Reactions of polyfl uoroalkanethioamides with tris(diethylamino)phosphine

Article abstract of DOI:10.1134/S1070428013110031

Structure of reaction products obtained from tris(diethylamino)phosphine with N,Ndialkylpolyfl uoroalkanethioamides depends on the length of the polyfl uoroalkyl substituent in the latter. In the case of morpholides of perfl uorothiopropionic and perfl uorothiobutyric acids the main reaction products are fl uoro-containing aminoacetylenes: 4-(perfl uoroalkan-1-yn-1-yl)morpholines, and also tris(diethylamino)phosphine sulfide and tris(diethylamino)difl uorophosphorane. From morpholides or piperidides of ω-H-perfl uorothiovaleric acid with a longer perfl uoroalkyl substituents amides of cis- and trans-perfl uoropent-2-enethiocarboxylic acids were obtained. Pleiades Publishing, Ltd., 2013.

Full text of DOI:10.1134/S1070428013110031

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 11, pp. 1572−1579. © Pleiades Publishing, Ltd., 2013.
Original English Text © N.V. Pikun, S.S. Mykhaylychenko, E.B. Rusanov, Yu.G. Shermolovich, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49,
No. 11, pp. 1597−1603.
Reactions of Polyfluoroalkanethioamides
with Tris(diethylamino)phosphine
N. V. Pikun, S. S. Mykhaylychenko, E. B. Rusanov, and Yu. G. Shermolovich
Institute of Organic Chemistry, National Academy of Sciences of Ukraine
Kiev, 02094 Ukraine
e-mail: sherm@ioch.kiev.ua
Received May 18, 2013
Abstract—Structure of reaction products obtained from tris(diethylamino)phosphine with N,N-
dialkylpolyfluoroalkanethioamides depends on the length of the polyfluoroalkyl substituent in the latter. In the
case of morpholides of perfluorothiopropionic and perfluorothiobutyric acids the main reaction products are
fluoro-containing aminoacetylenes: 4-(perfluoroalkan-1-yn-1-yl)morpholines, and also tris(diethylamino)phosphine
sulfide and tris(diethylamino)difluorophosphorane. From morpholides or piperidides of ω-Н-perfluorothiovaleric
acid with a longer perfluoroalkyl substituents amides of cis- and trans-perfluoropent-2-enethiocarboxylic acids
were obtained.
DOI: 10.1134/S1070428013110031
One of the widespread modern approaches to the
synthesis of organofluorine compounds consists in the uti-
lization of simple reactive fluorine-containing molecules
(building-blocks) for the preparation of more complex
substances. Compounds of diverse classes are used as
these building-blocks [1]. In particular, the research in
our laboratory on the synthetic opportunities provided by
chlorides, esters, and thioesters of perfluoroalkanethio-
carboxylic acids made it possible to develop procedures
for the preparation of fluorinated heterocyclic compounds
of diverse classes [2].Among the other derivatives of the
perfluoroalkanethiocarboxylic acids possessing promis-
ing opportunities for the application in organic synthesis
amides of these acids stand out against the acyl halides
and the esters due first of all to their higher availability
[3, 4].
We showed formerly that reactions of perfluoro-
alkanethioamides with organometallic compounds
(С-nucleophiles) could be used for the preparation of
fluorine-containing keten-N,S-acetals [5] and heterocyclic
substances [6], and the reaction of polyfluoroalkane-
thiocarboxylic acids N,N-dialkylamides I with trialkyl
phosphites led to the formation of fluorine-containing de-
rivatives of α-aminophosphonates of saturated and un-
Scheme 1.
X
O
S
P(OEt)2
P(OEt)3
RF
F
N
P(OAlk)3
RFCF2
F3C
100_150°C
150°C
N
N
P(OAlk)2
O
X
O
Iа, Ib
IIа, IIb
III
RF = CF3, X = O (а); RF = C2F5, X = CH2 (b).
1572

REACTIONS OF POLYFLUOROALKANETHIOAMIDES
1573
Scheme 2.
O
SEt
N
P(OEt)2
(EtO)3P
S
RF
RF
RF
150°C, 12 h
CH3
HN
CH3
CH3
HN
IVа, IVb
VIа, VIb
Vа, Vb
RF = CF3 (а), H(CF2)4 (b).
saturated structure [7] (Scheme 1).
already at room temperature. In the event of thioamides
Iа, Ib the main reaction products were 4-(perfluoroalkan-
1-yn-1-yl)morpholines VIIа, VIIb formed in the yields
no less than 90% (according to 19F NMR spectra of the
reaction mixture), and also tris(diethylamino)phosphine
sulfide and tris(diethylamino)difluorophosphorane
(Scheme 3). Ynamines VIIа, VIIb were isolated from the
reaction mixtures as solutions in diethyl ether by distilla-
tion in a vacuum into a trap cooled by liquid nitrogen. Like
the known compounds of this type with trifluoromethyl
substituent [8, 9] these compounds are thermally unstable
and slowly decompose at the attempt to isolate them in
the individual state by evaporation of diethyl ether at the
atmospheric pressure. The formation of ynamines VII
was proved by the hydrolysis of their ether solutions to
amides VIIIа, VIIIb (Scheme 3).
