CA2095433A1 - Substituted pyrido[2,3-d]pyrimidine-2,4(1h,3h)-diones - Google Patents

Abstract

Pyrido[2,3-d]pyrimidin-2,4(1H,3H)-diones are disclosed, having formulas (Ia) and (Ib), in which R1 and R2 stand for H, substituted or unsubstituted alkyl, cycloalkyl; R3 stands for H, substituted or unsubstituted alkyl; R4 stands for H, alkyl, alkoxycarbonyl, (alkylthio)carbonyl, alkoxy(thiocarbonyl), (alkylthio)thiocarbonyl, cyano or aminocarbonyl; or R3 and R4 represent together alkylene, alkenylene or 1,2-phenylene; R5 stands for H, alkyl, cyano, C(O)R7; R6 stands for alkyl, possibly substituted aralkenyl, aryl or hetaryl, CH2R8, alkoxycarbonyl, (alkylthio)carbonyl, alkoxy(thiocarbonyl), (alkylthio)thiocarbonyl, OH, SH, alkoxy, alkylthio, NH2, alkylamino, NHCXR9, NHSO2R10;
R5 and R6 represent together substituted alkylene, alkenylene or 1,2-phenylene, which may also contain carbonyl or thiocarbonyl groups; R7 stands for H, alkyl, OH, SH, alkoxy, alkylthio, alkoxycarbonyl, (alkylthio)carbonyl, alkoxy(thiocarbonyl), (alkylthio)thiocarbonyl, NH2 alkylamino, dialkylamino, possibly substituted aryl or arylamino; R8 stands for halogen, OH, SH, alkoxy, alkylthio, alkoxycarbonyl, (alkylthio)carbonyl, alkoxy(thiocarbonyl), (alkylthio)thiocarbonyl or the formula (a); R9 stands for alkyl, halogen alkyl, NR1R2 or OR1; R10 stands for alkyl, substituted or unsubstituted aryl; R11 stands for halogen, OH, SH, alkoxy, alkylthio, alkyl, nitro or amino; X stands for oxygen or sulphur. Also disclosed are the salts of compounds (Ia) and (Ib) that can be used in agriculture and that contain nitrogen or hydroxy substituants, as well as herbicides that contain 2-[4-(hetero)-aryloxy]-phenoxyacetic acid or propionic acid derivates and/or cyclohexenone derivates as active herbicidal substances and substituted pyrido[2,3-d[pyrimidin-2,4(1H, 3H)-diones, as well as the salts of (Ia) or (Ib) as antidotes when acid end groups or basic nitrogen atoms are present.

Description

20~3~33 .Z. 0050/42408 Substituted pyrido r 2 3-dlpyrLmLdLne-2,~(lH~3Hl-di~ne~

The present invention relate~ to pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione~ of the ~ormulae Ia and Ib R 2~,~R 4 R 2~R S
ol I N R6 Rl Rl Ia rb where R , R are hydrogen, Cl-C4-alkyl, Cl-C4-haloalkyl or C3-C7-cyC loalkyl;
R is hydrogen, Cl-C4-alXyl, amino, hydroxyl, : mercapto, C1-C4-alkylthio or Cs~ or C1O-aryl which can carry one to three of the groups . mentioned for R1l;
R4 i hydrogen,C1-C~-alkyl,Cl-C4-alkoxycarbonyl, . Cl-C~-(alkylthio)carbonyl, Cl-Cj-alkoxy(thio--. carbonyl), C1-C~-(alkylthio)thiocarbonyl, : 15 cyano or ~m i nocarbonyl; or . R3 and R~ together are C3-C6-alkylene, C3-Cs-alkenylene or 1,2-phenylene;
R5 i~ hydrogen, C1-C4-alXyl, cyano, C(O)R' or C(S)R7;
R8 i8 Cl-C4-alkyl, C8-aryl-C2-C~-alkenyl, Cg~l Clo~
or C1~-aryl, it being possible for each aryl to carry one to three of the group~ mentioned for R11, or i~ C~2Ra, C1-C~-alkoxycarbonyl, Cl-C~-(alkylthlo)carbonyl, C1-C~-alkoxy(thio-carbonyl), C1-C~-(alkylthio)thiocarbonyl, hydroxyl, mercapto, C1-C4-alkoxy, C1-C~-alkyl-thio, amino, Cl-C~-alkylamino, NHCXR9, : NHSO2Rl, 2-thienyl, 3-thienyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 2-indolyl, 3-indolyl, it being possible for each hetaryl to be sub~tituted once or twice by the groups ; ' 2~9~43'3 - 2 - O.Z. 0050/42008 mentioned for Rll; or R5 and R6 together are C3-C~-alkylene, C3-C5-alkenylene or 1,2-phenylene, each of whlch can be substituted by Cl-C4-alkyl, Cl-C4-haloalkyl or C3-C7-cycloalkyl or can al~o contain carbonyl or thiocarbonyl groups;
~: R7 is hydrogen, Cl-C4-al~yl, hydroxyl, mercapto, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C,-alkoxy-; carbonyl, C~-C~-(alkylthio)carbonyl, Cl-C4-alkoxy(thiocarbonyl), Cl-C4-(alkylthio)thio-car~onyl, amino, Cl-C~-alkylamino, di-(Cl-C4-alkyl)amino, C~- or C1O-aryl or C5- or C10-arylamino, it being possible for each aryl to carry one to three of the groups mentioned -for Rll;
Ra is halogen, hydroxyl, mercapto, Cl-C4-alkoxy, Cl-C,-alkylthio, Cl-C~-alkoxycarbonyl, Cl-C,-^~ (alkylthio)carbonyl, Cl-C~-alkoxy(thio-carbonyl), C~-C,-(alkylthio)thiocarbonyl or Ra i8 C1-C5-alkyl, C1-C~-haloalkyl, NR1R2 or OR1;
Rl i8 Cl-C,-alkyl, C~- or C1O-aryl which can carry one to three of the groups mentioned for Rll;
Rll i8 halogen, hydroxyl, mercapto, Cl-C~-alkoxy, C1-C,-alkylthio, C1-C,-alXyl, nitro or amino;
X i3 oxygen or sulfur;
with the provi~o that a) R1 and R2 are not both H, methyl or ethyl, b) R3 and R~ are not both H, c) R5 and R are not both H, d) if R1 i9 methyl, R2 i8 i-butyl and R3 i8 amino, R4 i8 not H, e) if R1 iS methyl, R2 is H and R5 i3 phenyl, R~ i8 not hydroxyl, - 3 - O.Z. 0050/42008 f) if R1 is methyl, R2 is H and R~ i8 amino, R5 ~ 8 not carboxyl or ethoxycarbonyl, g) if Rl is H, RZ is methyl and R5 i~ H, RB L~ not hydroxyl, 5 h) if Rl is H, R2 is methyl and R4 is ethoxycarbonyl, R6 is not methyl or amino, i) if R5 is cyano, R~ i~ hydroxyl and Rl is n-butyl, R2 is not H, j) if R5 is cyano, R~ is hydroxyl and R1 is n-propyl, R2 ; 10 is not n-propyl, and the agriculturally usable salts of those compounds Ia and Ib which contain a bacic nitrogen substituent or an acidic hydroxyl substituent.
The present invention also relates to processes : 15 for preparing the compounds Ia and Ib and to herbicidal agents which contain 2-(4-hetaryloxy)- or 2-(4-aryloxy)-phenoxyacetic or -propionic acid derivatives and~or cyclohexenone derivatives as herbicidal acti~e ingredi-ents and compounds Ia and Ib as antidotes, and to methods for the selective control of unwanted plant growth using these herbicidal agents.
The clas~ of 1,3-disubstituted 2,4-dioxopyrido-~2,3-d]pyrimidines has been known for a long time. Thus, Arch. Pharm. 311 (1978) 406 describes pyrido[2,3-d]-pyrimidine-2,4-diones substituted in position 7 and l-allyl- and 1,3-dimethylpyrido~2,3-d]pyrimidine-2,4-diones substituted in positions 6 and 7 (see also TabLe 5). At the same time, reference is made to the action of a few compound~ as antitumor agent~ or as sedatives. The 3yntheses of other 5,6- and 6,7-di3ubstituted 1,3-dimethylpyrido[2,3-d]pyrimidine-2,4-diones are described in J.Heterocycl. Chem. 22 ~1985) 345 and 1469 (~ee also Table 5).

