Synthesis of 2-element(Si, Ge, P, Fc)-substituted O,O-bis(trimethylsilyl) alkylphosphonites and their functionaized derivatives

Article abstract of DOI:10.1002/hc.20469

Addition of bis(trimethylsiloxy)phosphine to element(Si, Ge, P, Fc)-substituted alkenes is proposed as convenient procedures for the synthesis of new 2-element(Si, Ge, P, Fc)-substituted alkylphosphonites. Also the new functionalized derivatives of these

Full text of DOI:10.1002/hc.20469

Heteroatom Chemistry
Volume 19, Number 5, 2008
Synthesis of 2-Element(Si, Ge, P, Fc)-
Substituted O,O-Bis(trimethylsilyl)
Alkylphosphonites and Their
Functionalized Derivatives
Andrey A. Prishchenko, Mikhail V. Livantsov, Olga P. Novikova,
Ludmila I. Livantsova, and Valery S. Petrosyan
Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow 119991, Russia
Received 26 June 2007; revised 7 April 2008
ment fragments and various amino or amido groups
ABSTRACT: Addition of bis(trimethylsiloxy)phos-
present interest as promising ligands in a series
phine to element(Si, Ge, P, Fc)-substituted alkenes
of catalytic systems and biologically active com-
is proposed as convenient procedures for the syn-
pounds as organophosphorus biomimetics of amino
thesis of new 2-element(Si, Ge, P, Fc)-substituted
acids [3–6]. In the present work, we report here the
alkylphosphonites. Also the new functionalized deriva-
radical addition of bis(trimethylsiloxy)phosphine to
tives of these phosphonites including various amino
element(Si, Ge, P, Fc)-substituted alkenes, result-
and amido groups as well as certain properties of these
ing in formation of corresponding phosphonite in
ꢀ
C
compounds are presented.
2008 Wiley Periodicals,
high yield. Furthermore, amino- or amidomethyla-
tion of these phosphonites is resulting in the new
derivatives of organophosphorus acids containing
organoelement groups and various aminomethyl or
amidomethyl moiety.
Inc. Heteroatom Chem 19:500–505, 2008; Published on-
line in Wiley InterScience (www.interscience.wiley.com).
DOI 10.1002/hc.20469
RESULTS AND DISCUSSION
INTRODUCTION
So the radical addition of bis(trimethylsiloxy)-
phosphine A to element(Si, Ge, P, Fc)-substituted
ethylenes resulting in formation of phosphonites 1–4
in high yields (cf. [7]). The reaction was initiated by
azobis(isobutyronitrile) under conditions of its ther-
molysis (100–120◦C) (Eq. (1)).
Silicon-containing esters of trivalent phosphorus
acids are widely used in organophosphorus syn-
thesis as highly reactive synthons, which were
successfully added to a variety of unsaturated
substances to obtain promising types of organophos-
phorus compounds [1,2]. Functionalized derivatives
of organophosphorus acids containing organoele-
Correspondence to: Andrey A. Prishchenko; e-mail:
aprishchenko@yandex.ru.
Contract grant sponsor: Russian Foundation for Basic
Research.
Also the similar addition of phosphine A to vinyl-
and isopropenyl ferrocenes proceeds regioselectively
Contract grant number: 08-03-00282.
c
ꢀ
2008 Wiley Periodicals, Inc.
500

Synthesis of 2-Element(Si, Ge, P, Fc)-Substituted O,O-Bis(trimethylsilyl) Alkylphosphonites 501
to give 2-ferrocenyl-substituted alkylphosphonites
5, 6 in high yields (Eq. (2)).
Under similar conditions, the reaction of an
excess of phosphine A with methyl(phenyl)divinyl-
silane provides a mixture of phosphonite 7 and bis-
phosphonite 8 in equal amounts. Phosphonites 7
and 8 were isolated by distillation in good yields
(Eq. (3)).
Ferrocenyl-substituted phosphonites 5, 6 are
smoothly aminomethylated with bis(dimethyl-
amino)methane under similar conditions to form
phosphinates 22, 23 (Eq. (6)).
Note that the similar reaction of an excess of
phosphine A with phenyldivinylphosphine gives only
bisphosphonite 9 (Eq. (4)).
Silicon-substituted phosphonites 1, 2 readily re-
act with various N-chloromethylamides in methy-
lene chloride solution by the Arbuzov reaction
scheme to form phosphinates 24–27 (Eq. (7)).
To conclude, we proposed a convenient method
to give the new element(Si, Ge, P, Fc)-substituted
alkylphosphonites 1–9 (see Table 1), which are
the promising synthons in organophosphorus
chemistry.
