CA1288096C - 7-aminoazolo[1,5-a] pyrimidines, and fungicides containing these - Google Patents
7-aminoazolo[1,5-a] pyrimidines, and fungicides containing theseInfo
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- CA1288096C CA1288096C CA000517820A CA517820A CA1288096C CA 1288096 C CA1288096 C CA 1288096C CA 000517820 A CA000517820 A CA 000517820A CA 517820 A CA517820 A CA 517820A CA 1288096 C CA1288096 C CA 1288096C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
Disclosed are novel, specific 7-aminoazolo-[1,5-a]
pyrimidines of the formula:
Disclosed are novel, specific 7-aminoazolo-[1,5-a]
pyrimidines of the formula:
Description
~ 38~9~;
The present invention relates to novel, specific 7-aminoazoloLl~5-a]pyrimidines~ and to fungicides containing them.
It is known that 7-aminoazoloC1,5-a~pyrimidines, in particular 7-amino-6-phenyl-5-methyl-1,2,4-triazolo~1,5-a~pyrimidine, possess pharmacological properties (U.S.
Patent 2,553,500).
It is also known that 7-aminoazolo Cl,5-a~pyrimidines, in particular 7-amino-6-(4-tert-butoxybut-1-yl)-2,5-di-methylpyrazoloC1,5-a~pyraimidine, can be used as a fungicidal active ingredient (European Patent 141,317).
However, their fungicidal action is not adequate.
It has now been found that novel, specific 7-aminoazolo-[1,5-a3pyrimidines of the formula:
12~2 where Rl is aryloxyalkoxyalkyl, alkoxyalkoxyalkyl, alkoxyal-koxyalkoxyalkyl or dialkylaminoalkyl, in which the aryl moiety is unsubstituted or monosubstituted or polysubsti-tuted by straight-chain or branched alkyl, aryl, alkoxy, aryloxy, halogen, arylalkyl, arylalkoxy, dialkylamino or alkylarylamino, R2 and R3 are each hydrogen or alkyl and A
is =N-, =CH-, =CBr- or =CCl-, are superior to the known compounds in their fungicidal action, in particular in the case of Oomycetes.
More specifically, R is phenyl- or naphthyloxy-C2-C6-alkoxy-C2-C6-alkyl where the alkoxy and alkyl group have a straight-chain or are branched and the phenyl or naphthyl group can be monosubstittued or polysubstituted by ." ~
l3809~;
- la -straight-chain or branched C1-C10-alkyl, C1-C10-alkoxy, aryl, aryloxy, fluorine, chlorine, bromine, aryl-Cl-C4-alkyl, aryl-Cl-C4-alkoxy, di-Cl-Clo alkylamino or Cl-C10-alkylarylamino; aryl being phenyl or 1- or 2-naphthyl. R
may furthermore be C1-C10-alkoxy-C2-C6 alkoxy-C2-C6-alkyl, C1-ClO-alkoxy-c2-c6-alkoxy-c2-c6-al~oxy-c2-c6-alkyl~ where the alkoxy and alkyl group once again have a straight-chain or are branched, or di-C1-C10-alkyl-amino-C2-C6-alkyl.
R and R3 are each hydrogen or C1-C4-alkyl, methyl being preferred.
/
/
o~
7-aminoazoloC1,5-a]pyrimidines of the formula I are obtained, for example, by a method in ~hich an approp-riately substituted B-ketoester of the formula II
1 ~ OR
~ I 1, uhere R is lower alkyl, is reacted with an appropriate aminoazole of the formula III
H2~ III, to give a condensate of the formula V
R ~ R3 and this is halogenated at the hydroxyl group an'd reacted ~ith ammonia (process A).
The preparation of the B-ketoesters tII) can be carried out as described in Organic Synthesis Coll., vol. 1, page 248, or in German Laid-Open Application DOS3,227,388 The reaction (condensation) ~ith the aminoazoles' (III) can be carried out in the presence or absence of solvents.
Suitable solv'ents are, in particular, alcohols, such as ethanol, propanols, butanols, glycols or glycol monoethers, . .
? ~ ~ O~, 0.~. 0050/37984 diethylene glycols and their monoethers, amides, such as dimethylformamide, diethylformamide, dibutylformamide or N,N-dimethylacetamide, lower alkanoic acids, such as formic acid, acetic acid or propionic acid, and mixtures of these solvents with water. The reaction temperature is in general from 50 to 300C, preferably from 50 to 150C, when a solvent is employed.
The condensates are generally obtained in pure form and are washed tfor example with the same solvent or 10 with water) and then dried, after which they are halo-genated with, for example, a phosphorus halide at the reflux temperature, preferably at from 50 to 150C in excess phosphorus oxytrichloride. A stoichiometric amount or an excess of a base, eg. N,N-dimethylaniline, may be added.
The excess pho~phorus oxytrichloride is evaporated, after which the mixture is treated w;th icewater, with or without the addition of a water-immiscible solvent, and, if neces-sary, the base ;s removed by extract;on with hydrochloric acid.
The chLorination product finally obtained is gener-ally very pure and is therefore most advantageously reacted Jirectly with ammonia to give the novel 7-aminoazolol1,5-a]pyrimidines. This is preferably carried out using am-monia in an excess of from 1 to 10 moles per mole of the pyrimidine, under superatmospheric pressure (up to 100 bar) above about 100C and, if necessary, in a solvent.
The novel 7-aminoazolo~1,5-a~pyrimidines are gen-erally crystalline compounds obtained directly in very pure form.
The 7-aminoazolo~1,5-a]pyrimidines (I) may also be prepared by a method in which ar, appropriately sub-stituted ~-acylnitrile of the formula C=O IV, ~ ~8~309~
O.Z. ~050/37984 is reacted with an aminoazole of the formula (III) (process ~), this process too being carried out in the presence or absence of a solvent. The solvents and the process con-ditions are substantially similar to those recommended for process A. Process B gives the novel 7-aminoazolo~
S-a~pyr;midines directly; they are isolated as crystalline, generally very pure compounds, if necessary after evap-oration of the solvent or dilution with water. When !ower alkanoic acids (fatty acids) are used as solvents, it is advantageous to neutralize residual acid, if necessary after partial evaporation of the excess.
Some of the substituted ~-acylnitriles (VI) required for the preparation of the 7-amino-azolo~1,5-a]pyrimidines are known, individual unknown nitriles of this type may be prepared by a known method from nitriles possessing hydrogen and carboxylic esters using strong bases, eg.
alkali metal hydrides, alkali metal amides or metalalkyl-enes (J. Amer. Chem. Soc. 73, (1951), page 3766).
Preparat;on example Process A
7-amino-5-methyl-6-r2-(2-methoxy-1-ethoxy)-prop-1-yl]-1,2,4-triazoloC1,5-a]pyrimidine (corresponds to Example no. 97 in the Table) a) 7-hydroxy-5-methyl-6-r2-(2-methoxy-1-ethoxy)-prop-1-yl]-Z5 1,2,4-triazolo~1,5-a~pyrimidine 43.6 9 of 86 percent strength (corresponding to 37.5 9 of 100 percent pure material, 161 millimoles) of methyl 2-r2-(2-methoxy-1-ethoxy)-prop-1-yl]-acetoacetate are reacted with 16.8 9 (200 millimoles) of 3-amino-1~-1,2,4-triazole in 300 ml of propionic acid for 24 hours at 60~ under a protective gas. The mixturé is cooled, stirred into icewater and then neutralized with 2 N
NaOH, and any precipitate is filtered off. The aqueous phase is extracted four times with methylene chloride, and the extracts are dried and evaporated down. The resulting oil is triturated with diethyl ether and ~ ~8~309~i O.Z. OOS0/37984 the crystal~ ~hich separate out are filtered off under suction and dried. Yield: 17.5 9 (41% of theory);
mp. 127 - 128C. The infrared spectrum shows that the substance is predominantly in the form of the 7-oxo-4H
tautomer.
b) 7-Chloro-5-methyl-6-t2-(2-methoxy-1-ethoxy)-prop-1-yl3-1,2,4-triazolot1,5-a]pyrimidine 16.0 9 (56.2 millimoles) of the intermediate obtained as described in method a) are boiled for 20 hours in 300 ml of phosphorus oxytrichloride. Excess phosphorus oxytrichloride is then distilled off. The residue is treated first ~ith ~ater and then ~ith aqueous sodium bicarbonate solution. Extraction is carried out several times ~ith methylene chloride and the extract is extracted several times ~ith water. Drying and evaporat;ng down the extract gives 12~5 9 (78%, based on the intermediate) of an oil, which is used for the next stage c) ~ithout further purificat;on.
c) Active ingredient, corresponding to Example 97 in the Table 460 millimoles of gaseous ammonia are allo~ed to act on a solution of 12.0 9 (42.1 millimoles) of the chlorine compound from b) in 200 ml of dry 1,4-dioxane in an autoclave under an initial pressure of 100 bar at 130C
for 60 hours. The autoclave is cooled and let do~n, after which the mixture is taken up in water and ex-tracted several times with methylene chloride. The extract is dried, the solvent is distilled off and the residue is triturated ~ith n-pentane to give S.0 9 (45X, based on the chlorine compound) of a crystalline material of melting point 143-144C~
Preparation example Process P
7-amino-S-methyl-6-{3-t2-(2,4,6-trichlorophenoxy)-1-ethoxy~-prop-1-yl}-1,2,4-triazolot1~5-a]pyrimidine (Example no.
8 in the Table) 809~
0.~. 0050/37984 a) 2-acetyl-5-C2-(2,4,6-trichlorophenoxy)-1-ethoxy]-valeronitrile 245 9 (760 millimoles) of 5-l2-(2,4,6-trichlorophenoxy)-1-ethoxy]-valeronitrile are dissolved in 1 l of dried tetrahydrofuran and the solution is cooled to -68C
under a protective gas. 572 ml of a 1.5 molar solution of n-butyllithium in n-hexane (corresponding to 858 millimoles of n-butyllithium) are added dropwise in the course of 3 hours, and the mixture is stirred ~or a 1û further 3 hours at -60C. 74.0 ml (66.7 9; 758 milli-moles) of dry ethyl acetate, disso(ved in 200 ml of dry tetrahydrofuran, are then slowly added. The mixture is left for a further 3 hours at -60C and allowed to reach room temperature overnight. Excess butyllithium is destroyed by carefully adding water and the pH is brought to four by adding 2 N hydrochloric acid. Thereafter, the organic phase is separated off, washed with water, dried and evaporated down. The residue which remains comprises 267 9 ~crude yield 73Z) of a yellow oil, which can be used directly for reaction b).
b) Active ingredient, corresponding to Example 8 in the Table The total amount (732 mmoles) of the -acetylnitrile prepared as described above and 61.5 9 (731 mmoles) of 3-amino-1~-1,2,4-triazole in 1~0 l of propionic acid are kept at the boil for 24 hours, after which the mixture is allowed to cool and is filtered, and the filtrate is evaporated down. The residue is taken up in methylene chlor;de, and the solution is washed several times with water until the aqueous phase is neutral, and is then dried and evaporated down. 166 9 of (53%, based on the nitrile) of a crystalline mate-rial of melt;ng point 193-194C result.
309~
0.~. 0050/37984 Preparation example Process B
7-amino-5-methyl-6-{2-~N-(3,5,5-trimethylhex-1-yl)-N-methyl--amino]-1-ethyl}-1,2,4-triazolo[1,5-a]pyrimidine (Example no. 125) a) 2-acetyl-4-lN-(3,5,5-trimethylhex-1-yl)-N-~ethylamino]-butyronitrile As described above, 31.3 9 (139.5 mmoles) of 4-[N-(3, 5,5-trimethylhex-1-yl)-N-methylamino]-butyronitrile 1û in 300 ml of dry tetrahydrofuran are first reacted with 103 ml of 1.5 M n-butyllithium solution (154 mmoles) and the product is then reacted with 13.7 ml (12.4 9; 141 mmoles) of dry ethyl acetate in 50 ml of tetrahydrofuran at -68C. In working up the mixture, the pH is brought to 6 with 2 N hydrochloric acid.
The solvent is evaporated off to give 33.0 9 (crude yield 88%) of an oil, which is used directly for the subsequent product.
b) Active ;ngredient, corresponding to Example 125 Z0 The total amount (124 mmoles) of the resulting nitrile is reacted with 10.4 9 (1Z4 mmoles) of 3-amino-lH-1, 2,4-triazole in 300 ml of boiling propionic acid for 18 hours. The solvent is removed, the residue is tri-turated with n-pentane, the mixture is filtered under suction, the residue is taken up in methylene chloride and the solution is filtered over a short column of silica gel, with the addition of 5 percent by volume of methanol. The eluate is e~tracted by shaking with aqueous sodium carbonate solution, dried and evaporated down. 13.0 9 (32X, based on the nitrile) of a solid of melting point of 109-110C remain.
The active ingredients characterized more e~actly (melting point, state of aggregation, etc.) in the tables below are prepared by the stated processes (A or B).
Those compounds which are not characterized can readily be obtained by appropriately changing the starting materials and adapting the methods of preparation; because S09~
O.Z. 0050/37984 of their structural similarity, they are expected to have a si~ilar action.
- J ~3809~
- 9 - O.Z. 0050/37984 Tabls 1 a NH2 05 ~R)n (CH2)2 ~ N
No. (R)n -X- M.p. (C) 1 H -(CH2)2-2 H -cH(cH3)cH2-3 H -(CH2)3- 157-158 4 H -(CH2)4-lS 5 H . -(CH2)5-6 2,4,6-C13 -(CH2)2-7 2,4,6-C13 -CH(CH3)CH2-8 2,4,6-C13 -(CH2)3-9 2,4,6-C13 -(CH2)4-2010 2,4,6-C13 -(CH2)5-11 2-Cl -(CH2)2-12 2-C1 -cH(cH3)cH
13 2-Cl -(CH2)3-14 2-Cl -(CH2)4-2515 2-Cl -(CH2)5-16 4-C1 -(CH2)2-17 4-Cl CH(CH3)CH2 18 4-C1 -(CH2)3-19 4-C1 -(CH2)4-3020 4-Cl -(CH2)5-21 3-Cl -(CH2)2-22 3-Cl -CH(CH3)CH2-23 3-Cl -(CH2)3- 135-137 24 3-C1 -(CH2)4-3S25 3-C1 -(C~2)5-26 2-Br -(CH2)2-27 2-Br -cH(cH3)cH2-28 2-Br -(CH2)3- 161-163 29 2-Br -(CH2)4-~030 2-Br -(CH2)5-31 4-Br -(CH2)2-32 4-Br -cH(cH3) 33 4-9r -(CH2)3-U9~
- 10 - O.Z. 0050/37984 No. (R)n -X- M.p. (C) -34 4-Br -(CH2)4-05 35 4-Br -(CH2)5-36 2-CH3 -(CH2)2-37 2-CH3 -CH(CH3)CH2-38 2-CH3 -(CH2)3- 164-166 39 2-CH3 -(CH2)4-10 40 2-CH3 -(CH2)5- 220 (decomposition) 41 3-CH3 -(CH2)2-42 3-CH3 -CH(CH3)CH2-43 3-CH3 -(CH2)3- 147-149 44 3-CH3 -(CH2)4-lS 45 3-CH3 -(CH2)5-46 4-CH3 -(CH2)2-47 4-CH3 -CH(CH3)CH2-48 4-CH3 -(CH2)3- 155-158 49 4-CH3 -(CH2)4-20 50 4-CH3 -(CH2)5-51 2,4,6-(CH3)3 -(CH2)2-52 2,4,6-(CH3)3 -cH(cH3)cH2-53 2,4,6-(CH3)3 -(CH2)3- 190-191 54 2,4,6-(CH3)3 -(CH2)4-2S 55 2,4,6-(CH3)3 -(CH2)5- 157-160 56 tert.-C4Hg-CH2~C(cH3)2 -(CH2)2-57 tert.-C4Hg-CH2~C(cH3)2 -cH(cH3)cH
58 tert.-C4Hg-CH2~C(cH3)2 -(CH2)3-59 tert.-C4Hg-CH2~C(cH3)2 -(CH2)4-30 60 tert.-C4Hg-CH2~C(cH3)2 -(CH2)5- 149-151 61 4-C1-2~CH3 -(CH2)3- 144-145 62 2-(i-C3H7) -(CH2)3-63 2-(sec-C4Hg) -(CH2)3- 118-120 64 2-(sec-C4Hg) -(CH2)5- 154-156 ~5 65 4 C6H5 -(CH2)3- 176-179 66 4-C6H5 -(CH2)5- 172-174 67 4 H5C2 -(CH2)2- 162-163 68 4 H5C2 -CH(CH3)CH2- 158-160 69 4 H5C2 -(CH2)3-~0 70 4-H5C20 -(CH2)4-71 4 H5C2 -(CH2)5-72 4-H5C60 -(CH2)2-73 4-H5C60 -CH(CH3)CH2-809~i - 11 - O.Z. 0050/37984 No. (R)n -X- M.p. (C) 74 4-H5C60 -(CH2)3- 156-15805 75 4-H5C60 -(CH2)4-76 4-H5C60 -(CH2)5-77 2-(n-C4Hg)O -(CH2)3- 133-135 78 2-(n-C4Hg)O -(CH2)4-79 2-(n-C4Hg)O -(CH2)5-3-(n-C4Hg)O -(CH2)3-81 3-(n-C4Hg)O -(CH2)4-82 3-(n-C4Hg)O -(CH2)5-83 4-(n-C4Hg)O -(CH2)3-84 4-(n-C4Hg)O -(CH2)4-lS 85 4-(n-C4Hg)O -(CH2)5-86 2-(H5C6-CH2)0 -(CH2)3-87 2 (H5C6-cH2) -(CH2)5-88 3-(H5C6-cH2)0 -(CH2)3-89 3-(H5C6-cH2)0 -~CH2)5-20 90 4-(H5C6-CH2)0 -(CH2)3-91 4-(H5C6-CH2)0 -(CH2)5-92 3-(H5C2)N -(CH2)3-93 3-(H5C2)N -(CH2)5-Table 1 b NH
~ -(CH2~2--x ~ - N
CR n H3 N ~ CH3 No. (R)n -X- M.p. (C) 94 t-C4Hg-CH2-C(cH3)2~ -(CH2)3- 60 t-C4Hg-CH2-C(cH3)2~ -(CH2)5- (o~l) 38~
- 12 - O.Z. 0050t37984 Table 2 2 ) 2 ~N
No. R -X- M.p. (C) 96 CH3 -(CH2)2-97 CH3 -CH(CH3)CH2- 142-144 98 CH3 -(CH2)3-99 CH3 -(CH2)4-15100 CH3 -(CH2)5_ 101 n-C4H9 -(CH2)2-102 n-C4Hg -cH(cH3)cH
103 n-C4H9 -(CH2)3-1~4 n-C4Hg -(CH2)4-20105 n-C4Hg -(CH2)5-106 2-ethylhexyl -(CH2)2-107 2-ethylhexyl -CH(Ms)CH2_ 108 2-ethylhexyl -(CH2)3-109 2-ethylhexyl -(CH2)4-25110 2-ethylhexyl -(CH2)5-111 3,5,5-trimethylhexyl -(CH2)2-112 3,5,5-tr~methylhexyl -CH(CH3)CH2-113 3,5,5-trimethylhexyl -(CH2)3-114 3,5,5-trimethylhexyl -(CH2)4-30115 3,5,5-trimethylhexyl -(CH2)5-116 n-HgC4-0~(CH2)3 -(CH2)2-117 n-HgC4-0-(CH2)3 -cH(cH3)cH2- resin 118 n-H9C4~0~(CH2)3 -(CH2)3-119 n-HgC4-0~(CH2)3 -(CH2)4 35120 n-HgC4-0~(CH2)3~ -(CH2)5-121 n-HgC4-0~(CH2)2 -cH(cH3)cH2-122 CH20(CH2)2- -CH(CH3)CH2-H5C2-CH-n-c4H9 123 (CH2)20(CH2)2- -cH(cH3)cH
H3C-CH-CH2-t-C4Hg 8~309~
- 13 - O.Z. 0050~37984 Table 3 No. R5 R4 M.p. (C) 124 n-C6H13- n-C6H13- 139-140 125 3,5,5-trimethylhexyl- CH3- 109-110 lS Table 4 ,C l NH2 C l ~ 0 - ( C H 2 ) 2 - - ~ C H 2 ) 3~N- r C l R2 N AJ~ R3 No. R2 R3 A M.p. (C) 129 CH3 CH3 C-Or o9l~
- 14 - O.Z. 0050/37984 The novel active ingredients have a strong fungitoxic action on phytopathogenic fungi, especially from the Phycomycetes class. The novel compounds are therefore sl~itable for combatting Phytophthora infestans in tomatoes 05 and potatoes, Phytophthora parasitica in strawberries, Phytophthora cactorum in apples, Pseudoperonospora cubensis in cucumbers, Pseudoperonospora humuli in hops, Peronospora destructor in onions, Peronospora sparsa in roses, Peronospora tabacina in tobacco, Plasmopara viticola in grapes, Plasmopara halstedii in sunflowers, Sclerospora macrospora in Indian corn, Bremia lactucae in lettuce, Mucor mucedo in fruit, Rhizopus nigricans in beets,Erysiphe graminis in cereals, Uncinula necator in grapes, Podosphaera leucotricha in apples, Sphaerotheca fuliginea in roses, and Erysiphe cichoriacearum in cucumbers.
The active ingredients are well tolerated by plants.
Some of the active ingredients have curative properties, i.e., the agents may also be applied after the plants have been infected by the pathogen, and success is still ensured.
The fungicidal agents contain from 0.1 to 95, and preferably from 0.5 to 90, wt.% of active ingredient. The application rates depend on the type of effect desired, and range from 0.1 to 5 kg/ha.
The active ingredients may also be mixed and applied together with other active ingredients, e.g., herbicides, insecticides, growth regulators and other fungicides, or with fertilizers. When they are mixed with other fungicides, the spectrum of fungicidal action is often increased, i.e., the fungicidal action of the combination is greater than the sum of the actions of the individual components.
Examples of fungicides which may be combined with the novel compounds are:
sulfur dithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate - 15 - O.Z. 0050/37984 zinc dimethyldithiocarbamate zinc ethylenebisthiocarbamate manganese ethylenebisdithiocarbamate rnanganese zinc ethylenediaminebisdithiocarbamate 05 l:etramethylthiuram disulfides ammonia complex of zinc N,N'-ethylenebisdithiocarbamate ammonia complex of zinc N,N-propylenebisdithiocarbamate zinc N,N'-propylenebisdithiocarbamate and N,N-polypropylenebis(thiocarbamyl) disulfide nitro derivatives, such as dinitro (l-methylheptyl)-phenyl crotonate 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate 2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and diisopropyl 5-nitroisophthalate heterocyclic substances, such as 2-heptadecylimidazol-2-yl acetate 2,4-dichloro-6-(o-chloroanilino)-s-triazine 0,0-diethyl phthalimidophosphonothionate 5-amino-1-~bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4--triazole 2,3-dicyano-1,4-dithiaanthraquinone 2-thio-1,3-dithio- r 4,5-b]-quinoxaline methyl l-(butylcarbamoyl)-2-benzimidazole carbamate 2-methoxycarbonylaminobenzimidazole 2-[furyl-~2)]-benzimidazole 2-[thiazolyl-(4)]-benzimidazole N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide N-trichloromethylphthalimide N-dichlorofluoromethylthio-N+,N+-dimethyl-N-phenyl--sulfuric acid diamide 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole 2-thiocyanomethylthiobenzthiazole 1,4-dichloro-2,5-dimethoxybenzole 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone 2~thiopyridine l-oxide 8-hydroxyquinoline and its copper salt ~ ~S~09~;
- 16 - O.Z. 0050/37984 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 4,4-dioxide 2-methyl-5,6-dihydro-4-H-pyran-3-carboxanilide 05 2-methylfuran-3-carboxanilide 2,5-dimethylfuran-3-carboxanilide 2,4,5-trimethylfuran-3-carboxanilide 2,5-dimethyl-N-cyclohexylfuran-3-carboxamide N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide 2-methylbenzanilide 2-iodobenzanilide N-formyl-N-morpholine-2,2,2-trichloroethylacetal piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichlorethane 2,6-dimethyl-N-tridecyl-morpholine and its salts 2,6-dimethyl-N-cyclododecyl-morpholine and its salts N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-di-methylmorpholine N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]--l-H-1,2,4-triazole 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl--ethyl]-l-H-1,2,4-triazole N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N+-imidazolyl-urea1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)--butan-2-one 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-butan-2-ol alpha-(2-chlorophenyl)-alpha-(4-chlorophenyl)-5-pyrimidine-methanol 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine bis-(p-chlorophenyl)-3-pyridinemethanol 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene 2-cyano-N-(ethylaminocarbonyl)-2-(methoximino)-acetamide 309~;
- 17 - O.Z. 0050/37984 and various fungicides, such as dodecylguanidine acetate 3-[2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutar-amide 05 hexachlorobenzene DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)--alanate N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyro-19 lactone5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxa-zolidine 3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxa-zolidine-2,4-dione 3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-di-carboximide The novel active ingre~ients may be applied or instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the novel active ingre-dients as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be used direct or after emulsific-ation in water, mineral oil fractions of medium to highboiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as . methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanoll cyclohexanone, chlorobenzene, 09~
- 18 - O.Z. 0050/37~84 isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueou3 formulations may be prepared from emulsion con-05 centrates, pastes, oil dispersions or wettable powders byadding water. To prepare emulsions, pastes and oil dis-persions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsify-ing or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, lS naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalene-sulfonic acid, lauryl ether sulfate, fatty alcohol sul-fates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol poly-glycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
~.~88~9~
- 19 - O.Z. 0050/37984 Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, 05 kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnPsium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
Examples of formulations are given below.
I. 90 parts by weight of the compound of Example 3 is mixed with 100 parts by weight of N-methyl-alpha-pyrroli-done. A mixture is obtained which is suitable for applica-tion in the form of very fine drops.
II. 20 parts by weight of the compound of Example 8 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-mono-ethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
III. 20 parts by weight of the compound of Example 23 is dissolved in a mixture consisting of 30 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, and 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of the compound of Example 38 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 809~:i - 20 - O.Z. 0050/37984 lO parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
05 V. 20 parts by weight of the compound of Example 43 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
VI. 5 parts by weight of the compound of Example 94 is intimately mixed with 95 parts by weight of particulate kaolin. A dust is obtained containing 5~, by weight of the active ingredient.
VII. 30 parts by weight of the compound of Example 117 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 40 parts by weight of the compound of Example 124 is intimately mixed with 30 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion.
IX. 20 parts of the compound of Example 23 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenol-sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
The following experiments demonstrate the biological action of the novel compounds. The prior art compounds 7-amino-6-phenyl-5-methyl-[1,2,4]-triazole-~1,5-a]-pyrimi-~ 2~ 9~, - 21 - O.Z. 0050/37g84 dine (A) (U.S. 2,553,500) and 7-amino-6-(4-tert-butoxy)---5-methyl-2-methylpyrazolo-[1,5-a]-pyrimidine ~B) (EP 141,317) were used for comparison purposes.
~xperiment 1 05 Action on Plasmopara viticola Leaves of potted vines of the Muller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) 80% of active ingredient and 20~, of emulsifier. To assess the duraction of action, the plants were set up, after the sprayed-on layer had dried, for 10 days in the greenhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viticola. The plants were first placed for 16 hours in a water-vapor saturated chamber at 24C and then in a greenhouse for 8 days at from 20 to 30C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.
The results of the experiment show that for instance compounds nos. 3, 8, 23, 38, 43, 94, 117 and 124, applied as 0.05~ liquors, have a better fungicidal action (e.g., 97%) then comparative compounds A and B (e.g., 60~.).
Experiment 2 Action on PhYtoPhthora infestans in tomatoes Leaves of potted tomatoes of the "Gro~e Fleischtomate"
variety were sprayed with aqueous liquors containing (dry basis) 80~ of active ingredient and 20~, of emulsifier.
After the sprayed-on layer had dried, the leaves were infected with a zoospore suspension of Phytophthora infestans. The plants were then placed for 5 days in a water vapor-saturated chamber kept at 16 to 18C. After this period, the disease had spread on the untreated control plants to such an ex~ent that the fungicidal action of the compounds was able to be assessed.
The results of this experiment show that compounds 8, 63 and 124, applied for instance as 0.025~ liquors, have a better fungicial action ~e.g., 97%) than prior art active ingredient B (0~).
The present invention relates to novel, specific 7-aminoazoloLl~5-a]pyrimidines~ and to fungicides containing them.
It is known that 7-aminoazoloC1,5-a~pyrimidines, in particular 7-amino-6-phenyl-5-methyl-1,2,4-triazolo~1,5-a~pyrimidine, possess pharmacological properties (U.S.
Patent 2,553,500).
It is also known that 7-aminoazolo Cl,5-a~pyrimidines, in particular 7-amino-6-(4-tert-butoxybut-1-yl)-2,5-di-methylpyrazoloC1,5-a~pyraimidine, can be used as a fungicidal active ingredient (European Patent 141,317).
However, their fungicidal action is not adequate.
It has now been found that novel, specific 7-aminoazolo-[1,5-a3pyrimidines of the formula:
12~2 where Rl is aryloxyalkoxyalkyl, alkoxyalkoxyalkyl, alkoxyal-koxyalkoxyalkyl or dialkylaminoalkyl, in which the aryl moiety is unsubstituted or monosubstituted or polysubsti-tuted by straight-chain or branched alkyl, aryl, alkoxy, aryloxy, halogen, arylalkyl, arylalkoxy, dialkylamino or alkylarylamino, R2 and R3 are each hydrogen or alkyl and A
is =N-, =CH-, =CBr- or =CCl-, are superior to the known compounds in their fungicidal action, in particular in the case of Oomycetes.
More specifically, R is phenyl- or naphthyloxy-C2-C6-alkoxy-C2-C6-alkyl where the alkoxy and alkyl group have a straight-chain or are branched and the phenyl or naphthyl group can be monosubstittued or polysubstituted by ." ~
l3809~;
- la -straight-chain or branched C1-C10-alkyl, C1-C10-alkoxy, aryl, aryloxy, fluorine, chlorine, bromine, aryl-Cl-C4-alkyl, aryl-Cl-C4-alkoxy, di-Cl-Clo alkylamino or Cl-C10-alkylarylamino; aryl being phenyl or 1- or 2-naphthyl. R
may furthermore be C1-C10-alkoxy-C2-C6 alkoxy-C2-C6-alkyl, C1-ClO-alkoxy-c2-c6-alkoxy-c2-c6-al~oxy-c2-c6-alkyl~ where the alkoxy and alkyl group once again have a straight-chain or are branched, or di-C1-C10-alkyl-amino-C2-C6-alkyl.
R and R3 are each hydrogen or C1-C4-alkyl, methyl being preferred.
/
/
o~
7-aminoazoloC1,5-a]pyrimidines of the formula I are obtained, for example, by a method in ~hich an approp-riately substituted B-ketoester of the formula II
1 ~ OR
~ I 1, uhere R is lower alkyl, is reacted with an appropriate aminoazole of the formula III
H2~ III, to give a condensate of the formula V
R ~ R3 and this is halogenated at the hydroxyl group an'd reacted ~ith ammonia (process A).
The preparation of the B-ketoesters tII) can be carried out as described in Organic Synthesis Coll., vol. 1, page 248, or in German Laid-Open Application DOS3,227,388 The reaction (condensation) ~ith the aminoazoles' (III) can be carried out in the presence or absence of solvents.
Suitable solv'ents are, in particular, alcohols, such as ethanol, propanols, butanols, glycols or glycol monoethers, . .
? ~ ~ O~, 0.~. 0050/37984 diethylene glycols and their monoethers, amides, such as dimethylformamide, diethylformamide, dibutylformamide or N,N-dimethylacetamide, lower alkanoic acids, such as formic acid, acetic acid or propionic acid, and mixtures of these solvents with water. The reaction temperature is in general from 50 to 300C, preferably from 50 to 150C, when a solvent is employed.
The condensates are generally obtained in pure form and are washed tfor example with the same solvent or 10 with water) and then dried, after which they are halo-genated with, for example, a phosphorus halide at the reflux temperature, preferably at from 50 to 150C in excess phosphorus oxytrichloride. A stoichiometric amount or an excess of a base, eg. N,N-dimethylaniline, may be added.
The excess pho~phorus oxytrichloride is evaporated, after which the mixture is treated w;th icewater, with or without the addition of a water-immiscible solvent, and, if neces-sary, the base ;s removed by extract;on with hydrochloric acid.
The chLorination product finally obtained is gener-ally very pure and is therefore most advantageously reacted Jirectly with ammonia to give the novel 7-aminoazolol1,5-a]pyrimidines. This is preferably carried out using am-monia in an excess of from 1 to 10 moles per mole of the pyrimidine, under superatmospheric pressure (up to 100 bar) above about 100C and, if necessary, in a solvent.
The novel 7-aminoazolo~1,5-a~pyrimidines are gen-erally crystalline compounds obtained directly in very pure form.
The 7-aminoazolo~1,5-a]pyrimidines (I) may also be prepared by a method in which ar, appropriately sub-stituted ~-acylnitrile of the formula C=O IV, ~ ~8~309~
O.Z. ~050/37984 is reacted with an aminoazole of the formula (III) (process ~), this process too being carried out in the presence or absence of a solvent. The solvents and the process con-ditions are substantially similar to those recommended for process A. Process B gives the novel 7-aminoazolo~
S-a~pyr;midines directly; they are isolated as crystalline, generally very pure compounds, if necessary after evap-oration of the solvent or dilution with water. When !ower alkanoic acids (fatty acids) are used as solvents, it is advantageous to neutralize residual acid, if necessary after partial evaporation of the excess.
Some of the substituted ~-acylnitriles (VI) required for the preparation of the 7-amino-azolo~1,5-a]pyrimidines are known, individual unknown nitriles of this type may be prepared by a known method from nitriles possessing hydrogen and carboxylic esters using strong bases, eg.
alkali metal hydrides, alkali metal amides or metalalkyl-enes (J. Amer. Chem. Soc. 73, (1951), page 3766).
Preparat;on example Process A
7-amino-5-methyl-6-r2-(2-methoxy-1-ethoxy)-prop-1-yl]-1,2,4-triazoloC1,5-a]pyrimidine (corresponds to Example no. 97 in the Table) a) 7-hydroxy-5-methyl-6-r2-(2-methoxy-1-ethoxy)-prop-1-yl]-Z5 1,2,4-triazolo~1,5-a~pyrimidine 43.6 9 of 86 percent strength (corresponding to 37.5 9 of 100 percent pure material, 161 millimoles) of methyl 2-r2-(2-methoxy-1-ethoxy)-prop-1-yl]-acetoacetate are reacted with 16.8 9 (200 millimoles) of 3-amino-1~-1,2,4-triazole in 300 ml of propionic acid for 24 hours at 60~ under a protective gas. The mixturé is cooled, stirred into icewater and then neutralized with 2 N
NaOH, and any precipitate is filtered off. The aqueous phase is extracted four times with methylene chloride, and the extracts are dried and evaporated down. The resulting oil is triturated with diethyl ether and ~ ~8~309~i O.Z. OOS0/37984 the crystal~ ~hich separate out are filtered off under suction and dried. Yield: 17.5 9 (41% of theory);
mp. 127 - 128C. The infrared spectrum shows that the substance is predominantly in the form of the 7-oxo-4H
tautomer.
b) 7-Chloro-5-methyl-6-t2-(2-methoxy-1-ethoxy)-prop-1-yl3-1,2,4-triazolot1,5-a]pyrimidine 16.0 9 (56.2 millimoles) of the intermediate obtained as described in method a) are boiled for 20 hours in 300 ml of phosphorus oxytrichloride. Excess phosphorus oxytrichloride is then distilled off. The residue is treated first ~ith ~ater and then ~ith aqueous sodium bicarbonate solution. Extraction is carried out several times ~ith methylene chloride and the extract is extracted several times ~ith water. Drying and evaporat;ng down the extract gives 12~5 9 (78%, based on the intermediate) of an oil, which is used for the next stage c) ~ithout further purificat;on.
c) Active ingredient, corresponding to Example 97 in the Table 460 millimoles of gaseous ammonia are allo~ed to act on a solution of 12.0 9 (42.1 millimoles) of the chlorine compound from b) in 200 ml of dry 1,4-dioxane in an autoclave under an initial pressure of 100 bar at 130C
for 60 hours. The autoclave is cooled and let do~n, after which the mixture is taken up in water and ex-tracted several times with methylene chloride. The extract is dried, the solvent is distilled off and the residue is triturated ~ith n-pentane to give S.0 9 (45X, based on the chlorine compound) of a crystalline material of melting point 143-144C~
Preparation example Process P
7-amino-S-methyl-6-{3-t2-(2,4,6-trichlorophenoxy)-1-ethoxy~-prop-1-yl}-1,2,4-triazolot1~5-a]pyrimidine (Example no.
8 in the Table) 809~
0.~. 0050/37984 a) 2-acetyl-5-C2-(2,4,6-trichlorophenoxy)-1-ethoxy]-valeronitrile 245 9 (760 millimoles) of 5-l2-(2,4,6-trichlorophenoxy)-1-ethoxy]-valeronitrile are dissolved in 1 l of dried tetrahydrofuran and the solution is cooled to -68C
under a protective gas. 572 ml of a 1.5 molar solution of n-butyllithium in n-hexane (corresponding to 858 millimoles of n-butyllithium) are added dropwise in the course of 3 hours, and the mixture is stirred ~or a 1û further 3 hours at -60C. 74.0 ml (66.7 9; 758 milli-moles) of dry ethyl acetate, disso(ved in 200 ml of dry tetrahydrofuran, are then slowly added. The mixture is left for a further 3 hours at -60C and allowed to reach room temperature overnight. Excess butyllithium is destroyed by carefully adding water and the pH is brought to four by adding 2 N hydrochloric acid. Thereafter, the organic phase is separated off, washed with water, dried and evaporated down. The residue which remains comprises 267 9 ~crude yield 73Z) of a yellow oil, which can be used directly for reaction b).
b) Active ingredient, corresponding to Example 8 in the Table The total amount (732 mmoles) of the -acetylnitrile prepared as described above and 61.5 9 (731 mmoles) of 3-amino-1~-1,2,4-triazole in 1~0 l of propionic acid are kept at the boil for 24 hours, after which the mixture is allowed to cool and is filtered, and the filtrate is evaporated down. The residue is taken up in methylene chlor;de, and the solution is washed several times with water until the aqueous phase is neutral, and is then dried and evaporated down. 166 9 of (53%, based on the nitrile) of a crystalline mate-rial of melt;ng point 193-194C result.
309~
0.~. 0050/37984 Preparation example Process B
7-amino-5-methyl-6-{2-~N-(3,5,5-trimethylhex-1-yl)-N-methyl--amino]-1-ethyl}-1,2,4-triazolo[1,5-a]pyrimidine (Example no. 125) a) 2-acetyl-4-lN-(3,5,5-trimethylhex-1-yl)-N-~ethylamino]-butyronitrile As described above, 31.3 9 (139.5 mmoles) of 4-[N-(3, 5,5-trimethylhex-1-yl)-N-methylamino]-butyronitrile 1û in 300 ml of dry tetrahydrofuran are first reacted with 103 ml of 1.5 M n-butyllithium solution (154 mmoles) and the product is then reacted with 13.7 ml (12.4 9; 141 mmoles) of dry ethyl acetate in 50 ml of tetrahydrofuran at -68C. In working up the mixture, the pH is brought to 6 with 2 N hydrochloric acid.
The solvent is evaporated off to give 33.0 9 (crude yield 88%) of an oil, which is used directly for the subsequent product.
b) Active ;ngredient, corresponding to Example 125 Z0 The total amount (124 mmoles) of the resulting nitrile is reacted with 10.4 9 (1Z4 mmoles) of 3-amino-lH-1, 2,4-triazole in 300 ml of boiling propionic acid for 18 hours. The solvent is removed, the residue is tri-turated with n-pentane, the mixture is filtered under suction, the residue is taken up in methylene chloride and the solution is filtered over a short column of silica gel, with the addition of 5 percent by volume of methanol. The eluate is e~tracted by shaking with aqueous sodium carbonate solution, dried and evaporated down. 13.0 9 (32X, based on the nitrile) of a solid of melting point of 109-110C remain.
The active ingredients characterized more e~actly (melting point, state of aggregation, etc.) in the tables below are prepared by the stated processes (A or B).
Those compounds which are not characterized can readily be obtained by appropriately changing the starting materials and adapting the methods of preparation; because S09~
O.Z. 0050/37984 of their structural similarity, they are expected to have a si~ilar action.
- J ~3809~
- 9 - O.Z. 0050/37984 Tabls 1 a NH2 05 ~R)n (CH2)2 ~ N
No. (R)n -X- M.p. (C) 1 H -(CH2)2-2 H -cH(cH3)cH2-3 H -(CH2)3- 157-158 4 H -(CH2)4-lS 5 H . -(CH2)5-6 2,4,6-C13 -(CH2)2-7 2,4,6-C13 -CH(CH3)CH2-8 2,4,6-C13 -(CH2)3-9 2,4,6-C13 -(CH2)4-2010 2,4,6-C13 -(CH2)5-11 2-Cl -(CH2)2-12 2-C1 -cH(cH3)cH
13 2-Cl -(CH2)3-14 2-Cl -(CH2)4-2515 2-Cl -(CH2)5-16 4-C1 -(CH2)2-17 4-Cl CH(CH3)CH2 18 4-C1 -(CH2)3-19 4-C1 -(CH2)4-3020 4-Cl -(CH2)5-21 3-Cl -(CH2)2-22 3-Cl -CH(CH3)CH2-23 3-Cl -(CH2)3- 135-137 24 3-C1 -(CH2)4-3S25 3-C1 -(C~2)5-26 2-Br -(CH2)2-27 2-Br -cH(cH3)cH2-28 2-Br -(CH2)3- 161-163 29 2-Br -(CH2)4-~030 2-Br -(CH2)5-31 4-Br -(CH2)2-32 4-Br -cH(cH3) 33 4-9r -(CH2)3-U9~
- 10 - O.Z. 0050/37984 No. (R)n -X- M.p. (C) -34 4-Br -(CH2)4-05 35 4-Br -(CH2)5-36 2-CH3 -(CH2)2-37 2-CH3 -CH(CH3)CH2-38 2-CH3 -(CH2)3- 164-166 39 2-CH3 -(CH2)4-10 40 2-CH3 -(CH2)5- 220 (decomposition) 41 3-CH3 -(CH2)2-42 3-CH3 -CH(CH3)CH2-43 3-CH3 -(CH2)3- 147-149 44 3-CH3 -(CH2)4-lS 45 3-CH3 -(CH2)5-46 4-CH3 -(CH2)2-47 4-CH3 -CH(CH3)CH2-48 4-CH3 -(CH2)3- 155-158 49 4-CH3 -(CH2)4-20 50 4-CH3 -(CH2)5-51 2,4,6-(CH3)3 -(CH2)2-52 2,4,6-(CH3)3 -cH(cH3)cH2-53 2,4,6-(CH3)3 -(CH2)3- 190-191 54 2,4,6-(CH3)3 -(CH2)4-2S 55 2,4,6-(CH3)3 -(CH2)5- 157-160 56 tert.-C4Hg-CH2~C(cH3)2 -(CH2)2-57 tert.-C4Hg-CH2~C(cH3)2 -cH(cH3)cH
58 tert.-C4Hg-CH2~C(cH3)2 -(CH2)3-59 tert.-C4Hg-CH2~C(cH3)2 -(CH2)4-30 60 tert.-C4Hg-CH2~C(cH3)2 -(CH2)5- 149-151 61 4-C1-2~CH3 -(CH2)3- 144-145 62 2-(i-C3H7) -(CH2)3-63 2-(sec-C4Hg) -(CH2)3- 118-120 64 2-(sec-C4Hg) -(CH2)5- 154-156 ~5 65 4 C6H5 -(CH2)3- 176-179 66 4-C6H5 -(CH2)5- 172-174 67 4 H5C2 -(CH2)2- 162-163 68 4 H5C2 -CH(CH3)CH2- 158-160 69 4 H5C2 -(CH2)3-~0 70 4-H5C20 -(CH2)4-71 4 H5C2 -(CH2)5-72 4-H5C60 -(CH2)2-73 4-H5C60 -CH(CH3)CH2-809~i - 11 - O.Z. 0050/37984 No. (R)n -X- M.p. (C) 74 4-H5C60 -(CH2)3- 156-15805 75 4-H5C60 -(CH2)4-76 4-H5C60 -(CH2)5-77 2-(n-C4Hg)O -(CH2)3- 133-135 78 2-(n-C4Hg)O -(CH2)4-79 2-(n-C4Hg)O -(CH2)5-3-(n-C4Hg)O -(CH2)3-81 3-(n-C4Hg)O -(CH2)4-82 3-(n-C4Hg)O -(CH2)5-83 4-(n-C4Hg)O -(CH2)3-84 4-(n-C4Hg)O -(CH2)4-lS 85 4-(n-C4Hg)O -(CH2)5-86 2-(H5C6-CH2)0 -(CH2)3-87 2 (H5C6-cH2) -(CH2)5-88 3-(H5C6-cH2)0 -(CH2)3-89 3-(H5C6-cH2)0 -~CH2)5-20 90 4-(H5C6-CH2)0 -(CH2)3-91 4-(H5C6-CH2)0 -(CH2)5-92 3-(H5C2)N -(CH2)3-93 3-(H5C2)N -(CH2)5-Table 1 b NH
~ -(CH2~2--x ~ - N
CR n H3 N ~ CH3 No. (R)n -X- M.p. (C) 94 t-C4Hg-CH2-C(cH3)2~ -(CH2)3- 60 t-C4Hg-CH2-C(cH3)2~ -(CH2)5- (o~l) 38~
- 12 - O.Z. 0050t37984 Table 2 2 ) 2 ~N
No. R -X- M.p. (C) 96 CH3 -(CH2)2-97 CH3 -CH(CH3)CH2- 142-144 98 CH3 -(CH2)3-99 CH3 -(CH2)4-15100 CH3 -(CH2)5_ 101 n-C4H9 -(CH2)2-102 n-C4Hg -cH(cH3)cH
103 n-C4H9 -(CH2)3-1~4 n-C4Hg -(CH2)4-20105 n-C4Hg -(CH2)5-106 2-ethylhexyl -(CH2)2-107 2-ethylhexyl -CH(Ms)CH2_ 108 2-ethylhexyl -(CH2)3-109 2-ethylhexyl -(CH2)4-25110 2-ethylhexyl -(CH2)5-111 3,5,5-trimethylhexyl -(CH2)2-112 3,5,5-tr~methylhexyl -CH(CH3)CH2-113 3,5,5-trimethylhexyl -(CH2)3-114 3,5,5-trimethylhexyl -(CH2)4-30115 3,5,5-trimethylhexyl -(CH2)5-116 n-HgC4-0~(CH2)3 -(CH2)2-117 n-HgC4-0-(CH2)3 -cH(cH3)cH2- resin 118 n-H9C4~0~(CH2)3 -(CH2)3-119 n-HgC4-0~(CH2)3 -(CH2)4 35120 n-HgC4-0~(CH2)3~ -(CH2)5-121 n-HgC4-0~(CH2)2 -cH(cH3)cH2-122 CH20(CH2)2- -CH(CH3)CH2-H5C2-CH-n-c4H9 123 (CH2)20(CH2)2- -cH(cH3)cH
H3C-CH-CH2-t-C4Hg 8~309~
- 13 - O.Z. 0050~37984 Table 3 No. R5 R4 M.p. (C) 124 n-C6H13- n-C6H13- 139-140 125 3,5,5-trimethylhexyl- CH3- 109-110 lS Table 4 ,C l NH2 C l ~ 0 - ( C H 2 ) 2 - - ~ C H 2 ) 3~N- r C l R2 N AJ~ R3 No. R2 R3 A M.p. (C) 129 CH3 CH3 C-Or o9l~
- 14 - O.Z. 0050/37984 The novel active ingredients have a strong fungitoxic action on phytopathogenic fungi, especially from the Phycomycetes class. The novel compounds are therefore sl~itable for combatting Phytophthora infestans in tomatoes 05 and potatoes, Phytophthora parasitica in strawberries, Phytophthora cactorum in apples, Pseudoperonospora cubensis in cucumbers, Pseudoperonospora humuli in hops, Peronospora destructor in onions, Peronospora sparsa in roses, Peronospora tabacina in tobacco, Plasmopara viticola in grapes, Plasmopara halstedii in sunflowers, Sclerospora macrospora in Indian corn, Bremia lactucae in lettuce, Mucor mucedo in fruit, Rhizopus nigricans in beets,Erysiphe graminis in cereals, Uncinula necator in grapes, Podosphaera leucotricha in apples, Sphaerotheca fuliginea in roses, and Erysiphe cichoriacearum in cucumbers.
The active ingredients are well tolerated by plants.
Some of the active ingredients have curative properties, i.e., the agents may also be applied after the plants have been infected by the pathogen, and success is still ensured.
The fungicidal agents contain from 0.1 to 95, and preferably from 0.5 to 90, wt.% of active ingredient. The application rates depend on the type of effect desired, and range from 0.1 to 5 kg/ha.
The active ingredients may also be mixed and applied together with other active ingredients, e.g., herbicides, insecticides, growth regulators and other fungicides, or with fertilizers. When they are mixed with other fungicides, the spectrum of fungicidal action is often increased, i.e., the fungicidal action of the combination is greater than the sum of the actions of the individual components.
Examples of fungicides which may be combined with the novel compounds are:
sulfur dithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate - 15 - O.Z. 0050/37984 zinc dimethyldithiocarbamate zinc ethylenebisthiocarbamate manganese ethylenebisdithiocarbamate rnanganese zinc ethylenediaminebisdithiocarbamate 05 l:etramethylthiuram disulfides ammonia complex of zinc N,N'-ethylenebisdithiocarbamate ammonia complex of zinc N,N-propylenebisdithiocarbamate zinc N,N'-propylenebisdithiocarbamate and N,N-polypropylenebis(thiocarbamyl) disulfide nitro derivatives, such as dinitro (l-methylheptyl)-phenyl crotonate 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate 2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and diisopropyl 5-nitroisophthalate heterocyclic substances, such as 2-heptadecylimidazol-2-yl acetate 2,4-dichloro-6-(o-chloroanilino)-s-triazine 0,0-diethyl phthalimidophosphonothionate 5-amino-1-~bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4--triazole 2,3-dicyano-1,4-dithiaanthraquinone 2-thio-1,3-dithio- r 4,5-b]-quinoxaline methyl l-(butylcarbamoyl)-2-benzimidazole carbamate 2-methoxycarbonylaminobenzimidazole 2-[furyl-~2)]-benzimidazole 2-[thiazolyl-(4)]-benzimidazole N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide N-trichloromethylphthalimide N-dichlorofluoromethylthio-N+,N+-dimethyl-N-phenyl--sulfuric acid diamide 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole 2-thiocyanomethylthiobenzthiazole 1,4-dichloro-2,5-dimethoxybenzole 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone 2~thiopyridine l-oxide 8-hydroxyquinoline and its copper salt ~ ~S~09~;
- 16 - O.Z. 0050/37984 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 4,4-dioxide 2-methyl-5,6-dihydro-4-H-pyran-3-carboxanilide 05 2-methylfuran-3-carboxanilide 2,5-dimethylfuran-3-carboxanilide 2,4,5-trimethylfuran-3-carboxanilide 2,5-dimethyl-N-cyclohexylfuran-3-carboxamide N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide 2-methylbenzanilide 2-iodobenzanilide N-formyl-N-morpholine-2,2,2-trichloroethylacetal piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichlorethane 2,6-dimethyl-N-tridecyl-morpholine and its salts 2,6-dimethyl-N-cyclododecyl-morpholine and its salts N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-di-methylmorpholine N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]--l-H-1,2,4-triazole 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl--ethyl]-l-H-1,2,4-triazole N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N+-imidazolyl-urea1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)--butan-2-one 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-butan-2-ol alpha-(2-chlorophenyl)-alpha-(4-chlorophenyl)-5-pyrimidine-methanol 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine bis-(p-chlorophenyl)-3-pyridinemethanol 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene 2-cyano-N-(ethylaminocarbonyl)-2-(methoximino)-acetamide 309~;
- 17 - O.Z. 0050/37984 and various fungicides, such as dodecylguanidine acetate 3-[2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutar-amide 05 hexachlorobenzene DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)--alanate N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyro-19 lactone5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxa-zolidine 3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxa-zolidine-2,4-dione 3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-di-carboximide The novel active ingre~ients may be applied or instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the novel active ingre-dients as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be used direct or after emulsific-ation in water, mineral oil fractions of medium to highboiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as . methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanoll cyclohexanone, chlorobenzene, 09~
- 18 - O.Z. 0050/37~84 isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueou3 formulations may be prepared from emulsion con-05 centrates, pastes, oil dispersions or wettable powders byadding water. To prepare emulsions, pastes and oil dis-persions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsify-ing or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, lS naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalene-sulfonic acid, lauryl ether sulfate, fatty alcohol sul-fates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol poly-glycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
~.~88~9~
- 19 - O.Z. 0050/37984 Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, 05 kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnPsium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
Examples of formulations are given below.
I. 90 parts by weight of the compound of Example 3 is mixed with 100 parts by weight of N-methyl-alpha-pyrroli-done. A mixture is obtained which is suitable for applica-tion in the form of very fine drops.
II. 20 parts by weight of the compound of Example 8 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-mono-ethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
III. 20 parts by weight of the compound of Example 23 is dissolved in a mixture consisting of 30 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, and 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of the compound of Example 38 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 809~:i - 20 - O.Z. 0050/37984 lO parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
05 V. 20 parts by weight of the compound of Example 43 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
VI. 5 parts by weight of the compound of Example 94 is intimately mixed with 95 parts by weight of particulate kaolin. A dust is obtained containing 5~, by weight of the active ingredient.
VII. 30 parts by weight of the compound of Example 117 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 40 parts by weight of the compound of Example 124 is intimately mixed with 30 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion.
IX. 20 parts of the compound of Example 23 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenol-sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
The following experiments demonstrate the biological action of the novel compounds. The prior art compounds 7-amino-6-phenyl-5-methyl-[1,2,4]-triazole-~1,5-a]-pyrimi-~ 2~ 9~, - 21 - O.Z. 0050/37g84 dine (A) (U.S. 2,553,500) and 7-amino-6-(4-tert-butoxy)---5-methyl-2-methylpyrazolo-[1,5-a]-pyrimidine ~B) (EP 141,317) were used for comparison purposes.
~xperiment 1 05 Action on Plasmopara viticola Leaves of potted vines of the Muller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) 80% of active ingredient and 20~, of emulsifier. To assess the duraction of action, the plants were set up, after the sprayed-on layer had dried, for 10 days in the greenhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viticola. The plants were first placed for 16 hours in a water-vapor saturated chamber at 24C and then in a greenhouse for 8 days at from 20 to 30C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.
The results of the experiment show that for instance compounds nos. 3, 8, 23, 38, 43, 94, 117 and 124, applied as 0.05~ liquors, have a better fungicidal action (e.g., 97%) then comparative compounds A and B (e.g., 60~.).
Experiment 2 Action on PhYtoPhthora infestans in tomatoes Leaves of potted tomatoes of the "Gro~e Fleischtomate"
variety were sprayed with aqueous liquors containing (dry basis) 80~ of active ingredient and 20~, of emulsifier.
After the sprayed-on layer had dried, the leaves were infected with a zoospore suspension of Phytophthora infestans. The plants were then placed for 5 days in a water vapor-saturated chamber kept at 16 to 18C. After this period, the disease had spread on the untreated control plants to such an ex~ent that the fungicidal action of the compounds was able to be assessed.
The results of this experiment show that compounds 8, 63 and 124, applied for instance as 0.025~ liquors, have a better fungicial action ~e.g., 97%) than prior art active ingredient B (0~).
Claims (11)
1. A 7-aminoazolo[1,5-a]pyrimidine of the formula:
where R1 is phenyl- or naphthyloxy-C2-C6-alkoxy-C2-C6-alkyl where the alkoxy and alkyl group have a straight-chain or are branched and the phenyl or naphthyl group can be monosubstituted or polysubstituted by straight-chain or branched C1-C10-alkyl, C1-C10-alkoxy, aryl aryloxy fluorine, chlorine, bromine, aryl-C1-C4-alkyl, aryl-C1-C4-alkoxy, di-C1-C10 alkylamino or C1-C10-alkylarylamino, aryl being phenyl or 1- or 2- naphthyl, or R is C1-C10-alkoxy-C2-C6-alkoxy-C2-C6-alkyl, C1-C10-alkoxy-C2-C6-alkoxy-C2-C6-alkoxy-C2-C6-alkyl, where the alkoxy and alkyl group have a straight-chain or are branched, or di-C1-C10-alkyl-amino-C2-C6-alkyl;
R2 and R3 are each hydrogen or C1-C4-alkyl, and A is =N-, =CH-, =CBr or =CCl.
where R1 is phenyl- or naphthyloxy-C2-C6-alkoxy-C2-C6-alkyl where the alkoxy and alkyl group have a straight-chain or are branched and the phenyl or naphthyl group can be monosubstituted or polysubstituted by straight-chain or branched C1-C10-alkyl, C1-C10-alkoxy, aryl aryloxy fluorine, chlorine, bromine, aryl-C1-C4-alkyl, aryl-C1-C4-alkoxy, di-C1-C10 alkylamino or C1-C10-alkylarylamino, aryl being phenyl or 1- or 2- naphthyl, or R is C1-C10-alkoxy-C2-C6-alkoxy-C2-C6-alkyl, C1-C10-alkoxy-C2-C6-alkoxy-C2-C6-alkoxy-C2-C6-alkyl, where the alkoxy and alkyl group have a straight-chain or are branched, or di-C1-C10-alkyl-amino-C2-C6-alkyl;
R2 and R3 are each hydrogen or C1-C4-alkyl, and A is =N-, =CH-, =CBr or =CCl.
2. A process for combatting fungi, wherein the fungi or the materials, plants soil or seed to be protected against fungus attack are treated with a fungicidally effective amount of a compound as set forth in claim 1.
3. A fungicidal composition comprising a suitable diluent or carrier and a fungicidally effective amount of a compound as set forth in claim 1.
4. Amino-5-methyl-6-[2-(2-methoxy-1-ethoxy)-prop-1-yl]-1,2,4-triazolo[1,5a]-pyrimidine.
5. 7-Amino-5-methyl-6-{3-[2-(2,4,6-trichlorophe-noxy)-1-ethoxy]-prop-1-yl}-1,2,4-triazolo[1,5a] pyrimidine.
6. 7-Amino-5-methyl-6-{3-[2-(phenoxy)-1-ethoxy]-prop-1-yl}-1,2,4-triazolo[1,5a]-pyrimidine.
7. 7-Amino-5-methyl-6-{2-[N,N-dihexylamino]-1-ethyl}-,2,4-triazolo[1,5a]pyrimidine.
8. A process for combatting fungi, wherein the fungi or the materials, plants soil or seed to be protected against fungus attack are treated with a fungicidally effective amount of a compound as claimed in claim 4 or 5.
9. A process for combatting fungi, wherein the fungi or the materials, plants, soil or seed to be protected against fungus attack are treated with a fungicidally effective amount of a compound as claimed in claim 6 or 7.
10. A fungicidal composition comprising a suitable diluent or carrier and a fungicidally effective amount a compound as claimed in claim 4 or 5.
11. A fungicidal composition comprising a suitable diluent or carrier and a fungicidally effective amount of a compound as claimed in claim 6 or 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3533050.3 | 1985-09-17 | ||
| DE19853533050 DE3533050A1 (en) | 1985-09-17 | 1985-09-17 | 7-AMINO-AZOLO (1,5-A) PYRIMIDINE, METHOD FOR THE PRODUCTION THEREOF AND FUNGICIDES CONTAINING THEM, OR THEIR USE AS FUNGICIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1288096C true CA1288096C (en) | 1991-08-27 |
Family
ID=6281120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000517820A Expired - Lifetime CA1288096C (en) | 1985-09-17 | 1986-09-09 | 7-aminoazolo[1,5-a] pyrimidines, and fungicides containing these |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0215382B1 (en) |
| JP (1) | JPS6267084A (en) |
| AT (1) | ATE55131T1 (en) |
| AU (1) | AU583150B2 (en) |
| CA (1) | CA1288096C (en) |
| CS (1) | CS264282B2 (en) |
| DD (1) | DD249624A5 (en) |
| DE (2) | DE3533050A1 (en) |
| HU (1) | HU201652B (en) |
| IL (1) | IL80004A0 (en) |
| NZ (1) | NZ217593A (en) |
| PL (1) | PL148246B2 (en) |
| ZA (1) | ZA867018B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7629294B2 (en) | 2004-02-20 | 2009-12-08 | Bayer Cropscience Lp | Pyrazolopyrimidines |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3338292A1 (en) * | 1983-10-21 | 1985-05-02 | Basf Ag, 6700 Ludwigshafen | 7-AMINO-AZOLO (1,5-A) -PYRIMIDINE AND FUNGICIDES CONTAINING THEM |
| US4799952A (en) * | 1987-05-01 | 1989-01-24 | The Dow Chemical Company | Herbicidal imidazolo(1,2-a)pyrimidine-2-sulfonanilides |
| WO1999060858A1 (en) * | 1998-05-28 | 1999-12-02 | Sumitomo Chemical Company, Limited | Pyrazolopyrimidine compounds and utilization thereof |
| WO2002048146A2 (en) * | 2000-12-13 | 2002-06-20 | Basf Aktiengesellschaft | Use of substituted imidazoazines, novel imidazoazines, methods for the production thereof, and agents containing these compounds |
| JP2007527886A (en) * | 2004-03-10 | 2007-10-04 | ビーエーエスエフ アクチェンゲゼルシャフト | 5,6-Dialkyl-7-aminotriazolopyrimidines, their preparation, and their use for controlling harmful fungi, and compositions containing these compounds |
| CA2557815A1 (en) * | 2004-03-10 | 2005-09-22 | Basf Aktiengesellschaft | 5,6-dihydrocarbyl-7-amino-triazolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds |
| KR101306446B1 (en) | 2004-03-10 | 2013-09-09 | 바스프 에스이 | 5,6-dialkyl-7-amino-triazolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds |
| CN101133059A (en) * | 2005-03-01 | 2008-02-27 | 巴斯福股份公司 | 5,6-dialkyl-7-amino-azolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1620694C3 (en) * | 1966-10-03 | 1982-04-15 | VEB Deutsches Hydrierwerk Rodleben, DDR 4501 Rodleben | Process for the preparation of 5-methyl-7-diethylamino-s-triazolo [1,5-a] pyrimidine and its salts with acids |
| BE792533A (en) * | 1971-12-09 | 1973-06-08 | Int Chem & Nuclear Corp | NEW PYRAZOLO (1.5A) PYRIMIDINES AND THEIR PREPARATION PROCESS |
| DE3130633A1 (en) * | 1981-08-01 | 1983-02-17 | Basf Ag, 6700 Ludwigshafen | 7-AMINO-AZOLO (1,5-A) PYRIMIDINE AND FUNGICIDES CONTAINING THEM |
| DE3338292A1 (en) * | 1983-10-21 | 1985-05-02 | Basf Ag, 6700 Ludwigshafen | 7-AMINO-AZOLO (1,5-A) -PYRIMIDINE AND FUNGICIDES CONTAINING THEM |
-
1985
- 1985-09-17 DE DE19853533050 patent/DE3533050A1/en not_active Withdrawn
-
1986
- 1986-09-04 DE DE8686112217T patent/DE3673101D1/en not_active Expired - Lifetime
- 1986-09-04 AT AT86112217T patent/ATE55131T1/en not_active IP Right Cessation
- 1986-09-04 EP EP86112217A patent/EP0215382B1/en not_active Expired - Lifetime
- 1986-09-09 CA CA000517820A patent/CA1288096C/en not_active Expired - Lifetime
- 1986-09-10 IL IL80004A patent/IL80004A0/en not_active IP Right Cessation
- 1986-09-10 JP JP61211809A patent/JPS6267084A/en active Pending
- 1986-09-15 PL PL1986261406A patent/PL148246B2/en unknown
- 1986-09-16 HU HU863964A patent/HU201652B/en not_active IP Right Cessation
- 1986-09-16 AU AU62719/86A patent/AU583150B2/en not_active Ceased
- 1986-09-16 CS CS866677A patent/CS264282B2/en unknown
- 1986-09-16 DD DD86294440A patent/DD249624A5/en not_active IP Right Cessation
- 1986-09-16 ZA ZA867018A patent/ZA867018B/en unknown
- 1986-09-16 NZ NZ217593A patent/NZ217593A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7629294B2 (en) | 2004-02-20 | 2009-12-08 | Bayer Cropscience Lp | Pyrazolopyrimidines |
Also Published As
| Publication number | Publication date |
|---|---|
| HUT42289A (en) | 1987-07-28 |
| CS264282B2 (en) | 1989-06-13 |
| AU583150B2 (en) | 1989-04-20 |
| PL148246B2 (en) | 1989-09-30 |
| DD249624A5 (en) | 1987-09-16 |
| AU6271986A (en) | 1987-03-19 |
| EP0215382B1 (en) | 1990-08-01 |
| PL261406A2 (en) | 1988-03-31 |
| NZ217593A (en) | 1988-10-28 |
| EP0215382A1 (en) | 1987-03-25 |
| DE3673101D1 (en) | 1990-09-06 |
| ATE55131T1 (en) | 1990-08-15 |
| IL80004A0 (en) | 1986-12-31 |
| HU201652B (en) | 1990-12-28 |
| JPS6267084A (en) | 1987-03-26 |
| DE3533050A1 (en) | 1987-03-26 |
| ZA867018B (en) | 1987-05-27 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |