CN106966880A - A kind of preparation method of ligustral - Google Patents
A kind of preparation method of ligustral Download PDFInfo
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- CN106966880A CN106966880A CN201710295321.2A CN201710295321A CN106966880A CN 106966880 A CN106966880 A CN 106966880A CN 201710295321 A CN201710295321 A CN 201710295321A CN 106966880 A CN106966880 A CN 106966880A
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
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- C07C1/247—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by splitting of cyclic ethers
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- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
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Abstract
The present invention provides a kind of preparation method of ligustral, including prepares the dioxane of 2,4,4,6 tetramethyl 1,3, prepares the pentadiene of 2 methyl 1,3, synthesis ligustral.Course of reaction mild condition of the invention whole, almost without side reaction, and the used time is few, energy consumption is low, three-step reaction ligustral overall yield> 87%；The first step prepares the dioxane of 2,4,4,6 tetramethyl 1,3, yield>98%；Second step prepares the pentadiene of 2 methyl 1,3, yield>96%；3rd step synthesizes ligustral, yield>94%；With isobutene, the small molecule cheap and easy to get such as acetaldehyde is raw material, has innovated the process route for preparing the pentadiene of 2 methyl 1,3, it is to avoid cost is high in traditional handicraft, and the step such as the low condensation of yield, dehydration reduces cost 40% or so than traditional handicraft.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to by micromolecular compound acetaldehyde, isobutene, methacrylaldehyde system
The method of standby ligustral.
Background technology
Ligustral（Ligustral）, it is 2,4- dimethyl -3- cyclohexenes formaldehyde (I) and 3,5- dimethyl -4- cyclohexenes
The mixture of formaldehyde (II), general ratio is（Ⅰ）：（Ⅱ）=4：1, it is colourless or light yellow liquid, with the fragrance of a flower, the banksia rose and hay-scented
Breath can be harmonious very well, and dative is fluffy, citrus oils are very good with using.It clear fresh, available for perfume, cologne;It is used as enhancing
Agent, can reconcile citrus, pine, medicinal herbs and the banksia rose;The fragrance of a flower, aldehyde odor type and modern age new odor type are also applied for, natural sense can be given；It is fragrant
There is fresh fragrance with it in water, shampoo, perfumed soap, detergent essence；Can be fine with reference to dihydromyrcenol, " bergamot aldehyde ", lemongrass
It is equivalent to use, odor type can be innovated.Available in daily chemical essence formula, soap, synthetic detergent, cosmetic essence formula are particularly appropriate for
In.The fragrant effect of head as odor types such as the fragrance of a flower, blue or green perfume, fruity preferably, can increase the freshness and extension of essence, and most
It is stable in number medium.The current whole world is about 1000-2000 tons/year to the demand of ligustral.
The method for preparing ligustral in the prior art is to pass through Diels- by 2- methyl-1,3-pentylenes and methacrylaldehyde
Alder reactions are made, and 2- methyl isophthalic acids, and 3- pentadienes are dehydrated by 2- methyl -2,4- pentanediol and are made, 2- methyl -2,4- penta 2
Alcohol by acetone bimolecular be condensed to yield DAA hydrogenate again it is obtained.Patent CN201310131719 report using 2- methyl-
1,3-pentadiene carries out Diels-Alder reactions with methacrylaldehyde under certain temperature and pressure, and aged, washing, rectifying etc. is walked
Suddenly obtain not stating 2- methyl isophthalic acids in product, but patent, the source of 3- pentadienes.2- methyl-1,3-pentylenes are synthesis female
The important intermediate of loyal aldehyde, directly by 2- methyl isophthalic acids, 3- pentadienes carry out Diels-Alder reactions with methacrylaldehyde, should control
Reaction temperature, it is to avoid blunt temperature.
Patent US2422802 reports the method using reactive distillation, de- with simple substance catalysis of iodine 2- methyl -2,4- pentanediol
Water produces 2- methyl isophthalic acids, 3- pentadienes, while byproduct 4- methyl isophthalic acids are generated, 3- pentadienes, the yield of mixing diene is 84%.
This method uses elemental iodine as catalyst, and industrial production cost is higher.
Patent US20060058561 is reported in the presence of acidic catalyst, is taken away instead using polyethylene glycols
Should be hot, 2- methyl -2,4- pentanediols are dehydrated under the conditions of gasification temperature, 2- methyl isophthalic acids, 3- pentadienes and 4- first is generated
The mixture of base -1,3- pentadienes.This method reaction temperature is high, and needs a large amount of polyethylene glycol band reaction heat, and is not suitable for work
Industry is produced.
Document Baird, M, S. et al.Tetrahedron2002, 58(8):1581-1593. is reported with lattice
Family name's reagent E tMgBr is catalyst, under the conditions of T=- 60 DEG C, is condensed by acetone bimolecular and DAA is made, final production
Product yield is 80%.But this method reaction temperature is low, and RMgBr is seriously polluted, is not suitable for industrial applications.
From the foregoing, it will be observed that traditional handicraft prepared by ligustral need to be by condensation, hydrogenation, dehydration, Diels- since acetone
Alder etc. reacts, and route is long, and step is more, and accessory substance is more, and Atom economy is poor, particularly dehydration, and catalyst cost is high,
Target product selectivity is low.Above-mentioned reason restricts the production cost and market scale of ligustral product always.
The content of the invention
The purpose of the present invention be for ligustral prepare conventional processing routes deficiency there is provided one kind with isobutene, acetaldehyde
It is raw material etc. small molecule cheap and easy to get, product is obtained by cyclisation, cracking, D-A three-step reactions, to realize following invention mesh
's：
（1）The method of the present invention for preparing ligustral, three-step reaction ligustral overall yield> 87% ；
（2）Production cost is reduced, than traditional acetone method reduction by 40%；
（3）Reduce the temperature of 2,4,4,6- tetramethyl -1,3- dioxane cracking process；
Course of reaction is as follows：
For achieving the above object with solution above-mentioned technical problem, the technical scheme that the present invention takes is as follows：
A kind of preparation method of ligustral, including reaction（1）Prepare 2,4,4,6- tetramethyl -1,3- dioxane, reaction（2）System
Standby 2- methyl-1,3-pentylenes, reaction（3）Synthesize ligustral.
The following is the further improvement to above-mentioned technical proposal：
The reaction（1）2,4,4,6- tetramethyl -1,3- dioxane are prepared, are comprised the following steps：
Under certain temperature, pressure and catalysts conditions, with acetaldehyde prins reactions occur for isobutene in appropriate solvent, raw
Into 2,4,4,6- tetramethyl -1,3- dioxane.Gas chromatographic detection reaction process.After reaction terminates, cooling, stratification,
Aqueous phase containing catalyst continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, raw material and 2,4,4,6- tetramethyls -1,3-
Dioxane.Solvent uses lower batch reaction with raw material set, and dioxane is reacted（2）.
Reaction（1）Middle reaction temperature is 30 ~ 100 DEG C；It is preferred that 70-90 DEG C；
Reaction（1）Middle reaction pressure is 0.2 ~ 0.8 Mpa；
Reaction（1）The middle reaction time is 1.5-6.5h；It is preferred that 3-5h.
Reaction（1）Used in catalyst be trifluoroacetic acid, trifluoromethayl sulfonic acid, butter of tin, ferric trichloride, chlorination
The aqueous solution of one or more of mixing in zinc, indium trichloride, niter cake, potassium acid sulfate, pH scopes are 4.0 ~ 6.0；
Reaction（1）The mass ratio of solvent and aqueous catalyst solution is 11.5-17.5:1；
Reaction（1）Middle solvent for use is water, tetrahydrofuran, dichloromethane, toluene, the one or more in hexamethylene；
Reaction（1）The mol ratio of middle isobutene and acetaldehyde is 0.5 ~ 1.2；
Reaction（1）The mass ratio of middle isobutene and solvent is 0.01 ~ 0.1；
Reaction（1）Middle rotor mixing speed is 300 ~ 900 rpm.
The reaction（2）2- methyl isophthalic acids are prepared, 3- pentadienes are open loop cracking reaction, comprised the following steps that：
Will reaction（1）2,4,4,6- tetramethyl -1,3- dioxane that middle rectifying is obtained are diluted with appropriate solvent, in a constant temperature
Under degree, pressure and catalysts conditions, occur open loop cracking reaction, gas-chromatography monitoring reaction process.It is cold after reaction terminates
But, stratification, obtains acetaldehyde, 2- methyl isophthalic acids, 3- pentadienes and water, and the aqueous phase containing catalyst continues set and uses lower batch reaction,
Oil phase is rectifying to obtain solvent, acetaldehyde and 2- methyl isophthalic acids, 3- pentadienes, and solvent and acetaldehyde set use lower batch reaction, 2- methyl isophthalic acids,
3- pentadienes are reacted（3）.
Reaction（2）Middle reaction temperature is 80 ~ 140 DEG C；It is preferred that 90-105 DEG C；
Reaction（2）Middle reaction pressure is 0.25 ~ 0.85 Mpa；It is preferred that 0.6-0.8Mpa；
Reaction（2）The middle reaction time is 4.5-5h；
Reaction（2）Used in catalyst be nitric acid, trifluoroacetic acid, aluminum sulfate, ferric nitrate, phosphomolybdic acid, silico-tungstic acid, fluoroform
One or more of aqueous solution in sulfonic acid copper, trifluoromethayl sulfonic acid scandium, pH scopes are 4.0 ~ 6.5.
Reaction（2）In, the mass ratio of 2,4,4,6- tetramethyl -1,3- dioxane and aqueous catalyst solution is：17.8-
24.6:1；
Reaction（2）Middle solvent for use is water, tetrahydrofuran, dichloromethane, dimethylbenzene, the one or more in normal heptane.
Reaction（2）In 2,4,4,6- tetramethyl -1,3- dioxane and solvent mass ratio be 0.1 ~ 1.0；
Reaction（2）Middle rotor mixing speed is 200 ~ 1200 rpm；
Reaction（3）Ligustral is synthesized, is Diels-Alder reactions, comprises the following steps that：
By 2- methyl isophthalic acids, 3- pentadienes are mixed with methacrylaldehyde, under trace catalyst effect, in certain reaction temperature and pressure
Lower progress Diene-addition reaction, gas-chromatography monitoring reaction process.After reaction terminates, reaction solution is cooled to 20 DEG C, and rectifying is obtained
Ligustral product.
Reaction（3）Middle reaction temperature is 50 ~ 70 DEG C；
Reaction（3）Middle reaction pressure is 0.15~0.45 Mpa；
Reaction（3）The middle reaction time is 2.5-3.5h；
Reaction（3）The mol ratio of middle methacrylaldehyde and 2- methyl-1,3-pentylenes is 1.05 ~ 1.25；
Reaction（3）Used in catalyst be silver acetate, bismuth nitrate, acetyl acetone, ammonium metavanadate and cobalt naphthenate in one
Plant or several combinations；
Reaction（3）The mass ratio of the quality sum of middle catalyst and 2- methyl-1,3-pentylenes and methacrylaldehyde for 0.0002 ~
0.01；It is preferred that 0.002-0.009.
Reaction（3）Middle rotor mixing speed is 400 ~ 1200 rpm.
The present invention use isobutene and acetaldehyde as raw material, selects appropriate catalyst, obtained higher prins reactions with
Cracking reaction yield, while reducing cracking reaction temperature.Compared with ligustral prepares traditional route, this process route has letter
It is single, stably, the advantage of environmental protection, it is to avoid the dehydration in traditional route, Atom economy is high, is improving reaction yield
While greatly reduce reaction cost.
Compared with prior art, beneficial effects of the present invention are as follows：
1st, whole course of reaction mild condition, almost without side reaction, and the used time is few, energy consumption is low, and three-step reaction ligustral is totally received
Rate> 87%；The first step prepares 2,4,4,6- tetramethyl -1,3- dioxane, yield>98%；Second step prepares 2- methyl isophthalic acids, 3-
Pentadiene, yield>96%；3rd step synthesizes ligustral, yield>94%.
2nd, with isobutene, the small molecule cheap and easy to get such as acetaldehyde is raw material, has innovated preparation 2- methyl isophthalic acids, 3- pentadienes
Process route, it is to avoid cost is high in traditional handicraft, the step such as the low condensation of yield, dehydration, cost 40% is reduced than traditional handicraft
Left and right.
3rd, ligustral prepared by the present invention, content in crude product>92%, after crude product rectifying, purity reaches more than 99.7%.
4th, react（1）、（2）Middle used catalyst cost is low, and using water-oil phase reaction, convenient post-treatment, aqueous phase is urged
Agent can realize recycled, and environment-friendly, three waste discharge is few.
5th, the cracking reaction temperature of 2,4,4,6- tetramethyl -1,3- dioxane is reduced, cracking reaction temperature is 80 ~
140℃；Prior art is generally 270-300 DEG C.
Embodiment
The method prepared below in conjunction with specific embodiment to ligustral of the present invention is described in further detail：
A kind of preparation method of the ligustral of embodiment 1
Comprise the following steps：
（1）Prepare 2,4,4,6- tetramethyl -1,3- dioxane
In the 500ml autoclaves with magnetic agitation and temperature controller, 220.2 g acetaldehyde solutions are added（2 mol, 40%,
Mass fraction）, 175 g tetrahydrofurans, 10 g butters of tin-ferric chloride aqueous solutionses（Butter of tin and ferric trichloride mole
Than for 1:1.4, pH value of solution=4.0 ~ 4.5, catalyst content is regulated and controled by pH）, isobutene is slowly introducing afterwards to system
Pressure reaches 0.15 Mpa（1.5 mol）.Reactor is heated to 72 DEG C, the rpm of rotor speed 800,2.5 h of reaction to body
It is that pressure is down to 0.11 Mpa, gas chromatographic analysis acetaldehyde conversion is more than 98%.
It is water-cooled, extrudes reaction solution, stratification, the aqueous phase containing catalyst continues set and uses lower batch reaction, oil phase warp
Rectifying obtains solvent, raw material and 2,4,4,6- tetramethyl -1,3- dioxane (135.3 g, 0.94 mol).Solvent and raw material
Set uses lower batch reaction, and dioxane is reacted（2）.
（2）Prepare 2- methyl-1,3-pentylenes
In 500ml autoclaves, (135.3 g, 0.94 mol) 2,4,4,6- tetramethyl -1,3- dioxane, 205 g are added
Tetrahydrofuran, 5.5 g trifluoroacetic acids-trifluoromethayl sulfonic acid copper liquor（Trifluoroacetic acid is with trifluoromethayl sulfonic acid copper mol ratio
2.1 :1, pH value of solution=5.0 ~ 5.5）, reactor is heated to 125 DEG C, and the rpm of rotor speed 900 reacts 4.5 h,
System pressure is reached for 0.4 Mpa, tetramethyl -1, the 3- dioxane conversion ratio of gas chromatographic analysis 2,4,4,6- in course of reaction
More than 99.5%.
After reaction terminates, it is water-cooled, stratification, acetaldehyde, 2- methyl isophthalic acids, 3- pentadienes and water is obtained, containing catalyst
Aqueous phase continue set and use lower batch reaction, oil phase is rectifying to obtain solvent, acetaldehyde and 2- methyl isophthalic acids, 3- pentadienes (75 g,
0.92 mol), solvent uses lower batch reaction with acetaldehyde set, and 2- methyl isophthalic acids, 3- pentadienes are reacted（3）.
（3）Synthesize ligustral
In 200ml autoclaves, 75 g are added（0.92 mol）2- methyl isophthalic acids, 3- pentadienes, 58.9 g（1.05 mol）Third
Olefine aldehydr, 0.005 g ammonium metavanadates, 0.001 g cobalt naphthenates, reactor is heated to 65 DEG C, the rpm of rotor speed 1000, instead
System pressure in 2.5 h, course of reaction is answered to be reached for 0.3 Mpa, gas chromatographic analysis 2- methyl isophthalic acids, 3- pentadiene conversion ratios are big
In 98%.
After reaction terminates, reaction solution is water-cooled to 20 DEG C, rectifying obtains the ligustral product that content is more than 99.7%
(120.3 g, 0.87 mol), wherein 2,4- dimethyl -3- cyclohexenyl carbaldehydes and 3,5- dimethyl -3- cyclohexenyl group first
Aldehyde, ratio is 4.05: 1, consistent with the natural ligustral ratio extracted in nature；
Three-step approach prepares ligustral, and total recovery is 88.5%.
