CN109336750A - A kind of synthesis technology of isoamyl olefine aldehydr - Google Patents
A kind of synthesis technology of isoamyl olefine aldehydr Download PDFInfo
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- CN109336750A CN109336750A CN201811410133.0A CN201811410133A CN109336750A CN 109336750 A CN109336750 A CN 109336750A CN 201811410133 A CN201811410133 A CN 201811410133A CN 109336750 A CN109336750 A CN 109336750A
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- olefine aldehydr
- isoamyl olefine
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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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
Abstract
The present invention provides a kind of synthesis technology of isoamyl olefine aldehydr, using metal oxide as catalyst, under the conditions of existing for the auxiliary agent, isoamyl olefine aldehydr is prepared by catalytic material rearrangement of 2- methyl -3- butyne-2-alcohol, high catalytic efficiency of the present invention is selective good, yield is up to 93.9-96.1%, is suitble to industrialized production；Used catalyst of the present invention is cheap, and dosage is few, reduces production cost；Catalyst system of the present invention is simple, can simplify later separation step, reduces energy consumption cost；Conversion rate of the present invention is fast, and the reaction time only needs 20-40min；Catalyst stability of the present invention is good, applies more batches and still keeps superior performance, and after applying 20 times, yield reduces by 0.94%.
Description
Technical field
The invention belongs to field of chemical technology, are related to a kind of synthesis technology of isoamyl olefine aldehydr.
Background technique
Isoamyl olefine aldehydr, i.e. 3- methyl-2-butene aldehyde are colourless liquid.It is mainly as intermediate, for producing lemon
A variety of fine chemical products such as aldehyde, vitamin E and vitamin A and drug.
According to the difference of reaction raw materials, the synthetic route of isoamyl olefine aldehydr mainly has following three kinds.
Prenol is raw material: in DE-2517859 using tubular reactor at 150-300 DEG C, in excess of oxygen atmosphere
Under enclosing, copper catalysis oxidation prenol synthesizes isoamyl olefine aldehydr, and the by-product for reacting generation is more, and selectivity is poor.JP-60/
246340 reports are using the silver and the copper composite catalyst that are supported on carrier, and at 400-500 DEG C, prenol is oxidized by oxygen system
Isoamyl olefine aldehydr, selectivity need high temperature and prenol conversion ratio is lower up to 96%.CN101709026A uses 2,2,
6,6- tetramethyl piperidine nitrogen oxygen free radical compounds are catalyst, and nitrate is auxiliary agent, and oxygen-containing gas is oxidant, organic molten
In agent, catalysis oxidation prenol synthesizes isoamyl olefine aldehydr under room temperature or heating condition, and yield is up to 92.3%, but catalyst price
It is higher, it can not reuse and the reaction time is longer (> 6h).The price of prenol is higher, produces iso-amylene using it as raw material
Aldehyde it is at high cost, lack competitiveness.Synthetic route is as follows:
3- methyl -3- butene-1 alcohol is raw material: catalysis oxidation and rearrangement reaction being carried out joint operation in US4192820, by 3-
Methyl -3- butene-1 alcohol carries out catalysis oxidation on silver-colored crystal or load silver, and (while catalysis oxidation, part is reset
At isoamyl olefine aldehydr), mixture acid or alkali carry out reordering operations, can selectively stablize 91% or so, but reaction temperature 400-
460 DEG C of higher and alcohol conversion ratios 52% are lower.Synthetic route is as follows:
2- methyl -3- butyne-2-alcohol is raw material: Tetrahedron Letters, and 1988,29,6253 by 2- methyl -3- butine -
2- alcohol, four titanium butoxides, stannous chloride and p-methyl benzenesulfonic acid react in o-dichlorohenzene has obtained isoamyl olefine aldehydr, and the reaction time is
1h, yield 83%, which has used the big solvent o-dichlorohenzene of toxicity, and increases separation costs.Tetrahedron
Letters, 1996,37,853 by 2- methyl -3- butyne-2-alcohol, acetyl acetone, dibutyl sulfoxide, p-tert-butyl benzoic acid
