ZA200604397B

ZA200604397B - Plant growth regulation

Info

Publication number: ZA200604397B
Application number: ZA200604397A
Authority: ZA
Inventors: Henricus M M Bastiaans; Knittel Nathalie; Rees Richard; Donn Gunter; Martelletti Adrianna; Schwall Michael
Original assignee: Bayer Cropscience Gmbh
Priority date: 2004-05-12
Filing date: 2006-05-30
Publication date: 2007-11-28

Description

Plant growth regulation

Present invention relates to the technical field of agrochemicals and methods used in agriculture for plant growth regulation. In particular, the present invention relates to a new class of plant growth regulators for the treatment of plants in order to induce growth regulating responses which result in superior growth of treated plants, certain parts of the plants or, more generally, crop yield.

The term “method for plant growth regulation” or the term “growth regulation process” or the use of the words “plant growth regulation” or other terms using the word “regulate” as used in instant specification relate to a variety of plant responses which improve some characteristic of the plant. “Plant growth regulators” are compounds which possess activity in one or more growth regulation process(es) of a plant.

This type of plant growth regulation is distinguished from pesticidal action or growth reduction, sometimes also defined as a plant growth regulation, the intention of which, however, is to destroy or stunt the growth of a plant. For this reason, the compounds used in the practice of this invention are used in amounts which are non- phytotoxic with respect to the plant being treated but which stimulate the growth of the plant or certain parts thereof. Therefore, such compounds may also be called “plant stimulants”, their action may be called as “plant growth stimulation”.

Plant growth regulation is a desirable way to improve plants and their cropping so as to obtain improved plant growth and better conditions of agriculture practice compared to non-treated plants. This kind of molecules can either inhibit or promote cellular activities, often with a lower specificity compared to animal hormones. This means that plant growth regulators identified in plants most often regulate division, elongation and differentiation of plant cells in a way that, most often, they have multiple effects in plants.

. On the molecular basis, plant growth regulators may work by affecting membrane properties, controlling gene expression or affecting enzyme activity or being active in a combination of at least two of the before mentioned types of interaction.

Plant growth regulators are chemicals either of natural origin, also called plant hormones (like non-peptide hormones e.g. auxins, giberrellins, cytokinins, ethylene, brassinosteroids or abscisic acid, and salicilic acid), lipooligosaccharides (e.g. Nod factors), peptides (e.g. systemin), fatty acid derivatives (e.g. jasmonates), and oligosaccharins (for review see: Biochemistry & Molecular Biology of the Plant (2000); eds. Buchanan, Gruissem, Jones, pp. 558-562; and 850-929) , or they can be synthetically produced compounds (like derivatives of naturally occurring plant growth hormones, ethephon).

Plant growth regulators which work at very small concentrations can be found in many cells and tissues, but they seem to be concentrated in meristems and buds.

Beside the selection of the right compound it is also relevant to look for the optimal environmental conditions because there are several factors known that ray affect the action of growth hormones, like (a) the concentration of the plant growth regulator itself, (b) the quantity applied to the plant, (c) the time of application in relation to flowering date, (d) temperature and humidity prior to and after treatment, (e) plant moisture content, and several others.

Plant growth regulators can be either beneficial to the plant but sometimes can be used for weed control or to induce defoliation (like synthetic auxins 2,4-D and 2,4,5-T do).

The mode of action of existing plant growth regulators often is not known. Various targets are discussed and among those, most of the affected molecules are involved in cell division regulation, like arresting the cell cycle in stage G1 or G2, respectively, others for signaling drought stress responses (Biochemistry & Molecular Biology of the Plant (2000); eds. Buchanan, Gruissem, Jones, pp. 558-560). In any case, the hormone control can be identified as an extremely complex cascade of up and down regulations which, for example, can lead to a growth stimulation of one organ or cell typus of a plant but also can lead to a repression in other organs or cell typus of the same plant.

In many cases, kinases are involved either directly or indirectly in plant hormone control and among the kinases, protein kinases are central and highly specific control molecules in respect to cell cycle control. Such kinases are discussed as targets for several plant hormones, like it is the case for auxin and abscisic acid (Biochemistry & Molecular Biology of the Plant (2000); eds. Buchanan, Gruissem,

Jones, pp. 542-565 and pp. 980-985; Morgan (1997), Annu. Rev. Cell. Dev. Biol., 13, 261-291; Amon et al. (1993), Cell, 74, pp. 993-1007; Dynlacht et al. (1997), Nature, 389, pp. 149-152; Hunt and Nasmyth (1997), Curr. Opin. Cell. Biol., 9, pp. 765-767;

Thomas and Hall (1997), Curr. Opin. Cell. Biol., 9, pp. 782-787).

Patent publication WO 96/33614 already describes the use of a N-arylpyrazole or N- heteroarylpyrazole compound to regulate plant growth. Furthermore, Patent publication number US 4,810,283 describes the use of N-arylpyrazoles as herbicides.

Patent publication numbers WO 87/03781, EP 0295117, US 5556873, US 4771066 - and WO 02/066423 describe the control of insects, arachnids and helminths with 1- arylpyrazole compounds.

In view of the above, it now, surprisingly, turned out that certain 5-substituted-1- arylpyrazole-3-carboxylic acid derivatives, and especially certain 5-amino-1- arylpyrazole-3-carboxylic acid derivatives do not primarily act as herbicides but show a superior behaviour in respect to be used for plant growth regulation.

The present invention relates to the use of a compound for plant growth regulation, preferably by application of the compound to plants, to the seeds from which they grow or to the locus in which they grow, in an effective plant growth regulating, preferably non-phytotoxic amount, which compound is a 5-substituted-1- arylpyrazole-3-carboxylic acid derivative of formula (1) or an agriculturally acceptable salt thereof:

R2 R?

LX

RN”

Rf~="w “~

RS

0 wherein:

R'is CONRPR or COR;

Wis C-halogen or N;

R2 is H or S(O)mR®;

R?is NR'R", halogen, OH, (C;-Cs)-alkoxy, (C2-Cs)-alkenyloxy or (C2-Cg)-alkynyloxy;

R* is H or halogen, preferably H, Cl or Br;

Ris (C4-C4)-haloalkyl or (C1-Cs)-haloalkoxy, preferably CF3 or OCF3;

RS is H, (C1-Cs)-alkyl, (C1-Ce)-haloalkyl, (C1~Cg)-alkoxy-(C1-Cs)-alkyl, (C2-Cs)-alkenyl, (C2-Cg)-haloalkenyl, (C2>-Cg)-alkynyl, (C2-Cg)-haloalkynyl, (C3-C;)-cycloalkyl, (Cs-

Cr)-cycloalkyl-(C4-Cs)-alkyl, (C1-Ce)-alkoxy, (C1-Ce)-alkylthio, (CH2).R"?, (CH2),R™, (C+-Cs)-alkyl-CN, (C4-Ce)-alkyl-NR'"°R"" or (C4-C¢)-alkyl- S(O)R%; 16 Ris H, (C4-Cs)-alkyl, (Cs-Cs)-alkenyl or (C3-Cg)-alkynyl; or

R® and R” together with the attached N atom form a five- or six-membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-Cg)-alkyl and (C4-Cg)-haloalkyl;

R8is H, (C4-Cg)-alkyl, (C1-Cs)-haloalkyl, (C2-Ce)-alkenyl, (C2-Cs)-alkynyi or (CH2),R", preferably H or (C4-C4)-alkyl or C4-Cy)-haloalkyl, particularly methyl or ethyl;

R® is (C4-Cg)-alkyl or (C4-Cs)-haloalkyl;

R' and R" are each independently H, (C1-Cg)-alkyl, (C1-Cg)-haloalkyl, (C2-Cs)- alkenyl, (C2-Cs)-haloalkenyl, (C>-Cs)-alkynyl, (C3-Cg)-cycloalkyl, (Cs-Ce)-cycloalkyl-(C1-Cg)-alkyl, COR™ or COR; or

R'® and R"" together with the attached N atom form a five- or six-membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-Cg)-alkyl and (C1-Cs)- 5 haloalkyl;

R'2 is phenyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-Cs)-alkyl, (C1-Cs)-haloalkyl, (C4-Cs)-alkoxy, (C1-Cs)- haloalkoxy, CO,R'®, CN, NO2, S(O);R?, COR, CONR'™R"’, NR'®R'” and OH;

R'is heterocyclyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-C4)-alkyl, (C1-Cs4)-haloalkyl, (C4-C,)-alkoxy, (C+-

Ca)-haloalkoxy, NO2, CN, CO2R'®, S(0),R®, OH and oxo;

R* and R'® are each independently H, (C1-Cg)-alkyl, (C1-Ce)-haloalkyl, (C2-Cs)- alkenyl, (C2>-Cg)-haloalkenyl, (C2>-Cg)-alkynyl or (C4-Cs)-alkoxy-(C4-Ca)-alkyi;

R'® and R'" are each independently H, (C1+-Cg)-alky! or (C4-Cs)-haloalkyl; 16 m, q and r are each independently 0, 1 or 2; n and p are each independently 0, 1, 2, 3 or 4; and each heterocyclyl in the above-mentioned radicals is independently a heterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero atoms in the ring selected from the group consisting of N, O and S.

The invention also encompasses any stereoisomer, enantiomer, geometric isomer or tautomer, and mixtures of the compounds of formula (I) and the respective agricultirally acceptable salts thereof.

By the term " agriculturally acceptable salts” is meant salts the anions or cations of which are known and accepted in the art for the formation of salts for agricultural use.

Suitable salts with bases, e.g. formed by compounds of formula (I) containing a carboxylic acid group, include alkali metal (e.g. sodium and potassium), alkaline earth metal (e.g. calcium and magnesium) and ammonium salts. The ammonium salts include ammonium (NH,") and ammonium salts of organic amines, (e.g. the diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine salts), and quaternary ammonium salts (NR,") for example tetramethylammonium. ammonium salts. Suitable acid addition salts, e.g. formed by compounds of formula (1) containing an amino group, include salts with inorganic acids, for example hydrochlorides, sulphates, phosphates and nitrates and salts with organic acids for example acetic acid.

In the present patent specification, including the accompanying claims, the aforementioned substituents have the following meanings:

Halogen means fluorine, chlorine, bromine or iodine.

The term "halo" before the name of a radical means that this radical is partially or completely halogenated, that is to say, substituted by F, Cl, Br, or |, in any combination.

The expression “(C4-Cg)-alkyl” means an unbranched or branched non-cyclic saturated hydrocarbon radical having 1, 2, 3, 4, 5 or 6 carbon atoms (indicated by a range of C-atoms in the parenthesis), such as, for example a methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical. The same applies to alkyl groups in composite radicals such as “alkoxy-alkyl".

Alkyl radicals and also in composite groups, unless otherwise defined, preferably have 1 to 4 carbon atoms. "(C4-Cs)-Haloalkyi" means an alkyl group mentioned under the expression "(C4-Cs)- alkyl” in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, such as monohaloalkyl, perhaloalkyl, CF3,

CHF,, CH,F, CHFCHjz, CF3CH,, CF3CF2, CHF,CF,, CH2FCHCI, CH2Cl, CCl, CHCl» or CH2CHCI. “(C4-Cs)-Alkoxy-(C4-Cg)-alkyl” means (C4-Cg)-alkyl which is substituted by (C1-Cs)- alkoxy. "(C4-Cs)-Alkoxy" means an alkoxy group whose carbon chain has the meaning given under the expression "(C4-Cg)-alkyl". “Haloalkoxy” is, for example, OCF3, OCHF,

OCH,F, CF3CF,0, OCH;CF3 or OCH,CHCI. "(C.-Ce)-Alkenyl" means an unbranched or branched non-cyclic carbon chain having a number of carbon atoms which corresponds to this stated range and which contains at least one double bond which can be located in any position of the respective unsaturated radical. "(C,-Cs)-Alkenyl” accordingly denotes, for example, the vinyl, allyl, 2-methyl-2-propenyl, 2-butenyl, pentenyl, 2-methyipentenyl! or the hexenyl group. "(Cz-Ce)-Alkynyl" means an unbranched or branched non-cyclic carbon chain having a number of carbon atoms which corresponds to this stated range and which contains one triple bond which can be located in any position of the respective unsaturated radical. "(C2-Cg)-Alkynyl" accordingly denotes, for example, the propargyl, 1-methyl-2-propynyl, 2-butynyl or 3-butynyl group. "(C3-Cs)-Cycloalkyl" denotes monocyclic alkyl radicals, such as the cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl radical. ) "(C3-C7)-Cycloalkyl-(C4-Cg)-alkyl " means a (C4-Cg)-alkyl group which is substituted by a (Cs-C;)-cycloalkyl group, for example cyclopropylmethyl. "(C4-Cs)-Alkyl-CN” means a (C4-Cg)-alkyl group which is substituted by a CN group, for example cyanoethyl. "(C4-Ce)-Alkyl-S(O)R® means a (C4-Cs)-alkyl group which is substituted by a

S(O)R® group, for example methyithiomethyl.

A “heterocyclyl” group can be saturated, unsaturated or heteroaromatic; it preferably contains one or more, in particular 1, 2 or 3, hetero atoms in the heterocyclic ring, preferably selected from the group consisting of N, O and S; it is preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 to 7 ring atoms. The heterocyclic radical can be, for example, a heteroaromatic radical or ring (heteroaryl) such as, for example, a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more hetero atoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, furyl, pyrrolyl, pyrazolyl, imidazolyl and triazolyl, or it is a partially or fully hydrogenated radical such as oxiranyl, oxetanyi, oxolanyl (= tetrahydrofuryl), oxanyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyi, oxazolinyl, isoxazolinyl, oxazolidinyl, isoxazolidinyl and morpholinyl.

