Alkohol dan Fenol

• Alkohol dan fenol dapat dianggap sebagai turunan organik dari air di mana salah
satu hidrogen air digantikan oleh sebuah gugus organik: H-O-H vs R-O-H dan Ar-
OH
• Nama alkohol merujuk kepada senyawa yang memiliki gugus OH yang terikatan
pada carbon atom yang terhibridisasi Sp3, sementara gugus fungsi yang terikatan
pada vinilik, atom C terhibridisasi sp2 disebut senyawa enol
• 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
 Tata Nama Alkohol dan Fenol
Alkohol diklasifikasikan sebagai alkohol primer (1°), sekunder (2o), atau tersier
(3°). Tergantung pada jumlah ikatan organik dengan karbon yang memiliki
gugus hidroksil
Aturan Tata Nama Alkohol

• Pilih rantai karbon terpanjang yang mengandung gugus hidroksil,

jadikan sebagai nama induk dengan menggantikan nama alkananya
dengan akhiran ol. Misalnya propana menjadi propanol
• Penomoran rantai dimulai pada bagian ahir yang terdekat dengan
gugus hidroksil
• Penomoran substituent berdasarkan posisinya pada rantai utama
dan dituliskan berdasarkan urutan alfabet dan identifikasikan posisi
dimana gugus hidroksil melekat
 Penamaan Fenol

• Use “phene” (the French name for benzene) as the parent

hydrocarbon name, not benzene

• Name substituents on aromatic ring by their position from OH

Properties of alcohol and phenols
• 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
• Seperti air, alkohol dan fenol memiliki titik didih yang lebih tinggi karena adanya
ikatan hidrogen.
• Sebuah atom hidrogen -OH yang terpolarisasi positif dari satu molekul tertarik ke
sepasang elektron yang berada pada atom oksigen yang terpolarisasi
elektronegatif dari molekul lain, menghasilkan gaya lemah yang menyatukan
molekul-molekul tersebut
• Daya tarik antarmolekuler ini harus berkurang agar molekul air dapat memasuki
fase uap dari fase cairan. Akibatnya memerlukan suhu yang tinggi untuk
mengubah fase cair menjadi gas
• Kemiripan lain alkohol dan fenol dengan air adalah alkohol dan
fenol keduanya merupakan asam lemah dan basa lemah
• Sebagai basa lemah, keduanya secara reversibel menerima
proton dari asam kuat untuk menghasilkan ion oksonium,
ROH2+
Sebagai asam lemah, alkohol dan fenol sedikit terdisosiasi
dalam larutan air dengan menyumbangkan proton kepada air,
menghasilkan H₃O⁺ dan ion alkoksida, RO⁻, atau ion fenoksida,
ArO-.
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, the more stable it is. And the greater the
acidity of parents alcohol

• Steric effects are important

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Stronger acid

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Inductive Effects effect on acidity alcohol
• Electron-withdrawing groups make an alcohol a
stronger acid by stabilizing the conjugate base
(alkoxide)

Stronger acid

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Generating Alkoxides from Alcohols

• Karena alkohol adalah asam lemah, mereka tidak bereaksi dengan

basa lemah, seperti amina atau ion bikarbonat, dan mereka hanya
bereaksi dalam batas tertentu dengan hidroksida logam seperti NaOH.
• Namun, alkohol bereaksi dengan logam alkali dan basa kuat seperti
sodium hydride (NaH), sodium amide (NaNH2), dan reagen Grignard
(RMgX).
• Alkoksida sendiri adalah basa yang sering digunakan sebagai reagen
dalam kimia organik. Mereka dinamai secara sistematis dengan
menambahkan sufiks -ate pada nama alkohol. Misalnya, metanol
menjadi metanolat.

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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

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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

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p-Nitrobenzyl alcohol is more acidic than benzyl alcohol. Explain.

OH OH

O2N

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 Preparation of Alcohols: 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

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Review: Preparation of Alcohols by Regiospecific Hydration of
Alkenes
• Direct hidration of akenes with aqueous acid is generally a poor
reaction in laboratorium.
• Hydroboration/oxidation: syn, non-Markovnikov hydration
• Oxymercuration/reduction: Markovnikov hydration

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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

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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

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Reduction of Aldehydes and Ketones
• Aldehydes gives primary alcohols

• Ketones gives secondary alcohols

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• Literally dozens of reagents are used in the laboratory to
reduce aldehydes and ketones, depending on the
circumstances, but sodium borohydride, NaBH4, is
usually chosen because of its safety and ease of handling.
• Sodium borohydride is a white, crystalline solid that can
be weighed in the open atmosphere and used in either
water or alcohol solution to give high yields of products.
• Lithium aluminum hydride, LiAlH4, is another reducing
agent often used for reduction of aldehydes and ketones.
Agrayish powder that is soluble in ether and
etrahydrofuran, LiAIH4 is much more reactive than
NaBH4 but also more dangerous.
• It reacts violently with water and decomposes explosively
when heated above 120°C.
Reduction of Carboxylic Acids and Esters
• Carboxylic acids and esters are reduced to give
primary alcohols
• LiAlH4 is used because NaBH4 is not effective

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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

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31
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

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Examples of Reactions of Grignard Reagents with Carbonyl Compounds

• Formaldehyde reacts with Grignard reagents to yield primary

alcohols.

