DE2828265A1 - Improving tolerance to anilide herbicides of crop plants - by treating with amide to as to improve selectivity of the herbicide - Google Patents

Abstract

Tolerance of crops towards herbicidal anilides is improved by treatment with an amide of formula R1CONR2R3 (I). In (I), R1 is H, halo, alkyl (opt. substd. by halo, cycloalkyl, CN, (thio)cyanato, alkylthio, OH, alkoxysulphonyl or phenyl), alkenyl (opt. halo substd.), carbalkoxy, N-alkenylcarbamyl or N-alkyl-N-alkynylcarbamyl (both opt. as substitis. on alkyl or alkoxyalkyl), alkynyloxy, haloalkoxy, alkenylminoalkyl, alkylcarbonylalkyl, alkenylaminosulphonylalkyl, haloalkylcarbonyloxyalkyl, alkoxycarbonylalkyl, haloalkenyl-carbonyloxyalkyl, hydroxyhaloalkoxyalkyl, hydroxyalkylcarbonylalkoxyalkyl, furyl, thienyl, alkyldithiolenyl, thienalkyl, phenyl (opt. substd. by halo, alkyl, haloalkyl, alkoxy, CONH2, NO2, COOH (or salts) and/or haloalkylcarbamyl), phenyl-haloalkyl, phenyl-alkenyl (opt. substd. by halo, alkyl and/or alkoxy), halophenoxy, phenylalkoxy, phenylalkylcarboxyalkyl, phenylcycloalkyl, halophenylalkenoxy, halothiophenylalkyl, halophenoxyalkyl, bicycloalkyl, alkenyl- or alkynyl-carbamylpyridyl, dialkenylcarbamyl or alkynylcarbamyl-bicycloalkenyl. R2 and R3 are H, alkyl (opt. substd. by halo, CN, OH, alkylcarboxy, alkoxycarboxy, alkoxycarbonyl, alkoxy, mercapto, alkylsulphonyl and/or alkylamino), opt. halo substd. alkenyl, alkynyl, thioalkylcarboxyalkyl, alkylcarbamyloxyalkyl, NH2, HCO, haloalkyl-amido or -amido-alkyl (opt. N-alkyl substd.), haloalkylamidoalkenyl, alkylimino, cycloalkyl, alkylcycloalkyl, alkoxycarbonylalkenyl haloalkylcarbonyl, alkylcarbonyl, alkenyl- or cycloalkyl-carbamyloxyalkyl, alkoxy- or haloalkoxy- carbonyl, halophenylcarbamoyloxyalkyl, cycloalkenyl, phenyl or phenyl-sulphonyl (opt. substd. by alkyl, halo, haloalkyl, alkoxy, haloalkylamido, phthalamido, OH, alkyl- or alkenyl-carbamyloxy, alkylamido or alkylcarbonylalkenyl), phenyl-alkyl (opt. substd. by halo, alkyl, dioxyalkylene or halophenoxyalkylamidoalkyl). alkylthiodiazolyl, piperidylalkyl, thiazolyl or pyridyl (both opt. alkyl substd.) benzothiazolyl (opt. halo substd.), furylalkyl, alkyloxazolyl, tetra-hydrofurylalkyl, 3-cyano- or 4-,5-polyalkylene- thienyl, -haloalkylacetamidophenylalkyl (opt. ring substd. by NO2 or haloe or cyanoalkenyl; R2 is not H or halophenyl if R3 is H. Alternatively R2 + R3 complete piperidinyl (opt. substd. by 1 alkyl or by methylcyclohexyl; or with one CH2 replaced by CO), alkyltetrahydropyridyl, morpholino (opt. alkyl substd.) azabicyclononyl, benzoalkylpyrrolidinyl, oxazolidyl (opt. alkyl substd.), alkylaminoalkenyl, or perhydroquinolyl, 1,2,3,4-tetrahydroquinolyl, 1,2,3,4-tetra -hydroindolyl or perhydroindolyl (all opt. substd. by 1 alkyl.). (I) improves the selectivity of the herbicides e.g. in crops of maize, soya, cotton, sugar beet, cereals, rice and sugar cane.

Description

Use of amides to improve the crop

Zen compatibility of herbicidally active acetanilides The present Invention relates to the use of known amides as antagonists for improvement the crop plant tolerance of certain herbicidally active acetanilides. Furthermore, the present invention relates to new combinations of active ingredients, which are known from Amides and certain acetanilides exist and are particularly good selective herbicides Possess properties.

Under "antidotes" ("safener", antidote) are in the present context Understand substances that are capable of causing harmful effects from herbicides to specifically antagonize crops, i.e. to protect the crops, without noticeably influencing the herbicidal effect on the weeds to be controlled.

It is known that numerous herbicidally active acetanilides in Use for weed control in maize and other crops more or less strong Cause damage to the crops.

It is also known that numerous amides are suitable for preventing damage to reduce by herbicidal active ingredients, in particular thiol carbamates, on crop plants (cf. DE-OS 22 18 097). The applicability of these substances as an antidote is however to a certain extent depending on the respective herbicidal active ingredient.

It has now been found that the known amides of the formula in which R1 represents hydrogen, halogen, optionally alkyl substituted by halogen, cycloalkyl, cyano, cyanato, thiocyanato, alkylthio, cycloalkyl, hydroxy, alkoxysulfonyl or phenyl, furthermore alkyl optionally substituted by halogen, for carbalkoxy, N-alkenylcarbamylalkyl, N- Alkenylcarbamyl, N-alkyl-N-alkynylcarbamyl, N-alkyl-N-alkynylcarbamylalkyl, N-alkenylcarbamyl-alkoxyalkyl, N-alkyl-N-alkynylcarbamylalkoxyalkyl, alkynoxy, haloalkoxyl alkenylaminoalkyl, alkylcarbonylalkyl, alkenyl- aminosulfonyalkyl, halokenyl-aminosulfonyalkyl, haloalkyloxyalkyl, alkyloxycarbylalkyl, halokenyl-aminosulfonyalkyl, haloalkyloxyalkyl, alkyloxycarbylalkyl, halo-alkenylcarbamylcarbamylalkyl, halo-alkenylcarbamylalkyl, halokenyl-aminosulfony-alkyl , Hydroxy-haloalkyloxyalkyl, hydroxyalkylcarbonylalkoxyalkyl, furyl, thienyl, alkyldithiolenyl, thienalkyl, optionally phenyl substituted by halogen, alkyl, haloalkyl, alkoxy, carbamyl, nitro, carboxylic acid radicals and their salts and / or haloalkylcarbamyl, for phenylhaloalkyl, optionally substituted by halogen, alkyl and / or alkoxy substituted phenylalkeny l, also for halophenoxy, phenylalkoxy, phenylalkylcarboxyalkyl, phenylcycloalkyl, halophenylalkenoxy, halothiophenylalkyl, halophenoxyalkyl, bicycloalkyl, alkenylcarbamylpyridinyl, alkynylcarbamylpyridinyl, dialkenylcarbamylpyridinyl, dialkenylcarbamylpyridinyl, dialkenylcarbamylpyridinyl, dialkenylcarbamylbicycloamyl, or, optionally, are, and R 2 are different, and R 2 and R 2 are the same, and R 2 and R 2 are identical and R 2 and R 3 and R 2 are optionally hydrogen and R 2 cycloalkenyl or hydrogen , Hydroxy, alkylcarboxy, alkoxycarboxy, alkoxycarbonyl, alkoxy, mercapto, alkylsulfonyl and / or alkylamino-substituted alkyl, furthermore for optionally halogen-substituted alkenyl, alkynyl, thioalkylcarboxyalkyl, alkylcarbamyloxyalkyl, amino, formyl, haloalkyl-N-alkylamido, haloalkylamido, haloalkylamidoalkyl Haloalkyl-N-alkylamidoalkyl, haloalkylamidoalkenyl, alkylimino, cycloalkyl, alkylcycloalkyl, alkoxycarbonylalkenyl, haloalkylcarbonyl, alkylcarbonyl, alkenylcarbamyloxyalkyl, cycloalkylcarbamyloxyalkyl, alkoxycarbonyl, haloalkoxycarbonyl, halophe nylcarbamyloxyalkyl, cycloalkenyl, optionally substituted by alkyl, halogen, haloalkyl, alkoxy, haloalkylamido, phthalamido, hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido or alkylcarbonylalkenyl substituted phenyl or phenylsulfonyl, furthermore optionally substituted by halogen, alkyl, haloalkyl, alkyl, phenyliazoalkyl or halophenoxyalkylamido alkyl, phenyliazyl iodoalkyl or halophenoxyalkylamidoalkyl Piperidylalkyl, thiazolyl, alkylthiazolyl, benzothiazolyl, Halogenbenzothiazolyl, furylalkyl, pyridyl, alkylpyridyl, alkyloxazolyl, Tetrahydrofurylalkyl, 3-cyano-thienyl, 4,5-Polyalkylenthienyl, α-Halogenalkylacetamidophenylalkyl, α-Halogenalkylacetamido-nitrophenylalkyl, OC -Halogenalkylacetamido-halogenphenylalkyl or cyanoalkenyl are, where R2 is not hydrogen or halophenyl when R3 is hydrogen, and in addition R2 and R3 together with the adjacent nitrogen atom represent optionally one or more times through alkyl, in particular methyl and / or ethyl, or piperidinyl substituted by methylcyclohexyl, it being possible for one CH2 group of the piperidinyl residue to be replaced by a C = O group, furthermore for alkyltetrahydropyridyl, morpholinyl, alkylmorpholinyl, azabicyclononyl, benzoalkylpyrrolidinyl, oxazinoidyl, alkylamazolidyl, alkyloxazolidyl Perhydroquinolyl, optionally substituted one or more times by alkyl, in particular methyl, optionally one or more times substituted by alkyl, in particular methyl, 1,2,3,4-tetrahydroquinolyl, optionally substituted one or more times by alkyl, in particular methyl, 1 , 2,3,4-tetrahydroindolyl or perhydroindolyl optionally substituted one or more times by alkyl, in particular methyl, are eminently suitable as antidotes for improving the crop plant tolerance of herbicidally active acetanilides of the formula in which R stands for an optionally substituted N-containing heterocyclic radical, X and Y are identical or different and stand for alkyl, Z stands for halogen and n stands for 0, 1 or 2, as well as their herbicidally effective acid addition salts and metal salt complexes, - or the formula in which R4 is alkyl, halogen, haloalkyl, alkylthio, alkylsulfonyl, aminosulfonyl, cyano or nitro, R5 and R6 are identical or different and are hydrogen, alkyl, halogen, haloalkyl or optionally substituted phenyl, R7 is alkyl or optionally substituted phenyl stands and m stands for integers from 0 to 5, - or the formula in which A is oxygen, sulfur or the grouping NR13 NR13, R10 is hydrogen or alkyl, R11 is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, halogen, optionally substituted aryl and aralkyl or the groupings -OR14r -SR14 and NR13R14 R13 stands for hydrogen, alkyl or optionally substituted aryl, R14 stands for hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl or optionally substituted aralkyl, R8 stands for alkyl, R9 stands for alkyl or halogen, R12 stands for halogen and p stands for the numbers 0, 1 or 2.

It was also found that the new active ingredient combinations - an amide of the formula (I) and - at least one acetanilide of Formula (II), (III) or (IV) or an acid addition salt or metal salt complex an active ingredient of the formula II are excellently suited for selective weed control in crops of useful plants.

Surprisingly, the crop plants are tolerated by herbicides Active ingredients of the formulas (II), (III) and (IV) or of acid addition salts or Metal salt complexes of active ingredients of the formula (II) through the use of amides of formula (I) significantly improved. It is also unexpected that the invention Active ingredient combinations of an amide of the formula (1) and an acetanilide of the formula (II), (III) or (IV) or an acid addition salt or metal salt complex of a Active ingredient of the formula (II) have better selective herbicidal properties than the active ingredients in question alone.

The amides of the formula (I) which can be used according to the invention are already known (cf. DE-OS 22 18 097). They can be made by taking amines of the formula in which R2 and R3 have the meaning given above, with acyl chlorides of the formula in which R has the meaning given above, optionally in the presence of an acid binder such as triethylamine, dimethylbenzylamine or pyridine, and optionally in the presence of a diluent such as methylene chloride or acetonitrile, at temperatures between OOC and 600C. In this reaction, amine used in excess can also function as an acid binder at the same time. In this case there is no need to add an additional acid binding agent.

The practical preparation of amides of the formula (I) which can be used according to the invention can be seen from the following examples: Example 1 A solution of 50.8 g (0.4 mol) of 2-methyl-5-ethylpiperidine in 200 ml of acetonitrile is mixed with 29.6 g (0.2 mol) of dichloroacetyl chloride at room temperature while stirring. The mixture is then stirred at 40 ° C. for a further 2 hours. It is then allowed to cool and the reaction mixture is poured into water. The resulting mixture is extracted several times with methylene chloride. The combined organic phases are washed successively with dilute hydrochloric acid and water, dried over Na 2 SO 4 and concentrated under reduced pressure. The remaining residue is fractionally distilled.

In this way, 26 g of N-dichloroacetyl-2-methyl-5-ethyl-piperidine are obtained.

Boiling point: 1200 ° C. at 1 mm Hg The compounds listed by formula in Table t below are prepared in an analogous manner: Table 1 Example R1 R2 | R3 Sch'elzp. No. Siede-nkt Breduuosindex 2 -CHCl2 C n DO = 1D5931 3 CHCl2 DÜCH? P. 155-1560C 3 4 CHCl2 n2D0 = 1.5320 5 CHCl2 ¼ CH X m.p. 950C 6 CHCl2 3 Afp. 800C CH 7 CHCl2 C n DO = 1.5250 8 CHCl2 H3C ~ W n ° = 1.5231 9 CHC12 H n2D = 1.5247 10 CHCl2 H3 3 n D = 1.5226 3 D 11 CHCl2 H3c H3 bp. 1o60C at 2 Itkfl ~,,.

