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Title:
DIMETHYL FARNESYL AMINE OXIDE AND ITS USE AS SURFACTANT OR WETTING AGENT
Document Type and Number:
WIPO Patent Application WO/2018/149589
Kind Code:
A1
Abstract:
Dimethyl amine oxides comprising farnesyl residues are described. These amine oxides are advantageously suited as surfactants or wetting agents.

Inventors:
ROMANSKI, Steffen (Schillstr. 25, Wesel, 46483, DE)
LEINWEBER, Dirk (Merowingerweg 5b, Kelkheim, 65779, DE)
GUO, Xiaoqiang (Königsteiner Strasse 68, Frankfurt am Main, 65929, DE)
VORHOLT, Andreas (Friedrichstrasse 35c, Dortmund, 44137, DE)
BEHR, Arno (Hüttemannstrasse 46, Dortmund, 44137, DE)
FASSBACH, Thiemo Alexander (Hellweg 51, Essen, 45276, DE)
Application Number:
EP2018/051445
Publication Date:
August 23, 2018
Filing Date:
January 22, 2018
Export Citation:
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Assignee:
CLARIANT INTERNATIONAL LTD (Rothausstr. 61, 4132 Muttenz, 4132, CH)
International Classes:
C07C291/04; C11D1/75
Foreign References:
GB2297973A1996-08-21
FR2320280A11977-03-04
US5679633A1997-10-21
GB2032422A1980-05-08
US5679633A1997-10-21
US20110034363A12011-02-10
US5866718A1999-02-02
Other References:
VICTORIA G SÃ NCHEZ ET AL: "Synthesis, Surface-Active Properties, and Anthelmintic Activities of New Cationic Gemini Surfactants Against the Gastrointestinal Nematode,, In Vitro", JOURNAL OF SURFACTANTS AND DETERGENTS, SPRINGER/OACS, USA, vol. 15, no. 4, 8 March 2012 (2012-03-08), pages 463 - 470, XP035068162, ISSN: 1558-9293, DOI: 10.1007/S11743-012-1337-0
J. PAWLAS; Y. NAKAO.; M. KAWATSURA; J. F. HARTWIG: "A general nickel-catalyzed hydroamination of 1,3-dienes by alkylamines: Catalyst selection, scope, and mechanism", J. AM. CHEM. SOC., vol. 124, no. 14, 2002, pages 3669 - 3679, XP002514362, DOI: doi:10.1021/JA017575W
Attorney, Agent or Firm:
PACZKOWSKI, Marcus (Industriepark Höchst / G 860, Frankfurt, 65926, DE)
Download PDF:
Claims:
Patent Claims

1 . Amine oxide of the formula (I)

C LJ

Π '

i

N-0

(I) wherein

R is a radical of the formula

indicates the binding site and is a bond and indicates that the double bond connected thereto can be either cis or trans in configuration.

2. Amine oxide according to claim 1 of the formula (la)

3. Compound obtainable by reacting a dimethyl farnesyl amine with hydrogen peroxide in the presence of carbon dioxide.

4. Compound according to claim 3, characterized in that the reaction is performed in a solvent, preferably in a solvent comprising water and one or more further solvents different from water, and more preferably in water as the solvent, at a temperature of from 20 to 100 °C, preferably of from 30 to 70 °C, and furthermore preferably at atmospheric pressure.

5. Compound according to claim 3 or 4, characterized in that the molar ratio dimethyl farnesyl amine : hydrogen peroxide is of from 1 : 1 to 1 : 50, preferably of from 1 : 1 to 1 : 10 and even more preferably of from 1 : 1 to 1 : 3.

6. Compound according to one or more of claims 3 to 5, characterized in that the dimethyl farnesyl amine is obtained by reacting farnesene with dimethyl amine or a dimethyl amine source in the presence of a transition metal catalyst. 7. Compound according to claim 6, characterized in that the dimethyl amine source is selected from the group consisting of dimethyl amine hydrochloride, preferably to be used together with a base, and dimethyl ammonium dimethyl carbamate.

8. Compound according to claim 6 or 7, characterized in that the transition metal catalyst comprises a metal selected from group 10 of the periodic table and preferably selected from the group consisting of nickel, palladium and platinum. 9. Compound according to one or more of claims 6 to 8, characterized in that the molar ratio farnesene : (dimethyl amine or dimethyl amine source) is of from 1 : 1 to 1 : 10.

