Spiro-aromatic

Spiro-aromaticity (Section 1.5.5) is barely detectable. Explain why the spiro cation 1.54, might have more tt stabilisation by spiro conjugation than spiro-heptatriene 1.30. 

An ipso attack on the fluorine carbon position of 4-fIuorophenol at -40 °C affords 4-fluoro-4-nitrocyclohexa-2 5-dienone in addtion to 2-nitrophenol The cyclodienone slowly isomenzes to the 2-nitrophenol Although ipso nitration on 4-fluorophenyl acetate furnishes the same cyclodienone the major by-product is 4 fluoro-2,6-dinitrophenol [25] Under similar conditions, 4-fluoroanisole pnmar ily yields the 2-nitro isomer and 6% of the cyclodienone The isolated 2 nitro isomer IS postulated to form by attack of the nitromum ion ipso to the fluorine with concomitant capture of the incipient carbocation by acetic acid Loss of the elements of methyl acetate follows The nitrodienone, being the keto tautomer of the nitrophenol, aromatizes to the isolated product [26] (equation 20) Intramolecular capture of the intermediate carbocation occurs in nitration of 2-(4-fluorophenoxy)-2-methyIpropanoic acid at low temperature to give the spiro products 3 3-di-methyl-8 fluoro 8 nitro-1,4 dioxaspiro[4 5]deca 6,9 dien 2 one and the 10-nitro isomer [2d] (equation 21)... 

Chiralpak OT(+) dominates the branches built under the spiro and AROMATIC RING>1 molecular keys. 

Other polynuclear hydrocarbons may include bridged hydrocarbons, spiro hydrocarbons, mixed systems containing alicyclic and aromatic rings, and aliphatic chains, etc. Examples may be found in the CRC Handbook [63, Section C]. Physical properties of selected polynuclear aromatic compounds are given in [49, p. 967]. 

Facial selectivities of spiro[cyclopentane-l,9 -fluorene]-2-ones 30a-30e were studied by Ohwada [96, 97]. The carbonyl tz orbital can interact with the aromatic % orbital of the fluorene in a similar manner to spiro conjugation [98-102]. The ketones 30 were reduced to alcohols by the action of sodium borohydride in methanol at -43 °C. The anti-alcohol, i.e., the syn addition product of the reducing reagent with respect to the substituent, is favored in all cases, irrespective of the substituent at C-2 or C-4 of the fluorene ring (2-nitro 30b syn anti = 68 32), 4-nitro... 

In the epoxidation of an olefin with a peracid, the occupied n orbital of the olefin group HOMO) interacts with the vacant orbital (LUMO) of the peracid [143, 144]. The higher-lying aromatic n orbital of the substituted fluorenes (69) can interact with the orbital in a similar manner to spiro conjugation (Fig. 12). 

Benzo[fl]- (a), benzo[fc]- (b) and benzo[c]flnorenes (c) bearing a diene group (93) in spiro geometry are three possible combinatorial isomers wherein the direction of fnsion of the naphthalene is different (Fig. 15). The n reaction centers of the diene gronps are snbject to spiro-conjngation [98, 99, 102] with the planar aromatic n system. The effect of perturbation arising from spiro-conjngation on... 

In the Spiro systems 30, the aromatic orbitals unsymmetrize the carbonyl orbital. Simultaneously, the carbonyl group can perturb the orthogonal aromatic ring. Nitration of the fluorene derivatives (30) bearing a spiro substituent was studied (Fig. 17) [96, 97]. 

Ohwada extends his theory, unsymmetrization of n orbitals, to Orbital Phase Environment including the secondary orbital interaction (Chapter Orbital Phase Environments and Stereoselectivities by Ohwada in this volume). The reactions between the cyclopentadienes bearing spiro conjugation with benzofluorene systems with maleic anhydride exemplified the importance of the phase environment. The reactions proceed avoiding the out-of-phase interaction between dienophile LUMO and the HOMO at the aromatic rings. The diene 34 with benzo[b]fluorene favored syn addition with respect to the naphtalene ring, whereas the diene 35 with benzo[c]fluorene showed the reverse anti preference (Scheme 22) [28]. 

