Topic 9: Organic Chemistry

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Subtopic Carbon: A Unique Element Hydrocarbons: Compounds Containing

only Carbon and Hydrogen Alkanes: Saturated Hydrocarbons Alkene and Alkynes Aromatic Hydrocarbons Functional Groups

Tro: Chemistry: A Molecular Approach

Copyright 2011 Pearson Education, Inc.

What is Organic Chemistry?

The study of hydrocarbons (compounds of hydrogen and carbon) and their derivatives
Organic molecules = Carbon-based molecules Organic chemistry = Chemistry of carbon-based molecules

Carbon: can accept 4 electrons from other atoms, i.e. carbon is tetravalent (valency = 4) Carbon-Carbon bonds: especially strong covalent bonds Carbon: unique in its ability to catenate (the ability to form chains of atoms)
C C C C C C C C C C C C C C C C C C C

Linear molecules

Branched molecules

Cyclic molecules

Functional Groups
Functional group: an atom or group of atoms within a molecule that shows a characteristic set of physical and chemical properties. Functional groups are important for three reason; they are:
1. the units by which we divide organic compounds into classes;
2. the sites of characteristic chemical reactions; 3. the basis for naming organic compounds.

Tro: Chemistry: A Molecular Approach, 2/e

Copyright 2011 Pearson Education, Inc.

Saturated Hydrocarbons A saturated hydrocarbon has all CC single

bonds
it is saturated with hydrogens

Saturated aliphatic hydrocarbons are called

alkanes Chain alkanes have the general formula CnH2n+2 Ring alkanes have all CC single bonds, but have fewer hydrogens than a chain with the same number of carbons
7

Tro: Chemistry: A Molecular Approach, 2/e

Copyright 2011 Pearson Education, Inc.

Unsaturated Hydrocarbons
Unsaturated hydrocarbons have one or more
C=C double bonds or CC triple bonds Unsaturated aliphatic hydrocarbons that contain C=C are called alkenes
the general formula of a monounsaturated chain alkene is CnH2n remove two more H for each additional double bond

Unsaturated aliphatic hydrocarbons that contain

CC are called alkynes
the general formula of an alkyne with one triple bond is CnH2n2 remove four more H for each additional triple bond
Tro: Chemistry: A Molecular Approach, 2/e 8 Copyright 2011 Pearson Education, Inc.

Aromatic Hydrocarbons
Aromatic hydrocarbons contain a ring structure
that seems to have C=C, but doesnt behave that way The most prevalent example is benzene.
C6H6 Other compounds have the benzene ring with other groups substituted for some of the Hydrogens

Tro: Chemistry: A Molecular Approach, 2/e

Copyright 2011 Pearson Education, Inc.

How to write/draw a hydrocarbon structure?

Molecular Formula C4H10 Structural Formula

Condensed Structural Formula

How to write/draw a hydrocarbon structure?

Line Segment Structural Formula

Alkane

Alkene

Each line represents a covalent bond between C atoms, unless indicated otherwise. C-H bonds are not shown, but they are present.

Prefixes used in naming hydrocarbon compounds:

metha.. = 1 C etha = 2 C propa = 3 C buta = 4 C penta = 5 C hexa = 6 C hepta.. = 7 C octa = 8 C nona = 9 C deca = 10 C undeca..= 11 C dodeca..= 12 C

Alkanes
Alkanes have the general formula CnH2n+2 where n = 1,2,3,

Alkanes have only single covalent bonds.

Alkanes are saturated hydrocarbons because they contain the maximum number of hydrogen atoms that can bond with the number of carbon atoms in the molecule

CH4 methane

C 2H 6 ethane
24.2

Some points concerning the series of alkanes:

1. Series is generated by repeatedly adding CH2 to the previous member of the series. A series generated in this manner is known as Homologous Series. 2. Nomenclature (naming) the series share a common suffix: ane 3. An alkane with less one hydrogen atom is called an alkyl group, usually as branches.
Alkane Methane Ethane Propane Etc... Alkyl group Methyl (CH3) Ethyl (CH3CH2) Propyl (CH3CH2CH2)

Alkane Nomenclature
1. The parent name of the hydrocarbon is from the longest continuous chain of carbon atoms in the molecule.
CH3 branch CH3 CH2 CH2 CH CH2 CH2 CH3
Longest chain

1 7

2 6

3 5

4 4

5 3

6 2

7 1

4-methylheptane A branch exists at C atom no. 4. The longest carbon chain has 7 C atoms (suffix: hept).

Alkane Nomenclature
2. When one or more hydrogen atoms are replaced by other groups, the name of the compound must indicate the locations of carbon atoms where replacements are made. The numbers are in the direction that gives the smaller numbers for the locations of the branches.
CH3
CH3 1 CH 2 CH2 3 CH2 4 CH3 5 2-methylpentane

CH3
CH3 5 CH 4 CH2 3 CH2 2 CH3 1 4-methylpentane

Alkane Nomenclature
3. Use prefixes di-, tri-, tetra-, when there is more than one alkyl branch of the same kind.
CH3 CH3
1

CH3
CH
3

CH
2

CH2
4

CH2
5

CH3
6

2,3-dimethylhexane
CH3

CH3
1

CH
2

C
3

CH2
4

CH2
5

CH3
6

CH3 3,3-dimethylhexane
24.2

Identical substituents should be grouped together with a prefix, such as: di for two identical; tri for three; tetra for four.

2,2,4 - trimethylpentane

Note: Substituents must be named in alphabetical order.

Alkane Nomenclature
4. Use previous rules for other types of substituents.
Br
4 1 3

NO2
2 1

CH3

CH
2

CH
3

CH3
4

2-bromo-3-nitrobutane 3-bromo-2-nitrobutane Br
4 3

NO2
2 1

CH2
1

CH2
2

CH
3

CH3
4

1-bromo-3-nitrobutane 4-bromo-2-nitrobutane

24.2

Example:

3-ethyl-2,2,5-trimethylhexane

3,4-dichloro-4-ethyl-5-methylheptane

What is the IUPAC name of the following compounds?

CH3 C2H5 CH2
3

CH3
1

CH
2

CH
4

CH2
5

CH2
6

CH2
7

CH3
8

4-ethyl-2-methyloctane
1,2

C2H5
CH
3

CH3
CH2
4

CH3
1

CH
5

CH2
6

CH3
7

3,5 - dimethylheptane

24.2

Isomerism in Alkanes:

Structural isomers are molecules that have the same molecular formula but different structures.

24.2

Structural isomers are molecules with the same molecular formulae;

different structural formulae (different atom-to-atom connectivity); different physical properties.

Types of structural isomerism:

Chain isomerism: These isomers arise because of the possibility of branching in carbon chains. Position isomerism: In position isomerism, the basic carbon skeleton remains unchanged, but important groups are moved around on that skeleton.

How many structural isomers does pentane, C5H12, have?

H H C H H C H H C H H C H H C H H H H C H CH3 H C H C H H C H
24.2

H H C H H CH3 H C C H

n-pentane

CH3 H

2,2-dimethylpropane

2-methylbutane

Cycloalkanes
Alkanes whose carbon atoms are joined in rings are called cycloalkanes. They have the general formula CnH2n where n = 3,4,

24.2

Naming Cycloalkanes with Side Groups

Side group name goes in front of the cycloalkane name. Number the ring in the direction that gives the lowest numbers to the side groups.
CH3
methylcyclopentane

CH3 CH3
1,2-dimethylcyclopentane

CH3 CH3
1,2,4-trimethylcyclohexane

CH3

27

Alkenes
Alkenes have: the general formula CnH2n where n = 2,3, contain at least one carbon-carbon double bond; also called olefins
CH2
CH CH2 CH3

CH3

CH

CH

CH3

1-butene Cl C C Cl Cl C

2-butene H C

H H cis-dichloroethylene

H Cl trans-dichloroethylene
24.2

Naming Alkenes
When the carbon chain has 4 or more C atoms, number the chain to give the lowest number to the double bond. 1 2 3 4 CH2=CHCH2CH3 1-butene 1 2 3 4 CH3CH=CHCH3 2-butene but-1-ene

but-2-ene

Cis and Trans Isomers of Alkenes

The two carbons and the four atoms that make up the double bond in alkenes lie in a plane. Unlike carbon-carbon single bonds, rotation around carbon-carbon double bond is not possible. As a result, a new kind of isomerism is possible for alkenes. It is known as cis-trans isomers. Both cis and trans isomers have the same formula and connections between the atoms but have different 3-D structures because the way the groups are attached to the carbons.

A carbon-carbon double bond consists of a sigma () bond from the overlap of sp2 hybrid orbitals and a pi () bond from the overlap of pz orbitals. Double bonds are not free to rotate. Rotation about the carbon-carbon single bond in ethane occurs freely because rotating the carbons does not affect the overlap of the sp3 hybrid orbitals that make up the bond.

 In cis isomers, two methyl groups are close together on the same side of the double bond.

 In trans isomer, two methyl groups are far apart on opposite side of the double bond.

 Cis-trans isomerism occurs in an alkene whenever each double bond carbon is bonded to two different substituent groups. Cis-trans isomerism is not possible if one of the double bond carbons is attached to two identical groups.

Not a cis- or trans- isomer.

Alkynes
Alkynes have: the general formula CnH2n-2 where n = 2,3,4, contain at least one carbon-carbon triple bond.
CH C CH2 CH3 CH3 C C CH3

1-butyne

2-butyne

24.2

Aromatic Compounds
In the early days the word aromatics was used to described many fragrant molecules isolated from natural sources. Today the term aromatic is used to describe benzenelike molecules. Benzene is a flat, symmetrical molecule with the molecular formula C6H6. It has alternating three carbon-carbon double bonds and three single bonds.

The Structure of Benzene

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

C
C

C H

C
C

C H

24.3

 Benzenes relatively lack of chemical reactivity is due to its structure. There are two possible structures with alternating double and single bonds.

Simple aromatic compounds like benzene are non-polar, insoluble in water, volatile, and flammable. Several aromatic hydrocarbons are toxic. Benzene itself is implicated as a cancer causing chemical (carcinogenic).

Naming Aromatic Compounds

Aromatic compounds are named with benzene as the parent chain. One side group is named in front of the name benzene. No number is needed for mono-substituted benzene since all the ring positions are identical.

methylbenzene (toluene)

chlorobenzene

Aromatic Compound Nomenclature

ethylbenzene CH2CH3 Cl aminobenzene NH2 NO2

chlorobenzene Br Br Br

nitrobenzene

6
5 4

2
3

Br 1,2-dibromobenzene 1,3-dibromobenzene
24.3

When two groups are attached to benzene, the ring is numbered to give the lower numbers to the side groups. The prefixes ortho (1,2), meta (1,3-) and para (1,4-) are also used.

1,2-dimethylbenzene
(orthodimethylbenzene

1,3-dichlorobenzene
(metadichlorobenzene

1-chloro-4methylbenzene (parachloromethylbenzene

Alcohols
Alcohols contain the hydroxyl functional group and have the general formula R-OH.
H H - C-O-H Fu nctio nal gro up

Ethanol may also be written as a condensed structural formula:

CH3 -CH2 -OH

: :

H-C- C-O- H H H Ethan ol (an alco ho l)

or

CH3 CH2 OH

Alcohols
All alcohols contain the hydroxyl functional group, OH, attached to single bonded hydrocarbons. Alcohol have the general formula R-OH where R represents any chain of carbon and hydrogen atoms. Among the most common alcohols are: Methanol

Ethanol

alcohols are classified as primary (1), secondary (2), or tertiary (3) depending on the number of carbon atoms bonded to the carbon bearing the -OH group.

Naming alcohols:
Alcohols use the same formats as alkanes. To name alcohols: 1. Determine the parent chain. The parent chain must be the longest that includes the carbon holding the OH group. 2. Number according to the end closest to the -OH group regardless of where alkyl substituents are. 3. The format is as follows: (location of branch)-(branch name)(location of OH group)-(parent chain). 4. Change the parent chain -e ending and replace it with an -ol.

Example: Parent chain -OH location Substituent Name

: propane : C #1 : no substituent : propanol

Parent chain -OH location Substituent Name

: butane : C #2 : no substituent : 2butanol

Parent chain : butane -OH location : C #2 Substituent : methyl Substituent location : C #2 Name : 2methyl2butanol

Can you name this compound?

Ether Ethers have the general formula R-O-R.

Condensation Reaction
CH3OH + HOCH3
H2SO4
catalyst

CH3OCH3 + H2O

24.4

Ether
Ethers have the general formula R-O-R. Ethers can be named by: naming each of the two carbon groups as a separate word followed by a space and the word ether (common method). Or using OR group a substituent using the group name, alkoxy. In this case the smaller of the two alkyl groups is named as the alkoxy substituent (IUPAC method). CH3CH2OCH3 ethyl methyl ether OR methoxyethane

CH3CH2-O-CH2CH3 Diethyl ether OR ethoxyethane

24.4

Aldehyde & Ketone

Aldehyde and ketones contain the carbonyl functional group:

Aldehydes have the general formula:

Ketones have the general formula:

O H3C C CH3 acetone

H C H
formaldehyde

H C CH3
acetaldehyde

24.4

When naming aldehydes: 1. Identify the longest continuous chain of carbons with the carbonyl carbon as part of the chain. 2. Number the carbon chain so that the carbonyl carbon is always number one. 3. Locate and identify alphebetically the branched groups by prefixing the carbon number it is attached to. If more than one of the same type of branched group is involved use the prefixes di for 2, tri for three, etc. 4. After identifying the name, number and location of each branched group, use the alkane name that represents the number of carbons in the continuous chain. 5. Change the "e" ending and replace it with -al.

Methanal

Propanal 2,2-dimethylpropanal

When naming ketones: IUPAC method: start by choosing the longest carbon chain that includes the carbon from the carbonyl group and use the length of that carbon chain as the base name, change the ending by removing the -e and adding -one, and adding a number at the beginning of the name to indicate which carbon is double bonded to the oxygen. Then, if there are any side groups attached to the main chain, those are added to the front of the name with the appropriate numbers to show their location. Common method: take the carbonyl as the ketone group and then you look at what kind of alkyl groups are attached to that carbonyl group, name the ketone by naming each of those alkyl groups and then add the word "ketone."

Propanone (Dimethyl ketone)

2-Pentanone (Methyl propyl ketone)

Carboxylic Acid
Carboxylic acids contain the carboxyl (COOH ) functional group.
The primary suffix name for a carboxylic acid is based on the "longest carbon chain name" + "oic acid"

Methanoic acid (Formic acid)

Ethanoic acid (Acetic acid)

2-methylpropanoic acid

Benzoic acid 24.4

Ester
Esters have the general formula RCOOR, where R and R are hydrocarbon groups. Natural occurring esters of organic acids in fruits and flowers give them their distinctive odors. It also also used for food aroma and taste, perfumes, synthetic fibres, and solvents. To name esters: 1. Identify the alkyl group that is attached to the oxygen atom. 2. Number according to the end closest to the -CO- group regardless of where alkyl substituents are. 3. Determine the alkane that links the carbon atoms together. If there is a separation of a continuous link of carbon atoms due to the oxygen atom, individually name the two alkanes before and after the oxygen atom. The longer structural alkane is the one that should contain the carbonyl atom. 4. The format is as follows: (alkane far from carbonyl) (alkane closest to carbony)(parent chain) . 5. Change the parent chain -e ending and replace it with an -oate. 24.4

Methyl methanoate

Ethyl ethanoate

Butyl propanoate

Amines
Amines are organic bases with the general formula R3N. Amines are organic derivatives of ammonia, meaning that one, two, or three hydrocarbon groups have replaced the hydrogens. Amines have an extremely high solubility and have disagreeable odors (fish smell). Amines could be classified as primary, secondary, and tertiary depending on the amount of hydrogen that has been replaced by a hydrocarbon group.

primary amine

secondary amine

tertiary amine

Amines could also be found in plants which are called alkaloids and affect the central nervous system of many creatures 24.4

To name amines: 1. Identify the names of the alkyl groups bonded to the nitrogen atom. 2. Simply replace the alkane -e ending with -amine. 3. The format is as follows: (alkyl name)(-amine)

Methylamine (primary amine) Dimethylamine (secondary amine) Trimethylamine (tertiary amine)

Ethylamine

Propylamine 2-Propylamine