Synthesis of new functionalized aminomethylphosphonites and their derivatives

Article abstract of DOI:10.1002/hc.20620

The aminomethylation of the several esters of hypophosphorous acid using chloro-, alkoxy-, and amino-substituted methylamines of various structure is proposed as convenient method for the synthesis of new functionalized aminomethylphosphonites and bis(aminomethyl)phosphinates. Also O,O-diethyl(pivaloyl)phosphonite is successfully applied in the aminomethylation as a synthetic analog of unstable diethoxyphosphine.

Full text of DOI:10.1002/hc.20620

Heteroatom Chemistry
Volume 21, Number 6, 2010
Synthesis of New Functionalized
Aminomethylphosphonites 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 19 April 2010; revised 7 June 2010
velop convenient methods for the synthesis of
ABSTRACT: The aminomethylation of the several es-
aminomethylphosphonites that were not read-
ters of hypophosphorous acid using chloro-, alkoxy-,
ily available so far, we undertook a research
and amino-substituted methylamines of various
in the aminomethylation of the several alkyl
structure is proposed as convenient method for the
and trimethylsilyl esters of hypophosphorous
synthesis of new functionalized aminomethylphos-
acid. Highly reactive PH and POSi fragments
phonites and bis(aminomethyl)phosphinates. Also
along with a sufficiently nucleophilic phosphorus
O,O-diethyl(pivaloyl)phosphonite is successfully ap-
atom make these compounds prospective for the
plied in the aminomethylation as a synthetic analog of
aminomethylation (cf. [5–8]). Also chloro-, alkoxy-,
ꢀ
C
unstable diethoxyphosphine. 2010 Wiley Periodicals,
and amino-substituted methylamines were applied
as aminomethylating reagents, and three structural
types of resulting compounds were obtained de-
Inc. Heteroatom Chem 21:361–367, 2010; View this article
online at wileyonlinelibrary.com. DOI 10.1002/hc.20620
pending on the reactivity of starting substances. The
synthesized compounds contain the several moieties
of various amines, carboxamides, sulfonamides, and
amino acids and are promising synthons, ligands,
and bioactive substances.
INTRODUCTION
The numerous organophosphorus compounds
including the several PCH2N fragments are of great
interest as polydentate chelating ligands, extra-
gents, and promising biomimetics of amino acids
with interesting properties [1–4]. Here, we present
convenient methods for obtaining the new function-
alized aminomethylphosphonites that are the key
substances for synthesis of corresponding
organophosphorus compounds with four and
five coordinated phosphorus. In order to de-
RESULTS AND DISCUSSION
We
found
that
the
interaction
containing
of
two
bis(trimethylsiloxy)phosphine
highly reactive centers PH and POSi with
several chloromethylamines and chloromethy-
lamides under mild conditions allowed us to
obtain
both
aminomethylphosphonites
and
Correspondence to: Andrey A. Prishchenko; e-mail:
aprishchenko@yandex.ru.
Contract grant sponsor: Russian Foundation for Basic
Research.
bis(aminomethyl)phosphinates selectively with
a good yield. Thus, under equimolar ratio of starting
reagents only intermediate phosphonites A were
observed in the reaction mixture by NMR 31P
Contract grant number: 08-03-00282.
2010 Wiley Periodicals, Inc.
c
ꢀ
361

362 Prishchenko et al.
spectroscopy (for R = Et, δP 20.2 ppm, 1 JPH 582 Hz). Further addition of triethylamine to the reaction mixture
resulted in the N,N-disubstituted aminomethylphosphonites 1–10 in good yield (Eq. (1)).
Me3SiO
ClCH2NR2
3SiCl
Me3SiCl, Et3N
3N HCl
PCH2NR2
O
(Me3SiO)2PCH2NR2
(Me3SiO)2PH
H
1–10
A
NR = NMe (1), NEt (2), N(Bu-i) (3),
N
(4), N(Me)CHO (5), N(Me)Ac (6),
(7),
(8),
2
2
2
2
N
N
O
N(COOEt)CH2COOEt (9), N(Me)SO2Me (10).
