Phytochemistry, Vol. 34, No. 4, pp. 1194 1195, 1993 Printed in Great Britain.

MU--9422/93 %6.00+0.00 Q 1993 Pergamon Pres.~ Ltd

FLAVANOID

FROM

RESIN GLANDS

OF AZADIRACHT

INDICA

C. BALASUBRAMANIAN,P. S. MOHAN,* K. ARUMUGAsAMYt and K. UDAIYANt Department of Chemistry, Bharathiar University, Coimbatore 641046, T.N., India; TDepartment of Botany, Bharathiar University, Coimbatore 641046, T.N., India (Received in revisedform 28 April 1993) This paper is dedicated to Professor K. M. Marimuthu, Vice Chancellor, Bharathiar University on his 63rd birthday.

Key Word Index--Azadirachta

indica; Meliaceae; resin; shoot apices; nimbaflavone

derivative.

Abstract-A new isoprenylated flavanone has been isolated from the exudate of the resin glands present in shoot apices and young leaves of Azadirachta indica and characterized as 8-prenyl-5,7-dihydroxy-3-(3-hydroxy-3,3-dimethylbutyl)4-methoxyflavanone on the basis of physical and sp&ctroscopic data.

INTRODUCTION

R2 R HO :I r;; HO R PY~ P=nYl 0 :I OMe

The structure, development and nature of secretion of Azadirachta indica resinous glands were reported by J. A. Inamdar et al. Cl], The authors emphasized the need of chemical analysis of the secretory product to supplement morphological, structural and developmental characters for the classification of secretory tissue. Although there are reports [2-S] on the chemistry of neem, no work has been undertaken on its resin. We have now examined the exudate of resinous glands and isolated a new isoprenylated flavanone as a major compound. The minor constituents, one of which is presumed to be a triterpenoid, are being examined later. The new compound analysed for C,,H,,OB CM] 440 tn/z. Its IR spectrum in nujol exhibited bands in the region 3286 and 1635 cm-. The compound was identified as 1 based on the report of Garg and Bhakuni [6] who have characterized nimbaflavone, 8,3-di-isoprenyl-5,7-dihydroxy-4-methoxyflavanone (2). The structure ascribed for the isolated product contains the side chain moieties viz. 3-hydroxy-3,3_dimethylbutane (R) and prenyl group (R) instead of two prenyl groups (2R) as in nimbaflavone. In the HNMR spectrum the broad singlet at 66.65 integrated for one proton was for a hydroxyl function which could be positioned on the C-7 carbon of the phenyl ring A. The resonance at 6 12.02 ppm is assigned [7] to the hydroxyl group on C-S carbon. The mass spectrum showed a molecular ion peak at m/z 440 (10%). The fragmented ion peaks at m/z 220,205 and 165 were the same as in the case of nimbaflavone proposed by Garg. However, the spectrum documented the absence of prominent peaks viz. at m/z 202, 187 and 147; instead it registered a peak at m/z 353 accountable for the fragment arising due to the loss of side chain (R) from the
molecular ion.

0 R2
cH2cH2c(oH)Mea

1
2

PrenYl

EXPERIMENTAL Mp was uncorr. IR (Nujol). HNMR spectrum was recorded in CDCl, using TMS as int. reference on 220 MHz machine. TLC was performed on silica gel plates using iodine vapour chamber for detection. Isolation. Shoot apices and young reddish leaves (1 kg) were collected in August 1992, in the Bharathiar University campus which is located at the foot of Maruthamalai hills, Western ghats, South India. They were soaked in cold acetone (1 1).While soaking, care was taken to avoid the dissolution of the sap and also the leaves and shoot apices carrying artificially [S] induced gums. The acetone extract was coned in vacuum and the crude residual mass (5 g) was chromatographed in a column packed with silica gel. The flavanone mp 120 (decomp). (Found: C, 70.75; H, 7.42. CZ6HJ206 requires: C, 70.89; H, 7.32%) W ezH (nm): 288,355 IR(Nujo1) cm- : 3286 and 1635. H NMR (CDCI,): S(J=Hz) 1.64, 1.70 and 1.74 (12H, m, side chain methyl groups), 2.79 (2H, dd, 5=18.0, 3.6, C,-H), 3.06 (2H, m, R-methylene protons), 3.31 (4H, m, RI-methylene protons), 3.85 (3H, s, -OMe),*5.21 (lH, m, R-methine proton), 5.30 (lH, m, C,-H), 6.0 (lH, s, C,-H), 6.65 (lH,

*Author to whom correspondence should be addressed.

1194

Short Reports

1195

sbr,C,-OH), 6.87(1H,d,J=9.1, C,I-H), 7.20-7.27(2H, m, C,, and &t-H), 12.02 (lH, s, &-OH). Acknowledgements-We thank Dr K. M. Subramanian, OC, Mr Ragothma, SIF and Mr Gnanasekaran, IPC, IL%., Bangalore for HNMR spectrum, and Dr Seetha and Mr Ravikumar, INBRI, Bangalore for mass spectrum. The authors C.B. and K.A. thank CSIR, New Delhi for the award of SRF and RA, respectively.

REFERENCES

1. Inamdar, J. A., Subramanian, R. B. and Mohan, J. S. S. (1986) Ann. Botany 58, 425.

2. Tewari, D. N. (1992) in Monograph on Neem (Azadirachta indica Juss, A., ed.), pp. 147-191. International Book Distributors, Dehra Dun, India. 3. Siddiqui, S., Siddiqui, B. S., Faizi, S. and Mohamod, T. (1988) J. Nat. Prod. 57, 30. 4. Mark, L. S., Jay, O., Martin, P. S., James, K. A. (1988) Phytochemistry 27, 2773. T. N. (1978) [in 5. Nayak, B. R. and Pattabiraman, Indian] J. Biochem. Biophys. 15, 449. 6. Garg, H. S. and Bhakuni, D. S. (1984) Phytochemistry 23, 2115. 7. Venkata Rao, E. and Rajendra Prasad, Y. (1993) Phytochemistry 32, 183. 8. Nair, M. N. B., Shah, J. J. and Subramanyam, V. (1983) IA WA Bulletin 4, 103.