Philippine Handbook Organic Chemistry

in Chemical Engineering by Vergel Bungay

B2. ORGANIC CHEMISTRY

Organic Chemistry deals with the study of carbon-containing compounds. It also deals with
the relationship between molecular structure and the physical and chemical properties of the
compounds.

B2.1. NATURE OF ORGANIC COMPOUNDS

With the exception of carbonates and cyanides, organic compounds are carbon-containing
compounds. Carbon atoms have the ability to link with each other forming linear, cyclic and
branched backbone. It can form bonds with other atoms and also form multiple bonds. In
addition, organic molecules exhibit both structural isomerism and stereoisomerism. This is the
reason of its great abundance in nature. Likewise, organic compounds are highly covalent
compounds that account for its low melting point and boiling point and limited solubility in
water.

B2.2. STRUCTURAL THEORY, VALENCE BOND THEORY AND

MOLECULAR ORBITAL THEORY

One of the basic foundations of organic chemistry is the structural theory. This theory states
that the atoms of elements in an organic compound form a fixed number of bonds with other
atoms. Atoms can use one or more of its valences to bond with other atoms. A concrete
example is carbon atom. It can form single or multiple bonds with other carbon atoms. This
ability of carbon is called catenation.

The formation of covalent bonds is due to the overlap of atomic orbitals. The Valence Bond
theory is one way of interpreting this bond formation and the electronic structure of atoms.
This theory states that a stable molecule is formed when reacting atoms attained the minimum
potential energy as the atoms approach each other. Furthermore, when two atomic orbitals
overlap, each contains one electron of opposite spins and both atoms share the electron pair.

Another quantum mechanical approach is the Molecular Bond Theory. According to this
theory, the overlap of atomic orbitals leads to the formation of two molecular orbitals, one
with lower energy and highly stable compared to the atomic orbital from which it is formed
(bonding molecular orbital) and another orbital with greater energy and much higher stability
compared to the atomic orbital from which it is formed (antibonding molecular orbital). This
approach best explains the magnetic properties of molecules compared to the valence bond
theory.

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B2.3. HYBRIDIZATION

Based from quantum mechanics, the electronic configuration of carbon in its ground state is
1s2 2s2 2p2. This configuration, however, does not account for the tetravalency of carbon. To
explain the tetravalency of carbon, a mathematical approach is used that encompasses mixing
of wave functions of nonequivalent orbitals to form new sets of hybrid orbitals. This approach
is called hybridization.

One type of hybridization is sp3 hybridization. To explain the bonding in methane, one 2s
orbital and three 2p orbitals combine to form four 2sp3 hybrid orbitals. In the electronic
configuration of carbon using the rectangular arrow method, an electron is promoted from the
2s orbital to the 2p orbital as shown in Figure B2-1.

      
2s 2p 2s 2p

Figure B2 – 1. Excitation of an Electron from 2s Orbital to 2p Orbitals.

Even though there are four unpaired electrons that could form bonds with the hydrogen atom,
the bond angle between carbon and three hydrogens will be 90, which is not the true
molecular geometry observed for methane. Figure B2-2 shows the mixing of these orbitals to
form new hybrid orbitals.

109.5
109.5

2s 2py

109.5
109.5
2pz 2px

Figure B2 – 2. sp3 Hybridization.

The mathematical treatment of these hybrid orbitals further shows that the four 2sp3 hybrid
orbitals are 109.5 with each other. Thus, the shape of methane molecule is tetrahedral.

Other types of hybridization explain the existence of organic compounds in which the carbon
atoms share more than two electrons with another carbon atom. One is sp2 hybridization. In

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this hybridization, one 2s orbital is mixed with two of the 2p orbitals and the remaining 2p
orbital is unhybridized. From this hybridization, three 2sp2 hybrid orbitals are formed that are
oriented towards the corner of a triangle with the unhybridized 2p orbital perpendicular to it.
Thus, the geometry is said to be trigonal planar. Figure B2-3 shows this type of
hybridization.

unhybridized
120
2p orbital

2s 120

120

2pz 2px
Figure B2 – 3. sp2 Hybridization.

The other type of hybridization that explains organic compounds with carbon atoms triply
bonded to another carbon atom is the sp hybridization. Figure B2-4 shows the formation of
two sp hybrid orbitals from one 2s orbital and one of the three 2p orbitals.

unhybridized
2p orbitals

2s 2px

180
Figure B2 – 4. sp Hybridization.

In this type of hybridization, two sp hybrid orbitals are formed oriented at an angle of 180
with each other. It also has two unhybridized 2p orbitals that are perpendicular to each other.

The type of hybridization greatly influences the strength of a bond. Increase in the s character
of the bond orbital results in increase of bond strength, bond order and bond polarity. Bond

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order is the term that denotes the number of bonds shared between two atoms. Bond polarity
indicates the uneven distribution of electrons in a bond shared by two atoms due to their
difference in electronegativity.

B2.4. CLASSES OF ORGANIC COMPOUNDS

Organic compounds are classified as hydrocarbons and hydrocarbon derivatives.

Hydrocarbons are compounds that consist mainly of hydrogen and carbon while hydrocarbon
derivatives are those that contain other atoms such as oxygen, sulfur, nitrogen and halogens.

Hydrocarbons are further classified as aliphatic, alicyclic and aromatic hydrocarbons.

Aliphatic hydrocarbons are those that are arranged to form chains, may contain single, double
or triple bonds, and may also be branched. Aliphatic hydrocarbons containing single, double,
and triple bonds are called alkanes, alkenes and alkynes, respectively. Those that contain two
double bonds are called alkadienes.

Alicyclic hydrocarbons are the cyclic analogs of the aliphatic hydrocarbons or arranged to
form rings. The last types are aromatic hydrocarbons. Their structures are similar to alicyclic
hydrocarbons however they contain conjugated double bonds. Table B2-1 shows common
hydrocarbons.

