2-(chloromethoxy)propane

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

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

Procedure: Using pyrogallol in place of phloroglucinol used in Synthesis Example 13 and isopropoxymethylchloride obtained in Synthesis Example 2, the reaction and treatment were carried out in the same manner as described in Synthesis Example 13 to give the corresponding 1,2,3-tris(isopropoxymethoxy)benzene as a yellow oil. obtained in Synthesis Example 2 the reaction and treatment as described in Synthesis Example 13

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

Procedure: Using pyrogallol in place of phloroglucinol used in Synthesis Example 13 and isopropoxymethylchloride obtained in Synthesis Example 2, the reaction and treatment were carried out in the same manner as described in Synthesis Example 13 to give the corresponding 1,2,3-tris(isopropoxymethoxy)benzene as a yellow oil. obtained in Synthesis Example 2 the reaction and treatment as described in Synthesis Example 13

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4.6 mL diisopropylamine in 40 mL of dry THF at −20° C. was added dropwise first 12.0 ml of 2.5 M butyllithium and then 8.1 ml of tributyltinhydride. After 10 min this solution was cooled to −78° C., and 3.25 g of chloromethyl isopropyl ether (Molina et al, 1982 Synthesis, 944) was added dropwise. After 10 min the cooling bath was removed and the reaction mixture was stirred at ambient temperature for 1.5 h. The mixture was poured onto water and extracted with hexanes and the extracts were dried over sodium sulfate and evaporated. The crude product was distilled (0.2 mm, 110-130° C.) to afford 7.8 g of tributyl (isopropoxymethyl)tin as a colorless liquid. After 10 min the cooling bath was removed The mixture was poured onto water extracted with hexanes the extracts were dried over sodium sulfate evaporated The crude product was distilled (0.2 mm, 110-130° C.)

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

Procedure: 13 g (0.24 mol) of butadiene are introduced at 10°-15° during the course of 11/2 hours and while stirring into a suspension of 0.8 g of newly melted zinc chloride in 21.7 g (0.2 mol) of chloromethyl-isopropylether. The mixture which has now turned yellow is stirred at 10° for 1 hour. After this period 20 cc of 10% sodium carbonate solution are added dropwise, 100 cc of benzene are added and the aqueous phase is separated in a separatory funnel. The benzene solution is washed with 10% sodium carbonate solution and subsequently with water, is dried with magnesium sulphate and evaporated at reduced pressure. The residue is distilled at 90 mm. B.P. of 1-chloro-5-isopropoxy-2-pentene: 110°-112°/90 mm. nD20 = 1.4408. the aqueous phase is separated in a separatory funnel The benzene solution is washed with 10% sodium carbonate solution and subsequently with water is dried with magnesium sulphate evaporated at reduced pressure The residue is distilled at 90 mm 110°-112°/90 mm

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

Procedure: 13 g (0.24 mol) of butadiene are introduced at 10°-15° during the course of 11/2 hours and while stirring into a suspension of 0.8 g of newly melted zinc chloride in 21.7 g (0.2 mol) of chloromethyl-isopropylether. The mixture which has now turned yellow is stirred at 10° for 1 hour. After this period 20 cc of 10% sodium carbonate solution are added dropwise, 100 cc of benzene are added and the aqueous phase is separated in a separatory funnel. The benzene solution is washed with 10% sodium carbonate solution and subsequently with water, is dried with magnesium sulphate and evaporated at reduced pressure. The residue is distilled at 90 mm. B.P. of 1-chloro-5-isopropoxy-2-pentene: 110°-112°/90 mm. nD20 = 1.4408. the aqueous phase is separated in a separatory funnel The benzene solution is washed with 10% sodium carbonate solution and subsequently with water is dried with magnesium sulphate evaporated at reduced pressure The residue is distilled at 90 mm 110°-112°/90 mm

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

Procedure: Using pyrogallol in place of phloroglucinol used in Synthesis Example 13 and isopropoxymethylchloride obtained in Synthesis Example 2, the reaction and treatment were carried out in the same manner as described in Synthesis Example 13 to give the corresponding 1,2,3-tris(isopropoxymethoxy)benzene as a yellow oil. obtained in Synthesis Example 2 the reaction and treatment as described in Synthesis Example 13

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

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

Procedure: A solution of 1,3-propanediol (19.4 g, 255 mmol) in dry tetrahydrofuran (100 ml) under nitrogen at 0°-5° C. was treated with sodium hydride (2.04 g, 85 mmol) and stirred for 1 hour. Chloromethylisopropyl ether (9 g, 83 mmol) in dry tetrahydrofuran (15 ml) was added over 15 min. Stirring was continued for a further 2 hours. The reaction mixture was filtered and the filtrate was evaporated in vacuo. The residue was purified by column chromatography on silica eluting with dichloromethane:methanol (97:4) to give the title compound as a colourless oil. (5.3 g, 44%). νmax (Film) 3400, 2910, 2860, 2805, 2760, 1460, 1440, 1425, 1410 and 1380 cm-1 ; δH (CDCl3) 1.17 (3H, s, CH3), 1.20 (3H, s,CH3), 1.84 (2H, quintet, J=6 Hz CH2CH2CH2), 2.3 (1H, br s, D2O exchangeable OH), 3.72 (2H, t, J=6 Hz, CH2OCH2OCH(CH3)2) 3.76 (2H, t, J=6 Hz,CH2ON), 3.86 (1H, m, CH(CH3)2), 4.70 (2H, s, OCH2O). Stirring was continued for a further 2 hours The reaction mixture was filtered the filtrate was evaporated in vacuo The residue was purified by column chromatography on silica eluting with dichloromethane:methanol (97:4)

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

Procedure: 13 g (0.24 mol) of butadiene are introduced at 10°-15° during the course of 1 1/2 hours and while stirring into a suspension of 0.8 g of newly melted zinc chloride in 21.7 g (0.2 mol) of chloromethyl-isopropylether. The mixture which has now turned yellow is stirred at 10° for 1 hour. After this period 20 cc of 10% sodium carbonate solution are added dropwise, 100 cc of benzene are added and the aqueous phase is separated in a separatory funnel. The benzene solution is washed with 10% sodium carbonate solution and subsequently with water, is dried with magnesium sulphate and evaporated at reduced pressure. The residue is distilled at 90 mm. B.P. of 1-chloro-5-isopropoxy-2-pentene: 110°-112°/90 mm. nD20 = 1.4408. the aqueous phase is separated in a separatory funnel The benzene solution is washed with 10% sodium carbonate solution and subsequently with water is dried with magnesium sulphate evaporated at reduced pressure The residue is distilled at 90 mm 110°-112°/90 mm

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4.6 mL diisopropylamine in 40 mL of dry THF at −20° C. was added dropwise first 12.0 ml of 2.5 M butyllithium and then 8.1 ml of tributyltinhydride. After 10 min this solution was cooled to −78° C., and 3.25 g of chloromethyl isopropyl ether (Molina et al, 1982 Synthesis, 944) was added dropwise. After 10 min the cooling bath was removed and the reaction mixture was stirred at ambient temperature for 1.5 h. The mixture was poured onto water and extracted with hexanes and the extracts were dried over sodium sulfate and evaporated. The crude product was distilled (0.2 mm, 110-130° C.) to afford 7.8 g of tributyl (isopropoxymethyl)tin as a colorless liquid. After 10 min the cooling bath was removed The mixture was poured onto water extracted with hexanes the extracts were dried over sodium sulfate evaporated The crude product was distilled (0.2 mm, 110-130° C.)

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

Procedure: 13 g (0.24 mol) of butadiene are introduced at 10°-15° during the course of 11/2 hours and while stirring into a suspension of 0.8 g of newly melted zinc chloride in 21.7 g (0.2 mol) of chloromethyl-isopropylether. The mixture which has now turned yellow is stirred at 10° for 1 hour. After this period 20 cc of 10% sodium carbonate solution are added dropwise, 100 cc of benzene are added and the aqueous phase is separated in a separatory funnel. The benzene solution is washed with 10% sodium carbonate solution and subsequently with water, is dried with magnesium sulphate and evaporated at reduced pressure. The residue is distilled at 90 mm. B.P. of 1-chloro-5-isopropoxy-2-pentene: 110°-112°/90 mm. nD20 = 1.4408. the aqueous phase is separated in a separatory funnel The benzene solution is washed with 10% sodium carbonate solution and subsequently with water is dried with magnesium sulphate evaporated at reduced pressure The residue is distilled at 90 mm 110°-112°/90 mm