Acetamidines

Another common process iavolves reaction with C=C or C=N species having adjacent CH2 or CH groups. Initial attack of the isocyanate is on the electron-rich center of the double bond with subsequent migration and iasertion of the CONR group iato the CH bond. Suitable reagents iaclude A/-alkylated acetamidines, 1-methyl dihydroisoquiaoline, and 2-methyl-2-oxa2oline [1120-64-5] (35). 

Although the Pinner pyrimidine synthesis was discovered a century ago only a few reports on the reaction mechanism have appeared. The condensation of acetylacetone, methyl acetoacetate, or dimethyl malonate with acetamidine (6) has been studied by Katritzky et al. and the reaction mechanisms for these processes have been proposed by these authors. Outlined below is the proposed mechanism of the condensation of methyl acetoacetate (4) with acetamidine (6)7... 

In context with the formation of peraminosubstituted 1,4,5,8-tetraazaful-valenes of type 85 it must be mentioned that the bis-vinylogous compounds 94 can be easily prepared by reaction of acetamidine with bisimidoylchlo-rides derived from oxalic acid (96S1302). In the course of a complex reaction a cyclic ketene aminal was produced it immediately underwent an oxidative dimerization to yield deeply colored TAFs. Tlieir high chemical stability can be compared with that of indigoid dyes and manifests itself, for example, by the fact that they are soluble in hot concentrated sulfuric acid without decomposition. Tire same type of fulvalene is also available by cy-... 

Diethyl oxalate, condensation with o-mtrotoluene, 43, 40 N,N Diethyl-N -phenyl-2,2-dichloro-acetamidine, 41, 23... 

Similar reactions with the corresponding acetamidinate anion gave only the monomeric [MeC(NCy)2]2V(THF)2 and [MeC(NCy)2]2VCl, respectively (Scheme 108). Removal of THF from [MeC(NCy)2]2V(TFlF)2 or reduction of [MeC (NCy)2]2VCl led to formation of the homoleptic V(III) complex [MeC(NCy)2]3V instead of a metal-metal-bonded dimer. ° °... 

The square planar Ni11 complex (131) is formed upon reaction of MeCN with the dinuclear complex (132). A sequence of Ni-mediated hydrolytic transformations, MeCN —> acetamide and NH3 — acetamidine — TV-acetimidoylacetamidine, is proposed.488 While the A-acetimidoylacet-amidine ligands are isoelectronic with acac, they have a much stronger ligand field. 

Amino-2,6-dimethylpyrimidine has been prepared by heating the reaction product obtained from acetic anhydride and acetamidine 1 by treating 4-chloro-2,6-dimethylpyrimidine with ammonia 2 and by heating acetonitrile either with sodium ethox-ide in a sealed tube3 or with sodium.4 6... 

N-[3-(aminomethyl)benzyl]acetamidine (1400W) Fig 10 8 structure of 1400W. 

Hallinan, E. A., Tsymbalov, S., Finnegan, P. M., Moore, W. M., Jerome, G. M., Currie, M. G., Pitzele, B. S., Acetamidine lysine derivative, N-(5(S)-amino-6,7-dihydroxyheptyl)ethanimidamide dihydrochloride a highly selective inhibitor of human inducible nitric oxide synthase, /. Med. Chem. 41 (1998), p. 775-777... 

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