Table B2 – 1. Hydrocarbons.
CH3 CH3
H
C
Aliphatic CH CH3
H3C CH2
H3C C C CH3 H2C CH CH2
H3C C C C
Hydrocarbons H2 H H

Alkane Alkene Alkyne Alkadiene

Alicyclic
Hydrocarbons
Cycloalkane Cycloalkene Cycloalkyne

Aromatic
Hydrocarbons
Benzene Naphthalene Anthracene

Hydrocarbon may be further classified as saturated or unsaturated. Saturated hydrocarbons

are those that contains only single bonds while unsaturated hydrocarbons are those with
double or triple bonds.

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Hydrocarbon derivatives are classified according to other atoms attached to it. Derivatives
contain oxygen are alcohols, ethers, aldehydes, ketones, carboxylic acids, esters and acid
anhydrides. Alcohols are hydrocarbon derivatives with one or more hydrogen atom replaced
by an –OH. Phenol is a special name given to alcohols whose OH group is attached to
benzene ring. Ethers may be thought of as an alcohol derivative with the hydrogen replaced
by an alkyl group. Epoxides are cyclic ethers containing three carbons.
Compounds that contains C=O are called carbonyl compounds. Aldehydes, ketones and
carboxylic acids belong to this group. Aldehydes are represented as R–CH=O. When another
alkyl group replaces hydrogen, the compound is now a ketone. Carboxylic acids are
characteristics of the –COOH group. Its derivatives are obtained by the replacement of the
hydrogen with –R, and –OCR, converting it to esters and acid anhydrides, respectively. Table
B2-2 are examples of hydrocarbon derivatives containing oxygen atom.

Table B2 – 2. Hydrocarbon Derivatives Containing Oxygen Atom.

OH OH OH
OH

H3C CH CH CH
CH CH3
Alcohols H3C C
CH CH3 H3C CH CH3
H2
OH OH

Monohdric Alcohol Dihydric Alcohol Trihydric Alcohol

O
CH3
CH3
H2
Ether and C CH
O
Epoxide H3 C O CH3

Aliphatic Ether Aromatic Ether Epoxide

CH3
O
H2
H3C CH C
Aldehyde and H3C C
C C CH3
C H
Ketone H2
H2
O

Aldehyde Ketone

O O
O O
Carboxylic H2
Acid, Ester H3C C H3C C C
C C
C OH C O CH3
and Acid H2 H2
H3C O CH3

Anhydride Carboxylic Acid Ester Acid Anhydride

Derivatives with halogens are alkyl halides, aryl halides and acyl chlorides. Alkyl and aryl
halides are hydrocarbon derivatives with one or more hydrogen of the hydrocarbon replaced
by halogens. Acyl chlorides are carboxylic acid derivatives with the –OH group replaced by
chlorine. Table B2-3 are typical examples.

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Table B2 – 3. Hydrocarbon Derivatives Containing Halogens.

Cl
Cl

H3C CH
Alkyl Halide H3C CH
CH CH3
C CH3
H2
Br

Br Cl

Aryl Halide
CH3

O
CH3 O
C
Acyl Chloride CH C Cl
H3C C Cl
H2

Derivatives may also contain sulfur and nitrogen. Hydrocarbon derivatives with nitrogen may
be an amine, amide or nitriles. Amines are hydrocarbon derivatives with the hydrogen
replaced by –NH2. Amides are carboxylic acid derivatives with the –OH replaced by –NH 2.
Nitriles, on the other hand, are characteristic of the –CN group attached to an alkyl group.
Sulfur-containing organic compounds include thiols and disulfides. Thiols are similar to
alcohols only that the –SH group is present. Disulfides have the general formula R–S–S–R.
Table B2-4 shows examples of these derivatives.

Table B2 – 4. Hydrocarbon Derivatives Containing Nitrogen and Sulfur Atom.

CH3 O
C N
H3C CH H3C C
CH NH2 CH NH2

CH3 CH3

Amine Amide Nitrile

CH3

H3C CH H3C S
CH SH S CH3

CH3

Thiol Disulfide

B2.5. NOMENCLATURE OF ORGANIC COMPOUNDS

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Alkanes. Alkanes are named by determining the longest parent carbon chain. The name of the
parent alkane is obtained using the prefixes with the ending “ane”. In cases that there are two
different chains of equal length, choose the chain containing more substituents. The
International Union of Pure and Applied Chemistry (IUPAC) suggests the following prefixes
depending on the number of carbon atoms present in the molecule.

Table B2 – 5. IUPAC Prefixes.

No. of No. of No. of
Carbon Prefixes Carbon Prefixes Carbon Prefixes
Atoms Atoms Atoms
1 Meth- 11 Undec- 25 Pentacos-
2 Eth- 12 Dodec- 30 Triacont-
3 Prop- 13 Tridec- 31 Hentriacont-
4 But- 14 Tetradec- 32 Dotriacont-
5 Pent- 15 Pentadec- 33 Tritriacont-
6 Hex- 20 Icos- 40 Tetracont-
7 Hept- 21 Henicos- 50 Pentacont-
8 Oct- 22 Docos- 60 Hexacont-
9 Non- 23 Tricos- 70 Heptacont-
10 Dec- 24 Tetracos- 100 Hect-

After naming the parent chain, number the carbon atoms giving the lowest number to
substituents present. The substituents is named using the prefixes listed however with the
ending “yl”. If there are two substituents are present on the same carbon, the number is used
twice. Should there be two or more similar substituents present, the prefixes di, tri, and so
forth are used. Different substituents are written in alphabetical order. Hyphens are used to
separate the number and the name of the substituents while commas are used to separate the
numbers. Prefixes such as sec-, tert-, di-, tri- are not considered in the alphabetization of
substituents. IUPAC still considers the following common names of substituents:

Table B2 – 6. Common Names of Substituents.

