DD273436A5 - METHOD FOR PRODUCING SUBSTITUTED TETRAHYDROPHTHOLIMIDES AND THEIR USE OF THE HERBIDE - Google Patents

Abstract

The invention relates to a process for the preparation of novel substituted tetrahydrophthalimides which are applicable as herbicides. According to the invention, the compounds of the formula (I) or salts thereof in which the substituents have the meaning given in the description are prepared, for example by reacting a compound of the formula (II) with a compound of the formula (III) in a manner known per se and optionally converting these compounds into their salts. Formulas (I) to (III)

Description

Process for the preparation of substituted tetrahydrophthalimides and their use as herbicides

Field of application of the invention

The invention relates to a process for the preparation of substituted tetrahydrophthalimides which are used as herbicidal active ingredient.

Characteristic of the known state of the art

It is already known that tetrahydrophthalimides containing certain benzyl groups with Phosphorsäuresterresten have herbicidal properties, s. JP-A 1103-887 "However, these compounds have disadvantages in the application, such as. As an insufficient selectivity or too low efficiency.

Object of the invention

The invention provides a process for the preparation of novel tetrahydrophthalimides with other substituents on a benzylic carbon atom, which surprisingly have an advantageous selective herbicidal action.

Explanation of the essence of the invention

The object of the invention is to provide processes for the preparation of novel tetrahydrophthalimides which have a sufficient selectivity.

-1a-

17U3

The present invention therefore provides the compounds of the formula (I) or salts thereof

0X

(D,

CH-Z

wherein

Hydrogen or halogen, halogen

-WR ² , -NR ¹ R

-C = N-OR ³ , -0

² , J-OR ² , J-SR ² , -L ¹ R ² , -WL ² ,

, -C ^ N, -NH-C-NR ¹ R- * -CH ₀ WR ^ or 'j' 2

273 43

R = H or (C ₁ -C ₄ ) -alkyl

R ¹ = hydrogen, hydroxy, (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkylthio, amino, (C ₁ -C ₄ ) -alkylamino, (C ₁ -C ₄ ) -dialkylamino or cyano .

or R ¹ and Z together are a radical -W-CH ₂ -CH ₂ -W-

R ² = hydrogen, (C ₁ -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl, where the alkyl, alkenyl or alkynyl radical is in each case represented by (C _3- Cy) -cycloalkyl, halogen, (C ₁ -C ₄ ) -alkoxy, (C ₁ -C ₄ ) -alkylthio, di- (C ₁ -C ₄ -alkyl) -amino, cyano, nitro, phenyl, tri (C ₁ -C ₄ alkyl) silyl, benzyloxy or by a four- to seven-membered saturated or unsaturated heterocycle containing one to three nitrogen, oxygen or sulfur atoms, (C ₃ -Cy) cycloalkyl, unsubstituted or substituted by Halogen, cyano, (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy or phenoxy, which may be substituted by CF ₃ , halogen or (C ₁ -C ₄ ) -alkyl, substituted phenyl, further a remainder of the formulas

R ³ WR ³ WR ³ R ³

I Il ο I Il .. ο Il., - (C) _n -C-WR ³ , - (C) _n -C-NR ¹ R ³ , - (C) _n -W- (C) -WR ³ ,

A ¹ A ¹ R ¹ A ¹

R ³ R ³ 0 0 00

(C) _n -W- (C) -NR ¹ R ³ , - (U-NR ¹ -S-R ³ , -C-NH-P (OR ³ ) ₂ ,

I1 Ii I R ¹ R ¹ 0

ί? 3 Ϊ 3

-SOR " ³ or P (R ^

R ³ = hydrogen, (C ₁ -C ₄ ) -alkyl, (C ₃ -C ₇ ) -cycloalkyl, (C ₂ -C ₄ ). Alkenyl, (C ₂ -C ₄ ) alkynyl or phenyl which may be substituted by halogen, cyano, (C ₁ -C ₄ ) -alkyl or

η ~ O, 1 or 2 ρ β 1 or 2 and

W = oxygen or sulfur.

Preferred of these are compounds of the formula X wherein 10

X = H, F or Cl

Y = F, Cl or Br

2 β WR ² , WCR ² or -O \ J, in particular WR ² , R ¹ = H, (C ₁ -C ₄ ) -alkyl or

R ² = H, (C ₁ -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl, which is represented by (C ₁ -C ₄ ) -alkoxy, (C ₁ C ₄ ) alkylthio or halogen or a radical of the formulas

R ³ WR ³ WR ³ R ³ - (C) _n -C-WR ³ , - (C) _n -C-NR ¹ R ³ , - (C) _n -W- (C) -WR ³ , A ¹ R ¹ Rl Rl

R ³ e H, (C ₁ -C ₄ ) -alkyl or phenyl η = 0, 1 or 2 ρ = 1 or 2 and

W = O or S mean

 35

Alkyl, alkenyl, alkynyl or alkoxy can be straight-chain or branched in the abovementioned definitions. Halogen is preferably fluorine, chlorine or bromine.

