CN106905129B - A kind of preparation method of fragrance intermediates - Google Patents
A kind of preparation method of fragrance intermediates Download PDFInfo
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- CN106905129B CN106905129B CN201710175728.1A CN201710175728A CN106905129B CN 106905129 B CN106905129 B CN 106905129B CN 201710175728 A CN201710175728 A CN 201710175728A CN 106905129 B CN106905129 B CN 106905129B
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- Prior art keywords
- ionone
- catalyst
- preparation
- citral
- butanone
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003205 fragrance Substances 0.000 title claims abstract description 13
- 239000000543 intermediate Substances 0.000 title claims abstract description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- -1 methyl pseudo-ionone Chemical compound 0.000 claims abstract description 43
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229940043350 citral Drugs 0.000 claims abstract description 28
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims abstract description 28
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 58
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005255 carburizing Methods 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002077 nanosphere Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 244000248349 Citrus limon Species 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 125000002785 azepinyl group Chemical group 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000796 flavoring agent Substances 0.000 abstract description 3
- 235000013355 food flavoring agent Nutrition 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 229930183419 Irisone Natural products 0.000 description 7
- UZFLPKAIBPNNCA-BQYQJAHWSA-N alpha-ionone Chemical compound CC(=O)\C=C\C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-BQYQJAHWSA-N 0.000 description 7
- VPKMGDRERYMTJX-CMDGGOBGSA-N 1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1-penten-3-one Chemical compound CCC(=O)\C=C\C1C(C)=CCCC1(C)C VPKMGDRERYMTJX-CMDGGOBGSA-N 0.000 description 6
- JXJIQCXXJGRKRJ-KOOBJXAQSA-N pseudoionone Chemical compound CC(C)=CCC\C(C)=C\C=C\C(C)=O JXJIQCXXJGRKRJ-KOOBJXAQSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention belongs to essence and flavoring agent technical field, and in particular to a kind of preparation method of fragrance intermediates.The present invention is using azepine modified aluminas nanometer ball particle as catalyst, catalyzing citral and butanone reaction generation methyl pseudo-ionone, and the selectivity of positive methyl pseudo-ionone is high in the methyl pseudo-ionone.High catalytic efficiency of the present invention, the high conversion rate of citral, the selectivity of positive methyl pseudo-ionone is high, wherein the selectivity of positive methyl pseudo-ionone and different methyl pseudo-ionone is more than 25:1；Catalyst of the present invention is recyclable in addition applies mechanically, and the conversion ratio of selectivity and substrate on product is without influence.
Description
Technical field
The invention belongs to essence and flavoring agent technical field, and in particular to a kind of preparation method of fragrance intermediates.
Background technology
Methylionone is the homologue of irisone, but its odor grade is more excellent than irisone, and its grace is soft
Note and good stability deeply favored by people.Positive methyl pseudo-ionone is that purposes compares in perfume synthesis industry
A kind of extensive intermediate, it is to synthesize the essential raw material of positive methylionone, and the direct shadow of height of its content
Ring to the height of later stage positive methylionone content and the flavor situation of overall fragrance.
Irisone is generated by pseudo ionone, and pseudo ionone is typically in alkalescence by citral and acetone
Under the conditions of occur aldol condensation generation, reaction equation is such as（1）：
（1）
Positive methylionone is synthesized by positive methyl pseudo-ionone, and positive methyl pseudo-ionone is by lemon
With butanone aldol condensation generation occurs in the basic conditions for aldehyde, and reaction equation is such as（2）：
（2）
It is required in the basic conditions in either positive methyl pseudo-ionone or pseudo ionone building-up process
Reaction.Because the application value of positive methylionone is larger, so developing the preparation method tool of positive methyl pseudo-ionone
There is important meaning.
Liquid caustic soda is usually added into during positive methyl pseudo-ionone is prepared in the prior art as catalyst, such as hydrogen-oxygen
Change sodium, the aqueous solution of barium hydroxide, or system of caustic alcohol ethanol etc., at present with the aqueous solution catalytic system of sodium hydroxide most
To be common, but the environmental pollution of inorganic base catalyst system and catalyzing is big, catalyst can not reclaim, and prepare positive methyl pseudo-ionone
During can produce substantial amounts of different methyl pseudo-ionone, i.e. product selectivity is poor, and the later stage is unfavorable for isolating and purifying.
CN101816950A discloses a kind of method of hydrotalcite-like compound catalyst and its catalytic synthesis of pseudo-ionone,
It is proposed to prepare pseudo ionone with the hydrotalcite film in the aluminium collective for being grown in surface anodization in the invention, it is false
Property irisone be to be prepared by citral and condensation of acetone, and the product generated is more single, in the absence of asking for regioselectivity
Topic, and citral and the positive methylionone of butanone reaction generation and asking for different first first irisone domain of the existence selectivity
Topic, it is seen that this catalyst cannot be used for the preparation of positive methyl pseudo-ionone.
Have great importance so developing a kind of catalyst system and catalyzing of green high-efficient and preparing positive methyl pseudo-ionone.
The content of the invention
The purpose of the present invention is to overcome in the positive methyl pseudo-ionone preparation process of fragrance intermediates in the prior art to urge
Agent pollution is big and can not recycle, the selectively low technical problem of positive methyl pseudo-ionone, there is provided a kind of positive first
The preparation method of base pseudo ionone.
According to an aspect of the present invention, the invention provides a kind of preparation method of fragrance intermediates, in the spices
Mesosome is positive methyl pseudo-ionone, is comprised the following steps：
1）Citral and catalyst stirring reaction 20-30min are added in reactor；
2）45-50 DEG C is warming up to, butanone reaction is added dropwise；
3）After butanone is added dropwise, 45-50 DEG C of insulation reaction to citral is reacted completely；
4）Room temperature is cooled to, filters, filters off except catalyst obtains filtrate；
5）Filtrate carries out rectifying and obtains the positive methyl pseudo-ionone that gas chromatographic purity is more than 97%；
The catalyst is azepine modified aluminas nanometer ball particle, the azepine modified aluminas nanometer ball particle by with
It is prepared by lower preparation method：
1）Dispersion step：Alumina powder is added to DMF and in the mixed solution of water composition, ultrasound fully spreads at room temperature
Obtain diffusion liquid；
2）Corrosion process：2N sodium hydrate aqueous solution, stirring reaction are instilled at 40 DEG C；
3）Azepine process：After sodium hydroxide is added dropwise, 2-methylimidazole is added immediately, and it is small to react 2-3 at 80-90 DEG C
When；
4）Separation circuit：Filtering, washing, dry presoma；
5）Carbonation process：Presoma is placed in nitrogen atmosphere the carbonization that heats up, carburizing temperature is 200-450 DEG C；Then certainly
It is 700-900 m so to be cooled to room temperature to obtain specific surface area2 g-1Azepine modified aluminas nanometer ball particle.
The preparation method of fragrance intermediates of the present invention, its further technical scheme are that the weight of material is used in preparation process
It is citral to measure ratio：Butanone：Catalyst=2.1:1.0~1.5:0.02~0.10, preferably 2.1:1.1:0.03；
The preparation method of fragrance intermediates of the present invention, its further technical scheme are modified aluminas nanometer ball particle system
Aluminum oxide, sodium hydroxide, the dosage mol ratio of 2-methylimidazole are aluminum oxide during standby：Sodium hydroxide：2-methylimidazole=1：
0.8~1.5:2.0~2.6, preferably 1: 1.2 : 2.3；Aluminum oxide, sodium hydroxide, 2-methylimidazole are controlled in the present invention
Dosage, alumina part is reacted in sodium hydroxide, produce corrosion phenomenon, be i.e. partial oxidation aluminium and sodium hydroxide reacts
Sodium metaaluminate is generated, hole is formed and surface is modified；Then it is modified using 2-methylimidazole azepine, obtains presoma.
