Synthesis and Isomer Composition of 2-Polyfluoroalkoxy-1,3,2-dioxaphospholanes and -phosphinanes

Article abstract of DOI:10.1134/S107036321804014X

Polyfluoroalkanols readily reacted with 2-chloro-1,3,2-dioxaphospholanes and 2-chloro-1,3,2-dioxaphosphinanes in hexane in the presence of triethylamine (–10 to 25°C, 5 h) to give 2-polyfluoroalkoxy-1,3,2- dioxaphospholanes and 2-polyfluoroalkoxy-1,3,2-dioxaphosphinanes in 48–72% yield. The products were found to exist as mixtures of cis and trans isomers with the trans isomer predominating for the phospholanes and cis isomer predominating for the phosphinanes according to the ¹H, ¹³C, ¹⁹F, and ³¹P NMR data.

Full text of DOI:10.1134/S107036321804014X

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 4, pp. 705–712. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © N.K. Gusarova, S.I. Verkhoturova, S.N. Arbuzova, T.I. Kazantseva, A.I. Albanov, A.M. Nalibaeva, G.K. Bishimbaeva, K.A. Apartsin,
V.V. Kireeva, B.A. Trofimov, 2018, published in Zhurnal Obshchei Khimii, 2018, Vol. 88, No. 4, pp. 623–630.
Synthesis and Isomer Composition
of 2-Polyfluoroalkoxy-1,3,2-dioxaphospholanes
and -phosphinanes
N. K. Gusarovaa, S. I. Verkhoturovaa, S. N. Arbuzovaa, T. I. Kazantsevaa, A. I. Albanova,
A. M. Nalibaevab, G. K. Bishimbaevab, K. A. Apartsinc, V. V. Kireevac, and B. A. Trofimova*
a Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*e-mail: boris_trofimov@irioch.irk.ru
b Sokol’skii Institute of Fuel, Catalysis, and Electrochemistry, ul. Kunaeva 142, Almaty, 050010 Kazakhstan
c Medical and Biological Research and Technology Department, Irkutsk Scientific Center,
Siberian Branch, Russian Academy of Sciences, ul. Lermontova 134, Irkutsk, 664033 Russia
Received November 9, 2017
Abstract—Polyfluoroalkanols readily reacted with 2-chloro-1,3,2-dioxaphospholanes and 2-chloro-1,3,2-dioxa-
phosphinanes in hexane in the presence of triethylamine (–10 to 25°C, 5 h) to give 2-polyfluoroalkoxy-1,3,2-
dioxaphospholanes and 2-polyfluoroalkoxy-1,3,2-dioxaphosphinanes in 48–72% yield. The products were
found to exist as mixtures of cis and trans isomers with the trans isomer predominating for the phospholanes
and cis isomer predominating for the phosphinanes according to the 1H, 13C, 19F, and 31P NMR data.
Keywords: 2-chloro-1,3,2-dioxaphospholanes, 2-chloro-1,3,2-dioxaphosphinanes, polyfluoroalkanols, 2-poly-
fluoroalkoxy-1,3,2-dioxaphospholanes, 2-polyfluoroalkoxy-1,3,2-dioxaphosphinanes
DOI: 10.1134/S107036321804014Х
1,3,2-Dioxaphospholanes and 1,3,2-dioxaphosphinanes
possessing a three-coordinate phosphorus atom are
continuously used as promising intermediate products
for the design of medicinal agents [1–4], efficient
ligands for the preparation of metal complex catalysts
[5–7], fire retardants for the protection of polymeric
materials [8–10], building blocks for organometallic
synthesis [11–17], and models for structural studies
[18–21]. In recent time, particular attention has been
given to directed synthesis of fluorinated phospholanes
and phosphinanes that are needed as incombustible and
oxidative additives to electrolytes [22–24]. Further-
more, the presence of pharmacophoric fluoroalkyl
groups [25, 26] in phosphorus-containing heterocycles
suggests enhanced pharmacological activity of these
compounds.
2-Polyfluoroalkoxy-1,3,2-dioxaphospholanes 5a–5c
were synthesized in 48–63% yields by reaction of
2-chloro-1,3,2-dioxaphospholanes 1 and 2 with poly-
fluoroalkanols 3 and 4 in the system triethylamine–
hexane under mild conditions (–10 to 25°C, 5 h;
Scheme 1). Under analogous conditions, 2-chloro-
1,3,2-dioxaphosphinanes 6 and 7 reacted with poly-
fluorinated alcohols 3 and 4 to afford 48–72% of
2-polyfluoroalkoxy-1,3,2-dioxaphosphinanes
8a–8c
(Scheme 2). 2-Polyfluoroalkoxy-1,3,2-dioxaphosphi-
nanes 8d and 8e were also obtained according to a two-
step procedure including initial preparation of
2,2,3,3,4,4,5,5-octafluoropentyl phosphorodichloridite
(9) and subsequent reaction of the latter with alkane-
1,3-diols 10a and 10b (pyridine–diethyl ether, –10 to
25°C, 5 h). Compounds 8d and 8e were isolated in 45
and 53% yield, respectively (Scheme 3).
The goal of the present work was to synthesize new
2-polyfluoroalkoxy-1,3,2-dioxaphospholanes and 2-poly-
fluoroalkoxy-1,3,2-dioxaphosphinanes and study in
detail their isomer composition.
The isomer composition of phospholanes 5 and
1
phosphinanes 8 was studied by H, 13C, 19F, and 31P
NMR spectroscopy, including two-dimensional homo-
705

706
GUSAROVA et al.
Scheme 1.
R
R
Et3N_hexane
_10_25°C, 5 h
O
O
H(CF2)nCH2OH
O
O
+
_Et3N HCl
P
P
Cl
OCH2(CF2)nH
3, 4
1, 2
5а−5c
R = H (1, 5а, 5b), Me (2, 5c); n = 2 (3, 5а), 4 (4, 5b, 5c).
Scheme 2.
Et3N_hexane
_10_25°C, 5 h
R
R
R
R
+
H(CF2)nCH2OH
_Et3N
HCl
O
O
O
O
P
P
OCH2(CF2)nH
Cl
6, 7
8а_8c
3, 4
R = H (6, 8а, 8b), Me (7, 8c); n = 2 (3, 8а), 4 (4, 8b, 8c).
