Trichloro aniline

Sulphuryl chloride usually behaves as a chlorinating agent. For instance, with benzene chlorobenzene is formed with acetone mono- and di- chloroacetones with aniline trichloro-aniline, etc. 

Pigment Red 112 [653546-2] 12370 N aphthol AS coupling of dia2oti2ed 2,4,5-trichloro-aniline with 3-hydroxy-2-naphth-2 -methylanihde... 

A. N-Trijluoroacetanilide. In a two-necked, round-bottomed flask fitted with a thermometer, a Drierite tube, and a magnetic stirring bar are placed 4.56 ml. (4.66 g., 0.050 mole) of aniline [Benzenamine] (Note 1) and 15 ml. of dimethyl sulfoxide (Note 2). The resulting solution is stirred and cooled in an ice water bath, and when the internal temperature has dropped to 10-15°, 21.5 g. (0.10 mole) of 1,1,1-tri-chloro -3,3,3 -trifiuoroacetone [2 -Propanone, 1,1,1 -trichloro-3,3,3-tri-fluoro-] (Note 3) is added in portions through the condenser. A mild exotherm results, and the addition is extended over ca. 5 minutes to... 

Hydro-de-diazoniation seems to be an unnecessary reaction from the synthetic standpoint, as arenediazonium salts are obtained from the respective amines, reagents that are normally synthesized from the hydrocarbon. Some aromatic compounds, however, cannot be synthesized by straightforward electrophilic aromatic substitution examples of these are the 1,3,5-trichloro- and -tribromobenzenes (see below). These simple benzene derivatives are synthesized from aniline via halogenation, diazotization and hydro-de-diazoniation. Furthermore hydro-de-diazoniation is useful for the introduction of a hydrogen isotope in specific positions. 

Mizutani and coworkers57a confirmed the presence of polychloro(methylsulfonyl)biphenyls (159-170) as sulfur-containing metabolites of chlorobiphenyls (Cl-BP) in the feces of mice based on both GLC-mass spectrometry and chemical derivatization. In some cases comparison with authentic samples (161 and 162) was also made. When preparing 161 and 162,2,5-dichloro-3-(methylsulfonyl)aniline, 2,5-dichloro-l-iodo-3-(methylsulfonyl)benzene and 2,2, 5,5 -tetrachloro-3,3 -bis(methyl-sulfonyl)biphenyl were also obtained and their four peak El mass spectra reported572. Similar data were given for the corresponding 4-substituted intermediates, which were involved in the preparation of 162. Also 2,4, 5-trichloro-2 -(methylsulfonyl)-biphenyl was prepared and its four peak mass spectra given. Metabolites 163 and 164 were also identified by comparison with the authentic standards. 

Aniline, 4,4 -azodi-, 40,18 Aniline, reaction with hexachlotoace-tone to form a, ,a-trichloro-acetanilide, 40, 103 reaction with maleic anhydride, 41,94 Anisoin, reduction to deoxyanisoin by tin and hydrochloric add, 40, 16... 

B-trichloro-N-triphenylborazine, mp 290-292°C, was obtained in 86 yield following the procedure of Groszos and StafieJ (6). This material was then transformed into B-triamino-N-triphenyl-borazine in 67 yield using the method of Toeniskoetter and Hall (2)- B-trianilinoborazine and the novel B-tris[di(trimethylsilyl)-amlno]borazlne (mp, 131.5-132°C characterized by GC/MS, molecular ion 558 amu, and elemental analysis) were synthesized in 76 and 71 yields, respectively, by interaction of aniline and hexamethyl-disllazane with chloroborazine in the presence of triethylamine. 

Addition of acetone, ammonia, aniline or diphenylamine to the oxidant causes rapid exothermic reactions, with or without flame, and large amounts under confinement would explode. The trichloro analogue is similar, but less vigorous. 

Tris(picrylamino)-l,3,5-trinitrobenzene (113), the product from condensing three equivalents of aniline with 1,3,5-trichloro-2,4,6-trinitrobenzene followed by nitration with mixed acid, is a high-molecular weight explosive which shows good thermal stability (m.p. 234 °C) but is readily detonated. " ... 

Hydroxylamine hydrochloride (8) Hydroxylamine, hydrochloride (9) (5470-11-1) 2,2,2-Trichloro-1-ethoxyethanol Ethanol, 2,2,2-trichloro-1-ethoxy- (8,9) (515-83-3) 2-Fluoroaminobenzene Aniline, o-fluoro- (8) Benzenamine, 2-fluoro- (9) (348-54-9) 7-Fluoroisatin 1 H-lndole-2,3-dione, 7-fluoro- (8,9) (317-20-4)... 

As a starting material for the preparation of sym-trinitrotriazidobenzene, 1,3,5-trichlorobenzene is used. It is obtained by the chlorination of aniline and the removal of the amino group. Nitration to the trinitro derivative is described in Vol. I. The final reaction is simple powdered 1,3,5,-trichloro-2,4,6-trinitrobenzene is added to an aqueous alcohol solution of sodium azide. The precipitated product is washed with alcohol and water and dried at a moderate temperature. The product so obtained may be purified by crystallization from chloroform. 

It was first prepd in 1923 by Turek on treating 2,4,6-trichloro-l,3,5-trinitrobenzene with an alkali azide in ale, acet or w soln. It can be obtained also from aniline by chlorination to sym-trichloro-aniline, followed by diazotization, treatment with ale to give sym-trichlorobenzene, nitration with mixed nitric-sulfuric acid to trinitrotrichloro-benzene and finally treatment with an ale soln of Na azide(Refs 3,5,6a 8)... 

Other suitable diazo components are 4-nitroaniline (orange), 2,6-dichloro-4-(N,N-dimethylsulfamoy 1 )ani 1 ine (orange), 4-aminobenzophenone (yellow), 2,4,6-trichloro aniline (yellow), 2,4,6-tribromoaniline (yellow), 2,6-dibromo-4- nitro aniline (yellow-brown) [30], and 2-cyano-5- chloroaniline (orange). 

Tribromo- and -trichloro-aniline give nearly theoretical yields of 2,4,6-tribromo- Mid -trichloro- 1- nitrobenzene (100% Mid 98% respectively). 

GC-MS and HPLC analyses of electrolyzed solutions allowed the detection of aromatic intermediates such as p-benzoquinone and nitrobenzene for aniline, 4-chlorocatechol for 4-chlorophenol, 4-chlorophenol, 4-chlorocatechol, hydroquinone, and p-benzoquinone for 4-CPA, 4-chloro-o-cresol, mehylhy-droquinone, and methyl-p-benzoquinone for MCPA, 2,4-dichlorophenol, 4,6-dichlororesorcinol, chlorohydroquinone, and chloro-p-benzoquinone for 2,4-D, and 2,4,5-trichloro-phenol, 2,5-dichlorohydroquinone, 4,6-dichlororesorcinol, and 2,5-dihydroxy-p-benzoquinone for 2,4,5-T. In general, these by-products persisted in solution while the initial pollutant was degraded. 

Determination of Trichloromethyl Chloroformate. The quantitative determination of trichloromethyl chloroformate may be carried out by the aniline method according to Pancenko. unless mono- or dichloromethyl chloroformate is present. These both react with aniline in the same way as the trichloro derivative (see p. no). 

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