SI7710977A8 - Process for making herbicide compound with lower risk for user - Google Patents

Description

Process for the preparation of new herbicidal compositions with reduced risk to the life of the user

Technical field of the invention

MPK: A 01 N 9/22; C 07 D 213/22

The technical field of the invention is chemical technology and agronomy, and specifically relates to a process for the preparation of new herbicidal compositions, with high efficiency and reduced risk to the life of the user.

A technical problem

There was a need to prepare herbicidal compositions in a technologically simple and advanced manner that would contain highly effective bipyridylium quaternary salts but would not be hazardous to the user when ingested, without compromising efficiency and yield.

The state of the art

In recent years, a wide variety of pesticides have been developed for agricultural use in the control of fungi, insects and weeds. While these substances are toxic to some life forms, when used with due care and in accordance with officially authorized modes of delivery, they are not toxic to human life. However, the exclamation point for efforts to use safe ways of implementation by pesticide practitioners leads to cases of pesticide abuse. A particularly dangerous practice in the use of liquid pesticides is for a person to place a small amount of concentrated pesticide in a household container as a bottle. The danger with this practice, of course, is that when the bottle is reached, the child or careless adult may drink the contents, which can have serious consequences.

Description of solution to a technical problem with implementation examples

However, we have now found that the above-mentioned problem is solved by the process of preparing new herbicidal compositions which are unsafe for the user when ingested with unchanged herbicidal efficacy because they immediately cause vomiting by combining the salt of the herbicidal bipyridylium quaternary cation and s-triazolo / 1,5-a / pyrimidine derivative of formula (I)

- 3 Ί in which R is an amine, alkylamine, phenylalkylamine, dialkylamine, ureidic, carboxyl, hydroxyalkyl or carbamoyl 2 group, R is an alkyl, cycloalkyl or alkenyl group, R1 is hydrogen, halogen, alkyl or hydroxyalkyl group, one of X and Y stands for oxo or thioxo radical and the other of X and Y stands for hydrogen or alkyl radical and, when X stands for oxo or thioxo radical, the nucleus contains a double bond between the carbon atoms in positions 6 and 7, and when Y stands for oxo or a thioxo radical, the nucleus containing a double bond between the carbon atoms in positions 5 and 6, or the base addition salt of the acid-group triazolo / 1,5-a / pyrimidine derivative defined above, or an acylated derivative thereof or a base addition salt thereof.

In the process of the invention, the salt of the herbicidal bipyridylium quaternary cation and the s-triazolo / 1,5-a / pyrimidine derivative of the formula are preferably combined)

wherein R is hydrogen, an alkyl radical of 1 to 4 carbon atoms or

A COOEt radical in which Et represents an ethyl group is R is an alkyl radical of 1 to 4 carbon atoms or an allyl radical and R is an alkyl radical of 1 to 4 carbon atoms, or an addition salt thereof. The ring structure of s-triazolo / 1,5-a / pyrimidine is numbered as follows:

1

3

The 5-oxo 4,5,5-dihydro-s-triazolo / 1,5-a / pyritic derivatives are particularly useful in the process:

6-methyl-4-N-propyl-2-n-propylamino2-amino-6-methyl-4-allyl-2-amino-4,6-di-n-propyl2-ethoxycarbonylamino-6-methyl-4-n-propyl- .

Particularly useful in the process of the invention is 2 amino- 6 -methyl-5-oxo-4-n-propyl-4,5-dihydro- with -triazolo/1,5-a/pyrimidine of the formula

(II) salts for use in the process of the invention have the formulas

+ \ /

CH ₂ CH ₂

- C * J n

right

n1 in which R and R, which may be the same or different, stand for alkyl radicals having 1 to 4 carbon atoms which may be substituted by hydroxyl, halogen, carboxyl, lower alkoxyl, lower alkylcarbonyl, lower alkoxycarbonyl, carbamoyl or N-lower alkylsubstituted carbamoyl, / X / ⁿ represents an anion and n is an integer from 1 to 4.

