CN104829455B - A kind of method for catalyzing and synthesizing trifluoroacetic ethyl acetoacetate - Google Patents
A kind of method for catalyzing and synthesizing trifluoroacetic ethyl acetoacetate Download PDFInfo
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The invention discloses a kind of method for catalyzing and synthesizing trifluoroacetic ethyl acetoacetate, comprises the following steps：A divalence and trivalent metal salt mixed aqueous solution are mixed by () with NaOH and sodium carbonate mixed aqueous solution, make solution ph for after 8.5～10.5, aging, filter, dry, grind to obtain catalyst precarsor；B catalyst precarsor roasting that step (a) is obtained by (), cooling, are then added in the KF aqueous solution, stir, filter, wash and be vacuum dried, roasting is obtained catalyst；C catalyst that step (b) is obtained by () is 0.001～0.05 with ethyl acetate, Trifluoroacetic Acid Ethyl Ester in mass ratio：2～5：1,5～10h is reacted at 40～60 DEG C, rectifying, cooling obtain condensation product, add the mixed solution of formic acid and ethyl acetate again in the condensation product for obtaining, 0.5～3h, cooling is reacted at 30～55 DEG C, filter, filtrate decompression rectifying obtains trifluoroacetic ethyl acetoacetate.The present invention has the advantages that process is simple, high income, safety and environmental protection.
Description
Technical field
The present invention relates to the synthetic method of trifluoroacetic ethyl acetoacetate, more particularly to one kind catalyze and synthesize trifluoroacetyl acetic acid
The method of ethyl ester.
Background technology
Trifluoroacetic ethyl acetoacetate is the important intermediate of the fluorochemicals such as synthetic pesticide, medicine, with trifluoroacetyl second
Acetoacetic ester is raw material or as key intermediate, can produce all kinds of containing heterocyclic drug, efficient pesticides and highy potent herbicide, or
It is the important intermediate for obtaining synthesizing these products.The product variety that has developed at present has pyridines, miazines, pyroles, sulphur
Ureide derivative compound and fluorine-containing organic acid and its salt etc..In view of the important use of trifluoroacetic ethyl acetoacetate, study further,
Optimize its synthetic technology, accelerate its production industrially and application has great importance.
At present, the synthesis of trifluoroacetic ethyl acetoacetate mainly take in atent solvent and highly basic effect under, to trifluoro second
Acetoacetic ester and ethyl acetate carry out Claisen condensation.
If Edward Micinski is with hexamethylene (or dodecane) as solvent, in highly basic (metallic sodium, caustic alcohol or hydrogenation
Sodium) effect under Trifluoroacetic Acid Ethyl Ester and ethyl acetate are carried out Claisen condensation, unreacted reagent and life are removed by rectifying
The ethanol for becoming obtains condensation product；3- alkoxyl -3- is obtained afterwards with inorganic acid (hydrochloric acid, sulfuric acid or phosphoric acid) neutralization condensation product
Hydroxyl -4,4,4- trifluoroacetic acid ethyl ester；Again with the acetylation reagent such as carboxylic acid halides (or acetic anhydride) by its acetylation, separated after obtain
Trifluoroacetic ethyl acetoacetate (Edward Micinski.Preparation of Alkyl Trifluoroacetoacetate
[p].US:4647689,1987-3-3.).
And for example Louis Amiet and Bernard Langlois be with hexamethylene as solvent, by trifluoro under caustic alcohol effect
Ethyl acetate and ethyl acetate carry out Claisen condensation, and the ethanol for removing unreacted reagent and generation by rectifying is condensed
Product；Afterwards with Bronsted acid (formic acid) neutralize condensation product, then separated after obtain trifluoroacetic ethyl acetoacetate (Louis Amiet,
Bernard Langlois.Process for The Preparation of Ethyl Trifluoroacetoacetate
[p].US:4883904,1989-11-28.).
