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    • 专利摘要:
    The invention relates to agrochemical compositions comprising novel biodegradable bisaminopropylamides of formula (I) or of formula (II) and their uses in detergent compositions. In the agrochemical compositions, the bisaminopropylamides act as an adjuvant for the agrochemically active compounds such as pesticides, growth regulators or fertilizers.
    公开号:BE1021290B1
    申请号:E2012/0297
    申请日:2012-05-04
    公开日:2015-10-22
    发明作者:Kurt Buyse；Kristof Moonen
    申请人:Taminco；
    IPC主号:
    专利说明:

    Novel agricultural and detergent compositions containing a tertiary amide as an excipient or as a surfactant
    The present invention relates to agricultural compositions comprising a tertiary amide as a new auxiliary and to the use of this tertiary amide as an auxiliary in agrochemical compositions and detergent compositions containing an anionic surfactant.
    A whole range of agrochemicals is used to exert every possible biological effect when growing crops, for example pesticides, plant growth regulators or fertilizers. Many of these compounds are applied by spraying on the leaf, and must be absorbed through the surface of the leaf to exert their effect in the plant. That is why many of these agrochemicals have been formulated in agricultural compositions.
    Different effects can be obtained by formulating agrochemical substances in an agricultural composition. The agrochemical can be made in such a form that it is easy to handle (for example pourable, easy to dilute for further use, ...), that it is stable during storage and use (for example the formation of emulsions or suspensions, efficient spray droplets, ...), that they can be used more safely (for example by providing dust-free products or reducing drift during spray applications) or that the active ingredient is delivered more efficiently to the target organism. The latter can be achieved, for example, by improving the adhesion to the leaves, improving the spreading and wetting of the leaf surface or improving the penetration through the surface of the leaf.
    It is well known that the choice of surfactants in the agricultural composition has a major influence on the performance of the agrochemical. Surfactants in agricultural compositions can, for example, act as dispersants, wetting agents or auxiliaries. However, the ability of various surfactants to increase agrochemical effectiveness is very unpredictable. Moreover, the choice of a suitable surfactant is often highly dependent on the identity and physico-chemical properties of the active ingredient of the composition, but also on the other ingredients of the composition.
    Agrochemical formulation experts tend to use more concentrated solutions of their active ingredients. This also causes an increase in the surfactant concentration, which poses additional challenges to prevent a phase separation. Low temperature stability is a critical parameter for many agricultural compositions.
    As a result of the resistance of certain weeds to certain pesticides, more and more mixtures of pesticides are used. A common strategy is to use both a hydrophilic and a lipophilic pesticide in one application. This often requires the use of multiple surfactants that are effective for the individual active ingredients present therein. For many active ingredients, such as, for example, glyphosate, it is known that cationic types of surfactants are very efficient. Many cationic surfactants are often incompatible with anionic surfactants, which can be added to the composition for other purposes. Another and perhaps a preferred solution would be the use of one surfactant to increase the effectiveness of all active ingredients present. Excipients that work well with hydrophilic
    The pesticides sometimes work antagonistic with lipophilic pesticides and vice versa. Therefore, there is a need for adjuvants that are effective for a large number of pesticides, from very hydrophilic to very lipophilic.
    Another requirement nowadays is an increasing demand in most areas for substances that are easily biodegradable. This is also the case in the agrochemical area, where additives with a better biodegradability are combined with a good capacity to improve the uptake and effectiveness of pesticides and fertilizers.
    Therefore, there is a continuing need in the industry for more effective and compatible excipients, dispersants, and surfactants, particularly those used in compositions for delivery of pesticide components, among others. Higher effectiveness leads to lower application quantities to achieve the same effect. That is why agricultural compositions with improved efficacy lead to lower costs, increased product safety and a lower environmental impact.
    A variety of surfactants have been used for this purpose, and many are nitrogenous. The group of surfactants most commonly used in this context are fatty acid amine ethoxylates, but other types of compounds have also been described as adjuvants for pesticides or fertilizers. For example, WO2006 / 034426 shows the use of alkoxylated alkylamine quaternary surfactants as adjuvants for glyphosate. In EP 0 257 686 the incorporation of certain alkoxylated fatty acid amines, amidoamines or imidazolines is shown to improve the activity of herbicidal and fungicidal compositions.
    The biodegradability of surfactants can be improved by incorporating ester or amide functionalities into the structure. EP-A1-0 638 236 describes an agrochemical composition containing adjuvants of the class of esteramines. The esteramines described in that publication all relate to compounds with two fatty acid alkyl chains. WO2008 / 106466 shows the use of alkanolamine esters as an adjuvant / dispersant for pesticide formulations. However, ester-containing surfactants may have the disadvantage of being sensitive to hydrolysis, while amide groups are much more hydrolytically stable. EP-B1-1289 362 describes the use of amine compounds with an improved biodegradability as auxiliaries for pesticides and fertilizers. The compounds are based on dialkylamino-propylamine, wherein the alkyl groups are C1 to C5 fatty acid chains and which are converted to an amidoamine by reaction with a C8 to C22 fatty acid.
    In WO 97/05779, crop protection compositions are claimed that contain water-soluble active ingredients and one or more poly-ethoxylated amidoamines with two carbon atoms between the amido and amino groups. EP-B-1 289 362 describes agricultural compositions comprising a pesticide, a growth regulator or a fertilizer and amidoamines, in particular diethanolaminopropylamides or dialkylaminopropylamides, as a biodegradable excipient. The amidoamines described in this European patent are secondary amides, i.e., they include a -CONH amide group. For the preparation of these amidoamines, reference is made in this prior art patent to WO 98/047860 (= EP-B-0 977 727) in which a process is disclosed wherein a carboxylic acid is reacted with an amine to produce the corresponding amide . In the only preparation example described therein, N, N-dimethylamino-propylamine (DMAPA) is used as the primary amine that is reacted with decanoic acid to produce the corresponding secondary amide. The carboxylic acid amides thus produced are described in EP-B-0 977 727 for their use as surfactants.
