Interaction of PH3 with acetaldehyde in aqueous media and chemistry of [HO(Me)CH]4PCl

Article abstract of DOI:10.1134/S1070363213020047

The known phosphonium chloride [HO(Me)CH]₄PCl was prepared at ambient conditions from PH₃ and acetaldehyde in aqueous HCl, and characterized by elemental analysis and ¹H and ³¹{ ¹H} NMR spectroscopy. Attempts to obtain the tertiary phosphine [HO(Me)CH]₃P via reaction of [HO(Me)CH]₄PCl with Na ₂SO₃ or Et₃N in aqueous media under Ar revealed that [HO(Me)CH]₃P is unstable and equilibrates with the secondary phosphine [HO(Me)CH]₂PH and acetaldehyde. A 1:4 reaction of [HO(Me)CH]₄PCl with NaHSO₃ at room temperature under Ar affords first the oxide [HO(Me)CH]₂P(O)H and then the phosphinic acid [HO(Me)CH]₂P(O)OH. A 1:1 reaction of [HO(Me)CH]₄PCl with Na₂S₂O₃ affords the sulfide [HO(Me)CH] ₃PS. ³¹{¹H} and ¹H NMR data for all the (α-hydroxyethyl)phosphorus species are reported for the first time.

Full text of DOI:10.1134/S1070363213020047

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 2, pp. 252–259. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © D.V. Moiseev, B.R. James, A.V. Gushchin, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 2, pp. 198–205.
Interaction of PH3 with Acetaldehyde in Aqueous Media
and Chemistry of [HO(Me)CH]4PCl
D. V. Moiseeva,b, B. R. Jamesa, and A. V. Gushchinb
aDepartment of Chemistry, University of British Columbia, Vancouver,
British Columbia, V6T 1Z1 Canada
e-mail: moisdv@hotmail.com; brj@chem.ubc.ca.
bDepartment of Organic Chemistry, Lobachevsky State University of Nizhny Novgorod,
pr. Gagarina 23, Nizhny Novgorod, 603950 Russia
Received December 20, 2011
Abstract―The known phosphonium chloride [HO(Me)CH]4PCl was prepared at ambient conditions from PH3
1
and acetaldehyde in aqueous HCl, and characterized by elemental analysis and H and 31P{1H} NMR
spectroscopy. Attempts to obtain the tertiary phosphine [HO(Me)CH]3P via reaction of [HO(Me)CH]4PCl with
Na2SO3 or Et3N in aqueous media under Ar revealed that [HO(Me)CH]3P is unstable and equilibrates with the
secondary phosphine [HO(Me)CH]2PH and acetaldehyde. A 1:4 reaction of [HO(Me)CH]4PCl with NaHSO3 at
room temperature under Ar affords first the oxide [HO(Me)CH]2P(O)H and then the phosphinic acid [HO(Me)
CH]2P(O)OH. A 1:1 reaction of [HO(Me)CH]4PCl with Na2S2O3 affords the sulfide [HO(Me)CH]3PS. 31P{1H}
and 1H NMR data for all the (α-hydroxyethyl)phosphorus species are reported for the first time.
DOI: 10.1134/S1070363213020047
(α-Hydroxymethyl)phosphines and the correspond-
ing phosphonium salts have attracted much attention,
and this is exemplified by a recent review on the
diverse coordination chemistry of (HOCH2)3P and its
industrial applications [1]. This phosphine, readily
formed from the phosphonium salt (HOCH2)4PCl (or
the corresponding sulfate) has been used commercially
as a bleaching and brightness stabilizing agent of
mechanical pulps [2–6], and as a component for flame-
and glow-resistant polymers [7–9]. There is also a
patent on use of the oxide and sulfide derivatives,
(HOCH2)3PO and (HOCH2)3PS, in the manufacture of
fire-retardant polyurethanes [10]. The (HOCH2)4PCl
salt can be obtained by passing PH3 through a solution
of formaldehyde in the presence of HCl, a carbonyl-
hydrophosphination reaction [11–14], and treatment of
this salt with a base such as NaOH [15, 16], Et3N [17,
18], or Bu3P [19], or interaction with Na2SO3 [8, 20],
affords (HOCH2)3P, which is stable (even under air) in
aqueous media at pH 7.0–8.0 [21].
