CN104341255A - Preparation method of unsaturated alcohol - Google Patents
Preparation method of unsaturated alcohol Download PDFInfo
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Abstract
The invention provides a preparation method of unsaturated alcohol. The preparation method comprises the following steps: uniformly mixing unsaturated halogenated hydrocarbon, water, a catalyst and a non-polar organic solvent, adding an alkaline solution, adjusting the pH value to be 5-8, reacting at 20-150 DEG C, and purifying to obtain unsaturated alcohol. The method provided by the invention is simple in process, mild in condition, relatively less in three-waste emission, high in yield, and convenient in purification and separation of products.
Description
Technical field
The invention belongs to the synthesis field of organic molecule alcohol, be specifically related to a kind of preparation method of unsaturated alcohol.
Background technology
Unsaturated alcohol is the organism containing unsaturated link(age) and hydroxyl in a kind of structure, unsaturated link(age) in its structure and hydroxyl have very high chemical reactivity, can be polymerized, esterification, etherificate, replacement, oxidation, the chemical reaction process such as reduction, in fields such as pharmaceutical industries, fragrance industry and surfactant industry, there is widespread use.
The method of current synthesis unsaturated alcohol has a lot, mainly comprises the methods such as esterification saponification method, grignard reagent method, direct hydrolysis method, prins condensation method, oxidation reduction process.
Chinese patent application CN103242139A adopts esterification saponification method method, with methallyl chloride, carboxylate salt for raw material, take water as solvent, under the effect of 100-160 DEG C of condition and phase-transfer catalyst, prepares esterification intermediate; Esterification intermediate saponification in the alkaline aqueous solution of 10-80 DEG C of then will prepare, obtains methallyl alcohol after purifying.
Chinese patent application CN 102850186A adopts grignard reagent method method; with methallyl chloride, formaldehyde for raw material; under protection of inert gas and under being less than 40 DEG C of conditions; first methallyl chloride is prepared into grignard reagent, then reaction system is warming up to 40-70 DEG C, add formaldehyde wherein; there is grignard reaction; prepare the form intermediate that carbon atom number increases by, through the step such as quencher, purification, obtain 3-methyl-3-butene-1-alcohol.
U.S. Patent application US2072016 adopts direct hydrolysis method method, with batch reactor or tubular reactor for reaction unit, under 80-250 DEG C of condition, hydrochloric ether is direct hydrolysis in alkaline aqueous solution or alkaline suspension liquid, obtains corresponding alcohol through separating-purifying.
The advantage of above esterification saponification method, grignard reagent method and direct hydrolysis method avoids High Temperature High Pressure operation in reaction process, reduces the scale of investment of equipment and general facilities; But the output of its waste water, waste residue etc. is higher, therefore improve corresponding environmental protection and processing cost.
Chinese patent application CN103333048A adopts Prins condensation method, with iso-butylene, formaldehyde for raw material, has the γ-Al of metal phosphate with load
2o
3for catalyzer, by packed catalyst in calandria type fixed bed reactor, under the 200-300 DEG C of condition with 8-10MPa, the mixture of iso-butylene and formaldehyde continues through tubular reactor with certain speed, through steps such as separating-purifyings, obtain 3-methyl-3-butene-1-alcohol.
Chinese patent application CN103755523A adopts oxidation reduction process, take iso-butylene as raw material; The first step is 320-380 DEG C in temperature of reaction, and iso-butylene catalyzed oxidation is methacrylaldehyde; Second step is under 60-90 DEG C and 0.4-1MPa condition, and methacrylaldehyde intermediate, by Chemoselective reduction, generates 2-methallyl alcohol, after the steps such as separating-purifying, obtains 2-methallyl alcohol.
The advantage of above Prins condensation method and oxidation reduction process is that reaction process cleans, and unreacted product can recycle, and three waste discharge is few; But its reaction process needs High Temperature High Pressure, add the investment of equipment and general facilities.
Summary of the invention
Goal of the invention: in order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of reaction conditions gentleness, three waste discharge is less, productive rate is high, the synthetic method of the unsaturated alcohol of purification of products convenient separation.
