DD149992A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The invention relates to novel herbicidal compositions based on azolyloxycarbonsaeureamiden. The aim of the invention is an increase in activity over known compounds and a Selektivitaetsverbesserung. The novel compounds corresponding to general formula I, wherein R is a five-membered heteroaromatic monocycle containing an oxygen or a sulfur atom and additionally 1 to 3 nitrogen atoms and which may optionally be substituted; R & exp1! = H, alkyl; R & exp2! and R & exp3! = same or different with other meanings. The E ndprodukte have a significantly improved and a different herbicidal activity with good compatibility with crops.

Description

Herbicidal agents

Field of application of the invention

The invention relates to novel azolyloxy-carboxamides and their use as herbicides »

Well-known technical solutions

It has already become known that certain phenoxy-carboxylic acid amides, such as. B. 2,4-dichlorophenoxy-acetic acid amide, herbicidal v / are effective (see PR-PS 1 313 840). However, the known as herbicides Phenoxycarbonsäureamide show only a small effect against weed grasses at the usual rates and can not be used on the control because of lack of selectivity ·

Object of the invention

It is the object of the invention to bring about an increase in the efficiency and selectivity.

Explanation of the essence of the invention

The invention has for its object to provide new active herbicidal agents based on azolyloxy-carboxamides.

There have now been new Azolyloxy-carboxamides of the formula

HO-CH-CO-N E ¹

found in which

E is a five-membered heteroaromatic monocycle which contains one oxygen or one sulfur atom and additionally 1 to 3 nitrogen atoms and which is optionally substituted by halogen, nitro, cyano, amino, alkylamino, dialkylamino, alkylcarbonylamino, alkylcarbonyl, carboxy, alkoxycarbonyl, carbamoyl, Alkylaminocarbonyl, dialkylaminocarbonyl, arylaminocarbonyl optionally substituted by halogen, nitro or alkyl, aryl optionally substituted by halogen, nitro, cyano, alkyl, haloalkyl or alkoxy, optionally halogen substituted aralkyl, optionally halogen substituted alkoxy, alkenoxy, alkynoxy, alkoxycarbonylalkoxy, aralkoxy or aryloxy, optionally halogen-substituted alkylthio, alkenylthio, alkynylthio, alkoxycarbonylalkylthio, aralkylthio, arylthio, alkylsulfinyl or alkylsulfonyl, optionally halogen-substituted alkyl, alkenyl, alkynyl, alkoxyalkgcl, aralkoxyalkyl, aryloxyalkyl, alkylthioalkyl, Al kylsulfinylalkyl, alkylsulfonylalkyl, arylthioalkyl, arylsulfinylalkyl, arylsulfonylalkyl, carboxyalkyl, alkoxycarbony1-alkyl, optionally substituted aminocarbonylalkyl, cyanoalkyl or cycloalkyl, in which further

E is hydrogen or alkyl, and

and E ^ are the same or different and are individually hydrogen, each optionally substituted alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, aryl or a nitrogen-containing heterocyclic or together with the nitrogen atom to which they are attached, an optionally substituted, optionally partially form unsaturated and optionally benzo-fused mono- or bicyclic, which optionally contains further heteroatoms.

The azolyloxy-carboxamides of the formula (I) are obtained when 6-hydroxycarboxamides of the formula

HO-CH-CO-N

in which

E ', B ^ and E ^ have the meaning given above, with haloazoles of the formula

E-HaI (III)

E has the meaning given above and Hai is chlorine, bromine or iodine,

if appropriate in the presence of an acid acceptor and if appropriate using a diluent

Although some of the novel compounds of the formula (I) can also be synthesized in other ways, for example

from the corresponding hydroxy azoles (or the tautomeric azolones thereof) and oC-halocarboxamides, or from corresponding azolyloxycarboxylic acid esters and amines; however, the scope of application of these methods is relatively low.

The new azolyloxy-carboxamides of the formula (I) are distinguished by strong herbicidal activity.

Surprisingly, the new azolyloxy-carboxamides show a much better and different herbicidal action than the Phenoxycarbonsäureamide known from the prior art. In particular, surprised the fact that the compounds of the invention with good compatibility with crops in addition to their high activity against dicotyledonous weeds also show very good activity against weeds, while constitutionally similar phenoxy-alkanecarboxylic such as z, B. 2,4-dichlorophenoxy-acetic acid amide, only have little effect against Gramineae.

The invention preferably Azolyloxycarbonsäureamide of the formula

0-CH-CO-N (Ia)

in which

£ for CR ¹ "or N,

D stands for CE ⁵ or N, for CE ⁶ , N, 0 or S! is CE ^, N, 0 or S,

E is CE ⁶ , N, O or S and

with the proviso that at least one of the king members (A, D, B or G) is N and at least one of the Bing members is O or S;

in which further

B ^{1 is} hydrogen or methyl, Ir and R, which may be the same or different, individually represent hydrogen, alkyl, cyanoalkyl, alkoxyalkyl, alkylthioalkyl, alkenyl, alkynyl, each of up to 10 carbon atoms, cycloalkyl of up to 12 carbon atoms, aralkyl with 1 or 2 carbon atoms in the alkyl moiety and 6 or 10 carbon atoms in the aryl part which is optionally substituted by halogen, or aryl with 6 or 10 carbon atoms, wherein the aryl moiety is substituted by 1 to 3 halogen atoms, 1 to alkyl or haloalkyl groups each of 1 to 4 carbon atoms, nitro, cyano or alkoxy may be substituted with 1 to carbon atoms, or wherein the Eeste E and Ir together with the nitrogen atom to which they are attached, one optionally substituted by 1 to 3 alkyl groups each having 1 to 5 carbon atoms or by two geminal alkoxy groups each having 1 to 3 carbon atoms substituted or optionally by Dioxolanyliden- or Dioxa nylidene radicals spirocyclic-linked substituted, optionally partially unsaturated and / or benzannellated monocycle or bicyclic having up to 15 carbon atoms form, or wherein the Eeste E and E ^ together with the nitrogen atom to which they are attached, optionally by 1 to 3 Alkyl groups each having 1 to 5 carbon atoms, by phenyl, which may be

is substituted by C ^ -C ^ alkyl, C ^ -C ^ alkoxy, halogen, C ^ -C ₂ haloalkyl or nitro, substituted by benzyl or phenylethyl, saturated and another nitrogen atom, oxygen atom or sulfur atom-containing monocycle with bis to form 5 carbon atoms;

in which further H, Ir, E and K, which may be the same or different, individually represents hydrogen, halogen, nitro, cyano, amino, C 1 -C 4 -alkylamino, C 1 -C 4 -alkylamino, C 1 -C 8 -alkyl C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkylcarbonyl, carboxy, C 1 -C 4 alkoxy carbonyl, carbamoyl, C 1 -C 4 alkylaminocarbonyl, di-C 1 -C 4 alkylamino carbonyl, optionally phenyl-amino-carbonyl substituted by halogen, nitro or C 1 -C 4 -alkyl, optionally substituted by halogen, nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl or Си-С ^ -Аікоху Phenyl, optionally substituted by halogen substituted benzyl or phenylethyl, optionally substituted by halogen C ₁ -C ₂ J-AIkOXy, C ₂ -C ^ alkenoxy, C ₂ -C ^ alkynoxy, C ^ -C ^ - alkoxycarbonylmethoxy , Benzyloxy or phenoxy, for optionally halogen-substituted C 1 -C 4 -alkylthio, C ₂ -C 4 -alkenylthio, C ₂ -C 4 -alkynylthio, C 1 -C 4 -alkoxycarbonylmethylthio, benzylthio, phenylthio, C 1 -C 4 -alkylthio, -SC ^ - alkylsulfinyl or C ^ -C ^ alkylsulfo nyl, for optionally halogen-substituted C ^ -Cg-alkyl, C ₂ -C ₆ -alkenyl or C ₂ -Cg -alkynyl, for cyano-Cj-C ^ -alkyl, C ^ -C ^ - А1коху-Си-С ₂ -alcyl, phenoxy- and phenylthio-methyl, benzyloxy- and benzylthiomethyl, C 1 -C 4 -alkylthio-C 1 -C ₂ -alkyl, C 1 -C 4 -alkyl- and phenylsulfinyl-Oxy- alkyl,