Scheme 3.
R
R
O
Py_Et2O
_10_25°C, 5 h
_Py HCl
R
R
Cl
Cl
+
H(CF2)4CH2O
P
O
OH OH
P
OCH2(CF2)4H
8d, 8e
9
10а, 10b
R = H (8d, 10а), Me (8e, 10b).
and heteronuclear shift correlation techniques (COSY,
A considerably higher fraction of isomer A is likely
to be determined by higher thermodynamic stability of
the structure with trans orientation of the methyl
groups on C4 and C5. The isomers were identified on
1
HSQC, HMBC). According to the H, 13C, and 31P
NMR data, phospholanes 5a and 5b containing one
methyl group on the heterocycle exist as mixtures of
two isomers with cis and trans orientations of the
alkoxy group on the phosphorus atom and methyl
group on C4. The cis/trans isomer ratio was estimated
at 1:1.5, which reflected higher thermodynamic
stability of the trans isomer [27]. 4,5-Dimethyl-1,3,2-
phospholane 5c was found to exist as a mixture of
three isomers (Scheme 4). The major isomer (A, R,R/S,S
enantiomer pair) is characterized by trans orientation
of the two methyl groups, while the methyl groups in
the other two isomers, B and C (meso forms), are
oriented cis with respect to each other. The methyl
groups in B (R,S-cis, second abundant isomer) are oriented
cis with respect to the fluoroalkoxy substituent, and the
fluoroalkoxy group in C (R,S-trans, minor isomer)
appears in trans orientation with respect to both
methyl groups. The isomer ratio A:B:C is 7:2:1.
1
the basis of differences in their H, 13C, and 31P NMR
spectra [27, 28]. The phosphorus nucleus in the 2,4-
trans isomers of 5a and 5b resonated in the 31P NMR
spectra in a stronger field (by 3–4 ppm) relative to the
corresponding signal of their cis isomers. The 31P
signal of the R,S-trans isomer (C) is located in a
stronger field (δP 136–139 ppm) relative to those of the
R,R/S,S and R,S-cis isomers (A and B; δP 140–144 and
148–150 ppm, respectively). Protons of the methyl
groups oriented trans with respect to the substituent on
the phosphorus atom resonated 0.1 ppm upfield from
those of the cis-methyl groups. The 4-H and 5-H
signals of the trans isomer were located in a weaker
field (Δδ = 0.3–0.4 ppm). The vicinal coupling
3
constant JPC between the phosphorus nucleus and
methyl carbon nucleus in the trans position with
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SYNTHESIS AND ISOMER COMPOSITION
707
Scheme 4.
Me
Me
Me
O
P
O
P
O
P
Me
Me
Me
O
O
O
RO
RO
RO
B
C
A
respect to the fluoroalkoxy group is 3–6 Hz against
~1 Hz for the cis-methyl group.
(400.13, 101.61, 376.50, and 161.98 MHz, respec-
tively) from solutions in CDCl3; the chemical shifts
were measured relative to hexamethyldisiloxane (1H,
13C; internal standard), CFCl3 (19F, internal standard),
or 85% H3PO4 (31P, external standard). Signals in the
1H and 13C NMR spectra were assigned using two-
dimensional homo- and heteronuclear shift correlation
techniques (COSY, HSQC, HMBC). The IR spectra
were recorded from thin films on a Bruker IFS 25
spectrometer.
Phosphinanes 8a–8c were mixtures of two isomers
with cis and trans arrangements of the fluoroalkoxy
substituent on the phosphorus atom and methyl group
on C4 (C6), the cis isomer prevailing. The isomers were
identified on the basis of NMR data [29–31]. The 31P
signals of the trans isomers (axial orientation of the
substituent on the phosphorus atom) appeared in a
stronger field (by 4 ppm). The vicinal coupling constant
3JPC for the cis isomers was considerably higher (12–
16 Hz) than for the trans isomers (3JPC = 5 Hz)
[31, 32].
Initial 2-chloro-1,3,2-dioxaphospholanes 1 and 2
and 2-chloro-1,3,2-dioxaphosphinanes 6 and 7 were
synthesized from phosphorus trichloride and the cor-
responding diols [33]. 2,2,3,3,4,4,5,5-Octafluoropentyl
phosphorodichloridite (9) was synthesized from
phosphorus trichloride as described in [34].
It is known that unlike carbon analogs, 1,3-di-
oxanes, 2-substituted 1,3,2-dioxaphosphinanes prefer
axial orientation of the substituent on the phosphorus
atom [27, 32]. This is related to more favorable vicinal
interaction between lone electron pairs on the oxygen
atoms and vacant anti-bonding orbital of the P–X
bond. The fact that the major isomers of 8a–8c are cis
with equatorial orientation of the substituent on the
phosphorus atom is likely to be determined by the
length of the fluoroalkoxy group and kinetic control of
the reaction. The latter assumption was confirmed by
slow isomerization of 8a (with a relatively short
2-substituent) in CDCl3 solution: the initial cis/trans
ratio (8:1) changed to 1:1.3 in several days.
Analogous isomerization was observed previously
[32].
General procedure for the synthesis of 1,3,2-di-
oxaphospholanes 5a–5c and 1,3,2-dioxaphosphinanes
8a–8c. A solution of 2-chloro-1,3,2-dioxaphospholane
1 or 2 or 2-chloro-1,3,2-dioxaphosphinane 6 or 7 in
10 mL of hexane was added dropwise with stirring
over a period of 2 h to a solution of 0.05 mol of poly-
fluoroalkanol 3 or 4 and 6.1 g (0.06 mol) of tri-
ethylamine in 80 mL of hexane, maintaining the tem-
perature at –10 to –5°C. Triethylamine hydrochloride
separated from the solution as a white solid. The
cooling bath was removed, and the mixture was stirred
for 3 h at room temperature and left overnight. The
precipitate was filtered off and washed with hexane
(3×20 mL). The filtrate was combined with the
washings, the solvent was distilled off under reduced
pressure, and the residue was distilled in a vacuum.
