Alcohols Condensation Reaction CH3 – OH + HO – CH3 CH3 – O – CH3 + H2O H2SO4 CH3 – OH + HO – CH3 CH3 – O – CH3 + H2O two molecules combine to form larger molecule + water ether H2O alcohol + alcohol +

Ethers O- - R water alcohol ether H-bond acceptor no H-bond donor dipole-dipole interactions low b.p. soluble in polar solvents

Ethers “ether” bunny Common nomenclature : name both R groups + ether propyl 2 1 3 1 methyl propyl ether methyl methyl dimethyl ether O .. methyl “ether” bunny propyl people ether

Ethers Reactions Formation: Peroxide formation: condensation reaction H2SO4 condensation reaction Peroxide formation: peroxide

Aldehydes and Ketones 120o aldehyde ketone C=O carbonyl group C and O are sp2 hybridized polar higher b.p. than alkanes H-bond acceptor soluble in polar solvents no H-bond donor lower b.p. than alcohols

Aldehydes and Ketones Nomenclature 1. Longest chain with C=O is parent 2. Suffix is “-al” or “-one” 3. C1 is always C=O in aldehydes In ketones, C=O is given lowest number 4. C=O has precedence over -OH (called “hydroxy”)

2-bromo-3-methyl butan al 3- pentan one trans- 3-hydroxy- 2-methyl 4 2 1 3- pentan one 1 4 2 5 3 trans- 1 2 3-hydroxy- 2-methyl cyclobutanone 3

Reactions Reduction [R] = reducing agent LiAlH4 NaBH4 H2/Pt butan al 3 1 2 CH3- CH2- CH2- CHO CH3- CH2- CH2- CH2- OH butan al [R] 1 3 4 2 2- butan one

Nucleophilic addition ketone aldehyde O C : O C : + - C=O very polar Nucleophilic addition - O C : + H-Nu H Nu O C H Nu + H-OH H-OR H-NH2 + -

Nucleophilic addition C O-H R O-H C O R .. H C = O R .. H+ C = O R .. + H+ H H+ hydrate or diol C O R .. H C R O-H O-R + H+ + H-OH O .. H R .. O H N H .. C = O R .. + H-OR hemi-ketal C R O - H N - H2 + H+ C R N H + H2O + H-NH2 Schiffs base

Addition of alcohol H C O CH3 H3C H C O H3C H+ + CH3OH H OCH3 ketone hemi- ketal unstable aldehyde + alcohol = hemi- acetal unstable

_ more stable = -D-glucose b.p. = 150o -D-glucose b.p. = 146o CH2OH 3 OH 1 2 4 5 6 O CH2OH H more stable OH HO 1 2 3 4 5 6 CH2OH O = C _ H HO 1 2 OH 3 HO -D-glucose 4 b.p. = 150o OH 5 OH 3 OH 1 2 4 5 6 O CH2OH H 6 OH HO CH2OH CH2OH -D-glucose b.p. = 146o

Nucleophilic substitution .. .. hemi - acetal condensation reaction H3C H OH O - CH2 - CH3 O - CH2 - CH3 H .. .. H+ C H3C H OH O - CH2 - CH3 H+ .. OH - CH3 - CH2 .. .. + H2O hemi - acetal C H3C H O - CH2 - CH3 + H+ aldehyde alcohol + alcohol acetal + condensation reaction hemi-acetal + alcohol acetal + H2O

acetal propanal + 2 equivalents ethanol stable hemi- ketal 2-butanone + 1 equivalent methanol unstable

Carboxylic acids [O] [O] 1o alcohol aldehyde carboxylic acid methanol methanal methanoic acid H-bond acceptor - very high b.p. H-bond donor - + 2 H-bonds / molecule

Carboxylic acids Nomenclature 1. Carboxyl group (COOH) always C1 2. Family name is longest C chain with COOH 3. Suffix is “-oic acid” 4. Carbonyl groups (C=O) called “oxo” Hydroxy groups (OH) called “hydroxy”

Carboxylic acids 2-ethyl butan oic acid 2-ethyl 4-hydroxy 2-ethyl- CH3 – CH2 – CH – C CH2 – CH3 O OH 4 3 2 1 2-ethyl butan oic acid O CH3 – CH2 – CH – CH2 – CH – CO2H OH CH2 – CH3 2-ethyl 4-hydroxy 6 5 4 3 2 1 2-ethyl- 4-hydroxy hexan oic acid 2-ethyl- 4-oxo hexan oic acid add [O]

Carboxylic Acids Chemical properties = = OH C=O + Bronsted acid H+ donor HA H+ + A- H+ + weak acids, small dissociation Ka = [A-] [H+] Ka  1 x 10-5 pH  2.5 for 1M [HA]

Carboxylic Acids H+ + H+ + - resonance structure anion stabilized

Carboxylic Acids - acidity also affects solubility soluble short chain acids H-bonding long chain acids insoluble benzoic acid LDF - add a strong base (OH-) soluble ion-dipole

Reactions Acid-base reactions: + NaOH octanoic acid insoluble sodium octanoate + water soluble

Reactions Reduction: 5-oxo hexanoic acid 1,5- hexanediol 5-hydroxy LiAlH4 6 5 4 3 2 1 5-oxo hexanoic acid 1,5- hexanediol H2/ Pt NaBH4 5-hydroxy hexanoic acid