w, 1220 w,
1200 w, 1193 w, 1166 vw, 1130 w, 1114 m, 1075 m, 996 vw, 975 w,
924 m, 765 w, 742 w, 723 w, 703 w, 691 m, 672 w, 528 w, 501 m,
1
3
1
3
ortho
para
[ddd, 1F,
J
19.3÷20.1 Hz metaJFF 9.0÷11.3 Hz,
J
FF
FF
12.9÷13.0 Hz] ppm.31P{1H}
(CDCl3):
δ = 32.44
[d,
1P,
4JPP = 3.6 Hz], 17,63 [d, 1P, JPP = 3.6 Hz] ppm. IR (neat): 3429 m,
3057 w, 2955 w, 2924 m, 2854 w, 1701 m, 1618 s, 1579 vs, 1504 s,
1485 m, 1468 m, 1437 m, 1371 s, 1336 m, 1277 s, 1165 s, 1113 s,
1072 m, 1045 m, 997 m, 951 m, 891 w, 823 vw, 748 s, 721 s, 694 s,
4
486 w, 479 w, 426 w cm−1
. HRMS: calcd. for С45H26F8O4P2 [M]
844.1173; found 844.1175. Crystals suitable for XRD analysis were
grown from acetone–heptane (1:1) in the refrigerator in an open flask at
−5 °C.
665 m, 602 w, 548 m, 505 m, 420 vw cm−1
. HRMS: calcd. for
С37H26F4O4P2 [M] 672.1237; found 672.1230; Anal. calcd. for
С37H26F4O4P2*2CHCl3: C, 51.40; H, 3.10; found: C, 51.45; H, 3.13.
3,3′-(Propane-1,3-diylbis(diphenylphosphonionediyl))-bis(5,6,7,8-tet-
rafluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate) (4c): yellow powder,
Rf = 0.6 (ethyl acetate–hexane, 1:1), m.p. 145.9 °C followed by de-
composition. 1H NMR (CDCl3): δ = 7.54–7.62 (m, 8H, C6H5),
7.48–7.54 (m, 4H, C6H5), 7.37–7.45 (m, 8H, C6H5), 3.05–3.20 (m, 4H,
2CH2), 1.23–1.34 (m, 2H, CH2) ppm. 13C{1H} NMR (CDCl3): δ = 178.2
(m, C1or4), 178.1 (m, C1or4), 173.6 (m, C2), 147.1 [dd, 1JCF = 272.4 Hz,
4.5. The reaction of quinone 1 with Ph2P(CH2)4PPh2 2d in water-
containing dioxane or DMSO
A solution of 1 (100 mg, 0.376 mmol) in dioxane (10.0 mL) and
H2O (1.0 mL) was added slowly to a stirred solution of 2d (160 mg,
0.376 mmol) in dioxane (4.0 mL) and H2O (0.4 mL) at room tempera-
ture. Within 1 h, the reaction mixture changed its color from yellow to
orange. The solvents were distilled off, and the residue was purified by
TLC to isolate betaines 3d (129 mg, 50%) and 4d (63 mg, 18%).
A mixture of 1 (200 mg, 0.752 mmol), 2d (160 mg, 0.376 mmol),
DMSO (2.0 mL), and H2O (0.1 mL) was stirred for 1 h. Water (∼8 mL)
was added; a precipitate was centrifuged off, washed with water
(4 × 5 mL), and air dried to obtain compound 4d with a yield of
344 mg (100%).
2JCF = 9.2 Hz, C6or7], 146.7 [dd, JCF = 268.5 Hz, JCF = 10.8 Hz,
1
2
C6or7], 144.9 [dt, JCF = 269.0 Hz, JCF = 15.0 Hz, C5or8], 142.5 [dt,
1
2
1JCF = 261.6 Hz, 2JCF = 14.6 Hz, C5or8], 132.9 (br. s, C6H5), 132.0 [m,
3JCP = 10.3 Hz, C6H5], 129.0 [m, JCP = 12.8 Hz, C6H5], 121.6 [d,
2
1JCP = 91.0 Hz, C6H5], 119.0 (m, C10F4O2), 116.3 (m, C10F4O2), 88.7
1
1
3
[d, JCP = 95.1 Hz, C3], 25.8 [dd, JCP = 55.7 Hz, JCP = 17.1 Hz,
CH2], 18.0 (br. s, CH2) ppm. 19F NMR (CDCl3): δ = −138.9, −141.2,
ortho
−145.2, −150.1 [ddd, 1F,
J
19.6÷20.1 Hz metaJFF 9.0÷11.3 Hz,
For preparative chromatography on silica gel, the use of the 1:1
dioxane–hexane mixture instead of ethyl acetate as the eluent led to
conversion of 3d into 7d.
