4
612
U. Girreser et al. / Tetrahedron Letters 50 (2009) 4610–4612
Table 1
1
5N (30 MHz), 13C (75 MHz), 1H (300 MHz), COSY LR, HMBC and NOESY data for 2-(2-carboxy-4,5-dimethoxyphenyl)-6,7-dimethoxyisoquinolinium inner salt 3 in methanol-d
4
1
HMBC ( H–15N)d
1
No.
15N (d)a
13C (d)
1H (d, Hz)
COSY LRc
3, (4), 5
HMBC ( H–13C)
NOESY
0
0
1
2
3
4
147.5
9.47 d (1.5)
1 , (3), 4a, 8, 8a
(2)
6 , 8
b
0
0
ꢀ178.3 (ꢀ181.9)
(1), 3, (3 ), 4, 6
0
0
136.27
123.13
137.33
106.38
159.97
154.35
108.29
125.09
136.15
128.24
114.35
151.32
151.49
110.74
57.52
8.34 dd (6.8; 1.5)
8.16 d (6.8)
4
3, 8
1,1 , 4, 4a, (6), (8a)
(1), 3, 5, (8), 8a
2
2
6
5
4
5
6
7
8
8
1
2
3
4
5
6
6
7
2
4
5
a
7.64 s
7.57 s
3,6-OMe
4, 7-OMe
(1), 4, 6, 7, 8a
4, 6-OMe
1
1,(4), 4a, (5), 6, 7
7-OMe
a
0
0
0
0
0
0
0
0
0
0
0
ꢀ
0
0
0
0
7.58 s
4 -OMe, 6
1 , 2 , 2 -COO , 4 , 5 , 6
(2)
2
4 -OMe
0
0
0
0
ꢀ
0
0
0
0
7.15 s
4.13 s
3.98 s
3 ,5 -OMe
1 , 2 , 2-COO , (3 ), 4 , 5
5 -OMe
-OMe
-OMe
5
8
5, 6
7, 8
5
8
57.00
170.29
56.54
0
0
0
ꢀ
-COO
-OMe
-OMe
0
0
0
0
0
0
3.96 s
3.90 s
3
3 , 4
3
6
0
0
56.95
6
5 , 6
a
Chemical shift obtained from the 1H–15N HMBC NMR and referenced to nitromethane.
Chemical shift recorded in DMSO-d .
6
Weak signals in parentheses.
6
Spectrum recorded in DMSO-d .
b
c
d
served that fascaplysin, on treatment with a solution containing
This project was supported by a research Grant (No. NN 405 178
335) of The State Committee for Scientific Research (Poland).
ꢀ
OH ions, underwent a change in its colour indicative of its conver-
7
,14
sion to reticulatate.
In the case of 2 the tetracyclic structure is
converted into zwitterionic product 3 and the UV spectrum is
shifted to a shorter wavelength.
References and notes
Compound 2 was synthesized by irradiating a 0.3% (w/v) chlo-
roform solution of papaverinol with a low-pressure mercury lamp
at 254 nm for 4.5 h. The crude material dissolved on boiling in
methanol and crystallized as a black powder; yield up to 40%.
Compound 3 was obtained by dissolving 2 in a 0.4% aqueous
NaOH solution with heating for 2 h at 60 ꢀC . The solvent was evap-
1
.
Schmidt, J.; Boettcher, C.; Kuhnt, C.; Kutchan, T.; Zenk, M. Phytochemistry 2007,
8, 189–202.
2. Piotrowska, K.; Hermann, T.; Augustyniak, W. J. Pharm. Biomed. Anal. 2006, 41,
391–1395.
Girreser, U.; Hermann, T.; Piotrowska, K. Arch. Pharm. Pharm. Med. Chem. 2003,
36, 401–405.
6
3
1
3.
3
4. Gał e˛ zowska, E.; Masternak, A.; Rubi s´ , B.; Czyrski, A.; Rybczy n´ ska, M.; Hermann,
orated and the residue was dissolved in CHCl
3 3
–CH OH (1:1) mix-
T.; Juskowiak, B. Int. J. Biol. Macromol. 2007, 41, 558–563.
M a˛ dry, L.; Gał e˛ zowska, E.; Głuszy n´ ska, A.; Hermann, T.; Zabel, M.; Juskowiak, B.
Pol. J. Chem. 2006, 80, 921–929.
Hermann, T.; Lisowski, Z.; Wro n´ ski, A. Biul. Wojsk. Akad. Med. Lodz Poland 1965,
8, 235–241.
5.
6.
7.
8.
ture (yield of crude product was 15%). The product was isolated
by column chromatography on aluminium oxide (ECO-CHROM,
3 3 3
Germany), mobile phase: reagent grade CHCl , CHCl –CH OH
Czyrski A., Hermann T., Wyrzykiewicz E., Girreser U. Poland Patent P 387214,
(
20:1, 10:1, 5:1, 1:1 v/v) and finally reagent grade CH
3
OH. The
2009.
product was observed on the column as a white fluorescent band
using a UV365 lamp and was separated, washed with water and
chloroform and dried (yield of pure 3 = 10%). The purity was con-
firmed by TLC on aluminium oxide (POLYGRAM, MACHEREY-NA-
GEL, Germany) using chloroform–methanol (1:1; v/v) as the
Segraves, N.; Lopez, S.; Johnson, T.; Said, S.; Fu, X.; Schmitz, F.;
Pietraszkiewicz, H.; Valeriote, F.; Crews, P. Tetrahedron Lett. 2003, 44, 3471–
3
475.
Marek, R.; Humpa, O.; Slavik, J.; Sklená rˇ , V. Magn. Reson. Chem. 1999, 37, 195–
02.
9.
2
10. Zieli n´ ski, W.; Rajca, A. Metody spektroskopowe i ich zastosowanie do identyfikacji
zwi a˛ zków organicznych; Wydawnictwa Naukowo-Techniczne: Warsaw Poland,
f
mobile phase; R = 0.88.
2000. p. 362.
1
1. Katritzky, A.; Krutošiková, A.; Ramsden, C.; Lewis, J. Coll. Czech. Chem. Commun.
Acknowledgement
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1
1
The Department of Pharmaceutical Chemistry at Christian-Al-
brechts-University in Kiel (Germany) is acknowledged for a two-
month research fellowship to Andrzej Czyrski.
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