IE46876B1 - 4-substituted-2-chloro-3,5-diiodo pyridines and their use as herbicides - Google Patents
4-substituted-2-chloro-3,5-diiodo pyridines and their use as herbicidesInfo
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- IE46876B1 IE46876B1 IE893/78A IE89378A IE46876B1 IE 46876 B1 IE46876 B1 IE 46876B1 IE 893/78 A IE893/78 A IE 893/78A IE 89378 A IE89378 A IE 89378A IE 46876 B1 IE46876 B1 IE 46876B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/68—One oxygen atom attached in position 4
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- 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
- A01N47/02—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 no bond to a nitrogen atom
- A01N47/06—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 no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
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- 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
- A01N47/08—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 one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
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- 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
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- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The compounds of the formula I are new. The substituent in the formula I has the meaning given in Claim 1. The new compounds are prepared by iodination of 2-chloro-4-hydroxypyridine, followed if appropriate by its conversion to the corresponding salts or esters. The new compounds are notable for their good herbicidal action and are used to control unwanted plants.
Description
The present invention relates to certain novel 2chloro-3,5-diiodo pyridine derivatives and to processes Cor their preparation. The novel compounds possess interesting herbicidal activity.
According to one feature of the present invention there are provided compounds of the .general formula:-
T5
.
wherein R represents a hydrogen atom, one equivalent of an inorganic or organic cation,., the group -OC-Rj or -0C-ORp (in which R^ represents an alkyl group wiLh up to 17 carbon atoms, optionally substituted by halogen, an alkenyl group with up to 4 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, a phenyl group optionally chloro-, nitro- or methyl-substituted or a benzyl or styryl group), the group -OC-NR^R^ (in which R,, and Rj, which may he the same or different, each represent an alkyl group with 1 to 4 carbon atoms), or the group —O^S—(in which R^ represents an alkyl group with 1 to 4 carbon atoms or a phenyl group optionally substituted by methyl).
Where R in formula I represents one equivalent of an inorganic or organic cation the cations of alkali metal and alkaline earth niel.nl cation.-; are preI erred inorganic cations whilst alkyl ammonium c.atii ns. For example those derived from methylamincs, ethylamines, ethanolantine and piperidine are preferred organic cations.
Preferred compounds of formula I, by virtue of their especially interesting herbicidal activity, are those in which R represents the groups -OC-K^ and -OC-OK, wherein
R-j represents an alkyl group with 1 to 10 carbon atoms, especially 1.0 an alkyl group with up to 3 carbon atoms, optionally substituted by halogen. Halogen substituents in the groups -OC-Kj, and -(X'-Okj are preferably chlorine or bromine atoms.
An esptrin liy pre»erred compound of the present invention, by virtue of its particularly interesting
Γ) herbicidal activity, is 2-chloro-3,S-diiodo-4-acetoxy pyridine.
The present invention also relate.·; Lo the compounds of formula I together with at least one of:
(a) 3-(4-ehloropheny1)-1-methy1-1-(1-methyl-prop-2-yny1)20 urea;
(b) 3-(4-chlorophenyI)-1-methyl-l-methoxyurea;
(c) 3-(3-chloro-4-methoxyphenyl)-l,1-ditnethylurea;
4-6876 (d) 3-(3-chloro-4-methy 1 phony ()-1,1-d iineLliy (urea;
(e) 1-benzothiazol -2-yl-l, J-dimetliy (urea;
(f) 3-(4-isopropylphenyl) - 1,J-dimethylurea;
(g ) 6 -t-but yl-4- (2-me thy 1 -propy 1 ί dene Imino ) - .3 -me thy 1mercapto-4,5-dihydro-i,2,4-triazin -5-one;
(h) isobuty1-2-[4-(4-chlorophenoxy)-phenoxy]-proplonate;
(i) ethyl-2-(N-benzoyl-3,4-dichloroanilino)-propionate;
(j) l,2.-dimethyl-3,5~diphenylpyrazoliuin- methyl sulfate;
(k) 2-chloro-3-(4-chlorophenyl)-methylpropionate;
(l) methy1-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate;
(m) a mixture of 4-chloro-2-methylphenoxy acetic acid or a salt thereof, and 9-hydroxyfluorene-9-carboxylic acid or a salt thereof;
(n) 2-(4-chloro-2-methylphenoxy)-propionic acid or a salt thereof;
(o) 2-(2,4-dichlorophenoxy)-propionic acid or a salt • thereof;
(p) a mixture of 2,4-dichlorophenoxy acetic acid or a salt thereof, and 4chloro-2-methylphenoxy acetic acid or a salt thereof;
(q) 4-hydroxy-3,5-diiodobenzonitrile;
(r) 4-hydroxy-3,5-dibromobenzonitrile;
- 4 46876 (s) 3-isopropyl-[iH] -benzo-2,1,3-thiadiazin-4-one-2,2-dioxide;
(t) 3, r>-dibromo-4-hydroxybenzaldehyde-2,4-dinitropheny 1oxime:
(u) 2-(l-methyl-n-propyl)-4,6~dinitrophenylacetate; and (v) 4,6-dinitro-2-t-butylphenol.
Thus for example the invention includes, in combination, (i) a compound of formula I as hereinbefore defined, and (ii) a mixture of the dimethylamine salt of 4-ehloro-2methylphenoxy acetic acid and the dimethylamine salt of 9-hydroxyfluorene-9-carboxylic acid. The present invention also includes, in combination (i) a compound of formula I as hereinbefore defined, and (ii) a mixture of 2,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid (both in salt form).