FF
para
J
13.1÷13.4 Hz] ppm.31P{1H} (CDCl3): δ = 17.62 (s) ppm. IR
FF
(neat): 3437 w, 3394 w, 3059 vw, 2956 w, 2926 w, 2856 vw, 1703 m,
1618 s, 1581 vs, 1504 s, 1485 w, 1468 m, 1439 m, 1369 s, 1335 m,
1275 s, 1190 w, 1163 m, 1111 m, 1074 vw, 1045 w, 999 vw, 968 w,
951 m, 891 w, 768 m, 748 w, 725 m, 690 m, 665 vw, 602 w, 548 vw,
527 w, 505 w cm−1. HRMS: calcd. for С47H26F8O6P2 [M] 900.1071;
found 900.1065; Anal. calcd. for С47H26F8O6P2: C, 62.68; H, 2.91;
found: C, 62.93; H, 3.19.
3-((4-(Diphenylphosphoryl)butyl)diphenylphosphonio)-5,6,7,8-tetra-
fluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate (3d): red powder,
Rf = 0.2 (ethyl acetate), m.p. 95.3 °C followed by decomposition. 19F
NMR (CDCl3): δ = −135.8, −138.2, −142.2, −147.2 [ddd, 1F,
ortho
para
J
19.2÷20.4 Hz metaJFF 8.9÷11.3 Hz,
J
FF
12.3÷13.1 Hz]
FF
ppm.31P{1H} (CDCl3): δ = 32.54 (s), 18,29 (s) ppm. IR (neat): 3427 w,
3057 w, 3026 w, 3012 w, 2993 w, 2935 w, 2926 w, 2870 w, 1782 vw,
1703 m, 1616 s, 1581 vs, 1506 s, 1485 m, 1466 w, 1437 s, 1369 s,
1335 m, 1275 m, 1244 w, 1223 w, 1182 m, 1165 m, 1117 m, 1070 w,
1045 w, 1028 w, 997 w, 951 w, 924 vw, 893 w, 845 vw, 768 m, 746 m,
719 m, 694 s, 675 w, 602 w, 548 m, 509 m cm−1. HRMS: calcd. for
С38H28F4O4P2 [M] 686.1394; found 686.1386; Anal. calcd. for
2С38H28F4O4P2*CHCl3: C, 61.96; H, 3.85; found: C, 61.60; H, 3.67.
3,3′-(Butane-1,4-diylbis(diphenylphosphonionediyl))-bis(5,6,7,8-tetra-
fluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate) (4d): bright yellow
crystals, Rf = 0.9 (ethyl acetate), m.p. 234.6 °C followed by decom-
position. 1H NMR (CDCl3): δ = 7.63–7.75 (m, 8H, C6H5), 7.55–7.63 (m,
4H, C6H5), 7.44–7.55 (m, 8H, C6H5), 2.84–3.05 (m, 4H, CH2),
1.37–1.58 (m, 4H, CH2) ppm. 13C{1H} NMR (CDCl3): δ = 178.5 [d,
JCP = 12.9 Hz, C1or4], 178.2 [d, JCP = 5.1 Hz, C1or4], 173.9 [d,
2JCP = 3.9 Hz, C2], 147.2 [ddm, 1JCF = 272.0 Hz, 2JCF ∼ 10 Hz, C6or7],
2-((3-(Diphenylphosphoryl)propyl)diphenylphosphonio)-4,5,6,7-tetra-
fluoro-1-oxo-1H-inden-3-olate (7c): yellow crystals, Rf = 0.2 (dioxane-
hexane, 1:1), m.p. 216.1–216.8 °C. 1H NMR (CDCl3): δ = 7.54–7.69 (m,
10H, C6H5), 7.38–7.52 (m, 10H, C6H5), 3.07–3.20 (m, 2H, CH2),
2.41–2.53 (m, 2H, CH2), 1.79–1.95 (m, 2H, CH2) ppm. 13C{1H} NMR
(CDCl3): δ = 186.5 [d, 2JCP = 11.5 Hz, C1,3], 142.9 [dm,
1JCF ∼ 260 Hz, C4,7or5,6], 141.3 [dm, 1JCF ∼ 263 Hz, C4,7or5,6], 133.3
4
3
[d, JCP = 2.8 Hz, C6H5], 132.4 [d, JCP = 10.5 Hz, C6H5], 131.9 [d,
4JCP = 2.3 Hz, C6H5], 130.6 [d, JCP = 9.4 Hz, C6H5], 129.3 [d,
3
2JCP = 12.7 Hz, C6H5], 128.7 [d, JCP = 11.7 Hz, C6H5], 122.4 [d,
2
1JCP = 90.4 Hz, C6H5], 120.8 (m, C9F4O2), 73.8 [d, JCP = 112.1 Hz,
1
C2], 30.1 [dd, JCP = 71.0 Hz, JCP = 16.9 Hz, CH2], 29.7 [d,
1
3
2JCP = 3.4 Hz, CH2], 22.6 [dd, JCP = 55.5 Hz, JCP = 11.3 Hz, CH2]
1
3
ppm. 19F NMR (CDCl3): δ = –145.1 (m, 2F), −150.4 (m, 2F) ppm. 31P
{1H} (CDCl3): δ = 32.5 [d, 1P, JPP 3.0 Hz], 11.3 [d, 1P, JPP 3.0 Hz]
ppm. IR (neat): 3435 w, 3066 w, 3036 vw, 2937 w, 2922 w, 2868 vw,
2852 vw, 1641 s, 1612 vs, 1589 m, 1552 w, 1491 s, 1439 m, 1402 w,
1385 m, 1362 w, 1327 s, 1300 s, 1254 w, 1196 m, 1157 m, 1117 m,
1074 m, 1028 vw, 997 w, 968 w, 955 w, 922 m, 833 w, 764 w, 744 m,
4
4
146.4 [ddm, JCF = 268.0 Hz, 2JCF ∼ 10 Hz, C6or7], 145.0 [dm,
1
1JCF ∼ 264 Hz, C5or8], 142.7 [dm, 1JCF ∼ 262.0 Hz, C5or8], 133.0 [d,
3
4JCP = 3.1 Hz, C6H5], 132.2 [d, JCP = 10.2 Hz, C6H5], 129.2 [d,
1
2JCP = 12.8 Hz, C6H5], 122.1 [d, JCP = 90.2 Hz, C6H5], 119.4 [dm,
715 m, 692 m, 665 w, 550 m, 523 m, 500 m, 474 w, 424 w cm−1
.
