Synthesis of polyfunctional methylphosphine oxides

Full text of DOI:10.1134/S1070363212060230

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 6, pp. 1171–1173. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.P. Morgalyuk, T.V. Strelkova, E.E. Nifant’ev, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 6, pp. 1037–1039.
LETTERS
TO THE EDITOR
Synthesis of Polyfunctional Methylphosphine Oxides
V. P. Morgalyuk, T. V. Strelkova, and E. E. Nifant’ev
Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
e-mail: morgaliuk@mail.ru
Received November 3, 2011
DOI: 10.1134/S1070363212060230
In previous communications [1–4] it was shown
that the interaction of chlorodiphenylphosphine Ph2PCl
(I) with an excess of a dialkylformamide Alk2NC(H)O
(II) in the presence of catalytic amount (5–15 mol %)
shown that the autocatalytic reaction of synthesis of
compounds IV includes two stages (Scheme 1) [2]: the
synthesis of (dichloro)(diphenyl)[chloro(dialkylamino)
methyl]phosphoranes V in the reaction of I and III,
and the synthesis of the final products IV in
the reaction of halophosphorane V and amide II
accompanied by the recover of compound III,
which is involved in the next step of the interaction
cycle.
of
[Alk2N=C(H)Cl]+ Cl– (III) results in a high yield of the
corresponding chloro(dialkylamino)(diphenylphos-
a
dialkylchloromethyleneiminium
chloride
phoryl)methanes (IV). By an example of chloro(dialkyl-
amino)(diphenylphosphoryl)methane (IVa) we have
Alk
Alk
+
Cl_
+
Cl_
N
O
P CH
Ph
Ph
N
Cl
P
Cl
Ph
Ph
Ph
Ph
Alk2NC(H)O
Alk
Alk
Cl
H
Alk
Alk
Cl
H
Alk
Alk
+
N C
N C
+
Cl
P
CH
Cl
Cl
III
IV
III
I
V
Alk2N denotes the residues of dimethylamine (a), diethylamine (b), N-pyrrolidine (с), N-piperidine (d), and N-morpholine (e).
It seems reasonable to check this scheme using a
new synthetic method derived from this stepwise auto-
catalytic reaction scheme [4].
does not react with I [8, 9] or III [10, 11]. Compounds
III can be synthesized directly in the reaction medium
by reaction of amides II with oxalyl chloride (COCl)2
(VII) [12].
It follows from the scheme that compound IV can
be synthesized without the excesses of II. To do this,
one should add to the reaction medium a compound
capable of replacing the chlorine atoms at the phos-
phorus atom of halophosphorane V by oxygen atom
under mild conditions. Unfortunately, it was impos-
sible to use water or alcohols for this purpose, since
they led to a rupture of phosphorus–carbon bond in
compound IV [5]. However, it was found empirically
that, by analogy with PCl5 [6, 7], for this purpose
dimethoxymethane (MeO)2CH2 (VI) was suitable. It is
known from the literature that at low temperatures VI
The new version of the synthesis of IV also consists
of two stages: the synthesis of phosphorane V in the
reaction of I with an equimolar amount of III and the
synthesis of the final product IV in the reaction of V
with VI. The expected reaction co-products are methyl
chloride (VIII) and methoxy(chloro)methane (IX) [7].
Compounds I and IIIa, IIIb, IIId were introduced
into the reaction in the presence of 4- to 6-fold excess
of VI and a catalytic amount of dioxane [3] at 0°C.
The reaction duration was 4–7 days. During this time,
the [Alk2N=C(H)Cl]+Cl– (III) precipitate gradually
1171

1172
MORGALYUK et al.
Alk
N
+
Cl
Ph
Ph
Cl
P
Cl
Ph
Ph
Alk
Alk
Cl_
Alk
P
+
N C
CH
Cl
H
Cl
I
III
V
Alk
N
O
Ph
Ph
CH2(OMe)2
Alk
[MeCl + MeOCH2Cl]
VIII IX
+
P
CH
Cl
IV
dissolved with simultaneous precipitation of IV (a, b,
and d). The resulting compounds IVa, IVb, and IVd
by melting points and 1H and 31P NMR spectra
correspond to the products synthesized previously by
the autocatalytic reaction [3]. The yields of products
IV are in the range 46–72%. In the syntheses of chloro-
chlorodiphenylphosphine Ph2PCl I, 1,5 g (1.74 ml,
0.0202 mol) of dimethoxymethane and 5 drops of
dioxane. The reaction mixture was left at 0°C while
intermittently stirring. After 8 h a weak gas evolution
began, which ended after four days. The mixture left
standing for 1 day more at 0°C, then it was diluted
with 5 ml of benzene–hexane mixture, 5:1, cooled to
0°C, stirred for 1 min, and the liquid layer was
decanted. The operation was repeated four times. The
solid residue was dried in a vacuum of 12 mm Hg for 1 h,
than 2 days at 1 mm Hg over P2O5 and NaOH. We
obtained 1.91 g (72%) of compound IVa. Colorless
needles, mp 90–94°C with decomposition [2–5]. The
compound is hygroscopic. 31P NMR spectrum, δ, ppm:
(dimethylamino)(diphenylphosphoryl)methane
IVa
and chloro(N-pyrrolidino)(diphenylphosphoryl)methane
IVc a weak gas evolution was marked (presumably
methyl chloride VIII).
The synthesis of compounds IV along the proposed
scheme confirms the presence in the reaction medium
of V, being the adduct of I and III. Further V, as
expected, reacts with VI to give the final reaction
product IV. This in turn confirms the previously
proposed [1, 2] and later experimentally confirmed [4]
scheme of autocatalytic synthesis of chloro(dialkyl-
amino)(diphenylphosphoryl) methanes IV.
1
22.0 d (2JPH = 11.0 Hz). H NMR spectrum, δ, ppm:
2
8.00–7.93 m (4H, o-H, Ph), 7.89 d (1H, CH, JPH
=
11.0 Hz), 7.56–7.49 m (6H, m,p-H, Ph), 3.08 s [6H, N
(CH3)2].
1
The H and 31P NMR spectra (δ, ppm) were re-
By similar procedure also compounds IVc and IVd
were synthesized.
gistered on a Bruker Avance 300 spectrometer, operat-
ing frequency 300.11 and 121.50 MHz, respectively,
solvent CDCl3. The registration of H and 31P NMR
1
(Diphenylphosphoryl)(N-pyrrolidino)chloromethane
(IVc). The reaction duration 4 days. Yield 53%. A pale
yellow hygroscopic substance, mp 79–82°C with decom-
spectra of IV was performed immediately after their
dissolution in CDCl3 [3]. Dialkylformamides used in
the study were twice distilled over CaH2; dimethoxy-
methane, CDCl3, CH2Cl2, benzene, and hexane were
distilled over P2O5.
position [3]. 31P–{1H} NMR spectrum, δ, ppm: 19.3 s.
2
1H NMR spectrum, δ, ppm: 10.31 d (1H, CH, JPH
=
23.0 Hz), 8.20–8.13 m (4H, o-H,Ph), 7.61–7.49 m (6H,
m,p-H, Ph), 4.22 s (4H, 2NCH2), 1.35 d (4H, 2CH2).
Synthesis of chloro(dialkylamino)(diphenylphos-
phoryl)methane (IVa). To a solution of 0.33 g (0.35 ml,
0.0045 mol) of DMF (IIa) in 5 ml of CH2Cl2 at 0°C,
was slowly added dropwise at vigorous stirring 0.7 g
(0.48 ml, 0.0055 mol) of oxalyl chloride (COCl)2 (VII)
in 5 ml of CH2Cl2. After the end of gas evolution,
CH2Cl2 was distilled off in a vacuum of 50 mm Hg
(strong foaming) at 25°C. To the solid residue of
dialkylchloromethyleneiminium IIIa cooled to 0°C was
successively added 1.2 g (0.96 ml, 0.0054 mol) of
(Diphenylphosphoryl)(N-piperidino)chloromethane
(IVd). The reaction time 7 days. Yield 46%. A light
yellow hygroscopic substance, mp 85–88°C with
decomposition [3]. 31P–{1H} NMR spectrum, δ, ppm:
1
20.2 s. H NMR spectrum, δ, ppm: 9.78 d (1H, CH,
2JPH = 21.0); 8.17–8.09 m ( 4H, o-H, Ph), 7.62–7.51 m
3
(6H, m,p-H, Ph), 4.12 t (4H, 2NCH2, JHH = 6.0 Hz),
1.82 br.s (Δν1/2 = 11 Hz, 4H,CH2CH2CH2), 1.64
quintet (2H,CH2CH2CH2, 3JHH = 6.0 Hz).
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SYNTHESIS OF POLYFUNCTIONAL METHYLPHOSPHINE OXIDES
6. Whitmore, L., J. Am. Chem. Soc., 193, vol. 55, no. 4,
p. 1518.
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