13.

ORGANIC CHEMISTRY
I) SOME BASIC PRINCIPLES AND TECHNIQUES

Synopsis :
Introduction and classification : 1. Based on their source, chemical compounds are classified into 3 types by Lemery: i) Mineral source ii) Vegetable source iii) Animal source Vital force theory : Lavoiser found that the compounds from vegetable and animal sources contain similar composition. Then Berzelius classified the above 3 types into 2 types and he coined the new terms Organic and Inorganic. i) Organic compounds: These are present in living beings (plants, animals etc.) ii) Inorganic compounds: These are present in minerals But now based on the structure and chemical behaviour, the compounds are classified as i) Organic compounds ii) Inorganic compounds Organic compounds are carbon compounds and the study of chemistry of carbon compounds is called organic chemistry. Organic compounds contain Carbon, Hydrogen, essentially and Oxygen, Nitrogen, Sulphur, Phosphorus, Halogen etc frequently. Father of organic chemistry is Wohler who synthesized the first organic compound in laboratory from inorganic substances.
NH4Cl+KCNO
KCl

NH4CNO
ammonium cyanate

NH2 C NH2
|| O

With the synthesis of urea vital force theory of Berzelius was discarded, according to which organic compounds cannot be synthesized without any vital force. Kolbe synthesised CH3COOH from its elements. Berthelot synthesised CH4 Carbon is tetravalent as it contains four unpaired electrons in its excited state configuration. The tetravalency of carbon was given by Vanthoff and Lebel who were awarded the first nobel prize in chemistry. 1 o Ground state configuration of 'C' : 6 C 1s2 2s2 2p1 x 2p y 2p z
1 1 Excited state configuration of 'C' : 6 C 1s2 2s12p1 x 2p y 2p z

Carbon alone forms about 10 millions of organic compounds where as the remaining elements together could form just about 50000 compounds. Largest number of compounds formed by carbon because of its marked features. 1) Highest catenation 2) Tetravalency 3) Ease of formation of multiple bonds Natural sources of organic compounds are coal, petroleum, natural gas, animals and plants.

Organic Chemistry
Classification of organic compounds :
Classification based on carbon chain :

Open chain (Aliphatic or Acylic) Unsaturated Saturated Ex. Alkanes Ex. Alkenes, Alkynes Alicyclic Ex. Cycloalkanes

Closed chain (Ring or cylic ) Homocylic (Carbocyclic ) Heterocyclic Ex. Furan, Pyrrole, Pyridine, Aromatic Thiophene Ex. Benzene

Carbon compounds are classified into various types based on the nature of functional groups:
Name Formula Functional group Name of the functional group

1) Alkanes (paraffins) 2) Alkenes (olefins) 3) Alkynes (acetylenes) 4) Alkyl halides (Haloalkanes) 5) Alcohols (Alkanols) 6) Ethers 7) Amines (Amino alkanes) 8) Aldehydes (Alkanals) 9) Ketones (Alkanones) 10) Carboxylic acids(Alkanonic acids) 11) Esters (Alkyl alkanoates 12) Amides 13) Cyanides 14) Nitro compounds 15) Sulphonic acids

RH RCH =CH2 R C CH RX R OH R OR R NH2 R CHO R CO R R COOH R COOR R CONH2 R CN R NO2 R SO3H

CC > C = C< C C X OH O NH2 CHO >C=O COOH COOR CONH2 CN NO2 SO3 H

Single bond Double bond Triple bond Halogen Hydroxy Ether Amino Aldehyde Keto Carboxyl Ester Amide Cyanide Nitro Sulphonic Acid

Open chain compounds: Carbon atoms are linked to one another to form straight chains or branched ones but not rings. Open chain compounds are also called aliphatic compounds. Ex: Alkanes, alkenes, alkynes and their derivatives. Cyclic compounds: Carbon atoms are linked to one another to form ring. Based on the number of rings, they may be monocyclic or polycyclic. Homocyclic: Ring is formed by carbon atoms only. Ex: Benzene, Phenol, Toluene, Cyclopropane etc. 2

Organic Chemistry Heterocyclic: Along with carbons some hetero atom like, N, O, S, P, etc is involved in forming the ring. N N Pyridene H Pyrrole Alicyclic: These are cyclic compounds but resemble open chain compounds in properties. Ex.: Cycloalkanes, cycloalkenes, cycloalkynes Aromatic: The ring compounds which resemble benzene in structure and properties are called aromatic compounds. These may be homocyclic or heterocyclic. Ex.: O S Furan Thiophen
OH

