WO2008140338A1 - New ionic pairs with (4-chloro-2-methylphenoxy)acetate and their syntheses - Google Patents
New ionic pairs with (4-chloro-2-methylphenoxy)acetate and their syntheses Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers 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
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/14—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to a carbon atom of a six-membered aromatic ring
- C07C217/16—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to a carbon atom of a six-membered aromatic ring the six-membered aromatic ring or condensed ring system containing that ring not being further substituted
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
- C07C59/70—Ethers of hydroxy-acetic acid, e.g. substitutes on the ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
Definitions
- Herbs are serious problems not only in agricultural, garden and forest areas, but also in non-agriculture areas like squares, road sides, railways, water streams, and recreation areas.
- the economical loss due to presence of herbs influence especially the quality and level of crops like cereal, corn, sugar beet, vegetables, and fruits. It has been estimated that herbs reduce the cereal crops in temperate climate zone at the level of 10%, despite of available ways of reduction of herb grow.
- One of the first organic compounds which were applied for reduction herb grow were derivatives of (4-chloro-2-methylphenoxy) acetic acid, known under the acronym MCPA.
- That class of compounds was applied in agriculture at the fourties of the XX century and is still widely used, especially in cereal cultivation. According to current survey of the chemical factors influencing the plant grow in the countries - members of EU perfomed in order to evaluate the possible negative influence of those factors on human, animal life and generally the environment, the MCPA was admitted as herbicide used in EU.
- MCPA belongs to the class of herbicides which control the grow. It distributes fast in plant and deposits in meristematic zones. It penetrates through leafs and partially through roots. It is used as applied for leafs mostly for spring and winter cereals, seeding grass, flax, potato, as well as in gardening and lawn.
- the herbs sensitive to this herbicide are: common fumitory (Fumaria officinalis), charlock mustard (Sinapis arvensis), buttercup (Ranunculus arvensis), fat-hen (Chenopodium album), scarlet pimpernel (Anagalis arvensis), corn poppy (Papaver rhoeas), corn mint (Mentha arvensis), common hemp-nettle (Galeopsis tetrahit), wild radish (Raphanus raphanistrum), corn spurrey (Spergula arvensis), shephard's purse (Capsella bursa pastoris), field pennycress (Thlaspi arvensis), sun spurge (Euphorbia heliscopia). Moreover, this herbicide is one of the few retarding the grow of horsetail (Equisetum arvensis).
- This herbicide is soluble in water at the level up to 734 mg/dm 3 .
- K means ammonium cation of the formula 2 or 3 or 4 or 5 or 6, or pyridinium cation of the formula 7, or imidazolium cation of formula 8, or morpholinium cation of the formula 9, or piperidinium cation of the formula 10, or 8- hydroxyquinolinium cation of the formula 11, or pyrazolium cation of the formula 12, or 2-chloroethylmethylammonium cation of the formula 13, or pyrolidinium cation of the formula 14, where R means alkyl linear chain group containing 1 to 18 carbon atoms or mixture of linear alkyl chains from 1 to 20 carbon atoms (common names cocalkyl or hydrogenated tallowalkyl) or polyoxyethylene chain.
- K means ammonium cation of the formula 2 or 3 or 4 or 5 or 6, or pyridinium cation of the formula 7, or imidazolium cation of formula 8, or morpholinium cation of the formula 9, or piperidinium cation of the formula 10, or 8-hydroxyquinolinium cation of the formula 11, or pyrazolium cation of the formula 12, or 2-chloroethylmethylammonium cation of the formula 13, or pyrolidinium cation of the formula 14, where R means alkyl linear chain group containing 1 to 18 carbon atoms or mixture of linear alkyl chains from 1 to 20 carbon atoms (common names cocalkyl or hydrogenated tallowalkyl) or polyoxyethylene chain, based on the exchange reaction between chloride or bromide of K cation of specified formula 1-14 with (4-chloro-2-
- the herbicide activity of new ionic pair is due to the presence of (4-chloro-2- methylphenoxy)acetate; moreover the new ionic pairs posses additional advantageous features, i.e.: they are ionic and hence non volatile; their vapour pressure at ambient temperature is undetectable.
- the ionic pairs can be rendered hydrophobic or hydrophilic, depending on the kind of cation used, - they are thermally and chemically resistant and reveal the tendency to form glass phase below OC, they do not react with metal ions due to the absence of free carboxylate group and do not absorb in soil, they have limited tendency to deposit in natural environment and therefore are more environmentally friendly than parent herbicide - MCPA, new ionic pairs can be classified as ionic liquids according to the low melting points and therefore they can be named as herbicide ionic liquids, apart from herbicide activity the salts posses also the antibacterial and antifungicidal activity due to the presence of large cation, the obtained ionic pairs have cationic surfactants activity due to the presence of the cation with one or more long chain alkyl substituents, they reveal antielectrostatic properties due to their ionic structure and the presence of alkyl substituents.
- the physicochemical parameters were obtained by DSC as: glass temperature 223K, crystallization temperature 246K and melting temperature 29 IK.
- Example IV Syntehsis of 1-dodecylpyridinium (4-chloro-2-methylphenoxy)acetate - [C 12PIR][MCPA].
