Al Neirabeyeh, M.

Lopez, J.L.

Pais, M.

Pusset, J.

Veillon, Jean-Marie

Horizon / Pleins textes

Isolation and 2D NMR Studies of Alkaloids from 
ComptonelLa sessiZVoEioZa' 
Jacques P u ~ s e t " ~ .  José Luis Lopez4. Mary Pais'. Mamdouh Al Neirabeyeh"q and Jean-Marie Veillon5 
' Plants ofNew Caledonia; Part 132. For Part 131, see: Ska1tsounis.A.-L., Sbahi, S.. Demetzos. C., Pusset, J. (1990) 
Ann. Pharm. Fr.. in press. 
Institut de Chimie des Substances Naturelies. Centre National de la Recherche Scientifique. F-9119s. Gifsur Yvette, France 
Address for correspondence 
Centre ORSTOM. BP A5. Nouméa Cedex, Nouvelle-Calédonie 
Present address: United Arab Emirates University, Faculty ofSciences. BP 17551, Ai Ain, United Arab Emirates 
' Departamento de Química Orgánica. Facultad de Farmacia, Universidad de Salamanca, Spain 
Received: May 16.1990 
Abstract 
Six known furanoquinoline alkaloids have 
been isolated from the wood and trunk bark of Comp- 
tonella sessilifbliola (Guillaumin) Hartley (Rutaceae). 
2D NMR experiments gave the assignment of all the sig- 
nals for both 'H- and I3C-NMR spectra. Pteleine and 
kokusaginine were used as models. The two-dimen- 
sional carbon-proton correlation experiments, per- 
formed for the first time on furanoquinoline alkaloids, 
led us to correct l3C-NMR assignments previously de- 
scribed in the literature. 
Kev words '-. 
- &<;> -y 'f;c ?L.$j%. - Comptonella sessili,foliola, furanoquino- 
line alkaloids, 2D NMR, dictamnine, pteleine, evolitrine, 
kokusaginine, dutadrupine, li-pla playdesmine. 
Introduction 
Comptonella sessilifoliola (Guill.) Hartley 
(Rutaceae) is a tree that grows to 8 m  high with opposite 
trifoliolated leaves and four-lobed fruits. Phytochemical 
studies on different parts of the plant (trunk bark and wood) 
led to the isolation of six alkaloids. Their spectroscopic data 
(IR, 'H-NMR. UV, mass) showed that they all belong to the 
group of furanoquinoline alkaloids. They have been found 
to be identical with dictamnine (1) (l), pteleine (2) (21, evolit- 
rine (3) (31, kokusaginine (4) (41, dutadrupine (5) (5). and R-(+I- 
platydesmine (6) (2). From these only for dictsmnine were 
I3C-NMR data (6) previously available and some assign- 
ments of signals from proton spectra were not possible 
without I3C-NMR spectra. ' 
Since it is difficult, with the large number of 
quaternary aromatic carbon atoms, to assign the different 
"C-NMR signals to each atom without error, heteronuclear 
one bond and long-range carbon-hydrogen correlation ex- 
periments have been performed for two of the al- 
kaloids : pteleine (2) and kokusaginine (4). The results of 
these experiments, shown in Figs. 1 and 2, led us to assign 
5 
1 R' RZ R 3  
1 I H  H H OCH? 
6 
unambiguously all the signals of both carbon and proton 
spectra for the six alkaloids (Tables 1 and 2). 
For pteleine (2; Fig. 11, each of the signals of 
the proton spectrum can be identified as all the signals of 
aromatic protons show different coupling constants. The 
assignment of1 3C-NMR signals is clearly resolved by exami- 
nation ofthe 2D spectra. For example, in the heteronuclear 
long-range H/C correlation spectrum, the , signals at 
155.4ppm and l56.0ppm in the carbon spectrum are re- 
spectively correlated to methoxy signals at 4.30 ppm and 
3.85 ppm in the proton spectrum; furthermore, the latter 
13C signal is also correlated with H-8, which led us to assign 
the signal at 156.0ppm to C-6 and hence the former (at 
155.4ppm) to C-4. 
Two other signals of non-protonated car- 
bons at 103.6 ppm and 119.0ppm also show several corre- 
