Synthesis of bis(trimethylsilyl) pyrid-3-yl(trimethylsiloxy)- methylphosphonite and its derivatives

Full text of DOI:10.1134/S1070363208110315

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 11, pp. 2156–2159. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © А.А. Prishchenko, М.V. Livantsov, О.P. Novikova, L.I. Livantsova, Е.R. Milyaeva, 2008, published in Zhurnal Obshchei Khimii,
2008, Vol. 78, No. 11, pp. 1920–1923.
LETTERS
TO THE EDITOR
Synthesis of Bis(trimethylsilyl) Pyrid-3-yl(trimethylsiloxy)-
methylphosphonite and Its Derivatives
А. А. Prishchenko, М. V. Livantsov, О. P. Novikova, L. I. Livantsova, and Е. R. Milyaeva
Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
е-mail: aprishchenko@yandex.ru
Received April 8, 2008
DOI: 10.1134/S1070363208110315
The aryl-substituted trimethylsilyl methylphos-
phonites that we have prepared earlier [1] are key
compounds in the synthesis of various functionalized
hydroxymethylphosphinates, which are of interest as
potential ligands and biologically active substances
[2]. In the present work we developed a convenient
method of synthesis of pyrid-3-yl-substituted trimethyl-
siloxymethylphosphonite (I) and its derivatives
including pyridine fragments along with hydroxyl-
methyl groups. Thus, phosphonite I was obtained in
high yield in a reaction of bis(trimethylsiloxy)
phosphine with pyridine-3-carbaldehyde followed by
reaction of adduct А with bis(trimethylsilyl)amine (cf.
[1]).
Me3SiO
(Me3Si)2NH
PyCHO
(Me3SiO)2PH
PCH(OSiMe3)Py
(Me3SiO)2PC1H(OSiMe3)Py
_NH3
H
O
I
A
6
3
5
2
4
.
Py =
N
Note that we failed to obtain phosphonite (I) by
and pyridine-3-carbaldehyde taken in the ratio 1:1. In
method [3] directly from ammonium hypophosphite
this case only phosphinate (II) formed in a good yield.
(1) Me3SiCl; (2) PyCHO; (3) (Me3Si)2NH
NH4H2PO2
Me3SiOP[C1H(OSiMe3)Py]2
_NH4Cl, _NH3
O
II
Py =
.
N
Reaction of phosphinates II–IV and diphosphinate
V with methanol excess gives rise to new types of
hydroxymethylphosphinic acids containing pyridine and
2,6-di-tert-butyl-4-methylphenol (VI–IX) fragments.
Phosphonite I is a suitable synton for a series of
pyridine-containing hydroxymethylphosphinates includ-
ing 2,6-di-tert-butyl-4-methylphenol fragments. Thus,
phosphonite I added readily to the carbonyl group of
aldehyde B and reacts smoothly with chloroanhydride
С and benzalchloride D along the scheme of Arbuzov
reaction in methylene chloride medium to form
phosphinates III, IV, and diphosphinate V.
The functionalized phosphinic acids VI-IX
obtained are promising antioxidants and effective
ligands for complexes of various structure using both
pyridine fragments and phosphoryl groups.
2156

SYNTHESIS OF BIS(TRIMETHYLSILYL) PYRID-3-YL(TRIMETHYLSILOXY)-...
2157
C1H(OSiMe3)Py
C1H(OSiMe3)Py
ArCHO (B)
ArCOCl (C)
Me3SiOP
O
I
Me3SiOP
O
_Me3SiCl
C7H(OSiMe3)Ar
C7(O)Ar
ArCHCl2 (D)
_2 Me3SiCl
III
IV
C1H(OSiMe3)Py
ArC7H P
O
OSiMe3
2
V
Bu-t
OH .
Bu-t
Py =
; Ar =
N
C1H(OH)Py
3 MeOH
3 MeOH
II
HOP[CH(OH)Py]2
HOP
O
III
V
_3 Me3SiOMe
_3 Me3SiOMe
C7H(OH)Ar
VII
O
VI
C1H(OH)Py
HOP
C1H(OH)Py
2 MeOH
4 MeOH
ArC7H P
O
IV
_2 Me3SiOMe
_4 Me3SiOMe
C7(O)Ar
OH
O
2
VIII
IX
Bu-t
OH .
Bu-t
Py =
; Ar =
N
The NMR spectra of compounds I–IX contain
characteristic signals of PC1H(ОХ) fragments whose
parameters are given below. In accordance with the
NMR spectra compounds II–VII and IX are the
mixtures of two stereoisomers whose ratio was
determined from 31Р NMR spectra. Data on the pre-
vailing isomer are given first.
stirring until the ammonia liberation ceased, and then it
was distilled. Yield 87% (33.9 g), bp 118°С (1 mm
1
Hg). Н NMR spectrum, δ, ppm: –0.25 s, –0.18 s and
2
–0.06 s (Ме3Si), 4.13 d (С1Н, JPС 4 Hz), 6.9–7.0 m
and 7.3–7.4 m (С5Н and С6Н), 8.2–8.25 m (С3Н and
С4Н). 13С NMR spectrum, δ, ppm: –0.12 s (Ме3SiОС),
3
0.74 d (3JPС 3 Hz) and 1.08 d (Ме3SiОР, JPС 2 Hz),
1
2
79.56 d (С1, JPС 14 Hz), 134.59 d (С2, JPС 9 Hz),
Bis(trimethylsilyl) pyrid-3-yl(trimethylsiloxy)-
methylphosphonite (I). To a solution of 30 g of bis-
(trimethylsiloxy)phosphine in 60 ml of methylene
chloride was added dropwise a solution of 10.7 g of
pyridin-3-carbaldehyde in 25 ml of methylene chloride
at cooling to 10°С and stirring. The mixture was
stirred for 0.5 h and then heated to boiling. After the
solvent removal to the residue was added 20 g of bis
(trimethylsilyl)amine. The mixture was refluxed at
3
148.57 d (С3, JPС 4 Hz), 147.83 s (С4), 122.34 s (С5),
3
134.18 d (С6, JPС 4 Hz). 31Р NMR spectrum, δ, ppm:
137.91 s.
Trimethylsilyl
bis[pyrid-3-yl(trimethylsiloxy)-
methyl]phosphinate (II). A mixture of 8.3 g of ammo-
nium hypophosphite, 10.7 g of pyridine-3-carbalde-
hyde and 26 g of trimethylchlorosilane in 50 ml of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 11 2008

2158
PRISHCHENKO et al.
methylene chloride was refluxed at stirring for 2 h.
Then ammonium chloride was filtered off and the
solvent was removed. To the residue was added 65 g
of bis(trimethylsilyl)amine. The mixture was refluxed
at stirring until the ammonia liberation ceased, and
then it was distilled. Yield 78% (19.4 g), bp 167°С
(1 mm Hg), mp 69°С. The first isomer (content 60%),
1Н NMR spectrum, δ, ppm: –0.10 to 0.55 m (Ме3Si),
1.44 s (Ме3С), 5.35 d (С1Н, 2JPН 8 Hz), 6.15 br.s (ОН),
7.25–8.65 m (С5Н4N, С6Н2). 13С NMR spectrum, δ,
ppm: –0.5 to 1.8 m (Ме3Si), 29.93 s (Ме3С), 34.39 s
1
(Ме3С), 70.63 d (С1, JPС 109 Hz), 160.48 s (СОН),
1
200.03 d (С7, JPС 104 Hz), 122.9-149.1 m (С5Н4N,
С6Н2). 31Р NMR spectrum, δ, ppm: 14.43 s. The
1
second isomer, Н NMR spectrum, δ, ppm: –0.18 to
–0.16 m (Ме3Si), 1.44 s (Ме3С), 5.24 d (С1Н, 2JPН 6 Hz),
6.15 br. s (ОН), 7.25–8.65 m (С5Н4N, С6Н2). 13С
NMR spectrum, δ, ppm: –0.5 to 1.8 m (Ме3Si), 29.93 s
2
4.37 d (С1Н, JPН 12 Hz), 6.5–8.0 m (С5Н4N). 13С
NMR spectrum, δ, ppm: –0.8 to –0.5 m (Ме3Si), 69.45
d (С1, 1JPС 115 Hz), 122.2-149.5 m (С5Н4N). 31Р NMR
(Ме3С), 34.39 s (Ме3С), 69.36 d (С1, JPС 120 Hz),
1
1
1
spectrum, δ, ppm: 30.23 s. The second isomer, Н
160.30 s (СОН), 199.61 d (С7, JPС 106 Hz), 122.9–
NMR spectrum, δ, ppm: –0.10 to 0.55 m (Ме3Si), 4.60
d and 4.71 d (С1Н, 2JPН 8 Hz), 6.5–8.0 m (С5Н4N). 13С
NMR spectrum, δ, ppm: –0.8 to –0.5 m (Ме3Si), 68.47
149.1 m (С5Н4N, С6Н2). 31Р NMR spectrum, δ, ppm:
15.79 s. Found, %: С 58.81; Н 8.01. С27Н44NО5PSi2.
