JPS63165367A - Substituted pyrazolin-5-one derivative and its use - 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 The present invention relates in part to the use of known substituted pyrazolin-5-one derivatives as herbicides and fungicides and to novel substituted pyrazolin-5-one derivatives and their use as herbicides and fungicides. Regarding manufacturing methods.

It is already known that substituted pyrazolin-5-ones, such as 4-(cyanomethyloximino)-3-methyl-1-phenyl-pyrazolin-5-one, have fungicidal properties (see European Published Patent Application No. No. 0.166.171).

Substituted pyrazolin-5-ones such as [4-(2,4
It is also already known that methylpyrazol-5-yl]-4-methylphenylsulfonate has herbicidal properties (see DE 2.513.750).

However, the action of these compounds is not always satisfactory in all fields of application, especially at low application rates and concentrations.

Furthermore, 1-(4-chlorophenyl)-pyrazoline-5-
derivatives such as 1-(4-chlorophenyl)-3-methyl-4-piperidinomethylene-pyrazolin-5-one, 1-(4-chlorphenyl)-3-methyl-4-morpholino-methylene-pyrazolin-one 5-on, 1-(4
-Chlorphenyl)-4-[4-(fluorophenylamino)-methylene]-3-methyl-pyrazolin-5-one, ■-(4-chlorphenyl)-3-methyl-4-aminomethylene-pyrazoline- 5-one and 1-(2-ethylphenyl)-3-methyl-4-aminomethylene-pyrazolin-5-one are known. These compounds have particularly strong combustion inhibiting and fungicidal effects, and their herbicidal activity against dicotyledonous weeds has also been mentioned [see Kreuzberger et al., Arch.

Pharm, ), 319.865-871 (I986
) and 318.89-91 (I985)].

Furthermore, 4-aminomethylene-pyrazolin-5-one derivatives, such as 1-(4-bromphenyl)-3-methyl-4-methylaminomethylene-, which are described as complexing agents.
Pyrazolin-5-one [see AIam et al.
zh, Org Kim (Org.

Whim, ), ■ (4), 863-868 (I977)
] or 3-methyl-4-, which has been structurally studied.
Chlorphenylaminomethylenepyrazolin-5-one [
See J. E. Rockley et al., Aust, J. Chem, 34.
(5), 1117-1124 (I981)] are also known.

Furthermore, 1-(4-chlorophenyl)-3-methyl-4-
Anilinomethylene-pyrazolin-5-one is known as a starting compound for the preparation of nickel complexes of azines (see European Patent No. 0.020,299).

Furthermore, ■-phenyl-5-(4-methoxyphenyl)-
4-N,N-dimethylaminomethylidene-pyrazoline-
5-ones are known as starting compounds for the production of pharmaceutical products (see British Patent No. 887,509).
.

This time, in the formula (I) C, RI is hydrogen, alkyl, cycloalkyno-halogenoalkyl, optionally substituted alkenyl or alkynyl, halogenoalkenino-alkoxy, alkoxyalkyno-alkylthioalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl , alkoxycarbonylalkyl, dialkoxy(thio)phosphorylalkyl, each optionally substituted aryl, aralkyl, aryloxyalkyl or arylthioalkyl, or optionally substituted heterocycle or heterocycloalkyl,
or represents a group -NH-Go-R" or -CO-0-R", provided that R" and R" each independently represent alkyl or aryl, and R2 represents a group -NHR', -NR'R' or -NHOR6, where R3 represents hydrogen, alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, alkoxyalkyl, optionally substituted aralkyl or optionally substituted aryl, R4 represents alkyl, R8 represents alkyl, or R1 and R6 together with the nitrogen atom to which they are attached represent a heterocyclic ring which may contain further heteroatoms, R6 being hydrogen, alkyl, halogenoalkyl, alkenyl, halogenoalkenyl or optionally represents substituted aralkyl, wherein Ar represents optionally substituted aryl, optionally substituted and/or
or anel 1ated
represents a heterocycle or group, where n represents the number 1 or 2], the compound 1-(4-chlorophenyl)-3-methyl-
4-piperidino-methylene-birazolin-5-one, 1
-(4-chlorophenyl)-3-methyl-4-morpholine-methylene-pyrazolin-5-one, ■-(4-chlorphenyl)-4-[4-(fluorophenylamino)-methylene]-3 -Methyl-pyrazolin-5-one and 1-(4-''lorphenyl)-3-methyl-4-aminomethylene-pyrazolin-5-one [see Kreutzberger, A. and Kolter %, ), Arch.

der Phar, ), 319 (,10), 865
It has been discovered that some of the known substituted pyrazolin-5-one derivatives and their salts, except for 871 (I986)], exhibit strong herbicidal and fungicidal properties.

The compounds of formula (I) can exist as geometric isomers (E/Z isomers) or as isomeric mixtures of varying composition.

The use of both pure isomers and mixtures of isomers is claimed by the present invention.

Furthermore, some of the compounds of formula (I) exist in tautomeric equilibrium; for the sake of simplicity, hereinafter we mean both the pure compounds and their mixtures with varying amounts of tautomeric compounds. Reference is always made to the use of compounds of formula (I) as

Surprisingly, some known substituted pyrazolin-5-one derivatives of formula (I) are structurally similar compounds with the same mode of action, 4-(cyanomethyloximino)- It exhibits better fungicidal properties than 3-methyl-1-722ruvirazolin-5-one at appropriate application concentrations. Additionally, some known substituted pyrazolin-5-one derivatives of formula (I) are structurally similar compounds with the same mode of action, 14-(2,4-dichlorobenzoyl) known in the art. -1,3-dimethylpyrazolin-5-yl]-4-
It exhibits better herbicidal properties than methyl phenyl sulfonate at appropriate application concentrations.

Substituted pyrazoline-5- which can be used according to the invention
On derivatives are generally defined by formula (I).

R1 is hydrogen, a straight chain or branched alkyl having 1 to 8 carbon atoms,
Cycloalkyl having 3 to 7 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and the same or different nitrogen atoms, and optionally substituted alkenyl or alkyl having 2 to 6 carbon atoms, provided that Possible substituents are unsubstituted phenyl or mono-, di- or tri-substituted phenyl, the substituents may be the same or different, and the phenyl substituents are the aryl substituents listed under Ar. , halogenoalkenyl in which R1 further has 2 to 6 carbon atoms and 1 to 1.0 of the same or different halogen atoms, alkoxy having 1 to 8 carbon atoms, alkoxyalkyl and alkylthio in which each alkyl moiety has 1 to 8 carbon atoms; Alkyl, alkylsulfonylalkyl or alkylsulfinylalkyl, alkoxycarbonylalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, 5- or 6-membered, optionally fluorine, chlorine, methyl and/or ethyl represents a substituted heterocycle, R1 is further each aryl moiety optionally mono, with the same or different substituents;
represents aryl, arylalkyl, aryloxyalkyl or arylthioalkyl which is di-, tri-, tetra- or penta-substituted and has 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety if present; , with the proviso that suitable aryl substituents are the aryl substituents listed under Ar;
C0-RI0 or -Co-0-R'', where R1
11 and R11 each independently represent 01-C4 alkyl or phenyl, R2 represents a group -NHR3, -NR'R' or -NHOR6, and R3 is hydrogen, a straight chain or branched chain having 1 to 8 carbon atoms; alkyl,
1 to 6 carbon atoms and 1- same or different halogen atoms
12 halogenoalkyl, straight chain or branched alkenyl having 2 to 12 carbon atoms, straight chain or branched alkenyl having 2 to 6 carbon atoms and 1 to 10 same or different halogen atoms, number of carbon atoms in alkoxy or alkyl moiety, respectively alkoxyalkyl having 1 to 8 carbon atoms, a linear or branched alkyl moiety having 1 to 4 carbon atoms, and an aryl moiety having 6 to 10 carbon atoms;
Aralkyl, mono- or polysubstituted, optionally with the same or different substituents, aryl having from 6 to C and mono-, di-, tri-, tetra- or penta-substituted with a time- or different substituents, as appropriate The aryl substituents are halogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, and dialkylamino, C, -C, alkoxy, and halogeno C1 to C, alkyl, each having 1 to 4 carbon atoms in the alkyl moiety; R1 represents alkyl having 1 to 6 carbon atoms, R8 represents alkyl having 1 to 6 carbon atoms, or R4
and R11 together with the nitrogen atom to which they are bonded represent a 5- or 6-membered heterocyclic ring which can contain oxygen, sulfur and/or nitrogen as an additional petro atom, R6 is hydrogen, the number of carbon atoms is 1 to 8 straight or branched alkyl,
Halogenoalkynoyl having 1 to 6 carbon atoms and the same or different halogen atoms, straight chain or branched alkenyl having 2 to 12 carbon atoms, and having 2 to 6 carbon atoms and the same or different halogen atoms is 1 to 10 halogenoalkenyl,
represents an aralkyl mono- or polysubstituted with the same or different substituents, where the alkyl moiety has 1 to 4 carbon atoms and the aryl moiety has 6 to 10 carbon atoms, provided that a suitable aryl [[i is halogen, C, -C, alkyl, halogeno C
t "" C4 alkyl and nitro, and Ar represents an aryl having from 6 to 10 carbon atoms, optionally mono- or polysubstituted with the same or different substituents, provided that suitable aryl substituents include halogen, nitro, cyanide. , carboxyl, alkoxycarbonyl having 1 to 4 carbon atoms, C1 to
C, alkyl, cl-C, alkoxy, 01-C, alkylthio, Cs#C, alkynyloxy, halogeno C1-C4 each having the same or different halogen atoms number of 1-9
Alkyl, halogeno C3-C, alkoxy or halogeno C, -C.

Alkylthio, phenyl, ClNC4alkylsulfonyl and halogenoC1-C4alkylsulfonyl having the same or different 1 to 9 halogen atoms, and di-C1-C
, alkylamino, and Ar represents an optionally substituted and/or optionally anilated 6-membered aromatic heterocycle containing at least one nitrogen atom, provided that suitable substituents are as listed under Ar above. substituted pyrazolin-5-ones and salts thereof, other than the compounds listed under formula CI), or Ar represents a group and n represents the number 1 or 2; It is suitable to use.

Particularly preferred compounds of formula (I) according to the invention are those in which R1 is hydrogen, C1-C4 straight-chain or branched alkyl, C3
cycloalkyl having from 1 to 6 carbon atoms, halogenoalkyl having from 1 to 3 carbon atoms and the same or different halogen atoms, such as especially fluorine and chlorine atoms, optionally substituted alkenyl or alkynyl having from 2 to 4 carbon atoms, respectively; with the proviso that unsubstituted phenyl or phenyl mono-, di- or tri-substituted with the same or different substituents may be mentioned as substituents and suitable phenyl substituents are the aryl substituents listed under Ar. ; R' further has 3 or 4 carbon atoms and the same or different halogen atoms, such as 1 to 5 halogen atoms, especially fluorine and chlorine; halogenoalkenyl having 1 to 4 carbon atoms;
alkoxy, each alkyl moiety has I to 4 carbon atoms, alkoxyalkyl, each alkyl moiety has 1 carbon number
-4 alkylthioalkyl, alkylsulfonylalkyl or alkylsulfinylalkyl, alkoxycarbonylalkyl whose alkoxy moiety has 1 or 2 carbon atoms and alkyl moiety has 1 or 2 carbon atoms, 5- or 6-membered,
Heterocycle, optionally substituted with fluorine, chlorine, methyl and/or ethyl, in particular 7ranyl, thenyl, furanylmethyl, thenylmethyl, or phenyl, naphthyl, benzyl, in which R1 is further each optionally substituted with mono, di, tri, tetra or penta; , 7-enylethyl, phenoxymethyl, phenoxyethyl, phenylthiomethyl or phenylthioethyl, with the proviso that the substituents may be the same or different, and appropriate phenyl substituents are the phenyl substituents listed under Ar, respectively. group, and R1 is further a group -NH
-GO-R'' or -〇 〇 -0-R''L, thioRIO and R11 each independently represent 01-C, alkyl or phenyl, Hz is a group -NHR'', -NR'R' Mata bar N HOR
6, where R3 is hydrogen, a straight or branched alkyl having 1 to 4 carbon atoms,
halogenoalkyl having 1 to 4 carbon atoms and the same or different halogen atoms, such as in particular 1 to 9 fluorine and chlorine atoms; straight-chain or branched alkenyl having 2 to 6 carbon atoms; halogenoalkenyl having from 1 to 7 or different halogen atoms, such as in particular fluorine and chlorine atoms,
Each alkoxy or alkyl moiety has 1 to 4 carbon atoms.
alkoxyalkyl, phenylalkyl having 1 to 3 carbon atoms in the straight-chain or branched alkyl moiety, optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents; optionally the same or different substituents; Demono, di, tori,
represents tetra- or penta-substituted phenyl, in which suitable phenyl substituents include halogen, straight-chain or branched alkyl having 1 or 2 carbon atoms and dialkylamino, C, -C, each having 1 or 2 carbon atoms in the alkyl moiety; , alkoxy, halogeno-C3-C, alkyl, R4 represents alkyl having 1 to 4 carbon atoms, R6 represents alkyl having 1 to 4 carbon atoms, and R4 and R5 together with the nitrogen atom to which they are bonded are represents a 5- or 6-membered heterocyclic ring which may contain oxygen, sulfur and/or nitrogen as an additional petroatom, R'' is hydrogen, straight or branched alkyl having 1 to 6 carbon atoms,
halogenoalkyl having 1 to 3 carbon atoms and the same or different halogen atoms, such as in particular 1 to 7 fluorine or chlorine atoms;
Straight chain or branched alkenyl having 2 to 6 carbon atoms, 2 carbon atoms
or 3 and identical or different halogen atoms, such as halogenoalkenyl having from 1 to 5 fluorine and chlorine atoms, mono, di, tri, represents tetra- or penta-substituted phenylalkyl, with the proviso that the phenyl substituent is halogen, C1-C, alkyl, halogeno-C,-C2 alkyl and nitro, and Ar is optionally the same or different substituents, mono-, di- ,bird,
represents tetra- or penta-substituted phenyl, with the proviso that suitable phenyl substituents are halogen, nitro, cyanide, carboxyl, alkoxycarbonyl having 1 to 3 carbon atoms, 01
~C, alkino1G1~Cs alkoxy, C1~C, alkylthio, C1~C, alkynyloxy, halogeno-C3~ each having the same or different number of halogen atoms from 1 to 7
C, alkyl, halogeno-Cl'= C4 alkoxy or halogeno-C1-C, alkylthio, phenyl, C,
-C,alkylsulfonyl, halogeno-C8-C3alkylsulfonyl having 1 to 7 identical or different halogen atoms, and -C1-C,alkylamino, optionally substituted where Ar contains at least one nitrogen atom and/or optionally an aniled 6-membered aromatic heterocycle, with the proviso that suitable substituents are the phenyl substituents mentioned above for Ar, or Ar represents a group, with n being the number 1 or 2. , and their salts, excluding the compounds already mentioned under formula (I).

