Organic: module 4 revision guide

Hydrocarbon is a compound consisting of hydrogen and carbon only

Basic definitions to know

Saturated: Contain single carbon-carbon bonds only

Unsaturated : Contains a C=C double bond

Molecular formula: The formula which shows the actual number of each type of atom

Empirical formula: shows the simplest whole number ratio of atoms of each element in the compound General formula: algebraic formula for a homologous series e.g. CnH2n Structural formula (displayed formula): show all the covalent bonds present in a molecule Homologous series are families of organic compounds with the same functional group and same general formula. They show a gradual change in physical properties (e.g. boiling point). Each member differs by CH2 from the last. same chemical properties. Functional group is an atom or group of atoms which when present in different molecules causes them to have similar chemical properties

Drawing Displayed formulae

H H C H H C H H H C H C H H C H H

When drawing organic compounds add the hydrogen atoms so that each carbon has 4 bonds

Remember that the shape around the carbon atom is tetrahedral and the bond angle is 109.5o

H H H C C

H H H
code meth eth prop but pent hex no of carbons 1 2 3 4 5 6 7 8 9 10

General rules for naming carbon chains

Count the longest carbon chain and name appropriately Find any branched chains and count how many carbons they contain Add the appropriate prefix for each branch chain

Eg -CH3 methyl or -C2H5 ethyl C3H7 propyl

3,5-dimethyl heptane

hept oct non dec

When compounds contain more than one functional group, the order of precedence determines which groups are named with prefix or suffix forms. The highest precedence group takes the suffix, with all others taking the prefix form. However, double and triple C-Cbonds only take suffix form. Order of priority highest first: Carboxylic acids >carboxylic acid derivative>nitriles>aldehydes>ketones>alcohols>amines

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homologous series alkenes

functional group

prefix / suffix (* = usual use)

H H C H
H C H O H

example

suffix -ene suffix* -ol prefix hydroxy-

C H
H H C H H C H

alcohols

OH

H C H

H C H Cl

haloalkanes

halogen

prefix chlorobromoiodosuffix -al

C H

H H C H

O C H

aldehydes

prefix formyl-

ketones

O C

suffix* -one prefix oxo-

H H C H

O C

H C H H

suffix -oic acid

OH
H

H C H

O C OH

carboxylic acids

suffix -nitrile

H H C H

H C H
H C H H C H NH2

nitriles
C N

prefix cyano-

amines

NH2

suffix* -amine prefix amino-

H H C H

O C O

H C H H

esters

O C O

-yl oate

C H

Acyl chloride
C

-oyl chloride
Cl

CH 3

C Cl
O

Amide
C

-amide
NH2

CH3

C NH2

Acid Anhydrides
R C

O CH3 C O CH3 C O

O R C O

2
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General rules for naming functional groups

The functional group is indicated by a prefix or suffix. e.g. chloroethane
H H C3 H Br C2 H H C1 H H

The position of the functional group is given by a number counting from the end that gives the functional group the lowest number. (for aldehydes, carboxylic acids & nitriles, the functional group is position 1). H H H
H C H H C H H C C H H

C4 H

2-bromobutane

We only include numbers if they are needed.

methyl propane

CH2Cl2
Br CH3 CH CH3 C Br

dichloromethane

Where there are two or more of the same groups, di-, tri- or tetra are used and . Words are separated by numbers with dashes If there is more than one functional group/substituent, numbers are separated by commas and the groups are listed in alphabetical order (ignoring di, tri, etc.).

CH3

2,3-dibromo-2-methylbutane.

CH2ClCBr2CH2CH3 CH2ClCH2CHBrCH3 CH2OHCHClCH=CH2

2,2-dibromo-1-chlorobutane. 3-bromo-1-chlorobutane

The suffix for alkenes can go in front of other suffixes.

2-chlorobut-3-en-1-ol

Haloalkanes Class the halogen as a substituent on the C chain and use the suffix -fluoro, -chloro, -bromo, or iodo. (Give the position number if necessary:

H H C4 H

H C3 H

Br C2 H

H C1 H H

2-bromobutane

Alcohols These have the ending -ol in place of the last -e, and if necessary the position number for the OH group is added between the name stem and the ol If the compound has an OH group in addition to other functional groups that need a suffix ending then the OH can be named with the prefix hydroxy-):

OH

Butan-2-ol
CH3
1

CH
2

CH2
3

CH3
4

O H3C CH C OH
Ketones Ketones end in -one
H

2-hydroxypropanoic acid

OH
H C H O C

Aldehydes An aldehydes name ends in al It always has the C=O bond on the last carbon of the chain so it does not need an extra number

H C H H

Ethanal
Carboxylic acids These have the ending oic acid in place of the last -e, but no number is necessary for the acid group as it must always be at the end of the chain. The numbering always starts from the carboxylic acid end

When ketones have 5Cs or more in a chain then it needs a number to show the position of the double bond. E.g. pentan2-one The prefix oxo- should be used for compounds that contain a ketone group in addition to a carboxylic acid or aldehyde

Propanone

O H3C C O C OH

2-oxopropanoic acid
H C C C

If there are carboxylic acid groups on both ends of the chain then it is called a - dioic acid

Ethanoic acid

O
C C

Ethandioic acid
OH

HO
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Amines These end in amine. There is, however, rather confusingly two ways of using this suffix. The exam board tend to use the common version where then the name starts propylamine. The IUPAC version of the same chemical is propan-1-amine. If the amine is secondary and has two alkyl groups attached to the nitrogen the each chain is named

H H C H

H C H

H C H NH2

H2N

O C O H

propylamine Or propan-1-amine

If there is another CH functional group as well as the amine group then H3C the prefix amino is used.

2-aminopropanoic acid.

CH3CH2CH2NHCH3 N-methylbutylamine Or N-methylbutan-1-amine

H3C

CH2

NH

CH2

CH3

Diethylamine Or N-ethylethanamine

Nitriles These end in ile, but the C of the CN group counts as one of the chain. Note the stem of the name is different to : butanenitrile and not butannitrile.

H H C H

H C H

H3C
C H CN

OH C C N

H3C

butanenitrile

2-hydroxy-2-methylpropanenitrile

Carboxylic acid derivatives

Esters Esters have two parts to their names The bit ending in yl comes from the alcohol that has formed it and is next to the single bonded oxygen. The bit ending in anoate comes from the carboxylic acid. (This is the chain including the C=O bond) Acid Anhydrides This is called ethanoic anhydride. It is ethanoic because it is two ethanoate groups joined together. .
H

H C H

H C H

O C O

H C H H

methylpropanoate

O CH3 C O CH3 C O
If the groups are different then each one is named e.g. ethanoic propanoic anhydride

O CH3 C O CH3 CH2 C O

Acyl Chlorides

H3C

O CH C

O
Take the carboxylic acid name, remove the oic acid bit of the name and replace by oyl chloride

CH3

C
Cl

H3C

Cl

2-methylpropanoyl chloride

ethanoyl chloride

Amides

O
Take the carboxylic acid name, remove the oic acid bit of the name and replace by amide

CH3

C NH2

O
Secondary and tertiary amides are named differently to show the two (or three) carbon chains

H3C

CH2

NH

CH3

ethanamide

N-methyl propanamide

O H3C CH2 C

CH3 N CH3
H3C

CH3 O
CH C

CH3 N CH3

N,N-dimethylpropanamide

N,N,2-trimethylpropanamide

4
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Isomers Structural isomerism can arise from

Structural isomers: same molecular formula different structures (or structural formulae)

Chain isomerism Position isomerism Functional group isomerism

Chain isomers: Compounds with the same molecular formula but different structures of the carbon skeleton
H H C H H C H H C H H C H H

H H C H

H C H C H H

H C H

H C H H
H H H C H H

H C C C H H H H C H H

C H

pentane

2-methylbutane

2,2-dimethylpropane position isomers: Compounds with the same molecular formula but different structures due to different positions of the same functional group on the same carbon skeleton
H H C Br H C H H C H H

H C Br

H C H H

1-bromopropane

C H

2-bromopropane

Functional group isomers: Compounds with the same molecular formula but with atoms arranges to give different functional groups
H H C H H C H O H

H O C H H

ethanol: an alcohol

C H

Methoxymethane: an ether

H H C H C

H H C H

Cyclohexane- cyclo alkane

H H H H C C H C H

CH3CH2CH2CH2CH=CH2

hexene- alkene

Stereoisomerism Stereoisomers have the same structural formulae but have a different spatial arrangement of atoms
There are two types of stereoisomerism: geometrical (EZ isomerism) and optical isomerism

Alkenes can exhibit a type of isomerism called E-Z stereoisomerism E-Z isomers exist due to restricted rotation about the C=C bond Single carbon-carbon covalent bonds can easily rotate

E-Z stereoisomers arise when: (a) There is restricted rotation around the C=C double bond. (b) There are two different groups/atoms attached both ends of the restricted double bond

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H C H H

H H C H H H C C

H H C H

two different groups attached either end of the restricted double bond- leads to EZ isomers

H C H C

C H H

But-1-ene

Z- but-2-ene
H H C H C H H H C H C H

two identical groups attached to one end of the restricted double bond no E-Z isomers

These are two isomers as the lack of rotation around the double bonds means one cannot be switched to the other

But-1-ene is a structural isomer of But-2ene but does not show E-Z isomerism Naming E-Z stereoisomers On both sides of the double bond determine the priority group

E -butbut-2-ene
Priority group side 1 Priority group side 2 Z-1,2-dichloroethene If the priority atom is on the same side of the double bond it is labelled Z from the german zusammen (The Zame Zide!) Optical Isomerism Optical isomerism occurs in carbon compounds with 4 different groups of atoms attached to a carbon (called an asymmetric carbon). These four groups are arranged tetrahedrally around the carbon.
OH C H5C2 CH3 H
H3C H OH C C 2H 5
This causes two different isomers that are not superimposable to be formed. They are mirror images

PRIORITY Group: The atom with the bigger A is classed as the priority atom
r

E-1,2-dichloroethene

If the priority atom is on the opposite side of the double bond it is labelled E from the german entgegen (The Epposite side!)

H H C H

H C H

H C O H

H C H H

A carbon atom that has four different groups attached is called a chiral (asymmetric) carbon atom

A mixture containing a 50/50 mixture of the two isomers (enantiomers) is described as being a racemate or racemic mixture. Many naturally occurring molecules contain chiral C atoms, but are usually found in nature as a pure enantiomer Different systems of nomenclature are is existence for optical isomers. D/L or +/- are commonly used, but both have been superseded by the more useful and informative R/S system (this is not on the syllabus for information only).

Two compounds that are optical isomers of each other are called enantiomers.

Optical isomers have similar physical and chemical properties, but they rotate plane polarised light in different directions.
One enantiomer rotates it in one direction and the other enantiomer rotates it by the same amount in the opposite direction. One optical isomer will rotate light clockwise (+)(called dextrorotatory). The other will rotate it anticlockwise(-)(called laevorotatory). A mixture of equal amounts of the two optical isomers will not rotate plane-polarised light. The mixture is called a racemic mixture or a racemate

(-)-enantiomer (anticlockwise rotation)

(+)-enantiomer (clockwise rotation)

()-racemate (no overall effect)

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Chemical Reactions and Optical Isomers Formation of a racemate A racemate will often be formed in a reaction when a trigonal planar reactant or intermediate is approached from both sides by an attacking species

H
NC:

CH3 C
:CN

O
H NC C OH CH3

H H3 C C OH CN

There is an equal chance of either enantiomer forming so a racemate forms. No optical activity is seen

Nucleophilic addition of HCN to aldehydes and ketones (unsymmetrical) when the trigonal planar carbonyl is approached from both sides by the HCN attacking species: results in the formation of a racemate

Mechanism for the reaction (drawn the same for both enantiomers)

A racemate can also be formed in the AS reaction of the electrophilic addition of HBr to an unsymmetrical alkene

H
+

:Br C
+

H
The bromide can attack this planar carbocation from both sides leading to a racemate

H C Br CH2 CH3 CH3

H
CH

Br

CH2 CH3

C H3C CH2 CH3 Br

H3C

H2C

CH2 CH3

If the alkene is unsymmetrical, addition of hydrogen bromide can lead to isomeric products.

H
C
+

:Br H
C CH2 CH3
CH2

Major product s 90%

CH2 CH2 CH3

Br

Minor product

10%

Drug action and optical isomers Drug action may be determined by the stereochemistry of the molecule. Different optical isomers may have very different effects Thalidomide Ibuprofen
CH3 H3C HC CH2
Chiral carbon One enantiomer of thalidomide causes birth defects in unborn children whilst the other had useful sedative problems. Unfortunately is was given in a racemic mixture when first used.

CH CH C C HC CH CH HO

CH3

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