Chapter 2

Chapter
2: Chemistry of Alcohols and

Phenols, Ethers, Epoxides, Thiols and
Sulphides
John McMurry 9th Edition

Chapter 17: 17.1-17.10
Chapter 18: 18.1-18.8
Alcohols and Phenols
• Alcohols contain an OH group connected to a a saturated C (sp3)
• They are important solvents and synthesis intermediates
•
•
O
Phenols contain an OH group connected to a carbon in a benzene ring
Methanol, CH3OH, called methyl alcohol, is a common solvent, a fuel
additive, produced in large quantities
• Ethanol, CH3CH2OH, called ethyl alcohol, is a solvent, fuel, beverage
• Phenol, C6H5OH (“phenyl alcohol”) has diverse uses - it gives its name
to the general class of compounds
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Naming Alcohols
• General classifications of alcohols based on
substitution on C to which OH is attached
• Methyl (C has 3 H’s), Primary (1°) (C has two H’s,
one R), secondary (2°) (C has one H, two R’s),
tertiary (3°) (C has no H, 3 R’s),
Hydration of Alkene
AcidcatalyzedofAlkene Preparation of Alkene
Addition to
Unsymmetrical Alkene Markonikov'srule
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3
IUPAC Rules for Naming
Alcohols
• Select the longest carbon chain containing the hydroxyl group,
and derive the parent name by replacing the -e ending of the
corresponding alkane with -ol r
• Number the chain from the end nearer the hydroxyl group
• Number substituents according to position on chain, listing the
substituents in alphabetical order
COOCH

Many Alcohols Have
Common Names
• These are accepted by IUPAC

5
Naming Phenols
• Use “phene” (the French name for benzene) as the
parent hydrocarbon name, not benzene
• Name substituents on aromatic ring by their
position from OH

6
Properties of Alcohols and
Phenols: Hydrogen Bonding
• The structure around O of the alcohol or phenol is similar
to that in water, sp3 hybridized
• Alcohols and phenols have much higher boiling points than
similar alkanes and alkyl halides

Alcohols Form Hydrogen
Bonds
• A positively polarized ¾OH hydrogen atom from one molecule is
attracted to a lone pair of electrons on a negatively polarized oxygen
atom of another molecule
• This produces a force that holds the two molecules together
• These intermolecular attractions are present in solution but not in the
gas phase, thus elevating the boiling point of the solution

Properties of Alcohols and
Phenols: Acidity and Basicity
• Weakly basic and weakly acidic
K
• Alcohols are weak Brønsted bases
• Protonated by strong acids to yield oxonium ions, ROH2+
GReversible

Alchols and Phenols are Weak Brønsted
Acids As weak acid
• Can transfer a proton to water to a very small
extent Dissociateslightly in dilute solution
aqueous by donating
i • Produces H3O+ and an alkoxide ion, RO-, or a a proton

- to water
phenoxide ion, ArO

Brønsted Acidity I Ka Tpka
Measurements it acidic
• The acidity constant, Ka, measure the extent to which a

Brønsted acid transfers a proton to water
[A-] [H3O+]
Ka = ————— and pKa = -log Ka
[HA]
• Relative acidities are more conveniently presented on a
logarithmic scale, pKa, which is directly proportional to the
free energy of the equilibrium
• Differences in pKa correspond to differences in free energy
• Table 17.1 presents a range of acids and their pKa values

pKa Values for Typical OH Compounds
highly
substituted
I acidic

12
Relative Acidities of Alcohols
• 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
13
Inductive Effects
halogen
• Electron-withdrawing groups make an alcohol a stronger
acid by stabilizing the conjugate base (alkoxide)
more
by spreading
acidic
thecharge over
a largevolume

Generating Alkoxides
from Alcohols
• Alcohols are weak acids – requires a strong base to form an
on'treact
C alkoxide such as NaH, sodium amide NaNH2, and Grignard
th weak reagents (RMgX) s
base sodiumhydride
mine • Alkoxides are bases used as reagents in organic chemistry
or
carbonateion Methanol Methonalate