Very particularly preferred compounds of formula (I) according to the invention are those in which R1 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclopropyl, cyclohexyl, trifluoro methyl,
Vinyl, allyl, butenyl, propargyl, 2-phenylvinyl, chlorallyl, methoxy, ethoxy, methoxymethyl, ethoxymethyl, methylthiomethyl, ethylthiomethyl, methylsulfonylmethyl, methylsulfonylethyl, ethylsulfonylmethyl, ethylsulfonylethyl, methylsulfinyl Methyl, methylsulfinylethyl, ethylsulfinylmethyl, ethylsulfinylethyl, furanyl, furanylmethyl, chenyl, chenylmethyl, pyridyl, phenylthio, ethoxycarbonylmethyl, methoxycarbonylmethyl, R1
7enyl, naphthyl, benzyl, each of which is further optionally mono-, di- or tri-substituted with the same or different substituents;
represents phenylethyl, phenoxymethyl or phenylthiomethyl, with the proviso that suitable phenyl substituents are the phenyl substituents mentioned under Ar, and R1 further represents a group -N
H-Co-R" or -C00RII, provided that R" and R11 each independently represent methyl, ethyl or phenyl, R2 represents a group -NHR', -NR'R' or -NH○R6, However, R3 is hydrogen, methyl, ethyl, n-propyl, i-propyl, i-butyl, 2,2-dimethylpropyl, n-hexyl, triple ormethyl, 2-chloroethyl, 3-
Chlorpropyl, propenyl, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, 3-chlorallyl, α-methylbenzyl, phenyl optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents. with the proviso that suitable phenyl substituents are fluorine, chlorine, methyl, methoxy, ethoxy, trifluoromethyl, trifluoroethyl/lz, dimethylamino, R4 represents methyl or ethyl, R8 represents methyl or ethyl , R6 and R'' together with the nitrogen atom to which they are bonded represent piperidinyl, piperazinyl, morpholinyl or thiomorpholinyl, R6 is hydrogen, methyl, ethyl, i-propyl, trifluoromethyl, 2-chloroethyl , 3-chloroethyl, propenyl, 3-chloroallyl, representing benzyl optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents, with the proviso that suitable phenyl substituents are fluorine, chlorine, methyl, ethyl, trifluoromethyl and nitro, and Ar is mono, di, tri,
represents tetra- or penta-substituted phenyl, with suitable phenyl substituents being fluorine, chlorine, nitro, cyano, carboxyl, methoxycarbonyl, ethoxycarbonyl, ethyl, methoxy, ethoxy, propagyloxy, trifluoromethyl, 2- chloroethyl, 3-chloropropylene, methylthio, ethylthio, trifluoromethoxy, trifluoromethylthio, phenyl, methylsulfonyl, trifluoromethylsulfonyl, dimethylamino, diethylamino, where Ar is optionally the same or different substituent, mono, di or represents trisubstituted pyridyl, benzothiazolyl or benzoxazolyl, with the exception that suitable substituents which may be mentioned are nitro, chlorine, cyano, trifluoromethyl, methyl, ethyl, methoxy, ethoxy and trifluoromethoxy; and its salts, excluding compounds excluded from formula (I).

Some of the compounds of formula (I) that can be used according to the invention are not known to date. For example, the formula (Ia)^rl [wherein R1 represents hydrogen, alkyl, cycloalkyl, halogenoalkyl, optionally substituted alkenyl or alkynyl, provided that a suitable substituent is unsubstituted phenyl or mono-, di- or tri- Substituted phenyl, the substituents may be the same or different and suitable phenyl substituents are the aryl substituents listed under Ar, R1 furthermore being halogenoalkenyl, alkoxy, alkoxyalkyl, alkylthioalkyl , alkylsulfonylalkyl, alkylsulfinylalkyl, alkoxycarbonylalkyl or dialkoxy(thio)phosphorylalkyl, respectively optionally substituted aryl, aralkyl, aryloxyalkyl or arylthioalkyl, or optionally substituted heterocycle or heterocycloalkyl or the group -NH-Co-RI0 or -Co
-0-R'', provided that RIo and R11 each independently represent alkyl or aryl, and R7 represents alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, alkoxyalkyl, optionally substituted aralkyl, or optionally substituted aryl. and Ar' represents a substituted aryl, an optionally substituted and/or optionally anilated heterocycle or group, where n represents the number 1 or 2. and its salts are the compound 1-(4-bromo-phenyl)-3-methyl-
4-Methylamino-methylidene-pyrazolin-5-one [see AIam, L.

■、、KviLko、J、Ya
, El'tosov, A, V, ,
Zh, Org Kim, 13(4), 864-8 (I97
7)] and 1-(4-chlorophenyl)-4-[(4-
fluorophenylamino)-methylene]-3-methyl-pyrazolin-5-one [see Kreuzberger, A.
.

and Coltra-1K, Ark Farm, 319 (I0
), 865-871 (I986)] are new.

Formula (I b) □ ^r1 [wherein R1 is hydrogen, alkyl, cycloalkyl, halogenoalkyl, each optionally substituted alkenyl or alkynyl, halogenoalkenyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl , alkoxycarbonylalkyl, dialkoxy(thio)phosphorylalkyl, each optionally substituted aryl, aralkyl, aryloxyalkyl or arylthioalkyl, or optionally substituted heterocycle or heterocyclealkyl,
or represents a group -NH-C〇-R1° or -〇〇-0-R'', provided that RIG and R11 each independently represent alkyl or aryl, and R6 is hydrogen, alkyl, halogenoalkyl, alkenyl, halogenoalkenyl or i represents a substituted aralkyl, and Ar' represents a substituted aryl, an optionally substituted and/or optionally anilated heterocycle or group, where n represents the number 1 or 2. pyrazolin-5-one derivatives and salts thereof have been discovered.

Also, formula (I c) Ar' [wherein %R' is hydrogen, alkinocycloalkyl, halogenoalkyl, optionally substituted alkenyl or alkynyl, halogenoalkenyl, alkoxy, alkoxyalkyl, (alkylthioalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl,
Alkoxycarbonylalkynodialkoxy(thio)
phosphorylalkyl, each optionally substituted aryl, aralkyl, aryloxyalkyl or arylthioalkyl or optionally substituted heterocycle or heterocycloalkyl, or the group -NH-Co-R'' or -C0-Q R
1+, provided that Rlo and R11 each independently represent alkyl or aryl, Ar' represents a substituted aryl, optionally substituted and/or optionally anionated heterocycle or group, provided that n is a number 1 or 2] r) Substituted pyrazolin-5-one derivatives and sled salts are the compound 4-aminomethylene-1-(2-ethylphenyl)-3-methyl-pyrazolin-5-one [see Kreuz Berger, A., & Coulter, K., Ark.Pharm., 318.89-91 (I985) and 4-aminomethylene-1-(4l0ruphenyl)-3-methyl-
Pyrazolin-5-one [see Kreuzberger, A.
and Colter, K., Ark Farm, 319.86.
5-871 (I986)] and is new.

Formula (I d) ^ "1 E In the formula, R1 is hydrogen, alkyl, cycloalkyl, halogenoalkyl, optionally substituted alkenyl or alkynyl, halogenoalkenyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl , alkoxycarbonylalkyl, dialkoxy(thio)phosphorylalkyl, each optionally substituted aryl, aralkyl, aryloxyalkyl or arylthioalkyl, or optionally substituted heterocycle or heterocycloalkyl, or the group -NH-Go-R' or -CO()-Rl
1, provided that RIG and R11 each independently represent alkyl or aryl, Ar' represents a substituted aryl, optionally substituted and/or optionally anionated heterocycle or group, provided that n is a number 1 or 2] Substituted pyrazolin-5-one derivatives and salts thereof are compound 1-(4-nitrophenyl)-3-methyl-4
-N,N-dimethylamino-methylidene-pyrazoline-
5-one, 1-(4-chlorophenyl)-3-(2-nitrophenyl)-4-N,N-dimethylamino-methylidene-pyrazolin-5-one and 1-(3-trifluoromethylphenyl) Except for aminomethylidene-pyrazolin-5-one, it has not been described previously.

Formula (I f) [wherein R1-1 is alkoxy, dialkoxy (thio)]
Phosphorylalkynope optionally substituted alkenyl, substituted aryl, optionally substituted aralkyl, optionally substituted furanylalkyl or chenylalkyl, optionally substituted heterocycle or group -NH-CO-R10
, where R11+ represents alkyl or phenyl, R7-1 represents hydrogen, alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, alkoxyalkyl, optionally substituted aralkyl, or optionally substituted aryl, and Ht-2 represents represents hydrogen or methyl] substituted pyrazolin-5-one derivatives and salts thereof are compound 1-phenyl-3-(4-methoxyphenyl)
Except for -4-N,N-dimethylaminomethylidene-pyrrolidin-5-one (UK Patent No. 887,509), no description has been made so far.

Furthermore, novel substitutions of formula (I a) The resulting pyrazolin-5-one derivatives can be prepared by converting an amine of formula (II) R7-NH, (u) [wherein R7 is as defined above] into α) optionally in the presence of a diluent, the amine of formula ( I d) Ar' [wherein R1 and Ar' have the above-mentioned meanings falling within the present invention; or β) if appropriate; It is obtained by reacting it with a 4-formyl-pyrazolin-5-one derivative of the formula (IV) Ar' [wherein R1 and Ar' are as defined above] in the presence of a diluent.

Furthermore, novel substituted pyrazolin-5-one derivatives of formula (I b) □ Ar' [wherein R1, R6 and Ar' are as defined above] are furthermore novel substituted pyrazolin-5-one derivatives of formula (I d) □ Ar' according to the present invention. 4-( in the formula, R1 and Ar' have the same meanings as above)
dimethylaminomethylidene)-pyrazolin-5-one derivatives of the formula (V) H,N-OR' (V) [wherein R6 is as defined above] It has been discovered that they can be obtained by reacting with amines or the corresponding hydrochloride salts.

Furthermore, the formula (I c) ^r1 [wherein R1 and Ar' have the same meanings as above, provided that the formula (
I b) Novel substituted pyrazolin-5-one derivatives of the formula (I d) ^r1 according to the invention, in which R1 and Ar' are as defined above Novel 4-(dimethylaminomethylidene)-pyrazoline-5-
pyrazolin-5-one of formula (Vl), where R1 and Ar' are as defined above, with ammonia, if appropriate in the presence of a diluent; In the presence of the agent, the formula (■
) was found to be obtained by reacting with 1,3,5-triazine.

Furthermore, the compound 1-(4-nitrophenyl)-3-methyl-4-N of formula (I d) ^r1 [wherein R1 and Ar' are as defined above],
N-dimethylamino-methylidene-pyrazolin-5-one and 1-(4-sulfophenyl)-3-methyl-4-
N,N-dimethylamino-methylidene-pyrazoline-5
Novel substituted pyrazolin-5-one derivatives excluding -one can be obtained by diluting pyrazolin-5-one derivatives of formula (VT) Ar' [wherein R1 and Ar' are as defined above] by σ) dilution dimethylformamide and 10 to 1
It has been discovered that β) can be obtained by reaction with an N,N-dimethylformamide derivative of formula (■), optionally in the presence of a diluent, at a temperature of 10 to 150°C. T-ko.

Furthermore, novel substituted pyrazoline-color-one derivatives of the formula (If) [wherein R1, R2 and R7-2 are as defined above] are furthermore provided by novel substituted pyrazoline-color-one derivatives of the formula (II a) [wherein R7-1, R7-2 are as defined above], α) optionally in the presence of a diluent; a pyrazolin-5-one derivative, or β) optionally in the presence of a diluent of the formula (lVb)r, where R1-1 is as defined above]
-formyl-pyrazolin-5-one derivatives.

Furthermore, R1 represents a group -NH-CO-R", provided that R
Formula CI) or (I) where 10=alkyl or aryl
Substituted pyrazolin-5-one derivatives of a), (I b), (I c) and (I d) have the formula (X) Ar'-
An arylhydrazine of the formula (XVI) R 00C-CI, optionally in the presence of a diluent, is converted in a first step to
-L- (I-K. In formula 1, R1 represents methyl or ethyl) is reacted with a compound of formula (X■) R"0OC-C1h-C"NII Amount Ar'' is as defined above], and the compound (X
) in the second stage [see G.A.M.C.
Tsuku (J, Am, Chem, Soc,) 665185
1 (I944)], optionally in the presence of a diluent and in the presence of a strong base, to give 3-aminopyra of formula (X■) Ar', where Ar' is as defined above. The zolin-5-one derivative is prepared and then the compound (X■) is added to the formula (X ff), if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, where Rl 1 is The meaning is the same as above, and A is halogen, especially chlorine or bromine, or
- is acylated with a compound of the formula (Vla)Ar1 [wherein Arl and R11 are as defined above, which is then used in the method embodiment (Ic/
1.3.5-1-Ryazine of formula (■) according to β) or method embodiment (Id/α and β) I thus according to formula (■)
It has now been discovered that dimethylformamide can be obtained by reacting it with N,N-dimethylformamide dimethyl acetal under corresponding reaction conditions.

The thus obtained substituted pyrazolin-5-one derivative of formula (Ie) Ar' [wherein R11 and Ar' are as defined above] can be added to the substituted pyrazolin-5-one derivative of formula (Ie), if appropriate in the presence of a diluent and of the formula Hydrolysis in the presence of a base suitable to the reaction conditions described in the preparation of the starting material of (IV) gives the formula (IVb)^r' [wherein R'' and Ar' are as defined above 1 compound of formula (I), which is then further reacted according to process embodiment (I a/β) to give pyrazoline-5 of formula (I) according to the invention.
- can be turned on (see manufacturing example).

Analogously to the method described above, the group -NH-Co-R'' can also be introduced into the compound of formula (If).

As described for compounds of formula (I), compounds of formula (I a
), (Ib), (Ic), (Id) and (If) can exist as geometric isomers (E/Z isomers) or as isomer mixtures of different compositions. Both pure isomers and isomeric mixtures are claimed according to the invention as well as tautomeric compounds as described in formula CI).

Known compounds of formula CI) include formulas (I a), (Ib),
They can be prepared in a similar manner to the methods described above for the preparation of the new compounds (I c), (I d) and (If).

That is, a compound of formula (r) Ar 1, in which R1, R2 and Ar have the same meanings as above, except for compounds excluded from formula (I), is, for example, a compound of formula (III) Ar [wherein R1 and Ar is a compound of formula (IVa) Ar having the same meaning as above; , R7 has the same meaning as above].

In the following description, compounds already excluded in the main description are those of formulas (I a), (I c) and (I d).
Preferred, particularly preferred and very particularly preferred ranges of compounds are likewise excluded.

Preferred novel substituted pyrazolines-5 of formula (I a)
-one derivatives, R1 is hydrogen, a straight chain or branched alkyl having 1 to 8 carbon atoms,
Cycloalkyl having 3 to 7 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and the same or different 1 to 9 atoms, optionally substituted alkenyl or alkynyl having 2 to 6 carbon atoms, provided that Possible substituents are unsubstituted phenyl or mono-, di- or tri-substituted phenyl, the substituents may be the same or different, and the phenyl substituents are the aryl substituents listed under Ar. , halogenoalkenyl in which R1 further has 2 to 6 carbon atoms and 1 to 10 same or different halogen atoms, alkoxy in which each alkyl moiety has 1 to 8 carbon atoms, alkoxyalkyl, alkylthioalkyl, Alkylsulfonylalkyl or alkylsulfinylalkyl, alkoxycarbonylalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, 5- or 6-membered, optionally substituted with fluorine, chlorine, methyl and/or ethyl; represents a heterocycle; R′ is further represented by the same or different substituents in each aryl moiety, optionally mono;
Aryl, arylalkyl, which is di-, tetra- or penta-substituted and has 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety, if present;
represents aryloxyalkyl or arylthioalkyl, with the proviso that suitable aryl substituents are the aryl substituents listed under Ar, and R1 further represents a group -N H-CO
-Rl' or -〇〇-0-R'', where R111 and R11 are each independently C3 to C4
alkyl or phenyl, R7 is a straight-chain or branched alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and the same or different halogen atoms, such as especially fluorine and chlorine atoms;
Straight-chain or branched alkenyls having 2 to 12 carbon atoms, halogenoalkenyls having 2 to 6 carbon atoms and the same or different halogen atoms, such as especially 1 to 10 fluorine and chlorine atoms,
The number of carbon atoms in each of the alkoxy and alkyl moieties is 1 to 8
Alkoxyalkyl, aralkyl optionally mono- or polysubstituted with the same or different substituents, in which the linear or branched alkyl moiety has 1 to 4 carbon atoms and the aryl moiety has 6 to IO carbon atoms; IO represents aryl optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents, with the proviso that suitable aryl substituents are in each case hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, The alkyl moiety is dialkylamino, CI-C, alkoxy or halogeno-C8-C4 alkyl each having 1 to 4 carbon atoms; represents a substituted aryl, with the proviso that suitable aryl substituents include halogen, nitro, cyano, carboxyl, alkoxycarbonyl having 1 to 4 carbon atoms, C0
~C, alkyl, CI'= C4 alkoxy, C0~C
, alkylthio, cZ~C, alkynyloxy, each having the same or different halogen atoms from 1 to 9 halogen C1
-C, alkyl, halogenoC, -C, alkoxy or halogenoC1-C4 alkylthio, phenyl, C1-C4
alkylsulfonyl and halogeno C3-C4 alkylsulfonyl having 1 to 9 identical or different halogen atoms, and di-C3-C4 alkylamino, optionally substituted and/or in which Ar' contains at least one nitrogen atom; represents a six-membered aromatic heterocycle, optionally aniled, with the proviso that suitable substituents are the aryl substituents listed above under Ar', or Ar' represents a group, where n is the number 1 or It is something that represents 2.