H3C H3C CH3
CH3

CH CH C H3C C CH CH3 H3C C C

H2 H3C C H2
H3C H3C H2 CH3
CH3

Isopropyl Isobutyl Tert-butyl Sec-butyl Neopentyl

(sec-propyl or (2- (2,2- (1- (2,2-
1-methylethyl) methylpropyl) dimethylethyl) methylpropyl) dimethylpropyl)

Alkenes. Alkenes are named by choosing the longest parent carbon chain containing the C=C
and attaching the suffix “ene”. Numbers are assigned such that the carbon bearing the double
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bond is given the lowest number. If there are more than one double bond, the suffix “diene”,
“triene” and so forth is attached to the prefix used based on the number of carbon atoms
present. For disubstituted alkenes, the prefix “cis-” is attached to the name of the alkene
wherein the substituents are on the same side of the ethylenic carbons and “trans” if on the
opposite sides.

Alkynes. The same rule as alkanes is applied but the suffix “yne” is used for the name of the
parent carbon chain.

Aromatic Hydrocarbons. For monosubstituted benzene, the substituents are named with the
parent name “benzene”. IUPAC still accepts some common names listed.

Table B2 – 7. Common Names of Monosubstituted Benzene.

CH3
CH3 H
C OH C N
CH2
CH
CH3

Toluene Styrene Phenol Cumene Benzonitrile

O O O
O NH2
C C H CH3 C
OH CH3

Benzoic Acid Benzaldehyde Anisole Aniline Acetophenone

For disubstituted benzene, the prefixes ortho-, meta- and para- are used to signify 1,2, 1,3,
and 1,4 positions of the substituents. For polysubstituted benzene, the substituents are
numbered so that the lowest possible numbers are used. If the common names of the
monosubstituted benzene, the other substituents are numbered so as to have the lowest
possible number.

Alkyl Halides. Halogens attached are treated as substituents and named as fluoro-, chloro-,
bromo- and iodo-. The same rule for naming alkanes is applied.

Alcohols. The longest parent carbon chain is selected bearing the functional group –OH. The
longest parent carbon chain is named like alkanes but the “e” is dropped and replaced by “ol”.
For two or more hydroxyl groups present, the ending “diol”, “triol” and so forth are used. The
numbering is done in such a way that the carbon bearing the functional group is the lowest
possible number.

Thiols. Thiols are named similar to alcohols but the ending used is “thiol” instead of “ol”. If
the –SH group is treated as substituents, the prefix “mercapto” is used.

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Aldehydes. In naming aldehydes, the longest parent carbon chain must bear the –CHO group.
This group is numbered 1 and the parent carbon chain is named like alkanes but the “e” is
dropped and replaced by “al”. In cases the –CHO group is attached to a ring, the ring is
named first and the suffix “-carbaldehyde” is attached to it.

Ketones. The longest parent carbon chain containing the carbon bearing the oxygen. The “e”
of the alkane is dropped and replaced by “one”. The lowest number is assigned to the carbon-
bearing oxygen.

Ethers. The ether may be named as an alkoxy substituted hydrocarbon or simply naming the
alkyl groups substituted to the oxygen followed by the word “ether”.

Carboxylic acid. The corresponding alkane is named and the terminal “e” is dropped and
replaced by “oic acid”. Numbering starts with the –COOH group. If the functional group is
attached to a ring, the ring is named first followed by “carboxylic acid”.

Carboxylic Acid Derivatives. In naming esters, acyl chlorides, acid anhydrides and amides,
the carboxylic acid is named and the “-oic acid” is dropped. For esters, the suffix “-ate” is
used in place of the “-ic acid”. For acyl chlorides, the suffix “-oyl chloride” is used. For
amides, the suffix “-amide” is used as replacement for the “-oic acid”. For substituents present
on the nitrogen, these substituents are named first preceded by the letter “N” to indicate that
these substituents are attached to the nitrogen atom and then followed by the name of the
parent amide. For acid anhydrides, the two carboxylic acids are named. If the carboxylic acid
name is similar, the name is used once followed by the word “anhydride”. In cases that the
two carboxylic acids present are different, both are named in alphabetical order followed by
the word “anhydride”.

Amines. Amines are named by choosing the longest parent carbon chain containing the amino
group, –NH2. The “e” of the corresponding alkane name is dropped and replaced by “-amine”.
For complicated amines, the – NH2 group may be referred to as an “amino” substituents.

B2.6.1. Alkanes

Alkanes, also called paraffins, have the general formula CnH2n+2. Rich source of low
molecular weight alkanes is natural gas. Natural gas is rich in methane and also contains
ethane, propane and small amounts of other low molecular weight hydrocarbons. Petroleum is
also a rich source of alkanes and cycloalkanes. Alkanes contain sp3-hybridized carbons.

A. Physical Properties of Alkanes. The boiling point of alkanes increases as the molecular
weight increases. Increase in the size of the molecule also accounts for the increase in the
surface area forces between them known as van der Waals forces. Branching in alkanes, on
the other hand, decreases the surface area in contact thereby resulting to a decrease in the
boiling point as branching in molecules increases. In melting point of alkanes, an increase is

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observed for alkanes with even and odd numbered carbon. X-ray diffraction studies reveal
that alkanes with an even number of carbon atoms are closely packed in its crystalline state
and therefore attractive forces between molecules are greater. Cycloalkanes have much higher
melting point but much lower boiling points compared to their open-chain counterparts.
Alkanes and cycloalkanes are generally insoluble in water due to their low polarity and
inability to form hydrogen bonds with water.

