Synthesis of 2-substituted O, O-Bis(trimethylsilyl) alkylphosphonites with aryl and heterocyclic fragments and their amino or amido derivatives

Article abstract of DOI:10.1002/hc.20431

Free-radical addition of bis(trimethylsiloxyjphosphine to various functionalized alhenes with aryl and heterocyclic fragments is proposed as a convenient procedure for the synthesis of new 2-substituted alkylphosphonites of corresponding structures. Also the new functionalized derivatives of these phosphonites, including various amino and amido groups as well as certain properties of these compounds, are presented.

Full text of DOI:10.1002/hc.20431

Heteroatom Chemistry
Volume 19, Number 4, 2008
Synthesis of 2-Substituted
O,O-Bis(trimethylsilyl) Alkylphosphonites
with Aryl and Heterocyclic Fragments
and Their Amino or Amido 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 18 September 2007; revised 26 December 2007
phine to element(Si, Ge, P, Fe) substituted
ABSTRACT: Free-radical addition of bis(trimethyl-
alkenes [2]. Also the functionalized derivatives of
siloxy)phosphine to various functionalized alkenes
organophosphorus acids containing aryl or hete-
with aryl and heterocyclic fragments is proposed as
rocyclic fragments and various amino or amido
a convenient procedure for the synthesis of new 2-
groups have great interest as promising polyden-
substituted alkylphosphonites of corresponding struc-
tate ligands in a series of catalytic systems and
tures. Also the new functionalized derivatives of these
biologically active compounds as organophospho-
phosphonites, including various amino and amido
rus biomimetics of amino acids [3,4]. In the
groups as well as certain properties of these com-
present work, we report here the results of the
ꢀ
C
pounds, are presented.
2008 Wiley Periodicals, Inc.
radical addition of bis(trimethylsiloxy)phosphine
to styrene, 2-vinylfuran, isomeric vinylpyridines,
N-vinylcarbazole, N-vinyl-2-pyrrolidone, indene,
and aryl-substituted acetylenes, resulting in forma-
tion of corresponding phosphonites in high yield.
Futhermore, amino or amidomethylation of these
phosphonites results in the new derivatives of
organophosphorus acids containing aryl or het-
erocyclic fragments and various aminomethyl or
amidomethyl moieties.
Heteroatom Chem 19:345–351, 2008; Published online
in Wiley InterScience (www.interscience.wiley.com). DOI
10.1002/hc.20431
INTRODUCTION
The reaction of P H phosphines with organic
compounds, containing multiple bonds, provides
a convenient synthetic route to functionalized
organophosphorus compounds [1]. Recently we
have synthesized the new 2-element(Si, Ge, P, Fe)
substituted alkylphosphonites with high yields via
the radical addition of bis(trimethylsiloxy)phos-
RESULTS AND DISCUSSION
So the radical addition of bis(trimethylsiloxy)phos-
phine A to functionalized ethylenes with aryl groups
or heterocyclic fragments results in 2-substituted
ethylphosphonites 1–7 with high yields (cf. [5]). The
reaction was initiated by azobis(isobutyronitrile) un-
der thermolytic conditions (100–120◦C) (Eq. (1)).
Correspondence to: Andrey A. Prishchenko; e-mail: apr-
ishchenko@yandex.ru.
Contract grant sponsor: Russian Foundation for Basic Re-
search.
Contract grant number: 08-03-00282.
2008 Wiley Periodicals, Inc.
c
ꢀ
345

346 Prishchenko et al.
Also we showed that the excess of phosphine A
reacts with aryl-substituted acetylenes under similar
conditions via double regioselective addition to the
acetylene fragment to form bisphosphonites 11, 12
(Eq. (4)).
(1)
Also the similar addition of phosphine A to in-
dene proceeds regioselectively to give indan-2-yl-
phosphonite 8 in high yield (Eq. (2)).
(4)
To conclude, we proposed a convenient method
to give the new 2-substituted ethylphosphonites or
bisphosphonites with aryl or heterocyclic fragments
1–12 (see Table 1), which are the promising synthons
in organophosphorus chemistry.