The reaction of N-p-tolyl thioamides IVа, IVb with
triethyl phosphite under similar conditions provided
the derivatives of α-aminophosphonates Vа, Vb and
of S-ethylthioimidates VIа, VIb (Scheme 2). Yet the
polyfluoroalkanethiocarboxylic acids N-alkylamides did
not react with triethyl phosphite at a prolonged heating
at 150°С.
The disadvantage of these reactions consists in the
necessity of prolonged heating at relatively high tempera-
ture. Therefore the attempts to study in these reactions the
behavior of more nucleophilic derivatives of the three-
valent phosphorus appeared promising.
The goal of this study was the investigation of reac-
tions between N,N-dialkylperfluoroalkanethioamides
Iа–Id with such phosphorus-containing nucleophile as
tris(diethylamino)phosphine.
On the contrary, the main products of the reaction
of ω-Н-perfluorothiovaleric acid amides Ic, Id with
tris(diethylamino)phosphine were morpholide Xа and
We found that in contrast to trialkyl phosphites the
tris(diethylamino)phosphine reacted with thioamides I
Scheme 3.
S
P(NEt2)3
(Et2N)3P=S
RFCF2
RF
N
O
(Et2N)3PF2
Et2O, 20oC
N
VIIа, VIIb
O
5% HCl
Iа, Ib
O
N
RF
O
VIIIа, VIIIb
RF = CF3 (а), CF3CF2 (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

PIKUN et al.
1574
Scheme 4.
_
F
F
+
RF
S
S
RF
F
P(NEt2)3
P(NEt2)3
RFCF2
F
N
X
N
N
X
X
IXа, IXb
Xа, Xb
Ic, Id
Z/E 50 : 50 (Xа);
Z/E 60 : 40 (Xb).
I, RF = H(CF2)3, X = O (c); RF = H(CF2)3, X = CH2 (d); IX, RF = H(CF2)3, X = O (a); RF = H(CF2)3, X = CH2 (b); X, RF =
H(CF2)2, X = O (а); RF = H(CF2)2, X = CH2 (b).
piperidide Xb of perfluoro-2-pentenethiocarboxylic acid
existing as mixtures of cis- and trans-isomers. Besides
tris(diethylamino)phosphonium fluorides IXа, IXb were
isolated from the reaction mixture in 13−15% yield
(Scheme 4).
The structure of cis-isomer Xa was proved by XRD
analysis (see the figure).
Molecule of compound Xa has the cis-orientation of
the fluorine atoms with respect to the double bond С6=С7,
torsion angle F1C6C7F2 is –1.02(18)°. The C–F bond
lengths are in a fairly narrow range, 1.343(2)–1.3652(16)
Å. The morpholine ring has a common structure. The sum
of the bond angles at the atom N1 is 359.99(11)°, and
the bond C5–N1 is shortened to 1.3307(16) Å, which is
considerably less than the standard value of the ordinary
С–N bond (1.45 Å) because of the efficient conjugation
of the unshared electron pairs of the nitrogen atom with
the π-system of the C=S bond.
It should be noted that compounds X are the specimens
of previously virtually unknown type of derivatives of
α,β-unsaturated thiocarboxylic acids containing fluorine
atoms at the С=С bond. The first representative of this
type thioamide was described in [4].
The obtained experimental findings show that the
outcome of the reaction between polyfluoro-alkaneth-
ioamides and tris(diethylamino)phosphine is governed
by the length of the polyfluoroalkyl substituent. We sug-
gest a scheme of the reaction course including a series
of successive transformations: thiophilic attack of the
tris(diethylamino)phosphine on the thioamide molecule
giving a zwitter-ion XI that transforms into ylide XII
through a stage of formation of carbene XIII or three-
membered phosphorane XIV. The decomposition of
ylide XII occurs through the stage of formation of fluoro-
phosphoranes XVI and phosphonium fluorides IX which
convert into ynamines VIIа, VIIb. The intermediate
formation of compound IX was confirmed in the case of
thioamide Ib by the formation of phosphonium salt XV at
the addition to the reaction mixture of copper(II) triflate.
Phosphonium fluorides IXа, IXb were isolated in small
yields directly from the reaction mixtures in reactions of
thioamides Ic, Id but here the predominant direction of
zwitter-ion XI transformation was not the formation of
General view of the molecule of (2Z)-2,3,4,4,5,5-hexafluor-
opent-2-enethiocarboxylic acid morpholide (Xа). Main geo-
metric parameters are as follows: C5–C6 1.4934(18), C5–S1
1.6626(13), C6–C7 1.3214(19), C7–C8 1.4936(19), C8–C9
1.534(2) Ǻ; N1C5C6 115.49(11), C7C6C5 128.97(12), C6C7C8
128.28(12), C7C6F1 117.69(12), F1C6C5 113.34(11), C6C7F2
120.16(12), F2C7C8 111.54(11)°.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

REACTIONS OF POLYFLUOROALKANETHIOAMIDES
1575
Scheme 5.
+
S
S P(NEt2)3
P(NEt2)3
_
RFCF2CF2
RFCF2CF2
N
N
X
X
I
XI
RF = H(CF2)2
X = O, CH2
X = O
X = O
(Et2N)3P=S
P(NEt2)3
(Et2N)3P
F
P(NEt2)3
S
F
F
S
RFCF2CF2
RF
P(NEt2)3
RFCF2CF2
N
N
F
N
X
O
O
XIII
XIV
XVII
(Et2N)3P=S
(Et2N)3PF2
+
F
F
RFCF2
F
P(NEt2)3
RF
S
_
N
O
F
N
X
XII
Xа, Xb
_
F
F
+
+
RFCF2
P(NEt2)3
RFCF2
F
P(NEt2)3
RFCF2
F
P(NEt2)3
_
Cu(OTf)2
CF3SO2O
F
N
N
O
N
O
O
XV
IX
XVI
RF = CF3
(Et2N)3PF2
VIIа, VIIb
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

PIKUN et al.
1576
acetylenes, but of vinylthiophosphorane XVII whose de-
composition afforded unsaturated thioamides Xа, Xb
(Scheme 5).
16.1 reflection per parameter. A weight scheme was
used: ω = 1/[σ2(Fo2) + (0.0337P)2 + 0.161Р], where Р
= (Fo2 + 2Fc2)/3, the ratio of the maximum (average)
shift to the error in the last cycle 0.001 (0.000). The final
values of the divergence R1(F) 0.0351, wR2(F2) 0.0808
with respect to reflections with I > 2σ(I); R1(F) 0.0467,
wR2(F2) 0.0871, GOF 1.063 for all independent reflec-
tions. The residual electron density from the difference
Fourier series after the last refinement cycle was 0.37
and –0.27 е/Å3. The structural data are deposited in the
Cambridge Crystallographic Data Center, CCDC 931671.
EXPERIMENTAL
1H and 13C NMR spectra were registered on a spec-
trometer Bruker Avance 400 [operating frequencies
400.13 (1Н) and 100.62 MHz (13С)] in CDCl3, internal
reference TMS, 19F and 31P NMR spectra were taken
on a spectrometer Varian Gemini-200 [operating fre-
quencies 188.14 (19F) and 80.95 MHz (31P)] in CDCl3,
internal reference C6F6. IR spectra were recorded on an
instrument UR-20 from pellets with KBr. Mass spectra
were obtained on a GC/MS instrument Hewlett Packard
5890/5972 in the EI mode at 70 eV, mass spectra LC/MS
were measured on a spectrometerAgilent 1100 equipped
with a mass-selective detector Agilent LC/MSD SL;
ionization method ES-API. The elemental analyses were
carried out in the analytical laboratory of the Institute of
Organic Chemistry, National Academy of Sciences of
Ukraine. Melting points were measured on a Boёtius heat-
ing block. To column chromatography silica gel Merck 60
(70–230 μm) was applied. TLC was performed on plates
Macherey–Nagel; Polygram® Sil G/UV254, development
in iodine vapor. The reaction progress was monitored by
19F and 31P NMR spectroscopy. All solvents before use
were dried and distilled by standard procedures.
Reaction of N-p-tolyl polyfluoroalkanethioamides
IVа, IVb with triethyl phosphite. A mixture of
15.0 mmol of thioamide IVа, IVb and 7.47 g (45.0 mmol)
of triethyl phosphite was heated in an argon atmosphere
for 9 h at 150°C. The reaction mixture was distilled in
a vacuum (0.08 mm Hg) at 100–130°С with subsequent
purification by column chromatography on silica gel
(eluent hexane–ethyl acetate, 70 : 30). The correspond-
ing phosphonates Va, Vb and S-ethylthioimidates VIа,
VIb were isolated.
Diethyl 1-[(4-methylphenyl)amino](2,2,2-tri-
fluoroethyl) phosphonate (Vа). Yield 0.20 g (40%),
1
yellow crystals, mp 70–72°С (from hexane). Н NMR
spectrum, δ, ppm: 1.129 m (6Н, POCH2CH3), 2.25 s
(3Н, CH3), 4.18 m (5H, CH + POCH2CH3), 6.63 d
3
3
(2HAr, JH,H 8.4 Hz), 7.02 d (2HAr, JH,H 8.4 Hz).
13C NMR spectrum, δ, ppm: 16.4 m (POCH2CH3),
1
2
Crystals of compound Xa monoclinic. C9H9F6NOS,
M 293.23. Space group Р21/с; а 6.7128(2), b 8.6074(2),
c 10.6208(3) Å; α 69.709(1), β 76.664(1), γ 84.120(2)°,
V 559.89(3) Å3, Z 2, dcalc 1.739 g/cm3, μ 0.358 mm–1,
F(000) 296. XRD analysis of a single crystal of the size
0.44 × 0.25 × 0.12 mm was carried out at –100°C on
a diffractometer Bruker SmartApex II (λMoKα-radiation,
graphite monochromator, θmax 30.49°, spheric segment
−7 ≤ h ≤ 9, –12 ≤ k ≤ 12, –15 ≤ l ≤ 14). Overall 10178
reflections were collected, among them 3284 were inde-
pendent (R-factor of averaging 0.0322). The correction
for extinction was introduced by multiscanning procedure
using SADABS program (Tmin/Tmax = 0.8300/0.9583).
The structure was solved by the direct method and refined
by the least-squares method in the full-matrix anisotro-
pic approximation using Bruker SHELXTL software
[10]. All hydrogen atoms were placed geometrically
and refined in the rider model. The refinement was per-
formed using 3284 independent reflections, among them
2629 reflections with I > 2σ(I) (163 refined parameters,
20.5 s (CH3), 54.7 d.q (CH, JC,P 153.3, JC,F 31.5 Hz),
63.8 d (POCH2CH3, 2JC,P 7.7 Hz), 64.2 d (POCH2CH3,
2JC,P6.3 Hz), 113.9 s (CH,Ar), 124.1 q.d (CF3, 1JC,F 283.4,
2JC,P 10.9 Hz), 129.1 s (Ctert, Ar), 130.0 s (CH, Ar),
143.2 d (Ctert, Ar, JC,P 6.6 Hz). 19F NMR spectrum, δ,
3
ppm: – 69.8 m (3F, CF3). 31P{1H} NMR spectrum, δ,
ppm: 15.8 q (3JP,F 8.2 Hz). Mass spectrum, m/z (Irel, %):
326 [M + 1]+. Found, %: C 47.89; H 5.87; N 4.47; P 9.48.
C13H19F3NO3P. Calculated, %: C 48.00; H 5.89; N 4.31;
P 9.52. M 325.26.
Diethyl 1-[(4-methylphenyl)amino]-(2,2,3,3,4,4,5,5-
octafluoropentyl)phosphonate (Vb). Yield 0.14 g
(20%), yellow liqid. 1H NMR spectrum, δ, ppm: 1.27 m
(6H, POCH2CH3), 2.24 s (3H, CH3), 4.05–4.20 m (5H,
2
CH + POCH2CH3), 6.01 t.t (1H, HCF2, JH,F 52.0,
3JH,F 5.5 Hz), 6.60 d (2HAr, 3JH,H 8.4 Hz), 7.02 d (2H, Ph,
3JH,H 8.4 Hz). 19F NMR spectrum, δ, ppm: –112.8 d.m
2
(1F, CFAFB, JF,F 282.9 Hz), –118.1 d.m (1F, CFAFB,
2JF,F 282.9 Hz), –124.2 m (2F, CF2), –131.5 m (2F, CF2),
–138.7 m (2F, HCF2). 31PNMR spectrum, δ, ppm: 14.8 m.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

REACTIONS OF POLYFLUOROALKANETHIOAMIDES
1577
Mass spectrum, m/z (Irel, %): 457 (10.1) [M]+, 320 (100),
169 (15.7), 118 (13.0), 91 (11.3). Found, %: C 42.10;
H 4.47; N 3.04; P 6.74. C16H20F8NO3P. Calculated, %:
C 42.02; H 4.41; N 3.06; P 6.77. M 457.30.
15 mL). The combined organic solutions were dried with
Na2SO4, filtered, and evaporated. Amides VIIIa, VIIIb
were subjected to column chromatography on silica gel,
eluent hexane–ethyl acetate, 90 : 10.
Ethyl-N-(4-methylphenyl)-2,2,2-trifluoroetha-
neimidothionate (VIa). Yield 0.07 g (20%), yellow liq-
uid. 1H NMR spectrum, δ, ppm: 1.20 m (3H, SCH2CH3),
2.35 s (3H, CH3), 2.95 m (2H, SCH2CH3), 6.85 m (2H,
Ar), 7.18 m (2H,Ar). 19F NMR spectrum, δ, ppm: –68.9 s
(CF3). Mass spectrum, m/z (Irel, %): 247 [M]+, 186 (88.62),
150 (63.9), 91 (100), 65 (34.9). Found, %: C 53.39;
H 4.81; N 5.69; S 12.93. C11H12F3NS. Calculated, %:
C 53.43; H 4.89; N 5.66; S 12.97. M 247.28.
3,3,3-Trifluoropropanoic acid morpholide (VIIIа)
[11]. Yield 0.07 g (20%), colorless oily substance. 1H NMR
spectrum, δ, ppm: 3.18 q (2H, CH2, 3JH,F 10.1 Hz), 3.42 m
(2H, morph.), 3.62 m (6H, morph.). 19F, δ, ppm: –63.7 t
3
(3F, CF3, JF,H 10.1 Hz). Mass spectrum, m/z (Irel, %):
198 (100) [M + 1]+. Found, %: C 42.53; H 5.13; N 7.15.
C7H10F3NO2. Calculated, %: C 42.64; H 5.11; N 7.10.
M 197.16.
3,3,3,4,4-Pentafluorobutanoic acid morpholide
(VIIIb). Yield 0.22 g (50%), colorless crystals, mp
55–58°C. 1H NMR spectrum, δ, ppm: 3.22 t (2H, CH2,
3JH,F 17.4 Hz), 3.52 m (2H, morph.), 3.72 m (6H, morph.).
13C NMR spectrum, δ, ppm: 34.6 t (CH2, 2JC,F 21.7 Hz),
42.5 s (NCH2), 47.1 s (NCH2), 66.5 s (OCH2), 66.7 s
Ethyl-N-(4-methylphenyl)-2,2,3,3,4,4,5,5-octaflu-
oropentanimidothionate (VIb). Yield 0.34 g (60%),
1
yellow liquid. H NMR spectrum, δ, ppm: 1.10 t (3H,
3
SCH2CH3, JH,H 7.5 Hz), 2.36 s (3H, CH3), 2.67 q
(2H, SCH2CH3, 3JH,H 7.5 Hz), 6.21 t.t (1H, HCF2, 2JH,F
3
3
1
2
52.2, JH,F 5.6 Hz), 6.88 d (2HAr, JH,H 7.8 Hz), 7.18 d
(2HAr, 3JH,H 7.8 Hz). 13C NMR spectrum, δ, ppm: 14.7 s
(SCH2CH3), 21.1 s (CH3), 26.6 s (SCH2CH3), 105.2–
110.8 m [4CF2, H(CF2)4], 119.0 s (CH, Ar), 129.8 s (CH,
Ar), 135.7 s (Ctert, Ar), 144.2 s (Ctert, Ar), 152.8 t (C=N,
2JC,F 27.5 Hz). 19F NMR spectrum, δ, ppm: –109.9 m (2F,
CF2), –123.1 m (2F, CF2), –129.3 m (2F, CF2), –138.1 d.m
(2F, HCF2, 2JF,H 52.2 Hz). Mass spectrum, m/z (Irel, %):
379 (36.1) [M]+, 318 (75.6), 178 (61.2), 150 (79.1),
91 (100). Found, %: C 44.25; H 3.53; N 3.48; S 8.53.
C14H13F8NS. Calculated, %: C 44.33; H 3.45; N 3.69;
S 8.45. M 379.31.
(OCH2), 115.0 t.q (CF2, JC,F 256.7, JC,F 38.3 Hz),
118.6 q.t (CF3,1JC,F 286.3, 2JC,F 35.8 Hz), 161.3 s (C=O).
19F NMR spectrum, δ, ppm: –86.4 m (3F, CF3), –116.0 t
(2F, CF2, 3JF,H 17.4 Hz). Mass spectrum, m/z (Irel, %):
247 (32.86) [M]+, 232 (23.8), 161 (100), 86 (20.7), 56
(23.3). Found, %: C 38.87; H 4.10; N 5.68. C8H10F6NO2.
Calculated, %: C 38.88; H 4.08; N 5.67. M 247.16.
Perfluoropent-2-enethiocarboxylic acid amides Xа,
Xb and tris(diethylamino)phosphonium fluorides IXа,
IXb. To a solution of 0.5 g (15.0 mmol) of thioamide
Ic, Id in 20 ml of diethyl ether was added under argon
0.75 g (30.0 mmol) of tris(diethylamino)phosphine, the
reaction mixture was stirred for 24 h at room temperature.
The formed precipitate of fluoride IXа was filtered off,
washed with diethyl ether (2 × 15 mL), dried in a vacuum
(0.08 mm Hg). At obtaining fluoride IXb it separated as
an oily fluid insoluble in ether; the solvent was decanted,
the residue was washed with diethyl ether (2 × 15 mL),
and dried in a vacuum (0.08 mm Hg).At stirring the reac-
tion mixture for 4 days at room temperature the initially
formed phosphonium fluorides IXа, IXb disappeared.
Thus obtained reaction mixture was stirred for 1 h with
15 mL of 5% hydrochloric acid at room temperature.
The organic phase was separated and washed with water.
The water phase was extracted with diethyl ether (2 ×
15 ml). The combined organic solutions were dried with
Na2SO4, filtered, and evaporated. The compounds Xа,
Xb obtained as a mixture of cis- and trans-isomers were
subjected to column chromatography on silica gel, eluent
hexane–ethyl acetate, 90 : 10.
Fluorine-containing aminoacetylenes VIIа, VIIb
and polyfluoroalkanecarboxylic acids morpholides
VIIIа, VIIIb. To a solution of 18.0 mmol of thioamide
Iа in 20 ml of diethyl ether was added under argon 0.82 g
(33.0 mmol) of tris(diethylamino)phosphine, and the
mixture was stirred for 6 days at room temperature. The
solvent and the obtained ynamines VIIa, VIIb were dis-
tilled off in a vacuum (0.08 mm Hg) into a trap cooled
with liquid nitrogen. The signals of the СF3СF2 group in
the 19F NMR spectrum of ynamine VIIа are observed
at –87.0 (СF3), –97.0 ppm (2F, СF2), in the spectrum of
ynamine VIIb this signal of the СF3 group appears at
–47.0 ppm in agreement with the described spectra of
N,N-dibutyl(3,3,3-trifluoro-1-propynyl)amine [8]. The
solution of ynamine VIIa, VIIb in diethyl ether was
stirred for 1h with 15 mLof 5% HCl at room temperature.
The organic phase was separated and washed with water.
The water phase was extracted with diethyl ether (2 ×
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

PIKUN et al.
1578
Tris(diethylamino)(1-morpholino-2,3,3,4,4,5,5-
C 36.86; H 3.09; N 4.78; S 10.94. M 293.23.
heptafluoropent-1-en-1-yl)phosphonium fluoride
(IXа). Yield 0.12 g (15%), brown powder, mp 88–92°С.
1H NMR spectrum, δ, ppm: 1.29 t (18H, 6CH2CH3,
3JH,H 6.8 Hz), 3.05 m [4H, N(CH2)2], 3.28 m (12H,
6CH2CH3), 3.76 m [4H, O(CH2)2], 6.26 t.t (HCF2,
(2E)-2,3,4,4,5,5-Hexafluoropent-2-enethiocarbox-
ylic acid piperidide (Xb). Yield 0.08 g (20%), yellow
oily substance. IR spectrum, ν, cm–1: 2947 [N(CH2)2],
1
1493 (C=S). H NMR spectrum, δ, ppm: 1.76 m (6H,
СH2), 3.69 m (2H, NCH2), 4.17 m (2H, NCH2), 6.00 t.m
(1H, HCF2, 2JH,F 53.4 Hz). 13C NMR spectrum, δ, ppm:
24.0 s (CH2), 25.3 s (CH2), 26.9 s (CH2), 49.4 s (NCH2),
53.7 s (NCH2), 109.0 t.t.d (HCF2, 1JC,F 252.6, 2JC,F 37.8,
3JC,F 3.0 Hz), 111.1 t.m (CF2, 1JC,F 253.3 Hz), 135.9 d.d.t
(CF2CF, 1JC,F 248.4, 2JC,F 44.9, 2JC,F 30.8 Hz), 148.4 d.d.t
(CF–CS, 1JC,F 262.6, 2JC,F 47.9, 3JC,F 3.2 Hz), 180.0 d.d
3
2JH,F 51.9, JH,F 4.5 Hz). 13C NMR spectrum, δ,
3
ppm: 12.9 d [PN(CH2CH3)2, JC,P 2.4 Hz], 40.8 d
2
[PN(CH2CH3)2, JC,P 4.2 Hz], 50.6 s (NCH2), 66.2 s
(OCH2), 107.3–113.1 m (2CF2), 107.6 t.t (HCF2,
1JC,F 255.9, 2JC,F 37.8 Hz), 131.7 d.d (CF=C, 1JC,P 165.1,
2JC,F 22.8 Hz), 158.7 d.d.t (CF=C, 1JC,F 278.2, 2JC,F 32.0,
2JC,P23.3 Hz). 19F NMR spectrum, δ, ppm: –102.8 m (1F,
CF), –114.8 m (2F, CF2), –127.8 m (2F, CF2), –137.6 d.m
2
3
(C=S, JC,F 23.6, JC,F 2.9 Hz). 19F NMR spectrum, δ,
ppm: –122.3 m (2F, CF2), –134.1 d.t (1F, CF, 3JF,F 141.6,
3JF,F 23.6 Hz), –138.3 d.m (2F, HCF2, 2JF,H 53.4 Hz),
–166.6 d.m (1F, CF, 3JF,F 141.6 Hz). Mass spectrum, m/z
(Irel, %): 291 (61.8) [M]+, 190 (100), 157 (28.48), 55
(20.0), 41 (20.7). Found, %: C 41.26; H 3.80; N 4.82;
S 11.04. C10H11F6NS. Calculated, %: C 41.24; H 3.81;
N 4.81; S 11.01. M 279.18.
