6-Hydroxyisocaryophyllene and isocaryophyllenic acid from birches vegetative buds

Dmitriy Nikolaevich Vedernikov,Svetlana Vitalievna Teplyakova,Olesya V Khoroshilova

doi:10.14258/jcprm.2018033717

Abstract

The new isocaryophyllene derivatives were first detected in the birch vegetative buds. The structure of 6-hydroxyisocaryophyllene [(1R,4Z, 6R, 9S)-8-methylene-11,11-dimethylbicyclo[7.2.0]undec-4-ene-6-ol] isolated from the Betula pendula Roth. birch buds was determined by NMR spectroscopy. The structures of caryophyllenic acid and isocaryphyllenic acid isolated from the Betula grandifolia Litv., B. albo-sinensis Burk., B. fusca Pall.ex Georg, B. obscura A. Kotula, B. litwinowii Doluch., B. hallii Howell, B. grandifolia Litv. birch buds was determined by X-ray diffraction analysis. The physico-chemical characteristics and NMR data of 6-hydroxyisocaryophyllene, epoxide of 6-hydroxyisocaryophyllene and all the isolated acids are given. The gas chromatographic retention indices of all identified compounds were determined.

Highlights

We have earlier reported the hydrocarbon extract sesquiterpene alcohols composition of pendent white birch (Betula pendula Roth.) vegetative buds
The same pattern was observed in the analysis the birch buds Betula grandifolia Litv., B. albo-sinensis Burk., B. fusca Pall.ex
B. litwinowii Doluch. , birch of golden, bog birch B. hallii Howell, B. grandifolia Litv. extract obtained by extraction with ether

Summary

Introduction

We have earlier reported the hydrocarbon extract sesquiterpene alcohols composition of pendent white birch (Betula pendula Roth.) vegetative buds. The obtained neutral substances of the extract (17.8 g) of pendent white birch buds and the acids of bog birch extract (6.36 g) were separated by preparative liquid chromatography on silica gel with gradient elution using petroleum benzine (PE) (boiling range 40–70 °C) as an eluent with the addition of up to 30% MTBE. The acid fractions were methylated with diazomethane before analyzing by gas chromatography-mass spectrometry (GLC-MS) since the acids did not appear as peaks in the chromatogram. Mass spectrum of methyl ester (m/z): 248(2), 233(16), 216(6), 201(9), 189(31), 179(60), 173(25), 165(14), 156(3), 147(100), 145(30), 133(62), 119(72), 105(57), 91(96), 79( 80), 69(75), 59(14), 53(28). 13 C NMR in СDCl3 (d): 21.9 q (С-13) 29.8, q (С-12), 23.9 t (С-6), 25.9 t (С-2), 34.5 s (С-11), 36.3 t(С-3), 36.4 t (С-7), 36.9 t (С-10),36.9 d (С-9), 42.7d (C-1) 52.0 q (OCH3), 58.8 d (C-5), 83.6 t (СН2-N=N), 98.4 s (С-4), 111.2 t (С-15), 151.2 s (С-8), 168.0 s (С-14)

Results and discussion

C CH CH CH2 CH3 OH

C CH CH CH2 C CH2 CH3 OH

Conclusions