CA1096383A - Pyridine derivatives, their production and use - Google Patents
Pyridine derivatives, their production and useInfo
- Publication number
- CA1096383A CA1096383A CA302,519A CA302519A CA1096383A CA 1096383 A CA1096383 A CA 1096383A CA 302519 A CA302519 A CA 302519A CA 1096383 A CA1096383 A CA 1096383A
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Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
The invention relates to novel 2-chloro-3,5-diiodopyridine derivatives and to processes for their preparation, The novel compounds possess herblcidal activity and are effective via leaf or soil treatment.
The invention thus also relates to herbicidally compositions comprising the novel compounds as active ingredient as well as to the methods for controlling undesired vegetation using the novel compounds. The compositions of the present invention possess a marked herbicidal activity and in high concentrations serve as total herbicides. In lower concentrations, however, the compositions are of use in the selective control of broad-leaf weeds in the presence of crop plants. Processes for the production of the novel compounds are described and examples of certain of the novel compounds are given. Herbicidal compositions containing the active compounds are described and exemplified.
The invention relates to novel 2-chloro-3,5-diiodopyridine derivatives and to processes for their preparation, The novel compounds possess herblcidal activity and are effective via leaf or soil treatment.
The invention thus also relates to herbicidally compositions comprising the novel compounds as active ingredient as well as to the methods for controlling undesired vegetation using the novel compounds. The compositions of the present invention possess a marked herbicidal activity and in high concentrations serve as total herbicides. In lower concentrations, however, the compositions are of use in the selective control of broad-leaf weeds in the presence of crop plants. Processes for the production of the novel compounds are described and examples of certain of the novel compounds are given. Herbicidal compositions containing the active compounds are described and exemplified.
Description
10~63~33 The present invention relates to certain novel 2-chloro-3,5-diiodo pyridine derivatives and to processes for their preparation. The novel compounds possess interesting herbicidal activity.
According to one feature of the present invention there are provided compounds of the formula:-OR
I ~ I (I) ~ Cl wherein R represents a hydrogen atom, one equivalent of an inorganic or organic cation or the group -OC-Rl or -OC-ORl, (in which Rl represents an alkyl group with 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-NR2R3 (in which R2 and R3, which may be the : same or different, each represent an alkyl group with 1 to ; 4 carbon atoms), or the group -02S-R4 (in which R4 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 l~fi3~33 inorganic or organic cation the cations of alkali metal and alkaline earth metal cations are preferred inorganic cations whilst alkylammonium cations, for example those derived from methylamines, ethylamines, ethanolamine 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-Rl and -OC-ORl, wherein Rl represents a lower up to middle alkyl group, especially an alkyl group with up to 3 carbon atoms, optionally substituted by halogen. Halogen substituents in the groups -OC-Rl and -OC-ORl are preferably chlorine or bromine atoms.
An especially preferred compound of the present invention, by virtue of its particularly interesting herbicidal activity, is 2-chloro-3,5-diiodo-4-acetoxy ; pyridine.
The present invention also relates to the compounds of formula I together with at least one of:
ta) 3-(4-chlorophenyl)-1-methyl-1-(1-methyl-prop-2-ynyl)-urea;
(b) 3-(4-chlorophenyl)-1-methyl-1-methoxyurea;
(c) 3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea;
I
109~3~3 (d) 3-(3-chloro-4-methylphenyl)-l,l-dimethylurea;
(e) l-benzthiazole-2-yl-1,3-dimethylurea;
(f) 3-(4-isopropylphenyl)-1,1-dimethylurea;
(g) 6-t-butyl-4-(2-methyl-propylideneimino)-3-methyl-S mercapto-4,5-dihydro-1,2,4-triazlne-5-one;
(h) isobutyl-2-[4-(4-chlorophenoxy)-phenoxy]-propionate;
(i) ethyl-2-(N-benzoyl-3,4-dichloroanilino)-propionate;
:~ (j) l,l-dimethyl-3,5-diphenylpyrazolium-methosulfate;.
(k) 2-chloro-3-(4-chlorophenyl)-methylpropionate;
(1) methyl-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate;
(m) a mixture of 4-chloro-2-methylphenoxy acetic acid and 9-hydroxyfluorene-9-carboxylic acid and the salts thereof;
(n) 2-(4-chloro-2-methylphenoxy)-propionic acid and the salts thereof;
(o) 2-(2,4-dichlorophenoxy)-propionic acid and the salts thereof;
(p) a mixture of 2,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid and the salts thereof;
(q) 4-hydroxy-3,5-diiodobenzonitrile;
(r) 4-hydroxy-3,5-dibromobenzonitrile;
~ 38~
(s) 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide;
(t) 3,5-dibromo-4-hydroxybenzaldehyde-2,4-dinitrophenyl-oxime;
(u) 2-(1-methyl-n-propyl)-4,6-dinitrophenylacetate; and S (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-chloro-2-methylphenoxy 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-di-chlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid (in salt form).
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 a hydrogen atom or one equlvalent 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-4-hydroxypyridine into a compound of formula I in which R
1~963~3 represents an equivalent of an inorganic or organic cation.
