CA1108161A - Fungicidally active cyclopropanecarboxylic acid anilides - Google Patents
Fungicidally active cyclopropanecarboxylic acid anilidesInfo
- Publication number
- CA1108161A CA1108161A CA303,250A CA303250A CA1108161A CA 1108161 A CA1108161 A CA 1108161A CA 303250 A CA303250 A CA 303250A CA 1108161 A CA1108161 A CA 1108161A
- Authority
- CA
- Canada
- Prior art keywords
- compound
- anilide
- furyl
- oxoperhydro
- cyclo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a fungicidally active cyclopropanecarboxylic acid anilides of the general formula I
The present invention provides a fungicidally active cyclopropanecarboxylic acid anilides of the general formula I
Description
The present invention is concerned with new fungicidally active cyclopropanecarboxylic acid anilides, with the use of these compounds for controlling phytopathogenic fungi and also with a process for the manufacture of the new active compounds.
Agents that act against phytopathogenic fungi have already been known. Agents of this kind known in practice are, for example, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (United States Patent Specifications Nos. 3,260,588 and 3,260,725) and tetramethylthiuram disulphide (German Patent Specification No. 642,532). These agents, however, do not always have a satis-factory action against phytopathogenic fungi.
The problem upon which the present invention is based has been to provide an agent having an outstanding action against phytopathogenic fungi. This problem is now solved in accordance with the present invention by the compounds of the general formula I, as defined below.
The present invention provides compounds of the general ~-formula I
~0 ~ ) _ 0~ o-a / ¦ (I) in which Rl represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, R2 represents an unsubstituted phenyl group ~ or a phenyl group substituted by one or more substituents selected - from alkyl groups containing 1 to 4 carbon atoms, alkoxy groups containing 1 to 4 carbon atoms, alkylthio groups containing 1 to 4 carbon atoms, halogen `~
6~
atoms, trifluoromethyl groups, nitro groups, alkoxycarbonyl groups containing 1 to 4 carbon atoms in the alkoxy part, alkylcarbonyl groups containing 1 to 4 carbon atoms in the alkyl part, phenyl,and cyano groups, and n represents 1 or 2.
When the substituted phenyl group represented by R2 contains two or more substituents these substituents may be the same or different.
The action of the compounds of the present invention against phytopathogenic fungi is surprisingly superior to that of known agents having the same direc~ion of action and, moreover, these compounds are distinguished by a good plant tolerance and a sufficient duration of action. Since, in addition, they do not act phytotoxically when applied in the quantities that come into consideration in practice, they may accordingly be used advantageously in agriculture and in horticulture for controlling phytopathogenic fungi.
The compounds of the present invention have outstanding fungicidal properties against pathogenic fungi, for example false mildew fungi.
In contrast to known fungicidal agents having only a preventive action such as, for example, N-trichloromethyl thiophthalimide (United States Patent Specifications Nos.
Agents that act against phytopathogenic fungi have already been known. Agents of this kind known in practice are, for example, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (United States Patent Specifications Nos. 3,260,588 and 3,260,725) and tetramethylthiuram disulphide (German Patent Specification No. 642,532). These agents, however, do not always have a satis-factory action against phytopathogenic fungi.
The problem upon which the present invention is based has been to provide an agent having an outstanding action against phytopathogenic fungi. This problem is now solved in accordance with the present invention by the compounds of the general formula I, as defined below.
The present invention provides compounds of the general ~-formula I
~0 ~ ) _ 0~ o-a / ¦ (I) in which Rl represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, R2 represents an unsubstituted phenyl group ~ or a phenyl group substituted by one or more substituents selected - from alkyl groups containing 1 to 4 carbon atoms, alkoxy groups containing 1 to 4 carbon atoms, alkylthio groups containing 1 to 4 carbon atoms, halogen `~
6~
atoms, trifluoromethyl groups, nitro groups, alkoxycarbonyl groups containing 1 to 4 carbon atoms in the alkoxy part, alkylcarbonyl groups containing 1 to 4 carbon atoms in the alkyl part, phenyl,and cyano groups, and n represents 1 or 2.
When the substituted phenyl group represented by R2 contains two or more substituents these substituents may be the same or different.
The action of the compounds of the present invention against phytopathogenic fungi is surprisingly superior to that of known agents having the same direc~ion of action and, moreover, these compounds are distinguished by a good plant tolerance and a sufficient duration of action. Since, in addition, they do not act phytotoxically when applied in the quantities that come into consideration in practice, they may accordingly be used advantageously in agriculture and in horticulture for controlling phytopathogenic fungi.
The compounds of the present invention have outstanding fungicidal properties against pathogenic fungi, for example false mildew fungi.
In contrast to known fungicidal agents having only a preventive action such as, for example, N-trichloromethyl thiophthalimide (United States Patent Specifications Nos.
2,553,770, 2,553,771 and 2,553,776) and manganese ethylene bisdithiocarbamate (United States Patent Specifications Nos.
2,504,404,and 2,710,822), the compounds of the present invention ':~
~ 30 ' ' .:' ~ .
11~8~61 surprisingly also have the additional advantage of a curative and systemic action which, therefore, makes i~ possible also to control pathogenic agents that have already penetrated into the plants.
The present invention accordingly also provides a fungicidal preparation which comprises a compound of the general formula I, in admixture or conjunction with a suitable carrier.
The preparation may of course contain one or more compounds of the general formula I.
The present invention further provides a method of pro- ~
tecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the general formula I.
The present invention further provides a method of pro-tecting a crop area against phytopathogenic fungi, wherein the crop area is treated with a compound of the general formula I.
The present invention further provides a method of dressing seeds, wherein the seeds are treated with a compound of the general formula I.
The present invention further provides a pack which com-prises a compound of the general formula I together with in-structions for its use for controlling phytopathogenic fungi.
The compounds of the present invention that are especially distinguished by an outstanding fungicidal action are those of the general formula I given above in which Rl represents a hydrogen atom or a methyl or ethyl group and R2 represents a phenyl, methylphenyl, dimethylphenyl, ethylphenyl, isopropyl-phenyl, methoxyphenyl, ethoxyphenyl, methylthiophenyl, fluoro-phenyl, chlorophenyl, bromophenyl, dichlorophenyl, trifluoro-methylphenyl, nitrophenyl, cyanophenyl, methoxycarbonylphenyl, acetylphenyl or biphenylyl group.
The new active compounds may be applied singly or,
2,504,404,and 2,710,822), the compounds of the present invention ':~
~ 30 ' ' .:' ~ .
11~8~61 surprisingly also have the additional advantage of a curative and systemic action which, therefore, makes i~ possible also to control pathogenic agents that have already penetrated into the plants.
The present invention accordingly also provides a fungicidal preparation which comprises a compound of the general formula I, in admixture or conjunction with a suitable carrier.
The preparation may of course contain one or more compounds of the general formula I.
The present invention further provides a method of pro- ~
tecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the general formula I.
The present invention further provides a method of pro-tecting a crop area against phytopathogenic fungi, wherein the crop area is treated with a compound of the general formula I.
The present invention further provides a method of dressing seeds, wherein the seeds are treated with a compound of the general formula I.
The present invention further provides a pack which com-prises a compound of the general formula I together with in-structions for its use for controlling phytopathogenic fungi.
The compounds of the present invention that are especially distinguished by an outstanding fungicidal action are those of the general formula I given above in which Rl represents a hydrogen atom or a methyl or ethyl group and R2 represents a phenyl, methylphenyl, dimethylphenyl, ethylphenyl, isopropyl-phenyl, methoxyphenyl, ethoxyphenyl, methylthiophenyl, fluoro-phenyl, chlorophenyl, bromophenyl, dichlorophenyl, trifluoro-methylphenyl, nitrophenyl, cyanophenyl, methoxycarbonylphenyl, acetylphenyl or biphenylyl group.
The new active compounds may be applied singly or,
- 3 -", /
8~
alternatively, mixtures of at least two constitutionally different compounds of the general formula I may be applied. If aesired, other fungicides, nematocides, herbicides or other types of pest-controlling agents may be added, depending on the purpose.
The active substances are advantageously applied in the form of fungicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid vehicles or diluents and, if desired, of wetting, adhesive, emulsifying and/or dispersing agents.