According to a further feature of the present invention there is provided a process for the preparation of compounds of formula J as hereinbefore defined (wherein R represents a hydrogen atom or one equivalent of an inorganic or organic cation) which comprises iodinating 2«chloro-4-hydroxypyridine whereby 2-chloro-3,5-diiodo-4-hydroxypyridine is obtained and, if desired, converting the said 2-chloro-3,5-diiodo-4hydroxypyridine into a compound of formula 1 in which R
4687 6 represents an equivalent of an inorganic or organic cation. The iodination may, for example, be effected by Lhe use of iodine(I)-chloride or iodic acid/iodine. When usin», iodine(I)-chloride the reaction is preferably effected in the presence of acetic acid, aqueous hydrochloric acid or water, conveniently at an elevated temperature, for example at the boiling temperature of the reaction mixture. When the iodination is effected by the use of iodic acid/iodine, the iodination is preferably effected in the presence of water/ethanol. Other organic solvents miscible with waLer may conveniently be used instead of ethanol, if they are sufficiently inert under the reaction conditions, Cor example acetic acid.
, , The compounds of formula I wherein R represents a hydrogen atom or an equivalent of an inorganic or organic cation may, if desired, be employed as starting materials in the preparation of the remaining compounds of formula I.
ι
Thus according to a further feature of the present invention there is provided a process for the preparation of compounds of formula I as hereinbefore defined (wherein R represents the group -OC-R^, -OC-OR^, -OC-Ni^Rg or -O^S-R^ in which R^, R2, Rj and R^ are as hereinbefore defined)
- 6 4687 which comprises reacting 2-chloro-3,5-0110(10-4-117(1 roxypyridine with a compound of the formula :RpCO-X (II); R1O-CO-X (III); R2R.,N-CO-X (IV); or r4-so2-x (V) •5 (wherein Rp R2, R^ and R^ are as hereinbefore defined and
X represents ah atom or group removable as an anion) whereby a compound of formula I. as hereinbefore defined (wherein R represents the group R^-CO-, RjO-C.0-, l^R^N-COor R4”SO2- in which Rp Rp R^ and R^ are as hereinbefore defined) is obtained.
A compound of the formula II, III, IV or V is preferably used in which X represents a chlorine or bromine atom. ’
Where it is desired to prepare a compound of formula 1 15 in which R represents the group -DC-Rj, a compound of formula Π may conveniently be used in which X represents the group -O-OC-R^ (in which R^ is as hereinbefore defined) Thus the acylation may be effected by the use of an acid anhydride of formula R^-CO-O-OC-Rp
The compounds according to the present invention possess herbicldal activity, furthermore the compounds of formula I, wherein R represents a hydrogen atom or one
- 7 46876 equivalent of an inorganic or organic cation, may be used as intermediates in the production of herbicides.
According to a further feature of the present invention there are provided herbicidal compositions which comprise as active ingredient at least one compound of formula I as hereinbefore defined in association with an inert carrier or diluent.
The compositions preferably comprise 2-chloro-3,5diiodo-4-acetoxypyridine as active ingredient.
The compounds of the present invention are herbicidally active using leaf or soil treatment. At high dosages the compounds of the invention may serve as total herbicides, whereas at lower dosages (¢0.25 kg/ha) the compounds of the present invention may be used to selectively kill broad15 leaf weeds, for example in cereal fields by means of postemergence leaf-treatment.
The compositions of the present invention may, for example, be in the form of wettable powders, dusting powders, granulates, solutions, emulsifiable concentrates, emulsions or sprays. The active ingredient content of the compositions of the present invention may amount to about 90% by weight.
Compositions suitable for use without dilution
- 8 4 6 8 7 6 preferably contain from 0.001 to 5% by weight, preferably 0.005 to 1% by weight of the active ingredient of formula I, Dusting agents and, especially, ULV (ultra low volume) formulations may contain higher concentrations of active ingedient, for example, up to approximately 857, by weight.
The herbicidal compositions of the present invention may be formulated in conventional manner, at least one active ingredient of formula I being mixed with conventional carriers or excipients for example solvents, diluents,
IO wetting and adhesive agents, emulsifiers and dispersants, optionally together with other herbicides or biocides.
The superior activity of the compounds according to the invention is shown, for example, by the following comparative test (greenhouse test, leaf treatment):15 As 2-chloro-3,5-diiodo-4-acetoxypyridine (according to invention)
B: 2-chloro-3,5-diiodo-4-acetoxy-6-methylpyridine (U.S.
Patent 3,859,295)
In order to achieve 90% extermination of broad-leef weeds 20 0,043 kg/ha of A and 0.29 kg/ha of B are required.