The iodination may, for example, be effected by the use of iodine(I)-chloride or iodic acid/iodine. When using 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 water may conveniently be used instead of ethanol, if they are sufficiently inert under the reaction conditions, for 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.
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-Rl, -OC-ORl, -OC-NR2R3 or -O2S-R4 in which Rl, R2, R3 and R4 are as hereinbefore defined) - . . 1 1~9~3~3 - which comprises reacting 2-chloro-3,5-diiodo-4-hydroxy-pyridine with a compound of the formula:-Rl-C0-X (II); R10-C0-X (III); R2R3N-C0-X (IV); or 4 S 2 X (V) (wherein Rl, R2, R3 and R4 are as hereinbefore defined and X represents an atom or group removable as an anion) ; whereby a compound of formula I as hereinbefore defined J (wherein R represents the group Rl-C0-, R10-C0-, R2R3N-C0-or R4-S02- in which Rl, R2, R3 and R4 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 I
in which R represents the group -OC-Rl, a compound of formula II may conveniently be used in which X represents the group -0-OC-Rl (in which Rl is as hereinbefore defined).
Thus the acylation may be effected by the use of an acid anhydride of formula Rl-C0-0-OC-Rl.
The compounds according to the present invention possess herbicidal activity. Furthermore the compounds of formula I, wherein R represents a hydrogen atom or one -1~963~13 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-3,5-diiodo-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 broad-leaf weeds, for example in cereal fields by means of post-emergence 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 1~9~i;3~3~
, preferably contain from 0.001 to 5% by weight, preferably 0.005 to 1% by weight. Dusting agents and, especially, ULV
: (ultra low volume) formulations may contain higher concen-trations of active ingedient, for example, up to approximately 85% 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, 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):-A: 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 0.043 kg/ha of A and 0.29 kg/ha of B are required.
Tests which we have conducted show that the active _ g _ ,' ~91~38~
;, ingredient according to the invention, especially 2-chloro-3,5-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-1-(1-methyl-prop-2-ynyl)-urea;
(b) 3-(4-chlorophenyl)-1-methyl-1-methoxyurea;
(c) 3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea;
(d) 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea;
(e) l-benzthiazole-2-yl-1,3-dimethylurea;
(f) 3_(4-isopropylphenyl)-1,1-dimethylurea;
(g) 6-tert.-butyl-4-(2-methyl-propylideneimino)-3-methyl-mercapto-4,5-dihydro-1,2,4-triazine-5-one;
(h) isobutyl-2-[4-(4-chlorophenoxy)-phenoxy]-propionate;
(i) ethyl-2-(N-benzoyl-3,4-dichloroanilino)-propionate;
(j) 1,1-dimethyl-3,5-diphenylpyrazolium-methosulfate;
(k) 2-chloro-3-(4-chlorophenyl)-methylpropionate;
(1) methyl-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate;
(m) a mixture of 4-chloro-2-methylphenoxy acetic acid and 9-hydroxyfluorene-9-carboxylic acid and the salts 1~)63~33 thereof;
(n) 2-(4-chloro-2-methylphenoxy)-propionic acid and the salts thereof;
(o) 2-(2,4-dichlorophenoxy)-propionic acid and the salts . .
; 5 thereof;
(p) a mixture of 2,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid and the salts thereof;
(q) 4-hydroxy-3,5-diiodobenzonitrile;
(r) 4-hydroxy-3,5-dibromobenzonitrile;
(s) 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxlde;
(t) 3,5-dibromo-4-hydroxybenzaldehyde-2,4-dinitrophenyloxime;
(u) 2-(1-methyl-n-propyl)-4,6-dinitrophenylacetate; 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-hydroxy-fluorene-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-2-methylphenoxy acetic acid in salt form.
We have found that a more favourable spectrum of activities or a synergistic effect may be achieved by the ~`~963~33 use of such combinations. In such combinations the active - ingredient according to the invention, in particular the above-mentioned especially preferred compound, is advantageously used in a concentration of approximately 0.03 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
According to one feature of the present invention there are provided compounds of the formula:-OR
I ~ I (I) ~ Cl wherein R represents a hydrogen atom, one equivalent of an inorganic or organic cation or the group -OC-Rl or -OC-ORl, (in which Rl represents an alkyl group with 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-NR2R3 (in which R2 and R3, which may be the : same or different, each represent an alkyl group with 1 to ; 4 carbon atoms), or the group -02S-R4 (in which R4 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 l~fi3~33 inorganic or organic cation the cations of alkali metal and alkaline earth metal cations are preferred inorganic cations whilst alkylammonium cations, for example those derived from methylamines, ethylamines, ethanolamine 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-Rl and -OC-ORl, wherein Rl represents a lower up to middle alkyl group, especially an alkyl group with up to 3 carbon atoms, optionally substituted by halogen. Halogen substituents in the groups -OC-Rl and -OC-ORl are preferably chlorine or bromine atoms.
An especially preferred compound of the present invention, by virtue of its particularly interesting herbicidal activity, is 2-chloro-3,5-diiodo-4-acetoxy ; pyridine.
