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Received 10 December 2001; received in revised form 23 January 2002; accepted 15 March 2002
Abstract
The aim of this paper is to present a procedure that utilizes 13C NMR for identification of substituent groups which
are bonded to carbon skeletons of natural products. For so much was developed a new version of the program
MACRONO, that presents a database with 161 substituent types found in the most varied terpenoids. This new version
was widely tested in the identification of the substituents of 60 compounds that, after removal of the signals that did not
belong to the carbon skeleton, served to test the prediction of skeletons by using other programs of the expert system
SISTEMAT.
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Terpenoids; Natural products;
13
1. Introduction
The recognition of substructures, parts of a structure,
has always been one of the steps tracked during the
processes of spectral analysis, whose main objective is
the structural determination of a compound. However,
the automation of these processes is not simple, due to
the complexity and great structural diversity found, for
example, in natural product chemistry. In order to help
the user resolve these problems, numerous expert
systems have been developed and tested for automatic
identification of substructures (Lindsay et al., 1980;
Carhart et al., 1981; Shelley and Munk, 1982; Attias,
1983; Gray, 1986; Munk et al., 1986; Christie and Munk,
0097-8485/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 9 7 - 8 4 8 5 ( 0 2 ) 0 0 0 2 9 - 3
602
Fig. 1. Monoterpene used to demonstrated the influence of the signals of the substituents in the prevision of skeletons.
concerning the proposed skeletons, for certain substructures are only selected because of the presence of the
signals of the macronodes.
In order to demonstrate the influence of the signals of
the substituents in the prediction of skeletons, a monoterpene (Fig. 1) was chosen and tested with and without
the presence of the signals of 13C NMR of the
substituents. The results obtained through the program
SISCONST are shown in Table 1.
In attempting to improve the SISCONSTs performance
as well as to eliminate such problems originated from
macronodes, an initial version of the program
MACRONO (Rodrigues et al., 1997) was, then, developed.
After some tests on sesquiterpene lactones, it presented
the correct information of their most common types of
substituents at a high hit level. But, on the other hand,
when the same program was submitted to tests on other
terpene types, its performance was drastically reduced if
is compared with that obtained with the former compounds. Undoubtedly the defficient results were due to
Table 1
Results presented by the
SISCONST
program
Skeletal type
With substituents
Without substituents
Myrcane
Menthane
Ionane
Cyclogeraniolane
Bornane
25.0
13.9
35.0
20.0
16.1
84.7
10.6
4.7
/
/
603
604
programs
search.
Fig. 2 (Continued)
MACRONO
and
SISCONST
jointly in this
2. The program
MACRONOs
database
The initial version of the program MACRONO (Rodrigues et al., 1997) operated by comparing the 13C
NMR data obtained from a substance with information
contained in a database that presented only 58 macro-
605
Fig. 2 (Continued)
606
Fig. 2 (Continued)
607
Fig. 2 (Continued)
608
3. Results
In order to test the acting of the new program and to
evaluate its efficiency, we randomly selected from
the literature the 13C NMR spectra data of the 60
compounds bearing substituents of well-known structures (Table 2). The structures of these compounds,
used to test both programs jointly, are exhibited in Fig.
3.
Fig. 2 (Continued)
609
Fig. 2 (Continued)
610
Fig. 2 (Continued)
611
Fig. 2 (Continued)
1)
612
Table 2
Chemical shifts of the substances used to test the programs
1
2
3
4
5
6
7
8
9
10
OR
1
3
4
5
6
7
8
9
10
11
OMe
Gly-1?
2?
3?
4?
5?
6?
OR
1M
7P
8P
9W
10M
66.3
121.4
142.1
36.6
34.2
76.1
148.7
111.5
29.9
16.6
102.5
75.5
84.3
70.6
75.5
64.7
102.7
72.3
72.3
70.4
70.1
17.9
169.0
115.0
146.8
127.2
131.2
116.9
161.2
116.9
131.2
66.0
119.8
140.4
37.8
26.9
153.1
139.8
195.0
9.2
16.8
161.4
113.5
143.3
111.5
108.3
146.7
151.9
101.2
149.9
56.4
/
/
/
/
/
/
/
/
/
/
/
69.2
121.0
140.5
35.5
28.7
88.9
143.8
114.1
17.1
16.1
132.4
103.7
153.7
132.4
153.7
103.7
127.9
131.2
63.6
56.1
56.1q
/
/
/
/
/
/
/
/
/
/
139.6
138.6
67.4
46.8
73.8
195.0
60.5
27.8
19.7
19.6
165.8
143.4
124.8
66.6
21.5
170.0
21.0
/
/
/
/
/
/
/
/
/
/
/
/
/
/
139.7
124.6
69.2
40.2
68.9
65.9
63.0
26.7
20.1
20.0
167.0
128.3
138.2
11.9
14.5
167.0
128.3
138.2
11.9
14.5
170.4
21.3
/
/
/
/
/
/
/
/
/
45.0
37.4
118.2
31.9
50.6
141.9
83.4
26.5
22.7
22.6
99.0
73.9
75.4
73.7
70.7
63.1
171.0
20.8
171.8
21.0
/
/
/
/
/
/
/
/
/
/
/
88.7
85.8
44.5
105.7
43.6
22.7
71.3
61.2
101.5
19.6
100.1
74.9
78.0
71.6
75.0
64.7
130.4
129.8
128.6
133.2
128.6
129.8
166.2
122.7
131.8
114.1
163.6
114.1
131.8
166.4
55.2
88.7
85.8
44.5
105.7
43.6
22.7
71.4
60.6
101.5
19.6
100.1
74.7
78.0
71.6
74.9
64.6
121.1
132.2
115.9
163.4
115.9
132.2
166.4
123.3
131.8
114.0
163.7
114.0
131.8
166.0
55.2
48.8
37.6
75.2
83.6
40.0
82.3
13.9
47.3
17.7
17.6
101.8
73.8
76.8
70.5
76.5
61.5
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
37.1
48.2
202.0
126.0
165.8
56.7
128.7
138.1
76.5
20.9
27.7
28.0
23.8
100.9
79.2
77.8
71.4
77.9
62.6
110.7
78.5
80.6
75.3
66.0
/
/
/
/
/
/
/
11M
12W
13
14M
15M
16M
17M
18M
19M
20M
94.0
152.2
115.7
69.0
45.5
80.3
78.7
58.2
21.3
167.9
51.7
99.6
74.5
77.5
71.7
78.4
62.8
128.7
133.6
114.4
162.1
114.4
133.6
95.1
148.8
116.5
32.5
30.0
39.8
81.1
51.5
24.4
170.9
/
98.8
73.6
76.4
70.8
74.8
63.9
170.9
127.9
145.6
24.2
40.7
74.4
93.8
152.3
105.8
37.6
76.0
43.8
87.0
48.0
21.2
165.6
50.4
98.9
72.2
76.0
69.9
76.1
61.7
124.6
128.9
115.2
158.9
115.2
128.9
97.4
152.5
113.1
32.5
40.4
78.7
40.9
47.1
13.7
169.2
51.8
100.1
74.6
77.8
71.5
78.2
62.7
168.9
129.3
142.9
28.1
31.5
138.5
95.7
141.8
103.8
39.1
79.5
62.8
63.6
43.7
64.3
/
/
100.4
74.8
78.5
71.5
77.9
63.0
128.9
112.5
151.6
148.0
114.9
122.9
93.0
140.9
105.8
38.1
83.5
73.5
79.5
49.1
66.2
/
/
99.9
74.8
78.1
71.4
78.0
62.7
128.4
131.1
115.5
163.3
115.5
131.1
66.1
68.2
33.2
52.2
84.4
127.8
152.4
98.2
59.2
/
/
/
/
/
/
/
/
168.1
122.5
132.8
116.2
163.6
132.8
96.5
154.2
109.5
28.6
34.6
174.5
75.5
41.8
21.4
168.2
51.9
101.0
74.6
77.7
71.7
75.7
64.6
113.0
155.9
115.3
119.3
150.9
125.2
94.5
154.4
108.8
31.0
40.5
172.5
124.1
130.0
12.9
167.5
/
100.2
74.1
77.7
70.8
70.3
62.0
65.7
34.6
129.7
130.3
115.5
156.3
94.7
154.8
109.3
30.8
41.1
173.2
129.3
131.9
59.4
167.6
52.4
97.8
74.9
79.5
68.6
74.6
65.1
130.8
116.9
146.2
144.8
117.5
121.8
613
Table 2 (Continued )
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
OR
1
2
3
4
5
6
7
8
9
145.0
117.8
167.4
/
/
/
/
/
/
/
/
/
/
144.6
113.2
12.5
27.0
/
/
/
/
/
/
/
/
/
113.5
144.0
165.7
170.3
20.8
/
/
/
/
/
/
/
/
126.5
59.1
12.5
23.5
/
/
/
/
/
/
/
/
/
146.9
115.9
168.9
56.4
/
/
/
/
/
/
/
/
/
146.5
116.0
168.7
55.9
/
/
/
/
/
/
/
/
/
116.2
/
/
/
/
/
/
/
/
/
/
/
/
170.7
/
/
/
/
/
/
/
/
/
/
/
/
115.5
130.3
66.2
34.7
129.5
116.4
145.5
144.2
115.8
120.6
/
/
/
72.6
36.1
127.1
115.2
148.6
147.3
116.7
123.4
116.5
147.8
169.6
171.0
21.3
21M
22P
23
24
25
26
27A
28
29
30
130.3
147.5
143.4
130.3
122.6
136.5
44.6
24.1
77.2
34.1
35.9
19.3
22.4
17.2
14.8
105.5
75.5
77.6
71.2
66.9
107.8
75.4
78.3
71.7
78.0
62.8
103.8
75.3
78.4
71.7
78.0
70.1
225.6
53.2
46.1
81.6
125.0
141.7
29.9
71.3
64.2
21.5
19.2
6.2
9.9
27.4
67.8
99.6
75.4
78.4
72.1
78.9
63.1
/
/
/
/
/
/
/
/
/
/
/
36.5
25.6
72.9
85.7
48.6
140.1
145.1
200.3
57.6
40.0
71.7
28.9
29.1
18.5
18.7
167.0
127.8
138.1
15.7
20.6
170.7
22.8
/
/
/
/
/
/
/
/
/
/
77.5
29.3
76.2
37.2
46.7
22.5
117.0
134.9
57.7
37.4
98.2
69.4
27.1
15.5
9.1
169.7
20.8
170.0
20.8
170.9
21.0
/
/
/
/
/
/
/
/
/
/
/
124.3
21.3
31.3
31.9
42.5
72.1
119.7
151.3
26.3
135.3
117.4
138.2
8.7
16.6
15.1
177.0
34.4
19.4
18.7
/
/
/
/
/
/
/
/
/
/
/
/
/
209.0
36.0
29.8
30.3
44.1
67.9
116.0
149.8
22.3
51.1
119.4
138.4
8.2
17.8
14.8
176.6
41.2
26.4
17.0
11.7
/
/
/
/
/
/
/
/
/
/
/
/
64.5
135.6
132.6
77.0
77.0
33.7
39.7
22.1
44.8
37.6
44.5
43.5
39.8
72.4
27.1
172.0
105.5
166.1
101.6
163.7
112.5
144.6
24.3
/
/
/
/
/
/
/
/
/
48.2
80.3
41.6
85.6
54.6
70.5
40.6
133.6
124.6
35.0
37.0
18.2
17.7
20.1
25.8
166.6
122.6
113.7
131.6
163.5
131.6
113.7
55.3
/
/
/
/
/
/
/
/
/
41.2
48.8
205.3
144.0
174.6
21.1
40.4
85.5
207.2
42.8
25.3
20.1
20.5
30.1
21.4
167.6
127.0
140.3
15.9
20.5
/
/
/
/
/
/
/
/
/
/
/
/
69.7
67.6
41.2
72.2
91.1
78.7
50.2
34.4
68.8
53.6
84.8
26.4
30.0
24.6
65.8
170.3
21.4
109.9
118.7
143.7
148.9
161.8
11.3
11.6
15.3
16.4
25.5
26.5
40.6
41.6
174.5
175.1
31
32
33
34
35
36
37
38M
39
40
129.5
26.3
34.7
143.8
128.7
76.6
52.7
72.5
49.0
129.5
26.3
34.7
143.7
128.7
76.5
53.1
72.5
48.8
129.4
26.1
34.7
142.8
129.1
76.1
58.1
73.3
49.0
129.4
26.1
34.7
142.8
129.1
76.1
58.4
73.4
49.1
78.0
27.2
22.4
44.9
48.9
76.1
53.8
69.9
43.9
37.3
25.1
73.6
86.9
47.5
22.6
160.3
77.4
50.2
37.9
25.2
73.4
87.3
49.0
22.7
159.4
102.9
54.0
48.3
40.2
77.0
85.2
59.2
77.3
46.9
75.0
35.6
153.0
188.9
153.7
146.1
52.4
85.1
47.9
24.1
36.9
45.5
36.3
75.0
152.2
51.4
77.7
47.7
74.1
37.5
614
Table 2 (continued )
10
11
12
13
14
15
OR
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
OR
132.6
135.3
169.7
125.8
16.7
61.4
172.1
38.4
32.7
67.1
16.7
/
/
/
/
/
132.9
135.5
169.9
125.2
16.8
61.5
166.7
128.4
138.6
14.6
12.8
/
/
/
/
/
132.7
40.3
178.1
17.2
16.6
61.5
174.8
41.9
64.4
13.5
/
/
/
/
/
/
132.8
40.2
178.0
17.0
16.6
61.5
166.4
131.9
141.4
14.4
56.9
/
/
/
/
/
41.5
136.3
169.2
120.5
13.9
201.8
165.2
139.0
126.7
62.3
/
/
/
/
/
/
35.8
120.8
174.2
8.0
19.2
16.8
166.8
127.9
137.9
15.7
20.6
170.2
22.5
/
/
/
35.8
122.6
172.9
8.0
19.8
17.2
167.9
127.8
138.0
15.8
20.6
170.2
22.7
/
/
/
145.0
139.3
170.8
122.1
117.2
50.1
167.4
132.1
141.9
14.3
55.7
/
/
/
/
/
124.6
139.5
169.1
117.9
21.7
14.9
101.6
75.3
78.3
71.1
78.3
62.3
/
/
/
/
141.6
137.2
169.1
122.9
118.4
116.0
167.2
128.4
141.3
59.9
12.8
166.4
128.0
140.6
59.8
12.8
41
42
43
44
45
46
47
48
49
50M
46.2
86.2
78.1
49.5
68.1
143.3
68.0
73.8
205.5
48.5
136.3
133.3
44.8
210.7
91.5
17.6
113.0
22.5
27.7
20.3
170.4
170.1
169.5
169.2
169.2
22.1
21.4
20.9
20.8
20.6
175.7
33.5
19.1
18.5
/
46.3
86.2
78.1
49.5
68.0
143.3
68.0
73.9
205.5
48.5
136.3
133.3
44.8
210.7
91.5
17.7
113.1
22.6
27.8
20.3
170.4
170.1
169.5
169.2
169.2
22.1
21.4
20.9
20.8
20.6
174.2
40.4
26.7
16.3
11.1
131.6
136.4
82.3
84.9
74.6
136.2
128.1
43.1
205.5
72.0
38.4
30.8
24.2
23.4
27.6
24.5
65.1
16.8
15.5
66.5
170.9
20.9
168.2
127.8
139.7
15.8
20.7
168.2
127.1
137.8
15.7
20.6
/
/
/
131.6
136.2
82.8
84.7
77.5
138.3
122.1
42.6
205.1
72.0
38.1
35.2
68.7
28.8
34.1
18.6
65.6
17.8
15.9
21.8
170.8
21.2
168.4
126.9
140.2
15.6
20.7
166.7
130.2
129.7
128.4
132.9
128.4
129.7
/
31.7
29.6
76.7
73.4
116.5
140.2
76.4
71.3
24.9
25.3
31.1
70.5
43.6
207.2
71.2
17.0
17.4
24.5
62.6
13.3
172.2
21.2
170.6
20.6
166.8
138.5
128.4
14.6
12.2
166.4
138.0
128.1
14.5
12.0
/
31.5
29.5
76.9
73.3
117.2
139.7
76.2
71.5
24.7
19.3
30.7
70.6
43.1
207.6
71.1
16.9
17.6
29.0
16.1
13.4
170.5
21.0
170.4
20.9
170.3
20.5
171.8
43.5
26.0
22.2
22.1
/
/
/
/
38.9
18.8
36.0
37.4
56.1
24.4
38.3
147.0
56.0
39.6
21.3
27.4
171.0
115.2
174.3
73.1
107.0
27.5
67.0
15.1
177.6
28.9
28.9
172.2
/
/
/
/
/
/
/
/
/
/
/
39.3
18.0
36.3
36.3
46.9
26.2
74.2
75.0
54.4
38.4
24.1
34.9
147.1
138.7
113.5
115.8
22.9
27.0
67.3
15.3
126.9
132.1
115.1
157.3
115.1
132.1
143.8
116.7
167.4
/
/
/
/
/
/
27.3
70.2
36.9
61.4
45.1
72.2
33.3
36.4
39.7
42.5
84.6
30.8
46.1
101.8
146.9
107.6
16.2
49.7
61.8
13.9
170.6
21.2
170.1
21.1
175.3
41.4
26.7
11.7
16.6
/
/
/
/
/
/
41.9
20.3
39.1
44.1
49.0
36.9
77.1
51.7
49.6
40.8
19.0
34.2
43.5
35.7
80.8
160.3
109.1
29.3
181.4
16.4
136.0
130.0
129.2
131.3
129.2
130.0
145.5
120.1
168.1
/
/
/
/
/
/
615
Table 2 (continued )
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
OR
51P
52M
53
54P
55M
56M
57P
58M
59M
60
32.5
30.4
89.1
42.9
54.2
67.9
38.6
46.9
21.2
29.5
26.6
33.9
46.6
47.0
49.0
73.0
56.6
21.2
30.4
86.8
26.5
37.7
24.5
85.1
70.4
28.3
27.0
29.0
16.7
20.6
106.7
75.6
78.4
71.5
77.9
62.7
105.1
83.7
78.5
71.7
78.1
63.0
106.2
77.2
78.2
72.0
78.3
63.0
33.1
30.5
91.0
42.1
48.9
22.1
27.2
49.6
21.1
27.4
27.3
34.4
49.9
47.9
47.7
73.0
52.9
19.4
31.0
33.4
15.9
80.9
36.3
78.3
84.0
26.0
23.1
20.4
26.1
15.5
104.2
81.8
77.7
71.6
77.1
62.6
/
/
/
/
/
/
/
/
/
/
/
/
38.3
23.7
80.6
37.8
55.3
18.2
34.2
40.8
50.3
37.1
20.9
25.1
38.0
42.8
27.4
35.5
43.0
48.3
48.0
151.0
29.8
40.0
27.9
19.3
18.0
16.6
16.2
15.9
109.3
14.5
173.7
34.8
24.8
31.3
22.3
13.9
/
/
/
/
/
/
/
/
/
/
/
/
39.0
26.6
89.0
39.5
55.7
18.3
34.9
41.6
50.9
36.9
21.8
29.6
38.6
43.5
30.5
32.4
59.5
49.2
49.8
72.1
29.0
37.0
27.9
16.5
16.3
16.7
15.2
175.2
26.9
31.5
104.9
83.2
77.9
71.5
78.2
62.7
105.8
76.7
77.8
71.5
78.1
62.1
95.2
74.1
78.8
71.0
79.2
62.6
49.0
67.9
77.8
41.0
48.6
19.0
33.1
40.3
47.5
37.7
24.8
128.9
140.1
41.2
28.0
26.1
48.0
51.1
154.0
38.1
32.5
38.0
67.1
14.0
16.9
17.1
23.8
182.0
107.8
21.5
168.7
115.1
145.8
125.3
130.5
116.0
160.4
116.0
130.5
/
/
/
/
/
/
/
/
/
39.6
28.5
90.8
40.2
57.0
19.5
34.1
41.3
47.8
37.9
24.7
129.7
139.6
42.6
29.7
26.5
48.7
54.8
73.7
42.8
28.5
38.2
28.6
17.7
16.1
17.0
27.1
178.6
24.7
16.6
107.2
75.5
78.0
71.2
67.0
95.9
73.8
78.1
71.0
77.9
69.6
102.5
72.4
72.7
68.9
75.5
63.1
/
47.9
68.7
85.8
44.0
56.6
19.4
33.9
40.4
47.8
38.3
24.4
127.9
140.4
42.1
29.3
27.0
48.3
54.6
72.7
42.4
26.4
38.5
24.2
71.9
17.3
17.1
24.7
180.7
27.1
16.8
65.7
30.8
19.4
13.8
/
/
/
/
/
/
/
/
/
/
/
/
/
/
47.9
68.1
87.2
45.3
47.8
18.8
33.1
40.6
47.0
38.5
24.6
123.4
145.0
42.9
28.8
24.0
47.7
42.4
47.0
30.6
34.7
33.2
64.1
14.7
17.7
17.9
26.4
177.5
33.5
24.0
105.1
75.1
78.1
73.7
75.6
/
95.9
74.1
78.7
71.3
79.1
62.5
/
/
/
/
/
/
44.5
71.1
87.2
53.1
52.9
21.4
33.4
40.9
49.0
37.2
24.5
124.0
144.0
42.4
28.6
23.9
48.6
48.2
42.8
149.2
30.7
38.2
181.6
13.4
16.9
17.5
26.2
177.2
107.2
/
105.5
75.6
83.2
72.3
76.6
172.6
95.6
74.0
78.2
71.0
78.6
62.3
/
/
/
/
/
/
150.1
127.8
202.9
53.4
134.1
140.9
196.9
45.5
42.3
48.4
72.5
78.7
40.0
77.2
55.1
32.0
41.6
121.7
140.4
111.0
142.8
26.8
24.7
/
/
/
/
22.6
21.1
15.6
169.3
20.9
168.9
21.2
/
/
/
/
/
/
/
/
/
/
/
/
/
/
Solvents: CDCl3; M/CD3OD; P /C5D5N; W/D2O; A/Acetone-d6. Compound (Reference): (1) Tian et al., 1998; (2) Kwak et
al., 1997; (3) Ma et al., 1997; (4,5) Ahmed and Mahmoud, 1997; (6) Ragasa et al., 1997; (7,8) Lin et al., 1996; (9) Lemmich, 1995; (10)
Takeda et al., 1997; (11) Schuquel et al., 1998; (12) Taskova et al., 1998; (13) Tuntiwachwuttikul et al., 1998; (14) Damtoft et al., 1997;
(15,16) Sudo et al., 1997; (17) Kanai et al., 1996; (18) Tan and Kong, 1997; (19) Iossifova et al., 1998; (20) Hosny, 1998; (21) Otsuka et
al., 1996; (22) Castillo et al. 1997; (23) Guilhon and Muller, 1996; (24) Siems et al., 1996; (25,26) Torres et al., 1998; (27) Donnelly et al.,
1997; (28,29) Mahmoud, 1997; (30) Ujita et al., 1992; (31 /35) Lazari et al., 1998; (36,37) Guilhon and Muller, 1998; (38) Youssef, 1998;
(39) Ma et al., 1998; (40) Helal et al. 1997; (41,42,44) Jakupovic et al., 1998b; (43) Jakupovic et al., 1998a; (45,46) Marco et al., 1998;
(47) Galal et al., 1998; (48) Lin et al., 1998; (49) Bruno et al., 1998; (50) Lobitz et al., 1998; (51) Verotta et al., 1998; (52) Ahmad et al.,
1998; (53) Brum et al., 1998; (54) Elgamal et al., 1998; (55) Tommasi et al., 1998; (56) Baykal et al., 1998; (57) Wang and Jia, 1998; (58)
Pollmann et al., 1998; (59) Junkuszew et al., 1998; (60) Mulholland et al., 1998.
616
2)
3)
4)
617
Fig. 3 (Continued)
618
Fig. 3 (Continued)
were the second (test 55) and the fourth (test 59). In
the last case, we could deduce the following: the
biosynthetic precursor of such skeleton was that that
619
Fig. 3 (Continued)
5. Conclusions
The probable problem that led to the errors verified
during the tests may have been originated from the own
database structure, that does not allow yet, until these
experiments, the separation and consultation of the
macronodes of solvents employed usually in 13C
NMR. Because of this problem, when the database
620
Fig. 3 (Continued)
621
Fig. 3 (Continued)
622
Fig. 3 (Continued)
Fig. 3 (Continued)
623
624
Fig. 3 (Continued)
Fig. 3 (Continued)
625
626
Fig. 3 (Continued)
Table 3
Results obtained by the
Substance
SISCONST
and
MACRONO
Present substituents
programs
MACRONO
program
program
Skeletal type (%)a
SISCONST
Proposed substituents
Error
range
No. of
carbons
Trans -p -coumaroyl
Glucose-(10/3)-rhamnose
Trans -p -coumaroyl
Glucopyranosyl
Rhamnopyranosyl
0.267
1.250
1.033
9
6
6
Myrcane : 92.5
8nor-myrcane: 5.0
Menthane: 2.5
6OMe-7O-Cumarin
6OMe-7O-Cumarin
0.100
10
Myrcane : 96.5
Menthane: 2.3
10nor-myrcane: 1.2
Sinapyl-alcohol
Sinapyl-alcohol
0.823
11
Myrcane : 100.0
Acetoyl
2OH-et-acryloyl
Acetoyl
2OH-et-acryloyl
3OH-metacriloyl
0.500
0.600
1.050
2
5
4
Menthane : 96.8
Skeletal-09: 3.2
Tigloyl
Tigloyl
Acetoyl
Tigloyl
Tigloyl
Acetoyl
0.410
0.410
0.850
5
5
2
Menthane : 100.0
Glucopyranosyl-2?,6?diacetate
Glucopyranosyl-2?,6 acetate
0.515
10
Pinane : 85.8
Others: 5.2
7nor-pinane: 3.0
627
Table 3 (Continued )
Substance
Present substituents
MACRONO
program
program
Skeletal type (%)a
SISCONST
Proposed substituents
Error
range
No. of
carbons
p -MeO-benzoyl (anisate)
Benzoyl
Glucopyranosyl
p -MeO-benzoyl (anisate)
Benzoyl
Glucopyranosyl
0.413
1.814
1.067
8
7
6
Pinane : 69.4
Menthane: 30.6
p -MeO-benzoyl (anisate)
p -OH-benzoyl
Glucopyranosyl
p -MeO-benzoyl (anisate)
p -OH-benzoyl
Glucopyranosyl
0.300
0.850
1.033
8
7
6
Pinane : 84.7
Menthane: 15.3
Glucopyranosyl
Glucopyranosyl
0.633
Bornane : 95.0
2et-bornane: 3.7
Others: 1.4
10
Glucose-(10/6)-apiose(fur)
Apiofuranosyl
Glucopyranosyl
0.470
0.750
5
6
Ionane : 98.6
Cyclogeraniolane: 1.1
Others: 0.3
11
Glucopyranosyl
p -MeO-cis -cinnamoyl
Metoxi
Glucopyranosyl
p -MeO-cis -cinnamoyl
Metoxi
0.683
1.915
1.700
6
10
1
Iridane : 90.2
11nor-iridane: 9.8
12
Menthiafoloyl
Glucopyranosyl
Menthiafoloyl
Glucopyranosyl
Allopyranosyl
1.415
1.567
1.567
10
6
6
Iridane : 97.8
11nor-iridane: 1.2
Others: 1.0
13
Acetoyl
Glucopyranosyl
Cis -p -coumaroyl
Metoxi
Acetoyl
Glucopyranosyl
Cis -p -coumaroyl
Trans -p -coumaroyl
metoxi
0.750
1.483
2.217
2.367
0.650
2
6
9
9
1
Iridane : 78.5
7,8seco-iridane: 12.9
11nor-iridane: 5.8
14
Foliamenthoyl
Glucopyranosyl
Foliamenthoyl
Nerol-8oyl
Glucopyranosyl
0.880
1.140
0.617
10
10
6
Iridane : 90.1
7,8seco-iridane: 8.5
Others: 1.4
15
Glucopyranosyl
Isoferuloyl
Glucopyranosyl
Trans -feruloyl
Cis -feruloyl
Isoferuloyl
0.850
0.685
1.365
2.735
6
10
10
10
11nor-iridane : 94.2
10,11dinor-iridane: 2.5
10nor-iridane: 1.7
16
Glucopyranosyl
p -Meo-trans -cinnamoyl
Glucopyranosyl
p -Meo-trans -cinnamoyl
0.683
0.670
6
10
11nor-iridane : 73.6
Iridane: 20.5
17
p -OH-benzoyl
p -OH-benzoyl
0.321
11nor-iridane : 96.6
Iridane: 3.4
18
Gentisoyl
Glucopyranosyl
Gentisoyl
Glucopyranosyl
Acetoyl
0.443
0.933
0.600
7
6
2
7 ,8seco-iridane : 72.2
Iridane: 27.7
Others: 0.1
19
Glucopyranosyl
2[p -OH-phenyl]-ethoxide
2[3,4diOH-phenyl]-ethoxide
Glucopyranosyl
2[p -OH-phenyl]-ethoxide
2[3,4diOH-phenyl]-ethoxide
0.617
0.431
0.631
6
8
8
7,8seco-iridane : 95.1
Iridane: 4.9
20
Acetoyl
Trans -caffeoyl
2[3,4diOH-phenyl]-ethoxide
Glucopyranosyl
Metoxi
Acetoyl
Trans -caffeoyl
2[3,4diOH-phenyl]-ethoxide
Glucopyranosyl
Metoxi
0.450
0.517
0.781
2.167
0.825
2
9
8
6
1
7,8seco-iridane : 68.7
Iridane: 30.9
Others: 0.4
21
Glucose-(10/6)-xilose
Glucopyranosyl
Glucose-(10/6)-xilose
Glucopyranosyl
0.686
0.650
11
6
Cadinane : 37.9
Valerenane: 14.8
Eudesmane: 8.3
628
Table 3 (Continued )
Substance
Present substituents
MACRONO
program
program
Skeletal type (%)a
SISCONST
Proposed substituents
Error
range
No. of
carbons
22
Glucose
Glucose
1.092
Iludane : 100.0
23
Angeloyl
Acetoyl
Tigloyl
Acetoyl
1.300
1.050
5
2
Eudesmane : 86.2
Nardosinane: 5.3
Others: 5.0
24
Acetoyl
Acetoyl
Acetoyl
Acetoyl
Acetoyl
Acetoyl
0.250
0.450
0.500
2
2
2
Drimane : 86.7
Eudesmane: 8.1
Others: 4.0
25
Isobutiroyl
Propionyl
Isobutiroyl
0.800
2.825
3
4
Eremofilane : 73.3
Furodisane: 4.8
Germacrane: 3.3
26
2Me-isobutyroyl
Propionyl
2Me-isobutyroyl
0.733
1.030
3
5
Eremofilane : 36.7
1-3-Eudesmane: 27.8
Eudesmane: 8.2
27
Ortoselinoyl
Ortoselinoyl
0.537
protoiludane : 44.7
Trifarane: 23.1
Eudesmane: 5.8
28
p -MeO-benzoyl (anisate)
p -MeO-benzoyl (anisate)
0.550
Carotane : 90.7
Eudesmane: 4.5
Others: 2.8
29
Angeloyl
Isovaleroyl
Tigloyl
0.970
0.970
5
5
Carotane : 100.0
30
2Me-butyroyl
Acetoyl
2Me-butyroyl
Furoyl
2Me-butyroyl
Acetoyl
2Me-butyroyl
Furoyl
0.820
0.850
1.380
1.820
5
2
5
5
Eudesmane : 98.2
Others: 1.8
31
4OH-3Me-butiroyl
4OH-3Me-butiroyl
Etoxide
Isobutiroyl
0.010
1.125
1.425
5
2
4
Germacranolide : 53.2
Guaianolide: 38.3
Eudesmanolide: 8.5
32
Tigloyl
Tigloyl
Metacryloyl
0.830
0.925
5
4
Germacranolide: 65.8
Guaianolide: 23.7
Eudesmanolide: 10.5
33
4OH-isobutyroyl
4OH-isobutyroyl
2Me-butyroyl
0.900
1.210
4
5
Germacranolide : 54.7
Guaianolide: 30.7
Eudesmanolide: 14.7
34
5OH-tigloyl
5OH-tigloyl
Etoxide
0.540
1.025
5
2
Germacranolide : 62.5
Guaianolide: 27.8
Eudesmanolide: 9.7
35
3OH-metacryloyl
Metacryloyl
3OH-metacryloyl
Butoxi
1.750
0.550
3.663
4
4
4
Eudesmanolide : 86.2
Guaianolide: 13.1
Others: 0.7
36
Acetoyl
Angeloyl
Acetoyl
Tigloyl
Angeloyl
0.800
0.410
0.480
2
5
5
Eudesmanolide : 100.0
37
Angeloyl
Acetoyl
Angeloyl
Tigloyl
Acetoyl
0.480
0.690
1.200
5
5
2
Eudesmanolide : 87.1
Pseudoguaianolide: 6.5
Germacranolide: 6.5
38
5OH-tigloyl
5OH-tigloyl
0.920
Guaianolide : 76.9
Eudesmanolide: 23.1
629
Table 3 (Continued )
Substance
Present substituents
MACRONO
program
program
Skeletal type (%)a
SISCONST
Proposed substituents
Error
range
No. of
carbons
39
Glucopyranosyl
Glucopyranosyl
Etoxide
0.683
0.475
6
2
Guaianolide : 48.8
Eudesmanolide: 45.9
Pseudoguaianolide: 3.9
40
4OH-tigloyl
4OH-tigloyl
4OH-tigloyl
4OH-tigloyl
3OH-metacryloyl
0.260
0.480
2.425
5
5
4
Guaianolide : 80.4
Eudesmanolide: 19.6
41
(5) Acetoyl
Isobutyroyl
(5) Acetoyl
Isobutyroyl
0.250
0.513
2
4
Jatrophane : 97.2
Briarane: 2.8
42
(5) Acetoyl
2Me-butyroyl
(4) Acetoyl
2Me-butyroyl
Acetoyl
0.250
0.810
0.400
2
5
2
Jatrophane : 88.6
Briarane: 11.4
43
Angeloyl
Acetoyl
Angeloyl
Angeloyl
Tigloyl
Angeloyl
Acetoyl
Tigloyl
0.340
0.890
0.620
0.750
1.050
5
5
5
2
5
Ingenane : 100.0
44
Angeloyl
Acetoyl
Benzoyl
Angeloyl
Acetoyl
Benzoyl
0.620
0.750
1.357
5
2
7
Ingenane : 77.6
Latirane: 16.9
Abietane: 2.5
45
Tigloyl
Acetoyl
Tigloyl
Acetoyl
Tigloyl
Acetoyl
Tigloyl
Acetoyl
0.450
0.650
0.750
3.100
5
2
5
2
Latirane : 100.0
46
(3) Acetoyl
Isovaleroyl
(3) Acetoyl
Isovaleroyl
0.500
0.910
2
5
Latirane : 100.0
47
Succinoyl
Succinoyl
0.125
Labdane : 30.7
Ent-caurane: 26.2
48
Cis -p -coumaroyl
Cis -p -coumaroyl
Angeloyl
Butoxi
1.039
1.140
1.387
9
5
4
Labdane : 51.0
Others: 11.0
Ent-caurane: 10.7
49
Acetoyl
2Me-butyroyl
Acetoyl
Acetoyl
2Me-butyroyl
Acetoyl
0.350
0.590
0.650
2
5
2
Clerodane : 77.6
Ent-caurane: 9.1
Others: 9.0
50
Trans -cinnamoyl
Cis -cinnamoyl
Trans -cinnamoyl
0.456
0.811
9
9
Ent-caurane : 53.8
Others: 11.1
Isopimarane: 5.5
51
Sophoroside
Glucopyranosyl
Sophoroside
Cellobioside
0.983
1.104
1.442
6
12
12
Cicloartane : 47.5
Oleane: 11.9
Ursane: 8.2
52
Glucopyranosyl
Glucopyranosyl
0.783
Cicloartane : 66.3
Oleane: 6.0
Lupane: 5.0
53
n -Hexanoyl
n -Hexanoyl
0.283
Lupane : 34.5
Oleane: 21.4
Ursane: 9.7
54
Glucopyranosyl
Sophoroside
Glucopyranosyl
Sophoroside
Etoxide
0.700
1.163
0.225
6
12
2
Lupane : 30.5
Oleane: 20.3
Ursane: 15.5
630
Table 3 (Continued )
Substance
Present substituents
MACRONO
program
program
Skeletal type (%)a
SISCONST
Proposed substituents
Error
range
No. of
carbons
55
Trans -cinnamoyl
Trans -cinnamoyl
Cis -cinnamoyl
0.978
1.194
9
9
Oleane: 38.4
Ursane : 31.4
Others: 9.6
56
Glucose-(10/6)-allose
Xilopyranosyl
Glucose-(10/6)-allose
Butoxi
Xilopyranosyl
0.021
1.212
2.500
12
4
5
Ursane : 36.0
Oleane: 29.0
Lupane: 6.5
57
Butoxi
Butoxi
1.013
Ursane : 39.8
Oleane: 34.1
58
Glucuronic-acid
Glucopyranosyl
Glucuronic-acid
4OH-isobutyroyl
Butoxi
Glucopyranosyl
0.758
1.275
1.388
1.467
6
4
4
6
Oleane : 63.9
Ursane: 17.1
Lanostane: 5.6
59
Glucuronic-acid
Glucopyranosyl
Glucuronic-acid
Propionyl
Glucopyranosyl
0.692
1.600
1.650
6
3
6
Oleane: 44.9
Ursane: 18.7
Lupane: 14.0
30nor-oleane : 3.9
60
Acetoyl
Acetoyl
Acetoyl
Acetoyl
0.100
0.250
2
2
Meliacane : 74.4
Abeolimonoid: 8.3
Abeoursane: 7.4
Table 4
Summary of the analyses realized by the
MACRONO
program
Macronodes tested
Number of hits
Number of errors
trans -p -Coumaroyl
Glucopyranosyl-(1 0/6)-Rhamnopyranosyl
6OMe-7O-Cumarin
Sinapyl-alcohol
Acetoyl
2OH-et-acryloyl
Tigloyl
Glucopyranosyl-2?,6?diacetate
p -OMe-benzoyl (anisate)
Benzoyl
Glucopyranosyl
p -OH-benzoyl
Glucopyranosyl-(1 0/6)-Apiofuranosyl
p -MeO-cis -cinnamoyl
Metoxi
Menthiafoloyl
Cis -p -Coumaroyl
Foliamenthoyl
Isoferuloyl
p -MeO-trans -cinnamoyl
Gentisoyl
2[p -OH-phenyl]-ethoxide
1
1
1
1
32
1
5
1
3
2
18
2
1
1
3
1
2
1
/
1
1
1
/
/
/
/
/
/
/
/
/
/
1
/
/
/
/
/
/
/
1
/
/
/
631
Table 4 (Continued )
Macronodes tested
Number of hits
Number of errors
2[3,4-diOH-phenyl]-ethoxide
Trans -Caffeoyl
Glucose(61/1)Xilose
Angeloyl
Isobutyroyl
2Me-butiroyl
Ortoselinoyl
Furoyl
4OH-3Me-butiroyl
4OH-isobutiroyl
5OH-tigloyl
3OH-metacryloyl
4OH-tigloyl
Isovaleroyl
Succinoyl
Trans -cinnamoyl
Sophoroside
n -hexanoyl
Glucopyranosyl-(1 0/6)-Allopyranosyl
Xilopyranosyl
Butoxi
Glucuronic acid
2
1
1
4
2
5
1
1
1
1
2
1
2
1
1
1
2
1
1
1
1
2
/
/
/
3
/
/
/
/
/
/
/
/
/
/
/
1
/
/
/
/
/
/
Total
115
Acknowledgements
This work was supported by grants from the Fundacao de Amparo a` Pesquisa do Estado de Sao Paulo
(FAPESP), CAPES and by the Conselho Nacional de
Desenvolvimento Cientfico e Tecnologico (CNPq). The
authors thank Antonio J.C. Brant for helpful discussion
during the preparation of the manuscript.
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