2JCF = 11.4 Hz, C10F4O2], 116.5 (br. s, C10F4O2), 89.1 [d,
1
HRMS: calcd. for С36H26F4O3P2 [M] 644.1288; found 644.1285; Anal.
calcd. for С36H26F4O3P2: C, 67.09; H, 4.07; F, 11.79; found: C, 66.71; H,
1JCP = 94.2 Hz, C3], 24.9 [d, JCP = 54.8 Hz, CH2], 23.7 [dd,
3JCP = 17.7 Hz, JCP = 3.2 Hz, CH2] ppm. 19F NMR (CDCl3):
2
26

S.I. Zhivetyeva et al.
JournalofFluorineChemistry206(2018)19–28
[M] 700.1550; found 700.1542; Anal. calcd. for С39H30F4O4P2*4C3H6O
(acetone): C, 65.66; H, 5.83; found: C, 65.45; H, 5.86.
ortho
δ = –138.7, −141.3, −145.2, −150.1 [ddd, 1F,
J
FF
19.4÷20.1 Hz metaJFF 9.0÷11.1 Hz, paraJFF ∼ 13.5 Hz] ppm.31P{1H}
(CDCl3): δ = 18.47 (s) ppm. IR (neat): 3437 w, 3392 vw, 3080 vw,
3059 w, 2962 w, 2924 w, 2854 vw, 1701 m, 1618 s, 1579 vs, 1574 vs,
1504 s, 1485 w, 1462 w, 1439 m, 1373 s, 1365 s, 1335 m, 1275 s,
1221 w, 1190 w, 1163 m, 1115 m, 1074 vw, 1045 m, 1028 w, 999 w,
953 m, 893 w, 858 vw, 822 vw, 771 m, 746 m, 727 w, 721 w, 692 m,
675 w, 602 w, 550 w, 525 w, 507 w, 471 w, 417 vw cm−1. HRMS:
calcd. for С48H28F8O6P2 [M] 914.1228; found 914.1231; Anal. calcd.
for С48H28F8O6P2: C, 63.03; H, 3.09; found: C, 63.03; H, 3.48.
3,3′-(Pentane-1,5-diylbis(diphenylphosphonionediyl))-bis(5,6,7,8-tet-
rafluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate) (4e): Rf = 0.3 (ethyl
acetate–hexane, 2:1), m.p. 308.1 °C followed by decomposition. 1H
NMR (CDCl3): δ = 7.62–7.73 (m, 8H, C6H5), 7.53–7.60 (m, 4H, C6H5),
7.42–7.52 (m, 8H, C6H5), 2.80–2.90 (m, 4H, CH2), 1.43–1.54 (m, 2H,
CH2), 1.21–1.35 (m, 4H, CH2) ppm. 13C{1H} NMR (CDCl3): δ = 178.3
[d, JCP = 12.2 Hz, C1or4], 178.1 [d, JCP = 3.6 Hz, C1or4], 173.6 [d,
1
2
2JCP = 3.5 Hz, C2], 147.1 [dd, JCF = 271.2 Hz, JCF = 8.9 Hz, C6or7],
1
2
2-((4-(Diphenylphosphoryl)butyl)diphenylphosphonio)-4,5,6,7-tetra-
fluoro-1-oxo-1H-inden-3-olate (7d): yellow oil, Rf = 0.8 (acetonitrile),
m.p. 91.1 °C followed by decomposition. 1H NMR (CDCl3):
δ = 7.58–7.72 (m, 10H, C6H5), 7.47–7.53 (m, 6H, C6H5), 7.41–7.46 (m,
4H, C6H5), 2.81–2.90 (m, 2H, CH2), 2.23–2.32 (m, 2H, CH2), 1.71–1.82
(m, 2H, CH2), 1.54–1.64 (m, 2H, CH2) ppm. 13C{1H} NMR (CDCl3):
146.3 [dd, JCF = 267.9 Hz, JCF = 10.1 Hz, C6or7], 144.8 [dm,
2
1
1JCF = 264.0 Hz, JCF = 14.3 Hz, C5or8], 142.4 [dm, JCF = 262.2 Hz,
4
2JCF = 14.0 Hz, C5or8], 132.8 [d, JCP = 1.8 Hz, C6H5], 132.0 [d,
2
3JCP = 10.1 Hz, C6H5], 129.0 [d, JCP = 12.7 Hz, C6H5], 122.1 [d,
2
1JCP = 90.0 Hz, C6H5], 119.2 [d, JCF = 10.4 Hz, C10F4O2], 116.2 (br.
1
3
s, C10F4O2), 89.2 [d, JCP = 94.2 Hz, C3], 31.2 [t, JCP = 17.5 Hz,
δ = 186.4 [d, JCP = 11.6 Hz, C1,3], 143.0 [ddd, 1JCF ∼ 260 Hz,
CH2], 25.0 [d, JCP = 54.3 Hz, CH2], 21.4 (br. s, CH2) ppm. 19F NMR
2
1
2JCF ∼ 14 Hz, 3JCF ∼ 4 Hz, C5,6], 141.4 [dm, 1JCF ∼ 264 Hz, C4,7],
133.3 [d, 4JCP = 3.0 Hz, C6H5], 132.4 [d, 3JCP = 10.4 Hz, C6H5], 131.8
(CDCl3): δ = −135.8, −138.3, −142.3, −147.2 [ddd, 1F,
J
FF
ortho
19.5÷20.0 Hz metaJFF 8.9÷11.2 Hz,
J
13.2÷13.4 Hz] ppm.31
P
FF
para
4
3
[d, JCP = 2.6 Hz, C6H5], 130.7 [d, JCP = 9.3 Hz, C6H5], 129.3 [d,
{1H} (CDCl3): δ = 18.31 (s) ppm. IR (neat): 3435 w, 3392 w, 3061 vw,
2937 vw, 2902 vw, 1703 m, 1618 m, 1581 vs, 1504 s, 1485 w, 1468 w,
1439 m, 1369 s, 1333 m, 1277 s, 1234 vw, 1190 w, 1165 m, 1113 m,
1045 w, 1028 w, 999 w, 951 m, 895 w, 820 vw, 769 m, 744 m, 725 m,
702 w, 690 m, 675 w, 600 w, 525 w, 501 w, 471 w cm−1. HRMS: calcd.
for С49H30F8O6P2 [M] 928.1384; found 928.1387; Anal. calcd. for
С49H30F8O6P2: C, 63.37; H, 3.26; F, 16.37; P, 6.67; found: C, 63.14; H,
3.26; F, 16.31; P, 6.36.
2JCP = 12.6 Hz, C6H5], 128.7 [d, JCP = 11.6 Hz, C6H5], 122.6 [d,
2
1JCP = 90.2 Hz, C6H5], 120.9 (m, C10F4O2), 74.0 [dt, JCP = 112.1 Hz,
1
4JCF = 1.4 Hz, C2], 29.0 [d, JCP = 71.5 Hz, CH2], 23.7 [dd,
1
3JCP = 14.5 Hz, JCP = 3.0 Hz, CH2], 22.8 [dd, JCP = 18.4 Hz,
2
3
2JCP = 3.5 Hz, CH2], 21.9 [d, JCP = 56.0 Hz, CH2] ppm. 19F NMR
1
(CDCl3): δ = −145.1 (m, 2F), −150.4 (m, 2F) ppm. 31P{1H} (CDCl3):
δ = 32.08 (s), 11.87 (s) ppm. IR (neat): 3425 w, 3295 w, 3059 w,
2938 w, 2930 w, 1686 w, 1642 s, 1612 vs, 1588 m, 1572 w, 1552 w,
1490 s, 1438 m, 1381 m, 1343 w, 1326 m, 1299 m, 1245 vw, 1183 m,
1168 w, 1114 m, 1072 m, 1027 w, 997 w, 954 w, 923 m, 841 vw,
4.7. The reaction of quinone 1 with Et2P(CH2)2PEt2 2f in anhydrous C6H6
or water-containing dioxane
763 w, 746 m, 721 m, 694 m, 550 m, 518 w, 504 m, 484 w cm−1
.
HRMS: calcd. for С37H28F4O3P2 [M] 658.1444; found 658.1446.
Crystals suitable for XRD analysis were grown from methanol–heptane
(1:2) in the refrigerator in an open flask at −5 °C.
A solution of 1 (585 mg, 2.199 mmol) in anhydrous C6H6 (15.0 mL)
was added to a stirred solution of phosphane 2f (454 mg, 2.199 mmol)
in anhydrous C6H6 (15.0 mL). After stirring for 30 min, the reaction
mixture changed color from yellow to red. The solvent was distilled off,
the residue was purified by TLC to give compounds 3f (494 mg, 48%),
4f (184 mg, 12%) and 6f (26 mg, 3%).
