Kannelirovannye (oxa)-hydantoins, methods for their preparation, herbicide composition and method for control of weeds

 

(57) Abstract:

Usage: in the chemistry of heterocyclic compounds with herbicide activity. The inventive kannelirovannye (oxa)-hydantoins of the formula I:

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where R1and R2- H or (C1-C4)-alkyl; R3and R4- H, (C1-C4)-alkyl or phenyl, or R3and R4together form a carbocyclic ring, Q means the residue of Q1or Q5< / BR>
< / BR>
where W denotes O or S, R5- H or halogen; R6- halogen or CN; R7- H, OR11, CO2R11or NHSO2R16; R8, R9- H, R10- (C3-C6)-quinil; R11- (C1-C8)-alkyl, (C3-C8)-quinil, (C3-C8-alkoxycarbonylmethyl, (C2-C8-alkoxyalkyl or (C1-C8-haloalkyl, R16- (C1-C4)-alkyl, (C1-C4-haloalkyl; methods for their preparation, herbicide composition based on these compounds and a method of controlling weeds by treating the plants or the soil an effective amount of the compounds of formula 1. 4 C. and 6 C.p. f-crystals, 12 tab.

The invention relates to new annelated (oxa)-hydantoins of the formula I

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in which R1the ve herbicides.

As mentioned above, as herbicides can be used in certain (thio) hydantoins (see European patent application N 0 290 902) or heterocyclic imides (see European patent application NN 272 594, 0 070 389).

Unexpectedly found new bicyclic imides, which possess much better herbicide activity and high selectivity.

The present invention includes compounds of formula I

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in which

R1and R2independently of one another, denote hydrogen or a group number (C1-C4)-alkyl, (C1-C2)-haloalkyl or phenyl, which optionally can be substituted by fluorine,

R3and R4independently of one another, denote hydrogen, (C1-C4)-alkyl, phenyl, both optionally may be substituted by fluorine and/or chlorine, bromine or stands, (C1-C4)-alkoxy; or together form a carbocyclic ring, which optionally may be substituted (C1-C4)- alkyl,

Q represents the remains of Q1-Q7presented at the end of the text.

where W denotes O or S,

R5is hydrogen or halogen,

R6- (C1-C is hydrogen, (C1-C8)-alkyl, (C1-C8-haloalkyl, halogen, OR11, S(O)nR11, COR11, CO2R11C(O)SR11C(O)NR12R13CHO, CH=CHCO2R11, CO2N=CR14R15, NO2CN, NHSO2R16or NHSO2OTHER16,

R8is hydrogen, (C1-C3)-alkyl, (C1-C3-haloalkyl or halogen,

R9is hydrogen, (C1-C3)-alkyl, (C1-C3-haloalkyl or halogen; or if Q = Q-2 or Q-6, R8and R9together with the carbon atom to which they relate, can denote C=O;

R10- (C1-C6)-alkyl, (C1-C6-haloalkyl, (C2-C6-alkoxyalkyl, (C3-C6)-alkenyl or (C3-C6)-quinil,

R11- (C1-C8)-alkyl, (C3-C8-cycloalkyl, (C3-C8)-alkenyl, (C3-C8-quinil, (C1-C8-haloalkyl, (C2-C8-alkoxyalkyl, (C2-C8-alkylthiomethyl, (C2-C2-alkylsulfonyl, (C2-C8-alkylsulfonyl, (C3-C8-alkoxylalkyl, (C4-C8-cycloalkenyl, (C2-C4-carboxyethyl, (C3-C8-alkoxycarbonylmethyl, (C6-C8)-UB>6-C8-cycloalkenyl, (C4-C8-alkyloxyalkyl, (C3-C8-haloalkoxy, (C4-C8-haloalkaliphilic, (C4-C8-haloalkaliphilic, (C6-C8-cycloalkylcarbonyl, (C4-C8-alkenylacyl, (C4-C8-alkylalcohol, (C1-C4)-alkyl, substituted phenoxy - or benzyloxy groups, both optionally may be substituted with halogen, (C1-C3)-alkyl or (C1-C3-haloalkyl; (C4-C8-trialkylsilyl, (C3-C8-cianelli, (C3-C8-halachically, (C3-C8)-haloalkyl, (C5-C8)-alkoxyalkyl, (C5-C8)-haloalkoxy,

(C5-C8)-alkylthiophenes, (C3-C8-haloalkyl, (C5-C8-alkoxyalkyl, (C5-C8-haloalkoxy, (C5-C8-alkylthiophenes, (C2-C8-alkylsulphonyl,

benzyl optionally substituted with halogen, (C1-C3)-alkyl or (C1-C3-haloalkyl; CHR17COR18, CHR17P(O)(OR18)2, P(O)(OR18)2, CHR17P(S)(OR18)2, CHR17C(O)NR12R13, CHR17C(O)NH2, phenyl or (C1-C4)-alkoxy,

R12and R14, independently of one another, denote hydrogen or (C1-C4)-alkyl,

R13and R15, independently of one another, denote (C1-C4)-alkyl, phenyl, if necessary substituted with halogen, (C1-C3)-alkyl, (C1-C3-haloalkyl or (C1-C4)-alkoxy, or

R12and R13denoted -(CH2)5-, -(CH2)4- or-CH2CH2OCH2CH2- can be combined in a ring, and one or more hydrogen atoms in each ring optionally can be substituted (C1-C3)-alkyl, phenyl or benzyl;

R14and R15together with the carbon atom to which they are bound, may form a (C3-C8)-cycloalkyl group

R16- (C1-C4)-alkyl or (C1-C4-haloalkyl,

R17is hydrogen or (C1-C3)-alkyl,

R18- (C1-C6)-alkyl, (C3-C6)-alkenyl or (C3-C6)-quinil, and

n = 0, 1, 2.

