Synthesis of spirocyclic aminosilanes with electron withdrawing substituents at nitrogen

Article abstract of DOI:10.1515/znb-1998-0202

The first synthesis of spirocyclic tetrasulfonamidosilanes is described. According to the X-Ray structure analysis of the most stable tetratosylamidosilane obtained the Silicon is bonded to four Nitrogen atoms in a spirocycle and surrounded by four Oxygen

Full text of DOI:10.1515/znb-1998-0202

Synthesis of Spirocyclic Aminosilanes with Electron
Withdrawing Substituents at Nitrogen
Markus Wollenweber2, Reinhart Keese3’*, Helen Stoeckli-Evansb
a Department of Chemistry and Biochemistry, University of Bern,
Freiestrasse 3, CH-3012 Bern
b Institut de Chimie, Universite de Neuchätel, Avenue de Bellevaux 51, CH-2000 Neuchätel
Z. Naturforsch. 53 b, 145-148 (1998); received October 24, 1997
Spirocyclic Sulfonamidosilanes, 1,2-Phenylene Diamides, Capped Tetrahedron, X-Ray Data,
Chelation
The first synthesis of spirocyclic tetrasulfonamidosilanes is described. According to the
X-Ray structure analysis of the most stable tetratosylamidosilane obtained the Silicon is bonded
to four Nitrogen atoms in a spirocycle and surrounded by four Oxygen atoms which are located
above the planes of the SiN4 tetrahedron.
1. Introduction
with SiCU. Due to the poor solubility of the starting
material in methylene chloride, the Cl-substituted
compound 5 was separated by solid/liquid extrac-
tion of the concentrated reaction mixture while 4
could hitherto not be obtained as a pure compound.
The Si-compound 5 was highly sensitive to mois-
ture but was sufficiently stable in CDCI3 solutions
for NMR measurements.
Cyclic and spirocyclic aminosilanes have been
prepared for theoretical, structural and reactivity
reasons and for specific applications [1 - 4]. Despite
the chelating effect [5], substituents at both amino
groups of ethylene diamine are necessary for the for-
mation of spirocyclic aminosilanes. A survey of the
known spirocyclic aminosilanes shows, that hith-
erto bulky and cr-donating substituents are used for
enhancing the stability of these compounds. In the
course of our interest in bridged spiro aminosilanes
we investigated the formation of spiro aminosi-
lanes from o-phenylene diamine with the amino
groups bearing electron withdrawing substituents.
In view of the propensity of silanes with electroneg-
ative substituents to form penta- and hexacoordinate
complexes and to undergo substitution reactions
readily [6 ], the isolation of such spiro aminosilanes
is remarkable.
Information about the geometry of the central
SiN4 substructure in 5 was obtained by NMR studies
in CDCI3. The *H and 13C NMR spectra showed
only 2 signals of the same intensity for the CH3
groups of the mesyl substituents, indicative of a
tetrahedral coordination of the Si atom. In the case
of a planar arrangement, 5 would exist as a mixture
of two diastereomers leading to 3 NMR signals for
the methyl groups.
2
. Results and Discussion
In a first attempt we treated 1,2-phenylenedi-
amine with SiCU in the presence of base. Since
a stable product could not be isolated, we used the
1
,2-phenylene sulfonamides 1-3 [7-91 rather than
N,N'-dialkyl phenylene amines as bidentate ligands.
In contrast to 4 and 5, the spiro compound 6
The silaspiranes 4 - 6 were prepared by deprotona- with the bulky tosyl groups was sufficiently sta-
tion of the sulfonamides using n-BuLi and reaction ble to be purified by chromatography on silica gel
and was isolated in 29% yield. In the IR spectrum,
a new, intensive band was observed at 970 cm-1,
which is not present in 3. This band is most likely
Reprint requests to Prof. Dr. R. Keese.
0
939-5075/98/0200-0145 $ 06.00 (c) 1998 Verlag der Zeitschrift für Naturforschung. All rights reserved.
K
Brought to you by | New York University Bobst Library Technical Services
Authenticated
Download Date | 7/30/15 5:04 AM

1
46
M. Wollenweber et al. ■Synthesis of Spirocyclic Aminosilanes
Fig. 2. Drawing of 6 illustrating the octahedral co-
ordination. Selected nonbonded distances (A) and an-
gles (°): 0 (4 )-S i(l) 2.953(2), 0 (2 B )-S i(l) 2.982(2),
0
0
0
(3 B )-S i(l) 2.912(3); 0(2)-Si(l)-0(2B ) 101.5(1),
(2)-Si(l)-0(3B ) 86.3(1), 0(2)-Si(l)-0(4) 158.7(1),
(2B )-Si(l)-0(3B ) 158.4(1), 0(2B )-Si(l)-0(4) 88.3(1),
Fig. 1. Structure of 2,2'-spirobi[2-silabenzimidazoline-
,3-bis-p-toluenesulfonamide] (6) with 50% thermal el-
0(3B)-Si(l)-0(4) 91.5(1).
1
lipsoids. Selected bond lengths (A), bond and tor- Si-N-S-0 ±5°). This geometry can be described as
sional angles (°) N( 1)-C( 1) 1.446(4), N( 1)-S( 1) 1.653(2),
a distorted dodecahedral arrangement for a [4+4]
N (l)-Si(l) 1.728(3); N(2)-Si(l)-N(1B) 119.93(13), N (l)-
octacoordinated Si [14, 15] (Fig. 2). It is unclear,
Si(l)-N(2) 91.34(12), Si(l)-N(2)-C(6) 112.1(2), N(2)-
whether the average value of the short O -S i dis-
C(6)-C(l) 112.5(3), C(6)-C(l)-N(l) 11.6(3), C(l)-N (l)-
Si( 1) 112.4(2); Si( 1)-N( 1)-C( 1)-C(2) -176.70(27), Si( 1)- tances of 2.95(1) A indicates a bonding interaction
N(2)-C(6)-C(5) -178.51 (28), S( 1B)-N( 1B)-C( 1B)-C(2B)
or whether this structural feature is a result of crystal
packing.
1
.48(44).
caused by a Si-N vibration [10]. The 29Si NMR
spectrum showed a broad signal at -95.3 ppm rel-
ative to TMS. This value is closer to the signal
4
. Concluding Remarks
In contrast to Si[N(CH3)2]4 [17] and the com-
of Si(OCH3)4 at -79.0 ppm [11]) than to that of pounds 4 and 5 the spirocyclic tetrasulfonylamidosi-
lane 6 containing the bidentate ligand 3 is rather
stable to moisture. According to its spectrum the
Si nucleus is highly shielded in compound 6 . An
X-ray analysis reveals that one Oxygen atom of
each sulfonyl group is located above a plane of
Si[N(CH3)2]4 (-28.1 ppm [12 ]) and indicates, that
the Si nucleus is strongly shielded.
3
. X-Ray Structure Analysis
The structure analysis of 6 revealed two essen- the tetrahedron, defined by the central SiN4 unit of
tially planar silabenzimidazoline ring systems al- the spirocycle in 6 . The tetrahedral arrangement of
most orthogonal to one another (Fig. 1). The angle the central SiN4 substructure in 6 corroborates the
between the two planes defined by the silicon atom earlier observations of the 1,2 -dihydroxyphenylene
and the two N atoms, N(l)-Si(l)-N(2) and N(1B)- esters of Si(OH)4 which show tetrahedral coordi-
Si( 1)-N(2B), respectively, was found to be 88.4( 1)°. nation for the Si in the central Si0 4 substructures
The Si atom shows a tetrahedral coordination with [18-20], Whether further spirocyclic amidosilanes
smaller endocyclic (ca. 91.3(1)°) and larger exo- can be prepared from chelating diamines bearing
cyclic angles (ca. 119.2(1)°) [13]. The average value electron withdrawing substituents will be investi-
of the N-Si bond (1.733(2) A) is within the normal gated.
