1.1- diphenylhydrazine, oxidation

Hall et al. (1985) reported that no 1,2-diphenylhydrazine (less than pg/L) was detected in the Nanticoke River near the Chesapeake Bay. The analytical method involved liquid-liquid extraction, concentration, and. analysis by GC/MS. The Contract Laboratory Program statistical database (queried April 13, 1987) reported that 1 2-diphenylhydrazine has been detected n water at i of 357 hazardous waste sites at a concentration of (96 ppb (CLPSDB 1987), and has been reported at 7 of 117, sites. n the national Priority List database (ATSDR 1990) The U.S. EPA Contract laboratory Program uses GC methods to analyze the contaminants of interest. Since 1,2-diphenylhydrazine oxidize, to azobenzene in the GC injector port and both 1,2-diphenylhydrazine and azobenzene, have the same GC retention time and mass spectra, reports of 1,2-diphenylhydrazine from the Contract Laboratory Program may actually represent detections of 1,2-diphenylhydrazine, azobenzene, or both (see Chapter 6 for more details). 

Diphenylhydrazine (hydrazobenzene) [122-66-7] M 184.2, m 34°, 44°, 175°/10mm, 222°/40mm, pKe i -1.7. Crystd from hot EtOH containing a little ammonium sulfide or H2SO3 (to prevent atmospheric oxidation), preferably under nitrogen. Dried in a vacuum desiccator. Also crystd from pet ether (b 60-100°) to constant absorption spectrum. HCl, from EtOH has m 163-164°(dec). Picrate, from C6H6, has m 123°(dec). 

Interaction, in presence of diluent below 0°C, with isopropylamine or isobuty-lamine caused separation of explosive liquids, and with aniline, phenylhydrazine and 1,2-diphenylhydrazine, explosive solids [1], In absence of diluents, contact with most aliphatic or non-aromatic heterocyclic amines often leads to uncontrolled oxidation and/or explosions [2], During oxidation of two steroidal dienes in dry pyridine at —35 to —40°C, on one occasion each of the reactions was accompanied by violent explosions [3],... 

The oxidative properties of ditelluronium and diselenonium dications are similar to S-S dications. For instance, interaction of thiophenol or 1,2-diphenylhydrazine with either the diselenonium dication 113 or the ditelluronium dication 114 leads to almost quantitative formation of diphenyldisulfide or azobenzene and reduced bis-chalcogenides.113,114,124 Reduction of 113 and 114 with NaBH4 gives the same products as above but proceeds quantitatively via direct electron transfer (Scheme 47).128... 

Chemical/Physical. Wet oxidation of 1,2-diphenylhydrazine at 320 °C yielded formic and acetic acids (Randall and Knopp, 1980). 1,2-Diphenylhydrazine will not hydrolyze (Kollig, 1993). 

DIPT, see Isopropyl ether Dipentyl, see Decane Diphenyl, see Biphenyl 1,1 -Diphenyl, see Biphenyl 4,4 -Diphenylenediamine, see Benzidine p,p -Diphenylenediamine, see Benzidine Diphenylenemethane, see Fluorene o-Diphenylenemethane, see Fluorene Diphenylene oxide, see Dibenzofuran Diphenyl ether, see Phenyl ether s/m-Diphenylhydrazine, see 1,2-Diphenylhydrazine lV,A/ -Diphenylhydrazine, see 1,2-Diphenylhydrazine Diphenylnitrosamine, see IV-Nitrosodiphenylamine Diphenyl-lV-nitrosamine, see IV-Nitrosodiphenylamine A,lV-Diphenylnitrosamine, see IV-Nitrosodiphenylamine A,Al-Diphenyl-lV-nitrosamine, see IV-Nitrosodiphenylamine Diphenyl oxide, see Phenyl ether Diphenyltrichloroethane, see p,p -DDT Diphosphoric acid, tetraethyl ester, see Tetraethyl pyrophosphate... 

Very little information was located in the literature concerning the disposal of 1,2-diphenylhydrazine. Dietrich et al. (1985) reported that wet air oxidation (heating wastewater under pressure with the addition of an oxygen-containing gas such as air) would remove 99.88% of the... 

No information concerning the transport and partitioning of 1,2-diphenylhydrazine in the environment was located in the literature. In water, 1,2-diphenylhydrazine is not expected to volatilize because of its rapid oxidation in aerated water (near-surface water) to azobenzene and its low calculated Henry s Law constant (9.42 x 10 atm-m mof) (Lyman et al. 1982). The calculated log Koc (2.76) suggests that 1,2-diphenylhydrazine may sorb to sediments or suspended particles. This is based on the analysis of Kenaga (1980), who stated that chemicals with a K°<= <100 tend to be mobile in soil, while those with a K°<= >L000 tend to sorb. In soil, 1,2-diphenylhydrazine is not expected to leach to groundwater, based on its physical and chemical properties (i.e.. 1,2-diphenylhydrazine reacts rapidly under environmental conditions and, based on its K°c will not rapidly leach downward in the soil column). 

No ambient air monitoring for 1,2-diphenylhydrazine was located in the literature. This may be due to both the rapid oxidation of 1,2-diphenylhydrazine and its low vapor pressure, which limit the amount of 1,2-diphenylhydrazine entering the atmosphere. In addition, no information was located suggesting that any studies have sought but not found 1,2-diphenylhydrazine. 

