Phenylamination

The nitrogen of aHphatic and aromatic amines is alkylated rapidly by alkyl sulfates yielding the usual mixtures. Most tertiary amines and nitrogen heterocycles are converted to quaternary ammonium salts, unless the nitrogen is of very low basicity, eg, ia tn phenylamine. The position of dimethyl sulfate-produced methylation of several heterocycles with more than one heteroatom has been examined (22). Acyl cyanamides can be methylated (23). Metal cyanates are converted to methyl isocyanate or ethyl isocyanate ia high yields by heating the mixtures (24,25). 

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

Chemical Designations - Synortyms Aminobenzene Aniline Oil Blue Oil Phenylamine Chemical Formula C HjNHj. 

In the initial report by Corey and Chaykovsky, dimethylsulfonium methylide (2) reacted smoothly with benzalaniline to provide an entry to 1,2-diphenylaziridine 67. Franzen and Driesen reported the same reaction with 81% yield for 67. In another example, benzylidene-phenylamine reacted with 2 to produce l-(p-methoxyphenyl)-2-phenylaziridine in 71% yield. The same reaction was also carried out using phase-transfer catalysis conditions.Thus aziridine 68 could be generated consistently in good yield (80-94%). Recently, more complex sulfur ylides have been employed to make more functionalized aziridines, as depicted by the reaction between A -sulfonylimine 69 with diphenylsulfonium 3-(trimethylsilyl)propargylide (70) to afford aziridine 71, along with desilylated aziridine 72. ... 

N-tert-Butyloxyca rbony I- -a la nine-2,4,5-trichlorophenyl ester Pentagastrin 3-Butyl-1 -phenylamine Bufeniode 1 -Butyne... 

Primary amines are named in the IUPAC system in several ways. For simple amines, the suffix -amine is added to the name of the alkyl substituent. You might also recall from Chapter 15 that phenylamine, C6HSNH2, has the common name aniline. 

Triarylamines have been employed in arylene vinylene AB copolymers 38 by Horhold et al. using a Homer polycondensation route of aldehydes and ketones 36 with fois-phosphonate 37 (Scheme 1-12) 164]. Phenylamines have remarkably low redox potentials and their charge transport properties have been investigated extensively [65]. EL devices comprising triarylamines have demonstrated low driving voltages. 

Cations of weak bases (i.e. Bronsted acids such as the phenylammonium ion C6H5NH3) may be titrated with strong bases, and the treatment is similar. These were formerly regarded as salts of weak bases (e.g. aniline (phenylamine), Kb = 4.0 x 10 10) and strong acids an example is aniline hydrochloride (phenylammonium chloride). 

Data For Nitric Esters, Nitramines, Nitroalkyl-benzenes, and Derivatives of Phenol, Aniline, Urea, Carbamic Acid, Diphenylamine, and Tri-phenylamine , AnalChem 23,1740-7 (1951) CA 46, 5434 (1952) 71) T.L. Cottrel S. 

Nitroderivatives of toluene and/or naphthalene and/or di-phenylamine in which up to 4% of the total expl may be substituted with NC 20-30 20-30 15-20... 

No or little side reactions either with the unprotected hydroxy group present in the phenylamines, or with the unprotected hydroxyl group present in the carboxylic acids are observed. The catalytic amidation of unprotected a-hydroxycarboxylic acids also proceeds well under similar conditions. 

Carcinogens Cancer-producing agents Skin Respiratory Bladder/urinary tract Liver Nasal Bone marrow Coal tar pitch dust crude anthracene dust mineral oil mist arsenic. Asbestos polycyclic aromatic hydrocarbons nickel ore arsenic bis-(chloromethyl) ether mustard gas. P-naphthylamine benzidine 4-ami nodi phenylamine. Vinyl chloride monomer. Mustard gas nickel ore. Benzene. 

Scheme 9.8 General scheme for oxidative carbonylation of phenylamine with CO/O ...

These codes can be combined when a substance has multiple risks. Codes are then separated by a siash (for different means of penetration) or a dash (for risks of different nature). Thus 20/21/22 means that a substance is harmful by inhalation, skin contact and ingestion, if the substance is inflammable as well, it is 10-20/21/22. A compound can have different acute and chronic toxicity levels. For example, for phenylamine 20/21/22-40-48/23/24/25, ie harmful by inhalation, skin contact, ingestion possibility of irreversibie effects risk of toxic effects by inhalation, skin contact and prolonged ingestion. 

With benzene and aromatic hydrocarbons in general On particular phenylamine), the triozonide formed is insoluble and forms a very unstable gel. There was a violent detonation during the ozonisation of rubber dissolved in benzene. A gelatinous precipitate formed just before the detonation of this reaction. 

