Nitro phenylhydrazine

Filter, wash toluene with water, NaHC03, water and dry, evaporate in vacuum to get 100 g gamma-Cl-butyraldehyde (I) (can distill 28/2). 10 g (I), 20 g 3-nitro-phenylhydrazine dissolve in the minimum volume of hot ethanol containing 10% glacial acetic acid. Heat on steam bath one hour cool and add water until dark oil separates. Evaporate in vacuum the ethanol and decant the water to get the oily gamma-Cl-butyraldehyde-3-intro-phenylhydrazone(II). 29 g (11), 300 ml concentrated HC1, ZOO ml benzene stir three hours, replace benzene with fresh benzene and stir four hours. Combine the two benzene portions, wash with water and dry, evaporate in vacuum to get 4 g 3-(beta-Cl-ethyl)-4 and 6-nitroindole (m). 3.56 g (III), 200 ml ethanol, 200 ml 34% aqueous DMA (or other amine) and let stand at room temperature for one week. Evaporate in vacuum the ethanol, filter, dissolve the precipitate in dilute HC1 and filter. Basify the filtrate with dilute NaOH to precipitate 3 g 4 and 6-nitro-DMT (IV). 5.2 g (IV), 350 ml ethanol, 100 ml IN NaOH heat to 50° and add a solution of 3 g Na dithionite in 15 ml 0.2N NaOH. filter hot and evaporate in vacuum to get 2 g 4 and 6 amino-DMT (can purity by dissolving in HC1, filter, basify, extract with ether and dry and evaporate in vacuum the extract). 

Behandelt man 3-Nitro-benzoldiazoniumtetrafluoroborat mit Natriumboranat, so entsteht neben Nitro-benzol, 3-Nitro-anilin, 3-Nitro-phenylazid und 3-Nitro-phenylhydrazin auch zu 19% 3,3 -Dinitro-azoben-zol3. Mil anderen Aryldiazonium-tetrafluoroboraten erzielt man folgende Ergebnisse ... 

Selenium acetylacetone also undergoes the following reactions 1 One molecule of the compound reacts with two molecules of p-nitro-phenylhydrazine to give p-nitrobenzeneazoacetylacetone, 1-p-nitro-phenyl-3 5-dimethylpyrazole and di-p-nitrophenylhydrazinoacetyl-acetone. With one or two molecular proportions of aniline, selenium and 1 3-dianilinoacetylacetone are obtained,... 

Reaction CXXVlil. Action of Phenylhydrazine, etc., on Aldehydes and Ketones.—Phenylhydrazones of aldehydes and ketones are generally formed by warming these substances in aqueous-alcoholic solution with phenylhydrazine, phenylhydrazine acetate or phenylhydrazine hydrochloride in presence of excess sodium acetate. Derivatives of phenylhydrazine (e.g., p-nitro-phenylhydrazine) also react in a similar manner. 

Heat 0.25 g of the compound with 3 ml of ethanol, add 0.25 g of p-nitro-phenylhydrazine and heat the suspension until the reaction appears complete. The p-nitrophenylhydrazone soon separates. Filter, preferably after standing overnight, wash with a little cold ethanol and then recrystallise from ethanol. 

The yield of product melting at 156-157° (sintering a few degrees lower) is about 30 grams, or 70-80 per cent of the theoretical amount. This product is suitable for most purposes without further treatment. Recrystallization from 20 parts of alcohol gives completely pure p-nitro-phenylhydrazine in the form of slender brown plates with a bluish surface reflection, melting sharply at 157-158°. 

T Nitro Phenylhydrazine Reaction A An aqueous solution of /)-nitro phenylhydrazine hydrochloride, which should remain colourless on addition of a few drops of acetic acid, produces an orange-yellow precipitate with acrolein. This precipitate consists of small stellar crystals, easily visible under the microscope. 

Preparation. 1-Hydroxybenzotriazole is prepared by the reaction of o-nitro-phenylhydrazine with aqueous ammonia.1... 

