Ammonia mixtures with

TABLE 4. Measured and Correlated pH of Water-Ammonia Mixtures with no Acid Gas Present, 25°C... 

TABLE 15. Measured and Correlated Ammonia Mixtures with 0. Mole of NH3> 80°C pH of Water-258 Mole of H2S/ ... 

Synthesis of B-monosubstituted Borazine Derivatives. The photolytic reaction of borazine with a second reagent is a convenient method for synthesizing a number of B-monosubstituted borazine derivatives. B-monoaminoborazine, produced in the gas phase photolysis of borazine ammonia mixtures with 184.9 nm radiation, was first synthesized by Lee and Porter in 1967. This is the only method currenfly known for generating this compound. A detailed study of the photochemical reaction, under varying conditions of borazine and ammonia pressures, was reported by Neiss and Porter in 1972. The quantum yield for the production of H2 according to the overall Eq. (19) varies from 0.27 and 1.17 when the initial NH3 pressures are varied from 0.1 to 7.0 Torr and the borazine pressure is maintained at 5.0 Torr (Fig. 11). 

Base-promoted oxidation, which leads to oxidative dimerisation products, is another viable pathway for complexes based on pentan-2,4-dione bis-(S -alkylisothio-semicarbazones). It has been discovered [97, 98] that the mononuclear nickel(II) complex methylated at sulphur [Ni°(H2L63)]I l/2CH30H reacts in an ethanol/ ammonia mixture with dioxygen with formation of a dinuclear species formulated as [Ni2(L66)] (Eq. 2.39). 

Dissolve 5 g. of finely-powdered diazoaminobenzene (Section IV,81) in 12-15 g. of aniline in a small flask and add 2-5 g. of finely-powdered aniline hydrochloride (1). Warm the mixture, with frequent shaking, on a water bath at 40-45° for 1 hour. Allow the reaction mixture to stand for 30 minutes. Then add 15 ml. of glacial acetic acid diluted with an equal volume of water stir or shake the mixture in order to remove the excess of anihne in the form of its soluble acetate. Allow the mixture to stand, with frequent shaking, for 15 minutes filter the amino-azobenzene at the pump, wash with a little water, and dry upon filter paper Recrystallise the crude p-amino-azobenzene (3-5 g. m.p. 120°) from 15-20 ml. of carbon tetrachloride to obtain the pure compound, m.p. 125°. Alternatively, the compound may be recrystaUised from dilute alcohol, to which a few drops of concentrated ammonia solution have been added. 

Chemical Properties. Ammonium thiocyanate rearranges upon heating to an equiHbrium mixture with thiourea 30.3 wt % thiourea at 150°C, 25.3 wt % thiourea at 180°C (373,375). At 190—200°C, dry ammonium thiocyanate decomposes to hydrogen sulfide, ammonia, and carbon disulfide, leaving guanidine thiocyanate [56960-89-5] as a residue. Aqueous solutions of ammonium thiocyanate are weakly acidic a 5 wt % solution has a pH of 4—6. 

Chloral forms well-crystallized adducts (126) with diaziridines containing at least one NH group (B-67MI50800). Carbonyl addition products to formaldehyde or cyclohexanone were also described. Mixtures of aldehydes and ammonia react with unsubstituted diaziridines with formation of a triazolidine ring (128). Fused diaziridines like (128) are always obtained in ring synthesis of diaziridines (127) from aldehyde, ammonia and chloramine. The existence of three stereoisomers of compounds (128) was demonstrated (76JOC3221). Diaziridines form Mannich bases with morpholine and formaldehyde (64JMC626), e.g. (129). 

Figure 3 illustrates the shift and methanation conversion. The resulting methane is inert and the water is condensed. Thus purified, the hydrogen-nitrogen mixture with the ratio of 3H2 pressed to the pressure selected for ammonia synthesis. 

Aromatic steroids are virtually insoluble in liquid ammonia and a cosolvent must be added to solubilize them or reduction will not occur. Ether, ethylene glycol dimethyl ether, dioxane and tetrahydrofuran have been used and, of these, tetrahydrofuran is the preferred solvent. Although dioxane is often a better solvent for steroids at room temperature, it freezes at 12° and its solvent effectiveness in ammonia is diminished. Tetrahydrofuran is infinitely miscible with liquid ammonia, but the addition of lithium to a 1 1 mixture causes the separation of two liquid phases, one blue and one colorless, together with the separation of a lithium-ammonia bronze phase. Thus tetrahydrofuran and lithium depress the solubilities of each other in ammonia. A tetrahydrofuran-ammonia mixture containing much over 50 % of tetrahydrofuran does not become blue when lithium is added. In general, a 1 1 ratio of ammonia to organic solvents represents a reasonable compromise between maximum solubility of steroid and dissolution of the metal with ionization. 