4.6. The reaction of quinone 1 with Ph2P(CH2)5PPh2 2e in water-
containing dioxane or DMSO
A solution of 1 (141 mg, 0.528 mmol) in dioxane (5.0 mL) and H2O
(0.5 mL) was added to a stirred solution of 2f (109 mg, 0.528 mmol) in
dioxane (20.0 mL) and H2O (2.0 mL). Then the reaction mixture was
left open for 2 days. The solvents were evaporated, and the rest was
purified by TLC to isolate betaines 3f (91 mg, 37%) and 4f (73 mg,
20%). The same reaction of 2 eq. of quinone 1 (384 mg, 1.444 mmol)
with 2f (149 mg, 0.722 mmol) also gave betaines 3f (107 mg, 32%) and
4f (68 mg, 14%).
3-((2-(Diethylphosphoryl)ethyl)diethylphosphonio)-5,6,7,8-tetrafluoro-
1,4-dioxo-1,4-dihydronaphthalen-2-olate (3f): yellow powder, Rf = 0.3
(ethanol-ethyl acetate, 1:2), m.p. 153.2 °C followed by decomposition.
1H NMR (CDCl3): δ = 2.49–2.65 (m, 2H, CH2), 2.24–2.49 (m, 4H,
2CH2), 1.63–1.86 (m, 6H, 3CH2), 0.99–1.26 (m, 12H, 4CH3) ppm.
13C{1H} NMR (CDCl3): δ = 179.3 [dm, JCP = 6.1 Hz, C1or4], 178.1
[dm, JCP = 11.2 Hz, C1or4], 174.3 [dm, 2JCP = 3.5 Hz, C2], 147.2 [ddm,
1JCF = 273.0 Hz, 2JCF = 11.0 Hz, C6or7], 146.5 [ddm, 1JCF = 268.7 Hz,
A soilution of 1 (100 mg, 0.376 mmol) in dioxane (5.0 mL) and H2O
(0.5 mL) was added to a stirred solution of phosphane 2e (166 mg,
0.376 mmol) in dioxane (20.0 mL) and H2O (2.0 mL). The reaction
mixture was left open for 2 days, and a precipitate was separated by
centrifugation and air dried to obtain 4e with a yield of 24 mg (7%).
The mother liquid was evaporated, the residue was purified by column
chromatography on silica gel using ethyl acetate and then a mixture of
ethanol with hexane (1:1) as eluents to isolate betaine 3e (140 mg,
53%).
A mixture of 1 (200 mg, 0.752 mmol), 2e (166 mg, 0.376 mmol),
DMSO (2.0 mL), and H2O (0.1 mL) was stirred for 1 h. After addition of
water (∼8 mL), the precipitate was centrifuged off, washed with water
(3 × 6 mL), and air dried to obtain compound 4e (260 mg, 74%). The
aqueous fraction was extracted with chloroform (3 × 15 mL). The ex-
tracts were dried over MgSO4, filtered, and evaporated. The residue was
purified by TLC to form an additional amount of title compound 4e,
with a total yield of 349 mg (100%).
1
2
2JCF = 9.3 Hz, C6or7], 145.2 [ddm, JCF = 236.4 Hz, JCF = 14.3 Hz,
C5or8], 142.4 [ddm, JCF = 236.0 Hz, JCF = 13.8 Hz, C5or8], 119.0
1
2
2
3-((5-(Diphenylphosphoryl)pentyl)diphenylphosphonio)-5,6,7,8-tetra-
fluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate (3e): orange powder,
Rf = 0.2 (ethyl acetate), m.p. 79.2 °C followed by decomposition. 19F
[dm, JCF = 10.5 Hz, C10F4O2], 116.2 (m, C10F4O2), 86.7 [d,
1JCP = 88.2 Hz, C3], 20.0 [d, JCP = 66.9 Hz, CH2], 19.5 [dd,
1
1JCP = 60.2 Hz, JCP = 5.2 Hz, CH2], 14.3 [d, JCP = 52.9 Hz, CH2],
2
1
1
2
2
NMR (CDCl3): δ = –139.1, −143.1, −152.2, −156.8 [ddd, 1F, orthoJFF
13.8 [dd, JCP = 52.4 Hz, JCP = 3.3 Hz, CH2], 6.1 [d, JCP = 5.1 Hz,
20.0÷21.3 Hz metaJFF 2.7÷8.1 Hz,
J
12.7÷13.1 Hz] ppm.31P{1H}
CH3], 5.6 [d, JCP = 4.8 Hz, CH3] ppm. 19F NMR (CDCl3): δ = –138.6,
para
2
FF
ortho
(CDCl3): δ = 32.4 (s, 1P), 17.2 (s, 1P) ppm. IR (neat): 3415 m, 3232 w,
3076 w, 3074 w, 3057 w, 3014 w, 2991 w, 2931 m, 2866 w, 1709 m,
1616 m, 1578 vs, 1566 vs, 1508 m, 1481 m, 1464 m, 1437 s, 1398 m,
1362 s, 1335 s, 1273 m, 1223 w, 1176 s, 1113 s, 1070 w, 1053 m,
1028 w, 997 w, 976 w, 933 m, 868 vw, 796 w, 746 m, 719 m, 696 s,
675 w, 546 s, 515 m, 422 vw cm−1. HRMS: calcd. for С39H30F4O4P2
−141.8, −145.1, −150.0 [ddd, 1F,
J
19.4÷20.0 Hz metaJFF
FF
para
9.1÷11.2 Hz,
J
FF
13.4÷13.5 Hz] ppm.31P{1H} (CDCl3): δ = 51.4
3
3
[d, 1P, JPP = 45.0 Hz], 32.3 [d, 1P, JPP = 45.0 Hz] ppm. IR (neat):
3431 w, 2976 w, 2945 w, 2920 w, 2885 w, 1703 m, 1620 m, 1572 vs,
1504 m, 1462 m, 1402 w, 1369 s, 1331 m, 1277 m, 1244 w, 1198 w,
1167 s, 1113 w, 1047 w, 1032 m, 1024 m, 1005 w, 951 m, 899 w, 879
27

S.I. Zhivetyeva et al.
