DE19524617A1 - New tetrahydro:pyrimidinyl-benzyl hydroxylamine derivs. - useful as herbicides, desiccants and defoliants - Google Patents

Abstract

Tetrahydropyrimidinyl-benzylhydroxylamines (I) and their salts are new. Y = O or S; R1 = halo, CN, NO2 or CF3; R2 = H or halo; R3 = H, NH2 or Me; R4 = H, halo, 1-6C alkyl opt. substd. by halo, 1-6C alkylthio, 1-6C alkylsulphinyl or 1-6C alkylsulphonyl; R5 = H, halo or 1-6C alkyl; R6 = H, 1-6C alkyl opt. substd. by halo or 3-6C cycloalkyl; R7 = H, 1-6C alkyl, 3-8C cycloalkyl, etc, Het, Het-O, -COXR9, -OCO-XR9 or -NR9R10, PhCO, PhSO2, PhCONH or 3-8C cycloalkylcarbonyl opt. mono-, di or trisubstd. by Q; Ph = phenyl opt. mono-, di- or trisubstd. by Q; Het = satd. partly unsatd. or aromatic 3-7 membered heterocycle contg. 1-3 hetero atoms from 2 O atoms, etc.; Q = e.g. halo; R8 = H or 1-6C alkyl, 1-6C haloalkyl, etc.; X = bond, O, S or -NR10; Z = bond, O, S or -NR12-; R9, R11 = H, 1-6C alkyl opt. substd, by halo, 1-6C alkoxy, 1-6C alkoxy-carbonyl or Ph1, etc.; Ph1 = phenyl opt. mono-, di or trisubstd. by Q or 1-6C alkyl-carbonyl ;or X+R9 and/or Z + R11 = N-bonded satd. partly unsatd. or aromatic 3-7 membered heterocycle contg. 1-3 hetero atoms from 2 O atoms, 2 S atoms and 3 N atoms and opt. mono-, di- or trisubstd. by Q; R10, R12 = e.g. H.

Description

The present invention relates to new benzylhydroxylamines general formula I.

in which the variables have the following meaning:
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, C₃-C₆ cycloalkyl or C₁-C₆ halogen alkyl;
R⁷ is hydrogen, C₁-C₆-alkyl, C₃-C₆-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, where each of the latter 14 radicals can optionally 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-C₆alkylsulfinyl, 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-XR⁹, -OCO-XR⁹ 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-alkylsulfenyl, 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-ZR¹¹, -OCO-ZR¹¹ or -N (R¹¹) R¹²;

X is a chemical bond, oxygen, sulfur or -N (R¹⁰) -;
Z 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-halo-xyl, C₁-C₆-alkoxy or (C₁-C₆-alkyl) carbonyl or
X and R⁹ and / or Z and R¹¹ together for a nitrogen-bonded 3- to 7-membered heterocycle 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 may be aromatic and may, if desired, 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 of controlling undesirable plant growth and for 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, XI, XIV, XV, XVII and XXI 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) -N (R⁷) -OR⁸ carries an iminomethyl group.

According to the teaching of WO 95/06641 u. a. Compounds of 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-aryluracile, 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 3-uracil-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 for 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 3-uracil-benzylhydroxylamine I in the form of their agricultural useful salts are present, depending on the type of salt in usually doesn't arrive. Generally the salts come from such bases into consideration, in which the herbicidal activity in Compared to the free compound I not adversely affected is.

