[A MECHANISM FORTHE REACTION _ Mechanism for the Sy2 Reaction | Reaction HO + CH,cl —> CH,OH + cl Transition state Tho nogative hydroxido In the traneition Now the bond jon brings @ pair of state, a bond between the oxrven ‘electrons to the partially between oxygen ‘and carbon has positive carbon from ‘and carbon is formed and the the back side with partially formed chloride ion has respect to the leaving, ‘and the bond departed. The ‘group. The chlorine between carbon configuration of the bogine to move away and chlorine i carbon has inverted. ‘with the pair of partially broken. ‘electrons that ‘The configuration bonded ito ‘of the carbon the carbon. ‘atom begins to invert.[a MECHANISM FOR THE REACTION ~ Mechanism for the Sy1 Reaction ] Reaction ae f CHP: + 20 > CH F-GH + Hor + Ge oH, CH, Mechanism ‘Stop 1 CHy CH, ob SE ond e {% "He CH CH; ‘ded by the polar solvent, _This slow step proces Tickled depetawintic the Sowbocaton rec ‘locton pai that bonded iat anda chloride fon. I tie exten cease the lone are eohato nd stabized) by water ‘molecules,Step 2 ‘Step 3 on, stop 2 fest ae —H === cH-G—OtH rareo ‘cH, Is oH CH, H AG ‘Avrater molecule acting The products a ‘a5 a Lewis base donates —_tort-butyloxonium ion ‘an electron pair to the (or protonated = carbocation (a Lewis acid). __ tert-butyl alcohol). The shen she cette ateono. eacton coordinate carbon eight electrons. Hy 1H tN te ont ses cH C—O 6-H BE cH ‘Transition eh | I state 3 CHy H H CH, Hi ‘A.water molecule acting The products are tert-butyl a aBronsted base ‘alcohol and a hydronium is accepts a proton from jon. = — 8 the tert-butyloxonium ion. Reaction coordinateTABLE 6.5 FACTORS FAVORING Syi VERSUS Sy2 REACTIONS Factor Syl Sn2 Substrate 3° (requires formation of a relatively Methyl > 1° > 2° (requires stable carbocation) unhindered substrate) Nucleophile Weak Lewis base, neutral molecule, Strong Lewis base, rate increased by nucleophile may be the solvent high concentration of nucleophile (solvolysis) Solvent Polar protic (e.g., alcohols, water) Polar aprotic (e.g, DME, DMSO) Leaving group 1 > Br > Cl > F for both Syl and Sx2 (the weaker the base after the group departs, the better the leaving group)[a MECHANISM FORTHE REACTION _ Electrophilic Aromatic Bromination | Step 1 BB+ “Feb, = ae owe Olu W ae: Ye ale Sr—FeBr, or — ey — or + FeBre . a y ‘Arenivm ion Helpful Hint the penzene ring donates an electron pair tothe terminal bromine, forming the ‘Anooctostats patel _arenium ion and neutralizing the formal positive charge on the other bromine. as om, — CJ": is shown in Fig. 18.2. A proton is removed from the arenium jon to form bromobenzene ‘and regenerate the catalyst. Step 3of an Alkene [4 MECHANISM FOR THE REACTION | Scitcatalyzed Hydration CH, CH—H Hq Step 1 Pa é + dH Hc "CH, . ‘The alkene donates an electron pair to proton to form ‘the mote stable "carbocation. fe H CH, H Do tes rl ‘Step 2 + :0-H === CHr O—H HAC ‘CH, = Son, bY H, ‘The carbocation reacts with a molecule of water to ieee Hs — Hs H Step 3 Pe + a ae aan + nbn Hs by . Atranster of a proton to a molecule of water leads to the product.[4 MECHANISM FOR THE REACTION ~ The ldo! Addition “0° In this step the base (a hydroxide ion) removes a proton from the a carbon of one molecule of acetaldehyde to give a resonance-stabilized enolate. Step 1 Enolate | + HOH formation . 05 » k= Li, es The enolate then acts as a nucleophile and attacks the carbonyl carbon of a second molecule of acetaldehyde, producing an alkoxide anion. Step 2 Addition of the enolate An alkoxide anion: :0H ‘0° Step 3_ Protonation Ay + HOH = Ky + 30H of the alkoxide Stronger base The aldol product Weaker base The alkoxide anion now removes a proton from a molecule of water to form the aldol product.‘The Cannizzaro reaction takes place by nucleophilic addition of OH~ to an aldehyde to give a tetrahedral intermediate, which expels hydride ion as a leaving group and is thereby oxidized. A second aldehyde molecule accepts the hydride jon in another nucleophilic addition step and is thereby reduced. Benzalde- hyde, for instance, yields benzyl alcohol plus benzoic acid when heated with aqueous NaOH.[A MECHANISM FORTHE REACTION ~ Acid-Catalyzed Esterification aN L H-OSH 0 oe H—O: H A = Ie 2 out beon CH SG—H GH. G—H “cH a ee 3 5 :Q-H The carboxylic acid ‘The alcohol attacks the A proton is lost at accepts a proton from protonated carbonyl one oxygen atom the strong acid catalyst. group to give a and gained at another. tetrahedral intermediate. H “~ Tt Hoos | CH—C—O-—CH, == C. = . € M CHe~ ~O—CH, | HO H Loss of a molecule of water ‘Transfer of a proton to ives a protonated ester. base leads to the esterReimer — Tiemann reaction Phenol, on refluxing with chloroform and sodium hydroxide (aq) at 340 K followed by acid hydrolysis yield salicyladehyde (o- hydroxy benzaldehyde) and a very small amount of p- hydroxy benzaldehyde. However, when carbon tetrachloride is used, saalicylic acid (predominating product) is formed. This reaction is called Reimer — Tiemann reactionOH OH 340 K CHCl, +CHCl, + NaOH(aq.) ————> A ONa OH 2NaOH Ht > CHO CHO -2NaCl HO 2- Hydroxy benzoic acid (Salicylic acid)Mechanism The eletrophile, dichloromethyle :CCl, is used genrated from chloroform by the action of a base. OH"+CHCl, <= HOH+ :CCl,—> Cr +:CCh Chloroform Dichloro carbene (Electrophilic) Reimer — Tiemann reaction involve electrophilic substitution on the highly reactive phenoxide ring.(a) C,H;OH ——> C,H,O” + Ht Phenol Phenoxide (b) Attack of electrophile (:CCI,) on phenoxide ion. oO ° aN CCl, fcc. eeTT eee (0) (OC): m0 idea or" ° CHO eae Sade H,0 (d) o OH