N-phenyltetrahydrophthalimide compounds

Abstract

N-phenyltetrahydrophthalimides of the formula I ##STR1## where R.sup.1 is hydrogen or halogen, R.sup.2 is halogen and A is a substituent of the formula ##STR2## where X is oxygen or sulfur, n is zero or one, R.sup.3 is hydrogen or C.sub.1 -C.sub.6 -alkoxycarbonyl or C.sub.1 -14 C.sub.3 -alkyl which is unsubstituted or substituted by halogen, cyano, hydroxyl, mercapto, C.sub.1 -C.sub.6 -alkoxycarbonyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.3 -C.sub.6 -alkenyloxy, C.sub.3 -C.sub.6 -alkenylthio, C.sub.3 -C.sub.6 -alkynyloxy, C.sub.3 -C.sub.6 -alkynylthio or C.sub.1 -C.sub.4 -acyloxy, or is hydroxyl or carboxyl or is C.sub.1 -C.sub.4 -alkylthio-C.sub.1 - or C.sub.2 -alkyl or C.sub.1 -C.sub.4 -alkoxy-C.sub.1 - or -C.sub.2 -alkyl which is substituted in the alkyl ether or thioehter moiety by C.sub.1 -C.sub.6 -alkoxycarbonyl, R.sup.4 is hydrogen or C.sub.1 -C.sub.3 -alkyl, Z is methyleneoxymethylene, methylenethiomethylene or ethenylene (--CH.dbd.CH--) and R.sup.5 and R.sup.6 are each hydrogen or C.sub.1 -C.sub.3 -alkyl, which are useful as herbicides, are prepared.

Description

N-aryl-substituted tetrahydrophthalimides having a herbicidal action are known. For example, European Patent 207,894 describes tetrahydrophthalimides of the formula I' ##STR3## where the radicals have, for example, the following meanings: R.sup.a and R.sup.b are identical or different and each denotes hydrogen or a halogen atom;

R.sup.c and R.sup.d together denote a substituted or unsubstituted C.sub.2 -C.sub.3 -alkylene bridge, and R.sup.e denotes, inter alia, hydrogen, cyano or C.sub.1 -C.sub.4 -alkyl.

However, the action of these compounds at low application rates is unsatisfactory.

The object of the invention was therefore, to provide N-phenyltetrahydrophthalimide compounds which have, at low application rates, a better herbicidal action on unwanted plants without damaging crop plants.

This object is achieved by tetrahydrophthalimides of the formula I ##STR4## where R.sup.1 is hydrogen or halogen, R.sup.2 is halogen and A is a substituent of the formula ##STR5## where X is oxygen or sulfur, n is zero or one, R.sup.3 is hydrogen or C.sub.1 -C.sub.6 -alkoxycarbonyl or C.sub.1 -C.sub.3 -alkyl which is unsubstituted or substituted by halogen, cyano, hydroxyl, mercapto, C.sub.1 -C.sub.6 -alkoxycarbonyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.3 -C.sub.6 -alkenyloxy, C.sub.3 -C.sub.6 -alkenylthio, C.sub.3 -C.sub.6 -alkynyloxy, C.sub.3 -C.sub.6 -alkynylthio or C.sub.1 -C.sub.4 -acyloxy, or is hydroxyl or carboxyl or is C.sub.1 -C.sub.4 -alkylthio-C.sub.1 - or -C.sub.2 -alkyl or C.sub.1 -C.sub.4 -alkoxy-C.sub.1 - or -C.sub.2 -alkyl which is substituted in the alkyl ether or thioether moiety by C.sub.1 -C.sub.6 -alkoxycarbonyl, R.sup.4 is hydrogen or C.sub.1 -C.sub.3 -alkyl, Z is methyleneoxymethylene, methylenethiomethylene or ethenylene (--CH.dbd.CH--) and R.sup.5 and R.sup.6 are each hydrogen or C.sub.1 -C.sub.3 -alkyl, have an advantageous herbicidal action, particularly in the postemergence method, and are selective with respect to a number of crops.

Halogen as used above is fluorine, chlorine or bromine, and halogen radicals R.sup.1 are preferably fluorine and halogen radicals R.sup.2 are preferably chlorine.

Alkyl (alone or as part of a substituent) includes branched or straight-chain radicals, e.g. methyl or ethyl, n-propyl and isopropyl.

Alkenyl and alkynyl may likewise be branched or straight-chain. Examples of alkenyl radicals in the formula I are allyl, 2-butenyl, 3-butenyl, 2-isobutenyl, 2-pentenyl, 3-pentenyl and 4-pentenyl, in particular allyl or 2-butenyl, alkynyl is, as a rule, propargyl, 2-butynyl, 3-butynyl or isomeric pentynyl radicals; however, alkynyl is preferably propargyl or 2- or 3-butynyl.

As a substituent of the general formula I, alkoxy is methoxy, ethoxy, n-propoxy, isopropoxy and the four isomeric butoxy radicals, in particular methoxy, ethoxy or isopropoxy. Examples of alkylthio in the formula I are n-propylthio, isopropylthio and n-butylthio, and in particular methylthio and ethylthio.

In the case of substitution in the thioacetal moiety, the formula I embraces enantiomers, diastereomers and their mixtures.

The compounds of the formula I can be considered as N-substituted tetrahydrophthalimides; accordingly, they are obtainable from 3,4,5,6-tetrahydrophthalic anhydride and an aniline of the formula V, for example in a solvent, at from 0.degree. to 150.degree. C., preferably from 20.degree. to 100.degree. C. Examples of suitable solvents are lower alkanoic acids, such as glacial acetic acid and propionic acid, and aprotic solvents, such as toluene and xylene, in the presence of acidic catalysts, such as aromatic sulfonic acids.

Preferred compounds I are those in which R.sup.1 is hydrogen or fluorine, R.sup.2 is chlorine and A is dithiane, dithiolane, oxathiolane or their substituted analogs.

The anilines of the formula V can be obtained, for example, by reducing an appropriately substituted nitrobenzene IV with a reducing agent, such as iron or a tin(II) salt. ##STR6##

The reduction can also be carried out in the form of catalytic hydrogenation over a metal catalyst, such as platinum, palladium or Raney nickel, under relatively mild conditions.

The nitrobenzenes IV are obtainable by reacting a benzaldehyde II in a solvent with a dithiol or mercaptoalkanol of the formula IIIa or IIIb in the presence of an acid. ##STR7##

The recommended procedures given in the Examples below were used with appropriate modification of the starting compounds to obtain further compounds of the general formula I. The compounds are listed together with physical data in the Tables below. Compounds without such data can be obtained from corresponding substances in a similar manner. Because of their close structural relationship with the compounds prepared and investigated, they are expected to have a similar action.

EXAMPLE ##STR8## a) 9.9 g of ethane-1,2-dithiol are added to 18.6 g of 2-chloro-5-nitrobenzaldehyde and 0.5 g of p-toluenesulfonic acid in 250 ml of toluene, and the mixture is refluxed for 5 hours under a water separator. After the mixture has cooled, the solvent is removed, the residue is stirred with petroleum ether and the product is filtered off and dried. 25.5 g of 4-chloro-3-(1,3-dithiolan-2-yl)-nitrobenzene (mp. 130.degree.-131.degree. C.) are obtained.

b) 24.9 g of the above nitro compound are added a little at a time to a mixture of 15.9 g of iron powder in 50 ml of methanol and 75 ml of glacial acetic acid under reflux, and refluxing is continued for 2 hours. After the mixture has cooled, 250 ml of water are added and the solid is filtered off. The filtrate is extracted with 3 times 100 ml of ethyl acetate, the extracts are dried and evaporated down and the product is precipitated from petroleum ether, filtered off under suction and dried. 21.5 g of 4-chloro-3-(1,3-dithiolan-2-yl)-aniline (mp. 60.degree.-63.degree. C.) are obtained. c) 11.6 g of the above aniline and 7.6 g of cyclohexene-1,2-dicarboxylic anhydride in 150 ml of glacial acetic acid are stirred for 2 days at room temperature, and the precipitate which separates out is filtered off, washed with water and petroleum ether and dried. 13 g of N-[4-chlorophenyl-3-(1,3-dithiolan-2-yl)]-3,4,5,6-tetrahydrophthalimide (mp. 155.degree.-158.degree. C.) (Table 1 No. 1.001) are obtained.

Other examples of active ingredients which can be synthesized using this principle are shown in Tables 1 to 5.

