JPH06502152A - Substituted pyrido[2,3-d]-pyrimidine-2,4(1H,3H)-dione - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Substituted pyrido[2,3-d)-pyrimidine-2,4(IH,3H)-dione The present invention provides pyrido[2,3-d ]-pyrimidine-2,4(IH,3H)-dione, in the formula R1 and R mean hydrogen, c-c alkyl, C1-04 halogenalkyl, R3 is hydrogen, C-C alkyl, amihahydroxy, mercapto, C-C alkyl thio, C6- or C1o aryl (wherein 1 to 3 R are mentioned) R4 is hydrogen, C1-C4 alkyl, C1-04 Alcoquine carbonyl, C-C4 (alkylthio)-carbonyl, C-C alk xy(thiocarbonyl), C1-C4(alkylthio)-thiocarbonyl, means haaminocarbonyl, or R and R are combined to form C-C alkylene, C3-C6 alkenylene, I, 2-phenylene C) alkylene, c, c or C14 aryl (but a The lyl group may have from 1 to 3 groups mentioned for R11), CH2 F　, C-04 alkoxycarbonyl, C1-04 (alkylthio)carbonyl , C-C alkoxy (thiocarbonyl), C1-C4 (alkylthio)thiocal Bonyl, Hydroxy, Mercapto, C-C Alcoquine, Amino, C1-C4 Al Kylamino, NHCXR, NH30R, 2-chenyl, 3-chenyl, 2-pyri Dinyl, 3-pyridinyl, 4-pyrinonyl, 2-indolyl, 3-indolyl ( However, the heteroaryl group has one or two substituents as described in R11. or R5 and R6 can be combined to form c-c alkylene , C3-C-alkenylene, 1,2-phenylene (C-C4 alkoxy, C-C ha) Optionally substituted with rogene alkyl, C3-07 noxa, and roxy, and further may have a carbonyl or thiocarbonyl group), capto, C-C alkoxy/, Cl-C4 alkylthio, C-C alkoxycarbonyl, C-04 (Alkylthio)carbonyl, C-C4 alkoxy(thiocarbonyl), C-0 4(Alkylthio)thiocarbo■ Nil, Ami8C-C4 alkyl Amihashi (C1-C4 alkyl) Ami8C6 Moshi or C1o aryl, C6 or C arylamino (however, aryl is \ may have three Rl groups mentioned in 1 (LS), R is halogen, hydroxy, mercapto, C-C4 alkoxy, C-C alkyl Thio, C1-C4 alkoxycarbonyl, C-04 (alkylthio)carbonyl 1C means (alkylthio)thiocarbonyl or Kill, NR　R　,OR　means, RIO is c-c alkyl, C or C1o aryl (1 to 3 R with the group mentioned in (X may also be used), 11.

R is halogen, hydroxy, mercapto, C-C4 alcoquine, CI-64 means alkylthio, CI-C4 alkyl, nitro, amino, X means oxygen, sulfur, (a) R1 and R2 do not simultaneously mean H, methyl or ethyl; (b) R3 and R4 do not mean H at the same time; (c) R5 and R6 do not mean H at the same time. (d) R is methyl, R2 is i-butyl, R3 is amino (e) R is methyl, R2 is H, R5 means phenyl, R6 does not mean hydroxy, (f) R is methyl , R2 means H, R6 means amino, R5 is carboxy, etquin carbo does not mean nil; (g) When R is H, R2 is methyl, and R5 is H, R6 is hydroxy. without meaning, (h) When R is H, R2 is methyl, and R4 is ethoxycarbonyl, R 6 means methyl, amino, butyl, R2 does not mean H, (j ) When R is cyano, R6 is hydroxy, and RI is n-propyl, R2 is In the present invention, n-propyl refers to a basic substituent or an acidic hydroxyl substituent. Regarding the agriculturally usable salts of the above compounds (Ia) and (Ib) having do.

The present invention further provides a method for producing compounds (Ia) and (Ib) and 2-(4- heteroaryloxy)- or 2-(4-aryloxy)-phenoxyacetic acid derivatives or - excluding propionic acid derivatives and/or cyclohexanone derivatives. Contains compounds (Ia) and (rb) as antidotes as herbal active substances relates to herbicides and which preferably selectively control the growth of plants; This article relates to a method for suppressing

1.3-substituted 2.4-dioxopyrido-[2,3-d]-pyrimidines have been known for a long time. This is a previously known compound.

That is, on page 406 of Arch, Pharm, 311 (1978), 7 Pyrido-[2,3-d]-pyrimidine-2,4-dione substituted at the - position is , l-allyl substituted in the 6- and 7-positions and 1,3-dimethylpyrido- (2,3-d)-pyrimidine-2,4-diones are listed (Table 5 (See also). At the same time, individual compounds can be used as antitumor agents or as sedatives. It mentions its effect as a drug. Furthermore, at the 5-16-position and the 6-17-position 1,3-dimethylpyrido-(2,3-d)-pyrimidine-2 which is di-substituted with ,4-dione, J. Heterocycle, Chem, 22 (1985) It is described on pages 345 and 1469 (see also Table 5).

Also the formula ℃ 2-(4-heteroaryloxy)- or 2-(4-aryl) represented by oxy/)-phenoxyacetic acid-derived zuthiazyl or benzpyranonyl (these aromatic up to two aromatic cyclic groups, i.e. halogen, nitro, Rb is hydrogen, C- C alkyl or plant-acceptable cation equivalent; The herbicidal effect of R0 hydrogen or methyl is reported in various literatures, for example, Permission sub-publication No. 2223894, No. 2433067, No. 2576251, 3004 Publications No. 770 and No. B - Patent Application Publication Nos. 868875 and 858618 6 are publicly known (see also Table A).

These compounds have the effect of controlling undesirable plants of the Poaceae family, but their cultivation Tolerability by substances is extremely unfavorable.