Benzene

Phenol

Napthalene

Furan

Thiophene

Bonding in carbon compounds : In all its compounds, carbon undergoes only 3 types of hybridisation i.e. sp, sp2 and sp3. The tetravalency of carbon is possible in its excited state configuration, as it contains four unpaired electrons The energy required for the promotion of electron from 2s orbital to 2p orbital is 501.6 kJ/mol. sp3 hybridisation is found in alkanes. sp3 hybrid carbon forms four single bonds or four sigma bonds. The ratio of s character to p character in each sp3 hybrid orbital is 1 : 4. sp3 hybrid carbon forms C C and C H bonds. Shape of the molecule is tetrahedral and bond angle is 109. sp2 hybridisation is found in alkenes. sp2 hybrid carbon forms 3 sigma bonds and 1pi bond or one double bond and two sigma bonds. The ratio of s character to p character in sp2 hybrid orbital is 1 : 2. Shape of molecule is trigonal planar and bond angle is 120. sp hybridisation is found in alkynes and cumulative dienes. SP hybrid carbons forms 2 and 2 bonds i.e. 1 triple and 1 single or 2 double bonds. The ratio of s character to p character in sp hybrid orbital is 1 : 1. Shape of molecule is linear and bond angle is 180.

Organic Chemistry 3. STRUCTURAL FORMULAE (OR) CARBON SKELETON DIAGRAMS 1. In bond line diagrams the atoms other than C & H are only shown. Hydrogen atoms if they are bonded to Hetero atoms like N & O are shown.

2.

CH 3 CH 2 CH 2 CH 3 Butane CH 3 CH 2 CH 2 CH 2 NH 2 Butanamine

3. Cyclo propane

Cyclo propane

Cyclo butane

5.

Chloro cyclo pentane 6.

7.

Organic Chemistry
8.

I.

4.METHODS OF PURIFICATION OF ORGANIC COMPOUNDS Methods of purification of organic Compounds: Organic compounds obtained either from natural sources or synthetic processes in the laboratories are contaminated with impurities. These are purified by different methods. Methods of purification of solids: 1.Crystallisation:This method is useful to purify the solid organic compounds. The principle involved in this method is that the compound should be insoluble at low temperature but soluble at higher temperatures in the given solvent. Impurities are either insoluble or soluble and go into filtrate. The insoluble impurities are removed by filteration in hot condition. The crystals of the compound are seperated by filtering under reduced pressure using Buckner funnel. Repeated crystallisation is required and the coloured impurities are removed by adsorbing them with activated charcoal. 2. Sublimation : It is used to purify activated solid organic compounds which undergoes sublimation. If the compound is sublimating the impurity should not sublimate. If the compound to be purified has high vapour pressure below its melting point and sublimates readily on heating and the impurities dont sublimate. The pure compound is seperated by scratching the watch glass. If the sublimating substances have a low vapour pressure or decompose on heating before sublimation, then the sublimation is carried out under low pressure. Methods of purification of liquids:1.Simple distillation:- The vapourisation of a liquid by heating and subsequent condensation of vapours by cooling is known as distillation. This process is useful for purification of liquids contaminated with non volatile impurities. The liquids that have boiling point difference greater than 400 C can be purified by this method. 2.Fractional distillation:This process is useful for the purification of liquids having boiling point difference less than 400C. In this process, liquid with high b.p. is collected in the condenser and liquid with low b.p. is collected in the receiver. 3.Distillation under reduced pressure:This method is useful to purify liquids that have very high boiling points and those which decompose at or below their boiling points. At reduced pressure the boiling point of a liquid is also reduced. Hence its decomposition is prevented. 5

II.

