CA2153791A1

CA2153791A1 - Derivatives of azaanthraquinone and of azaxanthone and herbicides and plant growth regulators containing them

Info

Publication number: CA2153791A1
Application number: CA002153791A
Authority: CA
Inventors: Peter Plath; Costin Rentzea; Norbert Meyer; Juergen Kast; Uwe Kardorff; Matthias Gerber; Helmut Walter; Andreas Landes; Karl-Otto Westphalen
Original assignee: Individual
Current assignee: BASF SE
Priority date: 1993-01-20
Filing date: 1994-01-12
Publication date: 1994-08-04
Also published as: DE59405587D1; DE4301424A1; HU216892B; HU9502175D0; ATE164583T1; HUT72271A; JPH08505635A; KR960700248A; EP0680481B1; EP0680481A1; WO1994017070A1

Abstract

A process is disclosed for controlling undesirable plant growth and for regulating plant growth, by applying to the plants derivatives of azaanthraquinones and/or azaxanthones having formula(I'), in which X, Y, Z and the residues R1 to R5 have the following meanings:
R1 is hydrogen, methyl; R2-R5 are (a) hydrogen, (b) halogen, (c) nitro, (d) COOR6, in which R6 stands for C1-C4-alkyl (e) CONH2 and CONR6R7, in which R6 and R7 stand for C1-C4-alkyl, (f) C1-C8-alkyl, which may bear one to three of the following substituents; halogen, hydroxy, C1-C6-alkoxy, (g) C3-C6alkenyl, (h) C1-C4-alkoxy, (i) hydroxy, (j) amino or NR6R7, (k) phenyl, which may bear one to five halogen atoms or one to three of the following substituents nitro, C1-C4-alkoxy, C1-C4-alkyl, or C1-C4-alkyl halide: X, Y are N, N4-O- or CH, with the proviso that only a nitrogen atom or a N-oxide group be contained in the ring: Z is oxygen, sulphur or a C = O group: A
is oxygen or sulphur. Also disclosed are new azaanthraquinones and azaxanthones and herbicidal and bioregulatory agents containing the same.

Description

21~37~1 -Derivatives of azaanthraquinone and of azaxanthone and herbicides and plant growth regulators containing them 5 The present invention relates to novel azaanthraquinones and azaxanthones of the formula I

y ~ R3 ~`X~ ZJ~----~ R4 R

15 where Rl is hydrogen or methyl, R2-R5 are each a) hydrogen, b) halogen, c) nitro, d) COOR6, where R6 is C1-C4-alkyl, e) CONH2 or CONR6R7, where R6 and R7 are each C1-C4-alkyl, f) Cl-C8-alkyl which may carry from one to three of the following substituents: halogen, hydroxyl and Cl-C6-alkoxy, g) C3-C6-alkenyl, h) Cl-C4-alkoxy, i) hydroxyl, j) amino or NR6R7, or k) phenyl which may carry from one to five halogen atoms or from one to three of the following substituents:
nitro, Cl-C4-alkoxy, Cl-C4-alkyl or C1-C4-haloalkyl;

X and Y are each N, N+-0- or CH, with the proviso that only one nitrogen atom or one N-oxide group is present in the ring;
Z is oxygen, sulfur or a C=O group and A is oxygen or sulfur;

21~3791 and the salts of I with those acids which do not adversely affect the herbicidal or the plant growth-regulating action of I, with the proviso that the alkaloid cleistopholine and the azaxanthones of the formula Ia lo ~ RR Ia where R2, R3, R4 and R5 are identical or different and, independently of one another, are each hydrogen, fluorine, 15 chlorine, methyl, methoxy, COCH3, COOH, CF3, CCl3, tert-C4Hg, NO2, NH2 or phenyl, are excluded from the claim.

The publications by P.G. Waterman et al. (Phytochemistry, 24 (1985), 523) and by A. Cavé et al. (J. Nat. Prod. 50 (1987), 759) 20 disclose the alkaloid cleistopholine or 4-methylbenzo[g]quinoline-5,10-dione, which was isolated from the plant Cleistopholis patens. A large number of 5H-[l]benzopyrano[2,3-b~pyridin-5-ones are known from the publications by F.J. Villani et al. (J. Med. Chem., 18 (1975), 1) 25 and by P. Natka-Namirski (Acta Pol. Pharm. 34 (1977), 1). In the stated literature, these compounds are ascribed antihistAm; n; C, bronchodilatatory and anticandida properties. However, a herbicidal or plant growth-regulating action of these substances is not known.
Since the known compounds are not always satisfactory in their action, it is an object of the present invention to provide novel herbicides having a stronger herbicidal effect and novel plant growth regulators, preferably growth inhibitors. It is a further 35 object of the present invention to provide novel compounds having a herbicidal and plant growth-regulating action.

