DE19616719A1 - New 3-pyrimidinyl:benzyl-hydroxylamine derivs. - Google Patents

Abstract

N- or O-(3-(2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)benzyl)-hydroxylamine derivs. of formula (I) and salts of (I; R<3>, R<7> and/or R<8> = H) are new. X = -N(R<7>)-O-, with R<8> bonded to O or N; Y = O or S ; R<1> = halo, CN, NO2 or CF3; R<2> = H or halo; R<3> = H, NH2 or Me; R<4> = H, halo, alkyl, haloalkyl, alkylthio, alkylsulphinyl or alkylsulphonyl; R<5> = H, halo or alkyl; R<6> = H, alkyl, haloalkyl, 3-6C cycloalkyl or 2-6C alkenyl; R<7> = (i) H; (ii) alkyl, cycloalkyl, haloalkyl, alkenyl, alkynyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, alkoxycarbonyl, (2-6C)alkenyloxycarbonyl, (2-6C)alkynyloxycarbonyl, alkylthiocarbonyl, alkylsulphonyl or alkylcarbamoyl (all opt. substd. by 1-3 of NO2, CN, cycloalkyl, OH, alkoxy, cycloalkoxy, alkenyloxy, alkynyloxy, alkoxyalkoxy, alkylthio, alkylcarbonyl, alkylcarbonyloxy, alkylsulphinyl, alkylsulphonyl, 1-6C alkylideneaminoxy, alkylcarbamoyl, Ar, OAr, SO2Ar, Het, OHet, COZ<1>R<9>, OCOZ<1>R<9> and NR<9>R<10>); or (iii) cycloa lkylcarbonyl, benzoyl, phenylsulphonyl or phenylcarbamoyl (all opt. substd. by 1-3 of halo, NO2, CN, alkyl, alkoxy and haloalkyl); R<8> = H ; or alkyl, cycloalkyl, haloalkyl, alkenyl or alkynyl (all opt. substd. by 1-3 of NO2, CN, halo, cycloalkyl, OH, alkoxy, cycloalkoxy, alkenyloxy, alkynyloxy, alkoxyalkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, 1-6C alkylideneaminoxy, Ar, OAr, SO2Ar, Het, OHet, COZ<2>R<11>, OCOZ<2>R<11> and NR<11>R<12>); Z<1> = a bond, O, S or NR<10>; Z<2> = a bond, O, S or NR<12>; Ar = phenyl (opt. substd. by 1-3 of halo, NO2, CN, alkyl, haloalkyl and alkoxy); Het = 3-7 membered satd., partially or completely unsatd. or aromatic heterocycle contg. 1-3 heteroatoms selected from 2 O, 2 S and 3 N (opt. substd. by 1-3 of halo, NO2, CN, alkyl, alkoxy, haloalkyl and alkylcarbonyl); R<9>, R<11> = H, alkyl, haloalkyl, cycloalkyl, alkenyl, alkynyl, alkoxyalkyl or alkoxycarbonylalkyl, or phenyl or phenylalkyl (both opt. ring-substd. by 1-3 of NO2, CN, halo, alkyl, haloalkyl, alkoxy or alkylcarbonyl); or Z<1> + R<9> and/or Z<2> + R<11> may complete an N-bonded heterocycle as defined for Het (except that the optional substituents do not include alkylcarbonyl); R<10>, R<12> = H, OH, alkyl, cycloalkyl or alkoxy; unless specified otherwise, alkyl moieties have 1-6C, alkenyl or alkynyl moieties 3-6C and cycloalkyl moieties 3-8C.

Description

The present invention relates to new benzylhydroxylamines general formula I.

in which the variables have the following meaning:
X -N (R⁷) -O-, which can be bound to R⁸ via oxygen or nitrogen;
Y oxygen or sulfur;
R1 halogen, cyano, nitro or trifluoromethyl;
R² is hydrogen or halogen;
R³ is hydrogen, amino or methyl;
R⁴ is hydrogen, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl,
C₁-C₆ alkylthio, C₁-C₆ alkylsulfinyl or C₁-C₆ alkylsulfonyl;
R⁵ is hydrogen, halogen or C₁-C₆ alkyl;
R⁶ is hydrogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl or C₂-C₆ alkenyl;
R⁷ is hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl,
C₁-C₆ haloalkyl, C₃-C₆ alkenyl, C₃-C₆ alkynyl,
(C₁-C₆-alkyl) carbonyl, (C₃-C₆-alkenyl) carbonyl,
(C₃-C₆-alkynyl) carbonyl, (C₁-C₆-alkoxy) carbonyl,
(C₂-C₆-alkenyloxy) carbonyl, (C₂-C₆-alkynyloxy) carbonyl,
(C₁-C₆-alkylthio) carbonyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkyl carbamoyl, each of the latter 14 radicals optionally being able to carry one to three substituents, each selected from the group consisting of

• - Nitro, cyano, halogen, C₃-C₈ cycloalkyl, hydroxy, C₁-C₆-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-alkyl thio, (C₁-C₆-alkyl) carbonyl, (C₁-C₆-alkyl) carbonyloxy, C₁-C₆-alkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylidene aminoxy, C₁-C₆ alkylcarbamoyl,
• - The phenyl, phenoxy or phenylsulfonyl group, wherein the phenyl rings may be unsubstituted or one to three Can carry substituents, each selected from the Group consisting of halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆ alkoxy and C₁-C₆ haloalkyl,
• - A 3- to 7-membered heterocyclyl or hetero cyclyloxy group with one to three heteroatoms from the group consisting of two oxygen atoms, two Sulfur atoms and 3 nitrogen atoms, the hetero cycle saturated, partially or completely unsaturated or be aromatic and, if desired, one to three Can carry substituents, each selected from the Group consisting of halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl and (C₁-C₆-alkyl) carbonyl,
• - a group -CO-Z¹R⁹, -OCO-Z¹R⁹ or -N (R⁹) R¹⁰,

or
R⁷ C₃-C₈-cycloalkylcarbonyl, phenylcarbonyl, phenylsulfonyl or phenylcarbamoyl, where these 4 radicals can be unsubstituted or can carry one to three substituents, each selected from the group consisting of halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆- Alkoxy and C₁-C₆ haloalkyl;
R⁸ is hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-halogeno alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl, each of the latter 5 radicals optionally being able to carry one to three substituents, each selected from the group consisting of

• - Nitro, cyano, halogen, C₃-C₈ cycloalkyl, hydroxy, C₁-C₆-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-alkyl thio, C₁-C₆-alkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆ alkylidene aminoxy,
• - The phenyl, phenoxy or phenylsulfonyl group, wherein the phenyl rings may be unsubstituted or one to three Can carry substituents, each selected from the Group consisting of nitro, cyano, halogen, C₁-C₆-alkyl, C₁-C₆ alkoxy or C₁-C₆ haloalkyl,  
• - A 3- to 7-membered heterocyclyl or hetero cyclyloxy group with one to three heteroatoms from the group consisting of two oxygen atoms, two Sulfur atoms and 3 nitrogen atoms, the hetero cycle saturated, partially or completely unsaturated or be aromatic and, if desired, one to three Can carry substituents, each selected from the Group consisting of halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or (C₁-C₆-alkyl) carbonyl,
• - a group -CO-Z²R¹¹, -OCO-Z²R¹¹ or -N (R¹¹) R¹²;

Z¹ is a chemical bond, oxygen, sulfur or -N (R¹⁰) -;
Z² is a chemical bond, oxygen, sulfur or -N (R¹²) -;
R⁹, R¹¹ independently of one another are hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₈-cycloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, ( C₁-C₆-alkoxy) carbo nyl-C₁-C₆-alkyl, phenyl or phenyl-C₁-C₆-alkyl, where the phenyl group and the phenyl ring of the phenylalkyl group may be unsubstituted or may carry one to three radicals, each selected from the group consisting of from nitro, cyano, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy or (C₁-C₆-alkyl) carbonyl
or
Z¹ and R⁹ and / or Z² and R¹¹ each together for a nitrogen-bonded 3- to 7-membered heterocycle having one to three heteroatoms, selected from the group consisting of two oxygen atoms, two sulfur atoms and 3 nitrogen atoms, the heterocycle being saturated, partially or completely be unsaturated or aromatic and, if desired, can carry one to three substituents, each selected from the group consisting of nitro, cyano, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl and C₁-C₆-alkoxy;
R¹⁰, R¹² independently of one another are hydrogen, hydroxy, C₁-C₆-alkyl, C₃-C₈-cycloalkyl or C₁-C₆-alkoxy,
and the agriculturally useful salts of those compounds I in which R³, R⁷ and / or R⁸ are hydrogen.

The invention also relates to

• - The use of the compounds I as herbicides or for the desiccation and / or defoliation of plants,
• - herbicidal agents and agents for desiccation and / or Defoliation of plants which the compounds I as contain effective substances,
• - Methods to combat undesirable plant growth and for the desiccation and / or defoliation of plants with the Connections I,
• - Process for the preparation of herbicidal compositions for desiccation and / or defoliation of plants under Use of the compounds I, as well
• - new intermediates of formulas IV, V, XIII, XVI, XVII, XIX and XXIII from which the compounds I are obtainable.

WO 93/06090 and EP-A 408 382 already specify 3-Phenyluracile as herbicide and for desiccation / defoliation described by plants that - with a suitable choice of Substituents - of the present compounds I in particular differ in that the phenyl ring instead of the Substi tuenten -CH (R⁶) -X-R⁸ carries an iminomethyl group.

According to the teaching of WO 95/06641 u. a. Connections of the Formula II

where Ra is hydrogen, fluorine or chlorine and
R ^b for a hydroxyiminomethyl or oxyiminomethyl group
are also suitable as herbicides and for desiccation / defoliation of plants.

Finally, it is known from DE-A 42 37 920 that certain 3-aryluracils, u. a. the compounds of formula III

in which
R ^{c represents} hydrogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃ / C₄ alkenyl or C₃ / C₄ alkynyl;
R ^d and R ^{e are} hydrogen, C₁-C₈-alkyl, C₃-C₇-cycloalkyl or C₃-C₇-cycloalkyl-C₁-C₄-alkyl;
R ^f for hydrogen, C₁-C₅-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, C₁-C₅-halo alkyl, C₂- C₅-alkenyl, C₂-C₅-alkynyl, optionally subst. Aryl or benzyl or for a keto, ester or thioester group and
R⁵, represent hydrogen, halogen or C₁-C₄-alkyl, are suitable for weed control.

The herbicidal properties of the known compounds are but not always fully satisfactory. There were therefore these Invention new, in particular herbicidally active compounds Task based on which undesirable plants are better than have been targeted so far.