Organic Chemistry
4. Steam distillation:The liquids insoluble in water possess high boiling point and steam volatile and the impurities are not steam volatile are purified by this method. Principle in steam distillation is - sum of the vapour pressure of organic liquid (P1) and that of water (P2) is equal to atmospheric pressure (P) and mixture boils. The water layer and the organic liquid layer are seperated using separating funnel. Ex:- Aniline is purified by this method from Aniline - water mixture Relative masses obtained in steam distillation process is calculated by a formula = 0 WA n A M A p A M = = 0 A ; Where WA and WB are the masses of A and B WB nB M B p B M B
M A and M B are the molecular masses of A and B PA0 and PB0 are the vapour pressures of A and B At 98.50 C water and aniline have vapour pressures 717 torr and 43 torr. In steam distallation at WH 2O 717 18 = = 3.23 98.50 C , the relative masses obtained are WAniline 43 93 Solvent extraction( differential extraction) :In this method, organic compound is separated from its aqueous solution by using its solubility which is different with organic solvent and water. Chromatography:It was discoverd by Tswett in (1906). He separated chlorophyll and Xanthophyll and other compounds by using adsorbent CaCO3 . It is classified into three types based on the physical states of stationary phase and mobile phase. Chromatography involves the three steps a) Adsorption and retention of a mixture of substances on the stationary phase and separation of adsorbed substances by the mobile phase to different distance on the stationary phase. b) Recovery of the substances separated by a continuous flow of the mobile phase (known as elution) c) Qualitative and quantitative analysis of the eluted substances

5. 6.

S.No.
1. 2. 3. 4. 5. 6. 7.

Chromatography Process
Column chromatography (Adsorption) Liquid liquid partition chromatography Paper chromatography Thin layer chromatography (TLC) Gas liquid chromatography (GLC) Gas solid chromatography (GSC) Ionic change chromatography

Stationary Phase
Solid Liquid Liquid Liquid (or) solid Liquid Solid Solid

Mobile Phase
Liquid Liquid Liquid Liquid Gas Gas Liquid

Organic Chemistry Important chromatography techniques are 1) Adsorption chromatography : a) Column chromatography, b) Thin layer chromatography 2) Partition chromatography : a) Paper chromatography a) Column Chromatography The principle used in this method is differential adsorption. In the column chromatography the components of a mixture are separated by a column of adsorbent (stationary phase) packed in a glass tube. The mixture to be adsorbed on the adsorbent is placed at the top of the stationary phase. A suitable eluant, either a single solvent or a mixture of solvents is allowed to flow down the column slowly. The most readily adsorbed substances are retained near the top and others come down accordingly to various distances. b)Thin layer chromatography (TLC): This also based on the adsorption differences. The glass plate which is coated with adsorbent (Eg : Silica gel, alumina) as a thin layer (0.2mm thick) is called TLC plate or chromoplate. The plate is then kept in a closed jar containing the eluant. The relative adsorption of a component of the mixture is expressed in terms of RETARDATION FACTOR (Rf) value. Distance moved by the substance from base line (X) Rf = Distance moved by the solvent from base line (Y) The colourless compounds which fluorescence are detected with ultraviolet light. Spots of compounds are even detected by allowing them to adsorb iodine, when they give brown spots. Some times an appropriate reagent is sprayed, as ninhydrin solution to detect aminoacids. c) Partition Chromatography This is based on continuous differential partitioning of components of a mixture between the stationary phase and the mobile phase. In paper chromatography, a special paper called chromatography paper contains water trapped in it which acts as the stationary phase. The chromatography paper spotted with the solution of the mixture at the base is suspended in a suitable solvent or a mixture of solvents. This solvent (s) acts as the mobile phase. The solvent rises up the paper by capillary action and moves over the spot. The paper selectively retains different components as per their differing partition in mobile and stationary phases and is known as chromatogram. The spots of the separated coloured compounds are detected.

5. QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS Qualitative analysis of organic compounds 1) Detection of carbon and hydrogen Carbon and hydrogen are detected with - CuO (Cupric Oxide) If carbon is present, its forms CO2 gas. The CO2 gas turns lime water milky
Ca ( OH)2 + CO2 CaCO3

C + 2CuO 2Cu + CO2

Organic Chemistry

If hydrogen is present in the compound it forms H2O vapour. H2O vapours when passed over white anhydrous CuSO4 turns it blue by forming CuSO45H2O.
2H + CuO Cu + H2O CuSO 4 + 5H2 O CuSO4 5H2 O
( white ) (blue )

2) Detection of halogen, nitrogen and sulphur ( Lassaignes test or sodium extract test) In Lassaignes test, the compound is heated strongly in an ignition tube to fuse with sodium metal. Here nitrogen present in the organic compound is converted as .CN
Na + C + N NaCN

from organic compound sodium cyanide If sulphur is present in the organic compound is converted as S 2
2Na + S Na2 S

sodium sulphide If halogens are present in the organic compound are converted as X
2Na + X 2 2NaX(X = Cl, Br, I)

The above obtained fused mass is extracted with water by plunging the red hot ignition tube in distilled water and the contents are boiled for 10 minutes and filtered. The filtrate is called sodium extract. i) Test for nitrogen: Take a portion of the sodium extract, if it is not alkaline add NaOH solution to it and then freshly prepared ferrous sulphate solution. Now add 2 or 3 drops of FeCl3 solution, cool, acidify with conc HCl. A prussian blue or green precipitate (or) coloration is observed if nitrogen is present. FeSO4 + 2 NaOH Fe ( OH )2 + Na2 SO4

6 NaCN + Fe ( OH )2 Na4 Fe ( CN )6 + 2 NaOH

3

sodium ferrocyanide 3 Na4 Fe ( CN )6 + 4 FeCl3 Fe4 Fe ( CN )6 + 12 NaCl

Ferric ferrocyanide (prussian blue)

ii) Test for sulphur : To a portion of the Na extract add freshly prepared sodium nitroprusside solution. A deep violet colouration takes place.
S 2 + Fe ( CN )5 NO
2

Fe ( CN )5 NOS

nitroprusside violet If N,S both are present gives thiocyanate, Na + C + N + S NaSCN thiocyanate To this if FeCl3 solution is added, Fe3+ + SCN Fe ( SCN )6 . It gives only blood red colour. No Blood red colour or prussian blue colour indicates that there are no N or S. If sodium fusion is carried out with excess of Na the thiocyanate decomposes to yield CN and S2. Na SCN + 2 Na NaCN + Na2 S
3

Organic Chemistry

Sodium fusion extract is acidified with acetic acid and then lead acetate solution is added Pb 2 + S 2 PbS black ppt iii) Tests for halogens: The sodium fusion extract is acidified with nitric acid. Now it is treated with AgNO3 solution. Ag + + X AgX If white precipitate is formed that is soluble NH 4OH in solution, the halide is Cl . Hence chlorine is present. If pale yellow precipitate, sparingly soluble NH 4OH in solution is formed it is bromide ( Br ) and the halogen is bromine. If an yellow precipitate, almost insoluble in NH 4OH solution is formed it is ( I ) iodide and the halogen is iodide. c) Detection of phosphorus: The compound is heated with an oxidising agent say sodium peroxide. The P in the organic 3 compound is oxidised to PO4 . The solution is boiled with HNO3 and treated with ammonium molybdate. A canary yellow precipitate formation indicates the presence of phosphorous in the compound. . Na3 PO4 + 3HNO3 H 3 PO4 + 3 NaNO3
H 3 PO4 + 12 ( NH 4 )2 MoO4 + 21 HNO3 ( NH 4 )3 PO4 .12 MoO3 + 12 H 2O

ammonium phosphomolybdate

d) Detection of oxygen: There is no direct test for oxygen. The organic compound when heated in pure nitrogen atmosphere if water droplets are formed on the walls of the test tube oxygen is detected. Otherwise after determining the % composition of all elements in the compounds if it does not come to 100%, the remaining is of oxygen. Even by detecting functional groups like OH , CHO, COOH , NO etc oxygen is detected.
6. QUANTITATIVE ORGANIC ANALYSIS

Quantitative Organic Analysis 1. Estimation of Carbon and hydrogen:- (Leibig method) A known weight of the organic substance is taken and completely burnt in excess of air & Copper (II) oxide. Carbon changes to CO2 and hydrogen changes to H2O as follows.
y y CxHy + x + O2 xCO2 + H2 O 4 2

The CO2 and H2O obtained are passed through weighed U tubes Containing anhydrous CaCl2 and caustic potash respectively. The increased weight of these two tubes give the weight of H2O formed and weight of CO2 formed.
% of C =
% of H=

Wt.of CO2 formed 12 100 44 Wt. of Organic compound

Wt.of H2 O formed 2 100 18 Wt. of Organic compound

Organic Chemistry

2.

After calculating the percentage composition all C and H in the compound if their sum is not 100, then the difference is assumed as oxygen. Estimation of Nitrogen: There are two methods to estimate nitrogen in the given compound. They are i. Dumas method ii. Kjeldahls method

i.

Dumas method: In this method a known weight of organic compound is heated strongly with dry curpic oxide. Carbon and hydrogen get oxidised to carbondioxide and water vapour. Nitrogen if present is converted to N2 is collected over KOH solution and its volume is determined at S.T.P
y y z y CxHyNz + 2x + CuO xCO2 + H2O + N2 + 2x + Cu 2 2 2 2 28 Volume of Nitrogen at S.T.P % of N = 100 22400 Weight of organic compound

ii.

