4-Methoxyphenyl cation

The reaction of arenes with aryllead tricarboxylates performed in trifluoroacetic acid, affording biarenes, takes place via a cationic 7t-complex.162 Since azulenes form 7r-donor/acceptor complexes with various 7r-acids, the arylation of 4,6,8-trimethylazulene 108 was attempted with />-methoxyphenyllead triacetate 1 (Equation (135)).163 Only one isomer of 1-arylazulene 109 was formed although in a modest 27% isolated yield. Based on recovered unreacted azulene, the effective yield was 43%. A dimer 110, 3,3 -dianisyl-l,l -biazulene (4% yield), was suggested to result from the one-electron oxidation of the intermediate 4-methoxyphenyl cation in the 7t-complex. 

A highly innovative approach exploited the photolysis of various p-functionaHzed anisole precursors 55 in the presence of terminal alkynes such as 56, EtjN, and trifluoroethanol (TFE). The initially formed p-functionaUzed methoxyphenyl cations reacted with the terminal alkynes to provide the cross-coupled products 57 in yields between 60 and 90% (Scheme 9.19) [161]. This contains also the first reported alkynylation of aryl fluorides, mesylates, and phosphates. 

The stabilized fluorinated allylic cation, generated from cis- or trans-l-(p-methoxyphenyl)pentafluoropropene and antimony pentafluoride in sulfur dioxide, is solvolyzed by methanol to methyl 2-(p-methoxyphenyl)difluoroacrylate [36] (equation 37)... 

The functionalization of zinc porphyrin complexes has been studied with respect to the variation in properties. The structure and photophysics of octafluorotetraphenylporphyrin zinc complexes were studied.762 Octabromoporphyrin zinc complexes have been synthesized and the effects on the 11 NMR and redox potential of 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraarylporphyrin were observed.763 The chiral nonplanar porphyrin zinc 3,7,8,12,13,17,18-heptabromo-2-(2-methoxyphenyl)-5,10,15,20-tetraphenylporphyrin was synthesized and characterized.764 X-ray structures for cation radical zinc 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin and the iodinated product that results from reaction with iodine and silver(I) have been reported.765 Molecular mechanics calculations, X-ray structures, and resonance Raman spectroscopy compared the distortion due to zinc and other metal incorporation into meso dialkyl-substituted porphyrins. Zinc disfavors ruffling over doming with the total amount of nonplanar distortion reduced relative to smaller metals.766 Resonance Raman spectroscopy has also been used to study the lowest-energy triplet state of zinc tetraphenylporphyrin.767... 

If one compares the solvolyses of 2-bromo-l,l-diphenyl-4-(p-methoxyphenyl)-but-l-en-3-yne (57) and 4.4-diphenyl-1 -bromo-1 -(/ -mcthoxyphcny l)-buta-1,2,3-tricncs (58, X = Br) in aqueous ethanol (equation 21), the destabilization of the intermediate cation 59 by the large inductive effect of the triple bond as compared to its conjugative effect is evident42. Only in the case of 58 could the substitution product butatrienyl enol ether 60 be isolated in 40% yield, while it was only detected by UV and IR spectroscopy in the solvolysis product of 57. The faster observed reaction rate of 58 as compared to 57 was ascribed to a difference in their ground-state energies42. 

The photo-oxidation of the aryl-substituted cycloheptatrienes 7-(/ -methoxy-phenyl)cycloheptatriene and 7-, 1- and 3-(/ -dimethylaminophenyl)cycloheptatrienes to the corresponding radical cations in de-aerated acetonitrile solution was accomplished by electron transfer to the electronically excited acceptors 9,10-dicyanoanthracene, iV-methylquinolinium perchlorate, iV-methylacridinium perchlorate and l,T-dimethyl-4,4-bipyridinium dichloride. In the case of l- p-methoxyphenyl)cycloheptatriene (62), deprotonation of the radical cation occurs successfully, compared with back electron transfer, to give a cycloheptatrienyl radical (63) which undergoes a self-reaction forming a bitropyl. If the photooxidation is done in air-saturated acetonitrile solution containing HBF4 and one of the acceptors, the tropylium cation is formed. Back electron transfer dominates in the / -dimethylaminocycloheptatrienes and the formation of the cycloheptatrienyl radical is prevented. 