R~3PI.A~E~S13NT S~3T

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.

, , ~ :. `

209 ~)l133 - 3a - O . z . 0050/42008 J. Heterocyclic Chem. 17 (1980), 235 discloses 1-~2',4'-xylyl ) pyrido [ 2, 3-d ] pyrimidine-2, 4 ~ lH, 3H ) -dione, 3-ethyl-l-(2~4~-xylyl)pyrido[2~3-d]pyrimidine-2~4(lH~3H)-dione~
3 -crotyl -1- ( 2 ', 4 ~ -xylyl ) pyrido [ 2, 3 -d ] pyrimidine-2, 4 ( lH, 3H ) -dione, 3-benzyl- 1- ~ 2 ', 4 ' -xylyl ) pyrido [ 2, 3-d ] pyrimidine-2, 4 ~ lH, 3H ) -dione, 1-propylpyrido [ 2, 3-d ] pyrimidine-2, 4 ~ lH, 3H ) -dione, 3 -ethyl- 1-propylpyrido [ 2, 3-d ] pyrimidine-2, 4 ~ lH, 3H ) -dione, 3 -crotyl-l-propylpyrido ~ 2, 3-d ] pyrimidine-2, 4 ~ lH, 3H ) -dione, 3 -benzyl-1-propylpyrido [ 2, 3 -d ] pyrimidine-2, 4 ( lH, 3H ) -dione, 1-butyl-pyrido ~ 2, 3-d ] pyrimidine-2, 4 ( lH, 3H ) -dione and 1-crotyl-pyrido[ 2, 3-d]pyrimidine-2, 4 ~ lH, 3H) -dione .
EP-A 378 850 describes, inter alia, pyrido[2,3-d ] pyrimidine-2, 4 ( lH, 3H ) -diones o f the f ormula ., R ~ NJ~z _~m 0~ N N~
Rl R
and salts thereof for the preparation of drugs, the variables having the following meanings:
Rh is unsubstituted or substituted heterocyclyl, aryl or alkyl, Rl is cycloalkyl, trif luoromethyl, unsubstituted or 2 0 substituted alkyl or aryl, * is hydrogen, hydroxyl, cycloalkyl or unsubstituted or ~ubstituted alkyl, RL is unsub~tituted or substituted heterocyclyl, aryl, hydrogen, cycloalkyl, unsubstituted or substituted alkyl, unsubstituted or substituted amino, hydroxyl, unsubstituted or substituted alkoxy, trialkylsilyl-oxy, cycloalkoxy, unsubstituted or substituted aryl, alkylcarbonyloxy, arylcarbonyloxy or unsubstituted R13PLAC131OENT SI~BT

.' : ~ .

:.

.

2 0 9 ~ 3 - 3b - O.Z. 0050/42008 or substituted aminocarbonyloxy, Z is -CH2-CH2- or -CH=CH-, and R~ is 4-hydroxy-tetrahydropyran-2-on-6-yl, 4-alky1-4-hydroxytetrahydropyran-2-on-6-yl, -CH(OH)-CH2-CH~OH~-CH2-COORnor -CH(OH)-CH2-C(alkyl)(OH)-CH2-COORn, where R~ is hydrogen, alkyl, phenyl-substituted alkyl, aryl or a cation.
US 3,635,973 furthermore discloses a process for the preparation of, inter alia, herbicidal pyrido[2,3-d]pyrimidine-2,4(1H,3H)-diones which carry an alkyl, aralkyl, cycloalkyl, alkenyl or alkynyl group in the 3-position.
According to US 3,836,351, pyrido~3,2-d]pyrLmidine-2,4(1H,3H)-diones which carry an alkyl, dLmethoxyethyl, aralkyl, cycloalkyl, pyridylalkyl, alkenyl, tetrahydrofuryl, aryl, pyrrolidinyl, piperidinyl, homopiperidinyl or septamethyleneimino group in the 3-position and derivatives thereof substituted by alkyl in the l-position are also suitable for controlling plant growth.
The stated publications do not disclose that the known pyrido~2,3-d]pyrimidine-2,4(lH,3H)-diones and pyrido[3,2-d]pyrimidine-2,4~1H,3H)-diones have an antagonistic effect on herbicides.
EP-A 387 568 discloses substituted 1,8-naphthyridines and EP-A 368 212 naphthalene derivatives, which are suitable as antidotes for certain cyclohexenone derlv~tlve~.l ~
-REPLA~EMENT S~T

.~:

~.

209~433 - 4 - O.Z. 0050/42008 ///

.~ /

Cyclohexenone derivative~ of the formula XII

~ ~ ~n XII

where Rd iS C1-C~-alkyl;
A is C~-alkylene or C~-alkenylene, it being possible for each of these chains to carry one to three Cl-C3-alkyl groups and/or halogen atoms, or a 3-membered to 6-membered alkylene chain which, if desired, i9 substituted by Cl-C3-alkyl and which contains, as a ring member, an oxygen or sulfur atom which i8 not directly ad~acent to the oxime-ether moiety;
B is nitro, cyano, halogen, C1-C4-alkyl, C1-C4-alkoxy, Cl-C4-alkylthio, Cl-C,,-haloalkyl, Cl-C"-haloalkoxy, carboxyl, Cl-C4-alkoxycarbonyl, benzyloxycarbonyl REPLAC~ENT SE~T

~, . .. .

- .
.

2~9 J433 . - 4a - O.Z. 0050/42008 .
and/or phenyl, it being possible for the aromatlc radicals to carry one to three of the follow~ngz nitro, cyano, halogen, CL-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-haloalkyl, Cl-C4-haloalkoxy, carboxyl, Cl-C4-alkoxycarbonyl and/or benzyloxy-carbonyl;
,, //

., /

REPLACEXENT S~æET

:: ' .
~ .

2 0 9 ~ 4 3 3 - _ 5 _ O.Z. 0050/42008 and/or phenyl, it being possible for the aromatic radicals to carry one to three of the following~
nitro, cyano, halogen, C~-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-haloalkyl, Cl-C4-haloalkoxy, carboxyl, Cl-C~-alko~ycarbonyl and/or benzyloxy-carbonyl;
n is 0 to 3 or 1 to 5 when B is halogen;
R~ is C1-C4-alkoxy-C1-C6-alkyl or Cl-C4-alkylthio-Cl-C6-alkyl;
C3-C7-cycloalkyl or C5-C7-cycloalXenyl, it being possible for each of these groups to carry one to three of the following: Cl-C4-alXyl, Cl-C~-alkoxy, Cl-C4-alXylthio, Cl-C4-haloalkyl, hydroxvl and/or halogen;
a 5-membered saturated hatarocycl~ which contains one or two oxygen and/or ~ulfur atom~ as hetero atoms and which can carry up to three of the follow-ing: Cl-C~-alkyl, Cl-C~-alkoxy, Cl-C~-alkylthio and/or C1-C~-haloalkyl;
a 6- or ?-membered heterocycle containing one or two oxygen and/or sulfur atoms and up to two double bonds, it being pos3ible for this ring to carry one to three of the following: hydroxyl, halogen, C1-C~-alkyl, Cl-C~-alkoxy, Cl-C4-al~ylthio and/or Cl-C4-haloalkyl, a 5-membered heteroaromatic radical containing one or two nitrogen atoms and one oxygen or one sulfur atom, it being possible for this ring to carry one to three of the following: halogen, cyano, C1-C4-alkyl, C~-C~-alkoxy, C~-C~-alXylthio, Cl-C~-haloalkyl, C2-Cg-alkenyl, C2-C9-alkenyloxy, Cz-C6-haloalkenyl and/or C1-C~-alkoxy-C1-C~-alkyl, phenyl or pyridyl, it being possible for each of : these to carry one to three of the following:
halogen, nitro, cyano, C1-C4-alkyl, C1-C~-alkoxy, Cl-C~,-alkylthio, Cl-C~-haloalkyl, C3-C5-alkenyloxy, C3-C5-alkynyloxy and/or -NRrRB, where 2~9J~33 - 6 - O.Z. 0050/42008 I

I
R8 i8 hydrogen, C~-C4-alkyl,C3-C~-alkenyl, C3-C~-alkynyl, C~-C6-acyl or benzoyl whose aromatLc ring can carry one to three of the following: nitro, cyano, halogen, Cl-C~-alkyl, Cl-C4-alkoxy, C,-C4-alkylthio and/or Cl-C~-haloalkyl are described as herbicides in the earlier German Applications DE-A 4014985 and DE-A 4014986 and are mainly used for controlling unwanted grasses in dicotyledonous crops and in non-graminaceous grasses. Depending on the structure of the substituents and the application rate, compounds from this group can also be usad for sele~ s control of unwanted grasses in graminaceous crops such as wheat and rice.
It i8 an ob~ect of the present invention to provide compounds which diminish the disadvantages associated with the use of the abovementioned herbicides of the formula XII to an extent which is at least such that the harvested yield of the crop plants is now reduced negligibly, if at all.
We have found that this ob~ect is achieved by the compounds Ia and Ib defined above.
We have also found processes for preparing compounds Ia and Ib and methods for the combined treat-ment of crops with the compounds Ia and/or Ib on the one hand and wLth the herbicides XII on the other hand.
Certain derivatives Ia and Ib can be in the form of environmentslly compatible salts. Preferred in this connection are the al~ali metal salts, especially the potassium or sodium salt, alkaline earth metal salts, especially the calcium, magnesium or barium salt, mangan-ese, copper, zinc or iron salts, and ammonium, phosphon-ium, sulfonium or sulfoxonium salts, for example ammonium ~BPLASENBNT SHEBT
,; . .

20~433 . - 6a - O.Z. 0050/42008 -salts, tetraalkylammonium salts, benzyltriarylammonium salts, trialkylsulfonium salts or trialkylsulfoxon~um salts .

R~PLAC13~1BNT S~I13E3T

., ~ , , , `
`:

,, ~

209~4~3 - 7 - O.Z. 0050/42008 salt~.
With a ~iew to the intended u~e o the compound~
Ia and Ib as crop-protection agent~, preferred ~ubstitu-ents are the following:

5 R1 and R2 are hydrogen;
C~-C4-alkyl ~uch a~ methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methyl-propyl and 1,l-dLmethylethyl, especially methyl and ethyl;
C1-C4-haloalXyl, especially C1-C2-haloalkyl such as chloromethyl, dichloromethyl, trichloro-methyl, chlorofluoromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, dichloro-fluoromethyl, chlorodifluoromethyl, l-fluoro- -ethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, ; 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and penta-fluoroethyl;
C3-C,-cycloalkyl such as cyclopropyl, cyclo-pentyl, cyclohexyl, cycloheptyl, especially cyclopropyl;
R3 iq hydrogen, hydroxyl, mercapto, amino;
C1-C~-alkyl a~ mentioned for Rl, especially methyl and ethyl, C1-C~-alkylthio ~uch aq methylthio, ethylthio, propylthio, l-methylethylthio, butylthio, l-methylpropylthio, 2-methylpropylthio and l,l-dimethylethylthio;
C~- or C~0-aryl such a~ phenyl or naphthyl which can carry one to three of the groups mentioned ` for R11, preferably nitro, fluorine and chlorine;
R4 is hydrogen; C1-C~-alkyl aq mentioned for R1, preferably methyl and ethyl;
C1-C~-alXoxycarbonyl ~uch as methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, l-methyl-209 ~433 - 8 - O.Z. 0050/42008 ethoxycarbonyl, butyloxycarbonyl, l-methyl-propyloxycarbonyl, ~-methylpropyloxycarbonyl, 1,l-dimethylethoxycarbonyl;
Cl-C4-(alkylthio)carbonyl such as ~methylthio)-carbonyl, (ethylthio)carbonyl, ~propylthLo)-carbonyl, ~1-methylethylthio)carbonyl, (butyl-thio)carbonyl, ~l-methylpropylthio)carbonyl, ~2-methylpropylthio)carbonyl, ~l,l-dimethyl-ethylthio)carbonyl;
C~-C4-alkoxy(thiocarbonyl) such as methoxy(thio-carbonyl), ethoxy(thiocarbonyl), propyloxy-(thiocarbonyl), l-methylethoxy(thiocarbonyl), butyloxy(thiocarbonyl), l-methylpropyloxy(thio-carbonyl), 2-methylpropyloxy(thiocarbonyl), -1,l-dimethylethoxy(thiocarbonyl);
Cl-C~-(alkylthio)thiocarbonyl ~uch a~ (methyl-thio)thiocarbonyl, (ethylthio)thiocarbonyl, (propylthio)thiocarbonyl, (l-methylethylthio)-thiocarbonyl, (butylthio)thiocarbonyl, (1-methylpropylthio)thiocarbonyl, (2-methylpropylthio)thiocarbonyl, (l,1-dimethyl-ethylthio)thiocarbonyl;
R3 and R~ together are C3-C0-alkylene such as tri-, tetra-, penta- and hexamethylene, C3-C~-alkenyl-ene, especially C3-C~-alkenylene such a~
l-propen-1,3-ylene, 1-buten-1,4-ylene and 2-buten-1,4-ylene; 1,2-phenylene;
R5 i~ hydrogen, C~-C~-alkyl as mentioned for Rl, preferably methyl and ethyl;
- 30 C(o)R7 and C(S)R7 where R7 i8 preferably amino, methoxy, ethoxy, hydroxyl, methyl, ethyl, phenyl, methoxycarbonyl or ethoxycarbonyl;
R~ is C~-C~-alkyl as mentioned for Rl, preferably methyl and ethyl;
styryl;
C~- or C10-aryl ~uch as phenyl or naphthyl which can carry one to three of the groups mentioned .

209~4~3 - 9 - O.Z. 0050/42008 for Rl1, preferably chlorine, nitro and methyl;
CHzR8 where R9 i~ preferably chlorine, methoxy-carbonyl or hydroxycarbonyl;
Cl-C~-alkoxycarbonyl a~ mentioned for R4;
cl-c4-~alkylthio)carbonyl as mentioned for R4;
C~-Cq-alkoxy(thiocarbonyl) a~ mentioned for R~;
Cl-C4-(alkylthio)thiocarbonyl a~ mentioned for R4;
hydroxyl; amino;
C1-C4-alkoxy such as methoxy, ethoxy, propyloxy, l-methylethoxy, butyloxy, l-methylpropyloxy, 2-methylpropyloxy and 1,l-dimethylethoxy, particularly preferably l-methylethoxy;
C~-C~-alkylthio as mentioned for R3;
C1-C4-alXylamino ~uch as methylamino, ethyl-amino, propylamino, l-methylethylamino, butyl-amino, l-methylpropylamino, 2-methylpropyl-amino, l,l-dimethylethylamino;
NHCXR~ where X is preferably oxygen, especially methylcarbonylamino and ethylcarbonylamino;
NHSO2Rl, especially 4-toluenesulfonylamino;
2-thienyl, 3-thienyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-indolyl, particularly preferably 2-thienyl and 3-indolyl, it being possible for each of these groups to be substituted by one or two of the groups mentioned for Rl1;
~ R5 and R~ together are C3-C~-alkylene such as tri- and :i tetramethylene, C3-C5-alkenylene such as l-propen-1,3-ylene, 1-buten-1,4-ylene and 2-buten-1,4-ylene or 1,2-phenylene, each of which can be substituted once or twice by C1-C~-alkyl such a~ methyl and ethyl, C1-C~-haloalkyl such as trifluoromethyl and C3-C7-cycloalkyl x 8uch a8 cyclopropyl, cyclopentyl and cyclo-;~ 35 hexyl, and can also contain carbonyl or thio-:~ carbonyl groups; 1,3-propanediylcarbonyl, 2,2-dimethyl-1,3-propanediylcarbonyl and .
. .
.
' ' ~
.: .
- :. ... . . ...

209.~3 - 10 -O.Z. 0050/42008 1,2-phenylenecarbonyl areparticularly preferred;
R7 is hydrogen, hydroxyl, amino;
Cl-C~-alkyl aq mentioned for Rl, e~pecially methyl and ethyl;
C~-C4-alkoxy a~ mentioned for RB, especially methoxy and ethoxy;
Cl-C4-alkylthio a~ mentioned for R3, e~pacially methylthio and ethylthio;
Cl-C4-alkoxycar~onyl as mentioned for R4, especially methoxycar~onyl and ethoxycarbonyl;
C~-C4-(al~ylthio)car~onyl as mentioned for R4;
C~-C4-alkoxy(thiocar~onyl) a~ mentioned for ~4;
C,-C4-(alkylthio)thiocarbonyl as mentioned for _ R4;
Cl-C4-alkylamino as mentioned for R6;
di-(C~-C4-alkyl)amino ~uch as N,N-dimethylamino, ~ N,N-diethylamino, N,N-dipropylamino, N,N-di-(l-methylethyl)amino,N,N-dibutylamino,N,N-di-(1-methylpropyl)amino, N,N-di-(2-methylpropyl)-amino, N,N-di-(l,l-dimethylethyl)amino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-methyl-N-(l-methylethyl)amino, N-butyl-N-methylamino, N-methyl-N-(l-methylpropyl)-amino, N-methyl-N-(2-methylpropyl)amino, N-(l,l-dimethylethyl)-N-methylamino, N-ethyl-. N-propylamino, N-ethyl-N-(l-methylethyl)amino, N-butyl-N-ethylamino, N-ethyl-N-(l-methyl-propyl)amino, N-ethyl-N-(2-methylpropyl)amino~
N-ethyl-N-(l,l-dimethylethyl)amino, N-(l-methylethyl)-N-propylamino, N-butyl-N-propylamino, N-(1-methylpropyl)-N-propyl-. amino, N-(2-methylpropyl)-N-propylamino, N-(l,l-dimethylethyl)-N-propylamino, N-butyl-: 35 N-(l-methylethyl)amino, N-(l-methylethyl)-N-(l-methylpropyl)amino, N-(l-methylethyl)-N-(2-methylpropyl)amino, N-(l,l-dime~hylethyl)-' ., .
.~
;~ , ''-'' ~'`"" ' ' ; . "' ' .
.~ . . .

209 )~3 - 11 - O.Z. 0050/42008 N-(l-methylethyl)amino, N-butyl-N-(1-methyl-propyl)amino, N-butyl-N-(2-methylpropyl)amino, N-butyl-N-(l,l-dimethylethyl)amino, N-(1-methylpropyl)-N-(2-methylpropyl)amino, N-(1,l-dLmethylethyl)-N-(l-methylpropyl)amino and N-(l,l-dimethylethyl)-N-(2-methylpropyl)-amino;
C8- or C10-aryl and C6- or C1~-arylamino such as phenyl, naphthyl or phenylamino who~e aryl radicals can carry one to three of the groups mentioned for R11;
R8 is halogen, especially fluorin~ and chlorine;
hydroxyl; mercapto;
C,-C4-alkoxy as mentioned for R~; -C1-C4-alXylthio a~ mention~d fo- R3;
C1-C~-alkoxycarbonyl a~ mentioned for R4;
C1-C4-(alkylthio)carbonyl as mentioned for R~;
Cl-C~-alkoxy(thiocarbonyl) as mentioned for R~;
C1-C~-(alkylthio)thiocarbonyl as mentioned for i 20 R~;
: -O-C-R~
.,~ 1 .

where X i~ particularly preferably oxygen and R9 is hydrogen, methyl or ethyl;
R9 is C1-C~-alkyl as mentioned for R1, particularly preferably methyl and ethyl;
Cl-C~-haloal~yl a~ mentioned for R~;
NR1R2, preferably amino or dimethylamino;
ORl, preferably hydroxyl, methoxy or ethoxy;
R10 i8 Cl-C~-alkyl as ment~oned for R~;
; C~- or C10-aryl such as phenyl or naphthyl which can carry one to three of the groups mentioned . for Rl1, especially 2-methylphenyl, 3-methyl-phenyl or 4-methylphenyl;
Rll is halogen, especially fluorine and chlorine;
hydroxyl; mercapto; nitro; amino;

~,:

.: , :, .: '` :
. , ; , 209~43~
- 12 - O.Z. 0050/42008 ~ Cl-C~-alkoxy as mentioned for ~, e~pecially methoxy and ethoxy;
Cl-C~-alkylthio as mentioned for R3, e~pecially methylthio and ethylthio;
Cl-C4-alkyl as mentioned for Rl, preferably methyl, ethyl, propyl, 1-methylethyl and l,1-dimethylethyl;
X is oxygen or sulfur.
Particularly suitable compounds Ia and Ib are to 10 be found in Table~ 1 to 4 (see Examples).
The novel compounds I can be obtained in a variety of way~. Sub~tituted pyridopyrimidina~ ar~
obtained, for example, by condensing 4-aminopyrLmidines with ethoxymethylenemalonic acid derivatives or by _ reacting 4-amino-5-formylpyrimidines with ~-diketone~
(E. Lunt and C.G. Newton in 'Comprehensive Heterocyclic Chemistryl~, Vol. 3, Pergamon Pres~, Oxford, pp. 215-232).
Another route is the reaction of ~-dialkylamino ketones with 4-aminopyrimidines (R. TroschUtz and H.J. Roth:
Arch. Pharm. 311 (1978), 406, 542).
The pyridinepyrimidine tsic] derivatives Ia are obtained, for example, by reacting a 4-aminopyrimidine-2,4(lH,3H)-dione II with a ~-chloroalkenal III in an ; inert solvent and under a protecti~e gas atmosphere.
It is advisable to carry out this reaction by adding the alkenal III in liquid phase at room tempera-ture over the course of 5 to 30, preferably 10 to 20, min to the compound II.
A~ a rule, the reaction mixture i8 then heated to ; 30 from 20 to 150, preferably from 70 to 110C and left at this for 3 to 12, in particular 5 to 7 h, before it is cooled to room temperature. The products are generally solid and precipitate out on cooling and can be separated off by conventional methods. The molar ratio of compound II to alkenal III is generally chosen in the range from 0.7sl to 1.2~1.
The pyrimidine derivatives II are generally known .. . .