15
Phenol Acidity
• Phenols (pKa ~10) are much more acidic than alcohols (pKa
~ 16) due to resonance stabilization of the phenoxide ion
• Phenols react with NaOH solutions (but alcohols do not),
forming soluble salts that are soluble in dilute aqueous
• A phenolic component can be separated from an organic
solution by extraction into basic aqueous solution and is
isolated after acid is added to the solution
Reacidification
Phenol
ate
Substituted Phenols
• Can be more or less acidic than phenol itself
• An electron-withdrawing substituent makes a phenol more
acidic by delocalizing the negative charge
• Phenols with an electron-donating substituent are less
acidic because these substituents concentrate the charge

Nitro-Phenols
• Phenols with nitro groups at the ortho and para positions
are much stronger acids
• The pKa of 2,4,6-trinitrophenol is 0.6, a very strong acid

18
Preparation of Alchols:
an Overview
• Alcohols are derived from many types of compounds
• The alcohol hydroxyl can be converted to many other
functional groups
• This makes alcohols useful in synthesis

19
Review: Preparation of Alcohols by
Regiospecific Hydration of Alkenes
• Hydroboration/oxidation: syn, non-Markovnikov hydration
• Oxymercuration/reduction: Markovnikov hydration

Preparation of 1,2-Diols
• Review: Cis 1,2-diols from hydroxylation of an alkene with
OsO4 followed by reduction with NaHSO3
• Trans-1,2-diols from acid-catalyzed hydrolysis of epoxides
Syn ran
give
Cisdiol
Anti ran
give
transdid

Alcohols from Reduction of
Carbonyl Compounds
• Reduction of a carbonyl compound in general gives an
alcohol
• Note that organic reduction reactions add the equivalent of
H2 to a molecule

Reduction of Aldehydes and
Ketones
• Aldehydes gives primary alcohols
• Ketones gives secondary alcohols

Reduction Reagent: Sodium
Borohydride
• NaBH4 is not sensitive to moisture and it does not reduce
odium other common functional groups chosen because it's safety
and
orohydride
• Lithium aluminum hydride (LiAlH4) is more powerful, less easeof
specific, and very reactive with water more dangerous handling
explosively
• Both add the equivalent of “H-”

Mechanism of Reduction
• The reagent adds the equivalent of hydride to the carbon
of C=O and polarizes the group as well
protonated
by
positivepolarized
electrophilic C
Addition
of a nucleophilic hydrideion H
Rapid ran

Reduction of Carboxylic Acids
and Esters
• Carboxylic acids and esters are reduced to give primary
alcohols
Reduced • LiAlH4 is used because NaBH4 is not effective
ancarbonyl reduced ester
group veryslowly
notreduced Carboxylic acid
10
10
Alcohols from Reaction of Carbonyl
Compounds with Grignard Reagents
• Alkyl, aryl, and vinylic halides react with magnesium in
ether or tetrahydrofuran to generate Grignard reagents,
RMgX
• Grignard reagents react with carbonyl compounds to yield
alcohols
Addition of
Carboanion nucleophile
R Mg x

Examples of Reactions of Grignard
Reagents with Carbonyl Compounds

Reactions of Esters and Grignard
Reagents
• Yields tertiary alcohols in which two of the substituents
carbon come from the Grignard reagent
• Grignard reagents do not add to carboxylic acids – they
undergo an acid-base reaction, generating the hydrocarbon
of the Grignard reagent

Grignard Reagents and Other Functional
Groups in the Same Molecule
• Can't be prepared if there are reactive functional groups in
the same molecule, including proton donors

Mechanism of the Addition of a
Grignard Reagent
• Grignard reagents act as nucleophilic carbon anions
(carbanions, : R-) in adding to a carbonyl group
• The intermediate alkoxide is then protonated to produce
the alcohol

Some Reactions of Alcohols
• Two general classes of reaction
• At the carbon of the C–O bond
• At the proton of the O–H bond

