Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
0050/43806
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
R1 A R2
y ~ R3
~`X~ ZJ~----~ R4
1 5
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;
0050/43806
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
O R2
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.
7 0050/43806
, 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
0050/43806
21~3 79I
Table 1
R1 R2 R3 R4 R5 X Y Z
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 CH 0
H H H H H N+-0- CH 0
CH3 H H H H N CH 0
CH3 H H H H N+-0- CH 0
CH3 H H H H CH N 0
CH3 H H H H CH N+-O- 0
F H H H N CH C=0
H F H H H N CH 0
CH3 F H H H N CH 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
H H F H H N CH 0
CH3 H F H H N CH 0
25 CH3 H F H H CH N C=0
CH3 H F H H CH N 0
CH3 H H F H N CH C=0
H H H F H N CH 0
CH3 H H F H N CH 0
CH3 H H F H CH N C=0
CH3 H H H F N CH C=0
H H H H F N CH 0
CH3 H H H F N CH 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
H CH3 H H H N CH 0
CH3 CH3 H H H N CH 0
CH3 H CH3 H H N CH C=0
20 H H CH3 H H N CH 0
CH3 H CH3 H H N CH 0
CH3 H H CH3 H N CH C=0
H H H CH3 H N CH 0
25 CH3 H H CH3 H N CH 0
CH3 H H CH3 H N+-0- CH C=0
CH3 H H H CH3 N CH C=0
H H H H CH3 N CH 0
CH3 H H H CH3 N CH 0
30 CH3 H C2Hs H H N CH C=0
CH3 H C2Hs H H N CH 0
H H C2H5 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
0050/43806
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
H OCH3 H H H N CH O
CH3 OCH3 H H H N CH O
CH3 OCH3 H H H CH N C=O
CH3 H OCH3 H H N CH C=O
H H OCH3 H H N CH O
CH3 H OCH3 H H N CH O
15 CH3 H OCH3 H H N+-O- CH C=O
CH3 H H OCH3 H N CH C=O
H H H OCH3 H N CH O
CH3 H H OCH3 H N CH O
20 CH3 H H H OCH3 N CH C=O
H H H H OCH3 N CH O
CH3 H H H OCH3 N CH O
CH3 H OC2H5 H H N CH C=O
25 H H OC2H5 H H N CH O
CH3 H OC2H5 H H N CH 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
H CF3 H H H N CH O
35 CH3 CF3 H H H N CH O
CH3 H CF3 H H N CH C=O
H H CF3 H H N CH O
CH3 H CF3 H H N CH O
40 CH3 H H CF3 H N CH C=O
H H H CF3 H N CH O
CH3 H H CF3 H N CH O
CH3 H H CF3 H N+-O- CH C=O
CH3 H H H CF3 N CH C=O
45 H H H H CF3 N CH O
CH3 H H H CF3 N CH O
- 0050/43806
2~L~3791
g
Rl R2 R3 R4 R5 X Y Z
CH3 NO2 H H H N CH C=O
H NO2 H H H N CH O
5 CH3 N2 H H H N CH O
CH3 H N2 H H N CH C=O
H H NO2 H H N CH O
CH3 H NO2 H H N CH O
CH3 H H NO2 H N CH C=O
10 H H H NO2 H N CH O
CH3 H H NO2 H N CH O
CH3 H C6H5 H H N CH C=O
H H C6H5 H H N CH O
15 CH3 H C6H5 H H N CH O
CH3 H H C6H5 H N CH C=O
H H H C6H5 H N CH O
CH3 H H C6H5 H N CH O
20 CH3 H COOCH3 H H N CH C=O
CH3 H COOCH3 H H N CH O
CH3 H COOC2H5 H H N CH C=O
CH3 H COOC2H5 H H N CH O
25 CH3 H CONH2 H H N CH C=O
CH3 H CONH2 H H N CH 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
30 H F H F H N CH O
CH3 F H F H N CH O
CH3 F H H F N CH C=O
H F H H F N CH O
35 CH3 F H H F N CH O
CH3 H F F H N CH C=O
H H F F H N CH O
CH3 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 H F H F N CH O
CH3 F H CH3 H N CH C=O
H F H CH3 H N CH O
CH3 F H CH3 H N CH O
CH3 CH3 H F H N CH O
0050/43806
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
5 CH3 F H H CH3 N CH 0
CH3 CH3 H H F N CH C=0
CH3 CH3 H H F N CH 0
CH3 H F H CH3 N CH C=0
CH3 H F H CH3 N CH 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
25 CH3 CH30 H F H N CH 0
CH3 F H CH30 H N CH C=0
CH3 F H CH30 H N CH 0
CH3 F H H CH30 N CH C=0
CH3 F H H CH30 N CH 0
30 CH3 CH30 H H F N CH C=0
CH3 CH30 H H F N+-0- CH C=0
CH3 CH30 H H F N CH 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
H CH3 H CH3 H N CH 0
CH3 CH3 H CH3 H N CH
- 0050/43806
- ` . 2I~3791
12
Rl R2 R3 R4 R5 X Y Z
CH3 H CH3 CH3 H N CH C=0
CH3 H CH3 CH3 H N CH 0
5 CH3 H CH3 H CH3 N CH C=0
CH3 H CH3 H CH3 N CH 0
CH3 CH3 H H CH3 N CH C=0
CH3 CH3 H H CH3 N CH 0
CH3 CH3 H H CH3 CH N C=0
CH3 CH30 CH30 H H N CH C=0
H CH30 CH30 H H N CH 0
CH3 CH30 CH30 H H N CH 0
CH3 CH30 H CH30 H N CH C=0
15 CH3 CH30 H CH30 H N CH 0
CH3 H CH30 CH30 H N CH C=0
CH3 H CH30 CH30 H N CH 0
CH3 CH30 H H CH30 N CH C=0
20 H CH30 H H CH30 N CH 0
CH3 CH30 H H CH30 N CH 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
H H CH30 H CH30 N CH 0
CH3 H CH30 H CH30 N CH 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
0050/43806
21~3 '79I
13
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
-
14
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:
0050/43806 21 53 791
16
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
18
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
19
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.
0050/43806
. - 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
2 H H CH3 H H O N CH O155-157
3 H H H H H O N CH O183-185
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
9 H H H CH30 H O N CH O179-180
H H F H H O N CH O179-181
15 11 H H H F H O N CH O193-195
12 H H H CF3 H O N CH O170-172
13 H H CH3 H H O N CH O166-168
14 H H H CH3 H O N CH O151-152
H H C(CH3)3 H H O N CH O98-100
16 H H NO2 H H O N CH O235-238
17 H H H OH H O N CH O > 300
18 H H H H H O CH N O183-185
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
26 CH3 H F H H O N CH O192-193
27 CH3 H H H F O N CH O244-246
35 28 CH3 H H F H O N CH O167-168
29 CH3 F H H H O N CH O228-230
CH3 H F H F O N CH O208-210
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
34 CH3 H H H CH3 O N CH O188-190
CH3 H H H C2H5 O N CH O120-122
36 CH3 H CH3 H H O N CH O161-163
45 37 CH3 H C2H5 H H O N CH O96- 97
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)
39 CH3 H H H H O N CH O152-153
CH3 H H H H O N CH S109-111
5 41 CH3 H F H H O N CH S155-157
42 CH3 H Cl H H O N CH S188-190
43 CH3 H C(CH3)3 H H o N CH S114-116
44 CH3 H H H F O N CH S213-215
10 45 CH3 H CH(CH3)2 H H O N CH S 80- 82
46 CH3 H H H H S N CH O137-139
47 CH3 H Cl H H S N CH O160-168
48 CH3 H H Cl H S N CH O168-170
15 49 CH3 H F H H S N CH O175-176
CH3 H H F H S N CH O163-165
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
20 53 CH3 H H H F S N CH O161-163
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
57 CH3 H F H F S N CH O181-183
25 58 CH3 H F H H S N CH S152-154
59 CH3 H H H F S N CH S155-157
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.