B. Preparation of Alkanes. Alkanes are prepared using Grignard Synthesis. In this synthesis,
an alkyl halide is treated with magnesium metal in dry ether producing an alkylmagnesium
halide known as the Grignard Reagent. An alkane is produced from the hydrolysis of this
organometallic. The order of reactivity of organic halides is RI > RBr > RCl.
R CH3 R CH3
CH 1. Mg, dry ether CH

X
  
2. H 2 O
H

Another method is through the reduction of an alkyl halide with zinc followed by treatment
with an acid.
R CH3 R CH3
CH 1. Zn CH

2. HBr
X H

Preparation of symmetrical ethers is done using Wurtz Synthesis. An alkyl halide is treated
with sodium metal in dry ether producing an alkane with twice the number of carbon atoms.
H2
R X 1. Zn C R


2. HBr
C
H2 R C
H2

Many unsymmetrical alkanes are prepared using the Corey-Posner, House-Whitesides

Synthesis. The first step of this synthesis is to treat an alkyl halide with lithium metal in dry
ether solvent converting it to an organolithium compound, RLi. The alkyllithium is then
treated with cuprous iodide converting it to lithium dialkylcuprate, R 2CuLi. This compound
was first synthesized by Henry Gilman and often known as the Gilman Reagent. The lithium
dialkylcuprate is then treated with another alkyl halide that must be either methyl halide,
primary or secondary cycloalkyl halide to obtain a good yield.

R X R R
CH CH2 CH2

2Li Li 
CuI CuLi

CH3 CH3 CH3

2 2
H2
R
R C
CH2 H2
CuLi + C  CH R
R X
CH3
2 CH3

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C. Reactions of Alkanes. Alkanes react with halogens by free radical mechanism. They
usually react with fluorine, bromine and chlorine only. Chlorination of alkanes is light or heat
promoted. Radical chlorination of methane was observed to consist of three steps. The first
step is called chain-initiating step. In this step, chlorine radicals are formed from the
homolytic cleavage of chlorine molecules by the action of heat or light. The next step is
known as the chain-propagating steps. In this step, the chlorine atom abstracts a hydrogen
atom from methane generating a methyl radical. The last step is the chain-termination step
wherein chloromethane is formed together with HCl and other side products. Bromination, on
the other hand, is more selective. Bromine prefers to replace tertiary hydrogens than
secondary or primary hydrogens.
CH3 CH3
R
CH CH3 + Br2 heat
 / 
light
C CH3
R C C
H2 Br H2

Complete combustion of alkanes produces carbon dioxide and water.

CnH2n+2 + (3n+1)/2 O2  n CO2 + n+1 H2O

B2.6.2. Alkenes

Alkenes have the general formula CnH2n. These groups are often called olefins. They are
characteristic of double bond and sp2 hybridized carbons. Alkenes containing up to four
carbon atoms are gases at room temperature. Alkenes are generally non-polar, very slightly
soluble in water and are less dense than water.

A. Preparation of Alkenes. Alkenes are prepared via elimination reaction.

Dehydrohalogenation of alkyl halides using potassium hydroxide in alcohol produces more
substituted alkene. This rule is known as Saitsev’s Rule. A more substituted alkene is one that
contains more alkyl substituents in the C=C. The reaction is said to be bimolecular
elimination reaction, E2 that is favorable when a tertiary or secondary alkyl halide is used, the
temperature is high and in the presence of strong bases. Typical reagents are sodium ethoxide
in ethyl alcohol or potassium tert-butoxide in tert-butyl alcohol.
CH3
H3C CH3
CH CH3
R CH
  
alcoholic KOH
C C

R H
X

Another method is through dehydration of alcohols with strong acid like sulfuric acid or
phosphoric acid at higher temperature to favor elimination reaction over substitution reaction.

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In the synthesis, rearrangements may occur to form a more stable carbocation. The alkene
produced also follows Saitsev’s Rule producing a more alkyl-substituted alkene.
CH3
H3C CH3
CH CH3
R CH H2SO4  C C

R H
OH

Alkenes may also be obtained from debromination of vicinal dibromides in the presence of
NaI in acetone or Zn in acetic acid or ethyl alcohol.
Br
H CH3
CH CH3 NaI
  
in acetone/HAc C C
R CH
R H
Br

Through addition reaction, alkenes are produced from hydrogenation of alkynes in the
presence of poisoned palladium catalyst known as Lindlar’s catalyst or nickel boride, Ni2B
called P-2 catalyst. The alkenes produced using these catalysts are cis-alkenes. Trans-alkenes
are produced by hydrogenating alkynes in the presence of lithium or sodium metal in
ammonia or ethylamine at low temperature.
H H

H2 C C


Pb ( Pd )
R R'
cis-alkene
H H

H2 C C


 Ni 2 B
R C C R'
R R'
cis-alkene
H R'
H2
C C
Na / Li

in NH 3 R
trans-alkene
H

B. Reactions of Alkenes. Most reactions of alkenes fall under electrophillic addition. This
reaction results in the conversion of  bond to  bond. Pi () bonds result in the lateral
overlap of two orbitals while sigma () bonds result in the head-on overlap of two orbitals.

1. Addition of Hydrogen Halides. Addition of hydrogen halides follows Markovnikoff’s Rule.

This rule states that the halide ion attaches to the doubly bonded carbon atom that has fewer

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hydrogen atoms. However, the addition of HBr in the presence of organic peroxides does not
follow Markovnikoff’s addition but instead a free radical addition.

H H H H

C C H

Br
 R C C H

R H Br H

H H H
H
HBr
  
C C organic peroxide R C C H

R H H Br

2. Addition of Sulfuric Acid. Sulfuric acid adds to alkenes to form alkyl hydrogen sulfates and
upon heating with water produces an alcohol. The addition is said to follow Markovnikoff’s
rule.

H H H H H
H

C C H2SO4  R C C H
H2O,

heat R C C H

R H OSO3H H OH H

3. Acid-Catalyzed Addition of Water. The addition of water in the presence of an acid also
follows Markovnikoff’s rule and therefore produces higher order alcohols. The reaction
involves rearrangement due to the formation of carbocation intermediate.

H H H
H

C C H2O,

H
 R C C H

R H OH H

4. Oxymercuration-Demercuration. This reaction produces alcohols from alkenes via

Markovnikoff’s addition but does not involve rearrangements. The synthesis involves reaction
of the alkene with mercuric acetate in a mixture of tetrahydrofuran and water followed by
demercuration with sodium borohydride.

H H H
H
1. Hg(CH 3COO) 2 /THF - H 2O
C C 2. NaBH 4 , HO - R C C H

H
     
R OH H

5. Hydroboration-Oxidation. This reaction produces an alcohol of lower order via anti-

Markovnikoff’s addition of water. In the reaction, an alkene reacts with diborane, B 2H6
followed by oxidation and hydrolysis of the organoboron intermediate.

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H H H H
1. B 2 H 6
C C 2. H 2 O 2 , HO - R C C H

H
  

R H OH

6. Addition of Halogens. The addition of bromine in the presence of carbon tetrachloride

produces a vicinal dibromide via trans addition.
H Br
H H
R C C H
C C Br2 inCCl4 
Br H
R H
vicinal dihalide

7. Halohydrin Formation. If the addition of halogen is carried out in aqueous solution, the
major product is a halohydrin. The reaction follows Markovnikoff’s addition of the water
molecule.
H H
H H
R C C H
C C Br2 inH
2O

OH Br
R H
bromohydrin

Another type of reaction alkenes undergo is oxidation reactions. This reaction involves
oxidation of the carbon-carbon double bond.

8. Hydroxylation of Alkenes. Alkenes react with cold dilute KMnO4 producing a cis-diol. The
same product is obtained when an alkene is treated with osmium tetroxide followed by
treatment with sodium bisulfite or sodium sulfite.
H H

cold and dilute R C C H

  
KMnO 4
OH OH
H H
cis-diol
C C
H H
R H

1. OsO 4 R C C H

   
2. NaHSO 3 /Na 2SO 3
OH OH
cis-diol
9. Oxidative Cleavage Reactions. When an alkene is treated with hot basic potassium
permanganate solution, a carboxylic is produced after acidification. A monosubstituted carbon
atom of the double bond produces carboxylic acid while a disubstituted double bond produces
a ketone. Terminal CH2 group of an alkene is oxidized to CO2 and H2O.

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O
H H
1. KMnO 4 , heat , HO  C
C C
2. H  R OH + CO2 + H2O
     carboxylic
R H
acid
O
H3C CH3

1. KMnO 4 , heat , HO C
C
C 2. H 
     R CH3
R R
ketone

10. Ozonolysis of alkenes produces aldehydes and ketones. In this reaction, the alkene is
treated with ozone followed by reduction with zinc and acetic acid.
O O
H H
1. O 3
C
+ C
 

C C 2. Zn/HAc
R H H H
R H
aldehyde aldehyde
O
H3C CH3
1. O 3
C
 
2. Zn/HAc
C C
R CH3
R R
ketone

B2.6.3. Alkynes

This group, often called acetylenes, has a general formula of C nH2n–2. This group contains
triple bonds and sp hybridized carbon. Except for 2-butyne, alkynes containing up to four
carbons are gases at room temperature. Their trends in boiling points are the same as alkanes
and alkenes. Alkynes are insoluble in water and less denser than water.

A. Preparation of Alkynes. Alkynes are prepared from alkyl halides by elimination reaction in
the presence of a strong base like sodium amide, NaNH 2 or potassium tert-butoxide and
strong reducing agents like zinc.

An alkyne is produced by simultaneous dehydrohalogenation of a geminal and vicinal

dihalide in the presence of sodium amide in ammonia.
X H

R C C H
NaNH
 2 in
NH 3 R C C H

X H
geminal dihalide
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H H

R C C H
NaNH
 2 in
NH 3 R C C H

X X
vicinal dihalide

Another way of preparing alkynes is through the reaction of acetylide with an alkyl halide.
Acetylides are prepared from treatment of terminal alkynes with sodium amide in ammonia.
An alkyne is produced from the reaction of the acetylide with a primary alkyl halide.
- +
R C C Na
R C C H NaNH
 2 inNH3 
sodium acetylide
- +
R C C Na CH
 3X
 R C C CH3

B. Reactions of Alkynes. Reaction of alkynes is similar to alkenes however two moles of the
reagent are required. One reaction is hydrogenation of alkynes that yields either cis- or trans-
alkene. Halogenation of alkynes forms a tetrahalide in the presence of carbon tetrachloride.
Br Br

R C C H
R C C H 2Br
2 
in CCl 4

Br Br
tetrahalide

1. Addition of hydrogen halides to alkynes forms a geminal dihalide via Markovnikoff’s

addition.
Br H

R C C H
R C C H 2HBr

Br H
geminal dihalide

2. Hydration of Alkynes. Unlike alkenes, addition of water requires strong acid and mercuric
sulfate as catalysts since alkynes are less reactive than alkenes. The addition of water forms an
enol via Markovnikoff’s addition. However, the enol is unstable and a rearrangement occurs
that involves the loss of a proton from the hydroxyl group, the addition of the proton to the
adjacent doubly bonded carbon and the formation of a ketone. This rearrangement is known
as keto-enol tautomerism.

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R H R CH3
C

C C
R C C H H  
2 O, H , HgSO 4

HO H O

enol ketone

3. Oxidation of Alkynes. Alkynes when treated with ozone and hot basic KMnO4 produce
carboxylic acid. Terminal alkynes produce carboxylic acid and carbonic acid, which
dissociates into carbon dioxide and water.
O

1. KMnO 4 , heat, HO
R C C H
2. H 
C
+ CO2 + H2O
     R OH
carboxylic acid

B2.6.4. Aromatic Compounds

Aromatic compounds are generally categorized as one having cyclic structure, planar and
obey Huckel’s Rule. This rule states that the number of pi () electrons must be equal to 4n+2,
where n must be a whole number.

Benzene. The most common aromatic compound is benzene and its derivatives. Benzene is
obtained from catalytic dehydrogenation of cyclohexane and from coal tars. Its structure is
composed of a six-membered ring with alternating single and double bonds. It is stabilized by
the delocalization of pi electrons known as resonance. Due to its stability, it undergoes
electrophilic substitution.

A. Reactions of Benzene. Electrophilic aromatic substitution involves the generation of an

electrophile using a Lewis acid, attack to the benzene ring and restoration of the aromatic
ring.

1. Friedel-Crafts Alkylation. Benzene is treated with an alkyl halide in the presence of AlCl 3
or FeCl3 to produce alkyl benzene.
R

RX
(X  Cl or Br)
  AlCl3
alkylbenzene
2. Friedel-Crafts Acylation. Addition of acyl chloride in the presence of AlCl 3 to benzene
produces an aromatic ketone.

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O
C
R
+ C
AlCl
3 
R Cl
acyl chloride
aromatic ketone

3. Halogenation. Halogens such as chlorine and bromine add to the benzene ring in the
presence of AlCl3.
X
X2
(X 2  Cl 2 or Br2 )
    AlCl 3
halobenzene

4. Nitration. Treating benzene with concentrated nitric acid and sulfuric acid produces
nitrobenzene. Concentrated sulfuric acid is responsible for the formation of the nitronium ion,
NO2+.
NO2

HNO
 3 , H 2 SO 4


nitrobenzene

5. Sulfonation. Treatment of benzene with fuming sulfuric acid produces benzene sulfonic
acid. Fuming sulfuric acid contains sulfuric acid and sulfur trioxide or commonly known as
oleum.
O

S OH

  
fuming H 2 SO 4 O

benzenesulfonic acid

6. Reactions of Monosubstituted Benzene. Substitution to monosubstituted benzene is

influenced by the substituents initially present. The groups present affect the rate of reaction
and the site of the attack of the incoming electrophile. Substituent may be classified as
activating groups or deactivating groups. Activating groups are those that make the ring more
reactive than benzene by releasing electron to the ring. Deactivating groups are those that
withdraws electron from the ring making it less reactive than benzene itself. With respect to
the orientation of the incoming groups, substituent may be classified as ortho-para directing
and meta directing. Table B2-8 lists the different substituents.

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Table B2 – 8. Classification of Substituents in Electrophilic Aromatic Substitution.

Activating and Ortho-Para Directing Substituents
Very Strongly Activating Strongly Activating Activating
H O

R
N amino C acylamino alkyl
N R
H H
H

OR Ar
N alkylamino alkoxy aryl
R
R O

N dialkylamino C acyloxy
R' O R

OH
hydroxyl

Deactivating and Ortho-

Deactivating and Meta Directing Substituents
Para Directing Substituents
Very Strongly Deactivating Strongly Deactivating Deactivating
F
O
F
C F trifluoromethyl C formyl fluoro
H
F
O O
+ Cl
•N nitro C acyl chloro
-
O R
O
carboxylic Br
bromo
C
acid
OH
O
I
C ester iodo
OR
O

C acyl chloride
Cl

C N cyano
O

S H sulfonic acid
O

7. Other Reactions of Monosubstituted Benzenes. Some benzene derivatives are not directly
obtained from benzene. Benzoic acid is obtained from oxidation of alkyl benzenes.

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R C
1. KMnO 4 , heat , HO  OH
2. H 
    
benzoic acid

Phenols can be obtained by fusing benzenesulfonic acid with sodium hydroxide followed by
acidification. It can also be obtained by heating chlorobenzene with sodium hydroxide at
350C under high pressure.
OH
O

S OH 1. fuse with NaOH

2. H 
O    

phenol
OH
Cl
NaOH, heat
C
350 
phenol

Aniline is produced by reduction of nitrobenzene by iron and HCl. Other metals such as tin
and zinc can also be used.
NH2
NO2

Fe,
HCl

aniline

8. Reactions of Disubstituted Benzene. The orientation of the incoming electrophile to

disubstituted benzene is influenced by the initially present substituents. If two ortho-para
directing groups are present, the more activating substituent directs the incoming electrophile
to the positions ortho and para to it. If two meta directing substituents are present, the less
deactivating substituent direct the incoming electrophile meta to it. If ortho-para and meta
substituents are present, the ortho-para substituent directs the incoming substituent to the
position ortho and para to it.

B2.6.5. Alcohols and Ethers

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Alcohols are hydrocarbon derivatives that have the general formula, R–OH. They can be
classified based on the number of –OH groups present in the structure. Monohydric alcohols
are those that contain one hydroxyl group. Dihydric alcohols, known as diols and trihydric
alcohols, known as triols contain two and three hydroxyl groups, respectively. They can also
be classified as to the nature of carbon to which the functional group is attached. Primary,
secondary or tertiary alcohols are among this classification. Among the alcohols, methyl
alcohol and ethyl alcohol are of great importance. Methyl alcohol is obtained from the
destructive distillation of wood. It can also be obtained from the reaction of synthesis gas in
the presence of a catalyst. Ethyl alcohol can be obtained from fermentation of sugarcane.
Ethers are represented as R–O–R. Commonly used ether is diethyl ether. It was first employed
as anesthetics and is highly flammable.

A. Physical Properties of Alcohols and Ethers. Generally, alcohols have much higher boiling
points compared to ethers of the same molecular weight. The ability of alcohol molecules to
associate with each other through hydrogen bonding explains this trend in its boiling point.
Alcohols and ethers are soluble in water due to their ability to form hydrogen bonds with
water.

B. Preparation of Alcohols. From the previous sections, alcohols can be prepared using
alkenes as substrates. In this section, carbonyl compounds and Grignard reagents are used to
produce alcohols.

