ethyl octanoate

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: Toluene (1.0 ml), dried using MS 4A, was mixed with 1.48 ml of a n-hexane solution of 15% Me3Al. With the mixture being cooled in an ice-methanol bath, 0.25 ml (1.16 mmols) of 2-(2-aminoethyl)-1-methylpyrrolidine was added dropwise over about 2 minutes. After stirring for 20 minutes, the temperature was raised to room temperature, and 0.5 ml of a toluene solution of 0.2 g (1.16 mmols) of caprylic acid ethyl ester was added dropwise over 1 minute. After stirring for 2 hours at 70° C., the mixture was cooled with ice, and 10 ml of 1N NaOH was added dropwise. The mixture was stirred for 10 minutes, and water and ethyl acetate were added. Then, the mixture was separated into respective layers, and the organic layer was washed twice with 20 ml of a saturated aqueous solution of sodium chloride. After this layer was dried over anhydrous magnesium sulfate, it was concentrated under reduced pressure on a 30° C. water bath to obtain the captioned compound (yield 0.22 g). This compound was subjected to silica gel column chromatography (mobile phase: CHCl3:MeOH (19:1→9:1)) for purification. NMR and mass spectrum confirmed the purified compound to have the following structure: Toluene (1.0 ml), dried was mixed with 1.48 ml of a n-hexane solution of 15% Me3Al With the mixture being cooled in an ice-methanol bath After stirring for 2 hours at 70° C. was added dropwise The mixture was stirred for 10 minutes Then, the mixture was separated into respective layers the organic layer was washed twice with 20 ml of a saturated aqueous solution of sodium chloride After this layer was dried over anhydrous magnesium sulfate, it was concentrated under reduced pressure on a 30° C. water bath

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: Production of the spacer-gel derivative: Ethyl caprylate was converted into the corresponding hydrazide by hydrazinolysis, by initially admixing 10 ml. of this ethyl ester with 10 ml. of 98% hydrazine hydrate. Ethanol (22 ml.) was added as solvent, until the reaction mixture cleared, following which the solution was left at room temperature for 15 hours. The crystallized out resulting caprylhydrazide was filtered off and washed with ice water and then with aqueous methanol (1:1) of room temperature. The crystallized

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 2.1 g of sodium in 150 ml of absolute ethanol are added with stirring 15 g of p-(1-cyclooctenyl)-phenol. After stirring has continued for a further 30 minutes, 30 g of 2-bromo-octanoic acid ethyl ester are slowly added dropwise to this solution and the mixture is maintained at 50° C for 24 hours. After the solvent has been removed in vacuo the residue is partitioned at 0° C between ether and 2N sodium hydroxide solutuion. The organic phase is washed until neutral, dried over sodium sulphate and evaporated in vacuo, to thus yield the oily α-[p-cyclooctenyl)-phenoxy]-octanoic acid ethyl ester of the formula ##STR9## After the solvent has been removed in vacuo the residue is partitioned at 0° C between ether and 2N sodium hydroxide solutuion The organic phase is washed until neutral, dried over sodium sulphate evaporated in vacuo

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

Procedure: 2-4-Methoxy-phenylsulfanyl)-octanoic acid ethyl ester was prepared according to the general method as outlined in example 9. Starting from ethyl-2-bromooctanoate (11.8 g, 47.3 mmol) and 4-methoxythiophenol (6 g, 43 mmol). Yield: 7.24 g (57%); clear oil; MS: 311.2 (M+H)+, 2-4-Methoxy-benzenesulfonyl)-octanoic acid ethyl ester was prepared according to the general method as outlined in example 9. Starting from 2-(4-methoxy-phenylsulfanyl)-octanoic acid ethyl ester (4.0 g, 13.6 mmol). Yield 3.7 g (83%); clear oil; MS: 343.3 (M+H)+. 2-4-Methoxy-phenylsulfanyl)-octanoic acid ethyl ester was prepared

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

Procedure: Toluene (1.0 ml), dried using MS 4A, was mixed with 1.48 ml of a n-hexane solution of 15% Me3Al. With the mixture being cooled in an ice-methanol bath, 0.25 ml (1.16 mmols) of 2-(2-aminoethyl)-1-methylpyrrolidine was added dropwise over about 2 minutes. After stirring for 20 minutes, the temperature was raised to room temperature, and 0.5 ml of a toluene solution of 0.2 g (1.16 mmols) of caprylic acid ethyl ester was added dropwise over 1 minute. After stirring for 2 hours at 70° C., the mixture was cooled with ice, and 10 ml of 1N NaOH was added dropwise. The mixture was stirred for 10 minutes, and water and ethyl acetate were added. Then, the mixture was separated into respective layers, and the organic layer was washed twice with 20 ml of a saturated aqueous solution of sodium chloride. After this layer was dried over anhydrous magnesium sulfate, it was concentrated under reduced pressure on a 30° C. water bath to obtain the captioned compound (yield 0.22 g). This compound was subjected to silica gel column chromatography (mobile phase: CHCl3:MeOH (19:1→9:1)) for purification. NMR and mass spectrum confirmed the purified compound to have the following structure: Toluene (1.0 ml), dried was mixed with 1.48 ml of a n-hexane solution of 15% Me3Al With the mixture being cooled in an ice-methanol bath After stirring for 2 hours at 70° C. was added dropwise The mixture was stirred for 10 minutes Then, the mixture was separated into respective layers the organic layer was washed twice with 20 ml of a saturated aqueous solution of sodium chloride After this layer was dried over anhydrous magnesium sulfate, it was concentrated under reduced pressure on a 30° C. water bath