    A disadvantage of the use of such primary amino-propylamines, in particular of DMAPA, is that they already have many other large-scale applications, and that the production of these amines causes the formation of large amounts of by-products, in particular of the corresponding secondary bisaminopropylamines, for which there are insufficient commercial uses and which therefore must be removed from the process as a waste. Regarding the uses of DMAPA, DMAPA, for example, is an important intermediate for surfactants in the preparation of soft soaps and other products, as an intermediate for the preparation of betaines and fatty acid amine oxides. Ν, Ν-dimethylaminopropylamine is also used as a starting material for the preparation of flaking agents (through the conversion of the corresponding methacrylamide monomers), road marking paint, and polyurethanes. DMAPA has also been shown to inhibit corrosion in steam boiler water treatment, and is an intermediate for additives for gasoline and engine oil. Due to the widespread use of DMAPA, and the fact that the products with which it is associated are produced at a level of many millions of pounds a year, there is a constant challenge to produce the Ν, Ν-dimethylaminopropylamine with a high yield and selectivity due to the high costs associated with contamination by the by-product. These costs can of course also be reduced when new valuable applications of the by-products are found.
    One of the more common methods used for the commercial production of aliphatic amines such as dimethylaminopropylamine (DMAPA) is the catalytic hydrogenation of aliphatic nitriles using batch, fluidized bed, or trickle-bed hydrogenation techniques using ammonia to form secondary amines inhibit (in particular bisdimethylaminopropylamine or bisDMAPA). However, considerable amounts of ammonia are needed to be effective, and even then a few percent of secondary amines are formed. The operation of ammonia is expensive because it requires storage under pressure, it increases the lead time for loading and venting, and it can cause an environmental problem unless expensive recovery equipment is provided. Other processes and special hydrogenation catalysts were thus developed to enable the production of DMAPA without added ammonia. Reference can be made, for example, to the method described in US 5,869,653. However, there remains a problem that often a small percentage of the secondary amine by-product is still produced for which there are in practice only small-scale applications, so that relatively large quantities of it are eliminated. fall material.
    A first possible application of the secondary amine bisDMAPA is the use in the production of a polyurethane catalyst. This application is described, for example, in U.S. Pat. US 4 049 591 and US 6 458 860. US 3 234 153 describes in particular the use of N, N-bis (dimethylamino) -acetamide and US 6 458 860 the use of N, N-bis (dimethylamino) -formamide as a polyurethane catalyst. Only limited amounts of bisDMAPA are required for these applications.
    As described in US 2005/0202990, in particular in Examples XXII-XXV thereof, bisDMAPA can also be used as such in effervescent tablets which are used in particular to pre-treat a new item of clothing before it is first washed to fix the colors and prevent the dye from sprouting. Incidentally, BisDMAPA can also be used as an amine coupling unit in the production of complex polyol compounds for use in cleaning compositions. Such applications are described in US 7 332 467 and US 7 678 755.
    All of these applications are not sufficient in practice to find a market for the relatively large quantities of the secondary amine by-products produced in the production of the commercially valuable primary amine, and they are certainly not sufficient to be able to sustain the efforts to reduce those supplied in the production of the primary amines to inhibit the formation of the secondary amines so that more secondary amine by-products are formed.
    An object of the present invention is to find new, preferably industrial, applications on a larger scale for these secondary amine by-products.
    A further object of the present invention is to provide an adjuvant with broad compatibility for both charged, hydrophilic and lipophilic active ingredients and which effectively improves their performance.
    Another object of the present invention is to provide an adjuvant in agrochemical compositions, or a surfactant or a dissolving aid in detergent compositions, which exhibits good compatibility with anionic surfactants and which is compatible with aqueous and organic media, and even more, acts as a compatibilizer in high-load formulations.
    Yet another object of the present invention is to provide an adjuvant / surfactant with good biodegradability.
    The present invention provides a new agrochemical composition containing at least one active ingredient selected from the group consisting of pesticides, growth regulators and / or fertilizers (in particular leaf fertilizers), and further a tertiary amide according to formula (I)
    or according to formula (II) wherein:
    R 1 is an aliphatic group with 5-23 carbon atoms, and preferably a fatty acid chain; R 2, R 3, R 4 and R 5 are, independently, hydrogen, -CH 2 CH 2 OH, -CH 2 CH (CH 3) OH or an aliphatic group of 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms; R 6 is hydrogen or an aliphatic or aromatic group with 1 to 22 carbon atoms; and Y- is an anion.
    It also provides a novel detergent composition containing at least one tertiary amide of formula (I) or formula (II) and additionally at least one anionic surfactant, the detergent composition preferably being a water-based liquid composition. The detergent composition preferably comprises at least one soap.
    The term "an aliphatic group that has x-y carbon atoms" or "an aliphatic group with x-y carbon atoms" in the present specification is understood to mean a linear or branched Cx to Cy carbon chain (including Cx and Cy) that is saturated or unsaturated.
    As with DMAPA amides, amides can also be formed from bisDMAPA. In contrast to DMAPA amides, which are secondary amides, the amides resulting from the acylation of bisDMAPA are tertiary amides. It has surprisingly been found that these new tertiary amides have properties that differ considerably from the secondary DMAPA amides, but that they can still be used in the same or similar applications and moreover also in other applications, in particular as an adjuvant for biologically active compounds such as pesticides, growth regulators and fertilizers and as a dissolving aid or surfactant in detergent compositions. An important advantage of these tertiary amides is that they can be made from the secondary amine by-products, such as bisDMAPA, rather than the primary amines such as DMAPA. A further important advantage of these tertiary amides is that they are also biodegradable, as shown in Example 3.
    In a preferred embodiment, the R 2 and R 3 groups of the tertiary amide are the same as the R 4 and R 5 groups, i.e. the amide is a symmetrical amide.
