Organic Chemistry William H. Brown Christopher S. Foote Brent L. Iverson

Alkenes: Structure and Nomenclature Chapter 5

Unsaturated Hydrocarbons Unsaturated hydrocarbon: contains one or more carbon-carbon double or triple bonds Alkene: contains a carbon-carbon double bond and has the general formula C n H 2n Alkyne: contains a carbon-carbon triple bond and has the general formula C n H 2n-2

Unsaturated hydrocarbon: contains one or more carbon-carbon double or triple bonds

Alkene: contains a carbon-carbon double bond and has the general formula C n H 2n

Alkyne: contains a carbon-carbon triple bond and has the general formula C n H 2n-2

Unsaturated Hydrocarbons Arenes: benzene and its derivatives (Ch 21-22) we do not study arenes until Chapters 21 & 22 however, we show structural formulas of compounds containing the phenyl group before that time the phenyl group is not reactive under any of the conditions we describe in Ch 6-20

Arenes: benzene and its derivatives (Ch 21-22)

we do not study arenes until Chapters 21 & 22

however, we show structural formulas of compounds containing the phenyl group before that time

the phenyl group is not reactive under any of the conditions we describe in Ch 6-20

Structure of Alkenes A double bond consists of one sigma bond formed by the overlap of sp 2 hybrid orbitals and one pi bond formed by the overlap of parallel 2 p orbitals the two carbon atoms of a double bond and the four atoms bonded to them lie in a plane, with bond angles of approximately 120°

A double bond consists of

one sigma bond formed by the overlap of sp 2 hybrid orbitals and one pi bond formed by the overlap of parallel 2 p orbitals

the two carbon atoms of a double bond and the four atoms bonded to them lie in a plane, with bond angles of approximately 120°

Structure of Alkenes it takes approximately 264 kJ (63 kcal)/mol to break the pi bond in ethylene; that is, to rotate one carbon by 90° with respect to the other so that there is no overlap between 2 p orbitals on adjacent carbons

it takes approximately 264 kJ (63 kcal)/mol to break the pi bond in ethylene; that is, to rotate one carbon by 90° with respect to the other so that there is no overlap between 2 p orbitals on adjacent carbons

Cis,Trans Isomerism in Alkenes Cis,trans isomers: isomers that have the same connectivity but a different arrangement of their atoms in space due to the presence of either a ring or a carbon-carbon double bond

Cis,trans isomers: isomers that have the same connectivity but a different arrangement of their atoms in space due to the presence of either a ring or a carbon-carbon double bond

Index of Hydrogen Deficiency Index of hydrogen deficiency (IHD): the sum of the number of rings and pi bonds in a molecule To determine IHD, compare the number of hydrogens in an unknown compound with the number in a reference hydrocarbon of the same number of carbons and with no rings or pi bonds the molecular formula of the reference hydrocarbon is C n H 2n+2

Index of hydrogen deficiency (IHD): the sum of the number of rings and pi bonds in a molecule

To determine IHD, compare the number of hydrogens in an unknown compound with the number in a reference hydrocarbon of the same number of carbons and with no rings or pi bonds

the molecular formula of the reference hydrocarbon is C n H 2n+2

Index of Hydrogen Deficiency for each atom of a Group 7 element (F, Cl, Br, I), add one H no correction is necessary for the addition of atoms of Group 6 elements (O,S) to the reference hydrocarbon for each atom of a Group 5 element (N, P), subtract one hydrogen IDH = 2 (H reference - H molecule )

for each atom of a Group 7 element (F, Cl, Br, I), add one H

no correction is necessary for the addition of atoms of Group 6 elements (O,S) to the reference hydrocarbon

for each atom of a Group 5 element (N, P), subtract one hydrogen

Index of Hydrogen Deficiency Problem: isopentyl acetate has a molecular formula of C 7 H 14 O 2 . Calculate its IHD reference hydrocarbon C 7 H 16 IHD = (16-14)/2 = 1 Problem: calculate the IHD for niacin, molecular formula C 6 H 6 N 2 O reference hydrocarbon C 6 H 16 IHD = (16 - 6)/2 = 5 O O Isopentyl acetate

