GB2029223A - Oxime derivatives for the protection of cultivated crops - Google Patents

Oxime derivatives for the protection of cultivated crops Download PDF

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GB2029223A
GB2029223A GB7835335A GB7835335A GB2029223A GB 2029223 A GB2029223 A GB 2029223A GB 7835335 A GB7835335 A GB 7835335A GB 7835335 A GB7835335 A GB 7835335A GB 2029223 A GB2029223 A GB 2029223A
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lower alkyl
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/02—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

There is described a process for the protection of cultivated plants against harmful agricultural chemicals, which process comprises the use of oxime derivatives of the formula <IMAGE> (wherein the substituents R1, X and Q are as defined in the text) as antidotes. The cultivated area or the cultivated plants themselves, or parts of the plants (seed, tubers, sections of stalk, etc.), can be treated with these oxime derivatives.

Description

SPECIFICATION Oxime derivativesforthe protection of cultivated crops The present invention relates to the use of oxime derivatives of the general formula I
for the protection of cultivated plants against harm ful agricultural chemicals.
The symbols in the formula I have the following meanings: R1 is a radical -OR2 (in which R2 is an aliphatic group having a maximum of8 carbon atoms or an araliphatic group having a maximum of 15 carbon atoms, or a cycloaliphatic or aromatic group each having a maximum of 10 carbon atoms, and substituents of the aromatic radicals or of the cycloaliphatic radical can be halogen, -CH, -NO2, lower alkyl, lower alkoxy or haloalkyl); or a radical -NH-CO-NH-R4 or a radical -N (R3) (R4) (in which R3 is hydrogen or lower alkyl, and R4 is hydrogen or an aliphatic group having a maximum of 8 carbon atoms or an araliphatic group having a maximum of 15 carbon atoms or a cycloaliphatic or aromatic group each having a maximum of 10 carbon atoms, and possible substituents of the aromatic groups or of the cyloaliphatic radical are halogen,-CN, NO2, lower alkyl, lower alkoxy or haloalkyl); or a radical -N (R5) (us), (in which R5 and R6 together form a 5- or 6-membered heterocyclic rings which can also contain oxygen as a possible further hetero atom), X is hydrogen, -CN, halogen, lower alkyl, lower alkanoyl, -COOH, a carboxylic acid ester group or a carboxylic acid amide group, Q is hydrogen, a lower alkyl which can be interrupted by hetero atoms or can be substituted by halogen or cyano, or Q is lower alkenyl or haloalkenyl, lower alkynyl, C3-C7 cycloalkyl unsubstituted or substituted by halogen, or Q is a lower alkanecarboxylic acid ester group, a lower alkanecarboxylic acid thioester group, a lower alkanecarboxylic acid amide group, an aliphatic acyl group, an araliphatic, cycloaliphatic or substituted or unsubstituted aromatic or heterocyclic acyl group, an alkylsulfonyl group, a sulfonic acid amide group, a metal salt or an ammonium (e.g. quaternised) salt Halogen in the formula I is fluorine, chlorine, bromine or iodine.
Carboxylic acid esters and -thioesters are carboxylic acid lower alkyl esters and -lower alkylthioesters.
By acyl groups are meant carboxylic acid groups.
Carboxylic acid amides denote, besides-CON H2, also monoalkyl - substituted or symmetrically or unsymmetrically dialkyl - substituted amides, the alkyl groups being lower alkyl.
The term 'alkyl' on its own or as part of a sub stituent includes branched-chain or straight-chain C1- to C8-alkyl groups; and 'lower alkyl' on its own or as part of a substituent signifies C1-C4 alkyl.
Examples are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and also the higher homologues: amyl, isoamyl, hexyl, heptyl or octyl, together with isomers thereof. Obviously, alkanoyl or cyanalkyls contain an additional carbon atom; and, correspondingly, lower alkenyl or alkynyl groups contain a maximum of4 carbon atoms.
The term 'aliphatic group' includes radicals which are saturated (alkyls) and also unsaturated (alkenyls, alkadienyls or alkynyls), which are halogensubstituted, cyano-substituted and interrupted by oxygen, and which contain a maximum of 8 carbon atoms. The term 'aromatic group' includes phenyl and naphthyl. An 'araliphatic group' includes an unsubstituted or mono- to trisubstituted phenyl or naphthyl, which is bound by way of lower alkyl or lower alkenyl to the radical of the molecule. Exam ples are benzyl, phenethyl or phenylallyl, as well as homologues thereof.
The term 'heterocyclic acyl group' includes 5-to 6-membered heterocyclic carboxyl compounds having a ring hetero atom from the series N, O or S.
Examples are the radicals offurancarboxylic acid, thiophenecarboxylic acid, nicotinic acid, isonicotinic acid, and so forth. Cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
Cycloaliphatic radicals correspond to these ring systems, but in addition they may contain, if structurally possible, one or more double bonds.
Metal salts are to be understood as being cations of the I to IV groups of the periodic system, and also heavy metal salts. Examples are: Na, K, Ca, Mg, Al, Zn, Cu, Fe, Mn, Co and Ni.
Ammonium salts contain, as identical or different substituents, hydrogen, C1-C12 alkyl, lower hydroxyalkyl, benzyl, amino or di - lower - alkylamino, or form from two valencies and the N atom a 5- or 6membered heterocyclic ring having optionally a further hetero atom, namely N, O or S.
Oximes of the formula I are excellently suitable for protecting cultivated plants, such as rice, maize and varieties of cereals (cultivated millet, wheat, rye, barley or oats) from being attacked by agricultural chemicals harmful to cultivated plants, particularly by herbicides of the most varied classes of substances, in cases where these chemicals do not act selectively or not sufficiently selectively, that is to say, damage to a greater or less extent the cultivated plants in addition to destroying the weeds to be controlled.