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 -Dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 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-trimethylpropyl, 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;
• - The akenyl part of (C₂-C₆-alkenyloxy) carbonyl: vinyl or one of the radicals mentioned under C₃-C₆ alkenyl;
• - 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-methylpentylthio, 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-C₄-alkylsulfenyl: methylsulfenyl, ethylsulfenyl, n-propyl sulfenyl, 1-methylethylsulfenyl, n-butylsulfenyl, 1-methyl propylsulfenyl, 2-methylpropylsulfenyl, 1,1-dimethylethyl sulfenyl, n-pentylsulfenyl, 1-methylbutylsulfenyl, 2-methyl butylsulfenyl, 3-methylbutylsulfenyl, 2,2-dimethylpropyl sulfenyl, 1-ethylpropylsulfenyl, 1,1-dimethylpropylsulfenyl, 1,2-dimethylpropylsulfenyl, n-hexylsulfenyl, 1-methylpentyl sulfenyl, 2-methylpentylsulfenyl, 3-methylpentylsulfenyl, 4-methylpentylsulfenyl, 1,1-dimethylbutylsulfenyl, 2,2-dimethylbutylsulfenyl, 1,3-dimethylbutylsulfenyl, 2,2-dimethylbutylsulfenyl, 2,3-dimethylbutylsulfenyl, 3,3-dimethylbutylsulfenyl, 1-ethylbutylsulfenyl, 2-ethyl butylsulfenyl, 1,1,2-trimethylpropylsulfenyl, 1,2,2-trimethyl propylsulfenyl, 1-ethyl-1-methylpropylsulfenyl or 1-ethyl-2-methylpropylsulfenyl;
• - C₁-C₄ 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, Tetrahydropyrazine, 1,3,5-tetrahydrotriazinyl and 1,2,4-tetrahydrotriazinyl,
as well as the following 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, in each case individually or in combination:
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-XR⁹, -OCO-XR⁹ 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-cycloalkoxy₁ 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-ZR¹¹, -OCO-ZR¹¹ or -N (R¹¹) R¹²;

X is a chemical bond, oxygen, sulfur or -N (R¹⁰) -;
Z 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-alkoxy xy-C₁-C₆-alkyl or (C₁-C₆-alkoxy ) carbonyl-C₁-C₆-alkyl; or
X and R⁹ and / or z and R¹¹ 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 unsaturated or may be aromatic and may, if desired, 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-XR⁹, -OCO-XR⁹ 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 last 5 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-C Alkyl-alkylsulfenyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylidene aminoxy, a group -CO-ZR¹¹, -OCO-ZR¹¹ or -N (R¹¹) R¹².

Table 1 below is very particularly preferred led compounds Ia (= I with Y = oxygen, R¹ = chlorine, R² = Fluorine, R³ = amino, R⁴ = trifluoromethyl and R⁵, R⁶, R⁷ = water material):

Table 1

Furthermore, the following 3-uracilbenzylhydroxylamines are the Formula I particularly preferred:

• - The compounds Ib.01-Ib.86, which differ from the corresponding compounds Ia.01-Ia.86 only in that R¹ is cyano:
• - The compounds Ic.01-Ic.86, which differ from the corresponding compounds Ia.01-Ia.86 only in that R² is hydrogen:
• - The compounds Id.01-Id.86, which differ from the corresponding compounds Ia.01-Ia.86 only in that R¹ is cyano and R² is hydrogen:
• - The compounds Ie.01-Ie.86, which differ from the corresponding compounds Ia.01-Ia.86 only in that R³ is methyl:
• the compounds If.01-If.86, which differ from the corresponding compounds Ia.01-Ia.86 only in that R¹ is cyano and R³ is methyl:
• - The compounds Ig.01-Ig.86, which differ from the corresponding compounds Ia.01-Ia.86 only in that R² is hydrogen and R³ is methyl:
• - The compounds Ih.01-Ih.86, which differ from the corresponding compounds Ia.01-Ia.86 only in that R¹ is cyano, R² is hydrogen and R³ is methyl:

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

Table 2

Finally, there are the following 3-uracilo-benzylhydroxylamines I particularly preferred:

