Benzimidazoline

Benzimidazoline, 2,2-bis(trifluoromethyl)-synthesis, 5, 471 Benzimidazolines acidity, 5, 425 Benzimidazolinethiones Mannich reaction, 5, 390 synthesis, 5, 460 Benzimidazoline-2-thiones alkylation, 5, 444—445 S-alkylation, 5, 444 mercuration, 5, 445 reactions... 

Benzimidazolinone, 1,3-dimethyl-Friedel-Crafts reaction, 5, 429 Benzimidazolinone, 1,3-divinyl-synthesis, 5, 393 Benzimidazolinone, 6-methyl-Friedel-Crafts reaction, 5, 429 Benzimidazolin-2-one polymers, 1, 281 Benzimidazolinones alkylation, 5, 390 Friedel-Crafts reaction, 5, 429 Mannich reaction, 5, 390 nitration, 5, 429 reactions, 5, 442... 

The N-bis-silylated o-phenylenediamine 1511 reacts with DMF at 120°C to give benzimidazole, in 97% yield, and dimethylamine and hexamethyldisiloxane 7, whereas reaction of benzaldehyde with 1511 gives only 29% 2-phenylbenzimida-zole 1513, because the intermediate benzimidazoline 1512 is only rather slowly dehydrogenated to 1513 [52]. Heating of N,N -bis(trimethylsilyl)ethylenediamine 1514 with DMF affords imidazoline 1515 and dimethylamine and HMDSO 7 ]52] (Scheme 9.32). The lactam 1516 cycHzes analogously with SiCU 57/triethylamine in 63% yield to give 1517 ]53]. 

Nickel chloride promoted desulfurization and reductive cleavage of N,N -diarylthioureas gives corresponding anilines and tV-methylanilines (Scheme 69). While 7V,tV -dialkylthioureas undergo desulfurization to give formami-dines, and benzimidazoline-2-thiones underwent desulfurization to benzimidazoles (Scheme 69).159... 

Photolytic. Irradiation of trifluralin in hexane by laboratory light produced a,a,a-trifluoro-2,6-dinitro-A-propyl-jo-toluidine and a,a,a-trifluoro-2,6-dinitro-p-toluidine. The sunlight irradiation of trifluralin in water yielded a,a,a-trifluoro-A, 7 -dipropyl-5-nitrotoluene-3,4-diamine, a,a,a-trifluoro-A/ ,A/ -dipropyltoluene-3,4,5-triamine, 2-ethyl-7-nitro-5-(trifluoromethyl)benzimidazole, 2,3-dihydroxy-2-ethyl-7-nitro-l-propyl-5-(trifluoromethyl)benzimidazoline, and 2-ethyl-7-nitro-5-(trifluoromethyl)benzimidazole. 2-Amino-6-nitro-a,a,a-trifluoro-p-toluidine and 2-ethyl-5-nitro-7-(trifluoromethyl)benzimidazole also were reported as major products under acidic and basic conditions, respectively (Crosby and Leitis, 1973). In a later study, Leitis and Crosby (1974) reported that trifluralin in aqueous solutions was very unstable to sunlight, especially in the presence of methanol. The photodecomposition of trifluralin involved oxidative TV-dealkylation, nitro reduction, and reductive cyclization. The principal photodecomposition products of trifluralin were 2-amino-6-nitro-a,a,a-trifluoro-jo-toluidine, 2-ethyl-7-nitro-5-(trifluoromethyl)benzimida-zole 3-oxide, 2,3-dihydroxy-2-ethyl-7-nitro-l-propyl-5-(trifluoromethyl)benzimidazole, and two azoxybenzenes. Under alkaline conditions, the principal photodecomposition product was 2-ethyl-7-nitro-5-(trifluoromethyl)-benzimidazole (Leitis and Crosby, 1974). 

Dihydroxy-2-ethyl-7-nitro-l-propyl-5-(trifluoromethyl)benzimidazoline, see Trifluralin... 

For rhodium and iridium compounds alkoxo ligands take over the role of the basic anion. Using /z-alkoxo complexes of ( -cod)rhodium(I) and iridium(I)— formed in situ by adding the /r-chloro bridged analogues to a solution of sodium alkoxide in the corresponding alcohol and azolium salts—leads to the desired NHC complexes even at room temperature [Eq. (10)]. Using imidazolium ethoxyl-ates with [(r " -cod)RhCl]2 provides an alternative way to the same complexes. By this method, it is also possible to prepare benzimidazolin-2-ylidene complexes of rhodium(I). Furthermore, an extension to triazolium and tetrazolium salts was shown to be possible. ... 

Imidazolidinium salts can also be transformed into the corresponding diamino ortho-esters by alkaline alkoxylate, and upon alcohol elimination at elevated temperature the imidazolidin-2-ylidenes can be trapped. The reaction of tria-zolium salts with sodium methanolate in methanol yields 5-methoxy-4,5-dihydro-IH-triazole which also eliminates methanol upon heating in vacuo. The resulting triazolin-5-ylidenes can either be isolated or trapped by an appropriate metal precursor [Eq. (19)]. Benzimidazolin-2-ylidenes are similarly accessible by this route. 

Cyclic thiourea derivatives like l,3,4,5-tetramethylimidazole-2(3H)-thione— prepared by condensation of substituted thioureas with a-hydroxyketones—can be converted into the corresponding imidazolin-2-ylidene by desulfurization with sodium or potassium [Eq. (23)]. This method was used to prepare and isolate l,3-bis-neo-pentylbenzimidazolin-2-ylidene with Na/K. With LDA as the base it is also possible to generate free benzimidazolin-2-ylidenes in solution. ... 

