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Some Compounds with Oxygen, Sulfur, or Halogens

Laboratorium Kimia Organik ʹ Jurusan Kimia

Fakultas Matematikan dan Ilmu Pengetahuan Alam
Universitas Padjadjaran
2009
Some Compounds with Oxygen, Sulfur, or Halogen

1. How do alcohols, phenols, and ethers compare with water and alkanes?
Be able to describe the major differences in properties among members of
these families.
2. What are the distinguishing feature of ethers, sulfur-containing compounds, and
halogen-containing compounds?
Be able to describe the structures and outstanding properties of compounds
with these functional groups.
3. How are alcohols, phenols, ether, sulfur-containing compounds, and halogen-
containing cmpounds named?
Be able to give systematic names for the simple members of these families and
write their structures, given the names.
4. What are the general properties of alcohols and phenols?
Be able to describe such properties as polarity and hydrogen bonding, water
solubility, and boiling points.
5. What are alcohols and phenols weak acids?
Be able to show why alcohols and phenols are acids.
Some Compounds with Oxygen, Sulfur, or Halogen

]. What are the major chemical reactions of alcohols?

Be able to describe and predict the products of the dehydration and oxidation
of alcohols.
7. What are some of the significant application of alcohols, phenols, ethers, sulfur-
containing compounds, and halogen-containing compounds ?
Be able to describe and predict the products of the dehydration and oxidation
of alcohols.
 Alcohols, Phenols, and Ethers

Alcohol, a compound that contains an ͶOH functional group covalently

bonded to an alkane-like carbon atom (RͶOH).
Hydroxyl group, a name for the ͶOH group in an organic compound.
Phenol, a compound that has an ͶOH functional group bonded directly to
an aromatic, benzene-like ring.
Eteher, acompound that has an oxygen atom bonded to two carbon atoms
(RͶOͶR).
 Alcohols, Phenols, and Ethers

Ethyl alcohol, dimethyl ether, and propane have similar molecular weights, yet
ethyl alcohol boils more than 100YC higher than the other two.
In fact, the boiling point of ethyl alcohol is close to that of water.
Why should this be?
 Alcohols, Phenols, and Ethers

a b

The formation of hydrogen bonds in water (a) and alcohols (b).

Due to the attractive forces of the hydrogen bonds, the easy escape of
molecules into the vapour phase is prevented, resulting in high boiling points.
 Some Common Alcohols
Methyl Alcohol (CH3OH, Methanol), the simplest alcohol, is commonly known
as wood alcohol because it was once prepared by heating wood in the
absence of air.
Today it is made in large quantities from a mixture of carbon monoxide and
hydrogen,

Ethyl Alcohol (CH3CH2OH, Methanol), is one of the oldest known pure organic
chemicals, and it production by fermentation of grain and sugar goes back for
many thousans of years.
Sometimes called grain alcohol, ethyl alcohol is the ͞alcohol͟ present in all
table wines (10-13%), beers (3-5%), and distilled liquors (35-90%).
During fermentation, starches or complex sugars are converted to simple
sugars (C]H12O]) which are then converted to ethyl alcohol:
 Some Common Alcohols
Isopropyl Alcohol ((CH3)2CHOH, Isopropanol) or rubbing alcohol, is usedas a
70% mixture with water for rubdowns because it cools the skin through
evaporation and causes pors to close.
It͛s also used as a solvent for medicines, as a sterilant for instrument, and to
cleanse the skin before drawing blood or giving injection.

Ethylene Glycol (HOCH2CH2OH), a dialcohol, ethylene glycol is a colorless liquid

miscible with water and insoluble in non-polar solvent.
It͛s two major uses are in antifreeze and in making polymer film and fiber such
as Dacron.
Glycerol (HOCH2CH(OH)CH2OH), the trialcohol glycerol is a colorless liquid that
is miscble with water.
Unlike ethylene glycol, it͛s not toxic but has a sweet taste that͛s put to use in
candy and prepared foods.
Glycerol, often called glycerin, is also used in cosmetic and tobacco as a
moisturizer, in plasctics manufacture, in antifreeze and shock absorber fluids,
and as a solvent.
 aming Alcohols
Alcohol are classified according to the number of carbon substituents
bonded to the hydroxyl-bearing carbon.

