N-acyloxyalkyl-substituted dinitroanilines
United States Patent Kiehs et al. 1 Apr. 8, 1975 1 N-ACYLOXYALKYL-SUBSTITUTED [52] U.S. Cl. 260/487; 7l/10 G; 260/463; DINITROANILINES 260/465 D; 260/470; 260/471 C; 260/482 C; [75] Inventors: Karl Kiehs, Lamperthein; 260/490; 260/577 Karbfleinz Koenig Frankemhal, [51] Int. Cl. C07c 69/62 [58] Field of Search 260/487 490 Adolf Fischer, Mutterstadt. all of Germany [73] A B d h A T &amp; S d F b k [56] References Cited ssignee: a so e mm- 0 aa n .Aktiengesellschaft, Ludwigshafen. UNITED STATES PATENTS Rhine Germany 3,332,998 7/1967 Cambre et al 260/573 [22] Filed: 1972 Primary E.\&#39;uminerLorraine A. Weinberger 2 Appl. 2 4 Assistan! ExaminerPaul J. Killos Attorney. Agent, or FirmJohnston, Kell, Thompson Related U.S. Application Data &amp; Sh fl ff [62] Division of Ser. No. 170,278, Aug. 9, i971. Pat. No.  
  57 ABSTRACT [30] Foreign Application Priority Data New and valuable N-acyloxyalkyl-substituted dini- Sept. 2, 1970 Germany .v 2043442 troanilines having a good herbicidal action and process for controlling the growth of unwanted plants with these compounds.  
 7 Claims, No Drawings &#39;rides, isocyanates) to give the products of the inven- 1 2 N-ACYLOXYALKYL-SUBSTITUTED The suitably substituted secondary amines may also DINITROANILINES be reached direct to form the products of the invention RELATED APPLICATION in accordance w th the above equation. Starting materials and intermediates may be pro- Thl appllca n IS a dlVlSlOn Of Our p g pp 5 duced for instance by the processes of US. Pat. Nos. atlOfl Serlal Y filed A g 1971, HOW 2,257,093 and 3,227,734 and in accordance with Jour- US. at- N 3,770,779. nalofthe Chemical Society, London, 1949, 190, Suppl.  
 The present invention relates to new and&#39;valuable substituted dinitroanilines having a good herbicidal ac- EXAMPLE 1 tion and the use of these compounds as herbicides. 10 N-methylthioethyl-N-hydfoxyethyl-z,6-dinitl&#39;O-4- It is known to use 4-trifluoromethyl-2,6-dinitro-N,N- trifluoromethylanilinez dipropylaniline as a herbicide. However, its action is 54 parts (b w i ht) of2,6-dinitr0-4-triflu0r0methyl- HOI satisf orychlorobenzene is dissolved in 250 parts of tetrahydro- We have now found that substituted dinitroanilines furan or benzene; subsequently, a mixture of 28.4 parts of the formula of N-methylthioethylaminoethanol and 20.2 parts of triethylamine is slowly added, and the whole is stirred for 2 hours at 50 to 60C. After the triethylammonium N0 5 hydrochloride has been filtered off, the filtrate is con- 1 centrated in vacuo and the residue recrystallized from R t ethanol. Melting point: 60 to 62C; yield: 96 percent.  
  R EXAMPLE 2 N-n-butyl-N-(l3-chloroacetyloxy-n-propyl)-2,6- dinitro-4-trifluoromethylaniline:  
  17.5 parts of N-n-butyl-N-B-hydroxy-n-pr0pyl-2,6- dinitro-4-trifluoromethylaniline (m.p. 75 to 77C; prepared as in Example 1) is dissolved in 50 parts of toluene; 9.0 parts of chloroacetyl chloride is then slowly in- .troduced. The mixture is then first stirred for 12 hours at room temperature, and for a further 3 hours at 40 where one of the radicals R and R denotes nitro and the other denotes methyl, trifluoromethyl or methylsulfonyl, R denotes acyloxyethyl or 2-acyloxypropyl (acetyl, propionyl, chloroacetyl, dichloroacetyl, trichloroacetyl, a-chloropropionyl, B-chloropropionyl, chlorocarbonyl car.b0methO;(y or w i and R4 to 50C. The filtrated solution is concentrated in vacuo has the Same meamngs as R and W addmonaily de&#39; and the residue recrystallized from ethanol/ligroin. note hydrogen, bromoethyl, alkylthroalkyl (having up Melting point: 0 to 86C. to 4 carbon atoms), or linear or branched alkyl, alkenyl or alkynyl each having up to 4 carbon atoms, hydroxy- EXAMPLE 3 ethyl z&#39;hydroxypropyl alkoxyalkyl (methoxyethyh N-methoxyethyl-N-chloroacetyloxyethyl-2 6-dinitroethoxyethyl, 2-methoxypropyl, 2-ethoxypropyl), 4 methy]ani]ine, cyanornethyl, cyanoethyl or chloroethyl, having a good 225 parts of N methoxyethyl N hydr0xyethy| 26 m i i 40 dinitro-4methylaniline (prepared as in Example 1 from The action is particularly in evidence on millet spe- 2 6 dinino 4 methylchlorobenzene and cies when the compounds are used preemergence and methoxyethyl N hydroXyethylamine mp; to at application rates of 0.5 to 3 kg per hectare. The ac- 42C) is reacted as described in EXample 4, with 10 mgredlemS arehsultable a Commnmg i gi parts of chloroacetyl chloride. An oily reaction product plants in crops suc as soya eans, cotton or n ran 45 is Obtained; M25: 15400 corn.  
 The new active ingredients are yellow crystalline sub stances or non-distillable oils. EXAMPLE 4 The new compounds are produced in accordance N-allyl-N-chlorocarbonyloxyethyl-2,6-dinitro-4- with the following equation: trifluoromethylaniline;  
 where R and R have the meanings given above and R 67 parts of N-allyl-N-hydroxyethyl-2,6-dinitro-4- denotes y y y 0r y yp py and R4 trifluoromethylaniline (prepared as in Example M n notes the same radicals as R and additionally linear or 1 5 3 50 is dissolved i 100 parts of carbon m branched y alkenyl or y y each havmg &#34;P to ride; at room temperature phosgene is passed in, the carbon atoms alkoxyalkyl cyanomethyl or cyanoethy temperature rising to approximately 40C. After the re- The compounds thus obtained may be reacted in conventional manner with halogenating agents (COCl ,5 SOCL SOBr PBr or acylating agents (acid chloaction has subsided, the mixture is stirred for 30 minutes and subsequently concentrated; the residue is recrystallized from ethanol/ligroin. Melting point: to  
 tron. 82C.  
 EXAMPLE 5 Methyl-[H N-allyl-N-2,6-dinitro-4-trifluoromethylphenyl)-aminoethyl carbonate:  
  At 10 to 20C, 5.7 parts of methyl chloroformate is added to a solution of 16.8 parts of Nallyl-N- hydroxyethyl-2,6-dinitro-4-trifluoromethylaniline and as solutions, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.  
  For the preparation of solutions to be sprayed direct, hydrocarbons having boiling points higher than 150C, e.g. tetrahydronaphthalene or alkylated naphthalenes, or organic liquids having boiling points higher than 150C and having one or more than one functional group, e.g. the keto group, the ether group, the ester or the amide group, this group or these groups being attached as substituent(s) to a hydrocarbon chain or being a component of a heterocyclic ring, may be used as spray liquids.  
  Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents, e.g. polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent.  
  Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e.g. kieselguhr, talc, clay or fertilizers.  
  The following experiments demonstrate the biological action of the new compounds.  
 EXAMPLE 6 In a greenhouse, loamy sandy soil was filled into pots and sown with Zea mays, Gossypium hirsutum, Soja hispida, Poa trivialis, Lolium multiflorum, Echinochloa crus-galli, Digitaria sanguinalis and Setaria spec.  
  The soil was then treated with 3 kg per hectare of each of the following active ingredients, each amount being dispersed in 500 liters of water per hectare:  
 trifluoromethylaniline trifluoromethylaniline IV N,N-bis-[B-&#39;y-(chloroacetoxy)-ethyl]-2,6-dinitro- 4-trifluoromethylaniline and, for comparison,  
 V 4-trifluoromethyl-2,6-dinitro-N,N-dipropylaniline.  
  After 3 weeks, I, II, III and IV had, compared with V, superior compatibility with the crop plants combined with a good herbicidal action.  
 Active ingredient I II III IV V Crop plants Zea mays 0 0 O 0 35 G0ss \&#39;pium hirsurum 0 0 0 0 5 Svju lrispida O 0 O O 30 Unwanted plants Poa trii&#39;ialis 95 8O 75 95 Lolium muln&#39; lorum 90 75 7O 7O 90 Echinochloa crus-galli 90 75 75 95 Digimria sanguinalis 75 7O 7O Seturia spec. 8O 75 7O 70 80 0 no damage complete destruction EXAMPLE 7 20 parts by weight of the compound of Example 2 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02 percent by weight of the active ingredient.  
 EXAMPLE 8 parts by weight of the compound of Example 3 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid ob,  
 EXAMPLE 9 3 parts by weight of the compound of Example 4 is intimately mixed with 97 parts by weight of particulate kaolinv A dust is obtained containing 3 percent by weight of the active ingredient.  
 We claim:  
 1. A substituted dinitroaniline of the formula NO 3&#39; R g/R 2 \Ru R where one of the radicals R and R denotes nitro and the other denotes methyl, trifluoromethyl or methylsulfonyl, R denotes acyloxyethyl or 2-acyloxypropyl wherein the acyl group is acetyl, propionyl, chloroacetyl, dichloroacetyl, trichloroacetyl, a-chloropropionyl, or B-chloropropionyl, and R has the same meanings as R&#34; and may additionally denote hydrogen, bromoethyl, alkylthioalkyl having up to 4 carbon atoms, linear or branched alkyl having up to 4 carbon atoms, linear or branched alkenyl having up to 4 carbon atoms, linear or branched alkynyl having up to 4 carbon atoms, hydroxyethyl, Z-hydroxypropyl, alkoxyalkyl wherein the alkyl groups are lower alkyl, or chloroethyl.  
  2. 4-trifluoromethyl-2,6-dinitro-N-n-propyl-N-B- chloroacetoxyethylaniline.  
  3. 4-trifluoromethyl-2,6-dinitro-N,N-bis-(,B- chloroacetoxyethyl)-aniline.  
  4. A substituted dinitroaniline as claimed in claim 1 wherein the acyl group R denotes acetyl or propionyl.  
  5. A substituted dinitroaniline as claimed in claim 1 wherein the acyl group of R denotes chloroacetyl, dichloroacetyl, trichloroacetyl, or chloropropionyl.  
  6. A substituted dinitroaniline as claimed in claim 1 wherein the acyl group of R denotes acetyl or propionyl, and R denotes hydrogen, linear or branched alkyl having up to four carbon atoms, or allyl.  
  7. A substituted dinitroaniline as claimed in claim 1 wherein the acyl group of R denotes chloroacetyl, dichloroacetyl, trichloroacetyl, or chloropropionyl, and R denotes hydrogen, linear or branched alkyl having up to four carbon atoms, allyl, said alkylthioalkyl group, said alkoxyalkyl group, acetoxyethyl or chloroacetoxyethyl.