IE43245B1 - Dinitroanilines - Google Patents

Description

This invention relates to a new class of 2,6dinitroanilines. More particularly, this invention relates to novel 3-(substituted)-2,6-dinitroanilines.

Various 2,6-dinitroanilines have been described in the chemical literature. Hantzsch, Deutsche Chemische Gesellschaft Berichte, 43, 1662-1685 (1910) discloses N,N-dipropyl-4-methyl-2,6-dinitroaniline and N,N-dimethyl4-methyl-2,6-dinitroaniline. Joshi et al., C.A. 28, 469 (1934) disclose N,N-dimethyl-4-iodo-2,6-dinitroaniline, N,N-dimethyl-4-bromo-2,6-dinitroaniline; 4-iodo-2,6dinitrophenylpiperidine, and 4-bromo-2,6-dinitrophenylpiperidine. Borsche et al., C.A. 5, 2079 (1911) disclose 2,6-dinitrophenylpiperidine. Daudt et al., U.S. Patent No. 2,212,825, disclose a number of 2,6-dinitroanilines bearing a trifluoromethyl group in the 4-position.

The utility of 2,6-dinitroanilines in agriculture was first disclosed in Soper U.S. Patents Nos. 3,111,403; 3,257,190; 3,332,769; and 3,367,949. Soper disclosed such compounds to possess herbicidal activity, notably preemergent herbicidal activity. Following Soper, a large number of related dinitroanilines have also been shown to possess similar herbicidal activity. See, for example, U.S. Patents Nos. 3,321,292; 3,617,251; 3,617,252; 3,672,864; 3,672,866; 3,764,624,- and 3,877,924 and Belgian Patent 787,939.

This invention relates to a new class Of 3(substituted)-2,6-dinitroanilines of the general formulat -2124% (I) win-re in Q is NiiCN, N3, 5CN, S-iCpC^ alkyl) -CN or SCii.,CO.,ClL, ; R^ is hydrogen, C^-C5 nontertiary alkyl, C^-C^ alkenyl, chloro C-^-C^ alkyl, chloro C^-C^ alkenyl or cyclo propyImethyl; F is nontertiary alkyl, C^-C^ alkenyl, phenyl, chloro C2~C3 alkyl, chloro C3~C4 alkenyl, chlorophenyl., eyelopropyImethyl, C^-C^ alkynyl, tetrahydrofuryl o Cj-C-j alkyl, l-(N-melhyh:nrbamoyl)oihyl <.r· Mfrc ) · R1 is C,-C3 alkyl; provided that when is N{R^)7 R is hydrogen; and the triethylamine, pyridine and alkali metal salts thereof when Q is NHCN.

The compounds of formula 1 may be prepared by reacting a compound of the general formula ..: O . J< ill) Cf-: i 2 wherein K and R are defined as before, with a displacement agent. -34324S A preferred group of compounds are those of formula I wherein Q is SCN. Especially preferred of this 1 2 group are the compounds wherein R is hydrogen and R is 1 3-pentyl, R is ethyl and R is 2-methyl-3-propenyl, and R and R are both n-propyl.

Another class of preferred compounds are those of 1 2 formula I wherein Q is NHCH and both R and R are ethyl as 1 2 well as the compound wherein R is hydrogen and R is 3pentyl. Another preferred compound of this group is the one 2 in which R is hydrogen and R is n-propyl.

A third class of preferred compounds are those 1 2 of formula I wherein Q is N3 and R is hydrogen and R is nontertiary alkyl as well as the compounds wherein both R1 and R2 are alkyl.

As used in this specification, all the terms appearing in the above description of the compounds of formula I have their usual meanings. Exemplary of the compounds coming within the scope of formula X are the following; N-(2-butyi)-3-cyanamino-2,6-dinitro-4-tri£luoromethylaniline 3-cyanamino-N,N-diethyl-2,6-dinitro-4-trifluoromethylaniline 3-cyanamino-2,6-dinitro-N-(4-heptyl)-4-trifluoromethy laniline 3-cyanaraino-2,6-dinitro-N-ethyl-N-n-propyl-4trifluoromethylaniline N-(2-chloroethyl)-3-cyanamino-2,6-dinitro-N-npropyl-4-trifluoromethylaniline -4t-allyl- 3-cyana'ino-;.·. fc-e:..vitro-N-schy 1-4i ri? luiirci - „n : ; line -cyanamino-2,6-dini tro-;-i-e'chyi-;,T~r.e fch'iiyl4-1 a i f1uo rome thy1aπ i11πe a-n-butyl-3-cysr.aminc-2,0-2initro-i-i-efchyl-4t r i £ 1 uoroiiie t hylan ill ne 4- ' —ch 1] y i ’ - . , r-hinitro-N.u-propy! -1 --:. r ί 1' J toromerPyloni line l-cyananirno-N-eyclopropy line thy 1-2 /--i.ini tro-il4 2 r;-propy 1-1 - Lr i fluoromothylan ilino .’.:,;i-aiethyi-N’- (2.-6-ciinitro-3-thiocyanato-itr t f lucrome tiiy 1 pneri-'i) hydrazine N-a1lyi-2,6-dinitro-N-n-propy1-ΐ-thioeyerate4 - -: r i f 1 j o r om e t h y 1 a n i 1 ί n e N-cyolopropylaiethyl-f, 6-dinitro-N-s~:iyi-3-thiooyana to-4-1 ri f 1 uorometliy lani 1 i.ne 4- ! 2 —be ty I j -2 , 6 —i ί Γ1 i ‘ rn- 1- ’ i;; oeyor. : tn-4 - tr i N ijoro.oet-.hy I a π i I i ne ; 2-ch loroethyi i-2,6-dini tr tn-propyl - 3-thi o2 ϋ cy aηafco-4-cr i£ 1uoromethyIaηi 1 i n e N-{2-chloroallyl)-2,5-dinitro-M-ethyl-3-thiocyan a to-4-fc rj f1uoromet hylaniline , b-Ίi.n i fcro-H-ethy 1 -M-meth-i 1 lyl - 3-thiocyanatoil -1 ί ί f 1 > rr ·« fc ny 1 an i 1 ine 2b ι M-allyl-3-azido-2,6-dinitro-N-ethy1-4-trifluoroiiethyl -ι·.Ω 11. me i ύ ώ H U 3-azido-N-cyclopropylmethyl-2,6-dinitro-N-npropyl-4-l ri fluoromt* lhyl anil ine 3-azido-N-(2-butyl)-2,6-dinitro-4-trifluoromethylaniline The cyanamino compounds of formula I are sufficiently acidic to form salts with strong bases, such as tertiary amines and alkali metal hydroxides. Therefore, included within the scope of the compounds of formula I are the salts thereof, such as the triethylamine, pyridine, and alkali metal salts.

The 3-cyanamino-2,6-dinitroanilines are prepared by reaction of the corresponding 3-chloro compound of formula ΙΪ with cyanamide as the displacement agent in the presence of a base. The corresponding 3-chloro-2,6-dinitroaniline is, in turn, prepared by the reaction of the appropriate amine with 2,4-dichloro-3,5-dinitrobenzotrifluoride as described in U.S. Patent No. 3,617,252.

The reaction of cyanamide with a 3-chloro-2,6dinitroaniline is preferably conducted in an inert solvent at a temperature within the range from about 25°C. to 100°C. Suitable inert solvents include ethanol, dioxane and tetrahydrofuran. Examples of bases used in the reaction include triethylamine, pyridine, diazabicyclooctane, an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, an alkali metal methoxide such as sodium methoxide and potassium methoxide, and an alkali metal ethoxide such as sodium ethoxide and potassium ethoxide. The reaction is conveniently conducted at the reflux temperature of such solvent. Reaction times vary from a few -6hums 1.1» a hw day:-;, such as f.; -S.u -:i. .tf six ti’iurs f·') about six days. Upr-»n comp J fit ion ,: react, ion, n? reaction ,/<' '·: ι;; illowcd to cool ar d noury; './cr ; · to precipi dt; tho j if .'duct.

Trie compounds of formula I wherein Q is other than NiiCii or N3re readily prepared by the reaction of the oirresponding 3-chloro-2,S-dinitroaniJine of formula II with sodium sulfide and cyanogen chloride or other thio displacement agent. The reaction is conveniently conducted ir. an inert solvent, such as dimethylformamide, dimethylacetamide, dioxane, or tetrahydrofuran, at a temperature 'within the range of about 10”C. to 40°C. and preferably at aoout 10°C. to 25’C. Cyanogen chloride may be bubbled into a solu.cion of the chloro compound and sodium sulfide to effect thconversion to the thiocyanate. The ree.ee ion mixture is poured over ice to precipitate the product.