The same thing is the following formula■ This also applies to cyclohexenone derivatives represented by Darara chain consists of 1 to 3 C-03 alkyl and/or or may have a halogen) or substituted with C1-03 alkyl 1 m of 3- to 6-membered alkylene which may contain oxygen or sulfur as a ring member. (has an oxime ether moiety that is not directly adjacent to an atom) xycarbonyl, phenyl (however, aromatic groups may contain 1 to 3 of the following substituents, e.g. means nitro, cyano, and le), n is O to 3, but if B means halogen, it means 1 to 5; R is c, -C4alcokyne-c, -C6alkyl or c, -c4alkylthi o-cl-C6 alkyl, 1 to 3 of the following groups: C-C4 alkyl, ■ C1-C4 alkokene, C1-04 alkylthio, C1-C halogenalkyl, Hydroxy, C3-07-chloroalkyl which may have halogen or C 3-C7-chloroalkenyl, Contains 1 or 2 oxygen or sulfur heteroatoms and up to 3 of the following: substituents, i.e. 0l-c4alkynobeCIC, ialkoxy, Cl-C4a rukylthio, a 5-membered saturated heterocycle optionally having C-C halogenalkyl, It has one or two oxygen, sulfur, and three of the following substituents, such as Hydroxy, halokene, C1-C4 alkyl, Cl-C4 alkoxy, cl -c4 alkylthio, 6-membered or optionally C-C4 halogenalkyl 7-member heterocycle, It has 1 or 2 nitrogen and 1 oxygen or sulfur, and 1 to 3 The following substituents of i.e. halogen, cyano, Cl-04 alkyl, CI-C4 Alkoxy, C-C alkylthi, c-c halogen 4 1 4 Alkyl, C2-C6 alkenyl, C2-c6 alkenyloxy, C-C halogen Cl-C4 alkyl, Cl-C4 alcokyne-0-04 alkyl may have 5 member heteroaromatic, 1 to 3 of the following substituents: haloken, nylkyl, C-C alkenyl Oxy, C-C6 alkynyloxy, -NRfRg, where R is hydrogen, c- c means alkyl, C3-C6 alkenyl, C3-C3 alkynyl, and Rg is Hydrogen, c-c alkyl, C3-C6 alkenyl, C-C alkynyl, C-C 6 acyl, meaning benzoyl, and this aromatic ring has 1 to 3 substituents, all of which are That is, nitro, cyano, C-C4 alkyl, ■ c -c alkoxy, c, -c4 alkylthio, CI-04 halogenalkyl may have.

The above compounds are also known from the older West German patent applications Nos. 4014985 and 401498. It is described as a weeding wound in each publication No. 6, and is undesirable in dicotyledonous cultivated crops. It is effective in controlling weeds and weeds not belonging to the Poaceae family. Substituent structure and Depending on the amount used and the amount used, compounds belonging to this class can be used in grass crops, e.g. wheat, rice. can be used to selectively control undesirable weeds. The purpose of the invention is When using herbicides consisting of compounds of formulas (XI) and (X[[) as described above, disadvantages, at least significantly, and also almost reduce the yield of cultivated plants. The goal is to find and provide compounds that are not available.

In contrast, the novel compounds (Ia) and (Ib) described at the beginning were developed by the present inventor. It was discovered by et al.

Furthermore, methods for producing these compounds (Ia) and (Ib), as well as methods for producing these compounds (Ia) and (Ib), Ia) and/or (Ib) and the above-mentioned known compound (XI) and/or A method has been found for jointly treating cultivated plants with (Xff).

Salts of certain derivatives (Ia), (Ib) may be used as salts in a harmless manner to the environment. It can exist. Preference is given here to alkali metal salts, especially potassium salts or Sodium salts, alkaline earth metal salts, especially calcium, magnesium or Barium salts, manganese, copper, zinc or iron salts as well as ammonium, phosphonium salts um, sulfonium or sulfoxonium salts, such as ammonium salts, tet Raalkylammonium salt, benzyltriarylammonium salt, trialkylammonium salt These are sulfonium salts or trialkylsulfoxonium salts.

For the specific use of the compounds (Ia) and (Ib) of the present invention as plant protection agents, In view of this, the following groups are preferable as substituents.

R1 and R2 are hydrogen, C-C alkyl, such as methyl, ethyl, propyl, l-methylethyl, butyl , l-methylpropyl, 2-methylpropyl, l,l-dimethylethyl, especially Ken alkyl, such as chloromethyl, dichloromethyl, trichloromethyl, chloromethyl Rofluoromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, Dichlorofluoromethyl, chlorodifluoromethyl, l-fluoroethyl, 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, pen Tafluoroethyl, C-C chloroalkyl, e.g. chloropropyl, cyclopene Chyl, /chlorhexyl, cycloheptyl, especially chloropropyl.

R3 is hydrogen, hydroxy, mercapto, amino, C-C al as described for R. kill, especially methyl, ethyl, C-C alkylthio, such as methylthio, ethylthio, propylthio, 1-methythio ethylthio, butylthio, ■-methyl-propylthio, 2-methyl-propyl thio, I, I-dimethylethylthio, may have chlorine or chlorine).

R is hydrogen, C-C4 alkyl mentioned for R, nil, l-methylethoxycarbonyl, butyloxycarbonyl, ■-methylpropylene Lopyloxycarbonyl, 2-methylpropyloxycarbonyl, 1. l-jime (ethylthio)-carbonyl, (ethylthio)-carbonyl, (propylthio) )-carbonyl, (1-methylethylthio)-carbonyl, (butylthio)-carbonyl carbonyl, (l-methylpropylthio)-carbonyl, (2-methylpropylthio) o)-carbonyl, (1,l-dimethylethylmethoxy-(thiocarbonyl), Ethoxy=(thiocarbonyl), propyloxy~(thiocarbonyl), l-methoxy Tylethoxy-(thiocarbonyl), butyloxy-(thiocarbonyl), l- Methylpropyloxy-(thiocarbonyl), 2-methylpropyloxy-(thiocarbonyl) ocarbonyl), 1. ! -dimethylethoxy(thiocarbonyl), (methylthio)-thiocarbonyl, (ethylthio)-thiocarbonyl, (pro- Pyrthio)-thiocarbonyl, (1-methylethylthio)-thiocarbonyl, ( butylthio)-thiocarbonyl, (1-methylpropylthio)-thiocarbonyl , (2-methylethylthio)-thiocarbonyl, (l,1-dimethylprobylthio) o)-Thiocarbonyl.

