Organic Chemistry II

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Chapter 8 Properties of Alcohols

I. Nomenclature
A. Functional Groups
1) RCH2—OH = Hydroxy functional group
2) Alcohol = organic molecule having a hydroxy group
3) Replace one H of water with R: H—O—H  R—O—H
4) Ether = replace both H’s of water with R: R—O—R

B. Naming Alcohols
1) Modify the alkane name by dropping –e and adding –ol
a) CH3OH = methanol
b) CH3CH2CH2CH2OH = butanol
c) R-OH = alkanol

2) Branched Alcohols OH OH

a) Name based on longest


chain containing -OH 3-methylheptanol 4-methly-3-propyl-2-octanol
b) Number each carbon starting from the closest to –OH

OH
HO H OH
1-propanol (S)-3-hexanol 2,2,5-trimethyl-3-heptanol

3) Cyclic Alcohols = cycloalkanols


OH
Cl
1 OH
1 1 OH

cyclohexanol 1-methylcyclobutanol cis-3-chlorocyclopentanol

4) When referring to –OH as a substituent it is called hydroxy


5) Simple alcohols often have common names 3-hydroxypropylamine
CH3OH = methyl alcohol H2N OH
CH3CH2OH = ethyl alcohol
(CH3)2CHOH = isopropyl alcohol
(CH3)3COH = tert-butyl alcohol
II. Structural and Physical Properties of Alcohols
A. Structure
1) Alcohol structures are similar to water: sp3 O atom with 2 lone pairs

2) Steric effects of the R groups slightly alter bond angles


3) Electronegativity of O shortens and strenthens the O—H bond
compared to C—H
a) DHo(OH) = 104 kcal/mol
b) DHo(CH) = 98 kcal/mol

4) Electronegativity of O causes large molecular dipole moment for alcohols


R H
+
O

-
B. Hydrogen Bonding
1) Hydrogen bond = weak, partial bond between a heteroatom bound H and
another heteroatom (N, O, X, S, etc…)

2) DHo(OH…..H) = 5 kcal/mol

3) The sum of the multiple H-bonds in water or alcohols increases the


boiling points of these liquids relative to alkanes or haloalkanes
Methane = -162o Chloromethane = -24.2o Methanol = 65o
Nonpolar Polar Polar
No H-Bonds No H-Bonds H-Bonds
C. Solubility
1) Alcohols have high water solubility (Like dissolves Like)
a) Polarities of water and alcohols are similar OH
b) Hydroxy group is Hydrophilic (water loving)
c) Alkyl group is Hydrophobic (water fearing)
d) Alkanes have no solubility in water (hydrophobic)
e) Organic molecules with polar functional groups (-OH, -NH2, -CO2H)
have much higher water solubilities
2) The longer the alkyl group, the less water soluble the alcohol (more
soluble in hydrocarbons—like dissolves like)
3) MeOH and EtOH are very similar to water as solvents: many salts will
dissolve in them, because they are polar enough to separate the charges

III. Acid-Base Behavior of Alcohols


A. Alcohols are Amphoteric = can be acids or bases
B. Acidity of Alcohols Ka
1) R—OH + H2O R—O- + H3O+
alkoxide
[ H 3O  ][ RO  ] pKa   log Ka  pH at which acid is half dissociate d
Ka 
[ ROH ]
R pKa R pKa
2) Alcohols are relatively weak acids
H2O 15.7 t-BuOH 18
3) Electronegativity of R—O- allows MeOH 15.5 HCl -2.2
it to stabilize (-) charge, but not EtOH 15.9 RCO2H 4.7
very well
i-PrOH 17.1 CH4 50

4) Requires a strong base to fully deprotonate an alcohol


EtOH(pKa = 15.9) + OH-  EtO- + H2O (pKa = 15.7)
50% 50%

MeOH(pKa = 15.5) + NH2-  MeO- + NH3 (pKa = 35)

~ 0% 99.999%

5) Acidity: MeOH > 2-Propanol > t-Butyl Alcohol (1o > 2o > 3o)
Steric disruption of solvation
of deprotonated product
6) Inductive Effects = transmission of charge through s-bonds
a) Electronegative substituents increase an alcohol’s acidity
CCl3CH2OH > CHCl2CH2OH > CH2ClCH2OH > CH3CH2OH

b) Electronegative groups remove electron density from R—O-, which


stabilizes the anion. It is easier to deprotonate = more acidic.

C. Basicity of Alcohols
1) Lone pairs of electrons will accept H+ from strong acids
ROH + HA  ROH2+ + A-
weak Strong
base Conjugate
Acid pKa = -2

2) Conditions for Acid/Base behavior of Alcohols

Mild base Strong Base


ROH2+ ROH RO-
Strong acid Mild acid
IV. Synthesis of Alcohols by Nucleophilic Substitution
A. For Industrial Alcohol Synthesis, see your book
B. Lab Scale Reactions H2O
1) SN1 Reaction of Tertiary RX ROH
OH-
2) SN2 Reaction of Primary, Secondary RX ROH
3) Often harder to make the RX than the ROH (get RX from ROH)
4) E1/E2 products complicate these reactions
5) Use acetate (weak base) to prevent Elimination reactions
O O
- + SN2
CH3CH2Br + CH3C O Na CH3CH2O CCH3
acetate ester

O -
O
OH
CH3CH2O CCH3 CH3CH2OH + HO C CH3
Ester Hydrolysis Acetic acid

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