CN106045829B - A kind of epoxy carboxylic acids' ester prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal - Google Patents
A kind of epoxy carboxylic acids' ester prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal Download PDFInfo
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- FJCQUJKUMKZEMH-UHFFFAOYSA-N 2-methyl-4-(2,6,6-trimethylcyclohexen-1-yl)but-2-enal Chemical compound O=CC(C)=CCC1=C(C)CCCC1(C)C FJCQUJKUMKZEMH-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 150000002148 esters Chemical class 0.000 title claims abstract description 54
- 239000004593 Epoxy Substances 0.000 title claims abstract description 48
- 150000001735 carboxylic acids Chemical class 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 216
- 239000000243 solution Substances 0.000 claims abstract description 59
- 239000007787 solid Substances 0.000 claims abstract description 49
- 150000003839 salts Chemical class 0.000 claims abstract description 42
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 239000012043 crude product Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- MVOSYKNQRRHGKX-UHFFFAOYSA-N 11-Undecanolactone Chemical compound O=C1CCCCCCCCCCO1 MVOSYKNQRRHGKX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- WQHRXOFTZJVUGQ-UHFFFAOYSA-N CO.CC(C=O)=CCC1=C(CCCC1(C)C)C Chemical compound CO.CC(C=O)=CCC1=C(CCCC1(C)C)C WQHRXOFTZJVUGQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 150000001299 aldehydes Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- HTSABYAWKQAHBT-UHFFFAOYSA-N trans 3-methylcyclohexanol Natural products CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 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 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 14
- 239000002351 wastewater Substances 0.000 abstract description 14
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 150000002576 ketones Chemical class 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- -1 carbon aldehyde Chemical class 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 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 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 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 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 235000019155 vitamin A Nutrition 0.000 description 3
- 239000011719 vitamin A Substances 0.000 description 3
- 229940045997 vitamin a Drugs 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000003476 Darzens condensation reaction Methods 0.000 description 1
- 229930183419 Irisone Natural products 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- UZFLPKAIBPNNCA-BQYQJAHWSA-N alpha-ionone Chemical compound CC(=O)\C=C\C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-BQYQJAHWSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000013517 stratification 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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
The present invention relates to the green synthesis process that a kind of epoxy carboxylic acids' ester prepares 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, including：（1）Epoxy carboxylic acids' ester methanol solution is cooled to certain temperature in advance, and the reactant aqueous solution of appropriate A is added for a period of time；（2）Reaction mixture is through being obtained by filtration the methanol solution of solid salt and 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal；（3）Solid salt is dried after being washed to no organic substance residues with methanol；（4）The methanol solution of undecalactone is passed through enough sour gas B to alkalescent, and a small amount of solid salt of generation is through filtering and and above-mentioned steps（3）Solid salt handle together, obtained 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal methanol solution obtains 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude product through desolventizing.The invention avoids the discharges of high-COD waste water, decrease the usage amount of organic solvent, have the good value of environmental protection；The extraction, evaporation or rectifying for decreasing waste water simultaneously, reduce energy consumption；In addition, due to not having discharge of wastewater, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal product not to lose substantially, reaction yield also improves.
Description
Technical field
The present invention relates to the preparation processes of vitamin A intermediate, are specifically related to a kind of 14 carbon of epoxy carboxylic acids' ester preparation
The green synthesis process of aldehyde.
Background technology
2- methyl -4-（2,6,6- trimethyl -1- cyclohexene -1- bases）- 2- butene-1s-aldehyde（Abbreviation 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal or C14
Aldehyde）It is one of the important intermediate of Roche process routes synthesis vitamin A.The patent of invention of Publication No. CN103408410 carries
A kind of preparation facilities of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal has been supplied, by increasing the device of sodium methoxide concentration, the yield of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal has been made to reach
97%, reaction yield has been increased to 90%；The patent of invention of Publication No. CN101070277 provides a kind of vitamin A intermediate
The method of purification and its device of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal can stably obtain and contain by using high-performance fillers and the method for continuous rectification
The refined 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal of 98% or more 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal；The patent of Publication No. CN104892381A provides a kind of by by 14
2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal isomers is first isomerizated into 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal in carbon aldehyde rectifying low boiling by-product, then the method for carrying out rectifying separation, no
Only realize the recycling of β irisones in 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal rectifying low boiling by-product, at the same also achieve 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal and its
The recycling of isomers.
