Surfactant production process

Abstract

Processes for producing surfactants of formula (I), and surfactant compositions are provided. Additionally, specific surfactants and compositions thereof, and their use in a wide variety of applications, such as in all-purpose cleaning products, are provided. [Formula 1] JPEG2025510974000023.jpg33170

Description

[Technical field]

[0001] The present invention relates to a process for producing a surfactant. The present invention further relates to particular embodiments of a surfactant and a surfactant composition. [Background technology]

[0002] Surfactants are compounds that reduce the surface tension between two phases, especially between two liquids. Surfactants are generally organic amphiphilic compounds, i.e. compounds that contain both hydrophobic and hydrophilic groups. Such compounds are used, for example, as detergents, wetting agents, foaming agents, emulsifiers, and dispersants.

[0003] N-alkylamino acid based surfactants have been shown to be promising amphoteric surfactants. These surfactants have an amino acid as a polar zwitterionic head group. N-alkylamino acid based surfactants exhibit low critical micelle concentrations (CMC) and low surface tension values ​​at the CMC.

[0004] Being commodity surfactants, they are produced on a large scale, and especially from the economic point of view of biobased systems, there is an urgent need to develop direct and sustainable catalytic methods to obtain environmentally friendly and fully biobased alternatives.Despite the clear potential of N-alkylamino acids, there is a relative lack of selective catalytic methods to directly functionalize unprotected amino compounds, such as α-amino acids, to obtain these compounds.

[0005] Generally, N-alkylation of α-amino acids has been carried out using stoichiometric methods such as reductive amination of aldehydes with complexing salts or nucleophilic substitution with alkyl halides. One method described in the art involves the reductive amination of fatty aldehydes and amino acids in the presence of elemental hydrogen.

[0006] Several publications, such as Yan et al., J. Sep. Sci. 2017, 40, 1834-1842; Tanimura et al., J. Chromatogr. 1984, 284, 285-288; Tanimura et al., Anal. Chem. 1984, 56, 1152-1155; Tong et al., J. Sep. Sci. 2018, 41, 1479-1488; and Cussler et al., Am. Inst. Chem. Eng. 1992, 38, 10, 1493-1498, describe the reductive amination of dodecanal with L-proline or L-hydroxyproline in alcohol in the presence of palladium on carbon (Pd / C) at room temperature and 1 bar hydrogen pressure.

[0007] Joly et al., J. Chem. Soc. Perkin Trans. 2 2001, 998-1004, describes the reductive amination of dodecanal with L-proline or L-hydroxyproline in the presence of Pd / C in an alcoholic solvent at room temperature and 50 bar hydrogen pressure.

[0008] US 2019 / 0218170 A1 describes branched trialkylamine precursors for the production of surfactants. A number of starting materials, including 2-ethylhexanal and sarcosine, and a wide range of conditions for obtaining the precursors are described.

[0009] French Patent Application FR 2 469 395 A1 mentions the reductive amination of dodecanal with pipecolic acid in the presence of Pd / C, at 1 bar hydrogen and 50-55° C., with a volume ratio of ethanol to water of about 5:1. This is an example of a laboratory synthesis dealing with a very dilute reaction mixture and is not suitable for scale-up on an industrial scale.

[0010] Selective N-alkylation of unprotected amino acids remains challenging: most amino acids have limited solubility in non-polar organic solvents, and their zwitterionic properties make these substrates sensitive to changes in pH and basic or acidic reagents.

[0011] The reductive amination of the organic feed substrate may take place in a suitable solvent. A properly selected solvent may ensure the solubility of the feed substrate and the amination product. In addition, the solvent may provide advantages to such reductive amination reactions, such as improved hydrogen solubility, reduced viscosity of the reaction mixture, improved mixing efficiency, improved heat transfer, or limited formation of undesired by-products. However, highly dilute reaction mixtures may result in low space-time yields, which may make the process economically unattractive. If the reaction mixture is highly concentrated, the benefits of the solvent may be minimized, for example, the reagents may not be mixed well. Also, the organic feed substrate or its reductive amination product may tend to block or "block" the catalyst to hydrogen, slowing down the reductive amination. Such "blocking" of the catalyst occurs when one or more of the species present, whether the organic feed substrate or its reductive amination product, are poorly soluble or are strongly absorbed or adsorbed on the catalyst surface, thereby preventing the access of hydrogen molecules to the active catalytic sites.

[0012] Further, there remains a need to provide surfactants in high yields under environmentally beneficial conditions, particularly using bio-renewable starting materials, i.e., materials that are naturally available, available through biological processes, and / or materials that can be utilized through chemical processes from naturally available materials. Additionally, there is a need for new surfactants. Summary of the Invention [Means for solving the problem]

[0013] The present invention relates to a compound represented by the general formula (I) [ka] (In the formula, X is selected from COOH and CH2SO3H; R 1 is C5-C 17 -Alkyl and C5-C 17 -alkenyl, R 2 is selected from hydrogen, C1-C4-alkyl and CH2PO3H2, R 3 is selected from hydrogen and C1-C8-alkyl, C1-C8-alkyl being optionally substituted with one or more substituents selected from hydroxy, amino, C1-C8-alkylamino, carboxyl, C1-C8-alkylcarboxylate, C1-C8-alkylamido, thio, C1-C8-alkylthio, guanidino and aromatic groups optionally substituted with hydroxy groups, Or, R 2 and R 3 is R 2 The nitrogen atom to which R is bonded 3 together with the carbon atom to which it is attached form a 5- or 6-membered heterocyclic ring optionally substituted with hydroxy groups) or a salt thereof, This process comprises reacting a compound represented by the general formula (II) [ka] of aldehydes General formula (III) [ka] (In the formula, R 2 , R 3 and X is as defined above) or a salt thereof with an amino compound, In the presence of molecular hydrogen and a heterogeneous catalyst comprising an element from group 10 of the periodic table of elements, The reductive amination is carried out in a feed operation, in which an amino compound of the general formula (III) is provided, to which an aldehyde of the general formula (II) is metered, Reductive amination is at a pressure of molecular hydrogen of at least 1 bar, preferably in the range from more than 1 bar to less than 50 bar, - at a temperature of at least 25°C, and - a Hildebrand solubility parameter δ of 18-38 MPa at a solvent dilution ratio of less than 7.0 L / kg (the solvent dilution ratio is the total volume of the solvent relative to the total weight of the aldehyde of general formula (II) and the amino compound of general formula (III)); 1 / 2 The reaction is carried out in a solvent in the range of DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The term solvent dilution ratio as used herein refers to the total volume of solvent relative to the total weight of the aldehyde of general formula (II) and the amino compound of general formula (III). The term "total volume of solvent" includes the initial volume of solvent and the volume of solvent added during the reductive amination. The volume of solvent added during the reductive amination is, for example, the volume of solvent included in the solution of reactants metered in during the process of the feeding operation. When the solvent is composed of a mixture of different solvents, the volume of the mixture may be smaller than the sum of the volumes of the individual solvents. This phenomenon is known as "volume shrinkage". This may occur, for example, when the solvent is composed of an aliphatic alcohol and water. It is understood that the "total volume of solvent" takes into account the volume shrinkage.

[0015] This process can obtain high yields under mild reaction conditions and limited reaction volume.Furthermore, the aldehyde of formula (II) and the amino compound of formula (III) are typically naturally available, available through biological processes, and / or available through chemical processes from naturally available materials.Overall, this process can therefore obtain surfactants in an environmentally friendly way.

[0016] The process for producing surfactants of general formula (I) comprises the reductive amination of an aldehyde of general formula (II) with an amino compound of general formula (III) or a salt thereof: [ka] X is selected from COOH, CH2SO3H and COONa. Preferably, X is COOH.

