Ammonia Amyl alcohol

The solubility of many steroids in ammonia-tetrahydrofuran-/-butyl alcohol is about 0.06 A/, a higher concentration than has been reported in other solvent systems. Still higher concentrations may be possible in particular cases by suitable variation in the solvent ratios Procedure 3 (section V) describes such a reduction of estradiol 3-methyl ether at a 0.12 M concentration. A few steriods such as the dimethyl and diethyl ketals of estrone methyl ether are poorly soluble in ammonia-tetrahydrofuran-/-buty] alcohol and cannot be reduced successfully at a concentration of 0.06 even with a 6 hour reduction period. The diethyl ketal of estrone methyl ether is reduced successfully at 0.12 M concentration using a two-phase solvent system of ammonia-/-amyl alcohol-methylcyclohexane (Procedure 4, section V). This mixture probably would be useful for any nonpolar steroid that is poorly soluble in polar solvents but is readily soluble in hydrocarbons. 

Alkyl acids > C2 Alumina Ammonia Amyl alcohol Benzoic anhydride Benzophenone... 

Amination. Amyl alcohols can react with ammonia or alkylamines to form primary, secondary, or tertiary-substituted amines. Eor example, 3-methyl-butylamine [107-85-7] is produced by reductive ammonolysis of 3-methyl-1-butanol over a Ni catalyst at 150°C (59). Some diisoamyl- and triisoamyl amines are also formed in this reaction. Good selectivities (88%) of neopentyl amine [5813-64-9] are similarly produced by reductive ammonolysis of neopentyl alcohol (60). 

Decamethylene glycol has been prepared by the reduction of dimethyl sebacate and diethyl sebacate with sodium and ethyl alcohol by the reduction of sebacamide with sodium and amyl alcohol and by the reduction of dimethyl sebacate with sodium and liquid ammonia in absolute alcohol. The reduction of esters with sodium and alcohol has also been applied to the preparation of many other glycols. ... 

The reduction is carried out much as described in Procedure 2. Ammonia (950 ml) is distilled into a 5-liter reaction flask and 950 ml of /-amyl alcohol and a solution of the ketal in 950 ml of methylcyclohexane are added with good stirring. Sodium (57 g, 2.5 g-atoms) is added in portions. The reaction mixture becomes blue within 30-45 min after the sodium is added and the metal is consumed within about 3 hr after the blue color appears. After the mixture becomes colorless, 200 ml of ethanol is added and the ammonia is allowed to boil off through a mercury trap. Then 500 ml of water and 500 ml 0% potassium bicarbonate solution are added and the organic layer is separated. The organic layer is washed once with 10 % potassium bicarbonate... 

Birch reduction of the diethyl ketal of estrone 3-methyl ether in ammonia-methylcyclohexane-t-amyl alcohol,... 

The reaction can be performed under a variety of conditions. Origin-aiiyi2o,i26,234 acetylene and potassium in liquid ammonia were used. Subsequently, this was simplified by the use of potassium r-amylate in r-amyl alcohol and later this system was found to react selectively at C-17 in the presence of an A-ring a,j5-unsaturated ketone. A closer investigation of these reaction conditions revealed the formation of a small amount (2-3 %) of the disubstituted acetylene this can be avoided by reacting the 17-keto steroid with acetylenedimagnesium bromide in ether-tetrahydrofuran (see chapter 10.)... 

Lauryl alcohol has been prepared by the reduction of the aldehyde with zinc dust and acetic acid 1 by the reduction of esters of lauric acid with sodium and absolute alcohol 2 or with sodium, liquid ammonia, and absolute alcohol 3 by the reduction of lauramide with sodium and amyl alcohol.4 The method in the above procedure is essentially that described by Levene and Allen.5... 

Partial reduction of naphthols was accomplished by sodium in liquid ammonia. In the absence of alcohols small amounts of 5,8-dihydro-a-naphthol or 5,8-dihydro- -naphthol were isolated. In the presence of tert-amyl alcohol, a-naphthol gave 65-85% yield of 5,8-dihydro-a-naphthol while -naphthol afforded 55-65% of -tetralone [399] Procedure 26, p. 211). Lith-... 

Diammino-uranyl Nitrate, [U02(NH3)2](N03)2, is formed when dry gaseous ammonia is passed into a boiling solution of dry uranyl nitrate in amyl alcohol until the liquid is decolorised. A voluminous yellow precipitate is formed, which is collected and dried in vacuo over sulphuric acid. The product is only freed from amyl alcohol by repeated evacuation over fresh quantities of sulphuric acid. It is a yellow amorphous powder, which is insoluble in ether and amyl alcohol. If the diammine is prepared in ether the same reaction takes place, and, after evacuation over sulphuric acid, a bright yellow powder is obtained of composition [UO2(NH3)2](NO3)2.C2H10O this, on keeping in vacuo, gradually loses ether, yielding the diammino-nitrate. 

Diammino-uranyl Bromide, [U02(XH3)2]Br2, is prepared by passing ammonia gas through a solution of uranyl bromide in amyl alcohol till the solution is decolorised and a flocculent yellow precipitate is produced on drying in vacuo the substance is obtained as a yellow amorphous powder, hr properties it resembles the chloride. An ether derivative, of composition [UO2(XH3)2]Cl2.C2H100, is formed if ammonia is passed into an ethereal solution of uranyl bromide. Tri-ammino-uranyl bromide, [U02(XH3)3]Br2, and tetrammino -uranyl bromide, [U02(XH3)4]Br2, are prepared by an analogous method to that for the preparation of the corresponding chlorides, and the properties are similar. 

Azetidine has been prepared by the following procedures cyclization of 3-bromopropylamine with potassium hydroxide (low yield) 2 cleavage of 1 -p-toluenesulfonylazetidine with sodium and refluxing -amyl alcohol (85-100% yield)3,4 or sodium and liquid ammonia (30% yield) 6 hydrogenolysis of 1-benzylazetidine (50%) 6 cyclization of diethyl 3-N-(3-chloro-propyl)iminodipropionate with sodium carbonate without solvent (60-70% yield).7 A review of methods for preparing azetidine has been published.8... 

Girard s test. 50 c.c. of the wine are neutralised with 10% ammonia (D 0-960), a further quantity of 5 c.c. of the same ammonia solution being added and the liquid poured into a separating cylinder of about 100 c.c. capacity. 15 c.c. of amyl alcohol are added and the whole shaken slowly, to avoid emulsification, for about 10 minutes. After settling, the liquid below the amyl alcohol is run off and the alcoholic liquid washed three times with water (100 c.c. in all), filtered through a small dry filter and... 

To ascertain if the cognac is coloured with artificial organic colouring matters, the alcohol is evaporated off, ammonia solution added and the liquid extracted with amyl alcohol evaporation of the amyl alcohol gives the colouring matters, which may be detected by their characteristic reactions and by dyeing tests with wool in acid or alkaline solution (see also Wine, and Colouring Matters). 

P. F. G. Boullay gave 33-3 parts for the solubility of ammonia in 100 parts of alcohol at 38° J. Miiller said that one vol. of absolute alcohol dissolves 340 vols. of ammonia at 20° and 760 mm. and S. Pagliano and A. Emo said that ammonia is much less soluble in ethyl, propyl, or amyl alcohol than it is in water. C. A. Lobry de Bruyn represented the solubility of ammonia in absolute methyl alcohol, expressed in grams per 100 grms. of soln., by... 

Vide supra, for the heats of soln. of ammonia in methyl, ethyl, propyl, and isobutyl alcohols. W. Herz and H. Fischer measured the distribution of ammonia between amyl alcohol and water at 25° and, expressing the results in grams per 100 c.c., he found ... 

H. M. Dawson and J. McCrae, D. P. Konowaloff, and W. Gaus also used soln. of various salts of the alkali metals, and of potassium, sodium, cupric, or barium hydroxide in place of water and also copper sulphate, copper chloride, zinc sulphate, and cadmium iodide while M. 8. Sherrill and D. E. Russ examined the effect of ammonium chromate. W. Herz and A. Kurzer examined the distribution of ammonia between water and a mixture of amyl alcohol and chloroform. Observations on the distribution of ammonia between water and chloroform were made by T. S. Moore and T. F. Winmill, G. A. Abbott and W. C. Bray, and J. M. Bell. J. H. Hildebrand gave for the molar fraction N X104 of ammonia at 1 atm. press., and 25°, dissolved by ethyl alcohol, 2300 methyl alcohol, 2730 and water, 3300. 

Mitchells or Amyl System (14). 25 parts of tert-amyl alcohol, 25 parts of n-butyl alcohol, 25 parts of acetone, 10 parts of concentrated ammonia, and enough water to make 100 parts. 

The 10-mlnute Co82 produced by the Ni82(n,p) reaction has been extracted as the thiocyanate into an organic layer of amyl alcohol-ethyl ether (l l) from a weak hydrochloric acid solution saturated with ammonium thiocyanate and then back-extracted with 6 N ammonia solution (156,208). The 5-2-minute W17 produced by a Ta (p,3n) reaction has also been extracted as the thiocyanate of W(lV) Into ethyl acetate (268). 

In 1980, Klug reported a method to detect morphine in head hair of drug abusers by TLC. He dissolved the hair in sodium hydroxide and hydrolyzed the solution with HCL. He extracted the solution with amyl alcohol and separated the components by TLC. Detection and quantitation were made by fluorimetry. The findings were between traces and 4 ng/mg. A HPTLC method was used to determine morphine in human hair. From 20 to 200 mg of hair were washed four times with water to remove surface contamination. Then the hair was incubated in sodium hydroxide and subsequently in HCL at 80°C in both cases. After SPE (type "Extrelut 3"/Merck) the solution was dansylated, analyzed by HPTLC (methanol (MeOH)/ammonia 99 1), and quantitated by densitometry. 

Naphthalene is reduced to 1,4-dihydronaphthalene by sodium and alcohol. Isomerization of this product to 3,4-dihydronaphthalene occurs with sodamide in liquid ammonia. Tetrahydronaphthalene (tetralin) is formed from naphthalene by sodium in amyl alcohol or by reduction with nickel-aluminum alloy and aqueous alkali. Catalytic hydrogenation of naphthalene can be stopped at the tetralin stage over copper chromite, Raney nickel, or alkali metal catalysts. cis-Decahydronaphthalene is produced by high-pressure hydrogenation of tetralin over Adams catalyst, whereas a mixture of cis- and trans-decalins is obtained from naphthalene under the same conditions. ... 

Anthracene and phenanthrene may be partly or completely reduced by the above procedures. Sodium in either amyl alcohol or ammonia con-... 

---