2. Determine the product that would be formed from the S N 2 reaction of a. (R)-2-bromobutane and hydroxide ion (aprotic solvent) (S)-2-butanol

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1 1. Define and understand the following terms. (I will go over these if you have questions, but will expect that you have attempted to understand them on your own.) a. yperconjugation b. Basicity c. Nucleophile d. Nucleophilicity e. Electrophile f. Polarizability g. Aprotic solvent (give an example) h. Protic solvent (give an example) 2. Determine the product that would be formed from the S N 2 reaction of a. (R)-2-bromobutane and hydroxide ion (aprotic solvent) - - (R)-2-bromobutane (S)-2-butanol b. (S)-3-chlorohexane and hydroxide ion (aprotic solvent) - - (S)-3-chlorohexane (R)-3-hexanol 3. For each of the following pairs of S N 2 reactions, indicate which reaction occurs faster. a. C 3 C or C 3 C B/C - is better nuc than 2 b. C 3 C 2 + C 3 - or C 3 C 2 + C 3 S - in ethanol Ethanol is protic solvent, so C 3 S - is better nuc than C 3 - c. C 3 C 2 + I - or C 3 C 2 + I - in aprotic solvent B/C - is better LG (weaker base) than - 4. Determine the product(s) and indicate the probably mechanism (S N 1 or S N 2) for the following reactions a. (R)-2-bromobutane and water (in water) Page 1 of 8

2 + - (R)-2-bromobutane (R and S)-2-butanol a.k.a. S N 1 good LG ( - ) in polar protic solvent b. 1-bromo-2-butene and ethanol (in ethanol) 1-bromo-2-butene S N 1 - carbocation rearrangement tiny bit of S N 2 1-hydroxy-2-butene < (R and S)- S N 1 Good LG ( - ) in polar protic solvent (maybe a bit of S N 2) c. and water (in water). 2 (R and S) S N 1 Good LG ( - ) in polar protic solvent w/ extremely hindered substrate Page 2 of 8

3 5. Which alkyl halide would you expect to be more reactive in an 1) S N 1 reaction 2) S N 2 reaction with a given nucleophile? And why? a. or 1) bromide is weaker base, so better LG and more reactive 2) bromide is weaker base, so better LG and more reactive b. or 1) both will form 2 o carbocations, so equally reactive 2) 2-bromobutane b/c less steric hindrance c. or 1) 2-bromopentane b/c 2 o carbocation is more stable 2) 1-bromo-2-methylbutane b/c 1 o alkyl halide is less sterically hindered d. or 1) b/c 2 o carbocation 2) b/c less steric hindrance Additional Information: Definitions yperconjugation: Delocalization of e-s by overlap of a C- or C-C σ bond with an empty/ ½ empty p-orbital. Stabilizes carbocations/radicals. Basicity: Measure of how well a base shares its lone pair electrons with a proton (accept a proton by making a covalent bond). Nucleophile: An e- rich atom or molecule. Likes nuclei b/c they have protons. Nucleophilicity: Measure of how readily an atom or molecule with a pair of nonbonding e-s attacks an atom (electrophile). Electrophile: An e- deficient atom or molecule. Polarizability: Indication of the ease with which the e- cloud of an atom can be distorted. Page 3 of 8

4 Solvent Affects Table 8.7, pg 376 gives common solvents w/ dielectric constants. Protic solvent bonded to an or N (can hydrogen bond). Makes a strong base less nucleophilic by solvating the ion (ion-dipole interaction)/shielding it from reacting. EX. water, ammonia, ethanol, acetic acid all polar Aprotic solvent N bonded to an or N (can NT hydrogen bond). EX. polar nonpolar N S N,N-dimethylformamide DMF dimethyl sulfoxide DMS chloroform diethyl ether hexane S N 2 vs. S N 1 Rxns: S N 2: bimolecular nucleophilic substitution: Concerted rxn where nuc replaces LG w/ inversion of R stereochem (b/c of back side attack of nuc). Factors: Structure of Alkyl alide: S N 2:Less substituted alkyl halides are more reactive b/c less steric hindrance ( G ) methyl halide > 1 o > 2 o > 3 o (too unreactive w/ S N 2) Table 8.1 Rates of S N 2 Reaction w/ Alkyl omides Alkyl alide ass of Alkyl alide Rel. Rate methyl o 40 1 o 16 2 o 1 3 o Too slow Leaving Group (LG): W/ same alkyl halide and same nuc in aprotic solvent: Weaker bases are better LGs I - > - > - > F - (worst LG, ~ N S N 2) Nucleophile (Nuc): W/ same attacking atom/ atom of similar size: Stronger bases are better nucs Stronger Base/Better Nuc compared to - Weaker Base/Poorer Nuc 2 Page 4 of 8

5 C 3 - C 3 - N 2 N 3 C 3 C 2 N - C 3 C 2 N 2 - N 2 > - > F - Solvent A protic solvent makes a strong base less nucleophilic by solvating the ion (iondipole interaction)/shielding it from reacting (reverses trend in nucleophilicity; can think of nucleophilicity in terms of size/polarizability). I Nucleophilicity in APRTIC solvent Basicity Base F Size Nucleophilicity in PRTIC solvent Steric Affects A bulky nuc is not as good attacking an electrophile and a steric nuc is not as easy to attack. Tbl 8.3, pg 358: The Acidities of the Conjugate Acids of some LGs Acid pka Conjugate Base (LG) In Protic Solvent I I S S 3-2 S S 4 C C F 3.2 F - Better LG Better Nuc S 7.0 S - CN CN N N 3 C 3 C 2 S 10.5 C 3 C 2 S - (C 3 ) 3 N (C 3 ) 3 N C C C C 25 C C - Page 5 of 8

6 - N 2 N ~40 - Reversibility of S N 2 rxn: Depends on basicity of nuc and LG: S N 2 proceeds in direction that allows the stronger B (better nuc) to displace the weaker B (better LG), but if the basicity isn t that different, rxn will be reversible. S N 1: unimolecular nucleophilic substitution 2-step reaction where LG leaves, generates a cabocation intermediate (w/ possible rearrangement) and nuc attacks from top or bottom to give racemation. Factors: Structure of Alkyl alide: More substituted alkyl halides more reactive b/c carbocation formed is more stable (hyperconjugation). 3 o > 2 o > 1 o * & methyl halide* (*too unreactive w/ S N 1, can do S N 2) Table 8.4 Rates of S N 1 Reaction w/ Alkyl omides Alkyl alide ass of Alkyl alide Rel. Rate 3 o 1,200,000 2 o o 1.00* methyl 1.05* Carbocation Rearrangement: Carbocation will rearrange to form a more stable ion and then you may get BT S N 1 and S N 2 (constitutional isomers). Leaving Group (LG): W/ same alkyl halide and same nuc in aprotic solvent: Weaker bases are better LGs I - > - > - > F - Nucleophile (Nuc): N effect on rate of S N 1 rxn b/c NT involved in r.d.s.; usu. solvent is nuc (solvolysis: rxn w/ solvent). *Benzylic and allylic nucs: undergo S N 2 (unless 3 o ) and S N 1 (if stable carbocations). Vinylic and aryl nucs: do NT undergo S N 2 (b/c π e- cloud dbl bond or aromatic ring repels nuc) or S N 1 (b/c sp carbocation is not stable and sp 2 C- bonds are strong). Page 6 of 8

7 Table 8.5 Comparison of S N 1 and S N 2 Rxns S N 1 S N 2 2-step mech w/ carbocation intermed. Concerted mech Unimolecular r.d.s. Bimolecular r.d.s. Carbocation rearrangement N rearrangement Racemization P has inverted configuration Most reactive 3 o > 2 o > 1 o & methyl halide* Most reactive methyl halide > 1 o > 2 o > 3 o * * unreactive ow do I decide S N 1 vs. S N 2? Look at alkyl halide Table 8.6 Summary of Reactivity of Alkyl alides in Nucleophilic Substitution Reactions Methyl and 1 o alkyl halides S N 2 only 3 o alkyl halides S N 1 only 3 o benzylic and allylic halides S N 1 only 2 o alkyl halides S N 1 and S N 2 1 o and 2 o benzylic and allyic halides S N 1 and S N 2 Vinylic and aryl halides Neither Look at reaction conditions Inc. rate of S N 2 Inc. rate of S N 1 1. [nuc] Inc. [nuc] 2. Reactivity of nuc Good nuc Poor nuc (good or poor?) 3. Solvent* Aprotic polar (if nuc (-)) Protic polar *In general: inc. polarity of solvent Dec. rxn rt if 1 or more R in r.d.s. is charged. Inc. rxn rt if no R in r.d.s. is charged. The greater the charge on the solvated species, the stronger interaction w. polar solvent and the more stabilized. If charged R If charged T.S. (neutral R) Stabilize R more Stabilize T.S. more Inc. G Dec. G Dec. rxn rt. Inc. rxn rt. w/ S N 1: R (usu. neutral) T.S. (carbocation, so charged) T.S. more stabilized by polar solvent, so inc. rxn rt. w/ S N 2: IF Nuc (usu. (-)) + R (usu. neutral) T.S. ((-) over 2 atoms) R more stabilized by polar solvent, so dec. rxn rt. Page 7 of 8

8 IF Nuc (neutral) + R (usu. neutral) T.S. ((-)) T.S. more stabilized by polar solvent, so inc. rxn rt. Look at S N 1 S N 2 Reactant 3 o > 2 o 1 o > 2 o Nuc Weak Strong-Excellent LG Good-Excellent Bad-Excellent Solvent Polar protic Aprotic Products Racemate and carbocation rearrangement Inversion of reactant stereochemistry Page 8 of 8

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