In the above definitions, the term "alkyl" or when referring to compounds, as alkylthio" or "haloalkyl, you know straight or branched is XI, n-propoxy, isopropoxy and various isomers of butoxy. Alkenyl includes straight and branched alkenes, such as 1-propenyl, 2 - propenyl, 3-propenyl and various isomers butenyl. Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "halogen" or when referring to compounds as "haloalkyl, you know fluorine, chlorine, bromine or iodine. Further, when the designation of the connection use the term "haloalkyl", "alkyl" may be substituted partially or in combination with halogen atoms, which in turn may be the same or different. Examples of haloalkyl are CH2CH2F, CF2CF3and CH2CHFCl.

Preferred these residues, in which

R1and R2, independently of one another, denote hydrogen or a group number (C1-C4)-alkyl, (C1-C2-haloalkyl or phenyl, optionally substituted by fluorine,

R3and R4, independently of one another, denote hydrogen, (C1-C3)-alkyl, phenyl, optionally substituted by fluorine and/or chlorine, bromine, stands, (C1-C2)-alkoxy; or together form a carbocyclic ring, which optionally may be substituted (C1-C2)- The P>5is hydrogen or halogen,

R6- halogen or CN,

R7is hydrogen, (C1-C4)-alkyl, (C1-C4-haloalkyl, halogen, OR11, S(O)nR11, COR11, CO2R11C(O)SR11C(O)NR12R13CH=CHCO2R11, CO2N=CR14R15, NHSO2R16or NHSO2OTHER16,

R8is hydrogen, (C1-C3)-alkyl or (C1-C3-haloalkyl,

R9is hydrogen, (C1-C3)-alkyl or (C1-C3-haloalkyl; or if Q = Q-2 or Q-6, R8and R9together with the carbon atom to which they relate, can denote C=O;

R10- (C1-C4)-alkyl, (C1-C4-haloalkyl, (C2-C4-alkoxyalkyl, (C3-C6)-alkenyl or (C3-C6)-quinil,

R11- (C1-C4)-alkyl, (C3-C6-cycloalkyl, (C3-C6)-alkenyl, (C3-C6)-quinil, (C1-C4-haloalkyl, (C2-C4-alkoxyalkyl, (C2-C4-alkylthiomethyl, (C2-C4-alkylsulfonyl, (C2-C4-alkylsulfonyl, (C3-C6-alkoxylalkyl, (C4-C8-cycloalkenyl, (C2-C4-carboxyethyl, (C3-C6)-alcl, (C4-C6-altenately, (C6-C8-cycloalkenyl, (C4-C6-alkyloxyalkyl, (C3-C6-haloalkoxy, (C4-C8-haloalkaliphilic, (C4-C6-haloalkaliphilic, (C6-C8-cycloalkylcarbonyl, (C4-C6-alkenylacyl, (C4-C6-alkylalcohol, (C1-C2)-alkyl, substituted phenoxy - or benzyloxy groups, both optionally may be substituted with halogen, (C1-C3)-alkyl or (C1-C3-haloalkyl; (C4-C8-trialkylsilyl, (C3-C4-cianelli, (C3-C6-halachically, (C3-C6)-haloalkyl, (C5-C6)-haloalkoxy, (C5-C6)-alkylthiophenes, (C3-C6-haloalkyl, (C5-C6-alkoxyalkyl, (C5-C6-haloalkoxy,

(C5-C6-alkylthiophenes, (C2-C4-alkylaryl, benzyl optionally substituted with halogen, (C1-C2)-alkyl or (C1-C2-haloalkyl; CHR17COR18, CHR17P(O)(OR18)2, P(O)(OR18)2, CHR17P(S)(OR18)2, CHR17C(O)NR12R13, CHR17C(O)NH2, phenyl or PM or (C1-C4)-alkoxy,

R12and R14, independently of one another, denote hydrogen or (C1-C2)-alkyl,

R13and R15, independently of one another, denote (C1-C2)-alkyl, phenyl, if necessary substituted with halogen, (C1-C2)-alkyl, (C1-C2-haloalkyl or (C1-C2)-alkoxy, or

R12and R13denoted -(CH2)5-, -(CH2)4- or-CH2CH2OCH2CH2- can be combined in a ring, and one or more hydrogen atoms in each ring optionally can be substituted (C1-C2)-alkyl, phenyl or benzyl:

R14and R15together with the carbon atom to which they are bound, may form a (C3-C6)-cycloalkyl group

R16- (C1-C4)-alkyl or (C1-C4-haloalkyl,

R17is hydrogen or (C1-C3)-alkyl,

R18- (C1-C4)-alkyl, (C3-C4)-alkenyl or (C3-C4)-quinil.

Preferred these residues, in which

R1and R2, independently of one another, denote hydrogen or a group number (C1-C3)-alkyl, (C11-C3)-alkyl or together form a 5 - to 6-membered carbocyclic ring, which optionally may be substituted (C1-C4)-alkyl,

Q denotes (see end of text)

W represents O or S,

n = 0, 1, 2,

R5is hydrogen, fluorine or chlorine,

R6is chlorine, bromine or cyan,

R7is hydrogen, OR11or CO2R11,

R8and R9, independently of one another, denote hydrogen, (C1-C2)-alkyl or (C1-C2-haloalkyl,

R10- (C1-C2)-alkyl, (C1-C2-haloalkyl, (C3-C4)-alkenyl or (C3-C4)-quinil,

R11- (C1-C4)-alkyl, (C3-C6-cycloalkyl, (C3-C6)-alkenyl, (C3-C6)-quinil, (C1-C4-haloalkyl, (C2-C4-alkoxyalkyl, (C2-C4-alkylthiomethyl, (C2-C4-alkylsulfonyl, (C2-C4-alkylsulfonyl, (C3-C6-alkoxylalkyl, (C4-C8-cycloalkenyl, (C2-C4-carboxyethyl, (C3-C6-alkoxycarbonylmethyl, (C6-C8-alkenylcarbazoles, (C6-C8-alkyloxyalkyl, (C6-C6-haloalkoxy, (C4-C8-haloalkaliphilic, (C4-C6-haloalkaliphilic, (C6-C8-cycloalkylcarbonyl, (C4-C6-alkenylacyl, (C4-C6-alkylalcohol, (C1-C2)-alkyl, substituted phenoxy - or benzyloxy groups, both optionally may be substituted with halogen, (C1-C3)-alkyl or (C1-C3-haloalkyl; (C4-C8-trialkylsilyl, (C3-C4-cianelli, (C3-C6-halachically, (C3-C6)-haloalkyl, (C5-C6)-alkoxyalkyl, (C5-C6)-haloalkoxy,

(C5-C6)-alkylthiophenes, (C3-C6-haloalkyl, (C5-C6-alkoxyalkyl, (C5-C6-haloalkoxy, (C5-C6-alkylthiophenes, (C2-C4-alkylsulphonyl,

benzyl optionally substituted with halogen, (C1-C2)-alkyl or (C1-C2-haloalkyl; CHR17COR18, CHR17P(O)(OR18)2, P(O)(OR18)2, CHR17P(S)(OR18)2, CHR17C(O)NR12R13, CHR17C(O)NH, phenyl or pyridyl, both optionally may be substituted by fluorine, chlorine, bromine, (C1-C2 - (C1-C3)-alkyl, phenyl, if necessary substituted by fluorine, chlorine, bromine, (C1-C2)-alkyl, (C1-C2-haloalkyl or (C1-C2)-alkoxy, or R12and R13denoted -(CH2)5-, -(CH2)4- or-CH2CH2OCH2CH2- can be combined in a ring, and one or more hydrogen atoms in each ring optionally can be substituted (C1-C2)-alkyl;

R17is hydrogen or (C1-C2)-alkyl,

R18- (C1-C4)-alkyl, (C3-C4)-alkenyl or (C3-C4)-quinil.

Preferred these residues, in which

R1and R2, independently of one another, denote hydrogen or a group number (C1-C3)-alkyl, (C1-C2-haloalkyl or phenyl,

R3and R4, independently of one another, denote hydrogen, (C1-C3)-alkyl, or together may form a 5 - to 6-membered carbocyclic ring,

Q denotes

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where

R5is fluorine or chlorine,

R6- chlorine,

R7- OR11or CO2R11,

R11- (C1-C4)-alkyl, (C3-C6- cycloalkyl, (C33-C6-alkoxycarbonylmethyl, (C6-C8-alkenylcarbazoles or (C6-C8-alkyloxyaryl.

The invention applies not only to possible individual stereoisomers of the formula I, and mixtures of isomers. In comparison with other preferred stereoisomers configuration 2R, 3S.

According to the present invention, new kannelirovannye (oxa)-hydantoins of the General formula I get the General method A, in which the reaction come arylisocyanate General formula II

Q-N=C-O II

in which Q has the above meaning, and ester oxazolidinecarboxylate acid of General formula III

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in which R1, R2, R3and R4(R3= R4H) have the above significance, and R denotes H, (C1-C4)-alkyl, or an active ester according to method A, if necessary, can be entered acceptor acid or diluent.

Another object of the invention is a method B the manufacture of compounds of formula I, just to clarify further, where R1- R4and Q have the above significance, according to which the reaction enter the compounds of formula III in which R denotes H

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which poluchayut entered acceptor acid and a diluent, and the compound of formula II, if necessary, can be added to the acid acceptor and a solvent to obtain compounds of formula VI, in which R denotes H, (C1-C4)-alkyl, or an active ester

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then when the closure ring is converted into the compounds of formula I.