Technical scheme: the preparation method of a kind of unsaturated alcohol provided by the invention, comprises the following steps: after the mixing of unsaturated halohydrocarbon, water, catalyzer and non-polar organic solvent, add basic solution and adjust pH to 5-8, react at 20-150 DEG C, purifying, to obtain final product.
Preferably, described purification step, is specially: static, question response system layering, and upper strata is organic phase, and lower floor is aqueous phase; Organic phase comprises non-polar solvent, halohydrocarbon and unsaturated alcohol; Lower floor's aqueous phase comprises water, catalyzer and metal halide; Rectifying organic phase, obtains unsaturated alcohol; After filtering aqueous phase, reuse as reaction soln.
Unsaturated halohydrocarbon, water, catalyzer and non-polar organic solvent add in reactor with certain proportion by the method, under certain temperature and pressure, in reaction system, add basic solution gradually, control reaction system and maintain near a stable pH, until reacted.
After having reacted, stratification, shunting upper organic phase comprises non-polar solvent, halohydrocarbon and target alcohol, and after rectifying separation, obtain target alcohol, reaction solvent and unreacted halohydrocarbon are recycled as reaction raw materials; Lower floor's aqueous phase is the aqueous solution containing catalyzer and metal halide, when not having metal halide to separate out, this solution can directly reuse, when there being metal halide to separate out, solution after filtration recycles and reuses again, can use after the metal halide purification of filtering as chemical; Every secondary response terminates rear aqueous phase need supplement the water that halohydrocarbon hydrolysising loss falls, the catalytic efficiency of catalyzer visual response system and determining, when speed of reaction reduces, and suitable make-up catalyst.
The temperature of reaction of the method is between 20-150 DEG C, and pressure is normal pressure or high pressure.Basic solution and unsaturated halohydrocarbon equimolar amount that the method uses measures, by the pH of reaction system change adjust basic solution add speed.When reaction system pH no longer changes, be then considered as reaction and complete.So the reaction times of reaction system is fixed with the titration time of basic solution.The mensuration of pH value, adopts the pH value of the mode assaying reaction system of digital display pH meter insertion reaction still.
The reactor that the method uses is generally reactor, the pH of assaying reaction system time on the one hand at one's leisure, the phase on the other hand in reactor is the reaction between liquid-liquid diphase, uses reactor that reaction mass can be made to reach complete mixing flow, make fully to mix between reaction mass, improve speed of reaction.Certain the present invention can adopt tubular reactor equally or change material reaction phase is liquid phase reaction or gas-phase reaction, and these immobilized modes needing simply to change the kind of material, proportioning and catalyzer just can realize.Consider that in the present invention, the boiling point of part material is higher, the resistance toheat of catalyzer has certain temperature limitation, so tend to adopt churned mechanically closed reactor as reactor.
As preferably, the amount ratio of described catalyzer and unsaturated halohydrocarbon is (0.2-10) g:1mol; The volume ratio of described water, non-polar organic solvent and unsaturated halohydrocarbon is (1-5): (1-5): 1.If the aqueous solution after halohydrocarbon hydrolysis is recycled, then need the problem considering make-up catalyst and the moisture because of halohydrocarbon hydrolysising loss.If the catalytic efficiency of the catalyzer in the aqueous solution reduces, according to the 20-100% make-up catalyst of raw catalyst usage quantity, reach former catalytic levels with the catalytic efficiency of catalyzer and be as the criterion; The hydrolysis of each halohydrocarbon terminates rear needs and supplements water lose because participating in halohydrocarbon hydrolysis, generally and mole moisturizing such as halohydrocarbon.
Preferred as another kind, described catalyzer comprises one or more in phase-transfer catalyst and metal halide, described phase-transfer catalyst comprises triethylamine, methyl trioctylphosphine brometo de amonio, triethyl methyl brometo de amonio, tributyl-methyl phosphonium brometo de amonio, tetrabutylammonium chloride, Tetrabutyl amonium bromide, etamon chloride, phenyltrimethylammonium bromide, phenyl trimethicone ammonium chloride, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium Neutral ammonium fluoride, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride, cetyltriethylammonium bromide, octadecyl trimethyl ammonium chloride, myristyl trimonium brometo de amonio, Sodium dodecylbenzene sulfonate, the structural formula of described metal halide is M
xl
y, wherein M represents transition metal, comprises Fe, Co, Ni, Sn, Cu, Ag, Au, Pa, L represents haloid element, comprises F, Cl, Br, I, the numeral of x and y representative is subscript, is determined by the valency of metallic element and haloid element.
