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
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
  • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
• • 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
  • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
  • A01N47/44—Guanidine; Derivatives thereof

Definitions

• ABSTRACT Substituted amidophenylguanidines of the formula in which each X independently denotes a halogen atom, lower alkyl or lower alkoxy, n denotes 0,1 or 2, R denotes a hydrogen atom, or lower alkyl, R denotes alkyl with l12 carbon atoms, and R" denotes a hydrogen atom, alkyl with 1-18 carbon atoms, which may be substituted, cycloalkyl with 58 ring carbon atoms, aralkyl, which may be substituted, aryl, which may be substituted, or 2-furyl, which possess fungicidal properties.
• the present invention relates to and has for its objects the provision of particular new substituted amidophenylguanidines which possess fungicidal properties, active compositions-in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating fungi, with other and further objects becoming apparent from a study of the within specification and accompanying examples.
• guanidine derivatives can be used as fungicides, for example dodecylguanidine acetate (A) (see Belgian Patent Specification No. 568,612) which has attained a considerable importance in practice.
• the salts of phenylmercury which are toxic to mammals, used hitherto in the cultivation of pip fruit for the control of scab (Venturia inaequalis and Venturia pirina), may be replaced by the salts of dodecylguanidine for the curative combating of many fungal diseases.
• dodecylguanidine are only very slightly effective against powdery mildew fungi from the Erysiphaceae family, such as the causative organism of powdery mildew of apples, Podosp/zaera leut'orriclm.
• n denotes 0, l or 2
• R denotes a hydrogen atom or lower alkyl
• R denotes alkyl with ll2 carbon atoms
• R" denotes a hydrogen atom, alkyl with 1-18 carbon atoms (which may be substituted by halogen, cyano, lower alkoxy, alkoxycarbonyl with 2-5 carbon atoms, phenoxy, halophenoxy, alkylphenoxy or alkoxyphenoxy), cycloalkyl with 5-8 ring carbon atoms, aralkyl (which may be substituted by halogen, lower alkyl or lower alkoxy), aryl (which may be substituted by halogen, lower alkyl or lower alkoxy) or 2-furyl.
• the compounds of the formula (1) exhibit strong fungicidal properties.
• the present invention also provides a process for the production of the amidophenylguanidines of the formula (l) in which a Z-aminoaniline derivative of the formula in which:
• R is the same as defined above, and R"" stands for alkyl of l-4 carbon atoms in the presence of a diluent (which term includes a solvent).
• amidophenylguanidines according to the invention possess a higher fungidical activity against powdery mildew fungi than dodecylguanidine acetate.
• compounds according to the invention also exhibit a genuine systemic effectiveness against some important fungus-parasitic diseases.
• reaction course can be represented by the following equation:
• the Z-aminoaniline derivatives used as starting materials are defined by the formula (ll).
• X stands preferably for chlorine, bromine, fluorine, alkyl or alkoxy with 1-4 carbon atoms, and especially chlorine, methyl, ethyl, isopropyl, methoxy, ethoxy or isopropoxy;
• n stands preferably for 0 or I, R stands preferably for methyl, ethyl or especially hydrogen and R" stands preferably for alkyl with l] 8 carbon atoms, p-methylphenyl, p-chlorophenyl, pmethoxyphenyl, heptadecyl, phenyl and especially methyl, propyl, undecyl, l-furyl or phenoxymethyl.
• 2-aminoacetoanilide 2-amino-4- methylacetanilide, 2-amino-butyranilide, 2- aminolauranilide, 2-aminostearanilide, benzoic acid (2-am'ino-)-anilide, p-chlorobenzoic acid (2-amino)- anilide, phenoxyacetic acid (2-amino)-anilide, 2- furancarboxylic acid (2'-amino)-anilide, N-ethyl-N- acetyl-o-phenylenediamine, 2-amino-4- chloroacetanilide, and 2-amino-4-chloro-stearanilide.