Suitable liquid carriers are, for example, water, mineral oils or other organic solvents, for example xylene, chlorobenzene, cyclohexanol, dioxan, acetonitrile, ethyl acetate, dimethylformamide, isophorone and dimethyl sulphoxide.
Suitable solid carriers are, for example, lime, kaolin, chalk, talcum, attaclay and other clays as well as natural or synthetic silicic acid.
As surface-active agents there may be mentioned, for example, salts of ligninsulphonic acids, salts of alkylated benzenesulphonic acids, sulphonated acid amides and salts thereof, polyethoxylated amines and alcohols.
When the active substances are to be used for dressing seeds, they may also be admixed with dyestuffs in order to give the dressed seeds a clearly visible colour.
The proportion of active substance(s) in the fungicidal preparations may vary within wide limits, the exact concentra-tion of the active substances used for the preparations being primarily dependent on the quantity in which the preparations inter alia are to be used for treating soil or seeds or for ; 30 spraying leaves. The preparations may contain, for example, .
.~,~
.
approximately 1 to 80% by weight, preferably between 20 and 50~ by weiqht, of active compound(s), approximately 99 to 20~
by weight of liquid or solid carrier and also, if desired, up to 20~ by weight of surface-active agent(s).
The new compounds of the general formula I may be produced by the process of the present invention, as defined below.
The present invention further provides a process for the manufacture of a compound of the general formula I, wherein a compound of the general formula II .-(C~2)n- ~H~ R2 (~
l J~o ; ~/ ~o-- ~
. .
in which Rl, R2 and n have the meanings given above, is reacted ::
in the presence of an acid-binding agent and, if desired, a ; solvent with cyclopropanecarboxylic acid chloride of the formula ~ III
; 20 C'l ~ C0 - C~ ¦ (III) O
~H2 The amounts used of the compound of the general formula II and the compound of the formula III are preferably in equimolar proportions.
As acid-binding agents there may be used, for example, organic bases, for example pyridine, triethylamine or N,N-dimethylaniline, or inorganic bases, for example hydroxides, : oxides and carbonates of alkali metals and alkaline earth metals, for example sodium, potassium or calcium.
As a solvent that may optionally be used, there may bementioned, for example, ether, tetrahydrofuran, benzene or ethyl acetate. Liquid acid-binding agents, for example pyridine, may serve simultaneously as solvents.
The reaction is advantageously carried out at a temperature within the range of from -10C to 120C.
The products of the process of the present invention may be isolated in a manner known per se.
Some specific compounds of the present invention are - 10 listed in the following Table.
~ 30 -` ~q~16~
Compound Name Physical constant No.
. _ .
1 Cyclopropanecarboxylic acid [N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 104C
2 Cyclopropanecarboxylic acid [2,6-diethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 102-103C
3 Cyclopropanecarboxylic acid [2-methoxy-N-(2-oxoperhydro-~: 3-furyl)-anilide] M.p.: 175-176C : -: 4 Cyclopropanecarboxylic acid [2-methyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 108-109C
- ' ; 5 Cyclopropanecarboxylic acid :~
[2,6-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 114-116C :
6 Cyclopropanecarboxylic acid ~::
[2,5-dimethyl-N-(2-oxoperhydro- : :
3-furyl)-anilide] M.p.: 84C
7 Cyclopropanecarboxylic acid [3-methyl-N-(2-oxoperhydro-;. 3-furyl)-anilide] M.p.: 109C
8 Cyclopropanecarboxylic acid : [4-methyl-N-(2-oxoperhydro-- 3-furyl)-anilide] M.p.: 123C
9 Cyclopropanecarboxylic acid [3,4-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 99-100C
Cyclopropanecarboxylic acid [2,3-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 153C
11 Cyclopropanecarboxylic acid [2,4-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 85-86C
12 Cyclopropanecarboxylic acid [3,5-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 103C
:' .. ''~ ' 13 Cyclopropanecarboxvlic acid [2,4,6-trimethyl-N-(2-oxoper-hydro-3-furyl)-anilide] M.p.: 119 - 121C
14 CyclopropanecarboxYlic acid [4-chloro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 149 - 150C
Cyclopropanecarboxylic acid [3-chloro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 99 - 100C
16 Cyclopropanecarboxylic acid [4-isopropyl-N-(2-oxoper-hydro-3-furyl)-anilide] M.p.: 108 - 110C
. .
17 Cyclopropanecarboxylic acid [3-trïfluoromethyl-N-(2-oxoper-hydro-3-furyl)-anilide] M.p.: 104 - 105C
18 Cyclopropanecarboxylic acid [3-fluoro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 89C
19 Cyclopropanecarboxylic acid [3-hromo-N-(2-oxoperhydro-3-furyl)-anilide] M.p: 93 - 94C
: 20 Cyclopropanecarboxylic acid [2,6-diisopropyl-N-(2-oxoper-hydro-3-furyl)-anilide] ~1.p.: 215 - 216C
: 21 Cyclopropanecarboxylic acid [2-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 103C
22 Cyclopropanecarboxylic acid [4-ethvl-N-(2-oxoperhYdro-3-furyl)-anilide] M.p.: 107C
23 Cyclopropanecarboxvlic acid [4-methoxy-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 75C
24 Cyclopropanecarboxylic acid [4-bromo-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 144 - 145C
Cyclopropanecarboxy].ic acid . . [4-fluoro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 138 - 139C
: 26 Cyclopropanecarboxylic acid [2-ethoxy-N-(2-oxoperhydro-: 3-furyl)-anilide] M.p.: 143 - 145C
27 Cyclopropanecarboxyl;c acid [3-chloro-2-methyl-N-(2-oxoper-hydro-3-furyl)-anilide] M.p.: 121 - 124C
3~10831~ -28 Cyclopropanecarboxylic acid [5-chloro~2-methyl-N-(2-oxoper-hydro 3-furyl)~anil~de] M.p.: 114 - 116C
29 Cyclopropanecaxboxylic acid [4-methoxy-2 methvl-N~(2- 20 oxoperhydro~3-furyl)-anilide] nD = 1.5520 Cyclopropanecarboxylic acid [4-ethoxy-N-(2-oxoperhydro- 20 3-furyl)-anilide] nD = 1,4579 i~ 31 Cyclopropanecarboxylic acid [5-chloro-2-methoxy-N-(2-oxo-perhydro-3-furyl3-anilide] M.p.: 163 - 164C
32 Cyclopropanecarboxylic acid ~-[3-chloro-N-(5-methyl-2-oxo-perhydro-3-furyl)-anilide] M.p.: 95 - 97C
33 Cyclopropanecarboxylic acid [3-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 69 - 70C
- 34 Cyclopropanecarboxylic acid [3-cyano-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 142 - 143C
Cyclopropanecarboxylic acid [3-thiomethyl-N-(2-oxoperhvdro- 0 3-furyl)-anilide] nD = 1.5888 36 Cyclopropanecarboxylic acid [2,3-dichloro-N-(2-oxoperhydro-` 3-furyl)-anilide] M.p.: 136 - 137C
The compounds of the present invention are ingeneral almost colourless,odourless,cristalline substances which are prac-tically insoluble in water and benzine, but, in contrast, are verv readily soluble in polar organic solvents, for example acetone, dimethylformamide and dimethyl sulphoxide.
The starting compounds for the manufacture of the com-pounds of the present invention are known per se or may be produced ; according to processes known per se.
The following Examples illustrate the invention. Example 1 illustrates the manufacture of the compounds of the present invention and Examples 2 to 9 illustrate the possibilities of application of the co~pounds ~f the present inyention.
Example 1 .
Cyclopropanecarboxylic acid [~ (2-oxoperhydro-`3-furyl)-anilide]
(Compound No. 1) 6.30 g (0.06 mole) of cyclopropanecarboxylic acid chloride were added dropwise, at a 5 to 10C internal temperature, while stirring, to a solution of 10.62 a (0.06 mole) of 3-anilinoper-hydrofuran-2-one in 50 ml of pyridine. The mixture was then stirred for 1/2 hour at room temperature and then poured on to 200 a of water/ice and stirred well. After filtering with suction, the mixture was carefully washed with water and dried in a drying cupboard.
Yield: 10.25g = 70~ of the theoretical yield; m.p.: 104C.
Each of the other compounds of the present invention listed in the Tahle above may be produced in an analogous manner.
Example 2 -Limiting concentration test in the control of Py*hium ultimum _.
