Tris amine, formylation

The reaction of tertiary formamides with sulfur tetrafluoride in the presence of potassium fluoride leads to replacement of both the carbonyl oxygen and formyl hydrogen atoms by fluorine. The formyl group is directly converted into the trifluoromethyl group to give N-(trifluoromethyl)amines which are isolated in almost quantitative yield (see Section 8.2.10.). Thus, dimethylformamide, diethylformamide, piperidinc-l-carbaldehyde, morpholine-1-carbaldehyde and ethyl(phenyl)formamide were converted into the corresponding A -(tri-fluoromethyl)amines 11.175... 

Formylation of the less reactive phenol and anisole with CO in HF-BF3 was found to require at least stoichiometric amount of the acid for effective transformation (50 equiv. of HF, 2 equiv. of BF3, 50 bar CO, 45°C).445 Conversion increases with increasing reaction time but results in decreasing paralortho ratios suggesting a change from kinetic control to thermodynamic control and the reversibility of formylation. Furthermore, the amount of byproducts (mainly diphenylmethane derivatives) originating from reactions between substrates and products also increases. Additional studies in ionic liquids showed that imidazolium cations with increased chain lengths—for example, l-octyl-3-methylimidazolium salts—are effective in the formylation process. This was attributed to the enhanced solubility of CO in the ionic liquid medium. Tris(dichloromethyl)amine, triformamide, and tris (diformylamino)methane have recently been applied in the formylation of activated aromatic compounds in the presence of triflic acid at low temperature (— 10 to 20°C) albeit yields are moderate.446... 

Formylation of amines and alcohols. Behai,8 discoverer of the reagent, found that it reacts unidirectionally with simple alcohols to produce alkyl formates free from acetates. Hurd et al. J found that acetic-formic anhydride (prepared from formic acid and ketene) reacts quantitatively with aniline to give formanilide. Another study10 established that acetic-formic anhydride mixes endothermally with 2-nitro-2-methyl-l-propanol, exothermally with 2-nitro-2-methyl-l,3-propanediol, and displays no appreciable temperature effect with either 2-nitro-l-butanol or tris-(hydroxymethyl)-nitromethane. Formic esters are favored by avoiding a high reaction temperature and by not using sulfuric acid as catalyst. The mixed anhydride has been used for the preparation of formyl fluoride.11... 

The elaboration of routine synthetic methodologies such as the condensation reaction of 2-formyl- or 2-acyl-phenols with primary amines, sometimes followed by reduction, can be utilized in the synthesis of poly-aryloxide ligands including macro-cyclic examples. Some types of tris-aryloxides obtained in this way are shown in Scheme 6.7 (A) and Examples of a nonmacrocyclic tetra-aryloxide (C), and... 

After completion of the reaction, the catalyst was separated from the product by extraction with an aqueous NaOH solution. Acidification of the formed tris(sulfonylphenyl)phosphine sodium (TPPTS) and subsequent neutralization with bis(2-ethylhexyl)amine allowed the catalyst to be reused. The formyl alcohols, in turn, were converted into the corresponding nonadecandiols by hydrogenation on a heterogeneous Ni catalyst. A typical run with 330 g olefin carried out in a pilot plant is shown in Figure 6.14. 

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