(2)
Note that even with the excess of phosphine A
the considerable amount of phosphonites 9, 10 is
formed by the reaction with styrene and 2-vinylfuran
due to the propagation of the radical process on an
another molecule of substituted ethylene. Evidently,
formation of phosphonites 9, 10 is due to the chain
transfer to the substituted ethylene molecule via in-
termediate radicals B and C. So we showed that the
reaction of phosphine A with styrene at 1:1.7 molar
ratio gives phosphonite 9 with 22% yield together
with phosphonite 1. The use of solvents such as
bis(trimethylsilyl)amine and toluene reduces the for-
mation of polymeric tars but does not allow prepa-
ration of phosphonite 9 in a higher yield under the
given conditions. This may be due to high reactivity
of the P H bond in the radical processes [6] (Eq. (3)).
Phosphonites 1–12 were successfully used by
us for preparing new derivatives of functional-
ized organophosphorus acids containing aryl or
heterocyclic fragments. The aminomethylation of
element (Si, Ge, P, Fe) substituted alkylphospho-
nites was thoroughly investigated by us in [2].
Now, we present the new results of aminomethy-
lation of 2-alkylphosphonites with aryl or het-
erocyclic fragments. Phosphonites 1–9 undergo
facile aminomethylation under the action of
N-chloromethylamines, amides, or aminals, yield-
ing new functionalized phosphinates 13–27. So
phosphonites 1, 7, 9 readily react with various
N-chloromethylamides in the methylene chloride so-
lution by the Arbuzov reaction scheme to form phos-
phinates 13–18 (Eq. (5)).
(3)
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of 2-Substituted O,O-Bis(trimethylsilyl) Alkylphosphonites with Aryl and Heterocyclic Fragments 347
TABLE 1 Yields, Product Constants, and NMR Spectral Data for the PC1HmC2HnC3 Fragmentsa (δ, ppm; J, Hz) of Phospho-
nites 1–12
No.
Yield (%)
bp (◦C) (p, mm Hg)
δ (C1) d
1JPC
δ (C2) d
2JPC
δ (C3) d
3JPC
δ (P) s
1
91
64
90
89
93
86
76
83
22
25
78
74
83 (0.5)
92 (1)
43.80
38.97
41.52
43.22
42.09
39.69
39.82
46.27
50.43
46.09
40.27
39.60
25.8
25.1
25.6
26.7
26.3
27.2
27.1
20.3
28.8
28.1
31.7
30.0
27.93
19.64
30.34
24.56
26.97
35.74
36.04
31.99
39.84
33.76
50.72
49.07
14.5
15.1
13.8
14.7
14.5
13.3
16.2
19.7
12.4
6.9
143.27
156.19
162.80
134.94
151.44
140.21b
173.07c
143.06
146.28
157.81
139.81
130.75
9.3
10.6
9.3
9.1
9.1
–
159.10
157.22
159.65
158.27
157.52
156.87
158.24
155.56
160.48
158.33
160.89
164.33
2
3
114 (1)
120 (1)
116 (1)
185 (1)
133 (2)
126 (1)
149 (1)
135 (1)
133 (0.5)
133 (0.5)
4
5
6
7
–
8
5.6
4.5
4.6
3.1
3.4
9d
10d
11e
12e
9.6
11.3
aIn 1H NMR spectra, the signals of methylene groups of these fragments are multiplets and partially or completely overlap; all signals of the
alkyl, trimethylsilyl, aryl, and heterocyclic fragments are in the standard area.
bs, NC3.
cs, NC O.
3
dFragments PC1H2C2H(C3)C4H2C5H2C6, 13C NMR spectra, δ (ppm), J (Hz): 9: 40.23 d (C4, JPC 7.4), 34.0 s (C5); 142.39 s (C6); 10: 32.43 d
(C4, 3JPC 12.6), 25.35 s (C5); 155.39 s (C6).
eFragments P1C1H2C2H(C3)P2, 13C NMR spectrum, δ (ppm) (J (Hz): 11: 40.27 dd (C1, 1JPC 31.7, 2JPC 15.5), 50.72 dd (C2, 1JPC 30.3, 2JPC 9.6),
139.81 dd (C3, 2JPC 9.1, 3JPC 3.1); 31P NMR spectrum: 160.89 d (P1, 3JPP7.0), 148.84 d (P2, 3JPP7.0); 12: 13C NMR spectrum, δ (ppm) (J, Hz):
39.60 dd (C1, JPC 30.0, JPC 14.9), 49.07 dd (C2, JPC 27.6, JPC 11.3), 130.75 dd (C3, JPC 9.0, JPC 3.4), 55.02 s (OCH3), 157.85 s (OCAr);
1
2
1
2
2
3
31P NMR spectrum: 164.33 d (P1, 3JPP 8.4), 151.46 d (P2, 3JPP 8.4).
