Diformylation

Pyrrole, 1 -benzyl-2-(2-carboxybenzoyl)-intramolecular acylation, 4, 221 Pyrrole, l-benzyl-2,5-dichloro-3,4-diformyl-reactions... 

Pyrrole, 2,4-diethyl-3,5-dipropionyl-protodeacylation, 4, 208 Pyrrole, diformyl-reactions... 

Triazole has been prepared by the oxidation of substituted 1,2,4-triazoles, by the treatment of urazole with phosphorus pentasulfide, by heating equimolar quantities of formyl-hydrazine and formamide, by removal of the amino function of 4-amino-l,2,4-triazole, by oxidation of l,2,4-triazole-3(5)-thiol with hydrogen peroxide, by decarboxylation of 1,2,4-triazole-3(5)-carboxylic acid, by heating hydrazine salts with form-amide,by rapidly distilling hydrazine hydrate mixed with two molar equivalents of formamide, i by heating N,N -diformyl-hydrazine with excess ammonia in an autoclave at 200° for 24 hours, and by the reaction of 1,3,5-triazine and hydrazine monohydrochloride. ... 

Glutaraldehyde (1,3-diformyl propane) is a powerful, cold disinfectant. It is used principally in aqueous solution as a biocide and chemical disinfectant. It has been widely used in the health services, e.g. in operating theatres, endoscopy units, dental units and X-ray film processing. 

The most recent synthetic efforts in this area have focused on the preparation of mono- and diformyl-substituted indolo[3,2-l)]carbazoles 202 and 203, which are potent aryl hydrocarbon receptor (AHR) ligands (cf. Section V,C). 

During synthetic studies toward pynrolo-fiised indoles, the polymeric species 218 has been suggested as aproduct from the diformylation of 219 under Vilsmeier-Amold-Haack conditions, followed by heating with 35% aqueous sulfuric acid (Scheme 33) (9171,5035). With the deeper knowledge of the reactions of 3-formylIndoles now available (99CHE561), this assignment should be reconsidered. 

The reaction of diacetylene with cyanic acid (HCNO) proceeds at room temperature in the presence of sulfuric acid in aqueous methanol to give 3-formyl-5,5 -diisoxazol-3 -aldoxime (85) and 3,3 -diformyl-5,5 -diisoxazoldioxime (86), whose oxidation with potassium permanganate followed by esterification results in 3,3 -dicarbomethoxy-5,5 -diisoxazoles (87) (59G598). 

In contrast to biphenyl-2,2 -dicarbaldehyde, the corresponding diformyl derivative of 1,1 -binaphthyl can be transformed to the annulated 1,2-diazocine derivative.21... 

In contrast to the Vilsmeier formylation the formylation with trimethyl orthoformate in trifluoroacetic acid proceeds with high selectivity so that only the /3-monoformylated deuteroporphyrin derivatives 8 are formed without any methinc substituted or diformylated products.1073 6... 

Can be prepd by the nitration of 1-phenyltetrazole with fuming nitric acid, or by heating sym diformyl-hydrazine, OHC.HN.NH.CHO, and p-nitrobenzene-diazonium chloride, 02N.C6H4.N2C1, with dil Na hydroxide soln. Insol in w and ligr, diff sol in benz and eth, sol in ethanol and methanol, v sol in acet. Puffs off when heated above its mp Refs 1) Beil 26, 347 (109) 2)M. Freund ... 

Nieht reduzierbar sind l,l-Dialkyl-2-benzoyl-hydrazine und 1,2-Diformyl-hydrazin. 

Analog erhalt man aus Trimethyl-formyl-hydrazin Tetramethyl-hydrazin (55% d.Th. Kp 71-72°). Die Reduktion von l,2-Dimethyl-l,2-diformyl-hydrazin ergibt nur 15% d.Th. Tetramethyl-hydrazin5 (zur Arbeitsvorschrift s. ds. Handb., Bd. X/2, S. 50). 

Diformyl-1,1 -binaphthyl Ia6t sich praktisch quantitativ zu Anthanthren cyclisieren (get. Zelle, Ccllophan-Diaphragma Hg-Kathode, Graphit-Anode)1 ... 