• Aldehydes react with Grignard reagents to yield secondary alcohols.

• Ketones yield tertiary alcohols.

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Examples of Reactions of Grignard Reagents with Carbonyl Compounds

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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

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Reaction of 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

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Conversion of Alcohols into AIkyl Halides

• Tertiary alcohols react with either HCl or HBr at 0 °C by an

SN1 mechanism through a carbocation intermediate.
• Primary and secondary alcohols are much more resistant to
acid, however, and are best converted into halides by treatment
with either SOCl2 or PBr3 through an SN2 mechanism.
• The reaction of a tertiary alcohol with HX takes place by an
SN1 mechanism when acid protonates the hydroxyl oxygen
atom, water is expelled to generate a carbocation, and the
cation reacts with nucleophilic halide jon to give the alkyl
halide product.
• The reactions of primary and secondary alcohols with SOCl2
and PBr3 take place by SN2 mechanisms.
• Hydroxide ion itself is too poor a leaving group to be displaced
by nucleophiles in SN2 reactions, but reaction of an alcohol
with SOCl2 or PBr3 converts the -OH into a much better
leaving group, either a chlorosulfite(-OSOCl) or a
dibromophosphite (-OPBr2), that is readily expelled by
backside nucleophilic substitution.
Conversion of Alcohols into Tosylates
• Alcohols react with p-toluenesulfonyl chloride (tosyl
chloride, p-TosCI) in pyridine solution to yield alkyl
tosylates, ROTos .
• Only the O-H bond of the alcohol is broken in this
reaction; the C-0 bond remains intact, so no change
of configuration occurs if the oxygen is attached to a
chirality center.
• The resultant alkyl tosylates behave much like alkyl
halides, undergoing both SNI and SN2 substitution
reactions.
• One of the most important reasons for using tosylates in SN2
reactions is stereochemical. The SN2 reaction of an alcohol via
an alkyl halide proceeds with two inversions of configuration-
one to make the halide from the alcohol and one to substitute
the halides and yields a product with the same stereochemistry
as the starting alcohol.
• The SN2 reaction of an alcohol via a tosvlate, however,
proceeds with only one inversion and yields a product of
opposite stereochemistry to the starting alcohol. Figure 17.5
shows a series of reactions on the R enanliomer of 2-octanol
that illustrates these stereochemical relationships .
Dehydration of Alcohols to Yield Alkenes
• A third important reaction of alcohols, both in the
laboratory and in biological pathways. is their
dehydration to give alkenes.
• The C-O bond and a neighboring C-H are broken, and
an alkene bond is formed.
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  bond

• Specific reagents are needed

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Acid-Catalyzed Dehydration
• Tertiary alcohols are readily dehydrated with acid

• Secondary alcohols require severe conditions (75%

H2SO4, 100°C) - sensitive molecules don't survive

• Primary alcohols require very harsd conditions –

impractical

• Reactivity is the result of the nature of the carbocation

intermediate (See Figure 17-5)

• Note that Zaitsev’s rule is followed!

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49
Dehydration with POCl3
• Phosphorus oxychloride in the amine solvent pyridine
can lead to dehydration of secondary and tertiary
alcohols at low temperatures

• An E2 via an intermediate ester of POCl2 (see Figure

17.6)
N

pyridine

Follows an E2 mechanism
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Mechanism 1: Dehydration of Alcohol (2 or 3 )

HCl

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Conversion of Alcohols into Alkyl Halides
• 3° alcohols are converted by HCl or HBr at low
temperature (Figure 17.7)

• 1° and 2° alcohols are resistant to acid – use SOCl2 or

PBr3 by an SN2 mechanism (ether solvent)

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Mechanism 2:

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

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

• Converts secondary alcohol to ketone

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Oxidation of Primary Alcohols
• Jones’ Reagent: CrO3 in aqueous sulfuric acid.
• Oxidizes primary alcohols to carboxylic acids:

All of the oxidations occur via an E2 mechanism.

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Mechanism of Chromic Acid Oxidation
• Alcohol forms a chromate ester followed by
elimination with electron transfer to give ketone
• The mechanism was determined by observing the
effects of isotopes on rates

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 Oxidation of Secondary Alcohols

• Na2Cr2O7 in aqueous acetic acid is an inexpensive oxidizing agent:

Na2Cr2O7
CH3 OH CH3 O
acetic acid
4-tert-Methylcyclohexanol 4-tert-Methylcyclohexanone

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