Process for producing propargylcarbinol compounds
This application is a continuation of application Ser. No. 08/107,015, filed Aug. 17, 1993 abandoned; which in turn is a division of application Ser. No. 07/538,555, filed Jun. 15, 1990, now U.S. Pat. No. 5,258,529. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Industry 
     The present invention relates to a process for producing propargylcarbinols useful as intermediates for agrochemicals, pharmaceuticals, perfumes, resin monomers, and the like. 
     2. Description of Related Prior Art 
     Propargylcarbinols have been heretofore produced by a Grignard reaction of propargyl bromide or propargyl chloride and a ketone or aldehyde compound. 
     Since, however, propargyl bromide and propargyl chloride are detonable or capable of monopropellant-type burning, in view of safety, the inhibition of the detonability is required in the industrial bulk use thereof (Fire Technology, Vol. 5, p. 100, 1969, etc.). 
     Therefore, the above-mentioned process is not always an industrially advantageous one. 
     SUMMARY OF THE INVENTION 
     The present inventors have found a process for producing a propargylcarbinol by dehalogenation with a base through a haloallylcarbinol, derived from a ketone compound or an aldehyde compound and 2,3-dihalo-1-propene, without using propargyl bromide or propargyl chloride. 
     The present invention relates to a haloallylcarbinol-producing reaction (step 1) for producing a haloallylcarbinol compound of the formula (II) (sometimes referred to as haloallylcarbinol Compound II hereinafter) ##STR2## where R 1  and R 2  independently represent a hydrogen atom; a C 1  -C 15  alkyl group which may be substituted with at least one member selected from the group consisting of halogen atoms, a hydroxyl group, a phenyl group, an phenoxy group, a phenyl or phenoxy group substituted with at least one member selected from the group consisting of halogen atoms and hydroxyl, alkoxy, phenoxy, dialkylamino and methylenedioxy groups, and aralkyloxy group, a dialkylamino group, an alkylthio group, a phenylthio group, a biphenyl group and a phenylalkyl group; a C 2  -C 15  alkenyl group which may be substituted with at least one member selected from the group consisting of halogen atoms, a hydroxyl group, a phenyl group, a phenoxy group, a phenyl or phenoxy group substituted with at least one member selected from the group consisting of halogen atoms and hydroxyl, alkoxy, phenoxy, dialkylamino and methylenedioxy groups, a dialkylamino group, an alkylthio group, a phenylthio group, a biphenyl group and a phenylalkyl group; a C 2  -C 15  alkynyl group which may be substituted with at least one member selected from the group consisting of halogen atoms, a hydroxyl group, a phenyl group, a phenoxy group, a phenyl or phenoxy group substituted with at least one member selected from the group consisting of halogen atoms and hydroxyl, alkoxy, phenoxy, dialkylamino and methylenedioxy groups, a dialkylamino group, an alkylthio group, a phenylthio group, a biphenyl group and a phenylalkyl group; a C 3  -C 15  cycloalkyl group; a C 4  -C 15  cycloalkenyl group; or a phenyl, napthyl, furyl or thienyl group which may be substituted with at least one member selected from the group consisting of halogen atoms, and hydroxyl, alkyl, alkoxy, phenoxy, dialkylamino and methylenedioxy groups; or R 1  and R 2  together represent a C 2  -C 15  alkylene or alkenylene chain; and X 2  represents a chlorine, bromine or iodine atom, with proviso that the carbon atoms in the 1-positions of R 1  and R 2  do not together form tertiary carbon atoms and that when one of R 1  and R 2  is the furyl group, the other does not represent a hydrogen atom: which comprises reacting 
     a carbonyl compound of the formula (III) (referred to as Compound (III) hereinafter) ##STR3## where R 1  and R 2  are as defined above, with 
     a dihalopropene compound of the formula (IV) (referred to as Compound (IV) hereinafter) ##STR4## where X 1  and X 2  independently represent a chlorine, bromine or iodine atom in the presence of zinc and water. 
     Further, the present invention provides a process (step 2) for producing a propargylcarbinol compound (referred to as propargylcarbinol Compound (I) hereinafter) of the formula (I): ##STR5## where R 1  and R 2  are as defined above, which comprises reacting haloallylcarbinol Compound (II) obtained in the above step 1 with a base. 
     An object of the present invention is to provide a process, with safety and industrial advantage, for producing a propargylcarbinol compound useful as an intermediate for an agrochemical, pharmaceutical, perfume and resin monomer without using propargyl bromide or propargyl chloride. 
     PREFERRED EMBODIMENTS OF THE INVENTION 
     In the present invention, as preferred substituents R 1  and R 2 , each of R 1  and R 2  independently of the other represents a hydrogen atom, a C 1  -C 15  alkyl group which may be substituted with at least one member selected from the group consisting of halogen atoms and hydroxyl, phenyl, phenoxy, aralkyloxy, dialkylamino, alkylthio, phenylthio, biphenyl and phenylalkyl groups; a C 3  -C 9  cycloalkyl or cycloalkenyl group; a C 2  -C 9  alkenyl group which may be substituted with a phenyl group; a C 2  -C 6  alkynyl group; or a phenyl, napthyl, furyl or thienyl group which may be substituted with at least one member selected from the group consisting of halogen atoms and hydroxyl, alkyl, alkyloxy, phenoxy, dialkylamino and methylenedioxy groups. And, as more preferred substituents, each of R 1  and R 2  independently of the other represents a C 1  -C 15  alkyl group which may be substituted with a phenyl a C 2  -C 9  alkenyl group which may be substituted with a phenyl group; a C 5  -C 7  cycloalkyl or cycloalkenyl group; a phenyl, naphthyl or thienyl group which may be substituted with at least one member selected from the group consisting of halogen atoms, C 1  -C 3  alkyl, C 1  -C 3  alkoxy, phenoxy and methylenedioxy groups; or a hydrogen atom. 
     Each step of the present invention is detailed below. 
     Examples of Compound (III) used at the step 1 include C 1  -C 15  linear aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, propenal, butanal, pentanal, hexanal, heptanal, 6-heptynal, decanal, dodecanal, tetradecanal, hexadecanal, etc.; branched or cyclic aliphatic aldehydes such as 2-methylpropionaldehyde, 4-methyl-1-pentanal, 2-methyl-2-pentenal, citral, cyclohexanecarbaldehyde, etc.; halogen-substituted aliphatic aldehydes such as 2-chlorohexanal, 3-bromoheptanal, etc.; hydroxyl-substituted aliphatic aldehydes such as 3-hydroxybutanal, 6-hydroxyhexanal, etc.; aryl-containing aliphatic aldehydes such as phenylacetaldehyde, 2-phenylpropionaldehyde, biphenylacetaldehyde, cinnamic aldehyde, phenylpropynal, etc.; N,N-dialkylamino, alkylthio, arylthio, alkyloxy or aryloxy group-containing aliphatic aldehydes such as 2-(N,N-dimethylamino)-propionaldehyde, 4-(N,N-diethylamino)-1-butanal, 4-methylthio-1-butanal, 4-phenylthio-1-butanal, 6-methoxy-1-hexanal, benzyloxyacetaldehyde, 6-phenoxy-1-hexanal, etc.; aromatic aldehydes such as benzaldehyde, o-tolaldehyde, m-tolaldehyde, p-tolaldehyde, p-methoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, m-phenoxybenzaldehyde, p-chlorobenzaldehyde, o-bromobenzaldehyde, 2,4-dichlorobenzaldehyde, salicylaldehyde, 4-(N,N-dimethylamino)benzaldehyde, piperonal, etc.; thiophenecarbaldehydes such as 2-thiophenecarbaldehyde, 3-thiophenecarbaldehyde, etc.; linear, branched or cyclic alkyl, alkenyl or alkynyl-containing aliphatic ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl sec-butyl ketone, pinacolone, methyl pentyl ketone, methyl hexyl ketone, methyl heptyl ketone, methyl octyl ketone, methyl decyl ketone, methyl dodecyl ketone, methyl pentadexyl ketone, diethyl ketone, ethyl hexyl ketone, di-n-butyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, cyclopentenone, methyl vinyl ketone, methyl 2-methyl-1-propenyl ketone, ethyl 2-butynyl ketone, etc.; halogen-containing aliphatic ketones such as chloromethyl ethyl ketone, bromomethyl ethyl ketone, etc.; oxygen, sulfur or nitrogen-containing ketones such as methyl 2-hydroxyethyl ketone, methyl methoxymethyl ketone, methyl phenoxymethyl ketone, methyl methylthiomethyl ketone, methyl phenylthiomethyl ketone, methyl N,N-dimethylaminomethyl ketone, etc.; optionally substituted benzene ring-containing ketones such as acetophenone, methyl p-tolyl ketone, methyl 2,4-dimethylphenyl ketone, methyl m-methoxyphenyl ketone, methyl m-phenoxyphenyl ketone, methyl 2,4-dichlorophenyl ketone, methyl p-bromophenyl ketone, ethyl o-hydroxyphenyl ketone, methyl p-(N,N-dimethylamino)phenyl ketone, etc.; arylalkyl, arylalkenyl or arylalkynyl-containing ketones such as methyl benzyl ketone, methyl 2-phenylethyl ketone, benzalacetone, etc.; and thienyl or furyl-containing ketones such as 2-acetylthiophene, 2-acetylfuran, etc. 
