GB1563733A - Phosphorus-containing triazole derivatives - Google Patents

Phosphorus-containing triazole derivatives Download PDF

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Publication number
GB1563733A
GB1563733A GB47241/76A GB4724176A GB1563733A GB 1563733 A GB1563733 A GB 1563733A GB 47241/76 A GB47241/76 A GB 47241/76A GB 4724176 A GB4724176 A GB 4724176A GB 1563733 A GB1563733 A GB 1563733A
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Prior art keywords
formula
pests
triazole
compound
parts
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GB47241/76A
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Novartis AG
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Ciba Geigy AG
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Priority claimed from CH1479675A external-priority patent/CH602012A5/en
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of GB1563733A publication Critical patent/GB1563733A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518—Five-membered rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

(54) PHOSPHORUS-CONTAINING TRIAZOLE DERIVATIVES (71) We, CIBA-GEIGY AG., a body corporate organised according to the laws of Switzerland, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention provides derivatives of 1,2.4-triazole, a process for the manufacture thereof, and a method of controlling pests which comprises the use of these derivatives.
The 1,2,4-triazole derivatives have the formula
wherein each of R1, R2 and R3 independently represents a C1-C6-alkyl group and X represents an oxygen or sulphur atom.
The alkyl groups represented by R1 to R3 can be straight-chain or branched.
Examples of such groups include: methyl, ethyl, propyl, iso-propyl. n-butyl, iso butyl. sec.butvl, tert.butyl, n-pentyl, n-hexyl and isomers thereof.
Preferred compounds on account of their action are those of the formula I, wherein each of R,. R2 and R3 independently represents a methyl or ethyl group and X represents a sulphur atom.
The compounds of the formula I can be obtained by methods which are known pru Se, for example as follows:
A) CHJSCH, CH3 x I/OR1 .,id accepts' CH 1 XORr N-N OR2 /LNLOH R3S (III) (11) B) CH3OCH2 CH3 x CH )/OR, Hat - Hal - N- N cNILOM' OR, R35 (IV) lill) In the formulae II, III and IV, the symbols R, to R3 and X are as defined for formula I and Hal represents a halogen atom, preferably a chlorine or bromine atom, and Me represents a metal, in particular an alkali metal, or ammonium or substituted ammonium e.g. trialkylammonium.
Suitable acid acceptors are for example the following bases: tertiarv amines.
such as triethylamine. dimethyl aniline and pyridine: and inorganic bases, such as hydroxides and carbonates of alkali metals and alkaline earth metals. preferably sodium and potassium carbonate.
Processes A and B are generally carried out at a reaction temperature of 0 to 1'0 C, preferably at 200 to 800C, at normal pressure and in solvents or diluents.
Suitable solvents or diluents are for example: ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dioxan, dimethoxyethane and tetrahydrofuran; amides. such as N,N-dialkylated carboxamides: aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene. xylenes, chloroform and chlorobenzene; nitriles, such as acetonitrile; dimethyl sulphoxide; ketones, such as acetone and methyl ethyl ketone; and water.
The starting materials of the formula III are known. They can be prepared by analogy to known processes.
The starting materials of the formulae II and IV can be prepared according to the following known reaction scheme:
CH3OCH2 CH3 CH3OCH2 CH3 CH N NH NHCOOC2Hs NHCOOC2Hs ( ('u) NaHCO3 e.g. palladium-calcium carbonate or platinum-carbon C H30 CH 2 cH CH NC- N (pun) NHCOOC2Hs CH30CH2 CH3 CH30CH2 CH3 NaSR3 CH CH I cH (viz) N-N N-N N-N R3S N R3S (11) ( LV) In the formulae II, IV to VIII, R3 is as defined in formula I and Me represents a metal, in particular an alkali metal, or ammonium or substituted ammonium. The reaction of the compound VII with the compound VIII is generally carried out in a solvent at 100 to 1200C, preferably at 200 to 900C, and lasts a few minutes to several hours, depending on the substituents and reaction conditions. Suitable solvents are for example ketones, such as acetone or methyl ethyl ketone; tetrahydrofuran; and water.