Kjeldahls method: In this method the given organic compound is treated with Conc.H2SO4 in the presence of small amounts of CuSO4 to convert nitrogen into ammonium sulphate. Then ammonium sulphate is treated with excess of NaOH to liberate NH3 gas. The ammonia evolved is neutralised with excess of Conc H2SO4. which is relatively more in amount than that is required to neutralise NH3 gas. Now, the excess of acid is titrated with standard alkali solution. From this the amount of H2SO4 used to neutralise NH3 formed is calculated and from that percentage of nitrogen is calculated.
Oraganic compounds + H2SO4 (NH4 )2 SO4

(NH4 )2 SO4 + 2NaOH Na2SO4 + 2H2O + 2NH3 2NH3 + H2SO4 (NH4 )2 SO4
% of N =
1.4 N V Wt.of organic compound

Where N = Normality of acid V = Volume of acid (ml) neutralised by ammonia

3.

Estimation of halogens (Carius method) In this method a known weight of organic compound is heated with fuming nitric acid in the presence of Ag NO3 in a hard glass tube called Carius tube. Carbon and hydrogen of the compound are oxidised to CO2 and H2O. Halogen forms Silver halide (AgX). It is filtered, washed dried & weighed.
% of Halogen ( X ) = % of Cl = % of Br = % of I =
At.wt of X Wt.of Ag X 100 Mol.wt of AgX Wt of Oraganic compound

35.5 Wt.of AgCl formed 100 143.5 Wt of Oraganic compound 80 Wt.of AgBr formed 100 188 Wt of Oraganic compound

127 Wt.of Ag I formed 100 235 Wt of Oraganic compounds

10

Organic Chemistry

4.

Estimation of sulphur: A known weight of organic compound containing sulphur is heated with Na2O2 or fuming HNO3 in a carius tube. The sulphur in it is oxidised to H2SO4. The acid is precipitated as BaSO4 by adding excess of BaCl2 solution. The precipitate is filtered, washed, dried and weighed.
% of S =
Wt. of BaSO 4 32 100 233 Wt.of Oraganic compound

5.

Estimation of Phosphorus: To estimate phosphorus in the given organic compound, a known mass of organic compound is heated with fuming nitric acid in a Carius tube. Phosphorus is oxidised to phosphoric acid. The acid is precipitated as ammonium phosphomolybdate ( NH 4 )3 PO4 .12MoO3 by adding ammonia
and ammonium molybdate solutions. Sometimes, the acid is precipitated by adding magnesia mixture. Magnesia mixture is obtained by dissolving 100.0g. of MgCl2. 6 H2O and 100.0g.of NH4Cl in water, then adding 50.0 ml of conc.NH4OH and diluting the solution to 1000 ml. A Precipitate of magnesium ammonium phosphate ( Mg NH 4 PO4 ) is formed which on ignition gives magnesium pyrophosphate (Mg2P2O7). % of P = % of P =
Wt. of Mg 2 P2 O7 2 31 100 (or) 222 Wt.of Oraganic compound
31 Wt. of ( NH 4 )3 PO 4 .12MoO3 100 1877 Wt.of Oraganic compound

6.

Estimation of Oxygen: The percentage of oxygen in an organic compound is found indirectly by the difference between 100 and total percentage of other elements. In the direct method, a known mass of organic compound is decomposed by heating in a stream of nitrogen gas. The mixture of gaseous product containing oxygen is passed over red hot coke to convert all oxygen in those oxides to CO. Then the mixture is passed through warm iodine pentoxide ( I2 O5 ) to convert CO to CO2 and liberating iodine. Heat Compound O2 + other gaseous products ; N2
1373 K 2C + O2 2CO ; I 2O5 + 5CO I 2 + 5CO2

Homologous series : The series of organic compounds having a common difference of CH2 between any two successive members is called homologous series. The classification and study of the members of the homologous series is called homology and the members of the series are called homologues.
Characteristic features of homologous series :

i) ii) iii) iv) v)

There is a common difference of CH2 between two successive members. There is a common difference of 14 in molecular weight between two successive members. They possess similar chemical properties. There is regular gradation in their physical properties They can be prepared by similar methods. They can be represented by a general molecular formula.
11

