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Carbon-13 NMR spectroscopy of pyrrolizidine alkaloids
Phybchrmwtry, Prmted
Vol 29, No I” Great Bntam
1, pp 11-29, 1990
0+X-9422/90 $3 OOtOOO kc 1989 Pergamon Press plc
REVIEW
CARBON-13
ARTICLE
NMR SPECTROSCOPY E.
Pharmaceutical
Institute,
Unlverslty
alkaloids,
50
OF PYRROLIZIDINE
ALKALOIDS
ROEDER
Bonn, An der Immenburg 4, D-5300 Bonn 1, F R.G
(Recerued WIrewedform Key Word Index-Pyrrohzldlne
NUMBER
16 June 1989)
13C NMR spectral
analysis,
structure
elucldatlon
Abstract-13C NMR chemical shifts of more than 130 naturally occurring alkaloids published up to 1988 are listed. The utility of 13C NMR spectroscopy for the structure elucidatton of these compounds combmed with mass spectra IS discussed
which gives the molecular formula, the molecular weight and m addition some Important mformatron concerning the structure of the alkaloid. The tables contain only literature data which can defimtely be related to a compound If several authors described the same alkaloid, the average value for the chemical shift has been determined and listed. Obvrously wrong assignments have not been taken mto constderation or the values have been put into brackets. The same procedure has been applied, where an assignment was difficult to carry out. The values of acetyl groups, esterrfied to the hydroxy functions of the necimc acids or, m some cases, with the necme itself, have not been listed. For the carbonyl group the chemical shift IS about 6 169.2* 2 The signal for the methyl group appears at 621 3 f 1.5 (measured m CDCl, solutron) The signals for methoxy groups m the necmrc acids have not been listed Their methyl signals appear at 656.8&O 3
INTRODUCTION
The application of r3C NMR spectroscopy is playing an outstanding role m the structure eluctdatton of naturally occurring compounds [ 1,2]. Since the first application of ‘%NMR spectroscopy in 1974/75 by Htkicht [3] and Culvenor [4] It has been one of the standard analytical methods in the field of pyrrohzidme alkaloids In the meantime the ’ 3C NMR data of more than 130 alkaloids have been published. Unfortunately they are widely spread m the hterature and accordingly difficult to find. The reviews which were published m 1982/83 [l, 5-81 have not changed this srtuatton In the textbook ‘Carbon-13 NMR Spectroscopy’ by Brettmater and Voelter [2], in the chapter ‘Natural Products’, data has been mcluded on some pyrrohztdme alkalotds, but this mformatton can only be a ‘first aid’ for the mterpretatton of r3C NMR spectra After the pubhcatton of many papers during recent years, which describe the use of r3CNMR data for the structure eludtcatton of alkaloids, tt seems to be necessary to present a new revtew deahng with the 13CNMR data of pyrrohztdme alkaloids.
Nomenclature Apart from the necine ring system, the numbering of the C-atoms IS very arbitrary and different In the Chemical Abstracts there IS no obvrous regulatmg prmctple. Therefore, the numbering was standardized as tt IS shown m formula Z m combmatlon with the necmic acids ofthe basic types a-f For the macrocyclic alkalotds of the Crotalanan-, the Seneclonan- and Otonecan-type, the nomenclature and numbermg of Chemical Abstracts have been adopted. For all other macrocychc compounds only the numbering of Chemtcal Abstracts has been used
RESULTS
The amino alcohols forming the basis of the alkaloids, the necmes, and the sample alkaloids formed by the estertficatton with mono-carboxylic acids (necinic acids) have been listed in Tables l-4. The general structures of the necimc acids are given m the formulae a-f shown in Table 2. For the multttude of macrocyhc alkalotds based on drcarboxyhc acids, Tables 5, 7, 9 and 10 have been comptled for the 1l-, 12- and 13-membered rmg-systems. The otonecine-alkalotds, which belong to the 1 l- and 12-membered macrocycles, have been comptled in Tables 6 and 8 Atypical alkaloids have been summarized in Table 11 Generally for every structure eluctdatton of a natural product, a high-resolution mass-spectrum is presented
Solvents and standard The Tables also contain the solvent whtch served for the measurement of the spectra Most alkaloids have been measured m deuterochloroform solution (CDCI,). The spectra of salts and N-oxides, which are soluble m water, m most cases have been made m deuterated water (D,O). 11
E. ROEDER
12
Table
1. “C NMR data for alkaloids R
R 7
R
ZHZOH
-cl?5 1
8 \\
17.3)
6
5
N 4
'2
3
R=HorOH 1
Mass
Formula
139 141 141 155 155 155 157 157 157 171 171 *Solvents:
Name
CAS-Reg.
Supinidine Trachelanthamidine Isoretronecanole Heliotridine Retronecine Retronecine’ (HCI) Curassanecine Platynecine Dihydroretronecine Uspallatinecine Retronecine-4-oxide
551.-59-7 52664-l 526-63 -~6 520-6338 4X&-R5 ~3 875-22~~9 82842X0-0 52&--6221 520-62~7 98303-06-l 687G-3333
a=CDCI,;
h=D,O;
c==C,D,N;
No.
Compound No.
C-l
c-2
1.1 1.2 1.3 1.4 I.5 1.6 1.7 1.8 1.9 1.10 1.11
137.84 48.14 48.22 138.00 138.40 135.71) 80.32 45.80 43.90 131.00 138.30
121.02 31.95 31.81 127.10
126.00 120.50 39.15 30.40 28.60 135.90 122.50
d=(CD,)$jO
Table
2. 13C NMR data for pyrrolizidine
alkaloid
monoesters
a
6
sMe 3
5
R = necic acid R=H 2
Mass
Formula
Name
CAS-Reg.
237 237 237 239
C,aH,,NOa G,H,,NO, C,,H,,NO, G,H,,N%
Angeloyl-heliotridine Angeloyl-retronecine Senecioyl-retronecine Angeloyl-platynecine
723-78-4 602998229 63503-33-3 940543227
*Solvent:
a = CDCI,.
No.
d
Compound No.
C-l
C-2
c-3
C-5
Necinc C-6
2.1 2.2 2.3 2.4
137.7 138.1 138.X 43.9
126.5 127.7 121.8 28.7
63.2 62.1 61.8 S5.6
53.6 53.x 53.5 53.6
34.6 30.2 34.3 35.2
Pyrrohzldme with the necme base (structure
alkaloids
13
1)
c-3
c-5
C-6
c-7
C-8
c-9
Solvent*
Ref.
59.91 54 19 54 78 58.70 59 50 56.80 45 66 5120 55.30 62 40 80 50
56 64 5453 54 52 54 10 53 60 53.10 5329 5560 53 80 60 30 70.70
25 25 25 35 36 34 25 38 36 78 36
30 43 30 08 29 92 71 10 71.50 68 40 2184 7500 7130 76.70 72 20
7127 69 92 68 16 79 50 77 30 77 80 70 80 73 10 1300 14 60 9180
6190 65 25 64 97 6190 62 30 60 50 68 38 63 40 61 50 60 10 60 80
a
I?31 PI PI cw
90 75 69 10 30 20 42 30 50 60 60
with the necine base esterllied
m posltlon-7
oMe
4Me
(see structure
a a a
a, b, d
[S, 7,9-l l] [S, 13-161
b
PI c51 Cl11 Cl71
i b
[I, 10, 15, 16, 181
;
2)
Mes
0 C
b
4Me
Me
3’
f
e
r-f
c-7
C-8
c-9
Ester at c-7
14.1 77I
75.9 792
601 598
b b
1687 1676
1244 1253
205 20.5
-
1408 1399
-
724 15.1
76 3 69 2
594 627
c b
1680 167.0
1150 127 2
(208)
-
138.8 1394
27.6 -
C-l
c-2
c-2
Neclc acid C-2” c-3
c-3
c-5
Solvent*
Ref.
159 158
-
a a
Cl91
20.5 (158)
-
a a
~231 ~241
c-4
[20-221
E ROEDER
Table
Mass
Formula
239 253 253
C,,H,,NO,
255
C,A,NO,
255 283 285 285 285 285 285 299 299 299 299 299 299 299 313 329 345 383
CI~HZ~NO~ C,,H,,NO, G,H,,NO, C,,H,,NO, C,,H,WJ, CISH,PO, C,,HmNO, C,,H,,NO, C; ,H,aO>, C, xHz~NO~ C,zH.z,NO, C,,H,,NO, C, bH,,NOh C,,H,,NO, C,,H,,NO, C,,H,,NO, C,,H,,NQ, C,“H,,NO,
*Solvent
a=CDCI,,
Name Fuchslseneclonme Seneeoyl-retronecine-4oxide (Isosenaetnme) Angeloyl-retronecme-4oxide Angeloyl-platynecme-4oxide Hehfolme Supmme Coromandalme Hehocoromandalme Hehocurassavlcme Hehocurassavmme Hehovlcrne Echmatme Indlcmc Intermedme Lycopsamme Rmderme Curdssavme Hehocurassavme Hehotrme Europme Europmi%-4-nxlde (2’-Isovaleroyl) vlndlflaroylretronecme
h=D,O,f=CH,OD
CAS-Reg
No
3 ‘%I NMR data of pyrrohzldrne Compound No
C-l
C-2
c-3
alkaloid
Necme c-5
monoesters
C-6
C-l
51370-97-9
3.1
35.9
31 8
51 9
53 5
39 3
69 6
106283%394)
3.2
132.5
122 2
78 9
70 2
343
699
27773--86-o
3.3
1337
1202
78 3
69 3
352
69 4
94054-33-8 80787-564 551-5X--6 68473-86-9 823544334 X2354-34-5 82374-02.-5 68473-85-8 480-83-l 4&&82-o 10285-06-O 10285-07-l 6029-84-l 68385-70-6 82398-74--l 303-33-3 570-19-4 65582-5X3
3.4 3.5 3.6 3.1 3.8 3.9 3.10 3.11 3.12 X.13 3.14 3.15 3.16 3.17 3.18 3.19 3.20 3iIt
39 4 44 9 1379 448 44 7 44 2 442 44 1 1363 1377 1329 133 0 1362 44 8 44 7 136.4 1373 1322
30 I 71 7 1256 31 5 31 3 309 31 1 31 1 1259 1307 1304 1302 1268 31 6 31 4 1274 1259 !244
71 7 625 61 9 54 5 544 54 3 54 3 54 3 619 630 62 b 629 619 54 5 54 5 620 61 9 68 6
69 9 534 56 9 542 54 2 542 542 54 2 542 518 53 9 53 9 54 2 542 54 2 54 2 54 6 h! ?
35 7 37 3 25 9 25 6 25 6 25 1 250 25 0 33 8 363 36 3 362 340 25 6 25 6 34 3 346 33 6
724 75 7 30 2 302 30 0 29 9 29 3 29 3 74 6 71 4 702 710 74 9 30 3 30 1 75 6 794 713
with
15
Pyrrolmdme alkalotds
the necme base estertfied m positton-
(see structure 2)
C-8
c-9
Ester at c-9
142
661
C
1677
1359
-
131.9
97 1
59.9
c
1662
1148
-
966
60 5
b
1612
127 3
20.5
89 I 716 69 3 680 680 68.1 68 2 68 2 79 8 78 8 87 5 87 2 80 1 680 68 1 78 5 141 91 1
64.1 648 62.4 67.1 66.3 66.0 666 669 62.1 62 1 626 62.5 62 3 615 669 62 8 626 179
b
168 9
128 8
208
78 2
62 5
C-l
c-2
c-2
: e e e e e e e e e
169.5 175.2 1747 1746 175.5 1755 175 5 1740 175 4 175 4 1744
128.9 83.1 83 7 83.5 83.5 834 834 84.1 82.7 83 1 83 6
201 715 71 1 712 69 2 691 691 715 69 3 69 4 709
f
175.3 174.8 114.7 175.1 1742 114 4
834 842 844 82 6 842 86 1
695 709 71.2 80.1 803 79.7
172 2 173 5
81.6 433
715 -
f e e e e 2’C
C-2”
New actd c-3 C-3’
c-4
c-s
Solvent*
Ref
26.1
15.6
-
a
c251
1598
21.5
205
-
a
WI
-
1392
-
159
-
a
c271
-
1391 1391 33 1 32 2 32 2 32 8 32 7 32 6 32 3 32.4 33 1 324 330 39 1 39 1 31 8 73.1 74 3
173 160 179 17.3 169 16.9 17.3 17.2 17.2 17.4 172 12 1 12.1 17.1 26 3 264
16.1 160 170 178 160 17.0 17.3 17.3 178 176 17.3 174 172 24.8 249 16.4 27 2 264
12.1 12 1 @‘)-O-Me (2’)-O-Me @‘)-O-Me
f
c241
;
c51 VI PI Cf31 PI PI I%1 C61 C6,291 ~291 C61 181 II81 [5,(X301 c91 c311
32.3 25.1
17 5 222
163 22.2
-
a
~321
17 1 174 173 173 17 4 174 158 166 170 160 170 174 144 12.5 136 13.5 145
a a a a a a a a a a a a a a a
WI
16
E ROEDER
Table
Mass
4
‘~‘L‘iVkfR data of pyrrolizrdme
Formula
239
alkaiom
dresters wrth the necme base esterttkd- m poattton-7 Compound No
c-1
C-2
c-3
C-S
Necme C-7 C-6
a
Name
CAS-Reg
Retronecme-7,9-dtacetate
25471-78-7
4.1
133x
1271
612
537
344
740
7-Angeloyl-9-sarracmoylretronecine
87838-91-3
4.2
133.8
1276
609
598
346
689
Trtangularme
87340-27-o
4.3
1337
1274
625
53 7
345
736
Neotrrangularme
873922614
4.4
1338
1276
627
53 7
346
738
Sencalenme
95066-37-X
4.5
1336
1268
621
540
342
718
7-Senecioyl-9-sarracmoylretronecine
87838-91-3
4.6
1328
1273
61 7
537
344
730
2492-09-3
4.7
402
288
552
536
350
68 8
Lycopsamine-7-acetate
73544-48--6
4.8
1328
1305
629
53'5
340
713
Intermedme-7-acetate
74243-09-9
4.9
1329
1259
613
53 5
340
695
4.10
1337
1273
623
536
343
73 1
Sarracine
Dortasemne
No
and- -9. (see structure
120091-13-6
Hehotrme-7-acetate
26607.-98.-7
4.11
1353
1276
616
54 0
329
768
369
Dthydroxytrtangularme
93710-21-5
4.12
1393
1275
626
539
344
737
381
Symlandme
74410-74-5
4.13
1332
1270
622
535
343
710
381
Symphytme
22571-95-5
4.14
1332
1279
622
538
343
709
397
Heltosupme
32728-78-2
4.15
1343
1275
622
542
301
770
397
Echtmtdme
520-68-3
4.16
1329
1286
628
53 7
345
698
409
Lattfolme-4-oxide
987522-06 -8
4.17
1263
1224
803
696
321
723
411
Lastocarpme
303-344
4.18
1347
1285
622
542
304
782
425
9-(2’-Isovaleroyl) vtrtdtfloroyl-retronecme-7-dcetate
115793-79-g
4.19
1325
1259
(612)
532
339
728
31514-30-4
4.20
1345
1288
62 2
543
30 3
767
5764-58-6
4.21
135 I
1283
622
543
305
768
Hehosupme-7-acetate Lasiocarpine-(9)
*Solvent
a=CDCl,
3-acetate
Pyrrollzldme alkaloids
C-8
c-9
15 8
629
759
628
75 8
607
75.9
612
16.4
605
15.1
617
15.2
640
154
613
754
608
15 7
606
78.4
62.0
15 6
621
IS 6
619
15.6
619
19 1
626
15 9
628
93 8
613
78.9
624
75.2
(61.6)
78 8
621
78 I
62.2
POSltion
Ester
C-l
7 9
a
a
1710 1710
21.2 208-
1668 1666 1668 1667 1669 166 8 167 2 1649
7 9 I 9 I 9 7 9 1 9 I 9 7 9 7 9 I 9 I 9 7 9 I 9 7 9 I 9 7 9 7 9 I 9 7 9 2 I 9 I 9
c b b b a e a e E b a e b b b e b e b ; e b e b e
c-2
17
Neclc acid c-3 c-3
c-2
C-2”
-
-
-
-
1215 1316 121.4 1317 1276 131 I 1336 128 1
158 650 20.5 648 205 561 160
--
1392 1412 139.4 141 1 1393 141.3 1408 140.2
66 8 -
205 158 158 158 158 142 159 205
-
165 8 1660 166 8 167 0 1703 1743 1700 1749 1666 1660 1712 1741 1669 174 1 1669 1744 1669 1744 168.3 1743 1669 174 1 165.7 170.7 168 1 173 8
1159 131 6 127 1 1320 210840 21083 5 1129 1596 21283 2 128 1 82 5 128 5 83 8 128 5 83 7 1275 82 8 127 4 82 I 1308 83.7 1274 83 6
65.1 201 64.5
1578 1422 1395 1407 32 1 33 1 1318 1405 30.4 1335 693 1380 32 3 1380 32 3 1391 13 9 1391 17 1 1409 467 138 1 15.6
27.5 17 8 172 66.7 17 1 178 17 8 25 9 24 8 1751
204 158 15.5 15.7
-
174 -
-_
172 15.8 157
-
78.8 206 652 20.0 73 5 119 13.5 205 69 8 204 73 7 160 81 7 205 71 5
159 170 11.5 160 160 18 5 18 5 14 1 130
169 5 173 8 1717 1619 1732 1677 1730
208816 434 1216 82.8 127 7 837
138 (152) 125
-
717 21.0 726 204 78.7
731 13 1 643
321 25 5 1385 73 1 138.4 85 2
26 5 166 22 2 24 5 --17 1
c-4
17.1 @‘)-O-Me 158 175 14.5 174 145 174 159 248 15.7 258 204 8.8 158 24 5 (3)-O-Me
Solvent*
Ref
a
II51
WI [Zl, 22, 333 c331 c231
a
[20, 231
a
c20,
a
Cl91
a
Cl91
a
c341
a
[51
a
VI
a
c351
a
Cl91
a
c 91
a
C361
a
c371
a
lI5,6, 91
a
~321
-
_
171 222 158 26 6 158 17 1
a (2’)-O-acetate a @‘)-O-Me (3)-O-acetate
221
C381 c41
E
18
ROEDFR
5 13C NMR data for pyrrollzldme
Tdble
alkaloid
2oMe
macrocychc 17
1sMe
dlesters
Me
3a
Compound No
C-l
C-2
C-3
C-5
Necme C-6
Mass
Formula
Name
CAS-Reg
309 309 309 325 341
C,,HIxNO, C,,H,,NO, C,,H,,NO, C,,H,,NO, C,,H2,NO:
6024-88 -5 120154.-95-2 6029-87-4 315.-220
5.1 5.2 5.3 5.4
133 I 1328 1336 1323
1344 1357 1318 1342
585 610 607 604
542 532 53 6 53 7
351 353 367 369 383 409
C,,HZ,NO, C,,HZ,NO, C,,HZ,NO, C,,H,,NO, C,,HZ,NO, C,,,H2,N0,
Crlspnttne Crotaleschenme Fulvme Monocrotdhne Monocrotdhne-4oxide Grant&x Axlllarldme Spcctdblhne Axdlarlne Spectdblhne-4-oxide Monouotalme12.1 i-dlacetate
35337-98-S 83482-61-5 23506- 96-9 520 -55-8 I9637 -66-2 82503-65-9
5.5 5.6 5.7 5.8 5.9 5.10
1317 131 9 1335 1330 132 1 1315
1341 1369 1364 1344 1357 1350
78 x 614 622 599 614 795
25490 -6X-o
5.11
1330
1350
599
*Solvent
tr-CDCI,,
h=DzO.
No
C-7
C-8
C-9
3.3 5 33 6 -I? s 33 5
73 76 7s 74
4 3 6 6
78 3 75 5 77 0 76 8
614 618 hl 8 613
69 2 53 8 55 0 53 8 54 1 hX 9
33 39 34 32 34 33
74 8 75 6 74 7 73.3 72 4 73 0
Ybb 71 0 78 9 78 I 77 9 970
62 0 61 8 59 9 59 8 5Y 5 h2b
536
325
74 0
778
61 2
8 9 9 7 0 3
c-C,D,N
Table
6
13C NMR data for pyrrohzldme
alkalotd
IsMe
20Me 21
macrocyhc
dlestcrs
ITMe
Me
3b
Mass Formula __--_.-___ 367
C,<,H,,NO, .._-.___
*Solvent
(I = C DCI,
Name
CM-Keg
No
Compound No
C-l
C-2
1342
133 8
__-__Crownperlne ----___
30785-56-Y
6.1 -____
c-3 ____649 ~-l--_l_-.
C-5
C-6
522
73 2
Olonecme C-7 76 6 __--_
Pyrrohzidme
wtth an 11-membered
rmg of the Crotalanan-type
(structure
alkalords
3a)
c-11
c-12
c-13
c-14
Neclc acrd c-15 c-17
C-18
C-19
1770 175 9 1743 1748
45.8 76.5 47 5 78.6
73 8 376 75.4 777
494 48 0 512 442
174 1 1748 173 5 1743
24 1 272 205 224
142 185 127 182
12.4 114 12.5 143
1784 1692 t_752
79.8 820 1123
80 5 80.7 74 ?
449 48.6 527
177 1 1732 174 6
23 7 (259)
19.7 30.0
15.6 768
212
214
317
18.2
259
222
18.1
171.7 173 1 1784
770 82.2 792
85.6 69 9 88 5
43 6 51.4 45 0
1714 172 5 173 3
(190) 69 8 23 3
15.5 178 192
14 1 275 163
1692
88 7
857
416
1739
178
175
154
with an 1 l-membered
C-8
4-Me
rmg of the Otonecan-type
c-11
c-12
c-13
(structure
c-14
19
C-20
C-21
(13)-acetate 217
Solvent*
Ref
a a a a, b, c
C(5), 61 1871 161 17. 9, 10, 39, 401
a, b a
17, 101 161
B
[At!.
a
(13)-acetate
b
16 71 C4ll c71
(12)-acetate (13)-acetate
a
161
177
a
3b)
New c-15
acrd c-17
C-18
c-19
c-20
C-21
Solvent*
Ref.
E ROEDER
Table
%NMR
data for pyrrohzldme
alkaloid
macrocychc
dlesters
18 Me
21 Me
I
4a
Mass
Formula
Name
333 333 335 335 335 335 337 317 337 349 349 349 349 349 351 351 351 351 351 351 353 353 353 365 367 369 383 383
C,,H,,NO, C,$iHZANO, C,,H,,NO, C,,H,,NO, C,,HZ,NO, C,,H2,N0, C,,H2,N0, c,,H,,Na, C: &-NC), C,,H2,N0, (I: rrH ;$IQ:,. C,,H,,NO, C,,H,,NO, C,,H,,NO, C,,H,,NO, C,,H,,NO, C,.aH,,.No,. C: ,Ff I:.NO, C,,H,,NO, C,,HZSNO, C,,H2,N0, C,,H,,NO, C,,H2:N0, C,.s.H,,NO-. C!,H25NO-. C,,H,,NO, C,,H,,NO, C,,H,,NO,
Seneclphylhne Spartloldmz Integerrlmme Jacobme Seneciomne Seneclvernme Llguldrmme P!‘iIy$l~!llne Ne~pidly~hy!lme Eruclfolme .lac~~me Rtdelhme Swdzme Seneclphyllme-4-oxide Andcrotme Gynuramme
4%~81-9 5IGS9-2 48&79-5 687G-67 -3 1-10-O 1,x 72755-25-o 90364-90-2 48&78-4 2036I-76-6 40158.-95-6 iTQ-2.-(1 23246-964 38763-74-5 3X710-26-8 5096 -49-l 8561 l-434
%!JlfCCJ~~Wlr;4-WCldC
1_2xiK~~7-~2_
48&~4-6 15503-87-4 98264-41-6 3573-82-8 52@ 65-o 9820549-3 7M’i& l_l,-o
393
CZ,H,-I\IO:
395 395
CZ,H,-NO, CZ,)H,,NO,
Retrorunc Usnramlne Uspnllatme Hygrophyllme Rosmdrmme Dlhydroretrorsme Rldelhme-4-oxide Rctror\me-4-oxide Jawhe Alkaloid (adomfolm)* Dlhqdrouy-dlhydroerucrfolme Gqnuramme-19dcetatc Uspalidtlne-6-acetate ITolme
CAS-Reg
No
15503~-86-3 480-76-2 115712-88-4
Compound No
C-l
c-2
c-3
Necme c-5 C-6
7.1 1.2 7.3 7.4 7.5 7.6 7.7 ?;8 ?:9 7.10 7.11. 7.12 7.13 7.14 7.15 7.16 7-J-7 1.JQ 7.19 7.20 7.21 7.22 7.23 2.24. 7.2zX 7.26 7.27
1322 LIl_ 1 131 8 1312 112 2 1315 40 3 38 4 39 5 1312 I-Il. 7_ 1312 131 8 1322 1315 1313 1.33 4 1.23_2. 1317 1.11~0 41 6 49 1 394 1.21.9 1~334 1314 1313
1366 L370 1364 1364 l-16 I 136 1 29 6 i! 7 30 3 1343 I.16 7 1367 1366 1424 1365 1356 140.6 1.25L 1366 1~359 29 5 69 3 316 1.414. 141 I 1362 1360
627 62z 622 631 62z 607 547 536 515 62 1 61 0. 624 61 2 803 63 5 629 80 5 622 625 624 546 61 4 515 WE 807, 634 606
513 528 532 530 szo 532 525 5!9 528 534 510. 532 53 1 710 585 531 71.1) 1?4. 529 60-i 523 535 534 71-11 709 536 537
360 338 338 350 377 342 34 8 358 355 351 $50. 347 34 I 352 748 314 353 169 -337 7X6 35 3 345 353 111 353 345 352
106283%53.-8 85547-34-8 98264-42-7 3000&36-3
*Exact ndme 12,13.19-tr~hydroxy-15,20-epoxy-15,20-d~hydro-(l2s, ISolvent a=CDCI,. h=DZO
7.29 7.30 7.31
1314 1307 131 6
135 1 1364 1357
629 625 606
532 579 532
15R, 2OR)-seneclondn-11,16-dlone
342 71 1 346
C-7
C-S
C-9
749 7.1 I_ 754 759 7sx 765 75 1
777 17 I_ 774 176 770 765 68 9
742
695
739 750 76 1. 750 759 763 755 750 76 7 717 755 767 730 75 2 686 76.6. 76 7 766 779
690 772 77 5 773 776 98 I 744 776 92.3 767 769 748 736 69 3 739 9x0. 880 777 78 8
61-2 601 608 605 614 627 64 1 666 fih7 609 40.8. 622 622 626 607 607 62 2. 63 3 612 600 650 62 3 644 63.L 62 5 60.9 67.4
786
77 8
605
751 756 769
776 752 775
610 602 636
Pyrrohvdine alkalotds
21
wrth a 12-membered rmg of the Senectonan-type (structure 4a)
c-11
c-12
c-13
c-14
c-15
New C-16
actd C-18
1770 1765 1782 1779 1777 178.1 L75@ 178.7 1786 169 7 LVi4 174.3 1766 1785 1783 1768 1803 175 6 1756 1778 1782 1800 1755 1764 1780 1784 1699
764 76 1 76.4 77 1 76 7 77 7 75 7 75.8 64.4 765 79 2 774 79 5 768 780 804 81 3 81 3 766 78 1 774 802 82 5 848 77 7 74 1
1464 144.9 394 38.1 38.2 40.8 294. 37.4 36.5 65 9
37.2 29.0 296 360 38.3 35 9 XL9 39.2 39 3 35.3
I-4.3 4.
25 Z
724.Q
1_1_4,9
VLh?.
377 356 39.4 384 348 404 360 29.3 379 723 395 388 39 8 40.1 368 408
167.1 1680 169.2 1686 1675 168.8 t_473167 7 167.3 1682 l_fixI 1670 1681 1707 1696 167 4 171.5 167 3 1689 1669 166.9 1675 167.2 171.1 171.1 1758 167.5
24.9 24.7 25 2 24.3 250 26.2 t-7.P 26.2 26.4 149
1432 794 149 0 383 439 41 2 356 36.8 322 407 378 345 145.9 38 5 373 654
1314 131.8 134.1 64.1 133 2 147 4 t_xt_s. 131 8 131 8 1300 627-7 1312 143.1 1312 132.8 132.2 1313 1313 133 4 1324 1334 1326 1309 1312 1312 81 7 616
66.2 219 266 252 25.3 26.7 66.7 671 248 25.7 257 67 5 683 69.1 24.5 154
1147 417 116.9 11.3 58 5 13 1 11.6 12 3 10 8 58 117 13.8 117.7 13.6 14.1 63 2
135.9 169 1341 134.3 136.8 134.2 1362 135.7 1347 1351 134.4 136.1 1344 134.5 72.6 73.7
15.2 122.0 17.6 15.2 15 1 17 5 150 142 14.9 152 15 1 15.3 17.6 17 5 172 145
1695
654
61 5
409
74 1
167.2
145
67.3
737
154
177.3 1178 176 1
76.2 764 83 6
426 382 373
347 379 396
132.2 132.2 78.8
167.2 25.5 (166 7) 24.8 149 1721
62.2 10.9 15.9
77. 1_
C-19
C-20
1144 113.2 11.8 12.8 111 57
135 8 1356 135.3 560 1340 12.0
C-21 15.2 13.4 142 136 151 120 5
LX24
Llt.9
13 5 137 62.8
1365 156 1378 144 133.5 160
Ref
a
C6, 7, 431 c43,441 C6,46,471 C6,481 [7, 45, 47, 49-521
a
a a a a a.
354.
a
a a 4 a
132
136.9 15 1 135.2 14.9 333 74
Solvent7
; a a b a a a a a h”
b b a
(19)-acetate (6)-acetate (la)-acetate
c45, 531 (%4$ [6, 7, 50, 551 C6, 551 C561 [Q.
C6,71 Clll c71 C61 iI C7, 521 [5-7,11,14,45,47,51,58] c441 Cl71 [6, 7, 11] c33, s91 Cl71 c71 c71 C481
~521
a
C261
a
c571 Cl71 Clll
a a
E ROEDER
22
Table
8 ‘W NMR data for pyrrohdme
dlkalold
macrocychc
dlesters
18 Me
21 Me
0
20
Me 4b
Compound Mass Formula
Name
365 365 36.5 381 381 381 383
C,,H,,NO, C,,H;;NCI, Ci-&li;NOb C,,HZ,NO, C,,H,,NO, C,,H,,NO, C,,HZ,NO,
Emhe Neo_%nk&mnc ScnhrkLna Anonamme Otosemne Hydroxysenklrkrne Synellesme
407
C,,H,,NO;
SakLrkLm-12-wJat~
423
C,,H,,NO,
423 423 441 459
Fukmotoxme-12acetate C,,H,,NO, Florosemne C,,H,,NO, Ligularizine C,,H.<,NO, Florldanme C~iH3Jl.NO&ho.m~
*Solvent
(1 =
CAS-Reg
No
No
-
8.1 8J a 8.4 8.5 8.6 8.7 U
36506-99-7 57194-7w 211118-5 111566-66-6 16958-29-5 26782-43-4 55652m~65-8 530x-44-7
60409-51-O 16958&30--8 90364.-924 16958-31-9 6.036.7-O&2
8.9 8.10 8.11 8.12 813
C-l
c-2
C-3
Octonecine C-5 C-6
C-7
C-8
c-9
1357
1318
134 5
1374
L34 3
137 3
532 533 532 536 532 533 535 534
375 339 171 354 355 358 373 361
772 792 7RL 785 785 779 784 7RX
1915 1918 I.917 1917 1905 1853 1894 I.924
586 650 643 647 59 1 640 636 5X8
531 529 532 544
365 351 358 359
773 790 774 792
1900 1918 1902 191 1
589 58 9 58 9 60 2
546
36X
745
1411
6.45
1343
1374
1343
137 1
133 8
1367
1342
1360
134n
138 2
666 583 5X4 589 642 567 522 64X
1333 133 7 1355 1339 I.34 5
1387 1384 1383 136 7 I.36 8
641 64.6 63.7 640 593
-
--
CDCI, Table
9
13C NMR data for pyrroltzldme
alkaloid
macrocychc
dlesters
5 -_ Mass
Formula
Name
CAS-Reg
335 337
C,,H,SNO, C,,H,,NO,
Doronemne Bulgarsemne
74217-57-5 62018-77-3
*Solvent
a = CDCl,
No
Compound No
C-l
c-2
c-3
c-5
C-6
9.1 9.2
1320 316
1354 32 7
63 4 506
52 6 52 6
34 1 370
Necme C-7 77 1 72 6
Pyrrohzrdme
wtth a 1Zmembered
rmg of the Otonecan-type
alkalords
23
4b)
(structure
4-Me
C-11
C-12
C-13
C-14
C-15
New acid C-16 C-18
C-19
C-20
C-21
402 413 404 41 1 400 40.5 404 406
174.7 178.2 1780 178 3 1777 175 1 176.7 171 1
752 770 766 764 779 810 78 9 775
1465 396 386 38.3 385 356 41 2 409
31 1 29 1 369 303 37.1 372 74.3 374
469 132.7 131.7 132.3 637 1308 733 1320
177.6 167 9 166.5 1667 177.8 1609 1714 166.5
285 24.9 246 25.5 239 663 243 221
1179 11.6 109 12.5 125 113 58 11.5
26 5 138 I 137 0 1406 56.1 137.2 23.0 137.4
120 14 5 15 3 59 3 136 15 1 118 15 4
(12)-acetate
400 39.9 40 1 39.8 404
170.5 168.0 1712 171 4 1728
83 4 83 6 82.2 840 81 5
38.4 404 363 40.9 40.2
370 37.1 36.9 63 1 364
62.6 63.8 62.2 82.0 83.8
166.3 171.1 1660 174.7 1713
21.5 214 14.4 21 6 216
130 12.9 13.9 14.6 14.3
61.4 55.9 61.4 72.8 63 0
15 6 13 6 15 5 17 2 18 3
(12)-acetate (12)-acetate (12)-acetate (12)-acetate (12)-acetate
Necic actd C-16
c-17
c-19
c-20
c-21
Solvent*
Ref
167 7 1669
24.6 26.8
117 155
28.3 28.1
a a
1681 C681
wrth a 13-membered
rmg of the Doronenan-type
(structure
C-8
c-9
c-11
c-12
c-13
c-14
c-15
75 7 704
60 5 67.4
1777 1877
757 75.7
34.6 360
41.1 37.3
151.8 1544
Solvent*
Ref.
CW [47, 51, 611 [h, 7,45,51,52,62]
c511 [Sl, 63, 641 I511 C3, 6, 651 C661 c541 [47, 52, 641 c541 c641 C62,671
5)
118 5 118 3
24
E
ROEDER
Table
10 “C NMR data for pyrrohzrdme
alkaloid
macrocycllc
dlesterr
6
Mass
Formula
Name
351 367 393
C,,Hz5N0, C,,HZ5N0, CZ,H,,NO,
Madurensme Crotaflorme Madurensme-7-acetate
*Solvent
u = CDCI,
CAS-Reg 26126-78-3 112156-54-4 112156-53-3
No
Compound No
C-l
c-2
c-3
10.1 10.2 10.3
129 9 1354 1354
136 1 136 3 1361
53 3 66.4 665
Necme C-5 664 614 61 1
C-6
c-7
74 7 752 74 5
73 7 746 766
Pyrrolizidine
with a 13-membered
ring of the Madurensan-type
(structure
C-8
C-9
C-l
1
c-12
c-13
c-14
c-15
C-16
15.2 73.1 71.5
61.5 59.8 58.9
176.9 174.9 178.0
76.3 81.2 75.9
40.5 37.2 39.6
27.6 21.3 27.2
135.6 129.1 131.8
167.0 166.9 167.3
25
alkaloids
6)
Neck acid C-18 C-19 24.6 66.5 24.3
10.8 19.5 10.6
C-20
C-21
Solvent*
Ref.
142.5 143.0 142.1
15.0 15.0 15.0
a a u
II5 691 C691 C691
(7)-acetate
E
26
ROWER
Table
lla
1 1 “C NMR data for mtscellaneous
NH
llb
NH
$OH 12c
12b
Mass
Formula
Name
CAS-Reg
No
Compound No
C-l
c-2
C-3
C-5
C-6
C-7
(‘-8 _____
Necme c-9
Pyrrollzldme
pyrrohzldme
alkaloids
3
27
(7.-19)
ItIlt? Me4
Mea’
18s 1Ub
R=H R=A~
C-l’
alkaloids
c-2
C-3’
C-4
New acid or a condensed system C-5’ C-l” C-2” C-4’ C-3”
C-S”
C-6”
Solvent*
ReI c701 c711 c731
519 167 8 1696 1663 1680 1742
21 8 1136 1175 1404 1125 83 3
1742 1742
81 6 75 8
1760 1581 1189 1461 706 73 6 455
1395 218
1710
1282 205
518
~ 1279 1240
429
~ 1293 1304 32 5
14 3 1144 1171 16 I
1610 163 5
32 5 1348
16 1 1302
177 1282
1144 117 1
1296 1304
(4”)-O-Me
171
a
173,74, 751
b b b b b a b a a a
C761 1761 1771 C781 c791 WI [811 IQ1 I831 cf341 I851
a (3’)-acetate 1272
a ?
I851 Ml
E ROFDER
28
Only m a few cases was it necessary to apply perdeuteropyrldme (C,D,N), perdeutero-DMSO [(CD,),SO], perdeuteromethana1 (CD,,OD) or de~&xame+hanol (M&D). In all cases tetramethylsdane (TMS) was added as mtcrnal standard or the chemical shift was related to It
~.4SR~.~!.st.ry-Nu~~~~
30
31 32
C’A.S=Rellzstr~-Nunzher The
29
L1as hren
allows a fast access to the hterature CAS online-research
ti.
aIts.
of an Jkalold
gwxL,
via
31 34
Pyrrohzldme
65 Hlklchl, M and Furuya, T (1976) Chem Pharm. Bull 24, 3178. 66 Gonzalez, A G , De la Fuente, G , Rema, M and Loyola, L A_ (.l_wfi). erflwl. MpJi. l-fin 67 Riwiq. E,. WwIenfeJ~. H_ and_ Knwzqj~-Fwhp. P (1984) Planta Med 50, 203 68. Roeder, E., Wledenfeld, H and Frlsse, M (1980) Phytochemwry 19, 1275 69 Akr&izZ. R,. A~.nafq,.G .DwUP&,.H_ ami sJlti7kPt.G px7). Tetrahedron 43, 3263. 71). !hxh,. E,. Wwienfel&. H and Bonllriwel,. T (1986). be/~,g~ Ann Chem 1645 71 Roeder, E ,Wledenfeld, H and Bourauel, T (1985) Lleblgs Ann Chem 1708 72 Dannha&,.G (.L!85).(unplti1sh~&dat~. 7.2 Mahk,. G anil_ Rahmann,. K_ (.l_‘XQ Hpf~~~&_~ 27,. 7Q7 74 Wmkier, T and Heckendorn, R (1988) Heterocycles 27, 2331 75 Ster.m~tz,~F R~ and~LIEmp~eur,~K M (1988) TPtrnhedron~ Letters 4943
7.7.
Nash,. B. I,. EpJlnwq. L. E,. nJlln&_ I V ;_ Flw& G W I,. Derome, A E , Hamor, T A, Scofield, A M and Watkm, D
alkaloids
29
J (1988) Tetrahedron Letters 2487 78 Molyneux, R J, Benson, M , Wong, R Y, Tropea, J E. and Elbem, A. 0. (1988) J Nat. Prod. 51, 1198 79 Nash,. K I.,. F&X%. 16 E,. Plans,. A_ C,. Flm=&.G. W I;. DeUZmlq.L E,.Balt&P n ~.Hpgjvfy.,.M_ e and_Scsrfid~. AM. (1988) Tetrahedron 44, 5959. 80 Roeder, E , Wledenfeld, H and Jost, E -J (1981) Planta Med 43, 99. 8.1. I&u,. 9,. Gaw;td. D E,. PPJIPJXX,. S W! ,_Killlthq. G and Bhandary, K (1986) J. Nat Prod 49, 614 82 01ylq.T W,,.NeUl&xqD E.,.&&q.D M,.Mk&yj..l Ej. Gruhch, R E., McCabe, T. and Clardy, J (1980) .I Org. Chem 45, 1324 83 Ikhln, K., Ahond, A, Poupat, C, Pothler, P, Pusset, J and Siwenet,.T (.1987). I N& Pro/i .%I.626 84. D&son,. Cd D a& StFXmltz,. F R. (mfi)..Z Nat. Prd. 49,. 727 85. Abe, F. and Yamauchl, T. (1987) Chem Pharm Bulf 35,466l 86 Fupki, K, Shoyamq~Y ,~MIatsun&~K andN~sbmka, J (1988) Phytochemrstry 27, 1564 87. Smlti,. L. W ,. Edgar,. 1 A_,. Wdh~. R. I;. Cs;lhlq. R. W ;. Mackay,.!& E ,.SurI,.Q P ,&al,.C. K an&Culv.~~~mr,.C, C 1 (.1!%8).Ic~t. J! C&m. 4.!_.4%!
Vol 29, No I” Great Bntam
1, pp 11-29, 1990
0+X-9422/90 $3 OOtOOO kc 1989 Pergamon Press plc
REVIEW
CARBON-13
ARTICLE
NMR SPECTROSCOPY E.
Pharmaceutical
Institute,
Unlverslty
alkaloids,
50
OF PYRROLIZIDINE
ALKALOIDS
ROEDER
Bonn, An der Immenburg 4, D-5300 Bonn 1, F R.G
(Recerued WIrewedform Key Word Index-Pyrrohzldlne
NUMBER
16 June 1989)
13C NMR spectral
analysis,
structure
elucldatlon
Abstract-13C NMR chemical shifts of more than 130 naturally occurring alkaloids published up to 1988 are listed. The utility of 13C NMR spectroscopy for the structure elucidatton of these compounds combmed with mass spectra IS discussed
which gives the molecular formula, the molecular weight and m addition some Important mformatron concerning the structure of the alkaloid. The tables contain only literature data which can defimtely be related to a compound If several authors described the same alkaloid, the average value for the chemical shift has been determined and listed. Obvrously wrong assignments have not been taken mto constderation or the values have been put into brackets. The same procedure has been applied, where an assignment was difficult to carry out. The values of acetyl groups, esterrfied to the hydroxy functions of the necimc acids or, m some cases, with the necme itself, have not been listed. For the carbonyl group the chemical shift IS about 6 169.2* 2 The signal for the methyl group appears at 621 3 f 1.5 (measured m CDCl, solutron) The signals for methoxy groups m the necmrc acids have not been listed Their methyl signals appear at 656.8&O 3
INTRODUCTION
The application of r3C NMR spectroscopy is playing an outstanding role m the structure eluctdatton of naturally occurring compounds [ 1,2]. Since the first application of ‘%NMR spectroscopy in 1974/75 by Htkicht [3] and Culvenor [4] It has been one of the standard analytical methods in the field of pyrrohzidme alkaloids In the meantime the ’ 3C NMR data of more than 130 alkaloids have been published. Unfortunately they are widely spread m the hterature and accordingly difficult to find. The reviews which were published m 1982/83 [l, 5-81 have not changed this srtuatton In the textbook ‘Carbon-13 NMR Spectroscopy’ by Brettmater and Voelter [2], in the chapter ‘Natural Products’, data has been mcluded on some pyrrohztdme alkalotds, but this mformatton can only be a ‘first aid’ for the mterpretatton of r3C NMR spectra After the pubhcatton of many papers during recent years, which describe the use of r3CNMR data for the structure eludtcatton of alkaloids, tt seems to be necessary to present a new revtew deahng with the 13CNMR data of pyrrohztdme alkaloids.
Nomenclature Apart from the necine ring system, the numbering of the C-atoms IS very arbitrary and different In the Chemical Abstracts there IS no obvrous regulatmg prmctple. Therefore, the numbering was standardized as tt IS shown m formula Z m combmatlon with the necmic acids ofthe basic types a-f For the macrocyclic alkalotds of the Crotalanan-, the Seneclonan- and Otonecan-type, the nomenclature and numbermg of Chemical Abstracts have been adopted. For all other macrocychc compounds only the numbering of Chemtcal Abstracts has been used
RESULTS
The amino alcohols forming the basis of the alkaloids, the necmes, and the sample alkaloids formed by the estertficatton with mono-carboxylic acids (necinic acids) have been listed in Tables l-4. The general structures of the necimc acids are given m the formulae a-f shown in Table 2. For the multttude of macrocyhc alkalotds based on drcarboxyhc acids, Tables 5, 7, 9 and 10 have been comptled for the 1l-, 12- and 13-membered rmg-systems. The otonecine-alkalotds, which belong to the 1 l- and 12-membered macrocycles, have been comptled in Tables 6 and 8 Atypical alkaloids have been summarized in Table 11 Generally for every structure eluctdatton of a natural product, a high-resolution mass-spectrum is presented
Solvents and standard The Tables also contain the solvent whtch served for the measurement of the spectra Most alkaloids have been measured m deuterochloroform solution (CDCI,). The spectra of salts and N-oxides, which are soluble m water, m most cases have been made m deuterated water (D,O). 11
E. ROEDER
12
Table
1. “C NMR data for alkaloids R
R 7
R
ZHZOH
-cl?5 1
8 \\
17.3)
6
5
N 4
'2
3
R=HorOH 1
Mass
Formula
139 141 141 155 155 155 157 157 157 171 171 *Solvents:
Name
CAS-Reg.
Supinidine Trachelanthamidine Isoretronecanole Heliotridine Retronecine Retronecine’ (HCI) Curassanecine Platynecine Dihydroretronecine Uspallatinecine Retronecine-4-oxide
551.-59-7 52664-l 526-63 -~6 520-6338 4X&-R5 ~3 875-22~~9 82842X0-0 52&--6221 520-62~7 98303-06-l 687G-3333
a=CDCI,;
h=D,O;
c==C,D,N;
No.
Compound No.
C-l
c-2
1.1 1.2 1.3 1.4 I.5 1.6 1.7 1.8 1.9 1.10 1.11
137.84 48.14 48.22 138.00 138.40 135.71) 80.32 45.80 43.90 131.00 138.30
121.02 31.95 31.81 127.10
126.00 120.50 39.15 30.40 28.60 135.90 122.50
d=(CD,)$jO
Table
2. 13C NMR data for pyrrolizidine
alkaloid
monoesters
a
6
sMe 3
5
R = necic acid R=H 2
Mass
Formula
Name
CAS-Reg.
237 237 237 239
C,aH,,NOa G,H,,NO, C,,H,,NO, G,H,,N%
Angeloyl-heliotridine Angeloyl-retronecine Senecioyl-retronecine Angeloyl-platynecine
723-78-4 602998229 63503-33-3 940543227
*Solvent:
a = CDCI,.
No.
d
Compound No.
C-l
C-2
c-3
C-5
Necinc C-6
2.1 2.2 2.3 2.4
137.7 138.1 138.X 43.9
126.5 127.7 121.8 28.7
63.2 62.1 61.8 S5.6
53.6 53.x 53.5 53.6
34.6 30.2 34.3 35.2
Pyrrohzldme with the necme base (structure
alkaloids
13
1)
c-3
c-5
C-6
c-7
C-8
c-9
Solvent*
Ref.
59.91 54 19 54 78 58.70 59 50 56.80 45 66 5120 55.30 62 40 80 50
56 64 5453 54 52 54 10 53 60 53.10 5329 5560 53 80 60 30 70.70
25 25 25 35 36 34 25 38 36 78 36
30 43 30 08 29 92 71 10 71.50 68 40 2184 7500 7130 76.70 72 20
7127 69 92 68 16 79 50 77 30 77 80 70 80 73 10 1300 14 60 9180
6190 65 25 64 97 6190 62 30 60 50 68 38 63 40 61 50 60 10 60 80
a
I?31 PI PI cw
90 75 69 10 30 20 42 30 50 60 60
with the necine base esterllied
m posltlon-7
oMe
4Me
(see structure
a a a
a, b, d
[S, 7,9-l l] [S, 13-161
b
PI c51 Cl11 Cl71
i b
[I, 10, 15, 16, 181
;
2)
Mes
0 C
b
4Me
Me
3’
f
e
r-f
c-7
C-8
c-9
Ester at c-7
14.1 77I
75.9 792
601 598
b b
1687 1676
1244 1253
205 20.5
-
1408 1399
-
724 15.1
76 3 69 2
594 627
c b
1680 167.0
1150 127 2
(208)
-
138.8 1394
27.6 -
C-l
c-2
c-2
Neclc acid C-2” c-3
c-3
c-5
Solvent*
Ref.
159 158
-
a a
Cl91
20.5 (158)
-
a a
~231 ~241
c-4
[20-221
E ROEDER
Table
Mass
Formula
239 253 253
C,,H,,NO,
255
C,A,NO,
255 283 285 285 285 285 285 299 299 299 299 299 299 299 313 329 345 383
CI~HZ~NO~ C,,H,,NO, G,H,,NO, C,,H,,NO, C,,H,WJ, CISH,PO, C,,HmNO, C,,H,,NO, C; ,H,aO>, C, xHz~NO~ C,zH.z,NO, C,,H,,NO, C, bH,,NOh C,,H,,NO, C,,H,,NO, C,,H,,NO, C,,H,,NQ, C,“H,,NO,
*Solvent
a=CDCI,,
Name Fuchslseneclonme Seneeoyl-retronecine-4oxide (Isosenaetnme) Angeloyl-retronecme-4oxide Angeloyl-platynecme-4oxide Hehfolme Supmme Coromandalme Hehocoromandalme Hehocurassavlcme Hehocurassavmme Hehovlcrne Echmatme Indlcmc Intermedme Lycopsamme Rmderme Curdssavme Hehocurassavme Hehotrme Europme Europmi%-4-nxlde (2’-Isovaleroyl) vlndlflaroylretronecme
h=D,O,f=CH,OD
CAS-Reg
No
3 ‘%I NMR data of pyrrohzldrne Compound No
C-l
C-2
c-3
alkaloid
Necme c-5
monoesters
C-6
C-l
51370-97-9
3.1
35.9
31 8
51 9
53 5
39 3
69 6
106283%394)
3.2
132.5
122 2
78 9
70 2
343
699
27773--86-o
3.3
1337
1202
78 3
69 3
352
69 4
94054-33-8 80787-564 551-5X--6 68473-86-9 823544334 X2354-34-5 82374-02.-5 68473-85-8 480-83-l 4&&82-o 10285-06-O 10285-07-l 6029-84-l 68385-70-6 82398-74--l 303-33-3 570-19-4 65582-5X3
3.4 3.5 3.6 3.1 3.8 3.9 3.10 3.11 3.12 X.13 3.14 3.15 3.16 3.17 3.18 3.19 3.20 3iIt
39 4 44 9 1379 448 44 7 44 2 442 44 1 1363 1377 1329 133 0 1362 44 8 44 7 136.4 1373 1322
30 I 71 7 1256 31 5 31 3 309 31 1 31 1 1259 1307 1304 1302 1268 31 6 31 4 1274 1259 !244
71 7 625 61 9 54 5 544 54 3 54 3 54 3 619 630 62 b 629 619 54 5 54 5 620 61 9 68 6
69 9 534 56 9 542 54 2 542 542 54 2 542 518 53 9 53 9 54 2 542 54 2 54 2 54 6 h! ?
35 7 37 3 25 9 25 6 25 6 25 1 250 25 0 33 8 363 36 3 362 340 25 6 25 6 34 3 346 33 6
724 75 7 30 2 302 30 0 29 9 29 3 29 3 74 6 71 4 702 710 74 9 30 3 30 1 75 6 794 713
with
15
Pyrrolmdme alkalotds
the necme base estertfied m positton-
(see structure 2)
C-8
c-9
Ester at c-9
142
661
C
1677
1359
-
131.9
97 1
59.9
c
1662
1148
-
966
60 5
b
1612
127 3
20.5
89 I 716 69 3 680 680 68.1 68 2 68 2 79 8 78 8 87 5 87 2 80 1 680 68 1 78 5 141 91 1
64.1 648 62.4 67.1 66.3 66.0 666 669 62.1 62 1 626 62.5 62 3 615 669 62 8 626 179
b
168 9
128 8
208
78 2
62 5
C-l
c-2
c-2
: e e e e e e e e e
169.5 175.2 1747 1746 175.5 1755 175 5 1740 175 4 175 4 1744
128.9 83.1 83 7 83.5 83.5 834 834 84.1 82.7 83 1 83 6
201 715 71 1 712 69 2 691 691 715 69 3 69 4 709
f
175.3 174.8 114.7 175.1 1742 114 4
834 842 844 82 6 842 86 1
695 709 71.2 80.1 803 79.7
172 2 173 5
81.6 433
715 -
f e e e e 2’C
C-2”
New actd c-3 C-3’
c-4
c-s
Solvent*
Ref
26.1
15.6
-
a
c251
1598
21.5
205
-
a
WI
-
1392
-
159
-
a
c271
-
1391 1391 33 1 32 2 32 2 32 8 32 7 32 6 32 3 32.4 33 1 324 330 39 1 39 1 31 8 73.1 74 3
173 160 179 17.3 169 16.9 17.3 17.2 17.2 17.4 172 12 1 12.1 17.1 26 3 264
16.1 160 170 178 160 17.0 17.3 17.3 178 176 17.3 174 172 24.8 249 16.4 27 2 264
12.1 12 1 @‘)-O-Me (2’)-O-Me @‘)-O-Me
f
c241
;
c51 VI PI Cf31 PI PI I%1 C61 C6,291 ~291 C61 181 II81 [5,(X301 c91 c311
32.3 25.1
17 5 222
163 22.2
-
a
~321
17 1 174 173 173 17 4 174 158 166 170 160 170 174 144 12.5 136 13.5 145
a a a a a a a a a a a a a a a
WI
16
E ROEDER
Table
Mass
4
‘~‘L‘iVkfR data of pyrrolizrdme
Formula
239
alkaiom
dresters wrth the necme base esterttkd- m poattton-7 Compound No
c-1
C-2
c-3
C-S
Necme C-7 C-6
a
Name
CAS-Reg
Retronecme-7,9-dtacetate
25471-78-7
4.1
133x
1271
612
537
344
740
7-Angeloyl-9-sarracmoylretronecine
87838-91-3
4.2
133.8
1276
609
598
346
689
Trtangularme
87340-27-o
4.3
1337
1274
625
53 7
345
736
Neotrrangularme
873922614
4.4
1338
1276
627
53 7
346
738
Sencalenme
95066-37-X
4.5
1336
1268
621
540
342
718
7-Senecioyl-9-sarracmoylretronecine
87838-91-3
4.6
1328
1273
61 7
537
344
730
2492-09-3
4.7
402
288
552
536
350
68 8
Lycopsamine-7-acetate
73544-48--6
4.8
1328
1305
629
53'5
340
713
Intermedme-7-acetate
74243-09-9
4.9
1329
1259
613
53 5
340
695
4.10
1337
1273
623
536
343
73 1
Sarracine
Dortasemne
No
and- -9. (see structure
120091-13-6
Hehotrme-7-acetate
26607.-98.-7
4.11
1353
1276
616
54 0
329
768
369
Dthydroxytrtangularme
93710-21-5
4.12
1393
1275
626
539
344
737
381
Symlandme
74410-74-5
4.13
1332
1270
622
535
343
710
381
Symphytme
22571-95-5
4.14
1332
1279
622
538
343
709
397
Heltosupme
32728-78-2
4.15
1343
1275
622
542
301
770
397
Echtmtdme
520-68-3
4.16
1329
1286
628
53 7
345
698
409
Lattfolme-4-oxide
987522-06 -8
4.17
1263
1224
803
696
321
723
411
Lastocarpme
303-344
4.18
1347
1285
622
542
304
782
425
9-(2’-Isovaleroyl) vtrtdtfloroyl-retronecme-7-dcetate
115793-79-g
4.19
1325
1259
(612)
532
339
728
31514-30-4
4.20
1345
1288
62 2
543
30 3
767
5764-58-6
4.21
135 I
1283
622
543
305
768
Hehosupme-7-acetate Lasiocarpine-(9)
*Solvent
a=CDCl,
3-acetate
Pyrrollzldme alkaloids
C-8
c-9
15 8
629
759
628
75 8
607
75.9
612
16.4
605
15.1
617
15.2
640
154
613
754
608
15 7
606
78.4
62.0
15 6
621
IS 6
619
15.6
619
19 1
626
15 9
628
93 8
613
78.9
624
75.2
(61.6)
78 8
621
78 I
62.2
POSltion
Ester
C-l
7 9
a
a
1710 1710
21.2 208-
1668 1666 1668 1667 1669 166 8 167 2 1649
7 9 I 9 I 9 7 9 1 9 I 9 7 9 7 9 I 9 I 9 7 9 I 9 7 9 I 9 7 9 7 9 I 9 7 9 2 I 9 I 9
c b b b a e a e E b a e b b b e b e b ; e b e b e
c-2
17
Neclc acid c-3 c-3
c-2
C-2”
-
-
-
-
1215 1316 121.4 1317 1276 131 I 1336 128 1
158 650 20.5 648 205 561 160
--
1392 1412 139.4 141 1 1393 141.3 1408 140.2
66 8 -
205 158 158 158 158 142 159 205
-
165 8 1660 166 8 167 0 1703 1743 1700 1749 1666 1660 1712 1741 1669 174 1 1669 1744 1669 1744 168.3 1743 1669 174 1 165.7 170.7 168 1 173 8
1159 131 6 127 1 1320 210840 21083 5 1129 1596 21283 2 128 1 82 5 128 5 83 8 128 5 83 7 1275 82 8 127 4 82 I 1308 83.7 1274 83 6
65.1 201 64.5
1578 1422 1395 1407 32 1 33 1 1318 1405 30.4 1335 693 1380 32 3 1380 32 3 1391 13 9 1391 17 1 1409 467 138 1 15.6
27.5 17 8 172 66.7 17 1 178 17 8 25 9 24 8 1751
204 158 15.5 15.7
-
174 -
-_
172 15.8 157
-
78.8 206 652 20.0 73 5 119 13.5 205 69 8 204 73 7 160 81 7 205 71 5
159 170 11.5 160 160 18 5 18 5 14 1 130
169 5 173 8 1717 1619 1732 1677 1730
208816 434 1216 82.8 127 7 837
138 (152) 125
-
717 21.0 726 204 78.7
731 13 1 643
321 25 5 1385 73 1 138.4 85 2
26 5 166 22 2 24 5 --17 1
c-4
17.1 @‘)-O-Me 158 175 14.5 174 145 174 159 248 15.7 258 204 8.8 158 24 5 (3)-O-Me
Solvent*
Ref
a
II51
WI [Zl, 22, 333 c331 c231
a
[20, 231
a
c20,
a
Cl91
a
Cl91
a
c341
a
[51
a
VI
a
c351
a
Cl91
a
c 91
a
C361
a
c371
a
lI5,6, 91
a
~321
-
_
171 222 158 26 6 158 17 1
a (2’)-O-acetate a @‘)-O-Me (3)-O-acetate
221
C381 c41
E
18
ROEDFR
5 13C NMR data for pyrrollzldme
Tdble
alkaloid
2oMe
macrocychc 17
1sMe
dlesters
Me
3a
Compound No
C-l
C-2
C-3
C-5
Necme C-6
Mass
Formula
Name
CAS-Reg
309 309 309 325 341
C,,HIxNO, C,,H,,NO, C,,H,,NO, C,,H,,NO, C,,H2,NO:
6024-88 -5 120154.-95-2 6029-87-4 315.-220
5.1 5.2 5.3 5.4
133 I 1328 1336 1323
1344 1357 1318 1342
585 610 607 604
542 532 53 6 53 7
351 353 367 369 383 409
C,,HZ,NO, C,,HZ,NO, C,,HZ,NO, C,,H,,NO, C,,HZ,NO, C,,,H2,N0,
Crlspnttne Crotaleschenme Fulvme Monocrotdhne Monocrotdhne-4oxide Grant&x Axlllarldme Spcctdblhne Axdlarlne Spectdblhne-4-oxide Monouotalme12.1 i-dlacetate
35337-98-S 83482-61-5 23506- 96-9 520 -55-8 I9637 -66-2 82503-65-9
5.5 5.6 5.7 5.8 5.9 5.10
1317 131 9 1335 1330 132 1 1315
1341 1369 1364 1344 1357 1350
78 x 614 622 599 614 795
25490 -6X-o
5.11
1330
1350
599
*Solvent
tr-CDCI,,
h=DzO.
No
C-7
C-8
C-9
3.3 5 33 6 -I? s 33 5
73 76 7s 74
4 3 6 6
78 3 75 5 77 0 76 8
614 618 hl 8 613
69 2 53 8 55 0 53 8 54 1 hX 9
33 39 34 32 34 33
74 8 75 6 74 7 73.3 72 4 73 0
Ybb 71 0 78 9 78 I 77 9 970
62 0 61 8 59 9 59 8 5Y 5 h2b
536
325
74 0
778
61 2
8 9 9 7 0 3
c-C,D,N
Table
6
13C NMR data for pyrrohzldme
alkalotd
IsMe
20Me 21
macrocyhc
dlestcrs
ITMe
Me
3b
Mass Formula __--_.-___ 367
C,<,H,,NO, .._-.___
*Solvent
(I = C DCI,
Name
CM-Keg
No
Compound No
C-l
C-2
1342
133 8
__-__Crownperlne ----___
30785-56-Y
6.1 -____
c-3 ____649 ~-l--_l_-.
C-5
C-6
522
73 2
Olonecme C-7 76 6 __--_
Pyrrohzidme
wtth an 11-membered
rmg of the Crotalanan-type
(structure
alkalords
3a)
c-11
c-12
c-13
c-14
Neclc acrd c-15 c-17
C-18
C-19
1770 175 9 1743 1748
45.8 76.5 47 5 78.6
73 8 376 75.4 777
494 48 0 512 442
174 1 1748 173 5 1743
24 1 272 205 224
142 185 127 182
12.4 114 12.5 143
1784 1692 t_752
79.8 820 1123
80 5 80.7 74 ?
449 48.6 527
177 1 1732 174 6
23 7 (259)
19.7 30.0
15.6 768
212
214
317
18.2
259
222
18.1
171.7 173 1 1784
770 82.2 792
85.6 69 9 88 5
43 6 51.4 45 0
1714 172 5 173 3
(190) 69 8 23 3
15.5 178 192
14 1 275 163
1692
88 7
857
416
1739
178
175
154
with an 1 l-membered
C-8
4-Me
rmg of the Otonecan-type
c-11
c-12
c-13
(structure
c-14
19
C-20
C-21
(13)-acetate 217
Solvent*
Ref
a a a a, b, c
C(5), 61 1871 161 17. 9, 10, 39, 401
a, b a
17, 101 161
B
[At!.
a
(13)-acetate
b
16 71 C4ll c71
(12)-acetate (13)-acetate
a
161
177
a
3b)
New c-15
acrd c-17
C-18
c-19
c-20
C-21
Solvent*
Ref.
E ROEDER
Table
%NMR
data for pyrrohzldme
alkaloid
macrocychc
dlesters
18 Me
21 Me
I
4a
Mass
Formula
Name
333 333 335 335 335 335 337 317 337 349 349 349 349 349 351 351 351 351 351 351 353 353 353 365 367 369 383 383
C,,H,,NO, C,$iHZANO, C,,H,,NO, C,,H,,NO, C,,HZ,NO, C,,H2,N0, C,,H2,N0, c,,H,,Na, C: &-NC), C,,H2,N0, (I: rrH ;$IQ:,. C,,H,,NO, C,,H,,NO, C,,H,,NO, C,,H,,NO, C,,H,,NO, C,.aH,,.No,. C: ,Ff I:.NO, C,,H,,NO, C,,HZSNO, C,,H2,N0, C,,H,,NO, C,,H2:N0, C,.s.H,,NO-. C!,H25NO-. C,,H,,NO, C,,H,,NO, C,,H,,NO,
Seneclphylhne Spartloldmz Integerrlmme Jacobme Seneciomne Seneclvernme Llguldrmme P!‘iIy$l~!llne Ne~pidly~hy!lme Eruclfolme .lac~~me Rtdelhme Swdzme Seneclphyllme-4-oxide Andcrotme Gynuramme
4%~81-9 5IGS9-2 48&79-5 687G-67 -3 1-10-O 1,x 72755-25-o 90364-90-2 48&78-4 2036I-76-6 40158.-95-6 iTQ-2.-(1 23246-964 38763-74-5 3X710-26-8 5096 -49-l 8561 l-434
%!JlfCCJ~~Wlr;4-WCldC
1_2xiK~~7-~2_
48&~4-6 15503-87-4 98264-41-6 3573-82-8 52@ 65-o 9820549-3 7M’i& l_l,-o
393
CZ,H,-I\IO:
395 395
CZ,H,-NO, CZ,)H,,NO,
Retrorunc Usnramlne Uspnllatme Hygrophyllme Rosmdrmme Dlhydroretrorsme Rldelhme-4-oxide Rctror\me-4-oxide Jawhe Alkaloid (adomfolm)* Dlhqdrouy-dlhydroerucrfolme Gqnuramme-19dcetatc Uspalidtlne-6-acetate ITolme
CAS-Reg
No
15503~-86-3 480-76-2 115712-88-4
Compound No
C-l
c-2
c-3
Necme c-5 C-6
7.1 1.2 7.3 7.4 7.5 7.6 7.7 ?;8 ?:9 7.10 7.11. 7.12 7.13 7.14 7.15 7.16 7-J-7 1.JQ 7.19 7.20 7.21 7.22 7.23 2.24. 7.2zX 7.26 7.27
1322 LIl_ 1 131 8 1312 112 2 1315 40 3 38 4 39 5 1312 I-Il. 7_ 1312 131 8 1322 1315 1313 1.33 4 1.23_2. 1317 1.11~0 41 6 49 1 394 1.21.9 1~334 1314 1313
1366 L370 1364 1364 l-16 I 136 1 29 6 i! 7 30 3 1343 I.16 7 1367 1366 1424 1365 1356 140.6 1.25L 1366 1~359 29 5 69 3 316 1.414. 141 I 1362 1360
627 62z 622 631 62z 607 547 536 515 62 1 61 0. 624 61 2 803 63 5 629 80 5 622 625 624 546 61 4 515 WE 807, 634 606
513 528 532 530 szo 532 525 5!9 528 534 510. 532 53 1 710 585 531 71.1) 1?4. 529 60-i 523 535 534 71-11 709 536 537
360 338 338 350 377 342 34 8 358 355 351 $50. 347 34 I 352 748 314 353 169 -337 7X6 35 3 345 353 111 353 345 352
106283%53.-8 85547-34-8 98264-42-7 3000&36-3
*Exact ndme 12,13.19-tr~hydroxy-15,20-epoxy-15,20-d~hydro-(l2s, ISolvent a=CDCI,. h=DZO
7.29 7.30 7.31
1314 1307 131 6
135 1 1364 1357
629 625 606
532 579 532
15R, 2OR)-seneclondn-11,16-dlone
342 71 1 346
C-7
C-S
C-9
749 7.1 I_ 754 759 7sx 765 75 1
777 17 I_ 774 176 770 765 68 9
742
695
739 750 76 1. 750 759 763 755 750 76 7 717 755 767 730 75 2 686 76.6. 76 7 766 779
690 772 77 5 773 776 98 I 744 776 92.3 767 769 748 736 69 3 739 9x0. 880 777 78 8
61-2 601 608 605 614 627 64 1 666 fih7 609 40.8. 622 622 626 607 607 62 2. 63 3 612 600 650 62 3 644 63.L 62 5 60.9 67.4
786
77 8
605
751 756 769
776 752 775
610 602 636
Pyrrohvdine alkalotds
21
wrth a 12-membered rmg of the Senectonan-type (structure 4a)
c-11
c-12
c-13
c-14
c-15
New C-16
actd C-18
1770 1765 1782 1779 1777 178.1 L75@ 178.7 1786 169 7 LVi4 174.3 1766 1785 1783 1768 1803 175 6 1756 1778 1782 1800 1755 1764 1780 1784 1699
764 76 1 76.4 77 1 76 7 77 7 75 7 75.8 64.4 765 79 2 774 79 5 768 780 804 81 3 81 3 766 78 1 774 802 82 5 848 77 7 74 1
1464 144.9 394 38.1 38.2 40.8 294. 37.4 36.5 65 9
37.2 29.0 296 360 38.3 35 9 XL9 39.2 39 3 35.3
I-4.3 4.
25 Z
724.Q
1_1_4,9
VLh?.
377 356 39.4 384 348 404 360 29.3 379 723 395 388 39 8 40.1 368 408
167.1 1680 169.2 1686 1675 168.8 t_473167 7 167.3 1682 l_fixI 1670 1681 1707 1696 167 4 171.5 167 3 1689 1669 166.9 1675 167.2 171.1 171.1 1758 167.5
24.9 24.7 25 2 24.3 250 26.2 t-7.P 26.2 26.4 149
1432 794 149 0 383 439 41 2 356 36.8 322 407 378 345 145.9 38 5 373 654
1314 131.8 134.1 64.1 133 2 147 4 t_xt_s. 131 8 131 8 1300 627-7 1312 143.1 1312 132.8 132.2 1313 1313 133 4 1324 1334 1326 1309 1312 1312 81 7 616
66.2 219 266 252 25.3 26.7 66.7 671 248 25.7 257 67 5 683 69.1 24.5 154
1147 417 116.9 11.3 58 5 13 1 11.6 12 3 10 8 58 117 13.8 117.7 13.6 14.1 63 2
135.9 169 1341 134.3 136.8 134.2 1362 135.7 1347 1351 134.4 136.1 1344 134.5 72.6 73.7
15.2 122.0 17.6 15.2 15 1 17 5 150 142 14.9 152 15 1 15.3 17.6 17 5 172 145
1695
654
61 5
409
74 1
167.2
145
67.3
737
154
177.3 1178 176 1
76.2 764 83 6
426 382 373
347 379 396
132.2 132.2 78.8
167.2 25.5 (166 7) 24.8 149 1721
62.2 10.9 15.9
77. 1_
C-19
C-20
1144 113.2 11.8 12.8 111 57
135 8 1356 135.3 560 1340 12.0
C-21 15.2 13.4 142 136 151 120 5
LX24
Llt.9
13 5 137 62.8
1365 156 1378 144 133.5 160
Ref
a
C6, 7, 431 c43,441 C6,46,471 C6,481 [7, 45, 47, 49-521
a
a a a a a.
354.
a
a a 4 a
132
136.9 15 1 135.2 14.9 333 74
Solvent7
; a a b a a a a a h”
b b a
(19)-acetate (6)-acetate (la)-acetate
c45, 531 (%4$ [6, 7, 50, 551 C6, 551 C561 [Q.
C6,71 Clll c71 C61 iI C7, 521 [5-7,11,14,45,47,51,58] c441 Cl71 [6, 7, 11] c33, s91 Cl71 c71 c71 C481
~521
a
C261
a
c571 Cl71 Clll
a a
E ROEDER
22
Table
8 ‘W NMR data for pyrrohdme
dlkalold
macrocychc
dlesters
18 Me
21 Me
0
20
Me 4b
Compound Mass Formula
Name
365 365 36.5 381 381 381 383
C,,H,,NO, C,,H;;NCI, Ci-&li;NOb C,,HZ,NO, C,,H,,NO, C,,H,,NO, C,,HZ,NO,
Emhe Neo_%nk&mnc ScnhrkLna Anonamme Otosemne Hydroxysenklrkrne Synellesme
407
C,,H,,NO;
SakLrkLm-12-wJat~
423
C,,H,,NO,
423 423 441 459
Fukmotoxme-12acetate C,,H,,NO, Florosemne C,,H,,NO, Ligularizine C,,H.<,NO, Florldanme C~iH3Jl.NO&ho.m~
*Solvent
(1 =
CAS-Reg
No
No
-
8.1 8J a 8.4 8.5 8.6 8.7 U
36506-99-7 57194-7w 211118-5 111566-66-6 16958-29-5 26782-43-4 55652m~65-8 530x-44-7
60409-51-O 16958&30--8 90364.-924 16958-31-9 6.036.7-O&2
8.9 8.10 8.11 8.12 813
C-l
c-2
C-3
Octonecine C-5 C-6
C-7
C-8
c-9
1357
1318
134 5
1374
L34 3
137 3
532 533 532 536 532 533 535 534
375 339 171 354 355 358 373 361
772 792 7RL 785 785 779 784 7RX
1915 1918 I.917 1917 1905 1853 1894 I.924
586 650 643 647 59 1 640 636 5X8
531 529 532 544
365 351 358 359
773 790 774 792
1900 1918 1902 191 1
589 58 9 58 9 60 2
546
36X
745
1411
6.45
1343
1374
1343
137 1
133 8
1367
1342
1360
134n
138 2
666 583 5X4 589 642 567 522 64X
1333 133 7 1355 1339 I.34 5
1387 1384 1383 136 7 I.36 8
641 64.6 63.7 640 593
-
--
CDCI, Table
9
13C NMR data for pyrroltzldme
alkaloid
macrocychc
dlesters
5 -_ Mass
Formula
Name
CAS-Reg
335 337
C,,H,SNO, C,,H,,NO,
Doronemne Bulgarsemne
74217-57-5 62018-77-3
*Solvent
a = CDCl,
No
Compound No
C-l
c-2
c-3
c-5
C-6
9.1 9.2
1320 316
1354 32 7
63 4 506
52 6 52 6
34 1 370
Necme C-7 77 1 72 6
Pyrrohzrdme
wtth a 1Zmembered
rmg of the Otonecan-type
alkalords
23
4b)
(structure
4-Me
C-11
C-12
C-13
C-14
C-15
New acid C-16 C-18
C-19
C-20
C-21
402 413 404 41 1 400 40.5 404 406
174.7 178.2 1780 178 3 1777 175 1 176.7 171 1
752 770 766 764 779 810 78 9 775
1465 396 386 38.3 385 356 41 2 409
31 1 29 1 369 303 37.1 372 74.3 374
469 132.7 131.7 132.3 637 1308 733 1320
177.6 167 9 166.5 1667 177.8 1609 1714 166.5
285 24.9 246 25.5 239 663 243 221
1179 11.6 109 12.5 125 113 58 11.5
26 5 138 I 137 0 1406 56.1 137.2 23.0 137.4
120 14 5 15 3 59 3 136 15 1 118 15 4
(12)-acetate
400 39.9 40 1 39.8 404
170.5 168.0 1712 171 4 1728
83 4 83 6 82.2 840 81 5
38.4 404 363 40.9 40.2
370 37.1 36.9 63 1 364
62.6 63.8 62.2 82.0 83.8
166.3 171.1 1660 174.7 1713
21.5 214 14.4 21 6 216
130 12.9 13.9 14.6 14.3
61.4 55.9 61.4 72.8 63 0
15 6 13 6 15 5 17 2 18 3
(12)-acetate (12)-acetate (12)-acetate (12)-acetate (12)-acetate
Necic actd C-16
c-17
c-19
c-20
c-21
Solvent*
Ref
167 7 1669
24.6 26.8
117 155
28.3 28.1
a a
1681 C681
wrth a 13-membered
rmg of the Doronenan-type
(structure
C-8
c-9
c-11
c-12
c-13
c-14
c-15
75 7 704
60 5 67.4
1777 1877
757 75.7
34.6 360
41.1 37.3
151.8 1544
Solvent*
Ref.
CW [47, 51, 611 [h, 7,45,51,52,62]
c511 [Sl, 63, 641 I511 C3, 6, 651 C661 c541 [47, 52, 641 c541 c641 C62,671
5)
118 5 118 3
24
E
ROEDER
Table
10 “C NMR data for pyrrohzrdme
alkaloid
macrocycllc
dlesterr
6
Mass
Formula
Name
351 367 393
C,,Hz5N0, C,,HZ5N0, CZ,H,,NO,
Madurensme Crotaflorme Madurensme-7-acetate
*Solvent
u = CDCI,
CAS-Reg 26126-78-3 112156-54-4 112156-53-3
No
Compound No
C-l
c-2
c-3
10.1 10.2 10.3
129 9 1354 1354
136 1 136 3 1361
53 3 66.4 665
Necme C-5 664 614 61 1
C-6
c-7
74 7 752 74 5
73 7 746 766
Pyrrolizidine
with a 13-membered
ring of the Madurensan-type
(structure
C-8
C-9
C-l
1
c-12
c-13
c-14
c-15
C-16
15.2 73.1 71.5
61.5 59.8 58.9
176.9 174.9 178.0
76.3 81.2 75.9
40.5 37.2 39.6
27.6 21.3 27.2
135.6 129.1 131.8
167.0 166.9 167.3
25
alkaloids
6)
Neck acid C-18 C-19 24.6 66.5 24.3
10.8 19.5 10.6
C-20
C-21
Solvent*
Ref.
142.5 143.0 142.1
15.0 15.0 15.0
a a u
II5 691 C691 C691
(7)-acetate
E
26
ROWER
Table
lla
1 1 “C NMR data for mtscellaneous
NH
llb
NH
$OH 12c
12b
Mass
Formula
Name
CAS-Reg
No
Compound No
C-l
c-2
C-3
C-5
C-6
C-7
(‘-8 _____
Necme c-9
Pyrrollzldme
pyrrohzldme
alkaloids
3
27
(7.-19)
ItIlt? Me4
Mea’
18s 1Ub
R=H R=A~
C-l’
alkaloids
c-2
C-3’
C-4
New acid or a condensed system C-5’ C-l” C-2” C-4’ C-3”
C-S”
C-6”
Solvent*
ReI c701 c711 c731
519 167 8 1696 1663 1680 1742
21 8 1136 1175 1404 1125 83 3
1742 1742
81 6 75 8
1760 1581 1189 1461 706 73 6 455
1395 218
1710
1282 205
518
~ 1279 1240
429
~ 1293 1304 32 5
14 3 1144 1171 16 I
1610 163 5
32 5 1348
16 1 1302
177 1282
1144 117 1
1296 1304
(4”)-O-Me
171
a
173,74, 751
b b b b b a b a a a
C761 1761 1771 C781 c791 WI [811 IQ1 I831 cf341 I851
a (3’)-acetate 1272
a ?
I851 Ml
E ROFDER
28
Only m a few cases was it necessary to apply perdeuteropyrldme (C,D,N), perdeutero-DMSO [(CD,),SO], perdeuteromethana1 (CD,,OD) or de~&xame+hanol (M&D). In all cases tetramethylsdane (TMS) was added as mtcrnal standard or the chemical shift was related to It
~.4SR~.~!.st.ry-Nu~~~~
30
31 32
C’A.S=Rellzstr~-Nunzher The
29
L1as hren
allows a fast access to the hterature CAS online-research
ti.
aIts.
of an Jkalold
gwxL,
via
31 34
Pyrrohzldme
65 Hlklchl, M and Furuya, T (1976) Chem Pharm. Bull 24, 3178. 66 Gonzalez, A G , De la Fuente, G , Rema, M and Loyola, L A_ (.l_wfi). erflwl. MpJi. l-fin 67 Riwiq. E,. WwIenfeJ~. H_ and_ Knwzqj~-Fwhp. P (1984) Planta Med 50, 203 68. Roeder, E., Wledenfeld, H and Frlsse, M (1980) Phytochemwry 19, 1275 69 Akr&izZ. R,. A~.nafq,.G .DwUP&,.H_ ami sJlti7kPt.G px7). Tetrahedron 43, 3263. 71). !hxh,. E,. Wwienfel&. H and Bonllriwel,. T (1986). be/~,g~ Ann Chem 1645 71 Roeder, E ,Wledenfeld, H and Bourauel, T (1985) Lleblgs Ann Chem 1708 72 Dannha&,.G (.L!85).(unplti1sh~&dat~. 7.2 Mahk,. G anil_ Rahmann,. K_ (.l_‘XQ Hpf~~~&_~ 27,. 7Q7 74 Wmkier, T and Heckendorn, R (1988) Heterocycles 27, 2331 75 Ster.m~tz,~F R~ and~LIEmp~eur,~K M (1988) TPtrnhedron~ Letters 4943
7.7.
Nash,. B. I,. EpJlnwq. L. E,. nJlln&_ I V ;_ Flw& G W I,. Derome, A E , Hamor, T A, Scofield, A M and Watkm, D
alkaloids
29
J (1988) Tetrahedron Letters 2487 78 Molyneux, R J, Benson, M , Wong, R Y, Tropea, J E. and Elbem, A. 0. (1988) J Nat. Prod. 51, 1198 79 Nash,. K I.,. F&X%. 16 E,. Plans,. A_ C,. Flm=&.G. W I;. DeUZmlq.L E,.Balt&P n ~.Hpgjvfy.,.M_ e and_Scsrfid~. AM. (1988) Tetrahedron 44, 5959. 80 Roeder, E , Wledenfeld, H and Jost, E -J (1981) Planta Med 43, 99. 8.1. I&u,. 9,. Gaw;td. D E,. PPJIPJXX,. S W! ,_Killlthq. G and Bhandary, K (1986) J. Nat Prod 49, 614 82 01ylq.T W,,.NeUl&xqD E.,.&&q.D M,.Mk&yj..l Ej. Gruhch, R E., McCabe, T. and Clardy, J (1980) .I Org. Chem 45, 1324 83 Ikhln, K., Ahond, A, Poupat, C, Pothler, P, Pusset, J and Siwenet,.T (.1987). I N& Pro/i .%I.626 84. D&son,. Cd D a& StFXmltz,. F R. (mfi)..Z Nat. Prd. 49,. 727 85. Abe, F. and Yamauchl, T. (1987) Chem Pharm Bulf 35,466l 86 Fupki, K, Shoyamq~Y ,~MIatsun&~K andN~sbmka, J (1988) Phytochemrstry 27, 1564 87. Smlti,. L. W ,. Edgar,. 1 A_,. Wdh~. R. I;. Cs;lhlq. R. W ;. Mackay,.!& E ,.SurI,.Q P ,&al,.C. K an&Culv.~~~mr,.C, C 1 (.1!%8).Ic~t. J! C&m. 4.!_.4%!