Aniline dimethyl

Required Aniline, 4 ml. monomethylaniline, 4 ml. dimethyl-aniline, 4 ml. toluenc-/)-sulphonyl chloride, 16 g. 

Phosphorus trichloride reacts readily with three equivalents of an alcohol e.g, ethanol, in the presence of a tertiary amine such as pyridine, dimethyl-aniline, or diethylaniline, to form triethyl phosphite and hydrogen chloride, the latter being immediately neutralised by the tertiary amine. 

TEST Aniline 0- toluidine m-> toluidine P-. toluidine I- naphthyl- amine 2- naphthyl- amine mono- methyl- aniline diphenyl- amine dimethyl- aniline triphenyl- amine... 

I) An alternative procedure is to cool the solution containing the sodium sul. phanilate and sodium nitrite in a bath of crushed ice to about 5° and then add 10-5 ml. of concentrated hydrochloric acid diluted with an equal volume of water slowly and with stirring the temperature must not be allowed to rise above 10 and an excess of nitrous acid should be present (the solution is tested after standing for 5 minutes). The subsequent stages in the preparation—addition of dimethyl-aniline solution, etc.—are as above. 

Michler s ketone is prepared industrially by the interaction of phosgene (COCl,) and dimethyl aniline. 

Note 2. Prepared by introducing gaseous HCl at -10°C into a mixture of 30 g of paraformaldehyde (corresponding to 1 mol of formaldehyde) and 1 mol of ethanol, until copious fumes escaped from the mixture. This was cooled (without stirring) to -70°C and the upper layer was decanted from the solid (frozen hydrochloric acid) and mixed with 50 g of yy-diethyl(or dimethyl)aniline. Subsequent distillation in a partial water-pump vacuum afforded the desired chloroether (b.p. about 40°C/40-50 mmHg). 

The older methods have been replaced by methods which require less, if any, excess sulfuric acid. For example, sulfonation of naphthalene can be carried out in tetrachloroethane solution with the stoichiometric amount of sulfur trioxide at no greater than 30°C, followed by separation of the precipitated l-naphthalenesulfonic acid the filtrate can be reused as the solvent for the next batch (14). The purification of 1-naphthalenesulfonic acid by extraction or washing the cake with 2,6-dimethyl-4-heptanone (diisobutyl ketone) or a C-1—4 alcohol has been described (15,16). The selective insoluble salt formation of 1-naphthalenesulfonic acid in the sulfonation mixture with 2,3-dimethyl aniline has been patented (17). 

The central carbon atom is derived from an aromatic aldehyde or a substance capable of generating an aldehyde during the course of the condensation. Malachite green is prepared by heating benzaldehyde under reflux with a slight excess of dimethyl aniline in aqueous acid (Fig. 2). The reaction mass is made alkaline and the excess dimethylaniline is removed by steam distillation. The resulting leuco base is oxidized with freshly prepared lead dioxide to the carbinol base, and the lead is removed by precipitation as the sulfate. Subsequent treatment of the carbinol base with acid produces the dye, which can be isolated as the chloride, the oxalate [2437-29-8] or the zinc chloride double salt [79118-82-4]. 

The manufacture of crystal violet (1), however, is a special case which does not involve the isolation of the intermediate Michler s ketone (Fig. 3). Thus, phosgene is treated with excess dimethyl aniline in the presence of zinc chloride. Under these conditions, the highly reactive intermediate "ketone dichloride" is formed in good yield this intermediate further condenses with another mole of dimethyl aniline to give the dye. 

Methyl violet [8004-87-3] Cl Basic Violet 1 (17), is made by the air oxidation of dimethyl aniline in the presence of salt, phenol, and a copper sulfate catalyst. Initially, some of the dimethyl aniline is oxidized to formaldehyde and /V-methyl aniline under those conditions. The formaldehyde then reacts with dimethyl aniline to produce N,N,]S7,1S7-tetramethyldiaminodiphenylmethane, which is oxidized to Michler s hydrol [119-58-4]. The hydrol condenses with... 

V-methyl aniline formed in the initial step to give the leuco base of methyl violet. Treatment with aqueous acid produces the dye. Because Michler s hydrol may also react with dimethyl aniline instead of the /V-methyl aniline to give crystal violet, commercial-grade methyl violet is usually a mixture. A cobalt complex has converted 4,T-dimethylaminodipheny1methane and dimethyl aniline in the presence of atmospheric oxygen to crystal violet in one step (50). 

Condensation of phenol [108-95-2] C H O, withy -nitroso-N,N-dimethyl-aniline [138-89-6] CgH QN20, in acetic acid (9). 

Oxidative Couplings of Heterocyclic Hydrazones. This method has opened the way to the preparation of azo derivatives of diazo compounds unobtainable by other means, ie, heterocycHc compounds ia which the diazotizable amino group is conjugated with the heterocycHc nitrogen atom as ia 2- and 4-amiQopyridine, compounds which do not normally yield stable diazonium salts (38). The reaction occurs as illustrated by equation 7 for the iateraction of (A/-methylcarbostyryl)hydrazone [28219-37-6] and dimethyl aniline the overall process is oxidation. 

MA -Dimethylamino)phenyl]-2-ethylpropenal (5) was produced by reaction of A, A -dimethyl-aniline (/) with 2-ethyl-3-ethoxyacrolein (2) in the presence of phosphorus oxytrichloride. 

Recovery as liquid sulfur dioxide (absorption of clean dry off-gas in water or chemical absorbtion by ammonium bisulfite or dimethyl aniline),... 

Diethyl aniline, 54 Diethylcarbaniazine citrate, 54 Diethyl carbamyl chloride, 54 Diethyl chlorophosphate, 54 Diethylene triamine, 54 Diethyl ether, 54 Di(2-ethylhexyl) phthalate, 54 Diethyl ketone, 54 Diethyl-p-phenylenediamine, 54 Diethyl phthalate, 54 Diethylstilbestrol, 55 Diethyl sulfate, 55 Diethyl zinc, 55 Difluoromethane chloride, 55 Digitoxin, 55 Diglycidyl ether, 55 Digoxin, 55 Diisobutyl ketone, 55 Diisopropylamine, 55 Diisopropyl ether, 55 DIKAMIN , 2,4-D, 55 DIKONIRT , 2,4-D, 55 Dimefox, 55 Dimethoate, 55 3,3 -Dimethoxybenzidine, 55 n,n-Dimethylacetamide, 56 Dimethylamine, 56 4-Dimethylaminoazobenzene, 56 Dimethylaminoethanol, 56 n,n-Dimethyl aniline, 56 7,12-Dimethylbenz[a]anthracene, 56 3,3 -Dimethylbenzidine, 56... 

Dichloroquinazolines have been prepared from the corresponding 2,4-dihydroxy compounds by heating for a few hours with phosphorus oxychloride in the presence of dimethyl aniline or phosphorus penta-chloride. These are more stable than the monochloro compounds and can be distilled in vacuum without appreciable decomposition. 

QuinoxaIin-2-oncs are readily converted into the corresponding 2-chloroquinoxalines by treatment with phosphoryl chloride in the case of the highly insoluble 2,3-diones chlorination is effected conveniently with a mixture of phosphoryl chloride and dimethyl-aniline. The use of phosphorus pcntachloride may lead to side reactions, for example, quinoxalin-2-one (70) is converted into 2,3-... 

A mixture of 65 parts 1 -[4,4-di-(4-fluoro-phenvl)butyl] -piperazine, 4.33 parts N-(2-chloro-acetyl)-2,6-dimethyl-aniline, 3.2 parts sodium carbonate, a few crystals of potassium iodide in 200 parts 4-methyl-2-pentanone is stirred and refluxed for 70 hours. After cooling there are added 70 parts water. The organic layer is separated, dried over potassium carbonate, filtered and evaporated. The oily residue is dissolved in 80 parts diisopropyl-ether and the solution is filtered hot. After cooling the filtrate at 0°C, the formed solid is filtered off and recystallized from 80 parts ether, yielding 1-[4,4-di-(4-fluoro-phenyl)butyl] -4-[(2,6-dimethyl-anilino-carbonvl)-mathyl] -piperazine MP 159°Cto 161°C. 

The pH is adjusted to 5.5 and the water phase separated and extracted with additional ether in order to remove the surplus dimethyl anilin. After addition of an excess of ammonia to the solution, the reaction product, N-methylpipecolic acid 2,6-dimethyl anilide, is recovered by extraction with isoamyl alcohol. The isoamyl alcohol solution is evaporated to dryness, the product dissolved in dilute hydrochloric acid, treated with charcoal and reprecipitated with NaOH. N-methylpipecolic acid 2,6-dimethyl anilide is obtained in crystalline form. 

Tetryl. In the manufacture of Tetryl, it is usual not to nitrate dime thy laniline directly, but to dissolve it first in coned sulfuric acid and then to nitrate the dimethylaniline sulfate so obtained. Direct nitration of dimethylaniline proceeds so violently that it can be carried out only under specialized conditions. Many years experience of Tetryl manufacture has shown that the ratio of sulfuric acid to dimethylaniline should not be lower than 3 1, since a smaller amount of sulfuric acid may be detrimental to the nitration process. However, the ratio of sulfuric acid to dimethylaniline must not be too high, otherwise Tetryl yield is decreased. Temp must be maintained between 20-45° to avoid sulfonation of the benzene ring. Care must be exercised not to leave any unreacted dimethylaniline prior to introduction of nitric acid, because of the potential violence of the dimethyl-aniline-nitric acid reaction. Consequently, continuous methods of prepn are to be preferred as they inherently minimize accumulation of unreacted dimethylaniline... 

Basic Explosives Manufacture. The major quantities and the toughest problems are here. They include a) acid waters, treated with lime or soda ash, chemical washes, spills, washdowns b) Red Water from TNT purification. A complex, brick-red soln of Na nitrate, Na sulfate, Na sulfite, Na nitrite, and about 17% organics which include sulfonated nitrotoluene isomers and complex, unidentified dye-bodies c) dissolved expls, eg, Pink Water which is approx lOOppm TNT in w d) suspended expl particles — dust and chips and e) sometimes solvents such as acet, benz, and dimethyl aniline... 

Crotonic acid, esterification with sec-butyl alcohol, 41, 60 Crystal Violet, from condensation of oxalyl chloride with dimethyl-aniline, 41, 2-4... 

Benzenamine, 2-chloro- [Aniline, 2-chloro-], p-brommation of, 55, 23 Benzenamine, 3 chloro [Aniline, 3-chloro-J, p-bromination of, 55, 23 Benzenamine, jV.W-diethyl- [Aniline, N,N-diethyl-], p bromination of, 55, 23 Benzenamine, jV.A -dimcthyl [Aniline, N,N-dimethyl-], p-bromination of, 55, 23 Benzenamine, 2 3-dimethyl- [Aniline, 2,3-dimethyl-], p-bromination of, 55, 23 Benzenamine, 2,5-dimethyl- [Amhne, 2,5-dimethyl-], p-bromination of, 55, 23... 

Benzenamine, 3,5-dimethyl- [Aniline, 3,5-dimethyl ], p-biomination of, 55, 23 Benzenamine, 2,/V-dimethyl- [Aniline 2-methyl-A-methyl-]. p-biomination of, 55, 23... 

Pyridin-, Chinolin- und N,N-Dimethyl-anilin-N-oxid werden elektrolytisch an Queck-silber in Methanol/Tetramethylammoniumchlorid zu Pyridin (81% d.Th.), Chinolin (78% d.Th.) bzw. N,N-Dimethyl-anilin (78% d.Th.) (galvanostat. bei 5 A/65°C) redu-ziert1. Analog verhalten sich 2- und 4-Methyl-pyridin-N-oxide (2-Methyl-pyridin 96% 4-Meihyl-pyridin 80% d.Th.)1. 

Carbon monoxide cyanogen, hydrogen cyanide nitrites arsine aniline, dimethyl aniline, toluidine nitrobenzene hydrogen sulphide (causes respiratory paralysis by impairment of oxygen utilization in the central nervous system). 

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