It is reacted in o-dichlorohenzene with normal octane and has obtained isoamyl olefine aldehydr, reaction time 5h, up to 90%, which equally uses yield
Toxicity big solvent o-dichlorohenzene.Tetrahedron Letters, 1990,31,7521 are catalyzed using the vanadium of montmorillonite load
Agent reacts 2- methyl -3- butyne-2-alcohol in dimethylbenzene has obtained isoamyl olefine aldehydr, reaction time 1h, yield 82%, but
The method yield is lower.CN101381292B is logical using the composite catalyst of acetylacetone,2,4-pentanedione oxygen titanium, stannous chloride and benzoic acid composition
Crossing reactive distillation coupling technique realizes 2- methyl -3- butyne-2-alcohol to the continuous production of isoamyl olefine aldehydr, and comprehensive yield is reachable
88-93%, but catalyst price is higher and recovery is difficult.Synthetic route is as follows:
In conclusion preparing isoamyl olefine aldehydr using 2- methyl -3- butyne-2-alcohol as raw material in the prior art, have the disadvantage that
(1) catalyst price is higher；
(2) reaction time is long；
(3) isoamyl olefine aldehydr yield is low；
(4) recovery of catalyst is difficult；
(5) solvent big using toxicity.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of synthesis technology of isoamyl olefine aldehydr,
Realize following goal of the invention:
(1) catalyst is cheap, and dosage is few, reduces production cost；
(2) catalyst is easily separated, recycles；
(3) reaction time is short；
(4) catalyst choice is high, isoamyl olefine aldehydr high income；
(5) catalyst stability is good, applies more batches and still keeps superior performance.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of synthesis technology of isoamyl olefine aldehydr, using metal oxide as catalyst, under the conditions of existing for the auxiliary agent, with 2- methyl-
3- butyne-2-alcohol is raw material, carries out catalytically rearranging reaction and prepares isoamyl olefine aldehydr, after reaction, catalyst circulation is recovered by filtration
It applies, reaction solution rectifying is obtained into product isoamyl olefine aldehydr.
It is further improvement to above-mentioned technical proposal below:
The metal oxide catalyst be molybdenum trioxide, titanium dioxide, vanadic anhydride, chrome green, manganese dioxide,
One of di-iron trioxide or cobaltosic oxide；
The auxiliary agent is one of N,N-dimethylformamide, 4-dimethylaminopyridine or triethylamine；
The content of raw materials used 2- methyl -3- butyne-2-alcohol be greater than 98%, water content less than 0.5%, preferred water content be less than
0.1%。
Reaction temperature is 120-200 DEG C, preferably 150-180 DEG C.
The mass ratio of the catalyst and 2- methyl -3- butyne-2-alcohol is 0.001-0.05:1, preferably 0.005-
0.02:1。
The mass ratio of the auxiliary agent and 2- methyl -3- butyne-2-alcohol is 0.001-0.01:1, preferably 0.003-
0.005:1。
Reaction time is 20min-40min.
The catalyst being obtained by filtration can be applied, and test result shows after 20 times are applied, the activity of catalyst
It is substantially reduced with selectivity nothing.
The invention adopts the above technical scheme, compared with prior art, has the advantages that
(1) used catalyst of the present invention is cheap, and dosage is few, reduces production cost.
(2) catalyst system of the present invention is simple, can simplify later separation step, reduces energy consumption cost.
(3) conversion rate of the present invention is fast, and the reaction time only needs 20-40min.
(4) high catalytic efficiency of the present invention, selectivity is good, and isoamyl olefine aldehydr yield is up to 93.9-96.1%, preferred technical side
The isoamyl olefine aldehydr yield that case obtains is 95.1-96.1%.
(5) catalyst stability of the present invention is good, applies more batches and still keeps superior performance, and after applying 20 times, yield is reduced
0.94%。
The present invention is further illustrated combined with specific embodiments below.
Specific embodiment
A kind of synthesis technology of the isoamyl olefine aldehydr of embodiment 1
The following steps are included:
(1) it feeds
By 500g 2- methyl -3- butyne-2-alcohol (purity 99.7%), 5g molybdenum trioxide, 2.0g triethylamine is added to magnetic
In the 1L autoclave of power stirring and temperature controller.
