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Can. J. Chem. Vol. 81, 2003
dium hydroxide (1:2 molar ratio) followed by a vacuum dis-
tillation using a liquid N2 cooled trap (14). At 0 °C, the
solution of (2-chloroethyl)dimethylamine in THF (80 mL)
was added dropwise to a suspension of indenyl sodium
(55.3 g, 400.0 mmol) in THF (200 mL). Stirring overnight at
room temperature (r.t.) and subsequent refluxing for 2 h
gave a green reaction mixture. The volatile components
were evaporated and the residue was hydrolyzed with cooled
H2O (400 mL). After extraction of the resulting maroon so-
lution with petrol ether (bp 35/80) (4 × 125 mL), the com-
bined organic phases were washed with H2O (3 × 300 mL)
and dried (Na2SO4). The solvent was removed in vacuo and
the crude product was distilled to give 2a as a colourless,
slightly viscous liquid (25.16 g, 134.3 mmol, 34%), bp
128.0 (C2), 143.2 (C8), 144.3 (C9), 145.6 (C3). MS (EI,
70 eV) m/z (%): 243(1) [M+], 228(2) [M+ – CH3], 115(14)
+
[Ind+], 114(100) [i-Pr2NCH2 ]. Anal. calcd. for C17H25N
(243.40):C 83.89, H 10.35, N 5.75; found: C 83.63, H 10.39,
N 5.78.
Potassium [1-(2-(N,N-dialkylamino)ethyl)indenide] salts
(3a–3c)
General procedure
The solutions of the 3-(2-dialkylaminoethyl)indenes 2a–
2c (50 mmol) in 20 mL THF were added slowly to a suspen-
sion of potassium hydride (2.01 g, 50.1 mmol) in THF
(60 mL) at –40 °C. The reaction mixtures were allowed to
warm up to r.t. and stirred for 18 h. The solvent was re-
moved in vacuo and the residues washed with n-hexane (2 ×
50 mL). After removal of the solvent, the potassium salts
were obtained as green (3a) (49.1 mmol, 98%), yellow (3b)
(40.6 mmol, 81%), or brown (3c) (46.1 mmol, 92%) solids.
1
77 °C (0.5 mbar). H NMR (CDCl3) δ: 2.37 (s, 6H, N-CH3),
3
2.67 (t, 2H, JH,H = 7.7 Hz, N-CH2-CH2-), 2.79 (t, 2H,
3
3JH,H = 7.7 Hz, N-CH2-CH2-), 3.35 (d, 2H, JH,H = 1.5 Hz,
3
allyl-H), 6.27 (t, 1H, JH,H = 1.5 Hz, vinyl-H), 7.24 (pseudo
3
3
t, 1H, JH,H = 7.5 Hz, H5), 7.34 (pseudo t, 1H, JH,H
=
3
7.5 Hz, H6), 7.42 (d, 1H, JH,H = 7.5 Hz, H4), 7.48 (d, 1H,
3JH,H = 7.5 Hz, H7). 13C NMR (CDCl3) δ: 26.0 (N-CH2-
CH2-), 37.6 (C1), 45.3 (N-CH3), 58.2 (N-CH2-CH2-), 118.6
(C4), 123.4 (C7), 124.3 (C6), 125.8 (C5), 128.1 (C2), 142.2
(C8), 144.1 (C9), 145.1 (C3). MS (EI, 70 eV) m/z (%):
(3a)
1H NMR ([D]8 THF) δ: 1.89 (s, 6H, N-CH3), 2.35 (t, 2H,
3JH,H = 6.3 Hz, N-CH2-CH2-), 2.77 (t, 2H, 3JH,H = 6.3 Hz, N-
3
CH2-CH2-), 5.56 (d, 1H, JH,H = 3.2 Hz, H2), 6.06 (d, 1H,
3JH,H = 3.2 Hz, H1), 6.27–6.31 (m, 2H, H4, H7), 7.05–7.12
(m, 2H, H5, H6). 13C NMR ([D]8 THF) δ: 26.9 (N-CH2-CH2-),
45.2 (N-CH3), 62.9 (N-CH2-CH2-), 91.4 (C2), 104.9 (C1),
112.9 (C7), 113.6 (C4), 116.8 (C6), 117.5 (C5), 119.4 (C3),
126.0 (C8), 128.9 (C9).
+
187(1) [M+], 129(4) [IndCH2 ], 115(6) [Ind+], 58(100)
+
[Me2NCH2 ]. Anal. calcd. for C13H17N (187.30): C 83.37, H
9.15, N 7.48; found: C 83.40, H 9.44, N 7.05.
3-(2-(N,N-Diethylamino)ethyl)indene (2b)
(3b)
In the same manner as described above, 2b was obtained
by reaction of (2-chloroethyl)diethylamine (1b) (62.4 g,
460 mmol) with indenyl sodium (64.9 g, 470 mmol) in 59%
3
1H NMR ([D]8 THF) δ: 0.93 (t, 6H, JH,H = 7.2 Hz, N-
3
CH2-CH3), 2.50 (q, 4H, JH,H = 7.2 Hz, N-CH2-CH3), 2.62
3
3
1
(t, 2H, JH,H = 7.1 Hz, N-CH2-CH2-), 2.84 (t, 2H, JH,H
=
yield, bp 87 °C (0.5 mbar). H NMR (CDCl3) δ: 1.09 (t, 6H,
7.1 Hz, N-CH2-CH2-), 5.61 (d, 1H, 3JH,H = 3.3 Hz, H2), 6.16
3JH,H = 7.2 Hz, N-CH2-CH3), 2.64 (q, 4H, 3JH,H = 7.2 Hz, N-
3
3
(d, 1H, JH,H = 3.3 Hz, H1), 6.33–6.35 (m, 2H, H4, H7),
CH2-CH3), 2.74 (t, 2H, JH,H = 7.4 Hz, N-CH2-CH2-), 2.81
7.12 –7.15 (m, 2H, H5, H6). 13C NMR ([D]8 THF) δ: 11.5
(N-CH2-CH3), 26.5 (N-CH2-CH2-), 46.6 (N-CH2-CH3), 56.0
(N-CH2-CH2-), 91.5 (C2), 105.1 (C1), 112.8 (C7), 113.2
(C4), 116.8 (C6), 117.6 (C5), 119.5 (C3), 126.3 (C8), 128.9
(C9).
3
(t, 2H, JH,H = 7.4 Hz, N-CH2-CH2-), 3.33 (b, 2H, H1), 6.24
3
(b, 1H, H2), 7.20 (pseudo t, 1H, JH,H = 7.4 Hz, H5), 7.30
3
3
(pseudo t, 1H, JH,H = 7.4 Hz, H6), 7.39 (d, 1H, JH,H
=
7.4 Hz, H4), 7.45 (d, 1H, JH,H = 7.4 Hz, H7). 13C NMR
(CDCl3) δ: 11.6 (N-CH2-CH3), 25.0 (N-CH2-CH2-), 37.3
(C1), 45.3 (N-CH2-CH3), 51.2 (N-CH2-CH2-), 118.4 (C4),
123.3 (C7), 124.1 (C6), 125.6 (C5), 127.7 (C2), 142.4 (C8),
143.8 (C9), 145.0 (C3). MS (EI, 70 eV) m/z (%): 215(1)
3
(3c)
3
1H NMR ([D]8 THF) δ: 1.13 (d, 12H, JH,H = 6.6 Hz, N-
3
CH-(CH3)2), 2.59 (t, 2H, JH,H = 8.5 Hz, N-CH2-CH2-), 2.82
+
[M+], 143(10) [IndCH2CH2 ], 115(6) [Ind+], 86(100)
(t, 2H,3JH,H = 8.5 Hz, N-CH2-CH2-), 3.17 (sept, 2H, JH,H
=
3
+
[Et2NCH2 ]. Anal. calcd. for C15H21N (215.34): C 83.67, H
3
6.6 Hz, N-CH-(CH3)2), 5.64 (d, 1H, JH,H = 3.3 Hz, H2),
6.29 (d, 1H, JH,H = 3.3 Hz, H1), 6.32–6.36 (m, 2H, H4,
9.83, N 6.50; found: C 83.54, H 9.90, N 6.44.
3
3
3
H7), 7.13 (dd, 1H, JH5,H4 = 3.8 Hz, JH5,H6 = 2.5 Hz, H5),
3-(2-(N,N-Diisopropylamino)ethyl)indene (2c)
3
3
7.19 (dd, 1H, JH6,H7 = 3.8 Hz, JH6,H5 = 2.5 Hz, H6). 13C
NMR ([D]8 THF) δ: 21.7 (N-CH-(CH3)2), 32.4 (N-CH2-CH2-),
49.3 (N-CH2-CH2-), 49.5 (N-CH-(CH3)2), 91.2 (C2), 105.9
(C1), 112.4 (C7), 113.0 (C4), 117.0 (C6), 117.9 (C5), 118.9
(C3), 126.6 (C8), 128.9 (C9).
Compound 2c was prepared according to the procedures
described for 2a and 2b from (2-chloroethyl)diisopropyl-
amine (1c) (79.6 g, 486 mmol) and indenyl sodium (67.7 g,
1
490 mmol) in 62% yield, bp 110 °C (0.5 mbar). H NMR
(CDCl3) δ: 1.09 (d, 12H, 3JH,H = 6.6 Hz, N-CH-(CH3)2), 2.71
3
(t, 2H, JH,H = 6.5 Hz, N-CH2-CH2-), 2.77 (t, 2H,3JH,H
=
rac/meso-[Bis(3,3′-(2-(N,N-
dimethylamino)ethyl)indenyl)]dimethylsilane (4a)
6.5 Hz, N-CH2-CH2-), 3.12 (sept, 2H, 3JH,H = 6.6 Hz, N-CH-
(CH3)2), 3.35 (b, 2H, H1), 6.26 (b, 1H, H2), 7.22 (pseudo t,
1H, JH,H = 7.5 Hz, H5), 7.33 (pseudo t, 1H, JH,H = 7.5 Hz,
3
3
Typical procedure
3
3
H6), 7.41 (d, 1H, JH,H = 7.5 Hz, H4), 7.48 (d, 1H, JH,H
=
Potassium [1-(2-(N,N-dimethylamino)ethyl)indenide] (3a)
(5.00 g, 22.2 mmol) was dissolved in THF (35mL) and
cooled to –40 °C. After dropwise addition of dimethyl-
chlorosilane (1.15 g, 8.91 mmol) in THF (25 mL), the ma-
7.5 Hz, H7). 13C NMR (CDCl3) δ: 20.8 (N-CH-(CH3)2), 30.7
(N-CH2-CH2-), 37.8 (C1), 44.7 (N-CH2-CH2-), 48.9 (N-CH-
(CH3)2), 118.9 (C4), 123.7 (C7), 124.4 (C6), 126.0 (C5),
© 2003 NRC Canada