Isolation & Structure Elucidation of Flavonoids & Polyphenols From
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Isolation & Structure Elucidation Of Flavonoids & Polyphenols From The Bark Of Dracaena cinnabari Balf By Hiba Moustafa Al.Massri A Thesis Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science in Pharmaceutical Science at Petra University, Amman-Jordan June 2010 APPROVAL PAGE Isolation & Structure Elucidation Of Flavonoids & Polyphenols From The Bark Of Dracaena cinnabari Balf By Hiba Moustafa Al.Massri A Thesis Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science in Pharmaceutical Science at Petra University, Amman-Jordan June 2010 Major Professor Name Signature 1. Dr. Fadi Qadan .………………………. Examination Committee Name Signature 1. Dr. Riad Awad .…..…………………... 2. Dr. Wael Abu-Deya ..……………………... 3. Dr. Khalid Tawaha ……………………….. ii ABSTRACT Isolation & Structure Elucidation Of Flavonoids & Polyphenols From The Bark Of Dracaena cinnabari Balf By Hiba Moustafa Al.Massri Petra University, 2010 Under the Supervision of Dr. Fadi Qadan “Dragon’s blood” is the deep-red coloured resin exuded from injured bark obtained from various plants. The original source in Roman times was the dragon tree Dracaena cinnabari. Draceana cinnabari Balf F. belongs to the family Agavaceae, which is commonly known as "Dam El Akhawin" in Yemen. It is a tree endemic to the island socotra and the resin of it has been used as an astringent in the treating of diarrhea and dysentery, as a haemostatic and as anti- ulcer remedy. A series of compounds were isolated from Dracaena cinnabari, these compounds include; flavonoids ( including a triflavonoid and the biflavonoid cinnabarone), isoflavonoids, chalcones, sterols and triterpenoids, dracophane, a novel structural derivative of metacyclophane. In this study 3 compounds were isolated from Dracaena cinnabari Balf.; a glycosylated flavone, vitexin-2``-O-α-L-rhamnoside, one cinnamic acid derivative, (S)-N-trans- iii Coumaroyloctopamine, and one new compound, trans-feruloyl-2``-hexaracid lactone, and then these compounds were identified by using 13C-NMR, 1H-NMR, HSQC, HMBC, 1H-1H/COSY, ESI-MS and ESI-MS/MS. ……………………………… …………………………….... iv Acknowledgements First and foremost I would like to thank my thesis supervisor Dr. Fadi Qadan, who has shown a large and consistent interest in my project during the times. Our numerous scientific discussions and his many constructive comments have greatly improved this work. My deepest appreciation to my special father for supporting me, and being proud of me at all times and my mother for taking care of me always. Special thanks to my lovely brothers and sisters: Wesam, Hadeel, Mohammed, Hamsa, and very special thanks to Dania for her encouragement, understanding, and patience even during hard times of this study. My heartiest thanks to my very special fiancé, Mohammed, for encouraging, helping and being very supportive, especially at the last and difficult days. I would like to thank uncle Zuhair, aunt Latifa, Lina, Dima, Reema and Alaa for being such a great and wonderful family. I would also like to thank aunt Salma, Nada, Batool, Firas and suzan for taking care of me here in Jordan and treating me as a part of their family. This work would not have been completed without help and support of my best friend, Sara, thanks for being with me step by step from the beginning. I would sincerely like to thank my friend Rawan for encouraging me from the beginning and my friend Deema, for making me feel better every time I felt bad. v Table of Contents Page Approval page II Abstract III Acknowledgements V Table of contents VI List of figures VII List of tables X List of abbreviations XI 1. Chapter one: Introduction 1 1.1 Dragon blood 1 1.1.1 Definition 1 1.1.2 Sources 1 1.1.3 Traditional uses 2 1.2 Dragon`s blood tree 4 1.2.1 Habitat and ecology 5 1.2.2 Tree description 6 1.2.3 Chemical constituents reported from Dracaena cinnabari Balf. f. 8 1.2.4 Traditional uses 10 vi 1.2.5 Bioactivities and therapeutic uses 10 1.2.5.1 Antimicrobial and antiviral activity. 10 1.2.5.2 Antitumor and cytotoxic activity. 11 1.2.5.3 Antioxidative activity. 11 1.3 Polyphenolic compounds 13 1.3.1 Flavonoids 13 1.3.1.1 Occurrence in plants 15 1.3.1.2 Health benefits of flavonoids 16 1.3.1.3 Flavonoids structure 17 1.3.1.3.1 Chemistry 17 1.3.1.3.2 Classification 18 1.3.2 Cinnamic acid derivatives 19 2. Chapter two: Material and methods 21 2.1 General experimental procedure 21 2.2 Reagent 21 2.3 Plant material 22 2.4 Extraction and isolation 22 3. Chapter three: Results 23 3.1 Structure elucidation of isolated compounds 23 3.1.1 Structure elucidation of compound No.1 (S)-N-trans Coumaroyloctopamine. 23 3.1.2 Structure elucidation of compound No.2 trans-feruloyl-2``- vii hexaracid lactone 27 3.1.3 Structure elucidation of compound No. 3 (vitexin-2``-O-α-L-rhamnoside) 33 3.2 Isolation of polyphenols from Dracaena cinnabari Balf 36 4. Chapter four: Discussion 37 References viii Chapter one 1. Introduction 1.1 Dragon blood 1.1.1 Definition “Dragon’s blood” is the name applied to the deep-red coloured resin obtained from various plants. The original source in Roman times, used by many cultures and esteemed for its depth of colour and mystical association, was the dragon tree Dracaena cinnabari (Edwards et al., 2003). This deep red liquid exuding from injured bark is known in Arabia as ‘damm al.akhawin’ or ‘cinnabar’ (Adolt et al., 2003). 1.1.2 Sources Dragon's blood as a name has been applied to resins from quite different species from different continents. The resins known as dragon's blood differ widely from one another, not only on their degree of purity, but also in their appearance (Pearson et al., 2001). Various plants which dragon`s blood derived from involved in five different genera including Daemonorops (Palmaceae), Calamus (Palmaceae), Dracaena (Agavaceae), Pterocarpus (Leguminosae), and Croton (Euphorbiaceae), has been used 1 for the treatment of wounds, leucorrhea, fractures, diarrhea, piles, and peptic ulcers for a long time (Zhu et al., 2007). The resins of Dracaena species are highly unusual because their colour, unlike most natural resins, owes its depth not to the presence of impurities, minor components and pH, it`s colour depth is derived instead from highly coloured compounds such as dracorubin and dracorhodin (Pearson et al., 2001). The genus Dracaena comprises approximately 60 species. In wich 50 species; sensu are mainly found in tropical and subtropical Africa. At least 23 species occur in the Guinea-Congo region in western Africa. The genus also reaches hlacaronesia, Arabia, Socotra, Madagascar, southeastern Asia, northern Australia, and one species (D.americana Donn. Sm.) is found in the neotropics (Marrero A., 1998). The dragon tree group is formed of five arborescent species ( D. cinnabari Balf. F., D. draco (L.) L., D. ombet Kotschy & Peyr., D. serrulata Baker and D. schizantha Baker), wich provides one of the best known examples of disjunct distribution between Macaronesia, Rlorocco and East Africa (Marrero A., 1998) Dragon’s blood, a highly prized product of the ancient world , still makes the tree Dracaenas relatively famous (Adolt et al., 2003). 1.1.3 Traditional uses Local people from Socotra still use it to cure gastric sores, dye wool, glue and decorate pottery and houses (Adolt et al., 2003). 2 Fig 1 Five purported samples of dragon's blood from Dracaena cinnabari. Species Plant family Geographic origin Croton sp. Euphoriacea Tropics and subtropics worldwide Daemonorops Palmae South East Asia, especially propinquus Indonesia Dracaena Agavaceae Socotra cinnabari Dracaena draco Agavaceae Canary Island, Madeira Dracaena Agavaceae East Africa schizantha Table 1 Botanical and geographical origins of species used as source of dragon blood. 3 1.2 Dragon`s blood tree Table 2 Plant general informations. Kingdom Plantae Phylum Tracheophyta Class Liliopsida Order Liliales Family Dracaenaceae. Scientific name Dracaena cinnabari Species Authority Balf. F. Habitat Yemen : Socotra Soil Grit Water Minimum Sun Maximum Thickness 80 centimetres Height 9 meters Flower White Reproduction Seeds/cutting Pop names Socotra Dragon Tree, Inside- out Umbrella Tree 4 Fig 2 Dragon`s blood tree 1.2.1 Habitat and ecology Dracaena cinnabari is found on slopes of the highlands of northeastern Socotra. The plant community is under the influence of the northeastern humid monsoon. Mean average rainfall is approximately 400 mm. All the dragon tree species share similar ecological requirements. They tend to grow in areas with average temperatures of 18- 20°C. They are found between 10" N in Somalia and 33" N in Madeira, and there is a clear correlation between latitude and altitude. The populations of Madeira may be found at sea-level whilst those of Somalia never occur below 1400- 1800 m. In general, all these arborescent species with an umbrella-shaped canopy are 5 found mainly on the margins of the tropical-subtropical regions. plant community is usually intermixed with xerophilous formations. They are mostly linked to steep and rocky landscapes (Marrero A., 1998). It flowers in February and takes five months from flower to fully ripe fruit, It`s altitude is 500 to 1,550 m (Miller, A et al., 2004). The species is an evergreen tree with a typical umbrellashaped crown due to a ‘dracoid’ ramification of branches (Attorre et al., 2007). 1.2.2 Tree description This charismatic member of the Dracaenaceae family was described by Isaac Bayley Balfour in 1882. It is only found on the Yemen island (Socotra). It`s flowers are white and it grows among rocks and limestone, receiving little water and lots of sun. Depending on the environment, it will eventually reach three to nine meters with a stem up to 80 centimetres in diameter (Bihrmann, 2008).