S. Duda-Johner et al. / Journal of Organometallic Chemistry 686 (2003) 75Á
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3.1.3. (5-(Dimethyl(3-phthalimidopropyl)silyl)pentyl)-
dimethyl(3-phthalimidopropyl)ammonium bromide (3)
This compound was synthesized according to Ref. [2].
2.9. CI MS: m/z 634 (17) [MCation
[MCation
63.56; H, 6.36; N, 5.77. Calc. for C39H46BrN3O4Si
(Mrꢀ728.80): C, 64.27; H, 6.36; N, 5.77%.
ꢀ
/
CH2]ꢁ, 633 (2)
ꢀ
/
CH3]ꢁ, 95 (100) [BrCH4ꢁ]. Anal. found: C,
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3.1.4. (5-(Dimethyl(3-(1,8-naphthalimido)propyl)-
silyl)pentyl)dimethyl(3-(1,8-naphthalimido)propyl)-
ammonium bromide (4)
3.1.5. (5-(Dimethyl(3-phthalimidopropyl)silyl)pentyl)-
dimethyl(3-(1,8-naphthalimido)propyl)ammonium
bromide (5)
This compound was prepared from 13 (1.24 g, 3.13
mmol) and 14 (971 mg, 3.44 mmol) analogous to the
method reported for the synthesis of 4; 53% yield (1.13
A solution of 12 (1.36 g, 3.05 mmol) and 14 (968 mg,
3.43 mmol) in ethanol (12 ml) was heated under reflux
for 48 h. After the mixture was cooled to room
temperature, the solvent was removed at 30 mbar, and
ethyl acetate (50 ml) was added. The solution was
concentrated in vacuo to a volume of ca. 10 ml by
lowering the pressure slowly from 200 to 30 mbar. The
addition of ethyl acetate and subsequent evaporation of
the solvent were repeated until the product precipitated
almost quantitatively as a white amorphous solid. This
g, 1.66 mmol) of an amorphous white solid; m.p.: 147Á
148 8C. 1H-NMR ([D6]DMSO): d
0.12 (s, 6H,
SiCH3), 0.33Á0.48 (m, 4H, CCH2SiCH2C), 1.12Á1.30
(m, 4H, SiCH2(CH2)2(CH2)2Nꢁ), 1.42Á
1.69 (m, 4H,
NCH2CH2CH2Si, Si(CH2)3CH2CH2Nꢁ), 2.00Á
2.19 (m,
2H, NꢁCH2CH2CH2N), 3.04 (s, 6H, NꢁCH3), 3.21Á
3.33 (m, 2H, Si(CH2)4CH2Nꢁ), 3.36Á
3.50 (m, 2H,
NꢁCH2(CH2)2N, NCH2(CH2)2Si), 4.01Á
4.13 (m, 2H,
Nꢁ(CH2)2CH2N), 7.73Á
7.83 (m, 6H, C(O)C6H4C(O),
and H-3/H-6, naphth), 8.34Á8.43 (m, 4H, H-2/H-7 and
H-4/H-5, naphth). 13C-NMR ([D6]DMSO): d ꢂ
3.6
(SiCH3), 11.6 (N(CH2)2CH2Si), 14.2
/
ꢂ
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product was isolated by centrifugation (1100ꢃ
/g, 5
/
min), washed with n-pentane (2ꢃ20 ml), and dried in
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/
vacuo (2 h, 0.001 mbar, 20 8C) to give 4 as a white
amorphous solid. To purify the product, a boiling
saturated solution of the solid in acetone was concen-
trated by distillation at atmospheric pressure until the
product precipitated significantly. The precipitation was
completed by storing the suspension for 1 day at room
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(SiCH2(CH2)4Nꢁ), 21.2 and 21.4 (NꢁCH2CH2CH2N,
Si(CH2)3CH2CH2Nꢁ), 22.5 (NCH2CH2CH2Si), 22.9
(SiCH2CH2(CH2)3Nꢁ), 29.5 (Si(CH2)2CH2(CH)2Nꢁ),
36.9 (Nꢁ(CH2)2CH2N), 40.3 (NCH2(CH2)2Si), 49.9
temperature and for a further 3 days at ꢂ
product was isolated by centrifugation and washed with
n-pentane (2ꢃ20 ml), the purification procedure was
/
25 8C. The
/
(NꢁCH3),
60.7
(NꢁCH2(CH2)2N),
62.8
repeated twice, and the product was then dried in vacuo
(2 days, 0.001 mbar, 60 8C) to give 4 in 56% yield as an
(Si(CH2)4CH2Nꢁ), 121.8 (C-1/C-8, naphth), 122.8 (C-
3/C-6, C(O)C6H4C(O)), 127.1 (C-3/C-6, naphth), 127.2
(C-8a, naphth), 130.6 (C-2/C-7, naphth), 131.1 (C-4a,
naphth), 131.3 (C-1/C-2, C(O)C6H4C(O)), 134.3 (4C)
(C-4/C-5, naphth, and C-4/C-5, C(O)C6H4C(O)), 163.5
amorphous white solid (1.25 g, 1.72 mmol); m.p.: 193Á
194 8C. 1H-NMR ([D6]DMSO): d
0.10 (s, 6H,
SiCH3), 0.32Á0.55 (m, 4H, CCH2SiCH2C), 1.09Á1.32
(m, 4H, SiCH2(CH2)2(CH2)2Nꢁ), 1.41Á
1.71 (m, 4H,
NCH2CH2CH2Si, Si(CH2)3CH2CH2Nꢁ), 1.98Á
2.18 (m,
2H, NꢁCH2CH2CH2N), 3.05 (s, 6H, NꢁCH3), 3.21Á
3.34 (m, 2H, Si(CH2)4CH2Nꢁ), 3.34Á
3.49 (m, 2H,
NꢁCH2(CH2)2N), 3.77Á
3.88 (m, 2H, NCH2(CH2)2Si),
3.97Á 7.75 (m, 4H,
4.08 (m, 2H, Nꢁ(CH2)2CH2N), 7.66Á
H-3/H-6, 1,8-naphthalimido moiety (ꢁnaphth)), 8.23Á
8.32 (m, 8H, H-2/H-7 and H-4/H-5, naphth). 13C-NMR
3.5 (SiCH3), 11.8 (N(CH2)2CH2Si),
/
ꢂ
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(C ꢂ
NMR
(N(CH2)3Si),
([D6]DMSO): d 2.9. CI MS: m/z 584 (27) [MCation
CH2]ꢁ, 583 (3) [MCation CH3]ꢁ, 95 (100) [BrCH4ꢁ].
Anal. found: C, 61.79; H, 6.45; N, 6.27. Calc. for
C35H44BrN3O4Si (Mrꢀ678.74): C, 61.94; H, 6.53; N,
6.19%.
/
O, naphth), 167.8 (C ꢂ
([D6]DMSO):
208
/
O, C(O)C6H4C(O)). 15N-
327 (Nꢁ),
218
(Nꢁ(CH2)3N). 29Si-NMR
/
d
ꢂ
/
ꢂ
/
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ꢂ
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ꢀ
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ꢀ
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([D6]DMSO): d ꢂ
/
14.2 (SiCH2(CH2)4Nꢁ), 21.2 (NꢁCH2CH2CH2N), 21.3
(Si(CH2)3CH2CH2Nꢁ), 21.9 (NCH2CH2CH2Si), 22.8
(SiCH2CH2(CH2)3Nꢁ), 29.4 (Si(CH2)2CH2(CH2)2Nꢁ),
36.7 (Nꢁ(CH2)2CH2N), 42.4 (NCH2(CH2)2Si), 50.0
3.1.6. (5-(Dimethyl(3-(1,8-naphthalimido)propyl)-
silyl)pentyl)dimethyl(3-phthalimidopropyl)ammonium
bromide (6)
This compound was prepared from 12 (2.38 g, 5.33
mmol) and 15 (1.49 g, 6.41 mmol) analogous to the
method reported for the synthesis of 4; 73% yield (2.63
(NꢁCH3),
60.7
(NꢁCH2(CH2)2N),
62.8
(Si(CH2)4CH2Nꢁ), 121.56 (C-1/C-8, naphth), 121.65
(C-1/C-8, naphth), 126.90 (C-8a, naphth), 126.92 (4C)
(C-3/C-6, naphth), 127.1 (C-8a, naphth), 130.40 (C-2/
C-7, naphth), 130.44 (C-2/C-7, naphth), 130.94 (C-4a,
naphth), 130.99 (C-4a, naphth), 134.1 (C-4/C-5,
g, 3.87 mmol) of an amorphous white solid; m.p.: 201Á
/
1
202 8C (dec.) H-NMR ([D6]DMSO): d ꢂ
SiCH3), 0.36Á0.58 (m, 4H, CCH2SiCH2C), 1.13Á
(m, 4H, SiCH2(CH2)2(CH2)2Nꢁ), 1.47Á
1.70 (m, 4H,
NCH2CH2CH2Si, Si(CH2)3CH2CH2Nꢁ), 1.93Á
2.11 (m,
2H, NꢁCH2CH2CH2N), 3.01 (s, 6H, NꢁCH3), 3.20Á
3.30 (m, 2H, Si(CH2)4CH2Nꢁ), 3.30Á
3.41 (m, 2H,
NꢁCH2(CH2)2N), 3.61 (t, 3JHH
6.1 Hz, 2H,
/
0.07 (s, 6H,
/
/1.34
/
naphth), 134.2 (C-4/C-5, naphth), 163.0 ((C ꢂ
O)2N(CH2)3Si), 163.4 (Nꢁ(CH2)3N(C ꢂO)2). 15N-
NMR ([D6]DMSO): d ꢂ 205 and ꢂ206
327 (Nꢁ), ꢂ
(NCH2)3Si, Nꢁ(CH2)3N). 29Si-NMR ([D6]DMSO): d
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ꢀ
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