Protonation and alkylation of organophosphorus compounds with trifluoromethanesulfonic acid derivatives

Article abstract of DOI:10.1134/S1070363211030054

Protonation (alkylation) of triphenylphosphine, triethylphosphite, triphenylphosphine oxide, triethylphosphate, hexamethylphosporamide, and dimethylphosphite with trifluoromethanesulfonic acid, its bisimide, and methyl ester was studied and the corresponding ¹H, ¹³C, ¹⁹F, ³¹P NMR spectra were analyzed.

Full text of DOI:10.1134/S1070363211030054

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 3, pp. 474–480. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © L.L. Tolstikova, A.V. Bel’skikh, B.A. Shainyan, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 3, pp. 377–383.
Protonation and Alkylation of Organophosphorus Compounds
with Trifluoromethanesulfonic Acid Derivatives
L. L. Tolstikova, A. V. Bel’skikh, and B. A. Shainyan
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: bagrat@irioch.irk.ru
Received August 19, 2010
Abstract—Protonation (alkylation) of triphenylphosphine, triethylphosphite, triphenylphosphine oxide,
triethylphosphate, hexamethylphosporamide, and dimethylphosphite with trifluoromethanesulfonic acid, its
bisimide, and methyl ester was studied and the corresponding 1H, 13С, 19F, 31P NMR spectra were analyzed.
DOI: 10.1134/S1070363211030054
Phosphonium salts of the type R4P+X–, in parti-
cular, triaryl(alkyl)phosphonium salts, readily prepared
by the reaction of triarylphosphines with alkyl halides
[1], are widely used in organic synthesis for preparation
of olefins (Wittig reaction and its modifications, Wittig–
Horner or Horner–Wadsworth–Emmons reaction) [2].
In the recent time, papers appeared describing the
synthesis and application of the phosphonium salts [3,
4] and ionic liquids (IL) based on the phosphonium
cation R4P+, the so-called specifically designated ILs
[5, 6], including those containing the bis(trifluorometha-
nesulfonyl)imide anion. Bis(trifluoromethanesulfonyl)-
imide (CF3SO2)2NH (triflimide) attracts the attention
of researchers by its high acidity: its pKa in water is
1.7 [7], and the gas phase acidity is 291.8 kcal mol–1,
which is by 7.7 kcal mol–1 larger than that of the acid
CF3SO3Н itself [8]. Its lithium salt (CF3SO2)2NLi is
used in electrolytes for batteries [9–12], whereas the
salts of other metals [13] are used as water-resistant
Lewis acids in reactions of alkylation, acylation, nucleo-
philic substitution, and Diels–Alder cycloaddition [14–
19]. Lithium salt (CF3SO2)2NLi is also used in a two-
step synthesis of ILs, which includes quaterniza-tion of
the nitrogen or phosphorus atom followed by anionic
exchange [20], as shown in scheme (1) for the
phosphorus derivatives.
R1
P
R1
R1
R4
R4
R4X
Tf2NLi
+
P
+
P
X−
Tf2N −
R3
(1)
R2
R3
R2
R3
R2
Tf = CF3SO2.
Ph3P + HN(SO2F)2 → Ph3P+H[(FSO2)2N–],
Ph3PO + HN(SO2F)2 → Ph3PO·HN(SO2F)2.
(2)
(3)
Ionic liquids possessing anion (CF3SO2)2N– or its
analogs usually have the lowest melting points and
viscosity, and, besides, they are hydrophobic and
thermally and electrochemically stable [21–25], and
they found a wide application [26].
The structure of the former salt was proved by
XRD analysis, whereas the structure of the latter
product was not established unambiguously. Two
alternatives were considered: the hydrophosphonium
salt [Ph3POH]+[(FSO2)2N]– by analogy with hydroxy-
triphenylphosphonium chloride [Ph3POH]+Cl– [28], or
the H-complex Ph3P=O···HN(SO2F)2 similar to the
complex Ph3P=O···HN(SO2Me)2 [29].
At the same time, there are no data in the literature
on the reactions of triflimide with phosphines,
phosphine oxides, phosphites, phosphates, and other
phosphorus-containing nucleophiles. The closest study
is the paper of Hiemisch et al. [27], who investigated
the following reactions:
474

PROTONATION AND ALKYLATION OF ORGANOPHOSPHORUS COMPOUNDS
475
The reaction of magic acid HSO3F–SbF5 (1:1) with
Ph3P, Ph3P=O, and polyfluoroaromatic phosphines and
their derivatives C6F5PX2 (X = H, Me, Ph, C6F5, Cl, F,
NCS, CN, OMe, NEt2) was shown to lead to stable
phosphonium ions C6F5P+HX; in the latter case the
protonation occurs at the nitrogen atom C6F5(NEt2)·
(N+HEt2) [30].
of the Сi atom moves upfield by more than 20 ppm,
and the JPC coupling constant, in accordance with the
literature data [36], increases from ~10 to ~80 Hz.
The presence of anion Tf2N– in salt XII is also
corroborated by the IR spectrum, which is in
agreement with the literature data on a low-frequency
shift of the νas(SO2) band in the anions of bisimides
relative to the neutral molecules from ~1440 cm–1 to
1300–1350 cm–1 [7, 37–39].
1
It should be mentioned that this result is specific for
polyfluorinated phosphoramides since phosphines are
stronger nucleophiles than the corresponding amines
[31]. For example, the quaternization of dimethylamino-
dimethylphosphine (CH3)2PN(CH3)2 with methyl
iodide takes place at the phosphorus atom as proved by
the formation of dimethylamine at the hydrolysis of the
salt [32]. Apparently, the protonation of the nitrogen
atom in C6F5P(NEt2)2 [30] is due to a strong electron-
withdrawing effect of the pentafluorophenyl group.
We tried to prepare the tetraphenylphosphonium
salt of triflimide by the reaction of triphenylphosphine
I with N-phenyltriflimide IХ, but the reaction did not
occur even at long reflux in benzene (14 h), or with
microwave activation.
Tf2NPh + PPh3 → Ph3P+–Ph Tf2N–.
(5)
Triphenylphosphine is known to be alkylated with
esters of sulfonic acids at high temperatures (up to
170°С) with the formation of alkyltriaryl- and tetra-
alkylphosphonium sulfonates [40]. A higher nucleo-
fugacity of trifluoromethanesulfonyl group as com-
pared to the residues of other sulfonic acids allowed to
perform the reaction of phosphine I with ester X under
much milder conditions, in ~3 h at room temperature
in methylene chloride in quantitative yield.
In continuation of our studies of the triflic,
triflamide, and triflimide salts and ionic liquids [33,
34], we have now investigated the reaction of some
phosphorus-containing nucleophiles [Ph3P (I), (EtO)3P
(II), Ph3P=O (III), (EtO)3P=O (IV), (Me2N)3P=O (V),
(MeO)2P(O)H (VI)], with truifluoromethanesulfonic
acid CF3SO3H (VII) and its imide (CF3SO2)2NH
(VIII),
N-(phenyl)trifluoromethanesulfonylimide
(CF3SO2)2NPh (IX), and methyl ester CF3SO2OMe
(X). In a number of cases the products of the reactions
are readily hydrolized with the formation of un-
separable side-products, therefore, not for all products
the analytically pure samples could be obtained.
Ph3P + TfOMe → Ph3P+–Me TfO–.
(6)
XIII
The structure of salt XIII is proved by the shift of
1
the signal of the methyl protons in the H NMR
The reaction of triphenylphosphine I with strong
acids VII and VIII at room temperature in methylene
chloride or benzene affords the corresponding salts XI,
XII in quantitative yield.
spectrum by 1.3 ppm relative to ester X and by its
splitting with the coupling constant JPH 13Hz, as well
2
as by the presence of a doublet of the methyl carbon in
the 13С NMR spectrum with the coupling constant 1JPС
59 Hz and the coincidence of the aromatic part of the
13С NMR spectrum of salt XIII with that of salts XI,
XII.
YH + PPh3 → Ph3P+–H Y–,
(4)
XI, XII
Y = TfO (XI), Tf2N (XII); Tf = CF3SO2.
Similarly, the reaction of triethylphosphite II with
acids VII and VIII gives salts XIV and XV:
The structure of the formed phosphonium salts XI,
1
XII is confirmed by the presence in their H and 31P
YH + P(OEt)3 → (EtO)3P+–H Y–,
(7)
NMR spectra of the doublets of the РН group with
characteristic coupling constants JPH 531 Hz (XI) and
522 Hz (XII) (cf. [35]). The salt formation results in a
XIV, XV
Y = TfO (XIV), Tf2N (XV).
1
13
1
The Н and С NMR spectra of salts XIV, XV are
shift of the singlet of aromatic protons in the Н NMR
practically identical, in the proton spectra the doublets
of РН with the coupling constants JPH 745 Hz (XIV)
spectrum at 7.3 ppm in phosphine I to 7.6–7.8 ppm
and its splitting to multiplets of the о-, m- and p-
protons. In the 13С NMR spectrum, the signal of the Сp
atom moves downfield by 7–8 ppm, whereas the signal
1
and 729 Hz (XV) are observed, which coincide with
those in the 31Р NMR spectra (cf. with the NMR data
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476
TOLSTIKOVA et al.
for salt (EtO)3PH+FSO3– in FSO3H solution at –60°С
[41]).
Salts XIV, XV are hydrolyzed at standing with the
formation of ethanol and diethylphosphite XVI ac-
cording to scheme (8), as shown by the appearance of
Similar to triphenylphosphine, the triethylphosphite
does not react with compound IХ even at long reflux
in benzene.
13
the corresponding signals in the 1Н, С, and 31Р NMR
spectra.
H2O
(EtO)3PH+Y–
[(EtO)2P(OH)] → (EtO)2P(O)H
(8)
–EtOH, –HY
XVI
Triethylphosphite reacts with ester Х with the
NMR spectra, is diethylphosphite XVI. Taking into
account the literature data [42, 43], the following
scheme of transformations may be suggested:
formation of several products, which we failed to
1
separate. The major product, according to Н and 31Р
CH3
(EtO)3P
CH3 TfO−
(EtO)3P+
H
(EtO)3P + CH3OTf
CH2 CH2
P(OEt)3
O
P+ OEt TfO−
OEt
−TfOMe
(9)
− + (EtO)2P(Me)
O
(EtO)3P + XVI
(EtO)3P− H TfOH
−CH2=CH2
−TfOMe
XIV
The formation of salt (EtO)3P+Me TfO– is proved
by the presence of a doublet of multiplets of the РСН3
methyl group in the 1Н NMR spectrum with the
Similar to triphenylphosphine oxide III, triethyl-
phosphate IV reacts with trifluoromethanesulfonic acid
VII, bis(trifluoromethanesulfonyl)imide VIII, and
methyl triflate X. The reactions with the formation of
XX and XXI proceed smoothly in CH2Cl2 in high
yields at room temperature.
2
coupling constant JPСH 12.1 Hz, and the signal in the
31Р NMR spectrum at 50.4 ppm, which is characteristic
of such salts [43]. The formation of esters Х and
TfOEt is indicated by the presence of a signal at
–75 ppm in the 19F NMR spectrum, which coincides
with the 19F NMR signal of compound Х.
YR + (EtO)3P=O → (EtO)3P+–OR Y–,
(11)
Y = TfO, R = H (XX); Y = Tf2N, R = H (XXI); Y = TfO,
R = Me (XXII).
The reaction of triphenylphosphine oxide III with com-
pounds VII, VIII, and X gives rise to salts XVII–XIX.
In the 1Н NMR spectra of salts ХХ, XXI the signals
of the СН2 and СН3 groups are shifted downfield by
0.5–0.6 ppm relative to the starting ester IV and the
line shape of the multiplets is changed. For salt ХХ,
the signal of the СН2 group is a doublet of doublets of
YR + Ph3P=O → Ph3P+–OR Y–,
(10)
Y = TfO, R = H (XVII); Y = Tf2N, R = H (XVIII); Y =
TfO, R = Me (XIX).
3
3
Salts XVII and XIX are syrup-like liquids, and salt
XVIII is a crystalline compound with mp 78°С. In the
1Н NMR spectra of all salts the signal of the Нp
protons is shifted relative to the starting compound III
by ~0.3 ppm and becomes the most downfield
aromatic signal. In the 13С NMR spectra the signal of
Сp is shifted downfield by ~3 ppm, and the signal of Ci
is shifted upfield by ~10 ppm. The methyl group in IL
quartets with the coupling constants JНH, JНР and
5JНH, and the СН3 group gives rise to a triplet of
4
triplets due to the close small constants JНР and 6JНH.
In ester IV, the signal of the СН2 group is a doublet of
3
3
quartets with close constants JНH = 7.1 Hz and JНР
=
7.6 Hz, and the СН3 group looks like a a doublet of
4
triplets with a small constant JНР = 0.8 Hz. The reac-
tion of esters IV and X, apart from salt XXII, gives
rise to the products of transalkylation, (MeO)2(EtO)2P+ ·
TfO– and (EtO)4P+ TfO–, as proved by the presence of
XIX is split into a doublet with the coupling constants
1
J
PH = 12.1 Hz in the Н NMR spectrum and with JPС
=
1
7.7 Hz in the 13С NMR spectrum.
minor doublets of the МеО group in the Н and 13С
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PROTONATION AND ALKYLATION OF ORGANOPHOSPHORUS COMPOUNDS
477
4
NMR spectra, as well as the СН2 group in the 13С
coupling JНH = 0.5 Hz is observed. In the 13С NMR
spectrum the signal of the methoxy group is also
shifted downfield by ~2 ppm.
NMR spectrum. The ratio of the salts determined from
1
the intensity of the signals in the Н NMR spectrum is
~3:1:3.
The reaction of compound VI with ester Х does not
give the expected trimethoxyphosphonium triflate
(МеО)3РН+ TfO–. The NMR spectra of the reaction
product are practically identical with the spectra of the
starting VI, being slightly shifted downfield due to the
partial hydrolysis of ester Х and the acidity of the
medium. Apparently, the reversibly formed product
(МеО)3РН+ TfO– easily decomposes in the starting
components, and also eliminates methanol, as proved
by its formation and condensation in a cooled trap
when carrying out the reaction in thoroughly dried
methylene chloride.
The reaction of hexamethylphosphortriamide V
with acid VII and imide VIII results in a downfield
shift of the signals in the Н and 31Р NMR spectra by
1
1
0.4 and ~9 ppm, respectively. Also, in the Н NMR
spectra downfield signals of ОН are present with the
ratio of intensities ОН : NMe = 1 : 18. These data are
indicative of the formation of salts XXIII, XXIV:
(Me2N)3P=O + YH → (Me2N)3P+–OH Y–,
(12)
Y = TfO (XXIII), Tf2N (XXIV).
The presence in the IR spectrum of compound
XXIV of the band νas(SO2) at 1353 cm–1, which
belongs to anion Tf2N– (see above), proves its salt
nature.
EXPERIMENTAL
IR spectra were recorded on a Bruker Vertex 70 instru-
ment in thin film or in KBr. NMR spectra were taken
on a Bruker DPX 400 spectrometer at working
frequencies 400 (1Н), 100 (13С), 376 (19F), 162 (31P)
MHz in CDCl3, using the signals of the residual
The reaction of hexamethylphosphortriamide V
with ester X affords the O-methylation product, tris-
(dimethylamino)(methoxy)phosphonium triflate XXV.
1
In its Н and 13С NMR spectra, the doublets of the
1
ОМе and NMe groups are observed in the ratio of 1:6.
protons of the solvent (for Н), or carbon atoms (for
13С) as an internal reference, chemical shifts are given
relative to TMS (1Н, 13С), CCl3F (19F), Н3РО4 (31Р).
(Me2N)3P=O + CF3SO3Me
→ (Me2N)3P+–OMe CF3SO3–,
(13)
XXV
N-Phenyl-bis(trifluoromethanesulfonyl)imide
IX
and methyltrifluoromethanesulfonate X were prepared
as described earlier in [44] and [45, 46], respectively.
Dimethylphosphite VI reacts with acid VII and
imide VIII to give salts XXVI, XXVII:
(MeO)2P(O)H + YH → (MeO)2P+H–OH Y–,
(14)
Triphenylphosphonium trifluoromethanesulfonate
(XI). To the solution of 0.22 g (1.45 mmol) of acid
VII in 3 ml of methylene chloride or benzene the
solution of 0.38 g (1.45 mmol) of phosphine I in 2 ml
of the same solvent was added at vigorous stirring, the
mixture was stirred for 3 h at room temperature and
evaporated to give 0.60 g (100%) of salt XI as white
crystals with mp 98–99°С. IR spectrum, ν, cm–1: 3064,
2405, 1586, 1482, 1441, 1282, 1225, 1152, 1115,
Y = TfO (XXVI), Tf2N (XXVII).
1
The Н NMR spectra of these compounds contain
the OH group signal in a very low field (15 ppm for
salt XXVI and 13 ppm for salt XXVII). The signals of
the ОМе and РН protons are shifted downfield by
0.2 ppm with respect to the starting compound VI, and
1
the coupling constant JPH increases by 30–40 Hz. In
1
the reaction of dimethylphosphite VI with acid VII a
side reaction of transesterification is observed with the
formation of about 10% of methyl triflate Х and ester
МеОРН(О)(ОН). This is proved by the presence in the
19F NMR spectrum of the reaction product of the
signal at –74.3 ppm, in the 13С NMR spectrum, of a
minor doublet signal at 54.0 ppm with JPC 6 Hz, and in
1031, 907, 749, 722, 691, 638, 510, 492. Н NMR
spectrum, δ, ppm: 7.80–7.67 m (15H, Ar), 9.38 d (1H,
JPH 530.9 Hz). 13С NMR spectrum, δС, ppm: 115.62 d
(Сi, JCP 86.6 Hz), 120.02 q (СF3, JCF 319.1 Hz), 130.52
d (Сm, JCP 13.3Hz), 134.01 d (Сo, JCP 11.1 Hz), 135.49
d (Сp, JCP 2.6 Hz). 19F NMR spectrum, δF, ppm:
–78.23. 31Р NMR spectrum, δР, ppm: 3.89 d (PH, JPH
531.2 Hz). Found, %: С 56.04; Н 3.88; F 13.73; P
7.43; S 8.12. C19H16F3O3PS. Calculated, %: С 55.34; Н
3.91; F 13.82; P 7.51; S 7.78. Compounds XII–XXVII
were obtained similarly.
1
the Н NMR spectrum, of the singlet of the methyl
group at 3.69 ppm from Х and the doublet at 3.86 ppm
with the coupling constant ~12 Hz. For salt XXVI, a
weak splitting of the OMe signal with the long-range
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TOLSTIKOVA et al.
1
Triphenylphosphonium bis(trifluoromethanesulfo-
1188, 1124, 1025, 979, 731, 690, 635, 534. Н NMR
spectrum, δ, ppm: 7.78–7.64 m (15H, Ar), 10.71 s
nyl)-imide (XII). Yield 98%, colorless syrup-like
liquid. IR spectrum, ν, cm–1: 3066, 2426, 1588, 1484,
1442, 1352, 1197, 1136, 1057, 897, 743, 689, 615,
13
(1H). С NMR spectrum, δС, ppm: 119.57 q (СF3, JCF
318.6 Hz), 122.93 d (Сi, JCP 109.1 Hz), 129.70 d (Сm,
1
570, 510. Н NMR spectrum, δ, ppm: 7.82–7.68 m
JCP 13.6 Hz), 132.76 d (Сo, JCP 11.4 Hz), 135.13 d (Сp,
(15H, Ar), 8.94 d (Р–Н, JPН 521.8 Hz). 13С NMR
spectrum, δС, ppm: 115.75 d (Сi, JCP 73.7 Hz), 119.72
q (СF3, JCF 321.5 Hz), 130.48 d (Сm, JCP 13.3Hz),
133.78 d (Сo, JCP 11.8 Hz), 135.40 s (Сp). 19F NMR
spectrum, δF, ppm: –78.78. 31Р NMR spectrum, δР,
ppm: 5.28 d (PH, JPH 519.7 Hz). Found, %: С 44.83; Н
2.83; N 2.51; S 11.23. C20H16F6NO4PS2. Calculated,
%: С 44.20; Н 2.97; N 2.58; S 11.80.
JCP 1.8 Hz). 19F NMR spectrum, δF, ppm: –78.32. 31Р
NMR spectrum, δР, ppm: 53.12. Found, %: С 54.60; Н
2.97; F 14.18; P 6.58; S 7.13. C19H16F3O4PS.
Calculated, %: С 53.27; Н 3.76; F 13.31; P 7.23; S
7.49.
Hydroxytriphenylphosphonium bis(trifluorome-
thanesulfonyl)imide (XVIII). Yield 88%, white
crystals, mp 69°С. IR spectrum, ν, cm–1: 3438, 1439,
1356, 1334, 1200, 1142, 1125, 1050, 729, 692, 611,
Methyltriphenylphosphonium trifluoromethane-
sulfonate (XIII). Yield 100%, white crystals, mp 128°С.
IR spectrum, ν, cm–1: 3443, 1589, 1486, 1440, 1260,
1
574, 539. Н NMR spectrum, δ, ppm: 7.81–7.67 m
(15H, Ar), 9.94 s (1H). 13С NMR spectrum, δС, ppm:
119.16 q (СF3, JCF 320.9 Hz), 122.42 d (Сi, JCP 109.1 Hz),
129.83 d (Сm, JCP 13.6 Hz), 132.73 d (Сo, JCP 11.8 Hz),
135.40 d (Сp, JCP 2.2 Hz). 19F NMR spectrum, δF, ppm:
–77.60. 31Р NMR spectrum, δР, ppm: 55.59. Found, %:
С 42.73; Н 2.86; F 20.48; N 2.70; P 5.18; S 11.75.
C20H16F6NO5PS2. Calculated, %: С 42.94; Н 2.88; F
20.38; N 2.50; P 5.54; S 11.46.
1
1152, 1116, 1030, 903, 745, 690, 637, 501. Н NMR
spectrum, δ, ppm: 2.94 d (3H, CH3, JHP 12.6 Hz),
7.81–7.65 m (15H, Ar). 13С NMR spectrum, δС, ppm:
9.46 d (СH3, JCP 58.2 Hz), 119.72 q (СF3, JCF 321.5 Hz),
118.99 d (Сi, JCP 88.5 Hz), 130.48 d (Сm, JCP 13.3Hz),
133.08 d (Сo, JCP 10.3Hz), 135.19 d (Сp, JCP 2.21 Hz).
19F NMR spectrum, δF, ppm: –77.81. 31Р NMR
spectrum, δР, ppm: 24.43. Found, %: С 55.30; Н 4.48;
F 14.17; P 7.47; S 7.86. C20H18F3O3PS. Calculated, %:
С 56.34; Н 4.26; F 13.37; P 7.26; S 7.52.
Methoxytriphenylphosphonium trifluoromethane-
sulfonate (XIX). Yield 100%, light-yellow crystals,
mp 37°С. IR spectrum, ν, cm–1: 3066, 1440, 1267,
1
Triethoxyphosphonium trifluoromethanesulfonate
(XIV). Yield 87%, light-brown liquid. IR spectrum, ν,
cm–1: 2991, 2939, 2917, 2467, 1714, 1249, 1229, 1197,
1181, 1032, 639, 516. 1Н NMR spectrum, δ, ppm: 1.39
t (9Н, СН3, J 7.0 Hz), 4.28 d.q (6Н, СН2, JРН 8.65, JНН
7.23Hz), 6.97 d (1Н, JРН 743.0 Hz). 13С NMR
spectrum, δС, ppm: 15.83 d (СH3, JCP 6.2 Hz), 65.1 d
(СH2, JCP 6.2 Hz), 119.32 q (CF3, JCF 317.8 Hz).
19F NMR spectrum, δF, ppm: –78.18. 31Р NMR
spectrum, δР, ppm: 9.31 d (JPH 744.6 Hz).
1225, 1162, 1123, 1030, 732, 692, 638, 545, 531. Н
NMR spectrum, δ, ppm: 4.10 d (3Н, СН3, JНP 12.1 Hz),
7.88–7.57 m (19.2 H, Ar). 13С NMR spectrum, δС,
ppm: 58.03 d (СН3, JCP 7.7 Hz), 118.29 d (Сi, JCP
106.5 Hz), 130.53 d (Сm, JCP 13.6 Hz), 133.38 d (Сo,
JCP 11.9 Hz), 136.45 d (Сp, JCP 2.2 Hz). 19F NMR
spectrum, δF, ppm: –78.31. 31Р NMR spectrum, δР,
ppm: 65.19.
Triethoxy(hydroxy)phosphonium
trifluorome-
thanesulfonate (XX). Yield 98%, colorless syrup-like
Triethoxyphosphonium
bis(trifluoromethane-
liquid. IR spectrum, ν, cm–1: 2991, 2939, 2917, 1708,
1
sulfonyl)imide (XV). Yield 82%, light-brown liquid.
1313, 1200, 1034, 822, 638, 515. Н NMR spectrum,
IR spectrum, ν, cm–1: 3243, 2993, 2469, 1443, 1353,
δ, ppm: 1.36 t.t (9Н, СН3, 3JНH 7.1, 4JРH = 6JНH 1.3Hz),
4.20 d.q (6Н, СН2, 3JРH 8.1, 3JНH 7.0, 5JНH 1.2 Hz). 13С
NMR spectrum, δС, ppm: 15.68 d (СH3, JCP 6.6 Hz),
66.57 d (СH2, JCP 6.3 Hz), 119.59 q (СF3, JCF 318.1 Hz).
19F NMR spectrum, δF, ppm: –78.55. 31Р NMR
spectrum, δР, ppm: –2.04.
1
1196, 1139, 1061, 880, 791, 613, 572, 514. Н NMR
spectrum, δ, ppm: 1.40 t (9Н, СН3, J 7.1 Hz), 4.22 d.q
3
3
1
(6Н, СН2, JРН 9.1, JНН 7.1 Hz), 6.88 d (1Н, РН, JPH
729.1 Hz). 13С NMR spectrum, δС, ppm: 15.95 d (СH3,
JCP 6.3Hz), 64.13 d (СH2, JCP 5.9 Hz), 119.06 q (СF3,
J
CF 322.3Hz). 19F NMR spectrum, δF, ppm: –77.29. 31Р
Triethoxy(hydroxy)phosphonium
bis(trifluoro-
NMR spectrum, δР, ppm: 9.01 d (JPH 725.08 Hz).
methanesulfonyl)imide (XXI). Yield 96%, light
Hydroxytriphenylphosphonium trifluoromethane-
sulfonate (XVII). Yield 100%, syrup-like liquid. IR
spectrum, ν, cm–1: 3064, 1591, 1440, 1313, 1204,
yellow liquid. IR spectrum, ν, cm–1: 3265, 2993, 1445,
1
1353, 1195, 1140, 1037, 820, 616, 572, 514. Н NMR
spectrum, δ, ppm: 1.39 t (3Н, СН3, J 7.1 Hz), 4.20 q
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PROTONATION AND ALKYLATION OF ORGANOPHOSPHORUS COMPOUNDS
479
(9Н, СН2, J 7.2 Hz), 4.22 q (6Н, СН2, J 7.5 Hz), 14.41
s (1H). 13С NMR spectrum, δС, ppm: 15.75 d (СH3, JCP
6.6 Hz), 66.09 d (СH2, JCP 6.3 Hz), 119.36 q (СF3, JCF
321.6 Hz). 19F NMR spectrum, δF, ppm: –77.96. 31Р
NMR spectrum, δР, ppm: – 2.98.
NMR spectrum, δ, ppm: 2.85 d (18H, NСН3, JРH 10.1
Hz), 3.99 d (3H, ОСН3, JРH 11.6 Hz). 13С NMR
spectrum, δС, ppm: 36.90 d (NСH3, JCP 4.4 Hz), 56.09
d (ОСН3, JCP 6.6 Hz), 120.80 q (СF3, JCF 320.7 Hz).
19F NMR spectrum, δF, ppm: –78.13. 31Р NMR spec-
trum, δР, ppm: 38.76. Found, %: С 27.51; Н 5.03; F
15.56; N 12.51; P 8.95; S 10.15. C8H21F3N3O4PS.
Calculated, %: С 27.99; Н 6.17; F 16.60; N 12.24; P
9.02; S 9.34.
Triethoxy(methoxy)phosphonium trifluorome-
thanesulfonate (XXII) was prepared as a mixture with
the products of transalkylation (MeO)2(EtO)2P+ TfO–
and (EtO)4P+ TfO–, total yield 96%, light yellow liquid.
IR spectrum, ν, cm–1: 2989, 2916, 1447, 1396, 1274,
Dimethoxy(hydroxy)phosphonium trifluorome-
thanesulfonate (XXVI). Yield 100%, light liquid. IR
spectrum, ν, cm–1: 2963, 2918, 2859, 2459, 1709,
1
1225, 1166, 1031, 824, 639, 517. Н NMR spectrum,
δ, ppm: 1.20 t (9Н, СН3, J 7.3 Hz), 3.63 d (3Н, ОСН3,
J 11.3 Hz), 3.99 q (6H, ОСН2, J 7.3 Hz). 13С NMR
spectrum, δС, ppm: 15.50 d (СH3, JCP 6.3 Hz), 54.23 d
(ОСH3, JCP 6.3 Hz), 64.28 d (ОСH2, JCP 5.9 Hz),
119.99 q (СF3, JCF 317.7 Hz). 19F NMR spectrum, δF,
ppm: –78.56. 31Р NMR spectrum, δР, ppm: –1.18. In
the 1Н and 13С NMR spectra the signals of salt (MeO)2·
(EtO)2P+ TfO– are shifted downfield by ~0.1 ppm. The
signals of salt (EtO)4P+ TfO– are overlapped with the
signals of the other two salts. The 31Р signals in all
salts practically coincide.
1
1460, 1248, 1174, 1030, 639, 518. Н NMR spectrum,
δ, ppm: 3.85 d (6Н, СН3, JРH 12.2 Hz), 6.91 d (1Н, JРH
743.9 Hz), 15.08 s (1Н, ОН). 13С NMR spectrum, δС,
ppm: 53.81 d (СH3, JCP 5.9 Hz), 119.48 q (СF3, JCF
318.0 Hz). 19F NMR spectrum, δF, ppm: –78.43. 31Р
NMR spectrum, δР, ppm: 12.69 d.q (JPH 743.3, JPСH
11.8 Hz).
Dimethoxy(hydroxy)phosphonium bis(trifluoro-
methanesulfonyl)imide (XXVII). Yield 100%, light
brown liquid. IR spectrum, ν, cm–1: 2966, 2919, 2861,
2468, 1695, 1351, 1331, 1196, 1143, 1057, 609, 574,
Tris(dimethylamino)(hydroxy)phosphonium tri-
fluoromethanesulfonate (XXIII). Yield 100%, trans-
parent hygroscopic crystals. IR spectrum, ν, cm–1:
2952, 2922, 1465, 1310, 1227, 1181, 1005, 764, 638,
1
514. Н NMR spectrum, δ, ppm: 3.85 d (6Н, СН3, JРH
12.1 Hz), 6.80 d (1Н, JРH 731.9 Hz), 11.77 s (1Н, ОН).
13С NMR spectrum, δС, ppm: 53.33 d (СH3, JCP 5.5 Hz),
119.06 q (СF3, JCF 321.3Hz). 19F NMR spectrum, δF,
ppm: –77.29. 31Р NMR spectrum, δР, ppm: 10.23 d.m
(1JPH 732.0).
1
515, 467. Н NMR spectrum, δ, ppm: 2.75 d (18H,
СН3, JРH 10.1 Hz), 11.13 s (1H, ОН). 13С NMR
spectrum, δС, ppm: 36.37 d (СН3, JCP 5.2 Hz), 119.94 q
(СF3, JCF 318.9 Hz). 19F NMR spectrum, δF, ppm:
–78.55. 31Р NMR spectrum, δР, ppm: 34.85. Found, %:
P 9.89; S 10.49. C7H19F3N3O4PS. Calculated, %: P
9.41; S 9.74.
REFERENCES
1. Wittig, G. and Schöllkopf, U., Chem. Ber., 1954, vol. 87,
no. 9, p. 1318.
Tris(dimethylamino)(hydroxy)phosphonium bis-
(trifluoromethanesulfonyl)imide (XXIV). Yield
100%, a syrup-like mass or crystals. IR spectrum, ν,
cm–1: 3486, 2943, 2921, 1469, 1353, 1191, 1140, 1060,
2. Boutagy, J. and Thomas, R., Chem. Rev., 1974, vol. 74,
no. 1, p. 87.
3. Ma, K., Lee Kw.-M., Minkova, L., and Weiss, R.G.,
J. Org. Chem., 2009, vol. 74, no. 5, p. 2088.
1
1005, 764, 617, 571, 514. Н NMR spectrum, δ, ppm:
4. Roy, M.-N., Poupon, J.-C., and Charette, A.B., J. Org.
Chem., 2009, vol. 74, no. 22, p. 8510.
2.74 d (18H, СН3, JРH 9.9 Hz), 9.05 s (1H, ОН). 13С
NMR spectrum, δС, ppm: 36.51 d (СН3, JCP 4.4 Hz),
119.65 q (СF3, JCF 320.6 Hz). 19F NMR spectrum, δF,
ppm: –78.82. 31Р NMR spectrum, δР, ppm: 34.86.
Found, %: С 20.60; Н 4.09; F 24.74; N 12.12; P 5.73;
S 13.93. C8H19F6N4O5PS2. Calculated, %: С 20.87; Н
4.16; F 24.76; N 12.17; P 6.73; S 13.93.
5. Bradaric, Ch.J., Downard, A., Kennedy, Ch., Robertson, A.,
and Zhou, Y., Green Chem., 2003, vol. 5, no. 2, p. 143.
6. Dake, S.A., Kulkarni, R.S., Kadam, V.N., Modani, S.S.,
Bhale, J.J., Tathe, S.B., and Pawar, R.P., Synth.
Commun., 2009, vol. 39, no. 21, p. 3898.
7. Foropoulos, J. and DesMarteau Jr., D.D., Inorg. Chem.,
Tris(dimethylamino)(methoxy)phosphonium tri-
fluoromethanesulfonate (XXV). Yield 87%, white
crystals, mp 194°С. IR spectrum, ν, cm–1: 3437, 2929,
1469, 1319, 1269, 1151, 1033, 1003, 761, 638, 518. 1Н
1984, vol. 23, no. 23, p. 3720.
8. Koppel, I.A., Taft, R.W., Anvia, F., Zhu, S.-Z., Hu, L.-Q.,
Sung, K.-S., DesMarteau, D.D., Yagupolskii, L.M.,
Yagupolskii, Y.L., Ignat’ev, N.V., Kondratenko, N.V.,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

480
TOLSTIKOVA et al.
Volkonskii, A.Y., Vlasov, V.M., Notario, R., and
26. Klingshirn, M.A., Broker, G.A., Holbrey, J.D.,
Shaughnessy, K.H., and Rogers, R.D., Chem. Commun.,
2002, p. 1394.
Maria, P.-C., J. Am. Chem. Soc., 1994, vol. 116, no. 7,
p. 3047.
9. Gauthier, M., Belanger, A., Kapfer, B., Vassort, G., and
Armand, M., Polymer Electrolyte Reviews: 2, London:
Elsevier, 1989, p. 285.
10. Iwahori, T., Mitsuishi, I., Shiraga, S., Nakajima, N.,
Momose, H., Ozaki, Y., Taniguchi, S., Awata, H., Ono, T.,
and Takeuchi, K., Electrochim. Acta, 2000, vol. 45,
nos. 8–9, p. 1509.
27. Hiemisch, O., Henschel, D., Jones, P.G., and Blaschette, A.,
Z. Anorg. Allg. Chem., 1996, vol. 622, no. 5, p. 829.
28. Haupt von, H.J., Huber, F., Krüger, C., Preut, H., and
Thierbach, D., Z. Anorg. Allg. Chem., 1977, vol. 436,
no. 9, p. 229.
29. Blaschette, A., Wieland, E., Hamann, T., and Jones, P.G.,
Z. Anorg. Allg. Chem., 1990, vol. 589, no. 10, p. 167.
11. Wang, X., Yasukawa, E., and Kasuya, S., J. Electro-
chem. Soc., 2000, vol. 147, no. 7, p. 2421.
12. Broussely, M., Biensan, P., and Simon, B., Electrochim.
Acta, 1999, vol. 45, nos. 1–2, p. 3.
30. Furin, G.G., Krupoder, S.A., Rezvukhin, A.I., Kili-
na, T.M., and Yakobson, G.G., J. Fluor. Chem., 1983,
vol. 22, p. 345.
31. Kirby, A.J. and Warren, S.G., The Organic Chemistry of
Phosphorus, Moscow: Mir, 1971.
13. Favier, I. and Duñach, E., Tetrahedron Lett., 2003,
vol. 44, no. 10, p. 2031.
32. Burg, A.B. and Slota, P.J., J. Am. Chem. Soc., 1958,
14. Ishii, A., Kotera, O., Saeki, T., and Mikami, K., Synlett,
vol. 80, no. 5, p. 1107.
1997, no. 10, p. 1145.
33. Tolstikova, L.L. and Shainyan, B.A., Russ. J. Org. Chem.,
15. Nie, J., Xu, J., and Zhou, G., J. Chem. Res., S, 1999,
2006, vol. 42, no. 7, p. 1068.
vol. 999, no. 7, p. 446.
34. Tolstikova, L.L., Bel’skikh, A.V., and Shainyan, B.A.,
16. Mikami, K., Kotera, O., Motoyama, Y., Sakaguchi, H.,
Russ. J. Org. Chem., 2010, vol. 46, no. 3, p. 383.
and Maruta, M., Synlett, 1996, no. 2, p. 171.
35. Olah, G.A. and McFarland, C.W., J. Org. Chem., 1969,
17. Grieco, P.A. and Handy, S.T., Tetrahedron Lett., 1997,
vol. 34, no. 6, p. 1832.
vol. 38, no. 15, p. 2645.
36. Kühl, O., Phosphorus-31 NMR Spectroscopy:
A
18. Kobayashi, H., Nie, J., and Sonoda, T., Chem. Lett.,
1995, no. 4, p. 307.
19. Handy, S.T., Grieco, P.A., Mineur, C., and Ghosez, L.,
Concise Introduction for the Synthetic Organic and
Organometallic Chemist, Heidelberg: Springer-Verlag,
2008.
37. Singh, S. and DesMarteau, D.D., Inorg. Chem., 1990,
Synlett, 1995, p. 565.
vol. 29, no. 16, p. 2982.
20. Zhang, S., Lu, X., Zhang, Y., Zhou, Q., Sun, J., Han, L.,
Yue, G., Liu, X., Cheng, W., and Li, S., Ionic Liquids
and Relative Process Design; in: Molecular
Thermodynamics of Complex Systems, Berlin: Springer,
2009, vol. 131, p. 143.
21. Pringle, J.M., Golding, J., Baranyai, K., Forsyth, C.M.,
Deacon, G.B., Scott, J.L., and MacFarlane, D.R., New J.
Chem., 2003, vol. 27, no. 10, p. 1504.
38. Rey, I., Johansson, P., Lindgren, J., Lassegues, J.C.,
Grondin, J., and Servant, L., J. Phys. Chem., A., 1998,
vol. 102, no. 19, p. 3249.
39. Tu, M.-H. and DesMarteau, D.D., Spectrochim. Acta,
Part, A., 2005, no. 61, p. 1701.
40. Klamann, D. and Weyerstahl, P., Chem. Ber., 1964,
vol. 97, no. 9, p. 2534.
22. McFarlane, D.R., Sun, J., Golding, J., Meakin, P., and
Forsyth, M., Electrochim. Acta, 2000, vol. 45, nos. 8–9,
p. 1271.
41. Olah, G.A. and McFarland, C.W., J. Org. Chem., 1971,
vol. 36, no. 10, p. 1374.
42. Mark, V. and Van Wazer, J.R., J. Org. Chem., 1964,
vol. 29, no. 5, p. 1006.
23. Quek, S.K., Lyapkalo, I.M., and Huynh, H.V.,
Tetrahedron, 2006, vol. 62, no. 13, p. 3137.
43. Colle, K.S. and Lewis, E.S., J. Org. Chem., 1978,
24. Koch, V., R., Nanjundiah, C., Battista Appetecchi, G.,
and Scrosati, B., J. Electrochem. Soc., 1995, vol. 142,
p. L116.
25. Bonhôte, P., Dias, A., Papageorgiou, N., Kalyana-
sundaram, K., and Grätzel, M., Inorg. Chem., 1996,
vol. 35, p. 1168.
vol. 43, no. 4, p. 571.
44. Hendrickson, J.B., Bair, K.W., Bergeron, R., Giga, A.,
Skipper, P.L., and Sternbach, D.D., and Wareing, J.A.,
Org. Prep. Proc., 1977, vol. 9, no. 4, p. 173.
45. Beard, C.D., Baum, K., and Grakauskas, V., J. Org.
Chem., 1973, vol. 38, no. 21, p. 3673.
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