    In a further preferred embodiment, the tertiary amide is free from the corresponding secondary amides according to formula (III) and (IV):
    (wherein the different R groups have the same meaning as in formula (I) and (II)), or per 100 moles of said tertiary amide comprises at most 50 moles, preferably at most 25 moles, of these corresponding secondary amides according to formula (III) and (IV). R1 is preferably an aliphatic group, in particular a fatty acid chain, with 5-13 carbon atoms (i.e. a C5 to C13 carbon chain), preferably 5-9 carbon atoms. This embodiment is particularly advantageous when the amide is a diamine according to formula (I). It has indeed been found rather surprising that despite the absence of ionic groups, such tertiary amides are completely soluble in water and also in non-polar solvents such as dodecane. This is not only the case when one or more of the R 2, R 3, R 4 and R 5 groups are ethanol and / or tertiary propanol groups, but also when these groups are alkyl groups, in particular C 1 to C 3 alkyl groups. The R2, R3, and R4
    R 5 groups are preferably methyl groups. The corresponding DMA-PA amides, on the other hand, show only moderate water solubility. R1 can also be a longer chain aliphatic group, in particular an aliphatic group with 7-21 carbon atoms, preferably 9-17 carbon atoms. This embodiment is particularly advantageous when the amide is a diammonium salt according to formula (II). It has been found that such a diammonium salt can also act as a solvent (in particular in water) but in particular as a surfactant. As a surfactant, it is compatible with anionic surfactants, especially when R 6 is hydrogen or an aliphatic group with 1 to 3 carbon atoms, with R 6 preferably being a methyl group. In a preferred embodiment, R 1 is an aliphatic group with 9 to 15 carbon atoms, preferably 9 to 13 carbon atoms, to achieve optimum foam-forming properties in detergents.
    It was quite surprisingly found that the tertiary amides of formula I and formula II have specific properties compared to other amine-based surfactants and more particularly compared to the structurally related secondary amiamides (e.g. DMAPA amides).
    For example, when bisDMAPA is reacted with a C8 fatty acid methyl ester (or a C8 fatty acid), it was surprisingly found that the resulting compound is completely miscible with both water and dodecane at temperatures up to 40 ° C. This amphiphilic nature demonstrates that these molecules can be used as efficient dissolution aids, but also explains, with regard to their use in agricultural compositions, their broad compatibility with hydrophilic and lipophilic active ingredients. Furthermore, they can be used effectively in highly concentrated (so-called "high load") agrochemical compositions to prevent phase separation from occurring. The amphiphilic behavior of the bisDMAPA amides is further illustrated in Example 4.
    Given the nature of the amphiphilic tertiary amine, the agrochemical composition of the present invention preferably comprises at least two active ingredients, comprising at least one hydrophilic active ingredient and at least one lipophilic active ingredient.
    The hydrophilicity or lipophilicity of the active ingredient can be determined by its Kow value, i.e. by the octanol-water distribution coefficient. This coefficient is defined as the ratio (at equilibrium) of the concentration of active components in the octanol phase to its concentration in the aqueous phase of a two-phase octanol / water system. The higher the Kow value, the more non-polar (hydrophilic) the compound is. The parameter is measured using low concentrations of solute at room temperature (20 ° C). In the present description, a hydrophilic active component is defined as a compound with a log Kow value of less than 0, while a lipophilic active component is defined as a compound with a log Kow value of greater than or equal to 0 (measured at a temperature at 20 ° C). Since for charged compounds the Kow value depends on the pH, it is measured for such compounds at the pH of the agrochemical composition. Below are some examples of known log Kow values of active ingredients:
    Glyphosate -3.2 (at pH 7)
    Carfentrazone ethyl 3.4
    Phenoxaprop-P-ethyl 4.3
    Dicamba -1.9 (at pH 7)
    Atrazine 2,6 2,4-D -0,8 (at pH 7)
    Nicosulfuron 0 (at pH 7)
    Bentazon -0.5 (at pH 7)
    Another example of the special properties of the bisDMAPA amides was observed when the reaction product of bisDMAPA and a fatty acid was quaternized with methyl chloride to form a diquat surfactant. These diquat surfactants were still found to have good solubilities at low temperatures, as illustrated in Example 5.
    It was surprisingly found that this diquat surfactant was less toxic and irritating than a monoquat surfactant (prepared from the corresponding primary amine) and it was also surprisingly found that this diquat exhibited good compatibility with anionic surfactants and even exhibited foam reinforcing properties (Examples 6, 7).
    The tertiary amide of formula (I) or (II) can be added as an effective auxiliary to both liquid, such as water or solvent-based SL, EG and SC formulations, and to solid agricultural compositions (which in particular have a in powder form or granular form) containing pesticides, such as herbicides, acaricides, fungicides and insecticides, plant growth regulators and / or fertilizers. The liquid composition may be in the form of a solution, an emulsion (including microemulsions) or a suspension. The herbicide can be selected from the following chemical families (where the site of action is indicated in parentheses): glycines (inhibition of EPSP synthesis), phenoxycarboxylic acids (synthetic auxin), benzoic acid (synthetic auxin), thiazolinones (inhibition of protoporfyrinogen oxidase), phosphinic acids (inhibition of glutamine synthetase) diphenyl ether (inhibition of protoporphyrinogen oxidase), imidazoline (inhibition of acetolactate synthetase), sulphonylureas (inhibition of acetolactate synthetase), aryloxy-phenoxy-propionates (inhibition of acetyl coenzyme) and tri-azine inhibitor of photosynthesis in photosystem II).
    Typical examples of herbicides are various amine salts of glyphosate, such as the isopropylamine salt, the dimethylamine salt and the ethylenediamine salts; other salts of glyphosate, such as potassium, sesin sodium and trimethyl sulfonium salt; carfentrazone ethyl, glufosinate, salts and esters of 2,4-dichlorophenoxy acetic acid, salts and esters of 4-chloro-2-methylphenoxyacetic acid, biala-fos (= glufosinate ammonium), dicamba, atrazine, diphenyl ethers (such as bi-phenox , lactofen and fomesafen), imidazolinones (such as imazapic, imazapyr and imazethapyr) and sulphonylureas (such as nicosulfuron, prosulfuron and bensulfuronmethyl).
    The amino compounds of formula (I) and (II) are excellent auxiliaries for water-soluble herbicides, e.g. the widely used herbicide glyphosate (glyphosate = N- (phosphonomethyl) glycine), and its salts. Suitable examples of fungicides are conazole fungicides (such as epoxiconazole and propiconazole) and strobilurin fungicides (such as azoxystrobin and kresoximmethyl).
    Other examples of formulations in which the amino compounds are used as excipients are fertilizer solutions, in particular micronutrient solutions containing one or more micronutrients such as iron, manganese, copper, zinc, boron and molybdenum. The micronutrients can be complexed to, for example, amino carboxylates such as EDTA, DTPA, HEDTA, EDDHMA and EDDHA. In addition to micronutrients and chelating agents, the compositions may also contain macronutrients, such as nitrogen, phosphorus, potassium, magnesium, and sulfur, and pesticides may also be included. These above-mentioned compositions are particularly suitable for sheet applications.
