Synthesis of 2-γ-N-(aminoethyl)aminopropyl-2-methyl-6-alkyl(aryl,H)-1,3-dioxa-6- aza-2-silacyclooctanes

Article abstract of DOI:10.1081/SCC-100105331

Some new 2-γ-N-(aminoethyl)aminopropyl-2-methyl-1,3-dioxa-6-aza-2- silacyclooctane and 2-γ-N-(aminoethyl)aminopropyl-2-methyl-6-alkyl(aryl)-1,3-dioxa-6-aza- 2-silacyclooctanes have been synthesized from γ-chloropropyldimethoxymethyl silane by ethylenediamine substitution and diethanolamine or N-alkyl(aryl)diethanolamines substitution. The resulting silocanes have been characterized by elemental analyses, IR, and ¹H NMR.

Full text of DOI:10.1081/SCC-100105331

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SYNTHESIS OF 2-γ-N-(AMINOETHYL)AMINOPROPYL-2-
METHYL-6-ALKYL(ARYL,H)-1,3-DIOXA-6-AZA-2-
SILACYCLOOCTANES
a
b
a
Qinzheng Yang , Jimao Lin & Fangzheng Li
a
School of Chemistry and Environmental Science, Shandong University , Jinan,
Shandong, 250 100, P. R. China
b
School of Chemistry and Environmental Science, Shandong University , Jinan,
Shandong, 250 100, P. R. China
Published online: 15 Aug 2006.
To cite this article: Qinzheng Yang , Jimao Lin & Fangzheng Li (2001) SYNTHESIS OF 2-γ-N-(AMINOETHYL)AMINOPROPYL-2-
METHYL-6-ALKYL(ARYL,H)-1,3-DIOXA-6-AZA-2-SILACYCLOOCTANES, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 31:18, 2817-2822, DOI: 10.1081/SCC-100105331
To link to this article: http://dx.doi.org/10.1081/SCC-100105331
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SYNTHETIC COMMUNICATIONS, 31(18), 2817–2822 (2001)
SYNTHESIS OF 2-c-N-
AMINOETHYL)AMINOPROPYL-2-
(
METHYL-6-ALKYL(ARYL,H)-1,3-
DIOXA-6-AZA-2-SILACYCLOOCTANES
Qinzheng Yang, Jimao Lin,* and Fangzheng Li
School of Chemistry and Environmental
Science, Shandong University,
Jinan, 250 100, Shandong, P. R. China
ABSTRACT
Some new2- g-N-(aminoethyl)aminopropyl-2-methyl-1,3-dioxa-
6-aza-2-silacyclooctane and 2-g-N-(aminoethyl)aminopropyl-
2-methyl-6-alkyl(aryl)-1,3-dioxa-6-aza-2-silacyclooctanes have
been synthesized from g-chloropropyldimethoxymethyl
silane by ethylenediamine substitution and diethanolamine or
N-alkyl(aryl)diethanolamines substitution. The resulting silo-
canes have been characterized by elemental analyses, IR, and
1
H NMR.
In the 1960s, Fry et al. and Turley et al. first reported the synthesis
1
of penta-coordinate bridgehead silatranes. Since then many studies on
,2
3
–5
different substituted silatranes have been reported.
6
Silocanes(1,3-dioxa-
-aza-2-silacyclooctanes) have similar structure as silatranes, but only a few
*
Corresponding author.
2
817
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