Tests which we have conducted show that the active ingredient according to the invention, especially 2-chloro3,5-diiodo-4-acetoxypyridine, may be used with advantage in combination with other herbicides. Thus in one embodiment of the present invention the herbicidal compositions additionally contain as a further active ingredient at least one of the following:(a) 3-(4-chlorophenyl)-1-methyl-l-(l-methyl-prop-2-ynyl)urea;
(b) 3-(4-chlorophenyl)-1-methyl-l-methoxyurea;
(c) 3-(3-chloro-4-methoxyphenyl)-l,1-dimethylurea;
(d) 3-(3-chloro-4-methylphenyl)-i,1-dimethylurea;
(e) 1-benzothiazol - '2-yl-l,3-dimethylurea;
(f) 3-(4-isopropyIpheny1)-1,1-dimethylurea;
(g) 6-tert.-butyl-4-(2-methyl-propylideneimino)-3-methylmercapto-4,5-dihydro-1,2,4-triazin -5-pne;
(h) isobutyl-2-[4r(4-chlorophenoxy)-phenoxy]-propionate;
(i) ethy1-2-(N-benzoy1-3,4-dichloroanilino)-propionate;
( j) 1,2*'dimethy 1-3,5-diphenylpyrazolium-methyl sul fate;
(k) 2-chloro-3-(4-chlorophenyl)-methylpropionate;
(l) tnethyl-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate;
(m) a mixture of 4-chloro-2-methylphenoxy acetic acid pr a salt thereof and 9-hydro)(yfluorene-9-carboxylic acid or a salt thereof;
(n) 2-(4-chloro-2-methylphenoxy)-propionic acid or a salt thereof;
(o) 2-(2,4-dichlorophenoxy)-propionic. acid oj· a salt thereof;
(p) a mixture of 2,4-dichlorophenoxy acetic acid or a salt thereof and 4-chloro-2-methylphenoxy acetic acid or a salt thereof;
(q) 4-hydroxy-3,5-diiodobenzonitrile;
(r) 4-hydroxy-3,5-dibromobenzonitrile;
(s) 3-isopropyl-QhJ- benzo-2,1,3-thiadiazin-4-one-2,2-dioxide;
(t) 3,5-dibromo-4-hydroxybenzaldehyde-2,4-d ini trophenyloxime;
(u) 2-(1-methyl-n-propy1)-4,6-(1 ini trophenylacetnte; and (v) 4,6-dinitro-2-t-butylphenol,
In one embodiment of the present invention the further active ingredient comprises a mixture of the dimethylamine salts of 4-chloro-2-methylphenoxy acetic acid and 9-hydroxyfluorene-9-carboxylic acid. In a further embodiment of the present invention the further active ingredient comprises a mixture of 2,4-dichlorophenoxy acetic acid and 4-chloro-2methylphenoxy acetic acid, both in salt form. In a still further embodiment of the present invention there are provided herbicidal compositions which comprise 2-chloro-3,5-diiodo-4-acetoxy-pyridine and 3-isopropyl-(Th]benzo-2,1,3-thiadiazin-4-one-2,2~dioxide as active ingredient.
We have found that a more favourable spectrum of activities or a synergistic effect way be achieved by the use of such combinations. In such combinations the acLive ingredient according to the invention, in particular (.he above-mentioned especially preferred compound, is advantageously used in a concentration of approximately O.ui to 1.0, preferably 0.05 to 0.3 kg/ha. Each of the effective ingredients is conveniently used in from 50 to 100% of the normal dose. In typical combinations of the above-mentioned type, the following quantities of active ingredient may for example be used, together with from 0.05 - 0.2 kg/ha of
2-chloro-3,5-diiodo-4-acetoxypyridine and, for example, from
0.1 to 6.0 kg/ha of the further active ingredient preferably about:
1.0 kg/ha 3-(4-chlorophenyl)-l-methyl~l-(l-methyl-prop-2~ ynyl)-urea,
0.5 kg/ha 3-(4-chlorophenyl)-l-methyl-l-methoxyurea,
3.3 kg/ha 3-(3-chloro-4-methoxyphenyl)-l,1-dimethylurea,
2.0 kg/ha 3-(3-chloro-4-methylphenyl)-l,1-dimethylurea,
2.5 kg/ha 1-benzothiazol-2 -yl-l,3-dimethylurea,
1.5 kg/ha 3-(4-isopropylphenyl)-l,1-dimethylurea,
0.9 kg/ha 6-t-butyl-4-(2-methyl-propylideneimino)-3methylmercapto-4,5-dihydro-1,2,4-triazin-5-one,
0.9 kg/ha isobutyl-2-[4- {4-chlorophenoxy)-phenoxyJ-propionate,
1.6 kg/ha ethyl-2-(N-benzoyl-3,4-dichloroanilino)propionate,
1.0 kg/ha 1, 2-dimethyl-3,5-diphenylpyrazolium- methylsulfate. 4.0 kg/ha 2-chloro-3-(4-chlorophenyl)-methylpropionate,
1.0 kg/ha methyl-2-[4-(2,4-dichlorophenoxy)-phenoxy]propionate,
1.0 kg/ha a mixture of the dimethylamine salts of 4-chloro2-methylphenoxy acetic acid (760 g) and the dimethylamine salt of 9-hydroxy-fluorene-9-carboxyTic
Ιθ acid (240 g),
2.4 kg/ha 2-(4-chloro-2-methylphenoxy)-propionic acid or a salt thereof,
2.4 kg/ha 2-(2,4-dichiorophefioxy)-propionic acid or a salt thereof,
0.8 kg/ha a 1:1 combination by weight of 2,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid (both as salts),
0.4 kg/ha 4-hydroxy-3,5-diiodobenzonitrile,
0.4 kg/ha 4-hydroxy-3,5-dibromobenzonitrile,
2.0 kg/ha 3-isopropyl 0H-benzo-2,l ,3-thiadiazin-4-one]2,2-dioxide,
2.0 kg/ha 3,5-dibromo-4-hydroxybenzaldehyde-2,4-dinitrophenyloxime,
2.5 kg/ha 2-(l-methyl-n-propyl)-4,6-dinitrophenylacetate, or 3.0 kg/ha 4,6-dinitro-2-t-butylphenol.