The expression “one or more radicals selected from the group consisting of” in the definition is to be understood as meaning in each case one or more identical or different radicals selected from the stated group of radicals, unless specific limitations are defined expressly.

Compounds of the stated formula (1) according to the invention or their salts in which individual radicals have one of the preferred meanings which have already been stated or are stated hereinbelow and particularly those shown in the Table examples, or in particular those in which two or more of the preferred meanings which have already been stated or which are stated hereinbelow are combined, are of particular interest, mainly because of the more potent herbicidal action, better selectivity and/or greater ease of preparation.

Of particular interest are compounds of formula (1) where a radical selected from the group of radicals R', R?, R?, R*, R® and W is preferably defined as set forth below, wherein the definition of the radical is independent from the definitions of the other radicals of said group. Preferred compounds of formula (I) contain a combination of radicals of said group which comprise two or more preferred meanings set forth below.

In the following preferred definitions it is generally to be understood that where symbols are not specifically defined they are to be as previously defined in the description.

Preferably R'is CONR®R’.

Preferably W is C-Cl or C-Br (more preferably W is C-Cl).

Preferably R? is S(O)nR®, wherein R? is (C4-Cs)-alkyl or (C4-Cs)-haloalkyl (more preferably R® is CF3).

Preferably R? is NR'R"", halogen, OH or (C4-Cs)-alkoxy.

Preferably R* is Cl or Br (more preferably R*is Cl).

Preferably R® is CF3 or OCFa.

Preferably R? is H, (C1-C4)-alkyl, (C4-C4)-haloalkyl, (C4-C3)-alkoxy-(C1-Cs)-alkyl-, (Ca-

C.)-alkenyl, (C3-C4)-haloalkenyl, (C3-Cs)-alkynyl, (C3-Cs)-haloalkynyl, (Cs-

Ce)-cycloalkyl, (C3-Cs)-cycloalkyl-(C1-C3)-alkyl, (C1-Ca)-alkoxy, (C4-Cs)-alkyithio,

(CH2)aR"?, (CH2),R™3, (C4-Ce)-alkyl-CN, (C4-Ce)-alkyl-NR'R"" or (C-Cs)-alkyl-

S(O)R®.

Preferably R” is H, (C4-C4)-alky!, (C3-Cy)-alkenyl or (C3-Cs)-alkynyl; or preferably R® and R” together with the attached N atom form a five- or six-membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-Cz)-alkyl and (C4-C3)- haloalkyl.

Preferably R'® and R'! are each independently H, (C1-Cs)-alkyl, (C1-C3)-haloalkyl, (C3-Cs)-alkenyl, (Cs-C4)-haloalkenyl, (C3-C4)-alkynyl, (C3-Cs)-cycloalkyi, (Ca-Cs)-cycloalkyl-(C4-Ca)-alkyl, COR or COR"; or preferably R'® and R* together with the attached N atom form a five- or six- membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-C3)-alkyl and (C4-Cs)-haloalkyl.

Preferably R'? is phenyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-C3)-alkyl, (C+-C3)-haloalkyl, (Cs-

Cs)-alkoxy, (C+-Cs)-haloalkoxy, CO-R'¢, CN, NO2, S(O)R®, COR'®, CONR™R"’,

NR'R'" and OH.

Preferably R" is heterocyclyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-C3)-alkyl, (C+4-Cs)-haloalkyl, (C4-

Cs)-alkoxy, (C1-Ca)-haloalkoxy, NO», CN, CO2R6, S(O),R®, OH and oxo.

Preferably R™ and R'° are each independently H, (C1-C3)-alkyl, (C4-Ca)-haloalkyl, (CzCs)-alkenyl, (C2-Cs)-haloalkenyl or (C2-C3)-alkynyl, particularly (C4-Cs)-alkyl.

Preferably R'® and R" are each independently H, (C4-Cs)-alkyl or (C4-Cs)-haloalkyl.

Preferably each heterocyclyl in the above-mentioned radicals is independently a heterocyclic radical having 3 to 6 ring atoms and 1, 2 or 3 hetero atoms in the ring selected from the group consisting of N, O and S.

A preferred class of compounds of formula (1) for the use as plant growth regulators in the invention are those in which:

R'is CONR®R’;

W is C-Cl or C-Br (more preferably W is C-Cl);

RZ is S(O)mR%;

R® is NR'°R", halogen, OH, (C4-C3)-alkoxy, (C.-Cs)-alkenyloxy or (C2-Cg)-alkynyloxy, :

R* is Cl or Br (more preferably R* is Cl);

R® is CF; or OCF;

R® is H, (C1~C4)-alky!, (C1-Cs)-haloalkyl, (C1-C3)-alkoxy-(C1-C3)-alkyl, (C3-C4)-alkenyl, (C3-C.)-haloalkenyl, (C3-Ca)-alkynyl, (C3-Cs)-haloalkynyl, (C3-Ce)-cycloalkyi, (Ca-

Cs)-cycloalkyl-(C1-Ca)-alkyl, (C1-C3)-alkoxy, (C+-Cs)-alkylthio, (CH2).R" or (CH2)R™;

R’ is H, (C1~C4)-alkyl, (C3-C4)-alkenyl or (C3-C4)-alkynyl; or preferably R® and R together with the attached N atom form a five- or six-membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-C3)-alkyl and (C4-C3)- haloalkyl;

R® is (C4-Ca)-alky! or (C4-Cj3)-haloalkyl (more preferably R® is CFa);

R™ and R'' are each independently H, (C1-C3)-alkyl, (C1-Ca)-haloalkyl, (C3-Cs)- alkenyl, (C3-C4)-haloalkenyl, (C3-C4)-alkynyl, (Cs-Ce)-cycloalkyl, (Cs-Cs)-cycloalkyl-(Cs-Ca)-alkyl, COR™ or COR"; or

R'® and R together with.the attached N atom form a five- or six-membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-C3)-alkyl and (C4-Cs)- haloalkyl;

R' is phenyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-C3)-alkyl, (C4-C3)-haloalkyl, (C4-Cs)-alkoxy, (C4-C3)- haloalkoxy, CO2R®, CN, NO2, S(O)R®, COR", CONR"R", NR'"R"" and OH;

R'is heterocyclyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-Cs)-alkyl, (C+-C3)-haloalkyl, (C4-Cs)-alkoxy, (C+-

Cas)-haloalkoxy, NO2, CN, CO2R'®, S(0),R°, OH and oxo;

R™ and RS are each independently H, (C1-Cs)-alkyl, (C1-Cs)-haloalkyl, (C>-Cs)- alkenyl, (C>-C3)-haloalkenyl, (C>-C3)-alkynyl or (C1-Ce)-alkoxy-(C4-Cs)-alkyl;

R'® and R'" are each independently H, (C4-Cs)-alkyt or (C4-C3)-haloalkyl; and each heterocyclyl in the above-mentioned radicals is independently a heterocyclic radical having 3 to 6 ring atoms and 1, 2 or 3 hetero atoms in the ring selected from the group consisting of N, O and S.

A further preferred class of compounds of formula (1) for the use as plant growth regulators in the invention are those in which:

R'is CONR®R’;

Wis C-CI;

R? is H, or S(O)mR®;

R32 is NR'R", halogen, OH or (C+-Cs)-alkoxy;

R*is Cl;

Ris CF;

RO is H, (C1-C4)-alkyl, (C1-Ca)-alkoxy-(C4-C2)-alkyl, (C3-C4)-alkenyl, (C3-C4)-alkynyi, (C3-Ce)-cycloalkyl, (Cs-Cg)-cycloalkyl-(C4-Cz)-alkyl, (C4-Cs)-alkoxy, (C1-Ca)-alkyithio, (CH2)R™ or (CH2),R™;

R” is H, (C1-C3)-alkyl, (C3-C4)-alkenyl or (C3-Ca)-alkynyl;

Ris methyl, ethyl or CF3;

R™ and R"! are each independently H, (Cs-Cs)-alkyl, (C1-Ca)-haloalkyl, (Cs-Ca)- alkenyl, (C3-C4)-haloalkenyl, (C3-C4)-alkynyl, (Ca-Cs)-cycloalkyl, (Cs-Cs)-cycloalkyl-(C4-C3)-alkyl, COR™ or CO.R'; or

R'2 is phenyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-alkoxy, CO2R,

CN and NO;

R'3 is heterocyclyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-Cs3)-alkyl, (C1-C3)-haloalkyl, (C4-Cs)-alkoxy, (C:-

Ca)-haloalkoxy, NO», CN, CO2R®, S(O)qR®, OH and oxo;

Rand R" are each independently (C4-Cs)-alkyl;

Rand R'" are each independently H or (C4-Cs)-alkyl; and each heterocyclyl in the above-mentioned radicals is independently a heterocyclic radical having 3 to 6 ring atoms and 1, 2 or 3 hetero atoms in the ring selected from the group consisting of N, O and S.

A further preferred class of compounds for the use as plant growth regulators in the invention are of formula (la), as depicted hereinafter, in which:

R'is CONR®R’;

W is C-Cl;

R?is H, or S(O)mR;

R®is NHR";

R*is CI;

R% is CF3;

RE is H, (C1-Cs)-alkyl, (C1-C2)-alkoxy-(C1-Ca)-alkyl, (C3-Cs)-alkenyl, (C3-Cs)-alkynyl, (C3-Cs)-cycloalkyl, (Ca-Cs)-cycloalkyl-(C4-C2)-alkyl, furfuryl or tetrahydrofurfuryl;

RT" is Hor (C4-C3)-alkyl;

R® is methyl, ethyl or CF3; and

R'is H, methyl or ethyl.

A further preferred class of compounds for the use as plant growth regulators in the invention are of formula (Ib), as depicted hereinafter, in which:

R'is COR

Wis C-CI;

R2is H, or S(O)mR®;

R%is NR'R";

RYisCl :

R® is CFs;

R8 is H, methyl or ethyl;

R? is methyl, ethyl or CFs;

R'is H, methyl or ethyl; and

R"YisH.

A further preferred class of compounds for the use as plant growth regulators in the invention are of formula (Ic), as depicted hereinafter, in which:

R'is CONR®R’;

Wis C-Cl;

R?is S(O)mCF3;

R? is NR™R", halogen, OH or (C4-C2)-alkyl;

R*is CI;

R® is CFs;

R® is H or (C4-Ca)-alkylthio;

RisH;

R' is (C4-Ca)-alkyl, COR or COR";

R', Rand R'® are each independently (C1-Cs)-alkyi.

Some of the compounds of formula (1) are not known in the prior art. Therefore, a further feature of the invention relates to these novel compounds of formula (1).

Thus, according to a further feature of the invention there is provided a 5-substituted- 1-arylpyrazole-3-carboxylic acid derivative of formula (1), or a salt thereof as defined in formula (1),

R2 R?

IX

RN”

R4 ZW “~

Re () wherein: i) R'is CORY

RZ? is H or S(O)mR%;

R3 R% R®, W and m are as defined above;

R®is H; and

R® is (C2~Cq)-alkyl or (C4-Cs)-haloalkyl;

or i) R'is CONR’R";

R® is (C4-Cg)-alkyl, (C4-Cs)-haloalkyl, (C1-Cs)-alkoxy-(C1-Ce)-alkyl, (C2-

Cs)-alkenyl, (C2-Cg)-haloalkenyl, (C-Ce)-alkynyl, (C2-Ce)-haloalkynyl, (Cs-

C7)-cycloalkyl, (C3-C7)-cycloalkyl-(C4-Cs)-alkyl, (C4-Ce)-alkoxy, (C1

Ce)-alkylthio, (CH2)RR™2, (CH2),R", (C1-Cé)-alkyl-CN, (C1-Ce)-alkyl-NR'R"" or (C4-Ce)-alkyl- S(O)R; or

R® and R” together with the attached N atom form a five- or six-membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C+-

Ce)-alkyl and (C4-Cg)-haloalkyl; and

RZ, R%, RY R%, RR’, R%, R'%, R", R'2, R™}, W, n, p and r are as defined in formula (1); with the exclusion of the compound wherein:

R' is CON(CHs)z; R? is CF3S; R® is OH; R* is Cl; R® is CF3; and W is C-Cl.

The above compound is specifically excluded because it is known, however, its use as a plant growth regulator has not yet been reported.

Compounds of formula (I) above may be prepared by the application or adaptation of known methods (i.e. methods heretofore used or described in the literature).

In the following description where symbols appearing in formulae are not specifically defined, it is to be understood that they are “as hereinbefore defined” in accordance with the first definition of each symbol in the specification.

It is to be understood that in the descriptions of the following processes the sequences may be performed in different orders, and that suitable protecting groups may be required to achieve the compounds sought.

According to a feature of the invention compounds of formula (1) wherein R'is COzH,

RZ is H or S(O)mR®, R? is (C2-Cs)-alkyl or (C4-Cs)-haloalkyl, and the other values are as defined above, may be prepared by the reaction of a corresponding compound of formula (11):

R2 CN

Jp

RN” (1m

Réi~~="w ks

Ls wherein R2, R?, R*, R% and W are as defined above, using aqueous sulfuric acid, generally 40% to 60% sulfuric acid at a temperature of from 80°C to 170°C, preferably from 120°C to 150°C.

According to a further feature of the invention compounds of formula (I) wherein R'is

CO.H, R%is H, R% is NHR", and the other values are as defined above, may be prepared by the reaction of a corresponding compound of formula (Il) above wherein

R?is R®SO or R°SO; (preferably CFsSO or CF3S05), using aqueous sulfuric acid, generally 40% to 60% sulfuric acid at a temperature of from 80°C to 170°C, preferably from 120°C to 150°C.