Malondialdehyd wird zur Synthese von 3,4,5-unsubstituierten lH-Pyrazolen im allgemeinen als Tetra-O-acetal eingesetzt (s. S.413). Die Umsetzung des Ammonium-Salzes von Malonal-dehyd mit 4-Nitro-phenylhydrazin fuhrt zu l-(4-Nitro-phenyl)-lH-pyrazol [Bd. X/2, S. 589 (1967)]. In a-Stellung substituierte Malondialdehyde dienen zur Synthese von 4-substituier-ten 1 H-Pyrazolen. Die Reaktion wird in Ethanol, zumeist in Gegenwart von Mineralsaure, durch Erhitzen am RiickfluB durchgefiihrt. 

Filter, wash toluene with water, NaHCOs, water and dry, evaporate in vaeuum to get 100 g gamma-Cl-butyraldehyde (I) (ean distill 28/2). 10 g (1), 20 g 3-nitro-phenylhydrazine dissolve in the... 

Products formed from 1,3,5-triketones (XII-765) or 7-pyrones and p-nitro-phenylhydrazine had originally been assigned the structures XII-766 and XII-767.7 799 However, it has been shown that 4-pyrone and p-nitrophenyl-hydrazine give the p-nitrophenylhydrazone of the pyrazole (XII-768, R = H). ... 

Surfactants (surface active agents) are very important constituents of many industrial formulations. In these formulations, it is often not just one compound that is of interest. Rather, the overall identity, as determined by the presence and distribution of the individual components, is critical. Kondoh et al. [224] developed a method for determining non-ionic surfactants containing ester groups, such as sorbitan and sucrose fatty acid esters and polyoxyethylene fatty acid esters, as their o-nitro-phenylhydrazine derivatives. To remove the residual free fatty acid fraction, 6 mM triethylamine (TEA) was added to the 85/15 methanol/water starting mobile phase. The free fatty acids then eluted in the void volume and the separation of the analytes of interest was conducted on a C]g column (A = 550 nm). Elution and identification up to the penta-ester resulted when a 50-min 0/85/1575/25/0 ethanol/ methanol/water (6 mM TEA) gradient was used. 

Gyanomethyl N-benzoylglycinate refluxed 20-40 hrs. with 1.2 moles of p-nitro-phenylhydrazine in ethyl acetate -> hippuric acid p-nitrophenylhydrazide. Y 90%.—Similar reactions with the analogous methyl esters failed. F. e. s. P. Grud-zinska, Roczniki Ghem. 34, 1687 (1960). 

Brom.2-nitro-phenylhydrazin 15, 488. 2.Brom-4.nitro-phenylhydrazm 15 II 215. 

Aryl Hydrazones.—The phenylhydrazoncs of aldehydes and ketones of low molecular weight are generally liquids not adapted for derivatives. By using p-bromo-phenylhydrazine. p-nitro-phenylhydrazine, or ff-naphthylhydrazine, solid derivatives often may be obtained. On the other hand, among the aromatic compounds even the lower members yield solit phenylhydrazones. 

Postcolumn reactor alkaline hydrolysis of esters and detection of fatty acids by reaction with 2-nitro-phenylhydrazine absorbance at 550 nm UV, 220 nm... 

Hydroxyaminopyridazine 1-oxides are usually formed by catalytic hydrogenation of the corresponding nitro derivatives over palladium-charcoal in methanol, provided that the reaction is stopped after absorption of two moles of hydrogen. 3-Hydroxyaminopyridazine 1-oxide and 6-amino-4-hydroxyamino-3-methoxypyridazine 1-oxide are prepared in this way, while 5-hydroxyamino-3-methylpyridazine 2-oxide and 5-hydroxyamino-6-methoxy-3-methylpyridazine 2-oxide are obtained by chemical reduction of the corresponding nitro compounds with phenylhydrazine. 

V-nitramines too were reduced to disubstituted hydrazines. Electrolysis in 10% sulfuric acid over copper or lead cathodes reduced AT-nitrodimethylamine to. /V,JV-dimethylhydrazine (yield 69%), 7V-nitro-JV-methylaniline to N-methyl-JV-phenylhydrazine (yield 54%), W-nitropiperidine to JV,A -penta-methylenehydrazine (yield 52%) [734], and nitrourea to semicarbazide (yield 61-69%) [755]. 

