New phosphonium salts based on 3-(diphenylphosphino)propanoic and ω-haloalkanoic acids

Article abstract of DOI:10.1016/j.mencom.2021.03.032

Quarternization of 3-(diphenylphosphino)propanoic acid with ω-haloalkanoic acids affords novel phosphonium salts containing two carboxy groups. The phosphonium salts were treated with 1 M alkali solution to obtain corresponding carboxylate phosphabetaines

Full text of DOI:10.1016/j.mencom.2021.03.032

Mendeleev
Communications
Mendeleev Commun., 2021, 31, 242–243
New phosphonium salts based on 3-(diphenylphosphino)propanoic
and w-haloalkanoic acids
Semyon R. Romanov,*a Yana V. Dolgova,a Maxim V. Morozov,a Kamil A. Ivshin,b Dmitriy A. Semenov,c
Yulia V. Bakhtiyarova,a Irina V. Galkina,a Olga N. Kataevab and Vladimir I. Galkina
a A. M. Butlerov Institute of Chemistry, Kazan Federal University, 420008 Kazan, Russian Federation.
E-mail: semyonromanov@yandex.ru
b A. E. Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of the Russian
Academy of Sciences, 420088 Kazan, Russian Federation
c Elabuga Institute, Kazan Federal University, 423600 Elabuga, Russian Federation
DOI: 10.1016/j.mencom.2021.03.032
ꢁ
Ph2P Cꢀ2 Cꢀ2 COOꢀ
ꢂCꢀ2ꢃn COOꢀ
ꢀalꢄ
Quarternization of 3-(diphenylphosphino)propanoic acid
Ph2P Cꢀ2 Cꢀ2 COOꢀ ꢁ ꢀal
ꢂCꢀ2ꢃn COOꢀ
with w-haloalkanoic acids affords novel phosphonium salts
containing two carboxy groups. The phosphonium salts were
treated with 1 m alkali solution to obtain corresponding
carboxylate phosphabetaines. The structure of the
compounds was established by IR and NMR spectroscopy,
elemental analysis and X-ray single crystal diffraction.
Keywords: 3-(diphenylphosphino)propanoic acid, phosphonium salts, carboxylic acids, phosphabetaines, crystal structure.
Ph2P(CH2)2COOH +
The chemistry of phosphonium salts and carboxylate
phosphabetaines attracts attention owing to their wide
application. Phosphonium salts are used as ionic liquids,1–3
separation agents of rare-earth metals4 and catalysts;5,6 they
demonstrate high antimicrobial activity7–9 and possess anti-
cancer activity.10–12 Carboxylate phosphabetaines, analogues of
amino acids, are suitable ligands for metal complexes,13,14 can be
used as bifunctional catalysts15 and difluoromethylation agents.16
Zwitterionic structures in recent years have been actively
employed in hemodialysis membranes.17–19
In the last few years, our group has explored the synthesis,
structure and reactivity of phosphonium salts and carboxylate
phosphabetaines. Along with nucleophilic addition of tertiary
phosphines at unsaturated carboxylic acids,20,21 the
nucleophilic substitution of triphenylphosphine to w-halo-
alkanoic acids was found to be good synthetic strategy.22
Within the framework of this study, we were interested in
moving to another tertiary phosphine, namely, 3-(di-
phenylphosphino)propanoic acid 1. Along with the tertiary
phosphorus atom, this compound contains the carboxy group,
so its reactions with w-haloalkanoic acids should afford
phosphonium salts bearing two carboxy groups. Elongation of
polymethylene spacer in w-haloalkanoic acids should also
provide long-chained derivatives generally known for
improved antimicrobial activity.
Hal(CH2)nCOOH
1
Hal–
+
i
Ph2P CH2 CH2 COOH
(CH2)n COOH
2a–g
65–81%
CH2
CH2
O
a n = 1, Hal = Br
b n = 2, Hal = Br
c n = 3, Hal = Br
d n = 4, Hal = Br
e n = 7, Hal = Br
f n = 9, Hal = Br
g n = 2, Hal = Cl
+
C
Ph2P
ii
O
– H
2a–f
(CH2)n
C
O
3a–f
O
Scheme 1 Reagents and conditions: i, MeCN, 80 °C, 10 h; ii, NaOH,
MeCN, room temperature.
Table 1 Selected characteristics of prepared phosphonium compounds
2a–g.a
Com- Haloalkanoic
pound acid applied
n(COOH)/ 31P NMR,
cm–1
mp/°C
Yield (%)
d (D2O)
25.27
27.42
27.2
2a
2b
2c
2d
2e
2f
BrCH2COOH
1720
210–212 80
180–182 81
119–120 77
Br(CH2)2COOH 1720
Br(CH2)3COOH 1720
Br(CH2)4COOH 1715
Br(CH2)7COOH 1715
Br(CH2)9COOH 1715
Cl(CH2)2COOH 1736
27.2
oil
oil
oil
79
74
78
In fact, quaternization of phosphine 1 with w-bromoalkanoic
acids in MeCN at 80 °C for 10 h afforded stable at room
temperature phosphonium salts 2a–f in yields from 74 to 81%
(Scheme 1, Table 1).
Compounds2a–carecrystallinesubstanceswhilehomologues
2d–f are oils at room temperature (see Table 1). The structure of
the synthesized compounds was unambiguously proved by IR,
1H, 13C, 31P NMR spectroscopy and elemental analysis. In their
31P NMR spectra, single phosphorus signals were observed
corresponding to the obtained phosphonium salts. According to
26.8
26.9
2g
27.2
186–189 65
a For synthetic details and full NMR data, see Online Supplementary
Materials.
IR spectroscopy, all products had absorption bands in the region
of 1715–1735 cm–1 corresponding to two carboxyl groups of
phosphonium salts 2a–f. The structure of representative 2a was
© 2021 Mendeleev Communications. Published by ELSEVIER B.V.
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.
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Mendeleev Commun., 2021, 31, 242–243
scientific activities (grant no. 0671-2020-0063). X-ray diffraction
study was supported from the government assignment for FRC
Kazan Scientific Centre of RAS.
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2021.03.032.
Figure 1 A fragment of crystal packing of (2-carboxyethyl)(carboxy-
methyl)diphenylphosphonium bromide 2a showing hydrogen bonds of
carboxy groups with bromine anions.
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Scheme 1). The most informative method for carboxylate
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†
Crystal data for 2a. C17H18BrO4P, M = 397.19 g mol–1, triclinic, space
–
group P1(no. 2), Z = 2, a = 8.0672(5), b = 9.4323(6) and c = 12.7937(8) Å,
a = 88.123(3)°, b = 82.330(3)°, g = 65.723(3)°, V = 879.21(10) Å3,
rcalc = 1.500 g cm–3, μ = 2.445 mm–1, 42122 reflections collected
(–10 £ h £ 10, –12 £ k £ 12, –17 £ l £ 17), q range of 1.607° to
28.872°, 4578 independent (Rint = 0.0249) and 4437 observed reflections
[I ³ 2s(I)], 216 refined parameters, R1 = 0.0182, wR2 = 0.0472, GOOF
1.049, max(min). Residual electron density 0.362 (–0.482) eÅ–3. For
more details, see Online Supplementary Materials.
CCDC 2035123 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via http://www.ccdc.cam.ac.uk.
Received: 26th October 2020; Com. 20/6347
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