Preparation of grignard reagents of halodienes and preparation of dienols

Claim 1

A process for preparing a mixture of conjugated and allenic dienols which comprises the steps of: (1) adding (a) a solution of a 1- or 2-halo-1,3-hydrocarbyl diene in a diluent comprising an ether optionally with a hydrocarbon to (b) an ether dispersion of an effective amount and effective ratios of magnesium metal, a metal halide, and a saturated aliphatic halide promoter, under reaction conditions, thereby preparing a Grignard reagent of said 1- or 2-halo-1,3-hydrocarbyl diene, (2) contacting said Grignard reagent with an effective amount of a carbonyl compound which is an aldehyde or ketone, under reaction conditions, and (3) hydrolyzing the carbonyl-treated Grignard reagent from said step (2), thereby preparing said mixture of dienols, wherein when said ratio of said metal halide:said halo-1,3-hydrocarbyl diene is at least about 0.2:1 said mixture of dienols predominates in said conjugated dienol, and when said ratio of said metal halide:said halo-1,3-hydrocarbyl diene is less than about 0.2:1, said mixture of dienols predominates in said allenic dienol, wherein said ether in said diluent is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, dimethyl ether of ethylene glycol, dimethyl ether of diethylene glycol, diethyl ether of ethylene glycol, diethyl ether of diethylene glycol, alone, or in admixture, and wherein said metal salt is the chloride, bromide, or iodide of zinc, cadmium, mercury, or indium, said saturated aliphatic halide promoter is a saturated aliphatic chloride, bromide, or iodide, and wherein when said aliphatic halide promoter is said chloride, further employing iodine as a copromoter, and optionally otherwise, and wherein said 1-halo or 2-halo-1,3-hydrocarbyl diene is represented by the formula: ##STR5## wherein X is chlorine, bromine, iodine, and R is hydrogen or an alkyl radical of 1 to 4 carbon atoms per molecule.

Claim 26

A method for controlling the predominance of conjugated versus allenic dienols in a process of preparing dienols which comprises the steps of: (a) adding an ethereal solution of a 1- or 2-halo-1,3-hydrocarbyl diene to effective amounts and ratios of an ethereal dispersion of magnesium metal, a metal halide, and a saturated aliphatic halide promoter, under Grignard-forming conditions, employing a ratio of about 0.005:1 to 0.8:1 molar ratio of said metal halide:said 1- or 2-halo-1,3-hydrocarbyl diene, wherein said metal halide is the chloride, bromide, or iodide, of zinc, cadmium, mercury, or indium, said saturated aliphatic halide promoter is a chloride, bromide, or iodide, further with elemental iodine copromoter when said saturated aliphatic halide is the chloride, and optionally otherwise, and said ether is tetrahydrofuran, 1,4-dioxane, dimethyl ether of ethylene glycol, dimethyl ether of diethylene glycol, diethyl ether of ethylene glycol, diethyl ether of diethylene glycol, or mixture, thereby forming a Grignard reagent of said 1-halo- or 2-halo-1,3-hydrocarbyl diene, (b) reacting said Grignard reagent of said 1-halo- or 2-halo-1,3-hydrocarbyl diene with a carbonyl compound which is an aldehyde or ketone in an effective amount, under reaction conditions, and (c) hydrolyzing the reaction mixture from said step (b) under hydrolysis conditions, thereby preparing said dienols comprising a mixture of conjugated and allenic dienols, wherein said conjugated dienol predominates at a ratio of said metal halide:said 1- or 2-halo-1,3-hydrocarbyl diene above about 0.2:1, and wherein said allenic dienol predominates at a ratio of less than about 0.2:1, and wherein said 1-halo or 2-halo-1,3-hydrocarbyl diene is represented by the formula: ##STR6## wherein X is chlorine, bromine, or iodine, and R is hydrogen, or an alkyl radical containing 1 to 4 carbon atoms per molecule.

Claim 27

A method for controlling the predominance of conjugated versus allenic dienols in a process of preparing dienols which comprises the steps of: (a) adding an ethereal solution of a 1- or 2-halo-1,3-hydrocarbyl diene to effective amounts and ratios of an ethereal dispersion of magnesium metal, a metal halide, and a saturated aliphatic halide promoter, under Grignard-forming conditions, employing a ratio of about 0.005:1 to 0.8:1 molar ratio of said metal halide:said 1- or 2-halo-1,3-hydrocarbyl diene, wherein said metal halide is the chloride, bromide, or iodide, of zinc, cadmium, mercury, or indium, said saturated aliphatic halide promoter is a chloride, bromide, or iodide, further with elemental iodine copromoter when said saturated aliphatic halide is the chloride, and optionally otherwise, and said ether is tetrahydrofuran, 1,4-dioxane, dimethyl ether of ethylene glycol, dimethyl ether of diethylene glycol, diethyl ether of ethylene glycol, diethyl ether of diethylene glycol, or mixture, thereby forming a Grignard reagent of said 1-halo- or 2-halo-1,3-hydrocarbyl diene, (b) reacting said Grignard reagent of said 1-halo- or 2-halo-1,3-hydrocarbyl diene with a carbonyl compound which is an aldehyde or ketone in an effective amount, under reaction conditions, and (c) hydrolyzing the reaction mixture from said step (b) under hydrolysis conditions, thereby preparing said dienols comprising a mixture of conjugated and allenic dienols, wherein said conjugated dienol predominates at a ratio of said metal halide:said 1- or 2-halo-1,3-hydrocarbyl diene above about 0.2:1, and wherein said allenic dienol predominates at a ratio of less than about 0.2:1, and wherein said 1-halo or 2-halo-1,3-hydrocarbyl diene is represented by the formula: ##STR6## wherein X is chlorine, bromine, or iodine, and R is hydrogen, or an alkyl radical containing 1 to 4 carbon atoms per molecule.