Reaction of 3,3,5-trimethyl-2-chloro-1,2-oxaphospholene 2-oxide with grignard reagents, a convenient approach to the synthesis of dialkyl(diaryl)-(1-methyl-4-oxopent-2-yl)phosphine oxides

Full text of DOI:10.1134/S1070363210070297

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 7, pp. 1377–1379. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © D.A. Tatarinov, V.F. Mironov, A.A. Kostin, T.A. Baronova, B.I. Buzykin, 2010, published in Zhurnal Obshchei Khimii, 2010,
Vol. 80, No. 7, pp. 1211–1213.
LETTERS
TO THE EDITOR
Reaction of 3,3,5-Trimethyl-2-chloro-1,2-oxaphospholene
2-Oxide with Grignard Reagents,
a Convenient Approach to the Synthesis
of Dialkyl(diaryl)-(1-methyl-4-oxopent-2-yl)phosphine Oxides
D. A. Tatarinov, V. F. Mironov, A. A. Kostin, T. A. Baronova, and B. I. Buzykin
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
Received June 9, 2009
DOI: 10.1134/S1070363210070297
O
P
1
An important area in the chemistry of organo-
phosphorus compounds is the design of new types of
P-ligands containing, along with the phosphorus(III)
atom or phosphoryl group, one or more other
functional groups (amino, hydroxy, oxo, etc.). In this
regard, of particular interest is a modification of the
phosphine oxides, which are used widely and in
diverse applications. Thus, the complexes of phosphine
oxides with some metals show catalytic properties in a
number of organic reactions [1] and are used for the
preparation of ion-selective electrodes [2, 3], and in
high-performance extraction of various metals [4, 5].
Fluorescent complexes of phosphine oxides with
lanthanum group metals are used as light emitting
components in organic light emitting diodes and
devices based on them [6]. The functionalization of
phosphine oxides by introduction of additional
complexing groups extends their application, but is
hampered by the lack of simple approaches to their
synthesis allowing a wide variation of the nature of the
substituents, particularly at the phosphorus atom.
O
O
(1) 2 RMgX
R
R
3
6
P
4
O
2
(2) HCl, H2O
Cl
−MgClX
5
I
IIa−IIc
9
7
8
7
10
8
9
R = CH2CH2CH3 (а), CH2CH2CH2CH3 (b), Ph (c).
The structure of phosphine oxides II was confirmed
by H, 31P, and 13C NMR spectroscopy, IR spec-
1
troscopy, and mass spectrometry.
(1-Methyl-4-oxopent-2-yl)dipropylphosphine
oxide (IIa). To the Grignard reagent obtained by a
usual procedure from 3.3 g (0.1375 mol) of mag-
nesium and 12.5 ml (16.9 g, 0.1375 mol) of propyl
bromide in 50 ml of diethyl ether was added dropwise
10 g (0.0554 mol) of chlorophospholene I. The reac-
tion mixture was vigorously stirred for 30 min, then it
was neutralized with 30 ml of water and 12 ml of
concentrated hydrochloric acid at vigorous stirring and
boiling. The organic layer was separated from the
aqueous layer, the latter was extracted with three 200-
ml portions of methylene chloride, the extracts were
combined with the organic layer, the solvent was
distilled off, and the residue was dried in a vacuum
(12 mm Hg, 100°C). We isolated 12.0 g (93%) of com-
pound IIa as a light yellow oil, bp 122–124°C
(0.03 mm Hg), nD20 1.4760. IR spectrum, cm–1: 732,
782, 830, 907, 944, 990, 1034, 1080, 1134, 1161,
1249, 1365, 1414, 1463, 1647, 1713, 2876, 2935,
We developed a new approach to the synthesis of a
class of functionally substituted phosphine oxides
containing carbonyl group in the γ-position to the
phosphorus atom. It consists in the reaction of P-
heterocycles such as 3,3,5-trimethyl-2-chloro-1,2-
oxaphospholene 2-oxide (I) [7–9] with organo-
magnesium compounds in 1:2 ratio. After hydrolysis
of the reaction mixture dialkyl(diaryl)(1-methyl-4-
oxopent-2-yl)phosphine oxides (II) were isolated in
high yields (above 90%).
2966. 0.93 br t (H9, 6H, JHCCH 7.2–7.4), 1.19 d (H1,6,
3
1377