ORDER
REPRINTS
2
818
YANG, LIN, AND LI
6
–11
studies on the kinds of silocanes were reported.
In the present paper,
we wish to report the synthesis of some new kinds of silocanes: 2-g-N-
aminoethyl)aminopropyl-2-methyl-1,3-dioxa-6-aza-2-silacyclooctane (IIIa)
and 2-g-N-(aminoethyl)aminopropyl-2-methyl-6-alkyl(aryl)-1,3-dioxa-6-aza-
-silacyclooctanes (IIIb–f ). g-Chloropropyldimethoxymethylsilane reacts
(
2
with ethylenediamine (Scheme 1), to give 2-g-N-(aminoethyl)aminopropyl-
dimethoxymethylsilane (I). The request reagent diethanolamines are pre-
pared as depicted in Scheme 2. Compound I is treated with diethanolamine or
N-alkyl(aryl)diethanolamines (Scheme 3) to afford our target molecules III.
1
The structure of the newcompounds we re verified by IR,
and elemental analyses.
H NMR,
Scheme 1.
Scheme 2.
The infrared spectra exhibit two of the stronger bonds at
absorption.
128 ꢀ 7 cmꢁ and 1062 ꢀ 7 cm , respectively, due to the n
1
ꢁ1
ꢁ
1
Si-O-C
1
The frequencies at 523–536 cm showthe existence of a N ! Si bond
1
1
1
coordinate in the cyclic compounds. In H NMR (CDCl ) spectra, the
3
single peak at d 0.0–0.1 ppm is assigned to the CH Si group, Hg (for the
3
numbering of the different protons, see below) was observed in the region d
0.5–0.7 ppm, Ha, d, f overlap between d 1.2–1.7 ppm, Hl is assigned to the
CH group, Hb, c, e, j in IIIa–IIIe occur in the region d 2.3–2.9 ppm, but the
3
Hj in IIIf resonances at d 3.9–4.0 ppm due to the shifting effect of the phenyl
group, Hk in IIIb–IIIe exhibits resonance in the region d 2.3–2.9 ppm, and in

ORDER
REPRINTS
NEW KINDS OF SILOCANES
2819
IIIf in the region d 6.7–7.4 ppm, the d 3.6–3.7 ppm peaks are assigned to
OCH group, i.e. Hi.
2
2
H NCH
2
CH
2
NH(CH
I)
2
)
3
SiCH
3
(OCH
3
)
2
þ(HOCH
2 2 2
CH ) NR
(
(II)
H
a
2
NCH
b
2
CH
2
NHCH
2
CH
f
2
CH
2
SiCH
3
(OCH CH
2
2 2
) NR
c
d
e
g
h
I
j
R ¼ H CH CH CH CH CH CH CH CH CH CH CH CH CH CH C H
2
3
2
2
3
2
2
2
3
2
2
2
2
3
6
5
k
k
l
k
m
l
k
m
m
l
k
m
m
m
l
k
Scheme 3.
EXPERIMENTAL
ꢁ
1
IR spectra were recorded in the region 4000–400 cm on a Nicolet
1
0X infrared spectrophotometer. H NMR (CDCl ) spectra were obtained
5
3
on a FX 90Q nuclear magnetic resonance spectrometer. Elemental analyses
were carried out on Yanaco MT-3 element analyzer. Thermometer was not
corrected.
Synthesis of 2-c-N-(aminoethyl) aminopropylmethyl-
dimethoxysilane (I)
To a 100 mL three-necked flask fitted with condenser and thermo-
ꢂ
meter, 48.0 g (0.8 mol) ethylenediamine was added. At 118 C, 21.1 g (0.1 mol)
g-chloropropyldimethoxymethylsilane was added dropwise over 3 h. Then
reflux for another 3 h. The mixture was cooled to 80 C. 1 mL ethanol
ꢂ

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2
820
YANG, LIN, AND LI
and 2.3 g (0.1 mol) fresh sodium were added. When the sodium had dis-
appeared, the ethanol produced was distilled off. The reaction mixture
was then cooled to room temperature. NaCl was filtered and washed with
2
1
0 mL ethylenediamine. Vacuum distillation gave 21.0 g product. b.p.
ꢂ
18–122 C/7 mmHg, yield: 83%.
Synthesis of N-Alkyldiethanolamines (II)
Preparation of ethyl bromide. To a 250 mL three-necked flask installed
with thermometer and condenser, 138 g (3.0 mol) ethanol and 0.5 mL con-
ꢂ
centrated sulfuric acid were added. Heat the mixture to 75 C and induce
HBr gas, produced in another 500 mL three-necked flask by adding drop-
wise 176 g (1.2 mol) of bromine to 108 g (1.0 mol) of 4-methylphenol over
1
2 h. By neutralization with 30% sodium hydroxide solution, drying and
ꢂ
ꢂ
12
distillation, 108 g ethylbromide was obtained, b.p. 38–39 C (b.p. 38.2 C),
Yield: 83%.
Similarly, n-propylbromide was prepared with the yield 82% from
ꢂ
ꢂ
ꢂ
13
n-propanol at 90 C for 10 h, b.p. 71–72 C (b.p. 71 C). n-Butylbromide
ꢂ
was prepared with the yield 81% from n-butanol at 110 C for 10 h, b.p.
ꢂ ꢂ
12
01–102 C (b.p. 101.3 C). n-Pentyl bromide was prepared with the yield
1
7
ꢂ
ꢂ
ꢂ
13
8% from n-pentanol at 120 C for 10 h, b.p. 127–128 C (b.p. 127–128 C).
Preparation of N-ethyldiethanolamine (II). Diethanolamine 12.26 g
0.12 mol) was mixed with ethylbromide 18.30 g (0.17 mol) in a flask fitted
(
with a double coil type condenser cooled by circulating ice–water. After the
mixture was kept at reflux for 76 h, 12 g 50% sodium hydroxide solution and
5
ing 11.4 g of N-ethyldiethanolamine, b.p. 249–251 C (b.p. 117–118 C/
mL benzene was added. The organic layer was distilled in vacuum, yield-
ꢂ
ꢂ
1
4
3
mmHg). Yield: 72%.
Similarly, N-n-propyldiethanolamine b.p.108–110 C/2 mmHg (b.p.
ꢂ
ꢂ
14
22–123 C/2 mmHg), N-n-butyldiethanolamine b.p. 116–118 C/2 mmHg
ꢂ
1
(
2
ꢂ
15
ꢂ
b.p. 116–118 C/2 mmHg) and N-n-pentyldiethanolamine b.p. 125–127 C/
ꢂ
15
mmHg (b.p. 125–127 C/2 mmHg) were prepared from n-propylbromide,
n-butylbromide and n-pentylbromide for 36 h, 30 h, 30 h, with the yields:
9.4, 72 and 78% respectively.
7
Synthesis of 2-c-N-(Aminoethyl)aminopropyl-2-methyl-6-
alkyl(aryl,H)-1,3-dioxa-6-aza-2-silacyclooctanes (IIIa–f )
General procedure: To a 100 mL flask, 0.15 mol 2-g-N-(amino-ethyl)
aminopropylmethyldimethoxysilane (I), 0.15 mol diethanolamine or

ORDER
REPRINTS
NEW KINDS OF SILOCANES
2821
N-alkyldiethanolamines or N-phenyldiethanolamine, 50 mL toluene and
.1 g sodium were added. Reflux the mixture for 8 h. The methanol
produced was fractionally distilled off slowly, and then the solvent with
0 cm Vigreux column. By distillation in vacuum, the products were
received.
0
2
2
octane (IIIa): C H N O Si. Found: C 48.37, H 10.43, N 16.77;
-g-N-(Aminoethyl)aminopropyl-2-methyl-1,3-dioxa-6-aza-2-silacyclo-
1
0
25
3
2
ꢂ
Calcd.: C 48.55, H 10.18, N 16.98. b.p. 153–156 C/7 mmHg; yield: 89%;
1
H NMR d (ppm) 0.0 (3H, s), 0.5 (2H, t), 1.2–1.6 (6H, m), 2.4–2.9 (10H,
m), 3.6 (4H, t). IR (cm ) 3299 (nN-H), 1590 (dNH2), 1128 (n Si-O), 799
ꢁ
1
as
s
(
n
Si-O), 523 (n
).
N ! Si
2
-g-N-(Aminoethyl)aminopropyl-2-methyl-6-ethyl-1,3-dioxa-6-aza-2-
silacyclooctane (IIIb): C H N O Si. Found: C 52.12, H 10.33, N 15.48;
ꢂ
1
2
29
3
2
Calcd.: C 52.32, H 10.61, N 15.25. b.p. 162–165 C/10 mmHg; yield: 94%;
1
H NMR d (ppm) 0.0 (3H, s), 0.5 (2H, t), 1.5–1.6 (5H, m), 2.5–2.7 (12H, m),
ꢁ
1
as
3
7
.7 (4H, t), 1.0 (3H, t). IR (cm ) 3308 (nN-H), 1592 (dNH2), 1133 (n Si-O),
s
99 (n Si-O), 531 (n
)
N ! Si
2
-g-N-(Aminoethyl)aminopropyl-2-methyl-6-propyl-1,3-dioxa-6-aza-
2-silacyclooctane (IIIc): C H N O Si. Found: C 53.82, H 10.58, N 14.16;
Calcd.: C 53.94, H 10.79, N 14.52. b.p. 173–176 C/10 mmHg; yield: 91%;
1
3
31
3
2
ꢂ
1
H NMR d (ppm) 0.1 (3H, s), 0.6 (2H, t), 1.4–1.7 (7H, m), 2.4–2.8 (12H, m),
ꢁ1
as
3
8
.7 (4H, t), 0.9 (3H, t). IR (cm ) 3308 (nN-H), 1593 (dNH2), 1121 (n Si-O),
s
00 (n Si-O), 534 (n
).
N ! Si
2
silacyclooctane (IIId): C H N O Si. Found: C 55.10, H 10.61, N 13.61;
Calcd.: C 55.40, H 10.96, N 13.84. b.p. 182–185 C/10 mmHg; yield: 73%;
1
-g-N-(Aminoethyl)aminopropyl-2-methyl-6-butyl-1,3-dioxa-6-aza-2-
1
4
33
3
2
ꢂ
H NMR d (ppm) 0.0 (3H, s), 0.5 (2H, t), 1.3–1.5 (9H, m), 2.4–2.8 (12H, m),
ꢁ
1
as
3
8
.6 (4H, t), 0.9 (3H, t). IR (cm ) 3302 (nN-H), 1590 (dNH2), 1124 (n Si-O),
s
00 (n Si-O), 536 (n
).
N ! Si
2-g-N-(Aminoethyl)aminopropyl-2-methyl-6-pentyl-1,3-dioxa-6-aza-
-silacyclooctane (IIIe): C H N O Si. Found: C 56.65, H 11.35, N 13.22;
2
Calcd.: C 56.74, H 11.11, N 13.23. b.p. 190–192 C/10 mmHg; yield: 85%;
1
5
35
3
2
ꢂ
1
H NMR d (ppm) 0.1 (3H, s), 0.7 (2H, t), 1.3–1.6 (11H, m), 2.3–2.8 (12H,
ꢁ
1
as
m), 3.6 (4H, t), 0.9 (3H, t). IR (cm ) 3298 (nN-H), 1581 (dNH2), 1120 (n
O), 799 (n Si-O), 530 (n
Si-
s
).
N ! Si
2
-silacyclooctane (IIIf ): C H N O Si. Found: C 59.40, H 9.04, N
-g-N-(Aminoethyl)aminopropyl-2-methyl-6-phenyl-1,3-dioxa-6-aza-
2
1
1
6
29
3
2
ꢂ
2.99; Calcd.: C 59.32, H 9.08, N 12.81. b.p. 242–245 C/7 mmHg;
1
yield: 84%; H NMR d (ppm) 0.0 (3H, s), 0.6 (2H, t), 1.4–1.7 (5H,
m), 2.5–2.9 (6H, m), 3.7 (4H, t), 4.0 (4H, t), 6.7–7.4 (5H, m). IR (cm
s
3
ꢁ
1
)
as
308 (nN-H), 1598 (dNH2), 1135 (n Si-O), 800 (n Si-O), 528 (n
).
N ! Si

ORDER
REPRINTS
2
822
YANG, LIN, AND LI
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Received in the USA November 21, 2000

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