Calculated, %: С 58.99; Н 8.07.
1
1
d (С1, JPС 119 Hz) and 68.90 d (С1, JPС 112 Hz),
122.2–149.5 m (С5Н4N). 31Р NMR spectrum, δ, ppm:
31.59 s. Found, %: С 50.59; Н 7.42. С21Н37N2О4PSi3.
Calculated, %: С 50.78; Н 7.51.
Bis(trimethylsilyl) 3,5-di-tert-butyl-4-hydroxy-
phenylmethylenebis[pyrid-3-yl(trimethylsiloxy)me-
thylphosphinate] (V). Yield 89 %, mp 78°С. The first
1
isomer (content 60%), Н NMR spectrum, δ, ppm:
–0.2 to 0.2 m (Ме3Si), 1.36 s (Ме3С), 3.75 t (С7Н,
Trimethylsilyl [pyrid-3-yl(trimethylsiloxy)me-
thyl][3,5-di-tert-butyl-4-hydroxyphenyl-(trimethyl-
siloxy)-methyl]phosphinate (III). To a solution of
7.8 g of phosphonite I in 30 ml of methylene chloride
was added 4.7 g of 3,5-di-tert-butyl-4-hydroxy-
benzaldehyde at stirring and cooling to 0°С. The mix-
ture was stirred for 0.5 h. After the solvent removal the
residue was kept at 30°С in a vacuum (0.5 mm Hg) for
1 h. Yield 86% (10.7 g), viscous oily liquid. The first
2
2JPН 18 Hz), 4.81 d (С1Н, JPН 12 Hz), 7.0–8.6 m
(С5Н4N, С6Н2). 13С NMR spectrum, δ, ppm: –0.15 to
1.85 m (Ме3Si), 29.99 s (Ме3С), 34.41 s (Ме3С), 42.31
1
1
t (С7, JPС 78 Hz), 72.36 d (С1, JPС 115 Hz), 153.72 s
(СОН), 122.9–149.6 m (С5Н4N, С6Н2). 31Р NMR
spectrum, δ, ppm: 30.93 s. The second isomer, Н
1
NMR spectrum, δ, ppm: –0.2 to 0.2 m (Ме3Si), 1.37 s
2
2
(Ме3С), 3.49 t (С7Н, JPН 18 Hz), 4.88 d (С1Н, JPН
8
1
Hz), 7.0-8.6 m (С5Н4N, С6Н2). 13С NMR spectrum, δ,
ppm: –0.15 to 1.85 m (Ме3Si), 30.42 s (Ме3С), 34.28 s
(Ме3С), 43.31 t (С7, 1JPС 80 Hz), 71.91 d (С1, 1JPС 113
Hz), 153.72 s (СОН), 122.9–149.6 m (С5Н4N, С6Н2).
