A kind of preparation method of unsaturated alcohol
Technical field
The invention belongs to the synthesis field of organic molecule alcohol, be specifically related to the preparation method of a kind of unsaturated alcohol.
Background technology
Unsaturated alcohol is containing unsaturated bond and the Organic substance of hydroxyl, the unsaturated bond in its structure and hydroxyl in a kind of structure
Base has the highest chemical reactivity, it is possible to be polymerized, be esterified, be etherified, replace, aoxidize, the chemistry such as reduction anti-
Answer process, be widely used at field tools such as pharmaceuticals industry, fragrance industry and surfactant industry.
At present the method for synthesis unsaturated alcohol has a lot, mainly include esterification saponification method, grignard reagent method, direct hydrolysis method,
The methods such as prins condensation method, oxidation-reduction method.
Chinese patent application CN103242139A uses esterification saponification method method, is former with methallyl chloride, carboxylate
Material, with water as solvent, under the effect of 100-160 DEG C of condition and phase transfer catalyst, prepares esterification intermediate;So
After will prepare esterification intermediate saponification in the alkaline aqueous solution of 10-80 DEG C, purified after obtain methallyl alcohol.
Chinese patent application CN 102850186A uses grignard reagent method method, with methallyl chloride, formaldehyde as raw material,
Under inert gas shielding and less than under the conditions of 40 DEG C, first methallyl chloride is prepared as grignard reagent, then will be anti-
Answering system to be warming up to 40-70 DEG C, be added thereto to formaldehyde, grignard reaction occurs, preparing carbon atom number increases by one
Form intermediate, through the step such as quencher, purification, obtain 3-methyl-3-butene-1-alcohol.
U.S. Patent application US2072016 uses direct hydrolysis method method, is anti-with batch reactor or tubular reactor
Answering device, under the conditions of 80-250 DEG C, chlorohydrocarbon is direct hydrolysis in alkaline aqueous solution or alkaline suspension liquid, passes through
Separating-purifying obtains corresponding alcohol.
The advantage of above esterification saponification method, grignard reagent method and direct hydrolysis method is to avoid High Temperature High Pressure behaviour in course of reaction
Make, reduce the scale of investment of equipment and public work;But, the output of its waste water, waste residue etc. is higher, therefore carries
High corresponding environmental protection and processing cost.
Chinese patent application CN103333048A uses Prins condensation method, with isobutene., formaldehyde as raw material, with load
There is the γ-Al of metal phosphate2O3For catalyst, catalyst is filled in calandria type fixed bed reactor,
Under conditions of 200-300 DEG C and 8-10MPa, isobutene. continues through pipe with the mixed material of formaldehyde with certain speed
Formula reactor, through steps such as separating-purifyings, obtains 3-methyl-3-butene-1-alcohol.
Chinese patent application CN103755523A uses oxidation-reduction method, with isobutene. as raw material;The first step is in reaction temperature
Degree is for 320-380 DEG C, and isobutene. catalysis is oxidized to methacrolein;Second step under the conditions of 60-90 DEG C and 0.4-1MPa,
Methacrolein intermediate passes through Chemoselective reduction, generates 2-methallyl alcohol, after the steps such as separating-purifying,
To 2-methallyl alcohol.
The advantage of above Prins condensation method and oxidation-reduction method is course of reaction cleaning, and unreacted product can recycle,
Three waste discharge is few;But, its course of reaction needs High Temperature High Pressure, adds the investment of equipment and public work.
Summary of the invention
Goal of the invention: in order to overcome above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of reaction condition temperature
With, three waste discharge is less, productivity 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 that the present invention provides, comprises the following steps: unsaturated halogenated hydrocarbons,
After water, catalyst and non-polar organic solvent mixing, add alkaline solution and adjust pH to 5-8, react at 20-150 DEG C,
Purification, to obtain final product.