Table 1 (continued) Example- R1 R2 R3 Sctmelzp. No boiling point Refractive index Bp. 1120C at 12 CHCl2 C 2H 5 2 2mn Hg 13 CHCl2 H3C4CH3 n D = 1.5218 2 1 nD = H3 14 CHCl2 a b.p. 700C at 1 mrrn H3 CH3 Hg 15 CHCl2 l% H2 24 n D = 1.5222 According to the method described in Example 1, the compounds listed in the following Table 2 in terms of formulas are also prepared.

Table 2 Example no. R1 R² R³ 16 -CH (CH3) Br -CH2-CH = CH2 -CH2-CH = CH2 17 -C (CH3) Br -CH2-CH = CH2 -CH2-CH = CH2 18-CCl2-CH3 -CH2-CH = CH2 -CH2-CH = CH2 19-CCl = CCl2 -CH2-CH = CH2 -CH2-CH = CH2 20 -CF2-C2F5 -CH2-CH = CH2 -CH2-CH = CH2 21 -CHCl2 -CH2-CH = CH2 -CH2-CH = CH2 22 -CH2Cl -CH2-CH = CH2 -CH2-CH = CH2 23 -CHCl2 -CH2-CH # N -CH2-CH # N 24 -CHCl2 -CH2-CH = CH2 H 25 -CHCl2 -C3H7 -C3H7 26 -CHCl2 -C (CH3) 2-C # CH H 27 -CH2Cl -C (CH3) 2-C # CH H 28 -CCl3 -CH2-CH = CH2 H Table 2 (continued) Example no. R1 R² R³ 29 -CCl3 -CH2-CH = CH2 -CH2-CH = CH2 30 -CH2Cl -C (CH3) 2-C # CH CH3 31 -CHCl2 -C (CH3) 2-C # CH CH3 32-CCl3 -C (CH3) 2-C # CH CH3 33 -CHCl2 -CH3 -CH (CH3) -C # CH 34 -CHCl2 -CH2-CH = CH2 # 35 -CH2Cl H -CH2- # O 36 -CHCl2 H -CH2- # O C2H5 N 27 -CH2Cl H - # Table 2 (continued) Example no. R1 R² R³ C2H5 N 38 -CHCl2 H - # S. 39 -CHCl2 H - # N S. 40 -CHCl2 H - # N-CH3 S-CH3 41 -CHCl2 H - # NN N 42 -CHCl2 H - ## S. S Br 43 -CHCl2 H - ## N Table 2 (continued) Example no. R1 R² R³ O 44 -CO-C2H5 -CH3 -CH (CH3) C # CH O 45 -CO-C2H5 -CH2-CH = CH2 -CH2-CH = CH2 46 -CH2-CH (CH3) -CH2-t- C4H9 H -C (CH3) 2 -C # CH47 -C (CH3) 2 = C3H7 -CH2-CH = CH2 -CH2-CH = CH2 48 -CH2-t -C4H9 -CH3 -CH (CH3) 2-C #CH 49 -CH2-t -C4H9 H -C (CH3) 2-C # N 50 -CH (CH3) -C3H7 -CH2-CH = CH2 -CH2-CH = CH2 51 -CH (CH3) -C3H7 -CH3 -CH (CH3) -C # CH 52 -CH (CH3) -C3H7 H -C (CH3) 2-C # CH 53 i-C3H7 -CH3 -CH (CH3) C # CH Table 2 (continued) Example no . R1 R² R³ 54 -C13H27 CH2-CH = CH2 -CH2CH = CH2 55 -C11H23 CH2-CH = CH2 -CH2CH = CH2 56 -C11H23 H -C (CH3) -C # CH 57 -C9H19 -CH2-CH = CH2 - CH2-CH = CH2 58 -C9H19 H -C (CH3) 2-C # CH 59 -C6H13 -CH2-CH = CH2 -CH2-CH = CH3 60 -C6H13 -CH3 -CH (CH3) 2-C # CH 61 -C6H13 H -C (CH3) 2-C # CH 62 -C4H9 H -C (CH3) 2-C # CH 63 -C3H7 -CH2-CH = CH2 -CH2-CH = CH2 64 -C3H7 -CH3 -CH ( CH3) -C # CH 65 -C3H7 H -C (CH3) 2-C # OH 66 -CH3 -CH2-CH = CH2 -CH2-CH = CH2 Table 2 (continued) Example no. R1 R² R³ 67 -CH3 H -C (CH3) 2-C # CH 68 -C (CH3) = CH2 H -C (CH3) 2-C # CH 69 -CH = CH-CH3 -CH2-CH = CH2 -CH2-CH = CH2 70 -CH = CH-CH3 H -C (CH3) 2-C # CH 71 -CH = C (CH3) 2 -CH3 -CH (CH3) -C # CH 72-CH = C (CH3) 2 H -C (CH3) 2-C # CH 73 -CH = CH-CH = CH-CH3 -CH2-CH = CH2 -CH2-CH = CH2 74 -CH = CH-CH = CH-CH3 HC (CH3) 2C # CH CH2 75 -CH # -CH2-CH = CH2 -CH2-CH = CH2 CH2 CH2 76 -CH # -CH3 -CH (CH3) -C # CH CH2 Table 2 (continued) Example no. R1 CH2 77 -CH # H -C (CH3) 2-C # CH CH2 78 - # H # -CH2-CH = CH2 -CH2-CH = CH2 79 - # H # -CH3 -CH (CH3) -C # CH 80 - # H # H -C (CH3) 2-C # CH 81 -CH2-CH2- # H # -CH2-CH = CH2 -CH2-CH = CH2 82 -CH2-CH2- # H # -CH3 -CH (CH3) -C # CH Table 2 (continued) Example no. R1 R2 R3 83 - # -CH2-CH = CH2 -CH2-CH = CH2 84 - # -CH3 -CH (CH3) -C # CH 85 - # H -C (CH3) 2-C # CH 86 - # - F -CH2-CH = CH2 -CH2-CH = CH2 87 -CH = CH2 -CH3 -C (CH3) 2-C # CH 88 -CH = CH2 H -C (CH3) 2-C # CH 89 -CH2 # H # -CH2-CH = CH2 -CH2-CH = CH2 Table 2 (continued) Example no. R1 R2 R3 90 -CH2- # H # -CH3 -CH (CH3) -C # CH 91 -CH2- # H # H -C (CH3) 2-C # CH 92 - # -CH2-CH = CH2 -CH2-CH = CH2 CF3 93 - # -CH3 -CH (CH3) -C # CH CF3 94 - # -CH3 -CH (CH3) -C # CH I. 95 - # -CH3 -C (CH3) 2-C # CH I. Table 2 (continued) Example no. R1 R2 R3 96 -CBr -CH2-CH = CH2 -CH2-CH = CH2 97 -CBr -CH3 -CH (CH3) -C # CH 98 -CBr H -C (CH3) 2-C # CH 99 -CBr H -C (CH3) 2-C # CH 100 -CBr H -CH2-CH # CH2 101-CCl = CHCl -CH3 -CH (CH3) C # CH 102 - (CH2) 4-CH2-Br -CH2CH = CH2 -CH2CH = CH2 103 - (CH2) 4-CH2-Br-CH3 -CH2 (CH3) -C # CH 104 - # -CH2-CH = CH2 -CH2-CH = CH2 Cl 105 - # -CH3 -CH (CH3) -C # CH Cl Table 2 (continued) Example no. R1 R2 R3 106 - # -CH3 -CH (CH3) -C # CH Cl 107 - # - Cl -CH2-CH = CH2 -CH2CH = CH2 108 - # - Cl -CH3 -CH (CH3) -C # CH 109 - # - Cl H -C (CH3) 2-C # CH 110 - # - O-CH3 -CH2-CH = CH2 -CH2-CH = CH2 111 - # - O-CH3 -CH3 -CH (CH3) -C # CH 112 - # -CH3 -CH (CH3) -C # CH O CH3 Table 2 (continued) Example no. R1 R2 R3 113 - # H -C (CH3) 2-C # CH O CH3 OCH3 114 - # - OCH3 -CH3 -CH (CH3) -C # CH OCH3 OCH3 115 - # - OCH3 H -C (CH3) 2-C # CH OCH3 116 - # -CH3 -CH (CH3) -C # CH CH3 117 - # H -C (CH3) 2-C # CH CH3 Table 2 (continued) Example no. R1 R2 R3 118 - # -CH2-CH = CH2 -CH2-CH = CH2 CH3 119 - # -CH3 -CH (CH3) -C = CH CH3 120 - # - CH3 -CH2-CH = CH2 -CH2-CH = CH2 121 - # - CH3 -CH3 -CH (CH3) -C # CH 122 - # - CH3 H -C (CH3) 2 -C # CH 123 - # - Cl -CH3 -CH (CH3) -C # CH Cl Table 2 (continued) Example no. R1 R2 R3 124 - # - Cl H -C (CH3) 2-C # CH Cl 125 - # - Cl -CH3 -CH (CH3) -C # CH Cl 126 - # -CH2-CH = CH2 -CH2-CH = CH2 Br 127 - # -CH3 -CH (CH3) -C # CH Br 128 - # -CH2-CH = CH2 -CH2-CH = CH2 O 129 - # H -C (CH3) 2-C # CH O 130 - # -CH2-CH = CH2 -CH2-CH = CH2 S. Table 2 (continued) Example no. R1 R² R³ 131 - # H -C (CH3) 2-C # CH S. 132 -CHCl2 -C2H4OH -C2H4OH OO 133 -CHCl2 -CH2-CH2-OC-CHCl2 -CH2-CH2-OC-CHCl2 134 -CHCl2 -CH2-CH2-O-SO2-CH3 -CH2-CH-O-SO2-CH3 135 - # -CH3 -CH (CH3) -C # CH O 136 - # -CH3 -CH (CH3) -C # CH S. 137 -CHBr-CH3 -CH3 -CH (CH3) -C # CH 138 -CHBr-CH3 H -CH (CH3) -C # CH Table 2 (continued) Example no. R1 R² R³ 139 -CH2-CH2Cl -CH2-CH = CH2 -CH2-CH = CH2 140 -CH2-CH2Cl -CH3 -CH (CH3) -C # CH 141 -CH2-CH2Cl H -C (CH3) 2-C # CH 142 -CBr (CH3) 2 H -C (CH3) 2-C # CH 143 -CH2I -CH2-CH = CH2 -CH2-CH = CH2 144 -CH2I -CH3 -CH2 (CH3) -C # CH 145 -CH2I H -C (CH3) 2-C # CH 146 -CHCl2 -CH2-CH2Cl -CH2-CH2Cl OO 147 -CH2Cl2 -CH2-CH2-OC-NH-CH3 -CH2-CH2-OC-NH-CH3 OO 148 -CH2Cl2 -CH2-CH2-OCO-CH3 -CH2-CH2-OCO-CH3 Table 2 (continued) Example no. R1 R² R³ OO 149 -CHCl2 -CH2-CH2-OC-C2H5 -CH2-CH2-OC-C2H5 OO 150 -CHCl2 -CH2-CH2-OCS-C2H5 -CH2-CH2-OCS-C2H5 151 -CH2- # -CH2-CH = CH2 -CH2-CH = CH2 152 -CH2- # -CH3 -CH (CH3) -C # CH 153 -CH2- # H -C (CH3) 2-C # CH 154 -CH2-CH2- # -CH2-CH = CH2 -CH2-CH = CH2 155 -CH2-CH2- # -CH3 -CH (CH3) -C # CH Table 2 (continued) Example no. R1 R² R³ 156 - # -CH2-CH = CH2 -CH2-CH = CH2 157 - # -CH3 -CH (CH3) -C # CH O 158 -CH2-CN (CH2-CH = CH2) 2 -CH2-CH = CH2 -CH2-CH = CH2 O CH3 159 -CH2-CN-CH-C # CH -CH2 -CH2 (CH3) -C # CH CH3 O 160 -CH2-C-NH-C (CH3) 2C # CHH -C (CH3) 2-C # CH O 161 -CN (CH2-H = CH2) 2 -CH2-CH = CH2 -CH2-CH = CH2 162 -CN (CH3) -CH (CH3) -C # CH -CH3 -CH (CH3) -C # CH Table 2 (continued) Example no. R1 R² R³ O 163 -C-NH-C (CH3) 2-C # CH HC (CH3) 2-C # CH O 164 -CH2-CH2-CN (CH2-CH = CH2) 2 -CH2-CH = CH2 -CH2-CH = CH2 O 165 -CH2-CH2-CN (CH3) -CH (CH3) -C # CH -CH3 -CH (CH3) -C # CH O 166 - (CH2) 3-CN (CH2-CH = CH2) 2 -CH2-CH = CH2 -CH2-CH = CH2 O 167 - (CH2) 3-CN (CH3) -CH (CH3) -C # CH -CH3 -CH (CH3) -C # OH 168 - (CH2) 4-CN (CH2-CH = CH2) 2 -CH2-CH = CH2 -CH2-CH = CH2 Table 2 (continued) Example no. R1 R² R³ O 169 - (CH2) 4-CN (CH3) -CH (CH3) -C # CH -CH3 -CH (CH3) -C # CH O 170 -C (CH3) 2-CN (CH3) -CH (CH3) -C # CH -CH3 -CH (CH3) -C # CH O 171 - (CH2-C (CH3) 2-CH2-C-NH-C-CH3) 2-C # CH H -C (CH3) 2-C # CH O 172 -CH2-O-CH2-CN (CH2-CH = CH2) 2 -CH2-CH = CH2 -CH2CH = CH2 O 173 -CH2-O-CH2-CN (CH3) -CH (CH3) -C # CH -CH3 -CH (CH3) -C # CH 174 # -CH2-CH = CH2 -CH2-CH = CH2 C = O N (CH2-CH = CH2) 2 Table 2 (continued) Example no. R² R³ O 175 C # -CH3 -CH (CH3) -C # CH N (CH3) -CH (CH3) -C # CH 176 # H -C (CH3) 2-C # CH O = C N (CH3) - (CH3) 2 -C # CH 177 # -CH3 -CH (CH3) -C # CH O = C N (CH3) -CH (CH3) -C # CH 178 # -CH2CH = CH2 -CH2CH = CH2 O = C N (CH2CH = CH2) 2 Table 2 (continued) Example no. R1 R² R³ O 179 -C (CH3) 2-CN (CH2-CH = CH2) 2 -CH2-CH = CH2 -CH2-CH = CH2 O 180 -C (CH3) 2-C-NH-C (CH3) 2-C # CH H -C (CH3) 2-C # CH 181 - # -CH2-CH = CH2 -CH2-CH = CH2 NO2 182 - # H -C (CH3) 2-C # CH NO2 183 - # - NO2 -CH2-CH = CH2 -CH2-CH = CH2 184 - # - NO2 -CH3 -CH (CH3) 2-C # CH Table 2 (continued) Example no. R¹ R² R³ 185 - # - NO2 H -C (CH3) 2-C # CH 186 -CHCl- # -CH2-CH2 = CH2 -CH2-CH = CH2 187 -CHCl- # -CH3 -CH (CH3) -C # CH 188 -CHCl- # H -C (CH3) 2-C # CH # 189 -CH -CH3 -CH (CH3) -C # CH # 190 # -CH2-CH = CH2 -CH2-CH = CH2 O = C-OH Table 2 (continued) Example no. R¹ R² R³ 191 - # H -C (CH3) 2C # CH O = C-OH 192 - # H -C (CH3) 2C # CH O = C-ONa 193 - # O = CO-NH3 # C (CH3) 2-C # CH H -C (CH3) 2C'CH 194 -CHCl2 -C2H5 -C2H5 195 -CHCl2 i-C3H7 -CH2-CH = CH2 Table 2 (continued) Example no. R1 R2 R3 196 -CHCl2 -C3H7 -CH2-CH = CH2 197 -CHCl2 n-C4H9 -CH2-CH = CH2 198 -CHCl2 -CH2-CH = CH2 -CH2-CCl = CH2 199 -CHCl2 -C3H7 -CH2-CCl = CH2 200 -CHCl2 i-C4H9 -CH2-CH = CH2 201 -CHCl2 -CH2-C (CH3) = CH2 -CH2-CH = CH2 202 -CHCl2 n-C4H9 sec.-C4H9 203 -CHCl2 n-C4H9 i- C4H9 204 -CHCl2 n-C4H9 i-C3H7 205 -CHCl2 i-C4H9 i-C3H7 206 -CHCl2 i-C4H9 n-C3H7 207 -CHCl2 sec.-C4H9 n-C3H7 Table 2 (continued) Example no. R¹ R² R³ 208 -CHCl2 n -C4H9 n -C3H7 209 -CHCl2 -C2H5 i-C4H9 N # C 210 -CHCl2 H ## 211 -CHCl2 -CH3 -NH2 212 -Cl -CH2-CH = CH2 -CH2-CH = CH2 213 -CHCl2 = C [N (CH3) 2] 2 214 -CH2Cl = C [N (CH3) 2] 2 215 -O-CH2-C # C-CH3 -CH2-CH = CH2 -CH2-CH = CH2 Table 2 (continued) Example no. R¹ R² R³ 216 -O-C2H4Cl -CH2-CH = CH2 -CH2-CH = CH2 217 -O-CH2-CHCl2 -CH2-CH = CH2 -CH2-CH = CH2 218 -O - # - Cl -CH2-CH = CH2 -CH2-CH = CH2 219 -CH2-N (CH2-CH = CH2) 2 -CH2-CH = CH2 -CH2-CH = CH2 O # 221 -CHCl2 H -C (CH3) -C-CHCl2 O # 222 -CHCl2 -CH3 -N (C-CHCl2) 2 O # 223 -CH2-C-CH3 -CH2-CH = CH2 -CH2CH = CH2 Table 2 (continued) Example no. R¹ R² R³ 224 -CH2-C # N -CH2-CH = CH2 -CH2-CH = CH2 225 -CH2-OC # N -CH2-CH = CH2 -CH2-CH = CH2 O # 226 -CHCl2 -C2H5 -CH2-CH2-OC-CHCl2 227 -CHCl2 -CH2-CH2-C # N -CH2-CH-C # N 228 -CHCl2 H - # 229 -CHCl2 H - # C2H5 CH3 230 -CHCl2 H - # CH3 Table 2 (continued) Example no. R¹ R² R³ i-C3H7 231 -CHCl2 H - # i-C3H7 232 -CH2Cl H -CH2-CH (CH3) 2 CH2 233 -C = Cl2 H -CH CH2 234 -CHCl2 H i-C4H9 235 -CH2Cl H t-C4H9 236 -CHCl2 H t-C4H9 237 -CH2Cl H -CH (CH3) -CH2-CH (CH3) -CH3 Table 2 (continued) Example no. R¹ R² R³ 238 -CHCl2 H # 239 -CHCl2 H -CH2- # 240 -CHCl2 H -CH2 - # - Cl 241 -CHCl2 H -CH2 - # - Cl Cl 242 -CHCl2 H -CH2 - # - O O-CH2 243 -CH = CH- # -CH2-CH = CH2 -CH2-CH = CH2 Table 2 (continued) Example no. R¹ R² R³ 244 -CH = CH - # - CH3 -CH2-CH = CH2 -CH2-CH = CH2 245 -CH = CH - # - F -CH2-CH = CH2 -CH2-CH = CH2 Cl 246 -CH = CH - # - -CH2-CH = CH2 -CH2-CH = CH2 247 -CHCl2 - # -CH2-CH = CH2 248 -CHCl2 -t-C4H9 -CH = CH-CH2-CH3 249 -CHCl2 -C (CH3) 2-C = CH -CH = CH-CH2-CH3 CH2-CH3 250 -CHCl2 -C2H5 -C CH-CH3 251 -CHCl2 n -C4H9 -CH = CH-CH2-CH3 Table 2 (continued) Example no. R¹ R² R³ 252 -CHCl2 # n-C3H7 253 -ChCl2 -C (CH3) = CH-CH2-CH3 n -C3H7 254 -CH2-SO2-N (CH2-CH = CH2) -CH2-CH = CH2 -CH2-CH = CH2 255 -CH (S-C2H5) 2 -CH2-CH = CH2 -CH2-CH = CH2 256 -CHCl2 -CH3 -N = C (CH3) 2 O 257 -CH2-OC-CHCl2 -CH2-CH = CH2 -CH2-CH = CH2 258 -CH (O - # - Cl) 2 -CH2-CH = CH2 -CH2-CH = CH2 259 -CHCl2 sec-C4H9 -C2H5 Table 2 (continued) Example no. R¹ R² R³ 260 -CHCl2 t-C4H9 -C2H5 261 -CHCl2 sec-C5H11 -C2H5 262 -CHCl2 i-C3H7 -C2H5 263 -CHCl2 -CH3 # 264 -CHCl2 -C2H5 # 265 -CHCl2 n-C3H7 -CH2- # CH3 266 -CHCl2 CH3 sec-C5H11 267 -CHCl2 n-C3H7 sec-C5H11 Table 2 continued) Example no. R¹ R² R³ 268 -CHCl2 -n-C3H7 n-C5H11 269 -CHCl2 i-C4H9 sec.-C4H9 270 -CHCl2 -CH3 i-C3H7 271 -CHCl2 -CH3 -CH (CH3) -CH (CH3) -CH3 272 -CHCl2 -C2H5 # CH3 273 -CHCl2 -C2H5 # CH3 274 -CHCl2 -C2H5 # -CH3 275 -CHCl2 -CH3 sec-C4H9 Table 2 (continued) Example no. R¹ R² R³ 276 -CHCl2 -C2H5 n -C6H13 277 -CHCl2 n-C3H7 t-C4H9 278 -CHCl2 n -C3H7 -CH (CH3) -CH (CH3) ~ CH3 279 -CHCl2 n-C3H7 # 280 -CHCl2 n-C3H7 -CH2 - # - CH3 281 -CHCl2 n-C3H7 -CH2 - # - CH3 CH3 282 -CHCl2 n-C3H7 -CH2- # Cl CH3 283 -CHCl2 -C2H5 # CH3 Table 2 (continued) Example no. R¹ R² + R³ 284 -CHCl2 # -CH3 CH3 285 -CHCl2 # CH3 CH3 286 -CHCl2 # -CH3 C2H5 287 -CHCl2 # -C2H5 CH3 288 -CHCl2 # -CH (CH3) 2 Table 2 (continued) Example no. R¹ R² + R³ 289 -CHCl2 # C3H7 290 -CHCl2 # CH3 291 -CHCl2 # CH3 292 -CHCl2 # -CH3 Table 2 (continued) Example no. R¹ R² R³ 293 -CHCl2 # C2H5 293 -CHCl2 -CH3 -CH2- # Cl 294 -CHCl2 -CH3 -CH2- # Cl 295 -CHCl2 -CH3 -CH2 - # - Cl Table (continued) Example no. R¹ R² R³ CH3 297 -CHCl2 -C2H5 -CH2- # CH3 CH3 298 -CHCl2 n-C3H7 -CH2- # CH3 O # 299 -CHCl2 H -CH2-CH2-N (C2H5) -C-CHCl2 Table 2 (continued) Example no. R¹ R² R³ O # 300 -CHCl2 -C2H5 -CH2-CH2-N (C2H5) -C-CHCl2 O # 301 -CHCl2 -C3H6-NH-C-CHCl2 -C3H6-NH-C-CHCl2 O # 302 -CHCl2 - # -CH2-CO-C2H5 303 -CHCl2 -CH2-CH = CH2 - # 304 -CHCl2 -C2H5 - # 305 -CHCl2 n-C3H5 -CH2 - # - Cl Cl 306 -CHCl2 -CH2- # n-C3H7 Table 2 (continued) Example no. R¹ R² R³ 307 -CHCl2 -CH2- # n-C3H7 308 -CHCl2 n-C3H7 - # 309 -CHCl2 n -C3H7 n -C6H13 310 -CHCl2 -C2H4-O-CH3 -C2H4-O-CH3 311 -CHCl2 -C2H4-O-C2H5 -C2H4-O-C2H5 312 -CHCl2 -C2H5 -CH2- # 313 -CHCl2 n-C3H7 -CH2- # 314 -CHCl2 i-C3H7 -CH2- # Table 2 (continued) Example no. R¹ R² R³ 315 -CHCl2 n-C4H9 -CH2- # C2H5 316 -CHCl2 # C2H5 317 -CHCl2 # 318 -CHCl2 # 319 -CHCl2 -CH3 - # Table 2 (continued) Example no. R¹ R² R³ 320 -CHCl2 C2H4 # 321 -CHCl2 n-C3H7 - # 322 -CHCl2 i-C3H7 - # 323 -CHCl2 n-C4H9 - # 324 -CHCl2 sec.-C4H9 - # 325 -CHCl2 t -C4H9 -CH2-CH2OH 326 -CHCl2 -CH3 -CH2-CH2-C # N 327 -CHCl2 # Table 2 (continued) Example no. R¹ R² R³ 328 -CHCl2 n -C6H13 n -C6H13 329 -CHCl2 -CH3 -CH2-CH2OH CH3 330 -CHCl2 #O CH3 331 -CHCl2 -CH2-CH2-SH -CH2- # 332 -CHCl2 H -C (C2H5) 2-C = N 333 -CHCl2 H -C (C2H5) 2-C = N 334 -CHCl2 H - # Cl 335 -CHCl2 H - # CF3 Table 2 (continued) Example no. R¹ R² R³ CH3 # 336 -CHCl2 H # -CH3 CH3 # 337 -CH2Cl H # -CH3 Cl # 338 -CHCl2 H # # Cl C2H5 # 339 -CHCl2 H # # C2H5 340 -CHCl2 H # # O-C2H5 Table 2 (continued) Example no. R¹ R² R³ CH3 # 341 -CHCl2 H - # # CH3 342 -CHCl2 H -CH2-C (CH3) = CH2 343 -CH2Cl H -CH2-C (CH3) = CH2 344 -CHCl2 H -CH2-CH2-O-CH3 345 -CHCl2 H -CH2-CH2- # 346 -CH2Cl -CH3 -CH2-C # CH 347 -CHCl2 -CH3 -CH2-C # Ch Table 2 (continued) Example No. R¹ R² R³ 348 -CHCl2 H CH2- # 349 -CHCl2 H -CH2-CH2-N (C2H5) 2 350 -CHCl2 H -CH2-CH (OCH3) 2 O # 351 -CHCl2 H -CH2-CH2-NHC-CHCl2 F. # 352 -CH = CH- # -CH2CH = CH2 -CH2-CH = CH2 O # 353 -CHCl2 H -CH (NH-C-CHCl2) - # O # 354 -CHCl2 H -CH (NH-C-CHCl2) - # Table 2 (continued) Example no. R¹ R² R³ O # 355 CHCl2 H -CH (CH = CH2) -NH-C-CHCl2 O # 356 -CHCl2 H -CH (NH-C-CH2Cl) - # O # 357 -CHCl2 H -CH (NH-C-CH2Cl) - # # NO2 O Cl # # 358 -CHCl2 H -CH (NH-C-CH2Cl) - # # Cl 359 -HH -C (CH3) 2-C # N Table 2 (continued) Example No. R¹ R² R³ 360 # H -C (CH3) 