EXPERIMENTAL ORGANIC CHEMISTRY. LABORATORY MANUAL

• Chapter 1: Laboratory Safety
1.1 The lab as a safe place
1.2 Personal protective equipment
1.3 Emergency equipment for general purpose
1.4 GHS for classification and labeling of chemicals
1.5 Chemical incompatibility and storage
1.6 Substances with risk of fire and explosion
1.7 Waste treatment and disposal
• Chapter 2: Lab Notebook
2.1 Notebook structure
2.2 Experiment report for a practice course
2.3 Some guidelines for keeping a notebook
2.4 Example of an experiment description
2.5 Basic calculations
• Chapter 3: Laboratory Equipment
3.1 Introduction
3.2 Manufacture of lab equipment
3.3 Cleaning of glassware
3.4 General-purpose glassware
3.5 Fastening and anchoring
3.6 Pressure and vacuum equipment
3.7 Pressure reactors and hydrogenators
3.8 Other materials
• Chapter 4: Basic Laboratory Operations
4.1 Introduction
4.2 Weighing of solids and liquids
4.3 Measurement of liquid volumes or solutions
4.4 Transfer of solids and liquids
4.5 Techniques used in chemical reactions
4.6 Reflux
4.7 Isolation and purification of solids
4.8 Liquid-liquid extraction
4.9 Solid-liquid extraction (Soxhlet)
4.10 Removal of solvents under reduced pressure (rotary evaporator)
4.11 Distillation
4.12 Reactions in an inert atmosphere
4.13 Reaction and removing of gaseous products
4.14 Chromatographic techniques
• Chapter 5: Determining Physical and Spectroscopic Properties
5.1 Introduction
5.2 Determining physical properties
5.3 Determining spectroscopic properties
5.4 Preparation of samples for spectroscopy
• Chapter 6: Functional-Group Analysis
6.1 Introduction
6.2 Qualitative elemental analysis
6.3 Organoleptic and physical properties
6.4 Classification by solubility (solubility tests)
6.5 Functional-group analysis
6.6 Identification of an unknown substance
• Chapter 7: Basic Operation Experiments
7.1 Recrystallization and solubility tests: from water and from organic solvents
7.2 Stirring and decanting: preparing biodiesel from cooking oil
7.3 Simple distillation: isolation of alcohol from wine
7.4 Extraction and “rotary evaporator”: obtaining cloves and cinnamon oils
7.5 Liquid-liquid extraction (with centrifuge): isolation of caffeine from soluble coffee
7.6 Liquid-liquid extraction (with separatory funnel): separating components of a mixture
7.7 Reflux, simple, and fractional distillation: ethyl acetate preparation
7.8 Steam distillation and vacuum distillation: isolation of limonene from citrus peel
7.9 Solid-liquid extraction (Soxhlet): sunflower oil from seeds
7.10 TLC and CC chromatography: separation of the pigments from spinach leaf
Chapter 8: Organic Synthesis Experiments
8.1 Alkene oxidation: preparation of adipic acid from cyclohexene
8.2 Dehydration of alcohols: synthesis of cyclohexene from cyclohexanol
8.3 Oxidation of alcohols: 4-chlorobenzoic acid from 4-chlorobenzyl alcohol
8.4 Nucleophilic substitution reactions: synthesis of 1-bromobutane
8.5 Synthesis of an ether: preparation of ß-naphthyl methyl ether
8.6 Aromatic electrophilic substitution of an ester: methyl benzoate nitration
8.7 Electrophilic aromatic substitution (SEAr): preparation of a synthetic detergent
8.8 Synthesis of azo dyes: methyl orange
8.9 Auto-oxidation-reduction of aromatic aldehydes: cannizzaro reaction
8.10 Synthesis of a, ß-unsaturated ketones: Claisen-Schmidt reaction
8.11 Saponification reaction: preparation of soap from vegetable oil
8.12 Esterification: synthesis of aspirin
8.13 Difunctional compound chemoselectivity: reduction of 4-nitroacetophenone
8.14 Perkin reaction: cinnamic acid synthesis
8.15 Synthesis of imide: preparation of N-(p-chlorophenyl)-maleimide
8.16 Condensation polymerization reaction: synthesis of nylon 6,6
8.17 Radical polymerization: producing polystyrene
8.18 Multistep synthesis of a drug: paracetamol
8.19 Multistep synthesis of an anesthetic: preparation of benzocaine
8.20 Using protecting groups: multistep synthesis of p-nitroaniline
• Chapter 9: Advanced Organic Synthesis Experiments
9.1 Reductive amination: producing (±)-a-methylbenzylamme
9.2 Chiral resolution: (±)-a-methylbenzylamme
9.3 Stereospecific synthesis of glycols: preparation of trans-cyclohexane-1,2-diol
9.4 Reactivity of carbenes: preparation of 7,7-dichlorobicyclo [4.1.0] heptane
9.5 Regioselective halogenations: bromation of a-methylstyrene
9.6 Oxidative coupling of alkynes: the Glaser-Eglinton-Hay coupling
9.7 Diels-Alder reactions: butadiene and maleic anhydride
9.8 Wittig reaction: 4-vinylbenzoic acid synthesis
9.9 Grignard reagents: synthesis of triphenylmethanol (triphenylcarbinol)
9.10 Organometallic compounds: synthesis of acetylferrocene
9.11 Chemoselectivity: cinnamaldehyde reduction with LiAlH4
9.12 Electrophilic aromatic substitution (SEAr): 1,4-di-tert-butylbenzene
9.13 Hofmann rearrangement: synthesis of 2-aminobenzoic acid (anthranilic acid)
9.14 Radical coupling: synthesis of pinacol and pinacolone
9.15 Synthesis of a heterocyclic drug: n-butylbarbituric acid
9.16 Transformations of hydroxy ketone: synthesis and reactions of benzoin
9.17 Enamines as reaction intermediates: producing 2-acetylcyclohexanone
9.18 N-Heterocycle synthesis: producing benzotriazol
9.19 Synthesis of macrocycles: preparation of calix[4]pyrrole
9.20 Preparation of a sports dietary supplement: creatine synthesis
9.21 Claisen condensation: synthesis of ethyl acetoacetate
9.22 Terpene transformation: citral conversion in a- and ß-ionone
9.23 Carbohydrates: diisopropylidene derivative of glucose
9.24 Preparation of a nucleoside: multistep synthesis of uridine derivative
• Chapter 10: Microscale
10.1 Introduction
10.2 The scales in the Organic Chemistry laboratory
10.3 Pros of working at the microscale
10.4 Specific microscale lab equipment
10.5 Microscale laboratory techniques
• Chapter 11: Microscale Experiments
11.1 Addition of HX to alkenes: synthesis of 2-bromohexane
11.2 Production of margarine: partial hydrogenation of a vegetable oil with cyclohexene and Pd(C)
11.3 Isomerization of alkenes: derivatives of fumarie acid from maleic acid
11.4 Nucleophilic substitution reaction: ethyl iodide from ethanol
11.5 Methylketone reactivity: acetophenone oxidation with sodium hypochlorite
11.6 Electrophilic aromatic substitution (SEAr): preparation of 4-methyl-3- and 4-methyl-2-nitroacetanilide from 4-methylaniline
11.7 Sandmeyer reaction: 2-iodobenzoic acid synthesis
11.8 Synthesis of a carbohydrate derivative:preparation of 2,3:5,6-di-O-isopropylidene-a-d-mannofuranose
11.9 Free-radical halogenation: 9-bromoanthracene preparation
11.10 Alkylbenzene oxidation: reactivity of alkyl groups in aromatic compounds with KMnO4
11.11 Reduction of anthraquinone: anthrone synthesis
11.12 Compounds for the fragrance industry: ester synthesis
11.13 Tandem transesterification-esterification: wintergreen oil from aspirin tablets
11.14 Polyfunctional molecule reactivity: vanillin transformations
11.15 Multistep synthesis of N-heterocycles: triphenylpyridine preparation
11.16 Synthesis of five-membered heterocycles: 2,5-dimethyl-1-phenylpyrrole by Paal-Knorr reaction
Chapter 12: Green Chemistry
12.1 Introduction
12.2 The 12 principles of Green Chemistry
12.3 Goals of Green Chemistry
12.4 Parameters to evaluate chemical processes
12.5 Green Chemistry for undergraduate laboratories
• Chapter 13: Green Chemistry Experiments
13.1 Oxidative cleavage of alkenes: producing adipic acid with H2O2/Na2WO4
13.2 Halogen addition to alkenes: addition of bromine to cyclohexene
13.3 Green epoxidation: cyclohexene reaction with Oxone®
13.4 Acylation of aromatic amines: obtention of acetanilide with acetic acid and Zn
13.5 Solvent-free reductive amination: preparation of dibenzylamine hydrochloride
13.6 Friedel-Crafts alkylation: xylene reaction with 2-bromopropane catalyzed with graphite
13.7 Regiospecific nitration of phenols: obtention of ortho-nitrophenol
13.8 Oxidation of aromatic aldehydes: reaction of benzaldehyde with Oxone®
13.9 Green synthesis of ethers: preparation of benzyl butyl ether
13.10 Synthesis of an acetal in water: preparation of 5,5-bis(hydroxymethyl)-2-phenyl-1,3-dioxane
13.11 Reduction of a ketone alkaline solution: cyclohexanone reaction with NaBH4
13.12 Solvent-free Baeyer–Villiger reaction: oxidation of 4-tert-butylcyclohexanone
13.13 Enzymatic reduction of ß-ketoesters: synthesis of chiral ethyl 3-hydroxybutanoate
13.14 C–C Bond forming: suzuki reaction
13.15 C=C Bond formation in the absence of solvent: the Wittig reaction
13.16 Diels-Alder in water: reaction of 9-anthracenemethanol with N-methylmaleimide
13.17 Green synthesis of a p-cymene: preparation of p-cymene from limonene
13.18 Oxidative coupling reaction in water: synthesis of racemic 1,1'-bi-2-naphthol
13.19 Organic compounds from recycled polymer: phthalate derived from PET
13.20 Crosslinked biodegradable polymers: producing slime
13.21 Polymers from renewable raw materials: starch
13.22 Organocatalysis: reaction of 4-nitrobenzaldehyde and dimedone
13.23 Knoevenagel-Pinner reactions in water: synthesis of 7-hydroxy-3-carboxycoumarin
13.24 Biginelli reaction: synthesis of tetrahydropyrimidinone
13.25 Multi-component synthesis in water: Passerini reaction
13.26 Preparation of a dipyrrol derivative in water: meso-diethyl-2,2'-dipyrromethane
13.27 Ionic liquid in water: one-pot 1-butyl-3-methylimidazolium derivative preparation
13.28 Beckmann rearrangement: synthesis of laurolactam from cyclododecanone
13.29 Fluorescent natural product: preparation of 7-hydroxy-4-methyl-2H-chromen-2-one
13.30 Photochemical solid phase: [2+2] cycloaddition of cinnamic acid

• Organizes lab course coverage in a logical and useful way
• Features a valuable chapter on Green Chemistry Experiments
• Includes 84 experiments arranged according to increasing complexity

Authors
• Joaquín Isac-García, Universidad de Granada, Spain
• José A. Dobado, Universidad de Granada, Spain.
• Francisco G. Calvo-Flores, Universidad de Granada, Spain.
• Henar Martínez-García, Universidad de Valladolid, Spain