Electron-rich olefins are nucleophilic and therefore subject to thermal cleavage by various electrophilic transition metal complexes. As the formation of tetraaminoethylenes, i.e., enetetramines, is possible by different methods, various precursors to imidazolidin-2-ylidene complexes are readily available. " Dimerization of nonstable NHCs such as imidazolidin-2-ylidenes is one of the routes used to obtain these electron-rich olefins [Eq. (29)]. The existence of an equilibrium between free NHC monomers and the olefinic dimer was proven only recently for benzimidazolin-2-ylidenes. In addition to the previously mentioned methods it is possible to deprotonate imidazolidinium salts with Grignard reagents in order to prepare tetraaminoethylenes. " The isolation of stable imidazolidin-2-ylidenes was achieved by deprotonation of the imidazolidinium salt with potassium hydride in THF. ... 

Benzimidazolin-2-ylidene complexes are conveniently prepared from the corresponding enetetramines. In refluxing toluene the olefin is attacked, e.g., by [(f/ -cod)RhCl]2 to form the mono(NHC) or the bis(NHC) complex depending on the reaction conditions. ... 

Ruthenium(n) systems containing imidazol-2-ylidene or imidazolidin-2-ylidene have been used to catalyze the synthesis of 2,3-dimethylfuran starting at (Z)-3-methylpent-2-en-4-yn-l-ol [Eq. (54)]. The activity of the catalyst strongly depends on the nature of the NHC ligand. Benzimidazolin-2-ylidenes give the best results for this transformation. Similar systems have also been used for olefin metathesis reactions. ... 

In addition to the compounds listed above, a number of triazolium [36], thiazolium [37], and benzimidazolin-2-thione [32] derivatives as well as five-membered heterocycles with only one nitrogen atom [38, 39] or two phosphorus atoms [40] within the heterocycle, all of which are suitable for the generation of heterocyclic carbenes, have been described. 

Although these two methods have found widespread application for the synthesis of free carbenes, they failed for selected saturated imidazolidin-2-ylidenes and especially in the preparation of triazolin-5-ylidenes. In these cases the free carbene species 7 can be obtained from 2-alkoxyimidazolidines 6 [44] or 5-aUcoxytriazoles [36] by thermally induced ot-elimination of an alcohol (Fig. 5). In addition to 2-aUcoxyimidazolidmes, 2-(pentafluorophenyl)imidazolidines [45, 46] have also been used for the generation of NHCs by cx-elimination. The adduct 8 eliminates acetonitrile upon heating [47] to yield the benzimidazolin-2-ylidene 9. In a more exotic procedure, imidazolium salts have been reduced electrochemically to give the free imidazolin-2-ylidenes [48]. 

The reaction of the free carbene with a suitable metal complex is the simplest method for the preparation of an NHC complex (Fig. 8a). In addition, the cleavage of electron-rich enetetramines in the presence of coordinatively unsaturated metal complexes followed by coordination and stabilization of the NHC also constitutes an established method for the preparation of NHC complexes (Fig. 8b) [7, 95], which works particularly well for the preparation of complexes with benzimidazolin-2-ylidene ligands [56, 80, 96]. 

The exclusive coordination of the C5 carbon atom in complex 48 was achieved by a reduction of the bite angle [147]. Blocking of the C4 and C5 positions as seen in benzimidazolin-2-ylidenes led to the complex with the C2-metalated NHC ligand 49 [147]. No transformation of a C5-coordinated NHC ligand into a C2-coordinated one, i.e., conversion of 46 to 47 or vice versa, has been observed so far. 

Complex 61 is also accessible from the 2-nitrophenyl isocyanide complex 68 by reduction of the nitro group with Sn/HCl. Incomplete reduction of the nitro group in 68 with Raney-Nickel/hydrazine yields, after intramolecular cyclization, the complex 70 with the NH,NOH-stabilized benzimidazolin-2-ylidene ligand. Complex 69 with the 2-hydoxylamin-substituted phenyl isocyanide ligand presumably occurs as an intermediate in this reaction. The alkylation of both the NH,NH- and the NH, NOH-stabilized NHC ligands in 67 and 70, respectively, proceeds readily (Fig. 23) [184, 185]. 

Fig. 23 Template-controlled synthesis of benzimidazolin-2-ylidene ligands...

NHCs are often compared to phosphines and theoretical studies by Frenking et al. [211-213] showed that the substitution of the phosphines in 89 for two NHCs leads to compounds with a carbon(O) atom that is formally stabilized by two NHC C donor-acceptor bonds. The first carbodicarbene 90 was prepared by Bertrand et al. who selected benzimidazolin-2-ylidenes as carbene donors and the deprotonation of the conjugated acid of an allene as the synthetic strategy (Fig. 29)... 

Condensation monomers having the benzimidazolin-2-one ring system have found utility as modifiers in polyester synthesis. In particular, halogenated diols (73) and dicarboxylic acids (74) may be incorporated (78MI11100) into polyethylene terephthalate) or poly(butyl-ene terephthalate) at fairly low levels to impart flame retardancy. This can be accomplished without adverse effects upon other polymer properties. 

Benzimidazolone or o-Phenylene-urea (called N.-N -o-Phenylen-hamstoff 2-Oxy-benzimidazol 2-Oxo-benzimidazolin or Benzimidazolon in Ger), -NH... 

BENZIMIDAZOLINE-1 -PROPIONITRILE. 3- (1- (p-CHLORO-alpha-METHYLBENZYL) 4-PIPERIDYL) -2-0X0-. HYDROCHLORIDE... 

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