A kind of preparation method of the ligustral of embodiment 2
Comprise the following steps：
（1）Prepare 2,4,4,6- tetramethyl -1,3- dioxane
In the 500ml autoclaves with magnetic agitation and temperature controller, 220.2 g acetaldehyde solutions are added（2 mol, 40%,
Mass fraction）, 175 g tetrahydrofurans, the 15 g trifluoromethayl sulfonic acids-indium trichloride aqueous solution（Trifluoromethayl sulfonic acid and trichlorine
It is 1 to change indium mol ratio:1.4, aqueous solution pH=4.0-4.5, catalyst content is regulated and controled by pH）, isobutene is slowly introducing afterwards
0.15 Mpa is reached to system pressure（1.5 mol）.Reactor is heated to 74 DEG C, the rpm of rotor speed 800, reaction 2.5
H is down to 0.11 Mpa to system pressure, and gas chromatographic analysis acetaldehyde conversion is more than 98%.It is water-cooled, extrudes reaction solution, it is quiet
Layering is put, the aqueous phase containing catalyst continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, raw material and 2,4,4,6- tetramethyls
Base -1,3- dioxane (133.7 g, 0.93 mol).Solvent uses lower batch reaction with raw material set, and dioxane is reacted
（2）.
（2）Prepare 2- methyl-1,3-pentylenes
In 500ml autoclaves, (133.7 g, 0.93 mol) 2,4,4,6- tetramethyl -1,3- dioxane, 205 g are added
Tetrahydrofuran, the 7.5 g trifluoroacetic acids-trifluoromethayl sulfonic acid scandium aqueous solution（Trifluoroacetic acid is with trifluoromethayl sulfonic acid scandium mol ratio
2.1 :1, pH=5.0 ~ 5.5）, reactor is heated to 125 DEG C, and the rpm of rotor speed 900 reacts 4.5 h, reaction
During system pressure be reached for 0.4 Mpa, tetramethyl -1, the 3- dioxane conversion ratio of gas chromatographic analysis 2,4,4,6- is more than
99.5%.After reaction terminates, it is water-cooled, stratification, acetaldehyde, 2- methyl isophthalic acids, 3- pentadienes and water is obtained, containing catalyst
Aqueous phase continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, acetaldehyde and 2- methyl isophthalic acids, 3- pentadienes (74.5 g,
0.91mol), solvent uses lower batch reaction with acetaldehyde set, and 2- methyl isophthalic acids, 3- pentadienes are reacted（3）.
（3）Synthesize ligustral
In 200ml autoclaves, (74.5 g, 0.91mol) 2- methyl isophthalic acids, 3- pentadienes, 58.9 g are added（1.05
mol）Methacrylaldehyde, 0.005 g ammonium metavanadates, 0.002 g silver acetates, reactor is heated to 65 DEG C, rotor speed 1000
Rpm, reacts system pressure in 2.5 h, course of reaction and is reached for 0.3 Mpa, gas chromatographic analysis 2- methyl isophthalic acids, 3- pentadienes turn
Rate is more than 98%.After reaction terminates, reaction solution is water-cooled to 20 DEG C, rectifying obtains the ligustral product that content is more than 99.7%
(120.1 g, 0.87 mol), wherein 2,4- dimethyl -3- cyclohexenyl carbaldehydes and 3,5- dimethyl -3- cyclohexenyl group first
Aldehyde, ratio is 3.98: 1, consistent with the natural ligustral ratio extracted in nature；
Three-step approach prepares ligustral, and total recovery is 88%.
A kind of preparation method of the ligustral of embodiment 3
Comprise the following steps：
（1）Prepare 2,4,4,6- tetramethyl -1,3- dioxane
In the 2000 ml autoclaves with magnetic agitation and temperature controller, 880.9 g acetaldehyde solutions are added（8 mol ,
40%, mass fraction）, 700 g tetrahydrofurans, 60 g butters of tin-ferric chloride aqueous solutionses（Butter of tin rubs with ferric trichloride
You are than being 1:1.5, pH value of solution=5.5-6.0 catalyst contents are regulated and controled by pH）, isobutene is slowly introducing afterwards to system pressure
Power reaches 0.60 Mpa（6.0 mol）.Reactor is heated to 76 DEG C, the rpm of rotor speed 1000,3.5 h of reaction to system
Pressure is down to 0.35 Mpa, and gas chromatographic analysis acetaldehyde conversion is more than 98.5%.It is water-cooled, extrudes reaction solution, stands and divide
Layer, aqueous phase containing catalyst continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, raw material and 2, and 4,4,6- tetramethyls-
1,3- dioxane (535.2 g, 3.72 mol).Solvent uses lower batch reaction with raw material set, and dioxane is reacted（2）.
（2）Prepare 2- methyl-1,3-pentylenes
In 2000 ml autoclaves, (535.2 g, 3.72 mol) 2,4,4,6- tetramethyl -1,3- dioxane, 820 are added
G tetrahydrofurans, the 30.0 g trifluoroacetic acids-phosphomolybdic acid aqueous solution（Trifluoroacetic acid is 1.9 with phosphomolybdic acid mol ratio:1, solution
pH = 5.0 ~ 5.5）, reactor is heated to 125 DEG C, and the rpm of rotor speed 1100 reacts body in 5.0 h, course of reaction
It is that pressure is reached for 0.6 Mpa, tetramethyl -1, the 3- dioxane conversion ratio of gas chromatographic analysis 2,4,4,6- is more than 99 %.Instead
After should terminating, it is water-cooled, stratification, obtains acetaldehyde, 2- methyl isophthalic acids, 3- pentadienes and water, the aqueous phase containing catalyst continues
Set uses lower batch reaction, and oil phase is rectifying to obtain solvent, acetaldehyde and 2- methyl isophthalic acids, 3- pentadienes (298 g, 3.64mol),
Solvent uses lower batch reaction with acetaldehyde set, and 2- methyl isophthalic acids, 3- pentadienes are reacted（3）.