Industrial 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal is mainly using alpha, beta-lonone and methyl chloroacetate as raw material at present, using methanol as solvent, warp
Darzens condensation reactions prepare.When preparing 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal using the method, it is necessary to first obtain intermediate α, beta epoxide carboxylic acid
Ester, then hydrolysis decarboxylation and double-bond isomerism indexing occurs obtain 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal in strong alkaline aqueous solution, reaction process is as follows：
In the process, it will produce when preparing 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal by epoxy carboxylic acids' ester largely useless containing high concentration COD and salinity
Water, although industrially using organic solvent extraction, evaporation or the means such as rectifying partial organic substances therein can be removed, in waste water
Still there is large amount of organic residual, it is difficult to meet the environmental requirement being increasingly stringenter.It to be used largely just after technique hydrolysis
A part is dissolved in 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal product in methanol aqueous solution and extracted by the organic extractants such as hexane, dichloromethane or toluene,
The removal process of these extractants not only needs higher energy consumption, but also is discharged into air and produces because solvent can not all recycle
Raw serious exhaust emission.In addition, since the organic solvents such as the methanol that contains in waste water also have 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal certain dissolubility,
Part 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal product can not extract and enter in waste water, and yield is caused to reduce.
Based on this, proposing the present invention.
Invention content
The purpose of the present invention is being directed to the problem of above-mentioned epoxy carboxylic acids' ester prepares 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal process, one is provided
Kind epoxy carboxylic acids' ester prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, and the process employs the reaction systems that little water participates in, and keep away
The discharge of high-COD waste water is exempted from, the methanol solvate that solid washing process uses is identical as epoxy carboxylic acids' ester preparation process solvent simultaneously
It can be used for diluting epoxy carboxylic acids' ester solution, avoid the use of other organic solvents, there is the good value of environmental protection；Simultaneously
Extraction, the extractant removal process for reducing waste water reduce energy consumption and exhaust gas discharge；In addition, due to directly being recycled after hydrolysis
Methanol can be obtained 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude product, and product loss is less, to which yield also improves.
In order to achieve the above objectives, the present invention is achieved by the following technical solutions：
A kind of epoxy carboxylic acids' ester prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, includes the following steps：
（1）Mass concentration is that epoxy carboxylic acids' ester methanol solution of 10-50% is cooled to -40 DEG C -20 DEG C in advance, and the water of appropriate A is added
Solution reaction is for a period of time；The A is sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate；The aqueous solution quality of the A
A concentration of 10-50%；The molar ratio of the A and epoxy carboxylic acids' ester is 0.5-1.2：1, A with epoxy carboxylic acids' ester reaction time be 5-60
Minute, reaction temperature is 20-60 DEG C；
（2）Reaction mixture is through being obtained by filtration the methanol solution of solid salt and 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal；The methanol of the 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal
Water content is 0-10% in solution；
（3）Solid salt is dried after being washed to no organic substance residues with methanol；Wherein, washing methanol is for preparing epoxy carboxylic acids
Ester methanol solution merges with the methanol solution of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal；It can be recycled after solid salt washing and drying or as common solid
Useless processing；
（4）It is carbon dioxide that the methanol solution of undecalactone, which is passed through enough sour gas B, the sour gas B, so that
PH is 7.5-8.5, and a small amount of solid salt of generation is through filtering and and above-mentioned steps（3）Solid salt handle together, 14 obtained
Carbon aldehyde methanol solution, water content is 0-7% in the methanol solution of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, and 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude product is obtained through desolventizing.
The step（1）In epoxy carboxylic acids' ester be 3- methyl -3- [2-（2,6,6- 3-methyl cyclohexanol -1- alkenyls）Second
Alkenyl] ethylene oxide -2- carboxylate methyl esters.
The step（1）Middle A is sodium hydroxide or sodium carbonate.
The step（2）Middle 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal is 2- methyl -4-（2,6,6- trimethyl -1- cyclohexene -1- bases）- 2- fourths
Alkene -1- aldehyde.