The novel i-azido-2,δ-dinitroaniIjnes of formula (I) are prepared from the corresponding 3-ch.loro- 2,6dinitroanilines of formula (II! by reaction of the chloro compound with an alkali metal azide such as sodium azide as the displacement aqent, in an inert solvent. The reaction proceeds readily at temperatures within the range of from 10 to 50°C., preferably within the range of 25 to _>oJC. Suitable inert solvents include dimethylformamide, dimethylacetamide, tetrahydrofuran, and dimethyl sulfoxide.

Preferably, an aqueous solution of the alkali metai azide is added dropwise to a stirred solution of the i-i-h loro-i .. fi -d in it roan i 1 inc in a solvent, such as dimethylforin.jmide. Stirring of tin; reaction mixture is continued. 7~ preferably at room temperature, for from 30 minutes to 3 hours. Generally, the reaction will be complete in about 1 hour. The product is recovered by pouring the reaction mixture over ice and filtering.

The 3-chloro starting materials for the preparation of the compounds of formula (I) are prepared by reacting the appropriate amine or appropriate hydrazine with 2,4-dichloro-3,5-dinitrobenzotrifluoride as described in U.S. Patent No. 3,617,252. The amine or hydrazine is chosen to give the desired substitution pattern on the anilino nitrogen of the final product. The amine or hydrazine reacts preferentially with the chlorine atom between the two nitro groups of the 2,4-dichloro-3,5-dinitroben2Otrifluoride to give.the 3-chloro-2,6-dinitroaniline compound of formula (II).

The preparation of the cyanamines of formula I will be illustrated by the following Examples.

Example 1 A mixture of 40 gm. of 3-chloro-2,6-dinitro-N(3-pentyl)-4-trifluoromethylaniline, 10.5 qm. of cyanamide) and 30 gm. of triethyiamine in 250 ml. of 95% aqueous ethanol was heated under reflux for five days. The solution was allowed to cool and was poured over ice water. The product which precipitated was removed by filtration and recrystallized from 95% aqueous ethanol and water to give 36 gm. (71%) of the triethyiamine salt of 3-cyanamino-2,6dinitro-N-(3-pentyl)-4-trifluoromethylaniline, m.p. 135137°C. The structure was confirmed by the NMR and IR spectra and elemental analysis. -84 Ti 3245 Calculated: C, 49.35; li, 6. 12; N, 18.17 Found: C, 49.56; ii, 6.06; i'i, 18.37 Following the procedure of Example 1, the following additional represent ative compounds of formula Γ were prepared. All the compounds wore isolated as the triethylamine salt.

Example 2 3-cyanamino-2,6-dinitro-N,N-di-n-propyl-4trifluoromethylaniline, triethylamine salt, m.p. 102~103°C. Example 3 3-cyanamino-N,N~diethy1-2,6-dinitro-4-trifluoromethylani1ine, triethylamine salt, m.p. 122-124°C.

Example 4 j-cyanamino-2,6-dinit ro-N-ri-propy I - 4-t r i f i.uoromethylanilino, triethylamine salt, m.p. :30-131°C.

Example 5 3-cyanamino-2,6-dinitro-N-ethyi-.-!-im?thyl-4trifluoromethylaniline, triethylamine salt, m.p. 84-86°C. Example 6 3-cyanamino-2,6-di nitro-N-(2-propyny1)-4-trirluoromethylaniline, triethylamine salt, m.p. 129-132°C. Example 7 N-(2-chloro-2-propenyl)-3-cyanamino-2,6-dinitroN-n-propyl-4-tri t'luoromethylaniline, triethylamine salt, m.p. 63-70C. 3-cyanamino-2,6-dinitro-N-methy1-N-(2-tetrahydrofaryImethyl)-4-trifluoromethylaniline, triethylamine salt, m.p. 98-100°C. -9The following cyanamino free bases of formula I were prepared by neutralizing the corresponding triethylamine salts with dilute hydrochloric acid in diethyl ether at room temperature.

Example 9 3-cyanamino-N,N-diethyl-2,6-dinitro-4-trifluoromethylaniline, m.p. 195-198°C.

Example 10 3-cyanamino-2,6-dinitro-N-(3-pentyl)-4-trifluoromethylaniline, m.p. 106-110°C.

Example 11 3-cyanarnino-2,6-dinitro-N-n-propyl-4-trifluoromethylaniline, m.p. 140-143eC.

