FI58711C - HERBICIDKOMPOSITIONER - Google Patents

Description

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Patent- och regicterttyrelaen 'Amakan utitgd och uti. «KrtH« n public · nd 31. i <^. συ (32) (33) (31) Pyy4 «* y« resumes »—B« | ird priority 15. OU. 76 19 · 08.76 England-England (GB) 1558U / 76 34589/76 (71) Imperial Chemical Industries Limited, Imperial Chemical House, Mill Bank, London SW1, England-England (GB) (72) George Edward Davies, Wilmslow, Cheshire, David Mackie Foulkes, Henley-on-Thames, Oxon, England-England (GB) (74) Oy Kolster Ab (5U) Herbicidal Compositions - Herbicidal Compositions This invention relates to herbicidal compositions comprising as active ingredient a herbicidal bipyridyl quaternary salt.

Over the years, a large number of pesticides have been developed for agricultural use against fungicides, insect pests and weeds. Although these substances are necessarily toxic to certain life forms, they do not pose a risk to human life when used with due care and in accordance with the use laws approved by the public authorities. However, despite attempts to get people handling pesticides to adopt safe habits, there are cases of pesticide misuse. One very dangerous practice in the case of liquid pesticides is the user's way of transferring a small amount of a concentrated pesticide to a household container, such as a soft drink bottle, for home use. The danger associated with this practice is, of course, that a child or careless adult who, in the event of a bottle, could swallow the contents with potentially serious consequences.

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We have now identified the possibility of reducing the likelihood of serious consequences of such an accidental ingestion by causing vomiting. This can in some cases lead to the rapid elimination of the pesticide mixture from the stomach and digestive organs before the body has been able to digest lethal amounts of the pesticide. in the Coalition produces a mixture which, if swallowed, tends to cause vomiting and then the elimination of the mixture.

According to the invention there is provided a herbicidal mixture having reduced health risks, consisting of a salt of a herbicidal bipyridyl quaternary cation and an s-triazolo-1,5-a-pyrimidine derivative of formula (I):

Y

p3 JL

l2 (U

and wherein R 1 is amino, alkylamino, phenylalkylamino, dialkylamino, ureide, carboxyl, hydroxyalkyl or carboyl-2. 3 groups; R is an alkyl, cycloalkyl or alkenyl group; R is hydrogen or halogen or an alkyl or hydroxyalkyl group; one of X and Y represents an oxy or thio radical and the other of X and Y represents a hydrogen or alkyl radical and when X represents an oxy or thio radical the core contains a double bond between the carbon atoms of positions 6 and 7 and Y means an oxy or thio radical the core contains a double bond between positions 6 and 7 of the carbon atoms and when Y represents an oxy or thioxy radical the ring contains a double bond between positions 5 and 6; or a base addition salt of a triazolopyrimidine derivative as defined above containing an acidic group; or an acylated derivative or base addition salt thereof.

Preferably, the invention provides a herbicidal composition having reduced health hazards consisting of a herbicidal bipyridyl quaternary cation and the formula 3,58711

I y — NHRX

Salt of the s-triazolo [1,5-b] pyrimidine derivative according to CT '' 'R2 R2 ... wherein R is hydrogen, a C1-4 alkyl radical or a COOEt radical, R is 1_H ... 3.

A C 1-4 alkyl radical or an allyl radical 3a R is a C 1-4 alkyl radical; and its addition salts. The structure of the S-triazolo [1,5-a] pyrimidine ring is numbered as follows: 7 1 6 1/2 4 3

Preferred 5-oxo-4,5-dihydro-s-trihydro-s-triazolo [1,5-b] pyrimidine derivatives for use in the practice of the invention are: 6-methyl-4-n-propyl-2-n-propylamino; 2-Amino-6-methyl-4-allyl-2-amino-4,6-di-n-propyl-2-ethoxycarbonylamino-6-methyl-4-n-propyl.

Particularly useful triazolopyrimidine for use in the compositions of the invention is 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo [1,5-b] pyrimidine (II).

ch3V ^ N ^ Na I y-NH2 n-Pr (II) 5871 1

Preferred herbicidal bipyridyl quaternary melts for use in the compositions of the invention are the salts of the following formulas: wherein R and R 1, which may be the same, are R + R 2 R 2 R 2 or various alkyl radicals having 1 to 4 carbon atoms which may be substituted by hydroxyl, halogen, carboxyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, carbamoyl or N-substituted by a carbamoyl group; integer 1-4.

Particularly preferred herbicidal bipyridyl quaternary salts are listed below: 1,1-dimethyl-4,4'-bipyridyl di (methyl sulfate) (paraquat dimethosulfate) 1,1'-ethylene-2,2'-bipyridyl dibromide (diquat dibromide) 1.1 '-dimethyl-4,4'-bipyridyl dichloride (paraquat dichloride) 1,1'-di-2-hydroxyethyl-4,4'-bipyridyl dichloride 1- (2-hydroxyethyl-4,4'-bipyridyl dichloride 1,1'-di- carbamoylmethyl 4,4'-bipyridyl dichloride 1,1'-bis-N, N-dimethylcarbamoylmethyl-4,4'-bipyridyl dichloride 1,1'-dimethyl-4,4'-bipyridyl sulfate (paraquat sulfate) 1,1'-bis- N, N-diethylcarbamoylmethyl-4,4'-bipyridyl dichloride 1,1'-diacetonyl-4,4'-bipyridyl dichloride 1,1'-diethoxycarbonylmethyl-4,4'-bipyridyl dibromide.

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The names next to some of the compounds listed above in parentheses are the accepted generic names for these compounds. Thus, "paraquat" is the trivial name of 1,1'-dimethyl-4,4'-bipyridyl cation. Paraquat is a highly preferred bipyridyl cation for use in the compositions of the invention. A highly preferred anion is the chloride anion, for convenience and economy, but any anion that produces an easily water-soluble salt can be used if desired. The herbicidal effect is due only to the cation and therefore the concentration of the bipyridyl salt mixture in the herbicide has been repeatedly given based only on the cation. The amount of herbicidal bipyridyl quaternary salt used in the sweet compositions of the invention is generally between 1.0 and 99.9% by weight.

The compositions of the invention may contain a binder or diluent and may be solids, e.g. granules, or liquids, e.g. aqueous solutions.

In a preferred light, the invention provides a concentrated herbicidal mixture of an aqueous solution of a herbicidal bipyridyl quaternary cation and a triazolo-pyrimidine salt as defined above. Preferably, the herbicidal bipyridyl quaternary cation is paraquat.

The amount of herbicidal bipyridyl quaternary cation present in the aqueous solution is preferably between 50 g and 400 g per liter.

Preferably, the mixture also contains a surfactant.

Surfactants can be cationic, nonionic or anionic. In general, cationic and nonionic surfactants are preferred over anionic surfactants for use in the compositions of the invention because the latter can react adversely with the bipyridyl quaternary salt in the compositions. Examples of nonionic surfactants for use in the compositions of the invention include e.g. condensation products of ethylene oxide and alkylphenols such as octylphenol, nonylphenol and octylcresol. Other nonionics include partial esters derived from long chain fatty acids and hexitol hydrides, e.g. sorbitan monolaurate; condensation products of said partial esters and ethylene oxide; and lecithins. Examples of cationic surfactants are e.g. quaternary salts and condensation products of ethylene oxide and amines, e.g. substances sold under the trade name "Ethomeen", Ethoduomeen ", 6 58711" Douquad "and" Arquad ".

Particularly preferred surfactants are the combinations of surfactants described in GB Patent No. 998,264 for use in herbicidal bipyridyl quaternary salt preparations.

The preparation of triazolo-pyrimidines (I) is described in GB Pat. 1234635, which description is incorporated herein by reference.

The emetic properties of a mixture are mainly determined by the amount of triazolo-pyrimidine it contains. The effectiveness of the triazolo-pyrimidine derivative in relation to the toxicity of the herbicide must be taken into account in selecting the most suitable amounts of triazolo-pyrimidine for use in any mixture. The amount of triazolo-pyrimidine to be included is preferably such that any sample of the mixture containing a potentially lethal amount of herbicide contains sufficient triazolo-pyrimidine to produce an emetic effect. However, clearly lethal amounts and not emetic amounts can be directly measured in humans; they can only be deduced from animal test data.

