Synthesis and fugicidal activities of 2-silatranyl propylamino-4-substitued phenyl(hydrogen)-5,5-dimethyl-1,3,2-dioxaphosphinanes-2-oxides (sulfides)

Article abstract of DOI:10.1080/104265090968343

Phosphoryl-aminopropyl-silatranes 4 were synthesized by nucleophilic reactions of 2-Cl-1,3,2- dioxaphosphinanes 2 with α-aminopropyl-silatrane 3, which was obtained by the cyclization reaction of triethanolamine and γ-aminopropyltriethoxysilane. The structures of the products were characterized by ¹H NMR, ³¹P NMR, IR, MS, and elemental analyses. The target compounds 4 exhibited fungicidal activity. Copyright Taylor & Francis Inc.

Full text of DOI:10.1080/104265090968343

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Phosphorus, Sulfur, and Silicon
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Synthesis and Fugicidal
Activities of 2-Silatranyl
Propylamino-4-substitued
Phenyl(Hydrogen)-5,5-
dimethyl-1,3,2-
dioxaphosphinanes-2-oxides
(Sulfides)
Shi-Guan Wan a , Xing-Yu Yang a , Yan Yu a & Chang
Liu a
a Institute of Organic Synthesis, Central China
Normal University , Wuhan, People's Republic of
China
Published online: 19 Aug 2006.
To cite this article: Shi-Guan Wan , Xing-Yu Yang , Yan Yu & Chang Liu (2005)
Synthesis and Fugicidal Activities of 2-Silatranyl Propylamino-4-substitued
Phenyl(Hydrogen)-5,5-dimethyl-1,3,2-dioxaphosphinanes-2-oxides (Sulfides),
Phosphorus, Sulfur, and Silicon and the Related Elements, 180:12, 2813-2821, DOI:
10.1080/104265090968343
To link to this article: http://dx.doi.org/10.1080/104265090968343
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Phosphorus, Sulfur, and Silicon, 180:2813–2821, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090968343
Synthesis and Fugicidal Activities of 2-Silatranyl
Propylamino-4-substitued Phenyl(Hydrogen)-5,5-
dimethyl-1,3,2-dioxaphosphinanes-2-oxides
(Sulfides)
Shi-Guan Wan
Xing-Yu Yang
Yan Yu
Chang Liu
Institute of Organic Synthesis, Central China Normal University,
Wuhan, People’s Republic of China
Phosphoryl-aminopropyl-silatranes
tions of 2-Cl-1,3,2- dioxaphosphinanes
4
were synthesized by nucleophilic reac-
with γ -aminopropyl-silatrane 3,
2
which was obtained by the cyclization reaction of triethanolamine and γ -
aminopropyltriethoxysilane. The structures of the products were characterized by
1
31
H NMR, P NMR, IR, MS, and elemental analyses. The target compounds 4
exhibited fungicidal activity.
Keywords 2-Cl-1,3,2-Dioxaphosphinanes; fungicidal activity; synthesis; nucleophilic re-
actions; phosphoryl-aminopropyl-silatranes; γ -aminopropyl silatrane
INTRODUCTION
2-Cl-1,3,2-dioxaphosphinane is an important heterocycle which shows
good biological and pharmaceutical activity. Some derivatives were
found to exhibit good fungicidal or antitumor activities.1−5 As an impor-
tant intermediate compound, γ -aminopropyl silatrane has been found
to have good biological activity.6−9 Therefore, we became interested in
the synthesis of phosphoryl-aminopropyl-silatranes. Herein we have
synthesized a series of 2-Cl-4-substitued-1,3, 2-dioxaphosphinanes,
which were reacted with γ -aminopropyl silatrane to give the target
compounds phosphoryl-aminopropyl–silatranes 4. The synthetic route
Received November 8, 2004; in final form March 16, 2005.
We gratefully acknowledge financial support of this work by the Science Foundation
of Wuhan City (20021002052).
