Addition of trimethylsilyl esters of trivalent phosphorus acids to diethyl 3,5-di-tert-butyl-4-hydroxybenzoylphosphonate

Full text of DOI:10.1134/S107036320708035X

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 8, pp. 1477 1479.
Original Russian Text A.A. Prishchenko, M.V. Livantsov, O.P. Novikova, L.I. Livantsova, A.V. Maryashkin, E.R. Milaeva, 2007, published in Zhurnal
Obshchei Khimii, 2007, Vol. 77, No. 8, pp. 1400 1402.
Pleiades Publishing, Ltd., 2007.
LETTERS
TO THE EDITOR
Addition of Trimethylsilyl Esters of Trivalent Phosphorus Acids
to Diethyl 3,5-Di-tert-butyl-4-hydroxybenzoylphosphonate
A. A. Prishchenko, M. V. Livantsov, O. P. Novikova,
L. I. Livantsova, A. V. Maryashkin, and E. R. Milaeva
Lomonosov Moscow State University,
Vorob’evy Gory, Moscow, 119992 Russia
e-mail: liv@org.chem.msu.ru
Received December 25, 2006
DOI: 10.1134/S107036320708035X
Derivatives of substituted unsymmetrical hy-
t-Bu
t-Bu 4 3
droxymethylenediphosphorus acids containing two
phosphoryl groups with different extents of polariza-
tion are of interest as ligands and biologically active
compounds [1]. Here we report on a facile route to
new derivatives of unsymmetrical hydroxymethylene-
diphosphorus acids containing a 2,6-di-tert-butyl-
phenol fragment starting from diethyl (3,5-di-tert-
butyl-4-hydroxybenzoyl)phosphonate I detected pre-
viously as an intermediate [2]. Phosphonate I was
prepared in a high yield by the reaction of triethyl
phosphite with readily available 3,5-di-tert-butyl-4-
hydroxybenzoyl chloride A [3].
(
EtO)3P
5
2
1
HO
t-Bu
CCl
O
HO
C P(OEt)2
EtCl
O O
t-Bu
A
I
Tris(trimethylsilyl) phosphite as well as functiona-
lized trimethylsilyl phosphonites taken in excess read-
ily add to the carbonyl group of -keto phosphonate
I with the formation of diphosphonate II and phos-
phonate phosphinates III and IV, respectively, in
high yields.
O
O
1
1
(
EtO)2P
Ar
(Me SiO) P
(Me SiO) PY
(EtO)2P
Ar
3
3
3
2
C1
C1
I
2
(
Me SiO) P
OSiMe3
Me3SiO
P2
OSiMe3
3
2
Y
O
O
II
III, IV
4Bu-t
3
2
5
8
6
7
9
10
11
Ar =
OH , Y = C H C H
(III), C H C H C OOSiMe (IV).
2 2 3
2
2
Bu-t
The reactions of diphosphonate II and phospho-
nate phosphinates III and IV with excess methanol
gave substituted hydroxymethylenediphosphorus acids
V VII in high yields. Acid V is obtained as white
hygroscopic crystals decomposing on heating above
100 C, without definite melting point. Acids VI and
VII are viscous oils.
Previously unknown hydroxymethylenediphos-
phoryl compounds II VII containing a sterically
1477

1478
PRISHCHENKO et al.
O
1
(
EtO)2P
Ar
3
MeOH
2 C1
II
3
Me SiOMe
(HO)2P
OSiMe3
3
O
V
O
1
(
EtO)2P
Ar
2
MeOH
C1
III, IV
2
Me SiOMe
HO
Y
3
P2
OSiMe3
O
VI, VII
4Bu-t
3
2
5
8
6
7
9
10
11
Ar =
OH , Y = C H C H
(VI), C H C H C OOH (VII).
2
2
2
2
Bu-t
4
5
hindered phenolic fragment are promising complexing
agents and antioxidants. The NMR spectra of II VII
contain characteristic signals of methylenediphos-
(C ), 160.39 s (C ). 31P NMR spectrum, P, ppm:
0.05 s. Found, %: C 61.48; H 8.35. C H O P. Cal-
culated, %: C 61.61; H 8.43.
1
9
31
5
1
1 2
phoryl fragments P C P together with the signals of
substituted aromatic fragments and propionic acid
moieties. The methylene protons of III, IV, VI, and
Bis(trimethylsilyl) (3,5-di-tert-butyl-4-hydroxy-
phenyl)(trimethylsiloxy)(diethoxyphosphoryl)me-
thylphosphonate II. A solution of 10 g of tris(tri-
methylsilyl) phosphite in 5 ml of methylene chloride
was added with stirring and cooling (10 C) to a solu-
tion of 4.6 g of phosphonate I in 10 ml of methylene
chloride,. The mixture was refluxed for 2 h and kept
for 24 h, after which the solvent was distilled off, and
the residue was left for 24 h. Then 15 ml of hexane
was added to the residue, and the resulting solution
was cooled to 5 C. The precipitated white crystals
were filtered off and kept in a vacuum (0.5 mm Hg)
for 1 h to give 7.2 g (87%) of phosphonate II, mp
1
VII give in the H NMR spectra partly overlapping
1
3
multiplets. In the C NMR spectra of III and VI, the
signals of the phenyl fragment overlap with the
2
3
signals of C and C nuclei.
Diethyl (3,5-di-tert-butyl-4-hydroxybenzoyl)-
phosphonate I. A mixture of 3.8 g of 3,5-di-tert-bu-
tyl-4-hydroxybenzoic acid and 8 ml of thionyl chlo-
ride in 10 ml of hexane was refluxed for 0.5 h, after
which the solvent was distilled off in a vacuum, and
the residue was kept in a vacuum (0.5 mm Hg) for
1
0
1
.5 h. Then a solution of 4 g of triethyl phosphite in
0 ml of methylene chloride was added with stirring
110 C. H NMR spectrum, , ppm: 0.03 and 0.11 s
(Me SiOP), 0.15 s (Me SiOC), 1.01 t and 1.12 t (CH
CH O, J 7 Hz), 1.32 s (Me C), 3.6 4.0 m (CH O),
5.14 br. s (OH), 7.54 s (C H ). C NMR spectrum, C,
6 2
3
3
3
3
and cooling (10 C) to a solution of chloride A in
5 ml of methylene chloride. The mixture was stirred
2 HH 3 2
1
3
1
for 0.5 h and then heated to reflux, after which the
solvent was distilled off, 15 ml of hexane was added
to the residue, and the mixture was cooled to 10 C.
The oil that separated out was washed with cold hex-
ane and kept in a vacuum (0.5 mm Hg) for 1 h to
ppm: 0.77 s and 0.96 s (Me SiOP), 2.57 s (Me SiOC),
3 3
3
1
6.12 d and 16.16 d (CH CH O, J 6 Hz), 30.29 s
3 2 PC
(
Me C), 34.42 s (Me C), 62.77 d and 63.09 d (CH O,
JPC 8 Hz), 79.72 d.d [C , J
3 3 2
2
1 1
1
1
151 Hz, J 163 Hz],
P2C
P C
2
3
3
3
1
126.61 s (C ), 124.28 t [C , J
134.39 s (C ), 153.10 s (C ). P NMR spectrum, P,
ppm: 16.92 d (P ), 0.58 d (P ), J 45.4 Hz. Found,
P1C
= J
P2C
4 Hz],
obtain 4.6 g (81%) of phosphonate I as oil. H NMR
3
4
5
31
spectrum, , ppm: 1.32 t (CH CH O, J
8 Hz),
3
2
HH
1
2
2
1
8
.40 s (Me C), 4.15 4.25 m (CH O), 6.30 br.s (OH),
3
2
PP
1
3
.16 s (C H ). C NMR spectrum, C, ppm: 16.34 d
%: C 49.92; H 8.68. C H O P Si . Calculated, %:
6
2
28 58
8
2
3
3
C 50.27; H 8.74.
(
CH CH O, J 6 Hz), 29.97 s (Me C), 34.43 s
3 2 PC 3
2
1
(Me C), 63.52 d (CH O, J 8 Hz), 196.61 d (C ,
3 2 PC
Compounds III and IV were prepared similarly.
These compounds are extremely readily hydrolyzed,
1
2
3
JPC 171 Hz), 129.44 s (C ), 128.07 s (C ), 136.64 s
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 8 2007

ADDITION OF TRIMETHYLSILYL ESTERS OF TRIVALENT PHOSPHORUS ACIDS
1479
and therefore they were analyzed in the form of the
corresponding acids VI and VII.
Acids VI and VII were prepared similarly.
(3,5-Di-tert-butyl-4-hydroxyphenyl)hydroxy(di-
[
Trimethylsilyl [(3,5-di-tert-butyl-4-hydroxy-
phenyl)(trimethylsiloxy)(diethoxyphosphoryl)me-
ethoxyphosphoryl)methyl](2-phenylethyl)phos-
1
phinic acid VI. Yield 92%, oil. H NMR spectrum, ,
thyl](2-phenylethyl)phosphinate III. Yield 85%, oil.
ppm: 1.10 1.15 m (CH CH O), 1.32 s (Me C), 3.7
1
3
2
3
H NMR spectrum, , ppm: 0.05 (Me SiOP), 0.17 s
13
3
4.2 m (CH O), 7.0 7.7 m (C H , C H ). C NMR
2 6 2 6 5
(
Me SiOC), 1.1 1.15 m (CH CH O), 1.37 s (Me C),
3 3 2 3
spectrum, , ppm: 16.4 16.6 m (CH CH O), 30.85 s
C 3 2
3
.6 4.0 m (CH O), 5.75 br.s (OH), 7.0 7.5 m (C H ,
2 6 2
(Me C), 35.11 s (Me C), 63.5 64.0 m (CH O),
1
3
3
3
2
C H ). C NMR spectrum, C, ppm: 0.62 s and 0.96 s
1
1
1
6
5
77.77 d.d [C , J
C ), 153.52 s (C ), 31.66 (C , J 94 Hz), 27.84 s
(C ), 142.50 d (C , J 15 Hz). P NMR spectrum,
1
148 Hz, J
P2C
96 Hz], 138.15 s
P C
(
Me SiOP), 2.37 s (Me SiOC), 15.6 15.8 m (CH
4
5
6
1
3
3
3
(
PC
31
CH O), 30.03 s (Me C), 34.35 s (Me C), 62.5 63.3 m
2
3
3
7
8 3
1
1
1
PC
(CH O), 81.25 d.d [C , J
P1C
147 Hz, J
P2C
102 Hz],
2
1
2
2
4
5
6 1
, ppm: 17.97 d (P ), 43.59 d (P ), J 32.4 Hz.
P PP
1
2
35.58 s (C ), 153.30 s (C ), 32.08 d (C , J 93 Hz),
PC
7.82 d (C , J 3 Hz), 141.37 d (C , J 16 Hz).
P NMR spectrum, , ppm: 17.14 d (P ), 39.08 d
Found, %: C 59.65; H 7.74. C H O P . Calculated,
7
2
8
3
27 42
7 2
PC
PC
%: C 59.99; H 7.83.
3
1
1
P
2
2
(P ), J 43.7 Hz.
[(3,5-Di-tert-butyl-4-hydroxyphenyl)hydroxy(di-
PP
ethoxyphosphoryl)methyl](2-carboxyethyl)phos-
Trimethylsilyl [(3,5-di-tert-butyl-4-hydroxy-
1
phinic acid VII. Yield 92%, oil. H NMR spectrum,
phenyl)(trimethylsiloxy)(diethoxyphosphoryl)me-
thyl][2-(trimethylsiloxycarbonyl)ethyl]phosphinate
,
ppm: 1.0 1.15 m (CH CH O), 1.32 s (Me C), 3.7
3 2 3
13
4
.3 m (CH O), 7.53 s (C H ). C NMR spectrum, C,
1
2 6 2
IV. Yield 90%, oil. H NMR spectrum, , ppm: 0.16 s
ppm: 16.4 16.6 m (CH CH O), 30.78 s (Me C),
3
2
3
[
Me SiOC(O)], 0.05 s (Me SiOP), 0.26 s (Me SiOC),
3 3 3
1
3
5.06 s (Me C), 62.5 63.0 m (CH O), 77.70 d.d [C ,
3 2
93 Hz], 126.36 s (C ), 123.84
(C ), 138.05 s (C ), 153.45 s (C ), 22.21 d (C , J
94 Hz), 26.83 s (C ), 173.18 d (C , J 15 Hz).
NMR spectrum, , ppm: 17.93 d (P ), 43.10 d (P ),
1
.0 1.1 m (CH CH O), 1.28 s (Me C), 3.7 4.3 m
3 2 3
1
1
2
1
3
J
1
153 Hz, J
2
(
CH O), 5.30 br.s (OH), 7.54 s (C H ). C NMR
P C
P C
2
6
2
3
4
5
9 1
spectrum,
Me SiOP), 2.32 s (Me SiOC), 15.8 16.0 m (CH
, ppm: 0.67 s [Me SiOC(O)], 0.99 s
C
3
PC
31
1
0
11 3
(
3
3
3
P
PC
1
2
CH O), 30.03 s (Me C), 34.32 s (Me C), 62.5 63.0 m
2
3
3
P
1
1
1
2
(
1
(
(
CH O), 81.25 d.d [C , J
1
148 Hz, J
2
106 Hz],
2
P C
P C
JPP 35.6 Hz. Found, %: C 51.59; H 7.46. C H
22
38
2
3
4
26.99 s (C ), 123.62 s (C ), 135.21 s (C ), 153.42 s
O P . Calculated, %: C 51.97; H 7.57.
9 2
5
9 1
10
C ), 22.44 d (C , J 98 Hz), 28.50 s (C ), 172.45 d
PC
31
1
1
3
The NMR spectra were recorded on a Bruker
C , J
19 Hz). P NMR spectrum, P, ppm:
PC
Avance 400 spectrometer, solvents CDCl for I IV
1
2
2
3
1
7.15 d (P ), 38.95 d (P ), J 43.7 Hz.
1
PP
and (CD ) SO for V VII, references TMS ( H and
3
2
1
3
31
C) and 85% H PO in D O ( P).
(
3,5-Di-tert-butyl-4-hydroxyphenyl)hydroxy(di-
3
4
2
ethoxyphosphoryl)methylphosphonic acid V. Di-
phosphonate II, 7.2 g, was added to 30 ml of me-
thanol with stirring and cooling to 10 C. The mixture
was heated to reflux, the solvent was distilled off, and
the residue was washed with hexane and kept in a
vacuum (1 mm Hg) for 1 h to obtain 4.4 g (91%) of
ACKNOWLEDGMENTS
The study was financially supported by the Russian
Foundation for Basic Research (project nos. 05-03-
2864 and 06-03-32731).
3
1
acid IV as white crystals. H NMR spectrum, , ppm:
3
REFERENCES
1
(
.00 and 1.17 t (CH CH O, J
8 Hz), 1.39 s
3
2
HH
1
3
Me C), 3.7 4.2 m (CH O), 7.58 s (C H ). C NMR
3 2 6 2
1
. Ebetino, F.H., Phosphorus, Sulfur, Silicon, Relat Elem.,
1999, vols. 144 146, p. 9.
spectrum, , ppm: 16.45 d and 16.73 d (CH CH O,
C
3
2
3
JPC 6 Hz), 30.92 s (Me C), 35.08 s (Me C), 63.23 d
and 63.31 d (CH O, J 8 Hz), 76.54 t [C , J
3
3
2
1 1
P1C
=
2. Prishchenko, A.A., Livantsov, M.V., Novikova, O.P.,
Livantsova, L.I., Maryashkin, A.V., and Milaeva, E.R.,
Zh. Obshch. Khim., 2007, vol. 77, no. 8, p. 1397.
2
PC
1
2
3
J
2
146 Hz], 127.41 s (C ), 123.86 s (C ), 137.76 s
P C
4
5
31
(
1
C ), 153.16 s (C ). P NMR spectrum, P, ppm:
1
2
2
8.54 d (P ), 14.95 d (P ), J 38.9 Hz. Found, %:
3. Ivakhnenko, E.P., Shif, A.I., Prokof’ev, A.I., Olekhno-
vich, L.P., and Minkin, V.I., Zh. Org. Khim., 1989,
vol. 25, no. 2, p. 357.
PP
C 50.07; H 7.52. C H O P . Calculated, %: C 50.44;
1
9
34
8 2
H 7.57.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 8 2007