1378
TATARINOV et al.
3
3
6H, JPCCH 15.5), 1.52 m (H8, 4H, JHCCH 7.2–7.4,
3JHCCH 6.5–7.0), 1.73 and 1.82 two m (H7, 4H, АВ-part
of АВMХ2 spectrum), 2.08 s (H5, 3H), 2.69 d (H3, 2H,
3JPCCH 9.8). 13C NMR spectrum (D2O), δ, ppm (J, Hz)
2938, 2976. 1H NMR spectrum, δ, ppm (J, Hz): 1.43 d
(H1,6, 6H, 3JPCCH 15.9), 2.11 s (H5, 3H), 2.73 d (H3, 2H,
3JPCCH 7.3), 7.51–7.55 m (CH-m, CH-p, 6H, AA'B-part
of the AA'BMXX' spectrum), 7.99 br.d.d (CHO, 4H,
3
(in parentheses is shown the shape of the signal in the
XX'-part of the AA'BMXX' spectrum JHCCH 8.0–8.3,
13C–{1H} NMR spectrum): 20.22 q.m (s) (C1,6, JHC
3JPCCH 8.3–8.5). 31P–{1H} NMR spectrum: δP 39.7
ppm. Mass spectrum, m/z: 301 [M + H]+, 300 [M]+,
285 [M – CH3], 257 [M – C2H3O], 244 [M – C3H4O],
243 [M – C3H5O], 219 [M – C6H9], 202 [M – C6H10O],
201 [M – C6H11O], 155 [C12H11], 154 [C12H10], 125
[C6H7OP], 124 [C6H6OP], 99.0 [C6H11O], 81 [C6H9],
77, 57, 55, 43, 29. Found, %: C 71.93; H 7.09; P
10.27. C18H21O2P. Calculated, %: C 71.98; H 7.05; P
10.31.
1
1,6
128.6), 34.78 d.m (d) (C2, JPC 63.1, JHCC 4.2, JHCC
1
2
2
2
2
2
3.6), 46.83 br.t.m (br.s) (C3, JHC 128.0), 213.16 d.q.t
1
3
(d) (C4, JPCCC 11.4, JHC C 5.5–6.0, JHC C 5.5–6.0),
3
2
2
4
5
4
3
4
32.44 q.t.d (d) (C5, JHC 128.0, JHC CC 3.6, JPCCCC
1
3
4
5
3
5
5
1.8), 25.35 br.t.d.m (d) (C7, JH C 126.2, JPC 61.3,
1
1
7
7
2
3
8
9
JHC C7 3.0–4.0, JHC CC7 6.0–7.0), 15.61 t. d.q.t. (d),
1
2
2
2
(C8, JHC 128.6, JPCC 5.0, JHC C 4.2–4.5, JHC C 4.2–
8
8
7
8
9
8
4.5), 15.42 q.d.t.t (d), (C9, JHC 126.3, JPCCC 15.0,
1
3
9
9
JHC C 4.2, JH C CC 5.6–6.0). P–{1H} NMR spectrum:
2
3
31
8
9
7
9
1
13
13
The H, C, C–{1H}, and 31P–{1H} NMR spectra
δP 56.4 ppm. Found, %: C 62.24; H 10.65; P 13.23.
C12H25O2P. Calculated, %: C 62.04; H 10.85; P 13.33.
1
were recorded on Bruker Avance-600 (600 MHz, H,
150.9 MHz, 13C) and Bruker CXP-100 instruments
(36.48 MHz, 31P) in CDCl3 relative to internal HMDS
or the signal of solvent, and to the external H3PO4. The
IR spectra were taken on a Bruker Vector-22
instrument from suspensions of substances in mineral
oil, or from thin films between the KBr plates. The
mass spectra were recorded on a TRACE MS Finnigan
MAT instrument at the energy of ionizing electrons
70 eV and ion source temperature 200°C. Heating of
Dibutyl-(1-methyl-4-oxopent-2-yl)phosphine
oxide (IIb) was obtained by a similar method, yield
89%, bp 136°C (0.06 mm Hg), nD20 1.4745 (compare
with the data [10]). IR spectrum, cm–1: 460, 494, 723,
795, 900, 941, 966, 1049, 1092, 1145, 1168, 1308,
1
1361, 1381, 1413, 1465, 1714, 2872, 2959, 3416. H
NMR spectrum, δ, ppm (J, Hz): 0.92 br.t (H10, 6H,
3JHCCH 7.2), 1.38 d (H1,6, 6H, 3JPCCH 16.0), 1.45 m (H9,
3
4H, JHCCH 7.2–7.4), 1.57 and 1.69, two m (H8, 4H,
the evaporator ampule was carried out in a
3JHCCH 7.2–7.4), 2.20 and 2.03, two m (H7, 4H), 2.19 s
programmed mode from 35 to 150°C with a step 35
deg min–1. The processing of mass-spectral data was
performed using the program Xcalibur.
(H5, 3H), 2.90 br.d (H3, 2H, JPCCH 11.7). 13C NMR
3
spectrum, δ, ppm (J, Hz) (in parentheses is shown the
shape of the signal in the 13C–{1H} NMR spectrum):
20.99 q.m (s) (C1,6, JHC 129.5, JHC CC 4.2–4.5,
1
3
1,6
3
1,6
ACKNOWLEDGMENTS
3JHC
4.2–4.5), 34.63 br.d.m (d) (C2, JPC 60.5),
1
6,1CC1,6
2
47.87 br.t.m (br.s) (C3, JHC 125.7), 205.56 d.q.t (d)
1
3
This work was supported by the Russian
Foundation for Basic Research (grant no. 09-03-
97007-r_povolzhe_a).
(C4, 3JPCCC 10.2, 2JHC C 5.4–5.6, 2JHC C 5.4–5.6), 31.44
4
5
4
3
4
q.d (d) (C5, JHC1 127.8, JPCCCC 1.3), 22.19 br.d.t (d)
1
4
5
5
1
1
(C7, JP C 58.0, JH C 127.9), 23.45 t.d.m (d), (C8, JHC
7
7
8
2
2
2
3
8
9
8
8
10
8
REFERENCES
125.1, JPCC 5.1, JHC C 5.1, JHC7C 5.1, JHC CC 5.1–
5.3), 23.52 t.d.m (d), (C9, JHC 126.0, JPCCC 15.3,
1
3
9
9
2
2
3
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9
10
9
7
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JHC C 3.4–4.1, JHC C 3.4–4.1, JH C CC 3.4–4.1), 12.95
q.t.t (s), (C10, 1JHC 125.4, 2JHC C 3.4–4.1, 3JHC CC 3.4–
4.1). 31P–{1H} NMR spectrum: δP 52.3 ppm. Found,
%: C 64.47; H 11.35; P 11.86. C14H29O2P. Calculated,
%: C 64.59; H 11.23; P 11.90.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010

REACTION OF 3,3,5-TRIMETHYL-2-CHLORO-1,2-OXAPHOSPHOLENE 2-OXIDE
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