Particularly preferred novel compounds of formula (I a) are those in which R1 is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, or having 3 to 4 carbon atoms;
6 cycloalkyl, with 1 to 3 carbon atoms and the same or different halogen atoms, such as in particular 1 to 6 fluorine and chlorine atoms;
7 represents optionally substituted alkenyl or alkynyl each having 2 to 4 carbon atoms, provided that unsubstituted phenyl or phenyl mono-, di- or tri-substituted with the same or different substituents may be mentioned as substituent. and suitable phenyl substituents are the aryl substituents listed after Ar, and R1 is further a halogenoalkenyl having 3 or 4 carbon atoms and the same or different number of halogen atoms, such as especially the number of fluorine and chlorine ff11 to 5. , carbon number 1-4
alkoxy, each alkyl moiety has 1 to 4 carbon atoms, alkoxyalkyl, each alkyl moiety has 1 carbon number
-4 alkylthioalkyl, alkylsulfonylalkyl or alkylsulfinylalkyl, alkoxycarbonylalkyl whose alkoxy moiety has 1 or 2 carbon atoms and alkyl moiety has 1 or 2 carbon atoms, 5- or 6-membered,
a heterocycle optionally substituted with fluorine, chlorine, methyl and/or ethyl, in particular furanyl, chenyl, furanylmethyl, chenylmethyl, or phenyl, naphthyl, benzyl, in which R1 is further each optionally substituted with mono, di, tri, tetra or penta; represents phenylethyl, phenoxymethyl, phenoxyethyl, phenylthiomethyl or phenylthioethyl, with the proviso that the substituents may be the same or different and suitable phenyl substituents are respectively the phenyl substituents listed under Ar; ;R1 is further a group -NH
-Co'-R'' or -〇〇-〇-R11, where R'' and R'1 each independently represent 01-C4 alkyl or phenyl, and R7 is a straight chain or branched chain having 1 to 4 carbon atoms. chain alkyl, halogenoalkyl having 1 to 4 carbon atoms and the same or different halogen atoms, such as in particular 1 to 9 fluorine and chlorine atoms, straight-chain or branched alkenyl having 2 to 4 carbon atoms, having 2 to 4 carbon atoms;
4 and the same or different halogen atoms, e.g. halogenoalkyl having from 1 to 7 halogen atoms, in particular fluorine and chlorine atoms, alkoxyalkyl having from 1 to 4 carbon atoms in the alkoxy or alkyl moiety, carbon number in the linear or branched alkyl moiety, respectively. is optionally mono-, di-, tri-, tetra- or penta-substituted with 1 to 3 identical or different substituents, or optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents represents phenyl, provided that the appropriate phenyl substituents are halogen, 1 or 2 carbon atoms, respectively;
The number of carbon atoms in the alkyl moiety is 1 or 2, respectively.
dialkylamino, 01-C2 alkoxy or halogeno-C8-C2 alkyl, where Ar' is mono with the same or different substituents.

represents di-, tri-, tetra- or penta-substituted 7-enyl, provided that suitable phenyl substituents are halogen, nitro, cyano, carboxyl, alkoxycarbonyl having 1 to 3 carbon atoms, C1-C3 alkyl, 01-C3 alkoxy, C1
~C3 alkylthio, C, -C4 alkynyloxy, halogeno-C1-C, alkyl, halogeno-C1-C4 alkoxy or halogeno-CI-C, having the same or different halogen atoms from 1 to 7, furkylthio, phenyl,
A
r' represents an optionally substituted and/or optionally anilated 6-membered aromatic heterocycle containing at least one nitrogen atom, provided that suitable substituents are as described above for Ar'! ; is a phenyl substituent, or Ar' represents a group, provided that n is the number 1 or 2.

Very particularly preferred novel compounds of formula (I a) are R1
is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclopropyl, cyclohexyl, trifluoromethyl, vinyl, allyl, butenyl, frobagyl, 2-phenylvinyl, chlorallyl , methoxy, ethoxy, methoxymethyl, ethoxymethyl, methylthiomethyl, ethylthiomethyl, methylsulfonylmethyl, methylsulfonylethyl, ethylsulfonylmethyl, ethylsulfonylethyl, methylsulfinylmethyl, methylsulfinylethyl, ethylsulfinylmethyl, ethylsulfinylethyl, represents furanyl, furanylmethyl, chenyl, thenylmethyl, pyridyl, phenylthio, ethoxycarbonylmethyl, methoxycarbonylmethyl, and phenyl, naphthyl, benzyl, phenyl, in which R1 is further each optionally mono-, di-, or tri-substituted with the same or different substituents; represents ethyl, phenoxymethyl or phenylthiomethyl, with the proviso that suitable phenyl substituents are the phenyl substituents mentioned under Ar, and R1 further represents the group -NH-Co-R'' or -000R11; RIG and R11 each independently represent methinoethyl or phenyl, R7 is methyl, ethyl, n-propyl, i-propyl,
i-Butyl, 2,2-dimethylpropyl, n-hexyl, trifluoromethyl, 2-chloroethyl, 3-chloropropyl, propenyl, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, 3-chlorallyl, σ - methylbenzyl, representing phenyl substituted mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents, with the proviso that suitable phenyl substituents are fluorine, chlorine, methyl, methoxy, ethoxy, trifluoromethyl, trifluoromethyl; ethyl and dimethylamino, where Ar' represents phenyl, optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents, with the proviso that suitable phenyl substituents are fluorine, chlorine, nitro, cyano,
Carboxyl, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy, ethoxy, propagyloxy, trifluoromethyl, 2-chloroethyl, 3-chloropropyl, methylthio, ethylthio, trifluoromethoxy, trifluoromethylthio, phenyl, methylsulfonyl, trifluoro methylsulfonyl, dimethylamino, diethylamino, in which Ar' further represents pyridyl, benzothiazolyl or benzoxazolyl, optionally mono-, di- or tri-substituted with the same or different substituents, with the proviso that suitable substituents which may be mentioned are nitro, chlorine. , cyano, trifluoromethyl, methyl, ethyl, methoxy, ethoxy and trifluoromethoxy, or represents a group.

The following pyrazolin-5-one derived water of general formula (Ia) is:
In addition to the compounds mentioned in the preparation examples, it is possible to refer to: Table 1 RI R'Ar' Table 1
(continued) R'R'Ar' 1st
Table (continued) R'R'Ar' 1st
Table (Continued) Table 1 (Continued) Table 1 (Continued) Preferred and novel substituted pyrazolines-5 of formula (I b)
-one derivatives, R1 is hydrogen, a straight chain or branched alkyl having 1 to 8 carbon atoms,
cycloalkyl having 3 to 7 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and the same or different halogen atoms 1 to 9, optionally substituted alkenyl or alkynyl having 2 to 6 carbon atoms, with the proviso that The substituents may be unsubstituted phenyl or mono-, di- or tri-substituted phenyl, the substituents may be the same or different, and the phenyl substituents are the aryl substituents listed under Ar; RI further includes halogenoalkenyl having 2 to 6 carbon atoms and the same or different number of halogen atoms t-io, alkoxy having 1 to 8 carbon atoms, alkoxyalkyl, alkylthioalkyl, and alkyl each having 1 to 8 carbon atoms in each alkyl moiety; Sulfonylalkyl or alkylsulfinylalkyl, alkoxycarbonylalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, 5- or 6-membered, optionally substituted with fluorine, chlorine, methyl and/or ethyl Heterocycles especially furanyl or chenyl;
represents furanylmethyl or chenylmethyl; if RI is further optionally mono-, di-, tri-, tetra- or penta-substituted in each aryl moiety with the same or different substituents and each aryl moiety has 6 to 10 carbon atoms and, if present, an alkyl moiety; represents aryl, arylalkyl, aryloxyalkyl or arylthioalkyl having 1 to 4 carbon atoms, with the proviso that suitable aryl substituents are the aryl substituents listed under Ar; NH-Go-R" or -〇〇-〇-R11,
Note that RIG and R11 each independently represent 01-C4 alkyl or phenyl, R6 is hydrogen, a linear or branched alkyl having 1 to 8 carbon atoms,
halogenoalkyl having 1 to 6 carbon atoms and the same or different halogen atoms, such as in particular 1 to 12 fluorine and chlorine atoms; linear or branched alkenyl having 2 to 12 carbon atoms; halogenoalkyl having a number of or different halogen atoms, such as in particular fluorine and chlorine, from 1 to 10,
represents an aralkyl optionally mono- or polysubstituted with the same or different substituents, having 1 to 4 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part, provided that suitable aryl substituents include halogen, 01 to 10 carbon atoms; C.

alkyl, halogeno-C1-C4 alkyl and nitro, and Ar' represents aryl having from 6 to 10 carbon atoms, optionally mono- or polysubstituted with the same or different substituents, provided that suitable aryl substituents include halogen , nitro, cyano, carboxyl, alkoxycarbonyl having 1 to 4 carbon atoms, 01
-C4 alkyl, C1-C, alkoxy, C3-C4 alkylthio, 03-C, alkynyloxy, halogeno C1-C each having the same or different halogen atoms from 1 to 9
, alkyl, halogeno01-C, alkoxy or halogeno C1-C, alkylthisu, phenylated C1-C, alkylsulfonyl and the same or different halogen atom number 1
~9 halogenoCl-C4alkylsulfonyl, and di-Cl-c4alkylamino, optionally substituted and/or optionally anionated 6-membered aromatic heterocycle in which Ar' contains at least one nitrogen atom , with the proviso that suitable substituents are the aryl substituents listed above under Ar', or Ar' represents a group, with n representing the number 1 or 2.

Particularly preferred novel compounds of formula (Ib) are those in which R1 is hydrogen;
Straight chain or branched alkyl having 1 to 4 carbon atoms, 3 to 6 carbon atoms
cycloalkyl having 1 to 3 carbon atoms and the same or different halogen atoms, such as especially fluorine and chlorine atoms;
7 represents optionally substituted alkenyl or alkynyl each having 2 to 4 carbon atoms, provided that unsubstituted phenyl or phenyl mono-, di- or tri-substituted with the same or different substituents may be mentioned as substituent. Suitable phenyl substituents are the aryl substituents listed under Ar, and R1 further includes halogen atoms having 3 or 4 carbon atoms and the same or different halogen atoms, such as especially fluorine and chlorine atoms, having from 1 to 5. Alkenyl, alkoxy having 1 to 4 carbon atoms, alkoxyalkyl having 1 to 4 carbon atoms in each alkyl moiety, alkylthioalkyl having 1 to 4 carbon atoms in each alkyl moiety, alkylsulfonylalkyl or alkylsulfinylalkyl, Alkoxycarbonylalkyl having 1 or 2 carbon atoms and 1 or 2 carbon atoms in the alkyl moiety, 5- or 6-membered heterocycle optionally substituted with fluorine, chlorine, methyl and/or ethyl, especially 7ranyl, chenyl, furanylmethyl, chenylmethyl or R1 is further optionally mono-, di-, tri-, tetra- or penta-substituted phenyl, naphthyl,
represents benzyl, phenylethyl, phenoxymethyl, phenoxyethyl, phenylthiomethyl or phenylthioethyl, provided that the substituents may be the same or different, and suitable phenyl substituents are the phenyl substituents listed under Ar, respectively. and the R side is further a group -NH-Co-
R'° or -CO-0-R'', where R'' and R'' each independently represent C1-C, alkyl or phenyl, and R8 is hydrogen, a straight chain or branched chain having 1 to 6 carbon atoms. alkyl,
Halogenoalkyl having 1 to 3 carbon atoms and the same or different halogen atoms, such as 1 to 7 fluorine and chlorine atoms; straight-chain or branched alkenyl having 2 to 6 carbon atoms; or different halogen atoms, such as in particular fluorine and chlorine atoms, optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents having from 1 to 3 carbon atoms; represents phenylalkyl, with the proviso that suitable phenyl substituents are halogen, cI~C, alkinohalogenoC1~
C2 alkyl and nitro, and Ar' is mono, optionally with the same or different substituents.

represents di-, tri-, tetra- or penta-substituted phenyl, with the proviso that suitable phenyl substituents are halogen, nitro, cyano, carboxyl, alkoxycarbonyl having 1 to 3 carbon atoms, C1-C, alkyl, CI"" Cs alkoxy, C1-C, alkylthio, C3-C4 alkynyloxy, halogeno-CI-C, alkyl, halogeno-C8-C4 alkoxy or halogeno-CI-C, alkylthio; phenyl, C8- C, alkylsulfonyl, halogeno-C3-C, alkylsulfonyl having the same or different 1 to 7 halogen atoms, and di-C2-C, alkylamino, optionally substituted in which Ar' contains at least one nitrogen atom represents a 6-membered aromatic heterocycle, optionally aniled and/or optionally anionated, with the proviso that suitable substituents are the phenyl substituents mentioned above for Ar', or Ar' represents a group, where n is the number 1 or 2.

Very particularly preferred novel compounds of formula (Ib) are those in which R1 is hydrogen, methyl, ethyl, n-propyl, i-propyl,
n-butyl, i-butyl, tert-butyl, cyclopropyl, cyclohexyl, trifluoromethyl, vinyl, allyl, butenyl, propargyl, 2-phenylvininochloroallyl, methoxy, ethoxy, methoxymethyl, ethoxymethyl, methylthiomethyl, ethylthio Methyl, methylsulfonylmethyl, methylsulfonylethyl, ethylsulfonylmethyl, ethylsulfonylethyl,
methylsulfinylmethyl, methylsulfinylethyl, ethylsulfinylmethyl, ethylsulfinylethyl, furanyl, furanylmethyl, chenyl, chenylmethyl, pyridyl, phenylthio, ethoxycarbonylmethyl, methoxycarbonylmethyl, and R1 is each optionally the same or different substituent; represents mono-, di- or tri-substituted phenyl, naphthyl, benzyl, phenylethyl, phenoxymethyl or phenylthiomethyl, with the proviso that suitable phenyl substituents are those mentioned under Ar, and R1 is further Group -NH-Go-R1' or -COOR11
, provided that R" and R" each independently represent methyl, ethyl or phenyl, and R- is hydrogen, methyl, ethyl, i-propyl, trifluoromethyl, 2-chloroethyl, 3-chloropropyl,
Propenyl, 3-chloroallyl, represents benzyl optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents, with the proviso that suitable phenyl substituents are fluorine,
chlorine, methyl, ethyl, trifluoromethyl and nitro, and Ar' represents phenyl, optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents, with the proviso that suitable phenyl substituents are fluorine. , chlorine, nitro, cyano,
Carboxyl, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy, ethoxy, propagyloxy, trifluoromethyl, 2-chloroethyl, 3-chloropropyl, methylthio, ethylthio, trifluoromethoxy, trifluoromethylthio, phenyl, methylsulfonyl, trifluoro methylsulfonyl, dimethylamino, diethylamino, and A r ' further represents pyridinobenzothiazolyl or benzoxazolyl, optionally mono-, di- or tri-substituted with the same or different substituents, with the proviso that suitable substituents which may be mentioned are nitro, chlorine, cyano, trifluoromethyl, methyl, ethyl, methoxy, ethoxy and trifluoromethoxy or represents a group.