31Р NMR spectrum, δ, ppm: 30.49 s. Found, %: С
54.89; Н 7.94. С39Н68N2О7P2Si4. Calculated, %: С
55.03; Н 8.05.
isomer (content 55%). Н NMR spectrum, δ, ppm:
–0.25 to –0.14 m (Ме3Si), 1.26 s (Ме3С), 4.83 d (С1Н ,
2
2JPН 10 Hz) 5.19 d (С7Н, JPН 8 Hz), 7.0–8.5 m
(С5Н4N, С6Н2). 13С NMR spectrum, δ, ppm: –0.25 to
0.75 m (Ме3Si), 30.18 s (Ме3С), 30.21 s (Ме3С), 70.71
1
d (1JPС 108 Hz) and 71.89 d (С1, С7, JPС 107 Hz),
122.5–154.5 m (С5Н4N, С6Н2). 31Р NMR spectrum, δ,
1
ppm: 30.99 s. The second isomer. Н NMR spectrum,
Bis[pyrid-3-yl(hydroxy)methyl]phosphinic acid
(VI). A mixture of 19.4 g of phosphinate II and 50 ml
of methanol was heated to boiling. After the solvent
removal white crystals were kept in a vacuum (1 mm
Hg) for 1 h. Yield 94% (10.3 g), mp 204°С. The first
δ, ppm: –0.25 to –0.14 m (Ме3Si), 1.31 s (Ме3С), 4.57
d (2JPН 8 Hz) and 4.94 d (2JPН 6 Hz, С1Н and С7Н), 7.0-
8.5 m (С5Н4N, С6Н2). 13С NMR spectrum, δ, ppm: –
0.25 to 0.75 m (Ме3Si), 29.95 s (Ме3С), 34.95 s
(Ме3С), 68.99 d (1JPС 110 Hz) and 70.67 d (1JPС 112
Hz, С1 and С7), 122.5–154.5 m (С5Н4N, С6Н2). 31Р
NMR spectrum, δ, ppm: 33.12 s. Found, %: С 57.52;
Н 8.64. С30Н54NО5PSi3. Cal-culated, %: С 57.75; Н
8.72.
1
isomer (content 75%), Н NMR spectrum, δ, ppm:
2
5.56 d (С1Н, JPН 8 Hz), 7.95–8.95 m (С5Н4N). 13С
1
NMR spectrum, δ, ppm: 70.92 d (С1, JPС 98 Hz),
127.8-145.8 m (С5Н4N). 31Р NMR spectrum, δ, ppm:
1
29.42 s. The second isomer, Н NMR spectrum, δ,
2
ppm: 5.61 d (С1Н, JPН 8 Hz), 7.95–8.95 m (С5Н4N).
Phosphinates IV–V were similarly prepared.
1
13С NMR spectrum, δ, ppm: 71.08 d (С1, JPС 98 Hz),
Trimethylsilyl [pyrid-3-yl(trimethylsiloxy)methyl]-
3,5-di-tert-butyl-4-hydroxybenzoyl-phosphinate (IV).
Yield 88%, mp 108°С. The first isomer (content 60%),
1Н NMR spectrum, δ, ppm: –0.18 to –0.16 m (Ме3Si),
127.8–145.8 m (С5Н4N). 31Р NMR spectrum, δ, ppm:
30.80 s. Found, %: С 51.26; Н 4.72. С12Н13N2О4P.
Calculated, %: С 51.44; Н 4.68.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 11 2008

SYNTHESIS OF BIS(TRIMETHYLSILYL) PYRID-3-YL(TRIMETHYLSILOXY)-...
2159
(С5Н4N, С6Н2). 13С NMR spectrum, δ, ppm: 29.66 s
Acids VII–IX were similarly prepared.
1
(Ме3С), 34.13 s (Ме3С), 51.38 t (С7, JPС 84 Hz),
Pyrid-3-yl(hydroxy)methyl[3,5-di-tert-butyl-4-hyd-
roxyphenyl(hydroxy)methyl]phosphinic acid (VII).
Yield 96%, mp 208°С. The first isomer (content 55%),
1Н NMR spectrum, δ, ppm: 1.40 s (Ме3С), 5.09 d
(2JPН 7 Hz) and 5.48 d (2JPН 10 Hz, С1Н and С7Н),
7.2–8.9 m (С5Н4N, С6Н2). 13С NMR spectrum, δ, ppm:
29.51 s (Ме3С), 34.24 s (Ме3С), 67.84 d (1JPС 97 Hz)
and 70.56 d (1JPС 112 Hz, С1 and С7), 122.5–153.5 m
(С5Н4N, С6Н2). 31Р NMR spectrum, δ, ppm: 33.23 s.
