Dimethyl Farnesyl Amine Oxide And Its Use As Surfactant Or Wetting Agent

Abstract

Dimethyl amine oxides comprising farnesyl residues are described. These amine oxides are advantageously suited as surfactants or wetting agents.

Claims

1. An amine oxide of formula (I) ##STR00006## wherein R is a radical of the formula ##STR00007## wherein, * 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. The amine oxide according to claim 1 having the formula (Ia) ##STR00008##

3. A compound prepared by reacting a dimethyl farnesyl amine with hydrogen peroxide in the presence of carbon dioxide.

4. The compound according to claim 3, wherein the reacting is performed in a solvent, at a temperature of from 20 to 100 C.

5. The compound according to claim 3, wherein the molar ratio of dimethyl farnesyl amine to hydrogen peroxide is from 1:1 to 1:50.

6. The compound according to claim 3, wherein the dimethyl farnesyl amine is prepared by reacting farnesene with dimethyl amine or a dimethyl amine source in the presence of a transition metal catalyst.

7. The compound according to claim 6, wherein the dimethyl amine source is selected from the group consisting of dimethyl amine hydrochloride and dimethyl ammonium dimethyl carbamate.

8. The compound according to claim 6, wherein the transition metal catalyst comprises a metal selected from the group consisting of metals of group 10 of the periodic table.

9. The compound according to claim 6, wherein the molar ratio of farnesene to (dimethyl amine or dimethyl amine source) is from 1:1 to 1:10.

10. The compound according to claim 6, wherein the reacting is performed at a temperature of from 50 to 150 C.

11. The compound according to claim 6, wherein the farnesene is beta-farnesene.

12. A process for the preparation of an amine oxide or a compound according to claim 1, wherein the process comprises the step of reacting a dimethyl farnesyl amine with hydrogen peroxide in the presence of carbon dioxide.

13. A surfactant comprising at least one amine oxide or compound according to claim 1.

14. A wetting agent comprising at least one oxide or compound according to claim 1.

15. A crop protection composition, hard surface cleaning composition, laundry detergent composition or automatic dishwashing composition comprising at least one amine oxide or compound according to claim 1.

Description

EXAMPLES

[0096] The following abbreviations are used:

TABLE-US-00001 abbreviation meaning acac acetylacetonate cod 1,5-cyclooctadiene dba dibenzylideneacetone DimCarb dimethylammonium dimethylcarbamate DMF N,N-dimethylformamide g gram h hour hfacac 1,1,1,5,5,5-hexafluoroacetylacetonate mg milligram mL milliliter mmol millimol mol-% mol percent rpm revolutions per minute tfa trifluoroacetate wt.-% percent by weight

Example 1

Synthesis of Dimethyl Farnesyl Amine Oxide

Step 1Synthesis of Dimethyl Farnesyl Amine

[0097] 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 2Oxidation of Dimethyl Farnesyl Amine to Dimethyl Farnesyl Amine Oxide

[0098] 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 CO.sub.2 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 1Synthesis of Diethyl Farnesyl Amine

[0099] 10.6 mg Pd(tfa).sub.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 2Oxidation of Diethyl Farnesyl Amine to Diethyl Farnesyl Amine Oxide

[0100] 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

[0101] 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.

[0102] CMC (critical micelle concentration) and surface tension measurements These measurements were conducted with the Krss Tensiometer K 100 (Ring), which utilized the Du Noy ring method. Surface tension profiles of the amine oxides were measured at 25 C.

Determination of Wetting Ability by Immersion

[0103] 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

[0104] 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.

[0105] Table 1 shows a comparison of the properties of dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide.

TABLE-US-00002 TABLE 1 Properties of dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide Dialkyl Surface Wetting farnesyl CMC C.sub.20 tension time amine oxide (g/L) (g/L) (mN/m) (seconds) Foam ability Dimethyl 1.09 0.018 28.7 28 No foam was Diethyl No correct measurement was 54 generated (comparative) able to be obtained due to after 5 fast phase separation minutes C.sub.20: concentration of surfactant (here: dialkyl farnesyl amine oxide) to reduce the surface tension of water by 20 mN/m

[0106] 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

[0107] These measurements were conducted with the Krss 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.

[0108] 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).

[0109] 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 mN/m.

TABLE-US-00003 TABLE 2 Surface tension of dimethyl farnesyl amine oxide and diethyl farnesyl amine oxide at different surface ages Dialkyl Concen- farnesyl tration amine oxide (g/L) 20 ms 50 ms 100 ms 200 ms 400 ms Dimethyl 0.3 59.9 56.9 52.9 51.5 49.5 1.0 43.8 40.7 39.3 38.1 36.9 3.0 35.3 33.2 32.5 32.1 31.5 Diethyl 0.3 66.7 65.6 64.3 65.7 65.0 (comparative) 1.0 60.0 62.0 57.3 56.0 54.9 3.0 55.2 52.7 51.8 50.6 51.6

[0110] In general, if a surfactant compound can reduce the surface tension below 55 mN/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.

[0111] 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.