- Przvklad XI Synthesis of 3,5-diphenyl-l,2-dimethylpyrazolium (4-chloro-2- methylphenoxy)acetate
- trioctylmethylammonium chloride commercial Aliquat 336
- 0.11 mole of (4-chloro-2-methylphenoxy)acetic acid and 0.11 mole of sodium hydroxide were dissolved in 100 cm 3 DMSO.
- the mixture was heated at 373K for 12 hours.
- 250 cm 3 distilled water was added to cool solution.
- Organic phase was separated and washed with distilled water.
- the product was dried under vacuum to get trioctylmethylammonium (4-chloro-2-methylphenoxy)acetate .
- Biological activity of new ionic pairs was confirmed by separate studies as follows. The studies were performed on white mustard (Sinapis alba L.) in growth cell with controlled condition. The seeds of white mustard were seeded in compartments filled with soil to the level of 1 cm from bottom. After formation of leafs the number of plants were reduced to four in every compartment. After the third leaf was formed, the plants were treated with tested liquid containing studied ionic paits using TeeJet XR 11 002VP, moving sprinkler over the plants with the speed of 3.1 m/s. Technical parameters of sprinkling were as follows:
- the compounds containing ion pairs were dissolved in water/ethanol (1 :2 v/v) at the 0.001 molar concentration.
- the reference herbicide was Herbicide X containing 300 g MCPA as sodium nad potassium salts in 1 liter of solution. After the sprinkling was done the compartments containing tested plant were placed back in grow cell at 190K ( ⁇ 2) and air humidity 50%. The daylight illumination time was 16 hours per day. After next two weeks the plants were cut off straight over the ground level and weighed with the 0.1 g accuracy. The procedure was repeated 4 times at fully statistical mode. Based upon obtained results the mass loss of freshly cut plants was compared with standard (plants not sprayed with tested compounds).
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Abstract
New ionic pairs contain (4-chloro-2-methylphenoxy)acetate anion of the general formula 1, in which K means ammonium cation of the formula 2 or 3 or 4 or 5 or 6, or pyridinium cation of the formula 7, or imidazolium cation of formula 8, or morpholinium cation of the formula 9, or piperidinium cation of the formula 10, or 8-hydroxyquinolinium cation of the formula 11, or pyrazolium cation of the formula 12, or 2-chloroethylmethylammonium cation of the formula 13, or pyrolidinium cation of the formula 14, where R means alkyl linear chain group containing 1 to 18 carbon atoms or mixture of linear alkyl chains from 1 to 20 carbon atoms (common names cocalkyl or hydrogenated tallowalkyl) or polyoxyethylene chain. New compounds are obtained in the exchange reaction between chloride or bromide salts of K cation of specified formula and (4-chloro-2-methylphenoxy)acetic acid in presence of sodium or potassium salts used at molar ratio 1 : (from 0.8 to 3) : (from 0.8 to 4) at temperature from 273 to 373K in aqueous medium or organic solvent, followed by product isolation.
Description
New ionic pairs with (4-chloro-2-methylphenoxy)acetate and their syntheses
The matter of finding are new ionic pairs containing (4-chloro- 2-methylphenoxy)acetate and their syntheses. New compounds are useful active components for obtaining herbicides.
Herbs are serious problems not only in agricultural, garden and forest areas, but also in non-agriculture areas like squares, road sides, railways, water streams, and recreation areas. The economical loss due to presence of herbs influence especially the quality and level of crops like cereal, corn, sugar beet, vegetables, and fruits. It has been estimated that herbs reduce the cereal crops in temperate climate zone at the level of 10%, despite of available ways of reduction of herb grow.
The most efficient and most spread method of herb reduction - or, as it is called recently - the method of herb grow control, is the use of chemical compounds called herbicides. One of the first organic compounds which were applied for reduction herb grow were derivatives of (4-chloro-2-methylphenoxy) acetic acid, known under the acronym MCPA.
That class of compounds was applied in agriculture at the fourties of the XX century and is still widely used, especially in cereal cultivation. According to current survey of the chemical factors influencing the plant grow in the countries - members of EU perfomed in order to evaluate the possible negative influence of those factors on human, animal life and generally the environment, the MCPA was admitted as herbicide used in EU.
One of the advantages of MCPS is very limited possibility of acquired resistance of herbs against this herbicide, which might be the serious problem for crop protection
against herbs. The MCPA is used in Poland also due to relatively low cost in comparison with other herbicides.
MCPA belongs to the class of herbicides which control the grow. It distributes fast in plant and deposits in meristematic zones. It penetrates through leafs and partially through roots. It is used as applied for leafs mostly for spring and winter cereals, seeding grass, flax, potato, as well as in gardening and lawn. The herbs sensitive to this herbicide are: common fumitory (Fumaria officinalis), charlock mustard (Sinapis arvensis), buttercup (Ranunculus arvensis), fat-hen (Chenopodium album), scarlet pimpernel (Anagalis arvensis), corn poppy (Papaver rhoeas), corn mint (Mentha arvensis), common hemp-nettle (Galeopsis tetrahit), wild radish (Raphanus raphanistrum), corn spurrey (Spergula arvensis), shephard's purse (Capsella bursa pastoris), field pennycress (Thlaspi arvensis), sun spurge (Euphorbia heliscopia). Moreover, this herbicide is one of the few retarding the grow of horsetail (Equisetum arvensis).
This herbicide is soluble in water at the level up to 734 mg/dm3. The pKa of acidic group is 3.07, the half-time of decomposition in soil DT50 = 5-6 days, toxicity LD50 = 1160 mg/kg (according to: T. Praczyk, G. Skrzypczak, Herbicydy, Paήstwowe Wydawnictwo Rolnicze i Lesne, Poznaή, 2004 (in polish)).
Due to the presence of carboxylic group in MCPA it can react with soil components, including metal ions. Herbicide is absorbed by soil and therefore its biodegradation is slow. The metal binding by MCPA results in their immobilization which results in slower absorption of metal ions by plants. In the reaction between MCPA and metals insoluble compounds are formed, which are slowly biodegraded.
Obtaining effective herbicides, more environmental friendly enforces the search for new, better chemical compounds containing relevant fragments of this herbicide, which is the matter of this finding.
We claim new ionic pairs containing (4-chloro-2-methylphenoxy)acetate anion of the general formula 1, in which K means ammonium cation of the formula 2 or 3 or 4 or 5 or 6, or pyridinium cation of the formula 7, or imidazolium cation of formula 8, or morpholinium cation of the formula 9, or piperidinium cation of the formula 10, or 8- hydroxyquinolinium cation of the formula 11, or pyrazolium cation of the formula 12, or 2-chloroethylmethylammonium cation of the formula 13, or pyrolidinium cation of the formula 14, where R means alkyl linear chain group containing 1 to 18 carbon
atoms or mixture of linear alkyl chains from 1 to 20 carbon atoms (common names cocalkyl or hydrogenated tallowalkyl) or polyoxyethylene chain.
We claim the synthesis of new ionic pairs containing (4-chloro-2- methylphenoxy)acetate anion of the general formula 1 , in which K means ammonium cation of the formula 2 or 3 or 4 or 5 or 6, or pyridinium cation of the formula 7, or imidazolium cation of formula 8, or morpholinium cation of the formula 9, or piperidinium cation of the formula 10, or 8-hydroxyquinolinium cation of the formula 11, or pyrazolium cation of the formula 12, or 2-chloroethylmethylammonium cation of the formula 13, or pyrolidinium cation of the formula 14, where R means alkyl linear chain group containing 1 to 18 carbon atoms or mixture of linear alkyl chains from 1 to 20 carbon atoms (common names cocalkyl or hydrogenated tallowalkyl) or polyoxyethylene chain, based on the exchange reaction between chloride or bromide of K cation of specified formula 1-14 with (4-chloro-2-methylphenoxy)acetic acid in presence of sodium or potassium hydroxide at 1 : (from 0.8 to 3) : (from 0.8 to 4) molar ratio at temperature from 273 to 373K in water or organic solvent, using common methods of isolation of product. In case of phase separation water layer is removed while the residue is dried. In case when no separation of phases is achieved, the chloroform or ethyl acetate is added to reaction mixture. After the isolation of organic phase the solvent is removed under reduced pressure to get the product.
The herbicide activity of new ionic pair is due to the presence of (4-chloro-2- methylphenoxy)acetate; moreover the new ionic pairs posses additional advantageous features, i.e.: they are ionic and hence non volatile; their vapour pressure at ambient temperature is undetectable. The ionic pairs can be rendered hydrophobic or hydrophilic, depending on the kind of cation used,
- they are thermally and chemically resistant and reveal the tendency to form glass phase below OC, they do not react with metal ions due to the absence of free carboxylate group and do not absorb in soil, they have limited tendency to deposit in natural environment and therefore are more environmentally friendly than parent herbicide - MCPA, new ionic pairs can be classified as ionic liquids according to the low melting points and therefore they can be named as herbicide ionic liquids, apart from herbicide activity the salts posses also the antibacterial and antifungicidal activity due to the presence of large cation, the obtained ionic pairs have cationic surfactants activity due to the presence of the cation with one or more long chain alkyl substituents, they reveal antielectrostatic properties due to their ionic structure and the presence of alkyl substituents.
The synthetic protocol of new ionic pairs is exemplified as follows.
Example I. Synthesis of didecyldimethylammonium (4-chloro-2- methylphenoxy)acetate, [DDA] [MCPA] .
In a round-bottom flask equipped with dropping funnel and reflux condenser the 0.004 mole of (4-chloro-2-methyl-phenoxy)acetic acid was disperged in 40 cm3 of distilled water. To this mixture 0.0044 mole of 10% aqueous solution of NaOH was added dropwise with magnetic stirring and the mixture was heated to 343K until the mixture became clear solution. Then the stoichiometric amount of didecyldimethylammonium chloride was added. The product was formed as precipitate, which was isolated after 24 hours, dissolved in 30 cm3 of ethyl acetate and washed with copious amount of water to remove unreacted substrates and sodium chloride, which was formed in the reaction. After separation of water the ethyl acetate was stripped out from organic phase and remaining solid product was dried at 232K under reduced pressure for 24 hours. The didecyldimethylammonium (4-chloro-2-methylphenoxy)acetate was obtained as orange liquid at 95% yield. The structure of product was confirmed by 1H and C NMR spectra.
1H NMR (CDCl3) δ ppm = 0.88 (t, J = 6.7 Hz, 6H), 1.25 (m, 28H), 1.57 (q, J = 6.9 Hz, 4H), 2.24 (s, 3H), 3.12 (s, 6H), 3.21 (t, J = 4.3 Hz, 4H), 4.41 (s, 2H), 6.75 (d, J = 8.8 Hz,
IH), 7.04 (d, J = 0.6 Hz, IH), 7.05 (d, J - 0.8 Hz, IH); 13C NMR δ ppm = 14.0, 16.3,
22.5, 22.52, 26.1, 29.06, 29.12, 29.26, 29.30, 31.7, 51.1, 63.3, 68.4, 112.7, 124.1, 126.0,
128.4, 129.9, 156.1, 173.1.
The purity of obtained ionic pair was tested by elemental analysis for CHN for
C3IH56ClNO3 (M = 526.23): calculated: C = 70.75%, H = 10.73%, N = 2.66%; experimental: C = 70.54%, H = 10.52%, N = 2.98%.
The physicochemical parameters were obtained by DSC as: glass temperature 223K, crystallization temperature 246K and melting temperature 29 IK.
The obtained data corroborate well with the formula of ionc pair.
Example II. Synthesis of benzalkonium (4-chloro-2-methylphenoxy)acetate -
[BA][MCPA].
0.003 mole of (4-chloro-2-methyl-phenoxy)acetic acid was disperged in 30 cm3 of distilled water and 20% aqueous solution of KOH was added. The reaction mixture was heated at 313K for 30 minutes. Then the stoichiometric amount of benzalkonium chloride dissolved in 20 cm3 water was added. The product deposited as liquid on the bottom of flask. Chloroform (30 cm3) was added and the mixture was left until separation of phases. The separated organic phase was washed with distilled water until no chloride was present in water. After removal of chloroform the product was dried under reduced pressure at 333K. The viscous orange liquid was obtained at 97% yield with 237K glass temperature.
The 1H and 13 NMR spectra were recorded in order to confirm the structure of obtained product.
1H NMR (CDCl3) δ ppm = 0.88 (t, J = 6.7 Hz, 3H), 1.26 (m, max 22H), 1.68 (q, J = 6.9
Hz, 2H), 2.18 (s, 3H), 3.09 (s, 6H), 3.23 (t, J = 4.3 Hz, 2H), 4.45 (s, 2H), 4.70 (s, 2H),
6.76 (d, J = 8.8 Hz, IH), 6.98 (d, J = 0.8 Hz, IH), 6.99 (d, J = 0.6 Hz, IH), 7.40 (d, J =
1.9 Hz, 2H), 7.47 (t, J = 1.9 Hz, IH), 7.49 (t, J - 1.8 Hz, 2H); 13C NMR δ ppm = 14.0,
16.3, 22.5, 22.6, 26.2, 29.12, 29.19, 29.21, 29.27, 29.33, 29.45, 29.50, 29.53, 31.8, 49.4,
63.1, 67.2, 68.7, 112.7, 123.9, 125.9, 127.5, 128.3, 129.0, 129.8, 130.4, 132.9, 156.2,
173.1.
Example III. Syntehsis of domiphen (4-chloro-2-methylphenoxy)acetate -
[DOM][MCPA].
0.025 Mole of domiphen bromide was dissolved in 40 cm3 of distilled water. To this
0.023 mole of sodium (4-chloro-2-methyl-phenoxy)acetate in aqueous NaOH was
added and reaction mixture was stirred for 2 hours. The product deposited as bottom layer of liquid, which was separated and dried at 333K under reduced pressure for 24 hours. The glassy product had 232K glass temperature and was isolated at 98% yield. The structure of product was confirmed by 1H and 13 NMR spectra as follows: 1H NMR (CDCl3) δ ppm = 0.88 (t, J = 6.7 Hz, 3H), 1.25 (m, 18H), 1.68 (q, J = 6.9 Hz, 2H), 2.20 (s, 3H), 3.22 (s, 6H), 3.33 (t, J = 3.4 Hz, 2H), 3.93 (t, J = 4.0 Hz, 2H), 4.34 (t, J = 3.6 Hz, 2H), 4.38 (s, 2H), 6.72 (d, J = 8.5 Hz, IH), 6.88 (d, J = Ll Hz, 2H), 6.96 (t, J = 2.5 Hz, IH), 7.00 (d, J = 3.6 Hz, IH), 7.0 l(d, J = 3.0 Hz, IH), 7.29 (t, J = 1.5 Hz, 2H); 13C NMR δ ppm = 14.0, 16.3, 22.6, 22.7, 26.2, 29.1, 29.2, 29.3, 29.4, 29.46, 31.8, 51.7, 61.8, 62.1, 65.5, 68.5, 112.7, 114.2, 121.9, 124.1, 126.0, 128.4, 129.7, 129.9, 156,0, 156.9, 173.3.
Elemental analysis for CHN for obtained ionic pair of the formula C31H48ClNO4 (M = 534.17) showed: C = 69.49%, H = 9.42%, N = 2.68%. By comparison with calculated values: C = 69.70%, H = 9.06%, N = 2.62% one can conclude that obtained products are pure.
Example IV. Syntehsis of 1-dodecylpyridinium (4-chloro-2-methylphenoxy)acetate - [C 12PIR][MCPA].
0.006 mole of (4-chloro-2-methylphenoxy)acetic acid dissolved in 20 cm of distilled water was placed in 100 cm3 reactor equipped with magnetic stirrer and temperature was adjusted to 333 K. To this mixture the aqueous NaOH was added until the solution became clear. Then 0.005 mole of 1-dodecylpyridinium chloride dissolved in 10 cm3 water was added. The reaction mixture was maintained at 323K for 24 hours followed by evaporation of water. The residue was dissolved in 30 cm3 acetone. The sodium chloride was filtered off and acetone was removed on rotary evaporator from filtrate. The product was dried under reduced pressure at 333K. The resin product was obtained at 70% yield.
The structure of compound was confirmed based upon 1H and 13C NMR spectra. 1H NMR (CDCl3) δ ppm = 0.87 (t, J - 6.7 Hz, 3H), 1.24 (m, 16H), 1.92 (q, J = 6.6 Hz, 2H), 2.19 (s, 3H), 3.83 (q, J = 6.6 Hz, 2H), 4.44 (s, 2H), 4.76 (t, J = 7.4 Hz, 2H), 6.77 (d, J = 8.8 Hz, IH), 6.99 (d, J = 0.6 Hz, IH), 7.01 (d, J = 0.8, IH), 7.98 (t, J = 7.1 Hz, 2H), 8.34 (t, J = 7.7 Hz, IH), 9.35 (d, J = 5.8 Hz, 2H); 13C NMR δ ppm = 14.1, 16.4, 22.6, 26.1, 29.0, 29.24, 29.31, 29.44, 29.51, 31.8, 61.8, 68.7, 112.7, 123.9, 125.9, 128.0, 128.2, 129.7, 144.4, 145.1, 156.0, 173.2.
The purity of obtained salt was tested by elemental analysis for CHN. For the salt of the formula C26H38ClNO3 (M = 448.04): calculated values were: C = 69.70%, H = 8.55%, N = 3.13%; while experimental values were: C = 69.95%, H = 8.82%, N = 2.98%.
Example V. Synthesis of 1-hexadecylpyridinium (4-chloro-2-methylphenoxy)acetate -
[C 16PIR][MCPA]
To the suspension of 0.0045 mole of (4-chloro-2-methylphenoxy)acetic acid in 40 cm3 distilled water 10% aqueous KOH was added dropwise and the mixture was heated to
313K. To the clear solution the stoichiometric amount of 1-hexadecylopyridinium chloride was added and the mixture was stirred for 24 hours. The this water soluble product 40 cm3 chloroform was added. After mixing the orange product was present in chloroform layer. Organic layer was separated and washed with water until no chloride was present in water as monitored by analytical reaction with silver nitrate(V). The chloroform was removed and the solid residue was dried at 353K under vacuum. The product was obtained as orange solid at 74% yield.
The structure of obtained salt was confirmed by 1H NMR and 13C NMR spectra.
1H NMR (CDCl3) δ ppm = 0.88 (t, J = 6.7 Hz, 3H), 1.25 (m, 24H), 1.88 (q, J = 6.6 Hz,
2H), 2.20 (s, 3H), 3.80 (q, J = 6.8 Hz, 2H), 4.43 (s, 2H), 4.72 (t, J = 7.4 Hz, 2H), 6.76
(d, J = 8.5 Hz, IH), 7.00 (d, J = 0.6 Hz, IH), 7.01 (d, J = 0.8, IH), 7.97 (t, J = 7.1 Hz,
2H), 8.33 (t, J = 7.8 Hz, IH), 9.26 (d, J = 5.5 Hz, 2H); 13C NMR δ ppm = 14.1, 16.4,
22.7, 26.1, 29.03, 29.29, 29.34, 29.48, 29.55, 29.59, 29.63, 31.8, 31.9, 61.9, 68.7, 112.7,
123.9, 125.9, 128.0, 128.2, 129.8, 144.4, 145.0, 156.0, 173.2.
Elemental analysis for CHN fro C30H46ClNO3 (M = 504.14): calculated values: C =
71.47%, H = 9.20%, N = 2.78%; experimental values: C = 71.05%, H = 8.98%, N -
2.48%.
Example VI. Synthesis of l-methyl-3-octyl-imidazolium (4-chloro-2- methylphenoxy)acetate
0.005 Mole of (4-chloro-2-methylphenoxy)acetic acid were and 40 cm of distilled water were placed in a 100 cm3 round bottom flask equipped with magnetic stirrer. The mixture was heated at 323 K for 40 minutes. Then the stoichiometric amount of 1- methyl-3-octyl-imidazolium chloride in 10 cm3 of water was added and mixture was vigorously stirred for 24 hours, water was evaporated and 30 cm3 of acetone was added to the residue. The precipitate was filtered off and the acetone was evaporated on rotary
evaporator. The product was dried at 323K under reduced pressure. The resulting liquid product is well soluble in water. The yield was 99%.
The structure of synthesized salt was confirmed ba elemental analysis for CHN. For the compound of the general formula C2IH31ClN2O3 (M = 394.94) the calculated results were: C = 63.86%, H = 7.91%, N = 7.09% while those found were: C = 64.14%, H = 8.08%, N = 7.43%.
Example VII. Synthesis of 4-dodecyl-4-methyl-morpholine (4-chloro-2- methylphenoxy)acetate
0.01 Mole of 4-dodecyl-4-methyl-morpholine chloride and 40 cm3 distilled water were placed in 100 cm3 flask. Then the stoichiometric amount of sodium (4-chloro-2- methylphenoxy)acetate was added and the mixture was magnetically stirred at room temperature for 24 hours. The product was extracted with chloroform, the organic layer was washed with water until disappearance of chloride in water. The solvent was removed on rotary evaporator and the residue was dried at 333K under reduced pressure for 48 hours. The resin-like product was obtained.
The structure and purity of product was confirmed by elemental analysis for CHN. For the compound of the general formula C26H45ClNO4 (M = 471.09) the calculated values were: C = 66.29%, H = 9.63%, N = 2.97% and experimental ones were: C = 66.14%, H = 9.86%, N = 3.23%.
Example VIII. Synthesis of 1-hexyl-l-methyl-piperidinium (4-chloro-2- methylphenoxy)acetate
0.025 Mole of 1-hexyl-l-methylpiperidinium chloride was dissolved in organic solvent at 293K. Then 0.02 mole of potassium (4-chloro-2-methylphenoxy)acetate was added with vigorous stirring. The stirring of reaction mixture was continued for 30 minutes and the mixture was left for the next day at 293 K. The organic solvent was evaporated and to the residue 30 cm3 anhydrous acetone was added. The resulting precipitate was filtered off and acetone was removed from filtrate on rotary evaporator. The liquid product was obtained at high yield.
The structure and purity of product was confirmed by elemental analysis for CHN. For the compound of the general formula C2]H35ClNO3 (M = 384.96) the calculated values were: C = 65.52%, H = 9.16%, N = 3.64% while experimental ones were: C = 65.26%, H = 9.40%, N = 3.75%.
Example IX. Synthesis of 8-hydroxy-l-octyl-quinolinium (4-chloro-2- methylphenoxy)acetate
0.0065 Mole of 8-hydroxy-l-octyl-quinolinium bromide was dissolved in 40 cm3 methanol in 10 0 cm3 round bottom flask. To this vigorously stirred mixture 0.007 mole of sodium (4-chloro-2-methylphenoxy)acetate was added and the mixture was left for 12 hours. After that the methanol was removed on rotary evaporator, the solid residue treated with anhydrous acetone, the inorganic salt filtered off and the product was dried at 323K under reduced pressure. The resin-like product was obtained at 90% yield. Elemental analysis for the product of the general formula C26H33ClNO4 (M = 458.99) confirmed the structure and purity of obtained salts; calculated: C = 68.03%, H = 7.25%, N = 3.05%; experimental: C = 68.39%, H = 7.50%, N = 3.35%.
Example X. Synthesis of 2-chloroethyltrirnethylammonium (4-chloro-2- methylphenoxy)acetate
0.01 Mole of (4-chloro-2-methylphenoxy)acetic acid and 30 cm3 of distilled water were placed in round bottom 100 cm3 flask. To this an aqueous solution KOH was added and mixture was heated at 323K until solution became clear. Then the stoichiometric amount of 2-chloroethyltrimethylammonium chloride dissolved in 20 cm2 of water was added and the mixture was magnetically stirred for 24 hours. The water insoluble product was obtained, which was filtered off. The product was treated with 30 cm3 anhydrous acetone, the precipitate was filtered off and the acetone was distilled off from the filtrate. The solid residue was dried at 333K under reduced pressure. The obtained product was ionic pair.
Elemental analysis for the compound of the general formula C]4H22Cl2NO3 (M = 323.23) was: calculated: C = 52.02%, H = 6.86%, N = 4.33%; experimental: C = 52.37%, H = 7.00%, N = 4.45%.
Przvklad XI. Synthesis of 3,5-diphenyl-l,2-dimethylpyrazolium (4-chloro-2- methylphenoxy)acetate
0.009 Mole of 3,5-diphenyl-l,2-dimethylpyrazolium chloride dissolvedin 20 cm3 of distilled water at 323K was placed in 100 cm3 flask, equipped with magnetic stirrer. To this solution 0.01 mole of sodium (4-chloro-2-methylphenoxy)acetate was added dropwise and the mixture was vigorously stirred at 293K for 24 hours. Then 40 cm3 of
chloroform was added and organic layer was separated and washed couple of times with 30 cm3 water. The chloroform was removed and product was vacuum dried at 333K. The ionic pair was obtained at high yield.
Structure and purity of the compound of general formula C26H26ClN2O3 (M = 449.95) was confirmed by elemental analysis to get: calculated: C = 69.40%, H = 5.82%, N = 6.23%; experimental: C = 69.28%, H = 5.60%, N = 6.55%.
Example XI Synthesis of hexadecyltrimethylammonium (4-chloro-2- methylphenoxy)acetate
Stoichiometric amount of hexadecyltrimethylammonium chloride, (4-chloro-2- methylphenoxy)acetic acid and sodium hydroxide were placed in a flask and water was added to obtain the solution, which was vigorously stirred at room temperature for 2 hours. Organic phase was separated and washed with water until no chloride was present. The elemental analysis for CHN confirmed the structure of the synthesized salt. The deviations between experimental and calculated percentage for carbon, hydrogen and nitrogen did not excees 0.4%.
Example XIII. Synthesis trioctylmethylammonium (4-chloro-2- methylphenoxy)acetate
0.10 Mole of trioctylmethylammonium chloride (commercial Aliquat 336), 0.11 mole of (4-chloro-2-methylphenoxy)acetic acid and 0.11 mole of sodium hydroxide were dissolved in 100 cm3 DMSO. The mixture was heated at 373K for 12 hours. Then 250 cm3 distilled water was added to cool solution. Organic phase was separated and washed with distilled water. The product was dried under vacuum to get trioctylmethylammonium (4-chloro-2-methylphenoxy)acetate .
Example XIV. Synthesis of 1-dodecyl-l-methylpyrolidinium (4-chloro-2- methylphenoxy)acetate
1-Methylopyrolidone and stoichiometric amount of 1 -chlorododecane were placed at microwave oven for 20 minutes. After dissolving of product in water the 4-chloro-2- methylphenoxy)acetate chloride was determined by biphasic titration. The yield of 4- chloro-2-methylphenoxy)acetate chloride was 98%.
To the 98% water solution of 4-chloro-2-methylphenoxy)acetate chloride the stoichiometric amount of 4-chloro-2-methylphenoxy)acetate and potassium hydroxide were added. The product was extracted with chloroform, which was removed by distillation and the product was dried under reduced pressure. The 1-dodecyl-l- methylpyrolidinium (4-chloro-2-methylphenoxy)acetate was obtained at the yield above 90%, for which the elemental analysis for CHN showed the deviation for CHN percentage lower than 0.3%.
Biological activity of new ionic pairs was confirmed by separate studies as follows. The studies were performed on white mustard (Sinapis alba L.) in growth cell with controlled condition. The seeds of white mustard were seeded in compartments filled with soil to the level of 1 cm from bottom. After formation of leafs the number of plants were reduced to four in every compartment. After the third leaf was formed, the plants were treated with tested liquid containing studied ionic paits using TeeJet XR 11 002VP, moving sprinkler over the plants with the speed of 3.1 m/s. Technical parameters of sprinkling were as follows:
- the distance of sprinkler from top of plants - 40 cm, pressure - 2 bars,
- liquid feed - 0.65 dm3/min (circa 250 dm3 per 1 hectare).
The compounds containing ion pairs were dissolved in water/ethanol (1 :2 v/v) at the 0.001 molar concentration. The reference herbicide was Herbicide X containing 300 g MCPA as sodium nad potassium salts in 1 liter of solution. After the sprinkling was done the compartments containing tested plant were placed back in grow cell at 190K (± 2) and air humidity 50%. The daylight illumination time was 16 hours per day. After next two weeks the plants were cut off straight over the ground level and weighed with the 0.1 g accuracy. The procedure was repeated 4 times at fully statistical mode. Based upon obtained results the mass loss of freshly cut plants was compared with standard (plants not sprayed with tested compounds).
Totally 3 experiments were performed on white mustard plants. It has been found that tested ion pairs containing (4-chloro-2-methylphenoxy)acetate anion and ammonium or pyridinium cation reveal higher biological activity than standard Herbicide X. The results of the studies are collected in Tables 1 and 2.
Table 1. The influence of modified MCPA {benzalkonium (4-chloro-2- methylphenoxy)acetate - [BA][MCPA]) on white mustard plant (the mean of four experiments)
Table 2. Influence of various derivatives of MCPA on white mustard plants (2 weeks after use) <
Claims
1. New ionic pairs containing (4-chloro-2-methylphenoxy)acetate anion of the general formula 1, in which K means ammonium cation of the formula 2 or 3 or 4 or 5 or 6, or pyridinium cation of the formula 7, or imidazolium cation of formula 8, or morpholinium cation of the formula 9, or piperidinium cation of the formula 10, or 8-hydroxyquinolinium cation of the formula 11, or pyrazolium cation of the formula 12, or 2-chloroethylmethylammonium cation of the formula 13, or pyrolidinium cation of the formula 14, where R means alkyl linear chain group containing 1 to 18 carbon atoms or mixture of linear alkyl chains from 1 to 20 carbon atoms (common names cocalkyl or hydrogenated tallowalkyl) or polyoxyethylene chain.
2. The method of synthesis of new ionic pairs containing (4-chloro-2- methylphenoxy)acetate anion of the general formula 1, in which K means ammonium cation of the formula 2 or 3 or 4 or 5 or 6, or pyridinium cation of the formula 7, or imidazolium cation of formula 8, or morpholinium cation of the formula 9, or piperidinium cation of the formula 10, or 8- hydroxyquinolinium cation of the formula 11 , or pyrazolium cation of the formula 12, or 2-chloroethylmethylammonium cation of the formula 13, or pyrolidinium cation of the formula 14, where R means alkyl linear chain group containing 1 to 18 carbon atoms or mixture of linear alkyl chains from 1 to 20 carbon atoms (common names cocalkyl or hydrogenated tallowalkyl) or polyoxyethylene chain, characteristic of the method of synthesis based on the exchange reaction between chloride or bromide salt of ammonium cation of the formula 2 or 3 or 4 or 5 or 6, or pyridinium cation of the formula 7, or imidazolium cation of formula 8, or morpholinium cation of the formula 9, or piperidinium cation of the formula 10, or 8-hydroxyquinolinium cation of the formula 11, or pyrazolium cation of the formula 12, or 2- chloroethylmethylammonium cation of the formula 13, or pyrolidinium cation of the formula 14, where R means alkyl linear chain group containing 1 to 18 carbon atoms or mixture of linear alkyl chains from 1 to 20 carbon atoms (common names cocalkyl or hydrogenated tallowalkyl) or polyoxyethylene chain, undergoes the exchange with (4-chloro2- methylphenoxy)acetic acid in presence of sodium or potassium hydroxide used at molar ratio 1 : (from 0.8 to 3) : (from 0.8 to 4) at temperature from 273 to 373K in aqueous medium or organic solvent, followed by product isolation.
3 . The method as in point 2, characteristic of removal of water followed by drying of product.
4. The method as in point 2, characteristic of removal of organic solvent, addition of chloroform or ethyl acetate, separation of organic phase and isolation of product by evaporation the introduced solvent under reduced pressure.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013068302A1 (en) * | 2011-11-07 | 2013-05-16 | Bayer Intellectual Property Gmbh | Ionic compounds with an improved herbicidal activity |
| EP2880978A1 (en) * | 2013-12-09 | 2015-06-10 | Przedsiebiorstwo Produkcyjno-Consultingowe ADOB sp. z o.o. sp. k. | Herbicidal quaternary ammonium salts of (4-chloro-2-methylphenoxy)acetic acid |
| EP3092898A1 (en) | 2015-05-13 | 2016-11-16 | Przedsiebiorstwo Produkcyjno-Consultingowe ADOB sp. z o.o. sp. k. | Herbicidal ionic liquids with betaine type cation |
| PL239073B1 (en) * | 2019-02-06 | 2021-11-02 | Inst Ochrony Roslin Panstwowy Inst Badawczy | Method of obtaining herbicidal ionic liquids with 4-alkyl-4-methylmorpholine cation and 4-chloro-2-methylphenoxyacetate anion and their use as herbicides |
| PL447659A1 (en) * | 2024-01-31 | 2025-03-31 | Politechnika Poznańska | New quaternary ammonium salts containing an alkyl L-carnitate cation and a gentisate anion, method of preparing them and their use as new forms of antioxidants |
| PL448555A1 (en) * | 2024-05-14 | 2025-07-14 | Politechnika Poznańska | Use of ammonium salts containing the alkyl L-carnitate cation and the gentisate anion as rooting agents for dicotyledonous plants and a composition for rooting dicotyledonous plants |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| PL237908B1 (en) * | 2018-02-01 | 2021-06-14 | Przed Produkcyjno Consultingowe Adob Spolka Z Ograniczona Odpowiedzialnoscia Spolka Komandytowa | Herbicidal ionic liquid with 4-chloro-2-methylphenoxyacetic acid anion and eutectic mixture containing it |
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| GB1454907A (en) * | 1972-11-17 | 1976-11-10 | American Cyanamid Co | Compositions containing 1,2-dialkyl-3,5-diphenylpyrazolium wild oat herbicides and 1,2-dialkyl-3,5-diphenylpyrazolium salts useful therein |
| US4170464A (en) * | 1974-10-25 | 1979-10-09 | American Cyanamid Company | Herbicidal combinations |
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- 2007-05-11 PL PL382404A patent/PL382404A1/en not_active Application Discontinuation
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| GB1454907A (en) * | 1972-11-17 | 1976-11-10 | American Cyanamid Co | Compositions containing 1,2-dialkyl-3,5-diphenylpyrazolium wild oat herbicides and 1,2-dialkyl-3,5-diphenylpyrazolium salts useful therein |
| US4170464A (en) * | 1974-10-25 | 1979-10-09 | American Cyanamid Company | Herbicidal combinations |
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| DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; NISHIUCHI, YASUHIRO ET AL: "Toxicity of pesticides to some freshwater organisms. LIX", XP002497376, retrieved from STN Database accession no. 1980:88958 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013068302A1 (en) * | 2011-11-07 | 2013-05-16 | Bayer Intellectual Property Gmbh | Ionic compounds with an improved herbicidal activity |
| EP2880978A1 (en) * | 2013-12-09 | 2015-06-10 | Przedsiebiorstwo Produkcyjno-Consultingowe ADOB sp. z o.o. sp. k. | Herbicidal quaternary ammonium salts of (4-chloro-2-methylphenoxy)acetic acid |
| EP3092898A1 (en) | 2015-05-13 | 2016-11-16 | Przedsiebiorstwo Produkcyjno-Consultingowe ADOB sp. z o.o. sp. k. | Herbicidal ionic liquids with betaine type cation |
| PL239073B1 (en) * | 2019-02-06 | 2021-11-02 | Inst Ochrony Roslin Panstwowy Inst Badawczy | Method of obtaining herbicidal ionic liquids with 4-alkyl-4-methylmorpholine cation and 4-chloro-2-methylphenoxyacetate anion and their use as herbicides |
| PL447659A1 (en) * | 2024-01-31 | 2025-03-31 | Politechnika Poznańska | New quaternary ammonium salts containing an alkyl L-carnitate cation and a gentisate anion, method of preparing them and their use as new forms of antioxidants |
| PL448555A1 (en) * | 2024-05-14 | 2025-07-14 | Politechnika Poznańska | Use of ammonium salts containing the alkyl L-carnitate cation and the gentisate anion as rooting agents for dicotyledonous plants and a composition for rooting dicotyledonous plants |
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| WO2008140338A4 (en) | 2009-03-05 |
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