Synthesis of functionalized 1-trimethylsiloxy-substituted O-trimethylsilyl alkylphosphonites and their derivatives

Article abstract of DOI:10.1002/hc.20430

Nucleophilic addition of trimethylsilyl esters of tricoordinate organophosphorus acids to various functionalized aldehydes with vinyl, aryl, and heterocyclic fragments is proposed as a convenient method for the synthesis of new 1-trimethylsiloxysubstituted alkylphosphonites and their derivatives at mild conditions. Also the new functionalized derivatives of these phosphonites, including amino groups as well as certain properties of these compounds as important precursors of new functionalized 1-hydroxyalkylorganophosphorus acids, are presented.

Full text of DOI:10.1002/hc.20430

Heteroatom Chemistry
Volume 19, Number 4, 2008
Synthesis of Functionalized
1-Trimethylsiloxy-Substituted O-Trimethylsilyl
Alkylphosphonites and Their 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 2 October 2007; revised 26 December 2007
nites with aryl, heterocyclic, and organoelement
ABSTRACT: Nucleophilic addition of trimethylsi-
fragments in high yields via the radical addition
lyl esters of tricoordinate organophosphorus acids
of bis(trimethylsiloxy)phosphine to functionalized
to various functionalized aldehydes with vinyl,
alkenes [3,4]. Also the functionalized derivatives
aryl, and heterocyclic fragments is proposed as
of organophosphorus acids, containing aryl, hete-
a convenient method for the synthesis of new
rocyclic, or organoelement fragments, and various
1-trimethylsiloxysubstituted alkylphosphonites and
hydroxyl, amino, or amido groups have great in-
their derivatives at mild conditions. Also the new
terest as promising polydentate ligands in a series
functionalized derivatives of these phosphonites, in-
of catalytic systems and biologically active com-
cluding amino groups as well as certain proper-
pounds as organophosphorus biomimetics of hy-
ties of these compounds as important precursors of
droxyl and amino acids [5,6]. In the present work, we
new functionalized 1-hydroxyalkylorganophosphorus
report here the results of the nucleophilic addition of
ꢀ
C
acids, are presented.
2008 Wiley Periodicals, Inc.
bis(trimethylsiloxy)phosphine, trimethylsilyl phos-
phites, and phosphonites to various functional-
ized aldehydes with aryl or heterocyclic fragments
as well as crotonic and cinnamic aldehydes.
These reactions provide a convenient synthetic
route to new precursors of interesting function-
alized 1-hydroxyalkyl phosphonic and phosphinic
acids.
Heteroatom Chem 19:352–359, 2008; Published online
in Wiley InterScience (www.interscience.wiley.com). DOI
10.1002/hc.20430
INTRODUCTION
Synthetically directed reaction of silyl esters of
tricoordinate organophosphorus acids with or-
ganic compounds containing multiple bonds has
been widely used to obtain various functionalized
organophosphorus compounds [1,2]. Recently, we
have synthesized new 2-substituted alkylphospho-
RESULTS AND DISCUSSION
In the present work, we showed that the reac-
tion of bis(trimethylsiloxy)phosphine A with vari-
ous functionalized unsaturated and aromatic alde-
hydes and development on its basis are a convenient
route to functionalized O-trimethylsilyl trimethyl-
siloxymethylphosphonites 1–8. So phosphine A in
methylene chloride readily adds to the carbonyl
group of various functionalized aldehydes to form
Correspondence to: Andrey A. Prishchenko; e-mail: aprish
chenko@yandex.ru.
Contract grant sponsor: Russian Foundation for Basic
Research.
Contract grant number: 08-03-00282.
2008 Wiley Periodicals, Inc.
c
ꢀ
352

Synthesis of Functionalized 1-Trimethylsiloxy-Substituted O-Trimethylsilyl Alkylphosphonites and Their Derivatives 353
phosphonites 1–8 in high yields (Eq. (1); cf. [7, 8]).
acids also containing various aromatic fragments
(see Table 2), which are of great interest as potential
ligands and biologically active compounds [5,6].
Also, it was found that silyl phosphites B smoothly
add in methylene chloride to the carbonyl group of
various aromatic aldehydes to form functionalized
trimethylsiloxymethylphosphonates 16–28 in high
yields (Eq. (5); cf. [10]).