73436

In the case of R ^ or R ³ '= Waeeeretoff the compounds may exist as salts. Examples of suitable agricultural salts are Na, K ,, Mg, Ca, Zn salts or ammonium or organic mono- to tetrasubstituted ammonium, sulfonium, sulfoxonium or phosphonium salts, where all sub-substituents are, for example, alkyl, Hydroxyalkyl , cycloalkyl, phenyl radicals, etc. can act.

The compounds of the formula (I) have benzyl -CHR ¹ Z for R ¹ f H f Z an optically active center. Si "can therefore be present as stereoisomeric mixtures or in the form of pure stereoelomers or form diastereomers with further optically active substituents. The invention covers all these isomers or mixtures thereof.

The present invention also relates to processes for the preparation of compounds of the formula (I) and salts thereof, characterized in that

a) a compound of the formula (II) with a compound of the formula (III)

II H ₂ NU)> Y ΙΠ

b) an isocyanate of the formula (IV) with a compound of the formula (II)

27143 "

O = C = NZf WY IV

or c) a compound of the formula (V)

in which A "= a radical of the formulas -CHO, -CHR ¹ -Hai (Hal = Cl or Br), -CHR ¹ -OH or -CHR ¹ -COOR ³ , derivatized in a known manner to the compounds of the formula I. and the compounds obtained under a) to c) are optionally converted into their salts.

In the case of variant a), the reaction is expediently carried out in an inert solvent, for example an aromatic solvent, such as toluene, chlorobenzene or dichlorobenzene, or in glacial acetic acid. However, EtS is also possible to dispense with the solvent. Optionally, a catalyst such as p-toluene sulfonic acid may be added. Di-J reaction temperatures can vary between 1O ⁰ C and 16O ⁰ C. At these temperatures, the conversion for the Variant "b) takes place. In the latter case, for example, aromatic solvents such as toluene, xylene are used as the inert solvent. You can also work without solvents.

As Doriveti & ierungsreaktionen in case c) come, for example, esterifications, alkylations, acylations

or nucleophilm substitutions in question, the bIb

Standard Reactions Known to the Expert Bind. Likewise, the salt formation takes place by customary methods.

The outer compounds of formula II or III are known or accessible by conventional methods. The compounds of formula V are prepared analogously to Verfahrensvarlanten a) or b) from the compounds of formula II.

The compounds of the formula I according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dikotly harmful plants. Even difficult to control perennial weeds, which expel from rhizomes, WurzelStückchen or other permanent organs, are well detected by the active ingredients. Examples of such harmful plants are various types of Avena, LoIium, Alopecurus, Phalaris, Echinochloa, Dlgltarla, Setaria, Cyperue, Agropyron, Cynodon, Imperata, Sorghum, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abut11on, Sida, Convolvulus, Cirsium, Rurox, Artemisia, Sagittaria, Allsma, Eleocharis and Scirpus. It is immaterial whether the substances are applied in the pre-sowing, pre-emergence or postemergence process.

If the compounds according to the invention are applied to the surface of the earth prior to germination, either the emergence of the weed seedlings is completely prevented, or the weeds grow up to the cotyledon stage, but then cease their growth and finally die completely after three to four weeks. In application of the active ingredients «call the green parts of the plant In the casserole process also occurs very quickly after treatment, a drastic growth & top, and the weed plants remain in the existing at the application point point growth stage or

273 4

die after a given time more or less quickly, so that in this way a weed competition harmful to crops can be eliminated very early and sustainably by the use of the new compounds according to the invention.

Although the compounds according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crops of economically important crops, e.g. Wheat, barley, rye, rice, maize, sugar beet, cotton and soya only marginally or not at all damaged. For these reasons, the present compounds are very well suited for the selective control of undesired plant growth in agricultural crops.

In addition, the compounds according to the invention have growth-regulatory properties in crop plants. They regulate into the plant's own metabolism and can thus be used to facilitate harvesting such as. can be used by triggering desiccation, abscission and stunting. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous cultures, as storage can be reduced or completely prevented.

The compositions according to the invention can be used as wettable powders, emulsifiable concentrates, sprayable solutions, dusts, mordants, dispersions, granules or microgranules in the customary formulations.

273 4 3

Injectable powders are uniformly water-dispersible preparations which, in addition to the active ingredient except, if appropriate, a diluent or inert substance, are also wetting agents, e.g. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenylsulfonates and dispersants, 2.B. Ligninsulfonsauree sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonate sodium or oleoylmethyltaurine acid sodium. The preparation is carried out in the usual way, e.g. by grinding and mixing the components.

Emulsifiable concentrates may e.g. by dissolving the active ingredient in an inert organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. In the case of liquid active substances, the solvent content may also be omitted in whole or in part. Examples of emulsifiers which may be used are alkylarylsulfonic acid calcine salts such as calcium dodocylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycolic esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensate products, fatty alcohol / propylene oxide / ethylene oxide condensation products, alkyl polyglycol ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.

Dusts may be obtained by premilling the active ingredient with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite, pyrophyllite or diatomaceous earth obtained.

Granules can be prepared either by spraying the active ingredient onto adsorptive, granulated inert material or by applying

Drug concentrations by binders, e.g. Polyvinyl alcohol, sodium polyacrylate or mineral oils may also be granulated on the surface of carrier materials such as sand, kaolinites or granulated inert material, and suitable active ingredients may be granulated in the manner customary for the production of fertilizer granules, if desired as a mixture with fertilizers.

