Depnrtment of Chemistry, University of Rajastban, Jaipur, India
CHEMICAL EXAMINATION OF CASSIA JAVANICA By K. C. J o s ~ rM. , K. THOLIA and (Mrs.) TARA SHARMA
Abstract
Cassia javanica Linn. (Leguminosae) is a tree, reaching a height 20-22' and a girth of 2-2.5'. T h e bark is pale and smooth. T h e wood is strong and extremely hard. It is used in agriculture for making implements and in medicine for its cathartic properties [I]. A perusal of literature reveals that some work has been reported o n the flowers of this plant [2]. T h e present paper deals with the chemical examination of the heartwood, stem bark and leaves of this plant.
Experimental Extraction of the heartwood T h e air dried and coarsely powdered heartwood was extracted with benzene and the solvent removed. A residual brown setnisolid was obtained and was found to be a mixture of four compounds [(TLC, Benzene-Ethylacteate (1 : I), silicagel G)];separated by repeated column chromatography over Brockmann alumina (deactivated with 10% glacial acetic acid) and gave compounds I,]], 111 and IV. Compound I . 100% Pet. ether (60-80') eluted a crystalline conlpound, C,,H,,; m.p. 68' (EtOAC), (Found: C, 85.02; H, 14.86; calc. for C,,H,,: C, 85.32; H, 14.69%), , : :v 720-730 (CH,),,, M'436. From above data conlpound was identified as hentriacontane.
Cornpou,~d11. Pet. ether-benzene (4 : 1) fraction eluted a compound as cotourless flakes, m.p. 236-37' (MeOH). v::'F1 3400 ( O H ) cm-I, acetate (AC,O/py), m.p. 128'; benzoate, m.p. 143'. Compound IJ was identified as a (3-sitosterol. Compound 111. Benzene-Ethylacetate ( 4 : 1) eluted a colourless crystalline compound C,,H,,O,, m.p. 80-82' (Acetone), (Found: C, 78.09; H, 13.13; Calc. for C,,H,,O,: C, 78.78; H, 13.13%), ,:::v 1700 cm-', 720-30 cm-I, M '396. From these data compound I11 was found to be cerotic acid. Compound IV. 100% Methanol eluted a white compound, m.p. 285-86O (MeOH), (Found: C, 72.52; H, 10.23; Calc. for C,,H,,O,: C, 72.92; H, 10.42%). ,::v : 3400 (OH), 1375, 1275, 1080,
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Benzene extract of heartwood o f Cassia javanica afforded hentriacontane, Psitosterol, cerotic acid and B-sitosterol-D-glzrcoside. The pet. ether (60-80') extract of stem bark of the plant yielded n-octacosanol and ,8-sistosterol. The pet. ether extract of leaves gave heptacosane, octacosnne, hentriacontane, ceryl alcohol, octacosarzol and hentriacontanol.
Chemical Examination of Cassia javanica
191
1060, 1025 cm-'. Acetate, m.p. 166', gave positive Molisch test indicating its glycosidic nature. Compound was hydrolysed by refluxing with 7% ethanolic sulphuric acid for 2 hr and get aglycone as white shining flakes, m.p. 138-39' (MeoH and CHCI,); (Found: C, 83.98; H, 12.17; Calc. for C,,H,,O: C, 84.06; H, 12.08%).vi::. 3400 (OH) cm-l, Mc414, Acetate, m.p. 127'. From these data aglycone was identified as p-sitosterol. Glucose was identified in the hydrolysate by paper chromatography. From the above data, compound IV was identified as p-sitosterol-Dglycoside and further confirmed by Co-TLC and m.m.p. Extructior7 of the Stern Bark The air dried and ground bark was extracted with pet. ether (60-80'). The extract was concentrated and chromatographed over deactivated alumina and afforded compounds V and V1. Compound V. From pet. ether (100%) fraction, white crystalline compound, m.p. 83' (Acetone); 3350 (OH). Acetate, m.p. 66'; iodide, m.p. 64'; M'410. From above data compound V was indicated to be octacosanol.