The step（2）In 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal methanol solution in water content be 0-5%.
The step（2）Middle solid salt is villaumite, carbonate or the bicarbonate of sodium or potassium.
The step（2）It can be recycled after middle solid salt washing and drying or as common fixed-end forces.
The step（4）Middle sour gas B is carbon dioxide.
The step（4）Water content is 0-3% in the methanol solution of middle 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal.
The step（4）To obtain 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal thick through normal pressure or vacuum distillation removing solvent for middle 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal methanol solution
Product, crude product carry out rectification under vacuum, and the component that tower top outlet collects 80-120 DEG C is 14 aldehyde of high-purity C, tower reactor outlet discharge foot
Material.
Beneficial effects of the present invention are as follows：
Epoxy carboxylic acids' ester of the present invention prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, uses the reactant of little water participation
System, avoids the discharge of high-COD waste water, decreases the usage amount of organic solvent, has the good value of environmental protection；Also subtract simultaneously
The extraction, evaporation or rectifying for having lacked waste water, reduce energy consumption；In addition, due to there is no discharge of wastewater, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal product not to have substantially
There are loss, reaction yield also to improve.
Specific implementation mode
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
Comparative example 1
Using 500g β ketone as raw material, is passed through up to gloomy react with raw materials such as methyl chloroacetate, sodium methoxides and 3- methyl -3- is prepared
[2-（2,6,6- 3-methyl cyclohexanol -1- alkenyls）Vinyl] ethylene oxide -2- carboxylate methyl esters（Hereinafter referred to as epoxy carboxylic acids' ester）,
Then epoxy carboxylic acids' ester ester methanol solution that 2000ml methanol is configured to 25% or so is added, is cooled to 0 DEG C in advance, is then added
The aqueous sodium carbonate that 1500ml mass fractions are 40%, finishes and continuously adds 3000ml water, be stirred to react 1h, stratification obtains
To upper layer 2- methyl -4-（2,6,6- trimethyl -1- cyclohexene -1- bases）- 2- butene-1s-aldehyde（Hereinafter referred to as 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal）Product
Layer and lower layer's waste water layer；Lower layer's waste water layer extracts with 3000ml toluene and is layered to obtain upper toluene layer, lower layer's waste water layer rectifying
It is used as sewage disposal, COD 20000-40000ppm after recycling methanol；After upper toluene layer is mixed with gas producing formation, with a small amount of dilute
It is 7-9 that hydrochloric acid, which is neutralized to pH, and 500ml washings are added, and layering obtains 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude product toluene solution, vacuum distillation removing toluene
2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude product is obtained, rectification under vacuum obtains 461g 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal products,HPLC purity is 97.4%, it is counted using β ketone as raw material,Molar yield is 83.8%。
Embodiment 1
Using 500g β ketone as raw material, is passed through up to gloomy react with raw materials such as methyl chloroacetate, sodium methoxides and 3- methyl -3- is prepared
[2-（2,6,6- 3-methyl cyclohexanol -1- alkenyls）Vinyl] ethylene oxide -2- carboxylate methyl esters（Hereinafter referred to as epoxy carboxylic acids' ester）,
Then epoxy carboxylic acids' ester ester methanol solution that 2000ml methanol is configured to 25% or so is added, is cooled to -10 DEG C or so in advance, is added
The aqueous sodium carbonate that 520g mass fractions are 30% is warming up to 35 DEG C of reaction 1.5h, it is molten that 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude methanol is obtained by filtration
The hybrid solids salt such as liquid and sodium chloride, sodium carbonate, sodium bicarbonate；Solid salt three to four washes cleans of 2000ml methanol point,
The methanol cleaning solution being obtained by filtration gives over to matches epoxy carboxylic acids' ester solution next time, and solid obtains white solid salt after drying, passes through
Detection is substantially without organic substance residues；Obtained undecalactone crude methanol solution continues to be passed through carbon dioxide, until pH be 7.5-8.5 it
Between stop be passed through carbon dioxide, a small amount of solid salt being obtained by filtration is mixed with the above-mentioned solid salt of next group；Ten obtained after neutralization
Four aldehyde crude methanol solution,It is 3.15% that karl-Fischer method, which detects moisture,, 14 carbon are obtained after being evaporated under reduced pressure methanol removal
Aldehyde crude product, rectification under vacuum obtain 470g 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal products,HPLC purity is 97.8%, it is counted using β ketone as raw material,Molar yield is 85.7%。
Embodiment 2
Using 500g β ketone as raw material, is passed through up to gloomy react with raw materials such as methyl chloroacetate, sodium methoxides and 3- methyl -3- is prepared
[2-（2,6,6- 3-methyl cyclohexanol -1- alkenyls）Vinyl] ethylene oxide -2- carboxylate methyl esters（Hereinafter referred to as epoxy carboxylic acids' ester）,
Then epoxy carboxylic acids' ester ester methanol solution that 2500ml methanol is configured to 20% or so is added, is cooled to 0 DEG C or so in advance, 370g is added
The aqueous sodium carbonate that mass fraction is 45% is warming up to 40 DEG C of reaction 1h, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude methanol solution and chlorine is obtained by filtration
Change the hybrid solids salt such as sodium, sodium carbonate, sodium bicarbonate；Solid salt three to four washes cleans of 2500ml methanol point, are filtered
To methanol cleaning solution give over to and match epoxy carboxylic acids' ester solution next time, solid obtains white solid salt after drying, after testing base
This is without organic substance residues；Obtained undecalactone crude methanol solution continues to be passed through carbon dioxide, until pH stops between 7.5-8.5
It is passed through carbon dioxide, a small amount of solid salt being obtained by filtration is mixed with the above-mentioned solid salt of next group；The undecalactone obtained after neutralization is thick
Product methanol solution,It is 1.72% that karl-Fischer method, which detects moisture,, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude product is obtained after being evaporated under reduced pressure methanol removal,
Rectification under vacuum obtains 478g 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal products,HPLC purity is 98.6%, it is counted using β ketone as raw material,Molar yield is 87.9%。
Embodiment 3
Using 500g β ketone as raw material, is passed through up to gloomy react with raw materials such as methyl chloroacetate, sodium methoxides and 3- methyl -3- is prepared
[2-（2,6,6- 3-methyl cyclohexanol -1- alkenyls）Vinyl] ethylene oxide -2- carboxylate methyl esters（Hereinafter referred to as epoxy carboxylic acids' ester）,
Then epoxy carboxylic acids' ester ester methanol solution that 3000ml methanol is configured to 17% or so is added, is cooled to 0 DEG C or so in advance, 300g is added
The sodium hydrate aqueous solution that mass fraction is 20% is warming up to 35 DEG C or so reaction 1h, it is molten that 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude methanol is obtained by filtration
The hybrid solids salt such as liquid and sodium chloride, sodium carbonate, sodium bicarbonate；Solid salt three to four washes cleans of 2500ml methanol point,
The methanol cleaning solution being obtained by filtration gives over to matches epoxy carboxylic acids' ester solution next time, and solid obtains white solid salt after drying, passes through
Detection is substantially without organic substance residues；Obtained undecalactone crude methanol solution continues to be passed through carbon dioxide, until pH be 7.5-8.5 it
Between stop be passed through carbon dioxide, a small amount of solid salt being obtained by filtration is mixed with the above-mentioned solid salt of next group；Ten obtained after neutralization
Four aldehyde crude methanol solution,It is 1.65% that karl-Fischer method, which detects moisture,, 14 carbon are obtained after being evaporated under reduced pressure methanol removal
Aldehyde crude product, rectification under vacuum obtain 470g 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal products,HPLC purity is 98.1%, it is counted using β ketone as raw material,Molar yield is 85.9%。
Embodiment 4
Using 500g β ketone as raw material, is passed through up to gloomy react with raw materials such as methyl chloroacetate, sodium methoxides and 3- methyl -3- is prepared
[2-（2,6,6- 3-methyl cyclohexanol -1- alkenyls）Vinyl] ethylene oxide -2- carboxylate methyl esters（Hereinafter referred to as epoxy carboxylic acids' ester）,
Then epoxy carboxylic acids' ester ester methanol solution that 3000ml methanol is configured to 17% or so is added, is cooled to -10 DEG C or so in advance, is added
The sodium hydrate aqueous solution that 400g mass fractions are 20% is warming up to 25 DEG C or so reaction 1.5h, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude product is obtained by filtration
The hybrid solids salt such as methanol solution and sodium chloride, sodium carbonate, sodium bicarbonate；Solid salt three to four washings of 2000ml methanol point