1
69.95 d (С1, JPС 100 Hz), 153.05 s (СArОН), 121.5-
145.5 m (С5Н4N, С6Н2). 31Р NMR spectrum, δ, ppm:
1
31.22 s. The second isomer, Н NMR spectrum, δ,
ppm: 1.40 s (Ме3С), 4.32 t (С7Н, 2JPН 20 Hz), 5.59 d
(С1Н, 2JPН 8 Hz ), 7.3–9.0 m (С5Н4N, С6Н2). 13С NMR
spectrum, δ, ppm: 29.66 s (Ме3С), 34.13 s (Ме3С),
1
1
51.38 t (С7, JPС 84 Hz), 70.30 d (С1, JPС 100 Hz),
153.05 s (СArОН), 121.5–145.5 m (С5Н4N, С6Н2). 31Р
NMR spectrum, δ, ppm: 31.78 s. Found, %: С 57.52;
Н 6.49. С27Н36N2О7P2. Calculated, %: С 57.65; Н
6.45.
1
The second isomer, Н NMR spectrum, δ, ppm: 1.45 s
(Ме3С), 4.93 d (2JPН 8 Hz) and 5.27 d (2JPН 9 Hz, С1Н
and С7Н), 7.2–8.9 m (С5Н4N, С6Н2). 13С NMR
spectrum, δ, ppm: 29.45 s (Ме3С), 34.24 s (Ме3С),
70.38 d (1JPС 95 Hz) and 72.66 d (1JPС 110 Hz, С1 and
С7), 122.5–153.5 m (С5Н4N, С6Н2). 31Р NMR
spectrum, δ, ppm: 30.15 s. Found, %: С 61.59; Н 7.56.
С21Н31NО5P. Calculated, %: С 61.75; Н 7.65.
The NMR spectra were obtained on a Bruker
Avance-400 device using CDCl3 (I–V), CD3OD (VII)
and CD3COOD (VI, VIII, IX) as solvents and ТМS
(1H, 13C) and 85% H3PO4 in D2O solution (31Р) as
references.
Pyrid-3-yl(hydroxy)methyl(3,5-di-tert-butyl-4-hyd-
roxybenzoyl)phosphinic acid (VIII). Yield 95%, mp
ACKNOWLEDGMENTS
1
165°С. Н NMR spectrum, δ, ppm: 1.47 s (Ме3С),
This work was financially supported by the Russian
Foundation for Basic Research (grant No. 08-03-
00282).
2
5.78 d, (С1Н, JPН 8 Hz), 7.7–9.1 m (С5Н4N, С6Н2).
13С NMR spectrum, δ, ppm: 29.26 s (Ме3С), 34.18 s
1
(Ме3С), 69.05 d (С1, JPС 102 Hz), 126.0–145.3 m
(С5Н4N, С6Н2), 160.0 s (СArОН), 205.86 d (С7,
1JPС 115 Hz). 31Р NMR spectrum, δ, ppm: 18.78 s.
Found, %: С 61.98; Н 7.03. С21Н28NО5P. Calculated,
%: С 62.21; Н 6.96.
REFERENCES
1. Prishchenko, А.А., Livantsov, М.V., Novikova, О.P.,
Livantsova, and Kashulin, I.A., Zh. Obshch. Khim.,
2005, vol. 75, no. 10, p. 1748.
3,5-Di-tert-butyl-4-hydroxyphenylmethylenebis-
[pyrid-3-yl(hydroxy)methylphosphinic] acid (IX).
Yield 97%, mp 235°С. The first isomer (content 70%).
1Н NMR spectrum, δ, ppm: 1.40 s (Ме3С), 4.32 t
2. Koloyazhnyi, О.I., Usp. Khim., 2006, vol. 75, no. 3,
p. 254.
3. Prishchenko, А.А., Livantsov, М.V., Novikova, О.P.,
and Livantsova, L.I., Zh. Obshch. Khim., 2007, vol. 77,
2
(С7Н, 2JPН 20 Hz), 5.38 d (С1Н, JPН 8 Hz), 7.3–9.0 m
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 11 2008