S.-i. Takekuma et al. / Tetrahedron 67 (2011) 4780e4792
4789
137.9 (C-2000), 137.5 (C-6000), 135.9 (C-4000), 134.0 (C-8000), 132.1
(C-20,60), 130.5 (C-10), 129.4 (C-1000), 129.2 (C-200,600), 127.9 (C-100),
123.2 (C-5000), 121.9 (C-7000), 118.9 (C-3000), 117.2 (C-2), 113.0 (C-30,50),
112.7 (C-300,500), 40.2 ((CH3)2N-400), and 40.1 ((CH3)2N-40). The
numbering scheme of 3 is shown in Scheme 1.
30), 112.9 (C-300,500), 57.2 (C-1), 41.8 (C-2), and 40.4 ((CH3)2N-400). The
numbering scheme of 6 is shown in Scheme 1.
4.1.1.5. Compound 7. Blue needles [Rf¼0.55 on silica gel TLC
(solv. hexane/ethyl acetate¼50:50, v/v)]; IR nmax/cmꢁ1 (KBr), 2878,
2793 (CeH), 1616, 1519 (C]C), and 1357 (CeN); exact FABMS
(3-nitrobenzyl alcohol matrix), found m/z 521.2986, calcd for
C38H37N2: [MþH]þ, m/z 521.2957; 1H NMR (benzene-d6): signals
4.1.1.2. Compound 4. Dark green powder [Rf¼0.60 on silica gel
TLC (solv. hexane/ethyl acetate¼50:50, v/v)]; 1H NMR (benzene-
d6): signals based on an azulen-1-yl group:
d
6.59 (1H, dd, J¼9.8,
based on an equivalent of two azulen-1-yl groups: d 6.64 (2H,
9.7 Hz, H-70), 6.72 (1H, dd, J¼9.6, 9.4 Hz, H-50), 7.05 (1H, dd, J¼9.7,
9.6 Hz, H-60), 7.45 (1H, d, J¼3.8 Hz, H-30), 8.02 (1H, d, J¼9.4 Hz,
H-40), 8.05 (1H, d, J¼3.8 Hz, H-20), and 8.38 (1H, d, J¼9.8 Hz, H-80);
signals based on a non-equivalent of two 4-(dimethylamino)phenyl
dd, J¼9.8, 9.7 Hz, H-50), 6.73 (2H, dd, J¼9.8, 9.7 Hz, H-70), 7.09
(2H, dd, J¼9.8, 9.7 Hz, H-60), 7.31 (2H, d, J¼3.7 Hz, H-30), 7.88 (2H, d,
J¼9.7 Hz, H-40), 8.19 (2H, d, J¼3.7 Hz, H-20), and 8.36 (2H, d,
J¼9.8 Hz, H-80); signals based on an equivalent of two 4-(dime-
groups:
d
2.32 (6H, s, (CH3)2N-4000), 2.49 (6H, s, (CH3)2N-400), 6.22
thylamino)phenyl groups: d
2.32 (12H, s, (CH3)2N-400), 6.27 (4H, dd,
(2H, dd, J¼8.9, 2.5 Hz, H-3000,5000), 6.54 (2H, dd, J¼8.9, 2.5 Hz, H-
300,500), 7.00 (2H, dd, J¼8.9, 2.5 Hz, H-2000,6000), and 7.42 (2H, dd, J¼8.9,
2.5 Hz, H-200,600); a signal based on an ethylene unit (eHC2]C1o):
J¼8.9, 2.6 Hz, H-300,500), and 7.12 (4H, dd, J¼8.9, 2.6 Hz, H-200,600);
a signal based on an equivalent of an ethane unit (pHC1eC1Ho):
d
5.70 (2H, s, H-1); 13C NMR (benzene-d6): 148.8 (C-40), 141.3
d
d
7.45 (1H, s, H-2); 13C NMR (benzene-d6):
d
149.0 (C-4000), 145.0
(C-3a0), 137.7 (C-20), 136.8 (C-60), 136.3 (C-400), 135.8 (C-8a0), 135.0
(C-100), 134.0 (C-10), 133.6 (C-80), 129.2 (C-200,600), 122.1 (C-50), 121.6
(C-70),117.6 (C-30),112.9 (C-300,500), 49.4 (C-1), and 40.3 ((CH3)2N-400).
The numbering scheme of 7 is shown in Scheme 1.
(C-400), 140.3 (C-20), 137.6 (C-60), 136.6 (C-80), 135.9 (C-40), 134.1 (C-
100), 133.7 (C-1), 130.3 (C-2000,6000), 128.1 (C-200,600), 127.9 (C-1000), 127.8
(C-2), 122.9 (C-50), 122.8 (C-70), 118.3 (C-30), 112.7 (C-3000,5000), 112.3
(C-300,500), 40.2 ((CH3)2N-400), and 39.8 ((CH3)2N-4000). The C-10, C-3a0,
and C-8a0 carbon signals were included in other carbon signals. The
numbering scheme of 4 is shown in Scheme 1. The 1H and 13C NMR
spectral analyses of 4 (containing 3) were carried out because of
difficulty in obtaining a pure 4 by silica gel column chromatography
and recrystallization (several times).
4.1.1.6. Compound 8. Dark blue needles [Rf¼0.50 on silica gel TLC
(solv. hexane/ethyl acetate¼50:50, v/v)]; IR nmax/cmꢁ1 (KBr), 2851,
2797 (CeH), 1612, 1520 (C]C), and 1346 (CeN); exact FABMS
(3-nitrobenzyl alcohol matrix), found m/z 521.2987, calcd for
C38H37N2: [MþH]þ, m/z 521.2957; 1H NMR (benzene-d6): signals
based on an equivalent of two azulen-1-yl groups:
d 6.61 (2H,
4.1.1.3. Compound 5. Dark yellowish-brown paste [Rf¼0.40 on
silica gel TLC (solv. hexane/ethyl acetate¼50:50, v/v)]; UVevis
dd, J¼9.8, 9.2 Hz, H-50), 6.74 (2H, dd, J¼9.8, 9.8 Hz, H-70), 7.03 (2H, d,
J¼3.7 Hz, H-30), 7.09 (2H, dd, J¼9.8, 9.7 Hz, H-60), 7.78 (2H,
d, J¼9.7 Hz, H-40), 7.95 (2H, d, J¼3.7 Hz, H-20), and 8.44 (2H,
d, J¼9.8 Hz, H-80); signals based on an equivalent of two 4-(dime-
lmax/nm (log 3) in CH3CN, 204 (4.85), 269 (4.56), 309 (4.49), and
395 (4.40); IR nmax/cmꢁ1 (KBr), 2847, 2797 (CeH), 1609, 1520
(C]C), and 1350 (CeN); exact FABMS (3-nitrobenzyl alcohol
matrix), found m/z 657.3932, calcd for C46H49N4: [MþH]þ, m/z
657.3957; 1H NMR (benzene-d6): signals based on an azulene
thylamino)phenyl groups: d
2.43 (12H, s, (CH3)2N-400), 6.46 (4H, dd,
J¼8.9, 2.6 Hz, H-300,500), and 7.19 (4H, dd, J¼8.9, 2.6 Hz, H-200,600);
a signal based on an equivalent of an ethane unit (pHC1eC1Ho):
possessing two substituents at the C-1 and C-3 positions:
d
6.55
d 5.69 (2H, s, H-1). The numbering scheme of 8 is shown in Scheme 1.
(2H, dd, J¼9.8, 9.4 Hz, H-5,7), 7.02 (1H, dd, J¼9.8, 9.8 Hz, H-6),
7.76 (1H, s, H-2), and 8.16 (2H, d, J¼9.4 Hz, H-4,8); signals based
on an equivalent of two 2,2-bis[4-(dimethylamino)phenyl]ethenyl
4.1.2. X-ray crystal structure of 2-(azulen-1-yl)-1,1-bis[4-(dimethy-
lamino)phenyl]ethylene (3). A total of 10,568 reflections with
substituents:
d
2.51 (12H, s, (CH3)2N-4000), 2.55 (12H, s, (CH3)2N-
2
qmax¼55.0ꢀ were collected on a Rigaku AFCe5R automated four-
400), 6.51 (4H, dd, J¼8.8, 2.5 Hz, H-300,500), 6.61 (4H, dd, J¼8.8,
circle diffractometer with graphite monochromated Mo Ka radia-
tion (
2.5 Hz, H-3000,5000), 7.32 (4H, dd, J¼8.8, 2.5 Hz, H-200,600), 7.45 (2H, s,
l
¼0.71069 A, rotating anode: 50 kV, 180 mA) at ꢁ75 ꢀC. The
ꢀ
20
10
pC ]C He), and 7.53 (4H, dd, J¼8.8, 2.5 Hz, H-2000,6000); 13C NMR
structure was solved by direct methods (SIR92) and expanded
using Fourier techniques (DIRDIF94). Non-hydrogen atoms were
refined anisotropically. Hydrogen atoms were included but not
refined. The final cycle of full-matrix least-squares refinement was
based on F2. All calculations were performed using the teXsan
crystallographic software package. Crystallographic data have been
deposited with Cambridge Crystallographic Data Center: De-
position number CCDC-634525 for compound No. 3. Copies of the
Center, 12, Union Road, Cambridge, CB2 1EZ, UK; Fax: þ44 1223
(benzene-d6):
d
150.1 (C-4000), 149.8 (C-400), 141.7 (C-20), 139.0
(C-3a,8a), 138.0 (C-6), 137.8 (C-2), 134.2 (C-1000), 133.5 (C-4,8), 131.7
(C-200,600), 130.3 (C-100), 129.4 (C-2000,6000), 128.7 (C-1,3), 122.4
(C-5,7), 117.2 (C-10), 113.3 (C-300,500), 112.6 (C-3000,5000), 40.3
((CH3)2N-400), and 40.2 ((CH3)2N-4000). The numbering scheme of 5
is shown in Scheme 1.
4.1.1.4. Compound 6. Dark blue blocks [Rf¼0.50 on silica gel TLC
(solv. hexane/ethyl acetate¼50:50, v/v)], mp 216 ꢀC; IR nmax/cmꢁ1
(KBr), 2878, 2797 (CeH), 1612, 1516 (C]C), and 1353 (CeN); exact
FABMS (3-nitrobenzyl alcohol matrix), found m/z 521.2945, calcd for
C38H37N2: [MþH]þ, m/z 521.2957; 1H NMR (benzene-d6): signals
Crystallographic data for 3: C28H28N2 (FW¼392.54), dark
based on an equivalent of two azulen-1-yl groups:
d 6.59 (2H, dd,
green block (crystal size, 0.50ꢂ0.50ꢂ0.40 mm), triclinic, P-1
J¼9.6, 8.9 Hz, H-50), 6.64 (2H, dd, J¼9.8, 9.8 Hz, H-70), 7.03 (2H, dd,
J¼9.8, 9.6 Hz, H-60), 7.21 (2H, d, J¼4.0 Hz, H-30), 7.81 (2H, d, J¼8.9 Hz,
H-40), 8.04 (2H, d, J¼4.0 Hz, H-20), and 8.53 (2H, d, J¼9.8 Hz, H-80);
signals based on an equivalent of two 4-(dimethylamino)phenyl
(#2), a¼14.574(5) A, b¼14.619(4) A, c¼10.482(4) A,
a
¼95.60(3)ꢀ,
ꢀ
ꢀ
ꢀ
3
ꢀ
b
¼94.53(3)ꢀ,
g
¼89.48(3) , V¼2215.6(13) A , Z¼4, Dcalcd¼1.177 g/cm3,
ꢀ
m
(Mo K
a
)¼0.683 cmꢁ1, scan width¼(1.15þ0.30 tan
q
)ꢀ, scan type-
¼uꢁ2q
, scan rate¼8.0ꢀ/min, measured reflections¼10,168, observed
groups:
d
2.38 (12H, s, (CH3)2N-400), 6.36 (4H, dd, J¼8.8, 2.5 Hz, H-
reflections¼6601, No. of parameters¼598, R1¼0.0533, wR2¼0.1472,
and goodness of fit indicator¼0.949.
300,500), and 7.13 (4H, dd, J¼8.8, 2.5 Hz, H-200,600); signals based on an
ethane unit (pHC2eC1Ho):
d
5.16 (1H, d, J¼11.3 Hz, H-2) and 6.14
(1H, d, J¼11.3 Hz, H-1); 13C NMR (benzene-d6):
d
148.9 (C-400), 141.2
4.1.3. X-ray crystal structure of 1,1-d(iazulen-1-yl)-2,2-bis[4-(dim-
(C-3a0), 136.7 (C-60), 136.3 (C-20,40), 135.5 (C-8a0), 134.6 (C-10), 133.8
(C-100),133.4 (C-80),129.6 (C-200,600),122.1 (C-50),121.5 (C-70),117.7 (C-
thylamino)phenyl]ethane (6). A total 4405 reflections with
2
qmax¼55.0ꢀ were collected on a Rigaku AFCe5R automated