lations. The signal at 103.6 ppm is correlated with H-10 and 
H-11, the signal at 119.0 ppm with H-8; the first signal (at 
103.6ppm) can be assigned to C-3 and the second (at 
119.0 ppm) to C-9. The other assignments for this subtance 
are shown in Fig. 1. 
O. R,S.l7.3..M, Fonds Documentake 
Fig. 1 Heteronuclear correlations C-H for one bond and long-range 
couplings for pteleine (2). 
Table 1 %NMR chemical shifts for comoounds 1 to 6. 
Compounds 
6 I Carbon 1 1 2 3 4 
1 142.7 ' 142.9 ' 147.9 
2 168.9 162.5 161.3 163.1 64.5 169.0 
3 103.7 103.6 102.2 102.3 101.8 102.4 
4 157.0 155.4 157.3 155.6 157.2 159.2 
' 145.9 .' 141.3 ' 142.5 ' 
5 122.4 100.2 116.8 100.4 118.8 122.2 
6 123.8 156.0 123.6 147.9 122.9 123.5 
7 129.6 122.2 147.7 152.8 154.3 129.8 
8 128.0 129.0 106.0 106.7 113.8 127.1 
9 119.0 119.0 113.6 113.1 114.5 120.4 
11 143.7 143.3 142.5 142.4 142.5 86.6 
OMe-4 59.1 58.8 59.0 58.8 59.0 58.4 
OMe-6 55.4 56.0 
OMe-7 55.5 56.0 
10 104.8 104.4 104.9 104.5 104.8 29.1 
2' 76.9 
3' 116.1 
4' 128.4 
Me 28.1 
12 76.1 
Me-13 24.8 
Me-14 26.1 
CDCI,, TMS as internal standard, 6, ppm. 
The hvo-dimensional carbon-proton corre- 
lation experiments, performed for the first time on 
furanoquinoline alkaloids led us to complete and to correct 
the previous data in "C-NMR already published. For skim- 
Table 2 'H-NMR chemical shifts for compounds 1 to 6. 
Protons 1 2 3 1 4 .  I 5 6 
I I , ,  
5 
6 
7 
8 
10 
11 
OMe-4 
OMe-6 
OMe-7 
I 8.27dd(a.4,1.7) 
I 
7.45 ddd(8.4.8.4J.7) 
7.68 ddd(8.4,8.4,1.4) 
8.01 dd(8.4,1.4) 
7.08 d(2.8) 
7.69 d(2.8) 
4.45 s 
I I 
7.36 d(2.9) 8.15 d(9.3) 
7.31 dd(9.0,2.9) - 
7.87 d(9.0) 7.33 d(2.6) 
6.90 d(2.8) 7.05 d(2.8) 
4.30 s 4.43 s 
3.88 s - 
3.95 s 
7.09 dd(9.3,2.6), - 
7.50 d(2.8) 7.57 42.8) 
- 
I 
7.41 s 
- 
7.31 s 
6.97 d(2.7) 
7.52 d(2.7) 
4.37 s 
4.00 s 
4.02 s 
8.09 d19.1) 
6.97 d(9.1) - - 
7.00 d(2.8) 
7.53 42.8) 
4.38 s - 
- 
I 
7.89 d(8.2) 
7.23 ddd(8.3,8.2,1.4) 
7.49 ddd(a.4,8.3. I .4) 
7.67 d(a.4) 
3.53 dd(14.5,g.O) 
3.68 dd(14.5,7.4) 
4.64 dd(9.0,7.4) 
4.19s 
3' 5.68 d(lO.O) - 
4' 7.47d(10.0) - -; , 
Me 1.50s - 
1.28s Me-13 
Me-14 
CDCI,. TMS as internal standard, 6, ppm. 
1.49s 
. . . .  . . . . .  ....-: . . . . . . . . . . .  :. . .  .: . ,.... . . . . . . .  . . . . . . . .  . . . . . . . . . . . . . . . . . . . .  .  .--,,-.---.-., < .. . -.. . . .  
.:. 163.1 C I f- 
J. double intcnsitv: :3 one bond correlations: + lone-mnqe correlations 
Fig. 2 Heteronuclear correlations C-H for one bond and long-range 
couplings for kokusaginine (4). ' 
For kokusaginine (4; Fig. 21, signals of the 
'H-NMR at 4.00 ppm and 4.02 ppm can be assigned clearly 
to OMe-6 and OMe-7 respectively because they are con- 
nected, in the 2D long-range correlation spectrum, with the 
quaternary aromatic carbons at 147.9 ppm for the former 
signal and 152.8 ppm for the latter. These values corres- 
pond to carbons C-6 and C-7 respectively as other correla- 
tions with H-8 for the former and with H-5 for the latter are 
observed and this experiment had been optimised for a cou- 
pling constant "JH.c = 8 Hz, corresponding to the approxi- 
mate value 3JH.c,,m (7 Hz) for benzenic compounds and 
quite different from the value 2JH,c,,fh, (1 Hz) (7). 
As the signals of the non-protonated car- 
bons at 102.3ppm and 113.1 ppm show chemical shifts 
similar to those observed in the spectrum of pteleine (103.6 
and 119.0 ppm) together with identical correlations, they 
can be assigned to C-3 and C-9 respectively. 
. 
I 
S 
L 
inianine (7). t he  signals at 101.8 p p m  a n d  114% ppm were  
assigned (S) to C-9 a n d  c-3,  but  we have shown in this work 
that  it w a s  the  opposite. Similar assignments have been  
made for evosine (6). perfamine (9). (2-isopentenyloxyl- 
4,7-dimethoxyfurano[2.3-b]quinoline (10) and  have to be  
corrected. 
1Materials and Methods  
General 
Melting points were taken on a Kofler apparatus, 
optical rotations were measured on a Perkin-Elmer 241 instru- 
ment and W spectra [C2H50H, A,,,-, nml on a Perkin-Elmer 
Lambda 5 spectrometer. IR spectra (v, cm-', CHCI,) were recorded 
on a Perkin-Elmer 297 spectrometer. 'H-NMR, I3C-NMR spectra at 
30.3 MHz and 2-D experiments have been recorded on a Bruker 
WP 200 SY spectrometer in CDCI,. The 6 values are given in ppm 
with TMS as internal reference and coupling constants in Hz. Mass 
spectra were measured on a n  MS 50 instrument. Flash chromatog- 
raphy was performed on silica gel 60 (Merck) column and TLC on 
silica gel F 254 (Merck). . 
Material 
The plant was collected on Mount Koniambo in 
New-Caledonia around 800m on October 21, 1982. A voucher is 
kept in the Herbarium of PRSTOM Center in N o m e a  under the re- 
ference Pusset-Chauviere 453. 
Extractions and purifications 
The sawdust (8.7 kg), wet with NH40H, was ex- 
tracted with methylene chloride during 24 h yielding the crude al- 
kaloids (2.4 g, 0.027 % from startingmaterial). Chromatography on 
silica gel H60 Merck (with CH,Cl,-MeOH, 99 : 1) led to compounds 
1 (22 mg, 3 %), 2 (30 mg, 4.25 %), 3 (38 mg, 5.4 Yo), and 6 (600 mg. 
25 Yo). 
The trunk bark (6.4 kg), wet with NH,OH, was ex- 
tracted with methylene chloride during 48 h yielding the crude al- 
kaloids (16 g, 0.25 Yo from starting material). Chromatography on 
silica gel H60 Merck (with CH2C1,-MeOH. 99-1) led to compounds 2 
(1.74g. 10.8Yo), 3 (1.5g. 9.3%). 4 (4.23g. 26%), and 5 (1.72g. 
10.7 %). 
Dictumnine (1): m.p. 128-130°C; IR: 3144, 
2960,1627,1583,1470; UV(neutra1): 330,315,241,237; MS: nv'z 
= 199 (M+),184.156,128.101. 
Pteleine (2): m.p. 136-138°C; IR: 3130, 1623, 
1593, 1542,1383,1158; W (neutral) 349,307,296,249;MS: rrdz 
= 229 (MC), 214,186,158,156, 63. 
Evolitrine (31: m.p. 114°C; IR: 3122,2940,1626, 
1590, 1465.1158; W(neutra1) 333,320,308,247: MS: d z =  229 
[W), 214, 186. 
Kokusuginine (4): m.p. 168-169°C; IR: 3130, 
1623, 1592. 1552,1423; W(neutra1) 336,322,296,251: MS: nv'z 
= 259 244,216,201,186, 173. 
Dutadrupine (5): all data are identical with those 
published in the literature (5). 
R-(i)-Platydesmine (6): [alo = +51" (C 1, EtOH): 
m.p. 136-138°C; IR: 3040, 1636,1590,1470,1370; W(neutra1) 
321,307,283,263.237; MS: m/.z = 259 (M'l, 200.59. 
2-0 i W R  experiments 
Heteranuclear 1H-13C (200/50.3 MHz) correla- 
tion: The four experiments have been performed with the XHDEPT 
pulse sequence from the Bruker DISNMR 87 library program. For 
the two one bond correlations 128 FIDs of 1200 scans each. with 
1 sec recycle delay and incrementing tl from 5 psec to 640 msec, 
were acquired on a 0.5 M solution at 32°C. Polarization transfer 
was tuned for a value of = 135 Hz. After sine-bell multiplica- 
tion ofthe FID in both domains with one degree ofzero-filling in FI. 
a matrix of 256/1024 data points with digital resolution [DR) = 
7.2 Hdpt  in F2 and 7.8 Hupt  in FI was obtained. The long-range 
'H/13C correlation was performed in similar manner with "Jc.J = 
8 Hz and 2400 scans per FID. 
Acknowledgemen t s  
J. L. L. thanks La Caja de Ahorros de Salamanca 
for financial support. 
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Isolation and 2D NMR studies of alkaloids from Comptonella sessilifoliola

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