Dimethylamino-methyl)-2-hydroxymethyl-aus 2 -Carboxy-2-(dimethylaminocarbonyl)-biphenyl und Lithiumalanat 165 2,2 -Dinitro- 474, 476, 695 6,6 -Dinitro-2,2 -bis-[chlorcarbonyl]- 188 2,2 -Dinitro-4,4 -bis-[diathylamino]- 695 4,4 -Dinitro-2,2 -bis-rhydroxymethyl]- 213 6,6 -Dinitro-2,2 -bis-[hydroxymethyl]- 188 2,2 -Dinitro-4,4 -diamino- 695 6,6 -Dinitro-2,2 -diformyl- 694 4,4 -Dinitro-2,2 -dimethoxycarbonyl- 213 2,2 -Dinitro-4,4 -dimethyl- 695 6,6 -Dinitro-2 -formyl-2-carboxy- 694 2,2 -Dinitroso- 476 -4-hydroxamsaure-chlorid 537 4-(a-Hydroxy-benzyl)- 542 Methoxy- 678 2-Methyl- 556 Nitro- 672, 678 4-Nitro- 687... 

Disubstituted tetrazoles are conveniently prepared from acyl hydrazines (98) and diazonium salts.166 The reaction proceeds through the intermediate tetrazenes (99) followed by cyclization to the tetrazole (100) (Scheme 13). The intermediate can be isolated under mildly basic conditions. Symmetrically 1,2-diacylated hydrazines yield 1-substituted tetrazoles through the elimination of one of the acyl groups.166 - 168 Diformyl-hydrazine is a very convenient starting material for 1-substituted tetrazoles.166, Unsymmetrically 1,2-diacylated hydrazine usually results in mixtures.169... 

In contrast with the Schiff base salen, salicylaldehyde oxime (79) (salox) complexes of Co have received comparatively little attention, but a series of bis-bidentate divalent complexes of the form iraiis-Co(sa 1 ox)2( D M SO)2 have been reported.343 The heterocyclic bidentate oxime violurate (lH,3H-pyrimidine-2,4,5,6-tetrone 5-oximate, Hvi) (80) and its /V-methyl (mvi) and /V,/V -dimethyl (dmvi) derivatives form high-spin divalent [Co(vi)]+ and Co(vi)2 complexes, whereas [Co(vi)3] is low spin.344 The mixed-ligand Co(dmvi)2(phen) complex is also low spin. The crystal structure of m-Co(pxo)2Br2 (pxo = 2-acetylpyridine-l-oxide oxime) is isostructural with the Ni11 relative.345 The dichloro complex also adopts a cis configuration. The tridentate dioximes 2,6-diformyl-4-methylphenol dioxime and 2,6-diacetyl-4-methylphenol dioxime (Hdampo) form binuclear complexes of the type (81a) and (81b) respectively.346 Cobalt oxide nanoparticles were prepared by... 

Macrocyclic Schiff base compartmental ligands (750) (Robson-type ligands) derived from the [2 + 2] condensation of a 2,6-diformyl- or 2,6-diketo-substituted phenol and a diamine are very prominent in dinuclear Ni coordination chemistry.1901-1903 Particular interest lies in magnetic exchange interactions between the adjacent metal ions as well as in bioinorganic chemistry, where such dinuclear complexes have been proposed as synthetic analogues for bimetallosites. 

Using 2,6-diformyl-4-methylphenol dioxime, Tasker, Schroder, and their co-workers conducted a magnetostructural study on complex (374) (pseudo macrocyclic structure Cu-Cu 2.994 A 2J= — 904 cm-1).330 Using 2-hydroxy-5-nitro-benzaldehyde benzoylhydrazone as ligand, complex (375) (Cu-Cu 3.041 A 2J=—372cm 1) was reported.331 Using 3-formylsalicylic acid oxime Okawa and co-workers reported complex (376) (square-planar and SP geometry Cu-Cu 2.961 A).332... 

Amino-1,2,4-triazole has been obtained from orthoformic ester and hydrazine hydrate in a sealed tube at 120° 1 by heating formylhydrazine at 150-210° 2-3-4 by heating N,N -diformyl-hydrazine at 160° 5 by decarboxylation of 4-amino-1,2,4-tria-zoldicarboxylic acid 6 by fusion of l,2-dihydro-l,2,4,5-tetrazine 6 and by heating l,2-dihydro-l,2,4,5-tetrazinedicarboxylic add above its melting point.4-6-7... 

Spontaneous formation of the Schiff base [3 + 6] macrocycle being a derivative of 2,6-diformyl-4-methylphenol and polyamine has been shown by Schmidt et al. [10].26... 

---