• the 2-amino-aniline derivatives used as starting materials are for the most part known (see Beilsteins Handbuch der organischen Chemie, Volume 13, pages 32, Berlin 1930; Volume 13, l. Erganzungswerk (1st Supplement), pages 8-10, Berlin 1933; Volume 13, 2.Erganzungstechnik (2nd Supplement), pages l423, Berlin-G6ttingen-Heidelberg, 1950). They can also be obtained by reduction or catalytic hydrogenation of the appropriate nitro compounds.
• the isothiourea ethers used as starting materials are defined by the formula (III).
• R stands preferably for lower alkyl especially with 1-4 carbon atoms and most especially for methyl, ethyl or propyl.
• the radicals R may be the same or different.
• R' stands preferably for methyl or ethyl.
• polar organic solvents are suitable as the diluent in the process according to the invention. These include alcohols, such as methanol, ethanol, isopropanol; mixtures of alcohols with water; ketones, such as acetone, (optionally mixed with water); and ethers, such as dioxane or tetrahydrofuran.
• alcohols such as methanol, ethanol, isopropanol
• ketones such as acetone, (optionally mixed with water)
• ethers such as dioxane or tetrahydrofuran.
• reaction temperatures can be varied within a fairly wide range. In general, the work is carried out at from between about 50 to 120C, preferably from about 60 to 100C.
• 1 mole of isothiourea ether is preferably used per mole of Z-aminoaniline derivative. Amounts greater or lesser by up to 20% are possible without substantial diminution ofthe yield.
• the reaction is preferably carried out in a boiling solvent, an alkylmercaptan being formed as a by-product. The end products are obtained in crystalline form when the reaction mixture is cooled, and can be separated by suction filtration and, optionally, purified by re-dissolving or re-crystallization.
• the active compounds according to the invention exhibit a strong fungitoxic activity, In the concentrations necessary for the control of fungi, they do not damage cultivated plants, and have a low toxicity to warmblooded animals. For these reasons, they are suitable as crop protection agents for the control of fungi. Fungitoxic agents in crop protection are used for the control of Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi Imperfecti.
• the active compounds according to the invention have a very broad activity spectrum and can be applied 4 against parasitic fungi which infect above-the-soil parts of plants or attack the plants from the soil, as well as against seed-borne pathogenic agents.
• fungi which cause powdery mildew diseases.
• fungi there belong predominantly representatives from the Erysiphaceae family with the most important genera being Erysiphe, Uncinula (Oidium), Sphaerotheca and Podosphaera.
• Erysiphe cichoracearum As important fungi, there may be mentioned Erysiphe cichoracearum, Podosplzaera leucotri- (ha and Uncinula necator.
• the active compounds according to the invention also give good results in the control of rice diseases. Thus, they show an excellent activity against the fungi Piricularia oryzae and Pelli'cularia sasakii, by reason of which they can be used for joint control of these two diseases. This means a substantial advance, since up to now, agents of different chemical constitution were required against these two fungi. Surprisingly, the active compounds show not only a protective activity, but also a curative and systemic effect.
• the compounds according to the invention also act against other fungi which infect rice or other cultivated plants, such as Cochliobolus myiabeanus, Mycosphaerella musicola, Cercospora personata, Bolry- [is cinerea, Alternaria species, Verticillium alboatrum, Phialophora cinerescens and Fusarium species as well as against the bacterium Xanthomonas oryzae.
• fungi which infect rice or other cultivated plants, such as Cochliobolus myiabeanus, Mycosphaerella musicola, Cercospora personata, Bolry- [is cinerea, Alternaria species, Verticillium alboatrum, Phialophora cinerescens and Fusarium species as well as against the bacterium Xanthomonas oryzae.
• the active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles, such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc.
• conventional inert i.e. plant compatible or herbicidally inert
• pesticide diluents or extenders i.e. diluents or extenders of the type usable in conventional pesticide formulations or compositions
• conventional pesticide dispersible carrier vehicles such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble
• carrier vehicle assistants e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents.
• carrier vehicle assistants e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents.
• inert dispersible liquid diluent carriers including inert organic solvents, such as aromatic hydrocarbons (e.g.