Preferred novel substituted pyrazolines-5 of formula (I c)
-one derivatives, R1 is hydrogen, a straight chain or branched alkyl having 1 to 8 carbon atoms,
cycloalkyl having 3 to 7 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and the same or different halogen atoms, and optionally substituted alkenyl or alkynyl having 2 to 6 carbon atoms, which may be mentioned; The substituents are unsubstituted phenyl or mono-, di- or tri-substituted phenyl, the substituents may be the same or different, and the phenyl substituents are the aryl substituents listed under Ar; is further a halogenoalkenyl having 2 to 6 carbon atoms and the same or different halogen atoms, and 1 to 10 carbon atoms;
-8 alkoxy, alkoxyalkyl, alkylthioalkyl, each alkyl moiety having 1 to 8 carbon atoms,
Alkylsulfonylalkyl or alkylsulfinylalkyl, alkoxycarbonylalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, 5- or 6-membered, optionally substituted with fluorine, chlorine, methyl and/or ethyl; represents a heterocyclic ring, especially furanyl or chenyl; furanylmethyl, chenylmethyl, and R1 is optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents in each aryl part, and each aryl part has 6 to 6 carbon atoms; lO and, if present, aryl, arylalkyl, aryloxyalkyl or arylthioalkyl in which the alkyl moiety has 1 to 4 carbon atoms, with the proviso that suitable aryl substituents are the aryl substituents listed under Ar. and R1 is further a group -N
represents H-Co-R'° or -CO-O-R11, where RIG and R11 each independently represent 01-C4 alkyl or phenyl, and Ar' has 6 to 1O carbon atoms, the same or different as occasion demands; Represents aryl mono- or polysubstituted with a substituent, provided that suitable aryl substituents include halogen, nitro, cyano, carboxyl, alkoxycarbonyl having 1 to 4 carbon atoms, C1
'~C4 alkyl, C1~C, alkoxy, C1~C
, alkylthio, C1-C6 alkynyloxy, halogeno C each having the same or different halogen atoms from 1 to 9,
-C, alkyl, halogeno C1-C4 alkoxy or halogeno C1-C4 alkylthio, phenyl, C1-C,
Alkylsulfonyl and halogeno C1-C4 alkylsulfonyl having 1 to 9 identical or different halogen atoms, and di-C1-C, alkylamino, optionally substituted where Ar' contains at least one nitrogen atom and/
or an optionally aniled six-membered aromatic heterocycle, with the proviso that suitable substituents are the aryl substituents listed above under Ar', or Ar' represents a group, where n is a number. ) represents 1 or 2.

Particularly preferred novel compounds of formula (I c) are those in which R1 is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, or having 3 to 4 carbon atoms;
6 cycloalkyl, having 1 to 3 carbon atoms and the same or different halogen atoms, such as especially 1 fluorine and chlorine atoms;
~7 halogenoalkyno represents optionally substituted alkenyl or alkynyl each having 2 to 4 carbon atoms, provided that unsubstituted phenyl or mono-, with the same or different substituent,
Di- or tri-substituted phenyl may be mentioned as a substituent and suitable phenyl substituents are the aryl substituents listed under Ar; R′ further contains 3 or 4 carbon atoms and the same or different halogens. Halogenoalkenino, alkoxy having 1 to 4 carbon atoms, particularly fluorine and chlorine having 1 to 5 atoms, alkoxy having 1 to 4 carbon atoms in each alkyl moiety, and 1 to 4 carbon atoms in each alkyl moiety, respectively. ~
4 alkylthioalkyl, alkylsulfonylalkyl or alkylsulfinylalkyl, alkoxycarbonylalkyl having 1 or 2 carbon atoms in the alkoxy moiety and 1 or 2 carbon atoms in the alkyl moiety, 5- or 6-membered, optionally fluorine, -chlorine, methyl and/or ethyl-substituted heterocycle, especially furanyl, chenyl, 7-ranylmethyl, thenylmethyl, or phenyl, naphthyl, benzyl, phenyl, in which R' is further optionally substituted with mono, di, tri, su, tetra or penta, respectively. represents ethyl, phenoxymethyl, phenoxyethyl, phenylthiomethyl or phenylthioethyl, with the proviso that the substituents may be the same or different and suitable phenyl substituents are respectively the phenyl substituents listed under Ar; R1 is further a group -
NH-CO-RI0 or -Go-0-R; R16 and R11 each independently represent 01-C4 alkyl or phenyl; Ar' is optionally the same or different substituent; mono;

represents di-, tri-, tetra- or penta-substituted phenyl, with the proviso that suitable phenyl substituents are halogen, nitro, cyano, carboxyl, alkoxycarbonyl having 1 to 3 carbon atoms, C5-C3 alkyl, 01-C, alkoxy, C1
~C3 alkylthio, C8-C4 alkynyloxy, halogeno-C, -C, alkyl, halogeno-C1-C, alkoxy or halogeno-C3-C4 alkylthio, phenyl, each having the same or different halogen atoms from 1 to 7;
C□-C, alkylsulfonyl, halogeno-C8-C3 alkylsulfonyl having the same or different halogen atoms from 1 to 7, and di-C1-C, alkylamino, and A
r' represents an optionally substituted and/or optionally anilated 6-membered aromatic heterocycle containing at least one nitrogen atom, with the proviso that suitable substituents are the phenyl substituents mentioned above for Ar', or Ar' represents a group, provided that n is the number 1 or 2.

Very particularly preferred novel compounds of formula (I c) are R1
is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclopropyl, cyclohexyl, trifluoromethyl, vinyl, allyl, butenyl, propargyl, 2-phenylvinyl, chlorallyl , methoxy, ethoxy, methoxymethyl, ethoxymethyl, methylthiomethinoethylthiomethyl, methylsulfonylmethyl, methylsulfonylethyl, ethylsulfonylmethyl, ethylsulfonylethyl, methylsulfinylmethyl, methylsulfinylethyl, ethylsulfinylmethyl, ethylsulfinylethyl , furanyl, 7-ranylmethyl, chenyl, thenylmethyl, pyridyl, phenylthio, ethoxycarbonylmethyl, methoxycarbonylmethyl, and R1 is further mono-, di-, or tri-substituted with the same or different substituents as occasion demands, phenyl, naphthyl, benzyl , phenylethyl, phenoxymethyl or phenylthiomethyl, with the proviso that suitable phenyl substituents are the phenyl substituents mentioned under Ar, and R1 further represents a group -NH-Co-R" or -Co-0 -R represents 7-enyl, in which R10 and R11 each independently represent methyl, ethyl or phenyl, and Ar' is optionally substituted with mono-, di-, tri-, tetra- or penta-substituted , where suitable phenyl substituents are fluorine, chlorine, nitro, cyano,
Carboxyl, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy, ethoxy, propagyloxy, trifluoromethyl, 2-chloroethyl, 3-chloropropyl, methylthio, ethylthio, trifluoromethoxy, trifluoromethylthio, phenyl, methylsulfonyl, trifluoro methylsulfonyl, dimethylamino, diethylamino, and Arl further represents pyridyl, benzothiazolyl or benzoxazolyl, optionally mono-, di- or tri-substituted with the same or different substituents, provided that suitable substituents which may be mentioned are nitro, chlorine, Cyano, triple ormethyl, methyl, ethyl, methoxy, ethoxy and trifluoromethoxy, or represent a group.

Preferred novel substituted pyrazolines-5 of formula (I d)
-one derivatives, R1 is hydrogen, a straight chain or branched alkyl having 1 to 8 carbon atoms,
Cycloalkyl having 3 to 7 carbon atoms stands for halogenoalkyl having 1 to 4 carbon atoms and the same or different halogen atoms and 1 to 9 carbon atoms, optionally substituted alkenyl or alkynyl having 2 to 6 carbon atoms, provided that the substitutions that may be mentioned The radicals are unsubstituted phenyl or mono-, di- or tri-substituted phenyl, the substituents may be the same or different, and the phenyl substituents are the aryl substituents listed under Ar, and R1 is Furthermore, halogenoalkenyl having 2 to 6 carbon atoms and 1 to 10 same or different halogen atoms, 1 carbon number;
-8 alkoxy, alkoxyalkyl, alkylthioalkyl, each alkyl moiety having 1 to 8 carbon atoms,
Alkylsulfonylalkyl or alkylsulfinylalkyl, a 6-membered alkoxycarbonylalkyl heterocycle having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, optionally substituted with fluorine, chlorine, methyl and/or ethyl In particular, it represents furanyl or chenyl, furanylmethyl, chenylmethyl, and R1 is further optionally mono-, di-, tri-, tetra- or penta-substituted on the aryl moiety with the same or different substituents, and each aryl moiety has 6 to 10 carbon atoms and is present. If so, aryl, arylalkyl, where the alkyl moiety has 1 to 4 carbon atoms,
represents aryloxyalkyl or arylthioalkyl, with the proviso that suitable aryl substituents are the aryl substituents listed under Ar, and R1 further includes the group -NH-Co-
R" or -CO-O-R11, where R" and R11 each independently represent 01 to C. represents alkyl or phenyl, and Ar' represents aryl having 6 to 10 carbon atoms, optionally mono- or polysubstituted with the same or different substituents, provided that suitable aryl substituents include halogen, nitro, cyano, carboxyl, carbon Number 1 to 4 alkoxycarbonino mutter 01
~C4 alkyl, 01~C, alkoxy, Cl~C, alkylthio, c3~C, alkynyloxy, each having the same or different halogen atoms of 1 to 9 halogenoC, ~C
4 alkyl, halogenoC. -C, alkoxy or halogeno c1-c4 alkylthio, phenyl, C. -C, alkylsulfonyl and the same or different halogen atom t1
~9 halogenoC1-C, alkylsulfonyl, and di-C1-C4 alkylamino, optionally substituted and/or optionally anionated 6-membered aromatic where Ar' contains at least one nitrogen atom represents a heterocycle, provided that suitable substituents are the aryl substituents listed above under Ar', or Ar' represents a group, with n representing the number 1 or 2;

Particularly preferred and novel compounds of formula (I d) are those in which R1 is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, or having 1 to 4 carbon atoms;
cycloalkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 3 carbon atoms and the same or different norogen atoms, such as in particular 1 to 7 fluorine and chlorine atoms, optionally substituted alkenyl or alkynyl having 2 to 4 carbon atoms, respectively; , provided that unsubstituted phenyl or 1. % means that phenyl mono-, di- or tri-substituted with the same or different substituents can be mentioned as a substituent, and suitable phenyl substituents are the aryl substituents listed under Ar, and R1 is further represented by the number of carbon atoms. 3 or 4 and the number of the same or different 10 atoms, such as especially fluorine and chlorine, from 1 to 5, with 1 carbon number
-4 alkoxy, alkoxyalkyl each alkyl moiety has 1 to 4 carbon atoms, alkylthioalkyl each alkyl moiety has 1 to 4 carbon atoms, alkylsulfonylalkyl or alkylsulfinylalkyl, alkoxy moiety has 1 or 4 carbon atoms 2 and alkoxycarbonylalkyl having 1 or 2 carbon atoms in the alkyl moiety, a 5- or 6-membered heterocycle optionally substituted with fluorine, chlorine, methyl and/or ethyl, especially furanyl, chenyl, furanylmethyl, chenylmethyl, or R1 further represents phenyl, naphthyl, benzyl, phenylethyl, phenoxymethyl, phenoxyethyl, phenylthiomethyl or phenylthioethyl, each optionally substituted with mono, di, tri, tetra or penta, provided that the substituents may be the same or different. Common and suitable phenyl substituents are the phenyl substituents listed under Ar, respectively, where R1 further represents the group -NH-Go-R" or -Co-0-R", thioRIG and R11 each independently represents 01-C, alkyl or phenyl; Ar' is optionally the same or different substituents; mono;

represents di-, tri-, tetra- or penta-substituted phenyl, with the proviso that suitable phenyl substituents are halogen, nitro, cyano, carboxyl alkoxycarbonyl having 1 to 3 carbon atoms, CI-C, alkyl, C. ~C, alkoxy, 01
~C, alkylthio, C, ~C, alkynyloxy, halogeno-C1-C, alkyl, halogeno-C1-C4 alkoxy or halogeno-Cl-C, alkylthio, each having the same or different halogen atoms from 1 to 7; phenyl,
C, ~C, alkylsulfonyl, halogeno-C1-C, alkylsulfonyl of the same or different halogen atoms al~7, and di-C1-C, alkylamino, A
r' represents an optionally substituted and/or optionally anilated 6-membered aromatic heterocycle containing at least one nitrogen atom, with the proviso that suitable substituents are the phenyl substituents mentioned above for Ar'above; , or Ar' represents a group, provided that n is the number 1 or 2.

Very particularly preferred novel compounds of formula (I d) are R1
is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, cyclopropyl, cyclohexy/L=.

Trifluoromethyl, vinyl, allyl, butenyl, propargyl, 2-phenylvinyl, chlorallyl, methoxy, ethoxy, methoxymethyl, ethoxymethyl, methylthiomethyl, ethylthiomethyl, methylsulfonylmethyl.

Methylsulfonylethyl, ethylsulfonylmethyl, ethylsulfonylethyl, methylsulfinylmethyl, methylsulfinylethyl, ethylsulfinylmethinomethylethylsulfinylethyl, furanyl, 7ranylmethyl, chenyl, chenylmethyl, pyridyl, phenylthio, ethoxylponylmethinomethyl represents methoxycarbonylmethyl, R1 is further optionally mono-, di- or tri-substituted with the same or different substituents; represents phenyl, naphthinobenzyl, phenylethyl, phenoxymethyl or phenylthiomethyl, with the proviso that R1 represents a suitable phenyl The substituent is Ar
a phenyl substituent mentioned under Ar' represents phenyl, optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents, with the proviso that suitable phenyl substituents are fluorine, chlorine, nitro, cyano,
Carboxyl, methoxycarbonyl, ethoxycarbonyl, methyl, ethinomethyl, metquine, ethoxy, probagyloxy, trifluoromethyl, 2-chloroethyl, 3-
chloropropyl, methylthio, ethylthio, trifluoromethoxy, trifluoromethylthio, phenyl, methylsulfonyl, trifluoromethylsulfonyl, dimethylamino, diethylamino, where Ar' is optionally further mono-, di- or tri-substituted with the same or different substituents. pyridyl, benzothiazolyl or benzoxazolyl, where suitable substituents which may be mentioned are nitro, chlorine, cyano, trifluoromethyl, methyl, ethyl, methoxy,
It is ethoxy and trifluoromethoxy or represents a group.

Suitable compounds of formula (If) include R1-1 representing 01-C, alkoxy, alkenyl having 2 to 6 carbon atoms optionally substituted with unsubstituted phenyl or mono-, di- or tri-substituted phenyl; , provided that the substituents may be the same or different and the phenyl substituents that may be mentioned are C3-C4 alkyl, 01-C, alkoxy, halogeno-C, -C, alkyl and halogeno-C2-C4 alkoxy, and R1-1 further has 6 to 10 carbon atoms, mono-, di-, tri-, tetra- or penta-substituted aryl with the same or different substituents, or aryl part has 6 to 10 carbon atoms and alkyl part has 1 to 4 carbon atoms represents an optionally substituted aralkyl group, with the aryl substituents which may be mentioned respectively being halogen, nitro, cyan, carboxyl% CI-C4 alkoxycarbonyl, 01-C,
Alkyl, C0-C4 alkoxy, halogeno-C1-C
4 alkyl, halogeno-C1-C4 alkoxy, halogeno-C3-C, alkylthio, phenyl, C,-C4 alkylsulfonyl, halogeno-C1-C, alkylsulfonyl and di-C1-C, alkylamino, and R1-1 is 5 which may further contain l or two identical or different petroatoms, in particular nitrogen, oxygen and sulfur.
or a 6-membered heterocycle optionally substituted with fluorine, chlorine, methyl and/or ethyl; , or R1-1 further represents a group -NH-Co-R10, where RID represents C, -C, alkyl or phenyl, R7-1 is hydrogen, 01-C, alkyl, halogeno-c,
-C6 alkyl, C2-C6 alkenyl, halogeno-C
2-C6 alkenyl, C1-Ca alkoxy-C, -C
, alkyl, aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety, optionally mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents; represents an aryl substituted with 6 to 10 optionally mono-, di-, tri-, tetra- or penta-substituted substituents, with the proviso that the aryl substituents which may be mentioned in each case are halogen, C, -C4 alkyl, 01-C4
4-alkoxy, halogeno-C8-C4 alkyl and di-C,-C,alkylamino, and R7-2 represents hydrogen or methyl, and the compound l-phenyl-5-(4-methoxyphenyl)-4 -N,N-dimethylamino-pyrazoline-5
-On is excluded.

