Mono-formylation

For the porphyrin with the formyl substituents, the -CH=0 stretching mode (vch=o) also gives a prominent RR band. It is noted that the vch=o frequency of mono-formyl porphyrin is independent of the substituted position in an organic solution but when... 

In analogy to the hydroformylation of dienes, the doubly unsaturated sorbate ester gave no diformyl product but only the mono-formyl compound [60] (see also page 40). 

Active methylene or methine compounds, to which two EWGs such as carbonyl, alko.xycarbonyl, formyl, cyano, nitro, and sulfonyl groups are attached, react with butadiene smoothly and their acidic hydrogens are displaced with the 2,7-octadienyl group to give mono- and disubstituted compounds[59]. 3-Substituted 1,7-octadienes are obtained as minor products. The reaction is earned out with a /3-keto ester, /9-diketone, malonate, Q-formyl ketones, a-cyano and Q-nitro esters, cya noacetamide, and phenylsulfonylacetate. Di(octadienyl)malonate (61) obtained by this reaction is converted into an... 

The Vilsmeier formylation of copper deuteroporphyrin dimethyl ester (6) in which unsubstituted /3-positions are present yields a complex mixture of mono- and disubstituted formylation products which can be partially separated by chromatography on neutral alumina.106... 

A similar ambiguity concerning structure appears to arise for 1,4-imidoquinone diazides (4.6), which were synthesized many years ago by Dimroth et al. (1917) and by Morgan and Upton (1917), and were reinvestigated by Kazitsyna et al. (1965, 1967, 1968a). Such compounds are obtained by diazotization of 4-aminodiphenylamine and mono-acylated or -formylated 1,4-diaminobenzenes. Under the influence of the... 

The formylation of P-H bonds in mono and multiprimary phosphines, which result in the formation of hydroxymethyl phosphines, is among the facile useful reactions in organophosphorus chemistry. As shown in Scheme 9, formaldehyde in the presence of platinum catalysts transforms P-H bonds into hydroxymethyl (P-CHjOH) functionahties (Scheme 9) [52]. 

An unusual series of nonterpenoid aliphatic isothiocyanates from a Fijian Pseudaxinyssa sp. was evident by their strong IR absorption [68]. After silica gel and reverse-phase HPLC experiments, the structures of (Z,Z)-1,18-diisothiocyanooctadeca-1,17-diene (134, n = 14), mp 15°C, and seven other di-olefinic a,mono-olefinic a, o>bisisothiocyanates (135, n = 9-18) and three a-isothiocyano-co-formyl mono-olefins (136, n = 9, 15, 16) were also identified by spectral data... 

The transformation of lithio derivatives of dibenzothiophene into alkyl, alkenyl, hydroxyalkyl, formyl, acetyl, carboxylic acid, alkyl and arylsilyl, boronic acid, aryl and carbinol derivatives of dibenzothiophene is dealt with in the appropriate sections. In addition, the four mono-tritio derivatives of dibenzothiophene have been prepared from the corresponding lithio derivatives via hydrolysis with tritiated water (Section III, 0,2). ... 

Peracid oxidation of the D-homo-oestrone derivative (59) gave the C-ring aromatic compound (60). ° Mono- or tri-formylation with DMF-POCI3 of 17-methylene-steroids led to the unsaturated aldehydes (61) or the dimethylamino-bisaldehydes (62) which were readily converted with NHa-EtOH into the heterocycles (63). 14-Azidopregnanes are available from the reactions of A -... 

Melamine (MF) resins (Cymel, Melmac, Resimene) are produced by the formylation of melamine (2,4,6-triamino-1,3,5-triazine). Melamine has six active hydrogen atoms and hence forms mono-, di , tri-, tetra-, penta, and hexamethylo melamines. The methylol derivatives may be etherified with alcohols such as 1-butanol. A hexamethyl ether (hexamethoxymethylmela-mine) is commercially available and may be used as an intermediate. Some of the reactions leading to resinification of melamine are shown in Figure 15.6. 

Ferrocene is similar to other highly reactive aromatic systems, in that it is readily formylated by N-methylformanilide in the presence of phosphorus oxychloride (5, 29, 107, 113, 118). Only the mono-substituted product, ferrocene-carboxaldehyde (XVI), is produced even when a large excess of formylating agent is used. 

Substitution products can be obtained from some 1,4-dithiins. Thus, 2,5-diphenyldithiin is formylated under Vilsmeier conditions, and mono- or di-nitrated and brominated in the heterocyclic ring. 1,4-Benzodithiin shows similar properties (see Scheme 51). 

Acyclic Schiff base derivatives represent a resourceful class of compartmental ligands which are prepared by self-condensation of appropriate formyl and amine precursors. The condensation reaction is simple and generally leads to the desired product in high yield. Literature data on Lnm mono- and bimetallic complexes, as well as on 4f-d transition metal bimetallic entities with these derivatives are abundant and have been reviewed recently (Vigato and Tamburini, 2004). Extension to multimetallic systems and to complexes with 5f elements... 

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