Organic Chemistry Module 3 PDF

Module 3 ORGANIC CHEMISTRY Course audit 1  TABLE OF CONTENTS TOPIC 1: Organic Chemistry 1 TOPIC 2: Benzene Derivatives / Heterocycles / Isomers 4 TOPIC 3: Important Alcohols...

Module 3 ORGANIC CHEMISTRY Course audit 1  TABLE OF CONTENTS TOPIC 1: Organic Chemistry 1 TOPIC 2: Benzene Derivatives / Heterocycles / Isomers 4 TOPIC 3: Important Alcohols 9 TOPIC 4: Important Ethers 11 TOPIC 5: Important aldehydes 13 TOPIC 6: Important Ketones 15 TOPIC 7: Important Acid 17 TOTAL = 18 PAGES TOTAL = 11 PAGES (TO REVIEW)  TOPIC 1 Organic chemistry 1  ORGANIC CHEMISTRY B. UNSATURATED Branch of science that deals with the study of compounds containing Carbon with H, O, N, S, P, and ALKENES (Olefins) → double bond halides (F, Cl, Br, I) ALKYNES → with triple bond in structure ❗ BEQ: NO STRUCTURES in the past 10 years ONLY CHEMICAL FORMULAS but encouraged to familiarize the structurecs 2. AROMATIC HYDROCARBONS UREA Aka ARENES Presence of ring system with multiple bond ✏️ First organic compound synthesized from inorganic Benzene and its derivatives ❗ matter. POLYCYCLIC BENZENOIDS / POLYAROMATIC HC - Final waste product of protein metabolism BEQ Important compound Discovered by FRIEDRICH WOHLER (1828) from ➔ benzene rings fused together heating lead cyanate and ammonia (inorganic compound) VITAL FORCE A theory or principle organic substances could only originate from living material disproved by WOHLER - Cyanate and Ammonia are not living organism but synthesized urea which is an organic compound CLASSIFICATION OF ORGANIC COMPOUNDS MOCK BOARDS ONLY, NOT BEQ 2. ANTHRACENE ➔ Parent ring for anthraquinone glycosides 3. PHENANTHRENE ➔ Precursor for steroid nucleus 5. CHRYSENE ➔ Aka CALAT 3. ALICYCLIC HYDROCARBONS Chains that form a ring without a multiple bond - fused rings Behave like aliphatic hydrocarbons Cyclo - Meaning circle or ring 1. HYDROCARBONS 1. ALIPHATIC HYDROCARBONS HC compounds arranged in linear chain or branched form without any ring system involved Not cyclic, no benzene ring 2 TYPES OF ALIPHATIC HYDROCARBONS ALICYCLIC HYDROCARBONS A. SATURATED (ALKANES) CYCLOPROPANE 3 Carbon Aka PARAFFINS CYCLOBUTANE 4 Carbon Single bond only CYCLOPENTANE 5 Carbon CYCLOHEXANE 6 Carbon 2  SUMMARY OF EMPIRICAL FORMULAS 🧠 MEMORIZE 🧠 3. SULFUR-CONTAINING HYDROCARBONS Thio = Sulfur CnH2n + 2 – Alkane CnH2n – Alkene / Cycloalkane w/o multiple bonds THIOLS / R-SH – sulfur analogue of ➔ No +2 SULFHYDRYLS alcohols CnH2n – 2 – Alkyne / Cycloalkane w/ 1 double bond THIOETHERS R-S-R ➔ 1 double bond = -2 THIOESTERS R1COOSR2 CnH2n – 4 – Cycloalkene w/ 2 double bonds ➔ 2 double bonds = -4 Sulfur = R-SH Alcohol = R-OH 1. HC DERIVATIVES 1. OXYGEN-CONTAINING HYDROCARBONS 4. PHOSPHORUS-CONTAINING Any structures that contains OH is an alcohol HYDROCARBONS Phosphate Groups 1. ALCOHOLS R-OH – hydroxyl group Organophosphates ➔ Most common insecticide or agricultural 2. PHENOLS Ar-OH – hydroxyl group in an chemical aromatic - AR (Aromatic) ➔ Ex: rice fields to kill pest 3. ALDEHYDES R-CHO – always a terminal functional group - End 5. HALOGEN-CONTAINING 4. KETONES R1-CO-R2 HYDROCARBONS - 2 functional groups in between CO Alkyl halides Aryl halides 5. CARBOXYLIC R-COOH ACIDS 6. ESTERS R1COOR2 - 2 functional groups in between COO 2. NITROGEN-CONTAINING HYDROCARBONS Capable of forming 3 bonds: 1. AMINES amino group, -NH 2. PRIMARY one alkyl group connected AMINES (RNH2) to the amino group 