Primary alcohol, an alcohol in which the OH-bearing carbon atom is bonded

to one other carbon (and two hydrogens), RCH2OH.
Secondary alcohol, an alcohol in which the OH-bearing carbon atom is
bonded to two other carbon (and one hydrogens), R2CHOH.
Tertiary alcohol, an alcohol in which the OH-bearing carbon atom is bonded
to three other carbon (and no hydrogens), R3COH.
 aming Alcohols
Step 1. ame the parent compound
!ind the longest chain containing the hydroxyl group and name the chain by
replacing the ʹe ending by of the corresponding alkane with ʹol.
If the compound is cyclohexane, its name provides the root name, for example, the
cyclohexanol

Step 2. umber the carbon atoms in the main chain.

Begin at the end nearer the hydroxyl group, ignoring the location of other
substituents

In an OH-substituted cycloalkane, begin with the ʹOH group

 aming Alcohols
Step 3. Identify and number the hyroxyl group and the substituents

Step 4. Write the full name

lace the number that
locates the hydroxyl group
immediately before the
parent compound name
(with the-ol ending).
Number all other
substituents according to
their positions and list
them alphabetically.
Properties of Alcohols
 Properties of Alcohols

V Hdyrogen bonding is the major influence on the physical properties of

alcohols.
V Straight-chain alcohols with up to 2 carbons atoms are liquids, and each
boils at a higher temperature than similar alkanes.
V Low-molecular-weight alcohols such as methanol and ethanol are water-
like in their solubility behaviour.
V Methanol and ethanol are both infinitely solble i water, with which they
can form hydrogen bonds.
V Higher-molecular-weight alcohols, such as 1-heptanol, however, are
much more alkane-like and less water-like.
V Alcohols are hydrogen-bonded and higher boiling than similar alkanes.
V Common alcohols are liquids.
V Lower alcohols are miscible with water; higher dialcohols are more
water-soluble than similar monoalcohols.
V Alcohols are very weak acids (proton donors); water solution are neutral.
V Common alcohols are flammable; can be toxic.
V Dehydration and oxidation are major alcohol reactions.
 Properties of Alcohols

V Alcohols with two or more ͶOH groups can form more than one
hydrogen bond
V They are therefore higher boiling and water-soluble than similar alcohols
with one ͶOH group.
 Chemical Reactions of Alcohols
Dehydration of Alcohols
rlcohls undergo loss of water (dehydration) on treatmen with a strong acid
catalyst. The OH group is lost from adjacent carbon to yield an alkene
product:
 Chemical Reactions of Alcohols
Dehydration of Alcohols
rlcohls undergo loss of water (dehydration) on treatmen with a strong acid
catalyst. The OH group is lost from adjacent carbon to yield an alkene
product:

V In cases wheremore than one alkene can result from dehydration, a

mixture of products is usually formed.
V A good rule of thumb is that the major product is the one that has the
greater number of alkyl groups attached to the double-bond carbons.
 Chemical Reactions of Alcohols
Oxidation of Alcohols
rimary and secondary alcohols are converted into carbonyl-containing
compounds on treatment with oxidizing agent.

Carbonyl group is a functional group that has a carbon atom joined to an

oxygen atom by a double bond, C=O.
Oxidizing agents: potassium permanganate (KMnO4)
Sodium dichromate (a2Cr2O7)
tric acid (HO3)
We͛ll simply use the symbol [O] to indicate a generalized reagent.
 Chemical Reactions of Alcohols
Oxidation of Alcohols
rimary and secondary alcohols are converted into carbonyl-containing
compounds on treatment with oxidizing agent.