Phosphonites 1–9 were successfully used by
us for preparing new derivatives of functional-
ized organophosphorus acids containing stable
organoelement groups and aminomethyl group.
The aminomethylation of trimethylsilyl esters of
hypophosphorous and phosphorous acids was thor-
oughly investigated by us in [8]. Now we present the
new results of aminomethylation of element(Si, Ge,
P, Fc)-substituted alkylphosphonites. Hence, phos-
phonites 1–4,7 are easily aminomethylated with
bis(dialkylamino)methanes at 130◦C in the presence
of zinc chloride as a catalyst to give corresponding
phosphinates (10–21) in high yields (Eq. (5)). Note
that to obtain phosphinate 13, it is necessary to
The constants and NMR data of synthesized
phosphinates 10–27 are presented in Table 2.
Trimethylsilyl esters of several organophospho-
rus acids easily react with methanol to obtain a se-
ries of water-soluble acids [1]. So treatment of phos-
phonites 3–9 and phosphinates 16–23 with a dilute
solution of sodium methylate in methanol results
in formation of water-soluble sodium phosphonites
28–34 and sodium phosphinates 35–42, respectively
(Eq. (8)).
use
N-methoxymethylbis(trimethylsilyl)amine
MeOCH2N(SiMe)2
reagent.
as
an
aminomethylating
Heteroatom Chemistry DOI 10.1002/hc

502 Prishchenko et al.
TABLE 1 Yields, Product Constants, and NMR Spectral Data for the PC1H2C2HE Fragmentsa (δ, ppm; J, Hz) of Phosphonites
1–9a
No.
Yield (%)
bp( ◦C) (p (mmHg))
δ(C1)d
1JPC
δ(C2)d
2JPC
δ(P) s
1
89
87
78
83
88
85
48
45
87
108 (2)
103 (1)
113 (1)
164 (1)
162 (1)
165 (1)
133 (1)
178 (1)
192 (1)
34.92
33.91
35.67
36.44b
42.10
50.98
34.01
33.58
35.75e
26.3
25.8
25.7
27.2
24.3
27.5
25.7
26.0
26.4
1.34
1.09
10.1
11.9
–
13.3
16.2
14.7
6.8
159.74
159.34
158.30
157.23b
158.74
160.81
157.34
158.23
156.96e
2
3
3.70 s
18.54b
20.73
27.63
4.20
4
5c
6d
7
8
9
3.01
10.8
12.2
17.63e
aIn 1H NMR spectra, the signals of methylene groups of these fragments are multiplets and partially or completely overlap; all signals of the
alkyl, vinyl, phenyl, trimethylsilyl, and ferrocenyl fragments are in the standard area.
bdd, 2JPC = 10.7, 1JPC = 13.3, respectively; d, 3JPP = 22.5; δP (PPh2) = −15.17 d, 3JPP = 22.5.
c,dCherry-red liquids; 13C NMR spectrum, δ, ppm (J, Hz): 5: 89.77 d (CFc, 3JPC = 12.2); 6: 96.81 d (CFc, 3JPC = 7.8), 22.62 d (MePr, 3JPC = 8.4).
ed.d, 2JPC = 8.4, 1JPC = 15.1, respectively; d, 3JPP = 20.0; δP (PPh) = −20.67 t, 3JPP = 20.0.
