New di- and tricarboxylate phosphabetaines

Article abstract of DOI:10.1007/s11172-016-1453-5

New stable tricarboxylate phosphabetaines were synthesized based on 3-(diphenylphosphino)propionic acid and unsaturated dicarboxylic acids (maleic and itaconic). A new dicarboxylate phosphabetaine was synthesized based on 1,3-bis(diphenylphosphino)propane, which did not contain any proton-donor reagents in its crystal lattice.

Full text of DOI:10.1007/s11172-016-1453-5

1
308
Russian Chemical Bulletin, International Edition, Vol. 65, No. 5, pp. 1308—1312, May, 2016
New diꢀ and tricarboxylate phosphabetaines*
Yu. V. Bakhtiyarova, A. F. Aksunova, R. R. Minnullin, I. V. Galkina, and V. I. Galkin
Kazan (Volga Region) Federal University,
1
8 ul. Kremlevskaya, 420008 Kazan, Russian Federation.
Fax: +7 (843) 238 7901. Eꢀmail: vig54@mail.ru
New stable tricarboxylate phosphabetaines were synthesized based on 3ꢀ(diphenylꢀ
phosphino)propionic acid and unsaturated dicarboxylic acids (maleic and itaconic). A new
dicarboxylate phosphabetaine was synthesized based on 1,3ꢀbis(diphenylphosphino)propane,
which did not contain any protonꢀdonor reagents in its crystal lattice.
Key words: carboxylate phosphabetaines, unsaturated dicarboxylic acids, phosphonium salts.
Earlier, we have studied synthesis, structure, reactiviꢀ
phines.13—16 These reactions are accompanied by decarbꢀ
oxylation, however, we detected the formation of tricarbꢀ
ty, and biological activity of carboxylate phosphabetaines
based on various tertiary phosphines and unsaturated carbꢀ
oxylic acids.1
31
oxylate phosphabetaine 3a by P NMR spectroscopy. Iniꢀ
—11
31
tially, the P NMR spectra of the reaction mixture exhibꢀ
Recently, we have studied phosphorylation reactions
of 3ꢀ(diphenylphosphino)propionic acid (1) with unsatꢀ
urated monocarboxylic acids such as acrylic, crotonic,
methacrylic, and cinnamic to obtain stable dicarboxylate
phosphabetaines, the structure of which was established
by a combination of physicochemical methods.12
In the present work, we study reactions of acid 1 with
unsaturated dicarboxylic acids, namely, fumaric (2a),
maleic (2b), and itaconic (2c) (Scheme 1). It was supposed
that the final product would contain three carboxy groups.
ited two signals for the phosphorus atoms at δ 27 (3a) and
P
28.5 (4) (Scheme 2), with time, the intensity of the second
signal increased, while that of the second signal decreased.
The isolated crystalline product contains the only signal at
δP 28.5 (4). The IR and NMR spectra, as well as melting
points of the compound completely correspond to product 4
1
2
obtained in the studied earlier reaction of 3ꢀ(diphenylꢀ
phosphino)propionic (1) and acrylic acids (5) (see Scheme 2).
It is obvious that the reaction course is accompanied by
decarboxylation process.
Scheme 1
Scheme 2
2
a
b
c
R
H
R´
COOH
H
R´´
H
H
Product
3a
3a
COOH
H
H
CH COOH
3b
2
The reaction of fumaric acid (2a) with acid 1 proceeds
Such a behavior of fumaric acid (2a) in the reactions
similarly to already known reactions of tertiary phosꢀ
with tertiary phosphines accompanied by decarboxylation
1
3—16
of the intermediate product is quite expected.
Noneꢀ
31
*
Dedicated to Academician of the Russian Academy of Sciences
theless, in this case the P NMR spectrum of the reaction
mixture for the first time exhibited two signals (triꢀ and
O. G. Sinyashin on the occasion of his 60th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1308—1312, May, 2016.
066ꢀ5285/16/6505ꢀ1308 © 2016 Springer Science+Business Media, Inc.
