Fungicidal 5-phenyl substituted 2-(cyanoamino) pyrimidines

Details Fungicidal 5-phenyl substituted 2-(cyanoamino) pyrimidines Fungicidal 5-phenyl substituted 2-(cyanoamino) pyrimidines

2001-06-12

2003-10-14

Ford, John M. (Department: 1624)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Having -c-, wherein x is chalcogen, bonded directly to...

C514S269000, C514S272000, C544S320000, C544S321000, C544S324000

Reexamination Certificate

active

06632821

ABSTRACT:

The present invention relates to pyrimidines of formula I
in which
R
1
represents hydrogen or
C
1
-C
10
-alkyl, C
1
-C
10
-haloalkyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkynyl, C
4
-C
8
-alkadienyl, C
1
-C
10
-alkoxy, C
3
-C
8
-cycloalkyl, phenyl, or
5- or 6-membered heteroaryl or 5- or 6-membered heterocyclyl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or
tri-C
1
-C
6
-alkyl-silyl, formyl or C
1
-C
10
-alkoxycarbonyl;
wherein R
1
groups are unsubstituted or substituted by one to three groups R
a
R
a
halogen, nitro, cyano, hydroxy or
C
1
-C
10
-alkyl , C
3
-C
6
-cycloalkyl, C
3
-C
6
-cycloalkenyl, C
1
-C
10
-haloalkyl, C
3
-C
6
-halocycloalkyl, C
1
-C
10
-alkoxy, C
1
-C
10
-haloalkoxy, C
1
-C
10
-haloalkoxy, C
1
-C
6
-alkoxycarbonyl, tri-C
1
-C
4
-alkylsilyl, phenyl, halo- or dihalo-phenyl or 5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom;
R
2
represents phenyl, C
3
-C
6
-cycloalkyl or 5- or 6-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, which are unsubstituted or substituted by one to three groups R
a
;
R
3
represents hydrogen, halogen or
C
1
-C
10
-alkyl, C
1
-C
10
-alkoxy, C
1
-C
10
-alkylthio, C
1
-C
10
-alkylamino or di-C
1
-C
10
-alkylamino; which are unsubstituted or substituted by one to three groups R
a
;
R
4
represents hydrogen or
C
1
-C
10
-alkyl, C
2
-C
6
-alkenyl or C
2
-C
6
-alkynyl; which are unsubstituted or substituted by one to three groups R
a
; and
X represents O, S, NR
5
or a single bond, wherein R
5
represents hydrogen or C
1
-C
10
-alkyl; or
R
1
and R
5
together with the interjacent nitrogen atom form a heterocyclic ring.
Moreover, the invention relates to processes and intermediates for preparing these compounds, to compositions comprising them and to their use for controlling harmful fungi.
In Vestn. Slov. Kem. Drus. (1986), 33(3), 353-66 (ISSN: 0560-3110, CAN 107:39701) it is disclosed that the reaction of N-pyrimid-2-ylformamide oximes with N,N-dimethylformamide diethyl acetal yields 2-(N-cyano-N-ethylamino)pyrimidines. In J. Org. Chem. 39 (9) 1256-1252 (1974) N-glycosylated 2-(N-cyanoamino) pyrimidines are disclosed and in U.S. Pat. No. 4,711,959 a process for the preparation of 2-(N-cyanoamino)pyrimidines is described.
It is an object of the present invention to provide fungicidal compounds having improved activity.
We have found that this object is achieved by the compounds defined at the outset. Furthermore, we have found processes for their preparation, compositions comprising them and methods for controlling harmful fungi using the compounds I.
Compounds of formula I wherein R
4
is an optionally substituted alkyl, alkenyl or alkynyl group as defined above may be obtained by treating a compound of the formula II
in which R
1
through R
3
and X are as defined in formula I; with a strong base and an alkylation agent of formula III
R
4
—Y  III
in which R
4
is C
1
-C
6
-alkyl, C
1
-C
6
-alkenyl or C
l
-C
6
-alkynyl; which are unsubstituted or substituted by one to three groups R
a
, and Y represents a nucleophilic replaceable leaving group, preferably a halogen atom, in particular a iodine atom
Compounds of formula II are known for example from U.S. Pat. No. 5,593,996, WO-A 98/46608, FR-A 2,765,875, WO-A 99/41255 or WO-A 99/48893.
The reaction between the triazolopyrimidines of formula II, the strong base and the alkylation agent of formula III is preferably carried out in the presence of an inert solvent. Suitable solvents include ethers, such as dioxane, diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as dichloromethane, amides, such as dimethylformamide or N-methylpyrrolidone and aromatic hydrocarbons, for example toluene or mixtures of these solvents. The reaction is suitably carried out at a temperature in the range from −78° C. to 100° C., the preferred reaction temperature is from 10° C. to 80° C., particular at ambient temperature.
Suitable strong bases include metal hydrides, such as sodium hydride, potassium hydride or calcium hydride, and metal amides, such as sodium amide, potassium amide, lithium diisopropylamide or potassium hexamethyldisilazide, and metal alkanes such as methyllithium, n-butyllithium or tert-butyllithium.
Furthermore, the compounds of formula I wherein R
4
is an optionally substituted alkyl, alkenyl or alkynyl group may be prepared by reacting a N-pyrimid-2-ylformamide oxime of formula IV
in which R
1
through R
3
and X are as defined in formula I; with a N,N-dimethylformamide dialkyl acetate of formula V
in which R
4
is is C
1
-C
6
-alkyl, C
1
-C6-alkenyl or C
1
-C
6
-alkynyl; which are unsubstituted or substituted by one to three groups R
a
.
The reaction between the compounds of formula IV and the compounds of formula v can be carried out analogosly to the reaction described in Vestn. Slov. Kem. Drus. (1986), 33(3), 353-66.
Compounds of formula I wherein R
4
is hydrogen can preferably be prepared by treating sulfones of formula VI
in which R
1
through R
3
and X are as defined in formula I and R
6
is C
1
-C
6
-alkyl or C
1
-C
6
-haloalkyl; with cyanamide or with a metal salt of cyanamide. The use of a base and/or a solvent can be advantageous.
This process is preferably carried out in the presence of an inert solvent. Suitable solvents include aromatic hydrocarbons, such as, for example toluene or xylene, chlorinated hydrocarbons, such as, for example methylene chloride, chloroform, a chlorobenzene, ketones, such as, for example acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, nitriles, such as, for example acetonitrile or propionitrile ethers, such as, for example diethyl ether, diisopropyl ether, methyl tert-butylether, dimethoxyethane, tetrahydrofuran or dioxane, amides, such as, for example, dimethylacetamide or diethylacetamide, sulfoxides, such as, for example dimethylsulfoxide or sulfolane, or mixtures thereof.
The use of a base can be advantageous in this reaction. Suitable bases include alkali metal hydrides and earth alkaline metal hydrides, such as, for example, sodium, potassium or calcium hydrides, alkali metal hydroxides and alkaline earth metal hydroxides, such as, for example, sodium, potassium or calcium hydroxides, alkali metal carbonates and alkaline earth metal carbonates, such as, for example sodium carbonate, potassium carbonate or calcium carbonate, alkali metal bicarbonates and alkaline earth metal bicarbonates, such as sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, metal amides, such as, for example sodium amide, potassium amide, lithium diisopropylamide or potassium hexamethyldisilazide, metal alkanes, such as for example methyl lithium, n-butyl lithium or tert-butyl lithium or aprotic amines, such as, for example pyridine, tributylaine, N,N-dimethylbenzylamine or diazobicycloundecene.
Various qualities of cyanamide may be employed for the process. The use of an aqueous solution of cyanamide may be preferred for practical reasons. The use of metal salts of cyanamide, potassium cyanamide, dipotassium cyanamide or calcium cyanamide is also possible.
Dependant an the used cyanamide or salt of, cyanamide and dependant on the base an appropriate solvent is employed.
The reaction is suitable carried out at a temperature in the range from −78° C. to reflux temperature, the preferred reaction temperature is from 0° C. to 150° C., particular at ambient temperature.
In general 1 to 3 equivalents, preferably 1.5 to 2.5 equivalents of base are employed per equivalent of sulfone of the formula VI.
Generally 2 to 6 equivalents, preferably 3 to 5 equivalents of cyanamide or salt of cyanamide are employed per equivalent of the sulfone of the general formula VI.
Compounds of formula I wherein R
4
is is C
1
-C
6
-alkyl, C
1
-C
6
-alkenyl or C
1
-C
6
-alkynyl which are unsubstituted or substituted by one to three groups R
a
may be prepared by alkylation of compounds of formula I wherein

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