There have already been suggested as antidotes various substances able to specifically antagonise the harmful action of a herbicide on the cultivated plant, that is to say, able to protect the cultivated plant without noticeably affecting the herbicidal action against the weeds to be controlled. Depending on its properties, an antidote of this type (also called a safener) can be used for the preliminary treatment of the seed of the cultivated plant (dressing of the seed or of the seedlings); or it can be applied into the seed furrows before sowing; or it can be applied as a tank mixture, on its own or together with the herbicide, before or after emergence of the plants.The pre-emergencetreat- ment includes both the treatment of the cultivated area before sowing (ppi = pre plant incorporation) and the treatment of the sown cultivated area before emergence of the plants.
Thus, the British Patent Specification No. 1,277,557 describes the treatment of seed and seedlings of wheat and sorghum with certain esters and amides of oxamic acid before the attack by N - methoxymethyl - 2',6' - diethylchloroacetanilide (Alachlor).
Other publications (German Offenlegungsschriften Nos. 1,952,910 and 2,245,471, and French Patent Specification No. 2,021,611) suggest antidotes for the treatment of cereals, maize seed and rice seed to protect them against attack from herbicidal thiolcarbamates. In the German Patent Specification No.
1,576,676 and U.S. Patent Specification No.
3,131,509, hydroxyaminoacetanilides and hydantoins are suggested for the protection of cereal seeds against carbamates, such as IPC, ClPC, and so forth.
In further development, however, none of these products has proved adequate.
To be emphasised as antidotes are those compounds of the formula I of the present invention in which R, is a radical (R3) (R4), wherein R3 is hydrogen or lower alkyl, and R4 is hydrogen or a lower aliphatic group, or a phenyl group unsubstituted orsubsti- tuted a maximum of three times by halogen, -CN, NO2, lower alkyl, lower alkoxy or CF3, X is hydrogen, -CN, lower alkyl, acetyl, -COO lower alkyl, -COONH2, -COONH - lower alkyl or -COON (lower alkyl)2, and Q is hydrogen, lower alkyl unsubstituted or substituted by halogen or cyano, or Q is lower alkenyl, lower alkynyl, an alkanecarboxylicacid- lower- alkyl ester group having a maximum of 7 carbon atoms, acetamide (-CH2-CONH2), a lower aliphatic acyi group, a substituted or unsubstituted benzoyl group, a 2 - furanoyl group, an alkali metal salt or heavy metal salt, or an ammonium salt of which possible substituents are hydrogen, lower alkyl, benzyl or hydroxyethyl. This group of substances is to be referred to as compound group la.
Within the compound group la, compounds which are important as antidotes are those in which R1 is a radical -NH-R4 wherein R4 is hydrogen or a lower alkyl group, X has the meaning given for la, and Qis hydrogen, lower alkyl, lower cyanalkyl, C3-C4 alkenyl, propargyl, acetamide, -CH2COO - lower alkyl or-CH (CH2) COO - lower alkyl. This subgroup is to be called compound group Ib.
Another group, preferred on account of the antidote action of the compounds contained thereip, is the compound group wherein R, is a radical -NH-CO-NH-R4, wherein R4 is hydrogen or a lower alkyl group, and wherein X and Q have the meanings given for compound group la. This active-substance type is to be referred to as compound group Ic.
Where Q within this group has the meaning it has in the case of compound group Ib, this activesubstance type is to be described as compound group Id.
A further compound group preferred by virtue of the antidote action of the compounds therein is the group in which R1 is a radical -OR2, wherein R2 is an alkyl, alkenyl or alkynyl group having a maximum of 6 carbon atoms, and wherein X and Q have the meanings given for them in the case of compound group la. This active-substance group is to be called compound group le. Where Q within this group has the meaning it has in the case of group Ib, this active-substance group is to be designated as com pound group If.
Surprisingly, oximes of the formula I have the property of being able to protect cultivated plants against attack from agricultural chemicals which are harmful to such plants, particularly against attack from herbicides of the most diverse classes of sub stances, including 1,3,5 - triazines, 1,2,4 - triazinones, phenylurea derivatives, carbamates, thiolcarba mates, phenoxyacetates, phenoxypropionates, haloacetanilides, halophenoxyacetates, substituted phenoxyphenoxyacetates and -propionates, substi tuted pyridinephenoxyacetates and -propionates, benzoic acid derivatives, and so forth, in cases where these chemicals are not compatible, or not suffi ciently compatible, with the cultivated plants.
Depending on the purpose of application, such an antidote of the formula I can be used for pretreat ment of the seed of the cultivated plant (dressing of the seed or of the seedlings); or it can be applied to the soil before or after sowing; or it can be applied on its own or together with the herbicide before or after emergence of the plants. The treatment of the plants or of the seed with the antidote can therefore be carried out essentially independently of the point of time of application of the phytotoxic chemicals. It can however be carried out also simultaneously (tank mixture). Pre-emergence treatment includes both the treatment of the cultivated area before sow ing (ppi = pre plant incorporation) and the treatment of the sown area before emergence of the plants.
The applied amounts of the antidote in proportion to the amounts of herbicide depend largely on the type of application. If a field treatment is undertaken, the amounts of antidote of the formula I with respect to the amounts of the phytotoxic chemical are in the ratio of 1:100to 5:1, preferably 1:20to 1:1. Inthe case of seed dressing and similar specific protective measures, much smaller amounts of antidote are required however compared with the amounts of herbicide employed for example subsequently per hectare of cultivated area (for example about 1:3000 to to 1 :1000). There exists as a rule only a loose con nection between protective measures, such as seed dressing with an antidote of the formula I, and a possible subsequent field treatment with agricultural chemicals. Pretreated seed and plant material can later come into contact, in agriculture, horticulture and forestry, with a variety of chemicals.
The invention relates therefore also to composi tions for protecting cultivated plants, which compos itions contain as active substance merely an antidote of the formula I together with customary inert car riers. Compositions of this type can optionally be additionally mixed with those agricultural chemicals having an effect from which the cultivated plant is to be protected; for example they can be mixed with a herbicide.
Within the scope of the present invention, culti vated plants are all plants which produce in some form useful materials (seeds, roots, stalks, tubers, leaves, blossom, and components such as oils, sugar, starch, protein, and so forth), and which are cultivated and attended to for this purpose. These plants include for example all varieties of cereals, maize, rice, cultivated miliet, soya bean, beans, peas, potatoes, vegetables, cotton, sugar beet, sugar cane, peanuts, tobacco and hops, and also ornamental plants, fruit trees as well as banana, cocoa and natural rubber plants. This list of plant types does not constitute any limitation. An antidote can as a rule be used everywhere where a cultivated plant has to be protected against the phytotoxicity of a chemical.
The invention relates to a process for the protection of cultivated plants against harmful (phytotoxic) agricultural chemicals, in which process an oxime derivative of the formula I, which has an antidote action, is employed either before or after application of the agricultural chemical, or simultaneously with the agricultural chemical.
The invention relates also to the propagative organs of cultivated plants, which organs have been protected by treatment with an oxime derivative of the formula I. Bytheterm "propagative organs" are meant all generative plant parts which can be used for the propagation of the cultivated plants. These parts include seeds (seed in the narrower sense), roots, fruits, tubers, rhizomes, parts of stems, cuttings and other parts of plants. Also included however are germinated plants and seedlings which, after germination or emergence, are to be transplanted. Young plants of this kind can be specifically protected, by a complete or partial immersion treatment, before being transplanted.
Compounds of the formula I can be produced by known methods of oximation of compounds of the formula II R,-CO-CH2-X (II) (with the meanings given under the formula I) by reacting with nitrous acid (HNO2) or with an organic or inorganic nitrite; and then converting the resulting free oximes with bases into the salts, or acylating the free oximes with acids or acid halides, or converting them, with radicals splitting off halogen, into other oxime ethers mentioned under Q. The following may be cited as relevant literature: German Offenlegungsschriften Nos. 2,312,956 and 2,350,910; and also "Berichte der deutschen chem.
Gesellschaft"42, p. off. [1909].
Oximes are present in two stereoisomeric forms, the syn and anti form. By 'compounds of the formula I' are accordingly meant, within the scope of the present specification, both stereoisomeric forms, on their own or as mixtures with each other in any reciprocal ratio.
The Examples which follow illustrate the production of oximes of the formula I. Temperature values are given in degrees Centigrade.
Example 1 Production of
a - cyano - a - hydroxyimino - acetyl - urea 50 g of cyanacetylurea is added at 80"C in the course of 5 minutes, with vigorous stirring, to 50 g of sodium nitrite in 250 ml of water, and the temperature is then raised to 100". After the addition is completed, the reaction mixture is stirred at room temp eraturefor a further hour, and is subsequently cooled to 10" The formed sodium salt of the final product is filtered off, and dissolved, with heating, in 200 ml of water. To the solution is then added 70 ml of concentrated hydrochloric acid, and the mixture is finally cooled and filtered to yield a - cyano - a hydroxyiminoacetyl - urea having a melting point of 210-212 (with decomposition).
Example 2 Production of
a - cyano - a - allyloximino - acetamide To a solution of 11.3 g (0.1 mol) of a - cyano - a - oximino - acetamide in 100 ml of acetonitrile is added 10.1 g (0.1 mol) of triethylamine, and 12.1 g (0.1 mol) of allylbromide is then added dropwise.