For another example Cheong Kuoc Va etc. is condensed with Trifluoroacetic Acid Ethyl Ester under caustic alcohol effect with excessive ethyl acetate, rectifying
Neutralize condensation product with the concentrated sulfuric acid after separating, then be rectifying to obtain trifluoroacetic ethyl acetoacetate (Cheong Kuoc Va, Zheng Chunzhi. trifluoro
The synthesis [J] of ethyl acetoacetate. agricultural chemicals, 2007,46 (12):833-834.).
From the point of view of the result of study of existing report, it is synthesis three that Trifluoroacetic Acid Ethyl Ester and ethyl acetate carry out Claisen condensation
The committed step of acetyl fluoride ethyl acetate.Claisen condensation adopts strong alkali as a catalyst, predominantly metallic sodium, caustic alcohol or hydrogenation
Sodium etc., directly adopts metallic sodium, then react acutely and have hydrogen to generate, dangerous big；Sodium hydride activity is high, in the reaction
A large amount of hydrogen can be produced, thus dangerous high；According to caustic alcohol, in addition to it need to consume a large amount of caustic alcohols, also a large amount of ethanol are generated,
The separation of impact condensation product, in addition also has substantial amounts of sodium salt to generate during the course of the reaction, needs separation and recovery, high cost, environmental protection
Pressure is big.
Content of the invention
The present invention is for the catalysis conjunction in place of the deficiencies in the prior art, providing a kind of process is simple, high income, safety and environmental protection
The method for becoming trifluoroacetic ethyl acetoacetate.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is：One kind catalyzes and synthesizes trifluoroacetyl acetic acid
The method of ethyl ester, comprises the following steps：
A divalence and trivalent metal salt mixed aqueous solution are mixed by () with NaOH and sodium carbonate mixed aqueous solution, adjustment
After solution ph is 8.5～10.5, in 50～75 DEG C of aging 15～25h, filter cake is filtrated to get, by Washing of Filter Cake to neutrality, then
10～15h is dry at 70～90 DEG C, grind to obtain catalyst precarsor；
B catalyst precarsor that step (a) is obtained by () is cooled down, is then added to KF water in 400～550 DEG C of 2～5h of roasting
In solution, under room temperature, 20～48h is stirred, after filtering, wash and being vacuum dried, 3～8h of roasting at 400～550 DEG C, cooling,
Prepared catalyst；
C catalyst that step (b) is obtained by () is 0.001～0.05 with ethyl acetate, Trifluoroacetic Acid Ethyl Ester in mass ratio：
2～5：1,5～10h is reacted at 40～60 DEG C, rectifying, cooling obtain condensation product, then add in the condensation product for obtaining
Formic acid and the mixed solution of ethyl acetate, react 0.5～3h at 30～55 DEG C, cool down, and filter, filtrate decompression rectifying is obtained
To trifluoroacetic ethyl acetoacetate.
The total mole number of the total mole number of described divalent metal salt and trivalent metal salt and NaOH and sodium carbonate it
Than being preferably 0.4～0.5:.1.
Bivalent metal ion and trivalent metal ion mole in described divalent metal salt and trivalent metal mixed salt solution
Than being preferably 2～4:1.
In described NaOH and sodium carbonate mixture, NaOH is preferably 4～10 with the mass ratio of sodium carbonate:
1.
Described divalent metal salt is preferably Mg (NO3)2·6H2O、Co(NO3)2·6H2O、Cu(NO3)2·3H2O、Mn
(NO3)2·4H2The mixture of one or more in O.
Described trivalent metal salt is preferably Al (NO3)3·9H2O or Fe (NO3)3·9H2The mixture of O or both.
Described KF is preferably 1 with the ratio of the total mole number of divalent metal salt and trivalent metal salt:10～25.
The mixed solution of described formic acid and ethyl acetate is preferably 0.5～1.5 with the mass ratio of Trifluoroacetic Acid Ethyl Ester:1.
In the mixed solution of described formic acid and ethyl acetate, formic acid is preferably 1 with the mass ratio of ethyl acetate:0.3～3.