Thus, convenient procedures have been developed
for the synthesis of new 2-polyfluoroalkoxy-1,3,2-
dioxaphospholanes and 2-polyfluoroalkoxy-1,3,2-dioxa-
phosphinanes from accessible alkanediols, fluorinated
alcohols, and phosphorus trichloride, and isomer
compositions of the isolated compounds have been
studied in detail.
4-Methyl-2-(2,2,3,3-tetrafluoropropoxy)-1,3,2-di-
oxaphospholane (5a). Yield 6.3 g (53%, cis/trans ratio
1:1.5), colorless liquid, bp 93–94°C (24 mm). IR
spectrum, ν, cm–1: 2984 s, 2936 m, 2901 m, 1457 m,
1385 m, 1303 m, 1289 m, 1231 s, 1207 s, 1127 s, 1107
s, 1076 s, 1066 s, 989 s, 938 m, 916 m, 864 s, 833 s,
EXPERIMENTAL
1
785 s, 750 s, 668 m, 622 m, 544 s, 484 m. H NMR
The 1H, 13C, 19F, and 31P NMR spectra were recorded
on Bruker DPX 400 and Bruker AV-400 spectrometers
spectrum, δ, ppm: trans isomer: 1.33 d (3H, CH3, 3JHH
6.2 Hz), 3.57 t.d (1H, 5-H, JHH = 8.3, JHH = JPH
=
=
2
3
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 4 2018

708
GUSAROVA et al.
2
7.4 Hz), 4.16 d.d.t and 4.07 d.d.t (2H, CH2CF2, JHH
=
52.0 Hz), –130.4 m (CF2CHF2), –125.4 m (CF2CF2CHF2),
–120.5 m (CH2CF2). 31P NMR spectrum, δP, ppm:
142.0 t (4JPF = 6.9 Hz, trans), 145.1 t (4JPF = 6.9 Hz,
cis). Found, %: C 28.30; H 2.58; F 44.94; P 8.92.
C8H9F8O3P. Calculated, %: C 28.59; H 2.70; F 45.22; P
9.22.
3
3
6.0, JHF = 1.5, JHP = 12.4 Hz), 4.30 d.d.d (1H, 5-H,
2JHH = 8.3, JHH = 6.7, JHP = 2.8 Hz), 4.59 d.d.q (1H,
3
3
3
3
4-H, JHH = 7.4, JHH = 6.7, 6.2 Hz), 5.88 t.t (1H,
2
3
CHF2, JHF = 53.2, JHF = 4.7 Hz); cis isomer: 1.44 d
(3H, CH3, 3JHH = 6.2 Hz), 3.70 t (1H, 5-H, 2JHH = 3JHH
=
=
2
8.9 Hz), 4.16 d.d.t and 4.07 d.d.t (2H, CH2CF2, JHH
4,5-Dimethyl-2-(2,2,3,3,4,4,5,5-octafluoropentyloxy)-
1,3,2-dioxaphospholane (5c). Yield 11.0 g (63%,
isomer ratio 7:2:1), transparent liquid, bp 115–116°C
(10 mm), d420 = 1.4917, nD20 = 1.3765. IR spectrum, ν,
cm–1: 2986 s, 2937 s, 1457 s, 1445 s, 1386 s, 1332 m,
1302 m, 1289 s, 1264 m, 1244 m, 1173 s, 1132 s, 1093
s, 1076 s, 1060 s, 1043 s, 1020 m, 993 m, 960 m, 932
s, 900 m, 870 m, 855 m, 808 m, 785 s, 767 s, 713 m,
689 w, 674 w, 618 m, 545 m, 525 w, 471 w, 457 w, 438
3
3
6.0, JHF = 1.5, JHP = 12.4 Hz), 4.21 d.d.d (1H, 5-H,
2JHH = 8.9, JHH = 6.5, JHP = 13.2 Hz), 4.34 m (1H,
3
3
2
3
CH), 5.88 t.t (1H, CHF2, JHF = 53.2, JHF = 4.7 Hz).
19F NMR spectrum, δF, ppm: trans isomer: –139.6 d
2
(CHF2, JFH = 53.2 Hz), –125.9 m (CF2); cis isomer:
–139.4 d (CHF2, JFH = 53.2 Hz), –125.8 m (CF2). 31P
2
NMR spectrum, δP, ppm: 140.3 (trans), 143.7 (cis).
Found, %: C 30.12; H 4.13; P 12.63. C6H9F4O3P.
Calculated, %: C 30.52; H 3.84; P 13.12.
1
m. H NMR spectrum, δ, ppm: R,R/S,S isomer: 1.32 d
3
3
4-Methyl-2-(2,2,3,3,4,4,5,5-octafluoropentyloxy)-
1,3,2-dioxaphospholane (5b). Yield 8.1 g (48%, cis/
trans ratio 1:1.5), transparent liquid, bp 106–108°C
(17 mm), d420 = 1.5240, nD20 = 1.3712. IR spectrum, ν,
cm–1: 2985 s, 2939 m, 2904 m, 1475 w, 1458 s, 1402
m, 1386 s, 1360 m, 1291 s, 1266 m, 1243 m, 1223 m,
1204 m, 1172 s, 1131 s, 1093 m, 1070 m, 1046 m,
1014 m, 990 s, 961 m, 944 m, 902 s, 864 s, 808 s, 772
s, 754 s, 733 m, 713 m, 689 m, 675 w, 620 m, 607 m,
(3H, CH3, JHH = 6.0 Hz), 1.38 d (3H, CH3, JHH =
6.0 Hz), 3.78 d.q.d (1H, CH, 3JHH = 8.5, 6.0, 3JHP = 3.8
3
Hz), 4.04 d.q (1H, CH, JHH = 8.5, 6.0 Hz), 4.19 t.d
3
3
(2H, CH2, JHF = 13.8, JHP = 8.4 Hz), 6.03 t.t (1H,
CHF2 JHF = 52.0, 3JHF = 5.4 Hz); R,S-cis isomer: 1.32
1
3
3
d (6H, CH3, JHH = 6.0 Hz), 4.22 t.d (2H, CH2, JHF
=
3
3
13.8, JHP = 8.4 Hz), 4.38 q.d.d (2H, CH, JHH = 6.0,
2.0, 3JHP = 4.5 Hz), 6.03 t.t (1H, CHF2, 1JHF = 52.0, 3JHF
=
=
=
3
5.4 Hz); R,S-trans isomer: 1.19 d (6H, CH3, JHH
6.0 Hz), 4.53 m (2H, CH), 6.03 t.t (1H, CHF2, JHF
52.0, JHF = 5.4 Hz); signals of the CH2 protons were
1
1
573 w, 560 w, 545 m, 520 w, 492 m. H NMR
spectrum, δ, ppm: trans isomer: 1.33 d (3H, CH3, 3JHH
=
3
2
3
6.2 Hz), 3.57 d.d.d (1H, 5-H, JHH = 8.5, JHH = 7.1,
overlapped by more intense signals of the other
3JHP = 7.7 Hz), 4.19 m (2H, CH2CF2), 4.30 d.d.d (1H,
isomers. C NMR spectrum, δC, ppm: R,R/S,S isomer:
13
2
3
3
5-H, JHH = 8.5, JHH = 6.6, JPH = 2.7 Hz), 4.61 d.d.q
17.9 d (CH3, 3JCP = 5.5 Hz), 18.8 (CH3), 59.6 t.d (CH2,
(1H, 4-H, 3JHH = 7.1, 3JHH = 6.6, 6.2 Hz), 6.047 t.t (1H,
2JCF = 26.5, JCP = 19.5 Hz), 78.5 d (CH, JCP
=
2
2
2
3
2
CHF2, JHF = 52.1, JHF = 5.4 Hz); cis isomer: 1.44 d
7.4 Hz), 80.7 d (CH, JCP = 8.1 Hz), 107.5 t.t (CHF2,
3
2
(3H, CH3, JHH = 6.2 Hz), 3.72 d.d (1H, 5-H, JHH
=
1JCF = 254.0, 2JCF = 31.0 Hz), 110.0 t.q (CF2CHF2, 1JCF
=
=
=
3JHH = 8.9 Hz), 4.19 m (2H, CH2CF2), 4.22 m (1H,
264.3, JCF = 31.0 Hz), 110.8 t.q (CF2CF2CH2, JCF
2
1
2
2
1
5-H), 4.34 m (1H, 4-H), 6.051 t.t (1H, CHF2, JHF
=
265.0, JCF = 31.3 Hz), 114.7 t.t.d (CF2CH2, JCF
52.0, JHF = 5.5 Hz). 13C NMR spectrum, δC, ppm:
256.2, 2JCF = 30.6, 3JCP = 4.1 Hz); R,S-cis isomer: 16.5
(CH3), 59.5 t.d (CH2, 2JCF = 26.5, 2JCP = 18.4 Hz), 76.4
3
3
trans isomer: 19.5 d (CH3, JCP = 4.0 Hz), 59.7 t.d
(CH2CF2, 2JCF = 26.4, 2JCP = 17.2 Hz), 70.4 d (C5, 2JCP
=
d (CH, JCP = 8.5 Hz), 107.5 t.t (CHF2, JCF = 254.0,
2
1
7.7 Hz), 72.7 d (C4, JCP = 8.1 Hz), 107.7 t.t (HCF2,
2JCF = 31.0 Hz), 110.0 t.q (CF2CHF2, 1JCF = 264.3, 2JCF
=
=
=
2
1JCF = 254.6, 2JCF = 30.8 Hz), 110.2 t.q (CF2CHF2, 1JCF
=
=
=
31.0 Hz), 110.8 t.q (CF2CF2CH2, JCF = 265.0, JCF
31.3 Hz), 114.7 t.t.d (CF2CH2, JCF = 256.2, JCF
1
2
2
1
1
2
264.5, JCF = 31.3 Hz), 111.0 t.q (CF2CF2CH2, JCF
2
1
3
264.8, JCF = 33.0 Hz), 114.9 t.t.d (CF2CH2, JCF
30.6, JCP = 4.1 Hz); R,S-trans isomer: 15.7 d (CH3,
2
3
2
255.7, JCF = 30.5, JCP = 3.7 Hz); cis isomer: 19.6
3JCP = 3.3 Hz), 74.8 d (CH, JCP = 7.4 Hz), 107.5 t.t
2
2
1
2
(CH3), 59.8 t.d (CH2CF2, JCF = 26.8, JCP = 18.7 Hz),
(CHF2, JCF = 254.0, JCF = 31.0 Hz), 110.0 t.q
69.7 d (C5, JCP = 7.3 Hz), 74.8 d (C4, JCP = 9.5 Hz),
(CF2CHF2, JCF = 264.3, JCF = 31.0 Hz), 110.8 t.q
2
2
1
2
107.7 t.t (CHF2, 1JCF = 254.6, 2JCF = 30.8 Hz), 110.2 t.q
(CF2CF2CH2, JCF = 265.0, 2JCF = 31.3 Hz), 114.7 t.t.d
1
1
2
(CF2CHF2, JCF = 264.5, JCF = 31.3 Hz), 111.0 t.q
(CF2CH2, 1JCF = 256.2, 2JCF = 30.6, 3JCP = 4.1 Hz); the
CH2 multiplet was overlapped by more intense signals
of the other isomers. 19F NMR spectrum, δF, ppm:
(CF2CF2CH2, JCF = 264.8, 2JCF = 33.0 Hz), 114.9 t.t.d
1
(CF2CH2, 1JCF = 255.7, 2JCF = 30.5, 3JCP = 3.7 Hz). 19F
2
1
NMR spectrum, δF, ppm: –137.5 d (CHF2, JFH
=
–137.4 d (CHF2, JFH = 52.0), –130.4 m (CF2CHF2),
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SYNTHESIS AND ISOMER COMPOSITION
709
–125.4 m (CF2CF2CHF2), –120.4 m (CH2CF2). 31P
NMR spectrum, δP, ppm: 139.5 t (4JPF = 7.2 Hz, R,S-
d420 = 1.4660, nD20 = 1.3804. IR spectrum, ν, cm–1: 2981
s, 2938 m, 2904 w, 1475 w, 1459 w, 1444 m, 1429 w,
1402 w, 1388 m, 1377 w, 1361 w, 1334 w, 1289 m,
1252 m, 1226 m, 1173 s, 1132 s, 1097 m, 1074 s, 1034
s, 982 m, 966 m, 925 s, 901 m, 887 m, 842 m, 809 m,
767 m, 752 s, 728 m, 629 w, 609 m, 573 w, 561 w, 546
m, 538 w, 520 w, 508 w, 487 w. 1H NMR spectrum, δ,
ppm: cis isomer (eq,eq): 1.39 d (3H, CH3, 3JHH = 6.3 Hz),
trans), 144.1 t (4JPF = 6.9 Hz, R,R/S,S), 149.7 (4JPF
=
8.6 Hz, R,S-cis). Found, %: C 30.64; H 2.92; F 43.36;
P 8.58. C9H11F8O3P. Calculated, %: C 30.87; H 3.17; F
43.41; P 8.85.
