Reaction of trivalent phosphorus acids trimetylsilyl esters with 3,5-di-tret-butyl-4-hydroxybenzylidene dichloride

Full text of DOI:10.1134/S1070363206050288

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 5, pp. 832 834.
Original Russian Text A.A. Prishchenko, M.V. Livantsov, O.P. Novikova, L.I. Livantsova, D.B. Shpakovskii, E.R. Milaeva, 2006, published in Zhurnal
Obshchei Khimii, 2006, Vol. 76, No. 5, pp. 868 870.
Pleiades Publishing, Inc., 2006.
LETTERS
TO THE EDITOR
Reaction of Trivalent Phosphorus Acids Trimetylsilyl Esters
with 3,5-Di-tret-butyl-4-hydroxybenzylidene Dichloride
A. A. Prishchenko, M. V. Livantsov, O. P. Novikova,
L. I. Livantsova, D. B. Shpakovskii, and E. R. Milaeva
Lomonosov Moscow State University, Vorob’evy Gory, Moscow, 119992 Russia
e-mail: liv@org.chem.msu.su
Received December 30, 2005
DOI: 10.1134/S1070363206050288
We have offered earlier convenient methods for
the synthesis of some phosphorus-containing sterically
hindered phenols which are of interest as perspective
antioxidants and biologically active substances [1]. In
the present work the reaction of trivalent phosphorus
acids trimethylsilyl esters with readily available 3,5-
di-tert-butyl-4-hydroxybenzylidene dichloride A [2]
is shown to afford new methylenediphosphorus-
containing compounds that include a fragment of
sterically hindered phenol. Thus, trimethylsilyl
phosphites as well as functional trimethylsilyl phos-
phonites in methylene chloride readily react with the
chloride A according to the scheme of Arbuzov reac-
tion forming diphosphonates (I or II) or diphosphi-
nates (III or IV), respectively, in a high yield. Note-
worthy that sterically hindered hydroxy group of
chloride A does not enter in trimethylsilylation with
the trimethylsilyl phosphite or trimethylsilyl phos-
phonite excess (cf. [1]).
OH
Me3SiO
Y
t-Bu
Bu-t
2(Me3SiO)2PY
2Me3SiCl
C1HAr
2(XO)2POSiMe3
2Me3SiCl
P
[(XO)2P]2C1HAr
O
O
2
CHCl2
I, II
A
III, IV
O
Bu-t
13
3
4
8
2
C9H N
(IV).
OH, X = Et (I), Me3Si (II); Y = C6H2C7H2
(III),
5
12
Ar =
2
10 11
Bu-t
In reaction of diphosphonate (II), or diphosphinate
(III and IV) with excess methanol we obtained white
hygroscopic crystals of substituted acids with me-
thylenediphosphorus group (V VII).
1H NMR spectra of compounds (I VII) contain
characteristic signals of the methylenediphosphorus
fragments PC1HP and also signals of the substituted
Bu-t
OH .
Bu-t
4MeOH
II
[(HO)2P]2CH
O
4Me3SiOMe
V
832

REACTION OF TRIVALENT PHOSPHORUS ACIDS TRIMETYLSILYL ESTERS
833
Bis(trimethylsilyl) (3,5-di-tert-butyl-4-hydroxy-
Bu-t
OH ,
Bu-t
phenyl)methylenebis(2-phenylethylphosphinate)
1
HO
Y
(III). Yield 91%, mp 119 C. H NMR spectrum, ,
2MeOH
ppm: 0.18 s (Me3Si), 1.46 s (Me3C), 3.29 t (C1H, 2JPH
18 Hz), 7.0 7.3 m (C6H2, 2C6H5). 13C NMR spec-
trum, C, ppm: 1.23 s and 1.96 s (Me3Si), 30.33 s
III, IV
[
P]2CH
O
2Me3SiOMe
VI, VII
1
(Me3C), 34.39 s (Me3C), 49.98 t (C1, JP3C 78.5 Hz);
2
120.98 t (C2, JPC 7 Hz), 127.10 t (C3, JPC 6 Hz),
O
136.34 s (C4), 153.63 s (C5), 33.17 d (C6, 1JPC 96 Hz),
2
3
28.66 d (C7, JPC 4 Hz), 141.29 d (C8, JPC 16 Hz).