Photolysis of vinyl halides can induce both heterolysis of the C-X bond, thereby generating vinyl cations, and homolysis giving vinyl radicals. This competition between the two mechanisms was studied for 3-vinyl halides, 1,2,2-triphenylbromoethane (136) and 1-phenyl-2,2-bis(o-methoxyphenyl)-l-bromoethene and /3-styrene. Incursion of the photo-induced SrnI process, through the intermediate vinyl radical, is verified in the presence of reducing nucleophiles, such as the enolate ions of ketones and in part with (EtO)2PO . Incursion of the heterolytic pathway and the intermediacy of the radical cation, occurs in the presence of weak electron-donor anions, such as N02, Ns and Cl . The vinyl cation of /3-styrene gives phenylacetylene via an El-type elimination. 

The same way was used by Yoon and Kim (2005) for the preparation of 5-(p-methoxyphenyl)thian threnium ion incorporated in a calyx[4]arene. Namely, the ratio of starting materials, methoxycal-ixarene to the thianthrene cation-radical perchorate, was 1 10. The product of such 5-anisylation of thianthrene was further transformed into a calixarene bearing an additional o-phenylene thio-macrocycle. This macrocylization is beyond the scope of this book the original paper by Yoon and Kim (2005) could be recommended for those who interested in. It is worth noting only one practical importance of the calixarene-phenylene thiomacrocycle here It selectively extracts silver(l-l-) by both calixarene and thiomacrocycle. Each molecule of this combined complexon takes up two silver cations, so that extractability achieves 165%. 

Nitrenium ions can be viewed as products from two-electron oxidation of amines (Fig. 13.13) followed by loss of a proton. Thus they need to be considered as intermediates in the oxidation of amines. In two early studies, diarylnitrenium ions were shown to have formed in the oxidation of diarylamines. Svanholm and Parker carried out cyclic voltammetry on A,A-di-(2,4-methoxyphenyl)amine (25) in acetonitrile with alumina added to suppress any adventitious nucleophiles. The voltam-mogram revealed two sequential oxidation processes (1) formation of the cation radical 26, and (2) either the nitrenium ion 27 or its conjugate acid. In strongly acidic solution the latter was sufficiently stable that its absorption spectrum could be recorded. 

There are several examples of arylnitrenium ion additions to alkenes (Fig. 13.54). For example, Dalidowicz and Swenton trapped A-acetyl-A-(4-methoxyphenyl)-nitrenium ion 112 with 3,4-dimethoxy-l-propenylbenzene and isolated products resulting from addition of the alkene to the ortho position of the nitrenium ion, giving cation 113, followed by its cychzation onto N (yielding 114) or the acetyl carbonyl group (yielding 115). 

MS fragmentation of a series of 13 4-aryl-3,3-dichloro-2-oxetanes (18) has been reported to give the dichloroketene cation as the base peak in every case, except for the 4-(m-methoxyphenyl) compound. There the base peak was for the m-methoxybenzaldehyde cation. The results were in marked contrast to the cleavage seen on thermolysis, which gave carbon dioxide and the corresponding/3,j8-dichlorostyrene (78JHC1165). 

The development of mass spectrometric ionization methods at atmospheric pressures (API), such as the atmospheric pressure chemical ionization (APCI)99 and the electrospray ionization mass spectrometry (ESI-MS)100 has made it possible to study liquid-phase solutions by mass spectrometry. Electrospray ionization mass spectrometry coupled to a micro-reactor was used to investigate radical cation chain reaction is solution101. The tris (p-bromophenyl)aminium hexachloro antimonate mediated [2 + 2] cycloaddition of trans-anethole to give l,2-bis(4-methoxyphenyl)-3,4-dimethylcyclobutane was investigated and the transient intermediates 9 + and 10 + were detected and characterized directly in the reacting solution. However, steady state conditions are necessary for the detection of reactive intermediates and therefore it is crucial that the reaction must not be complete at the moment of electrospray ionization to be able to detect the intermediates. 

Gratzel and co-workers reported an N3-dye-sensitized nanocrystalline Ti02 solar cell using a hole-transport material such as 2,2, 7,7 -tetrakis (N, N-di-p-methoxyphenyl-amine) 9,9 -spirobifluorene (OMeTAD) as shown in Fig. 17, as a solid electrolyte [143]. OMeTAD was spin-coated on the surface of the N3 dye/Ti02 electrode and then Au was deposited by vacuum evaporation as the counterelectrode. The cell efficiency was 0.7% under 9.4 mW/cm2 irradiation, and 3.18 mA/cm2 of Jsc was obtained under AM 1.5 (100 mW/cm2) [143]. The maximum IPCE was 33% at 520 nm. The rate for electron injection from OMeTAD into cations of N3 dyes has been estimated as 3 psec, which is faster than that of the I ion case [144]. 

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