CN113698284B - Synthesis method of pseudo ionone - Google Patents
Synthesis method of pseudo ionone Download PDFInfo
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- CN113698284B CN113698284B CN202111027243.0A CN202111027243A CN113698284B CN 113698284 B CN113698284 B CN 113698284B CN 202111027243 A CN202111027243 A CN 202111027243A CN 113698284 B CN113698284 B CN 113698284B
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- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- JXJIQCXXJGRKRJ-KOOBJXAQSA-N pseudoionone Chemical compound CC(C)=CCC\C(C)=C\C=C\C(C)=O JXJIQCXXJGRKRJ-KOOBJXAQSA-N 0.000 title claims abstract description 29
- 238000001308 synthesis method Methods 0.000 title description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 26
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229940043350 citral Drugs 0.000 claims abstract description 21
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000007530 organic bases Chemical class 0.000 claims abstract description 5
- 238000006467 substitution reaction Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- 238000004817 gas chromatography Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 7
- 238000004445 quantitative analysis Methods 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000011534 incubation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 239000003205 fragrance Substances 0.000 description 6
- 229930002839 ionone Natural products 0.000 description 6
- 150000002499 ionone derivatives Chemical class 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical class CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- SFEOKXHPFMOVRM-UHFFFAOYSA-N (+)-(S)-gamma-ionone Chemical class CC(=O)C=CC1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-UHFFFAOYSA-N 0.000 description 2
- UZFLPKAIBPNNCA-UHFFFAOYSA-N alpha-ionone Natural products CC(=O)C=CC1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- UZFLPKAIBPNNCA-FPLPWBNLSA-N α-ionone Chemical class CC(=O)\C=C/C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-FPLPWBNLSA-N 0.000 description 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 description 1
- 235000013734 beta-carotene Nutrition 0.000 description 1
- 239000011648 beta-carotene Substances 0.000 description 1
- 229960002747 betacarotene Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- BCDGQXUMWHRQCB-UHFFFAOYSA-N glycine methyl ketone Natural products CC(=O)CN BCDGQXUMWHRQCB-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of pseudo ionone, which is characterized by comprising the following steps: adding acetone into a reaction kettle, adding auxiliary alkali, stirring for one time, adding an organic base catalyst and citral, performing nitrogen substitution, slowly heating to 60-150 ℃, preserving heat until the reaction is completed, and rectifying the reaction liquid to separate a pseudo ionone finished product, wherein the auxiliary alkali is any one or more of pyridine, piperidine, pyrrole, pyrazole or imidazole, as shown in the following formula 1. The invention adopts organic alkali and auxiliary alkali as condensation catalysts, thereby avoiding the corrosion of equipment and prolonging the service life of the equipment; the use of a milder catalyst system reduces the side reaction of raw materials and has higher reaction yield; the catalyst can be recycled through the rectification process, so that the production cost is reduced; after the reaction is finished, neutralization and washing operations are not needed, so that the generation of three wastes is reduced.
Description
Technical Field
The invention relates to the fields of essence and spice and chemical industry, in particular to a synthetic method of pseudo ionone.
Background
Ionone is a fragrance with ionone fragrance, comprising two isomers of alpha-ionone and beta-ionone. The alpha-ionone fragrance is similar to ionone fragrance, has costustoot smell and has fruit fragrance, and is mainly applied to essence blending and downstream spice synthesis, and the beta-ionone is largely applied to vitamin A and beta-carotene synthesis. Pseudoionone is an important intermediate for synthesizing ionone, and has very wide application in the fields of foods, fragrances, medicines and the like.
At present, pseudo-ionone and a synthetic method are prepared by using citral and acetone as raw materials through Aldol condensation reaction under alkaline conditions, and common condensation catalysts include alkali metal hydroxides, such as aqueous solution, alcohol solution and the like of sodium hydroxide and potassium hydroxide, and the method is adopted to produce the pseudo-ionone industrially. However, a large amount of strong alkaline aqueous solution has high requirements on corrosion resistance of equipment, neutralization and washing operations are needed after the reaction, a large amount of waste salt and waste water can be generated, and environmental protection pressure is high.
Aiming at the defects of the existing industrial production technology of false ionone, a supported KF solid base catalyst is introduced in Chinese patent CN 105562041A and is used for preparing the false ionone, so that the subsequent alkali neutralization operation when the liquid base catalyst is used is avoided, but the catalyst is recovered and needs to be regenerated, the complexity of the technology is increased, and the large-scale industrial production has a certain difficulty.
In the patent CN 1065481A, a macroporous anion exchange resin catalyst is used, and a continuous reaction mode is used for reaction, so that the operation procedure is simplified, but a solvent is required to be introduced into a reaction system, the energy consumption of post-treatment is increased, and the adopted catalyst has higher manufacturing cost and limits the practical application.
In the patent CN 103108857A, pure lanthanum oxide is used as a condensation catalyst for synthesizing pseudo ionone, the method avoids the characteristics of corrosiveness and large three wastes in the traditional process, the process flow is simple, the method has the defects of harsh reaction conditions, the catalyst can recover the reaction activity only by high-temperature regeneration, and the reaction selectivity of the regenerated catalyst is obviously reduced.
Disclosure of Invention
In order to overcome the defects of strong catalyst corrosiveness, large three-waste and low yield in the production process of the pseudo-ionone in the prior art, a method for synthesizing the pseudo-ionone by using organic base and auxiliary base catalysis is provided.
The catalyst is used for preparing pseudo-ionone through the condensation reaction of acetone and citral, so that the defects of the traditional liquid base catalyst production process are avoided, and meanwhile, the high-purity pseudo-ionone is prepared.
In order to achieve the purpose of the invention, the technical scheme adopted is as follows:
a preparation method of pseudo ionone comprises the following steps:
adding acetone into a reaction kettle, adding auxiliary alkali, stirring for one time, adding an organic alkali catalyst and citral, performing nitrogen replacement, slowly heating to 60-150 ℃, preserving heat until the reaction is completed, and rectifying the reaction liquid to separate a pseudo ionone finished product, wherein the formula 1 is as follows:
the auxiliary base is any one or more of pyridine, piperidine, pyrrole, pyrazole or imidazole.
In a preferred embodiment of the invention, the mass ratio of the acetone to the auxiliary base is 1:0.1-2.
In a preferred embodiment of the present invention, the mass ratio of the acetone to the organic base catalyst is 1:0.001-0.05.
In a preferred embodiment of the invention, the mass ratio of the acetone to the citral is 1:0.2-0.5.
In a preferred embodiment of the invention, the incubation reaction has a reaction time of 2 to 8 hours.
In a preferred embodiment of the present invention, the number of nitrogen substitutions is three.
In a preferred embodiment of the present invention, the quantitative analysis of the reaction solution was performed by gas chromatography when the pressure in the autoclave reached 0.6Mpa during the reaction.
In a preferred embodiment of the invention, the reaction is completed as a criterion that the composition of the reaction solution is substantially unchanged.
In a preferred embodiment of the invention, the rectification is carried out using a rectification column.
The invention has the beneficial effects that:
the invention adopts organic alkali and auxiliary alkali as condensation catalysts, thereby avoiding the corrosion of equipment and prolonging the service life of the equipment; the use of a milder catalyst system reduces the side reaction of raw materials and has higher reaction yield; the catalyst can be recycled through the rectification process, so that the production cost is reduced; after the reaction is finished, neutralization and washing operations are not needed, so that the generation of three wastes is reduced.
The invention basically solves some defects of the liquid alkali catalyst in the traditional production process, is green and environment-friendly, and has great application value.
Detailed Description
The invention is further illustrated by the following examples:
example 1
300g of acetone and 150g of pyridine are added into a 1L stainless steel high-pressure reaction kettle, after stirring and mixing uniformly, 3g of triethylamine is added, then 150g of citral is added, after nitrogen is replaced for three times, the temperature is slowly raised to 130 ℃, the temperature is kept, the pressure in the kettle is 0.6Mpa, sampling is carried out during the reaction, and quantitative analysis is carried out by using gas chromatography. After 6h of heat preservation, the composition of the reaction liquid is basically unchanged, the reaction is stopped, the temperature is reduced to room temperature, the reaction liquid is taken out, and the separation is carried out by using a rectifying tower. Under the pressure of 101.3kPa, collecting fractions at 56-120 ℃, wherein the main components are acetone, pyridine and triethylamine as a catalyst. Collecting the fraction at 70-80 ℃ under 300Pa, wherein the main component is citral, and collecting the fraction at 120-130 ℃ to obtain the pseudo ionone finished product with the product yield of 82.5%.
Example 2
To a 1L stainless steel autoclave, 300g of acetone and 150g of pyridine were added, and after stirring and mixing uniformly, 3g of triethylamine was added, then 100g of citral was added, and after three times of nitrogen substitution, the temperature was slowly raised to 130℃and then kept at 0.6MPa, and during the reaction, samples were taken and quantitative analysis was performed by using gas chromatography. After 4h of heat preservation, the composition of the reaction liquid is basically unchanged, the reaction is stopped, the temperature is reduced to room temperature, the reaction liquid is taken out, and the separation is carried out by using a rectifying tower. Under the pressure of 101.3kPa, collecting fractions at 56-120 ℃, wherein the main components are acetone, pyridine and triethylamine as a catalyst. Collecting the fraction at 70-80 ℃ under 300Pa, wherein the main component is citral, and collecting the fraction at 120-130 ℃ to obtain the pseudo ionone finished product with the product yield of 85.3%.
Example 3
To a 1L stainless steel autoclave, 300g of acetone and 150g of pyridine were added, and after stirring and mixing uniformly, 6g of triethylamine was added, then 100g of citral was added, and after three times of nitrogen substitution, the temperature was slowly raised to 130℃and then kept at 0.6MPa in the autoclave, and during the reaction, samples were taken and quantitative analysis was performed using gas chromatography. After 2h of heat preservation, the composition of the reaction liquid is basically unchanged, the reaction is stopped, the temperature is reduced to room temperature, the reaction liquid is taken out, and the separation is carried out by using a rectifying tower. Under the pressure of 101.3kPa, collecting fractions at 56-120 ℃, wherein the main components are acetone, pyridine and triethylamine as a catalyst. Collecting the fraction at 70-80 ℃ under 300Pa, wherein the main component is citral, and collecting the fraction at 120-130 ℃ to obtain the pseudo ionone finished product, and the product yield is 87.6%.
Example 4
Adding 300g of acetone and 150g of pyridine into a 1L stainless steel high-pressure reaction kettle, stirring and mixing uniformly, adding 6g of diethylamine, then adding 100g of citral, replacing nitrogen for three times, slowly heating to 130 ℃, preserving heat, sampling during the reaction, and quantitatively analyzing by using gas chromatography, wherein the pressure in the kettle is 0.6 Mpa. After the heat preservation is carried out for 8 hours, the composition of the reaction liquid is basically unchanged, the reaction is stopped, the temperature is reduced to the room temperature, the reaction liquid is taken out, and the separation is carried out by using a rectifying tower. Under the pressure of 101.3kPa, collecting fractions at 56-120 ℃, wherein the main components are acetone, pyridine and catalyst diethylamine. Collecting the fraction at 70-80 ℃ under 300Pa, wherein the main component is citral, and collecting the fraction at 120-130 ℃ to obtain the pseudo ionone finished product, and the product yield is 75.8%.
Example 5
Adding 300g of acetone and 150g of piperidine into a 1L stainless steel high-pressure reaction kettle, uniformly stirring and mixing, adding 6g of triethylamine, adding 100g of citral, replacing nitrogen for three times, slowly heating to 130 ℃, preserving heat, sampling during the reaction, and quantitatively analyzing by using gas chromatography, wherein the pressure in the kettle is 0.6 Mpa. After 4h of heat preservation, the composition of the reaction liquid is basically unchanged, the reaction is stopped, the temperature is reduced to room temperature, the reaction liquid is taken out, and the separation is carried out by using a rectifying tower. Under the pressure of 101.3kPa, collecting the fraction at 56-110 ℃, wherein the main components are acetone, piperidine and triethylamine as catalyst. Collecting the fraction at 70-80 ℃ under 300Pa, wherein the main component is citral, and collecting the fraction at 120-130 ℃ to obtain the pseudo ionone finished product with the product yield of 83.7%.
Example 6
Adding 240g of acetone and 240g of pyridine into a 1L stainless steel high-pressure reaction kettle, stirring and mixing uniformly, adding 4.8g of triethylamine, then adding 80g of citral, replacing nitrogen for three times, slowly heating to 130 ℃, preserving heat, sampling during the reaction, and quantitatively analyzing by using gas chromatography under the pressure of 0.6 Mpa. After 2h of heat preservation, the composition of the reaction liquid is basically unchanged, the reaction is stopped, the temperature is reduced to room temperature, the reaction liquid is taken out, and the separation is carried out by using a rectifying tower. Under the pressure of 101.3kPa, collecting fractions at 56-120 ℃, wherein the main components are acetone, pyridine and triethylamine as a catalyst. Collecting the fraction at 70-80 ℃ under 300Pa, wherein the main component is citral, and collecting the fraction at 120-130 ℃ to obtain the pseudo ionone finished product with the product yield of 88.4%.
Example 7
Adding 300g of acetone and 6g of triethylamine into a 1L stainless steel high-pressure reaction kettle, uniformly stirring and mixing, adding 100g of citral, replacing nitrogen for three times, slowly heating to 150 ℃, preserving heat, sampling during the reaction at 0.8Mpa, and quantitatively analyzing by using gas chromatography. After the heat preservation is carried out for 8 hours, the composition of the reaction liquid is basically unchanged, the reaction is stopped, the temperature is reduced to the room temperature, the reaction liquid is taken out, and the separation is carried out by using a rectifying tower. Under the pressure of 101.3kPa, collecting the fraction at 56-90 ℃ and the main components are acetone and triethylamine as catalyst. Collecting the fraction at 70-80 ℃ under 300Pa, wherein the main component is citral, and collecting the fraction at 120-130 ℃ to obtain the pseudo ionone finished product with the product yield of 38.5%.
No auxiliary alkali is added, the reaction speed is low, and the raw material conversion rate is low.
Claims (6)
1. The preparation method of the pseudo ionone is characterized by comprising the following steps:
adding acetone into a reaction kettle, adding auxiliary alkali, stirring for one time, adding an organic alkali catalyst and citral, performing nitrogen replacement, slowly heating to 60-150 ℃, preserving heat until the reaction is completed, and rectifying the reaction liquid to separate a pseudo ionone finished product, wherein the formula 1 is as follows:
the auxiliary base is any one or more of pyridine, piperidine, pyrrole, pyrazole or imidazole;
the mass ratio of the acetone to the auxiliary base is 1:0.1-2;
the mass ratio of the acetone to the organic base catalyst is 1:0.001-0.05;
the mass ratio of the acetone to the citral is 1:0.2-0.5;
the organic base catalyst is triethylamine or diethylamine.
2. The process for preparing pseudoionone according to claim 1, wherein the incubation is carried out for a reaction time of from 2 to 8 hours.
3. The method for preparing pseudoionone according to claim 1, wherein the number of nitrogen substitutions is three.
4. The method for preparing pseudoionone according to claim 1, wherein the quantitative analysis of the reaction solution is performed by gas chromatography when the pressure in the reactor reaches 0.6MPa during the reaction.
5. A process for the preparation of pseudoionone as claimed in claim 1, wherein the reaction is carried out with the standard that the composition of the reaction solution is substantially unchanged.
6. The method for preparing pseudoionone of claim 1, wherein the rectification is performed using a rectification column.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107670678A (en) * | 2017-10-19 | 2018-02-09 | 万华化学集团股份有限公司 | A kind of solid base catalyst and preparation method thereof and its method for being used to prepare pseudo ionone |
| CN108017525A (en) * | 2017-11-30 | 2018-05-11 | 山东新和成药业有限公司 | A kind of synthetic method of α-daphnone |
| CN111187152A (en) * | 2020-02-28 | 2020-05-22 | 浙江工业大学 | Method for synthesizing pseudo ionone under catalysis of alkaline immobilized ionic liquid |
| CN112479844A (en) * | 2020-11-19 | 2021-03-12 | 万华化学集团股份有限公司 | Preparation method of pseudo ionone |
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| CN107670678A (en) * | 2017-10-19 | 2018-02-09 | 万华化学集团股份有限公司 | A kind of solid base catalyst and preparation method thereof and its method for being used to prepare pseudo ionone |
| CN108017525A (en) * | 2017-11-30 | 2018-05-11 | 山东新和成药业有限公司 | A kind of synthetic method of α-daphnone |
| CN111187152A (en) * | 2020-02-28 | 2020-05-22 | 浙江工业大学 | Method for synthesizing pseudo ionone under catalysis of alkaline immobilized ionic liquid |
| CN112479844A (en) * | 2020-11-19 | 2021-03-12 | 万华化学集团股份有限公司 | Preparation method of pseudo ionone |
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| 假性紫罗兰酮合成条件;周袭非等;辽宁科技大学学报;第32卷(第3期);237-240 * |
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