Cyclophanes 5 paracyclophans

SJ paracyclophane etc.] refers to the benzene rings in the structure, i.e. [8]-paracyclophane, [2,2,2]-para-cyclophane. Systems based upon heterocyclic molecules are also known. 

As an illustrating example for the application of the Friedel-Crafts acylation in the synthesis of complex molecules, its use in the synthesis of [2.2.2]cyclophane 13 by Cram and Truesdale shall be outlined. The reaction of [2.2]paracyclo-phane 10 with acetyl chloride gives the acetyl-[2.2]paracyclophane 11, which is converted into the pseudo-geminal disubstituted phane 12 by a Blanc reaction, and further to the triple bridge hydrocarbon 13 ... 

Schneider and Busch have showed that tetraazafS 1 8 l paracyclophane catalyzes the nitration of alkyl bromides with sodiiun nitrite In dioxane-water d l at 30 C, the reaction of 2-bromomethylnaphthalene with sodiiun nitrite is accelerated by a factor of 20 in the presence of the catalyst Concomitantly, the product ratio of [R-ONO [RNO-, changes from 0 50 1 to 016 1 Thus, an acciuruiladon of nitrite ions at the positively charged cyclophanes or IRA-900-nitrite form provides a new method for selective nitration of alkyl halides... 

Optical Activity Caused by Restricted Rotation of Other Types. Substituted paracyclophanes may be optically active and 25, for example, has been resolved. In this case, chirality results because the benzene ring cannot rotate in such a way that the carboxyl group goes through the alicyclic ring. Many chiral layered cyclophanes (e.g., 26) have been prepared. ... 

These structural data demonstrate that 12 is a rather less distorted molecule than [2.2]paracyclophane. However, a dramatic effect of the strong cr(Si—Si)—w interaction was observed in UV spectra as shown in Fig. 5. In the UV spectrum of phenylpentamethyldisilane, an intramolecular crfSi—Si)—7T charge-transfer band appears around 231 nm (11a, 12). Octamethyltetrasila[2.2]ortho- (15) and metacyclophane (16) show similar absorptions, but the band splits into two bands at 223 nm (e = 19,100) and 263 nm (e = 22,500) in 12. This type of red shift in the UV spectra occurs only in 12 among other polysilapara-cyclophanes such as 13 and 14. 

To date the structure and reactivity of numerous complexes derived from aromatic compounds and nitrosonium cation have been studied (5, 56-63). However, relatively few studies are available on the nitrosonium complexes of cyclophanes (5, 57, 59, 61, 62), cf ref. (63). The interaction of [2.2]paracyclophane with nitrosonium tetrachloroaluminate was studied by H and 13C NMR spectroscopy using deuterium isotope perturbation technique (64). It was found that the resulting nitrosonium complexes containing one (25) or two NO groups (26) are involved in fast interconversion (on the NMR time scale) (Scheme 17). 

The properties of the cyclophanes are best illustrated by the para-cyclophanes. In contrast to the metacyclophanes and metapara-cyclophanes 2>, where aromatic nuclei come into close proximity, there are in paracyclophane molecules two aromatic nuclei pressed one on top... 

During the synthesis of [2.2]paracyclophanediene, Dewhirst and Cram 83> prepared the bis-geminal dibromides 4a and 4b, which were subsequently converted into the diketones 5 a and 5 b. The UV spectra of the bromides 4a and 4 b show maxima at 236 nm. A comparison with the Amax values of other [2.2]paracyclophanes brominated at the bridges suggests that the absorption at 236 nm is the 235 nm band of [2.2]para-cyclophane, shifted bathochromically by the inductive effect of the... 

In sharp contrast to 20a, 4,5,7,8,12,13,15,16-octamethyl[2.2]para-cyclophane 22 is extraordinarily unstable 61>. This substance polymerizes at room temperature, both in solution and in the solid state, even in an inert atmosphere. The reason is that the accumulation of pseudo-geminal methyl groups leads to steric overcrowding which cannot be circumvented because of the rigidity of the [2.2]paracyclophane system. Accordingly,... 

The following compounds which have a benzene moiety of [2.2]para-cyclophane replaced by a heteroring (e.g. furan) may be counted among the analogs of [2.2]paracyclophane, as their stereochemistry has many features in common with that of the carbophanes 64> 34—36. 