Y = CH2CH2Ph (VI), CH2N
(VII).
31P NMR spectrum, P, ppm: 37.96 s.
Bis(trimethylsilyl) (3,5-di-tert-butyl-4-hydroxy-
phenyl)methylenebis[N-(2-oxopyrrolidino)methyl-
phosphinate] (IV). Yield 94%, mp 71 C. The first
aromatic fragments and fragments of pyrrolidone.
According to the spectra, compound IV consists of
two stereoisomers. We determined their ratio by
means of 31P NMR spectroscopy, the data for prevail-
ing isomer are given first. The signal of methine
proton in the PC1HP fragment of the prevailing iso-
mer are overlapped by the proton signals of pyrroli-
done fragment. The methylene group proton signals
1
isomer, content 66%. H NMR spectrum, , ppm:
2
0.08 s (Me3Si), 1.24 s (Me3C), 3.94 t (C1H, JPH
17 Hz), 7.40 br.s (C6H2). 13C NMR spectrum, C, ppm:
0.90 s (Me3Si), 30.07 s (Me3C), 34.22 s (Me3C),
1
2
50.17 t (C1, JPC 78 Hz), 118.60 t (C2, JPC 7 Hz),
126.25 s (C3), 136.78 s (C4), 153.70 s (C5), 43.61 d
1
of compounds III, IV, VI, and VII in the H NMR
spectra are partially overlapped and appear as
multiplets.
(C9, 1JPC 108 Hz), 48.47 s (C10), 17.79 s (C11), 30.00 s
(C12), 174.66 d (C13, JPC 3 Hz). 31P NMR spectrum,
3
1
P, ppm: 29.91 s. The second isomer. H NMR spec-
Tetraethyl (3,5-di-tert-butyl-4-hydroxyphenyl)-
methylenediphosphonate (I). To a solution of 6.8 g
of diethyl trimethylsilyl phosphite in 20 ml of me-
thylene chloride at cooling to 0 C and stirring was
added a solution of 3.7 g of chloride A in 15 ml of
methylene chloride. The mixture was stirred for 0.5 h,
then heated to boiling and solvent was distilled off.
To the rest 20 ml of hexane was added and the mix-
ture was cooled to 0 C. The dropped white crystals
were filtered off and kept in 0.5 mm Hg vacuum for
1 h. We obtained 5.7 g of diphosphonate I, yield 90%,
trum, , ppm: 0.15 s (Me3Si), 1.24 s (Me3C), 7.40
br.s (C6H2). 13C NMR spectrum, C, ppm: 1.76 s
(Me3Si), 30.07 s (Me3C), 34.22 s (Me3C), 50.97 t (C1,
1JPC 77 Hz), 119.52 t (C2, 2JPC 5.5 Hz), 127.72 s (C3),
1
135.99 s (C4), 153.63 s (C5), 43.50 d (C9, JPC
106 Hz), 48.40 s (C10), 17.72 s (C11), 30.00 s (C12),
174.46 s (C13). 31P NMR spectrum, P, ppm: 29.18 s.