4-Methyl-2-(2,2,3,3-tetrafluoropropoxy)-1,3,2-
dioxaphosphinane (8a). Yield 9.0 g (72%, cis/trans
2
3
2.04 d.d.d.d (1H, 5-Heq, JHH = 14.3, JH-eq,H-ax = 10.8,
ratio 8:1), transparent liquid, bp 67°C (1 mm), d420
=
4
3JH-eq,H-ax = 7.3, JHP = 4.0 Hz), 2.15 m (1H, 5-Hax),
1.2936, nD20 = 1.4039. IR spectrum, ν, cm–1: 2980 s,
2937 s, 2904 m, 1476 m, 1457 m, 1413 w, 1386 s,
1351 w, 1337 w, 1253 s, 1233 s, 1209 m, 1106 s, 1066
s, 1034 s, 1005 m, 981 m, 966 m, 923 s, 886 m, 832 m,
748 s, 668 m, 653 w, 611 w, 583 w, 547 m, 523 m, 501
2
3
3
3.97 t.t.d (1H, 6-Hax, JHH ≈ JH-ax,H-ax = 11.3, JH-ax,H-eq
=
7.7, 3JHP = 4.4 Hz), 4.25 t.d (2H, CH2CF2, 3JHF = 14.0,
3JHP = 7.5 Hz), 4.33 m (1H, 6-He3q), 4.35 m (1H, 4-H),
2
6.04 t.t (1H, CHF2, JHF = 52.0, JHF = 5.5 Hz); trans
3
isomer (eq,eq): 1.20 d (3H, CH3, JHH = 6.3 Hz), 1.61
1
w, 487 w, 464 w, 398 w. H NMR spectrum, δ, ppm:
2
3
3
4
d.q (1H, 5-Heq, JHH = 14.3, JH-eq,H-eq ≈ JH-eq,H-eq ≈ JHP
≈
3
cis isomer (eq,eq): 1.40 d (3H, CH3, JHH = 6.6 Hz),
3JH-eq,H-ax ≈ 2.2 Hz), 2.06 m (1H, 5-Hax), 3.83 t.d.d (1H,
2
3
1.96 d.d.d.d (1H, 5-Heq, JHH = 14.9, JH-eq,H-ax = 10.8,
2
3
3
3
6-Hax, JHH ≈ JH-ax,H-ax = 10.8, JH-ax,H-eq = 4.7, JHP
=
7.3, 4JHP = 4.0 Hz), 2.12 m (1H, 5-Hax), 3.96 t.d.d (1H,
6-Hax, JHH ≈ JH-ax,H-ax = 11.3, JH-ax,H-eq = 7.3, JHP
4.2 Hz), 4.11 t.d (2H, CH2CF2, JHF = 12.6, JHP
1.9 Hz), 4.42 d.d.t (1H, 6-Heq, 2JHH = 10.6, 3JHP = 13.0,
2
3
3
3
=
=
3JH-eq,H-eq ≈ JH-eq,H-ax = 2.1 Hz), 4.55 m (1H, 4-H),
3
3
3
signals of the CH2CF2 and CHF2 protons were
overlapped by more intense signals of the cis isomer.
13C NMR spectrum, δC, ppm: cis isomer (eq,eq): 22.7
7.1 Hz), 4.31 m (1H, 6-Heq), 4.34 m (1H, 4-H), 5.92 t.t
2
3
(1H, CHF2, JHF = 53.3, JHF = 4.4 Hz); trans isomer
(eq,ax): 1.22 d (3H, CH3, 3JHH = 6.3 Hz), 1.62 d.q (1H,
3
2
(CH3), 32.8 d (C5, JCP = 11.8 Hz), 58.8 d (C6, JCP
=
2
3
3
4
5-Heq, JHH = 14.1, JH-eq,H-eq ≈ JH-eq,H-eq ≈ JHP
≈
2.6 Hz), 59.7 t.d (CH2CF2, 2JCF = 26.5, 2JCP = 21.4 Hz),
3JH-eq,H-ax ≈ 2.3 Hz), 2.08 m (1H, 5-Hax), 3.83 t.d.d (1H,
70.1 d (C4, JCP = 5.2 Hz), 107.7 t.t (HCF2, JCF
=
=
=
=
2
1
2
3
3
3
6-Hax, JHH ≈ JH-ax,H-ax = 10.7, JH-ax,H-eq = 4.5, JHP
=
=
=
2
1
254.3, JCF = 30.6 Hz), 110.0 t.q (HCF2CF2, JCF
254.1, JCF = 30.5 Hz), 111.0 t.q (CF2CF2CH2, JCF
265.0, JCF = 30.2 Hz), 115.2 t.t.d (CF2CH2, JCF
3
3
1.8 Hz), 4.11 t.d (2H, CH2CF22, JHF = 12.6, JHP
2
1
3
7.1 Hz), 4.42 d.d.t (1H, 6-Heq, JHH = 10.7, JH-eq,P
2
1
3
3
13.1, JH-eq,H-eq ≈ JH-eq,H-ax = 2.3 Hz), 4.55 m (1H, 4-H),
256.9, 2JCF = 30.6, 3JCP = 5.5 Hz); trans isomer (eq,ax):
21.2 d (CH32, 3JCP = 4.9 Hz), 35.4 d (C5, 3JCP = 4.8 Hz),
60.3 d (C6, JCP = 2.0 Hz), 66.6 (C4); signals of the H
(CF2)4CH2 fragment were overlapped by more intense
signals of the cis isomer. 19F NMR spectrum, δF, ppm:
cis isomer (eq,eq): –137.5 d.m (CHF2, 2JFH = 52.0 Hz),
–130.4 m (CF2CHF2), –125.4 m (CF2CF2CHF2),
–120.5 m (CH2CF2). 31P NMR spectrum, δP, ppm:
130.7 t (4JPF = 5.7 Hz, trans), 134.2 t (4JPF = 5.7 Hz,
cis). Found, %: C 30.61; H 3.16; F 43.62; P 9.12.
