CN103755538A - Synthetic method of dihydrogen geranyl acetone and dihydrogen nicky acetone - Google Patents
Synthetic method of dihydrogen geranyl acetone and dihydrogen nicky acetone Download PDFInfo
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- CN103755538A CN103755538A CN201410009481.2A CN201410009481A CN103755538A CN 103755538 A CN103755538 A CN 103755538A CN 201410009481 A CN201410009481 A CN 201410009481A CN 103755538 A CN103755538 A CN 103755538A
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Abstract
The invention relates to a Carroll reaction, and particularly relates to a synthetic method of dihydrogen geranyl acetone and dihydrogen nicky acetone. The method comprises the following steps: reacting dihydro linalool or dihydrogen nerolidol taken as a raw material and aluminium isopropoxide taken as a catalyst with methyl acetoacetate or ethyl acetoacetate to generate the dihydrogen geranyl acetone or dihydrogen nicky acetone, simultaneously generating carbon dioxide and methyl alcohol for treatment. The synthetic method is high in reaction yield, and high in purity, a by-product methanol can be fully recovered, environmental pollution is avoided, production is energy-saving and environment-friendly, meanwhile, the production cost is reduced, a carbon dioxide gas containing a little amount of methanol gas and low-boiling organic impurity gas enters a decarburization furnace to combust in by-product recovery, and the generated heat energy can be supplied to decarboxylic reaction in synthesis, so that heat cyclic utilization is achieved. The collected carbon dioxide is high in purity, and can be directly supplied to the required post, emission of atmosphere is reduced, production is energy-saving and environment-friendly, and meanwhile, the production cost is reduced.
Description
Technical field
The present invention relates to a kind of Karol reaction, relate in particular to the synthetic method of a kind of dihydro geranyl acetone and/or dihydro farnesyl acetone.
Background technology
Dihydro geranyl acetone is very important medicine and chemical intermediate, can prepare Oleum Pelargonii Graveolentis and food flavour etc., be widely used in essence and flavoring agent field, the more important thing is that dihydro geranyl acetone and dihydro farnesyl acetone are the important intermediate of synthesising complex E side chain different vegetable alcohol, vitamin-E is since being found, be widely used in medicine, health care medicinal, the field such as fodder additives and foodstuff additive, because it has the effects such as improving human body and animal body autoimmunity and enhances metabolism, have simultaneously and extend the effects such as old and feeble, therefore, the synthetic technology of dihydro geranyl acetone and dihydro farnesyl acetone enjoys people's concern.
CN1894190A (2007-1-10) discloses a kind of production method of THGAC, yet does not relate to the synthetic method of dihydro geranyl acetone or dihydro farnesyl acetone.
Summary of the invention
One of object of the present invention is to provide a kind of reaction yield and purity improves and the synthetic method of the dihydro geranyl acetone of production environmental protection.
Two of object of the present invention is to provide a kind of reaction yield and purity improves and the synthetic method of the dihydro farnesyl acetone of production environmental protection.
The first technical purpose of the present invention is achieved by the following technical programs:
The synthetic method of dihydro geranyl acetone, it comprises step successively:
(1) batching: take by weight dihydrolinalool 800-1200 part, aluminum isopropylate 25-35 part, methyl acetoacetate or methyl aceto acetate 700-820 part, standby;
(2) synthetic: described whole dihydrolinalools to be mixed with aluminum isopropylate, be warming up to 160-200 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 1.5-3h synthesizing dihydro geranyl acetone;
(3) by-product recovery: the carbonic acid gas generating during by reaction is cooling with methanol gas, separated, reclaim the methanol liquid of cooling generation, and the carbon dioxide of carrying methanol gas and the low organic impurity gas that boils secretly is introduced in decarbonylation stove, wherein methanol gas and the low organic impurity gas that boils generate carbonic acid gas and steam through burning fully in decarbonylation stove, gas mixture is again by separated, be converted into more than 99% carbon dioxide of purity, introduce the post that needs carbon dioxide.
Chemical equation of the present invention is as follows:
Advantage of the present invention is:
1. dihydrolinalool and methyl acetoacetate or methyl aceto acetate are as Karol reaction raw materials, select especially aluminum isopropylate as catalyzer, proportioning and the control of reacting order of addition(of ingredients), temperature by certain content, obtain high reaction yield and highly purified dihydro geranyl acetone through decarboxylic reaction;
2. by-product carbinol can fully be reclaimed, and avoids environment, and production energy-conserving and environment-protective, have reduced again production cost simultaneously;
3. in by-product recovery, carry a small amount of methanol gas and the low carbon dioxide that boils organic impurity gas secretly and entering the decarboxylic reaction that heat energy that decarbonizing furnace burning produces can supply with when synthetic again and use, realizing thermal cycling utilization;
4. the carbon dioxide purity of collecting during by-product recovery is higher, can directly supply with the post needing, and has reduced the discharge to atmosphere, and production energy-conserving and environment-protective have reduced again production cost simultaneously.
As preferably, described step (1) takes 1000 parts of dihydrolinalools, aluminum isopropylate 28-32 part, methyl acetoacetate or methyl aceto acetate 740-780 part by weight.
As preferably, described step (2) is mixed described whole dihydrolinalools with aluminum isopropylate, be warming up to 165-180 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, is added dropwise to complete follow-up continuous insulation reaction 1.8-2.5h synthesizing dihydro geranyl acetone.
More preferably, described step (2) is mixed described whole dihydrolinalools with aluminum isopropylate, is warming up to 170 ℃ and starts to drip methyl acetoacetate or methyl aceto acetate, is added dropwise to complete follow-up continuous insulation reaction 2h synthesizing dihydro geranyl acetone.
As preferably, the time for adding of described step (2) methyl acetoacetate or methyl aceto acetate is controlled at 2-3h.
As preferably, described step (3) decarbonylation stove comprises for the interior chamber of mixture combustion and is arranged on the described interior outdoor tortuous swirl type heating coil for the mistress to mixture combustion heat supply, the two ends of described interior chamber are respectively arranged with combi inlet port and mixed gas outlet, and described mistress's two ends are respectively arranged with hot oil inlet and hot oil outlet; On described combi inlet port pipeline, be provided with whirlwind-type flameholder; Before described combi inlet port, be provided with solenoid electric valve, before described solenoid electric valve, be provided with for the first T-valve of methanol gas circulation with for oxygen the second T-valve circulation and that communicate with described the first T-valve, before described the first T-valve, be provided with for preventing the gas flame-retardant device of gaseous combustion.
Advantage of the present invention is: add gas flame-retardant device and can prevent that gaseous combustion from causing whole reaction system burning to cause security incident; By the setting on the different valves roads such as T-valve and solenoid electric valve, regulate inflow and the flow of oxygen and methyl alcohol, and whirlwind-type flameholder is set with abundant combustion methanol at the interior chamber inlet of mixture combustion, by deep fat gas mixture heat supply during to burning in mistress's circulation, make methyl alcohol burning reclaim the most effective of carbonic acid gas simultaneously.
The second technical purpose of the present invention is achieved by the following technical programs:
The synthetic method of dihydro farnesyl acetone, it comprises step successively:
(1) batching: take by weight dihydro nerolidol 800-1200 part, aluminum isopropylate 25-35 part, methyl acetoacetate or methyl aceto acetate 700-820 part, standby;
(2) synthetic: described whole dihydro nerolidols to be mixed with aluminum isopropylate, be warming up to 160-200 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 1.5-3h synthesizing dihydro farnesyl acetone;
(3) by-product recovery: the carbonic acid gas generating during by reaction is cooling with methanol gas, separated, reclaim the methanol liquid of cooling generation, and the carbon dioxide of carrying methanol gas and the low organic impurity gas that boils secretly is introduced in decarbonylation stove, wherein methanol gas and the low organic impurity gas that boils generate carbonic acid gas and steam through burning fully in decarbonylation stove, gas mixture is again by separated, be converted into more than 99% carbon dioxide of purity, introduce the post that needs carbon dioxide.
Chemical equation of the present invention is as follows:
Why the present invention mentions the synthetic of dihydro geranyl acetone and dihydro farnesyl acetone simultaneously, because the reaction mechanism of the two is identical, using dihydrolinalool and dihydro nerolidol respectively as raw material, under catalysis at aluminum isopropylate as catalyzer, and there is CARROLL rearrangement (Karol rearrangement) reaction in methyl acetoacetate (or methyl aceto acetate), through decarboxylic reaction, synthesize respectively target product geranyl acetone and farnesyl acetone, simultaneously methanol and carbon dioxide again.
Advantage of the present invention is:
1. dihydro nerolidol and methyl acetoacetate or methyl aceto acetate are as Karol reaction raw materials, select especially aluminum isopropylate as catalyzer, proportioning and the control of reacting order of addition(of ingredients), temperature by certain content, obtain high reaction yield and highly purified dihydro farnesyl acetone through decarboxylic reaction;
2. by-product carbinol can fully be reclaimed, and avoids environment, and production energy-conserving and environment-protective, have reduced again production cost simultaneously;
3. in by-product recovery, carry a small amount of methanol gas and the low carbon dioxide that boils organic impurity gas secretly and entering the decarboxylic reaction that heat energy that decarbonizing furnace burning produces can supply with when synthetic again and use, realizing thermal cycling utilization;
4. the carbon dioxide purity of collecting during by-product recovery is higher, can directly supply with the post needing, and has reduced the discharge to atmosphere, and production energy-conserving and environment-protective have reduced again production cost simultaneously.
As preferably, described step (1) takes 1000 parts of dihydro nerolidols, aluminum isopropylate 28-32 part, methyl acetoacetate 740-780 part by weight.
As preferably, described step (2) is mixed described whole dihydro nerolidols with aluminum isopropylate, be warming up to 165-180 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, is added dropwise to complete follow-up continuous insulation reaction 1.8-2.5h synthesizing dihydro farnesyl acetone.
More preferably, described step (2) is mixed described whole dihydro nerolidols with aluminum isopropylate, be warming up to 180 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, is added dropwise to complete follow-up continuous insulation reaction 2h synthesizing dihydro farnesyl acetone.
As preferably, the time for adding of described step (2) methyl acetoacetate or methyl aceto acetate is controlled at 2-3h.
As preferably, described step (3) decarbonylation stove comprises for the interior chamber of mixture combustion and is arranged on the described interior outdoor tortuous swirl type heating coil for the mistress to mixture combustion heat supply, the two ends of described interior chamber are respectively arranged with combi inlet port and mixed gas outlet, and described mistress's two ends are respectively arranged with hot oil inlet and hot oil outlet; On described combi inlet port pipeline, be provided with whirlwind-type flameholder; Before described combi inlet port, be provided with solenoid electric valve, before described solenoid electric valve, be provided with for the first T-valve of methanol gas circulation with for oxygen the second T-valve circulation and that communicate with described the first T-valve, before the first T-valve, be provided with for preventing the gas flame-retardant device of gaseous combustion.
Advantage of the present invention is: by the setting on different valves road, regulate inflow and the flow of oxygen and methyl alcohol, and whirlwind-type flameholder is set with abundant combustion methanol at the interior chamber inlet of mixture combustion, by deep fat gas mixture heat supply during to burning in mistress's circulation, make methyl alcohol burning reclaim the most effective of carbonic acid gas simultaneously.
Accompanying drawing explanation
Fig. 1 is decarbonylation stove schematic diagram of the present invention;
Fig. 2 is the synthetic method schematic diagram of dihydro geranyl acetone of the present invention or dihydro farnesyl acetone;
In figure, 1-heating coil; Chamber in 11-; 12-mistress;
111-combi inlet port; 112-mixed gas outlet;
1111-the first T-valve; 1112-the second T-valve; 1113-solenoid electric valve; 1114-whirlwind-type flameholder, 1115-gas flame-retardant device; 121-hot oil inlet; 122-hot oil outlet.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment mono-
Synthesizing of dihydro geranyl acetone: the stainless steel cauldron of 5000L, add dihydrolinalool 1000kg, add aluminum isopropylate 30kg to make catalyzer, heat up about 180 ℃ and drip methyl acetoacetate 770kg, about 2.5 hours, dropwise, drip methyl acetoacetate and continue insulation reaction about 2 hours, carrying out along with reaction, constantly there are carbonic acid gas and methanol gas to overflow from reaction system, by cooling tower and film water cooler, enter gas-liquid separator separates and go out a large amount of methyl alcohol, carbon dioxide is carrying a small amount of acetone secretly and low boiling substance enters the rear chemical recycling of carbon dioxide of decarbonylation stove burning and water, by separator, isolate more than 99% carbon dioxide of purity, by guide pipeline, enter the pH value that ethynylation post regulates water again.By Gc detection reaction terminal, after reaction finishes, proceed to another and be equipped with the 5000L reactor of underpressure distillation system and evaporative condenser to carry out underpressure distillation, the high vacuum underpressure distillation component 1200kg that just boiling, be dihydro geranyl acetone, reaction molar yield 95.6%, product purity 96.3%.
Decarbonylation furnace structure as shown in Figure 1, comprise interior chamber 11 and the tortuous swirl type heating coil 1 for the mistress 12 to mixture combustion heat supply being arranged on outside described interior chamber 11 for mixture combustion, the two ends of described interior chamber 11 are respectively arranged with combi inlet port 111 and mixed gas outlet 112, and described mistress's 12 two ends are respectively arranged with hot oil inlet 121 and hot oil outlet 122; On described combi inlet port 111 pipelines, be provided with whirlwind-type flameholder 1114; Before described combi inlet port 111, be provided with solenoid electric valve 113, before described solenoid electric valve 113, be provided with for the first T-valve 1111 of methanol gas circulation with for being provided with for preventing the gas flame-retardant device 1115 of gaseous combustion before oxygen the second T-valve 1112, the first T-valve 1111 circulation and that communicate with described the first T-valve 1111.
The present invention has investigated the impact of temperature of reaction on productive rate in addition, and concrete data are as shown in the table:
Above data show: the productive rate that temperature of reaction is reacted in the time of 170 ℃ is higher.
In synthetic technology, the concentration of methyl alcohol, in 80% left and right, has other inflammable gass of 20% left and right, and the heat energy producing by the burning of decarbonylation stove is supplied with heat-conducting oil heating, then returns for Karol rearrangement reaction, so circulation.In this experiment, methyl alcohol is fully burnt, the heat energy producing while then reclaiming carbonic acid gas and burning.
The carbonic acid gas reclaiming, because purity is higher, can calculate economic benefit by market value.
Embodiment bis-
Synthesizing of dihydro farnesyl acetone: the stainless steel cauldron of 5000L, add dihydro nerolidol 1000kg, add aluminum isopropylate 27 kg to make catalyzer, heat up about 180 ℃ and drip methyl acetoacetate 540kg, about 2.5 hours, dropwise, drip methyl acetoacetate and continue insulation reaction about 2 hours, carrying out along with reaction, constantly there are carbonic acid gas and methanol gas to overflow from reaction system, by cooling tower and film water cooler, enter gas-liquid separator separates and go out a large amount of methyl alcohol, carbon dioxide is carrying a small amount of acetone secretly and low boiling substance enters the rear chemical recycling of carbon dioxide of decarbonylation stove burning and water, by separator, isolate more than 99% carbon dioxide of purity, by guide pipeline, enter the pH value that ethynylation post regulates water again.By Gc detection reaction terminal, after reaction finishes rear reaction and finishes, feed liquid is taken advantage of and proceeded to another and be equipped with the 5000L reactor of underpressure distillation system and evaporative condenser to carry out underpressure distillation, the high vacuum underpressure distillation component 1130kg that just boiling, be dihydro farnesyl acetone, reaction yield 95.9%, product purity 96.7%.
The present invention has investigated the impact of reaction times on reaction yield in addition, and data are as shown in the table:
By above data, show: soaking time reaction yield about 2 hours is higher.