phosphination reactions of PH3 with acetaldehyde and
propionaldehyde, respectively, in the presence of HCl
[22]. The chloride I and the [HO(R)CH]4PCl analogues
(R = n-C6H13 and n-C11H23) were similarly prepared in
the early 1960s, but characterized only by elemental
analysis and/or melting point [13]. In 1998,
[HO(R)CH]4PCl (R = n-C9H19 and again n-C11H23)
were synthesized by the same methodology, and their
1
characterization now included H-, 31P{1H}-, and 13C
{1H}-NMR data [23]. Reaction of aldehydes, branched
at the α-position, with PH3/HCl affords only secondary
(α-hydroxyalkyl)phosphine derivatives [13]. To the
best of our knowledge, the only reported example of a
tertiary tris(α-hydroxyalkyl)phosphine other than
(HOCH2)3P is [HO(Cl3C)CH]3P [24].
Following the discovery of the pulp-bleaching
activity of (HOCH2)3P, a strong reductant and nucleo-
phile [1–6], our group has investigated interactions of
tertiary or secondary phosphines with substituted
benzaldehydes [25], benzyl and cinnamyl alcohols
[26], quinones [27], and α,β-unsaturated aldehydes
[28–32]. The general conclusion is that the bleaching
activity occurs by the loss of conjugation in organic
frameworks. A general problem associated with the
use of (HOCH2)3P, and (α-hydroxyalkyl)phosphines, is
Reports on syntheses of other tetrakis(α-hydroxy-
alkyl)phosphonium chlorides are few, although tetrakis-
(α-hydroxyethyl)phosphonium chloride, [HO(Me)CH]4·
PCl (I), and the α-hydroxypropyl analogue [HO(Et)·
CH]4PCl were apparently prepared in 1888 via hydro-
252

INTERACTION OF PH3 WITH ACETALDEHYDE IN AQUEOUS MEDIA
253
(1)
RCHO
RCHO
RCHO
HCl
RCHO
[HO(R)CH]2PH
PH3
[HO(R)CH]PH2
[HO(R)CH]3P
[HO(R)CH]4PCl
the reversibility of their formation via phosphine/
aldehyde reactions as shown in Eq. (1) [21, 25, 28, 30,
31], and this led us to study the preparation, stability,
and chemical properties of tris(α-hydroxyethyl)
phosphine, [HO(Me)CH]3P (II).
ratios being 1:4:4. These ratios remain constant in all
the chloride I reactions studied, implying that the three
resonances are associated with the phosphonium
chloride [more correctly I-d4, as defined in Eq. (2)]
containing four identical, chiral C-centers bonded to a
tetrahedral P-atom. Theoretically, three 31P–{1H}
resonances corresponding to three possible diastereo-
mers should be observed in a 1:4:3 ratio: one (RRRR)/
(SSSS) isomer, four isomers of identical structures
where only one group is different [(RRRS)/(RSSS) =
(RRSR)/(SRSS) = (RSRR)/(SSRS) = (SRRR)/(SSSR)],
and three isomers with structures where two groups are
different [(RRSS)/(SSRR) = (RSRS)/(SRSR) = (RSSR)/
(SRRS)] (see Scheme 1). The smaller 27.6 ppm signal
is thus attributed to the (RRRR)/(SSSS) diastereomer.
The slight deviation from the expected ratio possibly
results from an equilibrium present in D2O (Eq. 2),
similar to the one established for (HOCH2)4PCl (pKd ~
7.1 [21, 35, 36]); this equilibrium might favor one of
three I-d4 diastereomers, because of steric hindrance
caused by the deuteroxyethyl groups within [DO(Me)
CH]3P (II-d3). For the phosphonium salts [HO(n-
C9H19)CH]4PCl and [HO(n-C11H23)CH]4PCl, three δP
resonances were detected in ratios of 2:3:5 and ~1:2:3,
respectively, and were reported as ‘nearly identical’ to
the statistical value [23].
This report describes NMR data for I and its
reactions with Et3N and Na2SO3 in attempts to obtain
the tertiary phosphine II. Interactions of I with
NaHSO3 and Na2S2O3, sulfur-containing salts that are
decomposition products of sodium dithionite
(Na2S2O4), are also described, the interest here being
associated with the synergic effect observed for a
combination of (HOCH2)3P and dithionite in pulp-
bleaching [33, 34].
Pure chloride I was prepared by a PH3/
acetaldehyde/HCl reaction in water, with a final
recrystallization of the isolated residue from EtOH; a
literature method used an aqueous/THF solvent and,
for the residue, a trituration procedure with MeCN
[13]. The product is highly water-soluble and its
solution is stable in air, as is (HOCH2)4PCl [21]. The
31P{1H} spectrum in D2O revealed three singlet
resonances: a smaller one at δP 27.6 ppm and two of
equal intensity at δP 28.3 and 27.8 ppm, the integration
Kd
[DO(Me)CH]4P+Cl
[DO(Me)CH]3P + MeCHO + DCl
(2)
I-d4
II-d3
The CH3 protons of the chloride I-d4 are seen in the
the CH proton is seen as a multiplet at δH 5.16 ppm,
1H spectrum as three overlapping doublets of doublets
which is presumably three doublets of quartets with a
3
2
1
(3JHH 7.1, JPH 14.3 Hz) centered at δH 1.78 ppm, and
small JPH coupling constant because, in the H–{31P}
Scheme 1.
OH
*
H
H
*
*
*
*
HO
HO
HO
HO
OH
*
HO
H
P+
P
P
P
*
*
*
HO
OH
*
HO
(R)/(S)
(RR)/(SS)
(RS)/(SR)
1:1
(RRR)/(SSS)
(RRRR)/(SSSS)
[(RRS)/(RSS),(RSS)/(SRR), [(RRRS)/(RSSS), RRSR)/(SRSS),
(RSR)/(SRS)]
(RSRR)/(SSRS), (SRRR)/(SSSR)]
[(RRSS)/(SSRR), RSRS)/(SRSR),
(RSSR)/(SRRS)]
1:3
1:4:3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 2 2013

254
MOISEEV et al.
spectrum, there is no significant change in the CH
proton pattern.
at δP –26.8, –28.5 and –31.6 ppm (1JPD 33 Hz) in a
1:2:1 ratio (Fig. 1a), instead of the expected two 1:1
resonances for the (RR)/(SS) and (RS)/(SR) diastereo-
mers (Scheme 1). A plausible rationalization is that in
the (RS)/(SR) enantiomers, the P-atom is chiral because
the hydroxyethyl groups with (R)- or (S)-chirality are
different, and so this generates two (RSR) and (SRS)
enantiomers that are apparently not NMR-identical. Of
interest, only one δP 15.6 ppm resonance was given for
[HO(Cl3C)CH]3P, and this was assigned to a preferred
(RRR)/(SSS) diastereomer of just two considered
possibilities: (RRR)/(SSS) and (RRS)/(RSS) [24]. In the
1H spectrum, the CH protons of II-d3 and III-d3 appear
as a broad multiplet at δH 4.69–4.43 ppm, which
overlaps with the CH resonance of DO(Me)C(H)
SO3Na, and a doublet of quartets at δH 4.38 ppm (3JHH
An NMR investigation of a 1:1 reaction of I with
Na2SO3 in D2O at room temperature (r.t., ~295 K)
under Ar revealed that the phosphine II-d3 is formed
initially in the first stage; the reaction stoichiometry is
presumably that shown in Eq. 3, which has been
established for (HOCH2)3P {Eq. (3), with Me replaced
by H [8, 20, 33]}; the deuteroxymethane-sulfonate salt
-
is formed via the reaction of HSO3 with acetaldehyde.
However, unlike (HOCH2)3P which is stable under
such conditions, the phosphine II-d3 partially
decomposes to the deuterated bis(α-hydroxyethyl)
phosphine [DO(Me)CH]2PD (III-d3) and acetaldehyde
[Eq. (4)]. In the 31P–{1H} spectrum recorded after
15 min, II-d3 is seen as the expected two singlets
(Scheme 1) at δP 8.4 and 7.1 ppm in a 1:3 ratio
(Fig. 1a). The phosphine III-d3 is seen as three triplets
2
7.3 and JPH 1.9 Hz), which is assigned to one of the
II-d3 diastereomers.
[DO(Me)CH]4P+Cl_ + Na2SO3
[DO(Me)CH]3P + DO(Me)C(H)SO3Na + NaCl
(3)
(4)
[DO(Me)CH]3P
[DO(Me)CH]2PD + MeCHO
II-d3
III-d3
(a)
II-d3
III-d3
I-d3
(b)
IV-d3
δ, ppm
Fig. 1. The 31P–{1H} spectrum of the reaction of I (present as I-d4) and Na2SO3 (1:1, Ar, D2O, r. t.) after: (a) 15 min; (b) 1 day.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 2 2013

INTERACTION OF PH3 WITH ACETALDEHYDE IN AQUEOUS MEDIA
255
The Me resonances of both phosphines form a
broad multiplet at δH 1.60–1.40 ppm. The CH and Me
protons of the deuteroxymethane-sulfonate anion,
After 1 day, the 31P–{1H} spectrum (Fig. 1b)
revealed a quintet at δP –110.2 ppm (1JPD 32 Hz)
assignable to deuterated mono(α-deuteroxyethyl)phos-
phine [DO(Me)CH]PD2 (IV-d3), the disproportiona-
tion product of III-d3 [Eq. (5)]. Use of a 2-fold excess
of Na2SO3 (D2O, r.t., Ar) completely consumed the I-d4
in 20 min, when II-d3 and III-d3 were present in a ratio
of 4:5; the acetaldehyde was detected only as the diol.
-
DO(Me)C(H)SO3 , are seen as a quartet at δH 4.60 and
a doublet at 1.51 ppm (3JHH 6.6 Hz), respectively.
Acetaldehyde (δH 9.70 quartet, 2.27 doublet, 3JHH 3.0 Hz)
and its diol, present as MeCH(OD)2 (δH 5.27 quartet,
1.35 doublet, 3JHH 5.2 Hz), are also observed.
(5)
[DO(Me)CH]2PD
[DO(Me)CH]3P + DO(Me)CHPD2
IV-d3
III-d3
II-d3
Neutralization of the chloride I with Et3N (1:1 or
1:2, r.t., Ar, D2O) also leads to a mixture of II-d3 and
III-d3, but now in a 2:1 ratio because the equilibrium
of Eq. (4) is shifted to the II-d3 side in the absence of
the SO32– that scavenges the acetaldehyde under these
conditions [see Eq. (3)].
tion product of V-d3, and the 1:1 intensities are
consistent with the presence of just the two chiral C-
1
centers. The H data (see below) are also consistent
with the loss of two aldehyde equivalents from the
chloride I-d4 in that the final DO(Me)C(H)SO3Na: VI-
d3 ratio is 2:1.
In the 1H spectrum of V-d3, instead of the
anticipated two sets of resonances due to two
diastereomers, three types of DO(Me)CH moieties
were detected. Multiplets of the CH and Me protons,
centered at δH 4.50 and 1.60 ppm, respectively (Fig. 3),
were simulated as three overlapping AM3X spin
systems using: (a) (a) JAM 7.3, JAX 4.2, JMX 16.0 Hz;
(b) JAM 7.3, JAX 4.6, JMX 16.0 Hz; and
(c) JAM 7.3, JAX 1.9, JMX 15.5 Hz (in all cases X is the
The instability of II, the first reported homolog of
the widely used (HOCH2)3P, in aqueous media (and
almost certainly in organic media) is consistent with
reported data that steric hindrance prohibits formation
of tris- and tetrakis(α-hydroxyalkyl)phosphorus deriva-
tives [13]. The instability is also consistent with our
findings that electron-donor groups facilitate decom-
position of (α-hydroxyalkyl)phosphines [30, 31].
Consistent with this, the use of the electron-accepting
CCl3 group generates the stable, but water-insoluble,
tris(α-hydroxyalkyl)phosphine [HO(Cl3C)CH]3P [24].
1
P-atom). This H pattern implies that the HO(Me)CH
groups of one diastereomer are anisochronous (Δ ~ 4 Hz).
The Me protons of two diastereomers of VI-d3 are seen
at δH 1.45 and 1.43 ppm (Fig. 4) as two doublets of
A 1:1 mixture of I and NaHSO3 (D2O, Ar, r.t.)
shows no immediate reaction, as reported for the
corresponding (HOCH2)4PCl system [33]. After 30 min
in a 1:4 chloride I and NaHSO3 reaction, the 31P–{1H}
spectrum revealed two equal intensity triplets at δP
50.1 and 48.3 ppm with 1JPD 72 Hz (Fig. 2a); these are
assigned to the two diastereomers of the deuterated bis-
(α-hydroxyethyl)phosphine oxide [DO(Me)CH]2P(O)D
(V-d3), the 1JPD value being essentially the same as that
found for [DOCH2]2P(O)D [33]. The triplets were
slowly replaced over a day by two 1:1 singlets seen
first at δP 44.8 and 43.8 ppm (Fig. 2a), but over 2 days
these shift downfield by ~2 ppm (Figs. 2b, 2c); at this
stage, only these two singlets could be seen along with
the small δP 64.4 and 62.9 ppm signals that are
assigned to the sulfide [DO(Me)CH]3PS (see below).
3
3
3
doublets (3JHH 7.1, JPH 14.8 Hz and JHH 7.3, JPH
14.3 Hz, respectively), while the CH protons are seen
as two overlapping quartets at δH 4.22 and 4.19 ppm
(implying no measurable 2JPH coupling). After 30 min,
both DO(Me)C(H)SO3Na and acetaldehyde diol were
detected, whereas only the sodium salt was observed
after 1 day. It should be noted that after 2 h of reaction,
an off-white suspension of elemental sulfur appeared;
the S8 could be identified by its characteristic
fragmentation pattern in a low-resolution EI mass
spectrum [37]. The increasing presence of the
suspension could well give rise to the minor shifts in
the NMR spectra. The observed changes (carried out
under Ar) are outlined in Scheme 2, although the
source of the [O] required for the oxidation is unclear;
trace O2 is considered unlikely, and the well
established OH- oxidation of phosphines with co-
generation of H2 [15, 21, 38] seems more plausible.
1
The new singlets, because of the absence of JPD
coupling, are assigned to the phosphinic acid
derivative [DO(Me)CH]2P(O)OD (VI-d3), the oxida-
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256
MOISEEV et al.
(a)
VI-d3
V-d3
VII-d3
(b)
(c)
VI-d3
δ, ppm
Fig. 2. The 31P–{1H} spectrum of the reaction of I (present as I-d4) and NaHSO3 (1:4, Ar, D2O, r. t.) after: (a) 30 min; (b) 1 day;
and (c) 2 days.
The earlier reported [33], corresponding slow
oxidations under Ar of (HOCH2)4PCl to give the oxide
and phosphinic acid derivative are similarly poorly
understood. It should also be noted that, in the reaction
of PH3 with benzaldehyde in basic conditions, a
transfer of the carbon-oxygen to the phosphorus with
the formation of a phosphine oxide or phosphinic acid
can take place [39, 40] but, in the presence of
NaHSO3, any acetaldehyde present would form
DO(Me)C(H)SO3– and prevent any such oxidation
process.
In a reaction of I with Na2S2O3 in D2O (1:1, Ar,
r.t.), the 31P{1H} resonances of I-d4 are replaced within
15 min by two lower field singlets at δP 64.4 and 62.9 ppm
in a diastereomeric ratio of 1:3.5 (see also Fig. 2). These
singlets are assigned to the sulfide [DO(Me)CH]3PS
(VII-d3), formed according to Eq. (6), by analogy with
δ, ppm
δ, ppm
Fig. 3. The experimental (top) and simulated (bottom)
AM3X 1H NMR patterns (X = P) for the CH and Me
protons of V-d3.
Fig. 4. The experimental (top) and simulated (bottom)
AM3X 1H NMR patterns (X = P) for the CH and Me
protons of VI-d3.
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INTERACTION OF PH3 WITH ACETALDEHYDE IN AQUEOUS MEDIA
257
Scheme 2.
O
O
[O]
[O]
+NaHSO3
[DO(Me)CH]2P
[DO(Me)CH]2PD
[DO(Me)CH]4PCl
[DO(Me)CH]2P
_DO(Me)C(H)SO3Na
D
OD
VI-d3
V-d3
the corresponding reaction of (HOCH2)4PCl with
Na2S2O3 under the same conditions [33]. The ratio of
the (RRR)/(SSS) and [(RRS)/(RSS), (RSS)/(SRR),
(RSR)/(SRS)] diastereomers is close to the expected 1:3
for three identical chiral centers (see Scheme 1).
atom, JAM 6.9, JAX 2.0, JMX 15.2 Hz), and an AM3 spin
system (JAM 6.5 Hz) for DO(Me)C(H)SO3Na. This
implies that the P-atom of the (RRS)/(RSS), (RSS)/
(SRR), and (RSR)/(SRS) enantiomers possesses one
DO(Me)CH group of opposite chirality, and is thus
prochiral, whereas the DO(Me)CH groups with
the same chirality become NMR nonequivalent
(anisochronous) and give rise to different 1H
resonances.
1
However, the H spectrum (Fig. 5, top) is surprisingly
complex, but can be simulated (Fig. 5, bottom) as four
equal intensity AM3X spin systems for the CH and Me
protons of four deuteroxyethyl groups (where X is a P-
(6)
[DO(Me)CH]3PS + DO(Me)C(H)SO3Na + NaCl
VII-d3
[DO(Me)CH]4PCl + Na2S2O3
D2O
EXPERIMENTAL
(relative to external SiMe4) and 85% aq. H3PO4 being
used as references. Elemental analyses were performed
by M. Lakha on a Carlo Erba 1108 analyzer in the
UBC department.
Before use, distilled water and D2O were stirred for
4 h under Ar. CD3OD (Cambridge Isotope Labor-
atories) and EtOH were used as received, as were the
Aldrich chemicals PH3 (electronic grade) and
acetaldehyde, and the Fisher Scientific products
Na2S2O3, Na2SO3, NaHSO3, and 37% aq. HCl. NMR
spectra were recorded on a Bruker AV300 spec-
Preparation of [HO(Me)CH]4PCl (I). PH3 was
bubbled for 1.5 h through an acetaldehyde (23 g)
solution in air-free water (100 ml) with dropwise
addition of HCl (37% aq., 52 ml). After removal of
water, the white residue was recrystallized from a
saturated solution in EtOH to give the chloride I in
1
31
trometer at 300 K (300 MHz for H; 121 MHz for P
{1H}) with a residual deuterated solvent proton
δ, ppm
Fig. 5. The experimental (top) and simulated (bottom) AM3X 1H NMR patterns (X = P) for the CH and Me protons of VII-d3; the
spectra also include the AM3 resonances for the CH protons (quartet at δH 4.60 ppm) and Me protons (doublet at δH 1.51 ppm) of
DO(Me)C(H)SO32–.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 2 2013

258
MOISEEV et al.
4. Hu, T.Q., James, B.R., Yawalata, D., Ezhova, M.B., and
Chandra, R., J. Pulp Paper Sci., 2005, vol. 31, no. 2,
p. 69.
~80% yield. Found, %: C 39.3, H 7.8. C8H20ClO4P.
1
31
Calculated, %: C 38.95, H 8.17. The H and P–{1H}
NMR data are discussed in the text.
5. Hu, T.Q., James, B.R., Yawalata, D., and Ezhova, M.B.,
NMR investigation of a 1:1 reaction of the
chloride I with Na2SO3. In a glove-box, I (30 mg,
0.12 mmol) was dissolved in a stirred, air-free D2O
solution (~1.5 ml) containing Na2SO3 (15.4 mg,
0.12 mmol). A sample of the solution (~0.7 ml) was
then placed in a J-Young NMR tube and the spectra
were recorded periodically at r.t. The same procedure
was used for studying 1:1 reactions of I with Et3N
(12.3 mg, 0.12 mmol), Na2S2O3 (19.2 mg, 0.12 mmol),
and NaHSO3 (12.7 mg, 0.12 mmol); reactions using
stoichiometries other than 1:1 were studied similarly.
J. Pulp Paper Sci., 2006, vol. 32, no. 3, p. 131.
6. Chandra, R., Hu, T.Q., James, B.R., Ezhova, M.B., and
Moiseev, D.V., J. Pulp Paper Sci., 2007, vol. 33, no. 1,
p. 15.
7. Reeves, W.A. and Guthrie, J.D., Ind. Eng. Chem., 1956,
vol. 48, no. 1, p. 64.
8. Frank, A.W., Daigle, D.J., and Vail, S.L., Textile Res.
J., 1982, vol. 52, no. 11, p. 678.
9. Frank, A.W., Daigle, D.J., and Vail, S.L., Textile Res.
J., 1982, vol. 52, no. 11, p. 738.
10. Hoye, P.A.T. and Coates, H., GB Patent 974033, 1964.
11. Hoffman, A., J. Am. Chem. Soc., 1921, vol. 43, no. 7,
CONCLUSIONS
p. 1684.
Tetrakis(α-hydroxyethyl)phosphonium
chloride,
12. Reeves, W.A., Flynn, F. F., and Guthrie, J. D., J. Am.
Chem. Soc., 1955, vol. 77, no. 14, p. 3923.
[HO(Me)CH]4PCl, is characterized for the first time by
1H and 31P{1H} NMR spectroscopy, which reveals that
the compound consists of three diastereomers in a
4:4:1 ratio. Reaction of [HO(Me)CH]4PCl with
Na2SO3 or Et3N in attempts to isolate [HO(Me)CH]3P
leads to an equilibrium between this tertiary phosphine
and the secondary phosphine [HO(Me)CH]2PH.
Except for (HOCH2)3P, tris(α-hydroxyalkyl)phos-
phines are generally unstable in aqueous media.
Established also is that the water-soluble phosphinic
acid [HO(Me)CH]2P(O)OH can be easily obtained by
a 1:4 reaction of [HO(Me)CH]4PCl with NaHSO3 (r.t.,
Ar), the secondary phosphine oxide [HO(Me)CH]2·
P(O)H being an intermediate in this process.
Interaction of [HO(Me)CH]4PCl with Na2S2O3 affords
the sulfide [HO(Me)CH]3PS. Plausible rationales are
presented for differences between the observed and
theoretical/statistical diastereomeric ratios in the (α-
hydroxyethyl)-containing phosphorus compounds.
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