We have found that these objects are achieved by the novel compounds I defined at the outset.
The present invention furthermore relates to herbicidal and bioregulatory, in particular plant growth-inhibiting, compositions containing the compounds I and processes for the preparation of the compounds I. We have furthermore found that 45 the compounds of the formula I', which correspond to the compounds of the formula I including the compounds Ia, are suitable for use as herbicides or plant growth regulators. A

0050/43806 2~ ~3 79 1 corresponding novel action is also shown by the known alkaloid cleistopholine.

Preferred novel compounds of the formula I are those in which Rl is hydrogen or in particular methyl, R2, R3, R4 and R5 are each hydrogen, fluorine, chlorine, bromine or straight-chain or branched Cl-C8-alkyl, in particular C1-C6-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl or 1-ethyl-1-methylpropyl;
straight-chain or branched C1-C8-alkyl, in particular Cl-C6-alkyl, which may carry up to 3 of the following substituents: halogen, such as fluorine, chlorine or bromine, hydroxyl and Cl-C6-alkoxy, in particular Cl-C4-alkoxy, such as methoxy, ethoxy or propoxy;

straight-chain or branched C3-C6-alkenyl, in particular vinyl, allyl, 2-methylallyl, 3-methylallyl, 2,3-dimethylallyl, 3,3-dimethylallyl, 2-pentenyl or 3-pentenyl;

Cl-C4-alkoxy, in particular methoxy, ethoxy or propoxy;

nitro, amino (NH2), an ester group, eg. COOCH3, COOC2Hs, COOC3H7 or COOC4Hg, or amido, such as C0-NH2, CO-N ( CH3 ) 2 or CO-N ( C2H5 ) 2; or phenyl which is unsubstituted or monosubstituted to trisubstituted by fluorine, chlorine, CF3, N02 or Cl-C4-alkyl;

R6 and R7 are each straight-chain or branched Cl-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;

X is N, N+-0- or CH;

Y is CH, N or N+-O-;
Z is oxygen, sulfur or a C=O`group; and 0050~43806 2I~7gl A is oxygen or sulfur.

Particularly preferred compounds of the formula I are those in which Rl is methyl. Furthermore, X is preferably nitrogen or the 5 N-oxide group and Y is CH.

The substitution pattern in the phenyl ring of the formula I
exhibits in particular mono- or disubstitution, unless all radicals R2 to R5 are hydrogen. Preferred substituents are 10 halogen, such as fluorine, chlorine or bromine, C1-C4-alkyl, for example branched alkyl, such as isopropyl, sec-butyl or tert-butyl, Cl-C4-haloalkyl, in particular trifluoromethyl, and nitro. Compounds in which R2 and R4 are each hydrogen and R3 and/or R5 are one of the stated substituents are also 15 advantageous.

Suitable acid addition salts are the salts of those acids which do not adversely affect the herbicidal action of the compounds I
and Ia, for example the hydrochlorides and hydrobromides, 20 sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates.

The azaanthraquinones and azaxanthones Ia are known or (in the case of I) are obtainable by a method known per se.
Where Y is CH, X is N, Rl is CH3 and Z is the C=0 group, the compounds I and Ia can be prepared according to the following scheme:

2 Rl Rl O R2 R33~Br ~ ~ ~R

N(CH3)2 ( 3)2 II III IV
- (CH3)2NH

Ina This process is disclosed, for example, in the publication by F. Bracher, Liebigs Ann. Chem. 1989, 87.

, 21~3791 The hetero Diels-Alder cycloaddition of `2-bromo-1,4-naphthoquinones (II) with crotonaldehyde dimethyl hydrazone (III) gives the dihydropyridine (IV) with elimination 5 of HBr. The thermal elimination of dimethylamine from (IV) gives the compounds I or Ia. This synthesis is carried out by heating (II) with (III) at from 100 to 160 C for several hours in an inert organic solvent. The cycloaddition and elimination are particularly advantageously carried out in a single-vessel 10 process, ie. without isolation of the intermediate IV. Possible inert organic solvents are in particular xylene, toluene, ethylbenzene, isopropylbenzene, chlorobenzene and chlorotoluene.

Where Y is CH, X is N, R~ is H or CH3 and Z is oxygen, the 15 azaxanthones I and Ia are preferably prepared by the process according to F.J. Villani et al. (loc. cit.):

~ ~ Polyphosphoric acid I I

V

The cyclization of the known 2-phenoxynicotinic acid (V) to the azaxanthones I and Ia is carried out in polyphosphoric acid at from 100 to 180 C, and the polyphosphoric acid can advantageously 30 be used also as a solvent and diluent.

The compounds I in which X or Y is N+-O- are synthesized by reacting the corresponding azaanthraquinones and azaxanthones with H2O2 or with an organic peroxy acid by a standard process 35 (cf. for example E. Ochiai, Aromatic Amine Oxides, Elsevier, Amsterdam, 1967, pages 200-250).