209a433 - 13 - o.Z~ 0050/42008 /

/

/
R5 is preferably hydrogen or Cl-C,-alkyl, especially methyl or ethyl, and Rl~ is C1-C,-alkyl, preferably methyl or ethyl.
i Another method for preparing the compounds Ib comprises reacting a pyrimidine derivative VIIa or VIIb in a conventional manner (see J. Heterocycl. Chem. 22 (19~5) 345) with a malonic acid derivative VIIIa, VIIIb or VIIIc. In this case, R~ is cyano, C(o)R7 or C(S)R7, Rl5 is C~-C~-alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or tert-butyl, especially ethyl; R~ C~-C,-alkyl a- mentioned for R15. especially methyl; C0-aryl-C2-C,-alkenyl such as styryl;
C~-, C10- or C1~-aryl such as phenyl or naphthyl, especially phenyl;
lt being possible for the aryl groups to carry one to R8~LACE~BNT S~BBT

:"
', . . .

209 ~433 - 14 - O.Z. 0050/42008 three of the groups mentioned for R11 or CH2R~.
The compounds Ib can also be prepared by resctln~
a compound Ib where R~ ls hydroxyl Ln a conventlonal manner (see P. Màtyus, P. Soh~r and H. Wamhoff, Lleblgs Ann. Chem. (1984) 1653) with the compound IX, which Ls R16-Nu. In this case, R18 is C1-C4-alkyl as mentLoned for R1, preferably i-propyl or n-butyl, and Nu is a nucleofugic leaving group such as a halogen, preferably iodine.
An additional method for preparin~ compounds Ib comprises reacting a compound Ib where R~ is amino in a conventional manner with a compound Xa, which is R9(CX)Nu, or Xb, which is R10-SO~-Nu.
Specific examples of herbicidal cyclohexenones of the formula XII whose tolerance by crop plants can be improved by the compounds Ia and Ib are listed in Tables B to R which follow (see German Applications DE-A 4014985 and DE-A-2822304).

REPLACE~ENT SHEET

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209a433 - 55 - O.Z. 0050/42008 - Herbicidal active ingredient~ and antldote compound~ can be applied together or separately after emergence to the leave~ and ~hoots of the crop plants and the unwanted gra~ses. The antidote is preferably applied at the same tLme as the herbicidal actLve ingredient.
Separate application with the antidote being applied fir~t, and then the herbicidal active ingredient, to the field is also posqible. This may entail the herbicidal active ingredient and antidote being formulated together or separately in a form which can be suspended, emulsi-fied or dissolved for spraying.
Also Lmportant in practice is treatment of the seeds of the crop plants with the antidote before sowing.
The herbicidal active ingrPdient is then applied alone in -a conventional manner.
The amounts of an antidote which are required vary when herbicidal (hetaryloxy)- or aryloxyphenoxy-acetic acid derivatives XI are used in different crops.
The ratios of amounts can be varied within wide limits.
They also depend on the structure of the (hetaryloxy)- or aryloxyphenoxyacetic acid derivative and the particular crop. Suitable ratios of antidote to herbicidal active ingredient are from O.Olsl to 10:1, preferably from 0.1:1 to 4:1, by weight.
The amounts of an antidote required for the cyclohexenone derivative XII vary for different crops.
The ratios of the amounts of a cyclohexenone derivative ~II and a compound Ia or Ib can be varied within wide li~its. They depend on the structure of the cyclohexenone derivatLve XII and of the compound Ia or Ib and on the particular crop. Suitable ratios of antidote to herbi-cidal active ingredient sre from 0.01:1 to 10:1, prefer-ably 0.25:1 to 4:1, by weight when applied either to-gether or ~eparately.
The novel herbicidal agent~ can contain, be~ide~
the compound Ia or Ib a~ antidote and a herbicide from the group of (hetaryloxy)- or aryloxyphenoxyacetic acids : .

. .

2~3~33 - 56 - O.Z. 0050/42008 XI or of cyclohexenones XII, other the herblcidal or ~- growth-regulating active ingredients with a different chemical structure, with retention of the antagoni~tic effect.
The agents according to the invention or, in the case of separate application, the herbicidal actLve ingredients or the antidote are applied, for example, in the form of directly sprayable solutions, powders, suspensions, including high-percentage aqueous, oily or other suspensions, or dispersions, emulsions, oil disper-sions, pastes, dusting or broadcasting agents or gran-ules, by spraying, atomizing, dusting, broadcasting or watering. The application forms depend entirely on the purposes for which they are used.
Suitable for preparing directly sprayable solu-tions, emulsions, pastes and oil dispersions are mineral oil fractions of medium to high boiling point such as kerosine or diesel oil, also coaltar oils, and oils of vegetable or animal origin, aliphatic, cyclic or aromatic hydrocarbons, eg. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or deriva-tives thereof, eg. methanol, ethanol, propanol, butanol, chloroform, tetrachloromethane, cyclohexanol, cyclohexan-one, chlorobenzene, isophorone, highly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methyl-pyrrolidone and water.
Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders or oil dispersions by adding water. To prepare emulsions, pastes or oil dispersions, the herbicidal active ingredient and/or antidote can be homogenized, as such or dissolved in an oil or solvent, using wetting agents, adhesion promoters, dispersants or emulsifiers, in water.
However, it is also possible to prepare concentrates, which are suitable for dilution with water, from herbi-cidal active ingredient and/or antidote, wetting agent, adhesion promoter, dispersant or emulsifier and, 209a433 .
- 57 - O.Z. 0050/42008 possibly, solvent or oil.
Suitable surfactants are alkalL metal, alkaline earth metal and ammonium salts of ligninsulfonic ac~d, naphthalenesulfonic acid, phenolsulfonic acid, alkylaryl sulfonates, alkyl sulfates, alkylsulfonates, al~ali metal and alXaline earth salts of dibutylnaphthalene~ulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, fatty acid alkali metal and alkaline earth metal calts, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated fatty alcohol glycol ethers, products of the condensation of sulfonated naphthalene and naph-thalene derivatives with formaldehyde, products of the condensation of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octyl-phenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethy-lene alkyl ether, ethoxylated polyoxypropylene, laurylalcohol polylglycol [sic] ether acetal, sorbitol ester, lignin sulfite waste liquors and methylcellulose.
Powders and dusting and broadcasting agents can be prapared by mixing or grinding together herbicidal active ingredient and/or antidote with a solid carrier.
Granules, eg. coated, impregnated or homogeneous granuies, can be prepared by binding the active ingredi-ents to solid carrier~. Examples of qolid carrier~ are mineral earths such as silica gel, silicic acids, sili-cates, talc, kaolin, attapulgite, limestone, chalk, bole,loe~, c18y, dolomite, diatomaceous earth, calcium and magnesium sulfates, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereals flour, bark meal, wood meal and nutshell meal, cellulose powder and other solid carriers.
The formulations contain from 0.01 to 95% by -"- ' '' 2 0 9 ~ ~3 3 - 58 - O.Z. 0050/42008 weight of herbicidal active ingredient and antldote, preferably from 0.5 to 90% by weight. The appllcatlon rates for herbicidal acti~e ingredient are from 0.2 to 5 kg/ha active substance.
The preparation of the novel compounds Ls explained in detail by the following examples.
PREPARATION EXAMPLES

5-Ethyl-1,3,6-trimethylpyrido[2,3-d]pyrimidine-2,4-(lH,3H)-dione O Et Me~

Me 11.6 g (75 mmol) of 4-amino-1,3-dimethylpyrimidine-2,4(lH,3H)-dione were introduced into 100 ml of absolute dimethylformamide under nitrogen at room temperature.
Then, over the course of 15 min, 13.2 g (100 mmol) of 3-chloro-2-pentene-2-carbaldehyde were added dropwise.
The reaction mixture was then heated to 95C over 30 min and kept at this temperature for 6 h. It was subsequently cooled to room temperature, and the product was removed by filtration. Drying resulted in 15.6 g (67~) of yellow crystalline product (active ingredient example 1.006).
` The products listed in Table 1 were prepared correspondingly:

. . ' ' ' .
~ ~ .

209~'133 : - 59 - O.Z. 0050/42008 TAB~E 1 Me`N~R 4 l~le Example No. R3 R4M.p.

1.001 Ph H145C
1.002 3-NO2-C6H4 H244-248C
1.003 4-Cl-C6H4 H165C
1.004 Me Ms15~-156C
1.005 Me Et90C
1.006 Et Me120-123C
1.007 Ph Me172C
1.008 -(CH2)3- 134C
1.009 -(CH2)~- 148-150C
1. 010 - (CH2) 5- 145C
1.011 -tCH2)0- 165C

EXA~PLE 2 1,3-Dimethyl-7-(3-nitrophenyl)pyrido~2,3-d]pyrimidine-2,4(lH,3H)-dione M~`~N 2 Me A mixture of 6.2 g (40 mmol) of 4-amino-1,3-dimethylpyrimidine-2,4(lH,3H)-dione and 11.6 g (45 mmol) of 3-nltro-~-dimethylaminopropiophenone hydrochloride in 100 ml of glacial acetic acid was refluxed for 3 h. After addition of 2 ml of concentrated hydrochloric acid, the mixture was ~tirred at the same temperature until the su~pension was colorless. Cooling and filtration resulted in 8.9 g (78~) of cry~talline product (acti~e ingredient example 2.001).

:
;

.
~ ' .
.
" .

209~433 - 60 - O.Z. 0050/42008 The products listed in Table 2 were prepsred ~n a sLmilar manner:

o R 2`NJ~R 5 O~N~N~R 6 Rl S Example No. R1 ~ R5 R6 M.p.
;
~` 2.001 ~e Me H 3-NO2-C5H~ 261C
2.002 Me Me H -CH=CH-Ph 100-110C
2.003 Me Me H 2-Thienyl 186-188C
10 2.004 ~e Me H 3-Indolyl 210-215C
2.005 Me Me Me 4-Cl-C6H~ 235-244C
2.006 Et H H 4-NO2-C6H~ > 250C

1,3-Dimethyl-6-methoxycarbonyl-7-methoxycarbonylmethyl-pyridot2,3d]pyrimidine-2,4(lH,3~)-dione tsic]
n Me ~ C02Me CH2C02Ma M~
A su~pen~ion of 4.85 g (20 mmol) of 5-dimethyl-aminomethylenepyrimidine and 3.48 g (20 mmol) of dimethyl acetonedicarboxylate in 100 ml of absolute ethanol was cooled to 0C. 2.4 g (24 mmol) of triethylamine were added dropwise over the course of 20 min, and the mixture was then ~tirred at room temperature for 2 h. It was then cooled to -15C, and the precipitate was filtered off and dried under reduced pressure. This resulted in 3.81 g 2S (59~) of product (active ingredient example 3.008).
The compounds listed in Table 3 can be prepared in a similar manner:
:

--: . : . .. ....
.. , ' :. ~ ' . ~ '' ` `
. , . ' ' .

209~433 - 61 - O. Z . 0050/42008 TABL~ 3 R 2`N~,R 5 oll~NJ~R6 R I

Example Rl R2 R5 R6 M.p.
No .
. .
3.001 Me Me CONH2 NH2 >250C
3.002 Me Me COHH2 Me >250C
3.003 Me Me CONHPh Ph ~250C
3.004 Me Me CO2Et CH2C189- 90C
3.005 Me Me COzEt Ph 155-157C
3.006 Me Me CO2Et CO2Et>250C
3.007 Me Me CO2Me NH2 >250C
3.008 Me Me C02~e CH2CO2Me164- 166C
3.009 Me Me C02H Me >250C
3.010 Me Me CO2H OH 263-266C
3.011 Me Me C02H CH2CO2H>250C
3.012 Me Me C02H Ph 217-219C
3.013 Me Me COMe Me 153C
3.014 Me Me COPh Ph >250C
3.015 Me Me COCO2Et Me >250C
3.016 Me Me COCO2Et Ph >250C
-OC
3.017 Me Me ~ >250C
3.018 Me Me -C-(CH2) 3 - >250C

3.019 Me Me -C-IClH2-cMe2-cH2- 181 - 192 C
O
: 3. 020 Et H C0Mc Me >250C
3.021 Et H CO2Et Me 250C
3.022 Et H CO2Et NH2 >250C
3.023 Et H CO2Et OH >250C
3.024 Et H C2~H2 Me 215C
3.025 Et H CO2H NH2 >250C
3.026 cyclo-Pr Et COMe Me >250C
; 3.027 cyclo-Pr Et CO2Et Me 240C
3.028 cyclo-Pr Et CN NH2 >250C
, 3.029 cyc l o-Pr Et CONH2 Me 83C
'` 3.030 cyclo-Pr Et CO2Et NH2 >250C
3.031 cycto-Pr Et CONH2 NH2 >250C
3.032 cyclo-Pr Et CO2MO OH 148-150C

:' :
.:.
: , ` ' ''~ - :
.' : `, ' ' . ` ' ' ' ' .:
` : `: .. .

209 ~433 - 62 - O.Z. 0050/42008 1,3-Dimethyl-7-ethoxycarbonyl-8-ethylcarbonylaminopyrido-[2,3-d]pyrimidine-2,4(lH,3H)-dione [~lc]

Me~N~CO ~E t OJ~N~NH I I E t Me o A mixture of 5.60 g (20 mmol) of ethyl 7-amino-1,3-dimethyl-2,4(1H,3H)-dioxopyrido[2,3-d]pyrimidine-6-carbo~ylat2 and 2.86 g (22 mmol) of propionic anhydride in 30 ml of propionic acid was refluxed for 24 h. Cooling and filtration resulted in 5.47 g (82%) of product (active ingredient 4.002).
The compounds listed in Table 4 were prepared in a similar manner:

~. .
.. O
Me~C02Et O'l~R 6 ., M~
:~ 15 Example No. R~ M.p.
., 4.001 -NHCOMe 148C
4.002 -NHCOEt 131-134C

4.003 -~SO ~ ~250-C

4.004 -OCHMe2 112C

:Compounds Ia and Ib which are di~closed in the literature or prepared by literature methods and which - are likewi~e able to increa~e the tolerance by crop plants of the herbicidal acti~e ingredient~ of the Sormulde XI and ~II are ll~ted ln T~ole 5 whlch ~ollowe.

' 209~3 - 63 - O.Z. 0050/42008 TABL~ 5 O R3 o Me~R 4 Me~NJ~R 5 oJ~ I N~J C~NJ~N~R6 Me Me la la Example R3 R' R5 - ~6 Llterature 5.001 OH C02Et - - 1 5 . 002 NH 2 CN - - *
5 . 003 OH H - - *
5 . 004 - - H Ph 2 5 . 005 - - H 4-Me-C6H4 2 S . 006 - - Me Ph 2 -CH2-(o-c6H4) 2 5.008 - ~ -(CH2) 2-(-C6H4) 2 5 . 009 - - - (CH2) 3- (o-COH4) 2 5,010 - - CN NH2 3 5.011 ~ ~ C02Et NH2 3 5.012 - - C02Et OH 3 . 5.013 - - C02Et Me 3 5.01~ - - C02H NH2 3 5. 015 ~ ~ -- C -- N - C -- N -- 3 5.016 - _ ~ C -- NH ~ 6 -- NH -- 3 S

1) G.L. Ander~on, J. Heterocyl. [~ic] Chem. 22 (1985) 1469.
2) R. TroschUtz, H.J. Roth, Arch. Pharm. 311 (1978) ` 406.
3) R. Hirota, Y. Ritade, S. Senda, J. Heterocycl. Chem.
22 (1985) 345.
~) prepared in a ~imilar manner to 1).
` Example~ of the biological a~-tion The effect of variou3 repre~entative~ of the :. . .
;; . ~ . . . :

- 64 - O.Z. 0050/42008 novel herbicidal agent~ or combinations thereo, composed of herbicide and antidote, on the growth of wanted and unwanted plants compared with the herbicldal actLve ingredient alone was demonstrated by the followlng examples from glasshouse tests:
The plants were grown in plastic flowerpots with a capacity of about 300 cm3 containing loamy sand with about 3.0% humus as substrate. The seeds of the te~t plants were sown shallowly, keeping the species separate, and were moistened. The pots were then covered with transparent plastic covers until the seeds had uniformly germinated and the plan~ ~ad star. d to grow.
For the post-emergence treatment, the test plants were grown to a height of from 3 to 20 cm, depending on -- 15 species, and only then treat2d. The herbicidal agents were suspended or emulsified in water as dispersant and were sprayed using finely distributing nozzles.
The example~ of cyclohexenone herbicides XII were fH3 OH ~N-oC2Hs C2HS-S-~ ~ H ~ B.15 n-C 3H7 ,~
~ ~{~(CH2)2C~=C ~ I
S Y ~ \ E.34 (~ C2H5 ' The~e herbicidal active ingredient-~ were each added as commercial formulation (100 g/l emulsion concentrate) to the preparation of the particular antidote and thus applied together with the latter.
For comparative test~, active ingredients B.15 and F.34 were each applied with a mixture of 80% by volume cyclohexanone and 20% by volume ethoxylated castor oil (formulation without antidote).
All the antidotes were prepared for the post-emergence treatment in a mixture composed of 80% by - volume cyclohexanone and 20% by volume ethoxylated castor ::`

209~33 - 65 - O.Z. 005~/42008 oil containing 10% by weight active ingredlent.
- List of test plants:
Abbreviation Lat. name English name S LOLMU Lolium multLflorum Italian ryegras~
SETVI Setaria viridi~ Green foxtail TRZAW Triticum aestivum Winter wheat ZEAMX Zea mays Indian corn The test vessels were placed in a glasshouse with the warm-loving species at 18 to 30C and those from temperate clLmatic zone~ at 10 to 25C.
The agents were suspended in water as carrier and dispersant and were applied to run-off to the plants using a mobile sprayer with finely di~persing nozzles.
- 15 The tests la~ted 3 to 5 week~ during which the plants were tended and their reaction to the individual treatments was recorded.
The damage caused by the chemical agents was assessed on a scale-from 0 to 100% by comparison with the untreated control plants. On this scale, 0 means no damage and 100 means complete destruction of the plants.
The following Tables 6 to ll document the antidote action of novel pyridot2,3-d]pyrimidine-2,4(1H,3H)-diones Ia and Ib.
The antidote compounds distinctly improve the tolerance of the herbicides B.15 and E.34 by graminaceous crop plants.
TA3LE 6:
Improvement in the tolerance of herbicide B.15 (sethoxy-dim) by corn and wheat on adding an antidote compound with post-emergence application; glasshouse test ~:.

.

' ;.
.
. .
. ~', '` '',, . ~' '' ,' 2~9~433 - 66 - O.Z. 0050/42~08 Application ra~e ~kg/ha] Test plsnts and d~mage ~%]
Anti- Herbicide Antidote Crop plant Unwanted plant dote Indian Winter Lolium No. corn wheat mLltiflorum - _ - 0.015 80 - 9~
3.001 0.015 0.06 lS - 98 - 0.06 - 40 100 1.004 0.06 0.25 - 0 100 Table 7:
Improvement in the tolerance of herbicide E.34 by corn and wheat on adding an antidote compound with po~t-emergence application; glasshouse test Application rate [kg/ha] Te~t plant~ and damage [%]
15 Anti- Herbicide Antidote Crop plant Unwanted plant : dote Indian Winter Lolium No. corn wheat multiflorum - 0.25 85 80 100 1.006 0.250.75 15 20 90 .
Table 8:
Improvement in the tolerance of herbicide E.34 by corn on ;~ adding an antidote compound with po~t-emergence applica-tion; glasshouse test Application rate lkg/ha] Test plants and damage [%]
Anti- Herbicide Antidote Crop plant Unwanted plant dote Indian Setaria No. corn virdis - 0.125 - 75 100 ; 1.001 0.1250.375 30 100 Table 9s Improvement in the tolerance of herbicide E.34 by corn on : adding a pyrido~2,3-d]pyrimidin having an antidote .~ 35 ef~ect; post emergence application in the greenhouse 2~9~3~
- 67 - O.Z. 0050/42008 Application rate [kg/ha] Test plants and ~Am~ge [%]
Anti- Herbicide Antidote Crop plant U~wanted plant dDte Corn LixisSetar~a No. variety viridis _ _ - 0.25 - 100 100 3.008 0.25 0.25 30 100 3.00S 0.25 0.25 20 100 3.004 0.25 0.25 30 100 3.006 0.25 0.25 0 100 1.007 0.25 0.25 20 95 1.006 0.25 0.25 30 100 ` 1.010 0.25 0.25 10 95 - 0.125 - 85 100 5.011 0.125 0.125 50 100 5.013 0.125 0.125 30 100 3.001 0.125 0.125 15 100 3.008 0.125 0.125 20 98 3.005 0.125 0.125 10 100 3.004 0.125 0.125 20 95 ~: 3.006 0.125 0.125 0 98 1.007 0.125 0.125 10 90 1.006 0.125 0.125 15 85 1.008 0.125 0.125 10 90 3.016 0.125 0.125 30 90 1.010 0.125 0.125 0 9o .~, Table 10 Improvement in the tolerance of the herbicide ~.34 by : corn and wheat on atding a pyrido~2l3-d]pyrimidine having ; 30 an antidote effect; postemergence application in the ~ greenhouse ~ . .
~. :

209~4~3 - 68 - O.Z. 0050/42008 Application rate [kg/ha] Te~t plants and damage ~%]
Anti- Her~icide Antidote Crop plant Unwanted plant dote Corn Spring Setaria No. I,l~ ~ wheat v~id~
variety Star - 0.06 - 60 90 100 5.011 0.06 0.06 20 - 100 3.013 0.06 0.06 0 - 75 3.001 0.06 0.06 0 _ 90 3.009 0.06 0.06 20 _ 85 - 3.003 0.06 0.06 20 _ 80 3.005 0.06 0.06 o - 80 3.004 0.06 0.06 0 65 85 3.006 0.06 0.06 0 10 90 : 1.007 0.06 0.06 10 20 80 1.009 0.06 0.06 10 65 90 3.016 0.06 0.06 10 50 95 Table 11 Improvement in the tolerance of herbicide E.34 by wheat by adding a pyridot2,3-d~pyrimidine having an antidote effect; postemergence application in the greenhouse Application rate [kg/ha] Test plants and damage [%]
Anti- Herbicide Antidote Crop plant Unwanted plant 2S dote Spring wheat Setaria No. Star viridis - 0.03 - 85 75 3.008 0.03 0.03 lO 60 3.005 0.03 0.03 lO 45 3.004 0.03 0.03 40 75 3.006 0.03 0.03 0 40 ;..... .

Claims (8)

We claim:

1. A pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione of the formula Ia or Ib Ia Ib where R1 is C1-C6-alkyl or C3-C7-cycloalkyl, R2 is hydrogen, C1-C4-alkyl or C3-C7-cycloalkyl;
R3 is C1-C4-alkyl, hydroxyl or phenyl which can carry one to three of the following groups:
halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl or nitro;
R4 is hydrogen, C1-C4-alkyl or cyano; or R3 and R4 together are C3-C7-alkylene;
R5 is hydrogen, C1-C4-alkyl, cyano or C(=O)R7;
R6 is amino, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxycarbonyl, phenyl-C2-C4-alkenyl or phenyl, it being possible for each of the phenyl rings to carry one to three of the following groups:
halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl or nitro;
2-thienyl or 3-indolyl, it being possible for each of these groups to carry one or two of the following groups : halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl or nitro;
CH2R8, NHC(O)R9 or NHSO2R10; or R5 and R6 together are C3-C8-alkylene or 1,2-phenylene, which can be substituted by C1-C4-alkyl or can contain carbonyl groups;
R7 is amino, hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxycarbonyl;
phenyl or phenylamino, it being possible for each phenyl ring to carry one to three of the following groups: halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl or nitro;
R8 is halogen or C1-C4-alkoxycarbonyl;
R9 is C1-C5-alkyl;
R10 is phenyl which can carry one to three of the following groups: halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl or nitro;
R11 is halogen, C1-C4-alkyl or nitro;
where - R1 is not methyl when R2 is hydrogen or methyl, - R1 and R2 are not both ethyl, and - R5 and R6 are not both methyl, and the agriculturally usable salts of those compounds Ia and Ib which contain a basic nitrogen substituent or an acidic hydroxyl substituent.

2. A process for preparing a compound Ia as claimed in claim 1, which comprises reacting a 4-aminopyrimidine-2,4(1H,3H)-dione of the formula II

II

with a .beta.-chloroalkenal of the formula III

III

where R3 is hydrogen, C1-C4-alkyl, C6- or C10-aryl which can carry one to three of the groups mentioned for R11, or reacting a compound II with a .beta.-alkoxyacrylic acid derivative of the formula IV

IV

where R12 is C2-C5-alkoxycarbonyl, C2-C5-alkoxythiocarbonyl or cyano, and R13 is C2-C5-alkyl, in a conventional manner to give the intermediate of the formula V

V

and converting the latter at elevated temperature into the compound Ia.

3. A process for preparing a compound Ib as claimed in claim 1, which comprises reacting a compound II in a conventional manner with a .beta.-dialkylamino ketone of the formula VI

VI

where R5 is hydrogen or C1-C4-alkyl and R14 is C1-C4-alkyl, or reacting a pyrimidine derivative of the formula VIIa or VIIb VIIa VIIb in a conventional manner with a malonic acid derivative of the formula VIIIa, VIIIb or VIIIc NC-CH2-R5" R15O2C-CH2-R5" R6'(CO)CH2-R5"
VIIIa VIIIb VIIIc where R5 is cyano, C(O)R7 or C(S)R7, R15 is C1-C4-alkyl and R8' is C1-C4-alkyl, C8-aryl-C2-C4-alkenyl, C8-, C10- or C14-aryl, it being possible for each aryl to carry one to three of the groups mentioned for R11, or is CH2R8, or reacting a compound Ib where R8 is hydroxyl in a conventional manner with a compound of the formula IX

where R15 is C1-C4-alkyl and Nu is a nucleofugic leaving group, or reacting a compound Ib where R6 is amino in a conventional manner with a compound of the formula Xa or Xb xa Xb

4. A herbicidal agent containing at lesst one pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione of the formula Ia or Ib as claimed in claim 1 and at least one herbicidal active ingredient from the group comprising the cyclohexenone derivatives of the formula XII

XII
where Rd is C1-C6-alkyl;
A is C4-alkylene or C4-alkenylene, it being possible for each of these chains to carry one to three C1-C3-alkyl groups and/or halogen atoms, or a 3-membered to 6-membered alkylene chain which, if desired, is substituted by C1-C3-alkyl and which contains, as a ring member, an oxygen or sulfur atom which is not directly adjacent to the oxime-ether moiety;
B is nitro, halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl;
n is 0 to 3 or 1 to 5 when B is halogen;
R? is C1-C4-alkylthio-C1-C5-alkyl;
C3-C7-cycloalkyl or C5-C7-cycloalkenyl, it being possible for each of these groups to carry one to three of the following: C1-C4-alkyl and/or C1-C4-alkylthio;
a 6-membered heterocycle containing one or two oxygen and/or sulfur atoms and up to two double bonds, it being possible for this ring to carry one to three of the followings hydroxyl, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio and/or C1-C4-haloalkyl, a 5-membered heteroaromatic radical containing one or two nitrogen atoms and one oxygen or one sulfur atom, it being possible for this ring to carry one to three of the following: C1-C4-alkyl and/or C1-C4-alkoxy-C1-C4-alkyl;
phenyl or pyridyl, it being possible for each of these to carry one to three of the follow-ing: halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C3-C8-alkynyloxy and/or -NRfR8, where Rf is hydrogen and R8 is benzoyl.

5. A herbicidal agent as claimed in claim 4, wherein the ratio of compound Ia or Ib to herbicidal active inqredient is from 0.01:1 to 10:1 by weight.

6. A method for the selective control of unwanted plant growth, which comprises applying a compound of the formula Ia or Ib as claimed in claim 4 and a cyclohexenone derivative of the formula XII as claimed in claim 4, simultaneously or successively, during or after the sowing of the crop plants or before or during the emergence thereof.

7. A method for preventing damage to crop plants by herbicidal cyclohexenone derivatives of the formula XII
as claimed in claim 4, which comprises treating the seeds of the crop plants with an antagonistic amount of a compound of the formula Ia or Ib as claimed in claim 4.

8. A method for the selective control of unwanted plant growth, which comprises treating the leaves of the crop plants and of the unwanted plants after emergence with a compound Ia or Ib and with a cyclohexenone derivative of the formula XII as claimed in claim 4, simultaneously or successively.