The catalyst that the present invention is prepared is stratified material, is a kind of polynary houghite, and its chemical composition is [M2+ 1- xM3+ x(OH)2]x+(An- x/n)·mH2O, M2+And M3+Divalence and trivalent metal ion, A are represented respectivelyn-Anion is represented, x is M3+/
(M2++M3+) mol ratio, M2+It is Ca2+、Mg2+、Co2+、Ni2+、Mn2+、Cu2+、Fe2+In one or more, M3+It is Fe3+、Al3 +、Cr3+、Sc3+In one or more, An-It is CO3 2-、OH-、NO3 -、Cl-、SO4 2-、PO4 3-In one or two.
The catalyst of the present invention can be recycled, further reduce three waste discharge, reduce into through simple regeneration
This.Catalyst recovery process is：By the catalyst being recovered by filtration, after fully being washed with organic solvent, go in Muffle kiln roasting
Except organic matter, sintering temperature are 300 DEG C～600 DEG C, preferably 400 DEG C～500 DEG C, room temperature is naturally cooled to.
Compared with prior art, the present invention has advantages below：
1st, process is simple, gently steadily, product is easily separated, catalyst reusable edible, it is easy to industrial metaplasia for course of reaction
Produce；
2nd, safety and environmental protection, in preparation process, the inflammable gas such as no hydrogen is generated, and catalyst can be circulated through simple regeneration
Utilize, three waste discharge is further reduced, reduces cost；
3rd, high income, good product quality, yield reach as high as 89.5% more than 87.5%；Product purity for
More than 99.2%, reach as high as 99.9%.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment, but protection scope of the present invention is not limited in
This.
Embodiment 1
(1) in four-hole bottle, by Mg (NO3)2·6H2O 48.08g(0.1875mol)、Al(NO3)3·9H2O 23.45g
(0.0625mol) I 70ml of mixed aqueous solution being configured to, with NaOH 20g (0.5mol) and sodium carbonate 3.31g
(0.03125mol) II 70ml of mixed aqueous solution for preparing is mixed to get mixed solution, and the pH value for adjusting mixed solution is 8.5, stirs
30min is mixed, in 65 DEG C of aging 18h, filter cake is filtrated to get, by Washing of Filter Cake to neutrality, at 80 DEG C, 12h is dry, grind and must be catalyzed
Agent precursor；
(2) roasting 3h at the catalyst precarsor for obtaining step (1) is put in Muffle furnace in 450 DEG C, nitrogen protection are lower certainly
Room temperature is so cooled to.Solid after roasting is added in the 100ml 0.1mol/L KF aqueous solution, under room temperature, stirs 48h, mistake
Filter, wash and be vacuum dried after, at 450 DEG C, roasting 8h, then naturally cools to room temperature under nitrogen protection, be obtained catalysis
Agent；
(3) in four-hole boiling flask, it is separately added into ethyl acetate 40g, Trifluoroacetic Acid Ethyl Ester 20g and step (2) is obtained urges
Agent 0.02g, reacts 6h at 40 DEG C, and rectifying removes unreacted ethyl acetate and the ethanol of generation obtains condensation product, cold
But, (formic acid is 1 with ethyl acetate mass ratio then to add formic acid and ethyl acetate in the condensation product for obtaining:1) mixing is molten
Liquid 10g, reacts 1h at 40 DEG C, cools down, and filters, filtrate decompression rectifying obtains trifluoroacetic ethyl acetoacetate, divides through GC/MS
Analysis, purity are 99.9%, and yield is 87.9%.
Embodiment 2
(1) in four-hole bottle, by Mg (NO3)2·6H2O 51.28g(0.2mol)、Al(NO3)3·9H2O 15.01g
(0.04mol)、Fe(NO3)3·9H2I 70ml of mixed aqueous solution that O 4.04g (0.01mol) is configured to, with NaOH
II 70ml of mixed aqueous solution that 20.00g (0.5mol) and sodium carbonate 2.65g (0.025mol) are prepared is mixed to get mixed solution,
The pH value of adjustment mixed solution is 9, stirs 30min, in 60 DEG C of aging 15h, is filtrated to get filter cake, by Washing of Filter Cake to neutrality,
15h is dry at 80 DEG C, grind to obtain catalyst precarsor；
(2) roasting 4h at the catalyst precarsor for obtaining step (1) is put in Muffle furnace in 400 DEG C, nitrogen protection are lower certainly
Room temperature is so cooled to.Solid after roasting is added in the 100ml 0.15mol/L KF aqueous solution, under room temperature, stirs 40h, mistake
Filter, wash and be vacuum dried after, at 400 DEG C, roasting 10h, naturally cools to room temperature under nitrogen protection, be obtained catalyst；
(3) in four-hole boiling flask, it is separately added into ethyl acetate 60g, Trifluoroacetic Acid Ethyl Ester 20g and step (2) is obtained urges
Agent 0.06g, reacts 7h at 45 DEG C, and rectifying removes unreacted ethyl acetate and the ethanol of generation obtains condensation product, cold
But, (formic acid is 1 with ethyl acetate mass ratio then to add formic acid and ethyl acetate in the condensation product for obtaining:2) mixing is molten
Liquid 12g, reacts 2h at 35 DEG C, cools down, and filters, filtrate decompression rectifying obtains trifluoroacetic ethyl acetoacetate, divides through GC/MS
Analysis, purity are 99.7%, and yield is 88.5%.
Embodiment 3
(1) in four-hole bottle, by Co (NO3)2·6H2O 17.46g(0.06mol)、Cu(NO3)2·3H2O 4.84g
(0.02mol)、Mn(NO3)2·4H2O 2.45g(0.01mol)、Al(NO3)3·9H2O 7.50g(0.02mol)、Fe(NO3)3·
9H2I 50ml of mixed aqueous solution that O 4.04g (0.01mol) is configured to, with NaOH 10g (0.25mol) and sodium carbonate 1.7g
(0.016mol) II 50ml of mixed aqueous solution for preparing is mixed to get mixed solution, and the pH value for adjusting mixed solution is 9.5, stirring
30min, in 55 DEG C of aging 20h, is filtrated to get filter cake, by Washing of Filter Cake to neutrality, dries 10h at 70 DEG C, grinds to obtain catalyst
Precursor；
(2) roasting 5h at the catalyst precarsor for obtaining step (1) is put in Muffle furnace in 500 DEG C, adds after cooling
In the 60ml0.15mol/L KF aqueous solution, under room temperature, 35h is stirred, after filtering, wash and being vacuum dried, roasting 4h at 500 DEG C,
Naturally cool to room temperature under nitrogen protection, catalyst is obtained；
(3) in four-hole boiling flask, it is separately added into ethyl acetate 80g, Trifluoroacetic Acid Ethyl Ester 20g and step (2) is obtained urges
Agent 0.1g, reacts 9h at 55 DEG C, and rectifying removes unreacted ethyl acetate and the ethanol of generation obtains condensation product, cold
But, (formic acid is 1 with ethyl acetate mass ratio then to add formic acid and ethyl acetate in the condensation product for obtaining:2.5) mixing
Solution 14g, reacts 3h at 45 DEG C, cools down, and filters, filtrate decompression rectifying obtains trifluoroacetic ethyl acetoacetate, through GC/MS
Analysis, purity are 99.5%, and yield is 88.8%.
Embodiment 4
(1) in four-hole bottle, by Co (NO3)2·6H2O 17.46g(0.06mol)、Cu(NO3)2·3H2O 7.25g
(0.03mol)、Al(NO3)3·9H2O 7.50g(0.02mol)、Fe(NO3)3·9H2It is mixed that O 4.04g (0.01mol) is configured to
I 50ml of Heshui solution, the mixed aqueous solution II for preparing with NaOH 10g (0.25mol) and sodium carbonate 1.7g (0.016mol)
50ml is mixed to get mixed solution, and the pH value for adjusting mixed solution is 10, stirs 30min, in 75 DEG C of aging 20h, is filtrated to get
Filter cake, by Washing of Filter Cake to neutrality, dries 14h at 85 DEG C, grinds to obtain catalyst precarsor；
(2) roasting 6h at the catalyst precarsor for obtaining step (1) is put in Muffle furnace in 500 DEG C, adds after cooling
In the 80ml0.15mol/L KF aqueous solution, under room temperature, 30h is stirred, after filtering, wash and being vacuum dried, roasting 4h at 500 DEG C,
Naturally cool to room temperature under nitrogen protection, catalyst is obtained；
(3) in four-hole boiling flask, it is separately added into ethyl acetate 100g, Trifluoroacetic Acid Ethyl Ester 20g and step (2) is obtained urges
Agent 0.2g, reacts 5h at 45 DEG C, and rectifying removes unreacted ethyl acetate and the ethanol of generation obtains condensation product, cold
But, (formic acid is 1 with ethyl acetate mass ratio then to add formic acid and ethyl acetate in the condensation product for obtaining:3) mixing is molten
Liquid 16g, reacts 0.5h at 50 DEG C, cools down, and filters, filtrate decompression rectifying obtains trifluoroacetic ethyl acetoacetate, through GC/MS
Analysis, purity are 99.2%, and yield is 87.5%.
Embodiment 5
(1) in four-hole bottle, by Co (NO3)2·6H2O 29.11g(0.1mol)、Cu(NO3)2·3H2O 15.70g
(0.0650mol)、Al(NO3)3·9H2O 30.95g (0.0825mol), I 80ml of mixed aqueous solution being configured to, with hydroxide
II 80ml of mixed aqueous solution that sodium 20g (0.5mol) and sodium carbonate 4.37g (0.04125mol) are prepared is mixed to get mixed solution,
Adjustment mixed solution pH value be 10.5, stir 30min, in 70 DEG C of aging 20h, be filtrated to get filter cake, by Washing of Filter Cake in
Property, 13h is dry at 75 DEG C, grinds to obtain catalyst precarsor；
(2) roasting 7h at the catalyst precarsor for obtaining step (1) is put in Muffle furnace in 500 DEG C, adds after cooling
In the 120ml0.1mol/L KF aqueous solution, under room temperature, 25h is stirred, after filtering, wash and being vacuum dried, roasting 4h at 500 DEG C,
Naturally cool to room temperature under nitrogen protection, catalyst is obtained；
(3) in four-hole boiling flask, it is separately added into ethyl acetate 50g, Trifluoroacetic Acid Ethyl Ester 20g and step (2) is obtained urges
Agent 0.5g, reacts 8h at 50 DEG C, and rectifying removes unreacted ethyl acetate and the ethanol of generation obtains condensation product, cold
But, (formic acid is 2 with ethyl acetate mass ratio then to add formic acid and ethyl acetate in the condensation product for obtaining:1) mixing is molten
Liquid 20g, reacts 2.5h at 55 DEG C, cools down, and filters, filtrate decompression rectifying obtains trifluoroacetic ethyl acetoacetate, through GC/MS
Analysis, purity are 99.3%, and yield is 88.5%.
Embodiment 6
(1) in four-hole bottle, by Co (NO3)2·6H2O 17.46g(0.06mol)、Mn(NO3)2·4H2O 7.50g
(0.03mol)、Al(NO3)3·9H2O 7.50g(0.02mol)、Fe(NO3)3·9H2It is mixed that O 4.04g (0.01mol) is configured to
I 50ml of Heshui solution, the mixed aqueous solution II for preparing with NaOH 10g (0.25mol) and sodium carbonate 1.7g (0.016mol)
50ml is mixed to get mixed solution, and the pH value for adjusting mixed solution is 9, stirs 30min, in 50 DEG C of aging 25h, is filtrated to get filter
Cake, by Washing of Filter Cake to neutrality, dries 10h at 90 DEG C, grinds to obtain catalyst precarsor；
(2) roasting 8h at the catalyst precarsor for obtaining step (1) is put in Muffle furnace in 550 DEG C, adds after cooling
In the 60ml0.1mol/L KF aqueous solution, under room temperature, 20h is stirred, after filtering, wash and being vacuum dried, roasting 4h at 500 DEG C,
Naturally cool to room temperature under nitrogen protection, catalyst is obtained；
(3) in four-hole boiling flask, it is separately added into ethyl acetate 100g, Trifluoroacetic Acid Ethyl Ester 20g and step (2) is obtained urges
Agent 1g, reacts 10h at 60 DEG C, and rectifying removes unreacted ethyl acetate and the ethanol of generation obtains condensation product, cooling,
(formic acid is 3 with ethyl acetate mass ratio to add formic acid and ethyl acetate again in the condensation product for obtaining:1) mixed solution
30g, reacts 1.5h at 30 DEG C, cools down, and filters, filtrate decompression rectifying obtains trifluoroacetic ethyl acetoacetate, divides through GC/MS
Analysis, purity are 99.5%, and yield is 89.5%.
Claims (6)
1. a kind of method for catalyzing and synthesizing trifluoroacetic ethyl acetoacetate, it is characterised in that comprise the following steps：
A divalent metal salt and trivalent metal salt mixed aqueous solution are mixed by () with NaOH and sodium carbonate mixed aqueous solution, institute
In the divalent metal salt that states and trivalent metal mixed salt solution, bivalent metal ion and trivalent metal ion mol ratio are 2～4:1,
Described divalent metal salt is Mg (NO3)2·6H2O、Co(NO3)2·6H2O、Cu(NO3)2·3H2O、Mn(NO3)2·4H2In O
One or more of mixture, described trivalent metal salt are Al (NO3)3·9H2O or Fe (NO3)3·9H2The mixing of O or both
Thing, after adjustment solution ph is 8.5～10.5, in 50～75 DEG C of aging 15～25h, is filtrated to get filter cake, by Washing of Filter Cake extremely
Neutrality, then 10～15h is dry at 70～90 DEG C, grind to obtain catalyst precarsor；
B catalyst precarsor that step (a) is obtained by () is cooled down, is then added to the KF aqueous solution in 400～550 DEG C of 2～5h of roasting
In, 20～48h is stirred under room temperature, after filtering, wash and being vacuum dried, 3～8h of roasting at 400～550 DEG C, cooling, it is obtained
Catalyst；
C catalyst that step (b) is obtained by () is 0.001～0.05 with ethyl acetate, Trifluoroacetic Acid Ethyl Ester in mass ratio：2～
5：1,5～10h is reacted at 40～60 DEG C, rectifying, cooling obtain condensation product, then add formic acid in the condensation product for obtaining
With the mixed solution of ethyl acetate, at 30～55 DEG C, 0.5～3h is reacted, cool down, filter, filtrate decompression rectifying obtains three
Acetyl fluoride ethyl acetate.
2. the method for catalyzing and synthesizing trifluoroacetic ethyl acetoacetate according to claim 1, it is characterised in that described divalence
The total mole number of slaine and trivalent metal salt is 0.4～0.5 with the ratio of the total mole number of NaOH and sodium carbonate:.1.
3. the method for catalyzing and synthesizing trifluoroacetic ethyl acetoacetate according to claim 1, it is characterised in that described hydrogen-oxygen
It is 4～10 with the mass ratio of sodium carbonate to change NaOH in sodium and sodium carbonate mixture:1.
4. the method for catalyzing and synthesizing trifluoroacetic ethyl acetoacetate according to claim 1, it is characterised in that described KF with
The ratio of the total mole number of divalent metal salt and trivalent metal salt is 1:10～25.
5. the method for catalyzing and synthesizing trifluoroacetic ethyl acetoacetate according to claim 1, it is characterised in that described formic acid
It is 0.5～1.5 with the mixed solution of ethyl acetate and the mass ratio of Trifluoroacetic Acid Ethyl Ester:1.
6. the method for catalyzing and synthesizing trifluoroacetic ethyl acetoacetate according to claim 1, it is characterised in that described formic acid
Mass ratio with formic acid in the mixed solution of ethyl acetate and ethyl acetate is 1:0.3～3.
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