The compositions according to the invention preferably contain 0.1 to 5 parts by weight of triazolo-pyrimidine (e.g. triazolo-pyrimidine II) per 100 herbicidal bipyridyl quaternary cationic parts (e.g. paraquat). The concentrated preparations according to the invention are corrosive. They should be handled with care to prevent splashes in the eyes or on the skin and should not be allowed to come into contact with corrosive metals before dilution.

The compositions of the invention may also contain colored dye or pigment compounds to give them a characteristic or distinctive color. Examples of such compounds are "Monastral Blue BNV Paste" and "Lissamine Turquoise VN 150".

The compositions of the invention may also contain a fragrance. Examples of such fragrances are: the alkylpyridines described in GB Pat. 1406881 (the description of which is incorporated herein by reference): n-valeric acid; and tetrahydro-thiophene.

If desired, the triazolo-pyrimidines (I) can be incorporated into thixotropic preparations of herbicidal quaternary salts. In particular, the triazolo-pyrimidines (I) can be incorporated in our U.S. Pat. 1395502, which is incorporated herein by reference, for bipyridyl quaternary salt preparations of the herbicide described herein. These preparations contain an aqueous solution of the bipyridyl quaternary salt of the herbicide containing a gelling agent, e.g. finely divided silicic acid, or a combination of xanthan gum and sodium metaborate sold under the tradename "Kelza". Xanthan gum is a complex polysaccharide.

The compositions of the invention may also contain a herbicide other than the herbicidal bipyridyl quaternary salt as defined above. Examples of miscellaneous herbicides are:

Amides (e.g. N, N-diallylchloroacetamide, 3,4-dichloropropionanilide, N- (3-chloro-4-methylphenyl) -2-methylpentamide).

Carbamates (e.g. isopropyl N-phenylcarbamate, isopropyl N- (3-chlorophenyl) carbamate, 4-chloro-2-but-2-ynyl-N- (3-chlorophenyl) -4-carbamate, 2-chloroallyl) n, n-diethyl-carbamate ditiokarba).

Urea / anilides (e.g. N, N'-di- (2,2,2-trichloro-1-hydroxyethyl) urea, 3,4-dichloroacetanilide, O-chloroisobutyranilide, o (_-bromo-3,4) -dichloroacetanilide, 3,4-dichloroformanilide, 2-acetamido-3-chlorotoluene) Diazines (e.g. 3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H-1,3,5- thiadiazine, 5-bromo-3-isopropyl-6-methyluracil-1,5-amino-4-chloro-2-phenyl-3-pyridazone, 1,2,3,6-tetrahydro-3,6-dioxopyridazine).

Triazines (e.g. 2-chloro-4,6-bisethylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-chloro-4,6-bisisopropylamino-1,3,5-triazine, 4-ethylamino-6-isopropylamino-2-methoxy-1,3,5-triazine, 4,6-bisisopropylamino-2-methoxy- l, 3,5-triazine).

The inclusion of triazolo-pyrimidine (X) in the compositions according to the invention does not have a significant reversal effect on the herbicidal activity of the compositions. The following examples illustrate this invention.

Example 1 This example illustrates a mixture of the invention containing 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo [1,5-a] pyrimidine (II) in aqueous solution.

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Ingredients% w / v.

Paraquat concentrate x (II) 0,05 water ad 100 ml (of which x gives 200 to 5 g / liter of paraquat cation.)

The paraquat concentrate is a solution of paraquat dichloride containing 25% to 30% by weight of 1,1'-dimethyl-4,4 * -bipyridyl cation. The amount used was selected to obtain a mixture containing 20% w / v paraquat cation. The mixture was prepared simply by mixing the ingredients together.

Example 2 This example illustrates a mixture of the invention containing triazolo-pyrimidine (II) in aqueous solution. The mixture contains the following ingredients.

Ingredients% w / v.

paraquat concentrate x sodium metaborate 1.3 sodium benzoate 2.0

Lissapol NX 1.1 DS 4392 4.1

Silcolapse 5000 0.06 (II) ad 100 ml (of which x gives 200-5 g / liter of paraquat cation) "Lissapol" NX is the trade name of the surfactant, which is 7-8 parts by weight of ethylene oxide and 1 molar part of p-nonylphenol condensate.

DS 4392 is the surfactant code number which is a condensate of soybean fatty acid derivative amine mixtures and about 15 mole parts of ethylene oxide.