[0017] R 1 is C5-C 17 -Alkyl and C5-C 17 -alkenyl, which may be linear or branched. 1 When R is an alkenyl group, 1 R can be monounsaturated or polyunsaturated. 1 is preferably C7-C 15 -Alkyl and C7-C 15 -alkenyl, more preferably C7-C 13 -Alkyl and C7-C 13 -alkenyl, most preferably C7-C 11 -Alkyl and C7-C 11 -alkenyl.

[0018] In a preferred embodiment, R 1 is C8-, C9- or C 11 -alkyl, especially C- or C 11 -alkyl, or R 1 is C9-C 17 -alkenyl, in particular C9-alkenyl.

[0019] The aldehyde of general formula (II) is an aliphatic aldehyde.Suitable aldehyde of general formula (II) includes octanal, nonanal, decanal, undecanal, dodecanal, tetradecanal, hexadecanal, 2-ethylhexanal and citral, in particular citral, dodecanal and tetradecanal.Citral is understood to be a mixture of two geometric isomers, specifically geranial (citral A) and neral (citral B).

[0020] R 2 can be selected from hydrogen, C1-C4-alkyl, which may be linear or branched, and CH2PO3H2. Preferably, C1-C4-alkyl is ethyl or methyl, in particular methyl.

[0021] R 3 can be selected from hydrogen and optionally substituted C1-C8-alkyl, which may be linear or branched. Preferably, C1-C8-alkyl is optionally substituted C1-C6-alkyl or optionally substituted C1-C4-alkyl, in particular optionally substituted methyl, optionally substituted ethyl, optionally substituted n-propyl or optionally substituted n-butyl.

[0022] In a preferred embodiment, R 2 is hydrogen or methyl, R 3 is optionally substituted C1-C4-alkyl.

[0023] R 3 is optionally substituted with one or more substituents selected from hydroxy groups, amino groups, C-C-alkylamino groups, carboxyl groups, C-C-alkylcarboxylate groups, C-C-alkylamido groups, thio groups, C-C-alkylthio groups, guanidino groups, and aromatic groups such as indolyl or imidazolyl groups, in which case the aromatic groups are optionally substituted with hydroxy groups.

[0024] In another embodiment, R 2 and R 3 is R 2 The nitrogen atom to which R is bonded 3 together with the carbon atom to which it is attached form a 5- or 6-membered heterocyclic ring, such as a pyrrolidinyl or piperidinyl group. The heterocyclic ring may be saturated or unsaturated, preferably saturated. The heterocyclic ring is optionally substituted with a hydroxy group.

[0025] Suitable amino compounds of general formula (III) include proteinogenic amino acids such as alanine, arginine, aspartic acid, asparagine, cysteine, selenocysteine, glycine, glutamic acid, glutamine, histidine, methionine, leucine, isoleucine, lysine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine and valine, in particular proline, as well as non-proteinogenic amino acids, amino acid derivatives and amino acid analogues, such as glyphosate, hydroxyproline, pipecolic acid, pyrrolysine, ornithine, carnitine, β-N-methylaminoalanine, N-methylalanine, sarcosine, taurine and N-methyltaurine, in particular N-methyltaurine, N-methylalanine and sarcosine.

[0026] The surfactant may be a non-ionic compound of general formula (I), an internal (zwitterionic) salt of a compound of general formula (I), or an external salt. The amino compound of general formula (III) may be a non-ionic compound or an external salt of a compound of general formula (III). The acid group of moiety X of formulas (I) and (III) is shown in its undissociated form and R 2 The nitrogen atom bearing is shown in its unprotonated form, but it is understood that the reaction product obtained in this process may be an internal (zwitterionic) salt in which the acid group dissociates and assumes a negative charge and the nitrogen atom is protonated and assumes a positive charge. However, it is also possible that only one of the aforementioned groups is charged, and this charge predominates and is compensated by a counterion. These "external salts" can be obtained under acidic or basic conditions. The same is true for any acidic and basic substituents.

[0027] In one embodiment, the process comprises neutralizing the surfactant of general formula (I) with an acid or base, particularly with an acid. In this way, the outer salt of the surfactant of general formula (I) is obtained. In another embodiment, the amino compound of general formula (III) is the outer salt. In this embodiment, the outer salt of general formula (I) is obtained directly by reaction with the aldehyde of general formula (II).

[0028] The acid may be selected from organic acids and mineral acids. Suitable mineral acids include hydrochloric acid, sulfuric acid, amidosulfuric acid, and phosphoric acid. Preferably, the mineral acid is selected from hydrochloric acid and sulfuric acid.

[0029] Suitable organic acids include carboxylic acids, sulfonic acids, carbonic acids, organic phosphonic acids, and aminocarboxylic acids. Preferably, the organic acid is selected from carboxylic acids, most preferably from formic acid, acetic acid, oxalic acid, propionic acid, hydroxypropionic acid, lactic acid, malic acid, maleic acid, succinic acid, tartaric acid, aconitic acid, citric acid, and glutamic acid.

[0030] The base can be selected from metal hydroxides and amines. Suitable metal hydroxides include alkali metals, especially sodium hydroxide and potassium hydroxide. Sodium hydroxide is particularly preferred. Suitable amines include ammonia, aliphatic amines such as monomethylamine, dimethylamine, monoethylamine, diethylamine, monopropylamine, dipropylamine, decylamine, dodecylamine, and tetradecylamine, alkanolamines such as ethanolamine and diethanolamine, and lysine. External salts obtained under basic conditions generally show improved solubility at higher pH values.

[0031] Neutralization of the amine surfactant of general formula (I) is typically carried out at room temperature, i.e. 25°C, and under atmospheric pressure. Neutralization is typically carried out in a solvent, preferably the above-mentioned solvents. The neutralized reaction product can be purified by typical means, such as evaporating the solvent, to obtain a crude material, which can be further purified, for example, by recrystallization.

[0032] The molar ratio of the total amount of the aldehydes of general formula (II) to the total amount of the amino compounds of general formula (III) is preferably in the range of 0.8:1 to 1.3:1, more preferably 0.9:1 to 1.2:1, and most preferably 0.95:1 to 1.15:1.

[0033] The reductive amination is carried out in the presence of a heterogeneous catalyst comprising an element from group 10 of the periodic table of elements. The element from group 10 may be selected from nickel (Ni), palladium (Pd), and platinum (Pt). Preferably, the element from group 10 is selected from nickel (Ni) and palladium (Pd), in particular palladium (Pd).

[0034] The metals can be used as such or can be applied to a support. Preferred supports are selected from aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, and activated carbon. Supported metals are particularly preferred. Preferred supports are activated carbon, aluminum oxide, and titanium dioxide. A particularly preferred support is activated carbon. A particularly preferred hydrogenation catalyst is palladium on activated carbon.

[0035] In a preferred embodiment, the heterogeneous catalyst is selected from Raney nickel and palladium on activated carbon, in particular palladium on activated carbon (Pd / C). When the heterogeneous catalyst is palladium on activated carbon, the catalyst may include a binder such as polytetrafluoroethylene (PTFE).

[0036] The catalyst is typically present in an amount of at most 2.5% by weight, calculated as Group 10 element relative to the weight of the amino compound of general formula (III), such as 0.01-2.5% by weight, preferably 0.01-1.5% by weight, more preferably 0.01-1.5% by weight, such as 0.3-1.2% by weight or 0.5-1.1% by weight. Thus, the process of the present invention requires relatively small amounts of catalyst.

[0037] The reductive amination is carried out at a molecular hydrogen pressure of at least 1 bar, preferably in the range of at least 1 bar to less than 50 bar, in particular in the range of more than 1 bar to less than 50 bar. Preferably, the molecular hydrogen pressure is in the range of 3 to 30 bar, more preferably 3 to 25 bar, most preferably 4 to 21 bar. A molecular hydrogen pressure of more than 1 bar advantageously shortens the reaction time and improves the efficiency of the process.

[0038] On the other hand, if the hydrogen pressure is too high, the aldehyde does not participate in the reductive amination and is reduced to the corresponding alcohol, which is extremely difficult to separate from the reaction mixture. Therefore, working with hydrogen pressures within the claimed range results in high selectivity and high efficiency of the process.