The preparation Of the compounds of formula I wherein Q is other than NHCN or N3 will be illustrated by the following examples.

Example 12 To a cold solution of 40 gm. of 3-chloro-2,6dinitro-N-(3-pentyl)-4-trifluoromethylaniline in 400 ml. of dimethylformamide was added a solution of 36 gm. of sodium sulfide nonahydrate in 100 ml. of water. The mixture was stirred for one half hour, then cyanogen chloride was bubbled into the cold solution for 10 minutes. At the end of this time, thin layer chromatography showed no starting material and the originally dark solution had become light red. The reaction mixture was poured over ice water and the product solidified. It was recovered by filtration and recrystallized from 95% aqueous ethanol and water to yield -10?7 gm. (K'J ) of 2,6-dinitro-N- ! 5-pcntyi)- 3-thioeyanato-4- trifluoromethylaniline, m.p. 97-99°C. The structure was confirmed by the NMR spectrum and eler snral analysis. Calculated: C, 41,27; H, 3.46; N, 14.81 5 Found: C, 41.02: H, 3.40; N, 14.56 Following the procedure of E xample 12, the fol- lowing additional representative compounds were prepared. Example 11 i, 6-di ni t ro-N-methyl-3-thi ocyanat.o-4-tr i r 1 uoroI!) methyl an j. i i tie, m.p. 125-126”C.

Example 14 Ν,N-dimethy1-2,6-dinitro-3-thiocyanato-4-trifluoromethylaniline, m.p. 153-155°C.

Example 15 Ν' - {2,6-dinitro-3-thiocyanato-4-trifluoromethy1phanyl)-Ν,N-dimethylhydrazine, m.p. 146-14it.

Exantpl e j 6 2.6- dinitro-N,N-di-n-propy1-3-thiocyanato-4trifluoroniethylaniline, oil Example 17 N,N-diethyl-2,b-dini tro-j-thiocyanato-4-tri fluoromethylani1ine, m.p. 116-118°C.

Example_ Ifi 2.6- dinitro-N-methyl-N-(2-tetrahydrofurylmethy1) 2b 3-thiocyanato-4-trifluoromethylaniline, m.p. 75-76°C.

Example 19 2,6-dinitro-N-methyl-N-(2-propynyl)-3-thiocyunato-4-trifluoromethylaniline, m.p. il4-8fi°c. -11Example 20 2,6-dinitro-N-ethyl-N-(2-methyl-2-propenyl)-3thiocyanato-4-trifluoromethylaniline, m.p. 92-94°C.

Example 21 To a cold solution of 3.6 gm. of 3-chloro-2,6-. dinitro-N-(3-pentyl)-4-trifluoromethylaniline and 1.1 gm. of methyl thioglycolate in 75 ml. of dimethylformamide was added dropwise 6.6 gm. of potassium hydroxide in 5 ml. of water. The mixture was allowed to come to room temperature and stirred for one hour. The reaction mixture was poured over ice water and the product solidified. It was recovered by filtration and recrystallized from ethanol to yield 1.6 gm. of 2,6-dinitro-N-(3-pentyl)-3-methoxycarbonylmethylthio-4-trifluoromethylaniline, m.p. 60-61°C. The structure was confirmed by the NMR spectrum and elemental analysis.

Calculated: C, 42.35; H, 4.27; N, 9.88 Found: C, 42.43; H, 4.14; N, 9.89 Example 22 . To 3.4 gm. of 3-chloro-N,N-diethyl-2,6-dinitro4-trifluoromethylaniline in 75 ml. of dimethylformamide was added 2.4 gm. of sodium sulfide nonahydrate in 10 ml. of water. The mixture was stirred at 25°C. for one hour, then 0.76 gm. of chloroacetonitrile was added. The mixture was stirred at 25°C. for 12 hours and then poured over ice water. The product solidified, was extracted with ether, dried, the solvent evaporated and the residue recrystallized from ethanol to yield 2.7 gm. of 3-cyanomethylthioN,N-diethyl-2,6-dinitro-4-trifluoromethylaniline, m.p. -12Z/'/t'O. Tin· sliucliilc· Will; coni i i moil by I.hi MMK :ψ··|ιιιιιι and elemental analysis.

