DE19535842A1 - New N-(substd. tert. alkyl)-3-substd. pyrrolinone derivs. - Google Patents

Abstract

N-substd. pyrrolinone derivs. of formula (I) are new. A = H, halo, 1-6C alkyl (opt. substd. by halo or 1-6C alkoxy), or Z; Z = OR4, SR4, SOR4, SO2R4 or NR5R6; R1 = Z; R2 = H, 1-6C alkyl, 1-6C alkoxy, halo, OH, NH2, 1-6C alkylamino or 1-6C dialkylamino; R3 = H, 1-6C alkyl or halo; R4, R6 = H, 1-6C alkyl (opt. substd. by halo or 1-6C alkoxy), 2-6C alkenyl, 2-6C haloalkenyl, 3-6C alkynyl, 3-6C cycloalkyl, Ar, CH2Ar or COR7; R5 = as R4 , OH or 1-6C alkoxy; or NR5R6 = pyrrolidino, piperidino or morpholino; Ar = phenyl (opt. substd. by Xm); R7 = H, 1-6C alkyl, 1-6C haloalkyl, 3-6C cycloalkyl or Ar; X = H, OH, 1-6C alkyl, 1-6C haloalkyl, 1-6C alkoxy-1-6C alkyl, 1-6C alkoxy, 1-6C haloalkoxy, SH, 1-6C alkylthio, 1-6C alkylsulphonyl, 1-6C alkylsulphinyl, NH2, 1-6C alkylamino, 1-6C dialkylamino, halo, CN, 1-6C alkoxycarbonyl, aminocarbonyl, 1-6C alkylaminocarbonyl, 1-6C dialkylaminocarbonyl or NO2; E = CO-R8, C(NOR9)R8, pyridyl, or a gp. of formula (a)-(c), all opt. substd. by Xm; Q = CH, or one Q is CH and the other is N; D = O, S, NH, or N-1-6C alkyl; R8 = H, OH, 1-6C alkyl, 2-6C alkenyl, 2-6C alkynyl, Ar, CH2Ar, OR9, OM or NR10R11; R9 = H, 1-6C alkyl, benzyl or phenyl (opt. substd. by 1-6C alkyl, 1-6C alkoxy, halo or NO2); R10, R11 = H, OH, 1-6C alkyl, 2-6C alkenyl, 3-6C alkynyl, 1-6C alkoxy, Ar or benzyl (opt. substd. by Xm); or NR10R11 = pyrrolidino, piperidino or morpholino; M = Li, Na, K, Zn, Mn, Ca, Ba or NH4.

Description

The invention relates to 3- or 3,4-hetero-substituted pyrrolinones, their preparation and their use as herbicidal agents.

It is already known that certain 3-phenylpyrrolin-2-ones (EP 372 586, EP 557691) possess herbicidal properties.

However, the herbicidal activity is often insufficient or selectivity occurs problems in main agricultural crops.

The object of the present invention is therefore to provide compounds which do not have these disadvantages and the biological properties of the previous known connections are superior.

This problem is solved by new 3- or 3.4-hetero-substituted pyrrolinone derivatives of the general formula I

in the
AH, halogen, C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, the group OR⁴, SR⁴, SOR⁴, SO₂R⁴ or -NR⁵R⁶,
R¹ is the group OR⁴, SR⁴, SOR⁴, SO₂R⁴ or -NR⁵R⁶,
R² H, C₁-C₆-alkyl, C₁-C₆-alkoxy, halogen, hydroxy, amino, C₁-C₆-alkylamino or C₁-C₆-dialkylamino,
R³ H, C₁-C₆ alkyl or halogen,
R⁴ H, C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, halogen-C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₃ -C₆-cycloalkyl, optionally substituted with the group X _m phenyl or benzyl or the group COR⁷,
R⁵ H, C₁-C₆-alkyl, halogen-C₁ -₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, halogen-C₂-C₆-alkenyl, C₃ -C₆-alkynyl, C₃-C₆- cycloalkyl, hydroxy, optionally substituted with the group X _m phenyl or benzyl or the group COR⁷,
R⁶ H, C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, halogen-C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₃ -C₆-cycloalkyl, optionally substituted with the group X _m phenyl or benzyl or the group COR⁷,
R⁵ and R⁶ together with the adjacent nitrogen atom form a pyrrolidino, piperidino or morpholino group,
R⁷ H, C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₃-C₆-cycloalkyl or phenyl, which can optionally be substituted by the group X _m ,
XH, hydroxy, C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkoxy, halogen-C₁-C₆-alkoxy, mercapto, C₁-C₆- Alkylthio, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylsulfinyl, amino, C₁-C₆-alkylamino, C₁-C₆-dialkylamino, halogen, cyano, C₁-C₆-alkoxycarbonyl, aminocarbonyl, C₁-C₆- alkylaminocarbonyl, C₁- C₆-dialkylaminocarbonyl or nitro,
m 1, 2 or 3, where in the case of m = 2 or 3 the substituent X can be the same or different,
E is the group -CB-R⁸ or one of the substituents from the group E-1 to E-6, which may optionally be substituted in each case by the group X _m ,

D oxygen, sulfur, NH or N-C₁-C₆-alkyl,
B oxygen or the group = NOR⁹,
R⁸ H, hydroxy, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, benzyl, optionally substituted with the group X _m phenyl or benzyl, the group OR⁹, the group OM or the group NR¹⁰R¹¹
R⁹ H, C₁-C₆-alkyl, benzyl, phenyl or a phenyl radical substituted by C₁-C₆-alkyl, C₁-C₆-alkoxy, halogen or nitro,
R¹⁰ H, hydroxy, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alkoxy, a phenyl or benzyl optionally substituted with the group X _m ,
R¹¹ is hydrogen, hydroxy, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alkoxy, a phenyl or benzyl optionally substituted by the group X _m ,
R¹⁰ and R¹¹ together with the adjacent nitrogen atom form a pyrrolidino, piperidino or morpholino group,
M is a cation from the group lithium, sodium, potassium, an equivalent from the group zinc, manganese, calcium, barium or an ammonium ion, have a superior activity compared to the known compounds.

The term "halogen" includes fluorine, chlorine, bromine and iodine. Under the terms "Alkyl", "alkenyl" and "alkynyl" are both straight chain and branched To understand hydrocarbon residues. The compounds of formula I can optionally in different enantiomers, tautomers or geometrical Shapes are available. These are also the subject of the invention.

The compounds according to the invention can be prepared in a manner known per se be, for example, by

• A) if the group A in the compounds of the general formula I according to the invention is hydroxy, a compound of the general formula II, in which R¹, R², R³, R⁹ and E have the meaning described in the general formula I, subject to an intramolecular cyclization, or
• B) if A in the compounds of the general formula I according to the invention represents the group OR⁴, a hydroxy compound of the general formula Ia obtained by process A), with an alkylating agent of the general formula R⁴-L, where R⁴ has the meaning given above and L represents halogen or another escape group customary for alkylating reagents, or
• C) if A in the compounds of general formula I according to the invention for the Group NR⁵R⁶ is a hydroxy compound obtained by process A) general formula Ia with an amine of the general formula HNR⁵R⁶, in which R⁵ and R⁶ have the meaning given above, implements, or
• D) if A in the compounds of general formula I according to the invention for the Group SR⁴ is a hydroxy compound obtained by process A) general formula Ia with a mercaptan of the formula HSR⁴, or
• E) if A in the compounds of general formula I according to the invention for is one of the groups SOR⁴ or SO₂R⁴, one obtained by process D) Compound of the general formula I in which A for the group SR⁴ is oxidized, or
• F) if A in the compounds of general formula I according to the invention is C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, a compound of general formula III R¹, R², R³ and E have the meaning described in the general formula I and Y is C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, is subjected to an intramolecular cyclization .

The intramolecular cyclization according to process A) is conveniently in Presence of a base or acid and optionally an inert solvent or Diluent carried out. Suitable bases are, for example, sodium or Potassium hydroxide, sodium methoxide or ethanolate, sodium hydride, sodium or Potassium carbonate or potassium tert-butoxide. Suitable acids are u. a. Hydrochloric acid, Sulfuric acid, acetic acid or Lewis acids such as aluminum chloride or zinc chloride. In particular, have been found as solvents or diluents Tetrahydrofuran, toluene and ethanol have proven their worth.

Processes B) and F) are preferably carried out in the presence of an inert solvent or Diluent and an acid-binding agent performed. As a solution or Diluents are suitable here, for example, acetonitrile, tetrahydrofuran, Dimethylformamide or toluene. Sodium or  Potassium hydroxide, sodium methoxide or ethanolate, sodium hydride, sodium or Potassium carbonate or potassium tert-butoxide can be used.

Processes C) and D) are carried out using solution or Diluents such as aliphatic or aromatic hydrocarbons, the can optionally be halogenated. Examples include toluene, Xylene, chlorobenzene, ligroin, hexane or cyclohexane. The implementation is preferred carried out under dehydrating conditions, for example with addition a water-binding agent such as sodium or potassium sulfate or Molecular sieve. Azeotropic distillation of water has also proven to be beneficial proven during the reaction.

Process E) is carried out using solvents or diluents such as aliphatic or aromatic hydrocarbons, which may or may not be halogenated can, performed. For example, m-chloroperbenzoic acid is an oxidizing agent suitable.

All reactions are preferably carried out under the pressure of the environment, although they are also carried out at elevated or reduced pressure could. They can be run within a wide temperature range. in the generally they are at a temperature between -20 ° C and the boiling point of the Reaction mixture, preferably carried out at 0 ° C to 180 ° C.

The presence of an additional reaction catalyst can be advantageous. As such catalysts are potassium iodide and onium compounds such as quaternary Ammonium, phosphonium, arsonium and sulfonium compounds are suitable. Likewise suitable are polyglycol ethers, in particular cyclic ones, such as, for example, 18-crown-6, and tertiary amines such as tributylamine. Quaternary are preferred Ammonium compounds such as benzyltriethylammonium bromide and Tetrabutylammonium bromide.

The inventive according to the methods described above Compounds can be isolated from the reaction mixture by the customary methods are, for example by distilling off the solvent in normal or reduced pressure, by precipitation with water or by extraction. An increased Purity can usually be determined by column chromatographic purification as well can be obtained by fractional distillation or crystallization.

The compounds of the invention are usually almost colorless and odorless Liquids or crystals that are partially soluble in water, aliphatic Hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane, readily soluble in halogenated hydrocarbons such as chloroform, methylene chloride and Carbon tetrachloride, aromatic hydrocarbons, such as benzene, toluene and xylene,  Ethers such as diethyl ether, tetrahydrofuran and dioxane, carbonitriles such as Acetonitrile, alcohols such as ethano and methanol, carboxamides such as Dimethylformamide, sulfoxides such as dimethyl sulfoxide or organic bases such as for example pyridine.

The precursors of general formula II or III required for processes A) and D) can be produced by methods known from the literature.

The compounds according to the invention show a good herbicidal action in broadleaved Weeds and grasses. A selective use is possible in different cultures, e.g. B. in Rice, rapeseed, beets, soybeans, cotton, corn, barley, wheat and others Cereals. Individual compounds are also available as selective herbicides in rice, beets, Cotton, soybeans, corn and cereals are particularly suitable. Likewise, the connections for weed control in permanent crops, such as. B. in forest, ornamental wood, fruit, wine, citrus, Nut, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops.

The compounds of the invention can e.g. B. can be used in the following plant species:
Dicotyledon weeds of the genera such as Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsiumum, Soncham , Veronica, Abutilon, Datura, Viola, Galeoppsis, Papaver, Centaurea and Chrysanthemum;
Monocotyledonous weeds of the genera such as Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Elymus, Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemum and Apera.

Depending on the type of application, the application rates fluctuate between pre and post 0.001 to 5 kg / ha.

The compounds according to the invention can either be used alone, in a mixture with one another or can be used with other active ingredients. A promotion of the active intensity and the Effectiveness can be increased, for example, by additions such as organic solvents, wetting agents and oils. Such additives therefore leave if necessary, a reduction in the dosage of active ingredient.

The active compounds according to the invention or their mixtures are expediently in the form of Preparations such as powders, sprinkling agents, granules, solutions, emulsions or Suspensions, with the addition of liquid and / or solid carriers respectively Diluents and optionally adhesives, wetting agents, emulsifying agents and / or dispersing agents applied.  

Suitable liquid carriers are, for example, aliphatic and aromatic Hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, Dimethylformamide, mineral oil fractions and vegetable oils.

Suitable solid carriers are minerals, such as bentonite, silica gel, talc, Kaolin, attapulgite, limestone and vegetable products such as flour.

Examples of surface-active substances include calcium lignin sulfonate, Polyethylene alkylphenyl ether, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted Benzenesulfonic acids and their salts.

The proportion of the active ingredient (s) in the various preparations can vary widely Limits vary. For example, the agents contain about 10 to 90 percent by weight Active ingredient, about 90 to 10 weight percent liquid or solid carriers as well optionally up to 20 percent by weight of surfactants.

The agents can be applied in the customary manner, for example using water as Carrier in spray liquor quantities from about 100 to 1000 liters / ha. An application of funds in So-called low-volume and ultra-low processes are just as possible as their application in Form of so-called microgranules.

The preparation of these preparations can be carried out in a manner known per se, for example be carried out by grinding or mixing processes. If you can Preparations of the individual components are also only mixed shortly before they are used, as it is done in practice, for example, using the so-called tank mix method.  

The following examples illustrate the preparation of the invention Links.

Example 1.1 1- [1- (3-Chlorophenylaminocarbonyl) -1-methylethyl] -3- (2-fluorophenoxy) -4-hydroxy-pyrrolin2-one

5.91 g (197 mmol) of sodium hydride (80%) are placed in 120 ml of toluene. This will be done at Reflux temperature 73.69 g (169 mmol) N- (2-fluorophenoxy) acetyl-N- (1- (3- chlorophenylaminocarbonyl) -1-methylethyl] aminoacetate in 100 ml of toluene dripped. The mixture is heated under reflux for four hours and then to room temperature cooled down. Then it is carefully mixed with water and with ethyl acetate extracted. The aqueous phase is acidified with 2N hydrochloric acid and with ethyl acetate extracted. The combined organic phases are dried over magnesium sulfate and constricted.

Yield: 31.69 g (46% of theory)
Mp: 185-186 ° C

Example 1.2 1- [1- (3-Chlorophenylaminocarbonyl) -1-methylethyl] -3- (2-fluorophenoxy) -4-methoxypyrrolin2-one

10.0 g (24.7 mmol) 1- [1- (3-chlorophenylaminocarbonyl) -1-methylethyl] -3- (2-fluorophenoxy) - 4- hydroxypyrrolin-2-one are suspended in 100 ml of acetonitrile and mixed with 1.83 mg (28.7 mmol) KOH powder added. 5.34 g (28.7 mmol) of p-toluenesulfonic acid are then added dropwise methyl ester, dissolved in 60 ml of acetonitrile, and heated under reflux for 3 hours. After this Cooling is combined with water and extracted with methylene chloride. The United organic phases are dried over magnesium sulfate and concentrated.

Yield: 9.9 g (95.7% of theory)
Rf value: 0.67 (EE) (EE = ethyl acetate)

Example 1.3 1- [1- (3-chlorophenylaminocarbonyl) -1-methylethyl] -3- (2-fluorophenoxy) -4-methylamino-3- phenylpyrrolin-2-one

2.0 g (4.94 mmol) 1- [1- (3-chlorophenylaminocarbonyl) -1-methylethyl] -3- (2-fluorophenoxy) - 4- hydroxypyrrolin-2-one are dissolved in a mixture of 10 ml of xylene and 5 ml of glacial acetic acid. To 5 ml of a 40% methylamine solution are added with stirring and the Reaction mixture under reflux for 4 hours using a water separator heated. Then it is mixed with ice water and extracted with methylene chloride. The combined organic phases are washed with water, over magnesium sulfate dried and concentrated.

Yield: 1.92 g (93% of theory)
Rf value: 0.52 (EE)

Example 1.4 1- [1- (3-Chlorophenylaminocarbonyl) -1-methylethyl] -3- (2-fluorophenoxy) -4-methylpyrrolin2-one

To 7.67 g (18 mmol) of N- [1- (3-chlorophenylaminocarbonyl) -1-methylethyl] -N- (2-oxopropanyl) -2-- (2-fluorophenoxy) acetic acid amide in 25 ml ethanol are refluxed 1.15 mg (18 mmol) KOH powder added and the reaction mixture heated under reflux for 4 hours. The Solvent is removed, the residue is mixed with saturated sodium chloride solution and extracted with ethyl acetate. The combined organic phases are with Washed water, dried over magnesium sulfate and concentrated. The so obtained The product is purified by column chromatography (hexane / ethyl acetate).

Yield: 3.26 g (45% of theory)
Mp: 152-153 ° C
The following compounds of the formula I are prepared analogously, where R² and R³ = H and

is.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

The following application examples explain the usability of the compounds of the invention.  

Example of use A

In the greenhouse, the plant species listed below were mixed with the Treated compounds listed in an application rate of 1.0 kg of active ingredient / ha. The For this purpose, active ingredients were spread evenly as an emulsion with 500 liters of water / ha sprayed the floor. Two weeks after the treatment, those according to the invention showed Compounds have high crop selectivity in cotton, corn and wheat excellent action against weeds.

Example of use B

The compounds listed in the table below were removed in the greenhouse Pipette applied to a water surface of approx. 170 cm², the test plants were used both in the pre-emergence and in the 1-2 leaf stage. Showed after 2 weeks themselves that the compounds according to the invention are highly effective against important rice weeds and at the same time are selective to water rice.

Claims (4)

1. 3- or 3,4-hetero-substituted pyrrolinone derivatives of the general formula I (I) in the
AH, halogen, C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, the group OR⁴, SR⁴, SOR⁴, SO₂R⁴ or -NR⁵R⁶,
R¹ is the group OR⁴, SR⁴, SOR⁴, SO₂R⁴ or -NR⁵R⁶,
R² H, C₁-C₆-alkyl, C₁-C₆-alkoxy, halogen, hydroxy, amino, C₁-C₆-alkylamino or C₁-C₆-dialkylamino,
R³ H, C₁-C₆ alkyl or halogen,
R⁴ H, C₁-C₆-alkyl, halogen-C ₁-C₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, halogen-C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₃-C₆-cycloalkyl, optionally substituted with the group X _m phenyl or benzyl or the group COR⁷,
R⁵ H, C₁-C₆-alkyl, halo-C ₁-C₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, halogen-C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₃-C₆- cycloalkyl, hydroxy, optionally substituted with the group X _m phenyl or benzyl or the group COR⁷,
R⁶ H, C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₁-C₆-alkoxy-C 1 -C₆-alkyl, C₂-C₆-alkenyl, halogen-C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₃-C₆-cycloalkyl, optionally substituted with the group X _m phenyl or benzyl or the group COR⁷,
R⁵ and R⁶ together with the adjacent nitrogen atom form a pyrrolidino, piperidino or morpholino group,
R⁷ H, C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₃-C₆-cycloalkyl or phenyl, which can optionally be substituted by the group X _m ,
XH, hydroxy, C₁-C₆-alkyl, halogen-C₁-C₆-alkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkoxy, halogen-C₁-C₆-alkoxy, mercapto, C₁-C₆- Alkylthio, C₁-C₆- alkylsulfonyl, C₁-C₆-alkylsulfinyl, amino, C₁-C₆-alkylamino, C₁-C₆-dialkylamino, halogen, cyano, C₁-C₆-alkoxycarbonyl, aminocarbonyl, C₁-C₆- alkylaminocarbonyl, C₁- C₆-dialkylaminocarbonyl or nitro,
m 1, 2 or 3, where in the case of m = 2 or 3 the substituent X can be the same or different,
E is the group -CB-R⁸ or one of the substituents from the group E-1 to E-6, which may optionally be substituted in each case by the group X _m , D oxygen, sulfur, NH or N-C₁-C₆-alkyl,
B oxygen or the group = NOR⁹
R⁸ H, hydroxy, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, benzyl, phenyl or benzyl optionally substituted with the group X _m , the group OR⁹, the group OM or the group NR¹⁰R¹¹,
R⁹ H, C₁-C₆-alkyl, benzyl, phenyl or a phenyl radical substituted by C₁-C₆-alkyl, C₁-C₆-alkoxy, halogen or nitro,
R¹⁰ H, hydroxy, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alkoxy,
a phenyl or benzyl optionally substituted with the group X _m ,
R¹¹ is hydrogen, hydroxy, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₆-alkoxy, a phenyl or benzyl optionally substituted by the group X _m ,
R¹⁰ and R¹¹ together with the adjacent nitrogen atom form a pyrrolidino, piperidino or morpholino group,
M is a cation from the group lithium, sodium, potassium, an equivalent from the group zinc, manganese, calcium, barium or an ammonium ion
mean. 2. Agents with herbicidal activity characterized by a content of at least one A compound according to claim 1. 3. Agents with herbicidal activity according to claim 2 in a mixture with carrier and / or Auxiliary materials. 4. Use of compounds according to claim 1 for combating monocot and dicot weeds.