Hquid ammonia reactions

Reaction with Ammonia. Although the Hquid-phase reaction of acrolein with ammonia produces polymers of Htde interest, the vapor-phase reaction, in the presence of a dehydration catalyst, produces high yields of [ -picoline [108-99-6] and pyridine [110-86-4] n.2L mXio of approximately 2/1. 

Compound (12) can also be obtained by dissolving metal reactions through treatment with an excess of lithium—hquid ammonia in tert-huty alcohol (54). 

Acetyhdes of the alkaU and alkaline-earth metals are formed by reaction of acetylene with the metal amide in anhydrous Hquid ammonia. 

Ethynylation. Base-catalyzed addition of acetylene to carbonyl compounds to form -yn-ols and -yn-glycols (see Acetylene-DERIVED chemicals) is a general and versatile reaction for the production of many commercially useful products. Finely divided KOH can be used in organic solvents or Hquid ammonia. The latter system is widely used for the production of pharmaceuticals and perfumes. The primary commercial appHcation of ethynylation is in the production of 2-butyne-l,4-diol from acetylene and formaldehyde using supported copper acetyHde as catalyst in an aqueous Hquid-fiHed system. 

A AlI lation. 1-Substitution is favored when the indole ring is deprotonated and the reaction medium promotes the nucleophilicity of the resulting indole anion. Conditions which typically result in A/-alkylation are generation of the sodium salt by sodium amide in Hquid ammonia, use of sodium hydride or a similar strong base in /V, /V- dim ethyl form am i de or dimethyl sulfoxide, or the use of phase-transfer conditions. 

Iron(III) bromide [10031-26-2], FeBr, is obtained by reaction of iron or inon(II) bromide with bromine at 170—200°C. The material is purified by sublimation ia a bromine atmosphere. The stmcture of inoa(III) bromide is analogous to that of inon(III) chloride. FeBr is less stable thermally than FeCl, as would be expected from the observation that Br is a stronger reductant than CF. Dissociation to inon(II) bromide and bromine is complete at ca 200°C. The hygroscopic, dark red, rhombic crystals of inon(III) bromide are readily soluble ia water, alcohol, ether, and acetic acid and are slightly soluble ia Hquid ammonia. Several hydrated species and a large number of adducts are known. Solutions of inon(III) bromide decompose to inon(II) bromide and bromine on boiling. Iron(III) bromide is used as a catalyst for the bromination of aromatic compounds. 

The ethynylation reaction takes place at 10—40°C and 2 MPa (20 atm) and hquid ammonia is the solvent. The methylbutynol is converted into methylbutenol by selective hydrogenation and then is dehydrated over alumina at 250—300°C. Polymerization-grade isoprene is obtained. 

Potassium superoxide is produced commercially by spraying molten potassium iato an air stream, which may be enriched with oxygen. Excess air is used to dissipate the heat of reaction and to maintain the temperature at ca 300°C. It can also be prepared ia a highly pure state by oxidizing potassium metal that is dissolved ia Hquid ammonia at —50° C. 

Trickle bed reaction of diol (12) using amine solvents (41) has been found effective for producing PDCHA, and heavy hydrocarbon codistiUation may be used to enhance diamine purification from contaminant monoamines (42). Continuous flow amination of the cycloaUphatic diol in a Hquid ammonia mixed feed gives >90% yields of cycloaUphatic diamine over reduced Co /Ni/Cu catalyst on phosphoric acid-treated alumina at 220°C with to yield a system pressure of 30 MPa (4350 psi) (43). 

Heating metallic lithium in a stream of gaseous ammonia gives lithium amide [7782-89-0] LiNH2, which may also be prepared from Hquid ammonia and lithium in the presence of platinum black. Amides of the alkaH metals can be prepared by double-decomposition reactions in Hquid ammonia. For example... 

Hydroisoquinolines. In addition to the ring-closure reactions previously cited, a variety of reduction methods are available for the synthesis of these important ring systems. Lithium aluminum hydride or sodium in Hquid ammonia convert isoquinoline to 1,2-dihydroisoquinoline (175). Further reduction of this intermediate or reduction of isoquinoline with tin and hydrochloric acid, sodium and alcohol, or catalyticaHy using platinum produces... 

Sodium forms unstable solutions in Hquid ammonia, where a slow reaction takes place to form sodamide and hydrogen, as foUows ... 

A hquid-phase reaction in which TiCl is reacted with hquid ammonia at —35 C to form an adduct that is subsequendy calcined at 1000°C has also been proposed (35). Preparation of titanium nitride and titanium carbonitride by the pyrolysis of titanium-containing polymer precursors has also been reported (36). 

Another exceUent method for preparing tertiary stibines involves the interaction of an organostibide and an alkyl or aryl haHde (91,92). This method is of particular value in preparing un symmetrical tertiary stibines. For example, an interesting hybrid ligand has been obtained by the foUowing reaction carried out in Hquid ammonia (93) ... 

Arsine is formed when any inorganic arsenic-bearing material is brought in contact with zinc and sulfuric acid. The arsenides of the electropositive metals are decomposed with the formation of arsine by water or acid. Calcium arsenide [12255-53-7] Ca2As2, treated with water gives a 14% yield of arsine. Better yields (60—90%) are obtained by decomposing a solution of sodium arsenide [12044-25-6] Na As, in Hquid ammonia with ammonium bromide (14,15). Arsine may be accidentally formed by the reaction of arsenic impurities in commercial acids stored in metal tanks, so that a test should be made for... 

This carboxyborane can undergo an amine exchange reaction with Hquid ammonia (eq. 7) to yield the boron analogue of glycine, the simplest alpha-amino acid (13). There has been a great deal of work on the pharmacological activity of these amino acid analogues (14). 

Halogen Reactions. Hydrolysis of chlorotoluenes to cresols has been effected by aqueous sodium hydroxide. Both displacement and benzyne formation are involved (27,28). o-Chlorotoluene reacts with sodium in Hquid ammonia to afford a mixture of 67% of o-toluidine [95-53-4] and 33% of yW-toluidine [108-44-1], C H CIN, as shown in equation 3 (29). 

Himethylformamide [68-12-2] can be produced from the reaction of hydrogen cyanide and methanol. Adenine [73-24-5] can be prepared from hydrogen cyanide in Hquid ammonia. Thioformamide [115-08-2] can be produced from hydrogen cyanide and hydrogen sulfide. 

The main method for the preparation of different types of organostannanes is the ancient Wilrtz reaction between triorganotin halides or diorganotindihalides. Reactions proceed with or without solvent. Usual solvents are benzene, toluene, xylene, diethyl ether and ethanol. Occasionally hquid ammonia is also used. The preferred metals for this reaction are sodium and lithium. In the case of triorganotin halides, the reaction leads to symmetric hexaorganoditin compounds72 ... 

Unsymmetric organostannanes can be prepared by the reaction of triorganotin sodium compounds in hquid ammonia with a triorganotin halide73,74 ... 

Lithium amide is obtained by dissolution of lithium metal in hquid ammonia. The reaction is slow, but may be catalyzed by cobalt nitrate ... 

This reaction is catalyzed by iron, cobalt, and nickel. Rate of reaction depends on temperature and concentration of sodium in hquid ammonia. At a temperature of -41.6°C and high concentration, the solution separates into two hquid phases that consist of a deep blue dilute solution at the bottom that is low in sodium, and a hghter solution of metalhc bronze color on the top with a high sodium. Molten sodium reacts with ammonia gas at 300 to 400°C to form sodium amide. 

Reaction of 2-alkynoic acids with an excess of sodamide in hquid ammonia followed by treatment with mineral acid (after evaporation of the ammonia) gives 3-alkynoiC acids in excellent yields [183], Presumably, the 2-alkynoic acid is convened into the disodium compound of the 3-alkynoic acid via a process of proton removal and proton donation ... 

Kraus and Flood found that hexaethyldigermane was not formed in the reaction of triethylbromogermane and sodium metal in boiling xylene. However, they produced hexaethyldigermane by heating Et3GeBr and Na in a sealed tube at 210-270 °C without solvent or by the reaction of EtsGeBr and Na in hquid ammonia. 

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