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4. Organic Compounds: Cycloalkanes and their Stereochemistry. Why this chapter?. Because cyclic molecules are commonly encountered in all classes of biomolecules : Proteins Lipids Carbohydrates Nucleic acids. We’ve discussed open-chained compounds up to this point

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4. Organic Compounds: Cycloalkanes and their Stereochemistry

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4. Organic Compounds: Cycloalkanes and their Stereochemistry

Why this chapter?

Because cyclic molecules are commonly encountered in all classes of biomolecules:

  • Proteins

  • Lipids

  • Carbohydrates

  • Nucleic acids


  • We’ve discussed open-chained compounds up to this point

  • Most organic compounds contain rings of carbon atoms

    e.g.

  • Prostaglandins

  • Steroids


Cycloalkanes

Cycloalkanes

  • Are cyclic alkanes.

  • Have 2H fewer than the open chain. (CnH2n)

  • Are named by using the prefix cyclo- before the name of the alkane chain with the same number of carbon atoms.


Cycloalkanes are saturated cyclic hydrocarbons

Have the general formula (CnH2n)

4.1 Naming Cycloalkanes


Cycloalkanes

The structural formulas of cycloalkanes are usually represented by geometric figures,

Cyclopropane

Cyclobutane

CyclopentaneCyclohexane


Naming Cycloalkanes

  • Find the parent. # of carbons in the ring.

  • Number the substituents


Naming Cycloalkanes


Learning Check

Name each of the following:

1. CH3

CH2─CH3

2.

Cl


Solution

Name each of the following:

methylcyclopropane

1-chloro-3-ethylcyclohexane

1. CH3

CH2─CH3

2.

Cl


What is the IUPAC name for the following molecule?

Learning Check

  • 1-(2-methylbutyl)cyclopentane

  • 2-(3-methylbutyl)cyclopentane

  • 2-(2-methylbutyl)cyclopentane

  • (1,2-dimethylpropyl)cyclopentane

  • (2,2-dimethylpropyl)cyclopentane


What is the IUPAC name for the following molecule?

Solution

  • 1-(2-methylbutyl)cyclopentane

  • 2-(3-methylbutyl)cyclopentane

  • 2-(2-methylbutyl)cyclopentane

  • (1,2-dimethylpropyl)cyclopentane

  • (2,2-dimethylpropyl)cyclopentane


How many secondary hydrogens are there in the cycloalkane shown below?

Learning Check

  • 2

  • 3

  • 4

  • 5

  • 6


How many secondary hydrogens are there in the cycloalkane shown below?

Solution

  • 2

  • 3

  • 4

  • 5

  • 6


4.2 Cis-Trans Isomerism in Cycloalkanes

  • Cycloalkanes are less flexible than open-chain alkanes

  • Much less conformational freedom in cycloalkanes (can’t rotate around single bonds)


Cis-Trans Isomerism in Cycloalkanes

  • Because of their cyclic structure, cycloalkanes have 2 faces as viewed edge-on

    “top” face “bottom” face

  • Therefore, isomerism is possible in substituted cycloalkanes

  • There are two different 1,2-dimethyl-cyclopropane isomers


Stereoisomerism

  • Compounds which have their atoms connected in the same order but differ in 3-D orientation


Glucosamine (R = H), a naturally occurring substance found in the exoskeleta of marine invertebrates, is believed by some to be helpful in relieving arthritic symptoms in humans. What are, respectively, the relative positions of the amino group to the CH2OH substituent and OR group?

Learning Check

  • cis, cis

  • trans, trans

  • cis, trans

  • trans, cis

  • cannot be determined from this kind of perspective drawing


Glucosamine (R = H), a naturally occurring substance found in the exoskeleta of marine invertebrates, is believed by some to be helpful in relieving arthritic symptoms in humans. What are, respectively, the relative positions of the amino group to the CH2OH substituent and OR group?