C9H11F8O3P. Calculated, %: C 30.87; H 3.17; F 43.41;
P 8.85.
5.93 t.t (1H, CHF2, JHF = 53.3, JHF = 4.4 Hz). 13C
2
3
NMR spectrum, δC, ppm: cis isomer (eq,eq): 22.8
3
2
(CH3), 32.8 d (C5, JCP = 11.4 Hz), 58.8 d (C6, JCP
=
2.6 Hz), 59.6 t.d (CH2CF2, 2JCF = 29.6, 2JCP = 18.7 Hz),
69.9 d (C4, JCP = 4.9 Hz), 109.2 t.t (HCF2, JCF
=
2
1
2
1
249.5, JCF = 34.9 Hz), 114.8 t.t.d (CF2, JCF = 253.3,
2JCF = 27.0, JCP = 6.5 Hz); trans isomer (eq,ax): 22.7
3
3
(CH3), 35.4 d (C5, JCP = 5.0 Hz), 60.0 t.d (CH2CF2,
2JCF = 29.5, 2JCP = 19.9 Hz), 60.2 d (C6, 2JCP = 2.6 Hz),
66.5 d (C4, JCP = 2.1 Hz), 109.3 t.t (HCF2, JCF
=
2
1
2
1
249.7, JCF = 35.3 Hz), 114.8 t.t.d (CF2, JCF = 250.0,
2JCF = 27.2, JCP = 6.5 Hz). 19F NMR spectrum, δF,
3
ppm: cis isomer (eq,eq): –138.9 d (CHF2, 2JFH = 52.6 Hz),
–125.4 m (CF2); trans isomer (eq,ax): –139.1 d (CHF2,
2JFH = 56.4 Hz), –125.6 m (CF2). 31P NMR spectrum,
δP, ppm: 129.8 (trans), 133.6 (cis). Found, %: C 33.59;
H 4.45; F 30.78; P 11.91. C7H11F4O3P. Calculated, %:
C 33.61; H 4.43; F 30.38; P 12.38.
4,4,6-Trimethyl-2-(2,2,3,3,4,4,5,5-octafluoropentyl-
oxy)-1,3,2-dioxaphosphinane (8c). Yield 9.14 g
(48%, cis/trans ratio 2:1), transparent liquid, bp 78–
79°C (1 mm), d420 = 1.4029, nD20 = 1.3874. IR spectrum,
ν, cm–1: 2982 s, 2938 s, 2880 m, 2832 m, 1459 m,
1383 s, 1374 s, 1336 m, 1307 s, 1289 s, 1281 s, 1245
m, 1229 m, 1206 m, 1173 s, 1132 s, 1089 s, 1045 s,
979 s, 963 s, 934 s, 901 s, 879 m, 827 m, 809 s, 764 s,
752 s, 726 m, 707 m, 688 w, 629 w, 606 m, 574 w, 563
4-Methyl-2-(2,2,3,3,4,4,5,5-octafluoropentyloxy)-
1,3,2-dioxaphosphinane (8b). Yield 12.6 g (72%, cis/
trans ratio 18:1), transparent liquid, bp 98°C (2 mm),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 4 2018

710
GUSAROVA et al.
w, 546 m, 538 w, 520 m, 478 w, 458 w, 393 w, 379 w.
ether was added dropwise over a period of 2 h with
stirring at that temperature. Pyridine hydrochloride
separated from the mixture as a white solid. The
cooling bath was removed, and the mixture was stirred
for 3 h at room temperature and left overnight. The
precipitate was filtered off and washed with diethyl
ether (3×20 mL). The filtrate was combined with the
washings, the solvent was distilled off under reduced
pressure, and the residue was distilled in a vacuum.