The preparation method of fragrance intermediates of the present invention, its further technical scheme are that drying temperature is 55- in separation circuit
65 DEG C, dry to weight no longer less loss；
The preparation method of fragrance intermediates of the present invention, its further technical scheme are that carburizing temperature is in carbonation process
370-420℃；Found in research process, carburizing temperature influences non-on the specific surface area of azepine modified aluminas nanometer ball particle
Chang great, carburizing temperature are less than 200 DEG C or higher than 500 DEG C, the azepine modified aluminas nanosphere specific grain surface prepared
Small, typically smaller than 500 m of product2 g-1, had a strong impact on the conversion ratio and reaction rate of citral；In addition when temperature is too high, urge
Changing efficiency not only reduces, and the selectivity of positive methyl pseudo-ionone reduces.
Compared with prior art, the invention has the advantages that：
1st, high catalytic efficiency of the present invention, the high conversion rate of citral, the selectivity of positive methyl pseudo-ionone is high, wherein
The selectivity of positive methyl pseudo-ionone and different methyl pseudo-ionone is more than 25:1；
2nd, catalyst of the present invention is beneficial to recovery, and filtering can remove, convenient post processing；
3rd, catalyst activity of the present invention is high, repeats and recycles, the conversion ratio of recovery catalyst and selective nothing
It is decreased obviously.
Embodiment
To make the object, technical solutions and advantages of the present invention of greater clarity, with reference to embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
Embodiment 1
1）The preparation of catalyst：
30g alumina powders are added in the mixed solution that 300ml DMF form with water（The volume ratio of DMF and water is 5:1）,
Ultrasound fully spreads to obtain diffusion liquid at room temperature；2N sodium hydrate aqueous solution, stirring reaction 30min are instilled at 40 DEG C；Hydrogen-oxygen
Change sodium to drip after solution adds, add 2-methylimidazole immediately（Wherein aluminum oxide：Sodium hydroxide：2-methylimidazole=1：0.8:
2.0）, at 80-90 DEG C reaction 2-3 hours filter, washing, 55-65 DEG C of dry presoma；Presoma is placed in nitrogen atmosphere
Heating carbonization, carburizing temperature are 200 DEG C；Then it is 720 m to naturally cool to room temperature and obtain specific surface area2 g-1Azepine be modified oxygen
Change aluminium nanometer ball particle.
2）Catalytic reaction
100g citrals and the catalyst stirring reaction 20-30min of above-mentioned preparation are added in reactor；It is warming up to 45-50
DEG C, butanone reaction is added dropwise（By weight calculating, citral：Butanone：Catalyst=2.1:1.5:0.02）；After butanone is added dropwise,
45-50 DEG C of insulation reaction is reacted completely to citral（Extract reaction solution and tested using GC）；Room temperature is cooled to, is filtered, is filtered off and remove
Catalyst obtains filtrate；Filtrate carries out rectifying and obtains positive methyl pseudo-ionone, send GC to detect positive methyl pseudo-ionone and different
Methyl pseudo-ionone content.
Embodiment 2
1）The preparation of catalyst：
30g alumina powders are added in the mixed solution that 300ml DMF form with water（The volume ratio of DMF and water is 5:1）,
Ultrasound fully spreads to obtain diffusion liquid at room temperature；2N sodium hydrate aqueous solution, stirring reaction 30min are instilled at 40 DEG C；Hydrogen-oxygen
Change sodium to drip after solution adds, add 2-methylimidazole immediately（Wherein aluminum oxide：Sodium hydroxide：2-methylimidazole=1：1.5:
2.0）, at 80-90 DEG C reaction 2-3 hours filter, washing, 55-65 DEG C of dry presoma；Presoma is placed in nitrogen atmosphere
Heating carbonization, carburizing temperature are 450 DEG C；Then it is 810m to naturally cool to room temperature and obtain specific surface area2 g-1Azepine it is modified oxidized
Aluminium nanometer ball particle.
