Process for Preparing Alcohols

In a 500 ml volume round bottom flask dried and flushed with nitrogen, there were charged granular magnesium (18.2 g), dry zinc chloride (13.6 g) and dry tetrahydrofuran (110 g). Propargyl bromide (0.88 g) was added thereto at 10.degree. C while stirring. The resultant mixture was kept in an adiabatic condition, whereupon the reaction proceeded. When the heat generation stopped, a mixture of 5-methylfurfural (55.06 g), propargyl bromide (61.6 g) and xylene (100 g) was dropwise added to the reaction mixture at 40.degree. C in 1.5 hours while stirring under cooling. The resultant mixture was kept at room temperature for 30 minutes while stirring. After completion of the reaction, the thus obtained mixture and an aqueous solution (225 g) of 1.82 % acetic acid and 13.6 % sulfuric acid were simultaneiously poured into water (250 g) at a temperature of not lower than 30.degree. C and at a pH of not less than 4 in 20 minutes while stirring and then kept at room temperature for 30 minutes under stirring. Upon termination of the reaction, the mixture was separated, and an aqueous layer was removed. The oily layer was washed with the aqueous solution of 5 % sodium carbonate. The solvent was removed, and the residue was distilled under reduced pressure (73.degree.-75.degree. C./0.75 mmHg) to give 2-(1-hydroxy3-butynyl)-5-methylfuran (63.1 g) in a yield of 84 % (based on the starting 5-methylfurfural).

In the same flask as in Example 1, there were charged granular magnesium (18.2 g), dry zinc chloride (10.2 g) and dry tetrahydrofuran (110 g). Propargyl bromide (0.88 g) was added thereto at 10.degree. C while stirring. The resultant mixture was kept in an adiabatic condition, whereupon the reaction proceeded. When the heat generation stopped, a mixture of furfural (48.0 g), propargyl bromide (73.5 g) and toluene (110 g) was dropwise added to the reaction mixture at 30.degree. C in 3 hours while stirring under cooling. The resultant mixture was kept at room temperature for 30 minutes while stirring. After completion of the reaction, the reaction mixture was treated in the same manner as in Example 1 and distilled under reduced pressure (65.degree.-66.degree. C./ 0.45 mmHg) to give 2-(1-hydroxy-3-butynyl)-furan (61.3 g) in a yield of 90% (based on the starting furfural).

In the same flask as in Example 1, there were charged granular magnesium (14.6 g), dry zinc chloride (6.8 g) and dry tetrahydrofuran (110 g). Propargyl bromide (0.88 g) was added thereto at 10.degree. C. while stirring. The resultant mixture was kept in an adiabatic condition, whereupon the reaction proceeded. When the heat generation stopped, a mixture of 5-methylfurfural (55.06 g), propargyl bromide (64.5 g), tetrahydrofuran (55 g) and isopropyl ether (55 g) was dropwise added to the reaction mixture at 50.degree. C. in 1.5 hours while stirring under cooling. The resultant mixture was kept at room temperature for 30 minutes while stirring. After completion of the reaction, the reaction mixture was treated in the same manner as in Example 1 to give 2-(1-hydroxy-3-butynyl)-5-methylfuran (60.5 g) in a yield of 81% (based on the starting 5-methylfurfural).

In the same flask as in Example 1, there were charged granular magnesium (24.3 g), dry zinc bromide (16.9 g) and dry tetrahydrofuran (110 g). Propargyl chloride (0.55 g) was added thereto at 10.degree. C. while stirring. The resultant mixture was kept in an adiabatic condition, whereupon the reaction proceeded. When the heat generation stopped, a mixture of 5-methylfurfural (55.06 g), propargyl chloride (47.9 g) and tetrahydrofuran (110 g) was dropwise added to the reaction mixture at 35.degree. C. in 2 hours while stirring under cooling. The resultant mixture was kept at room temperature for 30 minutes while stirring. After completion of the reaction, the reaction mixture was treated in the same manner as in Example 1 to give 2-(1-hydroxy-3-butynyl)-5-methylfuran (60.3 g) in a yield of 81% (based on the starting 5-methylfurfural).

In the same flask as in Example 1, there were charged granular magnesium (18.2 g), dry zinc chloride (20.4 g) and dry tetrahydrofuran (220 g). Propargyl chloride (0.55 g) was added thereto at 10.degree. C. while stirring. The resultant mixture was kept in an adiabatic condition, whereupon the reaction proceeded. When the heat generation stopped, a mixture of 5-methylfurfural (55.06 g), propargyl chloride (38.6 g), propargyl bromide (11.9 g) and toluene (55 g) was dropwise added to the reaction mixture at 30.degree. C. in 6 hours while stirring under cooling. The resultant mixture was kept at room temperature for 30 minutes while stirring. After completion of the reaction, the reaction mixture was treated in the same manner as in Example 1 to give 2-(1-hydroxy-3-butynyl)-5-methylfuran (64.4 g) in a yield of 86% (based on the starting 5-methylfurfural).

In the same flask as in Example 1, there were charged granular magnesium (18.2 g), dry zinc chloride (10.2 g) and dry tetrahydrofuran (100 g). 3-Chloro-1-butyne (0.66 g) was added thereto at 10.degree. C. while stirring. The resultant mixture was kept in an adiabatic condition, whereupon the reaction proceeded. When the best generation stopped, a mixture of furfural (48 g), 3-chloro-1-butyne (45.88 g) and toluene (125 g) was dropwise added to the reaction mixture at 45.degree. C. in 1.5 hours while stirring under cooling. The resultant mixture was kept at room temperature for 30 minutes while stirring. After completion of the reaction, the reaction mixture was treated in the same manner as in Example 1 and distilled under reduced pressure (66.degree.-68.degree. C./1 mmHg) to give 2-(1-hydroxy-2-methyl-3-butynyl)-furan (63.8 g) in a yield of 84% (based on the starting furfural).

In the same manner as in Example 1 but under the conditions as specified in Table 1, there were produced the alcohols (I) or (I') shown in Table 1. Starting materials Reaction Carbonyl compound Zinc or temperature Alcohols (I) or (I') Example Mg (II) or oxirane Propargyl its and add- A mount No. (g) compound (III) halide halide Solvent ing time Structure (Yield) B.P. 7 18.2 ##STR9## CHCCH.sub.2 Br(74.3 g) ZnBr.sub.2(16.9 g) THF (100 g)Furan (125 g) 30.degree. C.;2 hrs ##STR10## 67.2 g(92%) 75-77.degree. C./0.4 mm Hg 8 21.9 CH.sub.3 (CH.sub.2).sub.3 CHO(43.1 g) CHCCH.sub.2 Br(74.3 g) ZnCl.sub.2(12.3 g) THF (240 g) 35.degree. C.;1.5 hrs ##STR11## 49.7 g(78%) 62-64.degree. C./10 mm Hg 9 18.2 ##STR12## CHCCH.sub.2 Br(74.3 g) ZnCl.sub.2(10.2 g) THF (300 g) 35.degree. C.;2 hrs ##STR13## 60.3 g(86%) 55-57.degree. C./10 mm Hg 10 18.2 ##STR14## CHCCH.sub.2 Br(74.3 g) ZnCl.sub.2(10.2 g) THF (100 g)Toluene(125 g) 30.degree. C.; 2 hrs ##STR15## 52.2 g(84%) 60-62.degree. C./9 mm Hg 11 18.2 H.sub.2 CCHCOCH.sub.3(35.1 g) CHCCH.sub.2 Br(74.3 g) ZnCl.sub.2(10.2 g) THF (225 g) 55.degree. C.;1 hr ##STR16## 39.8 g(70%) 43-46.degree. C./15 mm Hg 12 22.1 ##STR17## CHCCH.sub.2 Br(77.3 g) ZnCl.sub.2(12.2 g) THF (245 g) 35.degree. C.;1.5 hrs ##STR18## 60.6 g(78%) 65-69.degree. C./4 mm Hg 13 18.2 ##STR19## CHCCH.sub.2 Br(74.3 g) ZnCl.sub.2(10.2 g) THF (225 g) 40.degree. C.;0.5 hr ##STR20## 36.1 g(70%) 55-58.degree. C./15 mm Hg 14 36.5 ##STR21## CHCCH(CH.sub.3)Br(83.1 g) Zn(9.8 g) THF (300 g) 35.degree. C.;2 hrs ##STR22## 63.9 g(84%) 76-80.degree. C./0.9 mm Hg 15 18.2 ##STR23## CHCCH.sub.2 Br(11.0 g)CHCCH.sub.2 Cl(38.6 g) ZnCl.sub.2(10.2 g) THF (175 g)Isopropylether(50 g) 30.degree. C.;3 hrs ##STR24## 67.7 g(89%) 74-78.degree. C./0.6 mm Hg