Phytochemistry 1 Lec 3 PDF

50 ‫المحارضة‬ ‫المحارضة‬ ‫حضور‬ ‫حضور‬ ‫عن عن‬ ‫يغين‬...

50 ‫المحارضة‬ ‫المحارضة‬ ‫حضور‬ ‫حضور‬ ‫عن عن‬ ‫يغين‬ ‫يغين‬ ‫العمل ال‬ ‫العمل ال‬ ‫هذاهذا‬ Phytochemistry I ‫هذا العمل ال يغين عن حضور المحارضة‬ 03 Chemistry of essential oils Chemistry of essential oils Alcohols and Phenols Alcohols have general formula R-OH, structurally similar to water but with one of the hydrogens replaced by an alkyl group. Their functional group is the hydroxyl group,-OH. Phenols have the same functional group, but it is attached to an aromatic ring General methods of isolation of alcohols. Fractional distillation Products of dehydration result in hydrocarbon Chromatographic methods Formation of crystalline derivatives The ease of alcohol dehydration is 3º>2°>1° ✓ Geraniol is exception of 1ry. Alc. which dehydrate readily ‫ عن‬tertiary alcohol ‫ وهذه العملية بتكون اسهل في‬hydrocarbon ‫ من المركب واحوله الي‬oH ‫ هو اني اشيل‬Dehydration ‫ بسهولة‬dehydration ‫ ولكن يحدث له‬primary alcohol ‫هو‬geraniol ‫ ما عدا ال‬more stable ‫ ألن‬primary ‫ عن ال‬scandary ‫ال‬ Additive compounds with CaCl2 Can form Esters ‫ممكن اكون منها استر وأمثلة االستر الي اقدر اكونها‬ Esters Borates Benzoates With anhydrides (H3BO3) 1°>2° (3º not react) ▪ 3° Not ➤ Acetic anhydride 1°>2°>3° ‫ مع االبوريك اسيد‬alcohol ‫لما تفاعل ال‬ ➤Phthalic anhydride (1º alc. primary ‫ و ال‬borate ester ‫فيعطي‬ ‫سهل إنه يكونه عن‬alcohol Only) ‫ال يكونه‬taritary ‫ وال‬scandaery ‫ال‬ 1  Phytochemistry I Chemistry of essential oils 03 Alcohol in volatile oils Alcohols are amongst the strongest antimicrobial compounds in essential oils but lack the irritant properties of other antimicrobial constituents like phenols. Alcohol ‫ودي تقسيمه ال‬alcohol ‫وخصوصا لو كان‬antimicrobial ‫بيكون‬V.O ‫قولنا قبل كدا إن أي‬ 1. Citronellol ➤ Oil of Citronella (d-form) ➤ Oil of Geranium and Rose (I-form) ➤ Fractional distillation. ➤ Hydrogenation of geraniol or nerol ➤Separated from geraniol and other terpene alcohols through the acid phthalate. citronellol ‫ لو كسرتها يتحول الي‬double bond ‫هو وجود ال‬geraniol ‫وال‬citronellol ‫الفرق بين ال‬ Separation of citronellol from geraniol With phthalic anhydride at 200°C Isolation Geraniol → decomposes to hydrocarbone Citronellol → phthalate ester which is taken and regenerated by alkali ‫ يتكسر اما‬geraniol ‫ مع ال‬phthalic anhydride‫لما تفاعل ال‬ alkil ‫ لما افاعله مع‬phthalate ester ‫يكون‬citronellol ‫مع ال‬ citrone‫يرجع ال‬ ➤ Lighter than water. Properties ➤More stable than geraniol Toward the action of formic acid and alkalies ➤Conversion to citronellyl ester of pyruvic acid (keto acid) ➤The semicarbazone of which melts at 110-111°C. (geraniol not) Identification ➤On oxidation with chromic acid ____ citronellal Citronellal ‫وهو ال‬ald ‫بيتحول ل‬Chromic acid ‫بال‬Oxidation ‫لما بيحصله‬ 2  Phytochemistry I Chemistry of essential oils 03 Formed from addition elimination reaction between ketones or aldehydes and semicarbazide ➤ Semicarbazones are crystalline compounds with definite M.P. Semicarbazone Determination of Citronellol (very stable) can be determined by forming ester with 100% formic acid Citronellol by where as other alcohols usually dehydrate by this concentration of formic acid. ‫ الي‬formaic acid ‫ فكمية ال‬formaide ester ‫يعطي‬formic acid ‫ لما افاعله مع ال‬citronellol‫ال‬ Formylation: ‫الي موجودة في العينة‬citronellol ‫تفاعلت هي نفسها كمية ال‬ Researches demonstrated the anticonvulsant activity of the citronellol Uses Citronellol inhibited P-gp (p-glycoprotein, multidrug resistance protein) (mediates the development of resistance to anticancer drugs). drug resistant ‫ الموجودة في خاليا الكانسر والمسئول عن ال‬p- glycoprotein ‫بيمنع بروتين‬ anticonvulsant ‫وكمان بيشتغل ك‬ 2. Geraniol Geraniol (trans form) Nerol (cis form) Oils of Palmerosa, rose Neroli (Orange flower) Citronella and geranium Oil of Petit grains Geraniol forms a crystalline derivative with anhydrous CaCl2, which is Isolation: of decomposed with water while nerol does not form such compound. geraniol from Petitgrain is Essential oil that is extracted from the green twigs of the bitter orange plant nerol nerol ‫ممكن افصله اما ال‬crystalline Derivatives ‫لما افاعله مع الكالسيوم كلوريد يعطي‬geraniol ‫ال‬ ‫ال يعطي‬ Geraniol is a colorless liquid, lighter than water, optically inactive, when exposed to air, it becomes, colored and less fragrant. OH Properties ‫بتاعته قليلة‬stabilty ‫ألن ال‬colored ‫لو عرضته للهواء لونه يغمق ويصبح‬ With 5% H2SO4,____ terpin hydrate. With H₃PO₄ or HCI gas, ____dipentene. Geraniol oxidation____citral To 1 ml of Geraniol, add 1 ml of acetic anhydride and 1 drop of phosphoric acid, keep warm for 10 minutes, add 1 ml of water, and shake in warm water for 5 Identification minutes. Cool and make slightly alkaline with anhydrous sodium carbonate solution. An odor of geranyl acetate is evolved. geranyl acetate order ‫ يعطي‬phosphoric acid ‫ و‬acetic anhydride ‫لو حطيت عليه‬ Geraniol is known to exhibit insecticidal and repellent properties with low toxicity. Geraniol has been suggested to represent a new class of chemoprevention agents for cancer. Recently Antimicrobial, anti-oxidant, anti-inflammatory. The effect of geraniol as a penetration enhancer for transdermal drug delivery has also attracted the attention of researchers and formulation scientists. ‫يزود االمتصاص بتاع المركبات عن طريق الجلد‬ 3  Phytochemistry I Chemistry of essential oils 03 3. Linalool ➤Oil of Coriander and oil of Nutmeg (d-form). ➤Oils of Bergamot, Lemon, lavender (I-form). ➤Present free OR as acetate ester (linalyl acetate) Fractional distillation (no definite crystalline derivative) Isolation Being a tertiary alcohol, it is very sensitive to organic acids Properties of linalool Recently Linalool, a natural compound of the essential oils, has been shown to have antinociceptive, antimicrobial, and anti-inflammatory properties. Liver protective effect. (2014) Aromatic Alcohols (str. +use) Benzyl alcohol Free or as ester of benzoic and cinnamic acids in balsams as Peru and Tolu, as ester of acetic acid as in oil of Jasmine Fractional distillation of original or saponified oils, or by the formation of complex addition Isolation product with anhydrous CaCl2. geraniol‫زي ال‬ ➤Colorless liquid with a faint aromatic odor, sparingly volatile with steam. liquid ‫نخلي بالنا من الحاجات ال‬ Properties ➤Soluble in ethanol; sparingly soluble in water. ➤On exposure to air ______benzaldehyde _______benzoic acid. ➤Through preparation of derivatives as acid phthalate,p-nitrobenzoate. Identification acid phthalate Derivatives ‫أو‬p-nitrobenzoate Derivatives ‫واحوله الي‬ ➤Oxidation with chromic oxide and H2SO4 or KMnO4 → benzoic acid. ➤In perfume; cosmetic and soap industries Uses ➤Synthesis of flower oils as Jasmine & gardenia. ➤Fixative and a diluents in perfume mixtures ‫مثبت للعطور‬. Other aromatic alcohols are phenyl ethyl alcohol and cinnamyl alcohol 4  Phytochemistry I Chemistry of essential oils 03 Monocyclic terpene Alcohols 1. Menthol (p.menthane, 3-ol) Occurs in I-form in various Peppermint oils ➤ (Mentha piperita) 50-65% menthol. ➤Mentha arvensis (Japanese mint) the oil is called Cornmint oil 75-90% menthol. Isolation Crystals of menthol is precipitated by a very slow cooling of the corn-mint oil, cooling ‫عن طريق‬crystalline ‫الي بيحصله‬v.o ‫مهم جدا نعرف مين ال‬ Menthol can be also synthesized by hydrogenation of thymol or pulegone: optically inactive ‫ المصنع بيكون‬menthol ‫ اما ال‬l.form ‫بيكون‬natural menthol ‫ال‬ Properties: White needle-shapes crystals with mint odor and a cooling taste. ➤Through preparation of derivatives as acid phthalate, p- nitrobenzoate. ➤Color test: Solution of menthol in H₂SO₄ + a drop of vanillin sulphuric acid Identification reagent ___orange yellow color, changing to violet on addition of water drops. drop if vanillin sulphuric acid ‫واضع‬H2so4 ‫ مع‬menthol ‫التفاعل ده اخذته في المعمل لما تفاعل ال‬ ‫ من المياه‬drops ‫لما احط عليه‬violet ‫يتحول الي‬orange yellow ‫ يعطي لوم‬reagent ➤An ingredient of itch-relieving creams. ➤In food technology. ➤In preparations used to decongest the upper respiratory tract in case of rhinitis. Uses ➤In oral hygiene products and shaving products. ➤kills the germs responsible for the bad breath. Therefore, instead of simply being a cover up for bad breath, it helps to eliminate the cause altogether. ‫هو يقضي علي رائحة الفم الكريهة ويقتل أيضا البكتريا المسئولة عن هذه الرائح‬ 2. α-terpineol ➤ Oil of Neroli (d-form) ➤Oils of camphor & lemon (I-form) ➤Oils of geranium (dl-form) 5  Phytochemistry I Chemistry of essential oils 03 Through the preparation of several compounds e.g nitrosochloride and phenyl Identification urethane. Isolation ➤ Fractional distillation. ➤ Formation of crystalline derivatives as phthalates. ➤ Synthetically from various pine oils which contain dipentene and α-pinene (commercial methods) ‫يعني كمية كبيرة‬ ‫فيعطى‬dehydration ‫ثم اعمل‬terrine hydrate ‫فيعطى‬H2so4 ‫في وجود‬dipentene ‫يصنعه من ال‬ a-terpineol specific catalysy ‫في وجود‬a-pinene ‫او اصنعه من ال‬ ➤Crystalline compound, sparingly soluble in water. Properties ➤With bromine → oily dibromide. Reaction Isomerization ➤ The isomerization of α-terpineol (1) catalyzed ➤ by dissolved or silica-supported heteropoly ➤acid H3PW12O40 (PW) yields 1,8-cineole (2) ➤and 1,4-cineole (3), both useful for flavoring and pharmaceutical applications, ‫ويعطى مركبين هما‬isomerization ‫يحصل له‬catalyst ‫لو فاعلته مع نوع معين من ال‬a-terpinol ‫ال‬ pharmaceutical ‫مهمين جدا في ال‬cineole -1,4 ‫و‬cineole -1,8 Applications ➤It is one of the most important compounds used in perfume, cosmetic, and soap industries because of its lilac like odor and the low price of the synthetic product. Uses ➤Recently, Linalool and α terpineol exhibited strong antimicrobial activity against periodontopathic and cariogenic bacteria. However, their concentration should be kept below 0.4 mg/ml ‫البكتيريا المسئولة عن التهابات اللثة‬antimicrobial activity against 6  Phytochemistry I Chemistry of essential oils 03 Bicyclic monoterpene alcohol ‫ وبتكون عبارة عن حلقتين‬OH ‫ يعني هي فيها‬bicyclic monoterpene alcohol ‫ هنتكلم دلوقتي عن ال‬ ‫ فوق وال تحت‬OH ‫ بيختلفوا على حسب مكان ال‬isoborneol ‫ أو‬Borneol ‫ بيبقى عندي بقى يا إما‬ ‫ مش‬Isoborneol ‫ اما الـ‬،،،، )naturally occurring( ‫ بيبقى موجود في الطبيعة‬Borneol ‫ ناخد بالنا من معلومة مهمة جدا‬ (synthetic ) ‫موجود في الطبيعة‬ d-Borneol(Borneo-camphor): L-borneol (Ngai-camphor): Oil of different species of (F.Dipterocarpaceae) , Oils of citronella, coriander and valerian roots. oils of rosemary and lavender 1. Borneol ✓ Borneol crystals can be precipitated from cooling the distillate of the Dryobalanops tree trunk. (‫هنا بيقولك ان انا ممكن افصله (ارسبه (على هيئة كريستاالت بالتبريد‬ ✓ Saponification of pine needle oil, removal of hydrocarbons by distillation, cooling → borneol Isolation ‫في هيئة‬Borneol ‫ فيها كمية كبيرة من من‬pine neddle oil ‫ال‬ ‫وعشان اكسر ال‬sponification ‫ فبعمل‬borneol acetate cooling ‫عن طريق‬borneol ‫وبعدين افصل ال‬acetate Methods for Separation of borneol from camphor ✓ Through formation of ester with phthalic or succinic acid. ‫كيتون مش هيكون استر‬camphor ‫ واكون استر اما ال‬acid ‫ عبارة عن كحول هفاعله مع اي‬borneol ‫ناخد بالنا ال‬. ✓ Through forming non-volatile esters with benzoic or stearic anhydride and removing camphor by distillation. ‫يترسب‬camphor ‫وال‬non volatile ester ‫ ويكون‬benzoic or stearic anhydride‫يتفاعل مع ا‬borneol ‫ال‬ ✓ Converting camphor to its oxime which is soluble in 25% H2SO4 ‫في صورة‬compher ‫ وبكدا انا فصلت ال‬H2So4‫وده بيدوب في ال‬oxime ‫ يدي‬NH2OH ‫لما بفعله مع ال‬compher ‫ال‬ borneol ‫ وتبقي ال‬oxime Separation of borneol from isoborneol : ✓ By heating with zinc chloride in benzene, isoborneol (unstable) give solid terpene hydrocarbon camphene. ✓ Borneol is purified through its crystalline acid phthalate. 7  Phytochemistry I Chemistry of essential oils 03 Prop. ✓ Crystalline compound with camphor like odor. ✓ Soluble in alcohol, ether, sparingly soluble in benzene. ✓ Volatile at ordinary temperature. ✓ Readily oxidized to camphor by (CuO, Cl2 ) ✓ Reduction of camphor by sodium and alcohol a mixture of borneol and isoborneol. ✓ Forms loose addition compounds with bromine and hydrogen halides. ‫عشان كدة‬borneol, isoborneol ‫ من ال‬mixture ‫ بيديني‬camphor ‫ناخد بالنا ان مثال لما باجي اعمل اختزال لل‬.‫الزم افصلهم عن بعض‬ ‫نفس طريقه تحضير‬ camphor Ident. ✓ Through the preparation of derivatives as nitrobenzoates Uses ✓ Borneol is used for scenting certain preparations. ✓ Borneol specifically inhibits the nAChR (Nicotinic acetylcholine receptor) -mediated effects nAChRs have been shown to be involved in smoking-induced cancer) ‫ للمدخنين‬anti cancer ‫ لذا يؤخذ‬nAChR ‫ لل‬inhibition ‫استخداماته انه بيعمل‬ Other Isoborneol, showed dual viricidal activity against herpes simplex virus 1 recent (HSV-1). First, it inactivated HSV-1 within 30 min of exposure, and second, uses isoborneol at a concentration of 0.06% completely inhibited viral replication inhibition viral replication ‫ ويعمل‬antivirus ‫ انه‬isoborneol ‫ بتاع ال‬recent uses ‫ناخد بالنا من ال‬ Sesquiterpene Alcohols α-Santalol ➤Perfumes, urinary disorders (diuretic and antiseptic) ➤β-Santalol exhibited anti-influenza A/HK (H3N2) virus activity of 86% with no cytotoxicity at the concentration of 100 μg/ml ➤α-Santalol, a major component of sandalwood oil showed anti-cancer activity in prostate cancer cells by inducing apoptosis and activation of caspase-3 activity apotosis ‫ لعمليه ال‬inducing ‫النه فيعمل‬anti cancer anti influenza ‫♧ يشتغل ك‬ ➤α- and β-santalols could be considered as neuroleptic by resemblance to the Uses pharmacological activities of Chloropromazin chloroprpmazin ‫ ألن االستراكشر بتاعها شبه اب‬neuroleptic ‫ يشتغلو‬santalol ‫االلفا والبيتا‬ ➤Use of α- and β-santalols major constituents of sandal wood oil, used in the treatment of warts, skin blemishes and other viral induced tumors.. ‫ ا وبيعالج السرطانات اللي بتحصل في الجلد بسبب الفيروسات‬warts ‫♧بيعالج برده ال‬ a-santalol‫بيفرق عن‬B-santalol.-‫زياده‬double bound ‫فى‬ 8  Phytochemistry I Chemistry of essential oils 03 Viscous yellowish liquid Isolation Properties with a sandalwood-like odor. Fractional distillation Oxidation with chromic oxide santalal, is aldehyde. Identification o the semicarbazone of which melts at 230 C. Determination of alcohol content in volatile oils: ➤ Through esterifying the alcohols with acetic anhydride and estimation of the resulting acetate by hydrolysis with alcoholic KOH. ➤ This method is not suitable for tertiary alcohols; othermethods can be used. ➤ Dehydration method: Some tertiary alcohols dehydrate quantitatively under the influence of certain reagents. The amount of resulting water is determined from which the percentage of alcohol can be calculated koH ‫ ليه بال‬titration ‫ اعمل‬acetate ‫ بيطلع‬acetic anhydride ‫مع ال‬alcohol‫ تفاعل ال‬v.o ‫في ال‬alcohol ‫ عشان اعرف كمية ال‬ ‫عشان أعالج‬tertiary alcohol ‫ والتجربة دي مبتنفعش مع ال‬alcohol ‫تساوي كمية ال‬titration ‫ الي تستخدم في ال‬KoH ‫وكمية ال‬ tertiary alcohol ‫ فكمية الماء الي هيطلع يساوي كمية ال‬tertiary alcohol ‫ مع ال‬Dehydration method ‫المشكلة دي بعمل ال‬ Phenols and phenolic ethers They are among the most important constituents of volatile oils. General methods of isolation: Phenols (weak acids) form water soluble salts with dilute alkali solutions (3-5%). Therefore the oil containing phenols is shaken with dilute aqueous solution of alkalis; the aqueous layer is separated then acidified (to liberate the phenol) and either steam distilled or extracted with ether. ‫ بيدي‬dilute alkali ‫ لما افاعلها مع‬weak acid ‫الفينول تعتبر‬ ‫عشان اكسره‬acid ‫ افاعله مع‬water soluble salt ‫ عشان اعرف كمية‬ether ‫ مع ال‬extraction ‫وبعدين اعمل‬ ‫الفينول الي معايه‬ Phenol sodium phenoxide General methods of isolation phenols and phenolic ethers: By cooling the oil or the suitable fraction, some phenols and phenolic ethers can be separated in crystalline form. crystals ‫للفينول عن طريق اني ابرده فهيترسب على هيئة‬isolation ‫نعمل‬ General characters of terpene phenols General characters of phenolic ethers With FeCl3___________ colored iron Do not react with alkali (neutral) and do not give reactions compounds. typical of phenols. Give corresponding phenols on treatment with hydrobromic Undergo some reactions characteristic of or hydroiodic acid. alcohols; as reactions with acetic anhydride, phenyl isocyanate..., Can be identified by formation of crystalline derivatives e/g: reaction with CISO3H acid (cl sulfonic a) sulfonyl chloride____ sulfonamide on treatment with NH3 or (NH4)2CO3. ‫ ودا‬sulfonyl chloride ‫ بيدي ال‬CLSO3H ‫افاعله مع ال‬phenolic ether ‫ال‬ sulfonamide‫بيدي ال‬NH3 ‫لو فاعلته مع ال‬ 9  Phytochemistry I Chemistry of essential oils 03 CLASSIFICATION: Phenols and phenolic ethers may be grouped into: ▪ Monohydric ▪ Dihydric ▪ Trihydric (myristicin) ▪ Tetrahydric (apiole) (thymol, anethole) (eugenol, safrole) ‫وهكذ‬monohydric ‫واحده يبقى‬oH ‫اللي على الحلقة يعني لو عندي‬OH ‫تصنيف الفينول بيكون على حسب عدد‬ Monohydric phenols: ‫واحده‬O ‫يعنى المركب بتاعنا فيه‬ Thymol: ( 3-Hydroxy-p-cymene) ➤Oil of Thyme,Thymus vulgaris, F Labiatae (Lamiaceae) Nomenclature ➤Oil of Ajowan, Carum copticum,F Umbelliferae (Apiaceae) ‫بيكون موجود في زيت الزعتر و االجوان‬ Isolation ➤ Fractional distillation ➤Cooling the oil -----crystals. ➤Using KOH (5%) Identification Through derivatives: as phenyl urethanes, dinitrobenzoate,… Large crystals with a thyme-like odour and a pungent taste. ‫ و له رائحة الزعتر و طعم الذع او حراق‬Large crystals ‫من الخصائص بتاعته انه عبارة عن‬ Properties ◼ Soluble (1:1200) in water, (1:1) in alcohol, soluble in ether, chloroform,…. Soluble ‫ بيكون‬alcohol ,ether & chloroform ‫ لكن في ال‬water ‫ في ال‬sparingly soluble ‫بيكون‬ ➤ Thymol+ gl. Acetic acid + 3 drops conc. H2SO4 + 1drop conc. HNO3------- greenish- Color blue colour reactions: ‫ و التفاعل‬gl. Acetic acid ‫ مع ال‬Thymol ‫ نتيجة تفاعل ال‬greenish-blue ‫مهم اوى نركز عن اللون اللى هيطلع‬ (chemical ‫ده اخدناه في المعمل‬ test) ➤Thymol+ conc. H2SO4----- thymol sulfonic acid +FeCl3 ------violet colour thymol ‫ اللى هو ال‬intermediate compound ‫ هيطلع‬Thymol+ conc. H2SO4 ‫تانى تفاعل معانا هو ال‬ ‫ هيتكون عندنا اللون األزرق‬FeCl3 ‫ اللى لو فاعلته مع ال‬sulfonic acid thymol ‫ طرق لتحضير ال‬3 ‫عندنا‬ isopropyl ‫ عن طريق اني احط عليه‬m-cresol ‫اول طريقه من ال‬ catalyst‫ و‬alcohol Synthesis FeCl3 ‫ في وجود ال‬Piperitone ‫تانى طريقة من‬ Br2/quinoline ‫ في وجود ال‬Menthone ‫تالت طريقه من‬ Thymol has disinfectant and antibacterial properties; employed in some antiseptic mixtures as gargles, mouthwashes and dental preparations. Also used as gastrointestinal disinfectant in fermentative gastritis, as well as antifungal and anthelmentic agent. It has anti- Uses inflammatory activity ‫ و ال‬gargles ‫ و بيستخدم في ال‬antibacterial‫ مطهر او ك‬antiseptic‫ او‬disinfectant ‫ ك‬Thymol ‫بنستخدم ال‬ disinfectant in fermentative gastritis, as well as antifungal ‫ ك‬git ‫ و بيستخدم في ال‬mouthwashes ‫ و كمان يستخدم كمضاد لاللتهاب‬and anthelmentic agent 10  Phytochemistry I Chemistry of essential oils 03 ◼ Among thymol, carvacrol, citronellal, eugenol and terpinen-4-ol, thymol showed the highest antibacterial activity against Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa ◼ International Journal of Pharmaceutics, Volume 434, Issues 1–2, 15 September 2012, ‫ أنواع‬5 ‫ بين ال‬2012 ‫في بحث سنة‬ ‫من الزيوت دول‬ ‫ اكثر واحد فيهم‬thymol ‫القوا ان ال‬ ‫ ضد ال‬antibacterial activity ‫له‬ staphylococcus aureus & pseudomonas aeruginosa Anethole: p-propenyl-methyl phenol or Anise camphor. ➤ Anise oil 84-93% E-anethole (trans) Nomenclature ➤ Bitter Fennel oil 50-80% ➤Sweet Fennel oil 80% F. Umbellifarae (Apiaceae) ‫ موجود في الينسون و الشمر و الزم اركز على نسبته في ال‬Anethole ‫ال‬ Sweet Fennel ‫ و ال‬Bitter Fennel Isolation Cooling oil or fraction rich in anethole--------- crystals ➤ By oxidation -----anisaldehyde, on further oxidation ------anisic acid. Identification anisic acid ‫ و لو زودت االكسده هيكون ال‬anisaldehyde ‫ هيكون ال‬Oxidizing agent ‫لو حطيت عليه‬ ➤Formation of nitroso-derivative or a condensation product with maleic anhydride. ➤White crystalline mass of intensely sweet odour and taste (anise fruit). ➤ Insoluble in water and soluble in organic solvents. ➤ Unstable under the influence of light, air or heat Properties p-p ̀-Dimethoxy stilbene ) Photoanethole) Anisaldehyde Anisic acid p-p -̀ Dimethoxy ‫ و‬Anisic acid ‫و‬Anisaldehyde : ‫ مركبات‬3 ‫ اتعرض للضوء او الحرارة هيكون‬Anethole ‫لو ال‬ stilbene ‫ مع ال‬anisole ‫لو فاعلت ال‬ propionaldehyde intermediate ‫هيطلعلنا مركب‬ Synthesis Pyridine ‫اللى لو فاعلته مع ال‬ Anethole ‫هيتكون ال‬ ➤ Anethole is widely used as a palatable flavour in confectionary and beverages, also in pharmaceutical preparations as dentifrices, mouthwashes and gargles. ‫ في المخبوزات و المستحضرات الصيدلية مثل المضمضة و غسول‬flavoring agent ‫ ك‬Anethole ‫يستخدم ال‬ ‫الفم و معجون االسنان‬ Uses ➤ Anethole suppressed cell survival and induced apoptosis in human breast cancer cells (June 2012, Phytomedicine) breast cancer cells ‫ لل‬reduction ‫ النه بيعمل‬anticancer activity ‫كمان له‬ 11  Phytochemistry I Chemistry of essential oils 03 Dihydric phenols: Eugenol: 4-allyl-2-methoxy phenol ➤ Oil of clove (F. Myrtaceae) ➤ Oil of Cinnamon leaves (F. Lauraceae) Nomenclature ➤ As glycoside, gein Geum urbanum (F. Rosaceae) ‫ و ان ال‬, bark ‫ مش ال‬Cinnamon leaves ‫ناخد بالنا انه موجود في ال‬ gein ‫ بتاعه موجود في نبات ال‬glycoside Isolation Using KOH (5%) ➤ Formation of derivatives as benzoate, phenyl urethane,… ➤ Microchemical test: a drop of oil + a drop of 3% NaOH saturated with NaBr crystals of sodium eugenate (needle and pear-like forms arranged in Identification rosette-like bunches). sodium ‫ النه يعطي‬NaBr ‫ لما افاعله مع‬crystal ‫بيتحول الي‬ needle or rose shap ‫ شكلها‬eugene crystal ➤Color reactions with FeCl3 ➤ Yellowish, viscous liquid with burning taste and clove-like odor. liquid ‫ناخد بالنا انه‬ ➤Heavier than water, sparingly soluble in water, soluble in Properties alcohol and caustic alkalis. ➤By heating with KOH---------- isoeugenol ‫ و ال = بتتحرك‬isomerization ‫بيحصله‬ ➤ Eugenol is used in toothache remedies; has local anesthetic properties (inhibits nerve conduction), also an anti-inflammatory. It is bactericidal at law concentration; used in formulation of mouthwashes. ➤ In vivo, eugenol (50–100 mg/kg; i.p.) inhibited carrageenan-induced rat paw oedema ( Uses 5 times more potent than aspirin). The results provide evidence that eugenol acts as a dual antagonist of AA and PAF (Phytomedicine, 1995). rat ‫ اسمه‬oedema ‫ ده نوع من أنواع الطحالب البحرية ممكن يتسبب في نوع من أنواع ال‬carrageenan ‫ال‬ paw oedema ➤Preparation of vanillin (aldehyde vol oil) Safrole: Allyl catechol methylene ether ➤Oil of Sassafras: 80% safrole ➤Oils of star anise, nutmeg and Nomenclature Cinnamon leaf. Isolation By cooling the oil or safrole containing fraction to about –10oC. Safrole or isosafrole + conc. H2SO4 ----------intense red color. oxidation Identification 12  Phytochemistry I Chemistry of essential oils 03 Safrole piperonal Piperonal ‫ اللى هو ال‬ald. ‫ هتتكسر و تتحول الى‬side chain ‫في االكسدة ال‬ Colorless liquid, insoluble in water, soluble in alcohol or ether, by cooling--------- crystalline mass. Properties ➤ By heating with alkali --------- Isosafrole ‫ و ال = اتحرك مكانها نتيجة ال‬isoeugenol ‫ اتحول الى‬eugenol ‫زي ال‬ Isomerization ➤Was widely used as flavour before it was banned; safrole induces the formation of hepatic tumours in rodents (carcinogen). carcinogenic effect ‫ لكن تم حذره حاليا النه له‬flavoring agent ‫كان بيستخدم ك‬ ➤ Safrole is an important raw material for the chemical industry because of two Uses derivatives: (Piperonal), which is widely used as a fragrance and flavoring agent, and piperonyl butoxide (PBO), a vital ingredient of pyrethroid insecticides. piperonyl ‫ و ال‬fragrance and flavoring agent ‫ اللى بيستخدم ك‬Piperonal ‫بقي الماده الخام لل‬ ‫ بيستخدم كمادة مبيدة للحشرات‬butoxide (PBO) Trihydric phenolic ether: Myristicin: Myristicin or 6-methoxy safrole ‫ الزيادة‬methoxy gp ‫ هو وجود ال‬safrole ‫الفرق بينه و بين ال‬ ➤Oil of nutmeg (Myristica fragrance, F. Nomenclature Myristicaceae) nutmeg ‫ بتاعة ال‬seed ‫موجود في ال‬ ➤Oil of mace (dried arillus of Myristica Fragrance) mace ‫ بتاعة ال‬seed ‫ بتاعة ال‬arillus ‫موجود في ال‬ ▪ On oxidation with KMnO4 gives the corresponding aldehyde/acid. Identification ▪ With bromine -------dibromomyristicin. ➤ Oily liquid with faint aromatic odor, does not congeal at low temperature, heavier than water. liquid ‫ يعنى هيفضل زى ما هو‬coiling ‫ بال‬solidification ‫يعنى مش بيحصله‬ Properties ‫في درجات الحرارة المنخفضة‬ ➤On boiling with alcoholic KOH -------isomyristicin ‫ بتاعه‬iso ‫ ال= هتتحرك و يتكون ال‬boiling ‫ تحت بال‬side chain ‫كل اللى عندهم‬ ➤ Nutmeg is used as stomachic, stimulant and carminative (spice). Low dose ‫بتستخدم في االكل بكمية صغيرة كفاتح للشهية و طارد للغازات‬ Uses ➤The psychotropic activity of nutmeg (euphoria, hallucination) seems linked to myristicin and closely related products: MMDA is thought to be formed in the body after ingestion of nutmeg by amination process on myristicin and may be the agent responsible for the euphoric and hallucinogenic effects of high doses of nutmeg. ‫ النه بيتكون داخل الجسم المركب‬psychotropic activity ‫لكن لو استخدم بكميات كبيرة بيكون له‬ Amphetamine ‫ يتحول الي‬MMDA ‫ و ال‬euphoric and hallucination ‫ اللى بيسبب‬MMDA 13  Phytochemistry I Chemistry of essential oils 03 Tetrahydric phenolic ether: Apiole: Apiole, Parsley camphor, 3-methoxy myristicin Nomenclature methoxy ‫ لكن زياده عليه مجموعة ال‬myristicin ‫ بتاع ال‬structure ‫شبه ال‬ ➤By cooling the oil and recrystallization from alcohol and pet. ether. Properties: ➤Long colourless needles with faint parsley odour, insoluble in water, soluble in Isolation alcohol and ether. ➤ On boiling with alcoholic KOH --------isoapiole boiling with alcoholic KOH ‫ فيها = لما يحصله‬side chain ‫زى ما قولنا فوق ان اى مركب عنده‬ ‫ بتاعه‬isoderivative ‫هيتحول لل‬ Apiole has carminative, diuretic and uterine stimulant properties, not used now Uses because of intoxication of high doses. ‫ و لكن لم يعد يستخدم حاليا النه بيعمل تسمم بالجرعات العاليه منه‬git ‫معظم استخداماته في ال‬ Determination of Phenols: ➤The general method is based on the fact that phenols react with alkali hydroxides to form phenolates, KOH is preferred; more soluble. Disadvantages of this method : ◼ Water-soluble materials (as alcohols,…) will go into solution and calculated as phenols. phenol ‫ الن فيه حاجه تانية هتذوب غير ال‬error ‫هيعمل‬ ◼ Aqueous solution of phenolates is a better solvent for the non-phenolic portion of the oil -------apparent higher content of phenols. more ‫ النه بيكون‬KOH ‫ و األفضل استخدم ال‬OH ‫ حاجه فيها‬alkali hydroxide ‫علشان احدد كمية الفينول اللى عندى هفاعله مع‬ ‫ هيتكون عندى البوتاسيوم فينوالت بيدوب في‬shake ‫ معينه و اعمل‬KOH ‫ معينه و كمية‬oily ‫ بجيب الفالسك و احط فيها كمية‬soluble ‫ وعشان اعرف كمية الفينول اطرح الكمتين‬oil ‫البوتاسيوم هيدروكسايد فيلم محمد ال‬ 2. HI method for ethers: 3. Chromatographic method Conversion of ethers into phenols by treating the oil with Gas chromatography HI and the resulted phenol determined as above. Retention time (Rt )-------- identification. Determination of free phenols (before HI) Area under the peak ---------quantitative Treatment with HI and determine the total phenols and determination phenolic ethers. Phenolic ethers are estimated by difference. ‫الطريقة التانية بتستخدم لاليثر هناخد االيثر نحوله للفينول بتاعه عن‬ Gas chromatography ‫الطريقة التالته معانا و هو ال‬ HI ‫طريق انى افاعله مع ال‬ ‫ بيحددلى العينة بتاعتى فيها فينول‬Retention time ‫ال‬ ‫ و‬HI ‫ قبل اما اضيف ال‬free ‫بتم عن طريق انى احدد كمية الفينول ال‬ ‫ او‬identification ‫ ايه يعنى بيعملى‬v.o ‫ايه او‬ ‫ و هيتحول االيثر الى فينول و بالتالى‬HI ‫ مع ال‬oil ‫بعدها هفاعل ال‬ Area under the ‫ لكن ال‬qualitative analysis ‫كمية الفينول هتزيد فهطرح الكميتين من بعض و الفرق هيكون كمية‬ ‫ بتحددلى الكمية اللى موجوده‬intensity ‫ او ال‬peak ‫االيثر‬ ‫من المركب ده او بمعنى اصح بيعمل‬ 14