JournalofFluorineChemistry206(2018)19–28
vw, 818 vw, 810 vw, 777 m, 764 m, 750 m, 729 w, 696 w, 652 w, 600
vw, 463 vw, 436 vw cm−1. HRMS: calcd. for С20H24F4O4P2 [M]
466.1081; found 466.1087.
D.T. Hendricks, M.R. Caira, J.-A. de la Mare, A.L. Edkins, A.V. Pinto, E.N. da Silva
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synthetic 1,4-naphthoquinones against oesophageal cancer cells, Eur. J. Med.
Chem. 62 (2013) 98–110.
3,3′-(Ethane-1,2-diylbis(diethylphosphonionediyl))bis(5,6,7,8-tetra-
fluoro-1,4-dioxo-1,4-dihydronaphthalen-2-olate) (4f): red powder,
Rf = 0.5 (ethanol-ethyl acetate, 1:2), m.p. 229.6–231.2 °C. 1H NMR
[2] (a) O. Pawar, A. Patekar, A. Khan, L. Kathawate, S. Haram, G. Markad, V. Puranik,
S. Salunke-Gawali, Molecular structures and biological evaluation of 2-chloro-3-(n-
alkylamino)-1,4-napthoquinone derivatives as potent antifungal agents, J. Mol.
Struct. 1059 (2014) 68–74;
2
(CDCl3): δ = 2.64 [d, 4H, JHP = 4.9 Hz, 2CH2], 2.35–2.58 (m, 8H,
(b) R. Pingaew, V. Prachayasittikul, A. Worachartcheewan, C. Nantasenamat,
S. Prachayasittikul, S. Ruchirawat, V. Prachayasittikul, Novel 1,4-naphthoquinone-
based sulfonamides: synthesis, QSAR, anticancer and antimalarial studies, Eur. J.
Med. Chem. 103 (2015) 446–459;
4CH2), 1.12–1.30 (m, 12H, 4CH3) ppm. 13C{1H} NMR (acetone-d6):
δ = 179.5 (br. s, C1or4), 179.0 (br. s, C1or4), 175.2 (br. s, C2), 147.7
[ddm, 1JCF = 266.8 Hz, 2JCF = 10.5 Hz, C6or7], 147.1 [ddd,
(c) E. Leyva, K.M. Baines, C.G. Espinosa-González, D.A. Magaldi-Lara, S.E. Loredo-
Carrillo, T.A. De Luna-Méndez, L.I. López, 2-(Fluoro-) and 2-(methoxyanilino)-1,4-
naphthoquinones. Synthesis and mechanism and effect of fluorine substitution on
redox reactivity and NMR, J. Fluor. Chem. 180 (2015) 152–160;
(d) E. Leyva, L.I. López, R.F. García de la Cruz, C.G. Espinosa-González, Synthesis
and studies of the antifungal activity of 2-anilino-/2,3-dianilino-/2-phenoxy- and
2,3-diphenoxy-1,4-naphthoquinones, Res. Chem. Intermed. 43 (2017) 1813–1827.
[3] (a) X. Lu, A. Altharawi, J. Gut, P.J. Rosenthal, T.E. Long, 1,4-Naphthoquinone
cations as antiplasmodial agents: hydroxy-, acyloxy-, and alkoxy-substituted ana-
logues, ACS Med. Chem. Lett. 3 (2012) 1029–1033;
(b) T.E. Long, X. Lu, M. Galizzi, R. Docampo, J. Gut, P.J. Rosenthal, Phosphonium
lipocations as antiparasitic agents, Bioorg. Med. Chem. Lett. 22 (2012) 2976–2979.