Totally, the methanol cleaning solution being obtained by filtration gives over to matches epoxy carboxylic acids' ester solution next time, and solid obtains white solid after drying
Salt, after testing substantially without organic substance residues；Obtained undecalactone crude methanol solution continues to be passed through carbon dioxide, until pH is 7.5-
Stop being passed through carbon dioxide between 8.5, a small amount of solid salt being obtained by filtration is mixed with the above-mentioned solid salt of next group；It is obtained after neutralization
Undecalactone crude methanol solution,It is 2.55% that karl-Fischer method, which detects moisture,, ten are obtained after being evaporated under reduced pressure methanol removal
Four carbon aldehyde crude products, rectification under vacuum obtain 475g 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal products,HPLC purity is 98.5%, it is counted using β ketone as raw material,Mole receive Rate is 87.2%。
Embodiment 5
Using 500g β ketone as raw material, is passed through up to gloomy react with raw materials such as methyl chloroacetate, sodium methoxides and 3- methyl -3- is prepared
[2-（2,6,6- 3-methyl cyclohexanol -1- alkenyls）Vinyl] ethylene oxide -2- carboxylate methyl esters（Hereinafter referred to as epoxy carboxylic acids' ester）,
Then epoxy carboxylic acids' ester ester methanol solution that 2000ml methanol is configured to 25% or so is added, is cooled to -10 DEG C or so in advance, is added
The sodium hydrate aqueous solution that 200g mass fractions are 40% is warming up to 40 DEG C or so reaction 1.5h, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude product is obtained by filtration
The hybrid solids salt such as methanol solution and sodium chloride, sodium carbonate, sodium bicarbonate；Solid salt three to four washings of 2000ml methanol point
Totally, the methanol cleaning solution being obtained by filtration gives over to matches epoxy carboxylic acids' ester solution next time, and solid obtains white solid after drying
Salt, after testing substantially without organic substance residues；Obtained undecalactone crude methanol solution continues to be passed through carbon dioxide, until pH is 7.5-
Stop being passed through carbon dioxide between 8.5, a small amount of solid salt being obtained by filtration is mixed with the above-mentioned solid salt of next group；It is obtained after neutralization
Undecalactone crude methanol solution,It is 1.04% that karl-Fischer method, which detects moisture,, ten are obtained after being evaporated under reduced pressure methanol removal
Four carbon aldehyde crude products, rectification under vacuum obtain 466g 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal products,HPLC purity is 98.3%, it is counted using β ketone as raw material,Mole receive Rate is 85.4%。
Above-described embodiment is only used for illustrating the inventive concept of the present invention, rather than the restriction to rights protection of the present invention,
All changes for carrying out unsubstantiality to the present invention using this design, should all fall into protection scope of the present invention.
Claims (9)
1. a kind of epoxy carboxylic acids' ester prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, it is characterised in that include the following steps：
（1）Mass concentration is that epoxy carboxylic acids' ester methanol solution of 10-50% is cooled to -40 DEG C -20 DEG C in advance, and the aqueous solution of appropriate A is added
Reaction a period of time；The A is sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate；The aqueous solution mass concentration of the A
For 10-50%；The molar ratio of the A and epoxy carboxylic acids' ester is 0.5-1.2：1, A with epoxy carboxylic acids' ester reaction time is 5-60 point
Clock, reaction temperature are 20-60 DEG C；
（2）Reaction mixture is through being obtained by filtration the methanol solution of solid salt and 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal；The methanol solution of the 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal
Middle water content is 0-10%；
（3）Solid salt is dried after being washed to no organic substance residues with methanol；Wherein, washing methanol is for preparing epoxy carboxylic acids' ester first
Alcoholic solution merges with the methanol solution of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal；
（4）The methanol solution of undecalactone is passed through enough sour gas B, and the sour gas B is carbon dioxide so that pH is
7.5-8.5, a small amount of solid salt of generation is through filtering and and above-mentioned steps（3）Solid salt handle together, obtained 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal
Methanol solution, water content is 0-7% in the methanol solution of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, and 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude product is obtained through desolventizing.