(1)
The reactions of aldehydes containing a hydroxyl
or carboxy group in the aromatic ring with the excess
of phosphine A under the similar conditions yield
phosphonites 9 and 10. Their formation is accompa-
nied by trimethylsilylation of these groups (Eq. (2)).
(5)
Arylaldehydes containing the hydroxyl or car-
boxy group in the aromatic ring react with the excess
trimethylsilylphosphites B to form phosphonates
29–32. Under these conditions, hydroxyl-containing
groups are readily silylated (Eq. (6)).
(2)
In contrast, the reaction of phosphine A with
mesityl oxide proceeds exclusively by way of 1,4-
addition involving the POSiMe3 fragment to yield
phosphonite 11 (Eq. (3)).
(3)
To conclude, we proposed
a
convenient
method to give the new trimethylsiloxy-substituted
alkylphosphonites with aryl or heterocyclic frag-
ments 1–11 (see Table 1), which are the promising
synthons in organophosphorus chemistry. So
readily accessible these O-trimethylsilyl trimethyl-
siloxymethylphosphonites 3–6 are smoothly
aminomethylated with bis(dimethylamino)methane
at 120–130◦C in the presence of zinc chloride to
form phosphinates 12–15 in high yields (Eq. (4); cf.
[9]).
(6)
Phosphonates 29 and 30 are also formed by the
addition of phosphites B to trimethylsilyl vanillin
derivative C that was specially prepared by the reac-
tion of vanillin with the excess of chlorotrimethylsi-
lane (Eq. (7)).
(7)
We found the unique route to novel func-
tionalized trimethylsiloxymethylphosphinates. So,
2-(triethylsilyl)ethyl- and indan-2-yl phosphonites,
which were recently prepared by us [3,4], easily add
to carbonyl groups of aromatic aldehydes to form
corresponding phosphinates 33–36 in high yields
(4)
Therefore, in this paper, we suggest convenient
routes to trimethylsilyl derivatives of substituted
dimethylaminomethyl(hydroxymethyl)phosphinic
Heteroatom Chemistry DOI 10.1002/hc

354 Prishchenko et al.
TABLE 1 Yields, Product Constants, and NMR Spectral Data for the HPC1HC2 Fragmentsa (δ, ppm; J, Hz) of Phosphonites
1–11
Yield Bp (◦C) (p, mmHg), Ratio
δ(H)
No. (%)
(mp, ◦C)
(%)
C1H, d 2JPH δ(H) PH, d 1JPH δ(C1) d 1JPC δ(C 2) d 2JPC δ(P) sc
1
2
3
4
74
81
83
87
87 (1)
60
40
60
40
60
40
58
42
55
45
53
47
61
39
57
43
57
43
59
4.10
4.30 m
4.45
4.70 m
4.78
4.67
4.80
–
–
–
–
6.78
6.70b
6.82
6.72b
6.82
6.72
6.84
6.73
6.74b
6.65b
6.80
6.71
6.90
6.78
6.73
6.65
6.77b
6.70b
6.99b
6.85
6.87
545.6 71.70 119.7 129.75
546.4 71.37 120.2 124.86
555.2 72.75 116.3 123.80
557.2 73.03 116.3 124.86
556.9 72.83 118.0 135.07
556.9 73.47 117.0 135.48
4.6
<1
5.1
<1
3.0
<1
20.40
22.36
19.76
21.55
23.04
23.40
22.39
23.25
22.74
23.44
23.09
23.81
22.07
22.65
21.44
22.03
23.20
22.93
22.38
23.15
28.54
139 (1)
144 (2)
4.0
11.9
4.0
12.0
8.0
10.0
4.0
7.9
8.0
12.0
4.0
13.9
8.0
12.0
7.9
13.8
8.8
142 (2),
(49)
172 (3)
556.9 72.33 118.0 131.02 2.5d
4.68
550.9 72.97 118.0 131.56 2.5d
5
6
7
8
9
86
83
85
78
82
4.67b
4.56b
4.69
552.9 72.44 120.2 126.90
552.9 73.00 120.0 127.31
548.9 72.75 121.9 122.19
550.9 73.25 121.0 122.49
560.0 72.43 116.0 129.29
560.0 73.07 115.0 129.48
560.9 70.63 116.0 130.78
562.8 71.16 117.0 131.26
554.8 72.71 119.4 128.59
554.9 73.33 119.4 128.83
562.8 72.97 115.0 131.04
560.8 73.66 114.0 131.24
3.0
<1
2.5
<1
<1
<1
3.0
<1
2.5
<1
4.0
4.0
4.2
159 (1)
4.59
4.95
4.84
4.72
116 (1),
(47)
162 (2)
4.60
164 (1)
4.67b
4.54b
5.01b
4.89
10
11
82
86
178 (1),
(66)
97 (1)
41
e
4.92
533.2 36.25
94.3 107.60
aIn 1H NMR spectra, the signals of these fragments for stereoisomers of 1 and 2 are multiplets and partially or completely overlap; all signals
of the alkyl, aryl, trimethylsilyl, and 3-pyridyl fragments are in the standard area. In 13C NMR spectra, the C3 and C4 signals of fragments
PC1HnC2H C3HmC4: 1, 129.31 d (C3, 3JPC 13.8), 18.5 s (C4); 2, 132.39 d (C3, 3JPC 12.3), 136.72 d (C4, 4JPC 7.1); 11, 149.39 d (C3, 3JPC 11.7),
4
23.62 d (C4, JPC 2.7). The signals of C O fragments, s: 7, 165.97, and 166.07; 10, 166.35 and 166.29. A ratio of isomers was determined
from the 1H and 31P NMR spectra.
