IL47009A - Process for the preparation of 3-pyrrolidinyl-(1)-propyl-dithiocarbamic acid and fungicidal compositions containing it - Google Patents
Process for the preparation of 3-pyrrolidinyl-(1)-propyl-dithiocarbamic acid and fungicidal compositions containing itInfo
- Publication number
- IL47009A IL47009A IL47009A IL4700975A IL47009A IL 47009 A IL47009 A IL 47009A IL 47009 A IL47009 A IL 47009A IL 4700975 A IL4700975 A IL 4700975A IL 47009 A IL47009 A IL 47009A
- Authority
- IL
- Israel
- Prior art keywords
- propyl
- pyrrolidinyl
- admixture
- dithiocarbamic acid
- diluent
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title claims description 7
- 230000000855 fungicidal effect Effects 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000003085 diluting agent Substances 0.000 claims description 14
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 10
- 241000233866 Fungi Species 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VPBWZBGZWHDNKL-UHFFFAOYSA-N 3-pyrrolidin-1-ylpropan-1-amine Chemical compound NCCCN1CCCC1 VPBWZBGZWHDNKL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
- TWIOETHNYAHVFS-UHFFFAOYSA-N propylcarbamodithioic acid Chemical compound CCCNC(S)=S TWIOETHNYAHVFS-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- -1 3-pyrrolidinyl- Chemical group 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000969 carrier Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 125000004575 3-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OPFTUNCRGUEPRZ-QLFBSQMISA-N Cyclohexane Natural products CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyrrole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
ProcesB for the preparation of 3-pyrrolidinyl (l)-propyl-dithiocarbaiaic acid and fungicidal compositions containing it BAYER AKTIENGESELLSCHAFT G:-44685 Type IVa The present application relates to an unobvious process for the preparation of the known fungicide, 3-pyrrolidinyl-( 1 )-propyl-dithiqcarbamic acid.
It has already been disclosed that 3-pyrrolidinyl-<-( 1 )-propyl-dithiocarbamic acid can be prepared by reacting 1 -(3-aminopropyl)-pyrrolidine and carbon disulphide in benzene at 25°C. According to statements in the literature (see U.S. Patent Specification 2,971,884, columns 3 and 4, Example 1 ) this method gives a preparation of melting point H7-1 9°G, the analysis of which however does not show satisfactory values. The compound was therefore probabl not in the pure form and the process of pre-*-paration is therefore probably unsuitable.
The present invention provides a process for the preparation of 3-pyrrolidinyl-(1 )-propyl-dithiocarbamic acid, which may be represented by the formula in which process 1 -(3-aminopropyl)-pyrrolidine of the formula is reacted with carbon disulphide in an aqueous medium in the temperature range -10° to +50°C.
It must be described as distinctly surprising that aa a result of the choice of water as the solvent, 3-pyrroli-dinyl-( 1 )-propyl-dithiocarbamic acid can be obtained i good yield and in the pure form, melting point 175°C. The process represents a technical advance since, according to the process known from the literature, the compound in question was not obtainable in a pure form (as must be concluded from the data given in U.S. Patent Specification 2,971,884).
The reaction can be represented by the following equation: The starting materials, 1 -(3-amihopropyl)-pyrrolidine (see Beilsteins Handbuch der organischen Chemie (Beilstein's Handbook of Organic Chemistry) H 20. E II 6) and carbon disulphide are generally known compounds.
The diluent used according to the invention is water; the amount of water is not of major importance with regard to yield and purity.
The reaction is carried out at temperatures of from -10° to + 50°C, preferably between 0° and 30°C.
To carry out the process, the reactants are preferably reacted with one another in the stoichiometric ratio; the sequence in which the reactants encounter one another is without any great influence on the course of the reaction.
The mixture is worked up by filtering off the reaction product and recrystallising it from water.
According to the literature, the compound obtainable according to the invention has a fungicidal action; for example, an action against Altemaria solani is mentioned (U.S.Patent Specification 2,971,884, columns 7 and 8).
The active compound obtainable according to the present invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compound with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chloroberizenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclo-hexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, e.g. aerosol propellants, such as halogenated hydrocarbons, e.g. freon.
As solid diluents or carriers, there are preferably-used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.
Preferred examples of emulsifying and foam-forming agents include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid egters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin hydrolyzation products; and preferred examples of dispersing agents include lignin sulphite waste liquors and methyl cellulose.
In general, the formulations contain from 0.1 to 95 per cent by weight of active compound, preferably 0.5 to 90 per cent by weight.
The active compound can be employed as such or in the form of its formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. It may be applied in the customary manner, for example by watering, squirting, spraying, dusting, sprinkling, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.
The present invention therefore also provides a fungicidal composition containing as active ingredient the compound prepared according to the present invention, in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating fungi which comprises applying to the fungi or a fungus habitat the compound prepared according to the present invention alone or in the form of a composition containing as active ingredient the compound prepared according to the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing the compound prepared according to the present invention was applied alone or in admixture with a diluent or carrier. It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The use of 3-pyrrolidinyl-( 1 )-propyl-dithiocarbamate specifically against fungi that cause cereal disease is the subject of German Patent Application P2415059.3 [Le A 15 566] filed 28th March, 1974.
Preparative Example 76 g (1 mole) of carbon disulphide were added dropwise to a solution of 128 g (1 mole) of 1 -(3-amino-propyl)-pyrrolidine in 600 ml of water whilst cooling, at a temperature of 10° to 1 °C The mixture was stirred for a further hour at room temperature and the crystals were filtered off, washed with ice water and methanol and dried. 194 g of 3-pyrrolidinyl-(1 )-propyl-dithiocarbamic acid of melting point 175 C, representing 9 of theory were obtained. The compound could be recrystallised from water, and this did not change the melting point (175°C, with decomposition).
