Reaction of Bis(trimethylsiloxy)phosphine with ethoxymethyleneimines hydrochlorides

Full text of DOI:10.1134/S1070363214030335

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 3, pp. 605–607. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © A.A. Prishchenko, M.V. Livantsov, O.P. Novikova, L.I. Livantsova, I.S. Ershov, V.S. Petrosyan, 2014, published in Zhurnal
Obshchei Khimii, 2014, Vol. 84, No. 3, pp. 521–523.
LETTERS
TO THE EDITOR
Reaction of Bis(trimethylsiloxy)phosphine
with Ethoxymethyleneimines Hydrochlorides
A. A. Prishchenko, M. V. Livantsov, O. P. Novikova,
L. I. Livantsova, I. S. Ershov, and V. S. Petrosyan
Lomonosov Moscow State University, Moscow, 119991 Russia
е-mail: aprishchenko@yandex.ru
Received November 28, 2013
DOI: 10.1134/S1070363214030335
Aminomethylenediphosphonites containing unsub-
tituted amino group are of interest as key synthons in
the preparation of a variety of aminomethylene-
the reaction of bis(trimethylsiloxy)phosphine with
easily accessible ethoxymethyleneimines hydrochlo-
rides [3]. Thus, the reaction of an excess of highly
active bis(trimethylsiloxy)phosphine with hydrochlo-
rides of substituted ethoxyimines proceeded in
methylene chloride to form diphosponite intermediates
Ia–IIIa. Refluxing the latter with a mixture of bis(tri-
methylsilyl)amine and trimethylchlorosilane afforded
diphosponites I–III in high yields.
diphosphorus-containing
compounds,
promising
ligands and biologically active substances [1].
Recently, we obtained some N-substituted amino-
methylenediphosponites by reacting bis(trimethyl-
siloxy)phosphine with N-substituted formamides and
ethoxymethyleneimines [2]. In this work we studied
NH2
XO
X2NH, XCl
EtOC(R)=NH HCl
[(XO)2P]2C(R)NH2
3(XO)2PH
PC(R)P(OX)2
_
NH4Cl
−XOEt, −XOP(O)H2, −XCl
H
O
_
_
I III
Iа IIIа
X = Me3Si; R = Me (I, Iа), Ph (II, IIа),
(III, IIIа).
N
Scheme 1.
Note that the intermediate diphosponite Ia was
isolated in good yield by distillation. The initial
formation of diphosponites IIa, IIIa was detected in
the reaction mixture by 31P NMR spectroscopy.
Further trimethylsilylation of diphosponites I–III with
a mixture of bis(trimethylsilyl)amine and trimethyl-
chlorosilane proceeded slowly to afford the target
diphosponites Ib–IIIb only in trace amounts (5–15%)
(Scheme 1).
X2NH, XCl
[(XO)2P]2C(R)NHX
I−III
−NH4Cl
Ib−IIIb
X = Me3Si; R = Me (I, Ib), Ph (II, IIb),
(III, IIIb).
N
Compounds I–VI contain reactive fragments (NH,
POSi, PH) and are convenient synthons for obtaining
new functionalized aminomethylenediphosphorus-con-
taining substances. NMR spectra of I–VI contain
Treating the diphosponites I–III with a diluted
solution of sodium methoxide in methanol yielded
diphosphonous acids salts IV–VI as white hygroscopic
crystalline substances (Scheme 2).
605

606
PRISHCHENKO et al.
1
Scheme 2.
0.9–1.1 m (Ме), 6.57 d (2РН, JРH 545.2 Hz), 1.12–
1.32 m (NH2). 13С NMR spectrum, δC, ppm: 55.47 d.d
(С1, 1JPС 32.7, 1JPС 66.3 Hz), 14.04 d (Ме, 2JPС 22.4 Hz),
0.8–1.2 m (3Me3Si). 31Р NMR spectrum, δP, ppm:
145.39 d (Р, 2JРР 41.6 Hz), 28.14 d (РН, 2JРР 41.6 Hz).
NaO
H
2MeONa, 4MeOH
I−III
P C(R)NH2
−4Me3SiOMe
O
1
2
Fourth isomer (content 15%). Н NMR spectrum, δ,
IV−VI
ppm: from –0.03 to 0.05 m (2Ме3Si), 0.03–0.05 m
(Ме3Si), 0.9–1.1 m (Ме), 6.54 d (2РН, 1JРH 546.8 Hz),
1.12–1.32 m (NH2). 13С NMR spectrum, δC, ppm:
R = Me (IV), Ph (V),
(VI).
