2-(6-bromohexoxy)oxane

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

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

Procedure: The above procedure was repeated except that methyl cyclopent-3-ene carboxylate (prepared as described by A. H. Schmid and A. W. Wolkoff, J. Org. Chem. 32, 254 (1967)) was used with the 6-tetrahydropyranyloxyhexyl bromide of part D of this example and 1-(6-tetrahydropyranyloxyhexyl)-1-hydroxymethylcyclopent-3-ene was obtained as an oil (IR 3400, 3010 cm-1, nmr τ 4.4, 5.4, 6.35, 7.8, 8.5). prepared

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

Procedure: The above procedure was repeated except that methyl cyclopent-3-ene carboxylate (prepared as described by A. H. Schmid and A. W. Wolkoff, J. Org. Chem. 32, 254 (1967)) was used with the 6-tetrahydropyranyloxyhexyl bromide of part D of this example and 1-(6-tetrahydropyranyloxyhexyl)-1-hydroxymethylcyclopent-3-ene was obtained as an oil (IR 3400, 3010 cm-1, nmr τ 4.4, 5.4, 6.35, 7.8, 8.5). prepared

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

Procedure: 6-[(Tetrahydropyran-2-yl)oxy]-1bromohexane (2.0 g) is added, with a mild exotherm, to a stirred mixture of lithium acetylide ethylenediamine (4.9 g) at 20°-25°. The mixture is stirred overnight, then is poured into ice and aqueous ammonium chloride and extracted with ether/pentane. The extracts are dried over magnesium sulfate and concentrated to give the title compound, NMR (CDCl3) 1.3-2.5, 3.3-4.1 and 4.7 δ. extracted with ether/pentane The extracts are dried over magnesium sulfate concentrated

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

Procedure: 6-[(Tetrahydropyran-2-yl)oxy]-1bromohexane (2.0 g) is added, with a mild exotherm, to a stirred mixture of lithium acetylide ethylenediamine (4.9 g) at 20°-25°. The mixture is stirred overnight, then is poured into ice and aqueous ammonium chloride and extracted with ether/pentane. The extracts are dried over magnesium sulfate and concentrated to give the title compound, NMR (CDCl3) 1.3-2.5, 3.3-4.1 and 4.7 δ. extracted with ether/pentane The extracts are dried over magnesium sulfate concentrated

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

Procedure: 6-bromo-1-(tetrahydropyranyloxy)hexane was synthesized in the same manner as in Example 1 (the formula (26): step 1). First, 197.8 g (1.09 mol) of 6-bromo-1-hexanol were fed into a 500 mL reactor vessel and cooled to 5° C. or less, and then 102.1 g (1.21 mol) of dihydropyran were dripped at 10° C. or less. After completion of dripping, the mixture was warmed to room temperature and stirred for one hour. The obtained residues were subjected to silica gel column and purified using a mixed solvent of hexane/diisopropylether (IPE) (volume ratio 5:1) as an eluting solvent, and thus 263.4 g of 6-bromo-1-(tetrahydropyranyloxy)hexane were obtained. The yield in this case was 90.9%. cooled to 5° C. or less were dripped at 10° C. or less purified

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

Procedure: 6-bromo-1-(tetrahydropyranyloxy)hexane was synthesized in the same manner as in Example 1 (the formula (26): step 1). First, 197.8 g (1.09 mol) of 6-bromo-1-hexanol were fed into a 500 mL reactor vessel and cooled to 5° C. or less, and then 102.1 g (1.21 mol) of dihydropyran were dripped at 10° C. or less. After completion of dripping, the mixture was warmed to room temperature and stirred for one hour. The obtained residues were subjected to silica gel column and purified using a mixed solvent of hexane/diisopropylether (IPE) (volume ratio 5:1) as an eluting solvent, and thus 263.4 g of 6-bromo-1-(tetrahydropyranyloxy)hexane were obtained. The yield in this case was 90.9%. cooled to 5° C. or less were dripped at 10° C. or less purified

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

Procedure: First, 38.0 g (0.567 mol) of pyrrole and 200 mL of dehydrated tetrahydrofuran (THF) were fed into a 2 liter reactor vessel under a stream of argon gas and cooled to 5° C. or less. Then, 354 mL (0.567 mol) of 1.6M n-butyl lithium hexane solution were dripped into this mixture at 10° C. or less. After stirring for one hour at the same temperature, 600 ml of dimethylsulfoxide were further added, and THF was removed by distillation by heating for solvent substitution. Then, 165.2 g (0.623 mol) of 6-bromo-1-(tetrahydropyranyloxy)hexane were further dripped at room temperature. After dripping, the mixture was stirred for 2 hours at the same temperature. Then, 600 mol of water were added to the resultant reaction mixture to extract hexane and the organic layer was washed with water. Furthermore, after drying with anhydrous magnesium sulfate, the solvent was removed by distillation. The resultant residues were purified by silica gel column with hexane/ethyl acetate=4/1, and thus 107.0 g of N-[6-(tetrahydropyranyloxy)hexyl]pyrrole were obtained. The yield was 75.2%. Formula (27) below shows the reaction formula of the step 2. cooled to 5° C. or less were dripped into this mixture at 10° C. or less were further added THF was removed by distillation by heating for solvent substitution were further dripped at room temperature reaction mixture to extract hexane the organic layer was washed with water Furthermore, after drying with anhydrous magnesium sulfate the solvent was removed by distillation The resultant residues were purified by silica gel column with hexane/ethyl acetate=4/1

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

Procedure: First, 197.8 g (1.09 mol) of 6-bromo-1-hexanol were fed into a 500 mL reactor vessel and cooled to 5° C. or less, and further 102.1 g (1.21 mol) of dihydropyran were dripped at a temperature of 10° C. or less. After completion of dripping, the mixture was warmed to room temperature to carry out a reaction under stirring for one hour. Residues obtained by this reaction were purified by silica gel column with hexane/IPE (diisopropylether)=5/1, and thus 263.4 g of 6-bromo-1-(tetrahydropyranyloxy)hexane were obtained. The yield was 90.9%. Formula (26) below shows the reaction formula of the step 1. cooled to 5° C. or less were dripped at a temperature of 10° C. or less a reaction Residues obtained by this reaction were purified by silica gel column with hexane/IPE (diisopropylether)=5/1

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

Procedure: First, 197.8 g (1.09 mol) of 6-bromo-1-hexanol were fed into a 500 mL reactor vessel and cooled to 5° C. or less, and further 102.1 g (1.21 mol) of dihydropyran were dripped at a temperature of 10° C. or less. After completion of dripping, the mixture was warmed to room temperature to carry out a reaction under stirring for one hour. Residues obtained by this reaction were purified by silica gel column with hexane/IPE (diisopropylether)=5/1, and thus 263.4 g of 6-bromo-1-(tetrahydropyranyloxy)hexane were obtained. The yield was 90.9%. Formula (26) below shows the reaction formula of the step 1. cooled to 5° C. or less were dripped at a temperature of 10° C. or less a reaction Residues obtained by this reaction were purified by silica gel column with hexane/IPE (diisopropylether)=5/1

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Bromohexanol (54.67 g) is dissolved in TBME (250 mL) and dried over Na2SO4. After filtration, TsOH (0.6 mmol) is added and the solution is cooled in an ice bath. 3,4-Dihydropyran (394 mmol) is added dropwise, while maintaining the temperature around 2-3° C. After complete addition the reaction mixture is allowed to reach ambient temperature overnight. The mixture is ished with sat. NaHCO3 (2×200 mL). The aqueous layer is extracted with TBME (200 mL) and the combined organic layers are ished with brine (200 mL). After drying over Na2SO4 (containing some K2CO3), the solvent is evaporated to yield (XX) as a colourless oil (90%), which is stored at 4° C. over K2CO3 and is used without further purification. dried over Na2SO4 is added the solution is cooled in an ice bath After complete addition the reaction mixture The aqueous layer is extracted with TBME (200 mL) After drying over Na2SO4 ( containing some K2CO3), the solvent is evaporated

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

Procedure: To a solution of 6-bromo hexan-ol (F) (2 g, 11 mmol) in CH2Cl2 (50 ml) was added dropwise dihyrdopyran (1.6 ml, 16.5 mmol) followed by para-toluenesulphonic acid (commercially available) (0.075 g). The reaction mixture was stirred at room temperature for 16 h. The dark blue solution was then washed with water (2×25 ml) then saturated hydrogen carbonate solution (25 ml) and finally with a saturated sodium chloride solution (25 ml). The organic phase was then dried (MgSO4) and the solvent was evaporated under reduced pressure. The crude material was then purified through flash silica gel chromatography (hexane/EtOAc, 10:1) to afford compound 2-(6-Bromo-hexyloxy)-tetrahydropyran (G) as an oil (0.5 g, 70%). The dark blue solution was then washed with water (2×25 ml) The organic phase was then dried (MgSO4) the solvent was evaporated under reduced pressure The crude material was then purified through flash silica gel chromatography (hexane/EtOAc, 10:1)