The preceding further active ingredients may, however, be used in varying doses. Thus, for example, the quantity of those herbicides which act primarily upon monocotyledons may be reduced to approximately 75% and the quantities of the other herbicides to approximately 50% of the quantities indicated above. If required, the quantity of the active ingredient according to the present invention employed in compositions comprising a further active ingredient may be increased, preferably within the range indicated above, at the same time as the quantity of further active ingredient is reduced. If desired, the further active ingredients listed above may be applied in a concentration increased by approximately 50% over that indicated in the list, in which case the active ingredients according to the present invention will be applied in a /
lower concentration than the range indicated above.
According to a still further feature of the present invention there is provided a method for controlling undesired vegetation which comprises applying to the locus of said undesired vegetation an effective amount of a composition as hereinbefore defined.
The following Examples illustrate the present invention:EXAMPLE 1
2-Chloro-3,5-diiodo-4-hydroxypyridlne
129.5 g (1 mol) of 2-chloro-4-hydroxypyridine and
203.2 g (0.8 mol) of iodine are added to 1 Itr. of ethanol and heated while stirring. At 60 to 70°C, a solution of 70.4 g (0.4 mol) of iodic acid dissolved in 200 ml of water is added dropwise to the reaction mixture. The reaction mixture is then refluxed for 30 minutes, allowed to cool and the crystals thus formed are filtered off with suction. The crystals are then rinsed with cold ethanol and dried at 100-110°C.
The yield is 366 g (96% of theory).
The substance decomposes at >290°C.
EXAMPLE 2
2-Chloro-3,5-diiodo-4-acetoxypyridine
191 g (0.5 mol) of 2-chloro-3,5-diiodo-4-hydroxypyridine are suspended in 400 ml of acetic anhydride and refluxed for minutes. A clear solution is obtained which is stirred 20 after cooling into 5 ltr. of water. The precipitating solid is filtered off with suction, washed with water and dried at 5O-6O°C. The yield amounts to 192 g (91% of theory);
m.p. 127-128°C (from ethanol).
EXAMPLE 3
2-Chloro-3,5-diiodo-4-hydroxypyridine sodium salt
381.5 g (1 mol) of 2-chloro-3,5-diiodo-4-hydroxy5 pyridine are added to a solution of 23 g (1 mol) of sodium in 200 ml of methanol. The methanol is completely distilled off from the solution obtained, under the current addition of toluene whereby a colourless powder precipitates, which is filtered off with suction and dried. The yield is quantitative.
EXAMPLE 4
2-Chloro-3,5-dliodo-4-methoxycarbonyloxypyridine
38.1 g (0.1 mol) of 2-chloro-3,5-diiodo-4-hydroxypyridine, 15 g (0.15 mol) of methyl chloroformate and 27.6 g (0.2 mol) of potassium carbonate are refluxed for 3 hours in 300 ml of acetonitrile. After cooling, the reaction mixture is poured onto water, extracted with methylene chloride, the organic phase is shaken with 1% sodium hydroxide solution and water, dried over sodium sulfate and evaporated. The remaining oil solidifies when cooling to form a crystal cake, which may be recrystaliized from cyclohexane. Yield: 35 g(82,7% of theory); m.p. 74-75°C.
EXAMPLE 5
2-Chloro-3,5-diiodo-4-(N,N-dimethylcarbamoyloxy)-pyridine
8.1 g (0.02 mol) of the sodium salt of Example 2 are boiled while stirring with 4.2 g (0.04 mol) of dimethyl5 carbamoyl chloride in 50 ml of toluene for 20 hours. The residue is then filtered off, the cooled solution is shaken with 0.5 N sodium hydroxide solution and water and evaporated. When triturated, the remaining oil solidifies and is crystallized from ethyl acetate. Yield: 6 g (64% of theory);
m.p. 148-149°C.
EXAMPLE 6 (a) 129,5 g (1 mol) of 2-chloro-4-hydroxypyridine and
203.2 g (0.8 mol) of iodine are suspended in a mixture of
1.6 ltr. of ethanol and 400 ml of 20% sulfuric acid, while stirring. The mixture is heated to 60'C and over a period of 30 minutes a solution of 86 g of potassium iodate in 200 ml of water is added dropwise to the mixture. The reaction mixture is refluxed for a further 30 minutes, allowed to cool and the suspension is then decolorized by the dropwise addition of 20 mis of a saturated solution of sodium hydrogen sulfite in water. The reaction mixture is then filtered off with suction, washed thoroughly with water and rinsed with a little cold ethanol. After drying at approximately 100C, 340 g (897, of theory) of 2-chloro-3,5-diiodo-4-hydroxypyridine are obtained.
(b) 129.5 g (1 mol) of 2-chloro-4-hydroxypyridine are 5 suspended in 4 ltr. of 10% hydrochloric acid. A solution of
324 g (2 mol) of iodine chloride in 650 ml of 10% hydrochloric acid is poured into the mixture while stirring and is slowly heated to boiling. The reaction mixture is allowed to cool, the separated product is filtered off with suction, washed thoroughly with water and dried at 110'’C. The yield of 2-chloro-3,5-diiodo-4-hydroxypyridine amounts to 320 g (84% of theory).
(c) 253 g (1 mol) of iodine are suspended in 1 ltr. of acetic acid. At room temperature 71 g of chlorine gas are introduced into the mixture in the course of one hour. To the solution thus obtained are added 129,5 g (1 mol) of 2-chloro-4-hydroxypyridine and the mixture is heated for 30 minutes to 100°C. The mixture is then cooled, poured onto 3 ltr. of water, filtered off with suction, washed thoroughly with water and dried at 110°C. The yield of 2-chloro-3,5diiodo-4-hydroxypyridine amounts to 340 g (89% of theory).
(d) a mixture of 129.5 g (1 mol) of 2-chloro-4-hydroxy18 4 68 7 6 pyridine and 253 g (1 mol) of iodine is suspended in I Itr. of acetic acid and heated to bO'C while stirring. Λ mixture of 30 ml of nitric acid (d 1.4) and 110 ml of sulfuric acid (d 1.84) is added dropwise to the suspension and subsequently the temperature is maintained at 60°C for 30 more minutes.
The reaction mixture thus obtained is then poured onto 3 itr. of water, filtered off with suction, washed thoroughly with water and dried at 110°C, The yield of 2-chloro-3,5-diiodo4-hydroxypyridine amounts to 335 g (88% of theory).
Corresponding to the preceding Examples, the compounds of the following table may also be obtained.
R Ijfglljinp Point Ο— “ 150-151 N02 NO? 'S_ 146-148 N02 — ch2-co- 119-120 -CH=CH-C0- 135-136 l-c3h7-o-co- 58-59 CH,-CH-0-C0- 147-149 ch3 ch3(ch2)12_14 -o-co- oil (mixture) ch3(ch2)3-ch-ch2-o-coC2h5 oil (C2H5 )^-00- 132-133 CH3-SO2- 133 H3C -S02- 158 C2H5-CO- 146-147
In the following Examples all percentages are by weight. llerbicidaL composition Examples
EXAMPLE A
Wettable Powder
% of 2-chloro-3,5-diiodo-4-acetoxypyridine
55% of kaolin
% of colloidal silicic acid
9% of lignine sulfonate (dispersing agent)
1% of sodium tetrapropylene benzosulfonate (wetting agent)
EXAMPLE B
Wettable Powder
80% of active ingredient according to the invention
8% of calcium lignine sulfonate
% of colloidal silicic acid
% of sodium sulfate
2% of diisobutyl-naphthalene sodium sulfonate
EXAMPLE C
Emulsifiable Concentrate
40% of active ingredient according to the invention 20 25% of * Shellsol A (liquid mixture of aromatic hydrocarbons)
% of N-inethylpyrrolidone
% of Emulsogen I 40 (anion-active emulsifier)
The concentrates indicated above are diluted to the desired concentration of active ingredient for use with water (0.001 to 5% by weight) Registered *Shellac is a/trade mark.
Claims (44)
1. Compounds of the OR 'Δ wherein R represents a hydrogen atom, one equivalent of an 5 inorganic or organic cation , the group -OC-R-j or -OC-OR^, (in which represents an alkyl group with up to 17 carbon atoms, optionally substituted by halogen, an alkenyl group with up to 4 carbon atoms, a cycloaikyl group with 3 to 6 carbon atoms, a phenyl group optionally chloro-, nitro- or 10 methyl-substituted or a benzyl or styryl group), the group -OC-NR 2 R 3 (in which R 2 and R^, which may be the same or different, each represent an alkyl group with 1 to 4 carbon atoms), or the group -O 2 S-R^ (in which R^ represents an alkyl group with Ί to 4 carbon atoms or phenyl group 15 optionally substituted by methyl),
2. Compounds as claimed in claim 1 wherein R represents one equivalent of an alkali metal or alkaline earth metal cation. •
3. Compounds-as claimed in claim 1 wherein R represents an alkylammonium cation.
4. Compounds as claimed in claim 3 wherein R 5. Represents a methylammonium, ethylammonium, ethanol ammonium or piperidinium cation.
5. Compounds as claimed in claim 1 wherein R represents the group -OC-R^ or -OC-OR^, in which R.| represents an alkyl group with 1 to 10 carbon atoms optionally 10 substituted by halogen.
6. Compounds as claimed in claim 5 wherein R represents the group -OC-R^ or -OC-OR^ in which R^ represents an alkyl group with up to 3 carbon atoms optionally substituted by halogen. 15
7. Compounds as claimed in any one of claims 1, 5 and 6 wherein R represents the group -OC-Rj or -OC-OR^ in which R^ represents an alkyl group substituted by a chlorine or bromine atom.
8. 2-Chloro-3,5-diiodo-4-acetoxypyridine. 20
9. Compounds as claimed in claim 1 as herein disclosed in any one of Examples 1 and 3 to 31. 4 6 8 7 6
10. A compound as claimed in any one of the preceeding claims together with at least one of: (a) 3-(4-chlorophenyl)-1-methy1-1-(1-methyl-prop-2-yny1)urea; 5 (b) 3-(4-chlorophenyl)-l-methyl-l-methoxyurea; (c) 3-(3-chloro-4-methoxyphenyl)-l,l-dimethylurea; (d) 3-(3-chloro-4-methylphenyl)-l,1-dimethylurea; (e) 1- benzothiazol -2-yl-l,3-dimethylurea; (f) 3-(4-isopropylphenyl)-l,1-dimethylurea; 10 (g) 6-t-butyl-4-(2-methyl-propylideneimino)-3-methylmercapto-4,5-dihydro-l,2,4-triazin -5-one; (h) isobutyl-2-[4-(4-chlorophenoxy)-phenoxy]-propionate; (i) ethyl-2-(N-benzoyl-3,4-dichloroanilino)-propionate; (j) 1,2 -dimethyl-3,5-diphenylpyrazolium- methyl sulfate; 15 (k) 2-chloro-3-(4-chlorophenyl)-methylpropionate; (l) methy1-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate; (m) a mixture of 4-chloro-2-methylphenoxy acetic acid or a salt thereof and 9-hydroxyfluorene-9-carboxylic acid or a salt thereof; (n) 2-(4-chloro-2-methylphenoxy)-propionic acid or a salt thereof; 468 76 (o) 2-(2,4-dichlorophenoxy)-propionic acid or a salt thereof; (p) a mixture of 2,4-dichlorophenoxy acetic acid or a salt thereof and 4-chloro-2-methylphenoxy acetic acid or a salt 5 thereof; (q) 4-hydroxy-3,5-diiodobenzonitrile; (r) 4-hydroxy-3;5-dibromobenzonitrile; (s) 3-isopropyl - [lH]- benzo-2 s l ,3-thiadiazin-4-one-2,2-dioxide; (t) 3,5-dibromo-4-hydroxybenzaldehyde-2,4-dinitrophenyl10 oxime; (u) 2-(l-methyl-n-propyl)-4,6-dinitrophenylacetate; and (v) 4,6-dinitro-2-t-butylphenol.
11. A combination of compounds as claimed in claim 10 which comprises (i) a compound of formula I as defined in claim 1, and (ii) a 15 mixture of the dimethylamine salt of 4-chloro-2-methylphenoxy acetic acid and the dimethylamine salt of 9-hydroxyfluorene9-carhoxylic acid.
12. A combination of compounds as claimed in claim 10 which comprises (i) a compound of formula I as defined in claim 1, and (ii) a 20 mixture of 2,4-dichlorophenoxy acetic acid and 4-chloro-2methylphenoxy acetic acid (both in salt form).
13. A process for the preparation of compounds of formula I as defined in claim 1 (wherein R represents a hydrogen atom or one equivalent of an inorganic or organic cation) which comprises iodinating 2-chloro-4-hydroxypyridine 5 whereby 2-chloro-3,5-diiodo-4“hydroxypyridine is obtained and, if desired, converting the said 2-chloro~3,5-diiodo-4hydroxypyridine into a compound of formula I in which R represents an equivalent of an inorganic or organic cation.
14. A process as claimed in claim 13 wherein the 10 iodination is effected by the use of iodine (I) chloride.
15. A process as claimed in claim 14 wherein the iodination is effected in the presence of acetic acid, aqueous hydrdchloric acid or water.
16. A process as claimed in claim 14 or claim 15 15 wherein the iodination is effected at an elevated temperature.
17. A process as claimed in claim 16 wherein the iodination is effected at the boiling temperature of the reaction mixture. 20
18. A process as claimed in claim 13 wherein the iodination is effected by the use of iodic acid/iodine.
19. , A process as claimed in claim 18 wherein the the iodination is effected in the presence of water/ethanoi.
20. A process for the preparation of compounds of formula I as defined in claim 1 (wherein R represents the group 5 -OC-Rp -0C-0Rp -0C-NR 2 R 3 or ° 2 S-R 4 in which Rp Rg, R 3 and R^ are as defined in claim 1) which comprises reacting 2-chloro-3,5-diiodo-4-hydroxypyridine with a compound of the formula:R^CO-X (II); R^-CO-X (III); R^N-CO-X (IV) 10 or R 4 -50 2 -X (V) (wherein Rp Rg, R 3 and R^ are as defined in claim I and X represents an atom or group removable as an anion) whereby a compound of formula I as defined in claim 1 (wherein R represents the group Rq-CO-, R^O-CO-, 15 R 2 R 3 N-C0- or R^-SOg- in which Rp Rg, R 3 and R^ are as defined in claim 1) is obtained.
21. A process as claimed in claim 20 wherein a compound of formula II, III, IV or V is used in which X represents a chlorine or bromine atom. 20
22. A process as claimed in claim 20 for the preparation of compounds of formula I as defined in claim 1 (in which R represents the group R^-CO-) wherein a compound of formula II is used in which X represents the group -O-CO-R 1 (in which is as defined in claim 1).
23. A process as claimed in claim 13 or claim 20 substantially as herein described.
24. A process for the preparation of compounds of 5 formula I as defined in claim 1 substantially as herein described in any one of Examples 1 to 31.
25. Compounds of formula I as defined in claim 1 when prepared by a process as defined in claim 13 or claim 20.
26. Herbicidal compositions which comprise as active 10 ingredient at least one compound as defined in any one of claims 1 to 9 in association with an inert carrier or diluent.
27. Compositions as claimed in claim 26 which comprise 2-chloro-3,5-diiodo-4-acetoxypyridine as active ingredient. 15
28. Compositions as claimed in claim 26 or claim 27 in the form of wettable powders, emulsifiable concentrates, dusting powders, solutions or granulates.
29. Compositions as claimed in any one of claims 26 to 28 suitable for use without dilution and containing from 20 0.001 to 5% by weight of the said active ingredient.
30. Compositions as claimed in claim 29 which contain from 0.005 to 1% by weight of the said active ingredient.
31. Compositions as claimed in claim 26 or claim 27 in the form of dusting agents or ultra low volume formulations which contain up to 85% by weight of the said active ingredient. 5
32. Compositions as claimed in any one of claims 26 to 31 which additionally contain as a further active ingredient at least one of the following:(a) 3-(4-chlorophenyl)-1-methyl-l-(l-methyl-prop-2-ynyl)urea; 10 (b) 3-(4-chlorophenyl)-1-methyl-l-methoxyurea; (c) 3-(3-chloro-4-methoxyphenyl)-l,1-dimethylurea; '(d) 3-(3-chloro-4-methylphenyl)-l,1-dimethylurea; (e) 1-benzothiazol -2-yl-l,3-dimethylurea; (f) 3-(4-isopropyIpheny1)-1,1-dimethylurea; 15 (g) 6-tert.-butyl-4-(2-methyl-propylideneimino)-3-methylmercapto-4,5-dihydro-1,2,4-triazin -5-one; (h) isobutyl-2-[4-(4-chlorophenoxy)-phenoxy]-propionate; (i) ethy1-2-(N-benzoy1-3,4-dichloroanilino)-propionate; (j) 1,2-dimethy1-3,5-diphenylpyrazolium -methyl sul fate; 20 (k) 2-chloro - 3-(4-chlorophenyl)-methylpropionate; (1) methyl-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate; (m) (n) a mixture of 4-chloro-2-methylphenoxy acetic acid or a salt thereof and 9-hydroxyfluorene-9-carboxylic acid or a salt thereof; 2-(4-chloro-2-methylphenoxy)-propionic acid O r a salt thereof; (o) 2-(2,4-dichlorophenoxy)-propionic acid or a salt thereof; (p) a mixture of 2,4-dichlorophenoxy acetic acid or a salt thereof and 4-chloro-2-methylphenoxy acetic acid cr a salt thereof; 10 (q) 4-hydroxy-3,5-diiodoben2onitrile; (r) 4-hydroxy-3,5-dibromobenzonitrile; (s) 3-isopropyl- [jH]- benzo-2,1,3-thiadiazin-4-one-2,2-dioxide; (t) 3,5-dibromo-4-hydroxybenzaldehyde-2,4-dinitrophenyloxime; (u) 2-(l-methyl-n-propyl)-4,6-dinitrophenylacetate; and 15 (v) 4,6-dinitro-2-t-butylphenol.
33. , Compositions as claimed in claim 32 wherein the further active ingredient is a mixture of the dimethylamine salts of 4-chloro-2-methylphenoxy acetic acid and 9-hydroxyfluorene-9-carboxylic acid. 20
34. Compositions as claimed in claim 32 wherein the further active ingredient is a mixture of 2.,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid, both in salt form.
35. Compositions as claimed in claim 32 which comprise 2-chloro-3,5diiodo -4-acetoxy-pyridine and 3-isopropyl-[Ϊη]- benzo-2,1,3-thiadiazin4-one-2,2-dioxide as active ingredient.
36. Compositions as claimed in claim 26 substantially as herein described.
37. Herbicidal compositions substantially as herein described in any one of Examples A to C.
38. A method for controlling undesired vegetation which comprises applying to the locus of said undesired vegetation an effective amount of a composition as defined in any one of claims 26 to 37.
39. A method as claimed in claim 38 wherein from 0.03 to 1.0 kg/ha of the said active ingredient is applied to the locus of said' undesired vegetation.
40. A method as claimed in claim 39 wherein from 0.05 to 0.3 kg/ha 6f the said active ingredient is applied to the locus of said undesired vegetation.
41. . A method as claimed in any one of claims 38 to 40. wherein from 0.05 to 0.2 kg/ha of 2-chloro-3,5-diiodo4-acetoxy pyridine is applied to the locus of said undesired vegetation.
42. A method as claimed in any one of claims 38 to 41 wherein from 0.1 to 6.0 kg/ha of the said further active ingredient (as defined in claim 32) is applied to the locus of said undesired vegetation.
43. A method as claimed in any one of claims 35 to 40 for the selective control of broad-leaf weeds in the presence of crop plants wherein less than 0.25 kg/ha of the said active ingredient is applied to the weeds.
44. Λ method as claimed in claim 38 substantialiy as herein described. Dated this 3rd day of May, 1978.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772719904 DE2719904A1 (en) | 1977-05-04 | 1977-05-04 | NEW PYRIDE DERIVATIVES, THEIR PRODUCTION AND USE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE780893L IE780893L (en) | 1978-11-04 |
| IE46876B1 true IE46876B1 (en) | 1983-10-19 |
Family
ID=6007986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE893/78A IE46876B1 (en) | 1977-05-04 | 1978-05-03 | 4-substituted-2-chloro-3,5-diiodo pyridines and their use as herbicides |
Country Status (28)
| Country | Link |
|---|---|
| JP (1) | JPS53137968A (en) |
| AR (1) | AR222012A1 (en) |
| AT (1) | AT364191B (en) |
| AU (1) | AU518477B2 (en) |
| BE (1) | BE866699A (en) |
| BR (1) | BR7802751A (en) |
| CA (1) | CA1096383A (en) |
| CH (1) | CH638788A5 (en) |
| DE (1) | DE2719904A1 (en) |
| DK (1) | DK193478A (en) |
| ES (2) | ES469387A1 (en) |
| FR (1) | FR2389607B1 (en) |
| GB (1) | GB1601609A (en) |
| GR (1) | GR64825B (en) |
| HU (1) | HU182008B (en) |
| IE (1) | IE46876B1 (en) |
| IL (1) | IL54625A (en) |
| IT (1) | IT1103860B (en) |
| LU (1) | LU79582A1 (en) |
| MX (1) | MX5292E (en) |
| NL (1) | NL7804747A (en) |
| NZ (1) | NZ187160A (en) |
| PL (1) | PL110684B1 (en) |
| SE (1) | SE7805138L (en) |
| SU (1) | SU1047376A3 (en) |
| TR (1) | TR20611A (en) |
| YU (1) | YU99078A (en) |
| ZA (1) | ZA782544B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL398870A1 (en) | 2012-04-18 | 2013-10-28 | Biosynergia Spólka Akcyjna | Fertilizer and the method of obtaining suspended organic phosphorus fertilizer from digestate waste |
| PL398871A1 (en) | 2012-04-18 | 2013-10-28 | Bio Technology Spólka Z Ograniczona Odpowiedzialnoscia | The method of obtaining mineral-organic fertilizer from digestate in agricultural biogas plants |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1242057A (en) * | 1968-07-04 | 1971-08-11 | Ici Ltd | Derivatives of 4-hydroxytetrafluoropyridine and the use thereof as plant growth regulators |
| GB1241869A (en) * | 1969-02-25 | 1971-08-04 | Ici Ltd | Process for making a halopyridine |
| IL44846A0 (en) * | 1973-05-24 | 1974-07-31 | Ici Ltd | Herbicidal pyridine derivatives |
-
1977
- 1977-05-04 DE DE19772719904 patent/DE2719904A1/en not_active Withdrawn
-
1978
- 1978-04-24 GR GR56074A patent/GR64825B/en unknown
- 1978-04-25 YU YU00990/78A patent/YU99078A/en unknown
- 1978-04-25 AT AT0295578A patent/AT364191B/en not_active IP Right Cessation
- 1978-04-27 TR TR20611A patent/TR20611A/en unknown
- 1978-04-28 AR AR271981A patent/AR222012A1/en active
- 1978-05-02 CH CH476478A patent/CH638788A5/en not_active IP Right Cessation
- 1978-05-02 JP JP5326378A patent/JPS53137968A/en active Pending
- 1978-05-02 IT IT49163/78A patent/IT1103860B/en active
- 1978-05-02 IL IL54625A patent/IL54625A/en unknown
- 1978-05-03 IE IE893/78A patent/IE46876B1/en unknown
- 1978-05-03 LU LU79582A patent/LU79582A1/en unknown
- 1978-05-03 HU HU78CE1164A patent/HU182008B/en unknown
- 1978-05-03 BE BE187389A patent/BE866699A/en not_active IP Right Cessation
- 1978-05-03 FR FR7813184A patent/FR2389607B1/fr not_active Expired
- 1978-05-03 GB GB17517/78A patent/GB1601609A/en not_active Expired
- 1978-05-03 MX MX787057U patent/MX5292E/en unknown
- 1978-05-03 PL PL1978206550A patent/PL110684B1/en unknown
- 1978-05-03 DK DK193478A patent/DK193478A/en unknown
- 1978-05-03 SE SE7805138A patent/SE7805138L/en unknown
- 1978-05-03 BR BR7802751A patent/BR7802751A/en unknown
- 1978-05-03 ES ES469387A patent/ES469387A1/en not_active Expired
- 1978-05-03 CA CA302,519A patent/CA1096383A/en not_active Expired
- 1978-05-03 AU AU35727/78A patent/AU518477B2/en not_active Expired
- 1978-05-03 NZ NZ187160A patent/NZ187160A/en unknown
- 1978-05-03 ZA ZA782544A patent/ZA782544B/en unknown
- 1978-05-03 NL NL7804747A patent/NL7804747A/en not_active Application Discontinuation
- 1978-05-03 SU SU782609553A patent/SU1047376A3/en active
- 1978-10-06 ES ES474005A patent/ES474005A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES469387A1 (en) | 1978-12-01 |
| AR222012A1 (en) | 1981-04-15 |
| BE866699A (en) | 1978-11-03 |
| GR64825B (en) | 1980-06-03 |
| TR20611A (en) | 1982-01-01 |
| IT7849163A0 (en) | 1978-05-02 |
| IL54625A0 (en) | 1978-07-31 |
| IL54625A (en) | 1981-09-13 |
| IE780893L (en) | 1978-11-04 |
| PL206550A1 (en) | 1979-04-09 |
| LU79582A1 (en) | 1979-06-13 |
| CH638788A5 (en) | 1983-10-14 |
| AU518477B2 (en) | 1981-10-01 |
| ZA782544B (en) | 1980-01-30 |
| DE2719904A1 (en) | 1978-11-09 |
| MX5292E (en) | 1983-06-06 |
| NL7804747A (en) | 1978-11-07 |
| YU99078A (en) | 1983-01-21 |
| CA1096383A (en) | 1981-02-24 |
| HU182008B (en) | 1983-12-28 |
| ATA295578A (en) | 1981-02-15 |
| SE7805138L (en) | 1978-11-05 |
| NZ187160A (en) | 1981-03-16 |
| GB1601609A (en) | 1981-11-04 |
| ES474005A1 (en) | 1979-05-01 |
| AU3572778A (en) | 1979-11-08 |
| SU1047376A3 (en) | 1983-10-07 |
| DK193478A (en) | 1978-11-05 |
| IT1103860B (en) | 1985-10-14 |
| FR2389607B1 (en) | 1983-06-17 |
| AT364191B (en) | 1981-09-25 |
| FR2389607A1 (en) | 1978-12-01 |
| JPS53137968A (en) | 1978-12-01 |
| BR7802751A (en) | 1979-04-10 |
| PL110684B1 (en) | 1980-07-31 |
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