(cf. [7, 8]); Eq. (6)).
(6)
On the other hand, phosphonites 2–6 are
smoothly aminomethylated with bis(dialkylamino)-
methanes at 130◦C in the presence of zinc chloride as
a catalyst to give corresponding phosphinates 19–25
in high yield (Eq. (7)).
(5)
Note that phosphonite 7 easily reacts with
various N-chloromethylamines (amides) with ini-
tial formation of viscous oils or crystals, presum-
ably phosphonium and immonium salts D and E.
Several singlets of intermediates D and E in the
reaction mixtures were observed in 31P NMR spec-
tra at 44.7, 46.5, 47.8, and 49.7 ppm in the ratio
30:30:15:25. These intermediates, when heated, de-
compose to trimethylchlorosilane and unsymmet-
rical phosphinates 14–16. The unusual stability of
the intermediates is undoubtedly connected with
(7)
the reversible formation of cyclic immonium salt E
Heteroatom Chemistry DOI 10.1002/hc

348 Prishchenko et al.
TABLE 2 Yields, Product Constants, and NMR Spectral Data for the PC1HmC2HnC3 and PC4H2NC5Hn Fragmentsa (δ, ppm;
J, Hz) of Phosphinates 13–27
20
Yield
bp (◦C)
nD
1
No
(%) (p, mm Hg) (mp, ◦C) δ(C1) d JPC δ(C 2) s δ(C 3) d 3JPC δ(C 4) d 1JPC
δ(C 5) d
3JPC δ(P) s
13
14
15
16
17
86
71
75
73
89
125 (2)
160 (2)
185 (2)
192 (2)
191 (2)
1.4935
1.4805
1.4885
1.4948
1.5239
30.95 91.4 28.62a 142.05
27.35 90.7 36.56
23.65 90.4 36.77
13.9 59.27 112.1
47.75
47.70
56.85
174.08b
47.64
47.40
55.84
55.74
46.60
56.03
54.60
56.03
54.88
55.22
46.72
46.51
46.61
35.29 s
161.65b
35.29 s
162.12b
9.6 38.69
7.5 37.45
9.3 37.24
173.54b
173.52b
173.75b
–
–
–
–
–
–
–
–
59.01 113.7
58.88 113.5
43.25 104.5
59.73 112.3
59.18 111.7
58.46 112.0
58.65 111.6
27.84 88.0 36.46
–
34.78
c
–
–
–
–
–
–
–
–
6.1 37.59
7.8 38.79
8.6 38.18
11.3 36.98
10.0 39.32
9.2 39.81
9.1 38.59
9.1 40.51
9.1 38.84
9.1 38.64
10.0 38.04
9.7 41.55
10.5
c
c
c
–
–
18
74
194 (0.5)
1.5250
–
19
20
21
22
23
24
25
26
83
78
86
95
90
93
83
74
118 (1)
158 (1)
152 (1)
178 (1)
190 (2)
184 (1)
197 (1)
141 (1)
1.4720
(42)
1.4848
1.5009
(45)
(39)
1.5117
1.5068
26.05 93.1 19.83
26.77 93.1 20.37
26.33 93.7 19.99
28.31 92.9 29.83
29.59 92.4 24.40
28.89 93.4 27.21
27.33 89.3 35.86
35.54 97.9 31.63
32.23
36.14 96.7 31.75
32.80
35.91 96.1 32.04
32.47
153.39
154.04
153.45
160.11
132.74
149.38
138.81d
140.53
140.70
140.78
140.93
140.33
140.46
16.4 57.67 113.7
16.4 57.79 113.8
16.0 56.85 112.7
14.6 57.95 113.3
14.3 57.34 112.4
18.6 57.74 113.5
–
58.38 115.0
9.1 56.66 112.1
9.1
8.9 42.50 101.0
8.6
27e
70
187 (1)
1.5131
–
–
–
–
38.81
8.8 46.89
8.4
99.5
38.26
aIn 1H NMR spectra, the signals of methylene groups of these fragments are multiplets and partially or completely overlap; all signals of the
alkyl, trimethylsilyl, aryl, and heterocyclic fragments are in the standard area. For 13: δ (C2) 28.62 d (2JPC 3.7). Compounds 17, 18, and 27 are
mixtures of two stereoisomers; note that the two C2H2C3 and C5H2 groups in compounds 26 and 27, which contain asymmetric phosphorus
centers are nonequivalent and give different signals in the 13C NMR spectra for each isomer. The ratio of stereoisomers was measured by 31
P
NMR.
bs, NC O.
cThe signals of the C1–C8 carbon atoms of the fragments PC1H2C2H(C3)C6H2C7H2C8 in the 13C NMR spectra of diastereomers of 17 and 18
are overlapping singlets and doublets at 30–40 and 140–145 ppm. The ratio of stereoisomers, 65:35 (17); 85:15 (18).
ds. NC3.
e 1H NMR spectrum: first isomer (75%): 7.78 s (CHO), 2.87 s (C5H3); second isomer (25%): 7.72 s (CHO), 2.77 s (C5H3).
Note that to obtain indanylphosphonites 26, 27
it may be used as aminomethylating reagents both
bis(dimethylamino)methane and N-chloromethyl-
N-methylformamide. So, phosphonite 8 undergoes
facile aminomethylation giving phosphinates 26, 27,
containing the bicyclic indane fragments in high
yields (Eq. (8)).
luted solution of sodium methylate in methanol
results in water-soluble sodium phosphonites 28–
39 and sodium phosphinates 40–42, respectively
(Eq. (9)).
(8)
The constants and NMR data of synthesized
phosphinates 13–27 are presented in Table 2.
Trimethylsilyl esters of several organophosphorus
acids easily react with methanol to give a series of
water-soluble acids (cf. [2]). So treatment of phos-
phonites 1–12 and phosphinates 25–27 with a di-
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of 2-Substituted O,O-Bis(trimethylsilyl) Alkylphosphonites with Aryl and Heterocyclic Fragments 349
acids 43–47 in high yields (Eq. (10)).
(10)
Synthesized salts 28–42 and acids 43–47 are
white hygroscopic crystals (see Tables 3 and 4) and
may be used as water-soluble ligands in promis-
ing catalytic complexes as well as biologically active
(9)
Also the phosphinates 14, 17, 18, 22, 23 were
easily transformed to corresponding phosphinic
compounds (cf. [3,4]). The elemental analysis data
of some synthesized compounds are summarized in
Table 5.
TABLE 3 Yields, Product Constants, and NMR Spectral Data for the HPC1HmC2HnC3 Fragmentsa (δ, ppm; J, Hz) of Sodium
Phosphonites 28–39a
No
Yield (%)
δ(H) PH, dt
1JPH
3JHH
δ(C1) d
1JPC
δ(C2) s
δ(C3) d
3JPC
δ(P) sb
28
29
30
31
32
33
34
35
36f
37f
97
94
96
98
95
95
97
97
95
93
7.02
6.88
6.93
6.94
6.90
6.90
6.94
6.83e
6.78
6.74
510.7
508.0
505.6
507.2
506.4
510.6
510.0
500.7
506.9
510.0
2.6
2.0
<1
<1
<1
1.8
2.0
2.2
2.9
2.4
31.25
29.71
31.55
30.49
31.81
31.46
29.56
38.84
40.37
36.33
87.1
89.4
88.4
89.7
88.5
84.8
86.5
94.5
87.7
89.5
27.40
20.17
29.39
23.12
26.97
36.70
36.55
32.19
39.97
33.18
141.12
155.55
160.46
133.81
152.65
140.14c
177.89d
142.66
145.26
156.88
16.9
15.5
16.7
15.9
15.7
–
24.10
26.15
34.74
24.75
25.55
21.92
22.30
32.81
22.21
23.53
–
9.1
7.1
6.7
aThe salts 28–37 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, aryl, and heterocyclic fragments are in the
1
1
3
standard area. Salt 38, yield 98%; fragment P1C1H2C2H(C3)P2; 1H NMR spectrum: 6.65 d (P1H, JPH 516.3), 6.78 dd (P2H, JPH 515.5, JHH
2.4). 13C NMR spectrum: 29.66 d (C1, JPC 89.5); 43.04 d (C2, JPC 82.9); 136.4–134.4 m (C3), 1P NMR spectrum: 29.06 dd (P1, JPH 516.3,
3JPP 55.6), 23.56 dd (P2, 1JPH 515.5, 3JPP 55.6). Salt 39, yield 96%; fragment P1C1H2C2H(C3)P; 1H NMR spectrum: 6.52 d (P1H, 1JPH 519.4),
6.81 dd (P2H, 1JPH 522.1, 3JHH 2.6). 13C NMR spectrum: 30.05 d (C1, 1JPC 90.3); 41.89 d (C2, 1JPC 83.7); 135.1–135.3 m (C3), 54.92 s (OCH3),
158.01 s (OCAr), 1P NMR spectrum: 35.83 dd (P1, 1JPH 519.4, 3JPP 57.1), 29.55 dd (P2, 1JPH 522.1, 3JPP 57.1).
1
1
1
1
bData of 31P{ H} spectra.
cs, NC3.
ds, NC O.
edd.
f Fragments PC1H2C2H(C3)C4H2C5H2C6, 13C NMR spectra: 36: 37.87 d (C4, 3JPC 6.7), 33.92 s (C5), 142.89 s (C6); 37: 33.74 d (C4, 3JPC 11.3),
25.14 s (C5), 155.58 s (C6).
Heteroatom Chemistry DOI 10.1002/hc

350 Prishchenko et al.
TABLE 4 Yields, Product Constants, and NMR Spectral Data for the PC1HmC2HnC3 and PC4H2NC5Hn Fragmentsa (δ, ppm;
J, Hz) of Sodium Phosphinates 40–42a and Phosphinic Acids 43–47
2
1
3
3
No Yield (%) Mp (◦C) δ , C 4H2 JPH δ (C 1) d JPC δ(C 2) s δ(C 3) d JPC δ(C 4) d 1JPC δ(C 5) d JPC δ(P) s
H
40
94
95
95
–
–
–
2.11
2.35c
7.71d
7.91d
3.05
3.17
2.97
2.45
2.61
8.8
–
–
30.97 87.0 37.58 140.07b
37.71 96.6 33.08 142.89
37.20 96.4 33.09 142.70
37.69 97.6 33.09 142.39
29.95 95.2 35.30 173.89b
31.74 97.1 27.38 153.13 15.2 55.25
31.76 93.7 24.75 136.81 15.1 56.56
39.07 76.8 39.73 145.40
39.92 85.6 40.35 144.67
–
59.21 110.4 47.93
7.8 32.61
4.2 37.83
41
9.9 57.46
9.3 43.67
8.6 43.52
99.1 46.84
94.2 36.56 s
94.4 36.62 s
90.2 47.59 s
81.9 55.87 s
89.7 54.47
79.7 44.78
80.4 53.99
42d
–
–
–
–
35.86
36.30
27.26
26.04
–
43
97
96
96
96
95
145
162
7.3
7.6
8.4
5.6
6.4
–
58.07
44
45
194
5.9 29.37
3.9 21.97
4.2 24.23
46e
47e
4.7 56.50
4.5 56.40
f
58
aThe salts 40–42 are very hygroscopic crystals; therefore, their melting points were not measured. In 1H NMR spectra, the signals of methylene
groups of these fragments are usually multiplets and partially or completely overlap; all signals of the alkyl, aryl, and heterocyclyc fragments
are in the standard area.
bs: NC3 (40), NC O (43).
cs, NMe2.
dCompound 42 is a mixture of two stereoisomers in ratio 55:45 (measured by 1H and 31P NMR); in 1H NMR spectrum signals of C4H2 groups
are multiplets; the fragments NCHO were given, δC (C O) 165.36 s and 164.51 s respectively.
e13C NMR spectra for fragments PC1H2C2H(C3)C6H2C7H2C8: 46: 39.61 d (C6, 3JPC 8.2), 32.68 s (C7), 142.38 s (C8); 47: 40.06 d (C6, 3JPC 12.4),
33.49 s (C7), 141.86 s (C8).
f Viscous oil.