For the preparation of compositions for controlling undesirable plant growth or for regulating plant growth, preferably used 40 compounds of the formula I are those in which R1 is hydrogen, R2 is hydrogen or halogen, R3 is hydrogen, halogen, C1-C4-alkyl or nitro, R4 is hydrogen, halogen, Cl-C4-alkyl, Cl-C4-alkoxy or hydroxyl, R5 is hydrogen or halogen, X is N, Y is CH, Z is oxygen, sulfur or C=O and A is oxygen or sulfur.
AMENDEDSHEET

0050/43806 2 1 5 ~ 7 9 1 5a Compounds I and I' preferred for biological use are shown in Table 1 below:

AMENDEDSHEET

21~3 79I

Table 1 5 CH3 H H H H N CH C=0 CH3 H H H H CH N C=0 CH3 H H H H N+-0- CH C=0 H H H H H N+-0- CH 0 CH3 H H H H N+-0- CH 0 CH3 H H H H CH N+-O- 0 F H H H N CH C=0 CH3 F H H H CH N C=0 20 CH3 F H H H CH N+-O- C=0 CH3 H F H H N CH C=0 25 CH3 H F H H CH N C=0 CH3 H H F H N CH C=0 CH3 H H F H CH N C=0 CH3 H H H F N CH C=0 35 CH3 H H H F CH N C=0 CH3 Cl H H H N CH C=0 H Cl H H H N CH 0 CH3 Cl H H H N CH 0 40 CH3 Cl H H H CH N C=0 CH3 H Cl H H N CH C=0 H H Cl H H N CH 0 CH3 H Cl H H N CH 0 CH3 H Cl H H CH N C=0 CH3 H H Cl H - N CH C=0 CH3 H H Cl H N CH 0 0050/43806 2 1 ~ 3 79 Rl R2 R3 R4 R5 X Y Z
H H H Cl H N CH 0 CH3 H H H Cl N CH C=0 5 H H H H Cl N CH 0 CH3 H H H Cl N CH 0 CH3 H H H Cl CH N C=0 CH3 H Br H H N CH C=0 H H Br H H N CH 0 CH3 H Br H H N CH 0 CH3 H H Br H N CH C=0 H H H Br H N CH 0 CH3 H H Br H N CH 0 15 CH3 CH3 H H H N CH C=0 CH3 H CH3 H H N CH C=0 CH3 H H CH3 H N CH C=0 CH3 H H CH3 H N+-0- CH C=0 CH3 H H H CH3 N CH C=0 30 CH3 H C2Hs H H N CH C=0 CH3 H C2Hs H H N CH 0 CH3 H -CH(CH3~ 2 H H N CH C=0 35 H H -CH(CH3) 2 H H N CH 0 CH3 H -CH(CH3) 2 H H N CH 0 CH3 H -CH2CH(CH3) 2 H H N CH C=0 H H -CH2CH(CH3) 2 H H N CH 0 40 CH3 H -CH2CH(CH3) 2 H H N CH 0 CH3 H -C4H9-n H H N CH C=0 CH3 H -C4Hg-n H H N CH 0 H H -C4Hg-n H H N CH 0 CH3 H -C4Hg-tert H H N CH C=0 CH3 H -C4Hg-tert H H N+-0- CH C=0 H H -C4Hg-tert H H N CH 0 215~91 Rl R2 R3 R4 Rs X Y Z
CH3 H -C4Hg-tert H H N CH O
CH3 H -C6H~3-n H H N CH C=O
5 CH3 H -C6Hl3-n H H N CH O
H H -C6Hl3-n H H N CH O
CH3 OCH3 H H H N CH C=O

CH3 OCH3 H H H CH N C=O
CH3 H OCH3 H H N CH C=O

15 CH3 H OCH3 H H N+-O- CH C=O
CH3 H H OCH3 H N CH C=O

20 CH3 H H H OCH3 N CH C=O

CH3 H OC2H5 H H N CH C=O

CH3 H OC4Hgn H H N CH C=O
H H OC4Hgn H H N CH O
CH3 H OC4Hgn H H N CH O
30 CH3 H Allyl H H N CH C=O
CH3 H Allyl H H N CH O
CH3 CF3 H H H N CH C=O