1

New diꢀ and tricarboxylate phosphabetaines
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 5, May, 2016
1309
dicarboxylate betaines), which confirmed the fact of the
intermediate formation of structure 3a.
were carried out in D O, since this compound is insoluble
2
in organic solvents and can be stored only under the layer
of diethyl ether. The chemical shift of the phosphorus
nucleus was found in the region indicative of phosphaꢀ
The reaction of acid 1 with maleic acid (2b) proceeds
within several minutes with the formation of a white preꢀ
cipitate. The 3 P NMR spectrum contains one signal for the
1
1
betaines with δP 27.6. The H NMR spectrum exhibited
phosphorus atom at δ 28.7. Product 3a with m.p. 80 °C is
signals for all the protons corresponding to this structure.
Another approach to the synthesis of dicarboxylate
phosphabetaines used in the present work became the studꢀ
ies of the reaction of 1,3ꢀbis(diphenylphosphino)propane
(9) with maleic acid (2b) (Scheme 4).
P
well soluble in water and ethyl alcohol and poorly in aceꢀ
13
tonitrile. Based on the C NMR data, it can be inferred
that the synthesized betaine 3a contains three carboxy
groups, the doublet signals (spinꢀspin interaction with the
phosphorus atom nucleus) of which are found in the inꢀ
dicative region: δC 169.5, 173.6, and 174.2 (see Experiꢀ
mental section). Elemental analysis data also correspond
to the tricarboxylate phosphabetaine.
Scheme 4
It is necessary to note that upon prolonged storage for
several months, product 3a shows signs of decarboxylaꢀ
tion. Apart from that, if the reaction of acid 1 with maleic
acid (2b) is carried out under influence of heat, the decarꢀ
boxylation occurs already in the course of this reaction to
yield dicarboxylate phosphabetaine 4 (see Scheme 2).
In this connection, we carried out additional studies of
phosphabetaine 3a by a combined method of thermoꢀ
gravimetry, differential scanning calorimetry, and mass
spectrometry TGꢀDSCꢀMS, which showed not very high
thermal stability of the synthesized betaine. The sample
was heated in the temperature range from 30 to 200 °C.
No mass loss was observed in the range of 30—80 °C,
whereas from 80 to 130 °C its mass changed by 13%, with
simultaneous liberation of carbon dioxide and water. Note
that three peaks are observed during heating the sample to
The reaction of bisphosphine 9 with maleic acid (2b)
in acetonitrile proceeds rapidly, it is also accompanied by
decarboxylation, and gives rise to colorless stable crystals
with m.p. 234 °C. Elemental analysis of synthesized diꢀ
carboxylate diphosphabetaine 10 shows that it does not
contain any foreign molecules in the crystal lattice, though
earlier we stated many times that the stabilization of carꢀ
boxylate phosphabetaines with water molecules and other
2
00 °C, which correspond to the liberation of carbon diꢀ
oxide, that also indicates the presence of three carboxy
groups in phosphabetaine 3a.
1
—11
protonꢀdonor reagents is their distinguishing feature.
The structure of product 10 was confirmed by IR spectroꢀ
Apart from that, the reactions of tertiary phosphines 6a—c
with maleic acid (2b) studied earlier1
3—16
showed that the first
1
13
31
scopy and H, C, and P NMR spectroscopy. The IR
spectrum exhibited one characteristic absorption band of
step led to the formation of dicarboxylate phosphabetaines
a—c, insoluble in organic solvents, which were relatively
–
1 13
7
carboxylate anion in the region of 1580 cm
.
C NMR
stable under the layer of a solvent, but with time anyway
underwent decarboxylation giving betaines 8a—c (Scheme 3).
spectrum showed the presence of only one signal for carbon
nuclei of both carboxylate groups, that indicates their magꢀ
netic equivalence. The spectrum also shows the presence
of signals for all the other carbon atoms.
Scheme 3
Such a dicarboxylate diphosphabetaine structure based
on 1,2ꢀbis(diphenylphosphino)ethane was described earꢀ
1
7
lier. It was shown that it contains four water molecules
per one betaine molecule. Apart from that, ethyleneꢀ
bis(diphenylphosphonio)propionate and propyleneꢀbisꢀ
(
diphenylphosphonio)propionate were used as ligands in
different complexes both with metals and organic comꢀ
1
8,19
pounds.
Earlier, we have studied the formation of stable dicarbꢀ
oxylate phosphabetaines in the reactions of tertiary phosꢀ
R = Ph (a), Bu (b), cycloꢀC H (c)
12—16,20
6
11
phines with itaconic acid (2c).
In the present work,
we carried out the reaction of 3ꢀ(diphenylphosphino)ꢀ
propionic acid (1) with itaconic acid (2c) to prepare triꢀ
carboxylate phosphabetaine 3b (Scheme 5).
In the present work, we additionally investigated beꢀ
taine 7a by H and P NMR spectroscopy. These studies
1
31

1
310
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 5, May, 2016
Bakhtiyarova et al.
Scheme 5
Experimental
IR spectra were recorded on a Perkin—Elmer Spectrum Two
IR Fourierꢀtransform spectrometer. NMR spectra were recordꢀ
ed on a Bruker Avance III 400 Nanobay NMR spectrometer in
D O, if another solvent is not indicated. Derivatograms TGꢀ
2
DSC were recorded on an STA 449 F1 Jupiter instrument of
TGꢀDTA/DSC synchronous thermal analysis conjugated with
a Netzsch QMS 403 D Aeolos mass spectrometer.
3
ꢀ[(1,2ꢀDicarboxyethyl)diphenylphosphonio]propanoate (3a).
The reaction proceeded similarly in both acetonitrile and ethyl
acetate. A solution of maleic acid (2b) (0.14 g, 0.0012 mol) in
ethyl acetate (3 mL) was added dropwise to a solution of
The reaction proceeded rapidly in ethyl acetate or
acetonitrile with the formation of the only crystalline prodꢀ
3
ꢀtridiphenylphosphinopropanoic acid (1) (0.3 g, 0.0012 mol) in
EtOAc (5 mL) with continuous stirring. The reaction reached
completion within several minutes to form a white precipitate,
which was filtered on a Shott funnel, washed with diethyl ether,
and dried in vacuo. The product 3a is well soluble in water and
ethanol with heating, insoluble in acetonitrile, m.p. 80 °C (from
uct 3b with m.p. 122 °C, δ 27. The IR spectrum exhibited
P
two absorption bands of carboxy groups in the region of
1
700 cm–1, as well as that of carboxylate anion in the
–
1
region of 1600 cm . The signals for the carbon nuclei of
–
1
13
ethanol). The yield was 0.381 g (86%). IR (Nujol), ν/cm : 1600
three carboxy groups were found in the C NMR spectrum,
as well as the signals for all the other carbon atoms. Eleꢀ
mental analysis correspond to the composition of product 3b.
Like the dicarboxylate betaine 11 based on triphenylphosꢀ
phine and itaconic acid (2c) (Scheme 6), betaine 3b is
stable and does not undergo decarboxylation with time.
To increase the yield of the target product, in the
present work we continued the studies of the reaction of
–
1
(
COO ); 1700 (COOH). H NMR, δ: 2.43—2.57 (m, 2 H,
PCH CH ; 1 H, CHCH ); 2.58—2.78 (m, 2 H, CHCH );
2
2
2
2
13
2
(
2
.43—2.57 (m, 2 H, PCH ); 7.53—7.80 (m, 10 H, Ar). C (δ: 17.39
2
d, PCH , J = 54.2 Hz); 26.0 (d, PCHCH , J = 1.3 Hz);
6.45 (d, PCH CH , JP,C = 1.3 Hz); 31.30 (d, PCH, JP,C
= 46.6 Hz); 114.60 (d, Cipso,
JP,C = 29.75 Hz); 133.57 (d, C , J = 9.4 Hz); 135.30 (d, Cp,
= 2.5 Hz); 169.51 (d, C(O)O, JP,C = 1.5 Hz); 173.58
d, C(O)O, J = 14.3 Hz); 174.09 (d, C(O)O, J = 17.1 Hz).
1
2
2 P,C 2 P,C
2
2
=
2
2
1
J
= 83.4 Hz); 130.05 (d, Co,
P,C
3
2
m
P,C
4J
3
P,C
3
2
(
3
triphenylphosphine (6a) with itaconic acid (2c) already
P,C P,C
1
started earlier.1
3,16
P NMR, δ: 28.7. Found (%): C, 57.69; H, 4.69; P, 7.12.
