Volatile constituents of Eupatorieae (Asteraceae). Compositional multivariate analysis of volatile oils from Southern Brazilian species in the subtribe Disynaphiinae Author de Souza, Tiago J. T. * & Faculdade de Farm´acia, Universidade Federal do Rio Grande do Sul (UFRGS), Av. Ipiranga, 2752, 90610 - 000, Porto Alegre, Brazil Author S Author Bordignon, ergio A. L. Programa de P´os-Graduaç ˜ ao em Avaliaç ˜ ao de Impactos Ambientais, Centro Universit´ario La Salle, Canoas, Brazil Author Apel, Miriam A. Author Henriques, Amelia T. text Phytochemistry 2021 112734 2021-06-30 186 1 23 http://dx.doi.org/10.1016/j.phytochem.2021.112734 journal article 10.1016/j.phytochem.2021.112734 1873-3700 8258534 2.2. Genus Raulinoreitzia Raulinoreitzia tremula (Hook. & Arn.) R.M.King & H.Rob. and Raulinoreitzia crenulata (Sprengel) R.M.King & H.Rob. (sampled in this study) are, together with R. leptophlebia , the only three species recognized in the genus Raulinoreitzia ( Koiti and Hattori, 2013 ) . The chemical composition of VOs obtained from both the leaves and inflorescences of R. tremula (syn. Eupatorium tremulum - common name: “chirca”, “vassour˜ao-do-brejo”), a 2–3 m tall, densely branched shrub, native to southern Brazil , Uruguay , and Northeastern Argentina ( King and Robinson, 1987 ; Matzenbacher, 1979 ) are quite similar with the predominance of sesquiterpenes (97.2 and 84.0%). Among the hydrocarbon sesquiterpenes (46.0 and 49.7%), compounds bearing a bisabolane nucleus were predominant: β- bisabolene (15.5 and 17.1%), β- sesquiphellandrene (7.9 and 7.1%); alongside the cadinane amorpha-4,7 (11)-diene (11.7 and 10.5%). Among the oxygenated sesquiterpenes, furanocadinanes verboccidentafuran (16.1 and 11.6%) and 3-oxo-verboccidentafuran (3.6 and 14.7%), and alcohols epi-α- bisabolol (9.6 and 10.7%) and amorpha-4-en-7-ol (7.5 and 6.6%) were the most abundant. The presence of sesquiterpene compounds with a bisabolane nucleus is not common in this subtribe, nor are furan compounds. However, other samples of R. tremula collected from different populations in RS have been reported to have qualitatively similar compositions ( de Souza et al., 2017 ). This species occurs in swampy humid fields and edges of floodable galleries ( Koiti and Hattori, 2013 ). Together with Hatschbachiella tweediena (Eupatoriinae subtribe), it is important in the reproductive biology of the rusty-collared seedeater Sporophila collaris ( Rosoni, 2017 ; Rosoni et al., 2019 ). This species has been implicated in cattle intoxication ( Lucioli et al., 2007 ) and its extracts exhibit cytotoxicity in vitro against tumor cells ( Monks et al., 2002 ). A direct link between these activities and a particular chemical compound has not been established to date, but the participation of their characteristic furanocadinenes cannot be ruled out. The chemical composition of VOs obtained from R. crenulata , a 2 m tall, white-flowered shrub native to Central, Southern, and Northeastern Brazil , Peru , Bolivia , and Northern Argentina ( King and Robinson, 1987 ; Matzenbacher, 1979 ) was quite similar to another sample of this species reported by our group and collected from the same area ( Souza et al., 2007 ), with a slight predominance of hydrocarbon monoterpenes over sesquiterpenes: β- pinene (19.1%) and α- pinene (14.6%) were the main monoterpenes, and β- caryophyllene (7.3%), germacrene D (11.4%), and Table 2 ( continued ) ˆes Cachoeiras

Genus	–	Acanthostyles	Raulinoreitzia		Campovassouria		Symphyopappus
Species	–	A. buniifolius	R. crenulata		R . tremula		C . bupleurifolia		S. casarettoi		S . itatiayensis	S . reticulatus
Sampling site	–	Guaíba	Canela	Canela	Guaíba	Morro Reuter		S˜ ao Francisco Paula			Imbe´Tr	Gravataí	Gravataí
Sampling time	–	Mai /05	Apr / 05	Apr / 05	Apr / 05	Oct / 05	Oct / 05	Apr / 05	Jan /11	Apr / 05	Oct / 05
Analyzed organs	RI a	i b	ap c	I	l d	l	i	l	i	l	i	l	i	ap	l	l	i
OM g HS h OS i Total	– – – –	– 78.0 – 96.4	0.2 33.4 4.7 98.0	– 47.0 0.7 99.5	0.2 32.0 1.2 99.6	– 49.7 34.4 91.5	– 46.0 47.7 94.8	1.8 27.4 19.5 98.2	0.8 37.1 30.4 95.6	– 9.6 67.2 91.2	2.1 5.6 74.7 94.1	0.3 27.3 0.8 99.9	0.7 45.8 4.4 94.5	– 62.5 22.2 85.0	– 63.1 2.3 99.3	0.1 63.1 11.3 97.6	– 78.0 – 96.4

Legend a Retention Index in a DB5 column b inflorescences c aerial parts d leaves e Aliphatics f Hydrocarbon Monoterpenes g Oxygenated Monoterpenes h Hydrocarbon Sesquiterpenes i Oxygenated Sesquiterpenes j traces. Table 3 Chemical composition of Volatile Oils from species in the Sutribe Disysnaphiinae of Eupatorieae (Asteraceae) from Southern Brazil. Grazielia and Disynaphia .

Genus	–	Grazielia	Disynaphia
Species	–	G. gaudichaudeana		G. intermedia		G. nummularia		G. serrata	D. ericoides	D. ligulifolia	D. spathulata
Sampling site	–	Canela	Paraíso do Sul		Guaíba	Guaíba	Sapiranga		Caxias do Sul	Gravataí	Sapiranga	Viam˜ ao	Canela	Viam˜ ao
Sampling time	–	Abr/05	Mar/06	Apr/05	Oct/05	Jan/06	Apr/05	Oct/05	Mar/06	Mar/06	Apr/05	Oct/05
Analyzed organs	-RI a	ap b	l c	i d	ap	l	i	ap	t e	ap	l	i	l	l i	l	i	l
(Z)-3-hexenol	858	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
N-hexanol	866	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
santolinatriene	880	–	–	–	–	–	–	–	–	–	–	–	–	– tr	tr	tr	–
tricyclene	911	–	tr k	tr	–	–	tr	tr	–	tr	tr	–	–	– –	–	–	–
α- thujene	916	10.1	0.1	0.2	0.1	0.1	0.2	0.2	tr	0.1	0.2	0.2	tr	0.5 0.2	0.4	0.3	tr
α- pinene	922	12.4	14.4	15.5	15.9	15.1	19.9	8.5	2.8	16.8	30.2	31.5	tr	2.6 1	11.6	7	2.3
α- fenchene	935	–	tr	–	–	–	–	tr	–	tr	–	–	–	– –	–	tr	–
thuja-2,4(10)-diene	941	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	tr	–
verbenene	947	–	tr	tr	–	–	–	–	–	–	–	–	–	– –	–	–	–
camphene	966	–	tr	0.1	–	tr	tr	tr	–	0.1	tr	0.1	–	tr –	–	–	–
sabinene	966	2.8	4.9	5.7	2.6	2.5	2.7	6	2.9	1	2.5	3.6	0.1	0.8 0.3	1.9	1.3	0.6
β- pinene	969	9.2	22.6	28.9	17.3	24.2	23.9	20.5	10	17	17	13.8	0.3	9.4 5.2	24.1	14.9	10.8
β- myrcene	979	1.9	1.7	2.6	10.8	3.6	4	2.5	1.2	8.1	3.6	5.4	tr	0.4 2.2	5.1	6.5	0.2
δ-2-carene	994	–	0.1	0.2	–	–	–	0.2	0.7	–	–	–	tr	tr 0.2	tr	0.1	–
α- phellandrene	995	0.3	tr	0.1	tr	tr	0.1	0.4	tr	0.1	tr	–	–	– tr	–	tr	–
α- terpinene	1007	0.2	tr	0.1	–	tr	tr	0.1	–	0.1	0.1	–	–	– tr	–	0.2	–
p-cymene	1015	1.6	1.4	3.7	0.4	0.6	0.9	1.8	5.5	0.9	0.1	0.2	1.2	0.1 0.1	0.3	0.2	0.7
limonene	1020	37.2	18.3	18.3	19.7	21.6	25.2	36.5	31.5	10.4	19.4	20.9	0.2	1.2 0.7	13.1	12.2	2.3
β- phellandrene	1021	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
(Z)-β- ocimene	1031	–	tr	0.1	tr	0.1	0.1	0.2	tr	0.3	0.2	0.1	0.1	– tr	0.1	0.5	–
(E)-β- ocimene	1042	0.7	0.2	0.3	2.4	2.6	2.9	1.6	0.2	1.8	2.7	1.9	3.2	– 4.2	2.3	13.3	–
γ- terpinene	1051	0.3	0.1	0.1	tr	tr	0.1	0.2	tr	0.1	0.1	–	–	– tr	–	0.4	–
terpinolene	1080	0.1	tr	–	tr	tr	0.1	0.2	tr	tr	0.1	tr	tr	– tr	–	0.2	–
linalool	1092	–	–	–	–	1.1	–	0.1	tr	tr	–	0.1	tr	tr –	1.3	0.3	0.3
1,3,8-p-menthatriene	1096	–	tr	–	–	–	–	–	–	–	–	tr	–	– –	tr	–	–
α- campholenal	1118	–	tr	tr	–	–	–	–	–	–	–	–	–	– –	–	–	tr
nopinone	1121	–	–	0.1	–	–	–	–	–	–	–	–	–	tr –	–	–	0.2
trans-sabinol	1128	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	tr	–
trans-pinocarveol	1130	–	0.5	0.7	–	–	–	tr	–	tr	–	–	–	0.2 –	tr	tr	0.9
trans-verbenol	1134	–	0.3	0.3	–	–	–	–	–	tr	tr	–	–	tr –	tr	–	tr
p-mentha-1,5-dien-8-ol	1150	–	tr	tr	–	–	–	–	–	–	–	–	–	– –	–	–	–
pinocarvone	1151	–	0.3	0.3	–	–	–	–	–	–	–	–	–	tr –	tr	–	tr
n-heptanoic acid	1170	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
terpinen-4-ol	1172	0.3	0.4	0.5	tr	0.3	0.5	0.5	0.2	0.3	0.3	0.3	tr	tr tr	0.3	0.8	tr
cryptone	1178	–	0.3	0.4	–	–	–	tr	tr	–	–	–	–	– –	–	–	0.4
α- terpineol	1183	tr	0.2	0.2	tr	0.5	0.2	0.1	tr	0.1	0.3	0.3	tr	tr tr	0.7	0.6	0.4
myrtenal	1188	–	0.4	0.6	–	–	tr	tr	tr	–	–	tr	–	tr –	–	–	0.5
myrtenol	1189	–	0.4	0.6	–	–	tr	tr	tr	tr	–	tr	–	tr –	–	–	0.4
neral	1200	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
nerol	1211	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
verbenone	1216	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	tr
carvone	1224	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	tr
thymol methyl ether	1225	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	tr
geraniol	1238	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
cis-chrysanthemyl acetate	1245	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
isobornyl acetate	1272	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
bornyl acetate	1273	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	tr	–
n-tridecane	1284	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–

( continued on next page )

Genus	–	Grazielia	Disynaphia
Species	–	G. gaudichaudeana		G. intermedia		G. nummularia		G. serrata	D. ericoides	D. ligulifolia	D. spathulata
Sampling site	–	Canela	Paraíso do Sul		Guaíba	Guaíba	Sapiranga		Caxias do Sul	Gravataí		Sapiranga	Viam˜ ao	Canela	Viam˜ ao
Sampling time	–	Abr/05	Mar/06	Apr/05	Oct/05	Jan/06	Apr/05	Oct/05	Mar/06	Mar/06	Apr/05	Oct/05
Analyzed organs	-RI a	ap b	l c	i d	ap	l	i	ap	t e	ap	l	i	l	l i	l	i	l
trans-sabinyl hydrate	1285	–	–	–	–	–	–	–	–	–	–	–	–	– –	tr	–	–
trans-pinocarvyl acetate	1289	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
silphiperfol-5-ene B	1308	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
δ- elemene	1326	–	–	–	–	–	–	–	–	tr	tr	tr	tr	tr tr	tr	tr	tr
verbenyl acetate	1327	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
7-epi-silphiperfol-5-ene	1328	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- cubebene	1336	–	–	–	–	–	–	–	–	–	tr	tr	–	tr tr	tr	tr	tr
neryl acetate	1351	–	–	–	–	–	–	–	–	–	–	–	–	tr –	tr	tr	2.4
cyclosativene	1352	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- ylanguene	1357	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- copaene	1362	tr	0.2	0.1	0.4	0.3	0.2	0.2	0.4	0.4	0.5	0.4	0.5	0.4 0.3	0.5	0.4	0.6
β- maaliene	1365	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
trans-myrtenyl acetate	1368	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	tr	–
geranyl acetate	1369	–	–	–	–	–	–	–	–	–	–	–	–	tr –	–	–	1.7
β- bourbonene	1370	tr	tr	–	–	–	tr	tr	tr	tr	0.1	tr	0.7	tr –	–	tr	–
β- cubebene	1376	tr	tr	tr	tr	tr	tr	0.1	0.1	0.1	0.2	0.1	tr	tr 0.1	0.1	tr	tr
β- elemene	1378	–	tr	tr	tr	0.2	tr	tr	tr	0.4	0.1	tr	9	1.4 1	0.6	0.4	2.4
isocaryophyllene	1390	tr	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
cyperene	1394	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- cedrene	1397	–	–	–	–	–	–	–	–	–	–	–	–	– tr	–	–	–
α- gurjunene	1400	–	–	–	–	–	–	–	–	tr	–	–	–	– –	–	tr	–
(E)-β- caryophyllene	1408	1.5	3.6	2.7	8.1	7.2	7.3	3.6	5.7	7.6	4.8	5.5	21.3	2.8 6.6	7	7.5	0.6
β- gurjunene	1414	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
γ- elemene	1414	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- trans-bergamotene	1420	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
aromadendrene	1422	–	–	–	–	0.1	0.2	–	–	0.3	0.1	0.1	tr	tr tr	–	0.1	0.5
α- guaiene	1423	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
(Z)-β- farnesene	1432	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- himachalene	1433	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- humulene	1437	0.2	0.2	0.1	0.4	0.4	0.3	0.3	0.6	0.5	0.2	0.3	3	1 1.5	0.8	0.7	tr
sesquisabinene	1438	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
(E)-β- farnesene	1442	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
allo-aromadendrene	1442	–	tr	tr	–	0.1	–	tr	–	0.3	0.1	tr	–	0.3 0.4	0.3	0.3	tr
dehydroaromadendrene	1443	–	–	–	–	–	–	–	–	–	–	–	tr	– –	–	–	–
β- santalene	1446	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
9-epi-(E)-caryophyllene	1451	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
drima-7,9(11)-diene	1453	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
cadina-1(6),4-diene	1456	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	tr	–
amorpha-4,7(11)-diene	1457	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
β- chamigrene	1459	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
cis-cadina-1(6),4-diene	1462	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
γ- muurolene	1463	–	–	–	–	0.1	0.1	tr	–	0.1	–	tr	tr	0.7 0.3	–	0.2	0.7
germacrene D	1467	11.3	1.6	1	4.9	3.5	2.3	10.1	26.3	7	–	–	8.6	tr 18.8	5.6	6.5	tr
amorpha-4,7(11)-diene	1468	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
ar-curcumene	1468	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	tr
β- selinene	1470	–	–	–	–	–	–	–	–	–	–	–	0.2	tr tr	tr	tr	tr
cis-β- guaiene	1472	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
epi-bicyclosesquiphellandrene	1476	tr	–	–	0.3	–	–	–	–	0.1	–	–	–	– –	tr	tr	–
α- selinene	1478	–	–	–	–	–	–	–	–	–	–	–	–	– –	tr	–	–

( continued on next page )

Genus	–	Grazielia	Disynaphia
Species	–	G. gaudichaudeana		G. intermedia		G. nummularia		G. serrata	D. ericoides	D. ligulifolia	D. spathulata
Sampling site	–	Canela	Paraíso do Sul		Guaíba	Guaíba	Sapiranga		Caxias do Sul	Gravataí	Sapiranga	Viam˜ ao	Canela	Viam˜ ao
Sampling time	–	Abr/05	Mar/06	Apr/05	Oct/05	Jan/06	Apr/05	Oct/05	Mar/06	Mar/06	Apr/05	Oct/05
Analyzed organs	-RI a	ap b	l c	i d	ap	l	i	ap	t e	ap	l	i	l	l i	l	i	l
viridiflorene	1478	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
valencene	1479	–	–	–	–	–	–	–	–	–	–	–	tr	– –	–	–	–
bicyclogermacrene	1482	7.6	0.9	0.3	9.4	4.7	2.3	2.7	4.8	16.9	–	–	15.1	– 11.6	3.4	6.7	–
α/β- chamigrene	1484	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- muurolene	1486	tr	tr	tr	0.6	0.3	0.3	0.1	0.1	–	0.2	0.1	0.1	1.8 1.2	0.6	0.7	1.2
germacrene A	1489	0.1	tr	tr	0.2	0.1	tr	0.1	0.2	0.2	0.1	tr	5.4	tr 1.3	0.8	0.5	–
(E,E)-α- farnesene	1490	–	–	–	–	–	–	–	–	–	–	–	–	tr 0.2	–	–	–
1,7-di-epi-β- cedrene	1494	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	tr
β- bisabolene	1494	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
trans-β- guaiene	1494	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
(Z)-α- bisabolene	1497	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
(Z)-γ- bisabolene	1497	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
γ- cadinene	1497	–	tr	–	–	0.1	0.1	tr	tr	0.2	tr	0.1	0.3	1.4 0.9	0.3	0.5	1
δ- amorphene	1499	–	–	–	–	–	–	–	–	–	–	–	–	0.8 tr	–	–	–
cubebol	1500	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
cis-cadina-1,4-diene	1502	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	0.5
7-epi-α- selinene	1503	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
germacrene C	1503	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
calamenene	1504	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
cis-calamenene	1505	–	–	–	–	–	–	tr	–	–	–	–	–	tr tr	tr	–	tr
δ- cadinene	1506	0.5	0.2	0.1	1.9	1.2	0.9	0.4	0.5	1	0.8	0.6	1.1	0.8 6.7	1.9	3.2	–
β- cadinene	1506	–	tr	–	–	–	–	tr	–	–	–	–	–	– tr	tr	tr	–
cadina-1,4-diene	1514	–	–	–	tr	–	–	tr	tr	tr	–	tr	–	– –	–	–	–
trans-cadina-1,4-diene	1514	–	–	–	–	–	–	–	–	–	–	–	–	tr 0.2	tr	tr	–
β- sesquiphellandrene	1515	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- cadinene	1520	–	–	–	–	tr	–	tr	tr	tr	–	tr	tr	tr 0.4	tr	tr	tr
liguloxide	1523	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- calacorene	1526	–	–	–	–	tr	–	–	–	–	–	–	tr	tr tr	tr	tr	tr
unknown	1529	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
elemol	1534	–	–	–	–	–	–	–	–	–	–	–	tr	– –	–	–	–
germacrene B	1542	–	–	–	–	tr	–	–	–	0.2	–	–	tr	– tr	–	–	–
cis-muurola-4(14),5-diene	1547	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
γ- calacorene	1549	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
β- calacorene	1551	–	–	–	–	–	–	–	–	–	–	–	–	tr –	–	–	–
germacrene D-4-ol	1563	–	–	–	–	–	–	–	–	–	–	–	tr	– 1.1	–	–	–
β- copaen-4-α- ol	1563	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
(E)-nerolidol	1566	–	–	–	–	–	–	tr	tr	–	–	0.2	0.5	0.7 0.2	0.5	0.5	1.3
ledol	1567	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
spathulenol	1569	1.5	20.5	9.4	1.3	3.5	2.5	1.4	2.5	3.8	1.8	2.6	8.5	11.8 1.3	5.7	4.2	22.6
caryophyllene oxide	1579	–	2	4	0.6	1	1	0.3	0.4	0.6	0.5	0.5	1.8	4.1 –	1	0.4	7
epiglobulol	1581	–	1.4	0.8	–	1.7	0.7	–	–	–	1.1	1.1	–	– –	–	–	–
globulol	1581	–	1	0.7	0.5	0.8	0.4	0.2	0.4	0.6	0.2	0.3	2	1.6 –	0.7	1.1	4.5
epi-globulol	1587	–	–	–	–	–	–	–	–	–	–	–	2.9	8.8 4.3	–	–	5.9
humulene epoxide I	1588	–	–	–	–	–	–	–	–	1.6	–	–	–	1 0.6	–	0.2	1.1
5-epi-7-epi-α- eudesmol	1591	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–

( continued on next page )

Genus	–	Grazielia	Disynaphia
Species	–	G. gaudichaudeana		G. intermedia		G. nummularia		G. serrata	D. ericoides	D. ligulifolia	D. spathulata
Sampling site	–	Canela	Paraíso do Sul		Guaíba	Guaíba	Sapiranga		Caxias do Sul	Gravataí	Sapiranga	Viam˜ ao	Canela	Viam˜ ao
Sampling time	–	Abr/05	Mar/06	Apr/05	Oct/05	Jan/06	Apr/05	Oct/05	Mar/06	Mar/06	Apr/05	Oct/05
Analyzed organs	-RI a	ap b	l c	i d	ap	l	i	ap	t e	ap	l	i	l	l i	l	i	l
humulene epoxide II	1601	–	0.1	0.2	–	–	–	–	–	–	–	–	tr	0.8 –	–	–	1.3
cis-cadin-4-en-7-ol	1612	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
1,10-di-epi-cubenol	1615	–	–	–	–	–	–	–	–	–	–	–	–	– tr	–	–	–
cadinol	1616	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
eudesmol*	1619	–	–	–	–	–	–	0.1	–	–	–	–	–	– –	–	–	–
caryophylladienol II	1620	–	–	–	–	–	–	–	–	–	–	–	0.5	– –	–	–	–
unknown	1622	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
amorpha-4-en-7-ol	1625	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
1-epi-cubenol	1626	–	–	–	–	–	–	–	–	–	–	–	–	0.8 0.4	0.1	tr	0.5
cubenol	1631	–	–	–	–	–	–	–	–	0.2	–	–	–	– –	–	–	–
isospathulenol	1631	–	0.6	0.4	–	0.1	0.1	–	tr	0.1	–	0.2	1	– tr	0.7	0.3	–
τ- cadinol/τ- muurolol	1636	–	–	–	–	0.6	–	0.2	0.1	0.1	–	–	0.7	13.3 7.9	2	2.2	5.7
α- muurolol	1643	–	–	–	–	tr	–	tr	tr	–	–	–	tr	2.6 1.4	0.4	0.4	1.5
β- eudesmol	1643	–	–	–	–	0.1	–	–	–	–	–	–	–	– 0.2	–	tr	0.7
α- cadinol	1655	–	–	–	–	1	–	0.5	0.5	0.4	–	–	1.9	23.9 14.6	3.2	3.3	12
verboccidentafuran	1662	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
cadalene	1663	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
α- bisabolol	1677	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
epi-α- bisabolol	1680	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
(2Z,6E)-farnesol	1687	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
dodecanal	1700	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
acetato de (E)-nerolidol	1710	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
(E,E)-farnesol	1711	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
laevigatin	1732	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
Z-lanceol	1758	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-octadecane	1795	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
3-oxo-verboccidentafuran	1856	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
hexa-hydrofarnesylacetone	1862	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
methyl n-hexadecanoate	1914	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-eicosane	1967	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-heneicosane	2180	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-docosane	–	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-tricosane	–	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-tetracosane	–	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-hexadecanoic acid	1982	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-nonadecanal	2107	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
trans-phytyl acetate	2208	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-pentacosane	2469	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-hexacosane	–	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-heptacosane	2638	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-octacosane	–	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
n-nonacosane	2796	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
AL f	–	–	–	–	–	–	–	–	–	–	–	–	–	– –	–	–	–
HM g	–	76.8	63.8	75.9	69.2	70.4	80.1	78.9	54.8	56.8	76.2	77.7	5.1	15.0 14.1	58.9	57.1	16.9

( continued on next page ) Table 3 ( continued ) bicyclogermacrene (9.7%), the main sesquiterpenes. In the previously reported sample, there were higher amounts of β- myrcene (15.3%) and limonene (22.8%), while the percentage of α- pinene (14.6%) and α- thujene (7.1%) were higher. This is an important species in the reproductive biology of black-bellied seedeaters ( Sporophila melanogaster ) (in the same way as Gyptidinae Barrosoa betoniciiformis ) ( Rovedder, 2011 ; Rovedder and Fontana, 2012 ), red-eyed Vireo ( Vireo olivaceus ), and Long-tailed Reed-Finch ( Donacospiza albifrons ) (similarly to Grazielia intermedia ) ( Maurício et al., 2013 ). The VOs were previously analyzed, yielding 0.54–0.68% (dry and fresh inflorescences, respectively), but the chemical composition was not reported ( Souza, 2015 ). Another report from Paran´a, Brazil , described limonene (39%) and δ- cadinene (8%) as the major compounds and their activity against the strawberry aphid Aphis forbesi ( Maleski et al., 2019 ) . Despite sharing the same origin, the chemical composition reported here shows qualitative differences regarding our previous report on this species, reflecting the known variability of volatile chemistry. The composition described for the Parana´samples was even more deviant in their values for limonene, to which the anti-aphid activity of R. crenulata oil was credited ( Maleski et al., 2019 ). To the best of our knowledge, the only known reports on the VOs of R. tremula are from RS ( de Souza et al., 2017 ) and no description has ever been given for the chemical composition of the other species in the genus R. leptophlebia . To date, the volatile chemistry of the genus Raulinoreitzia is very basal for R. crenulata in both Parana´and RS, and extremely atypical for R. tremula in RS. In this way, more samples of R. tremula and R. leptophlebia are needed to better describe this genus.