MINISTRY OF SCIENCE AND TECHNOLOGY

DEPARTMENT OF TECHNICAL AND VOCATIONAL EDUCATION

Ch-01012 ORGANIC CHEMISTRY

A.G.T.I(First Year)

(FC & PR)

PART ONE

CHAPTER I
Organic Chemistry:
1. Introduction. Organic chemistry may be defined as the chemistry of carbon compounds. Many different elements may occur in organic compounds but the one most commonly found in the order of their relative occurrence carbon, hydrogen, oxygen, nitrogen, phosphorous, sulphur, chlorine, bromine. It was formally believed that organic compounds were exclusively of plant or animal origin and that vital processes were essential for their formation. Various products of plant and animal life could not be produced without the aid of a vital force supplied by the living cells. The uses of this vital force theory was given up during the first half of the nineteenth century by the production of several organic substances from nonliving sources. Among the first organic compounds to be produced by synthetic means was urea, a product of the metabolism of protein and present in the urine of all animals. This was obtained in 1828 by Wohler (German Chemist) when he noticed that the evaporation of a solution of ammonium isocyanate converted a portion of this organic salt to urea. NH4CNO Ammonium isocyanate This experiment work led to the development of the concept that vital processes are not essential for the formation of organic compounds. A few years later Kolbe synthesized acetic acid from inorganic substances. The laboratory synthesis of their so-called organic compounds soon followed and by 1850 the vital force theory had been gradually overthrown. Out of this development has come synthetic products, such as plastic, detergents, textiles, dyes and many other useful materials. All of these substances contain carbon; hence the study of carbon compounds attains ever-increasing importance. More than a quarter of a million organic compounds are known. The existence of this large number of organic compounds is due to the unique capacity of H2N-CO-NH2 Urea

carbon atoms to unite with itself by means of covalent bonds without any limit, to form compounds containing long chains of carbon atoms or having a variety of ring system. The reasons why organic compounds are studied separately as a branch of chemistry are as follows: I. Carbon atoms are capable of forming a long and straight chain or a branched chain among themselves. No other elements can have such unique properties.

C C C C C C C C C C C C C C C Straight-chain compound
II.

C C C C C Cyclo- compound
So their

C C

Branched-chain compound

A majority of organic compounds are covalent compounds. chemical reactions are very low.

III.

Organic compounds are soluble in non-polar solvents like ether, alcohol, benzene, rather than polar solvent. Their melting points and boiling points are very low as compared to inorganic compounds. In addition, organic compounds in solution or in molten state conduct no electricity.

IV.

The term isomerism is found in all the organic compounds which have the some empirical and molecular formula, but which have distinctly different structure and consequently different properties. Isomerism: Compounds, which have same molecular formula but different

molecular structures and consequently different properties, are called isomers. Isomerism is due to different arrangements of carbon atoms in the molecule. As an example, ethyl alcohol and dimethyl ether have the same molecular formula but their properties are entirely different. For example, CH3CH2OH Ethyl alcohol CH3.O.CH3 dimethyl ether

CHAPTER II
Aliphatic Hydrocarbons:

2.1

Molecular formulae of some Hydrocarbons. Among organic compounds, hydrocarbons are simple compounds

containing only hydrogen and carbons. Some of their compounds are summarized as follows. Name Methane Ethane Propane n-Butane iso-Butane Molecular formula CH4 C2H6 C3H8 C4H10 C4H10 Molecular structure CH4 CH3.CH3 CH3.CH2.CH3 CH3.CH2. CH2.CH3
CH3 CH CH3 CH3

2.2

Homologous Series Inspection of the formulae for methane, ethane, propane, etcreveal

that the formula for one of these hydrocarbons differ from that of the hydrocarbon which immediately proceeds (or follows) it by one carbon atom and two hydrogen atoms. For example, subtraction of the formulaC2H6 fromC3H8 gives a difference of CH2. Such a series of compound in which the difference between successive members is CH2 is known as a homologous series. Any individual member of the series is a homologous of the others. 2.3 Aliphatic hydrocarbons. Aliphatic compounds are open chain or cyclic compounds and derive from the Greek word (Aliphos). Because of the fact that lower members of the hydrocarbons come of fatty acids, the term (aliphos) means fats.

Three types of hydrocarbons. (i) Paraffins or Alkanes: They are saturated hydrocarbons and may be presented by the general formula CnH2n+2. The carbon and hydrogen atoms are joined by single covalent bonds in alkane.
C C C C C

(ii)

Olefins or Alkenes: They are unsaturated hydrocarbons and may be represented by the

general formula CnH2n. In these compounds, the two carbon atoms are joined by a covalent double bond.

C C C C C

(iii) Acetylenes or Alkynes: They are also unsaturated compounds represented by the general formula CnH2n-2. In alkyne the two carbon atoms are joined by a covalent triple bond. (
C C

).

2.4 2.4.1

Paraffins or Alkanes. The Nomenclature of Paraffin Hydrocarbons. To easily study the organic chemistry, there is well-established naming

system for so many organic compounds. Basically three systems of naming the Paraffin hydrocarbons are as follows.

(i)

Since the existence of Paraffin hydrocarbons was known, methane, ethane, propane, etc have been called according to their original sources.

