Acetone hydrazine with

The forerun contains hydrazine. Material boiling above 126° contains much acetone azine. With a slow rate of distillation, disproportionation occurs and the yield of acetone hydrazone is reduced. If the forerun and material boiling above 126° are combined and reheated at 100° for 12-16 hours, they give more acetone hydrazone on redistillation. With further repetitions of this procedure, the yield is almost quantitative. 

For most uses, hydrazine is produced as hydrazine hydrate in a formulation with water. The hydrate may be produced commercially by three methods the Raschig process, the ketazine process, and the peroxide process. The Raschig process, the original commercial production process for hydrazine, involves oxidation of ammonia to chloramine with sodium hypochlorite, then further reaction of the chloramine with excess ammonia and sodium hydroxide to produce an aqueous solution of hydrazine with sodium chloride as a by-product. Fractional distillation of the product yields hydrazine hydrate solutions. Currently, most hydrazine is produced by the ketazine process, which is a variation of the Raschig process. Ammonia is oxidized by chlorine or chloramine in the presence of an aliphatic ketone, usually acetone. The resulting ketazine is then hydrolyzed to hydrazine. In the peroxide process, hydrogen peroxide is used to oxidize ammonia in the presence of a ketone. Anhydrous hydrazine is the formulation used in rocket fuels and is produced by dehydration of the hydrate by azeotropic distillation with aniline as an auxiliary fluid (Budavari et al. 1989 lARC 1974 Schmidt 1988 WHO 1987). 

The second pathway of conjugation to be presented here is the reaction of hydrazines with endogenous carbonyls (reaction 2) (92). This reaction occurs nonenzymatically and involves a variety of carbonyl compounds, including aldehydes (mainly acetaldehyde) and ketones (e.g., acetone, pyruvic acid... 

By a similar reaction ethanol gives acetaldehyde (tests, p. 341) and isopropanol gives acetone (tests, p. 345). -Butanol gives butyr dehyde (pleasant characteristic odour and precipitate with 2,4-dinitrophenyl-hydrazine, m.p. 122 ). 

The acetone test reagent consists of a 0 1 per cent, solution of 2 4-dinitro-phenylhydrazine and is prepared as follows Dissolve 0-25 g. of 2 4-dinitrophenyl-hydrazine in 60 ml. of water and 42 ml. of concentrated hydrochloric acid by warming on a water bath cool the clear yellow solution and dilute to 250 ml. with water. The acetone test is considered negative when 5 ml. of the reagent and 4-5 drops of the distillate give no cloudiness or precipitate of acetone 2 4-dinitro-phenylhydrazone within 30 seconds. After a negative test is obtained, it is stron y recommended that the mixture in the flask be refluxed for 5-10 minutes with complete condensation and then to collect a few drops of distillate for another test. If no acetone is now detected, the reduction is complete. 

Hydroxyl Group. The OH group of cyanohydrins is subject to displacement with other electronegative groups. Cyanohydrins react with ammonia to yield amino nitriles. This is a step in the Strecker synthesis of amino acids. A one-step synthesis of a-amino acids involves treatment of cyanohydrins with ammonia and ammonium carbonate under pressure. Thus acetone cyanohydrin, when heated at 160°C with ammonia and ammonium carbonate for 6 h, gives a-aminoisobutyric acid [62-57-7] in 86% yield (7). Primary and secondary amines can also be used to displace the hydroxyl group to obtain A/-substituted and Ai,A/-disubstituted a-amino nitriles. The Strecker synthesis can also be appHed to aromatic ketones. Similarly, hydrazine reacts with two molecules of cyanohydrin to give the disubstituted hydrazine. 

In the modified Raschlg process , used by Bayer A.G. and by Mobay Chem. Co. for large scale production of hydrazine, the intermediacy of an oxaziridine could be clearly evidenced (81MI50800). In this process ammonia and hypochlorite are reacted in the presence of acetone to form ketazine (302). Nitrogen-nitrogen bond formation is faster by a factor of about 1000 in the presence of acetone than in its absence. Thus acetone does not merely trap hydrazine after formation, but participates in the N —N bond forming reaction. Very fast formation of oxaziridine (301), which is isolable, is followed by its likewise fast reaction with ammonia. 

Sodium azide (Eastman, 97-99%) is activated by dissolving 100 g of the salt in 400 ml of distilled water and stirring with 14 ml of hydrazine hydrate for 15 min. The solution is filtered and added dropwise to 4 liters of rapidly stirred, dry acetone. The solid is collected by filtration and washed with 150 ml of dry acetone. The fine powder (57-85 g) is dried under vacuum at 50° for 2 hr. Sodium azide is extremely toxic and the fine powder should be handled with care to avoid breathing the dust. 

Although the addition of hydrazine and its derivatives to acetylenic ketones has been studied in considerable detail, their interaction with hydrazones and mono-alkylhydrazones is less well known. Yandovskii and Klindukhova (74ZOR730) have studied the reaction between hydrazones and alkylhydrazones of aliphatic ketones with dipropynylketones and showed that hydrazones of acetone, methyl-ethylketone, and cyclohexane easily add to one of the triple bonds of dipropynylketone to form 4-methyl-1,1,3-trialkyl-2,3-diaza-l,4-nonadien-7-yn-6-ones (yields... 

Condensation of ethyl acetoacetate with phenyl hydrazine gives the pyrazolone, 58. Methylation by means of methyl iodide affords the prototype of this series, antipyrine (59). Reaction of that compound with nitrous acid gives the product of substitution at the only available position, the nitroso derivative (60) reduction affords another antiinflammatory agent, aminopyrine (61). Reductive alkylation of 61 with acetone in the presence of hydrogen and platinum gives isopyrine (62). Acylation of 61 with the acid chloride from nicotinic acid affords nifenazone (63). Acylation of 61 with 2-chloropropionyl chloride gives the amide, 64 displacement of the halogen with dimethylamine leads to aminopropylon (65). ... 

The study [39] shows that similar equation is valid for adsorption of NH- and NH2-radicaIs, too. There are a lot of experimental data lending support to the validity of the proposed two-phase scheme of free radical chemisorbtion on semiconductor oxides. It is worth noting that the stationary concentration of free radicals during the experiments conducted was around 10 to 10 particles per 1 cm of gas volume, i.e. the number of particle incident on 1 cm of adsorbent surface was only 10 per second. Regarding the number of collisions of molecules of initial substance, it was around 10 for experiments with acetone photolysis or pyrolysis provided that acetone vapour pressure was 0,1 to 0,01 Torr. Thus, adsorbed radicals easily interact at moderate temperatures not only with each other but also with molecules which reduces the stationary concentration of adsorbed radicals to an even greater extent. As we know now [45] this concentration is established due to the competition between the adsorption of radicals and their interaction with each other as well as with molecules of initial substance in the adsorbed layer (ketones, hydrazines, etc.). 

Bromo-l-phthalimidopentane 3 was obtained in 72-82 g yield by refluxing 92 g of 1,4-dibromopentane 1, 55.5 g of potassium phthalimide 2, and 200 mL dry acetone on a steam bath for 30 h. Compound 3 (30 g) and 42 g 6-methoxy-8-aminoquinoline 4 refluxed at 130-135 °C for 6 h, extracted with benzene to separate insoluble 6-methoxy-8-aminoquinoline hydrobromide, the residue from evaporation of the benzene was refluxed with stirring with 100 mL of an alcoholic solution of 6 g hydrazine hydrate for 4 h, the solution was concentrated, made acidic to Congo red with 8 N hydrochloric acid, filtered, and washed with boiling water. The combined filtrate and washings was concentrated, made alkaline, extracted with benzene, and distilled in vacuo to give 20.5 g primaquine 6, which was treated with 19 mL 85% phosphoric acid in absolute ethanol, formed 42.5% primaquine diphosphate. 

Figure 1.110 The reaction of SANH with an amine-containing molecule results in an amide bond derivative that terminates in a protected hydrazine group. Reaction with an aldehyde-containing molecule results in release of the acetone-protecting group and formation of a stable hydrazone bond.

Bayer ketazine A process for making hydrazine by the reaction of sodium hypochlorite with ammonia in the presence of acetone. Acetone azine is an intermediate. Never commercialized. See also Raschig (1). 

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