Analysis: Calculated: N 13.7$; S 31.35$ Pound: N 13.8$; S 31.30$ In the case of a sample prepared in benzene as the diluent, according to the data in the literature (U.SoPatent Specification 2,971,884, Example 1), impurities were found in the infrared spectrum at 1 ,350 cm"~^ and 1 ,390 cm"*^ .
Claims (8)
1. A process for the preparation of 3-pyrrolidinyl-( 1 )· propyl-dithiocarbamic acid of the formula I N-GH2-CH2-GH2-NH-G-SH (i) in which 1 -(3-amino-propyl)-pyrrolidine of the formula is reacted with carbon disulphide, the reaction being carried out in an aqueous medium in the temperature range of -10° to +50°C.
2. A process according to claim 1 , in which the reaction is carried out at between 0° and 30°C.
3. A process according to claim 1 or 2 , in which the reactants are employed in stoichiometric amounts.
4. A process according to claim 1 for the preparation of 3-pyrrolidinyl-( 1 )-propyl-dithiocarbamic acid, substantially as described in the preparative Example.
5. 3-P rrolidinyl-(1 )-propyl-dithiocarbamic acid when prepared by a process according to any of claims 1 to 4.
6. A fungicidal composition containing as active ingredient the compound according to claim 5 in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent,
7. A method of combating fungi which c omprises applying to the fungi or a fungus habitat a compound according to claim 5 alone or in the form of a composition containing as active ingredient the compound according to claim 5 in admixture with a diluent or carrier.
8. Crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing the compound according to claim 5 was applied alone or in admixture with a diluent or carrier,. Fc lfr=> At !icams
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2417142A DE2417142A1 (en) | 1974-04-09 | 1974-04-09 | PROCESS FOR PREPARING 3-PYRROLIDINYL- (1) -PROPYL-DITHIOCARBAMIC ACID |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL47009A0 IL47009A0 (en) | 1975-06-25 |
| IL47009A true IL47009A (en) | 1977-11-30 |
Family
ID=5912516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL47009A IL47009A (en) | 1974-04-09 | 1975-04-04 | Process for the preparation of 3-pyrrolidinyl-(1)-propyl-dithiocarbamic acid and fungicidal compositions containing it |
Country Status (17)
| Country | Link |
|---|---|
| BE (1) | BE827187A (en) |
| CH (1) | CH597211A5 (en) |
| CS (1) | CS177043B2 (en) |
| DD (1) | DD119590A5 (en) |
| DE (1) | DE2417142A1 (en) |
| DK (1) | DK136472C (en) |
| FR (1) | FR2267320B1 (en) |
| GB (1) | GB1455683A (en) |
| HU (1) | HU172754B (en) |
| IE (1) | IE40891B1 (en) |
| IL (1) | IL47009A (en) |
| IT (1) | IT1049401B (en) |
| LU (1) | LU72226A1 (en) |
| NL (1) | NL7504119A (en) |
| PL (1) | PL93129B1 (en) |
| RO (1) | RO65068A (en) |
| SU (1) | SU520048A3 (en) |
-
1974
- 1974-04-09 DE DE2417142A patent/DE2417142A1/en not_active Withdrawn
-
1975
- 1975-03-26 SU SU2116859A patent/SU520048A3/en active
- 1975-03-26 BE BE154770A patent/BE827187A/en unknown
- 1975-03-26 DK DK134075A patent/DK136472C/en active
- 1975-03-27 IE IE687/75A patent/IE40891B1/en unknown
- 1975-03-27 GB GB1294075A patent/GB1455683A/en not_active Expired
- 1975-03-28 FR FR7509824A patent/FR2267320B1/fr not_active Expired
- 1975-04-04 IL IL47009A patent/IL47009A/en unknown
- 1975-04-07 DD DD185278A patent/DD119590A5/xx unknown
- 1975-04-07 LU LU72226A patent/LU72226A1/xx unknown
- 1975-04-07 IT IT22082/75A patent/IT1049401B/en active
- 1975-04-07 CH CH437775A patent/CH597211A5/xx not_active IP Right Cessation
- 1975-04-07 NL NL7504119A patent/NL7504119A/en not_active Application Discontinuation
- 1975-04-08 RO RO7581928A patent/RO65068A/en unknown
- 1975-04-08 CS CS2413A patent/CS177043B2/cs unknown
- 1975-04-08 PL PL1975179431A patent/PL93129B1/pl unknown
- 1975-04-09 HU HU75BA00003242A patent/HU172754B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK136472B (en) | 1977-10-17 |
| GB1455683A (en) | 1976-11-17 |
| DK134075A (en) | 1975-10-10 |
| DK136472C (en) | 1978-03-28 |
| IT1049401B (en) | 1981-01-20 |
| CH597211A5 (en) | 1978-03-31 |
| NL7504119A (en) | 1975-10-13 |
| IE40891L (en) | 1975-10-09 |
| HU172754B (en) | 1978-12-28 |
| IL47009A0 (en) | 1975-06-25 |
| DD119590A5 (en) | 1976-05-05 |
| DE2417142A1 (en) | 1975-10-30 |
| FR2267320B1 (en) | 1978-09-29 |
| LU72226A1 (en) | 1976-03-02 |
| FR2267320A1 (en) | 1975-11-07 |
| IE40891B1 (en) | 1979-09-12 |
| PL93129B1 (en) | 1977-05-30 |
| CS177043B2 (en) | 1977-07-29 |
| SU520048A3 (en) | 1976-06-30 |
| RO65068A (en) | 1979-02-15 |
| BE827187A (en) | 1975-09-26 |
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