In a series of tests 20~ pulverulent active substance preparations were mixed uniformlv with soil which was severely infected with P~thium ultimum. The treated soil was placed in clay dishes each having a capacity of 0.5 litre and, without a waiting period, 20 marrowfat peas of the "Xelvedon Wonder"
variety were sown in each dish. ~fter a cultivation period of three weeks at 20 to 24C the number of healthy peas was determined and an assessment (1 - 4 as defined below) of the roots was carried out.
The active substances used and their application ~uan-tities, and also the results, are given in the following Table.
g _ Active substance Num~er of Root Compound according to concentration in healthy assessment the invention mg/l soil _peas (1 - 4) Cyclopropanecarboxvlic 10 17 4 acid [N-(2-oxoperhydro- 20 17 4 3-furyl)-anilide] 40 18 4 Cyclopropanecarboxylic 10 16 4 ~ ,~
: acid [2~6-dimethyl-N- 20 20 4 (2-oxoperhydro-3~furyl)- 40 19 4 anilide]
Cyclopropanecarboxylic 10 19 4 ~: -acid [3-chloro-N-(2-oxo- 20 17 4 perhydro-3-furyl)-anilide] 40 17 4 Cyclopropanecarboxylic 10 10 10 acid [3-methyl-N-(2-oxo- 20 16 2 -:
perhydro-3-furyl)-anilide] 40 16 4 Cyclopropanecarboxylic 10 10 acid [2-methoxy-N-(2-oxo- 20 16 2 perhydro-3-furyl)-anilide] 40 20 4 Agent for comparison `
5-Ethoxy-3-trichloro- 10 2 methyl-1,2,4-thiadiazole 20 5 Control I
. . .
(3 repetitions) a) 1 1-Infected soil b) 0 c ) O
Control II
20 (3 repetitions) a) 19 4 Steamed soil b) 18 4 c) , ,18 4 Root assessment: 4 = white roots without fungal necroses;
3 = whi.te roots, slight fungal necroses;
2 = brown roots, considerably severe fungal necroses;
, 1 = severe fungal necroses, mouldy roots.
Example_3 . .
Dress.inq o`f su'~'arbeet . _ _ In a series of tests graded sugarbeet seeds of the variety "Dieckmann Suprapolyl' were dressed with-20% pulverulent active substance prepar~tions~ Clay dishes each of 2 litres capacity ~ ~ .
:; : : . .
(20 x 20 x 5 cm) were filled with normal compost soil (damping-off) and 100 of the sugarbeet seeds were sown in each dish .
After a cultivation period of 18 days at 19 to 21C in a green-house the numker of healthy seedlings was determined.
The active substances used and their application quan-tities, and also the results, are given in the following Table.
''' . .
. .
' ` ' X
Compound according to Active substance # of healthy the invention in g/ka seed seedlings from lOO.seeds .. . .
Cyclopropanecarboxylic acid 0.4 79 [N-(2-oxoperhydro-3-furyl)- 0.8 79 anilide] 1.6 75 Cyclopropanecarhoxylic acid 0.4 70 [2,6-dimethyl-N-(2-oxoper- 0.8 76 hydro-3-furyl)-anilide] 1.6 83 Cyclopropanecarboxylic acid 0.4 83 [3-chloro-N-(2-oxoperhydro- 0.8 82 3-furyl)-anilide] 1.6 93 Cyclopropanecarboxylic acid 0.4 77 10 [3-methyl~N-(2-oxoperhvdro- 0.8 71 3-furyl)-anilide] 1.6 85 Cyclopropanecarboxylic acid 0.4 83 [2-methoxy-N-(2-oxoperhydro- 0.8 87 3-furyl)-anilide] 1.6 87 Agents for comparison 5-Ethoxy-3-trichloromethyl- 0.4 26 1,2,4-thiadiazole 0.8 44 1.6 53 : Tetramethyl.thiuram 4.8 21 disulphide 9.6 50 : Control I
(3 repetitions) a) 5 Infected soil b) 7 c) 6 Control II
t3 repetitions) a) 83 Steamed soil b) 86 c) 81 1~ 6~ - -Example 4 Ef fect of prophylatic leaf treatment against Plasmopara viticola on vines in a greenhouse In a series of testsvoung vines having approximately 5 to 8 leaves were sprayed until dripping wet with the concentration of active substance indicated in the Table below and, after the spray coating had dried on, were sprayed on the undersides of the leaves with an aqueous suspension of sporangia of the fungus indi-cated in the heading above (approximately 20,000 per ml), and immediately incubated in a greenhouse at 22 to 24C in an atmos-phere as saturated with water vapour as possihle. From the second day onwards, the air humidity was reduced to the normal level for 3 to 4 days (approximately 30 to 70% saturation) and then maintained at water vapour saturation for a further day. The percentage proportion of the surface attacked hy fungi of each leaf was then recorded and the average per treatment was calculated as follows to determine the fungicidal effect:
100 - `100 x attack in treated plants = % effect . .
attack in untreated Plants : 30 Compound .csording to the %Effect ~qainst Concentration invention Plasmopara (%active vit~co~a ~) substance) Cyclopropanecarboxylic acid [2,6-diethyl-N-(2-oxoper-hydro-3-furyl)-anilide] 40 0.025 Cyclopropanecarboxylic acid [3-fluoro-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.025 Cyclopropanecarboxylic acid [3-bromo-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.025 Cyclopropanecarboxylic acid [2,6-diisopropyl-N-(2-oxoper-hydro-3-furyl)-anilide] 84 0.025 Cyclopropanecarboxylic acid [2-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] 83 0.025 Cyclopropanecarboxylic acid [4-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] 40 0~025 Cyclopropanecarboxylic acid [4-fluoro-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.025 Cyclopropanecarboxylic acid [2-ethoxy-N-(2-oxoperhydro-3-furyl)-anilide] 70 0.025 Cyclopropanecarboxylic acid [3-chloro-2-methyl-N-(2-oxoper-hydro-3-furyl)-anilide] 98 0.025 Cyclopropanecarboxylic acid [3-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] . 100 0.025 Cyclopropanecarboxylic.acid .
[3-cyano-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.025 Cyclopropanecarboxylic acid ~3-thiomethyl-N-(2-oxoper-hydro-3-furyl)-anilide] 70 0.025 Cyclopropanecarhoxylic acid [2,3-dichloro-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.025 Cyclopropanecarbox~tl;c acid [N-(2--oxoperhydro 3-furyl)-anilide] 100 0.001 Cyclopropanecarboxylic acid 13-chloro-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.001 ~.-- .
~ - 14 -+) Effect was calculated on 100% attack in the untreated control.
Example 5 -Effect of prophylactic leaf treatment against Phytophthora infestans in tomato plants or p.otato plants in .a greenhouse In a series of tests younq tomato plants having at least two developed foliage leaves and potato plants (for example from eye cuttings) at least 10 cm tall were sprayed until dripping wet with the concentration of active substance indicated in the Table below and, after the spray coatinq had driedon, were sprayed with 10 an aqueous suspension which contained per millilitre 50,000 to 80,000 sporangia of the fungus indicated in the heading above and which had been incubated in a refrigerator at 11C for approximately 2 hours. The plants were incubated at a high level of air humidity and at approximately 15 to 18C in a greenhouse and, after approxi-mately 5 days, the percentaae proportion of leaf surface that had been attackefl was assessed. The fungicidal effect was calculated as follows:
100 = 100 x attack in treated plants = ~ effect attack in untreated plants ~ Effect against Phytophthora infestansin potatoes +) Compound accordinq to the Concentration (~
invention active substance ) _. _ __ 0.005 Cyclopropanecarboxylic acid [N-(2-oxoperhydro-3-furyl)-anilide] - 95 Cyclopropanecarboxylic acid [2,6-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] 80 ?~
, - 15 -Agent for comparison ~anganese ethylene bisd~thio-carbamate 50 %Effect against Phytophthora infestans in tomatoes.+) _ _ .
~ompound accordina to the Concentration (%
invention active substance) . 0.005 -Cyclopropanecarboxvlic acid [N-(2-oxoperhydro-3-furyl)-anilide] 100 Cyclopropanecarboxylic acid [3-methyl-N-(2~oxoperhydro-3-10 furyl)-anilide] 81 Cyclopropanecarboxylic acid [3-chloro-N-(2-oxoperhydro-3-furyl)-anilide] 91 Agent for com~arison -Manaanese ethylene bisdithio-carbamate 67 : +) Effect was calculated on 100% attack in the untreated control : Example 6 Systemic effect of soil treatment against Phytophthora infestans in tomato p.lants o.r potatoplants in a areenhouse ..... _ : 20 In a series of tests the substances to be tested, which had been weighed out (weiqht be volume), were mixed with arable soil which was then placed in plant pots, and young tomato plants having at least two developed foliage leaves and potato plants (for example from eye cuttings) at least 10 cm tall were placed in these pots. After the desired pre-dose time (for .. example after 4 or 18 days? had expired, the plants were sprayed with an aqueous suspension which contained per millilitre S0,000 ~ to 80,000 sporangia of the fungus indicated in the heading above .. and which had been incubated in a refrigerator at 11C for approximately 2 hours. The plants were incubated at a high ~81~1 level of air humidity and at approximately 15 to 18C in a greenhouse and, aEter approximately 5 days, the percentage pro-portion of leaf surface that had been attacked was assessed.
l'he fungicidal effect was calculated as follows;
100 - 100 x attack in treated plants = % effect attack in ~ntreated plants Systemic effect of soil treatment against Phytophthora infestans 10in tomato plants Compound according to tne ppm active ~ Effect 4 +) of treatment invention substance days before 18 days before inoculation inoculation .. . .. . . ... ... .. _ . _ .
Cyclopropanecarboxylic acid 25 89 85 [N-(2-oxoperhydro-3-furyl)-5 70 39 anilide]
Cyclopropanecarboxylic acid 25 92 82 [2,6-dimethyl-I~-(2-oxoper-5 40 71 hydro-3-furyl)-anilide]
+) Effect was calculated on 100% attack in the untreated control ~0 ; Example 7 Curative effect of leaf treatment against Phytophthora infestans in tomato plants or potato plants in a greenhouse , In a series of tests young tomato plants having at least two developed foliage leaves or potato plants (for example from eye cuttings) at least 10 cm tall were sprayed with an aqueous suspension which contained per millilitre 50,000 to 80,000 sporangia of the fungus indicated in the heading above and which had been incubated in a refrigerator at 11C for approximately 2 hours. The plants were incubated at a high level of air humidity. After the desired pre-dose time had expired, the plants were sprayed until dripping wet, within the period of 8~
latent fungal attack, with the concentration to be tested of the fungicide indicated in the Table below. After the outbreak of fungal attack in the untreated control plants the percentage proportion of leaf surface that had been attacked was assessed.
The fungicidal effect was calculated as follows:
100 - 100 x attàck in treated plants = % effect ... .
attack in untreated plants .
Compound according to the ~ Active % Effect +) of treat-invention substance before ment 1 day sprayed inoculation after inoculation .. .. . _ _ Cyclopropanecarboxylic acid [~-(2-oxoperhydro-3-furyl)-anilide] 0.004 100 68 Cyclopropanecarboxylic acid [2,6-dimethyl-N-(2-oxoper-hydro-3-furyl)-anilide] 0.004 100 60 Agent for comparison Manganese ethylene bisdithio-carbamate 0.004 91 0 +) Effect was calculated on 100~ attack in the untreated control Example 8 Effect of treatment of barley grains against helminthosporium spec.
In a series of tests barley grains that had been attacked by helmintilosporium spec. were treated with S0 mg of .....
active substance per 100 g of grains. rrhe grains were then SOWII
in soil and incubated in an air-conditioned chamber at +1~C.
Tile tests were evaluated after 6 weeks and tile rexulting seed-lings exnibited a markedly reduced attack as compared with plantsof an untreated control group.
lhe results are given in the following Table.
Compound according to the % Effect invention . .
Cyclopropanecar~oxylic acid [4-metllyl-N-(2-oxoperllydro-3-furyl)-anilide] 40 Cyclopropanecarboxylic acid [~,4-dimethyl-N-(2-oxoper-hydro-3-furyl)-anilide] : ~ 40 Cyclopropanecarboxylic acid [4-ethyl-1~-(2-oxoperhydro-3-furyl)-anilide] 40 Untreated control o ~xample_ Limiting concentration test in the control of Pythium ultimum In a series of tests 20~ pulverulent active substance preparations were mixed uniformly with soil which was severely infected with Pythium ultimum. The treated soil was placed in clay dishes each having a capacity of 0.5 litre and, without a waiting period, 20 marrowfat peas (Pisum sativum L. convar.
medullare Alev.) of the "Kelvedon Wonder" variety were sown in each dish. After a cultivation period of 3 wee]cs at 20 to 40C
the number of healtlly peas was determined and an assessment (1 - 4 as defined below) of the roots was carried out.
The active substances used and their application cluantities, and also the results, are given in the following Table.
8~
alternatively, mixtures of at least two constitutionally different compounds of the general formula I may be applied. If aesired, other fungicides, nematocides, herbicides or other types of pest-controlling agents may be added, depending on the purpose.
The active substances are advantageously applied in the form of fungicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid vehicles or diluents and, if desired, of wetting, adhesive, emulsifying and/or dispersing agents.
Suitable liquid carriers are, for example, water, mineral oils or other organic solvents, for example xylene, chlorobenzene, cyclohexanol, dioxan, acetonitrile, ethyl acetate, dimethylformamide, isophorone and dimethyl sulphoxide.
Suitable solid carriers are, for example, lime, kaolin, chalk, talcum, attaclay and other clays as well as natural or synthetic silicic acid.
As surface-active agents there may be mentioned, for example, salts of ligninsulphonic acids, salts of alkylated benzenesulphonic acids, sulphonated acid amides and salts thereof, polyethoxylated amines and alcohols.
When the active substances are to be used for dressing seeds, they may also be admixed with dyestuffs in order to give the dressed seeds a clearly visible colour.
The proportion of active substance(s) in the fungicidal preparations may vary within wide limits, the exact concentra-tion of the active substances used for the preparations being primarily dependent on the quantity in which the preparations inter alia are to be used for treating soil or seeds or for ; 30 spraying leaves. The preparations may contain, for example, .
.~,~
.
approximately 1 to 80% by weight, preferably between 20 and 50~ by weiqht, of active compound(s), approximately 99 to 20~
by weight of liquid or solid carrier and also, if desired, up to 20~ by weight of surface-active agent(s).
The new compounds of the general formula I may be produced by the process of the present invention, as defined below.
The present invention further provides a process for the manufacture of a compound of the general formula I, wherein a compound of the general formula II .-(C~2)n- ~H~ R2 (~
l J~o ; ~/ ~o-- ~
. .
in which Rl, R2 and n have the meanings given above, is reacted ::
in the presence of an acid-binding agent and, if desired, a ; solvent with cyclopropanecarboxylic acid chloride of the formula ~ III
; 20 C'l ~ C0 - C~ ¦ (III) O
~H2 The amounts used of the compound of the general formula II and the compound of the formula III are preferably in equimolar proportions.
As acid-binding agents there may be used, for example, organic bases, for example pyridine, triethylamine or N,N-dimethylaniline, or inorganic bases, for example hydroxides, : oxides and carbonates of alkali metals and alkaline earth metals, for example sodium, potassium or calcium.
As a solvent that may optionally be used, there may bementioned, for example, ether, tetrahydrofuran, benzene or ethyl acetate. Liquid acid-binding agents, for example pyridine, may serve simultaneously as solvents.
The reaction is advantageously carried out at a temperature within the range of from -10C to 120C.
The products of the process of the present invention may be isolated in a manner known per se.
Some specific compounds of the present invention are - 10 listed in the following Table.
~ 30 -` ~q~16~
Compound Name Physical constant No.
. _ .