Dehydration of Alcohols to Yield
Alkenes
• The general reaction: forming an alkene from an alcohol
through loss of O-H and H (hence dehydration) of the
neighboring C–H to give p bond
• Specific reagents are needed

Acid- Catalyzed Dehydration
followZaitsev's Rule
• Tertiary alcohols are readily dehydrated with acid fastxD leadt
• Secondary alcohols require severe conditions (75% H2SO4,
100°C) - sensitive molecules don't survive
• Primary alcohols require very harsh conditions –
impractical
• Reactivity is the result of the nature of the carbocation
intermediate (See Figure 17-5)
stabili e
ran
morestable
Dehydration with POCl3
basic
• Phosphorus oxychloride in the amine solvent pyridine can
lead to dehydration of secondary and tertiary alcohols at
low temperatures at
• An E2 via an intermediate ester of POCl2

Conversion of Alcohols into
Alkyl Halides
• 3° alcohols are converted by HCl or HBr at low temperature
• 1° and alcohols are resistant to acid – use SOCl2 or PBr3 by
an SN2 mechanism

poorleaving
group
i use socle to
convert Ott to
better leaving group
Conversion of Alcohols
into Tosylates
• Reaction with p-toluenesulfonyl chloride (tosyl chloride, p-
TosCl) in pyridine yields alkyl tosylates, ROTos
• Formation of the tosylate does not involve the C–O bond so
configuration at a chirality center is maintained
• Alkyl tosylates react like alkyl halides

Stereochemical Uses of
Tosylates
• The SN2 reaction of an alcohol via a tosylate, produces
inversion at the chirality center
• The SN2 reaction of an alcohol via an alkyl halide proceeds
with two inversions, giving product with same arrangement
as starting alcohol

Oxidation of Alcohols
Ezrin
• Can be accomplished by inorganic reagents, such as
KMnO4, CrO3, and Na2Cr2O7 or by more selective, expensive
reagents

Oxidation of Primary
Alcohols
• To aldehyde: pyridinium chlorochromate (PCC,
C5H6NCrO3Cl) in dichloromethane
• Other reagents produce carboxylic acids

Oxidation of Secondary
Alcohols
• Effective with inexpensive reagents such as Na2Cr2O7 in
acetic acid
• PCC is used for sensitive alcohols at lower temperatures

Protection of Alcohols
• Hydroxyl groups can easily transfer their proton to a basic
reagent
• This can prevent desired reactions
• Converting the hydroxyl to a (removable) functional group
without an acidic proton protects the alcohol

Methods to Protect Alcohols
• Reaction with chlorotrimethylsilane in the presence of base
yields an unreactive trimethylsilyl (TMS) ether
• The ether can be cleaved with acid or with fluoride ion to
regenerate the alcohol
43
Protection-Deprotection
• An example of TMS-alcohol protection in a synthesis

Preparation and Uses of Phenols
• Industrial process from readily available cumene
• Forms cumene hydroperoxide with oxygen at high
temperature
• Converted into phenol and acetone by acid (See Figure
17.10)
Isopropylbenzene

Laboratory Preparation
of Phenols
• From aromatic sulfonic acids by melting with NaOH at high
temperature
• Limited to the preparation of alkyl-substituted phenols

Reactions of Phenols
• The hydroxyl group is a strongly activating, making phenols
substrates for electrophilic halogenation, nitration,
sulfonation, and Friedel–Crafts reactions
• Reaction of a phenol with strong oxidizing agents yields a
quinone
• Fremy's salt [(KSO3)2NO] works under mild conditions
through a radical mechanism

exercises 567
3. Oxidation of phenols to quinones (Section 17-10)

OH O
Na2Cr2O7
H2O
EXERCISES
VISUALIZING CHEMISTRY
(Problems 17-1–17-19 appear within the chapter.)
17-20 Give IUPAC names for the following compounds:
(a) (b)
(c) (d)
17-21 Draw the structure of the carbonyl compound(s) from which each of the
following alcohols might have been prepared, and show the products
you would obtain by treatment of each alcohol with (1) Na metal,
(2) SOCl2, and (3) Dess–Martin periodinane.
(a) (b)
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80485_ch17_0525-0567n.indd 567 2/2/15 2:09 PM

567a chapter 17 alcohols and phenols
17-22 Predict the product from reaction of the following substance (reddish
brown ! Br) with:
(a) PBr3 (b) Aqueous H2SO4 (c) SOCl2
(d) Dess–Martin periodinane (e) Br2, FeBr3
17-23 Predict the product from reaction of the following substance with:
(a) NaBH4; then H3O! (b) LiAlH4; then H3O!
(c) 2 CH3CH2MgBr; then H3O!
17-24 Name and assign R or S stereochemistry to the product(s) you would

obtain by reaction of the following substance with ethylmagnesium
bromide. Is the product chiral? Is it optically active? Explain.
MECHANISM PROBLEMS
17-25 Evidence for the intermediate carbocations in the acid-catalyzed dehy-
dration of alcohols comes from the observation that rearrangements
sometimes occur. Propose a mechanism to account for the formation of
2,3-dimethyl-2-butene from 3,3-dimethyl-2-butanol.
H3C CH3 H3C CH3
H2SO4
C CH3 C C + H2O
H3C C
H3C CH3
H OH
80485_ch17_0525-0567n.indd 1 2/2/15 2:09 PM

exercises 567b
17-26 Acid-catalyzed dehydration of 2,2-dimethylcyclohexanol yields a mix-

ture of 1,2-dimethylcyclohexene and isopropylidenecyclopentane.
Propose a mechanism to account for the formation of both products.
Isopropylidenecyclopentane
17-27 Epoxides react with Grignard reagents to yield alcohols. Propose a

mechanism.
H H
OH
1. CH3MgBr
O
2. H O+
3
H
H CH3
17-28 Treatment of the following epoxide with aqueous acid produces a

carbocation intermediate that reacts with water to give a diol product.
Show the structure of the carbocation, and propose a mechanism for
the second step.
CH3 CH3
H3 O+ H2O OH
Carbocation
HO
O H H
H3C CH3
H+
17-29 Reduction of 2-butanone with NaBH4 yields 2-butanol. Is the product

chiral? Is it optically active? Explain.
17-30 The conversion of 3° alcohols into 3° alkyl halides under acidic condi-
tions involves two cationic intermediates. For each reaction, draw the
complete mechanism using curved arrows.
(a) OH Cl
HCl
(b) OH Br
HBr
(c) OH Cl
HCl
80485_ch17_0525-0567n.indd 2 2/2/15 2:09 PM

567c chapter 17 alcohols and phenols
17-31 Identify the type of substitution mechanism (SN1, SN2) involved in the
conversion of the alcohol shown into the corresponding alkyl halide.
(a) OH Cl
HCl
(b)
PBr3
OH Br
(c) 1. p-TosCl,
OH pyridine Br
2. NaBr
17-32 The conversion of 3° alcohols into alkenes under acidic conditions

involves two cationic intermediates. For each reaction, draw the com-
plete mechanism using curved arrows.
(a) OH
H3O+
(b)
H3O+
OH
(c)
H3O+
OH
17-33 For each reaction, write the mechanism using curved arrows for the
conversion of the alcohol into the corresponding alkene with POCl3. In
each case, explain the regiochemistry of the elimination.
(a)
POCl3
Pyridine
OH
(b) OH
POCl3
Pyridine
(c) OH
POCl3
Pyridine
80485_ch17_0525-0567n.indd 3 2/2/15 2:09 PM

