Cyclohexanes strain

There are many possible quantitative evaluations of strain. This chapter uses related heats of formation (A/ ) and heats of combustion (A//°) to arrive at values for the strain energies of various rings. As rings increase in size, strain initially decreases, reaching a minimum at the strain-free cyclohexane. Strain then increases until large ring sizes are reached. 

FIGURE 3 14 (a) A ball and spoke model and (b) a space filling model of the boat confor mation of cyclohexane Torsional strain from eclipsed bonds and van der Waals strain involving the flagpole hydrogens (red) make the boat less stable than the chair... 

Disubstituted cyclopropanes exemplify one of the simplest cases involving stabil ity differences between stereoisomers A three membered ring has no conformational mobility so the ring cannot therefore reduce the van der Waals strain between cis sub stituents on adjacent carbons without introducing other strain The situation is different m disubstituted derivatives of cyclohexane... 

Section 3 7 Three conformations of cyclohexane have approximately tetrahedral angles at carbon the chair the boat and the skew boat The chair is by far the most stable it is free of torsional strain but the boat and skew boat are not When a cyclohexane ring is present m a compound it almost always adopts a chair conformation... 

Make molecular models of the two chair conformations of cis 1 tert butyl 4 phenyl cyclohexane What is the strain energy calculated for each conformation by molecular mechanics Which has a greater preference for the equatorial onentation phenyl or tert butyD... 

The chemical properties of cycHc ketones also vary with ring size. Lower members (addition reactions, than corresponding acycHc ketones. The Cg—C 2 ketones are unreactive, reflecting the strain and high enol content of medium-sized ring systems. Lactones are prepared from cycHc ketones by the Bayer-ViUiger oxidation reaction with peracids. S-Caprolactone is manufactured from cyclohexane by this process ... 

Fig. 1.6. Charge distributions in strained cyclic hydrocarbons in comparison with cyclohexane. Data are from K. B. Wiherg, R. F. W. Bader, and C. D. H. Lau, J. Am. Chem. Soc. 109 1001 (1987).

Studies of cyclodecane derivatives by X-ray crystallographic methods have demonstrated that the boat-chair-boat conformation is adopted in the solid state. (Notice that boat is used here in a different sense than for cyclohexane.) As was indicated in Table 3.7 (p. 146), cyclodecane is significantly more strained than cyclohexane. Examination of the boat-chair-boat conformation reveals that the source of most of this strain is the close van der Waals contacts between two sets of three hydrogens on either side of the molecule. 

If the heat of fonnation parameters are derived on the basis of fitting to a large variety of compounds, a specific set of parameters is obtained. A slightly different set of parameters may be obtained if only certain strainless molecules are included in the parameterization. Typically molecules like straight chain alkanes and cyclohexane are defined as strainless. Using these strainless heat of formation parameters, a strain energy may be calculated as illustrated in Figure 2.14. 

Figure 4.3 Cycloalkane strain energies, calculated by taking the difference between cycloalkane heat of combustion per CH2 and acyclic alkane heat of combustion per CH2, and multiplying by the number of CH2 units in a ring. Small and medium rings are strained, but cyclohexane rings are strain-free.

The data in Figure 4.3 show that Baeyer s theory is only partially correct. Cyclopropane and cyclobutane are indeed strained, just as predicted, but cyclopentane is more strained than predicted, and cyclohexane is strain-free. Cycloalkanes of intermediate size have only modest strain, and rings of 14 carbons or more are strain-free. Why is Baeyer s theory wrong ... 

Cyclohexane adopts a strain-free, three-dimensional shape, called a chair conformation because of its similarity to a lounge chair, with a back, a seat, and a footrest (Figure 4.7). Chair cyclohexane has neither angle strain nor torsional strain—all C—C-C bond angles are near 109°, and all neighboring C-H bonds are staggered. 

In addition to the chair conformation of cyclohexane, a second arrangement called the twist-boat conformation is also nearly free of angle strain. It does, however, have both sleric strain and torsional strain and is about 23 kj/mol (5.5 kcal/mol) higher in energy than the chair conformation. As a result, molecules adopt the twisl-boat geometry only under special circumstances. 

Cyclohexane is strain-free because it adopts a puckered chair conformation, in which all bond angles are near 109° and all neighboring C—H bonds are staggered. Chair cyclohexane has two kinds of positions axial and equatorial. Axial positions are oriented up and down, parallel to the ring axis, whereas equatorial positions lie in a belt around the equator of the ring. Each carbon atom has one axial and one equatorial position. 

Chair cyclohexanes are conformationally mobile and can undergo a ring-flip, which interconverts axial and equatorial positions. Substituents on the ring are more stable in the equatorial position because axial substituents cause 1,3-diaxial interactions. The amount of 1,3-diaxial steric strain caused by an axial substituent depends on its hulk. 

Amantadine is an antiviral agent that is active against influenza A infection and against some strains of H5NX avian flu. Draw a three-dimensional representation of amantadine showing the chair cyclohexane rings. 

Boat cyclohexane (Section 4.5) A conformation of cyclohexane that bears a slight resemblance to a boat. Boat cyclohexane has no angle strain but has a large number of... 

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