1 Cyclopropanecarboxylic acid [N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 104C
2 Cyclopropanecarboxylic acid [2,6-diethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 102-103C
3 Cyclopropanecarboxylic acid [2-methoxy-N-(2-oxoperhydro-~: 3-furyl)-anilide] M.p.: 175-176C : -: 4 Cyclopropanecarboxylic acid [2-methyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 108-109C
- ' ; 5 Cyclopropanecarboxylic acid :~
[2,6-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 114-116C :
6 Cyclopropanecarboxylic acid ~::
[2,5-dimethyl-N-(2-oxoperhydro- : :
3-furyl)-anilide] M.p.: 84C
7 Cyclopropanecarboxylic acid [3-methyl-N-(2-oxoperhydro-;. 3-furyl)-anilide] M.p.: 109C
8 Cyclopropanecarboxylic acid : [4-methyl-N-(2-oxoperhydro-- 3-furyl)-anilide] M.p.: 123C
9 Cyclopropanecarboxylic acid [3,4-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 99-100C
Cyclopropanecarboxylic acid [2,3-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 153C
11 Cyclopropanecarboxylic acid [2,4-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 85-86C
12 Cyclopropanecarboxylic acid [3,5-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 103C
:' .. ''~ ' 13 Cyclopropanecarboxvlic acid [2,4,6-trimethyl-N-(2-oxoper-hydro-3-furyl)-anilide] M.p.: 119 - 121C
14 CyclopropanecarboxYlic acid [4-chloro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 149 - 150C
Cyclopropanecarboxylic acid [3-chloro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 99 - 100C
16 Cyclopropanecarboxylic acid [4-isopropyl-N-(2-oxoper-hydro-3-furyl)-anilide] M.p.: 108 - 110C
. .
17 Cyclopropanecarboxylic acid [3-trïfluoromethyl-N-(2-oxoper-hydro-3-furyl)-anilide] M.p.: 104 - 105C
18 Cyclopropanecarboxylic acid [3-fluoro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 89C
19 Cyclopropanecarboxylic acid [3-hromo-N-(2-oxoperhydro-3-furyl)-anilide] M.p: 93 - 94C
: 20 Cyclopropanecarboxylic acid [2,6-diisopropyl-N-(2-oxoper-hydro-3-furyl)-anilide] ~1.p.: 215 - 216C
: 21 Cyclopropanecarboxylic acid [2-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 103C
22 Cyclopropanecarboxylic acid [4-ethvl-N-(2-oxoperhYdro-3-furyl)-anilide] M.p.: 107C
23 Cyclopropanecarboxvlic acid [4-methoxy-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 75C
24 Cyclopropanecarboxylic acid [4-bromo-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 144 - 145C
Cyclopropanecarboxy].ic acid . . [4-fluoro-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 138 - 139C
: 26 Cyclopropanecarboxylic acid [2-ethoxy-N-(2-oxoperhydro-: 3-furyl)-anilide] M.p.: 143 - 145C
27 Cyclopropanecarboxyl;c acid [3-chloro-2-methyl-N-(2-oxoper-hydro-3-furyl)-anilide] M.p.: 121 - 124C
3~10831~ -28 Cyclopropanecarboxylic acid [5-chloro~2-methyl-N-(2-oxoper-hydro 3-furyl)~anil~de] M.p.: 114 - 116C
29 Cyclopropanecaxboxylic acid [4-methoxy-2 methvl-N~(2- 20 oxoperhydro~3-furyl)-anilide] nD = 1.5520 Cyclopropanecarboxylic acid [4-ethoxy-N-(2-oxoperhydro- 20 3-furyl)-anilide] nD = 1,4579 i~ 31 Cyclopropanecarboxylic acid [5-chloro-2-methoxy-N-(2-oxo-perhydro-3-furyl3-anilide] M.p.: 163 - 164C
32 Cyclopropanecarboxylic acid ~-[3-chloro-N-(5-methyl-2-oxo-perhydro-3-furyl)-anilide] M.p.: 95 - 97C
33 Cyclopropanecarboxylic acid [3-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 69 - 70C
- 34 Cyclopropanecarboxylic acid [3-cyano-N-(2-oxoperhydro-3-furyl)-anilide] M.p.: 142 - 143C
Cyclopropanecarboxylic acid [3-thiomethyl-N-(2-oxoperhvdro- 0 3-furyl)-anilide] nD = 1.5888 36 Cyclopropanecarboxylic acid [2,3-dichloro-N-(2-oxoperhydro-` 3-furyl)-anilide] M.p.: 136 - 137C
The compounds of the present invention are ingeneral almost colourless,odourless,cristalline substances which are prac-tically insoluble in water and benzine, but, in contrast, are verv readily soluble in polar organic solvents, for example acetone, dimethylformamide and dimethyl sulphoxide.
The starting compounds for the manufacture of the com-pounds of the present invention are known per se or may be produced ; according to processes known per se.
The following Examples illustrate the invention. Example 1 illustrates the manufacture of the compounds of the present invention and Examples 2 to 9 illustrate the possibilities of application of the co~pounds ~f the present inyention.
Example 1 .
Cyclopropanecarboxylic acid [~ (2-oxoperhydro-`3-furyl)-anilide]
(Compound No. 1) 6.30 g (0.06 mole) of cyclopropanecarboxylic acid chloride were added dropwise, at a 5 to 10C internal temperature, while stirring, to a solution of 10.62 a (0.06 mole) of 3-anilinoper-hydrofuran-2-one in 50 ml of pyridine. The mixture was then stirred for 1/2 hour at room temperature and then poured on to 200 a of water/ice and stirred well. After filtering with suction, the mixture was carefully washed with water and dried in a drying cupboard.
Yield: 10.25g = 70~ of the theoretical yield; m.p.: 104C.
Each of the other compounds of the present invention listed in the Tahle above may be produced in an analogous manner.
Example 2 -Limiting concentration test in the control of Py*hium ultimum _.
In a series of tests 20~ pulverulent active substance preparations were mixed uniformlv with soil which was severely infected with P~thium ultimum. The treated soil was placed in clay dishes each having a capacity of 0.5 litre and, without a waiting period, 20 marrowfat peas of the "Xelvedon Wonder"
variety were sown in each dish. ~fter a cultivation period of three weeks at 20 to 24C the number of healthy peas was determined and an assessment (1 - 4 as defined below) of the roots was carried out.
The active substances used and their application ~uan-tities, and also the results, are given in the following Table.
g _ Active substance Num~er of Root Compound according to concentration in healthy assessment the invention mg/l soil _peas (1 - 4) Cyclopropanecarboxvlic 10 17 4 acid [N-(2-oxoperhydro- 20 17 4 3-furyl)-anilide] 40 18 4 Cyclopropanecarboxylic 10 16 4 ~ ,~
: acid [2~6-dimethyl-N- 20 20 4 (2-oxoperhydro-3~furyl)- 40 19 4 anilide]
Cyclopropanecarboxylic 10 19 4 ~: -acid [3-chloro-N-(2-oxo- 20 17 4 perhydro-3-furyl)-anilide] 40 17 4 Cyclopropanecarboxylic 10 10 10 acid [3-methyl-N-(2-oxo- 20 16 2 -:
perhydro-3-furyl)-anilide] 40 16 4 Cyclopropanecarboxylic 10 10 acid [2-methoxy-N-(2-oxo- 20 16 2 perhydro-3-furyl)-anilide] 40 20 4 Agent for comparison `
5-Ethoxy-3-trichloro- 10 2 methyl-1,2,4-thiadiazole 20 5 Control I
. . .
(3 repetitions) a) 1 1-Infected soil b) 0 c ) O
Control II
20 (3 repetitions) a) 19 4 Steamed soil b) 18 4 c) , ,18 4 Root assessment: 4 = white roots without fungal necroses;
3 = whi.te roots, slight fungal necroses;
2 = brown roots, considerably severe fungal necroses;
, 1 = severe fungal necroses, mouldy roots.
Example_3 . .
Dress.inq o`f su'~'arbeet . _ _ In a series of tests graded sugarbeet seeds of the variety "Dieckmann Suprapolyl' were dressed with-20% pulverulent active substance prepar~tions~ Clay dishes each of 2 litres capacity ~ ~ .
:; : : . .
(20 x 20 x 5 cm) were filled with normal compost soil (damping-off) and 100 of the sugarbeet seeds were sown in each dish .
After a cultivation period of 18 days at 19 to 21C in a green-house the numker of healthy seedlings was determined.
The active substances used and their application quan-tities, and also the results, are given in the following Table.
''' . .
. .
' ` ' X
Compound according to Active substance # of healthy the invention in g/ka seed seedlings from lOO.seeds .. . .
Cyclopropanecarboxylic acid 0.4 79 [N-(2-oxoperhydro-3-furyl)- 0.8 79 anilide] 1.6 75 Cyclopropanecarhoxylic acid 0.4 70 [2,6-dimethyl-N-(2-oxoper- 0.8 76 hydro-3-furyl)-anilide] 1.6 83 Cyclopropanecarboxylic acid 0.4 83 [3-chloro-N-(2-oxoperhydro- 0.8 82 3-furyl)-anilide] 1.6 93 Cyclopropanecarboxylic acid 0.4 77 10 [3-methyl~N-(2-oxoperhvdro- 0.8 71 3-furyl)-anilide] 1.6 85 Cyclopropanecarboxylic acid 0.4 83 [2-methoxy-N-(2-oxoperhydro- 0.8 87 3-furyl)-anilide] 1.6 87 Agents for comparison 5-Ethoxy-3-trichloromethyl- 0.4 26 1,2,4-thiadiazole 0.8 44 1.6 53 : Tetramethyl.thiuram 4.8 21 disulphide 9.6 50 : Control I
(3 repetitions) a) 5 Infected soil b) 7 c) 6 Control II
t3 repetitions) a) 83 Steamed soil b) 86 c) 81 1~ 6~ - -Example 4 Ef fect of prophylatic leaf treatment against Plasmopara viticola on vines in a greenhouse In a series of testsvoung vines having approximately 5 to 8 leaves were sprayed until dripping wet with the concentration of active substance indicated in the Table below and, after the spray coating had dried on, were sprayed on the undersides of the leaves with an aqueous suspension of sporangia of the fungus indi-cated in the heading above (approximately 20,000 per ml), and immediately incubated in a greenhouse at 22 to 24C in an atmos-phere as saturated with water vapour as possihle. From the second day onwards, the air humidity was reduced to the normal level for 3 to 4 days (approximately 30 to 70% saturation) and then maintained at water vapour saturation for a further day. The percentage proportion of the surface attacked hy fungi of each leaf was then recorded and the average per treatment was calculated as follows to determine the fungicidal effect:
100 - `100 x attack in treated plants = % effect . .
attack in untreated Plants : 30 Compound .csording to the %Effect ~qainst Concentration invention Plasmopara (%active vit~co~a ~) substance) Cyclopropanecarboxylic acid [2,6-diethyl-N-(2-oxoper-hydro-3-furyl)-anilide] 40 0.025 Cyclopropanecarboxylic acid [3-fluoro-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.025 Cyclopropanecarboxylic acid [3-bromo-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.025 Cyclopropanecarboxylic acid [2,6-diisopropyl-N-(2-oxoper-hydro-3-furyl)-anilide] 84 0.025 Cyclopropanecarboxylic acid [2-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] 83 0.025 Cyclopropanecarboxylic acid [4-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] 40 0~025 Cyclopropanecarboxylic acid [4-fluoro-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.025 Cyclopropanecarboxylic acid [2-ethoxy-N-(2-oxoperhydro-3-furyl)-anilide] 70 0.025 Cyclopropanecarboxylic acid [3-chloro-2-methyl-N-(2-oxoper-hydro-3-furyl)-anilide] 98 0.025 Cyclopropanecarboxylic acid [3-ethyl-N-(2-oxoperhydro-3-furyl)-anilide] . 100 0.025 Cyclopropanecarboxylic.acid .
[3-cyano-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.025 Cyclopropanecarboxylic acid ~3-thiomethyl-N-(2-oxoper-hydro-3-furyl)-anilide] 70 0.025 Cyclopropanecarhoxylic acid [2,3-dichloro-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.025 Cyclopropanecarbox~tl;c acid [N-(2--oxoperhydro 3-furyl)-anilide] 100 0.001 Cyclopropanecarboxylic acid 13-chloro-N-(2-oxoperhydro-3-furyl)-anilide] 100 0.001 ~.-- .
~ - 14 -+) Effect was calculated on 100% attack in the untreated control.
Example 5 -Effect of prophylactic leaf treatment against Phytophthora infestans in tomato plants or p.otato plants in .a greenhouse In a series of tests younq tomato plants having at least two developed foliage leaves and potato plants (for example from eye cuttings) at least 10 cm tall were sprayed until dripping wet with the concentration of active substance indicated in the Table below and, after the spray coatinq had driedon, were sprayed with 10 an aqueous suspension which contained per millilitre 50,000 to 80,000 sporangia of the fungus indicated in the heading above and which had been incubated in a refrigerator at 11C for approximately 2 hours. The plants were incubated at a high level of air humidity and at approximately 15 to 18C in a greenhouse and, after approxi-mately 5 days, the percentaae proportion of leaf surface that had been attackefl was assessed. The fungicidal effect was calculated as follows:
100 = 100 x attack in treated plants = ~ effect attack in untreated plants ~ Effect against Phytophthora infestansin potatoes +) Compound accordinq to the Concentration (~
invention active substance ) _. _ __ 0.005 Cyclopropanecarboxylic acid [N-(2-oxoperhydro-3-furyl)-anilide] - 95 Cyclopropanecarboxylic acid [2,6-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide] 80 ?~
, - 15 -Agent for comparison ~anganese ethylene bisd~thio-carbamate 50 %Effect against Phytophthora infestans in tomatoes.+) _ _ .
~ompound accordina to the Concentration (%
invention active substance) . 0.005 -Cyclopropanecarboxvlic acid [N-(2-oxoperhydro-3-furyl)-anilide] 100 Cyclopropanecarboxylic acid [3-methyl-N-(2~oxoperhydro-3-10 furyl)-anilide] 81 Cyclopropanecarboxylic acid [3-chloro-N-(2-oxoperhydro-3-furyl)-anilide] 91 Agent for com~arison -Manaanese ethylene bisdithio-carbamate 67 : +) Effect was calculated on 100% attack in the untreated control : Example 6 Systemic effect of soil treatment against Phytophthora infestans in tomato p.lants o.r potatoplants in a areenhouse ..... _ : 20 In a series of tests the substances to be tested, which had been weighed out (weiqht be volume), were mixed with arable soil which was then placed in plant pots, and young tomato plants having at least two developed foliage leaves and potato plants (for example from eye cuttings) at least 10 cm tall were placed in these pots. After the desired pre-dose time (for .. example after 4 or 18 days? had expired, the plants were sprayed with an aqueous suspension which contained per millilitre S0,000 ~ to 80,000 sporangia of the fungus indicated in the heading above .. and which had been incubated in a refrigerator at 11C for approximately 2 hours. The plants were incubated at a high ~81~1 level of air humidity and at approximately 15 to 18C in a greenhouse and, aEter approximately 5 days, the percentage pro-portion of leaf surface that had been attacked was assessed.
l'he fungicidal effect was calculated as follows;
100 - 100 x attack in treated plants = % effect attack in ~ntreated plants Systemic effect of soil treatment against Phytophthora infestans 10in tomato plants Compound according to tne ppm active ~ Effect 4 +) of treatment invention substance days before 18 days before inoculation inoculation .. . .. . . ... ... .. _ . _ .
Cyclopropanecarboxylic acid 25 89 85 [N-(2-oxoperhydro-3-furyl)-5 70 39 anilide]
Cyclopropanecarboxylic acid 25 92 82 [2,6-dimethyl-I~-(2-oxoper-5 40 71 hydro-3-furyl)-anilide]
+) Effect was calculated on 100% attack in the untreated control ~0 ; Example 7 Curative effect of leaf treatment against Phytophthora infestans in tomato plants or potato plants in a greenhouse , In a series of tests young tomato plants having at least two developed foliage leaves or potato plants (for example from eye cuttings) at least 10 cm tall were sprayed with an aqueous suspension which contained per millilitre 50,000 to 80,000 sporangia of the fungus indicated in the heading above and which had been incubated in a refrigerator at 11C for approximately 2 hours. The plants were incubated at a high level of air humidity. After the desired pre-dose time had expired, the plants were sprayed until dripping wet, within the period of 8~
latent fungal attack, with the concentration to be tested of the fungicide indicated in the Table below. After the outbreak of fungal attack in the untreated control plants the percentage proportion of leaf surface that had been attacked was assessed.
The fungicidal effect was calculated as follows:
100 - 100 x attàck in treated plants = % effect ... .
attack in untreated plants .