Particularly preferred herbicidal bipyridylium quaternary salts are the following:

1,1-dimethyl-4,4'-bipyridylium di (methylsulfate) (paraquatdimethosulfate)

1 _t 1'-ethylene-2,2'-bipyridylium dibromide (diquat-dibromide)

1,1'-dimethyl-4,4'-bipyridylium dichloride (paraquat dichloride) 1,1 '-di-2-hydroxyethyl-4,4'-bipyridylium dichloride

1- (2-hydroxyethyl-1'-methyl) -4,4'-bipyridylium dichloride 1,1'-di-carbamoylmethyl 1-4,4'-bipyridylium dichloride 1,1'-bis-N, N-dimethylcarbamoylmethyl-4 , 4'-bipyridylium dichloride 1,1'-dimethyl-4,4'-bipyridylium sulphate (paraquat sulphate)

1,1'-bis-N, N-diethylcarbamoylmethyl-4,4'-bipyridylium dichloride

1,1'-diacetonyl-4,4'-bipyridylium dichloride

1,1′-diethoxycarbonylmethyl-4,4′-bipyridylium dibromide.

The names in brackets for some of the compounds in the list above are accepted trivial names for these compounds. Paraquat is a trivial name for 1, 1 '-dimethyl-4,4'-bipyridylium cation. In the use of the compositions of the invention, bipyridylium cation is particularly preferred for paraquat. A particularly preferred anion / X / ⁿ 'is a chloride anion because it is suitable and economical, but any anion that gives a suitable water-soluble salt can be used if desired. The herbicidal effect is due only to the cation, and therefore the concentration of the composition of the herbicidal bipyridylium salt is often given in the form of a cation alone. The amount of the herbicidal bipyridylium quaternary salt present in the compositions of the invention is generally 1.0 to 99.9 wt. %.

In the process of the invention, a diluent may be added. The products may be solids, e.g. granules, or liquids, e.g. aqueous solutions.

In a preferred embodiment of the invention, a herbicidal composition comprising an aqueous solution of the above-defined salt of the herbicidal bipyridylium quaternary cation and a triazolo / 1,5-a / pyrimidine derivative is prepared. A preferred herbicidal bipyridylium quaternary cation is paraquat.

The amount of the herbicidal bipyridylium quaternary cation present in the aqueous solution is preferably 50 to 400 g per liter.

Preferably, a surfactant is also used in the process.

Surfactants may be cationic, nonionic or anionic. In general, when using the compositions of the invention, cationic and non-ionic surfactants are preferred over anionic surfactants because the latter may react unwantedly in the compositions with the bipyridylium quaternary salt. Examples of non-ionic surfactants useful in the process of the invention include the condensation products of ethylene oxide with alkylphenols, such as octylphenol, nonyl-

phenol and octylcresol. Other non-ionic agents are partial esters derived from long chain fatty acids and hexitol- anhydrides, e.g. sorbitan-monolaurate, condensing products of these ethylene oxide partial esters, and lecithins. Examples cationic

surfactants include quaternary salts and ethylene oxide condensates with amines, e.g. substances marketed under the trademarks Ethomeen, Ethoduomeen, Duoqad and

Arquad.

Particularly preferred surfactants are combinations of surfactants described in British Pat. 998 264 for use in the preparations of the herbicidal bipyridylium quaternary salts.

The preparation of triazolo-pyrimidines of formula I is described in British Pat. 1 234 635.

The emetic properties of the composition are primarily determined by the amount of triazolo-pyrimidine it contains. When deciding on

the most suitable amounts of triazolo-pyrimidine, which we use in any composition, we must consider efficiency triazolo- pyrimidine versus herbicide toxicity. Quantity triazolo- The pyrimidine to be included is preferably such that any

a sample of a composition containing a potential lethal dose of the herbicide contains enough triazolo-pyrimidine to give it an emetic effect. However, it is clear that neither the lethal doses nor the emetic doses can be directly measured in humans. We can only summarize them from animal data.

The process of the invention is carried out starting from 0, 1 to 5 wt. parts of triazolo-pyrimidine, e.g. of triazolo-pyrimidine of formula II, and 100 wt. parts of the herbicidal bipyridylium quaternary cation, e.g. paraquata. The amount of triazolo-pyrimidine used, e.g. triazolo-pyrimidine of formula II, 0.25 to 2.0 parts per 100 parts of the herbicidal bipyridylium quaternary cation, e.g. paraquata.