2）Catalytic reaction
100g citrals and the catalyst stirring reaction 20-30min of above-mentioned preparation are added in reactor；It is warming up to 45-50
DEG C, butanone reaction is added dropwise（By weight calculating, citral：Butanone：Catalyst=2.1:1.0~1.5:0.02~0.10）；Butanone
After being added dropwise, 45-50 DEG C of insulation reaction to citral is reacted completely（Extract reaction solution and tested using GC）；Room temperature is cooled to, is taken out
Filter, is filtered off except catalyst obtains filtrate；Filtrate carries out rectifying and obtains positive methyl pseudo-ionone, send GC to detect the positive false purple of methyl
Rowland ketone and different methyl pseudo-ionone content.
Embodiment 3
1）The preparation of catalyst：
30g alumina powders are added in the mixed solution that 300ml DMF form with water（The volume ratio of DMF and water is 5:1）,
Ultrasound fully spreads to obtain diffusion liquid at room temperature；2N sodium hydrate aqueous solution, stirring reaction 30min are instilled at 40 DEG C；Hydrogen-oxygen
Change sodium to drip after solution adds, add 2-methylimidazole immediately（Wherein aluminum oxide：Sodium hydroxide：2-methylimidazole=1:
1.2 : 2.3）, at 80-90 DEG C reaction 2-3 hours filter, washing, 55-65 DEG C of dry presoma；Presoma is placed in nitrogen
Heat up carbonization in atmosphere, and carburizing temperature is 200 DEG C；Then it is 860 m to naturally cool to room temperature and obtain specific surface area2 g-1Azepine
Modified aluminas nanometer ball particle.
2）Catalytic reaction
100g citrals and the catalyst stirring reaction 20-30min of above-mentioned preparation are added in reactor；It is warming up to 45-50
DEG C, butanone reaction is added dropwise（By weight calculating, citral：Butanone：Catalyst=2.1:1.1:0.03）；After butanone is added dropwise,
45-50 DEG C of insulation reaction is reacted completely to citral（Extract reaction solution and tested using GC）；Room temperature is cooled to, is filtered, is filtered off and remove
Catalyst obtains filtrate；Filtrate carries out rectifying and obtains positive methyl pseudo-ionone, send GC to detect positive methyl pseudo-ionone and different
Methyl pseudo-ionone content.
Embodiment 4
The catalyst for taking embodiment 3 to filter out is reclaimed, after DMF elution, again according to embodiment 3 after naturally dry
In reaction condition reacted.
Comparative example 1
Catalyst preparation is prepared according to the method for embodiment 3.
Taken in course of reaction catalyst, citral, butanone add together after 45-50 DEG C of insulation reaction it is complete to citral
Reaction.
Comparative example 2
Catalyst preparation is prepared according to the method for embodiment 3.
100g citrals and the catalyst stirring reaction 20-30min prepared are added in reactor；60-70 DEG C is warming up to, drop
Butanone is added to react（By weight calculating, citral：Butanone：Catalyst=2.1:1.1:0.03）；After butanone is added dropwise, 60-70
DEG C insulation reaction is reacted completely to citral（Extract reaction solution and tested using GC）；Room temperature is cooled to, filters, filters off except catalyst
Obtain filtrate；Filtrate carries out rectifying and obtains positive methyl pseudo-ionone, send GC to detect positive methyl pseudo-ionone and the vacation of different methyl
Property irisone content.
Comparative example 3
Catalyst preparation is prepared according to the method for embodiment 3.
