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Example 1 [0105] This example presents a comparison of various catalysts consisting of a metal deposited on a silicon media. All catalysts were prepared using ionic exchange starting from a colloidal silica stabilized with ammonium ions and metal chloride corresponding to the active species. These items were tested in regards to the functionalization reaction of methyl oleate by hydroxycitronellal which lead to the synthesis of 9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate and of 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate as illustrated in Diagram 2. [0106] The reaction was carried out in a 100 ml glass reactor with mechanical agitation. Twenty-five grams (25.0 g) of methyl ester of sunflower oil HTO (high oleic content-purity: 85% methyl oleate) as well as 13.0 g of hydroxycitronellal (FCC Grade: Purity?95%-Sigma-Aldrich, Ref. W258318) were introduced into the reactor. The solid catalyst of the metal type supported on silica contains 5% by weight of the quantity of methyl oleate engaged, i.e. 250 mg. The environment was heated to 80 C. with continuous air bubbling. The air flow was controlled by a ball flow meter at 70 ml/min. After 7 hours of reaction time, the air flow was stopped and the reaction medium was raised to 150 C. These parameters were maintained for 5 additional hours. Samples of the reaction medium were taken at regular intervals in order to determine the status of the reaction. The reagent conversion rates and the yield rates of the desired products after 7 and 12 hours of reaction time are shown in Table 1: [TABLE-US-00001] Conversion Function- into alized Conversion hydroxy- Epoxide products Type of Reaction into methyl citronellala yield yield catalyst time (hr.) oleate (%) (%) (%) (%) no catalyst 7 37 70 27 11 12 46 92 9 24 Ru/SiO2 7 75 95 52 24 12 80 100 13 39 Co/SiO2 7 76 100 31 19 12 77 100 16 29 Zn/SiO2 7 66 99 30 20 12 69 100 10 27 Ni/SiO2 7 51 90 34 15 12 59 98 13 25 Cr/SiO2 7 49 89 31 15 12 56 97 13 25 Cu/SiO2 7 34 90 24 16 12 38 97 11 22 Rh/SiO2 7 34 86 18 17 12 40 96 8 26 [0107] The composition of the reaction medium was determined by gas phase chromatographic analysis. The Agilent Technologies 6870N chromatograph is equipped with a capillary column (SGE-BPX-70-length: 30 m, inside diameter: 0.25 mm, film thickness: 0.25 mum), of a split/splitless injector and a flame ionization detector (temperature of the injector and the detector: 280 C.). The temperature program of the furnace was as follows: 80 C. (0 min.)-13 C./min.-180 C. (6 min.)-13 C./min.-220 C. (6 min.)-17 C./min.-250 C. (10 min.). [0108] The hold time for the various products under the conditions described above are as follows: dodecane (2.9 min.); hydroxycitronellal (8.9 min.); methyl oleate (12.6 min.); methyl trans-9,10epoxy-stearate (18.9 min.); methyl cis-9,10-epoxy-stearate (19.2 min). [0109] The conversion of reagents at time t is expressed as follows: (number of initial moles of reagent-number of moles of reagent at time t)/number of initial moles of reagent*100. [0110] The epoxide yield at time t was calculated as follows: number of moles of epoxide at time t/(number of initial moles of methyl oleate*relative response coefficient of 9,10-epoxystearate in relation to methyl oleate)*100. [0111] The functionalized products, i.e. the methyl octadecanoate 9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy) and the methyl octadecanoate 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy), were analyzed by steric exclusion chromatography. [0112] The Waters Alliance 2695 chromatograph is equipped with a refraction index detector (RI 410) and with two different columns (Styrage-HR 0.5 and Styragel-HR 1). The temperature of the furnace containing the columns is set at 30 C. and tetrahydrofurane (THF) is used as an eluent at a flow rate of 0.8 ml/min. [0113] Under these conditions, the hold times were as follows: products with high molecular weight (>1000 uma; 15.1 min); functionalized products (16.2 min.); methyl oleate and methyl 9,10-epoxy-stearate (18.1 min.); hydroxycitronellal (19.0 min.). [0114] The functionalized products yield is the relative surface area of the chromatographic peak expressed as a percentage of the total of all peaks.
52%Chromat.
With 5% Ru/SiO2; oxygen; at 80℃; for 7h;
Example 1 [0105] This example presents a comparison of various catalysts consisting of a metal deposited on a silicon media. All catalysts were prepared using ionic exchange starting from a colloidal silica stabilized with ammonium ions and metal chloride corresponding to the active species. These items were tested in regards to the functionalization reaction of methyl oleate by hydroxycitronellal which lead to the synthesis of 9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate and of 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy)methyl octadecanoate as illustrated in Diagram 2. [0106] The reaction was carried out in a 100 ml glass reactor with mechanical agitation. Twenty-five grams (25.0 g) of methyl ester of sunflower oil HTO (high oleic content-purity: 85% methyl oleate) as well as 13.0 g of hydroxycitronellal (FCC Grade: Purity?95%-Sigma-Aldrich, Ref. W258318) were introduced into the reactor. The solid catalyst of the metal type supported on silica contains 5% by weight of the quantity of methyl oleate engaged, i.e. 250 mg. The environment was heated to 80 C. with continuous air bubbling. The air flow was controlled by a ball flow meter at 70 ml/min. After 7 hours of reaction time, the air flow was stopped and the reaction medium was raised to 150 C. These parameters were maintained for 5 additional hours. Samples of the reaction medium were taken at regular intervals in order to determine the status of the reaction. The reagent conversion rates and the yield rates of the desired products after 7 and 12 hours of reaction time are shown in Table 1: [TABLE-US-00001] Conversion Function- into alized Conversion hydroxy- Epoxide products Type of Reaction into methyl citronellala yield yield catalyst time (hr.) oleate (%) (%) (%) (%) no catalyst 7 37 70 27 11 12 46 92 9 24 Ru/SiO2 7 75 95 52 24 12 80 100 13 39 Co/SiO2 7 76 100 31 19 12 77 100 16 29 Zn/SiO2 7 66 99 30 20 12 69 100 10 27 Ni/SiO2 7 51 90 34 15 12 59 98 13 25 Cr/SiO2 7 49 89 31 15 12 56 97 13 25 Cu/SiO2 7 34 90 24 16 12 38 97 11 22 Rh/SiO2 7 34 86 18 17 12 40 96 8 26 [0107] The composition of the reaction medium was determined by gas phase chromatographic analysis. The Agilent Technologies 6870N chromatograph is equipped with a capillary column (SGE-BPX-70-length: 30 m, inside diameter: 0.25 mm, film thickness: 0.25 mum), of a split/splitless injector and a flame ionization detector (temperature of the injector and the detector: 280 C.). The temperature program of the furnace was as follows: 80 C. (0 min.)-13 C./min.-180 C. (6 min.)-13 C./min.-220 C. (6 min.)-17 C./min.-250 C. (10 min.). [0108] The hold time for the various products under the conditions described above are as follows: dodecane (2.9 min.); hydroxycitronellal (8.9 min.); methyl oleate (12.6 min.); methyl trans-9,10epoxy-stearate (18.9 min.); methyl cis-9,10-epoxy-stearate (19.2 min). [0109] The conversion of reagents at time t is expressed as follows: (number of initial moles of reagent-number of moles of reagent at time t)/number of initial moles of reagent*100. [0110] The epoxide yield at time t was calculated as follows: number of moles of epoxide at time t/(number of initial moles of methyl oleate*relative response coefficient of 9,10-epoxystearate in relation to methyl oleate)*100. [0111] The functionalized products, i.e. the methyl octadecanoate 9-hydroxy-10-(7-hydroxy-3,7-dimethyloctanoyloxy) and the methyl octadecanoate 10-hydroxy-9-(7-hydroxy-3,7-dimethyloctanoyloxy), were analyzed by steric exclusion chromatography. [0112] The Waters Alliance 2695 chromatograph is equipped with a refraction index detector (RI 410) and with two different columns (Styrage-HR 0.5 and Styragel-HR 1). The temperature of the furnace containing the columns is set at 30 C. and tetrahydrofurane (THF) is used as an eluent at a flow rate of 0.8 ml/min. [0113] Under these conditions, the hold times were as follows: products with high molecular weight (>1000 uma; 15.1 min); functionalized products (16.2 min.); methyl oleate and methyl 9,10-epoxy-stearate (18.1 min.); hydroxycitronellal (19.0 min.). [0114] The functionalized products yield is the relative surface area of the chromatographic peak expressed as a percentage of the total of all peaks.
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