Synthesis of Non-Symmetric Functionalized Polyfluoroalkyl Phosphites

Article abstract of DOI:10.1134/S1070363220050138

Abstract: Two ways for the synthesis of new representatives of non-symmetric organicphosphites with polyfluoroalkyl substituents were developed based on organicdichlorophosphites. The reaction of polyfluoroalkyl dichlorophosphites withallyl alcohol, proce

Full text of DOI:10.1134/S1070363220050138

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 5, pp. 839–844. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 5, pp. 744–750.
Synthesis of Non-Symmetric Functionalized Polyfluoroalkyl
Phosphites
N. K. Gusarovaa, S. F. Malyshevaa, N. A. Belogorlovaa, S. I. Verkhoturovaa,
L. A. Oparinaa, S. N. Arbuzovaa, N. A. Chernyshevaa, A. M. Nalibayevab,
G. K. Bishimbayevab, S. V. Yas’koc, and B. A. Trofimova,*
a A.E. Favorskii Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, 664033 Russia
b Sokol’skii Institute of Fuel, Catalysis, and Electrochemistry, Almaty, 050000 Kazakhstan
c Irkutsk State University of Communications, Irkutsk, 664074 Russia
*e-mail: boris_trofimov@irioch.irk.ru
Received November 28, 2019; revised November 28, 2019; accepted December 5, 2019
Abstract—Two ways for the synthesis of new representatives of non-symmetric organic phosphites with polyfluo-
roalkyl substituents were developed based on organic dichlorophosphites. The reaction of polyfluoroalkyl dichloro-
phosphites with allyl alcohol, proceeding at a temperature of –10–22°C (2 h) in the presence of triethylamine, gave
diallyl polyfluoroalkyl phosphites in a yield of 75–77%. Under similar conditions (–30–22°C, 2–4 h, Et3N), alkyl
(or aryl) dichlorophosphites reacted with polyfluoroalkanols to form alkyl (or aryl) bis(polyfluoroalkyl) phosphites
(yield 56–67%). Unlike diallylpolyfluoroalkyl- and alkylbis(polyfluoroalkyl) phosphites, arylbis(polyfluoroalkyl)-
phosphites are symmetrized under storage conditions (room temperature, inert atmosphere), forming the corre-
sponding triaryl- and tris(polyfluoroalkyl) phosphites.
Keywords: dichlorophosphites, allyl alcohol, polyfluoroalkanols, diallyl polyfluoroalkyl phosphites,
alkylbis(polyfluoroalkyl) phosphites, arylbis(polyfluoroalkyl) phosphites
DOI: 10.1134/S1070363220050138
In recent years, special attention of researchers has
been given to fluorinated organic phosphites, which
are used as additives in lithium-ion battery electrolytes
to increase their fire and explosion safety [1–7], as
well as drug precursors [8–11], ligands for special
metal complexes [12–18], reactive building blocks for
organic synthesis [10, 11, 19–25]. Typical methods
for the synthesis of fluorine-substituted phosphites are
based on the use of phosphorus trichloride or diorganyl
chlorophosphites as phosphorylating reagents of alkanols
[10–12, 20, 22, 26]. Organic dichlorophosphites have
been much less studied in these reactions [27–30].
Polyfluoroalkylphosphites with allyl substituents are also
unknown; however the introduction of these moieties
allows the use of such compounds in the synthesis of
promising non-combustible polymeric materials [7].
with allyl alcohol and organic dichlorophosphites with
polyfluoroalkanols.
Polyfluoroalkyl dichlorophosphites 1a–1c reacted
with allyl alcohol under mild conditions (–10‒22°C,
2 h, CH2Cl2 or Et2O) in the presence of triethylamine to
furnish diallyl polyfluoroalkyl phosphites 2a–2c with a
yield of 75–77% (Scheme 1). The reaction proceeded
chemoselectively: no prototropic isomerization of
the allyl fragment to prop-1-enyl under the indicated
conditions was observed (31P NMR data). Compounds
2a–2c are stable during storage in an inert atmosphere
and do not undergo symmetrization with the formation
of triallyl and tris(polyfluoroalkyl) phosphites.
The developed method allows us to synthesize
new representatives of non-symmetric polyfluoroalkyl
phosphites starting from dichlorophosphites 3a–3c and
fluoroalkanols 4, 5. Under similar conditions (Et3N, an
organic solvent, –10‒22°С for ethyl dichlorophosphite
3a and –30‒22°С for aryl phosphites 3b, 3c) the
reaction proceeded within 2–4 h to afford organyl
Herein, we reported a convenient method for the
synthesis of new representatives of non-symmetric
functionalized polyfluoroalkyl phosphites based on
the reactions of polyfluoroalkyl dichlorophosphites
839

840
GUSAROVA et al.
Scheme 1.
O
O
Cl
Cl
Et3N,
–10–22°C, 2 h
P
+
R
P
FO
ꢀ
Et N
·HCl
OH
3
ORF
1a–1c
2a–2c (75–77%)
RF = CF3CH2 (a), H(CF2)2CH2 (b), H(CF2)4CH2 (c).
Scheme 2.
Et3N,
–30–22°C, 2–4 h
ORF
RO
Cl
Cl
P
+
R
FOH
RO
P
ꢀ
Et N
·HCl
3
ORF
3a–3c
4, 5
6a–6d (56–67%)
R = Et (ꢀɚ, ꢁɚ, 6b), 4-MeOC6H4 (3b, 6c), 4-FC6H4 (3c, 6d);
RF = CF3CH2 (4, ꢁɚ, 6c, 6d), H(CF2)4CH2 (5, 6b).
Scheme 3.
OR
OR
CF3
CF3
O
O
20–22°C
14 days
RO
P
+
F
3C
P
O
6c, 6d
7
8, 9
R = 4-MeOC6H4 (6c, 8), 4-FC6H4 (6d, 9).
bis(polyfluoroalkyl) phosphites 6a–6d with a moderate
yield of 56–67% (Scheme 2).
(400.13, 101.61, 376.50, and 161.98 MHz, respectively)
from CDCl3 solutions relative to internal HMDS (1Н,
13C), CFCl3 (19F), and external 85% H3PO4 (31P). IR
spectra were recorded on a Bruker IFS 25 spectrometer
from thin layer.
Alkyl phosphites 6a and 6b derived from ethyl
dichlorophosphite 3a are relatively stable upon standing
under standard conditions (room temperature, argon,
14 days), while 4-methoxyphenyl and 4-fluorophenyl
phosphites 6c and 6d under the same conditions
undergo conversions with the formation of symmetric
tris(trifluoroethyl) phosphite 7 and triaryl phosphites 8,
9 (Scheme 3). Within two weeks, the compounds ratio
was 6c : 7 : 8 = 24 : 1 : 0.5 and 6d : 7 : 9 = 24 : 2 : 1 (by
1H, 31P NMR data).
The starting polyfluoroalkyl dichlorophosphites 1a–1c
were obtained from PCl3 and polyfluoroalkanols in the
presence of triethylamine (1 mol %) [31]. The starting
ethyl dichlorophosphite 3a was synthesized according to
the procedure [32]. Aryl dichlorophosphites 3b and 3c
were obtained by a modified procedure [33] from PCl3
and 4-substituted phenols (1.5 : 1). All experiments were
carried out in a dry inert atmosphere (argon).
New representatives of non-symmetric functionalized
triorganyl phosphites with polyfluoroalkyl substituents
obtained by a convenient effective method can be used
as components for lithium-ion batteries, drug precursors,
and ligands for the production of metal complexes.
