11.[11 18]acampaquinone a novel phenanthraquinone isolated from the whole plant of acampae praemorsa

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11.[11 18]acampaquinone a novel phenanthraquinone isolated from the whole plant of acampae praemorsa

  1. 1. Journal of Biology, Agriculture and Healthcare www.iiste.orgISSN 2224-3208 (Paper) ISSN 2225-093X (Online)Vol 2, No.2, 2012 Acampaquinone a Novel Phenanthraquinone Isolated from the Whole Plant of Acampae praemorsa V.Anuradha1*,K.Sateesh kumar2, G.Jayalakshmi31 Department of BS & H ,Vignan’s Nirula Institute of Technology and Science, Guntur, (A.P.), India.2. Department of chemistry, A.C. College, Guntur,Andhra Pradesh, India..3. Department of Chemistry, Vignan Degree College, Guntur,Andhra Pradesh, India.* E-mail of the corresponding author :var_chemistry@rediffmail.comAbstractFrom the whole plant of Acampae praemorsa belonging to the family Orchidaceae, a novelphenanthra- quinone derivative was isolated. Its structure was elucidated as 2-hydroxy- 6-methoxy – 1,4 – phenanthra- quinone on the basis of spectroscopic data. This is the first report ofphenanthraquinone fromAcampae praemorsa.Keywords:Acampae praemorsa, Orchidaceae, Phenanthraquinone1. IntroductionIn In the course of our investigation on the chemical constituents of some south Indian orchids wereported the isolation and characterization of a numberof pyrans1-6, pyrones7-11, quinones12, bibenzyls13,phenantherene carboxylic acids14 and a novel pyrene15. In this paper we report the structuralelucidation of a new phenanthraquinone derivative Acampaquinone from Acampae praemorsa.1.2 Experimental: The plant material of Acampae praemorsa was collected in Araku Valley during Nov 2009. KBr EtoH 1Mpsuncorr . IR, ν max , UV λ max , HNMR δ ppm90MHz CDCl3, CC and TLC on silicagel1.2.1 Extraction and isolation:The air dried whole plant of Acampae praemorsa was extracted with hexane and methanol. Eachextract was impregnated on minimum amount of silicagel and washed with hexane, benzene, acetoneand methanol. The washes of the two extracts were compared on TLC and similar fractions weremixed. The benzene elute of methanol extract was subjected to column chromatography usinghexane, benzene, acetone and methanol. The combined chromatographic benzene elute (21-30) (2gms) 11
  2. 2. Journal of Biology, Agriculture and Healthcare www.iiste.orgISSN 2224-3208 (Paper) ISSN 2225-093X (Online)Vol 2, No.2, 2012was rechromatographed over a column of silicagel (30gm) using hexane + benzene, benzene + acetone.The hexane + benzene (8:2) elute upon recrystallisation from benzene yielded violet solid. Furtherpurification was carried out by preparative TLC. The compound was visible as a violet band and waspurified using PTLC. The compound was eluted with acetone, dried under vacuum and recrystallisedusing benzene. On crystallisation the compound was separated as violet needles. Yield = 7mg; m.p. 2320CIt gave a positive ferric chloride reaction characteristic of a phenol. It gave a pink colour withmethanolic magnesium acetate indicating it to be a hydroxy quinone. (found C, 71%, H, 4.0%)(C14H10O4 requires C 70.80%, H 3.91%) [UV λmax nm EtoH ] 220, 270, 300,450 and 520 nm[λ NaoMe max nm ] 220, 280, 350 and 440 nm1 HNMR [(CDCl3)] (ppm) 12.2 (1H,S, - OH), 8.17(2H,S, H-9, H-10) , 6.30(S, 1H, H-3), 4.00 (3H,S-OCH3), 7.55 (d,1H,J = 9Hz, H-8), 7.45 (dd,1H,J=9, 2.5Hz,H-7), 7.20 (d,1H,J=2.5Hz, H-5)The compound was identified as 2 – hydroxy, 6-methoxy-1, 4-phenanthraquinone.1.2.2 Acetylation of compound4 gm of compound was dissolved in 0.5ml of pyridine and 1ml of acetic anhydride. The mixture waskept at room temperature for about 36 hours. Excess pyridine was removed under vacuum. Theacetate formed was dissolved in CHCl3 and washed with 0.5% HCl to remove excess pyridine. Thenwashed with water, dried overanhydrous sodium sulphate and concentrated under vacuum. The residueobtained was recrystallised by using methanol.Yield = 3mg, m.p. 180-1820C (Found, C, 69%, H, 4.1%)C17H12O5, requires,C, 68.9%, H, 4.05%)1.3 Results and discussion 12
  3. 3. Journal of Biology, Agriculture and Healthcare www.iiste.orgISSN 2224-3208 (Paper) ISSN 2225-093X (Online)Vol 2, No.2, 2012The Compound melted at 2320C and analyzed for C15H12O4 ([M+] m/z=254). Compound gave apositive ferric chloride reaction for the presence of phenolic hydroxyl groups and Shibata’s testyielding a pink colour with methanolic magnesium acetate for a hydroxy quinone. KBr −1 The IR absorption bands at vmax 1620,1637cm indicated the presence of quinonecarbonyls.UV spectrum exhibited absorption bands at λ EtoH max 220, 270, 300, 450 and 520nm supported thepresence of a phenanthraquinone system. Alkali induced bathochromic shift from 270 ⇒ 280 and300 ⇒ 350 nm indicated phenolic nature. Compound formed an acetate (low melting; analyzed for C17H14O6) on treatment with aceticanhydride and pyridine for 24hrs at room temperature supported the presence of hydroxyl group. Themolecular formula indicated that it might be a monoacetate. The 90MHz1HNMR spectrum of compound showed the presence of one methoxyl atδ 4.00(3H , s ) ppm and one hydroxyl at δ 12.2 (1H, s) ppm. Thus, compound might be a mono-methoxy-mono-hydroxy-phenanthraquinone.The singlet signal integrating for two protons at δ 8.17 suggested the presence of 9, 10-dehydro-phenanthrene skeleton. Hence, the partial structures 1,2,3 and 4 might be proposed for compound. o O O -OMe -OMe A A O -OH -OH B B (1) (2) o o o -OMe -OMe A A -OH o -OH B B (4) (3)The UV absorption bands at λ EtoH max 220, 270 300, 450 and 520nm supported the para-quinone structurefor compound and ruled out the ortho-quinone structures (2 to 4) as a long wave length band beyondλ EtoH max 520nm was expected for ortho-quinone type of compounds which is not seen in the presentcompound. 13
  4. 4. Journal of Biology, Agriculture and Healthcare www.iiste.orgISSN 2224-3208 (Paper) ISSN 2225-093X (Online)Vol 2, No.2, 2012The positions of methoxyl and hydroxyl groups were assigned based on the 1HNMR data and massspectraldata and on biogenetic considerations.The characteristic one proton singlet at δ 6.30 ppm due to α protons in quinones indicated that one ofthe carbons C-3 or C-2 were substituted. The signal at δ 6.30 might be assigned to H-2 or H-3. The 16biogenetic consideration (Scheme) indicated that the oxy-substituent might be assigned to C-2 and notC-3. Hence, the above signal was assigned to H-3.Biogenetic pathway HO OH O O one cinnamoyl coA 1. cyclisation O O + 2. rearrangement three malonyl coA 3. decarboxylation HO HO OH O radical coupling O HO 1. oxidation at C-1 rearrangement to quinone OH HO HO 14
  5. 5. Journal of Biology, Agriculture and Healthcare www.iiste.orgISSN 2224-3208 (Paper) ISSN 2225-093X (Online)Vol 2, No.2, 2012The three aromatic signals appeared at δ 7.20 (d, 1H, J= 2.5Hz), 7.45 (dd, 1H, J=2.5, 9Hz) and 7.55 (d,1H, J=9Hz) ppm indicated ABX pattern of protons in B-ring, Thus, the two possible structures (5 and6) were proposed for compound. O O O O -H O -H O -Me -Me O O (5) (6)The hydroxyl group at δ 12.2ppm suggested that the hydroxyl was in close proximity to the carbonylcarbon. Thus, hydroxyl was allocated to C-2. the allocation of hydroxyl to C-2 was further supportedby the mass spectrum of compound. Thus, the two possible structures for compound were (8) and (7). OH OH O O O O MeO OMe (7) (8) 15