3. SECONDARY two alkyl groups AMINES (R2NH) connected to the amino group 4. TERTIARY three alkyl groups AMINES (R3N) connected to the amino group 5. HETEROCYCLIC important for the ❗ NITROGENOUS structures of alkaloids COMPOUNDS BEQ MODULE 2 PCOG - alkaloids 3  TOPIC 2 BENZENE Derivatives / heterocycles / ISOMERS 4  BENZENE DERIVATIVES II. DISUBSTITUTED Structural Modifications - different functions I. MONOSUBSTITUTED 1. CRESOL Aka O,M,P - METHYLPHENOL Ortho, Meta, Para 1. PHENOL/ Aka HYDROXYBENZENE 2. TOLUIDINE Aka METHYLANILINE Hydroxyl Group (- OH) Toxic metabolite of PRILOCAINE CARBOLIC ACID Discovered by JOSEPH LISTER ➔ Amide local anesthetic (Father of Antisepsis) ➔ Causes methemoglobinemia 1st antiseptic agent (oxides Hgb) PHENOL COEFFICIENT (PC) ➔ AD: 1% Methylene Blue ↑ PC = ↑ Antiseptic Activity 3. XYLENE Aka DIMETHYLBENZENE 2. ANILINE Aka AMINOBENZENE Amine group (-NH2) 4. SALICYLIC Aka 2-HYDROXYBENZOIC ACID ACID 3. TOLUENE Aka METHYLBENZENE 5. CATECHOL OTHER NAMES: Methyl group (-CH3) Ortho a. 1,2-DIHYDROXYBENZENE b. O-DIHYDROXYBENZENE 4. BENZALDEHYDE Formyl group (-CHO) Parent ring of catecholamines 1. Dopamine 2. Epinephrine, 5. BENZOIC ACID Carboxyl group (-COOH) Used as an antimicrobial 3. Norepinephrine preservative 6. RESORCINOL OTHER NAMES: 6. ANISOLE Aka METHOXYBENZENE Meta a. 1,3-DIHYDROXYBENZENE Methoxy (OCH3) b. M-DIHYDROXYBENZENE 7. STYRENE Aka ETHYNYLBENZENE 7. HYDROQUIN OTHER NAMES: ONE a. 1,4-DIHYDROXYBENZENE Para b. P-DIHYDROXYBENZENE ANESTHESIA 1i = ESTERS (Procaine) 2i = AMIDE (Prilocaine, Lidocaine) ❗ BEQ: LIDOCAINE → BRAND NAME: XYLOCAINE Ortho - Katabi Meta - 1 interval Para - Katapat 5  II. 6-CARBON IMPORTANT HETEROCYCLES 1. NITROGEN-CONTAINING I. 5-CARBON DIHYDROPYRIDINES Drugs that ends in “-dipines” Ca2+ Channel Blockers (CCB) 1. Amlodipine 2. Nifedipine 3. Felodipine 4. Nicardipine 5. Nimodipine PORPHYRIN PROCESS Condition of deficiency of enzyme PERHYDROGENATION (DHP → Piperidine) Composed of 4 fused pyrrole subunits interconnected at their alpha carbon atoms via methane bridges MOA Important in the structure of chlorophyll and Relaxes heart due to excessive pump of heart hemoglobin Not influx of Ca2+ (contractant) - relaxes BV Structure: Like a cross III. HETEROCYCLIC LEVETIRACETAM Ⓡ BRAND NAME: KEPPRA Pyrrolidine anticonvulsant CLONIDINE Ⓡ BRAND NAME: CATAPRES Imidazoline alpha adrenergic agonist 2 TYPES OF ANTIFUNGALS 1. IMIDAZOLE 🧠 MEMORIZE 🧠 Ketoconazole Clotrimazole Miconazole Isoconazole 2. TRIAZOLES (VIP) Voriconazole Itraconazole Posaconazole 6  2. OXYGEN-CONTAINING CARBONS ATOMIC NO: 6 5-CARBON GROUP: IV ATOMIC MASS: 12 PROPERTIES 1. AROMATIC AND No information MOLECULAR ORBITALS 2. STABILITY OCTET RULE ➔ 8 electrons in valence shell ➔ Giving same electronic configuration to nearest noble gas ➔ ONLY applicable to MAIN GROUP ELEMENTS / REPRESENTATIVE ELEMENTS 2 WAYS TO ACHIEVE STABILITY 1. REDUCTION & OXIDATION REACTION 2. COVALENT BONDS by combining C and other atoms to share electrons (INTERMOLECULAR FORCE) ❗ BEQ: Know the numbers of carbons OTHERS INTERmolecular Force = Sharing of How many C in FURAN? 