    The formulations of the invention may also contain other additives, such as other surfactants, hydrotropes, and preservatives; additives to further increase pesticide activity, such as ammonium sulfate; solvents; corrosion inhibitors; thickeners; sequestrants; antifreeze agents; anti-foaming agents; anti-gelling agents and colorants.
    The compositions may also contain viscosity-lowering agents such as glycerol, ethylene glycol, propylene glycol, and low molecular weight polyethylene or polypropylene glycols.
    The compositions can be concentrated, as well as diluted "ready to use" solutions. The concentrations can vary widely and a pesticidal composition would be 0.0199.9% by weight of a pesticide, 0-40% by weight ammonium sulfate and an amount of 0.01 - 70 weight% of an amino compound of formula (I) or (II) A suitable herbicide is glyphosate or a salt thereof, which is preferably present in an amount of 0.02 to 70% by weight. The present invention can also be used advantageously in combination with solid agrochemicals such as strobilurin.
    The dissolution of inorganic and organic compounds is an essential treatment in daily life, as well as in chemistry. This can be achieved by molecular solubilization in water or in organic solvents. For various reasons (toxicity, biodegradability, the simultaneous solubilization of both polar and non-polar compounds, etc.), chemists and formulation experts often prefer solubilization using added surfactants. Surfactants are also referred to as wetting agents and foam formers. Surfactants reduce the surface tension of the medium in which it is dissolved.
    Another approach to dissolving hydrophobic compounds in water is the use of amphiphilic solvents, which present an attempt to combine the benefits of solvents and surfactants. They are often used in the field of coatings, degreasing and many other applications (perfumery, ink, etc.). They exhibit the properties of both the solvents such as volatility and solubilization of organic substances, and the surfactants, e.g., surface activity, self-aggregation in water, and co-micelle with surfactants. They are commonly referred to as hydropropes. Sometimes hydrotropes are added to detergent compositions to prevent phase separation and thus increase stability and lower viscosity.
    In the present description, the term "dissolution aid" is used as a synonym for "hydrotrope." A hydrotrope is a compound that solubilizes hydrophobic substances in aqueous solutions. Typically, hydrotropes consist of a hydrophilic moiety and a hydrophobic moiety (such as surfactants), but the hydrophobic moiety is generally too small to cause spontaneous self-aggregation. Hydrotropes do not have a critical concentration above which self-aggregation "suddenly" begins to occur (as was found for micelle and vesi cell forming surfactants, which have a critical micelle concentration or cmc and a critical vesicle concentration or CVC, respectively). Instead, some hydrotropes aggregate in a step-by-step self-aggregation process, gradually increasing the aggregation size. However, many hydrotropes do not appear to self-aggregate at all unless a dissolution aid has been added. Hydrotropes are used industrially. Hydrotropes are used in detergent formulations to allow for more concentrated formulations of surface active. Examples of hydrotropes include sodium p-toluene sulfonate and sodium xylene sulfonate.
    The most common hydrotropes today are ethers derived from ethylene glycol. They have been studied extensively because they exhibit interesting properties, mainly due to the fact that they are soluble not only in water but also in most organic solvents. However, recent toxicological studies have suggested a possible reprotoxic activity. That is why a number of them were banned from medicines, medicines, and household products. Consequently, there is a need for new harmless amphiphilic solvents that have similar physico-chemical properties.
    Surprisingly, it was found that, for example, N, N-bis (3- (dimethylamino) propyl) octanamide exhibited good hydrotropic properties. Moreover, it was found that this compound is completely soluble in water and in dodecane and thus exhibited an amphiphilic nature.
    Detergents, cleaning agents, shampoos and other personal care products are usually based on an anionic surfactant. Examples of these anionic surfactants are, for example, sodium laureth sulfate (LES) or linear alkyl benzene sulfonates (LAS). Further ingredients for stability and property-enhancing reasons are added, such as cationic compounds, especially surfactants, to increase foam stability and improve the conditioning properties of the product. The cationic surfactants will adsorb on the negatively charged surface of the hair and will reduce friction as the hydrophobic tails will stick into the air. The concentration range of cationic amphiphiles is limited for such applications due to the formation of insoluble precipitates with anionic surfactants at a certain mixing ratio. Finding alternatives that are equivalent or even more powerful in performance and toxicity than the classically used cationic compounds is still the center of attention.
    Surprisingly, it was found that the amidoamine of formula (II) with two quaternary ammonium groups in the hydrophilic head group exhibited better compatibility with anionic surfactants. This property is also particularly advantageous for agrochemical compositions in which different types of surfactants must be used to achieve the desired results.
    It was also surprisingly found that the water solubility of these diquat surfactants is better than that of standard quaternary surfactants.
    The present invention therefore also relates to a detergent composition containing a tertiary amide according to formula (I) or (II) and additionally at least one anionic surfactant. The detergent composition can be a solid, in particular a granular material or a powder, but is usually a water-based liquid composition containing water.
    In the detergent composition, particularly when it is a water-based liquid composition, the tertiary amide of the invention can be used primarily as a dissolving aid. In this case, the tertiary amide is preferably a diamine of formula (I) wherein R1 is an aliphatic group with 5-11 carbon atoms and R2, R3, R4 and R5 are alkyl groups with 1 to 3 carbon atoms, preferably methyl groups. The tertiary amide of the invention can also be used as a surfactant in the detergent composition, particularly when it is a quaternary ammonium salt (diquat) of formula (II). To increase the compatibility between these two surfactants, R6 is preferably an aliphatic group with 1 to 3 carbon atoms, more preferably a methyl group.
    Although the details of the preparation method are described below with particular reference to the preparation of bisDMAPA amide, it will be understood that this preparation method is also used to prepare other bisaminopropylamides of the present invention.
    BisDMAPA amide excipients can be made from bisDMAPA (which can be recovered as a by-product in the production of DMAPA) and a suitable acylating agent. Carboxylic acid, esters, anhydrides or acyl halides (e.g. acid chloride) can be used as an acylating agent.
    When acid chlorides are used, the bis-DMAPA amide is obtained simultaneously with hydrochloric acid. Typically, the hydrochloric acid is captured by the addition of a base. This can be an excess of starting amine, or a cheaper tertiary amine that is not sensitive to acylation, for example, but not limited to, triethylamine, pyridine, etc. In the case of bisDMAPA amides, the final product also still has basic tertiary amine groups that can serve to catch the exempted hydrochloric acid. It is known that acid chlorides are highly reactive for primary and secondary amines, releasing a great deal of reaction heat. Therefore, acylations using acid chlorides are generally, but not necessarily, carried out at temperatures below 100 ° C to allow rapid removal of reaction heat, and diluted in a suitable solvent. A suitable solvent is usually a solvent that dissolves both starting materials and end products. Advantageously, any by-product generated during the acylation reaction can precipitate from the reaction medium. Suitable solvents can be, for example: ethers such as diethyl ether, tetrahydrofuran (THF), etc. .. Halogenated alkanes such as dichloromethane, chloroform, etc. Acylations of highly nucleophilic amines with acid chlorides can be carried out in water with the addition of inorganic bases such as NaOH or sodium carbonate (the so-called Schotten-Baumann reaction). Those skilled in the art know that organic catalysts can be used to increase the kinetics of the desired acylation reaction according to a principle known in the art as "nucleophilic catalysis". Catalysts such as dimethylaminopyridine (DMAP) or pyridine can be used for this purpose.
    Carboxylic acids or esters are generally cheaper reagents than the corresponding acid chlorides. Yet they are less reactive. However, bisDMAPA amides can also be formed from carboxylic acids or esters with procedures known to those skilled in the art. In the case of carboxylic acids, a salt is easily formed by adding the amine. Conversion to the corresponding amide is generally carried out by applying heat and by removing water of reaction. In general, temperatures above 100 ° C are required. Catalysts can be added to facilitate the condensation reaction, such as (solid) acids. Boric acid was also described as a suitable amidation catalyst for carboxylic acids. On the other hand, basic catalysts are usually used for esters. They can be selected from typical transesterification catalysts such as sodium methoxide, titanates, etc. Also in the case of esters, the reaction benefits from the removal of the alcoholic coproduct. Enzymes (lipases and proteases) can also be used as catalysts, whereby lower temperatures can be used.
    BisDMAPA appeared to be difficult to react with carboxylic acids and esters under random conditions. However, the optimization of the reaction parameters allows the amides to be obtained with a satisfactory yield and purity.
    Examples
    Example 1: Preparation of bisDMAPA amide by acvlerina of bisDMAPA with an acid chloride.
    To a solution of 10% by weight bisDMAPA in THF and 2 equivalents of triethylamine, a 1: 1 solution of octanoyl chloride in THF is added dropwise while the reaction temperature is maintained at a temperature of 40 ° C. A precipitate is formed during the addition. After the addition is complete, the reaction mixture is reacted for an additional hour at 40 ° C. The mixture is then cooled and the precipitate is removed by filtration. The filter cake is washed with diethyl ether which is combined with the original filtrate. The mixture is then poured into an equal volume of a saturated aqueous sodium bicarbonate solution in a separatory funnel. After vigorous shaking, the aqueous phase is separated from the organic phase and washed with a fresh amount of diethyl ether. Phase separation is repeated and the two organic phases are combined and dried over magnesium sulfate for 2 hours. The MgSCU is then removed by filtration and the solvent is removed by evaporation under reduced pressure. The oil obtained appears to be 95% pure bisDMAPA octyl amide (yield: 92%).
    Example 2: Preparation of bisDMAPA amide by addition of bisDMAPA with a carboxylic acid.
    A 1 to 1 molar mixture of bisDMAPA and octanoic acid was heated to a temperature of 200 ° C in an atmospheric reactor equipped with a stirrer and a distillation setup. During the reaction, water was removed by distillation. After four hours, the octanoic acid conversion was 72%. The pressure was then slowly reduced to 20 mbar, so that the unreacted starting material could be distilled off. After the starting materials were removed and collected for reuse, the pressure was further reduced to 10 mbar and the bisDMAPA could be collected in the distillation setup with a 95% purity.
    Example 3: Biodegradability
    The biodegradability of N, N-bis (3- (dimethylamino) propyl) octanamide was tested in a manometric respirometry test according to European Regulation 440/2008 / EC, Method C.4-D of May 30, 2008: Manometric Respirometry Test (EEG Publication N ° L142 / 496, May 2008).
    The percentage of biodegradability was 65% after 28 days. As a result, the compound was considered easily biodegradable.
    Example 4: Solubilizer effect
    Due to the unique structure of the tertiary amide compound of formula (I), it can also act as a dissolution aid. The solubilization effect through the condensation products of bisDMAPA with a C8 fatty acid methyl ester was tested. The result is shown in Figure 1.
    The solubilizing properties of the compound are investigated by spectroscopically studying the solubilization of the hydrophobic dye Disperse Red 13 (DR-13) in water using co-solvents. It is known that the solubilization of a hydrophobic compound in water by a co-solvent increases slightly and monotonously at low and medium concentrations of the co-solvent and exponentially at very high concentrations. The DR-13 solubilization curve obtained with a surfactant shows the classical development observed in the case of micellar solubilization, i.e. the DR-13 solubilization suddenly increases when micelles are formed for concentrations above the cmc.
    All tested compounds that have surfactant-like properties are very efficient at low concentrations. An excellent increase in the amount of dissolved hydrophobic dye is achieved by adding small amounts of the non-ionic tertiary amide according to formula (I). All substances exhibit higher yields compared to ordinary hydrotropes such as SXS (Sodium xylene sulfonate) or CHP (cyclohexylpyrrolidone). The amide naturally satisfies the optimum balance between water solubility and pronounced hydrophobicity, which directly correlates with hydrotropic efficiency.
    Example 5: Solubility of diauat surfactant
    In another example, when the reaction product of bisDMAPA and a fatty acid was quaternized with methyl chloride, a diquat surfactant was formed. These diquat surfactants have low solubility temperatures (see Table 1).
    Table 1: Solubility temperatures of 1% by weight solutions of compounds provided and classical anionic and cationic surfactants
    C8BnBr = Formula II with R1 = C7H15, R2, R3, R4, R5 = CH3, R6 = Benzyl, Y = Br C8MeCl = Formula II with R1 = C7H15, R2, R3, R4, R5 = CH3, R6 = CH3, Y = CI ClOMeCl = Formula II with R1 = C9 H19, R2, R3, R4, R5 = CH3, R6 = CH3, Y = CI
    C12 MeCl = Formula II with R1 = CnH23, R2, R3, R4, R5 = CH3, R6 = CH3, Y = CI
    C14 MeCl = Formula II with R1 = C13 H27, R2, R3, R4, R5 = CH3, R6 = CH3, Y = CI
    C 16 MeCl = Formula II with R 1 = C 15 H 31, R 2, R 3, R 4, R 5 = CH 3, R 6 = CH 3, Y = Cl
    C18 MeCl = Formula II with R1 = C17 H35, R2, R3, R4, R5 = CH3, R6 = CH3, Y = CI
    C80cBr = Formula II with R1 = C7H15, R2, R3, R4, R5 = CH3, R6 = C8H17, Y = CI
    C 10 DeBr = Formula II with R 1 = C 9 H 19, R 2, R 3, R 4, R 5 = CH 3, R 6 = C 10 H 21, Y = Cl
    C 12 Do Br = Formula II with R 1 = C 11 H 23, R 2, R 3, R 4, R 5 = CH 3, R 6 = C 12 H 25, Y = Cl
    NaCl 12 = Sodium laurate SDS = Sodium dodecyl sulfate CTAB = Cetrimonium bromide DTAB = Dodecyl trimethyl ammonium bromide
    Example 6: Compatibility with anionic surfactants
    Shampoos and other personal care products are usually based on an anionic surfactant, usually sodium laureth sulfate (LES). Further ingredients for stability and property-enhancing reasons are added, such as cationic compounds, especially surfactants, to increase foam stability and improve the conditioning properties of the product. The cationic surfactants will adsorb on the negatively charged surface of the hair and will reduce friction as the hydrophobic tails will stick into the air. The concentration range of cationic amphiphiles is limited for such applications due to the formation of insoluble precipitates with anionic surfactants at a certain mixing ratio. Finding alternatives that are equivalent or even more powerful in performance and toxicity than the classically used cationic compounds is still the center of attention.
    To determine the applicability of the diquats, the compatibility was tested in different ratios with LES in the temperature range of 0 ° C and 90 ° C. The results are summarized in Table 2. The methyl-quaternized derivatives in particular show very good compatibility with the anionic surfactant. Up to a carbon-hydrogen tail of 10 carbon atoms, no precipitation was observed and with increasing chain length, only a very narrow range of mixing ratios leads to an insoluble precipitate. In contrast, the octyl and benzyl quaternized derivatives precipitate in a wide range and therefore do not form good alternatives to the usual cationic compounds in the application where anionic surfactants are mixed.
    Table 2: Compatibility observations at ambient temperature of mixtures of sodium laureth sulfate (Texapone extract N70) with diquats (Formula II type of compounds: abbreviations see Table 1) of 1% by weight of total surfactant in water.
    Cl. = Clear; Blu. = Bluish; Visc. = Viscous; Prec. = Precipitation; Turb. = Cloudy
    Example 7: Foam-stimulating properties
    With the diquat surfactants of formula (II), foam can generally be produced with a higher efficiency than conventional surfactants such as SDS (sodium dodecyl sulfate) and DTAB (dodecyl trimethylammonium bromide). The results of the tests performed in this example are shown in Figures 2A and 2B.
    These figures show a comparison of the foam volume per second of pure tertiary amide compounds of formula (II) with conventional surfactants (SDS and DTAB), depending on the chain length of the R1 fatty acid chain (Fig. 2A) and in a mixture with sodium laureth sulfate (Fig. 2B). The foam volume per second reaches a maximum at a chain length of C14 and is then greatly reduced with an increasing number of carbon atoms in the hydrophobic tail. In general, the more efficient the surface tension is reduced with a surfactant, the more successful the foaming becomes. The effect of the surface tension reduction is less pronounced with chain lengths higher than C14, leading to very powerful foam formers with chain lengths of C12 and C14. A better foaming than DTAB or SDS is potentially achieved on the one hand by optimum diffusion rates within the film, since, in the case of too high diffusion rates, surface active molecules in the bulk of the liquid between the walls of the soap bubbles have a weak spot in the film before the surface transport is active. In this case the weak spot will not be repaired. On the other hand, the higher electrostatic repulsion caused by the double-charged main groups increases film stability. The thinning of a soap bubble wall continues until charged groups on opposite sides of the wall come close enough together to cause an electrical repulsion. This rejection prevents the film from becoming thinner.
    As can be seen in Figure 2B, the addition of 10% of the tertiary amide compound to a sodium laureth sulfate (Texapon N70) solution with 1 weight% of a surfactant in total leads to an increase in foaming. In particular, the short chain derivatives exhibit a highly efficient foam-stimulating behavior.
    Example 8: Excipient for glyphosate
    The purpose of this study is to test various tertiary amide compounds of the present invention for their ability to function as a vehicle for the highly polar and charged herbicide glyphosate. A good adjuvant for glyphosate, seen from a technical point of view, must have different functions. The adjuvant must provide good wetting of the leaf surface, facilitate the leaf penetration of glyphosate under very different climatic conditions and must have low or no phytotoxicity to prevent inhibition of glyphosate translocation in the weeds and to avoid crop damage when used in glyphosate resistant crops. In a previous study, a screening procedure for testing excipients for glyphosate was developed (Ruiter et al. 1998). Wheat plants are used as a model for hard-to-wet grasses and black nightshade is used as a model for a plant with an easy-to-wet but hard-to-penetrate leaf surface.
    Plant material. Black nightshade and winter wheat (cv. Iliad) are grown in a culture cabinet at 14 hours of light, at a temperature of 18/12 (± 0.5) ° C (day / night), and at a relative humidity of 70/80 ( ± 5)% (day / night). Light was provided by high-pressure mercury lamps and fluorescent lamps to give 160 pmol.m-2.s-1 at leaf level. The plants are grown in 11 cm diameter plastic pots filled with a mixture of sand and humus-rich potting soil (1: 2 in volume). The pots are placed on sub-irrigation mats that are moistened daily with a nutrient solution at half strength. After germination, the wheat seedlings are thinned to six plants per pot for the efficacy experiments. Seedlings of black nightshade are thinned to one plant per pot. Black nightshade and wheat are treated at the four and three leaf stages, respectively. The fresh weight of the plants is measured 14 days after the treatment (14 DAT, black nightshade) or 21 days after the treatment (21 DAT, wheat).
