Preliminary Investigation on the Volatile Constituents of Croton sonderianus Muell. Arg.: Habitat, Plant Part and Harvest Time Variation

Dourado, Regina C M

Abstract

The chemical composition of the oils obtained from the leaves of Croton sonderianus from different regions of Ceará State (northeast of Brazil) from the same population at different times were analyzed by GC/MS: α-pinene, myrcene, 1,8-cineole, β-caryophyllene and spathulenol. Representative constituents present in almost all analyses were used for comparison. The oils from different plant parts (leaves, flowers, roots and trunk barks) of a same specimen were also analyzed: β-phellandrene (20.4%, leaves), bicyclogermacrene (29.1% and 17.7%, flowers and leaves, respectively), β-elemene (17.8% and 22.8%, flowers and trunk bark, respectively), cyperene (14.2%, roots) and germacrene D (12.8%, trunk bark) were the major components.

Key Word Index

Croton sonderianus, Euphorbiaceae, essential oil composition, α-pinene, myrcene, 1,8-cineole, β-phellandrene, limonene, bicyclogermacrene, cyperene, β-caryophyllene, β-elemene, spathulenol.

Introduction

The "caatinga," clear or light forest in the native Brazilian Indian language, is a very characteristic flora of northeastern Brazil. Characterized by herbs, shrubs and small trees very well adapted to the drastic climatic conditions, the "caatinga" possesses a large number of plants rich in essential oils. In the Euphorbiaceae family, the Croton genus, due to high incidence and species dispersion, contains by far the largest number of oil producing plants in the Brazilian northeast (1). In the literature, the oil composition of several Croton species can be found: C. adenocalyx (2), C. lundianus and C. glandulosus (3), C. aff. nepetifolius (4), C. cajucam (5,6), C. flavens (7), C. ovalifolius (8), and C. stellulifer (9). Recently, several papers on the biological properties of Croton oils have also been published: C. zehntneri (10,11), C. cajucam (12-14) and C. nepetaefolius (15,16). C. sonderianus Muell. Arg., which is popularly known in northeast Brazil as "marmeleiro preto," is one of the most widely dispersed species all over Ceará State. oils of C. sonderianus may be responsible for some of its specific particularities such as inedible to termites or any herbivore either during the raining season (three to four months) when it flourishes even from burned stalks after the peasant people land preparation for corn or bean cropping, or during the drying season when it loses all of its leaves for eight to nine months only to revive after the first rainfall. Due to the durability of the wood, it is used to make fences, or it is used to build loam huts, or lobster traps, etc. It is also employed as a folk remedy for the treatment of gastric disturbance. In the past, we have addressed part of our research efforts to study the oils from Croton sonderianus (17). Here we are presenting a more detailed study related to its chemical composition variation of leaves from different habitats, time of harvest and several parts of a same specimen.

Experimental

Collection of plant material: For the harvest time variation profile, leaf samples A were collected in Caucaia County-Ceara (20 km from the UFC lab) in May 1998 starting at 6:00 AM until 6:00 PM, at 3 h intervals (five samples). Samples B were collected from the same population 22 days later from 6:00 u.c. until 3:00 PM (four samples). For the habitat influence, leaf sample I was collected in May 1998 from Caucaia County; leaf sample II in May 1999 from Cocalzinho County (300 km north of Fortaleza); leaf sample III in March 2000 from IcaraiCounty (20 km from Fortaleza, near the sea coast zone); and leaf sample IV in September 2000 from Garapa County (60 km south of Fortaleza). All plant parts from the same specimen were collected in Caucaia County in February 2000.

Oil isolation: All plant parts were separately subjected to hydrodistillation to yield clear oils. Fresh leaves of C. sonderianus were used for all harvest time variation analyses: Samples A (6:00 AM, 0.2%; 9:00 AM, 0.3%; 12:00 PM, 0.2%; 3:00 PM, 0.2%; 6:00 PM, 0.3%). Samples B (6:00 AM, 0.4%; 9:00 AM, 0.6%; 12:00 PM, 0.1%; 3:00 PM, 0.2%). Fresh leaves were also used to obtain leaf oil I (0.5%), leaf oil II (0.4%), leaf oil III (0.6%) and leaf oil IV (0.3%). Fresh leaves, flowers, ground trunk bark and ground roots (0.05%) of a same specimen were hydrodistilled yielding clear oils: 0.5%; 0.3%; 0.1% and 0.05%, respectively.

