2-ethylhexanoic acid

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

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

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

Procedure: To a well-stirred reaction vessel equipped with a thermometer and a pH electrode were added 45 g of water, 0.075 mole of a 33 wt % aqueous NaOH solution, 0.075 mole of 2-ethylhexanoic acid, and 0.23 g of Arquad CB50 (i.e. cocobenzyldimethylammonium chloride, ex Akzo Nobel) at 5° C. 0.075 mole of methyl chloroformate was dosed in 5 min at 5° C. The mixture was post-reacted for 30 min at 5° C. and a pH of 8. Then, the water layer was separated, giving 15.2 g of 2-ethylhexanoyl methyl carbonate having a content of 99.5% (determined by NMR) in a yield of 99.6%. To a well-stirred reaction vessel equipped with a thermometer The mixture was post-reacted for 30 min at 5° C. Then, the water layer was separated

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

Procedure: A procedure similar to that of Example 2 was used for the reaction with 2-EHA. Starting from the TAIT product described in the preceding paragraph (1.0 g, ca. 4.5 mmol), 2-ethylhexyl acrylate (0.82 g, 4.5 mmol) and cesium carbonate (0.75 g, 2.25 mmol) in acetonitrile (20 mL), the product was isolated as a yellow oil and solid mixture (1.8 g, 99 %). IR: 3325, 2933, 2860, 1732, 1480 cm−1.

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

Procedure: A mixture of TMIT (1.0 g, 6.33 mmol), 2-ethylhexyl acrylate (1.16 g, 6.33 mmol) and cesium carbonate (1.0 g, 3.3 mmol) in acetonitrile (15 mL) was stirred at room temperature for 24 h. The reaction mixture was filtered to separate solid cesium carbonate and solvent was evaporated from the filtrate to obtain the product as a colorless oil (1.9 g, 88 %). IR: 3325, 2961, 1732, 1595, 1480 cm31 1; 1H NMR (CDCl3, 500 MHz): δ3.96 (overlapping d, 2 H), 3.83 (t, 1.72 H), 3.22 (t, 0.28 H), 2.82 (t, 1.72 H), 2.71 (t, 0.28 H), 1.91 (bs, 1H), 1.42 (s, 6 H), 1.40 (s, 6H), 1.35-1.20 (m, 8 H), 0.85 (overlapping t, 6 H) ppm; 13C NMR (CDCl3, 125 MHz): δ205.8, 173.6, 171.9, 171.3, 130.2, 128.5, 88.7, 82.9, 70.35, 69.6, 67.2, 66.9, 66.8, 40.6, 38.6, 33.9, 31.4, 30.26, 30.21, 28.79, 28.71, 28.23, 25.8, 23.64, 22.83, 13.9, 10.9 ppm. The reaction mixture was filtered to separate solid cesium carbonate and solvent was evaporated from the filtrate

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

Procedure: 113 g of N-phenyl-N'-benzyl-urea were dissolved in 1000 g of o-dichlorobenzene; the solution was made acid with 2-ethyl-hexanoic acid and reacted with 72 g of dimethyl maleate. After a reaction time of 6 hours at 175° C, the solvent was distilled off and the residue triturated with ether. The product separated by suction filtration can be obtained pure by recrystallisation from toluene. The white crystals obtained have a melting point of 130° C and their structure was demonstrated by the IR and NMR spectra and elementary analysis. After a reaction time of 6 hours at 175° C, the solvent was distilled off the residue triturated with ether The product separated by suction filtration can be obtained pure by recrystallisation from toluene The white crystals obtained

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4 moles (744 grams) of Butyloctanol were charged to an autoclave, and 0.1% of Potassium Hydroxide was added as catalyst. The autoclave was purged with Nitrogen and 16 moles (928 grams) of Propylene Oxide were added at a temperature of 150–160° C. and a pressure of 30–40 psi. Upon completion, the batch was cooled to 80° C. and neutralized with Phosphoric Acid. The resultant product, PPG-4 Butyloctyl Ether, was a very pale yellow liquid. A four-neck flask was charged with 1,224 grams of the PPG-4 Butyloctyl Ether, along with 3 moles (432 grams) of 2-Ethyl Hexanoic Acid. A catalytic amount of p-Toluenesulfonic Acid was added and the reaction mixture was heated with agitation to 160° C. until an acid value of less than 5 mg KOH was obtained. The reaction mixture was cooled to 80° C., washed with a dilute Sodium Hydroxide solution sufficient to neutralize the residual acid present, followed by washing with water. The ester layer was separated and heated under vacuum until a moisture content of less than 0.2% was obtained, followed by vacuum filtration. The resultant product, PPG-4 Butyloctyl Ether Ethylhexanoate, was a clear very pale yellow liquid having an acid value of less than 0.1 mg KOH. was added as catalyst were added at a temperature of 150–160° C. was obtained washed with a dilute Sodium Hydroxide solution sufficient by washing with water The ester layer was separated heated under vacuum until a moisture content of less than 0.2% was obtained followed by vacuum filtration

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(2H-Benzotriazol-2-yl)-6-chloromethyl-4-methyl-phenol (10.0 g, 33 mmol) is suspended in a mixture of 2-ethylhexanoic acid (11.9 g, 82 mmol) and tetrahydrofuran (75 g) and stirred at 70° C. for 30 minutes. Sodium carbonate (10.5 g, 99 mmol) is added. The reaction mixture is stirred at 60° C. for 15 minutes and evaporated to dryness. The residue is dissolved in ethyl acetate and extracted with an aqueous potassium carbonate solution (10%) and brine. The organic layer is dried over sodium sulphate, filtered and evaporated to dryness. The crude product is purified by column chromatography (ethyl acetate/heptane 1:12) to yield 11.2 g of 2-Ethyl-hexanoic acid 3-(2H-benzotriazol-2-yl)-2-hydroxy-5-methyl-benzyl ester. The reaction mixture is stirred at 60° C. for 15 minutes evaporated to dryness The residue is dissolved in ethyl acetate extracted with an aqueous potassium carbonate solution (10%) and brine The organic layer is dried over sodium sulphate filtered evaporated to dryness The crude product is purified by column chromatography (ethyl acetate/heptane 1:12)

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

Procedure: To a slurry of NaBH4 (7.567 g, 200.0 mmol) in DCE (200 mL) was added 2-Ethylhexanoic acid (95.50 mL, 600.0 mmol) slowly over 30 minutes via addition funnel. The mixture was stirred at ambient temperature for 4 hours with venting to release H2. In a separate 1 L flask was added the product from Step B (23.53 g, 100 mmol), benzylamine (16.37 mL, 150.0 mmol) and DCE (400 mL). The hydride solution was then added via addition funnel to the mixture over 1 hours while cooling the reaction in a water bath. The reaction was stirred at ambient temperature for 2 days, then diluted with water (100 mL) and concentrated in vacuo to remove solvent. The residue was partitioned between EtOAc (300 mL) and a saturated aqueous Na2CO3 solution (2×75 mL). The mixture was shaken, the layers separated and the organic phase washed again with a saturated aqueous Na2CO3 solution (100 mL) and finally with brine (50 mL). The aqueous phases were extracted with CHCl3 (3×75 mL), and the organic phases were dried over Na2CO3, filtered and concentrated. The crude product was purified by column chromatography (EtOAc/Hexane) providing 19.55 g of the pure cis product and 5.0 g of a cis/trans mixture (80%). via addition funnel while cooling the reaction in a water bath The reaction was stirred at ambient temperature for 2 days concentrated in vacuo to remove solvent The residue was partitioned between EtOAc (300 mL) The mixture was shaken the layers separated the organic phase washed again with a saturated aqueous Na2CO3 solution (100 mL) and finally with brine (50 mL) The aqueous phases were extracted with CHCl3 (3×75 mL) the organic phases were dried over Na2CO3 filtered concentrated The crude product was purified by column chromatography (EtOAc/Hexane)

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(2H-Benzotriazol-2-yl)-6-chloromethyl-4-methyl-phenol (10.0 g, 33 mmol) is suspended in a mixture of 2-ethylhexanoic acid (11.9 g, 82 mmol) and tetrahydrofuran (75 g) and stirred at 70° C. for 30 minutes. Sodium carbonate (10.5 g, 99 mmol) is added. The slightly yellow reaction mixture is stirred at 60° C. for 15 minutes and evaporated to dryness. The residue is dissolved in ethyl acetate and extracted with an aqueous potassium carbonate solution (10%) and brine. The organic layer is dried over sodium sulphate, filtered and evaporated to dryness. The crude product is purified by column chromatography (ethyl acetate/heptane 1:12) to yield 11.2 g of 2-Ethyl-hexanoic acid 3-(2H-benzotriazol-2-yl)-2-hydroxy-5-methyl-benzyl ester. The slightly yellow reaction mixture is stirred at 60° C. for 15 minutes evaporated to dryness The residue is dissolved in ethyl acetate extracted with an aqueous potassium carbonate solution (10%) and brine The organic layer is dried over sodium sulphate filtered evaporated to dryness The crude product is purified by column chromatography (ethyl acetate/heptane 1:12)

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

Procedure: A solution of 120 g (3.0 moles) of sodium hydroxide was dissolved in 500 ml of distilled water. 2-Ethylhexanoic acid (475 g, 3.3 moles) was added with stirring to form sodium 2-ethylhexanoate. In a separate container, 200 g (0.5 mole) of chromium nitrate nonahydrate was dissolved in 500 ml of distilled water. The chromium nitrate solution was slowly added to the sodium 2-ethylhexanoate solution with good stirring. When the addition was complete, 500 ml of hexane were added and stirring was continued for 10 minutes. The layers were separated and the hexane layer containing the aquated chromium III tri-2-ethylhexanoate was washed with dilute sodium hydroxide solution, water, dilute sodium carbonate solution and finally with distilled water. The hexane solution was then dried over anhydrous magnesium sulfate. Most of the hexane was removed under reduced pressure and the resulting concentrate was slowly added to 500 ml of acetone. The resulting blue granular solid was filtered and air dried to yield 130 g (54%) of aquated chromium tri-2-ethylhexanoate. Molecular weight determination indicated that the compound is polymeric in nature, probably due to the oxygen bridging of chromium atoms.

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

Procedure: To a slurry of NaBH4 (7.567 g, 200.0 mmol) in DCE (200 mL) was added 2-Ethylhexanoic acid (95.50 mL, 600.0 mmol) slowly over 30 minutes via addition funnel. The mixture was stirred at ambient temperature for 4 hours with venting to release H2. In a separate 1 L flask was added the product from Step B (23.53 g, 100 mmol), benzylamine (16.37 mL, 150.0 mmol) and DCE (400 mL). The hydride solution was then added via addition funnel to the mixture over 1 hours while cooling the reaction in a water bath. The reaction was stirred at ambient temperature for 2 days, then diluted with water (100 mL) and concentrated in vacuo to remove solvent. The residue was partitioned between EtOAc (300 mL) and a saturated aqueous Na2CO3 solution (2×75 mL). The mixture was shaken, the layers separated and the organic phase washed again with a saturated aqueous Na2CO3 solution (100 mL) and finally with brine (50 mL). The aqueous phases were extracted with CHCl3 (3×75 mL), and the organic phases were dried over Na2CO3, filtered and concentrated. The crude product was purified by column chromatography (EtOAc/Hexane) providing 19.55 g of the pure cis product and 5.0 g of a cis/trans mixture (80%). via addition funnel while cooling the reaction in a water bath The reaction was stirred at ambient temperature for 2 days concentrated in vacuo to remove solvent The residue was partitioned between EtOAc (300 mL) The mixture was shaken the layers separated the organic phase washed again with a saturated aqueous Na2CO3 solution (100 mL) and finally with brine (50 mL) The aqueous phases were extracted with CHCl3 (3×75 mL) the organic phases were dried over Na2CO3 filtered concentrated The crude product was purified by column chromatography (EtOAc/Hexane)