CN109651118A - The preparation method of a plant ketone - Google Patents
The preparation method of a plant ketone Download PDFInfo
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- CN109651118A CN109651118A CN201811595250.9A CN201811595250A CN109651118A CN 109651118 A CN109651118 A CN 109651118A CN 201811595250 A CN201811595250 A CN 201811595250A CN 109651118 A CN109651118 A CN 109651118A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C45/72—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 reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—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 reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
The features such as present invention provides a kind of preparation method of new plant ketone, and this method has preparation cost low, green non-pollution.The preparation method provided by the invention for planting ketone, method Buddhist nun aldehyde is contacted with hydrogen carries out hydrogenation；Hydrogenation reaction product and acetone carry out aldol reaction under the catalysis of nitrogenous organic base；The plant ketone is made in hydrogenated reaction to aldol reaction product again.
Description
Technical field
The invention belongs to organic chemical synthesis fields, and the preparation method of ketone is planted more particularly, to one kind.
Background technique
Plant the important intermediate that ketone is synthesising complex E main ring.Meanwhile the but important centre of phytol, pristane
Body.Therefore, prospects for commercial application is wide.
The synthesis technology for planting ketone at present is broadly divided into two kinds:
Synthetic route 1/2:
1) geranyl acetone ethynylation obtains dehydrogenation nerolidol, then partial hydrogenation in the presence of Lindlar is catalyzed,
Then the derivative of the ester of acetoacetate is formed with diene reactive ketone, the ester being subsequently formed is reset to obtain through Carroll
Farnesyl acetone, finally hydrogenation obtains phytol ketone；
2) geranyl acetone is reacted with vinyl magnesium halide progress vinylation, then obtains farnesyl with diene reactive ketone
Acetone, finally hydrogenation obtain planting ketone.
Referred in Chinese patent CN1393435A with 6,10- dimethyl -2-, 11 carbon ketone be raw material, in catalyst
In the presence of its with acetylene reaction obtain -3 alcohol of 3,7,11- trimethyl, 12 carbon -1- alkynes, obtain 3,7,11- carrying out partial hydrogenation
- 3 alcohol of 12 carbon -1- alkene of trimethyl；Though being able to achieve the preparation of nerolidol in the invention, partial hydrogenation yield is lower, and deposits
Situation is separated in stock Product by-product difficulty, leads to higher production cost；It reacts simultaneously in carroll to be based on acetoacetic ester
Equimolar amounts uses alkali, forms a large amount of salt, needs to post-process, lead to higher cost.
And use vinyl magnesium halide very sensitive to water and oxygen, it needs to pay special attention to operation item in process of production
Part, operating environment.Meanwhile the magnesium salts of equimolar amounts is generated in reaction process, industrial production cost is high.
Synthetic route 3:
Using method Buddhist nun aldehyde as raw material, with acetone aldol reaction occurs for the route, obtains phytol ketone carrying out hydrogenation.
The third synthetic route step is few, and raw material is relatively stable, and Chinese patent CN97111523.0 is by 6,7-dihydro spiceleafs
Alcohol prepares hexahydro farnesyl acetone and new intermediate, wherein referring to 10,11- dihydro method Buddhist nun aldehyde and acetone are acted in sodium methoxide
Lower progress Claisen-Schmitt condensation reaction, then carry out Conventional catalytic and hydrogen is added to obtain planting ketone, since raw material occurs in system
The side reactions such as polymerization, cause the step reaction yield lower, and only 49%.Yield is low, and is unable to continuous production；Chinese patent
The production method of CN03817009.4 tetrahydrogeranylacetone, it is noted that citral and acetone aldol condensation, subsequent hydrogenation
Tetrahydrogeranylacetone is prepared, which makees catalyst using alkali metal hydroxide, due to aldol reaction liquid byproduct water
Lead to catalyst loss, while the alkali in product also needs sour neutralization, brings the cumbersome of post-processing.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of new plant ketone, this method has preparation cost low, green nothing
Pollution, and the features such as product yield high.
The preparation method provided by the invention for planting ketone, first method Buddhist nun aldehyde are contacted with hydrogen carries out hydrogenation, is hydrogenated
Method Buddhist nun's aldehyde；The hydrogenation reaction product and acetone carry out aldol reaction under the catalysis of nitrogenous organic base, form dehydrogenation and plant ketone；
The plant ketone is made in hydrogenated reaction to the aldol reaction product again.
As a kind of specific embodiment, the hydrogenation carries out in the presence of a hydrogenation catalyst；The hydrogenation is urged
Agent can be using various hydrogenation catalysts commonly used in this field, it is preferable to use palladium-carbon catalyst, can use commercially available business
Palladium-carbon catalyst can be common various specifications, such as Palladium Content in Catalyst is 0.5-10wt% etc..
Preparation method provided by the invention, the hydrogenation reaction and aldol reaction being related to are preferably disposed in same reactor
It carries out, and method Buddhist nun aldehyde first carries out hydrogenation, then carries out aldol reaction, can avoid polymerization side reactions, i.e., using this
Inventive method avoids polymerization reaction of the reaction intermediate under alkali environment.
It is equipped in preferred embodiment, in the reactor anti-for catalytic first hydrogenation of method Buddhist nun aldehyde and hydrogen
Answer area, be filled with hydrogenation catalyst in first hydrogenation reaction zone, reaction product obtained in first hydrogenation reaction zone from
Subsequent reactions are participated in again after opening the first hydrogenation reaction zone, prevent back-mixing, that is, prevent nitrogenous organic base catalyst from entering the first hydrogenation
In reaction zone.
In preferred embodiment, the reactor is tubular reactor, is from top to bottom equipped in the tubular reactor
More than two reaction zones, wherein first hydrogenation reaction zone is located at top layer；It is at least anti-in lowest level in remaining reaction area
It answers and is filled with hydrogenation catalyst in area；The feeding inlet of acetone and nitrogenous organic base, and the feeding inlet are equipped on tubular reactor
Below first hydrogenation reaction zone.
Preparation method provided by the invention can realize continuous production, be produced using continuous operation.It is preferred real
It applies in scheme, reaction raw materials are entered in the tubular reactor using continuous feed mode, are contained obtained in tubular reactor
The end reaction product for planting ketone is discharged using continuous discharge mode；The generation of side reaction can be reduced using continuous production, and is easy to
Realize industrialized production.
In certain preferred embodiments, the reaction time in tubular reactor is 100-300min.
In certain preferred embodiments, the preparation method specifically comprises the following steps:
Method Buddhist nun's aldehyde is added in reactor, reactor is added after preferably mixing method Buddhist nun aldehyde and excessive propanone；First
Hydrogenation reaction zone method Buddhist nun aldehyde contacts with hydrogen and carries out hydrogenation under hydrogenation catalyst effect, obtains hydrogenization method Buddhist nun's aldehyde；Hydrogen
Change reaction product leaves the first hydrogenation reaction zone and acetone and carries out aldol reaction, aldol condensation under nitrogenous organic base catalysis
Reaction product is contacted with the hydrogen in reactor carries out hydrogenation under hydrogenation catalyst effect again.
The key reaction process of preparation method of the present invention is as follows:
In certain preferred embodiments, the temperature control of the reactor is 25-120 DEG C, preferably 45-100 DEG C；Pressure
It is preferably controlled to 0.5MPa-3MPa (gauge pressure), more preferable 1.5-2.0MPa (gauge pressure).
In certain preferred embodiments, the nitrogenous organic base is selected from one of trimethylamine, n,N-Dimethylformamide
Or two kinds.Present inventor's discovery uses nitrogenous organic base, is avoided that in the prior art and is existed and urged using solid catalyst
The problem of agent is lost and brings therefrom, and it is easy blocking reactor according to inorganic base, cause reaction conversion ratio to reduce.
In certain preferred embodiments, in reaction system, total dosage of acetone is the 100-500% of method Buddhist nun aldehyde quality, excellent
Select 200-400%；Acetone both can be used as reaction raw materials, can also be used as the effect of solvent.The total dosage of acetone includes herein
As the sum of reaction raw materials and the dosage of solvent.
And/or the dosage of the nitrogenous organic base is the 1%-10% of method Buddhist nun aldehyde quality.
In certain preferred embodiments, the method Buddhist nun aldehyde is added in reaction system in the form of method Buddhist nun's aldehyde solution, and/or,
The nitrogenous organic base is added in reaction system in the form of nitrogenous organic base solution；The method Buddhist nun aldehyde solution described nitrogenous has
Solvent in machine aqueous slkali is selected from the combination of one or more of alcohols, ketones solvent, preferably acetone.
In certain preferred embodiments, by the aldol reaction product again it is hydrogenated react obtain containing plant ketone
Final product reaction solution carry out gas liquid separating filtering, obtained hydrogen is back in reaction system (the original as hydrogenation
Material), and reaction solution can by flash 0.01-0.1MPa vacuum degree under, obtain phytol ketone product, the light component flashed can
It is back to system.
Technical solution provided by the invention has the following beneficial effects:
The features such as a kind of preparation method of new plant ketone provided by the invention, has preparation cost low, green non-pollution；And
Continuous production can be used in the preparation method, carries out in same reactor.Using nitrogenous organic base catalyst, solve existing
In technology use curing catalysts when, because aldol condensation generate water due to cause solid catalyst to be lost the problem of.Experiment shows
The plant ketone high income of method preparation provided by the invention, can reach 90% or more, purity can reach 95% or more.
Detailed description of the invention
Fig. 1 is the reaction system schematic diagram in some embodiments；1 is the first hydrogenation reaction zone in figure.
Specific embodiment
For a better understanding of the technical solution of the present invention, below with reference to the embodiment content that the present invention is further explained,
But the contents of the present invention are not limited only to following embodiment.
" % " involved in hereafter refers both to mass percent or mass content if not specified.
In following embodiment or comparative example, used acetone, ethyl alcohol, trimethylamine, n,N-Dimethylformamide are analysis
It is pure, it is provided by western Gansu Province chemistry；Raw material method Buddhist nun's aldehyde, 98%, it is provided by Aladdin；Catalyst palladium carbon (palladium content 5wt%) is by West Asia
Reagent provides；Agents useful for same unless otherwise indicated, is not specially treated.
In following embodiment or comparative example, not specified specific experiment operation is the operation of this field routine experiment.
In following embodiment or comparative example, analytical conditions for gas chromatography used is as follows:
Chromatographic column: Agilent WAX (specification is 30m × 0.32mm × 0.25mm)；
Injector temperature: 230 DEG C；
Split ratio: 30:1；
Column flow: 1.5ml/min；
Column temperature: since 180 DEG C, 230 DEG C is increased to 5 DEG C/min, keeps 15min；
Detector temperature: 280 DEG C, H2Flow: 35ml/min, air mass flow: 350ml/min.
Embodiment 1
At 30 DEG C of temperature, acetone, method Buddhist nun aldehyde (98%) are added in method Buddhist nun's aldehyde storage tank, obtaining mass fraction is 20%
Method Buddhist nun's aldehyde acetone soln；
Acetone, trimethylamine are added in organic base tank, obtains 5% organic alkali solution of mass fraction；
Method Buddhist nun's aldehyde acetone soln enters the first hydrogenation reaction zone 1 of tubular reactor by metering pump, which includes
Palladium-carbon catalyst, the charging rate of method Buddhist nun's aldehyde are 300Kg/h, and hydrogen enters tubular reactor by flowmeter, and Hydrogen Vapor Pressure is
2MPa controls the reaction temperature in reactor at 45-50 DEG C；Organic alkali solution passes through metering pump (position at tubular reactor 1/3
Below the first hydrogenation reactor) enter tubular reactor, charging rate 60kg/h, reaction time 100min；Method
In the first hydrogenation reaction zone and hydrogen hydrogenation, the reaction product of the first hydrogenation reaction zone flows downward Buddhist nun's aldehyde, anti-with lower section
Acetone in area, organic base haptoreaction are answered, obtained Aldol Condensation Products continue to contact in palladium carbon with the hydrogen in reactor
Hydrogenation occurs under catalyst.
After reaction, the reaction solution of reactor bottom enters gas-liquid separator, and the hydrogen isolated is back to gas holder and (can return
With into reactor), liquid is after flash tank, and isolated light component enters UF membrane water removal, and heavy distillat is that product enters production
Product storage tank, the organic base that light component obtains after UF membrane enter organic base storage tank.It obtains planting ketone 70.56kg/h (gas-chromatography
Purity assay is 97%) yield 95.5%.
In the present embodiment, the total dosage of acetone is the 400% of method Buddhist nun aldehyde quality；The dosage of nitrogenous organic base is method Buddhist nun aldehyde quality
5%.