"Silcolapse" is the trade name of an antifoam containing a silicone derivative.

The mixture described above was prepared simply by mixing the ingredients together.

Example 3 This example illustrates a mixture according to the invention which contains a gelling agent in addition to triazolo-pyrimidine (II). The mixture contains the following ingredients.

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Ingredients Amount in grams paraquat concentrate x "Kelzan" 0.4 · (added as 1% aqueous solution) sodium metaborate 0.014

Lissapol NX 1.1 DS 4392 4.1 (II) 0.05

Silcolapse 5000 0.01 water ad 100 ml (where x gives 200 - 5 g / liter of paraquat ion)

The mixture described above was prepared simply by mixing the ingredients together and was prepared sufficiently fluid to be poured into containers. After standing for 15-20 minutes, the mixture formed a gel and could not be poured without stirring vigorously first.

.Example 4 This example illustrates a dry, free-flowing, granular mixture that is both stable on storage and easily converted to an aqueous solution for use by spraying.

A solution was prepared having the following composition in percentages by weight, paraquat dichloride 33.0 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo [1,5-b] pyramidine (II) 0.1 sodium metaborate 2.5 potassium phosphate 1.6

Lissapol NX 24.0 water 38.8 100 310 g of the above solution was then added in a thin stream to 690 g of dried magnesium sulfate which was HOBART C.E.

In a bowl of 100 dough mixers (“HOBART” is the trade name), the resulting product, which was dry, was then passed through a crusher and finally mixed in a 30 mesh linear inch screen to remove dust with a grain size of at least 0.9 mm and a dissolution rate of 150 seconds.

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Example 5 This example illustrates a mixture of the invention containing 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo-A, 5-7,7-pyrimidine (II) and a fragrance in aqueous solution.

Ingredients% w / v.

paraquat concentrate x n-valeric acid 1.0 II 0.05 DS 4 392 4, 0

Silcolapse 0.01

Lissapol NX 1.0 water ad 100 ml (where x gives 200 g / l paraquat ion).

The mixture described above was prepared simply by mixing the ingredients together.

Example 6 This example illustrates a mixture of the invention containing 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo [1,5-a] pyrimidine (II) in a thickened, colored aqueous solution.

Ingredients% w / v.

paraquat concentrate x

Synperonic 2 2.5

Synperonic 16 2.5

Nansa 1106 8.5

Monastral BNVS Paste 1.0

Pyridine base 1.0 l 0.05 water ad 100 ml (where x gives 200 g / l paraquat ion).

"Synperonic" and "Nansa" are trade names. Synperonic 2 is a condensation product of 67% C13 and 33% aliphatic alcohols and 2 equivalents of ethylene oxide. Synperonic 16 is a condensation product of 67% C13 and 33% C 1-4 aliphatic alcohols and 16 equivalents of ethylene oxide. Nansa 1106 is sodium dodecyl (mainly C 1-2 straight chain) benzenesulfonate. Monastral BNVS Paste is a dispersion of 15% w / v. copper phthalocyanine pigment in water. The pyridine base is mainly a mixture of alkylpyridines.

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Example 7 This example illustrates a mixture of the invention containing 2-amino-6-methyl-5-oxo * -4-n-propyl-4,5-dihydro-s-triazolo {1,5-a] pyrimidine (II) in aqueous solution. .

Ingredients,% w / v.

Diquat dibromide x sodium molybdate 0.18 potassium phosphate (as a mixture of dipotassium hydrogen phosphate and potassium hydrogen phosphate) 2.75 (II) 0.05 water ad 100 ml (where x gives 14-0-5 g / l diquat ion).

The fashion ion is 1,1 * -ethylene-2,21-bipyridyl cation. The mixture described above was prepared simply by mixing the ingredients together and had a pH of 6.5 to 0.3.

Example 8 This example illustrates a mixture of the invention containing 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo, 5-3'-pyrimidine (II) in aqueous solution.

Ingredients% w / v.

morphamquat dichloride x II 0.05 water ad 100 ml (where x gives 300-5 g / l morphamquat ion).

The morphamquat ion is 1,1'-bis (3,5-dimethylmorpholinocarbonylmethyl) -4,4'-bipyridyl ion. The mixture described above was prepared simply by mixing the ingredients together.

Example 9 This example illustrates a mixture of the invention containing 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo (1,5-section) pyrimidine (II) in aqueous solution.

Ingredients% w / v.

1,1'-Bis (diethylcarbamoylmethyl) -4,4'-bipyridyl dichloride x

Tween 20 8 (II) 0.05 water ad 100 ml 12 5871 l (where x gives 200-5 g / l 1,1'-bis (diethylcarbamoylmethyl.i) -4,4'-bipyridyl ion). The mixture described herein was prepared simply by mixing the ingredients together.

"Tween" is a trade name. Tween 20 is a condensation product of one mole of sorbitan monolaurate and 20 moles of ethylene oxide.

Example 10 This example illustrates a mixture of the invention containing 2-n-propylamino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo [1,5-a] pyridine. ves il solution.

Ingredients% w / v.

paraquat concentrate x 2-n-propylamino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triat-Solo {1,5-a.7 pyramidine 0.05 water ad 100 ml ( where x gives 200 + 5 g / l paraquat cation).

Example 11 This example illustrates a mixture of the invention containing 2-amino-5-oxo-4,6-di-n-propyl-4,5-dihydro-s-triazolo [1,2-a] pyrimidine in aqueous solution.

Ingredients% w / v.

paraquat concentrate x 2-amino-5-oxo-4,6-di-n-propyl-4,5-dihydro-s-triazolo [1,5-a] pyrimidine 0.05 water ad 100 ml (where x gives 200-5 g / 1 paraquat cation).

Example 12 This example illustrates a mixture of the invention containing 2-ethoxycarbonylamino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triacat Solo (1,5-a) pyrimidine in aqueous solution .

Ingredients% w / v.

paraquat concentrate x 2-ethoxycarbonylamino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo [1,5] pyrimidine 0.05 water ad 100 ml (where x gives 200-5 g / 1 paraquat cation).

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Example 13 This example illustrates a mixture according to the invention containing 2-amino-6-methyl-5-oxo-4-yl-over-4,5-dihydro-s-triazines Solo - (\ pyrimidine in aqueous solution.

Ingredients% w / v.

paraquat concentrate x 2-amino-6-methyl-5-oxo-4-allyl-4,5-dihydro-s-triazolo [1,5-b] pyramidine 0.05 water ad 100 ml.

Claims (2)

14 5871 1 Claims. A herbicidal mixture with reduced health hazards, characterized in that it contains a salt of a herbicidal bipyridyl quaternary cation and an s-triazolovfl, 5-a7pyrimidine of the formula R3 .. 1 1 L / nhr i * in which 1 ... 2 R is hydrogen or a C 1-6 alkyl radical, or a COOEt radical; R is 1 ~ 4. 3 C 1-6 alkyl radical or allyl radical; 3a a R is a C 1-1 alkyl radical; and wherein the salt of the herbicidal cation is a compound of formula 0-0 "" NN + \ / + CH2CH2 or R ~ ν3 * -C_yN "R1" n "wherein R and R3" which may be the same or different, represent 1-4 carbon atoms alkyl radicals, i.e. 5,871 l which may be substituted by hydroxyl, halogen, carboxyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, carbamoyl or N-substituted carbamoyl group; (Yjn represents an anion and n is an integer from 1 to 4; said mixture may optionally contain a diluent or carrier and may optionally contain a surfactant. A mixture according to claim 1, characterized in that the herbicidal bipyridyl cation is a y-NCh3 A compound according to ZTx_7 n "wherein (X) n is an anion and n is an integer from 1 to 3 and wherein s-triazolo [1,5-a] pyramidine is 2-amino-6-methyl-5-oxo-4-n- propyl-4,5-dihydro-s-triazolo [1,5-b] pyramidin. A herbicidal composition with a reducing risk, applied to a mixture of salt and a herbicidal quaternary bipyridylium cation and to a s-triazolo-5,5-pyrimide: 2 R 2 represents a C 1-6 alkyl radical or a C 1-6 alkyl radical, or a COOEt radical; o X 4 · 3, R 2 is a C 1-4 alkyl radical or an allyl radical; and R is en-alkyl; och color saltet of a herbicidal cation in the form of a mixture EfjL-0 + \ / + ch2ch2 or a color R och R ^, a fatty residue of an alkyl radical, a star of an alkyl radical of 1 to 4 cholaters hydroxyl,