[0039] The reductive amination is carried out at a temperature of at least 25° C. Preferably, the temperature is in the range of 25 to 120° C., more preferably 30 to 90° C., and most preferably 40 to 50° C. This temperature range allows the reductive amination reaction to proceed at a suitable rate under mild conditions.

[0040] Reductive amination is performed when the Hildebrand solubility parameter δ is 18 to 38 MPa. 1 / 2 in the range of 30 to 37 MPa 1 / 2 , more preferably 31 to 37 MPa 1 / 2 , and most preferably 32 to 35 MPa 1 / 2 The mixing is carried out in the presence of a solvent with a Hildebrand solubility parameter δ in the range of 0.1 to 0.5. Solvents with a Hildebrand solubility parameter δ in this range have been found to provide high solubility for both the starting material and the resulting surfactant. The solvent may be in the form of a single solvent or a mixture of two or more solvents. The Hildebrand solubility parameter δ is a numerical estimate of the degree of interaction between compounds and is therefore used as an indicator of solubility. Compounds with similar δ values ​​are considered to be highly miscible.

[0041] The Hildebrand solubility parameter δ is well known in the literature. The following table shows some representative solvents and their Hildebrand solubility parameters, as listed in Barton, Allan FM (1983), Handbook of Solubility Parameters and Other Cohesion Parameters, CRC Press.

[0042] [Table 1]

[0043] The Hildebrand solubility parameter, δ, of a solvent mixture can be determined by volume-averaging the Hildebrand values ​​of the individual solvents. For example, the Hildebrand solubility parameter of a mixture of two parts ethanol and one part water can be calculated as follows: δ = ((2 × 26.2 MPa 1 / 2 +48.0MPa 1 / 2 ) / 3)=33.5MPa 1 / 2 .

[0044] Selection of a solvent having a Hildebrand solubility parameter δ in the above range ensures that the solvent has suitable solubility properties for the amino compound of general formula (III) and that the reductive amination reaction proceeds at an appropriate rate.

[0045] In a preferred embodiment, the solvent comprises a protic solvent and / or an aprotic solvent containing an ether moiety, in particular a protic solvent. A protic solvent is one that can provide a proton (H + ) is understood to be a solvent that is capable of donating a proton to the solute. An aprotic solvent is not capable of donating a proton to the solute.

[0046] Preferably, the solvent comprises at least one protic solvent selected from water and an aliphatic alcohol. Preferred aliphatic alcohols include methanol, ethanol and isopropanol, especially ethanol. More preferably, the solvent comprises an aliphatic alcohol or a mixture of an aliphatic alcohol and water. In a preferred embodiment, the solvent is a mixture of an aliphatic alcohol and water in a volume ratio ranging from 1:1 to 4:1, preferably from 1.25:1 to 3:1, most preferably from 1.5:1 to 2:1. In a particularly preferred embodiment, the solvent is a mixture of ethanol and water in a volume ratio ranging from 1:1 to 4:1, preferably from 1.25:1 to 4:1, more preferably from 1.5:1 to 2:1, most preferably from 1.5:1 to 2:1. The volume ratio is understood to relate to the volume ratio of the individual solvents before mixing, i.e. ignoring any volume shrinkage that may occur on mixing.

[0047] In another embodiment, the solvent comprises at least one aprotic solvent containing an ether moiety, such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, or tetrahydropyran, in particular tetrahydrofuran. In one embodiment, the solvent is tetrahydrofuran.

[0048] In a further embodiment, the solvent comprises at least one aprotic solvent containing an ether moiety and at least one protic solvent. For example, the solvent can comprise a mixture of tetrahydrofuran and at least one protic solvent, particularly water or alcohol. In a preferred embodiment, the solvent is a mixture of tetrahydrofuran and water or ethanol, particularly a mixture of tetrahydrofuran and water.

[0049] The reductive amination is carried out at a solvent dilution rate of less than 7.0 L / kg, preferably at most 4.5 L / kg, more preferably at most 2.5 L / kg. Typically, the reductive amination is carried out at a solvent dilution rate of 1.0 to less than 7.0 L / kg, preferably at most 1.0 to 4.5 L / kg, more preferably at most 1.0 to 2.5 L / kg. When the concentrations of the aldehyde of general formula (II) and the amino compound of general formula (III) are within this range, the amino compound and the aldehyde can be reacted efficiently with high selectivity. A more dilute reaction mixture will result in a lower space-time yield, and in some cases where the reaction mixture is too concentrated, the benefit of the solvent may be minimized.

[0050] In one embodiment, the reductive amination is carried out at a molecular hydrogen pressure ranging from 3 to 30 bar, at a temperature ranging from 25 to 120° C., and at a pressure ranging from 18 to 38 MPa. 1 / 2 The reaction is carried out in a solvent having a Hildebrand solubility parameter δ in the range of 1.0 to 7.0 L / kg.

[0051] In a further embodiment, the reductive amination is carried out at a molecular hydrogen pressure ranging from 3 to 25 bar, preferably from 4 to 21 bar, at a temperature ranging from 25 to 120° C., and at a pressure ranging from 18 to 38 MPa. 1 / 2 The reaction is carried out in a solvent having a Hildebrand solubility parameter δ in the range of 1.0 to 7.0 L / kg.

[0052] In a further embodiment, the reductive amination is carried out at a pressure of molecular hydrogen in the range of 3 to 30 bar, at a temperature in the range of 30 to 90° C., more preferably 40 to 50° C., and at a pressure of 18 to 38 MPa. 1 / 2 The reaction is carried out in a solvent having a Hildebrand solubility parameter δ in the range of 1.0 to 7.0 L / kg.

[0053] In a further embodiment, the reductive amination is carried out at a molecular hydrogen pressure in the range of 3 to 30 bar, at a temperature in the range of 25 to 120° C., and at a pressure of 30 to 37 MPa. 1 / 2 , preferably 31 to 37 MPa 1 / 2 , more preferably 32 to 35 MPa 1 / 2The reaction is carried out in a solvent having a Hildebrand solubility parameter δ in the range of 1.0 to 7.0 L / kg.

[0054] In a further embodiment, the reductive amination is carried out at a molecular hydrogen pressure in the range of 3 to 30 bar, at a temperature in the range of 25 to 120° C., and at a pressure of 18 to 38 MPa. 1 / 2 The reaction is carried out in a solvent having a Hildebrand solubility parameter δ in the range of 1.0 to 4.5 L / kg, preferably 1.0 to 2.5 L / kg.

[0055] In a further embodiment, the reductive amination is carried out at a molecular hydrogen pressure in the range of 3-30 bar, a temperature in the range of 25-120° C., and a solvent dilution ratio of 1.0-7.0 L / kg, where the solvent is a mixture of an aliphatic alcohol, particularly ethanol, and water in a volume ratio of 1:1-4:1, preferably 1.25:1-3:1, most preferably 1.5:1-2:1.

[0056] In a further embodiment, the reductive amination is carried out at a molecular hydrogen pressure in the range of 3 to 30 bar, at a temperature in the range of 25 to 120° C., and at a pressure of 18 to 38 MPa. 1 / 2 in the range of 0.5-1.0 L / kg, at a solvent dilution rate of 1.0-7.0 L / kg, in which the heterogeneous catalyst is present in an amount of at most 2.5% by weight, such as 0.01-2.5% by weight, preferably 0.01-1.5% by weight, more preferably 0.01-1.5% by weight, such as 0.3-1.2% by weight or 0.5-1.2% by weight, calculated as the proportion of Group 10 element to the total amount of amino compounds of general formula (III).