Product nmr analysis result is as follows:
1H NMR (300MHz, CDCl3): δ 0.83-0.88 (m, 12H), 1.03-1.64 (m, 19H), 2.13 (s, 3H),
2.40 (t, J=7.4Hz, 2H)；
13C NMR(75MHz,CDCl3)δ19.5,19.6,21.3,22.5,22.6,24.1, 24.7,27.9,29.6,
32.6,32.7,36.4,37.1,37.2,37.3,39.3,44.0, 208.8.
Embodiment 2
At 30 DEG C of temperature, acetone, method Buddhist nun aldehyde (98%) are added in method Buddhist nun's aldehyde storage tank, obtaining mass fraction is 20%
Method Buddhist nun's aldehyde acetone soln；
Acetone, trimethylamine are added in organic base tank, obtains the organic alkali solution of mass fraction 10%；
Method Buddhist nun's aldehyde acetone soln enters the first hydrogenation reaction zone of tubular reactor by metering pump, which includes palladium
The charging rate of C catalyst, method Buddhist nun's aldehyde is 300Kg/h, and hydrogen enters tubular reactor into overcurrent meter, and Hydrogen Vapor Pressure is
1.5MPa controls reaction temperature at 60-65 DEG C；Organic base (it is anti-to be located at the first hydrogenation at tubular reactor 1/3 by metering pump
Answer below device) enter tubular reactor, charging rate 40kg/h, charging rate is that reaction time is 200min；Method Buddhist nun
Aldehyde flows downward, reacts with lower section in the first hydrogenation reaction zone and hydrogen hydrogenation, the reaction product of the first hydrogenation reaction zone
Acetone, organic base haptoreaction in area, obtained Aldol Condensation Products continue to contact with the hydrogen in reactor urges in palladium carbon
Agent catalysis is lower to occur hydrogenation.
After reaction, the reaction solution of reactor bottom enters gas-liquid separator, and hydrogen is back to gas holder, and liquid is through flash tank
Afterwards, isolated light component enters UF membrane water removal, and heavy distillat is that product enters product storage tank, and light component obtains after UF membrane
Organic base enter organic base storage tank.It obtains product and enters product storage tank.Obtaining plant ketone 69.67kg/h, (gas chromatographic analysis is pure
Degree is 97%) yield 94.3%.
In the present embodiment, the total dosage of acetone is the 400% of method Buddhist nun aldehyde quality；The dosage of nitrogenous organic base is method Buddhist nun aldehyde quality
6.67%.
Embodiment 3
At 30 DEG C of temperature, acetone, method Buddhist nun aldehyde (98%) are added in method Buddhist nun's aldehyde storage tank, obtaining mass fraction is 40%
Method Buddhist nun's aldehyde acetone soln；
Acetone, n,N-Dimethylformamide are added in organic base tank, obtains 6% organic alkali solution of mass fraction；
Method Buddhist nun's aldehyde acetone soln enters the first hydrogenation reaction zone of tubular reactor by metering pump, which includes palladium
The charging rate of C catalyst, method Buddhist nun's aldehyde is 150Kg/h, and hydrogen enters tubular reactor into overcurrent meter, and Hydrogen Vapor Pressure is
2.5MPa controls reaction temperature at 100-110 DEG C；Organic base (is located at the first hydrogenation at tubular reactor 1/3 by metering pump
Below reactor) enter tubular reactor, charging rate 40kg/h, reaction time 150min；Method Buddhist nun's aldehyde is first
Hydrogenation reaction zone and hydrogen hydrogenation, the reaction product of the first hydrogenation reaction zone flows downward, with third in the reaction zone of lower section
Ketone, organic base haptoreaction, obtained Aldol Condensation Products continue to contact with the hydrogen in reactor to be catalyzed in palladium-carbon catalyst
Lower generation hydrogenation.
After reaction, the reaction solution of reactor bottom enters gas-liquid separator, and hydrogen is back to gas holder, and liquid is through flash tank
Light component enters UF membrane water removal afterwards, and heavy distillat is that product enters product storage tank, and light component obtains organic after UF membrane
Alkali enters organic base storage tank.It obtains product and enters product storage tank.Obtain planting ketone 69.425kg/h that (gas chromatographic analysis purity is
96%), yield 93%.
In the present embodiment, the total dosage of acetone is the 150% of method Buddhist nun aldehyde quality；The dosage of nitrogenous organic base is method Buddhist nun aldehyde quality
4%.
Embodiment 4
At 30 DEG C of temperature, acetone, method Buddhist nun aldehyde (98%) are added in method Buddhist nun's aldehyde storage tank, obtaining mass fraction is 50%
Method Buddhist nun's aldehyde acetone soln；
Acetone, n,N-Dimethylformamide are added in organic base tank, obtains 2% organic alkali solution of mass fraction；
Method Buddhist nun's aldehyde acetone soln enters the first hydrogenation reaction zone of tubular reactor by metering pump, which includes palladium
The charging rate of C catalyst, method Buddhist nun's aldehyde is 160Kg/h, and hydrogen enters tubular reactor into overcurrent meter, and Hydrogen Vapor Pressure is
2.5MPa controls reaction temperature at 100-110 DEG C；Organic base (is located at the first hydrogenation at tubular reactor 1/3 by metering pump
Below reactor) enter tubular reactor, charging rate 40kg/h, reaction time 150min；Method Buddhist nun's aldehyde is first
Hydrogenation reaction zone and hydrogen hydrogenation, the reaction product of the first hydrogenation reaction zone flows downward, with third in the reaction zone of lower section
Ketone, organic base haptoreaction, obtained Aldol Condensation Products continue to contact with the hydrogen in reactor to be catalyzed in palladium-carbon catalyst
Lower generation hydrogenation.
After reaction, the reaction solution of reactor bottom enters gas-liquid separator, and hydrogen is back to gas holder, and liquid is through flash tank
Afterwards, isolated light component enters UF membrane water removal, and heavy distillat is that enter product storage tank light component organic after UF membrane for product
Alkali enters organic base storage tank.It obtains product and enters product storage tank.Obtain planting ketone 90.28kg/h that (gas chromatographic analysis purity is
96%), yield 93%.
In the present embodiment, the total dosage of acetone is the 100% of method Buddhist nun aldehyde quality；The dosage of nitrogenous organic base is method Buddhist nun aldehyde quality
1%.
Embodiment 5
At 30 DEG C of temperature, acetone, method Buddhist nun aldehyde (98%) are added in method Buddhist nun's aldehyde storage tank, obtaining mass fraction is 40%
Method Buddhist nun's aldehyde acetone soln；
Acetone, n,N-Dimethylformamide are added in organic base tank, obtains 15% organic alkali solution of mass fraction；
Method Buddhist nun's aldehyde acetone soln enters the first hydrogenation reaction zone of tubular reactor by metering pump, which includes palladium
The charging rate of C catalyst, method Buddhist nun's aldehyde is 150Kg/h, and hydrogen enters tubular reactor into overcurrent meter, and Hydrogen Vapor Pressure is
3.0MPa controls reaction temperature at 110-120 DEG C；Organic base (is located at the first hydrogenation at tubular reactor 1/3 by metering pump
Below reactor) enter tubular reactor, charging rate 40kg/h, reaction time 150min；Method Buddhist nun's aldehyde is first
Hydrogenation reaction zone and hydrogen hydrogenation, the reaction product of the first hydrogenation reaction zone flows downward, with third in the reaction zone of lower section
Ketone, organic base haptoreaction, obtained Aldol Condensation Products continue to contact with hydrogen middle in reactor to be catalyzed in palladium-carbon catalyst
Lower generation hydrogenation.
After reaction, the reaction solution of reactor bottom enters gas-liquid separator, and hydrogen is back to gas holder, and liquid is through flash tank
Afterwards, light component enters UF membrane water removal, and heavy distillat is that product enters the organic base entrance after UF membrane of product storage tank light component
Organic base storage tank.It obtains product and enters product storage tank.It obtains planting ketone 69.70kg/h (gas chromatographic analysis purity is 95%), receive
Rate is 92.4%.
In the present embodiment, the total dosage of acetone is the 150% of method Buddhist nun aldehyde quality；The dosage of nitrogenous organic base is method Buddhist nun aldehyde quality
10%.