For example methane is the original hydrocarbon of methyl alcohol, which was obtained by the destructive distillation of wood, and hence name wood sprit. The historical background of such hydrocarbon as methane now becomes totally absolute. However, these names age still use for the sake of simplicity. Those hydrocarbons above butane are named according to Roman Letters.e.g. C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 pentane Hexane Heptane Octane Nonane Decane, and so on.

In the case of isomers those, which have only, are long straight chain are normal, those, which have CH3 CH CH3 group, are iso and those, which have quaternary carbon atoms, are neo.
C

C C C C C C C niso C C C

C C C C C neo -

(ii)

Derived system. In this system, the carbon atom having greatest numbers of branched chain is taken as the original carbon of methane. E.g.,
CH3 CH3 CH CH2 CH3 CH3 CH3 C CH3 CH3 iso-pentane dimethyl-ethyl methane

neo-pentane Tetramethyl methane

(iii)

Geneva of IUPAC System. In this system the carbon atom having a longest straight chain is taken as original compound and branched chains as substituted radicals or groups. The carbon atoms in the chain are numbered consecutively from one end to the other, either right to left or left to right, in order to designate the positions of substitutent groups by the smallest possible figures.

The rules of the IUPAC system are:

1. 2. 3. 4.

Pick out the longest continuous chain of carbon atom. Identify that chain as an alkane. Pick out the alkyl groups attached to that chain. Number the carbon in the chain, starting at whichever end of the chain will give the smallest numbers to the carbon to which the alkyl groups are attached. Continue the numbering of this carbon chain in the same direction from one end to another.

5. 6.

List the numbers and the names of the alkyl groups. Use commas between numbers and a dash between a number and letter.

E.g.,
1

CH3
2 3

CH3 C CH2 CH3

CH CH3 CH3

2, 2, 4- trimethyl pentane.

CH3
1 2

CH3 CH CH CH2 CH2 CH3 CH3 2, 3- dimethyl hexane.

2.4.2 (i)

General Methods of Preparations for Paraffin Hydrocarbon. When unsaturated hydrocarbons are hydrogenated in the presence of finely divided nickel, or platinum black or palladium black, valencies of carbon atom are saturated.

RCH=CH2 Alkene

H2

Pd (or) Pt (or) Ni 200 - 300o

RCH2-CH3 Alkane

(ii)

Kolbes method: By electrolysis of a concentrated solution of sodium or potassium salt of fatty acid.

(CH3-CH2-CH3 + 2CO2) CH3COONa + Electrolysis

C2H5COONa + 2H2O (2NaOH + H2)

(iii)

By heating sodium salt of fatty acid with sodalime. Lower members of saturated hydrocarbons can be obtained. With sodium salt of higher fatty acid, it is better to use barium hydroxide of sodium methoxide.

RCOONa + NaOH (CaO)

RH + Na2CO3 (CaO)

(iv)

From Grignard reagent: Grignard reagent is first prepared by dissolving alkyl halide in anhydrous ether and continuously stirring with the addition of magnesium metal. Alkyl magnesium halides so formed are called Grignard reagent. This, being

unstable, decomposes on treatment with dilute acid or water, producing paraffin hydrocarbon.

RX

Mg

RMgX + H2O

dry ether dry ether

RMgX RH + MgX (OH) Cl Mg CH3CH3 + OH CH3CH3 + MgCl2

CH3CH2MgCl + H2O dry ether CH3CH2MgCl + HCl dry ether

(v)

Wurtz reaction: When alkyl halides are dissolved in dry ether and the solutions so obtained treated with small pieces of sodium metal paraffin hydrocarbon are obtained. RX + 2Na + XR/ CH3I + 2Na + ICH3

dry ether dry ether

R-R/ + 2NaX CH3-CH3 + 2NaI

For different alkyl halides, a mixture of hydrocarbon can be obtained.

dry ether CH3I + 2Na + CH3CH2I dry ether dry ether

CH3CH2CH3 + 2NaI Propane

2CH3CH2I

2Na

CH3CH2CH2CH3 + 2NaI Butane

2CH3I

2Na

CH3CH3 + 2NaI Ethane

2.4.3 1.

Properties of Paraffin Hydrocarbon. Their melting and boiling point are very low. But these values become higher with the increase of molecular weight.

2.

They are not soluble in water but soluble only in organic solvents like ether, benzene, chloroform etc.

3.

Since their valencies are saturated they can be undergo only substitution reaction with monovalent atom or radical.

Halogenation: The hydrocarbons undergo substitution reactions with chlorine and bromine. Iodine dose not substitute. The chlorine atom can substitute only one of the hydrogen atoms of hydrocarbon molecule. In doing so two types of compounds are formed depending on the experimental conditions.