The present invention also relates to the compounds of formula I together with at least one of:
ta) 3-(4-chlorophenyl)-1-methyl-1-(1-methyl-prop-2-ynyl)-urea;
(b) 3-(4-chlorophenyl)-1-methyl-1-methoxyurea;
(c) 3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea;
I
109~3~3 (d) 3-(3-chloro-4-methylphenyl)-l,l-dimethylurea;
(e) l-benzthiazole-2-yl-1,3-dimethylurea;
(f) 3-(4-isopropylphenyl)-1,1-dimethylurea;
(g) 6-t-butyl-4-(2-methyl-propylideneimino)-3-methyl-S mercapto-4,5-dihydro-1,2,4-triazlne-5-one;
(h) isobutyl-2-[4-(4-chlorophenoxy)-phenoxy]-propionate;
(i) ethyl-2-(N-benzoyl-3,4-dichloroanilino)-propionate;
:~ (j) l,l-dimethyl-3,5-diphenylpyrazolium-methosulfate;.
(k) 2-chloro-3-(4-chlorophenyl)-methylpropionate;
(1) methyl-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate;
(m) a mixture of 4-chloro-2-methylphenoxy acetic acid and 9-hydroxyfluorene-9-carboxylic acid and the salts thereof;
(n) 2-(4-chloro-2-methylphenoxy)-propionic acid and the salts thereof;
(o) 2-(2,4-dichlorophenoxy)-propionic acid and the salts thereof;
(p) a mixture of 2,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid and the salts thereof;
(q) 4-hydroxy-3,5-diiodobenzonitrile;
(r) 4-hydroxy-3,5-dibromobenzonitrile;
~ 38~
(s) 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide;
(t) 3,5-dibromo-4-hydroxybenzaldehyde-2,4-dinitrophenyl-oxime;
(u) 2-(1-methyl-n-propyl)-4,6-dinitrophenylacetate; and S (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-chloro-2-methylphenoxy 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-di-chlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid (in salt form).
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 a hydrogen atom or one equlvalent 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-4-hydroxypyridine into a compound of formula I in which R
1~963~3 represents an equivalent of an inorganic or organic cation.
The iodination may, for example, be effected by the use of iodine(I)-chloride or iodic acid/iodine. When using 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 water may conveniently be used instead of ethanol, if they are sufficiently inert under the reaction conditions, for 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.
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-Rl, -OC-ORl, -OC-NR2R3 or -O2S-R4 in which Rl, R2, R3 and R4 are as hereinbefore defined) - . . 1 1~9~3~3 - which comprises reacting 2-chloro-3,5-diiodo-4-hydroxy-pyridine with a compound of the formula:-Rl-C0-X (II); R10-C0-X (III); R2R3N-C0-X (IV); or 4 S 2 X (V) (wherein Rl, R2, R3 and R4 are as hereinbefore defined and X represents an atom or group removable as an anion) ; whereby a compound of formula I as hereinbefore defined J (wherein R represents the group Rl-C0-, R10-C0-, R2R3N-C0-or R4-S02- in which Rl, R2, R3 and R4 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 I
in which R represents the group -OC-Rl, a compound of formula II may conveniently be used in which X represents the group -0-OC-Rl (in which Rl is as hereinbefore defined).
Thus the acylation may be effected by the use of an acid anhydride of formula Rl-C0-0-OC-Rl.
The compounds according to the present invention possess herbicidal activity. Furthermore the compounds of formula I, wherein R represents a hydrogen atom or one -1~963~13 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-3,5-diiodo-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 broad-leaf weeds, for example in cereal fields by means of post-emergence 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 1~9~i;3~3~
, preferably contain from 0.001 to 5% by weight, preferably 0.005 to 1% by weight. Dusting agents and, especially, ULV
: (ultra low volume) formulations may contain higher concen-trations of active ingedient, for example, up to approximately 85% 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, 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):-A: 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 0.043 kg/ha of A and 0.29 kg/ha of B are required.
Tests which we have conducted show that the active _ g _ ,' ~91~38~
;, ingredient according to the invention, especially 2-chloro-3,5-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-1-(1-methyl-prop-2-ynyl)-urea;
(b) 3-(4-chlorophenyl)-1-methyl-1-methoxyurea;
(c) 3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea;
(d) 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea;
(e) l-benzthiazole-2-yl-1,3-dimethylurea;
(f) 3_(4-isopropylphenyl)-1,1-dimethylurea;
(g) 6-tert.-butyl-4-(2-methyl-propylideneimino)-3-methyl-mercapto-4,5-dihydro-1,2,4-triazine-5-one;
(h) isobutyl-2-[4-(4-chlorophenoxy)-phenoxy]-propionate;
(i) ethyl-2-(N-benzoyl-3,4-dichloroanilino)-propionate;
(j) 1,1-dimethyl-3,5-diphenylpyrazolium-methosulfate;
(k) 2-chloro-3-(4-chlorophenyl)-methylpropionate;
(1) methyl-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate;
(m) a mixture of 4-chloro-2-methylphenoxy acetic acid and 9-hydroxyfluorene-9-carboxylic acid and the salts 1~)63~33 thereof;
(n) 2-(4-chloro-2-methylphenoxy)-propionic acid and the salts thereof;
(o) 2-(2,4-dichlorophenoxy)-propionic acid and the salts . .