Embodiment 6
At 30 DEG C of temperature, acetone, method Buddhist nun aldehyde (98%) are added in method Buddhist nun's aldehyde storage tank, obtaining mass fraction is 40%
Method Buddhist nun's aldehyde acetone soln；
Acetone, n,N-Dimethylformamide are added in organic base tank, obtains 6% organic alkali solution of mass fraction；
Method Buddhist nun's aldehyde acetone soln enters the first hydrogenation reaction zone of tubular reactor by metering pump, which includes palladium
The charging rate of C catalyst, method Buddhist nun's aldehyde is 150Kg/h, and hydrogen enters tubular reactor into overcurrent meter, and Hydrogen Vapor Pressure is
0.5MPa controls reaction temperature at 25-30 DEG C；Organic alkali solution (is located at the first hydrogen at tubular reactor 1/3 by metering pump
Change below reactor) enter tubular reactor, charging rate 40kg/h, reaction time 150min；Method Buddhist nun aldehyde is
One hydrogenation reaction zone and hydrogen hydrogenation, the reaction product of the first hydrogenation reaction zone flows downward, in the reaction zone of lower section
Acetone, organic base haptoreaction, obtained Aldol Condensation Products continue to contact with the hydrogen in reactor urges in palladium-carbon catalyst
Change lower generation hydrogenation.
After reaction, the reaction solution of reactor bottom enters gas-liquid separator, and hydrogen is back to gas holder, and liquid is through flash tank
Light component enters UF membrane water removal afterwards, and heavy distillat is that product enters product storage tank, and light component organic base after UF membrane enters
Organic base storage tank.It obtains product and enters product storage tank.It obtains planting ketone 68.04kg/h (gas chromatographic analysis purity is 95%), receive
Rate is 90.2%.
In the present embodiment, the total dosage of acetone is the 150% of method Buddhist nun aldehyde quality；The dosage of nitrogenous organic base is method Buddhist nun aldehyde quality
4%.
Comparative example 1
At 30 DEG C of temperature, acetone, method Buddhist nun aldehyde (98%) are added in method Buddhist nun's aldehyde storage tank, obtaining mass fraction is 20%
Method Buddhist nun's aldehyde acetone soln；Method Buddhist nun's aldehyde acetone soln enters the tubular reactor containing palladium-carbon catalyst by metering pump, method Buddhist nun's aldehyde
Charging rate is 300Kg/h, and hydrogen enters tubular reactor into overcurrent meter, and Hydrogen Vapor Pressure 2.5MPa controls reaction temperature
At 100-110 DEG C, 5% sodium hydroxide alkali tank enters tubular reactor, charging rate by metering pump at tubular reactor 1/3
For 60kg/h, reaction time 150min, enter gas-liquid separator after reaction, hydrogen is back to gas holder, and liquid enters
UF membrane water removal, reaction solution progress letter steaming obtain product and enter product storage tank.It obtains planting ketone 164.6kg/h (gas chromatographic analysis
Purity is 59.3%) yield 56%.
In this comparative example, the total dosage of acetone is the 400% of method Buddhist nun aldehyde quality；The dosage of sodium hydroxide is method Buddhist nun aldehyde quality
5%.
Comparative example 2
Referring to 1 preparation method of embodiment, the difference is that nitrogenous organic base trimethylamine is replaced with organic base sodium acetate.
It obtains planting ketone 164.6kg/h (purity 77.4%), yield 75%.
It will be understood by those skilled in the art that under the introduction of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (10)
1. the preparation method of a plant ketone, which is characterized in that method Buddhist nun aldehyde is contacted with hydrogen carries out hydrogenation, hydrogenation reaction product
Aldol reaction is carried out under the catalysis of nitrogenous organic base with acetone, hydrogenated reaction is made aldol reaction product again
The plant ketone.
2. preparation method according to claim 1, which is characterized in that the hydrogenation is in the presence of a hydrogenation catalyst
It carries out；It is preferred that the hydrogenation catalyst is palladium-carbon catalyst.
3. preparation method according to claim 2, which is characterized in that hydrogenation reaction involved in the preparation method and hydroxyl
Aldehyde condensation reaction carries out in same reactor；
Preferably, it is equipped in the reactor for method Buddhist nun aldehyde and catalytic first hydrogenation reaction zone of hydrogen, first hydrogen
Change in reaction zone and be filled with hydrogenation catalyst, reaction product obtained in first hydrogenation reaction zone leaves the first hydrogenation
Subsequent reactions are participated in behind area again.
4. preparation method according to claim 3, which is characterized in that the reactor is tubular reactor, the tubular type
More than two reaction zones are from top to bottom equipped in reactor, wherein first hydrogenation reaction zone is located at top layer；It is anti-at remaining
It answers in area, is at least filled with hydrogenation catalyst in lowest level reaction zone；Acetone and nitrogenous organic is equipped on tubular reactor
The feeding inlet of alkali, and the feeding inlet is located at below first hydrogenation reaction zone.
5. the preparation method according to claim 4, which is characterized in that described in reaction raw materials are entered using continuous feed mode
In tubular reactor, discharged containing the end reaction product for planting ketone using continuous discharge mode obtained in tubular reactor；
Preferably, the reaction time in tubular reactor is 100-300min.
6. preparation method according to claim 5, which comprises the steps of:
Method Buddhist nun's aldehyde is added in reactor, contacted in the first hydrogenation reaction zone with hydrogen and carries out hydrogen under hydrogenation catalyst effect
Change reaction；It is anti-that hydrogenation reaction product leaves the first hydrogenation reaction zone and acetone the progress aldol condensation under nitrogenous organic base catalysis
It answers, aldol reaction product is contacted with the hydrogen in reactor carries out hydrogenation under hydrogenation catalyst effect again.
7. according to the described in any item preparation methods of claim 3-6, which is characterized in that the temperature of the reactor, which controls, is
25-120 DEG C, preferably 45-100 DEG C；Pressure is preferably controlled to 0.5MPa-3MPa (gauge pressure), more preferable 1.5-2.0MPa (gauge pressure).
8. preparation method according to claim 1-7, which is characterized in that the nitrogenous organic base is selected from front three
One or both of amine, N,N-dimethylformamide.
9. preparation method according to claim 1-8, which is characterized in that in reaction system, total dosage of acetone
For the 100-500% of method Buddhist nun's aldehyde quality, preferably 200-400%；
And/or the dosage of the nitrogenous organic base is the 1%-10% of method Buddhist nun aldehyde quality.
10. -9 described in any item preparation methods according to claim 1, which is characterized in that
The method Buddhist nun aldehyde is added in reaction system in the form of method Buddhist nun's aldehyde solution, and/or, the nitrogenous organic base is with nitrogenous organic
The form of aqueous slkali is added in reaction system；Solvent in the method Buddhist nun aldehyde solution or the nitrogenous organic base solution is selected from alcohol
The combination of one or more of class, ketones solvent, preferably acetone；
Preferably, by the aldol reaction product, the hydrogenated obtained reaction solution that reacts carries out gas liquid separating filtering again,
Obtained hydrogen is back in reaction system.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5673005A (en) * | 1979-11-16 | 1981-06-17 | Kuraray Co Ltd | Fungicide for agriculture and horticulture containing terpene carbonyl compound as effective component |
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| CN102531861A (en) * | 2012-01-05 | 2012-07-04 | 淮海工学院 | Novel method for preparing 5-ethyl-2-nonanone |
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| CN107200701A (en) * | 2017-07-03 | 2017-09-26 | 江苏威格瑞斯化工有限公司 | A kind of method of synthesizing cyclohexene type herbicides key intermediate |
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| JPS5673005A (en) * | 1979-11-16 | 1981-06-17 | Kuraray Co Ltd | Fungicide for agriculture and horticulture containing terpene carbonyl compound as effective component |
| CN1172795A (en) * | 1996-05-10 | 1998-02-11 | 巴斯福股份公司 | Preparation of hexahydrofarnesylacetone form 6, 7 -dihydrogeraniol, and novel intermadiates therefor |
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| JP2000191579A (en) * | 1998-12-25 | 2000-07-11 | Kuraray Co Ltd | Production of terpene-type ketone |
| CN1668564A (en) * | 2002-07-15 | 2005-09-14 | 巴斯福股份公司 | Method for the production of tetrahydrogeranylacetone |
| CN1894190A (en) * | 2003-12-15 | 2007-01-10 | 巴斯福股份公司 | Method for the production of tetrahydrogeranylacetone |
| CN102531861A (en) * | 2012-01-05 | 2012-07-04 | 淮海工学院 | Novel method for preparing 5-ethyl-2-nonanone |
| WO2017098050A1 (en) * | 2015-12-11 | 2017-06-15 | Dsm Ip Assets B.V. | Process for the manufacture of 6,10,14-trimethylpentadecan-2-one, isophytol and alpha-tocopherol |
| CN107200701A (en) * | 2017-07-03 | 2017-09-26 | 江苏威格瑞斯化工有限公司 | A kind of method of synthesizing cyclohexene type herbicides key intermediate |
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