5C electrons INTRAmolecular force = transfer of electrons 6-CARBON 3. CATENATION ability of atom to form multiple bonds to itself (unique feature of Carbons) 4. HYBRIDIZATION mixing of two or more non-equivalent atomic orbitals to form a new set of equivalent hybrid orbitals 5. ISOMERISM refers to the existence of 2 or more compounds having the SAME MOLECULAR FORMULA Sounds alike! BUT DIFFERENT STRUCTURE 3. SULFUR-CONTAINING THIO = Sulfur 7  CONSTITUTIONAL ISOMERS 2. THALIDOMIDE 1. CHAIN / SKELETAL ISOMERS ➔ Causes phocomelia Exhibited by alkanes due to possibility of branching ➔ Achiral molecule existing in 2 mirror images Different in branching / parent length ➔ initially a sedative and anti-nausea Different connectivity medication (1950s and 1960s) for pregnant involves breaking of bonds (before connectivity) women with morning sickness BUT causes Example: severe birth defects ➔ tragic thalidomide disaster = limb 1. PENTANE deformities and other developmental issues ➔ 3 chain isomers: n-pentane, isopentane, for babies neopentane ➔ S-THALIDOMIDE = therapeutic properties ➔ R-THALIDOMIDE = teratogenic effect 2. BUTANE (causes phocomelia) ➔ 2 chain isomers: n-butane, isobutane D. EPIMER 2. POSITIONAL ISOMERS differ in 1 carbon ❗ Compounds that differ only in the position of the substituent, functional group, or multiple bond BEQ Parent chain → not change , only substituent D-MANNOSE → c2 epimer of D-glucose change position D-GALACTOSE → c4 epimer of D-glucose Position of substituents, FG, multiple bonds → change E. ANOMER 3. FUNCTIONAL ISOMERS Differ in functional group differ at C1 Example: 1. ALCOHOL (-OH) and ETHER (-OR) When writing 𝜶 & 𝛃 2. ALDEHYDES (R-CHO) and KETONES (R-COR) Alpha 𝜶 → OH points downward 3. CARBOXYLIC ACIDS (RCOOH) and (R1COOR2) Beta 𝛃 → OH points upward ORGANIC REACTIONS STEREOISOMERS ELECTROPHILE electron loving, electron poor 1. GEOMETRIC ISOMERS NUCLEOPHILE nucleus loving, electron rich Exhibited by alkenes and cycloalkanes Donates electron to electrophile ➔ Acyclic = Cis-trans isomerism PROTONATION movement of one electron pair of a ➔ Cyclic = Cis-trans isomerism is attached to a double bond towards a proton cyclic structure proton is acting as an electrophile, attacking an electron pair in the double 2. CONFORMATIONAL ISOMERS bond Duality of the atom to flex or bend (reason is its CARBOCATION species with a positively charged carbon rotation along a single bond and torsional strain) atom ➔ Acyclic = stability, eclipsed formation, staggered FUNCTIONAL controls the reactivity of a molecule the formation, torsional strain GROUP higher the number of functional group and electronegative ➔ Cyclic Almost unstable functional group atoms on the FG = higher reactivity = lower stability 3. CONFIGURATIONAL ISOMERS Compounds that exhibit OPTICAL ACTIVITY SUMMARY OF ORGANIC REACTIONS ➔ a process which enables compound to rotate plane polarized light either to the left or right ✏️ REMEMBER 1. RADICAL SUBSTITUTION 1. Alkanes DEXTROROTATORY → right or ( d/+) 2. ELECTROPHILIC ADDITION 1. Alkenes LEVOROTATORY → left or (l / -) 2. Alkynes 3. ELECTROPHILIC SUBSTITUTION 1. Aromatics 4. OTHERS Exclusive to cyclic A. MESO COMPOUNDS structures 4. NUCLEOPHILIC ADDITION 1. Aldehydes have two chiral carbons that mirror each other 2. Ketones 5. NUCLEOPHILIC SUBSTITUTION 1. Alkyl Halides B. DIASTEREOMER 2. Alcohols 3. Amines more than 1 but not all are different 4. Carboxylic Acids Ex. D-mannose and D-galactose (COOH) C. ENANTIOMER mirror images but NOT superimposable Example: 1. D-glucose and L-glucose 8  TOPIC 3 IMPORTANT ALCOHOLS 9  IMPORTANT ALCOHOLS 7. PHENOL / CARBOLIC ACID Use as disinfectant for surgical instruments and 1. METHANOL utensils, etc (used in hospital) aka WOOD ALCOHOL Starting material in the manufacture: ➔ formerly obtained from destructive distillation 1. Aspirin ➔ Used to produce formaldehyde (a preservative) 2. Detergents A starting material for many plastics 3. Dyes (colorants) 4. Herbicides Good denaturant for ETHYL ALCOHOL 5. Explosives ➔ makes ethyl alcohol UNFIT for drinking ➔ because of its taste and POISONOUS properties 8. CRESOL 2. ETHANOL aka SAPONATED CRESOL (LYSOL ) Ⓡ Used as disinfectant which is BETTER and LESS Other names: TOXIC than phenol a. GRAIN ALCOHOL b. WINE SPIRIT c. SPIRITUS VINI RECTIFICATUS ALCOHOL PRESENT IN ALCOHOLIC BEVERAGES 9. RESORCINOL ✏️ REMEMBER It is obtained from FERMENTATION OF SUGARS AND Used as an antiseptic BUT NOT AS GOOD as STARCH PHENOL 70% solution → used as an antiseptic Solvent in medicinal preparations → preparation of RANK OF ANTISEPTIC & DISINFECTANT PROPERTY TINCTURES! ➔ CRESOL > PHENOL > RESORCINOL Unfit for use in intoxicating beverages by addition ➔ C (1) , P (2), R (3) of denatured alcohol (contains methanol and benzene) 10. HEXYLRESORCINOL Much better antiseptic and germicide property than resorcinol 3. ISOPROPYL ALCOHOL Commonly used in mouthwashes Component of RUBBING ALCOHOL Used as solvent like ethanol BUT not in medical preparation Intermediate in the production of ACETONE 11. MENTHOL From OIL OF PEPPERMINT 4. CHOLESTEROL 12. GERANIOL Complex alcohol that occurs in nature STEROL found in a cell membrane (CM) of animal From ROSE OIL cells USE: precursor for the synthesis of sex hormones and bile acids 13. GLUCOSE A carbohydrate basic unit 5. GLYCEROL Use in the manufacture of certain plastics (Methanol is starting Material) Solvent in liquid medications being a non-toxic ingredient in cosmetic formulation due to its moisturizing property Main constituent of suppositories 6. ETHYLENE GLYCOL Anti-freeze for automobiles Solvent HUMECTANT → aids in retaining moisture 9  QUIZ 1. 70% solution of this alcohol is ETHANOL used as antiseptic 2. A type of alcohol which is an ISOPROPYL ALCOHOL intermediate in the production of acetone 3. What is the brand name of LYSOL Saponated cresol 4. This type of alcohol is PHENOL / CARBOXYLIC ACID discovered by Joseph Lister and used it as disinfectant ❗BEQ 5. Commonly found and used as ETHYLENE GLYCOL anti-freeze in automobile 6. Aside from being used as an GLYCEROL ingredient in the manufacture of plastics, it is also a main constituent in the production of suppositories NOTE: Familiarize the brand names of pharmaceutical products (drugs, cosmetics, cleaning agents) 10  TOPIC 4 IMPORTANT ETHERS 11  IMPORTANT ETHERS 4. EUGENOL An important ether obtained from CLOVE OIL 1. DIETHYL ETHER When it is mixed with Zinc Oxide (ZnO), it forms a Once widely used as GENERAL ANESTHETIC CEMENT (used by dentists as temporary fillings) (induces sleepiness) ➔ it is safe in long surgical procedures Dangerous since it has an explosive property 5. NAPROXEN Solvent for waxes and fat Not really under ethers ADVERSE DRUG REACTION (ADRs) NSAID (Nonsteroidal Anti-inflammatory) used for pain relief, inflammation reduction and fever Irritates the mucous membranes reduction N/V Treat arthritis, menstrual cramps and other musculoskeletal conditions CHEMICAL STRUCTURE 2. ETHYLENE OXIDE Gas sterilant No ETHER (organic compounds with oxygen atoms Used to fumigate textiles and grains bonded to 2 alkyl or aryl groups) as FG ➔ FUMIGATE = Process of using chemical Contains CARBOLIC FG (COOH) substances in the form of fumes or gasses to AROMATIC RING → responsible for the eliminate pests, pathogens or any unwanted anti-inflammatory and analgesic property organisms in the object ➔ FUMIGATION = It is process itself; to control unwanted organisms on the object Raw material in the synthesis of other organic compounds 3. MONOBENZONE COSMETIC ingredient in whitening preparations MOA: ➔ Inhibits the formation of melanin ➔ if excessive = decreases to lighten or depigment skin PROS Depigmenting agent in cases of excessive melanin formation ➔ Normally, high melanin → brown complexion ➔ Using monobenzone → lighter effect (not its indication) Reduced melanin formation can be seen in whitening preparation Lightens the skin CONS Regulatory restrictions in other countries due to safety and potential S/E of prolonged usage of the product can lead to uneven skin color distribution, sensitivity to sunlight and other skin related conditions As pharmacists, educate and patient counseling of its disadvantages 12  TOPIC 5 IMPORTANT aldehydes 13  IMPORTANT ALDEHYDES 5. BENZALDEHYDE Before, it is called “OIL OF BITTER ALMOND” 1. FORMALDEHYDE ➔ present in almond seed Preservative for anatomical specimens because it Used as a flavoring agent causes skin hardening Intermediate in the manufacture: Effective disinfectant used in hospitals as embalming 1. Drugs fluid (FORMALIN - embalming fluid ) 2. Dyes 3. Other organic products ➔ NEVER MIX FORMALDEHYDE WITH SODIUM HYPOCHLORITE (a disinfectant) = Carcinogenic product by inhaling the fumes Creates a silver mirror on the walls of a test tube if 6. CINNAMALDEHYDE reacted with AgNO3 → TOLLEN’S TEST Chief constituent of the OIL OF CINNAMON BARK Responsible for the characteristic aroma and flavor NOTE: MEDICAL SCHOOL → used in cadavers for of cinnamon specimens THERAPEUTIC PROPERTIES 1. Anti-inflammatory effects 2. ACETALDEHYDE 2. Anti-oxidant ➔ helps and protects the cells from oxidative An intermediate in the manufacture of: stress and damage 1. Acetic 2. Ethyl acetate 3. Antimicrobial property 3. Vinyl acetate ➔ an effect against various microorganisms such Used in the production of synthetic rubber and as bacteria and fungi, for producing new water-based paints antimicrobial agents) 4. Neuroprotective effects ➔ implications for elderly with neurodegenerative disorders) 3. CHLORAL HYDRATE AKA KNOCKOUT DROPS ➔ placed in hankys and inhaled 7. VANILLIN Dissolves starch, resin, proteins Sedative and hypnotic medication Fragrant component of VANILLA BEANS ➔ insomnia Flavoring Agent ➔ pre anesthetic agent before surgery operation Cosmetics and perfumery → pleasant and familiar (should be metabolized first to be active) aroma makes it popular choice for various products TRICHLOROACETIC ACID (TCA) POTENTIAL PHARMACEUTICAL APPLICATION Metabolite 1. Antioxidant property Compound which forms as a result of the 2. Anti-inflammatory effects metabolism of chloral hydrate in the liver 3. Potential for having neuroprotective property Known toxic effects in liver and kidneys 4. Antimicrobial property 5. Cancer investigation/research ➔ potentially inhibits the growth of certain cancer cells) 4. BUTANAL AKA BUTARALDEHYDE Constituent of the aroma of fresh bread 8. CITRAL Strong pungent odor often described having similar smell of a rancid butter Major component of LEMON GRASS OIL Aldehyde USES OTHER USES 1. Starting material of different products 2. Natural component of essential oils which 1. Perfume contributes to characteristic flavor 2. Flavoring 3. Industrial production of plastics, resins, other 3. Antimicrobial chemicals 4. Anti-inflammatory 5. Anti-cancer (investigational stage) 14  TOPIC 6 IMPORTANT KETONES 15  IMPORTANT KETONES 4. MUSCALINE Pheromone produced by HOUSE FLIES 1. ACETONE Used as a solvent for products such as paints, lacquers and cellulose acetate because it is miscible with water and non-polar liquids 5. CHLOROACETOPHENONE USE: Nail polish remover Has a frothy smell → addictive Used as a lacrimator because it irritates the eyes ➔ drops for eye tearing like for actings Used as a tear gas 2. TESTOSTERONE Major constituent of the male sex hormones 6. PEPPER SPRAY Responsible for the development of secondary sex characteristics Contain “CAPSAICIN” Directly related to steroidal ketone ➔ constituent obtained from chili 3. MUSCONE 7. ACETOPHENONE Odorous principal component of MUSK (sex Has been used as a hypnotic but NOT USED attractant) ANYMORE → there’s already newer and safer drugs Released by a microorganism which helps for in the market sexual attraction Valued for its ability to enhance fragrances even when present in minute amounts → very potent Present in many of the expensive perfumes ➔ Perfumery (Use: fixative) 8. METHYL ETHYL KETONE (MEK) ➔ Some expensive perfume lines contain Solvent for lacquers, paints and plastics muscone MUSK natural substance with a strong sweet smell PHEROMONES produced by musk to attract sex, triggers sexual desire NOTE: A movie used a liquid which is sprayed to attract sexual desire 16  TOPIC 7 IMPORTANT ACIDS 17  IMPORTANT ACIDS 6. TARTARIC ACID Found in several fruits, particularly GRAPES 1. SALICYLIC ACID DIPROTIC ACID → able to transfer 2 protons MONOPROTIC ACID ➔ as an acid, it can donate 1 protein per 1 SALTS OF TARTARIC ACID molecule that undergoes dissociation 1. POTASSIUM HYDROGEN TARTRATE Used for the treatment of fungal infection and AKA CREAM OF TARTAR removal of warts and corns (found in feet) Use: in making baking powder Used as a keratolytic agent for the removal of dead skin cells 2. POTASSIUM SODIUM TARTRATE IMPORTANT PREPARATION Use: mild cathartic WHITFIELD’S OINTMENT Benzoic acid + Salicylic acid antifungal property to treat various fungal skin 7. BENZOIC ACID infections: 1. Ringworm MONOPROTIC ACID 2. Athlete’s foot Use: Antifungal agent 3. Jock itch 4. Fungal nail infection FORM SODIUM BENZOATE sodium salt used as a food preservative 2. ACETYLSALICYLIC ACID (ASPIRIN) THERAPEUTIC PROPERTIES 8. PARA-AMINOBENZOIC ACID 1. Analgesic AKA PABA 2. Antipyretic Used in suntan lotions to prevent the dangerous UV USE rays from reaching the skin Use sunblock even inside the house due to the UV 1. Treatment of colds rays emitted in gadgets which can cause skin 2. Headache pigmentation 3. Minor aches 4. Pains 9. ACETIC ACID VINEGAR, SPERMATOCIDE 3. ACETAMINOPHEN (PARACETAMOL, USP) Considered to be a universal precursor for: Substitute for ASPIRIN 1. Fatty acids 2. Lipids 3. Other organic plant products 4. CITRIC ACID GLACIAL ACETIC ACID TRIPROTIC ACID → can donate 3 protons AKA ETHANOLIC ACID Found in CITRUS FRUITS Important compound 5. LACTIC ACID SUPPLEMENTAL STUDY MATERIALS Found in SOUR MILK GenChem, OrgChem and OrgMedChem - RJAB Formed during fermentation of milk sugar (Lactose) InorganicChem - Laurete Responsible for the souring of spoiled milk Module 1 Pacop - Green and Pink LACTOSE Product of fermentation 18