Preferably, described purification step, particularly as follows: static, question response system layering, upper strata is organic facies, and lower floor is
Aqueous phase;Organic facies includes non-polar solven, halogenated hydrocarbons and unsaturated alcohol;Lower floor's aqueous phase includes water, catalyst and metal
Halogenide;Rectification organic facies, obtains unsaturated alcohol;After filtering aqueous phase, it is recycled as reaction solution.
Unsaturation halogenated hydrocarbons, water, catalyst and non-polar organic solvent are added in reactor with certain proportion by the method,
Under uniform temperature and pressure, gradually adding alkaline solution in reaction system, control reaction system maintains one and stablizes
PH near, until reacted.
After having reacted, stratification, shunting upper organic phase comprises non-polar solven, halogenated hydrocarbons and target alcohol, through essence
Fraction from after obtain target alcohol, reaction dissolvent and unreacted halogenated hydrocarbons as reaction raw materials recycle;Lower floor's aqueous phase is for containing
Having the aqueous solution of catalyst and metal halide, when not having metal halide to separate out, this solution can directly reuse,
When there being metal halide to separate out, the solution after filtration recycles and reuses again, and the metal halide filtered can after purifying
To use as chemicals;Every secondary response terminates rear aqueous phase and need to supplement the water that halogenated hydrocarbons hydrolysising loss falls, catalyst visual response
Depending on the catalytic efficiency of system, when reaction rate reduces, suitably supplement catalyst.
Between the reaction temperature of the method is 20-150 DEG C, pressure is normal pressure or high pressure.The method use alkaline solution with
Unsaturated halogenated hydrocarbons equimolar amounts metering, changes the addition speed adjusting alkaline solution by the pH of reaction system.When instead
When the system pH of answering no longer changes, then it is considered as reaction and completes.So the response time of reaction system is with the titration of alkaline solution
Depending on time.The mensuration of pH value, uses the mode of digital display pH meter insertion reaction still to measure the pH value of reaction system.
The reactor that the method uses is usually reactor, measures the pH of reaction system, on the other hand time the most at one's leisure
Phase in reactor is the reaction between liquid-liquid diphase, uses reactor that reaction mass can be made to reach complete mixing flow so that anti-
Answer storeroom to be sufficiently mixed, improve reaction rate.Certainly the present invention equally uses tubular reactor or changes material
Coke deposition be liquid phase reaction or gas phase reaction, these have only to simply change the kind of material, proportioning with
And the immobilized mode of catalyst just can realize.Higher in view of the boiling point of part material in the present invention, catalyst resistance to
Hot property has certain temperature limiting, so tending to use churned mechanically closed reactor as reactor.
As preferably, described catalyst is (0.2-10) g:1mol with the amount ratio of unsaturated halogenated hydrocarbons;Described water, non-pole
Property organic solvent and unsaturated halogenated hydrocarbons volume ratio be (1-5): (1-5): 1.If the aqueous solution after halogenated hydrocarbons hydrolysis
Recycle, then need to consider to supplement catalyst and the problem of the moisture because of halogenated hydrocarbons hydrolysising loss.If in aqueous solution
The catalytic efficiency of catalyst reduces, and supplements catalyst according to the 20-100% of raw catalyst usage amount, with the catalysis of catalyst
Efficiency reaches former catalytic levels and is as the criterion;Every time halogenated hydrocarbons hydrolysis requires supplementation with after terminating and to lose because participating in halogenated hydrocarbons hydrolysis
Water, general and halogenated hydrocarbons equimolar moisturizing.