2. epoxy carboxylic acids' ester as described in claim 1 prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, it is characterised in that：The step
Suddenly（1）In epoxy carboxylic acids' ester be 3- methyl -3- [2-（2,6,6- 3-methyl cyclohexanol -1- alkenyls）Vinyl] ethylene oxide -2-
Carboxylate methyl ester.
3. epoxy carboxylic acids' ester as described in claim 1 prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, it is characterised in that：The step
Suddenly（1）Middle A is sodium hydroxide or sodium carbonate.
4. epoxy carboxylic acids' ester as described in claim 1 prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, it is characterised in that：The step
Suddenly（2）Middle 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal is 2- methyl -4-（2,6,6- trimethyl -1- cyclohexene -1- bases）- 2- butene-1s-aldehyde.
5. epoxy carboxylic acids' ester as described in claim 1 prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, it is characterised in that：The step
Suddenly（2）In 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal methanol solution in water content be 0-5%.
6. epoxy carboxylic acids' ester as described in claim 1 prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, it is characterised in that：The step
Suddenly（2）Middle solid salt is villaumite, carbonate or the bicarbonate of sodium or potassium.
7. epoxy carboxylic acids' ester as described in claim 1 prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, it is characterised in that：The step
Suddenly（2）It can be recycled after middle solid salt washing and drying or as common fixed-end forces.
8. epoxy carboxylic acids' ester as described in claim 1 prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, it is characterised in that：The step
Suddenly（4）Water content is 0-3% in the methanol solution of middle 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal.
9. epoxy carboxylic acids' ester as described in claim 1 prepares the green synthesis process of 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, it is characterised in that：The step
Suddenly（4）Middle 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal methanol solution obtains 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal crude product through normal pressure or vacuum distillation removing solvent, and crude product is depressurized
Rectifying, the component that tower top outlet collects 80-120 DEG C are 14 aldehyde of high-purity C, tower reactor outlet discharge heel.
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| CS167108B1 (en) * | 1974-02-22 | 1976-04-29 | ||
| US3998856A (en) * | 1975-04-10 | 1976-12-21 | Hoffmann-La Roche Inc. | Preparation of epoxides |
| CN1348947A (en) * | 2000-10-18 | 2002-05-15 | 浙江新和成股份有限公司 | Prepn process of vitamin A intermediate |
| CN101268044A (en) * | 2005-09-16 | 2008-09-17 | 帝斯曼知识产权资产管理有限公司 | Process for the preparation of an epoxy compound and an aldehyde |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS167108B1 (en) * | 1974-02-22 | 1976-04-29 | ||
| US3998856A (en) * | 1975-04-10 | 1976-12-21 | Hoffmann-La Roche Inc. | Preparation of epoxides |
| CN1348947A (en) * | 2000-10-18 | 2002-05-15 | 浙江新和成股份有限公司 | Prepn process of vitamin A intermediate |
| CN101268044A (en) * | 2005-09-16 | 2008-09-17 | 帝斯曼知识产权资产管理有限公司 | Process for the preparation of an epoxy compound and an aldehyde |
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Application publication date: 20161026 Assignee: ZHEJIANG NHU SPECIAL MATERIALS Co.,Ltd. Assignor: SHANGYU NHU BIO-CHEM Co.,Ltd. Contract record no.: X2023980043740 Denomination of invention: A Green Synthesis Process for Preparing Tetradecanal from Epoxy Carboxylate Esters Granted publication date: 20180914 License type: Common License Record date: 20231019 Application publication date: 20161026 Assignee: ZHEJIANG NHU PHARMACEUTICAL Co.,Ltd. Assignor: SHANGYU NHU BIO-CHEM Co.,Ltd. Contract record no.: X2023980043734 Denomination of invention: A Green Synthesis Process for Preparing Tetradecanal from Epoxy Carboxylate Esters Granted publication date: 20180914 License type: Common License Record date: 20231019 |