Organic Chemistry

Ex. Alkanes CnH2n + 2 Alkenes CnH2n Alkynes Cn H2n 2 Alkyl halides CnH2n+1 X Alcohols and ethers CnH2n+2O Aldehydes and ketones CnH2nO Carboxylic acids and esters CnH2nO2 Types of Carbons and Hydrogens : Primary Carbon (1 carbon) : It is bonded to just one another carbon or to no other carbon. Secondary carbon (2 carbon) : It is bonded to two other carbons. Tertiary carbon (3 carbon) It is bonded to three other carbons. Quaternary carbon (4 carbon) : It is bonded to four other carbons. Types of hydrogens :

Primary hydrogen : Hydrogen attached to primary carbon. Secondary hydrogen : Hydrogen attached to secondary carbon. Tertiary hydrogen : Hydrogen attached to tertiary carbon.
1

Ex.

CH3 | 1 2 3 1 CH3 CH2 CH C CH3 | | CH CH3 3

1 1

In the above structure, five primary carbons, one secondary carbon, one tertiary carbon and one quaternary carbon are present. Similarly, the number of primary hydrogens 15, secondary hydrogens 2, tertiary hydrogen 1, and there is no quaternary hydrogen. IUPAC nomenclature: IUPAC name of compound consists of i) Root word ii) Suffix iii) Prefix Root word gives the number of carbons in parent skeleton Suffix gives the nature of the functional group Prefix gives the nature of the substituent. Side chains: i) Alkyl: It contains one hydrogen less than that of alkane. Ex. Methyl CH3 C2H5 Ethyl CH3 CH2 CH2 n propyl
CH3 CH | CH3

iso propyl nButyl Iso butyl Sec butyl 12

CH3 CH2 CH2 CH2

CH3 CH CH2 | CH3

CH3 CH CH2 CH3

|

Organic Chemistry
CH3 | CH3 C CH3 |

ter butyl n pentyl (Amyl) Iso pentyl (Iso amyl) Ter-Pentyl

CH3 CH2 CH2 CH2 CH2

CH3 CH CH2 CH2 | CH3 | CH3 C C2H5 | CH3
CH3 | CH3 C CH3 | CH3

Neo Pentyl

Alkenyl : It contains one hydrogen less than that of Alkene. Ex : CH2 = CH Ethenyl ( Vinyl) 1Propenyl CH3 CH = CH CH2 = CH CH2 Allyl CH3 CH2 CH = CH 1Butenyl Alkynyl: It contains one hydrogen less than that of alkyne Ex: HC C ethynyl H3C C C 1 propynyl H3C CH2 C C 1 butynyl When all the carbons are present in a straight chain, the alkane is called normal alkane. When all the carbons are not present in straight chain, it may be called iso alkane. Ex: CH3 CH2 CH2 CH3 n Butane Iso butane CH3 CH CH3
| CH3

Root word :

No. of carbons: 1 2 3 4 5 6 7 8 9 10

Root word Meth Eth Prop But Pent Hex Hept Oct Non Dec

13

Organic Chemistry

1. 2. 3. 4. 5. 6. 7. 8. 9.

Longest chain rule : Select the continuous chain of carbons having maximum number of carbon atoms. Lowest sum rule: Gives the lowest possible numbers to the substituents and functional groups. Longest chain rule can be violated to include the double bonds triple bonds, functional groups. If two or more functional groups are present, senior functional group is given suffix and junior functional group is given prefix. If two or more different substituents are present at various positions, consider the lowest sum irrespective of the nature of substituents. If two similar substituents are present at identical positions from opposite ends, then follow alphabetical order to give lowest number. If two or more carbon chains having the same number of carbons are present then the chain having more number of branches is selected as parent chain. If the compounds contact more than one functional group the principal group form the suffix while the other functional group is considered as the substitutent. The preference order is COOH > Acid derivatives > CHO > CN > C = O > OH > NH2 > O > C = C > C C. Name Formula Suffix Prefix

Carboxylic acid Acid chloride Acid amide Ester Aldehyde Cyanide Ketone Alcohol Amine Ether Alkene
Alkyne

COOH COCl CONH2 COOR CHO CN C = O

|

oic acid oyl chloride Amide ate al nitrile one ol amine ene
yne

carboxy Chloro formlye Carbomyl Alkoxy carbonyl Aldo or formyl Cyano Keto or oxo Hydroxy Amino Alkoxy ene
yne

OH NH2 O
C = C
| |

C C

Substituents: Which are given only prefixes: X (Cl, Br, I) halo ONO nitrite NO2 nitro NO nitroso OR Alkoxy R Alkyl

14

Organic Chemistry

EXERCISES : Structure

IUPAC name

1.