Refluxing is subsequently carried out for4 hours, and the solution is concentrated in vacuo. The residue is taken up in methylene chloride, the organic phase is repeatedly washed with water, dried over sodium sulfate, stirred up with active charcoal, and filtered until clear. The filtrate is concentrated by evaporation to yield 12.7 g (= 83.0'/c of theory) of final product having a melting point of 79-80".
In this manner or by one of the aforementioned methods, there can be produced the following compounds of the formula:
Camp. X Q - Physical No. constants 1 -CN H m.p. 185-187 2 -CN -CH2CN m.p. 165-167 3 -CN -CH2-coNH2 m.p. 194-196 4 -CN -CH2-CeCH m.p. 101-1030 5 -CN -CH(CH3) COOCH3 oil 6 -CN -CH(CH3) COOC2H5 oil 7 -CN -CH2-CH=CH2 m;p. 79-80 8 C1 -CH2CN 9 C1 C82 -CONH2 10 . C1 -CH1. -CH2-COOCH3 oil 11 Cl -CH(CH3) COOCH3 oil 12 Cl -3l(rlig) COOC2H5 oil 13 Cl -MZ-CCH viscous 14 -COCH3 -CH2-CN oil 15 -COCH3 < -12 CsCH oil 16 -COCH3 -COONH3 -CH2-f.OOCEJ3 oil 17 -COCH3 -CH(CE3)COOC2H5 oil 18 -COCH3 -CH2-COOC3H(iso) oil 19 -COCH3 -CH2-CONH2 viscous 20 -CN NH(083)2-c12H25(n) m.p. 74.75,50 21 -CN t NH3-CH3 m.p. 136-138 22 -CN (i3H2N O np. 153
Comp. X -Q Physical No. constants 23 -CN 1/3 Fe m . p . m.p. > 300' (decomp.j 24 -CN NH3 N(CH3)2 m.p. .133-1340 25 -CN CH3 m.p. 171 26 -CN C2115 m.p. 1260 27 -CN C3117 (iso) viscous 28 -CN 2-furanoyl m.p. 2000(decomp.) 29 -CN -COCH m.p. 141-143 CRI22 -OH 30 -CN (3 HN-C12H25 (n) oil CH2CH2011 31 -CN 6) NH3-sec . C4H9 m.p. 91-97 32 -CN NH2(CH3)2 m.p..145-1470 33 -CN O+H2NN'i2O+ m.p. 2400(decomp.) 34 -CN Cd15$2CH2 C6U5CR2-. N1-c121125(n) CH2CH2-OH 35 -CN OHZN(CH2CH29H)2 oil ;6 -CN O HN(CH3)3 m.p. 138-1420 and also following compounds of the formula:
Comp. R4 X Q Physical .No. constants 37 H2N-CO -CN CH2CN oil 38 H5C2NH-CO- -CN CH2CN oil 39 H5C6-NH-CO- -CN -CH2CN oil 40 H2N-CO- -CN -CH2-CONH2 oil 41 H2N-CO- -CN -CH2-COOCH3 oil 42 N5C2-NH-CO- -CN -CH2-COOC2H5 oil 43 H2N-CO- -CN -CH(CH3)-COOCK3 viscous 44 H5C2-NH-CO- -CN -CH(CH3)-COOC2H5 viscous 45 H5C6-NH-CO- -CN -CH2-COOCH3 oil 46 H2N-CO- Cl -CN2CN oil 47 H3C-NH-CO- C1 -CH2CN oil 48 H5C2-NH-CO- C1 -CH2CONH2 viscous 49 H2N-CO- C1 -CH2-COOCH3 oil 50 H2N-CO- Ci -CH(CH3COOC3H7 (iso) oil 51 H5C2-NH-CO- Cl -CH(CH3) COOC2H5 oil 52 H2N-CO- C C 3 -CH2CN oil 53 nH9C4-NH-CO- -COCH3 -CH2CN oil 54 H3C-NH-CO- -COCH3 -CH2CN oil 55 H2N-CO- -COCH3 -CH2COOCH3 oil 56 H5C2-NH-CO- -COCH3 -CH2COOC2H5 oil 57 H5C2-NH-CO- -COCH3 -CR(CR3)COOC2R5H Oil 58 H3C-NH-CO- -COCH3 -CH(CH3)COOCH3 oil 59 H2N-CO- - -COCH3 -CH2-CONH2 oil 60 H2N-CO- CN #H3NCH3 m.p. 176 (decomp.)
Comp. R4 X Q Physical No. constants 61 H2N-CO- CN 6 NH4 m.p. 209' (decomp.) 62 H2N-CO- CN Q+NH(CR3)2-NH2 m.p. 125-126 63 H2N-CO- CN o+H2N30 n.p. 160-165' 64 H2N-CO- CN Na O m.p. 250' (decomp.) 65 H2N-CO- CN H m.p. -210-2120 66 H2N-CO- CN Ji Zn *+ m.p.200 (decomp.) 67 H2N-CO- CN F Co ++ m.p. 2300%decomp.) 68 H2N-CO- CN 2-furanoyl m.p. 198 (decomp.) 69 H2N-CO- CN 4 Fe +F m.p. > 300 (decomp.) 70 H2N-CO- CN -CH2-C-CH m.p. 176-181 71 H2N-CO- CN O N;i(CH3)2-C12H25 (")m.p. 110-113 72 H2N-CO- CN O NH3-sec.c4H9 m.p. 149 73 H2N-CO- CN Q+NH(CR3)2-CR2CR2011n.p. 125-128 74 H2N-CO- CN &commat; ONH2(CH2CH2'0H)2 m.p. 136-138 75 H2N-Co- CN ONH2(CH3)2 m.p. 171-1720 76 H2N-CO- CN O NH(CH3)3 m.p. 160 (decomp.) 77 H2N-CO- COOCH3 -CH2CN oil 78 H3C-NH-CO COOCH3 -CH2COOCH3 oil 79 H3C-NH-CO COOCH3 -CH2CN oil 80 H3C-NH-CO COOCH3 -CH(CH3)COOCH3 oil 81 H5C6-NHCO COOCH3 -CH2CN - oil 82 H5C6NH-CO COOCH3 -CH(CH3)COOC2H5* > viol 83 H2N-CO CN sMn ++ m.p. > 300 84 H5C2NH-CO CN H m.p. 166.168' 85 H5C2NH-CO CN CH3 m.p. 62 86 cyclo- CN 4 Cu ++ m.p. 149.50 propyl (decomp.) 87 cyclo- CN. 4 Co ++ m.p. > 300 propyl (decomp.) 88 cyclo- CN H m.p. 202 hexyl 89 CH3 CN OH2Cn.p.121123' &commat;H2N 90 CH3 CN 6 H3N-N(CH3)2 solid 91 nC4H9 CN H m. p.125-126,50 92 CH3 CN 2-furanoyl m.p.187 (decomp.) 93 CH3 CN -CH2CN m.p.91-93 94 cyclopropyl CN H m.p. 181 CR2CR20H 95 CH3 CN 8 NH-C12H25(n) oil CH2CH20H 96 CH3 CN &commat; NH(CH3)2C12H25(n)m.p. 92-93 97 CH3 CN ss NH3-sec.C4H9 m.p.146-1480 98 CH3 CN ONH3-CH3 m.p.175 99 CH3 CN &commat; NH2(CH3)2 m.p.75-78 100 CH3 CN -CO-C6H3C12(3,4)m-p.167-168 101 2H3c0 -c6H4- CN H m.p.166-168" 102 C6H5- H H m.p.181,5" 103 ' 3,4(c12)c6H3- H H m.p. 167 104 3.5(c12)c6H3- H H m.p. 196 105 3-CF3-C6H4- H H m.p. 137 106 4-CF3-C6H4- H H m.p. 1?1' 107 4-C1,3-CF3-C6H3- H H m.p. 1780 108 2-CH3,4-C1-C6H3- H H n.p. 170-1740 109 3-C1-C6H4- H H rn.p. 146-150 110 3-(CR3) C6H4 - H H m.p. 125-1290 and also following compounds of the formula:
Comp. Q Physical No. constants 111 H m.p. 225 (decomp.) 112 t Cu++ m.p. 210'(decomp.) 113 Co++ m.p. > 330 (decomp.) 114 N++ m.p. 280 (decomp.) 115 # NH3-sec.C4H9 m.p. 112 116 #NH2(CH2CH2OH)2 oil 117 # NH2(CH3)2 oil 118 #NH(CH3)2-C12H25(n) oil and also following compounds of the formula:
Comp.R2 X Q Physical No. constants 119 C2H5 -CN H. m.p.133-136 120 C2H5 -CN -S02CH3 m.p.81-830 121 CH3 -CN -CH2COOCH3 oil 122 C2H5 -CN -CH(CH3) COOCH3 oil 123 C2H5 -CN -CH2-COOC2H5 oil 124 CH3 -CN -CH2CN oil 125 CH3 5 -CN -CH2CONH2 viscous 126 i-C3H7 -CN -CH2COOC3H7(iso) oil 127 cyclo- -CN -C92CN oil oil propyl Comp.R2 X Q Physical No. constants 128 CH3 C1 -CH2CN viscous 129 CH3 C1 -CH2COOCH3 viscous 130 cyclo- C1 -CH2CN oil propyl 131 C2H5 C1 -CH(CH3)COOC2H5 viscous 132 CH3 -COCH3 -CH2CN oil 133 CH3 -COCH3 -CH2CONH2 oil 134 C2H5 -COCH3 -CH2COOC2H5 oil 135 CH3 -COCH3 -CH(CH3) COOCH3 . oil 136 CH3 -CO-OCH3 -CH2CN oil 137 CH3 -CO-OCH3 -CH2CONH2 viscous 138 CH3 -CO-OCH3 -CH2COOCH3 oil 139 CH3 -CO-OCH3 -CH(CH3)COOCH3 oil 140 CH3 -COCH3 H oil 141 C2H5 CH3 H m.p. 95-96 142 C2H5 -COCH3 H solid 143 CH3 -CO-OCH3 -CH2-C=Ch semi-crystalline 144 C2H5 -CO-OC2H5 -CH2-C=CH viscous 145 C2H5 -CO-OC2H5 CH3 oil 146 02115 -CO-OC2H5 C2H5 oil 147 C2H5 -CO-OC2H5 -CH2CN oil 148 C H -COCH3 CH3 oil 149 C2H5 -COCH3 C2H5 oil 150 C2H5 -COCH3 -CR2-C=CH oil 151 C2H5 -COCH3 -CH2-CH=CH2 oil 152 C2H5 -CO-(C2H5 -CH2-CH=CH2 oil 153 .C2H5 -CN CH3 oil 154 C2115 -CN 02115 -oil 155 C2115 -CN C3H7(iso) oil 156 C2115 -CN -CH2-CH=CH2 viscous 157 02115 -CN CH2 -C=CH viscous and also following compounds of the formula:
Comp-.R' X Q Physical No. constants 158 -(CH2) 5- CN -CH2CN oil 159 -(CH2)5- CN -CH2-C=CH viscous 160 -(CH2)5- CN -CH2-COOCH3 oil 161 -CH2CH2-0-CH2CH2- CN -CH2CN oil 162 -CH2CH2-O-CH2CH2- -COCH3 -COCH3 viscous 163 -CH2CH2-O-CH2CH2- -COCH3 CH3 viscous 164 -(CH2) 5- -COCH3 02115 viscous 165 -(CH2)5- -COOCH3 -CH2-CH=CH2 oil 166 -(CH2)4- --CN -CH2-CONH2 resin 167 -(CH2)4- -CN -CH2-COOC3H7(n) resin 168 -(CH2)4- -COOC2H5 C2H5 resin 169 -(CH2)4- -COOC2H5 -CH(CH3)COOC2H5 resin 170 -(CH2)5- H C2H5 oil 171 -(CH2)4- H -CH2-CaCH resin 172 -CH2CH2-O-CH2CH2- H -CH(CH3)COSC2H5 oil 173 -(CH2)5- CH3 H oil 174 -(CH2)4- CH3 -CH2CO-NH2 resin 175 -CH2CH2-O-CH2CH2 CH3 SO2NH2 oil 176 -CH2CH2-O-CH2CH2 CH3 cycloproryl oil As already mentioned, various methods and tech niques are suitable for application of the compounds of the formula I for the protection of cultivated plants against agricultural chemicals: 1) Seed dressing a) Dressing of the seed with an active substance formulated as a wettable powder by shaking in a vessel until there exists a uniform distribution over the surface of the seeds (dry dressing). The amount of active substance of the formula I used for this purpose is about 10 to 500 g (40 g to 2 kg of wettable powder) per 100 kg of seed.
b) Dressing of the seed with an emulsion concentrate of the active substance of the formula I using method a) (wet dressing).
c) Dressing by immersion of the seed in a liquor containing 50-3200 ppm of active substance of the formula I for 1-72 hours and, optionally, subsequent drying of the seed (immersion dressing).
The dressing of the seed or the treatment of the germinated seedlings are naturally the preferred methods of application because the treatment with the active substance is directed completely at the target crop. There is used as a rule 10 g to 500 g, preferably 50 to 250 g, of active substance per 100 kg of seed, it being possible, depending on the method used, which method enables also the addition of other active substances or micronutrients to be made, to deviate either upwards or downwards from the given limiting concentrations (repeat dressings).
2) Application as a tank mixture A liquid preparation of a mixture of antidote and herbicide (reciprocal quantitative ratio between 1:20 and 5:1) is used, the applied amount of herbicide being 0.1 to 6 kg per hectare. A tank mixture of this kind is preferably applied before or immediately after sowing, or is worked into the unsown soil to a depth of 5-10 cm.
3) Application into the seed furrow The antidote is introduced, as an emulsion concentrate, wettable powder or granulate, into the open sown seed furrow and, after covering of the seed furrow in the normal manner, the herbicide is applied using the pre-emergence process.
Essentially, the antidote can therefore be applied before, together with, or after the herbicide, and its application to the seeds or to the field can be effected either before or after sowing, or in certain cases also after germination of the seed.
4) Controlled release of active substance The active substance in solution is absorbed onto mineral granulate carriers or onto polymerised granules (urea/formaldehyde), and the material is allowed to dry. It is possible if desired to apply a coating (coated granules), which enables the active substance to be released in controlled amounts over a specific period of time.
It is naturally possibleto employ also all other known methods of applying active substances.
Examples in this connection are given later in the text.
The compounds of the formula I can be used on their own or together with suitable carriers and/or other additives. Suitable carriers and additives can be solid or liquid and they correspond to the substances common in formulation practice, such as natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/orfertilisers.
The content of active substance in commerical compositions is between 0.1 and 90%.
The compounds of the formula I can be in the following forms for application (the weightpercentage figures in brackets signify advantageous amounts of active substance): solid preparations: dusts and scattering agents (up to 10%), and granulates [coated granules, impregnated granules and homogeneous granules] (1 to 80%); liquid preparations: a) water-dispersible concentrates of active substance: wettable powders and pastes (25 to 90% in the commercial packing, 0.01 to 15% in ready-for-use solutions); emulsion concentrates and solution concentrates (10 to 50 /O; 0.01 to 15% in ready-for-use solutions); b) solutions (0.1 to 20%) and aerosols.
The active substances of the formula I of the present invention can be formulated for example as follows.
Granulate: The following substances are used to produce a 5% granulate: 5 parts of active substance, 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, and 91 parts of kaolin (particle size 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, and the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed onto kaolin, and the acetone is subsequently evaporated off in vacuo.
Wettable powder: The following constituents are used to produce a) a 70% wettable powder and b) a 10% wettable powder: a) 70 parts of active substance, 5 parts of sodium dibutylnaphthylsulfonate, 3 parts of naphthalenesulfonic acid/phenolsulfonic acid/formaldehyde condensate 3:2:1, 10 parts of kaolin, and 12 parts of Champagne chalk; and b) 10 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulfates, 5 parts of naphthalenesulfonic acid/formaldehyde condensate, and 82 parts of kaolin.
The active substances are intimately mixed in suitable mixers with the additives, and the mixture is then ground in the appropriate mills and rollers.
There are obtained wettable powders which have excellent wetting and suspension properties, and which can be diluted with water to give suspensions of the desired concentration.
Emulsifiable concentrate: The following substances are used to produce a 25% emulsifiable concentrate: 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulfonate/ fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide, and 57.5 parts of xylene.
Emulsions of the desired concentration can be prepared from these concentrates by dilution with water.
Pre-emergence antidote test in nutrient solution A Hewitt nutrient solution is prepared, which contains the amount of herbicide given below and 10 ppm of the antidote to be tested.
There is used cultivated seed which could be expected to suffer damage from the employed herbicide at the given test concentration, and the seed is sown in granulated Zonolite (= expanded vermiculite) which is contained in a plastic flower pot having a pierced bottom (upper diameter 6 cm). This pot is placed into a second transparent plastic flower pot (upper diameter 7 cm), in which there is about 50 ml of the nutrient solution that has been prepared with herbicide and antidote; this solution then rises by capillary attraction in the filler material of the smaller pot and wets the seed and germinating plants. The loss of liquid is made up daily with pure Hewitt nutrient solution to 50 ml.Three weeks after commencement of the test, an evaluation is made on the basis of a linear scale from 1 to 9, with the rating 1 signifying total plant destruction, and the rating 9 signifying an unimpaired condition of health of the plants. The control solution used in a parallel test contains no antidote addition.
There are used the following: 1) 4 ppm of Prometryne = 2,4 - bis - (isopropylamino) - 6 - methylthio - s- triazine in sorghum-millet of the "Funk G-522" variety; 2) 4 ppm of 4 - ethylamino - 6 -tert - butylamino 2 - chloro - s - triazine in wheat of the "Farnese" variety; 3) 4 ppm of a - [4 - (p - trifluoromethylphenoxy) phenoxy] - propionic acid - n - butoxyethyl ester in barley of the "Mazurka" variety; 4) 5 ppm of Metolachlor = N - (1 - methyl - 2 methoxy- ethyl) - N - chloroacetyl -2 - ethyl - 6- methylaniline in sorghum-millet of the "Funk G-522" variety; and 5) 1 ppm of 2 - methoxy - 4,6 - bis - (z- methoxypropylamino) - s - triazine in sugar beet of the "Kleinwanzleben" variety.
Compounds of the formula I exhibited in these tests a good antidote action.
Post-emergence antidote test in nutrient solution General procedure Plastic flower pots (upper diameter 6 cm), which have a pierced bottom, are filled with granulated Zonolite and the cultivated seeds are sown therein.
The pot is placed into a second transparent plastic flower pot (upper diameter 7 cm) in which there is 50 ml of water, which rises by capillary attraction and wets the seeds. From the 5th day the continuous loss of water is compensated with Hewitt nutrient solution. From the 15th day, when the cultivated plants are in the 11/2-to 2-leaf stage, there is added to the nutrient solution, made up again to 50 ml, a) 10 ppm of the antidote to be tested + the amount of herbicide given below, and b) 1 ppm of the antidote to be tested + the amount of herbicide given below.
From the 16th day, the loss of liquid is again made up with pure Hewitt nutrient solution. During the entire duration of the test, the temperature is 20-23"C with a relative humidity of 60-70%. Three weeks after addition of the herbicide and antidote, an evaluation is made on the basis of a linear scale from 1 to 9, with 1 signifying total plant destruction, and 9 an unimpaired conditions of health of the cultivated plants.
Test variants 1) 15 ppm of a -[4 - 3,5 - dichloropyridyl - 2 - oxy) - phenoxy] - propionic acid propargyl thiol ester in wheat of the "Zenith" variety; 2) 4 ppm of 4 - ethylamino - 6 - tert - butylamino 2 - chloro - s - triazine in wheat of the "Zenith" variety; 3) 2 ppm of a - [4 - (p - trifluoromethylphenoxy) phenoxy] - propionic acid - n - butoxyethyl ester in maize of the "Orla" variety; 4) 8 ppm of a-[4- (p - trifluoromethylphenoxy) phenoxy] - propionic acid - n - butoxyethyl ester in sorghum-millet of the "Funk G-522" variety; 5) 4 ppm of Prometryne = 2,4 - bis - (isopropylamino) - 6 - methylthio - s - triazine in sorghum-millet of the "Funk G-522" variety; and 6) 8 ppm of a - [4 - (3,5 - dichloropyridyl - 2 - oxy) phenoxy] - propionic acid methyl ester in wheat of the "Zenith" variety.
Compounds of the formula I have a good antidote action in these tests, for example Compound No. 1.
Antidote test with seed soaking Rice seeds of the IR 8 variety are saturated during 48 hours with solutions of the test substances of 10 or 100 ppm concentration. The seeds are subsequently allowed to dry for about 2 hours, until they no longer stick together. Rectangular plastic pots (8 x 8 cm, 10 cm in height) are filled up to within 2 cm of the edge with sandy loam. In each pot is sowed 4 g of seed, and the seed is only very slightly covered (about the diameter of a seed). The soil is maintained in a moist (not boggy condition). There is then applied either the herbicide N - (1 - methyl - 2 - methoxyethyl) - N chloroacetyl - 2 - ethyl - 6 - methylaniline or N - propoxyethyl - N - chloroacetyl - 2,6- diethylaniline in dilute solution and in an amount which converted corresponds to 1.5 kg of active substance per hectare. An evaluation is made 18 days after planting on the basis of a linear scale from 1 to 9, according to which the rating 1 signifiestotal plant destruction, and the rating 9 an unimpaired condition of health of the plants.
Compounds of the formula I exhibit in this test a good antidote action.

Claims (32)

1. A process for the protection of cultivated plants against harmful agricultural chemicals, which process comprises applying to said plants or parts thereof, or to the locus of their growth a compound of the formula I
in which R, is a radical -OR2 (wherein R2 is an aliphatic group having a maximum of 8 carbon atoms or an araliphatic group having a maximum of 15 carbon atoms, or a cycloaliphatic or aromatic group each having a maximum of 10 carbon atoms, and substituents of the aromatic radicals or of the cycloaliphatic radical can be halogen, -CN, -NO2, lower alkyl, lower alkoxy or haloalkyl); or a rndical-NH-CNH-R4 ora radical-N (R3) (R4), (wherein R3 is hydrogen or lower alkyl, and R4 is hydrogen oran aliphatic group having a maximum of 8 carbon atoms or an araliphatic group having a maximum of 15 carbon atoms ora cycloaliphatic or aromatic group each having a maximum of 10 carbon atoms, and possible substituents of the aromatic groups or of the cycloaliphatic radical are halogen, -CN, NO2, lower alkyl, lower alkoxy or haloalkyl); or a radical -N (R5) (R6) (wherein R5 and R6 together form a 5- or 6-membered heterocyclic ring which can also contain oxygen as a possible further hetero atom), X is hydrogen, -CN, halogen, lower alkyl, lower alkanoyl, -COOH, a carboxylic acid ester group or a carboxylic acid amide group, Q is hydrogen, a lower alkyl which can be inter rupted by hetero atoms or can be substituted by halogen or cyano, or O is lower alkenyl or haloal kenyl, lower alkynyl, C3-C7 cycloalkyl unsubstituted or substituted by halogen, or O is a lower alkanecar boxylicacid ester group, a loweralkanecarboxylic acid thioester group, a lower alkanecarboxylic acid amide group, an aliphatic acyl group, an araliphatic, cycloaliphatic or substituted or u nsubstituted aromatic or heterocyclic acyl group, an alkylsulfonyl group, a sulfonic acid amide group, a metal salt or an ammonium salt.
2. A process according to Claim 1 wherein there is applied a compound of the formula I in which R1 is a radical -N (R3) (R4), wherein R3 is hydrogen or lower alkyl, and R4 is hydrogen or a lower aliphatic group, or a phenyl group unsubstituted or substituted a maximum of three times by halogen, -CN, NO2, lower alkyl, lower alkoxy or CF2, X is hydrogen, -CN, lower alkyl, acetyl, -COQ lower alkyl -COONH2, -COONH - lower alkyl or -COON (lower alkyl)2, and Q is hydrogen, lower alkyl unsubstituted or substituted by halogen or cyano, or Q is lower alkenyl, lower alkynyl, an alkanecarboxylic acid - lower - alkyl ester group having a maximum of 7 carbon atoms, acetamide, a lower aliphatic acyl group, a substituted or unsubstituted benzoyl group, a 2 - furanoyl group, an alkali metal salt or heavy metal salt or an ammonium salt, possible substituents being hyd rogen, lower alkyl, benzyl or hydroxyethyl.
3. A process according to Claim 2 wherein there is applied a compound of the formula I in which R1 is a radical -NH-R4 wherein R4 is hydrogen or a lower alkyl group, X is as defined in Claim 2, and Q is hyd rogen, lower alkyl, lower cyanalkyl, C3-C4 alkenyl, propargyl, acetamide, -CH2COO - lower alkyl or -CH(CH3)COO - lower alkyl.
4. A process according to Claim 1 wherein there is applied a compound oftheformula I in which R1 is a radical -NH-CNH-R4, wherein R4 is hydrogen or a lower alkyl group, and wherein X and Q are as defined in Claim 2.
5. A process according to Claim 4 wherein there is applied a compound of the formula I in which Qis as defined in Claim 3.
6. A process according to Claim 1 wherein there is applied a compound of the formula I in which R, is a radical -OR2, wherein R2 is an alkyl, alkenyl or alkynyl group having a maximum of 6 carbon atoms, and X and 0 are as defined in Claim 2.
7. A process according to Claim 6 wherein there is applied a compound of the formula I in which 0 is as defined in Claim 3.
8. A process according to Claim 1 wherein there is applied a compound of the formula I specifically identified herein.
9. A process according to any one of Claims 1 to 8, wherein the crop area of cultivated plants is treated with the compound of the formula I either before or after application of an agricultural chemical.
10. A process according to any one of Claims 1 to 8, wherein the crop area of cultivated plants is treated simultaneously with an agricultural chemical and the compound of the formula I.
11. A process according to any one of Claims 1 to 8, wherein the cultivated plants or parts thereof are treated with the compound of the formula I before cultivation.
12. A process according to Claim 11, wherein the generative parts of the plant are treated.
13. A generative part of the cultivated plant, which part is treated with a compound of the formula las defined in Claim 1.
14. A generative part of a cultivated plant, which part is treated with a compound of the formula las defined in any one of Claims 2 to 7.
15. A generative part of a cultivated plant, which part is treated with a compound of the formula I as defined in Claim 1 specifically identified herein.
16. A composition for the protection of cultivated plants against harmful agricultural chemicals, which composition contains an antidote, a compound of the formula I as defined in Claim 1, together with an inert carrier material.
17. A composition according to Claim 16, which contains, as antidote, a compound of the formula las defined in any one of Claims 2 to 7.
18. A composition according to Claim 16, which contains, as antidote, a compound of the formula I specifically identified herein.
19. An agricultural composition which contains an agricultural chemical, and, as antidote for cultivated plants, a compound of the formula I as defined in any one of Claims 1 to 8.
20. Acompositon according to Claim 19, wherein the agricultural chemical is a herbicide.
21. Acomposition according to Claim 20, wherein the herbicide is a 1,2,4 - triazine.
22. A composition according to Claim 20, wherein the herbicide is a chloroacetanilide.
23. A composition according to Claim 20, wherein the herbicide is a 4 - (phenoxy) - phenoxypropionic acid ester.
24. A composition according to Claim 20, wherein the herbicide is a 4 - (pyridyloxy) - phenoxypropionic acid ester.
25. A composition according to any one of claims 16 to 24 which contains a solid extender and, optionally, a surface active agent or a liquid diluent and a surface active agent.
26. A process according to claim 2 wherein there is applied a compound of the formula
wherein R3 and R4 independently represent hydrogen or methyl, or an alkali or alkaline earth metal salt thereof or an ammonium salt thereof wherein the ammonium group comprises one, two or three alkyl and/or hydroxyalkyl groups the sum of whose carbon atoms is at most 6.
27. A process according to claim 4 wherein there is applied a compound of the formula
or an alkali or alkaline earth metal salt thereof or an ammonium salt thereof wherein the ammonium group comprises one, two or three alkyl and/or hydroxyalkyl groups the sum of whose carbon atoms is at most 6.
28. A process according to claim 6 wherein there is applied the compound of the formula
29. A process according to any one of claims 26 to 28 wherein the crop area of cultivated plants is treated with the said compound either before or after application of a herbicide selected from 1,3,5 triazines or chloroacetanilides.
30. A process according to any one of claims 26 to 28, wherein the crop area of cultivated plants is treated simultaneously with the said compound and a herbicide selected from 1,3,5 - triazines or chloroacetanilides.
31. A process according to any one of claims 26 to 28 wherein parts of the plant are treated before cultivation.
32. Acomposition according to claim 16, wherein the compound of the formula I is as defined in any one of claims 26 to 28.
GB7835335A 1978-09-04 1978-09-01 Oxime derivatives for the protection of cultivated crops Expired GB2029223B (en)

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CH928978A CH637268A5 (en) 1978-09-04 1978-09-04 AGENT FOR THE PROTECTION OF PLANT CULTURES.

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EP0072970A1 (en) * 1981-08-22 1983-03-02 Bayer Ag Substituted anilinomethylene oximes, method for their preparation and their use as herbicides
EP0387499A2 (en) * 1989-02-16 1990-09-19 Bayer Ag Substituted oxine ethers and their use as pesticides
WO1995020569A1 (en) * 1994-01-27 1995-08-03 Ciba-Geigy Ag Process for the preparation of arylacetic ester derivatives via palladium-catalyzed cross coupling reaction

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DE3041998A1 (en) 1980-11-07 1982-06-09 Bayer Ag, 5090 Leverkusen PYRAZOLE-SUBSTITUTED OXIMINO-CYAN-ACETAMIDE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES
GR76342B (en) * 1981-02-02 1984-08-06 Fujisawa Pharmaceutical Co
CH654979A5 (en) * 1982-01-26 1986-03-27 Sandoz Ag FUNGICIDES AND THEIR USE.
DE3206235A1 (en) * 1982-02-20 1983-09-01 Bayer Ag, 5090 Leverkusen SUBSTITUTED OXIMINOACETANILIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PEST CONTROL
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Also Published As

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FR2434572A1 (en) 1980-03-28
FR2434572B1 (en) 1981-12-11
AT367268B (en) 1982-06-25
ATA635778A (en) 1981-11-15
LU80181A1 (en) 1979-05-15
DE2837863A1 (en) 1980-03-13
BE870067A (en) 1979-02-28
AU533146B2 (en) 1983-11-03
GB2029223B (en) 1982-09-15
CH637268A5 (en) 1983-07-29
NL7809000A (en) 1980-03-04
AU4464179A (en) 1980-03-06

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