Toluene amino-nitro

CHAPTER 10 THE PREPERATION OF AMINO NITRO BENZENES toluene, and the mixture treated with ammonia gas. An autoclave is used in the reaction between the 3,5-dichloro-2,4,6-trinitroanisole and ammonia. An autoclave is a special laboratory machine, which is widely available but expensive. Commercial Industrial note For related, or similar information, see Application No. 534,896, June 8, 1990, by The United States of America, to Donald G. Ott, Los Alamos, NM, Theodore M. Benziger, Santa Fe, NM. Part or parts of this laboratory process may be protected by international, and/or commercial/industrial processes. Before using this process to legally manufacture the mentioned explosive, with intent to sell, consult any protected commercial or industrial processes related to, similar to, or additional to, the process discussed in this procedure. This process may be used to legally prepare the mentioned explosive for laboratory, educational, or research purposes. 

The ring-chlorinated derivatives of toluene form a group of stable, industrially important compounds. Many chlorotoluene isomers can be prepared by direct chlorination. Other chlorotoluenes are prepared by indirect routes involving the replacement of amino, hydroxyl, chlorosulfonyl, and nitro groups by chlorine and the use of substituents, such as nitro, amino, and sulfonic acid, to orient substitution followed by their removal from the ring. 

Azidofurazans and -furoxans undergo dipolar cycloaddition reactions with unsaturated compounds, in some cases regiospecifically. Thus, reaction of 3-amino-4-azidofurazan with l-morpholinyl-2-nitroethene (toluene, reflux, 70 hours) gives 4-nitro-l,2,3-triazole 204 in 87% yield (99MI1, 000KGS406). Cycloaddition of the same azide to alkynes was accomplished by formation of a mixture of position isomers 205 and 206. Regiospecific addition was observed only in singular cases... 

Can be prepd by diazotization of 6-nitro-4-amino toluene-3-sulfonic acid with K nitrite and dil sulfuric acid. It has also been isolated by... 

After drying for 10 min in a stream of cold air 1,4-phenylenediamine (h/Jj 5-10), 2-amino-4-chlorophenol (h/ f 15-20), 4-nitroaniline (h/ f 25-30) and l,4-amino-3-nitro-toluene (h/ f 50-55) appeared as blue-violet chromatogram zones on a blue background. These could be recognized without difficulty for several days from the back of the chromatogram. 

Filter, wash toluene with water, NaHC03, water and dry, evaporate in vacuum to get 100 g gamma-Cl-butyraldehyde (I) (can distill 28/2). 10 g (I), 20 g 3-nitro-phenylhydrazine dissolve in the minimum volume of hot ethanol containing 10% glacial acetic acid. Heat on steam bath one hour cool and add water until dark oil separates. Evaporate in vacuum the ethanol and decant the water to get the oily gamma-Cl-butyraldehyde-3-intro-phenylhydrazone(II). 29 g (11), 300 ml concentrated HC1, ZOO ml benzene stir three hours, replace benzene with fresh benzene and stir four hours. Combine the two benzene portions, wash with water and dry, evaporate in vacuum to get 4 g 3-(beta-Cl-ethyl)-4 and 6-nitroindole (m). 3.56 g (III), 200 ml ethanol, 200 ml 34% aqueous DMA (or other amine) and let stand at room temperature for one week. Evaporate in vacuum the ethanol, filter, dissolve the precipitate in dilute HC1 and filter. Basify the filtrate with dilute NaOH to precipitate 3 g 4 and 6-nitro-DMT (IV). 5.2 g (IV), 350 ml ethanol, 100 ml IN NaOH heat to 50° and add a solution of 3 g Na dithionite in 15 ml 0.2N NaOH. filter hot and evaporate in vacuum to get 2 g 4 and 6 amino-DMT (can purity by dissolving in HC1, filter, basify, extract with ether and dry and evaporate in vacuum the extract). 

Polymers and resins Water purification, including removal of phenol, chlorophenols, ketones, alcohols, aromatics, aniline, indene, polynuclear aromatics, nitro- and chlor-aromatics, PCB, pesticides, antibiotics, detergents, emulsifiers, wetting agents, kraftmill effluents, dyestuffs recovery and purification of steroids, amino acids and polypeptides separation of fatty adds from water and toluene separation of aromatics from ahphatics separation of hydroquinone from monomers recovery of proteins and enzymes removal of colours from symps ... 

Haidour and Ramos (1996) analyzed the degradation products of 2,4,6-trinitrotoluene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene by the bacterium Pseudomonas sp. clone A under aerobic conditions. The bacterium utilized 2,6-dinitrotoluene as a source of nitrogen yielding two compounds 2-amino-6-toluene and 6,6 -dinitro-2,2 -azoxytoluene. 2-Hydroxylamino-6-nitro-toluene and subsequent formation of 2,6-dihydroxyaminotoluene were reported as intermediate products of 2,6-dinitrotoluene metabolism by Clostridium acetobutylicum. 2,6-Diaminotoluene was reported as the end product (Hughes et al., 1999). 

Hydrogenation of unsaturated nitro compound 37 (10% Pd/C, toluene) gives a saturated amino intermediate that can be treated with PTSA under Dean-Stark conditions to give the target keto isomer of cryptoheptine 38 in a 44% two-step yield (Scheme 7 (2000JNP643)). 

Chlorpromazine and other phenothiazines can be identified by their reactions with benzene-, toluene-o-, and toluene /j-stilbinic acids, and with p-hydroxy-, m-nitro-, w-amino-, and p-nitrobenzene stilbinic acids in an HCl medium. The reaction products are initially colorless masses but rapidly oxidize to yield colored products [32]. 

Chakrabarti and coworkers at Eli Lilly in the United Kingdom have reported the initial discovery and synthesis of olanzapine (Schemes 5 and,6). The thiophene 22 was synthesized by adding a DMF solution of malononitrile to a mixture of sulfur, propionaldehyde and triethylamine in DMF. The anion of amino thiophene 22 underwent a nucleophilic aromatic substitution with 2-fluoronitrobenzene to provide 23. The nitro group was reduced with stannous chloride and the resulting anihne cyclized with the cyano group to form amidine 24. Finally, a mixture of N-methylpiperazine and 24 were refluxed in DMSO/toluene to afford olanzapine (2). 

Dinitro4-(N -butyl-N-nitro)-amino toluene 2 B377-B378... 

Cyclization of 2-[(3-acetamido-2-pyridyl)amino]benzoic acid (202) in 0.5 N sulfuric acid gave 6-amino-ll//-pyrido[2,l-h]quinazolin-ll-one (203) (84MI3). 2-[(6-Methyl-, 5-nitro-, and 3-nitro-2-pyridyl)amino]benzoic acids were cyclized into 9-methyl, 8-nitro, and 6-nitro-l 1 //-pyrido[2,l -ujquina-zolin-ll-ones, respectively, by the action of 80% sulfuric acid. Ethyl 2-(2-pyridylamino)benzoate, prepared in the reaction of 2-chloropyridine and ethyl anthranilate in boiling toluene for 10 h, afforded ll//-pyrido[2,l-b]-quinazolin-ll-one (27) on heating at 200-210°C for 0.5 h (92MI2). 

The third 12-1. portion yields about 20 g. of 2-amino-3-nitro-toluene. The residue in the steam-distillation flask, about 20 g. of crude 2-amino-5-nitrotoluene, solidifies when cooled and may be separated by filtration. It can be recrystallized from 2 1. of hot water, yielding IT-15 g. of yellow plates, m.p. 130-131° (cor.). 

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