C H O P. Calculated (%): C, 58.30; H, 4.86; P, 7.19. Shows
We changed conditions of the syntheꢀ
18
19
4
sis of betaine 11, namely, we used diethyl ether as the
solvent for acid 2c (see Experimental section). This resultꢀ
ed in the preparation of the stable dicarboxylate phosphaꢀ
betaine 11 with m.p. 162 °C (see Scheme 6). Its structure
signs of decarboxylation upon prolonged storage (several months).
ꢀ[(2,3ꢀDicarboxypropyl)diphenylphosphonio]propanoate
3b). A solution of itaconic acid (2c) (0.15 g, 0.0012 mol) in ethyl
3
(
acetate (3 mL) was added dropwise to a solution of acid 1 (0.3 g,
0.0012 mol) in ethyl acetate (5 mL) with continuous stirring.
The reaction reached completion within several minutes to form
a white precipitate of 3b. The precipitate was filtered on a Shott
funnel, washed with diethyl ether, and dried in vacuo. The prodꢀ
uct 3b is well soluble in water and ethanol, poorly soluble in
acetonitrile, m.p. 122 °C (from acetonitrile). The yield was 0.379
1
31
was confirmed by IR spectroscopy and H and P NMR
spectroscopy. Elemental analysis confirmed the composiꢀ
tion of compound 11.
Scheme 6
–
1
–
g (84.2%). IR (Nujol), ν/cm : 1550 (COO ); 1700 (COOH).
1
H NMR (D O), δ: 2.43—2.57 (m, 2 H, PCH CH ; 1 H,
2
2
2
CHCH ); 2.58—2.78 (m, 2 H, CHCH ); 2.43—2.57 (m, 2 H,
2
2
1
3
PCH ); 7.53—7.80 (m, 10 H, Ar). C NMR, δ: 17.18 (d,
PCH CH , J = 54.3 Hz); 22.7 (d, PCH CH, J = 52.3 Hz);
6.7 (d, PCH CH , JP,C = 1.3 Hz); 37.07 (s, PCH CHCH );
2 2 2 2
7.98 (d, PCH CH, J
84.7 Hz); 130.05 (d, Co,
JP,C = 9.6 Hz); 135.30 (d, C , J
m, 2 C(O)O); 176.78 (d, C(O)O, 4JP,C = 3.1 Hz). P NMR,
2
1
1
2
2
P,C
2
P,C
2
2
3
=
3
2
1
= 12.8 Hz); 116.23 (d, C , J
=
P,C
2
P,C
ipso
2
J
= 12.4 Hz); 133.57 (d, Cm,
= 2.5 Hz); 175.05—175.35
P,C
P,C
4
p
31
(
δ: 27.0. Found (%): C, 60.99; H, 5.70; P, 7.98. C H O P. Calꢀ
2
0
21
6
culated (%): C, 61.86; H, 5.41; P, 7.99.
ꢀ[(1,2ꢀDicarboxyethyl)diphenylphosphonio]propanoate (3a)
and 3ꢀ[(2ꢀcarboxyethyl)diphenylphosphonio]propanoate (4). A solꢀ
ution of fumaric acid (1a) (0.22 g, 0.0019 mol) in hot distilled
water (5 mL) was added dropwise to a solution of acid 1 (0.5 g,
3
The characteristics of carboxylate phosphabetaines
obtained in the present work are given in the Experimental
section.
In conclusion, new stable diꢀ and tricarboxylate phosꢀ
phabetaines were synthesized in the course of these studꢀ
ies, their composition and structure were confirmed by
a combination of physicochemical methods.
0
.0019 mol) in acetonitrile (5 mL) with continuous stirring. The
31
reaction mixture was allowed to stand for 1 days. P NMR
spectrum of the reaction mixture (D O, δ: 26.6 (3a), 28.8 (4)
2
(both s). The second signal increased with time. Anhydrous

New diꢀ and tricarboxylate phosphabetaines
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 5, May, 2016
1311
diethyl ether was poured to the reaction mixture, a precipitate
formed was filtered on a Shott funnel, washed with diethyl ether,
and dried in vacuo. The product 4 is well soluble in water and
ethanol with heating, insoluble in acetonitrile, m.p. 236 °C (from
(s, CH C(O)); 38.98 (d, PCH CH, 2J
= 12.4 Hz); 117.74
P,C
2
2
1
2
(d, Cipso, J = 86.9 Hz); 129.91 (d, C , J = 12.7 Hz); 133.46
P,C
o
P,C
3
4
(d, C , J
= 9.6 Hz); 134.96 (d, C , J
= 2.0 Hz); 175.96,
m
P,C
p
P,C
–
31
31
176.98 (both s, COO , COOH)). P NMR, δ: 21.8. P NMR
–
1
ethanol). The yield was 0.591 g (82.08%). IR (Nujol), ν/cm
:
(CDCl ), δ: 23.6. Found (%): C, 70.67; H, 5.37; P, 7.68.
3
–
1
1
3
680 (COO ). H NMR (D O)), δ: 2.38—2.45 (m, 4 H, CH C(O));
C H O P. Calculated (%): C, 70.41; H, 5.36; P, 7.91.
2
2
23 21
4
13
.04—3.11 (m, 4 H, PCH ); 7.57—7.76 (m, 10 H, Ar). C NMR,
2
1
δ: 16.73 (d, PCH , JP,C = 53.0 Hz); 27.28 (d, PCH CH ,
This work was financially supported by the Ministry of
Education and Science of the Russian Federation (at the
expense of subsidy allocated to the Kazan Federal Univerꢀ
sity for the Project part of the State Assignment in Acaꢀ
demic Area).
2
2
2
2
1
JP,C = 3.0 Hz); 116.51 (d, Cipso, J = 85.0 Hz); 129.99 (d, Co,
JP,C = 13.0 Hz); 132.86 (d, C , J = 10.0 Hz); 135.03 (d, C ,
P,C
2
3
m
P,C
3
p
4J
= 3.0 Hz); 175.87 (d, C(O)O, JP,C = 14.5 Hz). P NMR,
31
P,C
δ: 28.8. Found (%): C, 66.27; H, 5.50; P, 9.09. C H O P.
18
19
4
Calculated (%): C, 65.45; H, 5.75; P, 9.39.
ꢀ[(Carboxymethyl)diphenylphosphonio]acetate (7a). A soluꢀ
2
References
tion of maleic acid (2b) (0.23 g, 0.0019 mol) in acetonitrile (3 mL)
was added dropwise to a solution of triphenylphosphine 6a (0.5 g,
0
.0019 mol) in acetonitrile (5 mL) with continuous stirring. The
1. V. I. Galkin, Yu. V. Bakhtiyarova, N. A. Polezhaeva, R. A.
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reaction reached completion within several minutes to form
a white precipitate of 7a, which was insoluble in organic solvents.
Attempted isolation of crystalline product 7a led to its decarbꢀ
oxylation. The precipitate remained stable under the layer of
diethyl ether. H NMR (D O), δ: 2.71—2.78 (m, 1 H, PCH);
2
PCH ); 7.54—7.85 (m, 15 H, Ar). P NMR, δ: 25.0. The decarbꢀ
oxylation product 8a was characterized by IR spectra, H, C,
and 3 P NMR spectra, and Xꢀray diffraction.
1
2
.89 (dd, 2 H, CH , J = 51.8 Hz, J = 17.1 Hz); 2.43—2.57 (m, 2 H,
2
31
2
1
13
1
5
3
,3´ꢀ[Propaneꢀ1,3ꢀdiylbis(diphenylphosphonionediyl)]dipropꢀ
anoate (10). A solution of maleic acid (2b) (0.28 g, 0.0024 mol)
in acetonitrile (5 mL) was added dropwise to a solution of 1,3ꢀbisꢀ
4. V. I. Galkin, Yu. V. Bakhtiyarova, N. A. Polezhaeva, I. V.
Galkina, R. A. Cherkasov, D. B. Krivolapov, A. T. Gubayꢀ
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Stakheev, V. I. Galkin, O. E. Zhil´tsova, O. V. Zhukova,
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(in Russian).
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Khabibullin, V. I. Galkin, R. A. Cherkasov, Phosphorus, Sulꢀ
fur, Silicon Relat. Elem., 2011, 186, 854.