    Herbicide application. The glyphosate solutions are applied with a laboratory sprayer operating on air pressure with 1.2 mm spray openings, provided with a perforated (0.6 mm) swirl pin and capable of delivering 200 L / ha at 303 kPa.
    Treatment solutions. A list of the excipients tested is shown in Table 3. The excipients are added to the unformulated glyphosate mono-isopropylamine salt [MON 8717 (glyphosate IPA salt 648 g ab / L = 2.84 M without excipient) (ab = active ingredient)] at a concentration of 0.25% (w / v) active additive compound. Demineralized water is used as a carrier. A suboptimal amount of glyphosate, which (ideally) gives a growth reduction of 0-20% without excipient, is used to demonstrate the effects of the excipient. Based on previous work, these quantities are 20.3 g ze / ha (equivalent to 0.6 mM) on a black nightshade and 77.8 g ze / ha (equivalent to 2.3 mM at 200 L / ha) on wheat (she = acid equivalent).
    Results. The results are shown in Table 3. The fresh weight of the untreated plants is taken as a reference (100%). The lower the fresh weight of the treated plant, the stronger the excipient. An industrial standard was also added to the test series.
    Table 3: Results of the excipient for glyphosate testing
    (1) Each excipient was added to 0.25% w / v (2.5 g / L) (2) IPA glyphosate: unformulated isopropylamine salt of glyphosate: for SOLNI: 0.6 mM (equivalent to 20.3 g of them / ha at 200 L / ha) & for WHEAT: 2.3 mM (equivalent to 77.8 g ze / ha at 200 L / ha) (ze = acid equivalent) (3) Agnique GPU: mixture of tallow of amine ethoxylates and glycols
    Example 9: Excipient for Carfentrazone Ethyl
    The purpose of this study is to test whether the N, N-bis (3- (dimethylamino) propyl) octanamide excipient exhibits efficacy relative to other (more lipophilic) herbicides. In this test we looked at the performance with carfentrazon-ethyl (Spotlight Plus from FMC) on white goose foot (Chenopodium album L; CHEAL).
    Plant material White goose foot (Chenopodium album L .; CHEAL) plants are grown in a grow box at 14 hours of light, at a temperature of 18/12 (± 0.5) ° C (day / night), and at a relative humidity of 70 / 80 (± 5)% (day / night). Light was provided by high pressure mercury lamps and fluorescent lamps to give 250 pmol.rrT2.s'1 at leaf level. The plants are grown in 11 cm diameter plastic pots filled with a mixture of sand and humus-rich potting soil (1: 2 in volume). The pots are placed on sub-irrigation mats that are moistened daily with a nutrient solution at half strength. After germination, the wheat seedlings are thinned to two plants per pot for the efficacy experiments. The white goose foot plants are treated at the four-leaf stage. The fresh weight of the plants is measured 7 days after the treatment (7 DAT).
    Herbicide application. The treatment solutions are applied with a pressure washer laboratory sprayer with 1.2 mm nozzles, equipped with a perforated (0.6 mm) swirl pin and capable of delivering 200 L / ha at 303 kPa. The following herbicide was used with the treatment solutions: carfentrazone-ethyl, Spotlight Plus (FMC) ME formulation, 60 g a.b./L.
    Treatment solutions. The excipient is added to the treatment solution at a concentration of 0.25% (w / v) active excipient compound. Demineralized water is used as a carrier. A sub-optimal amount of the herbicide, which (ideally) gives a growth reduction of 0-20% without excipient, is used to demonstrate the effects of the excipient.
    Experimental design and data analysis. The experiment was performed with four duplicates per experiment based on a completely random design.
    Results. The results (average values) are shown in Table 4. The addition of the excipient to the herbicide clearly increases the efficacy of the herbicide.
    Table 4: Results of the excipient for Carfentrazone ethyl test
    Example 10: Excipient for Dicamba
    The purpose of this study is to test whether the N, N-bis (3- (dimethylamino) propyl) octanamide excipient exhibits efficacy relative to other (more lipophilic) herbicides. This test looked at the performance with Dicamba DMA salt (Banvel formulation) on black nightshade.
    Plant material. Black nightshade (Solanum nigrum L .; SOLNI) is grown in a culture cabinet at 14 hours of light, at a temperature of 18/12 (± 0.5) ° C (day / night), and at a relative humidity of 70/80 (± 5)% (day / night). Light was provided by high-pressure mercury lamps and fluorescent lamps to give 250 pmol.m-2.s -1 at leaf level. The plants are grown in 11 cm diameter plastic pots filled with a mixture of sand and humus-rich potting soil (1: 2 in volume). The pots are placed on sub-irrigation mats that are moistened daily with a nutrient solution at half strength. After germination, the wheat seedlings are thinned to one plant per pot for the work experiments. The black nightshade is treated at the four-leaf stage. The fresh weight of the plants is measured 16 days after the treatment (16 DAT).
    Herbicide application. The treatment solutions are applied with a pressure washer laboratory sprayer with 1.2 mm nozzles, equipped with a perforated (0.6 mm) swirl pin and capable of delivering 200 L / ha at 303 kPa. The following herbicide was used with the treatment solutions: Dicamba DMA salt, Banvel formulation, 480 g a.b./L.
    Treatment solutions. The excipient is added to the treatment solution at a concentration of 0.25% (w / v) active excipient compound. Demineralized water is used as a carrier. A sub-optimal amount of the herbicide, which (ideally) gives a growth reduction of 0-20% without excipient, is used to demonstrate the effects of the excipient.
    Experimental design and data analysis. The experiment was performed with four duplicates per experiment based on a completely random design.
    Results. The results (average values) are reported in Table 5. The addition of the excipient to the herbicide clearly increases the efficacy of the herbicide.
    Table 5: Results of the excipient for Dicamba DMA salt test
    Example 11: Excipient for Fenoxaprop-P-ethyl
    The purpose of this study is to test whether the N, N-bis (3- (dimethylamino) propyl) octanamide excipient exhibits efficacy relative to other (more lipophilic) herbicides. This test looked at the performance with Fenoxaprop-P-ethyl.
    Plant material. Wild oats (Avena fatua L. AVEFA) are grown in a culture cabinet at 14 hours of light, at a temperature of 18/12 (± 0.5) ° C (day / night), and at a relative humidity of 70/80 ( ± 5)% (day / night). Light was provided by high-pressure mercury lamps and fluorescent lamps to give 250 pmol.m'2.s'1 at leaf level. The plants are grown in 11 cm diameter plastic pots filled with a mixture of sand and humus-rich potting soil (1: 2 in volume). The pots are placed on sub-irrigation mats that are moistened daily with a nutrient solution at half strength. After germination, the wheat seedlings are thinned to four plants per pot for the efficacy experiments. The plants are treated in the three-leaf stage. The fresh weight of the plants is measured 21 days after the treatment (21 DAT).
    Herbicide application. The treatment solutions are applied with a pressure washer laboratory sprayer with 1.2 mm nozzles, equipped with a perforated (0.6 mm) swirl pin and capable of delivering 200 L / ha at 303 kPa. The following herbicide was added to the treatment solutions: Phenoxaprop-P-ethyl, Puma EW formulation, 69 g a.b./L.
    Treatment solutions. The excipient is added to the treatment solution at a concentration of 0.25% (w / v) active excipient compound. Demineralized water is used as a carrier. A sub-optimal amount of the herbicide, which (ideally) gives a growth reduction of 0-20% without excipient, is used to demonstrate the effects of the excipient.
    Experimental design and data analysis. The experiment was performed with four duplicates per experiment based on a completely random design.
    Results. The results (average values) are reported in Table 6. The addition of the excipient to the herbicide clearly increases the efficacy of the herbicide.
    Table 6: Results of the excipient for the Fenoxaprop-P-ethyl test
    Example 11: Compatibility with high concentration formulations.
    High concentration formulations of the glyphosate IPA salt are prepared by mixing the components as indicated in Table 7. In each case, a formulation comprising a glyphosate content of about 450 g.e. / l (z.e. = acid equivalent) obtained.
    Table 7: Results of the compatibility improvement tests
    With DMAPA amides and Ethomeen® (tertiary tallow amine ethoxylate), poor mixing was observed and two-phase systems were already obtained at room temperature. Amides based on the bisDMAPA structure are much more compatible with water and lead to one-phase glyphosate formulations with a high cloud point. Indeed, when the bisDMAPA amide was used in conjunction with Ethomeen®, a stable one-phase composition was again obtained, indicating that, due to their amphiphilic properties, bisDMAPA amides can act as a compatibilizer and dissolution aid.
    权利要求:
    Claims (15)
    [1]
    CONCLUSIONS
    An agrochemical composition containing at least one active ingredient selected from the group consisting of pesticides, growth regulators and / or fertilizers, characterized in that it further comprises a tertiary amide according to formula (I)

    (I) or according to formula (II)

    (II) wherein: R 1 is an aliphatic group with 5-23 carbon atoms; R 2, R 3, R 4 and R 5 are, independently, hydrogen, -CH 2 CH 2 OH, -CH 2 CH (CH 3) OH or an aliphatic group of 1-5 carbon atoms, preferably 1 to 3 carbon atoms; R 6 is hydrogen or an aliphatic or aromatic group with 1-22 carbon atoms; and Y 'is an anion.
    [2]
    An agrochemical composition according to claim 1, wherein R 2 and R 3 are the same as R 4 and R 5.
    [3]
    An agrochemical composition according to claim 1 or 2, wherein the amide has the formula (I) and wherein R1 is preferably an aliphatic group with 5-13 carbon atoms, preferably 5-9 carbon atoms, wherein R1 more particularly a fatty acid chain.
    [4]
    An agrochemical composition according to claim 1 or 2, wherein the amide has the formula (II) and wherein R 1 is preferably an aliphatic group with 7-21 carbon atoms, preferably 9-17 carbon atoms.
    [5]
    An agrochemical composition according to any of claims 1 to 4, characterized in that it is free from the corresponding secondary amides according to formula (III) and (IV):

    or that per 100 moles of said tertiary amide comprises at most 50 moles, preferably at most 25 moles, of these corresponding secondary amides according to formula (III).
    [6]
    An agrochemical composition according to any of claims 1 to 5, characterized in that it is a liquid composition, in particular a solution, an emulsion or a suspension.
    [7]
    An agrochemical composition according to any of claims 1 to 5, characterized in that it is a solid composition that is in particular in a powder or granular form.
    [8]
    An agrochemical composition according to any of claims 1 to 7, characterized in that it additionally contains at least one anionic surfactant, the amide being in particular an amide according to formula (II).
    [9]
    An agrochemical composition according to any of claims 1 to 8, characterized in that it comprises at least two active ingredients, comprising at least one hydrophilic active ingredient and at least one lipophilic active ingredient.
    [10]
    An agrochemical composition according to any of claims 1 to 9, characterized in that it is formulated for sheet applications.
    [11]
    An agrochemical composition according to any of claims 1 to 10, characterized in that it comprises at least one pesticide selected from the group consisting of herbicides, acaricides, fungicides and insecticides.
    [12]
    Use of a tertiary amide as defined in any one of claims 1 to 5 as an adjuvant in an agrochemical composition containing a pesticide, a growth regulator and / or fertilizers.
    [13]
    A detergent composition, characterized in that it contains at least one tertiary amide as defined in any of claims 1 to 5, and at least one anionic surfactant, the detergent composition preferably being a water-based liquid composition.
    [14]
    A detergent composition according to claim 13, additionally comprising at least one soap.
    [15]
    A detergent composition according to claim 13 or 14, wherein said tertiary amine has the formula (II), wherein R 6 is preferably an aliphatic group with 1-3 carbon atoms, more preferably a methyl group.
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    同族专利:
    公开号 | 公开日
    WO2012150343A1|2012-11-08|
    AR086273A1|2013-12-04|
    US9992994B2|2018-06-12|
    CN103547151A|2014-01-29|
    EP2520166A1|2012-11-07|
    BR112013028013B1|2021-06-01|
    US20140080708A1|2014-03-20|
    BR112013028013A2|2020-07-21|
    EP2704567B1|2018-06-27|
    EP2704567A1|2014-03-12|
    CN103547151B|2016-05-25|
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    EP111648465|2011-05-04|
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