Gromov et al.
3
3
2-({4-[(E )-2-(2,3,5,6,8,9,11,12-Oct a h yd r o-1,4,7,10,13-
b e n zo p e n t a o x a c y c lo p e n t a d e c in -15-y l)-1-e t h e n y l]-1-
qu in olin iu m yl}m eth yl)-1-ben zen esu lfon ate (4d). Mp: 242-
0.1 Hz, J H-1,H-2 ) J H-3,H-4 ) 10.4 ( 0.25 Hz), 5.43 (m, 2 H,
cyclobutane H(C-1), H(C-3)), 6.58 (d, 2 H, 2 H(C-5′) in ben-
zocrown ether, J H-5,H-6 ) 8.4 Hz), 6.76 (d, 2 H, 2 H(C-2′) in
benzocrown ether, J H-2,H-6 ) 2.1 Hz), 6.86 (m, 2 H, 2 H(C-6′)
in benzocrown ether, J H-6,H-5 ) 8.4 Hz, J H-6,H-2 ) 2.1 Hz),
7.96 (m, 2 H, 2 H(C-6) in quinoline), 8.14 (m, 2 H, 2 H(C-7) in
quinoline), 8.22 (d, 2 H, 2 H(C-3) in quinoline, J H-3,H-4 ) 6.3
Hz), 8.25 (m, 2 H, 2 H(C-8) in quinoline, J H-8,H-7 ) 8.9 Hz),
8.65 (d, 2 H, 2 H(C-5) in quinoline, J H-5,H-6 ) 8.4 Hz), 9.17 (d,
2 H, 2 H(C-2) in quinoline, J H-2,H-3 ) 6.3 Hz).
1
247 °C. H NMR (DMSO-d6): δ 3.66 (m, 8 H, γ,γ′,δ,δ′-CH2O),
3.84 (m, 4 H, â,â′-CH2O), 4.20 and 4.26 (2 m, 4 H, R,R′-CH2O),
6.63 (s, 2 H, CH2N), 6.74 (d, 1 H, H(C-6′′) in sulfonatobenzyl,
J ) 7.0 Hz), 7.09 (d, 1 H, H(C-5′) in benzocrown ether, J ) 8.1
Hz), 7.22 (t, 1 H in sulfonatobenzyl), 7.35 (t, 1 H in sulfonato-
benzyl), 7.49 (d, 1 H, H(C-6′) in benzocrown ether, J ) 8.1 Hz),
7.63 (s, 1 H, H(C-2′) in benzocrown ether), 7.96 (m, 2 H), 8.09
(m, 3 H), 8.43 (d, 1 H, H(C-3) in quinoline, J ) 6.0 Hz), 8.53
(d, 1 H in quinoline, J ) 8.5 Hz), 8.95 (d, 1 H in quinoline, J
) 8.1 Hz), 9.31 (d, 1 H, H(C-2) in quinoline, J ) 6.0 Hz). Anal.
3-(4-{2,4-Di(2,3,5,6,8,9,11,12-octa h yd r o-1,4,7,10,13-ben -
zop en ta oxa cyclop en ta d ecin -15-yl)-3-[1-(3-su lfon a top r o-
pyl)-4-qu in olin iu m yl]cyclobu tyl}-1-qu in olin iu m yl)-1-pr o-
p a n esu lfon a te (10b). 1H NMR (MeCN-d3/D2O (10%)): δ 2.35
(m, 4 H, 2 CH2), 2.75 (m, 4 H, 2 CH2SO3-), 3.55-3.75 (m, 24
H, 2 â,â′,γ,γ′,δ,δ′-CH2O), 3.85 (m, 8 H, 2 R,R′-CH2O), 5.10 (m,
Calcd for
Found: C, 62.88; H, 5.41; N, 2.25.
C32H33NO8S‚H2O: C, 63.04; H, 5.79; N, 2.30.
