Alcoholic ammonia

Metal-ammonia-alcohol reductions of aromatic rings are known as Birch reductions, after the Australian chemist Arthur J Birch who demonstrated their usefulness begin nmg m the 1940s... 

Two different sets of experimental conditions have been used. Buu-Hoi et al. and Hansen have employed the method introduced by Papa et using Raney nickel alloy directly for the desulfurization in an alkaline medium. Under these conditions most functional groups are removed and this method is most convenient for the preparation of aliphatic acids. The other method uses Raney nickel catalysts of different reactivity in various solvents such as aqueous ammonia, alcohol, ether, or acetone. The solvent and activity of the catalyst can have an appreciable influence on yields and types of compounds formed, but have not yet been investigated in detail. In acetic anhydride, for instance, desulfurization of thiophenes does not occur and these reaction conditions have been employed for reductive acetylation of nitrothiophenes. Even under the mildest conditions, all double bonds are hydrogenated and all halogens removed. Nitro and oxime groups are reduced to amines. 

The following is an alternative method of preparation 1 gram 2-(7-chloropropyl)-s-tri-azolo-[4,3-al-pyridine-3-one and 5 ml saturated ammonia alcoholic solution are heated for 5 hours in a closed tube at 100°C. The contents of the tube are cooled, the ammonium chloride filtered out and the solvent is removed. There remains a residue of 0.9 grams 2-(7-aminopropyl)-s-triazolo-[4,3-al -pyridine-3-one. 

Ionic polysulfides dissolve only in media of high polarity hke water, liquid ammonia, alcohols, nitriles, amines, and similar solvents. In all of these solvents 8 can be reduced electrochemically to polysulfide anions. On the other hand, the electrochemical oxidation of polysulfide anions produces elemental sulfur ... 

Incompatibility Alkalis, ammonia, alcohols, copper NIOSH 1997... 

As far as propargyl thioethers are concerned, the substrates in this section follow all the principles discussed for propargyl ethers and propargylamines in the two preceding sections. For alkyl propargyl thioethers typical bases used are sodium amide in liquid ammonia, alcoholate or alkali metal hydroxide [178, 186-189, 191, 287-291], and again some derivatives of carbohydrates have been used successfully [292, 293], If an ester group is also present in the molecule, the reaction can be accompanied by a hydrolysis to the carboxylate [294]. 

Colorless or translucent bard crystalline mass or white cubic crystals or powder sharp taste odor of ammonia decomposes at 58°C slow decomposition at ambient temperatures readily dissolves in cold water decomposes in hot water insoluble in liquid ammonia, alcohol and carbon disulfide. 

White monoclinic deliquescent crystals or granules density 1.280 g/cm melts at 116°C highly soluble in water (102 g/100 g at 0°C), solubility rapidly increasing with temperature (i.e., 531 g/100 g at 80°C) soluble in liquid ammonia, alcohol and ether. 

Crystalline solid forming monochnic crystal hygroscopic melts at 149.6°C decomposes at 170°C density 1.305 g/cm highly soluble in water (128 g/100 mL at 0°C) soluble in liquid ammonia, alcohol, and acetone. 

EXAMPLE 2.2 Unsteady dissolution of a highly soluble pollutant (herbicides, pesticides, ammonia, alcohols, etc.) into groundwater (unsteady, one-dimensional solution with pulse boundary conditions)... 

The solvents that are leveling to both acids and bases are self-ionized solvents, e.g., water, ammonia, alcohols, carboxylic acids, nitric... 

Physical chemical studies of dilute alkali metal-ammonia solutions indicate the principal solution species as the ammoniated metal cation M+, the ammoniated electron e , the "monomer M, the "dimer" M2 and the "metal anion" M. Most data suggest that M, M2, and M are simple electrostatic assemblies of ammoniated cations and ammoniated electrons The reaction, e + NH3 - lf 2 H2 + NH2 is reversible, and the directly measured equilibrium constant agrees fairly well with that estimated from other thermodynamic data. Kinetic data for the reaction of ethanol with sodium and for various metal-ammonia-alcohol reductions of aromatic compounds suggest that steady-state concentrations of ammonium ion are established. Ethanol-sodium reaction data allow estimation of an upper limit for the rate constant of e + NH4+ 7, H2 + NH3. 

The Formation of Solvated Electrons and the Methodology of Investigating their Kinetics. Solvated electrons have been produced in polar, nonreactive solvents like water, ammonia, alcohols, and aliphatic amines by various processes ... 

Solid products are also formed with water, ammonia, alcohols and amines, when an insertion reaction probably also occurs. 

Hydrogen exchange reactions of heteroaromatics64 69, 65 carried out in strongly alkaline media, such as potassium amide/liquid ammonia, alcoholic solutions of alkoxides, or solutions of potassium <-butoxide in dimethyl sulfoxide, proceed through an entirely different mechanism (sometimes called protophilic ) involving a carbanion-type intermediate66, 67 they are not electrophilic substitutions as such and will not be treated in this review. 

Additional catalysts for the methyl chloride reaction are described in patents. For example, aluminum metal 271>, ammonia-water and ammonia-alcohol H4,ii5)> amines 37>116>, aluminum hydrides 313>, and various ethers 36,38-41,132,188,190) are discussed. 

ZSM-5 like alkanolamine diamine mono-n-alkylamine alcohols and ammonia alcohols template-free NHgQ Q OH propylamine C,Ho0H 4 (13-15) (16) (17-19) (20) (21) (22,23)... 

Nickel Bromate,2 Ni(Br03)2.6H20, may be prepared by double decomposition of barium bromate and nickel sulphate solutions. It crystallises in unstable octahedra which are green in colour. From its solution in aqueous ammonia, alcohol precipitates the diammoniate, Ni(Br03)2.2NH3. 

Reduction with alkali metals The solvents used for alkali metal reductions include hydrocarbons, ethers and, most commonly, liquid ammonia. Alcohols may also be used, but usually as co-solvents, since they react vigorously with these metals. Aldehydes are not usually reduced in this manner, because they react with ammonia to form unreactive imine condensation products. 

Alternatively, ketyls A may dimerize to pinacol salts E. Isolation of pinacol products F requires further protonation by acids at least as strong as water or ethanol. The notation refers to any of the several possible proton sources, including ammonia, alcohols and the ammonium cation (a strong acid in the liquid ammonia system) (Scheme 6.28). 

A similar change in product, this time dependent on temperature, takes place in the substitution of ammonia for both chlorides in [Co(en)2Cl2]. At low temperatures (-33° C or below, in liquid ammonia), there is inversion of configuration at higher temperatures (above 25° C in liquid ammonia, alcohol solution, or solid exposed to gaseous ammonia), there is retention. In both cases, there is also a small fraction of the trans isomer. 

Abstract The surfaces of model metal oxides offer many fundamental examples where the outcome of a specific chemical reaction might be linked to the surface structure and local electronic properties. In this work the reaction of simple molecules such as ammonia, alcohols, carboxylic and amino acids is studied on two metal oxide single crystals rutile TiO CllO) and (001) and fluorite UOj(l 11). Studies are conducted with XPS, TPD, and Plane Wave Density Functional Theory (DFT). The effect of surface structure is outlined by comparing the TiOj(llO) rutile surface to those of TiOjCOOl), while the effect of surface point defects is mainly discussed in the case of stoichiometric and substoichiometric UOjClll). 

The aromatic bromides which contain bromine in the benzene nucleus are either colourless liquids or crystals, which in contrast with the side-chain substituted isomers in part possess an aromatic odour, and their vapours do not attack the eyes and nostrils. The bromine is held very firmly in them, more firmly than in the aliphatic bromides, and cannot he detected by stiver nitrate. While the aliphatic bromides, as mentioned under bromethyl, decompose with ammonia, alcohol, alkalies, etc., to form amines, ethers, alcohols, etc., respectively, these reagents do not act on the aromatic bromides. The bromides containing the bromine in the side-chain, behave like their aliphatic analogues. 

Raney nickel modified with Mg or V can be used for the highly selective preparation of symmetrical amines by the alkylation of ammonia with n-propanol or i-butanol. Upon modifying the Raney nickel catalyst with 0.5 wt % V or Mg, 4-5 % increase in the selectivity to secondary amines was observed and the selectivities reached 70-80 % at 90-95 % conversions. In the alkylation of ammonia with an alcohol symmetrical secondary amines can be obtained with 70 % yield over Mg or V modified Raney nickel catalyst at 220-240 °C and ammonia/alcohol ratio of 1.5. In an industrial application 2-4 % increase of the selectivity results in an important finantial benefit. It was shown that pure (100 %) ethylamine and 70 % EtNH2 in water can be used for the preparation of N-ethyl-N-butylamine over a commercial Cu0-Zn0-Al203 catalyst. 

Appendix D explains how to make the red cabbage juice for Lesson 9 and the iodine, ammonia, alcohol, and detergent solutions for Lessons 8 and 15. 

The initial alcohol/amine ratio can determine the product distribution. In the synthesis of primary amines a rather high ammonia/alcohol molar ratio (up to 10-25), and usually high pressure, are required to compensate for the low reactivity of ammonia and suppress the formation of secondary amines. Selectivity for primary diamines could be improved in the amination of 1,3-dihydroxy compounds when using supercritical ammonia as solvent and reactant in a continuous fixed-bed reactor [12]. The remarkable changes in selectivity in the near-critical region (100-110 bar) are attributed to the increased concentration of ammonia on the metal surface as a result of elimination of mass-transport limitations in the two-phase system, and to suppression of hydrogenolysis and water elimination reactions which lead to monofunctional by-products. An example is shown in Figure 1. 

---