General procedure for the synthesis of diallyl poly-
fluoroalkyl phosphites 2a–2c. A solution of 40.3 mmol
of polyfluoroalkyl dichlorophosphite 1 in 20 mL of
dichloromethane was added dropwise with stirring for
1 h at –10–7°C to a solution of 89.5 mmol (6.45 g) of
allyl alcohol and 93.9 mmol (9.5 g) of triethylamine in
60 mL of anhydrous dichloromethane. The formation of
a white precipitate of triethylamine hydrochloride was
EXPERIMENTAL
1Н, 13C, 19F, 31Р NMR spectra were obtained on a
Bruker DPX 400 and a Bruker AV-400 spectrometers
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SYNTHESIS OF NON-SYMMETRIC FUNCTIONALIZED POLYFLUOROALKYL PHOSPHITES
841
observed. The reaction mixture was stirred for 1 h at
room temperature, then 100 mLof hexane was added and
the resulting mixture was kept overnight. Triethylamine
hydrochloride was filtered off, washed with hexane
(5 × 30 mL). Washings and the filtrate were combined,
the solvents were distilled off under reduced pressure,
and the residue was distilled in vacuum. Phosphite 2b
was synthesized in diethyl ether (120 mL).
(CF2). 31P NMR spectrum: δP 139.5 ppm. Found, %: C
39.12; H 4.85; F 27.65; P11.38. C9H13F4O3P. Calculated,
%: C 39.14; H 4.74; F 27.52; P 11.22.
Diallyl (2,2,3,3,4,4,5,5-octafluoropentyl) phosphite
(2c). Yield 11.4 g (75%), clear colorless liquid, bp
70‒72°C (1 mmHg), d420 1.3534, nD20 1.3882, η 3.63 cP.
IR spectrum, ν, cm–1: 3090 m, 3021 m, 2988 m, 2954 m,
2889 m, 1650 m, 1459 m, 1426 m, 1411 m, 1360 m,
1287 s, 1263 s, 1173 s, 1132 s, 1023 s, 988 s, 928 s, 904 s,
806 s, 689 w, 673 w, 628 m, 609 m, 546 m, 506 m. 1H
Diallyl (2,2,2-trifluoroethyl) phosphite (2a). Yield
7.4 g (75%), clear liquid, bp 38‒39°C (1 mmHg), d420
1.1649,nD20 1.4013,η1.37cP.IRspectrum,ν,cm–1:3089m,
3020 w, 2986 m, 2940 m, 2879 m, 1649 m, 1456 m,
1424 m, 1410 m, 1339 w, 1283 s, 1168 s, 1089 s, 1068 s,
1023 s, 988 s, 963 s, 924 s, 846 m, 794 s, 656 w, 558 w,
512 w. 1H NMR spectrum, δ, ppm: 4.12 d. q (2H, CF3CH2,
NMR spectrum, δ, ppm: 4.24 t. d. t (2H, CH2CF2, 3JHF
14.0, JHP = 6.5, JHF = 1.4 Hz), 4.36 d. d. d. d (4H,
=
3
4
3
3
4
4
CH2CH=, JHP = 8.4, JHH = 5.4, JHH = 1.4, JHH
=
3
0.7 Hz), 5.19 d. d. d. d (2H, =CH2, Hcis, Jcis = 10.4,
2JHH = 1.5, 4JHH = 1.4, 4JHH = 0.7 Hz), 5.28 d. d. t (2H,
=CH2, Htrans, 3Jtrans = 17.1, 2JHH = 1.5, 4JHH = 1.4 Hz),
3JHP = 7.1, 3JHF = 8.4 Hz), 4.36 d. d (4H, CH2CH=, 3JНР
=
=
8.1, JHH = 5.4 Hz), 5.19 d (2H, =CH2, Hcis, Jcis
5.91 d. d. t (2H, CH=, 3Jtrans = 17.1, 3Jcis = 10.4, 3JHH
=
3
3
10.4 Hz), 5.30 d (2H, =CH2, Htrans, Jtrans = 18.2 Hz),
5.4 Hz), 6.03 t. t (1H, CF2H, 2JHF = 51.9, 3JHF = 5.4 Hz).
3
5.90 d. d. t (2H, CH=, Jtrans = 18.2, Jcis = 10.4, JHH
13С NMR spectrum, δС, ppm: 58.4 t. d (CH2CF2, 2JCF
=
=
3
3
3
2
2
= 5.4 Hz). 13С NMR spectrum, δС, ppm: 59.0 q. d
26.3, JCP = 8.2 Hz), 63.9 d (CH2CH=, JCP
(CF3CH2, 2JCF = 36.2, 2JCP = 8.6 Hz), 63.6 d (CH2CH=,
12.1 Hz), 107.7 t. t (CF2H, 1JCF = 254.0, 2JCF = 31.0 Hz),
1
2
2JCP = 12.1 Hz), 116.8 (CH2=), 123.4 q. d (CF3, JCF
=
110.1 t. q (CF2CF2H,1JCF = 250.0, JCF = 29.0 Hz),
278.0, 3JCP = 6.0 Hz), 133.8 d (CH=, 3JCP = 5.2 Hz). 19F
NMR spectrum: δF –75.3 ppm. 31P NMR spectrum: δP
139.7 ppm. Found, %: C 39.12; H 4.78; F 23.48; P 12.48.
C8H12F3O3P. Calculated, %: C 39.36; H 4.95; F 23.34;
P 12.69.
110.9 t. q (CF2CF2CF2H, 1JCF = 264.7, 2JCF = 30.6 Hz),
115.1 t. t. d (CF2CH2, 1JCF = 256.5, 2JCF = 31.0, 3JСР
=
3
3.5 Hz), 117.0 (CH2=), 134.1 d (CH=, JCP = 5.2 Hz).
19F NMR spectrum, δF, ppm: –137.2 d (CF2H, JHF
2
=
51.9 Hz), –130.2 m (CF2CF2H), –125.3 m (CF2CF2CF2H),
–120.4 m (CF2CH2). 31P NMR spectrum: δP 140.8 ppm.
Found, %: C 35.10; H 3.47; F 40.18; P8.10. C11H13F8O3P.
Calculated, %: C 35.12; H 3.48; F 40.40; P 8.23.
Diallyl (2,2,3,3-tetrafluoropropyl) phosphite (2b).
Yield 8.6 g (77%), clear colorless liquid, bp 59‒60°C
20
(1 mmHg), d420 1.2067, nD 1.4076, η 1.80 cP. IR
spectrum, ν, cm–1: 3089 m, 3020 m, 2988 s, 2946 s, 2880 s,
1650 m, 1458 s, 1425 s, 1416 m, 1380 m, 1359 m,
1282 s, 1265 s, 1230 s, 1210 s, 1130 s, 1105 s, 1051 s,
1022 s, 989 s, 932 s, 835 s, 793 s, 680 m, 673 w, 645 w,
General procedure for the synthesis of organyl
bis(polyfluoroalkyl) phosphites 6a–6d. To a solution of
64.7 mmol of organyl dichlorophosphite 3 in 150 mL of
an organic solvent [diethyl ether (3a), dichloromethane
(60 mL) (3b), hexane (3c, 3d)] was added dropwise with
stirring a solution of 155 mmol of polyfluoroalkanol 4 or
5 and 155 mmol ( 15.7 g) of triethylamine in 30 mL of the
corresponding solvent for 1–2 h at low temperature [–10–8°C
(3a, 3b), –30–25°C (3c, 3d), dry ice–acetone]. The formation
of a white precipitate of triethylamine hydrochloride was
observed. The reaction mixture was stirred for 1–2 h at room
temperature, argonwaspassedtoremoveHCl, andthemixture
was kept overnight in the case of obtaining compounds 6a
and 6b. The precipitate (triethylamine hydrochloride) was
filtered off, washed (3 × 30 mL) with diethyl ether (3a) or
hexane (3b–3d). Washings and the filtrate were combined,
the solvents were distilled off under reduced pressure, and the
residue was distilled in vacuum. To prevent symmetrization
1
583 w, 549 m, 385 w. H NMR spectrum, δ, ppm:
3.96 t. d. t (2H, CH2CF2, 3JHF = 12.7, 3JHP = 6.2, 4JHF
1.6 Hz), 4.17 d. d. t (4H, CH2CH=, JHP = 8.4, JHH
=
=
=
=
3
3
4
3
5.3, JHH = 1.6 Hz), 5.03 d. m (2H, =CH2, Hcis, Jcis
10.5 Hz), 5.20 d. d. t (2H, =CH2, Htrans, 3Jtrans = 17.1, 2JHH
1.7, 4JHH = 1.6 Hz), 5.52 t. t. d (1H, CF2H, 2JHF = 53.1,
3JHF = 4.9, 5JHP = 1.5 Hz), 5.75 d. d. t (2H, CH=, 3Jtrans
=
17.1, Jcis = 10.5, JHH = 5.3 Hz). 13С NMR spectrum,
3
3
δС, ppm: 58.8 t. d (CH2CF2, 2JCF = 29.5, 2JCP = 7.9 Hz),
63.6 d (CH2CH=, 2JCP = 12.1 Hz), 109.5 t. t (CF2H, 1JCF
=
=
2
1
249.3, JCF = 34.4 Hz), 115.2 t. t. d (CH2CF2, JCF
249.7, 2JCF = 26.7, 3JCP = 5.0 Hz), 117.4 (CH2=), 134.5 d
(CH=, JCP = 5.1 Hz). 19F NMR spectrum, δ, ppm:
3
–139.2 d. t (CF2H, 2JHF = 53.1, 3JFF = 4.6 Hz), –125.7 m
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842
GUSAROVA et al.
of the aryl bis(polyfluoroalkyl) phosphites 6c and 6d, the
distillation flask was placed into a heated glycerin bath
(100–120°С) and distillation was carried out rapidly.
1444 s, 1413 s, 1283 s, 1250 s, 1207 s, 1167 s, 1090 s,
1058 s, 1036 s, 1009 m, 963 s, 925 m, 886 s, 848 s, 834 s,
797 s, 720 m, 698 m, 654 s, 637 w, 567 m, 548 s, 534 w,
1
522 s, 496 w. H NMR spectrum, δ, ppm: 3.71 s (3H,
Bis(2,2,2-trifluoroethyl) ethyl phosphite (6a). Yield
9.9 g (56%), clear colorless liquid, bp 23°C (1 mmHg),
d420 1.3743, nD20 1.3022, η 1.92 cP. IR spectrum, ν, cm–1:
2980 m, 2950 m, 2921 m, 2880 w, 2854 w, 1806 w,
1483 m, 1458 m, 1424 s, 1400 m, 1375 m, 1273 s, 1174 s,
1083 s, 1041 s, 965 s, 894 s, 842 s, 769 m, 661 s, 559 m,
3
3
СH3), 4.30 q (4H, CH2, JHP = JHF = 8.3 Hz), 6.87 d
3
3
(2H, C6H4, JHH = 8.9 Hz), 6.99 d (2H, C6H4, JHH
=
8.9 Hz). 13С NMR spectrum, δС, ppm: 55.4 (СH3),
59.5 q. d (CH2, 2JCF = 36.9, 2JCP = 7.6 Hz), 114.8 (C3,5,
C6H4), 121.0 d (C2,6, C6H4, JCP = 6.7 Hz), 123.5 q. d
3
(CF3, JCF = 275.3, JCP = 5.3 Hz), 144.4 d (C1, C6H4,
2JCP = 6.9 Hz), 156.5 (C4, C6H4). 19F NMR spectrum, δF,
ppm: –75.3 t. d (CF3, 3JFH = 8.2, 4JFP = 4.0 Hz). 31P NMR
spectrum: δP 132.5 ppm. Found, %: C 37.40; H 2.96; F
32.10; P 8.68. C11H11F6O4P. Calculated, %: C 37.52; H
3.15; F 32.37; P 8.80.
1
3
1
510 m, 483 m. H NMR spectrum, δ, ppm: 1.28 t (3H,
3
3
CH3, JHH = 7.1 Hz), 3.95 d. q (2H, CH3CH2, JHP
=
=
8.4, 3JHH = 7.1 Hz), 4.13 q (4H, CF3CH2, 3JHF = 3JHP
8.4 Hz). 13С NMR spectrum, δС, ppm: 16.4 d (CH3, 3JCP=
5.2 Hz), 59.5 q. d (CF3CH2, 2JCF = 36.9, 2JCP = 9.6 Hz),
59.9 d (CH3CH2, 2JCP = 12.5 Hz), 123.4 q. d (CF3, 1JCF
=
277.9, JCP = 5.9 Hz). 19F NMR spectrum, δF, ppm:
3
Bis(2,2,2-trifluoroethyl) (4-fluorophenyl) phosphite
(6d). Yield 14.6 g (66%), clear colorless liquid, bp
65‒68°C (2 mmHg), d420 1.4590, nD20 1.4082, η 2.89 cP.
IR spectrum, ν, cm–1: 3119 w, 3084 w, 3057 m, 2968 s,
2892 m, 1602 w, 1505 s, 1455 s, 1413 s, 1305 w, 1284 s,
1199 s, 1171 s, 1091 s, 1060 s, 1013 s, 964 s, 932 m, 888 s,
848 s, 841 s, 812 s, 718 m, 695 m, 654 s, 633 w, 564 m,
–75.5 t. d (CF3, JFH = 8.4, JFP = 4.5 Hz). 31P NMR
spectrum: δP 139.5 ppm. Found, %: C 26.08; H 3.51; F
41.33; P 11.50. C6H9F6O3P. Calculated, %: C 26.29; H
3.31; F 41.59; P 11.30.
3
4
Bis(2,2,3,3,4,4,5,5-octafluoropentyl) ethyl phosphite
(6b). Yield 22.6 g (65%), clear colorless liquid, bp
105°C (1 mmHg), d420 1.3466, nD20 1.5876, η 9.49 cP. IR
spectrum, ν, cm–1: 2989 m, 2950 m, 2897 m, 1481 w,
1457 m, 1402 m, 1395 m, 1361 m, 1331 m, 1291 s,
1172 s, 1133 s, 1058 s, 1030 s, 991 s, 958 s, 940 s, 904 s,
873 m, 806 s, 717 m, 690 m, 674 w, 629 m, 609 m,
546 m, 523 m, 453 w, 446 w. 1H NMR spectrum, δ, ppm:
1.30 t (3H, CH3, 3JHH = 7.1 Hz), 3.98 d. q (2H, CH3CH2,
1
548 s, 534 , 513 s, 477 m, 449 w. H NMR spectrum,
δ, ppm: 4.30 q (4H, CH2, 3JHF = 3JHР = 8.3 Hz), 7.03 m
(4H, C6H4). 13С NMR spectrum, δС, ppm: 60.2 q. d (CH2,
2
2
2JCF = 36.8, JCP = 7.7 Hz), 116.6 d (C3,5, C6H4, JCF
=
23.6 Hz), 121.6 t (C2,6, C6H4, 3JCF ≈ 3JCР = 7.5 Hz), 123.3 q
(CF3, JCF = 278.3 Hz), 147.1 (C1, C6H4), 159.7 d
1
1
(C4, C6H4, JCF = 243.4 Hz). 19F NMR spectrum, δF,
ppm: –118.6 q (FC6H4, 3JFH ≈ 4JFH = 6.1 Hz), –75.2 t. d
(CF3, 3JFH = 8.0, 4JFP = 4.0 Hz). 31P NMR spectrum: δP
133.5 ppm. Found, %: C 35.08; H 2.31; F 39.13; P 8.90.
C10H8F7O3P. Calculated, %: C 35.31; H 2.37; F 39.10;
P 9.11.
3JHP = 8.4, 3JHH = 7.1 Hz), 4.27 t. d (4H, CF2CH2, 3JHF
13.5, JHP = 6.6 Hz), 6.05 t. t (2H, CF2H, JHF = 52.2,
3JHF = 5.5 Hz). 13С NMR spectrum, δС, ppm: 16.6 d
=
3
2
3
2
(CH3, JCP = 5.2 Hz), 58.9 t. d (CF2CH2, JCF = 26.4,
2JCP = 9.2 Hz), 60.2 d (CH3CH2, JCP = 13.2 Hz),
107.8 t. t (CF2H, JCF = 253.7, JCF = 31.2 Hz),
111.1 t. q (CF2CF2CF2CF2H, JCF = 265.2, JCP
2
1
2
Symmetrization of phosphites 6c and 6d. Phosphite
6c or 6d (1 g) was placed in an ampoule, which was filled
with argon and then kept for 14 days. The reaction mixture
1
2
=
=
1
2
31.2 Hz), 115.0 t. t. d (OCH2CF2, JCF = 256.8, JCF
1
was analyzed with the H and 31P NMR spectroscopy
3
31.6, JCP = 4.4 Hz). 19F NMR spectrum, δF, ppm:
–137.4 d. m (CF2H, 2JHF = 52.0 Hz), –130.3 m (CF2CF2H),
–125.5 m (CF2CF2CF2H), –120.7 m (CH2CF2). 31PNMR
spectrum: δP 139.8 ppm. Found, %: C 26.68; H 2.11; F
56.33; P 5.55. C12H11F16O3P. Calculated, %: C 26.78; H
2.06; F 56.48; P 5.76.
methods. In the spectra, along with the signals of non-
symmetric phosphites 6c and 6d, there are the signals
of symmetric phosphites 7–9 (identified using authentic
samples). The ratio of compounds was 6c : 7 : 8 = 24 : 1 :
0.5 and 6d : 7 : 9 = 24 : 2 : 1. The spectral characteristics
of compounds 7–9 are identical to published data [34, 35].
Tris(2,2,2-trifluoroethyl) phosphite (7). 31P NMR
spectrum (CDCl3): δP 139.2 ppm (δP 139.3 ppm [34]).
Tris(4-methoxyphenyl) phosphite (8). 31P NMR
spectrum (CDCl3): δP 127.5 ppm (δP 128.9 ppm [35]).
4-Methoxyphenyl bis(2,2,2-trifluoroethyl) phosphite
(6c). Yield 15.3 g (67%), clear colorless liquid, bp
99‒100°C (1 mmHg), d420 1.4181, nD20 1.4314, η 5.27 cP.
IR spectrum, ν, cm–1: 3120 w, 3048 w, 3006 m, 2964 s,
2915 m, 2841 m, 1609 w, 1593 m, 1506 s, 1467 s, 1456 s,
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SYNTHESIS OF NON-SYMMETRIC FUNCTIONALIZED POLYFLUOROALKYL PHOSPHITES
843
Tris(4-fluorophenyl) phosphite (9). 31P NMR
spectrum (CDCl3): δP 127.7 ppm (δP 127.5 ppm [35]).
van Leeuwen, P.W.N.M., Eds., New York: John
Wiley and Sons, 2012, p. 81.
https://doi.org/10.1002/9781118299715.ch3
This work was performed using equipment of the Baikal
Analytical Center for Collective Use of the Siberian Branch
of the Russian Academy of Sciences.
13. Liu, R., Winston-McPherson, G.N., Yang, Z.-Y.,
Zhou, X., Song, W., Guzei, I.A., Xu, X., and Tang, W.,
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CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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