• emulsifying agents such as non-ionic and/or anionic emulsifying agents (e.g.
• polyethylene oxide esters of fatty acids polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl aryl-polyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.
• Such active compounds may be employed alone or in the form of mixtures with one another and/or with sucht solid and/or liquid dispersible carrier vehicles and/or with other known conpatible active agents, especially plant protection agents, such as other fungicides, or herbicides, insecticides, bactericides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.
• plant protection agents such as other fungicides, or herbicides, insecticides, bactericides, etc.
• composition mixtures in which the active compound is present in an amount substantially between about 0.l95%, and preferably 290%, by weight of the mixture
• carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10.0 preferably 001-1 .071, by weight of the mixture.
• the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surfaceactive effective amount of a carrier vehicle assistant, e.g.
• a su rface-active agent such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally about 00001-9570, and preferably 0.0l-95'/r, by weight of the mixture.
• 00001-107 by weight concentrations of the active compound are sufficiently effective, although aqueous preparations having concentrations of 0.014% by weight of the active compound are normally used.
• applied amounts of0.1 to g, preferably 0.2 to 2 g, of active compound per kg of seed are suitable.
• the active compounds according to the invention show also an insecticidal and acaricidal activity as well as an activity against some mould fungi and yeasts. in concentrations higher than those necessary for fungicidal activity, the substances inhibit plant growth.
• the active compound can also be used in accordance with the well-known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-16 fluid ounces/acre, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about or by weight of the active compound, or even the active substance alone, e.g. about 20-100% by weight of the active compound,
• the present invention contemplates methods of selectively killing, combating or controlling fungi, which comprises applying to at least one of (a) such fungi and (b) their habitat, i.e. the locus to be protected, a fungicidally effective or toxic amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above.
• the instant formulations or compositions are applied in the usual manner, for instance by squirting, spraying, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, and the like.
• concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases, it is possible to go above or below the aforementioned concentration ranges.
• the fungicidal effectiveness of the new compounds of the present invention is illustrated, without limitation, by the following Examples.
• EXAMPLE 1 Fusicladiu n test (apple scab) (Protective) The amount of active compound required for the desired concentration of the active compound in the spray liquid is mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water which contains the stated additions.
• Young apple seedlings in the four to six leaf stage are sprayed with the spray liquid until dripping wet.
• the plants remain in a greenhouse for 24 hours at 20C. and at a relative atmospheric humidity of 70%. They are then inoculated ith an aqueous conidiumsuspension of the apple scab causative organism (Fusicladium dendriticum el) and incubated for 18 hours in a humidity chamber at l8-20C. and at a relative atmospheric humidity of 100%.
• the plants are then placed in a greenhouse for 14 days.
• the infestation of the seedlings is determined as a percentage of the untreated but also inoculated control plants.
• the concentrate is diluted with the stated amount Infection as a percentage of the infection of thd untreated control with r a concentration of active compound (in of 0.0062
• the plants After standing for a suitable period of time, the plants are sprayed dripping wet with the spray liquid prepared in the manner described above. The plants are again placed in a greenhouse.
• the infestation of the cucumber plants is determined as a percentage of the untreated but also inoculated control plants. 0% means no infestation; that the infestation is exactly as great as in the case of the control plants. 7
• the plants so treated are, after the treat- Emulsifier: P t y weight Hlkyluryl p yg y ment, inoculated with an aqueous conidium suspension water: byweigm 60 of Fusicladium dendriticum el and incubated for
• the amount of active compound required for the desired concentration of the active compound in the liquid to be used for watering is mixed with the stated 5 18 hours in a humidity chamber at l820C and at a relative atmospheric humidity of The plants are then placed in a greenhouse for 14 days.
• the infection of the seed lings is determined as a percentage of the untreated but also inoculated control plants. 0% means no infection; 100% means that the infection is exactly as great as in the case of the control plants.
• alkylaryl polyglycol ether 40 parts by weight 20 cc of the liquid to be used for watering, in the stated concentration of active compound, with reference to 100 cc of soil.
• the plants so treated are, after the treat ment, inoculated with conidia of Podosphaera leucorri- 'cha Salm and placed in a greenhouse at a temperature of 2l-23C and at a relative atmospheric humidity of about 10 days after the inoculation, the infection of the seedlings is determined as a percentage of the untreated but also inoculated control plants.
• the active compounds, the concentrations of the active compounds and the results obtained can be seen from the following Table 5 Podosphaera test/systemic Infection as a percentage of the infection of the untreated control with a concentration of active coinpound of Active compound 30 ppm 15 ppm 0 H NH 1 CH 0 r 2 25 H2 3 OOH (known) (A) 100 100 Podos Eha era tes t /sys temic Infection as a percentage of the infection of the untreated control with a concentration of active compound of Active compound 30 ppm 15 ppm NH- U i OCH3 0 .o.5
• Plants of Vicia faba grown in standard soil are, in the i one to two leaf-pair stage, watered once in 1 week with 20 cc of the liquid to be used for watering, in the stated concentration of active compound, with reference to 100cc of soil.
• the lower two leaf-pairs are removed and, in each case, placed in a Petri dish lined with moist filter paper.
• Small discs of filter paper of 1 cm diameter are then dipped into an aqueous conidium suspension of the grey mould causative organism Botrytl's cinerea Pers. ex Fr. and laid on the leaves.
• the necroses visible under the small discs are evaluated according to frequency of occurrence (evaluation scheme O V). The evaluation values obtained are converted into percentage infection.
• % means no infection; 100% means that the infec-' tion is exactly as great as in the case of the control plants.
• Botrztis tes t/sys temic The amount of active compound required for the desired concentration of active compound in the spray liquor is mixed with the stated amount of solvent, and the concentrate is diluted with the stated amount of water containing the stated additives.
• a/ispersing agent 90.25 parts by weight sodium oleate
• the active compounds, the concentrations of the aco if 3: gelatin tive compounds and the results obtained can be seen TABLE 7 Piricularia (a) and Pellicularia (b) tes t
• 1 part by weight of the active compound is taken up in the stated amount of solvent.
• pr protective cur. curative Infection as a percentage of the infection of the. untreated control with a concentration of Active compound active compound (in Z) of 0.05 0.025 0.05 0.025
• EXAMPLE 8 tive compound the agar is poured into Petri dishes 50 under sterile conditions.
• test fungi from Agar plate test Test for fungitoxic effectiveness and breadth of the activity spectrum. pure Cultures are Inoculated to It In Small discs of 5 s l t t mm diameter.
• the Petri dishes remain at 20C for 3 0 ven I a e e Parts by weight: al 1830 days OI' Incubation. i I I b) 100 55 After this time, the inhibiting action of the active compound on the mycelium growth is determined in categories, taking into account the untreated control.
• 0 means no mycelium growth, either on the treated substrate or on the inoculum, the symbol means mycelium growth on the inoculum only no spread to the treated substrate; and the symbol means mycelium growth from the inoculum on to the treated substrate, similar to the spread to the untreated substrate of the control.
• EXAMPLE 9 Wheat seed is contaminated with 5 g of the chlamydospores of Tilletia caries per kg of seed. To apply the dressing, the seed is shaken with the dressing in a To Produce a Suitable y dressing, the active 65 closed glass flask. The seed, on moist loam under a Pound is extended with a mixture of equal Parts y cover ofa layer ofmuslin and 2 cm of moderately moist Weight of talc and kieselguhr to give a finely Powdered compost soil, is exposed to optimum germination conmixture with the desired concentration of the active di i f h Spores f 1() d at 10C i a f i compound. ⁇ 0L
• Seed dressing test/bunt of wheat seed-born mycosis
• the germination of the spores on the wheat grains 5
• the preparation of the active compound is uniformly each of which is contaminated with about 100,000 mixed with Fruhstorfer standard soil. which has first spores, is subsequently determined microscopically. been sterilized and then inoculated with pure cultures The smaller the number of spores which have germiof the test fungi. nated, the more effective is the active compound.
• Thesoil is filled into 5 pots, each of which is sown m with 10 seeds of the host plants.
