Hydrazine ethyl

Thiele discovered nitro- and amino-guanidine and described a preparation of hydrazine from aminoguanidine, also of hydrazoic acid from hydrazine, ethyl nitrite, and alkali, and at first independently proposed and adopted the correct linear formula N. N NH, which had been given by Angeli, but later reverted to Curtius s cyclic formula on the basis of misleading parachor results. Thiele and A. Lachman discovered nitramide by way of nitrourethane, C2H50-C0-NH-N02. They formulated it both as the amide, NH2 N02, or imide, NH NO OH, of nitric acid. Thiele later preferred the second formula. 

In 2010, Pitchumani and Kanagaraj reported the solvent-free multicomponent synthesis of pyranopyrazoles. The reaction of hydrazine, ethyl acetoacetate, malononitrile, and aromatic aldehydes catalyzed by per-6-amino-p-cyclodextrin at room temperature afforded the corresponding pyranopyrazoles in quantitative yields [56]. 

Synthesis of 4 H-pyrano[2,3-c]pyrazoles has been reported [113] via afonr-com-ponent cyclocondensation of hydrazine monohydrate/phenyl hydrazine, ethyl ace-toacetate, aldehydes, and malononitrile by using L-proline as catalyst in IL [BMIm] BF (Scheme 7.11). 

Protection of amino groups from nitrous acid by acylation is not always successful, for deacylation may occur during treatment of the esters with hydrazine. Ethyl 2,6-dibenzamidoisonicotinate when treated with hydrazine gives 2,6-diMmnoisonicotinyl hydrazide the ethyl ester of phthalylglycine is similarly cleaved to gly(yl hydrazide and phthalhydrazide, a gener reaction for phthalimides (see p. 381). 

Dissolve 10 g. of chloro- 2,4-dinitrobenzenet in 50 ml. of dioxan in a 250 ml. conical flask. Dilute 8 ml. of hydrazine hydrate with an equal volume of water and add this slowly with shaking to the dioxan solution, keeping the temperature between zo " and 25°. Heat under reflux for 10 minutes to complete the reaction and then add 5 ml. of ethanol and heat again for 5 minutes. Cool and filter oflF the orange 2,4-dinitrophenylhydra-zine. Recrystallise the dry product from ethyl acetate m.p. 200° (decomp.). Yield, 7 g. 

If ethyl acetoacetate is warmed with an equivalent quantity of phenyl hydrazine, the corresponding phenylhydrazone (A) is readily formed. On... 

Acid hjdrazides from esters. Meth and ethyl esters react with hydrazine to give acid hydrazides ... 

Place 1 0 ml. of hydrazine hydrate (CAUTION corrosive chemical) in a test-tube fitted with a short refiux condenser. Add 10 g. of the methyl or ethyl ester dropwise (or portionwise) and heat the mixture gently under refiux for 15 minutes. Then add just enough absolute ethanol through the condenser to produce a clear solution, refiux for a further 2-3 hours, distil oflF the ethyl alcohol, and cool. Filter oflF the crystals of the acid hydrazide, and recrystallise from ethanol, dilute ethanol or from water. 

Girard s reagent T is carbohydrazidomethyltrimethylammonium chloride (I) and is prepared by the reaction of the quaternary ammonium salt formed from ethyl chloroacetate and trimethylamine with hydrazine hydrate in alco-hoUc solution ... 

Girard s reagent P , C5H5NCH2C0NHNH2 C1. In a 1-htre threenecked flask, equipped as in the previous preparation, place 200 ml. of absolute ethyl alcohol, 63 g. (64 -5 ml.) of pure anhydrous pyridine and 98 - 5 g. (84 5 ml.) of ethyl chloroacetate. Heat the mixture under reflux for 2-3 hours until the formation of the quaternary salt is complete acidify a small test-portion with dilute sulphuric acid it should dissolve completely and no odour of ethyl chloroacetate should be apparent. Cool the mixture in ice and salt. Replace the thermometer by a dropping funnel, and add a solution of 40 g. of 100 per cent, hydrazine hydrate in 60 ml. of absolute ethanol all at once. A vigorous exothermic reaction soon develops and is accompanied by vigorous effervescence. The pro duct separates almost immediately. When cold, filter with suction, wash... 

When ethyl acetoacetate is warmed with an equivalent quantity of phenyl-hydrazine, the compound (I), which is not a true hydrazone, is first formed this undergoes ring formation (II) with loss of ethyl alcohol upon further heating. The product (II) is N or l-phenyl-3-methyl-5-pyrazolone. 

Ethyl-N-(2 thiazolyl)carbainate reacts with aqueous hydrazine to give 271 (Scheme 165) (263). 

Ascorbic acid + KI, citrate, CN , diethyldithiocarbamate, 2,3-dimercaptopropanol, ethyl-enediamine, EDTA, glycine, hexacyanocobaIt(III)(3—), hydrazine, E, NaH2P02,... 

The ionic hydrazides are extremely sensitive and explode on contact with ak or upon heating. The alkaline-earth hydrazides, which have the general formula M(N2H2), appear to be less sensitive (15). Hydrazides such as aluminum hydrazide [25546-96-7] Al(N2H2)3, have also been made (16). The hydrazide anion is more nucleophilic than hydrazine and undergoes reactions not possible using hydrazine itself (17). Thus, styrene in ethyl ether solution at 0°C is... 

The methyl ethyl ketazine forms an immiscible upper organic layer easily removed by decantation. The lower, aqueous phase, containing acetamide and sodium phosphate, is concentrated to remove water formed in the reaction and is then recycled to the reactor after a purge of water-soluble impurities. Organic by-products are separated from the ketazine layer by distillation. The purified ketazine is then hydrolyzed under pressure (0.2—1.5 MPa (2—15 atm)) to give aqueous hydrazine and methyl ethyl ketone overhead, which is recycled (122). The aqueous hydrazine is concentrated in a final distillation column. 

Automobile safety air bags use sodium azide [26628-22-8] NaN, for gas generation. It can be made from hydrazine by refluxing ethyl or Abutyl nitrite with hydrazine hydrate and sodium hydroxide in alcohol (209,210) ... 

Organic solutions of HOCl can be prepared in near quantitative yield (98—99%) by extraction of CU -containing aqueous solutions of HOCl with polar solvents such as ketones, nitriles, and esters (131). These organic solutions of HOCl have been used to prepare chlorohydrins (132) and are especially useful for preparation of water-insoluble chlorohydrins. Hypochlorous acid in methyl ethyl ketone has also been used to prepare Ca(OCl)2, by reaction with CaO or Ca(OH)2 (133), and hydrazine by reaction with NH3 (134). 

The most important synthesis of pyrazolones involves the condensation of a hydrazine with a P-ketoester such as ethyl acetoacetate. Commercially important pyrazolones carry an aryl substituent at the 1-position, mainly because the hydrazine precursors are prepared from readily available and comparatively inexpensive diazonium salts by reduction. In the first step of the synthesis the hydrazine is condensed with the P-ketoester to give a hydrazone heating with sodium carbonate then effects cyclization to the pyrazolone. In practice the condensation and cyclization reactions are usually done in one pot without isolating the hydrazone intermediate. 

Phthalic anhydride and diethyl phthalate are easily converted with hydrazine into 4-hydroxyphthalazin-l(2/f)-one. Its substituted derivatives have been prepared using substituted hydrazines, substituted phthalic anhydrides, or diesters or disodium salts of substituted phthalic acids (Scheme 81). However, condensation of phenylhydrazine with phthalic anhydride gives only a small amount of the corresponding phthalazine, the main product being 2-anilinophthalimide. This can be rearranged in the presence of base into the phthalazine derivative. For the preparation of 2,3-disubstituted derivatives, 1,2-disub-stituted hydrazines are reacted with the appropriate phthalic anhydrides or phthaloyl chlorides. Derivatives of 4-amino- or 4-hydrazino-phthalazin-l(2iT)-one have been prepared either from the corresponding monothiophthalimide and 3-aminoisoindolin-3-one (1S4) or from ethyl 2-cyanobenzoate (155) and hydrazine hydrate (Scheme 82). Similarly,... 

Carboxymethyl)tr(methy(ammonlum chloride hydrazlde (Reagent T ). A cooled soKilion of ethyl chioroacetate (984 g, 6.65 mol) was treated with irimethylamine (200 g, 3.39 mol). After 12-24 h a second portion of trimethylamlne (200 g, 3.39 mol) was added. After complete consumption of ethyl chioroacetate, hydrazine (4C0 g) was added. The product was tillered and dryed under vacuum (H2SO4) to afford 1100 g of T (90%). 

Ethyl carhazate (A-ethoxycarhonyl hydrazine) [4114-31-2] M 104.1, m 44-48 , 51-52 , h 95.5 /10m, 92-95 /12mm, 100-102 /llmm. Fractionated using a Vigreux column until the distillate crystallises [Allen and Bell Org Synth Coll Vol III 404 1955.]... 

NOTE - Petrochemical plants also generate significant amounts of solid wastes and sludges, some of which may be considered hazardous because of the presence of toxic organics and heavy metals. Spent caustic and other hazardous wastes may be generated in significant quantities examples are distillation residues associated with units handling acetaldehyde, acetonitrile, benzyl chloride, carbon tetrachloride, cumene, phthallic anhydride, nitrobenzene, methyl ethyl pyridine, toluene diisocyanate, trichloroethane, trichloroethylene, perchloro-ethylene, aniline, chlorobenzenes, dimethyl hydrazine, ethylene dibromide, toluenediamine, epichlorohydrin, ethyl chloride, ethylene dichloride, and vinyl chloride. 

Benzeneamine, N-hydroxy-N-nitroso,ammonium salt Nitrilotrlacetic acid 4,4 -Thiodianiline Ethyl acrylate Butyl acrylate Ethyleneimine (Aziridine) p-Nrtrosodiphenylamine Calcium cyanamide Hydrazine Aldrin... 

A number of other gases can undergo reactions that produce decomposition flames—for instance, ethylene, ethylene oxide, methyl nitrate, ethyl nitrate, and hydrazine (CCPS 1993). 

With Af-acyl or Af-sulfonyl hydrazines as nucleophiles, Zincke salts serve as sources of iminopyridinium ylides and ylide precursors.Reaction of the nicotinamide-derived Zincke salt 8 with ethyl hydrazino urethane 42 provided salt 43, while the tosyl hydrazine gave ylide 44 (Scheme 8.4.14). ° Benzoyl hydrazines have also been used in reactions with Zincke salts under similar conditions.Af-amino-1,2,3,6-tetrahydropyridine derivatives such as 47 (Scheme 8.4.15), which showed antiinflammatory activity, are also accessible via this route, with borohydride reduction of the initially formed ylide 46. ... 

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