The next subject of invention is a method C manufacture of compounds of the formula I, which is explained in further, where R1-R4have the above significance. In response enter the compound of the formula III in which R = H or (C1-C4)-alkyl, and phosgene or a substitute for obtaining compounds of formula VII, which react with compounds of formula VIII where Q have the above significance, to obtain the compounds of formula VI

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then when the closure ring is converted into the compounds of formula I.

The next subject of invention is a method D manufacture of compounds of the formula I, which is explained in further, where R1- R4and Q have the above significance, according to which the reaction enter the compound of the formula II and the compound of formula IX, optionally, may be added as the acid acceptor and a solvent to obtain compounds of formula X
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where

R1- R6have the above meaning and X denotes Q, S, or NH, and one of the halides of the formula XII, XIII or XIV,

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where

Z denotes a chlorine atom, bromine or iodine, and R11and R16have the above values.

Finally, it was found that the new kannelirovannye (oxa)hydantoins of the General formula I possess an unusual herbicide properties.

According to method A, in the case R = alkyl the reaction is carried out in an inert organic solvent, for example, in an aromatic solvent like toluene, chlorobenzene, halogenosilanes hydrocarbon as chloroform or methylene chloride, simple air, as diisopropyl ether, or acetonitrile or dimethylformamide, optionally catalyze with bases at temperatures between 20 and 120oC. as the bases used are preferably organic bases such as organic amines as triethylamine or pyridine (see European patent application N 0 272 594). Variations of the General method A described in European patent application N 0 070 389.

According to method B, which is particularly reliable when R3and R4= H, the solvent. In particular, the preferred working method, in which the compounds of formulas IV and V, optionally, salts of compounds of formula V, contribute together with an inorganic base, such as hydroxide, carbonate or hydrogencarbonate of alkali or alkaline earth metals such as sodium hydroxide or potassium carbonate, or organic base, for example, organic amine like triethylamine, and then stored for several days, preferably 3 to 10 hours at a temperature of between -40oC and +50oC, preferably -10oC and +10oC.

To the compound of formula III, which is formed in aqueous solution in equilibrium, dropwise with vigorous stirring add the isocyanate of formula II, dissolved in an inert organic solvent, for example toluene, chlorobenzene or chloroform.

The pH values of the aqueous phase is set to 1-3 using acids, preferably inorganic acids as water-salt of sulfuric acid or sulfuric acid. So produced urea derivatives of the formula VI then ciclitira according to known methods (see Hoyben-Weyl, Metoden der Organischen Chemie, Band XXV/1 und XXV/2 (1974)) at a temperature of between 50 and 100oC or, if necessary, by turning laiskotellen similarly well-known methods: see Hoyben-Weyl, Metoden der Organischen Chemie, Band VIII, 120 S. (1952); Hoyben-Weyl, Band IX, S. 875, 869 (1955); European patent application N 0 070 389; patent application U.S. No. 4 881 967; European patent application N 322 401; patent application U.S. No. 3 495 967; European patent application NN 300 307, 349 832.

Known amines of the formula III, which can be manufactured analogously to known methods in R3= R4H; see, for example, Seebach et al., Helv. Chim. Acta, Band 70, 1194 (1987).

Known amines of General formula IX, which are in accordance with European patent application N 3 073 569 can be manufactured in a similar manner as described there by the way.

The invention also concerns the use of compounds of the formula I as herbicides, as well as mixtures of herbicides that include an effective amount of the compounds of formula I and the filler. Suitable fillers are surface-active substances, solid or liquid diluents.

The invention also concerns the method of controlling weeds with weed plants or their environment (before or after puberty) put herbicide effective amount of a compound according to formula I.

Chemical examples

Example 1:

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Prepare a mixture of an ester of the m type 4-chloronicotinate (1.40 g, 0,009 M) dissolved in 20 ml of toluene. The reaction mixture was stirred for 15 h at 20oC and then washed with 10% aqueous hydrochloric acid (3 x 10 ml) and water (3 x 10 ml), dried using sodium sulphate and filtered. After concentrating the filtrate by evaporation, the residue is dissolved in diethyl ether and again precipitated in petroleum ether.

Obtain 2.28 g (81% of theoretical amount) of 7-(4-course)-5,5 - dimethyl-6,8-dioxo-4-oxa-1,7-diazabicyclo[3.3.0] octane with a melting point 97-98oC.

Example 2:

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A mixture of serine (of 1.05 g, 0.01 M), 37% aqueous solution formaldehyde (2 g) and an aqueous solution of sodium hydroxide (10 ml) is kept for 12 h at 4oC, cooled to 0oC and added dropwise to 4-chlorophenylalanine (1.55 g) dissolved in chlorobenzene (5 ml). Then the reaction mixture is stirred for half an hour at 0-5oC and about 2 hours at room temperature, the aqueous phase is shaken out with chloroform (3x10 ml) and remove all of the organic phase.

Then the aqueous phase is acidified with 5% aqueous hydrochloric acid to pH 1 and the product after shaking with ethyl acetate (3x10 ml) contribute to the organic phase, dried with sodium sulfate and filtered. After concentration of the imide (1,15 g, 0.01 M), and then added dropwise at 20oC to N,N'-dicyclohexylcarbodiimide from 2.06 g, 0.01 M) dissolved in acetonitrile (15 ml). The reaction mixture was stirred for 12 h at reverse flow, then filtered and the filtrate concentrated by evaporation. The remaining sediment was placed in acetone and again precipitate by adding water.

Get 7-(4-chlorophenyl)-6,8-dioxo-4-oxa-1,7-diazabicyclo[3.3.0]octane with a melting point of 74-76oC in the amount of 1.75 g (74% of theoretical amount).

Analogously to examples 1 and 2 and in accordance with the General description of the methods A-E according to the present invention can be obtained from compounds of General formula I given in the following table. 1 - 7.

Compounds

Suitable formulations of the compounds of formula I can be manufactured in a traditional way in the form of powders, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, etc. Directly, you can apply any of these forms. To spray the powder can be added suitable means, after which the spray powders in quantities from a few liters to several hundred liters per hectare. Highly concentrated preparations are used p is positive(CSOs) substances(a) and at least representative of the group (a) 0.1 to 20% of surface-active substances and (b) about 1 to 99.9% solid or liquid diluent. In particular, you can get these component parts in approximately the following amounts presented in the table. 8.

According to the purpose of the application and physical properties of the compounds may have a lower or higher content of effective substances. Sometimes, to get a higher ratio of the amounts of surface-active components can be entered into the composition of the necessary effective substances and mix them.

Typical solid diluents are described Watkins, et al, Handbook of Insecticide Dust Diluents and Carries (Reference diluents and carriers powdered insecticides), 2nd Ed., Dorland Books, Caldwell, New Jersey. Can be applied to other or conventional mining or industrial manufactured solid. As wettable powders the most preferred absorbent dust tight thinners. Typical liquid diluents and solvents are described in Marsden, Solvents guide, solvents), 2nd Ed., Interscience, New York, 1950. Among concentrated suspensions preferred suspension with a concentration below 0.1%. Among the concentrated solutions are preferred resistant to separation ew Jersey, and Sisely and Wood, Encyclopedia of Surface Active Agents (encyclopedia of surface - active substances), Chemical Publishing Co. , Inc. , New York, 1964, there is information about surfactants and recommended their use. All formulations can contain smaller amounts of additives to reduce foam, caking, corrosion, microbial growth, etc.

The methods of manufacture of such drugs are well known. Get solutions, which simply mix the components. Temporally solid preparations obtained by mixing and, usually, sylavania, for example, in a hammer mill or a jet mill. Suspension get by wet milling (see, for example, Littler, U. S. Patent 3,060,084). Receive granules and tablets, in which the effective substance is sprayed on the pre-formed carriers in granular form and in which glomeridae substance. Cm. J. E. Browning, Agglomeration, Chemical Engineering, December 4, 1967, p. 147 ff, and Perry's Chemical Engineer's-Handbook (Perry's Handbook of chemical technological means), 5th Ed., MC Graw-Hill, New York, 1973, S, 8-57 ff.

The following information concerning the technology of obtaining compositions for example:

H. M. Loux, U. S. Patent 3,235,361, 15. Februar, 1966, Spalte 6, 16 bis Zeile Spalte 7, Zeile 19 und Beispiele 10 bis 41;

R. W. Luckenbaugh, U. S. Patent 3, 309, 192, 14. Marz 1967, Sp 1959, Spalte 3, Zeile 66 bis Spalte 5, Zeile 17 und Beispiele 1 to 4;

G. C. Klingman, Weed Control as a Science (Unkrautbekampfung als Wissenschaft), John Wiley and Sons, Inc., New York, 1961, p. 81 -96 and

J. D. Fryer and S. A. Evans, Weed Control Handbook (Handbuch der Unkrautbekampfung), 5th Ed., Blackwell Scientific Publications, Oxford, 1968, P. 101-103.

B the following examples, we are talking about mass parts, because there is no other data.

An example of a

Wettable powder, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-4-oxo-1,7-diazabicyclo [3.3.0] octane - 80%

Alkylnaphthalene sodium - 2

Sodium lignosulphonate - 2

Synthetic amorphous silicic acid - 3

Kaolinite - 13

Integral part of the mix and Salavat in a hammer mill to a grain size of solids less than 50 μm, then re-mixed and packaged.

Example B

Wettable powder, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-4-oxo-1,7-diazabicyclo [3.3.0] octane - 50

Alkylnaphthalene sodium - 2

Methylcellulose low viscosity - 2

Diatomaceous earth - 46

Integral part of the mix, roughly pulverized in a hammer mill and then Salavat in the jet mill so that almost all the particles had a diameter less than 10 microns. Before packaging, the product is again stirred.

The use 20-40 holes; 0,84 - 0,42 mm) - 95

Suspension of wettable powder containing 25% solids sprayed in a cone mixer; then the granules are dried and Packed.

Example D

Extrusion tablets, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-4-oxa-1,7-diazabicyclo [3.3.0] octane - 25

Anhydrous sodium sulphate - 10

Raw ligninsulfonate calcium - 5

Calcium/magnesium bentonite - 59

Integral part of the mix, malavaud in a hammer mill and then moisturize approximately 12% of water. The mixture ekstragiruyut in cylinders with a diameter of approximately 3 mm, which are cut into pellets with a length of about 3 mm can be used directly after drying; dried tablets you can crush up to such an extent that they can pass through the filter N 20 U.S. standard (hole diameter 0.84 mm). The granules remaining on the filter N 40 U.S. standard (hole diameter of 0.42 mm), Packed for use, and the proportion of fine fractions are removed.