• - The compounds Ik.98-Ik.245, which differ from the corresponding compounds Ii.01-Ii.245 only in that R¹ is cyano:
• - The compounds Il.01-Il.245, which differ from the corresponding compounds Ii.01-Ii.245 only in that R² is hydrogen:
• - The compounds Im.01-Im.245, which differ from the corresponding compounds Ii.01-Ii.245 only in that R¹ is cyano and R² is hydrogen:
• - The compounds In.01-In.245, which differ from the corresponding compounds Ii.01-Ii.245 only in that R³ is methyl:
• - The compounds Io.01-Io.245, which differ from the corresponding compounds Ii.01-Ii.245 only in that R¹ is cyano and R³ is methyl:
• - The compounds Ip.01-Ip.245, which differ from the corresponding compounds Ii.01-Ii.245 only in that R² is hydrogen and R³ is methyl:
• - The compounds Iq.01-Iq.245, which differ from the corresponding compounds Ii.01-Ii.245 only in that R¹ is cyano, R² is hydrogen and R³ is methyl:

The 3-uracil-benzylhydroxylamines of the formula I are various available way, for example according to one of the following Method:

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 solution or diluent that is aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, Tetrahydrofuran and dioxane, in an aromatic such as benzene and Toluene or in a polar solvent such as dimethylformamide and Dimethyl sulfoxide. Mixtures of polar solvent and one Hydrocarbons such as n-hexane are suitable. Depending on the starting point Compound can also be water 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, into consideration. In the Using sodium hydride as the base has proven to be advantageous proven in an aliphatic or cyclic ether, in Dimethylformamide or work in dimethyl sulfoxide.  

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

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

R³ in formula IV or V means hydrogen, the Ver Get driving product as a metal salt, the metal to the Cation corresponds to the base used. The salt can be on isolated and cleaned in a known manner or if desired by means of acid in the free compound I with R³ = hydrogen be transferred.

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, and dimethyl sulfate, methanesulfonate (methyl mesylate), methyl benzenesulfonate, Methane p-tolyl sulfonate (methyl tosylate), methane p-bromobenzene sulfonate (methylbrosylate), trifluoromethanesulfonylmethane (methyl triflate) and diazomethane.

As a rule, one works in an inert organic solution medium, for example in a protic solvent such as the lower alcohols, preferably in ethanol, optionally in Mixture with water, or in an aprotic solvent, e.g. B. in an aliphatic or cyclic ether, preferably in 1,2-dimethoxyethane, tetrahydrofuran or dioxane, in an ali phatic ketone, preferably in acetone, in an amide, preferably as in dimethylformamide, in a sulfoxide, preferably in Dimethyl sulfoxide, in a urea such as tetramethyl urea and 1,3-Dimethyltetrahydro2 (1H) pyrimidinone, in a carboxylic acid  esters such as ethyl acetate, or in a halogenated ali phatic 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 up to 0 ° C the boiling temperature 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 process A) salt of I obtained without isolation from the reaction mixture, the excess base, e.g. B. sodium hydride, sodium alcoholate or sodium carbonate, may contain to methylate.

Unless directly described by method A) The cyclization can be produced under basic conditions Salts of those compounds I in which R³ is hydrogen, also in a manner known per se from the process products of Method A) can be obtained. For this purpose you put in for example the aqueous solution of an inorganic or organic base with the benzylhydroxylamine I, at the R³ for water fabric stands. Salt formation usually already occurs at 20-25 ° C with sufficient speed.

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

Salts of Benzylhydroxylamine I (R³ = H), the metal ion none Alkali metal ion can usually by salting the corresponding alkali metal salt prepared in aqueous solution  will. In this way, z. B. Benzylhydroxylamine Produce metal salts that are insoluble in water.

Process C)

Reaction of a benzylhydroxylamine of the formula I, where R³ is hydrogen, with an electrophilic amination reagent in the 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-sulfone acid (HOSA) are used, which are already from the literature is known as an amination reagent (see, for example, 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).

The implementation is usually carried out in a polar solution medium through, e.g. B. in dimethylformamide, N-methylpyrrolidone, Dimethyl sulfoxide or in ethyl acetate, which was previously known as has proven 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 Substituents before the amination in a manner known per se protect. This is particularly recommended if R⁷ or R⁸ Is hydrogen.

Procedure D)

Sulfurization of a 3-uracilo-benzylhydroxylamine of the formula I with Y = oxygen

The sulfurization is usually carried out in an inert solution or diluents, for example in an 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.

Phosphorus (V) is particularly suitable as a sulfurization reagent 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, based on the starting compound to be sulfurized, for a largely full constant implementation sufficient.

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

Procedure E)

Alkylation or acylation of a 3-uracilbenzylhydroxylamine of the formula I, in which R⁷ is hydrogen, in the presence of a base

The alkylation, for example with the halide, is preferred as the chloride or bromide, the sulfate, sulfonate, preferably methanesulfonate (mesylate), benzenesulfonate, p-toluenesulfonate (Tosylate), p-bromobenzenesulfonate (brosylate), the trifluoromethane sulfonate (triflate) or the diazo compound of an unsubsti tuiert or substituted alkane, cycloalkane, haloalkane, Alkens or alkins can be made.

Suitable acylating agents are e.g. B. the acid halides, especially the acid chlorides, the anhydrides, isocyanates and Sulfonyl chlorides of optionally substituted alkane, cyclo alkanoic, alkene, alkynic or phenylcarboxylic acids. But it will come also the free acids or their anhydrides into consideration, provided that then in the presence of a condensing agent such as carbonyldi imidazole and dicyclohexylcarbodiimide is worked.

Usually you work in an inert organic solution medium, preferably in an aprotic solvent, e.g. B. an aliphatic or cyclic ether such as 1,2-dimethoxyethane, Tetrahydrofuran and dioxane, an aliphatic 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 chlorine benzene.

Both inorganic bases, e.g. B. Alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, as  also organic bases, e.g. B. amines such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methanolate, ethanolate and potassium tert-butoxide.

The amount of base and alkylating agent is preferably included 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 is recommended Boiling temperature of the reaction mixture, in particular of 0 to 60 ° C.

Possible regioselectivity problems with starting compounds with R³ = Hydrogen can be used in a manner known per se (use of 2 equivalents of base, introduction of a protective group etc.) ver 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.

A reaction is recommended when using hydrogen leadership under acidic conditions, e.g. B. in an organic or inorganic acid as a solvent.

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

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

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

Procedure G)

Halogenation of a 3-uracil-benzylhydroxylamine of the formula I in which R⁵ is hydrogen

The halogenation is usually carried out in an inert organi solvent or diluent. For chlorination and Bromination comes, for example, as aliphatic carboxylic acids Acetic acid, or chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, in Consideration. For iodination are low boiling aliphatic Carboxylic acids such as acetic acid are particularly preferred.

Elemen are particularly suitable for chlorination and bromination tares chlorine or bromine, or sulfuryl chloride or sulfuryl bromide, at a reaction temperature of preferably 0 to 60 ° C, ins particularly 10 to 30 ° C.

If desired, chlorination and bromination can be carried out in the presence an acid-binding agent, sodium acetate and tertiary amines such as triethylamine, dimethylaniline and pyridine are particularly preferred.

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

The iodination proceeds particularly advantageously in the presence of a Mineral acid such as fuming nitric acid.  

The amount of halogenating agent is not critical; more normal wise use equimolar amounts of halogenating agent 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 saturated aqueous sodium bisulfite solution who removed the.

Procedure H)

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

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

As a rule, one works in an inert organic solution medium, especially aprotic solvents, e.g. B. aliphati cal or cyclic ethers such as preferably 1,2-dimethoxyethane, Tetrahydrofuran and dioxane, aliphatic ketones as preferred Acetone, amides such as preferably dimethylformamide, sulfoxides such as preferably dimethyl sulfoxide, ureas such as tetramethyl urine substance and 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, carboxylic acid esters such as ethyl acetate, or halogenated aliphatic or aromatic hydrocarbons such as dichloromethane and chlorine benzene.

Both inorganic bases, e.g. B. Carbonates like the alkali metal carbonates, especially sodium carbonate and Potassium carbonate, hydrogen carbonates such as the alkali metal hydrogen carbonates, 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 methanolate, sodium ethanolate and potassium tert-butoxide.  

The amount of base and alkylating agent IX is preferably each with 0.5 to 2 times the molar amount, based on the Amount of VIII.

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. according to one of the following procedures:

It is preferred to work essentially in an inert manner in an anhydrous manner Solvent or diluent, particularly preferably in Presence of an acidic or basic catalyst.

In particular, come as solvents or diluents Water azeotropically miscible organic solvents, for example wise aromatics such as benzene, toluene and the xylenes, halogenated Hydrocarbons such as methylene chloride, chloroform, tetrachlor carbon 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 cation exchangers like "Amberlyst 15" (from Fluka).

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

It is advisable to set XI and the β-ketoester X approximately stoichio metric quantities or one works with a small one Excess of one or the other component, up to about 10 mol%.

Usually the 0.5 to 2 times the molar amount of kata analyzer, based on the amount of one of the starting compounds, sufficient.

The reaction is generally carried out at one temperature from 60 to 120 ° C, for the rapid removal of water preferably at the boiling point of the reaction mixture.

L³ stands for C₁-C₄-alkyl or phenyl.

This reaction can, for example, in an inert, with water miscible, organic solvents, for example an ali phatic or cyclic ethers such as 1,2-dimethoxyethane, tetra hydrofuran and dioxane, or a lower alcohol, in particular Ethanol, are carried out, the reaction temperature nor sometimes at 50 to 100 ° C, preferably at the boiling temperature of the reaction mixture.

However, the reaction can also be in an aromatic dilution agents such as benzene, toluene and the xylenes are carried out, in which case the addition of either an acidic catalyst tors such as hydrochloric acid and p-toluenesulfonic acid or a base, e.g. B. an alkali metal alcoholate such as sodium methoxide and sodium ethanolate, is recommended. Even with this process variant the reaction temperature is usually 50 to 100 ° C, however, preferably at 60 to 80 ° C.

With regard to the proportions, the information applies to the method K).  

The implementation takes place in the presence of an essentially Lichen anhydrous aprotic organic solution or Ver fertilizer, for example an aliphatic or cycli 'ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydro furan and dioxane, an aliphatic or aromatic carbon hydrogen such as n-hexane, benzene, toluene and the xylenes, one halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic polar solvent such as Dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.

If desired, even in the presence of a metal hydride base such as sodium and potassium hydride, an alkali metal or alkaline earth limetal alcoholates such as sodium methoxide, ethanolate and potassium tert-butoxide, or an organic tertiary base such as tri ethylamine and pyridine are used, the organic Base can also serve as a solvent.

The starting compounds are expediently put into stoichiomas quantities or one works with a small excess shot of one or the other component up to about 10 mol%. At the Work without solvents in the presence of an organic base it is advisable to include the latter in a larger excess put.

Usually a reaction temperature of (-80) to 50 ° C, especially (-60) up to 30 ° C sufficient.

In a particularly preferred embodiment, the one obtained Enamine ester IV with excess base directly (i.e. "in situ") converted into the corresponding product of value I according to process A). Any by-products (e.g. C-alkylation products at Verbin dung with R Wasserstoff = hydrogen), can be separated using a conventional method procedures such as removing crystallization and chromatography.  

L⁴ represents C₁-C₄ alkyl or phenyl.

This reaction is conveniently carried out in an aprotic, polar solution or diluents such as dimethylformamide, 2-butanone, Dimethyl sulfoxide and acetonitrile, advantageously in counter were a base, such as an alkali metal or earth alkali metal alcoholate, especially a sodium alkanolate such as sodium methoxide, an alkali metal or alkaline earth metal carbonates, especially sodium carbonate, or an alkali metal hydrides such as lithium and sodium hydride.

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

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

Regarding the proportions of the starting compounds apply the information for method K).

In a particularly preferred embodiment, one is used Sodium alcoholate as the base and distilled it during the reak tion continuously produced alcohol. That way prepared enamine esters IV can be isolated from the reak without isolation tion mixture according to method A) to a salt of the corresponding 3-Uracilo-benzylhydroxylamine I cyclized.

This implementation is essentially carried out in one anhydrous, aprotic, organic solution or thinner medium, for example in the presence of an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetra hydrofuran and dioxane, an aliphatic or aromatic Hydrocarbon such as n-hexane, benzene, toluene and the xylenes, a halogenated aliphatic hydrocarbon such as Methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloro ethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and Dimethyl sulfoxide, or a mixture of the above Solvents.

If desired, 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-butanolate, or an organic nitrogen base such as tri ethylamine and pyridine are used, the organic Base can also serve as a solvent.

The starting compounds are expediently put into stoichio metric quantities or use one of the components in the Excess, up to about 20 mol%. When working without solvent in In the presence of an organic base, the latter is used advantageously stuck in an even larger surplus.

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

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 P):  

XVIII and XVII are preferably reacted in one anhydrous inert aprotic solvents, for example in a halogenated hydrocarbon such as methylene chloride, Chloroform, carbon tetrachloride and chlorobenzene, an aroma table hydrocarbon such as benzene, toluene and the xylenes, or an aliphatic or cyclic ether such as diethyl ether, Dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane.

The reaction temperature is in this reaction (from XVIII with XVII) generally at about 70 to 140 ° C, especially at 100 to 120 ° C.

The implementation of X with XVII 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 solution / dilution medium, especially in an aprotic solvent, for example in an aromatic such as toluene and the xylenes, or a halo Generated aromatics such as chlorobenzene is carried out.

Working in the presence of a basic is recommended Catalyst, for example a higher boiling amine [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 each in about stoichiometric amounts or you work with one slight excess of one or the other component, up to about 10 mol%. If you work in the presence of a basic catalyst,  this is normally 0.5 to 2 times the molar amount of catalyze sator, based on the amount of one of the starting materials, sufficient.

The subsequent implementation of the compounds thus prepared Formula XIX with the amine H₂N-COOL¹ is advantageous in a wide range going anhydrous solvent / diluent at normal pressure carried out, particularly preferably in the presence of an acid Catalyst.

Recommended for the production of enamine carboxylates V with R³ = amino it is compounds XX with a protected amino group (e.g. as Hydrazone) to use.

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 acids such as sulfuric acid, organic acids such as p-toluenesulfonic acid, Acids containing phosphorus such as orthophosphoric acid and poly phosphoric acid or acidic cation exchangers such as "Amberlyst 15" (Fluka).

In general, the reaction temperature is about 70 to 150 ° C; for the rapid removal of the water of reaction however, it is advantageous to work at the boiling point of the respective reaction mixture.

The compounds of formulas XI, XIV, XV and XIX are also New. They can also be made in a manner known per se, particularly advantageously from the compounds of the formula XVII:

Q): "Phosgenation" of compounds of the formula XVII and hydrolysis of the process products XIV with ammonia (derivatives)

The process can be carried out in an inert, essentially anhydrous Solvent / diluent or without solvent. The amino group is converted into the isocyanate group preferably by means of phosgene or chloroformic acid trichlor methyl ester.  

In particular, aprotic, organic solvents, for example aromatics such as toluene and the xylenes, halogenated hydrocarbons such as methylene chloride, Chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and Dioxane, esters such as ethyl acetate, and mixtures of these Solvent.

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

The phenyl isocyanates XIV usually arise during reaction temperatures from 50 ° C to the boiling point of the reaction mixture; you can then use ammonia or a reactive derivative of the ammonia to the phenylurea derivatives XI will.

R): Reaction with alkali metal cyanates

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

The reaction is usually carried out in an inert solution / Diluent, for example in an aromatic carbon hydrogen such as toluene and the xylenes, in an aliphatic or cyclic ethers such as tetrahydrofuran and dioxane, in one lower alcohol such as 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 of aniline Compound XVII and cyanate, however, an excess of Cyanate, up to about 100 mol%, offer advantages.

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

S): Reaction with esters L⁴O-CO-L⁵

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

Aroma, for example, are suitable as solvents / diluents table hydrocarbons such as toluene and the xylenes, halogenated Hydrocarbons such as methylene chloride, chloroform, 1,2-dichlor ethane and chlorobenzene, aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, esters such as vinegar acid ethyl ester, 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 the present an alkali metal hydroxide, carbonate or alcoholate 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.

The starting compounds and the base are expediently used in approximately stoichiometric amounts, but also one or other component in excess, up to about 100 mol% lie.

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

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

The aniline compounds of formula XVII are also new. Your Synthesis usually takes place from the corresponding nitro ver compounds XXI by hydrogenation or from anilines of the formula XXII, according to method F) in the corresponding aniline compounds of the formula XVII can be converted:

The nitro compounds of the formula XXI are also new. You leave according to known methods, e.g. B. by nitriding the corresponding benzylamines.

The compounds of the formula VII, VIII, IX, X, XII, XIII, XVI, XVIII and XXII are known or in a manner known per se can be represented (see, for example, 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. You can like in cultures Wheat, rice, corn, soybeans and cotton weeds and grass weeds fight very well without noticeable the crops damage. This effect occurs above all with little effort amounts on.

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, Ipomoealumisisumisum , 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 , Prunus persica, pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (see vulgare), Theobroma cacao, Trifolium pratense, T. riticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds I in cultures that by breeding and / or by means of genetic engineering methods against the Effects of I were made largely resistant.

3-Uracilo-benzylhydroxylamines I are also suitable for 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 herbicidal compositions comprising them can, for example, in the form of directly sprayable aqueous Solutions, powders, suspensions, including high-proof aqueous oily or other suspensions or dispersions, emulsions, Oil dispersions, pastes, dusts, spreading agents or granules laten by spraying, atomizing, dusting, scattering or Pouring can be applied. The application forms depend on the uses; in any case, they should, if possible finest distribution of the active ingredients according to the invention Afford.  

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 alkali, alkaline earth, Ammonium salts of aromatic sulfonic acids, e.g. B. lignin, Phenolic, naphthalene and dibutylnaphthalenesulfonic acid, as well as from Fatty acids, alkyl and alkyl aryl sulfonates, alkyl and lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols and fatty alcohol glycol ethers, condensates tion products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or Naphthalenesulfonic acids with phenol and formaldehyde, polyoxy ethylenoctylphenolether, 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, fertilizer tel such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urine substances and vegetable products such as flour, tree bark, Wood and nutshell flour, cellulose powder or other solid Carriers.

The concentrations of the active ingredients I in the ready-to-use Preparations can be varied in a wide range, for example from 0.01 to 95% by weight, preferably 0.5 to 90% by weight. The effect fabrics with a purity of 90% to 100% are preferred as 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 up to 10 moles of ethylene oxide in 1 mole of oleic acid-N-monoethanolamide, Parts by weight of calcium salt of dodecylbenzenesulfonic acid and Parts by weight of the adduct of 40 moles of ethylene oxide on 1 mole of castor oil. By pouring out and fine Distribute the solution in 100,000 parts by weight of water an aqueous dispersion containing 0.02% by weight of the active ingredient contains.
• 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 tion product of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles There is ethylene oxide in 1 mol of castor oil. By pouring and finely distribute the solution in 100,000 parts by weight of water an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient contains.
• 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 with a boiling point of 210 up to 280 ° C and 10 parts by weight of the adduct of There are 40 moles of ethylene oxide with 1 mole of castor oil. By input ate and finely distribute the solution in 100,000 parts by weight Water is obtained in an aqueous dispersion, the 0.02 wt .-% of Contains active ingredient.  
• IV. 20 parts by weight of active ingredient no. 1.04 are with 3 parts by weight of the sodium salt of diisobutylnaphthalene α-sulfonic acid, 17 parts by weight of the sodium salt one Lignin sulfonic acid from a sulfite waste liquor and 60 weight divide powdered silica gel well mixed and in ground in a hammer mill. By finely distributing the A mixture in 20,000 parts by weight of water contains one Spray liquor containing 0.1% by weight of the active ingredient.
• V. 3 parts by weight of active ingredient no. 1.05 are with 97 parts by weight of finely divided kaolin mixed. You get in this way a dusting agent containing 3% by weight of the active ingredient contains.
• 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 condensate sates and 68 parts by weight of a paraffinic mineral oil intimately mixed. A stable oily dispersion is obtained.

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 3-uracilo-benzylhydroxylamine I with numerous representatives of other herbicides or growth regulating drug groups mixed and applied together will. For example, diazines 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitro anilines, N-phenyl carbamates, thiol carbamates, halocarboxylic acids, Triazines, amides, ureas, diphenyl ethers, triazinones, uraciles, Benzofuran derivatives, cyclohexane-1,3-dione derivatives, which are in 2-st lung z. B. carry a carboxy or carbimino group, quinoline carboxylic acid derivatives, imidazolinones, sulfonamides, sulfonyl urine  substances, aryloxy, heteroaryloxyphenoxypropionic acids and their Salts, esters and amides, and others.

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 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 hydrofuran) 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-chlorophe nyl) -1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydro pyrimidine-2,4-dione (Compound No. 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.

In the following Table 3 are in addition to those described above other compounds 3-benzylhydroxylamines I added leads, which were produced in an analogous manner or can be produced are:  

Table 3

Examples of use (herbicidal activity)

The herbicidal activity of the 3-uracil-benzylhydroxylamine I let are shown by the following greenhouse tests:

Plastic flower pots with loamy sand also served as culture vessels about 3.0% humus as a substrate. 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 or 0.0078 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.

It was rated on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 no damage or 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 the connection No. 1.03 00937 00070 552 001000280000000200012000285910082600040 0002019524617 00004 00818 in the post-emergence procedure a very good one Effect against the above Plants.  

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 general formula I in which the variables have the following meaning:
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, C₃-C₆ cycloalkyl or C₁-C₆ haloalkyl;
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, where each of the latter 14 radicals can optionally 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-XR⁹, -OCO-XR⁹ 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-alkylsulfenyl, 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-ZR¹¹, -OCO-ZR¹¹ or -N (R¹¹) R¹²;

X is a chemical bond, oxygen, sulfur or -N (R¹⁰) -;
Z 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
X and R⁹ and / or Z and R¹¹ together for a nitrogen-bonded 3- to 7-membered heterocycle 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 may be aromatic and may, if desired, 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 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-alkylsulfinyl, C₁-C₆-alkyl sulfonyl, C₁-C₆-alkylideneaminoxy,
• - a group -CO-XR⁹, -OCO-XR⁹ 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, hydroxy, 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-alkyl sulfonyl, C₁-C₆-alkylideneaminoxy,
• - a group -CO-ZR¹¹, -OCO-ZR¹¹ or -N (R¹¹) R¹²;

X is a chemical bond, oxygen, sulfur or -N (R¹⁰) -;
Z 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
X and R⁹ and / or Z and R¹¹ together for a nitrogen-bonded 3- to 7-membered heterocycle 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 may be aromatic and may, if desired, 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 formula I and the land economically useful salts of I, according to claim 1, as Herbicides or for the desiccation and / or defoliation of Plants. 4. Herbicidal composition containing a herbicidally effective amount at least one benzylhydroxylamine of formula I or 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 adjuvant.   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 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 adjuvant. 6. Process for the preparation of herbicidally active agents, characterized in that a herbicidally effective amount at least one benzylhydroxylamine of formula I or 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 adjuvant 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 agricultural useful salt of I, according to claim 1, and at least an inert liquid and / or solid carrier and if desired, mixes at least one adjuvant. 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 XI in which the substituents R¹ to R³ and R⁶ to R⁸ have the meanings given in Claim 1. 13. Phenyl isocyanates of the formula XIV in which the substituents R¹, R² and R⁶ to R⁸ have the meanings given in Claim 1. 14. Aniline derivatives of the formula XV 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 XVII in which the substituents R¹, R² and R⁶ to R⁸ have the meanings given in Claim 1. 16. Nitro compounds of the formula XXI in which the substituents R¹, R² and R⁶ to R⁸ have the meanings given in Claim 1.