2
(2F, HCF2, JF,H 51.9 Hz). 31P{1H} NMR spectrum, δ,
ppm: 44.0 d (3JP,F 6.8 Hz). Mass spectrum, m/z (Irel, %):
527 (100) [M + 1]+. Found, %: C 46.24; H 7.20; N 10.23;
P 5.73. C21H39F8N4OP. Calculated, %: C 46.15; H 7.19;
N 10.25; P 5.67. M 546.52.
Tris(diethylamino)(1-piperidino-2,3,3,4,4,5,5-hep-
Tris(diethylamino)(1-morpholino-2,3,3,4,4,4-hexa-
fluorobut-1-en-1-yl)phosphonium trifluoromethyl-
sulfonate (XV). To a solution of 0.5 g (15.0 mmol) of
thioamide Ib in 20 ml of diethyl ether was added under
argon 0.8 g (30.0 mmol) of tris(diethylamino)phosphine,
and the mixture was stirred for 24 h at room temperature.
To the reaction mixture 0.1 g (3 mmol) of copper(II)
triflate was added. A brown oily substance separated,
immiscible with ether. The solvent was decanted, the
residue was washed with water (3 × 15 mL) and dried in
a vacuum (0.08 mm Hg). Yield 0.44 g (45%). 1H NMR
spectrum, δ, ppm: 1.23 m (18H, 6CH3), 3.02 m [4H,
N(CH2)2], 3.20 m (12H, 6CH2), 3.72 m [4H, O(CH2)2].
13C NMR spectrum, δ, ppm: 13.1 d [PN(CH2CH3)2,
3JC,P 3.1 Hz], 40.8 d [PN(CH2CH3)2, 2JC,P 4.0 Hz], 50.9 s
(NCH2), 66.5 s (OCH2), 108.0 t.m (CF2, 1JC,F 264.4 Hz),
117.7 q.t (CF3, 1JC,F 289.8, 2JC,F 35.2 Hz), 120.9 q (CF-
tafluorohex-1-en-1-yl)phosphonium fluoride (IXb).
Yield 0.11 g (13%), brown oily substance. H NMR
1
spectrum, δ, ppm: 1.24 m (18H, CH2CH3), 1.66 m (6H,
CH2), 2.92 m [4H, N(CH2)2], 3.21 (12H, CH2CH3), 6.23 t
(1H, HCF2, 2JH,F 51.9 Hz). 19F NMR spectrum, δ, ppm:
–105.2 m (1F, CF), –115.1 m (2F, CF2), –127.7 m (2F,
2
CF2), –137.5 d.m (2F, HCF2, JF,H 51.9 Hz). 31P NMR
spectrum, δ, ppm: 44.3 m. Mass spectrum, m/z (Irel, %):
527 (100) [M + 1]+. Found, %: C 50.35; H 7.94; N 10.73;
P 5.90. C22H41F8N4P. Calculated, %: C 50.28; H 7.86;
N 10.66; P 5.89. M 544.55.
(2Z)-2,3,4,4,5,5-Hexafluoropent-2-enethiocarbox-
ylic acid morpholide (Xа). Yield 0.15 g (34%), yellow
crystals, mp 60–62°С [40°С (0.08 mm Hg) sublimated].
1H NMR spectrum, δ, ppm: 3.69 m (4H, 2CH2), 3.82 t
(2H, OCH2,3JH,F 4.8 Hz), 4.22 t (2H, OCH2, 3JH,H 4.8 Hz),
3
6.16 t.t (1H, HCF2, 2JH,F 52.7, JH,F 4.8 Hz). 13C NMR
1
1
3SO2O, JC,F 321.5 Hz), 132.6 d.d (CF=C, JC,P 165.5,
1
2JC,F 25.1 Hz), 157.8 d.m (CF=C, JC,F 275.4 Hz).
spectrum, δ, ppm: 48.4 s (NCH2), 52.7 s (NCH2), 66.1 s
1
(OCH2), 66.3 s (OCH2), 108.6 t.t.d (HCF2, JC,F 253.7,
19F NMR spectrum, δ, ppm: –79.2 s (3F, CF3SO2O),
–82.5 m (3F, CF3), –101.7 m (1F, CF), –116.7 m (2F,
CF2). 31P NMR spectrum, δ, ppm: 43.3 m. Mass spec-
trum, m/z (Irel, %): 496 [M + 1]+, 148 [M – 1]–. Found, %:
C 39.02; H 6.15; N 8.55; P4.62; S 5.07. C21H38F9N4O4PS.
Calculated, %: C 39.13; H 5.94; N 8.69; P 4.81; S 4.97.
M 644.58.
2JC,F 35.1, 3JC,F 2.9 Hz), 110.8 t.m (CF2, 1JC,F 254.3 Hz),
135.7 d.d.t (CF2CF, 1JC,F 261.4, 2JC,F 30.7, 2JC,F 21.3 Hz),
145.9 d.d.t (CF–CS, 1JC,F 270.1, 2JC,F 15.3, 3JC,F 3.8 Hz),
2
180.0 d (C=S, JC,F 20.6 Hz). 19F NMR spectrum, δ,
ppm: –111.0ч–133.6 br.m (2F, CF2), –117.0 d (2F, CF,
3JH,F 9.2 Hz), –139.0 m (2F, HCF2), –157.2 m (1F, CF).
Mass spectrum, m/z (Irel, %): 293 (100) [M]+, 207 (58.8),
192 (88.5), 156 (16.2), 51 (17.0). Found, %: C 36.91;
H 3.12; N 4.80; S 10.79. C10H11F6NS. Calculated, %:
REFERENCES
1. Percy, J.M., Top. Curr. Chem., 1997, vol. 193, p. 131.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

REACTIONS OF POLYFLUOROALKANETHIOAMIDES
1579
and Portella, C., J. Fluor. Chem., 2006, vol. 127, p. 471.
2. Shermolovich, Yu.G., Timoshenko, V.M., Bouillon, J.-P.,
and Portella, C., Ros. Khim. Zh., 2005, vol. 49, p. 109;
Siry, S.A., Timoshenko, V. M., and Bouillon, J.-P., J. Fluor.
Chem., 2012, vol. 137, p. 6.
6. Grellepois, F., Timoshenko, V.M., Rusanov, E.B., Sher-
molovich, Yu.G., and Portella, C., J. Fluor. Chem., 2010,
vol. 131, p. 937.
7. Mykhaylychenko, S.S., Pikun, N.V., and Shermolo-
vich, Yu.G., Tetrahedron Lett., 2011, vol. 52, p. 4788.
8. Yamanaka, H., Mantani, T., Shiomi, K., and Ishihara, T.,
Chem. Lett., 1998, p. 615.
9. Ishihara, T., Mantani, T., Konno, T., and Yamanaka, H.,
Tetrahedron, 2006, vol. 62, p. 3783.
10. Sheldrick, G.M., Acta Cryst., 2008, vol. A64, p. 112.
11. Koroniak, H., Walkowiak, J., Grys, K., Rajchel,A.,Alty,A.,
and Boisson, R., J. Fluor. Chem., 2006, vol. 127, p. 1245.
3. Rudnichenko, A.V., Timoshenko, V.M., and Shermo-
lovich, Yu.G., J. Fluor. Chem., 2004, vol. 125, p. 439;
Rudnichenko, A.V., Kaminskaya, E.I., and Shermolovich,
Yu.G., Zh. Org. Pharm. Khim., 2006, vol. 4, p. 3.
4. Mikhailichenko, S.S., Rudnichenko, A.V., Timosh-
enko, V.M., Chernega, A.N., Shermolovich, Yu.G., Grel-
lepois, F., and Portella, C., J. Fluor. Chem., 2007, vol. 128,
p. 703.
5. Timoshenko, V.M., Shermolovich, Yu.G., Grellepois, F.,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013