Example E

The granulate low strength, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-4-oxa-1,7-diazabicyclo [3.3.0] octane - 1

N,N-Dimethylformamide - 9

The granulate from attapulgite (filter 20 to 40 U.S. standard) - 90

The effective substance is dissolved in dissolved is still a short time left in working condition, then pack the granules.

Example F

The granulate, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-4-oxa-1,7-diazabicyclo [3.3.0] octane - 80

Wetting agent - 1

Crude lignosulfonate (5 - 20% of the natural sugars) - 10

Attapulgite clay - 9

Integral part of the mix and Salavat up until they will not pass through the filter with 100 holes. This material is directed to a granulator with a fluidized bed, in which you installed the air flow so that the material easily enters the state pseudocapsule layer, and whereby the material in the state pseudocapsule layer sprayed a thin stream of water. Fluidization and coating continue to until the granules will not have the desired value. Then suspend the deposition and fluidization, in contrast, continue, if necessary, during the heat up until the water content has dropped to the desired value, generally below 1%. The material is then removed and filtered to the desired size range typically using a filter with a 14 - 100 holes (1410 - 149 microns), and then packaged for use.

Example G

Suspension in water, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-4-oxa-1,7-disabililties - 0,5

Diphosphate sodium - 1

Monophosphate sodium - 0,5

Polyvinyl alcohol - 1,0

Water - 56,7

Integral part of the mix and all Salavat into the flour until the consistency of sand thus, to obtain particles of a size substantially less than 5 microns.

Example H

Stable concentrate, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-4-oxa-1,7-diazabicyclo [3.3.0] octane - 99

The aerogel silica - 0,5

Synthetic amorphous silicic acid of 0.5

Integral part of the mix and Salavat in a hammer mill to obtain a material that can pass through the filter N 50 (holes 0.3 mm) U.S. standard. If necessary, the concentrate can contain other components.

Example I

Wettable powder, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-4-oxa-1,7-diazabicyclo [3.3.0] octane - 90,0

Dioctylsulfosuccinate sodium - 0,1

Synthetic purified silicic acid - 9,9

Integral part of the mix and Salavat in a hammer mill to obtain particles of a size substantially less than 100 microns. The material is filtered through a filter N 50 U.S. standard and then packaged.

Example J

Wettable powder, wt.%:

7-(4-chlorine is montmorillonite - 40

Component parts thoroughly mixed, roughly Salavat in a hammer mill and then Salavat in vostokstrojj mill to obtain particles of a size much less than 10 microns. The material is then re-mixed and packaged.

Example K

Oil suspension, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-4-oxa-1,7-diazabicyclo [3.3.0] octane - 35

A mixture of ethers of a polyhydric alcohol and carboxylato acid and oil-soluble petroleum sulfonate - 6

Xylene - 59

Integral part of the mix and Salavat into the flour until the consistency of sand to obtain particles of a size substantially less than 5 microns. The product can be applied directly diluted in oil or emulsified in water.

Example L

Dust, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-4-oxa-1,7-diazabicyclo [3.3.0] octane - 10

Attapulgite - 10

Pyrophyllite - 80

The effective substance is mixed with attapulgite and then placed in a hammer mill to obtain particles with a size significantly less than 200 μm. Then ground the concentrate is mixed with poroshkoobraznym pyrophyllite to homogeneity.

Example M

Suspension in oil, wt.%:

7-(4-Chlorophenyl)-5,5-dimethyl-6,8-dioxo-vodorodnoe oil - 70

All parts Salavat into the flour until the consistency of sand, until the size of the particles of the solids will not be less than 5 microns. Received a thick slurry can be used directly, it is mainly used after dilution in the oil or after emulsification in water.

Biological examples

The results of the experiments show that the compounds according to the present invention are effective herbicides. They are suitable for broadband control weeds before or after the occurrence of the seedlings on the surface, when it is necessary to control all vegetation weeds, for example, industrial areas, parks, open-air cinemas, advertising walls, streets and buildings of Railways. Some compounds are also suitable for the selective control of weeds in such crops as rice, wheat, barley, corn, soybeans, sugar beets and cotton.

The used amount of the compounds according to the present invention depends on several factors, among them is used as a selective or universal herbicides, the corresponding field crop, weed, weather and climate, the selected composition, the method primenen smaller amounts suitable for light soils and/or soils with low organic matter content or for cases when you need short duration, for example, in the case of application of herbicides in a plowed field.

Compounds according to the present invention can be used in combination with other standard herbicides.

In some experiments in greenhouses detected herbicide properties of the compounds according to the present invention. Testing methods and their results are presented below in table. A-D.

In Biological table. A-D the following compounds 1-18 (see end of text).