range [13].The torsion angle C(2)-C(l)-N(l)-S(l)
is 15.5(4)° indicating a slight pyramidalization of
Experimental
N (l) while the other N atoms are essentially trig-
General remarks. All chemicals were obtained from
onal planar. Strikingly, four sulfonamide oxygens
cap the (N)4Si tetrahedron each bisecting one of
the four tetrahedron faces, somewhat reminiscent
of nucleophilic additions to silicon (torsion angles:
Fluka, Buchs, and used as purchased. The silica gel
C 560, 60-200 mesh) for column chromatography
was purchased from CU Chemie Uetikon AG. TLC
(
plates (Alugram SIL G/UV254) were obtained from
Brought to you by | New York University Bobst Library Technical Services
Authenticated
Download Date | 7/30/15 5:04 AM

M. Wollenweber et al. • Synthesis of Spirocyclic Aminosilanes
147
Macherey-Nagel, Düren. Melting points (uncorrected)
were determined on a Büchi 510 apparatus. Infrared spec-
M.p. 199°C (203° corr. [9]); IR (KBr): 3220, 1596,
1498, 1326, 1148; 'H NMR (CDCU): 7.57 (d, J = 8 Hz,
tra were recorded on a Perkin Elmer 1600 series FTIR.
H-NMR (300 MHz) and 13C NMR (75 MHz) and 29Si
NMR (99.3 MHz) spectra were determined on Bruker
00 MHz and 400 MHz Spectrospin AC 300 and AC 400
instruments, <5 in ppm using TMS as internal standard.
Mass spectra were obtained on a Varian MAT CH 7A
spectrometer (70 eV, El), high resolution MS were per-
formed on a VG ZAB 2F instrument. All reactions were
run under Ar. Elemental analyses were performed by the
Lab. de Chimie Pharmaceutique, Universite de Geneve.
For further details see [21].
4 H), 7.22 (d, 4 H), 7.05 - 7.01 (m,2 H), 6.97 - 6.93 (m, 2
H), 6.93 (s, 2 H), 2.39 (s, 6 H); 13C NMR (CDCU): 144.2
(s, 2 C), 135.4 (s, 2 C), 130.8 (s, 2 C), 129.6 (d, 4 C),
127.6 (d, 4 C), 127.4 (d, 2 C), 126.2 (d, 2 C), 21.6 (q, 2
C); MS: 416 (M+, 22), 261(100), 182 (31), 91 (64).
'
3
2,2'-Spirobi( l,3-bismethylsulfonyl)-2-silabenz-
imidazoline (4)
To a suspension of 1 (2.00 g, 7.57 mmol) in THF
(
60 ml) was added 9.46 ml n-BuLi (1.6M solution in
hexane, 15.14 mmol) at 0°C. After stirring at 0°C for 15
min a soln. of SiCU (3.79 ml, 3.79 mmol) in THF was
added at 0°C. After reflux for 20 h the suspension was
concentrated to dryness, the residue taken up in CH2Cl2
To a soln. of 1,2-phenylenediamine (14.00 g, 129.5
mmol) in CH2CI2 (200 ml) and pyridine (42 ml) was
added a soln. of MsCl (20.1 ml, 259 mmol) in CH2C12
(
200 ml) at 0°C. After stirring at r. t. for 20 h H20 (300
(
60 ml), stirred at room temperature for 45 min and filtered
ml) and 300 ml 1N HC1 were added and 1 precipitated.
More 1 was obtained by evaporation of the CH2C12 soln..
Crude 1 was washed with IN HC1, acetic acid and dried
in vacuo to afford orange crystals 30.56 g (89%).
through celite. Crystallization from CH2CI2 at -20 °C
provided a mixture (370 mg) of 4 (11%) and 1 (7%) in
the ratio of 4:3 according to ' H NMR.
'
H NMR (CDCI3): 6 7.55 (4 H), 7.21 (4 H), 3.37 (s,12
H); MS: 552 (M+ -1, 1), 342 (14), 263 (71), 185(100),
07 (80); HR-MS: calc, for C ^ o ^ C ^ S i : 551.9933,
found 551.9933.
M .p. 206 - 208°C (214° corn [8 ]); IR (KBr): 3275,
3
020, 2932, 1332, 1152; 'H NMR (DMSO-</6): 8.93 (s, 2
H), 7.45 (m, 2 H), 7.25 (m, 2 H), 3.06 (s, 6 H); ,3C NMR
DMSO-dfi): 130.8 (s, 2 C), 126.6 (d, 2 C), 124.9 (d, 2 C),
1
(
4
0.1 (q, 2 C); MS: 264 (M \19), 185(100), 107 (70).
2
,2'-Spirobi(6-chloro-1,3-bismethylsulfonyl)-2-silabenz-
imidazoline (5)
4
-Chloro-N,N'-1,2-phenylenebismethanesuIfonamide (2)
Similarly to 4, 5 was prepared from 2 (2.00 g, 6.69
mmol) in THF (80 ml), 8.36 ml «-BuLi (1.6 M soln.
in hexane, 13.38 mmol) and a soln. of SiCU (3.35 ml,
Similarly to 1, 2 was obtained from 4-chloro-1,2-
phenylenediamine (7.00 g, 49.1 mmol), 15.8 ml pyridine
and MsCl (7.63 ml, 98.2 mmol) in 200 mL CH2CI2 at 0
3
.35 mmol) in THF first by stirring at 0°C then refiuxing
°C and stirring for 20 h at r. t. The precipitated 2 was re-
for 20 h. The solvent was evaporated and the residue
taken up in CH2CI2 (60 ml), stirred at r. t. for 45 min and
filtered through celite (sublimation at 170 °C/0.1 Torr or
GC failed). Crystallization from CH2CI2 at -20 °C gave
crystallized from acetic acid (ca. 300 ml) to give reddish
crystals of 2(9.12 g, 62%).
M.p. 194°C; Rf (ethyl acetate) 0.54; IR (KBr): 3264,
3
014, 2936, 1330, 1148; 'H NMR (DMSO-d6): 9.15 (s,
1
1
(
4
H), 9.07 (s, 1 H), 7.50-7.45 (m, 2 H), 7.30 (dd, J = 5 as colorless crystals (672 mg, 32%).
5.0, 2.3 Hz, 1 H), 3.19 (s, 3 H), 3.08 (s, 3 H); l3C NMR
M. p. 260°C (dec.); IR (KBr): 3030, 2936, 1356, 1156;
DMSO-fife): 132.5, 130.4, 129.1, 126.7, 126.0, 123.5,
0.4, 40.1; MS: 300 (M+ +1, 7), 298 (19), 219(100),
41 (85).
'H NMR (CDCI3): 7.55 (d, J = 2.2Hz, 2 H), 1 A I (d, J
= 8.8 Hz, 2 H), 7.19 (dd, J = 8 .8 , 2.2 Hz, 2 H), 3.38
(s,6 H), 3.35 (s, 6 H); l3C NMR (CDCI3): 130.1, 129.0,
1
1
6
26.8, 124.5, 115.0, 114.7,40.6,40.5; MS: 622(M +,89),
20(100), 543 (34), 541 (39), 341 (12), 141 (28); HR-
MS: calc, for Ci6 His Cl2 N4 0 8 S4 Si: 619.9154, found
Analysis for C8H, i C l ^ C ^ (298.77)
Calcd C 32.16 H3.71 Cl 11.87 N 9.38 S 21.46%,
Found C 32.35 H 3.74 Cl 11.99 N 9.16 S 21.11%.
6
19.9158.
N,N'-1,2-Phenylenebistoluenesulfonamide (3) [9]
2
,2'-Spirobi( 1,3-bistoluenesulfonyl)-2-silabenz-
As described above, 1,2-phenylenediamine (7.00 g,
imidazoline (6)
6
4.7 mmol), 20.8 ml pyridine and p-TsCl (24.67 g, 129.4
mmol) gave after stirring in 2 0 0 ml CH2CI2 at r. t. for
h, addition of water (200 mL) and extraction with 1N
HC1 (300 ml) crude 3 which was washed with IN HC1.
Recrystallization from acetic acid provided orange crys-
tals (26.49 g, 98%).
As described for 4 and 5,6 was prepared from 3 (2.00 g,
4.80 mmol) 6.00 ml n-BuLi (1.6 M in hexane, 9.60 mmol)
and SiCU (2.40 ml, 2.40 mmol) in dry THF at 0 °C. The
soln. was refluxed for 20 h and concentrated to dryness.
The residue was twice chromatographed on silica gel
3
Brought to you by | New York University Bobst Library Technical Services
Authenticated
Download Date | 7/30/15 5:04 AM

148
M. Wollenweber et al. • Synthesis of Spirocyclic Aminosilanes
(
(
cyclohexane / ethylacetate 1:1 + 1% triethylamine, R f
3) = 0.42, Rf (6 ) = 0.63]) providing 6 after recrystal-
Mo-KQradiation (A= 0.71073 Ä). The structures of 6 was
solved by direct methods using the program SHELXS-
90 [22]. The program SHELXL-93 [23] was used for
refinement. Hydrogen atoms were included in calculated
positions. Weighted full-matrix least-squares refinement
on F2 was used in all cases. Fig. 1 was prepared using
the program XTAL_GX [24], Further details are available
from the Cambridge Crystallographic Data Centre, on
quoting the full journal citation, and from H. St.-E.
6 : C4oH36N4 0 8S4Si, FW = 857.07, triclinic, space
group PI (No. 2), a = 12.887(3), b = 12.987(4), c =
14.020(5) A, a = 98.40( 1), ß = 95.92(2), 7 = 1 1 9.47( 1)°,
V= 1978.8(10) Ä3, Z = 2, pcaic. = 1.438 gem-3 , F(000) =
lization from acetonitrile as colorless crystals (595 mg,
2
9%).
M .p. 230°C; IR (KBr): 2924, 1598, 1482, 1348, 1170,
70; 'H NMR (CDC13): 8.18 (d, J = 8 Hz, 8 H), 7.32 -
.23 (m,12 H), 6.94 (m, 4 H), 2.37 (s,12 H); 13C NMR
CDCI3): 145.0(4 s), 135.1 (4 s), 129.7 (8 d), 128.8 (4 d),
28.5 (4 s), 123.5 (8 d), 114.5 (4 d), 21.6 (4 q); 29Si NMR
CDCI3): -95.3 (br. s); MS (El, 70 eV): 857 (M +, 100)
02 (23), 547 (5), 483 (30), 419 (15), 91 (13); HR-MS:
9
7
(
1
(
7
calc for C40 H36 N4 Os S4 Si: 856.1185; found 856.1193.
Analysis calc, for C4oH36N4 0 sS4Si (857.07)
Calcd C 56.06 H 4.23 N 6.54 S 14.96%,
Found C 56.01 H 4.27 N 6 .6 6 S 14.88%.
8
92, crystal size: 0.38 x 0.38 x 0.34 mm, reflections col-
lected 6942, independent reflections 6942, final R indices
I > 2cr(I)]: R 1 = 0.0454, wR2 = 0.0974.
[
X-Ray analysis of 6
Acknowledgements
Single crystals of 6 were grown by slow evaporation of
acetonitrile solutions at room temperature. Intensity data
were measured on a Stoe AED2 four-circle diffractometer
at room temperature, using graphite-monochromated
We thank the Swiss National Science Foundation
for financial support (Project No. 20-37270.93 and
20-43565.95 and PD Dr. P. Bigler for 29Si NMR mea-
surements.
[
1] D. Kummer, E. G. Rochow, Z. Anorg. Allg. Chem.
21,21 (1963).
2] C. H. Yoder, J. J. Zuckerman, Inorg. Chem. 3, 1329,
1964); ibid. 5, 2055 (1967); C. H. Yoder, J. J. Zuck-
[14] Similar values have been observed in the structure
of 2,2'-spirobi[l,3-dibenzyl-2-silaimidazoline] [4],
[15] Corriu has adopted the nomenclature [4+n\ to de-
scribe the geometry of capped tetrahedrons: four
covalent bonds around the Si atom + n coordinative
interactions [16].
3
[
(
erman, J. Am. Chem. Soc. 88, 2170 (1966); E. W.
Randall, C. H. Yoder, J. J. Zuckerman, Inorg. Chem.
6
,744(1967).
3] E. W. Abel, R. R Bush, J. Organomet. Chem. 3, 245
1965).
[16] F. Carre, C. Chuit, R. J. P. Corriu, A. Mehdi, C. Reye,
Angew. Chem. 106, 1152 (1994); Angew. Chem.,
Int. Ed. Engl. 33, 1097(1994).
[17] Guon-bin Rong, Youji Huaxue, 16, 68 (1996).
[18] W. Hönle, U. Dettlaff-Weglikowska, L. Walz, H.
G. v. Schnering, Angew. Chem. 101, 615 (1989);
Angew. Chem., Int. Ed. Engl. 28, 623 (1989).
[19] H. Meyer, G. Nagorsen, Angew. Chem. 91, 587
(1979); Angew. Chem., Int. Ed. Engl. 18, 551
(1979).
[
[
(
4] T. Schlosser, A. Sladek, W. Hiller, H. Schmidbaur,
Z. Naturforsch. 49b, 1247 (1994).
[
5] D.F. Shriver, R W. Atkins, C. H. Langford, In-
organic Chemistry, chapt. 7.7, Oxford University
Press, (1990).
[
6] C. Chuit, R. J. P. Corriu, C. Reye, J. C. Young, Chem.
Rev. 93, 1371 (1993).
[
7] H.-Y. Cheng, P.-H. Cheng, C.-F. Lee, S.-M. Peng,
Inorg. Chim. Acta 181, 145 (1991).
8] H. Stetter, Chem. Ber. 86, 197 (1953).
[20] J. W. Bibber, C. L. Barnes, D. van der Helm, J. J.
Zuckerman, Angew. Chem. 95,498 (1983); Angew.
Chem., Int. Ed. Engl. 22, 501 (1983).
[
[
9] H. Stetter, Chem. Ber. 86, 161 (1953).
[21] M. Thommen, A.L. Veretenov, R. Guidetti-Grept,
R. Keese, Helv. 79, 469 (1996).
[22] G. M. Sheldrick, SHELXS-90. Acta Crystallogr.
A46, 467 (1990).
[23] G. M. Sheldrick, SHELXL-93. Program for crys-
tal structure refinement, Universität Göttingen, Ger-
many (1993).
[24] S. Hall, D. du Boulay, XTAL.GX, eds. Hall and du
Boulay. University of Western Australia, Australia
(1995).
[
10] E. Pretsch, T. Clerc, J. Seibl, W. Simon, Tabellen zur
Strukturaufklärung organischer Verbindungen mit
spektroskopischen Methoden, p. 1 - 255, Springer
Verlag, Berlin, Heidelberg, New York, (1976).
[
[
[
11] H.-G. Horn, H. C. Marsmann, Makromol. Chem.
162, 255 (1972).
12] H. Jancke, G. Engelhardt, M. Mägi, E. Lippmaa, Z.
Chem. 13. 435 (1973).
13] G. Klebe, J. Organomet. Chem. 293, 147 (1985).
Brought to you by | New York University Bobst Library Technical Services
Authenticated
Download Date | 7/30/15 5:04 AM