Preferred as another kind, described catalyst includes one or more in phase transfer catalyst and metal halide;Institute
State phase transfer catalyst and include triethylamine, methyl trioctylphosphine ammonium bromide, triethyl methyl ammonium bromide, tributyl-methyl phosphonium bromination
Ammonium, tetrabutylammonium chloride, tetrabutyl ammonium bromide, tetraethylammonium chloride, phenyltrimethylammonium bromide, phenyl trimethicone chlorine
Change ammonium, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium ammonium fluoride, trimethyl bromine
Change ammonium, hexadecyltrimethylammonium chloride, cetyltriethylammonium bromide, octadecyl trimethyl ammonium chloride, lima bean
Cool base trimethylammonium bromide, dodecylbenzene sodium sulfonate;The structural formula of described metal halide is MxLy, wherein M generation
Table transition metal, including Fe, Co, Ni, Sn, Cu, Ag, Au, Pa;L represents halogen, including F,
Cl、Br、I;The numeral that x and y represents is subscript, the quantivalence of metallic element and halogen determine.
Preferred as another kind, described unsaturated halogenated hydrocarbons may contain linear alkyl groups, branched alkyl group, cycloalkanes
One or several in the groups such as base group, aromatic group, heterocyclic group, its carbon atom number is 3-20.
As further preferably, described unsaturated halogenated hydrocarbons include vinyl chloride, allyl chloride, 1-chlorine-2-methyl-1-propylene,
Methallyl chloride, allyl bromide, bromoallylene, 1-bromo-2-methyl-1-propylene, methallyl bromide, 1,3,2-CMB,
Bromo-3 methyl-2-butenes of 1-, the chloro-1-butylene of 3-, 3,3-dimethallyl bromide, allyl iodide, 1-chloro-1-cyclopentenes, 2-(chlorine
Methyl) pi-allyl-trimethyl silane, 2-chloroacrylonitrile, 2-bromopropene nitrile, methacrylic iodine, 6-chloro-1-hexene, 8-
Bromo-1-octene, the bromo-1-decene of 10-, 11-chloro-1-endecatylene, 11-bromo-1-endecatylene, cinnamyl chloride, 3-bromo-1-benzene
Base-1-propylene, 4-1-chloro-4-methyl-benzene.
Preferred as another kind, described non-polar organic solvent is poorly water-soluble, have the strongest acid-proof alkaline and it is steady
The qualitative solvent not affected by temperature and pressure change, including pentane, normal hexane, hexamethylene, normal heptane, isobutyltrimethylmethane.,
Petroleum ether, toluene, dimethylbenzene, biphenyl.This kind of non-polar organic solvent is layered with aqueous phase, and reactant is from non-polar solven
Entering aqueous phase in mutually and participate in hydrolysis, hydrolyzate is gradually extracted into non-polar solven phase from aqueous phase, thus in reaction
Hydrolyzate and the pre-separation of aqueous phase in still.Further, it is also possible to reduce halogenated hydrocarbons and hydrolyzate side reaction in aqueous phase
Probability of happening.
Preferred as another kind, described alkaline solution both can be the aqueous solution of alkaline matter can also be the outstanding of alkaline matter
Swim solution, including sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, Lithium hydrate, sodium hydroxide,
Potassium hydroxide, aluminium hydroxide, calcium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, calcium carbonate, calcium bicarbonate,
Metal-oxide, the metal hydrogen-oxygens such as brium carbonate, calcium oxide, magnesium oxide, Barium monoxide, aluminium sesquioxide, iron sesquioxide
The aqueous solution of one or more mixture in compound or metal carbonate.
Beneficial effect: the preparation method technique of the unsaturated alcohol that the present invention provides is simple, mild condition, three waste discharge are less,
Productivity is high, purification of products convenient separation.
Specifically, relative to prior art, there is advantage highlighted below:
First, hydrolysising condition is gentle, it is not necessary to high-temperature high-voltage reaction condition;
Second, the on-demand interpolation of alkaline solution, it is not necessary to the use of alkaline matter is greatly improved in order to improve the conversion ratio of halogenated hydrocarbons
Amount;
3rd, use non-polar organic solvent to be extracted into rapidly organic layer as extractant, the product after halogenated hydrocarbons catalyzing hydrolysis,
Thus reduce the probability of happening of side reaction;Meanwhile, organic extraction layer is easy to separate with aqueous layer, simplifies separation
Step, reduces separating-purifying energy consumption;
4th, aqueous solution can circulate recycling.On the one hand the catalyst of aqueous solution still has catalytic performance, if urged
Change hydraulic performance decline can suitably supplement and catalyst need not be added the most in a large number, the metal halogen on the other hand generated in aqueous solution
Compound salt has promotion halogenated hydrocarbons performance of dissolubility in water, thus improves the catalyzing hydrolysis efficiency of halogenated hydrocarbons.Aqueous solution
In metal halide salt need not deliberately remove, once it reaches saturation solubility in water, it is possible to from aqueous solution analyse
Out, it is only necessary to simple filtration step can remove metal halide salt.