10. Compound according to one or more of claims 6 to 9, characterized in that the reaction is performed at a temperature of from 50 to 150 °C, preferably of from 60 to 120 °C and even more preferably of from 70 to 100 °C.

1 1 . Compound according to one or more of claims 6 to 10, characterized in that the farnesene is beta-farnesene and preferably trans-beta-farnesene (trans-7,1 1 - dimethyl-3-methylene-1 ,6,10-dodecatriene).

12. Process for the preparation of an amine oxide or a compound according to one or more of claims 1 to 1 1 as described in one or more of the claims 3 to 1 1 . 13. Use of an amine oxide or a compound according to one or more of claims 1 to 1 1 as a surfactant.

14. Use of an amine oxide or a compound according to one or more of claims 1 to 1 1 as a wetting agent.

15. Crop protection composition, hard surface cleaning composition, laundry detergent composition or automatic dishwashing composition comprising one or more amine oxides or compounds according to one or more of claims 1 to 1 1 .

Description:
Dimethyl farnesyl amine oxide and its use as surfactant or wetting agent

The present invention relates to amine oxides comprising farnesyl residues (dimethyl farnesyl amine oxides) and compounds obtainable by reacting a dimethyl farnesyl amine with hydrogen peroxide in the presence of carbon dioxide, to a process for the preparation of these amine oxides or compounds, to their uses as surfactants or wetting agents, and to crop protection compositions, hard surface cleaning compositions, laundry detergent compositions, and automatic

dishwashing compositions comprising one or more of these amine oxides or compounds.

Trialkyl amine oxides are well-known as surfactants and foaming agents that are used in a variety of applications, including sanitizers, cleaners, emulsifiers, fabric softeners, oil drilling lubricants, and the like. The particular application for which a given amine oxide will be preferred depends upon its functional characteristics, which in turn depend upon the nature of the alkyl substituents. The functional properties include surface tension reduction, wetting ability, and the amount and quality of the foam produced. Structural parameters include the number of long chain alkyl groups, their length and their degree of branching.

US 5,679,633 discloses low foaming branched alkyl dimethyl amine oxides synthesized from branched fatty alcohol based on oil refinery products.

US 201 1/034363 describes highly branched trialkyl amine oxides which are synthesized from polyunsaturated and polybranched hydrocarbons such as farnesene by a multi-step process. The preparation of these surfactants e.g. starts with a hydroformylation of the polyunsaturated and polybranched hydrocarbons to the corresponding aldehydes. These aldehydes are subsequently hydrogenated to the fully saturated alcohols, followed by halogenation, amination and oxidation. The resulting amine oxides are said to have an enhanced foaming ability.

However, there is still a big need for low-foaming or non-foaming renewable substances that can be prepared in an atom economic way, exhibit superior surface tension reduction and wetting properties, and may be used in various applications, e.g. as crop protection adjuvant, dishwasher rinse aid, hard surface cleaning detergent or laundry detergent additive. Therefore, it was the object of the present invention to provide low-foaming or non- foaming renewable substances that can be prepared in an atom economic way, and exhibit superior surface tension reduction and wetting properties.

Surprisingly, it was found that this object is solved by the amine oxides of the formula (I)

Π

i ÷

R-N-0

I

CH

(I) wherein

R is a radical of the formula

* indicates the binding site and is a bond and indicates that the double bond connected thereto can be either cis or trans in configuration. Therefore, the subject matter of the present invention is amine oxides of the formula (I) f t *>

i

R-N-O '

I

(I) wherein

R is a radical of the formula

indicates the binding site and is a bond and indicates that the double bond connected thereto can be either cis or trans in configuration.

The inventive amine oxides of the formula (I) are dimethyl farnesyl amine oxides. The inventive dimethyl farnesyl amine oxides (as well as the inventive compounds described further below) provide advantageous surface tension reduction and wetting characteristics while producing no foam or no stable foam.