The task also extends to the provision of new ones desiccant / defoliant effective connections.

Accordingly, the benzylhydroxylamines of the formula I and their herbicidal activity found.

Furthermore, herbicidal compositions have been found which the compounds I contain and have a very good herbicidal effect. Furthermore Processes for the preparation of these agents and processes for Control of undesired plant growth with the compounds I found.

Furthermore, it was found that the compounds I also for Defoliation and desiccation of plant parts are suitable, for which crops such as cotton, potato, rapeseed, sunflower, Soybean or field beans, especially cotton come. In this regard, means of desiccation and / or Defoliation of plants, process for the preparation of these agents and methods for the desiccation and / or defoliation of plants with the compounds I found.

The compounds of formula I can, depending on the substitution pattern contain one or more chirality centers and then lie as enantiomer or diastereomer mixtures. Subject of Invention are both the pure enantiomers or diastereomers as well as their mixtures.  

If R³, R⁷ and / or R⁸ are hydrogen, the benzyl hydroxylamine I in the form of their agriculturally useful Salts are present, depending on the type of salt usually does not arrive. Generally the salts come from such bases considered in which the herbicidal activity compared to the free compound I is not adversely affected.

Those of the alkali are particularly suitable as basic salts metals, preferably sodium and potassium salts, the alkaline earth metals, preferably calcium and magnesium salts, which the over transition metals, preferably zinc and iron salts, and ammonium salts in which the ammonium ion, if desired, one to four C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl substituents and / or one Can carry phenyl or benzyl substituents, preferably Diisopropylammonium, tetramethylammonium, tetrabutylammonium, Trimethylbenzylammonium and trimethyl (2-hydroxyethyl) ammonium salts, furthermore phosphonium salts, sulfonium salts such as preferred as tri- (C₁-C₄-alkyl) sulfonium salts, and sulfoxonium salts such as preferably tri- (C₁-C₄-alkyl) sulfoxonium salts.

The for the substituents R⁴ to R¹² or as radicals on phenyl organic or molecular parts called ring or heterocycles set collective terms for individual lists of the individual group members. All carbon chains, so all alkyl, haloalkyl, alkoxy, alkylthio, alkylsulfenyl, Alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkenyl, Alkenyloxy, alkenylcarbonyl, alkynyl, alkynyloxy, alkynyl carbonyl and alkylidene aminooxy parts can be straight-chain or be branched. Unless otherwise stated, halogenated ones Substituents are preferably one to five identical or different Halogen atoms. Halogen means fluorine, Chlorine, bromine or iodine.

Also mean, for example

• - C₁-C₄-alkyl and the alkyl parts of (C₁-C₆-alkyl) carbonyl, (C₁-C₆-alkyl) carbonyloxy, C₁-C₆-alkylcarbamoyl, C₁-C₆-alkoxy- C₁-C₆-alkyl and (C₁-C₆-alkoxy) carbonyl-C₁-C₆-alkyl: Methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methyl propyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethyl propyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethyl propyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methyl pentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-tri  methylprop, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl;
• - C₁-C₆-haloalkyl: a C₁-C₆-alkyl radical as above called partially or completely by fluorine, chlorine, Bromine and / or iodine is substituted, ie z. B. chloromethyl, Dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, Trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorine difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro 2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoro ethyl, 2,2,2-trichloroethyl, petafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chlorine propyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1- (fluor methyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromine methyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, Nonafluorobutyl, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl or dodecafluorohexyl;
• - Phenyl-C₁-C₆-alkyl: z. B. benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl, 3-phenylbut-2-yl, 4-phenylbut-2-yl, 1- (phenylmethyl) -eth-1-yl, 1- (phenylmethyl) -1- (methyl) - eth-1-yl or 1- (phenylmethyl) prop-1-yl, preferably Benzyl, 2-phenylethyl or 2-phenyl-hex-6-yl;
• - C₃-C₆-alkenyl and the alkenyl parts of C₃-C₆-alkenyloxy and (C₃-C₆-alkenyl) carbonyl: prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, n-buten-1-yl, n-buten-2-yl, n-buten-3-yl, 1-methyl-prop-1-en-1-yl, 2-methyl-prop-1-en-1-yl, 1-methyl prop-2-en-1-yl or 2-methyl-prop-2-en-1-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methyl but-1-en-1-yl, 2-methyl-but-1-en-1-yl, 3-methyl-but-1-en- 1-yl, 1-methyl-but-2-en-1-yl, 2-methyl-but-2-en-1-yl, 3-methyl-but-2-en-1-yl, 1-methyl-but-3-en-1-yl, 2-methyl but-3-en-1-yl, 3-methyl-but-3-en-1-yl, 1,1-dimethyl-prop- 2-en-1-yl, 1,2-dimethyl-prop-1-en-1-yl, 1,2-dimethyl-prop- 2-en-1-yl, 1-ethyl-prop-1-en-2-yl, 1-ethyl-prop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methyl-pent-1-en-1-yl, 2-methyl-pent-1-en-1-yl, 3-methyl-pent-1-en-1-yl, 4-methyl-pent-1-en-1-yl, 1-methyl-pent-2-en-1-yl,  2-methyl-pent-2-en-1-yl, 3-methyl-pent-2-en-1-yl, 4-methyl-pent-2-en-1-yl, 1-methyl-pent-3-en-1-yl, 2-methyl-pent-3-en-1-yl, 3-methyl-pent-3-en-1-yl, 4-methyl-pent-3-en-1-yl, 1-methyl-pent-4-en-1-yl, 2-methyl-pent-4-en-1-yl, 3-methyl-pent-4-en-1-yl, 4-methyl-pent-4-en-1-yl, 1,1-dimethyl-but-2-en-1-yl, 1,1-dimethyl-put-3-en-1-yl, 1,2-dimethyl-but-1-en-1-yl, 1,2-dimethyl-put-2-en-1-yl, 1,2-dimethyl-but-3-en-1-yl, 1,3-dimethyl-put-1-en-1-yl, 1,3-dimethyl-but-2-en-1-yl, 1,3-dimethyl-put-3-en-1-yl, 2,2-dimethyl-but-3-en-1-yl, 2,3-dimethyl-put-1-en-1-yl, 2,3-dimethyl-but-2-en-1-yl, 2,3-dimethyl-put-3-en-1-yl, 3,3-dimethyl-but-1-en-1-yl, 3,3-dimethyl-put-2-en-1-yl, 1-ethyl-but-1-en-1-yl, 1-ethyl but-2-en-1-yl, 1-ethyl-but-3-en-1-yl, 2-ethyl-but-1-en-1-yl, 2-ethyl-but-2-en-1-yl, 2-ethyl-but-3-en-1-yl, 1,1,2-tri methyl-prop-2-en-1-yl, 1-ethyl-1-methyl-prop-2-en-1-yl, 1-ethyl-2-methyl-prop-1-en-1-yl or 1-ethyl-2-methyl-prop- 2-en-1-yl;
• - C₃-C₆-alkynyl and the alkynyl parts of C₃-C₆-alkynyloxy and (C₃-C₆-alkynyl) carbonyl: prop-1-in-1-yl, prop-2-in-1-yl, But-1-in-1-yl, but-1-in-3-yl, but-1-in-4-yl, but-2-in-1-yl, Pent-1-in-1-yl, n-pent-1-in-3-yl, n-pent-1-in-4-yl, n-pent-1-in-5-yl, n-pent-2-in-1-yl, n-pent-2-in-4-yl, n-pent-2-yn-5-yl, 3-methyl-but-1-yn-3-yl, 3-methyl but-1-in-4-yl, n-hex-1-in-1-yl, n-hex-1-in-3-yl, n-hex-1-in-4-yl, n-hex-1-in-5-yl, n-hex-1-in-6-yl, n-hex-2-in-1-yl, n-hex-2-in-4-yl, n-hex-2-in-5-yl, n-hex-2-in-6-yl, n-hex-3-in-1-yl, n-hex-3-in-2-yl, 3-methyl-pent-1-in-1-yl, 3-methyl-pent-1-in-3-yl, 3-methyl-pent-1-in-4-yl, 3-methyl-pent-1-in-5-yl, 4-methyl-pent-1-in-1-yl, 4-methyl-pent-2-in-4-yl or 4-methyl-pent-2-yn-5-yl;
• - C₂-C₆ alkenyl and the alkenyl part of (C₂-C₆ alkenyl oxy) carbonyl. Vinyl or one of the under C₃-C₆ alkenyl said residues;
• - The alkynyl part of (C₂-C₆-alkynyloxy) carbonyl: ethynyl or one of the radicals mentioned under C₃-C₆ Akinyl,
• - C₁-C₆-alkoxy and the alkoxy parts of C₁-C₆ alkoxy C₁-C₆- alkyl, (C₁-C₆-alkoxy) carbonyl and (C₁-C₆-alkoxy) carbonyl- C₁-C₆-alkyl: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethyl ethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,  2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1-methyl pentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethyl-propoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy;
• - C₁-C₆-alkylthio and the alkylthio part of (C₁-C₆-alkyl thio) carbonyl: methylthio, ethylthio, n-propylthio, 1-methyl ethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropyl thio, 1,1-dimethylethylthio, n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropyl thio, 1-ethylpropylthio, n-hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentyl thio, 3-methylpentylthia, 4-methylpentylthio, 1,1-dimethyl butylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethyl butylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio;
• - C₁-C₆-alkylsulfinyl: methylsulfinyl, ethylsulfinyl, n-propyl sulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methyl propylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethyl sulfinyl, n-pentylsulfinyl, 1-methylbutylsulfinyl, 2-methyl butylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropyl sulfinyl, 1-ethylpropylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, n-hexylsulfinyl, 1-methylpentyl sulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethyl butylsulfinyl, 1,1,2-trimethylprosulfinyl, 1,2,2-trimethyl propylsulfinyl, 1-ethyl-1-methylpropylsulfinyl or 1-ethyl-2-methylpropylsulfinyl;
• - C₁-C₆ alkylsulfonyl: methylsulfonyl, ethylsulfonyl, n-propyl sulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methyl propylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethyl sulfonyl, n-pentylsulfonyl, 1-methylbutylsulfonyl, 2-methyl butylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethylpropyl sulfonyl, 1-ethylpropylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, n-hexylsulfonyl, 1-methylpentyl sulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl,  1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethyl butylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethyl propylsulfonyl, 1-ethyl-1-methylpropylsulfonyl or 1-ethyl-2-methylpropylsulfonyl;
• - C₁-C₆-alkylidenaminoxy: acetylidenaminoxy, 1-propylidenamine oxy, 2-propylidene aminoxy, 1-butylidene aminoxy, 2-butylidene aminoxy or 2-hexylidenaminoxy;
• - C₃-C₆-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl or -hexyl;
• - C₃-C₈-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclo hexyl, cycloheptyl or cyclooctyl;
• - C₃-C₈-cycloalkoxy: cyclopropyloxy, cyclobutyloxy, cyclopentyl oxy, cyclohexyloxy, cycloheptyloxy or cyclooctyloxy.

