AU626913B2 - 2-amino-pyrimidine derivatives - Google Patents

Abstract

Compounds of the formula <IMAGE> in which: R1 denotes phenyl or phenyl which is monosubstituted to trisubstituted by R4; R2 denotes hydrogen, C1-C5-alkyl, C1-C5-alkyl substituted by the radicals OR5 or SR5, C3-C6-cycloalkyl, C3-C6-cycloalkyl monosubstituted to trisubstituted by C1-C4-alkyl or halogen, C2-C5-alkenyl, C2-C5-alkynyl or the formyl radical; R3 denotes hydrogen, C1-C4-alkyl, C1-C4-alkyl which is substituted by halogen, cyano or the radicals OR5 or SR5, C3-C6-cycloalkyl or C3-C6-cycloalkyl which is monosubstituted to trisubstituted by C1-C4-alkyl or halogen; R4 denotes halogen, C1-C3-alkyl, C1-C2-haloalkyl, C1-C3-alkoxy or C1-C3-haloalkoxy; R5 denotes hydrogen, C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl or the radical (CH2)n-X-C1-C3-alkyl; R7 denotes the group -NH2, <IMAGE> or <IMAGE>; R8 denotes hydrogen, C1-C3-alkyl or C1-C3-haloalkyl; R9 denotes hydrogen, C1-C8-alkyl, C1-C3-alkyl substituted by hydroxyl, OR12, SR12 or N(R12)2, C3-C6-cycloalkyl, cyclopropyl substituted by SR12, C3-C10-alkenyl, C1-C3-haloalkyl, phenyl, phenyl which is monosubstituted to trisubstituted by halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C2-haloalkyl, hydroxyl, nitro, cyano, amino or dimethylamino, 1- or 2-naphthyl, 1-, 2- or 3-pyridyl, <IMAGE> or <IMAGE>; R8 and R9, together with the carbon atom in the radical R7, form a saturated or unsaturated ring consisting of 4 to 7 carbon atoms; R10 denotes CH(R8)R9, phenyl, C3-C5-alkenyl, C3-C5-alkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R11 denotes hydrogen, C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R12 denotes CH3 or C2H5; X denotes oxygen or sulphur; Z denotes O, S, NH or NCH3; and n denotes 1 to 3; including their acid addition salts and metal salt complexes, have useful microbicidal properties. The novel active compounds can be employed in plant protection for preventing the attack of crop plants by phytopathogenic microorganisms or by harmful insects and for controlling these pests.

Description

P/00/011 Regulation 3.2

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

NOTICE

1. The specification should describe the invention in full and the best method of performing it known to the applicant.

2. The specification should be typed on as many sheets of good quality A4 International size paper as are necessary and inserted inside this form.

3. The claims defining the invention must start on a new page. if there is insufficient space on this form for the claims, use separate sheets of paper.

The words The claims defining the invention are as follows' should appear before claim 1. After the claims the date and the name of the applicant should appear in block letters.

4. This form must be accompanied by a true and exact copy of the description, claims and drawings (if any) and an additional copy of the claims.

(see Pamphlets explaining formal requirements of specifications and drawings) TO BE COMPLETED BY APPLICANT Name of Applicant.-' Address for Invention Title: l. S r vA xv Details of Associated Provisional Applications: Nos: T ollowing statement is a full description of this invention, including the best S etpod of performing it known to me:- \S f 11' 111.

5-17200/1+2/= Abstract Compounds of the formula R72 \R3 wherein: Ri is phenyl or phenyl mono- to tni-substituted by R 4

R

2 is Shydrogen, CI-C 5 alkyl, Cj-G 5 alkyl substituted by the radical ORB or by the *oaradical SR 5 C3-Cscycloalkyl, C3-C 6 cycloalkyl mono- to tni-substituted by CI-C~alkyl or by halogen, C-aleyC-CSalkynyl or the formyl radical; R 3 is hydrogen, CI-C~alkyl, C1-Ct~alkyl substituted by halogen, a..cyano or by the radical ORB or by the radical SR 5

C

3

-C

6 cycloalkyl or C3-Cscycloalkyl mono- to tni-substituted by C 1 -Ci 4 alkyl or by halogen; R 4 is halogen, Cl-C 3 alkyl, CI-C 2 haloalkyl, CI-C 3 alkoxy or CI-C 3 haloalkoxy;

R

5 is hydrogen, Cl-Csalkyl, C3-C5alkenyl, C3-C 5 alkynyl or the radical

(CH

2 n-X-Ci-C 3 -alkyl; nR

R

7 is the group -NH 2 ,-NC o R8 s hdroenCI-~alylor Cl-C 3 haloalkyl; R9 is hydrogen, C 1 -Caalkyl,

CI-C

3 alkyl substituted by hydroxy, 0R 12 SR1 2 or by N(Rl 2 2

C

3 -CsCYCloalkyl, cyclopropyl substituted by SR 12

C

3 -Cloalkenyl, Cl-C 3 haloalkyl, phenyl, phenyl mono- to tni-substituted by halogen, Cl-C 3 alkyl, C 1

-C

3 alkoxy, CI-C 3 haloalkoxy, C1-C2haloalkyl, hydroxy, nitro, cyano, amino or by dimethylamino, 1- or 2-naphthyl, 2- or 3-pyridyl, or* K

A/

n~-

IA-

Rs and R 9 together with the carbon atom in the radical R 7 are a saturated or unsaturated ring comprising 4 to 7 carbon atoms; Rio is CH(Rs)R 9 phenyl, C3-Csalkenyl, C 3 -Csalkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R 1 1 is hydrogen, Ci-Csalkyl, C 3 -Csalkenyl, C 3 -Csalkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R 1 2 is CH 3 or C 2 Hs; X is oxygen or sulfur; Z is 0, S, NH or NCH 3 and n is 1 to 3; including the acid addition salts and metal salt complexes thereof, have valuable microbicidal properties. The novel compounds can be used in plant protection for preventing attacks on cultivated plants by phytopathogenic microorganisms or by insect pests and for controlling those microorganisms and pests.

A 4 go 4 4 ,0 l

I

j^ 1.i 1 5-17200/1+2/= Pesticides The present invention relates to novel substituted 2-aminopyrimidine derivatives of formula I below. It also relates to the preparation of those compounds and to agrochemical compositions that contain at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or the compositions for controlling pests, especially plantdestructive microorganisms, particularly fungi.

The pyrimidine compounds according to the invention have the general formula I S.o R2 o 99 *o

R

7

N'R

s9 *\R3 wherein: R 1 is phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, Ci-Csalkyl, C 1 -Csalkyl substituted by the radical ORs or by the radical SRs, C3-C6cycloalkyl, C 3 -Cscycloalkyl mono- to tri-substituted by Cl-Cialkyl or by halogen, C2-Csalkenyl, Cz-Csalkynyl or the formyl radical; R 3 is hydrogen, Cl-C+alkyl, Cl-C4alkyl substituted by halogen, *cyano or by the radical ORs or by the radical SRs, C3-C6cycloalkyl or C3-C 6 cycloalkyl mono- to tri-substituted by CL-Calkyl or by halogen; R 4 is halogen, C 1 -Caalkyl, C1-C 2 haloalkyl, CI-C3alkoxy or Cl-C 3 haloalkoxy; Rs is hydrogen, C 1 -Csalkyl, C 3 -Csalkenyl, C3-Csalkynyl or the radical

(CH

2 -X-Ci-C 3 -alkyl;

R

7 is the group -NH 2 Or -NR .9 11

R

8 is hydrogen, Ci-C 3 alkyl or Ca-C3haloalkyl; R 9 is hydrogen, C1-Caalkyl, CI-Caalkyl substituted by hydroxy, OR 1 2

SR

12 or by N(R 12 2 C3-C6cycloalkyl, cyclopropyl substituted by SR 12 C3-Cloalkenyl, Cl-C3haloalkyl, LA 2 phenyl, phenyl mono- to tri-substituted by halogen, C 1

-C

3 alkyl, CI-C 3 alkoxy, Ci-C 3 haloalkoxy, Ci-Czhaloalkyl, hydroxy, nitro, cyano, amino or by dimethylamino, 1- or 2-naphthyl, 2- or 3-pyridyl, or

R

8 and R 9 together with the carbon atom in the radical R 7 are a saturated or unsaturated ring comprising 4 to 7 carbon atoms; Rio is CH(Rs)R 9 phenyl, C3-Csalkenyl, C 3 -Csalkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R 11 is hydrogen, Ci-Csalkyl, C3-Csalkenyl, C3-Csalkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R 12 is CH3 or C 2

H

5 X is oxygen or sulfur; Z is O, S, NH or NCH 3 and n is 1 to 3; including their acid addition salts and metal salt complexes.

Depending on the number of carbon atoms indicated, "alkyl" by itself or as a constituent of another substituent, such as haloalkyl, alkoxy or S haloalkoxy, is to be understood as being, for example, methyl, ethyl, I propyl, butyl or pentyl and isomers thereof, for example isopropyl, isobutyl, tert.-butyl or sec.-butyl. Halogen is fluorine, chlorine, bromine Sor iodine, preferably fluorine, chlorine or bromine. Haloalkyl and haloalkoxy are mono- to per-halogenated radicals, for example CHCl 2

CH

2

F,

CC1 3 CHzCl, CHF 2

CF

3

CH

2

CH

2 Br, C 2 C1 5

CH

2 Br, CHBrCl etc., preferably

CF

3 Depending on the number of carbon atoms indicated, cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

The compounds of formula I are oils, resins or solids that are stable at room temperature and are distinguished by valuable microbicidal properties. They can be used preventively or curatively in the agricultural sector or related fields for controlling plant-destructive micro- SI, organisms. The compounds of formula I according to the invention, when Sused in low concentrations, are distinguished not only by excellent insecticidal and fungicidal activity but also by particularly good plant compatibility.

ar~ Ill*aclr~' 3 The invention relates both to the free compounds of formula I and to their addition salts with inorganic and organic acids and to their complexes with metal salts.

Salts according to the invention are especially addition salts with non-harmful inorganic or organic acids, for example hydrohalic acids, for example hydrochloric, hydrobromic or hydriodic acid, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid or organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or 1,2-naphthalene-disulfonic acid.

Metal salt complexes of formula I comprise the fundamental organic molecule and an inorganic or organic metal salt, for example the halides, "a nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroo acetates, propionates, tartrates, sulfonates, salicylates, benzoates, etc. of the elements of the second main group, such as calcium and magnesium, and of the third and fourth main groups, such as aluminium, tin or lead, and of the first to eighth sub-groups, such as chromium, 4 S manganese, iron, cobalt, nickel, copper, zinc, etc.. The sub-group elements of the 4th period are preferred. The metals may be present in any of the various valencies attributed to them. The metal complexes may be mononuclear or polynuclear, that is to say, they may contain one or S more organic molecular components as ligands.

S Important groups of plant fungicides are compounds of formula I in which A the symbols have the following meanings: Group 1 (Substituents) SRI is phenyl or phenyl mono- to tri-substituted by R 4

R

2 is hydrogen, C1-Csalkyl, Ci-Csalkyl substituted by the radical ORs or by the radical SRs, C3-C6cycloalkyl, C3-Cscycloalkyl mono- to tri-substituted by CI-C4alkyl or by halogen, Cz-Csalkenyl, Cz-Csalkynyl or the formyl radical; R 3

LA

-4is C1-Coalkyl, C1-Cialkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, C 3 -Cscycloalkyl or C 3 -Cocycloalkyl mono- to tri-substituted by C1-Csalkyl or by halogen; R4 is halogen or C 1

-C

3 alkyl; Rs is hydrogen, CI-Csalkyl, C3-Csalkenyl, C 3 -Csalkynyl or the radical

(CH

2 )n-X-C 1

-C

3 alkyl; Rs is hydrogen, Ca-Csalkyl, C 3 -Cscycloalkyl, C 3

-C

5 alkenyl, CI-C 3 haloalkyl, phenyl or phenyl mono- to tri-substituted by halogen, methyl, methoxy, halomethoxy or by halomethyl; R 8 and R 9 together with the carbon atom in the radical R 7 are a saturated or unsaturated ring comprising 5 or 6 carbon atoms; R 7

R

0 io, R 11

R

12 and Z are as defined under formula I and halogen is preferably fluorine, chlorine or bromine, X is oxygen or sulfur; n is 1 to 3.

Group 2 (Substituents)

R

1 is phenyl or phenyl mono-substituted by halogen; R 2 is hydrogen, C1-Csalkyl, C 1 -Csalkyl substituted by ORs, C3-Cscycloalkyl, C3-C6cyclo- 0 o 00 alkyl mono- to tri-substituted by Ca-CLalkyl or by halogen, Cz-Csalkenyl, n0 0 @@0 S Cz-Csalkynyl or the formyl radical; R 3 is C 1 -C4alkyl, C-C 4 alkyl substituted by halogen, cyano or by ORs, C 3 -Cscycloalkyl or C 3 -Cscycloalkyl 0.0 substituted by methyl; Rs is hydrogen or C 1 -Czalkyl; R 9 is hydrogen, 0 0 C1-Csalkyl, Ca-C6cycloalkyl, C3-Csalkenyl, C 1 -C3haloalkyl, phenyl or "000 phenyl mono- to tri-substituted by halogen, methyl, methoxy, halomethoxy or by halomethyl; R 8 and R9, together with the carbon atom in the radical

R

7 are a saturated or unsaturated ring comprising 5 or 6 carbon atoms; S R7, Rio, R 11 and R 12 are as defined under formula I and halogen is preferably fluorine, chlorine or bromine.

Group 3 (Substituents)

R

1 is phenyl or phenyl mono- to tri-substituted by R4; R 2 is hydrogen,

C

1 -Csalkyl, C1-Csalkyl substituted by the radical ORs or by the radical C3-Cscycloalkyl, C 3 -Cscycloalkyl mono- to tri-substituted by CI-C 4 alkyl or by halogen, C 2 -Csalkenyl, C2-Csalkynyl or the formyl radical; R 3 is Cl-Cialkyl, Ci-C+alkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, C3-Cscycloalkyl or C3-Cscycloalkyl mono- to tri-substituted by C1-Calkyl or by halogen; R4 is halogen, CI-C3alkyl, CI-C2haloalkyl, C 1 -C3alkoxy or Ca-C3haloalkoxy; Rs is hydrogen, CI-C 5 tI alkyl, C 3 -Csalkenyl, C3-G 5 alkynyl or the radical (GH 2

-_X-G

1

-C

3 alkyl; R 7 is -NH 2 X is oxygen or sulfur; n is 1 to 3; including their acid addition salts and metal salt complexes.