• the pots are placed in The active compounds, the concentrations ofthe aca greenhouse at the stated temperatures and kept nortive compounds in the dressing, the amounts of dressmally moist. ing used and the percentage spore germination can be 3 weeks after sowing.
• the number of healthy plants is seen from the following Table9: determined as a percentage of the number of seeds l ilei Active compound Concentration of Applied amount Spore active compound dressing in Germinain the dressing g/kg seed tion in Z. in Z.
• Nike-0 H E M 10 sown. 0% means that no healthy plants have grown; so treating agent test/somber mycoss 100% means that healthy plants have resulted from all the seeds.
• the concentration of the acpound the active compound is extended with talc to a tive compounds in the soil, the test fungi, host plants, content of 5% and subsequently wth quartz sand to a greenhouse temperatures and the results obtained can content of 0.5% of active compound.
• each X independently denotes a halogen atom, lower alkyl lower loer alkoxy, I
• n denotes 0, l or 2
• R denotes a hhydrogen atom or lower alkyl
• R denotes alkyl with l-12 carbon atoms
• R" denotes a hydrogen atom, alkyl with l-l 8 carbon atoms which may be substituted by lower alkoxy, alkoxycarbonyl with 2-5 carbon atoms, phenoxy, or alkoxyphenoxy, cycloalkyl with 5-8 ring carbon atoms, or phenyl which may be substituted by halogen, lower alkyl or lower alkoxy.
• R denotes alkyl with l-l8 carbon atoms optionally substituted by alkoxy with l-4 carbon atoms, alkoxycarbonyl with 2-5 carbon atoms, phenoxy, alkoxyphenoxy cycloalkyl with 5-8 ring carbon atoms, or phenyl optionally substituted by halogen, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms.
• X denotes a chlorine, bromine or fluorine atom or alkyl or alkoxy with l-4 carbon atoms
• n denotes a hydrogen atom or methyl or ethyl
• R denotes alkyl with l-4 carbon atoms
• R denotes alkyl with 1-18 carbon atoms, phenyl, p-chlorophenyl, p-methylphenyl, pmethoxyphenyl or phenoxymethyl.

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• Life Sciences & Earth Sciences (AREA)
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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
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• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
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• Environmental Sciences (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Furan Compounds (AREA)

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Citations (1)

• 0
  • BE BE758607D patent/BE758607A/fr unknown
• 1969
  • 1969-11-06 DE DE19691955749 patent/DE1955749A1/de active Pending
• 1970
  • 1970-10-13 IL IL7035440A patent/IL35440A/en unknown
  • 1970-10-20 CH CH1549270A patent/CH508603A/de not_active IP Right Cessation
  • 1970-10-21 ZA ZA707167A patent/ZA707167B/xx unknown
  • 1970-10-22 US US083159A patent/US3869503A/en not_active Expired - Lifetime
  • 1970-10-26 RO RO64793A patent/RO58034A/ro unknown
  • 1970-10-27 BG BG015931A patent/BG17537A3/xx unknown
  • 1970-11-03 HU HUBA2493A patent/HU163069B/hu unknown
  • 1970-11-03 GB GB52217/70A patent/GB1282374A/en not_active Expired
  • 1970-11-05 DK DK563870AA patent/DK126499B/da unknown
  • 1970-11-05 ES ES385211A patent/ES385211A1/es not_active Expired
  • 1970-11-05 NL NL7016232A patent/NL7016232A/xx unknown
  • 1970-11-06 AT AT999970A patent/AT303751B/de not_active IP Right Cessation
  • 1970-11-06 FR FR7039983A patent/FR2069114A5/fr not_active Expired
  • 1970-11-06 PL PL1970144296A patent/PL69661B1/pl unknown
  • 1970-11-06 JP JP45097536A patent/JPS4811015B1/ja active Pending
  • 1970-11-06 JP JP45097535A patent/JPS4936705B1/ja active Pending
• 1973
  • 1973-12-31 MY MY1973142A patent/MY7300142A/xx unknown

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