Trifluoromethyl Aniline Research Articles

An Activated Trifluoromethyl Group as a Novel Synthon for a Substituted Vinyl Function: Facile Synthesis of 2-(Substituted 1-Alkenyl)anilines

Abstract Treatment of 2-(trifluoromethyl)aniline with an alkyl Grignard reagent results in an efficient transformation of the trifluoromethyl substituent into a substituted vinyl group.

High‐resolution solid‐state 19F‐NMR spectroscopy of the sorption and diffusion of fluorine‐containing aromatic molecules in polymeric media

AbstractHigh‐resolution 19F solid‐state NMR spectroscopy was employed to study the sorption properties of hexafluorobenzene (HFB) and 3,5‐bis (trifluoromethyl) aniline (TFMA) in polystyrene (PS) and butyl rubber (BR). The NMR spectra indicate that the penetrants undergo dual‐mode sorption in the glassy polymer (PS), but are highly mobile in the rubbery polymer (BR). In addition, the NMR method was utilized in the experimental determination of diffusion coefficients for the HFB/PS, TFMA/PS, and HFB/BR systems through desorption studies. The diffusion results for the TFMA/PS case agree very well with those previously obtained via resonance nuclear reaction analysis. © 1993 John Wiley & Sons, Inc.

Study of diffusion of a fluorinated hydrocarbon in ion beam irradiated poly(styrene) by nuclear resonance analysis

The diffusion of a fluorinated hydrocarbon into 30 keV-H+ irradiated glassy poly(styrene) (PS) was studied by using nuclear resonance reaction analysis. The diffraction coefficient and front velocity for diffusing a particular fluorinated hydrocarbon, 3, 5-bis (trifluoromethyl) aniline (TFMA) in PS (MW=400 000) are dramatically decreased on irradiation with 5×1013–1×1014 atoms/cm2 at 22.5 °C. These ion beam irradiation effects are similar to temperature effects on diffusion. A possible application of the observed effect is the control of diffusion of a vapor into cross-linked polymer glasses by means of ion beam implantation techniques. It is our belief that this is the first report of this phenomena due to the effects of ion beam irradiation.

Preparation of Amides of Carboxylic Acid Herbicides for Gas Chromatographic Analysis

Abstract Amides of 14 carboxylic acid herbicides were prepared by reacting the free acid with the amine in toluene for 1 hr at 80[ddot]C in the presence of PCl3 or P2I4. The acids include phenoxyacetic acids, arylacetic acids, and benzoic acids. Aniline, o-toluidine, 3,5-bis(trifluoromethyl)aniline, piperidine, and tetrahydroquinoline were the amine components. Excess of reagents and by-products of the reaction were removed by partitioning into aqueous acid and base. Retention times relative to 2,4-D anilide on 1% OV-22 and FSOT RSL-150 columns are listed for the anilides and should be useful for confirmation purposes. The anilides of 2,4-D, silvex and 2,4,5-T were obtained in better than 90% yield.

Effects of Flooding on Dinitroaniline Persistence in Soybean (Glycine max) – Rice (Oryza sativa) Rotations

A field study was conducted with fluchloralin [N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-(trifluoromethyl)aniline], profluralin [N-(cyclopropylmethyl)-α,α,α-trifluoro-2,6-dinitro-N-propyl-p-toluidine], and trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) at 1× and 2× rates in soybeans [Glycine max(L.) Merr.] for 2 consecutive yr to evaluate their persistence in soil and to determine their residual effect on rice (Oryza sativaL.). In another field study that was conducted to evaluate the effect of winter flooding on the persistence of 4× rates of the same herbicides, gas chromatographic analysis and bioassay procedures both revealed increased dissipation of these herbicides because of winter flooding. Flooding rice for 2 or 4 months during winter reduced the adverse effect from herbicidal residues. Laboratory studies evaluated the persistence and volatility of these herbicides at 4 and 25 C in two soils at three moisture contents (air-dried, field capacity, and flooded). The persistence of the three herbicides was similar in the field and in the laboratory and usually followed the order fluchloralin > profluralin = trifluralin. Volatility was most rapid with moisture at field capacity, but overall dissipation was most rapid in flooded soil. Significant dissipation and volatility losses of all three herbicides occurred at 4 C in flooded soil and in soil at field capacity. These studies indicated that winter flooding is effective in reducing the concentration of dinitroaniline herbicides in soil.

Effect of Three Dinitroaniline Herbicides on Rice (Oryza sativa) Growth

A field study was conducted for 3 yr to evaluate residual levels of fluchloralin [N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-(trifluoromethyl)aniline], profluralin [N-(cyclopropylmethyl)-α,α,α-trifluoro-2,6-dinitro-N-propyl-p-toluidine], and trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) for their effects on injury and yields of rice (Oryza sativaL.). All three herbicides consistently injured rice and reduced yield at application rates above 0.1 kg/ha. These herbicides were similar in their effects on rice, but trifluralin was slightly more phytotoxic than fluchloralin or profluralin. Bioassay showed fluchloralin and trifluralin to be more inhibitory than profluralin of root and shoot elongation. The order of toxicity of the vapors of these herbicides arising from treated soil was found to be trifluralin > profluralin > fluchloralin. Grain sorghum (Sorghum bicolorL. Moench) was slightly more sensitive to these herbicides than was rice when seedlings were grown in treated soil and over 10 times more susceptible than rice to injury from their vapors. Both plant species were less affected by the herbicides in silty clay than in silt loam soil.

Effect of DBCP on Fluchloralin Persistence

Three field studies were conducted over a 2-yr period to evaluate the persistence of fluchloralin [N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-(trifluoromethyl) aniline], and to determine whether DBCP (1,2-dibromo-3-chloropropane) affected persistence. Fluchloralin was applied to field plots at 1.1 kg/ha with and without DBCP at 20.5 kg/ha. In the first study, soil samples were taken periodically over a 1-yr period and assayed for fluchloralin by both gas chromatography (GC) and a sorghum (Sorghum bicolorL. Moench ‘AKS-516’) root-elongation bioassay. Both methods of analysis indicated that fluchloralin persistence was unaffected by DBCP. An oat (Avena sativaL. ‘Ora’) bioassay of soil from the field plots 41 weeks after treatment showed no residual herbicide activity. In the next two field studies, soil samples were taken periodically over a 32-week period and assayed by GC for fluchloralin. A greenhouse sorghum bioassay of soil samples taken from both tests 32 weeks after application showed residual activity of fluchloralin in one test, but differences were not attributable to DBCP. A two-phase process of fluchloralin dissipation in field soil was indicated from analysis of the data using a complex first-order regression, as opposed to a simple first-order regression. Half-life values describing fluchloralin persistence, using the complex first-order regression, ranged from 2.3 to 3.7 weeks for the first phase and 9.5 to 26.7 weeks for the second phase.

Performance of Six Substituted Dinitrobenzamine Herbicides Applied at Layby of Cotton (Gossypium hirsutum)

Six substituted dinitrobenzamine herbicides, including butralin [4-(1,1-dimethylethyl)-N-(1-methylpropyl)-2,6-dinitrobenzenamine], dinitramine (N4,N4-diethyl-α,α,α-trifluoro-3,5-dinitrotoluene-2,4-diamine), fluchloralin [N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-(trifluoromethyl)aniline], pendimethalin [N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine], profluralin [N-(cyclopropylmethyl)-α,α,α-trifluoro-2,6-dinitro-N-propyl-p-toluidine], and trifluralin (α,α,α,-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine), were evaluated as directed broadcast sprays applied and soil incorporated at time of last cultivation (layby) of cotton (Gossypium hirsutumL. ‘Acala SJ-2’). At the rates used, all herbicides provided more than 90% control of annual grasses. During 1976 and 1977, control of redroot pigweed (Amaranthus retroflexusL.) and smooth pigweed (Amaranthus hybridusL.) ranged from 90 to 100% and none of the herbicides differed significantly in their effect. However in 1975, butralin at 1.1 kg/ha did not improve pigweed control when compared to the untreated control. None of the herbicides consistently controlled black nightshade (Solanum nigrumL.) and except pendimethalin, none caused detectable cotton injury. In 2 of 3 yr, pendimethalin caused enlarged growth of the cotton stem in the cotyledonary node area contacted by the herbicide spray. Stem breakage following wind occurred in about 5% of the cotton plants; however, the injury was not manifested by reduced yield. None of the herbicides influenced cotton yield. Residues from soil samples collected 4 months after herbicide application reduced growth of Japanese millet [Echinochloa crus-galli(L.) Beauv. var.frumentacea(Link) Wright]3and grain sorghum [Sorghum bicolor(L.) Moench] 24 to 49%.

PERSISTENCE AND PHYTOTOXICITY OF DINITROANILINE HERBICIDES IN MANITOBA SOILS

The persistence and phytotoxicity of dinitramine (n4, N4-diethyl-α,α,α-trifluoro-3,5-dinitrotoluene-2,4-diamine), fluchloralin (N-(2-chloroethyl)-2, 6-dinitro- N-propyl-4- (trifluoromethyl)aniline), profluralin (N-(cyclopropylmethyl)α,α,α-trifluoro-2, 6-dinitro-N-propyl-p-toluidine), and trifluralin (α,α,α-trifluoro-2,6-dinitro-N-N-dipropyl-p-toluidine) were compared in three Manitoba soils: sandy loam, clay loam and clay. The phytotoxicities of all chemicals decreased with increased organic matter. The phytotoxicities of the dinitroanilines were: dinitramine > trifluralin > profluralin = fluchloralin. Increased organic matter increased the persistence of trifluralin and fluchloralin. Profluralin and dinitramine persistence increased with increased clay and organic matter content. Profluralin was the most persistent chemical over all soil types. Under environmental conditions that retard dinitroaniline loss from Manitoba soils, residues of some of these herbicides may cause crop injury the year after application.

Adsorption and Diffusion of Dinitroaniline Herbicides in Soils

Adsorption of benefin (N-butyl-N-ethyl-α,α,α-trifluoro-2,6-dinitro-p-toluidine), dinitramine (N4,N4-diethyl-α,α,α-trifluoro-3,5-dinitrotoluene-2,4-diamine), fluchloralin [N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-(trifluoromethyl)aniline], oryzalin (3,5-dinitro-N4,N4-dipropylsulfanilamide), profluralin [N-(cyclopropylmethyl)-α,α,α-tri-fluoro-2,6-dinitro-N-propyl-p-toluidine], and trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) was studied in 10 Wisconsin soils. Ratios of the quantity of each herbicide adsorbed and quantities remaining in the soil solution at equilibrium (Kd value) on a Piano silt loam (Typic Argiudoll fine-silty, mixed, mesic) remained relatively constant over a range of concentrations. Herbicide adsorption by the soils was related more closely to soil organic matter than to the other soil chemical and physical properties. Diffusion of the herbicides in Piano silt loam was affected by soil water. Diffusion of trifluralin, profluralin and benefin decreased as soil water increased. Diffusion of dinitramine and fluchloralin did not change significantly with change in water content. Diffusion of oryzalin increased at the highest soil water content. None of the herbicides moved more than 10 mm in the soil during a 17-day period. In unsaturated Piano silt loam, relative mobility of the herbicides was trifluralin ≥benefin>profluralin>fluchloralin>dinitramine≥oryzalin. Oryzalin reached highest mobility in water-saturated soil.

Vapor Absorption and Translocation of Dinitroaniline Herbicides in Oats (Avena sativa) and Peas (Pisum sativum)

Roots or shoots of oats (Avena sativaL. ‘Dal’) and peas (Pisum sativumL. ‘Early Perfection’) were exposed to vapors of14C-labeled benefin (N-butyl-N-ethyl-α,α,α-trifluoro-2,6-dinitro-p-toluidine), dinitramine (N4,N4-diethyl-α,α,α-trifluoro-3,5-dinitrotoluene-2,4-diamine), fluchloralin [N-(2-chloroethyl)-2,6 dinitro-N-propyl-4-(trifluoromethyl)aniline], oryzalin (3,5-dinitro-N4,N4-dipropylsulfanilamide), profluralin [N-(cyclopropylmethyl)-α,α,α-trifluoro-2,6-dinitro-N-propyl-p-toluidine], and trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine). All of the dinitroaniline herbicides except oryzalin were absorbed by roots and shoots of germinating oats and peas. Some root-shoot translocation of the herbicides was observed in peas, but no shoot-root transport could be detected in either peas or oats. In peas,14C from root-absorbed benefin, fluchloralin, profluralin and trifluralin was detected in shoots, and14C from benefin and trifluralin was detected in cotyledons. In general, vapor absorption was correlated with rates of herbicide volatilization.

Efficacy and Rotational Crop Response to Levels and Dates of Dinitroaniline Herbicide Applications

Trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine), dinitramine (N4,N4-diethyl-α,α,α-rifluoro-3,5-dinitrotoluene-2,4-diamine), profluralin [N-(cyclopropylmethyl)-α,α,α-trifluoro 2,6-dinitro-N-propyl-p-toluidine], fluchloralin [N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-(trifluoromethyl)aniline], pendimethalin [N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine], butralin [4-(1,1-dimethylethyl)-N-(1-methylpropyl)-2,6-dinitrobenzenamine], and USB 3153 (N3,N3-di-N-propyl-2,4-dinitro-6-trifluoromethyl-m-phenylenediamine) were applied to evaluate weed control, cotton (Gossypium hirsutumL. ‘Dunn 119′) tolerance, and effect on rotational crops. Each herbicide was applied at 1-month intervals for 6 months prior to planting at 1, 1.25, 1.5, and 2X the recommended rates. Pigweed (Amaranthus hybridusL. andA. retroflexusL.) population counts and visual control ratings showed that weed control improved when treatments were applied closer to planting. Applications in November and December at 1.25X profluralin, 1.5X trifluralin, fluchloralin, and pendimethalin, 1X USB 3153, and 2X butralin were required to give effective weed control. Spring applications of 1X rates of profluralin, trifluralin, fluchloralin, and USB 3153, 1.25X rates of pendimethalin and dinitramine and 1.5X rate of butralin were required for adequate weed control. USB 3153 at all rates and dates of application severely limited growth and yields of wheat (Triticum aestivumL. ‘Funk 332′) planted after harvest and also the following May. Spring applications of profluralin at 1.5 and 2X rates and trifluralin at the 2X rate resulted in significant injury of rotational sorghum [Sorghum bicolor(L.) Moench ‘Dekalb E-59+’].

Suppression of Pea(Pisum sativum)Root Rot by Dinitroaniline Herbicides

Nine substituted dinitronaline herbicides were studied to determine their effectiveness in controlling common root rot of peas(Pisum sativumL.) caused byAphanomyces euteichesDrechs. under field conditions. Most of the dinitroaniline herbicide treatments increased plant stand, plant fresh weight, and shelled pea yield due to root rot suppression in each of the three years studied. Weed control was good in all plots and did not contribute to yield differences. Root rot suppression and crop injury were the primary determinants of yields. The greatest yield increases when compared with the weeded control were 82% for 0.56 kg/ha of dinitramine(N4,N4-diethyl-α,α,α-trifluoro-3,5-dinitrotoluene-2,4-diamine) in 1974, 80% for 0.84 kg/ha of fluchloralin [N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-(trifluoromethyl) aniline] in 1975, and 26% for 1.68 kg/ha of pendimethalin [N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine] in 1976. The best average yield increases over all years were 54% for the combination of trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) and oryzalin (3,5-dinitro-N4,N4-dipropylsulfanilamide) at 0.56 + 0.56 kg/ha, 49% for fluchloralin at 0.84 kg/ha, and 43% for pendimethalin at 0.84 kg/ha. Annual applications of 0.84 kg/ha of trifluralin delayed the rate of pathogen infestation of a field repeatedly planted to peas.

Evaluation of Substituted Dinitrobenzamine Herbicides in Cotton(Gossypium Lirsutum)Plantings

Seven substituted dinitrobenzamine herbicides were evaluated at two rates as preplant soil-incorporated treatments for 2 yr. Herbicides were applied broadcast and incorporated 7 cm deep into a sandy loam with a power-driven rototiller before the preplanting irrigation and 3 weeks before crop planting. Cotton(Gossypium hirsutumL. ‘Acala SJ-1’) stands were reduced by the higher rate of nitralin [4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylaniline], dinitramine(N4,N4-diethyl-a,a,a-trifluoro-3,5-dinitrotoluene-2,4-diamine), fluchloralin [N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-(trifluoromethyl)aniline], and AN 56477 [N,N-di-(2-chloroethyl)-2,6-dinitro-4-methylaniline]. Cotton yields were reduced by the higher rate of nitralin, dinitramine, and AN 56477. The poorest weed control was obtained with the lower rate of nitralin, AN 56477, and butralin [4-(1,1-dimethylethyl)-N-(1-methylpropyl)-2,6-dinitrobenzenamine]. A bioassay with Japanese millet [Echinochloa crus-galli(L.) Beauv. var.frumentacea(Roxb.) Wight] and grain sorghum [Sorghum bicolor(L.) Moench] was used to evaluate herbicides remaining in soil sampled 1, 120, and 240 days after application. Residual herbicide phytotoxicity at 240 days indicated dinitramine < trifluralin(a,a,a-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) = butralin < profluralin [N-(cyclopropylmethyl)-a,a,a-trifluoro-2,6-dinitro-N-propyl-p-toluidine] = AN 56477 < nitralin < fluchloralin. In greenhouse experiments, cotton taproot elongation was retarded by both rates of nitralin, dinitramine, and AN 56477 and by the higher rate of fluchloralin. All herbicides inhibited lateral roots of cotton in the herbicide-treated zone of soil, but butralin and profluralin caused the least inhibition.

Johnsongrass Control in Soybeans with Soil-Incorporated Dinitroaniline Herbicides

Field experiments were conducted to study the feasibility of using several dinitroaniline herbicides for the selective control of johnsongrass [Sorghum halepense(L.) Pers.] from seed and rhizomes in soybeans [Glycine max(L.) Merr. ‘Bragg’]. The herbicides were incorporated into the soil with two disk cultivations immediately after application. These were trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) at 0.6 to 2.2 kg/ha, nitralin [4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylaniline] at 0.6 to 2.2 kg/ha, dinitramine (N4,N4-diethyl-α,α,α,-trifluoro-3,5-dinitrotoluene-2,4-diamine) at 0.4 to 1.5 kg/ha, fluchloralin [N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-(trifluoromethyl)aniline] at 0.6 to 2.2 kg/ha, profluralin [N-(cyclopropyl-methyl)-α,α,α-trifluoro-2,6-dinitro-N-propyl-p-toluidine] at 0.8 to 3.4 kg/ha, butralin [4-(1,1-dimethylethyl)-N-(1-methylpropyl)-2,6-dinitrobenzenamine] at 1.7 to 6.7 kg/ha, AC-92390 (N-sec-butyl-2,6-dinitro-3,4-xylidine) at 0.8 to 3.4 kg/ha, and AN-56477 [N,N-di(2-chloroethyl)-4-methyl-2,6-dinitroaniline] at 2.2 to 4.5 kg/ha. On Bosket sandy loam soil, the best average johnsongrass control over a 2-yr period was obtained following profluralin at 1.7 kg/ha and butralin at 3.4 kg/ha. These treatments also resulted in highest average soybean yields. On Sharkey clay soil, profluralin at 3.4 kg/ha and butralin at 6.7 kg/ha resulted in maximum johnsongrass control and soybean yields. Immediate incorporation of profluralin and butralin into both soils for 2 successive years effectively controlled johnsongrass from rhizomes without soybean injury and with greatly increased soybean yields. Trifluralin, nitralin, and fluchloralin also provided acceptable johnsongrass control within individual experiments, and greatly increased soybean yields.

DINITROANILINE HERBICIDES FOR GRASSY WEED CONTROL IN RAPESEED

Five substituted dinitroaniline herbicides applied as preplanting soil incorporation treatments were evaluated in six field experiments in 1971, 1973, and 1974 for controlling green foxtail (Setaria viridis (L.) Beauv.) and wild oats (Avena fatua L.), and for tolerance of rapeseed (Brassica campestris L. and B. napus L.). In these experiments, A-820 (N-sec-butyl-4-tert-butyl-2,6-dinitroapiline) had the least activity, while dinitramine (N4,N4-diethyl-α,α,α,-trifluoro-3,5-dinitrotoluene-2,4-diamine) had the greatest activity, and in some tests injured germinating rapeseed, resulting in thinned stands and reduced yield. The activity of fluchloralin [N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-(trifluoro-methyl) aniline] and profluralin [N(cyclopropyl-methyl)-α,α,α-trifluro-2, 6-dinitro-N-propyl-p-toluidine] was slightly weaker than that of trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine). All these herbicides gave good control of green foxtail and wild oats. In 1971, due to low populations of green foxtail, good weed control did not give rapeseed yield increases. In 1973, under normal climatic conditions, rapeseed yields were increased significantly when the application of dinitramine, fluchloralin, profluralin, and trifluralin controlled green foxtail and wild oats successfully. In 1974, under drought conditions, good weed control from four dinitroanilines and triallate [S-(2,3,3-trichloroallyl) diisopropylthiocarbamate] was not reflected in significant yield increases although profluralin gave a significant yield increase in one test. Disc soil incorporation (7.5–10 cm deep) of dinitramine and trifluralin gave slightly better weed control and higher, though not significant, yield increases than harrow soil incorporation (2.5–5 cm deep).

トリフルオルメチルアニリン誘導体をジアゾ成分とする有機顔料の研究

トリフルオルメチル基をもついろいろなアニリン誘導体をジアゾ成分とするモノアゾ系顔料を合成し, 置換基の色調, 耐光性などの顔料適性に及ぼす影響を研究した。2-, 3-トリフルオルメチルアニリンおよびそれらのアルコキシ, ク獄ル, ニトロ, エチルスルポニル, アルキルアミノスルホニル置換体を合成し, ジアゾ化後β-ナフトールとカップリングさせて16種の顔料を合成した。これらの顔料はいずれもあざやかな橙黄～赤色を示し, 耐光性は3-トリフルオルメチル-6-エチルスルホニル, 次いで-6-ジメチルアミノスルポエルおよび2-トリフルオルメチル-4-クロル置換体が良好であり, アルコキシ置換体はすべて劣っていた。