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The Syrian International Private University For Science And


Technology  

College of pharmacy

Organic Chemistry
Second year students

:: Alcohols and Ethers ::

Ass.Professor Dr.Musasthanna D.Saud


Reference: Organic Chemistry by Morrison and Boyed

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A
Alcohols
s
Stru
ucture of Alcohols :
Alcoohols are orrganic comppounds of thhe general formula
f R-OOH, where R is any alkkyl or substiituted alkyl
grouup. R groupp may be priimary, seconndary, or teertiary; it maay be open chain or cycclic. It may contain othher
funcctional grouup as well. For
F examplee:

2-Methyy-2-propanol 2-propen-1-ol
tert-Bu
utyl alcohol Allyl alcoholl Cyclohex
xanol

Benzzyl alcohol 2
2-chloroethanool 1,2,3-propaanetriol
Ethyylene chlorohy
ydrin Glycerrol

All alcohols coontain the hyydroxyl (-OOH) group, which


w is thee functional that determ
mine the propperties
charracteristic of
o this familyy. The diffeerence in thee R groups will affect the
t rate of wwhich the allcohol
undergoes certaain reactionns. It also may affect the kind of reeaction.

Phennols also coontain hydrooxyl group, but it is attached direcctly to the arromatic ringg and so, theey differ so
marrkedly form alcohols inn their physiical and cheemical properties and tyype of reacttions they undergo.
u

a primary, secondary, or tertiary according


Alcoohols couldd classifies as a too the kind oof carbon that bears thee
-OH
H group.

6.4 Nomencllature of alcohols:


a
Aasaslso the coommon nam mes are usedd for simple alcohols which
w consisst of the nam
me of the alk
kyl group
folloowed by thee word alcohol. For exaample:

E
Ethylalcohol Isoproppyl alcohol Isobutyl allcohol tert-buty
yl alcohol
(1o) (22o) (1o) (3o)

Thee most versaatile system is, of coursse, the IUPA


AC. The rules are:
1- Choosinng the longeest continuoous carbon chain
c that contains the –OH groupp.
2- Indicatee by a nasummber the poosition of thee –OH grouup in the preesent chain, generally using
u the low
west
assaposssible number of –OH.
3- Indicatee by numberr the positioons of otherr groups attaached to thee parent chaain.
M
Methanol 1
1-Propanol 1-bromo--2-propanol 1,2
2-Ethanediol

2,2-dimethyll-1-propanol 2-methyl-1-butanol
6.5 Physical properties
p s of Alcoh
hols:
Struucturally, ann alcohol is a compositee of an alkaane and wateer:
R-H
H H-OH R- OHH
An alkkane Water An alccohol
It coontains an alkane
a like alkyl
a group and water like
l hydroxy yl group. Thhe –OH grooup gives th he alcohol itts
charracteristic physical
p properties, andd the alkyl group
g depen
nding upon itsi size and shape, mod difies this
propperties.
Hyddroxyl groupp (-OH) is polar-it
p conttains hydroggen bondedd to the highhly electroneegative elem
ment oxygenn.
Throough the hyydroxyl grouup, an alcohhol is capabble of hydrog gen bondingg:

Beccause of hyddrogen bondding, alcohools have higgher boiling points thann compoundds of similarr molecular
weigght (aldehyde, ketons and
a ethers).
o alcohols in water is also
Thee solubility of a due to the polarity y of the hydrroxyl groupp and to the ability to foorm
hydrrogen bondds with wateer moleculess. But the efffect of the –OH groupp decreases w with increasse the size of
o
the alkyl
a groupp (the numbeer of carbonn atoms), i.ee., the non-p
polar portion of the alcohol molecu ule.

So, increasing the


t size of the
t alkyl grooup (non-poolar portionn) is associatted with deccrease the solubility in
wateer (aqueouss solubility).
Induustrial sourcce of Alcohols:
a- By hydrration of alkkenes obtainned from thee cracking of
o petroleumm
b- By the oxo
o process from alkennes, carbon monoxide
m and
a hydrogeen.
c- By fermmentation off carbohydraate.
Alcohols as acids and bases:
Like water, alcohols are weak acids and weak bases.
The oxygen with its unshared electrons pairs, that makes as alcohol basic.
ROH 2 + HSO4 -
+
R - OH + H 2 SO 4
In alcohols hydrogen is bonded to the very electronegative element oxygen. The polarity of the –OH bond
facilitate the breaking of –OH bond.
1
ROH + Na RONa + H2
2
An alcohol A sodium
(A weak acid) (alkoxide, a strong base)

RO - Na + + HOH NaOH + RO - H
Strong base strong acid weaker base weaker acid

Like water and ammonia, alcohols are stronger acids than alkanes, and readily displace them from their salts
from Grignard reagents
ROH + R ′ Mg X R ′ H + Mg(OR) X
Stronger acid weaker acid

Relative acidities H 2 O 〉 ROH 〉 NH 3 〉 RH

Relative basicities OH - 〉 OR - 〉 NH 2 - 〉 R -

Rule: one compound is shown to be a stronger acid than another by its ability to displace the second
compound from salts.
A-H + B- M + B - H + A -M +
Alcohols are weaker acids than water as we mentioned above, an alkoxide is not prepared by the reaction of
alcohols with sodium hydroxide because of the presence of water in the aqueous solution of sodium
hydroxide.
+ OH -
+
ROH + H O 2 ROH 2

Alkoxide are prepared by reaction of alcohols with the active metal itself (Na, K) in the absence of water.
1
ROH + Na RO - Na + + H2
2
Alkoxides are useful reagent, they are powerful bases-stronger than hydroxide.
6.10
0 Preparation of Alcohols:
1-O
Oxymercuraation-demeercuration:
Alkenes react with
w mercurric acetate inn the presennce of waterr to give hydroxymercuurial compo
ounds whichh on
reduuction yieldd alcohols.

Alkkene merccuricacetate Alcohol (Marrkovnikov rule)

2- hydroborati
h ion-oxidatiion:

Isobutylene utylalcohol (11o)


Isobu

3- Grignard
G synthysis:

4- Hydrolysis
H o alkyl hallides:
of
Reaaction of A
Alcohols: 
1-R
Reaction of
o alcoholss with hyd
drogen haalides. Acid
d catalysiss

Thee hydroxyl group


g in a poor leavingg group. Thiis is accomp
plished by thhe presencee of acid wh
hich protonaate
the hydroxyl
h grroup and coonvert it to good
g leavingg group.

a- The reaaction is cataalyzed by accids.


Even thhough the aqqueous hydrrogen halidees are themselves stronng acids, thee presence of
o additionaal
sulfuricc acid speedds up the forrmation of alkyl
a halidess.
b Rearranngement of the
b- t alkyl grroup occurs except, 1o alcohol.
a

c- The ordder of reactivvity of alcoohols towardd HX is 3o > 2o > 1o < CH


C 3

Sn2 mechanism:
m
most 1o alcohhols and methaanol
2-Fromation of alkyl sulfonates:
Sulffonic acids, ArSO3H, are
a related too sulfuric accid and are strong acids. This anioons, the sulffonates, are
weaak bases andd hence goood leaving group.
g
ArSO + H +

ArSO H 3 3

Strong accid Sulfonatee anion


Weak base
b
As a result, alkkyl sulphonaates undergoo nucleophiilic substituttion (and elimination) iin much thee same mannner
as alkyl
a halidess.
Likee alkyl haliddes, alkyl suulfonates arre readily made
m from allcohols.

6.15
5 Oxidatio
on of Alco
ohols:
Thee oxidation of
o an alcohool involves the
t loss of one
o or moree hydrogenss (α-hydrogeens) from th he carbon
bearring the –OHH group.
A prrimary alcoohol containns two α-hyddrogens, andd can eitherr loss one off them to foorm an aldeh
hyde,

Or both
b of them
m to form caarboxylic accid

A seecondary alcohol can loose its only α-hydrogenns to form a ketone.

A teertiary alcohhol containss no α-hydroogens and iss not oxidizzed.


