Aniline arsenate

To 1035 g. of syrupy arsenic acid (80-85 Per cent, sp. gr. 2.00/200 Note 1) in a 12-inch evaporating dish, is added 828 g. (800 cc.) of aniline (Note 2) in 100-cc. portions meanwhile, the lumps of aniline arsenate which are formed are broken up by rapid stirring with a porcelain spatula. When all the aniline has been added, the powdered solid is transferred to a 3-I. round-bottom flask equipped with a mechanical stirrer, a thermometer reaching to the lower part of the vessel, and a condenser arranged for downward distillation (Note 3) an additional 800 cc. of aniline is added and the flask slowly heated in an oil bath. The bath may be kept at a temperature not exceeding 170-175° as long as there is any considerable amount of unmelted material in the flask. When the contents of the flask have become liquid the temperature of the bath is dropped and the mixture held at 155-160° (inside temperature), with continual stirring, for at least four and a half hours. The mass will have assumed an intense violet color. 

Arsanilic acid was prepared by Bechamp 1 by heating aniline arsenate to 190-200°. The product was originally described as the anilide of arsenic acid, but Ehrlich and Bertheim 2 showed its structure to be that of a true aryl arsenic acid. 

B hamp 38) obtained a colorless product on heating aniline arsenate with excess aniline. This was subsequently identified as an arsanilic acid. 

Acenaphthene 6-Acetoxy-2,4-dimethyl-m-dioxane Alkyl dimethyl ethylbenzyl ammonium chloride 2-Amino-4-chloro-6-nitrophenol Ammonium polysulfide Ammonium thiosulfate Anilazine Aniline Arsenic pentoxide Basic yellow 2 Bromoacenaphthylene 3-Bromochloro-5,5-dimethyl hydantoin p-Bromo-p-nitrostyrene Cadmium Cadmium chloride Calcium oxide Calcium polysulfide Carvacrol Cetalkonium chloride Cetethyidimonium bromide... 

Aclonifen Amiprofos Ammonium biborate Ammonium borate Ammonium nitrate Ammonium sulfamate Aniline Arsenic trioxide Asulam Atrazine Aziprotryn Benazolin Benazolin-ethyl Bentazon Boron oxide Bromacil Bromobutide 2-s-Butyl-4,6-dinitrophenol o-s-Butylphenol Cacodylic acid... 

The success of the Bart reaction when applied to nuclear- substituted anilines is often much affected by the pH of the reaction-mixture. Furthermore, the yields obtained from some m-substituted anilines, which under the normal conditions are usually low, arc considerably increased by the modifications introduced by Scheller, and by Doak, in which the diazotisation is carried out in ethanolic solution followed by reaction with arsenic trichloride in the presence of a cuprous chloride or bromide catalyst. 

Nitrophenylarsonic acid has been prepared by heating p-nitrobenzenediazonium chloride with arsenious acid in hydrochloric acid, by the action of -nitrobenzenediazonium chloride on sodium arsenite, by the action of sodium arsenite on sodium -nitrobenzeneisodiazo oxide, by the diazotization of -nitro-aniline in acetic acid in the presence of arsenic chloride and cuprous chloride, and by the reaction of -nitrobenzenediazonium borofluoride with sodium arsenite in the presence of cuprous chloride. ... 

Rosaniline or magenta was originally obtained by oxidising with arsenic acid a mixture of aniline with 0- and />-toluidine. The product was then lixiviated and treated with common salt, which converted the ai senate into the hydrochloride of rosaniline. Pararosaniline was prepared in a similar way fiom a niixtuie of aniline and /-toluidine. The series... 

Acetylated aniline 21 was reacted under Skraup/Doebner-von Miller conditions in the presence of an arsenic salt to yield quinoline 22 with concurrent displacement of fluorine. ... 

In the former Soviet Union much use is made of industrial by-products to prepare acid inhibitors. The PB class is obtained by treating technical butyraldehyde with ammonia and polymerising the resulting aldehyde-ammonia. PB-5, for example, with O-Ol-O-15% of an arsenic salt is used in 20-25% HCl. A mixture of urotropine (hexamethyleneimine, hexamine) with potassium iodide, a regulator and a foaming agent is the ChM inhibitor. BA-6 is prepared from the condensation product of hexamine with aniline. A more recent development is the Katapin series which consists of /7-alkyl benzyl pyridine chlorides Katapin A, for example, is the /7-dodecyl compound. 

Continuous exposure to aniline vapors and arsenic compounds ulcerated workers noses, lips, and throats. Hoechst employees left work cov-... 

Arsanilic acid was first synthesised, in very poor yield, by melting arsenic acid with aniline ... 

The feasible methods of preparing arsanilic acid all depend upon the interaction between aniline and arsenic acid. Various temperatures ranging from 150 to 200° and various ratios of aniline to arsenic acid have been recommended.3... 

The main objection to most of the published methods is the fact that the authors leave it to be inferred that this is a smooth reaction. None of them points out the fact that an important side-reaction consists in the oxidizing action of arsenic acid upon aniline, with the production of a deeply purple-colored dye as well as much tarry material and some diaryl arsenic acid. 

Iodine is used in various forms in medicine—e.g. tincture of iodine, liquor iodi, iodized cotton, iodized wine, iodized water, oils and syrups iodides of potassium, mercury, iron, arsenic, lead, etc. and as methyl iodide or di-iodide iodoform, CHI3 ethyl iodide, C2H5I iodole, C4I4.NH aristole etc.—largely for external application as an antiseptic. Some iodides are used in photography, and in analytical operations and a considerable amount of iodine is used in the preparation of aniline dyes. 

Additive compounds are formed with aniline, piperazine, hexamethylenetetramine and quinoline 8 with pyridine, the two compounds, AsC13. C5H5N (m.pt. 138-9° C.) and AsC13.2CbHsN (m.pt. 61° C.), have been isolated.9 Addition of arsenic trichloride to dry 1 4-dioxan gives an oxonium compound, (C4H802)3.2AsC13 (m.pt. 62° C.).10... 

The oxidising agent usually employed is the nitro-compound corresponding to the amine, e.g., nitrobenzene when aniline is the base for p-toluidine, p-nitrotoluene serves, and so on. Arsenic acid, however, can be generally employed, and gives better results. The reaction is capable of very wide application nitro-, halogen-, hydroxy-, carboxy-quinolines can all be obtained from the corresponding amines the amino-naphthalenes also react. Diamines yield the so-called phen-anthrolines. (B., 16, 2519 23, 1016.)... 

Lastly, some of the substances already mentioned may be added as adulterants, and for the same purpose use may be made of such materials as potassium oxalate and oxalic add (found in fuchsine), and bronze powders (in colouring matters with metallic lustre). Arsenic may occur as impurity in certain aniline colouring matters, especially in certain fuchsines. 

Reactions of a,(3-unsaturated ketones with anilines are not very diverse and usually yield the appropriate quinolines [204, 205, 206, 207, 208, 209, 210, 211]. As catalysts in such reactions, hydrochloric acids are often used [204, 205, 206, 207]. In [208] besides hydrochloric acid, the use of arsenic acid and zinc chloride was proposed, which led to increase of the yields. In [209] it was reported that the catalyst used was 3-nitrobenzensulfonic acid (Scheme 3.74). 

The use of hypervalent iodine reagents for heteroatom-heteroatom bond forming reactions is well established in the context of classical oxidation chemistry [1-11]. For example, oxidations of anilines to azobenzenes, thiols to disulfides, and sulfides to sulfoxides with aryl-A3-iodanes were documented decades ago [1-5]. During the last ten years, particular attention has also been given to oxidative transformations of compounds derived from heavier elements, including the interception of reaction intermediates or initially formed products with external nucleophiles. A second important development is the utilization of sulfonyliminoiodanes, ArI = NS02R, for heteroatom-nitrogen bond formation, especially for imidations of sulfur, selenium, phosphorus and arsenic com-... 

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