Problem: isopentyl acetate has a molecular formula of C 7 H 14 O 2 . Calculate its IHD

reference hydrocarbon C 7 H 16

IHD = (16-14)/2 = 1

Problem: calculate the IHD for niacin, molecular formula C 6 H 6 N 2 O

reference hydrocarbon C 6 H 16

IHD = (16 - 6)/2 = 5

IUPAC Nomenclature 1. Number the longest chain of carbon atoms that contains the double bond in the direction that gives the carbons of the double bond the lowest numbers 2. Locate the double bond by the number of its first carbon 3. Name substituents 4. Number the carbon, locate and name substituents, locate the double bond, and name the main chain

1. Number the longest chain of carbon atoms that contains the double bond in the direction that gives the carbons of the double bond the lowest numbers

2. Locate the double bond by the number of its first carbon

3. Name substituents

4. Number the carbon, locate and name substituents, locate the double bond, and name the main chain

Common Names Despite the precision and universal acceptance of IUPAC nomenclature, some alkenes, particularly low-molecular-weight ones, are known almost exclusively by their common names

Despite the precision and universal acceptance of IUPAC nomenclature, some alkenes, particularly low-molecular-weight ones, are known almost exclusively by their common names

Common Names the common names methylene, vinyl, and allyl are often used to show the presence of the following alkenyl groups

the common names methylene, vinyl, and allyl are often used to show the presence of the following alkenyl groups

The Cis , Trans System Configuration is determined by the orientation of atoms of the main chain

Configuration is determined by the orientation of atoms of the main chain

The E , Z System uses priority rules (Chapter 3) if groups of higher priority are on the same side, the configuration is Z (German, zusammen ) if groups of higher priority are on opposite sides, the configuration is E (German, entgegen )

uses priority rules (Chapter 3)

if groups of higher priority are on the same side, the configuration is Z (German, zusammen )

if groups of higher priority are on opposite sides, the configuration is E (German, entgegen )

The E , Z System Example: name each alkene and specify its configuration by the E,Z system

Example: name each alkene and specify its configuration by the E,Z system

Cis,Trans Isomerism Cycloalkenes in small-ring cycloalkenes, the configuration of the double bond is cis these rings are not large enough to accommodate a trans double bond

Cycloalkenes

in small-ring cycloalkenes, the configuration of the double bond is cis

these rings are not large enough to accommodate a trans double bond

Cis,Trans Isomerism trans -cyclooctene is the smallest trans cyclooctene that has been prepared in pure form and is stable at room temperature the cis isomer is 38 kJ (9.1 kcal)/mol more stable than the trans isomer the trans isomer is chiral even though it has no chiral center

trans -cyclooctene is the smallest trans cyclooctene that has been prepared in pure form and is stable at room temperature

the cis isomer is 38 kJ (9.1 kcal)/mol more stable than the trans isomer

the trans isomer is chiral even though it has no chiral center

Dienes, Trienes, and Polyenes For alkenes containing two or more double bonds, change the infix - en - to - adien -, - atrien -, etc. those containing several double bonds are often referred more generally as polyenes following are three dienes

For alkenes containing two or more double bonds, change the infix - en - to - adien -, - atrien -, etc.

those containing several double bonds are often referred more generally as polyenes

following are three dienes

Dienes, Trienes, and Polyenes for alkenes with n double bonds, each of which can show cis,trans isomerism, 2 n stereoisomers are possible example: 2 2 = 4 cis,trans isomers are possible for 2,4-heptadiene

for alkenes with n double bonds, each of which can show cis,trans isomerism, 2 n stereoisomers are possible

example: 2 2 = 4 cis,trans isomers are possible for 2,4-heptadiene

Dienes, Trienes, and Polyenes vitamin A, a biologically important compound for which a number of cis,trans isomers is possible there are four double bonds about which cis,trans isomerism is possible, for 2 4 = 16 stereoisomers

vitamin A, a biologically important compound for which a number of cis,trans isomers is possible

there are four double bonds about which cis,trans isomerism is possible, for 2 4 = 16 stereoisomers

Physical Properties Alkenes are nonpolar compounds The only attractive forces between their molecules are dispersion forces The physical properties of alkenes are similar to those of alkanes

Alkenes are nonpolar compounds

The only attractive forces between their molecules are dispersion forces

The physical properties of alkenes are similar to those of alkanes

Terpenes Terpene: a compound whose carbon skeleton can be divided into two or more units identical with the carbon skeleton of isoprene

Terpene: a compound whose carbon skeleton can be divided into two or more units identical with the carbon skeleton of isoprene

Terpenes Myrcene, C 10 H 16 , a component of bayberry wax and oils of bay and verbena Menthol, from peppermint

Myrcene, C 10 H 16 , a component of bayberry wax and oils of bay and verbena

Menthol, from peppermint

Terpenes  -Pinene, from turpentine camphor, from the camphor tree

 -Pinene, from turpentine

camphor, from the camphor tree

Fatty Acids Animal fats and vegetable oils are both triesters of glycerol, hence the name triglyceride hydrolysis of a triglyceride in aqueous base followed by acidification gives glycerol and three fatty acids fatty acids with no C=C double bonds are called saturated fatty acid those with one or more C=C double bonds are called unsaturated fatty acids

Animal fats and vegetable oils are both triesters of glycerol, hence the name triglyceride

hydrolysis of a triglyceride in aqueous base followed by acidification gives glycerol and three fatty acids

fatty acids with no C=C double bonds are called saturated fatty acid

those with one or more C=C double bonds are called unsaturated fatty acids

Fatty Acids the most common fatty acids have an even number of carbons, and between 12 and 20 carbons in an unbranched chain the C=C double bonds in almost all naturally occurring fatty acids have a cis configuration the greater degree of unsaturation, the lower the melting point triglycerides rich in unsaturated fatty acids are generally liquid at room temperature and are called oils triglycerides rich in saturated fatty acids are generally semisolids or solids at room temperature and are called fats

the most common fatty acids have an even number of carbons, and between 12 and 20 carbons in an unbranched chain

the C=C double bonds in almost all naturally occurring fatty acids have a cis configuration

the greater degree of unsaturation, the lower the melting point

triglycerides rich in unsaturated fatty acids are generally liquid at room temperature and are called oils

triglycerides rich in saturated fatty acids are generally semisolids or solids at room temperature and are called fats

Fatty Acids the four most abundant fatty acids

the four most abundant fatty acids

Fatty Acids carbon chains of saturated fatty acids exist largely in the staggered, anti-conformation because of their high degree of order, they pack together well and are held together by dispersion forces as a result both saturated fatty acids and triglycerides derived from them are solids at room temperature following is a saturated triglyceride

carbon chains of saturated fatty acids exist largely in the staggered, anti-conformation

because of their high degree of order, they pack together well and are held together by dispersion forces

as a result both saturated fatty acids and triglycerides derived from them are solids at room temperature

following is a saturated triglyceride

Fatty Acids cis double bonds place kinks in the chains of unsaturated fatty acids unsaturated fatty acids and the triglycerides derived from them do not pack as well in a crystal lattice as their saturated counterparts, and have weaker dispersion forces between their molecules butter fat, for example, has a high content of saturated fatty acids and is a solid at room temperature salad oils (from plant oils) have a high content of polyunsaturated fatty acids and are liquid at room temperature

cis double bonds place kinks in the chains of unsaturated fatty acids

unsaturated fatty acids and the triglycerides derived from them do not pack as well in a crystal lattice as their saturated counterparts, and have weaker dispersion forces between their molecules

butter fat, for example, has a high content of saturated fatty acids and is a solid at room temperature

salad oils (from plant oils) have a high content of polyunsaturated fatty acids and are liquid at room temperature

Alkenes: Structure and Nomenclature End Chapter 5