（3）Synthesize ligustral
In 1000ml autoclaves, (298 g, 3.64mol) 2- methyl isophthalic acids, 3- pentadienes, 235.8 g are added（4.2
mol）Methacrylaldehyde, 0.02g ammonium metavanadates, 0.01 g bismuth nitrates, reactor is heated to 65 DEG C, the rpm of rotor speed 1000,
React system pressure in 3.5 h, course of reaction and finally reach 0.15Mpa, gas chromatographic analysis 2- methyl isophthalic acids, 3- pentadienes turn
Rate is more than 98%.After reaction terminates, reaction solution is water-cooled to 20 DEG C, rectifying obtains the ligustral product that content is more than 99.7%
(479.8 g, 3.46 mol), wherein 2,4- dimethyl -3- cyclohexenyl carbaldehydes and 3,5- dimethyl -3- cyclohexenyl group first
Aldehyde, ratio is 4.0: 1, consistent with the natural ligustral ratio extracted in nature；Three-step approach prepares ligustral, and total recovery is
88.4%。
A kind of preparation method of the ligustral of embodiment 4
Comprise the following steps：
（1）Prepare 2,4,4,6- tetramethyl -1,3- dioxane
In the 500ml autoclaves with magnetic agitation and temperature controller, 220.2 g acetaldehyde solutions are added（2 mol, 40%,
Mass fraction）, 175 g tetrahydrofurans, 10 g butters of tin-ferric chloride aqueous solutionses（Butter of tin and ferric trichloride mole
Than for 1:1.4, pH value of solution=4.0 ~ 4.5, catalyst content is regulated and controled by pH）, isobutene is slowly introducing afterwards to system
Pressure reaches 0.15 Mpa（1.5 mol）.Reactor is heated to 35 DEG C, the rpm of rotor speed 800,6.5 h of reaction to body
It is that pressure is down to 0.13 Mpa, gas chromatographic analysis acetaldehyde conversion is more than 99%.It is water-cooled, extrudes reaction solution, stands and divide
Layer, aqueous phase containing catalyst continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, raw material and 2, and 4,4,6- tetramethyls-
1,3- dioxane (121.5 g, 0.82mol).Solvent uses lower batch reaction with raw material set, and dioxane is reacted（2）.
（2）Prepare 2- methyl-1,3-pentylenes
In 500ml autoclaves, (121.5 g, 0.82mol) 2,4,4,6- tetramethyl -1,3- dioxane, 205 g are added
Tetrahydrofuran, 5.5 g trifluoroacetic acids-trifluoromethayl sulfonic acid copper liquor（Trifluoroacetic acid is with trifluoromethayl sulfonic acid copper mol ratio
2.1 :1, pH value of solution=5.0 ~ 5.5）, reactor is heated to 125 DEG C, and the rpm of rotor speed 900 reacts 4.5 h,
System pressure is reached for 0.4 Mpa, tetramethyl -1, the 3- dioxane conversion ratio of gas chromatographic analysis 2,4,4,6- in course of reaction
More than 99.5%.After reaction terminates, it is water-cooled, stratification, acetaldehyde, 2- methyl isophthalic acids, 3- pentadienes and water is obtained, containing catalysis
The aqueous phase of agent continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, acetaldehyde and 2- methyl isophthalic acids, 3- pentadienes (68 g,
0.81 mol), solvent uses lower batch reaction with acetaldehyde set, and 2- methyl isophthalic acids, 3- pentadienes are reacted（3）.
（3）Synthesize ligustral
In 200ml autoclaves, 68 g are added（0.81 mol）2- methyl isophthalic acids, 3- pentadienes, 58.9 g（1.05 mol）Third
Olefine aldehydr, 0.005 g ammonium metavanadates, 0.001 g cobalt naphthenates, reactor is heated to 65 DEG C, the rpm of rotor speed 1000, instead
System pressure in 2.5 h, course of reaction is answered to be reached for 0.3 Mpa, gas chromatographic analysis 2- methyl isophthalic acids, 3- pentadiene conversion ratios are big
In 98%.After reaction terminates, reaction solution is water-cooled to 20 DEG C, rectifying obtains the ligustral product (107.9 that content is more than 99.7%
G, 0.75 mol), wherein 2,4- dimethyl -3- cyclohexenyl carbaldehydes and 3,5- dimethyl -3- cyclohexenyl carbaldehydes, ratio is
3.95: 1, it is consistent with the natural ligustral ratio extracted in nature；Three-step approach prepares ligustral, and total recovery is 87%.
A kind of preparation method of the ligustral of embodiment 5
Comprise the following steps：
（1）Prepare 2,4,4,6- tetramethyl -1,3- dioxane
In the 500ml autoclaves with magnetic agitation and temperature controller, 220.2 g acetaldehyde solutions are added（2 mol, 40%,
Mass fraction）, 175 g tetrahydrofurans, 10 g butters of tin-ferric chloride aqueous solutionses（Butter of tin and ferric trichloride mole
Than for 1:1.4, pH value of solution=4.0 ~ 4.5, catalyst content is regulated and controled by pH）, isobutene is slowly introducing afterwards to system
Pressure reaches 0.15 Mpa（1.5 mol）.Reactor is heated to 95 DEG C, the rpm of rotor speed 800,1.5 h of reaction to body
It is that pressure is down to 0.12 Mpa, gas chromatographic analysis acetaldehyde conversion is more than 98%.It is water-cooled, extrudes reaction solution, stands and divide
Layer, aqueous phase containing catalyst continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, raw material and 2, and 4,4,6- tetramethyls-
1,3- dioxane (110.4g, 0.74mol).Solvent uses lower batch reaction with raw material set, and dioxane is reacted（2）.
（2）Prepare 2- methyl-1,3-pentylenes
In 500ml autoclaves, (110.4g, 0.74mol) 2,4,4,6- tetramethyl -1,3- dioxane, 205 g are added
Tetrahydrofuran, 5.5 g trifluoroacetic acids-trifluoromethayl sulfonic acid copper liquor（Trifluoroacetic acid is with trifluoromethayl sulfonic acid copper mol ratio
2.1 :1, pH value of solution=5.0 ~ 5.5）, reactor is heated to 125 DEG C, and the rpm of rotor speed 900 reacts 4.5 h,
System pressure is reached for 0.4 Mpa, tetramethyl -1, the 3- dioxane conversion ratio of gas chromatographic analysis 2,4,4,6- in course of reaction
More than 99.5%.After reaction terminates, it is water-cooled, stratification, acetaldehyde, 2- methyl isophthalic acids, 3- pentadienes and water is obtained, containing catalysis
The aqueous phase of agent continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, acetaldehyde and 2- methyl isophthalic acids, 3- pentadienes (63 g,
0.73 mol), solvent uses lower batch reaction with acetaldehyde set, and 2- methyl isophthalic acids, 3- pentadienes are reacted（3）.
（3）Synthesize ligustral
In 200ml autoclaves, 63 g are added（0.73 mol）2- methyl isophthalic acids, 3- pentadienes, 58.9 g（1.05 mol）Third
Olefine aldehydr, 0.005 g ammonium metavanadates, 0.001 g cobalt naphthenates, reactor is heated to 65 DEG C, the rpm of rotor speed 1000, instead
System pressure in 2.5 h, course of reaction is answered to be reached for 0.3 Mpa, gas chromatographic analysis 2- methyl isophthalic acids, 3- pentadiene conversion ratios are big
In 98%.After reaction terminates, reaction solution is water-cooled to 20 DEG C, rectifying obtains the ligustral product (97.3 that content is more than 99.7%
G, 0.69 mol), wherein 2,4- dimethyl -3- cyclohexenyl carbaldehydes and 3,5- dimethyl -3- cyclohexenyl carbaldehydes, ratio is
4.01: 1, consistent with the natural ligustral ratio extracted in nature, three-step approach prepares ligustral, and total recovery is 87.6%.
A kind of preparation method of the ligustral of embodiment 6
Comprise the following steps：
（1）Prepare 2,4,4,6- tetramethyl -1,3- dioxane
In the 2000 ml autoclaves with magnetic agitation and temperature controller, 880.9 g acetaldehyde solutions are added（8 mol ,
40%, mass fraction）, 700 g tetrahydrofurans, 60 g butters of tin-ferric chloride aqueous solutionses（Butter of tin rubs with ferric trichloride
You are than being 1:1.5, pH value of solution=5.5-6.0 catalyst contents are regulated and controled by pH）, isobutene is slowly introducing afterwards to system pressure
Power reaches 0.60 Mpa（6.0 mol）.Reactor is heated to 74 DEG C, the rpm of rotor speed 1000,3.2 h of reaction to system
Pressure is down to 0.35 Mpa, and gas chromatographic analysis acetaldehyde conversion is more than 98.5%.It is water-cooled, extrudes reaction solution, stands and divide
Layer, aqueous phase containing catalyst continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, raw material and 2, and 4,4,6- tetramethyls-
1,3- dioxane (535.2 g, 3.72 mol).Solvent uses lower batch reaction with raw material set, and dioxane is reacted（2）.
（2）Prepare 2- methyl-1,3-pentylenes
In 2000 ml autoclaves, (535.2 g, 3.72 mol) 2,4,4,6- tetramethyl -1,3- dioxane, 820 are added
G tetrahydrofurans, the 30.0 g trifluoroacetic acids-phosphomolybdic acid aqueous solution（Trifluoroacetic acid is 1.9 with phosphomolybdic acid mol ratio:1, solution
pH = 5.0 ~ 5.5）, reactor is heated to 90 DEG C, and the rpm of rotor speed 1100 reacts body in 5.0 h, course of reaction
It is that pressure is reached for 0.62 Mpa, tetramethyl -1, the 3- dioxane conversion ratio of gas chromatographic analysis 2,4,4,6- is more than 99 %.Instead
After should terminating, it is water-cooled, stratification, obtains acetaldehyde, 2- methyl isophthalic acids, 3- pentadienes and water, the aqueous phase containing catalyst continues
Set uses lower batch reaction, and oil phase is rectifying to obtain solvent, acetaldehyde and 2- methyl isophthalic acids, 3- pentadienes (298 g, 3.64mol),
Solvent uses lower batch reaction with acetaldehyde set, and 2- methyl isophthalic acids, 3- pentadienes are reacted（3）.
（3）Synthesize ligustral
In 1000ml autoclaves, (298 g, 3.64mol) 2- methyl isophthalic acids, 3- pentadienes, 235.8 g are added（4.2
mol）Methacrylaldehyde, 0.61g ammonium metavanadates, 0.45 g bismuth nitrates, reactor is heated to 65 DEG C, the rpm of rotor speed 1000,
React system pressure in 3.5 h, course of reaction and finally reach 0.15Mpa, gas chromatographic analysis 2- methyl isophthalic acids, 3- pentadienes turn
Rate is more than 98%.After reaction terminates, reaction solution is water-cooled to 20 DEG C, rectifying obtains the ligustral product that content is more than 99.7%
(479.8 g, 3.46 mol), wherein 2,4- dimethyl -3- cyclohexenyl carbaldehydes and 3,5- dimethyl -3- cyclohexenyl group first
Aldehyde, ratio is 4.0: 1, consistent with the natural ligustral ratio extracted in nature；Three-step approach prepares ligustral, and total recovery is
89.2%。
A kind of preparation method of the ligustral of embodiment 7
Comprise the following steps：
（1）Prepare 2,4,4,6- tetramethyl -1,3- dioxane
In the 2000 ml autoclaves with magnetic agitation and temperature controller, 880.9 g acetaldehyde solutions are added（8 mol ,
40%, mass fraction）, 700 g tetrahydrofurans, 60 g butters of tin-ferric chloride aqueous solutionses（Butter of tin rubs with ferric trichloride
You are than being 1:1.5, pH value of solution=5.5-6.0 catalyst contents are regulated and controled by pH）, isobutene is slowly introducing afterwards to system pressure
Power reaches 0.60 Mpa（6.0 mol）.Reactor is heated to 80 DEG C, the rpm of rotor speed 1000,4.3 h of reaction to system
Pressure is down to 0.30 Mpa, and gas chromatographic analysis acetaldehyde conversion is more than 98.5%.It is water-cooled, extrudes reaction solution, stands and divide
Layer, aqueous phase containing catalyst continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, raw material and 2, and 4,4,6- tetramethyls-
1,3- dioxane (535.2 g, 3.72 mol).Solvent uses lower batch reaction with raw material set, and dioxane is reacted（2）.
（2）Prepare 2- methyl-1,3-pentylenes
In 2000 ml autoclaves, (535.2 g, 3.72 mol) 2,4,4,6- tetramethyl -1,3- dioxane, 820 are added
G tetrahydrofurans, the 30.0 g trifluoroacetic acids-phosphomolybdic acid aqueous solution（Trifluoroacetic acid is 1.9 with phosphomolybdic acid mol ratio:1, solution
pH = 5.0 ~ 5.5）, reactor is heated to 97 DEG C, and the rpm of rotor speed 1100 reacts body in 5.0 h, course of reaction
It is that pressure is reached for 0.75 Mpa, tetramethyl -1, the 3- dioxane conversion ratio of gas chromatographic analysis 2,4,4,6- is more than 99 %.Instead
After should terminating, it is water-cooled, stratification, obtains acetaldehyde, 2- methyl isophthalic acids, 3- pentadienes and water, the aqueous phase containing catalyst continues
Set uses lower batch reaction, and oil phase is rectifying to obtain solvent, acetaldehyde and 2- methyl isophthalic acids, 3- pentadienes (298 g, 3.64mol),
Solvent uses lower batch reaction with acetaldehyde set, and 2- methyl isophthalic acids, 3- pentadienes are reacted（3）.
（3）Synthesize ligustral
In 1000ml autoclaves, (298 g, 3.64mol) 2- methyl isophthalic acids, 3- pentadienes, 235.8 g are added（4.2
mol）Methacrylaldehyde, 1g ammonium metavanadates, 1.5 g bismuth nitrates, reactor is heated to 65 DEG C, the rpm of rotor speed 1000, reaction
System pressure finally reaches 0.15Mpa in 3.5 h, course of reaction, gas chromatographic analysis 2- methyl isophthalic acids, 3- pentadiene conversion ratios
More than 98%.After reaction terminates, reaction solution is water-cooled to 20 DEG C, rectifying obtains the ligustral product that content is more than 99.7%
(479.8 g, 3.46 mol), wherein 2,4- dimethyl -3- cyclohexenyl carbaldehydes and 3,5- dimethyl -3- cyclohexenyl group first
Aldehyde, ratio is 4.0: 1, consistent with the natural ligustral ratio extracted in nature；Three-step approach prepares ligustral, and total recovery is
90.5%。
A kind of preparation method of the ligustral of embodiment 8
Comprise the following steps：
（1）Prepare 2,4,4,6- tetramethyl -1,3- dioxane
In the 2000 ml autoclaves with magnetic agitation and temperature controller, 880.9 g acetaldehyde solutions are added（8 mol ,
40%, mass fraction）, 700 g tetrahydrofurans, 60 g butters of tin-ferric chloride aqueous solutionses（Butter of tin rubs with ferric trichloride
You are than being 1:1.5, pH value of solution=5.5-6.0 catalyst contents are regulated and controled by pH）, isobutene is slowly introducing afterwards to system pressure
Power reaches 0.60 Mpa（6.0 mol）.Reactor is heated to 90 DEG C, the rpm of rotor speed 1000,5 h of reaction to system pressure
Power is down to 0.20 Mpa, and gas chromatographic analysis acetaldehyde conversion is more than 98.5%.It is water-cooled, extrusion reaction solution, stratification,
Aqueous phase containing catalyst continues set and uses lower batch reaction, and oil phase is rectifying to obtain solvent, raw material and 2,4,4,6- tetramethyls -1,3-
Dioxane (535.2 g, 3.72 mol).Solvent uses lower batch reaction with raw material set, and dioxane is reacted（2）.
（2）Prepare 2- methyl-1,3-pentylenes
In 2000 ml autoclaves, (535.2 g, 3.72 mol) 2,4,4,6- tetramethyl -1,3- dioxane, 820 are added
G tetrahydrofurans, the 30.0 g trifluoroacetic acids-phosphomolybdic acid aqueous solution（Trifluoroacetic acid is 1.9 with phosphomolybdic acid mol ratio:1, solution
pH = 5.0 ~ 5.5）, reactor is heated to 105 DEG C, and the rpm of rotor speed 1100 reacts body in 5.0 h, course of reaction
It is that pressure is reached for 0.8 Mpa, tetramethyl -1, the 3- dioxane conversion ratio of gas chromatographic analysis 2,4,4,6- is more than 99 %.Instead
After should terminating, it is water-cooled, stratification, obtains acetaldehyde, 2- methyl isophthalic acids, 3- pentadienes and water, the aqueous phase containing catalyst continues
Set uses lower batch reaction, and oil phase is rectifying to obtain solvent, acetaldehyde and 2- methyl isophthalic acids, 3- pentadienes (298 g, 3.64mol),
Solvent uses lower batch reaction with acetaldehyde set, and 2- methyl isophthalic acids, 3- pentadienes are reacted（3）.
（3）Synthesize ligustral
In 1000ml autoclaves, (298 g, 3.64mol) 2- methyl isophthalic acids, 3- pentadienes, 235.8 g are added（4.2
mol）Methacrylaldehyde, 2.3g ammonium metavanadates, 2.5 g bismuth nitrates, reactor is heated to 65 DEG C, the rpm of rotor speed 1000, instead
System pressure in 3.5 h, course of reaction is answered to finally reach 0.15Mpa, gas chromatographic analysis 2- methyl isophthalic acids, the conversion of 3- pentadienes
Rate is more than 98%.After reaction terminates, reaction solution is water-cooled to 20 DEG C, rectifying obtains the ligustral product that content is more than 99.7%
(479.8 g, 3.46 mol), wherein 2,4- dimethyl -3- cyclohexenyl carbaldehydes and 3,5- dimethyl -3- cyclohexenyl group first
Aldehyde, ratio is 4.0: 1, consistent with the natural ligustral ratio extracted in nature；Three-step approach prepares ligustral, and total recovery is
89.6%。
The preparation method of ligustral described in 1-8 of the embodiment of the present invention, 2,4- dimethyl -3- cyclohexenyl carbaldehydes and 3,5- bis-
Methyl -3- cyclohexenyl carbaldehydes, ratio is 3.95-4.05：1；Three-step approach prepares ligustral, and total recovery is 87-90.5%；Wherein
Embodiment 6-8 is preferred embodiment, and three-step approach prepares ligustral, and total recovery is 89-90.5%.
2,4- dimethyl -3- cyclohexenyl carbaldehydes and 3,5- dimethyl -3- cyclohexenyl carbaldehydes in the present invention, are different with dividing
Structure body.
Unless specifically indicated, ratio of the present invention, is mass ratio, and the percentage is mass percent.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
Art personnel are it should be appreciated that the present invention is not limited to the above embodiments, and described in above-described embodiment and specification is explanation
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (10)
1. a kind of preparation method of ligustral, it is characterised in that：Including preparing 2,4,4,6- tetramethyl -1,3- dioxane, system
Standby 2- methyl-1,3-pentylenes, synthesis ligustral.
2. a kind of preparation method of ligustral according to claim 1, it is characterised in that：The synthesis ligustral, by 2-
Methyl isophthalic acid, 3- pentadienes are mixed with methacrylaldehyde, under catalyst action, carry out Diene-addition reaction, and 2- is worked as in gas-chromatography monitoring
Methyl isophthalic acid, when the conversion ratio of 3- pentadienes is more than 98%, reaction terminates.
3. a kind of preparation method of ligustral according to claim 2, it is characterised in that：The synthesis ligustral, reaction
Temperature is 50 ~ 70 DEG C；Reaction pressure is 0.15~0.45 Mpa；
Reaction time is 2.5-3.5h；The mol ratio of methacrylaldehyde and 2- methyl-1,3-pentylenes is 1.05 ~ 1.25.
4. a kind of preparation method of ligustral according to claim 2, it is characterised in that：The catalyst be silver acetate,
One or more of combinations in bismuth nitrate, acetyl acetone, ammonium metavanadate and cobalt naphthenate；
The catalyst is 0.0002 ~ 0.01 with 2- methyl-1,3-pentylenes and the mass ratio of the quality sum of methacrylaldehyde.
5. a kind of preparation method of ligustral according to claim 1, it is characterised in that：2,4,4,6- tetramethyls of the preparation
Base -1,3- dioxane, isobutene is dissolved in solvent with acetaldehyde, is reacted under catalyst action, gas chromatographic detection
When acetaldehyde conversion is more than 98-98.5%, reaction terminates.
6. a kind of preparation method of ligustral according to claim 5, it is characterised in that：
The catalyst is trifluoroacetic acid, trifluoromethayl sulfonic acid, butter of tin, ferric trichloride, zinc chloride, indium trichloride, sulfuric acid
The aqueous solution of one or more of mixing in hydrogen sodium, potassium acid sulfate, pH scopes are 4.0 ~ 6.0.
7. a kind of preparation method of ligustral according to claim 5, it is characterised in that：
The mass ratio of the solvent and aqueous catalyst solution is 11.5-17.5:1；The mol ratio of the isobutene and acetaldehyde is 0.5
~ 1.2；The mass ratio of the isobutene and solvent is 0.01 ~ 0.1.
8. a kind of preparation method of ligustral according to claim 1, it is characterised in that：Preparation the 2- methyl isophthalic acids, 3-
Pentadiene, 2,4,4,6- tetramethyl -1,3- dioxane are diluted with solvent, water-soluble in certain temperature, pressure and catalyst
Under the conditions of liquid, occur open loop cracking reaction, the conversion ratio of tetramethyl -1, the 3- dioxane of gas chromatographic detection 2,4,4,6->99-
When 99.55%, after reaction terminates.
9. a kind of preparation method of ligustral according to claim 8, it is characterised in that：Preparation the 2- methyl isophthalic acids, 3-
Pentadiene, reaction temperature is 80 ~ 140 DEG C；Reaction pressure is 0.25 ~ 0.85 Mpa；The catalyst is nitric acid, trifluoro second
It is one or more of in acid, aluminum sulfate, ferric nitrate, phosphomolybdic acid, silico-tungstic acid, trifluoromethayl sulfonic acid copper, trifluoromethayl sulfonic acid scandium
The aqueous solution, pH scopes are 4.0 ~ 6.5.
10. a kind of preparation method of ligustral according to claim 8, it is characterised in that：Preparation the 2- methyl isophthalic acids, 3-
The mass ratio of pentadiene, 2,4,4,6- tetramethyl -1,3- dioxane and aqueous catalyst solution is：17.8-24.6:1；2,4,4,
The mass ratio of 6- tetramethyl -1,3- dioxane and solvent is 0.1 ~ 1.0.
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