Reaction of substituted benzalchlorides with phosphorous acid esters

Full text of DOI:10.1134/S107036320605029X

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 5, pp. 835 836.
Pleiades Publishing, Inc., 2006.
Original Russian Text
No. 5, pp. 871 872.
A.A. Prishchenko, M.V. Livantsov, O.P. Novikova, L.I. Livantsova, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76,
LETTERS
TO THE EDITOR
Reaction of Substituted Benzalchlorides
with Phosphorous Acid Esters
A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, and L. I. Livantsova
Moscow State University, Vorob’yevy Gory, Moscow, 119992 Russia
e-mail: liv@org.chem.msu.su
Received February 7, 2006
DOI: 10.1134/S107036320605029X
Functional methylenediphosphorus compounds are
interesting as prospective ligands and biologically
active compounds and also they are widely used in
organic synthesis [1]. For the synthesis of arylme-
thylenediphosphonates of new type we studied reac-
tions of triethyl- and tris(trimethylsilyl)phosphites
taken in excess with a series of substituted benzal-
chlorides A prepared alongside the methods described
esrlier [2]. We found that this reaction proceeds by
the scheme of Arbuzov rearrangement only at heating
the mixture to 150 160 C in the presence of zinc
chloride as a catalyst and results, depending on the
structure of the parent compounds, in formation of
substituted phosphonates I or diphosphonates II.
However, we failed to involve unsubstituted benzal-
chloride to this reaction under similar conditions.
(
XO)3P
2(EtO)3P
1
2EtCl
1
(
XO) P(O)C H(Cl)Ar
ArCHCl2
[(EtO) P(O)] C HAr,
2
2
2
XCl
Ia Ic
A
IIa, IIb
MeO 3 4 OMe
MeO 3 4
2
3
4
3
4
X = Et (Ia, Ib), Me Si (Ic); Ar = 2
5
F (Ia),
2
(Ib), 2
5
OMe (Ic, IIa),
(IIb).
5
5
3
7
6
OMe
The phosphonates Ia and Ic and diphosphonate IIa
can be easily hydrolyzed to form phosphonic III and
diphosphonic IV acids, respectively. Under these
conditions occurs also cleavage of chlorine carbon
bond.
NMR spectra of compounds I IV contain typical
signals of PC H and PC HP fragments and of substi-
tuted aromatic fragments.
1
1
Diethyl (4-fluorophenyl)chloromethylphos-
phonate (Ia). A mixture of 3 g 4-fluorobenzalchloride,
7 g of triethylphosphite and 0.1 g of zinc chloride
was heated at 150 160 C for 2 h and then was dis-
tilled. 3 g of phosphonate Ia was obtained, yield 64%,
H O, HCl
2
1
Ia, Ib
(HO) PC H(OH)Ar,
2
O
2
0
1
IIIa, IIIb
mp 152 C (2 mm Hg), n 1.4885. H NMR spectrum,
D
3
4
3
4
1
2
3
3
,
ppm: 4.75 d (C H, J 12 Hz), 6.82 d (C H, J
PH HH
2
5
F (a), 2
5
4
3
13
III, Ar =
OMe (b),
8 Hz), 7.32 d (C H, J 8 Hz). C NMR spectrum,
HH
1
1
2 2
C, ppm: 52.52 d (C , J 160 Hz), 130.16 t (C , J
=
PC
PC
4
3
3
3
H O, HCl
2
JFC 3.5 Hz), 130.69 d.d (C , J 6 Hz, J 8 Hz),
15.26 d (C , J 22 Hz), 162.68 d (C , J 248 Hz).
IIa
[(HO) P] CH
OMe.
PC FC
2
2
4
2
5 1
1
FC
FC
O
31
IV
P NMR spectrum, P, ppm: 16.89 s. Found, %:
835

836
PRISHCHENKO et al.