Particularly preferred compounds of formula (If) are those in which RI-1 is 01 to C6 alkoxy, optionally substituted with phenyl, or optionally substituted with phenyl, optionally mono-, di- or tri-substituted with the same or different substituents; represents 2-4 alkenyl, with the exception that phenyl substituents which may be mentioned are fluorine, chlorine, CI"" Cs alkyl, C3-C, alkoxy, halogeno-C1-C, alkyl and hyhalogeno-C2-C6 alkoxy, R'-' is further mono-, di-, tri-, tetra- or penta-substituted with the same or different substituents; represents benzyl or 7-enethyl, provided that suitable phenyl substituents are fluorine, chlorine, bromine, nitro, cyano, carboxyl, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy, ethoxy, in each case the same or different halogen atoms, such as fluorine or The number of chlorine is 1
~5 halogeno-C3-C2 alkyl, halogeno-C1
-C2 alkoxy, halogeno-C1-C2 alkylthio, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, dimethylamino and diethylamino, and R1-1 is further each optionally fluorine, chlorine, methyl and/
or ethyl-substituted 7ranylmethyl, furanylethyl, thenylmethyl or thenylethyl, or R1-1 further represents a group -NH-CO-R"', provided that Rlo represents 01-C4 alkyl or phenyl, and R7-1 Hydrogen, C1-C, alkyl, halogeno-Cr
~C, alkyl, C2-C4 alkenyl, halogeno-C
2-C, alkenyl, C1-C6 alkoxy 08-C
, alkyl, benzyl or phenethyl, each optionally substituted with mono, di, tri, tetra or penta with the same or different substituents, or phenyl, as appropriate with mono, di, tri, tetra or penta substituted with the same or different substituents. with the proviso that phenyl substituents which may be mentioned respectively are fluorine, chlorine, bromine, methyl, ethyl, halogeno-C3-C2
Alkyl, especially triple ormethyl, dimethylamino and diethylamino, especially those in which R7-2 represents hydrogen or methyl, and the compounds l-phenyl-5-(4-methoxyphenyl)-4-N,N -dimethylamino-pyrazolin-5-one is excluded.

Very particularly preferred compounds of formula (If) are those in which RI-1 is 0
1-C, alkoxy, vinyl, allyl, futhynyl, 2-
Phenylvinyl, 2-(2-trifluoromethylphenyl)-vinyl, phenyl mono-, di- or tri-substituted with the same or different substituents, or optionally mono-, di- or tri-substituted with the same or different substituents represents benzyl, provided that phenyl substituents which may be mentioned respectively are fluorine, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,
difluoromethyl, trifluoromethylsulfonyl, methylsulfonyl, dimethylamino and diethylamino, and Rl-1 is optionally further fluorine, chlorine, methyl and/or
or ethyl-substituted furanylmethyl or thenylmethyl or M-NH-C0-R", where R" represents methyl, ethyl or phenyl, and R1-1
is hydrogen, methyl, ethyl, n- or i-furovir, halogeno-C1-C2 alkyl, especially trifluoromethyl,
Allyl, propargyl, halogeno-C2-C3 alkenyl, C1-C2 alkoxy-C1-C2 alkyl, benzyl or phenethyl optionally mono-, di- or tri-substituted with the same or different substituents, or mono- or phenethyl with the same or different substituents. , represents di- or tri-substituted phenyl, with the proviso that the phenyl substituents which may be mentioned in each case are fluorine, chlorine, methyl, trifluoromethyl and dimethylamino, and R7-2 represents hydrogen or methyl, with the proviso that Compound 1-phenyl-5-(4-methoxyphenyl)-4-N,N-'; excluding methylamino-pyrazolin-5-one.

The following pyrazolin-5-one derivatives of formula (If) may be mentioned separately in addition to the compounds mentioned in the preparation examples: Table 2 Rl-I R+-I R7-Z Table 2 (continued) Rl - I R7-I R7-
tCμ HCI+.

-ku, SCF.

Table 2 (continued) R=l R''R'-2 Table 2 (continued) Table 2 (continued) Table 2 (continued) For example, 1-(2,6-dichloro-4-trifluoromethylphenyl) -4(N,N-'; methylaminomethylidene)-3-methyl-pyrazolin-5-one and methylamine are used as starting materials, the formula (I a The reaction process for the preparation of substituted pyrazolin-5-ones of ) can be described by the following formula: When formyl-3-methyl-pyrazolin-5-one and 2,4-dichloroaniline are used as starting materials, a substituted pyrazoline-of formula (Ia) according to the process embodiment (I a/β) of the invention The reaction process for the production of 5-one can be described by the following equation: CF.

For example, when using 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-(N,N-dimethylaminomethylidene)-pyrazolin-5-one and N-methylhydroxylamine hydrochloride as starting materials , formula (I
The reaction process for the preparation of substituted pyrazolin-5-one derivatives of b) can be described by the following formula: CF.

For example, when using 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-(N,N-dimethylaminomethylidene)-3-methylpyrazolin-5-one and ammonia as starting materials, process embodiments (I c/σ
The reaction process for the preparation of substituted pyrazolin-5-one derivatives of formula (Ic) according to When using (methylphenyl)-3-methyl-pyrazolin-5-one and 1,3,5-triazine as starting materials,
Process Embodiment (Ic/β) The reaction process for the preparation of substituted pyrazolin-5-one derivatives of formula (Ic) can be described by the following formula: , 6-dichloro-4-trifluoromethylphenyl)-3-methyl-pyrazolin-5-one and dimethylformamide in the presence of a diluent, the formula (Id
) can be described by the following formula: CF.

For example, when using 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-methyl-pyrazolin-5-one and N,N-dimethylformamide dimethyl acetal as starting materials, the method embodiment (Id/β ) The reaction process for the preparation of substituted pyrazolin-5-ones of formula (I d) can be described by the following formula: Formula (Iff), which can be used as starting material for the preparation of Some of the pyrazolin-5-one derivatives of ] are known [see, zh, Obs, Khimii
), 32 (I2), 4050 (I962)).

Which formula (Id) can be used as starting material for the preparation of substituted pyrazolin-5-one derivatives of formulas (Ia), (Ib) and (Ic)? Ar1 [wherein R' and Ar' are as defined above, but compound 1-(4-nitrophenyl)-3-methyl-4-(N,
N-dimethylamino-methylidene)pyrazolin-5-one and 1-(4-sulfophenyl)-3-methyl-4-
(N.

N-dimethylamino-methylidene)-pyrazoline-5~
The pyrazolin-5-ones according to the invention are new, constitute -i of the invention, and can be prepared as already described.

The compounds of formula (■) necessary for this are compounds generally known in organic chemistry.

In addition to the starting materials of the formula (In) mentioned in the preparation examples, the final products of the formula (I d) Ar' according to the invention may be mentioned separately at the same time: Table 3 Table 3 (Continued) R'Ar' Table 3 (continued) Table 3 (continued) R'Ar' Table 3 (continued) R'Ar' Table 3 (continued) Table 3 (continued) Table 3 (continued) R'Ar' Table 3 Table 3 (continued) RI A r 'formula CV
Some of the pyrazolin-5-one derivatives of I) are known,
and is in part the subject matter of a patent application filed by the applicant which does not belong to the prior art (see German Patent Application No. P36 2).
5 686).

New and known pyrazolin-5-one derivatives of the formula (Vl) are e.g.
independently of one another represents methyl or ethyl] are initially prepared in a first step, if appropriate in the presence of a diluent such as methanol or ethanol, of the formula (X) Ar' NHNH2(X) [wherein , Ar' is as defined above, at a temperature of 10 to 80°C, and if necessary, an intermediate of formula (U) [wherein HI, R1 and Ar' are defined as defined above] The product of , in the second step,
30 to 70, if appropriate in the presence of a diluent such as methanol and if appropriate in the presence of a base such as sodium hydroxide.
Obtained by decarboxylation at a temperature of °C.

Cyclization and subsequent decarboxylation can be done in one bot
The process may also be carried out in one reaction step [see, e.g. Liebigs Ann Kem.
, Chem, ), 373.142 (I910) and Preparation J0 Alkoxymethylene malonates of formula (II) are compounds generally known in organic chemistry.

Arylhydrazines of formula (X) are known or can be prepared by known methods [see, for example, Zupen (H
ouben) - Weyl, Methods of Organic Chemistry (M
ethoden der organischen C
hemie), Volume X2, page 203, Shemie Publishing (T
hieme Verlag Stuttgart), l
967 ], or the compound of formula <Vt> is 2) Formula (Xlll) RI-CO-CHx-COOR' (X m )
[wherein R1 and R'' are as defined above, the β-ketoester of 1 of formula arylhydrazine and 0-120℃
[See, e.g. J. Am. Chem.
where R9 is as defined above] is mixed with an arylhydrazine of formula (X) from 0 to 120, if appropriate in the presence of a diluent such as toluene.
and the formula (XV) Ar'-NH-NH-CH=CH-COOR"
(X V )1 in which Ar' and R1 are as defined above] in the presence of a strong base such as metrilam methylate and if appropriate in the presence of a diluent such as methanol, from 0 to 80 or 4) a compound of formula (X IV a ) 1 in which Rh-r is 01-C4 alkyl, especially methyl or ethyl, if appropriate in a diluent such as ethanol. an intermediate of formula (XVa) c in which Ar' and RI1 are as defined above; in the presence of a strong base such as sodium methylate and if appropriate a diluent such as ethanol.
It can be obtained by reacting at a temperature of 150°C.

The propiolate of formula (X N) and the compound of formula XIVa are compounds that are generally known in organic chemistry or can be prepared by known methods.

The following pyrazolin-5-one derivatives of formula (VI) may be mentioned separately in addition to the compounds mentioned in the Preparation Examples: Ar' Table 4 Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) According to the present invention Methods (I a / a ) and (I a /
In β), the amines which can further be used as starting materials are generally defined by formula (II). In this formula (I) R7 represents the radicals already mentioned for this substituent in connection with the description of the substances of formula (I a) according to the invention.

Amines of formula (I[) are compounds generally known in organic chemistry.

Ar of the formula (■a) which can be used as starting material for the preparation of substituted pyrazolin-5-one derivatives of the formula (I), in which R1 and Ar are associated with the description of the substance of the formula (I) and represents the groups already mentioned for the substituents of ] Some of the 4-formyl-pyrazolin-5-one derivatives of
ya), L, N,, Zh, Orgu Kim (
Org, Khim, ) 11(8), 1734 (I9
75)].

4-formyl-pyrazolin-5-one derivatives which can further be used as starting materials in the process (Ia/β) of the invention are generally defined by formula (IV). This formula (IV
), R' and Ar' are represented by the formula (I a
) represents the groups already mentioned for these substituents.

Compounds of formula (IV) are new and are part of the present invention.

The compound of formula (IV) is a 4-( of formula (I d) ■ ^rl [wherein R1 and Ar' are as defined above]
N,N-dimethylamino-methylidene)-pyrazoline-
The 5-one derivatives can be obtained by hydrolysis, if appropriate in the presence of a diluent and in the presence of a base.

The preparation of the starting material of formula (■) is preferably carried out using a diluent.

As such, virtually all inert organic solvents can be considered. These are preferably aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane,
hexane, heptane, cyclohexane, petroleum ether,
Benzine, ligroin, benzene, toluene, xylene, methylene monide, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene and 0-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane. , ketones such as acetone, methylethyl, methylisopropyl and methylisobutylketone, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and dimethylsulfoxide, tetramethylene Contains sulfone and hexamethylphosphoric triamide.

Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates and alkali metal alcoholates such as sodium and potassium carbonate, sodium methylate and potassium methylate; Sodium methylate or potassium methylate are suitable bases and are used in excess.

Hydroxylamines which can further be used as starting materials for the preparation of substituted pyrazolin-5-one derivatives of formula (I b) are generally defined by formula (V). This formula (V
), R6 preferably represents the groups already mentioned as suitable for this substituent in connection with the description of the substances of formula (Ib) according to the invention.

Hydroxylamine of formula (V) is a compound generally known in organic chemistry.

4-(N.

N-dimethylamino-methylidene)-pyrazoline-5-
On derivatives are generally defined by formula (I d).

The 1.3.5-) riazine of formula (■) which is additionally necessary for the preparation of substituted pyrazolin-5-one derivatives of formula (I c) according to process embodiment (I c /β) is generally known in organic chemistry. It is a compound of

Pyrazolin-5-ones which may further be used as starting materials for the preparation of substituted pyrazolin-5-one derivatives of formula (I c) according to process embodiment (I c /β) are generally of formula (V
I). In this formula (Vl) R1 and Ar' preferably represent the groups already mentioned as suitable for these substituents in connection with the description of the substances of formula (Ic) according to the invention.

Compounds of formula (VT) have already been mentioned above in the description of the starting materials for the preparation of novel compounds of formula (Id). formula(
The process for preparing the novel pyrazolin-5-one derivatives Ia), (Ib'), (Ic) and (Id) is preferably carried out using a diluent.

Virtually any inert organic solvent or aqueous system may be considered as a diluent. These are preferably alcohol N
, if methanol, ethanol, methoxyethanol, propane or tert-butanol, aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane,
hexane, heptane, cyclohexane, petroleum ether,
Benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene and. - dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and dioxane; Pionitrinoamides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and dimethylsulfoxide, tetramethylenesulfone and hexamethylphosphoric triamide, and aqueous or aqueous-organic diamides.
Phase mixtures include dichloromethane-water or toluene-water.

The reaction temperature can be varied over a relatively wide range in the process for preparing the novel pyrazolin-5-one derivatives of formulas (I a), (I b), ('rc) and (Id). Generally temperatures of 0 to 180°C, preferably 10 to 150°C are used.

The process for preparing the novel pyrazolin-5-one derivatives of formulas (Ia) to (Id) is generally carried out at atmospheric pressure.

However, under certain conditions, elevated or reduced pressures can also be used.

When carrying out the process for the preparation of the new pyrazolin-5-one derivatives of the formulas (I a), (I b) and (Ic), the respective required starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in a relatively large excess. The reaction mixture is stirred for several hours at the required temperature. This treatment and filtration are carried out by conventional methods.

The compounds of formulas (I a) to (I d) according to the invention or the compounds of formula (I) which can be used according to the invention can be converted into salt-lower compounds with acids or bases, if appropriate.

For the preparation of the acid addition salts of the compounds of formulas (I) to (Id), the following acids may suitably be considered: hydrohalic acids such as hydrochloric acid and hydrobromic acid, especially hydrochloric acid, and also phosphoric acid. , nitric acid, sulfuric acid, mono- and difunctional carboxylic acids and hydroxycarboxylic acids such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid and sulfonic acids such as p-toluenesulfonic acid and .5
- Naphthalenedisulfonic acid.

Acid addition salts of compounds of formulas (I) to (I d) can be prepared in a simple manner by conventional salt-forming methods, for example, compounds of formulas (I) to (I d
) in a suitable organic solvent, then adding an acid such as hydrochloric acid and separating in a known manner, for example by filtration.

This can be purified if appropriate by washing with an inert organic solvent.

For the preparation of the base addition salts of the compounds of formula (I b'), the following amines may suitably be considered: alkylamines such as methylamine and dimethylamine, cycloalkylamines such as cyclopentylamine and cyclohexylamine, Heterocyclic amines such as piperidine, pyrrolidine and pyrazole. Also alkali and alkaline earth metal hydroxides, such as sodium hydroxide and potassium hydroxide.

Salt preparation can be carried out as described for acid addition salts.

Formula (I
The process conditions for the preparation of the pyrazolin-5-one derivatives f) correspond to the reaction conditions already described in the description of the process (Ia/σ and β).

The amines required as starting materials in the process according to the invention (If/σ and β) are generally defined by the formula (Ila). In formula (IIa), R7-1 represents the formula (
In connection with the description under If), represents the groups already mentioned for this substituent. Amines of formula (Ira) are compounds known in organic chemistry.

Further required subject compounds of formula (II[a) are compounds of formula (III)
) has already been described in detail in the description of substances. In this formula (ma), R'-1 is the formula (If) according to the present invention
have the meanings already mentioned for these substituents in the description of the substances.

The 4-formyl-pyrazolin-5-one derivative of formula (IVb) required for the process (If/β) is the 4-formyl-pyrazolin-5-one derivative of formula (IV) described above.
include. R1-1 in formula (IVb) is represented by formula (If
) has the meaning already mentioned for this group in the description of substances.

R'--NH-Co-R" formula (I) or (I a),
The arylhydrazine of formula (X), the compounds of formula (xvr) and (xrX) necessary for the production of substituted pyrazolin-5-one derivatives of (I b), (I c) and (I d) are known or can be produced in a simple manner by known methods [see, for example, Chem Bell (Ch.
Em, Ber, ), 28.478 (I895)].

Formulas (X), (X■), (X■), (XU) and (VI
In a), Ar' and R11 are of the formula (I a), (I
In the description of the substances according to the invention b), (I c) or (I d), these substituents have the meanings already mentioned.

The first and second stages of the process are preferably carried out in the presence of a diluent.

Virtually all inert organic solvents can be considered as diluents. These are preferably alcohols such as methanol, ethanol, methoxyethanol, propatool or t-butanol, aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, Benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene and 0-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether,
Tetrahydrofuran and dioxane, ketones such as acetone, methylethyl, methylisopropyl and methylisobutylketone, esters such as methyl acetate and ethyl acetate, nitrites such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and dimethylsulfoxide. Contains phon and hexamethyl phosphoric acid triamide. The second step of the process is carried out in the presence of a strong base.

Preferably sodium methylate and sodium methylate are used.

The reaction temperature can be varied over a relatively wide range in both the first and second steps. Generally 0~180°
C, preferably temperatures between 10 and 150C are used.

When carrying out the first and second steps, the respective required starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in a relatively large excess.

Inert organic solvents can be considered as diluents for carrying out the acylation of the compounds of formula (X). Preferably aliphatic or aromatic optionally halogenated hydrocarbons, such as benzyl, benzene, toluene, xylene, pentane,
hexane, heptane, cyclohexane, petroleum ether,
Ligroin, methylene chloride, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene and 0-dichlorobenzene, ethers such as diethyl and diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone or butanone, methylisopropyl and methyl isobutylketone, esters such as methyl acetate, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide, N-
Methylpyrrolidone or hexamethylphosphoric triamide is used.

When the compound of formula (X Tx) is used in liquid form, it can be used as a diluent in a suitable excess.

All commonly used inorganic and organic bases can be considered as acid binders for acylation. Preferably, alkali metal hydroxides or alkali metal carbonates such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, and tertiary amines such as triethylamine, N,N-
Dimethylaniline, pyridine, 4-(N,N-dimethylamino)-pyridine, diazabicyclooctane (D
A B CO), diazabicyclononene (D B N)
Alternatively, diazabicycloundecene (DBU) is used.

In the case of acylation, the reaction temperature can be varied over a relatively wide range. Generally temperatures of 0 to 180°C, preferably 10 to 150°C are used.

If the acylation is carried out, generally 1 to 20 mol, preferably 1 to 15 mol of acylating agent of formula (XII) and generally 1 to 3 mol of acylating agent of formula (XII) per mole of 3-amino-pyrazolin-5-one of formula (X■) Preferably 1 to 2 moles of acid binder are used. The reaction, treatment and isolation of the compound of formula (Vla) can be carried out by conventional methods.

The active compounds according to the invention can be used as defoliants, desiccants, hardwood destroyers and, in particular, as weedicides. Weeds, in the broadest sense, mean any plants that grow where plants are not desired. The substances according to the invention act essentially as complete or selective herbicides depending on the amount used.

The compounds according to the invention can be used, for example, in connection with the following plants: Dicotyledonous weeds of the following genera: Mustard (S 1napis)
, L epidium %
Galium, St.
ellaria), Matricari
a) , Anthemis ,
Galinsoga (G a I insoga), Chenopodium (Chenopodium), Urti
ca), S. enecio, A.
maranthus), Portulaca sp.
laca), X anthium,
Convolvulus, Ipomoea, Polygonum
), S esbania , A mbrosia , Thistle ((: irs
ium), Carduus, S onchus, Solanum
), Rorippa, Rotala, L.
a), Lamium, Ver.

n1ca), A butilon, Emex, Datura genus (D a
tura), Viola (V +ola) % Gale.

psis), Papaver and Centaurea.

Dicotyledonous cultivated plants of the following genera: Gossypiu
m), soybean (Q Iycine), Swiss chard (B eta), Carrot (Daucus), Phaseolus (Phaseolus), Enthus genus (P
isum), Solanum, Linum (L.
inum), sweet potato genus (I pomoea),
Vicia (Vicia), Nicotiana (N. 1coti)
ana), Tomato genus (Lycopersicon)
, Arachis , Brassica (
Brassica), L act
uca), Cucumis and Cucurbita.

Monocotyledonous weeds of the following genera: E chinochlo
a), Setaria, P.
anicum), D 1g1taria
), Phleum, Poa, Festuca
, E 1eusine , Brachiaria , L.
olium), B romus
, Avena, Cyperus (
Cyperus), Sorghum
, A gropyron, Cynodon, Monocha
ria), F embristylis
), Sagittaria, E teocharis, S ci
rpus) N. passalum (P aspalum)
, r schaemum , S phanoclea , Dactytoctenium , A grost is , S phanoclea (
A 1 opeculus) and A pera
).

The following monocotyledonous cultivated plants: Oryza, Zea, Triticum
, Barley (Hordeum), Oat (A
vena), rye (S ecale), sorghum (S orghum), millet (panicum)
, Saccharum, Ananas, A spar
agus) and Allium.

However, the use of the active compounds according to the invention is in no way restricted to these genera, but extends in the same way to other plants.

Depending on the concentration, the compounds are suitable for complete control of weeds, for example in industrial areas and on railway lines, on roads and squares with or without trees. Equally, the compounds are useful for perennially cultivated plants, such as silviculture, ornamental trees, orchards, vineyards, citrus groves, walnut orchards, banana plantations, coffee plantations, tea plantations, rubber tree plantations, oil palm plantations. plantations, cocoa plantations, small fruit tree plantings, and hops can be used to control weeds in cultivated plants, and for the selective control of weeds in hand-grown plants.

The active compounds according to the invention can be used with particular success for selectively controlling monocot and dicot weeds in monocot and dicot crops by pre- and post-emergence methods.

The active compounds which can be used according to the invention exhibit inter alia a strong microbicidal activity and are effective against unwanted microorganisms (microorganisms).
rganism). Active compounds can be used, for example, as plant protection agents, especially fungicides.
It is suitable for use as a compound (gicide).

In plant protection, fungicides are Plasmodiophoromycetes
, Oomycetes, Chytridiomycetes, Zygomycetes, Ascon
ycetes), Basidiomycetes* (Basido+oyc
etetes), and Deuteromyce
tes) is used to control.

Examples include, but are not limited to, some initiators of fungi and bacterial diseases that fall into the general categories mentioned above: Pythium
ium) species, such as Pythium ultimum (Pythi
um ultimum; Phytophthora
phythora) species, such as Phytophthora infestans
s); Pseudoperonospora
onospora) species, e.g. Pseudoperonospora
cubensis (Pseud.

peronospora cubensis); plasmopara (Plasm.

para) species, such as Plasmopara biticola (Pla
smopara viticola) ; Tsuyu mold (P
eronospora) species, such as Peronospora pisi or P, brassicae;
rys 1phe) species, such as Erysiphe graminis; Sphaer.

theca) species, e.g.
phaerotheca fuliginea);
Podosphaera species, such as Podosphaera leucotoricha
a 1eucotricha); Venturia (Ve
nturia) species, such as Venturia 1naequalis; Pyrenophora species, such as Pyrenophora teres
) or P, graminea [conidia form: Drech
Syn: Helmintosporium; Uromyces species, such as Uromyces appendiculatus
ulatus); Pucc in ia
m, for example Puccinia recondita (Puccinium
ia recondita);
etia) species, such as Tilletia caries (Till
etiacaries); Smut fungus (Ustilago)
) species, such as Ustilago nuda.
uda) or Ustilag.

avenea); Pellicularia
aria) species, such as Pelicularia sasaki (Pel
liculariasasaki) ; Pyricularia species, rice blast fungus (Pyri
cularia oryzae); Fusarium (Fu
sarium) species, such as 7-sarium culmorum (
Fusarium culmorum; Botrytis species, such as Botrytis cinerea; Septoria species, such as Septorja nodorum; Leptosphaeria phaer ia) species, such as Leptosphae
ria nodorum); Cercospora (Cerco
spora) species, such as Cercospora canescens (C
ercospora canescens; Alternaria species, such as Alternaria brassicae (Alternariab?assi);
cae) and Pseudocercosporella (Pseudos
ercosporel la) species, such as Pseudosporella herpotrichoides
cosporella herpotrichoid
s) a. Due to the good tolerability of the active compounds by the plants at the concentrations required for controlling plant diseases, the treatment of the above-ground parts of the plants, the growing stems and seeds, and the soil is possible. .

When treating plant parts, the active compound concentration in the application forms can be varied within a substantial range. Generally the concentration is between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

When treating seeds, generally 0.00
1 to 50 g of active compound are required, preferably 0.01 to log.

When treating soil, generally 0°0000 is applied to the working area.
1-0.1% by weight, preferably o, oo.

Active compound concentrations of 1 to 0.02% by weight are required.

The active compounds which can be used according to the invention can be used with particular success against the tomato Phytophthora, both protectively and systemically.

Furthermore, the active compounds according to the invention can be used to control rice blast (Pyr).
It also shows bactericidal activity against ICU jar ia).

The active compounds which can be used in the invention, depending on their particular physical and/or chemical properties, can be found in common compositions, e.g.
Solutions, emulsions, suspensions, powders, foams, liniments, granules, aerosols, powders for seed treatment, natural and synthetic substances impregnated with active compounds, microscopic capsules in polymeric substances and coating compositions for seeds. products, compositions for use in combustion devices, such as fumigation cartridges, fumigation cans and fumigation coils, and ULV cold mist to warm mist compositions.

These compositions are prepared in known manner, for example, by mixing the active compounds with extenders, i.e. liquid solvents, liquefied gases under pressure and/or solid carriers, and optionally surfactants, i.e. emulsifiers and/or blowing agents. Ru. Furthermore, when water is used as an extender, for example, an organic solvent can also be used as an auxiliary solvent.

As liquid solvents, mainly aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane, or paraffins such as mineral oil fractions, alcohols such as butanol or glycols and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water are suitable; liquefied gases Extending agent or carrier means a liquid that is a gas at normal temperature and pressure, such as halogenated hydrocarbons and aerosol propellant bases such as butane, propane, nitrogen and carbon dioxide; as a solid carrier , crushed natural minerals such as kaolin,
clay, talc, chalk, quartz, attapulgite,
Suitable are montmorillonite or diatomaceous earth as well as ground synthetic minerals such as highly dispersed silicic acids, aluminas and silicates; as solid carriers for dusts,
from crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite and dolomite, as well as inorganic and organic limestone synthetic granules and granules of organic substances, such as sawdust, palm;
Corn cobs and tobacco stalks are suitable: as emulsifiers and/or blowing agents nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates. , alkyl sulfates, arylsulfonates and albumin hydrolysis products; suitable dispersants are, for example, lignin sulfite waste liquor and methylcellulose.

Adhesives such as carboxymethyl cellulose as well as powders,
Particulate or latex natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalin and lecithin, and synthetic phospholipids can be used in the composition.

Further additives can be mineral and vegetable oils.

Coloring agents such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue and organic dyes such as alizarin dyes and metal phthalocyanine dyes, and trace amounts of nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc are used. I can do it.

The preparations generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of active compound.

The active compounds according to the invention can also be used for controlling weeds, either as such or in the form of their preparations, in mixtures with known herbicides, finished formulations or seed mixtures being possible.

For mixtures, known herbicides such as N-(2-benzothiazolyl)-N,N'-dimethylurea, 3-(3-chloro-4-methylphenyl)-1°1-dimethylurea,
3-(4-inglobylphenyl)-1,1-dimethylurea, 3-(α, a.

σ-Tolufluoro-m-tolyl)-1,1-dimethylurea, 2-tert-butylamino-4-ethylamino-
6-methylthio-3-triazine, 2-chloro-N-(
[4-Methoxy-6-methyl-1,3,5-triazin-2-yl)-amino1-carbonyl)-benzenesulfonamide, 4-amino-6-(l,1-dimethylethyl)-3-methylthio -1,2,4-triazine-3(
4H)-one, 4-amino-6-(l,1-dimethylethyl)-3-ethylthio-1,2,4-triazine-3
(4H)-one, l-amino-6-ethylthio 3-(
2,2-dimethylpropyl)-1゜3.5-triazine-2,4-(IH,3H)-dione, 2-(4-[(
3-chloro-5-trifluoromethyl-2-pyridinyl)oxy]-phenoxy)-propionic acid, (trimethylsilyl)-methyl 2- (4-[(3,5-dichloro-2-pyridinyl)oxy]-phenoxy) -propionate, 2,4-dichlorophenoxyacetic acid, 2-(2,
4-dichlorophenoxy)-propionic acid, 2-(4-
Chlor-2-methyl-phenoxy)-propionic acid, 3
, 5-short-4-hydroxybenzonitrile, ((
4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]-acetic acid, 3-isopropyl-2,1
, 3-benzothiadiazin-4-one 2,2-dioxide, N-methyl-2-(l,3-benzothiazol-2-
yloxy)-acetanilide, a-chloro-2'.

6'-Diethyl-N-(2-propoxyethyl)-acetanilide, thioethylhexahydro-1H-azepine-1-carbamate, N,N-dimethyl-N'-(3,
4-dichlorophenoxy)-urea, 2-chloro-N-(
2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide, 2'-chloro-2-(4-chloro-o-tryloxy)-acetanilide, methyl 5-(2, 4-dichlorophenoxy)-2-
Nitropenzoate, methyl 2-[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)
-Amino]-carbonyl]-amine]-sulfonyl(((((4.6-Simethoxy2-pyrimidinyl)
-amino)-carbonyl)-amino-sul.

Honyl)-methyl)-benzoate, N~(3.

4-dichlorophenyl)-propanamide can be used.

Also, some mixtures exhibit surprisingly synergistic effects.

Also other known active compounds such as fungicides, insecticides (in
secticides) % acaricide (acar i
c ides), nematicides
Mixtures with , bird repellents, plant nutrients and soil amendments are possible.

The active compounds may be used as such or in the form of their formulations or further diluted formulations, such as preparation solutions, suspensions, emulsions, powders, coatings and granules. be able to. These are applied in the customary manner, for example by watering, spraying, atomizing or seat taring.

The active compounds according to the invention can be applied before or after germination of the plants. The compounds can also be mixed into the soil before sowing seeds.

The amount of active compound used can vary within a substantial range. This amount essentially depends on the nature of the desired effect. In general, the application rate is 0.000 active compound per hectare of soil surface. 9 to 15, preferably 0.05 to 1
It is between 0 kg/ha.

The use and preparation of active compounds according to the invention is illustrated in the following examples.

USE EXAMPLES In the following use examples, the following compounds are used as reference substances: 4-(cyanomethyloximino)-3-methyl-1-phenyl-pyrazolin-one (European Published Patent Application No. 0.1
66.171) [4-(2,4-dichlorobenzoyl)-1゜3-dimethylpyrazol-5-yl 1-
4-Methylphenylsulfonate (known from DE 2 513.750) Example A Pre-emergence test Solvent: Acetone 5 parts by weight Emulsifier: Alkylaryl polyglycol ether
To prepare a suitable preparation of 1 part by weight of active compound, 1 part by weight of active compound is mixed with the above amount of solvent and the above amount of emulsifier and the concentrate is diluted with water to the desired concentration.

The seeds of the test plants were sown in normal soil and after 24 hours were sprayed with the active compound preparation. The concentration of active compound in the preparation was not critical, only the amount of active compound applied per unit area.

After 3 weeks, the degree of damage to the plants was compared to the growth of the untreated control group and determined as % damage.

The numbers have the following meanings: 0% = ineffective (same as untreated control group) 100% - total kill In this test, for example, the compounds in Table A below showed significantly better herbicidal activity than the control substances. Ta.

Example B Post-germination test Solvent: Acetone 5 parts by weight Emulsifier: Alkylaryl polyglycol ether
To prepare a suitable preparation of 1 part by weight of active compound, 1 part by weight of active compound is mixed with the above amount of solvent and the above amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Test plants with a height of 5 to 15 cm were sprayed with the active compound preparation in such a way that the desired amount of active compound per unit area was applied. The concentration of the spray solution was chosen such that the desired amount of active compound was applied in 2.000 Q/ha of water. After 3 weeks, the degree of damage to the plants was compared with the growth of an untreated control group and evaluated as % damage. The numbers indicate the following meanings:
O% = no effect (same as untreated control group) 100% - total kill In this test, for example, the compounds of Table B below showed very good herbicidal activity, especially in rice and wheat.

Example C PhytophLhora Test (Tomato)/Systemic Solvent: Acetone 4.7 parts by weight Emulsifier: Alkylaryl polyglycol ether
To prepare a suitable preparation of 0.3 parts by weight of active compound, 1 part by weight of active compound was mixed with the above amount of solvent and the above amount of emulsifier and this concentrate was diluted with water to the desired concentration. .

To test the systemic activity, the preparation of the active substance was poured into standard soil in which young test plants were grown. 3 from treatment
After a day, the plants are
festans) was infected with an aqueous spore suspension.

The plants were placed in a greenhouse at 100% relative humidity and approximately 20°C. Evaluation was performed 3 days after infection.

In this test, for example, the substance according to the invention [(Ic)
-11, [(I c)-2], [(Ic)-51, [(
Ic)-6], [(Ic)-12], and [(Ic)
)-133 showed better activity than the control substance (A).

Table 0 Phytophthora test (tomato) / Systemic Table C (continued) Table 0 (continued) Phytophthora test (tomato) / Protective solvent: Acetone 4.7 parts by weight Emulsifier: Alkylaryl polyglycol ether
To prepare a suitable preparation of 0.3 part by weight of active compound, 1 part by weight of active compound is mixed with the above amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test the protective activity, young plants were sprayed with the active compound preparation until dripping wet. After the spray coating had dried, the plants were inoculated with an aqueous suspension of Phyto7sola infestans spores.

The plants were placed in a greenhouse at 100% relative atmospheric humidity and approximately 20°C.

Evaluation was performed 3 days after inoculation.

In this test, for example, the substance according to the invention [(Ic)
-11, [(I c)-21, [(IC)-6], [(
Ib)-111 and [(Ia)-111 are control substances (A
) showed better activity.

Table of contents Phytofusora test (tomato)/protection Active compound concentration 100 p.4 Table (continued) Manufacturing example Example 1: C.F.

[Aspect (I a/a)] 1-(4-trifluoromethyl-phenyl)-4-N,
5 g (0,0168 mol) of N-dimethylamino-methylidene-3-methyl-pyrazolin-5-one were dissolved in 50 rrl of methanol and the reaction was dissolved until completion (chromatographically monitored) after addition of 14 g of 30% methylamine solution. ) The mixture was stirred at room temperature. The solvent was then removed, the residue was stirred in petroleum ether and the product was filtered off with suction and dried.

3.8 g of 1-(4-trifluoromethylphenyl)-4-methylamino-methylidene-3-methylpyrazolin-5-one (79.1% of theory), melting point 129-130°C
) was obtained.

C.F.

1-(4-trifluoromethylphenyl)-3-methyl-pyrazolin-5-one 28.6g (0°12 mol)
in 150 mff of toluene and 10.9 g of N,N-dimethylformamide dimethyl acetal (0
, 129 mol), the mixture was stirred at room temperature until completion of the reaction (monitored by chromatography). The solvent was then removed, the residue was stirred with petroleum ether and the product was filtered off with suction and dried.

1-(4-1-lifluoromethylphenyl)-4-N, N-'; methylamino-methylidene-3-methyl-pyrazolin-5-one 29.4 with melting point 230-233°O
g (82.6% of theory) was obtained.

(Step 2) 22.2 g (0-17 mol) of ethyl acetoacetate and 4
-Trifluoromethylhydrazine 309 (0,170 mol) was stirred in toluene for 24 hours in the presence of a water separator after addition of a small amount of p-toluenesulfonic acid with a spatula. After cooling, the mixture was washed with water, dried and evaporated. The residue is stirred with petroleum ether, the product is filtered off with suction,
Dry.

1-(4-trifluoromethylphenyl)-3-methyl-pyrazolin-5-one 28, By
(69.5% of theory) was obtained.

Example 2 [Aspect (I a/β) 1 1-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-formyl-3-methyl-pyrazoline-5
-one 59 (0,0148 mol) in dioxane 50
2.4 g of 2.4-dichloroaniline in m12
After the addition of (0,0148 mol) the solution was heated to 80 °C for 30
Heated for minutes. The solvent was then removed, the residue was stirred with petroleum ether and the product was filtered off with suction and dried.

4-[(2,4-dichlorophenylamino)-methylidene]-1-(2°6-dichloro-4-trifluoromethylphenyl)-3-methyl-pyrazolin-5-one 5 with melting point 230-232°C .0 g (70% of theory) was obtained.

〇F.

1-(2,6-dichloro-4-trifluoromethylphenyl)-3-methyl-4-N,N-dimethylaminomethylidene-pyrazolin-5-one 7°32g (0,02
mol) was suspended in 70 r12 of water, and after addition of 1.129 (0.02 mol) sodium hydroxide, the suspension was stirred for 3 hours at 45-50°C. Then set this to 0
It was cooled to 0.degree. C., acidified with 10% hydrochloric acid, and the precipitated solid was filtered off with suction and dried.

1-(2,6-dichloro-4-
trifluoromethylphenyl)-4-formyl-3-methyl-pyrazolin-5-one 6°159 (theoretical amount 90
．． 4%).

1-(4-trifluoromethyl-2,6-dichlorophenyl)-3-methyl-pyrazolin-5-one 18.79
(0.06 mol) in 100 mQ of toluene,
7.59 (0,063 mol) of N,N-dimethylformamide dimethyl acetal was added at room temperature. The reaction mixture was then stirred at room temperature until the reaction was complete (monitored by chromatography). The solvent was removed, the residue was masticated with petroleum ether, filtered off with suction and dried.

1-(4-trifluoromethyl-2,6) with a melting point of 195°C
-dichlorophenyl)-3-methyl-4-N,N-dimethylamino-methylidene-pyrazolin-5-one21.
8 g (99% of theory) were obtained.

(Method 2) Ethyl acetoacetate 1169 (I mol) and 2°6-dichloro-4-trifluoromethyl-phenylhydrazine 2
45 g (1 mol) in toluene 112 were heated in the presence of a water separator until the reaction was complete (monitored by chromatography) after addition of a catalytic amount of p-1-luenesulfonic acid. The solution was then cooled in a water bath, the precipitated solid was filtered off with suction, stirred with petroleum ether, filtered off with suction and dried.

218.5 g (70.2% of theory) of 1-(4-trifluoromethyl-2,6-dichlorophenyl)-3-methylpyrazolin-5-one having a melting point of 174-175°C were obtained.

Analogously to Preparation Examples [(Ia)-11 and [(Ia)-2] and following the method described above, the following final product of formula (Ia) was prepared.

Ar' (, I Q
U (Jro)
To me
To ~ ω 1)
to .

h φ b
G O■ C%l
+1 ~ Mouth α to Sofuda
ni = niyaΩ must cQ rororo = = U e C,l(,l
α to −
So-ro Issun ~
Dimensions! r+
ω-koro - co
Zeng size!
1) N dimension
So-m--to ω to flash
of 0 (
o (to) low IJ (, 1 k = Q ○ ~ : - 1 Q -- k = eoe15 0' W cn w
■-e, I N
-Engineer hours
h! (To)
!啼 ro〇ceJN 美 to 田郎 澽 j
■ ro ■ ro flash
啼 ro (t) ro
-Co ~ C'J
Cym.

O] αko O
F-U. Month ! Mu.

Ω Lotto (To)
■ Q@I"-r
'−r+ ト (
I) Male Ro 00 4
F+UQOO FJ +n
O'l N%0
B ! Oo
00 Q Uu
uQo
.

○ Q (J Q
UU-Q-Q OQ Riri
6h 0p
Tadasu Tadashi
CL 17.
Mu.

engineering = engineering
==IJU
U ○ QO Sori ~
u3 ~00
etJ 彎
0 ω Rom+
eJ NN+1
~I o o Q
Q = E E E = = (J
CJ OC,) U
(,)NQQ -m c
Q ~E E
E E = (J
C) o
o Q=work bag; C33↓(J
IJC, 10Q
+p -roto
ωe4 N
FJN
〜匡Q ○ 0
0--
~ He'J
(, l U
IJQ meeting! -Rotoku -rih
Ri~ Ne'J
FJ C'v1Q
U IJU U
l〒Pig
, + V v
! ν Example 3 l-(4-1-realolmethyl-2,6-dichlorophenyl)4-N,N-dimethylamino-methylidene-pyrazolin-5-one 69 (0,0!7 mol) in 50 ml of ethanol After dissolving and adding 1.49 (0,017 mol) of 0-methylhydroxylamine hydrochloride, the mixture was stirred at room temperature for 2 hours. The solution was then concentrated on a rotary evaporator, the residue taken up in water and extracted with methylene chloride. - The combined organic phases were dried and the solvent was removed.

1-(4-1-Rialomethyl-2,6-dichlorophenyl)-4-methyloximino-methylidene-pyrazolin-5-oyl, melting point 154-160°C 3.59
(58.2% of theory).

Preparation of starting material 5-hydroxy-1-(2,6-dichloro-4-trifluoromethylphenyl)-pyrazole59 (0,0
179 mol) in 50 ml of toluene and N
, N-dimethylformamide dimethyl acetal 2.4
After addition of 9 (0.02 mol), the mixture was stirred at room temperature until the reaction was complete (monitored by chromatography). The precipitated solid was filtered off with suction and stirred with petroleum ether, and the product was filtered off with suction and dried.

As a result, 2°55 g of 1-(4-trifluoromethyl-2°6-dichlorophenyl)-4-N,N-dimethylamino-methylidene-pyrazolin-5-one (theoretical amount of 4
0.5%) was obtained.

'HNMR (CDCIs) [3,34 (s, 3H); 3. '42 (s, 3H);
7-64 (s, IH); 7.70 (s, 2H)
;7.85 (s, IH) 1059 (0,253 mol) of finely ground diethyl β-(2,6-dichloro-4-trifluoromethylphenyl)-hydrazine methylene-malonate was added to 1000 mol of water.
309 (0.75 mol) of sodium hydroxide in m12 was introduced portionwise with stirring at 80-85 DEG C. and the mixture was then stirred for a further 48 hours at 97-98 DEG C. The cooled reaction mixture was carefully acidified with concentrated hydrochloric acid to pH<2, and the precipitate thus obtained was filtered off with suction and dried on clay.

5-hydroxy-1-(2,6
-cyclo-4-triple-olmethylphenyl)-pyrazole 1009 (67% of theory) was obtained.

I Diethyl ethoxymethylenemalo*-t 115g (0,5
3 mol) of 2,6-dichloro-4-trifluoromethyl-phenylhydrazine in ethanol
22.59 (0.5 mol) solution at 70-75°C
The mixture was added dropwise over a period of 30 minutes with stirring, and after the addition was complete it was stirred for 5 hours at 70-75°C. For working up, the solvent was removed under vacuum, the residue was masticated with water, filtered off with suction and dried on clay.

Diethyl β-(2,6-dichloro-
4-Trifluoromethylphenyl)-hydrazinomethylene-malonate 2029 (97% of theoretical fl) was obtained.

I 3. 6.2 g (0,025 mol) of 4.5-dolchlor-trifluoromethylbenzene and 6.259 (0,125 mol) of hydrazine hydrate were dissolved in 12 mf of pyridine.
Heated under reflux for 48 hours at 115-120°C in f. For work-up, the solvent was distilled off, the residue was taken up in water and extracted three times with about 30 mQ of dichloromethane each time.

- The combined organic phases were dried over magnesium sulphate, evaporated under vacuum and the residue was then distilled.

5.19% of 2,6-dichloro-4-trifluoromethylphenylhydrazine (83% of theory), melting point 56-57°C
) was obtained.

C.F.

(Method 3) Methyl 1-(2,6-dichloro-4-trifluoromethyl-phenylhydrazine)-acrylate 2409
(0.73 mol) was dissolved in 730 mQ of methanol and, after addition of 151 g of 30% sodium methylate solution, the mixture was stirred at room temperature for 20 hours. The solution was then poured into 3Q of water, acidified with 80mQ of concentrated hydrochloric acid, and the solid was filtered off with suction, washed with water and dried.

210 g of 1-(2,6-dichloro-4-trifluoromethylphenyl)-pyrazolin-5-one, melting point 228°C
(96.9% of theory).

2.459 (I, 0 mol) of 2.6-dichloro-4-trifluoromethyl-phenylhydrazine and 2.459 (I, 2 mol) of methylpropiolate were dissolved in toluene 10
The solution was stirred at 95-100°C for 24 hours. The solvent was then removed under vacuum, the residue was stirred with petroleum ether and the precipitated solid was filtered off with suction.

245 g (74.5% of theory) of methyl 1-(2,6-dichloro-4-trifluoromethylphenylhydrazine)-acrylate having a melting point of 70 DEG C. are obtained.

Preparation Example [(Ib) The following final product of formula (Ib) was prepared in the same manner as in (Ib)-11 and according to the method described above: r 1 ○ l ! J
U U # C, +
(JC: C,
) C゛Ω Ω Co
C)
■Shi U
Q ○Soft
, +++,.

Φ a) co
+IP
Low = Q Q Q α Q
Mouth lCOω
m= -C Q Q Q
−−− Above 0−〇 = Q O U ○ C〇−Q Above Mountain ■ J 啼 ω ト Φ
Φ-u3
0(J.U.
(J (,) etc.
-9-- l Q Q
00 engineering = 0 α mouth
Q (J l mouth
+F Cn
%ll'l
”IF size Toma
o Oo
Low -: COU 5 v, +++
,+v,
+-4lcDcrIπ (J Q C,)
.

Dimensions -■ Soro Example 4 Aspect [(IC)-α] 1-(4-trifluoromethyl-2,6-dichlorophenyl)-3-methyl-4-N,N-dimethylamino-methylidene- Pyrazolin-5-one 10g (0,027
3 mol) was suspended in 40 mQ of toluene and 80 mQ of ammonia was added until the reaction was completed (monitored by chromatography).
Passed at °C.

The mixture was then cooled to 0°C and the solids were filtered off with suction.
Washed with petroleum ether\ether (2:1) and dried.

1-(4-trifluoromethyl-2,6-dichlorophenyl)-3-methyl-4-aminomethylidene-pyrazolin-5-one 6.29 (
67.2% of theory) was obtained.

Example 5 Embodiment [(Ic)-β] 27.5 g (0,105 mol) of 1-(4-trifluoromethyl-2,6-dichlorophenyl)-3-methyl-pyrazolin-5-one in 500 mQ of absolute ethanol ) of 5-triazine in 100 mQ of absolute ethanol.
It was added dropwise to a solution of 7 g (0.07 mol) over a period of 8 hours. The solution was then stirred at room temperature overnight and evaporated to dryness. The residual oil was purified by column chromatography on silica gel (eluent: chloroform and 2
0% methanol).

17.9 g of 1-(4-trifluoromethyl-2,6-dichlorophenyl)-3-methyl-4-aminomethylidene-pyrazolin-5-one, melting point 184-185°C (
50.4% of theory) was obtained.

In the same manner as in Preparation Example [(Ic)-1] and according to the method described above, the following final purified product of formula (Ic) was prepared: λ, 1 Ma Dimensions
[F]-t
-0'l m 170
(Fl t ψ
OCl He
- -i N engineering
1 engineering =
=Q mouth
IJUL
)mouth ψ t-(I:l O'l
−To
C^ (Heh, -I
CE + - Ω -s N ω
■ ψ ト J
O(”3aOω ■
To gi-he −− I ψ To
■ 0G
C71 -〇- -
Heh N
＋.

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o U
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■Stock, /v
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Ot-ON -〇■ ωto(YN w
w −△ desired C
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N NO TO ψ ■ 11 TO 11 1 Ω OO- TO -! pig
, 9 , 9
9 Hem C1 (Q l 1 1C^
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△ ψ t00 0'1 - ('I'l
('l'(j+'10
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to N b)-
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v +7O[F]
ψ Q
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C [F] ψ ψ
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The substituted pyrazolin-5-one derivatives of the formula (If) shown in Table 9 can be prepared, for example, in particular in Preparation Example [(Ta)-1
1 and [(I a)-2].

- Ki! (g) [F] pus [F] g
, LP+1I-LLL-I
I++- O, p ch c.

Oki to n111; shi ===' hill −−m− ■ −−to −− = 11I+m ++
"w Ll+-++1+-m- 71';1- 〒- ++ U CJ
U (J〒=! 0 0 −
Kokyu ---1110-QO (g)
- [F] Formula (rV) summarized by general formula (VIa), (IVa
), (tvb) or (rVc) as described in Example (IV
-1) and as in the method described above.

r ! .

---To - ^ ^ A A
.

-I -I
ν ＼〆
The intermediates of the formula (Vl) shown in Table ν Formula 11 or the formula (VIa) [wherein Ar2 represents a substituted phenyl] are prepared according to Production Examples (VI-1), (Vl-2) and (Vl-
3) and as in the previously described method. The compounds of formula (Vla) here served as intermediates for the preparation of the known compounds of formula (I).

■1-E-1-Eng■
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(J QQ 〒
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Q mouth
Q＾OP＠
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OQQ v
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Mouth ○ 0 wa ma
To O ('i
0 C-1=: O, Q ○ □ = ■ O〇- 1 -to 01tsu
Ta Shita Q
m hum
Ka ω1111 hill ″−−− Ka
('I'l ff1O-C Q Q OtJ ○
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Example ■-62 O2 Method 4 9.3 g (0-06 mol) of 4-nitrophenylhydrazine and ethyl-β,β-jethoxy acrylate 11
．． 4 g (0.06 mol) in 50 m (2 ml) of absolute ethanol
The mixture was heated under reflux for 30 minutes. After addition of 1.4 g (0.0 mol) of sodium in 40 rrl of absolute ethanol, the reaction mixture was heated under reflux for a further 20 minutes, then cooled and acidified with dilute acetic acid. The solids were then filtered off with suction, washed with water and dried (see U.S. Pat. No. 2,439,
No. 098).

3-nithoxy-1-(4-nitrophenyl)-pyrazolin-5-one with melting point 143 °C
3.6%).

Example 6 2.4 g of 1-(2,4,6-)lychlorphenyl)-4-formyl-3-methyl-pyrazolin-5-one (
0,0079 mol) was dissolved in 100 ml of dioxane and 0.79 (0,0079 mol) of morpholine was added. The mixture was heated to 100° C. for 1 hour, then the solvent was removed and the residue was stirred with petroleum ether. The product was filtered off with suction and dried.

1-(2,4,6-1lychlorophenyl)-3-methyl-4-mol 7 orinyl-methylidene-vilazolin-5-one 2°719 (theoretical amount of 9
1.8%).

Production Example 6 - Following formula (I) in the same manner as compound (I-1)
The compound was prepared: Table 12 Example Vl-136 CF.

1-(2,6-dichloro-4-trifluoromethylphenyl)-3-amino-pyrazolin-5-one 109
(0,032 mol) in 100 mQ of dioxane,
After addition of 4.5 g (0.032 mol) of benzoyl chloride, the mixture was then heated under reflux for 5 hours. The reaction mixture was then evaporated and stirred with water. The solid was filtered off with suction, washed several times with water and air-dried.

5.2 g (-39.9% of theory) of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-benzoylamino-pyrazolin-5-one having a melting point of 288 DEG C. were obtained.

Example! ■-1 C.F.

2.7 g (0,067 mol) of sodium was dissolved in 50 mfl of ethanol, and then ethyl β-(2°6-dichloro-4-trifluoromethylphenylhydrazino)-
β-imino-propionate 24y (0,068 mol) was added. The reaction mixture was heated under reflux for 1 hour and then evaporated under vacuum. After putting the residue in water,
The solution was extracted twice with ether and the aqueous phase was acidified with dilute hydrochloric acid.

The precipitated solid was filtered off with suction and dried.

1-(2,6-dichloro-4-
9.69 (45.9% of theory) of trifluoromethylphenyl-3-amino-pyrazolin-5-one were obtained.

Example
47.79 (0.3 mol) of β-ethoxypropionate were heated under reflux in 300 m<1 of toluene for 1 hour. After cooling, petroleum ether was added to the reaction mixture and the precipitated solid was filtered off with suction.

As a result, 60.39 (56.2% of the theoretical amount) of β-(2,6-dichloro-4-trifluoromethylphenylhydrazino)-β-iminopropionate was obtained.

Claims (1)

[Claims] 1. Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R^1 is hydrogen, alkyl, cycloalkyl, halogenoalkyl, even if each is optionally substituted. Good alkenyl or alkynyl, halogenoalkenyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkoxycarbonylalkyl, dialkoxy(
thio)phosphorylalkyl, each optionally substituted aryl, aralkyl, aryloxyalkyl or arylthioalkyl, or optionally substituted heterocycle or heterocycloalkyl, or the group -NH-C
Represents O-R^1^0 or -CO-O-R^1^1,
Here, R^1^0 and R^1^1 are each independently,
represents alkyl or aryl, R^2 is a group -NHR^3, -NR^4R^5 or -NH
OR^6, where R^3 represents hydrogen, alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, alkoxyalkyl, optionally substituted aralkyl, or optionally substituted aryl, and R^4 represents alkyl, R^5 represents alkyl, or R^4 and R^5 together with their bonded nitrogen atoms form a heterocyclic ring which may contain further heteroatoms. where R^6 represents hydrogen, alkyl, halogenoalkyl, alkenyl, halogenoalkenyl or optionally substituted aralkyl, and Ar is optionally substituted aryl, optionally substituted and/ or an optionally anellated heterocycle or group ▲a mathematical formula, a chemical formula, a table, etc.▼, where n represents the number 1 or 2] Derivatives and salts thereof (with the exception of compound 1-(4-chlorophenyl)-
3-Methyl-4-piperidino-methylene-pyrazoline-
5-one, 1-(4-chlorophenyl)-3-methyl-
4-morpholino-methylene-pyrazolin-5-one,
1-(4-chlorophenyl)-4-[4-(fluorophenylamino)-methylene]-3-methyl-pyrazolin-5-one and 1-(4-chlorophenyl)-3-methyl-4-amino A herbicide and fungicide containing at least one herbicide (excluding methylene-pyrazolin-5-one). 2. In formula (I), R^1 is hydrogen, a linear or branched alkyl having 1 to 8 carbon atoms, a cycloalkyl having 3 to 7 carbon atoms, 1 to 4 carbon atoms, and 1 same or different halogen atom. -9 halogenoalkyl, optionally substituted alkenyl or alkynyl each having 2 to 6 carbon atoms, with the proviso that substituents which may be mentioned are unsubstituted phenyl or mono-, di- or tri-substituted phenyl; The substituents may be the same or different, and the phenyl substituent is an aryl substituent listed under Ar; Halogenoalkenyl, alkoxy having 1 to 8 carbon atoms, alkoxyalkyl having 1 to 8 carbon atoms in each alkyl moiety, alkylthioalkyl, alkylsulfonylalkyl or alkylsulfinylalkyl, each alkoxy moiety having 1 carbon number
~4 and alkoxycarbonylalkyl having 1 to 4 carbon atoms in the alkyl moiety, a 5- or 6-membered heterocycle optionally substituted with fluorine, chlorine, methyl and/or ethyl; R^1 each further represents The aryl moiety may optionally be mono-, di-, tetra- or penta-substituted with the same or different substituents, and each aryl moiety has 6 carbon atoms.
~10 and if present, the number of carbon atoms in the alkyl moiety is 1~
4 represents aryl, arylalkyl, aryloxyalkyl or arylthioalkyl, with the proviso that suitable aryl substituents are the aryl substituents listed under Ar; represents R^1^0 or -CO-O-R^1^1, where R^1^0 and R^1^1 each independently represent C_
1-C_4 represents alkyl or phenyl, R^2 is a group -NHR^3, -NR^4R^5 or -NH
OR^6, where R^3 is hydrogen, a linear or branched alkyl having 1 to 8 carbon atoms, 1 to 6 carbon atoms, and 1 same or different halogen atom;
~12 halogenoalkyl, straight chain or branched alkenyl having 2 to 12 carbon atoms, straight chain or branched alkenyl having 2 to 6 carbon atoms and 1 to 10 same or different halogen atoms,
Each alkoxy or alkyl moiety has 1 to 8 carbon atoms.
Alkoxyalkyl, aralkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety and 6 to 10 carbon atoms in the aryl moiety, which may optionally be mono- or polysubstituted with the same or different substituents; represents an aryl which may be mono-, di-, tri-, tetra- or penta-substituted, optionally with the same or different substituents of numbers 6 to 10, where each suitable aryl substituent is a halogen, a straight substitute having 1 to 4 carbon atoms; Chain or branched alkyl, dialkylamino, C_1-C_4 alkoxy and halogeno C_1-C_4 alkyl, each of which has 1 to 4 carbon atoms in the alkyl moiety, R^4 represents alkyl having 1 to 6 carbon atoms, and R^5 represents alkyl having 1 to 6 carbon atoms, or R^4 and R^
5 together with their bonding nitrogen atoms, oxygen,
Represents a 5- or 6-membered heterocyclic ring that can contain sulfur and/or nitrogen as a further heteroatom, R^6 is hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, 1 carbon number ~6 and the same or different halogen atoms, halogenoalkyl having 1 to 12 carbon atoms, straight chain or branched chain alkenyl having 2 to 12 carbon atoms, having 2 to 6 carbon atoms and the same or different halogen atoms 1 to 10 Halogenoalkenyl represents an aralkyl having 1 to 4 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part, optionally optionally mono- or polysubstituted with the same or different substituents, where appropriate aryl substitution the radicals are halogen, C_1-C_4 alkyl, halogenoC_1-C_4 alkyl and nitro, and Ar represents aryl having 6 to 10 carbon atoms, optionally mono- or polysubstituted with the same or different substituents; However, suitable aryl substituents include halogen, nitro, cyano, carboxyl, alkoxycarbonyl having 1 to 4 carbon atoms, C_1 to C_4 alkyl, C_1 to C_4 alkoxy, C_1 to C_4 alkylthio, C_3 to C_6 alkynyloxy, each of which is the same or different halogen. Halogeno C_1-C_4 alkyl having 1 to 9 atoms, Halogeno C
_1-C_4 alkoxy or halogeno C_1-C_4 alkylthio, phenyl, C_1-C_4 alkylsulfonyl and same or different halogeno C_1-C_4 alkylsulfonyl having 1 to 9 halogen atoms, and di-C
_1-C_4 alkylamino, in which Ar represents an optionally substituted and/or optionally anilated 6-membered aromatic heterocycle containing at least one nitrogen atom, provided that suitable substituents is an aryl substituent listed under Ar above, or Ar represents a group ▲a mathematical formula, a chemical formula, a table, etc.▼, where n represents the number 1 or 2, substituted pyrazoline-5- The herbicide and fungicide according to claim 1, which contain at least one compound of the formula (I) described in claim 1) and its salt (excluding the compounds listed under formula (I) according to claim 1) agent. 3. A method for controlling weeds or fungi, which comprises causing a substituted pyrazolin-5-one derivative of formula (I) according to claim 1 or 2 to act on weeds or fungi or their environment. 4. Use of the substituted pyrazolin-5-one derivative of formula (I) according to claim 1 or 2 for the extermination of weeds or fungi. 5. Controlling weeds or fungi, characterized by mixing the substituted pyrazolin-5-one derivative of formula (I) according to claim 1 or 2 with an extender and/or a surfactant. A method for producing herbicides or fungicides. 6. Formula (Ia) ▲Mathematical formulas, chemical formulas, tables, etc.▼(Ia) [In the formula, R^1 is hydrogen, alkyl, cycloalkyl, halogenoalkyl, each optionally substituted alkenyl or alkynyl. , where suitable substituents are unsubstituted phenyl or mono-, di- or tri-substituted phenyl, the substituents may be the same or different, and suitable phenyl substituents are those listed under Ar. is an aryl substituent; R^1 further includes halogenoalkenyl, alkoxy, alkoxyalkyl, alkylthioalkyl,
Alkylsulfonylalkyl, alkylsulfinylalkyl, alkoxycarbonylalkyl or dialkoxy(thio)phosphorylalkyl, each representing optionally substituted aryl, aralkyl, aryloxyalkyl or arylthioalkyl, or optionally substituted hetero Ring or heterocyclic alkyl or group -NH-CO-R^1^0 or -CO-O-R^1
^1, where R^1^0 and R^1^1 each independently represent alkyl or aryl, and R^7 is alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, alkoxyalkyl, optionally substituted. represents optionally substituted aralkyl or optionally substituted aryl, and Ar^1 represents substituted aryl, optionally substituted and/or optionally anionated heterocycle or group ▲ , chemical formulas, tables, etc. ▼ , where n represents the number 1 or 2 ] Substituted pyrazolin-5-one derivatives and their salts (
However, the compound 1-(4-bromo-phenyl)-3-methyl-4-methylamino-methylidene-pyrazoline-5-
and 1-(4-chlorophenyl)-4-[(4-fluorophenylamino)-methylene]-3-methyl-pyrazolin-5-one). 7.Formula (I b) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I b) [In the formula, R^1 is hydrogen, alkyl, cycloalkyl, halogenoalkyl, each optionally substituted alkenyl or alkynyl. , halogenoalkenyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkoxycarbonylalkyl, dialkoxy(
thio)phosphorylalkyl, each optionally substituted aryl, aralkyl, aryloxyalkyl or arylthioalkyl, or optionally substituted heterocycle or heterocycloalkyl, or the group -NH-C
Represents O-R^1^0 or -CO-O-R^1^1,
Here, R^1^0 and R^1^1 each independently represent alkyl or aryl, and R^6 represents hydrogen, alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, or optionally substituted aralkyl. , and Ar^1 represents a substituted aryl, an optionally substituted and/or optionally anilated heterocycle or group ▲a mathematical formula, a chemical formula, a table, etc.▼, where n is a number 1 or 2] Substituted pyrazolin-5-one derivatives and salts thereof. 8. Formula (I c) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I c) [In the formula, R^1 is hydrogen, alkyl, cycloalkyl, halogenoalkyl, each optionally substituted alkenyl or alkynyl. , halogenoalkenyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkoxycarbonylalkyl, dialkoxy(
thio)phosphorylalkyl, each optionally substituted aryl, aralkyl, aryloxyalkyl or arylthioalkyl, or optionally substituted heterocycle or heterocycloalkyl, or the group -NH-CO
-R^1^0 or -CO-O-R^1^1, where R^1^0 and R^1^1 each independently represent alkyl or aryl, and Ar^1 is substituted aryl, optionally substituted and/or optionally anilated heterocycle or group ▲numerical formula, chemical formula, table, etc.▼, where n represents the number 1 or 2] Substituted pyrazolin-5-one derivatives and salts thereof (
However, the compounds 4-aminomethylene-1-(2-ethylphenyl)-3-methyl-pyrazolin-5-one and 4-aminomethylene-1-(4-chlorophenyl)-3-methyl-pyrazolin-5-one except). 9. Formula (I d) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ ( I d) [In the formula, R^1 is hydrogen, alkyl, cycloalkyl, halogenoalkyl, each optionally substituted alkenyl or alkynyl. , halogenoalkenyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkoxycarbonylalkyl, dialkoxy(
thio)phosphorylalkyl, each optionally substituted aryl, aralkyl, aryloxyalkyl or arylthioalkyl, or optionally substituted heterocycle or heterocycloalkyl, or the group -NH-CO
-R^1^0 or -CO-O-R^1^1, where R^1^0 and R^1^1 each independently represent alkyl or aryl, and Ar^1 is substituted aryl, optionally substituted and/or optionally anilated heterocycle or group ▲numerical formula, chemical formula, table, etc.▼, where n represents the number 1 or 2] Substituted pyrazolin-5-one derivatives and salts thereof (
However, the compound 1-(4-nitrophenyl)-3-methyl-4-N,N-dimethylamino-methylidene-pyrazolin-5-one, 1-(4-chlorophenyl)-3-(2
-nitrophenyl)-4-N,N-dimethylamino-methylidene-pyrazolin-5-one and 1-(3-trifluoromethylphenyl)-3-phenyl-4-N,N-
(excluding dimethylaminomethylidene-pyrazolin-5-one). 10. Formula (I f) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I f) [In the formula, R^1^-^1 is alkoxy, dialkoxy (
thio)phosphorylalkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted aralkyl, optionally substituted furanylalkyl or thienylalkyl, optionally substituted represents an optional heterocycle or group -NH-CO-R^1^0, where R^1^0
represents alkyl or phenyl, R^7^-^1 represents hydrogen, alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, alkoxyalkyl, optionally substituted aralkyl, or optionally substituted aryl, and R^7^-^2 represents hydrogen or methyl] and its salts (provided that the compound 1-phenyl-3-(4-methoxyphenyl)-4-
N,N-dimethylaminomethylidene-pyrrolidine-5-
(except on). 11. Compounds with formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼.