Methanimine

CH3I (methyl iodide) principal axes, 103 If rotation, 113 CH2NH (methanimine) interstellar, 120 Cr203 (chromium trioxide) in alexandrite laser, 347ff in ruby laser, 346ff HC3N (cyanoacetylene) interstellar, 120 HCOOH (formic acid) interstellar, 120 NH2CN (cyanamide) interstellar, 120... 

Haddlcton and coworkers314 reported the use of Cu1 complexes based on the methanimine ligands (e.g. 136-138) and have demonstrated their efficacy in the polymerization of methacrylates. The ligands can be prepared in situ from the appropriate amine and 2-pyridinc carboxaldchydc (Scheme 9.34). 

Polymerizations of S and MMA with in situ catalyst formation have also been carried out. Matyjaszewski et a ..355 reported on the use of FeBr2 together with various ligands such as PfQHs). , NiCiIIo. and 133 alone or in combination. The use of diearboxylic acid (iminodiacetic acid, isophthalic acid)356 and methanimine ligands " for MMA polymerization has also been reported. 

Benzotriazole-related methodology publications appeared in 2006. Reaction of 1-formylbenzotriazole with triphenylphosphine/carbon tetrachloride afforded l-(2,2-dichlorovinyl)benzotriazole, where lithiation followed addition of electrophiles gave a variety of functionalized M-(ethynyl)benzotriazoles <06T3794>. Novel mono- and symmetrical di-/V-hydroxy- and IV-aminoguanidines were readily prepared from the reaction of diverse hydroxylamines or hydrazines with reagent classes di(benzotriazol-l-yl)methanimine, (bis-benzotriazol-1 -y 1-methy lene)amines, benzotriazole-1 -carboxamidines, benzotriazole-1 -... 

Di(5-nonyl)-2,2 -bipyridine A-propyl(2-pyridyl)methanimine 2,2 6, 2" -Terpyridine 4,4, 4"-Tris(5-nonyl)-2,2 6, 2"-terpyridine N, N, N, N", /V -Pentamethy ldie(hyelenetriamine 1,1,4,7,10,10-Hexamethyltriethylenetetramine Tris[2-(dimethylaminoethyl]amine Tris[(2-pyridyl)methyl]amine... 

Chelating bis(imine) ligands such asA-alkyl(2-pyridyl)methanimine (AlkPMI) have also been successfully utilized in copper-mediated ATRP [74,75,76,77,78]. In... 

A successive refinement (MNDO-PM3) of the reaction of the Reformatsky derivative of methyl bromoacetate with both formaldehyde and methanimine was carried out including coordinated THF molecules. It identified a twist-boat transition structure as the most stable TS for the transformation of G into H7. 

The thermal decomposition of 2-azidoacetic acid (N3CH2CO2H) in the vapour phase has been shown, by photoelectron and matrix isolation infrared spectroscopy, to involve simultaneous formation of CO2 and methanimine (CH2NH) with concerted ejection of N2.52 No evidence was found for formation of intermediate nitrene (NCH2CO2H) or the imine (HNCHCO2H) to which it could be converted by 1,2-hydrogen shift. 

Fig. 2 Optimized geometric features of the first transition structure (a) and the intermediate (b) corresponding to the reaction between ketene and methanimine. Bond distances and angles are given in A and deg., respectively, to denotes the dihedral angle between the C4, Nl, C2 and C3 atoms...

Catalyses of the addition of HCN to methanimine by formamidine and by formamide has been studied computationally.81... 

In the carbonyl compounds FC(0)Y the C—F bond distances show a strong dependence on the substituent X and shorten from 136.2(2) pm in acetyl fluoride (Y = Me) to 131.6(1) pm carbonyl fluoride (Y = F). In formyl fluoride (Y = H) and carbonyl chloride fluoride (Y = Cl) the C—F bond lengths are intermediate. When CF2 groups are double-bonded to C, O, S or Se, the C—F bond distances are remarkably constant and range only from 131.5 to 131.9 pm. Such bond lengths, however, are shorter by ca 1.5 pm in compounds with C=N double bonds, such as methanimine or 2,3-diaza-l, 3-butadiene. In both compounds only mean values for the C—F bond distances can be derived from the ED experiments. Ab initio calculations for perfluoromethanimine predict that the C—F bond trans to N—F is longer by 0.4 pm than the cis bond. 

Orbital pictures for methanimine, CH2NH,and formaldehyde, CH20. 

Isobarbituric acid 2,4,5(3//)-Pyrimidinetrione, dihydro- Methylenimine Methanimine... 

Very few syntheses of tetrazoles were reported in 2003. Various a-dialkylated (3-keto esters 219 underwent Schmidt rearrangement with trimethylsilyl azide to give tetrazole 220, which could be elaborated further to azido acid 221, precursors to a-dialkylated a-amino acids <03TL3179>. Di(benzotriazolyl)methanimine 222 reacted with various secondary amines to generate 223, which when treated with sodium azide in the presence of acetic acid yielded N,N-disubstituted 5-aminotetrazoles 224 in moderate to good yields <03JOC4941>. 

Methanimin l-(4-Chlor-phenyl)-N-(trimethylsilyl-methyl)- E14b, 248 (R-CHO + R-N = PR3)... 

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