The shift of the aromatic protons of [2.2](4,4 )biphenylophane (47) 71> to higher field strength is smaller than in [2.2]paracyclophane (T(H)arom = 3.63 in CDCI3). Furthermore, the spectra of 47 and 4,4 -dimethyl-biphenyl differ less from each other than do the spectra of [2.2]para-cyclophane and p-xylene. 

Multilayered cyclophanes having three aromatic rings fixed in parallel planes above one another exhibit properties intermediate between those of the [2.2]paracyclophanes and the above-mentioned compounds 51 and 52. A cyclic compound of this type, (53), has apparently been isolated by Hubert 77>. The tetracyanoethylene complex of... 

Three-decker cyclophanes containing paracyclophane structural elements have been synthesized by Otsubo et a/.49>79> the [2.2](1,4)-(1,4) [2.2] (2,5) (1,4)cyclophane (55) and the methyl-substituted compounds 56. 

The relative rates of acetylation in competition experiments in the [m.n]paracyclophane series 38> may be interpreted in terms of trans-annular electronic and steric effects. If the rate of acetylation of [6.6]para-cyclophane [(7), m =n =6] is is taken as one, the relative acetylation rates of the [4.4]-, [4.3]-, and [2.2]paracyclophanes are 1.6, 11, and >48, respectively. As the aromatic rings come closer together, the rate of entry of the first acetyl group into the nucleus increases, while that of the second acetyl group decreases. Both effects clearly indicate that the positive. partial charge can be distributed over both benzene rings in the monoacetylation transition state (64). 

Reich and Cram 111>112> have reported the results of a series of experiments, which all indicate thermal cleavage of [2.2]paracyclophane to the p,p-dimethylenebibenzyl diradical (157). After heating [2.2]para-cyclophane (2) at 250 °C in p-diisopropylbenzene, they isolated p,p-dimethylbibenzyl in 21% yield as the sole non-polymerizable product. 

The first is a cyclophane-based system reported by Murakami et al. (Fig. 9.12a). [31] The sides of the host consist of tetraaza-[3.3.3.3]paracyclophane units, and its octaprotonated cation has been shown to bind anionic guests. The molecule possesses 48 asymmetric units of [(N/3)-(CH2)- (C6H4)/2 ]/2. 

Cyclophanes are naturally suited for MMPI (15b) calculations. The results ofsuch calculations regarding the structures and electronic spectra of the [m] paracyclophanes (n = 5-10) agreed well with the experimental data (169). Attempted X-ray analyses of [2.4]- and [2.5](9,10)-anthracenophanes (46) encountered serious disorder in the ahphatic bridges. MMPI calculations of all possible conformers of these molecules revealed four and six energy minima for 46a and 46b, respectively. Comparison of the calculated C10 C10 distances and bridge conformations with X-ray information unambiguously identified two conformations each for 46a and 46b as the final solutions. These and the calculated structures of photoisomer 47 were highly useful in the interpretation of fluorescence spectra and photoisomerization processes of 46 (170). 

Among the three isomers of bis(phenylmethylenyl) [2.2]paracyclophanes [38], pseudo-ort/jo- and pseudo-para-isomers (o-[38j and p-[38], respectively) satisfy McConnell s condition to give quintet ground states. They were produced by photolysis of the corresponding bis(a-diazobenzyl)[2.2]para-cyclophanes [38a] in 2-MTHF at cryogenic temperatures, and their esr fine structures were studied. 

As seen, cyclophane structures shown in Schemes 1.4b through 1.4e have the following unique feature The through-bond distance within the paracyclophane fragment is held constant, whereas the spatial distance between the ion-radicalized and neutral moieties is changed. Therefore, the relative importance of through-bond and through-space mechanisms for intramolecular electron transfer can be learned directly from experimental data on these molecules. 

Fig. 1. Plane of Chirality Enantio-morphous figures and corresponding torsional angles A—X—Y—Z 7). Molecular examples ([n]paracyclophane, [2.2]meta-cyclophane, bridged[10]anulene and ( )-cyclooctene) with descriptors (/ , S)...

The nomenclature of phanes is simple 32) It mainly defines the length(s) of the bridge(s) and their positions in the ring as illustrated by the following examples [6]para-cyclophane (2) 1,10-dioxa [10]paracyclophane (6), [2.2]paracyclophane (7), [2.2]meta-(8) and [2.2]metaparacyclophane (9) and [8](2,5)pyridinophane (70). The formulae show also the kind of projection used in this survey to illustrate stereochemical relations. 

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