V The net effect of an alcohol oxidation is the removel of two hydrogen

atoms.
V One hydrogen comes from the ͶOH group, and the other comes from
the carbon atom bonded to the ͶOH group.
V This hydrogens are converted into water during the reaction by the
oxidizing agent [O].
 Chemical Reactions of Alcohols
Oxidation of Alcohols
rimary and secondary alcohols are converted into carbonyl-containing
compounds on treatment with oxidizing agent.
V Different kind of carbonyl-containing product are formed depending on
the structure of the starting alcohol and on the exact reaction conditions.
V Thus, primary alcohols (RCH2H) are converted either into aldehyde
(RCH=O) if carefully controlled conditions are used, or into carboxylic
acids (RCOOH) if an excess of oxidant is used.
 Chemical Reactions of Alcohols
Oxidation of Alcohols
rimary and secondary alcohols are converted into carbonyl-containing
compounds on treatment with oxidizing agent.
V Secondary alcohols (R2CHOH) are converted into ketones (R2C=O) on
treatment with oxidizing agents.
 Chemical Reactions of Alcohols
Oxidation of Alcohols
rimary and secondary alcohols are converted into carbonyl-containing
compounds on treatment with oxidizing agent.

V Tertiary alcohols (R3COH) don͛t normaly react with oxidizing agents

because they don͛t have a hydrogen on the carbon atom next to the
͸OH group.
 Chemical Reactions of Alcohols
Oxidation of Alcohols
rimary and secondary alcohols are converted into carbonyl-containing
compounds on treatment with oxidizing agent.

V Alcohol oxidation are critically important steps in many biological

processes, example:
'hen lactic acid builds up in tired, overworked muscles, the liver removes
it by oxidizing it to pyruvic acid.
V Our bodies, of course, don͛t use a2Cr2O7 or KMnO4 for the oxidation;
they use specialized, highly selective enzymes to carry out their
chemistry
 Phenols
V The word phenol is the name both of a specific compound
(hydroxybenzene, C]H5OH) and of a family of compounds.
V The medical use of phenol is now restricted because it can cause severe
skin burns and has been found to be toxic, both by ingestion and by
absorption through the skin and inhalation.
V Phenols and substituted phenols such as the cresols (methylphenols) are
common as desinfectants in hospital and elsewhere.
 Phenols
V Phenols are usually named with the ending-phenol rather than ʹbenzene,
for example:

V The properties of phenols, like those of alcohols, are influenzed by

hydrogen bonding.
V Most phenols are water-soluble to some degree and have higher melting
point and boiling points than similarly substituted alkylbenzenes.
 Acidity of Alcohols and Phenols
V Alcohols and phenols are weakly acidic. They dissociate only slightly in
aqueous solution and therefore establish equilibria.

V Methanol and ethanol are no more acidic than water itself and are so
slightly dissociated in water that requir aqueous solution are neutral (pH 7).
V The anion of an alcohol, RO-, known as an alkoxide ion, is a strong base, as
expected for the anion of a weak acid.
V Alkoxides are prepared by reaction of an alcohol with an alkali metal, for
example:
 Acidity of Alcohols and Phenols

V Phenols are considerably more acidic than water. Phenol itself (Ka = 1x10-10),
for example, is close to HC (Ka = ]x10-10) and HCO3- (Ka = 5x10-11) in acidity.
V Phenols react as weak Bronsted-Lowry acids with hydroxide ion and are
soluble in dilute aqueous sodium hydroxide.
 ames and Properties of Ethers

V Ethers with simple alkyl or aryl groups are named just by identifying the
two groups bonded to oxygen and adding the word ether

V If both groups are the same, the͟di-͟ is often left out and we refer to
͞methyl ether͟ or ͞ethyl ether͟.
V A reference to just ͞ether͟ usually means diethyl ether.
V Compounds containing the C͸O͸C group in a ring are classified as cyclic
ethers but are not named as such.
 ames and Properties of Ethers
V The RO͸ group is reffered to as an alkoxy group; CH3O͸ is a methoxy,
CH3CH2O͸ is an ethoxy group, and so on.
V These names are used when the ether functional group is present with
other functional groups, for example:

V Though polar, ethers lack the hydroxyl group of water and alcohols, and
ether molecules do not hydrogen-bond to each other.
V Thus, the simple ethers are higher boiling point han comparable alkanes
but lower boiling than alcohols.
V The ether oxygen can hydrogen-bond with water, causing dimethyl ether
to be water-soluble and diethyl ether to be partially miscible with water.
V Higher ethers are not only slightly soluble or insoluble in water. Ether are
good solvent for most organic molecules.
 Properties of Ethers

V o hydrogen bonding occurs between ether molecules, but they

are polar, lower boiling than alcohols, but higher boiling than
alkanes.
V Lower ethers are volatile, flammable liquids.
V Ethers are slightly soluble or insoluble in water (except dimethyl
ether, which is water soluble).
V Are good solvents for organic compounds.
V Are not very reactive.
V Form explosive peroxide on standing in air.
 Some Common Ethers

Inhalation anesthetics
V Enflurane (trade name Enflurane) and
isoflurane (trade name Forane) are
widely used nonflamable, nonexplosive
anesthetics that produce a rapid
anesthesia from which recovery is also
rapid.
V They are both low-boiling liquids
administered as vapors (enflurane, bp
5].5YC; isoflurane, bp 48.5YC).
 Some Common Ethers
V Ethers exist throuhout the plant and animal kingdoms.
V Sme are present in essential oil and are used in perfumes; other have a
variety of biological roles.
V The threemembered epoxide ring in juvenile hormone is quite reactive
because the oxygen and carbon bond angles are highly strained in the
small ring.

Some biomolecules containing ether groups

Sulfur-containing Compounds: Thiols and Disulfides
V Thiols is the elements just below oxygen in the periodic table, and many
oxygen-containing compounds have sulfur analogs.
V Thiols (R͸SH), also called mercaptans, are sulfur analogs of alcohols.
V Mercaptan is an alternate name for a thiol, (R͸SH).
V The systematics parent name of a thiol is formed by adding ʹthiol to the
parent hydrocarbon name.
V Otherwise, thiols are named in the same way as alcohols.
Sulfur-containing Compounds: Thiols and Disulfides

V The most outstanding characteristic of thiols is their appaling odor.

V Thiol react with mild oxidizing agents to yield disulfide, R͸S͸S͸R.
V Two thiols joint together in this reaction, the hydrogen from each is lost,
and then the two sulfurs bond together.
Sulfur-containing Compounds: Thiols and Disulfides
V The reverse of this reaction occur easily in the presence of many reducing
agents, represented here by [H],

[O]
RSSR RSH + RSH

V Thiols are important biologically because they occur as a functional group

in the amino acid cystein, which is part of many proteins
Sulfur-containing Compounds: Thiols and Disulfides
V The easy formation of ͶSͶSͶ bond between cystein groups help to pull
large protein molecules into the shapes they need to function.
V Hair protein, for exanple, is unusually rich in SH groups.
V When hair is͟permed͟ , a mild oxidizing agent causes disulfide bonds to
form between SH groups, resulting in the introduction of bends and kinks
into the hair.

Sulfur bridges in hair. Chemistry can give you curly hair. A permanent wave
results when disulfide bridges are formed between SH groups in hair protein
molecules.
 Halogen-containing Compounds
V Halogen-containing organic compounds result from the replacement of
hydrogen atoms by halogen atoms
V The alkyl halide, RX, where R is an alkyl group and X is halogen.
V Their common names are formed by giving the name of the alkyl group
followd by the alogen name with an-ide ending.
V Systematic name for alkyl halides are derived like those of other families
of compounds, by identifying the hydrocarbon root, using the alkane
ending-ane, numbering the halogen substituens, and naming them as
fluoro-, chloro-, bromo-, or iodo- groups.
 Some Halogen-containing Compounds
V An iodine-containing hormone secreated by the thyroid gland.
V A deficiency of iodine in the human diet leads to a low thyroxine level,
which causes a condition called goiter and a resulting swelling of the
thyroid gland.
 Some Halogen-containing Compounds
V Agricultural use of herbicides such as 2,4-D and fungiside such as Captan
has resulted in vastly increased crop yield and also chlorinated pesticide
of DDT is responsible for the control of malaria and thypus
V But, chlorinated pesticide present problems becausr they are not broken
down by natural processes and persist in the environment.
V They remain in the fatty tissues of organism and accumulate up the food
chain as larger organism consume smaller one.