08 - Organic Derivatives of Water 2

ORGANIC DERIVATIVES OF WATER
CHEM 40 Basic Organic Chemistry

compounds arise from the replacement of one or two hydrogen
atoms of water with an organic group
Organic Derivatives of Water

CHEM 40 | Basic Organic Chemistry | AJAMagsino
GENERAL STRUCTURE
𝛂–carbon is sp3-hybridized
-OH is the hydroxyl group
CLASSIFICATION OF ALCOHOLS
primary alcohols secondary alcohols tertiary alcohols
Organic Derivatives of Water: Alcohol

NOMENCLATURE
isopropyl alcohol
methyl alcohol
neopentyl alcohol

PRACTICE! Give the common names of the following compounds
isobutyl alcohol
tert-butyl alcohol
sec-butyl alcohol

NOMENCLATURE (Open-Chain Alcohols)
1. Locate the longest continuous carbon chain as the

parent chain and use the suffix –ol instead of –e.
2. Number the carbons in the parent chain beginning from
the end closest to the hydroxyl group.
3. Number all the other substituents according to their
position in the chain.
5-nonanol
4-ethyl
1 4 6 6-isopropyl
3 5
2 3-methyl
7 9
8 4-ethyl-6-isopropyl-3-methyl-5-nonanol

NOMENCLATURE (Polyols)
The ring bearing the –OH group serves as the parent ring.
Position 1 is assign to the C bearing the –OH group and the
number proceeds in the direction that gives the lowest
number possible for other substituents. The position number
of the –OH group does not appear in the name.
cyclohexanol
1 2-isopropyl
6 2
5,5-dimethyl
5 3
4
2-isopropyl-5,5-dimethylcyclohexanol

NOMENCLATURE (Cyclic Alcohols)
If two or more –OH groups are present, the suffixes –diol, -triol
are attached to the alkane name of the parent chain. Indicate
the position numbers of the –OH groups before the alkane
name.
1 2 3 1 2 3 4
1,2,3-propanetriol 3-methyl-1,2-butanediol

NOMENCLATURE (Enols and Ynols)
§ Locate the parent chain – must contain both the double or
triple bond and the –OH group
§ Number the chain - the –OH group is given priority in
numbering the parent chain
§ Name the parent chain - combine the two functional group
(change “ene” to “en”, “yne” to “yn”) and indicate their
respective position
OH
6
5
3 2
2 4 4
1
1 3
3-buten-2-ol 3-methyl-4-hexyn-2-ol
PRACTICE! Give the IUPAC names of the following compounds
OH
OH
HO
5-methyl-2-cyclohexenol 5-isopropyl-1,3-cyclohexanediol

PROPERTIES
Boiling Point
compounds of comparable molecular weights:
BP alcohols > BP halides > BP alkanes
Solubility in water can form H-bonds!
generally soluble
increase in size, decreases the solubility
branching increases solubility

PROPERTIES
BP (°C) Solubility (g/100g H2O)
ethanol 78.5 Miscible
1-propanol 97.2 Miscible
1-butanol 117-118 7.9
1-pentanol 137.5 2.3
OH OH OH
BP (°C) 117-118 99.5 82.4
Solubility
7.9 12.5 miscible
(g/100g H2O)

CHEMICAL REACTIONS
Acid/base reactions

CHEMICAL REACTIONS
Acid/Base Strength: inductive effect
ERG intensifies the negative charge, enhancing basicity
most acidic least acidic
least basic most basic

CHEMICAL REACTIONS
EWG stabilizes the conjugate base RO- and makes the alcohol more acidic
CF3 CH3
STRONG F3C OH H3C OH WEAK

acid CF3 CH3 acid
pKa = 5.4 pKa = 18.0
CF3 CH3
WEAK F3C O H3C O STRONG
conjugate CF3
conjugate
CH3
base base

CHEMICAL REACTIONS
EWG stabilizes the conjugate base RO- and makes the alcohol more acidic

PRACTICE! For each pair, identify which is the stronger acid
OH
1. vs. OH
Cl
2. vs. OH
OH Cl
3. OH vs. CH2OH

CHEMICAL REACTIONS
Acid/Base Strength: resonance effect
delocalization of electrons makes it unavailable for bonding
O base
+
strength of conjugate
R H R O + H
base:
alkoxide ion RO->HO->ArO-
weak acid strong conjugate base
O base
H H H O + H+ strength of acid:
hydroxide ion ROH<HOH<ArOH
weak acid strong conjugate base
O
base needed:
H base
O + H+ Na or Li for ROH
NaOH for ArOH
phenoxide ion
strong acid weak conjugate base: resonance stabilized

CHEMICAL REACTIONS
Acid/Base Strength: resonance effect
delocalization of electrons makes it unavailable for bonding
O
base
H O + H+
phenoxide ion
strong acid weak conjugate base: resonance stabilized
O O
O
phenoxide ion

CHEMICAL REACTIONS Rate of bubbling
primary
Acid/base reactions fastest
secondary ¯
alkoxide formation (+): bubbling tertiary slowest
other metals: Li, K, Mg, Al, Ca, etc.; other bases: NaNH2
alkoxonium formation

CHEMICAL REACTIONS
Acid/base reactions
O-Na+
OH
1. Na
2. NaNH2
OH O-Na+

CHEMICAL REACTIONS
Acid/base reactions

CHEMICAL REACTIONS
Oxidation
OH [O] O
C C
conversion of alcohols to their

1o or 2o corresponding carbonyl compounds
OH
[O]
R C R NR
R

CHEMICAL REACTIONS
Oxidation
OH O O
PCC [O]
1o ROH R C H R C H R C OH
H
[O]
§ [O] = oxidizing Agents: warm KMnO4, CrO3/H+ (Jones test),

Na2Cr2O7/H2SO4
§ if pyridinium chlorochromate (PCC) is used, the reaction stops
at the aldehyde stage

CHEMICAL REACTIONS
Oxidation
§ [O] = oxidizing Agents: warm KMnO4, CrO3/H+ (Jones test),

Na2Cr2O7/H2SO4, PCC

CHEMICAL REACTIONS
Oxidation
Hot, acidic KMnO4
will only give positive result to 1o and
2o alcohols
CrO3/H+ or Na2Cr2O7/H2SO4 (Jones’ test)

will only give positive result to 1o and
2o alcohols

Complete the following reactions by supplying the
PRACTICE! structure of the substrate, major organic product/s
or reagent/s.

or reagent/s.
OH
Na2Cr2O7, H2SO4
1.
O
+
2. CrO3/H
OH
3. PCC
OH

CHEMICAL REACTIONS
Nucleophilic Substitution Reactions (SN1/SN2)
-OH group is a poor leaving group

(strong base)
must be protonated first
(always the 1st step in nucleophilic
substitution reaction)
α – carbon is electrophilic
can be attacked by the nucleophile

CHEMICAL REACTIONS
Common Reagents:
HCl/ZnCl2 (Lucas test, for 2o and 3o ROH), SOCl2, POCl3 and

PCl3 (SN2 chlorinating agents, for 1o and 2o ROH), HCl (for 3o
alcohols), HBr, HI, or MX/H2SO4 (for 1o, 2o, and 3o ROH)

CHEMICAL REACTIONS
SN2 mechanism for primary alcohols
H H H
H fast H
(1) C OH + H + C O
H
R R
oxonium
H H H H H
H H
slow H
(2) Nu: + C O Nu C O Nu C + H2O
H H
R R R
oxonium
inversion of
configuration

CHEMICAL REACTIONS
SN1 mechanism for secondary and tertiary alcohols
H H H
R fast R
(1) C OH + H + C O
H
R R
oxonium
H H RH
(2) R slow
C O C + H2O
H
R R
oxonium
Nu
(3) H
fast
Nu: + R C R H
R up or down
(50:50 chance)
R

CHEMICAL REACTIONS
Reaction with HX (alcohol to alkyl halide)
REACTIVITY: HI > HBr > HCl (uses ZnCl2 as catalyst, Lucas test)
(Weakest Bond, more reactive)
2o and 3o ROH: reacts via SN1
1o ROH: reacts via SN2

CHEMICAL REACTIONS
Reaction with HX (alcohol to alkyl halide)
Lucas Test (concentrated HCl, ZnCl2)

Visible Result: formation of cloudy mixture or
layers due to the formation of RCl
Reaction Rate: 3o ROH > 2o ROH
1o ROH: NR

CHEMICAL REACTIONS
Reaction with SOCl2 and PX3 (alcohol to alkyl halide)
PX3: PI3, PBr3, PCl3

reacts via SN2 (no rearrangement)
1o and 2o alcohols are more reactive
CHEMICAL REACTIONS
Reaction with SOCl2 and PX3 (alcohol to alkyl halide)

or reagent/s.
OH Br
1.
2. SOCl2
OH
3.
OH Br

CHEMICAL REACTIONS
Elimination/Dehydration (E1/E2) (alcohol to alkene)
R
H+
R C C OH C C + H2O
b a
H
Common reagents:
conc. H2SO4, high T; conc. H3PO4, high T; Al2O3 (alumina), high T
Follows Zaitsev’s Rule!

CHEMICAL REACTIONS
E2 mechanism for primary alcohol
H
+
H
(1) R C C O H R C C O H
fast
H H
H R
slow
(2) R C C O H C C + H3O+

CHEMICAL REACTIONS
E1 mechanism for secondary/tertiary alcohol
R R H
+
H
(1) R C C O H R C C O H
fast
H H
R H R H
slow
(2) R C C O H R C C + O H
H H
R H
R R
fast
(3) R C C + O H C C + H3O+
H

CHEMICAL REACTIONS
+
OH conc. H2SO4
1. D Zaitsev Pdt. Anti-Zaitsev Pdt.

major pdt. minor pdt.
2. OH conc. H3PO4
+ +
D
Zaitsev Pdt. Anti-Zaitsev Pdts.

major pdt. minor pdts.

Predict the product(s) of the following reactions.
PRACTICE! For multiple products, select the predominating
product.

STRUCTURE
-OH group attached to the
aromatic ring
OH G = any group attached to

the ring: ortho, meta, or para
G relative to the -OH group
FAMOUS PHENOLS
OH
OH
HO O
OH
Organic Derivatives of Water: Phenol

PROPERTIES
Solubility in Water: 9 g/100g water
phenols have the ability to form

H-bonds in the pure state and
with water
the large non-polar benzene

ring makes it insoluble in water H
O H
O
H

REACTIONS
Acid/Base reactions
OH O-Na+
1. + NaOH
stronger base
OH
2. + NaHCO3 NR
weaker base

REACTIONS
Acid/Base reactions
NaOH
G OH G O-
if G = EWG, acidity is if G = ERG, acidity is

enhanced decreased
the phenoxide ion is more the phenoxide ion is
stabilized (weak base) destabilized (strong base)

PRACTICE! Arrange the following phenols in increasing acidity:
OH OH OH OH OH
O2N NO2
NH 2 NO2 NO2 OCH 3

A B C D E
A<D<E<B<C

REACTIONS
Electrophilic Aromatic Substitution
EAS Reactions:
Nitration
Sulfonation
strong activator! Halogenation
ortho-, para- director Friedel-Crafts Alkylation
Friedel-Crafts Acylation

REACTIONS
Electrophilic Aromatic Substitution
Br
OH OH
Br2
H2O
Br Br
Br
OH OH
Br2
FeBr3
Br Br

PRACTICE! Predict the product/s of the following reactions:
CH3 CH3
OH OH
Br2
FeBr3
Br Br
CH3
CH3 CH3
OH
OH OH
Br2
+
CCl4
Br Br

REACTIONS
Oxidation
OH O
Other [O], oxidizing agents:
Na2Cr72O
NaCr O77 • ammoniacal AgNO3
H 2O • Hot, acidic, KMnO4
• CrO3, H+
O • H2CrO4
benzoquinone

ANALYSIS
§ Soluble in NaOH(aq) but not in NaHCO3(aq)

§ Bromine water test
§ Produces white ppt of 2,4,6-tribromophenol
§ Oxidation
§ KMnO4 – produces black ppt
§ H2CrO4 – opaque green color
§ Reaction with FeCl3
§ Forms a colored complex

DIFFERENTIATING ALCOHOLS AND PHENOLS
Hot,
Lucas FeCl3 Jones’
Compound acidic, Br2/H2O
Test Test Test
KMnO4
1o ROH + - - - +
2o ROH + + - - +
3o ROH - + - - -
ArOH + - + + +

STRUCTURE
the two hydrogen atoms in water
is replaced by alkyl or aryl groups
Ethers are functional isomers of

alcohols!
CLASSIFICATION (based on groups attached on the oxygen)
O
Ar R
R = alkyl group
Ar = aryl group
dialkyl ether alkyl aryl ether diaryl ether
Organic Derivatives of Water: Ethers
STRUCTURE
CLASSIFICATION (based on symmetry)
symmetrical ethers
O
O O
diethyl ether diphenyl ether dibenzyl ether

a common solvent
unsymmetrical ethers
O O
OCH3
tert-butyl methyl ether 3-methoxyhexane 1-ethoxypropane
a gasoline additive

NOMENCLATURE (common name)
symmetrical ethers: “dialkyl ether” or “alkyl ether”
diisopropyl ether or isopropyl ether diethyl ether or ethyl ether
unsymmetrical ethers: “alkyl alkyl ether” in alphabetical order
ethyl isopropyl ether isobutyl isopropyl ether

PRACTICE! Give the common name of the following ethers:
O O
cyclohexyl isopropyl ether methyl phenyl ether
O O
(di)cyclopropyl ether benzyl phenyl ether

NOMENCLATURE (IUPAC name)
named as an alkoxyalkane/ene/yne
The smaller alkyl group and the ether oxygen are taken
together as the alkoxy group. The alkoxy group is treated as a
substituent of the larger organic group.
smaller alkyl: larger alkyl:

a substituent 3 smaller alkyl:
the parent chain 2
2 3 1 a substituent
propane
1 larger alkyl:
the parent chain
2-methylpropane
or isobutane
NOMENCLATURE (IUPAC name)
named as an alkoxyalkane/ene/yne
combine the names of the small and large groups without a
space in between
smaller alkyl:
a substituent
3
larger alkyl: 2-ethoxypropane
2 the parent chain
2-ethoxy
propane
1
larger alkyl: 1-isopropoxy-2-methylpropane

3 smaller alkyl: 1-isopropoxyisobutane
the parent chain 2 a substituent
2 1-(2-propoxy)-2-methylpropane
2-methylpropane 3 1 1-isopropoxy 1-(2-propoxy)isobutane
isobutane 1
1-(2-propoxy)

PRACTICE! Give the IUPAC name of the following ethers:
O O
isopropoxycyclohexane methoxybenzene
O O
cyclopropoxycyclopropane o-phenoxytoluene

NOMENCLATURE (IUPAC)
the ethereal O is part of the ring; may be named by relating the cyclic
Cyclic ethers ether to the corresponding hydrocarbon ring and using the prefix oxa– to
(epoxides) indicate that an oxygen atom replaces a methylene or –CH2– group
O O
O O
oxacyclobutane oxacyclopentane 1,4-dioxacyclohexane
Substituted cyclic ethers

The atoms in the ring are numbered
3 2 oxacylopentane
by giving position 1 to the ethereal 1 2-isopropyl
oxygen and proceeds in the direction 4
4-methyl
that gives the lowest number possible
to the remaining substituents. 2-isopropyl-4-methyloxacyclopentane
PROPERTIES
weakly polar compounds
with weak residual dipole moment
partial cancellation of dipole
Boiling Point
BP ether ≈ BP alkanes (of comparable MW)
BP ether < BP alcohols (of comparable MW)
Solubility
in general, ethers are insoluble or slightly soluble in water
depends on the relative size of the polar and non-polar groups

PREPARATION OF EPOXIDES
m-CPBA O
C C
C C
m-CPBA
O

PREPARATION OF ETHERS
Williamson Ether Synthesis
major reaction for the preparation of ethers
an SN2 reaction between an alkyl halide and an alkoxide or phenoxide
does not work for 3o alkyl halides and aryl halides

Williamson Ether Synthesis
generation of alkoxide from alcohol
R OH + M R O M+ + 1/2 H2
alkoxide reacts with alkyl halide via SN2

Williamson Ether Synthesis (planning your synthesis)
POINTERS:
O Na+ + CH3Br
Small alkyl halides favor SN2:
always choose the less
substituted alkyl halide
E2 is competing with SN2:

If possible, halide must not
contain a 𝛽-hydrogen

Williamson Ether Synthesis (planning your synthesis)

PRACTICE! Propose a synthetic route for the following ethers:

REACTIONS
Cleavage reactions using HX (ethers to alkyl halides)
O H-X H-X
R R' R' X + R OH R X
reaction stops here if
dilute HX is used
O H-X
Ar R R' X + Ar OH
HX reactivity: HI > HBr >>> HCl

REACTIONS
1° / 2° alkyl ethers
I– or Br– attacks the protonated ether at the less hindered site

REACTIONS
3° alkyl ethers
cleavage by competing SN1 and E1 reactions
carbocation formation is favored
CH 3 H Br CH 3 H
H 3C C O CH 2CH 3 H 3C C O CH 2CH 3
CH 3 CH 3

REACTIONS
3° alkyl ethers

REACTIONS
O
dilute HI + I
OH

REACTIONS
O dil. HI OH
+ CH3I

REACTIONS
O O
HI H
I +

REACTIONS
O O
HI H
I +
O H
H I
(1)
O + I
H
I
(2) O OH + I
SN2

REACTIONS
O
HI
NR
dil. HBr
OH +
O Br

PRACTICE! Predict the products of the following reactions:
dil. HBr Br
O +
HO
O
dil. HBr
Br OH

REACTIONS
Cleavage reactions of epoxides
acid-catalyzed cleavage
nucleophile attacks the more substituted carbon!
trans-diol

REACTIONS
acid-catalyzed cleavage
other nucleophiles can be used
H
O O OH
H Br
C C C C C C
Br
Br

REACTIONS
acid-catalyzed cleavage (unsymmetrical ethers)
Epoxides with 1o and 2o oxirane carbon – SN2-like
(nucleophile attacks the primary carbon)

REACTIONS
acid-catalyzed cleavage (unsymmetrical ethers)
Epoxides with a 3o oxirane carbon – SN1-like (nucleophile
attacks the tertiary carbon)

PRACTICE! Predict the major product of the reaction
HBr Br
O
OH

REACTIONS
base-catalyzed cleavage
special reaction of epoxides (not observed in ethers!); the
nucleophile attacks the less substituted carbon of the
oxirane ring (SN2)

PRACTICE! Predict the product(s) of the reaction
CH3 CH3
OH
1. NaOCH3
O
2. H2O
OCH3
H H

PRACTICE! Predict the product(s) of the reaction
H OH
1. NaOCH3
O C C
2. H2O
H H3CO
C C
HO
HBr
C C
H
Br

DIFFERENTIATING ALCOHOLS, PHENOLS, and ETHERS
Hot,
Lucas FeCl3 Jones’
Compound acidic, Br2/H2O
Test Test Test
KMnO4
1o ROH + - - - +
2o ROH + + - - +
3o ROH - + - - -
ArOH + - + + +
ROR’ - - - - -
ethers are soluble in cold, concentrated H2SO4

PRACTICE! Predict the product(s) of the following reactions
OH Li O
Cl heat
OH
dil. HI
I +
O
O OH
HCl Cl
ether

PRACTICE! Determine the most probable set of compounds
that will form the ether shown via Williamson ether
synthesis


08 - Organic Derivatives of Water 2

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

08 - Organic Derivatives of Water 2

Uploaded by

Copyright:

Available Formats

ORGANIC DERIVATIVES OF WATER

CHEM 40 Basic Organic Chemistry

Organic Derivatives of Water

primary alcohols secondary alcohols tertiary alcohols

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

1. Locate the longest continuous carbon chain as the

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

least basic most basic

Organic Derivatives of Water: Alcohol

STRONG F3C OH H3C OH WEAK

pKa = 5.4 pKa = 18.0

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

conversion of alcohols to their

Organic Derivatives of Water: Alcohol

§ [O] = oxidizing Agents: warm KMnO4, CrO3/H+ (Jones test),

Organic Derivatives of Water: Alcohol

§ [O] = oxidizing Agents: warm KMnO4, CrO3/H+ (Jones test),

Organic Derivatives of Water: Alcohol

CrO3/H+ or Na2Cr2O7/H2SO4 (Jones’ test)

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

-OH group is a poor leaving group

Organic Derivatives of Water: Alcohol

HCl/ZnCl2 (Lucas test, for 2o and 3o ROH), SOCl2, POCl3 and

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Lucas Test (concentrated HCl, ZnCl2)

Organic Derivatives of Water: Alcohol

PX3: PI3, PBr3, PCl3

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Follows Zaitsev’s Rule!

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

1. D Zaitsev Pdt. Anti-Zaitsev Pdt.

Zaitsev Pdt. Anti-Zaitsev Pdts.

Organic Derivatives of Water: Alcohol

Organic Derivatives of Water: Alcohol

OH G = any group attached to

Organic Derivatives of Water: Phenol

phenols have the ability to form

the large non-polar benzene

Organic Derivatives of Water: Phenol

Organic Derivatives of Water: Phenol