The active substances of the formula I are suitable for controlling animal and plant pests. The invention provides a method of controlling animal or plant pests which method comprises applying a compound of the formula I to the pests, to a locus infested with the pests, or to a locus to be protected from the pests. The compounds of the formula I possess nematocidal properties and can be used for example, for controlling phytopathogenic nematodes. The active substances of the formula I are also partly suitable for use as herbicides and plant regulators and for controlling viruses, bacteria, and phytopathogenic fungi. Above all, however, they act on all development stages, such as eggs, larvae, nymphs, pupae and adults, of insects and representatives of the order Acarina, such as mites and ticks.
The compounds of the formula I have, for example, a lethal or repellant action on the following insects or representatives of the order Acarina: Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae. Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae. Diaspididae, Pseudococcidae, Chrysomilidae, Coccinellidae, Bruchidae, Scarabaeidae. Dermestidae, Tenebroionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae.
Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, and Pulicidae, and of the families: Ixodidae, Argasidae, Tetranychidae and Dermanyssidae.
The acaricidal and/or insecticidal action can be substantially broadened and adjusted to prevailing conditions by adding other insecticides and/or acaricides.
Examples of suitable additives include: nitrophenols and derivatives thereof: formamidines; ureas; pyrethroids: carbamates: and chlorinated hydrocarbons.
The compounds of formula I can be used as pure active substance or together with suitable carriers and/or additives. Suitable additives can be solid or liquid and correspond to the substances conventionally used in the art of formulation. such as natural or regenerated substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binding agents and/or fertilizers. Solid pesticidal compositions according to the invention may contain, as active ingredient, a compound of the formula I together with a solid extender and optionally, a surface active agent.
Liquid pesticidal compositions according to the invention may contain the active ingredient together with a liquid diluent and a surface active agent. For application, the compounds of the formula I can be processed to dusts, emulsion concentrates, granulates, dispersions, sprays, solutions and suspensions in conventional formulations, which are commonly employed in application technology. Mention is also to be made of cattle dips and spray races, in which aqueous preparations are used.
The compositions of the present invention may be obtained in known manner e.g. by intimately mixing and/or grinding active substances of formula I with the suitable carriers, with or without the addition of dispersants or solvents which are inert to the active substances.
The active substances can be in the form of and used in the following application forms: Solids dusts, tracking agents and granulates (coated granulates, impregnated granulates and homogeneous granulates): Liquids a) active substance concentrates which are dispersible in water: wettable powders, pastes and emulsions: b) solutions: The content of active substances in the compositions described above is generally between 0.1 and 95 ' by weight.
The active substances of formula I can for example be formulated as follows (parts and percentages are by weight).
Dust The following substances are used to prepare (a) a 50/, and (b) a 20" dust: a) 5 parts of active substance, 95 parts of talcum.
b) 2 parts of active substance, I part of highly dispersed silicic acid, 97 parts of talcum.
The active substance are mixed with the carriers and ground.
Granulate The following ingredients are used to prepare a 5 " granulate: 5 parts of active substance.
0.25 part of epichlorohydrine, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3 to 0.X mm).
The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The resultant solution is sprayed onto kaolin and the acetone is subsequently evaporated in vacuo.
Wettable Powder The following ingredients are used to prepare a) a 400,,, b) and c) a 25",, and d) a 100C wettable powder: a) 40 parts of active substance, 5 parts of sodium lignin sulphonate.
I part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid; b) 25 parts of active substance.
4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne-chalk/hydroxyethylcellulose mixture (1:1), 1.5 parts of sodium dibutyl-naphthalenesulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne-chalk, 28.1 parts of kaolin; c) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne-chalk/hydroxyethylcellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin: d) 10 parts of active substance, 3 parts of a mixture of sodium salts of saturated fatty alcohol sulphonates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate.
82 parts of kaolin.
The active substances are intimately mixed with the additives in suitable mixers and ground in appropriate mills and rollers to yield wettable powders, which can be diluted with water to give suspensions of the required concentration.
Emulsifiable Concentrates The following substances are used to prepare a) a l0?n, b) a 25?i,, c) a 50 " emulsifiable concentrate: a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts of a combination emulsifier, composed of fatty alcohol polyglycol ether and calcium alkylarylsulphonate, 40 parts of dimethyl formamide, 43.2 parts of xylene: b) 25 parts of active substance.
'.5 party of epoxidised vegetable oil, 10 parts of an alkylarylsulphonate/fatty alcohol pol > glycol ether mixture, 5 parts of dimethyl formamide 57.5 parts of xylene; c) 50 parts of active substance, 4.2 parts of tributylphenol polyglycol ether 8.5 parts of calcium dodecylbenzenesulfonate.
20 parts of cyclohexanone, 20 parts of xylene.
Emulsions of any required concentration can be prepared by diluting the above described concentrates with water.
Spray The following ingredients are used to prepare a) a 5Vn and b) a 95 /" spray: a) 5 parts of active substance, 1 part of epichlorohydrin, 94 parts of ligroin (boiling range 160--190"C); b) 95 parts of active substance, 5 parts of epichlorohydrin.
The following Examples will serve to illustrate the invention in more detail.
Example 1 a) Preparation of I -( I '-methyl-2'-methoxy-ethyl)-3-hydroxy-5-methylthio1,2,4-triazole 0.5 Mole of the compound of the formula
is added dropwise at room temperature to a solution consisting of 0.5 mole of sodium hydroxide in 100 ml of water and into which 0.5 mole of CH3SH has been introduced. The reaction proceeds exothermically (700 C). The reaction mixture is kept for 1 hour at 80"C. After cooling, the product which crystallises out is collected by filtration and recrystallised from ether/hexane to yield the compound of the formula
with a melting point of 1020-l040C. The compound of the formula
(m.p. 940--960C) is obtained in analogous manner.
b) Preparation of O,O-diethyl-O-( 1 -(1 '-methyl-2'-methoxyethyl)-5-methylthio- 1 ,2,4-triazolyl(3)-thiophosphoric acid ester 0.1 Mole of 1(1 '-methyl-2'-methoxy-ethyl)-3-hydroxy-5-methylthio- 1,2,4- triazole and 0.1 mole of potassium carbonate in 200 ml of methyl ethyl ketone are refluxed for 2 hours. After the dropwise addition of 0.1 mole of diethylthiophosphoric chloride at 40"C. the mixture is refluxed once more for 2 hours, then left to stand for 15 hours at 20 C.200C. 20 C.200C. The salts are filtered off and the filtrate is concentrated in vacuo. The oilv residue is purified through a column of silica eelgel eelgel with chloroform as eluant to yield the compound of the formula
in the form of an oil with a refractive index of n2 =l.5033. The following compounds are obtained in analogous manner:
nD = 1.5072n020-l,5072 nD = 1.5072n020-l,5072 nD = 1.4970n20=l.4970 nD = 1.4970n20=l.4970 n,20=1.4935n20-1.4935 n,20=1.4935n20-1.4935 nD = 1.4960n020=l.4960 nD = 1.4960n020=l.4960 n0=1.4770n020=l.4770 n0=1.4770n020=l.4770 1.5025 Example 2 A) Insecticidal stomach poison action Cotton plants were sprayed with a 0.05 -" aqueous emulsion of active substance (obtained from a 100 emulsifiable concentrate). After the spray coating had dried, the cotton plants were populated respectively with Spodoptera littoral is and Heliothis virescens larvae in the L1 stage.
In this test, the compounds of Example lb exhibited a good insecticidal stomach poison action on Spodoptera and Heliothis larvae.
B) System insecticidal action The systemic action was determined by immersing rooted bean plants (Vicia faba) in a 0.01% aqueous solution of active substance (obtained from a l00,n emulsifiable concentrate). After 24 hours the parts of the plants above the soil were populated with aphids (Aphis fabae). The aphids were protected from the contact and gas action by a special device. The test was carried out at 240C and 70 " relative humidity.
In this test, the compounds of Example lb exhibited systemic insecticidal action on Aphis fabae.
Example 3 Action on Chilo suppressalis Six rice plants of the variety Caloro were transplanted into each of a number of plastics pots having a diameter of 17 cm at the top, and reared to a height of approx. 60 cm. Infestation with larvae of Chilo suppressalis (L1 stage; 3 to 4 mm in length) took place 2 days after the active substance had been added to the paddy water in granulate form (rate of application; 8 kg of active substance/hectare).
Evaluation of the insecticidal action took place 10 days after addition of the granulate. The compounds of Example lb acted in this test on Chilo suppressalis.
Example 4 Acaricidal action Phaseolus vulgaris (dwarf beans) had an infested piece of leaf from a mass culture of tetranychus urticae placed on them 12 hours before the test for the acaricidal action. The mobile stages which had migrated to the plants were sprayed with the emulsified test preparations from a chromatography atomiser so that the sprayed preparation did not run off. The number of living and dead larvae, adults and eggs were evaluated after 2 to 7 days under a stereoscopic microscope and the result expressed in percentages. During the course of the test, the treated plants were kept in greenhouse compartments at 250C. The compounds of Example 1b acted in the above test on eggs, larvae and adults of Tetranychus urticae.
Example 5 Action on soil nematodes The action on soil nematodes was tested by applying the active substances in the respective concentration indicated to and intimately mixing them with soil infected with root gall nematodes (Meloidgyne arenaria). Immediately afterwards, tomato cuttings were planted in the thus prepared soil in a test run and after 8 days tomato seeds were sown in another test run.
In order to assess the nematocidal action, the galls present on the roots were counted 28 days after planting and sowing respectively. In this test the compounds according to Example lb exhibited good action on Meloidgyne arenaria.
Example 6 Action on ticks A) Rhipicephalus bursa Five adult ticks and 50 tick larvae were counted into each of a number of test tubes and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion containing a concentration of 100, 10, 1 or 0.1 ppm of test substance. Each test tube was then sealed with a cotton-wool plug and placed on its head to enable the cotton wool to absorb the active substance emulsion. The adults were evaluated after 2 weeks and the larvae after 2 days. Each test was repeated twice.
B) Boophilus microplus (larvae) Tests were carried out on 20 OP- sensitive and 20 OP-resistant larvae with aqueous emulsions similar to those used in test A. (The resistance refers to the tolerance towards diazinone). The compounds of Example lb acted in these tests on adults and larvae of Rhipicephalus bursa and OP-sensitive and of resistant larvae of Boophilus microplus.
Example 7 Action of Erysiphe graminis on Hordeum vulgare Barley plants (approx. 8 cm in height) were sprayed with a spray broth (active substance content: 0.059,) prepared from a wettable powder of the active substance.
After 48 hours the treated plants were dusted with conidia of the fungus. The infected barley plants were stood in a greenhouse at approx. 220C and the fungus attack was evaluated after 10 days.
The compounds of Example lb acted in this test on Erysiphe graminis.
WHAT WE CLAIM IS: 1. A 1,2,4-triazole of the formula
wherein each of R1, R2 and R3 independently represents a C1-C6-alkyl group and X represents an oxygen or sulphur atom.
2. A 1,2,4-triazole according to claim 1, wherein each of R1, R2 and R3 independently represents a methyl or ethyl group and X represents a sulphur atom.
3. A 1,2,4-triazole of the formula
4. A 1,2,4-triazole of the formula
5. A 1 2,4-triazole of the formula
6. A 1,2,4-triazole of the formula
7. A 1,2,4-triazole of the formula
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (25)

**WARNING** start of CLMS field may overlap end of DESC **. substance content: 0.059,) prepared from a wettable powder of the active substance. After 48 hours the treated plants were dusted with conidia of the fungus. The infected barley plants were stood in a greenhouse at approx. 220C and the fungus attack was evaluated after 10 days. The compounds of Example lb acted in this test on Erysiphe graminis. WHAT WE CLAIM IS:
1. A 1,2,4-triazole of the formula
wherein each of R1, R2 and R3 independently represents a C1-C6-alkyl group and X represents an oxygen or sulphur atom.
2. A 1,2,4-triazole according to claim 1, wherein each of R1, R2 and R3 independently represents a methyl or ethyl group and X represents a sulphur atom.
3. A 1,2,4-triazole of the formula
4. A 1,2,4-triazole of the formula
5. A 1 2,4-triazole of the formula
6. A 1,2,4-triazole of the formula
7. A 1,2,4-triazole of the formula
8. A 1,2,4-triazole of the formula
9. A 1,2.4-triazole of the formula
10. A process for the preparation of a compound of the formula I defined in claim I, which process comprises reacting a compound of the formula
wherein R1, R2 and X are as defined in claim 1 and Hal represents a halogen atom, with a compound of the formula
wherein R3 is as defined in claim 1 and Z represents a hydrogen atom, a metal, or ammonium or substituted ammonium, in the presence of an acid acceptor when Z represents a hydrogen atom.
11. A process according to claim 10 substantially as hereinbefore described.
12. A compound of the formula I defined in claim 1 when prepared by a process according to claim 10 or claim 11.
13. A solid pesticidal composition, which composition contains, an active ingredient, a compound according to any one of claims 1 to 4 together with a solid extender and, optionally, a surface active agent.
14. A liquid pesticidal composition, which composition contains, an active ingredient, a compound according to any one of claims 1 to 4 together with a liquid diluent and a surface active agent.
15. A pesticidal composition containing a compound according to claim 1 in the form of a dust, granulate, wettable powder, emulsifiable concentrate, or spray as hereinbefore described specifically.
16. A solid pesticidal composition, which composition contains, as active ingredient, a compound according to any one of claims 5 to 9 together with a sQlid extender and, optionally, a surface active agent.
17. A liquid pesticidal composition, which composition contains, as active ingredient, a compound according to any one of claims 5 to 9 together with a liquid diluent and a surface active agent.
18. A method of controlling animal or plant pests, which method comprises applying a compound according to any one of claims 1 to 4 to the pests, to a locus infested with the pests, or to a locus to be protected from the pests.
19. A method according to claim 18, wherein the pests to be controlled are insects and representatives of the order Acarina.
20. A method according to claim 18, wherein the pests to be controlled are phytopathogenic nematodes.
21. A method according to claim 18, wherein the pests to be controlled are phytopathogenic fungi.
22. A method of controlling animal or plant pests, which method comprises applying a compound according to any one of claims 5 to 9 to the pests, to a locus infested with the pests, or to a locus to be protected from the pests.
23. A method according to claim 22 wherein the pests to be controlled are insects and representatives of the order Acarina.
24. A method according to claim 22 wherein the pests to be controlled are phytopathogenic nematodes.
25. A method according to claim 22 wherein the pests to be controlled are phytopathogenic fungi.
GB47241/76A 1975-11-14 1976-11-12 Phosphorus-containing triazole derivatives Expired GB1563733A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1479675A CH602012A5 (en) 1975-11-14 1975-11-14 (5)-Alkylthio-(1,2,4)-triazolyl-(3)-(thio)phosphates
CH1200276 1976-09-22

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GB1563733A true GB1563733A (en) 1980-03-26

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GB47241/76A Expired GB1563733A (en) 1975-11-14 1976-11-12 Phosphorus-containing triazole derivatives

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JP (1) JPS5262277A (en)
AT (1) AT341830B (en)
CA (1) CA1074326A (en)
DE (1) DE2651556A1 (en)
FR (1) FR2331566A1 (en)
GB (1) GB1563733A (en)
NL (1) NL7612543A (en)
PH (1) PH12226A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265897A (en) * 1978-11-14 1981-05-05 Ciba-Geigy Corporation N-N-Dimethyl-1-(1'-methyl-2'-methoxyethyl)-1,2,4-triazolylcarbamates

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DE2651556A1 (en) 1977-05-26
JPS5262277A (en) 1977-05-23
PH12226A (en) 1978-11-29
CA1074326A (en) 1980-03-25
AT341830B (en) 1978-02-27
ATA844776A (en) 1977-06-15
NL7612543A (en) 1977-05-17
FR2331566A1 (en) 1977-06-10
FR2331566B1 (en) 1978-04-14

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