N methyl imine

Hexafluoroacetone imine has been prepared by the reaction of hexafluoroacetone with triphenyl phosphine imine,2 by the pyrolysis of N-phenyl-2,2-diaminohexafluoropropane,23 by the reaction of hexafluorothioacetone with hydrazoic acid,4 and by the reaction of ammonia and phosphorus oxychloride with hexafluoroacetone.4,5 The latter method, which is described here, is the most convenient for it does not require preparation of several intermediates or use of pressure equipment. This method has also been used to prepare the imines of other Huoroketones, including the imines of chloropentafluoroacetone, dichlorotetrafluoroacetone, and perfluorodiethyl ketone.5 Substitution of methylamine for ammonia in this procedure gives the N-methyl imine.5... 

Figure 1.1 Calculations ofthe LUMO energy in eV (geometry optimized at B3LYP/6 31C(d)) relative to N methyl imine derived from benzaldehyde.

Bolm et al. [108] prepared a C2-symmetric bis (sulfoximine) as ligand for the copper-catalyzed hetero-Diels-Alder reaction. The stereogenic sulfur atom being located near the AT-coordinating atom, these structures were assumed to be promising for asymmetric catalysis. Their Hgand (79 in Scheme 43) was synthesized by palladium-catalyzed N-aryl imination from 1,2-dibromobenzene and (S)-S-methyl-S-phenylsulfoximine with Pd2dba3 in 70% yield. 

Compounds of the general formula 69 are prepared by cycloaddition of N-methyl- or A(-arylmaleimides with arylidene imines of AAs and in the presence of an aromatic aldehyde. Stabilized azomethine ylides are formed as intermediates, which then afford the cycloadducts. Several isomers are formed, and the influence of various metal salts and solvents was investigated (87BCJ4067 88T557). Similar transformations have been performed with A-ailyl glycine esters (91TL1359). 

M. Shi and Y.-L. Shi reported the synthesis and application of new bifunctional axially chiral (thio) urea-phosphine organocatalysts in the asymmetric aza-Morita-Baylis-Hillman (MBH) reaction [176, 177] of N-sulfonated imines with methyl vinyl ketone (MVK), phenyl vinyl ketone (PVK), ethyl vinyl ketone (EVK) or acrolein [316]. The design of the catalyst structure is based on axially chiral BINOL-derived phosphines [317, 318] that have already been successfully utilized as bifunctional catalysts in asymmetric aza-MBH reactions. The formal replacement of the hydrogen-bonding phenol group with a (thio)urea functionality led to catalysts 166-168 (Figure 6.51). 

Aminocarbazoles are typical aromatic amines 3-aminocarbazoles, which are the most studied, form Schiff bases with aromatic aldehydes, and ketones. Use was made of such a benzaldehyde imine by methyla-tion with dimethyl sulfate and then by hydrolysis with acid to produce the mono-N-methylated amine. The dimethylated material was obtained via the trimethylammonium iodide, which gave 3-dimethylaminocarbazole on... 

For 5-alkylidenetetrazolines (33) three reaction paths have to be considered. They afford either N-methyl ketene imines and methyl azide, or, in addition to molecular nitrogen, a 3-alkylidenediaziridine (least-motion path) or a methyliminoaziridine (non-least-motion path). As was shown by... 

The preferred tautomer of the products derived from the condensation reaction of phenylenediamine with cyclic /3-keto esters (Scheme 5) is highly dependent on the structure of the /3-ketoester <2005JHC1001>. H and 13C NMR analysis of the l,5-benzodiazepin-2-one 34, formed from methyl 2-oxocyclohexanecarboxylate under micro-wave conditions, indicated the presence of the C(4)-N(5) imine <2005JHC1001>. In contrast, the products arising from condensation with methyl 2-oxocyclopentanecarboxylate and methyl l-alkyl-4-oxopiperidine-3-carboxylates were found to be in the enamine form 35. 

Similar to the addition to HFIPA, the /MCD-mediated addition of methyl, phenyl, and naphthyl acrylates to N-sulfonyl imines afforded the (S)-adduct, which is opposite to that observed with aldehydes (Table 5.12) [95]. The best conditions were found using either dichloromethane or acetonitrile as solvent. 

Imines (98) may be lithiated66 if (a) they have no other acidic protons a to C=N and (b) they are A-methyl imines or they have other activation towards a-lithiation. The N-allyl amidines 99, for example, give interesting chiral organolithiums 100 with BuLi.67... 

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