(Ann acidic oxiddizing agentt can, howevver, dehydrrate the alcoohol to an allkane and thhen oxidize this).
Of the
t many reagents that can be suedd to oxidize alcohols, we
w can consider only thhe most com
mmon ones,
thosse containinng Mn (VII)) or Cr (VI)).

Oxiddation of prrimary alcohhols to carbboxylic acidds is usually accomplishhed by use oof potassium
m
perm
manganate.

+1 +7 -8
R
RCH 2 OH + K Mn O 4 ROO − K + + MnnO 2 + KOH
H
1o alcohol purple solublle in water

H+

RCOOOH A carbooxylic acid innsoluble in watter


Oxiddation of alcohols to thhe aldehyde or ketone stage
s is usuaally accompplished by thhe use of Cr (VI) as
K2Cr
C 2O7 or CrO O3.

Prim u of special reagent ccalled pyridiinium


mary alcohools can be coonverted onnly to aldehyyde by the use
chloorochromatee .
:
::Ethers
s::

6.16
6 Structurre and nomenclature of Ethe
ers :
Etheers are comppounds withh the generaal formula R-O-R,
R Ar-O
O-R or Ar-O
O-Ar.

If thhe two groupps are identtical, the ethher is said too be symmeetrical (e.g.,, diethyletheer…..), if diifferent,
unsyymmetricall (tert-butylm metylether)).

6.17
7 Physical al properties of Ethers :

Etheer have dipoole momentt because thhe C-O-C boond angle iss not 180o. this
t weak poolarity don'tt affect to a high
exteend the boiliing points of
o ethers.

Etheers can form


m hydrogen bonding wiith water soo they have comparablee solubility in water to alcohols wiith
the same moleccular weightt.

6.18
8 Structurre and nomenclature of Ethe
ers :
A nuumber of syymmetrical ethers are prepared
p by the reaction
ns of the coorrespondingg alcohols with
w sulfuricc
acidd.

Thiss reaction iss a kind of dehydration


d n.

Alcoohols can undergo anotther kind off dehydratioon, involvin


ng eliminatioon, to give aalkenes.
Dehhydration to ethers rather than to alkenes in coontrolled by
y choice of the
t reactionn conditions. For exampple:

Etheers formatioon by dehyddration is ann example of o nucleophiilic substituution with allcohol playiing two rolees:
the protonated
p alcohol is thhe substratee, and the seecond moleccule of alcoohol in the nnucleophile. The reactioon
coulld be either Sn1 or Sn22.

On standing
s in contact witth air, most aliphatic etthers are con
nverted slow
wly into unsstable perox
xides:

The presence of peroxides, although in i only low concentratiions are veryy dangerouss, since they
y can cause
viollent explosioon during distillation
d thhat normallyy follow ex
xtraction witth ether.

The presence of peroxides is indicatedd by formattion of a red


d color with the ether thhough shakiing with an
aqueeous solutioon of ferrouus ammoniumm sulfate annd potassium
m thiocyanaate; the perooxides oxid
dizes ferrouss ion
to feerric ion; whhich react with
w thiocyaanate ion to give blood--red color of
o the compllex.

Perooxides couldd be removeed by distilllation with concentrateed H2SO4 orr by washingg with soluttion of ferroous
ion (which reduuce peroxiddes).
6.19
9 Preperation of Ethers :

Williamson
1.W n synthesiis:

In thhe Williamsson synthesis of ethers an alkyl haalide (or sub


bstitution alkkyl halide) is allowed to
t react withh
sodiium alkoxidde.

For example:

Reaaction involvves nucleopphilic substitution of alkkoxide ion for


f halide ioon; it is sim
milar to the formation
f off
alcoohols by treaatment of allkyl halidess with aqueoous hydroxide.

2.A
Alkoxymerrcuration--demercurration:
6.21 Reaction
ns of Ethe
ers, Cleavaage by accids

Reaactivity of HX
H : HI > HBr > HCl

Sn1 Mechanism
m:

Sn2 Mechanism
m:

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