Diethyl aqueous ammonia

To a solution of 0.30 mol of ethyllithium (note 1) in about 270 ml of diethyl ether (see Chapter II, Exp. 1) v/as added 0.30 mol of methoxyallene at -20°C (see Chapter IV, Exp. 4) at a rate such that the temperature could be kept between -15 and -2Q°C. Fifteen minutes later a mixture of 0.27 mol of >z-butyl bromide and 100 ml of pure, dry HMPT ivas added in 5 min with efficient cooling, so that the temperature of the reaction mixture remained below 0°C. The cooling bath was then removed and the temperature was allowed to rise. After 4 h the brown reaction mixture was poured into 200 ml of ice-water. The aqueous layer was extracted twice with diethyl ether. The combined solutions were washed with concentrated ammonium chloride solution (which had been made slightly alkaline by addition of a few millilitres of aqueous ammonia, note 2) and dried over potassium carbonate. After addition of a small amount (2-5 ml) of... 

A solution of a-lithiomethoxyallene was prepared from nethoxyal lene and 0.20 mol of ethyllithiurn (note 1) in about 200 ml of diethyl ether (see Chapter II, Exp. 15). The solution was cooled to -50°C and 0.20 mol of ethylene oxide was added immediately. The cooling bath was removed temporarily and the temperature was allowed to rise to -15 c and was kept at this level for 2.5 h. The mixture was then poured into 200 ml of saturated ammonium chloride solution, to which a few millilitres of aqueous ammonia had been added (note 2). After shaking the layers were separated. The aqueous layer was extracted six times with small portions of diethyl ether. The combined ethereal solutions were dried over sodium sulfate and subsequently concentrated in a water-pump vacuum. Distillation of the... 

A solution of 0.10 mol of lithiated methoxyallene in about 70 ml of hexane and 50 ml of THF (see Chapter II, Exp. 15) was cooled to -40°C. Ory, pure acetone (0.12 mol) was added dropwise during 10 min, while keeping the temperature at about -30°. Five minutes after the addition 100 ml of saturated NHi,Cl solution, to which 5 ml of aqueous ammonia had been added (note 1), were run in with vigorous stirring. The product was extracted three times with diethyl ether. The combined organic solutions were dried over potassium carbonate and subsequently... 

Reactions with Ammonia and Amines. Acetaldehyde readily adds ammonia to form acetaldehyde—ammonia. Diethyl amine [109-87-7] is obtained when acetaldehyde is added to a saturated aqueous or alcohoHc solution of ammonia and the mixture is heated to 50—75°C in the presence of a nickel catalyst and hydrogen at 1.2 MPa (12 atm). Pyridine [110-86-1] and pyridine derivatives are made from paraldehyde and aqueous ammonia in the presence of a catalyst at elevated temperatures (62) acetaldehyde may also be used but the yields of pyridine are generally lower than when paraldehyde is the starting material. The vapor-phase reaction of formaldehyde, acetaldehyde, and ammonia at 360°C over oxide catalyst was studied a 49% yield of pyridine and picolines was obtained using an activated siHca—alumina catalyst (63). Brown polymers result when acetaldehyde reacts with ammonia or amines at a pH of 6—7 and temperature of 3—25°C (64). Primary amines and acetaldehyde condense to give Schiff bases CH2CH=NR. The Schiff base reverts to the starting materials in the presence of acids. 

Cellulose for chromatography is purified by sequential washing with chloroform, ethanol, water, ethanol, chloroform and acetone. More extensive purification uses aqueous ammonia, water, hydrochloric acid, water, acetone and diethyl ether, followed by drying in a vacuum. Trace metals can be removed from filter paper by washing for several hours with O.IM oxalic or citric acid, followed by repeated washing with distilled water. 

S4N2 forms dark red needles (mp 23°C) upon recrystallization from diethyl ether. It sublimes readily at room temperature, but must be stored at -20°C to avoid decomposition. Several routes are available for the preparation of S4N2. The decomposition of Hg(S7N)2 at room temperature gives the best yield, while the reaction of S2CI2 with aqueous ammonia is quick, cheap and provides a purer product. 

The oily residue is taken up in 100 ml of 6 N aqueous hydrochloric acid and refluxed until a clear solution is obtained. The latter is made basic with aqueous ammonia and extracted with diethyl ether the organic solution is separated, washed, dried and evaporated. The residue is distilled under reduced pressure to yield 26.3 g of 1-(o-chlorophenyl)-2-methyl-2-propylamine, BP 116° to 118°C/16 mm. 

When diethyl aminomethylenemalonate (9, R1 = R2 = H) was reacted with aqueous ammonia at 100°C in a closed tube, malonamide was obtained. Decomposition of 9 (R1 = R2 = H) also occurred on the action of boiling aqueous barium hydroxide (1892JCS791). 