CH3 H CF3 H H N CH C=O

40 CH3 H H CF3 H N CH C=O

CH3 H H CF3 H N+-O- CH C=O
CH3 H H H CF3 N CH C=O

2~L~3791 g Rl R2 R3 R4 R5 X Y Z
CH3 NO2 H H H N CH C=O

CH3 H N2 H H N CH C=O

CH3 H H NO2 H N CH C=O

CH3 H C6H5 H H N CH C=O

CH3 H H C6H5 H N CH C=O

20 CH3 H COOCH3 H H N CH C=O

CH3 H COOC2H5 H H N CH C=O

25 CH3 H CONH2 H H N CH C=O

CH3 H CON(CH3)2 H H N CH C=O
CH3 H CON(CH3)2 H H N CH O
CH3 F H F H N CH C=O

CH3 F H H F N CH C=O
H F H H F N CH O

CH3 H F F H N CH C=O
H H F F H N CH O

40 CH3 H F H F N CH C=O
H H F H F N CH O

CH3 F H CH3 H N CH C=O

21~3791 Rl R2 R3 R4 R5 X Y Z
CH3 CH3 H F H N CH C=0 CH3 F H H CH3 N CH C=0 CH3 CH3 H H F N CH C=0 CH3 H F H CH3 N CH C=0 CH3 F H Cl H N CH C=0 CH3 F H Cl H N CH 0 CH3 Cl H F H N CH C=0 H Cl H F H N CH 0 15 CH3 Cl H F H N CH 0 CH3 H F H Cl N CH C=0 CH3 H F H Cl N+-0- CH C=0 CH3 H F H Cl N CH 0 20 CH3 H Cl H F N CH C=0 CH3 H Cl H F N CH 0 CH3 CH30 F H H N CH C=0 CH3 CH30 H F H N CH C=0 CH3 F H CH30 H N CH C=0 CH3 F H H CH30 N CH C=0 30 CH3 CH30 H H F N CH C=0 CH3 CH30 H H F N+-0- CH C=0 CH3 H CH30 H F N CH C=0 35 CH3 H CH30 F H N CH C=0 CH3 Cl H Cl H N CH C=0 CH3 Cl H Cl H N CH 0 CH3 Cl H H Cl N CH C=0 40 H Cl H H Cl N CH 0 CH3 Cl H H Cl N CH 0 CH3 H Cl Cl H N CH C=0 CH3 H Cl Cl H N CH 0 CH3 H Cl H Cl N CH C=0 CH3 H Cl H Cl. N+-0- CH C=0 CH3 H Cl H Cl CH N C=0 0050/43806 ~ 3 7 9 Rl R2 R3 R4 Rs X Y Z
CH3 H Cl H Cl N CH 0 CH3 H Cl H Cl N+-0- CH 0 5 CH3 H Cl H Cl CH N 0 H H Cl H Cl CH N 0 CH3 Cl H CH3 H N CH C=0 CH3 Cl H CH3 H N CH 0 CH3 CH3 H Cl H N CH C=0 CH3 CH3 H Cl H N CH 0 CH3 Cl H H CH3 N CH C=0 CH3 Cl H H CH3 N CH 0 CH3 CH3 H H Cl N CH C=0 15 CH3 CH3 H H Cl N CH 0 CH3 H Cl CH3 H N CH C=0 CH3 H Cl CH3 H N CH 0 CH3 H Cl H CH3 N CH C=0 20 CH3 H Cl H CH3 N CH 0 CH3 H CH3 H Cl N CH C=0 CH3 H CH3 H Cl N CH 0 CH3 Cl H CH30 H N CH C=0 25 H Cl H CH30 H N CH 0 CH3 Cl H CH30 H N CH 0 CH3 CH30 H Cl H N CH C=0 CH3 CH30 H Cl H N CH 0 CH3 Cl H H CH30 N CH C=0 30 H Cl H H CH30 N CH 0 CH3 Cl H H CH30 N CH 0 CH3 H Cl CH30 H N CH C=0 CH3 H Cl CH30 H N CH 0 35 CH3 H CH30 Cl H N CH C=0 CH3 H CH30 Cl H N CH 0 CH3 H Cl H CH30 N CH C=0 CH3 H Cl H CH30 N CH 0 40 CH3 H CH30 H Cl N CH C=0 CH3 H CH30 H Cl N CH 0 CH3 Cl H C2HsO H N CH C=0 CH3 Cl H C2H5 H N+-0- CH C=0 CH3 CH3 H CH3 H N CH C=0 - ` . 2I~3791 Rl R2 R3 R4 R5 X Y Z
CH3 H CH3 CH3 H N CH C=0 5 CH3 H CH3 H CH3 N CH C=0 CH3 CH3 H H CH3 N CH C=0 CH3 CH3 H H CH3 CH N C=0 CH3 CH30 CH30 H H N CH C=0 CH3 CH30 H CH30 H N CH C=0 CH3 H CH30 CH30 H N CH C=0 CH3 CH30 H H CH30 N CH C=0 CH3 H CH30 H CH30 N CH C=0 CH3 H CH30 H CH30 N+-0- CH C=0 25 CH3 H CH30 H CH30 CH N C=0 CH3 H CH30 H CH30 CH N+-0- C=0 30 The compounds I and I' and the herbicides containing them and their environmentally compatible salts of alkali metals and alkaline earth metals can control weeds and grass weeds very well in crops such as wheat, rice, corn, soya bean and cotton without damaging the crops, an effect which occurs in particular at low 35 application rates.