4-({4-[(E )-2-(2,3,5,6,8,9,11,12-Oct a h yd r o-1,4,7,10,13-
b e n zo p e n t a o x a c y c lo p e n t a d e c in -15-y l)-1-e t h e n y l]-1-
qu in olin iu m yl}m eth yl)-1-ben zen esu lfon ate (4e). Mp: 180-
4 H, 2 CH2N), 5.31 (m, 2 H, cyclobutane H(C-2), H(C-4),
3J H-2,H-3 ) 3J H-1,H-4 ) 7.61 ( 0.01 Hz, J H-1,H-2 ) 3J H-3,H-4
)
3
1
4
182 °C. H NMR (DMSO-d6): δ 3.64 (m, 8 H, γ,γ′,δ,δ′-CH2O),
10.29 ( 0.01 Hz, J H-2,H-4 ) 0.32 ( 0.02 Hz), 5.42 (m, 2 H,
4
3.81 and 3.85 (m, 4 H, â,â′-CH2O), 4.16 and 4.23 (2 m, 4 H,
R,R′-CH2O), 6.24 (s, 2 H, CH2N), 7.11 (d, 1 H, H(C-5′) in
benzocrown ether, J ) 8.4 Hz), 7.31 (d, 2 H in sulfonatobenzyl),
7.50 (d, 1 H, H(C-6′) in benzocrown ether, J ) 8.4 Hz), 7.59
(d, 2 H in sulfonatobenzyl), 7.72 (s, 1 H, H(C-2′) in benzocrown
ether), 7.99 and 8.16 (2 m, 2 H, H(C-6), H(C-7) in quinoline),
8.21 (s, 2 H, H(C-a), H(C-b)), 8.34 (d, 1 H in quinoline, J ) 9.1
Hz), 8.55 (d, 1 H, H(C-3) in quinoline, J ) 6.7 Hz), 9.08 (d, 1
H in quinoline, J ) 8.8 Hz), 9.52 (d, 1 H, H(C-2) in quinoline,
J ) 6.7 Hz). Anal. Calcd for C32H33NO8S‚2.5H2O: C, 60.36;
H, 6.02; N, 2.20. Found: C, 60.31; H, 6.04; N, 2.15.
cyclobutane H(C-1), H(C-3), J H-1,H-3 ) 0.49 ( 0.02 Hz), 6.56
(d, 2 H, 2 H(C-5′) in benzocrown ether, J H-5,H-6 ) 8.4 Hz), 6.81
(d, 2 H, 2 H(C-2′) in benzocrown ether, J H-2,H-6 ) 1.7 Hz), 6.82
(m, 2 H, 2 H(C-6′) in benzocrown ether, J H-6,H-5 ) 8.4 Hz,
J H-6,H-2 ) 1.7 Hz), 7.95 (m, 2 H, 2 H(C-6) in quinoline), 8.13
(m, 2 H, 2 H(C-7) in quinoline), 8.26 (d, 2 H, 2 H(C-3) in
quinoline, J H-3,H-4 ) 6.3 Hz), 8.36 (m, 2 H, 2 H(C-8) in
quinoline, J H-8,H-7 ) 9.0 Hz), 8.57 (d, 2 H, 2 H(C-5) in
quinoline, J H-5,H-6 ) 8.5 Hz), 9.20 (d, 2 H, 2 H(C-2) in
quinoline, J H-2,H-3 ) 6.3 Hz). The spin-spin coupling constants
for the protons of the benzocrown ether moiety and the
cyclobutane ring were obtained by analysis of the spectrum of
10b in D2O. The lower coherence of these protons in D2O and
the higher signal:noise ratio provided more precise values of
the constants.
1-Eth yl-4-[(E)-2-(2,3,5,6,8,9,11,12-octa h yd r o-1,4,7,10,13-
ben zop en ta oxa cyclop en ta d ecin -15-yl)-1-eth en yl]qu in o-
lin iu m Iod id e (4f). A mixture of 9 (1.0 mmol) and 7 (1.2
mmol) was dissolved in 10 mL of anhydrous EtOH, and then
5 mL of pyridine was added. The reaction mixture was heated
to reflux for 20 h and concentrated in vacuo. The residue was
treated with benzene to remove unreacted 7 and recrystallized
successively from MeOH and MeCN to give 4f in 33% yield.