100g citrals and the catalyst stirring reaction 20-30min prepared are added in reactor；30-40 DEG C is warming up to, drop
Butanone is added to react（By weight calculating, citral：Butanone：Catalyst=2.1:1.1:0.03）；After butanone is added dropwise, 30-40
DEG C insulation reaction is reacted completely to citral（Extract reaction solution and tested using GC）；Room temperature is cooled to, filters, filters off except catalyst
Obtain filtrate；Filtrate carries out rectifying and obtains positive methyl pseudo-ionone, send GC to detect positive methyl pseudo-ionone and the vacation of different methyl
Property irisone content.
GC testing results are as shown in table 1 after embodiment 1-4 and its comparative example 1-3 reaction solution and its distillation：
Note：Conversion ratio refers to：100% subtracts the surplus of citral in reaction solution, and yield refers to（Product of distillation weight multiplies
With the area percentage of positive methyl pseudo-ionone in distillate）Divided by theoretical amount, it is fixed in the calculating process of theoretical amount herein
The selectivity of adopted positive methyl pseudo-ionone is absolutely.
Result above shows, in catalytic reaction process, it is necessary to first add citral and catalyst action for a period of time, it is no
Then the selectivity of positive methyl pseudo-ionone is low；And reaction temperature also should not too high, too high positive methyl pseudo-ionone
Selectivity it is low, the conversion ratio of too low then citral is low.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's
In the case of spirit and scope, embodiments of the present invention can be made with various changes, replacement and change.
Claims (4)
1. a kind of preparation method of fragrance intermediates, the fragrance intermediates are positive methyl pseudo-ionone, including following step
Suddenly：
1）Citral and catalyst stirring reaction 20-30min are added in reactor；
2）45-50 DEG C is warming up to, butanone reaction is added dropwise；
3）After butanone is added dropwise, 45-50 DEG C of insulation reaction to citral is reacted completely；
4）Room temperature is cooled to, filters, filters off except catalyst obtains filtrate；
5）Filtrate carries out rectifying and obtains the positive methyl pseudo-ionone that gas chromatographic purity is more than 97%；
The catalyst is azepine modified aluminas nanometer ball particle, and the azepine modified aluminas nanometer ball particle is by following system
It is prepared by Preparation Method：
1）Dispersion step：Alumina powder is added to DMF and in the mixed solution of water composition, ultrasound fully spreads at room temperature
Diffusion liquid；
2）Corrosion process：2N sodium hydrate aqueous solution, stirring reaction are instilled at 40 DEG C；
3）Azepine process：After sodium hydroxide is added dropwise, 2-methylimidazole is added immediately, reacts 2-3 hours at 80-90 DEG C；
4）Separation circuit：Filtering, washing, dry presoma；
5）Carbonation process：Presoma is placed in nitrogen atmosphere the carbonization that heats up, carburizing temperature is 200-450 DEG C；Then it is naturally cold
But the azepine modified aluminas nanometer ball particle that specific surface area is 700-900 m2 g-1 is obtained to room temperature；
The weight consumption ratio of material is citral in preparation process：Butanone：Catalyst=2.1:1.0~1.5:0.02~0.10；
Aluminum oxide, sodium hydroxide, the dosage mol ratio of 2-methylimidazole are oxygen in modified aluminas nanosphere particulate production
Change aluminium：Sodium hydroxide：2-methylimidazole=1：0.8~1.5:2.0~2.6.
2. preparation method according to claim 1, it is characterised in that：The weight consumption ratio of material is lemon in preparation process
Aldehyde：Butanone：Catalyst=2.1:1.1:0.03.
3. preparation method according to claim 1, it is characterised in that：Oxygen in modified aluminas nanosphere particulate production
It is aluminum oxide to change aluminium, sodium hydroxide, the dosage mol ratio of 2-methylimidazole：Sodium hydroxide：2-methylimidazole=1: 1.2 :
2.3。
4. preparation method according to claim 1, it is characterised in that：Carburizing temperature is 370-420 DEG C in carbonation process.
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