In wettable powders, the drug concentration is e.g. about 10 to 90 wt .-%, the Reut to 100 wt .-% consists of conventional formulation ingredients. For emulsifiable concentrates, the concentration of active substance may be about 5 to 60% by weight. Dusty formulations usually contain 5 to 20 wt .-% of active ingredient, verprprühbare solutions about 2 to 20 wt .-%. In the case of granules, the active substance content depends, in part, on whether the active compound is liquid or solid and which granulation aids, fillers, etc. are used.

In addition, the active substance formulations mentioned optionally contain the usual adhesion, wetting, dispersing, emulsifying, penetrating, solvent, filling or excipients.

For use, the commercially available concentrates are optionally diluted in a conventional manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and sometimes also for microgranules by means of water. Dusty and granulated preparations and sprayable solutions are usually no longer diluted with other inert substances before use.

With the external conditions such as temperature, humidity and the like. the required application rate varies. It can vary within wide limits, e.g. between 0.005 and 10.0 kg / ha or more of active substance, preferably it is

. ". 273 4 3 «

however between 0.01 and 5 kg / ha.

Also mixtures odor mixed formulations with other agents, such. B, insecticides, acaricides, herbicides, fertilizers, growth regulators or fungicides may be possible.

The invention is further illustrated by the following examples.

embodiments

- Formulation case

A. A dusting agent is obtained by mixing 10 parts by weight of active compound and 90 parts by weight of talc or inert substance and comminuting in a hammer mill.

B. A wettable powder readily dispersible in water is obtained by mixing 25 parts by weight of active ingredient, 64 parts by weight of kaolin-containing quartz of inert, 10 parts by weight of potassium lignosulfonate and 1 part by weight of oleoylmethyltaurine sodium as a wetting and dispersing agent and grinding in a pin mill.

G. A dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of active compound with 6 parts by weight of alkylphenol polyglycol ether (Triton χ 207), 3 parts by weight of isotridecanol polyglycol ether (8 AeO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to 377 ^° C.) and ground in a ball mill to a fineness of less than 5 microns.

D. An emulsifiable concentrate is obtained from 15 parts by weight of active compound, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol (10AeO) as emulsifier.

Preparation Examples A. Precursors Compound 1

N- (4-chloro-3-hydroxymethyl) phenyl-4 / 5,6,7-tetrahydroisoindolin-1,3-dione

A solution of 26.0 g (0.17 mol) of 4-chloro-3-hydroxymethylaniline and 30.4 g (0.20 mol) of 3,4,5,6-tetrahydrophthalic anhydride in 100 ml of glacial acetic acid was refluxed for 5 hours , After addition of 100 ml of water, the reaction mixture was kept for 2 hours at 6O ⁰ C and sucked off after cooling the solid. This gave 22.5 g (46% of theory) of N- (4-chloro-3-hydroxymethyl) phenyl-4,5,6,7-tetrahydrolsoindolin-l, 3-dione of mp 125-127 ⁰ C.

Connection 2

N- (2,4-dichloro-5-hydroxymethyl) phenyl-4,5,6,7-tetrahydroisoindolin-1,3-dione

A solution of 50 g (0.26 mol) of 2,4-dichloro-5-hydroxymethyl-aniline, 49.5 g (0.33 mol) of 3,4,5,6-tetrahydrophthalic anhydride and 1.0 g of p Toluenesulfonic acid in 350 ml of o-dichlorobenzene for 2 hours under reflux. After concentration in vacuo, the residue was recrystallized from ethanol / isopropyl ether / hexane (3/3/6). Yield: 62.6 g (74% of theory) of mp 168-17O ⁰ C.

Connection 3

N- (4-chloro-2-fluoro-5-hydroxymethyl) phenyl-4,5,6,7-tetrahydroieoindolin-1,3-dione

2 7 3 4 3 rf

35 g (0.20 mol) of 4-chloro-2-fluoro-5-hydroxymethyl-aniline and 35 g (0.23 mol) of 3,4,5,6-tetrahydrophthalic-boric anhydride were dissolved in 400 ml of toluene. After addition of 0.5 g of p-toluenesulfonic acid was heated at reflux for 9 hours on a water. It was concentrated in vacuo and the product crystallized by stirring the residue in isopropyl ether. There were 37.6 g (61% of theory) of N- (4-chloro-2-fluoro-5-hydroxymethyl) phenyl-4,5,6,7-tetrahydroisoindolin-l, 3-dione of mp. 161-163 ⁰ C won.

B. end products Example 1

N-ethyl- [2-chloro-5- (4,5,6 _/ 7-tetrahydro-boindolin-l _/ 3-dion-2-yl)] benzylcarbamate

4.5 g (0.015 mol) of N- (4-chloro-3-hydroxymethyl) -phenyl-4,5,6,7-tetrahydroisoindoline-1,3-dione (see Compound 1) were dissolved in 25 ml of acetonitrile and At room temperature with 2.4 ml (0.030 mol) of ethyl isocyanate. After addition of 1 drop of triethylamine was heated θ hours at 60 ⁰ C, concentrated and the residue is stirred in IBopropylether from. This gave 3.5 g (65% of theory) of N-ethyl [2-chloro-O- (4,5,6,7-tetrahydroieoindoline-1,3-dione-2-yl)] - benzylcarbamate from M.p. 67-69 ⁰ C.

Example 2

N- [4-chloro-2-fluoro-5- (methoxy-methoxy) methyl] phenyl-4,5,6,7-tetrahydrolsoindolin-l, 3-dione

3.1 g (0.01 mol) of N- (4-chloro-2-fluoro-5-hydroxymethyl) -phenyl-4,5,6,7-tetrahydroisoindoline-1,3-dione (8th compound 3) dissolved in 30 ml of dimethoxymethane and portionwise

with 3 g Phoephorpentoxid and 0.1 g of lithium bromide added. After five hours of stirring at room temperature, the reaction mixture was poured into 60 ml of saturated sodium bicarbonate solution and extracted with 2 × 50 ml of diethyl ether. The combined organic extracts were dried over sodium sulfate and concentrated in a water-jet vacuum. There remained 2.9 g (82%) of N- [4-chloro-2-, fluoro-5- (methoxy-methoxy) -methyl] -phenyl-4 _/ 5,6 _/ 7-tetrahydroisoindoline-1,3-dione back as a resin.

In an analogous manner, the following compounds of formula I are prepared:

Table 1

0X

Ex. No. X

Mp. \ ° C]

Cl Cl CH ₃ OH

Cl

Cl

0-Cj-CH ₃

63/65

Cl

Cl

F ₃ 65/66

NO ₂ Cl

Cl

Cl

OCNHCH,

141/43

14

Continued table

Ex. No. X Schrcp. f ° C

Cl Cl H OC ¹ CHoCl

oil

Cl Cl H OCO-C ₆ H ₅

oil

Cl Cl H OCC ₂ H ₅

Cl Cl H OSO ₂ CH ₃

Oil 122/24

Cl Cl OH 0-CCH ₁

12 Cl Cl H O 0 -CCF ₃ oil O 13 Cl Cl H 0-CCCl ₃ 110/12 14 Cl Cl H OCH ₂ Cl oil O 15 Cl Cl H OCCH ₂ OCH ₃ oil 16 c :. Cl OCH ₃ OCH ₃ oil 17 Cl Cl H OCHoOCHo 61/63

19

Cl Cl OH

Cl Cl H

219/21

180/82

273 * 3 "

