Synthesis of Amido- and Diamidophosphites with Polyfluoroalkyl Substituents

Article abstract of DOI:10.1134/S1070363220020103

Abstract: Bis(polyfluoroalkyl) chlorophosphites and polyfluoroalkyl dichlorophosphites react easily with secondary amines (from –40 to –22°C, 1–3 h, CH₂Cl₂) in the presence or absence of triethylamine to form the corresponding bis(po

Full text of DOI:10.1134/S1070363220020103

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 2, pp. 229–234. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 2, pp. 250–256.
Synthesis of Amido- and Diamidophosphites
with Polyfluoroalkyl Substituents
S. F. Malyshevaa, N. K. Gusarovaa, N. A. Belogorlovaa, A. M. Nalibayevab, S. V. Yaskoс,
N. A. Chernyshevaa, S. I. Verkhoturovaa, G. K. Bishimbayevab, 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, 050010 Kazakhstan
c Irkutsk State University of Communications, Irkutsk, 664074 Russia
*e-mail: boris_trofimov@irioch.irk.ru
Received July 15, 2019; revised July 15, 2019; accepted July 18, 2019
Abstract—Bis(polyfluoroalkyl) chlorophosphites and polyfluoroalkyl dichlorophosphites react easily with second-
ary amines (from –40 to –22°C, 1–3 h, CH2Cl2) in the presence or absence of triethylamine to form the corresponding
bis(polyfluoroalkyl) diorganylamidophosphites or bis(diorganylamido) polyfluoroalkyl phosphites in the yield of
up to 74%. Bis(polyfluoroalkyl) diorganylamidophosphites were also synthesized from diorganylamidodichloro-
phosphites and polyfluoroalkanols (–25 to –22°C, 2 h, Et3N–CH2Cl2) with a yield of 56–60%.
Keywords: polyfluoroalkyl dichlorophosphites, bis(polyfluoroalkyl) chlorophosphites, secondary amines, diorga-
nylamidodichlorophosphites, polyfluoroalkanols
DOI: 10.1134/S1070363220020103
Amido and diamidophosphites are widely used as
ligands for metal complexes [1–7], starting compounds
for nucleotide synthesis [8–13] and biomedical materials
[14], and also as building blocks for organic synthesis
[15–17]. Of special interest are fluorine-containing or-
ganic phosphites, which are promising precursors of drugs
[18–20], including for the treatment of socially significant
diseases [21, 22]. Amidopolyfluoroalkylphosphites are
also used as components for the creation of innovative
materials, for example, as effective non-combustible and
oxidative additives to electrolytes for Li-ion chemical
current sources [23, 24].
(from –25 to –22°C, 2 h, CH2Cl2) to form bis(2,2,2-tri-
fluoroethyl) diallylamido- and bis(2,2,2-trifluoroethyl)
diphenylamidophosphites 3a and 3b with a yield of
60 and 56%, respectively (Scheme 1).
Under similar conditions (from –25 to –22°C, 3 h,
CH2Cl2), bis(2,2,2-trifluoroethyl) chlorophosphite reacted
with an excess of dimethylamine, which is involved into
this process not only in the formation of bis(2,2,2-triflu-
oroethyl) dimethylamidophosphite 4 (yield 42%), but is
also a dehydrochlorinating agent (Scheme 2).
The use of polyfluoroalkyl dichlorophosphites 5–7 in
the reaction with secondary amines 8–10 led to the forma-
tion of bis(diorganylamido) polyfluoroalkylphosphites
11a–11e. The reaction proceeded in a triethylamine–
dichloromethane medium (from–40 to –22°C, 1–3 h); the
yield of diamidophosphites 11a–ereaches 74% (Scheme 3).
In this regard, the development of convenient
methods for the preparation of amido and diamido-
phosphites containing polyfluoroalkyl substituents is
an urgent task. For the synthesis of new representatives
of bis(polyfluoroalkyl) diorganylamidophosphites, we
proposed two approaches based on the reaction of dior-
ganylamidodichlorophosphites with polyfluoroalkanols
and the reaction of bis(polyfluoroalkyl) chlorophosphites
with secondary amines. Thus, diallylamidodichloro- and
diphenylamidodichlorophosphites 1a, 1b reacted with
2,2,2-trifluoro-1-ethanol 2 (molar ratio of reactants is 1 : 2)
in the presence of triethylamine at a low temperature
It should be noted that the reaction of amidodichloro-
phosphites 1a and 1b with trifluoroethanol 2 (Scheme 1),
as well as the reaction of polyfluoroalkyl dichloro-
phosphites 5–7 with secondary amines 8–10 (Scheme 3)
proceed selectively and practically quantitatively, as
evidenced by 31P NMR spectra of the reaction mixtures.
Further work-up and isolation of the reaction products 3
and 11 by vacuum distillation led to a decrease in their
preparative yield.
229

230
MALYSHEVA et al.
Scheme 1.
R
R
R
R
F
3C
O
O
Et Nꢀ
CH2Cl2
3
+ 2CF
N
PCl2
P
3CH2OH
N
ꢀ
Et N
HCl
·
3
F
3C
ꢀɚ, 1b
2
ꢁɚ, 3b
R1ꢀ ꢀɋɇ2 ɋ+ɋ+2 (
ɚ), Ph (b).
Scheme 2.
Me
Me
F
3C
O
F
F
3C
3C
O
O
CH2Cl2
P
N
+ Me
2NH
P
Cl
Me NH
ꢀ
HCl
·
2
O
F
3C
4
Scheme 3.
R1
N
R1
R1
R1
R1
+
Et3N
R
FOPCl2
2
R
P
FO
NH
N
ꢀEt N HCl
·
3
ꢀ
8 10
R1
ꢀ
5 7
ꢀ
ꢀꢀɚ 11e
1
1
R = CF CH , R = Et (ꢀꢀɚ, 56%); R = CF CH , R = H C=CHCH (11b, 67%);
F
3
2
F
3
2
2
2
1
1
R = H(CF ) CH , R = Me (11c, 52%); R = H(CF ) CH , R = H C=CHCH (11d, 68%);
F
2 2
2
F
2 2
2
2
2
1
R = H(CF ) CH , R = H C=CHCH (11e, 74%).
F
2 4
2
2
2
In summary, the convenient methods were developed
romethane. In similar manner, bis(2,2,2-trifluoroethyl)
chlorophosphite was prepared from PCl5 and bis(2,2,2-
trifluoroethyl) H-phosphonate in dichloromethane [25].
The starting bis(2,2,2-trifluoroethyl) H-phosphonate was
obtained from PCl3 and trifluoroethanol in the presence of
water [26]. Polyfluoroalkyl dichlorophosphites 5–7 were
synthesized from PCl3 and polyfluoroalkanols according
to the procedure [27]. Dimethylamine was generated in
a separate flask from dimethylamine hydrochloride and
aqueous KOH and used to synthesize compounds 4 and
11c as a solution in CH2Cl2. All the experiments were
carried out in a dry inert atmosphere (argon).
for the synthesis of previously unknown functional or-
ganophosphites with amido and polyfluoroalkyl substitu-
ents, which are promising intermediates for drug design.
EXPERIMENTAL
1Н, 13C, 19F, 31Р NMR spectra were registered on a
Bruker DPX 400 and a Bruker AV-400 spectrometers
(400.13, 101.61, 376.50, and 161.98 MHz, respectively)
from CDCl3 solution relative to internal HMDS (1Н, 13C)
or CFCl3 (19F), and external 85% H3PO4 (31P). To signals
assignment in the 1H, 13C NMR spectra, two-dimensional
homo- and heteronuclear NMR spectroscopy techniques
were used (COSY, HSQC, HMBC). IR spectra were re-
corded on a Bruker IFS 25 spectrometer from a thin layer.