  6. 6. Journal of Biology, Agriculture and Healthcare www.iiste.org ISSN 2224-3208 (Paper) ISSN 2225-093X (Online) Vol 2, No.2, 2012 7 was an already reported quinone, ochrone-B isolated and reported as ochrone-B acetate from Coelogyne ochracea. The signals assigned for ochrone-B acetate were as shown in 7 OAc O OH 6.17(s,1H) O 6.3 O 8.23(d,J=8.5) O 8.17 8.08(d,J=8.5) (2H) 9.67(d,J=9.8) 7.27.46(d,J=9.8,2.4) 7.85(d,J=2.4) 7.55 4.0 MeO 7.45 OMe (8) (7A) The most downfield signal in the aromatic ABX pattern of protons of compound was observed at δ 7.55ppm. The most down field signal in ochrone acetate (7A) was at δ 9.67ppm and was allocated to H-5. The absence of a down field signal in compound and the absence of any co-relation in the aromatic regions between the chemical shifts of ochrone acetate (7A) and compound indicated that compound might not be ochrone. This was further supported by the non-super imposable IR and co- TLC of compound acetate and ochrone acetate. However, as there is no hydroxyl in ring-B, much chemical shift difference in ring- B protons were not expected between compound and its acetate. The above discussion suggested the structure 8 for compound which was further supported by the mass spectrum of compound. Thus, the methoxyl was assigned to C-6 and the signals at δ 7.20 (d, 1H, J=2.5Hz), 7.45(dd, 1H, J=9,, 2.5 Hz) and 7.55(d, 1H, J=9Hz ) were respectively allocated to H-5, H-7 and H-8 protons based on their coupling constants. 16
  7. 7. Journal of Biology, Agriculture and Healthcare www.iiste.orgISSN 2224-3208 (Paper) ISSN 2225-093X (Online)Vol 2, No.2, 2012. The allocation was further supported by the fragment ions at m/z239 and m/z169 in the massspectrum of compound. The other peaks at m/z197 (10) and m/z183 (40) were due to cleavage a. The peak at m/z155 might be attributed to [m/z183-CO]. The other significant peaks atm/z223[M -OCH3], 211[M -CH3-CO], 195[M -OCH3-2CO], 183[M+-CH3-2CO], 167[M+-OCH3- + + +2CO], 155[M+-CH3-3CO or M+-OCH3-68], 142[M+-CH3-CO-69] strongly supported the allocation ofmethoxyl at C-6 and hydroxyl at C-2. The peaks at m/z114 and m/z127 were due to 142-CO and 155-CO respectively which further supported the above allocation. * OH O O a O + -Me O OH O + m/z =169 a m/z =239 O O O + MeO + a Me + H M m/z=254 HO MeO m/z =183 m/z =1971.4 ConclusionThus, compound was assigned the structure 2-hydroxy-6-methoxy-phenanthraquinone and named asacampaquinone. This is a first report from nature and from Acampae praemorsa1.5 AcknowledgementsThe authors wish to express their sincere thanks to the management and the Principal of VignanInstitutions, Pedapalakaluru, Guntur for providing necessary facilities. 17
  8. 8. Journal of Biology, Agriculture and Healthcare www.iiste.org ISSN 2224-3208 (Paper) ISSN 2225-093X (Online) Vol 2, No.2, 2012 1.6 References1. Veerraju, P., Prakasarao, N.S., Jagan MohanRao , L., Jagannada Rao, K.V.J., and Mohan Rao, P.R. (1989) Phytochemistry, 28:950.2. Anuradha, V. and Prakasa Rao, N.S. (1994) Phytochemistry, 35(1):273.3. Anuradha V. and Prakasa Rao, N.S. (1994) Phytochemistry, 37(3):909.4. Anuradha, V. and Prakasa Rao. N.S. (1998) Phytochemistry, 48(1):181-182.5. Anuradha, V. and Prakasa Rao. N.S., (1998) Phytochemistry, 48(1):(183-184).6. Anuradha, V. and Prakasa Rao. N.S. (1998) Phytochemistry, 48(1):(185-186).7. Uday Bhaskr, M., Jaganmohanrao, L., Prakasa Rao, N.S., JaganadhaRao, K.V.J., and Mohan Rao, P.R. (1989) Phytochemistry 28:3435.8. Uday Bhaskr, M., Jaganmohanrao, L., Prakasa Rao, N.S., JaganadhaRao, K.V.J., and Mohan Rao, P.R. (1991) J. Nat. Prod., 54:386.9. Veerraju, P., Prakasa Rao, N.S., Jaganmohan Rao,L., Jagannadha Rao,K.V.J., and Mohan Rao, P.R. (1989) Phytochemistry, 28:3031.10. Anuradha,V., Prakasa Rao N.S., and Uday Bhaskar, M., Phytochemistry, (1994) 36(6):1515.11. Anuradha, V. L. Kalyani and B. Srikanth. (2011) Asian J. Research Chem (4), 8 1221-2412. Anuradha,V., Prakasa Rao N.S., and Uday Bhaskar, M. (1995) Phytochemistry, 39(6):429.13. Uday Bhaskar, M., Jaganmohan Rao,L. And Prakash Rao N.S. (1993) Ind.J. of Chemistry, 32B:975-977.14. Anuradha,V., Prakasa Rao N.S., and Uday Bhaskar, M. (1994) Phytochemistry, 36(6):1515-1517.15. Anuradha,V., Prakasa Rao N.S., and Uday Bhaskar, M. (1994) Phytochemistry, 39(6):1429-1431.16. R.H. Thomson and Chapman & Hall(1987) London:Naturally Occuring Quinones , 567 18
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