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Revista Brasileira de Farmacognosia

Print version ISSN 0102-695XOn-line version ISSN 1981-528X

Rev. bras. farmacogn. vol.18  suppl.0 João Pessoa Dec. 2008

http://dx.doi.org/10.1590/S0102-695X2008000500004 

ARTIGO

 

Cornoside and other constituents from the latex of Parahancornia amapa (Hub.) Ducke (Apocynaceae) a medicinal plant in Northern Brazil

 

Cornosídeo e outros constituintes do látex de Parahancornia amapa (Hub.) Ducke (Apocynaceae) uma planta medicinal no Norte do Brasil

 

 

Mário G. de CarvalhoI, *; Luis A. de AlbuquerqueI; Cássia C. F. AlvesI; Vera CasconII

IDepartamento de Química, Instituto de Ciências Exatas, Universidade federal Rural do Rio de Janeiro, BR 465, Km. 7, 23890-000 Seropédica-RJ, Brazil
IIFundação CINERJ, Rua Visconde de Niterói, 1364, Mangueira, 20943-001 Rio de Janeiro-RJ, Brazil

 

 


ABSTRACT

Latex of Parahancornia amapa which is known as "amapa milk" in folk medicine was extracted with hexane, dichloromethane and methanol. From the hexane and dichloromethane were identified mixtures of 3-O-acyl lupeol esters such as identified previously. In the methanol extract, a large amount of carbohydrates, the phenylethanoid glucoside known as cornoside, other phenylethanoids derivatives and methylmyoinositol were identified. The analysis of IR, NMR and GC-LRMS of the natural compounds and tetra-acetylcornoside and comparison with literature data were used to identify the compounds.

Keywords: Parahancornia amapa, amapá, phenylethanoids, carbohydrates, cornoside, lupeol esters.


RESUMO

O látex de Parahancornia amapa, popularmente conhecido como "leite do amapá" foi extraído com hexano, diclorometano e metanol. As frações obtidas com hexano e diclorometano forneceram misturas de 3-O-acil-lupeol e triterpenos confirmando resultados de estudos já realizados. No extrato metanólico identificou-se uma grande quantidade de mistura de carboidratos, metilmioinositol e derivados de feniletanóides tendo como principal constituinte o cornosídeo. Estes constituintes foram identificados através da análise de espectros de IV, RMN 1H e 13C e CG-EM das frações e do derivado acetilado do cornosídeo e do metilmioinositol.

Unitermos: Parahancornia amapa, amapa, feniletanóides, carboidratos, cornosídeo, ésteres de lupeol.


 

 

INTRODUCTION

Parahancornia amapa (Huber) Dicke (Apocynaceae) is a tree which occurs in the State of Amapá in the Brazilian Amazon region. It is commonly called "amapa milk", its latex is used in scars and bruises as plaster treatment, it is also mixed with honey, in equal quantities, to be used as a drink for treatment of asthma, bronchitis and physical weakness (Van den Berg, 1982). In the previous phytochemical study of this specie we reported the presence of sitosterol, stigmasterol, sitosterone, friedelin, lupeol, β-amyrin, α-amyrin, their acetyl derivatives, besides 3β-O-acyl lupeol esters in bark, latex and roots of this plant (Carvalho et al., 2001; Sobrinho et al., 1991). These pentacyclic triterpenes, its acyl derivatives and the mixtures of four n-acyl-lupeol, four 3β-hydroxy-n-acyl lupeol and two β,δ-dihydroxy-n-acyl-lupeol were identified in the non-polar fractions of the latex from P. amapa (Sobrinho et al., 1991). In this paper we describe an additional study directing the identification of polar constituents in the latex from P. amapa. The presence of phenyletanoid glycoside and acyl lupeol esters in Parahancornia reveal biochemical metabolism different from Himatanthus (Barreto et al., 1998; Veloso et al., 1999; Abdel-Kader et al., 1997; Silva et al., 1998), Plumeria (Adam et al., 1979; Hamburger et al., 1991; Coppen & Cobb, 1983; Kardono et al., 1990) and Allamanda (Coppen & Cobb, 1983; Abdel-Kader et al., 1997) that have been identified as source of iridoids. On the other hand, it is in agreement with Jensen et al (2005) that cornoside often substitutes iridoid glucosides in plants where these are expected to be present. Considering that these kinds of compounds have been found in important herbal medicine (Teshima et al., 1996), these phenylethanoids and inositol can be the active compounds in the used polar fraction from the latex of P. amapa called as "amapa milk" by the folk medicine. An additional consideration is that the unadvised people substitute the latex from P. amapa with the one from Hmatanthus that has iridoids and sugars as polar compounds in its latex (Barreto et al., 1998).

 

MATERIAL AND METHODS

General procedures

Melting points have not been corrected. IR spectra were recorded on a Perkin-Elmer 1605 FT-IT spectrophotometer. 1H (200.0 MHz) and 13C (50.3 MHz) NMR spectra were recorded on a Brüker AC 200 spectrometer using DMSO-d6, D3COD or CDCl3 with TMS as internal standard. Electron Ionization Mass Spectra (LREI-MS) were taken with Gas Chromatograph coupled to a Mass Spectrometer (GC-MS) on a Varian Saturn 2000 using ion trap and 70 eV. Column chromatography with silica gel (Vetec and Aldrich 0.05-0.20 mm) and Sephadex LH-20 (Sigma, USA); for preparative TLC was used silica gel F254 G (Vetec), and silica gel TLC plates w/UV254, aluminum backed (Sorbent) were used to analyze the fractions collected from column chromatography (CC) with visualization under UV (254 and 366 nm), Lieberman-Burchard and/or Godin reagents or exposure to iodine vapor.

Plant material

The used material was collected from one specimen identified by the botanist Benedito Vitor Rabello in State of Amapá, Brazil. The voucher specimen (nº 07231) is deposited at the Herbário Amapaense (HAMAB) of the Divisão de Botânica do Museu Ângelo Moreira da Costa Lima, Instituto de Estudos e Pesquisas do Amapá (IEPA), Macapá-AP, Brazil.

Extraction

The dried latex (100.0 g) was extracted by maceration three times with hexane, dichloromethane and with methanol at room temperature. The solutions were obtained by filtration and the solvents were removed by distillation under vacuum to afford the residues PALAH (37.5 g), PALAD (30.0 g) and PALAM (25.0 g).

 

RESULTS AND DISCUSSION

The analysis of PALAH and PALAD by 1H and 13C NMR spectra and TLC plate revealed the presence of a mixture of pentacyclic triterpenes (α-amyrin, β-amyrin and lupeol), those acetyl derivatives and a complex mixture of acyl-lupeol esters identified previously (Carvalho et al., 2001; Sobrinho et al., 1991). The residue PALAM (15.0 g) was dissolved in methanol and submitted to Sephadex LH-20 column chromatography, eluted with methanol, to yield 40 fractions. The 1H and 13C NMR spectra of fractions 18-21 (50.0 mg) collected from this column showed signals of glycopyranoside (1, identified in the fractions 22-24) together with signals compatible with other phenylethanoid derivatives such as 1b, 2, 2a, and 3. The GC-MS analysis of this group of fractions afforded a chromatogram whose analysis of each corresponding mass spectrum considering the main peaks let us to identify 1b [4-hydroxy-4-(2-hydroxyethyl)-2,5-cyclohexadien-1-one; Rt: 4.36 min; m/z(%): 154 (100, M+.), 135 (30), 123 (25), 108 (20), certainly yielded from 1]; 2 [ethanol-2-(ciclohexyl-1-hydroxy-5-methoxy-2-en-4-one; Rt: 2,33 min; m/z (%): 186 (2, M+.), 155 (20), 137 (34), 112 (31), 110 (33), 82 (100)] and 3 [4-hydroxyphenylethanol (tyrosol); Rt: 2.43 min; m/z (%): 138 (40, M+.), 121 (17), 107 (100), 94 (5), 77 (33)]. The absence of corresponding peak of 2a let us to propose to be a derivative from 2. The fraction 22-24 (gum, 2.0 g) was examined by IR, NMR spectra, including 2D-NMR experiments, besides mass spectrum and comparison with literature data (Khan et al., 1992) let to identify the quinol glucoside 1, known as cornoside (Jiménez and Riguera, 1994). 1 (50.0 mg) was treated with acetic anhydride and pyridine (1:1) at room temperature overnight, following usual work-up and filtration through a silica gel column, yielded the tetra-acetyl derivative 1a [m.p. 219-220 ºC, 40.0 mg); 1H NMR (CDCl3, 200 MHz): 6.8 (d, 8.0 Hz, H-3,5), 6.2 (d, 8.0Hz, H-2,6), 4.9-5.2 (m, 2',3',4'), 4.60 (d, 8Hz, H-1') 4.0-4.3 (m, H-6'), 3,6 (m, H-5'); 13C NMR (CDCl3, 50.3 MHz): 188.0 (C-1), 169.3-169.5 (OCOCH3), 147.8 (CH-3,5), 128.6 (CH-2,6), 100.3 (CH-1'), 72.7 (CH-3'), 71.8 (CH-5'), 71.1 (CH-2'), 68.4 (CH-4'), 63.9 (CH2-8), 61.9 (C-4), 61.7 (CH2-6'), 39.0 (CH2-7), 24.1-24.7 (OCOCH3)]. The analysis of 1H and 13C NMR spectra of a solid material (300.00 mg), obtained from the fractions 27-31, revealed the presence of carbohydrate (4). 30.0 mg of 4 was acetylated by the same methodology used for 1 to obtain the derivative 4a. The analysis of IR and NMR spectra of 4a, besides comparison with the same penta-acetyl derivative of carbohydrate isolated from Himatanthus articulata (Barreto et al., 1998) and from Ouratea hexasperma (Moreira et al., 1999), let us to identify 4 as methyl-myoinositol (mp 214-217 ºC). The 13C NMR spectrum of the remaing fractions was analyzed and revealed the presence of carbohydrates mixture. This is the first record, in Apocynacae, of 1-3 which are widespread in families such as Cornacae, Oleacae, and Scrophulariacae (Kenichiro, 2005), Plantaginaceae (Jesen et al., 2005) and Bignoniaceae (Teshima et al., 1996) (Figure 1).

 

 

ACKNOWLEDGEMENTS

The authors thank CNPq, CAPES and FAPERJ for grants and financial support.

 

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Received 14 May 2008
Accepted 21 October 2008

 

 

* E-mail: mgeraldo@ufrrj.br

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