exercises 567d
17-34 The trimethylsilyl (TMS) protecting group is one of several silicon pro-
tecting groups for alcohols. For each reaction, draw the mechanism
for the protection of (R)-3-bromo-1-butanol with the following silyl
chlorides, using triethylamine as the base:
(a) tert-butyldimethylsilyl chloride (TBS-Cl)
(b) triisopropylsilyl chloride (TIPS-Cl)
(c) triethylsilyl chloride (TES-Cl)
17-35 When the alcohol below is treated with POCl3 and pyridine, the
expected elimination product is formed. However, when the same
alcohol is treated with H2SO4, the elimination product is 1,2-dimethyl-
cyclopentene. Propose a mechanism for each pathway to account for
these differences.
POCl3 OH H2SO4
pyridine
17-36 Phenols generally have lower pKa’s than aliphatic alcohols because of
resonance stabilization with the aromatic ring. Draw all of the reso-
nance contributors for the phenolate ions below. Make note of how the
substituents either stabilize or destabilize the system.
(a)
O–
(b)
O–
NC
(c)
O–
OCH3
80485_ch17_0525-0567n.indd 4 2/2/15 2:09 PM

exercises 567j
General Problems
17-57 How would you carry out the following transformations?
(a) CO2H CO2H
?
(b) CO2H CH2OH

?
(c) CO2H CH2SH

?
17-58 Benzoquinone is an excellent dienophile in the Diels–Alder reaction.

What product would you expect from reaction of benzoquinone with
1 equivalent of 1,3-butadiene? From reaction with 2 equivalents of
1,3-butadiene?
17-59 Rank the following substituted phenols in order of increasing acidity,
and explain your answer:
OH OH OH OH
F CH3O N C
17-60 Benzyl chloride can be converted into benzaldehyde by treatment with

nitromethane and base. The reaction involves initial conversion of
nitromethane into its anion, followed by SN2 reaction of the anion with
benzyl chloride and subsequent E2 reaction. Write the mechanism in
detail, using curved arrows to indicate the electron flow in each step.
O
CH2Cl H O– C
H
+ C N+
H O–
Benzyl chloride Nitromethane anion Benzaldehyde
17-61 Reaction of (S)-3-methyl-2-pentanone with methylmagnesium bromide

followed by acidification yields 2,3-dimethyl-2-pentanol. What is the
stereochemistry of the product? Is the product optically active?
O
CH3CH2CHCCH3 3-Methyl-2-pentanone
CH3
80485_ch17_0525-0567n.indd 10 2/2/15 2:09 PM

567k chapter 17 alcohols and phenols
17-62 Testosterone is one of the most important male steroid hormones. When
testosterone is dehydrated by treatment with acid, rearrangement
occurs to yield the product shown. Propose a mechanism to account for
this reaction.
CH3 OH CH3
H
CH3 H H3O+ CH3 H
H H H H
O O
Testosterone
17-63 Starting from testosterone (Problem 17-62), how would you prepare the
following substances?
(a) (b) OH
CH3 O CH3
H
CH3 H CH3 H
H H H H
HO
O
H
(c) (d) OH
CH3 O CH3
H
CH3 H CH3 H
H H H H
HO
O
H
17-64 p-Nitrophenol and 2,6-dimethyl-4-nitrophenol both have pKa ! 7.15,

but 3,5-dimethyl-4-nitrophenol has pKa ! 8.25. Why is 3,5-dimethyl-4-
nitrophenol so much less acidic?
OH OH OH
H3C CH3
H3C CH3
NO2 NO2 NO2
pK a = 7.15 pK a = 7.15 pK a = 8.25
17-65 Compound A, C10H18O, undergoes reaction with dilute H2SO4 at 25 °C

to yield a mixture of two alkenes, C10H16. The major alkene product, B,
gives only cyclopentanone after ozone treatment followed by reduction
with zinc in acetic acid. Write the reactions involved, and identify A
and B.
80485_ch17_0525-0567n.indd 11 2/2/15 2:09 PM

exercises 567l
17-66 Compound A, C5H10O, is one of the basic building blocks of nature.

All steroids and many other naturally occurring compounds are built
from compound A. Spectroscopic analysis of A yields the following
information:
IR: 3400 cm!1; 1640 cm!1

1H NMR: 1.63 ! (3 H, singlet); 1.70 ! (3 H, singlet); 3.83 ! (1 H, broad
singlet); 4.15 ! (2 H, doublet, J ! 7 Hz); 5.70 ! (1 H, triplet, J ! 7 Hz)
(a) How many double bonds and/or rings does A have?
(b) From the IR spectrum, what is the identity of the oxygen-containing
functional group?
(c) What kinds of protons are responsible for the NMR absorptions listed?
(d) Propose a structure for A.
17-67 Dehydration of trans-2-methylcyclopentanol with POCl3 in pyridine
yields predominantly 3-methylcyclopentene. Is the stereochemistry of
this dehydration syn or anti? Can you suggest a reason for formation of
the observed product? (Make molecular models!)
17-68 2,3-Dimethyl-2,3-butanediol has the common name pinacol. On heat-
ing with aqueous acid, pinacol rearranges to pinacolone, 3,3-dimethyl-
2-butanone. Suggest a mechanism for this reaction.
HO OH O CH3
H3O+
C C C C + H2O
H3C CH3 CH3
H3C CH3 H3C CH3
Pinacol Pinacolone
17-69 As a rule, axial alcohols oxidize somewhat faster than equatorial alco-
hols. Which would you expect to oxidize faster, cis-4-tert-butylcyclo-
hexanol or trans-4-tert-butylcyclohexanol? Draw the more stable chair
conformation of each molecule.
17-70 Propose a synthesis of bicyclohexylidene, starting from cyclohexanone
as the only source of carbon.
Bicyclohexylidene
17-71 A problem often encountered in the oxidation of primary alcohols to

acids is that esters are sometimes produced as by-products. For exam-
ple, oxidation of ethanol yields acetic acid and ethyl acetate:
O O
CrO3
CH3CH2OH CH3COH + CH3COCH2CH3
Propose a mechanism to account for the formation of ethyl acetate. Take

into account the reversible reaction between aldehydes and alcohols:
O HO OR′
C + R′OH C
R H R H
80485_ch17_0525-0567n.indd 12 2/2/15 2:09 PM

Ethers and Epoxides;
Thiols and Sulfides
Ethers and Their Relatives
• An ether has two organic groups (alkyl, aryl, or vinyl)
bonded to the same oxygen atom, R–O–R¢
• Diethyl ether is used industrially as a solvent
• Tetrahydrofuran (THF) is a solvent that is a cyclic ether
• Thiols (R–S–H) and sulfides (R–S–R¢) are sulfur (for oxygen)
analogs of alcohols and ethers

Naming Ethers
• Simple ethers are named by identifying the two organic
substituents and adding the word ether
• If other functional groups are present, the ether part is
considered an alkoxy substituent

Structure, Properties and
Sources of Ethers
• R–O–R ~ tetrahedral bond angle (112° in dimethyl ether)
• Oxygen is sp3-hybridized
• Oxygen atom gives ethers a slight dipole moment
• Diethyl ether prepared industrially by sulfuric acid–
catalyzed dehydration of ethanol – also with other primary
alcohols

The Williamson Ether Synthesis
• Reaction of metal alkoxides and primary alkyl halides and
tosylates
• Best method for the preparation of ethers
• Alkoxides prepared by reaction of an alcohol with a strong
base such as sodium hydride, NaH

Reactions of Ethers: Acidic
Cleavage
• Ethers are generally unreactive
• Strong acid will cleave an ether at elevated temperature
• HI, HBr produce an alkyl halide from less hindered
component by SN2 (tertiary ethers undergo SN1)

Cyclic Ethers: Epoxides
• Cyclic ethers behave like acyclic ethers, except if ring is 3-
membered
• Dioxane and tetrahydrofuran are used as solvents