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Compound VI. From pet. ether-benzene (4 :1) fraction, white flakes, m.p. 136-37' (MeOH and CHCI,,),,::v,! 3400 (OH) cm-I; acetate, m.p. 128' C. This was found to be identical with 0-sitosterol.
Extraction of the Leaves The air dried and powdered leaves were extracted with pet. ether (60-80'). The pet, ether extract was concentrated and chromatographed over deactivated alumina gave compounds VII, VIII, IX, X, XI and XII. Coniporrnd V l l . Froni pet. ether (100%) fraction, white crystals, m.p. 59O, crystallized in EtOAC, Nuio' crn I , 730-720 (CH,),,; M'380. These data indicate that compound VII was heptacosane max. and this was further confirmed by Co-TLC, IR spectra and m.m.p. Compound V l l l . Frorn pet. ether-benzene (4: I), colourless crystals, n1.p. 6S.SC, crystallized in MeOH, v?:' 730-720 cm-I, M'392. From above data compound VIlI seemed to be octacosane and identity was confirmed by Co-TLC, superposable IR spectra and m.m.p. Coinpound I X . From pet. ether-benzene (3: 2) fraction, m.p. 68' colourless flakes, crystallized with EtOAC, v ~ 730-720cm-', ~ ~ ' M'436. These data showed that compound IX was hentriacontane. Corrlpor!nd X. Froni pet. ether-benzene (1 : I), white needles, n1.p. 81' C (Acetone), negative ~ 3340, ~ T N M test, (Found: C, 81.90; H, 14.11%, Calc. for C,,H;,O: C, 81.67; H, 14.13%),v 2900, 2830, 1062, 730-720 cmP; acetate (Py/AC,O), colourless compound, m.p. 64.5' (EtOH); (Found: C, 79.11; H, 13.09% Calc, for Ct8HjoOL:C, 79.24; H, 13.21%); iodide (Phosphorusiodine), colourless flakes, m.p. 58-9' [(EtOAC: CHCI,) (4 : I)]; (Found: C, 63.29; H, 10.53 Calc. for C,,H,,,I; C, 63.43; H, 10.77%) From above data compound X was identified to be ceryl alcohol and confirmed by Co-TLC and identical I. R. spectra. Conrpoz~vdXI. Benzene (100%) fraction, m.p. 83' (EtOAc);'(Found C, 81.90; H, 13.80; Calc. for C,,H,,O: C, 81.92; H, 14.10%); \ * ~ 3350 ~ ~ (OH), ' 1060, 730-720c1n-1, M'410; acetate (Py/ AC,O), colourless needle, m.p. 64.5" [(Pet. ether-ethanol) (1 :4)], The compound octacosanol was identified by rn.p., m.m.p., Co-TLC (3-solvents), and IR spectral measurements.
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Compound XII. Benzene-ethylacetate (9 :1) fraction, colourless flakes, m.p. 85" (MeOH), (Found: C, 82.24; H, 14.03; Calc. for C,,H,,40; C, 82.22; H, 14.25%). v ~ 3325 ~ (OH) ~ cm-', ' M+452; NMR (CDCI,) 3H at 6 0.86 (J = SHz), terminal methyl protons, [(CH,),] 6 1.28, one proton singlet 6 2.01 as+gned to hydrogen of hydroxyl group; Acetate (Py/AC,O), white crystals, m.p. 70.5' (EtOH); iodide m.p. 6S0, The compound was identified as hentriacontanol.
Acknowledgements Thanks are also due to Dr. V. D. GUPTA(Jaipur) for recording I. R. spectra; and C. D. R. I., Lucknow, for recording mass, I. R. and NMR spectra. Two of us (M. K. T. and T. S.) acknowledge the receipt of financial assistance from C. S. I. R. and U. G. C., New Delhi respectively.
[I] The Wealth of India, ,,A Dictionary of Indian Raw Materials and Industrial Products" 11, . (1948) P. 96 and 98 [2] TIWARI,R. D. and YADAVA, 0. P.: Phytochemistry 10, 2256-63 (1971); Chern. Abstr. 75, 137486 f (1971) Address: Prof. Dr. K. C . Joshi, Department of Chemistry, University of Rnjastban, Jaipur-302004, Indin
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References
CHEMICAL EXAMINATION OF CASSIA JAVANICA By K. C. J o s ~ rM. , K. THOLIA and (Mrs.) TARA SHARMA
Abstract
Cassia javanica Linn. (Leguminosae) is a tree, reaching a height 20-22' and a girth of 2-2.5'. T h e bark is pale and smooth. T h e wood is strong and extremely hard. It is used in agriculture for making implements and in medicine for its cathartic properties [I]. A perusal of literature reveals that some work has been reported o n the flowers of this plant [2]. T h e present paper deals with the chemical examination of the heartwood, stem bark and leaves of this plant.
Experimental Extraction of the heartwood T h e air dried and coarsely powdered heartwood was extracted with benzene and the solvent removed. A residual brown setnisolid was obtained and was found to be a mixture of four compounds [(TLC, Benzene-Ethylacteate (1 : I), silicagel G)];separated by repeated column chromatography over Brockmann alumina (deactivated with 10% glacial acetic acid) and gave compounds I,]], 111 and IV. Compound I . 100% Pet. ether (60-80') eluted a crystalline conlpound, C,,H,,; m.p. 68' (EtOAC), (Found: C, 85.02; H, 14.86; calc. for C,,H,,: C, 85.32; H, 14.69%), , : :v 720-730 (CH,),,, M'436. From above data conlpound was identified as hentriacontane.
Cornpou,~d11. Pet. ether-benzene (4 : 1) fraction eluted a compound as cotourless flakes, m.p. 236-37' (MeOH). v::'F1 3400 ( O H ) cm-I, acetate (AC,O/py), m.p. 128'; benzoate, m.p. 143'. Compound IJ was identified as a (3-sitosterol. Compound 111. Benzene-Ethylacetate ( 4 : 1) eluted a colourless crystalline compound C,,H,,O,, m.p. 80-82' (Acetone), (Found: C, 78.09; H, 13.13; Calc. for C,,H,,O,: C, 78.78; H, 13.13%), ,:::v 1700 cm-', 720-30 cm-I, M '396. From these data compound I11 was found to be cerotic acid. Compound IV. 100% Methanol eluted a white compound, m.p. 285-86O (MeOH), (Found: C, 72.52; H, 10.23; Calc. for C,,H,,O,: C, 72.92; H, 10.42%). ,::v : 3400 (OH), 1375, 1275, 1080,
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Benzene extract of heartwood o f Cassia javanica afforded hentriacontane, Psitosterol, cerotic acid and B-sitosterol-D-glzrcoside. The pet. ether (60-80') extract of stem bark of the plant yielded n-octacosanol and ,8-sistosterol. The pet. ether extract of leaves gave heptacosane, octacosnne, hentriacontane, ceryl alcohol, octacosarzol and hentriacontanol.
Chemical Examination of Cassia javanica
191
1060, 1025 cm-'. Acetate, m.p. 166', gave positive Molisch test indicating its glycosidic nature. Compound was hydrolysed by refluxing with 7% ethanolic sulphuric acid for 2 hr and get aglycone as white shining flakes, m.p. 138-39' (MeoH and CHCI,); (Found: C, 83.98; H, 12.17; Calc. for C,,H,,O: C, 84.06; H, 12.08%).vi::. 3400 (OH) cm-l, Mc414, Acetate, m.p. 127'. From these data aglycone was identified as p-sitosterol. Glucose was identified in the hydrolysate by paper chromatography. From the above data, compound IV was identified as p-sitosterol-Dglycoside and further confirmed by Co-TLC and m.m.p. Extructior7 of the Stern Bark The air dried and ground bark was extracted with pet. ether (60-80'). The extract was concentrated and chromatographed over deactivated alumina and afforded compounds V and V1. Compound V. From pet. ether (100%) fraction, white crystalline compound, m.p. 83' (Acetone); 3350 (OH). Acetate, m.p. 66'; iodide, m.p. 64'; M'410. From above data compound V was indicated to be octacosanol.
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Compound VI. From pet. ether-benzene (4 :1) fraction, white flakes, m.p. 136-37' (MeOH and CHCI,,),,::v,! 3400 (OH) cm-I; acetate, m.p. 128' C. This was found to be identical with 0-sitosterol.
Extraction of the Leaves The air dried and powdered leaves were extracted with pet. ether (60-80'). The pet, ether extract was concentrated and chromatographed over deactivated alumina gave compounds VII, VIII, IX, X, XI and XII. Coniporrnd V l l . Froni pet. ether (100%) fraction, white crystals, m.p. 59O, crystallized in EtOAC, Nuio' crn I , 730-720 (CH,),,; M'380. These data indicate that compound VII was heptacosane max. and this was further confirmed by Co-TLC, IR spectra and m.m.p. Compound V l l l . Frorn pet. ether-benzene (4: I), colourless crystals, n1.p. 6S.SC, crystallized in MeOH, v?:' 730-720 cm-I, M'392. From above data compound VIlI seemed to be octacosane and identity was confirmed by Co-TLC, superposable IR spectra and m.m.p. Coinpound I X . From pet. ether-benzene (3: 2) fraction, m.p. 68' colourless flakes, crystallized with EtOAC, v ~ 730-720cm-', ~ ~ ' M'436. These data showed that compound IX was hentriacontane. Corrlpor!nd X. Froni pet. ether-benzene (1 : I), white needles, n1.p. 81' C (Acetone), negative ~ 3340, ~ T N M test, (Found: C, 81.90; H, 14.11%, Calc. for C,,H;,O: C, 81.67; H, 14.13%),v 2900, 2830, 1062, 730-720 cmP; acetate (Py/AC,O), colourless compound, m.p. 64.5' (EtOH); (Found: C, 79.11; H, 13.09% Calc, for Ct8HjoOL:C, 79.24; H, 13.21%); iodide (Phosphorusiodine), colourless flakes, m.p. 58-9' [(EtOAC: CHCI,) (4 : I)]; (Found: C, 63.29; H, 10.53 Calc. for C,,H,,,I; C, 63.43; H, 10.77%) From above data compound X was identified to be ceryl alcohol and confirmed by Co-TLC and identical I. R. spectra. Conrpoz~vdXI. Benzene (100%) fraction, m.p. 83' (EtOAc);'(Found C, 81.90; H, 13.80; Calc. for C,,H,,O: C, 81.92; H, 14.10%); \ * ~ 3350 ~ ~ (OH), ' 1060, 730-720c1n-1, M'410; acetate (Py/ AC,O), colourless needle, m.p. 64.5" [(Pet. ether-ethanol) (1 :4)], The compound octacosanol was identified by rn.p., m.m.p., Co-TLC (3-solvents), and IR spectral measurements.
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Planta medica Vol. 28 1975
Compound XII. Benzene-ethylacetate (9 :1) fraction, colourless flakes, m.p. 85" (MeOH), (Found: C, 82.24; H, 14.03; Calc. for C,,H,,40; C, 82.22; H, 14.25%). v ~ 3325 ~ (OH) ~ cm-', ' M+452; NMR (CDCI,) 3H at 6 0.86 (J = SHz), terminal methyl protons, [(CH,),] 6 1.28, one proton singlet 6 2.01 as+gned to hydrogen of hydroxyl group; Acetate (Py/AC,O), white crystals, m.p. 70.5' (EtOH); iodide m.p. 6S0, The compound was identified as hentriacontanol.
Acknowledgements Thanks are also due to Dr. V. D. GUPTA(Jaipur) for recording I. R. spectra; and C. D. R. I., Lucknow, for recording mass, I. R. and NMR spectra. Two of us (M. K. T. and T. S.) acknowledge the receipt of financial assistance from C. S. I. R. and U. G. C., New Delhi respectively.
[I] The Wealth of India, ,,A Dictionary of Indian Raw Materials and Industrial Products" 11, . (1948) P. 96 and 98 [2] TIWARI,R. D. and YADAVA, 0. P.: Phytochemistry 10, 2256-63 (1971); Chern. Abstr. 75, 137486 f (1971) Address: Prof. Dr. K. C . Joshi, Department of Chemistry, University of Rnjastban, Jaipur-302004, Indin
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References