[0057] In a further embodiment, the reductive amination is carried out at a molecular hydrogen pressure in the range of 3-30 bar, a temperature in the range of 25-120° C. and a solvent dilution rate of 1.0-7.0 L / kg, in which the solvent is a mixture of aliphatic alcohol and water, in particular ethanol and water, in a volume ratio of 1:1-4:1, preferably 1.25:1-3:1, most preferably 1.5:1-2:1, and the heterogeneous catalyst is present in an amount of at most 2.5% by weight, such as 0.01-2.5% by weight, preferably 0.01-1.5% by weight, more preferably 0.01-1.5% by weight, such as 0.3-1.2% by weight or 0.5-1.2% by weight, calculated as the proportion of group 10 element on the total amount of amino compounds of general formula (III).

[0058] The process of the present invention can be carried out in any reactor suitable for maintaining the molecular hydrogen pressure in the desired range and at the desired temperature, such as an autoclave.

[0059] The process of the invention is carried out in a feeding operation, in which the amino compound of general formula (III) is provided (i.e. initially charged) and the aldehyde of general formula (II) is metered thereto. Providing the amino compound of general formula (III) is understood to also include providing a solution of the amino compound of general formula (III). Similarly, metering the aldehyde of general formula (II) thereto includes metering a solution of the aldehyde of general formula (II) thereto. The solvent contained in the solution of the amino compound of general formula (III) and the solvent contained in the solution of the aldehyde of general formula (II) together constitute the solvent in which the reductive amination takes place. The solvents contained in the two solutions can be the same or different. In the latter case, the solvent in which the reductive amination takes place will be a mixture of solvents.

[0060] Generally, the aldehyde of general formula (II) is added at a constant feed rate, which can avoid undesirable side reactions. Thus, on the one hand, the reduction of aldehyde to the corresponding alcohol is suppressed, the surfactant of general formula (I) is obtained with higher selectivity, and the removal of the corresponding alcohol, which is difficult to separate, is avoided.On the other hand, the aldol condensation of aldehyde with itself to form aldehyde dimer is avoided.This again allows higher selectivity, and furthermore suppresses the formation of dimeric surfactants with less favorable properties.

[0061] The reaction product obtained in the process of the present invention can be purified by typical means such as filtering the reaction mixture to remove the heterogeneous catalyst, followed by evaporating the solvent from the filtrate to obtain a crude material. A suitable additional solvent, in particular ethanol, can be added to completely dissolve the reaction product in the reaction mixture obtained before filtration. The crude material can be further purified, for example, by recrystallization.

[0062] In one embodiment, the aldehyde of general formula (II) and / or the amino compound of general formula (III) are bio-based compounds. In this embodiment, the process allows obtaining surfactants in a particularly environmentally friendly manner.

[0063] Radiocarbon and isotope ratio mass spectrometry can be used to determine the biobased content of a material. For example, ASTM International has established a standard method for assessing the biobased content of a material. The ASTM method is designated ASTM-D6866.

[0064] The application of ASTM-D6866 to determine the "bio-based content" of a material is based on the same concepts as radiocarbon dating, but does not use a dating equation. The analysis is based on the determination of the radiocarbon ( 14This is done by deriving the ratio of the amount of biological material present in a sample to the amount of radiocarbon in a modern reference standard. This ratio is reported as a percentage in units called "pMC" (percent modern carbon). When the material being analyzed is a mixture of modern radiocarbon and fossil carbon (which does not contain radiocarbon), the resulting pMC value directly correlates to the amount of biological material present in the sample.

[0065] The modern reference standard used in radiocarbon dating is the NIST standard of known radiocarbon content approximately equivalent to the year 1950. The year 1950 was chosen because it represents the era before thermonuclear weapons testing, when each explosion released large amounts of excess radiocarbon (called "bomb carbon") into the atmosphere. The 1950 reference represents 100 pMC.

[0066] Details of the evaluation of materials to determine whether they are bio-based can be found, for example, in WO 2007 / 095262 A2.

[0067] The surfactants of general formula (I) are preferably at least partially biodegradable, preferably at least 20%, more preferably at least 60% (all percentages are in weight % based on total solids) within 28 days according to OECD 301.

[0068] The process avoids the deleterious aldol condensation of aldehydes with themselves to form aldehyde dimers, thus allowing for higher selectivity, but it is believed that dimerization cannot be completely avoided. It has now been found that the use of small amounts of dimeric surfactants has a beneficial effect on important surfactant properties such as foam volume, wetting time, surface tension and contact angle.

[0069] The present invention therefore further provides a surfactant composition comprising a surfactant of general formula (I) or a salt thereof as defined above in an amount of at least 90% by weight, relative to the weight of the surfactant composition, and a compound of general formula (IV) or a salt thereof in an amount of 0.01 to 5.0% by weight, relative to the weight of the surfactant composition. [ka] (In the formula, X, R 2 and R 3 is defined as above, and R 4 is C 10 -C 34 -Alkyl and C 10 -C 34 -alkenyl, where R 4 The number of carbon atoms in the surfactant R 1 Unlike the number of carbon atoms in 4 The number of carbon atoms in R of the surfactant of general formula (I) is preferably 1 For example, R of the surfactant of general formula (I) 1 (The condition is that the number of carbon atoms is twice that of the The compounds of general formula (IV) are preferably obtained by reductive amination of the aldehyde dimer resulting from the self-aldol condensation of an aldehyde of formula (II) as defined above with an amino compound of general formula (III) as defined above.

[0070] In one embodiment, the surfactant composition comprises the compound of general formula (IV) in an amount of 0.01 to 4.5 wt %, preferably 0.05 to 4.5 wt %, more preferably 0.1 to 4.0 wt %, and most preferably 0.5 to 3.0 wt %, based on the weight of the surfactant composition.

[0071] In one embodiment, the surfactant composition comprises the surfactant of general formula (I) in an amount of at least 93 wt.%, preferably at least 94 wt.%, more preferably at least 95 wt.%, such as at least 96 wt.% or at least 97 wt.%, based on the weight of the surfactant composition.

[0072] The surfactant composition may further comprise by-products of the process of the present invention, such as unreacted starting materials or by-products, such as alcohol.Preferably, the surfactant composition comprises less than 5 wt.%, more preferably less than 4 wt.%, and most preferably less than 3 wt.%, of compounds other than the surfactant of general formula (I) and the compound of general formula (IV).

[0073] Preferably, the surfactant composition is obtained according to the process of the present invention. The surfactant composition can be mixed with further ingredients to obtain surfactants for a wide variety of applications, including detergents, as described in detail below.

[0074] In another embodiment, the present invention further provides a surfactant composition comprising a surfactant of general formula (I) or a salt thereof as defined above and a compound of general formula (IV) or a salt thereof [ka] (In the formula, X, R 2 and R 3 is defined as above, and R 4 is C 10 -C 34 -Alkyl and C 10 -C 34 -alkenyl, where R 4 The number of carbon atoms in the surfactant R 1 Unlike the number of carbon atoms in 4 The number of carbon atoms in R of the surfactant of general formula (I) is preferably 1 For example, R of the surfactant of general formula (I) 1 (The condition is that the number of carbon atoms is twice that of the In this case, the weight ratio of the total amount of the surfactant of general formula (I) and its salt to the total amount of the compound of general formula (IV) and its salt is 15:1 to 10,000:1, preferably 20:1 to 1,000:1, more preferably 25:1 to 100:1, for example, 25:1 to 75:1; The compounds of general formula (IV) are preferably obtained by reductive amination of the aldehyde dimer resulting from the self-aldol condensation of an aldehyde of formula (II) as defined above with an amino compound of general formula (III) as defined above.

[0075] In the process of the present invention, the surfactant of general formula (I) is obtained together with a small amount of the compound of general formula (IV) as a by-product.Preferably, the compound of general formula (IV) contained in the surfactant composition of the present invention is derived from the self-aldol condensation product of the aldehyde (II) used in the process of the present invention.The compound of general formula (IV) can be obtained in a concentrated form from the crude reaction product of the process of the present invention, for example, by recrystallization.The ratio of the surfactant of general formula (I) and the compound of general formula (IV) can be determined by gas chromatography (after silylation) or gas chromatography-mass spectrometry (GC-MS).