2-C # CH 361 # H -C (CH3) 2-C # N O # #CN (CH2-CH = CH2) 2 362 - # -CH2-CH = CH2 -CH2CH = CH2 #CN (CH2-CH = CH2) 2 # O Table 2 (continued) Example No. R¹ R² R³ O # # C-NH-C (CH3) 2-C # N 363 # H -C (CH3) 2C # N # C-NH-C (CH3) 2-C # N # O 364 -CH (OCH3) - # -CH2-CH = CH2 -CH2-CH = CH2 O # 365-CH (OC-CH3) - # H -C (CH3) 2-C # CH O # 366 -CH (OC-CH3) - # H -C (CH3) 2-C # N Table 2 (continued) Example No. R¹ R² R³ 367 ### - CNN (CH2-CH = CH2) 2 -CH2-CH = CH2 -CH2-CH = CH2 N 368 ### - C-NH-C (CH3) 2-C # CH -CH2-CH = CH2 -CH2-CH = CH2 N O # 369 (CH2 = CH-CH2) -NC- # -CH2-CH = CH2 -CH2-CH = CH2 O # 370 HC # CC (CH3) 2-NH-C- # H -C (CH3) 2-C # CH 371 -H- # -CH2-CH = CH2 -CH2-CH = CH2 Table 2 (continued) Example No. R¹ R² R³ 372 -H- # H -C (CH3) 2-C # CH O # 373 -CH2-CH2-CO-CH3 H -C (CH3) 2-C # CH 374 -CHCl2 H -C (CH3) 2-C # N # CH3 S- # # # 375 -CH # -CH2-CH = CH2 -CH2-CH = CH2 # # S- # # O # # 376 -CHCl2 H NH-C-CHCl2 Table 2 (continued) Example No. R¹ R² R³ O # 377 CHCl2 -C-CH3 -CH2-CH (CH3) 2 378 CHCl2 -CHO -CH2-CH (CH3) 2 379 - # H -C (CH3) 3 # Cl 380 -CH = CH- # H -C (CH3) 3 381 - ### H -C (CH3) 2-C # CH O 382 - ### CH3 -CH (CH3) -C # CH S. 383 - # - F CH3 -CH (CH3) 2-C # N Table 2 (continued) Example No. R¹ R² R³ 384 -CH2- # H -C (CH3) 2-C # N S. 385 -CH2-C (CH3) 3 H -C (CH3) 2-C # N 386 -CH (C2H5) - # H -C (CH3) 2-C # CH 387 -CH-CH - # - CH3 H -C (CH3) 2-C = CH # CH3 388 -CH-CH- # H -C (CH3) 2-C = CH # CH3 389 -CH-CH- # H -C (CH3) 2-C = N Table 2 (continued) Example No. R¹ R² R³ 390 -CH-CH- # -CH3 -CH (CH3) -C # CH 391 -CH-CH-O - # - Cl H -C (CH3) 2-C # CH 392 -C (CH3) = CH- # H -C (CH3) 2-C # N C2H5 # 393 HH # C2H5 # 394 -CH2-OC-CCl = CCl-CCl = CCl -CH2-CH2 = CH2 -CH2-CH2 = CH2 395 -CHCl2 # O Table 2 (continued) Example No. R¹ R² R³ O Cl # # 396 -CH2Cl H -CH2-NH-C-CH2-O - # - Cl O # 397 -CCl3 H -CH2-NH-C-CH2Cl #OH 398 -CHCl2 H - # O # # OC-NH-C2H5 399 -CHCl2 H - # O # # OC-NH-CH2-CH = CH2 400 -CHCl2 H - # O # 401 -CHCl2 H -CO-C2H5 Table 2 (continued) Example No. R¹ R² R³ O # 402 -CHCl2 H -CO-C2H4Cl 403 CH3 H -C (CF3) 2-OH O # # NH-C-CHCl2 404 -CHCl2 H - # O # # NH-C-C2H5 405 -CHCl2 H - # 406 -CH2-OC (CHCl2) 2-OH -CH2-CH = CH2 -CH2-CH = CH2 407 -CH2-OC (CHCl2) (CCl3) -OH -CH2-CH = CH2 -CH2-CH = CH2 Table 2 (continued) Example No. R¹ R² R³ Cl O # # 408 -CH2Cl H -OH (#) - NH-C-CH2-Cl # Cl Cl # # CH = CH-CC (CH3) 3 409 -C - # - Cl H - # # O O # # CH = CH-CC (CH3) 3 410 -C - # - Cl H - # # Cl O Cl # # 411 -C (CO-CH3) = C (CH3) -OH H - # # Cl 413 -CH2Cl -CH3 -CH2-CH2 = C # N Table 2 (continued) Example No. R¹ R² R³ 414 -CH2Cl n -C6H13 n -C6H13 415 -CH2Cl -C2H5 - # 416 -CH2Cl n-C3H7 -CH2- # 417 -CH2Cl i-C3H7 -CH2- # 418 -CH2Cl -CH3 -CH2- # # Cl 419 -CH2Cl -CH3 -CH2 - # - Cl CH3 # 420 -CH2Cl -C2H5 -CH2- # # CH3 Table 2 (continued) Example No. R¹ R² R³ 421 -CH2Cl n-C3H7 - # 422 -CH2Cl # # C2H5 # 423 -CH2Cl # # C2H5 424 -CH2Cl # # CH3 425 -CH2Cl -CH3 i-C3H7 426 -CH2Cl -CH3 -CH (CH3) -CH (CH3) -CH3 Table 2 (continued) Example No. R¹ R² R³ 427 -CH2Cl -C2H5 - # - CH3 428 -CH2Cl n -C3H7 i-C4H9 429 -CH2Cl n -C3H7 sec -C5H11 430 -CH2Cl n -C3H7 t -C4H9 431 -CH2Cl i-C4H9 sec-C4H9 432 -CH2Cl -C2H5 sec -C4H9 433 -CH2Cl i-C4H9 i-C3H7 434 -CH2Cl n -C4H9 i-C3H7 435 -CH2Cl n -C4H9 i-C4H9 436 -CH2Cl -CH2-CH2-O-CH3 -CH2-CH2-O-CH3 Table 2 (continued) Example No. R¹ R² R³ 437 CH2Cl -CH2CH2-O-C2H5 -CH2-CH2-O-C2H5 438 CH2Cl -CH2 - ## -n-C3H7 O 439 CH2Cl -CH2 - ## -n-C3H7 O 440 CH2Cl -n-C3H7 -CH2 - # - Cl # Cl 441 CH2Cl -n-C3H7 -CH2 - # - Cl # Cl 442 CH2Cl -n-C3H7 - # Table 2 (continued) Example No. R¹ R² R³ 443 CH2Cl -C2H5 -CH2- # # Cl 444 CH2Cl -C2H5 -CH2 - # - CH3 # CH3 445 CH2Cl n-C3H5 -CH2- # # CH3 446 CH2Cl -C2H5 -CH2 - # - CH3 447 CH2Cl -CH3 -CH2- # # CH3 Table 2 (continued) Example No. R¹ R² R³ 448 -CHCl2 -CH3 -CH2- # # CH3 449 -CHCl2 -C2H5 -CH2 - # - CH2 450 -CHCl2 -n-C3H7 -CH2- # # CH3 451 -CHCl2 -C2H5 -CH2 - # - CH3 # CH3 452 -CHCl2 -C2H5 -CH2- # # Cl 453 -CHCl2 -CH3 n -C4H9 Table 2 (continuation) Example No. R¹ R² R³ 454 -CH2Cl -CH3 n-C4H9 455 -CHCl2 -CH3 sec-C4H9 456 -CH2Cl -CH3 sec-C4H9 457 -CHCl2 -CH3 n-C3H7 458 -CH2Cl -CH3 n- C3H7 459 -CHCl2 -n-C4H9 t-C4H9 460 -CHCl2 i-C3H7 sec-C4H9 461 -CH2Cl i-C3H7 sec-C4H9 462 -CHCl2 i-C3H7 n-C5H11 463 -CH2Cl i-C3H7 n-C5H11 464 -CHCl2 i-C3H7 sec-C5H11 Table 2 (continued) Example No R¹ R² R³ 465 -CHCl2 HN 466 -CHCl2 HN 467 -CHCl2 H CH3 N 468 -CHCl2 HO 469 -CHCl2 HO = C NH O = C Table 2 (continued) Example No. R¹ R² R³ 470 -CHCl2 -CH2-O-CH3 C2H5 C2H5 O 471 -CHCl2 H -C (CH3) -CH-CO-C2H5 O 472 -CHCl2 H -NH-C-CHCl2 Cl 473 -CHCl2 -CHO Cl O 474 -CHCl2 -CH2CH (CH3) 2 -C-CHCl2 475 -CHCl2 H - (CH2) 3-O-CH (CH3) 2 Table 2 (continued) Example No. R¹ R² R³ Cl 476 -CHCl2 H -CH2- Cl 477 -CHCl2 H -C (C2H5) (CH3) 2 478 -CHCl2 H -CH (CH3) - 479 -CH2Cl H -C (C2H5) (CH3) 2 480 -CH2Cl H -C2H4-O-CH3 481 -CH2Cl H -CH2-CH (OCH3) 2 482 -CH-CHH-C (CH3) 2-CN F. Table 2 (continued) Example No. R¹ R² R³ O 483 -NH-C-CH2Cl H -C (CH3) 2-C-CH OO 484 -CHCl2 -CH2-CH2-OCN (CH3) 2 -CH2-CH2-OCN (CH3) 2 O 485 -CHCl2 -CH2-CH2-OC-NH-CH2-CH-CH2 -CH2-CH2-OC-NH-CH2-CH-CH2 OO 486 -CHCl2 -CH2-CH2-OC-NH-CH2-CH-CH2 -CH2-CH2-OC-NH-CH2-CH-CH2 OO 487 -CHCl2 -CH2-CH2-OC-NH-i-C3H7 -CH2-CH2-OC-NH-i-C3-H7 OO 488 -CHCl2 -CH2-CH2-OC-NH-C4H9 -CH2-CH2-OC.NH-C4H9 OO 489 -CH2Cl -CH2-CH2-OC-NH-CH3 -CH2-CH2-OC-NH-CH3 OO 490 -CH2Cl -CH2-CH2-OC-NH-CH2-CH-CH2 -CH2-CH2-OC-NH-CH2-CH-CH2 Table 2 (continued) Example No. R¹ R² R³ OO 491 -CH2Cl -CH2-CH-OC-NH-H-CH2-CH2-OC-NH-H OO 492 -CH2Cl -CH2-CH2-OC-NH- Cl -CH2-CH2-OC-NH- Cl Cl Cl 493 -CHCl2 H -CH2-CH2-OH 494 -CH2Cl -CH2-CH2-OH -CH2-CH2-OH 495 -CHCl2 H -CH2-CH (OH) (CH3) 496 -CHCl2 H - (CH2) 3-OH 497 -CHCl2 -CH2-CH (OH) (CH3) -CH2-CH (OH) (CH3) O 498 -CHCl2 CH3 CH3 Table 2 (continued) Example No. R¹ R² R³ 499 -CH2OH -C2H5 -C2H5 500 -CH3 -SO2 501 -CH2-S- -Cl H -CH2-CH (CH3) 2 502 -CH2-SO2-O-CH3 -C2H5 -C2H5 503 -C3H6Br H -SO2Cl 504 -CHCl2 CH3 CH3 505 -CCl3 -C3H7 -C3H7 506-CCl3 Table 2 (continued) Example No. R¹ R² R³ 507-CCl3 CH3 CH3 508 -CH2Cl CH3 CH3 509 -CCl3 -CH3 -CH3 510 -CH2Cl H -C2H4Br 511 -CCl3 H -C2H4Br 512 -CHCl2 H -C2H4Br 513 -CHCl2 -C2H5 -n-C4H9 514 -CHCl2 -i-C3H7 -i-C3H7 Table 2 (continued) Example No. R¹ R² R³ 515 -CHCl2 -n-C4H9 -n-C4H9 516 -CCl3 -C2H5 -n-C4H9 517 -CCl3 -i-C3H7 -i-C3H7 518 -CCl3 -i-C4H9 -i-C4H9 519 -CHCl2 H C2H5 C2H5 520-CCl3 H -C (CH3) (C2H5) -CN 521 -CH2Cl H -C (CH3) (C2H5) -CN 522 -CHCl2 H -C (CH3) (C2H5) -CN 523 -CHCl2 CH3 CH3 CH3 Table 2 (continued) Example No. R¹ R² R³ 524 -CHCl2 CH3 C2H5 C2H5 525 -CHCl2 CH3 CH3 CH3 526 -CHCl2 CH3 iC3H7 527 -CHCl2 C2H5 C2H5 528 -CHCl2 CH3 C2H5 Table 2 (continued) Example No. R¹ R² R³ 529 -CHCl2 H C2H5 C2H5 530 -CHCl2 H CH3 C2H5 531 -CHCl2 HC (CH3) 3 532 -CHCl2 H CH3 CH3 533 -CHCl2 H CH3 CH3 Table 2 (continued) Example No. R¹ R² R³ 534 -CHCl2 -CH2-CH-OCH3 C2H5 CCl C2H5 isomer mixture, CH2 in which the two -CHCl2 -CH-CH2-OCH3 C2H5 components approximately im CCl C2H5 ratio 1: 1 forward CH2 lie. 535 -CHCl -CH2-N C2H5 N C2H5 536 -CHCl2 -CH2-N CH3 N C2H5 The amides of the formula (I) which can be used according to the invention are suitable - as already mentioned - for improving the crop plant tolerance of herbicidally active acetanilides of the formulas (II), (III) and (IV) or

of acid addition salts or metal salt complexes of active ingredients of formula (II).

Specific examples of acetanilides of the formula (II) or of acid addition salts derived therefrom are: 2-methyl-6-ethyl-N- (pyrazol-1-yl-methyl) -chloroacetanilide 2,6-diethyl-N - (Pyrazol-1-yl-methyl) -chloroacetanilide 2,6-diethyl-N- (1,2,4-triazol-1-yl-methyl) -chloroacetanilide 2,6-dimethyl-N- (1,2, 4-triazol-1-yl-methyl) -chloracetanilide 2-methyl-N- (pyrazol-1-yl-methyl) -chloroacetanilide 2, 5-dimethyl-N- (pyrazol- 1 -yl-methyl) -chloroacetanilide 2, 3-dimethyl-N- (pyrazol-1-yl-methyl) -chloroacetanilide 2-methyl-6-ethy1-N- (pyrazol-1-yl-methyl) -chloroacetanilide hydrochloride 2,6-diethyl-N- (pyrazole-1 -yl-methyl) chloroacetanilide hydrochloride 2,6-diethyl-N - [(3,5-dimethyl-pyrazol-1-yl) -methyl] -chloroacetanilide 2,6-diethyl-N - [(3-chloro-1, 2,4-triazolyl) methyl] chloroacetanilide 2-methyl-6-ethyl-Nz (3,5-dimethyl-pyrazol-1-yl) -methyl7-chloroacetanilide 2-tert-butyl-N- (pyrazole -1-yl-methyl) -chloroacetanilide 2-methyl-6-ethyl-N - [(3-bromo-5-methyl-pyrazolyl) -methyl] -chloroacetanilide 2-methyl-6-ethyl-NZ (4-ch loropyrazol-1-yl) methyl7-chloroacetanilide 2-methyl-6- # thyl-N - [(3-chloro-1,2,4-triazolyl) methyl] chloroacetanilide 2,6-diethyl-NZ ( 4-chloro-pyrazol- 1 -yl) methyl / chloroacetanilide Examples of acetanilides of the formula (III) are: 2,6-dimethyl-N- (benzyl-methyl) -chloroacetanilide 2,6-dimethyl- N- (4-chlorobenzoyl-methyl) chloroacetanilide 2-methyl-6-thyl-N- (benzoyl-methyl) -chloroacetanilide Examples of acetanilides of the formula (IV) are: 2,6-diethyl-N (2-methyl-1,3,4-oxadiazol-5-yl) -methyl7-chloroacetanilide 2,6-dimethyl-N - [(2-methyl-1,3,4-oxidiazol-5-yl) -methyl] chloroacetanilide 2-ethyl-6-methyl-N - [(2-methyl-1,3,4-oxadiazol-5-yl) methyl] chloroacetanilide 2-tert-butyl-N - [(2-methyl- 1,3,4-oxadiazol-5-yl) methyl / chloroacetanilide The herbicidally active acetanilides of the formula (II) and their acid addition salts and metal salt complexes are not yet known. However, they can be prepared by a) N-halomethyl-haloacetanilides of the formula in which X, Y, Z and n have the meaning given above and Hal represents halogen, in particular chlorine or bromine, with heterocycles of the formula RM (VIII) in which R has the meaning given above and M represents hydrogen or an alkali metal, optionally reacted in the presence of a diluent and an acid-binding agent and optionally then adding an acid or a metal salt.

If 2,6-diethyl-N-chloromethyl-chloroacetanilide and pyrazole are used as starting materials, the course of the reaction in process (a) can be represented by the following equation: The N-halomethyl-haloacetanilides to be used as starting materials in process (a) are generally defined by the formula (VII). In this formula, X and Y are identical or different and preferably represent straight-chain or branched alkyl having 1 to 4 carbon atoms. Z preferably represents the halogens chlorine or bromine and the index n has the meaning given above.

The N-halomethyl-haloacetanilides of the formula (VII) are known or can be produced by known methods (see US Pat. No. 3,630 716 and 3 637 847).

They are obtained, for example, by combining corresponding anilines with paraformaldehyde in the presence of catalytic amounts of potassium hydroxide and the resulting phenylazomethines with a haloacetyl halide, for example chloroacetyl chloride, added.

The N-halomethyl-haloacetanilides of the formula (VII) can also be obtained by a new process by using known haloacetanilides of the formula in which X, Y, Z and n have the meaning given above, with at least 1 mol of formaldehyde or formaldehyde-releasing substances, for example paraformaldehyde, and a halogenating agent, such as a hydrohalic acid or an inorganic or organic acid halide, and a water-binding agent, for example sodium sulfate , in a manner known per se at temperatures between -10 ° C. and 1500 ° C., preferably between 10 and 70 ° C., optionally in the presence of an inert organic solvent, for example toluene (cf. German Offenlegungsschriften 2 119 518 and 2 210 603). When using inorganic acid halides, such as thionyl chloride, it is possible to dispense with the use of a special water-binding agent (cf. also preparation examples).

The heterocycles also to be used as starting materials are generally defined by the formula (VIII).

In this formula, R preferably represents those which are optionally substituted Azolyl radicals pyrazol-1-yl, imidazol-1-yl, 1,2,4-triazol-1-yl; 1,2,3-triazol-1-yl; 1,3,4-triazol-1-yl and 1,2,3,4-tetrazol-1-yl as well as optionally substituted Pyrrol-1-yl. Preferred substituents are: halogen, in particular Fluorine, chlorine and bromine, as well as alkyl with 1 to 4 carbon atoms. M preferably stands for hydrogen and the alkali metals sodium and potassium.

The heterocycles of the formula (VIII) are generally known compounds of organic chemistry.

Use as diluents for the implementation according to process (a) preferably inert organic solvents. These preferably include Ketones such as diethyl ketone, especially methyl isobutyl ketone; Nitriles, such as propionitrile, especially acetonitrile; Ethers such as tetrahydrofuran or dioxane; aliphatic and aromatic hydrocarbons such as petroleum ether, benzene, toluene or xylene, halogenated Hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform or Chlorobenzene; Esters, such as ethyl acetate; and formamides, such as, in particular, dimethylformamide.

Acid binders which can be used in process (a) are all customarily usable inorganic and organic acid acceptors are used. For this preferably include alkali carbonates, for example sodium carbonate, potassium carbonate and sodium hydrogen carbonate: also lower tertiary alkylamines, aralkylamines, aromatic amines or cycloalkylamines, such as triethylamine, dimethylbenzylamine, Pyridine and diazabicyclooctane. It is also possible to use an appropriate excess to use on azole, including in the present case a compound of the formula (VIII) is to be understood.

The reaction temperatures can in process (a) in a larger Range can be varied. Generally one works between about 0 and 1200C, preferably between 20 and 800C, when carrying out method (a) sets is preferred to 1 mole of the compounds of the formula (VII) 1 to 2 mol of the heterocycle of the formula (VIII) and 1 mol of acid binder. For isolation of the compounds of the formula (II), the reaction mixture is filtered, the filtrate washed with water, dried and concentrated. The residue is optionally purified by fractional crystallization or distillation.

The reaction mixture is cooled in a special working-up form to about 0 ° C, filtered and passed into the filtrate at 5 to -15 ° C hydrogen chloride a. The precipitating chloride salts are sucked off with an organic solvent, for example ethyl acetate, washed and in a mixture of an organic Solvents, for example ethyl acetate and water with a pH of around 12, are distributed. The organic phase is separated off and the compounds of the formula (11) are isolated in the usual way.

For the preparation of acid addition salts of the compounds of the formula (II) all physiologically compatible acids come into question. These preferably include the hydrohalic acids, such as hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, Maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, Sorbic acid, lactic acid, and sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalene disulfonic acid.

The salts of the compounds of the formula (II) can be used in a simple manner by customary salt formation methods, e.g.

by dissolving a compound of formula (II) in a suitable inert one Solvent and adding the acid such as hydrochloric acid and in a known manner, for example by filtering off. isolated and if necessary by Wash with an inert organic solvent.

For the preparation of metal salt complexes of the compounds of the formula (II) are preferably salts of metals from II. To IV. Main and I. and II. And IV. To VIII. Subgroup in question, whereby copper, zinc, manganese, magnesium, Tin, iron and nickel may be mentioned as examples. Come as anions of the salts those that are derived from physiologically acceptable acids are considered. For this preferably include the hydrohalic acids such as hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulfuric acid.

The metal salt complexes of the compounds of the formula (II) can be used in can easily be obtained by conventional methods, for example by dissolving the Metal salt in alcohol, e.g. ethanol, and adding to the compound of the formula (II). Metal salt complexes can be isolated in a known manner, for example by filtering off and, if necessary, purify by recrystallization.

The practical production of acetanilides of the formula (II) starts the following examples.

Example 537 A mixture of 68 g (1 mol) of pyrazole and 106 g (1.05 mol) of triethylamine is added to 274.2 g (1 mol) of 2,6-diethyl-N-chloromethyl-chloroacetanilide in 250 ml of anhydrous ethyl acetate with stirring 150 ml of anhydrous ethyl acetate, the temperature rising to 30 ° C. The mixture is stirred for 1 hour at room temperature. There are two possibilities for working up: 1) The reaction mixture is filtered, the filtrate is washed neutral with water, dried over sodium sulfate and evaporated in vacuo. According to a faction.

th crystallization with ligroin one receives 171.2 g (56% of theory) 2,6-Diethyl-N- (pyrazol-1 -yl-methyl) -chloroacetanilide of melting point 670C in Form of colorless crystals.

2) The reaction mixture is cooled to OOC, filtered and the The filter residue was washed with 10 ml of cold ethyl acetate. Be in the filtrate initiated at 0 to -10 ° C 50 g (1.4 mol) of dry hydrogen chloride.

The precipitated hydrochloride salts are then filtered off with suction and washed with 50 ml of cold ethyl acetate and distribute the solid residue between 0.5 1 ethyl acetate and 0.5 1 aqueous sodium hydroxide solution with a pH value of 12. The organic phase is separated off, twice with 0.5 l of sodium chloride solution each time washed, dried over sodium sulfate and evaporated in vacuo. The colorless one 60 ml of gasoline are added to the oily residue, whereupon it crystallizes. You get 220.2 g (72% of theory) 2,6-diethyl-N- (pyrazol-1-yl-methyl) -chloroacetanilide vom Melting point 6700 in the form of colorless crystals.

The compounds listed in the table below are prepared in an analogous manner: Table 3 Ex. Melting Point No. X Yn ZR (° C) 538 C2H5 6-C2H5 Cl 1,2,4-triazolyl-1-yl 112,539 i-C3H7 6 i C3 7 C1 pyrazol-1-yl 134,540 CH3 6-C2H5 C1 1,2,4-triazol-1-yl 92,541 CH3 6-C2H5 Cl pyrazol-1-yl 57,542 C2H5 4,6- (CH3) 2 Cl pyrazol-1-yl 82,543 CH3 4,6- (CH3 ) 2 Cl pyrazol-1-yl 92 544 C2H5 4-CH3 Cl pyrazol-1-yl 78 6-C2H5 545 i-C3H7 6-i-C3H7 Cl 1,3,4-triazol-1-yl 196 546 i-C3H7 6-i-C3H7 Cl 1,2,4-triazol-1-yl 138 Table 3 (continued) Ex. Melt-No. X Yn ZR point (° C) 547 C2H5 6-C2H5 Cl pyrrol-1-yl oil 548 i C3H7 C1 1,2,4-triazol-1-yl 118 549 CH3 6-C2H5 Cl 1,2,3,4- Tetrazol-1-yl oil 550 i-C3H7 - Cl pyrazol-1-yl oil 551 C2H5 - Cl 1,2,4-triazol-1-yl 81 552 CH3 6-CH3 Cl pyrazol-1-yl 82 553 CH3 6- CH3 Cl 1,2,4-Triazol-1-yl 110 554 CH3 5-CH3 Cl 1,2,4-Triazol-1-yl Oil 555 CH3 - Cl Pyrazol-1-yl 56 556 CH3 - Cl 1,2, 4-Triazol-1-yl 88 557 CH3 5-CH3 Cl pyrazol-1-yl oil 558 CH3 3-CH3 Cl 1,2,4-triazol-1-yl 114 559 CH3 3-CH3 Cl pyrazol-1-yl 102 560 C2H5 6-CH3 Cl pyrazol-1-yl (xHCl) 87 561 C2H5 6-C2H5 Cl pyrazol-1-yl (xHCl) 67 562 C2H5 6-C2H5 Cl 3,5-dimethylpyrazol-1-yl 111 563 C2H5 6- C2H5 Cl Bromo-methylpyrazolyl 145 564 C2H5 6-C2H5 Cl 3-chloro-1,2,4-triazol-1-yl 110 565 CH3 6-C2H5 Cl 3,5-dimethylpyrazol-1-yl 90 566 C2H5 6-C2H5 Cl 3-Methylpyrazol-1-yl 89 567 C2H5 6-CH3 Cl 3-Methylpyrazol-1-yl 113 568 C (CH3) 3 - Cl Pyrazol-1-yl Oil 569 C (CH3) 3 - Cl 1,2,4- Triazol-1-yl 118 570 C2H5 6-CH3 Cl Bromo-methylpyrazolyl 80 571 CH3 6-C2H5 Cl 4-chloropyrazol-1-yl 91 572 CH3 6-C2H5 Cl 3-chloro-1,2,4-triazol-1-yl 121 573 C2H5 6-CH3 Cl 2,4,5-trichloroimidazol-1-yl 158 Table 3 (continued) Ex.

No. X Yn ZR Melting Point (° C) 574 C2H5 6-C2H5 Cl 4-Chlorpyrazol-1-yl 110 575 C2H5 6-C2H5 Cl 1,2,3,4-Tetrazol-1-yl 110 576 C2H5 6-C2H5 Br Pyrazol-1-yl 68 577 CH3 6-C2H5 Br pyrazol-1-yl 67 578 C2H5 6-C2H5 Cl imidazol-1-yl oil 579 C2H5 6-C2H5 Br 1,2,4-triazol-1-yl 90 580 CH3 6-C2H5 Br 1,2,4-Triazol-1-yl 78 Preparation of Starting Products Example 538a (Variant oC) 45 g (1.5 mol) of paraformaldehyde are added to a solution of 225.7 g (1 mol) of 2,6-diethyl chloroacetanilide in 1.5 1 of toluene. The mixture is warmed to 40 ° C. and 179 g (1.5 mol) of thionyl chloride are added dropwise with stirring, with vigorous evolution of gas commencing. The mixture is allowed to stir at 40 ° C. until the evolution of gas has ended. It is then filtered and the filtrate is concentrated in vacuo. After degassing the residue in a high vacuum, 268.7 g (98% of theory) of 2,6-diethyl-N-chloromethyl-chloroacetanilide are obtained as a colorless oil.

(Variant β) To a solution of 225.7 g (1 mol) of 2,6-diethyl chloroacetanilide in 1.5 l of anhydrous toluene, 45 g (1.5 mol) of paraformaldehyde and 100 g of anhydrous Given sodium sulfate. While stirring and heating to 500C one passes dry as long Hydrogen chloride until the milky suspension of paraformaldehyde disappeared is. Then another 100 g of anhydrous sodium sulfate are added, one hour stirred at 5000 and filtered. The filtrate is concentrated in vacuo. To degasing 263.2 g (96 96 of theory) of 2,6-diethylchloroacetanilide are obtained from the residue as a colorless oil.

The compounds in the table below are analogous to Example 538a 4 received.

Table 4 E.g. melting point no. X Yn Z Hal or refractive index 539 a i-03H7 6-i-C3H7 Cl Cl not isolated 540 a CH3 6-C2H5 Cl Cl 91 542 a C2H5 4,6- (CH3) 2 Cl Cl not isolated 543 a CH3 4,6- (CH3) 2 Cl Cl not isolated 544 a 0 2H5 4-OH3 Cl Cl not isolated 6-C2H5 548 a i-C3H7 - Cl Cl 90 551 a C2H5 - Cl Cl not isolated 552 a CH3 6 -CH3 Cl Cl 88 554 a CH3 5-CH3 Cl Cl not isolated 558 a CH3 3-CH3 Cl Cl 40 568 a C (CH3) 3 - Cl Cl not isolated 576 a C2H5 6-C2H5 Br Br not isolated 577 a CH3 6 -C2H5 Br Br not isolated The acetanilides of the formula (II) have strong herbicidal effects, in particular against grasses. They can therefore be used for selective weed control and, in particular, weed control.

The herbicidally active acetanilides of the formula (III) are also not yet known. However, they can be prepared by b) N-acylmethylanilines of the formula in which R4, R51R6, R7 and m have the meaning given above, is reacted with chloroacetyl chloride in the presence of a diluent.

If 2,6-dimethyl-N-benzoylmethyl-aniline and chloroacetyl chloride are used as starting materials, the course of the reaction in process (b) can be represented by the following equation: The N-acylmethyl-anilines to be used as starting materials in process (b) are generally defined by formula (X). In this formula, R4 preferably represents straight-chain or branched alkyl having 1 to 6, in particular 1 to 4 carbon atoms, halogen, in particular fluorine, chlorine and bromine, haloalkyl having up to 3 carbon and up to 5 identical or different halogen atoms, where the halogens in particular are fluorine and chlorine, trifluoromethyl may be mentioned by way of example; also preferably for alkylthio and alkylsulfonyl with 1 to 4 carbon atoms in the alkyl part and for aminosulfonyl, cyano and nitro. R5 and R6 are identical or different and preferably represent hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, halogen, in particular fluorine, chlorine and bromine, haloalkyl with up to 3 carbon and up to 5 identical or different halogen atoms, where as Halogens, in particular fluorine and chlorine, and preferably optionally mono- or polysubstituted phenyl, the radicals mentioned for R4 preferably being possible as substituents. R7 preferably represents straight-chain or branched alkyl having 1 to 6, in particular 1 to 4 carbon atoms and optionally mono- or polysubstituted phenyl, the radicals already mentioned for R4 and phenyl and phenoxy, which can also be substituted by R4, as substituents , come into question.

The N-acylmethyl-anilines of the formula (X) are known (see, inter alia, Chem. Ber. 25, 2865 (1892) and Chem. Soc.

1943, 63) or can be determined by known methods produce. They are obtained, for example, by combining anilines with i, -halo ketones in the presence of a organic solvent, such as ethanol, converts (see also the preparation examples).

The diluents for the implementation according to process (b) are preferably inert organic solvents. These preferably include Ketones such as diethyl ketone, especially acetone and methyl ethyl ketone; Nitriles, like Propionitrile, especially acetonitrile; Ethers such as tetrahydrofuran or dioxane; aliphatic and aromatic hydrocarbons such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, Chloroform or chlorobenzene; and esters, such as ethyl acetate.

The reaction temperatures can be used when carrying out the process (b) can be varied over a wide range. Generally one works between 0 and 1200C, preferably between 20 and 1000C.

When carrying out method (b), preference is given to starting 1 mole of the compound of formula (X) has 1 to 3 moles of chloroacetyl chloride. The isolation of the compounds of the formula (III) is carried out in the customary manner.

The practical preparation of acetanilides of the formula (III) can be seen from the following examples: Example 581 16 ml (0.2 mol) of chloroacetyl chloride are added dropwise to a solution of 18.5 g (0.068 mol) of 2,6-dimethyl-N- (4-chlorobenzoylmethyl) aniline in 150 ml of benzene. The mixture is then stirred under reflux for 15 hours and concentrated by distilling off the solvent and the excess chloroacetyl chloride in vacuo. The residue is triturated with a mixture of ether / petroleum ether (1: 3), and the resulting crystalline residue is filtered off with suction and dried. 17.7 g (75% of theory) of 2,6-dimethyl-N- (4-chlorobenzoylmethyl) chloroacetanilide with a melting point of 1280 ° C. are obtained.

Manufacture of the starting product 46.7 g (0.2 mol) of UJ-bromo-4-chloroacetophenone in 40 ml of ethanol are added to 48.4 g (0.4 mol) of 2,6-dimethylaniline in 40 ml of ethanol and heated to 50 ° C. for 20 minutes.

It is then cooled to OOC and the crystals formed are filtered off off and washes with a little ethanol. 30 g (55% of theory) of 2,6-dimethyl-N- (4-chlorobenzoylmethyl) aniline are obtained of melting point 820C.

Example 5ß2 23.3 g (0.1 mol) of 2-ethyl-6-methyl-N-pivaloylmethyl-aniline are dissolved in 100 ml of benzene, and 24 ml (0.3 mol) of chloroacetyl chloride are added. The mixture is then stirred under reflux for 15 hours and concentrated by distilling off the solvent and the excess chloroacetyl chloride in vacuo. The oily residue is stirred with petroleum ether, decanted, stirred with activated charcoal, filtered and concentrated in vacuo. The residue is stirred with n-hexane, and the resulting solid is filtered off with suction and dried. 13.7 g (45% of theory) of 2-ethyl-6-methyl-N-pivaloylmethyl-chloroacetanilide with a melting point of 860 ° C. are obtained.

Manufacture of the starting product 108 g (0.8 mol) of 2-ethyl-6-methyl-aniline and 53.8 g (0.4 mol) of monochloropinacoline are heated to 110 ° C. in 300 ml of toluene for 25 hours. It is allowed to cool, filtered, the filtrate is washed with water, dried over sodium sulfate and concentrated by distilling off the solvent in vacuo. The residue is fractionally distilled. 24.1 g (26% of theory) of 2-ethyl-6-methyl-N-pivaloylmethyl-aniline with a boiling point of 138 to 1550 ° C./0.7 mm and a refractive index of n20 = D 1.5168 are obtained.

Those listed in Table 5 below are analogous Connections made.

Table: 5 Ex. R4 R5 R6 R7 Melting point (00) or No. m R refractive index 583 2-CH3 HH t 138 584 2-CH3 HH 4 so1 140 585 2,6- (C2H5) z HH oC1 134 586 2,6- (O2H3) 2 HH> 116 587 2-C1 HH-O1 124 588 2,6- (CH3) 2 HHO 100 589 4-C1 HH oC1 114 590 2,6- (CH3) 2 CH3 H CH3 104 591 26- (W3H7) 2 HH oC1 200 592: 2.6 (O2) 2,), HH) 112 4-CH, 593 2,6- (ic3H ,,) 2 HHO 140 594 2,6- (CH3) 2 HH qH3 90 OH3 595 2-C24, HH wFC1 7o 596 2,6- (CH3) 2 HH HoCH, 114 OCH3 597 62- (5CH3) 2 @ nD ° = 1.5680H HD = 1.5680 4,6- (oH3) 2 598 2,6- (CH3) 2 HH bF - 104 599 2,4,6- (CH3) 3 HH oC1 "'134 Table 5 (continued) Ex. R 4 5 6 R7 melting point (° C) or No. RRRR refractive index 600 2,4,6- (CH3) 3 HH at n2D = 1.5610 601 2,6- (CH3) 2 H t oC1 149 602 2,6- (CH3) 2 H CH3 O 84 The compounds listed in Table 6 below can be used in an analogous manner At- R4 R6 R7 m 603 3,5- (CF, \ HH --cl I. 604 2,6- (CH, \ H ENT, 605 2,6- (CH3) 2 HH ON 606 2,6- (OH3) 2 HH-O (OH3) 3 607 2,6- (CH3) 2 HH -C1 4-SO2 NH2 608 2-C1, 6-CH3 H H-C1 609 2-C2H5, 6-CH3 CH3 CH3 610 2-c2 H5, 6-CH3 CH3 CH3 - 611 2-02H5,6-0H3 CH3 CH3 612 2-C2Hs, 6-CH3 CH3 CH3 -C1 613 2-C2 H5, 6-CH3 CH3 CH3 -C1 614 2-C2H5, 6-CH3 H CH3 t-C1 615 2-C2 H5 6-CH3 H CH3 teC1 616 2,6- (CH, H4-C1 O1 617 2, 6- (CH3) 2 H -F -C1 618 2,6- (CH3) 2 H -CH3 619 2,6- (CH3) 2 H. 620 2,6- (CH3) 2 HO1 O 621 2,6- (CH3) 2 H CH3 tC1 The acetanilides of the formula (III) have strong herbicidal properties. They are therefore suitable for weed control. In particular, they can be used for selective weed and weed control.

The herbicidally active acetanilides of the formula (IV) are likewise not yet known. However, they can be prepared by c) N-azolylalkylanilines of the formula in which R8, R9, R10, R11, A and p have the meaning given above, with haloacetic acid chlorides or anhydrides of the formulas R¹²-CH2-CO-Cl (XIIa) or

(R12 -0H2-O0) 20 (XIIb) in which R12 has the meaning given above, is reacted in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent. If 2,6-diethyl-N- (3-methylthio-4-methyl-1,2,4-triazol-5-yl-methyl) aniline and chloroacetyl chloride are used as starting materials, the course of the reaction in process (c) can be carried out the following equation can be reproduced: The formula (XI) provides a general definition of the N-azolylalkylanilines required as starting materials when carrying out process (c). In this formula, A preferably represents oxygen, sulfur or the group -NR2, in which R preferably represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms and aryl having 6 to 10 carbon atoms, in particular phenyl, where each these aryl radicals can be substituted by halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, cyano, nitro and / or haloalkyl with up to 2 carbon and up to 5 identical or different halogen atoms, fluorine and chlorine in particular being mentioned as halogens. R10 preferably represents hydrogen or methyl. R11 in the formula (XI) preferably represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, haloalkyl having up to 3 carbon atoms and up to 5 identical or different halogen atoms, the halogens in particular being fluorine and chlorine, an example being trifluoromethyl mentioned, also preferably for alkenyl and alkynyl with 2 to 4 carbon atoms, cycloalkyl with 5 to 7 carbon atoms and for halogen, in particular fluorine, chlorine or bromine. R11 furthermore preferably represents aryl with 6 to 10 carbon atoms, in particular phenyl, it being possible for each of these aryl radicals to be substituted by halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, cyano, nitro and / or haloalkyl with up to 2 carbon atoms and up to 5 identical or different halogen atoms, the halogens in particular being fluorine or chlorine and trifluoromethyl being specifically mentioned as an example of haloalkyl. R11 also preferably represents aralkyl with 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, in particular benzyl, where each of these aralkyl radicals in the aryl part can be substituted by halogen, alkyl with 1 to 4 carbon atoms, alkylthio with 1 or 2 carbon atoms , Alkylthio with 1 or 2 carbon atoms, oyano, nitro and / or haloalkyl with up to 2 carbon atoms and up to 5 identical or different halogen atoms, where the halogens are in particular fluorine or chlorine and trifluoromethyl is specifically mentioned as an example of haloalkyl. In addition, R11 stands for the groupings -R14, -SR14 and 1314, in which R13 preferably stands for those radicals which have already been mentioned above as preferred for this radical, R14 in these groupings stands for hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms Haloalkyl with 3 carbon atoms and up to 5 identical or different halogen atoms, where the halogens are in particular fluorine and chlorine, trifluoromethyl may be mentioned by way of example, furthermore preferably alkenyl and alkynyl with 2 to 4 carbon atoms, cycloalkyl with 5 to 7 carbon atoms and aralkyl with 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, in particular for benzyl, where each of these aralkyl radicals in the aryl part can be substituted by halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 Carbon atoms, cyano, nitro and / or haloalkyl with up to 2 carbon atoms and up to z u 5 identical or different halogen atoms, where the halogens are in particular fluorine or chlorine and trifluoromethyl is specifically mentioned as an example of haloalkyl.

In the formula (XI), R8 is preferably straight-chain or branched Alkyl of 1 to 4 carbon atoms.

R9 in the formula (XI) preferably represents straight-chain total or branched alkyl with 1 to 4 carbon atoms or for the halogens fluorine, Chlorine and bromine; the index p stands for the numbers 0, 1 or 2.

The N-azolylalkylanilines of the formula (XI) required as starting materials in process (c) are not yet known. They are obtained when d) anilines of the formula in which 89 R, R9 and p have the meaning given above, with azole derivatives of the formula in which 10 11 A, R and R11 have the meaning given above and Hal 'stands for chlorine or bromine, in the presence of an acid binder such as potassium or sodium carbonate, and in the presence of an inert organic solvent such as dimethylformamide or toluene Reacts temperatures between 20 and 160 ° C., an excess of aniline of the formula (XIII) preferably being used (cf. also preparation examples), or e) hydrazine derivatives of the formula in which 8 9 10 R, R, R and p have the meaning given above with isocyanates or mustard oils of the formula R¹³-NCB (XVI) in which B is oxygen or sulfur and R13 has the meaning given above, in the presence of an organic one Solvent, such as an alcohol, ether or hydrocarbon, at temperatures between 0 and 80 ° C., the resulting compounds of the formula in which B, R8, R91R10, R13 and p have the meaning given above, cyclized in the presence of a strong base such as sodium or potassium hydroxide, and in the presence of a solvent such as ethanol or water at temperatures between 20 and 1000C and the resulting triazolones or triazolthiones of the formula in which B, R8, R9, R10, R¹³ and p have the meaning given above, with halides of the formula HalU -R15 (XIX) in which Hal 'stands for chlorine or bromine and R15 stands for the radicals of the substituent R14, where hydrogen is excluded, in the presence of a strong base, such as sodium hydroxide solution, and in the presence of an inert organic solvent, such as toluene or methylene chloride, at temperatures between -20 and 80oC, with phase transfer catalysis and other alkylating reagents, such as dimethyl sulfate can (cf. also preparation examples), or f) hydrazine derivatives of the formula (XV) with formic acid or acid chlorides or acid anhydrides of the formulas R1 6 -CO-C1 (XXa) or

16 in which R16 represents alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, optionally substituted aryl or optionally substituted aralkyl in the presence of an inert organic solvent, such as an ether, hydrocarbon or halogenated hydrocarbon, at temperatures between 0 and 500C and the resulting compounds of formula in which R8, R9, R10, R16, R, R, R and p have the meaning given above, either with diphosphorus pentasulfide in a manner known per se (cf. Chem. Ber. 32, 797 (1899) and J.prakt.

Chemie 69, 145 (1904) cyclized to thiadiazole derivatives, or also converted in a known manner with customary dehydrating reagents to oxadiazole derivatives (cf. Elderfield, Heterocyclic Compounds, Vol. 7 (1961) or g) hydrazine derivatives of the formula (XV) with nitriles of the formula R17-CN (XXII) in which R17 is optionally substituted alkyl or optionally substituted aryl converts to triazole derivatives in a manner known per se (cf. Chem.Ber. 96, 1064 (1963)), or h ) Hydrazine derivatives of the formula (XV) with imino ethers of the formula in which R16 is alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, optionally substituted aryl or optionally substituted aralkyl and R18 is methyl or ethyl, in a manner known per se under reflux and in the presence of an inert organic solvent such as ethanol Reacts oxadiazole derivatives, or j) the anilines of the formula (XIII) with azole aldehydes of the formula in which R11 has the meaning given above, in the presence of an inert organic solvent, such as, for example, toluene, at temperatures between 80 and 1200C, and the resulting compounds of the formula in which A, R8 9 11, R, R and p have the meaning given above, reduced in a generally known manner; for example by reaction with complex hydrides such as sodium borohydride, if appropriate in the presence of a polar organic solvent such as methanol, at temperatures between 0 and 8000.

The compounds required as starting materials in process d) of the formulas (XIII) and (XIV) are known or can be according to what is known in principle Establish process (see Helv.Chim.Acta 55, 19 9 ff (1972), Chem.Ber. 32, 797 ff (1899) and Chem. Ber. 96, 1049 ff (1963)).

The starting materials of the formula (XV) required for process (e) are not yet known. However, they can be produced by known processes by using known esters (cf., inter alia, German Offenlegungsschrift 2,350,944 and 2,513,730) of the formula in which R8, R9, R10 and p have the meaning given above and R18 is methyl or ethyl, with hydrazine hydrate, preferably in the presence of an organic solvent, such as ethanol, dioxane or dimethylformamide, at temperatures between 20 and 1200C (cf. also Manufacturing examples).

The reaction components of the formulas required for process (e) (XVI) and (XIX) are generally known compounds in organic chemistry.

Those required as reaction components in processes (f), (g) and (h) Substances of the formulas (XXa), (XXb), (XXII) and (XXIII) are also known.

Those to be used as reaction components in process (j) Azole aldehydes of the formula (XXIV) are also known or can be according to im Establish the principle of known processes (cf. Elderfield, "Heterocyclic Compounds", Vol. 7 (1961) and "Advances in Heterocyclic Chemistry, Vol. 9 (1968)).

The also for the implementation of process (c) as starting materials Haloacetic acid chlorides or anhydrides to be used are indicated by the formulas (XIIa) and (XIIb) generally defined. In these formulas, R12 is preferably for chlorine, bromine and iodine.

The haloacetic acid chlorides and anhydrides of the formulas (XIIa) and (XIIb) are generally known compounds in organic chemistry.

The diluents used for reaction (c) are preferably inert ones organic solvents in question. These preferably include ketones, such as diethyl ketone, in particular acetone and methyl ethyl ketone; Nitriles, such as propionitrile, in particular Acetonitrile; Ethers such as tetrahydrofuran or dioxane; aliphatic and aromatic Hydrocarbons such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; and esters, like ethyl acetate.

Process (c) can, if appropriate, be carried out in the presence of acid binders (Hydrogen chloride acceptors) carried out will. As such all common acid binders can be used. These preferably include organic bases such as tertiary amines, for example triethylamine, or such as pyridine; also inorganic bases, such as alkali hydroxides and alkali carbonates.

The reaction temperatures can be used when carrying out the process . (c) can be varied within a larger range. Generally one works between 0 and 12000, preferably between 20 and 1000C.

When carrying out process (c), it is preferable to start up 1 mole of the compound of the formula (XI) 1 to 1.5 moles of haloacetylating agent and 1 to 1.5 moles of acid binder. The compounds of the formula (VI) are isolated in the usual way.

The practical production of acetanilides of the formula (IV) starts out the following examples.

Example 622 16.3 g (0.07 mol) of 2-ethyl-6-methyl-N-n2-methyl-1,3,4-oxadiazol-6-yl) -methyu-aniline and 6 g (0.076 mol) of anhydrous pyridine become heated to boiling in 100 ml of absolute tetrahydrofuran with stirring and treated dropwise with a solution of 8 g (0.07 mol) of chloroacetyl chloride in 20 ml of tetrahydrofuran. After the end of the dropwise addition, the mixture is stirred for 10 minutes, concentrated by distilling off the solvent and the residue is stirred with 150 ml of water. The reaction product which crystallizes out is filtered off with suction, washed with water and dried. 18.7 g (87% of theory) beige-colored crystals of 2-ethyl-6-methyl-Nt (2-1,3,4-oxadiazol-5-yl) methyl y-chloroacetanilide with a melting point of 67 to are obtained 7000.

Manufacture of the starting product A mixture of 101.2 g (0.76 mol) of 2-ethyl-6-methylaniline, 40 g (0.3 mol) of 5-chloromethyl-1,3,4-oxadiazole, 41.4 g (0.3 Mol) powdered potassium carbonate and 76 ml of dimethylformamide are heated to 1000C for 5 hours while stirring. The reaction mixture is then filtered, the filtrate is diluted with methylene chloride and washed several times with water. The methylene chloride phase is dried over sodium sulfate and concentrated in vacuo by distilling off the solvent. The residue is distilled in vacuo. 46.8 g (67.5% of theory) of a yellowish oil of 2-ethyl-6-methyl-Nt (2-methyl-1,3,4-oxadiazol-5-yl) -methyi7-aniline with a boiling point of 140 are obtained up to 1420C / 0.1 mm with a 94% purity (determined by gas chromatography).

Example 623 5 g (0.017 mol) of 2,6-diethyl-N-R1-methyl-2-methylthio-1, 3,4-triazol-5-yl) -methyl7-aniline and 1.6 g (0.02 mol) of pyridine are stirred in 100 ml of absolute tetrahydrofuran and 2.3 g (0.02 mol) of chloroacetyl chloride are added dropwise at room temperature, the temperature rising to approx. The mixture is stirred for 2 hours, partially concentrated by distilling off the solvent and mixed with water. The product which crystallizes out is filtered off with suction, dried and recrystallized from diisopropyl ether / ethyl acetate. 5 g (80% of theory) of 2,6-diethyl-N-1-methyl-2-methylthio-1,3,4-triazol-5-yl) methyl] chloroacetanilide with a melting point of 121 to 1230 ° C. are obtained.

Manufacture of the preliminary stages 13.9 g (0.05 mol) of 2,6-diethyl-N-nl-methyl-2-thiono-1,3,4-triazol-S-yl) -methyl7-aniline are mixed at room temperature in a two-phase mixture of 150 ml of toluene and 40 ml of 50% or sodium hydroxide solution with the addition of 1.5 g of triethylbenzylammonium chloride (TEBA) as a catalyst and treated dropwise with 6.3 g (0.05 mol) of dimethyl sulfate, the temperature rising to about 350C .

The mixture is stirred for 5 hours, the toluene phase is separated off, washed several times with water, dried over sodium sulfate and concentrated by distilling off the solvent. The remaining oil is made to crystallize by adding petroleum ether. After recrystallization from petroleum ether, 6.7 g (40% of theory) of 2,6-diethyl-N [(1-methyl-2-methylthio-1,3,4-triazol-5-yl) methyl7-aniline vom Melting point 65 to 6700.

29.6 g (0.1 mol) of 1-methyl-4-C (2,6-diethyl-anilino) -acetylJ-thiosemicarbazide are suspended in 150 ml of ethanol and after adding 7 g of potassium hydroxide in 20 ml of water for 1 hour Heated to reflux. Most of the solvent is then distilled off and 250 ml of water are added to the residue. After acidification with glacial acetic acid to pH 5, the resulting precipitate is filtered off with suction and washed thoroughly with water. After drying, 27 g (97% of theory) of 2,6-diethyl-N-R1-methyl-2-thiono-1,3,4-triazol-5-yl) methyl-7-aniline with a melting point of 117 to 12,100 are obtained .

44.2 g (0.2 mol) of 2,6-diethylanilinoacetic acid hydrazide and 14.8 g (0.2 mol) of methyl mustard oil are dissolved in 250 ml of ethanol and heated to reflux temperature for one hour. After the subsequent cooling to room temperature, the precipitate formed is filtered off with suction and washed twice with 50 ml of ethanol each time. After drying, 46 g (78,96 of theory) of 1-methyl-4- (2,6-diethylanilinoacetyl) thiosemicarbazide are obtained in the form of a colorless crystalline substance with a melting point of 166.degree 58.7 g (0.25 mol) of ethyl 2,6-diethyl anilino-acetate and 25 g of hydrazine hydrate are left to stand in 200 ml of ethanol for 24 hours. It is then concentrated by distilling off the solvent and the residue is stirred up with water. After drying, 50.5 g (91% of theory) of colorless crystals of 2,6-diethylanilinoacetic acid hydrazide with a melting point of 71 ° to 73 ° C. are obtained are.

Table 7 Ex. 10 11 9 R8 A 12 No.RRRAR enamel point (OC) 624 H CH3 02H5 6-C2H5 O C1 79-82 625 H CH3 CH3 6-OH3 O C1 91-93 626 H CH3 C (CH3) 3 ° C C1 102-04 627 H -S-CH2-CH = CH2 6-02H5 6 Cl 5, C1 67-70 CH3 628 H -S-CH2H) CH3 6-C3H5 XN 'C1 115-20 CH3 F raw 3 629 H 02H5 OH3 6-O2H5 O C1 57-59 630 HO2H5 02H5 6-C, Hg O C1 43-47 631 H i C3H7 CH3 6-C2H5 0 C1 viscous oil 632 H CH3 CH3 3-CH3 N 'C1 glass-like IOr LI3 solidified CH3 633 H CH3 O2H5 6-CHO Br 800 634 H CH3 iC, H 6-iC, H70 C1 92-940C 635 H CH3 i-C3H7 6-i-03H7 O C1 135-370 After one or more of the processes described in the application, the starting products listed in the table below by their formulas are obtained.

Table 8 Example point No. 10 R11 R9 R8 AL o7 p or refractive index XI-1 H OH3 C2H5 6-C2H, 0 n22 = 1.540 XI-2 H CH3 CH3 6-C2H O 92 = 1.547 XI-3 H CH3 CH3 6-CH3 O nD2 ~ 1.552 OH3 OH3 6-OH3 D XI-4 H CH3 - (CH3) 3 - O 52-55 XI-5 H CH3 3 7 6-isl, O 96-99 HH O2H5 O2H5 6-C2H5 O 22 = 1.534 91 XI-7 H 02H5 CH3 6-C2H5 0 ni, = 1.542 XI-8 H i-O 3 H 7 CH 3 6-O 0 1 = 1.531 D. XI-9 H SCH3 O2H5 6-C2H5) N "QI3 65-57 XI-10 H 21 = 1.577 S-012 H 6-C2H5 O9i 6-C2H5 n nD = CH2 F XI-11 H S-CH24> cH3 to N-CHi tough o1 XI-12 H CH3 CH3 3-013 142-143 013 The acetanilides of the formula (IV) have strong herbicidal, in particular selective herbicidal, properties which are not always sufficient. They are therefore suitable for weed control. In particular, they can be used for selective weed and weed control.

The amides of the formula which can be used according to the invention as antidotes (I) are particularly suitable for improving the tolerance of herbicidally active substances Acetanilides of the formulas (II), (III) and (IV) or of acid addition salts or Metal salt complexes of active ingredients of the formula (II) in important cultivated plants, such as corn, soybeans, cotton, sugar beets, cereals, rice and sugar cane.

The active ingredient combinations according to the invention show very good results Effect against weeds and grass weeds in numerous crops of useful plants. You can therefore used for selective weed control in numerous crops of useful plants will. - Weeds in the broadest sense are to be understood as meaning all plants that grow in places where they are undesirable.

The inventive active ingredient combinations can, for example, at following plants are used.

Dikctv le weeds of the genera: Sinapis, Lepicium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, IFooea, Polygonum, Sesbania, Ambrosia, cirsium, - Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Powder, Centaurea.

Dicc.yle cultures of the genera: Gossypium, Glycine, Beta, Daucls, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cuburbita.

Monckotyle weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, 5rachiara, Lolium, Bromus, Avena, cyperus Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocot cultures of the genera: Oryza, Zea, Triticum, hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

The active ingredient combinations according to the invention are particularly suitable for selective weed control in maize, soybeans, cotton, sugar beet, grain, Rice and sugar cane.

The selective herbicidal effectiveness of the active compound combinations according to the invention is particularly pronounced when herbicidal active ingredient and antidote in certain Conditions exist. However, the weight ratios of the herbicidal active ingredient to antidotes in the active ingredient combinations according to the invention in relatively large Areas fluctuate. Generally account for 1 part by weight of one herbicidal Active ingredient of the formula (II), (III) or (IV) 0.05 to 1.0 parts by weight, preferably 0.1 to 0.5 parts by weight of an antidote of the formula (I).

These antidotes of the formula (I) or the active compound combinations according to the invention of an antidote and a herbicidal Active ingredient can be converted into the usual formulations, such as solutions, Emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble Powders, granulates, suspension emulsion concentrates, seed powders, impregnated with active ingredients Natural and synthetic materials, finest encapsulation in polymer materials and in Hü11 masses for seeds.

These formulations are prepared in a known manner, for example by Mixing of an antidote that can be used according to the invention or one according to the invention Active ingredient combination of antidote and herbicidal active ingredient with extenders i.e. liquid solvents, pressurized liquefied gases and / or solid carriers, optionally with the use of surface-active agents, that is, emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents, for example, can also be used can be used as co-solvents. The liquid solvents used are essentially in question: aromatics such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol as well as their ethers and esters, Ketones, such as acetone, Methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g. aerosol propellants such as halogenated hydrocarbons and butane, Propane, nitrogen and carbon dioxide; as solid carriers come into question: z .. natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock powder such as highly dispersed Silica, alumina and silicates; come as solid carriers for granules in question: e.g. broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic Flours and granules made from organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks; as emulsifying and / or foam-producing agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azole-metal phthalocyanine dyes and trace nutrients-such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight on an antidote that can be used according to the invention or on one according to the invention Active ingredient combination of antidote and herbicidal active ingredient, preferably contained they are between 0.5 and 90 percent by weight.

The antidotes that can be used according to the invention or those according to the invention Combinations of active ingredients, as such or in their formulations, can also be used as a mixture with known herbicides for weed control use, finished formulation or tank mixing is possible. Also a mixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, bird repellants, Growth substances, plant nutrients and soil structure improvers are possible.

The antidotes that can be used according to the invention or those according to the invention Combinations of active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders and granules can be applied. The application happens in the usual way, e.g. by watering, spraying, spraying, dusting, scattering, Dry pickling, wet pickling, wet pickling, slurry pickling or encrusting.

The antidotes which can be used according to the invention can be according to the for such Antidotes are applied using the usual methods. So can be used according to the invention Against- agent applied either before or after the herbicide or applied together with the herbicide.

Furthermore, crop plants can be treated with the antidotes by treating the seeds be protected from damage before sowing (dressing) if the herbicide before or after the sowing is applied. Another possible use is that the antidote is applied in the seed furrow when sowing. If it is with the plants are cuttings, they can be removed with the Antidotes to be treated.

The amount of antidote applied is in principle independent of the herbicide and the application rate of herbicidal active ingredient.

In general, the application rates of the antidote are for surface treatment between 0.1 and 5 kg / ha, preferably between 0.2 and 4 kg / ha. When treating seeds the application rates of antidote are generally between 10 and 300 g per Kilogram of seed, preferably between 25 and 200 g per kilogram of seed. the Application rates of active ingredient combinations according to the invention can to a certain extent Range can be varied. In general they are between 0.5 and 10 kg / ha, preferably between 1 and 5 kg / ha.

The application rates of herbicidal active ingredient generally vary between 0.1 and 5 kg / ha, preferably between 0.2 and 4 kg / ha.

The good effectiveness of the antidotes which can be used according to the invention or the active ingredient combinations according to the invention can be found in the following example emerged.

Example A Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether 1 part by weight of the antidote or herbicidal active ingredient is mixed in the preparation of the active compound or a mixture of antidote and herbicidal active ingredient with the specified Amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Seeds of the test plants are sown in normal soil and after 24 hours with the antidote preparation or

Herbicide preparation or watered with the preparation of antidote and herbicidal active ingredient. The amount of water per unit area is expediently kept constant. The concentration of active ingredient in the preparation is irrelevant, only the amount of active ingredient applied per unit area is decisive. After three weeks, the degree of damage to the plants is rated in% damage in comparison to the development of the untreated control. The figures mean: 0% = no effect (like untreated control) 100% = total destruction Active ingredients, application rates and results are shown in the table below: Table A Pre-emergence test Active ingredient active ingredient active ingredient maize Echinochloa Herbicide effort, antidote effort Herbicide antidote kg / ha kg / ha CH3 3 - - 90 100 O C-CH2Cl N CH2-N C2H5 N - - N 3 0 10 CO-CHCl2 - - H5C2 3 0 0 N CH3 CO-CHCl2 - - CH3 3 0 0 H3C N CH3 CO-CHCl2 Table A (continued) Pre-emergence test Active ingredient active ingredient active ingredient maize Echinochloa Herbicide effort, antidote effort Herbicide antidote kg / ha kg / ha - - CH3 3 0 0 HN CO-CHCl2 - - CH3 3 0 0 N CH3 CO-CHCl2 CH3 ON 3 40 100 N C-CH2Cl CO-CHCl2 CH2-N C2H5 N CH3 O H5C2 3 20 100 N C-CH2Cl N CH3 CH2-N CO-CHCl2 C2H5 N Table A (continued) Pre-emergence test Active ingredient active ingredient active ingredient maize echinochloa Herbicide effort, antidote effort Herbicide antidote kg / ha kg-ha CH3 3 CH3 3 30 100 N CO-CH2Cl H3C N CH3 CH2-N CO-CHCl2 C2H5 N CH3 3 CH3 3 40 100 N CO-CH2Cl HN CH2-N CO-CHCl2 C2H5 N CH3 3 CH3 3 0 100 N CO-CH2Cl N CH3 CH2-N CO-CHCl2 C2H5 N

Claims (6)

Claims 1. Use of amides of the formula (I) in which represents hydrogen, halogen, optionally substituted by halogen, cycloalkyl, cyano, cyanato, thiocyanato, alkylthio, cycloalkyl, hydroxy, alkoxysulfonyl or phenyl, furthermore represents optionally halogen-substituted alkenyl, carbalkoxy, N-alkenylcarbamylalkyl, N-alkenylcarbamyl , N-alkyl-N-alkynylcarbamyl, N-alkyl-N-alkynylcarbamylalkyl, N-alkenylcarbamyl-alkoSyalkyl, N-alkyl-N-alkynylcarbamylalkoxyalkyl, alkynoxy, haloalkoxy, alkenylaminoalkyl, alkylcarbonylalkyl, alkenylaminosulfonylalkyl, haloalkylcarbonyloxyalkyl, alkalkenylaminosulfonylalkyl, haloalkylcarbonyloxyalkyl, alkaloxonyloxyalkyl, haloalkylcarbonyloxyalkyl, alkalkenylaminosulfonylalkyl, haloalkylcarbonyloxyalkyl, halogenoalkylcarbonyloxyalkyl, N-alkenylcarbamyl-carbamyl-alkyl -haloalkyloxyalkyl, hydroxyalkylcarbonylalkoxyalkyl, furyl, thienyl, alkyldithiolenyl, thienalkyl, optionally phenyl substituted by halogen, alkyl, haloalkyl, alkoxy, carbamyl, nitro, carboxylic acid radicals and their salts and / or haloalkylcarbamyl, for phenylhaloalkyl, optionally substituted by halogen, alkyl and / or alkoxy substituted phenylalkenyl, we iterhin for halophenoxy, phenylalkoxy, phenylalkylcarboxyalkyl, phenylcycloalkyl, halophenylalkenoxy, halothiophenylalkyl, halophenoxyalkyl, bicycloalkyl, alkenylcarbamylpyridinyl, alkynylcarbamylpyridinyl, dialkenylcarbamylpyridinyl, dialkenylcarbamylpyridinyl, dialkenylcarbamylbicycloamyl, or, optionally, are halo, and R 2 are, and R 2 are different, halo, and R 2 are, and R 2 are, hydrogen, and R 2 oxy-bicycloalkenyl or Alkylcarboxy, alkoxycarboxy, alkoxycarbonyl, alkoxy, mercapto, alkylsulfonyl and / or alkylamino-substituted alkyl, furthermore for optionally halogen-substituted alkenyl, alkynyl, thioalkylcarboxyalkyl, alkylcarbamyloxyalkyl, amines, formyl, haloalkyl-N-alkylamido, haloalkylamido, haloalkyl-N-alkylamidoalkyl, haloalkylamido, haloalkylamidoalkyl -alkylamidoalkyl, haloalkylamidoalkenyl, alkylimino, cycloalkyl, alkylcycloalkyl, alkoxycarbonylalkenyl, haloalkylcarbonyl, alkylcarbonyl, alkenylcarbamyloxyalkyl, cycloalkylcarbamyloxyalkyl, alkoxycarbonyl, haloalkoxycarbonyl, halophenylcarba myloxyalkyl, cycloalkenyl, optionally substituted by alkyl, halogen, haloalkyl, alkoxy, haloalkylamido, phthalamido, hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido or alkylcarbonylalkenyl substituted phenyl or phenylsulfonyl, also optionally substituted by halogen, alkyl, dioxyalkylene or halophenoxythylamidoalkyl diazolyl, piperidylalkyl, thiazolyl, alkylthiazolyl, benzothiazolyl, halobenzothiazolyl, furylalkyl, pyridyl, alkylpyridyl, alkyloxazolyl, tetrahydrofurylalkyl, 3-cyano-thienyl, 4,5-polyalkylenethienyl, -halogenaIkylacetylamido-alkyl, -halogenaIkylacetylphenyalkyl, -halogenaIkylacetylphenyalkyl, -halogenaIkylacetamidylphenyalkyl, -halogenaIkylacetylphenyalkyl, , where R2, however, does not stand for hydrogen or halophenyl, if R3 stands for hydrogen, and in addition R2 and R3 together with the adjacent nitrogen atom for optionally one or more times by alkyl, in particular methyl and / or ethyl, or piperidinyl substituted by methylcyclohexyl, it being possible for one CH2 group of the piperidinyl radical to be replaced by a C =O group; Perhydroquinolyl several times substituted by alkyl, in particular methyl, optionally 1,2,3,4-tetrahydroquinolyl substituted once or several times by alkyl, in particular methyl, 1,2,3 optionally substituted once or several times by alkyl, in particular methyl, 4-Tetrahydroindolyl or perhydroindolyl optionally substituted one or more times by alkyl, in particular methyl, as antidotes for improving the crop plant tolerance of herbicidally active acetanilines of the formula in which R stands for an optionally substituted N-containing heterocyclic radical, X and Y are identical or different and stand for alkyl, Z stands for halogen and n stands for 0, 1 or 2, as well as their herbicidally effective acid addition salts and metal salt complexes - or the formula in which R4 is alkyl, halogen, haloalkyl, alkylthio, alkylsulfonyl, aminosulfonyl, cyano or nitro, R5 and R6 are identical or different and are hydrogen, alkyl, halogen, haloalkyl or optionally substituted phenyl, R7 is alkyl or optionally substituted phenyl stands and m stands for integers from 0 to 5, - or the formula in which A stands for oxygen, sulfur or the grouping> NR13, R10 stands for hydrogen or alkyl, 11 R stands for hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, halogen, optionally substituted aryl and aralkyl or the group - OR14, -SR14 and NR13R14 13, R is hydrogen, alkyl, or optionally substituted aryl, R is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl or optionally substituted aralkyl, R8 is alkyl, R9 is alkyl or halogen, R stands for halogen and p stands for the numbers 0, 1 or 2. 2. Process for improving the crop plant tolerance of herbicidally active acetanilides of the formulas (II), (III) and (IV) according to claim 1 or of acid addition salts or metal salt complexes of active ingredients of the formula (II) according to claim 1, characterized in that amides of the formula (I) according to Claim 1 can act on the cultivated plants and / or their habitat. 3. means for selective weed control in crops of useful plants, characterized by a content of an active ingredient combination consisting of - an amide of the formula (I) according to claim 1 and - at least one acetanilide of Formula (II), (III) or (I5J) according to Claim 1 or an acid addition salt or Metal salt complexes of an active ingredient of the formula (II) according to Claim 1. 4. Methods for selective weed control in crops of useful plants, characterized in that an active ingredient combination according to claim 3 on the Weeds or their habitat can act. 5. Use of an active ingredient combination according to claim 3 for selective Weed control in crops of useful plants. 6. Process for the manufacture of compositions for selective weed control in crops of useful plants, characterized in that active ingredient combinations according to claim 3 mixed with extenders and / or surface-active agents.