54.73 d.d (С1, JPС 34.3, JPС 71.1 Hz), 13.61 d (Ме,
1
1
N
2JPС 20.8 Hz), 0.8–1.2 m (3Me3Si). 31Р NMR spectrum,
characteristic signals of the fragment A, whose struc-
2
2
δP, ppm: 144.97 d (Р, JРР 55.4 Hz), 31.91 d (РН, JРР
ture is shown below.
55.4 Hz).
4
4
3
3
2
2
P2C1(R)NH2,
,
5
According to NMR data, diphosphonite Ia contains
10% of diphosphonite I.
5
R = Me,
N
6
A
O,O,O,O-Tetra(trimethylsilyl)-1-aminoethylidene-
diphosphonite (I). A mixture of 5.4 g diphosphonite
Ia, 20 g of bis(trimethylsilyl)amine, and 5 g of tri-
methylchlorosilane was refluxed until sublimation of
ammonium chloride ceased, and then the reaction mix-
ture was distilled. Yield 5.6 g, 88%, bp 124°C
According to NMR spectra, compound Ia is a
mixture of four stereoisomers and compounds IIa, IIIa
are mixtures of two stereoisomers, whose ratio was
determined by 31P NMR. Instead of readily oxidizable
compounds I–III elemental analysis was carried out
for their stable derivatives IV–VI.
1
(1 mm Hg). Н NMR spectrum, δ, ppm: 0.92 t (NH2,
3
3JРH 13.2 Hz), 0.76 t (Ме, JРH 12.4 Hz), 0.01 br.s
O,O,O-Tris(trimethylsilyl)-1-aminoethylidenedi-
phosphonite (Ia). A solution of 13 g of bis(tri-
methylsiloxy)phosphine in 10 mL of methylene chlo-
ride was added to a suspension of 2.5 g of 1-ethoxy-
ethylideneimine hydrochloride in 25 mL of methylene
chloride with stirring. The mixture was stirred for 1 h,
and then the solvent was removed in a vacuum. To the
residue was added 20 mL of bis(trimethylsilyl)amine.
The mixture was heated until the evolution of am-
monia ceased. Excess of bis(trimethylsilyl)amine was
distilled off, and the residue was distilled. Yield 5.4 g,
68%, bp 121°C (1 mm Hg). First isomer (content
35%). 1Н NMR spectrum, δ, ppm: –0.03–0.05 m
(4Ме3Si). 13С NMR spectrum, δC, ppm: 60.30 t (С1,
2
1JPС 32.8 Hz), 14.55 t (Ме, JPС 17.6 Hz), 1.24
(4Me3Si). 31Р NMR spectrum: δP 154.54 ppm.
According to NMR data, diphosphonite I contains
15% of diphosphonite Ib. 13С NMR spectrum, δC,
1
2
ppm: 62.36 t (С1, JPС 33.5 Hz), 13.09 t (Ме, JPС
19.2 Hz). 31Р NMR spectrum: δP 151.21 ppm.
Diphosphonites II, III were prepared similarly.
O,O,O,O-Tetra(trimethylsilyl)-1-aminobenzyl-
idenediphosphonite (II). Yield 74%, bp 144°C (1 mm
1
Hg). Н NMR spectrum, δ, ppm: –0.16 s (2Me3Si),
3
3
(2Ме3Si), 0.03–0.05 m (Ме3Si), 0.88 d.d (Ме, JРH
0.04 s (2Me3Si), 1.60 t (NH2, JРH 7.6 Hz), 6.9–7.4 m
13.2, 3JРH 17.4 Hz), 6.58 d (2РН, 1JРH 550.8 Hz), 1.12–
1.32 m (NH2). 13С NMR spectrum, δC, ppm: 55.81 d.d
(С1, 1JPС 34.3, 1JPС 67 Hz), 15.18 d (Ме, 2JPС 19.1 Hz),
0.8–1.2 m (3Me3Si). 31Р NMR spectrum, δP, ppm:
1
(С6H5). 13С NMR spectrum, δC, ppm: 70.35 t (С1, JPС
41.5 Hz), 138.75 t (С2, 2JPС 10.4 Hz), 126.73 t (С3, 3JPС
8.8 Hz), 127.43 (С4), 125.26 (С5), 0.92 (2Me3Si), 1.35
(2Me3Si). 31Р NMR spectrum: δP 149.74 ppm.
According to 31Р NMR diphosphonite II contains 5%
of diphosphonite IIb (δР 141.14 ppm).