Also, R and R can be combined to form C3-C6 alkylene, such as tri-, tetra-, and penetra- form a center and hexamethylenenylene.

R is hydrogen, C-C4 alkinobenynyl, methoxycarbonyl mentioned for R , preferably ethoxycarbonyl).

I R is Cl-04 alkyl as defined above for R, especially methyl, ethyl, Styril, C or C1o aryl, e.g. phenyl, naphthyl (l to 3 R11) may also contain the groups mentioned below, in particular chlorine, nitro, methyl).

(preferably means roquine carbonyl), C-C (al Kirchio) - Power] 4 ocarbonyl, NHCX R9 (X preferably means oxygen), especially methylcarbonyl Ruamino, to ethylcarponylamino (optionally substituted with the groups mentioned above).

In addition, R and R6 are combined to form tri- and tetrapentyl, cyclohexyl may be mono- or di-substituted with C3-07 cycloalkyl, such as carbonyl, tricarbonyl), especially providinyl-1 3-carbonyl, 2,2-dimethylprovidinyl-1,3-carbonyl, 1.2 - form phenylenecarbonyl.

Especially methylthio, ethylthio, C-C alkoxycarbonyl, especially methoxycarbonyl, as mentioned above for R4. Nyl, ethoxycarbonyl, C-C(alkylthio)monocarbonyl as described above for R4, C-C(alcoquino)monothiocarbonyl as described above for R4, C-C(alkylthio)monothiocarbonyl as described above for R4, C-C4 alkylamino, di(C-C4 alkyl)a as described above for R; For example, N,N-dimethylamino, N,N-diethylamino, N,N-dipro Pyramino, N,N-di(l-methylethyl)-amino, N,N-dibutylamino Mino, N,N-di(1-methylpropyl)-amino, N,N-di(2-methyl di(1,l-dimethylethyl)-amino, N,N-di(1,l-dimethylethyl)-amino,N -ethyl-N-methylamino, N-methyl-N-propylamino, N-methyl- N-(1-methylethyl)-amino, N-butyl-N-methylamino, N-methy -N-(methylpropyl)-amino, N-methyl-N-(2-methylpropyl) )-amino, N-(1,1-dimethylethyl)-N-methylamino, N-ethyl -N-propylamino, N-ethyl=N (1-methylethyl)-amino, N- Butyl-N-ethylamino, N-ethyl-N-(1-methylpropyl)-amino , N-ethyl-N-(2-methylpropyl)-amino, N-ethyl-N-(1, 1-dimethylethyl)-amino, N-(1-methylethyl)-N-propylamine N-butyl-N-propylamino, N-(1-methylpropyl)-N-propylamino, Pylamino, N-(2-methylpropyl)-N-propylamine, N-(1,1 -dimethylethyl)-N-propylamino, N-butyl-N-(1-methylethyl) )-amino, N-(1-methylethyl)-N-(1-methylpropyl)-a Mino, N-(1-methylethyl)-N-(2-methylpropyl)-amino, N- (1,1=dimethylethyl)-N-(1-methylethyl)-amino N-butyl- N-(methylpropyl)-amino, N-butyl-N-(2-methylpropyl)- Amino, N-butyl-N-(1,1-dimethylethyl)-amino, N-(l-methyl methylpropyl)-N(2-methylpropyl)-amino, N-(1,1-dimethyl ethyl) -N-(1-methylpropyl)-amino, N-(1,1-dimethylethyl) methyl)-N-(2-methylpropyl)-amino, C or C aryl, C or 010 arylamino, such as phenyl, naphthyl, phenylamino (arylamino) R may have 1 to 3 substituents as mentioned for R). Taste.

R8 is l-logen, especially fluorine, chlorine, hydroxy, mercapto, C-04 alkoxy as described above for R, C as described above for R -C4 alkylthio, as mentioned above for R Bonil, C-C4 (alkylthio)carbonyl as described above for R; C-C alkokyne-(thiocarbonyl) as described above for R; C-C(alkylthio)thiocarbonyl as described above for R; base (X especially means oxygen, R means hydrogen, methyl, ethyl).

R9 is C-04 alkyl as described above for R1, especially methyl, ethyl, C-04 alkyl as mentioned above for R1, especially methyl, ethyl, C-C-rokenalkyl as described above for R1, NR　R　, -toniamino, dimethylamino, OR1, especially human 0kin, meth Kino, meaning etokino.

R is C-C4 alkyl, C or C1o alkyl as described above for R. for example phenyl, naphthyl (groups mentioned for I to three R11) ), especially 2-methylphenyl, 3-methylphenyl, 4- Means methylphenyl.

R11 is halogen, especially fluorine, chlorine, hydroxy, mercapto, nitro, amino of, C-C alkoxy as mentioned above for R6, especially methoxy, ethoxy, C-C alkylthio as mentioned above for R3, especially methylthio, ethylthio, C-C alkyl as mentioned above for R1, especially methyl, ethyl, propyl, l -Methylethyl, meaning 1,1-dimethylethyl.

X means oxygen or sulfur.

Particularly suitable compounds (Ia), (Ib) are listed in Tables 1 to 4 (in practice) (see examples).

Compound (I) of the present invention can be obtained by various methods. Substituted pyridopyrimidines include, for example Condensation of 4-aminopyrimidine and ethoxymethylenemalonic acid derivative or 4-aminopyrimidine It is carried out by the reaction of mino-5-formylpyridine and β-diketone (pergamon Published by Press, “Conbrigensueve, Heterocyclic, Chemistry” 3 E. Lunt, C. G. Newton, Vol. 215-232). Sara Another method is the reaction of β-dialkylaminoketone with 4-aminopyrimidine. (Arch, Ph, arm.

311 (1978) pp. 406, 542 R. Tronjutz, H. J. Roth's paper).

Pyridinepyrimidine derivative (Ia) is, for example, 4-aminopyrimine no 2.4 - (IH,3H)-dione (II) in an inert solvent in a protective atmosphere, Obtained by reacting with β-chloroalkenal (DI).

In this case, compound (II) is first loaded, and alkenal (I[ [) is preferably added over a period of 5 to 30 minutes, especially 20 minutes starting from 1O.

As a rule, the reaction mixture is heated to 20 to 150°C, preferably 70 to 110'C. and left undisturbed for 3 to 12 hours, especially 5 to 7 hours, before cooling to room temperature. be placed.

It generally solidifies during cooling and this solid product can be separated by conventional methods. combination The ratio of compound (II) to alkenal (I[r) is generally from 07.I to Selected in the range of 1.2:1.

Pyrimidine derivatives (ff) are generally known and easily produced (as described above). Pergamon in Kusford, published by Press, ``Complete Suive, Heterosai'' Click, Chemistry, Vol. 3, pp. 106-142, by J. Brown. reference).

The production of β-taloloalkenal (I[[) is described, for example, in J.

Performed similarly to the method in Chem, Soc, (C) (1970) p. 2484. I can.

Yet another method for producing the pyridopyrimidine derivative (Ia) is to prepare the compound (n). , J. HeterocyclicChem, 22 (1985) p. 1469. with the β-alkoxyacrylic acid derivative (IV) in a manner known per se. In principle, the intermediate product (V) is isolated and converted to compound (Ia) by heating. Is Rukoto. In this case, the starting material β-alkoxyacrylic acid derivative (IV) is , in this formula, R is C-C alkoxycarbonyl, C2-05 alkoxythiocar Bonyl or cyano, and R13 is C-C5 alkyl, such as ethyl, n -propylene, ■-methylethyl, n-butyl, I,1-dimethylpropyl or is a compound when it means n-pentyl, and this compound (IV) is a known compound. Yes, and can be easily manufactured.

Starting compound (Ib) can be prepared by converting compound (ff) into β-aminoalcohol by, for example, a known method. Obtained by reacting with chirketone (VI) (Arch, Pharm, 311 ( (1978) p. 406). In case 2, Ro is hydrogen, C-C4 alkoxy, methyl, ethyl, R4 means C1-04 alkyl, especially methyl, ethyl It is preferable to

Yet another method for producing compound (Ib) is to use a pyrimidine derivative (■a) or (~・1b) by a method known per se (J, Heterocycle, Ch. Em, 22 (1985) 345), malonic acid derivatives (~1lla), ( ~l1lb) or (■C). In this case, R5″ is Aha means C(0)R7 or C(S)R7, where R is C1-04 alkyl; Methyl, ethyl, n-propyl, i-propyl, n-butyl, 1-butyl, 5ec-butyl, tert-butyl, especially ethyl, R6' is R15 C1-C4 alkyl, especially methyl, C6 aryl (C2- C4)-alkenyl, especially styryl, C, CIo or also the compound (I) b) Compound (Ib) (wherein R6 means hydroxy) is itself a publicly known Methods of Knowledge (P in LiebigsAnn, Chem (1984) 1653 Metius, P. Zobert, H. Wamhoff), compound (IX) (R16 means -Nu). In this case, R is R as mentioned above. Nu means C1-C4 alkyl, especially 1-propyl, n-butyl, Nu means cough halogen, especially iodine.

Compound (Ib) is a compound (Ib) (R6 means amino) known per se. Compound (Xa), R9(CX)Nu, Xb, R10-502-Nu It is obtained by reacting with

Formula (XI) whose tolerability in cultivated plants is improved by compounds (Ia) and (Ib) Herbicide heteroaryloxy or aryloxyphenoquine acetic acid derivatives An example is shown in Table A below.

Furthermore, the compounds (Ia) and (rb) improve the tolerability of cultivated plants. Examples of the herbicide cyclohexenone in l) are shown in Tables B to R below (West German patent application publication). References to publications No. 4014985 and No. 2822304 Table ^ A, 2 + F3 r) -c4H@CH3 Belgian patent 86813754.3 　℃；＝：１９． C2145CH3 Herkey BiM s5a61se: e　e　:? Everyone's bag is all over the place. Iso Iso person & Tsubo Shun - Roku - Iso ;Vote;Vote 100;;100 −−to − affirmation prayer pot prayer Iso Gā pot prayer Ken Iso Buki Iso − 100 100 100 votes 100 votes 100 ;:!　100　100　; 　100　100　　; 　100　100? ＋Heato -He -% +-'F-kHe-Toh +HTo °To Field 娀　----υ　Iso　Shi　Suggestion　--111111　-bo, Oda　a　& 6 people, 6 people.

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acci ace ahshinaa-aωo-ata-a-a-a-== Herbicides and detoxifying compounds can be grown together or separately and preferably It is sprayed on the surface of weeds and young shoots. Antidotes are preferably applied together with herbicides. However, it is also possible to apply the antidote first and then the herbicide. herbicide and solution What about the poison? Possible to cloud, emulsify or 1g! possible form, combined or separate Individually made into a propellant.

An important mode of use in practice is the treatment of the seeds of cultivated plants with an antidote before sowing. Therefore, in this case, the herbicidal active substance is applied alone in the same manner as before.

Herbicides, heteroaryloxy- or aryloxy-phenoxyacetic acid derivatives When (XI) is used in various cultivated plants, the amount of detoxifying compound will vary accordingly. must be changed accordingly. The usage ratio of both can be changed over a wide range. can be heteroaryloxy or aryloxo-phenoxy It is determined depending on the structure of the acetic acid derivative and the cultivation purpose in each case. Detoxified A suitable quantity ratio of active substance to herbicidal active substance is between 0.01:1 and 10:1, in particular 0.01:1 to 10:1. ．． 1:1 to 4:1 parts by weight.

Similarly, for cultivated round products with different cyclohexenone derivatives (XI[) When used, this cyclohexenone derivative (X[l) and the compound of the present invention (I The proportion of amounts used with a) or Ib) can also be varied within a wide range. This is cyclohex The structure of the cenone derivative (X[l), the compound (Ia) or Ib) of the present invention Determined by Appropriate amount ratio of detoxifying effective substance to above herbicidal effective substance in case of merger Also for individual use, from 0.01:1 to 101, especially from 0.25:I to 4:1 It is a quantity part.

The new herbicide contains a new compound (Ta) or Ib) as an antidote and Teroaryloxy- or aryloxy-phenoxyacetic acid (XI) or In addition to the clohexenone derivative (X[l), the herbicidal activity of other chemical structures or Growth control agents may be included, which provide a cultivation effect.

The agents according to the invention or herbicidal active substances or antidotes when applied separately are examples of For example, directly sprayable solutions, powders, suspensions, and also highly aqueous or oil-based or Hasonoike @ Turbid liquid or dispersion, emulsion, oil dispersion, paste, dust agent , by spraying, misting, dusting, scattering or injection in the form of a dusting agent or granules. Can be applied. The application format is determined entirely by the intended use.

For producing directly splashable solutions, emulsions, pastes or oil dispersions, medium Mineral oil fractions with the highest boiling point, such as kerosene or diesel oil, as well as coal tar oil, etc. as well as aliphatic, cyclic and aromatic hydrocarbons of vegetable or animal origin, e.g. linzole, doluol, quidylol, paraffin, tetrahydronaphthalene, Lucyl-substituted phthaline or its derivatives, methanol, ethanol, propatool , butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexane strong polar solvents such as dimethylform, chlorbenzole, and infuron Amide, dimethyl sulfoxide, N-methylpyrrolidone and water are used.

Aqueous use forms are emulsion concentrates, pastes, or wettable powders (spray powders) and oil dispersions. It can be produced by adding water from a liquid. emulsion, paste or oil dispersion For production, the herbicidal active substance and/or antidote can be added neat or in oil or solvent. dissolved in water and uniformly mixed in water with wetting agents, adhesives, dispersants or emulsifiers. can be done. In addition, herbicidal active substances and/or antidotes, wetting agents, adhesives, Concentrates consisting of powders or emulsifiers and optionally solvents or liquids can also be prepared. , which is suitable for dilution with water.

Surface-active substances include: lignin sulfonic acid, naphthalene. Alkali salts, alkaline earth salts, and alkaline salts of phenolsulfonic acid and phenolsulfonic acid. ammonium salts, alkylaryl sulfonates, alkyl sulfates, alkaline Kill sulfate, alkali salts of dibutylnaphthalene sulfonic acid and alkali Earth salts, lauryl ether sulfate, fatty alcohol sulfate, fatty acids alkali and alkaline earth salts and sulfated hexadecanol, heptadecano salts of alcohol and octadecanol, and sulfated fatty alcohol glycol ethers salts, sulfonated naphthalene and naphthalene derivatives and formaldehyde condensation products of naphthalene or naphthalene sulfonic acid with phenol and Condensation product with maldehyde, polyoxyethylene-octylphenol ether , ethoxylated isooctylphenol, octylphenol, nonylphenol alkylphenol polyglycol ether, tributylphenyl polyglycyl Recall ether, alkylaryl polyether alcohol, isotridecyl Alcohol, fatty alcohol ethylene oxide condensate, ethoxylated Himashiura , polyoxyethylene alkyl ether, or ethoxylated polyoxypropylene lauryl alcohol polyglycol ether acecool, sorbitol lignin-sulfite waste liquor and methyl cellulose.

Powders, sprays and sprinkles contain herbicidal active substances and/or antidotes and solid carrier substances. It can be produced by mixing or grinding together.

Granules, e.g. coated, permeable and homogeneous granules, bind the active substance to the solid carrier material. It can be manufactured by Solid support materials may be minerals, e.g. Kagel, silicic acid, silicate gel, silicate, talc, kaolin, atakulay, limestone, lime , chalk, agglomerate granular soil, calcareous yellow clay, clay, dolomite, diatomaceous earth, calcium sulfate, Magnesium sulfate, magnesium oxide, ground synthetic resin, fertilizers such as ammonium sulfate ammonium phosphate, ammonium nitrate, urea and vegetable products such as grains. Flour, bark, wood and walnut shell flour, cellulose powder and other solid carrier materials.

The use form is herbicidal active substance and antidote Q, OI to 95% by weight, in particular 0.5 to 90% by weight. % by weight. The amount of herbicidal active substance used is active substance (a, s) 0.2 to 5 Kg/ha.

The method for producing the compound of the present invention will be explained in more detail with reference to the following examples.

] Example L.

5-Ethyl-1,3,6-1-limethyl-pyrido(2,3-d)-pyrimidine- 2,4-(LH.

3H)-dione First, 11.6 g (75 mmol) of 4-amino-1°3-dimethylpyrimidine- 2,4-(IH,3H)-dione was added to 100 ml of 2,4-(IH,3H)-dione at room temperature under a nitrogen atmosphere. of anhydrous dimethylformamide. 1 for 15 minutes. 3.2 g (100 mmol) of 3-chloro-2-pentene-2-carbalde Add Hyde.

The reaction mixture was then heated to 95°C for 30 minutes and maintained at this temperature for 6 hours. do. It is then cooled to room temperature and the debris is filtered off. 15.6g (67% ) was obtained in the same manner (Example No. 1.006 in the table below). The products shown in Table 1 were obtained.

Table 1 -pyrido[2,3-d:l-pyrimidine-2,4-(IH,3H)-dione 6.2 g (40 mmol) of 4-amino-1,3-dimethylpyrimidine-2,4 -(IH,3H)-dione and 11.6 g (45 mmol) of 3-nitro-β- 100ml of dimethylaminopropiophenone hydrochloride After heating under reflux in glacial acid for 3 hours and adding 2 milliliters of concentrated hydrochloric acid, the temperature was reduced to The mixture was heated until the suspension became colorless. After cooling and filtering, 8.9g (78%) A crystalline product of (Table 2.001 below) was obtained.

In the same manner, the products shown in Table 2 were obtained.

Table 2 Husband Jl Yu ], 3-dimethyl-6-medoxycarbonyl-7-methquinecarbonylmethylpi Lido[2,3-d)-pyrimidine-2,4-(IH,3H)-dione First 4.8 5 g (20 mmol) of 5-dimethylaminomethylenepyridine and 3',4 A suspension of 8 g (20 mmol) of acetone dicarboxylic acid dimethyl ester was added to 0 2.4 g (24 mm mol) of triethylamine was added dropwise and stirred for 2 hours at room temperature. then (-15) Cooled to 0C, filtered off the precipitate, dried under vacuum, 3.81g (59%) of the product was obtained (Table 3.008 below).

