CN101723818A - Method for synthesizing 3-hydroxy-2-butanone - Google Patents
Method for synthesizing 3-hydroxy-2-butanone Download PDFInfo
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- CN101723818A CN101723818A CN200910310247A CN200910310247A CN101723818A CN 101723818 A CN101723818 A CN 101723818A CN 200910310247 A CN200910310247 A CN 200910310247A CN 200910310247 A CN200910310247 A CN 200910310247A CN 101723818 A CN101723818 A CN 101723818A
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Abstract
The invention provides a method for synthesizing 3-hydroxy-2-butanone. In a self-generated pressure reaction kettle, cheap and stable paracetaldehyde is used as raw material, thiazole salt is used as a catalyst, the catalytic synthesis of the 3-hydroxy-2-butanone by a 'one-pot' method is realized by the continuous reaction of the high-temperature depolymerization of the paracetaldehyde and the coupling condensation of acetaldehyde by catalysis, the conversion rate of the paracetaldehyde is 90-98%, and the selectivity of the 3-hydroxy-2-butanone is 85-95%. The invention has the obvious characteristics that the use of the raw material of the volatilizable acetaldehyde is avoided, the conversion rate of the raw material of the paracetaldehyde is high, the paracetaldehyde is utilized to a maximum limit, the technological operation is simple, the cost is low, the product is easy to separate, and a novel preparation method is provided for the industrial production of the 3-hydroxy-2-butanone.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind of method of synthetic 3-hydroxyl-2-butanone.
Background technology
3-hydroxyl-2-butanone, have another name called acetoin, it has pleasant cream fragrance, is used for cream, the flavor potentiator of cheese, coffee, fruit, essence as configuration cream, dairy products, sour milk and strawberry type etc. also is widely used in tobacco, medicine etc., has high using value, China GB2760-86 stipulates that it is the food spice that allows use, in addition, and the intermediate of still synthetic many flavor compounds of 3-hydroxyl-2-butanone and medicine.Though 3-hydroxyl-2-butanone is of many uses, and is present in the numerous food products such as corn, grape, cocoa, apple, banana, cheese, meat naturally, its content is extremely low, is difficult to extract.The highly purified 3-hydroxyl-2-butanone of domestic use relies on import basically, and costs an arm and a leg.Therefore, the research of carrying out this respect has better industrial application prospect.Relevant in recent years 3-hydroxyl-2-butanone synthetic research has report more, its main preparation method has acetylactis depickling method, dimethyl diketone selective reduction method, sorbose bacterium or living film bacterium act on 2,3-butyleneglycol selective oxidation method obtains, perhaps pass through aspergillus tubigensis, fungies such as Penicillium notatum act on sugar cane juice and obtain, and aforesaid method is because cost or technical requirements are too high, still can not industrial application, it is raw material with the butanone that report is arranged recently, 200810143190.7), but because its technology needed for two steps bromate is that oxygenant prepares acetoin (Chinese patent, application number:, reaction is complicated, the product separate complex, and yield is low, is difficult to use in industrial acquisition.Someone adopts acetaldehyde is raw material, prepare acetoin by the coupling condensation reaction, the advantage of this method has " Atom economy " feature, realized method (Chinese patent by the synthetic 3-hydroxyl-2-butanone of acetaldehyde, application number: 200410021240.6), but owing to acetaldehyde boiling point low (boiling point is 21 ℃), easy volatile etc. cause transportation and store difficulty, and in operational process of craft, there is the serious problem of significant loss, the volatilization of acetaldehyde has not only increased industrial cost, and produces the unsafe factor in contaminate environment and the operation.Therefore, directly adopting acetaldehyde on industrial application is that feedstock production 3-hydroxyl-2-butanone will inevitably be subjected to certain restriction.
Summary of the invention
The invention provides a kind of by " treat different things alike " novel method of the synthetic 3-hydroxyl-2-butanone of method catalysis of paraldehyde.This method is raw material with the paraldehyde, depolymerizes to acetaldehyde by paraldehyde in self autoclave pressure, and the acetaldehyde that depolymerization produced self coupling condensation reaction takes place under the thiazole salt catalyst action immediately generated 3-hydroxyl-2-butanone.This operational path has made full use of the acetaldehyde raw material of new generation, has avoided the volatilization loss and the raw material transportation difficulty of acetaldehyde, has simplified the technological process of production, saved raw materials cost, have simple to operately, feed stock conversion and selectivity height, product separate characteristics such as simple.
Technical solution of the present invention is as follows:
With the paraldehyde is raw material, with the thiazole salt is catalyzer, and the mass ratio of paraldehyde and thiazole salt is 40: 1-400: 1, with the pH value of NaOH solution conditioned reaction mixed solution to 8-11, temperature of reaction is 120-180 ℃, directly synthetic 3-hydroxyl-2-butanone under the autogenous pressure condition.
The mass ratio of described paraldehyde and thiazole salt is preferably 100: 1-200: 1.Reaction times is 1-10 hour, and temperature of reaction is preferably 140-160 ℃.
Described thiazole salt contains molecular structural formula shown in the formula 1:
Formula 1
The concrete structural formula of thiazole salt is suc as formula 2:
Formula 2
R in the structural formula
1Can be C
1-C
30Long-chain fat family group is preferentially selected C
1-C
10Alkyl is because of radicals R
1Group has very big influence to the solvability of thiazole salt in substrate, carries out in order to make to be reflected in the homogeneous phase, and according to the reaction mechanism of thiazole salt catalysis acyloin condensation, excessive R
1Group can cause sterically hindered to reaction, so preferentially select as butyl octyl, C usually
6-C
14Aryl, especially phenyl, naphthyl, anthryl, phenanthryl is generally selected phenyl, C
7-C
15Aralkyl, particularly benzyl, styroyl, naphthyl methylene, preferential group is a benzyl, styroyl C
3-C
10Cycloalkyl or cycloalkenyl group, C
5-C
20Heterocyclylalkyl or heterocycloalkenyl, as piperidyl, piperazinyl, pyrrolidyl, imidazolidyl, tetrahydrofuran base, thiazolidyl, tetrahydro-thienyl, imidazolinyl, thiazolinyl is generally imidazolidyl, thiazolidyl, R
2Be hydrogen, halogen atom, as, fluorine, chlorine, bromine, iodine, hydroxyl, nitro, amino or cyano group, C
1-C
10Long-chain fat family group can be methyl, ethyl, and octyl group can substituted C
7-C
14Aryl or aralkyl, for example, phenyl, benzyl, styroyl, C
4-C
15Heteroaryl, particularly furyl, thienyl, pyrryl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, R
3Be C
1-C
10Alkyl, methylimidazolyl, thiazolyl, hydroxyl, amino or bromine atoms and above-mentioned R
2The same, these groups are slight to the influence of the catalytic performance of thiazole salt, generally select hydroxyl, methylimidazolyl, thiazolyl; X
-For being used for and the single or multiple negative charge cation equivalents of thiazole salt cationic charge, as F
-, Cl
-, Br
-, I
-, NO
3 -, SO
4 2-, PO
4 3-, CF
3COO
-, PF
6 -, ClO
4 -, generally select F
-, Cl
-, Br
-, I
-, NO
3 -
Characteristics of the present invention are paraldehyde depolymerization fully voluntarily under higher temperature conditions, in the subsequent reactions process, can make full use of the acetaldehyde that himself depolymerization produces and prepare 3-hydroxyl-2-butanone, and paraldehyde is cheap to be easy to get, boiling point is higher, stable in properties, transportation and storage are all very convenient.Therefore, use paraldehyde to be raw material among the present invention, in comparatively high temps and autogenous pressure still, by the paraldehyde depolymerization is acetaldehyde, under the thiazole salt catalyst action, generates 3-hydroxyl-2-butanone by acetaldehyde coupling condensation reaction again, the reaction of coupling condensation has taken place in acetaldehyde that the paraldehyde depolymerization produces immediately, the raw material paraldehyde is fully used, and has reduced raw materials cost, has also simplified technical process.Having reduced is the loss and the transportation storage problem of the raw material that caused of feedstock production 3-hydroxyl-2-butanone with acetaldehyde, is fit to industrial production, for the preparation of 3-hydroxyl-2-butanone provides a kind of novel method.The present invention is the synthetic 3-hydroxyl-2-butanone of material catalysis with the paraldehyde, and the paraldehyde transformation efficiency is 90-98%, and the selectivity of 3-hydroxyl-2-butanone is 85-95%, and synthetic 3-hydroxyl-2-butanone product can be purified by simple separation.
Know-why of the present invention is as shown in Figure 1: with the paraldehyde is raw material, in self autoclave pressure, at first depolymerize to acetaldehyde by paraldehyde, self coupling condensation reaction takes place in acetaldehyde that depolymerization produced immediately under the thiazole salt catalyst action, generate 3-hydroxyl-2-butanone.Be characterized in: in reaction process, the paraldehyde depolymerization produces acetaldehyde, the coupling condensation reaction takes place under catalyst action immediately produce 3-hydroxyl-2-butanone, reaction conversion ratio height, the selectivity of 3-hydroxyl-2-butanone is good, thereby the yield height of 3-hydroxyl-2-butanone.Though can directly prepare the method for 3-hydroxyl-2-butanone by acetaldehyde, but the acetaldehyde raw material must be separated by the paraldehyde depolymerization under acidic conditions earlier, not only increased by a procedure, and the acetaldehyde boiling point has only 20.8 ℃, highly volatile and cause significant loss and cause the yield of 3-hydroxyl-2-butanone to reduce.And the boiling point of paraldehyde is 65-82 ℃, transportation stores convenient, the raw material availability height, therefore this operational path has made full use of the acetaldehyde raw material of new generation, has avoided the volatilization loss of acetaldehyde and raw material transportation to store difficulty, has simplified the technological process of production, saved raw materials cost, have simple to operately, have feed stock conversion and selectivity of product height, product separates advantages such as simple.
Description of drawings
Fig. 1 is a know-why synoptic diagram of the present invention.
Embodiment
Following embodiment and embodiment are intended to further specify the present invention, rather than limitation of the present invention.
The preparation of thiazole salt
According to document (Hermann, Stetter.Angew.Chem.Int.Engl.15 (1976) 639-647),, following two kinds of thiazole salt catalyzer have been synthesized with corresponding thiazole raw material and corresponding halohydrocarbon
Embodiment 1
Get the 20g paraldehyde and 0.2g thiazole salt (I) (1wt%) joins in the autoclave together, with the pH value of the sodium hydroxide solution conditioned reaction mixed solution of 2M to 9-10, extract the air in the reactor earlier, stir also and slowly be heated to 140 ℃, reaction 3h, cold naturally the going in reaction back, product is through gas chromatographic analysis, the transformation efficiency 91% of paraldehyde, the selectivity of 3-hydroxyl-2-butanone are 92%.
Embodiment 2
Get the 20g paraldehyde and 0.2g thiazole salt (I) (1wt%) joins in the autoclave together, with the pH value of the sodium hydroxide solution conditioned reaction mixed solution of 2M to 9-10, extract the air in the reactor earlier, stir also and slowly be heated to 150 ℃, reaction 3h, cold naturally the going in reaction back, product is through gas chromatographic analysis, the transformation efficiency 94% of paraldehyde, the selectivity of 3-hydroxyl-2-butanone are 95%.
Embodiment 3
Get the 20g paraldehyde and 0.2g thiazole salt (I) (1wt%) joins in the autoclave together, with the pH value of the sodium hydroxide solution conditioned reaction mixed solution of 2M to 9-10, extract the air in the reactor earlier, stir also and slowly be heated to 160 ℃, reaction 4h, cold naturally the going in reaction back, product is through gas chromatographic analysis, the transformation efficiency 96% of paraldehyde, the selectivity of 3-hydroxyl-2-butanone are 90%.
Embodiment 4
Get the 20g paraldehyde and 0.1g thiazole salt (I) (0.5wt%) joins in the autoclave together, with the pH value of the sodium hydroxide solution conditioned reaction mixed solution of 2M to 9-10, extract the air in the reactor earlier, stir also and slowly be heated to 160 ℃, reaction 4h, cold naturally the going in reaction back, product is through gas chromatographic analysis, the transformation efficiency 94% of paraldehyde, the selectivity of 3-hydroxyl-2-butanone are 85%.
Embodiment 5
Get the 20g paraldehyde and 0.2g thiazole salt (II) (1wt%) joins in the autoclave together, with the pH value of the sodium hydroxide solution conditioned reaction mixed solution of 2M to 9-10, take out the air in the most reactor, stir also and slowly be heated to 160 ℃, reaction 4h, cold naturally the going in reaction back, product is through gas chromatographic analysis, the transformation efficiency 97% of paraldehyde, the selectivity of 3-hydroxyl-2-butanone are 92%.
Embodiment 6
Get the 20g paraldehyde and 0.1g thiazole salt (II) (0.5wt%) joins in the autoclave together, with the pH value of the sodium hydroxide solution conditioned reaction mixed solution of 2M to 9-10, extract the air in the reactor earlier, stir also and slowly be heated to 160 ℃, reaction 4h, cold naturally the going in reaction back, product is through gas chromatographic analysis, the transformation efficiency 98% of paraldehyde, the selectivity of 3-hydroxyl-2-butanone are 90%.
Claims (7)
1. the method for a synthetic 3-hydroxyl-2-butanone is characterized in that, is raw material with the paraldehyde, is catalyzer with the thiazole salt, and the mass ratio of paraldehyde and thiazole salt is 40: 1-400: 1; To 8-11, is 120-180 ℃ condition under synthetic 3-hydroxyl-2-butanone in temperature of reaction with the pH value of NaOH solution conditioned reaction mixed solution.
2. the method for synthetic 3-hydroxyl-2-butanone according to claim 1 is characterized in that, the mass ratio of paraldehyde and thiazole salt is 100: 1-200: 1.
3. the method for synthetic 3-hydroxyl-2-butanone according to claim 1 is characterized in that, the reaction times is 1-10 hour.
4. the method for synthetic 3-hydroxyl-2-butanone according to claim 1 is characterized in that, temperature of reaction is 140-160 ℃.
5. the method for synthetic 3-hydroxyl-2-butanone according to claim 1 is characterized in that, described thiazole salt contains molecular structural formula shown in the formula 1:
6. the method for synthetic 3-hydroxyl-2-butanone according to claim 5 is characterized in that, the concrete structural formula of described thiazole salt is suc as formula 2:
R1 is a C1-C30 long-chain fat family group in the structural formula, C6-C14 aryl, C7-C15 aralkyl, C3-C10 cycloalkyl, C3-C10 cycloalkenyl group, C5-C20 Heterocyclylalkyl or C5-C20 heterocycloalkenyl; R2 is a hydrogen, halogen atom, hydroxyl, nitro, amino, cyano group, C1-C10 long-chain fat family group, C7-C14 aryl, C7-C14 aralkyl or C4-C15 heteroaryl; R3 is the C1-C10 alkyl, have the C1-C10 alkyl of oh group, methylimidazolyl, thiazolyl, amino or halogen atom; X-is F-, Cl-, Br-, I-, NO3-, SO42-, PO43-, CF3COO-or PF6-.
7. the method for synthetic 3-hydroxyl-2-butanone according to claim 6 is characterized in that, R1 is the C1-C10 alkyl in the structural formula, phenyl, naphthyl, anthryl, phenanthryl, benzyl, styroyl, naphthyl methylene, piperidyl, piperazinyl, pyrrolidyl, imidazolidyl, tetrahydrofuran base, thiazolidyl, tetrahydro-thienyl, imidazolinyl or thiazolinyl; R2 is a methyl, ethyl, octyl group, phenyl, benzyl, styroyl, furyl, thienyl, pyrryl, imidazolyl, thiazolyl or isothiazolyl; X-is F-, Cl-, Br-, I-or NO3-.
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| CN200910310247A CN101723818A (en) | 2009-11-23 | 2009-11-23 | Method for synthesizing 3-hydroxy-2-butanone |
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| CN200910310247A CN101723818A (en) | 2009-11-23 | 2009-11-23 | Method for synthesizing 3-hydroxy-2-butanone |
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Application publication date: 20100609 |