[4] (a) S.W. Ham, J.I. Choe, M.F. Wang, V. Peyregne, B.I. Carr, Fluorinated quinoid
inhibitor: possible “pure” arylator predicted by the simple theoretical calculation,
Bioorg. Med. Chem. Lett. 14 (2004) 4103–4105;
2
3
1JCF = 265.0 Hz, JCF = 11.0 Hz, JCF = 3.3 Hz, C6or7], 145.5 [dddd,
1JCF = 259.1 Hz, 2JCF = 17.0 Hz, 3JCF = 12.4 Hz, 4JCF = 3.3 Hz,
C5or8], 143.2 [dddd, JCF = 257.6 Hz, JCF = 16.6 Hz, JCF = 12.5 Hz,
1
2
3
4JCF = 2.7 Hz, C5or8], 120.7 (m, C10F4O2), 117.8 (m, C10F4O2), 87.1 [d,
1JCP = 88.0 Hz, C3], 15.0 [d, JCP = 49.0 Hz, CH2], 14.6 [d,
1
1JCP = 52.8 Hz, CH2], 6.4 [d, 2JCP = 2.3 Hz, CH3], 6.4 [d,
2JCP = 2.3 Hz, CH3] ppm. 19F NMR (CDCl3): δ = −135.2, −138.5,
ortho
−141.6, −146.4 [ddd, 1F,
J
19.4÷22.2 Hz metaJFF 9.2÷11.3 Hz,
FF
para
J
12.5÷13.4 Hz] ppm.31P{1H} (CDCl3): δ = 32.61 (s) ppm. IR
FF
(neat): 3446 vw, 2983 w, 2966 w, 2947 w, 1703 m, 1643 m, 1630 s,
1616 m, 1574 vs, 1504 s, 1462 m, 1412 m, 1369 s, 1335 m, 1281 s,
1238 w, 1200 w, 1163 m, 1111 w, 1045 m, 1032 w, 993 vw, 951 m,
887 w, 822 vw, 775 m, 764 m, 748 w, 723 vw, 696 vw, 625 vw,
598 w cm−1. HRMS: calcd. for С30H24F8O6P2 [M] 694.0915; found
694.0920; Anal. calcd. for С30H24F8O6P2: C, 51.89; H, 3.48; F, 21.89;
found: C, 51.96; H, 3.56; F, 21.91. Crystals suitable for XRD analysis
were grown from chloroform.
(b) S. Kar, M. Wang, S.W. Ham, B.I. Carr, Fluorinated Cpd 5, a pure arylating K-
vitamin derivative, inhibits human hepatoma cell growth by inhibiting Cdc25 and
activating MAPK, Biochem. Pharmacol. 72 (2006) 1217–1227;
(c) H. Park, B.I. Carr, M. Li, S.W. Ham, Fluorinated NSC as a Cdc25 inhibitor,
Bioorg. Med. Chem. Lett. 17 (2007) 2351–2354;
(d) O.A. Zakharova, L.I. Goryunov, N.M. Troshkova, L.P. Ovchinnikova,
V.D. Shteingarts, G.A. Nevinsky, Cytotoxicity of new n-butylamino and sulfur-
containing derivatives of polyfluorinated 1,4-naphthoquinone, Eur. J. Med. Chem.
45 (2010) 270–274;
(e) O.A. Zakharova, L.P. Ovchinnikova, L.I. Goryunov, N.M. Troshkova,
V.D. Shteingarts, G.A. Nevinsky, Cytotoxicity of new alkylamino- and phenylamino-
containing polyfluorinated derivatives of 1,4-naphthoquinone, Eur. J. Med. Chem.
45 (2010) 2321–2326;
(f) O.A. Zakharova, L.P. Ovchinnikova, L.I. Goryunov, N.M. Troshkova,
V.D. Shteingarts, G.A. Nevinsky, Cytotoxicity of new polyfluorinated 1,4-naphtho-
quinones with divers substituents in the quinone moiety, Bioorg. Med. Chem. 19
(2011) 256–260.
5,6,7,8-Tetrafluoro-1,4-dioxo-3-(triethylphosphonio)-1,4-dihy-
dronaphthalen-2-olate (6f): orange powder, Rf = 0.8 (ethyl acetate),
m.p. 145.6 °C followed by decomposition. 1H NMR (CDCl3):
δ = 2.31–2.49 (m, 6H, 3CH2), 1.10–1.27 (m, 9H, 3CH3) ppm. 13C{1H}
NMR (CDCl3): δ = 179.3 [d, JCP = 5.9 Hz, C1or4], 178.4 [d,
2
JCP = 10.7 Hz, C1or4], 174.7 [d, JCP = 2.7 Hz, C2], 147.3 [ddm,
1JCF = 270.0 Hz, 2JCF = 10.6 Hz, C6or7], 146.6 [ddm, 1JCF = 267.0 Hz,
[5] G.A. Nevinsky, O.D. Zakharova, L.I. Goryunov, S.I. Zhivetyeva, V.D. Shteingarts,
Phosphorus-containing fluorinated 1,4-naphthoquinone derivatives, possessing cy-
totoxic activity with respect to human cancer cells in culture, RU Patent 2535676
2014.
[6] O.D. Zakharova, L.P. Ovchinnikova, S.I. Zhivetyeva, L.I. Goryunov,
V.D. Shteingarts, E.V. Tretyakov, G.A. Nevinsky, Synthesis and evaluation of cy-
totoxicity and antioxidant properties of polyfluorinated phosphorus-containing 1,4-
benzoquinones and 1,4-naphthoquinones, Adv. Res. 6 (2016) 1–12.