CH3 | CH3 CH C CH3 | | CH3 CH3

CH3 CH CH CH3 CH3 CH2 CH3

2, 2, 3 trimethyl butane

2.

2, 3 dimethyl pentane

3. 4.

CH3 CH CH CH | | CH3 C2H5 CH3 CH2 CH CH CH2 CH3 | | CH3 C2H5

CH3 CH2 CH2 CH CH CH3
CH3 CH2 CH2 CH CH

2, 3 dimethyl pentane 3ethyl 4 methyl hexane

CH3

CH2

CH2

5.

4 (1 methyl ethyl ) heptane

CH3
CH2 CH2 CH3

CH3 CH3 CH3

6.

CH CH3

2, 3, 6 trimethyl 4 propyl heptane

CH3 CH2

CH2

CH2

CH CH

CH2 CH3 CH3

CH2

C2H5

7.
CH3

C CH3

5 (1, 2, 2 trimethyl propyl) nonane

8. 9. 10. 11. 12. 13.

CH3

CH

CH2

CH3

CH = CH2

3 methyl pent 1 ene But 1, 3 diene

CH2 CH2 CH2 CH3

CH2 = CH CH = CH2
CH3 CH2 CH2 CH CH

3 propyl hex 1 ene Pent 3 ene 1 yne But 1 en 3 yne 2 Bromo 3 chloro butane

CH C CH = CH CH3 CH C CH = CH2
CH3 CH CH CH3 | | Cl Br

15

Organic Chemistry

14. 15. 16. 17.

CH3 CH CH CH CH CH2 CH2 CH3 | | | NO2 Cl Br

4 bromo 3 chloro 2 nitro octane Methoxy ethane Ethoxy ethane 2 Methoxy propane

CH3 O C2H5 C2H5 O C2H5

CH3 O CH CH3 | CH3 CH3 CH = CH CH CH2 CH3 | OC2H5 CH3 CH CH3 | OH CH3 CH CH = CH CH3 | OH CH3 | CH3 C OH | CH3
CH3 CH CH CH2 CH3

18. 19. 20.

4 Ethoxy hex 2 ene propan 2 ol pent 3 en 2 ol

21.

2 methyl propan 2 ol

22.

OCH3 OH

2 Methoxy pentan 3 ol

23. 24. 25. 26. 27. 28.

O || H C | H

Methanal Ethanal 2 Methyl propanal 3 Hydroxy 2 Methyl Butanal 2 Hydroxy But 3 enal Propanone

CH3 CHO
CH3 CH CHO | CH3 OH CH3 | | H3 C CH CH CHO CH2 CH CH CHO | OH CH3 C CH3 || O
O || H3 C C CH CHO | CH3

29.

3 keto 2 Methyl Butanal

16

Organic Chemistry
O || H C | OH
CH3 | H3 C CH COOH CHO | H3 C CH2 CH CH COOH | CH3

30.

Methanoic acid

31.

2 Methyl propanoic acid

32.

3 Aldo 2 Methyl pentanoic acid

33. 34. 35. 36. 37. 38.

COOH | COOH

Ethan dioic acid Methyl methanoate Ethyl ethanoate Methyl 2 chloro propanoate Ethanamine Propan 2 amine

H C OCH3 || O

CH3 COOC2 H5
CH3 CH C O CH3 | || Cl O

CH3 CH2 NH2

CH3 CH CH3 | NH2 CH3 CH CH CH3 | | OH NH2

39. 40. 41. 42.

3 Amino Butan 2 ol N methyl amino methane N Methyl amino ethane N, N Dimethyl amino methane

CH3 NH CH3 CH3 NH C2 H5

CH3 N CH3 | CH3
CH3 N C2 H5 | CH3

43. 44. 45. 46.

N, N Dimethyl amino ethane Methane nitrile Ethane nitrile 2 methyl propane nitrile

H CN CH3 CN
CH3 CH CN | CH3 CH2 CH2 | | CN CN

47.

butane 1, 4 Dinitrile

17

Organic Chemistry

48.

CH2 CH2 CH2 | | | CN CN CN

COOCH3 CH2 COOCH3 CH2 COOCH3

3cyano pentane 1, 5 dinitrile

49.

Dimethyl propane dioate

50.
CH2 COOC2H5

Ethyl methyl butane dioate

1. 2. 3. 4. 5. 6. 7. 8. 9.

Common Name Acetic acid Formic acid Acetaldehyde

Structure CH3 COOH HCOOH CH3CHO

CH3 C CH3 || O

Acetone Vinyl cyanide Vinyl alcohol Acetonitrile Methyl carbinol Trimethyl carbinol

CH2 = CH CN CH2 = CH OH CH3 CN CH3 CH2 OH

CH3 | CH3 C OH | CH3

10.

Ter Butyl alcohol

CH3 | CH3 C OH | CH3

CH3 C Cl || O

11. 12. 13. 14. 15. 16. 17. 18. 19.

Acetyl chloride Acetamide Methyl acetylene Pyrene Formaldehyde Phenyl isocyanide Dimethyl ketone Ethyl acetate Aldol

CH3 C NH2 || O

CH3 C CH CCl4 HCHO C6H5 NC

CH3 C CH3
||

CH3OOC2H5
CH3 CH CH2 CHO | OH

18

Organic Chemistry

20.

Marsh gas

CH4
CH3 | H3 C C H2 C HC CH3 | | CH CH 3 3

21.

2, 2, 4 Trimethyl pentane

22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35.

Hept 2 enal Pent 3 en 1 yne 2 Hydroxy Butanoic acid 2 methoxy propane 4 Keto pentanal Ethyl methanoate Ethoxy ethane Ethanoyl chloride Ethanamide Propan 2 amine N ethyl amino ethane N, N diethyl amino propane Ethane nitrile Methyl carbyl amine

OHC HC = CH H2C H2C H2C CH3 HC C HC = CH CH3

HOOC HC H2C CH3 | OH

CH3 CH CH3 | OCH3

OHC H2C H2C C CH3 || O

HCOOC2H5 C2H5 O C2H5

CH3 C Cl || O
CH3 C NH 2 || O
CH3 CH CH3 | NH2

C2H5 NH C2H5
C 2H5 N CH 2 CH 2 CH3 | C2H5

CH3 CN CH3 NC

(a) (b) (c)

WRITING THE STRUCTURE OF THE COMPOUND WHOSE NAME IS GIVEN Observe the word root and write the continuous carbon chain. Number the carbon atoms in a suitable way and attach the functional groups, substituents and multiple bonds at their respective carbon atoms. Carbon has tetravalency. Attach the required number of hydrogen atoms at each carbon atom to satisfy its tetra valency. Now the structure is complex. Example : 3 Bromo 2 Methyl pentan 2 ol

a) As per the word root pent we have C C C C C

19

Organic Chemistry

OH | C C C C C | | b) As per the name CH 3 Br c) To satisfy the tetravalency of each carbon atom hydrogen atoms ate added to each carbon atom as per requirement. H OH H H H | | | | | HCCCCCH | | | | | H CH 3 Br H H Hence, the structure is complete Let us see the nomenclature of cyclic compounds.
1 2 3 4 5

Cyclohexene 3-Chlorocyclohexene Cyclohexyne Cyclohexan 1-ol

Nomenclature of substituted benzene compounds

The common names of the above compounds are given in brackets wherever necessary. Substituents are mentioned in alphabetical order giving lowest number to the first substituent. 1) Methylbenzene IUPAC (Toluene) 4) 1, 2-dibromobenzene (orthodibromobenzene) 2) Methoxybenzene (Anisole) 5) 1, 3-dichlorobenzene (metadichlorobenzene) 3) Bromobenzene

6) 1-chloro-4-nitrobenzene

7) Benzene carbaldehyde 8) Benzene carboxylic acid (benzaldehyde) (benzoic acid) 10) Phenol 11) Acetophenone 20

9) Styrene

Organic Chemistry

Dimethyl derivatives of benzene are called Xylenes. 1, 2-dimethyl benzene (O - xylene)

Consider

It is named as 2, 4, 6 - trinitro toluene taking toluene as the base

name. Similarly

is named as 4-ethyl - 2 - fluroanisole.

When no simple base name other than benzene is possible, the positions are numbered so as to give the lowest locate at the first point of difference. Example :

1-Chloro-2, 4-dinitrobenzene (not 4-chloro -1, 3-dinitrobenzene)

4-ethyl-1-fluoro-2-nitrobenzene

If benzene ring is named as substituent it is named as phenyl . Similarly an arene is named as aryl.

2-phenylethanol Benzyl Chloride

21