The inventive dimethyl farnesyl amine oxides of the formula (I) may be

synthesized from dimethyl farnesyl amine by oxidation with hydrogen peroxide in the presence of carbon dioxide (oxidation reaction). The dimethyl farnesyl amine may be obtained by reacting farnesene with dimethyl amine or with a dimethyl amine source (hydroamination reaction). The starting farnesene is 100 % renewable. Even starting from farnesene, the process enables to produce the inventive amine oxides (as well as the inventive compounds described further below) in only two steps, and is highly atom economic. The product is highly renewable.

The inventive amine oxides (as well as the inventive compounds described further below) have an advantageous water-solubility. Among the inventive amine oxides according to formula (I) the amine oxide of the formula (la) is preferred

In the inventive amine oxide of the formula (la) the double bond located closest to the dimethyl amine oxide functional group is in trans configuration. This amine oxide e.g. may be synthesized starting from dimethyl farnesyl amine wherein the double bond located closest to the dimethyl amine functional group is trans in configuration. The dimethyl farnesyl amine in turn may preferably be synthesized from trans-beta-farnesene.

As already stated above, the inventive dimethyl farnesyl amine oxides of the formula (I) may be synthesized from dimethyl farnesyl amine by oxidation with hydrogen peroxide in the presence of carbon dioxide. A further subject matter of the present invention therefore is compounds

obtainable by reacting a dimethyl farnesyl amine with hydrogen peroxide in the presence of carbon dioxide. These inventive compounds are mixtures of different substances wherein the mixtures comprise one or more inventive amine oxides according to formula (I) and preferably the inventive amine oxide according to formula (la).

The oxidation of alkyl amines to alkyl amine oxides, and in particular using hydrogen peroxide in the presence of carbon dioxide (which may be used as such or which may be generated from a carbon dioxide source such as sodium bicarbonate), is a reaction well known to the person skilled in the art (see e.g. US 5,866,718).

Preferably, the oxidation reaction to prepare the inventive amine oxides or inventive compounds is performed in a solvent, more preferably in a solvent comprising water and one or more further solvents different from water, and even more preferably in water as the solvent.

Preferred further solvents different from water for the oxidation reaction to prepare the inventive amine oxides or inventive compounds are selected from the group consisting of organic liquids in which the tertiary amine and tertiary amine oxide are soluble at the reaction temperature and which are capable of forming an azeotrope with water. However, to avoid the danger of explosion, these solvents should be substantially inert.

Particularly preferred further solvents different from water for the oxidation reaction to prepare the inventive amine oxides or inventive compounds are the lower alkyl alcohols, such as the O-e alcohols, and especially the C1-4 alcohols, containing one or more hydroxyl groups. Exemplary alcohols include methanol, ethanol, 1 -propanol, 2-propanol, 1 -butanoi, 2-butanol, 1 -pentanol, 2-pentanol, 3-pentanol, tert-butyl alcohol, 1 -hexanol, 2-hexanol, 3-hexanol, 2-methyl-1 -propanol, 2-methyl- 2-propanol, tert-amyl alcohol, 2-methyl-1 -butanoi, 3-methyl-1 -butanoi, 3-methyl-2- butanol, neopentyi alcohol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 1 -hexyl alcohol, 2-hexanol, 3-hexanol, and the like as well as various mixtures thereof. Especially preferred solvents include 1 -propyl alcohol, 2-propyl alcohol, -butanol, and 2-butanol. Preferably, the oxidation reaction to prepare the inventive amine oxides or inventive compounds is performed at a temperature of from 20 to 100 °C and more preferably at a temperature of from 30 to 70 °C.

Preferably, the oxidation reaction to prepare the inventive amine oxides or inventive compounds is performed at atmospheric pressure.

Preferably, in the oxidation reaction to prepare the inventive amine oxides or inventive compounds, the molar ratio dimethyl farnesyl amine : hydrogen peroxide is of from 1 : 1 to 1 : 50, preferably of from 1 : 1 to 1 : 10 and even more preferably of from 1 : 1 to 1 : 3.

Preferably, the oxidation reaction to prepare the inventive amine oxides or inventive compounds may be performed in the presence of chelating agents, e.g. diethylenetriamine-pentaacetic acid or salts thereof, such as the pentasodium salt, ethylenediaminetetraacetic acid (EDTA) or salts thereof, in order to protect the hydrogen peroxide from decomposition caused by metal ions.

In a preferred embodiment of the invention the dimethyl farnesyl amines are those wherein the double bond located closest to the dimethyl amine functional group is trans in configuration.

In another preferred embodiment of the invention the dimethyl farnesyl amines are mixtures of head and tail products without any selectivity on the trans or cis configuration of the double bond located closest to the dimethyl amine functional group.

As already stated above, the dimethyl farnesyl amine used in the oxidation reaction to prepare the inventive amine oxides or inventive compounds may be obtained by reacting farnesene with dimethyl amine or a dimethyl amine source in a hydroamination reaction.

The hydroamination of unsaturated hydrocarbons to respective amines, and in particular using dimethyl amine or a dimethyl amine source, is a reaction well known to the person skilled in the art. (see e.g. J. Pawlas; Y. Nakao.;

M. Kawatsura; J. F. Hartwig. A general nickel-catalyzed hydroamination of

1 ,3-dienes by alkylamines: Catalyst selection, scope, and mechanism. J. Am. Chem. Soc. 2002, 124 (14), 3669-3679.).

Preferably, the dimethyl farnesyl amine used in the oxidation reaction to prepare the inventive amine oxides or the inventive compounds is obtained by reacting farnesene with dimethyl amine or a dimethyl amine source in the presence of a transition metal catalyst.

Preferably, the dimethylamine source used in the hydroamination reaction to prepare dimethyl farnesyl amine is selected from the group consisting of dimethyl amine hydrochloride, preferably to be used together with a base, and dimethyl ammonium dimethyl carbamate.

The hydroamination reaction to prepare dimethyl farnesyl amine may be

performed in diverse solvents, such as in organic aliphatic or aromatic solvents, preferably in polar or polar aprotic hydrocarbons or ionic liquids. Particularly preferred are e.g. the following solvents:

- Aliphatic hydrocarbons, such as n-pentane, n-hexane, n-octane, iso-octane;

Alcohols, such as methanol, ethanol, iso-propanol, tert-butanol;

Aromatic hydrocarbons, such as toluene, xylene, mesitylene;

Nitriles, such as acetonitrile, 3-methoxy propionitrile;

Amides, such as dimethyl formamide, dimethylacetamide;

- Ethers, such as diethyl ether, methyl-tert-butyl ether, anisole;

Carbonates, such as ethylene-, propylene- or butylene carbonate;

Ionic liquids, such as dimethyl ammonium dimethyl carbamate (DimCarb);

Highly polar solvents, such as dimethyl sulfoxide, N-methyl pyrrolidone. Even more preferred solvents for the hydroamination reaction to prepare dimethyl farnesyl amine are anisole, dimethyl formamide, dimethylacetamide, methanol, iso-propanol, dioxane, dimethyl sulfoxide (DMSO), dimethyl ammonium dimethyl carbamate (DimCarb) and acetonitrile.

Depending on the dimethyl amine source used, the hydroamination reaction to prepare dimethyl farnesyl amine may also be performed without additional solvent. This is e.g. the case when DimCarb is used, because in this case the DimCarb is used as solvent and also as a reactant.

In a preferred embodiment of the present invention, the weight ratio solvent :

reactants in the hydroamination reaction to prepare dimethyl farnesyl amine is 1 : 1 to 15 : 1 , preferably 2 : 1 to 10 : 1 and more preferably 3 : 1 to 5 : 1 .

As catalyst in the hydroamination reaction to prepare dimethyl farnesyl amine, transition metals selected from group 10 of the periodic table and preferably selected from the group consisting of nickel-, palladium- and platinum-precursors, are used.

Therefore, the transition metal catalyst for the hydroamination reaction to prepare dimethyl farnesyl amine preferably comprises a metal selected from group 10 of the periodic table and more preferably comprises a metal selected from the group consisting of nickel, palladium and platinum.

In the hydroamination reaction to prepare dimethyl farnesyl amine the transition metal catalyst is completely dissolved in the reaction mixture and is modified by an organic ligand. The catalyst and the farnesene are used in the hydroamination reaction to prepare dimethyl farnesyl amine preferably in a molar ratio catalyst : farnesene of from 1 : 10 to 1 :1000, more preferably of from 1 : 10 to 1 :200, and even more preferably of from 1 :10 to 1 :125. Preferred precursors are selected from the following group:

Nickel precursors, such as Ni°(cod)2, Ni"(acac)2, Ni"(hfacac)2, Ni"Cl2;

Palladium precursors, such as Pd°2dba3, Pd"(acac)2, Pd"(hfacac)2,

Platinum precursors, such as Pt"Cl2, Pt M (cod)Cl2, Pt"(acac)2, K 2 Pt N Cl4.

Particularly preferred are palladium precursors with fluorinated leaving groups, such as Pd"(tfa)2 or Pd"(hfacac)2.

In a preferred embodiment of the invention the catalyst used in the hydroamination reaction to prepare dimethyl farnesyl amine may be recycled after the reaction.

One possibility for the separation of the catalyst is the use of a polar phase and a catalyst with polar ligands for the preparation of nonpolar products. The nonpolar products may then be extracted with nonpolar hydrocarbons such as n-decane or n-dodecane. The catalyst remains in the polar phase and may be used for further reactions. In the case of using ammonium carbamates for the hydroamination reaction to prepare dimethyl farnesyl amine, such as dimethylammonium dimethylcarbamate (DimCarb), and suitably sulfonated ligands for the catalyst, such as TPPMS, TPPTS or DPPBTS, the catalyst complex may be immobilized in the polar phase and may be separated from the product that forms a distinct phase that may optionally be extracted with additional DimCarb. The catalyst may be used for further reactions, e.g. by adding fresh farnesene to the polar phase and starting a new hydroamination reaction to prepare dimethyl farnesyl amine.

The transition metal catalyzed hydroamination reaction to prepare dimethyl farnesyl amine may be performed either with or without ligands. Preferably, phosphor ligands are used. The following list comprises some selected examples for ligands:

Triphenylphosphane (PPh3); sodium 3-(diphenylphosphanyl)benzenesulfonate (TPPMS);

sodium 3,3\3"-phosphanetriyltribenzenesulfonate (TPPTS);

Triphenyl phosphite (P(OPh)3);

tris(2-methoxyphenyl)phosphane (TOMPP);

Tricyclohexylphosphane (PCy3);

Triethylphosphane (PEt3);

Tri-teff-butylphosphane (PfBu3);

1.2- bis(diphenylphosphanyl)ethane (DPPE);

1.3- bis(diphenylphosphanyl)propane (DPPP);

1 ,4-bis(diphenylphosphanyl)butane (DPPB);

sodium 3,3',3",3'"-(butane-1 ,4-diylbis(phosphanetriyl))tetrabenzenesulfonate (DPPBTS);

1 ,7-bis(diphenylphosphanyl)heptane (DPPH);

1 ,1 '-bis(diphenylphosphino)-ferrocene (DPPF);

(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) (XantPhos);

sodium 4,5-bis(diphenylphosphanyl)-9,9-dimethyl-9H-xanthene-2,7-dis ulfonate (Sulfo-XantPhos);

4,6-bis(diphenylphosphanyl)-1 OH-phenoxazin (NiXantPhos);

(oxybis(2,1 -phenyl))bis(diphenylphosphane) (DPEPhos).

Preferably, the molar ratio metal : ligand (e.g. palladium : ligand) is of from 1 :1 to 1 :50, more preferably of from 1 :2 to 1 :30, and even more preferably of from 1 :2 to 1 :16. Preferably, the molar ratio farnesene : (dimethylamine or dimethyl amine source) in the hydroamination reaction to prepare dimethyl farnesyl amine is of from 1 :1 to 1 :10 and more preferably of from 1 :2 to 1 :5.

Preferably, the hydroamination reaction to prepare dimethyl farnesyl amine is performed in the presence of an inert gas, more preferably in the presence of argon or nitrogen. Preferably, the hydroamination reaction to prepare dimethyl farnesyl amine is performed at a pressure of from 1 to 10 bar, more preferably at a pressure of from 2 to 8 bar, and even more preferably at a pressure of from 3 to 6 bar. Preferably, the hydroamination reaction to prepare dimethyl farnesyl amine is performed at a temperature of from 50 to 150 °C, more preferably at a temperature of from 60 to 120 °C, and even more preferably at a temperature of from 70 to 100 °C. In the context of the present invention "farnesene" is understood to encompass alpha-farnesene and beta-farnesene. Among those beta-farnesene is preferred and trans-beta-farnesene (trans-7,1 1 -dimethyl-3-methylene-1 ,6,10-dodecatriene) is particularly preferred. Farnesene such as trans-beta-farnesene is commercially available.

The process described above that is used to prepare the inventive amine oxides or the inventive compounds (either in one step via the oxidation reaction or in two steps via the hydroamination reaction in addition to the oxidation reaction) is a further subject matter of the present invention.

The inventive amine oxides and the inventive compounds are advantageously suited as surfactants and preferably as low-foaming surfactants, furthermore preferably in crop protection applications, hard surface applications, laundry applications or automatic dishwashing.

Therefore, a further subject matter of the present invention is the use of inventive amine oxides or inventive compounds as surfactants and preferably as low- foaming surfactants, furthermore preferably in crop protection applications, hard surface applications, laundry applications or automatic dishwashing.

The inventive amine oxides and the inventive compounds are furthermore advantageously suited as wetting agents, preferably in crop protection

applications, hard surface applications or laundry applications. Therefore, a further subject matter of the present invention is the use of inventive amine oxides or inventive compounds as wetting agents, preferably in crop protection applications, hard surface applications or laundry applications.

The inventive amine oxides or inventive compounds can be blended with other substances to provide formulations useful in a variety of industrial and other applications in which low foam, high surface tension reduction, and fast wetting times are desired. Non-limiting examples of such substances include alkalizing agents, amphoteric surfactants, quaternary ammonium compounds, sequestering agents, dyes and fragrances. In general, these agents should not contribute significant amounts of foam to the formulation. In the case of (inventive amine oxide or inventive compound)/amphoteric surfactant blends, the respective weight ratio inventive amine oxide : amphoteric surfactant in the blend is generally between 5:1 and about 1 :5.

Examples of alkalizing agents that can be used with the inventive amine oxides or inventive compounds include sodium hydroxide, sodium carbonate and sodium metasilicate.

A further subject matter of the present invention are crop protection compositions, hard surface cleaning compositions, laundry detergent compositions and automatic dishwashing compositions comprising one or more inventive amine oxides and/or one or more inventive compounds.

The inventive crop protection compositions, hard surface cleaning compositions, laundry detergent compositions and automatic dishwashing compositions may comprise further ingredients. These further ingredients may be selected from those generally used in such compositions.

The following examples describe the synthesis and evaluation of the inventive amine oxides and/or the inventive compounds. These examples are intended to illustrate the invention without limiting its scope. Examples:

The following abbreviations are used:

Example 1 - Synthesis of dimethyl farnesyl amine oxide Step 1 - Synthesis of dimethyl farnesyl amine

In a 25 mL stainless steel autoclave 3066.4 mg trans-beta-farnesene and 6039.2 mg DimCarb (= dimethylammonium dimethylcarbamate) are added to 10.6 mg Pd(tfa)2 and 100.0 mg DPPBTS. The autoclave is sealed and heated to 100 °C for 3 h, and stirred with a magnetic stir bar at 500 rpm. To stop the reaction, the autoclave is cooled to room temperature and the developed gas pressure is released. The reaction mixture is transferred into a Schlenk tube under a counter flow of argon. In the Schlenk tube, a spontaneous phase separation occurs. The lower, polar phase is transferred back into the autoclave. The nonpolar product phase is extracted using 1073.8 mg DimCarb. After the phases separate again, the polar phase is transferred into the autoclave together with 3065.7 mg farnesene and the reaction is started again. The product phase may be purified using column chromatography. Between 2543 and 3366 mg of product is obtained in several runs.

Step 2 - Oxidation of dimethyl farnesyl amine to dimethyl farnesyl amine oxide In a 100 ml_ reaction vessel with a magnetic stir bar, dimethyl farnesyl amine (15 g, 0.058 mol) was suspended in deionized water (32.4 g). The vessel was sealed with a cap. Diethylenetriamine-pentaacetic acid pentasodium salt solution (40 wt.-% in water, 0.036 g, 0.028 mmol) was then added. The reaction mixture was heated to 50 °C under CO2 atmosphere. Hydrogen peroxide (35 wt.-% in water, 5.77 g, 0.059 mol) was added dropwise over a period of 3 h. The reaction was then kept at 50 °C for another 1 h. Amine value was measured to monitor the reaction. Dimethyl farnesyl amine oxide was obtained as a light yellow aqueous solution (30 wt.-%, 38.7 g).

Comparative example - Synthesis of diethyl farnesyl amine oxide Step 1 - Synthesis of diethyl farnesyl amine

10.6 mg Pd(tfa)2 and 137.8 mg DPEPhos are weighed into a 25 ml_ stainless steel autoclave and are dissolved in 5 ml_ methanol. Thereafter, 817.7 mg trans- beta-farnesene and 297.1 mg diethyl amine are added. The autoclave is sealed and pressurized with 5 bar of argon. The autoclave is heated to 100 °C for 5 h and stirred with a magnetic stir bar at 500 rpm. To stop the reaction, the autoclave is cooled to room temperature and thereafter, the argon is cautiously released. The solvent is removed from the reaction solution obtained under reduced pressure and the product is purified using column chromatography. 960.4 mg (89 %) of hydroamination products are obtained. Step 2 - Oxidation of diethyl farnesyl amine to diethyl farnesyl amine oxide

This synthesis follows the same procedure as described in Example 1 , using 17 g (0.057 mol) diethyl farnesyl amine and 13.63 g (0.15 mol) hydrogen peroxide to produce diethyl farnesyl amine oxide as a suspension, which went quickly into phase separation.

Example 2 - Evaluation of surfactant properties of dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide Dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide were tested for their surface tension reduction properties, wetting abilities and foam ability. The products were tested in the methods described below.

CMC (critical micelle concentration) and surface tension measurements

These measurements were conducted with the Kruss Tensiometer K 100 (Ring), which utilized the Du Nouy ring method. Surface tension profiles of the amine oxides were measured at 25 °C. Determination of wetting ability by immersion

This measurement was modified based on the European Standard EN 1772:2000. A 500 ml_ 0.1 wt.-% aqueous solution of test surfactant was prepared. The test solution was kept at room temperature to stabilize for 1 h. A raw cotton disc (30 mm diameter, wfk Testgewebe GmbH), was clamped in a gripper and immersed in the solution. Stopwatch was started at the moment when the lower part of the disc touched the solution and stopped when the disc began to sink of its own accord. The arithmetic mean of five measurements was calculated and recorded as the wetting time. Measurement of foam creation and decay on a SITA foam tester This method monitors foam generation and decay at room temperature over time. A surfactant solution of 0.01 g/L was pumped into the SITA foam tester R2000. The speed of the stirring plate was set to 1200 rpm. Foam creation was recorded in a 10 second interval for 5 minutes and decay was recorded in a 30 second interval for 15 minutes at room temperature.

Table 1 shows a comparison of the properties of dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide.

Table 1 Properties of dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide

C20: concentration of surfactant (here: dialkyl farnesyl amine oxide) to reduce the surface tension of water by 20 mN/m

Diethyl farnesyl amine oxide has very poor solubility in water. This made the measurement of surface tension impossible and resulted in a longer wetting time. However, dimethyl farnesyl amine oxide on the other hand showed very effective surface tension reduction properties and a good wetting time, while producing no foam at all. Example 3 - Comparison of dynamic surface tension Dynamic surface tension measurements

These measurements were conducted with the Kruss PocketDyne BP2100, which utilized the maximum bubble pressure method of surface tension analysis. Surface tension profiles of dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide at the desired concentration were measured in deionized water at 25 °C.

When surfactants are used in crop protection applications, usually 0.1 - 10 g/L, preferably 0.3 - 3 g/L, of each surfactant is present, and the average time for surfactant solution spraying from nozzle to crop leaves is between 20 to 400 ms (ms: milliseconds).

Table 2 shows the results of a comparison of the dynamic surface tension at surface ages of 20 ms, 50 ms, 100 ms, 200 ms and 400 ms for dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide. The results in table 2 are given in mlM/m.

Table 2 Surface tension of dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide at different surface ages

In general, if a surfactant compound can reduce the surface tension below 55 mlM/m at the surface age of 200 ms, it is considered as a good wetting agent in crop protection applications. The data of table 2 show that dimethyl farnesyl amine oxide is a significantly better wetting agent than diethyl farnesyl amine oxide.

The evaluation of dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide revealed significant differences in application tests, in which dimethyl farnesyl amine oxide showed better surface tension reduction, better wetting ability and no foam.