bdd, all 3JHH 4.
cData of 31P{ H} spectra.
e The compound 11 consists of one isomer.
1
4
dIn 13C NMR spectra, 131.02 t (C2, 2JPC = JFC 2.5), 131.56 d (C2, 4JFC 2.5); 162.14 d (CF, 1JFC 246.3), the same signals for two isomers.
TABLE 2 Yields, Product Constants, and NMR Spectral Data for the PC1HC2 and PC3H2NC4H3 Fragmentsa (δ, ppm; J, Hz)
of Phosphinates 12–15 and Sodium Phosphinates 51–54
Yield Bp (◦C) (p, mmHg), δ(H)
No. (%)
2
1
1
3
(mp, ◦C)
C 1H, d JPH δ(H) C4H3, s δ(C 1) d JPC δ(C 2) s δ(C 3) d JPC δ(C 4) d JPC δ(P) s
12
13
14
15
91
74
78
70
140 (1)
4.95
4.85 12.0
5.06 8.0
4.94 11.0
4.96 8.0
4.85 10.0
4.91 9.0
4.82 11.8
8.0
2.23
2.15
2.36
2.29
2.29
2.22
2.17
2.09
2.30
2.31
2.33
2.89
71.37 113.0 136.46 54.30 112.0 47.30 10.0 36.16
72.06 114.0 136.15 54.30 112.0 47.13 10.0 35.56
130 (1),
(72)
152 (1)
71.16 115.3 132.53 54.87 113.6 47.74
72.35 117.8 133.03 54.78 110.3 47.55
71.30 117.8 128.49 54.75 111.9 47.54
9.9 35.98
9.9 35.60
9.9 36.25
71.96 117.0 128.98 54.62 110.3 47.42 11.1 35.89
69.38 114.4 132.78 54.47 114.4 47.28 10.8 35.50
69.95 116.9 132.95 54.65 112.8 47.15 10.0 35.07
144 (1)
b
b
b
b
51
52
53
54
95
96
96
94
4.81
4.81
4.76
8.0
8.0
8.0
74.32 101.0 138.01 56.20 101.0 46.49
73.05 102.0 133.76 56.25 101.0 46.50
73.20 104.0 130.53 56.17 100.0 46.47
3.0 30.69
8.0 30.47
7.0 30.56
3.0 23.17
4.84 12.0
70.78 115.0 133.48 56.46
84.0 45.35
aAll signals of alkyl, trimethylsilyl, aryl, and 3-pyridyl fragments are in the standard area. According to the NMR spectra, compounds 12–15
are mixtures of two stereoisomers. Their ratio was determined from the 1H NMR and 31P NMR spectra as 55:45 for all phosphinates 12–15.