Continued table

Example No. XYR ^J

Mp. [ ⁰ CT

Il

Cl Cl H OCNH-CH (CH ₃ ) 2 152/53 Cl Cl H OcWc ₂ H ₅

H Cl C ₂ H ₅ OH 158/59

Cl Cl H

CH (CH ₃ ) ₂ 164/66

24 Cl Cl H

H Cl H

O

.11 ··

ÖCNHS

Cl 0

OCC ₂ H ₅

92/94

oil

Il

Cl Cl to OC-cyclo-C ₃ H ₅

92/94

Cl H

OCNH-CH,

Cl

CH ₃ OH79 / ei

H Cl

CH ₃ OCNHC ₂ K ₅

Cl Cl H OCNHCH ₂ CH ₂ CH ₃ 101/03 Cl Cl H OC-C (CH ₃ ) 3

oil

714

16

Continued table

Example No. XY R ^J Mpp. [ ⁰ Ci

Cl Cl H OC-Cyclu-C ₄ H ₇

oil

Il

Cl Cl H OC-CyClO-C ₆ H ₁₁

oil

O

34 Cl Cl H OCNH ^ (OCH ₃ ) 134/36

35 F Cl H OCNHC ₂ H ₅ 36 F Cl H OCH ₂ SCH ₃ 37 H Cl H OCh ₂ OCH ₃ 38 H Cl H OO OCNHi (OC ₂ Hg) ₂

93/100

52/53

66/68

H Cl H OC-CyClO-C ₃ H ₅

oil

H Cl H OC-CyClO-C ₆ H ₁₁ 57/59

41 H

Cl H 0 (5-C (CH ₃ ) .60 / 62

F Cl

H OC oil

H Cl H OCNHP (OCH ₃ ) ₂ 183/85

17 273

Continued Table Ex. No. X m.p. f ° Cl

44 45 46 47 48 49 50 51

52 53 5 "55 56 57

Cl

H Cl H

OCNHSO

Cl Cl H COOH

Cl Cl H COOC ₂ H ₅

Cl Cl H CONH-nC ₄ H ₉ Cl Cl H COOCH ₂ CF ₂ CHF ₂

Cl Cl H COOCH,

Cl Cl H COO-CaH

₆ H ₅

Cl Cl H

CH, i ³ N

Cl Cl H CONH-CH ₂ -C ₆ H ₅ Cl Cl H CON (CH ₃ ) ₂

Cl Cl H C00CH ₂ C «CH

Cl Cl H CONHCH

Cl Cl H COO-CH-COOC ₂ H ₅

CHo 163/65

216/18

80/82

216/19

81/83

84/85

176/80

wax

Cl Cl H CONH-CH-C-OC ₂ H ₅ 181/83

226/28 141/44 110/12 225/26 Wax

58

Cl Cl H COONa 147/50

16

4 3

Continued table

Ex. No. XY R ^J

59Cl Cl H CON

CH ₉ CN

60 Cl Cl H COOCH ₂ CH = CH ₂

Mp. [ ⁰ Ci

193/96

guard

62

64

Cl Cl H CSC ₂ H ₅

66 H 67 F 68 F 69 F 70 F

wax

Cl Cl H CS-CH ₂ COOC ₂ H ₅ wax

wax

Cl Cl H CS-CH ₂ CH = CH ₂

O Cl Cl Cl H OCNHP (OC ₂ H ₅ J ₂ 107/09

Ο O Ο Η F Cl H OCNHP (OCH ₃ ) ₂ 126/28

Cl H OCNH-CH (CH ₃ ) ₂

Cl H COOH

O Cl H OCNHCH

Cl H COONa

Cl H COOCH ₂ CH ₂ OCH ₃

92/94 182/84

65/68 82/84 60/62

7.1 4 3

Continuation Table 1

Example no. X Y R * Z Mp. ° C | 71 F Cl H CONHCH ₂ CH ₂ OCh ₃ 162/64 12 F Cl H COOCH ₃ 101/03 S 73 Cl Cl H 0-CNH- (CH ₂ J ₃ CH ₃ 163/65 74 F Cl H 0-CH (CH ₃ ) -OCH ₃ 109/111 75 Cl Cl H UCH ₂ OC ₂ H ₅ wax 76 Cl Cl H 0-CH (CH ₃ ) -OCH ₃ guard 77 Cl Cl H 0 H C-ON = C (CH ₃ ) -COOC ₂ H ₅ wax 78 Cl Cl H OPH (CH ₃ J-OC ₂ H ₅ wax 79 Cl Cl H OCH ₃ 77-79 80 Cl Cl H D 0 wax 81 F Cl H OCH ₃ 79-81 82 F Cl H OCH ₂ OC ₂ H ₅ wax 83 F Cl OCH ₃ OCH ₃ wax 84 F Cl H OCH (CH ₃ ) OC ₂ H ₅ wax 85 Cl Cl H OCoHr wax

20

73 4 3

Continued table

Ex. No. X mp f ° Cl

O Cl H OC-CaH

6 ⁿ 5

Cl H OC-CH (CH ₃ J ₂

0 Cl H OC-CH ·:

Cl Cl -O-CH ₉ CH 4 O-145/47 wax

Wax wax

90 91 92 93 94 95 96 97 98 99 100

F Cl H OCNH (CH ₂ J ₃ CHi

H Br H OCH wax

Br H OCH,

F BR H OCH ₂ OCH ₃ H Br CH ₃ OCH (CH ₃ ) OCH ₃

H BR OCH ₃ OCH ₃

FFH OCH ₂ OC ₂ H ₅

Cl H SCH-

F Cl CH ₃ SCH ₂ COOC ₂ H ₅

Cl Cl HN (CH ₃ ) ₂

F Cl H NHCH ₂ CONH ₂

21 Continuation Table 1

Example no . XYR ¹ Z mp.

