CN117964470A - Synthesis method of beta-ionone - Google Patents
Synthesis method of beta-ionone Download PDFInfo
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- CN117964470A CN117964470A CN202311738874.2A CN202311738874A CN117964470A CN 117964470 A CN117964470 A CN 117964470A CN 202311738874 A CN202311738874 A CN 202311738874A CN 117964470 A CN117964470 A CN 117964470A
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- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 title claims abstract description 136
- SFEOKXHPFMOVRM-UHFFFAOYSA-N (+)-(S)-gamma-ionone Natural products CC(=O)C=CC1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 claims abstract description 67
- JXJIQCXXJGRKRJ-KOOBJXAQSA-N pseudoionone Chemical compound CC(C)=CCC\C(C)=C\C=C\C(C)=O JXJIQCXXJGRKRJ-KOOBJXAQSA-N 0.000 claims abstract description 67
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 47
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 11
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229940043350 citral Drugs 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 5
- 239000003205 fragrance Substances 0.000 abstract description 19
- 229930002839 ionone Natural products 0.000 abstract description 9
- 150000002499 ionone derivatives Chemical class 0.000 abstract description 9
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 61
- 239000000203 mixture Substances 0.000 description 45
- 239000011259 mixed solution Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 18
- 230000001276 controlling effect Effects 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000012074 organic phase Substances 0.000 description 14
- 230000001105 regulatory effect Effects 0.000 description 14
- UZFLPKAIBPNNCA-UHFFFAOYSA-N alpha-ionone Natural products CC(=O)C=CC1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-UHFFFAOYSA-N 0.000 description 12
- UZFLPKAIBPNNCA-FPLPWBNLSA-N α-ionone Chemical compound CC(=O)\C=C/C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-FPLPWBNLSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 235000009508 confectionery Nutrition 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- -1 cyclic aliphatic compounds Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000001707 (E,7R,11R)-3,7,11,15-tetramethylhexadec-2-en-1-ol Substances 0.000 description 1
- BLUHKGOSFDHHGX-UHFFFAOYSA-N Phytol Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C=CO BLUHKGOSFDHHGX-UHFFFAOYSA-N 0.000 description 1
- HNZBNQYXWOLKBA-UHFFFAOYSA-N Tetrahydrofarnesol Natural products CC(C)CCCC(C)CCCC(C)=CCO HNZBNQYXWOLKBA-UHFFFAOYSA-N 0.000 description 1
- SHGAZHPCJJPHSC-NWVFGJFESA-N Tretinoin Chemical compound OC(=O)/C=C(\C)/C=C/C=C(C)C=CC1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-NWVFGJFESA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BOTWFXYSPFMFNR-OALUTQOASA-N all-rac-phytol Natural products CC(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)=CCO BOTWFXYSPFMFNR-OALUTQOASA-N 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
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 150000001588 beta-ionone derivatives Chemical class 0.000 description 1
- 229960002747 betacarotene Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229930007090 gamma-ionone Natural products 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- BOTWFXYSPFMFNR-PYDDKJGSSA-N phytol Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCC\C(C)=C\CO BOTWFXYSPFMFNR-PYDDKJGSSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930002330 retinoic acid Natural products 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 229960001727 tretinoin Drugs 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A 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
- SFEOKXHPFMOVRM-BQYQJAHWSA-N γ-ionone Chemical compound CC(=O)\C=C\C1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-BQYQJAHWSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing beta-ionone. The synthesis method comprises the following steps: is prepared from the following raw materials in parts by mass through cyclization under the catalysis of inorganic acid; and (3) a component A: all-trans pseudo-ionone, component B: ionone isomers, distinguished from all-trans pseudoionone, component C: as distinguished from other components comprising the total pseudoionone of the a and B components. The obtained product has the advantages of less than 100ppm of impurity alcohol, strong fragrance, low chromaticity value, low normal-temperature viscosity, good fluidity and good commercial competitiveness.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a synthesis method of beta-ionone.
Background
Beta-ionone is a pale yellow liquid and is an important medical synthesis intermediate. In particular, it is an important raw material for synthesizing vitamins A, E, beta-carotene, retinoic acid and phytol, etc. The purity of the beta-ionone product and the residual range of impurity components have significant effects on the chromaticity and aroma of the beta-ionone. At present, the production technology for industrially preparing the beta-ionone is mainly monopoly abroad. The production process mainly uses pseudoionone as raw material and concentrated sulfuric acid as catalyst, and produces product ionone through cyclization reaction. The instantaneous exothermic power of the reaction is high, the total exothermic amount is severe, the reaction process is difficult to control accurately, and the selectivity of the product beta-ionone is poor. The reaction product is usually a mixture of several isomers, such as alpha-ionone, beta-ionone, gamma-ionone, which are similar in their physicochemical properties and are relatively difficult to separate from each other.
In order to remove a large amount of the heat of reaction during the reaction and to increase the selectivity, german patent DE-PS1080105 and 1668505 both mention that aliphatic or cyclic aliphatic compounds can be added to remove part of the heat. In order to enhance mass transfer and increase selectivity of beta-ionone, basf patent CN1218455A discloses cyclization and quenching of pseudoionone with concentrated sulfuric acid in a multistage series stirred tank at 20-90 ℃ with a reaction yield of only 77.5-85.5% and a beta-ionone purity of only about 90%. In patent CN101333154a, germany bayer corporation mentions a process for enhancing heat transfer by a microchannel reactor, the conversion rate of raw materials is about 97%, the selectivity of beta-ionone is 92%, but the reactor and equipment are too fine, the material is special alloy too expensive, and the reactor and equipment are not suitable for mass production on a large scale.
There are few large enterprises in China that can independently produce beta-ionone. Patent CN95111793.9 discloses a process for cyclizing pseudo-ionone to beta-ionone at low temperature, but the process requires a large amount of water dilution to quench the reaction, and the concentrated sulfuric acid is severely diluted, so that the cost of recovering the concentrated sulfuric acid is excessive. Patent CN1508113 discloses a method for reducing reaction temperature by adding dry ice in the cyclization reaction process, the conversion rate of beta-ionone can be up to 96% under the condition of low temperature, the yield is about 80%, but the defect is obvious in the large-scale production of the reaction process, and the excessive consumption of dry ice not only increases the production cost, but also increases the complexity of the process operation, thus being not suitable for industrial production. In order to adapt to continuous industrial scale production, chinese patent CN106278853a discloses a method for continuously synthesizing beta-ionone by using a micro-chemical technology, the pseudo-ionone and concentrated sulfuric acid are continuously passed through a micro-channel reactor, the yield of beta-ionone can reach 82%, but the defect of easy blockage is also brought by the tiny channel size, and the consumption and recovery of the concentrated acid are problems to be solved.
As known, pseudoionone undergoes more side reactions during cyclization reaction to produce alcohol compounds as impurities, which greatly affect the chromaticity, aroma and flowability of the product. Thus, for controlling the color and aroma of the product beta-ionone, patent CN113603577 reports controlling the color and aroma of the product by controlling the content of the fusel substances in the product to be less than 300 ppm. The inventor researches and discovers that the fusel substances are main factors influencing the fragrance of the product. Thus, the neutralizing agent such as ethanolamine, triethanolamine and the like is added into the cyclization reaction liquid to remove the fusel substances, but the additional substances also need subsequent rectification separation, so that the process is relatively complex. In addition, the introduction of organic alkali can also cause the upgrading of equipment materials, thereby improving the production cost.
Furthermore, we studied that β -ionone with purity > 99.5% is a product with a faint scent and is not suitable as a raw material for downstream flavors and fragrances, whereas β -ionone sold by chemical synthesis on the market is a mixture with a content of 95% -99.5%. The beta-ionone products obtained by each manufacturer have extremely different chromaticity, strong fragrance and fluidity, which leads to strong and weak market competitiveness. The color value of the beta-ionone of basf is less than 50Hazen after being evaluated, the product has comfortable ionone fragrance and sweet fragrance, and the normal temperature viscosity of the product is less than 20cP, so that the product has excellent circulation value in the market.
Therefore, the product with low color value, strong fragrance and good fluidity is obtained, and the method for preparing the beta-ionone with high efficiency and simplicity has good commercial prospect.
Disclosure of Invention
In order to overcome the defects in the prior art, one of the purposes of the invention is to provide a method for synthesizing beta-ionone, and the product obtained by the method has low color value, strong fragrance and good fluidity.
In order to achieve the aim of the invention, the following specific technical scheme is adopted:
a synthesis method of beta-ionone, which comprises the following steps: is prepared from the following raw materials in parts by mass through cyclization under the catalysis of inorganic acid,
And (3) a component A: 30 to 70 parts by mass, preferably 40 to 60 parts by mass,
And the component B comprises the following components: 25 to 60 parts by mass, preferably 30 to 50 parts by mass,
And C, component: 1 to 10 parts by mass, preferably 1 to 5 parts by mass, of other components than the total pseudoionone comprising the A and B components.
In one embodiment of the present invention, the A, B and C components are configured as a solution, preferably at a concentration of 5wt% to 60wt%, more preferably 10wt% to 40wt%.
In one embodiment of the invention, the C component comprises 0-50% moisture, 10-60% diacetone alcohol, 40-90% citral.
In one embodiment of the invention, the mineral acid is a protic acid, preferably one or more of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid; preferably, the inorganic acid mass fraction is 80-100%, preferably 93-98%.
In one embodiment of the invention, the mass ratio of the total mass of the A and B components to the mineral acid is 1:1 to 1:10, preferably 1:2 to 1:5.
In one embodiment of the invention, the method adds an organic solvent; preferably, the organic solvent is one or more of alkane, chloralkane and benzene homolog which are liquid at normal temperature, wherein the chloralkane is one or more of trichloromethane, dichloromethane and dichloroethane, the benzene homolog is benzene and/or toluene, and the alkane is n-heptane and/or n-hexane.
In one embodiment of the invention, the cyclisation reaction is carried out at a pressure of 0-1.0MPaG, preferably 0.1-0.5MPaG; the reaction temperature is 5-50 ℃ and 10-40 ℃.
In an exemplary preferred embodiment, the cyclization reaction may be carried out in 2 stages, stage 1 reaction temperature of 5 to 30 ℃, preferably 10 to 25 ℃, and reaction residence time of 1 to 10s, preferably 2 to 6s; the reaction temperature of the 2 nd stage is 20-50 ℃, preferably 25-40 ℃, and the reaction residence time is 15-60s, preferably 25-40s.
In one embodiment of the invention, the reactor outlet material is quenched after the cyclization reaction is complete; preferably, quenching is carried out by mixing with water, preferably the mass flow rate of the outlet material and water is (1-10): 1, more preferably (2-5): 1.
It is another object of the present invention to provide a beta-ionone.
The beta-ionone is prepared by the synthesis method, the content of fusel in the beta-ionone is less than 100ppm, the chromaticity value is less than 30Hazen, and the normal temperature viscosity is less than 10cP.
The composition of the beta-ionone is preferably 98.0% -99.9% of all-trans beta-ionone (calculated by total beta-ionone), 0.4% -1.0% of cis beta-ionone, 0.04% -0.1% of alpha-ionone, 0-100ppm of heavy component fusel and 0.02% -0.1% of other components.
In the invention, the diacetone alcohol has the following structural formula:
The structural formula of citral is as follows:
The structural formula of the all-trans pseudo ionone is as follows:
the cis-pseudoionone has the structural formula:
The structural formula of the fusel is shown below and is marked as a recombinant.
The inventors found that: (1) The citral compound can be recombined with the fusel to form an acetal compound with a low boiling point, so that on one hand, the fusel substance of the system is consumed, the fusel content in the product is reduced, and the fluidity and the color value of the product are better. On the other hand, the acetal compound with low boiling point is rapidly separated in the light removal process, so that the content of the hetero-alcohol compound in the product beta-ionone is less than 100ppm.
(2) The presence of diacetone alcohol and water in the organic phase can dilute the H+ active center of the cyclization reaction, so that the byproduct alpha-ionone in the obtained product is controlled at a small level.
(3) Cis-forms contained in the raw material, such as cis-pseudoionone, also produce cis-isomer of beta-ionone, alpha-ionone and all-trans beta-ionone during the cyclization reaction. The product thus obtained is a mixture of the cis-isomer, the stereoisomers (alpha, beta), the all-trans-isomer and the fusel of ionone. Such mixtures of ionones are known in the chemical industry as "beta-ionones", and are actually a mixture, rather than a single compound.
The mixture of ionones gives the final product a stronger ionone aroma, and only a single pure beta-ionone (all-trans beta-ionone with a purity of > 99.9%) is only slightly ionone-aroma, not accompanied by a strong ionone aroma and sweetness. In addition, from the economical point of view, more rectifying equipment is needed for synthesizing the all-trans beta-ionone with the purity of more than 99.9 percent, so that the energy consumption is larger, and the method has no commercial utilization value. Therefore, the preparation of the beta-ionone with a special composition has technical creation value and is also the technical innovation point of the application.
In the process of preparing the product beta-ionone, the following reaction occurs, and the specific equation is as follows:
Wherein, the equation 1 generates main reaction to generate beta-ionone and isomer of beta-ionone, the equation 2 generates side reaction to generate byproduct alpha-ionone, and the equation 3 generates side reaction to generate fusel which is marked as heavy component.
Compared with the traditional synthesis process of the beta-ionone, the invention has the following beneficial effects:
(1) The conversion rate of the raw materials of the synthesis reaction of the beta-ionone is more than 99 percent, and the selectivity is more than 85 percent.
(2) The obtained product has the impurity alcohol content of less than 100ppm, the beta-ionone which is nearly colorless can be obtained without complex and additional post-treatment measures, the chromaticity value is less than 30Hazen, the product has obvious ionone fragrance and sweetness, the normal temperature viscosity is less than 10cP, and the fluidity is good and the quality is excellent.
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, but the present invention is not limited to the following examples.
Methanol (AR, 99.5%), ethanol (AR, 99.5%), n-heptane (AR, 99.5%), dichloroethane (AR, 99.5%), dichloromethane (AR, 99.5%), hydrochloric acid (AR, 36%), sulfuric acid (AR, 80-100%, customizable) and the like were all analytically pure (AR), all purchased from ala Ding Shiji inc. Pseudoionone is purchased from wuhan's biotechnology limited and has a purity and content of each component that is within the scope of the present application. Specifically, the total trans content of the pseudoionone mixture is 30-70%, such as 30%, 40%, 50%, 60% and 70%; cis-forms account for 20-60%, such as 25%, 35%, 49%, 57% and 60%; the total amount of other components than total pseudoionone is 1-10%, such as 1%, 3%, 5% and 10%. Water is present in the other components (calculated as the total amount of the other components) in a proportion of 0-50%, such as 0%, 1%, 3%, 5% and 10%, diacetone alcohol is present in the other components (calculated as the total amount of the other components) in a proportion of 10-60%, such as 10%, 20%, 30%, 40% and 60%, and citral is present in the other components in a proportion of 40-90%, such as 40%, 55%, 67%, 70% and 89%.
The reactor, vacuum pump, magneton, separating funnel, etc. were purchased from Chongqing Xinweil glass instruments limited.
In the experimental process, the raw material gas chromatograph is Agilent GC-2022 edition, the temperature of a chromatographic column Agilent WAX is 280 ℃, the gas carrying capacity is 3mL/min, and the temperature raising program is as follows: maintaining at 50deg.C for 5min, heating to 80deg.C at 4deg.C/min, maintaining for 0min, heating to 280 deg.C at 25deg.C/min, maintaining for 2min, and detecting at 280 deg.C. The aroma of the product beta-ionone is analyzed by Beijing dazhengyuan technology Co., ltd, and the chromaticity value is measured by an LIC0690 colorimeter.
Example 1
A sufficient amount of pseudoionone mixture was selected under nitrogen for use, the specific composition shown in the following table, the% being wt%.
The pseudo-ionone mixture shown in the above table was used as a solute, and dissolved in n-heptane to prepare an n-heptane solution with a mass fraction of 25% and a total mass of 4kg, wherein 0.95kg of pseudo-ionone was contained, while preparing an aqueous solution of 93wt% sulfuric acid. The two materials are mixed according to the mass ratio of the pseudo-ionone mixture to 93wt% sulfuric acid water solution of 1:2, and the temperature of the mixed system is ensured to be-25 ℃. The temperature regulator of the reactor is opened, the two sections of temperature intervals of the reactor are respectively regulated to 10 ℃ and 25 ℃, and the back pressure valve is used for controlling the system pressure of the reaction section to be 0.1MPaG. Regulating the feeding flow rate by a horizontal flow pump, continuously pumping the mixed solution into a reactor to carry out cyclization reaction, determining the residence time of the mixed solution in the 1 st stage reactor to be 2s and the residence time of the mixed solution in the 2 nd stage reactor to be 25s, fully mixing the materials at the outlet of the reactor with water according to the mass of 2:1 after the system is stabilized, and quenching to terminate the continuous reaction. Collecting quenched organic phase, controlling the feeding flow of the mixed solution of pseudoionone to 5g/min, taking the liquid (containing the pseudoionone 11.875 g) which is continuously fed for 10min after the system is stable and the liquid which is continuously discharged for 10min, collecting and analyzing the mass of the pseudoionone in the continuously discharged liquid to be 0.023g, 10.41g of the product beta ionone, and calculating the raw material conversion rate of the pseudoionone to be 99.8%, and the selectivity of the beta ionone to be 87.8%.
The quenched organic phase is subjected to light component solvent removal at 150 ℃ and 0.05KPaA to obtain the product.
The composition of the gas phase analysis was as follows: the total content of all-trans beta-ionone is 99.05%, the content of beta-ionone cis-isomer is 0.6%, the content of alpha-ionone is 0.2%, the total content of other components is 0.1%, and the content of heavy component fusel is 41ppm and less than 100ppm. After color value, viscosity and aroma evaluation, the color value of the obtained product is 18Hazen, the viscosity is 8.5cP at normal temperature, the fluidity is good, and the product has rich violet aroma, sweet aroma and costustoot.
Example 2
A sufficient amount of pseudoionone mixture was selected under nitrogen for use, the specific composition shown in the following table, the% being wt%.
The pseudo-ionone mixture shown in the above table was used as a solute, and dissolved in methylene chloride to prepare a methylene chloride solution having a mass fraction of 5%, and the total mass was 4kg, wherein 0.18kg of pseudo-ionone was contained (4 kg of material was sufficient for the continuous experiment to stabilize the reaction system). And simultaneously preparing 80wt% sulfuric acid water solution. The two materials are mixed according to the mass ratio of the pseudo-ionone mixture to the 80wt% sulfuric acid water solution of 1:5, and the temperature of the mixed system is ensured to be-30 ℃. The temperature regulator of the reactor is opened, the two sections of temperature intervals of the reactor are respectively regulated to 5 ℃ and 20 ℃, and the back pressure valve is used for controlling the system pressure of the reaction section to be 0.2MPaG. Regulating the feeding flow rate by a horizontal flow pump, continuously pumping the mixed solution into a reactor to carry out cyclization reaction, determining the residence time of the mixed solution in the 1 st stage reactor to be 10s, determining the residence time of the mixed solution in the 2 nd stage reactor to be 15s, fully mixing the materials at the outlet of the reactor with water according to the mass ratio of 3:1 after the system is stabilized, and quenching to terminate the continuous reaction. Collecting quenched organic phase, controlling the feeding flow of the pseudo-ionone mixed solution to 5g/min, taking liquid (containing 2.25g of pseudo-ionone) which is continuously fed for 10min after the system is stable and liquid which is continuously discharged for 10min, collecting and analyzing the mass of the pseudo-ionone in the continuously discharged liquid to be 0.011g, carrying out 1.941g of beta-ionone as a product, and calculating the conversion rate of the raw material of the pseudo-ionone to be 99.5%, wherein the selectivity of the beta-ionone is 86.7%.
The quenched organic phase is subjected to light component solvent removal at 100 ℃ and 0.01KPaA to obtain the product.
The composition of the gas phase analysis was as follows: the total content of all-trans beta-ionone is 98.95%, the content of beta-ionone cis-isomer is 0.80%, the content of alpha-ionone is 0.1%, the total content of other components is 0.1%, and the content of heavy component fusel is 58ppm and less than 100ppm. The color value, viscosity and aroma evaluation of the obtained product are carried out, the color value of the product is 17Hazen, the viscosity is 7.7cP at normal temperature, the fluidity is good, and the product has rich violet fragrance, sweet fragrance and costustoot.
Example 3
A sufficient amount of pseudoionone mixture was selected under nitrogen for use, the specific composition shown in the following table, the% being wt%.
The pseudoionone mixture shown in the above table was used as a solute, and dissolved in dichloroethane to prepare a 10% strength by mass dichloroethane solution having a total mass of 4kg and containing 0.38kg of pseudoionone (4 kg of material was sufficient to stabilize the reaction system for continuous experiments). And simultaneously preparing 90wt% sulfuric acid water solution. The two materials are mixed according to the mass ratio of the pseudo-ionone mixture to the 90wt% sulfuric acid water solution of 1:1, and the temperature of the mixed system is ensured to be-10 ℃. The temperature regulator of the reactor is opened, the two sections of temperature intervals of the reactor are respectively regulated to 15 ℃ and 30 ℃, and the back pressure valve is used for controlling the system pressure of the reaction section to be 0.3MPaG. Regulating the feeding flow rate by a horizontal flow pump, continuously pumping the mixed solution into a reactor to carry out cyclization reaction, determining the residence time of the mixed solution in the 1 st section reactor to be 4s and the residence time of the mixed solution in the 2 nd section reactor to be 60s, fully mixing the materials at the outlet of the reactor with water according to the mass ratio of 1:1 after the system is stabilized, and quenching to terminate the continuous reaction. Collecting quenched organic phase, controlling the feeding flow of the pseudo-ionone mixed solution to 5g/min, taking liquid (containing 4.75g of pseudo-ionone) which is continuously fed for 10min after the system is stable and liquid which is continuously discharged for 10min, collecting and analyzing the mass of the pseudo-ionone in the continuously discharged liquid to be 0.033g, 4.127g of beta-ionone as a product, and calculating the conversion rate of the raw material of the pseudo-ionone to be 99.3%, wherein the selectivity of the beta-ionone is 87.5%.
The quenched organic phase is subjected to light component solvent removal at 200 ℃ and 0.2KPaA to obtain the product.
The composition of the gas phase analysis was as follows: the total content of all-trans beta-ionone is 98.85%, the content of beta-ionone cis-isomer is 0.90%, the content of alpha-ionone is 0.1%, the total content of other components is 0.1%, and the content of heavy component fusel is 28ppm and less than 100ppm. After color value, viscosity and aroma evaluation, the color value of the obtained product is 15Hazen, the viscosity is 8.2cP at normal temperature, the fluidity is good, and the product has rich violet aroma, sweet aroma and costustoot.
Example 4
A sufficient amount of pseudoionone mixture was selected under nitrogen for use, the specific composition shown in the following table, the% being wt%.
The pseudo ionone mixture shown in the above table was used as a solute, and dissolved in toluene to prepare a toluene solution with a mass fraction of 40% and a total mass of 4kg, wherein 1.552kg of pseudo ionone was contained (for continuous experiments, 4kg of material was sufficient to stabilize the reaction system). And simultaneously preparing 85wt% sulfuric acid water solution. The two materials are mixed according to the mass ratio of the pseudo-ionone mixture to 85wt% sulfuric acid water solution of 1:10, and the temperature of the mixed system is ensured to be 0 ℃. The temperature regulator of the reactor is opened, the two sections of temperature intervals of the reactor are respectively regulated to 25 ℃ and 40 ℃, and the back pressure valve is used for controlling the system pressure of the reaction section to be 0.4MPaG. Regulating the feeding flow rate by a horizontal flow pump, continuously pumping the mixed solution into a reactor to carry out cyclization reaction, determining the residence time of the mixed solution in the 1 st stage reactor to be 6s, determining the residence time of the mixed solution in the 2 nd stage reactor to be 30s, fully mixing the materials at the outlet of the reactor with water according to the mass of 10:1 after the system is stabilized, and quenching to terminate the continuous reaction. Collecting quenched organic phase, controlling the feeding flow of the pseudo-ionone mixed solution to 5g/min, taking liquid (19.4 g of pseudo-ionone is contained) which is continuously fed for 10min after the system is stable and liquid which is continuously discharged for 10min, collecting and analyzing the mass of the pseudo-ionone in the continuously discharged liquid to be 0.019g, carrying out 16.648g of beta-ionone as a product, and calculating the conversion rate of the raw material of the pseudo-ionone to be 99.9%, wherein the selectivity of the beta-ionone is 85.9%.
The quenched organic phase is subjected to light component solvent removal at 120 ℃ and 0.5KPaA to obtain the product.
The composition of the gas phase analysis was as follows: the total content of all-trans beta-ionone is 99.1%, the content of beta-ionone cis-isomer is 0.8%, the content of alpha-ionone is 0.05%, the total content of other components is 0.04%, and the content of heavy component fusel is 10ppm and less than 100ppm. The color value, viscosity and aroma evaluation of the obtained product are carried out, the color value of the product is 19Hazen, the viscosity is 5.1cP at normal temperature, the fluidity is good, and the product has rich violet fragrance, sweet fragrance and costustoot.
Example 5
A sufficient amount of pseudoionone mixture was selected under nitrogen for use, the specific composition shown in the following table, the% being wt%.
The pseudoionone mixture shown in the above table was used as a solute, and dissolved in benzene to prepare a 60% benzene solution having a total mass of 4kg and containing 2.376kg of pseudoionone (4 kg of material was sufficient to stabilize the reaction system for continuous experiments). While 100wt% fuming sulfuric acid was formulated. The two materials are mixed according to the mass ratio of the pseudo-ionone mixture to 100wt% sulfuric acid of 1:8, and the temperature of the mixed system is ensured to be 10 ℃. The temperature regulator of the reactor is opened, the two sections of temperature intervals of the reactor are respectively regulated to 30 ℃ and 50 ℃, and the back pressure valve is used for controlling the system pressure of the reaction section to be 0.5MPaG. Regulating the feeding flow rate by a horizontal flow pump, continuously pumping the mixed solution into a reactor to carry out cyclization reaction, determining the residence time of the mixed solution in the 1 st section reactor to be 8s and the residence time of the mixed solution in the 2 nd section reactor to be 50s, fully mixing the materials at the outlet of the reactor with water according to the mass ratio of 5:1 after the system is stabilized, and quenching to terminate the continuous reaction. Collecting quenched organic phase, controlling the feeding flow of the pseudo-ionone mixed solution to 5g/min, taking liquid which is continuously fed for 10min after the system is stable (29.7 g of pseudo-ionone is contained) and liquid which is continuously discharged for 10min, collecting and analyzing the mass of the pseudo-ionone in the continuously discharged liquid to be 0.089g, carrying out 26.028g of beta-ionone as a product, and calculating the conversion rate of the raw material of the pseudo-ionone to be 99.1%, wherein the selectivity of the beta-ionone is 87.9%.
The quenched organic phase is subjected to light component solvent removal at 180 ℃ and 1.0KPaA to obtain the product.
The composition of the gas phase analysis was as follows: the total content of all-trans beta-ionone is 99.25%, the content of beta-ionone cis-isomer is 0.5%, the content of alpha-ionone is 0.1%, the total content of other components is 0.03%, and the content of heavy component fusel is 5ppm and less than 100ppm. The color value, viscosity and aroma evaluation of the obtained product are carried out, the color value of the product is 16Hazen, the viscosity is 9.5cP at normal temperature, the fluidity is good, and the product has rich violet fragrance, sweet fragrance and costustoot.
Comparative example 1
The process conditions were the same as in example 1, except that the raw material composition was changed (as shown below) as compared with example 1.
A sufficient amount of pseudoionone mixture was selected under nitrogen for use, the specific composition shown in the following table, the% being wt%.
The pseudo-ionone mixture shown in the above table was used as a solute, and dissolved in n-heptane to prepare a 25% by mass n-heptane solution, with a total mass of 4kg, containing 0.95kg of pseudo-ionone (4 kg of material was sufficient for the continuous experiment to stabilize the reaction system). Meanwhile, 93wt% sulfuric acid aqueous solution is prepared. The two materials are mixed according to the mass ratio of the pseudo-ionone mixture to 93wt% sulfuric acid water solution of 1:2, and the temperature of the mixed system is ensured to be-25 ℃. The temperature regulator of the reactor is opened, the two sections of temperature intervals of the reactor are respectively regulated to 10 ℃ and 25 ℃, and the back pressure valve is used for controlling the system pressure of the reaction section to be 0.1MPaG. Regulating the feeding flow rate by a horizontal flow pump, continuously pumping the mixed solution into a reactor to carry out cyclization reaction, determining the residence time of the mixed solution in the 1 st stage reactor to be 2s and the residence time of the mixed solution in the 2 nd stage reactor to be 25s, fully mixing the materials at the outlet of the reactor with water according to the mass of 2:1 after the system is stabilized, and quenching to terminate the continuous reaction. Collecting quenched organic phase, controlling the feeding flow of the mixed solution of pseudoionone to 5g/min, taking the liquid (containing the pseudoionone 11.875 g) which is continuously fed for 10min after the system is stable and the liquid which is continuously discharged for 10min, collecting and analyzing the mass of the pseudoionone in the continuously discharged liquid to be 0.023g, 10.41g of the product beta ionone, and calculating the raw material conversion rate of the pseudoionone to be 99.8%, and the selectivity of the beta ionone to be 87.8%.
The quenched organic phase is subjected to light component solvent removal at 150 ℃ and 0.05KPaA to obtain the product.
The composition of the gas phase analysis was as follows: the total content of all-trans beta-ionone is 99.8%, the content of beta-ionone cis-isomer is 0.05%, the content of alpha-ionone is 0.1%, the total content of other components is 0.05%, and the content of heavy component fusel is 41ppm and less than 100ppm. After color value, viscosity and aroma evaluation, the obtained product has only weak light fragrance, and the application value of the product serving as downstream perfume and essence is greatly reduced.
As is clear from comparative example 1, when the cis-pseudoionone content in the raw material system is low, the content of all-trans-beta-ionone in the product is increased to 99.8% under the same process conditions, and the extremely pure beta-ionone has only weak light fragrance, so that the application value of the product as downstream perfume and essence is greatly reduced, and the product is not ideal.
Comparative example 2
Except for the change in the raw material composition (as shown below), the process conditions were the same as in example 1.
A sufficient amount of the pseudoionone mixture was prepared under nitrogen for use, the specific composition is shown in the following table, and the% is wt%.
The pseudo-ionone mixture shown in the above table was used as a solute, and dissolved in n-heptane to prepare a 25% by mass n-heptane solution, with a total mass of 4kg, containing 0.95kg of pseudo-ionone (4 kg of material was sufficient for the continuous experiment to stabilize the reaction system). Meanwhile, 93wt% sulfuric acid aqueous solution is prepared. The two materials are mixed according to the mass ratio of the pseudo-ionone mixture to 93wt% sulfuric acid water solution of 1:2, and the temperature of the mixed system is ensured to be-25 ℃. The temperature regulator of the reactor is opened, the two sections of temperature intervals of the reactor are respectively regulated to 10 ℃ and 25 ℃, and the back pressure valve is used for controlling the system pressure of the reaction section to be 0.1MPaG. Regulating the feeding flow rate by a horizontal flow pump, continuously pumping the mixed solution into a reactor to carry out cyclization reaction, determining the residence time of the mixed solution in the 1 st stage reactor to be 2s and the residence time of the mixed solution in the 2 nd stage reactor to be 25s, fully mixing the materials at the outlet of the reactor with water according to the mass of 2:1 after the system is stabilized, and quenching to terminate the continuous reaction. The quenched organic phase is collected, the conversion rate of the gas phase analysis raw material pseudoionone is 99.9 percent, and the selectivity of beta-ionone is 84.5 percent
The solvent is removed to obtain the product with the content of beta-ionone of 95.0%, the content of alpha-ionone of 3.5% and the content of fusel of 1.5%, the color value of the product is 152Hazen, and the product is placed as orange yellow liquid at room temperature. The evaluation result is: slightly contains light violet flower fragrance. The viscosity at normal temperature is 102cP, the fluidity is poor, the adhesive wall is easy to be stuck in a tetrafluoro or glass vessel, and the adhesive cannot be completely poured out.
As is clear from comparative example 2, when the starting material has no other components (water, diacetone alcohol), the cyclization reaction rate increases under the same conditions, so that the selectivity of the resulting product β -ionone is lower. When the content of citral in other components is reduced, the content of fusel in the product is obviously increased under the same separation condition, the color value of the product is obviously deepened, the fragrance is not strong enough, and the product performance is poor.
Claims (7)
1. The synthesis method of the beta-ionone is characterized by comprising the following steps: is prepared from the following raw materials in parts by mass through cyclization under the catalysis of inorganic acid,
And (3) a component A: 30 to 70 parts by mass, preferably 40 to 60 parts by mass,
And the component B comprises the following components: 25 to 60 parts by mass, preferably 30 to 50 parts by mass,
And C, component: 1 to 10 parts by mass, preferably 1 to 5 parts by mass, of other components than the total pseudoionone comprising the A and B components.
2. The synthesis method according to claim 1, wherein the a, B and C components are configured as solutions, preferably at a concentration of 5wt% to 60wt%, more preferably 10wt% to 40wt%.
3. The synthetic method according to claim 1 or 2, wherein the C component comprises 0-50% of water, 10-60% of diacetone alcohol, 40-90% of citral.
4. A synthetic method according to any one of claims 1-3, characterized in that the mineral acid is a protic acid, preferably one or more of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid;
preferably, the mass fraction of the inorganic acid is 80-100%, preferably 93-98%;
and/or the mass ratio of the total mass of the component A and the component B to the inorganic acid is 1:1-1:10, preferably 1:2-1:5.
5. The synthetic method according to any one of claims 1 to 4, wherein an organic solvent is added to the method;
Preferably, the organic solvent is one or more of alkane, chloralkane and benzene homolog which are liquid at normal temperature, wherein the chloralkane is one or more of trichloromethane, dichloromethane and dichloroethane, the benzene homolog is benzene and/or toluene, and the alkane is n-heptane and/or n-hexane.
6. The synthetic method according to any one of claims 1 to 5, characterized in that the pressure of the cyclization reaction is 0-1.0MPaG, preferably 0.1-0.5MPaG; the reaction temperature is 5-50 ℃ and 10-40 ℃;
And/or quenching the reactor outlet material after the cyclization reaction is completed;
preferably, quenching is carried out by mixing with water, preferably the mass flow rate of the outlet material and water is (1-10): 1, more preferably (2-5): 1.
7. A beta-ionone prepared by the synthetic method of any one of claims 1-6, wherein the content of fusel in the beta-ionone is less than 100ppm, the chromaticity value is less than 30Hazen, and the normal temperature viscosity is less than 10cP.
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