Examples of 3- to 7-membered heterocycles are oxiranyl, aziridiny, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, dioxolanyl such as 1,3-dioxolanane 4-yl, dioxanyl such as 1,3-dioxan-2-yl and 1,3-dioxan-4-yl, dithianyl such as 1,3-dithian-2-yl, further 1,2,4-oxadiazolidinyl, 1, 3,4-oxadiazolidinyl, 1,2,4-thiadiazolidinyl, 1,3,4-thiadiazolidinyl, 1,2,4-triazolinyl, 1,3,4-triazolidinyl, 2,3-dihydrofuryl, 2,5-dihydrofuryl , 2,3-dihydrothienyl, 2,5-dihydrothienyl, 2,3-pyrrolinyl, 2,5-pyrrolinyl, 2,3-isoxazolinyl, 3,4-isoxazolinyl, 4,5-isoxazolinyl, 2,3-isothiazolinyl, 3,4-isothiazolinyl, 4,5-isothiazolinyl, 2,3-dihydropyrazolyl, 3,4-dihydropyrazolyl, 4,5-dihydro pyrazolyl, 2,3-dihydrooxazolyl, 3,4-dihydrooxazolyl, piperidinyl, tetrahydropyridazinyl, tetrahydropyrimidinyl, Tetrahydropyrazi nyl, 1,3,5-tetrahydrotriazinyl and 1,2,4-tetrahydrotriazinyl, and the fo lying heteroaromatics:
Furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl and 3-thienyl, pyrrolyl such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as 2-oxazolyl, 4-oxazolyl and 5-oxazolyl, thiazolyl such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, Imidazolyl such as 2-imidazolyl and 4-imidazolyl, oxadiazolyl such as 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and 1,3,4-oxadiazol-2-yl, thiadiazolyl such 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl and 1,3,4-thiadiazol-2-yl, triazolyl such as 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl and 1,2,4-triazol-4-yl, pyridinyl such as 2-pyridinyl, 3-pyridinyl and 4-pyridinyl, pyridazinyl such as 3-pyridazinyl and 4-pyridazinyl, pyrimidinyl such as 2-pyrimidinyl, 4-pyrimidinyl and 5-pyrimidinyl, furthermore 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl, in particular pyridyl, pyrimidyl, furanyl and thienyl .

All phenyl and heterocyclic rings are preferred unsubstituted or carry a halogen, methyl, trifluor methyl or methoxy substituents.

With regard to the use of the compounds of the formula I according to the invention as herbicides and / or as defoliant / desiccant compounds, the variables preferably have the following meanings and were in each case individually or in combination:
X is -N (R⁷) -O- bonded to R⁸ via oxygen;
X -ON (R⁷) - bound to R⁸ via nitrogen;
Y oxygen;
R1 halogen or cyano;
R² is hydrogen, fluorine or chlorine;
R³ amino or methyl;
R⁴ C₁-C₆-alkyl, C₁-C₆-haloalkyl or C₁-C₆-alkylsulfonyl, particularly preferably C₁-C₄-haloalkyl, in particular trifluoromethyl, chlorodifluoromethyl or pentafluoroethyl;
R⁵ is hydrogen or halogen;
R⁶ is hydrogen or C₁-C₄ alkyl, particularly preferably hydrogen;
R⁷ hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-halogeno alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, (C₁-C₆-alkyl) carbonyl, (C₃-C₆-alkenyl) carbonyl, (C₃-C₆-alkynyl) carbonyl, (C₁-C₆-alkoxy) carbonyl, (C₂-C₆-alkenyloxy) carbonyl, (C₂-C₆-alkynyloxy) carbonyl, (C₁-C₆-alkylthio) carbonyl, C₁-C₆ Alkylcarbamoyl, each of the latter 13 radicals being able to carry one or two substituents if desired, each selected from the group consisting of

• - Nitro, cyano, halogen, C₃-C₈ cycloalkyl, hydroxy, C₁-C₆-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkylsulfenyl, C₁-C₆-alkylsulfonyl, C₁-C₆ alkylidene aminoxy,
• - a group -CO-Z¹R⁹, -OCO-Z¹R⁹ or -N (R⁹) R¹⁰;

R⁸ is hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-halogen alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl, each of which the latter 5 residues, if desired, one or two Can carry substituents, each selected from the group consisting of

• - Nitro, cyano, halogen, C₃-C₈ cycloalkyl, hydroxy, C₁-C₆-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkylsulfenyl, C₁-C₆-alkylsulfonyl, C₁-C₆ alkylidene aminoxy,
• - a group -CO-Z²R¹¹, -OCO-Z²R¹¹ or -N (R¹¹) R¹²; Z¹ is a chemical bond, oxygen, sulfur or -N (R¹⁰) -;

Z² is a chemical bond, oxygen, sulfur or -N (R¹²) -;
R⁹, R¹¹ independently of one another hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alk oxy-C₁-C₆-alkyl or (C₁-C₆-alkoxy ) carbonyl-C₁-C₆-alkyl; or
Z¹ and R⁹ and / or Z² and R¹¹ each together for a nitrogen-bonded 3- to 7-membered heterocycle having one to three heteroatoms, selected from the group consisting of two oxygen atoms, two sulfur atoms and 3 nitrogen atoms, the heterocycle being saturated, partially or completely be unsaturated or aromatic and, if desired, can carry one to three substituents, each selected from the group consisting of nitro, cyano, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl and C₁-C₆-alkoxy;
R¹⁰, R¹² independently of one another are hydrogen or C₁-C₆-alkyl.

R⁷ particularly preferably stands for:
Hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, (C₁-C₆-alkyl) carbonyl, (C₃-C₆-alkenyl) carbonyl, (C₃-C₆-alkynyl) carbonyl, (C₁-C₆-alkoxy) carbonyl or C₁-C₆-alkylcarbamoyl, where each of the last 10 radicals can also carry one of the following substituents: nitro, cyano, halogen, C₃-C₈-cycloalkyl, Hydroxy, C₁-C₆-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkyl sulfenyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylideneaminoxy, a group CO-Z¹R⁹, -OCO-Z¹R⁹ or -N (R⁹) R¹⁰.

R⁸ particularly preferably stands for:
Hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl, where each of the latter 5 residues can also carry one of the following substituents:
Nitro, cyano, halogen, C₃-C₈-cycloalkyl, hydroxy, C₁-C₆-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylidene aminoxy, a group -CO-Z²R¹¹, -OCO-Z²R¹¹ or -N (R¹¹) R¹².

Table 1 below is very particularly preferred led compounds Ia (, I with X = -NH-O-, Y = oxygen, R¹ = chlorine, R² = fluorine, R³ = amino, R⁴ = trifluoromethyl and R⁵, R⁶ = hydrogen):

Table 1

Furthermore, the following are benzylhydroxylamines of formula I. very particularly preferred

• - The compounds Ib.01-Ib.84, which differ from the corresponding compounds Ia.01-Ia.84 only in that R¹ is cyano:
• - The compounds Ic.01-Ic.84, which differ from the corresponding compounds Ia.01-Ia.84 only in that R² is hydrogen:
• - The compounds Id.01-Id.84, which differ from the corresponding compounds Ia.01-Ia.84 only in that R¹ is cyano and R² is hydrogen:
• - The compounds Ie.01-Ie.84, which differ from the corresponding compounds Ia.01-Ia.84 only in that R³ is methyl:
• - The compounds If.01-If.84, which differ from the corresponding compounds Ia.01-Ia.84 only in that R¹ is cyano and R³ is methyl:
• - The compounds Ig.01-Ig.84, which differ from the corresponding compounds Ia.01-Ia.84 only in that R² is hydrogen and R³ is methyl:
• - The compounds Ih.01-Ih.84, which differ from the corresponding compounds Ia.01-Ia.84 only in that R¹ is cyano, R² is hydrogen and R³ is methyl:

Furthermore, those listed in Table 2 below Compounds Ii (I with Y = oxygen, R¹ = chlorine, R² = fluorine, R³ = amino, R⁴ = trifluoromethyl, R⁵ and R⁶ = hydrogen, R⁸ = methyl) is particularly preferred:

Table 2

The following benzylhydroxylamines I are also very special prefers:

• - The compounds Ik.98-Ik.243, which differ from the corresponding compounds Ii.01-Ii.243 only in that R¹ is cyano:
• - The compounds Il.01-Il.243, which differ from the corresponding compounds Ii.01-Ii.243 only in that R² is hydrogen:
• - The compounds Im.01-Im.243, which differ from the corresponding compounds Ii.01-Ii.243 only in that R¹ is cyano and R² is hydrogen:
• - The compounds In.01-In.243, which differ from the corresponding compounds Ii.01-Ii.243 only in that R³ is methyl:
• - The compounds Io.01-Io.243, which differ from the corresponding compounds Ii.01-Ii.243 only in that R¹ is cyano and R³ is methyl:
• - The compounds Ip.01-Ip.243, which differ from the corresponding compounds Ii.01-Ii.243 only in that R² is hydrogen and R³ is methyl:
• - The compounds Iq.01-Iq.243, which differ from the corresponding compounds Ii.01-Ii.243 only in that R¹ is cyano, R² is hydrogen and R³ is methyl:

In addition, those listed in Table 3 below Compounds Ir (I with Y = oxygen, R¹ = chlorine, R³ = methyl, R⁴ = trifluoromethyl, R⁵ and R⁶ = hydrogen) very particularly prefers:

Table 3

Finally, the following benzylhydroxylamines I are complete particularly preferred:

• - The compounds Is.01-Is.46, which differ from the corresponding compounds Ir.01-Ir.46 only in that R¹ is cyano:
• - The compounds It.01-It.46, which differ from the corresponding compounds Ir.01-Ir.46 only in that R³ is amino:
• - The compounds Iu.01-Iu.46, which differ from the corresponding compounds Ir.01-Ir.46 only in that R¹ is cyano and R³ is amino:

The benzylhydroxylamines of formula I are in different ways available, for example by one of the following methods:  

Procedure A)

Cyclization of an enamine ester of formula IV or an enamine carboxylate of formula V in the presence of a base:

L¹ means low molecular weight alkyl, preferably C₁-C₄ alkyl, or phenyl.

As a rule, one cyclizes in an inert organic Solvent or diluent that is aprotic for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, all in one Aromatics such as benzene and toluene or in a polar solvent such as dimethylformamide and dimethyl sulfoxide. Mixtures too from polar solvent and a hydrocarbon such as n-hexane are suitable. Depending on the starting compound, water can also be used be suitable as a diluent.

Alkali metal alcoholates are preferably used as bases especially the sodium alcoholates, alkali metal hydroxides, ins special sodium hydroxide and potassium hydroxide, alkali metal carbonates, especially sodium carbonate and potassium carbonate, and metal hydrides, especially sodium hydride. When using sodium hydride as the base, it has proven to be proven advantageous in an aliphatic or cyclic Ether, in dimethylformamide or in dimethyl sulfoxide work.  

Usually the 0.5 to twice the molar amount is on Base, based on the amount of IV or V, for success the reaction is sufficient.

In general, the reaction temperature is (-78) ° C up to the boiling point of the respective reaction mixture, especially at (-60) to 60 ° C.

If R³ in formula IV or V is hydrogen, it becomes Process product obtained as a metal salt, the metal corresponds to the cation of the base used. The salt can isolated and cleaned in a manner known per se or if desired using acid in the free compound I with R³ = hydrogen.

Procedure B)

Methylation of a compound I in which R³ is hydrogen, in the presence of a base:

Examples of methylating agents are methyl halides, preferably methyl chloride, iodide or bromide, as well as dimethyl sulfate, methanesulfonate (methyl mesylate), methyl benzenesulfonate, methane p-tolylsulfonate (methyl tosylate), Methane p-bromobenzenesulfonate (methyl brosylate), trifluoromethane sulfonylmethane (methyl triflate) and diazomethane.

As a rule, one works in an inert organic Solvents, for example in a protic solution medium like the lower alcohols, preferably in ethanol, optionally in a mixture with water, or in one aprotic solvent, e.g. B. in an aliphatic or cyclic ether, preferably in 1,2-dimethoxyethane, tetra hydrofuran or dioxane, in an aliphatic ketone preferably in acetone, in an amide, preferably in dimethyl formamide, in a sulfoxide, preferably in dimethyl sulfoxide, in a urea such as tetramethyl urea and 1,3-Dimethyltetrahydro2 (1H) -pyrimidinone, in a carbon acid esters such as ethyl acetate, or in a halogenated  aliphatic or aromatic hydrocarbon such as Dichloromethane and chlorobenzene.

Suitable bases are inorganic bases, e.g. B. carbonates like Sodium carbonate and potassium carbonate, hydrogen carbonates such as Sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, as well as organic bases, e.g. B. amines such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methoxide, sodium ethanolate and potassium tert-butoxide.

The amount of base and methylating agent is preferably each at 0.5 to twice the molar amount, based on the amount of starting compound.

In general, the reaction temperature is from 0 ° C to Height of the boiling point of the reaction mixture, in particular at 0 to 60 ° C.

A preferred method variant is that of Cyclization of IV (R³ = H) or V (R³ = H) according to the procedure A) salt of I obtained without isolation from the reaction mixture, the excess base, e.g. B. sodium hydride, May contain sodium alcoholate or sodium carbonate methylate.

Unless directly described by method A) bene cyclization can be prepared under basic conditions, can the salts of those compounds I in which R³ Hydrogen means, also in a manner known per se from the Process products of method A) are obtained. To this For example, the aqueous solution is added to a purpose inorganic or organic base with the benzylhydroxyl amine I, in which R³ represents hydrogen. Salt formation usually takes place at 20-25 ° C with sufficient Speed.

It is particularly advantageous to dissolve the sodium salt of benzylhydroxylamine I (R³ = hydrogen) in aqueous To produce sodium hydroxide solution at 20-25 ° C, about equivalent amounts of benzylhydroxylamine and sodium hydroxide be used. The salt of the benzylhydroxylamine can then e.g. B. by precipitation with a suitable inert solvent or isolated by evaporation of the solvent.  

Salts of Benzylhydroxylamine I (R³ = H), their metal ion is not an alkali metal ion, usually by salting of the corresponding alkali metal salt in aqueous solution be put. In this way, z. B. Benzyl Produce hydroxylamine metal salts that are insoluble in water are.

Process C)

Implementation of a benzylhydroxylamine of formula I, wherein R³ water substance means with an electrophilic amination reagent in Presence of a base:

So far, 2,4-dinitrophenoxyamine has been used as an amination reagent especially proven, however, e.g. B. also hydroxylamine-O- sulfonic acid (HOSA) used, from the literature is already known as an amination reagent (see e.g. E. Hofer et al., Synthesis 1983, 466; W. Friedrichsen et al., Heterocycles 20 (1983) 1271; H. Hart et al., Tetrahedron Lett. 25 (1984) 2073; B. Vercek et al., Months. Chem. 114 (1983) 789; G. Sosnousky et al., Z. Naturforsch. 38 (1983) 884; R.S. Atkinson et al., J. Chem. Soc. Perkin Trans. 1987, 2787).

The amination can be carried out in a manner known per se (see e.g. T. Sheradsky, Tetrahedron Lett. 1968, 1909; M.P. Wentland et al., J. Med. Chem. 27 (1984) 1103 and in particular EP-A 240 194, EP-A 476 697, EP-A 517 181 and WO 95/06641, where the amination of uracil is taught).

Usually you do the implementation in a polar Solvent through, e.g. B. in dimethylformamide, N-methylpyrro lidon, dimethyl sulfoxide or in ethyl acetate, which was previously has proven to be particularly suitable.  

Suitable bases are, for example, alkali metal carbonates such as Potassium carbonate, alkali metal alcoholates such as sodium methylate and potassium tert-butoxide or alkali metal hydrides such as Sodium hydride.

The amount of base and aminating agent is preferably each at 0.5 to twice the molar amount, based on the amount of starting compound.

Depending on the meaning of R⁷ and R⁸, it may be necessary these substituents before the amination in a known per se Way to protect. This is particularly recommended if R⁷ or R⁸ is hydrogen.

Procedure D)

Sulfurization of a benzylhydroxylamine of formula I with Y = acid material:

The sulfurization is usually carried out in an inert Solvents or diluents, for example in one aromatic hydrocarbon such as toluene and the xylenes, in an ether such as diethyl ether, 1,2-dimethoxyethane and Tetrahydrofuran, or in an organic amine such as pyridine.

Are particularly suitable as a sulfurization reagent Phosphorus (V) sulfide and 2,4-bis (4-methoxyphenyl) -1,3,2,4- dithiadiphosphetane-2,4-dithione ("Lawesson's reagent").

Usually 1 to 5 times the molar amount is based on the starting compound to be sulfurized, for a far full implementation sufficient.

The reaction temperature is usually 20 to 200 ° C, preferably at 40 ° C to the boiling point of the reaction mixed.  

Procedure E)

Alkylation or acylation of a benzylhydroxylamine of the formula I, in which R⁷ is hydrogen, in the presence of a base:

The alkylation can be carried out, for example, with the halide preferably the chloride or bromide, the sulfate, sulfonate, preferably methanesulfonate (mesylate), benzenesulfonate, p-toluenesulfonate (tosylate), p-bromobenzenesulfonate (brosylate), the trifluoromethanesulfonate (triflate) or the diazo compound an unsubstituted or substituted alkane, cyclo alkane, haloalkane, alkene or alkyne.

Suitable acylating agents are e.g. B. the acid halides, especially the acid chlorides, the anhydrides, isocyanates and Sulfonyl chlorides of optionally substituted alkane, Cycloalkanoic, alkene, alkynic or phenylcarboxylic acids. It but also the free acids or their anhydrides come in Consider if then in the presence of a condensing agent worked like carbonyldiimidazole and dicyclohexylcarbodiimide becomes.

Usually you work in an inert organic Solvent, preferably in an aprotic solution medium, e.g. B. an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an ali phatic ketone such as acetone, an amide such as dimethylformamide, a sulfoxide such as dimethyl sulfoxide, a urea such as Tetramethyl urea and 1,3-dimethyltetrahydro-2 (1H) - pyrimidinone, a carboxylic acid ester such as ethyl acetate, or a halogenated aliphatic or aromatic Hydrocarbon such as dichloromethane and chlorobenzene.

Both inorganic bases, e.g. B. Alkali metal carbonates such as sodium carbonate and potassium carbonate, Alkali metal bicarbonates such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, as well as organic bases, e.g. B. Amines like Triethylamine, pyridine and N, N-diethylaniline, or alkali  metal alcoholates such as sodium methoxide, ethanolate and Potassium tert-butoxide.

The amount of base and alkylating agent is preferably at 0.5 to twice the molar amount, based on the Amount of I with R⁷ = hydrogen.

In general, a reaction temperature of 0 ° C to the boiling point of the reaction mixture, ins special from 0 to 60 ° C.

Any regioselectivity problems with parent compounds with R³ = hydrogen can in a known manner (Ver application of 2 equivalents of base, introduction of a protection group etc.) can be avoided.

Procedure F)

Reduction of an oximino compound of the formula VII:

Suitable reducing agents are, for example, hydrides such as Borane complexes, e.g. B. borane dimethyl sulfide or borane pyridine Complexes, further silanes such as triethylsilane and diphenyl methylsilane, or molecular hydrogen using a catalyst like platinum on coal.

When using hydrogen, a reak is recommended tion management under acidic conditions, e.g. B. in an organi or inorganic acid as a solvent.

The hydrogen pressure is usually up to normal pressure about 10 bar overpressure.

The reduction is generally successful at temperatures of (-5) to + 50 ° C.

The amount of reducing agent is not critical. It can with a smaller amount of reducing agent, based on the Amount of VII, or with an excess, up to about 15 times  molar amount. Preferably used 0.5 to twice the molar amount of reducing agent, based on the oximino compound VII.

Procedure G)

Cleavage of an alkylidene aminoxy compound of the formula VIII:

The cleavage is conveniently carried out using a Brønsted acid Catalyst carried out. Usually the 0.5- up to 2 times the molar amount of acid, based on the amount of VIII, sufficient. Consider z. B. organic acids such as acetic acid and inorganic acids such as sulfuric acid and Hydrochloric acid.

The reaction can be carried out directly in the acid or in an inert Solvents, e.g. B. in toluene.

The cleavage is preferably carried out in the presence of an oxime such as hydroxylamine and methylhydroxylamine, the oxime then approximately equimolar or in excess up to 20 times the mole Ren amount, based on the amount of VIII, is used.

In general, a reaction temperature of 0 ° C to the boiling point of the reaction mixture.