Food Chain Bioaccumulation. 1,2-Diphenylhydrazine reacts rapidly in water to form azobenzene and other oxidation products (half-life in wastewater is 60 minutes). Because of this and based upon the log octanol/water partition coefficient, no bioaccumulation is expected in any aquatic organism. 

The addition of a phenylsulfoxide moiety to the end of the side chain markedly changes the activity of this class of compounds. This product, sulfinpyrazone (97-11), stimulates uric acid excretion, making it a valuable dmg for dealing with the elevated serum uric acid levels associated with gout. The compound is stiU one of the more important uricosuric agents available today. The starting ester (96-9) is available by alkylation of the dianion from ethyl malonate with 2-chloroethylphenyl thioether. Condensation with diphenylhydrazine (97-3) in the presence of a base then affords the pyrrazolodione (97-10). Oxidation of sulfur with a controlled amount of hydrogen peroxide leads to the sulfoxide and thus sulfinpyrazone (97-11) [107]. 

Diphenylhydrazine [530-50-7] M 184.2, m 126 . Crystd from hot EtOH containing a little ammonium sulphide or H2SO3 (to prevent atmospheric oxidation), preferably under nitrogen. Dried in a vacuum desiccator. 

Anodic oxidation of 1,1-diphenylhydrazine in neutral acetonitrile gives a relatively stable diphenyldiazenium ion 39, which may add to styrene in the... 

Diphenylhydrazine (Ph2NNH2) is converted into indazole (215) by Cl2C = NMe2. Oxidative cyclizations are also known thus, fully methylated 6-(benzylidenehydrazino)uracils (216) on photolysis or in hot AcOH give the pyrazolo[3,4-d]pyrimidines (217) (75BCJ1484,92KGS219). 

Aluminium, 0048 Ammonium phosphinate, 4549 Barium phosphinate, 0210 f Benzaldehyde, 2727 1,4-Benzenediol, 2326 Bis(hydrazine)tin(II) chloride, 4064 Calcium acetylide, 0582 Calcium phosphinate, 3925 Chromium(II) chloride, 4046 Chromium(II) oxide, 4235 Chromium(II) sulfate, 4238 Copper(I) bromide, 0264 Diacetatotetraaquocobalt, 1774 Diisobutylaluminium hydride, 3076 f 1,2-Dimethylhydrazine, 0951 1,2-Diphenylhydrazine, 3511 Dipotassium phosphinate, 4425 f Ethanedial, 0719 f Formaldehyde, 0415 Formic acid, 0417 Gallium(I) oxide, 4405 Glucose, 2513 f Hydrazine, 4515 Hydroxylamine, 4493 Hydroxylaminium phosphinate, 4550 Hyponitrous acid, 4464 Iron(II) chloride, 4055 Iron(II) hydroxide, 4386 Iron(II) sulfate, 4393 Fead(II) phosphinate, 4526 Fead(II) phosphite, 4530 Fithium dithionite, 4682 Magnesium, 4685 Magnesium phosphinate, 4512 Manganese(II) phosphinate, 4514 f Methylhydrazine, 0500 Phenylhydrazine, 2366 Phosphinic acid, 4498 Phosphonic acid, 4499 Phosphonium iodide, 4510 Potassium, 4640 Potassium hypoborate, 0163... 

The intermediately formed hydrazine linkages would be oxidized to azolinkages in a subsequent reaction considerably faster than the oxidation of the amine as shown by Terent ev (28, 29) for diphenylhydrazines. 

Diphenylhydrazine is oxidized to diphenylnitrosamine (50%) by potassium superoxide. The same reagent also oxidizes 1-methyl-1-phenylhydrazine, but here the nitrosamine is a minor product the major reaction is deamination. A better meAod of oxidative deamination of some 1,1-disubstituted hydrazines and hydrazinium salts is reaction with nitrous acid. Thus, several hydrazinium salts MezRN NHi X were deaminated to the tertiary amine by treatment with nitrous acid. The method has also been used to deaminate IV-aminoheterocyclic compounds for example, some 1,2,3-triazoles are conveniently prepared by deamination of the corresponding 1-aminotriazoles with nitrous acid. °... 

With 1,2-diphenylhydrazine (PhNHNHPh), the azobenzene anion radical is rapidly oxidized by dioxygen to azobenzene, which also is true for the phenazine and lumi-flavin anion radicals. Hence, 02 acts as an initiator for the autoxidation of these compounds (equation 153). For 1,2-diphenylhydrazine, turnover numbers in excess of 200 substrate molecules per 02 have been observed. The 1,2-diphenylhydrazine autoxidation cycle can be initiated by HO , which indicates that 02 is formed in the HO initiated process. Superoxide ion also initiates the autoxidation of dihydrophenazine, which is a model for dihydroflavin. For example, the addition of 1 mM (Me4N)02 in DMF to 10 mM H2Phen in an 02-saturated DMF solution results in the complete oxidation of the substrate (about 80% recovered as phenazine) and the production of 9 -10 mM HOOH. 

Y -[2,4,6-tns(tnfluoromethylsulfonyl)phenyl]-A, fV-diphenylhydrazine is oxidized to the stable hydrazyl radical by lead dioxide [84] (equation 76). 

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