O
(1)
The conceivable scheme of this process involves the Arbuzov reaction of bis(trimethylsiloxy)phosphine with
chloromethylamine or chloromethylamide followed by the silylation of the intermediate phosphonite A by
trimethylchlorosilane in the presence of triethylamine. This must be the first example for a successful Arbuzov
reaction of bis(trimethylsiloxy)phosphine, which was reported to give only a complex mixture of compounds
in the reactions with alkyl halides [9]. The application of an excess of chloromethylamine or amide in similar
reactions in the presence of triethylamine gave N,N-disubstituted bis(aminomethyl)phosphinates 11–23 in
high yields (Eq. (2)). All the reported reactions (Eqs. (1), (2)) took place in dichloromethane solution at room
temperature.
2 ClCH2NR2, Et3N
Me3SiOP(CH2NR2)2
(Me3SiO)2PH
3N HCl, Me3SiCl
O
11–23
(17),
N
(16),
N
NR2 = NMe2 (11), NEt2 (12), NBu2 (13), N(Bu-i)2 (14), N(Am-i)2 (15),
O
(20),
(21),
N(COOEt)CH2COOEt (22), N(Me)SO2Me (23).
N(Me)CHO (18), N(Me)Ac (19),
N
N
O
O
(2)
Also alkoxy(trimethylsiloxy)phosphines and bis(trimethylsiloxy)phosphine reacted with 2 equivalents of
bis(dialkylamino)methanes under heating at 100–130◦C in the presence of zinc chloride as a catalyst to
give bis(aminomethyl)phosphinates 11–17,24–29 in good yield (Eq. (3)).
Me3SiO
2 (R2N)2CH2, ZnCl2
XOP(CH2NR2)2
PH
2NSiMe3
2
XO
O
11–17, 24–29
(25);
(17),
(24),
NR2 = NMe2 (11,28), NEt2 (12,26,27,29), NBu2 (13), N(Bu-i)2 (14), N(Am-i)2 (15),
X = Me3Si (11–17,24,25), Et (26), Pr (27), Bu (28,29).
N
(16),
N
O
N
N
COOMe
(3)
Under equimolar ratio of the starting compounds, this reaction yields a mixture of products. For exam-
ple, the reaction of bis(trimethylsiloxy)phosphine and bis(diethylamino)methane resulted in a mixture of
phosphinate 12, intermediate phosphonites 2, A, and the starting bis(trimethylsiloxy)phosphine that were
detected by NMR 31P spectroscopy. The course of the process suggests that the intermediate complex B
can be decomposed in two ways giving phosphonites 2 and A, respectively. Phosphonites 2 and A are more
nucleophilic than the starting phosphine and are involved in further aminomethylation to give the same
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of New Functionalized Aminomethylphosphonites and Their Derivatives 363
product, bis(aminomethyl)phosphinate 12 (Eq. (4)).
(R2N)2CH2
2NX
(XO)2PCH2NR2
2NH
R2N
2
(R2N)2CH2
(XO)2PCH2NR2
XOP(CH2NR2)2
(XO)2PH
H
O
XO
(R2N)2CH2
2NH
12
PCH2NR2
B
2NX
H
O
A
R = Et, Me3Si.
(4)
It should also be noted that the similar reaction of bis(trimethylsiloxy)phosphine with more reactive
alkoxymethylamines proceeded under mild conditions and provided new aminomethylphosphonites 30–35
with PH fragments in high yields (Eq. (5)).
Me3SiO
R1OCH2NH2
+
(Me3SiO)2PCH2NR2 OR1
PCH2NR2
(Me3SiO)2PH
3SiOR1
H
O
H
30–35
R1 = Alkyl; NR = NEt (30, NPr (31),
(35).
COOMe
(33),
(34),
N
(32),
N
O
2
2
2
N
N
(5)
In contrast, dibutoxyphosphine reacted exothermically with N-butoxymethyl dialkylamines to give dialky-
laminomethylphosphonites 36–38 in good yield (Eq. (6)).
+
BuOCH2NH2
(BuO)2PCH2NR2
(BuO)2PCH2NR2 OBu
(BuO)2PH
H
36–38
C
R = Me (36), Et (37), Pr (38).
(6)
The suggested scheme of this reaction includes an electrophilic attack of the methylene group of N-
butoxymethyl dialkylamine on the trivalent phosphorus followed by the destruction of the intermediate
complex C with butanol being eliminated. However, this method is applicable only to dibuthoxyphos-
phine due to the unstability of dialkoxyphosphines with less-bulky substituents [10]. We showed that
O,O-diethyl(pivaloyl)phosphonite containing labile P C bond [11,12] may be successfully applied in the
aminomethylation as a synthetic analog of unstable diethoxyphospine. Thus, pivaloylphosphonite D reacted
exothermically with N-ethoxymethyl diethylamine in the presence of ethanol to give phosphonite 39 in good
yield. The scheme of this reaction involves the cleavage of the P C bond of the starting phosphonite by
ethanol resulting in diethoxyphosphine (δP 169 ppm, 1 JPH 200 Hz), which undergoes further aminomethyla-
tion similarly to dibutoxyphosphine (Eq. (7)).
EtOH
EtOCH2NEt2
EtOH
(EtO)2PCH2NEt2
(EtO)2PC(O)Bu-t
(EtO)2PH
39
D
(7)
Ethoxymethylamines with bulky substituents at nitrogen undergo analogous reaction only under heating to
70◦C and in the presence of boron trifluoride etherate as a catalyst resulting in phosphonites 40–44 (Eq. (8)).
EtOH, EtOCH2NR2, BF3
Et2O
(EtO)2PC(O)Bu-t
(EtO)2PCH2NR2
D
40–44
(44).
(43),
N
(42),
N
O
NR2 = NPr2 (40), N(Pr-i)2 (41),
N
COOMe
(8)
Heteroatom Chemistry DOI 10.1002/hc

364 Prishchenko et al.
Thus, the aminomethylation of the esters of
hypophosphorous acid may be successfully
applied in the synthesis of several types of
the mixture was filtrated. The solvent was distilled
off in a vacuum, and the residue was distilled to give
6 g phosphonite 1.
functionalized
aminomethylphosphonites
and
The phosphonites 2–10 were obtained analo-
gously.
bis(aminomethyl)phosphinates. The trimethylsilyl
substituted aminomethyl organophosphorus com-
pounds with highly reactive O Si bonds were easily
transformed into various aminomethyl organophos-
phorus derivatives (cf. [13]). So trimethylsilyl
containing bis(aminomethyl)phosphinates easily
reacted with an excess of methanol forming the
water-soluble bis(aminomethyl)phosphinic acids
45–53 (Eq. (9)).
O - Trimethylsilylbis(dimethylaminomethyl)phos -
phinate (11). To
bis(trimethylsiloxy)phosphine and 3.7
a
solution of 7.6
g
g
of
of
triethylamine in 40 mL of diethyl ether, a solu-
tion of 6.7 g of N-(chloromethyl) dimethylamine in
50 mL of methylene chloride was added dropwise
under stirring at 20◦C. The mixture was stirred for
MeOH
HOP(CH2NR2)2
O
Me3SiOP(CH2NR2)2
O
3
11–17,24,25
45–53
(9)
(53).
(51),
(52),
NR2 = NMe2 (45), NEt2 (46), NBu2 (47), N(Bu-i) (48), N(Am-i) (49),
N
(50),
N
O
2
2
N
N
COOMe
Therefore, we developed convenient meth-
ods for the synthesis of previously unavail-
able aminomethylphosphonites and bis(amino-
methyl)phosphinates that might be applied as
polydentate ligands and as precursors for the
synthesis of biologically active compounds.
The structures of functionalized aminomethyl-
phosphonites and their derivatives were confirmed
by the 1H, 13C, and 31P NMR spectra, which indicated
the characteristic signals of the PC1H2NC2Hn frag-
ments (see Tables 1–3). The element analysis data of
synthesized compounds are summarized in Table 4.
1 h, then the solvent was removed, and 150 mL of
diethyl ether was added to residue. The mixture
was filtrated, the solvent was distilled off, and the
residue was distilled in a vacuum to give 7.7 g of
phosphinate 11.
The phosphinates 12–23 were obtained analo-
gously.
O-Ethyl
bis(diethylaminomethyl)phosphinate
(26). A mixture of 6 g of ethoxy (trimethyl-
siloxy)phosphine, 13.7 g of bis (diethylamino)-
methane, and 0.2 g of zinc chloride was heated at
100◦C for 1.5 h, and then distilled in a vacuum to
give 7.5 g of phosphinate 26.
The phosphinates 17,24,25,27–29 were pre-
pared similarly.
EXPERIMENTAL
The 1H, 13C, and 31P NMR spectra were registered on
a Varian VXR-400 and Bruker Avance-400 spectrom-
eter (400, 100, and 162 MHz, respectively) in C6D6,
CDCl3 (1–44), or CD3OD, D2O (45–53). All reactions
were carried out under dry argon in anhydrous sol-
vents. The starting compounds were prepared as de-
scribed in [9–12,14–17].
O-Trimethylsilyl diethylaminomethylphosphonite
(30). To a solution of 17.9 g of bis(trimethyl-
siloxy)phosphine in 50 mL of methylene chloride,
a solution of 6.8 g of N-butoxymethyl diethylamine
in 10 mL of methylene chloride was added dropwise
under stirring at 10◦C. The mixture was heated to
reflux, the solvent was removed, and the residue was
distilled in a vacuum. Phosphonite 30, 6.7 g was ob-
tained.
O,O-Bis(trimethylsilyl)
phosphonite (1). To
dimethylaminomethyl-
solution of 7.2 of
a
g
bis(trimethylsiloxy)phosphine in 30 mL of methy-
lene chloride, a solution of 3.2 g of N-chloromethyl
dimethylamine in 35 mL of methylene chloride
was added dropwise under stirring at 20◦C. The
mixture was stirred for 1 h, 3.6 g of triethylamine
was added under stirring, and the mixture was left
for 2 h. The solvent was distilled off in a vacuum,
150 mL of pentane was added to the residue, and
The phosphonites 31–35 were prepared simi-
larly.
O,O-Dibutyl dimethylaminomethylphosphonite
(36). A mixture of 6.5 g of dibutoxyphosphine and
5.4 g of N-butoxymethyl dimethylamine was left for
3 h and then distilled in a vacuum to obtain 7.3 g of
phosphonite 36.
Phosphonites 37,38 were prepared similarly.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of New Functionalized Aminomethylphosphonites and Their Derivatives 365
TABLE 1 Yields, Products Constants, and NMR Spectral Data (δ, ppm, J, Hz) for the PC1H2NC2Hn Fragmentsa of
Aminomethylphosphonites 1–10,36–44
No.
Yield (%)
Bp (◦C) (p, mmHg)
δ(H) C1H2d
2JPH
δ(C1)d
1JPC
δ(C2)d
3JPC
δ(C O) s
δ sb
P
1
2
3
4
5
65
61
60
51
72
48 (1)
65 (1)
95 (1)
77 (1)
107 (2)
2.40
9.0
–
72.15
66.42
69.21
71.77
58.90
54.93
58.54
60.76
53.42
59.24
58.66
58.28
58.90
65.19
59.56
60.92
59.45
59.07
51.48
64.86
64.20
58.58
17.5
16.0
17.3
17.1
25.8
29.1
28.0
25.4
27.0
28.6
26.1
25.7
28.4
9.4
7.3
6.3
7.1
6.7
3.0
8.6
9.1
9.9
48.26
49.61
66.28
57.29
31.85
35.89
38.21
35.31
31.74
51.18
50.58
50.52
36.59
48.59
49.57
57.52
49.53
57.00
49.78
57.97
56.92
66.85
7.8
6.6
6.8
7.9
4.2
3.0
1.9
4.4
<1
<1
<1
<1
4.2
7.4
7.1
7.2
6.9
6.9
4.8
8.1
7.7
9.3
–
–
–
–
153.17
152.54
154.48
152.66
143.51
149.95
149.51
153.52
151.96
151.13
149.40
148.47
145.72
172.93
173.12
175.01
173.67
174.47
176.09
171.83
170.78
170.43
c
2.54
2.35
2.81
3.23
3.11
8.6
9.2
12.2
9.6
11.3
9.0
–
8.8
9.6
10.1
9.2
7.6
7.7
8.1
7.7
7.7
8.5
6.9
6.5
–
162.14
161.58
168.70
169.07
173.27
174.04
169.31
169.31
6
42
93 (1)
3.37
c
7
8
9
42
68
52
102 (1)
126 (1)
130 (2)
3.44
3.47
3.38
2.75
2.62
2.71
2.72
2.73
2.76
2.81
2.65
10
36
37
38
39
40
41
42
43
44
87
85
81
85
88
75
67
73
78
66
126 (1)
85 (1)
95 (1)
99 (1)
56 (1)
62 (1)
57 (1)
64 (1)
68 (1)
103 (1)
–
–
–
–
–
–
–
–
–
2.60
c
173.52
aAll signals of alkyl and trimethylsilyl fragments are in the standard area. According to the NMR spectra, the compounds 5,6,9 are the mixtures
of two stereoisomers. Their ratio was determined from the 1H, 31P NMR spectra. The spectral parameters of the major isomer are given first,
their ratio for compounds: 5, 60 : 40; 6, 55 : 45; 9, 70 : 30. In 1H NMR spectra, fragments of compounds, s: NCHO of 5, 7.89 and 7.86;
NCH2C(O) of 9, 4.15 and 4.05. In 13C NMR spectra, fragments of compounds: NC(O) of 9, 156.51 s and 156.15 s; NCH2 of 44, 54.86 d, 3JPC
5.0.
1
bData of 31P { H} spectra.
cOverlapping multiplets.
TABLE 2 Yields, Products Constants, and NMR Spectral Data (δ, ppm, J, Hz) for the PC1H2NC2Hn Fragmentsa of
Bis(aminomethyl)phosphinates 11–29, 45–53
No.
Yield (%)
Bp (◦C) (p, mmHg) (mp (◦C))
n2D0
δ (C1)d
1JPC
δ (C2)d
3JPC
δ (C O) s
δ sb
P
11
12
13
14
15
16
17
85
90
88
91
89
86
89
73 (1)
92 (7)
1.4445
1.4510
1.4504
1.4490
1.4520
1.4740
–
57.18
51.80
53.28
54.83
55.13
57.02
56.51
114.2
112.8
103.7
104.9
104.4
114.0
114.8
47.85
48.52
55.04
65.39
53.79
56.91
55.83
8.7
8.1
6.9
7.2
8.0
8.9
9.0
–
–
–
–
–
–
–
37.85
40.09
41.88
39.17
40.54
40.03
37.80
162 (1)
134 (1)
168 (1)
137 (1)
143 (1)
(44)
18
19
68
40
198 (1)
1.4905
1.4830
44.13
48.51
47.37
50.68
42.78
46.83
46.72
98.8
98.3
97.9
35.51
31.53
37.47
37.82
30.24
49.74
49.53
<1
<1
<1
<1
<1
<1
<1
162.45
162.59
169.72
169.91
173.98c
174.68
169.57
30.15
30.32
34.61
35.16
33.86
34.07
30.19
175 (1)
94.7
20
21
22
42
49
37
182 (1)
210 (1)
196 (2)
1.4935
1.4905
1.4594
100.2
103.2
104.3
(Continued)
O,O-Diethyl
diethylaminomethylphosphonite
mixture was distilled in a vacuum to obtain 5.0 g of
phosphonite 39.
(39). A mixture of 5.7 g of O,O-diethyl pivaloylphos-
phonite, 4.3 g of N-ethoxymethyl dimethylamine,
and 2 mL of ethanol was left for 3 h. Then the
The phosphonites 40–44 were obtained sim-
ilarly via heating of the mixtures at 70◦C for
Heteroatom Chemistry DOI 10.1002/hc

366 Prishchenko et al.
TABLE 2 Continued
No.
Yield (%)
Bp (◦C) (p, mmHg) (mp (◦C))
n2D0
δ (C1)d
1JPC
δ (C2)d
3JPC
δ (C O) s
δ sb
P
46.44
47.10
55.88
52.25
50.77
50.73
55.85
50.79
57.09
57.47
51.86
54.40
53.91
57.60
57.79
58.52
52.73
100.4
107.4
113.0
111.8
110.0
109.1
111.3
110.3
99.5
100.1
99.9
101.8
103.6
99.6
49.73
34.17
57.89
66.20d
48.60
48.63
47.81
48.65
45.39
47.49
53.08
64.57
53.45
55.53
55.01
58.68
65.63d
<1
<1
7.7
11.7
7.8
7.8
10.1
7.8
5.8
5.9
6.1
5.2
6.9
6.4
6.4
4.3
8.6
169.57
30.73
28.86
39.01
38.58
43.40
49.33
47.21
47.64
25.52
22.18
23.21
25.45
27.20
23.25
21.25
19.03
22.01
23
24
25
26
27
28
29
45
46
47
48
49
50
51
52
53
86
81
93
79
92
93
91
95
92
95
93
93
91
96
96
97
210 (2)
149 (1)
183 (0.5)
88 (1)
118 (1)
81 (1)
125 (1)
(126)
(119)
oil
oil
oil
(188)
(204)
(79)
1.4808
1.4865
1.4810
1.4557
1.4570
1.4530
1.4575
–
–
173.63
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
100.8
96.9
100.7
oil
171.70
aAll signals of alkyl and trimethylsilyl fragments are in the standard area. According to the NMR spectra, the compounds 18,19,22 are the
mixtures of two stereoisomers. The spectral parameters of the major isomer isomer are given first; their ratio for compounds: 18, 65 : 35;
2
2
2
19, 80 : 20; 22, 70 : 30. In 1H NMR spectra, fragment C1H2 of compounds, d: 23, 3.23, JPH 7.2; 45, 2.71, JPH 9.6; 48, 3.10, JPH 7.8; 51,
2.80, JPH 9.6; the signals of the diastereotopic protons of methylene groups C1H2 of 25 and 53 are characteristic ABX multiplets δ (HA), δ
2
(HB), 2J(HAHB), 2J(PHA), 2J(PHB) for compounds: 25, 3.18, 2.68, 14.8, 10.4, 7.7; 53, 2.79, 2.60, 14.2, 11.2, 9.2; the signals of fragment C1H2
for other compounds are in the overlapping multiplets. In 1H NMR spectra, fragment NCHO of compound 18, s, 7.85 and 7.87. In 13C NMR
spectra, fragments of compounds, s: NC(O) of 22, 156.36 and 156.04; NCH2 of 25, 54.90 and 53, 54.44.
1
bData of 31P { H} spectra.
cd, 3JPC, 2.1.
dFragment NCHC(O), for compounds, δH: 25, overlapping multiplets, 53, 3.60 dd, 3JHH 8.4, and 5.2.
TABLE 3 Yields, Products Constants, and NMR Spectral Data (δ, ppm, J, Hz) for the HPC1H2NC2Hn Fragmentsa of
Aminomethylphosphonites 30–35
Bp (◦C)
No. Yield (%) (p, mmHg)
n2D0
δ (H) HP d t 1JPH 3JHH δ (C1)d 1JPC δ (C2)d 3JPC
δ dt
P
1JPH
2JPH
30
31
32
33
34
35
68
72
75
80
78
83
80 (2)
96 (2)
91 (1)
102 (2)
115 (2)
142 (2)
1.4401
1.4429
1.4633
1.4688
1.4615
1.4690
7.12
7.16
7.18
7.05
7.03
7.15b
538.9 2.1
538.0 2.1
541.7 2.0
545.1 2.0
538.4 2.1
54.21 117.5 48.92
55.33 117.1 57.86
59.73 115.3 56.70
59.08 113.9 55.72
58.82 115.1 57.57
8.4 22.95 538.9
8.1 23.08 538.0
9.5 20.36 541.7
9.1
9.0
9.7
9.6 17.21 545.1 10.0
7.8 19.38 538.4 8.5
548.7 1.6b 54.38 114.3 66.18c 12.4 17.71d 548.7 11.2d
aAll signals of alkyl and trimethylsilyl fragments are in the standard area. In 1H NMR spectra, fragments PC1H2NC2Hm of compounds 30–32,34
2
3
look as overlapping multiplets. In 1H NMR spectrum, fragment PC1H2N of compound 33: 2.32 dd, JHH 10.0, JHH 2.0. In 13C NMR spectrum,
fragment NCH2 of compound 35: 54.67 d, 3JPC 2.8.
bIn 1H NMR spectrum, fragment HMPCHAHBN of compound 35: δ (HM) 7.15 ddd, 1J(PHM) 548.7, 3J(HAHM) 1.6, 3J(HBHM) 3.2, δ (HA) 3.01, δ
(HB) 2.71, 2J(HAHB) 14.8, 2J(PHA) 11.2, 2J(PHB) 9.2, 3J(HMHA) 1.6, 3J(HMHB) 3.2.
cIn NMR spectra, fragment NCHC(O): δC (C O) 173.21 s, δH (CH) 3.24 dd, 3JHH 7.2 and 5.6.
dIn 31P NMR spectrum, ddd, 2JPH 11.2 and 9.2.
0.5 h in the presence of 0.1 g of boron trifluoride
etherate.
Bis(dimethylaminomethyl)phosphinic acid (45).
The solution of 4.8 g of phosphinate 11 in 10 mL
of diethyl ether was added dropwise under stirring
at 10◦C to 20 mL of methanol. The resulting mixture
was heated to a boil, the solvent was distilled off in
a vacuum, and the residue was kept in a vacuum
(1 mmHg) for 1 h to give 3.3 g of acid 45 as colorless
hydroscopic crystals.
The acids 46–53 were obtained simi-
larly.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of New Functionalized Aminomethylphosphonites and Their Derivatives 367
TABLE 4 Elemental Analyses Data of Compoundsa
REFERENCES
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Aminophosphinic Acids. Chemistry and Biological
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Phosphorus Sulfur 1988, 35, 329–334.
Calcd. (%) Found (%)
Empirical
Formula
Formula
weight
No.
C
H
C
H
11 C9H25N2O2PSi
12 C13H33N2O2PSi
252.37 42.84 9.99 42.86 10.12
308.48 50.62 10.78 50.48 10.64
420.70 59.95 11.74 59.81 11.62
420.70 59.95 11.74 59.78 11.65
476.80 62.98 12.05 62.72 11.96
332.50 54.19 10.00 54.02 9.89
336.45 46.41 8.69 46.26 8.58
280.34 38.56 7.55 38.46 7.37
308.40 42.84 8.17 42.59 8.29
332.42 46.97 7.58 46.69 7.39
388.51 52.55 8.56 52.26 8.47
13
14
C
C
21H49N2O2PSi
21H49N2O2PSi
15 C25H57N O PSi
16 C15H33N22O22PSi
17 C13H29N2O4PSi
18 C9H21N2O4PSi
19 C11H25N2O4PSi
20 C13H25N2O4PSi
21
C17H33N2O4PSi
22 C19H37N2O10PSi 512.56 44.52 7.28 44.39 7.03
23 C9H25N2O6PS2Si 380.50 28.41 6.62 28.26 6.49
24 C17H37N2O2PSi
360.55 56.63 10.34 56.49 10.23
420.51 48.55 7.91 48.23 7.80
264.35 54.52 11.06 54.67 11.23
278.36 56.09 11.22 55.92 11.15
236.28 50.83 10.67 50.68 10.54
292.39 57.51 11.38 57.40 11.26
223.33 43.02 9.93 43.15 10.02
251.38 47.78 10.43 47.59 10.34
235.34 45.93 9.42 45.74 9.26
237.31 40.49 8.50 40.28 8.45
249.37 48.17 9.70 47.99 9.59
279.35 42.99 7.94 42.73 7.89
235.31 56.15 11.14 55.92 10.88
263.36 59.29 11.48 59.15 11.62
291.41 61.83 11.76 61.69 12.04
207.26 52.16 10.70 52.03 10.61
235.31 56.15 11.14 56.23 11.20
235.31 56.15 11.14 55.97 11.03
219.27 54.78 10.11 54.63 10.01
221.24 48.86 9.10 48.69 9.03
263.28 50.18 8.42 50.32 8.36
180.19 40.00 9.51 36.61 9.60
236.30 50.83 10.66 50.45 10.85
348.52 62.03 11.86 61.89 11.74
348.52 62.03 11.86 61.78 11.68
404.62 65.30 12.21 64.97 12.05
260.32 55.37 9.68 55.72 9.72
264.26 45.45 8.01 45.55 8.28
288.37 58.31 10.14 58.03 9.98
348.33 48.27 7.23 48.03 7.16
25
26
C
C
17H33N2O6PSi
12H29N2O2P
27 C13H31N2O2P
28 C10H25N2O2P
29
30 C8H22NO2PSi
31 10H26NO2PSi
C14H33N2O2P
C
32 C9H22NO2PSi
33 C8H20NO3PSi
34 C10H24NO2PSi
35 C10H22NO4PSi
36 C11H26NO2P
13H30NO2P
15H34NO2P
39 C9H22NO2P
40 11H26NO2P
41 C11H26NO2P
42 C10H22NO2P
43 C9H20NO3P
44 C11H22NO4P
45 C6H17N2O2P
46 C10H25N2O2P
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Livantsova, L. I.; Petrosyan, V. S. Heteroatom Chem
2010, 21, 71–77.
[14] Wozniak, L.; Chojnowski, J. Tetrahedron 1989, 45,
2465–2524.
37
38
C
C
C
[15] Hilgetag, G.; Martini, A. Weygand-Hilgetag. Organ-
isch-Chemische
Experimentierkunst;
Khimia:
Moscow, 1968 (in Russian).
[16] Boehme, H.; Koch, L.; Koehler, E. Chemische
Berichte 1962, 95, 1849–1858.
[17] Orlova, N. A.; Shipov, A. G.; Savostyanova, I. A.;
Baukov, Yu. I. Zh Obsh Khim 1991, 61, 2024–2031
(in Russian).
47
C18H41N2O2P
48 C18H41N2O2P
49 C22H49N2O2P
50 C12H25N2O2P
51 C10H21N2O4P
52 C14H29N2O2P
53
C14H25N2O6P
aThe compounds 1–10 are very unstable in an air atmosphere; there-
fore, these substances were analyzed as their derivatives, corre-
sponding phosphinates.
Heteroatom Chemistry DOI 10.1002/hc