CA2011538A1 - Substitued 1,8-naphthyridines, their preparation and their use as antidotes - Google Patents
Substitued 1,8-naphthyridines, their preparation and their use as antidotesInfo
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- CA2011538A1 CA2011538A1 CA002011538A CA2011538A CA2011538A1 CA 2011538 A1 CA2011538 A1 CA 2011538A1 CA 002011538 A CA002011538 A CA 002011538A CA 2011538 A CA2011538 A CA 2011538A CA 2011538 A1 CA2011538 A1 CA 2011538A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
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Abstract
O.Z. 0050/40631 ABSTRACT OF THE DISCLOSURE: Substituted 1,8-naphthyridines of the general formula I
I, where:
R1 is mercapto, benzylthio, sulfonyl, amino or NR2R3, where R2 is C1-C12-alkyl, C3-C6-alkenyl, C3-C8-cycloalkyl, substituted or unsubstituted phenyl or phenyl-(C1-C3)-alkyl, or a group -?-A, where A is C1-C8-alkyl, substituted or unsubstituted phenyl, or is amino, alkyl- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, phenylamino, morpholino or piperidyl, and R3 is hydrogen, C1-C12-alkyl or C3-C8-cycloalkyl, or R2 and R3 are bonded to one another to form a saturated or unsaturated 5-membered or 6-membered heterocyclic structure which, in addition to the nitrogen atom to which they are bonded, may contain a further heteroatom such as oxygen or nitrogen;
hydroxyl, mercapto, halogen or XR4, where X is oxygen or sulfur and R4 is C1-C12-alkyl, C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, C5-C8-cycloalkyl, or substituted or unsubstituted phenyl or phenyl-C1-C3-alkyl, R5 and R7 are each hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, substituted or unsubstituted phenyl or phenyl-(C1-C3)-alkyl, hydroxyl, halogen, mercapto, C1-C4-alkoxy, C1-C4-alkylthio, amino, mono- or dialkylamino where each alkyl is of 1 to 6 carbon atoms, substituted or unsubstituted phenoxy or phenylthio, halo-(Cl-C3)-alkyl, C1-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, C1-C4-acyloxy, substituted or unsubstituted hydrazino, cyano and thiocyanato, and O.Z. 0050/40631 R5 is hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, substituted or unsubstituted phenyl or phenyl-(C1-C3)-alkyl, halogen, halo-(C1-C3)-alkyl, Cl-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, carboxyl or C1-C4-alkoxy-carbonyl, their plant-tolerated salts, processes for their manufacture, and their use as safeners.
I, where:
R1 is mercapto, benzylthio, sulfonyl, amino or NR2R3, where R2 is C1-C12-alkyl, C3-C6-alkenyl, C3-C8-cycloalkyl, substituted or unsubstituted phenyl or phenyl-(C1-C3)-alkyl, or a group -?-A, where A is C1-C8-alkyl, substituted or unsubstituted phenyl, or is amino, alkyl- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, phenylamino, morpholino or piperidyl, and R3 is hydrogen, C1-C12-alkyl or C3-C8-cycloalkyl, or R2 and R3 are bonded to one another to form a saturated or unsaturated 5-membered or 6-membered heterocyclic structure which, in addition to the nitrogen atom to which they are bonded, may contain a further heteroatom such as oxygen or nitrogen;
hydroxyl, mercapto, halogen or XR4, where X is oxygen or sulfur and R4 is C1-C12-alkyl, C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, C5-C8-cycloalkyl, or substituted or unsubstituted phenyl or phenyl-C1-C3-alkyl, R5 and R7 are each hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, substituted or unsubstituted phenyl or phenyl-(C1-C3)-alkyl, hydroxyl, halogen, mercapto, C1-C4-alkoxy, C1-C4-alkylthio, amino, mono- or dialkylamino where each alkyl is of 1 to 6 carbon atoms, substituted or unsubstituted phenoxy or phenylthio, halo-(Cl-C3)-alkyl, C1-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, C1-C4-acyloxy, substituted or unsubstituted hydrazino, cyano and thiocyanato, and O.Z. 0050/40631 R5 is hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, substituted or unsubstituted phenyl or phenyl-(C1-C3)-alkyl, halogen, halo-(C1-C3)-alkyl, Cl-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, carboxyl or C1-C4-alkoxy-carbonyl, their plant-tolerated salts, processes for their manufacture, and their use as safeners.
Description
O.Z. 0050/40631 Substituted l 8-naphthYridines, their pre~aration and their use as antidote~
The present invention relates to substituted 1,8-naphthyridines of the general formula I
R7~RI
where Rl is mercapto, benzylthio, sulfonyl, amino or NR2R3, R2 i9 Cl-Clz-alkyl, C3-C~-alkenyl, C3-C~-cycloalkyl, phenyl, phenyl-C1-C3-alkyl or phenyl or phenyl-Cl-C3-alkyl which is monosubstituted to trisubstituted by halogen, Cl-C4-alkyl, Cl-C4-alkoxy, amino, or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or a group -C--A
where A is C1-Ca-alkyl or is phenyl which is unsubstituted or monosubstituted to trisubstituted by halogen, C1-C4-alkyl, Cl-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or is amino, alkylamino or dialkylamino where each alkyl radical i8 of 1 to 6 carbon atoms, phenylamino, mor-pholino or piperidyl, and R3 is hydrogen, C1-C12-alkyl or C3-Ca-cycloalkyl, or R2 and R3 are bonded to one another to form a saturated or unsaturated 5-membered or 6-membered heterocyclic struc-ture which, in addltion to the nitrogen atom to which they are bonded, may contain a further heteroatom, such as oxygen or nitrogen, hydroxyl, mercapto, halogen or XR4 where X is oxygen or sulfur and R4 is Cl-C12-alkyl, Cl-C4-alkoxycarbonyl-C1-C4-alkyl, C5-Ca-cycloalkyl, phenyl or phenyl-Cl-C3-alkyl, where the aromatic rings may carry from one to three of the following radicals: halogen, Cl-C4-alkyl, Cl-C4-alkoxy, amino or mono- or dialkylamino,
The present invention relates to substituted 1,8-naphthyridines of the general formula I
R7~RI
where Rl is mercapto, benzylthio, sulfonyl, amino or NR2R3, R2 i9 Cl-Clz-alkyl, C3-C~-alkenyl, C3-C~-cycloalkyl, phenyl, phenyl-C1-C3-alkyl or phenyl or phenyl-Cl-C3-alkyl which is monosubstituted to trisubstituted by halogen, Cl-C4-alkyl, Cl-C4-alkoxy, amino, or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or a group -C--A
where A is C1-Ca-alkyl or is phenyl which is unsubstituted or monosubstituted to trisubstituted by halogen, C1-C4-alkyl, Cl-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or is amino, alkylamino or dialkylamino where each alkyl radical i8 of 1 to 6 carbon atoms, phenylamino, mor-pholino or piperidyl, and R3 is hydrogen, C1-C12-alkyl or C3-Ca-cycloalkyl, or R2 and R3 are bonded to one another to form a saturated or unsaturated 5-membered or 6-membered heterocyclic struc-ture which, in addltion to the nitrogen atom to which they are bonded, may contain a further heteroatom, such as oxygen or nitrogen, hydroxyl, mercapto, halogen or XR4 where X is oxygen or sulfur and R4 is Cl-C12-alkyl, Cl-C4-alkoxycarbonyl-C1-C4-alkyl, C5-Ca-cycloalkyl, phenyl or phenyl-Cl-C3-alkyl, where the aromatic rings may carry from one to three of the following radicals: halogen, Cl-C4-alkyl, Cl-C4-alkoxy, amino or mono- or dialkylamino,
- 2 - O.Z. 0050/40631 where each alkyl radical is of 1 to 6 carbon atoms, R5 and R7 are each hydrogen, Cl-C12-alkyl, or C3-C8-cyclo-alkyl, phenyl or phenyl-C~-C~-alkyl, where the phenyl nucleus in each case may in turn carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C~-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of l to 4 carbon atoms;
hydroxyl, halogen, mercapto, Cl-C4-alkoxy, Cl-C4-alkylthio, amino, mono- or dialkylamino, where each alkyl radical is of 1 to 6 carbon atoms, phenoxy or phenylthio, where the phenyl nucleus in each case may in turn carry from one to three of the following groups: halogen, C1-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, amino or mono- or dialkyl-amino where each alkyl radical is of 1 to 4 carbon atoms;
halo-C,-C3-alkyl,Cl-C4-alkoxy-Cl-C3-alkyl,Cl-C4-alkylthio-Cl-C3-alkyl, amino-Cl-C3-alkyl, Cl-C4-acyloxy, hydrazino which may carry from one to three C1-C4-alkyl radicals and/or a C1-C~-acyl radical; cyano or thiocyanato, and R6 is hydrogen, Cl-Cl2-alkyl, C3-C~-cycloalkyl, phenyl or phenyl-C1-C3-alkyl, where the phenyl nucleus in each case may in turn carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C~-C4-halo-alkyl, amino or mono- or dialkylamino, where each alkyl radical is of 1 to 4 carbon atoms; halogen, halo-C1-C3-alkyl, Cl-C4-alkoxy-Cl-C3-alkyl, Cl-C~-alkylthio-Cl-C3-alkyl, amino-C,-C3-alkyl, carboxyl or C,-C~-alkoxycarbonyl, and their plant-tolerated salts.
: The present invention furthermore relate~ to a process for the preparation of the compounds I and herb-icide~ which contain the 2-(4-hetaryloxy)- or 2-(4-aryl-oxy)-phenoxyacetic acid derivatives or propionic acid derivatives and/or cyclohexenone derivative~ as herb-icidal active ingredients and substituted 1,8-naph-thyridines as antidotes, and methods for selectively con-trolling undesirable plant growth with these herbicides.
An overview of the preparation of various 1,8-naphthyridine derivatives is given by P.A. Lowe in
hydroxyl, halogen, mercapto, Cl-C4-alkoxy, Cl-C4-alkylthio, amino, mono- or dialkylamino, where each alkyl radical is of 1 to 6 carbon atoms, phenoxy or phenylthio, where the phenyl nucleus in each case may in turn carry from one to three of the following groups: halogen, C1-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, amino or mono- or dialkyl-amino where each alkyl radical is of 1 to 4 carbon atoms;
halo-C,-C3-alkyl,Cl-C4-alkoxy-Cl-C3-alkyl,Cl-C4-alkylthio-Cl-C3-alkyl, amino-Cl-C3-alkyl, Cl-C4-acyloxy, hydrazino which may carry from one to three C1-C4-alkyl radicals and/or a C1-C~-acyl radical; cyano or thiocyanato, and R6 is hydrogen, Cl-Cl2-alkyl, C3-C~-cycloalkyl, phenyl or phenyl-C1-C3-alkyl, where the phenyl nucleus in each case may in turn carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C~-C4-halo-alkyl, amino or mono- or dialkylamino, where each alkyl radical is of 1 to 4 carbon atoms; halogen, halo-C1-C3-alkyl, Cl-C4-alkoxy-Cl-C3-alkyl, Cl-C~-alkylthio-Cl-C3-alkyl, amino-C,-C3-alkyl, carboxyl or C,-C~-alkoxycarbonyl, and their plant-tolerated salts.
: The present invention furthermore relate~ to a process for the preparation of the compounds I and herb-icide~ which contain the 2-(4-hetaryloxy)- or 2-(4-aryl-oxy)-phenoxyacetic acid derivatives or propionic acid derivatives and/or cyclohexenone derivative~ as herb-icidal active ingredients and substituted 1,8-naph-thyridines as antidotes, and methods for selectively con-trolling undesirable plant growth with these herbicides.
An overview of the preparation of various 1,8-naphthyridine derivatives is given by P.A. Lowe in
- 3 - O.Z. 0050/40631 Comprehensive Heterocyclic Chemistry (editors:
A.R. Ratritzky and C.W. Rees), Vol. 2, 1st edition (1984), Chapter 2.11. The synthesis of 1,8-naphthyridine derivatives is also described by P. Caluwe in Tetrahedron 36 (1980), 2359-2407, in particular 2391-2394.
The crop protection activity of this class of compound is not evident from the prior art.
Herbicidal active ingredients from the group con-sisting of the 2-(4-hetaryloxy)- or 2-(4-aryloxy)-phen-oxyacetic acid derivatives of the formula IV
RC
Ra ~ CH-CO2Rb IV
where R~ is a phenyl ring, a pyridyl ring, a benzoxazyl radical, a benzthiazyl radical or a benzopyrazinyl -radical, and these aromatic ring systems may carry up to two of the following radLcals: halogen, nitro, Cl-C4-alkyl, Cl-C4-haloalkyl and/or Cl-C~-haloalkoxy, * is hydrogen, Cl-C4-alkyl or one equivalent of a plant-tolerated cation and Rc is hydrogen or methyl, ~re disclosed in the literature, for example in DE-A-22 23 894, DE-A-24 33 067, DE-A-25 76 251, DE-A-30 04 770, BE-A-868 875 and BE-A-858 618.
They are used for controlling undesirable plants from the Gramineae family. However, the tolerance of these substances by crops varies between commercially acceptable and non-tolerated, depending on the substitu-ents and application rate.
The same situation is encountered with cyclo-hexenone derivatives of the formula v ORi Rf ~ NodRe V
where Rd is C1-C4-alkyl;
R- i3 Cl-C4-alkyl, C3- or C4-alkenyl, C3- or C~-alkynyl, C3-_ 4 _ o.z. 0050/40631 or C4-haloalkylene or thenyl which may be substituted by a halogen atom;
R is Cl-C4-alkyl which may be monosubstituted or disub-stituted by Cl-C4-alkylthio or Cl-C4-alkoxy;
a 5-membered or 6-membered saturated or monounsaturated ring system which, in addition to carbon members, may contain an oxygen or sulfur atom or a sulfGxyl or sulfon-yl group, and this ring may carry up to three of the following radicals: hydroxyl, halogen, Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy and/or Cl-C4-alkylthio;
a 10-membered saturated or monounsaturated heterocyclic structure which contains two oxygen atoms or sulfur atoms and may be substituted by up to three Cl-C4-alXyl groups and/or methoxy groups;
a phenyl, pyridyl, thiazolyl, pyrazolyl, pyrrolyl or isoxazolyl radical which may carry up to three of the following groups: Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy,Cl-C4-alkylthio,C3-C6-alkenyloxy,C3-C5-alkynyloxy, Cl-C4-alkoxy-Cl-C3-alkyl, Cl-C~-dialkoxy-Cl-C3-alkyl, formyl, halogen and/or benzoylamino, R~ is hydrogen or hydroxyl or, when R~ is Cl-Cs-alkyl, is Cl-C6-alkyl;
Rh is hydrogen, cyano, halogen, C1-C4-alkoxycarbonyl or a Cl-C~-alkylketoxime group and Rl is hydrogen or one equivalent of an environmentally compatible cation.
They are likewise described in the literature (eg. EP-A 228 598, EP-A 230 235, EP-A 238 021, US-A 4 432 786, DE-A 24 39 104) as herbicide~ and are predominantly used for controlling undesirable grasses in dicotyledon crops and in grasses which do not belong to the Gramineae family. Depending on the structure of the substituents and the application rate, compounds of this group can also be used for selectively controlling undesirable grasses in gramineous crops, such as wheat and rice.
It is an ob~ect of the present invention to pro-vide compounds which at least reduce the disadvantages ~. J ~ i 3 - 5 - O.Z. 0050/40631 encountered in using the abovementioned herbicides of the formulae IV and V to such an extent that the harvest yield of the crops is not significantly reduced, if at all.
5We have found that this object is achieved by the substituted 1,8-naphthyridines I defined at the outset.
We have also found processes for the preparation of these compounds I and for the ~oint use of these compounds with the herbicides IV and V for influencing undesirable plant 10growth. The present invention furthermore relates to agents which contain the compounds I, and it is unimpor-tant whether the herbicidal active ingredient and the antidote compound are formulated and applied together or separately or, in the case of separate application, in 15which order the herbicidal active ingredient and the antidote are applied.
The novel compounds I are obtainable by reacting 2,6-diaminopyridine II with a B-dicarbonyl compound III.
The substitution pattern can be varied within a 20wide range by appropriate choice of the B-dicarbonyl com-pound III; in addition to 1,3-diketones, malonaldehydes or their acetal~ and B-ketoaldehydes or their acetals, it is also possible to use malonic esters, B-keto esters and B-formyl esters or their acetals for the cyclocondensa-25tion to give I.
~he preparation of I is illustrated by the following equations:
a) C=O R5 R 7 0 H 2~NH 2 --2H 2 R 7~NH 2 Ill 11 where, for example, R5 and R7 are each H, alkyl, cyclo-alkyl, phenyl, phenylalkyl, haloalkyl or alkoxyalkyl and R6 is H, alkyl, cycloalkyl, phenyl, phenylalkyl, halogen, - 6 - O.Z. 0050/40631 haloalkyl or alkoxyalkyl b) RS
l=o R S OH
R6--CH I J~ ' ~ R6~
O=C-OAlkyl H2N N NH2 --AlkylOH H N N NH2 RS N N NH2 111 II 1~ bzw. Ib The structural isomers Ia and Ib are formed as a mixture but can be obtained individually by conventional separation method~, for example by recrystallization or chromatography.
c) OA 1 ky I
~C--O OH
R 6-. I H + ~ R~
o=C-OAlkyl H2 N NH2 --2 A1ky1OH H N N NH2 1ll II Ic 2- or 4-hydroxy-1,8-naphthyridines Ia and Ib and 2,4-dihydroxy-1,8-naphthyridines Ic react with a halogen-ating agent, such as phosphorous oxychloride or -bromide to give 2- or 4-halonaphthyridines or 2,4-dihalonaph-thyridines, respectively. By reactions to exchange the halogen for N, S or O nucleophile~ and C nucleophiles, such as cyanide, the substitution pattern of I can be varied within a wide range.
Furthermore, the primary amino function of the substituted 1,8-naphthyridines I can be derivatized in a conventional manner, for example alkylated or acylated.
It i9 also possible to convert the primary amino group of I into a hydroxyl group by diazotization in acidic aqueous solution and boiling of the resulting diazonium salt.
The substituted 1,8-naphthyridines I where Rl is OH, which are prepared in this manner, react with halogenating agents, such as phosphorus oxychloride or _ 7 _ o.Z. 0050/40631 -bromide in a manner similar to that described above to give the corresponding 1,8-naphthyridines I where Rl is halogen.
The halogen introduced in this manner in place of the primary amino function of I can undergo the above-mentioned nucleophilic exchange reaction~ so that further variations of the substitution pattern of I are possible.
Usually, the starting materials II and III are used in a stoichiometric ratio. However, an excess of one or other may be quite advantageous in specific cases.
The reaction can be carried out continuously or batchwise under atmospheric, superatmospheric or reduced pressure using the conventional methods. The reaction temperature is in general from 20 to 400C, in particular from 50 to 300C, advantageously in the boiling range of the solvent.
Advantageously used solvents and condensing agents are acids, such as sulfuric acid, phosphoric acid, acetic acid and mixtures thereof, and relatively high-boiling ethers, such as dipheny} ether, dioxane or tetra-hydrofuran. In certain cases, it may also be advan-tageous to heat the two starting compounds I and II in the absence of a solvent.
In addition to the abovementioned solvents, how-~5 ever, other suitable ones are aliphatic and aromatichydrocarbons and chlorohydrocarbons.
In view of the intended use of the compounds I as crop protection agents, suitable substituents are the following radicals~
Rl is mercapto, benzylthio, hydroxyl, Cl-C4-alkoxy, sulfonyl (S03H), amino or NR2R3, where R2 is C1-Cl2-alkyl, C3-C3-alkenyl, C3-C3-cycloalkyl, phenyl, phenyl-Cl-C3-alkyl or phenyl or phenyl-C1-C3-alkyl which is substituted by halogen, Cl-C4-alkyl, C,-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or a group R
--C--A
ci 3 - 8 - O.Z. OOS0/40631 where A is Cl-C8-alkyl or is phenyl which is unsubstituted or monosubstituted to trisubstituted by halogen, C1-C~-alkyl, Cl-C4-alkoxy, amino or mono- or dialk~lamino where each alkyl radical is of 1 to 6 carbon atoms, or is S amino, alkyl- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, phenylamino, morpholino or piperidyl, and R3 is hydrogen, C1-Cl2-alkyl or C3-C8-cycloalkyl, or R2 and R3 are bonded to one another to form a saturated or unsaturated S-membered or 6-membered heterocyclic struc-ture which may contain a further heteroatom, such as oxy-gen or nitrogen;
hydroxyl, mercapto, halogen, in particular fluorine, chlorine or bromine, or XR4 where X is oxygen or sulfur and R~ is Cl-Cl2-alkyl, Cl-Cj-alkoxycarbonyl-C1-C~-alkyl, C5-C8-cycloalkyl, phenyl which is un3ubstituted or substituted by halogen, C1-C~-alkyl, C1-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or unsubstituted or substituted phenyl-C1-C3-alkyl, R5 and R7 are each hydrogen, C1-C12-alkyl, in particular C1-C~-alkyl, particularly preferably C1-C~-alkyl as stated for R2, C3-C8-cycloalkyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, phenyl or phenyl-C1-C3-alkyl, where the phenyl nucleus in each case is unsubstituted or substituted by C1-C~-alkyl, halogen, such as fluorine, chlorine or bromine, C1-C~-alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy or tert-butoxy, C1-C~-haloalkyl, eg. CF3, amino or mono- or dialkylamino where each alkyl radical is of 1 to
A.R. Ratritzky and C.W. Rees), Vol. 2, 1st edition (1984), Chapter 2.11. The synthesis of 1,8-naphthyridine derivatives is also described by P. Caluwe in Tetrahedron 36 (1980), 2359-2407, in particular 2391-2394.
The crop protection activity of this class of compound is not evident from the prior art.
Herbicidal active ingredients from the group con-sisting of the 2-(4-hetaryloxy)- or 2-(4-aryloxy)-phen-oxyacetic acid derivatives of the formula IV
RC
Ra ~ CH-CO2Rb IV
where R~ is a phenyl ring, a pyridyl ring, a benzoxazyl radical, a benzthiazyl radical or a benzopyrazinyl -radical, and these aromatic ring systems may carry up to two of the following radLcals: halogen, nitro, Cl-C4-alkyl, Cl-C4-haloalkyl and/or Cl-C~-haloalkoxy, * is hydrogen, Cl-C4-alkyl or one equivalent of a plant-tolerated cation and Rc is hydrogen or methyl, ~re disclosed in the literature, for example in DE-A-22 23 894, DE-A-24 33 067, DE-A-25 76 251, DE-A-30 04 770, BE-A-868 875 and BE-A-858 618.
They are used for controlling undesirable plants from the Gramineae family. However, the tolerance of these substances by crops varies between commercially acceptable and non-tolerated, depending on the substitu-ents and application rate.
The same situation is encountered with cyclo-hexenone derivatives of the formula v ORi Rf ~ NodRe V
where Rd is C1-C4-alkyl;
R- i3 Cl-C4-alkyl, C3- or C4-alkenyl, C3- or C~-alkynyl, C3-_ 4 _ o.z. 0050/40631 or C4-haloalkylene or thenyl which may be substituted by a halogen atom;
R is Cl-C4-alkyl which may be monosubstituted or disub-stituted by Cl-C4-alkylthio or Cl-C4-alkoxy;
a 5-membered or 6-membered saturated or monounsaturated ring system which, in addition to carbon members, may contain an oxygen or sulfur atom or a sulfGxyl or sulfon-yl group, and this ring may carry up to three of the following radicals: hydroxyl, halogen, Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy and/or Cl-C4-alkylthio;
a 10-membered saturated or monounsaturated heterocyclic structure which contains two oxygen atoms or sulfur atoms and may be substituted by up to three Cl-C4-alXyl groups and/or methoxy groups;
a phenyl, pyridyl, thiazolyl, pyrazolyl, pyrrolyl or isoxazolyl radical which may carry up to three of the following groups: Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy,Cl-C4-alkylthio,C3-C6-alkenyloxy,C3-C5-alkynyloxy, Cl-C4-alkoxy-Cl-C3-alkyl, Cl-C~-dialkoxy-Cl-C3-alkyl, formyl, halogen and/or benzoylamino, R~ is hydrogen or hydroxyl or, when R~ is Cl-Cs-alkyl, is Cl-C6-alkyl;
Rh is hydrogen, cyano, halogen, C1-C4-alkoxycarbonyl or a Cl-C~-alkylketoxime group and Rl is hydrogen or one equivalent of an environmentally compatible cation.
They are likewise described in the literature (eg. EP-A 228 598, EP-A 230 235, EP-A 238 021, US-A 4 432 786, DE-A 24 39 104) as herbicide~ and are predominantly used for controlling undesirable grasses in dicotyledon crops and in grasses which do not belong to the Gramineae family. Depending on the structure of the substituents and the application rate, compounds of this group can also be used for selectively controlling undesirable grasses in gramineous crops, such as wheat and rice.
It is an ob~ect of the present invention to pro-vide compounds which at least reduce the disadvantages ~. J ~ i 3 - 5 - O.Z. 0050/40631 encountered in using the abovementioned herbicides of the formulae IV and V to such an extent that the harvest yield of the crops is not significantly reduced, if at all.
5We have found that this object is achieved by the substituted 1,8-naphthyridines I defined at the outset.
We have also found processes for the preparation of these compounds I and for the ~oint use of these compounds with the herbicides IV and V for influencing undesirable plant 10growth. The present invention furthermore relates to agents which contain the compounds I, and it is unimpor-tant whether the herbicidal active ingredient and the antidote compound are formulated and applied together or separately or, in the case of separate application, in 15which order the herbicidal active ingredient and the antidote are applied.
The novel compounds I are obtainable by reacting 2,6-diaminopyridine II with a B-dicarbonyl compound III.
The substitution pattern can be varied within a 20wide range by appropriate choice of the B-dicarbonyl com-pound III; in addition to 1,3-diketones, malonaldehydes or their acetal~ and B-ketoaldehydes or their acetals, it is also possible to use malonic esters, B-keto esters and B-formyl esters or their acetals for the cyclocondensa-25tion to give I.
~he preparation of I is illustrated by the following equations:
a) C=O R5 R 7 0 H 2~NH 2 --2H 2 R 7~NH 2 Ill 11 where, for example, R5 and R7 are each H, alkyl, cyclo-alkyl, phenyl, phenylalkyl, haloalkyl or alkoxyalkyl and R6 is H, alkyl, cycloalkyl, phenyl, phenylalkyl, halogen, - 6 - O.Z. 0050/40631 haloalkyl or alkoxyalkyl b) RS
l=o R S OH
R6--CH I J~ ' ~ R6~
O=C-OAlkyl H2N N NH2 --AlkylOH H N N NH2 RS N N NH2 111 II 1~ bzw. Ib The structural isomers Ia and Ib are formed as a mixture but can be obtained individually by conventional separation method~, for example by recrystallization or chromatography.
c) OA 1 ky I
~C--O OH
R 6-. I H + ~ R~
o=C-OAlkyl H2 N NH2 --2 A1ky1OH H N N NH2 1ll II Ic 2- or 4-hydroxy-1,8-naphthyridines Ia and Ib and 2,4-dihydroxy-1,8-naphthyridines Ic react with a halogen-ating agent, such as phosphorous oxychloride or -bromide to give 2- or 4-halonaphthyridines or 2,4-dihalonaph-thyridines, respectively. By reactions to exchange the halogen for N, S or O nucleophile~ and C nucleophiles, such as cyanide, the substitution pattern of I can be varied within a wide range.
Furthermore, the primary amino function of the substituted 1,8-naphthyridines I can be derivatized in a conventional manner, for example alkylated or acylated.
It i9 also possible to convert the primary amino group of I into a hydroxyl group by diazotization in acidic aqueous solution and boiling of the resulting diazonium salt.
The substituted 1,8-naphthyridines I where Rl is OH, which are prepared in this manner, react with halogenating agents, such as phosphorus oxychloride or _ 7 _ o.Z. 0050/40631 -bromide in a manner similar to that described above to give the corresponding 1,8-naphthyridines I where Rl is halogen.
The halogen introduced in this manner in place of the primary amino function of I can undergo the above-mentioned nucleophilic exchange reaction~ so that further variations of the substitution pattern of I are possible.
Usually, the starting materials II and III are used in a stoichiometric ratio. However, an excess of one or other may be quite advantageous in specific cases.
The reaction can be carried out continuously or batchwise under atmospheric, superatmospheric or reduced pressure using the conventional methods. The reaction temperature is in general from 20 to 400C, in particular from 50 to 300C, advantageously in the boiling range of the solvent.
Advantageously used solvents and condensing agents are acids, such as sulfuric acid, phosphoric acid, acetic acid and mixtures thereof, and relatively high-boiling ethers, such as dipheny} ether, dioxane or tetra-hydrofuran. In certain cases, it may also be advan-tageous to heat the two starting compounds I and II in the absence of a solvent.
In addition to the abovementioned solvents, how-~5 ever, other suitable ones are aliphatic and aromatichydrocarbons and chlorohydrocarbons.
In view of the intended use of the compounds I as crop protection agents, suitable substituents are the following radicals~
Rl is mercapto, benzylthio, hydroxyl, Cl-C4-alkoxy, sulfonyl (S03H), amino or NR2R3, where R2 is C1-Cl2-alkyl, C3-C3-alkenyl, C3-C3-cycloalkyl, phenyl, phenyl-Cl-C3-alkyl or phenyl or phenyl-C1-C3-alkyl which is substituted by halogen, Cl-C4-alkyl, C,-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or a group R
--C--A
ci 3 - 8 - O.Z. OOS0/40631 where A is Cl-C8-alkyl or is phenyl which is unsubstituted or monosubstituted to trisubstituted by halogen, C1-C~-alkyl, Cl-C4-alkoxy, amino or mono- or dialk~lamino where each alkyl radical is of 1 to 6 carbon atoms, or is S amino, alkyl- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, phenylamino, morpholino or piperidyl, and R3 is hydrogen, C1-Cl2-alkyl or C3-C8-cycloalkyl, or R2 and R3 are bonded to one another to form a saturated or unsaturated S-membered or 6-membered heterocyclic struc-ture which may contain a further heteroatom, such as oxy-gen or nitrogen;
hydroxyl, mercapto, halogen, in particular fluorine, chlorine or bromine, or XR4 where X is oxygen or sulfur and R~ is Cl-Cl2-alkyl, Cl-Cj-alkoxycarbonyl-C1-C~-alkyl, C5-C8-cycloalkyl, phenyl which is un3ubstituted or substituted by halogen, C1-C~-alkyl, C1-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or unsubstituted or substituted phenyl-C1-C3-alkyl, R5 and R7 are each hydrogen, C1-C12-alkyl, in particular C1-C~-alkyl, particularly preferably C1-C~-alkyl as stated for R2, C3-C8-cycloalkyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, phenyl or phenyl-C1-C3-alkyl, where the phenyl nucleus in each case is unsubstituted or substituted by C1-C~-alkyl, halogen, such as fluorine, chlorine or bromine, C1-C~-alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy or tert-butoxy, C1-C~-haloalkyl, eg. CF3, amino or mono- or dialkylamino where each alkyl radical is of 1 to
4 carbon atoms, particularly suitable phenylalkyl radi-cals being unsubstituted or substituted benzyl or phenyl-ethyl, hydroxyl, mercapto, halogen, such as chlorine or bromine, Cl-C~-alkoxy or alkylthio, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy or the corresponding alkylthio radicals, amino, mono- or - 3 - O.Z. 0050/40631 dialkylamino where each alkyl radical is of 1 to 6 carbon atom~, for example as stated for R2, phenoxy or phenylthio, where the phenyl nucleus in each ca~e may carry the substituents stated for phenyl or phenyl-C1-C3-alkyl, halo-Cl-C3-alkyl, eg. trifluoromethyl, trichloromethyl or 1,2-difluoroethyl, C1-C4-alkoxy- or -alkylthio-C1-C3-alkyl, eg. methoxymethyl or methylmercaptomethyl, amino-Cl-C3-alkyl, eg. dimethylaminomethyl, Cl-C4-acyloxy, hydrazino which is unsubstituted or substituted by one to three Cl-C4-alkyl radicals, in particular by two geminal or vicinal C1-Cj-alkyl radicals, eg. methyl or ethyl, or is monoacylated, suitable acyl radicals being C~-C4-acyl, in particula~ acetyl, cyano or thiocyanato, and R6 is hydrogen, Cl-C1z-alkyl, in particular Cl-C~-alkyl as stated for R2, C3-C~-cycloalkyl, in particular cyclopropyl, cyclopentyl, cyclohexyl, unsubstituted or substituted phenyl or phenyl-C1-C3-alkyl as stated for R5 and R7, halogen or halo-C1-C3-alkyl, in each case a~ stated for Rs and R7, - 25 Cl-C4-alkoxy- or -alkylthio- or amino-Cl-C3-alkyl, in each case as stated for R5 and R7, carboxyl and Cl-C~-alkoxycarbonyl, eg. methoxycarbonyl or ethoxy-carbonyl.
Suitable ~alts of the compounds of the formula I
are agriculturally suitable salts, for example alkali metal salts, in particular the potas4ium or sodium salt, alkaline earth metal salts, in particular the calcium, magnesium or barium salt, manganese salts, copper salts, zinc salts or iron salts and ammonium, phosphonium, sulfonium or sulfoxonium salts, for example ammonium salts, tetraalkylammonium salts, benzyltrialkylammonium - 10 - O.Z. 0050/40631 salts, trialkylsulfonium salts or trialkylsulfoxonium salts.
Specific examples herbicidal (hetaryloxy)- or aryloxyphenoxyacetic acid derivatives of the formula IV
whose toleration by crops can be improved by substituted 1,8-naphthyridine~ of the formula I are listed in Table A below.