- and phenylsulfonyl Cj - ^ - alkyl, carboxy ^C 1 ~ ^C 2 ^{"alkyl" G} ^ i ^ -C alkoxy-caxbony 1-C ^ -al -C _2] sy 1, C ^ -C ^ alkylamino carbODyI-C ₁ -C ₂ -SIk ^ l, di-C ^ -C ^ -alkyl-aminocarbonyl-C _/ jC ₂ alkyl, Phenylaminocarbonylalkyl or Co-C ^ ₂ · are -Cyсloalkyl

The invention particularly relates to compounds of the formula (I) in which

R * ^{1 is} hydrogen,

E is hydrogen, СЦ-Сс-Аікуі, cyanoethyl, ethyl, allyl, propargyl, 1-methyl-propargyl, 1,1-dimethylpropargyl, cyclopentyl, cyclohexyl, phenyl or benzyl,

R ^{3 is} C ₁ -C ₅ -alkyl, cyanoethyl, Oj-C ^ alkoxy-ethyl, allyl, P propargyl, 1-methyl-propargyl, 1,1-dimethylpropargyl, cyclopentyl, cyclohexyl, benzyl, naphthyl or phenyl, which optionally substituted by 1 to 3 radicals (methyl, fluorine, chlorine, trifluoromethyl, cyano, nitro or methoxy),

or wherein the radicals R and R ^ together with the nitrogen atom to which they are attached represent pyrrolidyl, monoalkyl or dialkyl-pyrrolidyl having 1 to 3 carbon atoms per alkyl group, morpholinyl or dialkylmorpholinyl having 1 to 3 carbon atoms per alkyl group, piperidyl, monoalkyl -, dialkyl or trialkylpiperidyl having 1 to 3 carbon atoms per alkyl group, for 4,4-dialkoxy-piperidyl having 1 to 3 carbon atoms per alkoxy group, for spiro-substituted piperidyl of the formula

Orin η is 2 or 3, perhydroazepinyl (hexamethyleneimino radical), trimetyl-perhydroazepinyl, for the heptamethyleneimino radical, for the dodecamethyleneimino radical, for 1,2,3,4-tetrahydroindolyl, for monoalkyl, dialkyl or trialkyl-1,2,3,4-tetrahydroindolyl having up to 3 carbon atoms per alkyl group, perhydroindolyl, monoalkyl, dialkyl or trialkylperhydroindolyl having from 1 to 3 carbon atoms per alkyl group, 1,2,3,4-tetrahydroquinolyl or 1,2,3,4-tetrahydro-iso-quinolyl, monoalkyl, dialkyl or Trialky1-1,2,3,4-tetrahydroquinolyl or -iBochinolyl having 1 to 3 carbon atoms per alkyl group for perhyaroquinolyl or perhydro-iso-quinolyl , Monoalkyl, dialkyl or trialkylperhydroquinolyl or perhydroisoquinolyl having from 1 to 3 carbon atoms per alkyl group, perhydrothiazolyl, perhydrooxazolyl, perhydrooxazinyl, the remainder

-N N-E »

wherein E ^{f is} C ^ -C ^ alkyl, optionally substituted by Cj-C ₂ alkyl, C ^ -C ₂ ~ alkoxy, fluorine, chlorine, bromine, trifluoromethyl ω2d / or nitro substituted phenyl, benzyl or phenylethyl or wherein the radicals E ^ and E ^ together with the nitrogen atom to which they are attached, for the Eest

stand, in which further

E represents one of the following azolyl radicals

Λ O

, 11

13

E ²⁰

17

лъ

15

19

wherein

Each X is oxygen or sulfur and the moiety E to R 3, which may be the same or different, individually represents hydrogen, bromine, chlorine, nitro, cyano, Ⓒ, ω-co-alkoxycarbonyl, optionally through Fluorine, chlorine or bromine, methyl, halomethyl, hethoxy, nitro and / or cyano mono- or di-substituted phenyl, phenoxy or phenylthio, C ₁ -C 4 -alkyl or C 1 -C 4 -alkoxy, C C 1 -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl, C 1 -C 4 -alkyl, trifluoromethyl, trichloromethyl, cyano-C 1 -C 4 -alkyl, C ₂ -C 4 -alkenyl, benzyloxymethyl, C ₁ -C 4 -alkylsulfinyl or C 1 -C 4 -alkylsulfonyl; ^ -С ^ -Аікуі-атіпо, N-Cj-C ^ - alkyl-N-Си-С ^ -аікуі-атіпосагЬопуі, benzylthio or phenoxymethyl

If, for example, 2,4,5-trichloro-thiazole- (i, 3) and hydroxyacetic acid-piperidide are used as starting materials, the course of the reaction according to the process according to the invention can be represented by the following formula scheme:

^/ ^ -HCl

HO-CH ₂ -CO-N У

Cl 0 -CH ₂ -CO-N

The C-hydroxycarboxylic acid amides to be used as starting materials are defined by formula (II). In this formula, E, E and B are preferably or in particular for those best, which are already mentioned in the context of the substituent definitions of the formula (I) preferably or as particularly preferred.

As starting materials of the formula (II), mention may be made, for example:

Hydroxyacetic acid-methylamide, -ethylamide, -n-propylamide, -iso-propylamide, -n-butylamide, -iso-butylamide, -dimethylamide, -diäthylamid, -di-n-propyl-amide, -di-iso-propylamide, - N-methyl-N, iso -propyl-amide, -N-methyl-N-iso-butyl-amide, -N-methyl-N-sec-butyl-amide, -N-propyl-N-sec-butyl -amide, -N-methyl-N- (2-cyano-ethyl) -amide, -di- (2-methoxy-ethyl) -amide, -di-allyl-amide, -N-methyl-N-propargyl-amide , -N-methyl-N- (i-metbyl-propargyl) -amide, -dipropargyl-amide, -cyclopentyl-amide, -N-methyl-N-cyclopentyl-amide, -cyclohexyl-amide, -N-methyl-N -cyclohexyl-amide, -anilide, -2-nitro, -3-nitro-4-nitro-phenyl-amide, 2-chloro, 3-chloro and 4-chlorophenyl-amide, -2,4-dichloro , 2,5-dichloro, ЗС ^^ ісЫог- and 3,5- <3-chloro-phenyl-amide, -2-methyl, -3-methyl- and -A-methyl-phenyl-amide, -N-methyl -anilide, -N-methyl-N- (2-nitro-phenyl) -, -N-methyl-N- (3-nitro-phenyl) -, -N-methyl-N- (4-nitro-phenyl) - amide, -N-methyl-N- (2-chloro-phenyl) -, -N-methyl-N- (3-chloro-phenyl) -, -N-methyl-N- (4-chlorophenyl) -amide , -N-methyl- N- (3-nitro-6-methyl-phenyl) -amide, -N-ethylanilide, -N-ethyl-N- (2-nitro-phenyl) -, -N-ethyl-N- (3-nitrophenyl) - , -N-ethyl-N- (4-nitrophenyl) -amide, -H-ethyl-N- (2-chlorophenyl) -, -N-ethyl-N- (3-chlorophenyl) -, -N-ethyl-N- (4-chloro-phenyl) -amide, -N-ethyl-N- (3-nitro-6-methyl-phenyl) -

amide, -N-propyl-anilide, -N-propyl-N- (2-nitro-phenyl) -, -N-propyl-N- (3-nitro-phenyl) -, -N-propyl-N- (4 -nitro-phenyl) -amide, -N-propyl-N- (2-chlorophenyl) -, -N-propyl-NO-chloz * -phenyl) -, -N-propyl-NC-i-chloro> _phenyl ) -amide, -N-propyl-N- (2-tetramethylphenyl) -, N-propyl-N- (3-niethyl-phenyl) -, -N-p3 -phenyl-N- (4-methyl-phenyl) phenyl) -amide, -N-propyl-N- (3-nitro-6-methylphenyl) -amide, -N-butyl-anilide, -N-butyl-N- (2-nitrophenyl) -, --N- Butyl-N- (3-nitro-phenyl) -, -N-butyl-N, N-n-ciphenyl) -amide, N-butyl-N- (2-chloro-phenyl) -, -N-butyl-N- (3-chlorophenyl), -N-butyl-N- (4-chloro-3-phonon) -amide, -N-butyl-N- (2-methyl-phenyl) -, -N-butyl-N- (3-methyl-phenyl) -, -N-butyl-N- (4-methylphenyl) -amide, -N-butyl-NG-pi-gob-ib-methyl-phenyl) -amide, -N-isobutyl-anilide , -N-iso-butyl-N- (2-nitro-phenyl) -, -N-iso-butyl-N- (3-nitro-phenyl) -, -N-isobutyl-N- (4-nitro-phenyl ) -amide, -N-iso-butyl-N- (2-chlorophenyl) -, -N-isobutyl-N-chloro-phenyl) -, N-isobutyl-N- (4-chloro-2-phenyl) -amide , -N-iso-butyl-N- (2-methyl-phen3'l) -, -N-iso-butyne LN- (3-methyl-phenyl) -, -N-iso-butyl-N- (4-methylphenyl) -amide, -N-iso-butyl-N- (3-nitro-6-methyl-phenyl) -amide , naphthyl (1) ylamide, naphth (2) ylamide, N-methyl-N-naphth (i) -ylamide, N-methyl-N-naphth (2) ylamide, N-ethyl-N-naphth (i) -ylamide, -N-ethyl-1-naphth (2) ylamide, -N-propyl-N-naphth (2) -ylamide, -N-iso-propyl-N-naphth (2) ylamide, Nn-butyl-N-naphth (2) ylaraid, N, ieo-butyl-N-naphth (2) ylamide, benzylamide, dibenzylamide, N-methyl-N-benzylamide, N-ethyl-N-benzylamide , -N-propyl-N-benzylamide, -N-butyl-N-benzylamide, -pyrrolidide, -2-methyl-pyrrolidide, -morpholide, -piperidide, -2-methyl-piperidide, -4-methyl-piperidide, - 2,4-dimethyl-piperidide, -2,4,6-trimethyl-piperidide, -2-ethyl-piperidide,

4-ethyl-piperidide, 2,4-diethyl-piperidide, -2,4,6-triethyl-piperidide, 1-methyl-1-ethyl-piperidide, 2-methyl-piperidide, 2-methyl 5-ethyl-piperidide, -g-methyl-piperidide, ~ 2-methyl-6-ethyl-piperidide, -1,2,3,4-tetrahydroindolide, -2-methyl-1,2,3,4-tetrahydroindolide , -perhydroindolide, ^ -methylperhydroindolide, -2,2-dimethylperhydroindolide, -1,2,3,4-tetrahydroquinolide, -2-methyl-1 »2» 3, ^ -tetrahydroquinolide, -perhydroquinolide, 2-methylperhydroquinolide, i ^^^ - tetrahydro-isoquinolide and -perhydroisoquinolide.

The oC-hydroxycarboxylic acid amides of the formula (II) are known in some cases (see US Pat. Nos. 3,399,988 and 5,647,481 to DS-OS * 2,201). They can be prepared starting from oC-chloro-carboxylic acid chlorides, as outlined in the following scheme:

Cl-CH-CO-Cl

(IV)

-HCl

Cl-CH-CO-N (VI)

E ²

+ CHoCOQNa (K) -NaCl (KCl)

+ NaOH (KOH) -CH ₃ COONa (K)

CHO-CO-O-CH-CO-N ¹

(VII)

HO-CH-CO-N (ID

For this purpose, the literature known c-chlorochlorochlorochlorides chlorides of formula (IV) with amines of the formula (V) - wherein R, R and R- * have the abovementioned meaning - optionally in the presence of an acid binder such. For example, triethylamine and optionally using an inert diluent such as. B. 1,2-dichloroethane, at temperatures between -20 and 100 ⁰ C, preferably between -10 and 50 ⁰ C in the corresponding chlorocarboxylic acid amides of the formula (VI). The workup of these products is carried out by conventional methods by washing with water, drying the organic phase and distilling off the solvent.

The compounds of formula (VI) are treated with sodium or potassium acetate, optionally using a diluent such as. B, acetic acid or dimethyl sulfoxide, at temperatures between 20 and 150 ⁰ C, preferably between 50 and 120 ⁰ C, to the corresponding o ε -Acetoxycarbonsäureamiden the formula (VII). As far as the products are crystalline, they are isolated by suction. Otherwise, the workup is carried out by conventional methods, for example by distilling off the solvent in vacuo, taking up the residue in methylene chloride, washing with water and distilling off the solvent.

By reaction with aqueous-alcoholic sodium hydroxide or potassium hydroxide at temperatures between 0 and 100 ⁰ C, preferably between 10 and 50 ⁰ C, the compounds of formula (VII) can be deacylated to the compounds of formula (II). The solvents are isolated to isolate the products

distilled off in vacuo, the residue with an organic solvent such as. As methylene chloride or ethyl acetate, the solution was dried and the solvent distilled off.

The equatorial halogenazoles to be used as starting materials are defined by formula (III). In this formula, E is preferably or in particular for those which are already preferably mentioned in the context of the substituent definitions of the formula (I) or which are particularly preferred, and Hal is preferably chlorine or bromine.

Abs starting materials of the formula (III) may be mentioned, for example:

2-chloro- and 2-bromo-oxazole and -thiazole, 2,4-dichloro, 2,5-dichloro and 2,4,5-trichloro-oxazole and -thiazole, 4-methyl-, 5-methyl- , 4-tert, -butyl, 4,5-dimethyl, 4-methyl-5-chloro, 5-methyl-4-chloro, 4-metbyl-5-methoxycarbonyl, 4-methyl-5-ethoxycarbonyl -, ^ - methyl - ^ - isopropoxycarbonyl, 4-methyl-5-acetyl, 5-phenyl, 4,5-diphenyl, 4-chloro-5-phenyl, 4-chloro-5- (3, ^ -dichlorophenyl) - and 4-

Methyl 5-phenylthio 2-chloro-oxazole, -2-bromo-oxazole, -2-

chlorothiazole and 2-bromothiazole; 3- * 6rt-butyl-4-cyano, 3-but-3-en-1-yl, 3,4-bis-ethoxycarbonyl, 3-phenyl, 3-ethyl-4-phenyl-5- chloro-isoxazole, -5-chloro-isothiazole, -5-bromo-isoxazole and -5-bromo-isothiazole; 3 »5-bis-ethoxycarbonyl-4-chloro and 5-bis-ethoxycarbonyl-4-bromo-isoxazole and -isothiazole; -^ -БісЬіог-І ^ Д-охааіагоі, 3-methyl, 3-ethyl, 3-a-propyl, 3-iso-propyl, 3-tert-butyl, 3-trifluoromethyl, 3 Trichloromethyl, 3-methylthio, 3-methylsulfinyl, 3-methylsulfonyl-5-chloro-1,2,4-thiadiaol and -5-bromo-1,2,4-thiadiazole | 4-methyl-5-cyano-2-chloro and

} 4-methyl, 4-ethyl,

4-n-propyl and 4-iso-propyl 3-chloro-1,2,5-thiadiazole and

- ^ - bromo-i ^ j ^ -thiadiazol; 2-chloro and 2-bromo-1,3,4-oxadiazole, 2-chloro and 2-bromo-1,3,4-thiadiazole, 5-methyl, 5-butyl, 5-n-propyl , 5-isopropyl, 5-tert-butyl, 5-bromo, 5-methylsulfinyl, 5-ethylsulfinyl, 5-propylsulfinyl-5-methylsulfonyl, 5-ethylsulfonyl, 5- Propylsulfonyl, 5-methoxycarbonyl, 5-ethoxycarbonyl, 5- (i-cyano-2-methylpropyl) -, ^ - benzyloxymethyl, 5-acetylamino, 5-nitro, 5-propylthio, 5-trifluoromethyl, 5-trichloromethyl, 5-methylamino and ^ - (N-hetbyl-N-tert-butylcarbonyl-amino) -2-chloro-1,3,4-oxadiazole, 2-bromo 1,3 » ^z * -oxadiazole, 2-chloro-1,3,4-thiadiazole and -2-bromo-1,3» 4-thiadiazole

Halogenazoles of the formula (III) are known (see Elderfield, Heterocyclic Compounds VoI £ (1957), p. 298 and p. 452; Vol. 2. (1961), p. 463 and p. 541; Weissberger, The Chemistry of Heterocyclic Compounds, (a) "Five-Membered Heterocyclic Compounds viith Nitrogen and Sulphur or Nitrogen, Sulfur and Oxygen ¹¹ (1952), p. 35 and p. 81, (b)" Five-and Six-Membered Compounds with Nitrogen and Oxygen "( 5, pp. 245 and p.263; Advances in Heterocyclic Chemistry, Vol. Д (1965), p.1199, Vol. £ (1966), p.183; Vol. £ (1968), p Synthesis 1978 , 803, Tetrahedron Letters 1968 , 829, Chem, Ber · 8 $., 107, p.165 and p.183; Vol. 12 (1974), p. 99 and Vol. 20 (1976), p , (1956), 1534-i £ 0 (1957), 182; Q2 (1959) 1928; J. Org. Chem., 2, p. (1962), 2589, pi-OS 2 213 865).

Some of the haloazoles to be used as starting materials are not yet described in the literature. Various halogen-azoles is obtained for example by dissolving appropriate amino-azole with hydrohalic acids in water and reacting under Siskühlung with sodium nitrite, the mixture is stirred for some hours at temperatures between 10 and 50 ⁰ C, the products extracted with toluene and after washing and drying the organic phase worked up by distillation (see DE-OS 2,144,326).

The process according to the invention for preparing the novel azolyloxycarboxamides (I) is preferably carried out using suitable solvents or diluents. As such, virtually all inert organic solvents are suitable. These include in particular alcohols such as methanol, ethanol, n- and iso-propanol, n-, І80-, sec- and tert-butanol, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and Methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, and the highly polar solvents dimethylformamide, dimethyisulfoxide, sulfolane and hexamethylphosphoric triamide,

As acid acceptors in the process according to the invention, it is possible to use virtually all customary acid binders: these include, in particular, alkali and alkaline earth hydroxides or oxides, such as sodium and potassium hydroxide and calcium oxide or calcium hydroxide,

Alkali metal and alkaline earth metal carbonates such as sodium, potassium and calcium carbonate, alkali metal alkoxides such as sodium methoxide, ethylate and tert-butylate, potassium methoxide, ethylate and tert-butylate, furthermore aliphatic, aromatic or heterocyclic amines such as triethylamine , Dimethylaniline, dimethylbenzylamine, pyridine, diazabicyclooctane and diazabicycloundecene.

The reaction temperature can be varied within a wide range. In general carried out between -50 and +150 ⁰ C, preferably at -20 to + 100 ⁰ C.

The process of the invention is generally carried out at atmospheric pressure.

In carrying out the process according to the invention, 1.0 to 1.4 mol of oC- hydroxycarboxamide of the formula (II) are employed per mole of haloazole of the formula (III). The reaction is generally carried out in a suitable diluent and the reaction mixture is stirred at the required temperature for several hours.

The products are isolated by customary methods. If appropriate, part of the diluent is distilled off under reduced pressure and the reaction mixture is poured into water. Insofar as the products are obtained in crystalline form, they are isolated by suction.

Otherwise, the organic products with a water-immiscible solvent such. For example, toluene or methylene chloride extracted; After washing and drying, the solvent is then distilled off from the organic phase in vacuo. The remaining products are characterized by their melting point or their refractive index.

The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, germ inhibitors and in particular as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides essentially depends on the amount used.

The active compounds according to the invention can, for. B. be used in the following plants:

Dicotyledonous weeds of the genera:

Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecic, Amaranthus, Portulaca, Xanthium, Convolvulus, Impomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Eorippa, Eotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicotyle cultures of the genera:

Gossypiuin, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cuburbita _e

Monocotyledonous weeds of the genera:

Echinochloa, Setaria, Panicum, Digitaria, Pheieum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ishaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocotyl cultures of the genera:

Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

The compounds are suitable depending on the concentration for total weed control z. B. on industrial and railway tracks and on paths and squares with and without Baumbevmchs. Likewise, the compounds for weed control in permanent crops z · B, forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber,

oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops.

In addition to a very good action against grassy weeds, the active compounds according to the invention also have a good herbicidal action on broad-leaved weeds. Selective use of the agents of the invention is possible in various cultures, e.g. In turnips, soybeans, cotton, rice and other cereals. In this case, individual active ingredients are particularly suitable as selective herbicides in beets, cotton and cereals.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, active-ingredient-impregnated natural and synthetic substances, microencapsulations in polymeric substances.

These formulations are prepared in a known manner, for. B. by mixing the active compounds with extenders, ie liquid solvents and / or solid Txäge substances, optionally with the use of surfactants, emulsifiers and / or dispersants and / or schaiinierzeugenden agents. In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. When

Liquid solvents are essentially: aromatics, viie xylene, toluene, or Alky! naphthalenes, chlorinated aromatic or chlorinated aliphatic ^ hydrocarbons such as chlorobenzenes, Chloräthyleno or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, z. B. petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulfoxide and water,

Suitable solid carriers are: z. B, natural gesture inmehie, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as finely divided silica, alminium oxide and silicates ·, as solid carriers for granules are: z. B, crushed and fractionated natural rocks such as CaIcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-producing agents are in question: z. Nonionic and antionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as dispersants in question: z. As lignin-sulphite liquors and methylcellulose,

Bs can be used in the formulations adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate ·

It possible to use colorants such as inorganic pigments, for example, _# Bisenoxid, titanium oxide, Forrocyanblau and organic dyestuffs, such as alizarin dyestuffs, metal phthalocyanine, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds in admixture with known herbicides, ready-to-use formulation or tank mixing being possible. It is also possible to mix it with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, growth substances, plant nutrients and soil conditioners.

The active compounds can be used as such, in the form of their formulations or the preparation forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is carried out in a customary manner, for example by pouring, spraying, spraying, spreading or dusting,

The active compounds according to the invention can be applied both before and after emergence of the plants. The application is preferably made before the emergence of the plants, so in the pre-emergence process, · They can also be incorporated before sowing in the soil.

The amount of active ingredient used can vary within larger ranges. It depends essentially on the type of effect desired. In general, the application rates are between 0.01 and 10 kg.Wirkstoff per ha, preferably between 0.1 and 5 kg / ha.

Some of the active compounds according to the invention also have a growth-regulating action at certain application concentrations.

The following examples serve to illustrate the invention.

Production Examples Example 1

14.8 g (0.09 mol) of hydroxyacetic acid N-methylanilide are dissolved in 100 ml of isopropanol, the solution is stirred with 5.6 g of powdered potassium hydroxide and cooled to -15 ⁰ C. At -15 ⁰ C 13.1 g (0.07 mol) of 2,4,5-trichlorothiazole are added dropwise in one hour. The mixture is left for 3 hours at -10 ⁰ C stirring and then the temperature to rise to ⁰ ° C, stirred for 2 hours at ⁰ C and then 10 hours at Hardly temperature · Then, distilled ЗА of the solvent, the residue is poured into water and the precipitated Sucked solids and dried. The yield is 18 g (81% of theory)} Melting point: 82 ⁰ Cj -0- (4,5-dichloro-1,3-thiazol-2-yl) oxyacetic acid-N-methylanilide -

Example 2 Cl

r.

O N

9 g (0.05 mol) of hydroxyacetic acid N-methylanilide are dissolved in 100 ml of acetonitrile. Then 7.6 g of potassium carbonate are added. At -10 ⁰ C Vierden 6.9 g of 3,5-dichloro-1,2,4-oxadiazol slowly added dropwise. The mixture is then stirred for 2 hours at -10 ⁰ C ₁ 3 hours.bei O - 5 ⁰ C and stirred for 20 hours at room temperature · Then the acetonitrile is distilled off in vacuo to 1/4, poured the residue on water and the product with toluene extracted. After distilling off the toluene, the substance crystallizes. The yield is 9 g (70% of theory); Melting point 73 ^° C .; OO-chloro-1,2,4-oxadiazol-5-yl) -oxyacetic acid N-methylanilide

Example 3

CH ₂ -CO-Ii (CH ₃ )

8i ⁶ g (0.082 mol) of hydroxyacetic acid dimethylamide are stirred in 150 ml of tert-butanol together with 11.2 g of potassium tert-butylate. At 20 ⁰ C slowly 13 »3 S 5-chloro-3-isopropyl-1,2,4- 6hiadiazol are added dropwise. It is allowed to stir for 4 hours at about 40 ⁰ C. Then the tert-butanol is distilled off in vacuo to 3/4 and poured the residue to 7 / asser. The precipitated oil is extracted with toluene. After distilling off the toluene, the product remains as a crystallizate back in a yield of 9 g (50 % of theory) and having a boiling point of 67 ⁰ C; 0- (3-Isopropyl-1,2,4-thiadiazol-5-yl) -oxyacetic acid dimethylamide -

Example 4

N ^ CH ₃

8.7 g (0.05 mol) of 2-Hyd: roxyessigsäure-N-methylanilide are stirred together with 3 g of calcium oxide in 60 ml of dimethylsulfoxide for 1 hour at 50 ⁰ C. Then, at 50 ⁰ C are added dropwise 11.6 g of 5-bromo-2-trifluonnethyl-1,3,4-thiadiazole and 40 hours at 50 ⁰ C stirred · The solution is then poured onto 1 1 of water and the precipitated oil with methylene chloride extracted. After distilling off the methylene chloride, the product remains as an oil back in a yield

21 out of 10 g with a refractive index of n £: 1.54-04 ·;

O- (2-trifluoromethyl-1-1,3,4-thiadiazol-5-yl) -oxyacetic acid N-methylanilide

Example 5 CH ^ S

0-CH ₂ -CO-N

H V

8.3 g (0.05 mol) of 5-chloro-3-methylthio-1,2,4-thiadiazole are added at 20-30 ^° C. to a mixture of 8.5 g (0.05 mol) of 2-hydroxyacetic acid, Added 4-dimethylpiporidid, 3.4 g (0.06 mol) of potassium hydroxide powder, 1 g of copper powder and 100 ml of isopropanol. The mixture is stirred for several hours

and then diluted with water, then the product is extracted with toluene, the organic phase is washed with water, dried, filtered and the solvent is removed from the filtrate in vacuo. The yield is 9 g (60 % of theory); Refractive index: nip = 1.54-60; O- (3-methylthio-1,2,4-thiadiazol-5-yl) -oxyacetic acid N- (2,4-dimethylpiperidide) -

Analogously to one of Examples 1 to 5, the following compounds of the formula Ib

Cl Cl

0-CH ₂ -CO-IT

getting produced:

Table 1

Bei- / Br Physical. dates

game -N о (refractive index;

No. ⁴ JT melting point ^U C)

б ^CH 3 n * ³ : 1.5449

38

8 -N (CH 1) ρ 85

* i 1,5399

At game no. -N (CH ₂ -CH = CH ₂ J ₂ Physical. Data (refractive index, melting point ⁸ C) io -N «T)) ₂ n ^ ³ : 1.5418 11 127 12 -O-O 125 13 -N (C ₃ H ₇ -ISO) ₂ 62 63 15 CH ₃ 68 16 -N-CH-CSCH n £ ¹ : l, 55lo 17

C C

H ₃ C CH ₃

18 -N (CH ₂ -CH ₂ -OCH ₃ ) ₂

19 -N-CH-CH ₅ -CH, 1 * - CH,

n _D ²⁵ : 1.5357

2o

CH, CH 3 ι

88-90

Example no.

-Nv physical data (refractive index, melting point ⁰ C)

СЛІ

21 22

-N H

.CH

CH,

CH CH ₃

CH,

99

9o

.CH,

CH ₁ n * ¹ : 1.5549

25 -N

/ ^C 2 ^H 5

26

103

27

Example no.

-nv

Physical. Data (refractive index;

Melting point ⁰ C)

28 -N

CH

n ²² : 1.5972

n ²² : 1.5432

3o

: l, 55oo

Analogously, the following compounds can be prepared:

CH ₃ S Strukturforme1 n ²³ : l, 556o 31 ^ V »Τ ν CH ₃ S ₁ IL ^ ^ S "^ 0-CH ₂ -CO-N 98 32 О "^ S ^ ⁴ O-CH-j-CO-N-

CH,

33 CH ₃ S

^ CH ₂ -CO-N (C ₂ H ₅ ) ₂ 68

Example no.

Structural formula Physical data

(Refractive index, melting point

34 CH ₃ S

0-CH ₂ -CO-N (CH ₃ ) ₂ 15ο

CH ₃ S

'Ν

о-сн

, -CO-N0

36 CH ₃ S

^ S ^ O

156

37 ei

Cl

VlP CH ₃

As- <O-CH-CO-

: 1.5584

-N

η-

n | ³ .1.5675

CH,

Example No. Structural Formula Physikai.Data (refractive index, melting point ⁰ C)

N-N I

39 CH ₃ -SO ₂

-У "о ·

CH,

N-N

4о C ₂ H ₅ -SO ₂ -

п | ³ , 1.5321

CH,

41 CH,

CH-

42 iso-C, H.

43 ISO-C ₃ H ₇

| _N _ _s

44 iso-

v *

| _ _s X) -o-ch ₂ -co-n (c ₂ h ₅ ) ₂

44

Example structural formula

No physical data (refractive index, melting point)

NS, -CO-N (CH ₂ -CH = CH ₂ ) ₂

"L'.i.

-O-CH ₂ -CO-I

47

N-S54

48

Cl 4

egg//

CH,

118

49

⁷ T \) - о-сн ₂ -со- / н) -

CH ₃

| j V0-ηΓ: 1.523ο

1 CH,

CH,

51

η _τ

: 1.5155

CH

Example No. Structural Formula Physical Data (refractive index, melting point QC)

52 iso-C ₃ H ₇ ^ __ _N

CH-

53 1SO-C ₃ H

: 1.4987

54 iso-C,

-O-CH ₉ -CO-N

: 1,515ο

І SO-C ₃ H,

7 V-N ν,

Π ^ -O-CH ₂ -CO-N-CH-CH ₂ -CH ₃ 46-48

^N ~ ^S CH,

CH,

-CH ₀ -CO-N

CH

n ^ ¹ : l, 5428

Example No. Structural Formula Physical Data (refractive index, melting point OC)

57

l · '

85-86

CH,

58

(ch ₃ ) ₃ c

CH, Vo-CH ₂ -CO-Nl?)

84-85

Cl

59

n * °: 1.5881

6o

ISO-C ₃ H ₇ , 2o.

-0-CH ₉ -CO-N-CH ₀ CH ₉ CH, η ^υυ : 1.4949 ℓ t * - ^ - J D

CH-CH ₂ -CH ₃ CH ₃

(CH 78

1оЗ

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

CH ₂ -CO-N H

116

N? ^H 3

А-0-СН ₉ -С0-Й-? Н-СН ₉ -СН,

0 ^/ * CH ₃ ^£ 134

65 r

CH

llo

⁴ Vo-CH ₂ -CO-N (CH ₂ -CH ₂ -92

143

Example No. Structural Formula Physical Data (refractive index, melting point oc)

143

Vo-CH ₂ -CO-N

CH

CH;

133

"Λ] T ⁴ )" ⁰ " ^CH 2"

^C0 "

H ₃ CCH ₃ CH ₃ 9o

73 V *

138

Example No. Structural Formula Physical Data (refractive index, melting point oc)

CH Ho

76 C ₉ Hc-OCO

CO-OC ₂ H ₅ n * ¹ : 1.5334

CH,

CH ₃ -CH-O-OC CH,

l ⁴ CH 0-CH ₂ -CO-N - //

115

114

CH 0-CH ₂ -CON -? /

IO7

Cl

CH

Example No. Structural Formula - Physical Data (refractive index;

81 CH,

Cl

CH

CH ₅ OC

CH

I6O

83H, C, CH

(CH _{5) 5} C

H ₅ C

H ₅ CO-OC

CH.

Vo-CH ₂ -CO-N- ('_?)

Belspiel No. Structural formula Physical data (refractive index, melting point OC)

148

CH

89 н ₃ с I o-a- ^ JH ₃ C-OC 9ο C ₂ H ₅ -nv -S ' ² H ₃ C _n

CH

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

CH

CH,

) -CH ₂ -CO-N- ^

CO-OC ₅ H, -

0-CH ₂ -CO-N (CH ₂ -CH ₂ -OCH ₃ ) _{2 82}

CN

(ch ₃ ) ₂ ch-ch

N, N

И _л Jl CH

96

Example no.

Structural formula Physical data (refractive index, melting point OC)

CH, O-CH ₂ -CO-N- /

: 1,539ο

98

0-СН -CO-N нѴсН, V- /

CH,

78

99 п-С ₃ Н ₇

CH,

0-CH ₂ -CO-N - //

loo

CH-

22

: 1,4791

lol iso-C, H

0-CH ₂ -CO-N

ng ² .1.5632

H ₃ C

CH ι

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

H, C

0-CH ₂ -CO-N H

n ²² : 1.4885

CH,

Io4 CH ₃ S

XJL

0-CH ₂ -CO-N HVC ₂ H ₅ 87

Ю5 CH ₃ S

0-CH ₂ -CO-N

Io6 CH ₃ S

0-CH ₂ -CO-

n ²³ : I ₄ 5547

CH ₂ -CO-NH \ CH,: 1.5300

At game no. Structure frame Physical data (refractive index! Melting point ⁰ C) Io8 H ₃ C ₂ 0-CH ₂ -CO-N- ^ N п ²² : 1.5578 N N I! I I 1 1 ^ Ч Io9 H ₅ C ₂ ' ^{/ S /} ^ O-CH ₂ -CO-N ~ Y ^] η ²² : 1.5225

Ho H ₅ C ₂

0-CH ₂ -CO-N H) -CH,

n ²² : 1, 5ol9

CH-

CH, -CH ₂ -CO-N- ^

n ²³ : 1.5831

112 nC ₃ H _? S

₃ H _?

0-CH ₂ -CO-

n ²² : l, 5624

113 NH ₂ '

-CH ₅ -CO-N

H ₃ C

η ²² : 1.5539

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

Cl

0-CH ₀ -CO-N Ν - (/ Λ ² Ѵ_У \ /

n £ ² : l, 6lo2

Cl

CY

0-CH ₂ -CO-N N

6o

116 cl

Cl '"' O-CH ₂ -CO-N N- (

n ²² : 1.5585

117 Cl ₄

he ^s

CH ₃ O

n ²² : l, 558o

118 cl

/ - \

0-CH ₂ -CO-N H

CH,

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

119 CH, p

ΓΝ

CH,

0-CH ₂ -CO-N

190 *

120

Cl

^ -O-CH ₂ -CO-N

75 ^C

CH,

121

n ^ ⁰ : 1.5020

0-CH ₂ -C0-N (CH ₂ -CH = CH _2).

122 cl

86 °

O ^ O-CH ₅ -CO-N ρ

123 Cl

48 ^е

Example No. Structural formula Physical data (refractive index! Melting point ⁰ C)

124 Cl χ _N

'ι ι}

0-CH ₂ -CO-N (CH ₃ ) ₂

64 <

125 cl

0-CH

₂ -CO- / ИЛ

CH,

126 cl

J-CH ₂ -CO-N (C ₂ H ₅ ).

2o η: 1.5052 '

η? ⁰ : 1,4851

127

0-CH ₂ -CO-N ^с зѴ ^п

CH-CH ₂ -CH ₃

CH,

128 ClCl

CH-CH ₂ -CH ₃ CH,

129 CH ₃ S

0-CH ₂ -CO-N (CH ₂ -CH = CH ₂ )

: 1.5549

130 CH,

68 ° -69 ° ^C

/ - \ 0 -CH ₂ -CO-N )

CH ₃

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

131 CH, S _ч

³ V-TN n ^21: 1.5309

0-CH ₀ -CO-NCC, H ₇ -n) _o D f c-

132 ei

Cl

: 1.5579

133 CH ₃

120 '

134

135

136

^2H 5

C ₃ H ₇ -is ·

η ²³ : 1.5291

CH,

137 " ^A N-CO-CH

/ Nt ^X SN

C, H ₇ -is ·

75

H ₃ C CH ₃

₁₃ 8

H ₃ C CH ₃ n ²³ : 1.5212

Physikal.Daten

Bei- (refractive index, melting

No. Structural formula point ⁰ C)

NN n? ³ : 1.5125

C ₂ H ₅ /

i40is.-C ₃ H ₇₄ _ Nj-if ^C 3 ^H 7- ^{is #} 4 /

C ₂ H ₅ / ^N

141 ise-C, H ₇₄ .Ν- / n ^23: 1.5385

^{3 7} ; N-CO-CH ₂ -OZ / »D

C ₂ H ₅

142 <Г ^ - ^С ° - ^СН 2- ° - ^ Il n ^ ³ : 1,5268

-C ^S ^ 4C H

CH ₃ 143 (^ N-CO-CH ₂ -O - // Й n ²³ : 1.5172

C ₂ H ₅

А- < ^СНЗ 144 (Vc0-CH ₂ -0 - ^ _s Jn n ²³ : 1,4980

C ₂ H ₅

-O- (Z T

145 CJN-CO-CH ₉ -O- (ZT n ²³ : 1.5559

У / ^{2 4} J ^D

Physikal.Daten

Bei- (refractive index, melting

Kr. Structural formula point ⁰ C)

f ^ /^NY 23

146 / N-CO-CH ₂ -O- (ZI χς ⁵ : 1.5371

) ^P

C ₂ H ₅

147 O N-Ca-CH ₉ -O- (ZI nr *: 1.5367

У ^ M ₄ C ₂ H ₅

CH ₃ ^

148 Q VcO-CH ₉ -O - // I n ² 3: 1.5162

₃ - () i-C0-CH ₂ -0 - (/ [I

149 CH ₃ - () i-C0-CH ₂ -0 - (/ [I ^ n: 1.5162

/ - (

(N

/ ( / ^NN ? ^ Ζ

150 (N-CO-CH ₅ -OV H n °: 1.5124

ѴУ ^{2 X} Jk () D

C ₂ H ₅

/ N-N.

151 (> J-C0-CH ₉ -0 - (/ Π 84-85

CH ₃

example

Structural formula Physical data (refractive index! Melting point © С)

152 CH ₃

NJP: 1,51i6

N-N

C ₂ H ₅ C (CHj) ₃

NJP: 1.5185

C (CH,)

3'3

155

156

157

N-N

τξ ³ : 1.5865

C ₂ H ₅

-CO-CH ₉ -O - (^ I 2 \ <з_K rf: 1.5760

Is-C ₃ H ₇ OI ₁₁ о

сн, _ч

\\ - ο-л_г ς /

CH

CH ₂ -CO-N

158

Cl

CH ₂ -CSCH

\

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

tt

159 HC ₃ H ₇ S / ^^ oc ^ -co-N н

n ²⁰ : 1.5461

CH,

160

CH,

²⁰ : 1.5193 D

0-CH ₂ -CO-N (CH ₂ -

CH ₉ -C 1 CH

J-CH ₂ -CO-N-CH ₂ - ^ _

162

1 Ir CH ₃

ng ⁰ : 1.4947

1 0 -CH ₂ -CO-N (CH ₂

163 Cl

Cl

CH, 47 ^° C

0-CH ₂ -CO-N (CH ₂ J ₃ CH ₃

164

Ti-Г ^ ^С 2 ^Н 5

-CO-N (CH ₂ J ₃ CH ₃

165

_c ? 2

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

166 Cl

_Cl , 4S ^ NO-CH ₂ -CO-N ₄ H

167 Cl

Cl

2 ⁿ 5

0-CH ₂ -CO-N (CH ₂ ).

168

xl

As ^A o- (

_cl / w V-CH ₂ -CO-N H

CH, 1.5505

169

₇₄

0-CH ₂ -CO-N H

CH,

170 iSe-C ₅ H ₇ .

0-CH ₂ -CO-N

171 Cl

_C1 / ^ -> 0-CH ₂ -CO-N. > -CH ₃

-CO-I / У

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

CH,

172

CH,

173

N-N

S-Lc (CH ₃ ) ₃

85-8S

174 (CH ₃ )

ft 3-0-CH ₉ -CO-N

: 1.5134

175

CO-OCH

CH 1

176

108

177

= - ° <ίί

CH, 1.5816

178

C ₂ H ₅ 1.5805

examples

game

No. Structural formula Physical data (refractive index, melting point ⁰ C)

179

H ^ N-CO-CH ₂

^X SN

η Ι ⁹ : 1.5750

CH,

180 (hJN- ^c ° - ^CH 2 "

₁₃ 9

CH,

, -QMCOfe-O-Q S-СНоЧ /

^y : 1.5585

H ₅ C CH ₃

182 (H ^ i-CO-CH ₂ -

^S " ^CH 2A-7

n ¹⁹ : 1.6247

183 (H VcO-

n ^ ⁹ : 1.5895

S-N

184 CH,

L. ^

NC

CH ₃ 120 ⁰ C

Physikal.Daten

At- (refractive index-index

No. Structural formula point ⁰ C)

185 CH

iN ^CH 3

0-CH ₀ -CO-N-CH-CH ₅ -CH

² 6h

186 CH

? 3

0-CH ₂ -CO-N-CH-CH ₂ -CH ₃

сн ₃

187 CH, S \ n ^ ⁰ : 1.5410

CH

-ι

CH

-CH ₂ -CO-N-CH-CH ₂ -CH ₃ CH ₃

188 CH, S ^ c ₄

³ YN \ <

189 Cl _v

Cl, Γ Vo-ch ^ -co-n ^ Vch, _n _q / * ^ - / * 2o η J1 479 190 Cl, -Vo-CH ₂ -CO-NCc ₃ H ₇ -Ii) ₂ η: 1 , 502 191 Il ^ч ) -о-сн ₂ -со-іГЛ ^ CH,

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

192 cl

CH ₃ у NO

^ 4

CH,

193

JpVo-CH ₂ -CO-NQ

194

Ir ¹ Vo-CH ₂ -CO-N 1 -) CH ₃

CH95 CH ₃ S

Τ;

r ^ 71 "

196

^C 2 ^H 5

118 '

197

N-S

198

CH,

-

0-CH ₂ -CO-N-CH-CH ₂ -CH ₃ CH,

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

199

₃ 0 -CH ₂ -CO-N-CH-CSCH

CH ₅

200

Cl.

TN CH,

N, ₃ X 0 -CH ₂ -CO-N-ZH

202 Cl

vtn

CH,

I ·>

203

CH, O-CH ₂ -CO-N - (/

204

N-O

? 2 ^H 5

205 cl

ТУ-

0-0

CH ₃

CH ₉ -CO-N-CH-CSCH CH,

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

206 cl

CH,

V ^N \ 'I \ .o-ch ₂ -cc-n-ch-ch ₂ -ch ₃

N-O

сн ₃

, N-N

njp: 1.5550

CH,

208 (N-CO-CH

CH,

/ NN ⁸ ^: 1.5738

S-CH.

2Л_

210 CH,

-N

0-CH ₂ -CO-N ₄ Ji _x

211 CH

110 °

212 CH,

n2o _: 1.5130

0-CH ₂ -CO-N (C ₂ H ₅

Example no.

Structural formula Physical data (refractive index, melting point ⁰ C)

213

0-CH ₂ -CO-N

214

".N119

0-CH ₂ -CO-

CH,

215

128 '

} -CH ₂ -C0 -N Ѵ

H, С-г- N ₄

* I ⁴ Vo-CH ₃ -CO-NCH ₀ -ISe 216 is © - C ₃ H ₇ O-OC-JS / * ^ ^у

217

H ₃ C- -OC-CH;

) -ch ₂ -co-ny ^ n *

CH ^

²¹ S ^C1 > pN ₄

7-0CH,

Example N'r. Structural formula Physical data (refractive index, melting point ⁰ C)

219 ISe-C ₃ H ₇

ff? ^H 3

0-CH ₂ -CO-N-CH ₂

220

'2 ^Π 5

J / "O-CH ₂ -CO-N- (H

221

> CH ₂ -S, O-CH ₂ -CO-N 0

CH,

222

¹ N

CH

IJ '''" ³

0-CH ₂ -CO-N

²²³ O " ^CH 2- ^S -n N

CH ₂ -CH = CH ₂

224

IsO-C ₃ H ₇

) -CH ₂ -CO-NH

Example no.

Structural formula Physical data (refractive index, melting point ⁰ C)

²²⁵

^CF 3-vJ> CH,

226

CF,

0-CH

227

228

₂₂₉

CH,

CH,

230

CF,

Example no.

Structural formula Physical data (refractive index! Melting point ⁰ C)

231

CH, ι ·>

0-CH ₂ -CO-N - (/

232

F ₃ C

N;

CH,

233

CF

CH

234

CH,

л,

235

Cl

Cl

CH ₃

Cl

236

Cl CH,

Example no.

Structural formula Physical data (refractive index, melting point ⁰ C)

237

CH, S

CH ι

Cl

CH, t

-CH ₂ -CO-N - //

Cl

CH,

iSO-C ₇ H ₇

CH,

11 If '> ¹ ^ S ^ 0-CH ₂ -CO-N - // ^

CH,

CH, S «

N-S

CH, ' г

H ₃ C-

CH

л "тт"

Example No. Structural Formula Physical Data (refractive index, melting point ⁰ C)

243 i SO-C ₃ H? ^H 3 -CO-N- ^ V-CF

244

245

OCH

246 nC ₃ H ₇ -SO ₂ OCH

247 CH, S

CH, ·>

" ^0CH

CH,

248 CH,

-CO-CH ₂ -O

: 1.5298

CH,

The compounds of the formula (II) to be used as starting materials can be prepared as follows:

Example a: HO-CH ₀ -CO-N- ^ N u 2 \ ~ /

A suspension of 183.5 g (1 mol) of chloroacetic acid N-methylanilide, 82 g (1 mol) of anhydrous sodium acetate and 32o ml of toluene is heated for 4 hours at 115-12o ° C and then cooled to room temperature. The mixture is filtered off with suction and the residue is washed with cold toluene. Of the solvent and evaporation of the residue in the steam-jet vacuum at a bath temperature of 8o-85 ° C 2o7 gt ^ are selected from the toluenic solution after Abdestil- ^ ⁰ lose acetoxy-acetic acid-N-methylanilide obtained which crystallizes on standing - GC: = 98 %, melting point 54-56 ⁰ C; Yield 99% of theory.

The reaction mixture of 211.2 g (1 mol) of C ^ -Acetoxyessig-acid N-methylanilide (98%), o, 2 g of sodium hydroxide and 16o g of methanol is heated under reflux for 4 hours. The mixture of methanol and methyl acetate is distilled off. The liquid distillation residue - [17o g yield of hydroxyacetic acid N-methylanilide, quantitative, GC: 98%, melting point: 52-53 ° C solidified on cooling.

GC = according to gas chromatograirane

Analogously, the following compounds of the formula (II) are obtained:

HO-CH-CO- /, (II)

example

TABLE

Melting point ( ⁰ C); Refractive index;

-N H

CH

C Ή -N (CH ₂ -CH ₂ -OCHj) ₂ 36 η * ⁵ : 1.4662

e H

CHj

CHj

-N-CH-CSCH CH, 83 п £ ^э j1,4859

CH n £ ⁵ : 1.4816

g H

-NJT H 55

example

-я

-N H

-N НУ-СН,

Melting point ( ⁰ C) {refractive index:

80

Example A

Рге-βmergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a zvjeckmaßigen active compound preparation, 1 part by weight of active compound with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with V / asser to the desired concentration

Seeds of the test plants are sown in normal soil and watered after 24 hours with the preparation of active ingredient. It is advisable to keep the amount of water per unit area expediently constant. The concentration of active ingredient in the preparation does not matter, only the application rate of the active ingredient per unit area is decisive. After three weeks, the degree of damage of the plants is rated in % damage in comparison to the development of the untreated control. Ss mean:

O % = no effect (as untreated control) 100 % = total destruction

In this test, z. For example, the following compounds of Preparation Examples have an excellent effect:

No. 1, 2, 8, 17, 19, 31, 41, 99, 104, 107, 108, 118, 119,

120, 121, 122, 123, 124, 125, 126, 129, 130, 131, 132, 141,

142, 145, 154, 155, 156, 159, 160, 162, 163, 168, 180, 184,

187, 188, 189, 190, 193, 194, 195, 196, 248.

Example В

Рге-emergence test / transplanted rice water

Water treatment before raising the seeds of rice field weeds in submerged fields (pot test)

Preparation of the material preparation: Solvent: 5 parts by weight of acetone Emulsifier: 1 part of benzyloxypolyglycol ether

To prepare a suitable Wirkstoffzübere iter tion 1 Blend part of active ingredient with the stated amount of solvent, is the indicated amount of emulsifier and dilutes the concentrate with Y / asser to the desired concentrate ion ·

Test methods:

Waffertöpfe (1/5000 a) are filled with Reisfelderde · Then 2 ice plants (variety "Kinmaze") in the 2-3 ~ leaf stage (from about 10 cm in height) are planted in each pot.

The seeds of the test plants (Echinochloa crus-galli, Cyperus sp., Eleocharis acicularis and breitblättrigeη weeds) introduced into the pot, which is kept wet, Z ¹ ^ ei days after planting • each pot 3 is ctn. set deep under water and doused with the preparation of active ingredient · It keeps the amount of water per unit area zvieckmäßervervise constant. The concentration of active compound in the preparation does not matter, only the application rate of the active ingredient per unit area is decisive.

After the treatment, 2-3 cm of water are allowed to drain off each pot for two days, then the pots are placed under water again 3 cm deep. Four weeks after the treatment with the active compound preparation, the herbicidal action of the active compounds according to the invention and the phytotoxicity to ice plants are evaluated according to the scale below.

Compared to the untreated control area, the effect of the active compounds according to the invention is evaluated as follows;

Abtötungs ^ rad more than 95 % 5 more than 80 % 4 more than 50% 3 more than 30 % 2 more than 10% 1 fewer than 10% О

Compared to the untreated control area, the phytotoxicity to rice plants is assessed as follows:

phytotoxicity more than 90 % (total damage) 5 more than 50 % 4 more than 30 % 3 fewer when 30% 2 fewer when 10% 1 0 % (no phytotoxicity) 0

In this test, z. For example, the following compounds of the Hexstellungsbeispiele an excellent effect:

1, 6, 7, 8, 9, 10, 13, 16, 17, 19, 20, 21, 24, 26, 29, 32,

41, 51, 52, 54, 55, 56, 77, 78, 97, 99, 104, 106, 108, 111,

130, 131, 132, 134, 135, 138, 141, 142, 146, 149, 153, 154, 155, 156, 248.

Claims (8)

invention claim 1 · Herbicidal agent, characterized in that it contains as active compound Azolyloxy-carboxamides of the formula I. RO-CH-CO-N ₄ (I) R ^{1 R} contained in which R is a five-membered heteroaromatic monocycle which contains one oxygen or one sulfur atom and additionally contains 1 to 3 nitrogen atoms and is optionally substituted by halogen, nitro, cyano, amino, alkylamino, diacylamino, alkylcarbonylamino, alkylcarbonyl, carboxy, alkoxycarbonyl, Carbamoyl, alkylamino carbonyl, dialkylaminocarbonyl, optionally substituted by halogen, nitro or alkyl-substituted arylaminocarbo-ure1 optionally substituted by halogen, nitro, cyano, alkyl, haloalkyl or alkoxy-substituted aryl, optionally substituted by halogen aralkyl, optionally halogen-substituted alkoxy, alkenoxy, alkynoxy, alkoxycarbonylalkoxy , Aralkoxy or aryloxy, optionally halogen-substituted alkylthio, alkenylthio, alkynylthio, alkoxycarbonylalkylthio, aralkylthio, arylthio, alkylsulfinyl or alkylsulfonyl, optionally halogen-substituted alkyl, alkenyl, alkynyl, alkoxyalkyl, aralkoxyalkyl, aryloxyalkyl, alkylthioalkyl, Alkylsulfinylalkyl, alkylsulfonylalkyl, arylthioalkyl, arylsulfinylalkyl, arylfulfonylalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aminocarbonylalkyl, cyanoalkyl or cycloalkyl; in which further R is Y / oxygen or alkyl, R and R 1 are the same or different and each individually represents Y, each optionally substituted alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, aryl or a nitrogen-containing heterocyclic radical or together with the nitrogen atom to which they are attached, an optionally substituted , optionally partially unsaturated and optionally further heteroatoms, in addition to conventional extenders and / or surface-active agents. ₂ -C0-NH> contain. 2 # A method for controlling unwanted plant growth, characterized in that one lets act Azolyloxycarbonsäureamide according to item 1 on the unwanted plants or their habitat. Use of azolyloxycarboxamides according to item 1, characterized in that they are used for controlling unwanted plant growth. 4. A process for the preparation of herbicidal LIittein, characterized by mixing azolyloxy-carboxamides according to item 1 with extenders and / or surface-active agents. 5. Composition according to item 1, characterized in that it is an azolyloxy-carboxamide of Pormel Cl Cl S N (1) О - CH ₂ - СО contain. 6, agent according to item 1, characterized in that it is an azolyloxy-carboxamide of the formula N И / -ч ^ S - ^^ O-CH ₂ -CO-U Ю -C ₂ H ₅ (104) contain· 7 · Composition according to item 1, characterized in that it is an azolyloxy-carboxamide of the formula Cl ) X \ 0 ~ f! W -ΠΛ i \ T w \ (118) 8 # Composition according to item 1, characterized in that it is an azolyloxy-carboxamide of the formula Cl -CH ₂ -CO-Ii (CHg) ₃ CK ₃ (163) contain.