The alkylidenaminoxy compounds VIII are in turn z. B. available from benzyl derivatives IX:

The reaction is usually carried out in an inert solvent / diluent with the desired alkylidene aminohydroxide HO-N = C (Ra, R ^b ). If IX is used as the benzyl halide (IXa), it is recommended to work in the presence of an organic base such as triethylamine or an inorganic base such as sodium and potassium carbonate. On the other hand, if you start from a benzyl alcohol (IXb), a condensation aid such as carbodiimidazole is required.

Aromatics such as toluene are used as solvents and the xylenes, esters such as ethyl acetate, ethers such as Diethyl ether and tetrahydrofuran, halogenated aliphatics such as Methylene chloride or basic solvents such as pyridine and Dimethylformamide into consideration.

Advantageously, IX and alkylidene aminohydroxide in about stoichiometric amounts used, or you work with a slight excess of one or the other compo nente, up to about 10 mol%.

In general, the reaction is carried out at a Temperature from 0 ° C to the boiling temperature of the reaction mixture nice.

Procedure H)

Reaction of benzyl alcohols IXa with hydroxylamines HO-N (R⁷) -R⁸:

It is preferred to work in the presence of condensation auxiliaries such as carbodiimidazole, the amount of which is usually at 0.5 to 2 times the molar amount, based on the amount to IXa.

The reaction is usually carried out in an inert organic Solvents, e.g. B. a hydrocarbon such as toluene and the xylenes, an ester such as ethyl acetate or one Ethers such as diethyl ether and tetrahydrofuran performed.  

It is expedient to set IXa and Xa approximately stoichiometric Amounts, or you work with a small excess one or the other component, up to about 10 mol%.

In general, a reaction temperature of 0 ° C to the boiling point of the reaction mixture.

Procedure K)

Halogenation of a benzylhydroxylamine of the formula I in which R⁵ Hydrogen means:

The halogenation is usually carried out in an inert organic solvents or diluents. For the Chlorination and bromination come for example aliphatic Carboxylic acids such as acetic acid, or chlorinated aliphatic Hydrocarbons such as methylene chloride, chloroform and tetra chlorocarbon. For iodination are low especially boiling aliphatic carboxylic acids such as acetic acid prefers.

Chlorination and bromination are particularly suitable elemental chlorine or bromine, or sulfuryl chloride or Sulfuryl bromide, at a preferred reaction temperature as 0 to 60 ° C, especially 10 to 30 ° C.

If desired, the chlorination and bromination in In the presence of an acid-binding agent, wherein Sodium acetate and tertiary amines such as triethylamine, dimethyl aniline and pyridine are particularly preferred.

Elemental iodine is particularly preferred as the iodine, in which case the reaction temperature is about 0 to 110 ° C, preferably 10 to 30 ° C.

The iodination is particularly advantageously carried out in the presence a mineral acid such as fuming nitric acid.  

The amount of halogenating agent is not critical; nor sometimes equimolar amounts of halogenation are used medium or an excess of up to about 200 mol%, based on the starting compound (I with R⁵ = hydrogen).

Excess iodine can, for example, after the reaction using saturated aqueous sodium bisulfite solution be removed.

Procedure L)

Alkylation of a hydroxylamine or a hydroxamic acid with a benzyl halide or benzyl alcohol derivative of the formula XI in the presence of a base:

L² means halogen or lower alkyl sulfonate, lower halogen alkyl sulfonate or phenyl sulfonate, which may be substituted can.

As a rule, one works in an inert organic Solvents, especially aprotic solvents, e.g. B. aliphatic or cyclic ether such as preferably 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aliphatic Ketones such as preferably acetone, amides such as preferably Dimethylformamide, sulfoxides such as preferably dimethyl sulfoxide, ureas such as tetramethyl urea and 1,3-dimethyltetrahydro-2 (1H) pyrimidinone, carboxylic acid ester such as ethyl acetate, or halogenated aliphatic or aromatic hydrocarbons such as dichloromethane and Chlorobenzene can be considered.

Both inorganic bases, e.g. B. Carbonates such as the alkali metal carbonates, in particular Sodium carbonate and potassium carbonate, hydrogen carbonates such as the alkali metal bicarbonates, especially sodium and Potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, as well as organic bases, e.g. B. Amines such as triethylamine, pyridine and N, N-diethylaniline, or  Alkali metal alcoholates such as sodium methoxide, sodium ethanolate and potassium tert-butoxide.

The amounts of base and alkylating agent XI are more normal wise at 0.5 to 2 times the molar amount, based on the amount of X.

In general, one works at a reaction temperature of (-78) ° C to the boiling point of the reaction mixture, ins especially at (-60) to 60 ° C.

The enamine esters of formula IV are new. Your manufacture can done according to known methods, e.g. B. after a of the following procedures:

It is preferable to work essentially water-free in one inert solvents or diluents, particularly preferred in the presence of an acidic or basic catalyst.

In particular, come as solvents or diluents Water azeotropically miscible organic solvents for example aromatics such as benzene, toluene and the xylenes, halogenated hydrocarbons such as methylene chloride, chloro form, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and Dioxane, or cyclohexane, but also alcohols such as methanol and Ethanol.

Strong minerals are preferred as acid catalysts acids such as sulfuric acid and hydrochloric acid, containing phosphorus Acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid and acidic cations exchangers like "Amberlyst 15" (Fa. Fluka).  

As basic catalysts are z. B. metal hydrides such Sodium hydride and particularly preferably metal alcoholates such as Sodium methoxide and ethanolate.

Appropriately, XIII and the β-ketoester XII are set approximately stoichiometric amounts, or you work with one slight excess of one or the other component, until about 10 mol%.

Usually, 0.5 to 2 times the molar amount is on Catalyst, based on the amount of one of the starting connections, sufficient.

In general, the reaction is carried out at a Temperature from 60 to 120 ° C, for the rapid removal of water formed preferably at the boiling temperature of the reaction mixture.

L³ stands for C₁-C₄-alkyl or phenyl.

This implementation can take place, for example, in an inert, with Water-miscible organic solvents, for example an aliphatic or cyclic ether such as 1,2-dimethoxy ethane, tetrahydrofuran and dioxane, or a lower Alcohol, especially ethanol, are carried out, the Reaction temperature normally at 50 to 100 ° C, preferably as at the boiling point of the reaction mixture.

However, the reaction can also be carried out in an aromatic ver thinning agents such as benzene, toluene and the xylenes be performed, in which case the addition either an acidic catalyst such as hydrochloric acid and p-toluenesulfone acid or a base, e.g. B. an alkali metal alcoholate such as sodium methoxide and sodium ethanolate, recommended is. The reaction is also in this process variant  temperature normally at 50 to 100 ° C, but preferred at 60 to 80 ° C.

With regard to the proportions, the information applies to Method M).

The reaction is conveniently carried out in the presence of an im essential anhydrous aprotic organic solvent or diluent, for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, Tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and Xylenes, a halogenated, aliphatic hydrocarbon substance such as methylene chloride, chloroform, carbon tetrachloride substance, 1,2-dichloroethane and chlorobenzene, an aprotic polar solvents such as dimethylformamide, hexamethyl phosphoric acid triamide and dimethyl sulfoxide, or one Mixture of the solvents mentioned.

If desired, can also be in the presence of a metal hydride base such as sodium and potassium hydride, an alkali metal or Alkaline earth metal alcoholates such as sodium methoxide, ethanolate and potassium tert-butoxide, or an organic tertiary Base such as triethylamine and pyridine are worked, wherein the organic base also serve as a solvent can.

The starting compounds are expediently placed in stoichio metric quantities or one works with a small one Excess of one or the other component up to about 10 mol%. When working without solvent in the presence An organic base is recommended, the latter in one use a larger excess.  

Usually a reaction temperature is from (-80) to 50 ° C, in particular (-60) to 30 ° C is sufficient.

In a particularly preferred embodiment, the Enamine ester IV obtained with excess base directly (i.e. "in situ") according to method A) into the corresponding value product I transferred. Any by-products (e.g. C-alkyllie tion products for compounds with R⁵ = hydrogen) by means of conventional separation processes such as crystallization and Remove chromatography.

L⁴ represents C₁-C₄ alkyl or phenyl.

This reaction is conveniently carried out in an aprotic polar solvents or diluents such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, before partial in the presence of a base, for example an alka lime metal or alkaline earth metal alcoholate, especially one Sodium alkanolates such as sodium methoxide, an alkali metal or alkaline earth metal carbonates, especially sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.

Usually 0.5 to 2 times the molar amount of base, based on the amount of XV or XVII, sufficient.

The reaction temperature is generally 80 to 180 ° C, preferably at the boiling point of the reaction mixed.

With regard to the proportions of the starting compounds the information for method M) applies.

In a particularly preferred embodiment, one uses a sodium alcoholate as the base and distilled the course alcohol formed continuously from the reaction. The on  Enamine esters IV prepared in this way can be used without iso lation from the reaction mixture according to process A) to a Salt of the corresponding benzylhydroxylamine I cyclized will.

This implementation is essentially carried out in one anhydrous, aprotic, organic solution or diluent agent, for example in the presence of an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, Tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and Xylenes, a halogenated, aliphatic hydrocarbon substance such as methylene chloride, chloroform, carbon tetrachloride substance, 1,2-dichloroethane and chlorobenzene, an aprotic polar solvent such as dimethylformamide, hexamethyl phosphoric acid triamide and dimethyl sulfoxide, or one Mixture of the solvents mentioned.

If desired, in the presence of a metal hydride base such as sodium and potassium hydride, an alkali metal or earth alkali metal alcoholates such as sodium methoxide, ethanolate and Potassium tert-butoxide, or an organic nitrogen base how to work triethylamine and pyridine, the organic base can simultaneously serve as a solvent.

The starting compounds are expediently put in stoichiometric amounts or one of the Components in excess, up to about 20 mol%. At work without solvent in the presence of an organic base the latter is advantageously used in an even larger one Excess.

The reaction temperature is generally from (-80) to 150 ° C, preferably at (-30) ° C to the boiling point of the respective Reaction mixture.  

The enamine carboxylates of formula V are also new; you too can be produced in a manner known per se, for example wise from an aniline derivative of the formula XV according to the following reac tion scheme R):

XX is preferably converted into XIX in one anhydrous inert aprotic solvent, for example wise in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and the xylenes, or an aliphatic or cyclic ether such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetra hydrofuran and dioxane.

The reaction temperature for this reaction is (from XX with XIX) in general at about 70 to 140 ° C, in particular at 100 to 120 ° C.

The implementation of XII with XIX is a Aminolysis, which is usually either without a solvent [cf. e.g. B. J. Soc. Dyes Col. 42, 81 (1926), Ber. 64, 970 (1931); Org. Synth., Coll. Vol. IV, 80 (1963) and J. Am. Chem. Soc. 70, 2402 (1948)] or in an inert anhydrous Solvent / diluent, especially in an aprotic Solvents, for example in an aromatic such as toluene and Xylenes, or a halogenated aromatic such as chlorobenzene, is carried out.