The spectral parameters of the major isomer are given first. The signals of the diastereotopic protons of methylene groups C3H2 of 12–15 and
51–54 are characteristic of ABX multiplets in the range of 2–3 ppm. In the spectra of stereoisomers of phosphinates 12–15 and 51–54, the
signals of these protons partially overlap. The signals of the protons of C4H3 groups are doublets for two isomers of compounds: 14 (4JPH 4),
4
15 (4JPH 2.2). In 13C NMR spectra, the signals of compounds: 12: 136.15 d (C2, 2JPC 3); 13: 132.53 t (C2, 2JPC = JFC 3.3), 133.03 d (C2, 4JFC
2.3), 162.37 d (CF, 1JFC 245.5), 162.50 d (CF, 1JFC 246.3); 15: 132.25 d (C2, 2JPC 3.3). For compounds 12, 14, 15; n2D0: 1.4797, 1.4875, 1.4815,
respectively.
bThe salts 51–54 are decomposed by heating; therefore, their melting points were not measured.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Functionalized 1-Trimethylsiloxy-Substituted O-Trimethylsilyl Alkylphosphonites and Their Derivatives 355
(Eq. (8)).
Thus we propose a convenient method for
the synthesis of new functionalized trimethyl-
siloxymethylphosphonates 16–32 and phosphinates
33–36 including various aryl and heterocyclic frag-
ments (see Table 3).
Trimethylsilyl esters of several functionalized
organophosphorus acids were useful to obtain a se-
ries of water-soluble acids and their sodium salts
(cf. [1–4]). So 1-trimethylsiloxyalkylphosphonites 1–
10 smoothly react with diluted solutions of sodium
methylate in methanol, giving stable crystalline
sodium salts of 1-hydroxyalkylphosphonous acids
37–46 (see Table 4; Eq. (9)).
(8)
TABLE 3 Yields, Product Constants, and NMR Spectral Data for the PC1HC2 Fragmentsa (δ, ppm; J, Hz) of Phosphonates
16–32a and Phosphinates 33–36a
Bp (◦C)
Yield
(%)
(p, mmHg),
No.
(mp, ◦C)
δ(H) C1H, d
2JPH
δ(C1) d
1JPC
δ(C 2) s
δ(P) s
16
17
18
19
20
21
22
23
24
25
26
27
28c
29
30
31
32
33
87
85
83
80
83
89
81
78
78
82
84
90
80
81
85
82
83
86
145 (3)
142 (3)
133 (1), (69)
152 (2)
182 (3)
164 (1), (55)
144 (2)
142 (1)
152 (2)
146 (1), (42)
172 (3)
4.60
4.66
4.51
4.62
4.50
4.64
4.77
4.74
4.70
4.85
4.66
4.72
4.60
4.73
4.73
4.95
4.98
4.99
4.83
4.91
5.03
4.79
4.82
4.68
4.79
14.0
14.8
12.0
12.0
12.8
16.0
12.0
12.5
14.4
16.0
16.0
12.4
13.2
12.0
16.0
16.0
16.0
7.2
71.12
72.01
71.31
71.76
68.91
71.76
66.17
70.85
69.25
70.12
70.98
73.49
68.40
71.56
72.17
71.57
72.07
74.11
74.46
74.09
74.04
66.86
67.78
70.70
71.19
170.6
178.4
178.0
180.0
163.2
182.0
188.0
181.4
172.5
179.0
175.0
174.2
165.7
172.0
180.0
170.0
177.0
109.9
111.9
114.9
115.3
119.8
118.6
114.4
112.5
136.58
137.82
133.79
129.92
124.76
125.16
151.94
144.02
132.94
148.96b
147.57
111.67
84.99b
130.60
131.74
130.84
130.64
138.16
138.02
137.17b
137.10
149.77
150.00
132.31
132.55
17.45
1.17
3.28
3.96
18.30
4.44
0.49
3.24
16.51
2.69
1.81
(92)
174 (1)
168 (1)
4.64
16.72
20.64
4.08
19.36
2.79
39.87
38.68
40.45
39.42
37.38
36.66
38.81
39.51
170 (1), (60)
182 (1)
194 (2), (65)
157 (1)
10.0
9.6
7.6
10.0
10.8
9.2
34
35
36
83
82
85
182 (1), (92)
169 (1)
187 (1), (83)
7.2