Preferred as another kind, described unsaturated halohydrocarbon may contain in the groups such as linear alkyl groups, branched alkyl group, group of naphthene base, aromatic group, heterocyclic group one or several, its carbon atom number is that 3-20 is individual.
As preferred further, described unsaturated halohydrocarbon comprises vinylchlorid, chlorallylene, 1-chlorine-2-methyl-1-propylene, methallyl chloride, allyl bromide 98, the bromo-2-methyl-1-propylene of 1-, methacrylic bromine, 1,3,2-CMB, bromo-3 methyl-2-butenes of 1-, the chloro-1-butylene of 3-, 3, 3-dimethyl-allyl bromine, allyl iodide, the chloro-1-cyclopentenes of 1-, 2-(chloromethyl) allyl group-trimethyl silane, 2-chloroacrylonitrile, 2-bromopropylene nitrile, methacrylic iodine, the chloro-1-hexene of 6-, the bromo-1-octene of 8-, the bromo-1-decene of 10-, the chloro-1-undecylene of 11-, the bromo-1-undecylene of 11-, cinnamyl chloride, the bromo-1-phenyl of 3--1-propylene, 4-1-chloro-4-methyl-benzene.
Preferred as another kind, described non-polar organic solvent is poorly water-soluble, there is very strong acid-proof alkaline and its stability by the solvent of temperature and pressure variable effect, comprise Skellysolve A, normal hexane, hexanaphthene, normal heptane, octane-iso, sherwood oil, toluene, dimethylbenzene, biphenyl.This kind of non-polar organic solvent and aqueous phase layering, reactant from non-polar solvent mutually enter aqueous phase and participate in hydrolysis reaction, hydrolysate is extracted into non-polar solvent phase gradually from aqueous phase, thus the pre-separation of hydrolysate and aqueous phase in a kettle..In addition, halohydrocarbon and the side reaction probability of occurrence of hydrolysate in aqueous phase can also be reduced.
Preferred as another kind, the aqueous suspension of described basic solution both can be the aqueous solution of alkaline matter also can be alkaline matter, comprise sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, Quilonum Retard, lithium hydroxide, sodium hydroxide, potassium hydroxide, aluminium hydroxide, calcium hydroxide, magnesium hydroxide, calcium hydroxide, hydrated barta, calcium carbonate, Calcium hydrogen carbonate, barium carbonate, calcium oxide, magnesium oxide, barium oxide, aluminium sesquioxide, the metal oxides such as ferric oxide, the aqueous solution of one or more mixtures in metal hydroxides or metal carbonate.
Beneficial effect: preparation method's technique of unsaturated alcohol provided by the invention is simple, mild condition, three waste discharge are less, productive rate is high, purification of products convenient separation.
Specifically, relative to prior art, there is following outstanding advantage:
The first, hydrolysising condition is gentle, does not need high-temperature high-voltage reaction condition;
The second, basic solution adds as required, does not need the transformation efficiency in order to improve halohydrocarbon and significantly improves the consumption of alkaline matter;
3rd, adopt non-polar organic solvent as extraction agent, the product after halohydrocarbon catalytic hydrolysis is extracted into organic layer rapidly, thus reduces the probability of occurrence of side reaction; Meanwhile, organic extraction layer is easy to be separated with aqueous layer, simplifies separating step, reduces separating-purifying energy consumption;
4th, the aqueous solution can be cycled to repeat utilization.The catalyzer of the aqueous solution still has catalytic performance on the one hand, can suitably supplement if catalytic performance declines and catalyzer need not be added at every turn in a large number, the metal halide salt generated in the aqueous solution on the other hand has the performance promoting halohydrocarbon solubleness in water, thus improves the catalytic hydrolysis efficiency of halohydrocarbon.Metal halide salt in the aqueous solution does not need deliberately to remove, and the solubleness once it reaches capacity in water, can separate out from the aqueous solution, only needs simple filtration step to remove metal halide salt.