TABLE 1______________________________________ ##STR9##No. R.sup.1 R.sup.3 R.sup.4 n X mp. [.degree.C.]______________________________________1.001 H H H 0 S 155-1581.002 F H H 0 S 160-1611.003 H 4-CH.sub.3 H 0 S 101-1021.004 F 4-CH.sub.3 H 0 S 138-1391.005 H 4-CH.sub.2 CH.sub.3 H 0 S1.006 F 4-CH.sub.2 CH.sub.3 H 0 S1.007 H 4-(CH.sub.2).sub.2 CH.sub.3 H 0 S1.008 F 4-(CH.sub.2).sub.2 CH.sub.3 H 0 S1.009 H 4-CH(CH.sub.3).sub.2 H 0 S1.010 F 4-CH(CH.sub.3).sub.2 H 0 S1.011 H 4-CH.sub.2 Cl H 0 S 109-1101.012 F 4-CH.sub.2 Cl H 0 S1.013 H 4-CH.sub.2 Br H 0 S1.014 F 4-CH.sub.2 Br H 0 S1.015 H 4-CH.sub.2 CN H 0 S 82-841.016 F 4-CH.sub.2 CN H 0 S1.017 H 4-CH.sub.2 OH H 0 S 88-901.018 F 4-CH.sub.2 OH H 0 S1.019 H 4-CH.sub.2 SH H 0 S 96-971.020 F 4-CH.sub.2 SH H 0 S1.021 H 4-CH.sub.2 COOCH.sub.3 H 0 S1.022 F 4-CH.sub.2 COOCH.sub.3 H 0 S1.023 H 4-CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 S1.024 F 4-CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 S1.025 H 4-CH.sub.2 OCH.sub.3 H 0 S1.026 F 4-CH.sub.2 OCH.sub.3 H 0 S1.027 H 4-CH.sub.2 OCH.sub.2 CH.sub.3 H 0 S1.028 F 4-CH.sub.2 OCH.sub.2 CH.sub.3 H 0 S1.029 H 4-CH.sub.2 SCH.sub.3 H 0 S oil1.030 F 4-CH.sub.2 SCH.sub.3 H 0 S1.031 H 4-CH.sub.2 CH.sub.2 SCH.sub.3 H 0 S1.032 F 4-CH.sub.2 CH.sub.2 SCH.sub.3 H 0 S1.033 H 4-CH.sub.2 OCH.sub.2 CHCH.sub.2 H 0 S1.034 F 4-CH.sub.2 OCH.sub.2 CHCH.sub.2 H 0 S1.035 H 4-CH.sub.2 OCH.sub.2 CCH H 0 S1.036 F 4-CH.sub.2 OCH.sub.2 CCH H 0 S1.037 H 4-CH.sub.2 OCOCH.sub.3 H 0 S 80-811.038 F 4-CH.sub.2 OCOCH.sub.3 H 0 S1.039 H 4-CH.sub.2 OCOCH.sub.2 CH.sub.3 H 0 S1.040 F 4-CH.sub.2 OCOCH.sub.2 CH.sub.3 H 0 S1.041 H 4-CO.sub.2 CH.sub.3 H 0 S1.042 F 4-CO.sub.2 CH.sub.3 H 0 S1.043 H 4-CO.sub.2 CH.sub.2 CH.sub.3 H 0 S1.044 F 4-CO.sub.2 CH.sub.2 CH.sub.3 H 0 S1.045 H 4-COOH H 0 S1.046 F 4-COOH H 0 S1.047 H 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 H 0 S oil1.048 F 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 H 0 S1.049 H 4-CH.sub. 2 SCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 S1.050 F 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 S1.051 H 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.3 H 0 S1.052 F 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.3 H 0 S1.053 H 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 S1.054 F 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 S1.055 H 4-CH.sub.3 5-CH.sub.3 0 S1.056 F 4-CH.sub.3 5-CH.sub.3 0 S1.057 H 4-CH.sub.2 SCH.sub.2 CHCH.sub.2 H 0 S oil1.058 F 4-CH.sub.2 SCH.sub.2 CHCH.sub.2 H 0 S1.059 H 4-CH.sub.2 SCH.sub.2 CCH H 0 S oil1.060 F 4-CH.sub.2 SCH.sub.2 CCH H 0 S1.061 H 4-CH.sub.2 SCH(CH.sub.3)CO.sub.2 CH.sub.3 H 0 S oil1.062 F 4-CH.sub.2 SCH(CH.sub.3)CO.sub.2 CH.sub.3 H 0 S______________________________________ TABLE 2__________________________________________________________________________ ##STR10##No. R.sup.1 R.sup.3 R.sup.4 n X mp. [.degree.C.]__________________________________________________________________________2.001 H H H 0 O 141-1422.002 F H H 0 O2.003 H 4-CH.sub.3 H 0 O oil2.004 F 4-CH.sub.3 H 0 O oil2.005 H 4-CH.sub.2 CH.sub.3 H 0 O2.006 F 4-CH.sub.2 CH.sub.3 H 0 O2.007 H 4-(CH.sub.2).sub.2 CH.sub.3 H 0 O2.008 F 4-(CH.sub.2).sub.2 CH.sub.3 H 0 O2.009 H 4-CH(CH.sub.3).sub.2 H 0 O2.010 F 4-CH(CH.sub.3).sub.2 H 0 O2.011 H 4-CH.sub.2 Cl H 0 O2.012 F 4-CH.sub.2 Cl H 0 O2.013 H 4-CH.sub.2 Br H 0 O2.014 F 4-CH.sub.2 Br H 0 O2.015 H 4-CH.sub.2 CN H 0 O2.016 F 4-CH.sub.2 CN H 0 O2.017 H 4-CH.sub.2 OH H 0 O 91-932.018 F 4-CH.sub.2 OH H 0 O2.019 H 4-CH.sub.2 SH H 0 O2.020 F 4-CH.sub.2 SH H 0 O2.021 H 4-CH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.022 F 4-CH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.023 H 4-CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.024 F 4-CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.025 H 4-CH.sub.2 OCH.sub.3 H 0 O2.026 F 4-CH.sub.2 OCH.sub.3 H 0 O2.027 H 4-CH.sub.2 OCH.sub.2 CH.sub.3 H 0 O2.028 F 4-CH.sub.2 OCH.sub.2 CH.sub.3 H 0 O2.029 H 4-CH.sub.2 SCH.sub.3 H 0 O2.030 F 4-CH.sub.2 SCH.sub.3 H 0 O2.031 H 4-CH.sub.2 CH.sub.2 SCH.sub.3 H 0 O2.032 F 4-CH.sub.2 CH.sub.2 SCH.sub.3 H 0 O2.033 H 4-CH.sub.2 OCH.sub.2 CHCH.sub.2 H 0 O2.034 F 4-CH.sub.2 OCH.sub.2 CHCH.sub.2 H 0 O2.035 H 4-CH.sub.2 OCH.sub.2 CCH H 0 O2.036 F 4-CH.sub.2 OCH.sub.2 CCH H 0 O2.037 H 4-CH.sub.2 OCOCH.sub.3 H 0 O2.038 F 4-CH.sub.2 OCOCH.sub.3 H 0 O2.039 H 4-CH.sub.2 OCOCH.sub.2 CH.sub.3 H 0 O2.040 F 4-CH.sub.2 OCOCH.sub.2 CH.sub.3 H 0 O2.041 H 4-CO.sub.2 CH.sub.3 H 0 O2.042 F 4-CO.sub.2 CH.sub.3 H 0 O2.043 H 4-CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.044 F 4-CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.045 H 4-COOH H 0 O2.046 F 4-COOH H 0 O2.047 H 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.048 F 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.049 H 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.050 F 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.051 H 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.052 F 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.053 H 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.054 F 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.055 H 4-CH.sub.3 5-CH.sub.3 0 O2.056 F 4-CH.sub.3 5-CH.sub.3 0 O2.057 H H 5-CH.sub.3 0 O2.058 F H 5-CH.sub.3 0 O2.059 H H 5-CH.sub.2 CH.sub.3 0 O2.060 F H 5-CH.sub.2 CH.sub.3 0 O2.061 H H 5-(CH.sub.2).sub.2 CH.sub.3 0 O2.062 F H 5-(CH.sub.2).sub.2 CH.sub.3 0 O2.063 H H 5-CH(CH.sub.3).sub.2 0 O2.064 F H 5-CH(CH.sub.3).sub.2 0 O2.065 H 5-CH.sub.2 Cl H 0 O2.066 F 5-CH.sub.2 Cl H 0 O2.067 H 5-CH.sub.2 Br H 0 O2.068 F 5-CH.sub.2 Br H 0 O2.069 H 5-CH.sub.2 CN H 0 O2.070 F 5-CH.sub.2 CN H 0 O2.071 H 5-CH.sub.2 OH H 0 O2.072 F 5-CH.sub.2 OH H 0 O2.073 H 5-CH.sub.2 SH H 0 O2.074 F 5-CH.sub.2 SH H 0 O2.075 H 5-CH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.076 F 5-CH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.077 H 5-CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.078 F 5-CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.079 H 5-CH.sub.2 OCH.sub.3 H 0 O2.080 F 5-CH.sub.2 OCH.sub.3 H 0 O2.081 H 5-CH.sub.2 OCH.sub.2 CH.sub.3 H 0 O2.282 F 5-CH.sub.2 OCH.sub.2 CH.sub.3 H 0 O2.083 H 5-CH.sub.2 SCH.sub.3 H 0 O2.084 F 5-CH.sub.2 SCH.sub.3 H 0 O2.085 H 5-CH.sub.2 OCH.sub.2 CHCH.sub.2 H 0 O2.086 F 5-CH.sub.2 OCH.sub.2 CHCH.sub.2 H 0 O2.087 H 5-CH.sub.2 OCH.sub.2 CCH H 0 O2.088 F 5-CH.sub.2 OCH.sub.2 C CH H 0 O2.089 H 5-CH.sub.2 OCOCH.sub.3 H 0 O2.090 F 5-CH.sub.2 OCOCH.sub.3 H 0 O2.091 H 5-CH.sub.2 OCOCH.sub.2 CH.sub.3 H 0 O2.092 F 5-CH.sub.2 OCOCH.sub.2 CH.sub.3 H 0 O2.093 H 5-CO.sub.2 CH.sub.3 H 0 O2.094 F 5-CO.sub.2 CH.sub.3 H 0 O2.095 H 5-CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.096 F 5-CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.097 H 5-COOH H 0 O2.098 F 5-COOH H 0 O2.099 H 5-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.100 F 5-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.101 H 5-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.102 F 5-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 0 O2.103 H 5-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.104 F 5-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.105 H 5-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.3 H 0 O2.106 F 5-CH.sub.2 OCH.sub. 2 CO.sub.2 CH.sub.3 H 0 O__________________________________________________________________________ TABLE 3______________________________________ ##STR11##No. R.sup.1 R.sup.3 R.sup.4 n X mp. [.degree.C.]______________________________________3.001 H H H 1 S 198-2003.002 F H H 1 S3.003 H 4-CH.sub.3 H 1 S 158-1593.004 F 4-CH.sub.3 H 1 S3.005 H 4-CH.sub.2 CH.sub.3 H 1 S3.006 F 4-CH.sub.2 CH.sub.3 H 1 S3.007 H 4-(CH.sub.2).sub.2 CH.sub.3 H 1 S3.008 F 4-(CH.sub.2).sub.2 CH.sub.3 H 1 S3.009 H 4-CH(CH.sub.3).sub.2 H 1 S3.010 F 4-CH(CH.sub.3).sub.2 H 1 S3.011 H 4-CH.sub.2 Cl H 1 S3.012 F 4-CH.sub.2 Cl H 1 S3.013 H 4-CH.sub.2 Br H 1 S3.014 F 4-CH.sub.2 Br H 1 S3.015 H 4-CH.sub.2 CN H 1 S3.016 F 4-CH.sub.2 CN H 1 S3.017 H 4-CH.sub.2 OH H 1 S3.018 F 4-CH.sub.2 OH H 1 S3.019 H 4-CH.sub.2 SH H 1 S3.020 F 4-CH.sub.2 SH H 1 S3.021 H 4-CH.sub.2 CO.sub.2 CH.sub.3 H 1 S3.022 F 4-CH.sub.2 CO.sub.2 CH.sub.3 H 1 S3.023 H 4-CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 1 S3.024 F 4-CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 1 S3.025 H 4-CH.sub.2 OCH.sub.3 H 1 S3.026 F 4-CH.sub.2 OCH.sub.3 H 1 S3.027 H 4-CH.sub.2 OCH.sub.2 CH.sub.3 H 1 S3.028 F 4-CH.sub.2 OCH.sub.2 CH.sub.3 H 1 S3.029 H 4-CH.sub.2 SCH.sub.3 H 1 S3.030 F 4-CH.sub.2 SCH.sub.3 H 1 S3.031 H 4-CH.sub.2 CH.sub.2 SCH.sub.3 H 1 S3.032 F 4-CH.sub.2 CH.sub.2 SCH.sub.3 H 1 S3.033 H 4-CH.sub.2 OCH.sub.2 CHCH.sub.2 H 1 S3.034 F 4-CH.sub.2 OCH.sub.2 CHCH.sub.2 H 1 S3.035 H 4-CH.sub.2 OCH.sub.2 CCH H 1 S3.036 F 4-CH.sub.2 OCH.sub.2 CCH H 1 S3.037 H 4-CH.sub.2 OCOCH.sub.3 H 1 S3.038 F 4-CH.sub.2 OCOCH.sub.3 H 1 S3.039 H 4-CH.sub.2 OCOCH.sub.2 CH.sub.3 H 1 S3.040 F 4-CH.sub.2 OCOCH.sub.2 CH.sub.3 H 1 S3.041 H 4-CO.sub.2 CH.sub.3 H 1 S3.042 F 4-CO.sub.2 CH.sub.3 H 1 S3.043 H 4-CO.sub.2 CH.sub.2 CH.sub.3 H 1 S3.044 F 4-CO.sub.2 CH.sub.2 CH.sub.3 H 1 S3.045 H 4-COOH H 1 S3.046 F 4-COOH H 1 S3.047 H 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 H 1 S3.048 F 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 H 1 S3.049 H 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 1 S3.050 F 4-CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 1 S3.051 H 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.3 H 1 S3.052 F 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.3 H 1 S3.053 H 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 1 S3.054 F 4-CH.sub.2 OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 H 1 S3.055 H 4-CH.sub.3 6-CH.sub.3 1 S3.056 F 4-CH.sub.3 6-CH.sub.3 1 S3.057 H 5-CH.sub.3 5-CH.sub.3 1 S3.058 F 5-CH.sub.3 5-CH.sub.3 1 S______________________________________ TABLE 4______________________________________ ##STR12##No. R.sup.1 R.sup.5 R.sup.6 Z mp. [.degree.C.]______________________________________4.001 H H H CHCH4.002 F H H CHCH4.003 H 4-CH.sub.3 H CHCH4.004 F 4-CH.sub.3 H CHCH4.005 H 4-CH.sub.2 CH.sub.3 H CHCH4.006 F 4-CH.sub.2 CH.sub.3 H CHCH4.007 H 4-CH.sub.2 CH.sub.2 CH.sub.3 H CHCH4.008 F 4-CH.sub.2 CH.sub.2 CH.sub.3 H CHCH4.009 H 4-CH(CH.sub.3).sub.2 H CHCH4.010 F 4-CH(CH.sub.3).sub. 2 H CHCH4.011 H 4-CH.sub.3 7-CH.sub.3 CHCH4.012 F 4-CH.sub.3 7-CH.sub.3 CHCH4.013 H H H CH.sub.2 OCH.sub.2 134-1354.014 F H H CH.sub.2 OCH.sub.24.015 H 4-CH.sub.3 H CH.sub.2 OCH.sub.24.016 F 4-CH.sub.3 H CH.sub.2 OCH.sub.24.017 H 4-CH.sub.2 CH.sub.3 H CH.sub.2 OCH.sub.24.018 F 4-CH.sub.2 CH.sub.3 H CH.sub.2 OCH.sub.24.019 H 4-CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.2 OCH.sub.24.020 F 4-CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.2 OCH.sub.24.021 H 4-CH(CH.sub.3).sub.2 H CH.sub.2 OCH.sub.24.022 F 4-CH(CH.sub.3).sub.2 H CH.sub.2 OCH.sub.24.023 H 4-CH.sub.3 8-CH.sub.3 CH.sub.2 OCH.sub.24.024 F 4-CH.sub.3 8-CH.sub.3 CH.sub.2 OCH.sub.24.025 H H H CH.sub.2 SCH.sub.24.026 F H H CH.sub.2 SCH.sub.24.027 H 4-CH.sub.3 H CH.sub.2 SCH.sub.24.028 F 4-CH.sub.3 H CH.sub.2 SCH.sub.24.029 H 4-CH.sub.2 CH.sub.3 H CH.sub.2 SCH.sub.24.030 F 4-CH.sub.2 CH.sub.3 H CH.sub.2 SCH.sub.24.031 H 4-CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.2 SCH.sub.24.032 F 4-CH.sub.2 CH.sub.2 CH.sub.3 H CH.sub.2 SCH.sub.24.033 H 4-CH(CH.sub.3).sub.2 H CH.sub.2 SCH.sub.24.034 F 4-CH(CH.sub.3).sub.2 H CH.sub.2 SCH.sub.24.035 H 4-CH.sub.3 8-CH.sub.3 CH.sub.2 SCH.sub.24.036 F 4-CH.sub.3 8-CH.sub.3 CH.sub.2 SCH.sub.2______________________________________ TABLE 5______________________________________ ##STR13##No. R.sup.1 R.sup.3 R.sup.4 X mp. [.degree.C.]______________________________________5.001 H H H S5.002 F H H S 104-1065.003 H CH.sub.3 H S5.004 F CH.sub.3 H S 110-1125.005 H H H O5.006 F H H O5.007 H CH.sub.3 H O5.008 F CH.sub.3 H O oil______________________________________

The herbicidal agents, or the active ingredients on which they are based, may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).

The application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from 0.005 to 3.0, preferably 0.01 to 0.5, kg/ha.

The action of the active ingredients of the formula I on the growth of plants is illustrated in greenhouse experiments.

The vessels employed were plastic flowerpots having a volume of 300 cm.sup.3 and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.

For the postemergence treatment, either plants which had been sown in the pots and grown there were selected, or they were cultivated separately as seedlings and transplanted to the pots a few days before being treated.

Depending on growth form, the plants were grown to a height of from 3 to 15 cm before being treated with the active ingredients which were suspended or emulsified in water and sprayed through finely distributing nozzles. The application rates for postemergence treatment were 0.015 and 0.03 kg/ha.

The pots were set up in the greenhouse, species from warmer climates in warmer areas (20.degree. to 36.degree. C.) and species from moderate climates at 10.degree. to 20.degree. C. The experiments were run for from 2 to 4 weeks. During this time the plants were tended and their reactions to the various treatments assessed.

The assessment scale was 0 to 100, 100 denoting nonemergence or complete destruction of at least the visible plant parts, and 0 denoting no damage or normal growth.

The plants used in the greenhouse experiments belonged to the following species:

______________________________________CODE Botanical name Common name______________________________________ABUTH Abutilon theophrasti velvet leafAMARE Amaranthus spp. pigweedCHYCO Chrysanthemum corinarium crown daisyDEDTO Desmodium tortuosum Florida beggarweedGALAP Galium aparine catchweed bedstrawIPOSS Ipomoea spp. morninggloryLAMAM Lamium amplexicaule henbitMERAN Mercurialis annua annual mercurySOLNI Solanum nigrum black nightshadeSTEME Stellaria media chickweedTRZAS Triticum aestivum spring wheatZEAMX Zea mays Indian corn______________________________________

In view of the numerous application methods possible, the compounds according to the invention, or agents containing them, may be used in a large number of crop plants for removing unwanted plants. The following crops are examples:

______________________________________Botanical name Common name______________________________________Allium cepa onionsAnanas comosus pineapplesArachis hypogaea peanuts (groundnuts)Asparagus officinalis asparagusAvena sativa oatsBeta vulgaris spp. altissima sugarbeetsBeta vulgairs spp. rapa fodder beetsBeta vulgaris spp. esculenta table beets, red beetsBrassica napus var. napus rapeseedBrassica napus var. napobrassica swedesBrassica napus var. rapa turnipsBrassica rapa var. silvestrisCamellia sinensis tea plantsCarthamus tinctorius safflowerCarya illinoinensis pecan treesCitrus limon lemonsCitrus maxima grapefruitsCitrus reticulata mandarinsCitrus sinensis orange treesCoffea arabica (Coffea canephora, coffee plantsCoffea liberica)Cucumis melo melonsCucumis sativus cucumbersCynodon dactylon BermudagrassElais guineensis oil palmsFragaria vesca strawberriesGlycine max soybeansGossypium hirsutum (Gossypium arboreum, cottonGossypium herbaceum, Gossypium vitifolium)Helianthus annuus sunflowersHelianthus tuberosus Jerusalem artichokeHevea brasiliensis rubber plantsHordeum vulgare barleyHumulus lupulus hopsIpomoea batatas sweet potatoesJuglans regia walnut treesLinum usitatissimum flaxLycopersicon lycopersicum tomatoesMalus spp. apple treesManihot esculenta cassavaMedicago sativa alfalfa (lucerne)Mentha piperita peppermintMusa spp. banana plantsNicotiana tabacum (N. rustica) tobaccoOlea europaea olive treesOryza sativa ricePanicum miliaceum panic grassPhaseolus lunatus limabeansPhaseolus mungo mungbeansPhaseolus vulgaris snapbeans, green beans, dry beansPennisetum glaucum pearl milletPetroselinum crispum spp. tuberosum parsleyPicea abies Norway spruceAbies alba fir treesPinus spp. pine treesPisum sativum English peasPrunus avium cherry treesPrunus domestica plum treesPrunus dulcis almond treesPrunus persica peach treesPyrus communis pear treesRibes sylvestre redcurrantsRibes uva-crispa gooseberriesRicinus communis castor-oil plantsSaccharum officinarum sugar caneSecale cereale ryeSesamum indicum sesameSolanum tuberosum Irish potatoesSorghum bicolor (s. vulgare) sorghumSorghum dochna sorgoTheobroma cacao cacao plantsTrifolium pratense red cloverTriticum aestivum wheatVaccinium corymbosum blueberriesVaccinium vitis-idaea cranberriesVicia faba tick beansVigna sinensis (V. unguiculata) cow peasVitis vinifera grapesZea mays Indian corn, sweet corn, maize______________________________________

To increase the spectrum of action and to achieve synergistic effects, the N-phenyltetrahydrophthalimides of the formula I may be mixed with each other, or mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acids, (hetero)-aryloxyphenoxypropionic acids and salts, esters and amides thereof, etc.

It may also be useful to apply the N-phenyltetrahydrophthalimides of the formula I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.

TABLE 6______________________________________Herbicidal action and tolerance by a crop on postemergenceapplication of 0.03 kg/ha of compound no. 1.001 in the greenhouse ##STR14## comp. no. 1.001Test plants Damage (%)______________________________________TRZAS 0AMARE 100GALAP 100IPOSS 100MERAN 100______________________________________ TABLE 7______________________________________Herbicidal action on postemergence application of compoundno. 1.003 at a rate of 0.03 kg/ha in the greenhouse ##STR15## comp. no. 1.003Test plants Damage (%)______________________________________ABUTH 100AMARE 100DEDTO 100GALAP 100IPOSS 100MERAN 100SOLNI 100STEME 100______________________________________ TABLE 8__________________________________________________________________________Control of unwanted broadleaved plants and tolerance by a crop onpostemergence application of 0.015 kg/ha in the greenhouse ##STR16##Comp. no. R.sup.1 R ZEAMX CHYCO GALAP LAMAM SOLNI STEME__________________________________________________________________________1.002 F H 10 100 100 100 100 1001.003 F CH.sub.3 15 100 100 100 100 100__________________________________________________________________________

Claims

1. An N-phenyltetrahydrophthalimide of the formula I: ##STR17## wherein R.sup.1 is hydrogen or halogen, R.sup.2 is halogen, A is a substituent of the formula: ##STR18## wherein X is oxygen or sulfur; n is 0 or 1; R.sup.3 is hydrogen or C.sub.1 -C.sub.6 -alkoxycarbonyl or C.sub.1 -C.sub.3 -alkyl which is unsubstituted or substituted by halogen, cyano, hydroxy, mercapto, C.sub.1 -C.sub.6 -alkoxycarbonyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.3 -C.sub.6 -alkenyloxy, C.sub.3 -C.sub.6 -alkenylthio, C.sub.3 -C.sub.6 -alkynyloxy, C.sub.3 -C.sub.6 -alkynylthio or C.sub.1 -C.sub.4 -acyloxy, or is hydroxy or carboxy or is C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.2 -alkyl or C.sub.1 -C.sub.4 -alkylthio-C.sub.1 -C.sub.2 -alkyl which is unsubstituted or substituted in the alkylether or thioether moiety by C.sub.1 -C.sub.6 -alkoxycarbonyl; R.sup.4 is hydrogen or C.sub.1 -C.sub.3 -alkyl; Z is methyleneoxymethylene, methylenethiomethylene or ethenylene; R.sup.5 is hydrogen or C.sub.1 -C.sub.3 -alkyl; and R.sup.6 is hydrogen or C.sub.1 -C.sub.3 -alkyl, independently of the steric configuration, with the proviso that n is 1 when R.sup.3 and R.sup.4 are both hydrogen.

2. The N-phenyltetrahydrophthalimide of claim 1, wherein R.sup.1 is hydrogen or fluorine, R.sup.2 is chlorine and A is dithiolane or oxathiolane rings, which are unsubstituted or substituted.

3. The N-phenyltetrahydronaphthalimide of claim 1, wherein A is ##STR19##

4. The N-phenyltetrahydronaphthalimide of claim 1, wherein A is ##STR20##

5. The compound of claim 2 having the formula: ##STR21##

6. A compound according to claim 2 wherein R.sup.1 is H, R.sup.2 is chloro, and A is ##STR22##

7. A compound according to claim 2 wherein R.sup.1 is F, R.sup.2 is Cl, and A is ##STR23##

8. A compound according to claim 2 wherein R.sup.1 is H, R.sup.2 is Cl, and A is ##STR24##

9. A compound according to claim 2, wherein R.sup.1 is F, R.sup.2 is F, and A is ##STR25##

10. A compound according to claim 2 wherein R.sup.1 is F, R.sup.2 is F, and A is ##STR26##

11. A compound according to claim 2 having the formula: ##STR27##

12. A herbicidal agent, comprising an effective amount of one or more compounds of the formula I as set forth in claim 4, and one or more auxiliaries, extenders or diluents.

13. The herbicidal agent of claim 12, wherein for the compound of the formula I, R.sup.1 is hydrogen or fluorine, R.sup.2 is chlorine and A is dithiolane or oxothiolane rings, which are unsubstituted or substituted.

14. A process for combating the growth of unwanted plants, which comprises applying to said plants or their habitat or both a herbicidally effective amount of one or more N-phenyltetrahydrophthalimide compounds of the formula I as set forth in claim 1.

15. The process of claim 14, wherein for the compound of the formula I, R.sup.1 is hydrogen or fluorine, R.sup.2 is chlorine and A is dithiolane or oxothiolane rings, which are unsubstituted or substituted.

16. The process of claim 14, wherein said herbicidally effective amount is from about 0.005-3.0 kg/ha.

17. The process of claim 16, wherein said herbicidally effective amount is from about 0.01-0.5 kg/ha.

18. The process of claim 16, wherein said herbicidally effective amount is from about 0.015-0.03 kg/ha for post-emergence treatment.