A solution of trifluoroacetic acid in toluene was found to be advantageous for cyclization of pyruvate hydrazoncs having nitro substituents[4], p-Toluene-sulfonic acid or Amberlyst-15 in toluene has also been found to give excellent results in preparation of indole-2-carboxylate esters from pyruvate hydra-zones[5,6J. Acidic zeolite catalysts have been used with xylene as a solvent to convert phenylhydrazines and ketones to indoles both in one-flask procedures and in a flow-through reactor[7]. 

Other reagents that have been used to reduce support-bound aromatic nitro compounds include phenylhydrazine at high temperatures (Entry 5, Table 10.12), sodium borohydride in the presence of copper(II) acetylacetonate [100], chromium(II) chloride [196], Mn(0)/TMSCl/CrCl2 [197], lithium aluminum hydride (Entry 3, Table... 

Side-reactions can occur, especially in the presence of excess base at elevated temps and prolonged times of reaction, K hydroxide (Ref 82) and anhydrous, ammonia (Ref 20) can form nitrite ion by cleavage of nitro groups. 2,4,5-Trinitrophenol and 3,5-dinitrophenol have been isolated from the reaction of TNT with NaOH (Ref 77). Redox reactions give polymeric materials via the formation of azo and azoxy groups, as noted with phenylhydrazine (Ref 58) ... 

The effectiveness of an oxidant as an electrophile is roughly proportional to its acidity or lack of basicity. Phenylhydrazine, a weak base, is a very weak oxidant however, substitution of nitro groups on the aromatic ring decreases the basicity and increases the potency of the hydrazine as an oxidant. 

Experimental Details.20 1—A solution of 2.2 g. of o-erj/yield from sirupy D-erythrose without the isolation of intermediates) in 50 cc. of absolute ethanol was shaken with hydrogen at room temperature and atmospheric pressure in the presence of 0.2 g. of freshly prepared palladium black. The hydrogenation was interrupted after twenty minutes when 1.05 mole-equivalents of hydrogen had been absorbed and the rate had become slow. The sirup obtained after filtration and concentration was stirred with a mixture of 40 cc. of 1 AT sodium hydroxide solution and 10 cc. of ethanol. After the sirup had dissolved, the solution was added dropwise to a stirred mixture of 5 cc. of sulfuric acid and 7.5 cc. of water at 0°. The reaction mixture was then diluted with ice-water and neutralized by stirring with solid barium carbonate. After filtration, a few drops of glacial acetic acid were added to the filtrate and it was concentrated at reduced pressure to a sirup. The sirup was taken up in a small volume of 75% ethanol and 1.5 cc. of a-benzyl-a-phenylhydrazine added. Slow evaporation of this solution then gave 1.4 g. (59%) of D-erytkro-2-desoxypentose benzylphenylhydrazone. 7 After recrystallization from aqueous ethanol, the pure hydrazone melted at 127-128° and showed [a] — 17.7° in pyridine, c 2. 

The reactivity of the carbonyl group in a,/3-unsaturated dialdoses was studied in more detail. The interaction with phenylhydrazine and its derivatives led to different results. 3-0-Benzyl-l,2-0-cyclo-hexyl idene-5,6-dideoxy-a-D-xyZo-hept-5-e nodialdo-l,4-furanose (56) gave57 a (2,4-dinitrophenyl)hydrazone. Action of (2,4-dinitrophenyl)-hydrazine on derivatives 67 led18 to complex mixtures. In the case of the acetylated derivatives (66), as well as of branched-chain derivatives (69), the interaction with (2,4-dinitrophenyl)hydrazine resulted in the formation of the expected hydrazones (Refs. 24 and 51, respectively). The interaction with phenylhydrazine was, however, proved to proceed by two paths in this case. Only the nitro derivatives (66, R = p-nitrophenyl) and (69, R = p-nitrophenyl) were shown24,51 to form the expected hydrazones. The phenyl derivative 66 (D-galacto, R = Ph) and p-methoxyphenyl derivative 69 (R = p-MeOC8H4) afforded substituted pyrazolines (74) (Ref. 24) and (75) (Ref. 51), respectively, as a result of subsequent intramolecular addition of a... 

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