Solution

  • cis, cis

  • trans, trans

  • cis, trans

  • trans, cis

  • cannot be determined from this kind of perspective drawing


4.3 Stability of Cycloalkanes: Ring Strain

  • Rings larger than 3 atoms are not flat

  • Cyclic molecules can assume nonplanar conformations to minimize angle strain and torsional strain by ring-puckering

  • Larger rings have many more possible conformations than smaller rings and are more difficult to analyze


Stability of Cycloalkanes: The Baeyer Strain Theory

  • Baeyer (1885): since carbon prefers to have bond angles of approximately 109°, ring sizes other than five and six may be too strained to exist

  • Rings from 3 to 30 C’s do exist but are strained due to bond bending distortions and steric interactions


Summary: Types of Strain

  • Angle strain - expansion or compression of bond angles away from most stable

  • Torsional strain - eclipsing of bonds on neighboring atoms

  • Steric strain - repulsive interactions between nonbonded atoms in close proximity


4.4 Conformations of Cycloalkanes

Cyclopropane

  • 3-membered ring must have planar structure

  • Symmetrical with C–C–C bond angles of 60°

  • Requires that sp3based bonds are bent (and weakened)

  • All C-H bonds are eclipsed


Bent Bonds of Cyclopropane

  • In cyclopropane, the C-C bond is displaced outward from internuclear axis


Cyclobutane

  • Cyclobutane has less angle strain than cyclopropane but more torsional strain because of its larger number of ring hydrogens

  • Cyclobutane is slightly bent out of plane - one carbon atom is about 25° above

    • The bend increases angle strain but decreases torsional strain


Cyclopentane

  • Planar cyclopentane would have no angle strain but very high torsional strain

  • Actual conformations of cyclopentane are nonplanar, reducing torsional strain

  • Four carbon atoms are in a plane

    • The fifth carbon atom is above or below the plane – looks like an envelope


What kind of strain is relieved the most by ring puckering in cyclopentane?

Learning Check

  • torsional

  • steric

  • angle

  • steric and angle

  • torsional and steric


What kind of strain is relieved the most by ring puckering in cyclopentane?

Solution

  • torsional

  • steric

  • angle

  • steric and angle

  • torsional and steric


4.5 Conformations of Cyclohexane

  • Substituted cyclohexanes occur widely in nature

  • The cyclohexane ring is free of angle strain and torsional strain

  • The conformation is has alternating atoms in a common plane and tetrahedral angles between all carbons

  • This is called a chair conformation


How to Draw Cyclohexane


4.6 Axial and Equatorial Bonds in Cyclohexane

  • The chair conformation has two kinds of positions for substituents on the ring: axial positions and equatorial positions

  • Chair cyclohexane has six axial hydrogens perpendicular to the ring (parallel to the ring axis) and six equatorial hydrogens near the plane of the ring


Axial and Equatorial Positions

  • Each carbon atom in cyclohexane has one axial and one equatorial hydrogen

  • Each face of the ring has three axial and three equatorial hydrogens in an alternating arrangement


Drawing the Axial and Equatorial Hydrogens


Conformational Mobility of Cyclohexane

  • Chair conformations readily interconvert, resulting in the exchange of axial and equatorial positions by a ring-flip


Which of the following does not contribute to the overall energy of a cycloalkane?

Learning Check

  • torsional strain

  • angle strain

  • hydrogen bonding

  • steric strain

  • All of these contribute to the overall energy of a cycloalkane.


Which of the following does not contribute to the overall energy of a cycloalkane?

Solution

  • torsional strain

  • angle strain

  • hydrogen bonding

  • steric strain

  • All of these contribute to the overall energy of a cycloalkane.


4.7 Conformations of MonosubstitutedCyclohexanes

  • Cyclohexane ring rapidly flips between chair conformations at room temp.

  • Two conformations of monosubstituted cyclohexane aren’t equally stable.

