Cyclohexane energies

The experimental data in Table 3.1 show that the calculated values of total angle strain are approximately correct only for cyclopropane, cyclobutane, and cyclopentane. Cyclohexane is definitely not the strained compound Baeyer s theory predicts, and the larger ring compounds are also not very strained. Any chemist today can explain the discrepancy between these calculated and experimental values of strain energy cyclohexane is not planar. In either the chair or boat conformations (Figure 3.12), all bond angles can be approximately 109.5°. In the chair conformation of cyclohexane, all bonds are staggered, and there are no apparent van der Waals repulsions in the molecule. ... 

Figure 2.27 The four conformations of a cyclohexane ring shown in order of increasing energy. Cyclohexanes prefer to exist as chair conformations whenever possible.

From stochastic molecnlar dynamics calcnlations on the same system, in the viscosity regime covered by the experiment, it appears that intra- and intennolecnlar energy flow occur on comparable time scales, which leads to the conclnsion that cyclohexane isomerization in liquid CS2 is an activated process [99]. Classical molecnlar dynamics calcnlations [104] also reprodnce the observed non-monotonic viscosity dependence of ic. Furthennore, they also yield a solvent contribntion to the free energy of activation for tlie isomerization reaction which in liquid CS, increases by abont 0.4 kJ moC when the solvent density is increased from 1.3 to 1.5 g cm T Tims the molecnlar dynamics calcnlations support the conclnsion that the high-pressure limit of this unimolecular reaction is not attained in liquid solntion at ambient pressure. It has to be remembered, though, that the analysis of the measnred isomerization rates depends critically on the estimated valne of... 

The activation energy for cyclohexane ring inversion is 45 kJ/mol (10 8 kcal/mol) It IS a very rapid process with a half life of about 10 s at 25°C... 

A potential energy diagram for nng inversion m cyclohexane is shown m Figure 3 18 In the first step the chair conformation is converted to a skew boat which then proceeds to the inverted chair m the second step The skew boat conformation is an inter mediate in the process of ring inversion Unlike a transition state an intermediate is not a potential energy maximum but is a local minimum on the potential energy profile... 

FIGURE 3 18 Energy diagram showing the inter conversion of various con formations of cyclohexane... 

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... 

A modified boat conformation of cyclohexane, known as the twist boat (Fig. 1.8), or skew boat, has been suggested to minimize torsional and nonbounded interactions. This particular conformation is estimated to be about 1.5 kcal moE (6 kJ moE ) lower in energy than the boat form at room temperature. 

Regardless of the techniques used to purify the KA oil, several waste streams are generated during the overall oxidation—separation processes and must be disposed of. The spent oxidation gas stream must be scmbbed to remove residual cyclohexane, but afterwards will stiU contain CO, CO2, and volatile hydrocarbons (especially propane, butane, and pentane). This gas stream is either burned and the energy recovered, or it is catalyticaHy abated. 

Stereochemistry. Cyclohexane can exist ia two molecular conformations the chair and boat forms. Conversion from one conformation to the other iavolves rotations about carbon—carbon single bonds. Energy barriers associated with this type of rotation are low and transition from one form to the other is rapid. The predominant stereochemistry of cyclohexane has no influence ia its use as a raw material for nylon manufacture or as a solvent. 

Some processes use only one reactor (57) or a combination of liquid- and vapor-phase reactors (58). The goal of these schemes is to reduce energy consumption and capital cost. Hydrogenation normally is carried out at 2—3 MPa (20—30 atm). Temperature is maintained at 300—350°C to meet a typical specification of less than 500 ppm benzene in the product at higher temperatures, thermodynamic equiUbrium shifts to favor benzene and the benzene specification is impossible to attain. Also, at higher temperatures, isomerization of cyclohexane to methylcyclopentane occurs typically there is a 200 ppm specification limit on methylcyclopentane content. 

The overall picture of the many results which have been obtained with hetero-substituted cyclohexane rings is a very consistent one. Cyclohexane itself in its lowest energy conformation adopts the so-called chair conformation, as depicted in Figure 3 by the two outer formulae (a, b). These are contained in energy wells ca. 42 kJ moP deep. Another conformation, of low abundance in cyclohexane at normal temperatures, but which is important in some substituted derivatives, is the twist form (c, d). This is ca. 22 kJ moP less stable than the chair forms, and it lies on the lowest-energy pathway between them. 

Figure 3 Shapes and relative energies of cyclohexane conformations...

Concern for the conservation of energy and materials maintains high interest in catalytic and electrochemistry. Oxygen in the presence of metal catalysts is used in CUPROUS ION-CATALYZED OXIDATIVE CLEAVAGE OF AROMATIC o-DIAMINES BY OXYGEN (E,Z)-2,4-HEXADIENEDINITRILE and OXIDATION WITH BIS(SALI-CYLIDENE)ETHYLENEDIIMINOCOBALT(II) (SALCOMINE) 2,6-DI-important industrial method, is accomplished in a convenient lab-scale process in ALDEHYDES FROM OLEFINS CYCLOHEXANE-CARBOXALDEHYDE. An effective and useful electrochemical synthesis is illustrated in the procedure 3,3,6,6-TETRAMETHOXY-1,4-CYCLOHEX ADIENE. ... 

Fig. 3.4. Energy diagram for ring inversion of cyclohexane. [For a rigorous analysis of ring inversion in cyclohexane, see H. M. Pickett and H. L. Strauss, J Am. Chem. Soc. 92 7281 (1979).]...

Energy differences between conformations of substituted cyclohexanes can be measured by several physical methods, as can the kinetics of the ring inversion processes. NMR spectroscopy has been especially valuable for both thermodynamic and kinetic studies. In NMR terminology, the transformation of an equatorial substituent to axial and vice versa is called a site exchange process. Depending on the rate of the process, the difference between the chemical shifts of the nucleus at the two sites, and the field strength... 

The free-energy difference between conformers is referred to as the conformational free energy. For substituted cyclohexanes, it is conventional to specify the value of — AC ° for the equilibrium... 

When two or more substituents are present on a cyclohexane ring, the interactions between the substituents must be included in the analysis. The dimethylcyclohexanes provide an example in which a straightforward interpretation is in complete agreement with the experimental data. For 1,2-, 1,3-, and 1,4-dimethylcyclohexane, the free-energy change of the equilibrium for the cis trans isomerization is given below. ... 

The decalin (bicyclo[4.4.0]decane) ring system provides another important system for study of conformational effects in cyclohexane rings. Equilibration of the cis and trans isomers reveals that the trans isomer is favored by about 2.8 kcal/mol. Note that this represents a change in configuration, not conformation. The energy difference can be analyzed by noting that the cis isomer has three more gauche butane interactions that are... 

The effect of introducing -hybridized atoms into open-chain molecules was discussed earlier, and it was noted that torsional barriers in 1-alkenes and aldehydes are somewhat smaller than in alkanes. Similar effects are noted when sp centers are incorporated into six-membered rings. Whereas the fiee-energy barrier for ring inversion in cyclohexane is 10.3 kcal/mol, it is reduced to 7.7 kcal/mol in methylenecyclohexane and to 4.9 kcal/mol in cyclohexanone. ... 

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