Ammonia yields

Reaction with AlCl gives lithium aluminum hydtide, which is the main apphcation of hthium hydtide. Reaction with ammonia yields hthium amide... 

Dual-Pressure Process. Dual-pressure processes have a medium pressure (ca 0.3—0.6 MPa) front end for ammonia oxidation and a high pressure (1.1—1.5 MPa) tail end for absorption. Some older plants still use atmospheric pressure for ammonia conversion. Compared to high monopressure plants, the lower oxidation pressure improves ammonia yield and catalyst performance. Platinum losses are significantiy lower and production mns are extended by a longer catalyst life. Reduced pressure also results in weaker nitric acid condensate from the cooler condenser, which helps to improve absorber performance. Due to the spHt in operating conditions, the dual-pressure process requires a specialized stainless steel NO compressor. 

However, when either P(CgH )(CH2)2 or P(CgH )2(CH2) is used to form cis- or /n j -M(N2)2(PR3)4j M = Mo or W, respectively, followed by treatment with acid, ammonia yields of about 2 mol or 0.7 mol pet mole of complex for M = W and Mo, respectively, are produced (193,194). These and related data have been used to suggest a possible stepwise sequence for the reduction and protonation of N2 on a single molybdenum atom ia nitrogeaase (194). However, acidificatioa leads to complete destmctioa of the complex. Using both the stabilizing effect of the chelating phosphine triphos,... 

Certain ketones, eg, cyclohexanone, react with hydrogen peroxide in the presence of ammonia, yielding 1,2,4-dioxazohdines (159) ... 

Isopropa.nola.mines. Reaction of propylene oxide with ammonia yields mono-, di-, and triisopropanolamines. These products find use as soluble oils and solvents, emulsifiers, waterless hand cleaners, cosmetics, cleaners, and detergents. In industrial apphcations isopropanolamines are used in adhesives, agricultural products, corrosion inhibitors, coatings, epoxy resins, metalworking, and others (51). 

Iodine reacts with sulfuryl chloride ia the presence of aluminum chloride as catalyst-forming iodine chlorides. Sulfuryl chloride reacts with anhydrous ammonia yielding a series of sulfamides of the general formula NH2S02(NHS02) NH2, where n > 0. A cycHc compound of the formula... 

Metliylpyridine can also be prepared by the condensation of acrolein and ammonia. Yields of 40—50% are obtained with pyridine as a by-product. Higher yields have been claimed when both propionaldehyde and acrolein have been used. A recent U.S. patent claims better selectivity if the cyclization is carried out in the presence of 2eohtes (3). 

Bismuth trichloride shows considerable tendency to form addition compounds. Reaction with ammonia yields the colodess, easily volatili2ed bismuth trichloride triammine [66172-89-2] BiCl ANH, as well as the red, thermally unstable bismuth trichloride hemiammine [66172-90-5] 2BiCl2 NH. Compounds of formula BiCl NO, BiCl 2N02, and BiCl NOCl may be isolated these are stable in dry air but are decomposed by moisture. Bismuth... 

Toray. The photonitrosation of cyclohexane or PNC process results in the direct conversion of cyclohexane to cyclohexanone oxime hydrochloride by reaction with nitrosyl chloride in the presence of uv light (15) (see Photochemical technology). Beckmann rearrangement of the cyclohexanone oxime hydrochloride in oleum results in the evolution of HCl, which is recycled to form NOCl by reaction with nitrosylsulfuric acid. The latter is produced by conventional absorption of NO from ammonia oxidation in oleum. Neutralization of the rearrangement mass with ammonia yields 1.7 kg ammonium sulfate per kilogram of caprolactam. Purification is by vacuum distillation. The novel chemistry is as follows ... 

Reaction of ethyl chloride with an alcohoHc solution of ammonia yields ethylamine, diethylamine, triethylamine, and tetraethyl ammonium chloride (10,11) (see Amines, lower aliphatic). 

Reduction of linearly conjugated 4,6-dien-3-ones with lithium-ammonia yields either 5-en-3-ones or 4-en-3-ones depending upon the work-up procedure. Protonation of the dienyl carbanion intermediate (58) occurs at C-7 to give ultimately the enolate ion (59) kinetic protonation of (59) occurs largely at C-4 to give the 5-en-3-one (60). ... 

The acetates of vicinal diols undergo reductive elimination on treatment with metal-ammonia yields of olefin are only significant if one ester is tertiary and the arrangement is tran -diaxial. ... 

Anhydrous ammonia adds tofluorooleftns to produce nitriles Tins phenomenon IS used to characterize chemically the terminal difluoromethylene olefin that IS claimed to be m equilibrium with the internal isomer [4] (equation 2) Thus isomerization to the terminally unsaturated isomer prior to attack by ammonia yields the cyanoenamine... 

The base, which has a brown colour, is filtered and dissolved m hot spirit, with the addition of a few diops of concentrated ammonia. Yield, about 8 grams. 

The amination of 2-chloropyridine-A-oxide (53) with potassium amide in liquid ammonia yielded a mixture of 2-(55) and 3-amino-pyridine-A-oxide (56) in 5-10% total yield.This rearrangement might be explained by an aryne mechanism involving 2,3-pyridyne-A-oxide (54). Since the structure of 56, with its quaternary nitrogen atom, is more analogous to that of 3-methoxybenzyne (39) than to that of 2,3-pyridyne (26), an orientation effect directing the amide ion to C-3 can be expected here. 

The almost quantitative formation of free ammonia can be used for an estimation of the oxazirane. With pure oxaziranes, ammonia yields of 93-96% are obtained. 

Treatment of the hydrobromide with a slight excess of ethanolic ammonia yields the base which may then be converted to the hydrochloride. 

Chlorsulfonic acid and 3-chloroaniline react to give an intermediate which when treated with ammonia yields 5-chloro-2,4-disulfamylaniline. 

Alkynes can be reduced to yield alkenes and alkanes. Complete reduction of the triple bond over a palladium hydrogenation catalyst yields an alkane partial reduction by catalytic hydrogenation over a Lindlar catalyst yields a cis alkene. Reduction of (he alkyne with lithium in ammonia yields a trans alkene. 

Interestingly, photolysis of phenyl azide in liquid ammonia yields 3//-azepin-2-amine (39)35 (see experimental procedure in Houben-Weyl, Vol.4/5b, pi268). 

The reaction of methyl 2-[benzyl(bromoacetyl)amino]benzoate with ammonia yields the benzo-diazepinedione 32.209... 

Historical. MEDINA was first isolated as a degradation prod from the nitrolysis of hexa-mine (WWI1 work done at the Univ of Bristol, cited in Ref 5). It was prepd by the hydrolysis of PCX (qv) in boiling et ale and isolated as the Ba salt (Ref 4) and by the hydrolysis of N,N -DiacetylMEDINA with aq ammonia, yield 25% (Ref 5)... 

Polymer 1 is decomposed by reaction with ammonia, yielding methylamine and the intermediate A-trimethyl-.8-tri(amino)borazine 2, which was partially sublimed resulting in a major loss of fiber integrity (scheme 2). 

Ugi and Domling have shown that the U-4CR can also be combined with other MCRs, thus creating sequences which involve up to nine different substrates [33]. An example of such an approach is the combination of an Ugi-4CR with the as-yet not mentioned Asinger reaction (A-3CR or A-4CR). The latter allows the formation of thiazolines from ammonia, carbonyl compounds and sulfides [34]. As shown in Scheme 9.7, a mixture of a-bromoisobutyraldehyde, isobutyraldehyde, sodium hy-drogensulfide and ammonia yields the imine 9-38 which, by reaction with t-butyl-isocyanide, methanol, and C02, led to the final product 9-39 [35]. 

This was a development of the Andrussov process by which methane yields hydrogen cyanide. In one important version, propylene and ammonia yield acrylonitrile ... 

Treatment of an N-(2-bromoahyl)alkylamine with sodium amide in liquid ammonia yields the N-alkylallenimine together with a small amount of the N-alkylpropargylamine. -7 Similar... 

In contrast to the above-discussed cyclizations, two syntheses including ring closure of the five-membered ring have been described for [l,2,4]triazolo[l,5- ][l,3,5]triazines. The chemical transformations are shown in Scheme 38. Caulkett et al. published that the 2-hydrazino[l,3,5]triazine derivative 188 when treated with acid chlorides underwent ring closure and subsequent treatment with ammonia yielded the 5-amino compound 190 <1995J(P1)801>. 

M[pz(A4)] A = S2ML2. The octakis(.V-R)porphyra/,ines reported by Schramm and Hoffman (2), M[pz(S-R)8 (M = Ni, Cu), (60), can be converted to the octathiolate M[pz(S )g] (Scheme 11) via reductive cleavage of the sulfur-carbon bond when R = benzyl (Bn), and this tetra-bis(dithiolate) can then be peripherally capped with metal-ligand systems to yield peripherally tetrametalated star porphyrazines. The benzyl dinitrile 57 can be macrocyclized around magnesium butoxide to form [Mg[pz(S-Bn)8] (58) (35-40%), which can then be demetalated with trifluoroacetic acid to form 59 (90%), which is subsequently remetalated with nickel or copper acetate to form 60a (95%) and 60b (70%) (Scheme 11) (3, 23, 24). Deprotection of 60a or 60b with sodium in ammonia yields the Ni or Cu tetra-enedithiolates, 61a or 61b to which addition of di-ferf-butyl or n-butyl tin dinitrate produces the peripherally metalated star porphyrazines 62a (37%), 62b (80%), and 62c (41%). 

In a quite analogous way ammonia yields hydrocyanic acid. 

The photohydrolysis of 2-fluoro-4-nitroanisole to 2-methoxy-5-nitrophenole is sensitized by benzophenone and completely quenched by sodium sorbate The excited state multiplicity in photoaminations has also been studied. Photolysis of mNA in liquid ammonia yields m-nitroaniline. If the amination is carried out in a large excess of benzophenone, 2-methoxy-4-nitroaniline is formed instead and thus an excited singlet state as reacting species is envisaged in the unsensitized photoamination loo.ioi). it may well be that uptake of the nucleophile present in high concentration successfully competes with intersystem crossing. 

Amination of 4-methyl-, 4-A -methylamino-, and 4-anilino-5-bromopyrim-idine with potassium in liquid ammonia yields the corresponding 6-... 

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