aAll signals of alkyl, trimethylsilyl, aryl, and heterocyclic fragments are in the standard area. Compounds 33–36 are the mixtures of two
stereoisomers in ratio 60:40 (33,34) and 55:45 (35,36), which were measured by 1H and 31P NMR. The spectral parameters of major isomer
1
are given first. In 13C NMR spectra, the signals of compounds: 18, 162.05 d (CF, JCF 246.1); fragment C O, s: 31, 166.30; 32, 169.47;
1
2
1
2
fragment P1C3H2C4H2Si: 33, 20.71 d (C3, JPC 90.7), 1.97 d (C4, JPC 7.5) and fragment
: 20.46 d (C3, JPC 88.6), 2.31 d (C4, JPC
7.8); 34, 34.74 d (C3, 1JPC 95.4), 32.94 s (C4), 33.39 s (C4), 141.98 d (C5, 3JPC 9.3); 142.09 d (C5, 3JPC 8.2) and 35.16 d (C3, 1JPC 96.3), 33.74
s (C4), 34.07 s (C4), 141.83 d (C5, 3JPC 9.2), 141.98 d (C5, 3JPC 9.3); 35, 34.97 d (C3, 1JPC 96.7), 32.34 s (C4), 32.82 s (C4), 141.32 d (C5, 3JPC
10.6); 141.42 d (C5, JPC 11.3) and 37.44 d (C3, JPC 97.4), 32.76 s (C4), 33.14 s (C4), 141.01 d (C5, JPC 12.1), 141.10 d (C5, JPC11.9); 36,
3
1
3
3
37.26 d (C3, 1JPC 98.1), 31.11 s (C4), 31.37 s (C4), 140.38 d (C5, 3JPC 9.0); 140.43 d (C5, 3JPC 10.5) and 33.80 d (C3, 1JPC 95.6), 32.12 s (C4),
32.53 s (C4), 140.84 d (C5, JPC 9.1), 140.88 d (C5, JPC 8.9). Note that the two C4H2C5 groups in compounds 34–36 are nonequivalent and
3
3
give different signals in the 13C NMR spectra for each isomer (cf. [4]).
bd, 2JPC: 25, 3.0; 28, 4.7; 34, 4.0.
cCherry-red liquid.
Heteroatom Chemistry DOI 10.1002/hc

356 Prishchenko et al.
TABLE 4 Yields, Product Constants, and NMR Spectral Data for the HPC1HC2C3 Fragmentsa (δ, ppm; J, Hz) of Sodium
Phosphonites 37–47a
Yield
(%)
δ(H)
δ(H)
PH, d
No.
C1H, d
2JPH
1JPH
δ(C1) d
1JPC
δ(C2) s
δ(C3) d
3JPC
δ(P) sb
c
c
37
38
39
40
41
42
43e
44
95
96
95
95
97
96
97
97
–
–
6.69
6.78
6.82
6.75
6.76
6.76
6.84
6.77
514.4
525.2
522.3
520.0
517.2
516.0
524.0
524.2
72.08
72.58
72.78
73.01
72.98
73.29
73.52
71.34
106.9
105.5
104.0
105.3
106.2
106.0
101.0
104.1
130.60c
131.69c
130.67
133.07
129.63
128.22
128.38
133.73
125.02 s
124.87 s
127.94
128.65d
128.49
128.15
126.70
146.99
135.87 s
110.96
119.80
126.28
214.78
–
–
24.93
23.97
26.98
26.30
27.13
26.97
25.91
25.16
4.62
4.60
4.57
4.52
4.78
4.66
8.0
8.0
7.9
8.0
8.0
8.1
6.2
5.8
6.1
6.0
5.2
5.0
–
4.2
6.0
5.0
12.3
45
96
4.51
7.8
6.76
516.4
73.09
105.2
129.54
26.71
46e
47
97
94
4.80
8.2
11.2
6.87
6.57
526.3
506.1
73.89
33.65
102.0
92.6
129.26
48.07
25.64
37.13
2.55f
aThe salts 37–47 are very hydroscopic crystals; therefore, their melting points were not measured. In 1H NMR spectra, all signals of the alkyl,
vinyl, phenyl, and ferrocenyl fragments are in the standard area.
1
bData of 31P{ H} spectra.
cThe C1H proton signals are multiplets in the range 4–4.4 ppm and the C2H C3H proton signals, in the range of 5.4–6.3 ppm; in 13C NMR
spectrum, (C2H, d): 37, 2JPC 11.7; 38, 2JPC 10.8.
ddd, 2JFC 8.3.
eIn 13C NMR spectrum, δ(C O), s: 43, 169.01; 46, 169.33.
f Fragment C1Me2C2H2C3(O)Me, 1H NMR spectrum: 1.04 d (Me2, 3JPH 16.8), 2.20 s (Me); 13C NMR spectrum: 19.82 s (Me2), 32.10 s (Me).
crystals (Eq. (11)).
(9)
Note that the methanolysis of phosphonite 11 is
accompanied by the rearrangement of the interme-
diate unstable enol D, forming salt 47 (Eq. (10)).
(10)
Also the treatment of phosphonates 22, 23, 27
and phosphinates 12–15 and 33–36 with the diluted
solution of sodium methylate in methanol results
(11)
in water-soluble disodium phosphonates 48–50 and
sodium phosphinates 51–58 as white hygroscopic
Also phosphonates 17–19, 21, 25, 26, 30,
32 were easily transformed to corresponding
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Functionalized 1-Trimethylsiloxy-Substituted O-Trimethylsilyl Alkylphosphonites and Their Derivatives 357
TABLE 5 Yields, Product Constants, and NMR Spectral Data for the PC1HC2 Fragmentsa (δ, ppm; J, Hz) of Disodium
Phosphonates 48–50, Sodium Phosphinates 55–58, and Phosphonic Acids 59–66a
No.
Yield (%)
δ(H) C1H, d
2JPH
δ(C1) d
1JPC
δ(C2) s
δ(P) s
48
95
94
95
97
98
97
96
97
96
98
96
97
96
95
97
4.51
4.81
4.67
4.78
4.80
4.65
4.75
4.69
4.70
4.63
4.54
5.02
5.04
4.20
4.78
12.1
12.0
12.2
7.5
66.45
69.35
77.56
75.26
72.48
69.57
71.72
70.80
70.05
70.23
70.51
65.10
69.94
80.85
70.69
148.1
146.2
154.3
104.5
105.7
106.4
104.8
159.2
160.0
160.0
161.0
183.1
178.2
164.0
157.5
152.07
144.55
114.69
136.52
137.26
151.49
133.06
140.46
136.67
132.28
128.09
152.30
150.22
127.41
129.66
13.32
14.02
16.92
33.65
34.65
33.14
34.53
18.83
18.51
20.76
19.44
13.54
12.70
16.16
17.68
49
50b
55c
56d
57d
58d
59
9.8
10.2
12.0
16.1
12.1
12.0
12.2
16.0
16.1
16.0
16.2
60
61
62
63
64
65e
66f
◦
aThe melting point of compounds (in C): 59, 168; 60, 69; 61, 78; 62, 152; 65, 144. The other acids and salts are very hygroscopic crystals;
therefore, their melting points were not measured. In 1H and 13C NMR spectra, all signals of the alkyl, aryl, and heterocyclic fragments are in
the standard area. In 13C NMR spectra.
3
3
bFragment
(C9).
: 127.55 d (C3, JPC 5.1); 130.47 d (C4, JPC 8.0) 121.28 s, 121.64 s, 123.52 s (C5, C6, C7), 113.83 s (C8), 137.82 s
cFragment PC3H2C4H2Si: 20.04 d (C3, 1JPC 87.5), 1.89 d (C4, 2JPC 7.2).
1
3
3
dFragment
: 56, 36.59 d (C3, JPC 96.7), 33.45 s (C4), 33.78 s (C4), 142.95 d (C5, JPC 10.3); 143.39 d (C5, JPC 10.1); 57, 36.79 d
(C3, 1JPC 97.3), 33.38 s (C4), 33.48 s (C4), 143.30 d (C5, 3JPC 10.1); 143.40 d (C5, 3JPC 10.1); 58, 35.72 d (C3, 1JPC 95.8), 33.51 s (C4), 33.85 s
(C4), 142.97 d (C5, 3JPC 10.0); 143.21 d (C5, 3JPC 9.8).
eCAr–O: 146.64 s, 147.59 s.
f C O: 167.8.
TMS (1H, 13C) and 85% H3PO4 in D2O (31P). All reac-
tions were carried out under dry argon in anhydrous
solvents.
phosphonic acids 59–66 in high yields (Eq. (12)).
O-Trimethylsilyl-1-(trimethylsiloxy)but-2-enyl-
phosphonite (1)
To a solution of 35 g of phosphine A in 60 mL of
methylene chloride, a solution of 8.5 g of crotonic
aldehyde in 30 mL of methylene chloride was added
dropwise with stirring and cooling to 10◦C. The re-
action mixture was kept for 1 h at 20◦C, the solvent
was then removed, and the residue was distilled in a
vacuum to obtain 25.2 g of phosphonite 1.