[7] S.I. Zhivetyeva, O.D. Zakharova, L.P. Ovchinnikova, D.S. Baev, I.Yu. Bagryanskaya,
V.D. Shteingarts, T.G. Tolstikova, G.A. Nevinsky, E.V. Tretyakov, Phosphonium
betaines derived from hexafluoro-1,4-naphthoquinone: synthesis and cytotoxic and
antioxidant activities, J. Fluor. Chem. 192 (2016) 68–77.
[8] L.I. Goryunov, S.I. Zhivetyeva, G.A. Nevinsky, V.D. Shteingarts, Synthesis of di-
phenyl(X)phosphonium betaines (X = CH3, C6H5, 2,5-F2C6H3) from hexafluoro-1,4-
naphthoquinone, ARKIVOC 8 (2011) 185–191.
[9] S.I. Zhivetyeva, G.A. Selivanova, L.I. Goryunov, I.Yu. Bagryanskaya,
V.D. Shteingarts, Triphenylphosphanodefluorination of fluoranil and its derivatives,
J. Fluor. Chem. 180 (2015) 21–32.
1
2
2JCF = 11.0 Hz, C6or7], 145.1 [ddd, JCF = 263.6 Hz, JCF = 17.1 Hz,
3JCF = 12.3 Hz, JCF = 3.0 Hz, C5or8], 142.7 [ddd, JCF = 261.7 Hz,
4
1
2JCF = 15.9 Hz, JCF = 12.5 Hz, JCF = 3.0 Hz, C5or8], 119.4 [dm,
3
4
2JCF = 10.6 Hz, C10F4O2], 116.4 (m, C10F4O2), 86.9 [d, 1JCP = 88.5 Hz,
C3], 13.6 [d, JCP = 53.0 Hz, CH2], 6.2 [d, JCP = 4.9 Hz, CH3] ppm.
1
2
19F NMR (CDCl3): δ = −138.8, −142.1, −145.3, −150.4 [ddd, 1F,
ortho
para
J
19.3÷20.1 Hz metaJFF 9.0÷11.0 Hz,
J
= 13.6 Hz] ppm.31
P
FF
FF
{1H} (CDCl3): δ = 32.49 (s) ppm. IR (neat): 2978 w, 2943 w, 2885 w,
1711 m, 1628 m, 1566 vs, 1504 s, 1462 w, 1410 w, 1365 s, 1338 m,
1275 s, 1238 w, 1159 m, 1107 w, 1045 m, 1012 w, 949 w, 887 w, 820
vw, 766 m, 744 w, 725 w, 694 w, 623 w, 600 vw cm−1. HRMS: calcd.
for С16H15F4O3P [M] 362.0690; found 362.0693. Crystals suitable for
XRD analysis were grown from acetone–heptane (1:1) in the re-
frigerator in an open flask at −5 °C.
[10] (a) J.F. Corbett, The chemistry of hydroxyquinones. Part 1. The reaction of 2-hy-
droxybenzoquinones with alkaline hydrogen peroxide, J. Chem. Soc. (C) (1966)
2308–2311;
Acknowledgements
(b) J.F. Corbett, The chemistry of hydroxyquinones. Part II. The autoxidation of
3,6-dimethylbenzene-l,2,4-triol, J. Chem. Soc. (C) (1967) 611–620;
(c) J.F. Corbett, The chemistry of hydroxy-quinones. Part V. The oxidation of 5-
Alkyl- and 2,5-dialkyl-3-hydroxybenzoquinones in the presence of Alkali, J. Chem.
Soc. (C) (1970) 1912–1916;
(d) J.F. Corbett, The chemistry of hydroxy-quinones. Part VI. Formation of 2-
Hydroxy-semiquinones during the autoxidation of benzene-1,2,4-triols in alkaline
solution, J. Chem. Soc. (C) (1970) 2101–2106.
This work was financially supported by the Russian Foundation for
Basic Research (grant No. 16-33-00005 mol_a). The authors would like
to acknowledge the Multi-Access Chemical Service Center SB RAS for
spectral and analytical measurements.
[11] G.C. Yakobson, V.D. Shteingarts, N.N. Vorozhtsov Jr., Reaction of octa-
fluoronaphthalene with nitric acid, Zh. Vses. Khim. Ob-va 9 (1964) 702–704
(Chem. Abstr., 62, 1965, 9078b).
Appendix A. Supplementary data
[12] G.M. Sheldrick, SHELX-97, Programs for Crystal Structure Analysis (Release 97-2),
University of Göttingen, Germany, 1997.
[13] SADABS, v. 2008-1, Bruker AXS, Madison, WI, USA, 2008.
[14] (a) A.L. Spek, PLATON, A Multipurpose Crystallographic Tool (Version 10M),
Utrecht University, Utrecht, The Netherlands, 2003.
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M. Towler, J. Van De Streek, Mercury: visualization and analysis of crystal struc-
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Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.jfluchem.2017.11.010.
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28