SN2 rxns w/ROH HCl, ZnCl2 (replaces OH w/Cl) HBr (replaces OH w/Br) 1. TsCl, pyridine (convert OH into -OTs)/2.

/2. nucleophile SOCl2,pyridine (replaces OH w/Cl) PBr3 (replaces OH w/Br) E rxns with ROH (to alkenes) H2SO4 (strong acid) (E1) TsCl, NaOEt (so acid + base wont react)E2 Chromate oxidation of ROH (forms C=O compounds) CrO3, H3O+, acetone/H2CrO4/Na2Cr2O7, H2SO4, H2O (just turn COH to C=O) o ROOH from 1o ROH, ketone from 2o ROH PCC, CH2Cl2 (to get aldehyde from 1o ROH) Hydrohalogenation (works on both alkene, alkyne) HX (Markovnikov) HX, ROOR (anti-Markovnikov) (ROOR=peroxide) Mixture of (E) and (Z) alkene products formed when on alkyne Acid catalyzed hydration Dilute strong acid, H2O Use other nuc besides H2O to add something besides OH (Ex. EtOH, MeOH) ***To do dehydration, use concentrated acid Oxymerc-demerc (hydration) 1. Hg(OAc)2, H2O/2. NaBH4 Use other nuc- besides H2O to add something besides OH (Ex. EtOH, MeOH, ROH) Markovnikov & avoids carbocation rearrangment Hydroboration-oxidation (hydration)

1. BH3*THF/2. H2O2, NaOH (anti-Markovnikov & syn)

Halogenation (alkenes, alkynes)

X2, CHCl3 (anti-addition) (cis vs. trans may yield different

products) Halohydrin

X2, H2O (anti-addition) (OH- to more substituted side) (pg. 428)

Anti-dihydroxylation (anti-addition) 1. (RCO3H) like CH3CO3H or MCPBA/2. Acid (H3O+, H2SO4 etc.) (pg. 431) Use another nucleophile to add group besides OH (EtOH, MeOH, ROH) *Epoxide formation 1. (RCO3H) like CH3CO3H or MCPBA Syn-dihydroxylation (OsO4, , t-butyl hydroperoxide, or KMnO4) Na2SO3 or NaHSO3, H2O (syn-addition) *Oxidative cleavage (cleaves C=C into 2 C=O) 1. O3/2. One of either DMS or Zn/H2O Dihalide to alkyne 1. NaNH2/NH3/2. H2O Acid catalyzed hydration (of alkynes)enol tautomerizes into a ketone, NOT an enol H2SO4, H2O, HgSO4 (Markovnikov) pg. 471tautermerization Here, tautomerization is acid catalyzed Produces ketone Hydroboration-oxidation (of alkynes)enol tautomerizes into aldehyde, NOT an enol 1. R2BH (9-BBN or Disiamylborane)/2. H2O2, NaOH (BH3*THF works too) (anti-Markovnikov) Here, tautomerization is base catalyzed (pg. 474tautomerization) Used to produce aldehyde *Preparing nitriles 1. React alkyl halide with CN (NaCN, HCN) (SN2) 2. Dehydrate amides using SOCl2 (pg. 1011) Hydrolysis of nitriles (to form amide) 1. Can be acid catalyzedH3O+, heat (pg. 1012) + 2. Can be base catalyzed1. NaOH, H2O/2. H3O (pg. 1012) Nitrile to ketone 1. RMgBr/2. H3O+ Reduction of nitriles (to amines) 1. LAH/2. H2O Acid catalyzed preparation of ethers o Ex. (H2SO4), but only works on 1 alcoholsso impractical (pg. 630) Williamson ether synthesis (from alcohols) 1. A strong base (ex. NaH, NaOH)/2. RXto produce R-OR (pg. 631) Alkoxymercuration-demercuration (another way of ether synthesis) 1. Hg(OAc)2, ROH/2. NaBH4 (pg. 411) Notice here, instead of using H2O as nucleophile, an alcohol (ROH) is used Halogenation (of alkynes) X2, CCl4 (anti-addition) (forms tetrahalide) Allylic halides to dienes (E2) Sterically hindered base Hydrohalogenation (of dienes) HX (Markovnikov) Halogenation (of dienes) X2 Preparing epoxides 1. From alkenes: (recall) use peroxy acids (RCO3H)ex. MCPBA (pg. 431) 2. From halohydrins: NaOH (Pg. 638) Recall: halohydrins can be form from alkenes via X2, H2O 3. From allylic OH bearing compounds: t-butyl-O-O-H, Ti[OCH(CH3)2]4, (+) or (-)-DET Opening epoxide rings (Inversion of configuration occursSN2) 1. Strong nucleophile (depending on what group you want to add) (Pg. 643) (nucleophile attacks less substituted edge of epoxide) (NaOH, RONa, NaCN, NaSH, RMgBr, LAH), H2O 2. Acid catalyzed: (Pg. 647) HXX and OH groups result H+, H2Otwo OH groups result + H , ROH ether and OH groups result SNAr reaction A nucleophile (e.g. NaOH, NaOCH3) (pg. 898) H3O+ (H+ source) is needed if NaOH is used Addition-elimination (pg. 901) 1. NaOH, 350OC/2. H3O+ 1. NaNH2, NH3/2. H3O+ Benzyne is formed and nucleophile can attack either side of the carbon-carbon triple bond Reactions at the benzylic position (requires H atom at benzylic position) Na2Cr2O7, H2SO4, H2O or KMnO4, H2O, heat (converted into benzoic acid regardless) Recall: benzylic halides can undergo SN1 & SN2 Benzylic halides and alcohols also undergo E1 & E2

Hydration of C=O compounds 1. Acid catalyzed (pg. 924) + H2O, H 2. Base catalyzed (pg. 924) H2O, OHAcetal formation ROH, H+ (acid such as TsOH & H2SO4) (pg. 925) Can serve as protecting group (removed by adding H2O) Imine formation o + 1 amine, H (acid) (Pg. 932) Enamine formation o 2 amine, H+ (acid) (pg. 936) Wolf-Kishner reduction (on hydrazonesR=N-NH2) KOH, H2O, heat (pg. 939) Conversion of imine, enamine, acetal back to C=O Excess H2O, acid catalyzed (mechanism is exact opposite of its formation) Thioacetal formation RSH, H+ (acid) (mechanism analogous to acetal formation) Desulfurization (converts thioacetalsalkane) Raney Ni (Raney nickel) Reduction of C=O compounds into alcohols with hydride agents 1. LAH/2. H2O NaBH4, MeOH Reaction between Grignard reaction and C=O compound 1. XMgBr/2. H2O (Pg. 948) Cyanohydrin formation (pg. 949) 1. KCN, HCN 2. KCN, HCl Wittig reaction (converts ketone into alkene) CH2PPH3 (Wittig reagent) (Pg. 951) Preparating of Wittig reagents 1. CH3I (an alkyl halide)/2. BuLi (added to PPh3)BuLi=CH3CH2CH2CH2Li (pg. 952) Bayer-Villiger Oxidation of Aldehydes and Ketones (into esters) RCO3H (Pg. 954) Hydrolysis of nitriles into carboxylic acids H3O+, heat Carboxylation of Grignard reagents 1. CO2/2. H3O+ Reduction of carboxylic acids to alcohols + 1. LAH/2. H3O BH3*THF (selective) Reactions of acid chlorides SOCl2 (preparation from ROOH) H2O, pyridine (makes ROOH) ROH, pyridine (makes esters) o o Ammonia, 1 and 2 amines (makes amides) 1. LiAl(OR)3H/2. H2O (makes aldehydes) 1. RMgBr/2. H2O (makes ROH) Me2CuLi (makes ketones) Reactions of acid anhydrides Sodium carboxylate (preparation from ROOH) All reactions above apply here (see above) Acetic anhydride is often used to acetylate an alcohol or an amine Preparation & reactions of esters Strong base (formation from ROOH) ROH, acid (formation from ROOH) 1. NaOH/2. H3O+ (makes ROOH) H3O+ (makes ROOH) 1. LAH/2. H2O (makes ROH) Grignard reagent (makes ROHtwo alkyl groups added) Reaction of amides H3O+, heat (makes ROOH) + 1. NaOH, heat/2. H3O (makes ROOH) 1. LAH/2. H2O (makes amines) Preparation & reactions of nitriles Treat RX w/CN (preparation) Dehydrate amide using SOCl2 (preparation) H3O+ (makes amides first, then ROOH) 1. NaOH/2. H3O+ (makes amides) 1. RMgBr/2. H3O+ (makes ketones) 1. LAH/2. H2O (makes amines) Preparation of amines NH3, H+, H2, (Ni, Pt, Pd) (from ketones and aldehydes) NaBH3CN, H+, NH3 (from ketones & aldehydes) Preparation alcohols via reduction H2, (Pd, Pt, or Ni) (from ketones & aldehydes) NaBH4 or LAH, H+ source (EtOH, MeOH, H2O) (from ketones & aldehydes) Alpha halogenation of enols and enolates H3O+, X2 1. Br2, PBr3/2. H2O (from ROOH) Base, X2 o Methyl ketone under these conditions + acid work up=ROOH Aldol formation and reactions NaOH, H2O (enolate + aldehyde react) (formation) Condensation: (acidic or basic conditions), heat (causes unsaturation between & positions) Claisent condensations (esters undergoing condensation) + Base (NaOEt)/2. H3O Choose a base that has the same OR group as that on the ester to prevent transesterification (which converts on OR group on the ester to another) Crossed claisen condensation (LDA used as base) Alkylation of the alpha position 1. Base (LDA, NaH)/2. RX (via enolate ions) 1. NaOEt, EtOH/2. RX/3. H3O+, heat (from Diethyl Malonate and transform a halide into a carboxylic acid with the addition of two new Cs) 1. NaOEt, EtOH/2. RX/3. H3O+, heat (from ethyl acetoacetate and converts an alkyl halide into a methyl ketone with the addition of 3 new Cs)

Halogenation X2, AlX3 (pg. 860) Sulfonation Fuming H2SO4 (Pg. 864) SO3H group can be removed via dilute H2SO4 Nitration HNO3, H2SO4 (Pg. 866) NO2 can be converted into NH2 via Zn or Fe and HCl Friedel-Crafts alkylation CH3X, AlX3 (Pg. 869) Friedel-Crafts acylation XC=OCH2CH3, AlX3 (Pg. 872) Avoids rearrangement (which occurs in F-C alkylation) Clemmensen reduction (just remove O) Acyl group can be converted to alkyl group via Zn [Hg], HCl Formation of N-nitrosamines (Pg. 1116two mechanisms) NaNO2, HCl (used on 2o amines) Formation of diazonium salt (diazotization) NaNO2, HCl (used on 1o amines) (Pg. 1117) Aryldiazonium salt reactions Sandmeyer reaction: CuX (where X=halogen or CN- group) Fluorination: NaBF4 Replacing -N2 with OH group: H2O, heat Replacing -N2 with H: H3PO2 Azo coupling: activated benzene ringPhR (where R=activating group) (pg. 1121)