(a)

No reaction takes place in a dark room. However, when methane and chlorine are mixed and placed in bright sunlight, carbon and hydrochloric acid are formed with violent explosion. CH4 + 2Cl2 C + 4HCl

(b)

On the other hand when the reaction is allowed to undergo indifferent sunlight, chlorine with successively substitutes the hydrogen atoms in methane molecule. diffused CH4 + Cl2 sunlight diffused sunlight CH3Cl + HCl Methyl chloride CH3Cl + Cl2 CH2Cl2 + HCl Methylene chloride

10

CH2Cl2 + Cl2

diffused sunlight diffused sunlight

CHCl3

+ HCl

Chloroform CHCl3 + Cl2 CCl4 + HCl

Carbontetra chloride

Nitration: They are not attacked by acids, alkalies or metals like sodium or potassium. Oxidizing agents and reducing agents have no action under ordinary conditions. Fuming or concentrated nitric acid oxidized them. Therefore when heated in a sealed tube with dilute nitric acid one of the hydrogen atoms in hydrocarbon molecules is replaced by a nitro (-NO2) group. The process is called nitration. The ease of the nitration also depends on the structure of the hydrocarbons. Thus the tertiary hydrogen atom is more readily nitrated than the secondary hydrogen atom and the primary hydrogen atom is less readily nitrated than the secondary. CH3CH2*CH3 + HNO3 Primary carbon CH3 *CH2CH3 + HNO3 Secondary carbon CH3 CH3*CHCH3 + HNO3 CH3CHCH3 NO2 CH3 CH3 C CH3 NO2 + H2O + H2O

CH3CH2CH2NO2 +

H2O

Tertiary carbon

Nitration rate: Tertiary > Secondary > Primary

11

2.5

Olefins as Alkenes. Olefins or Alkenes are another homologous series of hydrocarbons

having the general formula CnH2n. They are unsaturated hydrocarbons containing a double bond each, commonly called olefnic double bond.

2.5.1 (1)

Nomenclature of Alkenes. Trivial system.

- ane

- ylene

CH4

Methane

CH2

Methylene (Not exist in nature)

C2H6

Ethane

C2H4

Ethylene

C3H8

Propane

CH3CH=CH2
H C C H H H

Propylene

C4H10

Butane

CH3CH2CH=CH2

Butylenes -Butylene

CH3CH=CHCH3

-Butylene

CH3 CH3

C CH2

Isobutylene

12

(1)

Naming as a derivatives of ethylene. CH3.CH=CH3 CH3.CH=CH.CH3 Methyl ethylene Dimethyl ethylene

(2)

IUPAC system - ane - ene

CH3 CH3 CH3 CH2 CH3 CH3 CH2 CH2 CH3 CH3 CH CH2 CH2 CH3 CH3

Ethane Propane Butane Isohexane

CH2= CH2 CH3CH=CH2 CH3CH2CH=CH2 CH3CH=CHCH3 CH3 CH CH CH CH3 CH3

Ethene Propene 1-Butene 2-butene

4 -methyl, 2-pentene

CH3 CH3 C CH2 CH CH2 CH CH2 CH3 CH3

4, 6, 6trimethyl, 1-heptene

2.5.2 1.

General Method of Preparation for Alkenes. Dehydration of monohydric alcohol: 160o C H 2SO4 160o C H 2SO4

RCH2CH2OH

RCH=CH2 +

H2O

CH3CH2CH2OH

CH3CH=CH2 +

H2O

13

CH3 CH CH3 OH

AL2O3 350o C

CH3CH=CH2 +

H2O

2.

Alkenes are formed when alkyl halides are boiled with alcoholic KOH: alcohol

RCH2CH2X + KOH

RCH=CH2 + KX + H2O

2.5.3

Properties of Alkenes.

C2 to C4 C5 to C15 C16 to onwards (i) (ii)

gas liquid (at room temperature) solid.

Olefins are lighter than water and insoluble. When they burn in air carbon dioxide and water are formed. C2H4 + 3O2 2CO2 + 2H2O

(iii)

Since each molecule of olefins has a double bond, they undergo addition reaction.

(a) Addition reaction with Hydrogen: Ni 200 300o C

CH2=CH2 + H2

CH3CH3

(b) Addition with Halogen: (X = Cl, Br) CCl 4 R.CH=CH2 + X2 R.CHX.CH2.X

14

(c) Addition with HCl: There is no problem when HX adds on a symmetrical olefin molecule to produce one product. However there are possibilities of obtaining two products when HX adds on unsymmetrical molecule of olefin. Practically only the isopropyl halide is formed in accordance with the Markownikoffs rule. CH3.CH=CH2 + HX
CH3 CH CH3 X

Markownikoffs Rule: When an unsymmetrical molecule such as HX reacts with unsymmetrical olefin molecule, the negative part of HX goes to that carbon atom which carrier the least number of hydrogen atoms.