Detailed description of the invention
Embodiment 1
Unsaturated halogenated hydrocarbons is allyl chloride;Alkaline matter is sodium hydroxide, consumption and unsaturated halogenated hydrocarbons equimolar;Urge
Agent is tetrabutyl ammonium bromide, and consumption is 0.2g/mol unsaturation halogenated hydrocarbons;Reaction temperature 25 DEG C;Reaction pressure is body
It it is pressure itself;Reaction system pH controls at pH=5;Non-polar organic solvent is normal hexane, water and the consumption of normal hexane
For halogenated hydrocarbons volume 1 times.
Take allyl chloride 1mol, catalyst tetrabutyl ammonium bromide 0.2g, water isopyknic with allyl chloride and normal hexane one
Rise and add in reactor.By pH meter control reaction system pH=5, when reaction system pH > 5 when, reduce hydrogen-oxygen
Change the rate of addition of sodium solution;When pH < when 5, improves the rate of addition of sodium hydroxide solution.When system pH no longer becomes
During change, reaction completes;Stratification, distributes upper organic layer, and 1-propenol-3 is isolated in rectification, and productivity is 90%, pure
Degree is 98%, moisture content 0.08%.
Lower aqueous solution phase, filters out because reaching the sodium chloride that saturation solubility separates out, reclaims and continue as reacting next time
Aqueous solution and supplement because unsaturated halogenated hydrocarbons hydrolyzes the moisture 1mol consumed.If catalyst efficiency declines, then supplement
Suitable when catalyst makes at least unsaturated with the catalysis for the first time halogenated hydrocarbons hydrolysis of the catalytic efficiency of catalyst.
Embodiment 2
Unsaturated halogenated hydrocarbons is methallyl chloride;Alkaline matter is sodium carbonate, consumption and unsaturated halogenated hydrocarbons equimolar;
Catalyst is octadecyl trimethyl ammonium chloride, and consumption is 1g/mol unsaturation halogenated hydrocarbons;Reaction temperature 35 DEG C;Instead
Answering pressure is system pressure itself;Reaction system pH controls at pH=6;Non-polar organic solvent is pentane, water with just
The consumption of pentane is 3 times of halogenated hydrocarbons volume.
Take methallyl chloride 1mol, catalyst Cetyltrimethylammonium bromide 1g, the 3 of methallyl chloride volume
Water again adds in reactor together with pentane.Reaction system pH=6 is controlled, when reaction system pH by pH meter > 6
When, reduce the rate of addition of sodium carbonate liquor;When pH < when 6, improves the rate of addition of sodium carbonate liquor.Work as body
Being pH when no longer changing, reaction completes, and stratification distributes upper organic layer, and methallyl alcohol is isolated in rectification,
Productivity is 92%, and purity is 97.2%, moisture content 0.05%.
Lower aqueous solution phase, filters out because reaching the sodium chloride that saturation solubility separates out, reclaims and continue as reacting next time
Aqueous solution and supplement because unsaturated halogenated hydrocarbons hydrolyzes the moisture 1mol consumed.If catalyst efficiency declines, then supplement
Suitable when catalyst makes at least unsaturated with the catalysis for the first time halogenated hydrocarbons hydrolysis of the catalytic efficiency of catalyst.
Embodiment 3
Unsaturated halogenated hydrocarbons is 1,3,2-CMB;Alkaline matter is sodium bicarbonate, consumption and unsaturated halogenated hydrocarbons etc.