; 5 thereof;
(p) a mixture of 2,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid and the salts thereof;
(q) 4-hydroxy-3,5-diiodobenzonitrile;
(r) 4-hydroxy-3,5-dibromobenzonitrile;
(s) 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxlde;
(t) 3,5-dibromo-4-hydroxybenzaldehyde-2,4-dinitrophenyloxime;
(u) 2-(1-methyl-n-propyl)-4,6-dinitrophenylacetate; 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-hydroxy-fluorene-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-2-methylphenoxy acetic acid in salt form.
We have found that a more favourable spectrum of activities or a synergistic effect may be achieved by the ~`~963~33 use of such combinations. In such combinations the active - ingredient according to the invention, in particular the above-mentioned especially preferred compound, is advantageously used in a concentration of approximately 0.03 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)-1-methyl-1-(1-methyl-prop-2-ynyl)-urea, 0.5 kg/ha 3-(4-chlorophenyl)-1-methyl-1-methoxyurea,
; 1.0 kg/ha 3-(4-chlorophenyl)-1-methyl-1-(1-methyl-prop-2-ynyl)-urea, 0.5 kg/ha 3-(4-chlorophenyl)-1-methyl-1-methoxyurea,
3.3 kg/ha 3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea, 2.0 kg/ha 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 2.5 kg/ha 1-benzothiazole-2-yl-1,3-dimethylurea, 1.5 kg/ha 3-(4-isopropylphenyl)-1,1-dimethylurea, 0.9 kg/ha 6-t-butyl-4-(2-methyl-propylideneimino)-3-methylmercapto-4,5-dihydro-1,2,4-triazine-5-one, : 0 9 kg/ha isobutyl-2-[4-chlorophenoxy)-phenoxy]-propionate, 1~9~,383 1.6 kg/ha ethyl-2-(N-benzoyl-3,4-dichloroanilino)-propionate, 1.0 kg/ha 1,1-dimethyl-3,5-diphenylpyrazolium-methosulfate,
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-chloro-2-methylphenoxy acetic acid (760 g) and 9-hydroxy-fluorene-9-carboxylic acid (240 g), 2.4 kg/ha 2-(4-chloro-2-methylphenoxy)-propionic acid and the salts thereof, 2.4 kg/ha 2-(2,4-dichlorophenoxy)-propionic acid and the salts thereof, 0.8 kg/ha a 1:1 combination of 2,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid (as salts), 0 4 kg/ha 4-hydroxy-3,5-diiodobenzonitrile, 0 4 kg/ha 4-hydroxy-3,5-dibromobenzoinitrile, 2.0 kg/ha 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, 2.0 kg/ha 3,5-dibromo-4-hydroxybenzaldehyde-2,4~dinitro-phenyloxime, 2.5 kg/ha 2-(1-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 lS 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.
1~963~13 The following Examples illustrate the present invention:-2-Chloro-3,5-diiodo-4-hydroxypyridine - 129.5 g (1 mol) of 2-chloro-4-hydroxypyridine and 203.2 g (0.8 mol) of iodine are added to 1 ltr. of ethanol and heated while stirring. -At 60 to 70C, 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 100-110C.
! The yield is 366 g (96% of theory).
The substance decomposes at >290C.
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 30 minutes. A clear solution is obtained which is stirred after cooling into 5 ltr. of water. The precipitating solid is filtered off with suction, washed with water and dried at 50-60C. The yield amounts to 192 g (91% of theory);
~9G3~3 m.p. 127-128C (from ethanol).
2-Chloro-3,5 diiodo-4-hydroxypyridine sodium salt 381.5 g (1 mol) of 2-chloro-3,5-diiodo-4-hydroxy-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.
2-Chloro-3,5-diiodo-4-methoxycarbonyloxypyridine 38.1 g (0.1 mol) of 2-chloro-3,5-diiodo-4-hydroxy-pyridine, 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 recrystallized from cyclo-hexane Yield: 35 g(82.7% of theory); m.p 74-75C, 1~9~;3~3 -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 dimethyl-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.
(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 mls 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 1~9~ 3 a little cold ethanol. After drying at approximately 100C, 340 g (89% of theory) of Z-chloro-3,5-diiodo-4-hydroxy-pyridine are obtained.
(b) 129.5 g (1 mol) of 2-chloro-4-hydroxypyridine are suspended in 4 ltr. of 10% hydrochloric acid. A solution of 324 g (2 mol) of iodine chloride in 650 ml of 10% hydro-chloric 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 110C. 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 100C. The mixture is then cooled, poured onto 3 ltr. of water, filtered off with suction, washed thoroughly with water and dried at 110C. The yield of 2-chloro-3,5-` diiodo-4-hydroxypyridine amounts to 340 g (89% of theory).
(d) a mixture of 129.5 g (1 mol) of 2-chloro-4-hydroxy-1~ 9G~3~ 3 pyridine and 253 g (1 mol) of iodine is suspended in 1 ltr.
of acetic acid and heated to 60C while stirring. A 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 60C for 30 more minutes.
The reaction mixture thus obtained is then poured onto 3 ltr.
of water, filtered off with suction, washed thoroughly with water and dried at 110C. The yield of 2-chloro-3,5-diiodo-4-hydroxypyridine amounts to 335 g (88% of theory).
Corresponding to the preceding Examples, the compounds of the following table may also be obtained.
` - ~
1~96383 Example No. R [8Cl] ing Point ,. , , . .-n-C 3H7-C0- 58-60 . CH3 9 n C7H15 C0 oil 11 CH3-CH=CH-C0 113-114 12 Cl-CH2-CH2-C0 99-100 Br : C12CH-CO- 99-100 ~ C0- 93-95 17 ~ C0- 149-151 :.:
18 Cl ~ C0- 115-120 19 CH3 -~ C0- 158-159 .
..
~ 1~963~33 Example ~lc~in~ Point ¢3~ C0- 150-151 .. N02 21 ~ - C0 146-148 22 ~ - CH2-C- 119-120 23 <~3--CH=CH-Co_ 135-136 24 n C3 7 0 C0 58-59 26 CH3 ( CH2) 12-14 C0 o ll : ( mixture) 27 CH3( CH2 ) 3-CH-CH2-0-C0- oil 28 (C2H5)2N-C0- 132-133 H3C ~ S2- 158 ,. .1 ~96383 In the following Examples all percentages are by weight.
Herbicidal composition Examples EXAMPLE A
Wettable Powder 25% of 2-chloro-3,5-diiodo-4-acetoxypyridine 55% of kaolin 10% 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
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 lS 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.
1~963~13 The following Examples illustrate the present invention:-2-Chloro-3,5-diiodo-4-hydroxypyridine - 129.5 g (1 mol) of 2-chloro-4-hydroxypyridine and 203.2 g (0.8 mol) of iodine are added to 1 ltr. of ethanol and heated while stirring. -At 60 to 70C, 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 100-110C.
! The yield is 366 g (96% of theory).
The substance decomposes at >290C.
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 30 minutes. A clear solution is obtained which is stirred after cooling into 5 ltr. of water. The precipitating solid is filtered off with suction, washed with water and dried at 50-60C. The yield amounts to 192 g (91% of theory);
~9G3~3 m.p. 127-128C (from ethanol).
2-Chloro-3,5 diiodo-4-hydroxypyridine sodium salt 381.5 g (1 mol) of 2-chloro-3,5-diiodo-4-hydroxy-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.
2-Chloro-3,5-diiodo-4-methoxycarbonyloxypyridine 38.1 g (0.1 mol) of 2-chloro-3,5-diiodo-4-hydroxy-pyridine, 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 recrystallized from cyclo-hexane Yield: 35 g(82.7% of theory); m.p 74-75C, 1~9~;3~3 -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 dimethyl-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.
(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 mls 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 1~9~ 3 a little cold ethanol. After drying at approximately 100C, 340 g (89% of theory) of Z-chloro-3,5-diiodo-4-hydroxy-pyridine are obtained.
(b) 129.5 g (1 mol) of 2-chloro-4-hydroxypyridine are suspended in 4 ltr. of 10% hydrochloric acid. A solution of 324 g (2 mol) of iodine chloride in 650 ml of 10% hydro-chloric 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 110C. 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 100C. The mixture is then cooled, poured onto 3 ltr. of water, filtered off with suction, washed thoroughly with water and dried at 110C. The yield of 2-chloro-3,5-` diiodo-4-hydroxypyridine amounts to 340 g (89% of theory).
(d) a mixture of 129.5 g (1 mol) of 2-chloro-4-hydroxy-1~ 9G~3~ 3 pyridine and 253 g (1 mol) of iodine is suspended in 1 ltr.
of acetic acid and heated to 60C while stirring. A 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 60C for 30 more minutes.
The reaction mixture thus obtained is then poured onto 3 ltr.
of water, filtered off with suction, washed thoroughly with water and dried at 110C. The yield of 2-chloro-3,5-diiodo-4-hydroxypyridine amounts to 335 g (88% of theory).
Corresponding to the preceding Examples, the compounds of the following table may also be obtained.
` - ~
1~96383 Example No. R [8Cl] ing Point ,. , , . .-n-C 3H7-C0- 58-60 . CH3 9 n C7H15 C0 oil 11 CH3-CH=CH-C0 113-114 12 Cl-CH2-CH2-C0 99-100 Br : C12CH-CO- 99-100 ~ C0- 93-95 17 ~ C0- 149-151 :.:
18 Cl ~ C0- 115-120 19 CH3 -~ C0- 158-159 .
..
~ 1~963~33 Example ~lc~in~ Point ¢3~ C0- 150-151 .. N02 21 ~ - C0 146-148 22 ~ - CH2-C- 119-120 23 <~3--CH=CH-Co_ 135-136 24 n C3 7 0 C0 58-59 26 CH3 ( CH2) 12-14 C0 o ll : ( mixture) 27 CH3( CH2 ) 3-CH-CH2-0-C0- oil 28 (C2H5)2N-C0- 132-133 H3C ~ S2- 158 ,. .1 ~96383 In the following Examples all percentages are by weight.
Herbicidal composition Examples EXAMPLE A
Wettable Powder 25% of 2-chloro-3,5-diiodo-4-acetoxypyridine 55% of kaolin 10% 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
5% of colloidal silicic acid 5% of sodium sulfate 2% of diisobutyl-naphthalene sodium sulfonate EXAMPLE C
Emulsifiable Concentrate 40% of active ingredient according to the invention 25% of Shellsol A (liquid mixture of aromatic hydrocarbons) 25% of N-methylpyrrolidone 10% of Emulsogen I 40 (anion-active emulsifier) 1~9~;3133 The concentrates indicated above are diluted to the desired concentration of active ingredient for use with water (0.001 to 5% by weight).
Emulsifiable Concentrate 40% of active ingredient according to the invention 25% of Shellsol A (liquid mixture of aromatic hydrocarbons) 25% of N-methylpyrrolidone 10% of Emulsogen I 40 (anion-active emulsifier) 1~9~;3133 The concentrates indicated above are diluted to the desired concentration of active ingredient for use with water (0.001 to 5% by weight).
Claims (27)
1. Compounds of the formula:
(I) wherein R represents a hydrogen atom, one equivalent of an inorganic or organic cation or the group -OC-R1 or -OC-OR1, (in which R1 represents an alkyl group with 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-NR2R3 (in which R2 and R3, which may be the same or different, each represent an alkyl group with 1 to 4 carbon atoms), or the group -O2S-R4 (in which R4 represents an alkyl group with 1 to 4 carbon atoms or a phenyl group optionally substituted by methyl).
(I) wherein R represents a hydrogen atom, one equivalent of an inorganic or organic cation or the group -OC-R1 or -OC-OR1, (in which R1 represents an alkyl group with 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-NR2R3 (in which R2 and R3, which may be the same or different, each represent an alkyl group with 1 to 4 carbon atoms), or the group -O2S-R4 (in which R4 represents an alkyl group with 1 to 4 carbon atoms or a phenyl group 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.
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 represents a methylammonium, ethylammonium, ethanol ammonium or piperidinium cation.
5. Compounds as claimed in claim 1 wherein R represents the group -OC-R1 or -OC-OR1, in which R1 represents a lower or middle alkyl group optionally substituted by halogen.
6. Compounds as claimed in claim 5 wherein R represents the group -OC-R1 or -OC-OR1 in which R1 represents an alkyl group with up to 3 carbon atoms optionally substituted by halogen.
7. Compounds as claimed in any one of claims 1, 5 or 6 wherein R represents the group -OC-R1 or -OC-OR1 in which R1 represents an alkyl group substituted by a chlorine or bromine atom.
8. 2-Chloro-3,5-diiodo-4-acetoxypyridine.
9. A herbicidal agent which comprises one or more compounds of formula (I) as defined in claim 1 in admixture with a known herbicide.
10. Compounds as claimed in claim 1 together with at least one of:
(a) 3-(4-chlorophenyl)-1-methyl-1-(1-methyl-prop-2-ynyl)-urea;
(b) 3-(4-chlorophenyl)-1-methyl-1-methoxyurea;
(c) 3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea;
(d) 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea;
(e) 1-benzthiazole-2-yl-1,3-dimethylurea;
(f) 3-(4-isopropylphenyl)-1,1-dimethylurea;
(g) 6-t-butyl-4-(2-methyl-propylideneimino)-3-methyl-mercapto-4,5-dihydro-1,2,4-triazine-5-one;
(h) isobutyl-2-[4-(4-chlorophenoxy)-phenoxy]-propionate;
(i) ethyl-2-(N-benzoyl-3,4-dichloroanilino)-propionate;
(j) 1,1-dimethyl-3,5-diphenylpyrazolium-methosulfate;
(k) 2-chloro-3-(4-chlorophenyl)-methylpropionate;
(l) methyl-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate;
(m) a mixture of 4-chloro-2-methylphenoxy acetic acid and 9-hydroxyfluorene-9-carboxylic acid and the salts thereof;
(n) 2-(4-chloro-2-methylphenoxy)-propionic acid and the salts thereof;
(o) 2-(2,4-dichlorophenoxy)-propionic acid and the salts thereof;
(p) a mixture of 2,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid and the salts thereof;
(q) 4-hydroxy-3,5-diiodobenzonitrile;
(r) 4-hydroxy-3,5-dibromobenzonitrile;
(s) 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide;
(t) 3,5-dibromo-4-hydroxybenzaldehyde-2,4-dinitro-phenyloxime;
(u) 2-(1-methyl-n-propyl)-4,6-dinitrophenylacetate;
and (v) 4,6-dinitro-2-t-butylphenol.