General procedure for the synthesis of bis(2,2,2-
trifluoroethyl) organylamidophosphites 3a, 3b. A
solution of 0.1 mol of diorganylamidodichlorophosphite
1a or 1b in 50 mL of CH2Cl2 was added dropwise with
stirring over 1 h at a temperature from –25 to –20°C (dry
ice–acetone) to a solution of 0.2 mol (20.01 g) of 2,2,2-tri-
fluoro-1-ethanol 2 and 0.2 mol (20.24 g) of triethylamine
in 20 mL of CH2Cl2. In this case, a white precipitate was
formed (triethylammonium hydrochloride). Cooling
The starting N,N-diallylamidodichlorophosphite 1a
was obtained by an improved procedure [25] from N,N-di-
allylamine and PCl3 (1 : 1) in the presence of triethylamine
(3 mol %) in dichloromethane. Using the same procedure
[25], N,N-diphenylamidodichlorophosphite 1b was syn-
thesized from N,N-diphenylamine and PCl3 in dichlo-
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SYNTHESIS OF AMIDO- AND DIAMIDOPHOSPHITES
231
was removed, the reaction mixture was stirred at room
temperature for another 1 h, then 100 mL of hexane was
added. The resulting mixture kept overnight, after which
it was analyzed by 31P NMR. The spectra record the dis-
appearance of signals of the starting dichlorophosphites
(at 163.1 ppm for 1a and at 150.4 ppm for 1b) and the
appearance of signals of the final reaction products 3a
or 3b. Triethylammonium hydrochloride was filtered off
and washed with hexane (5 × 30 mL). Hexane washing
solution and the solvent from the filtrate were combined,
the solvents were distilled off under reduced pressure, the
residue was distilled in vacuum.
NMR spectrum: δP 141.8 ppm. Found, %: C 48.54; H
3.38; F 28.55; N 3.37; P7.68. C16H14F6NO2P. Calculated,
%: C 48.38; H 3.55; F 28.69; N 3.53; P 7.80.
Bis(2,2,2-trifluoroethyl) N,N-dimethylamido-
phosphite (4). To a solution of bis(2,2,2-trifluoroethyl)
chlorophosphite (0.08 mol, 21.16 g) in 120 mLof CH2Cl2
cooled to from –25 to –20°C (dry ice–acetone) was added
a freshly prepared solution of dimethylamine (0.44 mol,
19.84 g) in 60 mL of CH2Cl2 for 1 h with stirring. The
reaction mixture was stirred for another 1 h at –20°C and
1 h at room temperature, then kept overnight. Dimeth-
ylamine hydrochloride was filtered off and washed with
30 mL of CH2Cl2. Washings and the solvent from the
filtrate were combined, CH2Cl2 was removed under re-
duced pressure, and the residue was distilled in vacuum.
Yield 9.18 g (42%), clear liquid, bp 24–25°C (1 mmHg)
(bp 25°C (1 mmHg) [23]), nD20 1.3820 (nD20 1.3823 [21]).
1H NMR spectrum, δ, ppm: 2.67 d (6H, Me, 3JHP = 9.2
Hz), 3.99 quintet (2H, CH2, 3JHF = 3JHP = 8.4 Hz), 4.00
quintet (2H, CH2, 3JHF = 3JHP = 8.7 Hz). 31P NMR spec-
trum: δP 51.0 ppm. Found, %: C 26.17; H 3.44; F 41.91;
P 11.12. C6H10F6NO2P. Calculated, %: C 26.39; H 3.69;
F 41.74; P 11.34.
