Diethyl carbonate, with hydrazine

Diethyl carbonate, with hydrazine hydrate to give ethyl hydrazinecarboxylate, 51,... 

O 17,76%. NHjNHCONHNH,. Prepd by refluxing diethyl carbonate with hydrazine hydrate Mohr et at., Inorg. Syn. 4, 32 (1953). 

In a scheme intended to produce a more highly substituted oxazolidone, epichlorohydrin is condensed with morpholine in the presence of strong base to give the aminoepoxide, 27. Ring opening of the oxirane by means of hydrazine gives the hydroxy-hydrazine (28). Ring closure with diethyl carbonate leads to the substituted oxazolidone (29). Condensation with 18 affords furaltadone (30). ... 

The reaction mixture is then warmed on the steam bath for an additional two hours (90°C to 95°C). The excess hydrazine hydrate is removed in vacuo. The residue of viscous 1-hy-drazlno-3-morpholinyl-2-propanol Is not distilled, but is mixed with 10.16 g (0.0B6 mol) diethyl carbonate and a solution of 0.3 g sodium metal in 15 ml methyl alcohol. The mixture is refluxed about 2 hours under a 15 cm Widmer column, the alcohol being removed leaving a thick, green liquid residue, which is cooled and the precipitate which forms is removed by filtration and washed well with ether. Yield B2%, MP114°C to 116°C. Recrystallization from isopropanol gives purified 3-amino-5-(N-morpholinyl)-methyl-2-oxazolidone, MP 120°C as the intermediate. 

Diaminobiuret has been prepared only from N-tricarboxylic ester and hydrazine hydrate.1 Ethyl hydrazinecarboxylate has been prepared by reduction of nitrourethan electrolytically2 or with zinc dust and acetic acid,3 and by the action of hydrazine hydrate on diethyl carbonate,4 6 ethyl chlorocarbonate,6 and N-tricarboxylic ester.1... 

Ethyl diazoacetate, as source of car-bethoxycarbene, 50, 94 Ethylene, with p-methoxyphenyl-acetyl chloride and aluminum chloride to give 6-methoxy- 3-tetralone, 51,109 Ethyl hydrazinecarboxylate, from hydrazine hydrate and diethyl carbonate, 51,121 Ethylidenecyclohexylamine, 50,66 Ethyl 1-iodopropionate, from ethyl... 

A. Ethyl hydrazinecarboxylate. To 100 g. (97 ml., 2.0 moles) of 100% hydrazine hydrate, contained in a 1-1. round-bottomed Hank, iH added 236 g. (243 ml., 2.0 moles) of diethyl carbonate (Note I). The flask is fitted with a calcium chloride-containing drying tube and is shaken vigorously to mix the two liquids. After about 5 minutes, the milky emulsion becomes warm, and shaking is continued until a clear solution is obtained (approximately 20 minutes). The flask is equipped with a reflux condenser fitted with a calcium chloride-containing drying tube and is heated on a steam bath for 3.5 hours. The reaction mixture is transferred to a 500-ml. round-bottomed flask and is... 

Hydrazine Azide (formerly called Hydrazine Azoimide,Hydrazine Trinitride or Hydrazonium Azide) (called by Curtius Diammonium Azide, N,H ), NaH, HN, mw 75.08, N93.29% rhmb, hygr crysts mp 75.4(Ref 6) v sol in w, sol in hydrazine(190% at 23 ), methanol (6.1% at 23°) and in ale (1.2% at 23°C), not appreciably sol in chlf, carbon tetrachloride benz, carbon disulfide, ethyl acetate or diethyl ether (Ref 6). First prepd by Curtius in I89I (Ref 1) by neutralizing hydrazoic acid with hydrazine... 

Single-batch Preparation. Three hundred fifty-four grams of diethyl carbonate (3.0 mols) and 388 g. of 85% hydrazine hydrate (6.6 mols) are placed in a 1-1. round-bottomed flask equipped with a thermometer. The reactants are only partially miscible at first the flask is shaken until a single phase is formed. This process [eq. (1)] is accompanied by the evolution of heat, causing the temperature to rise to about 55°. 

A stock solution is prepared by shaking 856 g. of diethyl carbonate (7.25 mols) with 938 g. of 85% hydrazine hydrate (15.95 mols) until a single liquid phase is formed. The equipment described above is used to effect reaction and removal of volatile products. 

The reagent can be prepared in 90% yield by the reaction of 85% hydrazine hydrate with diethyl carbonate. It condeniei with a variety of aldehydes and... 

The reaction of diethyl 3,4-dimethylthieno[2,3-Z ]thiophene-2,5-dicarboxylate (117, R = Me, EWG = C02Et) with hydrazine hydrate afforded dihydrazide 231, which was subjected to various transformations. For example, the reactions with acetylacetone, ethyl acetoacetate or malononitrile (93BCJ2011) are accompanied by the closure of the exocyclic pyrazole ring to form the corresponding derivatives 232-234. The reaction of dihydrazide 231 with carbon disulfide in the presence of KOH followed by decomposition with dilute HCl or concentrated H2SO4 produces di(oxadiazole) (235) or di(thiadiazole) derivative (236). Condensation of di(oxadia-zolyl)thienothiophene 235 with hydrazine hydrate affords di(triazolyl)thienothio-phene 237. 

When aqueous solutions of rare earth salts are treated with solutions of ammonium carbonate in hydrazine hydrate (N2H5COON2H3), rare earth metal hydrazine carboxylate hydrate complexes are formed [15]. Initially, a precipitate forms that dissolves with the addition of excess reagent. On keeping the solution for a couple of days crystalline solids separate. The crystals are washed with alcohol and then diethyl ether and stored in a vacuum desiccator. The composition of the crystals determined by chemical analysis and infrared spectra has been found to be Ln(N2H3C00)3-3H20 ... 

Acyclic ADC compounds, which are more correctly named as derivatives of diazene, are generally prepared from hydrazine derivatives. For example, diethyl azodicarboxylate (Chemical Abstracts name diethyl diazene-1,2-dicarboxylate)5 is prepared from hydrazine by treatment with ethyl chloro-formate followed by oxidation with chlorine in benzene-water.6 Other oxidants which have been used include JV-bromosuccinimide,7 nitric acid,8 inorganic nitrates,9 potassium dichromate,10 silver carbonate on celite,11 and phenyl iodosotrifluoroacetate.12 The hydrazine derivative may also be... 

Coupling of excess (Z)-l,2-dichloroethene (217) with propargyl alcohol first led to the enyne 218, which, when subjected to a second Pd-catalyzed coupling step with trimethylsilylacetylene, provided the mixed diacetylene 219. With all carbon atoms assembled, the allene function was generated by first producing the (unprotected) hydrazine derivative 220, which on treatment with either diethyl azodicarboxylate (DEAD) or 4-methyl-l,2,4-triazoline-3,5-dione (MTAD) under anaerobic conditions at 0 °C yielded the hydrocarbon 27. According to mechanistic studies, the latter process leads first to a mixture of ( )- and (Z)-diazenes. Sigmatropic elimination of... 

Z,Z)-Distyryl Tellurium2 A mixture of 12.8 g (0.1 mol) tellurium, 20.4 g (0.2 mol) phenylacetylene, 84 g (1.5 mol) potassium hydroxide, 120 ml (2.5 mol) hydrazine hydrate, 24 ml water, 40 ml toluene, and 1 g trialkylmethylammonium chloride is stirred and heated at 100 to 110° for 6 h. The mixture is diluted with water and extracted with benzene. The organic layer is washed with water, dried with potassium carbonate, filtered and the solvent evaporated from the filtrate. The residue is dissolved in diethyl ether, and the solution is poured into ethanol. After several days in the refrigerator yellow crystals of distyryl tellurium formed yield 50%. 

Ignition or explosive reaction with metals (e.g., aluminum, antimony powder, bismuth powder, brass, calcium powder, copper, germanium, iron, manganese, potassium, tin, vanadium powder). Reaction with some metals requires moist CI2 or heat. Ignites with diethyl zinc (on contact), polyisobutylene (at 130°), metal acetylides, metal carbides, metal hydrides (e.g., potassium hydride, sodium hydride, copper hydride), metal phosphides (e.g., copper(II) phosphide), methane + oxygen, hydrazine, hydroxylamine, calcium nitride, nonmetals (e.g., boron, active carbon, silicon, phosphoms), nonmetal hydrides (e.g., arsine, phosphine, silane), steel (above 200° or as low as 50° when impurities are present), sulfides (e.g., arsenic disulfide, boron trisulfide, mercuric sulfide), trialkyl boranes. 

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