octadec-9-ene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A process according to claim 1, wherein (a) is 1-decene or 9-octadecene and (b) is a mixture of 2-tetradecene with 2-hexadecene or 1-pentadecene, whereby a mixture of 9-tricosene and 9-heneicosene is formed.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 9-triscosene and 9-heneicosene was prepared by following the process described in Example 8, namely by conducting, over 39 g. of the aforedescribed rehenium-containing catalyst, at 60° C., a mixture of 196 g. (0.79 mole) of 9-octadecene, 58 g. (0.26 mole) of 2-hexadecene, and 16 g. (0.08 mole) of 2-tetradecene. After a reaction time of 5 hours and with a throughput of 200 ml. of olefin mixture per hour, 3.2% by weight of tricosene and 1.4% by weight of heneicosene were obtained. The content of the cis-isomer was 24%. was prepared of the aforedescribed rehenium-containing catalyst, at 60° C., a mixture of 196 g After a reaction time of 5 hours

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the procedure outlined in Example 6, 142 g. (0.56 mole) of 9-octadecene and 82 g. (0.37 mole) of 2-hexadecene were reacted at a reaction temperature of 100° C. After 5 hours and with a throughput of 200 ml. of olefin mixture per hour, 7.4% by weight of tricosene was obtained.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Example 1 was repeated, with the difference that 20 ml. of 1-decene was utilized in place of 9-octadecene. Within 5 minutes, 4.8% by weight of tricosene was formed and within 30 minutes, 5.7% by weight of tricosene was obtained.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In 1994 (Choo, Ooi, & Ooi, 1994), synthesis of Civetone was reported from Palm oil. In this process Oleic acid (C18:1) was obtained from Palm oil by hydrolytic splitting with 99% purity. See FIG. 2. The pure Oleic acid was esterified under acidic conditions using concentrated sulfuric acid at 110° C. Self-metathesis of ethyl oleate was performed using WCl6 and SnMe4 to give two products, 9-Octadecene and Diethyl 9-Octadecenedioate, with almost quantitative yields of 97 and 99% respectively. Silica-gel chromatography was used to separate the two products. The Diethyl 9-Octadecenedioate was cyclized using base catalyzed Dieckmann Condensation under inert conditions. Dieckmann Condensation was carried out under argon using potassium hydride (KH) in dry THF at 55° C. for 3 hours to give 2-ethoxycarbonyl-9-cycloheptadecenone with 63% yield which was purified by silica-gel chromatography. Civetone was synthesized by hydrolysis followed by decarboxylation of 2-ethoxycarbonyl-9-cycloheptadecenone using 5% NaOH/THF/Ethanol with 93% yield which was also purified by silica-gel chromatography. at 110° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Several other runs were carried out to demonstrate the use of embodiment A for the disproportionation of unsaturated esters. In run 201, 21 mmoles of methyl oleate, 0.22 mmoles of (methoxyphenylcarbene)pentacarbonyltungsten(0), 2.2 mmoles of SnCl4, and 2.2 mmoles of SiCl4 in about 18 ml of chlorobenzene were stirred at 55° C. for 72 hours. The reaction product mixture contained a 16% yield of 9-octadecene and about a 10% yield of dimethyl 9-octadecen-1,18-dioate. The yield of 9-octadecene is increased over the yield of run 168 which did not use SiCl4.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a particular embodiment, the metathesis of methyl oleate with ethylene will yield cross-metathesis products of 1-decene and methyl-9-decenoate. In addition to the desired products, the methyl oleate may homometathesize to produce small amounts of 9-octadecene, a less desirable product, and 1,18-dimethyl-9-octadecenedioate, a second less desirable product. Yield was calculated as 100×[micromoles of ethenolysis products obtained from the GC]/[micromoles of methyl oleate weighed into reactor]. 1-decene selectivity is shown as a percentage and was calculated as 100×[GC peak area of 1-decene & methyl-9-decenoate]/[sum of GC peak areas of 1-decene, methyl-9-decenoate, and the homometathesis products, 9-octadecene, and 1,18-dimethyl-9-octadecenedioate]. Catalyst turnovers for production of the 1-decene was calculated as the [micromoles of 1-decene obtained from the gas chromatograph]/([micromoles of catalyst].

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In 1994 (Choo, Ooi, & Ooi, 1994), synthesis of Civetone was reported from Palm oil. In this process Oleic acid (C18:1) was obtained from Palm oil by hydrolytic splitting with 99% purity. See FIG. 2. The pure Oleic acid was esterified under acidic conditions using concentrated sulfuric acid at 110° C. Self-metathesis of ethyl oleate was performed using WCl6 and SnMe4 to give two products, 9-Octadecene and Diethyl 9-Octadecenedioate, with almost quantitative yields of 97 and 99% respectively. Silica-gel chromatography was used to separate the two products. The Diethyl 9-Octadecenedioate was cyclized using base catalyzed Dieckmann Condensation under inert conditions. Dieckmann Condensation was carried out under argon using potassium hydride (KH) in dry THF at 55° C. for 3 hours to give 2-ethoxycarbonyl-9-cycloheptadecenone with 63% yield which was purified by silica-gel chromatography. Civetone was synthesized by hydrolysis followed by decarboxylation of 2-ethoxycarbonyl-9-cycloheptadecenone using 5% NaOH/THF/Ethanol with 93% yield which was also purified by silica-gel chromatography. at 110° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In 1994 (Choo, Ooi, & Ooi, 1994), synthesis of Civetone was reported from Palm oil. In this process Oleic acid (C18:1) was obtained from Palm oil by hydrolytic splitting with 99% purity. See FIG. 2. The pure Oleic acid was esterified under acidic conditions using concentrated sulfuric acid at 110° C. Self-metathesis of ethyl oleate was performed using WCl6 and SnMe4 to give two products, 9-Octadecene and Diethyl 9-Octadecenedioate, with almost quantitative yields of 97 and 99% respectively. Silica-gel chromatography was used to separate the two products. The Diethyl 9-Octadecenedioate was cyclized using base catalyzed Dieckmann Condensation under inert conditions. Dieckmann Condensation was carried out under argon using potassium hydride (KH) in dry THF at 55° C. for 3 hours to give 2-ethoxycarbonyl-9-cycloheptadecenone with 63% yield which was purified by silica-gel chromatography. Civetone was synthesized by hydrolysis followed by decarboxylation of 2-ethoxycarbonyl-9-cycloheptadecenone using 5% NaOH/THF/Ethanol with 93% yield which was also purified by silica-gel chromatography. at 110° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In the 1990s, it was demonstrated that homogeneous ruthenium-based catalysts were effective in catalyzing olefin metathesis; moreover, these catalysts, in contrast to the tungsten and rhenium catalysts, often tolerate functionally substituted alkenes (Grubbs, R. H., Handbook of Metathesis, Wiley-Vch, Verlag GmbH & Co. KGaA, Weinheim (2003)). Such ruthenium-based catalysts have been used to prepare α,ω-dicarboxylate esters via metathetic routes. For example, a two-step process was reported using Grubbs catalysts to prepare long-chain unsaturated α,ω-dicarboxylate methyl esters (Warwel, S., et al., Polym. Sci. Part A: Polym. Chem., 39: 1601-1609 (2001)). Cross-metathesis of monounsaturated carboxylic acid methyl esters with ethylene in the presence of the first generation catalyst 1 (FIG. 1) in solution initially gave terminally unsaturated monocarboxylate methyl esters. The resulting terminal monounsaturated esters then underwent self-metathesis in the presence of catalyst 1 to give long-chain α,ω-dicarboxylic acid methyl esters with an overall yield between 38-40% (Warwel, S., et al., Polym. Sci. Part A: Polym. Chem., 39: 1601-1609 (2001); Warwel, S., et al., Ind. Crops & Prod., 20: 301-309 (2004); Warwel, S., et al., Macromol. Chem. Phys., 202: 1114-1121 (2001); Warwel, S., et al., Macromol. Chem. Phys., 202: 849-855 (2001); Warwel, S., et al., Chemosphere, 43: 39-48 (2001)). Self-metathesis of methyl oleate in dichloromethane was reported using the second generation Grubbs catalyst 2 (FIG. 1) and gave the long chain α,ω-dicarboxylic methyl ester 5a (FIG. 2, Eq. 1) in ˜45% conversion (Dinger, M. B., and J. C. Mol, et al., Adv. Synth. Catal., 344: 671-677 (2002)). The self-metathesis of oleic acid in the presence of Cl2(PCy3)2Ru=CH—CH═CPh2 in dichloromethane solution was reported to give 1,18-octadec-9-enedioic acid (5b) and octadec-9-ene (4) in 42% yield (U.S. Pat. No. 5,728,917). However, this process gave low conversion (about 50%) of monounsaturated fatty acids and low yields of dicarboxylic acids. In addition, the reaction was performed in a solvent, dichloromethane, which is an environmental concern.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 9-triscosene and 9-heneicosene was prepared by following the process described in Example 8, namely by conducting, over 39 g. of the aforedescribed rehenium-containing catalyst, at 60° C., a mixture of 196 g. (0.79 mole) of 9-octadecene, 58 g. (0.26 mole) of 2-hexadecene, and 16 g. (0.08 mole) of 2-tetradecene. After a reaction time of 5 hours and with a throughput of 200 ml. of olefin mixture per hour, 3.2% by weight of tricosene and 1.4% by weight of heneicosene were obtained. The content of the cis-isomer was 24%. was prepared of the aforedescribed rehenium-containing catalyst, at 60° C., a mixture of 196 g After a reaction time of 5 hours