Group 4 (Substituents) RI is phenyl or phenyl mono- to tni-substituted by R4; R 2 is hydrogen, Cl-Csalkyl, Cl-C 5 alkyl substituted by the radical OR 5 or by the radical SRS, C 3 -C~cycloalkyl, C 3 -C~cycloalkyl mono- to tni-substituted by C 1 -Ct4alkyl or by halogen, C 2 -Gsalkenyl, C 2 -Csalkynyl or the fornyl radical; R 3 is Cl-C4alkyl, Cl-Ci~alkyl substituted by halogen, cyano or by the radical or by the radical SR5, G 3 -Cscycloalkyl or C 3

-C

6 cycloalkyl mono- to tni-substituted by Cl-CL~alkyl or by halogen; R4 is halogen; R 5 is hydrogen, CI-Csalkyl, C 3 -Csalkenyl, C 3 -Csalkynyl or the radical

(CH

2 _X-CI-C3alkyl; X is oxygen or sulfur; n is 1 to 3.

09 Group 5 (Substituents) SRI is phenyl or phenyl mono- to tni-substituted by halogen; R 2 is 2 hydrogen, CI-Csalkyl, Ci-Csalkyl substituted by the radical OR5 or by the 'radical SR5, C3-Cscycloalkyl, C 3 -C~cycloalkyl mono- to tni-substituted by CI-C~alkyl or by halogen, C2-Csalkenyl, C 2

-C

5 alkynyl or the formyl radical; R 3 is CI-Cz~alkyl, CI-Ct 4 alkyl substituted by halogen, cyano or by the radical ORs or by the radical SR5, C 3 -Cscycloalkyl or C 3 -C~cycloalkyl mono- to tni-substituted by Cl-Ci~alkyl or by halogen; Rs is hydrogen, Cl-Osalkyl, C3-Csalkenyl, G3-Csalkynyl or the radical (Gil 2 n-X-Cl--G 3 alkyl; X is oxygen or sulfur; n is 1 to 3.

Group 6 (Substituents)

R

1 is phenyl or phenyl mono-substituted by chlorine or by fluorine; R 2 is CI-Osalkyl, or is Ci-C 2 alkyl substituted by ORs, C3-Cscycloalkyl, C 3 -C6- ~tcycloalkyl mono- to tni-substituted by CI-C~alkyl or by halogen, C 2 -Cs-' alkemyl, C 2 -Csalkynyl or the formyl radical; R 3 is Cl-Ci~alkyl, Cl-C4haloalkyl, C 3 -Cscycloalkyl or C3-C6cycloalkyl substituted by methyl; R 5 is hydrogen or Ci-C2alkyl.

-6- Especially preferred are compounds of groups 5 and 6 wherein R 3 is: methyl, fluoromethyl, chioromethyl, bromomethyl, C 3 -C~cycloalkyl or me thoxyme thyl.

The following groups of individual compounds are preferred: Group 1 (Compounds) 4 -fluoromethyl-6-cyclopropylpyrimid-2-yl)-N-phenylhydrazine; 4 -me thyl-6-cyclopropylpyrimid-2-yl) -N-rn-fluorophenylhydrazine;

N-(

4 -methyl-6-cyclopropylpyrimid-2-yl)-N-p-fluorophenylhydrazine; Group 2 (Compounds)

N-(

4 -methyl-6-cyclopropylpyrimid-2-yl)-N-phenylhydrazine; N-(4,6-dimethylpyrimid-2-yl)-N--phenylhydrazine; N-(4-methyl-6-methoxymethyl- 4 00 pyrimid-2-yl)-N-phenylhydrazine; Group 3 (Compounds)

N-(

4 6 -dimnethylpyrimid--2-yl)-N-phenylpropionaldehyde hydrazone;

N-(

4 ,6-dimethylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone;

N-(

4 -methyl-6-methoxymethylpyrimid-2-yl)--N-phenylisobutyraldehyde hydrazone; 4 -methyl-6--methoxymethylpyrimid-2-yl)-N-phenylpropionaldehyde hydrazone; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-Nphenylpropionaldehyde hydrazone; N-(4--methyl-6-cyclopropylpyrimid-2-yl)- N-phenyl-n-butyraldehyde hydrazone; N-( 4 -methyl-6-cyclopropylpyrimid-2yl)-N-phenylisobutyraldehyde hydrazone; N-( 4 -methyl--6-cyclopropylpyrimid- 2-yl)-N-phemyltrichloroacetaldehyde hydrazone; N-( 4 -methyl-6-cyclopropylpyrimid-2-yl)-N-p-fluorophenylacetaldehyde hydrazone; N-(4-methyl-6cyclopropylpyrimid-2-yl).-N--p-fluorophenylisobutyraldehyde hydrazone;

N-(

4 -methyl- 6 -cyclopropylpyrimid-2-yl)-N-rn-fluorophenylisobutyraldehyde hydrazone; G-dimethylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N-46dmtyprmd2y)NpeylN-iehlyrzn;N(,-i N,dmethylpyrimid-2-yl)-N-phenyl-N'-diethylhydrazine; 6-diyinypyrimid-2--yl)pe-N-iyl'n-oylhydrazine; N-(4,thl6-methoy-tyl pyrimid-2-yl) -N-phenyl-N' -isotylhydrazine; 4 -methyl-6-mehoxymethylpyrimid-2-yl)-N-phenyl-N' -methoylhydrazine; 4 -methyl-6-methoxymetylpyrimid-2-yl)-N-phenyl.-N '-dimethylhydrazine; N-C 4 -methyl-6-cyclopropyl- -7pyrimid- 2 -yl)-N-phenyl-N'-methylhydrazine; N-(4-niethyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-isobutylhydrazine; N-(4-methyl-6-cyclopropylpyrimid- 2 -yl)-N-phenyl-N'-dimethylhydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-diethylhydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl) -N-phenyl-N -methyl-N'-et'hylhydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-p-fljorophenyl-N'-ethylh~drazine; N-(4-methyl-6methoxymethylpyrimid-2-yl)-N-m--fluorophenyl-N' -isopropyihydrazine.

The compounds of formula I are prepared as follows: Process (a) Reaction of a pyrimidine derivative of formula II \R3 with a phenylhydrazine derivative of formula III

R

1 -NH-NH-R

I)

im the presence of a base, in an aprotic solvent and at temperatures of to 150'C, preferably -300 to 80'C, wherein Y is halogen, preferably chlorine, the radical S0 2 R6 or N G)(CH 3 3

R

6 is Cl-C~+alkyl, phenyl or phenyl substituted by methyl or by chlorine and R is as defined for RIO and R 11 and the latter and also RI-R 3 are as defined under formula I.

Process (b) Reaction of a pyrimidine hydrazime derivative of formula IV with am aldehyde or ketone of formula V to form a compound of formula VII with the removal of water RB\ R I N- R

/I

(IV) M 9 (VII) R 8 in any desired solvent, in the presence of an acid and at temperatures of -200 to 120 0 C, preferably 100 to 50 0 C, Ri-R 3 and Re and R 9 being as defined under formula I.

Azeotropic distillation or molecular sieves can be used to remove water from the reaction mixture. Drying agents, for example CaCl 2 or Na 2 SOu, can also be used. In the case of the reaction of derivative (IV) with an aldehyde, the removal of water from the reaction mixture can often be dispensed with.

Process (c) Reduction of a hydrazone derivative of formula VII R 2 /R2 R N- N-.

\Re N reduction RI- S I C=S R9' \3 \R3 CHRs(Rg) 11 (VII) (VIII) ,using a reducing agent, for example a borohydride etherate, NaBH 4 NaCNBH3 or LiAlH 4 in an inert solvent, for example a suitable alcohol, tetrahydrofuran, dioxane, ethyl acetate or toluene, at temperatures of 00 4 to 50 0 C or by catalytic hydrogenation using catalysts, for example nickel, platinum, palladium or rhodium.

Process (d) Reductive alkylation of a pyrimidine hydrazine derivative of formula IV

N-.

R,

(IV)

\R

3 with an aldehyde or ketone of formula V Re--R (V) 9in the presence of a reducing agent, for example a borohydride etherate, NaBH4, NaCNBH 3 or LiAlH 4 in an inert solvent, for example a suitable alcohol, tetrahydrofuran, dioxane, ethyl acetate or toluene, at temperatures of 00 to 50 0 C, preferably 100 to 40 0

C.

Process (e) Alkylation of a pyrimidine hydrazine of formula IV or VIII with an alkyl halide R Hal o /2 R 2

N-*

RI-- R Hal RI-- H2 0 \3 R R R3 o o (IV) (IX) /R2 72

N-*

Ri- R Hal Ri- 0N=

\N=

CHR

8

(R

9 R CHR 8

(R

9 0 S1 (vIII) (x) in an inert solvent, in the presence of a base and at temperatures of 00-60 0 C, preferably 10 0 -40 0 C, R being Ci-Ctalkyl. Other suitable 0 S alkylating agents are dialkyl sulfates.

In processes described above, RI-R 9 are as defined under formula I.

SIn the processes described, it is possible, if necessary, to use both inorganic and organic bases, for example the following: the hydroxides, oxides or carbonates of lithium, sodium, potassium, magnesium, calcium, A strontium and barium or, alternatively, hydrides, for example sodium hydride, and alcoholates, for example potassium tert.-butanolate, and tertiary amines, such as triethylamine, triethylenediamine or pyridine.

Solvents and diluents that may be used as reaction media in conformity with the particular reaction conditions are, for example, the following: aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, I

I

10 petroleum ether; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; N,N-dialkylated amides, such as dimethylformamide; and also mixtures of such solvents with one another.

The pyrimidine derivatives of formula II in which Y is halogen can be prepared according to known methods (see D.J. Brown, The Pyrimidines, Interscience Publishers, 1962).

An often-used method of synthesis consists in the condensation of urea with B-diketones to form 2-hydroxypyrimidines which are subsequently reacted to form 2-halopyrimidines as follows: /0 HzN\ =N -OH -Hal 0 H N R3 R 3 There may be used as halogenating agents especially phosphorus oxychloride or phosphorus oxybromide.

*t Another possible method of obtaining the 2-halopyrimidines of formula II is to prepare them by way of the 2-aminopyrimidines. The 2-aminopyrimidines are obtained by known methods (see D.J. Brown, The Pyrimidines, Interscience Publishers, 1962), then diazotised, and converted by the Sandmeyer process into the halopyrimidines. The 2-aminopyrimidines are obtained, for example, by condensing B-diketones with guanidine in the following manner.

HN 1) NaNOz/H N S+ C-NH 2

N-NH

2 \-Hal R 2) Hal /Cu R3 Ra R 3

II

El' likewise known (see D.J. Brown, The Pyrimidines, Interscience Publishers, 1962).

Apart from the condensation of the corresponding diketones as described above, pyrimidines of formula II in which the radical R3 is haloalkyl can also be obtained by reacting the hydroxyalkyl derivatives with phosphorus halide or thionyl halide in the presence of tertiary bases in inert solvents.

Some of the intermediates of formula II R2 Y- (II),

N=.

R3 in which Y is halogen or SOz-R6 and R 6 is C1-C 4 alkyl or aryl and R 2 and R 3 are as defined under formula I, are known.

The following groups of compounds of formula II are novel: 1. Compounds wherein R 2 is Ci-Csalkyl or Ci-Csalkyl substituted by the radical OR 5 or by the radical SR 5 Ra is Ci-C4alkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs; Rs is hydrogen, Ci-Csalkyl, C 3 -Csalkenyl, C 3 -Csalkynyl or the radical S (CH 2 )n-X-C 1

-C

3 alkyl; X is oxygen or sulfur; n is 1 to 3; Y is halogen, preferably chlorine, or S0 2 R6; and R 6 is C1-Cqalkyl or aryl, with the att exception of the compounds 2-chloro-4-methyl-6-methoxymethylpyrimidine (t and 2-chloro-4-methyl-6-trichloromethylpyrimidine.

t t 2. Compounds wherein R 2 is hydrogen, CI-Csalkyl or Ci-Csalkyl substituted by the radical ORs or by the radical SR 5

R

3 is Cz-Csalkenyl or C2-Csalkynyl; Rs is hydrogen, Ci-Csalkyl, C3-Csalkenyl, C3-Csalkynyl or the radical (CH 2 -X-Ci-C 3 alkyl; and Y is halogen.

i

I

i:;ti ''*sF 12 The novel compounds of formula II form part of the present invention.

The hydrazine derivatives of formula III are known or can be prepared by methods known to the person skilled in the art.

Surprisingly, it has been found that the compounds of formula I have, for practical field application purposes, a very advantageous biocid-l spectrum for the control of phytopathogenic microorganisms, especially fungi. They have very advantageous curative, preventive and, in particular, systemic properties, and can be used for protecting numerous cultivated plants. With the compounds of formula I it is possible to inhibit or destroy the pests which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which grow later are also protected, for example, from attack by phytopathogenic microorganisms.

a The compounds of formula I are effective, for example, against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (especially Botrytis, and also Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, Alternaria); and Basidiomycetes (e.g.

Rhizoctonia, Hemileia, Puccinia). They are also effective against the Ascomycetes class Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and the Oomycetes class Phytophthora, Pythium, Plasmopara). The compounds of formula I can also be used as dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings o against fungus infections as well as against phytopathogenic fungi which ,t occur in the soil. In addition, compounds of formula I are effective against insect pests, for example against pests on cereals, especially t rice.

The invention also relates to compositions containing as active s ingredient compounds of formula I, especially plant-protecting compositions, and to their use in the agricultural sector or related fields.

hi i

F

13 The present invention further embraces the preparation of those compositions, which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds described herein. The invention furthermore relates to a method of treating plants, which comprises applying thereto the novel compounds of formula I or the novel compositions.

Target crops to be protected within the scope of the present invention comprise e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related crops); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); 1 leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (cucumber, marrows, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, *o cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor), or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, l simultaneously or in succession, with further compounds. These compounds can be fertilisers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or A mixtures of several of these preparations, if desired together with further carriers, surfactants or application-promoting adjuvants 4'0. customarily employed in the art of formulation.

Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g.

natural or regenerated mineral substances, solvents, dispersants, wetting i agents, tackifiers, thickeners, binders or fertilisers.

L' 14 A preferred method of applying a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application. The number of applications and the rate of application depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) if the locus of the plant is impregnated with a liquid formulation, or if the compounds are applied in solid form to the soil, e.g. in granular form (soil application). In paddy rice crops, such granulates may be applied in metered amounts to the flooded rice field. The compounds of formula I may, however, also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation containing the active ingredient, or coating them with a solid formulation.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of tat, t'r formulation, and are for this purpose advantageously formulated in known S.manner e.g. into emulsifiable concentrates, coatable pastes, directly 1 :t sprayable or dilutable solutions, dilute emulsions, wettable powders, 0 soluble powders, dusts, granulates, and also encapsulations in e.g.

polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the t prevailing circumstances. Advantageous rates of application are normally from 50 g to 5 kg of active ingredient per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to 600 g a.i./ha.

4444 The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, 4 44 e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

LA1 15 Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive S* carriers are porous types, for example pumice, broken brick, sepiolite or o* S bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic S surfactants having good emulsifying, dispersing and wetting properties.

The term "surfactants" will also be understood as comprising mixtures of surfactants.

C

Both so-called water-soluble soaps and also water-soluble synthetic surface-active compounds are suitable anionic surfactants.

I

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids

(C

1

-C

2 2 e.g. the sodium or potassium salts of oleic or stearic

I

16 acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyllaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially alkanesulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylsulfonates.

The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C 2 2 -alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene o oxide adducts. The sulfonated benzimidazole derivatives preferably 00 contain 2 sulfonic acid groups and one fatty acid radical containing 8 to o O 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium 0oco0 or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.

Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and a° 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon L Ci 17 atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cs-C 2 2 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of S halides, methylsulfates or ethyisulfates, e.g. stearyltrimethylammonium Schloride or benzyldi(2-chloroethyl)ammonium bromide.

0o 9 co Further surfactants customarily employed in the art of formulation are known to the person skilled in the art or can be taken from the relevant specialist literature.

The agrochemical compositions usually contain 0.1 to 99 by weight, preferably 0.1 to 95 by weight, of a compound of formula I, 99.9 to 1 by weight, preferably 99.9 to 5 by weight, of a solid or liquid adjuvant, and 0 to 25 by weight, preferably 0.1 to 25 by weight, of a t' surfactant.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also contain further auxiliaries such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.

ij .i 18 The following Examples serve to illustrate the invention in more detail without limiting it.

1. Preparation Examples Example 1.1: 2 -hydroxy-4-methyl-6-cyclopropylpyrimidine hydrochloride (starting material) YH3 HI HC1 HU' HO g (0.10 mol) of urea and 12.6 g (0.10 mol) of cyclopropylbutane-1,3dione are dissolved at room temperature (~200C) in 35 ml of ethanol and ml of 32 aqueous hydrochloric acid. After standing for 10 days at room temperature, the solution is concentrated using a rotary evaporator 4, at a bath temperature of maximum 450C. The residue is dissolved in 20 ml S of ethanol; after a short time, the product begins to separate out in the 4 4form of the hydrochloride. 20 ml of diethyl ether are slowly added with S stirring, the product is separated from the solvent by filtering off with S suction and is washed with a mixture of diethyl ether and ethanol and dried at 600C in vacuo to give 7.14 g (38.2 of the theoretical yield) of 2 -hydroxy- 4 -methyl-6-cyclopropylpyrimidine hydrochloride. The filtrate is concentrated and, after recrystallisation from 10 ml of ethanol and 20 ml of diethyl ether, a further 5.48 g (29.2 of the theoretical yield) of the title compound are obtained.

Analysis: CaHIoN20-HCl (mol. wt.: 186.64) a calc. found C 51.48 51.47 H 5.94 5.97 S* N 15.01 15.15 Cl 18.99 18.89 it 19 Example 1.2: 2-chloro-4-methyl-6-cyclopropylpyrimidine hydrochloride (starting material) Cl \N 52.8 g (0.24 mol) of 2-hydroxy- 4 -methyl-6-cyclopropylpyrimidine hydrochloride are introduced into a mixture of 100 ml of phosphorus oxychloride and 117 g (0.79 mol) of diethylaniline and stirred; the exothermic reaction slowly begins, the temperature rising from room temperature to 63 0 C. The batch is then heated in an oil bath for 2 hours at 100-110 0 C internal temperature. After cooling to room temperature, the mixture is poured, with stirring, into a mixture of ice-water and methylene chloride. After one hour, the organic phase is separated in a separating funnel and is washed neutral with NaHCO 3 solution. After removing the solvent, 116.4 g of crude product comprising 2-chloro-4- *oo methyl-6-cyclopropylpyrimidine and diethylaniline are obtained. Chromatographic separation using silica gel and a mixture of 25 ethyl acetate t and 75 hexane as eluant affords 35.7 g (89.4 of the theoretical yield) of pure 2 -chloro-4-methyl-6-cyclopropylpyrimidine in the form of a colourless oil.

Example 1.3: 2-amino-4-diethoxymethyl-6-cyclopropylpyrimidine (starting material) 2I H z N N CH(OC 2

H

5 2 74.8 g (0.42 mol) of guanidine carbonate and 74.1 g (0.35 mol) of 4 -cyclopropyl-2,4-dioxobutyraldehyde diethyl acetal are boiled for hours in 250 ml of ethanol. The batch is then concentrated using a rotary evaporator and the residue is extracted with water and ethyl i 20 acetate. After evaporating the ethyl acetate, 79.2 g of crude product remain which are recrystallised from hexane to give 70.4 g (85.8 of the theoretical yield) of the pure title compound. M.p. 77-78 0

C.

Example 1.4: 2 -chloro- 4 -formyl-6-cyc)opropylpyrimidine (starting material) Cl/ NI \CHO 70.3 g (0.30 mol) of 2 -amino- 4 -diethoxymethyl-6-cyclopropylpyrimidine are dissolved in 340 ml of 32 aqueous hydrochloric acid and cooled to using dry ice. A solution of 40.9 g (0.59 mol) of sodium nitrite in 80 ml of water are then slowly added dropwise at -20 to -25 0 C, nitrogen evolving and a solid product separating out. After 2 hours the cooling means are removed and the mixture is allowed to rise to room temperature and is extracted with ethyl acetate. The extract is dried with sodium sulfate and the solvent is removed to give 21.9 g of crude product in the form of an oil. Further purification by means of column chromatography S (silica gel, eluant 30 parts ethyl acetate and 70 parts hexane) affords 16.1 g of the pure title compound in the form of a colourless liquid.

Refractive index [n] 2 5 1.5603.

D

Analysis: CsH 7 ClN 2 0 (mol. wt.: 182.61) 't calc. found C 52.6 52.6 S H 3.9 4.1 N 15.3 14.8 Cl 19.4 18.7 t,

C~

V

21 Example 1.5: 2-chloro-4-hydroxymethyl-6-cyclopropylpyrimidine (starting material) Cl \CH 2 0H 15.4 g (0.084 mol) of 2-chloro-4-formyl-6-cyclopropylpyrimidine are dissolved in 125 ml of methanol and reduced by the addition of 1.6 g of sodium borohydride. The batch is concentrated and extracted with ethyl acetate and the solvent is removed using a rotary evaporator to give 14.5 g of crude product which is recrystallised from a mixture of 20 ml of toluene and 20 ml of cyclohexane. The yield of the pure title compound is 13.7 g (88.4 of the theoretical yield); m.p. 102-104 0

C.

Analysis: C 8

H

9 ClN 2 0 (mol. wt.: 184.63) calc. found S C 52.04 52.05 O H 4.91 4.90 N 15.17 15.27 S Cl 19.20 19.28 4 a Example 1.6: 2-chloro-4-hydroxymethyl-6-cyclopropylpyrimidine methanesulfonate (starting material) Cl '\CH 2 0S0 2

CH

3 g (0.05 mol) of 4-hydroxymethylpyrimidine and 5.7 g of triethylamine are placed in 150 ml of tetrahydrofuran, and a solution of 6.5 g of ,tt i methanesulfonic acid chloride in 30 ml of tetrahydrofuran is added dropwise with cooling. Triethylamine hydrochloride separates immediately and is filtered off with suction. Concentration yields 14.7 g of crude product which is chromatographed on silica gel (25 parts ethyl acetate and 75 parts hexane) to give 13.6 g of the pure title compound.

M.p. 64-66 0

C.

Sll -22- Analysis: C9HiiClN 2 OaS (mol. wt.: 262.71) caic. found C 41.15 41.32 H 4.22 4.33 N 10.66 10.56 S 12.20 12.16 Example 1.7: 2-chloro-4-fluoromethyl-6-cyclopropylpyrimidine (starting K material) Cl/ \N CH 2

F

13.4 g (0.05 mol) of methanesulfonate are boiled under reflux for 5 hours C4 q U o in 70 ml of propionitrile with 9.4 g (0.16 mol) of potassium fluoride and 0.8 ml of 18-crown-6 as catalyst. Removal of the solvent and subsequent 400 extraction with water and ethyl acetate gives a crude product which is 6 :purified by coumn chromatography (silica gel; 15 parts ethyl acetate and too.00 85 parts hexane). The yield of the pure title compound is 7.5 g (78.6 000 of the theoretical yield); m.p. 37-39'C.

Analysis: CBHBClFN 2 (mol. Wt-: 186.62) calc. %found S C 51.49 51.73 H 4.32 4.45 N 15.01 14.90 C F 10.18 10.26 S Cl 19.00 18.50 4Example 1.8: 2-chloro-4-methyl-6-( 2-methylcyclopropyl) -pyrimidine 44 (starting material) C 3 Cl/"N V' CH 3 23 76.4 g (0.47 mol) of 2 -amino-4-methyl-6-(2-methylcyclopropyl)-pyrimidine, produced by boiling guanidine carbonate with acetylmethyl-2-methylcyclopropyl ketone in ethanol, are dissolved in 536 g of 32 hydrochloric acid and cooled to -25 0 C. 2 g of copper powder are then added and a solution of 71.4 g (1.03 mol) of sodium nitrite in 200 ml of water is added dropwise at -25 0 C over a period of 3 hours during which nitrogen and nitrous gases evolve. The mixture is then allowed to rise to room temperature, is extracted with ethyl acetate and the extracts are washed with water and dried with sodium sulfate. After removing the solvent, 27.7 g of crude product remain as residue which is purified by chromatography on silica gel with a mixture of 20 parts ethyl acetate and parts hexane as eluant to give 32.2 g of the pure title compound; refractive index [n] 24 1.5334.

D

Analysis: CgH 1 IC1N 2 calc. found 0 C 59.18 59.16 S o H 6.07 6.15 o N 15.34 15.25 Cl 19.41 19.20 a o Example 1.9: 2-(a-phenylhydrazino)-4,6-dimethylpyrimidine (Comp. 1.12) I II =*/CH 3 H2N-- 6H".

N-.

0 \CH3 O' 4.77 g (0.033 mol) of phenylhydrazine hydrochloride are suspended under nitrogen in 60 ml of tetrahydrofuran, and 7.41 g (0.066 mol) of potassium tert.-butanolate are added. A solution of 5.59 g (0.030 mol) of 0 *0 2-methylsulfonyl-4,6-dimethylpyrimidine in 15 ml of tetrahydrofuran is then added dropwise at 25 0 -35 0 C and, after 2 hours, the mixture is extracted with ethyl acetate and water with the addition of a small amount of acetic acid at pH6. After drying the organic phase with sodium sulfate and removing the solvent using a rotary evaporator, 5.88 g of crude product are obtained which are subjected to chromatographic 4" 4 ruplrr~ 24 purification using silica gel and a mixture of 35 parts ethyl acetate and parts hexane to give 2.89 g of the pure title compound which, after recrystallisation from n-hexane, melts at 41-43 0

C.

Example 1.30: 2-(-phlenylhydrazino)-4,6-dimethylpyrimidine (comp. 1.12) CH 3

N=.

H

2ZNN--~

\CH

3 7.06 g (0.035 mol) of 2-trimethylammonium-4,6-dimethylpyrimidine chloridel and 5.78 g (0.04 mol) of phenylhydrazine hydrochloride are suspended in 50 ml of tetrahydrofuran, and a solution of 5.04 g (0.045 mol) of potassium tert.-butanolate in 25 ml of tetrahydrofuran is added dropwise under a nitrogen atmosphere. The exothermic reaction is maintained at 5 0 -10 0 C by cooling. When the mixture has warmed to 20 0 C, it is extracted with ethyl acetate and water and the extract is dried with sodium sulfate. After concentration, 5.9 g of crude product are obtained which is purified by column chromatography (silica gel, eluant: mixture of 25 parts ethyl acetate and 75 parts hexane) to give 3.94 g of the pure title compound.

Example 1.11: N-(4-metiyl-6-cyclopropylpyrimidin-2-yl)-N-phenylhydrazine (Comp. 1.4) a 0 000 Sa 00.

0r i t

YH,

H2N 2.20 g (0.013 mol) of 2-chloro-4-methyl-6-cyclopropylpyrimidine and 1.62 g (0.015 mol) of phenylhydrazine are dissolved in 20 ml of tetrahydrofuran. A solution of 2.02 g (0.018 mol) of potassium tert.- W. Klotzer, Monatshefte i. Chemie 87, 131 (1956) I J- 3 alkynyl; R 5 is hydrogen, Ci-Csalkyl, C 3 -Csalkenyl, Ca-Csalkynyl or the radical (CHz)n-X-Ci-C 3 alkyl; and Y is halogen.

25 butanolate in 20 ml of tetrahydrofuran is added dropwise to this solution with cooling at 20-25 0 C. After 30 minutes, no further starting pyrimidine is detected by thin layer chromatography. The mixture is then extracted with water and ethyl acetate and, after removing the ethyl acetate using a rotary evaporator, 3.13 g of crude product are obtained which are purified by column chromatography on silica gel (eluant: 35 ethyl hexane). 2.83 g of the purified product are obtained (90.2 of the theoretical yield) which are recrystallised from a mixture of 8 ml of n-hexane and 1 ml of cyclohexane, affording 1.62 g of the title compound 46 0 The mother liquor is concentrated and is recrystallised again to give a further 0.42 g of that compound 45-46 0

C).

The total yield of the recrystallised compound is 2.04 g (65.3 of the theoretical yield).

Analysis: C 14 Hi 6 N4 (mol. wt.: 240.31) 0@ 9 calc. found C 69.98 69.81 H 6.71 6.77

I

N 23.32 23.49

S

Oteel Example 1.12: (N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenylisobutyraldehyde hydrazone (Comp. 3.26) I SN==CHCH(CH3)2 6.25 g (0.026 mol) of N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenylhydrazine and 2.25 g (0.031 mol) of isobutyraldehyde are dissolved in ml of methanol, producing a slightly exothermic reaction. After standing for two hours at room temperature, the solvent is removed using a rotary evaporator to give 7.8 g of crude product in the form of a viscous oil of which 3.2 g are purified by column chromatography on silica gel (eluant: 72 hexane/18 ethyl acetate/10 methanol). The

J

i i: IIICI" L*I~ l~ri-- 26 yield is 2.92 g of the pure title compound having a melting point of 53-55 0 C. This corresponds to a yield of 93 of the theoretical yield in terms of purification of all of the crude product.

Analysis: C8Hz2 2 N4 (mol. wt.: 294.40) calc. found C 73.44 73.25 H 7.53 7.64 N 19.03 18.92 Example 1.13: N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenyl-N'isobutylhydrazine (Comp. 4.87) o 3 v CH 3 H1rCH 2

CH(CH

3 2 8.55 g (0.029 mol) of N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenylisobutyraldehyde hydrazone are dissolved in 30 ml of methanol and 2 ml of glacial acetic acid. 2.14 g (0.029 mol) of sodium cyanoborohydride are then added in portions with stirring. The reaction proceeds exothermically; the temperature is maintained at 10-15 0 C by cooling. After 1 hour, the batch is worked up by extraction with ethyl acetate and water and the tre organic phase is concentrated using a rotary evaporator to give 8.5 g of crude product. Purification by column chromatography on silica gel (eluant: 85 hexane/15 ethyl acetate) affords 7.6 g (89 of the theoretical yield) of the title compound in the form of an oil having a refractive index of [n] 25 1.5733.

D

Analysis: Ci 8

H

2 4N 4 (mol. wt.: 296.42) calc. found C 72.94 72.90 H 8.16 8.21 N 18.90 18.83 .iI^ -1 -27- Example 1.14: N-(4-methyl-6-methoxymethylpyrimidin-2-yl)-N-phenyl-N'methyihydrazine (Comp. 4.17) H3 y\N'CH,0CH,

THCH

3 3.70 g (0.033 mol) of potassium tert.-butanolate are dissolved in 25 ml of tetrahydrofuran dried with molecular sieves, 3.67 g (0.03 mol) of N-methyl-N'-phenylhydrazine 2are added and a solution of 4.22 g (0.025 mol) of 2-chloro-4-methyl-6-methoxymethylpyrinidine in 30 ml of anhydrous tetrahydrofuran is added dropwise under nitrogen at -20 0 C to 0 give a yellow-brown suspension which is gradually allowed to rise to room temperature. After 4 hours, the batch is extracted with water and ethyl 0acetate and the crude product is isolated by evaporating the solvent and purified by column chromatography on silica gel (eluant: 65 hexane/35 ethyl acetate). The pure title compound is obtained in the form of an oil having a refractive index of [n]2 4 1.5793.

Analysis: C 1 i4H 18

N

4 0 (mol. wt.: 258.33) calc. found C 65.09 65.08 H- 7.02 7.09 N 21.69 21-05 Example 1.15: N-(4,6-dimiethylpyrimidin-2-yl)-.N-phenyl-N'-methylhydrazine (Comp. 4.1) 4 ?H 3 1(CH 3 z 2K. Kratzl, Monatshefte f. Chemie 89, 83 (1958) 28 4.03 g (0.02 mol) of 2-trimethylammonium-4,6-dimethylpyrimidine hydrochloride 3 are stirred with 3.05 g (0.025 mol) of N-methyl-N'-phenylhydrazine under nitrogen in 30 ml of anhydrous tetrahydrofuran, and a solution of 3.36 g (0.03 mol) of potassium tert.-butanolate in 15 ml of tetrahydrofoiran is added dropwise at room temperature. The batch is left overnight at room temperature to complete the reaction and is then extracted with water and ethyl acetate, the solvent is removed and the crude product is purified by column chromatography on silica gel (eluant: hexane/30 ethyl acetate) to give 3.09 g of the title compound in the form of an oil.

Analysis: Ci 3 H16N4 calc. found C 68.40 68.01 H 7.07 7.09 24.54 24.13 Qo 9 o e e 00 0 0o o o o00 Example 1.16: N-(4,6-dimethylpyrimidin-2-yl)-N-phenyl-N'-dimethylhydrazine (Comp. 4.13) H3 N CH3

N(CH

3 )2 3.42 g (0.016 mol) of N-(4,6-dimethylpyrimidin-2-yl)-N-phenylhydrazine are dissolved in 20 ml of methanol together with 3.28 g (0.042 mol) of 38 formaldehyde and 2 ml of glacial acetic acid, and 1.33 g (0.018 mol) of sodium cyanoborohydride are added in portions at approximately 5 0

C.

The reaction proceeds exothermically and is complete after one hour. The batch is extracted with ethyl acetate and water and the solvent is o* removed using a rotary evaporator to give 3.25 g of crude product which is purified by chromatography using silica gel and a mixture of 76 hexane, 19 ethyl acetate and 5 methanol to give 1.80 g (46.4 of the theoretical yield) of the pure title compound in the form of an oil; [n]2 5 1.5673.

D

W. Kltzer, onatshefte f. Che-ie 87, 131 (1956) W. Klbtzer, Monatshefte f. Chemie 87, 131 (1956) 29 Example 1.17: N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenyl-N'methyl-N'-isobutylhydrazine (Comp. 4.102) H3

CH

3

CH

2

CH(CH

3 2 4.55 g (0.0153 mol) of N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-Nphenyl-N'-isobutylhydrazine are dissolved with 1.45 g (0.0184 mol) of 38 formaldehyde in 25 ml of methanol and 2-ml of glacial acetic acid, and 1.24 g (0.0168 mol) of sodium cyanoborohydride are added in portions at 10 0 C. The reaction proceeds exothermically and, after one hour, the mixture is extracted with water and ethyl acetate. After removing the 04 .a solvent, 4.95 g of crude product are obtained which is purified by column chromatography on silica gel (eluant: 85 hexane/15 ethyl acetate) to give 4.4 g of the title compound in the form of an oil; refractive index [n] 3 0 1.5613.

SAnalysis: C1 9

H

2 6N4 (mol. wt.: 310.45) calc. found C 73.51 73.94 H 8.44 8.58 S N 18.05 17.93 6 4 ,i t ct i i t

I

30 Table I: Compounds of formula /R3 Gomp.

No.j physical constant 4a 0 a 0~ a

Q

*0 a o a 00 0 a 1.5 1.6 1.7 1.8 1.9 1.10 1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18 1.19 1.20 1.21 1.22 1.23 1.24

C

6 H5 4-CF 3

C

6

H

4 4-F-C 6

HL.

C

6

HS

C6H5 C6H5 0 6

H

5 O 6

HS

C6Hs 3,4-(C 2

H

5 0) 2

-C

6

H

3

C

6 H5

C

6 H5 4-CH 3 0-C 6 H4 06115 3, 5-Cl 2

-C

6

H

3 3, 5-C1 2 -CsH 3 3, 5-C1 2

-C

6

H

3 3, 5-C1 2 -C6H 3 3,4-(C 2 HS0) 2 -0 6

H

3 4-CH 3 0-C 6 H4 4-CH 3 0-C 6

H.

3,4-(C 2

H

5 0) z-C6H 3 C6HS 4-CH 3

-C

6

H

4

H

CH

3

H

CH

3 C(0H 3

CH

2 0CH 3

CH

3 CH 002H5

CH

2

OCH(CH

3

)C

2 Hs

CH

3

OH

3

C(CH

3 3

OH

3

CH

3 CH3 c(CH 3 3 Oii 2

OC

2 H5

OH

3

OH

2

OC

2 H5

OH

3

OH

3

OH

3

OH

3

H

OH

2 0CH 3 0H2 0CH 3 o(oH 3

OH

3 CH2002 CH2 00 2

H

OH

3 CH2002 CHC1 2 0H2002

OH

3 OH2 OC 2 0H20CH 3 o(0H 3

OH

3

OH

3 CHzOOH 3

OH

2 00H 2

CH=CH

2

OH

3 m.p. 129-1 3100 m.p. 45-46oC m.p. 37-38'C m.p. 60-61'C m.p. 41-43oC a a a a aa 0

C

m. p. 154-156 00 m.p. 90-92%O n 30 1.604

D

31 Continuation: Table 1 0*

U.

U

U

U

U

U

*UUU

ettt I U U I tL U C Ut U I I i Ut Comp. R 1 2R physical No. constant 1.25 4-OCH 3

-C

6 H4 -KJ Hz CH 3 1.26 3,5-C1 2

-C

6

H

3

CH

3

CH

2 0CH(CH 3

)C

2

H

1.27 4-OCH 3 -C6H4 CH 3

CH

2 0CH(CH 3

)G

2

H

1.28 2-Br-C6H4 OH 3

CH

3 m.p. 55-57'C 1.29 3,5-C1 2 -C6H 3

CH

2 0CH 2

GH=CH

2

CH

3 1.30 4-CH 3 0-C 6 H4 C(CH 3 3

CH

2 0CH 3 1.31 3,5-Cl 2

-C

6

H

3

OH

3 CHC1 2 1.32 3-Cl-C6H 4

CH

3

OH

3 n.p. 47-48'C 1.33 3,4-(C 2

H

5 0) 2

-C

6

H

3

CH

3

CH

2

OCH(CH

3

)C

2 Hs 1.34 4-CH 3 0-C 6 H4 OH 3

CH

2

OCH

3 1.35 3,4-(C 2 HSo) 2 -C6H 3

C(CH

3 3

CH

2 0CH 3 1.36 3,5-C1 2

-C

6

H

3

OH

3

CH

2

OCH

3 1.37 2,4,6-C1 3

-C

6

H

2

CH

3

CH

3 m.p.150-152 0

C

1.38 3,4-(C 2

H

5 0) 2

-C

6

H

3

CH

3

CH

2 0CH 3 1.39 3,5-Gl2-C 6

H

3 CH20CH2C=-CH OH 3 1.40 C 6

H

5

CH

2 0CH 2 C=CH CH 3 1.41 4-CH 3 o-C 6

H

4

CH

2 0CH 2 C=-CH OH 3 1.42 3,5-(CF 3 2 -C6H 3

CH

3

OH

3 m.p. 88-90%G 1.43 C 6

H

5

CH

2 0CH 3

CH

2 00H 3 1.44 C 6

H

5

CH

2

SCH

3

OH

3 1.45 C6Hs OH 3

CH(OCH

3 2 1.46 1CSH5 OH 3 GH(0C 2 Hs) 2 -7 32 Continuation: Table :I Conip. RI R 2 R3physical No. constant o St 5*5, S a 5C a o a o t eta a

II

I a.

1 .47 1.48 1 .49 1 .50 1 51 1 .52 1 .53 1 .54 1 .55 1 .56 1 .57 1 .58 1.59 1 .60 1 .61 1 .62 1.63 1.64 1 .65 1 .66

C

6

H

5 4-Br-C 8

H

4

C

6 Hs

C

6

H

5

C

6

H

5

C

6 C6H5 3-CH 3 -C6H4

C

6 H5 CsH5 C sHs

C

6 H5

C

6 lis C6H 5 C6H5 C6H5

C

6 H5 CsH5 4-F-C 6

H.

C6H5

CU

3

CU

3

CH

3

CH

3

C

2 H5

CH

3 CH(CH3) 2

CH

2

OCH

3

CH

2

OCH

3

CHO

CH

2 0CH 3

CH

2

CH

2

CH

3 CH(CH3) 2

CU

3

CH

2 0OH CH3 CH3 CYClo-C6H1 1

CF

2 C1

CF

3

CF

2 C1

CH

3

\I//CH

3 C3

CH(OCH

3 2 CH2CH(CH3) 2

CH

2 0CHi 3

CH

2

OCH

3

-ICH

3 m.p. 92-93'C m.p. 72-73'C 25 1.6063

D

1.6072 n 2 5 1.-5883

D

33 Continuation: Table 1 '8 0 Comp.

No.

1.7 1.68 1.69 1 .70 1.71 1 .72 1.73 1 .74 1.75 1.76 1.77 1 .78 1.79 1.80 1.81 1.82 1.83 1.84 1.85 1.86 1.87 1.88 physical constant I t CdHs

C

6 H5 06115 06115

C

6 H5 C6H5 ,4-F-C 6

H+

4-01-C6H11 4-F-C 611

C

6 Hs O 6

H

5 CsH5 Cells 06H5 06115 C6H5 06115 06115 06115 4-0F3-6H1.

4-Br-C6H (C11 2 3 C1 3

C

2 11 5 011200113

CH

2 0CH3

CH

2 13 0113 0113 011200113 011(013)02115 (0112)30113 (0112)20113 -<1i 0113 0113 011200113 011200113

OF

2 C1 011(00113)2 0113 0113 0112 Br

CF

2

CF

3

OH

2

F

011200113 011200113 0112011(013)2 011200113 011200113 n41.5923 m.p. 78-79'C m.p. 101-102'C n51.5723 n21.6150 *44d t e t 4.

4 7 34 Continuation: Table 1 Comp. RIR2 R 3 physical No. constant 1.89 C61i 5 CH20H CH 2

OCH

3 1.90 C 6

H

5 C2C3 1.91 C6H5 CH 2

OCH

3 CRi 2 Cl 1.92 4-CH 3 -C6H4 CH 2

OCH

3

CH

3 1.93 CsH5 CH(OC 2 H5)2 n 25 1.5763 i D 1.94 2-CF 3

-C

6 H4 CH- 3

CH

2 0CH 3 C Cl 1.95 C6H5 CH3 /"I 1.96 C6H 5

CH

3

CHO

1.97 C6H C3/I 1.98 4-Cl-C 6 H4 CH3 CH 2

OCH

3 1.99 4-Cl-3-CF 3 -C6H 3 CH3 CH 2

OCH

3 1.100 3-CH 3

-C

6

H

4 CH3 CH 2 0CH 3 1.101 3-F-C6H 4 C113 CH(0C 2

H

5 2 1.102 3-CF 3

-C

6 H4 CH 2 0CH 3

CH

3 1.103 3-Cl-C 6 H4 CH 2 0CH 3

CH

3 1.104 3-F-C 6

H

4

CH

2 0CH 3

CH

3 n 2 4 1.5863

D

1.105 4-F-C6H4 CH 2

OCH

3

CH

3 mn.p. 70-72'C 1.106 4-Cl-C6H. CH3 K 44 4 4 4 4 o o4 4 40 0t 4 4,4444 4440 4444 444.

4 4 4 44 4 44 44.4 4 4 4 44 4 44 44 4 4 44 35 Continuation: Table 1 C. C 4 S 4e*e #4 @4 4 *4944C 4 400#4 4 t CC I I C It Coinp. RR2R 3 physical No. constant 1.107 Cells CH 3

CH

2 0H 1.108 4-F-C6H4 Gil 3 m.p. 93-95'C 1.109 C6H5 CH 2

OCH

3

CH

2 Br 1.110 C 6 Hs CH 3

CH

2 Cl 1.111 4-Cl-3-CF 3

-C

6 l 3 -*jHGi 3 1.112 Cell 5

CH

2 0CH 3

CH

2

F

1.114 Cells Gil 3

CH

2 Br 1.115 CeH5 CH 3

CH

2

F

1.116 C6H5C(C3) C(CH 3 3 1.117 C6H5(C2)H Gil 3 1.118 Cells C 2 H5 C 2 ils n 25 1.5923

D

1.119 C6H5 CH 3

C

2 ils n 30 1.5953

D

1.120 Cells CH 3

C=-CH

1.121 CeH5 Gil 3 C=CCl 3 1.122 3-F-Cll 4 Gil 3 n.p. 41-42'C 1.123 3-F-C 6

H-

4 CH 2

F

1.124 3-F-Cell Gil 3 n 2 5 1 .5943 *-CH3

D

1.125 Cells H 1.126 Cells Cil 2 Ci 2 CH(Cil 3 2 Gil 3 -36 Continuation? Table 1 Comp. RIR 3physical No. constant 1.127 4-F-C 6 H4 C 2 11 5

C

2 Hs n 2 5 1 .5743

D

1.128 4-F-c6H4 CH2OCH 3 -2m.p. 56-57'C 1.129 3-F-C 6 H4 CH 3

CH

3 m.p. 60-62'C 1.130 3-F-C6H4 CH 3

C

2

H

5 n 3 0 1.5873

D

1.131 3-F-C6H 4

CH

2 0CH 3 n 2 5 1.5873

D

1.132 C6H 5 CH3 CF 3 n 2 4 1.5543

D

1.133 4-F-C 6

H

4

CH

2 0CH 3

C

2

H

5 D2 .53 1.134 2-F-C 6

H

4 CH3 CH 3 n 23 1.5863

D

1.135 2-F-C6H4 CH3 CH 2 0CH 3 n 23 1.5773

D

1.136 2-F-C 6

H

4

CIT

3 n" n 37 1.5811

D

1.137 4-F-CGH4 C 2 H5 n 22 1.5813

D

1.138 3-F-C 6

H

4

C

2 HS n 2 3 1.5894

D

1.139 C6H5 CH 2

CH

2

CH

3

CH

2

CH

2

CH

3 n 23 1.5743 D 1.140 3-F-c6H4 CH 2

CH

2

CH

3

CH

2

CH

2

CH

3 n 23 1.5633

D

1.141 2-F-C 6 H4 3

CH

3 n 2 4 1.5854

D

1.142 C6Hs H H m.p. 75-77'C 4* 4.

0 44 p 4 0* 4 4*4*4 900444 4 4*4, 'Oat Li I. I 14 37 Table 2: Compounds of formul~a N-/R3 Comp.

No.

physical constant

S

5*& 44I~ S 2.1 2.2 2.3 2.4 2.6 2.7 2.8 2.9 2.10 2.11 2.12 2.13 2.14 2.15 2.16 2.17 2.18 2.19 2.20 2.21 2.22 2.23 2.24

CHO

t-bu tyl

OH

3

OH

3

OH

3

OH

3

CH

3

CH

2 0CH 3

OH

2

OCH

3

CH

3

OH

3

CH

3

OH

2 0CH 3 OH(00 2

H

5 2 n-propyl iso-propyl n-butyl

CH

2 0CH 3

CH

2 0CH 3

OH

2 0CH 3

CH

2 0OH

CH

2 00H 3 C2 OCH 3

OH

3

OH

2 0C 2

H

5

CH

2 0CH(CH 3

)C

2

H

5

OH

2 002H5 CHC1 2

OH

2 0COH 2

CH=CH

2

OH

2 0CH 2

C-=CH

OH

2 0CH 3 CH(00H 3 2

OH(O

2 Hs) 2

OF

2 Cl

OF

3

OH

2 00H 3

OH

2 00H 3 OH(00H 3 2

OF

2

OF

3 0H 2 00H 3

OH

2 Cl

OH

2

F

CH

2 0CH 3 01 Cl Cl Cl Cl Cl Cl 01 01 01 01 01 Cl Cl Cl 01 Cl 01 01 Cl Cl Cl 01l

SO

2

OH

3 n 25 1.5603

D

in 2 5 1.5344

D

oil n24 1.5064

D

I

S +1 Table 3: Compounds of formula

R/R

R

9 \2 Comp No RIR 8R physical Comp.o.{ constant 3.1 3.2 3.3 3.4 3.6 3.7 3.8 3.9 3.10 3.11 3.12 3.13 3.14 3.15 3.16

C

6

H

5 C6115

C

6 H5 C6H5

C

6 H5 C sil Cs C 6115

C

6

H

5 3-F-C 6HI4

C

6

H

5 4-N0 2

-C

6 H4.

C

6 H5 C6H 5 C6H5 C6H 5 Gil 3

CH

3 CH3

C"

3 Gil 3 Gil 3 Gil 3 Gil 3

CH

3 Gil 3 Cil 3 C2H5

CH

3 Gil 3 Gil 3

CH

3

CF

3

CF

3 Gil 3 cyclo-C3Hs cyclo-G3is Gil 3

CH

2

OCH

3 cyclo-C3H5 C2115

GH

2

OCH

3 Cil 3 C2115 n-C 3

H

7 CYC10-C3H5 CYClo-C3HS cvclo-CiHs

H

H

H

H

H

H

H

H

Gil 3 Gil 3

C

2 H5

H

Gil 3

CH

3 Gil 3 2-CH 3 -C6H.

C 2

CH

3 Gil 3

C

2 5

G

2 H5

G

2 Hs n-C 317 Gil 3 Gil 3 Gil 3 n-G3H17 m.p. 188-190'G m.p. 117-118'C m.p. 137-138 0

C

m.p. 103-105'G in.p. 46-49'C m.p. 51-53%G n 25 1.5862 1. 5678 1.5830 n 21.5982

CH

2

OGH

3 a p.

a

C

C. C a a C

C

Table 3: (continuation) Comp. RR2R3

R

8 R9physical constant 3.17 4-CF 3

O-C

6 H. CH3 cyclo-G3H5 H (CH 3 2

CH

3.18 4-CF 3 O-C6H4 CH 3 cyclo-G 3 H5 H GB 3 p.0-6C 3.19 3-F-C 6 H4 CH3 CH 2 0CH 3 H C(CH 3 3 mp.0-6C 3.20 3-F-G 6 H4 GB 3

GH

2

OGH

3 H G 2

H

5 m.p. 95-97*C 3.21 4-CH 3 0-C 6 H4 GB 3

CB

3 H C 2

H

5 m.p. 81-82'C 3.22 4-CH 3 -CrH4 (GH 3 3 C GB 3 H n-C 3

H

7 3.23 4-CB 3

-G

6 H. n-C 3

H

7 n-G 3

H

7 H C2H 3.24 G 6 Hs C 2 Hs G 2

H

5 H C 2 Hs 3.25 C 6 Bs CH3 CH 3 H (CH 3 )zCH m.p. 83-84 0

C

3.26 CsH 5 Cl-b cyclo-C3H5 H (CH 3 2 CH in.p. 53-55 0

C

3.27 C 6

H

5

CH

3 -C=C cyc10-C3HS H CH 3 3.28 3F-C 6

H

4

CB

3 CYC10-C3H5 CYClo-C3H5 GB 3 3.29 4F-C 6 H. GB 3 CYClo-C 3 H5 GB 3

CF

3 3.30 4-(CH 3 2 CH-CSH4 CH3 GB 3

C

2

H

5

CH

3 3.31 C 6

H

5

CH

3

CH

3

-(GB

2 3.32 2-F-c 6 Ib. GB 3 n-C 3

H

7 -C24 3.33 4-I-C 6 H4 'rH 3

GB

3

C

2 H5 H 3.34 4-I-C&H. CYClO-C3H5 CH 3

(CH

3 2 CH H 3.35 C 6 Hs cyclo-C3H5 GB 3

CH

3 CH=CH- H m.p.121-122 0

C

3.36 C 6

H

5 CYC10-C3H5 CH 3

CF

3

H

3.37 C 6

H

5 CH3 1

CH

3 CB\/ Cp2\\C H &H3 3.38 C 6 Hs C(CB 3 3

C(CH

3 3

(CH

3 2 CH- H 3.39 C6H5 C(CH 3 3

C(CHB,,)

3

C

2 H5 GB 3 3.40 C6H5 CH3 CYC1o-C 3 H5 H CC1 3 m.p.139-141'C

C

I

Table 3: (continuation) Comp. RR2RR8R 9 physical constant 3.41 C6s Gil 3 CM3 -ZC 3 H m.p. 94-96*C 3.42 C6H 5

CH

3

CH

3 H BrCH 2 3.43 C6H 5

CH

2

OCH

3 Gil 3 2-CH 3

-C

6 H4 H myn.143-145 0

C

3.44 C 6 Hs GM 3

CYCIO-C

3 H5 2-CH 3

-C

6 H4 H M.p.107-109 0

C

3.45 C 6 H5 CH 3 CYC1o-C 3

H

5 2-F-C 6 H4 CH 3 3.46 C 6

H

5

CM

3 n-CsilII 3-CH 3 0-C 6

H

4

CH

3 3.47 C6s CH 3

CH

3

C

6

H

5 H m.p.138-140'C 3.48 4-(cH 3 2

CH-C

6 H4 CM 3

CM

3

-(CH

2 )3- HO\ I 3.49 4-Br-C 6 H4 CH 3

CH

3 H \m.p.255-256 0

C

3.50 4-F-c 6

H

4 CYC1o-C3H5 GM 3

CH

3 H m.p.162-164 0

C

3.51 4-F-C 6

H

4 CYC1o-C 3

H

5

CH

3

CH

3

CM

3 3.52 4-F-C 6 H4 CYC1o-0 3

H

5 Gil 3

(CH

3 2 CH H m.p. 58-60'C 3.53 C 6

H

5 Gil 3

CM

3 H 4-(Cii 3 2

N-C

6 lH 3.54 C 6 H5 CH 3

CH

3 H 4-CN-C6H4 3.55 C 6

H

5

GM

3

GH

2

OCH

3 H 2-OH-C 6

H

4 3.56 C 6

H

5

CM

3

GM

3 H 2,3-Cl 2

-C

6

H

3 m.p.221-222 0

C

3.57 C6H 5

CH

3

GM

3 H GH 2

=CH-

3.58 C6H 5

CM

3

GM

3

-CH=CHGM

2

CH

2

CH

2 3.59 C 6 Hs CM 3 CYC1o-C 3

H

5

-GH=CHCH

2

GH

2 3.60 G 6 Hs GM 3

GM

3 __C2)

-A

r a. a 4 a Table 3: (continuation) Comp. R R 2 R aR physical constant 3.61 C 6

H

5

CH

3 CYClo-C3H5 CH 3

CF

3 3.62 C6H 5

CH

3 CYClo-C3H5 CF 3 CF3 3.63 3,5-(CF 3 2 -C6H 3

CH

3

CH

3

C

2 H5 H n 25 1.4990 3.64 C6H 5

CH

3 CYClO-C3H5 H

CH

2 H

D

3.65 C 6

H

5

GH

3 CYC1o-C 3

H

5 H 2-pyridyl 3.66 C 6 Hs CH 3 CYC10-C3H 5 H 3-pyridyl 3.67 C6H5 CH 3 CYC1o-C 3 H5 H 4-pyridyl 3.68 C 6

H

5

CH

3

CH

2

OCH

3 H m.p.155-156 0

C

3.69 CsH5 CH 3

CH

3 H *m.p.177-179 0

C

S

3.70 C6H5 CIA 3 CYClo-C 3

H

5

CH

3 SCH2CH 2

H

3.71 CsH 5

CH

3

CIA

3

.CIA

3 3.72 C 6 Hs CH 3

CIA

3 C6H5 CF 3 3.73 C 6

H

5

CH

3 CYC1o-C 3

H

5

C

6 H5 CH 3 3.74 C 6 H5 CH 3

CH

2

OCH

3

CIA

3

CH

2

N(CH

3 2 3.75 Cr.H 5

CH

3 CYClo-C 3 Hs H CHC1 2 3.76 1C6Hs CIA 3 CYC1o-C 3

H

5 H CBr 3

S

on .0*0 o e a 0 0 0 0. 4 00 0 4 0 0 o 00* 000 00 400 Table 3: (continuation) Comp. RR2RR8R 9 physical constant 3.77 C 6