The carbonic acid gas reclaiming, because purity is higher, can calculate economic benefit by market value.Specific as follows: by producing 1000 kilograms of dihydro geranyl acetones every day, to calculate, approximately 448.9 kilograms of recyclable high concentration carbon dioxides, by the dihydro farnesyl acetone of producing 1000 kilograms every day, calculate, approximately 332.7 kilograms of callable high concentration carbon dioxides, by 2 yuan of/kilogram of calculating of commercially available carbon dioxide minimum rate, the economic benefit of the carbon dioxide generating that reclaim every day can reach 1560 yuan/day, the economic benefit producing for 1 year is about for 46.8 ten thousand/year, above two kinds of products can generate the methyl alcohol of 9.7kmoL every day, the heat energy of calorific value approximately 70,000 kilojoules that burning produces, be equivalent to the heat that 1.4 tons of coals produce, meanwhile, the annual alternative approximately 20 tons of industrial acetic acids of carbonic acid gas that reclaim are for regulating the pH value of reaction, the more important thing is the discharge that has reduced toxic and harmful, reduced better the pollution to environment.
Embodiment tri-
The synthetic method of dihydro geranyl acetone comprises step:
(1) batching: take by weight 800 parts of dihydrolinalools, 25 parts of aluminum isopropylates, 700 parts of methyl acetoacetates, standby;
(2) synthetic: whole dihydrolinalools to be mixed with aluminum isopropylate, be warming up to 160 ℃ and start to drip methyl acetoacetate, be added dropwise to complete follow-up continuous insulation reaction 1.5h synthesizing dihydro geranyl acetone;
(3) by-product recovery: the carbonic acid gas generating during by reaction is cooling with methanol gas, separated, reclaim the methanol liquid of cooling generation, and the carbon dioxide of carrying methanol gas and the low organic impurity gas that boils secretly is introduced in decarbonylation stove, wherein methanol gas and the low organic impurity gas that boils generate carbonic acid gas and steam through burning fully in decarbonylation stove, gas mixture is again by separated, be converted into more than 99% carbon dioxide of purity, introduce the post that needs carbon dioxide.
Embodiment tetra-
The synthetic method of dihydro geranyl acetone comprises step:
(1) batching: take by weight 1200 parts of dihydrolinalools, 35 parts of aluminum isopropylates, 820 parts of methyl aceto acetates, standby;
(2) synthetic: whole dihydrolinalools to be mixed with aluminum isopropylate, be warming up to 200 ℃ and start to drip methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 3h synthesizing dihydro geranyl acetone;
(3) by-product recovery: the carbonic acid gas generating during by reaction is cooling with methanol gas, separated, reclaim the methanol liquid of cooling generation, and the carbon dioxide of carrying methanol gas and the low organic impurity gas that boils secretly is introduced in decarbonylation stove, wherein methanol gas and the low organic impurity gas that boils generate carbonic acid gas and steam through burning fully in decarbonylation stove, gas mixture is again by separated, be converted into more than 99% carbon dioxide of purity, introduce the post that needs carbon dioxide.
Embodiment five
With embodiment tri-, different is that step (1) takes 1000 parts of dihydrolinalools, 28 parts of aluminum isopropylates, 740 parts of methyl acetoacetates by weight; Step (2) is mixed described whole dihydrolinalools with aluminum isopropylate, be warming up to 165 ℃ and start to drip methyl acetoacetate, is added dropwise to complete follow-up continuous insulation reaction 1.8h synthesizing dihydro geranyl acetone.
Embodiment six
With embodiment tetra-, different is that step (1) takes 1000 parts of dihydrolinalools, 32 parts of aluminum isopropylates, 780 parts of methyl aceto acetates by weight; Step (2) is mixed described whole dihydrolinalools with aluminum isopropylate, be warming up to 180 ℃ and start to drip methyl aceto acetate, is added dropwise to complete follow-up continuous insulation reaction 2.5h synthesizing dihydro geranyl acetone.
Embodiment seven
The synthetic method of dihydro farnesyl acetone, it comprises step successively:
(1) batching: take by weight 800 parts of dihydro nerolidols, 25 parts of aluminum isopropylates, 700 parts of methyl acetoacetates, standby;
(2) synthetic: described whole dihydro nerolidols to be mixed with aluminum isopropylate, be warming up to 160 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 1.5h synthesizing dihydro farnesyl acetone;
(3) by-product recovery: the carbonic acid gas generating during by reaction is cooling with methanol gas, separated, reclaim the methanol liquid of cooling generation, and the carbon dioxide of carrying methanol gas and the low organic impurity gas that boils secretly is introduced in decarbonylation stove, wherein methanol gas and the low organic impurity gas that boils generate carbonic acid gas and steam through burning fully in decarbonylation stove, gas mixture is again by separated, be converted into more than 99% carbon dioxide of purity, introduce the post that needs carbon dioxide.
Embodiment eight
The synthetic method of dihydro farnesyl acetone, it comprises step successively:
(1) batching: take by weight 1200 parts of dihydro nerolidols, 35 parts of aluminum isopropylates, 820 parts of methyl aceto acetates, standby;
(2) synthetic: described whole dihydro nerolidols to be mixed with aluminum isopropylate, be warming up to 200 ℃ and start to drip methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 3h synthesizing dihydro farnesyl acetone;
(3) by-product recovery: the carbonic acid gas generating during by reaction is cooling with methanol gas, separated, reclaim the methanol liquid of cooling generation, and the carbon dioxide of carrying methanol gas and the low organic impurity gas that boils secretly is introduced in decarbonylation stove, wherein methanol gas and the low organic impurity gas that boils generate carbonic acid gas and steam through burning fully in decarbonylation stove, gas mixture is again by separated, be converted into more than 99% carbon dioxide of purity, introduce the post that needs carbon dioxide.
Embodiment nine
With embodiment seven, different is that step (1) takes 1000 parts of dihydro nerolidols, 28 parts of aluminum isopropylates, 740 parts of methyl acetoacetates by weight; Step (2) is mixed described whole dihydro nerolidols with aluminum isopropylate, be warming up to 165 ℃ and start to drip methyl acetoacetate, is added dropwise to complete follow-up continuous insulation reaction 1.8h synthesizing dihydro farnesyl acetone.
Embodiment ten
With embodiment eight, different is that step (1) takes 1000 parts of dihydro nerolidols, 32 parts of aluminum isopropylates, 780 parts of methyl aceto acetates by weight; Step (2) is mixed described whole dihydro nerolidols with aluminum isopropylate, be warming up to 180 ℃ and start to drip methyl aceto acetate, is added dropwise to complete follow-up continuous insulation reaction 2.5h synthesizing dihydro farnesyl acetone.
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art can make to the present embodiment the modification that there is no creative contribution as required after reading this specification sheets, but as long as within the scope of claim of the present invention, are all subject to the protection of patent law.
Claims (10)
1. the synthetic method of dihydro geranyl acetone, is characterized in that comprising successively step:
(1) batching: take by weight dihydrolinalool 800-1200 part, aluminum isopropylate 25-35 part, methyl acetoacetate or methyl aceto acetate 700-820 part, standby;
(2) synthetic: described whole dihydrolinalools to be mixed with aluminum isopropylate, be warming up to 160-200 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 1.5-3h synthesizing dihydro geranyl acetone;
(3) by-product recovery: the carbonic acid gas generating during by reaction is cooling with methanol gas, separated, reclaim the methanol liquid of cooling generation, and the carbon dioxide of carrying methanol gas and the low organic impurity gas that boils secretly is introduced in decarbonylation stove, wherein methanol gas and the low organic impurity gas that boils generate carbonic acid gas and steam through burning fully in decarbonylation stove, gas mixture is again by separated, be converted into more than 99% carbon dioxide of purity, introduce the post that needs carbon dioxide.
2. the synthetic method of dihydro geranyl acetone according to claim 1, is characterized in that: described step (1) takes 1000 parts of dihydrolinalools, aluminum isopropylate 28-32 part, methyl acetoacetate or methyl aceto acetate 740-780 part by weight.
3. the synthetic method of dihydro geranyl acetone according to claim 2, it is characterized in that: described step (2) is mixed described whole dihydrolinalools with aluminum isopropylate, be warming up to 165-180 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 1.8-2.5h synthesizing dihydro geranyl acetone.
4. the synthetic method of dihydro geranyl acetone according to claim 3, it is characterized in that: described step (2) is mixed described whole dihydrolinalools with aluminum isopropylate, be warming up to 170 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 2h synthesizing dihydro geranyl acetone.
5. the synthetic method of dihydro farnesyl acetone, is characterized in that comprising successively step:
(1) batching: take by weight dihydro nerolidol 800-1200 part, aluminum isopropylate 25-35 part, methyl acetoacetate or methyl aceto acetate 700-820 part, standby;
(2) synthetic: described whole dihydro nerolidols to be mixed with aluminum isopropylate, be warming up to 160-200 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 1.5-3h synthesizing dihydro farnesyl acetone;
(3) by-product recovery: the carbonic acid gas generating during by reaction is cooling with methanol gas, separated, reclaim the methanol liquid of cooling generation, and the carbon dioxide of carrying methanol gas and the low organic impurity gas that boils secretly is introduced in decarbonylation stove, wherein methanol gas and the low organic impurity gas that boils generate carbonic acid gas and steam through burning fully in decarbonylation stove, gas mixture is again by separated, be converted into more than 99% carbon dioxide of purity, introduce the post that needs carbon dioxide.
6. the synthetic method of dihydro farnesyl acetone according to claim 5, is characterized in that: described step (1) takes 1000 parts of dihydro nerolidols, aluminum isopropylate 28-32 part, methyl acetoacetate or methyl aceto acetate 740-780 part by weight.
7. the synthetic method of dihydro farnesyl acetone according to claim 6, it is characterized in that: described step (2) is mixed described whole dihydro nerolidols with aluminum isopropylate, be warming up to 165-180 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 1.8-2.5h synthesizing dihydro farnesyl acetone.
8. the synthetic method of dihydro farnesyl acetone according to claim 7, it is characterized in that: described step (2) is mixed described whole dihydro nerolidols with aluminum isopropylate, be warming up to 180 ℃ and start to drip methyl acetoacetate or methyl aceto acetate, be added dropwise to complete follow-up continuous insulation reaction 2h synthesizing dihydro farnesyl acetone.
9. the synthetic method of dihydro geranyl acetone according to claim 4 or dihydro farnesyl acetone claimed in claim 8, is characterized in that: the time for adding of described step (2) methyl acetoacetate or methyl aceto acetate is controlled at 2-3h.
10. the synthetic method of dihydro geranyl acetone according to claim 9 or dihydro farnesyl acetone, it is characterized in that: described step (3) decarbonylation stove comprises for the interior chamber (11) of mixture combustion and is arranged on the outer tortuous swirl type heating coil (1) for the mistress (12) to mixture combustion heat supply in described interior chamber (11), the two ends of described interior chamber (11) are respectively arranged with combi inlet port (111) and mixed gas outlet (112), and described mistress's (12) two ends are respectively arranged with hot oil inlet (121) and hot oil outlet (122); On described combi inlet port (111) pipeline, be provided with whirlwind-type flameholder (1114); The front solenoid electric valve (113) that is provided with of described combi inlet port (111), described solenoid electric valve (113) is front to be provided with for first T-valve (1111) of methanol gas circulation with for oxygen the second T-valve (1112) circulation and that communicate with described the first T-valve (1111), and described the first T-valve (1111) is front to be provided with for preventing the gas flame-retardant device (1115) of gaseous combustion.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104478679A (en) * | 2014-11-21 | 2015-04-01 | 山东新和成药业有限公司 | Preparation process and purification method of advanced gamma and delta-unsaturated ketone |
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| US2795617A (en) * | 1957-06-11 | |||
| CN1546449A (en) * | 2003-11-28 | 2004-11-17 | 中国林业科学研究院林产化学工业研究 | Process for producing geranyl acetone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2795617A (en) * | 1957-06-11 | |||
| CN1546449A (en) * | 2003-11-28 | 2004-11-17 | 中国林业科学研究院林产化学工业研究 | Process for producing geranyl acetone |
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| 许青青等: "法尼基丙酮的合成方法及其结构的量子化学研究", 《计算机与应用化学》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104478679A (en) * | 2014-11-21 | 2015-04-01 | 山东新和成药业有限公司 | Preparation process and purification method of advanced gamma and delta-unsaturated ketone |
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