     Of the above Compounds (III), the aldehydes are referred to as aldehyde Compound (III-1) and the ketones as ketone Compound (III-2) hereinafter. 
     Examples of Compound (IV) include 2,3-dichloro-1-propene, 2,3-dibromo-1-propene, 2,3diiodo-1-propene, 2-chloro-3-bromo-1-propene, 2-chloro-3-iodo-1-propene, 2-bromo-3-chloro-1-propene, 2-bromo-3-iodo-1-propene, 2-iodo-3-chloro-1-propene, and 2-iodo-3-bromo-1-propene. 
     Commercially available zinc in a variety of forms may be used as the zinc for the present reaction, and zinc in a powder or granular from is preferred. In particular, zinc in a powder form is more preferred. 
     The amount of the zinc to be used is 1 to 4 parts by mole, preferably 1.2 to 2 parts by mole, based on the aldehyde Compound (III-1) and 1 to 10 parts by mole, preferably 2 to 6 parts by mole, based on the ketone Compound (III-2). 
     The amount of water to be used is 1 to 24 parts by weight, preferably 2 to 9 parts by weight, based on Compound (III). 
     The amount of Compound (IV) to be used is usually 1 to 10 parts by mole based on the ketone Compound (III-2) and 1 to 4 parts by mole based on the aldehyde Compound (III-1). 
     The reaction of dehalogenation in the step 1 may be carried out in an organic solvent as required. Examples of such an organic solvent are diethyl ether, tetrahydrofuran, dioxane, toluene, benzene, monochlorobenzene, ethylene dichloride, chloroform, ethyl acetate, methanol, etc. 
     The amount of the organic solvent used is not specially limited. However, it is preferably not more than 5 parts by weight, more preferably not more than 3 parts by weight based on the water. 
     The reaction temperature is in a range of 0° to 100° C., preferably 20° to 60° C. 
     The reaction time is usually 1 to 24 hours. 
     In addition, the reaction time can be shortened by adding a small amount of an acid, such as acetic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, or the like. 
     Concerning the amount of the acid added in terms of a concentration in an aqueous solution thereof, when the aldehyde Compound (III-1) is used, the use of not more than 5% by weight of acetic acid or not more than 0.1% by weight of hydrochloric acid, hydrobromic acid, sulfuric acid or phosphoric acid is preferred. When the ketone Compound (III-2) is used, the use of not more than 20% by weight of acetic acid or not more than 1% by weight of hydrochloric acid, hydrobromic acid, sulfuric acid or phosphoric acid is preferred. 
     After the haloallylcarbinol Compound (II)-producing reaction is completed, the resultant mixture is treated in an ordinary manner, e.g. filtered, separated, concentrated or distilled, whereby the haloallylcarbinol Compound (II) can be obtained. 
     For step 2 for the production of the propargylcarbinol Compound (I) by dehydrohalogenation of the haloallylcarbinol Compound (II), a suitable combination of a base and a solvent is required. 
     Examples of the combination are: 
     (1) a polar aprotic solvent and an alkali metal hydroxide or alkali metal alkoxide, 
     (2) a solvent selected from the group consisting of a mixed solvent of a hydrophobic hydrocarbon with water, a mixed solvent of a hydrophobic halogenated hydrocarbon with water, and water, and an alkali metal hydroxide in the presence of a phase transfer catalyst, and 
     (3) an organic solvent and an alkali metal hydroxide or alkali metal alkoxide in the presence of a diamine. 
     Examples of the alkali metal hydroxide used in the reaction at the step 2 are sodium hydroxide, potassium hydroxide, etc. Examples of the alkali metal alkoxide are sodium methoxide, sodium ethoxide, potassium t-butoxide, etc. 
     Examples of the polar aprotic solvent used in the above combination (1) are acetonitrile, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, and hexamethylphosphoric acid triamide, etc. 
     Examples of the hydrophobic hydrocarbon and the hydrophobic halogenated hydrocarbon used in the above combination (2) are pentane, hexane, benzene, toluene, xylene, methylene chloride, chloroform, ethylene dichloride, and monochlorobenzene, etc. 
     Examples of the phase transfer catalyst are organic quaternary ammonium salts such as tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-pentylammonium bromide, tetra-n-pentylammonium iodide and benzyltriethylammonium chloride, and polyethylene glycols having a molecular weight of 200, 300, 600 or the like. 
     Examples of the organic solvent used in the above combination (3) are ethyl ether, tetrahydrofuran, dioxane, diglyme, triglyme, triethylamine, pyridine and such solvents as are specified concerning the combinations (1) and (2). 
     Examples of the diamine are ethylenediamine, N,N,N&#39;,N&#39;-tetramethylethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diazabicyclo[5,4,0]undec-7-ene, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,4-diazabicyclo-[2,2,2]octane. When ethylenediamine, 1,2-diaminopropane or 1,3-diaminopropane is used, the solvent is not necessarily required. 
     The amount of the base is usually 1 to 10 parts by mole, preferably 1 to 4 parts by mole, based on the haloallylcarbinol Compound (II). 
     The amount of the solvent other than water is not specially limited. However, it is usually 0.1 to 20 parts by weight based on the haloallylcarbinol Compound (II). 
     When water is used, its amount is usually 1 to 5 parts by weight based on the alkali metal hydroxide. 
     The amount of the phase transfer catalyst in the combination (2) is 0.5 to 10 parts by mole, preferably 0.5 to 5 parts by mole, based on the haloallylcarbinol Compound (II). 
     The amount of the diamine in the combination (3) is usually 1 to 20 parts by mole, preferably 1 to 15 parts by mole base don the haloallylcarbinol Compound (II). 
     The reaction temperature of the above step 2 is usually in a range of -20° to 100° C., preferably 0° to 60° C. 
     The reaction time is not specially limited, and the reaction can be quenched when the haloallylcarbinol Compound (II), a starting material, is not detected any longer. 
     After the reaction, the resultant mixture is treated, i.e. by filtering, addition of water, extraction, separation, concentration or distillation, whereby the propargylcarbinol Compound (I) can be obtained. 
     In the present invention, the formation of a by-product, an allene compound of the formula (V) which is an isomer of the propargylcarbinol Compound (I), is low, and the propargylcarbinol Compound (I) can be obtained highly selectively. ##STR6## 
     The propargylcarbinol Compound (I) obtained according to the above-detailed process is useful as a compound shown below or as an intermediate therefor. ##STR7## 
    
    
     The present invention is explained further in detail hereinbelow by reference to the Examples. 
     EXAMPLE 1 
     45.23 Grams of 2,3-dichloro-1-propene were added dropwise to a mixture of 20.00 g of cyclohexanone, 60 g of toluene, 60 g of water and 26.65 g of zinc powder at 35° C., and after the addition, the resultant mixture was maintained at the same temperature for 5 hours. After the reaction was completed, zinc-derived insolubles were filtered off, and the resultant filtrate was separated. The organic phase thereof was washed with a 7% sodium carbonate aqueous solution, and dried over magnesium sulfate. The desiccant was filtered off, and the resultant toluene solution was concentrated under reduced pressure to give 32.75 g of 1-(2&#39;-chloroallyl)-1-cyclohexanol; n D   20  =1.495, EI-MS m/e 156 (M-H 2  O + ), 158 (M-H 2  O+2 + ). 
     10.00 Grams of the 1-(2&#39;-chloroallyl)-1-cyclohexanol obtained above were dissolved in 94 g of N,N-dimethylformamide, and 9.65 g of potassium hydroxide in a flake form were added. The mixture was stirred at room temperature for 6 hours, and neutralized with a 20% acetic acid aqueous solution. The resultant mixture was subjected to extraction with toluene. The toluene phase was washed with water and dried over magnesium sulfate. The desiccant was filtered off and the toluene was distilled off under reduced pressure to give 7.68 g of 1-propargyl-1-cyclohexanol; m.p.=53°-54° C., FI-MS m/e 138(M + ) (Propargyl compound/allene compound=100.0/0.0), 
     bp 48°-49° C./1 mmHg FI-MS m/e 138 (M + ), 120 (M-H 2  O + ) IR (neat) 3440, 3320, 2120 cm -1 ,  1  H-NMR (CDCl 3 , internal standard TMS), δ 1.25-1.70 (m, 10H), 1.83 (2, 1H), 2.08 (t, 1H, J=2.6Hz), 2.36 (d, 2H, J=2.6Hz). 
     EXAMPLE 2 
     45.23 Grams of 2,3-dichloro-1-propene were added dropwise to a mixture of 20.00 g of methyl 2-methyl-1-propenyl ketone, 60 g of toluene, 60 g of water and 26.65 g of zinc powder at 35° C., and after the addition, the resultant mixture was maintained at the same temperature for 5 hours. After the reaction was completed, zinc-derived insolubles were filtered off, and the filtrate was separated. The organic phase was washed with 7% sodium carbonate aqueous solution and dried over magnesium sulfate. The desiccant was filtered off and the toluene was distilled off under reduced pressure. The resultant oily substance was purified by silica gel column chromatography to give 31.11 g of 2-chloro-4,6-dimethyl-1,5-heptadien-4-ol; n D   25  =1.474, FI-MS m/e 174(M), 176(M+2). 
     10.00 Grams of the 2-chloro-4,6-dimethyl-1,5-heptadien-4-ol obtained above were dissolved in 94 g of N,N-dimethylformamide, and 9.65 g of potassium hydroxide in a flake form were added. The resultant mixture was stirred at room temperature for 4 hours and neutralized with a 20% acetic acid aqueous solution, and the resultant mixture was subjected to extraction with toluene. The toluene phase was washed with water and then dried over magnesium sulfate. The desiccant was filtered off, and then the toluene was distilled off under reduced pressure. The resultant oily substance was purified by silica gel column chromatography to give 6.32 g of methyl 2-methylallylpropargylcarbinol; n D   25  =1.496, FI-MS m/e 138 (M + ) (Propargyl compound/allene compound=100.0/0.0). 
     EXAMPLE 3 
     33.26 of 2,3-dichloro-1-propene were added dropwise to a mixture of 20.00 g of acetophenone, 40 g of ethylene dichloride, 60 g of 5% acetic acid and 19.52 g of zinc powder at 50° C., and the resultant mixture was allowed to react at the same temperature for 10 hours. After the reaction was completed, zinc-derived insolubles were filtered off, and the resultant filtrate was separated. The organic phase was washed with 7% sodium carbonate aqueous solution and dried over magnesium sulfate. The desiccant was filtered off, and the ethylene dichloride was distilled off under reduced pressure. The resultant oily substance was purified by silica gel column chromatography to give 22.24 g of 2-chloro-4-phenyl-1-penten-4-ol; n D   25  =1.536, FI-MS m/e 178(M-H 2  O + ), 180 (M-H 2  O+2 + ). 
     20.00 Grams of the 2-chloro-4-phenyl-1-penten-4-ol were dissolved in 50 g of toluene, and 30.5 g of a 40% sodium hydroxide aqueous solution and 65.57 g of tetra-n-butylammonium bromide were added. The mixture was allowed to react at 50° C. for 30 hours and then was subjected to separation. The organic phase was washed with water, and the toluene was distilled off under reduced pressure. The resultant oily substance was purified by silica gel column chromatography to give 11.37 g of 4-phenyl-1-pentyn-4-ol; n D   21  =1.537 FI-MS m/e 160(M + ) (Propargyl compound/allene compound 100.0/0.0). 
     EXAMPLE 4 
     47.53 Grams of 2,3-dibromo-1-propene were added dropwise to a mixture of 15.00 g of 2-acetylthiophene, 30 g of toluene, 50 g of 0.01% hydrochloric acid and 15.55 g of zinc powder at 45° C., and the mixture was allowed to react at the same temperature for 9 hours. After the reaction was completed, zinc-derived insolubles were filtered off, and the resultant filtrate was subjected to separation. The organic phase was washed with a 7% sodium carbonate aqueous solution, and the toluene was distilled off under reduced pressure. The resultant oily substance was purified by silica gel column chromatography to give 15.55 g of α-(2-bromo-2-propenyl)-α-(2-thiophene)ethanol; n D   25  =1.539, FI-MS m/e 246(M), 248(M+2). 
     12.00 Grams of the α-(2-bromo-2-propenyl)-α-(2-thiophene)ethanol obtained above were dissolved in 108 g of N-methyl-2-pyrrolidone, and 6.30 g of sodium methylate were added. The mixture was allowed to react at 40° C. for 2 hours and then neutralized with concentrated hydrochloric acid, and insolubles were filtered off. An oily substance obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography to give 5.77 g of α-propargyl-α-(2-thiophene)ethanol; n D   25  =1.516, FI-MS m/e 166(M) (Propargyl compound/allene compound 100.0/0.0). 
     EXAMPLE 5 
     5.00 Grams of 2-iodoallylmethyl-α-naphthylcarbinol were dissolved in 50 g of dimethylformamide, and 1.18 g of sodium hydroxide in a flake form were added. The resultant mixture was stirred at room temperature for 8 hours. After the reaction was completed, the reaction mixture was neutralized with concentrated hydrochloric acid, insolubles were filtered off, and the remaining filtrate was concentrated under reduced pressure. The concentration residue was subjected to extraction with toluene, and washed with a 7% sodium carbonate aqueous solution. Then, the toluene was distilled off under reduced pressure to give 2.77 g of methyl-α-naphthylpropargylcarbinol; n D   25  =1.5141, FI-MS m/e 210 (M) (Propargyl compound/allene compound 100.0/0.0). 
     EXAMPLE 6 
     58.30 Grams of 2,3-dichloro-1-propene were added dropwise to a mixture of 30.00 g of heptanol, 90 g of toluene, 120 g of water and 34.35 g of zinc powder at 45° C., and then the resultant mixture was allowed to react at the same temperature for 10 hours. After the reaction finished, zinc-derived insolubles were filtered off, and the resultant filtrate was subjected to separation. The organic phase was washed with a 7% sodium carbonate aqueous solution and then dried over sodium sulfate. The desiccant was filtered off, and then the toluene was distilled off under reduced pressure to give 47.14 g of 2-chloroallyl-n-hexylcarbinol. The results were as follows. 
     Yield 94.1% bp 74°-75° C./0.7 mmHg n D   20  1.460 FI-MS m/e 190 (M + ), 192 (M+2 + ) IR (neat) 3370, 1640 cm -1 ,  1  H-NMR (CDCl 3 , internal standard TMS), δ 0.89 (m, 3H), 1.30-1.74 (m, 10H), 1.82 (brs, 1H), 2.38-2.52 (m, 2H), 3.93 (m, 1H), 5.25 (m, 1H), 5.28 (d, 1H, J=1.3Hz). 
     20.00 Grams of the 2-chloroallyl-n-hexylcarbinol obtained above were dissolved in 200 g of N,N-dimethylformamide, and 8.39 g of sodium hydroxide in a flake form were added. The resultant mixture was stirred at 25° C. for 10 hours. After the reaction was completed, the reaction mixture was neutralized with concentrated hydrochloric acid, and insolubles were filtered off. After the filtrate was concentrated under reduced pressure, the concentration residue was subjected to extraction with toluene, washed with a 7% sodium carbonate aqueous solution and then dried over sodium sulfate. The desiccant was filtered off, and the toluene was distilled off. The resultant oily substance was distilled under reduced pressure to give 15.70 g of n-hexylpropargylcarbinol. The results were as follows. 
     Yield 97.0% (propargyl compound/allene compound 98.0/2.0) bp 66.5°-68.5° C./0.8 mmHg n D   21  1.449 FI-MS m/e 154 (M + ), 136 (M-H 2  O + ) IR (neat) 3380, 3310, 2120 cm -1 ,  1  H-NMR (CDCl 3 , internal standard TMS), δ 0.89 (m, 3H), 1.29-1.56 (m, 10H), 2.06 (t, 1H, J=2.6Hz), 2.20 (d, 1H, J=4.9Hz), 2.27-2.47 (m, 2H), 3.75 (m, 1H). 
     EXAMPLE 7 
     125.40 Grams of 2,3-dichloro-1-propene were added dropwise to a mixture of 60.00 g of benzaldehyde, 180 g of toluene, 240 g of 5% acetic acid and 73.88 g of zinc powder at 45° C., and then the mixture was allowed to react at the same temperature of 3 hours. After the reaction was completed, zinc-derived insolubles were filtered off, and the resultant filtrate was subjected to separation. The organic phase was washed with a 7% sodium carbonate aqueous solution and dried over sodium sulfate. The desiccant was filtered off, and then the toluene was distilled off under reduced pressure to give 98.23 g of 2-chloroallylphenylcarbinol. The results were as follows. 
     Yield 95.2% bp 103°-104° C./2.5 mmHg n D   19  1.543 FI-MS m/e 182 (M + ), 184 (M+2 + ) IR (neat) 3390, 1640 cm -1 ,  1  H-NMR (CDCl 3 , internal standard TMS), δ 2.22 (brs, 1H), 2.60-2.80 (m, 2H), 5.00 (dd, 1H, J=8.9, 4.3Hz), 5.20 (d, 1H, J=1.0Hz), 5.26 (d, 1H, J=1.3Hz), 7.23-7.38 (m, 5H). 
     40.00 Grams of the 2-chloroallylphenylcarbinol obtained above were dissolved in 400 g of N,N-dimethylformamide, and 17.52 g of sodium hydroxide in a flake form were added. The mixture was stirred at 25° C. for 7 hours. After the reaction was completed, the reaction mixture was neutralized with concentrated hydrochloric acid, and insolubles were filtered off. The filtrate was concentrated under reduced pressure, and then the concentration residue was subjected to extraction with toluene, washed with a 7% sodium carbonate aqueous solution and dried over sodium sulfate. The desiccant was filtered off, and the toluene was distilled off under reduced pressure. The resultant oily substance was distilled under reduced pressure to give 30.84 g of phenylpropargylcarbinol. The results were as follows. 
     Yield 96.3% (propargyl compound/allene compound 93.2/6.8) bp 74°-76° C./0.5 mmHg n D   20  1.546 FI-MS m/e 146 (M + ), 128 (M-H 2  O + ) IR (neat) 3390, 3300, 2120 cm -1 ,  1  H-NMR (CDCl 3 , internal standard TMS), δ 2.06 (t, 1H, J=2.6Hz), 2.47 (d, 1H, J=3.6Hz), 2.63 (dd, 2H, J=6.3, 2.6Hz), 4.85 (m, 1H), 7.24-7.40 (m, 5H). 
     EXAMPLE 8 
     47.50 Grams of 2,3-dichloro-1-propene were added dropwise to a mixture of 20.00 g of crotonaldehyde, 40 g of ethylene dichloride, 60 g of 3% acetic acid and 18.65 g of zinc powder at 40° C., and the resultant mixture was allowed to react at the same temperature for 5 hours. After the reaction was completed, zinc-derived insolubles were filtered off and, the resultant filtrate was subjected to separation. The organic phase was washed with a 7% sodium carbonate aqueous solution and dried over magnesium sulfate. The desiccant was filtered off, and the ethylene dichloride was distilled off under reduced pressure to give 37.15 g of 2-chloro-1,5-heptadien-4-ol; n D   25  =1.471, FI-MS m/e 146(M + ), 148(M+2 + ). 
     20.00 Grams of the 2-chloro-1,5-heptadien-4-ol obtained above were dissolved in 50 g of toluene, and 40.9 g of a 40% sodium hydroxide aqueous solution and 87.94 g of tetra-n-butylammonium bromide were added. The resultant mixture was allowed to react at 50° C. for 24 hours and then separated, and the organic phase was washed with water. The toluene was distilled off under reduced pressure. The resultant oily substance was purified by silica gel column chromatography to give 10.72 g of hept-5-en-1-yn-4-ol; n D   25  =1.493, FI-MS m/e 110(M + ), propargyl compound/allene compound 94.0/6.0. 
     EXAMPLE 9 
     49.93 Grams of 2,3-dibromo-1-propene were added dropwise to a mixture of 20.00 g of phenylacetaldehyde, 40 g of toluene, 60 g of 0.01% hydrochloric acid and 16.33 g of zinc powder at 30° C., and the mixture was allowed to react at the same temperature for 3 hours. After the reaction was completed, zinc-derived insolubles were filtered off, and the resultant filtrate was separated. The organic phase was washed with a 7% sodium carbonate aqueous solution, and the toluene was distilled off under reduced pressure. The resultant oily substance was purified by silica gel column chromatography to give 24.01 g of 2-bromo-5-phenyl-1-penten-4-ol; n D   25  =1.536, FI-MS m/e 240(M + ), 242(M+2 + ). 