H

5

CH

3 Cu 3

H

3.78 3-F-CsH4 CH 3

OCH

2

CH

3 H (CH 3 2 CH m.p. 83-84%C 3.79 C 6 Hs CH 3 0CH 2

CH

3 H (CH 3 2 CH n 3 5 1.5673

D

3.80 C6H5 CYClo-C3H5 OH 3 2,3-C1 2

-C

6

H

3 H m.p.179-182 0

C

3.81 4-CF 3

-C

6 H4 OH 3

CH

3

OH

3

CH

3 3.82 4-cF 3

-C

6 H4 OH 3

CH

3 H 0 2

H

3.83 CsH 5

CH

3

CH

3

CH

3

(CH

2 6

H

3.84 0 6

H

5

CH

3 CYClo-C3H5 H C 2

H

3.85 4-F-C 6 H4 CYClo-C 3

H

5

OH

3 H m.io.132-134 0 0 3.86 3-F-C 6 H. CYClo-O3H5 CH 3 H m.p. 111-112'C L3 3.87 CsH 5

CH

2

OCH

3

CH

3

OH

3 H rn.p.112-114'C 3.88 C 6 Hs OH 3

CH

3 CYClo-C3H5 OH 3 n 2 4 1.600

D

3.89 3-F-c 6 H4+ OH 3 CYClo-C 3 H5 H OH 3 m.p.114-116'C 3.90 3-F-C 6 H4. OH 3 CYClo-C3H5 H 0 2

H

3.91 3-F-C 6

H

4

OH

3 CYClo-C3H5 H n-C3H7 m.p. 46-47%C 3.92 3-F-C 6

H

4

OH

3 CYClo-C3H5 H (CH 3 2 CH xn.p. 45-46%O *4 *4 *4 "A 4 0 0 0 40 0 4 a a ~o 0~ 6 0 Table 3: (continuation) Comp. RiR 3R 8

R

9 physical constant 3.93 G 6

H

5

CH

3 cyclo-G3H5 H -CH=GH 2 3.94 4-F-G 6

H

4

GH

3 CYClo-C3il5 G 2

H

5 H m.p. 79-80%G 3.95 4-F-C 6 H4i Gil 3 cyclo-G3H5 n-C 3

H

7 H m.p. 80-81%C 3.96 C 6

H

5

CH

3 CYClo-C 3 H5 H H2 /CH 3.97 C 6 H5 GH 3 CYC10-C3H5 G 2

H

5

CH

3 3.98 3-F-C 6 H4 GH 3 CYC10-C 3

H

5

GH

3

CH

3 3.99 3-F-C6H. CH 3 CYC10-C3H5 CH 3

C

2 Hs 3.100 3-F-G 6 H4 CH 3 CYC1o-C3HS Gil 3

CF

3 3.101 4-F-G 6 H4 Gi 3 CYClo-C3H5 CCd 3

H

3.102 4-F-G 6 H4. Gi 3 CYC10-C3H5 GH 2

OGH

3 Gil 3 3.103 CsH5 CH 2

OGH

3 CYC10-C 3 H5 H 1-naphthyl m.p.127-128 0

C

3.104 3-F-C6H4 CH 2

OCH

3 Gil 3 H 2-pyridyl 3.105 3-F-C 6

H

4 CYClo-C3l5 GH 3

CH

3

SCH

2

CH

2

H

3.106 3-F-c 8 H4+ CYC1o-C 3

H

5

CH

3

(GH

3 3 C H m.p.104-105'C 3.107 C6H 5 CYC10-G3il 5 Gil 3

(CH

3 3 C H m.p.100-102'C 3.108 C6H5 CYClo-C3il5 CH 3 H m.p. 90-92%G 3.109 GsH 5 CYClo-G3H5 Gil 3 H CYClo-C 3

H

3.110 G6iS Gil 3 Gil 3 2-pyridyl Gil 3 3.111 G 6

H

5 Gil 3 Gil 3 Gil 3 2,4-C1 2 -COi 3 3.112 sHs Gil 3 Gil 3 Gil 3

(CH

2 7

GH

3 3.113 3-F-C6H4 Gil 3

CH

2

OGH

3 4-pyridyl H w.:).190-192 0

G

Table 3: (continuation) Comp. RIR 2 R3R R 9 physical 3.114 C 6 H5 CH 3

CH

2 00H 3 H 2,3-Cl2-C 6

H

3 m.p.185-186 0

C

3.115 0 6 Hs 0113 CH 2

OCH

3 m.p.121-122 0

C

113 3.116 3-F-C 6 11 4

CH

3

CHZOCH

3 C11 3 H m.p.144-145 0

C

3.117 C 6 H5 CH 3

CH

2

OCH

3 H n-C 3

H

7 n 2 5 1.5756

D

3.118 CsH5 CH 3 0113 H C(CH 3 3 m.p. 73-74*C 3.119 C 6

H

5

CH

3

CH

2 0C1 3 H C(CH 3 3 m.P.100-101 0

C

3.120 06115 CH 3

CH

3 H n-C3H7 n 25 1.5860

D

3.121 3-F-C 6

H

4 C11 3

CH

2 0CH 3 H n-C3H7 m.p. 47-48%C 3.122 4-FC 6

H

4

CH

3 jH C(CH 3 3 m.p. 27-128%C

I.

a- Table 4: Compounds of formula Ri ,R3 RioR( i) \N Comp. RiR2 R 3 Ri iLphysical I constant 4.1 C6H5 CH 3

OH

3 H CH 3 n 25 1.5963

D

4.2 C6H 5

OH

3

CH

3 H C 2

H

4.3 C 6

H

5

OH

3

CH

3 H CH 2

CH=CH

2 4.4 C 6

H

5

CH

3

CH

3 H n-C3H 7 n 24 1.5740

D

C

6

H

5 cyclo-C 3 H5 CH 3 H CH 2 C CH 4.6 4-CH 3

O-CHL

4

CH

3

CH

3 H n-C 5

H

1 1

/CH

2 4.7 C6H5 OH 3 CYC1o-C 3 H5 H n 25 1.6160

SD

3,4-(CH3) 2

-C

6 H3 CH C7 WL 0 en La S fl 0 4, 5 4 a a. a a CC 0 C S 009 Table 4: (continuation) Comp. R 1

R

2

R

3 R2.o R1 1 physical constant

/GH

2 4.9 4-CF 3

-C

6 H4 CH 3

CH

3 "*CH3 4.10 3-F-C6H 4

CH

3 CYC1o-C 3 H5 n-C 3

H

7 n-C 3

H

7 n 27 1.5510

D

4.11 C 6 H5 CH 2 00H3 CH 3

CH

2

C(CH

3 3

H

4.12 C6H5 CH20CH 3

CH

3

,.-CH

2

H

4.13 CsH5 CH 3

CH

3

CH

3

CH

3 n 2 5 1.5673

D

4.14 C6Hs Gil 3

CH

3 C6H 5

CH

2 H M.D. 56-57'C 4.15 CsH 5

CH

3 CYC1o-C3H5 2

H

4.16 4-F-C6H 4 Gil 3 CYC1o-C3Hs aCH 2 H M.P. 83-84 0

C

4.7Gi5CH0H3C 3 H CH 3 n 24 1.5793 4.18 CsH5 CH 2

OGH

3 Gil 3

CH

3

CH=CHCH

2

H

4.19 Crils CH 2

OCH

3 Cil 3

CF

3

CH

2

H

4.20 Coils CH 2

OCH

3

GH

3 n-C 3

H

7 H n 25 1.5635

D

Os...

0 a Table 4: (continuation) Camp. R 10 i R 11 physical constant

\/CH

2 4.21 C6H 5

CH

2

OCH

3

CH

3 H H

OH

4.22 4-F-C 6

H

4

CH

3 CYCIO-C3H5 C 2

H

5 H n 23 1.5693

D

4.23 3-Br-C6H 4

CH

3 cyclo-C3H5 n-C 4

H

9

CH

3 4.24 2-Cl.-4-CF 3

-C

6

H

3

CH

3

CH

3

CH

3

C

2 Hs 4.25 C 6 H5 C 2

H

5

CH

3 H CH 3 4.26 C6H5 n-C 3 H5 CH 3 H Gil 3 4.27 C 6 H5 CH(CH 3 2 CHl(C1 3 2 H Gil 3 4.28 C 6 Hs CH 3 c(cH 3 3 H CH 3 4.29 C6H 5

C

2 H5 C 2

H

5 H CH 3 4.30 C 6 Hs CH 3 CH2OCH 3 H *CH 2 4.31 4-F-C 6 H+i CH 3

CH

3

C

2

H

5

C

2

H

5 n 25 1.5533 4.32 4-F-C 6 H4 CH- 3

CH

3

CH

3 H D 579C 4.33 C 6

H

5 Gil 3

CH

3

CH

2 CCl 3

H

4.34 C 6

H

5 Gil 3 GH3 CH3_H 4.35 C 6

H

5

CH

3

CH

3

(CH

3 2 C1 H 4.36 C6H5 CYC1o-C 3

H

5

CH

3

(CH

3 2 CH H n 2 4 1.5772 4.37 C 6

H

5 CYC1o-C3H5 Gil 3

C

2

H

5

(CH

3 )CH- HD 4.38 C 6 H5 CH 3

CH

3 Br 3

GCH

2

H

4.39 C 6

H

5 Gil 3

CH

3

CH

2

CH

2 CYK H 4.40 C 6 H5 Gil 3 Gil 3

CH

2

CH

2 CT1 CH 2

CH

2

CN

4.41 CsH5 CH- 3 CYClo-C 3

H

5

CH

2

GH

2 CN CH 2

CH

2

CN

C. CC C C C

C

C C C C 0 CC C

CCC

Table 4: (continuation) Comp. RiR 3R.oR ,pnysical 4 4.42 C 6 H5 Gil 3 Cyclo-C3H5 CH 2

CH

2 CN H 4.43 CsHs CH3 CYC1o-C3H5 cyc1o-C6HIl H m.p. 75-77*C 4.45 C6Hs CH 3 cyclo-C3H5 Gil 3 H n 2 5 1.5830

D

4.46 3-F-C 6 H. CH 3 CYC10-C3H5 Gil 3 H n 3 b 1.5842

D

4.47 3-F-C 6 H4 CH3 cyclo-C3H5 C 2 H5 H n 23 1.5778 4.48 4-F-C 6

H

4 Gi 3 CYC1o-C 3

H

5

C

2

H

5

(CH

3 )CH H D 4.49 C 6 H5 CH3 Gil 3 H CYClo-C6Hh1 4.50 C 6 H5 CH3 CH3 H\ 4.51 C 6 H5 CH3 Gil 3 H cyclo-CsH 9 m.p. 84-86 0

C

4.52 C 6

H

5

CH

2

OCH

3 CH3 CH 3

OCH

2 (CH3)CH- H n 2 4 1.5565 4.53 C6Hs

GH

2

OCH

3 CH3 (CH 3 2

NGH

2

(CH

3 )GH- HD 4.54 3-F-c 5 H4 CH 2 OCH3 CH 3 H (CH 3

)CHCH

2 4.55 3-F-C 6 H. CH 2 OCH3 Gil 3 H n-C 3

H

7 4.56 3-F-C6H. CH 2

OCH

3 CH3 (CH 3 )zCH H n 23 1.5450

D

4.57 4-I-C 6 H4 Gil 3

CH

3 NC-- >-CH 2

H

4.58 C 6 H5 Cil3 CYClO-G3HS H CYClo-C6Hl1 m.p. 75-77'C 4.59 Gsl 5 Gil 3 CYClO-C3HS H- H 0 a.

0 r Table 4: (continuation) comp. RI

R

2

R

3 RioR 0 physical constant 4.60 CSs CH 3 cyclo-C3H5 H n-C 3 H7 p.217C 4.61 C6H 5

CH

3 cyclo-C 3 H5 H COHS p.5-2 0 4.62 C6H 5

CH

3 cyclo-03H5 CF 3

CH

2

H

4.63 2-F-C6H4 OH 3 cyclo-C3H5 Br 3 CCH2 H 4.64 2-F-CsH4 O 2 H5 CH 3 C1 2

CHCH

2

H

4.65 4-F-C 6 H. CH 3 cyclo-C3H5 H3CH H

F

3

C

4.66 4-F-C 6 H4 CH 3 CYC10-C3H5 H 4.67 4-F-C 6 H. CH 3 CYC10-C3H5 H n-C 3

H

7 4.68 4-F-CsH4 CH 3 cyclo-C3Hs H (CH 3 2

CHCH

2 4.69 C6H 5

OH

3

CH

2 0CH 3 CH3 OH 3 n 2 4 1.5595 4.70 C 6

H

5

CH

3

CH

2 0CH 3 n-C 3

H

7 n-C 3

H

7 n 23 1.5483

D

4.71 C 6 H5 CH 3

CH

2 0CH 3 H CH 3

(CH

2 7 4.72 OsHs CH 3 CH20CH 3 BrCH 2 CHO H 4.73 COHS CH 3

CH

2 0CH 3 H3 CH2 H m.p. 67-68'C 4.74 CeHs CH 3

CH

3 H C 2

H

5

(CH

3 )CH- n 23 1.5638 4.75 C 6

H

5

OH

3

CH

3

C

6 Hs(CF 3 )CH- H

A

4 C U. S C S cm r 4 CC S 5* S S S 50 0 PU) Table 4: (continuation) Comp. R 10 R3Ro i physical constant /SCH 3 4.76 C6H5 CH 3

OH

3 H "CH 2 4.77 C 6 H5 0113 CH 3

(CH

3 2

CHCH

2 H n 2 4 1.5623

D

4.78 C 6 HS OH 3

OH

3 H -CH 2 n 25 1.6175

SD

4.79 C 6

H

5

OH

3

CH

3 l>-CH 2

H

4.80 C6Hs CH 3

CH

3

CF

3

CH

2

H

4.81 C 6 H5 CH 3 CYC1o-C3H5 01H 02115 n 2 4 1.5803

D

4.82 C6H5 0113 CYClo-C3H5 H Br 3 C0H 2 4.83 Cs CH 3 CYClo-C3H5 !\I-CH 2

H

CH

4.84 CgH 5

CH

3 CYC10-C 3

H

5 H /I H mIi.p. 62-63'C

CH

2

U

4 S 0 0 *4 00 0 0 0 0 0 0 0 0 *00 S 0 a a 000 Table 4: (continuation) Comp. RI R R 3 Roilphysical constant 48 rsC3cclo--C3H5 H /I II mn.p. 67-68 0

C

4.86 C 6

H

5

CH

3 CYClo-C3Hs /-CH 2

H

4.87 CsH 5 Gil 3 cyclo-C3H5 H- (CH 3 2 CHCH2- n 2 5 1.5733 4.88 C 6 Hs CH 3 CYClo-C3H5 H CH 3

CH=CHCH

2 4.89 CGHs CH 3 CYCIO-G3H5 C 6 H5CH2 H 4.90 4-F-C 6 H4 013 cyclo-C3H5 n-C 3 H7 n-C 3 H7 n 23 1.5483 4.91 3-F-C 6 H4 CH 3 0CH 2

CH

3 H ICH 3 4.92 3-F-C 6 H4 CH30CH2 0113 H C 2

HS

4.93 3-F-C6H4 CH 3

OCH

2

CH

3 H n-C4H9 4.94 4-CF 3 0-C6H4~ CH 3 0CH 2

CH

3 H 02115 4.95 4-CF 3

O-C

8 114 CH 3 0CH 2

CH

3

CH

3

CH

3 4.96 4-I-05114 CH 3 CYClo-C3HS H n-C3H7 4.97 4 -I-C6H4 CH 3 CYClO-C3H5 H (CH 3 2

CHCH

2 4.98 C6Hs Gil 3 CYCIO-C3H5 0113 CH 3 n 3 l 1.5813 4.99 C 6 Hs CH3 CYClO-C3H5 02115 C 2 Hs n24 1.5762

D

4.100 C 6 Hs 0113 CYClo-C3HS H CH 2

=CHCH

2 4.101 CsH5 OH 3 CYClo-C 3 H5 CH 3

SCH

2 CH2CH 2

H

4.102 06Hs CH 3 CYClo-C311s CH 3

CH

2

GH(CH

3 2 n 3 0 1.5613 D3 bM6a a P a.

6 0 S.C C 6 aba a a Ca 0 0 P 0 O0 6* C 0*0 00 *C~ Table 4: (continuation) Comp. RIR2

R

3

R

10 R1 physical constant 4.103 C635 CH 3 CYClo-C 3 H5 H 4.104 C 6 H5 C 2

H

5

CH

2

OCH

3 H CH 3 n 2 4 1.5753

D

4.105 C6HS CH 3

CH

3

CH

2

-CH

2

H

4.106 C6Hs CYC10-C 3 H5 CH 3

CH

3

OCH

2

(CH

3 )CH- CH 3 4.107 C 6 H5 cyclo-C 3 H5 CH 3

CF

3

(CH

3 )CH- CH 3 4.108 C6H 5 CYC10-C 3 H5 CH 3

(CF

3 2 CH- H 4.109 3-F-c 6 H. n-C 3

H

7 n-C 3

H

7 H n-C--H' 7 4.110 3-F-C 6 H. CH 3

ICH

3 CH 3 n 2 3 1.5765

D

4.111 C6s CH 3

-ICH

2

C(CH

3 3 H m.p. 69-70'C 53 2. Formulation Examples for liquid active (throughout, percentages are by weight) ingredients of formula I i ii 2.1. Emulsifiable concentrates a compound of Table 1 2 calcium dodecylbenzenesulfonate castor oil polyethylene glycol ether (36 moles of ethylene oxide) tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) cyclohexanone xylene mixture 6.

Emulsions of any desired concentration trates by dilution with water.

a) 5% 5 b) 40 8% c) 50 6% 12 15 5 25 4% 20 20 4 r4 I Ir I I 'd can be produced from such concen- 2.2. Solutions a compound of Table 1 ethylene glycol monomethyl ether polyethylene glycol (mol. wt. 400) N-methyl-2-pyrrolidone epoxidised coconut oil petroleum fraction (boiling range 160-190 0

C)

a) 80 20 b) 10 c) d) 5 95 70 20 1% S 94 These solutions are suitable for application in the form of micro-drops.

2.3. Granulates a compound of Table 1 kaolin highly dispersed silicic acid attapulgite a) 5 94 1 b) 10 90 r L~LLI I _i i i i -a 54 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

2.4. Dusts a compound of Table 1 highly dispersed silicic acid talcum kaolin a) 2% 1% 97 b) 90 Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.

Formulation Examples for solid active ingredients of formula I (throughout, percentages are by weight) r

I,

*i I

I..

Wettable powders a compound of Table 1 sodium lignosulfonate sodium laurylsulfate sodium diisobutylnaphthalenesulfonate octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) highly dispersed silicic acid kaolin a) 25 5% 3% b) 50 c) 75 6 10 5% 62 2% 10 27 10 The active ingredient is thoroughly mixed with the adjuvants and the S mixture is thoroughly ground in a suitable mill, affording wettable i t powders which can be diluted with water to give suspensions of the desired concentration.

2.6. Emulsifiable concentrate a compound of Table 1 octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 10 3% I

F

55 calcium dodecylbenzenesulfonate 3 castor oil polyglycol ether moles of ethylene oxide) 4 cyclohexanone 34 xylene mixture 50 Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

2.7. Dusts a) b) a compound of Table 1 5 8 talcum 95 kaolin 92 S" Ready-for-use dusts are obtained by mixing the active ingredient with the I carrier and grinding the mixture in a suitable mill.

2.8. Extruder granulate a compound of Table 1 10 sodium lignosulfonate 2 carboxymethylcellulose 1 kaolin 87 The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.

2.9. Coated granulate ti a compound of Table 1 3 polyethylene glycol (mol. wt. 200) 3 kaolin 94 The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

I'

i I n ar~--sp 56 2.10. Suspension concentrate a compound of Table 1 ethylene glycol nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) sodium lignosulfonate carboxymethylcellulose 37 aqueous formaldehyde solution silicone oil in the form of a 75 aqueous emulsion water 40 10 6 10 1 0.2 0.8 32 a go Sr o r The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

3. Biological Examples Example 3.1: Action against Venturia inaequalis on apple shoots Residual protective action Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.006 active ingredient) prepared from a wettable powder formulation of the test compound. The treated plants are infected S 24 hours later with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100 relative humidity and stood in a greenhouse for a further 10 days at 20-24 0 C. Scab infestation is evaluated 15 days after infection.

Compounds of the Tables exhibit good activity against Venturia (infestation: less than 20 For example, compounds 1.79, 1.108, 1.122 and 4.45 reduce Venturia infestation to 0 to 10 On the other hand, Venturia infestation is 100 on untreated and infected control plants.

I

F

i -I -r 57 Example 3.2: Action against Botrytis cinerea on apples Residual protective action Artificially damaged apples are treated by dripping onto the damaged areas a spray mixture (0.002 or 0.02 active ingredient) prepared from a wettable powder formulation or an emulsifiable concentrate of the tesc compound. The treated fruits are then inoculated with a spore suspension of the fungus and incubated for one week at high humidity and about 20 0

C.

Evaluation of the fungicidal action of the test compound is made by counting the number of damaged areas that have rotted.

Compounds of the Tables exhibit good activity against Botrytis (attack: less than 20 For example, compounds 1.4, 1.6, 1.7, 1.12, 1.17, 1.48, 1.55, 1.56, 1.65, 1.68, 1.79, 1.104, 1.108, 1.118, 1.119, 1.122, 1.124, 1.129, 1.137, 1.138, 3.5, 3.6, 3.7, 3.8, 3.10, 3.11, 3.25, 3.26, 3.35, 3.40, 3.41, 3.50, 3.52, 3.78, 3.79, 3.113, 3.115, 4.1, 4.4, 4.15, 4.17, 4.20, 4.45, 4.56, 4.73, 4.74, 4.87 and 4.98 reduce Botrytis attack to 0 to 10 On the other hand, Botrytis attack is 100 on untreated and infected control plants.

4 400909 0 4 Example 3.3: Action against Erysiphe graminis in barley a) Residual protective action Barley plants about 8 cm in height are sprayed with a spray mixture (0.02 active ingredient) prepared from a wettable powder formulation of S the test compound. The treated plants are dusted with conidia of the fungus after 3 to 4 hours. The infected barley plants are stood in a greenhouse at about 22 0 C and the fungus attack is evaluated after days.

Compounds of the Tables exhibit good activity against Erysiphe (attack: less than 20 For example, compounds 1.32, 1.56, 1.104, 1.122, 1.124, 3.8, 3.44 and 3.52 reduce the Erysiphe attack to 0 to 10 On the other hand, Erysiphe attack is 100 on untreated and infected control plants.

_i I_ _i 58 Example 3.4: Action against Helminthosporium gramineum Wheat grains are contaminated with a spore suspension of the fungus and dried. The contaminated grains are dressed with a suspension of the test compound prepared from a wettable powder (600 ppm of active ingredient bascd on the 'Teight of the seeds). Two days later the grains are placed in suitable agar dishes and after a further 4 days the development of the fungus colonies around the grains is evaluated. Evaluation of the test compound is made according to the number and size of the fungus colonies.

Compounds of the Tables inhibit fungus attack substantially (less than fungus attack).

Example 3.5: Action against Colletotrichum lagenarium on cucumbers Cucumber plants are grown for 2 weeks and are then sprayed with a spray mixture (concentration 0.002 prepared from a wettable powder formulation of the test compound. 2 days later, the plants are infected with a t spore suspension (1.5 x 0l spores/ml) of the fungus and incubated for 36 hours at 23 0 C and high humidity. Incubation is then continued at normal humidity and approximately 22-23 0 C. The fungus attack which occurs is evaluated 8 days after infection. Fungus attack is 100 on untreated and infected control plants.

Compounds of the Tables exhibit good activity and prevent the disease from spreading. Fungus attack is reduced to 20 or less.

Example 3.6: Action against Puccinia graminis in wheat Wheat plants are sprayed 6 days after sowing with a spray mixture (0.02 active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated t t for 48 hours at 95-100 relative humidity and about 20 0 C and then stood in a greenhouse at about 22 0 C. Evaluation of rust pustule development is made 12 days after infection.

59 Compounds of the Tables exhibit good activity against Puccinia (attack: less than 20 For example, compound no. 3.10 reduces Puccinia attack to 0 to 10 On the other hand, Puccinia attack is 100 on untreated and infected control plants.

Example 3.7: Action against Phytophthora on tomato plants a) Residual protective action After a cultivation period of 3 weeks, tomato plants are sprayed with a spray mixture (0.02 active ingredient) prepared from a wettable powder formulation of the test compound. The treated plants are infected 24 hours later with a sporangia suspension of the fungus. Evaluation of the fungus attack is made after the infected plants have been incubated for 5 days at 90-100 relative humidity and 20 0

C.

b) Systemic action After a cultivation period of 3 weeks, tomato plants are watered with a spray mixture (0.002 active ingredient based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The treated plants are infected 48 hours later with a sporangia suspension of the fungus. Evaluation of the fungus attack is made after the infected plants have been incubated for 5 days at 90-100 relative humidity and 20 0

C.

Compounds of the Tables exhibit good activity against Phytophthora (attack: less than 20 For example, compounds 1.104, 1.122, 4.31 and 4.98 reduce Phytophthora attack to 0 to 10 On the other hand, Phytophthora attack is 100 on untreated and infected control plants.

Claims (20)

1. A compound of formula I Rl> I R\R wherein: R, is phenyl or phenyl mono- to tni-substituted by R4; R2 is hydrogen, Ci-Osalkyl, G 1 -Csalkyl substituted by the radical ORB or by the radical SR5, C3-C6cycloalkyl, C3-C~cycloalkyl mono- to tni-substituted by C 1 -Cz~alkyl or by halogen, C 2 -Csalkenyl, C 2 -C 5 alkynyl or the formyl radical; R 3 is hydrogen, Cl-CL~alkyl, CI-Ci~alkyl substituted by halogen, cyano or by the radical ORB or by the radical SR5, C 3 -Cscycloalkyl or C3-C6cycloalkyl mono- to tni-substituted by CI-C 4 alkyl or by halogen; R 4 is halogen, CI-C 3 alkyl, Cl-C 2 haloalkyl, Ci-C 3 alkoxy or Cl-C3haloalkoxy; *tt~ R 5 i~s hydrogen, Cl-Csalkyl, C 3 -Csalkenyl, C3-Csalkynyl or the radical (CH2) -X-Cl-C 3 -alkyl; 114n /R8 114 R7 is the group -N911, or Ra is hydrogen, CI-C 3 alkyl or Cl-C3haloalkyl; R 9 is hydrogen, Ci-C 8 alkyl, CI-Caalkyl substituted by hydroxy, 0R 12 SR1 2 or by N(Rl2) 2 C3-C6cyclo- alkyl, cyclopropyl substituted by SR 12 C3-Cloalkenyl, C 1 -C 3 haloalkyl, phenyl, phenyl mono- to tni-substituted by halogen, Cl-C 3 alkyl, CI-C3- alkoxy, Cl-C 3 haloalkoky, Cl-C2haloalkyl, hydroxy, nitro, cyano, amino or by dimethylamino, 1- or 2-naphthyl, 2- or 3-pyridyl, Ra and R 9 toehrwt the carbon atom in the radical R7, are a saturated or unsaturated ring comprising 4 to 7 carbon atoms; Rio is CH(R 8 )R 9 phenyl, C 3 -Csalkenyl, C 3 -Csalkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; Ril is hydrogen, Cl-Osalkyl,

03-Osalkenyl, C3-Csalkynyl or cyanoalkyl having 2 or 3 carbon atoms -61 in the alkyl radical; R 1 2 is CH 3 or C 2 Hs; X is oxygen or sulfur; Z is 0, S, NH or NCH 3 and n is 1 to 3; including the acid addition salts and metal salt complexes thereof. 2. A compound of formula I according to claim 1, wherein: RI is phenyl or phenyl mono- to tri-substituted by R4; L 2 is hydrogen, C 1 -Csalkyl, Ci-Csalkyl substituted by the radical ORs or by the radical SRs, C 3 -C6- cycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by Ci-C4alkyl or by halogen, Cz-Csalkenyl, C 2 -Csalkynyl or the formyl radical; R 3 is CI-C 4 alkyl, C1-Cialkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, Ca-C6cycloalkyl or C3-Cscycloalkyl mono- to tri-sub- stituted by Ci-Cialkyl or by halogen; R4 is halogen or Ci-C3alkyl; Rs is hydrogen, Ci-Csalkyl, C 3 -Csalkenyl, C 3 -Csalkynyl or the radical (CH 2 -X-C 1 -C 3 alkyl; R 9 is hydrogen, Ci-Csalkyl, C3-Cscycloalkyl, C 3 -Cs- alkenyl, C 1 -C3haloalkyl, phenyl or phenyl mono- to tri-substituted by halogen, methyl, methoxy, halomethoxy or by halomethyl; R 8 and Rg, Stogether with the carbon atom in the radical R7, are a saturated or un- Ssaturated ring comprising 5 or 6 carbon atoms; R 7 Rio, R 1 1 R12 and Z S are as defined under formula I; X is oxygen or sulfur; and n is 1 to 3. 4I 3. A compound of formula I according to claim 1, wherein: RI is phenyl or phenyl mono-substituted by halogen; R 2 is hydrogen, C1-Csalkyl, C 1 -Cs- alkyl substituted by ORs, C 3 -Cscycloalkyl, C 3 -Cscycloalkyl mono- to tri- substituted by Ci-Coalkyl or by halogen, Cz-Csalkenyl, Cz-Csalkynyl or the formyl radical; R3 is Ci-C4alkyl, Ci-C.alkyl substituted by halogen, cyano or by ORs, C3-Cscycloalkyl or C 3 -Cscycloalkyl substituted by methyl; Rs is hydrogen or CI-Czalkyl; R 9 is hydrogen, C 1 -Csalkyl, Ca-Cs- cycloalkyl, Ca-Csalkenyl, Ci-Cahaloalkyl, phenyl or phenyl mono- to tri- substituted by halogen, methyl, methoxy, halomethoxy or by halomethyl; Re and R 9 together with the carbon atom in the radical R 7 are a saturated or unsaturated ring comprising 5 or 6 carbon atoms; and R7, Rio, RI 1 and R 1 2 are as defined under formula I.

4. A compound of formula I according to claim 1, wherein: Ri is phenyl or phenyl mono- to tri-substituted by R4; R 2 is hydrogen, Ci-Csalkyl, Ci-Cs- alkyl substituted by the radical ORs or by the radical SRs, C3-Cscyclo- Ii I -62- alkyl, G3-C6cycloalkyl mono- to tni-substituted by CI-Cialkyl or by halogen, C 2 -Gsalkenyl, C 2 -C 5 alkynyl or the formyl radical; R 3 is Cl-C4- alkyl, C 1 -Ci~alkyl substituted by halogen, cyano or by the radical ORs or by the radical SR5, C3-C6cycloall-yl or C 3 -Cs~cycloalkyl mono- to tri- substituted by CI-C4alkyl or by halogen; R4 is halogen, Cl-C 3 alkyl, Cl-C 2 haloalkyl, CI-C 3 alkoxy or CI-C 3 haloalkoxy; R 5 is hydrogen, CI-C 5 alkyl, C 3 -Csalkenyl, C 3 -G 5 alkynyl or the radical (CH 2 n-X-Cl-C 3 alkyl; R 7 is -NH 2 X is oxygen or sulfur; and n is 1 to 3; including the acid4 addition salts and metal salt complexes thereof. A compound of formula I according to claim 4, wherein: R, is phenyl orT phenyl mono- to tni-substituted by R4; R 2 ishbydrogen, Cl-C 5 alkyl, Cv-Csalkyl substituted by the radical OR5 or by the radical SR 5 C 3 -C6- cycloalkyl, C 3 -C 6 cycloalkyl mono- to tni-substituted by CI-Ci~alkyl or by :halogen, C 2 -C 5 alkenyl, C2-C5alkynyl or the formyl radical; R 3 is C 1 -C 4 alkyl, C3 1 -C~alkyl substituted by halogen, cyano or by the radical OR5 or by the radical SR 5 C 3 -Cscycloalkyl or C3-C6cycloalkcyl mono- to tni-sub- stituted by CI-Ci~alkyl or by halogen; R4. is halogen; R5 is hydrogen, CI-C 5 alkyl, C 3 -C 5 alkenyl, C3-Csalkymyl or the radical (CH 2 -X-Ca-C 3 n- alkyl; X is oxygen or sulfur; and n is 1 to 3.

6. A compound of formula I according to claim 1, wherein: R, is phenyl or phenyl mono- to tni-substituted by halogen; R 2 is hydrogen, C 1 -Csalkyl substituted by the radical ORS or by the radical SR 5 C 3 -C 6 cycloalkyl, C3-Cscycloalkyl mono- to tni-substituted by Ca-Ci~alkyl or by halogen, C 2 -C 5 alkenyl, C 2 -Csalkynyl or the formyl radical; R 3 is Cl-C 4 alkyl, CI-Ci~alkyl substituted by halogen, cyano or by the radical OR5 or by the radical SR 5 C3-C6cycloalkyl or C 3 -C~cycloalkyl mono- to tni-sub- stituted by CI-Ct~alkyl or by halogen; R 5 is hydrogen, Cl-C 5 alkyl, C 3 -C 5 alkenyl, C 3 -Csalkynyl or the radical (CH 2 )n-X-Cj-C:~alkyl; X is oxygen or sulfur; and n is 1 to 3.

7. A compound of formula I according to claim 1, wherein: R, is phenyl or phenyl mono-su'lstituted by chlorine or by fluorine; R 2 is Cl-Csalkyl, or is Cl-C 2 alkyl substituted by 0R5, C 3 -Cscycloalkyl, C3-C6cycloalkyl mono- to tni-substituted by CI-Ci~alkyl or by halogen, C2-Csalkenyl, C 2 -CS- V -63- alkynyl or the formyl radical; R 3 is Cl-Cqalkyl, CI-C~haloalky1, C 3 -C 6 cycloalkyl or C3-Cscycloalkyl substituted by methyl; and R 5 is hydrogen or CI-C 2 alkyl.

8. A compound of formula I according to claims 6 and 7. wherein R 3 is: methyl, fluoromethvl, chioromethyl, bromomethyl, C 3 -C 6 cycloalkyl or methoxymethyl.

9. A compound of formula I according to claim 1 from the group: 4-fluoromethyl-6-cyclopropylpyrimid-2-yl) -N-phenylhydrazine; 4 -methyl-6-cyclopropylpyrimid-2-yl)-N-m-fluorophenylhlydrazine; 4 -methyl--6-cyclopropylpyrimid-2-yl) -N-p-fluorophenylhydrazine. V 10. A compound of formula I according to claim 5 from the group: N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenylhydrazine; 6-di- methylpyrimid-2-yl)-N-phenylhydrazine; N-(4-methyl-6-methoxymethyl- pyrimid-2-yl)-N-pheny'lhydrazine.

11. A compound of formula I according to claim 1 from the group: 4, 6-dimethylpyrimid-2-yl) -N-phenylpropionaldehyde hydrazone; o 6-dimethylpyrimid-2-yl>--N-phenylisobutyraldehyde hydrazone; $fall N-(4-methyl-6--methoxymethylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; 4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenylpropionaldehyde hydra zone; 4-methyl-6-cyclopropylpyrimid-2-yl) -N-phenylpropionaldehyde hydrazone; N-( 4 -methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-n-butyraldehyde hydrazone; a' N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; 4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyltrichloroacetaldehyde hydrazone; 4-methyl-6-cyclopropylpyrimid-2-yl) -N-E-fluorophenylacetaldehyde hydra zone; 4-methyl-6-cyclopropylpyrimid-2-yl) -N-p-fluorophenylisobu tyraldehyde hydra zone; -64- 4 -methyl-6-cyclopropylpyrimid-2-yl)-N-m-fluorophenylisobutyraldehyde hydra zone; N-( 4 ,6-dkimethylpyrimid--2-yl)-N-phenyl-N'-methylhydrazine; 4, 6-dimethylpyrimid-2-yl) -N-phenyl-N' -dimethyihydrazine; N-( 4 ,6-diriethylpyrimid-2-yl)-N-phenyl-N'-n-propylhydrazine; N-(4,6-dimethylpyrimid-2-y1)-N-phenyl-N'-isobutylhydrazine; 4 -me thyl-6-methoxymethylpyrimid-2-yl)-N-phenyl-N' -methylbydrazine; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenyl-N' -n-propylhydrazine; i 4 -me thyl-6-methoxyme thylpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N' -methyihydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-isobutylhydrazine; 4 -methyl--6-cyclopropylpyrimid-2-yl) -N--phenyl-N' -dimethyihydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-diethylhydrazine; 4-methyl-6-cyclopropylpyrimid-2-yl) -N-phenyl-N' -methyl-N' -ethyl- hydrazine; 4 -methyl-6-cyclopropylpyrimid-2-yl) -N-p-fluorophenyl-N'-ethyl- hydrazine; N 4 -metbyl-6-methoxymethylpyrimid-2-yl)-N-m-fluoropenyl-N'-isopropyl- hydrazine. 3. 4 4 t12. A process for the preparation of a compound of formula I according to 44k claim 1, which comprises a) reacting a pyrimidine derivative of formula II /,R2 N-" \R3 with a phenylhydrazine derivative of formula III R 1 -NH-NH-R (III) 65 in the presence of a base, in an aprotic solvent and at temperatures of to 150 0 C, wherein Y is halogen, the radical SO 2 R 6 or N (CH 3 3 R 6 is Ci-C4alkyl, phenyl or phenyl substituted by methyl or by chlorine and R is as defined for Rio and R 11 and th lattr and also RI-R 3 are as defined under formula I or b) reacting a pyrimidine hydrazine derivative of formula IV with an aldehyde or ketone of formula V to form a compound of formula VII with the removal of water /R2 NH2 N=. (R3) (IV) RB^ C=o R9/ (VII) 4 t 1 4I '4'IC 4 4 1. in any desired solvent, in the presence of an acid and at temperatures of -200 to 120 0 C, RI-R 3 and R 8 and R 9 being as defined under formula I or c) reducing a hydrazone derivative of formula VII reduction /R2 R 1 1i \N=-l \3 CHR 8 (R 9 (VIII) (VII) using a reducing agent, in an inert solvent and at temperatures of 00 to 0 C or by catalytic hydrogenation using catalysts, or 66 d) subjecting a pyrimidine hydrazine derivative of formula IV /R2 /N- Ri (IV) NH2N=/ \R3 to reductive alkylation with an aldehyde or ketone of formula V R e -g-R 9 (V) in the presence of a reducing agent, in an inert solvent and at temperatures of '0 to 50 0 C, or 0 0 0 o o: e) alkylating a pyrimidine hydrazine of formula IV or VIII with an alkyl halide R Hal O Ra- R Hal R T \R3 R \R3 0 0 (IV) (IX) I R 2 R 2 N-* S.R-6 R Ha l and 3 CH CHRa(R9) R CHRs(R9) 0 (VIII) (X) in an inert solvent, in the presence of a base and at temperatures of 0O-600C, R being CI-C4alkyl and Ri-R9 in processes described above being as defined under formula I.

13. A composition for controlling or preventing attacks by insect pests or destructive microorganisms, which composition contains as active ingredient at least one compound of formula I according to claim 1 together with a suitable carrier. r 4, Z t 67

14. A composition according to claim 13, which contains ingredient at least one compound of formula I according A composition according to claim 13, which contains ingredient at least one compound of formula I according

16. A composition according to claim 13, which contains ingredient at least one compound of formula I according

17. A composition according to claim 13, which contains ingredient at least one compound of formula I according as active to claim 4. as active to claim 9. as active to claim as active to claim 11.

18. A method of controlling or preventing attacks on cultivated plants by t insect pests or phytopathogenic microorganisms, which method comprises S applying to the plant, parts of the plant or the locus thereof, as active ingredient, a compound of formula I according to claim 1.

19. A method according to claim 18, which comprises applying as active ingredient a compound according to any one of claims 2 to 11. I I:1 i i: *3i. _i A method according to claim 18, which comprises controlling phytopathogenic fungi. t I

21. A process for the preparation of an agrochemical composition according to claim 13, which process comprises homogeneously mixing at least one compound of formula I according to claim 1 with suitable solid or liquid adjuvants and/or surfactants. Z3 P pA p nr.nngj S. f A .PMIR T /R2 Y-. \N wherein R 2 is Ci-C9~akl or Ci-Csalkyl substituted by the radical ORs or by the r *al SRs; R 3 is Ci-C 4 alkyl substituted by halogen, cyano or by Sradical OR 5 or by the radical SRs; R 5 is hydrogcn, Gi-Calkyl, ,T s- -68

22. Substituted 2-amino pyrimidine derivatives, substantially as hereinbefore described with reference to any one of Examples 1.9 to 1.17, or Tables 1, 3 or 4.

23. A process for preparing substituted 2-amino pyrimidine derivatives, substantially as hereinbefore described with reference to any one of Examples 1.9 to 1.17.

24. A composition for controlling or preventing attacks by insect pests or destructive microorganisms, substantially as hereinbefore described with reference to any one of Examples 2.1 to 2.10.

25. A compound of formula I of claim 1, whenever prepared by a process according to claim 12.

26. A method for controlling microorganisms, which method comprises applying to the plant, parts of the plant or the locus thereof, as active ingredient a compound according to claim 22 or 25, or a composition according to any one of claims 13 to 17 or 24. DATED this TWENTY FIFTH day of MAY 1992 P'at" Ciba-Geigy AG °Patent Attorneys for the Applicant 20 SPRUSON FERGUSON S*, 4 1 I$ i4 i