Working in the presence of a person is recommended basic catalyst, for example a higher boiling Amines [see e.g. B. Helv. Chim. Acta 11, 779 (1928) and US 2,416,738] or of pyridine.  

The reaction temperature is preferably about 20 to 160 ° C.

The starting compounds are expediently set in each case in about stoichiometric amounts or you work with a slight excess of one or the other component, up to about 10 mol%. Do you work in the presence of a basic Catalyst, is usually 0.5 to 2 times the molar Amount of catalyst, based on the amount of one of the starting materials, sufficient.

The subsequent implementation of the compounds thus produced of formula XXI with the amine HN (R³) -COOL¹ is advantageous in a largely water-free solvent / diluent Normal pressure carried out, particularly preferably in the presence an acid catalyst.

For the production of enamine carboxylates V with R³ = amino it is recommended to use compounds XXII with protected amino group (e.g. as a hydrazone).

The solvents / diluents come in particular with water azeotropically miscible organic liquids, for example Aromatics such as benzene, toluene and the xylenes, or halogenated Hydrocarbons such as carbon tetrachloride and chlorobenzene, into consideration.

Suitable catalysts are in particular strong mineral acid such as sulfuric acid, organic acids such as p-toluenesulfone acid, phosphorus-containing acids such as orthophosphoric acid and Polyphosphoric acid or acidic cation exchangers such as "Amber lyst 15 "(from Fluka).

In general, the reaction temperature is about 70 to 150 ° C; for the rapid removal of the resulting reaction However, water is conveniently worked at the boilers temperature of the respective reaction mixture.

The compounds of the formulas XIII, XVI, XVII and XXI are flat if new. They too can be made in a manner known per se represent, particularly advantageous from the compounds of formula XIX:  

S) "Phosgenation" of compounds of formula XIX and Hydrolysis of process products XVI with ammonia (derivatives)

The process can be carried out in an inert, essentially water free solvent / diluent or without solvent be performed. The conversion of the amino into the isocyanate Group is preferably carried out using phosgene or chlorine trichloromethyl formate.

In particular come as solvents / diluents aprotic, organic solvents, for example aromatics such as toluene and the xylenes, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorine benzene, aliphatic or cyclic ethers such as 1,2-dimethoxy ethane, tetrahydrofuran and dioxane, esters such as ethyl acetate esters, as well as mixtures of these solvents.

Depending on the aniline derivative XIX used, the addition a base such as triethylamine may be advantageous, for example in 0.5 to 2 times the molar amount, based on the amount of XIX.

The phenyl isocyanates XVI usually arise from Reaction temperatures from 50 ° C to the boiling point of the reak mixture of ions; you can then with ammonia or a reactive derivative of ammonia to the phenylurea derivatives XIII are implemented.

T) Reaction with alkali metal cyanates

M⁺ stands for the equivalent of a metal ion, in particular for an alkali metal ion such as sodium and potassium.

The reaction is usually carried out in an inert solution / Diluent, for example in an aromatic Hydrocarbon like toluene and the xylenes, in one aliphatic or cyclic ethers such as tetrahydrofuran and Dioxane, in a lower alcohol like methanol and ethanol, in water or in a mixture of the solvents mentioned.  

The amount of cyanate is not critical; for a complete Implementation requires at least equimolar amounts Aniline compound XIX and cyanate, however, can also be a Excess cyanate, up to about 100 mol%, offer advantages.

The reaction temperature is generally from 0 ° C to Boiling temperature of the reaction mixture.

U) implementation with esters L⁴O-CO-L⁵

L⁵ represents halogen, preferably chlorine or bromine C₁-C₄ alkoxy or for phenoxy.

Suitable solvents / diluents are, for example aromatic hydrocarbons such as toluene and the xylenes, halogenated hydrocarbons such as methylene chloride, chloro form, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and Dioxane, esters such as ethyl acetate, alcohols such as methanol and ethanol, or water.

Mixtures of an organic solvent and water is being brought up for consideration.

It is preferred to work in the presence of a base, e.g. B. in Presence of an alkali metal hydroxide, carbonate or alcoholates such as sodium hydroxide, carbonate, methanolate and ethanolate, or a tertiary amine such as pyridine and Triethylamine.

If desired, a catalyst, e.g. B. a Lewis acid such as antimony trichloride can be added.

The starting compounds and are expediently set the base in about stoichiometric amounts, however also one or the other component in excess, up to approx. 100 mol%.  

The amount of catalyst is generally 1 to 50 mol%, preferably 2 to 30 mol%, based on the amount on aniline compound XIX used.

The reaction normally succeeds at reaction temperatures from (-40) ° C to the boiling point of the reaction mixture.

The aniline compounds of formula XIX are also new. Your Synthesis usually takes place from the corresponding nitro ver Bonds XXIII by hydrogenation or from anilines of the formula XXIV, which according to method F) in the corresponding aniline ver bonds of the formula XIX can be transferred:

The nitro compounds of the formula XXIII are also new. she can be made according to methods known per se, e.g. B. by Nitration of the corresponding benzylamines.

The compounds of formula VII, X, XI, XII, XIV, XV, XVIII, XIX and XXIV are known or can be represented in a manner known per se (see e.g. WO 92/02088 and DE-A 42 37 920).

Unless otherwise stated, all are described above NEN method expediently at atmospheric pressure or below the intrinsic pressure of the respective reaction mixture.

Depending on the substitution pattern of the target compounds, it can the sequence of individual reaction steps should be recommended to be exchanged so that certain by-products are not or in less amount.  

The reaction mixtures are usually worked up after methods known per se, for example by removing the Solvent, distribute the residue in a mixture Water and a suitable organic solvent and Auf work the organic phase towards the product.

The benzylhydroxylamines of the formula I can have one or more Chirality centers usually contain and fall as Mixtures of enantiomers or diastereomers, if none targeted synthesis is carried out on an isomer. The If desired, mixtures can be prepared according to the usual methods Methods, e.g. B. by means of crystallization or chromatography an optically active adsorbate, into the largely pure isomers be separated. Pure optically active isomers can be for example also from corresponding optically active output manufacture materials.

Benzylhydroxylamine I, in which R³, R⁷ or R⁸ hydrogen means, in a manner known per se, in their salts, preferably convert into their alkali metal salts.

Salts of I whose metal ion is not an alkali metal ion can by salting the corresponding alkali metal salt in the usual way Be produced in the same way, as well as ammonium, phosphonium, Sulfonium and sulfoxonium salts using ammonia, phosphonium, Sulfonium or sulfoxonium hydroxides.

The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of pure isomers - as herbicides. The herbicides containing I Agents fight plant growth on non-cultivated areas very well, especially with high application rates. In crops like wheat, rice, Corn, soybeans and cotton act against weeds and damage grasses without significantly damaging the crops. This The effect occurs especially at low application rates.

Depending on the particular application method, the compounds I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants. The following cultures are examples:
Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea libericaus), Cucumodison , Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batinas, linus lensinarium, Jupomoea batinaris, Jupomoea batinaris, Jupomoea batinaris, Jupomoea batatisum, Jupomoea batinaris, Jupomoea batinaris Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus av Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. Vulgare), Theobroma cacao, Trifolium pratense, Tr iticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds I can also be used in cultures which through breeding including genetic engineering methods against the The effects of herbicides are tolerant.

3-Uracilo-benzylhydroxylamines I are also suitable for the desiccation and / or defoliation of plants.

As desiccants, they are particularly suitable for drying out the aerial parts of crops such as potatoes, rapeseed, Sunflower and soybean. So that a completely mechani harvests these important crops.

Ease of harvest is also of economic interest, due to the concentrated or falling time the adherence to the tree with citrus, olives or other types and varieties of pome, stone and shell fruit light becomes. The same mechanism, that is, the promotion of Formation of separating tissue between fruit or leaf and Shoot part of the plants is also for a well controllable Defoliation of crops, especially cotton, essential.

In addition, the shortening of the time interval in which the individual cotton plants become mature, to an increased fiber quality after harvest.

The compounds I or the compositions containing them can be added for example in the form of directly sprayable aqueous solutions, Powders, suspensions, including high-proof aqueous, oily or other suspensions or dispersions, emulsions, oil dispersers sions, pastes, dusts, sprinkles or granules Spraying, atomizing, dusting, scattering or pouring be applied. The application forms depend on the uses  purposes; in any case, they should be the finest Ensure distribution of the active ingredients according to the invention.

As inert auxiliaries for the production of directly sprayed solutions, emulsions, pastes or oil dispersions come in essential considerations: mineral oil fractions from medium to high boiling point such as kerosene and diesel oil, as well as coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. B. paraffins, Tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, Ethanol, propanol, butanol and cyclohexanol, ketones such as cyclo hexanone, strongly polar solvents, e.g. B. amines such as N-methyl pyrrolidone and water.

Aqueous use forms can be made from emulsion concentrates, Suspensions, pastes, wettable powders or water dispersants granules can be prepared by adding water. For The production of emulsions, pastes or oil dispersions Substrates as such or dissolved in an oil or solvent, using wetting agents, adhesives, dispersants or emulsifiers in water be homogenized. But it can also be made from an active substance, Wetting, adhesive, dispersing or emulsifying agents and possibly Concentrates containing solvents or oil are produced, which are suitable for dilution with water.

The surface-active substances (adjuvants) are the alkali, Alkaline earth metal, ammonium salts of aromatic sulfonic acids, e.g. B. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkyl and alkylarylsulfonates, alkyl, Lauryl ether and fatty alcohol sulfates, as well as sulfated salts Hexa-, hepta- and octadecanols as well as fatty alcohol glycol ether, Condensation products of sulfonated naphthalene and its Derivatives with formaldehyde, condensation products of naphthalene or the naphthalenesulfonic acids with phenol and formaldehyde, poly oxyethylene octylphenol ether, ethoxylated isooctyl, octyl or Nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or Polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, Sorbitol esters, lignin sulfite waste liquors or methyl cellulose in Consideration.

Powders, materials for spreading and dusts can be mixed or mixed joint grinding of the active substances with a solid Carrier are manufactured.  

Granules, e.g. B. coating, impregnation and homogeneous granules can Herge by binding the active ingredients to solid carriers be put. Solid carriers are mineral soils like pebbles acids, silica gels, silicates, talc, kaolin, limestone, lime, Chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and Magnesium sulfate, magnesium oxide, ground plastics, fertilizers agents such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or others solid carriers.

The concentrations of the active ingredients I in the ready-to-use Preparations can be varied in a wide range. The Formulations generally contain about 0.001 to 98% by weight, preferably 0.01 to 95% by weight of at least one active ingredient. The Active ingredients are in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

The following formulation examples illustrate the Her provision of such preparations:

• I. 20 parts by weight of compound no. 1.01 are in one Dissolved mixture that alkylated from 80 parts by weight Benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide in 1 mole of oleic acid-N-monoethanol amide, 5 weight steep calcium salt of dodecylbenzenesulfone acid and 5 parts by weight of the adduct of There are 40 moles of ethylene oxide with 1 mole of castor oil. By off pour and finely distribute the solution in 100,000 weight divide water you get an aqueous dispersion that Contains 0.02% by weight of the active ingredient.
• II. 20 parts by weight of compound no. 1.02 are in one Dissolved mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the plant approximately 7 moles of ethylene oxide to 1 mole of isooctyl phenol and 10 parts by weight of the adduct of There are 40 moles of ethylene oxide with 1 mole of castor oil. By one pour and finely distribute the solution in 100,000 weight divide water you get an aqueous dispersion that Contains 0.02% by weight of the active ingredient.  
• III. 20 parts by weight of active ingredient no. 1.03 are in one Dissolved mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts of the deposit product of 40 moles of ethylene oxide with 1 mole of castor oil consists. By pouring in and finely distributing the solution an aqueous solution is obtained in 100,000 parts by weight of water Dispersion containing 0.02% by weight of the active ingredient.
• IV. 20 parts by weight of active ingredient no. 1.04 are with 3 parts by weight of the sodium salt of diisobutyl naphthalene-α-sulfonic acid, 17 parts by weight of sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 weight steep powdered silica gel well mixed and ground in a hammer mill. By fine Distribute the mixture in 20,000 parts by weight of water you hold a spray liquor, the 0.1 wt .-% of the active ingredient contains.
• V. 3 parts by weight of active ingredient no. 1.05 are with 97 parts by weight of finely divided kaolin mixed. Man receives a dusting agent that contains 3% by weight contains the active substance.
• VI. 20 parts by weight of active ingredient No. 1.16 are with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight share sodium salt of a phenol-urea-formaldehyde Condensates and 68 parts by weight of a paraffinic Mineral oil mixed intimately. A stable oily is obtained Dispersion.
• VII. 1 part by weight of active ingredient No. 1.17 is in a Dissolved mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and There are 10 parts by weight of ethoxylated castor oil. Man receives a stable emulsion concentrate.
• VIII. 1 part by weight of active ingredient No. 1.18 is in a Mixture dissolved from 80 parts by weight of cyclohexanone and 20 parts by weight of Emulphor EL (= ethoxylated Castor oil). A stable emulsion is obtained concentrate.

The application of the active ingredients I or the herbicidal compositions can pre-emergence or post-emergence. Are the Active ingredients for certain crops less tolerable, so application techniques can be used in which the herbicidal agents are sprayed with the help of sprayers, that the leaves of sensitive crops if possible not to be taken while the active ingredients are on the leaves including growing unwanted plants or the uncovered Floor space (post-directed, lay-by).

The amount of active ingredient I depends on the control target, season, target plants and growth stage 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.S.).

To broaden the spectrum of activity and to achieve syner The benzylhydroxylamines I with number rich representatives of other herbicides or growth regulators Active ingredient groups are mixed and applied together. For example, 1,2,4-thiadiazoles come as mixing partners, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, Aminotriazoles, anilides, aryloxy / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and their derivatives, benzothia diazinone, 2- (hetaroyl / aroyl) -1,3-cyclohexanedione, heteroaryl- Aryl ketones, benzylisoxazolidinones, meta-CF₃-phenyl derivatives, Carbamates, quinoline carboxylic acid and their derivatives, chloroacetani lide, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and their derivatives, dihydrobenzofurans, dihydrofuran-3-ones, Dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, Halogenated carboxylic acids and their derivatives, ureas, 3-phenyl uracile, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydro phthalimides, oxadiazoles, oxiranes, phenols, aryloxy and hetero aryloxyphenoxypropionic acid esters, phenylacetic acid and their Derivatives, 2-phenylpropionic acid and their derivatives, pyrazoles, Phenylpyrazoles, pyridazines, pyridinecarboxylic acid and their Derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, Triazines, triazinones, triazolinones, triazolecarboxamides and Uracile into consideration.

It may also be useful to use the compounds I alone or in combination with other herbicides also with others Plant protection products mixed, to apply together, at for example with means to control 08299 00070 552 001000280000000200012000285910818800040 0002019616719 00004 08180 of pests or phytopathogenic fungi or bacteria. It is also of interest the miscibility with mineral salt solutions, which are used to eliminate Nutritional and trace element deficiencies are used. It can non-phytotoxic oils and oil concentrates can also be added.

Manufacturing examples example 1 3- (4-chloro-3-methoxyaminomethylphenyl) -1-methyl-6-trifluoro methyl-1,2,3,4-tetrahydro-pyrimidine-2,4-dione (compound No. 1.01)}

To a solution of 3- (4-chloro-3-methoxyiminomethyl-phenyl) -1- methyl-6-trifluoromethyl-1,2,3,4-tetrahydro-pyrimidine-2,4-dione (3.6 g) in a mixture of 30 ml dichloromethane and 50 ml Trifluoroacetic acid, triethylsilane (1.9 ml) was added dropwise. After The solution was distilled for 20 hours at room temperature medium down. The residue was taken up in 200 ml of dichloromethane then take the organic phase four times with 50 ml of water washed, dried over sodium sulfate and finally turned on was narrowed. After crystallization with diisopropyl ether and petroleum ether the title compound was obtained (mp. 83-85 ° C).

Example 2 3- (4-chloro-3-ethoxyaminomethyl-phenyl) -1-methyl-6-trifluoromethyl- 1,2,3,4-tetrahydropyrimidine-2,4-dione (Compound No. 1.02)

To a solution of 3- (4-chloro-3-ethoxyiminomethyl-phenyl) -1- methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (3.8 g) in 40 ml of ethanol were successively borane at 0 ° C Pyridine complex (3 ml) and 10 percent hydrochloric acid (30 ml) dripped. Another 12 ml were then added within 16 hours Borane-pyridine complex added. Then you stirred the Solution 4 hours at reflux temperature, after which the solvent was distilled off. The residue was taken up in 200 ml dichlor methane on. The organic phase was twice with 50 ml Washed water, then dried over sodium sulfate and closed restricted. The title compound was obtained as an oil.

Example 3 3- (3- [acetyl- (methoxyamino) methyl] -4-chlorophenyl) -1-methyl-6- trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 1.04)

To a suspension of sodium hydride (0.17 g in 50 ml tetra hydrofuan) was 3- (4-chloro-3-methoxyaminomethyl-phenyl) -1- methyl-6-trifluoromethyl-1,2,3,4-tetrahydro-pyrimidine-2,4-dione (1.6 g in 30 ml of tetrahydrofuran). After one hour acetyl chloride (0.4 g in 20 ml of tetrahydrofuran) was added. The mixture was stirred at room temperature for 20 hours and on finally mixed with water (100 ml). From the aqueous phase the product of value was extracted with twice 100 ml of dichloromethane.  

The combined organic phases were washed three times with water washed, dried over sodium sulfate and from the solvent exempted. After chromatography on silica gel (mobile phase: dichlor methane / ethyl acetate = 9: 1) and crystallization with petroleum ether the title compound was obtained (mp. 160-161 ° C).

Example 4 3- (3 - [(methoxy-methylamino) methyl] -4-chlorophenyl) -1-methyl-6- trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 1.06)

To a mixture of methoxymethylamine (0.06 mol), potassium carbonate (0.012 mol) and 100 ml of dimethylformamide 3- (3-bromomethyl) -4-chloro-2-fluorophenyl) -1-methyl-6-trifluoro methyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (0.005 mol) was added. After 5 hours at room temperature, the reaction solution was concentrated. The residue was mixed with 100 ml of methylene chloride, after which the organic phase washed 3 times with 30 ml of water, then dried over sodium sulfate and finally concentrated. The oil thus obtained was obtained by adding petroleum ether the desired product of value.

Example 5 3- (3- [ethoxycarbonylaminooxy-methyl] -4-chloro-6-fluorophenyl) -1- amino-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (Ver Binding No.It. 10)

To a solution of 1.8 g of 3- (3-hydroxymethyl-4-chloro-6-fluorine phenyl) -1-amino-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine- 2,4-dione in 100 ml of tetrahydrofuran were 0.9 g of carbonyldi given imidazole. After stirring for 1 hour, the reaction was added mixture with 0.58 g of N-ethoxycarbonyl-hydroxylamine. Subsequently the mixture was stirred for a further 14 hours at 20 ° C., after which the Removed solvent by distillation. The backlog was in 100 ml of methylene chloride added. The organic obtained Phase was washed with water, dried over sodium sulfate and finally narrowed down. The crude product was cleaned using chromatography on silica gel (eluent: methylene chloride). Yield: 0.2 g.

In the following Table 4 are in addition to those described above other compounds listed further benzylhydroxylamines I, which were manufactured in an analogous manner or can be produced:  

Table 4

Examples of use (herbicidal activity)

The herbicidal activity of the benzylhydroxylamines I was demonstrated by the following greenhouse tests:
Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to species.

In pre-emergence treatment, the or suspended in water emulsified active ingredients directly after sowing using fine ver dividing nozzles applied. The vessels were lightly sprinkled, to promote germination and growth, and then with through visible plastic covers until the plants have grown were. This cover causes the test to germinate evenly plant, unless this is affected by the active ingredients has been.

For the purpose of post-emergence treatment, the test plants were each depending on the growth habit, only get raised to a height of 3 to 15 cm gene and only then with the suspended or emulsified in water treated active ingredients. The test plants were either sown directly and grown in the same containers or them were first grown separately as seedlings and a few days transplanted into the test vessels before treatment. The effort amount for post-emergence treatment was 0.0156, 0.0078, 0.0039 or 0.0019 kg / ha a.S. (active substance).

The plants became species-specific at temperatures from 10 to 25 ° C or 20 to 35 ° C kept. The trial period extended yourself over 2 to 4 weeks. During this time, the plants cared for, and their response to each treatment was evaluated.

Was rated on a scale from 0 to 100. Here means 100 no emergence of the plants or complete destruction at least the above-ground parts and 0 no damage or more normal Growth course.  

The plants used in the greenhouse experiments settled composed of the following types:

At a rate of 0.0156 or 0.0078 kg / ha a.S. showed compound no. 1.03 in the post-emergence process a very good one Effect against Abutilon theophrasti, Solanum nigrum and various those Veronica species.

At a rate of 3.9 or 1.9 g / ha a.S. showed the Compound No. It. 10 post-emergence a very good one Effect against Galium aparine, Sinapis alba and Solanum nigrum.

Examples of use (desiccative / defolian effectiveness)

Young, 4-petals (without cotyledons) served as test plants Cotton plants grown under greenhouse conditions (relative humidity 50 to 70%; day / night temperature = 27/20 ° C).

The young cotton plants were dripping wet with water-based treatments the active ingredients (with the addition of 0.15% by weight of the fat alcohol alkoxylate Plurafac LF 700, based on the spray mixture) leaf treated. The amount of water applied was converted 1000 l / ha. After 13 days, the number of those discarded Leaves and the degree of defoliation determined in%.

No leaf fall occurred in the untreated control plants.

Claims (20)

1. Benzylhydroxylamines of the formula I. in which the variables have the following meaning:
X -N (R⁷) -O-, which can be bound to R⁸ via oxygen or nitrogen;
Y oxygen or sulfur;
R1 halogen, cyano, nitro or trifluoromethyl;
R² is hydrogen or halogen;
R³ is hydrogen, amino or methyl;
R⁴ is hydrogen, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl or C₁-C₆-alkyl sulfonyl;
R⁵ is hydrogen, halogen or C₁-C₆ alkyl;
R⁶ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl or C₂-C₆-alkenyl;
R⁷ is hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, (C₁-C₆-alkyl) carbonyl, (C₃-C₆-alkenyl) carbonyl ,
(C₃-C₆-alkynyl) carbonyl, (C₁-C₆-alkoxy) carbonyl, (C₂-C₆-alkenyloxy) carbonyl, (C₂-C₆-alkynyloxy) carbonyl,
(C₁-C₆-alkylthio) carbonyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylcarbamoyl, each of the latter 14 radicals optionally being able to carry one to three substituents, each selected from the group consisting of

• - Nitro, cyano, halogen, C₃-C₈-cycloalkyl, hydroxy, C₁-C₆-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy , C₁-C₆-alkylthio, (C₁-C₆-alkyl) carbonyl, (C₁-C₆-alkyl) carbonyloxy, C₁-C₆-alkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylidene aminoxy, C₁-C₆-alkylcarbamoyl,
• - The phenyl, phenoxy or phenylsulfonyl group, where the phenyl rings may be unsubstituted or carry one to three substituents, each selected from the group consisting of halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy and C₁ -C₆ haloalkyl,
• - A 3- to 7-membered heterocyclyl or heterocyclyloxy group with one to three heteroatoms, selected from the group consisting of two oxygen atoms, two sulfur atoms and 3 nitrogen atoms, the heterocycle being saturated, partially or completely unsaturated or aromatic and, if desired, one to can carry three substituents, each selected from the group consisting of halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl and (C₁-C₆-alkyl) carbonyl,
• - A group -CO-Z¹R⁹, -OCO-Z¹R⁹ or -N (R⁹) R¹⁰, or

R⁷ C₃-C₈-cycloalkylcarbonyl, phenylcarbonyl, phenylsulfonyl or phenylcarbamoyl, where these 4 radicals can be unsubstituted or can carry one to three substituents, each selected from the group consisting of halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆- Alkoxy and C₁-C₆ halo alkyl;
R⁸ is hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-halogeno alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl, each of the latter 5 radicals optionally being able to carry one to three substituents, each selected from the group consisting of

• - Nitro, cyano, halogen, C₃-C₈-cycloalkyl, hydroxy, C₁-C₆-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy , C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-alkyl sulfonyl, C₁-C₆-alkylideneaminoxy,
• - The phenyl, phenoxy or phenylsulfonyl group, where the phenyl rings may be unsubstituted or carry one to three substituents, each selected from the group consisting of nitro, cyano, halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁ -C₆ haloalkyl,
• - A 3- to 7-membered heterocyclyl or heterocyclooxy group with one to three heteroatoms, selected from the group consisting of two oxygen atoms, two sulfur atoms and 3 nitrogen atoms, the heterocycle being saturated, partially or completely unsaturated or aromatic and, if desired, one to can carry three substituents, each selected from the group consisting of halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or (C₁-C₆-alkyl) carbonyl,
• - a group -CO-Z²R¹¹, -OCO-Z²R¹¹ or -N (R¹¹) R¹²; Z¹ is a chemical bond, oxygen, sulfur or -N (R¹⁰);

Z² is a chemical bond, oxygen, sulfur or -N (R¹²);
R⁹, R¹¹ independently of one another are hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₈-cycloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, ( C₁-C₆-alkoxy) carbonyl-C₁-C₆-alkyl, phenyl or phenyl-C₁-C₆-alkyl, where the phenyl group and the phenyl ring of the phenylalkyl group may be unsubstituted or may carry one to three radicals, each selected from the group consisting of nitro , Cyano, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy or (C₁-C₆-alkyl) carbonyl or
Z¹ and R⁹ and / or Z² and R¹¹ each together for a nitrogen-bonded 3- to 7-membered heterocycle having one to three heteroatoms, selected from the group consisting of two oxygen atoms, two sulfur atoms and 3 nitrogen atoms, the heterocycle being saturated, partially or completely be unsaturated or aromatic and, if desired, can carry one to three substituents, each selected from the group consisting of nitro, cyano, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl and C₁-C₆-alkoxy;
R¹⁰, R¹² independently of one another are hydrogen, hydroxy, C₁-C₆-alkyl, C₃-C₈-cycloalkyl or C₁-C₆-alkoxy,
and the agriculturally useful salts of those compounds I in which R³, R⁷ and / or R⁸ are hydrogen. 2. Benzylhydroxylamines of formula I according to claim 1, wherein the variables have the following meaning:
Y oxygen;
R1 halogen or cyano;
R² is hydrogen, fluorine or chlorine;
R³ amino or methyl;
R⁴ C₁-C₆ alkyl, C₁-C₆ haloalkyl or C₁-C₆ alkylsulfonyl;
R⁵ is hydrogen or halogen;
R⁶ is hydrogen or C₁-C₄ alkyl;
R⁷ hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-halogeno alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, (C₁-C₆-alkyl) carbonyl, (C₃-C₆-alkenyl) carbonyl,
(C₃-C₆-alkynyl) carbonyl, (C₁-C₆-alkoxy) carbonyl, (C₂-C₆-alkenyloxy) carbonyl, (C₂-C₆-alkynyloxy) carbonyl, (C₁-C₆-alkylthio) carbonyl, C₁-C₆-alkylcarbamoyl , each of the latter 13 radicals being able, if desired, to carry one or two substituents, each selected from the group consisting of

• - Nitro, cyano, halogen, C₃-C₈-cycloalkyl, hydroxy, C₁-C₆-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy , C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-alkyl sulfonyl, C₁-C₆-alkylideneaminoxy,
• - a group -CO-Z¹R⁹, -OCO-Z¹R⁹ or -N (R⁹) R¹⁰;

R⁸ is hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl, each of the latter 5 radicals optionally being able to carry one or two substituents, each selected from the group consisting of

• - Nitro, cyano, halogen, C₃-C₈-cycloalkyl, hydroxy, C₁-C₆-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy , C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-alkyl sulfonyl, C₁-C₆-alkylideneaminoxy,
• - a group -CO-Z²R¹¹, -OCO-Z²R¹¹ or -N (R¹¹) R¹²;

Z¹ is a chemical bond, oxygen, sulfur or -N (R¹⁰) -;
Z² is a chemical bond, oxygen, sulfur or -N (R¹²) -;
R⁹, R¹¹ independently of one another are hydrogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₆-alkyl or (C₁-C₆-alkoxy) carbonyl-C₁-C₆-alkyl; or
Z¹ and R⁹ and / or Z² and R¹¹ each together for a nitrogen-bonded 3- to 7-membered heterocycle having one to three heteroatoms, selected from the group consisting of two oxygen atoms, two sulfur atoms and 3 nitrogen atoms, the heterocycle being saturated, partially or completely be unsaturated or aromatic and, if desired, can carry one to three substituents, each selected from the group consisting of nitro, cyano, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl and C₁-C₆-alkoxy;
R¹⁰, R¹² independently of one another are hydrogen or C₁-C₆-alkyl. 3. Use of the benzylhydroxylamines of the formula I and agriculturally useful salts of I, according to claim 1, as herbicides or for desiccation and / or defoliation of Plants. 4. Herbicidal composition containing a herbicidally effective amount at least one benzylhydroxylamine of formula I or one agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or solid Carrier and, if desired, at least one upper surfactant.   5. means for the desiccation and / or defoliation of plants, containing a desiccant and / or defoliantly effective amount at least one benzylhydroxylamine of formula I or one agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or solid Carrier and, if desired, at least one upper surfactant. 6. Process for the preparation of herbicidally active agents, characterized in that a herbicidally effective amount at least one benzylhydroxylamine of formula I or one agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or solid Carrier and, if desired, at least one upper surfactant mixes. 7. Process for the production of desiccant and / or defoliant effective means, characterized in that one desiccant and / or defoliant effective amount of at least one Benzylhydroxylamine of formula I or an agriculture Lich usable salt of I, according to claim 1, and min at least an inert liquid and / or solid carrier and, if desired, at least one surface-active Fabric mixes. 8. methods for controlling undesirable plant growth, characterized in that a herbicidally effective amount at least one benzylhydroxylamine of formula I or of an agriculturally useful salt of I, according to Claim 1, on plants, their habitat or on seeds can act. 9. method for desiccating and / or defoliation of plants, characterized in that a desiccant and / or effective amount of at least one benzylhydroxylamine of formula I or an agriculturally useful salt of I, according to claim 1, can act on plants. 10. Enamine ester of the formula IV in which L¹ is C₁-C₆-alkyl or phenyl and the substituents R¹ to R⁸ have the meanings given in Claim 1. 11. Enamine carboxylates of the formula V in which L¹ is C₁-C₆-alkyl or phenyl and the substituents R¹ to R⁸ have the meanings given in Claim 1. 12. Phenylurea derivatives of the formula XIII in which the substituents R¹ to R³ and R⁶ to R⁸ have the meanings given in Claim 1. 13. Phenyl isocyanates of the formula XVI in which the substituents R¹, R² and R⁶ to R⁸ have the meanings given in Claim 1. 14. Aniline derivatives of the formula XVII in which L⁴ is C₁-C₄ alkyl or phenyl and the substituents R¹, R² and R⁶ to R⁸ have the meanings given in Claim 1. 15. Aniline compounds of the formula XIX in which the substituents R¹, R² and R⁶ to R⁸ have the meanings given in Claim 1. 16. Nitro compounds of the formula XXIII in which the substituents R¹, R² and R⁶ to R⁸ have the meanings given in Claim 1.