Mole;Catalyst is dodecylbenzene sodium sulfonate, and consumption is 1.5g/mol unsaturation halogenated hydrocarbons;Reaction temperature 45 DEG C;
Reaction pressure is system pressure itself;Reaction system pH controls at pH=8;Non-polar organic solvent is hexamethylene, water with
The consumption of hexamethylene is 5 times of halogenated hydrocarbons volume.
Take 1,3,2-CMB 1mol, catalyst dodecylbenzene sodium sulfonate 1.5g, 1,3,2-CMB body
The water of long-pending 5 times adds in reactor together with hexamethylene.Control reaction system pH=8 by pH meter, work as reaction system
The when of pH > 8, reduce the rate of addition of sodium bicarbonate solution;When pH < when 8, improves the dropping of sodium bicarbonate solution
Speed.When system pH no longer changes, reaction completes, and stratification distributes upper organic layer, and 1-is isolated in rectification
Alcohol-3-methyl-2-butene, productivity is 92.9%, and purity is 96.4%, moisture content 0.03%.
Lower aqueous solution phase, filters out because reaching the sodium chloride that saturation solubility separates out, reclaims and continue as reacting next time
Aqueous solution and supplement because unsaturated halogenated hydrocarbons hydrolyzes the moisture 1mol consumed.If catalyst efficiency declines, then supplement
Suitable when catalyst makes at least unsaturated with the catalysis for the first time halogenated hydrocarbons hydrolysis of the catalytic efficiency of catalyst.
Embodiment 4
Unsaturated halogenated hydrocarbons is 3,3-dimethallyl bromide;Alkaline matter is potassium bicarbonate, consumption and unsaturated halogenated hydrocarbons
Equimolar;Catalyst is ferrous chloride, and consumption is 2g/mol unsaturation halogenated hydrocarbons;Reaction temperature 55 DEG C;Reaction pressure
Power is system pressure itself;Reaction system pH controls at pH=7;Non-polar organic solvent is petroleum ether, water and petroleum ether
Consumption is halogenated hydrocarbons volume 2 times.Step such as embodiments 1-3 such as synthesis, separating-purifying and water-soluble liquid phase recycling
Shown in.
Embodiment 5
Unsaturated halogenated hydrocarbons is 4-1-chloro-4-methyl-benzene;Alkaline matter is potassium carbonate, consumption and unsaturated halogenated hydrocarbons equimolar;
Catalyst is Cu-lyt., and consumption is 2.5g/mol unsaturation halogenated hydrocarbons;Reaction temperature 60 DEG C;Reaction pressure is system
Pressure itself;Reaction system pH controls at pH=6;Non-polar organic solvent is toluene, and water is halo with the consumption of toluene
1 times of hydrocarbon volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Embodiment 6
Unsaturated halogenated hydrocarbons is 8-bromo-1-octene;Alkaline matter is potassium hydroxide, consumption and unsaturated halogenated hydrocarbons equimolar;
Catalyst is cobaltous chloride, and consumption is 3g/mol unsaturation halogenated hydrocarbons;Reaction temperature 70 DEG C;Reaction pressure be system from
Body pressure;Reaction system pH controls at pH=7;Non-polar organic solvent is dimethylbenzene, and water is halogen with the consumption of dimethylbenzene
For hydrocarbon volume 3 times.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Embodiment 7
Unsaturated halogenated hydrocarbons is 11-chloro-1-endecatylene;Alkaline matter is calcium carbonate, and consumption rubs with unsaturated halogenated hydrocarbons etc.
You;Catalyst is stannous chloride, and consumption is 4g/mol unsaturation halogenated hydrocarbons;Reaction temperature 80 DEG C;Reaction pressure is
System pressure itself;Reaction system pH controls at pH=6;Non-polar organic solvent is biphenyl, and water with the consumption of biphenyl is
4 times of halogenated hydrocarbons volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Embodiment 8
Unsaturated halogenated hydrocarbons is 3-bromo-1-phenyl-1-propylene;Alkaline matter is magnesium carbonate, and consumption rubs with unsaturated halogenated hydrocarbons etc.
You;Catalyst is phenyl trimethicone ammonium chloride, and consumption is 5g/mol unsaturation halogenated hydrocarbons;Reaction temperature 100 DEG C;Instead
Answering pressure is system pressure itself;Reaction system pH controls at pH=5;Non-polar organic solvent is toluene, water and toluene
Consumption is halogenated hydrocarbons volume 3 times.Step such as embodiments 1-3 such as synthesis, separating-purifying and water-soluble liquid phase recycling
Shown in.
Embodiment 9
Unsaturated halogenated hydrocarbons is 1-chlorine-2-methyl-1-propylene;Alkaline matter is lithium carbonate, and consumption rubs with unsaturated halogenated hydrocarbons etc.
You;Catalyst is triethylamine, and consumption is 8g/mol unsaturation halogenated hydrocarbons;Reaction temperature 150 DEG C;Reaction pressure is system
Pressure itself;Reaction system pH controls at pH=5;Non-polar organic solvent is normal heptane, and water with the consumption of normal heptane is
1 times of halogenated hydrocarbons volume.The steps such as synthesis, separating-purifying and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Embodiment 10
Unsaturated halogenated hydrocarbons is vinyl chloride;Alkaline matter is Lithium hydrate, consumption and unsaturated halogenated hydrocarbons equimolar;Catalysis
Agent is methyl trioctylphosphine ammonium bromide, and consumption is 10g/mol unsaturation halogenated hydrocarbons;Reaction temperature 20 DEG C;Reaction pressure is
System pressure itself;Reaction system pH controls at pH=5;Non-polar organic solvent is isobutyltrimethylmethane., water and the use of isobutyltrimethylmethane.
Amount is 2 times of halogenated hydrocarbons 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, the difference is that only: use triethyl methyl ammonium bromide as catalyst, use
Allyl bromide, bromoallylene, as unsaturated halogenated hydrocarbons, uses aluminium hydroxide as alkaline matter.
Embodiment 12
Basically identical with embodiment 1, the difference is that only: use tributyl-methyl phosphonium ammonium bromide as catalyst, use
1-bromo-2-methyl-1-propylene, as unsaturated halogenated hydrocarbons, uses aluminium hydroxide as alkaline matter.
Embodiment 13
Basically identical with embodiment 1, the difference is that only: use tetrabutylammonium chloride as catalyst, use methyl
Allyl bromide, bromoallylene, as unsaturated halogenated hydrocarbons, uses iron sesquioxide as alkaline matter.
Embodiment 14
Basically identical with embodiment 1, the difference is that only: use tetraethylammonium chloride as catalyst, use 1-bromine
-3 methyl-2-butenes, as unsaturated halogenated hydrocarbons, use calcium hydroxide as alkaline matter.
Embodiment 15
Basically identical with embodiment 1, the difference is that only: use phenyltrimethylammonium bromide as catalyst, use
Cinnamyl chloride, as unsaturated halogenated hydrocarbons, uses magnesium hydroxide as alkaline matter.
Embodiment 16
Basically identical with embodiment 1, the difference is that only: use benzyltriethylammoinium chloride as catalyst, use
The chloro-1-butylene of 3-, as unsaturated halogenated hydrocarbons, uses calcium hydroxide as alkaline matter.
Embodiment 17
Basically identical with embodiment 1, the difference is that only: use benzyl triethyl ammonium bromide as catalyst, use
Allyl iodide, as unsaturated halogenated hydrocarbons, uses barium hydroxide as alkaline matter.
Embodiment 18
Basically identical with embodiment 1, the difference is that only: use benzyl triethyl ammonium ammonium fluoride as catalyst, use
1-chloro-1-cyclopentenes, as unsaturated halogenated hydrocarbons, uses calcium carbonate as alkaline matter.
Embodiment 19
Basically identical with embodiment 1, the difference is that only: use Dodecyl trimethyl ammonium chloride as catalyst,
Use 2-(chloromethyl) pi-allyl-trimethyl silane as unsaturated halogenated hydrocarbons, use calcium bicarbonate as alkaline matter.
Embodiment 20
Basically identical with embodiment 1, the difference is that only: use hexadecyltrimethylammonium chloride as catalyst,
Use 2-chloroacrylonitrile as unsaturated halogenated hydrocarbons, use brium carbonate as alkaline matter.
Embodiment 21
Basically identical with embodiment 1, the difference is that only: use cetyltriethylammonium bromide as catalyst,
Use 2-bromopropene nitrile as unsaturated halogenated hydrocarbons, use magnesium oxide as alkaline matter.
Embodiment 22
Basically identical with embodiment 1, the difference is that only: use myristyl trimonium ammonium bromide as catalyst,
Use methacrylic iodine as unsaturated halogenated hydrocarbons, use Barium monoxide as alkaline matter.
Embodiment 23
Basically identical with embodiment 1, the difference is that only: use silver iodide as catalyst, use 6-chloro-1-hexene
As unsaturated halogenated hydrocarbons, use aluminium sesquioxide as alkaline matter.
Embodiment 24
Basically identical with embodiment 1, the difference is that only: use borontrifluoride gold as catalyst, use the bromo-1-of 10-
Decene, as unsaturated halogenated hydrocarbons, uses aluminium hydroxide as alkaline matter.
Embodiment 25
Basically identical with embodiment 1, the difference is that only: use tetrabormated protactinium as catalyst, use the bromo-1-of 11-
Endecatylene, as unsaturated halogenated hydrocarbons, uses aluminium hydroxide as alkaline matter.
Yield, purity and the moisture content of table 1 embodiment 4 to 25 unsaturated alcohol
Comparative example 1
Unsaturated halogenated hydrocarbons is the bromo-1-decene of 10-;Alkaline matter is Barium monoxide, consumption and unsaturated halogenated hydrocarbons equimolar;
Catalyst is benzyl triethyl ammonium bromide, and consumption is 10g/mol unsaturation halogenated hydrocarbons;Reaction temperature 170 DEG C;Reaction
Pressure is system pressure itself;Reaction system pH controls at pH=6;Non-polar organic solvent is hexamethylene, water and hexamethylene
The consumption of alkane is 2 times of halogenated hydrocarbons volume.Step such as embodiments 1-3 such as synthesis, separating-purifying and water-soluble liquid phase recycling
Shown in.
Comparative example 2
Unsaturated halogenated hydrocarbons is cinnamyl chloride;Do not use alkaline matter;Catalyst is Cu-lyt., and consumption is 2g/mol
Unsaturated halogenated hydrocarbons;Reaction temperature 70 DEG C;Reaction pressure is system pressure itself;Reaction system pH is by reacting generation
Acid decision;Non-polar organic solvent is toluene, water and consumption is halogenated hydrocarbons volume 6 times of toluene.Synthesis, separation
The steps such as purification and water-soluble liquid phase recycling are as shown in embodiment 1-3.
Comparative example 3
Unsaturated halogenated hydrocarbons is 1-chloro-1-cyclopentenes;Alkaline matter is sodium hydroxide, and consumption is unsaturated halogenated hydrocarbons molal quantity
3 times;Catalyst is tetrabutyl ammonium bromide, and consumption is 5g/mol unsaturation halogenated hydrocarbons;Reaction temperature 60 DEG C;Instead
Answering pressure is system pressure itself;Reaction system pH controls at pH=11;Non-polar organic solvent is toluene, water and first
The consumption of benzene is 1 times of halogenated hydrocarbons volume.Step such as embodiments 1-3 such as synthesis, separating-purifying and water-soluble liquid phase recycling
Shown in.