     20.00 Grams of the 2-bromo-5-phenyl-1-penten-4-ol obtained above were dissolved in 160 g of N-methyl-2-pyrrolidone, and 11.20 g of sodium methylate were added. The mixture was allowed to react at 30° C. for 14 hours and then was neutralized with concentrated hydrochloric acid. Insolubles were filtered off, and the filtrate was concentrated under reduced pressure. The resultant oily substance was purified by silica gel column chromatography to give 9.96 g of 5-phenyl-1-pentyn-4-ol, n D   25  =1.519, FI-MS m/e 160(M + ), propargyl compound/allene compound 97.9/2.1. 
     EXAMPLE 10 
     19.5 Grams of 2-chloroallylphenylcarbinol were dissolved in 100.0 g of 1,3-diaminopropane, and 9.2 g of sodium methylate were added. The mixture was allowed to react at 30° C. for 16 hours. Then, the reaction mixture was neutralized with concentrated hydrochloric acid, and insolubles were filtered off. The filtrate was concentrated under reduced pressure, and the resultant oily substance was purified by silica gel column chromatography to give 12.6 g of phenylpropargylcarbinol, n D   20  =1.546, FI-MS m/e 146(M + ), propargyl compound/allene compound=93.0/7.0. 
     EXAMPLE 11 
     5.00 Grams of 2-iodoallyl-α-naphthylcarbinol were dissolved in 50 g of dimethylformamide, and 1.23 g of sodium hydroxide in a flake form were added. The mixture was stirred at room temperature for 6 hours. After the reaction was completed, the reaction mixture was neutralized with concentrated hydrochloric acid, insolubles were filtered off, and the filtrate was concentrated under reduced pressure. The concentration residue was subjected to extraction with toluene and washed with a 7% sodium carbonate aqueous solution, and then the toluene was distilled off under reduced pressure to give 2.78 g of α-naphthylpropargylcarbinol; n D   25  =1.549, FI-MS m/e 196(M + ). 
     EXAMPLES 12-34 
     Propargylcarbinol compounds (I) were produced from haloallylcarbinol compounds (II) shown in Table 1 according to conditions described in Example 11. The results are shown in Table 1. 
     
         TABLE 1
  Haloallylcarbinol Base Solvent Reaction Reaction Propargylcarbinol (I)
 Ex-  Amount  Amount  Amount tempera- time  Yield Propargyl compound/
 ample Name (g) Name (g) Name (g) ture (°C.) (hr) Name (%) allene
 compound n.sub.D MS
   12 2-Chloroallyl- 30.00 NaOH 12.11 Ethylene- 121.28 25 8.5 Isopropylpro
 paragyl- 94.9 97.7/2.3 1.447 FI-MS  isopropylcarbinol    diamine
 carbinol   (20° C.) 112 (M.sup.+) 13 n-Butyl-2-chloro- 15.00 &#34;
 7.36 Dimethyl- 150 40 4 n-Butylpropargyl- 95.9  87.5/12.5 1.447 FI-MS
 allylcarbinol    formamide    carbinol   (24° C.) 126 (M.sup.+)
 14 2-Chloroallyl-n- &#34; &#34; 6.80 Dimethyl- &#34; &#34; &#34; n-Pentylpropargyl- 96.6
 87.6/12.4 1.449 FI-MS  pentylcarbinol    formamide    carbinol
 (24° C.) 140 (M.sup.+) 15 2-Chloroallyl-n- 10.00 KOH 8.81
 Dimethyl- 100 25 6 n-Hexylpropargyl- 94.9 90.6/9.4  hexylcarbinol
 formamide    carbinol 16 2-Chloroallyl- 20.00 NaOH 8.48 Dimethyl- 200 &#34;
 10 Cyclohexylpropargyl- 99.0 99.5/0.5 1.486 FI-MS  cyclohexylcarbinol
 formamide    carbinol   (20° C.) 152 (M.sup.+) 17 10-Chloro-2,6-
 &#34; &#34; 6.99 Dimethyl- &#34; &#34; &#34; 2,6-Dimethylundeca- &#34; Unknown 1.488 FI-MS
 dimethyl-2,6,10-    formamide    2,6-dien-10-yn-8-ol   (21° C.)
 192 (M.sup.+)  undecatrien-8-ol 18 5-Chloro-2-phenyl-5- &#34; &#34; 7.59
 Dimethyl- &#34; 20 8 2-Phenyl-5-hexyn-3- 93.3 100.0/0.0
   mp FD-MS  hexen-3-ol    formamide    ol   64° C. 174 (M.sup.+)
 19 trans-5-Chloro-1- 24.43 &#34; 9.37 Dimethyl- 244.3 25 &#34; trans-1-Phenyl-hex
 a- 92.9 98.2/1.8 1.573 FD-MS  phenyl-1,5-hexadien-    formamide
 1-en-5-yn-3-ol   (21°
  C.) 172 (M.sup.+)  3-ol 20 2-Chloroallylphenyl- 40.00 NaOH 17.52
 Dimethyl- 400 25 7 Phenylpropargyl- 96.3 93.2/6.8  carbinol    formamide
    carbinol 21 2-Chloroallyl-p- 15.00 &#34; 6.12 Dimethyl- 150 40 4 Propargyl
 -p- 93.9
  83.9/16.1 1.543 FD-MS  tolylcarbinol    formamide    tolylcarbinol
 (24° C.) 160 (M.sup.+) 22 2-Chloroallyl-p- &#34; &#34; 5.64 Dimethyl- &#34; &#34;
 &#34; p-Methoxyphenyl- 98.3  84.2/15.8 1.553 FD-MS  methoxyphenylcarbinol
 formamide    propargylcarbinol   (24° C.) 176 (M.sup.+) 23
 2&#39;-Chloroallyl-3,4- 23.00 &#34; 8.12 Dimethyl- 230 25 10 3,4-Methylenedioxy-
 97.0 91.6/8.4 1.565 FD-MS  methylenedioxyphenyl-    formamide
 phenylpropargyl-   (21° C.) 190 (M.sup.+)  carbinol
 carbinol 24 2&#39;-Chloroallyl-3,4- &#34; &#34; &#34; Dimethyl- &#34; 40 4 3,4-Methylenedioxy
 - 96.5
  85.2/14.8  methylenedioxyphenyl-    formamide    phenylpropargyl-
 carbinol        carbinol 25 2-Chloroallyl-p- &#34; &#34; 8.47 Dimethyl- &#34; 25 10
 p-Chlorophenyl- 99.5 92.1/7.9 1.557 FI-MS  chlorophenylcarbinol
 formamide    propargylcarbinol   (21° C.) 180 (M.sup.+)
    182 (M +
  2.sup.+) 26 2-Chloroallyl-p- &#34; &#34; &#34; Dimethyl- &#34; 40 3 p-Chlorophenyl-
 95.1  86.1/13.9  chlorophenylcarbinol    formamide    propargylcarbinol
  27 2&#39;-Chloroallyl-2,4- 15.00 &#34; 4.76 Dimethyl- 150 25 12 2,4-Dichlorophen
 yl- 92.9 90.6/9.4 mp FD-MS  dichlorophenyl-    formamide    propargylcarb
 inol   44.5-45.5° C. 214 (M.sup.+)  carbinol            216 (M +
 2.sup.+)              218 (M + 4.sup.+) 28 2&#39;-Chloroallyl-2- 20.00 &#34;
 8.48 Dimethyl- 200 &#34; &#34; Propargyl-2- 90.4 91.0/9.0 1.559 FI-MS  thienylcar
 binol    formamide    thienylcarbinol   (20° C.) 152 (M.sup.+) 29
 1-(2&#39;-Chloroallyl)- 20.00 NaOH 8.57 Dimethyl- 200 25 10 1-Propargylcyclo-
  92.9 100.0/0.0
    cyclohexan-1-ol    formamide    hexan-1-ol 30 2-Chloro-4-methyl-1- &#34;
 &#34; 9.06 Dimethyl- &#34; &#34; 12 4-Methyl-1-octyn-4- 91.4 &#34; 1.446 FI-MS  octen-4-o
 l    formamide    ol   (21°
  C.) 140 (M.sup.+) 31 5-Chloro-3-methyl-1- &#34; &#34; 7.12 Dimethyl- &#34; &#34; &#34;
 3-Methyl-1-phenyl-5- 98.8 &#34; 1.525 FD-MS  phenyl-5-hexen-3-ol    formamide
     hexyn-3-ol   (20° C.) 188 (M.sup.+) 32 5-Chloro-3-methyl-1-
 18.49 &#34; 6.64 Dimethyl- 184.9 &#34; &#34; 3-Methyl-1-phenyl- 97.7 &#34; 1.567 FD-MS
 phenyl-1,5-hexadien-    formamide    hexan-1-en-5-yn-3-ol   (21°
 C.) 186 (M.sup.+)  3-ol 33 4-Chloro-2-phenyl-4- 20.00 &#34; 8.14 Dimethyl-
 200 &#34; 5 2-Phenyl-4-pentyn-2- 96.0 &#34; 1.537 FI-MS  penten-2-ol    formamide
     ol   (21° C.) 160 (M.sup.+) 34 5-(2&#39;-Chloroallyl)- 17.50 &#34;
 6.40 Dimethyl- 175 &#34; 12 5-Propargylnonan-5- 96.6 &#34; 1.452 FI-MS  nonan-5-o
 l    formamide    ol   (21°
  C.) 182 (M.sup.+)
 
    
     EXAMPLE 35 
     58.30 Grams of 2,3-dichloro-1-propene were added dropwise to a mixture of 30.00 g of heptanal, 90 g of toluene, 120 g of 5% acetic acid and 34.35 g of zinc powder at 45° C., and then the mixture was allowed to react at the same temperature for 3 hours. After the reaction was completed, zinc-derived insolubles were filtered off, and the resultant filtrate was subjected to separation. The organic phase was washed with a 7% sodium carbonate aqueous solution and dried over sodium sulfate. The desiccant was filtered off, and then the toluene was distilled off under reduced pressure to give 46.31 g of 2-chloroallyl-n-hexylcarbinol. The yield thereof was 92.4%. 
     EXAMPLE 36 
     40.00 Grams of 2-chloroallylphenylcarbinol were dissolved in 400 g of dimethylformamide, and 36.85 g of potassium hydroxide in a flake form were added. The mixture was stirred at room temperature for 2 hours and then neutralized with a 20% acetic acid aqueous solution. The resultant mixture was subjected to extraction with toluene. The toluene phase was washed with water and then dried over magnesium sulfate. The desiccant was filtered off, and the toluene was distilled off under reduced pressure to give 31.35 g of phenylpropargylcarbinol, n D   20  =1.546, FI-MS m/e 146 (M + ), propargyl compound/allene compound=92.3/7.7. 
     EXAMPLES 37-52 
     Haloallylcarbinol compounds (II) were produced from aldehyde compounds (III-1) shown in Table 2 according to conditions described in Example 7. The results are shown in Table 2. 
     
         TABLE 2
    Reaction Re-  Aldehyde (III-1)  tempera- action Haloallylcarbinol
 (II) Ex-  Amount Organic ture time  Yield mp bp     ample Name (g)
 solvent (°C.) (hr) Name (%) (°C.) (°C.) n.sub.D MS
 IR .sup.1
  H-NMR (CDC13, internal standard TMS)                             37
 Acetaldehyde 30.00 Ethyl 32 3 2-Chloro- 97.6  42 1.459 FI-MS neat
 δ 1.25(d, 3H, J=7.1Hz), 1.91(brs, 1H), 2.39-2.54    ether
 allylmethyl-   (5 mm (25° C.) 120 (M.sup.+) 3370 cm.sup.-1 (m,
 2H), 4.15(m, 1H), 5.24(m, 1H), 5.27(d, 1H,       carbinol   Hg)  122 (M
 + 2.sup.+) 1640 cm.sup.-1 J=1.3Hz) 38 Propion- &#34; Ethyl &#34; &#34; 2-Chloro-
 98.0  54 1.457 FI-MS neat δ 0.98(t, 3H, J=7.1Hz), 1.45-1.61(m,
 2H), 1.82  aldehyde  ether   allylethyl-   (5 mm (25° C.) 134
 (M.sup.+) 3380 cm.sup.-1 (brs, 1H), 2.39-2.53(m, 2H), 3.82-3.91(m, 1H),
      carbinol   Hg)  136 (M + 2.sup.+) 1640 cm.sup.-1 5.25(m, 1H),
 5.27(d, 1H, J=1.3Hz) 39 2-Methyl- &#34; Ethyl &#34; &#34; 2-Chloro- 99.7  38-40
 1.459 FI-MS neat δ 0.96(d, 6H, J=6.9Hz), 1.68-1.80(m, 2H), 2.36-
 propion-  ether   allylisopro-   (5 mm (20° C.) 148 (M.sup.+)
 3420 cm.sup.-1 2.53(m, 2H), 3.72(ddd, 1H, J=8.9, 5.3, 3.6Hz),  aldehyde
    pylcarbinol   Hg)  150 (M + 2.sup.+) 1640 cm.sup.-1 5.26(dt, 1H,
 J=1.3, 0.7Hz), 5.29(d, 1H, J=1.3Hz) 40 Pentanal &#34; Toluene 35 1.5
 Butyl-2- 98.9  55-57 1.459 FD-MS neat δ 0.93(t, 3H, J=7.0Hz),
 1.29-1.54(m, 6H), 1.74       chloroallyl-   (3 mm (25° C.) 163 (M
 + H.sup.+) 3380 cm.sup.-1 (brs, 1H), 2.34-2.52(m, 2H), 3.93(m, 1H),
 5.25(m,       carbinol   Hg)  165 (M + H + 2.sup.+) 1640 cm.sup.-1 1H),
 5.27(d, 1H, J=1.3Hz) 41 Hexanal &#34; &#34; &#34; 2 2-Chloro- 99.0  66 1.459 FD-MS
 neat δ 0.89(m, 3H), 1.25-1.50(m, 8H), 1.76(brs, 1H),
 allylpentyl-   (3 mm (25° C.) 177 (M + H.sup.+) 3380 cm.sup.-1
 2.36-2.55(m, 2H), 3.92(m, 1H), 5.24(m, 1H), 5.29       carbinol   Hg)
 179 (M + H + 2.sup.+) 1640 cm.sup.-1 (d, 1H, J=1.3Hz) 42 Cyclohexane- &#34;
 &#34; 45 3 2-Chloro- 95.7  72-75 1.490 FI-MS 188 neat δ 0.99-1.45(m,
 6H), 1.67-1.85(m, 6H), 2.37-2.55  carbaldehyde     allylcyclo-   (0.5 mm
 (19° C.) (M.sup.+), 190 3400 cm.sup.-1 (m, 2H), 3.71(dt, 1H,
 J=3.6, 9.1Hz), 5.25(m, 1H),       hexylcarbinol   Hg)  (M + 2.sup.+ )
 1635 cm.sup.-1 5.29(d, 1H, J=1.3Hz)            170 (M - H.sub.2 O.sup.+)
            172 (M - H.sub.2 O +            2.sup.+) 43 Citral 30.00
 Toluene 45 3 2-Chloro- 95.7  117-119 1.4919 FD-MS neat δ
  1.60-1.75(m, 10H), 1.98-2.20(m, 4H), 2.38-2.47       allyl   (0.8 mm
 (21° C.) 228 (M.sup.+) 3370 cm.sup.-1 (m, 1H), 2.52-2.63(m, 1H),
 4.72(m, 1H), 5.05-5.21       2&#39;,6&#39;-di-   Hg)  230 (M + 2.sup.+) 1640
 cm.sup.-1 (m, 2H), 5.23(m, 1H), 5.26(d, 1H, J=1.0Hz)       methyl-1&#39;,5&#39;-
       heptadienyl-       carbinol 44 2-Phenyl- &#34; &#34; &#34; &#34; 2-Chloro- 94.9
 48-56   FD-MS KBr δ
  1.36(d, 3H, J= 6.9Hz), 1.84(brs, 1H), 2.28-2.40  propional-
 allyl-1&#39;-     210 (M.sup.+) method (m, 2H), 2.80(quint, 1H, J=6.9Hz),
 4.03(ddd, 1H,  dehyde     phenylethyl-     212 3420 cm.sup.-1 J=7.6,
 6.6, 5.0Hz), 5.20(d, 1H, J=0.7Hz),       carbinol     (M + 2.sup.+) 1640
 cm.sup.-1 5.25(d, 1H, J=1.3Hz), 7.19-7.35(m, 5H) 45 Cinnamic &#34; &#34; &#34; &#34;
 2-Chloro- 74.2  132-134 1.5761 FD-MS neat δ 2.10(brs, 1H),
 2.55-2.70(m, 2H), 4.63(m, 1H),  aldehyde     allylstyryl-   (0.8 mm
 (19° C.) 208 (M.sup.+) 3400 cm.sup.-1 5.27(m, 1H), 5.30(d, 1H,
 J=1.3Hz), 6.21(dd, 1H,       carbinol   Hg)  210 (M + 2.sup.+) 1640
 cm.sup.-1 J=15.8, 6.6Hz), 6.65(dd, 1H, J=15.8, 1.0Hz),
 7.18-7.57(m, 5H) 46 p-Tolalde- &#34; &#34; 35 &#34; 2-Chloro- 98.2  96-98 1.5338
 FD-MS neat δ 2.21(brs, 1H), 2.33(s, 3H), 2.56-2.77(m, 2H),  hyde
   allyl-p-   (0.5 mm (25° C.) 196 (M.sup.+) 3400 cm.sup.-1
 4.95(dd, 1H, J=9.0, 4.9Hz), 5.19(m, 1H), 5.24(d,       tolylcarbinol
 Hg)  198 (M + 2.sup.+) 1640 cm.sup.-1 1H, J=1.3Hz), 7.11-7.23(m, 4H) 47
 p-Methoxy- &#34; &#34; &#34; &#34; 2-Chloro- 96.0  122-123 1.5455 FD-MS neat δ
 1.97(brs, 1H), 2.59-2.81(m, 2H), 3.80(s, 3H),  benzaldehyde     allyl-p-
   (0.6 mm (25° C.) 212 (M.sup.+) 3430 cm.sup.-1 4.98 dd, 1H,
 J=8.7, 5.2Hz), 5.20(m, 1H), 5.26(d,       methoxy-   Hg)  214 (M +
 2.sup.+) 1640 cm.sup.-1 1H, J=1.3Hz), 6.88(m, 2H), 7.28(m, 2H)
 phenyl       carbinol 48 Piperonal &#34; &#34; 45 &#34; 2-Chloro- 93.7 56-57   FD-MS
 KBr δ 2.11(d, 1H, J= 2.6Hz), 2.57-2.79(m, 2H),       allyl-
 226 (M.sup.+) method 4.94(m, 1H), 5.22(m, 1H), 5.27(d, 1H, J=1.3Hz),
   3&#39;,4&#39;-methyl-     228 3380 cm.sup.-1 5.95(s, 2H), 6.75-6.89(m, 3H)
   enedioxy-     (M + 2.sup.+) 1640 cm.sup.-1       phenyl-
 carbinol 49 p-Chloro- 30.00 Toluene 45 3 2-Chloro- 95.0 48-50   FD-MS
 KBr δ 2.28(d, 1H, J=3.3Hz), 2.57-2.77(m, 2H),  benzaldehyde
 allyl-     216 (M.sup.+) method 4.99(m, 1H), 5.20(m, 1H), 5.27(d, 1H,
 J=1.3Hz),       p-chloro-     218 (M + 2.sup.+) 3390 cm.sup.-1 7.31(s,
 4H)       phenyl-     220 (M + 4.sup.+) 1635 cm.sup.-1       carbinol 50
 2,4- &#34; &#34; 35 &#34; 2-Chloro- 93.6 41   FD-MS KBr δ 2.34(s, 1H),
 2.44-2.56(m, 2H), 5.29(m, 1H),  Dichloro-     allyl-     250 (M.sup.+)
 method 5.33(d, 1H, J=1.3Hz), 5.43(m, 1H), 7.08-7.27  benzaldehyde
 2&#39;, 4&#39;-di-     252 (M +
  2.sup.+) 3420 cm.sup.-1 (m, 3H)       chlorophenyl-     254 (M +
 4.sup.+) 1635 cm.sup.-1       carbinol 51 m-Phenoxy- &#34; &#34; 45 &#34; 2-Chloro-
 96.4  169-170 1.5804 FD-MS neat δ 2.17(brs, 1H), 2.60-2.78(m, 2H),
 4.99(dd, 1H,  benzaldehyde     allyl-   (0.6 mm (25°
  C.) 274(M.sup.+) 3410 cm.sup.-1 J=8.6, 4.6Hz), 5.21(m, 1H), 5.28(d, 1H,
 J=       m-phenoxy-   Hg)  276 (M + 2.sup.+) 1635 cm.sup.-1 1.0Hz),
 6.89-7.37(m, 9H)       phenyl-       carbinol 52 2-Thiophene- &#34;  &#34; &#34; &#34;
 2-Chloro- 92.1  84-86 1.5585 FI-MS neat δ 2.39(d, 1H, J=3.3Hz),
 2.73-2.92(m, 2H), 5.25-  carbaldehyde     allyl-2&#39;-   (0.9 (19°
 C.) 170 (M - H.sub.2 O.sup.+) 3390 cm.sup.-1 5.31(m, 3H), 6.98(m, 2H),
 7.25(dd, 1H, J=5.0,        thienyl-   mmHg)  172 (M - 1640 cm.sup.-1
 1.3Hz)       carbinol     H.sub.2 O +
  2.sup.+)
 
    
     EXAMPLE 53 
     56.53 Grams of 2,3-dichloro-1-propene were added dropwise to a mixture of 25.00 g of cyclohexanone, 75 g of toluene, 100 g of 5% acetic acid and 34.35 g of zinc powder at 45° C., and then the mixture was allowed to react at the same temperature for 3 hours. After the reaction was completed, zinc-derived insolubles were filtered off, and the resultant filtrate was subjected to separation. The organic phase was washed with a 7% sodium carbonate aqueous solution and dried over sodium sulfate. The desiccant was filtered off, and then the toluene was distilled off under reduced pressure to give 44.05 g of 1-(2&#39;-chloroallyl)-1-cyclohexanol. The results were as follows. 
     Yield 99.0% bp 62°-65° C./0.5 mmHg n D   20  1.4950 FI-MS m/e 156 (M-H 2  O + ), 158 (M-H 2  O+2 + ) IR (neat) 3460, 1630 cm -1 ,  1  H-NMR (CDCl 3 , internal standard TMS), δ 1.26-1.71 (m, 10H), 1.82 (s, 1H), 2.54 (s, 2H), 5.21 (d, 1H, J=0.8Hz), 5.34 (d, 1H, J=0.8Hz). 
     EXAMPLES 54-65 
     Haloallylcarbinol compounds (II) were produced from ketone compounds (III-2) shown in Table 3 according to the conditions described in Example 53. The results are shown in Table 3. 
     
                                           TABLE 3                                 
__________________________________________________________________________
                         Acetic acid                                      
                                  Amount of  Re-  Re-                     
                         Con-     2,3-di-                                 
                                        Amount                            
                                             action                       
                                                  actio                   
Ketone (III-2) Organic solvent                                            
                         centra-  chloro-1-                               
                                        of   tempera-                     
                                                  n                       
Ex-       Amount    Amount                                                
                         tion                                             
                             Amount                                       
                                  propene                                 
                                        zinc ture time                    
ample                                                                     
    Name  (g)  Name (g)  (%) (g)  (g)   (g)  (°C.)                 
                                                  (hr)                    
__________________________________________________________________________
54  Methyl n-                                                             
          10.00                                                           
               Toluene                                                    
                    30   5   40   22.15 13.05                             
                                             45   5.5                     
    butyl                                                                 
    ketone                                                                
55   &#34;    &#34;    None  0   &#34;   &#34;    &#34;     &#34;    &#34;    3                       
56   &#34;    &#34;     &#34;   &#34;    10  &#34;    33.23 19.58                             
                                             &#34;    &#34;                       
57  Methyl 2-                                                             
          20.00                                                           
               Toluene                                                    
                    60   5    80  29.96 17.65                             
                                             45   5                       
    phenyl-                                                               
    ethyl                                                                 
    ketone                                                                
58  Methyl 2-                                                             
          20.00                                                           
               Toluene                                                    
                    60   5    80  59.92 35.30                             
                                             45   2                       
    phenyl-                                                               
    ethyl                                                                 
    ketone                                                                
59   &#34;    &#34;     &#34;   &#34;    &#34;   &#34;    89.88 52.95                             
                                             &#34;    &#34;                       
60  Benzal-                                                               
          30.00                                                           
                &#34;   90   &#34;   120  45.54 26.83                             
                                             &#34;    &#34;                       
    acetone                                                               
61   &#34;    &#34;     &#34;   &#34;    &#34;   &#34;    136.62                                  
                                        80.49                             
                                             &#34;    &#34;                       
62  Aceto-                                                                
          30.00                                                           
               Toluene                                                    
                    90    5  120  55.42 32.65                             
                                             45   2                       
    phenone                                                               
63   &#34;    &#34;     &#34;   &#34;    &#34;   &#34;    110.84                                  
                                        65.30                             
                                             &#34;    &#34;                       
64   &#34;    &#34;     &#34;   &#34;    &#34;   &#34;    166.26                                  
                                        97.95                             
                                             &#34;    &#34;                       
65  di-n-Butyl                                                            
          &#34;    None  0   10  &#34;    210.65                                  
                                        124.11                            
                                             &#34;    &#34;                       
    ketone                                                                
__________________________________________________________________________
tertiary Haloallylcarbinol (II)                                           
                                          .sup.1 H-NMR                    
      Yield mp bp                         (CDCl.sub.3, internal           
Name  (%)   (°C.)                                                  
               (°C.)                                               
                    n.sub.D                                               
                         Ms         IR    standard TMS)                   
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2-Chloro-                                                                 
      52.2     54-56                                                      
                    1.461                                                 
                         FI-MS      neat  δ 0.92 (m, 3H), 1.25 (s,  
4-methyl-      (5 mm                                                      
                    (20°C.)                                        
                         177(M + H.sup.+)                                 
                                    3450 cm.sup.-1                        
                                          3H), 1.32-1.57 (m, 6H),         
1-octen-4-     Hg)       179(M + H + 2.sup.+)                             
                                    1630 cm.sup.-1                        
                                          1.86 (brs, 1H), 2.54 (m,        
ol                       158(M - H.sub.2 O.sup.+)                         
                                          2H), 5.22 (d, 1H,               
                         160(M - H.sub.2 O + 2.sup.+)                     
                                          J = 1.0Hz), 5.35 (d, 1H,        
                                          J = 1.0Hz)                      
 &#34;    77.3                                                                
 &#34;    94.0                                                                
5-Chloro-                                                                 
      29.9     126- 1.530                                                 
                         FI-MS      neat  δ 1.33 (s, 3H),           
                                          1.82-1.88                       
3-methyl-      128  (21° C.)                                       
                         206(M - H.sub.2 O.sup.+)                         
                                    3470 cm.sup.-1                        
                                          (m, 3H), 2.61 (d, 2H,           
1-phenyl-      (0.9      208(M - H.sub.2 O + 2.sup.+)                     
                                    1640 cm.sup.-1                        
                                          J = 4.0Hz), 2.70-2.79 (m,       
5-hexen-3-     mmHg)                      2H), 5.24 (m, 1H), 5.37         
ol                                        (d, 1H, J = 1.3Hz), 7.15-       
                                          7.32 (m, 5H)                    
5-Chloro-                                                                 
      59.5                                                                
3-methyl-                                                                 
1-phenyl-                                                                 
5-hexen                                                                   
3-ol                                                                      
 &#34;    93.1                                                                
5-Chloro-3-                                                               
      27.1          1.5648                                                
                         FD-MS      neat  δ 1.46 (s, 3H), 1.68 (s,  
methyl-1-           (19° C.)                                       
                         222(M.sup.+)                                     
                                    3440 cm.sup.-1                        
                                          1H), 2.70 (s, 2H), 5.25         
phenyl-1,5-              224(M + 2.sup.+)                                 
                                    1630 cm.sup.-1                        
                                          (d, 1H, J = 1.0Hz);             
hexadien-3-                               5.35 (d, 1H J =                 
ol                                        1.0Hz), 6.33 (d, 1H,            
                                          J = 15.8Hz), 6.65               
                                          (d, 1H, J = 15.8Hz),            
                                          7.09-7.43 (m,5H)                
 &#34;    78.8                                                                
4-Chloro-                                                                 
      42.4     84-85                                                      
                    1.5395                                                
                         FI-MS      neat  δ 1.64 (s, 3H), 2.37      
                                          (brs,                           
2-phenyl       (0.5 (20° C.)                                       
                         178(M - H.sub.2 O.sup.+)                         
                                    3460 cm.sup.-1                        
                                          1H), 2.82 (d, 1H,               
4-phenten-     mm Hg)    180(M - H.sub.2 O + 2.sup.+)                     
                                    1635 cm.sup.-1                        
                                          J = 14.7Hz), 2.91 (d, 1H,       
2-ol                                      J = 14.7Hz), 5.07 (d,1H,        
                                          1.3Hz), 5.27 (d, 1H, J =        
                                          1.3Hz), 7.22-7.47 (m, 5H)       
 &#34;    71.5                                                                
 &#34;    93.7                                                                
5-(2&#39;-                                                                    
      59.2     77-79                                                      
                    1.4613                                                
                         FI-MS      neat  δ 0.91 (m, 6H), 1.32 (m,  
chloro-        (0.5 (19° C.)                                       
                         200(M - H.sub.2 O.sup.+)                         
                                    3480 cm.sup.-1                        
                                          8H), 1.51 (m, 4H), 1.78         
allyl)-        mm Hg)    202(M- H.sub.2 O + 2.sup.+)                      
                                    1630 cm.sup.-1                        
                                          (s, 1H), 2.53 (s, 2H),          
nonan-5-ol                                5.21 (d, 1H, J = 1.0Hz),        
                                          5.34 (d, 1H, J                  
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                                          = 1.0Hz)