ep101 sen lnt 006 alcohol may11
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EP101 / EG101 2
Alcohols
.
This family of organic compounds is characterized by the hydroxyl group: -OH. Note that when an R group (an alkyl group) replaces one H in the water molecule, an alcohol results
::
the alcoholfunctional group
C O-H
105o
water
HO
H
109o
an alcohol
RO
H
OH is the function group which is the center of the reactivity
EP101 / EG101 3
Classification of Alcohols
.
Alcohols are classified as primary, secondary or tertiary according to the structure around the carbon to which the hydroxyl group is attached
ethyl alcohol
CH3CH2OH
a 1o alcohol
CCH3
H
HOH
isopropyl alcohol
(CH3)2CHOH
a 2o alcohol
CCH3
CH3
HOH
tertiary-butyl alcohol
(CH3)3COH
a 3o alcohol
CCH3
CH3OH
CH3
Aromatic (phenol): -OH is bonded to a benzene ring
OH
EP101 / EG101 4
Nomenclature of Alcohols
In the IUPAC naming system, there may be asmany as four components to the name:
Locant indicates the position of a substituent.Prefix names the substituent group.
Parent is the parent alkane.
Suffix names a key function.
Examples
CH3CH2CHCH3
OHCH3CHCH2CH2OH
CH3
2-butanol 3-methyl-1-butanol
locant parentsuffix
locant prefix locantsuffix
parent
EP101 / EG101 5
IUPAC Rules for Naming Alcohols
(1) Select the longest continuous chain containing the hydroxyl group as the parent. Drop the "e" in the alkane name and add the suffix "ol."
.(2) Number the chain from the end that gives a lower number to the position of the hydroxyl group
CH3CH2CHCH2OHCH3
4 3 2 1
2-methyl-1-butanol
CH3CHCHCH3CH3
OH
3-methyl-2-butanol
EP101 / EG101 6
Common Names of Alcohols
Alkyl group names are approved by IUPAC for naming alcohols:"alkyl group + alcohol."
CH3CH2OH CH3CHCH3
OHCH3CCH2OH
CH3
CH3
ethyl alcohol isopropyl alcohol neopentyl alcohol
"Glycol" is a common name for compounds containing two hydroxyl groups. In the IUPAC system, they are diols.
HOCH2CH2OH CH3CHCH2OHOH
ethylene glycol(1,2-ethanediol)
propylene glycol(1,2-propanediol)
.
Note: The glycol name uses the common name of the alkene that yields the diol upon hydroxylation
EP101 / EG101 7
Name these:
CH3 CH
CH3
CH2OH
CH3 C
CH3
CH3
OH
CH3 CH
OH
CH2CH32-methyl-1-propanol
2-methyl-2-propanol
2-butanol
OH
Br CH3
3-bromo-3-methylcyclohexanol
EP101 / EG101 8
Unsaturated Alcohols Hydroxyl group takes precedence over double and triple bonds. Assign carbon with –OH the lowest number. Use alkene or alkyne name.
4-penten-2-olpent-4-ene-2-ol orCH2 CHCH2CHCH3
OH
HO OH 1,6-hexanediol
Glycols 1, 2 diols (vicinal diols) are called glycols. Common names for glycols use the name of the alkene from which they were made.
CH2CH2
OH OH
1,2-ethanediol
ethylene glycol
CH2CH2CH3
OH OH
1,2-propanediol
propylene glycol
EP101 / EG101 9
Naming Phenols Phenol is an aromatic compound. Hydroxyl (-OH) group attach to a benzene ring. -OH group is assumed to be on carbon 1. For common names of disubstituted phenols, use ortho- for 1,2; meta- for 1,3; and para- for 1,4. Methyl phenols are cresols.
OH
Cl
3-chlorophenolmeta-chlorophenol
OH
H3C
4-methylphenolpara-cresol
EP101 / EG101 10
Solubility decreases as the size of the alkyl group increases.
Physical Properties of Alcohols: 1. Solubility
OH group is the hydrophilic part of alcohol (ROH) which form H bond with water molecules.
Therefore, ROH is soluble in water. BUT when C chain increased, the solubility in water decreased. (increase the hydrophobicity)
Increase branching increased the ROH solubility.
WHY??? Because the C atom (hydrophobic part) become more compact and smaller.
EP101 / EG101 11
2. Boiling Points
• ROH has bp higher than any HC of similar molecular mass.
•The large difference in bp is due to the intermolecular hydrogen bond in alcohol and phenol.
• Presence of –OH group causes polarization in the molecule to form intermolecular hydrogen bonds.
• van der waals < hydrogen bonds ; the energy/strength increase for H bonds. So more energy needed to break bonds.
• bp reduces by increased the branching of molecule due to smaller surface area and its reduce the dipole inter-reaction between molecules and less energy needed to break bonds.
•
EP101 / EG101 12
3. Acidity of Alcohol & Phenol ROH are weak acid In aqueous, ROH donate proton to water to form alkoxide ion
If given disassociation constant, Ka, the smaller the Ka the more acidic the ROH
Delocalization of electron in the benzene ring makes phenoxide ion more acidic & stable in its form of as compared to alkoxide ion.
Presence of e withdrawing grp phenol acidity.
R-OH + H2O R-O- + H3O+
aaa KpKwherebyROH
ROOHK log][
]][[ 3 Smaller pKa=
more acidic!!
EP101 / EG101 13
Molecular Structure and AcidityResonance delocalization of charge in A-
the more stable the anion, the farther the position of equilibrium is shifted to the right
ionization of the O-H bond of an alcohol gives an anion for which there is no resonance stabilization
CH3CH2O-H H2O CH3CH2O - H3O++An alcohol An alkoxide ion
+ pKa = 15.9
EP101 / EG101 14
Molecular Structure and AcidityElectron-withdrawing inductive effect
the polarization of electron density of a covalent bond due to the electronegativity of an adjacent covalent bond
stabilization by the inductive effect falls off rapidly with increasing distance of the electronegative atom from the site of negative charge
C-CH2O-HH
HH
C-CH2O-HF
FF
EthanolpKa 15.9
2,2,2-TrifluoroethanolpKa 12.4
CF3-CH2-OH CF3-CH2-CH2-OH CF3-CH2-CH2-CH2-OH2,2,2-Trifluoro-
ethanol(pKa 12.4)
3,3,3-Trifluoro-1-propanol(pKa 14.6)
4,4,4-Trifluoro-1-butanol
(pKa 15.4)
EP101 / EG101 15
Solvation & Steric Effect
Simple alcohols are about as acidic as water. Alkyl groups make an alcohol a weaker acid. The more easily the alkoxide ion is solvated by water the more its formation is energetically
favored. Steric effects are important.
EP101 / EG101 17
Acidity of Phenols• Phenols and alcohols both contain hydroxyl groups however they are classified as separate functional groups. Why?
Answer: Phenols have different properties than alcohols, most noteworthy is their acidity (pKa difference of 106)
OH O
+ H2O + H3O+ pKa = 9.95
H3C
H2C
OH + H2O H3C
H2C
O+ H3O+ pKa = 15.9
Solutions of alcohols in water are neutral, whereas a solution of 0.1 M phenol is slightly acidic (pH 5.4).
EP101 / EG101 18
• Why are phenols more acidic?
Resonance. The charge is delocalized around the ring.
O O O O
This gives a qualitative explanation as to why phenols are more acidic than alcohols but for quantitative comparison, pKa’s must be determined experimentally.
• Ring substituents, especially halogens and nitro groups have marked effects on the acidity of phenol by a combination or resonance and inductive effects. Both m-cresol and p-cresol are weaker acids than phenol with pKa’s of 10.01 and 10.17 respectively.
OH OH
CH3CH3
m-cresolp-cresol
EP101 / EG101 19
Influence of substituents on the acidity of phenol:Alkyl groups decrease the acidity of phenol where halogens increase the acidity of phenol through inductive effects.
O
CH3
Electron donating alkyl group destabilizesthis resonance structure
OH
XX = F, Cl, Br
X
OElectron withdrawing halogen groups stabilize the delocalized negative charge
Fluorine is most electronegative of the halogens, and therefore has the greatest influence on the acidity of halophenols. This trend follows electronegativity: Chlorine has less of an effect than fluorine and bromine an even smaller effect than chlorine.
OH
Cl
m-chlorophenol
pKa = 8.85
OH
CH3
p-cresol
pKa = 10.17
EP101 / EG101 20
Synthesis of Alcohol
Reduction of carbonyl Catalytic hydrogenation if aldehyde & ketone Reduction of aldehyde & ketone by hidride
From Alkene Hydration of alkene Hydroboration-oxidation of alkene Hydroxylation of alkene
Addition of grignard to carbonyl
EP101 / EG101 21
.Alkenes react with water in the presence of acids to give alcohols directly. Addition does not occur in the absence of acids
H3C
H3C H
H
+ H2OH+ OH
Acid-Catalyzed Direct Hydration of AlkenesA1.
A. Synthesis From Alkene
EP101 / EG101 22
Mechanism of Direct Hydration of Alkenes
Step 1: electrophilic addition
++ slow
H OH
H + + H2O
Step 2: nucleophilic addition
+ + :
: fastOH
H+
tert-butyloxonium ion
OH2
+ :
: fast+OH
HOH2
Step 3: deprotonation
+OH+
H OH
H
Note: Hydronium ion is reformed, so the reaction is catalyzed by acid.
EP101 / EG101 23
Alcohols through Oxidation of Alkylboranes
Reaction of an alkylborane with hydrogen peroxide (H2O2) and base (NaOH) leads to replacement of the borane group with a hydroxyl group.
The sequence of hydroboration-oxidation of an alkene yields an alcohol with anti-Markovnikov orientation.
an alkene
OH
anti-Markovnikov product
A2.
NaOH, H2OH2O2
BH2 HH
OH HHretention
EP101 / EG101 24
Oxidations of Alkenes--Syn Hydroxylation
The stereospecific formation of 1,2-diols (or glycols) from alkenes may be carried out in two ways:
KMnO4, HO-
cold H2O HO OH
(i) OsO4, pyridine(ii) Na2SO3/H2O or NaHSO3/H2O HO OH
A3.
EP101 / EG101 25
B. Reduction of Carbonyl Reduction of aldehyde yields 1º alcohol. Reduction of ketone yields 2º alcohol. 2 Methods of reduction of carbonyl
Catalytic hydrogenation of aldehyde & ketone, and Reduction of aldehyde & ketone by hydride.
EP101 / EG101 26
B1. Catalytic Hydrogenation Add H2 with Raney nickel catalyst. Also reduces any C= bonds. Hydrogenation of Ketone yields 20 alcohol Hydrogenation of Aldehyde yields 10 alcohol
H2, NiCO
COH
H
EP101 / EG101 27
Sodium Borohydride Hydride ion, H-, attacks the carbonyl carbon, forming an alkoxide ion. Then the alkoxide ion is protonated by dilute acid. Only reacts with carbonyl of aldehyde or ketone, not with carbonyls of esters or carboxylic acids.
HC
O
HC
H
OHC
H
OH HH3O+
B2. Reduction of aldehyde & ketone by hydride.
EP101 / EG101 28
Comparison of Reducing Agents
LiAlH4 is stronger. LiAlH4 reduces more stable compounds
which are resistant to reduction.
EP101 / EG101 29
Reaction with Carbonyl R- attacks the partially positive carbon in the carbonyl. The intermediate is an alkoxide ion. Addition of water or dilute acid protonates the alkoxide to produce an alcohol.
R C O R C O
HOHR C OH
OH
C. Addition of Grignard to Carbonyl
C
CH3
RO
R MgBr + C
CH3
R
OR MgBr
HOH
C
CH3
R
OHR
EP101 / EG101 30
Some Grignard ReagentsBr
+ Mgether MgBr
CH3CHCH2CH3
Clether
+ Mg CH3CHCH2CH3
MgCl
CH3C CH2
Br + Mgether CH3C CH2
MgBr
EP101 / EG101 31
C1-Synthesis of 1° AlcoholsGrignard + formaldehyde yields a primary alcohol with one additional carbon.