Calculated: C, 41.27; H, 1.46; '1, 14.81 Found: C, 41.15; H, 3.25; '1, 14.65 Example 23 To a cold solution of 6.0 gm. of i-chloro-2,6dir,i t: ro-N-methyl-4-tr i f 1 uoroinethyl ani 1 i ne and 4.0 nil. of 3-mercaptopropionitrile was added dropwise with stirring 0.6 gm, of lithium hydroxide in 100 ml. of dimethylformamide.

The solution was warmed to 25°C. and stirred for 12 hours. The reaction mixture was poured over ice water and the product solidified. It was recovered by filtration and recrystallized from ethanol to yield 5.8 gm. of 3-cyanoethylthio-2,6-dinitro-N-methyl-4-trifluoromethylaniline, lh in.p. 116-117°C. The structure was confirmed by the IMS spectrum and elemental analysis.

Calculated: C, 37.72; II, 2.5'); :J, 1),. 00 Found: C, 37.96: 11, 2.84; I, if,.29 13xample_ 24 uu To a cold solution of 21. ί gm. of l-chloro-2,6il j ni tro-N-( i-pent'/l)-4-tr i f Luoromel Ir/1-,n i 1 ί ru> and 10 ml. of β-mercnptopropionitrile was added dropwise with stirring 2.0 gm. of lithium hydroxide in 200 ml. of dimethylformamide.

The mixture was warmed to 25°C. and stirred for 2 hours.

The reaction mixture was poured over ice water and the product separated as an oil. The solution was extracted with ether, washed with water, dried and concentrated to leave an oil. The product was chromatographed on a r,i 1 icg-qel column wi.lh benzene and the solvent removed to yield 2.0 gm. -1343345 of 3-cyanoethylthio-2,6-dinitro-N-(3-pentyl)-4-trifluoromethylaniline. The structure was confirmed by the NMR spectrum and elemental analysis.

Calculated: C, 44.33; H, 4,22; N, 13.79 Found: C, 44.29; H, 4.22; N, 13.63 The following Examples illustrate the preparation of the compounds of formula (I) wherein Q is N-j.

Example 25 Λ solution of 2.3 gm. of sodium azide in 15 ml. of water Was added dropwise to a solution of 7 gm. of 3chloro-N,N-dimethyl-2,6-dinitro-4-trifluoromethylaniline in 90 ml. of dimethylformamide at room temperature. The mixture was stirred at room temperature for one hour, poured over ice water, and filtered to recover 6.9 gm. (94%) of 3azido-M,N-dimethyl-2,6-dinitro-4-trifluoromethylaniline, m.p. 66-67°C. The structure was confirmed by the NMR spectrum and elemental analysis.

Calculated:· C, 33.76; H, 2.20; N, 26.25 Found: C, 33.98; H, 2.19; N, 26.53 Example 26 A solution of 0.75 gm. of sodium azide in 15 ml. of water was added dropwise to a solution of 3.5 gm. of N-n-butyl-3-chloro-2,6-dinitro-N-ethyl-4-trifluoromethylaniline in 75 ml. of dimethylformamide at room temperature. The mixture was stirred at room temperature for 2 hours and poured over icewater. The product separated as an oil. The mixture was extracted three times with nethylene chloride, the methylene chloride evaporated to iryness, the residue taken up in et.her, and the ether -143245 solution extracted three times with water. Evaporation of the ether left 3.1 gm. (92-) of l-azido-N-n-butyl-2,6dini.tro-;i-othyl-4-trifluoromethylaniline as an oil. The structure was confirmed by the NMR spectrum and elemental 5 analysis.

Calculated: C, 41.49; 11, 4.02; N, 22.33 Found: C, 41.39; II, 3.89; N, 22.10 Example 27 A solution of 1.0 gm. of sodium azide in 10 ml. [0 of water was added dropwise to a solution of 3.2 gm. of N(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-Ν', N'dimethylhydrazine in 80 ml. of dimethylformamide at room temperature. The mixture was stirred at room temperature for 1 hour, poured over ice water, and filtered. The solid j, product was dried and recrystallized from .ibsolnte ethanol to yield 1.1 gm. (937) of N-{3-azido-2,6-dinitro-1-trifluot:oniethylphenyl)-N’,N'-dimethylhydrazine, m.p. J2?“125°C. The structure was confirmed by the NMR spectrum and elemental analysis.

Calculated: C, 32.25; H, 2.41; N, 29.25 Found: C, 32.21; H, 2.39; N, 29.34 Example 28 to 40 Following the procedure of one of Examples 2527, the following additional compounds of formula (T) 2'j where ϋ is were prepared. -15Melting Point, °C.

N3C2H5C2H5 OilW3 H ch(ch3:)c3h7 25 (Oil) ' n3 H ch(ch3)c2h5 77-78N3 H ch[ch(ch3)2]2 OilN3 H CH(C2H5)C3H? 27-28N3 H ch3 118-120N3C2Hs n-C3H7 OilN3 H 4-ClC,H. 6 4 119-121N3 H ch(c2h5)2 77-79N3 n-C3H7 n-C3H? OilN3 H CH(CH3)CONHCH3 163(dec.)N3 H n-C3H7 70-72N3C2H5 methallyl 46-48 The novel 2 ,6-dinitroanilines of formula I are useful in the control of Plasmopara viticola, the causative organism of grape downy mildew. They also exhibit some herbicidal activity. When used as fungicides. they are employed in accordance with techniques known in the agricultural art.

Tests against fungal foliar phytopathogens have demonstrated the powerful plant protective effect of the compounds Of formula I. The following test describes the use of the compounds to reduce both the incidence and severity of grape downy mildew. In the test described below, the compounds were applied as a solution or emulsion prepared by mixing 70 mg. of test compound with 1.925 ml. of a mixture prepared from 500 ml. of acetone, 500 itil. of ethanol and 100 ml. of polyoxyethylene sorbitan monolaurate. -16The composition containing the test compound was then . diluted with deionized water to obtain the desired concentration, measured in parts per million by weight (ppm.).

In the tests, the host plant was Vitis vinifero & The pathogen employed was Plasmopara yiticola. Stock grape plants were grown in a greenhouse to serve as a supply of leaves for test use. On the test day, young expanding leaves were detached from the vines. One leaf was placed bottom side up in a plastic petri plate (100 x 20 mm.) and a water-soaked wad of cotton was wrapped around the petiole base. The petri plate contained a Whatman filter paper (Whatman is a Trade Mark) planed on top of an expanded plastic mat. The mat and filter paper kept the leaf above water flooding the bottom of the petri plate. Each test chemical was sprayed on the under side of the leaf and allowed to dry. All the test leaves were then inoculated by atomizing a conidial suspension over the under leaf surface and then each plate was covered. All the plates were placed on a shelf in a mist room at a temperature of 18-20°C. and a light/dark cycle of ,0 8/16 hours. Illumination was obtained from cool white fluorescent lamps ranging between 9,140-10,760 lumen/m.

Seven days after treatment, the leaves were examined and symptoms of disease were observed and results recorded using a scale of 1 to 5, wherein 1 indicates severe disease or no ,5 control and 5 indicates no disease or complete control.

The conidia employed as the inoculum for the test were obtained from recently infected leaf tissue stored in a chillroom at 5’C. The conidia were washed off the leaf surface with a brush and suspended in deionized water. The -17suspension was sprayed on leaf surfaces with a Devilbiss atomizer. (Devilbiss is a Trade Mark).

In each test, two non-treated control leaves were sprayed with water containing the solvent-surfactant system.

The results obtained with a number of compounds of formula I are summarized in the following table. A wide range of concentrations of the test compounds was employed.

A blank space in the table indicates that the compound was not tested at the indicated concentration. An asterisk indicates that the compound was phytotoxic at the indicated concentration. When a compound was tested more than once at the same concentration, the result given is an average. The 3-cyanamino compounds were tested as the triethyiamine salt. Testing of 3-cyanamino-N,N-diethyl-2,6-dinitro-4-trifluoromethylaniline as the triethyiamine salt and the free compound showed both forms performed essentially the same. -18ml + Γμ| Ή ΟΙ + ι mi ΓΠ r-i c\j 4* ro ο) + + ο I r~t| + + (Ν r-4 -h + *3· <Ν ol ο) ιη * 04 ί r—i i ro •sr + , Ο «ς}' ol ο in (Ν 'ΤΙ + + ro si· Ol 4· o in in ι-m co I cu m *3· in + ro k-4 ω C5 ω CU oi CJ CJ X CJ ro X υ r-4 m r\j Γ- OJ m X Γ- ΙΕ If) ro X ro X γο X ro ro X X CM X o Cj CM CJ CJ ΓΜ u CJ CJ -—- 1 cj 1 1 CJ z Cl ·—' Cl Cl X X CJ CJ X t-* Γ- m X X X fO ro ro r*j χ X X X CJ X CJ X CJ u t 1 Cl Cl ro X z z o CJ z CJ z CM CM CJ z CU Z z z z z z u o X CU CJ X u CJ CJ CJ CJ CJ ω CJ CJ X w cj ω ω ω X X X cu CM CJ CU z z z X X ω X CJ CJ CJ ω ω cn -1943345 I I CN CN CN ft ΙΠ E CN u in *cn +> c ft ΙΛ E CN U tn E fN O UJ + xa* r-i n* + + + «τ cn xa* I CN E Q CN E a II H υ-υ CN E a U ii U CN E U E a II u CN E U r* E cn cn cn cn Ε O EE υ ι, ο u c 2 z z z z z z υ u □ u u u u ω E ω s E cn E Z z z Z 3245 Downy Mildew Control (pp ml • + CM CM ml ι γμ I ro of ι + + m I M' cm m oj l ol m m + CM I ro 0)+ + + + ol rf rf rf cn cm! ol + o m m rr cm rfl Oi + ΟI m in m rf oo | I + PO r-l ί rf I •cf rf <· + •cf rf CM + m rr rf + m m co I + I rc, ni I f CO rf -¥ ro cm I CM CM co + <-o rf rf rf rf oo + m rf in m in + po + CM ι m rf co I m m ro + m co X CM X r~( X Γ' CM cn X-. ro o >1 Γ cm υ X CJ X CM m CJ X X r—I X X— X co cj X—. PO χ—. ro rf co H co ro z U CO PO X CM m X CJ CJ Φ U X o 1 X X X CJ CJ X υ 1 ! A 1 υ u Cl U o cj CM Cl Cl 4J Cl ' .— 1 ·—* X a z P X X X cj ·—· £ X U υ - υ X u cj X u Oi m co X EC X x (Μ O u ac x ro g co Z co po p Z Z *Z, > PO m m m X X X X X ro CJ CM CM U CJ CJ CJ 1 Cl co ro co Z Z Z ro co ro Z Z Z 21· The compounds of formula I are preferably employed in liquid, powder, or dust compositions containing one or more of the active compounds. In preparing such compositions, the compounds can be modified with one or more of a plurality of additaments including organic solvents, petroleum distillates, water or other liquid carriers, surface active dispersing agents, and finely divided inert solids.

In such compositions, the compound of formula I can be present in a concentration from about 2 to 98% by weight.

In the preparation of dust compositions, the compounds of formula I can be formulated with any of the finely divided solids, such as pyrophyllite, talc, chalk and gypsum. In such operations, the finely divided carrier is ground or mixed with the compound or is wet with a solution of the compound in a volatile organic solvent. Similarly, dust compositions containing the active compound can be prepared with various solid surface active dispersing agents, such as fuller's earth, bentonite, attapulgite, and other clays. Depending Upon the proportions of ingredients, these dust compositions may be employed as such or may be diluted with an additional solid surface active dispersing agent or with pytophyllite, chalk, talc, gypsum, and the like, to obtain the desired amount of active ingredient in the final composition. Also, such dust compositions can be dispersed in water with or without the aid of dispersing agents to form liquid sprayable mixtures.

The compounds of formula I or a liquid or dust concentrate composition containing one or more of such -224 3 2 4 5 compounds can be incorporated in intimate mixture with surface active dispersing agents, such as nonionic emulsifying agents, to form spray compositions. Such compositions may be employed as such or may be dispersed in liquid carriers to form diluted sprays containing the active compound in any desired amount.

Similarly, the active compound, of formula I can be formulated with a suitable water-immiscible organic liquid and a surface active dispersing agent to produce emulsifiable concentrates which can be further diluted with water and/or oil to form spray mixtures in the form of oil-water emulsions. Preferred dispersing agents to be employed in these compositions are oil-soluble and include the nonionic emulsifiers, such as condensation products of alkylene oxides with phenols, sorbitan esters and complex ether alcohols. Suitable organic liquids which can be employed include petrol.-urn oils and distillates, toluene, and the synthetic organic oils. The surface active dispersing agents are usually employed in liquid compositions in the amount of from 0.1 to 20% by weight of the composition.

The amount of the compound of formula I for use in the control of grape downy mildew can vary widely, provided that an effective amount is used. The amount which is effective is dependent upon the particular compound employed and the severity of the downy mildew infection. In general, good results are obtained using liquid compositions containing from about 2,000 to about 10 ppm. of the active compound. When dusts are used, good results are usually -23stained with compositions containing from about 0.05 to □out 5% or more by weight of the active compound. In sneral, when used in the control of downy mildew, the impounds are employed at a rate of from about 10 gm. to 2 }. per hectare. For such use, the compounds are applied to le foliage of the host plant.

Claims (22)

1. ciaiw;:1. A 3-(substituted)-2,6-dinitroaniline of the general formula: wherein Q is NHCN, N 3 , SCN, S»(C 1 -C 4 alkyl)-CN or SCH 2 CO 2 CH 3 ; is hydrogen, C^-Cg nontertiary alkyl, C 3 -C 4 alkenyl, chloro C 2 ~C 3 alkyl, chloro Cg-C 4 alkenyl or cyclopropylmethyl; 10 R is nontertiary alkyl, C 3 ~C 4 alkenyl, phenyl, chloro C 2 -C 3 alkyl, chloro C 3 ~C 4 alkenyl, chlorophenyl, cyclopropyImethyl, C 3 ~C 4 alkynyl, tetrahydrofuryl C^~C 3 alkyl, i-(N-methyloarbamoyl)ethyl or N(R°) 2 ; R 3 is Cj^-Cj alkyl; provided that when R 3 is N(R 3 ) 0 R 3- is 15 z hydrogen; and the triethylamine, pyridine and alkali metal salts thereof when Q is NHCN. 2. A compound of Claim 1 wherein Q is NHCN. 20 3. A compound of Claim 1 wherein Q is n 3 . 4. A compound of Claim 1 wherein Q is SCN. -25i3245 5 · 2,6-Dinitro-N-(3-pentyl)-3-thioeyanato-4trifluoromethylaniline

2. 6. 2,6-Dinitro-N,N-di-n-propyl-3-thiocyanato-4trifluoromethylaniline

3. 7. 2,6-Dinitro-N-ethyl-N-(2-methyl-2-propenyl) 3-thiocyanato-4-trifluoromethylaniline

4. 8. 3-Cyanamino-2,6-dinitro-N-(3-pentyl)-4-trifluoromethylaniline

5. 9 · 3-Cyanamino-2,6-dinitro-N,N-diethyl-4-trifluoromethylaniline

6. 10. 3-Cyanamino-2,6-dinitro-N-n-propyl~4-trifluoromethylaniline

7. 11. 3-Azido-2,6-dinitro-N-(3-pentyl)-4-trifluoro methylaniline

8. 12. 3-Azido-2,6-dinitro-N-(2-pentyl)-4-trifluoro Methylaniline

9. 13. 3-Azido-2,6-dinitro-N,N-di-n-propyl-4-triEluoromethylaniline

10. 14. 3-AzidO-N-n-butyl-2,6-dinitro-N-ethyl-4:rifluorontethylanxline

11. 15. 3-Azido-2,6-dinitro-N-*ethyl-N-(2-methyl-2jropenyl) -4-trif lujoromethylaniline 4 5

12. 16. A compound of formula (I) as claimed in claim 1 substantially as hereinbefore described with reference to any one of the foregoing Examples.

13. 17. A process for preparing a compound of formula (I) as claimed reacting a compound of (II) 1 2 wherein R and R are as defined in claim 1, with a displacement agent.

14. 18. The process of claim 17 wherein Q is SON and the displacement agent is sodium sulfide and cyanogen chloride.

15. 19. The process of claim 17 wherein Q is NHCN and the displacement agent is cyanamid.

16. 20. The process of claim 17 wherein Q is N g and the displacement agent is sodium azide.

17. 21. A fungicidal composition which comprises an inert carrier and as active ingredient a compound of the general formula (I) as claimed in any one of claims 1 to 16.

18. 22. A process as claimed in claim 17 substantially as hereinbefore described with reference to any one of the Examples.

19. 23. A composition as defined in claim 21 substantially as hereinbefore described. - 27 HZS4S

20. 24. A method of treating plants susceptible to or suffering from attack by 'fungal foliar phytopathogens which comprises applying a compound of formula 1, as claimed in any one of claims 1 to 16, or a composition as claimed in claim 21, to the plant.

21. 25. A method according to claim 24 wherein the phytopathogen ie grape downy mildew.

22. 26. A compound of formula 1 whenever prepared by a process according to any one of claims 17 to 20 or 22.