Cross benzamides

Benzazepinones can be prepared on cross-linked polystyrene by intramolecular Heck reaction (Entry 6, Table 15.35). In the presence of sodium formate, the intramolecular Heck reaction of iodoarenes with alkynes yields methylene benzazepinones (Entry 7, Table 15.35). Surprisingly, when this reaction was performed in solution, the main product (65% yield) was a dehalogenated, non-cyclized benzamide. In the synthesis on cross-linked polystyrene, however, this product was not observed [419]. 

A rational extension of ortho-tolyl benzamide metalation [68], part of the broadly encompassing lateral metalation protocol [69] that can be DoM-connected, is the DreM equivalent, 154 —> 155 (Scheme 41), which provides a general regioselective route to 9-phenanthrols (156, 157, 158) [70] and may be extended to diaryl nitriles, hydroxylamine ethers, and hy-drazones 160, which provide the corresponding 9-amino derivatives 161 of similar generality 162-165 (Scheme 42), as may also be applied in natural product synthesis [71]. Further opportunities for DoM-cross-coupling and reduction/oxidation chemistry (159) have also been demonstrated [70a]. 

Representative compounds believed to bind at the benzamide site on the basis of evidence from competitive binding or cross-resistance studies (discussed below) are shown in Fig. 16.1.3. Although these compounds differ from zoxamide in their relative toxicity toward different organisms, they appear to bind to the same domain on y -tubulin. Selective toxicity may be governed by structural differences between organisms in this domain. 

Great improvements in the TFC membranes were also experienced by Chen et al. [56] by incorporating water-soluble amine reactants—sulfonated cardo poly(arylene ether sulfone) (SPES-NH2)—into an aqueous solution containing MPD. Under optimum preparation conditions, the TFC membranes prepared from SPES-NH2 showed remarkable increase in water permeability (51.2 L/m h) with a slight decrease in salt rejection (97.5% at 2000 ppm NaCl, 2 MPa) compared to membranes prepared without SPES-NH2 (37.4 L/m h and 99%). The improved results are attributed to the incorporation of hydrophilic SPES-NH2 to PAs and/or a higher degree of cross-linking formed in the thin selective layer. In view of the importance of hydrophilicity on TFC membrane performance, a novel amine monomer—3,5-diamino-A-(4-aminophenyl) benzamide (DABA)—with three amino... 

The authors have made an approximate estimate of the dimensions of the unit cell for poly(p-benzamide) from X-ray diffraction photographs (Fig. 9) and find the cell to be orthorhombic with a = 5-2 A, b = 7-7 A, c = 12-95 A. While the values of a and b will probably need refining as better diffraction photographs become available the cross-sectional area... 

Perhaps structurally the most simple primary amide gelators, 3,4,5-tris-(alkoxy) benzamides 1 and 2 (Fig. 1), have been prepared by amidation of tris(alkoxy)benzoic acids and shown to gel both polar (MeOH, EtOH, DMF) and highly lipophilic organic solvents (n-octane, w-decane, toluene) at minimal gelation concentrations (mgc) lower than 2.5 wt % [5]. The gel aggregates can be embedded into cross-linked polymer matrices using monomer/cross-linker mixtures as organic solvents. 

This book has been divided into three areas chemical detection, biological detection, and decontamination. The subject matter in the chapters include cross-linked divinyl benzene-substituted methacrylate polymers (Chapter 2), porous silicon (Chapter 3), reactive glass surfaces (Chapter 4), polycarbosilanes (Chapter 5), non-aqueous, chemically cross-linked polybutadiene gels (Chapter 6), conducting polyaniline nanofibers (Chapter 7), organically doped polystyrene and polyvinyltoluene (Chapter 8), electroplated polymer cast resins (Chapter 9), self assembled monolayers (Chapter 10), amphiphilic functionalized norbomene polymers (Chapter 11), transition metal substituted polyoxometalates (POMs) (Chapter 12), cross-linked divinyl-benzamide phospholipids (Chapter 13), and silica and organo silyl polymers (Chapter 14). 

Thus, cross-coupling of the DoM-derived benzamide boronic acid 99 with bro-mobenzenes 100, which may also be prepared by DoM chemistry, furnishes biaryls 101 that under either HCl or BBrj/HOAc conditions produce the methyl ether or free phenol dibenzopyranones 102, respectively. Establishment of regiochemistry by DoM in the thereby derived biaryls 103 and hence the unusually substituted... 

A most instructive demonstration of the power of the combined DoM-cross-coupHng-DreM strategy concerns the synthesis of MK-7285 143 (Scheme 14.29), a powerfiil anti-inflammatory agent In the large-scale synthesis of 143, a one-pot DoM-Suzuld-Miyaura cross-coupling, starting from benzamide 139 and bro-mobenzene 140, leads to the biaryl derivative 141 in excellent yields. Treatment with lithium diethylamide results in a lateral remote metallation of 141, subsequently inducing a cychzation to the phenanthrol derivative 142, which is converted in several steps to 143 [143]. 

Later, Yu et al. reported the first example of Ru(n)-catalysed direct C-H amination of benzamides with N-benzoyloigramines at room temperature. This reaction is compatible with halogenated arenes, which are usually prone to react in cross-coupling reactions. Both fluorinated and chlorinated arenes reacted and provided the corresponding aminated products in 40-69% yields. Whereas, brominated arenes were less compatible giving lower yields. Other heteroarenes including pyrazole. 

Ni-CaUdyzed Reactions The nickel-mediated decarbonylative cross-coupling of dia-rylzinc reagents with phthaUmides, in the role of electrophilic coupling partner, has been reported, using reaction conditions similar to those described in Scheme 22.4 [9]. This reaction provides a highly efficient means to construct ort/io-substituted benzamides (Scheme 22.30). 

The thermo-oxidative cross-linking of nylon 6 and the resistance to oxidation of its graft copolymers with polyacrylonitrile have been studied. The thermal and thermal oxidative degradation of poly(/w-phenylene isophthalamide) and other aromatic polyamide compositions, together with comparative studies on the mechanisms of degradation of poly(p-benzamide) and poIy(p-phenylene terephalamide) have all been reported. 

Figure 4.27 A cross-section of results for Rh-catalyzed oxidative orfho-acylation of benzamides with aldehydes as reported by Park et al. [59].

Ohishi et al. have reported homopolymer-arm, block-arm, and miktoarm star polymers consisting of poly(N-octylm-benzamide) and poly(N-H-m-benzamide) by means of a core cross-linking method [74]. The H-NMR spectra of the star polymers in DMSO revealed that the poly(N-octyl-m-benzamide) segments and arms of the block-arm and miktoarm star polymers, respectively. Star 2 and star 3 before deprotection showed rather similar solubility, and they were soluble in many kinds of organic solvents, except for alcohols. After deprotection, star 4 was only soluble in polar aprotic solvents, such as DMF and DMSO, whereas starS was soluble in dichloromethane (E>CM), CHCI3, and DMF and insoluble in DMSO. Hence, the character of the external segment of the arms dominates the solubility and aggregability of the block-arm star polymers. 

Activation by rhodium complexes has been used to achieve direct exchange of ketone methyl or aryl groups with an aryl group on ArB(OH)2, selective C(CO)-C bond cleavage on reaction of ketones with water, oxidative acylation between secondary benzamides and aryl aldehydes with subsequent intramolecular cyclization to 3-hydroxyisoindolin-l-ones, " cross dehydrogenative coupling to form xanthones from 2-aryloxybenzaldehydes, and activation of the aldehydic C-H bond to achieve hydroacylation of unactivated alkenes by salicylaldehyde derivatives and of vinylsilane by benzaldehyde. ... 

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