(a) 3-(4-chlorophenyl)-1-methyl-1-(1-methyl-prop-2-ynyl)-urea;
(b) 3-(4-chlorophenyl)-1-methyl-1-methoxyurea;
(c) 3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea;
(d) 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea;
(e) 1-benzthiazole-2-yl-1,3-dimethylurea;
(f) 3-(4-isopropylphenyl)-1,1-dimethylurea;
(g) 6-t-butyl-4-(2-methyl-propylideneimino)-3-methyl-mercapto-4,5-dihydro-1,2,4-triazine-5-one;
(h) isobutyl-2-[4-(4-chlorophenoxy)-phenoxy]-propionate;
(i) ethyl-2-(N-benzoyl-3,4-dichloroanilino)-propionate;
(j) 1,1-dimethyl-3,5-diphenylpyrazolium-methosulfate;
(k) 2-chloro-3-(4-chlorophenyl)-methylpropionate;
(l) methyl-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate;
(m) a mixture of 4-chloro-2-methylphenoxy acetic acid and 9-hydroxyfluorene-9-carboxylic acid and the salts thereof;
(n) 2-(4-chloro-2-methylphenoxy)-propionic acid and the salts thereof;
(o) 2-(2,4-dichlorophenoxy)-propionic acid and the salts thereof;
(p) a mixture of 2,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid and the salts thereof;
(q) 4-hydroxy-3,5-diiodobenzonitrile;
(r) 4-hydroxy-3,5-dibromobenzonitrile;
(s) 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide;
(t) 3,5-dibromo-4-hydroxybenzaldehyde-2,4-dinitro-phenyloxime;
(u) 2-(1-methyl-n-propyl)-4,6-dinitrophenylacetate;
and (v) 4,6-dinitro-2-t-butylphenol.
11. Compounds as claimed in claim 10 which comprises (i) a compound of formula I as defined in claim 1, and (ii) a mixture of the dimethylamine salt of 4-chloro-2-methylphenoxy acetic acid and the dimethylamine salt of 9-hydroxyfluorene-9-carboxylic acid.
12. Compounds as claimed in claim 10 which comprise (i) a compound of formula I as defined in claim 1, and (ii) a mixture of 2,4-dichlorophenoxy acetic acid and 4-chloro-2-methylphenoxy acetic acid (in salt form).
13. A process for the preparation of compounds of formula I as defined in claim 1, which comprises (a) for the preparation of compounds I wherein R
represents a hydrogen atom or one equivalent of an inorganic or organic cation, 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-4-hydroxypyridine into a compound of formula I in which R represents an equivalent of an inorganic or organic cation, or (b) for the preparation of compounds of formula I
wherein R represents the group -OC-R1, -OC-OR1, -OC-NR2R3 or -O2S-R4 in which R1, R2, R3 and R4 are as defined in claim 1, reacting 2-chloro-3,5-diiodo-4-hydroxypyridine with a compound of the formula:-R1-CO-X (II); R1O-CO-X (III); R2R3N-CO-X (IV); or R4-SO2-X (V) wherein R1, R2, R3 and R4 are as defined in claim 1 and X
represents an atom or group removable as an anion.
represents a hydrogen atom or one equivalent of an inorganic or organic cation, 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-4-hydroxypyridine into a compound of formula I in which R represents an equivalent of an inorganic or organic cation, or (b) for the preparation of compounds of formula I
wherein R represents the group -OC-R1, -OC-OR1, -OC-NR2R3 or -O2S-R4 in which R1, R2, R3 and R4 are as defined in claim 1, reacting 2-chloro-3,5-diiodo-4-hydroxypyridine with a compound of the formula:-R1-CO-X (II); R1O-CO-X (III); R2R3N-CO-X (IV); or R4-SO2-X (V) wherein R1, R2, R3 and R4 are as defined in claim 1 and X
represents an atom or group removable as an anion.
14. A process as claimed in claim 13 wherein the iodination is effected by the use of iodine chloride.
15. A process as claimed in claim 14 wherein the iodination is effected in the presence of acetic acid, aqueous hydrochloric acid or water.
16. A process as claimed in claim 14 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.
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 iodination is effected in the presence of water/ethanol.
20. A process as claimed in claim 13 wherein a compound of formula II, III, IV or V is used in which X represents a chlorine or bromine atom.
21. A process as claimed in claim 13 for the preparation of compounds of formula I as defined in claim 1 (in which R
represents the group R1-CO-) wherein a compound of formula II
is used in which X represents the group -O-CO-R1 (in which R1 is as defined in claim 1).
represents the group R1-CO-) wherein a compound of formula II
is used in which X represents the group -O-CO-R1 (in which R1 is as defined in claim 1).
22. A method for controlling undesired vegetation which comprises applying to the locus of said undesired vegetation an effective amount of a compound as claimed in claim 1 or a herb-icidal agent as defined in claim 9.
23. A method as claimed in claim 22 wherein from 0.03 to 1.0 kg/ha of the active ingredient is applied to the locus of said undesired vegetation.
24. A method as claimed in claim 22 wherein from 0.05 to 0.3 kg/ha of the active ingredient is applied to the locus of said undesired vegetation.
25. A method as claimed in any one of claims 22 to 24 wherein from 0.05 to 0.2 kg/ha of 2-chloro-3,5-diiodo-4-acetoxy pyridine is applied to the locus of said undesired vegetation.
26. A method as claimed in any one of claims 22 to 24 wherein from 0.1 to 6.0 kg/ha of the said further active ingred-ient is applied to the locus of said undesired vegetation.
27. A method as claimed in any one of claims 22 to 24 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 plants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2719904.8 | 1977-05-04 | ||
| DE19772719904 DE2719904A1 (en) | 1977-05-04 | 1977-05-04 | NEW PYRIDE DERIVATIVES, THEIR PRODUCTION AND USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1096383A true CA1096383A (en) | 1981-02-24 |
Family
ID=6007986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA302,519A Expired CA1096383A (en) | 1977-05-04 | 1978-05-03 | Pyridine derivatives, their production and use |
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 AT AT0295578A patent/AT364191B/en not_active IP Right Cessation
- 1978-04-25 YU YU00990/78A patent/YU99078A/en unknown
- 1978-04-27 TR TR20611A patent/TR20611A/en unknown
- 1978-04-28 AR AR271981A patent/AR222012A1/en active
- 1978-05-02 JP JP5326378A patent/JPS53137968A/en active Pending
- 1978-05-02 IL IL54625A patent/IL54625A/en unknown
- 1978-05-02 IT IT49163/78A patent/IT1103860B/en active
- 1978-05-02 CH CH476478A patent/CH638788A5/en not_active IP Right Cessation
- 1978-05-03 MX MX787057U patent/MX5292E/en unknown
- 1978-05-03 NL NL7804747A patent/NL7804747A/en not_active Application Discontinuation
- 1978-05-03 PL PL1978206550A patent/PL110684B1/en unknown
- 1978-05-03 AU AU35727/78A patent/AU518477B2/en not_active Expired
- 1978-05-03 ES ES469387A patent/ES469387A1/en not_active Expired
- 1978-05-03 NZ NZ187160A patent/NZ187160A/en unknown
- 1978-05-03 HU HU78CE1164A patent/HU182008B/en unknown
- 1978-05-03 IE IE893/78A patent/IE46876B1/en unknown
- 1978-05-03 LU LU79582A patent/LU79582A1/en unknown
- 1978-05-03 FR FR7813184A patent/FR2389607B1/fr not_active Expired
- 1978-05-03 CA CA302,519A patent/CA1096383A/en not_active Expired
- 1978-05-03 ZA ZA782544A patent/ZA782544B/en unknown
- 1978-05-03 BR BR7802751A patent/BR7802751A/en unknown
- 1978-05-03 GB GB17517/78A patent/GB1601609A/en not_active Expired
- 1978-05-03 SE SE7805138A patent/SE7805138L/en unknown
- 1978-05-03 SU SU782609553A patent/SU1047376A3/en active
- 1978-05-03 BE BE187389A patent/BE866699A/en not_active IP Right Cessation
- 1978-05-03 DK DK193478A patent/DK193478A/en unknown
- 1978-10-06 ES ES474005A patent/ES474005A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| PL206550A1 (en) | 1979-04-09 |
| BR7802751A (en) | 1979-04-10 |
| ZA782544B (en) | 1980-01-30 |
| ATA295578A (en) | 1981-02-15 |
| MX5292E (en) | 1983-06-06 |
| FR2389607B1 (en) | 1983-06-17 |
| NZ187160A (en) | 1981-03-16 |
| GR64825B (en) | 1980-06-03 |
| HU182008B (en) | 1983-12-28 |
| AU518477B2 (en) | 1981-10-01 |
| FR2389607A1 (en) | 1978-12-01 |
| ES469387A1 (en) | 1978-12-01 |
| IL54625A (en) | 1981-09-13 |
| LU79582A1 (en) | 1979-06-13 |
| PL110684B1 (en) | 1980-07-31 |
| SU1047376A3 (en) | 1983-10-07 |
| JPS53137968A (en) | 1978-12-01 |
| DK193478A (en) | 1978-11-05 |
| CH638788A5 (en) | 1983-10-14 |
| IT1103860B (en) | 1985-10-14 |
| IL54625A0 (en) | 1978-07-31 |
| AR222012A1 (en) | 1981-04-15 |
| GB1601609A (en) | 1981-11-04 |
| AU3572778A (en) | 1979-11-08 |
| IT7849163A0 (en) | 1978-05-02 |
| SE7805138L (en) | 1978-11-05 |
| BE866699A (en) | 1978-11-03 |
| NL7804747A (en) | 1978-11-07 |
| YU99078A (en) | 1983-01-21 |
| AT364191B (en) | 1981-09-25 |
| DE2719904A1 (en) | 1978-11-09 |
| IE780893L (en) | 1978-11-04 |
| IE46876B1 (en) | 1983-10-19 |
| ES474005A1 (en) | 1979-05-01 |
| TR20611A (en) | 1982-01-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |