Organic Reactions Susbstitution S N. Dr. Sapna Gupta
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1 Organic Reactions Susbstitution S N 2 Dr. Sapna Gupta
2 Kinetics of Nucleophilic Reaction Rate law is order of reaction 0 order is when rate of reaction is unaffected by change in concentration of the reactants 1 st order is when rate of reaction doubles when one of the reactants is doubled 2 nd order is when rate of reaction quadruples when two of the reactants are doubled Order of reaction explains the reaction mechanism Dr. Sapna Gupta/Substitution Reactions 2
3 Nucleophilic Substitution Reactions In this reaction a nucleophile is a species with an unshared electron pair which reacts with an electron deficient carbon A leaving group is substituted by a nucleophile Examples of nucleophilic substitution Dr. Sapna Gupta/Substitution Reactions 3
4 The S N 2 Reaction 2 nd order substitution reaction S=substitution N (subscript) = nucleophilic 2 = (bimolecular) both nucleophile and substrate in characteristic step Inversion of stereochemistry occurs Dr. Sapna Gupta/Substitution Reactions 4
5 An S N 2 Reaction The initial rate of the following reaction is measured The rate is directly proportional to the initial concentrations of both methyl chloride (substrate) and hydroxide (nucleophile) 3 The rate equation reflects this dependence S N 2 reaction: substitution, nucleophilic, 2nd order (bimolecular) Dr. Sapna Gupta/Substitution Reactions 5
6 A Mechanism for the S N 2 Reaction A transition state is the high energy state of the reaction It is an unstable entity with a very brief existence (10-12 s) In the transition state of this reaction bonds are partially formed and broken Both chloromethane and hydroxide are involved in the transition state and this explains why the reaction is second order Dr. Sapna Gupta/Substitution Reactions 6
7 S N 2 Energy Diagram One-step reaction. Transition state is highest in energy. Dr. Sapna Gupta/Substitution Reactions 7
8 Examples of Nucleophilic Substitution Negatively charged nucleophiles like HO and HS are used as salts with Li +, Na +, or K + counterions to balance the charge. Since the identity of the counterion is usually inconsequential, it is often omitted from the chemical equation. When a neutral nucleophile is used, the substitution product bears a positive charge. Dr. Sapna Gupta/Substitution Reactions 8
9 Uses for S N 2 Reactions Synthesis of other classes of compounds. Halogen exchange reaction. Dr. Sapna Gupta/Substitution Reactions 9
10 Factors Affecting S N 2 1. Nucleophile Strength 2. Size of the nucleophile 3. Substrate (steric effect) 4. Leaving group 5. Effect of solvent Dr. Sapna Gupta/Substitution Reactions 10
11 1) Nucleophilic Strength Stronger nucleophiles react faster. Strong bases are strong nucleophiles, but not all strong nucleophiles are basic*. Strength of Nu is based on: Charge: In a conjugate acid-base pair, the base (anion) is stronger: OH - > H 2 O, NH 2- > NH 3 Periodicity: Decreases left to right on the Periodic Table. More electronegative atoms less likely to form new bond: OH - > F -, NH 3 > H 2 O Size: Increases down Periodic Table, as size and polarizability increase: I - > Br - > Cl - * Bases are characterised by their ability to abstract a proton while nucleophiles reacts with electrophiles. Dr. Sapna Gupta/Substitution Reactions 11
12 Nucleophiles Some examples Dr. Sapna Gupta/Substitution Reactions 12
13 2) Size of Nucleophile Larger nucleophiles are not good for S N 2 because they will not be able to access the electrophilic carbon. E.g. EtO better than tbuo - even though tbuo - is a stronger base. Note: Alkoxides as Nucleophiles. CH 3 O - Na +, CH 3 CH 2 O - K + - alkoxides are synthesized as salts potassium or sodium. They are synthesized by dissolving solid sodium or potassium in the respective alcohol in a moisture and oxygen free environment. CH 3 OH + Na CH 3 O - Na + + H 2 Nomenclature: CH 3 O - Na +, sodium methoxide, CH 3 CH 2 O - K + potassium ethoxide, (CH 3 ) 3 CO - Na + sodium t-butoxide Dr. Sapna Gupta/Substitution Reactions 13
14 3) Substrate: Steric Hindrance - 1 Nucleophile approaches from the back side hence the electrophilic carbon should not be hindered. Best substrates for S N 2 are primary halides. 1 o > 2 o >3 o Dr. Sapna Gupta/Substitution Reactions 14
15 3) Substrate: Steric Hindrance - 2 The more alkyl groups connected to the reacting carbon, the slower the reaction Dr. Sapna Gupta/Substitution Reactions 15
16 4) Leaving Group Should be electron-withdrawing to provide an electrophilic carbon Stable once it has left (not a strong base) Usually halides are good LG. Weaker bases make best LG. NOTE: weaker base cannot displace stronger base in a S N 2 reaction Examples of leaving groups Dr. Sapna Gupta/Substitution Reactions 16
17 5) Solvents 3 kinds of solvents Solvent Polar protic polar aprotic non polar Examples H 2 O CH 3 OH, CH 3 CH 2 OH DMF (dimethyl formamide), DMSO (dimethyl sulfoxide) Shown below. Hexane Toluene Diethyl ether Dichloromethane Comments Will form H-bonds with Nu and therefore need more energy to form transition state Does not form H- bond with Nu but still helps to solvate ions hence the best kind for S N 2 Not good for S N 2 since they will not stabilize the ions formed. Dr. Sapna Gupta/Substitution Reactions 17
18 The Stereochemistry of S N 2 Reactions Backside attack of nucleophile results in an inversion of configuration In cyclic systems a cis compound can react and become trans product Dr. Sapna Gupta/Substitution Reactions 18
19 S N 1 Reaction Unimolecular nucleophilic substitution. Two step reaction with carbocation intermediate. Rate is first order in the alkyl halide, zero order in the nucleophile. Racemization occurs. Dr. Sapna Gupta/Substitution Reactions 19
20 The S N 1 Reaction Mechanism Dr. Sapna Gupta/Substitution Reactions 20
21 S N 1 Energy Diagram There are three transition states. Step1 crosses the highest energy barrier and is rate determining Dr. Sapna Gupta/Substitution Reactions 21
22 Stereochemistry of S N 1 Racemization: inversion and retention Dr. Sapna Gupta/Substitution Reactions 22
23 Factors Affecting Rates of S N 1 Reactions 1. Substrate: 3 > 2 > 1 >> CH 3 X 2. Leaving group: should be weak base(like S N 2) 3. Nucleophile: no effect since its not part of the transition state but in general weak Nu can also react. 4. Solvent: Polar protic solvent best, it solvates ions strongly with hydrogen bonding. Dr. Sapna Gupta/Substitution Reactions 23
24 1) Nature of Substrate Substrate: 3 > 2 > 1 >> CH 3 X a) Order follows stability of carbocations (opposite to S N 2) b) More stable ion requires less energy to form c) Resonance can also stabilize cation (e.g. allyl cation C=C-C + ) Dr. Sapna Gupta/Substitution Reactions 24
25 2) Leaving Group Leaving group is key in forming the carbocation intermediate for transition state. Larger halides ions are better leaving groups In acid, OH of an alcohol is protonated and leaving group is H 2 O, which is still less reactive than halide p-toluenesulfonate (TosO - ) is excellent leaving group 3) Nucleophile Does not matter since nucleophile is not part of the rate determining step. Dr. Sapna Gupta/Substitution Reactions 25
26 4) Solvent Polar solvents help with ionization and stability of the carbocation. Dr. Sapna Gupta/Substitution Reactions 26
27 S N 2 or S N 1? S N 2 S N 1 Substrate Primary or methyl Tertiary Nucleophile Strong nucleophile Weak nucleophile (may also be solvent) Solvent Polar aprotic solvent Polar protic solvent, silver salts Kinetics [substrate][nu] [substrate] Stereochemistry Inversion Racemic mixture Rearrangement No Yes Dr. Sapna Gupta/Substitution Reactions 27
28 Solved Problems Predict mechanism and stereochemistry of each product Cl + (R)-2-Ch lorobutane CH 3 OH/ H 2 O OH OCH HCl Predict mechanism of the following reaction Br + Na + CN - CN + DMSO Na + Br - Predict mechanism and stereochemistry of each product Br CH 3 S - Na + Na + Br - + acetone + SCH 3 (R)-2- Bromobutane Dr. Sapna Gupta/Substitution Reactions 28
29 Key Words/Concepts Substitution Reaction Nucleophile Electrophile Leaving group 1 st order reaction (unimolecular) 2 nd order reaction (bimolecular) Transition state Rate determining step Carbocation Polar protic solvent Polar aprotic solvent Non polar solvent Solvolysis
Organic Reactions Susbstitution S N. Dr. Sapna Gupta
Organic Reactions Susbstitution S N 2 Dr. Sapna Gupta Kinetics of Nucleophilic Reaction Rate law is order of reaction 0 order is when rate of reaction is unaffected by change in concentration of the reactants
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