The chloromethylpyrimido[5,4-( ]-l,2,4-triazine 86 is an extremely versatile starting material (see Section 10.20.7.2, Equation 12) and was synthesized from the commercially available thiol 151 as shown in Scheme 25. Thus, 6 -methylation of compound 151 gave the sulfide 152, which was nitrosated to allow access to the nitroso-thiomethyl derivative 153. Nucleophilic substitution of the thiomethyl group by hydrazine gave the cyclization precursor 154, which underwent cyclization with chloroacetaldehyde diethyl acetal under acidic conditions to give the chloro-methylpyrimido[5,4-( ]-l,2,4-triazine 86 after workup with aqueous ammonia <2003BML2895>. 

N aqueous ammonia are added to the mixture. The insoluble constituents are filtered off and washed ion-free with diethyl ether and water. The filter cake is dried and there is obtained l-(p-methoxybenzoyl)-2-pyrrolidinone having a melting point of 119.5°-120.5°C. 

The acidic extracts are mixed and purified from traces of dichloroethane by means of shaking out with diethyl ether. Under stirring and cooling to 15° to 20°C, about 200 ml of a 25% aqueous ammonia solution is then added up to alkaline litmus reaction (the pH is in the range of 7 to 8). Different from the indications in the art, the companion alkaloids do not precipitate. The alkaline solution is saturated with salt and extracted with diethyl ether. 

Bromo-1 i/-pyrrolo[2,3-6]pyridine (73) can be readily converted to an amino derivative in good yield using aqueous ammonia at elevated temperatures. Similarly, ethylenediamine and diethyl-enetriamine also reacted, though in lower yields (Equation (15)) <92BCJ2992>. Under these conditions the 6-chloro isomer did not undergo the reaction. 

Diethyl Tellurium Chloride Hydroxide4 Diethyl tellurium dichloride is added to an excess of aqueous ammonia and the mixture is carefully heated until the tellurium compound has dissolved. The solution is then concentrated until the product crystallizes. The product is recrystallized from ethanol. 

Triturate the residue with diethyl ether (50 mL), then add concentrated (35%) aqueous ammonia solution (20 mL) and stir at room temperature overnight. 

In order to allow for this side reaction the mixture, from which a portion of the acet-w-phenetidine has crystallized, is again subjected to similar treatment with one-half the initial quantities of alkali and diethyl sulfate. It is then allowed to stand overnight after adding 100 cc. of concentrated aqueous ammonia to assist in the decomposition of any remaining excess of diethyl sulfate, the ammonia being alkylated just as any other amine. 

A 74.3% mixture of a- and 9-2-methyl-4-oxooctahydro-1 -pyrincline (203) and (204) is obtained from the condensation of propenyl 1-cyclo-pentenyl ketone and aqueous ammonia.137 Chromatography on aluminum oxide (2 1 diethyl ether-petroleum ether) gave 40% 203 and 42%... 

When 5-nitrosopyrimidine-4,6-diamines are treated with excess dimethylformamide diethyl acetal followed by warming with 10% aqueous ammonia in the presence of ethanol at 80 C for 20 minutes, the corresponding 8-(dimethylamino)adenine derivatives 5 are obtained in almost quantitative yield. ... 

Triphenyloxazole (5g), formamide (40g) and liquid ammonia (lOOtnl) are heated in an autoclave at 200-210°C (5h). The brownish reaction product is poured into water, and the flocculent precipitate is filtered, washed with water and recrystallized from ethanol (4.3 g, 85%), m.p. 273°C. Similarly prepared are 2,5-diethyl-4-phenyl- (25%), 2-methyl-4,5-dipropyI-(70%) [41], 4-eihyl-5-phenyl- (50%), 4-phenyl-5-propyl- (40%) and4-benzyl-5-ethyl imidazoles (5%) [40]. From 2-methyloxazole-4-carboxylic acid boiled at 150°C in a sealed tube with aqueous ammonia is obtained 2-methylimidazole (22%) boiling with aniline gives 2-methyl-l-phenylimidazole (67%) [52]. 

The parent compound of this series, pyrazine, was first prepared in trace amounts by Wolff (30) by heating aminoacetaldehyde diethyl acetal [H2NCH2CH(OEt)2] with anhydrous oxalic acid at 110-190°C, and later in better yield by heating the mercuric or platinic chloride double salts (of the aminoacetaldehyde acetal) with hydrochloric acid (31) it was also obtained from aminoacetaldehyde with mercuric chloride in sodium hydroxide (23). Wolff in 1893 (22) also prepared pyrazine by decarboxylation of the tetracarboxylic acid, obtained by oxidation of tetramethyl-pyrazine and Stoehr (32) prepared it by the distillation of piperazine with lime and zinc dust. Brandes and Stoehr (33) in 1896 described the preparation of pyrazine by heating glucose with 25% aqueous ammonia at 100°C. 

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