Methine condensation

Naturally occurring porphyrins are usually symmetrically substituted about the 15-methine bridge. These porphyrins can be synthesized by the condensation of two dipyrroiic intermediates. Typical dipyrroiic intermediates in current use arc the dipyrromethanes and the dipyrromethenes. Both methods will shortly be described. This again is a highly specialized... 

The three methine carbons of the chain can be provided by 1.3.3-triethoxypropene (method C) or /S-anilinoacroleinanil, vinylog of diphenyl formamidine issued from the condensation of aniline on tetraal-koxypropane (method A). 

The electronic structure of a trimethine asymmetrical cyanine, controls the attack of a ketomethylene (Scheme 54). There is a condensation of the nucleophilic carbon on the electrophilic central carbon atom of the methine chain, leading to a neutrodimethine cyanine and simultaneously elimination of the more basic nucleus. 

Iron Porphyrins. Porphyrias (15—17) are aromatic cycHc compouads that coasist of four pyrrole units linked at the a-positions by methine carbons. The extended TT-systems of these compounds give rise to intense absorption bands in the uv/vis region of the spectmm. The most intense absorption, which is called the Soret band, falls neat 400 nm and has 10. The TT-system is also responsible for the notable ring current effect observed in H-nmr spectra, the preference for planar conformations, the prevalence of electrophilic substitution reactions, and the redox chemistry of these compounds. Porphyrins obtained from natural sources have a variety of peripheral substituents and substitution patterns. Two important types of synthetic porphyrins are the meso-tetraaryl porphyrins, such as 5,10,15,20-tetraphenylporphine [917-23-7] (H2(TPP)) (7) and P-octaalkylporphyrins, such as 2,3,7,8,12,13,17,18-octaethylporphine [2683-82-1] (H2(OEP)) (8). Both types can be prepared by condensation of pyrroles and aldehydes (qv). 

Another alternative makes use of the condensation of 5,5 -dimethyidipyrryimethenes8and 5,5 -dibromodipyrrylmethenes 9 in organic melts. In this case, the method allows the synthesis of more diversely substituted porphyrins 10. To avoid constitutionally isomeric porphyrins it is neccessary to start with one dipyrrylmcthene which is symmetrically substituted about the methine carbon. 

The formation of porphyrins from 1,19-dideoxybi)enes-/r can be achieved starting either from the 1-methyl derivatives or from l,19-dideoxybilene-Z>-l,19-dicarboxylic acid esters. In the first case the desired methine bridge of the porphyrin stems from the 1-methyl group whereas in the latter case orthoformates have to be added in the condensation step as a precursor for the methine unit. The 1-methyl- and also 1,19-dimethyl-l,19-dideoxybilene- > salts can be cy-clized to the corresponding porphyrins with copper(II) acetate in methanol.56 However, when the bilenes contain /i-acceptor substituents, the yields of porphyrins obtained by this method are very low.57... 

The synthesis of [261hexaphyrin(l. 1.1.1.1.1) which is formally derived from porphyrin by extension of two pyrrole subunits and the corresponding methine bridges follows a classical analogous McDonald [3 + 3] approach by condensation of two tripyrrane building blocks.2 2a d... 

CINNOLINES AND QUINOXALINES Replacement of a methine in oxolinic acid (46) by nitrogen is apparently consistent with retention of antibacterial activity. One approach begins with reduction of nitroacetophenone 144 to afford the corresponding aminoketone (145). Treatment of this intermediate with nitrous acid leads to the diazonium salt the diazonium group condenses with the ketone methylene group (as its enol form) to lead to the cyclized product, cinnoline 147. Bromination proceeds at the position adjacent the enol grouping (148) ... 

The name of this structural class ( quinoline ) in the Colour Index is not ideal because quinoline derivatives feature in other related classes, such as the methine basic dyes with a quinolinium cationic group. The class is more precisely associated with quinophthalone (1.15), the characteristic chromogen derived by condensation of quinoline derivatives with phthalic anhydride. This small class of yellow compounds contributes to the disperse, acid, basic and solvent ranges of dyes. 

Uncharged styryl (methine) disperse dyes were originally introduced to provide greenish yellow colours on cellulose acetate fibres. One such dye still in use is Cl Disperse Yellow 31 (6.226), which is made by condensing 4-(N-butyl-N-chloroethylamino)benzaldehyde with ethyl cyanoacetate. Suitable compounds for polyester usually contain the electron-accepting dicyanovinyl group, introduced with the aid of malononitrile. An increased molecular size leads to improved fastness to sublimation, as in the case of Cl Disperse Yellow 99 (6.227). A novel polymethine-type structure of great interest is present in Cl Disperse Blue 354 (6.228), which is claimed to be the most brilliant blue disperse dye currently available [85]. 

Quinophthalone (6.229) and its derivatives [86] also fall into the methine category, although they appear in the Colour Index under quinoline colouring matters. The parent compound was discovered in 1882 by Jacobsen, who condensed 2-methylquinoline (quinaldine) with phthalic anhydride. The product, quinoline yellow, is used as a solvent dye (Cl Solvent Yellow 33). The light fastness is improved by the presence of a hydroxy group in the quinoline ring system. Derivatives of this type provide greenish yellow disperse dyes for polyester. The moderate sublimation fastness of Cl Disperse Yellow 54 (6.230 R = H) is improved by the introduction of an adjacent bromine atom in Cl Disperse Yellow 64 (6.230 R = Br). 

In chlorophyll iron as complex-forming metal is replaced by magnesium (Willstatter). The structure of chlorophyll differs from that of haemin as follows. In chlorophyll one propionic acid chain (a) in oxidised form has condensed with a methine carbon atom to form a cyclopentane ring which takes the position at (c) of the vinyl ethyl. Further the two carbonyl groups are esterified and one of the four pyrrole rings is partially hydrogenated... 

The bis(triazolopyrimidyl)methanes 39 were quaternized with methyl p-toluenesulfonate to give 254, whose treatment with base gave the mesoionic methine dyes 255 (82UKZ79). The methylene group of 39 was active to be condensed with aldehydes (Scheme 48). 

The chemistry of 1,3-diketone complexes of nonmetallic elements (B, Si, Ge, Sb, Te) has been reviewed.68 Condensation of acetylacetone with TeCl4 yields Te(CH2COCH2COCH2)Cl2 (8a), which may be reduced to Te(CH2COCH2COCFI2) (8b). The crystal structures of these compounds demonstrate an unusual coordination of tellurium to the terminal carbons of the diketonate.61 72 In the dichloride complex, Teiv exhibits a distorted trigonal bipyramidal geometry with a stereochemi-cally active lone electron pair in the equatorial plane. In S2(MeCOCHCOMe)2 the acetylacetonate methine carbons are bonded to a disulfur unit.73... 

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