(Chloromethyl)phosphoryl compounds in the arbuzov reaction [2]

Full text of DOI:10.1023/A:1015564225238

Russian Journal of General Chemistry, Vol. 72, No. 3, 2002, pp. 486 487. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 3, 2002,
pp. 521 522.
Original Russian Text Copyright
2002 by Yarkevich, Tsvetkov.
LETTERS
TO THE EDITOR
(
Chloromethyl)phosphoryl Compounds in the Arbuzov Reaction
A. N. Yarkevich and E. N. Tsvetkov
Institute of Physiologically Active Compounds, Russian Academy of Sciences, Chernogolovka, Russia
Received April 4, 2001
The synthesis of di- and triphosphoryl compounds
(
BuO)3P
containing the potent complex-forming methylenedi-
phosphoryl fragments was carried out with the pur-
pose of searching for effective extractants and selec-
tive complex-forming agents.
ClCH P(O)CH Cl
(BuO) P(O)CH P(O)CH Cl
2
2
2
2
2
OBu
OBu
IV
A
(Chloromethyl)diphenylphosphine oxide (I) was
used as the haloalkyl component in the Arbuzov reac-
tion for preparing unsymmetrical diphosphoryl com-
pounds containing a phosphine oxide group. It was
previously shown [1, 2] that the reactivity of com-
pound I is relatively low, and we took this into
account when choosing reaction conditions.
O
OBu
O
BuO
(
BuO) P(O)CH P(O)CH P(O)(OBu)
2 2 2 2
P
P
OBu
O
V
VI
phosphite it undergoes intramolecular cyclization lead-
ing to diphospholane VI. In this case, the high tem-
perature of the process and removal of butyl chloride
from the reaction sphere favor cyclization. Similar
formation of stable five-membered rings, (1,2-oxa-
phospholanes) was previously observed on attempted
preparation of (3-halopropyl)phosphonates [3, 4] and
also while using them as alkylating agents in polar
media [4].
By reacting phosphine oxide I with tributyl phos-
phite and dibutyl phenylphosphonite at 190 210 C,
respectively, we synthesized dibutyl (diphenylphos-
phorylmethyl)phosphonate (II) and butyl (diphenyl-
phosphorylmethyl)phenylphosphinate (III).
P(OBu)3
Ph P(O)CH P(O)(OBu) ,
2
2
2
II
Ph P(O)CH Cl
2
2
Ph(OBu)2
The reaction was carried out in a Claisen flask
equipped with a dropping funnel for adding tributyl
phosphite and a condenser with a receiver for collect-
ing condensate. For a more complete removal of the
evolving butyl chloride and prevention of its participa-
tion in the Arbuzov reaction, reduced pressure
180 mm) was maintained in the reaction vessel. The
reaction completion was detected by the amount of
the condensate. The reaction progress was also con-
I
Ph P(O)CH P(O)Ph(OBu)
2
2
III
Butyl bis(chloromethyl)phosphinate (IV) was
chosen as the haloalkyl component for preparing tri-
phosphoryl compounds. The reaction of phosphinate
IV with tributyl phosphite in a 1:2 molar ratio gives
pentabutyl ester V, a traditional Arbuzov product. At
an equimolar ratio of the starting compounds, cyclic
diphospholane VI was obtained instead of the ex-
pected butyl (chloromethyl)(dibutoxyphosphoryl-
methyl)phosphinate (A), according to the above-
presented scheme.
(
31
trolled by P NMR spectroscopy.
The starting chloromethyl compounds I and II
were prepared by known procedures [5, 6]. Tributyl
phosphite and dibutyl phenylphosphonite were distil-
led in a vacuum before use.
(
Chloromethyl)phosphonophosphinate A formed
in the first stage is likely to react with tributyl phos-
Dibutyl (diphenylphosphorylmethyl)phospho-
phite to give ester V, while in the absence of tributyl
nate (II). Tributyl phosphite, 7.28 g, was added for
5
h at 190 200 C (bath temperature) and a residual
pressure of 180 mm to a melt of 5.13 g of Ph P(O)
2
Deceased.
CH Cl (I). The resulting mixture was kept for 2 h at
2
1
070-3632/02/7203-0486$27.00 2002 MAIK Nauka/Interperiodica

(CHLOROMETHYL)PHOSPHORYL COMPOUNDS IN THE ARBUZOV REACTION
487
the same temperature. The volatile fraction containing,
CH PCH ), 4.10 m (10 H, 5CH O). 31P NMR spec-
2
2
2
3
1
according to the P NMR spectra, mainly (BuO) P,
trum, P, ppm: 20.19 d and 38.34 t (JPP 3.2 Hz).
Found, %: C 49.24, 49.18; H 8.81, 8.97; P 17.38,
17.32. C H O P . Calculated, %: C 49.43; H 9.24;
3
(
BuO) PO, and (BuO) P(O)Bu was removed in a
3 2
water-jet-pump vacuum at 130 140 C (10 mm). The
residual oil was chromatographed on a column of
Silica gel L (100 160 m), eluent hexane isopropa-
nol, 7:1, to obtain 0.609 g (75%) of phosphonate II,
2
2
49
8 3
P 17.38.
2
,4-Dibutoxy-1,2,4-oxadiphospholane (VI) was
1
prepared similarly to phosphonate II from 5.48 g of
mp 53 54 C. H NMR spectrum, , ppm: 0.96 t (6H,
phosphinate IV and 6.26 g of tributyl phosphite. Yield
2
2
7
Me), 1.24 m (4H, 2CH CCO0, 1.46 m (4H,
1
2
5
.87 g (83%), bp 200 205 C (0.5 mm). H NMR
CH CO), 3.00 m (2H, PCH P), 3.96 m (4H, 2CH O),
2
2
2
3
1
spectrum, , ppm: 0.94 t (6H, 2 Me), 1.44 m (4H,
CH CCO), 1.72 m (4H, 2CH CO), 2.68 m (2H,
.44 m (6H) and 7.82 m (4H) (2Ph). P NMR spec-
2
2
2
trum, P, ppm : 20.22 d and 24.80 d (JPP 14.6 Hz).
PCH P), 3.84 m (2H, PCH OP), 4.18 m (4H, 2CH O).
2
2
2
Found, %: C 61.62, 61.60; H 7.29, 7.22; P 14.61,
31
P NMR spectrum, P, ppm: 19.29 s and 39.24 s.
Found, %: C 42.00, 41.86; H 8.10, 8.04; P 17.38,
1
4.56. C H O P . Calculated, %: C 61.76; H 7.40;
21 30 4 2
P 15.71.
1
7.32. C H O P. Calculated, %: C 42.25; H 7.80,
1
0
22
5
Butyl (diphenylphosphorylmethyl)phenylphos-
phinate (III). a. The synthesis was performed by a
procedure similar to that applied for phosphonate II,
by heating 6.27 g of Ph P(O)CH Cl and 9.33 g of
P 21.80.
1
31
The H and P NMR spectra were registered on a
1
Bruker CXP spectrometer at 200 ( H) and 81 MHz
31
2
2
(
P) in CDCl against internal TMS and external
3
PhP(OBu) at 200 210 C. The oily reaction product
2
8
5% phosphoric acid. The melting points were mea-
(
7.20 g, 70%) was crystallized by treatment with ether.
sured on a Boetius PHMK 05 device.
Crystallization from isoamyl acetate gave 6.00 g
1
(58%) of phosphinate III, mp 99.5 100.5 C. H NMR
ACKNOWLEDGMENTS
spectrum, , ppm: 0.86 t (3H, Me), 1.16 m (2H,
CH CCO), 1.38 m (2H, CH CO), 3.16 m (2H,
2
2
The authors express their gratitude to V.O. Za-
vel’skii for measuring the NMR spectra and to
V.V. Ragulin for discussing the resulting data.
PCH P), 3.76 m (2H, CH O), 7.40 m (9H) and
2
2
3
1
7
2
6
.82 m (6H) (3Ph). P NMR spectrum, , ppm:
4.48 d and 34.38 d (JPP 12.6 Hz). Found, %: C 66.84,
6.91; H 5.97, 6.01; P 15.25, 15.47. C H O P .
2
3
26
3
2
REFERENCES
Calculated, %: C 66.98; H 6.36; P 15.02.
1
2
. Hellmann, H. and Bader, J., Tetrahedron Lett., 1961,
no. 20, pp. 724 729.
b. A mixture of 7.50 g of Ph P(O)CH Cl and
2
2
1
2
(
1.22 g of PhP(OBu) was heated for 8 h at 200
2
. Kreutzkamp, N, Herberg, K., Lammerhirt, K., and
Schmidt-Samoa, E., Arch. Pharm., 1971, vol. 304,
no. 12, pp. 896 899.
10 C (bath temperature) in a water-jet-pump vacuum
20 30 mm). The reaction mixture was cooled, and
the resulting oil was crystallized by treatment with
ether to obtain 10.50 g (85%) of phosphinate III, mp
3. Pudovik, A.N., Muratova, A.A., and Savel’eva, V.A.,
9
7 99 C.
Zh. Obshch. Khim., 1964, vol. 34, no. 8, pp. 2582 2586.
4
5
. Rozhko, L.F., Ragulim, V.V., and Tsvetkov, E.N., Zh.
Obshch. Khim., 1996, vol. 66, no. 7, pp. 1093 1095.
Butyl bis(dibutoxyphosphorylmethyl)phos-
phinate (V) was prepared similarly to phosphonate II
from 5.48 g of phosphinate IV and 18.77 g of tributyl
. Patsanovskii, I.I., Ishmaeva, E.A., Sundukova, E.N.,
Yarkevich, A.N., and Tsvetkov, E.N., Zh. Obshch.
Khim., 1986, vol. 56, no. 3, pp. 567 576.
1
phosphite. Yield 12.23 g (92%), oil. H NMR spec-
trum, , ppm: 0.92 t (15H, 5 Me), 1.40 m (10 H,
5
CH CCO), 1.66 m (10 H, 5CH CO), 2.80 m (4H,
6. Maier, L., Helv. Chim. Acta, 1969, vol. 52, p. 827.
2
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 3 2002