11 O.Z. 0050/40631 Table A RC
Ra ~ CH-CO2Rb IV
a b c No. R R R Lit IV.1 ~Cl CH3 CH3 DE-A 22 23 894 IV.2 ~ CF3 n-C4Hg CH3 BE-A 868 875 IV.3 ~Cl C2H5 CH3 BE-A 858 618 N
IV.4 ~ CF3 CH3 CH3 BE-A 868 875 Cl IV.5 ~N ~ Cl C2H5 CH3 DE-A 30 04 770 Specific examples of cyclohexenones of the formula V whose tolerance by crop plants can be improved by substituted 1,8-naphthyridines of the
Suitable ~alts of the compounds of the formula I
are agriculturally suitable salts, for example alkali metal salts, in particular the potas4ium or sodium salt, alkaline earth metal salts, in particular the calcium, magnesium or barium salt, manganese salts, copper salts, zinc salts or iron salts and ammonium, phosphonium, sulfonium or sulfoxonium salts, for example ammonium salts, tetraalkylammonium salts, benzyltrialkylammonium - 10 - O.Z. 0050/40631 salts, trialkylsulfonium salts or trialkylsulfoxonium salts.
Specific examples herbicidal (hetaryloxy)- or aryloxyphenoxyacetic acid derivatives of the formula IV
whose toleration by crops can be improved by substituted 1,8-naphthyridine~ of the formula I are listed in Table A below.
11 O.Z. 0050/40631 Table A RC
Ra ~ CH-CO2Rb IV
a b c No. R R R Lit IV.1 ~Cl CH3 CH3 DE-A 22 23 894 IV.2 ~ CF3 n-C4Hg CH3 BE-A 868 875 IV.3 ~Cl C2H5 CH3 BE-A 858 618 N
IV.4 ~ CF3 CH3 CH3 BE-A 868 875 Cl IV.5 ~N ~ Cl C2H5 CH3 DE-A 30 04 770 Specific examples of cyclohexenones of the formula V whose tolerance by crop plants can be improved by substituted 1,8-naphthyridines of the
5 formula I are given in Table B below.
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?, 17 O.z. 0050/40631 The herbicidal active ingredients and antidotes may be applied together or separately to the leaves and shoots of the crop plants and unwanted plants. Preferably, the antidote is applied together with the herbicidal active ingredient. If the components are applied separately, the antidote 5 is applied first to the field and then the herbicidal active ingredient.
The herbicidal active ingredient and antidote may be formulated together or separately as spray agents in the form of suspensions, emulsions or solutions.
10 Treatment of the crop plant seed with the antidote prior to sowing is also feasible. The herbicidal active ingredient is then applied on its own in conventional manner.
For herbicidal (heteroaryloxy)-phenoxyacetic acid derivatives, the amount 15 of antidotally active compound varies, depending on the crop. The ratios may vary over a wide range, and are also dependent on the structure of the ~heteroaryloxy)phenoxyacetic acid derivatives and on the crop involved.
Suitable ratios of herbicidal active ingredient to antidote are from 1:10 to 1:0.01, and preferably from 1:4 to 1:0.1, parts by weight.
For the same cyclohexenone derivative, the amount of antidote varies, depending on the crop. The ratios in which a cyclohexenone derivative and a l,8-naphthyridine derivative I are used may vary over a wide range, and are dependent on the structure of the cyclohexenone derivative, the naph-25 thyridine derivative I and the crop involved. Suitable ratios of herbicid-al active ingredient to safener are from 1:10 to 1:0.01, and preferably from 1:4 to 1:0.25, parts by weight.
The novel herbicidal agents may contain, in addition to the naphthyridine 30 derivative I as safener and the herbicide from the group of the (hetero-aryloxy)phenoxyacetic acids IV or cyclohexenones V, other herbicidal or growth-regulating active ingredients of different chemical structure without the safening effect being impaired.
35 The agents according to the invention, or - when applied separately - the herbicidal active ingredients and the safener, are applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or others), dispersions, emulsions, oil dis-persions, pastes, dusts, broadcasting agents or granules by spraying, 40 atomizing, dusting, broadcasting or pouring. The forms of application de-pend entirely on the purpose for which the active ingredients are to be used.
Q ~
18 O.Z. 0050/40631 For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vege-table or animal origin, aliphatic, cyclic and aromatic hydrocarbons such 5 as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, lO etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the herbicidal active ingredients and/or anti-15 dotes as such or dissolved in an oil or solvent may be homogenized inwater by means of wetting or dispersing agents, adherents or emulsifiers.
Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalene-sulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and 25 alkyl, lauryl ether and fatty alcohol sulfates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sul-fate, fatty alcohol sulfates, and salts of sulfated hexadecanols, hepta-decanols, and octadecanols, salts of fatty alcohol glycol ethers, conden-sation products of sulfonated naphthalene and naphthalene derivatives with 30 formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonyl-phenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene 35 oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grind-40 ing the herbicidal active ingredients and/or antidote with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of 19 o.Z. 0050~40631 solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium S sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably from 0.5 to 90,10 wt% of herbicidal active ingredient and antidote. The herbicidal active ingredient is applied at rates of from 0.2 to 5 kg/ha.
The present invention is further illustrated by the following examples.
15 Example 1 2-Amino-S-chloromethyl-7-hydroxy-1,8-naphthyridine 32.9 9 (0.2 mol) of ethyl 4-chloroacetoacetate is dripped into a suspen-20 sion of 21.8 9 (0.2 mol) of 2,6-diaminopyridine in 100 ml of 85% strength phosphoric acid. The reaction mixture is stirred for 3 hours at 90C, cooled and poured into ice water, followed by neutralization with concen-trated aqueous ammonia solution. The precipitate is suction filtered, stirred into water again and finally boiled with acetonitrile. 22.8 9 25 (54%) of the title compound is obtained; m.p.: >280C.
Example 2 2-Amino-5-methoxymethyl-7-hydroxy-1,8-naphthyridine A mixture of 21.8 9 (0.2 mol) of 2,6-diaminopyridine and 29.2 9 (0.2 mol) of methyl 4-methoxyacetoacetate in 400 ml of glacial acetic acid is stirred under reflux for 3 hours. After cooling, the precipitate is suction filtered and stirred with 150 ml of cold ethanol. 8 9 (20~) of the 35 title compound is obtained; m.p.: >290C.
Example 3 Acetylation of 2-amino-5,7-dihydroxy-1,8-naphthyridine A mixture of 17.7 g tO.l mol) of 2-amino-5,7-dihydroxy-1,8-naphthyridine prepared in accordance with Lit.3) and 250 ml of acetic anhydride is stirred under reflux for 30 minutes. After cooling, the precipitate is suction filtered, washed with acetone and dried. There is obtained 20.9 9 (8~%~ of a mixture of 2-acetylamino-5-hydroxy-7-acetoxy-1,8-naphthyridine and 2-acetylamino-5-acetoxy-7-hydroxy-1,8-naphthyridine; m.p.: >300C.
2 ~ 3 O.Z. 0050/40631 This mixture can be used direct in the chlorination with POC13 described below.
Example 4 2-Amino-5,7-dichloro-1,8-naphthyridine A suspension of 63 9 (0.241 mol) of the mixture prepared in Example 3 and 600 ml of POC13 is slowly heated to the reflux temperature and then 10 stirred for 2 hours under reflux. Subsequently, the reaction mixture, which has been concentrated to about half its volume, is carefully dripped with ice cooling into 2.5 liters of ice water. The resulting mixture is stirred for one hour at 95-100C and then cooled, the residue is filtered off and the filtrate is brought to a pH of 6. The precipitate is suction 15 filtered, washed thoroughly with warm water and dried. There is obtained 47.9 9 (92%) of the title compound; m.p.: 213-216C.
Example 5 20 2-Amino-5-methyl-7-methylthio-1,8-naphthyridine 77.5 g (0.4 mol) of 2-amino-5-methyl-7-chloro-1,8-naphthyridine prepared in accordance with Lit.5) is introduced into a solution of 112 9 (1.6 mol) of sodium thiomethanolate in 700 ml of water, and the resulting suspension 25 is refluxed for 4 hours. After cooling, the residue is suction filtered, washed with water and dried. There is obtained 68 9 (83%) of the title compound; m.p.: 204-209C.
Example 6 2-Hydroxysulfonyl-5,7-dimethyl-1,8-naphthyridine 9.6 9 (50 mmol) of 2-chloro-5,7-dimethyl-1,8-naphthyridine prepared in accordance with Lit.8)~9) is introduced into a solution of 8.2 9 (65 mmol) 35 of sodium sulfite in 40 ml of water which has been adjusted to a pH of 7-8 with dilute aqueous hydrochloric acid. The suspension which is obtained is heated for 12 hours under reflux. After cooling, solid residues are removed from the solution and the solution itself is acidified with aqueous hydrochloric acid (pH about 1). The acidified solution is left for 40 12 hours at O to 5C, the product crystallizing out. There iS obtained 7.7 9 (65%) of the title compound; m.p.: >280C.
The compounds listed in Table 1 below were prepared from corresponding starting materials after appropriate modification of the details of Examples 1 to 6.
2 0 ~ , 3 21 O.Z. 0050/40631 Table 1 R 6~HR 1 ExampleRl R5 R6 R7 mp (C)Lit.a) No.
1.1 HNCOCH3 OH H H 264-26510) 1.2 NH2 Cl H Cl 213-216 1.3 NH2 OH H H >3Q0 10) 1.4 NH2 CH3 H H >300 1) 1.5 HNCOCH3phenyl H CH3 207-2135) 1.6 HNCOCH3 CH3 H OC6Hs 203-205 1.7 NH2 OH C02H H >300 10) 1.8 NH2 H H Cl >300 1.9 HNCOCH3 OH CO2C2Hs H >300 10) 1.10 NH2 CH2CI H Cl >280 1.11 NH2 CH2OCH3 H OH >290 1.12 HNCOCH3 H H OH >280 11) 1.13 NH2 H H CH3 238 (decomp) 12) 1.14 NH2 H H OH >280 2), 11) 1.15 NH2 C6H5 H CH3 246 (decomp) 4) 1.16 NH2 CH3 H SCH3 204-209 1.17 NH2 CH3 H OC6H5 206-2105) 1.18 NH2 CH3 H C6H5 >2801), 4) 1.19 HNCOCH3 CH2CI H OH >280 1.20 NH2 CH2Cl H OH >280 1.21 NH2 Sr H Br 208-212 1.22 NH2 CH3 H Br ~300 1.23 NH2 CH3 H N(CH3)2 >300 1.24 NH2 H C02C2Hs OH >300 11) 1.25 SH CH3 H CH3 272-274 ~ ~ v 3 j 22 O . Z . 0050/40631 Table 1 Example R1 R5 R6 R7 mp (~C) Lit.a) No.
1.26 NH2 CF3 H CF3 204-208 13) 1.27 NH2 OH H OH 325 (decomp) 3) 1.28 SCH2C6H5 CH3 H CH3 98-104 1.29 NH2 CH3 H OCH3 229-232 1.30 NH2 CH3 H Cl 256-261 5) 1.31 HNCOCH3 CH3 H Cl 238-240 5) 1.32 OCH3 CH3 H CH3 37-40 9) 1.33 Cl CH3 H CH3 138-141 8), 9) 1.34 HNCOCH3 CH3 H OH 395 5) 1.35 OH CH3 H CH3 253-257 8), 9) 1.36 NH 2 CH3 H OH >300 6) 1.37 NH2 CH3 H CH3 218-220 7) 1.38 NH2 CF3 H CH3 185-187 13) 1.39 NH2 CH3 H CF3 244-246 13) 1 40 NH2 OCH3 H OCH3 230-232 13) 1.41 SO3H CH3 H CH3 >280 a) Literature sources 5 1) R.A. Henry and P.R. Hammond, J. Het. Chem. 14, 1109 (1977) 2) S. Carboni, A. Da Settimo and G. Pirisino, Ann. di Chim. 54, 883 ~1964) 10 3) G. R. Lappin, Q.R. Petersen and C.E. Wheeler, J. Org. Chem. IS, 377 (1950) 4) A. Mangini and M. Colonna, Gazz. chim. ital. 73, 330 (1943) lS 5) V. Petrow, E. L. Rewald and B. Sturgeon, J. Chem.Soc. London, 1407 (1947)
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?, 17 O.z. 0050/40631 The herbicidal active ingredients and antidotes may be applied together or separately to the leaves and shoots of the crop plants and unwanted plants. Preferably, the antidote is applied together with the herbicidal active ingredient. If the components are applied separately, the antidote 5 is applied first to the field and then the herbicidal active ingredient.
The herbicidal active ingredient and antidote may be formulated together or separately as spray agents in the form of suspensions, emulsions or solutions.
10 Treatment of the crop plant seed with the antidote prior to sowing is also feasible. The herbicidal active ingredient is then applied on its own in conventional manner.
For herbicidal (heteroaryloxy)-phenoxyacetic acid derivatives, the amount 15 of antidotally active compound varies, depending on the crop. The ratios may vary over a wide range, and are also dependent on the structure of the ~heteroaryloxy)phenoxyacetic acid derivatives and on the crop involved.
Suitable ratios of herbicidal active ingredient to antidote are from 1:10 to 1:0.01, and preferably from 1:4 to 1:0.1, parts by weight.
For the same cyclohexenone derivative, the amount of antidote varies, depending on the crop. The ratios in which a cyclohexenone derivative and a l,8-naphthyridine derivative I are used may vary over a wide range, and are dependent on the structure of the cyclohexenone derivative, the naph-25 thyridine derivative I and the crop involved. Suitable ratios of herbicid-al active ingredient to safener are from 1:10 to 1:0.01, and preferably from 1:4 to 1:0.25, parts by weight.
The novel herbicidal agents may contain, in addition to the naphthyridine 30 derivative I as safener and the herbicide from the group of the (hetero-aryloxy)phenoxyacetic acids IV or cyclohexenones V, other herbicidal or growth-regulating active ingredients of different chemical structure without the safening effect being impaired.
35 The agents according to the invention, or - when applied separately - the herbicidal active ingredients and the safener, are applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or others), dispersions, emulsions, oil dis-persions, pastes, dusts, broadcasting agents or granules by spraying, 40 atomizing, dusting, broadcasting or pouring. The forms of application de-pend entirely on the purpose for which the active ingredients are to be used.
Q ~
18 O.Z. 0050/40631 For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vege-table or animal origin, aliphatic, cyclic and aromatic hydrocarbons such 5 as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, lO etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the herbicidal active ingredients and/or anti-15 dotes as such or dissolved in an oil or solvent may be homogenized inwater by means of wetting or dispersing agents, adherents or emulsifiers.
Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalene-sulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and 25 alkyl, lauryl ether and fatty alcohol sulfates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sul-fate, fatty alcohol sulfates, and salts of sulfated hexadecanols, hepta-decanols, and octadecanols, salts of fatty alcohol glycol ethers, conden-sation products of sulfonated naphthalene and naphthalene derivatives with 30 formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonyl-phenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene 35 oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grind-40 ing the herbicidal active ingredients and/or antidote with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of 19 o.Z. 0050~40631 solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium S sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably from 0.5 to 90,10 wt% of herbicidal active ingredient and antidote. The herbicidal active ingredient is applied at rates of from 0.2 to 5 kg/ha.
The present invention is further illustrated by the following examples.
15 Example 1 2-Amino-S-chloromethyl-7-hydroxy-1,8-naphthyridine 32.9 9 (0.2 mol) of ethyl 4-chloroacetoacetate is dripped into a suspen-20 sion of 21.8 9 (0.2 mol) of 2,6-diaminopyridine in 100 ml of 85% strength phosphoric acid. The reaction mixture is stirred for 3 hours at 90C, cooled and poured into ice water, followed by neutralization with concen-trated aqueous ammonia solution. The precipitate is suction filtered, stirred into water again and finally boiled with acetonitrile. 22.8 9 25 (54%) of the title compound is obtained; m.p.: >280C.
Example 2 2-Amino-5-methoxymethyl-7-hydroxy-1,8-naphthyridine A mixture of 21.8 9 (0.2 mol) of 2,6-diaminopyridine and 29.2 9 (0.2 mol) of methyl 4-methoxyacetoacetate in 400 ml of glacial acetic acid is stirred under reflux for 3 hours. After cooling, the precipitate is suction filtered and stirred with 150 ml of cold ethanol. 8 9 (20~) of the 35 title compound is obtained; m.p.: >290C.
Example 3 Acetylation of 2-amino-5,7-dihydroxy-1,8-naphthyridine A mixture of 17.7 g tO.l mol) of 2-amino-5,7-dihydroxy-1,8-naphthyridine prepared in accordance with Lit.3) and 250 ml of acetic anhydride is stirred under reflux for 30 minutes. After cooling, the precipitate is suction filtered, washed with acetone and dried. There is obtained 20.9 9 (8~%~ of a mixture of 2-acetylamino-5-hydroxy-7-acetoxy-1,8-naphthyridine and 2-acetylamino-5-acetoxy-7-hydroxy-1,8-naphthyridine; m.p.: >300C.
2 ~ 3 O.Z. 0050/40631 This mixture can be used direct in the chlorination with POC13 described below.
Example 4 2-Amino-5,7-dichloro-1,8-naphthyridine A suspension of 63 9 (0.241 mol) of the mixture prepared in Example 3 and 600 ml of POC13 is slowly heated to the reflux temperature and then 10 stirred for 2 hours under reflux. Subsequently, the reaction mixture, which has been concentrated to about half its volume, is carefully dripped with ice cooling into 2.5 liters of ice water. The resulting mixture is stirred for one hour at 95-100C and then cooled, the residue is filtered off and the filtrate is brought to a pH of 6. The precipitate is suction 15 filtered, washed thoroughly with warm water and dried. There is obtained 47.9 9 (92%) of the title compound; m.p.: 213-216C.
Example 5 20 2-Amino-5-methyl-7-methylthio-1,8-naphthyridine 77.5 g (0.4 mol) of 2-amino-5-methyl-7-chloro-1,8-naphthyridine prepared in accordance with Lit.5) is introduced into a solution of 112 9 (1.6 mol) of sodium thiomethanolate in 700 ml of water, and the resulting suspension 25 is refluxed for 4 hours. After cooling, the residue is suction filtered, washed with water and dried. There is obtained 68 9 (83%) of the title compound; m.p.: 204-209C.
Example 6 2-Hydroxysulfonyl-5,7-dimethyl-1,8-naphthyridine 9.6 9 (50 mmol) of 2-chloro-5,7-dimethyl-1,8-naphthyridine prepared in accordance with Lit.8)~9) is introduced into a solution of 8.2 9 (65 mmol) 35 of sodium sulfite in 40 ml of water which has been adjusted to a pH of 7-8 with dilute aqueous hydrochloric acid. The suspension which is obtained is heated for 12 hours under reflux. After cooling, solid residues are removed from the solution and the solution itself is acidified with aqueous hydrochloric acid (pH about 1). The acidified solution is left for 40 12 hours at O to 5C, the product crystallizing out. There iS obtained 7.7 9 (65%) of the title compound; m.p.: >280C.
The compounds listed in Table 1 below were prepared from corresponding starting materials after appropriate modification of the details of Examples 1 to 6.
2 0 ~ , 3 21 O.Z. 0050/40631 Table 1 R 6~HR 1 ExampleRl R5 R6 R7 mp (C)Lit.a) No.
1.1 HNCOCH3 OH H H 264-26510) 1.2 NH2 Cl H Cl 213-216 1.3 NH2 OH H H >3Q0 10) 1.4 NH2 CH3 H H >300 1) 1.5 HNCOCH3phenyl H CH3 207-2135) 1.6 HNCOCH3 CH3 H OC6Hs 203-205 1.7 NH2 OH C02H H >300 10) 1.8 NH2 H H Cl >300 1.9 HNCOCH3 OH CO2C2Hs H >300 10) 1.10 NH2 CH2CI H Cl >280 1.11 NH2 CH2OCH3 H OH >290 1.12 HNCOCH3 H H OH >280 11) 1.13 NH2 H H CH3 238 (decomp) 12) 1.14 NH2 H H OH >280 2), 11) 1.15 NH2 C6H5 H CH3 246 (decomp) 4) 1.16 NH2 CH3 H SCH3 204-209 1.17 NH2 CH3 H OC6H5 206-2105) 1.18 NH2 CH3 H C6H5 >2801), 4) 1.19 HNCOCH3 CH2CI H OH >280 1.20 NH2 CH2Cl H OH >280 1.21 NH2 Sr H Br 208-212 1.22 NH2 CH3 H Br ~300 1.23 NH2 CH3 H N(CH3)2 >300 1.24 NH2 H C02C2Hs OH >300 11) 1.25 SH CH3 H CH3 272-274 ~ ~ v 3 j 22 O . Z . 0050/40631 Table 1 Example R1 R5 R6 R7 mp (~C) Lit.a) No.
1.26 NH2 CF3 H CF3 204-208 13) 1.27 NH2 OH H OH 325 (decomp) 3) 1.28 SCH2C6H5 CH3 H CH3 98-104 1.29 NH2 CH3 H OCH3 229-232 1.30 NH2 CH3 H Cl 256-261 5) 1.31 HNCOCH3 CH3 H Cl 238-240 5) 1.32 OCH3 CH3 H CH3 37-40 9) 1.33 Cl CH3 H CH3 138-141 8), 9) 1.34 HNCOCH3 CH3 H OH 395 5) 1.35 OH CH3 H CH3 253-257 8), 9) 1.36 NH 2 CH3 H OH >300 6) 1.37 NH2 CH3 H CH3 218-220 7) 1.38 NH2 CF3 H CH3 185-187 13) 1.39 NH2 CH3 H CF3 244-246 13) 1 40 NH2 OCH3 H OCH3 230-232 13) 1.41 SO3H CH3 H CH3 >280 a) Literature sources 5 1) R.A. Henry and P.R. Hammond, J. Het. Chem. 14, 1109 (1977) 2) S. Carboni, A. Da Settimo and G. Pirisino, Ann. di Chim. 54, 883 ~1964) 10 3) G. R. Lappin, Q.R. Petersen and C.E. Wheeler, J. Org. Chem. IS, 377 (1950) 4) A. Mangini and M. Colonna, Gazz. chim. ital. 73, 330 (1943) lS 5) V. Petrow, E. L. Rewald and B. Sturgeon, J. Chem.Soc. London, 1407 (1947)
6) 0. Seide, Chem. Ber. LIX, 159 (1926).
20 7) J. Bernstein et al., J. Am. Chem. Soc. 69, 1157 (1947) 8) A. Mangini and M. Colonna, Gazz. chim. ital. 73, 323 (1943) 2~ r~,3 23 O.Z. 0050/40631 9) E. Ochiai and K. Miyaki, Chem. Ber. 74, 1115 (1941) 10) S. Carboni, A. Da Settimo, P.L. Ferrarini and 1. Tonetti, Gazz. chim.
ital. 101, 129 (lg71) 11) S. Carboni, A. Da Settimo and P.L. Ferrarini, Gazz. chim. ital. 95, 1492 (1965) 12) E.V. Brown, J. Org. Chem. 30, 1607 (1965) 13) E. Eichler, C.S. Rooney and H.W.R. Williams, J. Het. Chem. 13, 41 (1976) 15 Example 7 2-Amino-6-bromo-5,7-dimethyl-1,8-naphthyridine 173 9 (1 mol) of 2-amino-5,7-dimethyl-1,8-naphthyridine is suspended in 20 500 ml of glacial acetic acid. At 60C and with stirring, 160 9 (1 mol) of bromine is dripped in, the solid going into solution. After all has been added, the mixture is stirred overnight at room temperature (20C) and then poured into 1 liter of water. Excess bromine is reduced by adding a small amount of NaHSO3. The pH is brought to 4 with concentrated NH3 25 solution. The mixture is stirred for about 30 minutes and the precipitate is filtered off and dried under reduced pressure to give 132 9 of a pale brown solid.
Example 8 30 2-Amino-5,6-dimethyl-7-phenylthio-1,8-naphthyridine 13 g of a 30~ strength methanolic sodium methylate solution is introduced into 5.0 9 (24 mmol) of 2-amino-7-chloro-5,6-dimethyl-1,8-naphthyridine and 8.0 9 (72 mmol) of thiophenol in 100 ml of anhydrous methanol. The 35 mixture is boiled under reflux for 3 hours and stirred overnight at room temperature. 200 ml of water is added, the mixture is stirred for 1 hour, and the precipitated solid is filtered off, washed with a small amount of methanol and dried under reduced pressure. There is obtained 4.7 9 of a pale yellow solid.
24 O.Z. 0050~40631 Example 9 2-Acetamino-7-hydroxy-5,6-dimethyl-1,8-naphthyridine 5 142 9 (0.75 mol) of 2-amino-7-hydroxy-5,6-dimethyl-1,8-naphthyridine and 640 ml of acetic anhydride are boiled under reflux for 30 minutes. After the mixture has been cooled, the product is filtered off and purified by stirring with CH2C12 and methanol. There is obtained 64.1 9 (37%) of a gray solid.
10 1H_NMR (200 MHz, (F3-(02D): ~ = 2.42 ts, 3H, CH3), 2.58 (s, 3H, CH3), 2.69 (s, 3H, CH3), 7.46 (d, lH, Ar-H), 8.84 (d, lH, Ar-H).
Example 10 15 2-Amino-7-chloro-5,6-dimethyl-1,8-naphthyridine 34.6 g (0.15 mol) of 2-acetamino-7-hydroxy-5,6-dimethyl-1,8-naphthyridine and 380 ml of phosphorus oxychloride are boiled under reflux for 30 minutes, the starting material dissolving. Excess POC13 is distilled off, 20 the residue poured onto ice and concentrated hydrochloric acid is added.
After the mixture has been boiled under reflux for 30 minutes, it is made alkaline with 50% strength sodium hydroxide solution. The precipitate is suction fi.ltered and recrystallized from 4 liters of methanol. There is obtained 28.7 g (92%) of a pale brown solid which is further reacted 25 without any purification.
The compounds listed in Table 2 below were prepared from corresponding starting materials with appropriate modification of the details of Examples 7, 8, 9 and 10.
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28 O.Z. 0050/40631 Examples demonstrating biological action The influence of various representatives of the herbicidal agents, or combinations of herbicide and antidote, according to the invention on the 5 growth of unwanted and crop plants compared with the herbicidal active ingredient alone is illustrated in the following greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm3 and filled with a sandy loam containing about 3.0% humus. The seeds of the 10 test plants were sown separately, according to species, and then moisten-ed. The vessels were then covered with transparent plastic hoods until the plants had taken root.
For the postemergence treatment, the plants were grown, depending on 15 growth form, to a height of 3 to 20 cm before being treated with the active ingredients, which were suspended or emulsified in water and sprayed through finely distributing nozzles.
As an example of a herbicidal active ingredient of the formula V, the 20 cyctohexenone derivative V.2 was used in the biological experiments:
H5C2SCHcH2 ~ C\ V.2 O C3H7n The herbicidal active ingredient v.2 was used ~on its own and together with the safener) in the spray liquor as a commercially formulated product (184 9/1 EC) together with the same amounts of solvent system XXII given 25 in the table for the safener.
For the postemergence treatment, all the safeners were formulated in a mixture consisting of ô0~ of cyclohexenone and 2~ of Emulphor EL
(formulation XXII) with 10wt~ of active ingredient.
The test plants employed were Hordeum vulgare, Lolium multiflorum, Oryza sativa, Setaria italica, Sorghum, Triticum aestivum and Zea mays.
The vessels were set up in the greenhouse, heat-loving species at from 18 35 to 30C and species from more moderate climates at from 10 ta 25C.
29 O.Z. 0050/40631 The experiments were run for from 3 to 5 weeks. During this period, the plants were tended and their reactions to the various treatments assessed.
Damage by the chemical agents was assessed on a scale from 0 to 10WO
5 compared with the untreated control plants, 0 denoting no damage and 100 denoting complete destruction of the plants.
The tables below document the safening action of compounds nos. 1.10, 1.16, 1.8, 1.17 and 2.13 according to the invention. These compounds 10 significantly improve the tolerance of the herbicide V.2 by wheat.
Table 1: Improvement in the tolerance of the herbicide V.2 by wheat by admixing a safening compound and applying the mixture post-emergence in the greenhouse Appl. rate Test plants and % damage kg/ha Crop plant Unwanted Herbicide Safener Triticum plant V.2 1.10 aestivum* Lolium multif .
0.03 - 65 100 0.06 - 95 100 0.03 0.125 0 100 0.06 0.25 30 100 *Variety: "Okapi"
Table 2: Reduction in the phytotoxicity of the herbicide V.2 in wheat by combining it with an example of a safener and applying the mixture postemergence in the greenhouse Appl. rate Test plants and ~ damage kg/ha Crop plant Unwanted 35 Herbicide SafenerTriticum plant V.2 1.16 aestivum* Lolium multif .
0.03 - 65 100 0.03 0.125 0 100 *Variety: "Okapi"
~ 3 O.Z. 0050/40631 Table 3: Reduction in the phytotoxicity of the herbicide V.2 in wheat by combining it with an example of a safener and applying the mixture postemergence in the greenhouse Appl. rate Test plants and % damage kg/ha Crop plant Unwanted Herbicide Safener Triticum plant V.2 [No ] aestivum* Lolium multif .
0.03 - 65 100 0.03 0.125 30 100 [1.8]
0.03 0.125 20 100 ~1.17]
*Variety: "Okapi"
Table 4: Reduction in the phytotoxicity of the herbicide V.2 in rice by combining it with an example of a safener and applying the mixture postemergence in the greenhouse Appl. rate Test plants and % damage tkg/ha] Crop plant Unwanted plant 25 Herbicide Safener Oryza sativa* Setaria italica 2.13 0.03 50 95 0.03 0.06 10 80 ~ 30 .~ * Variety: "Bahia"
20 7) J. Bernstein et al., J. Am. Chem. Soc. 69, 1157 (1947) 8) A. Mangini and M. Colonna, Gazz. chim. ital. 73, 323 (1943) 2~ r~,3 23 O.Z. 0050/40631 9) E. Ochiai and K. Miyaki, Chem. Ber. 74, 1115 (1941) 10) S. Carboni, A. Da Settimo, P.L. Ferrarini and 1. Tonetti, Gazz. chim.
ital. 101, 129 (lg71) 11) S. Carboni, A. Da Settimo and P.L. Ferrarini, Gazz. chim. ital. 95, 1492 (1965) 12) E.V. Brown, J. Org. Chem. 30, 1607 (1965) 13) E. Eichler, C.S. Rooney and H.W.R. Williams, J. Het. Chem. 13, 41 (1976) 15 Example 7 2-Amino-6-bromo-5,7-dimethyl-1,8-naphthyridine 173 9 (1 mol) of 2-amino-5,7-dimethyl-1,8-naphthyridine is suspended in 20 500 ml of glacial acetic acid. At 60C and with stirring, 160 9 (1 mol) of bromine is dripped in, the solid going into solution. After all has been added, the mixture is stirred overnight at room temperature (20C) and then poured into 1 liter of water. Excess bromine is reduced by adding a small amount of NaHSO3. The pH is brought to 4 with concentrated NH3 25 solution. The mixture is stirred for about 30 minutes and the precipitate is filtered off and dried under reduced pressure to give 132 9 of a pale brown solid.
Example 8 30 2-Amino-5,6-dimethyl-7-phenylthio-1,8-naphthyridine 13 g of a 30~ strength methanolic sodium methylate solution is introduced into 5.0 9 (24 mmol) of 2-amino-7-chloro-5,6-dimethyl-1,8-naphthyridine and 8.0 9 (72 mmol) of thiophenol in 100 ml of anhydrous methanol. The 35 mixture is boiled under reflux for 3 hours and stirred overnight at room temperature. 200 ml of water is added, the mixture is stirred for 1 hour, and the precipitated solid is filtered off, washed with a small amount of methanol and dried under reduced pressure. There is obtained 4.7 9 of a pale yellow solid.
24 O.Z. 0050~40631 Example 9 2-Acetamino-7-hydroxy-5,6-dimethyl-1,8-naphthyridine 5 142 9 (0.75 mol) of 2-amino-7-hydroxy-5,6-dimethyl-1,8-naphthyridine and 640 ml of acetic anhydride are boiled under reflux for 30 minutes. After the mixture has been cooled, the product is filtered off and purified by stirring with CH2C12 and methanol. There is obtained 64.1 9 (37%) of a gray solid.
10 1H_NMR (200 MHz, (F3-(02D): ~ = 2.42 ts, 3H, CH3), 2.58 (s, 3H, CH3), 2.69 (s, 3H, CH3), 7.46 (d, lH, Ar-H), 8.84 (d, lH, Ar-H).
Example 10 15 2-Amino-7-chloro-5,6-dimethyl-1,8-naphthyridine 34.6 g (0.15 mol) of 2-acetamino-7-hydroxy-5,6-dimethyl-1,8-naphthyridine and 380 ml of phosphorus oxychloride are boiled under reflux for 30 minutes, the starting material dissolving. Excess POC13 is distilled off, 20 the residue poured onto ice and concentrated hydrochloric acid is added.
After the mixture has been boiled under reflux for 30 minutes, it is made alkaline with 50% strength sodium hydroxide solution. The precipitate is suction fi.ltered and recrystallized from 4 liters of methanol. There is obtained 28.7 g (92%) of a pale brown solid which is further reacted 25 without any purification.
The compounds listed in Table 2 below were prepared from corresponding starting materials with appropriate modification of the details of Examples 7, 8, 9 and 10.
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28 O.Z. 0050/40631 Examples demonstrating biological action The influence of various representatives of the herbicidal agents, or combinations of herbicide and antidote, according to the invention on the 5 growth of unwanted and crop plants compared with the herbicidal active ingredient alone is illustrated in the following greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm3 and filled with a sandy loam containing about 3.0% humus. The seeds of the 10 test plants were sown separately, according to species, and then moisten-ed. The vessels were then covered with transparent plastic hoods until the plants had taken root.
For the postemergence treatment, the plants were grown, depending on 15 growth form, to a height of 3 to 20 cm before being treated with the active ingredients, which were suspended or emulsified in water and sprayed through finely distributing nozzles.
As an example of a herbicidal active ingredient of the formula V, the 20 cyctohexenone derivative V.2 was used in the biological experiments:
H5C2SCHcH2 ~ C\ V.2 O C3H7n The herbicidal active ingredient v.2 was used ~on its own and together with the safener) in the spray liquor as a commercially formulated product (184 9/1 EC) together with the same amounts of solvent system XXII given 25 in the table for the safener.
For the postemergence treatment, all the safeners were formulated in a mixture consisting of ô0~ of cyclohexenone and 2~ of Emulphor EL
(formulation XXII) with 10wt~ of active ingredient.
The test plants employed were Hordeum vulgare, Lolium multiflorum, Oryza sativa, Setaria italica, Sorghum, Triticum aestivum and Zea mays.
The vessels were set up in the greenhouse, heat-loving species at from 18 35 to 30C and species from more moderate climates at from 10 ta 25C.
29 O.Z. 0050/40631 The experiments were run for from 3 to 5 weeks. During this period, the plants were tended and their reactions to the various treatments assessed.
Damage by the chemical agents was assessed on a scale from 0 to 10WO
5 compared with the untreated control plants, 0 denoting no damage and 100 denoting complete destruction of the plants.
The tables below document the safening action of compounds nos. 1.10, 1.16, 1.8, 1.17 and 2.13 according to the invention. These compounds 10 significantly improve the tolerance of the herbicide V.2 by wheat.
Table 1: Improvement in the tolerance of the herbicide V.2 by wheat by admixing a safening compound and applying the mixture post-emergence in the greenhouse Appl. rate Test plants and % damage kg/ha Crop plant Unwanted Herbicide Safener Triticum plant V.2 1.10 aestivum* Lolium multif .
0.03 - 65 100 0.06 - 95 100 0.03 0.125 0 100 0.06 0.25 30 100 *Variety: "Okapi"
Table 2: Reduction in the phytotoxicity of the herbicide V.2 in wheat by combining it with an example of a safener and applying the mixture postemergence in the greenhouse Appl. rate Test plants and ~ damage kg/ha Crop plant Unwanted 35 Herbicide SafenerTriticum plant V.2 1.16 aestivum* Lolium multif .
0.03 - 65 100 0.03 0.125 0 100 *Variety: "Okapi"
~ 3 O.Z. 0050/40631 Table 3: Reduction in the phytotoxicity of the herbicide V.2 in wheat by combining it with an example of a safener and applying the mixture postemergence in the greenhouse Appl. rate Test plants and % damage kg/ha Crop plant Unwanted Herbicide Safener Triticum plant V.2 [No ] aestivum* Lolium multif .
0.03 - 65 100 0.03 0.125 30 100 [1.8]
0.03 0.125 20 100 ~1.17]
*Variety: "Okapi"
Table 4: Reduction in the phytotoxicity of the herbicide V.2 in rice by combining it with an example of a safener and applying the mixture postemergence in the greenhouse Appl. rate Test plants and % damage tkg/ha] Crop plant Unwanted plant 25 Herbicide Safener Oryza sativa* Setaria italica 2.13 0.03 50 95 0.03 0.06 10 80 ~ 30 .~ * Variety: "Bahia"
Claims (8)
31 O.Z. 0050/40631 We claim:
1. Substituted 1,8-naphthyridines of the general formula I
I, where:
R1 is mercapto, benzylthio, sulfonyl, amino or NR2R3, where R2 is C1-C12-alkyl, C3-C6-alkenyl, C3-C8-cycloalkyl, phenyl, phenyl-(C1-C3)-alkyl or phenyl or phenyl-(C1-C3)-alkyl which is monosubstituted to trisubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, amino, or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or a group -?-A, where A is C1-C8-alkyl or is phenyl which is unsubstituted or monosubstituted to trisubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or is amino, alkyl- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, phenylamino, morpholino or piperidyl, and R3 is hydrogen, C1-C12-alkyl or C3-C8-cycloalkyl, or R2 and R3 are bonded to one another to form a saturated or unsaturated 5-membered or 6-membered heterocyclic structure which, in addition to the nitrogen atom to which they are bonded, may contain a further heteroatom such as oxygen or nitrogen;
hydroxyl, mercapto, halogen or XR4, where X is oxygen or sulfur and R4 is C1-C12-alkyl, C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, C5-C8-cycloalkyl, phenyl or phenyl-C1-C3-alkyl, where the aromatic rings may carry from one to three of the following radicals: halogen, C1-C4-alkyl, CA, KR
32 O.Z. 0050/40631 C1-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, R5 and R7 are each hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, or phenyl or phenyl-(C1-C3)-alkyl, where the phenyl nucleus in each case may carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
hydroxyl, halogen, mercapto, C1-C4-alkoxy, C1-C4-alkylthio, amino, mono- or dialkylamino where each alkyl is of 1 to 6 carbon atoms, phenoxy or phenylthio, where the phenyl nucleus in turn may carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
halo-(C1-C3)-alkyl, C1-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, C1-C4-acyloxy which may bear from one to three C1-C4-alkyl radicals and/or a C1-C4-acyl radical; hydrazino, cyano and thiocyanato, R6 is hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, phenyl or phenyl-(Cl-C3)-alkyl, where the phenyl nucleus in each case may in turn carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
halogen, halo-(C1-C3)-alkyl, C1-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, carboxyl or C1-C4-alkoxycarbonyl, and their plant-tolerated salts.
I, where:
R1 is mercapto, benzylthio, sulfonyl, amino or NR2R3, where R2 is C1-C12-alkyl, C3-C6-alkenyl, C3-C8-cycloalkyl, phenyl, phenyl-(C1-C3)-alkyl or phenyl or phenyl-(C1-C3)-alkyl which is monosubstituted to trisubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, amino, or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or a group -?-A, where A is C1-C8-alkyl or is phenyl which is unsubstituted or monosubstituted to trisubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or is amino, alkyl- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, phenylamino, morpholino or piperidyl, and R3 is hydrogen, C1-C12-alkyl or C3-C8-cycloalkyl, or R2 and R3 are bonded to one another to form a saturated or unsaturated 5-membered or 6-membered heterocyclic structure which, in addition to the nitrogen atom to which they are bonded, may contain a further heteroatom such as oxygen or nitrogen;
hydroxyl, mercapto, halogen or XR4, where X is oxygen or sulfur and R4 is C1-C12-alkyl, C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, C5-C8-cycloalkyl, phenyl or phenyl-C1-C3-alkyl, where the aromatic rings may carry from one to three of the following radicals: halogen, C1-C4-alkyl, CA, KR
32 O.Z. 0050/40631 C1-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, R5 and R7 are each hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, or phenyl or phenyl-(C1-C3)-alkyl, where the phenyl nucleus in each case may carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
hydroxyl, halogen, mercapto, C1-C4-alkoxy, C1-C4-alkylthio, amino, mono- or dialkylamino where each alkyl is of 1 to 6 carbon atoms, phenoxy or phenylthio, where the phenyl nucleus in turn may carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
halo-(C1-C3)-alkyl, C1-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, C1-C4-acyloxy which may bear from one to three C1-C4-alkyl radicals and/or a C1-C4-acyl radical; hydrazino, cyano and thiocyanato, R6 is hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, phenyl or phenyl-(Cl-C3)-alkyl, where the phenyl nucleus in each case may in turn carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
halogen, halo-(C1-C3)-alkyl, C1-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, carboxyl or C1-C4-alkoxycarbonyl, and their plant-tolerated salts.
2. A process for the manufacture of compounds I as set forth in claim 1, wherein a 2,6-diaminopyridine of the formula II
II
is reacted with a .beta.-dicarbonyl compound of the general formula III
III
CA,KR
33 O.Z. 0050/40631 and, if desired, by preparation of a derivative thereof or by sub-stitution of radicals R1 and/or R5 and/or R6 and/or R7 in conventional manner.
II
is reacted with a .beta.-dicarbonyl compound of the general formula III
III
CA,KR
33 O.Z. 0050/40631 and, if desired, by preparation of a derivative thereof or by sub-stitution of radicals R1 and/or R5 and/or R6 and/or R7 in conventional manner.
53. A herbicidal agent containing at least one substituted 1,8-naph-thyridine of the general formula I
I, where:
R1 is mercapto, benzylthio, sulfonyl, amino or NR2R3, where R2 is C1-C12-alkyl, C3-C6-alkenyl, C3-C8-cycloalkyl, phenyl, phenyl-(C1-C3)-alkyl or phenyl or phenyl-(C1-C3)-alkyl which is monosubstituted to trisubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, amino, or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or a group , where A is C1-C8-alkyl or is phenyl which is unsubstituted or monosubstituted to trisubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or is amino, alkyl- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, phenylamino, morpholino or piperidyl, and R3 is hydrogen, C1-C12-alkyl or C3-C8-cycloalkyl, or R2 and R3 are bonded to one another to form a saturated or unsaturated 5-membered or 6-membered heterocyclic structure which, in addition to the nitrogen atom to which they are bonded, may contain a further heteroatom such as oxygen or nitrogen;
hydroxyl, mercapto, halogen or XR4, where X is oxygen or sulfur and R4 is C1-C12-alkyl, C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, C5-C8-cycloalkyl, phenyl or phenyl-C1-C3-alkyl, where the aromatic rings may carry from one to three of the following radicals: halogen, C1-C4-alkyl, CA,KR
34 O.Z. 0050/40631 C1-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, R5 and R7 are each hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, or phenyl or phenyl-(C1-C3)-alkyl, where the phenyl nucleus in each case may carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
hydroxyl, halogen, mercapto, C1-C4-alkoxy, C1-C4-alkylthio, amino, mono- or dialkylamino where each alkyl is of 1 to 6 carbon atoms, phenoxy or phenylthio, where the phenyl nucleus in turn may carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
halo-(C1-C3)-alkyl, C1-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, C1-C4-acyloxy which may bear from one to three C1-C4-alkyl radicals and/or a C1-C4-acyl radical; hydrazino, cyano and thiocyanato, R6 is hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, phenyl or phenyl-(C1-C3)-alkyl, where the phenyl nucleus in each case may in turn carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
halogen, halo-(C1-C3)-alkyl, C1-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, carboxyl or C1-C4-alkoxycarbonyl, or a plant-tolerated salt thereof, and at least one herbicidal active ingredient selected from the group consisting of a) 2-(4-heteroaryloxy)- or 2-(4-aryloxy)-phenoxyacetic acid derivatives of the formula IV
Ra-O--?H-CO2Rb IV, where:
Ra is a phenyl ring, a pyridyl ring, a benzoxazyl radical, a benzo-thiazyl radical or a benzopyrazinyl radical, where these aromatic ring systems may carry up to two of the following radicals:
halogen, nitro, C1-C4-alkyl, C1-C4-haloalkyl and/or C1-C4-halo-alkoxy, CA,KR
O.Z. 0050/40631 Rb is hydrogen, C1-C4-alkyl or one equivalent of a plant-tolerated cation, and Rc is hydrogen or methyl and b) cyclohexenone derivatives of the formula V
V
where:
Rd is C1-C4-alkyl;
Re is C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C3-C4-haloalkylene or thenyl which may be substituted by a halogen atom;
Rf is C1-C4-alkyl which may be mono- or disubstituted by C1-C4-alkylthio or C1-C4-alkoxy;
a 5- or 6-membered saturated or monounsaturated ring system which, in addition to carbon members, may contain an oxygen or sulfur atom or a sulfoxyl or sulfonyl group, and this ring system may carry up to three of the following radicals: hydroxyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and/or C1-C4-alkylthio;
a 10-membered saturated or monounsaturated heterocyclic structure which contains two oxygen atoms or sulfur atoms and may be substituted by up to three C1-C4-alkyl groups and/or methoxy groups;
phenyl, pyridyl, thiazolyl, pyrazolyl, pyrrolyl or isoxazolyl, where these groups may carry up to three of the following radicals: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C4-alkoxy-C1-C3-alkyl, C1-C4-dialkoxy-C1-C3-alkyl, formyl, halogen and/or benzoylamino;
Rg is hydrogen, hydroxyl or, when Rf is C1-C6-alkyl, a C1-C6-alkyl group;
CA, KR
36 O.Z. 0050/40631 Rh is hydrogen, cyano, halogen, C1-C4-alkoxycarbonyl or a C1-C4-alkylketoxime and Ri is hydrogen or one equivalent of an environmentally compatible cation.
I, where:
R1 is mercapto, benzylthio, sulfonyl, amino or NR2R3, where R2 is C1-C12-alkyl, C3-C6-alkenyl, C3-C8-cycloalkyl, phenyl, phenyl-(C1-C3)-alkyl or phenyl or phenyl-(C1-C3)-alkyl which is monosubstituted to trisubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, amino, or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or a group , where A is C1-C8-alkyl or is phenyl which is unsubstituted or monosubstituted to trisubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, or is amino, alkyl- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, phenylamino, morpholino or piperidyl, and R3 is hydrogen, C1-C12-alkyl or C3-C8-cycloalkyl, or R2 and R3 are bonded to one another to form a saturated or unsaturated 5-membered or 6-membered heterocyclic structure which, in addition to the nitrogen atom to which they are bonded, may contain a further heteroatom such as oxygen or nitrogen;
hydroxyl, mercapto, halogen or XR4, where X is oxygen or sulfur and R4 is C1-C12-alkyl, C1-C4-alkoxycarbonyl-(C1-C4)-alkyl, C5-C8-cycloalkyl, phenyl or phenyl-C1-C3-alkyl, where the aromatic rings may carry from one to three of the following radicals: halogen, C1-C4-alkyl, CA,KR
34 O.Z. 0050/40631 C1-C4-alkoxy, amino or mono- or dialkylamino where each alkyl radical is of 1 to 6 carbon atoms, R5 and R7 are each hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, or phenyl or phenyl-(C1-C3)-alkyl, where the phenyl nucleus in each case may carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
hydroxyl, halogen, mercapto, C1-C4-alkoxy, C1-C4-alkylthio, amino, mono- or dialkylamino where each alkyl is of 1 to 6 carbon atoms, phenoxy or phenylthio, where the phenyl nucleus in turn may carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
halo-(C1-C3)-alkyl, C1-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, C1-C4-acyloxy which may bear from one to three C1-C4-alkyl radicals and/or a C1-C4-acyl radical; hydrazino, cyano and thiocyanato, R6 is hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, phenyl or phenyl-(C1-C3)-alkyl, where the phenyl nucleus in each case may in turn carry from one to three of the following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, amino or mono- or dialkylamino where each alkyl radical is of 1 to 4 carbon atoms;
halogen, halo-(C1-C3)-alkyl, C1-C4-alkoxy-(C1-C3)-alkyl, C1-C4-alkylthio-(C1-C3)-alkyl, amino-(C1-C3)-alkyl, carboxyl or C1-C4-alkoxycarbonyl, or a plant-tolerated salt thereof, and at least one herbicidal active ingredient selected from the group consisting of a) 2-(4-heteroaryloxy)- or 2-(4-aryloxy)-phenoxyacetic acid derivatives of the formula IV
Ra-O--?H-CO2Rb IV, where:
Ra is a phenyl ring, a pyridyl ring, a benzoxazyl radical, a benzo-thiazyl radical or a benzopyrazinyl radical, where these aromatic ring systems may carry up to two of the following radicals:
halogen, nitro, C1-C4-alkyl, C1-C4-haloalkyl and/or C1-C4-halo-alkoxy, CA,KR
O.Z. 0050/40631 Rb is hydrogen, C1-C4-alkyl or one equivalent of a plant-tolerated cation, and Rc is hydrogen or methyl and b) cyclohexenone derivatives of the formula V
V
where:
Rd is C1-C4-alkyl;
Re is C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C3-C4-haloalkylene or thenyl which may be substituted by a halogen atom;
Rf is C1-C4-alkyl which may be mono- or disubstituted by C1-C4-alkylthio or C1-C4-alkoxy;
a 5- or 6-membered saturated or monounsaturated ring system which, in addition to carbon members, may contain an oxygen or sulfur atom or a sulfoxyl or sulfonyl group, and this ring system may carry up to three of the following radicals: hydroxyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and/or C1-C4-alkylthio;
a 10-membered saturated or monounsaturated heterocyclic structure which contains two oxygen atoms or sulfur atoms and may be substituted by up to three C1-C4-alkyl groups and/or methoxy groups;
phenyl, pyridyl, thiazolyl, pyrazolyl, pyrrolyl or isoxazolyl, where these groups may carry up to three of the following radicals: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C1-C4-alkoxy-C1-C3-alkyl, C1-C4-dialkoxy-C1-C3-alkyl, formyl, halogen and/or benzoylamino;
Rg is hydrogen, hydroxyl or, when Rf is C1-C6-alkyl, a C1-C6-alkyl group;
CA, KR
36 O.Z. 0050/40631 Rh is hydrogen, cyano, halogen, C1-C4-alkoxycarbonyl or a C1-C4-alkylketoxime and Ri is hydrogen or one equivalent of an environmentally compatible cation.
4. A herbicidal agent as set forth in claim 3, containing a substituted 1,8-naphthyridine I as set forth in claim 3 and a herbicide a) or a herbicide b), the weight ratio being from 10:1 to 0.01:1.
5. A process for the selective control of unwanted plants, wherein a substituted 1,8-naphthyridine of the formula I as set forth in claim 3 and a 2-(4-heteroaryloxy)- or 2-(4-aryloxy)-phenoxyacetic acid deriv-ative of the formula IV or a cyclohexenone derivative of the formula V
as set forth in claim 3 are applied either simultaneously or one after the other in any order before, during or after sowing of the crop plants or before or during emergence of the crop plants.
as set forth in claim 3 are applied either simultaneously or one after the other in any order before, during or after sowing of the crop plants or before or during emergence of the crop plants.
6. A process for preventing damage to crop plants by herbicidal 2-(4-heteroaryloxy)- or 2-(4-aryloxy)-phenoxyacetic acid derivatives of the formula IV or herbicidal cyclohexenone derivatives of the formula V as set forth in claim 3, wherein the seed of the crop plants is treated with an antagonistically effective amount of a substituted 1,8-naph-thyridine of the formula I as set forth in claim 3.
7. A process for the selective control of unwanted plants, wherein the leaves of the crop plants and the unwanted plants are treated post-emergence and either simultaneously or one after the other with a substituted 1,8-naphthyridine of the formula I as set forth in claim 3 and with a 2-(4-heteroaryloxy)- or 2-(4-aryloxy)-phenoxyacetic acid derivative of the formula IV or with a cyclohexenone derivative of the formula V as set forth in claim 3.
8. A process as set forth in any of claims 5 to 7, where the crop plants are barley, wheat, Indian corn, sorghum and rice.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3907937A DE3907937A1 (en) | 1989-03-11 | 1989-03-11 | SUBSTITUTED 1,8-NAPHTHYLRIDINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS ANTIDOTS |
| DEP3907937.6 | 1989-03-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2011538A1 true CA2011538A1 (en) | 1990-09-11 |
Family
ID=6376110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002011538A Abandoned CA2011538A1 (en) | 1989-03-11 | 1990-03-06 | Substitued 1,8-naphthyridines, their preparation and their use as antidotes |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0387568B1 (en) |
| JP (1) | JPH02268183A (en) |
| KR (1) | KR900014377A (en) |
| CA (1) | CA2011538A1 (en) |
| DE (2) | DE3907937A1 (en) |
| DK (1) | DK0387568T3 (en) |
| ES (1) | ES2066890T3 (en) |
| HU (1) | HU206427B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514642A (en) * | 1992-08-22 | 1996-05-07 | Basf Aktiengesellschaft | Cyclohexenone oxime ethers, their preparation and their use |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE903911A1 (en) * | 1989-11-20 | 1991-05-22 | Ici Plc | Diazine derivatives |
| GB9023289D0 (en) * | 1990-10-25 | 1990-12-05 | Ici Plc | Herbicides |
| DE4035479A1 (en) * | 1990-11-08 | 1992-05-14 | Basf Ag | SUBSTITUTED PYRIDO (2,3-D) PYRIMIDINE-2,4 (1H, 3H) DIONE |
| DE4131029A1 (en) * | 1991-09-18 | 1993-07-29 | Basf Ag | SUBSTITUTED PYRIDO (2,3-D) PYRIMIDINE AS ANTIDOTS |
| WO2007022946A1 (en) | 2005-08-21 | 2007-03-01 | Abbott Gmbh & Co. Kg | Heterocyclic compounds and their use as binding partners for 5-ht5 receptors |
| GB0805318D0 (en) * | 2008-03-20 | 2008-04-30 | Syngenta Ltd | Herbicidal compounds |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3601688A1 (en) * | 1986-01-17 | 1987-07-23 | Schering Ag | NAPHTHYRIDINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS AGENTS WITH HERBICIDAL ACTION |
| DE3644825A1 (en) * | 1986-12-31 | 1988-07-14 | Basf Ag | SUBSTITUTED 1,8-NAPHTHYRIDINE DERIVATIVES AND FUNGICIDES CONTAINING THEM |
| DE3804990A1 (en) * | 1988-02-18 | 1989-08-31 | Basf Ag | HERBICIDALLY EFFECTIVE, HETEROCYCLICALLY SUBSTITUTED SULFONAMIDES |
-
1989
- 1989-03-11 DE DE3907937A patent/DE3907937A1/en not_active Withdrawn
-
1990
- 1990-02-24 DK DK90103619.4T patent/DK0387568T3/en active
- 1990-02-24 EP EP90103619A patent/EP0387568B1/en not_active Expired - Lifetime
- 1990-02-24 ES ES90103619T patent/ES2066890T3/en not_active Expired - Lifetime
- 1990-02-24 DE DE59007969T patent/DE59007969D1/en not_active Expired - Lifetime
- 1990-03-06 CA CA002011538A patent/CA2011538A1/en not_active Abandoned
- 1990-03-09 JP JP2056793A patent/JPH02268183A/en active Pending
- 1990-03-09 HU HU901384A patent/HU206427B/en not_active IP Right Cessation
- 1990-03-10 KR KR1019900003281A patent/KR900014377A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514642A (en) * | 1992-08-22 | 1996-05-07 | Basf Aktiengesellschaft | Cyclohexenone oxime ethers, their preparation and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2066890T3 (en) | 1995-03-16 |
| EP0387568A1 (en) | 1990-09-19 |
| HU206427B (en) | 1992-11-30 |
| EP0387568B1 (en) | 1994-12-14 |
| DE3907937A1 (en) | 1990-09-13 |
| DE59007969D1 (en) | 1995-01-26 |
| DK0387568T3 (en) | 1995-01-23 |
| HUT53773A (en) | 1990-12-28 |
| KR900014377A (en) | 1990-10-23 |
| JPH02268183A (en) | 1990-11-01 |
| HU901384D0 (en) | 1990-05-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |