UNIT - V ORGANIC REACTIONS 5.1 BASIC CONCEPTS OF ORGANIC REACTIONS Carbonium ion or Carbocation Organic ions which contain a positively charged carbon atom are called carbonium ion or carbocation. | C2 Carbonim Ion Where, Z is more electronegative than carbon. Example: CH}, CH,CH} and (CHs), C* Carbanions Organic ions which contain a negatively charged carbon atom are called carbanions. | oe ae aid Where, Z is less electronegative than carbon. Carbanion Example: CH352 Engineering Chemistry Free Radicals Free radical is an atom or group of atoms containing odd or unpaired electron. Methyl free radical (CH3), ethyl free radical, chlorine free radical (CI*) are some of the examples. Carbenes Carbenes are neutral divalent chemical species which contain a carbon atom having 6 electrons in their valence shell out of which 2 are unshared. z Carbene Example: Methylene (: CH), dichlorocarbene (: CC) Electrophiles A reagent which can accept an electron pair in a reaction is called electrophile. It contains electron deficient atoms. Examples: H’*,Cl*, Br*, NO}, BF3, AIC; etc. Nucleophiles A reagent which can donate an electron pair in a reaction is called nucleophile. It contains an atom having an unshared or lone pair of electrons. Examples: CI”, Br”, I”, CN”, OH’, H,0, NH etc.Organic Reactions 5.3 5.2 TYPE OF ORGANIC REACTIONS The reactions of organic compounds can be classified Cyclization Reaction Oxidation Reaction into: Addition Reaction Type of Reactions E ‘limination Reaction 5.3 SUBSTITUTION REACTION Reactions which involve the replacements or substitution of one or more atoms or groups or a compound by other atoms. or groups are known as substitution reactions. Example: UV light CH, + Cl, ——> CH,CI+HCI ‘Methane Methyl Chloride Types of substitution reaction 1. Electrophilic substitution reaction When a substitution reaction involves the attack by electrophiles, the reaction is referred to as electrophilic substitution reaction.54 Engineering Chemistry Example: The bromination of benzene in the presence of FeBr; FeBr, + Br, —> Br + HBr Benzene Bromo benzene 2. Nucleophilic substitution reaction When a substitution reaction involves the attack of a nucleophile, the reaction is referred to as nucleophilic sustitution reaction (Sy). S stands for substitution and N for a nucleophile. Example: Hydrolysis of alkyl halides by aqueous NaOH. RX +OH ——> Row+x- Nucleophile Leaving group 3. Free radical substitution reaction These reactions are initiated by free radicals. The chlorination of methane in the presence of ultraviolet light is an example of free radical substitution reaction. E nple: UV light CH Oa CHCl HCl Methane Methyl ‘Chloride 5.4 ADDITION REACTION Addition reactions are those in which atoms or groups of atoms are simply added to a double or triple bond without the elimination of any atom or other molecules. These reactions may be initiated by electrophiles, nucleophiles or free radicals.Qnganic Reactions Example: GREG Bs ae, C- oh Ethylene He Br Br 1,2-dibromoethane Types of addition reaction 1. Electrophilic addition reaction When an addition reaction involves the initial attack by an electrophile, the reaction is referred to as electrophilic addition reaction. S Example: The addition of HBr to ethylene. CH,=CH,+ HBr ——» ae es fe H Br Ethyl bromide 2. Nucleophilic addition reaction When an addition reaction involves the initial attack by a nuclephile, the reaction is referred to as nucleophilic addition reaction. ; Example: Aldehydes and ketones which contain carbon oxygen double bonds undergo such reactions. oy ll CH,-C-CH, + HCN ——> Cis tas poe CN Acetone Cyanchydrin 3. Free radical addition reaction Free radicals add to an unsaturated molecule to give a new radical intermediate which further reacts to give final product. The radical is generated by photolight or spontaneous dissociation.5.6 Engineering Chemistry Example: R-O-O-R —» 2RO+HBr —» ROH+ Br’ RB B ek hv os =C&qy + HBr arena Pa Alken Hydrogen —_peroxi i : halide aqueous conditions H H a are sufficient to Alkyl halide supply peroxide 5.5 ELIMINATION REACTION . Elimination reactions are reverse of addition reactions. Two or four atoms or groups attached to the adjacent carbon atoms in the substrate molecule are eliminated to form a multiple bond. Example: The dehydrohalogenation of alkyl halides with alcoholic alkalis. R-cH,-cH-x HL R-CHaCH, + H,0 +x” Types of elimination reaction 1, E2 reaction E2 stands for bimolecular elimination. When the rate of an elimination reaction depends upon the concentration of a substrate and nucleophile, the reaction is of second order and is represented as E2. Example: R-cH,-cH,x 8 R-cHecH, + 4,0 +x- 2. E1 reaction El stands for unimolecular elimination. When the rate of an elimination reaction depends only on the concentration of the substrate, the reaction is of first order and is designed as El.A nnnsessiniiidiiinsaainaatonse Organic Reactions 57 Example: Step 1: The alkyl halide ionizes to give the carbonium ion. cH, CH, cy} —- cx, —e + Bro CH, CH, Sect-baty! bromide Carbonim Ion Step 2: A proton is abstracted by the base from the adjacent B-carbon atom to give the alkene. CH, ony CH, oye a no iy HO) CH, CH, Carbonim Ton 2-Methyl propene 5.6 OXIDATION REACTION Oxidation is defined as the addition of oxygen or removal of hydrogen from a compound. ° 9 I {0} I C. aes HCC a HC OH Acetaldehyde Acetic acid Example: Aldehydes are oxidized to form acids. Some typical oxidation reactions 1. Alkenes are oxidized to glycols with cold dilute potassium permanganate. we-cH, eH panel cae OH OH Ethylene glycolXS 58 Engineering Chemistry 2. Treatment of alkenes with hot alkaline potassium permanganate results in the cleavage of the molecule at the 1 bond. 9 [0] ll aes a H,C~ Non (2-Butene Acetic acid 3. Alcohols and aldehydes when oxidized with a mixture of potassium dichromate and sulfuric acid ultimately yield carboxylic acids. [Oo] noe ae om +o Ethanol Acetaldehyde co OH o7™ ae pe 0 Acetaldehyde Acetic acid 5.7 REDUCTION REACTION Reduction is defined as the addition of hydrogen to an organic compound or replacement of oxygen by hydrogen. Example: uc-cn, “1, H,C-CH, Ethylene Ethane ° H im, “cy HC H,C-cH, i Ethylene Ethane 2. Reduction with Lithium aluminium hydride Lithium aluminium hydride general reducing agent for aldehydes, ketones and nitriles. } Example: In this method, the compound is first treated with LiAIHy and then water. ° OH il () LialH, L c. e aN, aa @HO H. HC” cu, bic BC ice Acetone Isopropyl alcohol 3. Reduction with metals Some metals have found use in the reduction of certain functional groups. Example: Treatment of nitrobenzene with iron fillings in hydrochloric acid yields aniline. Nitrobenzene Aniline5.10 Engineering Chemistry 5.8 RING OPENING REACTION A cyclic ring opening reaction is a reaction in which a % bond of a cyclic reactant is cleaved to form a conjugated product with one more 7 bond. Fy aay 1,2 dimethyl cyclobut-3-ene Hexa-2,4-diene Example: Type of ring opening reactions 1. Electrocyclic ring opening reaction In the electrocyclic ring opening, a C— Co bond breaks to give a conjugated m system in which the termini used to be bound. Example: a 4 ~~ Za J ES) — Cyclobutene 1,3 butadiene 2. Ring opening reactions of epoxides Depending upon the nature of epoxides and on the reaction conditions, ring opening reaction can proceed by either Sy? or Sy! mechanismOrganic Reactions Example: Basic ring opening HG, Pr a NaOCH, He a HC’ 1H . HC cH, Acidic ring opening mea H,S0, HC. OH JA —— > com) — Sa ro 5 aoe : cs H,CO a 5) 5.9 CYCLIZATION An electrocyclic reaction is a type of pericyclic rearrangement where the net result id one m bond being converted into one o bond. Example: Gr —— YA Octa-2,4,6-triene 5,6-dimethyl-1,3-cyclohexadienc Type of cyclization reaction 1. Electrocyclic ring closure It is an intermolecular reaction that forms a cyclic product containing one more o bond and one fewer m bond than the reactant. g+Q Hexa-1,3,S-triene Benzene Example: (i) By heat5.12 Engineering Chemistry (ii) By photon hv or A i ‘1,3 Butadiene 2. Cycloaddition A cycloaddition reaction is a reaction between two compounds with = bonds to form a cyclic product with two Cyclobutene new o bonds. Example: (i) By heat a 7 cl “> S 1,3Buiadine Ethylene Cyclohexene COOCH, ‘OOCH, a A CC en ~ ‘COOH, COOCH, 1,3 Butadine (ii) By photon | bo + ae Ethylene Cyclobutane 5.10 DRUG A drug is any substance which, whrn taken into the body, alters the body’s function either physically and/or phychologically. Example: Analgesics, Anesthetics, Diuretics, Antipsychotics and Antibiotics.Organic Reactions 5.19 Synthesis of some commonly used drug molecules 1. Paracetamol © Paracetamol is known as acetaminophen and acetyl para aminophen (APAP), is a medicine used to treat pain and fever. It is typically used for mild to moderate pain relief. © It is widely used an analgestic and fever reducing agent. * The molecular formula of paracetamol is CsHoNO> — of Paracetamol deed 2-Nitrophenol 2 4-Nitrophenol al OH CH,COOH + Acetic acid a 4 ssh Y Paracetamol Steps: e Involves the nitration of phenol with sodium nitrate gives a mixture of two isomers namely 2-nitrophenoloe Engineering Chemistry and 4-nitrophenol which the wanted 4-nitrophenol (bp 279°C) can easily be separated by steam distillation. © The nitro group is then reduced to an amine, giving 4-aminophenol using sodium borohydride. © Finally, the resultant 4-nitrophenol is acetylated with acetic anhydride and it gives paracetamol. The product is washed, dried and recrystallized. 2. Aspirin © Aspirin also known as acetylsalicyclic acid, is a medication used to treat pain, fever, or inflammation © Aspirin exhibits analgesic, fever-reducing and anti-inflammatory action, reduces aggregation of thrombocytes. Aspirin given shortly after a heart attack decreases the risk of death. Synthesis of Aspirin O O Con.H,SO, oe DA ww Chow + HAC CH, oO ‘Acetic anhydride HC 2 Salicylic acid +CH,COOH Acetic acid OH Acetylsalicylic acidOrganic Reactions Steps: Salicylic acid interacts with acetic anhydride in the presence of few drops of concentrated sulfuric acid to gives aspirin and acetic acid. Questions iL 2. 33 4. 5. a2 ll. 12. Explain the following reactions with examples (i) Addition (ii) Elimination (iii) Substitution What are Electrophiles? Give two examples. Write an addition reaction with an example. (May 20/9) What are Nucleophiles? Give two examples. Write notes on: (i) Oxidation reaction and (ii) Reduction reaction. What is cyclization reaction? (May 2019) Explain any two common drug syntheses in detail? Mention the importance of the drug? (May 2019) What is ring opening reaction? Explain the following reactions with examples (i) Substitution (ii) Elimination and (iii) Oxidation (May 2019) Give an example for nucleophilic substitution reaction? (Dec 2018) Write the addition reaction of olefins. (Dec 2018) Explain the following with suitable examples. (i) Oxidation reaction (ii) Elimination reaction (Dec 2018) Explain in detail the (i) Cyclization reaction’ and (ii) Reduction reaction (Dec 2018) Give an example for electrophilic addition reaction? Explain the following terms: (i) Carbonium ion (ii) Carbanion (iii) Free radicals and (iv) Carbenes