Up to now, nine classes of different polyphosphazenes are known and characterized substituted with aliphatic alcohols [40,41,262-281] or phenols [41,95, 277,282-297],with aliphatic [42,298-300] or aromatic [301-304] amino groups, with di-functional spiro hydroxy (e.g. dihydroxybiphenyl [305] or di hydroxy-... 

Nowhere, perhaps, is this phenomenon better illustrated than in the phenothiazine class. The earlier volume devoted a full chapter to the discussion of this important structural class, which was represented by both major tranquilizers and antihistamines. The lone phenothiazine below, flutiazin (130), in fact fails to show the activities characteristic of its class. Instead, the ring system is used as the aromatic nucleus for a nonsteroidal antiinflammatory agent. Preparation of 130 starts with formylation of the rather complex aniline 123. Reaction with alcoholic sodium hydroxide results in net overall transformation to the phenothiazine by the Smiles rearrangement. The sequence begins with formation of the anion on the amide nitrogen addition to the carbon bearing sulfur affords the corresponding transient spiro intermediate 126. Rearomatization... 

Knolker and coworkers also used a domino [3+2] cycloaddition for the clever formation of a bridged tetracyclic compound 4-172, starting from a cyclopentanone 4-168 and containing two exocydic double bonds in the a-positions (Scheme 4.36) [57]. The reaction of 4-168 with an excess of allylsilane 4-169 in the presence of the Lewis acid TiCLj led to the spiro compound 4-170 in a syn fashion. It follows a Wag-ner-Meerwein rearrangement to give a tertiary carbocation 4-171, which acts as an electrophile in an electrophilic aromatic substitution process. The final step is the... 

Only three examples of ibogan-type oxindole alkaloids are known, and two of them, crassanine (156) and tabemoxidine (155), were found in Tabernaemon-tana. Crassanine (C23H30N2O5, MP 191°C, [a]D +21°) was isolated in minute amounts by Cava et al. from T. crassa (79). Its IR spectrum indicated the presence of two carbonyl groupings (1739 and 1709 cm - ), while its UV spectrum was almost superimposable on that of known 10,11-dimethoxyoxindoles such as kisantine (200). In addition to the carbomethoxy methyl at 3.47 ppm and two aromatic methoxyls at 3.83 ppm (6H), the H-NMR spectrum of 156 exhibited two singlets (1H) at 6.50 and 7.01 ppm and the low-field oxindole NH at 9.30 ppm. The latter values are similar to those recorded for kisantine, and on this basis Cava et al. proposed the structure 102 for crassanine. To date, no evidence is available on the configuration at the C-7 spiro center. 

Addition of carbenes to Jt-electron excessive aromatic compounds, or those which possess a high degree of bond fixation, is well established. Dihalocarbenes react with naphthalenes with ring expansion to produce benztropylium systems (Scheme 7.8). Loss of hydrogen halide from the initially formed product leads to an alkene which reacts with a second equivalent of the carbene to yield the spirocyclopropyl derivatives in high yield (>95%) [14, 50]. Insertion into the alkyl side chain (see Section 7.2) also occurs, but to a lesser extent [14]. Not unexpectedly, dichlorocarbene adds to phenanthrenes across the 9,10-bond [9, 10, 14], but it is remarkable that the three possible isomeric spiro compounds could be isolated (in an overall yield of 0.05% ) from the corresponding reaction with toluene [14]. 

In addition, it should be useful to mention that silicon as a spiro atom is able to conjugate its mutually orthogonal aromatic constituents, and thus, secures a release of an unpaired electron in a cation-radical. Scheme 3.61 shows such a phenomenon, revealed by Hirao et al. (2007). Obviously, vacant d orbitals of silicon provide the cation-radical with the possibility of delocalizing spin density. 

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