Compound according to the ~ Active % Effect +) of treat-invention substance before ment 1 day sprayed inoculation after inoculation .. .. . _ _ Cyclopropanecarboxylic acid [~-(2-oxoperhydro-3-furyl)-anilide] 0.004 100 68 Cyclopropanecarboxylic acid [2,6-dimethyl-N-(2-oxoper-hydro-3-furyl)-anilide] 0.004 100 60 Agent for comparison Manganese ethylene bisdithio-carbamate 0.004 91 0 +) Effect was calculated on 100~ attack in the untreated control Example 8 Effect of treatment of barley grains against helminthosporium spec.
In a series of tests barley grains that had been attacked by helmintilosporium spec. were treated with S0 mg of .....
active substance per 100 g of grains. rrhe grains were then SOWII
in soil and incubated in an air-conditioned chamber at +1~C.
Tile tests were evaluated after 6 weeks and tile rexulting seed-lings exnibited a markedly reduced attack as compared with plantsof an untreated control group.
lhe results are given in the following Table.
Compound according to the % Effect invention . .
Cyclopropanecar~oxylic acid [4-metllyl-N-(2-oxoperllydro-3-furyl)-anilide] 40 Cyclopropanecarboxylic acid [~,4-dimethyl-N-(2-oxoper-hydro-3-furyl)-anilide] : ~ 40 Cyclopropanecarboxylic acid [4-ethyl-1~-(2-oxoperhydro-3-furyl)-anilide] 40 Untreated control o ~xample_ Limiting concentration test in the control of Pythium ultimum In a series of tests 20~ pulverulent active substance preparations were mixed uniformly with soil which was severely infected with Pythium ultimum. The treated soil was placed in clay dishes each having a capacity of 0.5 litre and, without a waiting period, 20 marrowfat peas (Pisum sativum L. convar.
medullare Alev.) of the "Kelvedon Wonder" variety were sown in each dish. After a cultivation period of 3 wee]cs at 20 to 40C
the number of healtlly peas was determined and an assessment (1 - 4 as defined below) of the roots was carried out.
The active substances used and their application cluantities, and also the results, are given in the following Table.
Claims (56)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the general formula I
in which R1 represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, R2 represents an unsubstituted phenyl group or a phenyl group substituted by one or more substituents selected from alkyl groups containing 1 to 4 carbon atoms, alkoxy groups containing 1 to 4 carbon atoms, alkylthio groups containing 1 to 4 carbon atoms, halogen atoms, trifluoromethyl groups, nitro groups, alkoxy-carbonyl groups containing 1 to 4 carbon atoms in the alkoxy part, alkyl carbonyl groups containing 1 to 4 carbon atoms in the alkyl part, phenyl, and cyano groups, and n represents 1 or 2.
in which R1 represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, R2 represents an unsubstituted phenyl group or a phenyl group substituted by one or more substituents selected from alkyl groups containing 1 to 4 carbon atoms, alkoxy groups containing 1 to 4 carbon atoms, alkylthio groups containing 1 to 4 carbon atoms, halogen atoms, trifluoromethyl groups, nitro groups, alkoxy-carbonyl groups containing 1 to 4 carbon atoms in the alkoxy part, alkyl carbonyl groups containing 1 to 4 carbon atoms in the alkyl part, phenyl, and cyano groups, and n represents 1 or 2.
2. A compound as claimed in claim 1, wherein R1 repre-sents a hydrogen atom or a methyl or ethyl group and R2 repre-sents a phenyl, methylphenyl, dimethylphenyl, ethylphenyl, iso-propylphenyl, methoxyphenyl, ethoxyphenyl, methylthiophenyl, fluorophenyl, chlorophenyl, bromophenyl, dichlorophenyl, tri-fluoromethylphenyl, nitrophenyl, cyanophenyl, methoxycarbonyl-phenyl, acetylphenyl or biphenylyl group.
3. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [N-(2-oxoperhydro-3-furyl)-anilide].
4. A compound as claimed in claim 1 which is-cyclopropanecarboxylic acid [2,6-diethyl-N-(2-oxoperhydro-3-furyl)-anilide].
5. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [2-methoxy-N-(2-oxoperhydro-3-furyl)-anilide].
6. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [2-methyl-N-(2-oxoperhydro-3-furyl)-anilide].
7. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [2,6-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].
8. A compound as claimed in claim 1 which is cyclo propanecarboxylic acid [2,5-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].
9. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [3-methyl-N-(2-oxoperhydro-3-furyl)-anilide].
10. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [4-methyl-N-(2-oxoperhydro-3-furyl)-anilide].
11. A compound as claimed in claim 1 which is cylco-propanecarboxylic acid [3,4-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].
12. A compound as claimed in claim 1 which is cylco-propanecarboxylic acid [2,3-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].
13. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [2,4-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].
14. A compound as claimed in claim 1 which is cylco-propanecarboxylic acid [3,5-dimethyl-N-(2-oxoperhydro-3-furyl)-anilide].
15. A compound as claimed in claim 1 which is cylco-propanecarboxylic acid [2,4,6-trimethyl-N-(2-oxoperhydro-3-furyl)-anilide].
16. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [4-chloro-N-(2-oxoperhydro-3-furyl)-anilide].
17. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [3-chloro-N-(2-oxoperhydro-3-furyl)-anilide].
18. A compound as claimed in claim 1 which is cylco-propanecarboxylic acid [4-isopropyl-N-(2-oxoperhydro-3-furyl)-anilide].
19. A compound as claimed in claim 1 which is cylco-propanecarboxylic acid [3-trifluoromethyl-N-(2-oxoperhydro-3-furyl)-anilide].
20. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [3-fluoro-N-(2-oxoperhydro-3-furyl)-anilide].
21. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [3-bromo-N-(2-oxoperhydro-3-furyl)-anilide].
22. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid (2,6-diisopropyl-N-(2-oxoperhydro-3-furyl)-anilide].
23. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [2-ethyl-N-(2-oxoperhydro-3-furyl) anilide].
24. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [4-ethyl-N-(2-oxoperhydro-3-furyl) anilide].
25. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [4-methoxy-N-(2-oxoperhydro-3-furyl)-anilide].
26. A compound as claimed in claim 1 which is cylco-propanecarboxylic acid [4-bromo-N-(2-oxoperhydro-3-furyl)-anilide].
27. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [4-fluoro-N-(2-oxoperhydro-3-furyl)-anilide].
28. A compound as claimed in claim 1 which is cylco-propanecarboxylic acid [2-ethoxy-N-(2-oxoperhydro-3-furyl)-anilide].
29. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [3-chloro-2-methyl-N-(2-oxoperhydro-3-furyl)-anilide].
30. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [5-chloro-2-methyl-N-(2-oxoperhydro-3-furyl)-anilide].
31. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [4-methoxy-2-methyl-N-(2-oxoperhydro-3-furyl)-anilide.
32. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid (4-ethoxy-N-(2-oxoperhydro-3-furyl)-anilide].
33. A compound as claimed in claim 1 which is cylco-propanecarboxylic acid [5-chloro-2-methoxy-N-(2-oxoperhydro-3-furyl)-anilide].
34. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [3-chloro-N-(5-methyl-2-oxoperhydro-3-furyl)-anilide].
35. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [3-ethyl-N-(2-oxoperhydro-3-furyl)-anilide].
36. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [3-cyano-N-(2-oxoperhydro-3-furyl)-anilide].
37. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [3-thiomethyl-N-(2-oxoperhydro-3-furyl) anilide].
38. A compound as claimed in claim 1 which is cyclo-propanecarboxylic acid [2,3-dichloro-N-(2-oxoperhydro-3-furyl)-anilide].
39. A process for the manufacture of a compound of the general formula I
in which R1 represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, R2 represents an unsubstituted phenyl group or a phenyl group substituted by one or more substituents selected from alkyl groups containing 1 to 4 carbons atoms, alkoxy groups containing 1 to 4 carbon atoms, alkylthio groups containing 1 to 4 carbon atoms, halogen atoms, trifluoromethyl groups, nitro groups, alkoxycar-bonyl groups containing 1 to 4 carbon atoms in the alkoxy part, alkylcarbonyl groups containing 1 to 4 carbon atoms in the alkyl part, phenyl, and cyano groups, and n represents 1 or 2, wherein a compound of the general formula II
in which R1, R2 and n have the meanings given above, is reacted in the presence of an acid-binding agent with cyclopropane-carboxylic acid chloride of the formula III
in which R1 represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, R2 represents an unsubstituted phenyl group or a phenyl group substituted by one or more substituents selected from alkyl groups containing 1 to 4 carbons atoms, alkoxy groups containing 1 to 4 carbon atoms, alkylthio groups containing 1 to 4 carbon atoms, halogen atoms, trifluoromethyl groups, nitro groups, alkoxycar-bonyl groups containing 1 to 4 carbon atoms in the alkoxy part, alkylcarbonyl groups containing 1 to 4 carbon atoms in the alkyl part, phenyl, and cyano groups, and n represents 1 or 2, wherein a compound of the general formula II
in which R1, R2 and n have the meanings given above, is reacted in the presence of an acid-binding agent with cyclopropane-carboxylic acid chloride of the formula III
40. A process as claimed in claim 39, wherein the reaction is carried out in the presence of a solvent.
41. A process as claimed in claim 39 or 40, wherein the amounts used of the compound of the general formula II and the compound of the formula III are in equimolar proportions.
42. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 1, 2 or 3.
43. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 4, 5 or 6.
44. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 7, 8 or 9.
45. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 10, 11 or 12.
46. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 13, 14 or 15.
47. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 16, 17 or 18.
48. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 19, 20 or 21.
49. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 22, 23 or 24.
50. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 25, 26 or 27.
51. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 28, 29 or 30.
52. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 31, 32 or 33.
53. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 34, 35 or 36.
54. A method of protecting a living plant against phytopathogenic fungi, wherein the living plant is treated with a compound of the meanings given in claim 37 or 38.
55. A method of protecting a crop area against phytopathogenic fungi, wherein the crop area is treated with a compound given in claim 1, 2 or 3.
56. A method of dressing seeds, wherein the seeds are treated with a compound given in claim 1, 2 or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2724786.5 | 1977-05-27 | ||
| DE2724786A DE2724786C2 (en) | 1977-05-27 | 1977-05-27 | Cyclopropanecarboxylic acid [N- (2-oxoperhydro-3-furyl) anilide], processes for their preparation and fungicidal agents containing these compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1108161A true CA1108161A (en) | 1981-09-01 |
Family
ID=6010435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA303,250A Expired CA1108161A (en) | 1977-05-27 | 1978-05-12 | Fungicidally active cyclopropanecarboxylic acid anilides |
Country Status (39)
| Country | Link |
|---|---|
| JP (1) | JPS53147061A (en) |
| AR (1) | AR220710A1 (en) |
| AT (1) | AT360803B (en) |
| AU (1) | AU520353B2 (en) |
| BE (1) | BE867556A (en) |
| BG (1) | BG28688A3 (en) |
| BR (1) | BR7803382A (en) |
| CA (1) | CA1108161A (en) |
| CH (1) | CH633784A5 (en) |
| CS (1) | CS203192B2 (en) |
| CY (1) | CY1163A (en) |
| DD (1) | DD136093A5 (en) |
| DE (1) | DE2724786C2 (en) |
| DK (1) | DK233878A (en) |
| EG (1) | EG13373A (en) |
| ES (1) | ES470195A1 (en) |
| FI (1) | FI68397C (en) |
| FR (1) | FR2392019A1 (en) |
| GB (1) | GB1603730A (en) |
| GR (1) | GR72966B (en) |
| HU (1) | HU184201B (en) |
| IE (1) | IE46923B1 (en) |
| IL (1) | IL54719A (en) |
| IT (1) | IT1096326B (en) |
| KE (1) | KE3241A (en) |
| LU (1) | LU79711A1 (en) |
| MX (1) | MX5224E (en) |
| MY (1) | MY8300210A (en) |
| NL (1) | NL7805404A (en) |
| NO (1) | NO149430C (en) |
| PH (1) | PH15700A (en) |
| PL (1) | PL110646B1 (en) |
| PT (1) | PT68075B (en) |
| RO (1) | RO75072A (en) |
| SE (1) | SE442868B (en) |
| SU (2) | SU784770A3 (en) |
| TR (1) | TR20568A (en) |
| YU (1) | YU40192B (en) |
| ZA (1) | ZA783036B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440780A (en) * | 1979-06-01 | 1984-04-03 | Chevron Research Company | Fungicidal 3-(N-acyl-N-arylamino)-and 3-(N-thionoacyl-N-arylamino)-gamma-butyrolactones and gamma-thiobutyrolactones |
| EP0016985A1 (en) * | 1979-03-16 | 1980-10-15 | F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft | Substituted anilides, processes for their preparation, fungicides containing such compounds, and use of such compounds or fungicides in combating plant fungi |
| DE2920435A1 (en) * | 1979-05-19 | 1980-12-04 | Basf Ag | 2-AMINOPROPANAL ACETALS, METHOD FOR THE PRODUCTION THEREOF, THEIR USE AS FUNGICIDES AND METHOD FOR THE PRODUCTION OF SUBSTITUTED ANILINES |
| US4599351A (en) * | 1981-08-14 | 1986-07-08 | Chevron Research Company | Fungicidal 3-(N-acyl-N-arylamino) lactones |
| JPS61186735U (en) * | 1985-05-14 | 1986-11-21 |
-
1977
- 1977-05-27 DE DE2724786A patent/DE2724786C2/en not_active Expired
-
1978
- 1978-04-24 FI FI781264A patent/FI68397C/en not_active IP Right Cessation
- 1978-05-09 YU YU1102/78A patent/YU40192B/en unknown
- 1978-05-11 MX MX787079U patent/MX5224E/en unknown
- 1978-05-12 CA CA303,250A patent/CA1108161A/en not_active Expired
- 1978-05-15 PH PH21136A patent/PH15700A/en unknown
- 1978-05-16 IL IL54719A patent/IL54719A/en unknown
- 1978-05-18 NL NL7805404A patent/NL7805404A/en not_active Application Discontinuation
- 1978-05-18 TR TR20568A patent/TR20568A/en unknown
- 1978-05-23 GB GB21326/78A patent/GB1603730A/en not_active Expired
- 1978-05-23 PT PT68075A patent/PT68075B/en unknown
- 1978-05-23 CY CY1163A patent/CY1163A/en unknown
- 1978-05-24 IE IE1029/78A patent/IE46923B1/en unknown
- 1978-05-24 JP JP6212278A patent/JPS53147061A/en active Granted
- 1978-05-24 EG EG333/78A patent/EG13373A/en active
- 1978-05-24 AT AT380578A patent/AT360803B/en not_active IP Right Cessation
- 1978-05-24 ES ES470195A patent/ES470195A1/en not_active Expired
- 1978-05-24 AR AR272308A patent/AR220710A1/en active
- 1978-05-24 PL PL1978207069A patent/PL110646B1/en unknown
- 1978-05-25 RO RO7894166A patent/RO75072A/en unknown
- 1978-05-25 CS CS783406A patent/CS203192B2/en unknown
- 1978-05-25 SE SE7805994A patent/SE442868B/en not_active IP Right Cessation
- 1978-05-25 IT IT23774/78A patent/IT1096326B/en active
- 1978-05-25 DD DD78205587A patent/DD136093A5/en unknown
- 1978-05-25 LU LU79711A patent/LU79711A1/en unknown
- 1978-05-26 BG BG7839862A patent/BG28688A3/en unknown
- 1978-05-26 DK DK233878A patent/DK233878A/en not_active Application Discontinuation
- 1978-05-26 CH CH580678A patent/CH633784A5/en not_active IP Right Cessation
- 1978-05-26 BE BE188101A patent/BE867556A/en not_active IP Right Cessation
- 1978-05-26 SU SU782621101A patent/SU784770A3/en active
- 1978-05-26 AU AU36529/78A patent/AU520353B2/en not_active Expired
- 1978-05-26 FR FR7815747A patent/FR2392019A1/en active Granted
- 1978-05-26 GR GR56344A patent/GR72966B/el unknown
- 1978-05-26 ZA ZA00783036A patent/ZA783036B/en unknown
- 1978-05-26 BR BR7803382A patent/BR7803382A/en unknown
- 1978-05-26 NO NO781838A patent/NO149430C/en unknown
- 1978-05-26 SU SU782621053A patent/SU727107A3/en active
- 1978-05-26 HU HU78SCHE646A patent/HU184201B/en unknown
-
1982
- 1982-10-28 KE KE3241A patent/KE3241A/en unknown
-
1983
- 1983-12-30 MY MY210/83A patent/MY8300210A/en unknown
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