Synthesis of new organophosphorus-substituted mono-and bis(trimethylsilyl) amines with pch2n fragments and their derivatives

Article abstract of DOI:10.1002/hc.20580

Convenient procedures for the synthesis of new organophosphorus-substituted monoand bis(trimethylsilyl)amines with PCH₂N moiety are proposed, starting from trimethylsilyl esters of organophosphorus acids, as well as 1,3,5-trialkylhexahydro-1,3,

Full text of DOI:10.1002/hc.20580

Heteroatom Chemistry
Volume 21, Number 2, 2010
Synthesis of New
Organophosphorus-substituted Mono- and
Bis(trimethylsilyl)amines with PCH N
2
Fragments 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 8 September 2009; revised 21 January 2010
rus compounds including PCH2NH2, PCH2NC(O),
ABSTRACT: Convenient procedures for the syn-
and PCH2NSO2 fragments, which are also of inter-
thesis of new organophosphorus-substituted mono-
est as biologically active compounds and promising
and bis(trimethylsilyl)amines with PCH2N moiety
ligands [2,3]. In this work, we propose the conve-
are proposed, starting from trimethylsilyl esters
nient way for synthesis of new organophosphorus-
of organophosphorus acids, as well as 1,3,5-
substituted N-trimethylsilylamines and their deriva-
trialkylhexahydro-1,3,5-triazines and N-alkoxymethyl
tives such as organophosphorus-substituted amides
bis(trimethylsilyl)amines
as
aminomethylating
and sulfonamides of various structures. Starting
trimethylsilyl esters of trivalent organophosphorus
acids [1], symmetrical trialkylhexahydrotriazines
[4], and N-alkoxymethyl bis(trimethylsilyl)amines
[5–7] were used by us.
reagents. Certain properties of the resulting com-
ꢀ
C
pounds are presented.
2010 Wiley Periodicals, Inc.
Heteroatom Chem 21:71–77, 2010; Published online in
Wiley InterScience (www.interscience.wiley.com). DOI
10.1002/hc.20580
RESULTS AND DISCUSSION
INTRODUCTION
Thus an excess of diethyl trimethylsilyl phos-
phite reacts with symmetrical hexahydrotri-
azines A on heating to 130◦C in the presence
of zinc chloride as a catalyst forming N-tri-
methylsilylaminomethylphosphonates 1–4 with
a good yield. Also the bisphosphonates 5–8 are
isolated as the by-products after distillation of the
N-Trimethylsilylated amines are widely used in
organophosphorus chemistry [1], but the N-
trimethylsilyl-substituted organophosphorus com-
pounds remained unavailable. At the same time,
the latter compounds are the key precursors for
various interesting types of new organophospho-
Correspondence to: Andrey A. Prishchenko; e-mail:
aprishchenko@yandex.ru.
Contract grant sponsor: Russian Foundation for Basic
Research.
Contract grant number: 08-03-00282.
2010 Wiley Periodicals, Inc.
c
ꢀ
71

72 Prishchenko et al.
reaction mixture (cf. [8]; Eq. (1)).
R
N
ZnCl2
3 (EtO)2POSiMe3
+
3 (EtO)2PCH2N(SiMe3)R + [(EtO)2PCH2]2NR + RN(SiMe3)2
RN
NR
O
O
5–8
A
1–4
B
R = Me (1,5), Et (2,6), CH2=CHCH2 (3,7), Bu (4,8).
(1)
Hence the splitting of triazines A proceeds mainly by symmetrical way via formation of highly reactive
intermediates C following by the addition of trimethylsilyl phosphite (Eq. (2)).
R
N
3 ZnCl2
3 (EtO)2POSiMe3
–3 ZnCl2
1–4
3 CH2=NR ZnCl2
RN
NR
A
C
(2)
The proposed scheme of the minor unsymmetrical splitting of triazines A includes the formation of
unstable aminales D and bis(trimethylsilyl)amines B in the mixture with starting compounds (Eq. (3)). The
yields of bisphosphonates 5–8 are about 10–15%.
R
N
2 (EtO)2POSiMe3, ZnCl2
[(EtO)2PCH2]2NR + [R(SiMe3)N]2CH2
RN
NR
O
5–8
D
ZnCl2
RN(SiMe3)2
+
CH2=NR ZnCl2
[R(SiMe3)N]2CH2
C
B
1–4
CH2=NR ZnCl2
+
(EtO)2POSiMe3
– ZnCl2
(3)
Under the same conditions, tris(trimethylsilyl)phosphite reacts with triazine E to form phosphonate 9
and bisphosphonate 10 (Eq. (4)).
Me
N
ZnCl2
3 (Me3SiO)3P +
3 (Me3SiO)2PCH2N(SiMe3)Me + [(Me3SiO)2PCH2]2NMe
MeN
NMe
O
O
E
9
10
(4)
Analogously functionalized phosphonites react with triazine E giving only functionalized phosphinates
11,12 with high yields due to the sterical factors (Eq. (5)).
EtO
3
PCH(OEt)2, ZnCl2
CH(OEt)2
(CH2)2COOSiMe3
Me3SiO
3 (Me3SiO)2P(CH2)2COOSiMe3, ZnCl2
3 EtOP
O
E
3Me3SiOP
O
CH2N(SiMe3)Me
CH2N(SiMe3)Me
11
12
(5)
The interaction of triazine F even with an excess of bis(trimethylsilyl)phosphine proceeds as double
aminomethylation via highly reactive intermediate phosphonite G, yielding phosphinate 13 (Eq. (6)).
Et
N
CH2NHEt
3(Me3SiO)2PH, ZnCl2
F, ZnCl2
3 Me3SiOP
3 (Me3SiO)2PCH2NHEt
EtN
NEt
CH2N(SiMe3)Et
O
F
G
13
(6)
Heteroatom Chemistry DOI 10.1002/hc

New Organophosphorus-substituted Mono- and Bis(trimethylsilyl)amines with PCH2N Fragments and Their Derivatives 73
Thus we proposed the convenient methods for preparing N-trimethylsilyl-substituted aminomethyl
organophosphorus compounds using symmetrical hexahydrotriazines as aminomethylation reagents. The
aminomethyl organophosphorus compounds with N,N-bis(trimethylsilyl) moiety are synthesized by us using
N-alkoxymethyl bis(trimethylsilyl)amines as aminomethylating reagents. So the corresponding phosphonate
14 and phosphinate 15 are synthesized through the reaction of N-ethoxymethyl bis(trimethylsilyl)amine
with trimethylsilyl phosphite and phosphonite under heating to 130◦C in the presence of zinc chloride as a
catalyst (cf. [6]; Eq. (7)).
Me
POSiMe3, ZnCl2
Me
(EtO)2POSiMe3, ZnCl2
– EtOSiMe3
EtO
(EtO)2PCH2N(SiMe3)2
PCH2N(SiMe3)2
O
EtOCH2N(SiMe3)2
EtO
– EtOSiMe3
O
14
15
(7)
N-methoxymethyl
Also
we
found
that
of
bis(trimethylsiloxy)phosphine
reacts
with
bis(trimethylsilyl)amine at 120◦C in the presence of trimethylchlorosilane as a catalyst, resulting in
formation of phosphonite 16 in high yield (Eq. (8)).
Me3SiO
Me3SiCl
PCH2N(SiMe3)2
(Me3SiO)2PH + MeOCH2N(SiMe3)2
– MeOSiMe3
H
O
16
(8)
Treatment of phosphonite 16 with excess N-trimethylsilylpiperidine readily produces phosphonite 17
with a tricoordinated phosphorus atom (cf. [9]; Eq. (9)).
16 + Me3SiN(CH2)5
(Me3SiO)2PCH2N(SiMe3)2
– HN(CH2)5
17
(9)
Previously unavailable phosphonites 16,17 are the key precursors for various organophosphorus com-
pounds with a PCH2N(SiMe3)2 fragment such as the unsymmetrical phosphinates 18–20. Thus phosphonite
16 smoothly adds to trimethylsilyl acrylate to give phosphinate 18, and phosphonite 17 is easily aminomethy-
lated with substituted chloromethylamines, yielding phosphinates 19,20 (Eq. (10)).
CH2N(SiMe3)2
16 + CH2=CHCOOSiMe3
Me3SiOP
O
CH2CH2COOSiMe3
18
CH2N(SiMe3)2
17 + ClCH2NR2
Me3SiOP
O
– Me3SiCl
CH2NR2
19,20
NR = NEt (19),
N
O (20)
2
2
(10)
Mono- and bis-N-trimethylsilyl-substituted aminomethyl organophosphorus compounds with highly
reactive N Si bonds are easily transformed into various aminomethyl organophosphorus derivatives. So
trimethylsilyl-containing phosphonate 9 and phosphinates 13 and 18 easily reacted with methanol to obtain
the water-soluble organophosphorus acids 21–23 (Eq. (11)).
3 MeOH
(HO)2PCH2NHMe
9
– 3 MeOSiMe3
O
21
2 MeOH
HOP(CH2NHEt)2
13
– 2 MeOSiMe3
O
22
CH2NH2
HOP
4 MeOH
18
– 4 MeOSiMe3
CH2CH2COOH
O
23
(11)
Heteroatom Chemistry DOI 10.1002/hc

74 Prishchenko et al.
In the present work, we have developed the convenient methods for preparing novel organophosphorus-
substituted amides containing PCH2NC(O) and PCH2NSO2 fragments. It was found by us that easily
available N-trimethylsilyl aminomethylphosphonates 1–4 are convenient synthons for preparing promis-
ing phosphorus-containing carboxamides and sulfonamides. Thus N-trimethylsilylamines 1–4 easily react
with various carboxylic acid chlorides and substituted sulfonyl chlorides in methylene chloride to form
functionalized phosphonates 24–39 in high yields (cf. [10]; Eq. (12)).
R
R
R
ClSO2X
ClC(O)X
(EtO)2PCH2NSO2X
(EtO)2PCH2NSiMe3
(EtO)2PCH2NC(O)X
– Me3SiCl
– Me3SiCl
O
O
O
24–32
1–4
33–39
R = Me (24-26, 33-36), Et (27,28,37), CH2=CHCH2 (29-31, 38), Bu (32,39);
X = Me (33,37–39),
4-IC6H4 (26), 4-MeC6H4 (34).
(30,32), t-Bu (29), 2-FC6H4 (24,31), 3-FC6H4 (28), 2-ClC6H4 (25), 4-ClC6H4 (35), 2-BrC6H4 (27), 4-BrC6H4 (36),
(12)
TABLE 1 Yields, Products Constants, and NMR Spectral Data (δ, ppm; J, Hz) for the PC1H2NC2 Fragmentsa of Amines 1–23
δ(H)
Yield
Compound (%)
Bp (◦C) (p, mmHg)
(mp (◦C))
C1H2
d
2JPH
δ(C1) d
1JPC
δ(C2)
36.47s
δP, sb
20
nD
1
71
75
78
80
12
15
10
10
76
13
82
78
54
70 (1)
102 (1)
103 (1)
104 (1)
154 (1)
155 (1)
158 (1)
168 (1.5)
98 (1)
157 (1)
132 (1.5)
145 (1.5)
125 (1)
1.4375
1.4390
1.4505
1.4435
1.4520
1.4482
1.4580
1.4500
1.4332
1.4392
1.4358
1.4375
1.4515
2.96
3.08
3.06
3.09
2.97
3.12
3.16
3.13
2.82
3.01
3.0–3.3
2.79
2.81
2.83
3.12
2.8–2.9
2.9–3.1
2.88
1.6–2.0
2.2–2.7
2.2–2.6
3.68
7.5
7.1
6.8
6.8
9.6
9.2
9.6
9.2
7.6
9.2
–
5.6
11.1
10.4
9.2
–
–
9.6
–
–
–
12.4
10.4
9.6
47.64
42.89
42.69
43.27
53.93c
50.09c
50.05c
50.60c
48.25
56.08c
47.48
51.88
47.97
47.97
46.21
45.03
157.6
157.4
156.6
154.9
157.4
156.3
156.8
155.3
165.4
161.7
97.9
107.6
105.7
105.7
159.5
106.4
23.51
26.15
23.93
23.92
21.59
22.22
22.00
22.30
7.35
2
41.91s
50.20 s
47.56 s
42.26 td
51.03 td
60.05 td
56.92 td
35.85 s
45.75 td
36.89 s
36.53 s
46.08 s
45.93 s
–
–
–
–
–
–
–
3
4
5
6
7
8
9
10
11
12
13
4.38
36.86
40.03
39.84
14
78
74
59
81
87
85
82
94
95
85
87 (0.5)
102 (1)
105 (2)
102 (1)
140 (1)
140 (1)
147 (1)
(169)
1.4420
1.4572
26.40
48.92
24.21
151.90
38.55
35.24
34.77
6.62
16.64
29.45
15e
f
16
46.73
106.2
f
17
18
19
20
21
22
23
56.64
45.93
41.05
43.36
45.76
45.79
37.57
23.1
105.2
106.3
104.8
138.2
99.9
1.4558
1.4568
1.4678
–
–
–
34.84 d
45.24 d
–
(58)
(168)
2.96
3.04
90.9
aAll signals of alkyl and trimethylsilyl fragments are in the standard area. In 1H NMR spectra the signals of the diastereotopic protons of
methylene groups C1H2 of 11,15,18–20 are characteristic ABX multiplets, δ(HA), δ(HB), 2J (HAHB), 2J (PHA),2J (PHB) for compounds: 11, 3.23,
3.09, 15.6, <1, 5.6; 18, 3.00, 2.94, 16.0, 2.0, 7.6; 19, 3.08, 2.86, 16.0, 1.8, 6.6; 20, 3.12, 2.91, 16.2, 1.5, 6.4; fragment HMPCHAHBN of
compound 16: δ (HM) ddd, 1J (PHM) 528.4, 3J (HAHM) 2.8, 3J (HBHM) 1.6, δ(HA) 3.04, δ(HB) 2.94, 2J (HAHB) 16.4, 2J (PHA) 8.4, 2J (PHB) 6.4, 3J
(HMHA) 2.8, 3J (HMHB) 1.6. In 13C NMR spectra fragment PC1H2C2H2C3(O) of compounds, δ(C1), 1JPC; δ(C2), 2JPC; δ(C3), 3JPC: 12, 24.49, 93.4;
29.92, 3.0; 172.77, 15.2; 18, 24.32, 86.3; 28.95, 3.0; 172.61, 13.6; 23, 24.42, 97.1; 27.01, 3.1; 177.31, 13.8.
1
bData of 31P { H} spectra.
c dd, 3JPC for compounds: 5, 10.4; 6, 7.6; 7, 7.8; 8, 7.1; 10, 9.4.
d 3
J
for compounds: 5, 7.9; 6, 8.0; 7, 8.6; 8, 8.4; 10, 7.9; 21, 7.5;22, 12.1.
PC
eFragment PCH3 for compound 15: δH 1.08 d, 2JPH 12.8; δC 11.76 d, 1JPC 84.9.
f The compounds 16 and 17 are air-sensitive.
Heteroatom Chemistry DOI 10.1002/hc

New Organophosphorus-substituted Mono- and Bis(trimethylsilyl)amines with PCH2N Fragments and Their Derivatives 75
TABLE 2 Yields, Products Constants, and NMR Spectral Data (δ, ppm; J, Hz) for the PC1H2N(C2)C3(O) Fragmentsa of Amides
24–32
Bp (◦C) (p,
mmHg)
δ (H)
Yield
Compound (%)
n2D0
C1H2d
2JPH
δ (C1) d
1JPC
δ (C2) s δ (C3) s
δP (b), sc
24
25
26
27
28
29
30
31
32
82
81
85
83
79
78
84
81
86
170 (1)
194 (1)
210 (1)
202 (1)
183 (1)
119 (0.5)
138 (2)
162 (1)
145 (1)
1.4978
1.5160
3.53
–
3.57
2.76
3.71
–
11.6
–
11.6
10.0
11.2
–
41.79
–
41.04
45.40
42.19
–
37.72
42.92
38.52
–
40.55
–
39.53
41.36
38.42
43.01
39.82
42.48
155.0
–
154.3
157.3
153.5
–
155.0
159.0
155.2
–
154.8
–
155.8
159.4
155.4
157.9
155.3
159.3
37.61
–
36.17
32.82
38.19
–
42.91
39.75
43.51
–
50.40
–
49.23
47.61
51.11
46.93
46.96
45.73
168.29
–
166.96
167.32d
169.18
–
167.65
166.65
168.86
–
176.70
–
172.12
171.92
166.10
166.00
171.62
171.74
19.35 (95)
18.19 (5)
18.95 (90)
18.00 (10)
19.50 (95)
18.24 (5)
19.21 (83)
18.27 (17)
19.67 (95)
18.42 (5)
21.03 (98)
20.22 (2)
19.68 (79)
18.65 (21)
19.23 (83)
18.33 (17)
19.83 (85)
18.60 (15)
1.5578
1.5109
1.4902
1.4635
1.4785
1.5035
1.4680
3.62
10.0
3.60
9.6
e
e
–
3.57
–
–
11.2
–
3.32
10.8
e
e
e
e
e
e
3.41
3.43
11.2
9.0
aAll signals of alkyl and aryl groups are in the standard area. In the 13C NMR spectra fragments CHal for compounds: 24, 161.24 d, 1JCF 246.7;
25, 129.03 s and 128.96 s; 26, 95.33 s; 27, 117.99 s and 117.86 s; 28, 161.48 d 1JCF 246.1; 31, 157.52 d 1JCF 246.8.
bAccording to the NMR spectra, the amides 24–32 are mixtures of two stereoisomers. Their ratio was determined from the 1H and 31P NMR
spectra. The spectral parameters of the major isomer are given first; for compounds 24, 26, 28, 29 there are only 31P NMR spectral parameters
for minor isomers due to its low contents.
1
c Data of 31P { H} spectra.
d d, 3JPC 3.5.
eOverlapping multiplets.
TABLE 3 Yields, Products Constants, and NMR Spectral Data (δ, ppm; J, Hz) for the PC1H2N(C2)SO2C3 Fragmentsa of
Sulfonamides 33–39
Yield
(%)
Bp (◦C) (p, mmHg)
(mp (◦C))
Compound
n2D0
δ(H) d
2JPH
δ (C1) d
1JPC
δ (C2) s
δ (C3) s
δP, sb
33
34
35
36
37
38
39
74
75
70
72
78
73
78
184 (4)
195 (1)
188 (0.5) (53)
241 (1) (65)
182 (4)
1.4559
1.5100
–
3.22
3.16
3.14
3.33
3.34
3.42
3.29
10.0
11.2
11.2
11.6
9.2
8.8
8.8
44.08
44.78
44.58
45.09
40.62
40.08
40.89
160.0
163.7
163.5
163.7
159.4
159.0
157.4
35.35
36.11
35.90
36.42
42.51
49.55
47.06
35.52
143.30
138.80
135.31
38.48
39.14
38.15
18.46
17.93
17.56
17.68
19.13
19.14
19.19
–
1.4518
1.4642
1.4569
162 (1)
166 (1)
aAll signals of alkyl and aryl groups are in the standard area. The 1H NMR spectra fragment NMe, s for compounds: 33, 2.74; 34, 2.68; 35,
2.64; 36, 2.86; fragment SO2Me, s for compounds: 33, 2.63; 37, 2.67, 38, 2.80, 39, 2.61. Fragment MeAr, s; 34: δH 2.22, δC 20.92. In the 13C
NMR spectra, fragment CHal, s for compounds: 35, 134.35; 36, 127.99.
1
bData of 31P { H} spectra.
of synthesized compounds are summarized in
Table 4.
The
novel
organophosphorus-substituted
amines 5–8, 21–23, and amides 24–39 present
interest as promising ligands and biologically active
compounds. The structures of organophosphorus-
substituted amines and amides 1–39 were con-
EXPERIMENTAL
The 1H, 13C, and 31P NMR spectra were registered on
the Varian VXR-400 and Bruker Avance-400 spec-
trometer (400, 100, and 162 MHz, respectively) in
CDCl3 (1–20,24–39) or D2O (21–23) against TMS
firmed by the H, 13C, and 31P NMR spectra, which
1
show characteristic signals of the PC1H2NC2,
PC1H2N(C2)C3(O), and PC1H2N(C2)SO2C3 fragments
(see Tables 1–3). The elemental analysis data
Heteroatom Chemistry DOI 10.1002/hc

76 Prishchenko et al.
TABLE 4 Elemental Analyses Data of Compounds
Calcd. (%)
Found (%)
Compound
Empirical Formula
C9H24NO3PSi
Formula Weight
C
H
C
H
1
253.36
267.39
279.40
295.44
331.24
345.27
357.32
373.36
341.61
507.81
311.44
397.67
324.54
311.51
281.48
311.58
383.75
455.83
396.73
410.71
125.06
180.19
167.10
303.27
319.72
411.17
378.20
317.30
291.33
275.28
329.31
291.33
259.27
335.37
355.79
400.24
273.30
285.31
301.35
42.67
44.92
47.29
48.78
39.89
41.74
43.70
45.03
38.68
35.48
46.28
42.28
44.41
42.41
42.67
38.55
40.69
42.16
45.41
43.86
19.21
39.99
28.75
51.48
48.83
37.97
44.46
52.99
53.59
52.36
54.71
53.59
32.43
46.56
40.51
36.01
35.16
37.89
39.86
9.55
9.80
9.38
10.24
8.21
8.47
8.18
8.91
9.44
8.53
9.71
9.12
10.25
9.71
10.03
9.71
9.98
9.29
10.42
9.57
6.44
9.51
6.03
6.31
5.99
4.66
5.60
6.67
9.00
8.05
6.43
9.00
7.00
6.61
5.38
4.78
7.38
7.07
8.03
42.54
44.78
47.12
48.69
39.74
41.59
43.54
44.90
38.52
35.28
46.03
42.12
44.29
42.26
42.55
38.26
40.50
41.97
45.12
43.64
19.03
39.75
28.64
51.26
48.69
37.69
44.28
52.87
53.35
52.23
54.62
53.40
32.28
46.40
40.40
35.87
34.97
37.68
39.69
9.43
9.69
9.33
10.16
8.15
8.40
8.03
8.78
9.26
8.42
9.64
9.06
10.04
9.66
9.98
9.57
9.83
9.07
10.39
9.66
6.49
9.39
6.08
6.23
5.90
4.52
5.48
6.59
8.74
7.94
6.30
8.83
6.87
6.52
5.26
4.64
7.29
6.97
7.92
2
C10H26NO3PSi
3
C11H26NO3PSi
C12H30NO3PSi
C11H27NO6P2
C12H29NO6P2
C13H29NO6P2
C14H33NO6P2
4
5
6
7
8
9
C11H32NO3PSi3
C15H43NO6P2Si4
10
11
12
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
C12H30NO4PSi
C14H36NO4PSi3
C12H33N2O2PSi2
C11H30NO3PSi2
C
10H28NO2PSi2
C10H30NO2PSi3
13H38NO2PSi4
C
C16H42NO4PSi4
C15H41N2O2PSi3
C
15H39N2O3PSi3
C2H8NO3P
C6H17N2O2P
C4H10NO4P
C H FNO4P
13 19
C13H19ClNO4P
13H19INO4P
C14H21BrNO4P
14H21FNO4P
13H26NO4P
C
C
C
C12H22NO4P
C15H21FNO4P
C13H26NO4P
C7H18NO5PS
C
13H22NO5PS
C12H19ClNO5PS
C12H19BrNO5PS
C8H20NO5PS
C9H20NO5PS
C10H24NO5PS
(1H and 13C) and 85% H3PO4 in D2O (31P). All re-
actions were carried out under dry argon in anhy-
drous solvents. The starting trimethylsilyl esters of
trivalent organophosphorus acids and aminomethy-
lating reagents were prepared as described in
[4,5,11].
5. Phosphonates 2–4,9, phosphinates 11–13, and
bisphosphonates 6–8,10 were prepared similarly.
O,O-Diethyl N,N-Bis(trimethylsilyl)aminomethyl-
phosphonate (14). A mixture of 12 g of diethyl
trimethylsilyl phosphite, 10 g of N-ethoxymethylbis-
(trimethylsilyl)amine, and 0.2 g of zinc chlo-
ride was heated at 120–140◦C with distillation of
ethoxy(trimethyl)silane for 2 h, and then distilled in
a vacuum to give 11.1 g of phosphonate 14.
Phosphinate 15 and phosphonite 16 were ob-
tained analogously.
O,O-Bis(trimethylsilyl) N,N-bis(trimethylsilyl)-
aminomethylphosphonite (17). A mixture of 6.2 g of
phosphonite 16, 4.7 g of N-trimethylsilylpiperidine,
O,O-Diethyl
N-methyl-N-trimethylsilylamino-
methylphosphonate (1). A mixture of 22.2 g of
diethyl trimethylsilyl phosphite, 3.9 g of 1,3,5-
trimethylhexahydrotriazine, and 0.2 g of zinc chlo-
ride was heated at 130◦C for 1 h and then distilled to
give 16.3 g of phosphonate 1. Repeated distillation
of the high-boiling fraction gave 1.2 g of N-
methyl-N,N-bis(diethoxyphosphorylmethyl)amine
Heteroatom Chemistry DOI 10.1002/hc

New Organophosphorus-substituted Mono- and Bis(trimethylsilyl)amines with PCH2N Fragments and Their Derivatives 77
and 0.1 g of zinc chloride was heated at 120–130◦C
for 2 h, and then distilled in a vacuum to give 6.2 g
of phosphonite 17.
The amides 24–28 and 30–32 were prepared
similarly.
O,O-Diethyl N-methyl-N-(methylsulfonyl)amino-
methylphosphonate (33). To a solution of 1 g of
methanesulfonyl chloride in 5 mL of methylene chlo-
ride was added dropwise with stirring and cool-
ing at 10◦C to a solution of 2 g of phosphonate 1
in 5 mL of methylene chloride. The mixture was
heated to the boil, the solvent was removed, and the
residue was distilled in a vacuum to obtain 1.7 g of
O-Trimethylsilyl
N,N-bis(trimethylsilyl)amino-
methyl 2-(trimethylsiloxycarbonyl)ethylphosphinate
(18). To a solution of 4.7 g of phosphonite 16 in
5 mL of methylene chloride, 3.5 g of trimethylsilyl
acrylate and 2 mL of pyridine were added. Then the
solvent was distilled off, and the residue was heated
at 100◦C for 1 h and then distilled in a vacuum to
give 6 g of phosphinate 18.
phosphonate 33.
The sulfonamides 34–39 were obtained analo-
O-Trimethylsilyl
N,N-bis(trimethylsilyl)amino-
gously.
methyl N,N-diethylaminomethylphosphinate (19).
To a solution of 5.8 g of phosphonite 17 in
20 mL of methylene chloride, a solution of 1.8 g of
N-(chloromethyl)diethylamine in 20 mL of methy-
lene chloride was added dropwise with stirring
at 0◦C. The reaction mixture was heated to room
temperature and then to the boil, and the solvent
was distilled off. The residue was distilled in a
vacuum to give 5.1 g of phosphinate 19.
REFERENCES
[1] Wozniak, L.; Chojnowski, J. Tetrahedron 1989, 45,
2465–2524.
[2] Kolodiazhnyi, O. I. Usp Khim 2006, 75, 254–282 (in
Russian).
[3] Kukhar, V. P.; Hudson, H. R. Aminophosphonic and
Aminophosphinic Acids. Chemistry and Biological
Activity; Wiley: New York, 2000.
Phosphinate 20 was obtained analogously.
N-Methyl aminomethylphosphonic acid (21). To
a solution of 10.9 g of phosphonate 9 in 10 mL of
diethyl ether was added dropwise with stirring at
10◦C in 30 mL of methanol. The resulting mixture
was heated to boil, the solvent was distilled off in
a vacuum, and the residue was kept in a vacuum
(1 mmHg) for 1 h to give 3.8 g of acid 21 as colorless
hydroscopic crystals.
The acids 22 and 23 were obtained similarly.
O,O-Diethyl N-allyl-N-pivaloylaminomethylphos-
phonate (29). To a solution of 11 g of phosphonate 3
in 20 mL of methylene chloride, a solution of 4.5 g of
pivaloyl chloride in 10 mL of methylene chloride was
added dropwise with stirring at 10◦C. The mixture
was heated to reflux, the solvent was removed, and
the residue was distilled in a vacuum. Phosphonate
29, 8.5 g was obtained.
[4] Hilgetag, G.; Martini, A. Weygand- Hilgetag.
Organisch-Chemische Experimentierkunst; Khimia:
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[5] Bestmann, H. J.; Woelfel, G. Angew Chem 1984, 96,
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[6] Morimoto, T.; Aono, M.; Sekiya, M. J Chem Soc,
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[7] Morimoto, T.; Takahashi, T.; Sekiya, M. J Chem Soc,
Chem Commun 1984, 794–795.
[8] Courtois, G.; Miginiac, L. Synth Commun 1991, 21,
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[9] Prishchenko, A. A.; Livantsov, M. V.; Novikova, O. P.;
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Heteroatom Chemistry DOI 10.1002/hc