(
diphenylphosphino)propane (9 (0.5 g, 0.0012 mol)) in acetoꢀ
nitrile (5 mL) with continuous stirring. The reaction mixture was
allowed to stand for 1 days at room temperature, showing signs
of decarboxylation. The solvent was removed in vacuo. A precipꢀ
itate formed was filtered on a Shott funnel, washed with diethyl
ether, and dried in vacuo, which resulted in the formation of
colorless crystals with m.p. 234 °C (from acetonitrile). The yield
–1
–
1
was 0.510 g (65.4%). IR (Nujol), ν/cm : 1580 (COO ). H NMR
(
(
(
(
1
D O), δ: 1.38—1.52 (m, 2 H, PCH CH CH ); 2.14—2.27
2
2
2
2
m, 4 H, CH C(O)); 2.83—3.01 (m, 8 H, PCH ); 7.44—7.78
2
2
1
3
m, 20 H, Ar). C NMR, δ: 17.59 (s, CH CH CH ); 19.92
d, PCH CH C(O)O, J = 52.2 Hz); 23.71 (dd, PCH CH CH ,
2 2 P,C 2 2 2
JP,C = 52.3 Hz, J = 16.9 Hz); 31.04 (s, CH C(O)O); 118.72
d, Cipso, J = 85.0 Hz); 132.61 (d, C , J = 6.3 Hz); 135.18
P,C o P,C
2
2
2
1
1
P,C
2
1
2
(
(
=
3
3
d, C , J
= 4.3 Hz); 137.70 (s, C ); 179.89 (d, C(O)O, J
p P,C
m
P,C
3
1
12.3 Hz). P NMR, δ: 27.8. Found (%): C, 70.73; H, 5.90;
9. A. V. Salin, A. A. Sobanov, Yu. V. Bakhtiyarova, A. A.
Khabibullin, V. I. Galkin, R. A. Cherkasov, Phosphorus, Sulꢀ
fur, Silicon Relat. Elem., 2011, 186, 857.
P, 11.00. C H O P . Calculated (%): C, 71.22; H, 6.11; P, 11.15.
33
34
4 2
3
ꢀCarboxyꢀ2ꢀ[(triphenylphosphonio)methyl]propanoate (11).
A solution of itaconic acid (2c) (0.81 g, 0.0062 mol) in diethyl
ether (5 mL) was added dropwise to a solution of triphenylphosꢀ
phine 6a (1.63 g, 0.0062 mol) in acetonitrile (10 mL) with conꢀ
tinuous stirring. The reaction mixture was allowed to stand for
one week at room temperature. The solvent was evaporated
in vacuo to give a white crystalline product. The precipitate was
filtered on a Shott funnel, washed with diethyl ether, and dried
in vacuo, m.p. 162 °C (from ethanol). The yield was 1.537 g
10. A. V. Salin, A. A. Sobanov, Yu. V. Bakhtiyarova, A. A.
Khabibullin, V. I. Galkin, Russ. J. Gen. Chem. (Engl. Transl.),
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Pozdeev, S. N. Egorova, R. A. Cherkasov, V. I. Galkin,
J. Chem., 2013, http://dx.doi.org/10.1155/2013/302937.
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Cherkasov, V. I. Galkin, Russ. J. Gen. Chem. (Engl. Transl.),
2015, 85, 2037 [Zh. Obshch. Khim., 2015, 85, 1453].
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ullin, I. A. Litvinov, Phosphorus, Sulfur, Silicon Relat. Elem.,
2002, 177, 2063.
–
1
–
(
1
62.99%). IR (Nujol), ν/cm : 1590 (COO ); 1720 (COOH);
1
730 (COOH). H NMR (D O), δ: 2.26—2.54 (dd, 2 H, PCH CH ,
2
2
2
J = 51.51 Hz, J = 7.25 Hz); 2.85 (m, 1 H, CH); 3.11—3.63 (dd,
H, PCH , J = 130.29 Hz, J = 13.83 Hz); 7.30—7.81 (m, 15 H,
2
2
13
1
Ar). C NMR, δ: 23.65 (d, PCH2, JP,C = 53.9 Hz); 37.92

1
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Received November 9, 2015