Toluene is a useful co-solvent in metal-ammonia reductions as first reported by Chapman and his colleagues. The author has found that a toluene-tetrahydrofuran-ammonia mixture (1 1 2) is a particularly useful medium for various metal-ammonia reductions. Procedure 8a (section V) describes the reduction of 17-ethyl-19-nortestosterone in such a system. Ethylene dibromide is used to quench excess lithium. Trituration of the total crude reduction product with methanol affords an 85% yield of 4,5a-dihydro-17-ethyl-19-nortestosterone, mp 207-213° (after sintering at 198°), reported mp 212-213°. For the same reduction using Procedure 5 (section V), Bowers et al obtained a 60% yield of crude product, mp, 196-199°, after column chromatography of the total reduction product. A similar reduction of 17-ethynyl-19-nortestosterone is described in Procedure 8b (section V). The steroid concentration in the toluene-tetrahydrofuran-ammonia system is 0.05 M whereas in the ether-dioxane-ammonia system it is 0.029 M. 

The general reaction procedure and apparatus used are exactly as described in Procedure 2. Ammonia (465 ml) is distilled into a 2-liter reaction flask and to this is added 165mlofisopropylalcoholandasolutionof30g(0.195 mole) of 17/ -estradiol 3-methyl ether (mp 118.5-120°) in 180 ml of tetrahydrofuran. The steroid is only partially soluble in the mixture. A 5 g portion of sodium (26 g, 1.13 g-atoms total) is added to the stirred mixture and the solid dissolves in the light blue solution within several min. As additional metal is added, the mixture becomes dark blue and a solid (matted needles) separates. Stirring is inefficient for a few minutes until the mass of crystals breaks down. All of the sodium is consumed after 1 hr and 120 ml of methanol is then added to the mixture with care. The product is isolated as in Procedure 4h 2. After being air-dried, the solid weighs 32.5 g (ca. 100% for a monohydrate). A sample of the material is dried for analysis and analyzed as described in Procedure 2 enol ether, 91% unreduced aromatics, 0.3%. The crude product may be crystallized from acetone-water or preferably from hexane. 

When the reaction of S2CI2 with ammonia is carried out in a polar solvent, e.g., DMF, the hydrolysis of the reaction mixture with aqueous HCl produces a mixture of the cyclic sulfur imides S7NH, 1,3-, 1,4- and 1,5-S6(NH)2 and 1,3,5- and 1,3,6-S5(NH)3, which can be separated by chromatography on silica gel using CS2 as eluant (Section 6.2.1). °... 

When the 4,4 -dinitroazoxyfurazan 240 reacted with ammonia in anhydrous CHCI3, a mixture of live compounds was formed (Scheme 162) (000HAC48). Compound 241 (59%) was the predominant product. However, the most interesting result of this reaction is the isolation of 3-azido-4-nitrofurazan (3%) and triazene 242 (13%). The formation of these compounds could be explained by reacting the intermediate diazotate generated from the leaving nitrofurazanazoxy moiety with ammonia and with 3-amino-4-nitrofurazan, respectively. 

All these syntheses form variations of the same reaction. The three-membered ring is formed from an A-halogenoamine with ketone-ammonia mixtures or the Schiff s base 3,4-dihydroisoquinoline. Starting from these first observations the three groups of authors were able to generalize their diaziridine syntheses quickly in the years 1959-1962 they were extended to generally applicable reactions. In numerous variations of the syntheses, large numbers of diaziridincs were prepared. 

Preparation of 1 -(/3-D-arabinofuranosyl)-2-thiocytosine A solution of 2.0 g of 1 -(2, 3, 5 -0-triacetyl-/3-D-arabinofuranosyl)-2,4-dithiouracil in 100 ml of methanol is saturated with anhydrous ammonia at 0°C. The mixture, in a glass liner, is heated in a pressure bomb at 100°C for three hours. The reaction mixture is concentrated to a gum in vacuo, and most of the byproduct acetamide is removed by sublimation at 60°C/0.1 mm. The residue is chromatographed on 100 g of silica gel. Elution of the column with methylene chloride-methanol mixtures with methanol concentrationsof 2-25% gives fractions containing acetamide and a series of brown gums. The desired product is eluted with 30% methanol-methylene chloride to give a total yield of 0.386 g (30%), MP 175°-180°C (dec.). Recrystallization from methanol-iso-propanol furnishes an analytical sample, MP 180°-182°C (dec.). 

In about 250 cc of liquid ammonia (cooled with dry ice and acetone) are dissolved about 7.5 g of potassium and into the solution acetylene is passed until the blue color has disappeared (about 3 hours). Then slowly a solution or suspension of 3 g of estrone in 150 cc of benzene and 50 cc of ether is added. The freezing mixture is removed, the whole allowed to stand for about 2 hours and the solution further stirred overnight. Thereupon the reaction solution is treated with ice and water, acidified with sulfuric acid to an acid reaction to Congo red and the solution extracted five times with ether. The combined ether extracts are washed twice with water, once with 5% sodium carbonate solution and again with water until the washing water is neutral. Then the ether is evaporated, the residue dissolved in a little methanol and diluted with water. The separated product is recrystallized from aqueous methanol. The yield amounts to 2.77 g. The 17-ethiny I-estradiol-3,17 thus obtained melts at 142°C to 144°C . 

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