1H NMR spectrum, δ, ppm: cis isomer (eq,eq): 1.29 d
3
(3H, 6-CH3, JHH = 6.0 Hz), 1.35 s and 1.39 s (3H
2
each, 4-CH3), 1.68 d.d.d (1H, 5-Heq, JHH = 14.5,
4
2
3JH-eq,H-ax = JHP = 3.4 Hz), 2.44 d.d (1H, 5-Hax, JHH
=
=
=
3
3
14.5, JH=ax,H-ax = 13.1 Hz), 4.20 t.d (2H, CH2CF2, JHF
13.6, JHP = 7.0 Hz), 4.36 d.q.d.d. (1H, 6-Hax, JH-ax,H-ax
13.1, JH-ax,CH3 = 6.0, JH-ax,H-eq = 3.4, JHP = 2.8 Hz),
6.06 t.t (1H, CHF2, JHF = 52.0, JHF = 4.7 Hz); trans
3
3
3
3
3
2
3
3
isomer (eq,ax): 1.25 d (3H, 6-CH3, JHH = 6.2 Hz),
2-(2,2,3,3,4,4,5,5-Octafluoropentyloxy)-1,3,2-di-
1.29 s and 1.50 s (3H each, 4-CH3), 1.63 d.d.d (1H,
oxaphosphinane (8d). Yield 7.6 g (45%), transparent
2
3
4
5-Heq, JHH = 13.9, JH-eq,H-ax = 3.2, JHP = 2.0 Hz), 1.84
liquid, bp 73–74°C (1 mm), d420 = 1.5228, nD20
=
2
3
d.d (1H, 5-Hax, JHH3 = 13.9, JH-ax,H-ax = 11.6 Hz), 4.19
1.3804. IR spectrum, ν, cm–1: 2975 s, 2940 m, 2902 s,
2846 w, 1674 w, 1638 w, 1541 w, 1480 w, 1466 w,
1431 w, 1402 w, 1373 w, 1361 w, 1331 w, 1302 w,
1290 m, 1280 m, 1264 m, 1240 s, 1172 s, 1132 s, 1095
s, 1056 s, 1016 w, 992 m, 958 m, 938 s, 902 m, 891 m,
867 s, 809 m, 770 s, 745 s, 729 s, 689 m, 675 w, 629
w, 602 m, 574 w, 562 w, 547 m, 539 m, 522 w, 505 m,
3
t.d (2H, CH2CF2, JHF = 14.2, JHP = 7.2 Hz), 4.62
3
3
d.q.d.d (1H, 6-Hax, JH-ax,H-ax = 11.6, JH-ax,CH3 = 6.2,
3JH-ax,H-eq = 3.2, 3JHP = 2.8 Hz), 6.06 t.t (1H, CHF2, 2JHF
=
52.0, JHF = 5.6 Hz). 13C NMR spectrum, δC, ppm: cis
3
isomer (eq,eq): 23.6 (6-CH3), 28.2 d (4-CH3, ax, 3JCP
=
1.5 Hz), 31.7 (4-CH3, eq), 43.6 d (C5, JCP = 16.1 Hz),
3
59.7 d.t (CH2CF2, JCF = JCP2 = 26.5 Hz), 67.8 d (C6,
2
2
1
449 w, 411 m, 395 m. H NMR spectrum, δ, ppm:
2JCP = 6.1 Hz), 75.9 d (C4, JCP = 6.1 Hz), 107.6 t.t
2
3
1.61 d.t.t.d (1H, 5-Heq, JHH = 14.4, JH-eq,H-ax = 4.5,
1
2
(HCF2, JCF = 254.3, JCF = 31.4 Hz), 110.4 t.t
3JH-eq,H-eq = JHP = 2.0 Hz), 2.47 d.t.t (1H, 5-Hax, JHH
14.4, JH-ax,H-ax = 12.8, JH-ax,H-eq = 4.5 Hz), 3.85 d.d.d.d
(2H, 4-Heq, 6-Heq, JHH = 12.8, JHP = 10.0, JH-eq,H-ax
=
4
2
1
2
(HCF2CF2, JCF = 264.0, JCF = 30.6 Hz), 111.0 t.t
3
3
(CF2CF2CH2, JCF = 265.0, 2JCF = 30.0 Hz), 115.2 t.t.d
1
2
3
3
=
=
=
=
1
2
3
(CF2CH2, JCF = 255.8, JCF = 31.0, JCP = 7.3 Hz);
trans isomer (eq,ax), 22.7 d (6-CH3, JCP = 3.2 Hz),
3
3
4.5, JH-eq,H-eq = 2.0 Hz), 4.27 t.d (2H, CH2CF2, JHF
3
13.8, 3JHP = 7.4 Hz), 4.48 br.t (2H, 4-Hax, 6-Hax, 2JHH
3
28.0 (4-CH33, ax), 32.6 d (4-CH3, eq, JCP = 4.1 Hz),
3
2
12.8, JH-ax,H-ax = 12.8 Hz), 6.07 t.t (1H, CHF2, JHF
46.1 d (C5, JCP = 5.5 Hz), 59.9 d.t (CH2CF2, JCF
=
2
52.1, 3JHF = 5.6 Hz). 13C NMR spectrum, δC, ppm: 28.2
26.0, 2JCP = 24.9 Hz), 62.8 d (C6, 2JCP = 2.9 Hz), 76.6 d
d (C5, JCP = 5.5 Hz), 59.9 d (C4, C6, JCP = 1.8 Hz),
3
2
(C4, 2JCP = 7.4 Hz), 107.6 t.t (HCF2, 1JCF = 254.3, 2JCF
=
=
=
=
2
2
60.1 t.d (CH2CF2, JCF = 26.7, JCP = 21.3 Hz), 107.7
t.t (HCF2, JCF = 254.4, JCF = 31.0 Hz), 110.1 t.t
(HCF2CF2, JCF = 264.6, JCF = 30.8 Hz), 111.0 t.t
1
2
31.4 Hz), 110.4 t.t (HCF2CF2, JCF = 264.0, JCF
30.6 Hz), 111.0 t.t (CF2CF2CH2, JCF = 265.0, JCF
1
2
1
2
1
2
1
2
30.0 Hz), 115.2 t.t.d (CF2CH2, JCF = 255.8, JCF
1
2
(HCF2CF2CF2, JCF = 264.5, JCF = 31.6 Hz), 115.2
31.0, JCP = 7.3 Hz). 19F NMR spectrum, δF, ppm: cis
3
t.t.d (CF2CH2, 1JCF = 256.7, 2JCF = 30.4, 3JCP = 6.1 Hz).
2
isomer (eq,eq): –137.4 d.m (CHF2, JFH = 52.0 Hz),
19F NMR spectrum, δF, ppm: –137.4 d.m (CHF2, 2JFH
=
–130.4 m (CF2CHF2), –125.3 m (CF2CF2CHF2),
–120.2 m (CH2CF2); trans isomer (eq,ax): –137.4 d.m
52.1 Hz), –130.3
m
(CF2CHF2), –125.3
m
(CF2CF2CHF2), –120.5 m (CH2CF2). 31P NMR
spectrum: δP 132.2 ppm. Found, %: C 28.30; H 2.50; F
45.50; P 9.39. C8H9F8O3P. Calculated, %: C 28.59; H
2.70; F 45.22; P 9.22.
2
(CHF2, JFH = 52.0 Hz), –130.4 m (CF2CHF2), –125.4
m (CF2CF2CHF2), –120.5 m (CH2CF2). 31P NMR
spectrum, δP, ppm: 130.5 t (4JPF = 6.3 Hz, trans), 131.4
t (4JPF = 6.3 Hz, cis). Found, %: C 34.76; H 4.13; F
40.04; P 8.01. C11H15F8O3P. Calculated, %: C 34.93; H
4.00; F 40.19; P 8.19.