The compounds I and I' and the herbicides containing them can be used, for example, in the form of directly sprayable solutions, powders, suspensions, including concentrated aqueous, oily or 40 other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting agents, broadcasting agents or granules, by spraying, atomizing, dusting, broadcasting or pouring. The application forms depend on the intended uses; they should in any case ensure very fine distribution of the novel active 45 ingredients 21~3 '79I

The compounds I and I' are suitable in general for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions. Suitable inert additives are mineral oil fractions having a medium to high boiling point, such as kerosene 5 or diesel oil, as well as coal tar oils and oils of vegetable or An;m~l origin, aliphatic, cyclic and aromatic hydrocarbons, eg.
toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, alkylated benzenes or derivatives thereof, methanol, ethanol, propanol, butanol, 10 cyclohexanol, cyclohexanone, chlorobenzene or strongly polar solvents, such as N-methylpyrrolidone or water.

Aqueous application forms may be prepared from emulsion concentrates, dispersions, pastes, wettable powders or 15 water-dispersible granules by adding water. For the preparation of emulsions, pastes or oil dispersions, the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adherents, dispersants or emulsifiers.
However, concentrates which consist of active ingredient, wetting 20 agents, adherents, dispersants or emulsifiers and possibly solvents or oil and which is suitable for dilution with water can also be prepared.

Suitable surfactants are the alkali metal, alkaline earth metal 25 and ammonium salts of aromatic sulfonic acids, eg. lignin-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkane- and alkylarylsulfonates, alkylsulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol 30 glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-, octyl-or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl 35 polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, ligninsulfite waste liquors or methylcellulose.
Powders, broadcasting agents and dusting agents can be prepared by mixing or milling the active ingredients together with a solid carrier.

45 Granules, for example coated, impregnated and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths, such as silica 0050/43806 2 1 S 3 7g 1 -gel, silicas, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, kieselguhr, calcium sulfate, magnesium sulfate, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate 5 and ureas, and vegetable products, such as grain flour, bark meal, wood meal, nutshell meal, cellulosic powders and other solid carriers.

The formulations contain in general from 0.01 to 95, preferably 10 from 0.5 to 90, ~ by weight of active ingredient. The active ingredients are used in a purity of from 90 to 100%, preferably from 95 to 100% (according to NMR/HPLC/GC spectrum).

Examples of such formulations are:
I. 20 parts by weight of compound No. 1 are dissolved in a mixture which consists of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of from 8 to 10 mol of ethylene oxide with 1 mol of N-monoethanololeamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion which contains 0.02% by weight of the active ingredient is obtained.

II. 20 parts by weight of compound No. 1 are dissolved in a mixture which consists of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide with 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion which contains 0.02% by weight of the active ingredient is obtained.

III. 20 parts by weight of active ingredient No. 1 are dissolved in a mixture which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a ~ineral oil fraction boiling within the range from 210 to 280 C
and 10 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion which 0050/43806 2 l S~ 7g 1 contains 0.02% by weight of the active ingredient is obtained.

IV. 20 parts by weight of active ingredient No. 1 are thoroughly mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-~-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor and 60 parts by weight of silica gel powder, and the mixture is milled in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor which contains 0.1% by weight of the active ingredient is obtained.

15 V. 3 parts by weight of active ingredient No. 1 are mixed with 97 parts by weight of finely divided kaolin. A
dusting agent which contains 3% by weight of the active ingredient is obtained in this manner.

20 VI. 20 parts by weight of active ingredient No. 1 are thoroughly mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the - sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

The herbicides or the active ingredients can be applied by the preemergence or postemergence method. If the active ingredients 30 are less well tolerated by certain crops, it is possible to use application methods in which the herbicides are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crops are as far as possible not affected while the active ingredients reach the leaves of undesirable plants growing 35 underneath or the uncovered soil surface (post-directed, lay-by).

The application rates of active ingredient are from 0.001 to 5.0, preferably from 0.01 to 2.0, kg/ha of active ingredient (a.i.), depending on the aim of control, the season, the target plants 40 and the stage of growth.

In view of the versatility of the application methods, the novel compounds I and I' or compositions cont~i n; ng them can also be used in a further number of crops for eliminating undesirable 45 plants. For example, the following crops are suitable:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp.
rapa, Brassica napus var. napus, Brassica napus var.
napobrassica, Brassica rapa var. silvestris, Camellia sinensis, 5 Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), 10 Helianthus annuus, Hevea brasiliensis, Hordeumrvulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.
rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, 15 Phaseolus mungo, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum 20 durum, Vicia faba, Vitis vinifera and Zea mays.

The growth-regulating compounds I and I' can influence virtually all stages of development of a plant in various ways. The versatility of action of the plant growth regulators depends in 25 particular a) on the plant species and plant variety, b) on the time of application, based on the stage of development of the plant, and on the season, 30 c) on the place and method of application (for example seed dressing, soil treatment, foliage application or trunk injection in the case of trees)~
d) on climatic factors, for example temperature, amount of precipitation and also length of day and light intensity, 35 e) on the soil characteristics (including application of fertilizer ), f) on the formulation or application form of the active ingredient and finally g) on the concentration in which the active ingredient is used.

Some the various possible uses of the plant growth regulators of the formula I or I' in plant cultivation, in agriculture and in horticulture are mentioned below.

0050/43806 2~ 53 7~1 _ 17 A. The vegetative growth of the plants can be greatly inhibited by means of the compounds which can be used according to the invention, this being manifested in particular in a reduction in the growth in length.

The treated plants accordingly exhibit stunted growth; in addition, a darker leaf color is observed.

A reduced intensity of growth of grasses and crops susceptible to lodging, such as cereals, corn, sunflowers and soyabean, proves to be advantageous in practice. The resulting shortening and strengthening of the stems reduce or eliminate the danger of lodging of plants under unfavorable weather conditions prior to harvesting.
The use of growth regulators for inhibiting the growth in length and for changing the time of ripening in the case of cotton is also important. This permits completely mechanized harvesting of this important crop.
In the case of fruit trees and other trees, pruning costs can be saved by means of the growth regulators. In addition, the alternation of fruit trees can be broken by growth regulators.
By using growth regulators, it is also possible to promote or inhibit the lateral branching of plants. This is of interest when, for example in the case of tobacco plants, the formation of suckers is to be inhibited in favor of foliar growth.

The frost resistance can also be considerably increased by means of growth regulators, for example in winter rape. On the one hand, the growth in length and the development of foliage and plant mass which is too luxurious (and therefore particularly susceptible to frost) are inhibited. On the other hand, the young rape plants are held back in the vegetative stage of development after sowing and before the onset of the winter frosts, in spite of favorable growth conditions.
This also eliminates the danger of frost to those plants which tend to lose the inhibition of blooming prematurely and to go over into the generative phase. In other crops too, for example winter cereals, it is advantageous if the crops are well tillered in the fall as a result of treatment with the novel compounds but do not begin the winter with growth which is too luxurious. This makes it .

0050/43806 2I ~ 3 7 possible to avoid the increased sensitivity to frost and, owing to the relatively small amount of foliage or plant mass, attack by various diseases (for example fungal disease).

B. Greater yields of both plant parts and plant ingredients can be achieved by means of the growth regulators. For example, it is possible to induce the growth of relatively large amounts of buds, blooms, leaves, fruits, seed kernels, roots and tubers, to increase the content of sugar in sugar beet, sugar cane and citrus fruits, to increase the protein content of cereals and soya bean and to stimulate rubber trees to produce more latex flow.

The compounds of the formula I or I' can increase yields by intervening in the plant metabolism or by promoting or inhibiting vegetative and/or generative growth.

C. Finally, plant growth regulators can be used both to shorten or lengthen the stages of development and to accelerate or delay the ripening of the harvested plant parts before or after the harvest.

For example, facilitating harvesting is of commercial interest, this being permitted by concentrated dropping or reduction of the adhesion to the tree in the case of citrus fruits, olives or other species and varieties of pomes, drupes and hollow-shelled fruits. The same mechanism, ie. promotion of the formation of abscission tissue between fruit or leaf part and stem part of the plant is also essential for readily controllable defoliation of crops such as cotton.

D. Furthermore, the water consumption of plants can be reduced by means of growth regulators. By using the novel substances, it is possible to reduce the intensity of irrigation and hence to carry out more economical farming because, inter alia, the opening of the stomata is reduced, a thicker epidermis and cuticles are formed, root penetration of the soil is improved and the microclimate in the crop is advantageously influenced by a more compact growth.

Compounds I and I' are particularly suitable for shortening the 45 stems of crops such as barley, rape and wheat.

0050/43~06 2~3791 The active ingredients to be used according to the invention and of the formula I or I' can be fed to the crops both via the seed (as seed dressing) and via the soil, ie. through the root and, particularly preferably, via the foliage by spraying.

Owing to the good toleration by plants, the application rate of active ingredient is not critical. The optimum application rate varies depending on the aim of control, the season, the target plants and stages of growth.
In the case of seed treatment, in general from 0.001 to 50 g, preferably from 0.01 to 10 g, of active ingredient are required per kilogram of seed.

15 For foliar and soil treatment, in general doses of from 0.001 to 10, preferably from 0.01 to 3, in particular from 0.01 to 0.5, kg/ha are to be considered as sufficient.