Epoxides (Oxiranes)
• Three membered ring ether is called an oxirane (root “ir”
from “tri” for 3-membered; prefix “ox” for oxygen; “ane”
for saturated)
• Also called epoxides
• Ethylene oxide (oxirane; 1,2-epoxyethane) is industrially
important as an intermediate
• Prepared by reaction of ethylene with oxygen at 300 °C and
silver oxide catalyst

Epoxides from Halohydrins
• Addition of HO-X to an alkene gives a halohydrin
• Treatment of a halohydrin with base gives an epoxide
• Intramolecular Williamson ether synthesis

Ethylene Glycol
• 1,2-ethanediol from acid catalyzed hydration of ethylene
• Widely used as automobile antifreeze (lowers freezing
point of water solutions)

Addition of Grignards to
Ethylene Oxide
• Adds –CH2CH2OH to the Grignard reagent’s hydrocarbon
chain
• Acyclic and other larger ring ethers do not react

Thiols and Sulfides
• Thiols (RSH), are sulfur analogs of alcohols
• Named with the suffix -thiol
• SH group is called “mercapto group” (“capturer of
mercury”)

Sulfides
• Sulfides (RSR¢), are sulfur analogs of ethers
• Named by rules used for ethers, with sulfide in place of
ether for simple compounds and alkylthio in place of
alkoxy

Thiols: Formation and
Reaction
• From alkyl halides by displacement with a sulfur
nucleophile such as -SH
• The alkylthiol product can undergo further reaction
with the alkyl halide to give a symmetrical sulfide,
giving a poorer yield of the thiol

Using Thiourea to Form Alkylthiols
• Thiols can undergo further reaction with the alkyl halide to
give dialkyl sulfides
• For a pure alkylthiol use thiourea (NH2(C=S)NH2) as the
nucleophile
• This gives an intermediate alkylisothiourea salt, which is
hydrolyzed cleanly to the alkyl thiourea

Oxidation of Thiols to
Disulfides
• Reaction of an alkyl thiol (RSH) with bromine or iodine
gives a disulfide (RSSR)
• The thiol is oxidized in the process and the halogen is
reduced

Sulfides
• Thiolates (RS-) are formed by the reaction of a thiol with a
base
• Thiolates react with primary or secondary alkyl halide to
give sulfides (RSR’)
• Thiolates are excellent nucleophiles and react with many
electrophiles

Sulfides as Nucleophiles
• Sulfur compounds are more nucleophilic than their oxygen-
compound analogs
• 3p electrons valence electrons (on S) are less tightly
held than 2p electrons (on O)
• Sulfides react with primary alkyl halides (SN2) to give
trialkylsulfonium salts (R3S+)

Oxidation of Sulfides
• Sulfides are easily oxidized with H2O2 to the sulfoxide
(R2SO)
• Oxidation of a sulfoxide with a peroxyacid yields a sulfone
(R2SO2)
• Dimethyl sulfoxide (DMSO) is often used as a polar aprotic
solvent

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Chapter

2: Chemistry of Alcohols and

John McMurry 9th Edition

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i • Produces H3O+ and an alkoxide ion, RO-, or a a proton

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• The acidity constant, Ka, measure the extent to which a

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3. Oxidation of phenols to quinones (Section 17-10)

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17-24 Name and assign R or S stereochemistry to the product(s) you would

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17-26 Acid-catalyzed dehydration of 2,2-dimethylcyclohexanol yields a mix-

17-27 Epoxides react with Grignard reagents to yield alcohols. Propose a

17-28 Treatment of the following epoxide with aqueous acid produces a

17-29 Reduction of 2-butanone with NaBH4 yields 2-butanol. Is the product

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17-32 The conversion of 3° alcohols into alkenes under acidic conditions

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(b) CO2H CH2OH

(c) CO2H CH2SH

17-58 Benzoquinone is an excellent dienophile in the Diels–Alder reaction.

17-60 Benzyl chloride can be converted into benzaldehyde by treatment with

Benzyl chloride Nitromethane anion Benzaldehyde

17-61 Reaction of (S)-3-methyl-2-pentanone with methylmagnesium bromide

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