1. Reduction of Carbonyl Compounds. Carboxylic acids, esters, ketones and aldehydes can be
used as substrates to synthesize alcohols. A strong reducing agent like lithium aluminum
hydride, LiAlH4 and sodium borohydride, NaBH4 can be used.
O
H2
R C
R C
C OH
C OH LiAlH
4  H2
H2
primary alcohol
carboxylic acid
O H2
R C
R C C OH
C OCH3 LiAlH
4  H2
+ CH3OH
H2 primary
ester alcohol
O OH

R C R CH
C CH3 LiAlH
 4 / 
NaBH 4
C CH3
H2 H2

ketone secondary alcohol

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O
H2
R C
R C
C OH
C H LiAlH
 4 / 
NaBH 4
H2
H2
primary alcohol
aldehyde

2. Addition of Grignard Reagents. Alcohols are also obtained by the addition of Grignard
reagents to aldehydes, ketones, esters and epoxides.
O OH

R C R CH
C H R'MgX
 C R'
H2 H2

aldehydes secondary alcohol

O R'

R C R C C CH3
C CH3 R'MgX
 H2
H2 OH
ketone tertiary alcohol
O OH

C
R'MgX
 CH
H H H R'
methanal primary alcohol
H2
O
R' C
C OH
H2 C CH2 R'MgX
 H2
epoxide primary alcohol

C. Reactions of Alcohols. Due to the polarity of the carbon-oxygen bond, the carbon atom is
susceptible to a nucleophilic attack. On the other hand, the polarity of the oxygen-hydrogen
bond makes the alcohol a weak acid.

1. Conversion to Alkyl Halides. Alcohols reacts with hydrogen halides, phosphorus

tribromide, PBr3 and thionyl chloride, SOCl2 to produce alkyl halides. Reaction with
hydrogen halides is best for tertiary alkyl halides thus the synthesis is susceptible to
rearrangements. Primary and secondary alkyl halides are produced using PBr3 and SOCl2.
CH3

CH3
R C C CH3
H2 HX
  

(HI, HBr, HCl) R C C CH3
OH H2
tertiary alcohol X
3>2>1>methyl

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H2 H2
R C R C
C OH C Br
H2 PBr
3  H2

1 or 2 alcohol 1 alkyl bromide

H2 H2
R C R C
C OH C Cl
H2 SOCl
2  H2

1 or 2 alcohol 1 alkyl chloride

2. Oxidation of Alcohols. Primary alcohols can be oxidized to aldehydes and carboxylic acids
while secondary alcohols are oxidized to ketones. Tertiary alcohols are not oxidized under
mild conditions.
O
H2
R C
C OH
1. KMnO 4 , heat , HO  R C
2. H 
H2
     C
H2
OH

1 alcohol carboxylic acid

O
H2
R C
C OH
pyridinium chlorochromate R C
CH 2 Cl 2 , heat
H2
    C
H2
H

1 alcohol aldehyde
OH O

R CH R C
C CH3 H2 CrO
4  C CH3
H2 H2

2 alcohol ketone

D. Preparation of Ethers. Acid-catalyzed dehydration of alcohols produces ethers under

conditions of low temperature and excess concentration of the alcohol. This synthesis is used
to produce symmetrical ethers. Williamson Synthesis is used to produce unsymmetrical ethers
from lower order alkyl halide and alcohol. In the synthesis, the alcohol is treated with sodium
or potassium metal to produce an alkoxide. This alkoxide is then reacted with methyl alcohol
or any primary alcohol to produce unsymmetrical ether.

Acid Catalyzed Dehydration of Alcohols

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CH3 CH3
CH3
H 2 SO 4 R CH CH R
140C

R CH C O C
C OH H2 H2
H2
1 alkyl chloride

Williamson Synthesis of Unsymmetrical Ethers

CH3
CH3

Na/K/NaH
  CH
-
CH R O Na+
R OH
sodium alkoxide
CH3 H2 CH3
C

CH + R' X  
Na/K/NaH
CH
H2
C
R
-
O Na+ methyl or 1 alkyl halide R O R'

E. Reaction of Ethers. Due to low reactivity of ethers, one reaction that is of importance is
the acid-catalyzed cleavage reaction. In this reaction, the ether is cleaved in the presence of an
excess hydrogen halide producing alcohol and alkyl halide. The alcohol may further react
with the hydrogen halide to produce another alkyl halide.
CH3

CH3 H2
CH C

CH
H2
C  
HBr / HI
R X + R' OH

R O R' higher order alkyl lower order alcohol

halide

B2.6.6. Aldehydes and Ketones

Aldehydes and ketones are compounds containing the acyl group, R–C=O attached to either
an alkyl group or hydrogen.

A. Physical Properties. Generally, these compounds have higher boiling point than
hydrocarbons of the same molecular weight but lower than alcohols due to their inability to
hold strong hydrogen bonds between its molecules. Low molecular weight aldehydes and
ketones are soluble in water.

B. Preparation of Aldehydes and Ketones. Aldehydes can be obtained from the oxidation of
primary alcohols and ozonolysis of alkenes. Other substrates can be reduced to aldehydes
such as acyl chlorides, esters and nitriles using lithium tri-tert-butoxyaluminum hydride or
diisobutylaluminum hydride.

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O
O
R C 1. LiAlH(O- tert - butyl)
    
2. H 2O
C Cl R C
H2 C H
H2
acyl chloride
O
O
R C 1. DIBAL-H
 
2. H 2O
C OR' R C
H2 C H
H2
ester
O
R C N
C 1. DIBAL-H
 
2. H 2O
H2 R C
C H
nitrile H2

Ketones are synthesized from alkenes, secondary alcohols and alkynes as shown from the
previous sections.

C. Reactions of Aldehydes and Ketones. Aldehydes and ketones are susceptible to

nucleophilic addition to the carbon-oxygen double bond. Addition of hydrogen cyanide
produces cyanohydrins.
OH
O

R C H
C
HCN

R H
CN
aldehyde cyanohydrin
OH
O

R C R'
C
HCN

R R'
CN
aldehyde cyanohydrin

Addition of Grignard reagent to aldehydes and ketones produces secondary and tertiary
alcohols, respectively.
O OH

R C R CH
C H R'MgX
 C R'
H2 H2

aldehydes secondary alcohol

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Philippine Handbook Organic Chemistry
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O R'

R C R C C CH3
C CH3 R'MgX
 H2
H2 OH
ketone tertiary alcohol

Addition of alcohols produces a hemiacetal and further addition of alcohol followed by

acidification converts it to an acetal.
O R O H R O R'

R'OH C R'OH C
C
H  /RO - H  /RO -
R H   H O R'   H O R'

aldehyde hemiacetal acetal

O R O H R O R'

R'OH C R'OH C
C  -  -
R R" H/RO
 R'' O R' H/RO
 R'' O R'
ketone hemiacetal acetal

Aldehydes may undergo further oxidation to carboxylic acid using KMnO 4 in the presence of
silver oxide followed by acidification.
O O
-
1. Ag 2 O, HO
C C
2. H 
R H   
 R OH
aldehyde carboxylic acid

B2.6.7. Carboxylic Acids and Derivatives

Carboxylic acids are represented as RCOOH. Most of these compounds occur naturally. One
common carboxylic acid is acetic acid, a component of vinegar. These acids are relatively
weak and readily react with aqueous solutions of NaOH and Na2CO3. The presence of electron
withdrawing groups such as halogens increases its acidity. Derivatives of carboxylic acid
include esters, acyl halide, acid anhydride and amides. Esters occur naturally as fraction of oil
of fruits and flowers. Low molecular weight esters are volatile and characteristic of fruity
odors. Acyl halides are the most reactive among the carboxylic acid derivatives. The most
common of the acyl halide is acyl chloride. Acid anhydrides may be thought of as union of
two carboxylic acids accompanying a loss of water molecule. Amides or carboxamides are
solids at room temperature. They occur naturally in plants and animals and usually employed
as pain reliever and antipyretic.

A. Physical Properties. Carboxylic acids have high boiling points due to their ability to form
hydrogen bonds with each other and water. They are highly soluble in water but tend to
decline as the carbon chain increases. These compounds are highly polar. Esters due to their
lack of hydroxyl groups have lower boiling points compared to alcohols of the same

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molecular weight. Low molecular weight esters are soluble in water but increase in chain
length decreases its solubility. Amides form hydrogen bonds making it soluble in water.

B. Preparation of Carboxylic Acid. Carboxylic acids are prepared from oxidation of alkenes,
primary alcohols, aldehydes and alkylbenzenes as shown from previous sections. Other means
of its preparation include oxidation of methylketones known as iodoform reaction. This
reaction produces a yellow precipitate of iodoform, CHI 3 that is used as a test for methyl
groups attached to a functional carbon.

C. Reactions of Carboxylic Acid. Reactions of carboxylic acids involve nucleophilic addition-

elimination at the acyl carbon. Its reactions are also means of preparing different derivatives.

1. Conversion to Acyl Chloride

O CH3

C    
SOCl 2 / PCl 3 / PCl 5
CH
H2
C
R OH R O R'

2. Conversion to Acid Anhydride

O O O O

C + C

pyridine
C C
R OH R' Cl R O R'

O O O O

C + C
 C C
-
R OH R' O Na+ R O R'

3. Conversion to Ester (Esterification)

O O
H2
+ H2

C
C 
H
C C
R' OH
R OH R O R'

4. Conversion to Amide
O
O
N
C
+


C
H H 
H
H
H R N
R OH
H

O
O
N
C
+


C
R H 
H
H
H R N
R OH
R

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O
O
N
C
+


C
R R 
H
R
H R N
R OH
R

B2.6.8. Amines

Amines are ammonia derivatives. Amines are highly polar and water-soluble due to their
ability to form hydrogen bonds. Low molecular weight amines are characteristic of fish-like
aroma. They contain lone pairs making them basic and nucleophilic. Important reactions of
amines are alkylation and acylation.

A. Preparation. Amines are prepared from reduction of amides and nitriles using LiAlH4.
O

1. LiAlH 4 , ether H2
C C
R NH2   
2. H 2 O
R NH2

amide

R C N 1. LiAlH 4 , ether H2
C
nitrile   
2. H 2 O
R NH2

1. Alkylation of Ammonia
R X N N
+
-
H H HO

 R H
alkyl halide H H

2. Reduction of Nitro Compounds. Aromatic amines are prepared from reduction of nitro
compounds using iron and HCl.
NH2
NO2

Fe,
HCl

aniline

3. Reduction of Nitriles and Oximes

R C N H2
Raney
  Ni
 C
nitrile R NH2

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R N
H2
C OH
H Na
in 
alcohol C
R NH2
oxime

B. Reactions of Amines

1.Reaction with Nitrous Acid. Amine reacts with nitrous acid to produce unstable diazonium
salts, which serve as an intermediate in the formation of various organic compounds. Nitrous
acid is a weak acid prepared by treating sodium nitrite with a strong acid.

H  
3 PO 2 , H 2 O

benzene
OH

Cu 2 O, Cu 2
 H 2O

phenol
F

HBF
4 

fluorobenzene
+ Cl
NH2 N N

HNO
2  CuCl

aryldiazonium salt chlorobenzene

Br

Cu
Br


bromobenzene
I


KI

iodobenzene
C N

Cu
CN


benzonitrile

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Organic Chemistry, B2 - 1

alcohols, B2 - 5, 8, 21, 22, 23, 24

aldehydes, B2 - 5, 9, 24, 25, 26
alkanes, B2 - 7, 9, 10, 11
alkenes, B2 - 8, 11, 12, 14
alkynes, B2 - 8, 15, 16, 17
amines, B2 - 6, 9, 28, 29
aromatic compounds, B2 - 17
carboxylic acids and derivatives, B2 - 26
ethers, B2 - 5, 9, 21, 23, 24
hybridization, B2 - 2
ketones, B2 - 9, 24, 25
molecular orbital theory, B2 - 1
organic compounds, classes of, B2 - 4
organic compounds, nature of, B2 - 1
organic compounds, nomenclature of, B2 - 7
structural theory, B2 - 1
valence bond theory, B2 - 1

B2 - 30