101 II Cl CHg NHCH (CHg) CONHCH ₃

102 H Br SCH ₃ SCH ₃

103 Cl Br H NHCH ₃

104 H Cl H COOCH (CHg) -OC ₂ H ₅

105 H Cl CH ₃ COOCH ₂ OCH ₂ -C ₆ H ₅

106 H Cl H CONHCH ₂ -C ₆ H ₅

107 H Cl CHg CONH (CH ₂ J ₂ OCHg

108 Cl Cl CN CN

109 Cl Cl CH ₃ NH CH ₃ NH

110 F Cl C ₂ H ₅ NH C ₂ H ₅ NH

111 F Cl CH ₃ NH COOC ₂ H ₅

112 F Cl CH ₃ NHCOCH ₂ CH ₂ OCH ₃

113 F Cl C ₂ H ₅ NHCONH-CH ₂ CH ₂ OC ₂ H ₅

114 F Cl C ₂ H ₅ NH CSNHCH ₃

115 F Cl C ₂ H ₅ NH NHCWHCH ₃

116 F Cl CH ₃ NHCNHCH ₃

273430

Continuation Table 1 Example No. XYR ¹ Z Mpp. [ ⁰ Ci

117 F Cl CHo NHCNH-OCH ₁

3, ι J

118 F Cl CTI ₃ NHCNH- (CH ₂ ) ₂ CH ₃

113 F Cl CH ₃ NHCNHCH (CH ₃ ) 2

120 F CI CN CN

121 F Cl OH CH ₃ 122 F Cl OH

123 F Cl OH SCH ₃ 124 F Cl OH CH ₂ CH ₂ OCH ₃ 125 F Cl OH CH ₂ COOCH ₂ -C ₆ H ₅ 126 H Br OH OC ₂ H ₅ 127 H Br OH SCCl ₃

128 H BrOH OH

129 FFH OCH ₃

130 FFH OCH ₂ OCH ₃

131 FFH OCH (CH ₃ ) OCH ₃

Continuation Table 1 Example No. XYR ¹ Z Mp. F ° Ci

132 FFH OCH ₂ CH ₂ SCH ₃

133 FFH OCH ₂ CH ₂ N (CH ₃ ) ₂

134 FFH COOCH ₂ CH ₂ OCH ₃

135 FFH COOCH ₂ CH ₂ OS1 (CH ₃ ) 3

136 FFH CONHCH ₃

137 FFH CONH (CH ₂ ) ₂ 0CH ₃

138 FF CH ₃ CONH (CH ₂ ) ₂ C (OCH ₃ ) 2

139 FF CH ₃ CSNHCH ₂ CH (CH ₃ ) 2

140 FF CH ₃ OCH ₂ CH ₂ "

Γ1

141 FF CH ₃

142 H CL H CONHCH ₂ -O) V ^Cl

143 H Cl CH ₃ CONHCH ₂

144 H Cl C ₂ H ₅ CONH-CH ₂

145 HF CoHc COOCHo / Γ lV- ^0CH

24

Continued table

Example No. X m.p. [ ⁰ C i

147

148

HFC ₂ H ₅

Cl Cl H

Cl Cl H

0-CH

Il "II

149 150 151 152 153

Cl Cl H

Cl H

Cl H

0-CH

OCH ₂ CH ₂ CNOCH ₂ CH ₂ CH ₂ -NO ₂

F Cl CH ₃ OCi ₁₂ CH ₂ Cl F Cl CH ₃ O (CH ₂ ) ₃ CH ₂ Br

154 155 156

F Cl CH ₃ OCH ₂ CH ₂ SS-CH ₃

H Cl H

H Cl HOCH (CH ₃ ) -CH ₂ Cl OCH (CHg) -COOC ₂ H ₅

157 158

Cl H

Cl HOCNHCH ₂ CN! NHCH (CH ₃ ) CN

273

Continuation Table 1

Ex. No. XYR ^J Schtnp

159 H Cl H S-CNH (CH ₂ J ₄ CH ₃

160 H Cl H OCH ₂ OCH ₂

Cl

161 H 162 F 163 F 164 F

Cl SCH ₃ COOCH ₃

Cl SCH ₃ SCH ₃

Cl H C00CH, -S-

Cl -S-CH ₂ -CH ₂ -S-

loUUUUo

165 H Cl H

166

F Cl H F

O-CH

167 Cl Cl H O-CH

26 Continuation Tab. 1

Example No. XYR ¹ Z m.p. [ ⁰ Cl

H Br CH ₃ O-CH

169 H Cl H C-CH ₂ OI ₂ -S-OI ₂

170 H Cl H C

CH

171 F Cl H C

CH ₂ -COOC ₂ H ₅

172 F Cl CH ₃ OCH ₂ OI = OI ₂

173 F Cl CH ₃ OCH ₂ CECH

174 F Cl H OCH ₂ CHCl-CH ₂ Cl

175 F Cl NHCH ₃ NHCH ₂ OI = OI ₂

176 F Cl CH ₃ OCH ₂ OI ₂ -O

177 F Cl H 0 -CH ₉ -OI,

CH ₂

178 F Br SCH ₃ C-SCH ₂ COOOI ₃

179 F Br S (CH ₂ ) ₃ CH ₃ S (CH ₂ J ₃ OI ₃

180 FJH 00I ₃

27

Continuation Table 273

36

Ex. No. X

R ^J mp. F ° Ci

H Br H O DCNHCoH

2 ⁿ 5

88-90

182

H Cl H

OCH-88-90

183 184 185

Cl H

OCNHCH (CH ₃ ) ₂

H Cl OCH ₃ OCH ₃

OH

116-118

87-89 128-130

186 187 188 189 190 191

Cl

F H F H br H Cl H br H br H

OCNHC ₂ H ₅ 99-101

OCKo 75-77

COOH 206-208

COOCH ₂ CH = CH-C ₂ F ₅ 59-61

COOCH ₂ C = CH 108-110

COOCH-COOC ₂ H ₅ wax CHo

192

Br H CONHCH ₂ Ch ₂ OCH ₃

197-199

193

Br H COOCH-NHCCH (CH ₃ ) ₂ CCIo

196-198

194

Br H CONH-CH-COOC ₂ H ₅

111-113

Continued Tf.belle 1

Example No. XYR ^J

Schmp. [ ⁰ Cl

195 H Br H CH ₂ OCH ₂ OCH ₃

66-68

196

H Br H

CH ₂ OCNHCH ₃

wax

197

H Br H CH ₂ OCCH ₃

resin

27343 *

29 Biological examples

Damage to weed plants or crop plant compatibility was scored according to a key in which the effectiveness is expressed by values of 0-5. Where:

0 = no effect or damage

1 = 0 - 20% effect or damage 2 = 20 - 40% effect or damage

3 = 40 - 60% effect or damage

4 = 60 - 80% effect or damage

5 = 80 - 100% effect or damage

1. weed effect in pre-emergence

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were placed in sandy loam soil in plastic pots (diameter: 9 cm) and covered with soil. The compounds according to the invention formulated in the form of wettable powders or emulsion concentrates were then applied to the surface of the cover soil as aqueous suspensions or emulsions having a water application rate of 600 to 800 l / ha in different dosages.

After the treatment, the pots were placed in the greenhouse and kept under good growth conditions for the weeds (temperature: 23 plus / minus 2 degrees Celsius, relative humidity: 60-80 ⁰ C).

The visual assessment of the plant or the impact damage occurred after the emergence of the test plants after a test period of 3-4 weeks compared to untreated controls. Like the rating values in table

2 73 4 3 *

show, the compounds of the invention have a good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds.

2. weed effect postemergence

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in sandy loam soil in plastic pots (diameter = 9 cm), covered with soil and grown in the greenhouse under good growth conditions. Three weeks after sowing, the test plants were treated at the trefoil stage.

The compounds of the invention formulated as wettable powders or as emulsion concentrates were sprayed onto the green parts of the plant in different dosages with a conversion rate of 600-800 l / ha and after about 3-4 weeks the test plants were left in the greenhouse under optimum growth conditions (temperature: 23 plus / min s 2 degrees Celsisus, relative humidity 60-80%) the effect of the preparations optically scored compared to untreated controls.

The compositions according to the invention also have good herbicidal activity against post-emergence against a broad spectrum of economically important weeds and weeds (Table 2).

3. crop compatibility

In further experiments in the greenhouse, seeds of a larger number of crops and weeds were laid in sandy loam soil and covered with soil.

31

714

One part of the pots was immediately treated as described under 1, the rest being set up in the greenhouse until the plants had developed two to three true leaves and then sprayed with the substances according to the invention in different dosages as described under 2.

Four to five weeks after application and service life in the greenhouse it was found by optical assessment that the compounds according to the invention have two-leaved cultures, e.g. Soy, cotton, oilseed rape, sugar beets and potatoes pre-emergence and post-emergence even with high doses of active ingredient undamaged. In addition, some substances also protect graminaceous crops such as e.g. Barley, wheat, rye, sorghum millet, corn or rice. The compounds of the formula I thus have a high selectivity when used for controlling undesired plant growth in agricultural crops.

Table 2: Pre-emergence effect of the invention

links

Ex. dose SIA herbicidal effect ECG No. kg a.i./ha 5 CRS STM 5 6 2.5 4 5 2 5 16 2.5 3 5 2 5 27 2.5 3 5 5 5 1 2.5 5 5 5 4 35 2.5 5 5 5 5 2 2.5 4 5 5 5 37 2.5 2 5 5 3 38 2.5 4 5 2 5 41 2.5 5 5 5 5 42 2.5 5 5 5 5 65 2.5 5 5 5 5 66 2.5 5 5

27343 (5

Continuation Table 2

Ex. dose SIA herbicidal effect ECG No. kg a.i./ha 3 CRS STM 3 67 2.5 5 4 3 5 68 2.5 5 5 5 4 69 2.5 2 5 2 2 70 2.5 5 5 2 5 74 2.5 3 5 5 5 75 2.5 4 5 3 5 76 2.5 5 5 2 5 78 2.5 5 5 2 4 79 2.5 5 5 2 5 80 2.5 5 5 2 5 81 2.5 5 5 5 5 82 2.5 5 5 5 5 83 2.5 5 5 5 5 64 2.5 5 5 5 3 85 2.5 5 5 2 4 87 2.5 5 * ^ tä 5 5 88 2.5 3 5 4 3 86 2.5 4 5 2 4 72 2.5 5 5 4 5 89 2.5 5 5 5 5 90 2.5 4 5 5 5 181 2.5 5 5 5 5 93 2.5 3 5 5 3 91 2.5 3 4 4 3 182 2.5 5 4 4 4 183 2.5 2 5 5 4 184 2.5 4 5 5 3 185 2.5 5 5 2 5 130 2.5 5 5 5 5 186 2.5 3 5 4 4 187 2.5 4 5 2 3 129 2.5 2 5 2 2 196 2.5 5 3

33 27343c *

Abbreviations:

SIA = Sinapis alba, CRS = Chrysanthemum segetum, STM = Stellaria media, ECG = Echinochloa crus-galli, a.i. = active substance

Table 3: Post-emergence effect of the compounds according to the invention

Ex. dose SIA herbicidal effect ECG No. kg a.i./ha 5 CRS STM 2 6 2.5 5 3 4 4 16 2.5 4 5 2 3 27 2.5 4 4 4 4 1 2.5 5 5 5 5 35 2.5 5 5 5 5 2 2.5 5 5 5 3 37 2.5 5 4 5 3 38 2.5 4 5 5 3 41 2.5 5 5 4 4 42 2.5 5 5 5 4 65 2.5 5 5 4 4 66 2.5 5 5 4 3 67 2.5 5 5 3 5 68 2.5 5 5 5 2 69 2.5 5 5 4 4 70 2.5 5 5 3 5 74 2.5 5 5 5 3 75 2.5 5 5 3 5 76 2.5 5 5 4 5 78 2.5 5 5 4 4 79 2.5 5 5 4 4 80 2.5 5 5 3 5 81 2.5 5 5 5 5 82 2.5 5 5 5 5 83 2.5 5 5 5 5 84 2.5 5 5 5 4 85 2.5 4 3

Ex. dose SIA herbicidal effect ECG No. kg a.i./ha 5 CRS STM 4 87 2.5 5 5 5 5 88 2.5 5 5 5 4 86 2.5 5 5 4 5 72 2.5 5 5 5 5 89 2.5 5 5 5 5 90 2.5 5 5 5 4 181 2.5 5 5 5 5 93 2.5 5 5 5 3 91 2.5 5 5 5 3 182 2.5 5 5 5 5 183 2.5 5 5 5 3 184 2.5 5 5 5 4 185 2.5 5 4 4 5 130 2.5 5 5 5 5 186 2.5 4 5 4 2 187 2.5 4 3 2 2 188 2.5 5 4 4 5 129 2.5 5 5 4 3 195 2.5 4 5 4 2 189 2.5 5 5 2 4 190 2.5 5 5 3 4 191 2.5 5 5 4 4 196 2.5 5 5 3 4 197 2.5 3 5 4 3 192 2.5 3 2

Abbreviations as in Table 2.

Claims (5)

2 73 i 3d claims 1. A process for the preparation of substituted tetrahydrophthalimides of the formula I or their Salae, (D worm X κ is hydrogen or halogen, Y = halogen 0 W W 0 9 19 H 9 * P I '1 P I' P Z = -WR, -NR ¹ R, -C-OR, -C-SR, -CNR ¹ R, -WCR, 0, -CSN, - ^ HC-ITR ¹ R ³ , -CH ₉ VZR ² or V ^ R = H or R ¹ = hydrogen, hydroxy, (C ₁ -C.) - alkyl, (C ₁ -Cj- (Cj-Cj-alkylthio, amino, (C ₁ -C.) - alkylamino, (C ₁ -C). - Dialkylamino or cyano, or R and Z together represent a radical -W-CH ₂ -CHp-W-, R ² = Y / aoserstoff, (Cj-Cj-alkyl, (C ₃ -C) -alkenyl, (C ₂ -C.) - alkynyl, wherein the alkyl, alkenyl or alkynyl radical in each case by (C ₀ - C ₇ ) -cycloalkyl, halogen, (CpC) -alkoxy, (C ₁ -C 4) -alkylthio, di- (C ₁ -C -alkyl ₎ -amino, cyano, nitro, phenyl, TrI- (C ₁ - C.sub.-alkyl) silyl, benzyloxy or may be substituted by a four-bia seven-membered saturated or unsaturated heterocycle containing one to three nitrogen, oxygen or sulfur atoms; (Cj-C ₇₎ cycloalkyl; unsubstituted or substituted by halogen, cyano, (C ₁ -C.) Alkyl, (C ₁ -C .) -Alkoxy or by phenoxy, which may be substituted by CF ~, halogen or (C ₁ -C.) - Alkyl subatituted Pheiyl; a remainder of the formulas R ³ WR ³ WR ³ R ³ (C) _n -C-WR ³ , - (C) _n -C -NR ¹ R ³ , - (C) _n -W- (C) -WR ³ , »1» 1 M »1 R ¹ R ¹ R ¹ R ¹ R ³ R ³ OO 0 0 - (C) -W- (C) -NR ¹ R ^3, -C-NR ¹ -SR ^{3, n} P Ii R ¹ R ¹ O O -S (O) OR ³ or -P (R _^3)? . I ' -.57 · 27343 (5 R = Hydrogen, (CpC J-Al-yl, (G -C ₇ ) -cycloalkyl, (alkenyl, (C ₂ -C)) alkynyl or phenyl, which by halogen, cyano, (Cj-C.) - Alkyl or (C 1 -C 4) -alkoxy may be substituted, η = 0, 1 or 2 ρ = 1 or 2 and W = oxygen or sulfur mean, characterized in that a) a compound of formula II with a compound of formula III II CH-Z or b) an isocyanate of formula (IV) with a compound of formula II O = C = N IV or CH-Z ♦ 1 E ¹ - 38- c) a compound of the formula (V) 0X wherein A = a radical of the formulas -GHO, -GHR-Hal (Hal = Cl or Br), -GHR ¹ -OH or CHR ¹ -COOR ³ means in a conventional manner to the compounds of formula I derivatized us under A. ) to c) optionally converted iri their salts. 2. The method according to claim 1, characterized in that compounds of the formula I of claim 1 or salts thereof are prepared v / orin X = H, F or Eq Y = F, GI or Br 0
Z ~ V / R ² , -V / CR ² or -0-JL _n J , in particular V / R ² , R ¹ = H, (Cj-C ₄ ) alkyl or R ² = H, (C ₁ -C ₄ ) -alkyl, (C ₃ - these radicals being alkoxy, (λ ^ "^ λ) 'alkylthio or halogen may be substituted by (C.-C ₄₎ or a radical of the formulas R ³ WR ³ V / R ⁵ R ³ Il It - (G) -C-WR ³ , - (G) -G-NR ¹ R ³ , - (C) _n -W- (G) -WR ³ , 'η' ^v 'η »1 M MM R ¹ R ¹ R ¹ R ¹ R ^J = H, (C ₁ -C ₄ ) -alkyl or phenyl η = 0, 1 or 2 ρ = 1 or 2 and V / = 0 or S. 3. A herbicidal composition, characterized in that they contain an effective amount of a compound of formula I of claims 1 or 2 or their salts in addition to conventional excipients and carriers. 4. Use of compounds of the formula I of claims 1 or 2 or salts thereof characterized in that they are used as herbicides. 5. A method for controlling unwanted plants, characterized in that applied to these or the effective areas an effective amount of a compound of formula I of claims 1 and 2 or their salts.