1,2-bis(2-chloroethoxy)ethane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Some 1,8-bis[(2-pyridyl)(phenyl)phosphino]-3,6-dioxaoctane was prepared substantially in the same way as the diphosphine of Example 2, except that instead of dichloromethane, 1,8-dichloro-3,6-dioxaoctane was employed.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: This compound is obtained by reacting 1,5-dimercapto-3-thiapentane with 1,8-dichloro-3,6-dioxaoctane in the presence of cesium carbonate in dimethylformamide (DMF): ##STR2## This compound is obtained

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: This compound is obtained by reacting 1,5-dimercapto-3-thiapentane with 1,8-dichloro-3,6-dioxaoctane in the presence of cesium carbonate in dimethylformamide (DMF): ##STR2## This compound is obtained

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: J. Gatto, et al. in "4,13-Diaza-18-Crown-6 (1,4,10,13-Tetraoxa-7,16-diazacyclooctadecane)," Organic Synthesis, Vol. 68, 1989, pp. 227-233, teach the preparation of the title compound by a three-step procedure that might be considered the standard preparation for these materials. First, benzylamine is reacted with 1,2-bis(2-chloroethoxy)ethane to produce 1,10-dibenzyl-4,7-dioxa-1,10-diazadecane. The product of the first step is then reacted in the presence of 1,2-bis(2-iodoethoxy)ethane, anhydrous sodium carbonate and sodium iodide in acetonitrile to give N,N'-dibenzyl-4,13-diaza-18-crown-6 in the second step. The phenyl groups of the second step product are then removed in a third, hydrogenation step over a palladium catalyst on a carbon support. the standard preparation for these materials

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: J. Gatto, et al. in "4,13-Diaza-18-Crown-6 (1,4,10,13-Tetraoxa-7,16-diazacyclooctadecane)," Organic Synthesis, Vol. 68, 1989, pp. 227-233, teach the preparation of the title compound by a three-step procedure that might be considered the standard preparation for these materials. First, benzylamine is reacted with 1,2-bis(2-chloroethoxy)ethane to produce 1,10-dibenzyl-4,7-dioxa-1,10-diazadecane. The product of the first step is then reacted in the presence of 1,2-bis(2-iodoethoxy)ethane, anhydrous sodium carbonate and sodium iodide in acetonitrile to give N,N'-dibenzyl-4,13-diaza-18-crown-6 in the second step. The phenyl groups of the second step product are then removed in a third, hydrogenation step over a palladium catalyst on a carbon support. the standard preparation for these materials

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 1,8-dichloro-3,6-dioxaoctane (40 g) and potassium hydroxide (11.8 g) in ethylene glycol (100 ml) was stirred at 100° C. for 18 h. The mixture was then cooled, filtered and the residue washed with acetone (2×35 ml). The combined filtrate was then distilled to yield the product as a clear oil (13.5 g, 30%), b.p. 120°-122° C./0.2 mm Hg; I.r. (liquid film) 3430 cm-1. The mixture was then cooled filtered the residue washed with acetone (2×35 ml) The combined filtrate was then distilled

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 1,8-dichloro-3,6-dioxaoctane (40 g) and potassium hydroxide (11.8 g) in ethylene glycol (100 ml) was stirred at 100° C. for 18 h. The mixture was then cooled, filtered and the residue washed with acetone (2×35 ml). The combined filtrate was then distilled to yield the product as a clear oil (13.5 g, 30%), b.p. 120°-122° C./0.2 mm Hg; I.r. (liquid film) 3430 cm-1. The mixture was then cooled filtered the residue washed with acetone (2×35 ml) The combined filtrate was then distilled

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 1,8-dichloro-3, 6-dioxaoctane (40 g) and potassium hydroxide (11.8 g) in ethylene glycol (100 ml) was stirred at 100° C. for 18 h. The mixture was then cooled, filtered and the residue washed with acetone (2×35 ml). The combined filtrate was then distilled to yield the product as a clear oil (13.5 g, 30%), b.p. 120°-122° C. /0.2 mm Hg; I.r. (liquid film) 3430 cm-1. The mixture was then cooled filtered the residue washed with acetone (2×35 ml) The combined filtrate was then distilled

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Some 1,8-bis[(2-pyridyl)(phenyl)phosphino]-3,6-dioxaoctane was prepared substantially in the same way as the diphosphine of Example 2, except that instead of dichloromethane, 1,8-dichloro-3,6-dioxaoctane was employed.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 1,8-dichloro-3, 6-dioxaoctane (40 g) and potassium hydroxide (11.8 g) in ethylene glycol (100 ml) was stirred at 100° C. for 18 h. The mixture was then cooled, filtered and the residue washed with acetone (2×35 ml). The combined filtrate was then distilled to yield the product as a clear oil (13.5 g, 30%), b.p. 120°-122° C./0.2 mm Hg; I.r. (liquid film) 3430 cm-1. The mixture was then cooled filtered the residue washed with acetone (2×35 ml) The combined filtrate was then distilled

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 500 mg (2.75 mmol) 4,5-dimethoxy-3-hydroxybenzaldehyde 1 and 860 μl (1.03 g, 5.50 mmol) 1,2-bis(2-chloroethoxy)ethane in 20 ml DMF was treated with 2.24 g (6.88 mmol) caesium carbonate and heated to 55° C. for 20 hrs. After cooling the mixture was poured into 100 ml of ice water and extracted with chloroform. The organic extracts were washed twice with 50 ml of water and with brine, dried over sodium sulfate and evaporated. The resulting yellow oil was flash-chromatographed (petroleum ether/ethyl acetate 2/1) to yield 3-{2-[2-(2-chloroethoxy)ethoxy]ethoxy}-4,5-dimethoxybenzaldehyde (730 mg, 2.20 mmol, 80%), which was directly used for the next synthesis step. After cooling the mixture extracted with chloroform The organic extracts were washed twice with 50 ml of water and with brine dried over sodium sulfate evaporated The resulting yellow oil was flash-chromatographed (petroleum ether/ethyl acetate 2/1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Some 1,8-bis[(2-pyridyl)(phenyl)phosphino]-3,6-dioxaoctane was prepared substantially in the same way as the diphosphine of Example 2, except that instead of dichloromethane, 1,8-dichloro-3,6-dioxaoctane was employed.