Embodiment
Embodiment 1
Unsaturated halohydrocarbon is chlorallylene; Alkaline matter is sodium hydroxide, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is Tetrabutyl amonium bromide, and consumption is the unsaturated halohydrocarbon of 0.2g/mol; Temperature of reaction 25 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=5; Non-polar organic solvent is normal hexane, and the consumption of water and normal hexane is 1 times of halohydrocarbon volume.
Get chlorallylene 1mol, catalyzer Tetrabutyl amonium bromide 0.2g, add in reactor together with normal hexane with the isopyknic water of chlorallylene.Control reaction system pH=5 by pH meter, when reaction system pH>5 time, reduce the rate of addition of sodium hydroxide solution; As pH<5, improve the rate of addition of sodium hydroxide solution.When system pH no longer changes, reaction completes; Stratification, distributes upper organic layer, and rectifying separation goes out vinyl carbinol, and productive rate is 90%, and purity is 98%, water ratio 0.08%.
Lower aqueous solution phase, filters out the sodium-chlor because of the solubleness precipitation that reaches capacity, and reclaims and continues as the aqueous solution reacted next time and supplement because unsaturated halohydrocarbon is hydrolyzed used up moisture 1mol.If catalyst efficiency declines, then suitable when make-up catalyst makes the catalytic efficiency of catalyzer at least be hydrolyzed with the unsaturated halohydrocarbon of first time catalysis.
Embodiment 2
Unsaturated halohydrocarbon is methallyl chloride; Alkaline matter is sodium carbonate, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is octadecyl trimethyl ammonium chloride, and consumption is the unsaturated halohydrocarbon of 1g/mol; Temperature of reaction 35 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=6; Non-polar organic solvent is Skellysolve A, and the consumption of water and Skellysolve A is 3 times of halohydrocarbon volume.
Get methallyl chloride 1mol, catalyzer Cetyltrimethylammonium bromide 1g, the water of 3 times of methallyl chloride volume adds in reactor together with Skellysolve A.Control reaction system pH=6 by pH meter, when reaction system pH>6 time, reduce the rate of addition of sodium carbonate solution; As pH<6, improve the rate of addition of sodium carbonate solution.When system pH no longer changes, reaction completes, and stratification distributes upper organic layer, and rectifying separation goes out methallyl alcohol, and productive rate is 92%, and purity is 97.2%, water ratio 0.05%.
Lower aqueous solution phase, filters out the sodium-chlor because of the solubleness precipitation that reaches capacity, and reclaims and continues as the aqueous solution reacted next time and supplement because unsaturated halohydrocarbon is hydrolyzed used up moisture 1mol.If catalyst efficiency declines, then suitable when make-up catalyst makes the catalytic efficiency of catalyzer at least be hydrolyzed with the unsaturated halohydrocarbon of first time catalysis.
Embodiment 3
Unsaturated halohydrocarbon is 1,3,2-CMB; Alkaline matter is sodium bicarbonate, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is Sodium dodecylbenzene sulfonate, and consumption is the unsaturated halohydrocarbon of 1.5g/mol; Temperature of reaction 45 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=8; Non-polar organic solvent is hexanaphthene, and the consumption of water and hexanaphthene is 5 times of halohydrocarbon volume.
Get 1,3,2-CMB 1mol, catalyzer Sodium dodecylbenzene sulfonate 1.5g, the water of 5 times of 1,3,2-CMB volume adds in reactor together with hexanaphthene.Control reaction system pH=8 by pH meter, when reaction system pH>8 time, reduce the rate of addition of sodium hydrogen carbonate solution; As pH<8, improve the rate of addition of sodium hydrogen carbonate solution.When system pH no longer changes, reaction completes, and stratification distributes upper organic layer, and rectifying separation goes out 1-alcohol-3-methyl-2-butene, and productive rate is 92.9%, and purity is 96.4%, water ratio 0.03%.
Lower aqueous solution phase, filters out the sodium-chlor because of the solubleness precipitation that reaches capacity, and reclaims and continues as the aqueous solution reacted next time and supplement because unsaturated halohydrocarbon is hydrolyzed used up moisture 1mol.If catalyst efficiency declines, then suitable when make-up catalyst makes the catalytic efficiency of catalyzer at least be hydrolyzed with the unsaturated halohydrocarbon of first time catalysis.
Embodiment 4
Unsaturated halohydrocarbon is 3,3-dimethyl-allyl bromine; Alkaline matter is saleratus, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is iron protochloride, and consumption is the unsaturated halohydrocarbon of 2g/mol; Temperature of reaction 55 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=7; Non-polar organic solvent is sherwood oil, and the consumption of water and sherwood oil is 2 times of halohydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Embodiment 5
Unsaturated halohydrocarbon is 4-1-chloro-4-methyl-benzene; Alkaline matter is salt of wormwood, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is cuprous chloride, and consumption is the unsaturated halohydrocarbon of 2.5g/mol; Temperature of reaction 60 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=6; Non-polar organic solvent is toluene, and the consumption of water and toluene is 1 times of halohydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Embodiment 6
Unsaturated halohydrocarbon is the bromo-1-octene of 8-; Alkaline matter is potassium hydroxide, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is cobalt chloride, and consumption is the unsaturated halohydrocarbon of 3g/mol; Temperature of reaction 70 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=7; Non-polar organic solvent is dimethylbenzene, and the consumption of water and dimethylbenzene is 3 times of halohydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Embodiment 7
Unsaturated halohydrocarbon is the chloro-1-undecylene of 11-; Alkaline matter is calcium carbonate, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is tin protochloride, and consumption is the unsaturated halohydrocarbon of 4g/mol; Temperature of reaction 80 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=6; Non-polar organic solvent is biphenyl, and the consumption of water and biphenyl is 4 times of halohydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Embodiment 8
Unsaturated halohydrocarbon is the bromo-1-phenyl of 3--1-propylene; Alkaline matter is magnesiumcarbonate, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is phenyl trimethicone ammonium chloride, and consumption is the unsaturated halohydrocarbon of 5g/mol; Temperature of reaction 100 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=5; Non-polar organic solvent is toluene, and the consumption of water and toluene is 3 times of halohydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Embodiment 9
Unsaturated halohydrocarbon is 1-chlorine-2-methyl-1-propylene; Alkaline matter is Quilonum Retard, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is triethylamine, and consumption is the unsaturated halohydrocarbon of 8g/mol; Temperature of reaction 150 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=5; Non-polar organic solvent is normal heptane, and the consumption of water and normal heptane is 1 times of halohydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Embodiment 10
Unsaturated halohydrocarbon is vinylchlorid; Alkaline matter is lithium hydroxide, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is methyl trioctylphosphine brometo de amonio, and consumption is the unsaturated halohydrocarbon of 10g/mol; Temperature of reaction 20 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=5; Non-polar organic solvent is octane-iso, and the consumption of water and octane-iso is 2 times of halohydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.Embodiment 11
Basically identical with embodiment 1, difference is only: adopt triethyl methyl brometo de amonio as catalyzer, adopts allyl bromide 98 as unsaturated halohydrocarbon, adopts aluminium hydroxide as alkaline matter.
Embodiment 12
Basically identical with embodiment 1, difference is only: adopt tributyl-methyl phosphonium brometo de amonio as catalyzer, adopts 1-bromo-2-methyl-1-propylene as unsaturated halohydrocarbon, adopts aluminium hydroxide as alkaline matter.
Embodiment 13
Basically identical with embodiment 1, difference is only: adopt tetrabutylammonium chloride as catalyzer, adopts methacrylic bromine as unsaturated halohydrocarbon, adopts ferric oxide as alkaline matter.
Embodiment 14
Basically identical with embodiment 1, difference is only: adopt etamon chloride as catalyzer, adopts bromo-3 methyl-2-butenes of 1-as unsaturated halohydrocarbon, adopts calcium hydroxide as alkaline matter.
Embodiment 15
Basically identical with embodiment 1, difference is only: adopt phenyltrimethylammonium bromide as catalyzer, adopts cinnamyl chloride as unsaturated halohydrocarbon, adopts magnesium hydroxide as alkaline matter.
Embodiment 16
Basically identical with embodiment 1, difference is only: adopt benzyltriethylammoinium chloride as catalyzer, adopts the chloro-1-butylene of 3-as unsaturated halohydrocarbon, adopts calcium hydroxide as alkaline matter.
