1
506
GRIGOROVA et al.
N-[4-(3-{2-[Di(quinolin-2-yl)amino]ethyl}ada-
(82 mg) of 6-chloroquinoline, 12 mg (8 mol %) of
mantan-1-yl)phenyl]quinolin-2-amine (XXIII) was
isolated as by-product in the synthesis of XXI accord-
ing to b. Yield 18 mg (16%; CH Cl –MeOH, 200:1),
Pd(dba) , 9 mg (9 mol %) of DavePhos, and 72 mg
2
(1.5 equiv) of sodium tert-butoxide in 2.5 ml of anhy-
drous dioxane was heated for 7 h under reflux. Chro-
matographic separation (CH Cl –MeOH, 50:1) gave
2
2
1
yellow amorphous material. H NMR spectrum, δ,
2
2
ppm: 1.68–1.93 m (14H, Ad, AdCH ), 2.22 br.s (2H,
57 mg (43%) of XXVII as a green–yellow viscous oily
material. H NMR spectrum, δ, ppm: 1.53–1.57 m (2H,
2
1
2
-H, Ad), 4.59–4.63 m (2H, CH N), 6.89 br.s (1H,
2
3
C H NH), 6.97 d (1H, 3″-H, J = 8.8 Hz), 7.23–7.29 m
AdCH ), 1.60–1.65 m (4H, Ad), 1.72 br.s (4H, Ad),
6
4
2
(
(
7
7
4
7
3H, 6″-H, m-H), 7.32–7.36 m (4H, 3′-H, 6′-H), 7.50 d
1,89 br.s (4H, Ad), 2.21 br.s (2H, 2-H, Ad), 3.22–
3
2H, o-H, J = 8.7 Hz), 7.54–7.64 m (3H, 7′-H, 7″-H),
3.26 m (2H, CH N), 3.90 br.s (1H, CH NH), 6.60 br.s
2
2
3
3
4
.61 d (1H, 5″-H, J = 8.2 Hz), 7.70 d (2H, 5′-H, J =
(1H, C H NH), 6.68 d (1H, 5′-H, J = 2.4 Hz), 7.06 d.d
(1H, 7′-H, J = 9.0, J = 2.5 Hz), 7.18 d (2H, m-H, J =
8.6 Hz), 7.22–7.27 m (2H, 3′-H, 3″-H), 7.30 d (1H,
5″-H, J = 2.4 Hz), 7.33 d (2H, o-H, J = 8.6 Hz),
7.39 d.d (1H, 7″-H, J = 9.1, J = 2.5 Hz), 7.86 d (1H,
8′-H, J = 9.1 Hz), 7.88 d (1H, 4′-H, J = 8.1 Hz),
.90 d (1H, 4″-H, J = 7.6 Hz), 7.95 d (1H, 8″-H, J =
.0 Hz), 8.59 d.d (1H, 2′-H, J = 4.3, J = 1.6 Hz),
.68 d.d (1H, 2″-H, J = 4.2, J = 1.5 Hz). C NMR
6 4
3
3
4
3
.8 Hz), 7.78 d (1H, 8″-H, J = 8.1 Hz), 7.79 d (1H,
″-H, J = 8.2 Hz), 7.86 d (2H, 8′-H, J = 8.5 Hz),
.95 d (2H, 4′-H, J = 8.8 Hz). Mass spectrum:
3
3
3
4
3
+
3
4
m/z 652.340 [M + H] . C H N . Calculated: (M + H)
6
4
5
42
5
3
3
52.344.
3
3
7
9
8
N-(4-{3-[2-(Quinolin-4-ylamino)ethyl]adaman-
3
4
tan-1-yl}phenyl)quinolin-4-amine (XXVI). A mix-
ture of 0.25 mmol (68 mg) of diamine III, 0.5 mmol
(
Pd(dba) , 9 mg (9 mol %) of DavePhos, and 72 mg
(
drous dioxane was heated for 7 h under reflux. Chro-
matographic separation (CH Cl –MeOH, 3:1) gave
3
rial. H NMR spectrum (DMSO-d ), δ, ppm: 1.56–
1
3
4
13
spectrum, δ , ppm: 29.1 (2C, CH ), 32.1 (1C, C ),
82 mg) of 4-chloroquinoline, 12 mg (8 mol %) of
C
Ad
Ad
3
4
4
6.0 (1C, CH2Ad), 36.4 (1C, C ), 38.5 (1C, AdCH ),
Ad 2
2
1.6 (2C, CH2Ad), 42.5 (2C, CH ), 43.4 (1C, CH N),
1.5 equiv) of sodium tert-butoxide in 2.5 ml of anhy-
2Ad
2
7
′
7″
8.5 (1C, CH ), 102.5 (1C, C ), 108.4 (1C, C ),
2Ad
m
119.2 (2C, C ); 121.3 (1C), 121.4 (2C), 122.8 (1C)
2
2
o
4a″
(
(
(
(
quinoline); 125.8 (2C, C ), 129.6 (1C, C ), 130.0
1C, quinoline), 130.1 (1C, C ); 130.3 (1C), 133.6
1C), 134.1 (1C) (quinoline); 139.6 (1C, C ), 142.1
1C, C ), 143.0 (1C, C ), 144.0 (1C, C ), 144.7 (1C,
2 mg (37%) of XXVI as a yellow viscous oily mate-
4
a′
1
6
i
.60 m (2H, AdCH ), 1.61 br.s (4H, Ad), 1.68 br.s (2H,
2
p
8a′
8a″
Ad), 1.72 br.s (2H, Ad), 1.83 br.s (4H, Ad), 2.14 br.s
(
6
″
2′
6′
2″
C ), 145.8 (1C, C ), 146.3 (1C, C ), 147.2 (1C, C ).
Mass spectrum: m/z 525.298 [M + H] . C H N . Cal-
2H, 2-H, Ad), 3.34–3.40 m (2H, CH N), 6.50 d (1H,
2
+
3
3
3
7
8
7
7
8
8
′-H, J = 5.7 Hz), 6.86 d (1H, 3″-H, J = 5.3 Hz),
.30 d (2H, m-H, J = 8.6 Hz), 7.41 d (2H, o-H, J =
.6 Hz), 7.44 t (1H, quinoline, J = 7.7 Hz), 7.49–
.53 m (2H, quinoline, PhNH); 7.64 t (1H, J =
.7 Hz), 7.68 t (1H, J = 7.6 Hz), 7.79 d (1H, J =
.5 Hz), 7.86 d (1H, J = 8.5 Hz), 8.29 d (1H, J =
.5 Hz), 8.39–8.43 m (3H) (quinoline). C NMR spec-
36 37
4
3
3
culated: (M + H) 525.302.
3
N-[4-(3-{2-[Di(quinolin-6-yl)amino]ethyl}ada-
mantan-1-yl)phenyl]-N-(quinolin-6-yl)quinolin-6-
amine (XXVIII) was isolated as by-product in the
synthesis of XXVII. Yield 40 mg (41%; CH Cl –
3
3
3
3
3
2
2
1
3
MeOH, 25:1), green–yellow viscous oily material.
1
trum (DMSO-d ), δ , ppm: 28.7 (2C, CH ), 32.6 (1C,
C ), 35.6 (1C, CH ), 36.3 (1C, C ), 37.5 (1C,
AdCH ), 40.8 (2C, CH2Ad), 41.5 (1C, CH ), 42.2
6
C
Ad
H NMR spectrum, δ, ppm: 1.60–1.75 m (10H, Ad,
Ad
2Ad
Ad
AdCH ), 1.90 br.s (4H, Ad), 2.23 br.s (2H, 2-HAd),
2
3
2
2Ad
4.01–4.06 m (2H, CH N), 7.13 d (2H, m-H, J =
8.7 Hz), 7.29 d (2H, 5′-H, J = 2.0 Hz), 7.30–7.34 m
2
3
′
4
(
(
2C, CH ), 47.4 (1C, CH N), 98.0 (1C, C ), 101.1
2Ad 2
3
″
4a′
4a″
1C, C ), 118.5 (1C, C ), 119.6 (1C, C ), 122.5 (2C,
(
6H, quinoline, o-H), 7.37–7.40 m (2H, quinoline),
m
3
4
C ); 122.0 (1C), 122.1 (1C), 124.2 (1C), 124.5 (1C)
7
7
8
.48 d.d (2H, 7′-H, J = 9.2, J = 2.5 Hz), 7.35 d.d (2H,
o
3
4
3
(
quinoline); 125.7 (2C, C ); 127.3 (1C), 128.9 (1C),
″-H, J = 9.1, J = 2.4 Hz), 7.89 d (2H, 4′-H, J =
.2 Hz), 7.96–7.80 m (6H, 4″-H, 8′-H, 8″-H), 8.76 d.d
i
1
1
(
29.2 (1C), 129.5 (1C) (quinoline); 137.9 (1C, C ),
p
8a′
4′
3
4
46.2 (1C, C ), 146.3 (1C, C ), 148.1 (1C, C ), 148.7
(
2H, 2′-H, J = 4.0, J = 1.6 Hz), 8.78 d.d (2H, 2″-H,
8
a″
2′
2″
3
4
13
1C, C ), 149.1 (1C, C ), 150.4 (1C, C ), 150.8 (1C,
J = 4.2, J = 1.4 Hz). C NMR spectrum, δ , ppm:
C
4
″
+
C ). Mass spectrum: m/z 525.295 [M + H] . C H N .
Calculated: (M + H) 525.302.
3
6
37
4
2
3
9.1 (2C, CH ), 32.1 (1C, C ), 36.1 (1C, CH2Ad),
Ad Ad
6.7 (1C, C ), 40.5 (1C, AdCH ), 41.3 (1C, CH2Ad),
Ad
2
N-(4-{3-[2-(Quinolin-6-ylamino)ethyl]adaman-
tan-1-yl}phenyl)quinolin-6-amine (XXVII). A mix-
ture of 0.25 mmol (68 mg) of diamine III, 0.5 mmol
41.4 (1C, CH2Ad), 42.5 (2C, CH ), 47.6 (1C, CH N),
2Ad 2
7
′
7″
48.3 (1C, CH ), 111.5 (2C, C ), 119.1 (2C, C ),
2
m
Ad
121.5 (4C, C , quinoline); 125.0 (2C), 125.8 (2C),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 12 2012