[0076] The present invention further provides a compound selected from: - (2S,4R)-Nn-nonyl-4-hydroxypyrrolidine-2-carboxylic acid, - (2S,4R)-1-(2-ethylhexyl)-4-hydroxypyrrolidine-2-carboxylic acid, - (2S,4R)-1-(3,7-dimethyloctyl)-4-hydroxypyrrolidine-2-carboxylic acid, - (3,7-dimethyloctyl)-L-proline, - Nn-nonyl-N-(phosphonomethyl)glycine, - N-(2-ethylhexyl)-N-(phosphonomethyl)glycine, - N-(3,7-dimethyloctyl)-N-(phosphonomethyl)glycine, - 1-(3,7-dimethyloctyl)piperidine-2-carboxylic acid, - N-(3,7-dimethyloctyl)-N-methylglycine, - 2-((2-ethylhexyl)(methyl)amino)ethane-1-sulfonic acid, - 2-((3,7-dimethyloctyl)(methyl)amino)ethane-1-sulfonic acid, - N-(2-ethylhexyl)-N-methylalanine, - N-(3,7-dimethyloctyl)-N-methylalanine, - Nn-nonyl-L-leucine, - Nn-nonyl-L-isoleucine, - 2-(nonylmethylamino)ethanesulfonic acid, and - Nn-nonyl-L-glutamic acid, Or its salt.

[0077] The compounds of the invention may be obtained by the process of the invention.

[0078] The present invention further provides compositions comprising at least one compound of the present invention.

[0079] The present invention further provides the use of the compound of the present invention or the composition of the present invention as surfactant.The surfactant and composition of the present invention are understood to include the surfactant composition of the present invention, and can be used as surfactant in a wide variety of applications, including detergents such as granular laundry detergents, liquid laundry detergents, liquid dishwashing detergents, and in various formulations such as multi-purpose cleaners, liquid soaps, shampoos, shower gels, and liquid polishes.In addition, the compound and composition of the present invention can be used as surfactant in facility and industrial cleaning formulations such as kitchen cleaners, industrial laundry detergents, vehicle cleaners, and disinfectant cleaners.In addition, the compound and composition of the present invention can be used as adjuvant in pesticide formulations, such as insecticide formulations.

[0080] The compounds and compositions of the present invention are particularly used as surfactants in detergents, particularly laundry detergents and manual dishwashing products. They are generally composed of several components other than the compounds of the present invention. The compositions typically contain a total amount of the compounds of the present invention of 0.1-15% by weight based on the weight of the composition. Typical compositions are known to the expert.

[0081] Laundry detergents typically contain other surfactants of the anionic, nonionic, amphoteric or cationic type, builders such as phosphates, aminocarboxylates and zeolites, organic cobuilders such as polycarboxylates, bleaches and their activators, foam control agents, enzymes, hair anti-greying agents, optical brighteners, and stabilizers.

[0082] Liquid laundry detergents generally contain the same ingredients as granular laundry detergents, but generally contain less builder. In addition, liquid detergent formulations often contain hydrotropic materials. All-purpose cleaners may contain other surfactants, builders, suds suppressors, hydrotropes, and solubilizing alcohols.

[0083] Builders can be included in amounts up to 90% by weight, preferably about 5-35% by weight, to enhance cleaning action. Examples of common inorganic builders are phosphates, polyphosphates, alkali metal carbonates, silicates and sulfates. Examples of organic builders are polycarboxylates, aminocarboxylates, such as ethylenediaminetetraacetates, nitrilotriacetates, hydroxycarboxylates, citrates, succinates, and substituted and unsubstituted alkanedicarboxylic acids and polycarboxylic acids.

[0084] Another type of builder useful in granular and built liquid laundry agents includes various substantially water-insoluble materials that can reduce water hardness, such as by an ion exchange process. In particular, the complex sodium aluminosilicates known as Type A zeolites are useful for this purpose.

[0085] Laundry detergents may also contain bleaching agents such as percompounds, for example perborate, percarbonate, persulfate, and organic peroxy acids. Formulations containing percompounds may also contain stabilizers, such as magnesium silicate, sodium ethylenediaminetetraacetate, or sodium salts of phosphonic acids. In addition, bleach activators can be used to increase the efficiency of inorganic persalts at lower wash temperatures. Particularly useful for this purpose are substituted carboxylic acid amides, for example, tetraacetylethylenediamine, substituted carboxylic acids, for example, isononyloxybenzenesulfonic acid, and sodium cyanamide.

[0086] Examples of suitable hydrotropic materials are alkali metal salts of benzene, toluene and xylene sulfonic acid, alkali metal salts of formic acid, citric acid and succinic acid, urea, mono-, di- and triethanolamine. Examples of solubilizing alcohols are ethanol, isopropanol, mono- or polyethylene glycol, monopropylene glycol and ether alcohols.

[0087] Examples of foam control agents are high molecular weight fatty acid soaps, paraffinic hydrocarbons, and silicon-containing antifoamers. In particular, hydrophobic silica particles with silicon adsorbed thereon are effective foam control agents in these laundry detergent formulations.

[0088] Examples of enzymes known to be useful in laundry detergents are proteases, amylases, cellulases, mannanases, and lipases, among others. Enzymes that perform optimally under the conditions for which the detergent is designed are preferred.

[0089] A large number of optical brighteners have been described in the literature. For laundry detergent formulations, derivatives of diaminostilbene disulfonic acid and substituted distyrylbiphenyls are particularly suitable.

[0090] As the antigraying agent, organic water-soluble colloids are preferably used, examples of which include water-soluble polyanionic polymers such as polymers and copolymers of acrylic acid and maleic acid, and cellulose derivatives such as carboxymethylcellulose, methyl and hydroxyethylcellulose.

[0091] In addition to one or more of the other surfactants and other detergent composition ingredients mentioned above, laundry detergent compositions typically include one or more inactive ingredients. For example, the remainder of a liquid detergent composition is typically an inert solvent or diluent, most commonly water.

[0092] The manual dishwashing products may contain, in addition to the compounds obtained by the process of the present invention, other surfactants of the anionic, nonionic, amphoteric or cationic type, solvents, diamines, carboxylic acids or their salts, polymeric foam stabilizers, enzymes, builders, fragrances, and / or chelating agents.

[0093] Suitable solvents include diols, polymeric glycols, and mixtures thereof. Preferred diols include propylene glycol, 1,2-hexanediol, 2-ethyl-1,3-hexanediol, and 2,2,4-trimethyl-1,3-pentanediol.

[0094] Polymeric glycols containing ethylene oxide (EO) and propylene oxide (PO) groups may also be included in the present invention. These materials are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains. Preferred polymeric glycols are polypropylene glycols having an average molecular weight in the range of 1,000 to 5,000 g / mol. When polymeric glycols are present, it may be beneficial to include a diol and / or an alkali metal inorganic salt such as sodium chloride to obtain sufficient physical stability. The appropriate amount of diol to obtain physical stability is in the range of amounts described above.

[0095] Further suitable solvents include glycols or alkoxylated glycols, ethers and diethers having 4 to 14 carbon atoms, preferably 6 to 12 carbon atoms, aromatic alcohols, alkoxylated aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, linear C1-C5 alcohols, alkoxylated linear C1-C5 alcohols, C8-C 14 Alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-C 16 glycol ethers, and mixtures thereof.

[0096] Suitable alkoxylated glycols are methoxyoctadecanol and / or ethoxyethoxyethanol. Suitable aromatic alcohols include benzyl alcohol. Suitable aliphatic branched alcohols include 2-ethylbutanol and / or 2-methylbutanol. Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and / or 2-methylbutoxyethanol. Suitable linear C1-C5 alcohols include methanol, ethanol, and / or propanol.

[0097] Manual dishwashing compositions typically contain from 0.01 to 20% by weight of the solvent, based on the total weight of the composition. The solvent can be used in combination with an aqueous liquid carrier, such as water, or in the absence of any aqueous liquid carrier.

[0098] The manual dishwashing composition may further comprise one or more diamines.

[0099] The composition preferably comprises 0.1 to 15 wt. % of at least one diamine, based on the total weight of the composition.

[0100] Suitable diamines include organic diamines with pK1 and pK2 in the range of 8.0 to 11.5, such as 1,3-bis(methylamine)-cyclohexane (pKa=10-10.5), 1,3-propanediamine (pK1=10.5, pK2=8.8), 1,6-hexanediamine (pK1=11, pK2=10), 1,3-pentanediamine (pK1=10.5, pK2=8.9), 2-methyl-1,5-pentanediamine (Dytek A) (pK1=11.2, pK2=10.0). The pKa values ​​referred to herein can be obtained from the literature, for example, "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, NY and London, 1975. The pKa of a diamine is determined for a total aqueous solution at 25°C with an ionic strength of 0.1-0.5M.

[0101] Other preferred materials are primary diamines having two primary amino groups with an alkylene spacer in the C4 to C8 range.

[0102] The composition according to the invention may comprise a linear or cyclic carboxylic acid or salt thereof. When present, the acid or salt thereof is linear, it preferably contains from 1 to 6 carbon atoms, whereas when the acid is cyclic, it preferably contains more than 3 carbon atoms. The linear or cyclic carbon-containing chain of the carboxylic acid or salt thereof may be substituted with a substituent selected from the group consisting of hydroxyl, ester, ether, aliphatic groups having from 1 to 6, more preferably from 1 to 4, carbon atoms, and mixtures thereof.

[0103] Preferred carboxylic acids are those selected from the group consisting of salicylic acid, maleic acid, acetylsalicylic acid, 3-methylsalicylic acid, 4-hydroxyisophthalic acid, dihydroxyfumaric acid, 1,2,4-benzenetricarboxylic acid, pentanoic acid, and their salts and mixtures thereof. When the carboxylic acid is present in the form of a salt, the cation of the salt is preferably selected from alkali metals, alkaline earth metals, monoethanolamine, diethanolamine, or triethanolamine, and mixtures thereof.

[0104] The carboxylic acid or salt thereof is preferably present in an amount of from 0.1% to 5% by weight, based on the total weight of the composition.

[0105] The composition can include a polymeric foam stabilizer. These polymeric foam stabilizers extend the foam volume and foam duration without sacrificing the grease-cutting ability of the liquid detergent composition. Suitable polymeric foam stabilizers include (N,N-di(C1-C8 alkyl)amino)(C1-C8) alkyl acrylate ester homopolymers, and their copolymers.

[0106] The molecular weight of the polymeric foam stabilizer is preferably in the range of 1,000 to 2,000,000 g / mol, most preferably 20,000 to 500,000 g / mol. The polymeric foam stabilizer may be present in the form of a salt, for example, a citrate, sulfate, or nitrate salt of an (N,N-dimethylamino) alkyl acrylate ester. One preferred polymeric foam stabilizer is an (N,N-dimethylamino) alkyl acrylate ester. The polymeric foam stabilizer is preferably present in an amount of 0.01% to 15% by weight, based on the total weight of the composition.

[0107] Suitable builders include aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediaminetetraacetate, aminopolyphosphonates, particularly sequestering agents such as ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Phosphate builders can also be used, although less preferred for obvious environmental reasons.

[0108] Suitable polycarboxylate builders include citric acid and succinic acid derivatives, preferably in the form of water-soluble salts.Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, 2-tetradecenyl succinate.Succinic acid builders are preferably used in the form of their water-soluble salts, such as sodium, potassium, ammonium and alkanolammonium salts.Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic acid and tartrate disuccinic acid, as described in U.S. Pat. No. 4,663,071.

[0109] Suitable fatty acid builders include saturated and unsaturated C 10 - 18 These include fatty acids, as well as the corresponding soaps. Preferred saturated species have 12 to 16 carbon atoms in the alkyl chain. A preferred unsaturated fatty acid is oleic acid. Other preferred builder systems for liquid compositions are based on dodecenyl succinic acid and citric acid.

[0110] The builder is preferably present in an amount of from 0.5% to 50% by weight, more preferably from 5 to 25% by weight, based on the total weight of the composition.

[0111] Suitable enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, or mixtures thereof. The enzymes may be present in an amount of 0.0001% to 5% by weight of active enzyme, based on the total weight of the composition.

[0112] Preferred proteolytic enzymes are selected from the group consisting of Alcalase® (Novo Industri A / S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred. Preferred amylase enzymes include TERMAMYL®, DURAMYL®, and the amylase enzymes described in WO 9418314 to Genencor International and WO 9402597 to Novo.

[0113] Suitable chelating agents include iron and / or manganese chelating agents. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof. Suitable aminocarboxylates include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, and ethanoldiglycine, their alkali metal, ammonium, and substituted ammonium salts, and mixtures thereof. Suitable aminophosphonates include ethylenediaminetetrakis(methylenephosphonate). Suitable polyfunctionally substituted aromatic chelating agents include dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene.

[0114] The chelating agent may be present in an amount of 0.00015% to 15% by weight, based on the weight of the composition.

[0115] The present invention will now be described in further detail by the following examples. EXAMPLES

[0116] Overview Reductive amination of aldehydes with amino compounds was carried out in a 300 mL autoclave at temperatures ranging from 25 to 90° C. and hydrogen pressures ranging from 5 to 20 bar according to Table 1 below.

[0117] Analyses were performed by gas chromatography (after silylation) or gas chromatography-mass spectrometry (GC-MS) and the structures were confirmed by nuclear magnetic resonance (NMR) spectroscopy.

[0118] method The foam volume was measured according to EN 12728 at 2 g / L in tap water with a hardness of 10°d.

[0119] The wetting time of cotton was measured according to EN 1772 at 1 g / L in deionized water with 10 wt% Na2CO3.

[0120] Dynamic surface tension was measured at 23°C after 0.1 s at 1 g / L in deionized water using a SITA T60 online bubble pressure tensiometer.

[0121] The interfacial tension against hexadecane was measured at 1 g / L in deionized water after 10 minutes at 23° C. using a DataPhysics instrument OCA25.

[0122] Contact angles were measured on polyethylene at 40° C. after 10.0 seconds at 0.2 g / L in deionized water using a DataPhysics instrument OCA25.

[0123] Comparative Example 1 Palladium on carbon black (10 wt%, 2.5 g) was added to a solution of L-proline (99%, 25 g) and dodecanal (95%, 43 g) in tetrahydrofuran (120 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar) and hydrogen gas (3 times at 5 bar). Stirring (700 rpm) was performed with an initial hydrogen gas pressure of 5 bar. The reaction mixture was warmed to 30° C. and the hydrogen pressure was maintained at 5 bar.

[0124] The reaction mixture was stirred under these conditions for 12 hours, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar). The catalyst was then filtered and the filter cake was washed 3 times with tetrahydrofuran. The solvent was removed by evaporation to give the crude material as a grey solid (purity: 84%, 61 g, yield: 83%). 83%). Recrystallization from heptane / toluene (19:1) gave the product as a micaceous solid (36 g, purity: 90%, yield: 53%). 53%).

[0125] Comparative Examples 2 to 7 Comparative Examples 2 to 7 were carried out in the same manner as Comparative Example 1, as shown in Table 1.

[0126] Comparative Example 8 Palladium carbon black (10 wt%, 1 g) was added to a solution of trans-4-hydroxy-L-proline (99%, 10 g) and dodecanal (95%, 16 g) in a mixture of tetrahydrofuran (50 mL) and water (50 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar) and hydrogen gas (3 times at 5 bar). Stirring (700 rpm) was performed with an initial hydrogen pressure of 20 bar. The reaction mixture was warmed to 90° C. and the hydrogen pressure was maintained at 20 bar.

[0127] The reaction mixture was stirred under these conditions for 24 hours, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar). The catalyst was then filtered and the filter cake was washed 3 times with tetrahydrofuran. The solvent was removed by evaporation to give the crude material as a solid (15 g, purity: 81%, yield: 52%). 52%)

[0128] Comparative Example 9 Palladium carbon black (10 wt%, 2 g) was added to a solution of L-proline (99%, 20 g) and dodecanal (95%, 35 g) in ethanol (135 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar) and hydrogen gas (3 times at 5 bar). Stirring (700 rpm) was performed with an initial hydrogen pressure of 5 bar. The reaction mixture was warmed to 25° C. and the hydrogen pressure was maintained at 5 bar.

[0129] The reaction mixture was stirred under these conditions for 12 hours, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar).The catalyst was then filtered (the filter cake was washed twice with ethanol) and the solvent was removed by evaporation to give the crude material as a solid (53 g, purity: 72%, yield: 79%).

[0130] Comparative Example 10 Comparative Example 10 was carried out in the same manner as Comparative Example 9, as shown in Table 1.

[0131] Comparative Example 11 Palladium carbon black (10% by weight, 2 g) was added to a solution of sarcosine (100%, 20 g) in water (100 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar) and hydrogen gas (3 times at 5 bar). Stirring (700 rpm) was performed with an initial hydrogen pressure of 20 bar. The reaction mixture was warmed to 50° C. Dodecanal (95%, 46 g) was then continuously metered into the reaction mixture over a period of 6 hours. The temperature (50° C.) and hydrogen pressure (20 bar) were maintained.

[0132] After complete addition of the aldehyde, the reaction mixture was stirred at a temperature of 50° C. and a hydrogen pressure of 20 bar for 6 hours, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar).Then, the catalyst was filtered (the filter cake was washed with ethanol) and the solvent was removed by evaporation to give the crude material as a solid (61 g, purity: 49%, yield: 52%).

[0133] Example 12 Palladium carbon black (10% by weight, 2 g) was added to a solution of L-proline (100%, 20 g) in a mixture of ethanol (50 mL) and water (40 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar) and hydrogen gas (3 times at 5 bar). Stirring (700 rpm) was performed with an initial hydrogen pressure of 5 bar. The reaction mixture was warmed to 40° C. Then, dodecanal (95%, 35 g) in ethanol (20 mL) solution was continuously metered into the reaction mixture over a period of 5 hours. The temperature (40° C.) and hydrogen pressure (5 bar) were maintained.

[0134] After complete addition of the aldehyde solution, the reaction mixture was stirred at a temperature of 40° C. and 5 bar hydrogen pressure for 1 h, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar). The catalyst was then filtered and the filter cake was washed twice with ethanol. The solvent was removed by evaporation to give the crude material as a solid (51 g, purity: 92%, yield: 96%).

[0135] Examples 13 to 21 Examples 13 to 21 were carried out in the same manner as Example 9, as shown in Table 1.

[0136] Comparative Example 22 Palladium carbon black (3 wt%, 5.2 g) was added to a solution of rac-pipecolic acid (99%, 5.2 g) and dodecanal (95%, 9.7 g) in a mixture of ethanol (102 mL) and water (20.5 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar) and hydrogen gas (3 times at 5 bar). Stirring (700 rpm) was performed with an initial hydrogen gas pressure of 1 bar. The reaction mixture was warmed to 55° C. and the hydrogen pressure was maintained at 1 bar.

[0137] The reaction mixture was stirred under these conditions for 4 h, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar).The catalyst was then filtered (the filter cake was washed 3 times each with ethanol and water) and the solvent was removed by evaporation to give the crude material as a solid (14 g, purity: 70%, yield: 79%).

[0138] Examples 23 to 33 Examples 23 to 33 were carried out in the same manner as Example 12, as shown in Table 1.

[0139] [Table 2]

[0140] [Table 3]

[0141] [Table 4]

[0142] [Table 5]

[0143] [Table 6]

[0144] [Table 7]

[0145] [Table 8]

[0146] Example 34 Palladium carbon black (10% by weight, 2 g) was added to a mixture of L-proline (98%, 20 g) in ethanol (70 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar) and hydrogen gas (3 times at 5 bar). Stirring (700 rpm) was performed with an initial hydrogen pressure of 5 bar. The reaction mixture was warmed to 30° C. Then, dodecanal (95%, 66 g) in ethanol (20 mL) solution was continuously metered into the reaction mixture over a period of 6 hours. The temperature (30° C.) and hydrogen pressure (5 bar) were maintained.

[0147] After complete addition of the aldehyde solution, the reaction mixture was stirred at a temperature of 30° C. and 5 bar hydrogen pressure for 6 hours, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar). The catalyst was then filtered and the filter cake was washed twice with ethanol. The solvent was removed by evaporation to give the crude material as a solid.

[0148] Example 35 Palladium carbon black (10 wt%, 2 g) was added to a mixture of L-proline (98%, 20 g) and dodecanal (95%, 66 g) in ethanol (90 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar) and hydrogen gas (3 times at 5 bar). Stirring (700 rpm) was performed with an initial hydrogen pressure of 5 bar. The reaction mixture was warmed to 30° C. The temperature (30° C.) and hydrogen pressure (5 bar) were maintained and the reaction mixture was stirred for 12 hours, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar). The catalyst was then filtered and the filter cake was washed twice with ethanol. The solvent was removed by evaporation to give the crude material as a solid.

[0149] Example 36 Palladium carbon black (10% by weight, 2 g) was added to a mixture of sarcosine (100%, 20 g) in ethanol (50 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar) and hydrogen gas (3 times at 5 bar). Stirring (700 rpm) was performed with an initial hydrogen pressure of 5 bar. The reaction mixture was warmed to 30° C. Then, dodecanal (95%, 87 g) in ethanol (20 mL) solution was continuously metered into the reaction mixture over a period of 6 hours. The temperature (30° C.) and hydrogen pressure (5 bar) were maintained.

[0150] After complete addition of the aldehyde, the reaction mixture was stirred at a temperature of 30° C. and 5 bar hydrogen pressure for 6 hours, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar).The catalyst was then filtered (the filter cake was washed with ethanol) and the solvent was removed by evaporation to give the crude material as a solid.

[0151] Example 37 Palladium carbon black (10% by weight, 2 g) was added to a mixture of sarcosine (100%, 20 g) and dodecanal (95%, 87 g) in ethanol (70 mL) in an autoclave. The reaction vessel was closed and then purged with nitrogen gas (3 times at 5 bar) and hydrogen gas (3 times at 5 bar). Stirring (700 rpm) was performed with an initial hydrogen pressure of 5 bar. The reaction mixture was warmed to 30° C. Maintaining the temperature (30° C.) and hydrogen pressure (5 bar), the reaction mixture was stirred for 12 hours, then cooled to room temperature and purged with nitrogen gas (3 times at 5 bar). The catalyst was then filtered and the filter cake was washed twice with ethanol. The solvent was removed by evaporation to give the crude material as a solid.

[0152] [Table 9]

[0153] In Examples 34 and 36, the process was carried out in a feed operation in which dodecanal was continuously added to a solution of the amino compound, whereas in Comparative Examples 35 and 37, the amino compound and dodecanal were provided as a mixture.

[0154] C in the obtained crude material 12 Surfactants with chains and C 24 The proportions of surfactants having a C chain are shown in Table 2. 24 The proportion of surfactants with chains is determined by the fact that the aldehyde undergoes aldol condensation with itself to form an aldehyde dimer, which then reacts to form C 24 The degree of side chain surfactant formation is shown. It is clear that the feeding procedure carried out in Examples 34 and 36 significantly suppresses the self-aldol condensation of aldehydes, which allows higher selectivity and also suppresses the excessive formation of dimeric surfactants with less favorable properties.

[0155] Example 38 The reaction product of L-proline and dodecanal obtained in Example 33b was analyzed, and the self-aldol condensation product of dodecanal, i.e., C 2 H 2 O 3 derived from (2-decyltetradecyl)proline, was found to be 24 It was found to contain less than 0.1% by weight of proline-based dimeric surfactant with chains.

[0156] 3.0 parts by weight of the product obtained in Example 35 was mixed with 97 parts by weight of the product obtained in Example 33b to obtain C 24 A surfactant composition containing about 2% by weight of a proline-based dimeric surfactant having a chain was obtained.

[0157] 7.5 parts by weight of the product obtained in Example 35 was mixed with 92.5 parts by weight of the product obtained in Example 33b to obtain C 24 A surfactant composition containing about 5% by weight of a proline-based dimeric surfactant having a chain was obtained.

[0158] 44.7 parts by weight of the product obtained in Example 35 was mixed with 55.3 parts by weight of the product obtained in Example 33b to obtain C 24 A surfactant composition containing about 30% by weight of a proline-based dimeric surfactant having a chain was obtained.

[0159] The product of Example 33b and C 24The resulting mixtures with proline-based dimeric surfactants having chains were subjected to surfactant testing, and the results are shown in Table 3.

[0160] [Table 10]

[0161] Example 39 The reaction product of sarcosine and dodecanal obtained in Example 25 was analyzed, and the self-aldol condensation product of dodecanal, i.e., C derived from N-(2-decyltetradecyl)-N-methylglycine, was found to be 24 It was found to contain less than 0.22 wt. % of a dimeric sarcosine-based surfactant having a chain.

[0162] 3.4 parts by weight of the product obtained in Example 37 was mixed with 96.6 parts by weight of the product obtained in Example 25 to obtain C 24 A surfactant composition containing about 2% by weight of a sarcosine-based dimeric surfactant having a chain was obtained.

[0163] 8.5 parts by weight of the product obtained in Example 37 was mixed with 91.5 parts by weight of the product obtained in Example 25 to obtain C 24 A surfactant composition containing about 5% by weight of a sarcosine-based dimeric surfactant having a chain was obtained.

[0164] 50.8 parts by weight of the product obtained in Example 37 was mixed with 49.2 parts by weight of the product obtained in Example 25 to obtain C 24 A surfactant composition containing about 30% by weight of a sarcosine-based dimeric surfactant having a chain was obtained.

[0165] The product of Example 25 and C 24 The resulting mixtures with the sarcosine-based dimeric surfactants having chains were subjected to surfactant testing, and the results are shown in Table 4.

[0166] [Table 11]

Claims

1. General formula (I) 【Chemistry 1】 (In the formula, X is COOH and CH ２ SO ３ H; R １ is C ５ -C １７ -Alkyl and C ５ -C １７ -alkenyl, R ２ is hydrogen, C １ -C ４ -Alkyl and CH ２ P.O. ３ H ２ is selected from R ３ is hydrogen and C １ -C ８ - alkyl, C １ -C ８ -Alkyl is a hydroxy group, an amino group, １ -C ８ -Alkylamino group, carboxyl group, C １ -C ８ - alkyl carboxylate group, C １ -C ８ -Alkylamide group, thio group, C １ -C ８ - optionally substituted with one or more substituents selected from alkylthio groups, guanidino groups, and aromatic groups optionally substituted with hydroxy groups; Or, R ２ and R ３ is R ２ and the nitrogen atom to which R is bonded. ３ (R) taken together with the carbon atom to which it is attached forms a 5- or 6-membered heterocyclic ring optionally substituted with hydroxy groups, or a salt thereof, comprising the steps of: General formula (II) 【Chemistry 2】 (In the formula, R １ is defined as above) of the aldehyde General formula (III) 【Chemistry 3】 (In the formula, R ２ , R ３ and X is as defined above) or a salt thereof with an amino compound, In the presence of molecular hydrogen and a heterogeneous catalyst comprising an element from Group 10 of the Periodic Table of the Elements, The reductive amination is carried out in a feed operation, in which the amino compound of general formula (III) is provided, to which the aldehyde of general formula (II) is metered, The reductive amination is at a molecular hydrogen pressure of at least 1 bar, at a temperature of at least 25° C., and - a Hildebrand solubility parameter δ between 18 and 38 MPa at a solvent dilution ratio of less than 7.0 L / kg (said solvent dilution ratio being the total volume of solvent relative to the total weight of said aldehyde of general formula (II) and said amino compound of general formula (III)); １／２ The production process is carried out in a solvent in the range of

2. R １ is C ７ -C １７ -Alkyl, especially C ７ -, C ８ - or C １１ -alkyl, or R １ is C ９ -C １７ -Alkenyl, especially C ９ -alkenyl.

3. R ２ is C １ -C ３ - alkyl, in particular methyl, R ３ The process of claim 1 or 2, wherein is hydrogen.

4. R ２ and R ３ is R ２ The nitrogen atom to which R is bonded ３ 3. The process of claim 1 or 2, wherein together with the carbon atom to which it is attached, forms an optionally substituted pyrrolidinyl group or an optionally substituted piperidinyl group.

5. 5. The process according to any one of claims 1 to 4, wherein the heterogeneous catalyst is present in an amount of at most 2.5% by weight, calculated as group 10 element relative to the weight of the amino compound of general formula (III).

6. The process according to any one of claims 1 to 5, wherein the group 10 elements are selected from nickel, palladium and platinum, preferably nickel and palladium, most preferably palladium.

7. 7. The process of claim 6, wherein the heterogeneous catalyst is palladium on activated carbon.

8. The process of any one of claims 1 to 7, wherein the solvent comprises a protic solvent and / or an aprotic solvent containing an ether moiety.

9. 9. The process of claim 8, wherein the solvent is an aliphatic alcohol or a mixture of an aliphatic alcohol and water.

10. 10. The process according to claim 9, wherein the solvent is a mixture of an aliphatic alcohol, in particular ethanol, and water in a volume ratio ranging from 1:1 to 4:

1.

11. The process according to any one of claims 1 to 10, wherein said aldehyde of general formula (II) and / or said amino compound of general formula (III) are bio-based compounds.

12. A surfactant of the general formula (I) or a salt thereof according to any one of claims 1 to 4 in an amount of at least 90% by weight, based on the weight of the surfactant composition, and a surfactant of the general formula (IV) in an amount of 0.01 to 5.0% by weight, based on the weight of the surfactant composition 【Chemistry 4】 (In the formula, X, R ２ and R ３ is defined as above, R ４ is C １０ -C ３４ -Alkyl and C １０ -C ３４ -alkenyl, where R ４ The number of carbon atoms in R １ and a compound of formula (I) or a salt thereof, provided that the number of carbon atoms in the compound is different from that in formula (I).

13. (2S,4R)-N-nonyl-4-hydroxypyrrolidine-2-carboxylic acid, (2S,4R)-1-(2-ethylhexyl)-4-hydroxypyrrolidine-2-carboxylic acid, (2S,4R)-1-(3,7-dimethyloctyl)-4-hydroxypyrrolidine-2-carboxylic acid, (3,7-dimethyloctyl)-L-proline, N-nonyl-N-(phosphonomethyl)glycine, N-(2-ethylhexyl)-N-(phosphonomethyl)glycine, N-(3,7-dimethyloctyl)-N-(phosphonomethyl)glycine, 1-(3,7-dimethyloctyl)piperidine-2-carboxylic acid, N-(3,7-dimethyloctyl)-N-methylglycine, 2-((2-ethylhexyl)(methyl)amino)ethane-1-sulfonic acid, 2-((3,7-dimethyloctyl)(methyl)amino)ethane-1-sulfonic acid, N-(2-ethylhexyl)-N-methylalanine, N-(3,7-dimethyloctyl)-N-methylalanine, N-nonyl-L-leucine, N-nonyl-L-isoleucine, 2-(nonylmethylamino)ethanesulfonic acid, and - Nn-nonyl-L-glutamic acid.

14. A composition comprising at least one compound according to claim 13.

15. 15. Use of a compound according to claim 14 or a composition according to claim 12 or 13 as a surfactant.

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