Address correspondence to Xing-Yu Yang, Institute of Organic Synthesis,Central
China Normal University, Wuhan 430079, People’s Republic of China. E-mail:
wsg stone@tom.com
2813

2814
S.-G. Wan et al.
is shown in Scheme 1. The structures of the products was verified by 1H
NMR, 31P NMR, IR, MS, and elemental analyses. Some of the products
possess potential fungicidal activity.
SCHEME 1
RESULTS AND DISCUSSION
The easily accessible substituted benzaldehydes reacted with isobu-
tyraldehyde in the presence of potassium hydroxide to give diols 1,
which readily were reacted with phosphorus oxychloride or phospho-
rus thiochloride to give 2-Cl-1,3,2-dioxaphosphinanes 2. Reaction of 2
with γ -aminopropyl silatrane 3 gave target compounds 4 in good yields
(see Table I).
The formation of 4 was a nucleophilic substitution reaction. Initially,
2-Cl-1,3,2-dioxaphosphinanes 2 in methylene dichloride were added
dropwise to γ -aminopropyl silatrane 3 to obtain target compounds 4,
but the reaction required 5–6 h and the yields were low. Next, triethy-
lamine was used as an acid-binding agent. In the presence of triethy-
lamine, the reaction times were shorter and the yields were higher.
Although the reactivity of 2a∼f were different from 2g∼l, when the re-
actions were carried out at 20∼30◦C, only the reaction times were dif-
ferent. With the use of triethylamine, the best reaction time was 2–4 h
and the yields were about 80% (see Table I).
The structures of 4 have been verified spectroscopically. For example,
the 1H NMR spectral data for 4c showed the signals of Si CH2 at 0.14–
0.17 ppm as a triplet; the protons of the 5-position methyl groups of the
phosphorus heterocycle appeared as two single peaks at 0.73 ppm and
0.92 ppm, as the two methyl groups are located in different magnetic

Dioxaphosphinanes
2815
TABLE I Preparation of Phosphoryl-
Aminopropyl-Silatranes 4
Compound
X
R
Reaction time (h) Yield (%)a
4a
4b
4c
4d
4e
4f
4g
4h
4i
O
O
O
O
O
O
S
S
S
S
S
H
Ph
2
2
2
2
3
3
3
3
3
3
4
4
85
83
78
76
70
79
80
79
77
75
65
74
4-Cl-C6H4
4-CH3-C6H4
4- CH3O-C6H4
2,4-Cl2- C6H4
H
Ph
4-Cl-C6H4
4-CH3-C6H4
4- CH3O-C6H4
2,4-Cl2- C6H4
4j
4k
4l
S
aIsolated yields based on 2-Cl-1,3,2-dioxaphosphinanes used.
The reactions were run in the presence of Et3N.
environments; and the chemical shift of the multiplets due to P N CH2
overlapped with the multiplets due to N CH2 at 2.52–2.79 ppm and
O CH2 at 3.29–3.60 ppm. An addition of the silatrane unit resonances
include a triplet for NH at 5.18–5.24 ppm, and a singlet for O CH at
5.30 ppm . The aromatic signals of the R group appear at 7.39–7.47 ppm
as multiplets. For 31P NMR spectra, the phosphorus atom appeared as
a singlet with a chemical shift of 7.65 ppm. In the IR spectral data of 4c,
the NH stretching frequency of N H appears as a broad peak at 3234
cm−1, the strong stretching frequency of P O appears at 1211 cm−1
,
the stretching frequency of P O C showed a strong absorption at
1089 cm−1 and 995 cm−1, and the strong absorption due to Si O C
appeared at 1045 cm−1. The MS spectrum of 4c showed a molecule ion
peak at m/z 490.5 with a 19% abundance and the other main fragmen-
tation peaks were in accordance with the structure of 4c. As for the
corresponding compound of 4i, the 1H NMR spectral data and MS spec-
trum are similar to 4c; in the IR spectral data of 4i, the strong stretching
frequency of P S appears at 752 cm−1; and for the 1P NMR spectra of
4i, the chemical shift for the phosphorus atom appeared at 69.9 ppm.
The biological activity of 4 was investigated, and the results indi-
cated a moderate-to-good fungicidal activity. For example, 4l showed
87% inhibition of Botrytis cinerepers and 4f showed 85% inhibition of
Bipilaris maydis in 50 mg/L (see Table II).
EXPERIMENTAL
All reagents were analytically pure. Solvents were purified according to
standard procedures. Melting points were uncorrected. MS data were

2816
S.-G. Wan et al.
TABLE II The Fungicidal Activities of Phosphoryl-Aminopropyl-
Silatranes 4 (50 mg/L, Relative Inhibition Ratio %)
Fusarium Rhizoctonia Botrytis Gibberella Dothiorella Bipilaris
Compound oxysporium
solani
cinerepers
zeae
gregaria
maydis
4a
4b
4c
4d
4e
4f
4g
4h
4i
24
15
29
29
28
39
29
29
34
24
30
43
54
16
30
53
51
58
33
6
40
55
52
60
70
57
40
20
72
80
64
70
30
61
59
87
37
12
37
37
31
40
37
33
37
46
35
55
58
37
16
27
45
43
43
6
32
43
41
64
79
65
55
45
63
85
70
45
60
55
70
81
4j
4k
4l
obtained on a Finnigan Trace MS spectrometer. IR were recorded on a
PE-983 infrared spectrometer as KBr pellets with absorption in cm−1
.
1H NMR and 31P NMR spectra were recorded on a VARIAN MERCURY-
PLUS 400 spectrometer with TMS and 85% H3PO4 as the internal and
external reference, respectively, in DMSO-d6 as the solvent. Reson-
nces are given in ppm (δ). Elementary analysis were obtained on a
Perkin-Elmer CHN 2400 elementary analysis instrument.
Preparation of Phosphoryl-Aminopropyl-Silatranes 410−16
100 mmol (substitued) and benzaldehyde and 200 mmol isobutyralde-
hyde were added into a 250 mL three-necked flask, and a solution of
100 mmol KOH in 90 mL dry ethanol was added dropwise at a bath tem-
perature between 50∼60◦C with for stirring 5 h. Then the solvent was
removed under reduced pressure, and 100 mL of cold water was added
to the residual mixture. After standing for 12 h, filtration provided a
solid which was washed twice with heptane and was recrystallized from
toluene to give the diols 1.
To a solution of 10 mmol 1 prepared as above in 50 mL dry methylene
dichloride, 10 mmol phosphorus oxychloride was added dropwise over
1 h at 35◦C, and the mixtrre was stirred under reflux for 2 h. The solvent
was removed under reduced pressure, and the residual mixture was
recrystallized from toluene to give 2-Cl-1,3,2-dioxaphosphinanes 2a∼f
.
10 mmol of 1, 10 mmol of phosphorus thiochloride and 16 mL of dry
tetrahydrofuran were added to a 100 mL three necked-flask. A solu-
tion of 20 mmol triethylamine in 8 mL dry tetrahydrofuran was added
dropwise over 1 h at ice-bath temperatures from the foltrate, then at

Dioxaphosphinanes
2817
room temperture with stirring for 14 h. After filtration, the solvent was
removed under reduced pressure, and the residual mixture was recrys-
tallized from cyclohexane to give 2-Cl-1,3,2-dioxaphosphinanes 2g∼l
.
100 mmol of triethanolamine and 100 mmol of γ -aminopropy-
ltriethoxysilane were added to a 250 mL three-necked flask, which was
fitted with a thermometer and a Dean Stark trap. The mixture was
heated slowly to reflux, and reflux continued until the ethanol sub-
stantially was removed. The reaction product remaining in the flask
was γ -aminopropyl-silatrane 3, which was used directly without fur-
ther purification.
5 mmol of γ -aminopropyl-silatrane 3, 5 mmol of triethylamine, and
30 mL of dry methylene dichloride were added to a 100 mL three-necked
flask; a solution of 5 mmol 2 in 8 mL of dry methylene dichloride was
added dropwise for 1 h at a bath temperture of 10◦C and kept at room
temperture with stirring for 2∼4 h. The solvent was removed under re-
duced pressure and the residual mixture was washed twice with a little
water and was recrystallized from ethanol–water to give phosphoryl-
aminopropyl-silatranes 4.
2-Silatranyl Propylmino-5,5-dimethyl-1,3,2-dioxaphosphinane-
2-oxide (4a)
White crystals, m.p. 228–229◦C, 1H NMR (DMSO-d6, 400 MHz) δ =
4.93–4.97 (t, 1H, NH), 3.76–3.98 (m, 10H, O-CH2), 2.63–2.76 (m, 8H,
N-CH2), 1.40–1.42 (m, 2H, C-CH2), 1.02 (s, 3H, CH3), 0.87 (s, 3H,
CH3), 0.06–0.10 (t, 2H, Si-CH2); 31P NMR (DMSO-d6, 400 MHz) δ =
7.71; IR (KBr) (υmax/cm−1), 3283 (N H), 1263 (P O), 1096 and 1006
(P O C), 1052 (Si O C); MS(m/z, %), 380 (M, 14.9), 336 (50.4), 322
(93.8), 207 (7.2), 174 (100), 149 (2.9), 129 (51.0). Elemental anal. calcd.
for C14H29N2O6PSi: C, 44.21; H, 7.63; P, 8.16. Found: C, 44.28; H, 7.69;
P, 8.08.
2-Silatranyl Propylmino-4-phenyl-5,5-dimethyl-1,3,2-
dioxaphosphinane-2-oxide (4b)
White crystals, m.p. 186–188◦C, 1H NMR (DMSO-d6, 400 MHz) δ =
7.31–7.39 (m, 5H, Ph H), 5.32 (s, 1H, O CH), 5.21–5.27 (t, 1H, NH),
3.32–3.63 (m, 8H, O CH2), 2.51–2.80 (m, 8H, N CH2), 1.41–1.43 (m,
2H, C CH2), 0.89 (s, 3H, CH3), 0.70 (s, 3H, CH3), 0.12–0.16 (t, 2H, Si-
CH2); 31P NMR (DMSO-d6, 400MHz) δ = 7.68; IR (KBr) (υmax/cm−1),
3210 (N H), 1229 (P O), 1098 and 993 (P O C), 1051 (Si O C);
MS(m/z), 456 (M+, 1.3), 411 (5.9), 313 (1.0), 283 (2.0), 254 (4.1), 174
(100), 129 (4.9), 91 (10.8). Elemental anal. calcd. for C20H33N2O6PSi:
C, 52.63; H, 7.24; P, 6.80. Found: C, 52.57; H, 7.29; P, 6.85.

2818
S.-G. Wan et al.
2-Silatranyl Propylmino-4-(4-chloro-phenyl)-5,5-dimethyl-
1,3,2-dioxaphosphinane-2-oxide (4c)
White crystals, m.p. 210–211◦C, 1H NMR (DMSO-d6, 400 MHz) δ =
7.39–7.47 (m, 4H, Ph H), 5.30 (s, 1H, O CH), 5.18–5.24 (t, 1H, NH),
3.29–3.60 (m, 8H, O CH2), 2.52–2.79 (m, 8H, N CH2), 1.46–1.53 (m,
2H, C CH2), 0.92 (s, 3H, CH3), 0.73 (s, 3H, CH3), 0.14–0.17 (t, 2H,
Si-CH2); 31P NMR (DMSO-d6, 400MHz) δ = 7.65; IR (KBr) (υmax/cm−1),
3234 (N-H), 1211 (P O), 1089 and 995 (P O C), 1045 (Si O C); (m/z),
490.5 (M+, 19.2), 460 (11.2), 313 (27.7), 281 (37.1), 254 (69.0), 174 (100),
129 (25.4), 91 (12.0). Elemental anal. calcd. for C20H32ClN2O6PSi: C,
48.93; H, 6.52; P, 6.32. Found: C, 48.86; H, 6.60; P, 6.38.
2-Silatranyl Propylmino-4-(4-methyl-phenyl)
-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide (4d)
White crystals, m.p. 209–210◦C,1H NMR (DMSO-d6, 400 MHz) δ =
7.20–7.21 (m, 4H, Ph H), 5.26 (s, 1H, O CH), 5.20-5.23 (t, 1H, NH),
3.34–3.63 (m, 8H, O CH2), 2.51–2.80 (m, 8H, N-CH2), 2.31 (s, 3H,
Ar–CH3), 1.45–1.54 (m, 2H, C CH2), 0.93 (s, 3H, CH3), 0.67 (s, 3H,
CH3), 0.12–0.16 (t, 2H, Si CH2); 31P NMR (DMSO-d6, 400MHz) δ =
7.78; IR (KBr) (υmax/cm−1), 3215 (N H), 1211 (P O), 1095 and 994
(P O C), 1047 (Si O C); MS (m/z), 470 (M+, 0.1), 313 (2.5), 281 (5.6),
254 (24.3), 174 (100), 129 (9.0), 91 (11.0). Elemental anal. calcd. for
C21H35N2O6PSi: C, 53.62; H, 7.45; P, 6.60. Found: C, 53.58; H, 7.41; P,
6.63.
2-Silatranyl propylmino-4-(4-methoxyl-phenyl)
-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide (4e)
Pale yellow crystals, m.p. 205–206◦C, 1H NMR (DMSO-d6, 400 MHz)
δ = 7.32–7.38 (m, 4H, Ph H), 5.33 (s, 1H, O CH), 5.20–5.25 (t, 1H,
NH), 3.71 (s, 3H, O CH3) 3.30–3.62 (m, 8H, O CH2), 2.53–2.78 (m,
8H, N CH2), 1.48–1.56 (m, 2H, C CH2), 0.86 (s, 3H, CH3), 0.68 (s,
3H, CH3), 0.11–0.15 (t, 2H, Si CH2); 31P NMR (DMSO-d6, 400MHz)
δ = 7.70; IR (KBr) (υmax/cm−1), 3243 (N-H), 1238 (P O), 1091 and 995
(P O C), 1045 (Si O C); MS (m/z), 486 (M+, 3.0), 313 (4.1), 281 (7.2),
254 (20.5), 174 (100), 129 (11.3), 91 (16.6). Elemental anal. calcd. for
C21H35N2O7PSi: C, 51.85; H, 7.20; P, 6.38. Found: C, 51.79; H, 7.18; P,
6.42.
2-Silatranyl Propylmino-4-(2,4-dichlorophenyl)
-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide (4f)
White crystals, m.p. 249–250◦C ,1H NMR (DMSO-d6, 400 MHz) δ =
7.46–7.69 (m, 3H, Ph H), 5.67 (s, 1H, O CH), 5.35–5.40 (t, 1H, NH),

Dioxaphosphinanes
2819
3.33–3.62 (m, 8H, O CH2), 2.57–2.80 (m, 8H, N CH2), 1.44–1.50 (m,
2H, C CH2), 1.00 (s, 3H, CH3), 0.74 (s, 3H, CH3), 0.12–0.16 (t, 2H,
Si CH2); 31P NMR (DMSO-d6, 400MHz) δ = 7.69; IR (KBr) (υmax/cm−1),
3235 (N H), 1243 (P O), 1097 and 996 (P O C), 1048 (Si O C); MS
(m/z), 525 (M+, 0.2), 313 (1.6), 281 (7.1), 254 (21.5), 174 (100), 129 (5.1),
91 (3.1). Elemental anal. calcd. for C20H31Cl2N2O6PSi: C, 45.71; H, 5.90;
P, 5.90. Found: C, 45.66; H, 5.87; P, 5.94.
2-Silatranyl Propylmino-5,5-dimethyl-1,3,2-
dioxaphosphinane-2-sulfide (4g)
White crystals, m.p. 179–180◦C, 1H NMR (DMSO-d6 ,400 MHz) δ =
5.70–5.75 (t, 1H, NH), 3.70–4.13 (m, 10H, O CH2), 2.75–2.82 (m, 8H,
N CH2), 1.43–1.46 (m, 2H, C–CH2), 1.14 (s, 3H, CH3), 0.79 (s, 3H,
CH3), 0.07–0.11 (t, 2H, Si CH2); 31P NMR (DMSO-d6 ,400MHz) δ =
69.6; IR (KBr) (υmax/cm−1), 3219 (N H), 1104 and 1009 (P O C), 1035
(Si O C), 757 (P S); MS (m/z), 396 (M+, 2.1), 353 (5.3), 339 (26.0), 223
(7.4), 174 (100), 129 (14.2). Elemental anal. calcd. for C14H29N2O5PSSi:
C, 42.42; H, 7.32; P, 7.83. Found: C, 42.38; H, 7.37; P, 7.86.
2-Silatranyl Propylmino-4-phenyl-5,5-dimethyl-1,3,2-
dioxaphosphinane-2-sulfide (4h)
Pale yellow crystals, m.p. 156–158◦C, 1H NMR (DMSO-d6, 400 MHz)
δ = 7.32–7.41 (m, 5H, Ph H), 5.95–5.99 (t, 1H, NH), 5.35 (s, 1H,
O CH), 3.35–3.90 (m, 8H, O CH2), 2.51–2.98 (m, 8H, N CH2), 1.51–
1.60 (m, 2H, C CH2), 0.90 (s, 3H, CH3), 0.73 (s, 3H, CH3), 0.15–0.19
(t, 2H, Si CH2); 31P NMR (DMSO-d6, 400MHz) δ = 69.8; IR (KBr)
(υmax/cm−1), 3231 (N H), 1091 and 1019 (P O C), 1027 (Si O C),
751 (P S); MS (m/z), 472 (M+, 3.9), 329 (3.3), 299 (3.4), 270 (6.2), 174
(100), 129 (8.0), 91 (16.9). Elemental anal. calcd. for C20H33N2O5PSSi:
C, 50.85; H, 6.99; P, 6.57. Found: C, 50.80; H, 7.05; P, 6.63.
2-Silatranyl Propylmino-4-(4-chloro-phenyl)-
5,5-dimethyl-1,3,2-dioxaphosphinane-2-sulfide (4i)
Pale yellow crystals, m.p. 165–167◦C, 1H NMR (DMSO-d6, 400 MHz)
δ = 7.41-7.49 (m, 4H, Ph H), 5.91–5.97 (t, 1H, NH), 5.36 (s, 1H,
O CH), 3.36–3.85 (m, 8H, O CH2), 2.52–2.93 (m, 8H, N CH2), 1.49–
1.58 (m, 2H, C CH2), 0.89 (s, 3H, CH3), 0.72 (s, 3H, CH3), 0.16–0.19
(t, 2H, Si CH2); 31P NMR (DMSO-d6, 400MHz) δ = 69.9; IR (KBr)
(υmax/cm−1), 3238 (N H), 1079 and 1001 (P O C), 1028 (Si O C),
752 (P S); MS (m/z), 506.5 (M+,6.2), 329 (2.5), 299 (0.8), 270 (4.1), 174
(100), 129 (6.4), 91 (3.6). Elemental anal. calcd. for C20H32ClN2O5PSSi:
C, 47.38; H, 6.32; P, 6.12. Found: C, 47.31; H, 6.37; P, 6.15.

2820
S.-G. Wan et al.
2-Silatranyl Propylmino-4-(4-methyl-phenyl)-5,5-dimethyl-
1,3,2-dioxaphosphinane-2-sulfide (4j)
Pale yellow crystals, m.p. 167–168◦C, 1H NMR (DMSO-d6, 400 MHz)
δ = 7.17–7.22 (m, 4H, Ph H), 5.91–5.96 (t, 1H, NH), 5.29 (s, 1H,
O CH), 3.43–3.88 (m, 8H, O CH2), 2.51–2.96 (m, 8H, N CH2), 2.31
(s, 3H, Ar CH3),1.50–1.59 (m, 2H, C CH2), 0.89 (s, 3H, CH3), 0.70 (s,
3H, CH3), 0.15–0.19 (t, 2H, Si CH2); 31P NMR (DMSO-d6, 400MHz)
δ = 70.2; IR (KBr) (υmax/cm−1), 3237 (N H), 1084 and 1002 (P O C),
1028 (Si O C), 751 (P S); MS (m/z), 486 (M+, 0.2), 329 (1.5), 299
(0.2), 270 (4.7), 174 (100), 129 (6.5), 91 (6.8). Elemental anal. calcd. for
C21H35N2O5PSSi: C, 51.85; H, 7.20; P, 6.38. Found: C, 51.78; H, 7.25; P,
6.34.
2-Silatranyl Propylmino-4-(4-methoxyl-phenyl)-5,5-dimethyl-
1,3,2-dioxaphosphinane-2-sulfide (4k)
Pale yellow crystals, m.p. 163–164◦C, 1H NMR (DMSO-d6, 400 MHz)
δ = 7.31–7.37 (m, 4H, Ph H), 5.91–5.97 (t, 1H, NH), 5.35 (s, 1H,
O CH), 3.75 (s, 3H, O CH3) 3.32 3.67 (m, 8H, O CH2), 2.54–2.90
(m, 8H, N CH2), 1.49–1.57 (m, 2H, C CH2), 1.05 (s, 3H, CH3), 0.72 (s,
3H, CH3), 0.14–0.18 (t, 2H, Si CH2); 31P NMR (DMSO d6, 400MHz)
δ = 70.1; IR (KBr) (υmax/cm−1), 3233 (N H), 1089 and 1001 (P O C),
1031 (Si O C), 752 (P S); MS (m/z), 502 (M+,1.2), 329 (2.3), 299 (0.7),
270 (6.2), 174 (100), 129 (7.5), 91 (11.8). Elemental anal. calcd. for
C21H35N2O6PSSi: C, 50.20; H, 6.97; P, 6.18. Found: C, 50.27; H, 6.91; P,
6.23.
2-Silatranyl Propylmino-4-(2,4-dichloro-phenyl)-5,5-dimethyl-
1,3,2-dioxaphosphinane-2-sulfide (4l)
Pale yellow crystals, m.p. 184–185◦C, 1H NMR (DMSO-d6, 400 MHz)
δ = 7.45–7.70 (m, 3H, Ph H), 6.04–6.08 (t, 1H, NH), 5.80 (s, 1H,
O CH), 3.33–3.94 (m, 8H, O CH2), 2.51–2.94 (m, 8H, N CH2), 1.49–
1.55 (m, 2H, C CH2), 1.48 (s, 3H, CH3), 1.02 (s, 3H, CH3), 0.14–0.18
(t, 2H, Si CH2); 31P NMR (DMSO-d6, 400MHz) δ = 70.1; IR (KBr)
(υmax/cm−1), 3229 (N-H), 1096 and 1005 (P O C), 1027 (Si O C), 751
(P S); MS (m/z), 541 (M+,0), 329 (0.6), 299 (1.5), 270 (6.7), 174 (100),
129 (7.8), 91 (2.6). Elemental anal. calcd. for C20H31Cl2N2O5PSSi: C,
44.36; H, 5.73; P, 5.73. Found: C, 44.39; H, 5.70; P, 5.77.
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