(3,5-Di-tert-butyl-4-hydroxyphenyl)methylene-
diphosphonic acid (V). To 30 ml of methanol at
cooling to 10 C and stirring was added 7.6 g of di-
phosphonate II. The mixture was heated to boiling,
solvent was distilled off, the residue was kept in
vacuum of 1 mm Hg for 1 h. 4.2 g of acids V was
1
mp 140 C (cf. [3]). H NMR spectrum, , ppm: 1.11 t
3
and 1.28 t (CH3CH2O, JHH 6 Hz), 1.42 s (Me3C),
3.8 4.2 m (CH2O), 3.62 t (C1H, 2JPH 24 Hz), 5.45 br.s
(OH), 7.24 s (C6H2). 13C NMR spectrum, C, ppm:
16.13 t and 16.34 t (CH3CH2O, 3JPC 3.5 Hz), 30.27 s
(Me3C), 34.32 s (Me3C), 62.62 d and 63.33 d (CH2O,
1
isolated, yield 97%, mp 201 C. H NMR spectrum, ,
ppm: 1.26 s (Me3C), 3.60 t (C1H, 2JPH 26 Hz), 7.22 s
(C6H2). 13C NMR spectrum, C, ppm: 29.66 s (Me3C),
1
2JPC 3 Hz), 45.19 t (C1, JPC 132 Hz), 120.12 t (C2,
1
34.17 s (Me3C), 45.85 t (C1, JPC 126 Hz), 123.42 t
3
2JPC 6 Hz), 127.25 t (C3, JPC 6 Hz), 135.87 s (C4),
(C2, 2JPC 7.5 Hz), 127.04 t (C3, 3JPC 5.5 Hz), 139.87 s
(C4), 152.26 s (C5). 31P NMR spectrum, P, ppm:
18.35 s. Found, %: C 47.19; H 6.97. C15H26O7P2.
Calculated, %: C 47.37; H 6.89.
153.35 s (C5). 31P NMR spectrum, P, ppm: 19.39 s.
Compounds II IV were prepared similarly.
Tetra(trimethylsilyl) (3,5-di-tert-butyl-4-hyd-
roxyphenyl)methylenediphosphonate (II). Yield of
Acids VI VII are similarly prepared.
1
89%, mp 156 C. H NMR spectrum, , ppm: 0.13 s
2
(Me3Si), 1.41 s (Me3C), 3.40 t (C1H, JPH 26 Hz),
(3,5-di-tert-butyl-4-hydroxyphenyl)methylene-
bis(2-phenylethylphosphinic) acid (VI). Yield 95%,
mp 202 C. 1H NMR spectrum, , ppm: 1.37 s (Me3C),
5.16 br.s (OH), 7.17 s (C6H2). 13C NMR spectrum,
,
C
ppm: 0.78 s (Me3Si), 30.18 s (Me3C), 34.26 s (Me3C),
2
3.82 t (C1H, JPH 18 Hz), 7.36 s (C6H2). 13C NMR
48.79 t (C1, 1JPC 140 Hz), 122.89 t (C2, 2JPC 8.5 Hz),
127.31 t (C3, 3JPC 6 Hz), 135.70 s (C4), 153.16 s (C5).
31P, P, ppm: 0.17 s.
spectrum, C, ppm: 30.89 s (Me3C), 35.03 s (Me3C),
1
2
49.27 t (C1, JPC 75 Hz), 123.14 t (C2, JPC 5.5 Hz),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 5 2006

834
PRISHCHENKO et al.
127.63 t (C3, 3JPC 6 Hz), 139.47 s (C4), 153.40 s (C5),
I IV, D2O for compound V or (CD3)2SO for com-
pounds VI and VII, reference compounds TMS (1H,
1
2
31.59 d (C6, JPC 94 Hz), 27.96 d (C7, JPC 3 Hz),
3
142.26 d (C8, JPC 17 Hz). 31P NMR spectrum,
,
13C) and 85% H3PO4 in D2O (31P).
P
ppm: 43.20 s. Found, %: C 66.68; H 7.69. C31H42
O5P2. Calculated, %: C 66.89; H 7.60.
ACKNOWLEDGMENTS
(3,5-di-tert-butyl-4-hydroxyphenyl)methylene-
bis[N-(2-oxopyrrolidino)methylphosphinic] acid
This work was performed under support of Russian
Foundation for Basic Research (grant nos. 05-03-
32864 and 06-03-32731).
1
(VII). Yield of 96%, mp 122 C. H NMR spectrum,
2
, ppm: 1.37 s (Me3C), 3.64 t (C1H, JPH 20 Hz),
7.27 s (C6H2). 13C NMR spectrum, C, ppm: 30.81 s
1
(Me3C), 34.94 s (Me3C), 49.36 t (C1, JPC 74 Hz),
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2
121.57 t (C2, JPC 5.5 Hz), 127.84 s (C3), 138.76 s
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NMR spectra were registered on a Bruker Avance
400 spectrometer, solvents: CDCl3 for compounds
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 5 2006