Testing methods

Produced planting seeds Rosicky (Digitaria spp.), the ordinary barnyard grass (Echinochloa crus-galli), spickle (Setaria feberii), wild oats (Avena fatua), fire rye (Bromus secalinus), cantica (Abutilon theophrasti), ipomea (Ipomoea spp.), cocklebur (Xanthium pensilvanicum) and tubers sorghum (Sorghum), which before germination was treated by an experienced chemicals dissolved in negoitations solvent.

In addition, these weeds were treated with a certain drug to be applied on the soil and on the foliage. At the time of processing plants had a height of 2 to 18 see the Treated plants and control plants were kept in a greenhouse for 16 days, after which all instances with the control plants contained 16 days in th is Ki. Estimates are presented in table. A numeric scale from 0 = no damage, 10 = full damage.

These characters have the following meanings:

C = chlorosis/necrosis,

B = burning,

H = formative effects,

E = inhibition of growth of seedlings,

G = growth promotion.

1. Kannelirovannye (oxa)-hydantoins of the General formula I

< / BR>
where R1and R2independently from each other hydrogen or C1- C4-alkyl;

R3and R4independently from each other hydrogen, C1- C4-alkyl or phenyl or together form a carbocyclic ring;

Q is the residue of Q1< / BR>
< / BR>
or Q5< / BR>
< / BR>
where W is O or S;

R5is hydrogen or halogen;

R6- halogen or CN;

R7is hydrogen, OR11, CO2R11or NHSO2R16;

R8is hydrogen,

R9is hydrogen,

R10- C3- C6-quinil;

R11- C1- C8-alkyl, C3- C8-quinil, C3- C8-alkoxycarbonylmethyl, C2- C8-alkoxyalkyl or C1- C8-haloalkyl;

R16- C1- C4-alkyl, C1- C4-haloalkyl.

2. Kannelirovannye (oxa)-hydantoins of the formula I is other - hydrogen, C1- C3-alkyl or phenyl or together form a carbocyclic ring, R11- C1- C4-alkyl, C3- C6-quinil, C3- C6-alkoxycarbonylmethyl or C1- C4-haloalkyl.

3. Kannelirovannye (oxa)-hydantoins of the formula I on p. 1, where W, R8, R9and R16matter under item 1, R1and R2independently from each other hydrogen or C1- C3-alkyl, R3and R4independently from each other hydrogen, C1- C3-alkyl or together form a 5 - to 6-membered carbocyclic ring, R5is hydrogen, fluorine or chlorine, R6is chlorine, bromine or cyan, R7is hydrogen, OR11or CO2R11, R10- C3- C4-quinil, R11- C1- C4-alkyl, C3- C6-quinil, C1- C4-haloalkyl, C3- C6-alkoxycarbonylmethyl.

4. Kannelirovannye (oxa)-hydantoins of the formula I on p. 1, where R1and R2independently from each other hydrogen or the group number C1- C3-alkyl, R3and R independently from each other hydrogen, C1- C3-alkyl or together may form a 5 - to 6-membered carbocyclic ring, R5is fluorine or chlorine, R6is chlorine, R7- -haloalkyl or C3- C6-alkoxycarbonylmethyl.

5. The method of obtaining annelated (oxa)-hydantoins of the formula I under item 1

< / BR>
where R1and R2independently from each other hydrogen or C1- C4-alkyl;

R3and R4independently from each other hydrogen or C1- C4-alkyl or phenyl or together form a carbocyclic ring;

Q is the residue of Q1< / BR>
< / BR>
or the remainder of Q5< / BR>
< / BR>
where W is O or S;

R5is hydrogen or halogen;

R6- halogen or CN;

R7is hydrogen, OR11, CO2R11or NHSO2R16;

R8is hydrogen;

R9is hydrogen;

R10- C3- C6-quinil;

R11- C1- C8-alkyl, C3- C8-quinil, C3- C8-alkoxycarbonylmethyl, C2- C8-alkoxyalkyl or C1- C8-haloalkyl;

R16- C1- C4-alkyl, C1- C4-haloalkyl,

characterized in that the compound of General formula II

Q-N=C=O,

where Q has the value

subjected to interaction with the compound of General formula III

< / BR>
where R1- R4have the specified values;

R is hydrogen, C1- C
< / BR>
where Q, R1- R4have the specified values;

R is hydrogen,

which when the closure ring is converted into a compound of formula I.

6. The method of obtaining annelated (oxa)-hydantoins of the General formula I under item 1

< / BR>
where R1- R4, Q, W, R5- R11and R16matter under item 1, characterized in that the compound of General formula IV

< / BR>
where R3and R4are specified in paragraph 1 values

subjected to interaction with the compound of General formula V

< / BR>
where R1and R2matter under item 1,

optionally, in the presence of a diluent and optionally in the presence of an acid acceptor intermediate the formed reaction product of General formula III

< / BR>
where R1- R4have the specified values;

R is hydrogen,

if necessary reacts with the compound of General formula II

Q-N=C=O,

where Q is specified in paragraph 1 values

optionally, in the presence of acid and diluent, and get the compound of General formula VI

< / BR>
where R is hydrogen,

then when the closure ring is converted into a compound of formula I.

7. Way floor - R11and R16have the meanings specified in paragraph 1 of the formula

characterized in that the compound of General formula III

< / BR>
where R is hydrogen or C1- C4-alkyl,

with phosgene or a substitute for phosgene transform primarily in connection with the General formula VII

< / BR>
where R1- R4and R have the above values,

which compound of General formula VIII

Q-NH2,

where Q has the value

forms a compound of General formula VI

< / BR>
from which when the closure ring get the connection formula I.

8. The method of obtaining annelated (oxa)-hydantoins of the General formula I under item 1

< / BR>
where R1- R4, Q, W, R5- R11and R16have the meanings specified in paragraph 1 of the formula

characterized in that the compound of General formula XI

< / BR>
where R1- R6have the specified values, X Is O or NH,

subjected to interaction with one of the compounds of formula XII

R11- Z

or formula XIII

R11SO2-Z

where R11has the specified values,

Z is chlorine, bromine or iodine,

and get the compounds of formula I.

9. Herbicide composition containing the active substance and additives target different those who

10. The method of controlling weeds by treating the plants or the soil on which they grow, the active substance, characterized in that the active substance use compounds of formula I on p. 1 in an effective amount.

 

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FIELD: agriculture.

SUBSTANCE: invention describes a method for feeding potato and tomato with 6-benzylaminopurine an aqueous solution taken in the concentration 10-4 M and growing pants up to preparing harvest according to technology accepted for the culture crop. Invention proposes 3-fold treatment of plants for vegetation: at the lateral branching phase, at onset of forming economically value organs and immediately after the growth termination. Method provides the effective enhancing the productivity of the most important vegetable crops - tomato and potato.

EFFECT: improved enhancing method.

6 tbl, 4 ex

FIELD: organic chemistry, chemical technology, herbicides.

SUBSTANCE: invention describes a method for preparing compounds of the formula (I):

wherein each R1, R2, R3 means independently of one another (C-C6)-alkyl; R can represent also pyridyl; R4 and R5 in common with nitrogen atoms to which they are joined form unsaturated 5-8-membered heterocyclic ring that can be broken by oxygen atom; G means hydrogen atom. Method involves interaction of compound of the formula (II):

wherein R1, R2 and R3 have above given values; R6 is a group RR9N-; R7 is a group R10R11N-; each among R8, R, R10 and R11 means independently of one another hydrogen atom or (C1-C6)-alkyl in inert organic solvent being optionally with the presence of a base with compound of the formula (IV) ,

(IVa)

or (IVb) ,

wherein R4 and R have above given values; H x Hal means hydrogen halide. The prepared compound of the formula (I) wherein G represents ammonium cation is converted to the corresponding compound of the formula (I) by treatment with Brensted's acid wherein G represents hydrogen atom. Also, invention describes compound of the formula (II) wherein R1, R2, R3, R6 and R7 have above indicated values.

EFFECT: improved preparing method.

9 cl, 12 ex

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes a synergistic composition of herbicides comprising components (A) and (B) wherein (A) represents herbicide taken among the group of the formula (I):

wherein R1 means (C1-C4)-alkyl; R2 means (C1-C4)-alkyl; R3 means hydrogen atom; X and Y mean (C1-C4)-alkoxy-group; (B) represents one or two herbicides taken among the group of compounds or their acceptable forms: alachlor, metolachlor, acetochlor, dimetenamide, atrazine, cyanasin, metribusin, fluthiamide, nicosulfuron, rimsulfuron, primisulfuron, pendimetalin, sulcotrion, dicamba, mesotrion, isoxachlortol, metosulam, anilofos, fenoxaprop-ethyl, setoxydim, diclofop-methyl, MCPA, bromoxynil, pyridat, clopyralid, iodosulfuron-methyl, ethoxysulfuron, amidosulfuron, gluphosinat-amminium, isopropylammonium-glyphosate, imasetapir wherein components (A) and (B) are taken in the effective doses. Also, invention describes a method for control of weeds by using above indicated herbicide composition. Invention provides the development of the synergistic herbicide composition eliciting high activity.

EFFECT: improved method for control, valuable properties of composition.

6 cl, 26 tbl, 3 ex

FIELD: agriculture, plant science, plant protection.

SUBSTANCE: the suggested herbicidal composition of selective action contains, except generally accepted additional substances for the composition, a mixture as an active substance including a) herbicidally efficient quantity of compound of formula (I) , where R1 and R3 each independently means ethyl, ethynyl, C1- or C2alkoxy; R4 and R5 forms together the group Z2-CR14(R15)-CR16(R17)-O-CR18(R19)-CR20(R21)-(Z2); R14, R15, R16, R17, R18, R19, R20 and R21 means hydrogen; G means hydrogen, -C(X1)-R30, -C(X2)-X3-R31; X1, X2, X3 means oxygen; R30, R31 each independently means C1-C10alkyl, or salts or diastereoisomer of compound of formula (I), and b) efficient quantity of antidote of formula IIa to prevent harmful action of herbicide, where R22 means hydrogen, alkaline-earth metal or ethyl, or of formula IIb , where R23 means hydrogen, alkaline-earth metal or ethyl, and method for selective control for weed plants and grasses in cultivated plants. Thus, the antidote decreases the damage of cultivated plants induced by herbicide of formula (I).

EFFECT: higher efficiency of plant protection.

3 cl, 4 ex, 4 tbl

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