Ammonia in toluene

All reported syntheses of TATB to date involve the nitration of substrates containing leaving groups which are subsequently replaced by amino groups. The current industrial synthesis of TATB (14) involves the nitration of 1,3,5-trichlorobenzene (33) to 1,3,5-trichloro-2,4,6-trinitrobenzene (34) followed by reaction with ammonia in toluene under pressure. Both nitration and amination steps require forced conditions with elevated temperatures. 

The nitration of l,3,5-trichloro-2-nitrobenzene (8) to l,3,5-trichloro-2,4-dinitrobenzene (9) with dinitrogen pentoxide in absolute nitric acid goes to completion in only 2-4 minutes at 32-35 °C. Further nitration of (9) would yield l,3,5-trichloro-2,4,6-trinitrobenzene (10) which undergoes ammonolysis on treatment with ammonia in toluene to give the thermally stable explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) (11). The same sequence of reactions with l,3-dichloro-2-nitrobenzene provides a route to l,3-diamino-2,4,6-trinitrobenzene (DATE). Such reactions are clean and occur in essentially quantitative yield. 

Polymethyldimethylsilazanes are synthesised by the coammonolysis of a mixture of methyltrichlorosilane and dimethyldichlorosilane in the 3 1 mole ratio with gaseous ammonia in toluene solution ... 

Polydimethylphenylsilazane varnishes (types A and B) are obtained by the coammonolysis of dimethyldichlorosilane and phenyltrichlorosilane (in the equimolar ratio) with gaseous ammonia in toluene medium ... 

An older route is based on just toluene and ammonia in the absence of air with separate catalyst regeneration (77). 

Aminoalkoxy pentaerythritols are obtained by reduction of the cyanoethoxy species obtained from the reaction between acrylonitrile, pentaerythritol, and lithium hydroxide in aqueous solution. Hydrogen in toluene over a mthenium catalyst in the presence of ammonia is used (34). The corresponding aminophenoxyalkyl derivatives of pentaerythritol and trimethyl olpropane can also be prepared (35). 

These effects can be attributed mainly to the inductive nature of the chlorine atoms, which reduces the electron density at position 4 and increases polarization of the 3,4-double bond. The dual reactivity of the chloropteridines has been further confirmed by the preparation of new adducts and substitution products. The addition reaction competes successfully, in a preparative sense, with the substitution reaction, if the latter is slowed down by a low temperature and a non-polar solvent. Compounds (12) and (13) react with dry ammonia in benzene at 5 °C to yield the 3,4-adducts (IS), which were shown by IR spectroscopy to contain little or none of the corresponding substitution product. The adducts decompose slowly in air and almost instantaneously in water or ethanol to give the original chloropteridine and ammonia. Certain other amines behave similarly, forming adducts which can be stored for a few days at -20 °C. Treatment of (12) and (13) in acetone with hydrogen sulfide or toluene-a-thiol gives adducts of the same type. 

A solution of the ketol diacetate (15 g, 0.028 mole) in toluene (200 ml) is dried by concentration to 150 ml at normal pressure. The solution is cooled to room temperature and then added with vigorous stirring to a solution of calcium turnings (4.2 g, 0.11 g-atom) in liquid ammonia (500 ml). The addition is made in 5 min, the mixture is stirred for a further 3 min, and excess calcium is then destroyed by the dropwise addition of bromobenzene ca. 4 ml). Water (5 ml) is added cautiously and the ammonia is allowed to evaporate. The toluene is removed by distillation on a steam-bath under reduced pressure and methanol (200 ml) is added to the residue, followed by a solution of potassium hydroxide (5 g) in water (10 ml). The mixture is boiled for 1 hr, water (50 ml) is added, and the mixture is warmed on the steam bath for 30 min in order to coagulate the product. Water (250 ml) and acetic acid (15 ml) are added, the mixture is cooled and the product filtered, washed thoroughly with water and dried to give 12.3 g of crude 11-ketotigogenin, mp 209-218° Md, -31°. 

A solution of 23.7 grams of 2-bromoacetamido-2 -fluorobenzophenone in tetrahydrofuran (100 cc) was added to liquid ammonia (approximately 500 cc) and allowed to evaporate overnight. The residue was treated with water (1 liter) and the crystals filtered off and refluxed in toluene (100 cc) for 30 minutes. The mixture was treated with decolorizing carbon (Norite) and filtered over Hyflo. The solution was concentrated to a small volume (25 cc) cooled, diluted with 20 cc of ether and allowed to stand. The product was re-crystallized from acetone/hexane to give 5-(2-fluorophenyl)3H-1,4-benzodiazepin-2(1 H)-one as white needles melting at 180° to 181°C. 

A mixture of 20 g (0.1 mol) of 1 -azaphenothiazine, 4.3 g (0.11 mol) of sodamide and 300 ml of dry toluene is stirred and refluxed for eight hours. A slow stream of dry nitrogen gas is used to sweep out the ammonia as formed. The mixture is cooled and 110 ml of a 1 M solution of 3-dimethylaminopropyl chloride in toluene is added dropwise, with stirring. Subsequently, the mixture is stirred and refluxed for fifteen hours, cooled, and concentrated in vacuo. The viscous residue is refluxed with 500 ml of chloroform and filtered hot. The chloroform filtrate is treated with activated charcoal and again filtered. The filtrate is concentrated and the residue distilled to give about 19.B g (69% yield) of product, an oil distilling at about 195 C to 19B°C (under 0.5 mm pressure of mercury). 

A solution of 1.5 mol equiv of butyllithium in hexane is added to 1.5 mol equiv of a 1 M solution of hexabutylditin in THF at 0 C under nitrogen, and the mixture is stirred for 20 min. The solution is cooled to — 78 °C and a solution of 1.5 mol equiv of diethylaluminum chloride in toluene is added. After stirring for 1 h at — 78 °C, a solution of 0.05 mol equiv of [tetrakis(triphenyl)phosphine]palladium(0) in THF is added followed by a solution of the allyl acetate in THF. The mixture is warmed to r.t., and stirred until the allyl acetate has reacted (TLC). The solution is cooled to 0°C, and an excess of aq ammonia slowly added. After an aqueous workup, the products arc isolated and purified by flash chromatography on silica gel using 1 % triethylamine in the solvent to avoid acid-induced loss of stannane. 

A typical chem manufg operation is the production of trinitrotoluene — TNT, the dominant mil expl. It involves the manuf of huge quantities of nitric and sulfuric acids, from sulfur and ammonia, in chem plants exactly similar to those which make nitric and sulfuric acids in the civilian economy. Mixed nitric and sulfuric acid is then combined with liq toluene in a series of reaction kettles... 

Anon., Univ. Safety Assoc., Safety Newsletter, 1982-1984 A solution of the chloride (120 ml) in toluene (750 ml) was treated (apparently without effective stirring) with excess sodium bicarbonate solution to destroy it. When reaction had ceased, the organic layer was poured into a waste solvent drum. Vigorous evolution of sulfur dioxide and hydrogen chloride then ensued from reaction with ethanol (toluene-soluble) in the waste drum. For destruction of solutions of sulfinyl chloride in water-insoluble solvents, extremely good agitation is necessary to ensure proper contact with a basic reagent. Ammonia is more soluble in toluene than is water, so ammonia solution should be used after bicarbonate treatment to ensure complete destruction. 

The ONSH reaction of the carbanion of 2-phenylpropionitrile (45 c) with nitrobenzene in liquid ammonia at -70 °C involves rate-limiting Carom—H bond breaking, as evidenced by the 9.8 times faster rate than for reaction of the analogous substitution of deuterium in 4-<7-nitrobenzene and perdeuterionitrobenzene. Reactions of the carbanion derived from (45c) with 4-chloro-3-trifluoromethylnitrobenzene and 4-chloronitrobenzene in toluene under phase transfer catalysis has also been studied." ... 

Sulphur, Selenium, and Tellurium Compounds.—The crystal structure of the metal-rich zirconium sulphide Zr Sj has been determined and each sulphur atom shown to be at the centre of a square antiprism of zirconium atoms. The reaction of ZrS2 with potassium in liquid ammonia has been shown to give four K ZrS2 phases (.x = 1, 0.86, 0.71, or 0.71—0.22) which differ in the nature of the co-ordination sites occupied by the potassium atoms between the ZrS2 layers. ZrCl reacts with NaS2P(OEt)2 in toluene to form [Zr S2P-(OEt)2 4], which appears to involve a trigonal-dodecahedral arrangement of sulphur atoms about the metal. ... 

The acidic/basic properties of zeolites can be changed by introdnction of B, In, Ga elements into the crystal framework. For example, a coincorporation of alnminnm and boron in the zeolite lattice has revealed weak acidity for boron-associated sites [246] in boron-snbstitnted ZSM5 and ZSMll zeolites. Ammonia adsorption microcalorimetry gave initial heats of adsorption of abont 65 kJ/mol for H-B-ZSMll and showed that B-substituted pentasils have only very weak acidity [247]. Calcination at 800°C increased the heats of NH3 adsorption to about 170 kJ/mol by creation of strong Lewis acid sites as it can be seen in Figure 13.13. The lack of strong Brpnsted acid sites in H-B-ZSMll was confirmed by poor catalytic activity in methanol conversion and in toluene alkylation with methanol. 

A reexamination of the ammonia-toluene coadsorption shows that ammonia prevents the formation of benzyl-species at room temperature in the presence of ammonia, in fact, toluene only weakly adsorbs at r.t. in a reversible form. This agrees with the strong inhibiting effect of toluene conversion by ammonia due to the competitivity of the two reactants on the same adsorption sites (77,72). The spectrum... 

The synthetic and industrial importance of this reaction lies in its generality, and the ease with which the amino substituent in the products can be subsequently transformed into other functionalities. Pyridine itself is more difficult to aminate than quinoline or isoquinoline, and it does not react with potassium amide in liquid ammonia even on prolonged treatment. However, pyridine is aminated in good yield by sodamide in toluene, and di- and tri-amination can be achieved with excess sodamide at higher temperatures. The 4-position is substituted last in triamination y-amination is very difficult indeed and only takes place when all a -positions are occupied. 

Alkylpyridines are aminated preferentially at the 2-position, but reaction is slower than in the parent system. Quinoline is difficult to aminate and only a low yield of 2-aminoquinoline (32%) is obtained from reaction with sodamide in toluene. When dimethylaniline is employed as solvent, 2-amino-3,4-dihydroquinoline (24%) becomes the major product, and the yield of 2-aminoquinoline drops to 7%. The best yields of 2-aminoquinoline (53-69%) have been obtained by using barium or potassium amide in liquid ammonia. Use of the potassium salt also produces a 10% yield of the 4-amino isomer. The... 

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