5,5-Dimethyl-2-(2,2,3,3,4,4,5,5-octafluoropentyl-
oxy)-1,3,2-dioxaphosphinane (8e). Yield 9.7 g (53%),
transparent liquid, bp 82°C (1 mm), d420 = 1.4467,
nD20 = 1.3839. IR spectrum, ν, cm–1: 2965 s, 2939 s,
2912 m, 2889 s, 1722 w, 1674 w, 1632 w, 1475 s, 1464
s, 1399 s, 1372 m, 1331 m, 1309 s, 1303 s, 1290 s,
1246 s, 1224 s, 1173 s, 1133 s, 1098 s, 1052 s, 1009 s,
964 s, 944 s, 910 s, 902 s, 867 w, 809 s, 793 s, 784 s,
754 s, 704 s, 689 s, 674 m, 624 s, 608 m, 573 m, 563
m, 546 m, 538 m, 522 w, 506 w, 461 m, 415 m, 383 m.
General procedure for the synthesis of 1,3,2-
dioxaphosphinanes 8d and 8e. A solution of 16.7 g
(0.05 mol) of 2,2,3,3,4,4,5,5-octafluoropentyl phosphoro-
dichloridite (9) in 150 mL of diethyl ether was cooled
to –10 to –5°C, and a solution of 0.05 mol of propane-
1,3-diol (10a) or 2,2-dimethylpropane-1,3-diol (10b)
and 7.9 g (0.1 mol) of pyridine in 15 mL of diethyl
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 4 2018

SYNTHESIS AND ISOMER COMPOSITION
711
1H NMR spectrum, δ, ppm: 0.75 s (3H, Me), 1.25 s
Döring, M., Polym. Adv. Technol., 2011, vol. 22, no. 7,
p. 1182. doi 10.1002/pat.1990
2
3
(3H, Me), 3.37 t (2H, 4-Heq, 6-Heq, JHH = 10.8, JHP
=
10.8 Hz), 4.13 br.d (2H, 4-Hax, 6-Hax, 2JHH = 10.8 Hz),
4.24 t.d (2H, CH2CF2, 3JHF = 13.9, 3JHP = 7.3 Hz), 6.06
10. Wendels, S., Chavez, T., Bonnet, M., Salmeia, K.A., and
Gaan, S., Materials, 2017, vol. 10, no. 7, p. 784. doi
10.3390/ma10070784
11. Lavrov, V.I., Atavin, A.S., Stankevich, V.K., Kalikhman, I.D.,
Parshina, L.N., and Trofimov, B.A., Zh. Org. Khim.,
1977, vol. 13, no. 4, p. 857.
12. Mironov, V.F., Konovalova, I.V., Burnaeva, L.M., and
Ofitserov, E.N., Russ. Chem. Rev., 1996, vol. 65, no. 11,
p. 935. doi 10.1070/RC1996v065n11ABEH000270
13. Kukhareva, T.S., Vasyanina, L.K., Antipin, M.Yu.,
Lysenko, K.A., Nifant’ev, E.E., and Soboleva, N.O.,
Russ. J. Gen. Chem., 2001, vol. 71, no. 4, p. 512. doi
10.1023/a:1012362630312
2
3
t.t (1H, CHF2, JHF = 52.1, JHF = 5.5 Hz). 13C NMR
spectrum, δC, ppm: 22.2 (CH3), 22.5 (CH3), 32.6 d (C5,
3JCP = 4.4 Hz), 60.0 t.d (CH2CF2, JCF = 26.4, JCP
=
2
2
21.6 Hz), 69.3 (C4, C6), 107.7 t.t (HCF2, JCF = 254.3,
1
2JCF = 31.0 Hz), 110.1 t.t (HCF2CF2, JCF = 265.2,
1
2JCF = 31.0 Hz), 111.0 t.t (CF2CF2CH2, JCF = 265.6,
1
2JCF = 30.4 Hz), 115.1 t.t.d (CF2CH2, JCF = 256.4,
1
2JCF = 30.6, JCP = 6.3 Hz). 19F NMR spectrum, δF,
3
2
ppm: –137.4 d.m (CHF2, JFH = 52.1 Hz), –130.4 m
(CF2CHF2), –125.4 m (CF2CF2CHF2), –120.6 m
(CH2CF2). 31P NMR spectrum: δP 123.6 ppm, t (4JPF
=
14. Constant, S. and Lacour, J., Top. Curr. Chem., 2005,
5.7 Hz). Found, %: C 33.21; H 3.72; F 42.02; P 8.62.
C10H13F8O3P. Calculated, %: C 32.98; H 3.60; F 41.74;
P 8.51.
vol. 250, p. 1. doi 10.1007/b100980
15. Freytag, M., Grunenberg, J., Jones, P.G., and
Schmutzler, R., Z. Anorg. Allg. Chem., 2008, vol. 634,
no. 8, p. 1256. doi 10.1002/zaac.200700514
16. Mironov, V.F., Dimukhametov, M.N., Efimov, S.V.,
Aminova, R.M., Karataeva, F.Kh., Krivolapov, D.B.,
Mironova, E.V., and Klochkov, V.V., J. Org. Chem.,
2016, vol. 81, no. 14, p. 5837. doi 10.1021/acs.joc.6b00356
17. Khasiyatullina, N.R., Mironov, V.F., Mironova, E.V.,
Krivolapov, D.B., and Litvinov, I.A., Russ. J. Gen.
Chem., 2016, vol. 86, no. 3, p. 551. doi 10.1134/
S1070363216030105
ACKNOWLEDGMENTS
This study was performed under financial support
by the President of the Russian Federation (program
for support of leading scientific schools, project no.
NSh-7145.2016.3) using the facilities of the Baikal
Joint Analytical Center, Siberian Branch, Russian
Academy of Sciences.
18. Vereshchagina, Ya.A., Ishmaeva, E.A., Chachkov, D.V.,
and Alimova, A.Z., Russ. J. Org. Chem., 2012, vol. 48,
no. 10, p. 1326. doi 10.1134/S1070428012100119
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