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Orbital Symmetry Subject

Only one exception to the clean production of two monomer molecules from the pyrolysis of dimer has been noted. When a-hydroxydi-Zvxyljlene (9) is subjected to the Gorham process, no polymer is formed, and the 16-carbon aldehyde (10) is the principal product in its stead, isolated in greater than 90% yield. This transformation indicates that, at least in this case, the cleavage of dimer proceeds in stepwise fashion rather than by a concerted process in which both methylene—methylene bonds are broken at the same time. This is consistent with the predictions of Woodward and Hoffmann from orbital symmetry considerations for such [6 + 6] cycloreversion reactions in the ground state (5). [Pg.428]

C=N, and O2 can also act as dienopbiles to give heterocycHc products. These types of concerted reactions have been the subject of extensive orbital symmetry studies (118,119). [Pg.344]

Cheletropic processes are defined as reactions in which two bonds are broken at a single atom. Concerted cheletropic reactions are subject to orbital symmetry analysis in the same way as cycloadditions and sigmatropic processes. In the elimination processes of interest here, the atom X is normally bound to other atoms in such a way that elimination gives rise to a stable molecule. In particular, elimination of S02, N2, or CO from five-membered 3,4-unsaturated rings can be a facile process. [Pg.591]

Cheletropic processes are defined as reactions in which two bonds are broken at a single atom. Concerted cheletropic reactions are subject to orbital symmetry restrictions in the same way that cycloadditions and sigmatropic processes are. [Pg.403]

In some cases, steric interactions can prevent unimolecular reactions. Tetrahe-drane (18) has been the subject of a number of studies, and the conclusion is that, if formed, it would rapidly decompose to form two molecules of acetylene. However, tetra-tert-butyltetrahedrane (19) is a quite stable substance, and on heating rearranges to tetra-tert-butylcyclobutadiene. An orbital symmetry " analysis of the cleavage of tetrahedrane to acetylene indicates that it involves a torsional motion that in the case of the tert-butyl substituted derivative would bring the tert-butyl groups very close to each other. As a result, this mode of reaction is not possible, and the compound is relatively stable. [Pg.731]

Dimerization of lff-azepines is an extensively studied phenomenon and involves a temperature dependent cycloaddition process. At low (0°C for 1 R = Me) or moderate (130 °C for 1 R = C02R or CN) temperatures a kinetically controlled, thermally allowed [6 + 4] dimerization to the exo -adduct (73) takes place, accompanied by a small amount (<10%) of symmetrical dimer (74). The latter are thermodynamically favored and become the major products (83%) when the Iff-azepines are heated briefly at 200 °C. The symmetrical dimers probably arise by a non-concerted diradical pathway since their formation from the parent azepines by a concerted [6+6]tt cycloaddition, or from dimer (73) by a 1,3-sigmatropic C-2, C-10 shift are forbidden on orbital symmetry grounds. Dimerization is subject to steric restraint and is inhibited by 2-, 4- and 7-substituents. In such cases thermolysis of the lif-azepine brings about aromatization to the correspondingly substituted JV-arylurethane (69JA3616). [Pg.508]

It is evident from a comparison of 5 and 4 that the reflection transforms >pi into i/j2. The reader should verify that the a reflection and the C2 rotation also transform symmetry correct. The result we have found will generally hold when molecular orbitals constructed by the LCAO method from hybrid atomic orbitals are subjected to symmetry operations. Each of those orbitals in the set of MO s that is not already symmetry correct will be transformed by a symmetry operation into another orbital of the set. [Pg.546]

Theoretical chemistry rates some special mention in this context. Nowadays this activity tends to be quite mathematical [1], but history shows us that theoretical chemistry need not be mathematical at all. From the first years of the crystallization of chemistry as a subject distinct from alchemy, chemists have utilized theory, in the sense of disciplined speculation. Nonmathematical examples are found in the structural theory of organic chemistry [2] and in most applications of the powerful Woodward-Hoffman orbital symmetry rules [3]. [Pg.587]

The Hiickel molecular orbital (HMO) model of pi electrons goes back to the early days of quantum mechanics [7], and is a standard tool of the organic chemist for predicting orbital symmetries and degeneracies, chemical reactivity, and rough energetics. It represents the ultimate uncorrelated picture of electrons in that electron-electron repulsion is not explicitly included at all, not even in an average way as in the Hartree Fock self consistent field method. As a result, each electron moves independently in a fully delocalized molecular orbital, subject only to the Pauli Exclusion Principle limitation to one electron of each spin in each molecular orbital. [Pg.537]

This question is the subject of much debate, because the mechanism by which the oxaphosphetane is formed is not entirely understood. One possible explanation relies on rules of Orbital symmetry, which you will meet in Chapters 35 and 36—we need not explain them in detail here but suffice it to say that there is good reason to believe that, if the ylid and carbonyl compound react... [Pg.816]

Eberson and co-workers have recently discussed the probability that the interaction of ion-radicals with nucleophiles and electrophiles is subject to orbital symmetry constraints.31,32 This follows the observation that with perylene the cation-radical (18) the preferred course of reaction with halide ions is electron transfer rather than nucleophilic addition, whereas with the phenothiazine cation-radical (19) nucleophilic attack by Cl" and Br occurs. [Pg.217]

Bonding in uranocene has been the subject of controversy for some 30 years. It was early on pointed out that orbital symmetry interactions, involving f orbitals, could be drawn analogous to those in ferrocene (Figure 13.16). [Pg.221]

D A superb presentation of this subject can be found in the book Woodward, R. B., Hoffmann, R. The conservation of orbital symmetry. Weinheim Verlag Chemie 1970. [Pg.42]


See other pages where Orbital Symmetry Subject is mentioned: [Pg.126]    [Pg.474]    [Pg.27]    [Pg.335]    [Pg.150]    [Pg.928]    [Pg.205]    [Pg.58]    [Pg.210]    [Pg.252]    [Pg.162]    [Pg.72]    [Pg.326]    [Pg.520]    [Pg.72]    [Pg.1016]    [Pg.152]    [Pg.3028]    [Pg.1163]    [Pg.1122]    [Pg.1122]    [Pg.81]    [Pg.149]    [Pg.71]    [Pg.72]    [Pg.1016]    [Pg.210]    [Pg.252]    [Pg.458]    [Pg.292]    [Pg.123]   


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