In the same manner, the compounds shown in Table 3 were produced.

Example RI R2As R6 melting point Back 10 rough work 1.3-dimethyl-7-ethoxycarbonyl-8=ethylcarbonylamino-pi LidoC2,3-d]-pyrimidine-2,4-(IH,3)()-dione 5.60 g (20 mmol) of -7-amino-1,3-dimethyl-2,4-(l) (, Ethyl 3H)-dioxypyrido(2,3-cl)-pyrimidine-6-carboxylate A mixture of ester and 2.86 g (22 mmol) of propionic anhydride, Heat under reflux for 24 hours in 30 ml of propionic acid, cool, and filter. 547 g (82%) of product was obtained (Table 4.002 below).

In the same manner, the compounds shown in Table 4 were obtained.

Table 4 4.002 -NHCOEt 131-1340C Table 5 below shows the known literature or lists compounds (Ia) and (Ib) obtained by a method similar to the method described in the literature. This also increases the tolerability of herbicidal substances Oa) and (Xll) to cultivated plants. You can

Table 5 Actual IN example +13, +14 R5R6 literature 5.001 0HCO2εt-1 5,002N82 CN 5.003 08H 5,004HPh2 5.005 H4-Me-C6M4 25.006 - 14e Ph 2 5.007 -CH2-(0-C6HJ 25.008 -TCs21z-(o -CsH4) 25.009 -(CHzh-(6-C6H) 25.010 CN NO33 5,011C02Et NO33 5,012CQ2Et OH3 5,0+3 C02Et Me 3 5.014 C02HN142 3 +1 G, L, ^nc+@rson, ko, +et@rocy1. CM+m, 22 (198511469゜2) Ro roschLitz, H, Ko, Rot h, Arc, ρharn+, 311 (+9781 406°31 K, 5trata, Y, (ltad*, 5.5@nda, Ko, Hatar ocyl, Chars, 22 (19851345゜ -11).

・Go to Herbicides or herbicide mixtures according to the invention, i.e. mixtures of herbicides and detoxifying compounds. Herbicides have an excellent effect on the growth of desirable and undesirable plants. Examples of the following biological effects in greenhouse experiments compared to when used alone: This can be demonstrated by

As a cultivation container, the internal volume is 300 crn3, and it contains 3°0% humus as a culture medium. Seeds of test plants were placed in plastic pots containing loamy sandy soil. Seeds were sown separately for each type and irrigated. Next, cover the flowerpot with a transparent plastic sheet. The plants were covered and left until the seeds germinated en masse and the plants took root.

For post-treatment, test plants were grown to a height of 3 to 20 cm, and then First, the herbicide was added to water to disperse or emulse it, and then treated with a sprayer.

A cyclohexenone derivative (■) was used as an experimental herbicide.

These herbicidal active substances are commercially available preparations (100g/liter emulsion J degree). were respectively combined with a preparation of a detoxifying active compound and treated thereby.

For comparative experiments, the active substances B15 and H34 were each added to 80% by volume of cyclohexane. A mixture of xenon and 20% by volume ethoxylated castor oil (vs. containing no antidote) It was applied as a comparative agent).

80% by volume of cyclohexanone 80 for post-treatment of all detoxifying active compounds % by volume, 10% by weight was added to a mixture of 20% by volume of ethoxylated castor oil.

List of test plants Lolium multiflorum taria viricljs) wheat (Triticum aestivu) m) Zea mays All experimental flower pots were heated to 30°C for tropical test plants, and 30°C for temperate test plants. Place it in a greenhouse at 25°C from IO! did.

The agent is dispersed in water, which acts as a carrier and dispersion medium, and dripped onto the test plants using a moving bed device. The experimental period was extended to 3 to 5 weeks, during which time the trial planting compared with untreated control plants, which were grown in strength and observed for response to each treatment. Evaluate the damage caused by chemical agents on a scale of O to 100%; 0% means no damage at all. ″;-1100% means complete death of the plant!

Tables 6 to 11 below show novel compounds according to the present invention, pyrido E2゜3-d]-pyrimidine. shows the detoxifying effect of ion-2,4-(LH,3H)-dione (Ia), (Ib) .

This allows detoxifying compounds to be applied to herbicides B15 and H34 by various grasses. It can be seen that this significantly improves acceptability.

1 mutual Mixture of detoxifying compound and post-treatment of herbicide B15 (Sethoxydim) Improvement of tolerability by corn and wheat in the case of food (greenhouse experiment) usage amount (kg/’ha) Test plant (%) Damage iyu Corn in the case of detoxification compound mixture and post-treatment of herbicide E34 Improvement of tolerability with strained and barley (greenhouse experiment) Usage amount (kg/’ha) Test plant (%) Damage table - Tortoise In the case of post-treatment of herbicide E34 by mixing detoxifying compounds and post-treatment. Improvement of tolerability by corn (greenhouse experiment) Usage amount (kg/ha) Test plant C%) Damaged old two 2 Detoxifying effect of herbicide E34 in the case of pyrido[2,3-d]-pyrimidine mixture Improving tolerability with corn (greenhouse experiment, post-treatment) Usage amount (kg/ha) Test plants (%) Damage table Detoxification effect of herbicide E34 Pyrido[2,3-d]-pyrido usage amount (kg/ha) Test plant (%): Detoxifying effect of the damaging herbicide E34, pyrido[2,3-d]-pyrimidine Improving tolerability with corn and wheat in the case of corn and wheat mixtures (greenhouse experiments) , post-treatment) Usage amount (kg/ha) Test plant C%) Damage

Claims (8)

[Claims] 1. The present invention has general formulas (Ia) and (Ib)▲Mathematical formulas, chemical formulas, tables, etc.▼ Ia▲There are mathematical formulas, chemical formulas, tables, etc.▼Pyrido represented by Ib [2,3- d]-pyrimidine-2,4(1H,3H)-dione, in which R1 and R2 are hydrogen, C1-C4 alkyl, C1-C4 halogenalkyl, R3 is hydrogen, C1-C4 alkyl, amino, hydroxy, mercapto, C1-C 4 alkylthio, C6- or C10 aryl (with 1 to 3 R11 ), R4 is hydrogen, C1-C4 alkyl C1-C4 alkoxycarbonyl, C1-C4 (alkylthio)-carbonyl C1-C4 alkoxy(thiocarbonyl), C1-C4(alkylthio)- means thiocarbonyl, cyano, aminocarbonyl, or R3 and R4 are combined to form C3-C6 alkylene, C3-C6 alkenylene, 1,2 - form phenylene, R5 is hydrogen, C1-C4 alkyl, cyano, C(O)R 7, meaning C(S)R7; R6 is C1-C4 alkyl, C6 aryl-(C2-C4) alkylene, C6, C10 or C14 aryl (however, the aryl group has 1 to 3 R11 ), CH2R8, C1-C4 alkoxycarbonyl C1-C4(alkylthio)carbonyl, C1-C4alkoxy(thiocarboxyl) carbonyl), C1-C4 (alkylthio)thiocarbonyl, hydroxy, mercap t, C1-C4 alkoxy, amino, C1-C4 alkylamino, NHCXR9 , NHSO2R10, 2-thienyl, 3-thienyl, 2-pyridinyl, 3-pyridinyl Dinyl, 4-pyridinyl, 2-indolyl, 3-indolyl (however, heteroaryl The group may have one or two substituents as described in R11). or R5 and R6 are combined to form C3-C6 alkylene, C3-C5 alkylene. Kenylene, 1,2-phenylene (C1-C4 alkyl, C1-C4 halogen alkyl) optionally substituted with carbonyl, C3-C7 cycloalkyl, and carbonyl, may have a thiocarbonyl group), R7 is hydrogen, C1-C4 alkyl Kyl, hydroxy, mercapto, C1-C4 alkoxy, C1-C4 alkylthi E, C1-C4 alkoxycarbonyl, C1-C4 (alkylthio)carbonyl , C1-C4 alkoxy(thiocarbonyl), C1-C4(alkylthio)thio Carbonyl, amino, C1-C4 alkylamino, di(C1-C4 alkyl)a mino, C6 or C10 aryl, C6 or C10 arylamino (just aryl may have 1 to 3 groups mentioned in R11) means, R8 is halogen, hydroxy, mercapto, C1-C4 alkoxy, C1-C4 Alkylthio, C1-C4 alkoxycarbonyl, C1-C4 (alkylthio) Carbonyl, C1-C4 alkoxy (thiocarbonyl), C1-C4 (alkyl) thio)thiocarbonyl or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ means, R9 is C1-C5 alkyl, C1-C4 halogenalkyl, NR1R2, OR1 means, R10 is C1-C4 alkyl, C6 or C10 aryl (1 to 3 R1 1), which may have the groups mentioned in 1. R11 is halogen, hydroxy, mercapto, C1-C4 alkoxy, C1-C 4 alkylthio, C1-C4 alkyl, nitro, amino, X means oxygen, sulfur, (a) R1 and R2 do not simultaneously mean H, methyl or ethyl; (b) R3 and R4 do not mean H at the same time; (c) R5 and R6 do not mean H at the same time. (d) R1 is methyl, R2 is i-butyl, R3 is amino (e) R1 is methyl, R2 is H, R5 means phenyl, R6 does not mean hydroxy, (f) R1 is methyl , R2 means H, R6 means amino, R5 is carboxy, ethoxycarbo does not mean nil; (g) When R1 means H, R2 means methyl, and R5 means H, R6 means hydroxy. without meaning, (h) When R1 means H, R2 means methyl, and R4 means ethoxycarbonyl, R 6 does not mean methyl or amino, (i) When R5 means cyano, R6 means hydroxy, and R1 means n-butyl, R 2 does not mean H, (j) R5 is cyano, R6 is hydroxy, R1 is n-propyl pyrido [characterized in that R2 does not mean n-propyl] 2,3-d]-pyrimidine-2,4-(1H,3H)-dione, and basic nitrogen The above compounds (Ia) and (I b) agriculturally usable salt; 2. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼4-aminopyrimidine-2 represented by II ,4-(1H,3H)-dione of general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼β-chloroalkenal III (R3 in the formula ' is hydrogen, C1-C4 alkyl, having 1 to 3 groups as mentioned above for R11 C6 or C10 aryl), or Compound (II) is represented by the general formula (IV)▲There are mathematical formulas, chemical formulas, tables, etc.▼Represented by IV β-alkoxy acrylic acid derivative (wherein R12 is C2-C5 alkoxy Rubonyl, C2-C5 alkoxythiocarbonyl or cyano, R13 is C2 -C5 alkyl) by a method known per se to obtain the general formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼V The intermediate product represented by is heated and further converted to compound (Ia). The method for producing compound (Ia) according to claim 1, characterized in that: 3. Compound (II) is prepared by a method known per se into general formula (VI)▲mathematical formula, chemical formula, There are tables, etc. ▼ β-dialkylaminoketone of VI (in the formula, R5' is hydrogen or means C1-C4 alkyl, R14 means C1-C4 alkyl) mosquito, Or general formula (VIIa) or (VIIb) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼VIIa▲There are mathematical formulas, chemical formulas, tables, etc.▼Pirimi represented by VIIb gin derivatives of the general formulas (VIIIa) and (VIIIb) by a method known per se. Or (VIIIc) NC-CH2-R5'' (VIIIa) R15O2C -CH2-R5'(VIIIb)R6'(CO)CH2-R5'(VIIIc) A malonic acid derivative represented by (wherein R5'' is cyano, a group C(O)R7 or The group C(S)R7, R15 is C1-C4 alkyl, R6' is C(S)R7, C6 alkyl. Ryl - (C2-C4)alkenyl, meaning C6, C10 or C14 aryl Aryl may have from 1 to 3 groups as mentioned for R11, R6 ' additionally means a group CH2R8), or Alternatively, compound (Ib) (in the formula R6 means hydroxy) can be converted into a compound known per se. In the method, general formula (IX) R16-Nu (IX) A compound represented by (wherein R16 is C1-C4 alkyl, Nu represents a nucleophilic starting group) or compound (Ib) (wherein R6 represents amino ) by a method known per se, general formula (Xa) or (Xb) ▲There are mathematical formulas, chemical formulas, tables, etc.▼Xa▲There are mathematical formulas, chemical formulas, tables, etc.▼Xb The compound (I) according to claim 1, characterized in that it is reacted with a compound represented by b) Manufacturing method. 4. General formula (Ia) or (Ib) ▲There are mathematical formulas, chemical formulas, tables, etc.▼Ia▲There are mathematical formulas, chemical formulas, tables, etc.▼Ib At least one type of pyrido[2,3-d]-pyrimidine-2,4( 1H, 3H)-dione (wherein R1, R2, R3, R4, R5, R6 are defined in claim 1) has the meaning stated in (and satisfies exceptional conditions (a) to (j)); and (a) General formula (XI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼Represented by XI, Ra is phenyl, pyridyl, benzoxazyl, benzthiazyl or benz Pyrazinyl (up to two of these aromatic cyclic groups, i.e. halogen, nitrate) B, C1-C4 alkyl, C1-C4 halogenalkyl, C1-C4 halogena may have lucoxy), Rb means hydrogen, C1-C4 alkyl or a plant-acceptable cation equivalent, At least one type of 2-(4-hetero) when Rc means hydrogen or methyl aryloxy)-or 2-(4-aryloxy)-acetic acid derivative or (b) General formula (XII) ▲There are mathematical formulas, chemical formulas, tables, etc.▼Represented by XII, Rd means C1-C6 alkyl, A is a C4 alkylene chain or a C4 alkenylene chain (these chains have 1 to 3 C1-C3 alkyl and/or halogen) or C A 3- to 6-membered alkylene chain optionally substituted with 1-C3 alkyl (this is having an oxime ether moiety as a ring member that is not directly adjacent to an oxygen or sulfur atom B is nitro, cyano, halogen, C1-C4 alkyl, C1- C4 alkoxy, C1-C4 alkylthio, C1-C4 halogenalkyl, C1 -C4 halogenalkoxy, carbonyl, C1-C4 alkoxycarbonyl, base ndyloxycarbonyl, phenyl (however, aromatic groups have 1 to 3 of the following substitutions) groups, i.e. nitro, cyano, halogen, C1-C4 alkyl, C1-C4 alkyl Coxy, C1-C4 alkylthio, C1-C4 halogenalkyl, C1-C4 ha Rogenalkyloxy, carbonyl, C1-C4 alkoxycarbonyl, benzyl (may contain hydroxycarbonyl), n is 0 to 3, provided that when B means halogen, it means 1 to 5; Re is C1-C4 alkoxy-C1-C6 alkyl or C1-C4 alkyl thio-C1-C6 alkyl, 1 to 3 of the following groups: C1-C4 alkyl C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 halogenal C3-C7 cycloalkyl which may have halogen, hydroxy, or halogen or C5-C7 cycloalkenyl, Contains 1 or 2 oxygen or sulfur heteroatoms and up to 3 of the following: substituents, i.e. C1-C4 alkyl, C1-C4 alkoxy, C1-C4 a Rukylthio, 5-membered saturated heterocycle optionally having C1-C4 halogenalkyl , It has 1 or 2 oxygen, sulfur, and 1 to 3 of the following substituents, such as Hydroxy, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1 -C4 alkylthio, 6-membered which may have C1-C4 halogenalkyl 7-membered heterocycle, It has 1 or 2 nitrogen and 1 oxygen or sulfur, and 1 to 3 The following substituents of i.e. halogen, cyano, C1-C4 alkyl, C1-C4 Alkoxy, C1-C4 alkylthio, C1-C4 halogenalkyl, C2-C 6 alkenyl, C2-C6 alkenyloxy, C2-C6 halogenalkyl, C 5-membered heteroaromatic which may have 1-C4 alkoxy-C1-C4 alkyl , 1 to 3 of the following substituents: halogen, nitro, cyano, C1-C4 Alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 halogen alkyl, C3-C6 alkenyloxy, C3-C6 alkynyloxy, -N RfRg means hydrogen, C1-C4 alkyl, C3-C6 alkenyl, C3-C3 alkynyl, Rg is hydrogen, C1-C4 alkyl, C3-C6 means alkenyl, C3-C6 alkynyl, C1-C6 acyl, benzoyl, The aromatic ring contains one to three substituents as follows: nitro, cyano, C1-C 4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 halo At least one cyclohexenone derivative optionally having a gen-alkyl A herbicide containing a conductor. 5. Weight of compound (Ia) or (Ib) and herbicidal active substance (a) or (b) Claim 4, characterized in that the amount ratio is from 0.01:1 to 10:1 parts by weight. Herbicide. 6. Compound (Ia) or (Ib) according to claim 4 and 2-( according to claim 4) 4-heteroaryloxy)- or 2-(4-aryloxy)-phenoxy citric acid derivative (blade) or cyclohexenone derivative (XII) to cultivated plants. before, during or after sowing, before or during the growth of cultivated plants, or at the same time. Selective control of undesirable plants characterized by application to or one after the other how to. 7. Cultivated plants with a detoxifying effective amount of a compound of formula (Ia) or (Ib) according to claim 4. Herbicide 2-(4-heterogeneous) according to claim 4, characterized in that it treats the seeds of aryloxy)- or 2-(4-aryloxy)-phenoxyacetic acid derivative (XI) or the herbicide cyclohexenone derivative (XII) of cultivated plants. How to element damage. 8. Claim (4): The leaf surfaces of cultivated plants and undesirable plants are treated by a post-treatment method. Compound (Ia) or (Ib) and 2-(4-heteroaryloxy) according to )- or 2-(4-aryloxy)-phenoxyacetic acid derivative (XI) or treated with cyclohexenone derivative (XII) simultaneously or one after another. A method for selectively inhibiting the growth of undesirable plants.