Mp: 136 °C. 1H NMR (DMSO-d6): δ 1.60 (t, 3 H, Me), 3.65 (s,
8 H, γ,γ′,δ,δ′-CH2O), 3.82 (m, 4 H, â,â′-CH2O), 4.15 and 4.22
(2 m, 4 H, R,R′-CH2O), 5.00 (q, 2 H, CH2N), 7.10 (d, 1 H, H(C-
5′) in benzocrown ether), 7.46 (d, 1 H, H(C-6′) in benzocrown
ether), 7.70 (s, 1 H, H(C-2′) in benzocrown ether), 8.05 and
8.25 (2 m, 2 H, H(C-6), H(C-7) in quinoline), 8.15 (d, 2 H, H(C-
a), H(C-b), 8.45 (d, 1 H, H(C-3) in quinoline), 8.54 and 9.07 (2
d, 2 H, H(C-5) and H(C-8) in quinoline), 9.32 (d, 1 H, H(C-2)
in quinoline). Anal. Calcd for C27H32NO5I: C, 56.16; H, 5.59;
N, 2.43. Found: C, 55.96; H, 5.53; N, 2.51.
1-Eth yl-4-[(E)-2-(2,3,5,6,8,9,11,12-octa h yd r o-1,4,7,10,13-
ben zop en ta oxa cyclop en ta d ecin -15-yl)-1-eth en yl]qu in o-
lin iu m P er ch lor a te (4g). Compound 4f (0.03 g, 0.05 mmol)
was dissolved with heating in 5 mL of methanol, and then 57%
HClO4 (0.09 mL, 0.75 mmol) was added. After cooling, the
resulting precipitate was filtered and washed with cold
methanol. The yield of 4g was 0.03 g (95%). The 1H NMR data
for 4g in MeCN-d3 are given in Table 4.
4-(4-{2,4-Di(2,3,5,6,8,9,11,12-octa h yd r o-1,4,7,10,13-ben -
zopen taoxacyclopen tadecin -15-yl)-3-[1-(4-su lfon atobu tyl)-
4-qu in olin iu m yl]cyclobu tyl}-1-qu in olin iu m yl)-1-bu ta n e-
1
su lfon a te (10c). H NMR (MeCN-d3/D2O (25%)): δ 1.74 (m,
4 H, 2 CH2 in the tetramethylene chain), 2.09 (m, 4 H, 2 CH2
in the tetramethylene chain), 2.81 (m, 4 H, 2 CH2SO3-, J )
7.6 Hz), 3.5-3.73 (m, 24 H, 2 â,â′,γ,γ′,δ,δ′-CH2O), 4.12 and
4.16 (m, 8 H, 2 R,R′-CH2O), 4.93 (m, 4 H, 2 CH2N, J ) 7.6 Hz),
5.33 (m, 2 H, cyclobutane H(C-2), H(C-4), 3J H-2,H-3 ) 3J H-1,H-4
3
3
) 7.3 ( 0.2 Hz, J H-1,H-2 ) J H-3,H-4 ) 10.1 ( 0.2 Hz), 5.42
(m, 2 H, cyclobutane H(C-1), H(C-3)), 6.57 (d, 2 H, 2 H(C-5′)
in benzocrown ether, J H-5,H-6 ) 8.3 Hz), 6.82 (m, 2 H, 2 H(C-
6′) in benzocrown ether, J H-6,H-5 ) 8.3 Hz, J H-6,H-2 ) 1.9 Hz),
6.84 (d, 2 H, 2 H(C-2′) in benzocrown ether, J H-2,H-6 ) 1.9 Hz),
7.95 (m, 2 H, 2 H(C-6) in quinoline), 8.13 (m, 2 H, 2 H(C-7) in
quinoline), 8.26 (d, 2 H, 2 H(C-3) in quinoline, J H-3,H-4 ) 6.2
Hz), 8.31 (m, 2 H, 2 H(C-8) in quinoline, J H-8,H-7 ) 8.9 Hz),
8.66 (d, 2 H, 2 H(C-5) in quinoline, J H-5,H-6 ) 8.6 Hz), 9.15 (d,
2 H, 2 H(C-2) in quinoline, J H-2,H-3 ) 6.2 Hz).
2-[(4-{2,4-Di(2,3,5,6,8,9,11,12-octa h yd r o-1,4,7,10,13-ben -
zop en ta oxa cyclop en ta d ecin -15-yl)-3-[1-(2-su lfon a toben -
zyl)-4-qu in olin iu m yl]cyclobu tyl}-1-qu in olin iu m yl)m eth -
yl]-1-b en zen esu lfon a t e (10d ). 1H NMR (MeCN-d3/D2O
(25%)): δ 3.5-3.88 (2 m, 24 H, 2 â,â′,γ,γ′,δ,δ′-CH2O), 4.12 and
4.16 (m, 8 H, 2 R,R′-CH2O), 5.37 (m, 2 H, cyclobutane H(C-2),
Syn th esis of Cyclobu ta n es 10a -d . The corresponding
styryl dye (i.e., 4a -d , 0.01 mmol) and Mg(ClO4)2 (0.011 mmol)
were dissolved in 5 mL of anhydrous MeCN. The solution was
irradiated with a 405 nm light source; after complete con-
sumption of the dye (monitoring by spectrophotometry), MeCN
was evaporated in vacuo. The solid residue was dissolved in a
3
3
H(C-4), J H-2,H-3
)
3J H-1,H-4 ) 7.6 ( 0.1 Hz, J H-1,H-2
)
3J H-3,H-4 ) 10.6 ( 0.1 Hz, J H-2,H-4 ) 0.2 ( 0.1 Hz), 5.52 (m,
4
4
2 H, cyclobutane H(C-1), H(C-3), J H-1,H-3 ) 0.7 ( 0.1 Hz),
1
MeCN-d3/D2O mixture and analyzed using H NMR spectros-
6.28 (d, 2 H, 2 H(C-6) sulfonatobenzyl, J H-6,H-5 ) 7.6 Hz), 6.41
and 6.69 (2 d, 4 H, 2 CH2N, 2 J CHH ) -16.5 Hz), 6.57 (d, 2 H,
2 H(C-5′) in benzocrown ether, J H-5,H-6 ) 8.3 Hz), 6.82 (m, 2
H, 2 H(C-6′) in benzocrown ether, J H-6,H-5 ) 8.3 Hz, J H-6,H-2
) 1.9 Hz), 6.84 (d, 2 H, 2 H(C-2′) in benzocrown ether, J H-2,H-6
) 1.9 Hz), 7.44 (m, 2 H, 2 H(C-4) in sulfonatobenzyl), 7.47 (m,
2 H, 2 H(C-5) in sulfonatobenzyl), 7.90 (m, 2 H, 2 H(C-6) in
quinoline), 7.98 (m, 2 H, 2 H(C-7) in quinoline), 8.01 (d, 4 H,
2 H(C-3) in sulfonatobenzyl, J H-3,H-4 ) 7.8 Hz), 8.28 (m, 2 H,
2 H(C-8) in quinoline, J H-8,H-7 ) 9.0 Hz), 8.35 (d, 2 H, 2 H(C-
copy. The NMR spectra demonstrated that the photolysis
afforded cyclobutanes 10a -d in almost quantitative yields.
2-(4-{2,4-Di(2,3,5,6,8,9,11,12-octa h yd r o-1,4,7,10,13-ben -
zopen taoxacyclopen tadecin -15-yl)-3-[1-(2-su lfon atoeth yl)-
4-qu in olin iu m yl]cyclobu tyl}-1-qu in olin iu m yl)-1-eth a n e-
1
su lfon a te (10a ). H NMR (MeCN-d3/D2O (25%)): δ 3.34 (m,
4 H, 2 CH2SO3-), 3.5-3.68 (m, 24 H, 2 â,â′,γ,γ′,δ,δ′-CH2O),
3.87 (m, 8 H, 2 R,R′-CH2O), 5.22 (m, 4 H, 2 CH2N), 5.32 (m, 2
3
3
H, cyclobutane H(C-2), H(C-4), J H-2,H-3 ) J H-1,H-4 ) 7.7 (
6124 J . Org. Chem., Vol. 68, No. 16, 2003