Synthesis of γ-N-arylideneaminopropyl-2-methyl-6-phenyl-1,3-dioxa-6-aza-2- silacyclooctanes

Article abstract of DOI:10.1081/SCC-100107022

Several new γ-N-arylideneaminopropyl-2-methyl-6-phenyl-1,3-dioxa-6-aza-2- silacycloo ctanes have been prepared by the reaction of γ-aminopropyldimethoxymethylsilane with phenyldiethanolamine first and then with arylaldehydes. The products were identified

Full text of DOI:10.1081/SCC-100107022

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SYNTHESIS OF γ-N-ARYLIDENEAMINOPROPYL-2-
METHYL-6-PHENYL-1,3-DIOXA-6-AZA-2-
SILACYCLOOCTANES
Fangzheng Li a , Jimao Lin b & Qinzheng Yang a
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: 16 Aug 2006.
To cite this article: Fangzheng Li , Jimao Lin & Qinzheng Yang (2001) SYNTHESIS OF γ-N-ARYLIDENEAMINOPROPYL-2-
METHYL-6-PHENYL-1,3-DIOXA-6-AZA-2-SILACYCLOOCTANES, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 31:23, 3715-3720, DOI: 10.1081/SCC-100107022
To link to this article: http://dx.doi.org/10.1081/SCC-100107022
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SYNTHETIC COMMUNICATIONS, 31(23), 3715–3720 (2001)
SYNTHESIS OF c-N-
ARYLIDENEAMINOPROPYL-
2-METHYL-6-PHENYL-1,3-DIOXA-
6-AZA-2-SILACYCLOOCTANES
Fangzheng Li, Jimao Lin,*
and Qinzheng Yang
School of Chemistry and Environmental Science,
Shandong University, Jinan, 250 100,
Shandong, P. R. China
ABSTRACT
Several new g-N-arylideneaminopropyl-2-methyl-6-phenyl-
1,3-dioxa-6-aza-2-silacyclooctanes have been prepared by
the reaction of g-aminopropyldimethoxymethylsilane with
phenyldiethanolamine first and then with arylaldehydes. The
products were identified by elemental analyses, IR and
1H NMR.
Silatranes1,2 containing Schiff’s base component (Figure 1) have been
synthesized and studied.3–5 It has been reported that some of them show
definite antitumor activity.3,4 In those compounds, the main groups, are the
pentacoordinate bond as a result of transannular dative bonding between
* Corresponding author.
3715
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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3716
LI, LIN, AND YANG
Figure 2.
Figure 1.
the nitrogen and silicon atoms1 and the Schiff’s base component. To study
6
further those structures and their analogies, several newpseudosilatranes
(III in Figure 2) which contain Schiff’s base component and an eight
member heterocycle bridged by weak nitrogen-silicon interaction,7,8 have
been prepared by the condensation of arylaldehydes with 3-aminopropyl-
2-methyl-6-phenyl-1,3-dioxa-6-aza-2-silacyclooctane II.
Our synthesis started with an alcohol exchange reaction on silane I
with phenyldiethanolamine (Scheme 1). In the first step, the principal
side reaction is the polymerization. In order to obtain a good yield, a
solvent/reactant ratio of 2:1 was used.
CH3
j
ðHOCH2CH2Þ2NC6H5
H2NCH2CH2CH2 SiðOCH3Þ2
ÀÀÀÀÀÀÀÀÀÀÀÀÀÀÀ!
I
CH3
j
H2NCH2CH2CH2 SiðOCH2CH2Þ2NC6H5
II
Scheme 1:
The final products were synthesized as depicted in Scheme 2. In this
step anhydrous K2CO3 was used as desiccant and dry benzene as solvent.
Residual water was removed by azeotropic distillation.

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3717
Scheme 2.
The results are listed in the Table.
Table. Reaction Time, Yield, and Physicochemical Data
Reaction Yield
Reaction Time (h)
Entry
Ar
Physical Data
(R.T.) (for scheme 2) Scheme 2 Total Reaction
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
IIIh
IIIi
C6H5
Light yellow(oil)
Light yellow(oil)
Yellow2 h
3 h
2 h
99%
99%
80%
80%
p-C6H4F
o-C6H4Cl
o-C6H4Br
p-C6H4Cl
99%
80%
Yellow(oil)
Light yellow(oil)
2 h
2 h
6 h
99%
99%
98%
99%
99%
98%
80%
80%
79%
80%
80%
79%
p-C6H4SCH3 Light yellow(oil)
p-C6H4OCH3 Yellow(oil)
m,p-C6H3Cl2 Light yellow(oil)
10 h
2 h
m,p-C6H3
(OCH3)2
Yellow(oil)
12 h
EXPERIMENTAL
IR spectra were recorded with VECTOR 22 IR spectrometer in
the region 4000–400 cmÀ1. Proton nuclear resonance spectra were obtained
on a FX90Q spectrometer using CDCl3 as solvent. Elemental analyses were
carried out on a Yanaco MT-3 elemental analyzer. Thermometers were not
corrected.

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LI, LIN, AND YANG
Synthesis of c-Aminopropyl-2-methyl-6-
phenyl-1,3-dioxa-6-aza-2-silacyclooctane(II)
To a 500 mL dry flask, 35.05 g (0.218 mol) I (distilled in 184–187ꢀC),
39.45 g (0.218 mol) phenyldiethanolamine and 250 mL toluene were added.
The mixture was refluxed for 8 h. The reaction product about 12.5 g metha-
nol was distilled off. The mixture was heated for another 10 h at 100ꢀC.
Toluene was removed and the crude product was distilled in vacuum to give
49.90 g III. b.p 188–190ꢀC/10 mmHg; yield: 81%. IR (cmÀ1): 3370, 3022,
1
3058, 2920, 2877, 1134, 1067, 537, 505; H NMR (CDCl3): d (ppm): 0.05
(3H, s; CH3-Si), 0.58(2H, t; CH2-Si), 1.55 (4H, m; CH2-C-Si, H2N), 2.68
(2H, t; CH2-C-C-Si), 3.75 (4H, m; CH2-N), 4.07 (4H, t; CH2-O), 6.70–7.45
(5H, m; Ar-H); Anal. Calcd (%). for C14H24N2O2Si: C 59.96, H 8.63, N
9.99, Found (%): C 59.87, H 8.59, N 9.84.
Synthesis of c-N-Arylideneaminopropyl-2-methyl-6-
phenyl-1,3-dioxa-6-aza-2-silacyclooctanes(IIIa–i)
General Procedure (Using IIIb as Example)
All aryl aldehydes were distilled in vacuum prior to use.
Into a dried 25 mL round bottomed flask, 2.321 g (8.29 mmol), II,
1.03 g (8.29 mmol) 4-fluorobenaldehyde, 15 mL dry benzene and 2 g of
K2CO3 were added. The mixture was shaken and then allowed to stand at
room temperature for over 2 h. K2CO3 was filtered off. The flask was fitted
with 20 cm Vigreux column and the benzene was distilled slowly. Additional
benzene was added continuously to keep about 10 mL solvent in the flask
for 1 h. The solvent was distilled first under normal pressure and then
in vacuum (110ꢀC/5–10 mmHg) for 3 h to obtain product IIIb: 3.32 g
Yield: 99%.
IIIa–i were prepared by the similar procedure. The chemical name, IR,
1H NMR, and elemental analyses data are listed below.
c-N-Benzylideneaminopropyl-2-methyl-6-phenyl-1,3-dioxa-6-aza-2-
silacyclooctane (IIIa): IR (cmÀ1): 3025, 3058, 1645, 1136, 1069, 534, 505;
1HNMR (CDCl3): d (ppm): À0.04 (3H, s; CH3-Si), 0.54 (2H, t; CH2-Si), 1.75
(2H, m; CH2-C-Si), 3.52 (6H, m; CH2N), 3.88 (4H, t; CH2-O), 6.70–7.45
(10H, m; Ar-H), 8.08 (1H, s; CH¼N); Anal. Calcd (%). for C21H28N2O2Si:
C 68.44, H 7.66, N 7.60, Found (%): C 68.15, H 7.55, N 7.73.
c-N-( p-Fluorobenzylidene)aminopropyl-2-methyl-6-phenyl-1,3-dioxa-6-aza-
2-silacyclooctane (IIIb): IR (cmÀ1): 3062, 3039, 1648, 1136, 1069, 535, 505;
1H NMR (CDCl3): d (ppm): 0.01 (3H, s; CH3-Si), 0.64 (2H, t; CH2-Si), 1.79

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3719
(2H, m; CH2-C-Si), 3.55 (6H, m; CH2N), 4.01 (4H, t; CH2-O), 6.69–7.81
(9H, m; Ar-H), 8.17 (1H, s; CH¼N); Anal. Calcd (%). for C21H27N2O2SiF:
C 65.25, H 7.04, N 7.25, Found (%): C 65.60, H 7.03, N 7.43.
c-N-(o-Chlorobenzylidene)aminopropyl-2-methyl-6-phenyl-1,3-
dioxa-6-aza-2-silacyclooctane (IIIc): IR (cmÀ1): 3063, 3025, 1637, 1137,
1
1069, 535, 505; HNMR (CDCl3): d (ppm): À0.05 (3H, s; CH3-Si), 0.56
(2H, t; CH2-Si), 1.75 (2H, m; CH2-C-Si), 3.55 (6H, m; CH2N), 3.95 (4H,
t; CH2-O), 6.57–7.98 (9H, m; Ar-H), 8.53 (1H, s; CH¼N); Anal. Calcd (%)
for C21H27N2O2SiCl: C 62.59, H 6.75, N 6.95, Found (%): C 62.35, H 6.55,
N 6.89.
c-N-(o-Brombenzylidene)aminopropyl-2-methyl-6-phenyl-1,3-
dioxa-6-aza-2-silacyclooctane (IIId): IR (cmÀ1): 3062, 3024, 1635, 1137,
1
1069, 535, 505; H NMR (CDCl3): d (ppm): À0.06 (3H, s; CH3-Si), 0.54
(2H, t; CH2-Si), 1.74 (2H, m; CH2-C-Si), 3.55 (6H, m; CH2N), 3.95 (4H,
t; CH2-O), 6.57–8.02 (9H, m; Ar-H), 8.55 (1H, s; CH¼N); Anal. Calcd (%).
for C21H27N2O2SiBr: C 56.37, H 6.08, N 6.26, Found (%): C 56.37, H 6.33,
N 6.16.
c-N-( p-Chlorobenzylidene)aminopropyl-2-methyl-6-phenyl-1,3-
dioxa-6-aza-2-silacyclooctane (IIIe) : IR (cmÀ1): 3062, 3024, 1645, 1137,
1
1069, 537, 505; H NMR (CDCl3): d (ppm): À0.01 (3H, s; CH3-Si), 0.49
(2H, t; CH2-Si), 1.61 (2H, m; CH2-C-Si), 3.46 (6H, m; CH2N), 3.88 (4H,
t; CH2-O), 6.50–7.55 (9H, m; Ar-H), 8.00 (1H, s; CH¼N); Anal. Calcd (%).
for C21H27N2O2SiCl: C 62.59, H 6.75, N 6.95, Found (%): C 62.42, H 6.85,
N 7.08.
c-N-( p-Methylthiobenzylidene)aminopropyl-2-methyl-6-phenyl-1,3-dioxa-
6-aza-2-silacyclooctane (IIIf): IR (cmÀ1): 3023, 1641, 1135, 1069, 536, 506;
1H NMR (CDCl3): d (ppm): À0.06 (3H, s; CH3-Si), 0.51 (2H, t; CH2-Si), 1.71
(2H, m; CH2-C-Si), 2.48 (3H, S:CH3S), 3.56 (6H, m; CH2N), 3.94 (4H, t; CH2-
O), 6.57–7.65 (9H, m; Ar-H), 8.09 (1H, s; CH¼N); Anal. Calcd (%). for
C22H30N2O2SSi: C 63.73, H 7.29, N 6.76, Found (%): C 63.58, H 7.01, N 6.86.
c-N-( p-Methoxybenzylidene)aminopropyl-2-methyl-6-phenyl-1,3-dioxa-
6-aza-2-silacyclooctanes (IIIg): IR (cmÀ1): 3062, 1637, 1137, 1069, 536, 505;
1H NMR (CDCl3): d (ppm): À0.03 (3H, s; CH3-Si), 0.56 (2H, t; CH2-Si),
1.75 (2H, m; CH2-C-Si), 3.55 (9H, m; CH3O, CH2N), 3.93 (4H, t; CH2-O),
6.59–7.98 (9H, m; Ar-H), 8.65 (1H, s; CH¼N); Anal. Calcd (%).
for C22H30N2O3Si: C 66.30, H 7.59, N 7.03, Found (%): C 66.30, H 7.59,
N 7.13.
c-N-(m,p-Dichlorobenzylidene)aminopropyl-2-methyl-6-phenyl-1,3-dioxa-
6-aza-2-silacyclooctane (IIIh): IR (cmÀ1): 3062, 1647, 1137, 1069, 536, 505;
1H NMR (CDCl3): d (ppm): À0.01 (3H, s; CH3-Si), 0.55 (2H, t; CH2-Si),
1.77 (2H, m; CH2-C-Si), 3.55 (6H, m; CH2N), 3.99 (4H, t; CH2-O),
6.61–7.83 (8H, m; Ar-H), 8.08 (1H, s; CH¼N); Anal. Calcd (%). for

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LI, LIN, AND YANG
C21H26N2O2SiCl2: C 57.66, H 5.99, N 6.40. Found (%): C 57.55, H 6.40,
N 6.39.
c-N-(m,p-Dimethoxybenzylidene)aminopropyl-2-methyl-6-phenyl-1,3-
dioxa-6-aza-2-silacyclooctane (IIIi): IR (cmÀ1): 3061, 1644, 1135, 1069, 536,
505; 1H NMR (CDCl3): d (ppm): 0.03 (3H, s; CH3-Si), 0.60 (2H, t; CH2-Si),
1.70 (2H, m; CH2-C-Si), 3.61-3.72 (12H, S: CH3O, CH2N), 4.01 (4H, t; CH2-
O), 6.66–7.49 (8H, m; Ar-H), 8.16 (1H, s; CH¼N); Anal. Calcd (%).
for C23H32N2O4Si: C 64.45, H 7.52, N 6.55, Found (%): C 64.45, H 7.42,
N 6.41.
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4. Kato Shozo, Jpn. Kokai Tokkyo Koho, JP 62,221,692, Chem. Abstr.
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5. Ji-Mao, Lin.; Li, Fang.; Wen-Tao, Huang. Synth. Research. Inorg.
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Received in the USA February 9, 2001

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