Anilines trifluoromethylation

The dipole moments of aniline,/-(trifluoromethyl)anihne, and (trifluoromethyl)benzene are 1.3, 4.3, and 2.9 D, respectively. Explain how these data are used to deduce the direction of the dipole moment of anihne. 

Chloro-4-(triHuoromethyl)phenoxy)-3- methylthio 1 CI2. Ethyl methylthioacetate 2 4-[2-Chloro-4-(trifluoromethyl)phcnoxyl]aniline 3 Et,N 49, [16]... 

Bromo-Ar,Ar-dimethyl-3-(trifluoromethyl)aniline has been prepared by the methylation of 4-bromo-3-(trifhioromethvl)aniline with trimethyl phosphate in 70-80% yield.3 The present method, which effectively uses 3-(trifluoroinethyl)aniline as starting material, offers advantages in cost, yield, and ease of purification. 

Aniline, 2-chloro- [Benzenamine 2-chloro-], p-bromination of, 55, 23 Aniline, 3 chloro- [Benzenamine, 3-chloro-], p bjomination of, 55, 23 Aniline, //.A -diethyl- [Benzenamine, N,N-diethyl-], p-bromination of, 55, 23 Aniline,TV,//-dimethyl- [Benzenamine, N,N-dimethyl-], p-brommation of, 55, 23 Aniline, 2,3-dimethyl- [Benzenamine, 2,3-dimethyl-], p-bromination of, 55, 23 Aniline, 2,5-dimethyl- [Benzenamine, 2,5-dimethyl-], p-biomination of, 55,23 Aniline, 3,5-dimethyl [Benzenamine, 3,5-dimethyl ], p bromination of, 55,23 Aniline, Ar,iV-dimethyl-3-(trifluoromethyl) [Benzenamine, At,Ar-dimethyl-3-tn-fluoromethyl-], 55,21 Aniline, 3-methoxy- [Benzenamine, 3-methoxy-], p-bromination of, 55, 23 Aniline, TV-methyl- [Benzenamine, //-methyl-], p-biomination of, 55, 23 Aniline, 2-methyl-//,JV-dimethyl- [Benzen-amme, 2/V,/V-tnmethyl-], p-bromina-tion of, 55, 23... 

A,A-Dibenzyl-2-(ethoxycarbonylmethyl)amino-4-(trifluoromethyl)aniline (27) underwent reductive debenzylation and spontaneous cyclization to 6-trifluoro-methyl-3,4-dihydro-2(17/)-quinoxalinone (28) [Pd(OH)2/C, EtOH, H2 (3 atm), 3 days 97%]. " °... 

However, when an electron-withdrawing group, e.g., a trifluoromethyl group, is attached to the anilines this procedure is not applicable. A way to circumvent this problem was enlightened by Glasnov et al. [53] who treated the malondianilide 14 with Eaton s reagent, a 7.7% solution of phosphorus pen-toxide in methanesulfonic acid (a. Scheme 6) [54]. This reaction is, however, sensitive to time, temperature, and concentration. More reactive malondian-... 

In addition to military uses, it should be noted that aromatic nitro compounds such as trifluralin (2,6-dinitro-A,A-dipropyl-4-(trifluoromethyl)aniline and dinoseb (2,4-dinitro-6-5 ec-butylphenol)... 

The major metabolic pathways of flutolanil in plants are para-hydroxylation of the aniline ring and hydr-oxylation of the isopropoxy side chain. For potatoes, flutolanil anddesisopropyl-flutolanil (M-4) are selected as the target analytes. For rice plant, other metabolites containing 2-(trifluoromethyl)benzanilide moiety are also selected as the target analytes. For soil and water samples, flutolanil is selected as the only target analyte. 

Interestingly, a substance somewhat closely related to flunixin, triflocin (30), is a diuretic rather than an antiinflammatory agent. It can be prepared by nucleophilic aromatic displacement on 4-chloronicotinic acid (29) with m-trifluoromethyl-aniline.8... 

Dan et al. found that Brij-35 also produces an enhancement of the CL intensity of the reaction of fti.v AL[2-(A, -rnclhyl-2 -pyridiniumyl)ethyl]-AL [(trifluoromethyl)sulfonyl]]oxamide with hydrogen peroxide in the presence of some fluorophors [40], To be precise, the CL intensity increased by a factor of 130 for 8-aniline-1-naphthalenesulfonic acid (ANS) and 5.6 forrhodamine B (RH B), compared to the CL intensity in the absence of surfactant. This leads to an increase of 2-3 orders of magnitude in the linear dynamic ranges and a more precise determination of these analytes. However, improvement of the detection... 

Chlorotriethylamine, d328 2-Chloro-2-(trifluoromethyl)aniline, al41 Chloro-a,a,a-trifhiorotoluenes, c60, c61, c62 4 -Chloro- a,a, a-trifhioro-o-toluidine, a 142... 

Fluorothane, b308 Fluorotrichloromethane, t237 2-Fluoro-5-(trifluoromethyl)aniline, al79 Formal, d507... 

Triethylene glycol, el39 2-(Trifluoromethyl)aniline, al26 4,4,4-Trifluoro-1 -(2-thienyl)-1,3-butanedione, tl 32... 

Triethylene glycol dimethyl ether, b211 3-(Trifluoromethyl)aniline, al27 a,a,a-Trifluorotoluidines, al26 thru al28... 

An iridium(I) complex with the l,2-bis(tcrt-butylmethylphosphino)ethane (4) and tetrakis(3,5-bis(trifluoromethyl)phenyl)borate as the counter anion catalyzes the hydrogenation of several acyclic aromatic Ai-arylimines under atmospheric hydrogen pressure at room temperature, giving the desired chiral amines with high-to-excellent enantioselectivities (up to 99%, Fig. 6) [19]. The authors also tested (S )-BINAP (Fig. 1) and (/ )-Ph-PHOX (PHOX = 2-[2-(diphenylphosphino) phenyl]-4,5-dihydrooxazole) hgands with lower enantioselectivities [19]. Both steric and electronic properties of the ligand and the combination with the BArF anion are in the base of the efficacy of this catalytic system. On the other hand, attempted hydrogenations of Ai-(2,2,2-trifluoro-l-phenylethylidene)aniline and M-(l,2,2-trimethyl-propylidene)aniline under the same conditions resulted in... 

The product is free from secondary aniline product on the basis of infrared and n.m.r. proton analysis. If equimolar amounts of aniline and phosphate are employed, the product is obtained in a higher yield (12.3 g., 65%), but it contains a trace of w-trifluoromethyl-N-methylaniline as detected by infrared analysis. This secondary aniline is readily removed by heating the product to reflux with 1 ml. of acetic anhydride followed by... 

The described method of dialkylation of anilines is essentially that of Billman and co-workers. It has not previously been applied to m-trifiuoromethylaniline. m-Trifluoromethyl-N,N-dimethylaniline has been prepared in 29% yield by alkylating m-trifluoromethylaniline with methyl iodide. ... 

Plant. Degrades to a demethylated intermediate which subsequently is degraded to the aniline moiety (possibly 3-trifluoromethylaniline) (Hartley and Kidd, 1987 Humburg et al, 1989). Duke et al. (1991) reported that fluometuron degrades in plants via the following degradative pathway fluometuron to TV-methyl-A -(3-(trifluoromethyl) phenyl) urea which undergoes demethylation to... 

The trifluoromethylating order of reactivity of a series of 5-, Se-, and Te-(trifluoromethyl)dibenzothiophenium, -selenophenium, and -telluro-phenium triflates was determined by relative reaction rates with aniline. 

Aniline was smoothly trifluoromethylated with the most powerful dinitro S-salt 39 to give a mixture of o- and p-CFs isomers (Eq. 24). 

Kinetic studies of the trifluoromethylation of aniline with 5-salt 17, dinitro 5-salt 39, and nonheterocyclic 5-salt 29 were carried out and the activation parameters determined (Table I). 

Kinetic Parameters for the Trifluoromethylation of Aniline with 5-(Trifluoromethyl)dibenzothiophenium Triflate (17), S-(Trifluoromethyl)diphenylsulfonium Triflate (29), AND 5-(Trifluoromethyl)-3,7-DINITRODIBENZOTHIOPHENIUM TrIFLATE (39) IN DMF-d7 AT 25°C... 

Chlorotrifluoromethyl aniline (no. 73.) was found in the sediment samples. This compound is used as a reactant with chloro-aniline (no. 72) in the preparation of 4,4 -dichloro-3-(trifluoromethyl)-carbanilide, a disinfectant. Two other related compounds also found in some of the sediments were chlorophenyl isocyanate (no. 74) and chloro(-trifluoromethyl)phenyl isocyanate (no. 75). This suggests that some of the 4,4 -dichloro-3-(trifluoromethyl)-carbanilide may, in fact, exist in the sediment extracts but is decomposed in the injection port of the gas chromatograph, since it is very doubtful that the easily hydrolyzable isocyanates exist as such in the sediments. To strengthen this hypothesis some 3,4,4 -trichlorocarbanilide [none of the 4,4 -dichloro-3-(trifluorome-thyl)-carbanilide was available] was analyzed by GCMS. The injection port temperature was 300°C. As expected, none of the parent compound eluted from the column. However, mass spectra were obtained for chlorophenyl isocyanate, dichlorophenyl isocyanate, chloroaniline, and dichloroaniline. The presence of the carbanilides themselves (no. 76, 77, 78) was confirmed with the help of HPLC and mass spectral identification. 

Finally, a few miscellaneous compounds which were identified in the Delaware River and which have not been previously reported as water contaminants will be discussed Chloro (trifluoromethyl) aniline and chloro (trifluoromethyl) nitrobenzene (no. 55 and 56) were identified in the water, they had maximum concentrations at river mile 78. Both compounds represent common sub-structures in various pesticide and dye molecules, and several of the companies located along the river have patents using these compounds (30-32j. It is possible that these compounds are actually present in the river water as such, but it is also possible that they are formed in the GC injection port by pyrolytic degradation of larger pesticide or dye molecules (see above). All three binaphthyl-sulfone isomers (no. 92) were identified in the river water near Philadelphia. Product literature for one of the companies in the area indicates production of condensed sulfonated polymers derived from naphthalene sulfonic acid and maleic anhydride. It seems likely that the binaphthylsulfones are formed as by-products during preparation of this commercial product. 

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