  • The equatorial conformer of methyl cyclohexane is more stable than the axial by 7.6 kJ/mol


1,3-Diaxial Interactions

  • Difference between axial and equatorial conformers is due to steric strain caused by 1,3-diaxial interactions

  • Hydrogen atoms of the axial methyl group on C1 are too close to the axial hydrogens three carbons away on C3 and C5, resulting in 7.6 kJ/mol of steric strain

2 x 3.8 = 7.6


Relationship to Gauche Butane Interactions

  • Gauche butane is less stable than anti butane by 3.8 kJ/mol because of steric interference between hydrogen atoms on the two methyl groups

  • The four-carbon fragment of axial methylcyclohexane and gauche butane have the same steric interaction

  • In general, equatorial positions give more stable isomer


4.8 Conformational Analysis of DisubstitutedCyclohexanes

  • In disubstituted cyclohexanes the steric effects of both substituents must be taken into account in both conformations

  • There are two isomers of 1,2-dimethylcyclohexane. cis and trans

  • In the cis isomer, both methyl groups are on the same face of the ring, and compound can exist in two chair conformations


Cis 1,2-Dimethylcyclohexane

  • Consider the sum of all interactions

  • In cis-1,2, both conformations are equal in energy

2 x 3.8 = 7.6

3.8

= 11.4 kJ

2 x 3.8 = 7.6

3.8

= 11.4 kJ


Trans-1,2-Dimethylcyclohexane

  • Methyl groups are on opposite faces of the ring

  • One trans conformation has both methyl groups equatorial and only a gauche butane interaction between methyls (3.8 kJ/mol) and no 1,3-diaxial interactions

  • The ring-flipped conformation has both methyl groups axial with four 1,3-diaxial interactions


Trans-1,2-Dimethylcyclohexane

  • Steric strain of 4  3.8 kJ/mol = 15.2 kJ/mol makes the diaxial conformation 11.4 kJ/mol less favorable than the diequatorial conformation

  • trans-1,2-dimethylcyclohexane will exist almost exclusively (>99%) in the diequatorial conformation

3.8

2 x 3.8 = 7.6

= 15.2 kJ

2 x 3.8 = 7.6


Table 4-1, p. 124


Cis-1-t-butyl-4-chlorocyclohexane

2 x 1.0 = 2.0

2 x 11.4 = 22.8


(Haworth Projection)

OH’s preferred Equatorial

p. 126


Which of the above molecules represents the most stable conformation of trans-1,3-dimethylcyclohexane?

Learning Check

  • a

  • b

  • c

  • d

  • e


Which of the above molecules represents the most stable conformation of trans-1,3-dimethylcyclohexane?

Solution

  • a

  • b

  • c

  • d

  • e


Which of the following statements is true?

Learning Check

  • An axial group encounters more steric strain than an equatorial group.

  • All substituted cycloalkanes possess axial and equatorial bonds.

  • Only cyclopentane rings possess axial and equatorial bonds.

  • Cyclohexane derivatives are more stable with axial substituents than with equatorial substituents.

  • A cyclic compound cannot contain a double bond.


Which of the following statements is true?

Solution

  • An axial group encounters more steric strain than an equatorial group.

  • All substituted cycloalkanes possess axial and equatorial bonds.

  • Only cyclopentane rings possess axial and equatorial bonds.

  • Cyclohexane derivatives are more stable with axial substituents than with equatorial substituents.

  • A cyclic compound cannot contain a double bond.


Which of the following statements is true concerning the isomers cis-1,2-dimethylcyclohexane and cis-1,3-dimethylcyclohexane?

Learning Check

  • They are not constitutional isomers.

  • They represent different conformations of the same molecule.

  • The favored conformer of the 1,3-isomer is more stable than that of the 1,2-isomer.

  • The favored conformer of the 1,3-isomer and that of the 1,2-isomer are equal in energy.

  • The relative stability of the two molecules cannot be determined.


Which of the following statements is true concerning the isomers cis-1,2-dimethylcyclohexane and cis-1,3-dimethylcyclohexane?

Solution

  • They are not constitutional isomers.

  • They represent different conformations of the same molecule.

  • The favored conformer of the 1,3-isomer is more stable than that of the 1,2-isomer.

  • The favored conformer of the 1,3-isomer and that of the 1,2-isomer are equal in energy.

  • The relative stability of the two molecules cannot be determined.