HOHCH3 CH
CH3
CH2 CH2 C
H
H
O H
C OH
HCCH3
H3C CH2 C MgBrH
HHCH3 CH
CH3
CH2 CH2 CH
HO MgBr
C2- Synthesis of 2º AlcoholsGrignard + aldehyde yields a secondary alcohol.
MgBrCH3 CH
CH3
CH2 CH2 C
CH3
H
OC
CH3
H3C CH2 C MgBr
H
HH
C OH
H3C
CH3 CH
CH3
CH2 CH2 C
CH3
H
O HHOH
EP101 / EG101 32
C3- Synthesis of 3º AlcoholsGrignard + ketone yields a tertiary alcohol.
MgBrCH3 CH
CH3
CH2 CH2 C
CH3
CH3
OC
CH3
H3C CH2 C MgBr
H
HH
C OH3C
H3C
CH3 CH
CH3
CH2 CH2 C
CH3
CH3
O HHOH
EP101 / EG101 35
Reaction of Alcohol
Oxidation of ROH Reduction of ROH Breaking of Carbon–OH bond
ROHRX ROHC=C
Breaking of O-H Formation of esther
EP101 / EG101 36
A. Oxidation of Alcohol-ROH is main source of C=O (carbonyl)C=O (carbonyl)-Oxidation of primary and secondary alcohol will give aldehyde and ketone respectively.
+ Cr3+ (green)
Cu or
CrO3/pyridine(C5H5N)
Chromic acid
H2CrO4
EP101 / EG101 37
1o & 2o Alcohol Oxidations Primary alcohols aldehydes
PCC/CH2Cl2 (pyridinium chlorochromate, C5H5NH+ClCrO3-)
CrVI in one form or another (H2CrO4 or K2Cr2O7) MnVII (KMnO4/NaOH/H2O/heat)
Color of reagents can be useful. CrVI is yellow; CrIII is blue
Cu or
CrO3/pyridine(C5H5N)
Chromic acid
H2CrO4
EP101 / EG101 38
3o Alcohol Oxidations Tertiary alcohols cannot be oxidized under
normal conditions. Heat them too much in the presence of
strong oxidizers; start cleaving C-C bonds.
Why? When an alcohol is oxidized, a hydrogen is removed from the carbon. If that hydrogen is
not present, no oxidation can occur.
H
OHO
[O]
OH
NRX
EP101 / EG101 39
B. Reduction of Alcohol
alcoholCH3CHCH3
OHTsCl
CH3CHCH3
OTsLiAlH4
alkaneCH3CH2CH3
tosylate
EP101 / EG101 41
Reaction with HCl Chloride is a weaker nucleophile than bromide. Add ZnCl2, which bonds strongly with
-OH, to promote the reaction. The chloride product is insoluble. Lucas test: ZnCl2 in conc. HCl
1° alcohols react slowly or not at all. 2 alcohols react in 1-5 minutes. 3 alcohols react in less than 1 minute.
Limitations of HX Reactions HI does not react Poor yields of 1° and 2° chlorides May get alkene instead of alkyl halide Carbocation intermediate may rearrange.
EP101 / EG101 42
C2.2. Reaction with tionyl chloride, SOCl2
Produces alkyl chloride, SO2, HCl S bonds to -OH, Cl- leaves Cl- abstracts H+ from OH C-O bond breaks as Cl- transferred to C
EP101 / EG101 43
P bonds to -OH as Br- leaves Br- attacks backside HOPBr2 leaves
C2.3. Reaction with Phosphorus halogen, PX3
EP101 / EG101 44
Dehydration of AlcoholsAlkenes are also generally prepared by the dehydration of alcohols in the presence of a strong acid.
heatH+
C
H
C
OH
+ H2O
C3.
EP101 / EG101 45
D1. Esterification Fischer: alcohol + carboxylic acid Tosylate esters Sulfate esters Nitrate esters Phosphate esters
Acid + Alcohol yields Ester + Water Sulfuric acid is a catalyst. Each step is reversible.
CH3 C OH
O
+ CH2CH2CHCH3
CH3
OHH+
CH3C
O
OCH2CH2CHCH3
CH3
+ HOH
EP101 / EG101 46
aldehyde RCOOHketone
ROR
alkyne
alkene
RH
RX
ROH
Alcohols are central to organic syntheses
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