Bis(2,2,2-trifluoroethyl) N,N-diallylamido-
phosphite (3a). Yield 19.6 g (60%), clear liquid, bp 53°C
(1 mmHg), d420 1.3918, nD20 1.2514. IR spectrum, ν, cm–1:
3085 m, 2995 s, 2936 s, 2918 m, 2865 m, 1643 m, 1455
m, 1444 m, 1419 s, 1360 m, 1300 s, 1282 s, 1168 s, 1100
m, 1074 s, 994 m, 965 s, 927 s, 890 m, 848 s, 795 m, 772
s, 730 m, 652 m, 588 m, 553 m, 536 m, 509 w, 435 m, 422
m. 1H NMR spectrum, δ, ppm: 3.63 d. d. t (4H, NCH2,
3JHP = 9.4, 3JHH = 6.2, 4JHH = 1.0 Hz), 3.98 d. d. q and
4.07 d. d. q (4H, OCH2, 2JHН = 12.4, 3JHP = 6.6, 3JHF
8.8 Hz), 5.15 d. d. t (2H, CH2=, Htrans, 3JНН = 16.8, 2JHH
1.5, JHH = 1.0 Hz), 5.17 d. m (2H, CH2=, Hcis, JНН
=
=
=
General procedure for the synthesis of polyfluo-
roalkyl bis(diorganylamido)phosphites 11a–11e. A
solution of 0.25 mol of the secondary amine 8–10 and
0.25 mol (25.30 g) of triethylamine in 50 mL of CH2Cl2
was cooled to from –40 to –35°C (in the case of diethyl-
amine), from –25 to –20°C (when using dimethylamine)
or from –10 to –5°C (in the case of diallylamine).Asolu-
tion of 0.125 mol of polyfluoroalkyl dichlorophosphite
5–7 in 20 mL of CH2Cl2 was added dropwise to the
resulting solution at the indicated temperature over
20 min (using 2,2,2-trifluoroethyl dichlorophosphite or
2,2,3,3,4,4,5,5-octafluoropentyl dichlorophosphite) or
1 h (in the case of 2,2,3,3-tetrafluoropropyl phosphite).
Aprecipitate of triethylamine hydrochloride was formed.
The temperature of the reaction mixture was brought to
room temperature for 1 h with stirring, then 100 mL of
hexane was added. The mixture was kept overnight, after
4
3
10.6 Hz), 5.67 d. d. t (2H, CH=, 3JHH = 16.8, 3JHH = 10.6,
3JHH = 6.2 Hz). 13C NMR spectrum, δС, ppm: 46.2 d
2
2
(CH2N, JСP = 20.1 Hz), 61.5 q. d (CH2O, JCF = 36.1,
2JСР = 16.1 Hz), 117.7 (CH2=), 123.9 q. d (CF3, 1JCF
=
278.1, 3JCP = 8.7 Hz), 135.3 d (CH=, 3JCP = 2.7 Hz). 19F
NMR spectrum, δF, ppm: –75.5 t. d (CF3, 3JFН = 8.8, 4JFР =
6.1 Hz). 31P NMR spectrum: δP 151.3 ppm. Found, %: C
37.08; H 4.61; F 35.23; N 4.53; P 9.50. C10H14F6NO2P.
Calculated, %: C 36.93; H 4.34; F 35.05; N 4.31; P 9.52.
Bis(2,2,2-trifluoroethyl) N,N-diphenylamido-
phosphite (3b). Yield 22.2 g (56%), clear liquid, bp
103–104°C (1 mmHg). IR spectrum, ν, cm–1: 3402 m,
3087 w, 3039 m, 2938 m, 2888 w, 1594 s, 1510 m, 1490 s,
1451 m, 1416 m, 1301 s, 1281 s, 1258 m, 1168 s, 1096 s,
1067 s, 1030 m, 1007 w, 964 s, 915 w, 889 m, 847 m, 797 m,
1
31
751 s, 693 s, 655 m, 611 w, 555 m, 532 m, 487 w. H
which it was analyzed by P NMR. In the spectra, the
NMR spectrum, δ, ppm: 4.10 d. d. q and 4.14 d. d. q (4H,
disappearance of signals of the initial dichlorophosphites
5–7 in the range of 180–182 ppm and the appear-
ance of signals of the final products 11a–11e at 137–
142 ppm were recorded. The precipitate was filtered off
and washed with hexane (5×30 mL). Hexane washings
were combined with the filtrate solvent. The solvents were
distilled off under reduced pressure, and the residue was
distilled in vacuum.
2
3
3
OCH2, JHН = 12.4, JHP = 6.0, JHF = 8.4 Hz), 7.24 m
(4H, o-Ph), 7.36 m (4H, m-Ph), 7.33 m (2H, p-Ph). 13C
NMR spectrum, δС, ppm: 61.9 q. d (CH2O, 2JCF = 36.3,
1
3
2JCP = 16.8 Hz), 123.4 q. d (CF3, JCF = 278.4, JCP
=
8.0 Hz), 125.2 (Cp), 125.9 d (Co, JCP = 6.9 Hz), 129.3
(Cm), 143.6 d (Cipso, 2JCP = 10.3 Hz). 19F NMR spectrum,
δF, ppm: –75.0 t. d (CF3, 3JFH = 8.4, 4JFP = 6.5 Hz). 31P
3
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MALYSHEVA et al.
2,2,2-Trifluoroethyl bis(diethylamido)phosphite
5.90 t. t (1H, HCF2, 2JHF = 53.3, 3JHF = 5.1 Hz). 13C NMR
(11а). Yield 19.2 g (56%), clear liquid, bp 78–80°C
(1 mmHg). Compound 11a crystallizes when distilled,
colorless crystals, mp 56–69°С. IR spectrum, ν, cm–1:
2971 s, 2934 s, 2871 s, 2726 w, 1463 s, 1415 m, 1377 s,
1345 w, 1281 s, 1190 m, 1189 m, 1162 s, 1100 s, 1074 s,
1024 s, 1011 s, 965 s, 923 m, 845 m, 789 m, 768 w,
672 m, 649 w, 560 w, 533 w, 526 w, 496 w, 479 w. H
NMR spectrum, δ, ppm: 1.02 t (12H, Me, 3JHH = 7.1 Hz),
2.93 and 3.05 d. d. q (8H, NCH2, 2JHH = 16.6, 3JHP = 9.7,
spectrum, δС, ppm: 36.2 and 36.4 (Me), 61.4 t. d (CH2,
2
1
2JCF = 29.5, JCP = 17.6 Hz), 109.2 t. t (HCF2, JCF
=
249.3, 2JCF = 34.80 Hz), 115.2 t. t. d (CF2, 1JCF = 249.9,
2JCF = 26.4, 3JCP = 8.5 Hz). 19F NMR spectrum, δF, ppm:
–149.3 d (HCF2, 2JHF = 53.3 Hz), –126.3 (CF2). 31PNMR
spectrum: δP 142.0 ppm. Found, %: C 33.59; H 6.13; F
30.58; N 11.09; P 12.33. C7H15F4N2OP. Calculated, %:
C 33.61; H 6.04; F 30.38; N 11.20; P 12.38.
1
2,2,3,3-Tetrafluoropropyl bis(diallylamido)phos-
phite (11d). Yield 30.1 g (68%), viscous pale yellow
liquid, bp 98–99°C (1 mmHg), d420 1.1390, nD20 1.4527.
IR spectrum, ν, cm–1: 3082 m, 3009 m, 2982 m, 2917 m,
2858 m, 2793 w, 2732 w, 2670 w, 2423 w, 1679 w, 1642 m,
1442 m, 1419 s, 1359 m, 1280 s, 1259 s, 1231 s, 1207 s,
1109 s, 1049 m, 993 s, 927 s, 833 m, 762 m, 670 w, 548
m. 1H NMR spectrum, δ, ppm: 3.47 d. d. d (4H, NCH2,
2JHH = 15.2, 3JHP = 9.0, 3JHH = 6.1 Hz), 3.60 d. d. d (4H,
NCH2, 2JHH = 15.2, 3JHP = 8.7, 3JHH = 6.4 Hz), 3.92 t. d
(2H, CH2O, 3JHF = 12.5, 3JHP = 6.1 Hz), 5.12 br. d (4H,
CH2=, Htrans, 3JHH = 17.9 Hz), 5.13 br. d (4H, CH2=, Hcis,
3JHH = 9.4 Hz), 5.68 m (4H, CH=), 5.92 t. t (1H, HCF2,
2JHF = 53.3, 3JHF = 5.4 Hz). 13C NMR spectrum, δС, ppm:
3JHH = 7.1 Hz), 3.86 d. q (2H, CH2O, 3JHP = 7.7, 3JHF
8.8 Hz). 13C NMR spectrum, δС, ppm: 14.6 d (Me, 3JCP
=
=
2.3 Hz), 38.9 d (NCH2,2JCP = 19.5 Hz), 61.9 q. d (CH2O,
2JCF = 35.2, 2JCP = 21.0 Hz), 124.3 q. d (CF3, 1JCF = 278.4,
3JCP = 10.7 Hz). 19F NMR spectrum, δF, ppm: –75.2 t. d
(CF3, 3JFH = 8.8, 4JFР = 6.8 Hz). 31P NMR spectrum: δP
140.7 ppm. Found, %: C 43.54; H 8.18; F 20.55; N 10.07;
P 11.38. C10H22F3N2OP. Calculated, %: C 43.79; H 8.09;
F 20.78; N 10.21; P 11.29.
2,2,2-Trifluoroethyl bis(diallylamido)phosphite
(11b). Yield 26.9 g (67%), clear liquid, bp 82–83°C
(1 mmHg), d420 1.0981, nD20 1.4520. IR spectrum, ν, cm–1:
3080 m, 3009 w, 2981 m, 2903 m, 2848 m, 1640 m,
1439 m, 1417 s, 1349 m, 1280 s, 1162 s, 1095 s, 1049 m,
47.8 d (NCH2, 2JCP = 18.8 Hz), 61.9 t. d (CH2O, 2JCF
30.3, 2JCP = 19.9 Hz), 109.2 t. t (HCF2, 1JCF = 249.6, 2JCF =
=
1
993 s, 921 s, 846 m, 759 s, 648 w, 585 w, 555 m. H
1
2
NMR spectrum, δ, ppm: 3.46 d. d. d (4H, NCH2, 2JHH
=
34.3 Hz), 115.2 t. t. d (CF2, JCF = 250.0, JCF = 26.5,
3JCP = 10.2 Hz), 116.8 (CH2=), 136.0 (CH=). 19F NMR
15.2, 3JHP = 8.9, 3JHH = 6.1 Hz), 3.61 d. d. d (4H, NCH2,
3
3
2
2JHH = 15.2, JHP = 8.4, JHH = 6.1 Hz), 3.92 d. q (2H,
CH2O, 3JHР = 8.2, 3JHF = 8.7 Hz), 5.10 d (4H, CH2=, Htrans
3JНН = 17.9 Hz), 5.10 d (4H, CH2=, Hcis, 3JНН = 9.7 Hz),
spectrum, δF, ppm: –139.9 d (HCF2, JHF = 53.3 Hz),
,
–125.9 (CF2). 31P NMR spectrum: δP 137.5 ppm. Found,
%: C 50.81; H 6.53; F 21.40; N 7.89; P 8.71. C15H23F-
4N2OP. Calculated, %: C 50.85; H 6.54; F 21.45; N 7.91;
P 8.74.
3
3
3
5.67 d. d. t (4H, CH=, JНН = 17.9, JНН = 9.7, JHH
=
6.1 Hz). 13C NMR spectrum, δС, ppm: 47.7 d (NCH2,
2JCP = 18.4 Hz), 62.4 q. d (CH2O, JCF = 35.6, JCP
2
2
=
2,2,3,3,4,4,5,5-Octafluoropentyl bis(diallylamido)-
phosphite (11e). Yield 42.0 g (74%), yellow liquid,
bp 123–124°C (1 mmHg), d420 1.2302, nD20 1.4318. IR
spectrum, ν, cm–1: 3082 m, 3010 m, 2983 m, 2909 m,
2852 m, 1641 m, 1441 m, 1419 s, 1359 m, 1289 m,
1259 m, 1233 m, 1172 s, 1132 s, 1094 m, 1046 m, 993 s,
20.8Hz), 117.0(CH2=), 124.1q. d(CF3, 1JCF =278.0,3JCP =
10.8 Hz), 136.0 d (CH=, 3JCP = 2.4 Hz). 19F NMR spec-
trum: δF –75.1 ppm. 31P NMR spectrum: δP 139.7 ppm.
Found, %: C 52.02; H 6.78; F 17.48; N 8.54; P 9.98.
C14H22F3N2OP. Calculated, %: C 52.17; H 6.88; F 17.68;
N 8.69; P 9.61.
1
923 s, 905 m, 848 w, 808 m, 763 m, 672 w, 547 m. H
2,2,3,3-Tetrafluoropropyl bis(dimethylamido)phos-
phite (11c). Yield 16.3 g (52%), clear liquid, bp 30–31°C
(1 mmHg), d420 1.1619, nD20 1.4067. IR spectrum, ν, cm–1:
2994 m, 2972 m, 2923 s, 2884 s, 2839 s, 2795 s, 1484 m,
1462 s, 1454 s, 1409 w, 1352 w, 1277 s, 1229 s, 1201 s,
1134 m, 1121 s, 1082 s, 976 s, 955 s, 832 s, 771 s, 685 s,
659 m, 584 w, 548 s, 532 w, 506 w, 456 w, 409 m. H
NMR spectrum, δ, ppm: 2.52 s and 2.55 s (12H, Me),
3.87 t. d. t (2H, CH2, 3JHF = 12.6, 3JHP = 6.9, 4JHF = 1.6 Hz),
NMR spectrum, δ, ppm: 3.46 d. d. d and 3.59 d. d. d (8H,
NCH2, 2JHH = 15.3, 3JHP = 8.3, 3JHH = 6.1, 3JHH = 6.6 Hz),
3
3
4
4.02 t. d. t (2H, CH2O, JHF = 14.0, JPH = 6.8, JHF
=
3
1.4 Hz), 5.10 br. d (4H, CH2=, Htrans, JHH = 17.7 Hz),
5.10 br. d (4H, CH2=, Hcis, 3JHH = 9.5 Hz), 5.65 d. d. d. d
3
3
3
3
(4H, CH=, JHH = 17.7, JHH = 9.5, JHH = 6.1, JHH
=
6.6 Hz), 6.03 t. t (1H, HCF2 JHF = 52.0, 3JHF = 5.6 Hz).
1
2
13C NMR spectrum, δС, ppm: 47.7 d (NCH2, JCP
=
2
19.0 Hz), 61.6 t. d (CH2O, 2JCF = 25.9, 2JCP = 21.6 Hz),
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SYNTHESIS OF AMIDO- AND DIAMIDOPHOSPHITES
233
107.7 t. t (HCF2, 1JCF = 253.5, 2JCF = 31.0 Hz), 109.9 m
(CF2CF2CF2), 111.0 t. quintet (HCF2CF2, 1JCF = 264.2,
9. Uzagare, M.C., Claussnitzer, I., Gerrits, M., and Bann-
warth, W., ChemBioChem, 2012, vol. 13, p. 2204.
https://doi.org/10.1002/cbic.201200528
1
2JCF = 30.6 Hz), 115.6 t. t. d (CF2CH2, JCF = 256.5,
2JCF = 30.2, 3JCP = 9.5 Hz), 116.9 (CH2=), 136.0 d (CH=,
3JCP = 2.6 Hz). 19F NMR spectrum, δF, ppm: –137.2 d. m
10. Durantie, E., Huwiler, S., Leroux, J.-Ch., and Cast-
agner, B., Org. Lett., 2016, vol. 18, no. 13, p. 3162.
https://doi.org/10.1021/acs.orglett.6b01374
11. Jud, L. and Micura, R., Chem. Eur. J., 2016, vol. 23,
no. 14, p. 3406.
2
(2F, HCF2, JHF = 51.9 Hz), –130.3 m (2F, HCF2CF2),
–125.2 m (2F, HCF2CF2CF2), –120.0 m (2F, CF2CH2).
31P NMR spectrum: δP 139.8 ppm. Found, %: C 44.83; H
5.09; F 33.18; N 6.04; P6.76. C17H23F8N2OP. Calculated,
%: C 44.94; H 5.10; F 33.45; N 6.17; P 6.82.
https://doi.org/10.1002/chem.201605056
12. Michaelides, I.N., Tago, N., Viverge, B., and Carell, T.,
Chem. Eur. J., 2017, vol. 23, no. 63, p. 15894.
https://doi.org/10.1002/chem.201704216
ACKNOWLEDGMENTS
13. Pujari, S.S. and Tretyakova, N., Chem. Res. Toxic., 2017,
vol. 30, no. 1, p. 434.
https://doi.org/10.1021/acs.chemrestox.6b00392
14. Skorenrski, M., Oleksyszyn, J., and Sienrczyk, M.,
Tetrahedron Lett., 2013, vol. 56, p. 1566.
This work was performed using the equipment of the Baikal
Analytical Center for Collective Use of the Siberian Branch of
the Russian Federation.
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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