CN104326890B - A kind of Carroll reacts continuous process method - Google Patents
A kind of Carroll reacts continuous process method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000010924 continuous production Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 122
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 150000002148 esters Chemical class 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 238000006462 rearrangement reaction Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000009413 insulation Methods 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 26
- -1 diethyl methyl Chemical class 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 6
- 230000008707 rearrangement Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 12
- 150000002576 ketones Chemical class 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002912 waste gas Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 description 4
- 238000006563 Carroll rearrangement reaction Methods 0.000 description 4
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- WHWDWIHXSPCOKZ-UHFFFAOYSA-N hexahydrofarnesyl acetone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)=O WHWDWIHXSPCOKZ-UHFFFAOYSA-N 0.000 description 4
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006114 decarboxylation reaction Methods 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 241000036316 Callitropsis Species 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004808 allyl alcohols Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 125000002370 organoaluminium group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- HNZUNIKWNYHEJJ-FMIVXFBMSA-N geranyl acetone Chemical compound CC(C)=CCC\C(C)=C\CCC(C)=O HNZUNIKWNYHEJJ-FMIVXFBMSA-N 0.000 description 1
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004801 process automation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
- C07C45/673—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 change of size of the carbon skeleton
- C07C45/676—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 change of size of the carbon skeleton by elimination of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of Carroll and react continuous process method, comprise the following steps: ester exchange, rearrangement reaction, decarboxylic reaction, insulation reaction and raw materials recovery operation.Reaction raw materials R alcohol and acylating agent carry out ester exchange reaction, generate acetoacetate R ester, and ester generates R ketone acid through resetting；Along with reaction temperature is stepped up, R ketone acid generates product R ketone through decarboxylic reaction.Reaction is divided into three section of five still to be carried out continuously by the way of autoclave is connected by this invention, the mode of point still temperature control, makes the reaction of each step fully carry out thoroughly.Present invention process method makes reaction carry out thoroughly, and side reaction is few, and yield is greatly improved；The waste gas CO of stable output2, comprehensive reutilization；On-the-spot realization full-automation, improves production safety coefficient.
Description
Technical field
The present invention relates to a kind of Carroll and react continuous process method, specifically, relate to critical process Carroll reaction process and autoclave series connection continuous reaction method in a kind of phytol ketone synthesis, belong to field of fine chemical.
Background technology
Phytol ketone is colourless or flaxen oily liquids, has delicate fragrance, due to its preferable fixation and light feature, it is widely used in blending, it is suitable for the preparation of bouquet type composition, is the most valuable spices of one, especially a kind of important high added value intermediate product of synthesising complex E.Vitamin E has the metabolism of promotion human body because of it, build up health vigor, reduce tissue aging, adjust reproductive function, promote blood circulation and prevent the multiple use of artery sclerosis, in recent years, the most progressively it is valued by the people, demand increases year by year, causes phytol ketone demand to increase year by year, and this technology mainly studies critical process Carroll reaction in phytol ketone synthesis.
Industrialize at present or there is the Carroll reaction of industrial prospect and substantially used batch production process, also had part to use tubular type continuous, but fully different according to reaction mechanism, cause reaction yield low, it is impossible to effectively to reclaim CO2Deng, it is not belonging to green chemical industry technique.Reaction expression is as follows:
In known synthetic method, there is the tertiary allyl alcohol compounds of a fixed structure and acetoacetic ester under the catalytic action of known catalyst organoaluminum salt, carry out Carroll be synthesized and increase the ketone compounds of 3 carbon atoms, be the classical synthetic reaction of a comparison.
Main literature report is as follows:
The method manufacturing geranyl acetone that Zhao Zhendong etc. relate in CN1546449A; it it is the mode that reaction raw materials and product are used " treating different things alike "; its process modification mainly drips acylating agent, recovery catalyst, is greatly increased the intermittent reaction that product yield is more general.
C. oersted etc. refer to a kind of method preparing beta-unsaturated ketone continuously including special reaction device in CN1251832, various unsaturated alcohols and various Acetacetic acid alkyl esters (mol ratio 0.8-1.2) react in fractionating column, generating the acetoacetic ester of unsaturated alcohol, the alcohol additionally produced steams (tower top separation) through tower top;At tower bottom, the acetoacetic ester of unsaturated alcohol forms beta-unsaturated ketone (separating at the bottom of tower) through organo-aluminium catalytically rearranging, discharges CO simultaneously2(return and use), residence time of material 0.25-6 h.
C. oersted etc. are primarily related to the preparation method of higher unsaturated ketone in CN1271716, the most various substituted a, β mono-unsaturated alcohol (high-carbon) in the presence of 0.1-0.5% organo aluminum catalyst, carry out Carroll reaction with various substituted Acetacetic acid alkyl esters.Its process modification is mainly reflected in, and adds Acetacetic acid alkyl ester or logical inert gas flow by mixing nozzle, to improve the mixing of mixture and to promote distilling alcohols accessory substance.
H. the CN1348434 such as outstanding Dick, it is primarily related to prepare γ with Karol reaction, delta unsaturated ketone, various replacement allyl alcohols or propargyl alcohol and various substituted Acetacetic acid alkyl esters (refer mainly to and ester that high-boiling point alcohol is formed), 150-220 DEG C of reaction (organo-aluminium is catalyst), and distill out the alkanol (boiling point is more than 140 DEG C) of generation simultaneously.
All batch tank reported above produce, and the mode that i.e. " ester exchange → rearrangement → decarboxylation " employing " is treated different things alike " is carried out simultaneously.The method causes:
(1) R-alcohol and acylating agent yield are the highest.Decomposing serious, byproduct of reaction is many, and yield is relatively low.The molar yield of general ketone is 88%, and the yield of acylating agent is 84%；
(2) waste gas cannot recycle.The CO of irregular discharge2Middle meeting entrainment portions organic matter, it is impossible to recycle, not environmentally.
(3), there is potential safety hazard in unrealized full-automation.
As can not be effectively solved, above-mentioned yield is low and safety and environmental protection requirement, and not only product cost loses the market competitiveness, and safety and environmental protection aspect exists especially and faces the risk being eliminated.
Summary of the invention
The problem to be solved in the present invention is for above not enough, it is provided that a kind of Carroll reacts continuous process method, it is achieved following goal of the invention: making reaction carry out thoroughly, side reaction is few, and yield is greatly improved；The waste gas CO of stable output2, comprehensive reutilization；On-the-spot realization full-automation, improves production safety coefficient.
For solve above-mentioned technical problem, the present invention by the following technical solutions:
A kind of Carroll reacts continuous process method, comprises the following steps: ester exchange, rearrangement reaction, decarboxylic reaction, insulation reaction and raw materials recovery operation.
The following is and the further of technique scheme is improved:
Described step of transesterification, first by a part of reactant liquor crude product standby in the first normal-pressure reaction kettle, heats up, and according to certain ratio dropping, the raw material tertiary alcohol and acylating agent diethyl methyl esters and catalyst organoaluminum salt is entered the first normal-pressure reaction kettle, carries out ester exchange reaction.
The tertiary alcohol of described addition: acylating agent: the mol ratio of catalyst is 0.8-3:1:0.02.
The temperature of ester exchange reaction is 96-101 DEG C, time of staying 2-3h.
Described rearrangement reaction, the product after ester exchange slowly enters the second normal-pressure reaction kettle by still overfall and carries out ester rearrangement reaction；Described rearrangement reaction temperature 120-130 DEG C, time 2-3h.
Described decarboxylic reaction, the product after rearrangement slowly enters the 3rd normal-pressure reaction kettle by still overfall and carries out decarboxylic reaction, part by-product carbinol and CO2Respectively enter groove by overhead condenser and gas holder recycles；Described decarboxylic reaction temperature 155-165 DEG C, time 2-3h.
Described insulation reaction, the material after decarboxylic reaction enters the 4th normal pressure heat-insulating still through still overfall and continues reaction, controls temperature 150-170 DEG C and time of staying 2-3h.
Described raw materials recovery; material after insulation reaction enters the 5th recovered under reduced pressure still through still overfall; control temperature, vacuum and the time of staying, raw material R-alcohol complete for unreacted and acylating agent recovery are entered next step operation to the first normal-pressure reaction kettle, grade product R-ketone.
Described raw materials recovery temperature 160-180 DEG C, vacuum-8～-12KPa, time of staying 1-1.5h.
Use described method, alcohol yield >=95.8%, diethyl methyl esters yield >=94.1%.
The present invention uses above technical scheme, compared with prior art, has the advantage that
1, this reaction substantially " ester exchange, rearrangement, decarboxylation " three-step reaction, current technique all uses three steps to carry out simultaneously, it is difficult to control; side reaction is a lot, and product yield is relatively low, and the yield of reaction raw materials R-alcohol is 88%; acylating agent diethyl methyl esters yield is about 84%, and production cost is higher；The present invention is directed to that domestic and international yield is low, energy consumption is high, CO2Can not effectively utilize the shortcomings such as many, independent research goes out a low production cost, and technical process is environmentally friendly, the green synthesis techniques route that process operation parameter is relatively mild.This technique is different according to course of reaction, point still temperature control design, is greatly improved selectivity and the yield of product, and the yield of alcohol is promoted to 96.14% by original 88%, and acylating agent yield is promoted to 94.4% by original 84%, is greatly saved production cost.
2, reaction changes multi-floating bodies into, and point still temperature control, product quality is more stable, and yield increases substantially.
3, operation achieves automation, and not only product quality is more stable, and by by-product waste gas CO2Carry out unifying to reclaim, turn waste into wealth, comprehensive utilization.
4, prior art is treated different things alike and is needed the cooling that constantly heats up in procedure, there is potential safety hazard in course of reaction, this process automation mechanized operation, makes course of reaction stable, improves safety coefficient.
Accompanying drawing illustrates:
Figure
1
It it is process chart in the embodiment of the present invention.
The 1-raw material tertiary alcohol feeds；2-acylating agent feeds；3-catalyst charge；4-the first normal-pressure reaction kettle；5-the second normal-pressure reaction kettle；6-the 3rd normal-pressure reaction kettle；7-the 4th normal pressure heat-insulating still；8-the 5th recovered under reduced pressure still；9-reactant liquor crude product discharging；10-reflux column.
Detailed description of the invention
Hereinafter the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is merely to illustrate and explains the present invention, is not intended to limit the present invention.Except as otherwise noted, the percentage employed in the present invention is percentage by volume.
The initial reaction stage of this reaction is Exchange Ester Process, reacts temperature required relatively low, and reaction raw materials R-alcohol and acylating agent carry out ester exchange reaction, generates acetoacetate-R-ester, and ester generates R-ketone acid through resetting；Along with reaction temperature is stepped up, R-ketone acid produces product R-ketone through decarboxylic reaction.According to this reaction mechanism, work out and utilize temperature and reaction process difference, be divided into three section of five still to be carried out continuously by the way of autoclave is connected reaction, the mode of point still temperature control, make the reaction of each step fully carry out thoroughly.
First by a part of reactant liquor crude product standby in the first normal-pressure reaction kettle; it is warming up to each still and controls temperature; after raw material R-alcohol and acylating agent and catalyst organoaluminum salt dripped according to the ratio of 0.8-3:1:0.02 enter normal-pressure reaction kettle; carry out ester exchange reaction; control temperature 80 DEG C-120 DEG C; preferably 96-101 DEG C, it is ensured that the 1-5 hour time of staying, preferably 2-3 hour；
First normal-pressure reaction kettle product acetoacetate-R-ester slowly enters the second normal-pressure reaction kettle by still overfall and carries out ester rearrangement reaction, controls temperature 100 DEG C-150 DEG C, preferably 120-130 DEG C, it is ensured that the 1-5 hour time of staying, preferably 2-3 hour；
Second normal-pressure reaction kettle product R-ketone acid slowly enters the 3rd normal-pressure reaction kettle by still overfall and carries out decarboxylic reaction, controls reaction temperature 140 DEG C-180 DEG C, preferably 155-165 DEG C, it is ensured that the 1-5 hour time of staying, preferably 2-3 hour.Part by-product carbinol and CO2Respectively enter groove by overhead condenser and gas holder recycles；
3rd normal-pressure reaction kettle material enters the 4th normal pressure heat-insulating still through still overfall and continues decarboxylic reaction completely, control temperature 140 DEG C-200 DEG C, preferably 150-170 DEG C, it is ensured that the 1-5 hour time of staying, preferably 2-3 hour；
4th normal pressure heat-insulating still material through still overfall enter the 5th recovered under reduced pressure still, control temperature 140 DEG C-210 DEG C, preferably 160-180 DEG C, vacuum-1Kpa～-20Kpa, preferably-8 pa～-12Kpa, it is ensured that the 1-3 hour time of staying, preferably 1-1.5 hour；
Raw material R-alcohol complete for unreacted and acylating agent recovery are entered next step operation to the first normal-pressure reaction kettle, grade product R-ketone.
Above-mentioned five still successive reactions are divided into three sections, mainly by reaction mechanism desired reaction temperature and the difference of the time of staying, controlling to make ester exchange, rearrangement, decarboxylation three step react at first three reactor respectively by temperature parameter, the 4th still continues reaction completely, and the 5th still reclaims raw material.
Embodiment:
According to the process chart shown in Fig. 1, a kind of Carroll reacts continuous process method, comprises the following steps:
a
, ester exchange:
First by a part of reactant liquor crude product standby in the first normal-pressure reaction kettle; heat up; the raw material tertiary alcohol and acylating agent diethyl methyl esters and catalyst organoaluminum salt are entered the first normal-pressure reaction kettle according to certain ratio dropping, carries out ester exchange reaction, control transesterification reaction temperature and the time of staying；
b
, rearrangement reaction:
First normal-pressure reaction kettle product slowly enters the second normal-pressure reaction kettle by still overfall and carries out ester rearrangement reaction, controls rearrangement reaction temperature, it is ensured that certain time of staying；
c
, decarboxylic reaction:
Second normal-pressure reaction kettle product slowly enters the 3rd normal-pressure reaction kettle by still overfall and carries out decarboxylic reaction, controls decarboxylic reaction temperature and the time of staying.Part by-product carbinol and CO2Respectively enter groove by overhead condenser and gas holder recycles；
d
, insulation reaction:
3rd normal-pressure reaction kettle material enters the 4th normal pressure heat-insulating still through still overfall and continues reaction, controls temperature and the time of staying；
e
, raw materials recovery:
4th normal pressure heat-insulating still material enters the 5th recovered under reduced pressure still through still overfall, controls temperature, vacuum and the time of staying, to the first normal-pressure reaction kettle, grade product R-ketone, raw material R-alcohol complete for unreacted and acylating agent recovery are entered next step operation.
According to the processing step of above-described embodiment, using different raw material process conditions to test, its process conditions and alcohol yield, diethyl methyl esters yield see table:
Comparative examples: (as a example by raw material nerolidol and acylating agent diethyl methyl esters)
Raw material is got the raw materials ready according to the ratio of 1:1.2:0.02 according to nerolidol and acylating agent diethyl methyl esters and catalyst organoaluminum salt; first nerolidol and catalyst are put into reactor; it is warming up to 150-170 degree; start to drip acylating agent diethyl methyl esters; drip 8 hours, drip and finish, insulation reaction 3 hours; then it is decompressed to-100pa and raw material R-alcohol complete for unreacted and acylating agent recovery, grade product R-ketone are entered next step operation.
Through purification of products and test analysis, nerolidol yield 88%, diethyl methyl esters yield 84%.
As can be seen from the above table, embodiment 1-6 alcohol yield reaches 95.8-96.6%, and diethyl methyl esters yield reaches 94.2-94.8%.Comparing with comparative examples, alcohol yield and diethyl methyl esters yield are all greatly improved.
In reaction, each technological parameter is preferred:
1, according to the processing step of embodiment, constant to remaining technological parameter in embodiment 2, only change the first normal-pressure reaction kettle temperature, test, result of the test is as follows:
The conversion ratio of ester exchange reaction is affected relatively big by temperature, and temperature low-conversion is low, and ester exchange speed simultaneously is low, and the reaction time extends.In the case of other conditions constant, being tested reaction temperature, result of the test can be seen that, temperature reaches optimum between 96-101 DEG C, incomplete less than this thermotonus, can volatilize higher than raw material during this value, is all unfavorable for the carrying out of reaction.
2, according to the processing step of embodiment, constant to remaining technological parameter in embodiment 2, only change the second normal-pressure reaction kettle temperature, test, result of the test is as follows:
Generating to R-ketone acid being reset by acetoacetate-R-ester, temperature is different, and rearrangement product is different, and therefore, the temperature under reacting this has made experiment.Under the effect of catalyst, acetoacetate-R-ester is reset, and generates R-ketone acid.As can be seen from the above table, between preferred temperature range is 120-130 DEG C.
3, according to the processing step of embodiment, constant to remaining technological parameter in embodiment 2, only change the 3rd normal-pressure reaction kettle temperature, test, result of the test is as follows:
During ketone acid dehydration, temperature is very big on its impact, and the product under different temperatures can be different.Reaction temperature is high so that the key between carboxyl and carbon is more easily broken off, and decarboxylic reaction is easier to occur, and temperature is the lowest, it is likely that form acid anhydrides.As can be seen from the above table, preferred range is 155-165 DEG C.
4, according to the processing step of embodiment, constant to remaining technological parameter in embodiment 2, only change the temperature retention time of the 4th normal pressure heat-insulating still, test, result of the test is as follows:
The temperature retention time of the 4th normal pressure heat-insulating still is also one of key factor affecting ultimate yield, and temperature retention time is too short, and reaction is not the most sufficiently carried out；Temperature retention time is long, then the generation of accessory substance can increase, and therefore, temperature retention time is tested by we.
As seen from the above table, temperature retention time is the longest, and raw material residual is the fewest, but this does not imply that the content of product is the highest.Reaction time is oversize, and the probability that in reaction, accessory substance produces is the biggest, and effecting reaction is the most not enough, and preferably temperature retention time is at 2-3h.
5, according to the processing step of embodiment, constant to remaining technological parameter in embodiment 2, only change the vacuum of the 5th recovered under reduced pressure still, test, result of the test is as follows:
Reduced pressure contributes to point R-OH sub-argument from still before reaction, in order to avoid affecting the carrying out of subsequent reactions, generating non-targeted compound, affecting subsequent reactions yield, cause difficulty to separation.As seen from the above table, pressure is too small, and front point of residual is serious, subsequent reactions and separation can be caused puzzlement；Pressure is excessive so that product yield can not be guaranteed.Drawing from data above analysis, the optimum pressure condition of Depressor response still is-8 kPa～-12kPa.
Last it is noted that the foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, although the present invention being described in detail with reference to previous embodiment, for a person skilled in the art, technical scheme described in foregoing embodiments still can be modified by it, or wherein portion of techniques feature is carried out equivalent.All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (4)
1. a Carroll reacts continuous process method, it is characterised in that: comprise the following steps: ester exchange, rearrangement reaction, decarboxylic reaction, insulation reaction and raw materials recovery operation；
Described step of transesterification, first by a part of reactant liquor crude product standby in the first normal-pressure reaction kettle, heats up, and according to certain ratio dropping, the raw material tertiary alcohol and acylating agent diethyl methyl esters and catalyst organoaluminum salt is entered the first normal-pressure reaction kettle, carries out ester exchange reaction；
The temperature of described ester exchange reaction is 96-101 DEG C, time of staying 2-3h；
Described rearrangement reaction, the product after ester exchange slowly enters the second normal-pressure reaction kettle by still overfall and carries out ester rearrangement reaction；Described rearrangement reaction temperature 120-130 DEG C, time 2-3h；
Described decarboxylic reaction, the product after rearrangement slowly enters the 3rd normal-pressure reaction kettle by still overfall and carries out decarboxylic reaction, part by-product carbinol and CO2Respectively enter groove by overhead condenser and gas holder recycles；Described decarboxylic reaction temperature 155-165 DEG C, time 2-3h；
Described insulation reaction, the material after decarboxylic reaction enters the 4th normal pressure heat-insulating still through still overfall and continues reaction, controls temperature 150-170 DEG C and time of staying 2-3h；
Described raw materials recovery, the material after insulation reaction enters the 5th recovered under reduced pressure still through still overfall, controls temperature, vacuum and the time of staying, and by raw material complete for unreacted and acylating agent recovery to the first normal-pressure reaction kettle, grade product enters next step operation.
2. a kind of Carroll as claimed in claim 1 reacts continuous process method, it is characterised in that: the tertiary alcohol of described addition: acylating agent: the mol ratio of catalyst is 0.8-3:1:0.02.
3. a kind of Carroll as claimed in claim 1 reacts continuous process method, it is characterised in that: described raw materials recovery temperature 160-180 DEG C, vacuum-8～-12KPa, time of staying 1-1.5h.
4. a kind of Carroll as claimed in claim 1 reacts continuous process method, it is characterised in that: use described method, alcohol yield >=95.8%, diethyl methyl esters yield >=94.1%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6300524B1 (en) * | 1998-11-16 | 2001-10-09 | Basf Aktiengesellschaft | Process for preparing higher unsaturated ketones |
| CN1348434A (en) * | 1998-09-07 | 2002-05-08 | Basf公司 | Preparation of γ,δ-Unsaturated Ketones by Carroll Reaction |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348434A (en) * | 1998-09-07 | 2002-05-08 | Basf公司 | Preparation of γ,δ-Unsaturated Ketones by Carroll Reaction |
| US6300524B1 (en) * | 1998-11-16 | 2001-10-09 | Basf Aktiengesellschaft | Process for preparing higher unsaturated ketones |
Non-Patent Citations (1)
| Title |
|---|
| 合成法尼基丙酮的优化实验条件;许青青等;《化学试剂》;20061231;第28卷(第1期);第59-60页 * |
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