Short Communications
188
Pigments from the Stem Bark of Dillenia indica K. P. Tiwari and Smt. Savitri Devi Srivastava Department of Chemistry, University of Allahabad, Allahabad, India.
The chemical investigation of the stem bark of Dillenia indica resulted in the isolation and identification of 3',S-dihydroxy4',3-dimethoxy fla~0ne-7-O-p-D-gl~C0pymnoside; 4,5,7,3',4'-pentahydroxy flavan3-0-,!?-D-glucopyranoside; 1,8-dihydroxy2-methyl anthraquinone-3-0-,!?-D-glucopyranoside and 5,7-dihydroxy-4'-methoxy flavone-3-O-~-~-~~ucopyranoside. Dillenia indica (Dilleniaceae) possesses a number of medicinal properties [I, 21. I n the present communication the authors wish to report the study of four pigments isolated from the stem bark. The powdered air dried stem bark of the plant was extracted with ethanol under reflux. Four conpounds were isolated from the ethanolic extract. 3'S,7-trihydroxy-4',3-dimethoxy flavone: C2,H2,012 underwent positive colour reactions and Molisch's test for a flavone glycoside. O n hydrolysis it gave glucose (PC and Osazone) and a yellow coloured aglycone, m.p. 238' (d.) which showed the characteristic colour reactions for a flavone. The aglycone C1,H,,O, analysed for three hydroxyls (acetate, I R 3350 cm-1) and two methoxyl groups (Zeisel's, IR 2850 and 1170 cm-1). The spectral studies of the aglycone are in confirmity with hydroxyl groups at 5 and 7 (bathochromic shift with AlCl, and NaOAc [3, 41) and also by its specific colour reactions. The aglycone gave a hypsochromic shift of 15 nm in Band-I as comparing with the spectral shift of demethyl-
ated aglycone (HBrIAcOH), showign the presence of one methoxyl group at position-3. KMnO, oxidation gave isovanillic acid and alkali degradation of the aglycone gave phloroglucinol and isovanillic acid, showing the presence of one O H at 3' and one -OCH, at 4' position. The aglycone on demethylation (HBrIAcOH) gave a product identified as quercetin by its m.p., m.m.p., spectral data and co-tlc. Thus the aglycone is 3',5,7-trihydroxy-4',3 dimethoxy-flavone. The position of the sugar linkage has been shown to be with the 7-hydroxyl group by the study of the spectral shift using NaOAc and colour reaction. As a result of periodate oxidation it has been shown that sugar is in glucopyranose form. The glycoside was hydrolysed with emulsin which showed it was ,!?-linked.This aglycone has been reported earlier [5] but the glcoside of the present structure is being reported for the first time. Leucoanthocyanin: C2,H2,0,, was identified [6, 7,] by its m.p., m.m.p., Rf values, specific colour reactions and cochromatography with an authentic sample. 2-methyl, 1,3,8-trihydroxy anthraquinone: C21H20010underwent positive colour reactions [8, 91 and Molisch's test for an anthroquinone glycoside. O n hydrolysis it gave glucose (PC and Osazone) and a yellowish brown coloured aglycone, m.p. 23Z0, gave characteristic colour reactions of a hydroxy anthraquinone. Zn-dust distillation of the a g l ~ c o n egave 2-methyl anthracene which supported the anthraquinone
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Key Word Index: Dillenia indica; Flavonoids; Anthraquinones; Leucoanthocyanidin.
skeleton. The aglycone Cl,H,oO, analysed for three hydroxyls (acetate, I R 3345 cm-1). The aglycone formed a complex with CuSO, in ethanol showing the presence of one O H in a-position [ l o ] and dissolved in 5O10 aqueous Na,CO, showing another hydroxyl group-in j3-position [ I l l . When treated with 5010 methanolic magnesium acetate on a filter paper and subsequently heated a t 80-100' for few minutes, the aglycone developed pink colour showing that 8 - O H occupies position-3 with respect to a - O H group [12]. The aglycone on treatment with zirconium nitrate in acetone gave red precipitate insoluble in H C l [13, 141, fixing the other O H group a t position-8. Thus from the above discussion the structure of the aglycone comes to be 2-methyl1,3,8-trihydroxy anthraquinone. The position of the sugar linkage has been shown to be with the 3-hydroxyl group by the study of the colour reactions as in [10-12]. The periodate oxidation and emulsin hydrolysis of the glycoside indicated sugar as @-linked glucopyranose form. This aglycone had been reported earlier [IS] but the glycoside of the present structure is being reported for the first time.
3,5,7-Tuihydroxy-4'-methoxy-flavone: C,,H,,O,, gave characteristic reactions of flavonoid and was found to be a glycoside. On hydrolysis it gave glucose (PC and Osazone) and a yellow coloured aglycone, m.p. 223-25O, which showed the characteristic colour reactions of flavonol. The aglycone Cl,H,,O, analysed for three hydroxyls (acetate, IR 3450 cm-1) and one methoxyl group (Zeisel's, IR 2850 and 1170 cm-1). The spectral studies of the aglycone are in confirmity with the hydroxyl groups a t 5 and 7 (bathochromic shifts with AlCl, and NaOAc and also colour reactions.) The KMnO, oxidation of the aglycone gave anisic acid and alkali degradation gave phloroglucinol and anisic acid, showing the presence of methoxyl group a t position-4'. The aglycone gave positive test with Znl
H C l and spectral shift with AlCl, showing the presence of 3-hydroxyl group. The aglycone on demethylation (HBrIAcOH) gave a compound which was identified as Kaempferol by its m.p., m.m.p. and coTLC. Thus the aglycone is 3,5,7-trihydroxy4'-methoxy flavone. The sugar linkage has been shown to be with 3-hydroxyl group by the study of spectral shift using AlCl,/ HCl and colour reactions. As a result of periodate oxidation, it has been shown that sugar is in glucopyranose form. The glycoside was hydrolysed by emulsion. This indicates that it is j3-linked. The aglycone has been reported earlier [7, 161 but the glycoside of the present structure is being reported for the first time.
Acknowledgement The authors are thankful to SCST, Ludcnow (India) for providing financial assistance for the research project.
References 1. Kirtikar, K. R. and B. D. Basu: Indian Mcdical Plants, 1, 53 (1935). 2. Chopra, R. N., S. L. Nayar and I. C. Cho-
pra: Glossary of Indian Medicinal Plants, 97 (1956). 3. Horowitz, R. M.: J. Am. Chem. Soc., 79, 6561 (1957). 4. Jurd, L. and R. M. Horowitz: J. Org. Chem., 21, 1395 (1956). 5. Kupchan, S. M. and E. Bauerschmidt: Phytochemistry, 10, 664 (1971). 6. Schou, S. A.: Helv. Chim. Acta, 10, 907 (1957). 7. Kubitzki, K.: Ber. Deut. Bot. Ges., 81, 238
(1968). 8. Karrer, P.:Organic Chemistry, 541 (1950).
9. Robinson, T.:The Organic Constitutents of higher plants, 107 (1963). 10. Sommigyi, J.: Biochem. J., 19, 195 (1952). 11. Graebe, C.:Annalen, 211, 349 (1906).
Downloaded by: Universite de Sherbrooke. Copyrighted material.
Short Communications
Short Communications 16. Hasegawa, (1959).
M.: J.
Org. Chem., 24, 408
Address: Smt. Savitri Devi Srivastava, C/O Dr. K . P. Tiwari, Department of Chemistry, University of Allahabad, Allahabad-2 11 002 (India)
Downloaded by: Universite de Sherbrooke. Copyrighted material.
12. Shibata, S., M. Takido and 0 . Tanaka: J. Am. Chem. Soc., 72, 2789 (1950). 13. Morst, W. B. and B. Zattman: Biol. InstQuim. Agri, 34. 17 (1954). 14. Feigl, F.: Spot tests in Organic Chemistry, 347-49 (1966). 15. Tiwari, R. D. and 0. P. Yadav: Planta Med., 19, 299-305 (1971).
188
Pigments from the Stem Bark of Dillenia indica K. P. Tiwari and Smt. Savitri Devi Srivastava Department of Chemistry, University of Allahabad, Allahabad, India.
The chemical investigation of the stem bark of Dillenia indica resulted in the isolation and identification of 3',S-dihydroxy4',3-dimethoxy fla~0ne-7-O-p-D-gl~C0pymnoside; 4,5,7,3',4'-pentahydroxy flavan3-0-,!?-D-glucopyranoside; 1,8-dihydroxy2-methyl anthraquinone-3-0-,!?-D-glucopyranoside and 5,7-dihydroxy-4'-methoxy flavone-3-O-~-~-~~ucopyranoside. Dillenia indica (Dilleniaceae) possesses a number of medicinal properties [I, 21. I n the present communication the authors wish to report the study of four pigments isolated from the stem bark. The powdered air dried stem bark of the plant was extracted with ethanol under reflux. Four conpounds were isolated from the ethanolic extract. 3'S,7-trihydroxy-4',3-dimethoxy flavone: C2,H2,012 underwent positive colour reactions and Molisch's test for a flavone glycoside. O n hydrolysis it gave glucose (PC and Osazone) and a yellow coloured aglycone, m.p. 238' (d.) which showed the characteristic colour reactions for a flavone. The aglycone C1,H,,O, analysed for three hydroxyls (acetate, I R 3350 cm-1) and two methoxyl groups (Zeisel's, IR 2850 and 1170 cm-1). The spectral studies of the aglycone are in confirmity with hydroxyl groups at 5 and 7 (bathochromic shift with AlCl, and NaOAc [3, 41) and also by its specific colour reactions. The aglycone gave a hypsochromic shift of 15 nm in Band-I as comparing with the spectral shift of demethyl-
ated aglycone (HBrIAcOH), showign the presence of one methoxyl group at position-3. KMnO, oxidation gave isovanillic acid and alkali degradation of the aglycone gave phloroglucinol and isovanillic acid, showing the presence of one O H at 3' and one -OCH, at 4' position. The aglycone on demethylation (HBrIAcOH) gave a product identified as quercetin by its m.p., m.m.p., spectral data and co-tlc. Thus the aglycone is 3',5,7-trihydroxy-4',3 dimethoxy-flavone. The position of the sugar linkage has been shown to be with the 7-hydroxyl group by the study of the spectral shift using NaOAc and colour reaction. As a result of periodate oxidation it has been shown that sugar is in glucopyranose form. The glycoside was hydrolysed with emulsin which showed it was ,!?-linked.This aglycone has been reported earlier [5] but the glcoside of the present structure is being reported for the first time. Leucoanthocyanin: C2,H2,0,, was identified [6, 7,] by its m.p., m.m.p., Rf values, specific colour reactions and cochromatography with an authentic sample. 2-methyl, 1,3,8-trihydroxy anthraquinone: C21H20010underwent positive colour reactions [8, 91 and Molisch's test for an anthroquinone glycoside. O n hydrolysis it gave glucose (PC and Osazone) and a yellowish brown coloured aglycone, m.p. 23Z0, gave characteristic colour reactions of a hydroxy anthraquinone. Zn-dust distillation of the a g l ~ c o n egave 2-methyl anthracene which supported the anthraquinone
Downloaded by: Universite de Sherbrooke. Copyrighted material.
Key Word Index: Dillenia indica; Flavonoids; Anthraquinones; Leucoanthocyanidin.
skeleton. The aglycone Cl,H,oO, analysed for three hydroxyls (acetate, I R 3345 cm-1). The aglycone formed a complex with CuSO, in ethanol showing the presence of one O H in a-position [ l o ] and dissolved in 5O10 aqueous Na,CO, showing another hydroxyl group-in j3-position [ I l l . When treated with 5010 methanolic magnesium acetate on a filter paper and subsequently heated a t 80-100' for few minutes, the aglycone developed pink colour showing that 8 - O H occupies position-3 with respect to a - O H group [12]. The aglycone on treatment with zirconium nitrate in acetone gave red precipitate insoluble in H C l [13, 141, fixing the other O H group a t position-8. Thus from the above discussion the structure of the aglycone comes to be 2-methyl1,3,8-trihydroxy anthraquinone. The position of the sugar linkage has been shown to be with the 3-hydroxyl group by the study of the colour reactions as in [10-12]. The periodate oxidation and emulsin hydrolysis of the glycoside indicated sugar as @-linked glucopyranose form. This aglycone had been reported earlier [IS] but the glycoside of the present structure is being reported for the first time.
3,5,7-Tuihydroxy-4'-methoxy-flavone: C,,H,,O,, gave characteristic reactions of flavonoid and was found to be a glycoside. On hydrolysis it gave glucose (PC and Osazone) and a yellow coloured aglycone, m.p. 223-25O, which showed the characteristic colour reactions of flavonol. The aglycone Cl,H,,O, analysed for three hydroxyls (acetate, IR 3450 cm-1) and one methoxyl group (Zeisel's, IR 2850 and 1170 cm-1). The spectral studies of the aglycone are in confirmity with the hydroxyl groups a t 5 and 7 (bathochromic shifts with AlCl, and NaOAc and also colour reactions.) The KMnO, oxidation of the aglycone gave anisic acid and alkali degradation gave phloroglucinol and anisic acid, showing the presence of methoxyl group a t position-4'. The aglycone gave positive test with Znl
H C l and spectral shift with AlCl, showing the presence of 3-hydroxyl group. The aglycone on demethylation (HBrIAcOH) gave a compound which was identified as Kaempferol by its m.p., m.m.p. and coTLC. Thus the aglycone is 3,5,7-trihydroxy4'-methoxy flavone. The sugar linkage has been shown to be with 3-hydroxyl group by the study of spectral shift using AlCl,/ HCl and colour reactions. As a result of periodate oxidation, it has been shown that sugar is in glucopyranose form. The glycoside was hydrolysed by emulsion. This indicates that it is j3-linked. The aglycone has been reported earlier [7, 161 but the glycoside of the present structure is being reported for the first time.
Acknowledgement The authors are thankful to SCST, Ludcnow (India) for providing financial assistance for the research project.
References 1. Kirtikar, K. R. and B. D. Basu: Indian Mcdical Plants, 1, 53 (1935). 2. Chopra, R. N., S. L. Nayar and I. C. Cho-
pra: Glossary of Indian Medicinal Plants, 97 (1956). 3. Horowitz, R. M.: J. Am. Chem. Soc., 79, 6561 (1957). 4. Jurd, L. and R. M. Horowitz: J. Org. Chem., 21, 1395 (1956). 5. Kupchan, S. M. and E. Bauerschmidt: Phytochemistry, 10, 664 (1971). 6. Schou, S. A.: Helv. Chim. Acta, 10, 907 (1957). 7. Kubitzki, K.: Ber. Deut. Bot. Ges., 81, 238
(1968). 8. Karrer, P.:Organic Chemistry, 541 (1950).
9. Robinson, T.:The Organic Constitutents of higher plants, 107 (1963). 10. Sommigyi, J.: Biochem. J., 19, 195 (1952). 11. Graebe, C.:Annalen, 211, 349 (1906).
Downloaded by: Universite de Sherbrooke. Copyrighted material.
Short Communications
Short Communications 16. Hasegawa, (1959).
M.: J.
Org. Chem., 24, 408
Address: Smt. Savitri Devi Srivastava, C/O Dr. K . P. Tiwari, Department of Chemistry, University of Allahabad, Allahabad-2 11 002 (India)
Downloaded by: Universite de Sherbrooke. Copyrighted material.
12. Shibata, S., M. Takido and 0 . Tanaka: J. Am. Chem. Soc., 72, 2789 (1950). 13. Morst, W. B. and B. Zattman: Biol. InstQuim. Agri, 34. 17 (1954). 14. Feigl, F.: Spot tests in Organic Chemistry, 347-49 (1966). 15. Tiwari, R. D. and 0. P. Yadav: Planta Med., 19, 299-305 (1971).
