CN109438200A - Metallic catalyst prepares the synthesis technology of 3,3- dimethyl butyraldehyde - Google Patents
Metallic catalyst prepares the synthesis technology of 3,3- dimethyl butyraldehyde Download PDFInfo
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- CN109438200A CN109438200A CN201811209301.XA CN201811209301A CN109438200A CN 109438200 A CN109438200 A CN 109438200A CN 201811209301 A CN201811209301 A CN 201811209301A CN 109438200 A CN109438200 A CN 109438200A
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- metallic catalyst
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- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
Abstract
The present invention relates to a kind of synthesis technologies of metallic catalyst preparation 3,3- dimethyl butyraldehyde, belong to technical field of organic synthesis.The synthesis technology includes the following steps: to carry out cooling processing to dichloromethane solvent using liquid nitrogen cryogenics device；It sequentially adds tert-butyl chloride and metallic catalyst is sufficiently mixed dissolution；Vinylacetate is added in the mixed liquor of step 2, obtains crude reaction；Distillation processing is carried out to crude reaction；Ice cube is added in the distillate of step 4；Sodium carbonate is added in distillate in steps of 5, carries out second distillation；Obtain pure 3,3- dimethyl butyraldehyde.Synthesis technology provided by the present invention, it is scientific and reasonable, it is simple and easy, have the characteristics that low production cost, high income, environmentally protective and with high purity.
Description
Technical field
The present invention relates to a kind of synthesis technologies of metallic catalyst preparation 3,3- dimethyl butyraldehyde, belong to organic synthesis technology
Field.
Background technique
Neotame (N- [N- (3,3- dimethylbutyl)-L- α-aspartic acid]-L-phenylalanine -1-- first in sweetener
Ester) it is the high sweetener developed by the Lars Niu Te Vit, the U.S., it has a high sugariness, low in calories, that stability is high etc. is excellent
Point, it is safe to the human body harmless, it is the very excellent non-nutritive intense sweetener of a kind of performance, there is huge market potential,
And 3,3- dimethyl butyraldehydes are the important intermediates of neotame, due to its market price valuableness, cause product price that can not reduce, because
This needs to study a method that is not only economic but also specially preparing the intermediate.3,3- dimethyl butyraldehydes, chemical structural formula are as follows
Shown in formula:
The preparation method of 3,3- dimethyl butyraldehydes has very much: in CN101311151 is prepared by raw material of ethylene gas, so
And ethylene gas transport, storage, in terms of all have higher requirement, and this preparation method process compared with
Long, energy consumption is high, it is also necessary at a high temperature of 300 DEG C or more using inert gas be carrier gas by 3,3- dimethyl butyrate alcohol and water mixed steam
After change, catalytic dehydrogenation is obtained under the noble metal existence condition, high production cost, and production security is low；In CN1301247A public affairs
The method opened is raw material using 3,3- dimethylbutyl chlorine, and cost of material price is high, and generates stench in process of production
Dimethyl disulfide ethers compound, environmental pollution is heavier, administers this pollution and needs higher production cost, should not carry out industry
Metaplasia produces；It is hydrolyzed and is prepared with chloro- 3, the 3- bismethane of 1,1- bis- in US5994593, the shortcomings that this preparation method is raw material
Valuableness is not suitable for large-scale industrial production；Using chloro- 3, the 3- dimethyl butyrate alkoxide preparation of 1-, this method in US5856584
The shortcomings that be to make catalyst using iodide, expensive and bad recycling, and react generate stench dimethyl disulfide ethers pair
Product, processing cost are high.It is low all to there is yield in other technologies of preparing, pollutes the problems such as big, at subsequent industrialized production sewage
Reason brings difficulty.Using vinylacetate and tert-butyl chloride, the selection of catalyst is especially heavy in the reaction of base stock
It wants, some technique uses strong solid acid catalyst, can not complete to react well by verification experimental verification, strong solid acid catalyst
It is easy to inactivate, and part company uses ferric trichloride or alchlor technique, but this catalyst system reusing is poor,
Contaminated wastewater is very big, and actual operation is not strong.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of metallic catalysts to prepare 3,3- dimethyl butyraldehyde
Synthesis technology, it is scientific and reasonable, it is simple and easy, have the characteristics that low production cost, high income, environmentally protective and with high purity.
Metallic catalyst of the present invention prepares the synthesis technology of 3,3- dimethyl butyraldehyde: being system with liquid nitrogen cryogenics device
Cold source is catalyzed and synthesized using tert-butyl chloride and vinylacetate as raw material by metallic catalyst, and ice cube is added and is hydrolyzed,
3,3- dimethyl butyraldehyde is made after distillation.
The synthesis technology of metallic catalyst preparation 3, the 3- dimethyl butyraldehyde, includes the following steps:
1) cooling processing is carried out to dichloromethane solvent using liquid nitrogen cryogenics device；
2) it sequentially adds tert-butyl chloride and metallic catalyst is sufficiently mixed dissolution；
3) vinylacetate is added in the mixed liquor of step 2, obtains crude reaction；
4) distillation processing is carried out to crude reaction；
5) ice cube is added in the distillate of step 4；
6) sodium carbonate is added in distillate in steps of 5, carries out second distillation；Obtain pure 3,3- dimethyl butyrate
Aldehyde.
The metallic catalyst is that alchlor or ferric trichloride are obtained by Sepabeads EC-HA is carrier immobilized
Catalyst system.
It will be immersed in Sepabeads EC-HA carrier dissolved with the deionized water of alchlor or ferric trichloride, particle surface
Whole uniform adsorptions fill column, obtain Sepabeads EC-HA immobilization metal catalyst after Sepabeads EC-HA carrier.
Catalyst activity component surface has coated resin, is fixed on active component on resin, increases the contact of reaction
Area and uniformity enhance the catalytic activity in unit volume, increase substantially the yield of reaction.
In the step 1, dichloromethane solvent is cooled to -10-30 DEG C by liquid nitrogen cryogenics device.
Active component accounts for the 10-20% of catalyst system gross mass in the metallic catalyst.
In the step 3, vinylacetate time for adding is 60-90min.
In the step 4, vapo(u)rizing temperature is 50-100 DEG C.
In the step 5, the mole ratio of mole and vinylacetate that ice cube is added is 1-15:1；Reaction temperature
Degree is -10-15 DEG C.
Preferably, the mole of addition ice cube and the mole ratio of vinylacetate are 2:1.
In the step 6, the quality that sodium carbonate is added is the 5-10% of dichloromethane solvent quality；Distillate pH is 8-
12；Second distillation temperature is 50-100 DEG C.
The metallic catalyst active component: methylene chloride: tert-butyl chloride: the mass ratio of vinylacetate is 1:4-
7:4-6:4-6。
Compared with prior art, the invention has the following beneficial effects:
1. replacing traditional solid strong acid to urge using the carrier immobilized ferric trichloride of Sepabeads EC-HA or alchlor
Agent or simple metals catalyst, reactivity is higher, and reusable, environmentally protective；
2. solving reaction temperature release in reaction process, acutely, reaction can not stablize using the addition of ice cube substitution water
Control, improves the yield and purity of product, while required raw material is easy to get, from a wealth of sources, reduces production cost, it is easier to
Production application；
3. synthesis technology of the present invention, scientific and reasonable, simple and easy.
Specific embodiment
The present invention will be further explained with reference to the examples below.
Embodiment 1
Cooled down using the dichloromethane solvent that liquid nitrogen cryogenics device is 22% to 1500 gram mass scores, is cooled to 15
DEG C, add 460 grams of tert-butyl chlorides and 600 grams of carrier immobilized aluminum trichloride catalysts of Sepabeads EC-HA, active group
Dividing content is 13%, and after dissolution is mixed, 450 grams of vinylacetates are added dropwise after mixing evenly, is reacted 10 hours, vinyl acetate
Ester time for adding is 60min, is distilled 3 hours at 70 DEG C, adds 1200 grams of ice cube, and reaction temperature is 10 DEG C, and carbonic acid is added
75 grams of sodium, distillate pH is 10, distills 4 hours at 70 DEG C, obtains 3,3- dimethyl butyraldehyde purity 99.5%, molar yield
73%, it is higher than traditional yield 60%.
Embodiment 2
Cooled down using dichloromethane solvent of the liquid nitrogen cryogenics device to 1500 gram mass scores 30%, is cooled to 10
DEG C, add 530 grams of tert-butyl chlorides and 600 grams of carrier immobilized aluminum trichloride catalysts of Sepabeads EC-HA, active group
Dividing content is 15%, and after dissolution is mixed, 400 grams of vinylacetates are added dropwise after mixing evenly, is reacted 10 hours, vinyl acetate
Ester time for adding is 80min, is distilled 3 hours at 80 DEG C, adds 1100 grams of ice cube, and reaction temperature is 5 DEG C, adds carbonic acid
90 grams of sodium, distillate pH is 11, distills 4 hours at 75 DEG C, obtains 3,3- dimethyl butyraldehyde purity 99.6%, molar yield
74%, it is higher than traditional yield 60%.
Embodiment 3
Cooled down using dichloromethane solvent of the liquid nitrogen cryogenics device to 1200 gram mass scores 26.7%, is cooled to 5
DEG C, add 400 grams of tert-butyl chlorides and 500 grams of carrier immobilized aluminum trichloride catalysts of Sepabeads EC-HA, active group
Dividing content is 16%, and after dissolution is mixed, 422.2 grams of vinylacetates are added dropwise after mixing evenly, is reacted 10 hours, acetic acid second
Enester time for adding is 90min, is distilled 3 hours at 60 DEG C, adds 176.56 grams of ice cube, and reaction temperature is 8 DEG C, is added
80 grams of sodium carbonate, distillate pH is 10, distills 4 hours at 75 DEG C, obtains 3,3- dimethyl butyraldehyde purity 99.7%, mole receipts
Rate 75% is higher than traditional yield 60%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications done without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of synthesis technology of metallic catalyst preparation 3,3- dimethyl butyraldehyde, it is characterised in that: be with liquid nitrogen cryogenics device
Refrigeration source is catalyzed and synthesized using tert-butyl chloride and vinylacetate as raw material by metallic catalyst, and ice cube is added and carries out water
3,3- dimethyl butyraldehyde is made in solution after distillation.
2. the synthesis technology of metallic catalyst preparation 3,3- dimethyl butyraldehyde according to claim 1, it is characterised in that: packet
Include following steps:
1) cooling processing is carried out to dichloromethane solvent using liquid nitrogen cryogenics device；
2) it sequentially adds tert-butyl chloride and metallic catalyst is sufficiently mixed dissolution；
3) vinylacetate is added in the mixed liquor of step 2, after reaction, obtains crude reaction；
4) distillation processing is carried out to crude reaction；
5) ice cube is added in the distillate of step 4；
6) sodium carbonate is added in distillate in steps of 5, carries out second distillation；Obtain pure 3,3- dimethyl butyraldehyde.
3. the synthesis technology of metallic catalyst preparation 3,3- dimethyl butyraldehyde according to claim 2, it is characterised in that: gold
Metal catalyst is that alchlor or ferric trichloride pass through the carrier immobilized obtained catalyst system of Sepabeads EC-HA.
4. the synthesis technology of metallic catalyst preparation 3,3- dimethyl butyraldehyde according to claim 2, it is characterised in that: step
In rapid 1, dichloromethane solvent is cooled to -10-30 DEG C by liquid nitrogen cryogenics device.
5. the synthesis technology of metallic catalyst preparation 3,3- dimethyl butyraldehyde according to claim 2, it is characterised in that: gold
Active component accounts for the 10-20% of catalyst system gross mass in metal catalyst.
6. the synthesis technology of metallic catalyst preparation 3,3- dimethyl butyraldehyde according to claim 2, it is characterised in that: step
In rapid 3, vinylacetate time for adding is 60-90min.
7. the synthesis technology of metallic catalyst preparation 3,3- dimethyl butyraldehyde according to claim 2, it is characterised in that: step
In rapid 4, vapo(u)rizing temperature is 50-100 DEG C.
8. the synthesis technology of metallic catalyst preparation 3,3- dimethyl butyraldehyde according to claim 2, it is characterised in that: step
In rapid 5, the mole and vinylacetate mole ratio that ice cube is added are 1-15:1；Reaction material liquid temperature is -10-15 DEG C.
9. the synthesis technology of metallic catalyst preparation 3,3- dimethyl butyraldehyde according to claim 2, it is characterised in that: step
In rapid 6, the quality that sodium carbonate is added is the 5-10% of dichloromethane solvent quality；Second distillation temperature is 50-100 DEG C.
10. the synthesis technology of metallic catalyst preparation 3,3- dimethyl butyraldehyde according to claim 2, it is characterised in that:
Metallic catalyst active component: methylene chloride: tert-butyl chloride: the mass ratio of vinylacetate is 1:4-7:4-6:4-6.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283057A (en) * | 2019-06-28 | 2019-09-27 | 山东奔月生物科技股份有限公司 | Microchannel plate answers method to prepare the synthesis technology of 3,3- dimethyl butyraldehyde |
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| CN102295541A (en) * | 2011-08-16 | 2011-12-28 | 济南诚汇双达化工有限公司 | Preparation method of 3,3-dimethyl butyraldehyde |
| CN104130115A (en) * | 2014-08-20 | 2014-11-05 | 山东奔月生物科技有限公司 | Method for preparing 3,3-dimethyl butyraldehyde |
| CN104478681A (en) * | 2014-12-31 | 2015-04-01 | 济南诚汇双达化工有限公司 | Hydrolysis method for 1-chlorine-3,3-dimethylbutyl acetate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283057A (en) * | 2019-06-28 | 2019-09-27 | 山东奔月生物科技股份有限公司 | Microchannel plate answers method to prepare the synthesis technology of 3,3- dimethyl butyraldehyde |
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