C 46.89; H 5.26. C H ClFO P. Calculated, %: C
distilled off in a vacuum. 2 g of acid IIIa was ob-
1
1
15
3
1
4
7.07; H 5.39.
Compounds Ib, Ic, and II were obtained by similar
procedure.
Diethyl (2,3-dimethoxyphenyl)chloromethyl-
phosphonate (Ib). Yield 68%, mp 184 C (2 mm Hg),
tained, yield 92%, mp 69 C. H NMR spectrum, ,
1
2
3
ppm: 4.72 d (C H, J 12 Hz), 7.10 7.15 m (C H),
PH
13
4
7
7
(
.41 7.44 m (C H). C NMR spectrum, C, ppm:
1
1
2
0.10 d (C , J 160 Hz), 136.71 s (C ), 129.66 s
PC
3
4
2
5 1
C ), 114.69 d (C , J 21 Hz), 161.76 d (C , J
FC FC
2
44 Hz). 31P NMR spectrum, P, ppm: 18.52 s (see
[3]).
2
0
1
1
n
1.5139. H NMR spectrum, , ppm: 5.35 d (C H,
16 Hz), 3.60 s and 3.65 s (OMe), 6.64 7.17 m
D
2
J
PH
5
6
7
13
Compounds IIIb and IV were prepared by similar
procedure.
(C H, C H, C H). C NMR spectrum, C, ppm:
1
1
4
5.63 d (C , J 163 Hz), 55.52 s and 55.73 s (OMe),
PC
2
2
3 3
4
-Methoxyphenyl(hydroxymethyl)phosphonic
1
1
21.56 d (C , J 4 Hz), 146.59 d (C , J 9 Hz),
PC PC
52.04 s (C ), 124.04 s (C ), 117.97 s (C ), 112.81 d
1
4
5
6
acid (IIIb). Yield 96%, mp 78 C. H NMR spectrum,
ppm: 4.71 d (C H, J 12 Hz), 3.44 s (OMe),
.67 d (C H, J 8 Hz), 7.12 d (C H, J 8 Hz).
C NMR spectrum,
160 Hz), 129.02 s (C ), 55.16 s (OMe), 128.52 d (C ,
JPC 6 Hz), 113.87 s (C ), 158.29 s (C ). P NMR
spectrum, P, ppm: 20.76 s, (see [3]).
1
2
7
3
31
,
(C , J 3 Hz). P NMR spectrum, P, ppm: 17.96 s.
PH
PC
3
3
4
3
6
PH PH
Bis(trimethylsilyl) (4-methoxyphenyl)chloro-
13
1
1
, ppm: 69.77 d (C , J
PC
C
methylphosphonate (Ic). Yield 81%, mp 166 C
2
3
1
(
0
1 mm Hg), mp 65 C. H NMR spectrum, , ppm:
3
4
5
31
1
2
.09 s and 0.19 s (Me Si), 4.71 d (C H, J 12 Hz),
3 PH
3
3
4
3
.72 s (MeO), 6.80 d (C H, J 8 Hz), 7.36 d (C H,
HH
3
13
(
4-Methoxyphenyl)methylenediphosphonic acid
JHH 8 Hz). C NMR spectrum, C, ppm: 0.63 s and
1
1
1
(
IV). Yield 96%, mp 86 C. H NMR spectrum, ,
0
(
6
.79 s (Me Si), 54.63 d (C , J 168 Hz), 55.21 s
3 PC
1
2
2
2
3 3
ppm: 3.49 t (C H, J 26 Hz), 3.57 s (OMe), 6.65 d
MeO), 126.90 t (C , J 3 Hz), 130.21 d (C , J
PH
PC
PC
3
3
4
3
13
4
5
31
(
C H, J 8 Hz), 7.20 d (C H, J 8 Hz). C NMR
Hz), 113.75 s (C ), 159.94 s (C ). P NMR spec-
PH PH
1
1
trum, P, ppm: 0.79 s.
spectrum,
, ppm: 45.06 t (C , J 126.5 Hz),
C PC
2
2
3 3
1
1
24.96 t (C , J 7.5 Hz), 131.08 t (C , J 6 Hz),
17.72 s (C ), 157.76 s (C ), 54.74 s (OMe). P NMR
PC
PC
31
Tetraethyl (4-methoxyphenyl)methylenedi-
phosphonate (IIa). Yield 78%, mp 202 C (2 mm Hg),
4
5
2
0
1
1
spectrum, P, ppm: 17.72 s. Found, %: C 33.94;
H 4.38. C H O P . Calculated, %: C 34.06; H 4.29.
n
1.4982. H NMR spectrum, , ppm: 3.47 t (C H,
D
2
3
3
8
12
7 2
JPH 24 Hz), 3.54 s (MeO), 6.63 d (C H, J 8 Hz),
.17 d (C4H, J
ppm: 44.37 t (C , J 132.5 Hz), 54.89 s (MeO),
HH
3
13
7
8 Hz). C NMR spectrum, C,
NMR spectra were registered on a Bruker Avance
00 instrument, solvents: CDCl for compounds I and
HH
1
1
4
3
PC
2
2
3 3
II, D O for compounds III and IV; references TMS
1
1
21.66 t (C , J 8 Hz), 131.29 t (C , J 6.5 Hz),
13.69 s (C ), 158.90 s (C ). P NMR spectrum, P,
2
PC
PC
1
13
31
4
5
31
(
H and C) and 85% H PO in D O ( P).
3 4 2
ppm: 18.74 s. Found, %: C 48.59; H 7.05. C H
1
6
28
ACKNOWLEDGMENTS
O P . Calculated, %: C 48.73; H 7.16.
7
2
Tetraethyl (2,5-dimethoxyphenyl)methylenedi-
phosphonate (IIb). Yield 76%, mp 212 C
This work was performed under financial support
of Russian Foundation for Basic research (grant
nos. 05-03-32864, 06-03-32731).
2 mm Hg), n2 1.5008. H NMR spectrum, , ppm:
0
1
(
3
6
D
1
2
.52 s and 3.55 s (MeO), 4.35 t (C H, J 26 Hz),
.45 6.60 m (C H, C H), 7.18 s (C H). C NMR
PH
13
4
5
7
REFERENCES
1
1
spectrum, , ppm: 35.48 t (C , J 133 Hz), 55.29 s
and 56.30 (OMe), 119.28 t (C , J 8 Hz), 150.78 t
C
PC
2
2
1. Prishchenko, A.A., Novikova, Z.S., and Lutsenko, I.F.,
Zh. Obshch. Khim., 1977, vol. 47, no. 12, p. 2689;
Teulade, M.-P., Savignac, P., Aboujaoude, E.E.,
Lietge, S., and Collignon, N., J. Organometal. Chem.,
1986, vol. 304, p. 283.
PC
3
3
4
5
(C , J 7 Hz), 111.78 s and 113.94 s (C , C ),
PC
6
7
3
31
1
53.08 s (C ), 116.21 t (C , J 4.5 Hz). P NMR
PC
spectrum, P, ppm: 19.05 s. Found, %: C 48.02;
H 7.06. C H O P . Calculated, %: C 48.11; H 7.13.
1
7
30
8 2
2
. Weigand, C. and Hilgetag, G., Organish-Chemishe
Experimentierkunst, Moscow: Khimiya, 1968.
4
-Fluorophenyl(hydroxymethyl)phosphonic acid
(
IIIa). A mixture of 3 g of phosphonate Ia and 20 ml
of conc. hydrochloric acid was heated on a boiling
water bath for 4 h and then evaporated to dtryness at
7
3. Prishchenko, A.A., Livantsov, M.V., Novikova, O.P.,
Livantsova, L.I., and Maryashkin, A.V., Russ. J. Gen.
Chem., 2005, vol. 76, no. 12, p. 1965.
mm Hg. 30 ml of water was added which was thed
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 5 2006