(12)
Synthesized salts 48–58 and acids 59–66 are
white hygroscopic crystals (see Tables 2 and 5) and
may be used as water-soluble ligands in promis-
ing catalytic complexes as well as biologically active
compounds (cf. [5, 6]). The elemental analysis data
of some synthesized compounds are summarized in
Table 6.
Phosphonites 2–11 were prepared similarly.
EXPERIMENTAL
O-Trimethylsilyl(dimethylaminomethyl)[phenyl-
(trimethylsiloxy)methyl]phosphinate (12)
The 1H, 13C, and 31P NMR spectra were registered on
the Varian VXR-400 and Bruker Avance-400 spec-
trometers (400, 100, and 162 MHz, respectively) in
CDCl3 (1–36) or D2O and (CD3)2SO (37–66) against
A mixture of 7.6 g of O-trimethylsilyl[phenyl-
(trimethylsiloxy)methyl]phosphonite 3, 4.9 g bis-
(dimethylamino)methane, and 0.1 g zinc chloride
Heteroatom Chemistry DOI 10.1002/hc

358 Prishchenko et al.
TABLE 6 Elemental Analyses Data of Synthesized Compoundsa
Calcd. (%)
Found (%)
No.
Empirical Formula
Formula Weight
C
H
C
H
16
20
24
28
29
31
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
C14H25O4PSi
C16H30NO4PSi
316.41
359.49
317.40
424.34
434.62
432.60
158.07
220.13
194.10
212.10
224.13
237.17
252.14
195.10
240.13
238.11
186.12
236.08
238.12
271.12
251.20
269.19
281.22
252.18
336.43
310.27
300.22
311.26
188.12
206.11
218.15
231.19
189.11
189.11
234.15
232.13
53.14
53.46
49.19
50.95
49.74
49.98
30.39
49.10
43.32
39.64
42.87
45.58
42.87
36.94
40.02
40.36
38.72
30.53
25.22
39.87
47.81
44.62
46.98
42.87
53.55
61.94
56.01
57.88
44.69
40.79
44.05
46.76
38.11
38.11
41.04
41.39
7.96
8.41
7.62
6.89
8.12
7.69
5.10
4.58
4.15
3.33
4.50
5.52
4.00
3.62
4.20
3.38
6.50
2.99
2.12
2.97
6.02
5.24
6.09
5.60
7.79
5.20
4.70
4.86
4.82
3.91
5.08
6.10
4.26
4.26
4.74
3.91
52.93
53.28
48.87
50.83
49.57
49.71
30.02
48.83
43.08
39.49
42.69
45.40
42.65
36.81
39.86
40.28
38.49
30.35
25.07
39.68
47.65
44.49
46.81
42.68
53.41
61.72
55.66
57.61
44.52
40.65
43.90
46.64
37.94
37.89
40.92
41.23
7.88
8.30
7.54
6.81
8.03
7.60
5.14
4.69
4.09
3.38
4.57
5.57
4.08
3.70
4.22
3.43
6.64
3.03
2.05
2.92
6.09
5.28
6.16
5.66
7.72
5.22
4.65
4.78
4.74
4.05
5.12
6.16
4.12
4.15
4.81
3.86
C13H24NO4PSi
C18H29FeO4PSi
C18H35O6PSi2
C18H33O6PSi2
C4H8NaO3P
C9H10NaO3P
C7H8NaO3P
C7H7FNaO P
C8H10NaO43P
C9H13NNaO3P
C9H10NaO5P
C6H7NNaO3P
C8H10NaO5P
C8H8NaO5P
C6H12NaO3P
C6H7Na2O5P
C5H5Na2O4PS
C9H8NNa2O4P
C10H15NNaO3P
C10H14FNNaO3P
C11H17NNaO4P
C9H14N2NaO3P
C
15H26NaO3PSi
C16H16NaO3P
14H14NaO4P
C
C15H15NNaO3P
C7H9O4P
C7H8F O5P
C8H11O5P
C9H14NO4P
C6H8NO4P
C6H8NO4P
C8H11O6P
C8H9O6P
aThe other compounds are unstable in the air atmosphere; therefore, these substances were analyzed as their sodium salts.
was heated at 110–140◦C for 1.5 h and then was dis-
tilled to give 8.2 g of phosphinate 12.
3-Methoxy-4-(trimethylsiloxy)benzaldehyde (C)
A mixture of 7.6 vanillin and 30 g of chlorotrimethyl-
silane was refluxed under argon until hydrogen chlo-
ride no longer evolved. The solvent was removed,
and the residue was distilled in vacuum to give 8.7 g
(87%) of compound C, bp 133◦C (1 mmHg). The
1H NMR spectrum, δ (ppm): 0.24 s (CH3Si), 3.83 s
(CH3O), 6.9–7.4 m (C6H3), 9.80 s (CHO). 13C NMR
spectrum, δC (ppm): 0.45 s (CH3Si), 55.40 s (CH3O),
150.81 s, and 151.44 s (OC ), 190.87 s (CHO).
Phosphinates 13–15 were prepared similarly.
O,O-Diethyl-phenyl(trimethylsiloxy)methylphos-
phonate (16)
To a solution of 12.6 g of diethyl trimethylsilyl phos-
phite in 30 mL of methylene chloride, a solution of
5.3 g of benzaldehyde in 10 mL of methylene chlo-
ride was added dropwise with stirring at 10◦C. The
reaction mixture was stirred for 0.5 h and heated to
boil. The solvent was removed, and the residue was
distilled in a vacuum to give 13.8 g of phosphonate
16 (cf. [10]).
Sodium(1-hydroxybut-2-enyl)phosphonite (37)
To 60 mL of methanol, a solution of 18 g of phospho-
nite 1 in 20 mL of diethyl ether was added at 10◦C
with stirring and cooling, followed by a solution of
3.7 g of sodium in 75 mL of methanol. The resulting
Phosphonates 17–32 and phosphinates 33–36
were prepared similarly. Phosphonate 27 was crys-
tallized from hexane.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Functionalized 1-Trimethylsiloxy-Substituted O-Trimethylsilyl Alkylphosphonites and Their Derivatives 359
[2] Kutyrev, G. A.; Cherkasov, R. A. Usp Khim 1984, 53,
1675–1708 (in Russian).
[3] Prishchenko, A. A.; Livantsov, M. V.; Novikova, O.
P.; Livantsova, L. I.; Petrosyan, V. S. Heteroat Chem
2008, 19 (in press).
[4] Prishchenko, A. A.; Livantsov, M. V.; Novikova, O.
P.; Livantsova, L. I.; Petrosyan, V. S. Heteroat Chem
2008, 19 (in press).
[5] Kolodiazhnyi, O. I. Usp Khim 2006, 75, 254–282 (in
Russian).
[6] Kukhar, V. P.; Hudson, H. R. Aminophosphonic and
Aminophosphinic Acids. Chemistry and Biological
Activity; Wiley: New York, 2000.
[7] Pudovik, A. N.; Konovalova, I. V.; Romanov, G. V.;
Nazmutdinov, R. J. Phosphorus 1975, 5, 105–
107.
[8] Pudovik, A. N.; Romanov, G. V.; Nazmutdinov, R. J.
Zh Obsh Khim 1970, 49, 257–264 (in Russian).
[9] Prishchenko, A. A.; Livantsov, M. V.; Petrosyan, V. S.
Zh Obsh Khim 1994, 64, 1316–1330 (in Russian).
[10] Novikova, Z. S.; Lutsenko, I. F. Zh Obsh Khim 1970,
40, 2129 (in Russian).
mixture was heated to the boil, the solvent was re-
moved in a vacuum, and the residue was kept in a
vacuum (1 mm) for 1 h to obtain 9.6 g of salt 37 as
colorless hygroscopic crystals.
The salts 38–58 were obtained similarly.
Phenyl(hydroxy)methylphosphonic acid (59)
A solution of 10.5 g of phosphonate 17 in 10 mL of di-
ethyl ether was added dropwise with stirring at 10◦C
to 30 mL of methanol. The resulting mixture was
heated to boil, the solvent was distilled in a vacuum,
and the residue was kept in vacuum (1 mmHg) for
1 h to give 4.7 g of acid 59 as colorless hygroscopic
crystals (cf. [11]).
The acids 60–66 were obtained similarly.
REFERENCES
[11] Kharasch, M. S.; Mosher, R. A.; Bengelstorf, I. S. J
Org Chem 1960, 25, 1000.
[1] Wozniak, L.; Chojnowski, J. Tetrahedron 1989, 45,
2465–2524.
Heteroatom Chemistry DOI 10.1002/hc