CONRPR’; R® is (C1-Cg)-alkyl, (C1-Cs)-haloalkyl, (C1-Cs)-alkoxy-(C4-Ce)-alkyl, (C2

Ce)-alkenyl, (C2-Cs)-haloalkenyl, (C2-Cg)-alkynyl, (C2-Ce)-haloalkynyl, (Cs-

Cy)-cycloalkyl, (Cs-Cr)-cycloalkyl-(C4-Cg)-alkyl, (C1-Ce)-alkoxy, (CH2)R™, (CH2)R™, (C4-Ce)-alkyl-CN, (C1-Cs)-alkyl-NR'°R'" or (C4-Ce)-alkyl- S(O)R®; R’ is as defined above; or

R® and R’ together with the attached N atom form a five- or six-membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C-Cg)-alkyl and (C+-Cs)-haloalkyl; and the other values are as defined above, may be prepared by the reaction of a corresponding compound of formula (1) wherein R'is COzH, with N,N’- carbonyldiimidazole to give the corresponding imidazolide of formula (ll): 0

R2 NY

N =

Rd N

R4 ~~ (ny) ~

RS followed by the reaction, preferably in situ, with an amine of formula (IV):

HNRCR’ (Vv) wherein R® and R7 are as defined above. The reaction is generally performed in a solvent such as tetrahydrofuran or dioxan, at a temperature of from 20°C to 100°C, preferably from 30°C to 70°C. :

According to a further feature of the invention compounds of formula (I) wherein R3is

NR'°R"! in which at least one of R'® and R"! is not H, and the other values are as defined above, may be prepared by the alkylation or acylation of the corresponding compound of formula (I) wherein R3 is NH., using an alkylating or acylating agent of formula (V) or (VI):

RYO.L Vv) RL! v1) wherein R'® and R' are as defined above with the exclusion of H, and L and L* are each a leaving group.

Alkylations, where R'® and/or R'! are each (C+-Csg)-alkyl, (C1-Cs)-haloalkyl, (C3-Ce)- alkenyl, (Cs-Cs)-haloalkenyl, (Cz-Ce)-alkynyl, (Cs-Cs)-cycloatkyl or (C3-Ce)-cycloalkyl-(C4-Cg)-alkyl, and L and L' are each preferably halogen, alkylsulfonyloxy or arylsulfonyloxy (more preferably chlorine, bromine, iodine, methylsulfonyloxy or p-toluenesulfonyloxy), are generally carried out in the presence of a base, in an inert solvent such as tetrahydrofuran, dioxan, acetonitrile, toluene, diethyl ether, dichloromethane, dimethylsulfoxide or N,N-dimethylformamide, at a temperature of from -30°C to 200°C, preferably at 20°C to 100°C. The base is generally an alkali metal hydroxide such as potassium hydroxide, an alkali metal hydride such as sodium hydride, an alkali metal carbonate such as potassium carbonate or sodium carbonate, an alkali metal alkoxide such as sodium methoxide, an alkaline earth metal carbonate such as calcium carbonate, or an organic base such as a tertiary amine, for example triethylamine or ethyldiisopropylamine, or pyridine, or 1,8-diazabicyclo[5.4.0Jundec-7-en (DBU). Acylations, where R' and/or R'! are each COR™ or CO;R", and L and L" are each preferably chlorine or bromine (more preferably chlorine), are performed optionally in the presence of a base. The bases, solvents and temperatures which may be used are similar to those employed for the alkylations.

By performing sequential alkylation or acylation reactions, compounds of formula 0] wherein R® is NR'R"! in which R' and R'! have different values may be prepared.

CONRER’, RZ is S(O)mR®, R? is (C1-Cg)-alkoxy, R® is (C1-Cg)-alkyithio, and the other values are as defined above, may be prepared by the reaction of a corresponding compound of formula (I) wherein R' is CONHR’, with a compound of formula (Vil):

R®-L 2 (vi) wherein R® is (C-Cs)-alkylthio, and L2 is a leaving group, generally halogen and preferably CI.

According to a further feature of the present invention compounds wherein mis 1 or 2, and the other values are as defined above, may be prepared by oxidising a corresponding compound in which mis 0 or 1. The oxidation is generally performed using an oxidising agent such as m-chloroperbenzoic acid or sodium periodate in an inert solvent for example methylene chloride at a temperature from -40°C to the reflux temperature of the solvent.

Compounds of formula (1) wherein R' is CONH, may be prepared from the corresponding compounds in which R' is CN according to known methods, for example by the reaction with concentrated sulfuric acid at a temperature of from 50°C to 150°C.

Intermediate compounds of formula (I) wherein R® is NR'°R"! or halogen may be prepared according to methods described in Patent Publication numbers WO 87/03781, EP 295117 and US 5232940.

Intermediate compounds of formula (Il) wherein R® is (C4-Cg)-alkoxy may be prepared according to methods described in Patent Publication numbers EP 035809 156 and US 5047550.

Intermediate compounds of formula (Il) wherein R® is OH may be prepared according to methods described in Patent Publication number WO 01/40195.

Compounds of formula (lll) are novel and as such form a further feature of the invention, and may be prepared as described above.

Compounds of formula (11), (IV), (V), (V!) and (VII) are known or may be prepared according to known methods.

A collection of compounds of formula (I) which can be synthesized by the above- mentioned processes can additionally be prepared in parallel fashion, which can be effected manually, partly automated or fully automated. In this context, it is possible to automate the procedure of the reaction, work-up or purification of the products or intermediates. In total, this is to be understood as meaning a procedure which is described, for example, by S. H. DeWitt in “Annual Reports in Combinatorial

Chemistry and Molecular Diversity: Automated Synthesis”, Volume 1, published by

Escom, 1997, pages 69 to 77.

For carrying out the reaction and work-up in parallel fashion, a series of commercially available apparatuses can be used as they are available from, for example, Stem Corporation, Woodrolfe Road, Tollesbury, Essex, CM9 8SE, England or Radleys Discovery Technologies, Saffron Walden, Essex, CB11 3AZ, ENGLAND.

To carry out the parallel purification of compounds (I) or of intermediates obtained during the preparation, there are available, inter alia, chromatographic equipment, for example from ISCO, Inc., 4700 Superior Street, Lincoin, NE 68504, USA. The : equipment mentioned makes possible a modular procedure, where the individual steps are automated, but manual operation has to be carried out between the steps.

This can be circumvented by employing partly or fully integrated automation systems, in which the automation modules in question are operated by, for example, robots. Such automation systems can be obtained from, for example, Zymark

Corporation, Zymark Center, Hopkinton, MA 01748, USA.

In addition to the above-described methods, compounds of formula (I) can be prepared in full or partly by solid-phase supported methods. To this end, individual intermediates or all intermediates of the synthesis or of a synthesis adapted to the procedure in question are bound to a synthesis resin. Solid-phase supported synthetic methods are described extensively in the specialist literature, for example:

Barry A. Bunin in “The Combinatorial Index”, published by. Academic Press, 1998.

The use of solid-phase supported synthesis methods permits a series of protocols known from the literature which, in tum, can be carried out manually or in an automated fashion. For example, the “teabag method” (Houghten, US 4,631,211;

Houghten et al., Proc. Natl. Acad. Sci., 1985, 82, 5131 — 5135) can be partly automated with products of IRORI, 11149 North Torrey Pines Road, La Jolla, CA 92037, USA. Solid-phase supported parallel synthesis can be automated successfully for example using equipment by Argonaut Technologies, Inc., 887

Industrial Road, San Carlos, CA 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany.

The preparation in accordance with the processes described herein yields compounds of formula (1) in the form of substance collections or substance libraries.

Subject matter of the present invention are therefore also libraries of the compounds of formula (1) which contain at least two compounds of formula ([), and of their precursors.

The following non-limiting Examples illustrate the preparation of the compounds of formula (1).

A. Chemical Examples

In the Examples which follow, quantities (also percentages) are weight based unless stated otherwise. Ratios of solvents are volume based.

Example 1. 5-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethyithio-1H-pyrazole-3- carboxylic acid (Compound 2.10)

A stirred mixture of 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4- trifluoromethyithio-1H-pyrazole-3-carbonitrile (35.5 g, 84.3 mmol) and sulfuric acid : (50%, 600 ml) was heated to 135°C for 7 hours. The cooled mixture was added to ice water and the precipitate filtered off, washed with water and air-dried. Trituration with tetrachloromethane gave the title compound as off-white crystals (30.6 g, yield 82%), mp 199°C, "TH NMR(DMSO-d8): 6.66 (bs, 2H, NH), 8.23 (s, 2H, Ar-H), and 13.03 (bs, 1H, COOH).

Example 2. 5-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethyithio-1 H-pyrazole-3- carboxylic acid amide (Compound 1.4)

A mixture of 5-amino-1-(2,6-dichioro-4-trifluoromethylphenyl)-4-trifluoromethyithio- 1H-pyrazole-3-carboxylic acid (1.00 g, 2.27 mmol) and 1,1-dicarbonylimidazole (0.45 g, 2.72 mmol) in dioxane was heated to 50°C for 2 hours. An aqueous solution of ammonia (33%, 80 ml) was then added and stirring continued at 50°C for 4 hours.

The cooled mixture was diluted with water and extracted with ethyl acetate/heptane (1:1). The combined organic phase was washed with aqueous potassium hydrogensuifate (5%), dried over magnesium sulfate and evaporated to give the title compound (0.980 g, yield 98%) as a white foam, 'H NMR(CDCls): 4.36 (bs, 2H,

NH), 5.60 and 6.69 (bs, 2H, C(O)NH,), and 7.82 (s, 2H, Ar-H).

Example 3. 5-Amino-1-(2,6-dichloro-4-trifluoromethylphenyi}4-trifluoromethyithio-1H-pyrazole-3- carboxylic acid cyclopropylamide (Compound 1.1)

A mixture of 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethyithio- 1H-pyrazole-3-carboxylic acid (0.85 g, 1.83 mmol) and 1,1-dicarbonylimidazole (0.36 g, 2.20 mmol) in dioxane was heated ta 55°C for 2 hours. Cyclopropylamine (0.20 ml, 2.83 mmol) was then added and stirring continued at 55°C for 6 hours. The cooled mixture was diluted with water, extracted with ethyl acetate, washed with aqueous potassium hydrogensulfate (5%), dried over magnesium sulfate and evaporated to give the title compound (0.762 g, yield 87%) as off-white crystals, mp 193°C, 'H NMR(CDCl3): 0.64 (m, 2H, cyclopropyl), 0.83 (m, 2H, cyclopropyl), 2,87 (m, 1H, cyclopropyl), 4.31 (bs, 2H, NH), 6.82 (bs, 1H, C(O)NH), and 7.80 (s, 2H, Ar-

H).

Example 4. 5-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl}-4-trifluoromethylsulfinyl-1 H- pyrazole-3-carboxylic acid propargylamide (Compound 1.134) :

To a suspension of 5-amino-1-(2,6-dichloro-4-trifluoromethyiphenyl)-4- trifluoromethylthio-1H-pyrazole-3-carboxylic acid propargylamide (0.71 g, 1.43 mmol) in dichloromethane was slowly added a solution of m-chloroperbenzoic acid (70%, 0.41 g, 1.68 mmol) in dichloromethane. After stirring for 17 hours at 20°C, an aqueous solution of sodium sulfite/sodium hydrogen carbonate (5%:5%, 25 ml) was added and stirring continued for 15 minutes. The aqueous phase was extracted with dichloromethane, dried over magnesium sulfate, evaporated and purified by flash chomatography (silica, heptane/ethyl acetate) to give the title compound (0.604 g, yield 86%) as white crystals, mp 207°C, 'H NMR(CDCl,): 2.28 (t, 1H, propargyl), 4.20 (m, 2H, propargyl), 5.17 (bs, 2H, NH), 6.88 (bt, 1H, C(O)NH), and 7.83 (s, 2H,

Ar-H).

Example 5. 5-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl }-4-trifluoromethylsulfonyl-1H- pyrazole-3-carboxylic acid amide (Compound 1.268)

A stirred mixture of 5-amino-1-(2,6-dichioro-4-triflucromethylphenyl)-4- trifluoromethylsulfonyl-1H-pyrazole-3-carbonitrile (1.06 g, 2.21 mmol) and concentrated sulfuric acid (1 ml) was heated to 100°C for 3 hours. The cooled mixture was added to ice water and the precipitate filtered off, washed with water and air-dried. Purification by flash chomatography (silica, chloroform) gave the title compound (0.869 g, yield 83%) as off-white crystals, mp 217°C, 'H NMR(DMSO-d6): 7.39 (bs, 2H, NH), 7.57 and 7.78 (bs, 2H, C(O)NHz), and 8.25 (s, 2H, Ar-H).

Example 6. 5-Amino-1-(2,6-dichloro-4-trifluoromethyiphenyl)-1 H-pyrazole-3-carboxylic acid (Compound 2.1)

A stirred mixture of 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4- trifluoromethylsulfinyl-1H-pyrazole-3-carbonitrile (5.00 g, 11.4 mmol) and sulfuric acid (50%, 100 ml) was heated to 135°C for 3 hours. The cooled mixture was added to ice water and the pH adjusted to 4 by the addition of aqueous sodium hydroxide (6

N, approx. 230 ml), and then extracted with ethyl acetate. The organic phase was dried over magnesium sulfate, evaporated to dryness and purified by flash chomatography (silica, chloroform/ethanol) with subsequently trituration with tetrachloromethane to give the title compound (3.00 g, yield 77%) as off-white

- crystals, mp 213°C, H NMR(DMSO-d6): 5.69 (bs, 2H, NH), 5.76 (s, 1H, pyrazole-

H), and 8.20 (s, 2H, Ar-H).

Example 7. 1-(2,6-Dichloro-4-trifluoromethylphenyl)-5-ethoxy-4-trifluoromethyithio-1H-pyrazole- 3-carboxylic acid amide (Compound 3.3) a) To a stirred suspension of sodium hydride (0.41 g, 60%, 10.3 mmol) in dioxane (150 ml) was added a solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-5-hydroxy- 4-trifluoromethylthio-1H-pyrazole-3-carbonitrile (4.00g, 8.53 mmol) in dioxane (50 ml). After gas evolution had ceased the mixture was heated to reflux and diethyl sulfate (1.25 ml, 9.47 mmol) added, and then heated under reflux for 6 hours. The "cooled mixture was acidified with aqueous potassium hydrogensulfate (5%), extracted with dichloromethane, and the organic phase dried over magnesium sulfate and evaporated. The resulting gum was triturated with pentane to give 1-(2,6- dichloro-4-trifluoromethylphenyl)-5-ethoxy-4-trifluoromethyithio-1H-pyrazole-3- carbonitrile (2.68 g, yield 70 %) as off-white crystals, mp 106°C, '"H NMR(CDCls): 1.36 (t, 3H, CH3), 4.71 (q, 2H, OCH), and 7.76 (s, 2H, Ar-H). b) A stirred mixture of 1-(2,6-dichloro-4-trifluoromethylphenyl)-5-ethoxy-4- trifluoromethyithio-1H-pyrazole-3-carbonitrile (0.55g, 1.22 mmol) and concentrated sulfuric acid (0.55 ml) was heated at 100°C for 3 hours. The cooled mixture was added to ice water and the precipitate filtered off, washed with water and air-dried.

The crude product was dissolved in heptanes/ethyl acetate (1:1) and filtered. The filtrate was evaporated to give the title compound (0.42 g, yield 73%) as yellowish crystals, mp 161°C, 'H NMR(CDCI5): 1.32 (t, 3H, CH), 4.68 (q, 2H, OCHz), 5.54 and 6.69 (bs, 2H, C(O)NHy), and 7.77 (s, 2H, Ar-H).

The following preferred compounds of formula (la), (Ib) and (ic) shown in Tables 1 to 3 also form part of the present invention, and are obtained by, or analogously to, the above Examples 1 to 7 or the above-described general methods.

The following abbreviations are used in the Tables 1 to 3:

“Cpd” means Compound Number. Compound numbers are given for reference purposes only. RF means retention time determined from thin layer chromatography on silica gel, using ethyl acetate as eluent.

Table 1: Compounds of formula (la)

Oo

R1ON NY : nen (la)

CF,

I I I A IA id 2

I IC A NC I a

IE I CT NC I RL

IE EC NA BC CB En a

EC CCI IL ILA ca wn | owes |W || fas)

Ml CC BCC I LN BA

IE ET NCC UN UB

I NC I

I IC EO

EE I I I HL I

I CC HC IC

0 i 2 Hl

EE Cc CI I

Ec ccc I IL A

Ec cc IIL ccc OL 0 a] son | owemsow | w |W]

Cc ccc cI cE il) a re cl cc He LN cc I ccc LN a ccc He LN ccc cc ccc cl ccc HL 0 cc ccc cc cc ccc Wc a cc cL a cc a ccc cL lc cL lc cc cL cl cc I

I cc cc cc LI. lc ccc I. i ccc LI cl cB A 1 a cc cL. a Ec I

I 0 el 2) al cc Le a J cc I cA

A . ccc

I ec Le

EE cc ccc A cH

EE ccc A ci

Ec ccc

Ec ccc A ci) roo ser, | omononoon | wow

Ec ccc cc a cL ccc Lc ccc a cc LO a Nc LL a cc sc) a ccc LY 0 cL

Tw] son | owen |W foul cc. a ee) I cy ac Nc Cc)

a a 0 il 2 lc ccc 0 cc We a ac CN Be or sn | owen [ow owl cc ccc lc ccc rw] son | omen | on [ow

Fc ce ct

Fcc ccc

Fc ec

Fc cc cc)

Fc ccc a

Fa cc ccc cc)

Fc ccc

Fd Oc cc a ct io] son | ouonenoon | on [oa] son | onowos | on [on

Fc cc cc) i] son | women | Gu jon] son | owomen | on [on

Tc ccc

Fc cc

FE ccc a ro] son | soma | Go fon

EE ce ay cE A a 5) son | awones | ov [on]

Fc cc ce

Fal ra son | owen Jowom [on]

Nc cc I a ccc 0 ar son | onowoonon [wl

Rd cc IL

Soo | oheion | ww | we oo ro] soon | aww | |W | wi Joon

Rc J I LB BC a

SOF | omowoc | i | | [om

Fd I IL aE I I ad 0

Fcc cc CI I

Fc cc dc cc

Fc ccc

Fl ccc A

Fc ccc A I

Fc ccc NL A

Fd lc cc A I

Fc ccc A I soon | owomen | Ww]

Fc ccc I

Fd cc cc A

Fc cc LI soon | sowwway | ww

Ft cc I IL

Fc cc IIL I soon | ononsene | & |W]

Fl cc I

Fc cc I soon | owomeon | an |W

Soon | onowon | Gb | Wen [00

Fc NC LA LN es] Soon | oon | on | ww [our

Fc cS HC I rr] soon | owomen | [w]

CE A WL al 2 al

Fc Cc NC IL

Fc ccc Mc LH

FE ec

Fc cI

FC cc I

Fc ccc

Fc ec

Fc ccc

Fc ccc er] sion | anononoon [an [wl

Fc ccc

Fc ccc cI

Fc cc cI

Fc ccc

Fc cc I

Fc Nc

Fc a cL

Fd cc

Fc ccc cL

Fc ccc IL ec IL

Fc Cc CI cy

Soon | oweneon | Hon

Fc ccc sc)

a EE A I od ic)

Fc Hc LA YB

Fc cc Lc an] soon | ononon |W Jon

Fc Nc cL. 2] Soon | _owomen | w_ fon]

Fl cL. a] soon | oweoon |W _jon

Fad a soon | zw | woe

Fc cc cc) a] soon | owen | w fon ao] SOR | hemo |W fon]

Fl ca

Fc ccc Le

Fi ccc sc 20] soon, | owowon | we

Fc cc IL.

Fd cc 26] Soon | owomon | won

FE ca ccc Le 26] soon | own |W jou]

Fc ca A

Fc cc A cI

Fc cc I

Soon | owner |W jonl

Fcc cc WI a

A i 2

Rad ec

Fd Cr

Ed cc ee

Fd cc 0 cr

Fd cc a 7] Soe | ononon | on [on]

Rc cc ce dc ccc ce lc cc cc

Rl cc

SO | zen | on [on]

Ec sop | owen | om Jon lc ccc

El cr a

El cc

NE cc cs 2 Soe | owomon | ow Jon]

I a EA 0 il cl on] Soon | sony | oh [on]

Fc cc YN

Es] Soon | owen |W

Fc ccc IL

Fl Cc cc cc IL A

Fc cc)

Fc ccc YN

Soon | owonooken [on a cc ce YN

Fad Cc I I

Soc | _oneeor | Ww

Fc ccc NL A

Fl cc NL A LB a

Fl Hc NC SCI IL

Ft cB NL IL

Fe ccc NL LN

Fo cc cB NA I

Ft ccc NA

Fc cc I

Fi ccc WI IL cE A id LC)

Fc rc LI

Fd LI IL as soon | owen | ww on Son | owner |W [Ww

Fl ccc I

FE cc I

Fl ccc

Fd ccc I

Fd ec I soon | oon |W [w

Fl cc I

FE ccc I I sour, | one |W [WC soon | owosere | ww

Fd ccc I cL I

Fd cc IL 7] son | owoneon | on [

Fl cc Hc

Fd I Hc IL

Fl CN IL on] soon | omenon [on |W]

Cl EJ A Ll) al

Fc cc CL CN

Fc ccc CL

Fc Nc CN

Fd a ccc

Fl cc Mc LH

FE cc Fc LH

Fc cc Hc

Fc ccc Fc LI

Fc cc Hc A

FE ccc

Fc ccc Hc

Fl ca ccc A 5] Son | oRonson | on

Fl a ccc cc

Fl ccc I

FE cc

Fc cc cL

Fc cc HL

Fl cc CC

Fa ccc ca

Fd cc ca

Fal ec Cc Le

Fc ccc Le

HF [WW [Ro mrol

Soon | owen | Hn (onl dc I NO Ml

Fc I I cB

Fc cc I

Fd cc I a

Fl cc I

Fd ccc I cB 5% SOR | omen |W [on

Fd ccc I ed

Rd I a I ct NO

Fd a I cd

Fd cc NO A YI

FE ccc 2

FE ccc LT

Fc 2 Wc Le lc cc LT a

Fcc OL

Fl ccc ec

Fc cc

Fc ccc

Fc ccc 56 sown | owomson | wn [onl lc I ec

Fc cr I 2c cc LO

Rc cr Lc cE A 0 a 2 dl

Fc cr CI cc) dc Wc I ic cr

Fc Cc

Fc ccc cc

Fc cc

Fc Ce

Fc cc TO Hc

Son | onemon | on [on son | oMow | on [on

Fc cc Wc

SO | owen | on fon]

Ft cc cc

Fa a

Fc Nc YN

Fl cc

FE ccc cc

FE rc HY

Fc ccc

Fa ccc

Fa ccc ca

Fc ccc a

Son | owen | oh [on]

FE cc Wc

Fc cc cc cc Wc a)

cE A 0 i 2) cl

Fd cc cc 0

Fc ce eR

Fd cc eR

Fd cc ec

Fd 2c cc 0 i ccc a 2c crc ror sown | oven [ower W rom sown | oven [owen [on]

Fc ccc LH

Fd ccc A

Fc ccc a

Sow | onowmonnon |W

Son | owomen [on] ow son | momen [an]

Fc ccc

To | Sor, | onomonnon [Gh

Fad cc IC

Fl ccc A mw | owowos |W |W] a om

Fc III

Fc cc a

Fl ccc I.

Fad cc I raw | owowen |W [W cE 0 a 0 aw | owen | [wl

Ed ccc WL LH

Fd ec I I

Fd cL 0

RE NB BL a

FE ccc NL cc

FE ccc I

FE ccc

FE ccc I LO

FEA cc A

FE ccc I

Fl cc LI

Fl ccc LO

Fc cL cc

Fl ccc A

Fa cc LL

Ft cc LI

Fa ccc CO

Fad a) I

Fd cc cL

Fd ccc He

FO ccc I

Fc cS NC LN a 0 ed 2

Fd cc Hc ew | owown [ow wl

El Nc ew owomon [ow [wl

FE Nc aw | owen [ow |W]

Fd ec

Fd rc

Fl cc I

Rc ccc

Fd cc

Rl ccc

RE cc Sc

Fl ccc ew | owomon [ow [wl ww | owomson | ow [Wl

FE cc Sc

FE

Fl cc a

Fcc cL

Fl cc I I

FE cc I I

Rd CI NC I cE NL i

Fc] Cc Ie.

Fd cco ccc I.

FE ICI 1

FE IL.

Fl cc

Fc ccc

Fd ccc I

Fl. I.

FE cc I.

Fc ccc A cH

Fl ccc I.

FT ccc I ccc I aw | omoworoon | fon

Fa ccc I)

Fc cc IL.

Fd ccc I) ON

Fl ccc A an | omowsow |W jow

Fc NL.

Fl cc I)

a A 0 id 2 al

Fc cc

Fd cL

Ed cc

Rc ccc cc

Fd tc a

Hd Cc

Rl cc 0

El cc

Fc cc)

Fl cc Sc cr w| owner [on [on

Fd ccc

Fl ccc Wc

Fa ee cB

Ft ccc 0 cH lO ec

Fc cc

Fc Ec

RE

FT ccc 0 ca)

Rca ccc cc

Fd ccc cc an | owononoon | ow [onl

Fc cc 0c

Ew | ows ae Jou

El I NC

CC J 0 i 52) cl on | owomon | jos]

FE cc ce dE SO N.Y

FE cc lc

FE cc ce.

FT cc cc oe | owes [on fos

Fd cc cc

FE cc a

FE cc vc)

Fa cc ce.

Fc cc. I

Fd ccc 0

El ccc A a cc ccc I

I cc

I cc er | ononooion ow om | owoomenon [on dc crc WL A ow sonon | _omereon | w [Ww

Fc ccc LI I lc IO NL HN

Fc cS

Fc ccc NL 0 id i) al

FE IL ear soon | owonson |W |W]

FE ow | sonom | _onowoon |W Jw

FE We

EE

FE cc

Fc ccc sono | women | Ww lc dc

Nc ec LI

EE LI IL rear] sono | owencm |W |W

EE cc I

RE I ow | son | emo | |W oi] sono | _ononeon | ob [w]

cE A a 5) Ml

Rd Re I cc C0

RE CT

Rol Cc He LH ro son | omenon | on |W dc cc

Rc cc IL ow | Soh | amown | on [W] 5% | Son | owonoon | om |W

Nl ee I

Fc cL

Rc cL

Ec ccc Hc

Fac ca Wc I

Fc ccc LI

Nc ccc

Fd cL ow Sonn | onew | on [W ow | son | onsen | ob |W

Re NL

I i 2 ow | son | onsore | Go |W]

Rl Co ca I I row] son | oon | W_fon

Rc Oc

FE cc A cS

FE ccc oz] sono | onomon | ® Jom ois] owen | owes | {on cl EC A BL a 2 ou] oven | om |W jonl

FE cc cr LY

FE cc Lc

FE ce cc A cd

FE cL 50] Sonor | rohan |W [onl

Fl acc

Fl ca Cc ce

Fc ccc cc

Fc cs om] soho | non | ow [onl

Fc cc Wc ec

Fc cc

Fc Fc ccc cc)

Soho | amen | on [On 0] Shon | ononoon | on [on

Soon, | ri | o% [o6 cc ec) re] Sowon, | owen | on [ow] ccc ce

Fe cc ce cc Wc a

Fd ca ccc cc)

Tl Sonn, | onronoy | oh [on oo] Sonn | onenson | on [on]

EN M0 il 2

Fc Hc 0 YR ror senor | owcraowon | 06 [Gh

Rd Co 0 lc cc Wc

Fc SO ca

Fc cc 0

Fl cc a ro son | oven [owen ow soon | oon [owen on]

Fc cc

Fa cc. a ccc

Fd ccc ro Sono | owen [on] ow Sonn, | owomen [oh

Fd cc ow | Soren, | oomGHoRe [0h

Fc OC I

Fd ccc os [SOmon | _onovon | ww]

Fc EL 0 ow [soem | ow | WF]

cE I A Ll) row Sopon | oon |W |W ]

Fc cc I IL

Fd cc NL I NO ro | SOpon | _owemon |W [A]

FEC Cc A

FE i cc I A

FE Na A

Fc I

Fa Nc I A

FN cc A

FE cc A a

RE ccc A

Fc cc I

Fl ccc om | soon | _anoon | mW]

Fe cc LI

Fc ccc

Fl ccc LA I

Fd ccc I

Fd NL

Fd cc NL A

Fd cc I I

Fc ec IC

EA NN Ld CC

Rd NC HC om | Soon | oreo | a [7]

Fd Occ cL

Fd cc FO dc cc Hc I

Rd ccc a dc cc

Fd ccc He A

Nl cc cL

FE ccc cL 702 SOF | zion | oh |W

FE

FR cc LH

Fd ccc cL

Fd cc Hc

Fad 0 coc a

FE ccc a 70 soon | _onerionoon | on | #

FE ccc cL soon | Ron | on [Wn]

FE cc

NE cc ccc a

FEA cc ccc

Ec cc cL

FEA ec TI cL

RE ec cc LI

EN EA od): 70] Soon | Geert | Go |W]

FE a NC I

Fd a Wc

Rd a cv

Fi a NC sc a cc LL 7 Soong | onoon |W fon]

Fd cc NL. A

Fc NC LL.

Fl a cc Ls.

Fi cc ccc I.

Fc cc Lc

Fa acc LL

Fl cc NL ey

Fc ccc Lc

Fe a Lc

Fcc Le

Fe cc LL

Fe cc

Fl a ccc

Fo cc ccc I cB 70] sono | come | Won]

cL EL 0 el 2 rer Soon | Gomon | w_jon 76s Sgro | Goro |W [on

REA] NCS NL

FE I

RE cc

FE LY

7 soon | _owoncn |W Jon]

CE 0 ad 0 7 Soros |_onononoon | oh [on]

RE cc ec 72 soon |_okern | ow jon

RE] ccc ce 77 soon | women | os [om

REA cc

FE cc cc

Fc Nc a)

NEA cc cc

FE ce 70 Soon | owner | on [on] 781 Somwon [Groner | on Jon]

Fd a a 7s Sopvion |__ower [owen | w

Fc ccc

Fc ccc Ml

Fc ccc

FE cc ccc A 7 SOpon | omc [oa] 7 Soon | owomen Jon 791] Soon | Gonoonon Jon]

Fd cc

Fd 2 Cc I

Fd 2 ccc BNI

Fd ccc IL od 5) Ml

RE Ce I WL

RE Oc A.

FE cS om soso [oom | mW]

RE cn cc

Fc J II

RE ccc NL

RE

Ra

Rc cc cB I

Fc ccc A

Fc cc NL

Fc ccc A a

Rc ccc

RE i ccc I

FE a ccc I i cc cc I. I

NE ccc A I

Ri cc LA sown | oon | BW

RE cc

Nc Oc I

RE cc cc A I

Fe Cc CC I

Fl eC I LN A cE A WL 0 Ld 2) cl

Fc cc NL I

Fl ac) LA HL

Fd ca Cc CH

Fd cc 0 I 8 [soncrion | owen | On

Fa cc cS cH

Fd Oc He IL a coc cI

Fl cc Lc He AL

Fe cc Wc A NO

Fd I AL 55 [soucnon | ovonoon | on

Fd a Wc LN

Fd I Wc I NO

Fd cc 0 I

Fu ccc Wc Ml

Fd i ccc I

Fd i ca HL

Fl cc Wc I

Fd cc Wc I

Fc a ccc Ne I

Fl cc eS IC

Fad cc ML

Fd cc cc NL I

Fl cc cc NO I

Fc cc I

Kl 0 Ll 2 al

Road OC cL

RE I

RR] EC I sour | awonor | on [W]

RE cr I I

RE ee Co HL

RE ec CI cc)

Rd cc Ic) os souoon, | oonon | won

Rd ce BS II cc)

RC I cr) de 2 0 sCyoon | ono | [oR

RE ec I

Rd ce

RE ce I cc)

SCyorion, | nono | won

RE

FE ce Cc ar sCyoron | ono | won

SG | Goren | Wom

Rl

Rl Cc I a

RE cs I 72 [Sonor |_omcnovoon | Won

RO EL A cc Ea 0 i 2)

FE cc cr CA YN

FE ce ccc NC YN

Fc ccc LA tN

Fa ccc

FE a cc I

Fd cc ct

Fd cc

FE cr ec

Fc cc

Fl cc ec

Fe

Fc Cc ct

Fc cc cc

Fl cc i)

Fc cc YR

Fd a cc cc)

Fc ccc Wc ct

Fl Oc cy

Fc cc Wc ct

Fa Cc cc oo Sonn | owenoon | on [ow

Fn cc ey

Fe ct

Fd i cc Hc ct 6 Soom | Gonon | on [on

Fc cc cd

EN id) al

Fl cc cc Ce

Fc Ce

Fd ec ca om [sooner | _ononson, | [onl

Fd cc cc Ne

Fd 2 cc a

Fd 2c ce

Fd cc ec cc rom [sooReR | oom | on fon] lc ca ro [sooner | sory | oh [onl

FE 2 cr on [SORT oronem | on [onl 70 [SOR | Chonmren | on Jon]

FE a ec a

Fd 2c ccc

FE Ec cc SO ce I

Fd cc ccc

Fd cc ccc [SOR oworoon |W

Fl cc ccc

Fe ccc AL

Fc ccc ci)

Fd ccc

Fc ccc ca

Table 2: Compounds of formula (Ib) 0) ry

R10R11N NN nex (Ib)

CF, (cd RJ RF [RU] RT [mo] RF

EE I I CN IL

23 ow [ow Jom ow [|] (24 Ww Jom [HW |] woe [oem | |]

NE I Hc 0

JE EI 0% I NC FR

TE ec

IE I ccc ao] sm | ow | | ow | wow

A cL CN CN I 2 cc CO NL LI EE 0 cc CO 0 NI EN I

I cc 0 FN

Ec I

Ec cL

Ec cc A cc I A

Ec cc Hc I cc A cc LF

Ec I

To sonon |W [ow | on a sonon | ow | ww [ a cc

Ec cc aT I I I cl I Nl A CR NL a Mc cc Hc I EO zis | soon | owen | om | on

Ec LO I A EN

Zo [Somos |W [on | Aw || _

Ec cc. I

El I A NN le cc NN

El cc RN i cc I A RR 2 [soon oven | on |W

I LI NS i cc A cl I NN i) son [own [ WW

Ea I cc cL son oe [om [ow 2c LL som [wow [A 2 0 el som [on | nw a cc cL ze soon | on [on | ow

Ec cc LS oo | som [owen [ow | A

Ec ccc

Ec I A NO

Ec Lc NL I 2c Lc

Ec NL NL I

Ea 2c cL 2c cc 2 | soon [oven | A |W lc NL I alc ccc CL I ccc LL NL I

Ec Lc NL cl cc I cI NN i cc cL I FO a ca cc LI I

I a NC BL Kc) a cc Wc

I cc I IL EO lc cc Wc LA NN

Ec cc WC

Ecc I I HR i oor, | wom [wo

Ec cc EN RO io | Soeor, | on | w

Fc cL HR sopor | on [on [ow

Ec cc NL I A

Ec cL cc cc ER

Ec A HL

Fc cL iw soo | Won [ow

Fc LL

Cc cc LT zi] soon | on [on [ow

Ee cc NL LI

Ed cc NL

EA ccc cc I lc LL

Ec Hc NL

Fc CF

Fc LA LI a a A RL CR cc cL NN wa or | on om | ow

Fc cc LL NS cc A I ccc cc 0c LY

Fc cL NY

Fc cc

Frc LL a wooo | on [on

Soper | on ow | ow

Fc cc NL

Fc cc Nc NL NY

Fr cc Nc

Fd ccc LL RN

Ec cL

Fc cc

Ec co LL mr soon | on [ow mw soon | on [on | on aie] soos [oe | Ww

Fc cc LT

Fc ccc I

Table 3: Compounds of formula (Ic) 0]

R? NN aes (Ic)

CF, oi ® [ ® [® [moo]

EE Fc A A CA I cc RL NN NN 55 son [oonom | ww | we | om

Se Sor | oon, | sonGmn_| | war | oa

Selon | om | wow

I ccc IC NC arson | wow |W [wl cc) A wo son [Wowpoem 1 cc NB HL I I srsoon | on | ww a sogr | oon | WH 5 06n | oon | sow |W soon [oom | wR]

Ca ca I I I io sopn | wom |_

Ee I NL I ol ® W@W [7 [wo] w_

Ec LC) NC

Ec IC cc

Ec cc I lc co ccc HL cI NN LH cc cc HL ccc cc cc LN ccc

Cc cc ccc LI

GN Kar a cc LC ccc LO ccc ccc i cc ol Socr, | Nom: | avosonoos cc ccc cI cc NL ccc cc cc

Fc cc cc LH

Ec NN cE EC EN Wa tc

Sos | Wo: | sana |B

EE IC Nc NC I soon | We | owners | W 7 son |_wow, | ens |W sof soen | wos | Cm | * imidazolyl 0 Sor | Wom | ome [o

EN Cr cc a soon, | Wom | aweon [on 52 soon | wow | avon] 5 soon | Wow | owen [on

Ed LC Cc 5 soon | Now| oem (on 5s Soon, | Wom | owen | oh

Ea NC IC es I 5 SO | Wor _|_onomeon_| oh cd

Fc LC

Ea CC Cc ey NI

I Cc a 55] SOF, | Wow: | Orson | 0

Fa TO cons a

Fc cc oC

So SOR | Wom: | ovenenoas [oh

Fd a CT Wc IY

Fc ca

I A LA IL CC i) CC Cv Kc I

Ed) CC SN YN

El a a Py

Fd CCE NN a

Ed CC cc a

EE IC uc Kc

EY LC I

75 SO | Wow | oon [on 377] SOICFs | NCH: | OnCHedpyrod [CH ooo |r Jo imidazolyl ome | oe

El CT a I

Fc I cc NO

Fc NC ce NO

S06, | Wow, | onsen

ERE) I IL BL

Sw lsomn | oon |W |W

S30 [src [Gowen |W | WO dc) NL A I NO = [SOp0r [Wompoes | |W i cc I I NO

Another aspect of the invention is a method for plant growth regulation which plants are monocotyledoneous or dicotyledoneous crop plants, preferably selected from the group of economically important field crops such as, for example wheat, barley, rye, triticale, rice, maize, sugar beet, cotton, or soybeans, particularly maize, wheat, and soybean, as well as vegetables and ornamentals, said method comprising applying to said plants, to the seeds from which they grow or to the locus in which they grow, a non-phytotoxic, effective plant growth regulating amount of one or more compounds of formula (i).

A further aspect of the invention is a method for plant growth regulation, which plants are monocotyledoneous or dicotyledoneous crop plants, preferably selected from the group of economically important field crops such as, for example wheat, barley, rye, triticale, rice, maize, sugar beet, cotton, or soybeans, particularly maize, wheat, and soybean, as well as vegetables and ornamentals, said method comprising applying to said plants, to the seeds from which they grow or to the locus in which they grow, a non-phytotoxic, effective plant growth regulating amount of a compound having the formula (I) in a mixture with carriers and/or surfactants.

A further aspect of the invention is a method for plant growth regulation, which plants are monocotyledoneous or dicotyledoneous crop plants, preferably selected from the group of economically important field crops such as, for example wheat, barley, rye, triticale, rice, maize, sugar beet, cotton, or soybeans, particularly maize, wheat, and soybean, as well as vegetables and ornamentals ,said method comprising applying to said plants, to the seeds from which they grow or to the locus in which they grow, a non-phytotoxic, effective plant growth regulating amount of a compound having the formula (I) together with a further active compound selected from the group consisting of acaricides, fungicides, herbicides, insecticides, nematicides or plant growth regulating substances not identical to compounds defined by formula (i).

Incase thatit is intended to apply the compound having formula (1) either alone or together with a further active compound directly to the seed, there are several ways on how to perform such seed treatment, like by “filmcoating” which is characterized by the creation of a liquid formulation containing an applicable polymer which will be applied to the seed, thereby improving the adherence, the coverage and the distribution of the compounds on the seed.

Among the further active compounds to be applied together with a compound having the formula (1), either applied as one further active compound or applied in a combination of several further active compounds, the following compounds are specifically named as examples of such further active compounds: 2-Phenylphenol; 8-Hydroxyquinoline sulfate; Acibenzolar-S-methyl; Actinovate;

Aldimorph; Amidoflumet; Ampropylifos; Ampropylfos-potassium; Andoprim; Anilazine;

Azaconazole; Azoxystrobin; Benalaxyl; Benodanil; Benomyl; Benthiavalicarb- isopropyl; Benzamacril; Benzamacril-isobutyl; Bilanafos; Binapacryl; Biphenyl;

Bitertanol; Blasticidin-S; Boscalid; Bromuconazole; Bupirimate; Buthiobate;

Butylamine; Calcium polysulfide; Capsimycin; Captafol; Captan; Carbendazim;

Carboxin; Carpropamid; Carvone; Chinomethionat; Chlobenthiazone; Chlorfenazole; Chloroneb; Chlorothalonil; Chlozolinate; cis-1-(4-chlorophenyl}-2-(1H-1,2,4-triazole- 1-yl)-cycloheptanol; Clozylacon; Cyazofamid; Cyflufenamid; Cymoxanil;

Cyproconazole; Cyprodinil; Cyprofuram; Dagger G; Debacarb; Dichlofluanid;

Dichlone; Dichlorophen; Diclocymet; Diclomezine; Dicloran; Diethofencarb;

Difenoconazole; Diflumetorim; Dimethirimol; Dimethomorph; Dimoxystrobin;

Diniconazole; Diniconazole-M; Dinocap; Diphenylamine; Dipyrithione; Ditalimfos;

Dithianon: Dodine; Drazoxolon; Edifenphos; Epoxiconazole; Ethaboxam; Ethirimol;

Etridiazole; Famoxadone; Fenamidone; Fenapanil; Fenarimol; Fenbuconazole;

Fenfuram; Fenhexamid; Fenitropan; Fenoxanil; Fenpiclonil; Fenpropidin;

Fenpropimorph; Ferbam; Fluazinam; Flubenzimine; Fludioxonil; Flumetover; Flumorph; Fluoromide; Fluoxastrobin; Fluquinconazole; Flurprimidol; Flusilazole;

Flusulfamide: Flutolanil; Flutriafol; Folpet; Fosetyl-Al; Fosetyl-sodium; Fuberidazole;

Furalaxyl; Furametpyr; Furcarbanil, Furmecyclox; Guazatine; Hexachlorobenzene;

Hexaconazole; Hymexazol; Imazalil; Imibenconazole; iminoctadine triacetate;

Iminoctadine tris(albesilate); lodocarb; Ipconazole; Iprobenfos; Iprodione;

Iprovalicarb; Irumamycin; Isoprothiolane; Isovaledione; Kasugamycin; Kresoxim- methyl; Mancozeb; Maneb; Meferimzone; Mepanipyrim; Mepronil; Metalaxyl;

Metalaxyl-M; Metconazole; Methasulfocarb; Methfuroxam; methyl 1-(2,3-dihydro-2,2-

dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate; Methyl 2-[[[cyclopropyl[(4- methoxyphenyl)imino]methyi]thiojmethyl]-.alpha.-(methoxymethylene)- benzeneacetate; Methyl 2-[2-[3-(4-chloro-phenyl)-1-methyi- allylideneaminooxymethyl]-phenyl]-3-methoxy-acrylate; Metiram; Metominostrobin;

Metrafenone; Metsulfovax; Mildiomycin; monopotassium carbonate; Myclobutanil;

Myeclozolin; N-(3-Ethyl-3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy- benzamide; N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide; N-butyl-8-(1,1- dimethylethyl)-1-oxaspiro[4.5]decan-3-amine; Natamycin; Nitrothal-isopropyt;

Noviflumuron; Nuarimol; Ofurace; Orysastrobin; Oxadixyl; Oxolinic acid;

Oxpoconazole; Oxycarboxin; Oxyfenthiin; Paclobutrazol; Pefurazoate; Penconazole;

Pencycuron; Penthiopyrad; Phosdiphen; Phthalide; Picobenzamid; Picoxystrobin;

Piperalin; Polyoxins; Polyoxorim; Probenazole; Prochloraz; Procymidone;

Propamocarb; Propanosine-sodium; Propiconazole; Propineb; Proquinazid;

Prothioconazole; Pyraclostrobin; Pyrazophos; Pyrifenox; Pyrimethanil; Pyroquilon; Pyroxyfur; Pyrrolnitrine; Quinconazole; Quinoxyfen; Quintozene; Silthiofam;

Simeconazole; Sodium tetrathiocarbonate; Spiroxamine; Sulfur; Tebuconazole;

Tecloftalam; Tecnazene; Tetcyclacis; Tetraconazole; Thiabendazole; Thicyofen;

Thifluzamide; Thiophanate-methyl; Thiram; Tiadinil; Tioxymid; Tolclofos-methyl;

Tolylfluanid; Triadimefon; Triadimenol; Triazbutil, Triazoxide; Tricyclamide;

Tricyclazole; Tridemorph; Trifloxystrobin; Triflumizole; Triforine; Triticonazole;

Uniconazole; Validamycin A; Vinclozolin; Zineb; Ziram; Zoxamide; (2S)-N-[2-[4-[[3- (4-chlorophenyi)-2-propynyfloxy]-3-methoxyphenyijethyl}-3-methyl- 2- [(methylsulfonyl)amino]-butanamide; 1-(1-naphthalenyl)-1H-pyrrole-2,5-dione; 2,3,5,6-tetrachloro-4-(methylisulfonyl)-pyridine; 2,4-Dihydro-5-methoxy-2-methyl-4- [[[1-[3-(trifluoromethyl)-phenyl]-ethylidene}-amino}-oxy]-methyl]-phenyi}-3H-1,2,3- triazol-3-one; 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N-(2,3- dihydro-1,1,3-trimethyl-1H-inden-4-yl}-3-pyridincarboxamide; 3,4,5-trichloro-2,6- pyridinedicarbonitrile; 3-[(3-Bromo-6-fluoro-2-methyl-1H-indol-1-yl)sulfonyl]-N,N- dimethyl-1H-1,2,4-triazole-1-sulfonamide; Copper salts and Copper preparations, like Bordeaux mixture; Copper hydroxide; Copper naphthenate; Copper oxychloride;

Copper sulfate; Cufraneb; Cuprous oxide; Mancopper; Oxine-copper;

Alanycarb, Aldicarb, Aldoxycarb, Allyxycarb, Aminocarb, Bendiocarb, Benfuracarb,

Bufencarb, Butacarb, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran,

Carbosulfan, Cloethocarb, Dimetilan, Ethiofencarb, Fenobucarb, Fenothiocarb,

Formetanate, Furathiocarb, Isoprocarb, Metam-sodium, Methiocarb, Methomyl,

Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Thiodicarb, Thiofanox,

Trimethacarb, XMC, Xylylcarb, Acephate, Azamethiphos, Azinphos (-methyl, -ethyl),

Bromophos-ethyl, Bromfenvinfos (-methyl), Butathiofos, Cadusafos, Carbopheno- thion, Chlorethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos (-methyl/-ethyl),

Coumaphos, Cyanofenphos, Cyanophos, Chlorfenvinphos, Demeton-S-methyi,

Demeton-S-methylsulphon, Dialifos, Diazinon, Dichlofenthion, Dichlorvos/DDVP,

Dicrotophos, Dimethoate, Dimethylvinphos, Dioxabenzofos, Disulfoton, EPN, Ethion,

Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitrothion, Fensulfothion,

Fenthion, Flupyrazofos, Fonofos, Formothion, Fosmethilan, Fosthiazate,

Heptenophos, lodofenphos, Iprobenfos, Isazofos, Isofenphos, Isopropyl O-salicylate,

Isoxathion, Malathion, Mecarbam, Methacrifos, Methamidophos, Methidathion,

Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion (- methyl/-ethyl), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon,

Phosphocarb, Phoxim, Pirimiphos (-methyl/-ethyl), Profenofos, Propaphos,

Propetamphos, Prothiofos, Prothoate, Pyraclofos, Pyridaphenthion, Pyridathion,

Quinalphos, Sebufos, Sulfotep, Sulprofos, Tebupirimfos, Temephos, Terbufos,

Tetrachlorvinphos, Thiometon, Triazophos, Triclorfon, Vamidothion, Acrinathrin,

Allethrin (d-cis-trans, d-trans), Beta-Cyfluthrin, Bifenthrin, Bioallethrin, Bioallethrin-S- cyclopentyl-isomer, Bioethanomethrin, Biopermethrin, Bioresmethrin, Chlovaporthrin,

Cis-Cypermethrin, Cis-Resmethrin, Cis-Permethrin, Clocythrin, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin (alpha-, beta-, theta-, zeta-), Cyphenothrin,

Deltamethrin, Empenthrin (1R-isomer), Esfenvalerate, Etofenprox, Fenfluthrin,

Fenpropathrin, Fenpyrithrin, Fenvalerate, Flubrocythrinate, Flucythrinate, Flufenprox,

Flumethrin, Fluvalinate, Fubfenprox, Gamma-Cyhalothrin, Imiprothrin, Kadethrin,

Lambda-Cyhalothrin, Metofluthrin, Permethrin (cis-, trans-), Phenothrin (1R-trans isomer), Prallethrin, Profluthrin, Protrifenbute, Pyresmethrin, Resmethrin, RU 15525,

Silafluofen, Tau-Fluvalinate, Tefluthrin, Terallethrin, Tetramethrin (-1R- isomer),

Tralomethrin, Transfluthrin, ZXI 8901, Pyrethrins (pyrethrum), DDT, Indoxacarb,

Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Nithiazine,

Thiacloprid, Thiamethoxam, Nicotine, Bensultap, Cartap, Camphechlor, Chlordane,

Endosulfan, Gamma-HCH, HCH, Heptachlor, Lindane, Methoxychlor Spinosad,

Acetoprole, Ethiprole, Fipronil, Vaniliprole, Avermectin, Emamectin, Emamectin- benzoate, lvermectin, Milbemycin, Diofenolan, Epofenonane, Fenoxycarb,

Hydroprene, Kinoprene, Methoprene, Pyriproxifen, Triprene, Chromafenozide,

Halofenozide, Methoxyfenozide, Tebufenozide, Bistrifluron, Chlofluazuron,

Diflubenzuron, Fluazuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron,

Novaluron, Noviflumuron, Penfluron, Teflubenzuron, Triflumuron, Buprofezin,

Cyromazine, Diafenthiuron, Azocyclotin, Cyhexatin, Fenbutatin-oxide, Chlorfenapyr, ~ Binapacyrl, Dinobuton, Dinocap, DNOC, Fenazaquin, Fenpyroximate, Pyrimidifen,

Pyridaben, Tebufenpyrad, Tolfenpyrad, Hydramethyinon, Dicofol, Rotenone,

Acequinocyl, Fluacrypyrim, Bacillus thuringiensis strains, Spirodiclofen,

Spiromesifen, 3-(2,5-Dimethylphenyl)-8-methoxy-2-oxo-1-azaspiro[4.5]dec-3-en-4-yl ethyl carbonate (alias: Carbonic acid, 3-(2,5-dimethylphenyl}-8-methoxy-2-oxo-1- azaspiro[4.5]dec-3-en-4-yl ethyl ester, CAS-Reg.-No.: 382608-10-8) and Carbonic acid, cis-3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-azaspiro[4.5]dec-3-en-4-yl ethyl ester (CAS-Reg.-No.: 203313-25-1), Flonicamid, Amitraz, Propargite, N2-[1,1-

Dimethyl-2-(methylsulfonyl)ethyl]-3-iodo-N1-[2-methyl-4-[1,2,2,2-tetrafluoro-1- (trifluoromethyl)ethyllphenyl]-1,2-benzenedicarboxamide (CAS-Reg.-No.: 272451- : 65-7), Thiocyclam hydrogen oxalate, Thiosultap-sodium, Azadirachtin, Bacillus spec., Beauveria spec., Codlemone, Metarrhizium spec., Paecilomyces spec.,

Thuringiensin, Verticillium spec., Aluminium phosphide, Methyl bromide, Sulfuryl fluoride, Cryolite, Flonicamid, Pymetrozine, Clofentezine, Etoxazole, Hexythiazox,

Amidoflumet, Benclothiaz, Benzoximate, Bifenazate, Bromopropylate, Buprofezin,

Chinomethionat, Chlordimeform, Chlorobenzilate, Chloropicrin, Clothiazoben, Cyclo- prene, Dicyclanil, Fenoxacrim, Fentrifanil, Flubenzimine, Flufenerim, Flutenzin,

Gossyplure, Hydramethylnone, Japonilure, Metoxadiazone, Petroleum, Piperonyl butoxide, Potassium oleate, Pyridalyl, Sulfluramid, Tetradifon, Tetrasul, Triarathene,

Verbutin.

Another aspect of the invention is a method for growth regulation in plant tissue cultures of monocotyledoneous or dicotyledoneous plants said method comprising applying to plant tissue cultures an appropriate amount of a compound having the formula (1) either alone or together with at least one further active compound selected from the group of plant growth regulators or plant hormones.

The compounds of formula (1) can preferably be employed as plant growth regulators in crops of useful monocotyledoneous or dicotyledoneous crop plants, preferably selected from the group of economically important field crops such as, for example wheat, barley, rye, triticale, rice, maize, sugar beet, cotton, or soybeans, particularly maize, wheat, and soybean, as well as vegetables and ornamentals that have been rendered thus by means of genetic engineering.

Traditional ways of generating nove! plants which have modified characteristics in comparison with existing plants consist, for example, in traditional breeding methods and the generation of mutants. However, it is also possible to generate novel plants with altered characteristics with the aid of genetic engineering methods (see, for example, EP-A-0221044, EP-A-0131624). For example, several cases have been described of - genetic engineering modifications of crop plants with the purpose of modifying the starch synthesized in the plants (for example WO 92/11376, WO 92/14827, WO 91/19806), : - transgenic crop plants which are resistant to certain herbicides of the glufosinate type (cf., for example, EP-A-0242236, EP-A-242246) or the glyphosate type (WO 92/00377) or the sulfonylurea type (EP-A-0257993, US-A-5013659), - transgenic crop plants, for example cotton, which are capable of producing

Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to specific pests (EP-A-0142924, EP-A-0193259), - . transgenic crop plants whose fatty acid spectrum is modified (WO 91/13972).

A large number of techniques in molecular biology by means of which novel transgenic plants with altered characteristics can be generated are known in principle; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory

Manual, 2nd Ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or

Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim 2nd Edition 1996, or Christou, "Trends in Plant Science" 1 (1996) 423-431).

In order to perform such genetic engineering manipulations, nucleic acid molecules may be introduced into plasmids which allow mutagenesis or a sequence change by means of recombination of DNA sequences. It is possible, for example, with the aid of the abovementioned standard methods to perform base exchanges, to remove subsequences or to add natural or synthetic sequences. To connect the DNA fragments to each other, adaptors or linkers may be attached to the fragments.

For example, plant cells with a reduced activity of a gene product can be generated by expressing at least one corresponding antisense RNA, a sense RNA to achieve a cosuppressory effect or by expressing at least one ribozyme of suitable construction which specifically cleaves transcripts of the abovementioned gene product.

To this end it is possible to make use of, on the one hand, DNA molecules which "encompass the entire coding sequence of a gene product inclusive of any flanking sequences which may be present, on the other hand DNA molecules which only encompass parts of the coding sequence, but these parts must be long enough in order to effect, in the cells, an antisense effect. Use may also be made of DNA sequences which show a high degree of homology to the coding sequences of a gene product, but which are not completely identical.

When nucleic acid molecules are expressed in plants, the protein which has been synthesized may be located in any desired compartment of the plant cell. However, to achieve localization in a particular compartment, it is possible, for example, to link the coding region with DNA sequences which guarantee localization in a particular compartment. Such sequences are known to the skilled worker (see, for example,

Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci.

USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).

The transgenic plant cells may be regenerated by known techniques to give complete plants. In principle, the transgenic plants can be plants of any desired plant species, that is to say monocotyledonous and also dicotyledonous plants.

This allows transgenic plants to be obtained which exhibit altered characteristics by means of overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or by means of expression of heterologous (= foreign) genes or gene sequences.

The compounds of formula (I) can preferably be employed in transgenic crops which are resistant to herbicides from the group of the sulfonylureas, glufosinate- ammonium or glyphosate-isopropylammonium and analogous active substances or in analogous showing altered phenotypes, like but not limited to features as for content modification, altered flowering time, male or female sterile plants, environmentally resistant plants due to expression or repression of endogenous or exogeneous genes in the transgenic crop.

The use according to the invention for plant growth regulation also includes the case where the compounds of formula (I) are only formed in the plant or the soil from a precursor (“prodrug”) after its application to the plant. .

The compounds of formula (I) can be employed in the conventional preparations as wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules.

The invention therefore also relates to plant growth regulating compositions which comprise compounds of formula (I).

According to a further feature of the present invention, there is provided a plant growth regulating composition comprising an effective amount of a compound of formula (1) as defined above or an agriculturally acceptable salt thereof, in association with, and preferably homogeneously dispersed in, one or more compatible agriculturally- acceptable diluents or carriers and/or surface active agents

[i.e. diluents or carriers and/or surface active agents of the type generally accepted in the art as being suitable for use in herbicidal compositions and which are compatible with compounds of the invention]. The term "homogeneously dispersed” is used to include compositions in which the compounds of formula (I) are dissolved in other components. The term "growth regulating composition” is used in a broad sense to include not only compositions which are ready for use as herbicides but also concentrates which must be diluted before use (including tank mixtures).

The compounds of formula (1) can be formulated in various ways, depending on the prevailing biological and/or chemico-physical parameters. Examples of possible formulations which are suitable are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), dispersions on an oil or water basis, solutions which are miscible with oil, capsule suspensions (CS), dusts (DP), seed-dressing products, granules for broadcasting and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.

These individual formulation types are known in principle and described, for example, in: Winnacker-Kuchler, "Chemische Technologie” [Chemical Technology],

Volume 7, C. Hauser Verlag, Munich, 4th Edition 1986; Wade van Valkenburg, "Pesticide Formulations”, Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying

Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers”, 2nd Ed., Darland Books,

Caldwell N.J.; H.v. Olphen, "Introduction to Clay Colloid Chemistry”, 2nd Ed., J.

Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1963;

McCutcheon's "Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood

N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents”, Chem. Publ. Co.

Inc., N.Y. 1964; Schénfeldt, "Grenzflichenaktive Athylenoxidaddukte® [Surface- active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-

Kichler, "Chemische Technologie” [Chemical Technology}, Volume 7, C. Hauser

Verlag, Munich, 4th Ed. 1986.

Based on these formulations, it is also possible to prepare combinations with pesticidally active substances such as, for example, insecticides, acaricides, herbicides, fungicides, and with safeners, fertilizers and/or growth regulators, for example in the form of a readymix or a tank mix.

Wettable powders are preparations which are uniformly dispersible in water and which, besides the compounds of formula (I), also comprise ionic and/or nonionic surfactants (wetters, dispersants), for example, polyoxyethylated alkylphenols, } polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglyco! ether sulfates, alkanesulfonates or alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6"-disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurinate, in addition to a diluent or inert substance. To prepare the wettable powders, the compounds of formula (1) are, for example, ground finely in conventional apparatuses such as hammer mills, blower mills and air-jet mills and mixed with the formulation auxiliaries, either concomitantly or thereafter.

Emulsifiable concentrates are prepared, for example, by dissolving the compounds of formula (1) in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of these, with addition of one or more ionic and/or nonionic surfactants (emulsifiers). Emulsifiers which can be used are, for example: calcium salts of alkylarylsulfonic acids, such as calcium dodecylbenzenesulfonate or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty acid esters.

Dusts are obtained by grinding the active substance with finely divided solid substances, for example talc or natural clays, such as kaolin, bentonite or pyrophyllite, or diatomaceous earth.

Suspension concentrates may be water- or oil-based. They can be prepared, for example, by wet grinding by means of commercially available bead mills, if appropriate with addition of surfactants, as they have already been mentioned above for example in the case of the other formulation types.

Emulsions, for example oil-in-water emulsions (EW), can be prepared for example by means of stirrers, colloid mills and/or static mixtures using aqueous organic solvents and, if appropriate, surfactants as they have already been mentioned above for example in the case of the other formulation types.

Granules can be prepared either by spraying the compounds of formula (I) onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carriers such as sand, kaolinites or of granulated inert material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or alter- natively mineral oils. Suitable active substances can also be granulated in the manner which is conventional for the production of fertilizer granules, if desired in a mixture with fertilizers.

Water-dispersible granules are prepared, as a rule, by the customary processes such as spray-drying, fluidized-bed granulation, disk granulation, mixing in high- speed mixers and extrusion without solid inert material. To prepare disk, fluidized- bed, extruder and spray granules, see, for example, processes in “Spray-Drying

Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration",

Chemical and Engineering 1967, pages 147 et seq.; "Perry's Chemical Engineer's

Handbook", 5th Ed., McGraw-Hill, New York 1973, p. 8-57.

For further details on the formulation of crop protection products, see, for example,

G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed.,

Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

As a rule, the agrochemical preparations comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of compounds of formula (1).

The concentration of compounds of formula (1) in wettable powders is, for example, approximately 10 to 90% by weight, the remainder to 100% by weight being composed of customary formulation components. In the case of emulsifiable concentrates, the concentration of compounds of formula (I) can amount to approximately 1 to 90, preferably 5 to 80% by weight. Formulations in the form of dusts usually comprise 1 to 30% by weight of compounds of formula (1), preferably in most cases 5 to 20% by weight of compounds of formula (I), while sprayable solutions comprise approximately 0.05 to 80, preferably 2 to 50% by weight of compounds of formula (I). In the case of water-dispersible granules, the content of compounds of formula (I) depends partly on whether the compounds of formula (1) are in liquid or solid form and on which granulation auxiliaries, fillers and the like are being used. The water-dispersible granules, for example, comprise between 1 and 95% by weight of active substance, preferably between 10 and 80% by weight.

In addition, the formulations of compounds of formula (I) mentioned comprise, if appropriate, the adhesives, wetters, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors, pH regulators and viscosity regulators which are conventional in each case.

Suitable formulations for plant growth regulating compositions are known. A description of suitable formulations which may be used in the method of the invention can be found in international patent publications WO 87/3781, WO 93/6089, and WO 94/21606 as well as in European patent application EP 295117, and US Patent 5,232,940. Formulations or compositions for plant growth regulating uses can be made in a similar way, adapting the ingredients, if necessary, to make them more suitable to the plant or soil to which the application is to be made.

The compounds of the formula (1) or their salts can be employed as such or in the form of their preparations (formulations) as combinations with other pesticidally active substances, such as, for example, insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or further growth regulators, for example as a premix or as tank mixes.

It has been found that, surprisingly, the compounds of formula (I) and most especially compounds 1.1; 1.2; 1.3; 1.4; 1.5; 1.6; 1.7; 1.8; 1.9; 1.10; 1.11; 1.12; 1.13; 1.34; 1.35; 1.36; 1.37; 1.65; 1.96; 1.123; 1.133; 1.134; 1.135; 1.136; 1.137: 1.138; 1.139; 1.140; 1.141; 1.142; 1.143; 1.144; 1.145; 1.166; 1.167; 1.168; 1.169; 1.197; 1.228; 1.255; 1.268; 1.3291.399; 1.400; 1.461; 1.532; 1.664; 1.796; 2.1; 2.10; 2.11: 16 3.2; 3.3; 3.4; and 3.10 display a significant role concerning plant growth properties, which can be different due to an application at various crops. For example example, compound 1.136 show significant effects of approximately the same size by being used as plant growth regulator in maize and wheat but at different concentration.

Compound 1.141 shows a remarkable effect as plant growth regulator in maize and a superior effect in wheat.

By virtue of the practice of the present invention a wide variety of plant growth responses, including the following (non-ranked listing), may be induced: a) more developed root system b) tillering increase

Cc) increase in plant height d) bigger leaf blade e) less dead basal leaves f) stronger tillers g) greener leaf color h) less fertilizers needed i) less seeds needed i) more productive tillers

Kk) less third non-productive tillers 1) earlier flowering m) early grain maturity n) less plant verse (lodging) 0) longer panicles p) increased shoot growth q) improved plant vigour r) early germination ’

Ss) more fruit and better yield

It is intended that as used in the instant specification the term “method for plant growth regulation” or “method for plant growth regulation” means the achievement of any of the aforementioned nineteen categories of response or any other modification of plant, seed, fruit or vegetable (whether the fruit or vegetable is nor harvested or harvested) so long as the net result is to increase growth or benefit any property of the plant, seed, fruit or vegetable as distinguished from any pesticidal action (unless the present invention is practised in conjunction with or in the presence of a pesticide, for example a herbicide). The term “fruit” as used in the instant specification is to be understood as meaning anything of economic value that is produced by the plant.

Preferably, at least an increase of 10% of one or more of the respective plant growth response is obtained.

The 5-amino-1-arylpyrazole-3-carbocylic acid derivative of formula (I) may be applied for plant growth regulating purposes to the foliage of plants and/or to the soil in which said plants are growing. Applications to the soil are often in the form of granules which are usually applied in sufficient amount to provide a rate of from about 0.00001 kg/ha to about 0.5 kg/ha of active ingredient, preferably between 0.00001 and 0.1 kg/ha, more preferably between 0.00001 kg/ha and 0.01 kg/ha.

A preferred embodiment of the invention is a method for plant growth regulation comprising applying to the seeds from which said plants grow, prior to said seeds, a non-phytotoxic, effective plant growth regulating amount of a compound having the formula (I). The seed may be treated, especially by coating or embedding or impregnation or soaking or dipping in liquid or paste formulations which are known per se and are subsequently dried. Seed comprising 0.1 to 1000 gram per 100 kg of a compound of formula (I), preferably 0.1 to 800 g per 100 kg, most preferably 0.1 to 250 g per 100 kg are particularly appropriate for this purpose.

The precise amount of 5-amino-1-arylpyrazole-3-carbocylic acid derivative of formula (1) to be used will depend, inter afia, upon the particular plant species being treated.

A suitable dose may be determined by the man skilled in the art by routine experimentation. The plant response will depend upon the total amount of compound used, as well as the particular plant species which is being treated. Of course, the amount of 5-amino-1-arylpyrazole-3-carbocylic acid derivative of formula (I) should be non-phytotoxic with respect to the plant being treated.

Although the preferred method of application of the compounds used in the process of this invention is directly to the foliage and stems of plants, the compounds can be applied to the soil in which the plants are growing.

The following examples are illustrative of methods of plant growth regulation according to the invention, but should not be understood as limiting the invention as modifications in materials and methods will be apparent to the skilled worker. All measurements of plant growth regulating effects were determined either by using a protoplast screening assay and/or by using a root growth assay and/or by applying the compounds pre-selected the before defined assay system under natural growth conditions in field trials. In all cases, untreated protoplasts, plants or plants parts , or seeds were taken as a control.

B. Biological Examples : Example 1. Plant Protoplast System

The present invention features a so called high throughput assay for a rapid screening of chemical compounds that modulate cell growth. The assay in general involves: a) plant protoplasts grown in liquid medium, b) a library of chemical compounds, and c) screening the protoplasts to identify the compounds which affect significantly the cell growth and development.

Protoplast preparation:

Preferably the protoplasts were prepared from cell suspensions derived from maize callus. The protoplasts were obtained by enzymatic digestion of the cell aggregates in the suspension. The cells were digested for 3-6 hours at room temperature in a cellulase-pectolyase mix, Protoplasts were released by gentle shaking, filtered through a 45 um mesh and collected by centrifugation. After digestion, the protoplasts were washed several times to remove cell debris and enzyme residues and then re-suspended in culture medium. The protoplasts were plated in 50 - 100 pl aliquots in microtiter wells at a density ranging from 100.000 - 2,000.000 protoplasts per ml, preferably at a concentration of 800.000 protoplasts/ml.

Screening assay:

To identify chemical compounds that modulate the cell growth, maize protoplasts were incubated with a library of chemical compounds in 96-well microtiter plates.

Following the incubation at 25°C for 1-14 days, preferably 7-10 days, the protein content was measured by Coomassie dye based colorimetric assays. The growth of the cells treated with the chemical compounds invoived in the test was detected by comparison with untreated protoplasts.

Treatment with a section of compounds derived from formula (1) show an increase of more than 50% over the untreated control.

Claims

1. Use of a compound of formula (1) or an agriculturally acceptable salt thereof for plant growth regulation R2 Ri TT R3 N~

PN. “~ Re 0) wherein: R'is CONR®R” or CO.R®,; W is C-halogen or N; : R?is H or S(O)mR’; R®is NR"R", halogen, OH, (C1-Cg)-alkoxy, (C2-Cg)-alkenyloxy or (C2-Cs)-alkynyloxy; R*is H, or halogen; R® is (C4-Cq)-haloalkyl or (C4-C4)-haloalkoxy; R® is H, (C1-Cs)-alkyl, (C1-Cg)-haloalkyl, (C4-Cs)-alkoxy-(C4-Ce)-alkyl, (Co- Cs)-alkenyl, (C2-Cg)-haloalkenyl, (C2-Cé)-alkynyl, (C2-Cg)-haloalkynyl, (Cs- Cr)-cycloalkyl, (C3-Cy)-cycloalkyl-(C4-Cs)-alkyi, (C4-Cs)-alkoxy, (C+- Ce)-alkylthio, (CH2)aR"?, (CH2),R", (C4-Ce)-alkyl-CN, (C1-Cg)-alkyl-NR'°R"! or (C1~Cg)-alkyl- S(O)R®; R’ is H, (C1-Cg)-alkyl, (C3-Cs)-alkeny! or (C-Cg)-alkynyl; or R® and R’ together with the attached N atom form a five- or six-membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C,- Ce)-alkyl and (C4-Cs)-haloalkyl;

R®is H, (C4-Cs)-alkyl, (C1-Ce)-haloalkyl, (C>-Cs)-alkenyl, (C,-Ce)-alkynyl or (CH2).R'% R? is (C1-Ce)-alkyl or (C1-Cs)-haloalkyl; R' and R" are each independently H, (C1-Ce)-alkyl, (C1-Ce)-haloalkyl, (Cz- Ce)-alkenyl, (C>-Cg)-haloalkenyl, (C2-Cg)-alkynyl, (C3-Cs)-cycloalkyl, (Cs-Ce)-cycloalkyl-(C+-Cs)-alkyl, COR™ or CO.R'S; or R' and R™ together with the attached N atom form a five- or six-membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (Cs- Ce)-alkyl and (C4-Cg)-haloalkyl; R'is phenyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C;-Ce)-alkyl, (C4-Cs)-haloalkyl, (C4-Cs)- alkoxy, (C1-Cg)-haloalkoxy, CO,R'€, CN, NO, S(0),R°, COR'S, CONR'R", NR'"R' and OH; R'is heterocyclyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-Ca)-alkyl, (C1-Cs)-haloalkyl, (C4-Ca)-alkoxy, (C4-Cs)-haloalkoxy, NO, CN, COR, S(0),R®, OH and oxo; R™ and R" are each independently H, (C;-Cs)-alkyl, (C1-Cg)-haloalkyl, (Cx- Ce)-alkenyl, (C2-Ce)-haloalkenyl, (C2-Ce)-alkynyl or (C4-Cs)-alkoxy-(C1- Cs)-alkyl; R'® and R" are each independently H, (C1-Ce)-alkyl or (C1-Cg)-haloalkyl; m, q and r are each independently 0, 1 or 2; n and p are each independently 0, 1, 2, 3 or 4; and each heterocyclyl in the above-mentioned radicals is independently a heterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 heteroatoms in the ring selected from the group consisting of N, O and S.

2. The use of a compound as defined in claim 1, in which in which R'is CONR®R’; Wis C-Clor C-Br RZ is S(O)nR%;

0 90 R%is NR'"R", halogen, OH, (C;-Cs)-alkoxy, (C2-Cs)-alkenyloxy or (C2-Ce)-alkynyloxy; R*is Cl or Br; R® is CF3 or OCF3;

R®is H, (C1-Ca)-alkyl, (C1-C4)-haloalkyl, (C4-Csa}-alkoxy-(C4-C3)-alkyl, (Ca- Ca)-alkenyl, (C3-Cq4)-haloalkenyl, (C3-C4)-alkynyi, (Cs-Ca)-haloalkynyl, (Cs- Ce)-cycloalkyl, (C3-Ce)-cycloalkyi-(C4-Cs)-alkyl, (C4-Cs)-alkoxy, (C4- Ca)-alkylthio, (CH2)aR? or (CH,),R™;

Ris H, (C4-Cs)-alkyl, (Ca-Cy)-alkenyl or (C3-Cy4)-alkynyl; or preferably R® and R’ together with the attached N atom form a five- or six- membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C+-Cs)-alkyl and (C+-Cs)-haloalkyl; R? is (C1-Cs)-alkyl or (C+-Ca)-haloalkyl (more preferably R® is CF); ~ Rand R" are each independently H, (C1-Ca)-alkyl, (C1-C3)-haloalkyl, (Cs- Ca)-alkenyl, (C3-Cs)-haloalkenyl, (C3-C,)-alkynyl, (C3-Cs)-cycloalkyl, (C3-Cs)-cycloalkyl-(C4-C3)-alkyl, COR™ or COR; or R' and R"" together with the attached N atom form a five- or six-membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from 0,8 and N; the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C;- Ca)-alkyl and (C4-C3)-haloalkyi; R'is phenyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-Cs)-alkyl, (C1-Cs)-haloalkyl, (C1-C3)- alkoxy, (C1-Cs)-haloalkoxy, COR", CN, NO,, S(0),R®, COR’, CONR'R", NR'R' and OH; R™ is heterocyclyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-Cs)-alkyl, (C4-C3)-haloalky}, (C1-Ca)-alkoxy, (C4-Cs)-haloalkoxy, NO, CN, COR, S(O),R®, OH and oxo;

y 91 R™ and R" are each independently H, (C1-Cs)-alkyl, (C1-Ca)-haloalkyl, (Cz- Ca)-alkenyl, (C2-Cs)-haloalkenyl, (C,-Cs)-alkynyl or (C1-Ce)-alkoxy-(C- Cs)-alkyl; R'™ and R" are each independently H, (C1-Cs)-alkyl or (C1-C;)-haloalkyl; and each heterocyclyl in the above-mentioned radicals is independently a heterocyclic radical having 3 to 6 ring atoms and 1, 2 or 3 hetero atoms in the ring selected from the group consisting of N, O and S.

3. The use of a compound as defined in claim1, in which R'is CONR®R"; Wis C-CI; R?is H, or S(O)mR%; R® is NR'™R", halogen, OH or (C4-Cs)-alkoxy: Ris Cl; R®is CFs; R® is H, (C4-Cy)-alkyl, (C1-C3)-alkoxy-(Cq-Co)-alkyl, (C3~C4)-alkenyl, (Cs- Ca)-alkynyl, (C3-Cs)-cycloalkyl, (C3-Cg)-cycloalkyl-(C4-Cy)-alkyl, (C4-C3)-alkoxy, (C1-Ca)-alkylthio, (CH2).R" or (CH2),R™; R” is H, (C4-Cs)-alkyl, (C3-Cs)-alkenyl or (C3-C4)-alkynyl; R® is methyl, ethyl or CFs; R'® and R"" are each independently H, (C+-Ca)-alkyl, (Cs-Cs)-haloalkyl, (Cs- C4)-alkenyl, (C3-Cy)-haloalkenyl, (C3-C4)-alkynyl, (C3-Ce)-cycloalkyl, (C3-Cs)-cycloalkyl-(C4-C3)-alkyl, COR or COR"; or R* is phenyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-Cs)-alkyl, (C4-C3)-haloalkyl, (C4-C3)- alkoxy, CO2R'®, CN and NO; R™ is heterocyclyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C4-Cs)-alkyl, (C4-Cs)-haloalkyl, (C+-Ca)-alkoxy, (C4-Cs)-haloalkoxy, NO,, CN, COR", S(0),R®, OH and oxo; R™ and R" are each independently (C1-Cs)-alkyl; R' and R"” are each independently H or (Cs-Cs)-alkyl: and each heterocyclyl in the above-mentioned radicals is independently a heterocyclic radical having 3 to 6 ring atoms and 1, 2 or 3 hetero atoms in the ring selected from the group consisting of N, O and S.

4 The use of a compound as defined in claim 1, in which R'is CONR®R’; Wis C-CI; RZ is H, or S(O)}mR?; R®is NHR"; Riis CI; R%is CFs; R%is H, (C1-Cs)-alkyl, (C1-Co)-alkoxy-(C+-Cz)-alkyl, (C3-C4)-alkenyl, (Cs- Ca)-alkynyi, (C3-Cg)-cycloalkyl, (Cs-Ce)-cycloalkyl-(C4-C,)-alkyl, furfuryl or tetrahydrofurfuryl; R” is H or (C4-Ca)-alkyl: R? is methyl, ethyl or CF3; and R'is H, methyl or ethyl.

5. The use of a compound as defined in claim 1, in which R'is COR, Wis C-CI; RZ is H, or S(O)mR?; Ris NR'R"", R*is CI; R®is CFs; R® is H, methyl! or ethyl; R? is methyl, ethyl or CFs; R'is H, methyl or ethyl; and R'is H.

6. The use of a compound as defined in claim 1, in which R'is CONR®R;

Wis C-CI; R? is S(O)mCF3; R®is NR"R", halogen, OH or (C4-C,)-alkyl; Ris Cl; RS is CF3; R® is H or (C4-Ca)-alkylthio: Ris H; R'is (C4-Ca)-alkyl, COR" or COR": R", R"and R* are each independently (C+1-C3)-alkyl.

7. A composition for plant growth regulation, which comprises one or more compounds of formula (I) as defined in anyone of claims 1 to 6 or an agriculturally acceptable salt thereof, carriers and/or surfactants useful for plant protection formulations.

8. The composition as claimed in claim 7 , which comprises a further active compound selected from the group consisting of acaricides, fungicides, herbicides, insecticides, nematicides or plant growth regulating substances not identical to compounds defined by formula (1) of claim 1. :

9. The use of a composition as claimed in anyone of claims 7 to 8 for plant growth regulation, in which the plant is a monocotyledoneous or dicotyledoneous crop plant.

10. The use as claimed in claim 9, wherein the plant is selected from the group consisting of wheat, barley, rye, triticale, rice, maize, sugar beet, cotton, or soybeans.

11. A method for growth regulation in field crop plants, which comprises applying an effective amount of a compound of formula (I) as defined in claims 1 to 6 to the site where the action is desired said method comprising applying to plants, to seeds from which they grow or to the locus in which they grow, a non-

phytotoxic, effective plant growth regulating amount of one or more compounds of formula (1).

12. A method as claimed in claim 11 that results into a yield increase of at least 10% concerning the plants to which it is applied.

13. A compound as defined by formula (1), or a salt thereof, R2 RY: JI R3 N~ R~—~Z"w ~ RS mH wherein:

i. R'is COR? RZ? is H or S(O)nR®; R? R*, R5 W and m are as defined in claim 1: R8is H; and R?® is (C2-Ce)-alkyl or (C;-Cg)-haloalkyl; or i. R'is CONR®R’; Ris (C4-Ce)-alkyl, (C4-Cs)-haloalkyl, (C4-Ce)-alkoxy-(C4-Cg)-alkyl, (Co- Ce)-alkenyl, (C2-Cg)-haloalkenyl, (C2-Cs)-alkynyl, (C2-Ce)-haloalkynyl, (C3-Cr)-cycloalkyl, (C3-C7)-cycloalkyl-(C+-Cs)-alkyi, (C4-Ce)-alkoxy, (C4- Ce)-alkyithio, (CH)sR"2, (CH2),R™, (C4-Cs)-alkyl-CN, (C4-Ce)-alkyl-NR'"R" or (C1-Cs)-alkyl- S(O}R®: or

R® and R together with the attached N atom form a five- or six- membered saturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-Ce}-alkyl and (C4-Cs)-haloalkyl; and

RZ R3, RY, RP RT, R% RO, R", R™ R™ W,n, p and rare as defined in formula (1);

with the exclusion of the compound wherein:

R'is CON(CHa)y; R? is CF3S; R® is OH; R* is Cl; R® is CF; and W is C-Cl.