Qualitative and quantitative analysis: The oils were analyzed by GC/MS on an HP-5971 apparatus using a 30 m × 0.25 mm, 0.1 µm film thickness, dimethylpolysiloxane DB-S column, helium as carrier gas (1 mL/min flow rate) and temperature programmed from 35°- 180°Cat4°C/min. Compound identification was initially made by using a MS library search with retention indices as a preselection routine (18-20) followed by visual confirmation to report standard MS obtained from literature (21). Percentage of individual constituents are based on electronic integration of TIC data.

Results and Discussion

Harvest tinte variation profile: Four leaf samples from Caucaia County, near the Fortaleza, the capital of Ceará state, collected at 3-h intervals, 6:00 AM until 3:00 PM, in May 1998 at 22-day intervals were extracted and analyzed. The results are shown in Table I. It is worth noticing, from Table I, that a-pinene (11.7-25.7%), myrcene (2.3-16.7%), 1,8-cineole (16.3-37.7%), β-caryophyllene (3.4-9.2%) and spathulenol (3.5-12.0%) were the major components present in all analyses .Minor compounds were α-thujene (1.0-2.0%), sabinene (0.8-4.7%) and a-humulene (1.0-2.0%). 1,8-Cineole was the major compound in all analyzed oils except for sample B, at 9:00 am, where it was absent and β-pliellandrene (26.6%) was the major compound appearing only is this sample. In addition, sample B oils contained limonene (2.8-3.5%), aromadendrene (1.2-2.2%) and bicyclogermacrene (5.9-13.2%). These components were not detected in sample A oils. These are unusual results that cannot be explained at this time. Further studies will be addressed to these dramatic major component changes at a later time. Similarly, β-pinene and p-cymene were present mostly in sample A oils. A graphical analysis of the five major compounds, present in almost all analysis (Figure 1), reveals the higher proportion of 1,8-cineole (except for sample B at 9:00 AM) relative to α-pinene, the second major compound (except for sample B at 6:00 AM), and the steady relative proportion of β-caryophylene and spathulenol. The behavior of myrcene is the most anomalous.

Different populations from different habitats: Four samples, collected at different dates, from different places were also analyzed. The results are shown in Table II. It is worth noticing that the same five components (α-pinene, myrcene, I,8-cineole, β-caryophyllene and spathulenol) were present along with sabinene, α-humulene and bicyclogermacrene, in all analyses. Once again the absence of 1,8-cineole in contrast to the higher content of β-phellandrene can be seen in leaf oil II, and to a minor extent in leaf oil III.

Different plant parts of a same specimen: A specimen collected at Caucaia-Ceará, in February 2000, was separated into leaves, flowers, trunk bark and trunk wood, and roots. The resulting data from each part is shown in Table III. No trunk wood oil was obtained. β-Elemene, gennacrene D, (E)nerolidol, spathulenol and globulol were the only components present in all plant parts. A lower content of 1,8-cineole versus β-phellandrene for the leaf sample was noticed again.

In several small peasant villages, C. sonderianus leaves are placed inside the bags of bean on corn when they are to be stored for a long time for eventual use as food for humans and/or animals during the dry season. In a previous screening, the use of Lavandula latifolia Medic, (spike lavender) against Tribolium castaneum (a plague common to stored grains) produced promising results (22). A fractionation guided by insecticide activity has led to the identification of 1,8-cineole as the component responsible forinsecticidal activity. As can be seen, 1,8-cineole is major component of the leaf oil of C. sonderianus, as a result, this could justify the folkloric use of it.

From our findings one can speculate about the validity of most reports dealing with the oil composition based on a single collection. In these cases at least the harvest time and season of collection should be provided. This also widens the possibility of new insights being acquired after re-analysis of several plant oils already published in the literature, taking in consideration either geographical or ecological influences.

Acknowledgments

The authors uAsh to thank Afranio G. Fernandes (Departamento de Biohigia, Universidade Federal do Ceara) for plant identification; Olga Ranws (Central Analitica/DQOI, Universidade federal do Ceara) for recording the GC/MS data; to CNPq for Research Fellowship awards and CAPES, FINEP/PADCT/FUNCAP/PRONEX for financial support.

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Regina C.M. Dourado and Edilberto R. Silveira*

Curso de Pós-Graduaçõo em Química Orgânica, Departamento de Química Orgânica e Inorgânica, Laboratório de Produtos Naturais, Universidade Federal do Ceará, Caixa Postal 12.200, Fortaleza-CE, 60,021-970, Brazil

* Address for correspondence

Received: June 2001

Revised: November 2001

Accepted: December 2001

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