TABLE 2 Yields, Product Constants, and NMR Spectral Data for the PC1H2C2H2E and PC3H2NC4Hn Fragmentsa (δ, ppm;
J, Hz) of Phosphinates 10–27a
No. Yield (%) bp(◦C) (p, mmHg)
nD20
δ(C1) d JPC δ(C2) d 2JPC δ(C3) d 1JPC
δ(C4)d
3JPC
δ(P) s
1
10
11
12
13
14
15
16
17
18
19
20
21
22d
23e
81
83
85
65
74
72
78
72
67
68
65
68
75
72
115 (1)
151 (2)
132 (1)
147 (2)
146 (1)
152 (1)
141 (1)
189 (2)
160 (1)
152 (1)
208 (1.5)
202 (1)
182 (1)
174 (0.5)
1.4575 22.85 91.2
1.4705 23.05 90.2
1.4713 23.04 91.9
1.4458 22.24 85.5
1.4502 20.76 93.0
1.4498 21.03 95.0
1.5019 21.81 91.5
1.5085 21.60 91.2
1.4755 23.36 89.7
1.4785 23.38 90.7
2.74
2.91
2.82
1.54 s
1.23
1.45
4.84
4.78
2.71
1.94
7
58.25 110.7
57.91 110.8
57.30 109.7
45.26 102.8
57.45 109.6
56.14 111.4
57.14 111.9
56.31 117.7
56.59 111.1
56.03 110.8
57.84 113.5
56.86 112.6
57.93 113.3
58.95 112.2
58.90 112.3
42.08 101.6
46.95 101.3
42.05 102.3
46.20 105.4
47.79
56.97
56.07
–
9.1
8.4
8.9
–
41.34
41.48
40.74
40.78
42.87
41.80
42.99
43.32
43.63
42.35
41.32b
39.95c
40.90
40.60
40.70
39.35
40.25
39.09
39.97
7.3
7.4
–
6.6
6.5
7.2
6.7
8.3
8.2
4.6
2.6
–
–
–
7.4
7.4
4.2
3.5
55.76
54.90
47.08
55.68
56.16
55.05
56.31
54.83
47.13
47.22
45.38
48.11 s
50.71 s
48.69
49.20
9.0
8.8
10.0
8.3
8.9
9.1
9.2
9.1
9.8
9.4
3.8
–
1.5495 24.91b 91.2 19.87b
1.5505 24.43c 91.5 19.52c
1.5435 29.04 92.3 21.40 s
1.5422 36.52 92.2 27.38 s
36.36 91.2 27.18 s
1.4785 23.54 88.9
1.4835 23.53 88.0
1.4527 22.84 90.7
1.4480 22.21 89.5
24
25
26
27
82
78
73
69
154 (1)
175 (2)
159 (1)
176 (1)
2.45
2.47
1.26
2.15
–
8.1
7.3
aIn 1H NMR spectra, the signals of methylene groups of these fragments are multiplets and partially or completely overlap; all signals of the
alkyl, vinyl, phenyl, trimethylsilyl, and ferrocenyl fragments are in the standard area.
bdd, 2JPC = 15.0, 1JPC = 14.9, respectively; d, 3JPP = 50.5; δP (PPh2) = –14.69 d, 3JPP = 50.5.
cdd, 2JPC = 15.2, 1JPC = 14.8, respectively; d, 3JPP = 49.7; δP (PPh2) = – 15.18 d, 3JPP = 49.7.
(MePr, 3JPC = 3.0); 23, second isomer: 95.53 d (CFc, 3JPC = 14.4), 22.26 d (MePr, 3JPC = 2.8); ratio of stereoisomers 7:3 (measured by 31P NMR).
d,eCherry-red liquids; 13C NMR spectrum, δ, ppm (J, Hz): 22: 87.81 d (CFc
,
3JPC = 18.2); 23, first isomer: 95.65 d (CFc
,
3JPC = 15.2), 22.17 d
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of 2-Element(Si, Ge, P, Fc)-Substituted O,O-Bis(trimethylsilyl) Alkylphosphonites 503
TABLE 3 Yields, Product Constants, and NMR Spectral Data for the PC1H2C2H2E fragmentsa (δ, ppm; J, Hz) of Sodium
Phosphonites 28–34a
No.
Yield (%)
δ(H) PH, d t
1JPH
3JHH
δ(C1) d
1JPC
δ(C2) d
2JPC
δ(P) sb
28
97
96
96
94
95
94
93
6.82
6.88 d
6.84
6.95 d
7.03 d
6.83
497.2
508.0
495.6
501.2
502.4
499.2
506.4
2.0
–
1.6
–
–
1.8
–
26.95
28.99c
25.84
33.24
41.07
25.46
27.70e
87.2
87.5
88.3
88.5
89.2
88.0
86.8
2.18
19.32c
5.23
5.9
<1
5.2
–
–
32.13
27.29c
30.93
27.22
25.69
31.06
27.43e
29
30
31d
32d
33
21.72 s
28.22 s
4.33
5.4
<1
34
6.90 d
18.47e
aIn 1H NMR spectra, the signals of methylene groups of these fragments are multiplets and partially or completely overlap; all signals of the
alkyl, vinyl, phenyl, and ferrocenyl fragments are in the standard area.
1
bData of 31P{ H} spectra.
cdd, 2JPC = 13.8, 1JPC = 10.1, respectively; d, 3JPP = 53.7; δP (PPh2) = −15.61 d, 3JPP = 53.7.
dOrange crystals; 13C NMR spectrum, δ, ppm (J, Hz): 31: 89.98 d (CFc, 3JPC = 18.9); 32: 87.28 d (CFc, 3JPC = 15.0), 22.36 d (MePr, 3JPC = 5.3).
edd, 2JPC = 10.3, 1JPC = 7.9, respectively; d, 3JPP = 46.4; δP (PPh) = −19.29 t, 3JPP = 46.4.
The synthesized salts are white (28–30, 33–40)
or orange (31, 32, 41, 42) hygroscopic crystals (see
Tables 3 and 4) and may be used as water-soluble lig-
ands in promising catalytic complexes as well as bio-
logically active compounds (cf. [9,10]). The elemen-
tal analysis data of some synthesized compounds are
summarized in Table 5.
EXPERIMENTAL
The 1H, 13C, and 31P NMR spectra were registered on
a Varian VXR-400 spectrometer (400, 100, and 162
MHz, respectively) in CDCl3 (1–27) or D2O (28–42)
against TMS (1H, 13C) and 85% H3PO4 in D2O (31P).
All reactions were carried out under dry argon in
anhydrous solvents.
O,O- Bis(trimethylsilyl)2-(triethylsilyl)ethyl-
phosphonite (1)
A mixture of 31 g of bis(trimethylsiloxy)phosphine,
14 g of triethyl(vinyl)silane, and 0.3 g of azo-
bis(isobutyronitrile) was heated to 100◦C, and then
the temperature was gradually raised to 120◦C in
2 h. Distillation of the reaction mixture gave 30.9 g
of phosphonite 1.
Phosphonites 2–9 were prepared similarly.
O-Trimethylsilyl(dimethylaminomethyl)-2-
(triethylsilyl)ethylphosphinate (10)
A mixture of 13.2 g of phosphonite 1, 5 g of
bis(dimethylamino)methane, and 0.1 g of zinc chlo-
ride was heated at 110–130◦C for 1.5 h and then dis-
tilled to obtain 10.2 g of phosphinate 10.
Phosphinates 11–23 were prepared similarly.
Heteroatom Chemistry DOI 10.1002/hc

504 Prishchenko et al.
TABLE 4 Yields, Product Constants, and NMR Spectral Data for the PC1H2C2H2E and PC3H2NC4Hn Fragmentsa (δ, ppm;
J, Hz) of Sodium Phosphinates 35–42a
No.
Yield (%)
δ(C1)d
1JPC
δ(C2)d
2JPC
δ(C3)d
1JPC
δ(C4)d
3JPC
δ(P) s
35b
36b
37
95
93
95
96
95
95
95
93
24.30
25.01
26.69
25.53
28.08c
27.81d
31.59
39.73
89.7
88.5
87.5
88.2
92.6
89.7
89.7
88.5
6.27
6.57
4.26
6.4
6.6
5.4
5.2
<1
<1
58.06
57.83
57.77
57.38
59.27
58.78
58.94
60.22
99.4
98.6
98.3
102.2
105.2
103.3
100.9
101.0
47.27
56.19
56.38
55.58
56.80
55.60
47.33
47.55
7.9
7.0
7.1
8.1
4.9
7.5
8.0
8.0
37.95
38.66
38.62
38.82
34.09c
34.16d
36.44
35.01
38
3.45
39
21.57c
21.79d
22.49 s
28.37 s
40
41e
42e
–
–
aThe salts 35–42 are very hydroscopic crystals; therefore, their melting points were not measured. In 1H NMR spectra, the signals of methylene
groups of these fragments are multiplets and partially or completely overlap; all signals of the alkyl, vinyl, phenyl, and ferrocenyl fragments are
in the standard area.
b1H NMR spectrum, δ, ppm (J, Hz): 35: 4.49 d (C3H2, 2JPH = 9.2), 2.23 c (C4H3); 36: 3.50 d (C3H2, 2JPH = 9.2); 2.42 t (C4H2, 2JHH = 5.2).
cdd, 2JPC = 12.1, 1JPC = 11.8, respectively; d, 3JPP = 47.1; δP (PPh2) = – 14.43 d, 3JPP = 47.1.
dd. d, 2JPC = 12.5, 1JPC = 12.1, respectively; d, 3JPP = 48.4; δP (PPh2) = – 14.97 d, 3JPP = 48.4.
eOrange crystals; 13C NMR spectrum, δ, ppm (J, Hz): 41: 90.46 d (CFc, 3JPC = 18.6); 42: 98.04 d (CFc, 3JPC = 14.9), 22.84 c (MePr).
TABLE 5 Elemental Analyses Data of Synthesized Compoundsa
Calcd. (%)
Found (%)
No.
Empirical Formula
Formula Weight
C
H
C
H
10
11
12
13
14
15
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
C14H36NO2PSi2
C17H40NO2PSi2
C16H38NO3PSi2
337.58
377.64
379.62
501.90
425.66
427.63
377.60
405.65
425.61
501.66
284.80
300.21
262.30
300.05
314.08
350.28
338.13
319.39
359.46
371.95
373.92
397.38
399.35
357.16
371.19
49.81
54.07
50.62
43.08
47.97
44.94
50.90
53.30
45.15
43.10
34.97
56.01
50.37
48.04
49.71
37.72
35.52
52.65
56.80
45.21
41.76
60.45
57.15
50.45
51.77
10.75
10.68
10.09
9.64
9.47
8.96
9.61
9.94
8.52
8.04
7.37
5.04
6.15
4.70
5.14
5.18
4.47
7.26
7.57
8.40
7.88
6.60
6.06
5.93
6.24
49.52
53.86
50.49
42.83
47.75
44.72
50.95
53.04
44.96
42.93
34.72
55.87
50.26
47.89
49.52
37.59
35.30
52.57
56.64
45.02
41.65
60.26
56.83
50.28
51.49
10.60
10.59
9.97
9.57
9.39
8.81
9.54
9.98
8.43
7.89
7.49
5.12
6.09
4.75
5.22
5.10
4.59
7.12
7.49
8.52
7.82
6.69
6.16
6.02
6.14
C
C
18H48NO5PSi4
17H40NO5PSi2
C16H38NO6PSi2
C16H36NO3PSi2
C
18H40NO3PSi2
C16H36NO6PSi2
18H40NO9PSi2
C
C8H20GeNaO2P
C14H15NaO2P2
C11H16NaO2PSi
C12H14FeNaO2P
C13H16FeNaO2P
C11H18Na2O4P2Si
C10H15Na2O4P3
C14H23NNaO2PSi
C17H27NNaO2PSi
C
C
14H31GeNNaO2P
13H29GeNNaO3P
C20H26NNaO2P2
19H24NNaO3P2
C15H21FeNNaO2P
16H23FeNNaO2P
C
C
aThe other compounds are unstable in the air atmosphere; therefore, these substances were analyzed as their sodium salts.
chloride. The resulting mixture was heated to boil-
ing, the solvent was removed, and the residue was
distilled in a vacuum to obtain 5.8 g of phosphinate
24.
O-Trimethylsilyl(2-oxopyrrolidino)methyl-2-
(triethylsilyl)ethylphosphinate (24)
A solution of 2.6 g of N-chloromethylpyrrolidone-2
in 10 mL of methylene chloride was added dropwise
to a solution of 6.6 g of 1 in 15 mL of methylene
Phosphinates 25–27 were prepared similarly.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of 2-Element(Si, Ge, P, Fc)-Substituted O,O-Bis(trimethylsilyl) Alkylphosphonites 505
[3] Voronkov, M. G.; Dyakov, V. M. Silatranes; Nauka:
Sodium 2-(triethylgermyl)ethylphosphonite (28)
Novosibirsk, USSR, 1978.
A solution of 4 g of phosphonite 3 in 5 mL of diethyl
ether was added with stirring at 10◦C to a solution
of 0.55 g of sodium methylate in 30 mL of methanol.
The reaction mixture was heated to boiling, the sol-
vent was distilled off, and the residue was subjected
to vacuum (1 mmHg) for 1 h to give 2.7 g of salt 28.
The salts 29–42 were prepared similarly.
[4] Lutsenko, I. F. Pure Appl Chem 1972, 30, 409–425.
[5] Lesbre, M.; Mazerolles, P.; Satge, J. The Or-
ganic Compounds of Germanium; Academic Press:
London, 1971.
[6] Jemilev, U. M.; Porodko, N. R.; Kozlova, E. V. Metal
Complex Catalysis in Organic Synthesis; Khimiya:
Moscow, 1999.
[7] Voronkov, M. G.; Marmur, L. Z.; Dolgov, O. N.;
Pestunovich, V. A.; Pokrovskii, E. I.; Popel, Yu. I. Zh
Obsh Khim 1971, 41, 1987–1991 (in Russian).
[8] Prishchenko, A. A.; Livantsov, M. V.; Petrosyan, V. S.
Zh Obsh Khim 1994, 64, 1316–1330 (in Russian).
[9] Kukhar, V. P.; Hudson, H. R. Aminophosphonic and
Aminophosphinic Acids. Chemistry and Biological
Activity; Wiley: New York, 2000.
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Heteroatom Chemistry DOI 10.1002/hc