(2) synthetic reaction
It is replaced 3 times with nitrogen, control reaction temperature is at 180 DEG C, and 500rpm is stirred, continuous sampling, through gas chromatographic analysis, raw material
The content of 2- methyl -3- butyne-2-alcohol from 99.7% be down to 56% after no longer change, i.e., conversion ratio is constant, reaction balance, reach eventually
Point, 20 min of coreaction.
(3) separating catalyst
Then room temperature being down to water, extruding reaction solution, filter to isolate catalyst, catalyst is recyclable to be applied.
(4) rectifying
After rectifying, recycling raw material 2- methyl -3- butyne-2-alcohol feeds intake again to be applied reaction solution, and final acquisition product is different
Pentenals 480.5g, purity 99.3%, comprehensive yield 96.1%.
Catalyst is applied, the results are shown in Table 1 for experiment:
1 catalyst of table applies the influence to reaction result.
It applies 20 times, yield reduces by 0.94%.
Embodiment 2-9
Using the method for embodiment 1, change reaction temperature, the results are shown in Table 2.
Influence of 2 temperature of table to reaction result.
Embodiment 10-11
Using the method for embodiment 1, change auxiliary agent type, the results are shown in Table 3.
Influence of the 3 auxiliary agent type of table to reaction result.
Embodiment 12-25
Using the method for embodiment 1, change catalyst and auxiliary dosage, the results are shown in Table 4.
The influence of 4 catalyst of table and auxiliary dosage to reaction result.
Embodiment 15,16,20,21 is preferred embodiment.
Embodiment 26-31
Using the method for embodiment 1, change the type of metal oxide catalyst, the results are shown in Table 5.
Influence of the 5 different metal oxides catalyst of table to reaction result.
Product yield of the invention is obtained comprehensive yield after applying the raw material of recycling again.
The above is preferred embodiments of the present invention.Implement according to the technical essence of the invention to above
Any simple modification, equivalent change and modification that example is done, fall within the protection scope of the present invention.
Claims (10)
1. a kind of synthesis technology of isoamyl olefine aldehydr, it is characterised in that: using metal oxide as catalyst, the condition existing for auxiliary agent
Under, isoamyl olefine aldehydr is prepared using 2- methyl -3- butyne-2-alcohol as catalytic material rearrangement.
2. a kind of synthesis technology of isoamyl olefine aldehydr according to claim 1, it is characterised in that: the metal oxide is
One in molybdenum trioxide, titanium dioxide, vanadic anhydride, chrome green, manganese dioxide, di-iron trioxide or cobaltosic oxide
Kind.
3. a kind of synthesis technology of isoamyl olefine aldehydr according to claim 1, it is characterised in that: the auxiliary agent is N, N- bis-
One of methylformamide, 4-dimethylaminopyridine or triethylamine.
4. a kind of synthesis technology of isoamyl olefine aldehydr according to claim 1, it is characterised in that: the catalytically rearranging, reaction
Temperature is 120-200 DEG C.
5. a kind of synthesis technology of isoamyl olefine aldehydr according to claim 4, it is characterised in that: the reaction temperature is 150-
180℃。
6. a kind of synthesis technology of isoamyl olefine aldehydr according to claim 1, it is characterised in that: the catalyst and 2- first
The mass ratio of base -3- butyne-2-alcohol is 0.001-0.05:1；The mass ratio of the auxiliary agent and 2- methyl -3- butyne-2-alcohol is
0.001-0.01:1。
7. a kind of synthesis technology of isoamyl olefine aldehydr according to claim 1, it is characterised in that: reaction time 20min-
40min。
8. a kind of synthesis technology of isoamyl olefine aldehydr according to claim 1, it is characterised in that: the catalyst and 2- first
The mass ratio of base -3- butyne-2-alcohol is 0.005-0.02:1.
9. a kind of synthesis technology of isoamyl olefine aldehydr according to claim 1, it is characterised in that: raw materials used 2- methyl -3-
The water content of butyne-2-alcohol is less than 0.5%.
10. a kind of synthesis technology of isoamyl olefine aldehydr according to claim 1, it is characterised in that:
Catalyst is recovered by filtration after reaction, by obtained reaction solution in catalytically rearranging.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028392A (en) * | 2019-04-29 | 2019-07-19 | 山东新和成药业有限公司 | A kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr |
| CN110330415A (en) * | 2019-07-01 | 2019-10-15 | 万华化学集团股份有限公司 | A kind of preparation method of isoamyl olefine aldehydr |
| CN110368937A (en) * | 2019-08-09 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of method of 3-M2BOL synthesis isoamyl olefine aldehydr |
| CN111167471A (en) * | 2020-01-17 | 2020-05-19 | 浙江新和成股份有限公司 | Metal oxide coated ceramic corrugated plate catalyst, preparation and application thereof in preparation of citral key intermediate |
| US10974225B1 (en) | 2020-01-17 | 2021-04-13 | Zhejiang Nhu Company Ltd. | Metal oxide coated ceramic corrugated plate catalyst, preparation and application in preparation of key intermediates of citral |
| CN113956138A (en) * | 2021-11-15 | 2022-01-21 | 江苏宏邦化工科技有限公司 | Method for continuously synthesizing isopropenal through tubular reactor |
| CN115160113A (en) * | 2022-07-06 | 2022-10-11 | 江苏宏邦化工科技有限公司 | Method for simultaneously synthesizing two citral intermediates |
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2018
- 2018-11-23 CN CN201811410133.0A patent/CN109336750A/en not_active Withdrawn
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028392A (en) * | 2019-04-29 | 2019-07-19 | 山东新和成药业有限公司 | A kind of method of methyl butynol iso-synthesis isoamyl olefine aldehydr |
| WO2020220944A1 (en) * | 2019-04-29 | 2020-11-05 | 浙江新和成股份有限公司 | Method for synthesizing isopentenol by isomerization of methyl butynol |
| DE112020000129B4 (en) | 2019-04-29 | 2022-04-07 | Shandong Nhu Pharmaceutical Co., Ltd. | Process for the synthesis of isopentenal by isomerization of methylbutynol |
| DE112020000129T5 (en) | 2019-04-29 | 2021-07-22 | Shandong Nhu Pharmaceutical Co., Ltd. | Process for the synthesis of isopentenal by isomerization of methylbutynol |
| CN110330415A (en) * | 2019-07-01 | 2019-10-15 | 万华化学集团股份有限公司 | A kind of preparation method of isoamyl olefine aldehydr |
| CN110330415B (en) * | 2019-07-01 | 2022-04-22 | 万华化学集团股份有限公司 | Preparation method of isopentenal |
| CN110368937B (en) * | 2019-08-09 | 2022-02-22 | 中触媒新材料股份有限公司 | Method for synthesizing isopentenal from 3-methyl-2-butene-1-ol |
| CN110368937A (en) * | 2019-08-09 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of method of 3-M2BOL synthesis isoamyl olefine aldehydr |
| CN111167471A (en) * | 2020-01-17 | 2020-05-19 | 浙江新和成股份有限公司 | Metal oxide coated ceramic corrugated plate catalyst, preparation and application thereof in preparation of citral key intermediate |
| US10974225B1 (en) | 2020-01-17 | 2021-04-13 | Zhejiang Nhu Company Ltd. | Metal oxide coated ceramic corrugated plate catalyst, preparation and application in preparation of key intermediates of citral |
| CN111167471B (en) * | 2020-01-17 | 2020-10-02 | 浙江新和成股份有限公司 | Metal oxide coated ceramic corrugated plate catalyst, preparation and application thereof in preparation of citral key intermediate |
| CN113956138A (en) * | 2021-11-15 | 2022-01-21 | 江苏宏邦化工科技有限公司 | Method for continuously synthesizing isopropenal through tubular reactor |
| CN115160113A (en) * | 2022-07-06 | 2022-10-11 | 江苏宏邦化工科技有限公司 | Method for simultaneously synthesizing two citral intermediates |
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Application publication date: 20190215 |