The concentrated aqueous preparations of the invention are corrosive. They should be handled with care to avoid eye or skin contamination and should not be allowed to come into contact with corroding metals prior to dilution.

In the process of the invention, dyes or pigments may also be used to give them a characteristic or distinctive color. Examples of such compositions are Monastral Blue BNV Paste and

Lissamine Turquoise VN 150.

An odorant agent may also be used in the process of the invention. Examples of such odorants are alkylpyridines as described in British Pat. 1 406 881, n-valeric acid and tetrahydrothiophene.

Optionally, triazolo-pyrimidines of formula I can be incorporated into thixotropic compositions of the herbicidal quaternary salts. In particular, the triazolo-pyrimidines of formula I may be incorporated into the preparations of the herbicidal bipyridylium quaternary salts described in our British patent no. 1 395 502. These preparations contain an aqueous solution of a herbicidal bipyridylium quaternary salt containing a gelling agent, e.g. finely divided silica or a combination of the xanthan gum sold under the Kelzan brand with sodium metaborate. Xanthan gum is a complex polysaccharide.

In the process of the invention, other herbicides may be used in addition to the herbicidal bipyridylium salt defined above. Examples of such herbicides are:

amides, e.g. N, N-diallyl chloroacetamide, 3,4-dichloropropionanilide, N- (3-chloro-4-methyl-phenyl) -2-methylpentamide, carbamates, e.g. isopropyl-N-phenylcarbamate, isopropyl-N- (3-chlorophenyl) -carbamate, 4-chloro-2-but-2-ynyl-N- (3-chlorophenyl) -carbamate, 2-chloroaryl-N, N-diethyl- dithiocarbamate, ureas / anilides, e.g. N, N'-di- (2,2,2-trichloro-1-hydroxy-ethyl) urea, 3,4-dichloroacetanilide, O-chloroisobutyranilide, οό-bromo3,4-dichloroacetanilide, 3,4-dichloroformanilide, 2- acetamido-3-chloro toluene, diazines, e.g. 3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H-1,3,5 thiadiazine, 5-bromo-3-isopropyl-6-methyluracil, 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-1,3,5-triazine.

The incorporation of triazolo-pyrimidine of formula I into the compositions of the invention has no significant adverse effect on the herbicidal efficacy of the compositions.

The invention is illustrated by the following examples:

EXAMPLE 1

This example illustrates the preparation of a composition containing 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine of formula II in aqueous solution.

Ingridients wt./vol% paraquate concentrate X a compound of formula II 0.05 water up to 100 ml

(where x gives 200 + 5 g / liter of paraquat cation)

Paraquat concentrate is a solution of paraquat dichloride containing 25 to 30 wt. % 1,1'-dimethyl-4,4'-bipyridylium cation. The quantity used was chosen to be obtained

a composition that contained 20 wt./vol% paraquat cation. The composition was prepared by combining the ingredients at shaking. EXAMPLE 2

This example illustrates the preparation of a composition containing triazolo-pyrimidine of formula II of the invention in aqueous solution. The composition contains the ingredients listed.

Ingridients wt./vol% paraquate concentrate X sodium metaborate 1.3 sodium benzoate 2.0 Lissapol NX 1.1

DS 4392 4.1

Silcolapse 5000 0.06 Compound of Formula II 0.05 Water to 100 ml (where x gives 200 + 5 g / liter paraquat cation)

Lissapol NX is a surfactant brand containing 7 to 8 moles of ethylene oxide and 1 mol of p-nonylphenol. DS 4392 is a code for a surfactant containing 1 mol of a mixture of amines derived from soy fatty acids with approximately 15 moles of ethylene oxide. Silcolapse is a trademark for a foaming agent containing a silicone derivative. The composition described above was prepared by combining the ingredients upon shaking.

EXAMPLE 3

This example illustrates the preparation of a composition comprising a gelling agent in addition to the triazolo-pyrimidine of formula II. The composition contains the ingredients listed.

Ingredients Amount in grams

paraquate concentrate X Kelzan 0,4 (added as 1% solution in water) sodium metaborate 0.014 Lissapol NX 1.1 DS 4392 4,1 a compound of formula II 0.05 Silcolapse 5000 0, 01

water up to 100 ml (where x gives 200 + 5 g / liter of paraquat cation)

The composition described above was prepared by combining the ingredients upon shaking, and when prepared, it was sufficiently fluid to be poured into containers. At the 15- to 20-minute condition, the composition formed a gel that, if not shaken vigorously, could not be poured.

EXAMPLE 4

This example shows a dry, granular, granular composition that is stable during storage and can be easily converted to an aqueous solution for use as a spray.

We formed a solution with a composition in which percentages are mass percentages.

paraquat dichloride 33.0

2-amino-6-methyl-5-oxo-4-n-propyl

4,5-dihydro-s-triazolo / 1,5-a / -pyrimidine 0.1 sodium metaborate 2.5 potassium phosphate 1.6

Lissapol NX 24.0 Water 38.8

100,0

310 g of the above solution was then placed in a thin stream of 690 g of dried magnesium sulfate contained in a sphere of HOBART C.E. dough mixer (HOBART is a trademark). The dry product obtained was then passaged through a granulation machine and finally shaken in a sieve that had a linear loop of 2.54 cm 30 loops to remove dust. The granules obtained had a size of at least 0.9 mm and had a dissolution rate of 150 seconds.

EXAMPLE 5

This example illustrates a composition of the invention containing 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine of formula II agent in aqueous solution.

Ingredients w / v% paraquate concentrate n-valeric acid compound of formula II

DS 4392

Silcolapse

Lissapol NX water x

1.0

0.05

4.0

0.01

1.0 to 100 ml (where x gives 200 g / liter of paraquat cation)

The composition described above was prepared by combining the ingredients upon shaking.

EXAMPLE 6

This example illustrates the preparation of a composition containing 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine of formula II in concentrated, colored , aqueous solution.

Ingredients w / v% concentrate

Synperonic

Synperonic paraquata

2.5

2.5

Nansa 1106 8.5

Monastral BNVS Paste 1.0 Pyridine Base 1.0 Compound of Formula II 0.05 Water to 100 ml (where x gives 200 g / liter of paraquat cation).

Synperonic and Nansa are trademarks. Synperonie 2 is a condensation product of a mixture of 1 equivalent of aliphatic alcohols with 67% alcohol with 13 carbon atoms and 33% alcohol with 15 carbon atoms with 2 ethylene oxide equivalents. Synperonic 16 is a condensation product of a mixture of 1 equivalent of aliphatic alcohols with 67% alcohol with 13 carbon atoms and an alcohol with 15 carbon atoms with 16 equivalents of ethylene oxide. Nansa 1106 is sodium dodecylbenzenesulfonate in which the dodecyl residue has a straight chain. The BNVS monastral paste is a dispersion containing 15% by weight of copper phthalocyanine pigment in water. The pyridine base is a mixture essentially of alkylpyridines.

EXAMPLE 7

This example shows the preparation of a composition containing

2-amino-6-methyl-5-oxo ~ 4-n-propyl-4,5,5-dihydro-s-triazolo / 1,5-a / pyrimidine of formula II in aqueous solution.

Ingredients w / v% diquat-dibromide x sodium molybdate 0, 18 potassium phosphate (as a mixture of dicalium hydrogen phosphate and potassium dihydrogen phosphate) 2.75 compound of formula II 0.05 water to 100 ml (where x gives 140 + 5 g / liter diquat cation)

Diquat's cation is 1, 1'-ethylene-2,2'-bipyridylium cation. The composition described above was prepared by combining the ingredients upon shaking and had a pH of 6.5 + 0.3.

EXAMPLE 8

This example illustrates the preparation of a composition containing 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine of formula II in aqueous solution.

Ingredients w / v% morphamquate dichloride x compound of formula II 0.05 water to 100 ml (where x gives 300 + 5 g / liter of morphamquate cation)

The morphamquat cation is 1,1'-bis (3,5-dimethylmorpholinocarbonylmethyl) -4,4'-bipyridylium cation. The composition described above was prepared by combining the ingredients upon shaking.

EXAMPLE 9

This example illustrates the preparation of a composition containing 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine of formula II in aqueous solution.

Ingredients wt./vol%

1,1'-bis (diethylcarbamoylmethyl) -4,4 'bipyridylium dichloride x

Tween 20 8.0 compound of Formula II 0.05 water to 100 ml (where χ gives 200 + 5 g / liter 1,1′-bis (diethylcarbamoylmethyl)

4,4 '-bipyridylium ion)

The composition described above was prepared by combining the ingredients upon shaking.

Tween is a trademark, Tween 20 is a condensation product of 1 mole of sorbitan monolaurate with 20 moles of ethylene oxide.

EXAMPLE 10

This example illustrates the preparation of a composition containing 2-n-propylamino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine in aqueous solution.

Ingredients w / v% paraquate concentrate x

2-n-propylamino-6-methyl-5-oxo-4-propyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine 0.05 water to 100 ml (where x gives 200 + 5 g / liter of paraquat cation)

EXAMPLE 11

This example illustrates the preparation of a composition containing 2 amino-5-oxo-4,6-di-n-propyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine in aqueous solution.

Ingredients w / v% paraquate concentrate x

2-amino-5-oxo-4,6-di-n-propyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine 0.05 water to 100 ml (where x gives 200 + 5 g / liter paraquat cation)

EXAMPLE 12

This example illustrates the preparation of a composition containing 2 ethoxycarbonylamino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-tri azolo / 1,5-a / pyrimidine in aqueous solution.

Ingredients w / v% paraquate concentrate x

2-ethoxycarbonylamino-6-methyl-5-oxo4-n-propyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine 0.05 water to 100 ml (where x gives 200 + 5 g / liter paraquat cation)

EXAMPLE 13

This example illustrates the preparation of a composition containing 2-amino-6-methyl-5-oxo-4-allyl-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine in aqueous solution.

Ingredients paraquate concentrate

2-amino-6-methyl-5-oxo-4-allyl-4,5-dihydros-triazolo / 1,5-a / pyrimidine water to w / v% x

0.05

100 ml (where x gives 200 + 5 g / liter of paraquat cation).

Claims (5)

PATENT APPLICATIONS A process for the preparation of a herbicidal composition with reduced risk to the life of the user, characterized in that the salt of the herbicidal bipyridylium quaternary cation is combined with the emetically usable amount of the s-triazolo / 1,5-a / pyrimidine derivative of the formula NHR '' N '' N in which R is hydrogen, an alkyl radical of 1 to 4 carbon atoms or 2 A COOEt radical in which Et represents an ethyl group, R is an alkyl 3 radical of 1 to 4 carbon atoms or an allyl radical and R is an alkyl radical of 1 to 4 carbon atoms, or an addition salt thereof in a ratio of 0.25 to 2.0 parts pyrimidine derivatives per 100 parts of the herbicidal bipyridylium quaternary cation under shaking and, if necessary, in the presence of a diluent or carrier. A process according to claim 1, characterized in that a compound of the formula ^£ Ζ7Χ-7 n + is used as the salt of the herbicidal bipyridylium quaternary cation R-N 2ΓΧ.7 n20 1 in which R and R, which may be the same or different, stand for alkyl radicals having 1 to 4 carbon atoms which may be substituted by hydroxyl, halogen, carboxyl, lower alkoxyl, lower alkylcarbonyl, lower alkoxycarbonyl, carbamoyl, or N- lower alkylsubstituted carbamoyl, / X / ^n_ represents an anion and n is an integer from 1 to 4. A process according to any one of claims 1 and 2, characterized in that a compound of the formula wherein X is an anion is used as a salt of the herbicidal bipyridylium quaternary cation. Process according to any one of claims 1 to 3, characterized in that the pyrimidine derivative is selected from the group consisting of 6-methyl-4-n-propyl-2-n-propylamino-5-oxo-4,5-dihydro-1-triazolo / 1,5-a / pyrimidine, 2-amino-6-methyl-4-allyl-5-oxo-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine, 2-amino-4,6-di-n-propyl-5-oxo-4,5-dihydro-s-triazolo / 1,5-a / pyrimidine, 2-ethoxycarbonylamino-6-methyl-4-n-propyl-5-oxo-4,5-dihydro-striazolo / 1,5-a / pyrimidine and 2-amino-6-methyl-5-oxo-4-n-propyl-4,5-dihydro-s-triazolo- [1,5-a] pyrimidine. Method according to any one of the preceding claims, characterized in that the diluent or carrier is water, optionally mixed with a surfactant, an odorant or a colorant or pigment.