What isomer of dichlorocyclohexane is represented by the Newman projection shown below?

Learning Check

  • 1-axial; 3-axial

  • 1-equatorial; 4-equatorial

  • 1-equatorial; 3-equatorial

  • 1-equatorial; 3-axial

  • 1-equatorial; 4-axial


What isomer of dichlorocyclohexane is represented by the Newman projection shown below?

Solution

  • 1-axial; 3-axial

  • 1-equatorial; 4-equatorial

  • 1-equatorial; 3-equatorial

  • 1-equatorial; 3-axial

  • 1-equatorial; 4-axial


Which of the above structures represents the most stable conformation of 1-tert-butyl-3,5-dimethylcyclohexane?

Learning Check

  • a

  • b

  • c

  • d

  • e


Which of the above structures represents the most stable conformation of 1-tert-butyl-3,5-dimethylcyclohexane?

Solution

  • a

  • b

  • c

  • d

  • e


What is the energy difference between the two chair conformations of trans-1,2-dimethylcyclohexane?

Learning Check

  • zero

  • one gauche interaction

  • two gauche interactions

  • three gauche interactions

  • four gauche interactions


What is the energy difference between the two chair conformations of trans-1,2-dimethylcyclohexane?

Solution

  • zero

  • one gauche interaction

  • two gauche interactions

  • three gauche interactions

  • four gauche interactions


What happens to a substituent in a chair conformation of cyclohexane when all bonds rotate in a synchronized fashion?

Learning Check

  • nothing, it stays where it was

  • it “flips” to an alternative position on the same carbon

  • it moves to the next carbon

  • the carbon to which the substituent is attached changes hybridization

  • it moves from a cis to a trans position


What happens to a substituent in a chair conformation of cyclohexane when all bonds rotate in a synchronized fashion?

Solution

  • nothing, it stays where it was

  • it “flips” to an alternative position on the same carbon

  • it moves to the next carbon

  • the carbon to which the substituent is attached changes hybridization

  • it moves from a cis to a trans position


Dipole moments usually are measured on collections of molecules, and represent average values for all conformations present. Which of the following collections of molecules will not show a dipole moment?

Learning Check

  • 1,2-dibromoethane

  • trans-1,2-dibromocyclohexane

  • cis-1,2-dibromocyclohexane

  • cis-1,4-dibromocyclohexane

  • trans-1,4-dibromocyclohexane


Dipole moments usually are measured on collections of molecules, and represent average values for all conformations present. Which of the following collections of molecules will not show a dipole moment?

Solution

  • 1,2-dibromoethane

  • trans-1,2-dibromocyclohexane

  • cis-1,2-dibromocyclohexane

  • cis-1,4-dibromocyclohexane

  • trans-1,4-dibromocyclohexane


Which of the above will have the highest energy after the chair flip?

Learning Check

  • a

  • b

  • c

  • d

  • e


Which of the above will have the highest energy after the chair flip?

Solution

  • a

  • b

  • c

  • d

  • e


4.9 Conformations of Polycyclic Molecules

  • Decalin consists of two cyclohexane rings joined to share two carbon atoms (the bridgehead carbons, C1 and C6) and a common bond

  • Two isomeric forms of decalin: trans fused or cis fused

  • In cis-decalin hydrogen atoms at the bridgehead carbons are on the same face of the rings

  • In trans-decalin, the bridgehead hydrogens are on opposite faces

  • Both compounds can be represented using chair cyclohexane conformations

  • Flips and rotations do not interconvert cis and trans


Fig. 4-17, p. 128


Steroids

Cholesterol

p. 136


p. 129


p. 129


p. 129


p. 135


What are the relative geometries of ring fusions (starting from the left) for the steroid shown below?

Learning Check

  • cis, cis, cis

  • cis, cis, trans

  • cis, trans, trans

  • trans. cis, cis

  • trans, trans, cis


What are the relative geometries of ring fusions (starting from the left) for the steroid shown below?

Solution

  • cis, cis, cis

  • cis, cis, trans

  • cis, trans, trans

  • trans. cis, cis

  • trans, trans, cis


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