EXPERIMENTAL
O-Trimethylsilyl Dimethylaminomethyl-
(2-phenylethyl)phosphinate (13)
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(28–47)
against TMS (1H, 13C) and 85% H3PO4 in D2O (31P).
All reactions were carried out under dry argon in
anhydrous solvents.
A solution of 1 g of (chloromethyl)dimethylamine in
10 mL of methylene chloride was added dropwise
with stirring to a solution of 3.5 g of phosphonite
1 in 10 mL of methylene chloride. The mixture was
heated to the boil, the solvent was removed, and the
residue was distilled in a vacuum to give 2.8 g of
phosphinate 13.
Phosphinates 14–18, 27 were prepared simi-
larly.
O,O-Bis(trimethylsilyl)-2-phenylethylphos-
phonite (1) and O,O-bis(trimethylsilyl)-
2,4-diphenylbutylphosphonite (9)
(a) A mixture of 23 g of bis(trimethylsilyloxy)-
phosphine, 10.4 g of styrene, and 0.3 g of azo-
bis(isobutyronitrile) was heated to 100◦C, and then
within 2 h the temperature was gradually raised to
130◦C. The resulting mixture was distilled in a vac-
uum to give 28.6 g of phosphonite 1.
O-Trimethylsilyl[2-(2-furyl)ethyl](dimethyl-
aminomethyl)phosphinate (19)
A mixture of 7 g of phosphonite 2, 2.8 g of
bis(dimethylamino)methane, and 0.1 g of zinc chlo-
ride was heated at 130◦C for 1 h and then distilled to
obtain 5.5 g of phosphinate 19.
(b) A mixture of 12.6 g of bis(trimethylsiloxy)-
Phosphinates 20–26 were prepared similarly.
phosphine, 10.4
g of styrene, 0.3 g of azo-
bis(isobutyronitrile), 20 mL of bis(trimethylsilyl)-
amine, and 10 mL of toluene was heated to 100◦C.
After that the temperature was raised to 120◦C over
a period of 1 h, vacuum distillation of the resulting
mixture gave two fractions with bp 80–130◦C (2 mm)
and 150–180◦C (2 mm). Repeated distillation of the
first fraction gave 10 g (32%) of phosphonite 1, and
repeated distillation of the second fraction gave 4.5 g
(22%) of phosphonite 9.
Sodium 2-Phenylethylphosphonite (28)
A solution of 7.3 g of phosphonite 1 in 10 mL of
diethyl ether was added at 10◦C with cooling and
stirring to 30 mL of methanol, followed by a so-
lution of 1.25 g of sodium methylate in 27 mL of
methanol. The mixture was heated to the boil, the
solvent was removed, and the residue was kept in a
vacuum (1 mm) for 1 h to obtain 4.3 g of salt 28 as
colorless hygroscopic crystals.
Phosphonites 2–8 and 10–12 were prepared
similarly.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of 2-Substituted O,O-Bis(trimethylsilyl) Alkylphosphonites with Aryl and Heterocyclic Fragments 351
TABLE 5 Elemental Analyses Data of Synthesized Compoundsa
Calcd. (%)
Found (%)
No
Empirical Formula
Formula Weight
C
H
C
H
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
C14H26NO2PSi
C12H27N2O3PSi
299.43
306.46
346.48
346.49
403.58
445.62
289.38
317.43
319.41
340.48
356.47
342.45
388.52
311.43
325.42
192.13
182.09
193.12
207.15
193.12
281.22
199.13
204.14
296.28
276.20
278.10
308.12
338.32
261.23
275.22
234.23
268.30
284.29
331.40
373.44
56.15
47.03
52.00
48.53
65.47
64.69
49.81
52.97
48.88
56.44
53.91
52.61
61.83
57.85
55.37
50.01
39.58
43.54
46.39
43.54
59.79
36.19
52.95
64.86
52.18
34.55
35.08
60.35
55.17
52.37
46.15
58.20
54.92
68.86
67.54
8.75
8.88
9.02
7.86
8.49
8.14
8.36
8.89
8.21
8.59
8.20
7.95
7.52
8.42
7.43
5.25
4.43
4.70
5.35
4.70
4.66
5.57
4.94
6.12
5.11
3.62
3.92
5.96
6.54
5.49
8.18
7.89
7.45
7.91
7.56
55.94
46.90
51.83
48.31
65.09
64.32
49.52
52.72
48.59
56.12
53.78
52.49
61.67
57.64
50.29
49.83
39.34
43.42
46.26
43.48
59.58
35.97
52.68
64.72
51.87
34.43
34.94
60.07
54.94
52.02
45.93
57.98
54.84
68.49
67.18
8.58
8.74
8.84
7.68
8.57
8.01
8.20
8.78
8.07
8.45
8.05
7.82
7.41
8.28
7.23
5.30
4.59
4.78
5.42
4.74
4.81
5.64
5.03
6.16
5.19
3.69
3.98
6.09
6.65
5.57
8.07
7.76
7.37
7.81
7.47
C15H31N2O3PSi
C14H27N2O4PSi
C22H34NO2PSi
C24H36NO3PSi
C12H24NO3PSi
C14H28NO3PSi
C
13H26NO4PSi
16H29N2O2PSi
C16H29N2O3PSi
15H27N2O3PSi
C
C
C20H29N2O2PSi
C15H26NO2PSi
C15H24NO3PSi
C8H10NaO2P
C6H8NaO3P
C7H9NNaO2P
C8H11NNaO2P
C7H9NNaO2P
C14H13NNaO2P
C6H11NNaO3P
C9H10NaO2P
C16H18NaO2P
C12H14NaO4P
C8H10Na2O4P2
C9H12Na2O5P2
C17H20N2NaO2P
C12H17NNaO2P
C
12H15NNaO3P
C9H19N2O3P
C
13H21N2O2P
C13H21N2O3P
C19H26NO2P
21H28NO3P
C
aThe other compounds are unstable in the air atmosphere therefore these substances were analyzed as their sodium salts.
[2] Prishchenko, A. A.; Livantsov, M. V.; Novikova, O. P.;
Livantsova, L. I.; Petrosyan, V. S. Heteroatom Chem
2008, 19 (in press).
The salts 29–42 were prepared similarly.
[3] Kukhar, V. P.; Hudson, H. R. Aminophosphonic and
Aminophosphinic Acids. Chemistry and Biological
Activity; Wiley: New York, 2000.
Dimethylaminomethyl-2-[N-(2-oxopyrrolidino)]-
ethylphosphinic Acid (43)
[4] Kolodiazhnyi, O. I. Usp Khim 2006, 75, 254–282 (in
Russian).
To a solution of 5.4 g of phosphinate 14 in 15 mL
of diethyl ether, 25 mL of methanol was added
with stirring. The resulting mixture was refluxed for
10 min, the solvent was removed, and the residue
was kept in a vacuum (1 mm). Four grams of acid
43, was obtained as colorless hydroscopic crystals.
The acids 44–47 were prepared similarly.
[5] 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).
[6] Rakhimov, A. I. Synthesis of Organophosphorus
Compounds. Homolytic Reactions; Nauka: Moscow,
1985 (in Russian).
[7] Kramarova, E. P.; Oleneva, G. I.; Shipov, A. G.;
Macharashvili, A. A.; Shklover, V. E.; Struchkov, Yu.
T.; Baukov, Yu. I. Izv Akad Nauk, Ser Khim 1986,
2156 (in Russian).
REFERENCES
[1] Regitz, M. Methoden der Organischen Chemie
(Houben-Weil); Georg Thieme Verlag: Stuttgart,
1982; E1, E2.
[8] Shipov, A. G.; Kramarova, E. P.; Artamkina, O. B.;
Oleneva, G. I.; Nepomnyashchaya, N. A.; Baukov, Yu.
I. Zh Obsh Khim 1995, 65, 272–280 (in Russian).
Heteroatom Chemistry DOI 10.1002/hc