CH3.CH=CH2 + HCl

CH3 CH CH3 Cl

In the presence of oxygen or peroxide, HBr does not obey the Markownikoffs Rule. This departure from the rule in known as abnormal reaction. HCl, HF, and HI do not exhibit the abnormal reaction. H 2O 2 CH3.CH=CH2 + HBr CH3.CH2.CH2.Br

(d) Other addition reactions: CH3.CH=CH2 +

HO Cl CH3 CH CH2Cl OH Propylene chlorohydrin

Hypochlorus acid

CH3.CH=CH2 +

NO Cl

CH3 CH CH2.NO Cl 1 nitro, 2-chloro propane

Nitrosyl chloride or bromide

15

CH3.CH=CH2 +

H2SO4

CH3 CH CH3 SO4H isopropyl hydrogen sulphate

Sulphuric acid
(iv)

When ethylene is passed into an alkaline solution of KMnO4, ethylene glycol is formed. KMnO CH2=CH2 + [O] + H2O 4

CH2.CH2 OH OH Ethylene glycol

(v)

Ozonolysis: Ozonolysis takes place when ozone adds on olefin molecules; the ozonide so produced can proceed to undergo hydrolysis.
O H2C O CH2 O

CH2=CH2 + O3

CHCl 3

H 2O Zn dust

CH3CH C

CH3 CH3

O3 CHCl3

O CH3 CH O C O

CH3 CH3

H2O Zn dust

CH3CHO + CH3COCH3 + H2O2

2.6

Acetylenes or Alkynes. The acetylenes are unsaturated hydrocarbons that contain one triple

bond. The simplest number of the series is acetylene HC CH ,

and

hence

this

homologous series is often referred to as the acetylene series. The acetylenes have the general formula CnH2n-2 and the triple bond is known as acetylene bond.

16

2.6.1

Nomenclature. Derivative method:

HC CH C.H3C CH C.H3C C.CH3 Acetylene Methyl acetylene Dimethyl acetylene

IUPAC: (-yne)
HC CH C.H3C CH C.H3C.H2C CH C.H3C C.CH3 (CH3)CHC C.CH3 Ethyne Propyne 1-butyne 2-butyne 4-methyl, 2-pentyne

2.6.2

General Methods of Preparation.

(i)

Acetylene is usually obtained on commercial scale when a mixture of limestone and coke is strongly heated in an electric furnace and calcium carbide so produced is allowed to react with water. 2000 o C

CaO + 3 C Quick line

CaC2

+ CO

CaC2 + 2H2O Calcium carbide

Ca(OH)2

+ C2H2 Ethyne

Slaked line

17

(ii)

Pure acetylene is formed in the laboratory when ethylene dibromide is heated with alcoholic KOH.

H H X C C H Vic-dihalide X + 2 KOH H alcohol CH CH + 2 KX + 2H2O

H X H C C H Gem- dihalide X + 2 KOH H alcohol CH CH + 2 KX + 2H2O

(iii)

Acetylene is also obtained by the electrolysis of a strong solution of sodium or potassium salt of maleic or fumeric acid.

CH COONa CH COONa Maleic acid

Electrolysis

CH COO CH COO + 2Na

2 H2O

CH CH + CO2 + 2 NaOH + H2

CH COONa NaOOC CH Fumeric acid

(iv)

Acetylene is also formed by heating iodoform with silver powder . 2CHI3 + 6Ag

HC CH + 6AgI

18

2.6.3 (i)

Properties of Acetylene. Acetylene is a colorless gas and has an ethereal-odor in a pure state. It is soluble sparingly in water but extremely in alcohol and acetone. Acetylene will explode violently when it is stored under a pressure greater than two atmospheres or it is converted into liquid.

(ii)

Acetylene burns with a luminous, smoky flame.

CH CH
(iii)

+ 5 O2 2

2CO2 +

H2O

Since alkynes are more unsaturated than alkenes they undergo addition reactions with four monovalent atoms or radicals. H2 Ni, 300oC Cl 2 H2 Ni, 300oC Cl 2 CHCl=CHCl Br 2 Br 2 CHCl2=CHCl2 CHBr2=CHBr2

CH CH

CH2=CH2

CH3CH3

CH CH
CH CH

CHBr=CHBr

Acetylene adds on iodine with difficulty. However in ethyl alcohol the reaction takes place smoothly. Acetylene diiodide is obtained. I2 EtOH

CH CH

CHI = CHI

(iv)

Water molecules add on acetylene when it is passed into a dilute sulphuric acid and HgSO4 at 60oC. H2SO4

CH CH

+ H2O

HgSO4, 60oC

CH2=CHOH Vinyl alcohol

CH3CHO Ethanal

19

(v)

When acetylene is passed into dilute HCl containing HgCl2 at 65oC, vinyl chloride is formed. Hg2+,
Cl

CH CH

65 oC

CH2=CHCl Vinyl chloride

CH2 CH

Polyvinyl chloride (PVC)

(vi)

When acetylene is passed into a solution of acetic acid containing Hg2+, ethylidene acetate is formed.

CH CH

Hg2+, + CH3COOH CH2=CH (OCOCH3) CH3CH (COCOCH3)2 Ethylidene acetate

(vii)

Acetylene also undergoes substitution reactions with alkali and coinage metal. When acetylene is passed into ammonical silver nitrate or ammonical cuprous chloride solutions respectively, silver acetylide and cuprous acetylides are precipitated.
CH CH + Na CH CNa Na NaC CNa diacetylide

mono sodium acetylide

These acetylides do not decompose when they are in contact with water. But in the presence of dilute acid they decompose to yield the original acetylene.
NaC CNa + 2HCl CH CH + 2NaCl

20

(viii) KMnO4 solution can easily oxidize the triple bond of acetylene molecule.

CH CH

+ [H2O]

KMnO 4 HCOOH + HCOOH H 2SO 4

(ix)

Ozonolysis:
O CH CH + O3 HC O CHO CHO Glyoxal + H2O2 O2 HCOOH + CH O HCOOH H2O

(x)

When acetylene is introduced into a red hot tube, it is converted into benzene.

H C 3 CH CH HC HC C H CH CH

(xi)

When acetylene is passed into Cu2Cl2 dissolved in NH4Cl solution, vinyl acetylene and divinyl acetylene are formed.

CH CH + CH CH

CH2 CH C CH vinyl acetylene

21

CHAPTER III

Monohydric Alcohols:
3. Monohydric Alcohols. Alcohols are hydroxyl-substituted compounds. They can be regarded being formed from the hydrogen atom of alkane by replacement with OH group. Alcohols are classified depending upon the number of OH groups present. Example, RCH2CH2OH
R CH CH2OH OH R CH CHCH2OH OH OH

Monohydric alcohol Dihydric alcohol

Trihydric alcohol

Those contain more than three hydroxyl groups are polyhydric alcohols. Monohydric alcohols are presented formula CnH2n+1OH. Monohydric alcohol: CH3OH CH3CH2OH Dihydric alcohol: Methyl alcohol Ethyl alcohol

CH2 CH2 OH OH
Trihydric alcohol:

Ethylene glycol

CH2 CH CH2 OH OH OH

Glycol or glycerin

22

3.1 (i)

Nomenclature. Common system: CH3OH CH3CH2OH CH3CH2CH2OH

CH3 CH CH3 OH

Methyl alcohol Ethyl alcohol n-propyl alcohol Iso-propyl alcohol

(ii)

Carbinol system: In this naming system, methyl alcohol is taken as carbinol and other alcohols can be considered as derivatives of methyl alcohol. CH3OH CH3CH2OH CH3CH2CH2OH
CH3 CH CH3 OH

Carbinol methyl carbinol Ethyl carbinol Dimethyl carbinol

CH3CH2CH2CH2OH
CH3 CH CH2OH CH3

n-propyl carbinol Iso-propyl carbinol

(iii) IUPAC system:

-e
CH3 CH3CH3 C3H8 Methane Ethane Popane CH3OH CH3CH2OH CH3CH2CH2OH
CH3 CH CH3 OH

- ol
Methanol Ethanol 1-propanol 2-propanol

C4H10

Butane

CH3CH2CH2CH2OH
CH3 CH2 CH CH3 OH

Butan-1-ol Butan-2-ol

23

CH3 CH CH2OH CH3 CH3 CH3 C CH3 OH

2-methyl, propan-1-ol (or) iso- butyl alcohol 2-methyl, propan-2-ol (or) Tertiary butyl alcohol 1-pentan, n-amyl alcohol Pentan, 2-ol Pentan, 3-ol

C5H12

Pentane

CH3CH2CH2CH2CH2OH

CH3 CH2 CH2 CH CH3 OH CH3 CH2 CH CH2 CH3 OH

CH3 CH CH2 CH2 OH CH3

3-methyl, butan-1-ol

Monohydric alcohols are divided into three classes vis: Primary, secondary, and Tertiary alcohols. Primary alcohol contains Secondary alcohol contains Primary alcohol contains CH2OH (functional group)
CHOH (functional group)

C OH (functional group)

3.2. (i)

General Methods of Preparation. By the hydrolysis of alkyl halides with aqueous NaOH or AgOH: RX + NaOH ROH + NaX (X = Cl, Br)

CH3CH2CL + AgOH (ii)

CH3CH2OH + AgCl

By the hydrolysis of esters with KOH:

Hydrolysis RCOOR/ + KOH

(iii) Bonveault-blane reduction: Na/EtOH RCHO + 2[H]

R/OH +

RCOOK

RCH2OH

24

RCOOR/ + 4[H RCOR + 2[H]

Na/EtOH Na/EtOH

RCH2OH + R/OH Primary alalcohol RCHOHR Sec: alcohol

(iv) By heating ether with dilute sulphuric acid under pressure: ROR + H2O (v) S/A Pr essure ROH + ROH

By the reaction of grignard reagent on aldehyde and ketones, sec: alcohols and ter: alcohols are obtained respectively: CH3CHO + CH3MgBr CH3 CH OMgBr CH3
H2O

CH3 CH3

CHOH

iso propanol

H3C H3C

CH3

C O + CH3MgBr

CH3 C OMgBr CH3

H2O

CH3 CH3 C OH CH3

Ter-butanol +

Mg

OH Br

(vi)

By the reaction of sulphuric acid on olefins. SO4H RCH=CH2 + H-SO4H R CH CH3 Hydrolysis OH R CH CH3 Sec: alcohol

3.3

Properties of Alcohols. Alcohols are neutral compounds. The lower members of alcohols are

soluble in water. They are liquid at room temperature and have peculiar smell. Higher members are Wax-like compounds and as the molecular weight increases the solubility in water decreases. As the alcohols with low molecular weight are supposed to

associate themselves through hydrogen bonding they are high boiling liquids and nonvolatile at low temperature.
O H O H O H

H-bonding

25

Chemical reactions: (i) Although alcohols are neutral compounds the hydrogen atom is acidic in character and readily reacts with most electropositive atom like Na, K, etc. ROH + Na RONa +
1 2

H2 H2

Sodium alkoxide CH3OH + Na CH3ONa +

1 2

Sodium methoxide

(ii)

Esterification: ROH + R COOH

/

H+

R/COOR Ester H+

H2O + H2O

CH3CH2OH + CH3COOH

CH3COOC2H5 Ester

(iii)

In the reactions of alcohols with phosphorous halides and thionyl chloride, the halogen atom will replace the OH groups of alcohols. 3ROH + PCl3 ROH ROH + PCl5 + SOCl2 3RCl + H3PO3 RCl + HCl + POCl3 RCl + HCl + SO2

Thionyl chloride (iv) Dehydration: When alcohols are heated with conc. S/A at 160oC, water molecule is removed and alkenes are formed. H 2SO4 160O C

CH3CH2OH

CH2=CH2 + H2O

Al2O3 at 350oC, phosphoric acid and ZnCl2 can be used as dehydrating agent.
CH3 CH CH3 OH

Al2O3 350oC

CH3.CH=CH2 +

H2O

26

(v)

Dehydrogenation: When vapors of alcohols are passed through freshly reduced copper powder, oxidation will take place with removal of H2 from alcohol molecules. RCH2.CH2.CH2 OH

Cu 300oC

RCH2CH2CHO + H2 H2

Cu
R CH CH3 OH

300oC

R C CH3 + O Ketone

However, dehydration will take place when vapors of tertiary alcohol are allowed to pass through freshly reduced copper power. R R C OH CH3 CH3 CH3 C OH CH3

Cu 300oC Cu 300 C
o

R R C CH2 + H2O

CH3 CH3

C CH2 + H2O

iso butene

This reaction is useful to distinguish primary, secondary, or tertiary alcohols.

(vi)

Oxidation: When primary alcohols are oxidized with strong oxidizing agent like acid dichromate, aldehydes are first formed. On further oxidation, they are converted into acids containing the same number of carbon atoms.

[O]
RCH2 CH2OH Alcohol RCH2.CHO Aldehyde

[O]
RCH2.COOH Acid (the same number of carbon atoms)

27

When secondary alcohols are oxidized they give ketone containing the same number of carbon atoms, which, on further oxidation, are converted into a mixture of acids containing less number of carbon atoms.

CH3 CH CH3 OH

[O]
CH3 C CH3 O

[O]

CH3COOH + HCOOH

It is very difficult to oxidize tertiary alcohols. When they are successfully oxidized, a mixture of ketone and acids containing less number of carbon atoms. CH3 CH3 C OH CH3 (vii) Reduction: Alcohols cannot be reduced directly. They are usually converted into alkyl halide and then reduced with Zn-Cu couple.

3[O]

CH3 C O + HCOOH + H2O CH3

ROH

HX

RX

ZnCl2 + 2[H]

RH + HX

3.4

Ethyl Alcohol: (Ethanol) Preparation of ethyl alcohol:

(i)

Ethylene is absorbed in concentrated sulphuric acid (98 percent) at 75o- 78oC, under pressure. Ethyl hydrogen sulphate and ethyl sulphate are formed. C2H4 + (HO2)SO2 C2H5OSO2.OH + C2H4 C2H5OSO2.OH (C2H5O)2SO2

The reaction mixture is then diluted with about an equal volume of water, and warmed. CH3CH2SO4H + H2O (C2H5O)2SO2 + 2H2O (C2H5O)2SO2 + C2H5OH C2H5OH + 2C2H5OH + H2SO4 H2SO4

C2H5OC2H5 + C2H5O.SO2.OH

28

Some diethyl ether is formed. The ether is kept to minimum by separating the ethyl sulphate from the reaction products. (ii) Ethanol is manufactured by the direct hydration of ethylene with steam under pressure in the presence of a suitable catalyst. C2H4 + H2O (iii) CH3 CH2 OH

Acetaldehyde (from acetylene) is catalytically reduced to ethanol by passing its vapor, mixed with hydrogen over finely divided nickel at 100-140oC. CH3CHO + H2 CH3CH2OH

(iv) Fermentation method: (Industrial method). Starting material is starch. Common source of starch are wheat, barley, potato, etc. Molasses has also been used as the starting material for ethanol. The grain, e.g., wheat or barley is mashed with hot water and then heated with malt (germinated barley) at 50oC for one hour. Malt contains the enzyme diatase which by hydrolysis, converts starch into the sugar, maltose. (C6H10O5)n + n H2O 2

diatase

n C12H22O11 2

If molasses is used, this step is no needed to carry out, since it contains carbohydrate already present as sugar, which can be fermented. The liquid is cooled to 30oC and fermented with yeast for 1-3 days. Yeast contains various enzymes, among which maltase, which converts the maltose into glucose, and zymase which converts the glucose into ethanol.

C12H22O11 + H2O C6H12O6

maltase zymase

2 C6H12O6 2 C2H5OH + 2 CO2

Fractional distillation is carried out to obtain the rectified spirit. Absolute alcohol can be obtained by distillation the rectified spirit with calcium oxide and Ca metal.

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Properties of ethanol: Ethanol is a colorless, inflammable liquid, b.p 75%. It is miscible with water in all proportions. (i) It burns with a pale blue flame forming CO2 and water. CH3CH2OH + 3O2 (ii) 2CO2 + 3H2O

Except that the iodoform reaction is given by ethyl alcohol are similar in all aspects.

CH3CH2OH + 4 I2 + 6 NaOH

CHI3 + HCOONa + 5 NaI + 5 H2O

Isopropyl alcohol can be also give iodoform reaction but n-propyl alcohol will not.

CH3 CH3

CHOH + 4 I2 + 6 NaOH

CHI3 + CH3.COONa + 5 NaI + 5 H2O no reaction.

CH3CH2 CH2 OH + 4 I2 + 6 NaOH

(iii) When ethyl alcohol and chlorine are mixed together, chlorine will oxidize the alcohol and then replace the acetaldehyde so formed.

C2H5OH + Cl2 CH3 CHO + Cl2

CH3CHO + 2HCl CCl3.CHO + 3HCl Chloral

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CHAPTER IV

Alkyl Halides:
4. Alkyl Halides. The halogen derivatives of the paraffin are divided into mono-, di, tri, etc, substitution products according to the number of halogen atoms in the molecules.

Mono:

Di:

C2H5Cl CH3.CHBr.CH3 (CH3)3.C.Cl

ethyl chloride isopropyl bromide ter-butyl chloride

CH2Cl. CH2Cl CH3CHCl2 CH2Cl.CH2CH2CH2Cl

Vic- dihalide Gen-dihalide Ethylidene chloride 1,4-dichloro Butane

Monohalogen derivatives are generally called alkyl halides with the general formula CnH2n+1 X or RX, where X denotes chlorine, bromine, or iodine.

4.1 (i)

General Methods of Preparation. When hydrogen chloride is passed into the alcohol in the presence of anhydrous Zinc chloride, ethyl chloride is formed.
ZnCl2 100oC

C2H5OH + HCl (ii)

C2H5Cl + H2O

Alkyl bromide may be prepared by refluxing the alcohol with excess constant boiling hydrobromic acid, in the presence of a little sulphuric acid.
H+

CH3CH2OH + HBr

H2SO4

CH3CH2Br + H2O

31

By heating the alcohol with potassium bromide and concentrated sulphuric acid in excess. ROH + KBr + H2SO4 (iii) RBr + KHSO4 + H2O

By the action of phosphorous halide on alcohols, alkyl halide can be obtained. ROH + PCl5 3ROH + PCl3 RCl + HCl + POCl3 3RCl + H3PO3

(iv)

When alcohols are refluxed with thionyl chloride in the presence of pyridine, alkyl chlorides are formed. ROH + SOCl2 Pyridine RCl + SO2 + 2HCl

(v)

Potohalogenation: Potohalogenation is carried out by trating the alkane (especially methane) with chloride in the presence of diffused sunlight. CH4 + Cl2 CH3Cl + HCl Methyl chloride CH3Cl + Cl2 CH2Cl2 + Cl2 CCl3 + Cl2 CH2Cl2 + HCl Methylene chloride CHCl3 + HCl Chloroform CCl4 + HCl Carbon tetrachloride

4.2 (i)

General Reaction of Alkyl halide. When alkyl halides are reduced with nascent hydrogen or molecular hydrogen. RX + 2H RX + H2 Zn/HCl
Ni or Pd 200-300oC

RH + HX RH + HX

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CHAPTER V
Ether: They form a homologous series with the general formula CnH2n+2.O. They can be regarded as being formed by replacing two hydrogen atoms in water by two alkyl groups.
H O H R O R

Ethers are isomeric with alcohols containing the same number of carbon atoms, e.g., dimethyl ether (CH3.O.CH3) is isomeric form of ethyl alcohol C2H5OH. Methyl ethyl ether is isomeric with propyl alcohol, C3H7OH. When two alkyl groups in ether molecule are the same, it is simple ether. If different, then it is called mixed ether, e.g., R-O-R R-O-R/ simple ether mixed ether (R R/)

5.1 (i)

Nomenclature. Common name: CH3OC2H5 C2H5O C2H5 methyl ethyl ether diethyl ether

(ii)

IUPAC system: According to this system of nomenclature, the ethers are regarded as hydrocarbons inwhich hydrogen atom is replaced by an alkyl group OR, the lager radical being chosen as alkane. CH3O CH3 CH3O C2H5 C2H5O C2H5 C2H5O C3H7 Methoxy methane Methoxy ethane Ethoxy ethane Ethoxy proane 3-methoxy hexane

CH3CH2CH2CHCH2CH3 OCH3

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5.2 (i)

Methods of Preparation. Williamson synthesis: RONa + RX CH3ONa + C2H5I CH3ONa + CH3Br ROR + NaX CH3O C2H5
+

NaI

CH3OCH3 + NaBr

(ii)

From alcohol: Both primary and secondary alcohols will give simple ethers. Both alcohols react with concentrated sulphuric acid at 140oC to give simple ether. C2H5OH + H.SO4H C2H5 SO4H + C2H5OH Net reaction: 2 C2H5OH CH3 CH3 CHOH H2SO4 140o 110o C 140 o C H 2SO 4 140o C C2H5 SO4H + H2O C2H5O C2H5 + H2SO4H C2H5O C2H5 + H2O CH3 CH3 + H2O

CH3 CH.O.CH.CH3 di-iso prropyl ether

Excess of alcohol should be used. The catalysts such as alumina, thoria and under pressure can be used in the preparation of ether. (iii) By heating with alkyl halide with silver oxide. 2RX + Ag2O ROR + 2AgX

5.3

Properties of Ether. There is no hydrogen bonding between ether molecules although they have one oxygen atom. Because the oxygen atom is linked with two carbon atoms in the molecule. CH3.O.CH3 Thus they have low boiling points compared to the corresponding alcohols having the same molecular weights. They are colorless volatile liquid with pleasant smell.

35

When heated with dilute sulphuric acid under pressure, ethers form the corresponding alcohols. R2O + H2O H 2SO 4 2ROH CH3OH + C2H5OH

CH3OC2H5 + H2O

Ethers are readily attacked by concentrated hydrochloric acid or hydrobromic acids; the final products depend on the temperature of the reaction. In the cold: ROR + HI RI + ROH

In the case of mixed ether the iodine atom attaches itself to the smaller alkyl radical. CH3OC2H5 + HI When heated: R2O + 2HI CH3I + C2H5OH 2RI + H2O

When heated with chlorine or bromine, ethers undergo substitution, the extent of which depends on the conditions. CH3CH2OCH2CH3 Cl 2 CH3CHCl.O.CHClCH3 1,1/-dichloro diethyl ether Acid chlorides react with ether when heated in the presence of anhydrous ZnCl2 or AlCl3 etc. ZnCl 2 R2O + CH3COCl RCl + CH3COOR

Ethers react with CO at 125-180oC under 500 atms pressure in the presence of BF3 and a little water. R2O + CO RCOOR (ester)

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CHAPTER VI
Aldehydes and Ketones:

Aldehydes and ketones both have general formula CnH2nO. Their functional groups are: for aldehyde for ketone
C C O C O C H

, which can occur at the end of the chain, and , which cannot occur at the end of the chain.

6.1

Nomenclature. Aldehyde: HCHO CH3 CHCHO CH3 CH3.CH2.CHOH.CH2.CHO IUPAC system: CH3CHO CH3.CH2CHO
2 3 4 5

formaldehyde (comes from formic acid) iso butyraldehyde (comes from butyric acid) -hydroxy, butyraldehyde

Ethanal (from ethane) Porpanal (from propane) 2-ethyl, 3-methyl, pentanal

CH3.CH2.CH.CH.(CH 3).CH 2.CH3 1 CHO

Ketone: CH3.CO.CH3 CH3.CH2.CO.CH.(CH3)2 IUPAC system: CH3.CO.CH2.CH2.CH3 (CH3)2.CH.CO.CH. (CH3).CH2.CH3 Propan-2-one 2, 4-dimethyl, 3-pentanone Dimethyl ketone (acetone) Ethyl isopropyl ketone

37

Since aldehydes and ketones both contain the carbonyl group, it might be expected that they would assemble one another. Therefore, general methods of preparation and properties of both aldehydes and ketones are described together.

6.2 (i)

General Methods of Preparation of Aldehydes and Ketones. Aldehyde: By the oxidation of a primary alcohol: RCH2OH [O ] RCHO + H2O

Oxidizing agents may be acid dichromate. By passing the alcohol vapor mixed with air over heated silver (250oC) as catalyst. Dehydrogenation of alcohols can occur by heating at 300oC with copper as catalyst.
Cu

CH3CH2OH

300oC

CH3CHO + H2
Ag

CH3CH2CH2OH

250oC

CH3CH2CHO + H2

Ketone: By the oxidation of a secondary alcohol or by dehydrogenation over heated copper; RCH(OH)R/ RCH(OH)R/
[O]

RCOR/ + RCOR/ +

Cu 300oC

H2O H2

(ii)

Aldehyde: By heating a mixture of the calcium salts of formic acid and any one of its homologues: (RCOO)2Ca + (HCOO)2Ca 2RCHO + 2CaCO3 2 CH3CHO + 2CaCO3

(CH3COO)2Ca + (HCOO)2Ca

39

Ketone:
R2 C CR/2 O3 CHCl3 O R2 C O C R/2 O H2O Zn dust R2CO + R/2CO + H2O2

(vi) Aldehyde: When passed into hot dilute sulphuric acid in the presence of mercuric sulphate as catalyst, is converted into acetaldehyde. CH CH Ketone: All homologues of acetylene, treated in same way as acetylene, forms ketone. R.C C.CH3 + H2O HgSO4 H2SO4, 60o HgSO4 H2SO4, 60o CH3.CO.R + H2O HgSO4 H2SO4, 60o CH3CHO

CH3C CCH3 + H2O

CH3COCH2CH3

(vii) Aldehyde: Stephens reaction: Ether SnCl2 HCl H2O RCHO H2O

R.C N

+ HCl

R.C NH Cl

R.CH NH2 SnCl6

4RCN + LiAlH4

R.CH N

LiAl

RCHO

Ketone: No analogous method.

PART TWO