Embodiment 17
Basically identical with embodiment 1, difference is only: adopt benzyl triethyl ammonium bromide as catalyzer, adopts allyl iodide as unsaturated halohydrocarbon, adopts hydrated barta as alkaline matter.
Embodiment 18
Basically identical with embodiment 1, difference is only: adopt benzyl triethyl ammonium Neutral ammonium fluoride as catalyzer, adopts 1-chloro-1-cyclopentenes as unsaturated halohydrocarbon, adopts calcium carbonate as alkaline matter.
Embodiment 19
Basically identical with embodiment 1, difference is only: adopt Trimethyllaurylammonium bromide as catalyzer, adopts 2-(chloromethyl) allyl group-trimethyl silane as unsaturated halohydrocarbon, adopts Calcium hydrogen carbonate as alkaline matter.
Embodiment 20
Basically identical with embodiment 1, difference is only: adopt palmityl trimethyl ammonium chloride as catalyzer, adopts 2-chloroacrylonitrile as unsaturated halohydrocarbon, adopts barium carbonate as alkaline matter.
Embodiment 21
Basically identical with embodiment 1, difference is only: adopt cetyltriethylammonium bromide as catalyzer, adopts 2-bromopropylene nitrile as unsaturated halohydrocarbon, adopts magnesium oxide as alkaline matter.
Embodiment 22
Basically identical with embodiment 1, difference is only: adopt myristyl trimonium brometo de amonio as catalyzer, adopts methacrylic iodine as unsaturated halohydrocarbon, adopts barium oxide as alkaline matter.
Embodiment 23
Basically identical with embodiment 1, difference is only: adopt Silver iodide as catalyzer, adopts 6-chloro-1-hexene as unsaturated halohydrocarbon, adopts aluminium sesquioxide as alkaline matter.
Embodiment 24
Basically identical with embodiment 1, difference is only: adopt borontrifluoride gold as catalyzer, adopts the bromo-1-decene of 10-as unsaturated halohydrocarbon, adopts aluminium hydroxide as alkaline matter.
Embodiment 25
Basically identical with embodiment 1, difference is only: adopt tetrabormated protactinium as catalyzer, adopts 11-bromo-1-undecylene as unsaturated halohydrocarbon, adopts aluminium hydroxide as alkaline matter.
The yield of table 1 embodiment 4 to 25 unsaturated alcohol, purity and water ratio
Comparative example 1
Unsaturated halohydrocarbon is the bromo-1-decene of 10-; Alkaline matter is barium oxide, consumption and unsaturated halohydrocarbon etc. mole; Catalyzer is benzyl triethyl ammonium bromide, and consumption is the unsaturated halohydrocarbon of 10g/mol; Temperature of reaction 170 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=6; Non-polar organic solvent is hexanaphthene, and the consumption of water and hexanaphthene is 2 times of halohydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Comparative example 2
Unsaturated halohydrocarbon is cinnamyl chloride; Do not use alkaline matter; Catalyzer is cuprous chloride, and consumption is the unsaturated halohydrocarbon of 2g/mol; Temperature of reaction 70 DEG C; Reaction pressure is system pressure itself; Reaction system pH is determined by the acid of reacting generation; Non-polar organic solvent is toluene, and the consumption of water and toluene is 6 times of halohydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Comparative example 3
Unsaturated halohydrocarbon is the chloro-1-cyclopentenes of 1-; Alkaline matter is sodium hydroxide, and consumption is 3 times of unsaturated halohydrocarbon mole number; Catalyzer is Tetrabutyl amonium bromide, and consumption is the unsaturated halohydrocarbon of 5g/mol; Temperature of reaction 60 DEG C; Reaction pressure is system pressure itself; Reaction system pH controls at pH=11; Non-polar organic solvent is toluene, and the consumption of water and toluene is 1 times of halohydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Claims (8)
1. a preparation method for unsaturated alcohol, is characterized in that: comprise the following steps: after the mixing of unsaturated halohydrocarbon, water, catalyzer and non-polar organic solvent, and add basic solution and adjust pH to 5-8, react at 20-150 DEG C, purifying, to obtain final product.
2. the preparation method of a kind of unsaturated alcohol according to claim 1, it is characterized in that: described purification step, is specially: static, question response system layering, upper strata is organic phase, lower floor is aqueous phase; Organic phase comprises non-polar solvent, halohydrocarbon and unsaturated alcohol; Lower floor's aqueous phase comprises water, catalyzer and metal halide; Rectifying organic phase, obtains unsaturated alcohol; After filtering aqueous phase, reuse as reaction soln.
3. the preparation method of a kind of unsaturated alcohol according to claim 1, is characterized in that: the amount ratio of described catalyzer and unsaturated halohydrocarbon is (0.2-10) g:1mol; The volume ratio of described water, non-polar organic solvent and unsaturated halohydrocarbon is (1-5): (1-5): 1.
4. the preparation method of a kind of unsaturated alcohol according to claim 1, is characterized in that: described catalyzer comprises one or more in phase-transfer catalyst and metal halide, described phase-transfer catalyst comprises triethylamine, methyl trioctylphosphine brometo de amonio, triethyl methyl brometo de amonio, tributyl-methyl phosphonium brometo de amonio, tetrabutylammonium chloride, Tetrabutyl amonium bromide, etamon chloride, phenyltrimethylammonium bromide, phenyl trimethicone ammonium chloride, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium Neutral ammonium fluoride, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride, cetyltriethylammonium bromide, octadecyl trimethyl ammonium chloride, myristyl trimonium brometo de amonio, Sodium dodecylbenzene sulfonate, the structural formula of described metal halide is M
xl
y, wherein M represents transition metal, comprises Fe, Co, Ni, Sn, Cu, Ag, Au, Pa, L represents haloid element, comprises F, Cl, Br, I.
5. the preparation method of a kind of unsaturated alcohol according to claim 1, is characterized in that: the carbon atom number of described unsaturated halohydrocarbon is 3-20.
6. the preparation method of a kind of unsaturated alcohol according to claim 1, it is characterized in that: described unsaturated halohydrocarbon comprises vinylchlorid, chlorallylene, 1-chlorine-2-methyl-1-propylene, methallyl chloride, allyl bromide 98, the bromo-2-methyl-1-propylene of 1-, methacrylic bromine, 1,3,2-CMB, bromo-3 methyl-2-butenes of 1-, the chloro-1-butylene of 3-, 3, 3-dimethyl-allyl bromine, allyl iodide, the chloro-1-cyclopentenes of 1-, 2-(chloromethyl) allyl group-trimethyl silane, 2-chloroacrylonitrile, 2-bromopropylene nitrile, methacrylic iodine, the chloro-1-hexene of 6-, the bromo-1-octene of 8-, the bromo-1-decene of 10-, the chloro-1-undecylene of 11-, the bromo-1-undecylene of 11-, cinnamyl chloride, the bromo-1-phenyl of 3--1-propylene, 4-1-chloro-4-methyl-benzene.
7. the preparation method of a kind of unsaturated alcohol according to claim 1, is characterized in that: described non-polar organic solvent comprises Skellysolve A, normal hexane, hexanaphthene, normal heptane, octane-iso, sherwood oil, toluene, dimethylbenzene, biphenyl.
8. the preparation method of a kind of unsaturated alcohol according to claim 1, is characterized in that: described basic solution is the aqueous solution of one or more mixtures in metal oxide, metal hydroxides or the metal carbonates such as sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, Quilonum Retard, lithium hydroxide, sodium hydroxide, potassium hydroxide, aluminium hydroxide, calcium hydroxide, magnesium hydroxide, calcium hydroxide, hydrated barta, calcium carbonate, Calcium hydrogen carbonate, barium carbonate, calcium oxide, magnesium oxide, barium oxide, aluminium sesquioxide, ferric oxide.
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| CN108191604A (en) * | 2017-12-22 | 2018-06-22 | 浙江大学 | A kind of continuous method for preparing 2- methallyl alcohols |
| CN116354791A (en) * | 2021-12-28 | 2023-06-30 | 江苏优嘉植物保护有限公司 | A kind of method that chloroalkene prepares isopentenol |
| CN116396155A (en) * | 2022-12-08 | 2023-07-07 | 辽宁众辉生物科技有限公司 | Synthesis method of 1- (4-chlorophenyl) -2-cyclopropyl-1-acetone |
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| CN104341255B (en) | 2016-08-24 |
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