A very similar explosive reaction was obtained with the same epoxide and with phenylamine, heterocyclic amines and N-substituted amines. In the Ie case, the reaction was described as not dangerous below 60 C and dangerous above 70 C. The large number of accidents that bring this epoxide and the amines mentioned into play were all caused by the fact that the reaction exothermicity was badly controlled. 

The reaction below can only be controlled at 30-80°C when phenylamine and aluminium chloride are present the reactants are diluted in an aromatic solvent and the order in which they are added is phenylamine, aluminium chloride and then aziridine ... 

With ozone, phenylamine forms a triozonide, which separates in the form of a gelatinous mass that is extremely unstable. 

Amine/hydrogen peroxide mixtures are explosive when they are prepared using specific proportions. Accidents have been reported with phenylamine and quinoline. 

When phenylamine comes into contact with sodium peroxide and water (formation of hydrogen peroxide) it combusts spontaneously. 

Performic acid at 90% gives rise to a very violent reaction with phenylamine. 

A drop of amine added to benzoyl peroxide is enough to cause a deflagration or a detonation of the peroxide, depending on to what extent the apparatus is confined. Phenylamine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine react the same way. 

This is also the case when a drop of phenylamine, ethylenediamine or N,N-dimethylaniline is added to diisopropyl diperoxycarbonate ... 

When gaseous fluorine comes into contact with phenylamine, N,N-dimethylaniline or pyridine, there is incandescence. 

Amines combust immediately when they are in contact with fuming nitric acid. The accidents described mainly involved aromatic amines (phenylamine, N-ethylaniiine, o-toluidine, xyiidines, benzidine) but also triethylamine. In the last case the ignition can take place at a temperature starting at -60°C. 

However, 96% nitric acid is not thought to ignite phenylamine except if sulphuric acid is present. 

When bases are present, nitromethane gives rise to explosive mixtures that are sensitive. Potassium hydroxide, sodium carbonate, ammonia, phenylamine, 1,2-diaminoethane, morpholine and methylamine have been involved in accidents of this nature. 

A mixture made of 80.5% of phenylamine and 19.5% of tetranitromethane combusts after a period of induction of 35 to 55 seconds and then detonates, if the liquid height exceeds a certain level in the container . In the same way a mixture of pyridine and tetranitromethane sometimes detonates after a period... 

Chloropicrin reacts violently with phenylamine in excess at 145°C. An accidental mixture of this nitrated derivative with sodium hydroxide in an alcoholic solution... 

A reaction of the same type is responsible for an accident that brought into play the effect of formol on phenylamine in the presence of perchloric acid ... 

The activity of both Pd and sulfided Pt catalysts for the synthesis of N-(l,3-dimethylbutyl)-N-phenylamine from aniline and MIBK was lower than that with acetone. This could be attributed to the steric hindrance effect (14). The selectivity over sulfided Pt catalysts was higher compared to unsulfided Pd catalysts due to formation of byproducts as with aniline-acetone reaction. 

The rare example of synergistic action of a binary mixture of 1-naphthyl-A-phcnylaminc and phenol (1-naphthol, 2-(l,l-dimethylethyl)hydroquinone) on the initiated oxidation of cholesterol esters was evidenced by Vardanyan [34]. The mixture of two antioxidants was proved to terminate more chains than both inhibitors can do separately ( > /[xj). For example, 1-naphtol in a concentration of 5 x 10 5 mol L-1 creates the induction period t=170s, 1 -naphthyl-A-phenylamine in a concentration of 1.0 x 10-4 mol L 1 creates the induction period t = 400s, and together both antioxidants create the induction period r = 770 s (oxidation of ester of pelargonic acid cholesterol at 7= 348 K with AIBN as initiator). Hence, the ratio fs/ZfjXi was found equal to 2.78. The formation of an efficient intermediate inhibitor as a result of interaction of intermediate free radicals formed from phenol and amine was postulated. This inhibitor was proved to be produced by the interaction of oxidation products of phenol and amine. 

The proposed mechanisms are similar in both cases and involve in particular an (aryl)(hydrido)ruthenium intermediate in which the ruthenium is additionally coordinated by an in. ( ////-generated /V-phenylimine moiety tethered to the same Ru-bound aromatic ring. The C-C bond-forming step for the construction of the corresponding heterocyclic framework proceeds via insertion of the C=N double bond into the C-Ru bond with transfer of the (hydrido) ruthenium complex to the now phenylamine nitrogen. The desired heterocycles 158 and 159 were obtained after successive reductive elimination, deamination, and dehydrogenation. 

Der Sprengstoff ist nicht giftig und sprengtechnisch dem Hexanitrodi-phenylamin sehr ahnlich, wenig loslich in Alkohol und Ether, leichter loslich in Eisessig und Aceton. 

---