2
145.83 d (Р), 30.74 d (РН), JРР 53.6 Hz. Second
1
isomer (content 30%). Н NMR spectrum, δ, ppm:
–0.03–0.05 m (2Ме3Si), 0.03–0.05 m (Ме3Si), 0.9–1.1
1
In the spectrum of the reaction mixture there were
m (Ме), 6.64 d (2РН, JРH 551.2 Hz), 1.12–1.32 m
(NH2). 13С NMR spectrum, δC, ppm: 56.15 d.d (С1,
the signals of diphosphonite IIa. First isomer (content
2
80%). 31Р NMR spectrum, δP, ppm: 142.45 d (Р, JРР
1
2
1JPС 34.4, JPС 68.7 Hz), 15.29 d (Ме, JPС 18.3 Hz),
0.8–1.2 m (3Me3Si). 31Р NMR spectrum, δP, ppm:
146.34 d (Р, 2JРР 51.5 Hz), 29.05 d (РН, 2JРР 51.5 Hz).
2
65.4 Hz), 28.88 d (РН, JРР 65.4 Hz). Second isomer
(content 20%). 31Р NMR spectrum, δP, ppm: 141.04 d
(Р, 2JРР 71.4 Hz), 24.96 d (РН, 2JРР 71.4 Hz).
1
Third isomer (content 20%). Н NMR spectrum, δ,
ppm: –0.03–0.05 m (2Ме3Si), 0.03–0.05 m (Ме3Si),
O,O,O,O-Tetra(trimethylsilyl)-1-amino-1-(pyrid-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 3 2014

REACTION OF BIS(TRIMETHYLSILOXY)PHOSPHINE
607
3-yl)methylenediphosphonite (III). Yield 72%, bp
145°C (1 mm Hg). 1Н NMR spectrum, δ, ppm: –0.13 s
(2Me3Si), –0.28 s (2Me3Si), 1.42 t (NH2, JРH 9.6 Hz),
1-Amino-1-(pyrid-3-yl)methylenediphosphonousacid
disodium salt (VI). Yield 94 %. 1Н NMR spectrum, δ,
ppm: 6.82 d (2РH, 1JPH 541.2 Hz), 7.2–8.5 m (С5Н4N).
3
3
3
1
6.92 d.d (С4H, JНH 4.8, 8 Hz), 7.52 d (С3H, JНH
13С NMR spectrum, δC, ppm: 60.34 t (С1, JPС 75.9
8 Hz), 8.10 d (С5H, JНH 4.8 Hz), 8.48 s (С6H). 13С
Hz), 151.59 (С2), 135.90 (С3), 136.14 (С4), 146.30 (С5),
147.43 (С6). 31Р NMR spectrum: δP 27.84 ppm. Found, %:
С 25.59; Н 2.97. С6Н8N2Na2О4P2. Cal-culated, %: С
25.73; Н 2.88.
3
NMR spectrum, δC, ppm: 69.16 t (С1, JPС 41.5 Hz),
1
151.61 (С2), 134.05 t (С3, JPС 7.2 Hz), 135.03 (С4),
3
146.07 (С5), 148.28 t (С6, 3JPС 9.6 Hz), 0.80 (2Me3Si),
1.14 (2Me3Si). 31Р NMR spectrum, δP: 148.07 ppm.
According to 31Р NMR data, diphosphonite III
contains 5% of diphosphonite IIIb (δP 141.18 ppm).
NMR spectra were recorded on a Bruker Avance-
400 spectrometer in CDCl3 (I–III) or D2O (IV–VI),
internal reference TMS (1H, 13C) or external reference
85% phosphoric acid solution in D2O (31Р).
In the spectrum of the reaction mixture there were
the signals of diphosphonite IIIa. First isomer (content
2
70%). 31Р NMR spectrum, δP, ppm: 142.15 d (Р, JРР
AKCNOWLEDGMENTS
2
61.4 Hz), 27.51 d (РН, JРР 61.4 Hz). Second isomer
(content 30%). 31Р NMR spectrum, δP, ppm: 141.24 d
(Р, 2JРР 65.4 Hz), 23.61 d (РН, 2JРР 65.4 Hz).
This work was supported by the Russian Founda-
tion for Basic Research (grants nos. 12-03-00003 and
14-03-00001).
1-Aminoethylidenediphosphonous acid disodium
salt (IV). To a solution of 1.3 g of sodium methylate in
30 mL of methanol was added 5.6 g diphosphonite I in
20 mL of diethyl ether with stirring under cooling to
10°C. Then the solvent was removed. White crystals
were kept in a vacuum (1 mm Hg) for 1 h. Yield 2.5 g,
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3
97%. Н NMR spectrum, δ, ppm: 1.07 t (Ме, JPH
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1
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1
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1
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С7Н9NNa2О4P2. Calculated, %: С 30.13; Н 3.25.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 3 2014