In order to broaden the action spectrum and to achieve 20 synergistic effects, the azaanthraquinones and azaxanthones of the general formula I and I' can be mixed with a large number of typical members of other groups of herbicidal or growth-regulating active ingredients and applied together with them. Suitable components for the mixture are, for example, 25 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 which carry, for example, a 30 carboxyl or carbimino group in the 2-position, quinolinecarboxylic acid derivatives, imidazolinones, sulfonamides, sulfonylureas, and aryloxy- and heteroaryloxyphenoxypropionic acids and their salts, esters and amides and others.
It may also be useful to apply the compounds I or I', alone or in combination with other herbicides, also as a mixture with further crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. The miscibility 40 with mineral salt solutions which are used for eliminating nutrient and trace element deficiencies is also of interest.
Nonphytotoxic oils and oil concentrates may also be added.

The preparation and the use of the active ingredients I or I' are 45 evident from the examples below.

. - 2l~37~a Preparation Examples:

Example 1 5 4-Methylbenzo[g]quinoline-5,10-dione (cleistopholine) 18.5 g (0.165 mol) of crotonaldehyde dimethyl hydrazone, dissolved in 50 ml of xylene, were added to a solution of 30 g of 2-bromo-1,4-naphthaquinone (0.126 mol) in 250 ml of xylene.
lO Stirring was carried out for 8 hours at 140 C, after which the mixture was cooled to 20 C and extracted with 2 N H2SO4. The combined, aqueous extracts were brought to pH 9 with solid potassium carbonate and extracted with ethyl acetate. The combined organic phases were dried over K2CO3 and evaporated down 15 under reduced pressure. 13.4 g (36.3% of theory) of 4-methylbenzo[g]quinoline-5,10-dione were obtained as slightly yellow crystals of melting point 204-206C.

Example 2 7-Methyl-5H-[l]benzopyrano[2,3-b]pyridin-5-one A mixture of 49.5 g (0.19 mol) of ethyl 2-(4-methylphenoxy)-nicotinate and 460 g of polyphosphoric acid 25 were stirred for 8 hours at 140 C, cooled, stirred into 800 g of ice and rendered alkaline with a 28% strength, aqueous ammonia solution, and the resulting precipitate was filtered off with suction, washed successively with water and with a little cold ethanol and dried. 29.3 g (73% of theory) of 30 7-methyl-5H[l]benzopyrano[2,3-b]pyridin-5-one were obtained as yellowish crystals of melting point 155-157 C.

The compounds of the formula I or I' shown in Table 2 were obtained similarly to Preparation Examples 1 and 2 and according 35 to the general instructions for preparation.

Table 2 1~ A R4 ` 0050/43806 2 1 53 7 9 1 Ex. Rl R2 R3 R4 R5A X Y Z M;p.
No. ( C) 1 CH3 H H H H O N CH C=O 204-206 4 H Cl H H H O N CH O160-161 H H Cl H H O N CH O202-205 6 H H H Cl H O N CH O199-200 107 H H H H Cl O N CH O188-190 8 H H Cl H Cl O N CH O198-201 H H C(CH3)3 H H O N CH O98-100 17 H H H OH H O N CH O > 300 19 CH3 H H H Cl O N CH O242-243 CH3 H Cl H Cl O N CH O220-221 21 CH3 H H Cl H O N CH O201-203 22 CH3 Cl H H H O N CH O210-211 23 CH3 H Cl H H O N CH O208-210 30 24 CH3 H CH(CH3)2 H H O N CHO 87- 88 CH3 H C(CH3)3 H H O N CH O156-158 31 CH3 H Br H H O N CH O187-188 32 CH3 H H H i-C3H7 N CH O97- 98 33 CH3 H H H t-C4Hg O N CHO 118-120 38 CH3 H H H Br O N CH O233-237 - 0050/43806 21 ~ 3 79 1 Ex. R1 R2 R3 R4 R5A X Y Z M.p.
No. ( C) 42 CH3 H Cl H H O N CH S188-190 43 CH3 H C(CH3)3 H H o N CH S114-116 10 45 CH3 H CH(CH3)2 H H O N CH S 80- 82 47 CH3 H Cl H H S N CH O160-168 48 CH3 H H Cl H S N CH O168-170 51 CH3 H CH(CH3)2 H H S N CH O 64- 66 52 CH3 H C(CH3)3 H H S N CH O 73- 75 54 CH3 H Br H H S N CH O184-186 CH3 H H H Cl S N CH O161-164 56 CH3 H Cl H Cl S N CH O180-182 CH3 H CH(cH3)2 H H S N CH S 63- 65 61 CH3 H C(CH3)3 H HS N CH S
Use Examples The herbicidal action of the azaanthraquinones and azaxanthones of the formula I or I' was demonstrated by greenhouse 35 experiments The culture vessels used were plastic flowerpots cont~ining loamy sand with about 3.0% of humus as a substrate. The seeds of the test plants were sown separately according to species.

In the preemergence treatment, the active ingredients suspended or emulsified in water were applied by means of finely distributing nozzles, directly after sowing. The vessels were lightly sprinkle-irrigated in order to promote germination and 45 growth and were then covered with transparent plastic covers until the plants had begun to grow. This covering results in ooso/43806 2 1 ~ 3 7 9 1 uniform germination of the test plants, unless this was impaired by the active ingredients.

For the purpose of the postemergence treatment, the test plants, 5 at a height of growth of from 3 to 15 cm, depending on the form of growth, were treated with the active ingredients suspended or emulsified in water. The application rate for the postemergence treatment was 3.0 kg/ha of a.i.

10 The plants were kept at 10-25 C or 20-35 C, according to species.
The experimental period covered from 2 to 4 weeks. During this time, the plants were tended and their reaction to the individual treatments was evaluated.

15 Evaluation was based on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 means no damage or normal course of growth.

20 The plants used in the greenhouse experiments consisted of the following species:

Botanical name Common name 25 Centaurea cyanus Cornflower Equinochloa crus-galli Barnyard grass Ipomoea ssp. Morning glory The results confirm the good herbicidal action of cleistopholine.
30 A very good growth-inhibiting action is achieved by the azaxanthone mentioned under Example 7, in the crops winter wheat and rape.

Claims

1. A novel azaanthraquinone or azaxanthone of the formula I

where R1 is hydrogen or methyl, R2-R5 are each a) hydrogen, b) halogen, c) nitro, d) CONH2 or CONR6R7, where R6 and R1 are each C1-C4-alkyl, e) C1-C8-alkyl which may carry from one to three of the following substituents: halogen, hydroxyl and C1-C6-alkoxy, f) C3-C6-alkenyl, g) C1-C4-alkoxy, h) hydroxyl, i) amino or NR6R7, or j) phenyl which may carry from one to five halogen atoms or from one to three of the following substituents: nitro, C1-C4-alkoxy, C1-C4-alkyl or C1-C4-haloalkyl;

X and Y are each N, N+-o- or CH, with the proviso that only one nitrogen atom or one N-oxide group is present in the ring, and Z and A are each oxygen or sulfur, and the salts of I with those acids which do not adversely affect the herbicidal or plant growth-regulating action of I, with the proviso that the azaxanthones of the formula Ia Ia where R2, R3, R4 and R5 are identical or different and, independently of one another, are each hydrogen, fluorine, chlorine, methyl, methoxy, CF3, CCl3, tert-C4H9, NO2, NH2 or phenyl, are excluded from the claim.

2. A compound of the formula I as claimed in claim 1, in which R1 is methyl.

3. A compound of the formula I as claimed in claim 1, in which X
is nitrogen or an N-oxide group and Y is CH.

4. A herbicide containing a herbicidal amount of a compound of the formula I as claimed in claim 1.

5. A plant growth regulator containing a bioregulatory amount of a compound of the formula I as claimed in claim 1 and inert additives.

6. A method for controlling undesirable plant growth, wherein a herbicidal amount of a compound of the formula I' where R1 is hydrogen or methyl, R2-R5 are each a) hydrogen, b) halogen, c) nitro, d) COOR6, where R6 is C1-C4-alkyl, e) CONH2 or CONR6R7, where R6 and R7 are each C1-C4-alkyl, f) C1-C8-alkyl which may carry from one to three of the following substituents: halogen, hydroxyl and C1-C6-alkoxy, g) C3-C6-alkenyl, h) C1-C4-alkoxy, i) hydroxyl, j) amino or NR6R7, or k) phenyl which may carry from one to five halogen atoms or from one to three of the following substituents: nitro, C1-C4-alkoxy, C1-C4-alkyl or C1-C4-haloalkyl;

X and Y are each N, N+-O- or CH, with the proviso that only one nitrogen atom or one N-oxide group is present in the ring;

Z is oxygen, sulfur or a C=O group and A is oxygen or sulfur;

and the salts of I with those acids which do not adversely affect the herbicidal or plant growth-regulating action of I, is allowed to act on plants or their habitat or on seed.

7. A method for regulating plant growth, wherein the plants, their habitat or their seeds is or are treated with a bioregulatory amount of a compound of the formula I' as claimed in claim 6.

8. A method for controlling undesirable plant growth and for regulating plant growth, wherein the plants, their habitat or their seeds is or are treated with a bioregulatory amount of cleistopholine.

9. Use of a compound of the formula I' as claimed in claim 6, in which R1 is hydrogen, R2 is hydrogen or halogen, R3 is hydrogen, halogen, C1-C4-alkyl or nitro, R4 is hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy or hydroxyl, R5 is hydrogen or halogen, X is N, Y is CH, Z is oxygen, sulfur or C=O and A
is oxygen or sulfur, for the preparation of compositions for controlling undesirable plant growth or for regulating plant growth.

10. Use of cleistopholine for the preparation of compositions for controlling undesirable plant growth or for regulating plant growth.