CN1636422B - Process for preparing beta-diketone compound and process for preparing metal complex thereof - Google Patents

Process for preparing beta-diketone compound and process for preparing metal complex thereof Download PDF

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CN1636422B
CN1636422B CN02826972.1A CN02826972A CN1636422B CN 1636422 B CN1636422 B CN 1636422B CN 02826972 A CN02826972 A CN 02826972A CN 1636422 B CN1636422 B CN 1636422B
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tetramethyl
heptadione
solvent
compound
pinacolone
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CN1636422A (en
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斋藤信
植田隆
谷隆士
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Resonac Holdings Corp
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Showa Denko KK
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Abstract

Disclosed is a process for preparing 2,2,6,6-tetramethyl-3,5-heptanedione, comprising reacting a pivalic acid alkyl ester with pinacolone in the presence of an alkali metal alkoxide catalyst using a pivalic acid alkyl ester as a solvent but using no other solvent or reacting them in an amide type or urea type solvent in the presence of an alkali metal alkoxide catalyst. Also disclosed is a process for preparing a 2,2,6,6-tetramethyl-3,5-heptanesione metal complex using the 2,2,6,6-tetramethyl-3,5-heptanedione obtained by the above process. The process for preparing 2,2,6,6-tetramethyl-3,5-heptanedione is an industrially advantageous process in which an alkali metal alkoxide that is easy to handle can be used as a catalyst for preparing 2,2,6,6-tetramethyl-3,5-heptanedione from a pivalic acid alkyl ester and pinacolone.

Description

The preparation method of beta-diketone compound and the preparation method of metal complexes thereof
The cross reference of related application
The application is an application of submitting according to U.S.C. § 111 (a).According to U.S.C. § 119 (e) (1), the application enjoys the applying date of provisional application 60/384,393, and this provisional application is submitted on June 3rd, 2002 according to U.S.C. § 111 (b).
Technical field
The present invention relates to be suitable as the preparation method of the beta-diketone compound of volatility organometallic complex part, wherein organometallic complex is as for example parent material of MOCVD (metal organic chemical vapor deposition), particularly preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione.
The invention still further relates to and use 2,2,6,6-tetramethyl--3,5-heptadione preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes.
Background of invention
As the method for producing inorganic or metallic film, MOCVD has obtained widespread use, and has developed metal alkoxide, beta-diketone complex etc. as the MOCVD raw material.Wherein, known 2,2,6,6-tetramethyl--3, the 5-heptadione can form the volatility title complex with multiple metal, but does not also reach the degree that industrialization is popularized because this compound costs an arm and a leg.
Using gram to come the method for gloomy condensation is the preparation 2,2,6 of common general knowledge, 6-tetramethyl--3, the method for 5-heptadione.For example, at (the J.Am.Chem.Soc. of U.S. chemical institute magazine,) in the 66th phase the 1220th page (1944), and PIVALIC ACID CRUDE (25) ethyl ester and Pinacolone (3,3-dimethyl-2-butanone, tertiary butyl methyl ketone) under the sodium amide catalyst, reacts Synthetic 2,2,6,6-tetramethyl--3,5-heptadione, productive rate are 28%.Also described with sodium ethylate making methyl ketone and ester carry out acylation reaction in this report, it is reported that reactive behavior reduces when using senior ester.
In the 27th phase of organic chemistry magazine (J.Org.Chem..) the 1036th page (1962), methyl pivalate and Pinacolone are the catalyst reaction Synthetic 2 with the sodium hydride, 2,6, and 6-tetramethyl--3,5-heptadione, productive rate are 60-70%.
Use gram to come gloomy condensation reaction preparation 2,2,6,6-tetramethyl--3, other example of 5-heptadione is also reported.But in any method therein, sodium hydride or sodium amide were handled to other similar all being difficult to of metallization sodium of use, thereby had safety problem.And security measures here is necessary, therefore uses these methods to be difficult to realize industrialization.
Except aforesaid method, also reported the synthetic method of the Grignard reaction that utilizes malonyl chloride and t-BuMgCl (t-Bu is the tertiary butyl) and utilized malonyl chloride and the synthetic method of t-BuCu (Li) SPh reaction.But, must use-70 ℃ extremely low temperature approximately in these methods, and handle very difficulty.Therefore, aspect industrial practice, also have problems.
In sum, also do not learn so far any wherein 2,2,6,6-tetramethyl--3, therefore the 5-heptadione can need further to improve by the simple industrialization advantageous method that is easy to operation with the low cost preparation.
Goal of the invention
The object of the present invention is to provide a kind of industrialization advantageous method, wherein can obtain with following formula
(3) Dai Biao beta-diketone compound:
CR 1R 2R 3COCHR 8COCR 5R 6R 7(3)
R wherein 1-R 3And R 5-R 7Be the alkyl of 1-3 carbon atom independently of one another, R 8Alkyl for hydrogen or 1-4 carbon atom.
Specifically, the object of the present invention is to provide a kind of wherein 2,2,6,6-tetramethyl--3, the industrialization advantageous method that the 5-heptadione can easily obtain with low cost.
Or rather, the object of the present invention is to provide the beta-diketone compound method of a kind of following formula of preparation (3) representative, wherein alkali metal alkoxide catalyst can be used in the reaction of the ester cpds and the ketone compound that following formula (2) is represented of following formula (1) representative:
CR 1R 2R 3COOR 4(1)
R wherein 1-R 3Be the alkyl of 1-3 carbon atom independently of one another, R 4Be alkyl,
CR 5R 6R 7COCH 2R 8(2)
R wherein 5-R 7Be the alkyl of 1-3 carbon atom independently of one another, R 8Alkyl for hydrogen or 1-4 carbon atom.
That is to say that the purpose of this invention is to provide a kind of is feedstock production 2,2,6 with new pentane acid alkyl ester and Pinacolone, 6-tetramethyl--3, the method for 5-heptadione, wherein alkali metal alcoholates can be used as catalyzer.
Another object of the present invention provides a kind of by 2,2,6 of above-mentioned preparation, 6-tetramethyl--3,5-heptadione and reacting metal salt preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes.
In order to solve the problem relevant with above-mentioned prior art, the inventor has carried out conscientiously research, found that 2,2,6,6-tetramethyl--3,5-heptadione are can be in the presence of easy-to-handle alkali metal alkoxide catalyst synthetic by new pentane acid alkyl ester and Pinacolone reaction, wherein do not use other solvent in the reaction beginning but react as solvent or in amides or urea type solvent with new pentane acid alkyl ester.The present invention finishes on the basis of this discovery.
In addition, the inventor also find by thus the preparation 2,2,6,6-tetramethyl--3, the reaction of 5-heptadione and metal-salt can easily obtain 2,2,6,6-tetramethyl--3,5-heptadione metal complexes.
Summary of the invention
In brief, the present invention is as described below.
[1] method of the beta-diketone compound of a kind of following formula of preparation (3) representative comprises step 1: in the presence of alkali metal alkoxide catalyst, make the ester cpds of following formula (1) representative and the ketone compound reaction of following formula (2) representative,
CR 1R 2R 3COOR 4(1)
R wherein 1-R 3Be the alkyl of 1-3 carbon atom independently of one another, R 4Be alkyl,
CR 5R 6R 7COCH 2R 8(2)
R wherein 5-R 7Be the alkyl of 1-3 carbon atom independently of one another, R 8Be the alkyl of hydrogen or 1-4 carbon atom,
CR 1R 2R 3COCHR 8COCR 5R 6R 7(3)
R wherein 1-R 3And R 5-R 8Meaning identical with above-mentioned definition.
[2] according to above-mentioned [1] the described method for preparing beta-diketone compound, at least a compound of ester cpds, amide type solvent and urea type solvent that wherein is selected from following formula (1) representative is as solvent,
CR 1R 2R 3COOR 4(1)
R wherein 1-R 3Be the alkyl of 1-3 carbon atom independently of one another, R 4Be alkyl.
[3] according to above-mentioned [1] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione, the compound of its Chinese style (1) representative is R wherein 1-R 3Respectively the do for oneself new pentane acid alkyl ester of methyl, the compound of formula (2) representative are R wherein 5-R 7Methyl and R respectively do for oneself 8Be the Pinacolone of hydrogen, the compound of formula (3) representative is R wherein 1-R 3And R 5-R 7Methyl and R respectively do for oneself 8Be 2,2,6 of hydrogen, 6-tetramethyl--3,5-heptadione.
[4] according to above-mentioned [3] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione, wherein being reflected at the new pentane acid alkyl ester is to carry out under solvent and the situation of not using other solvent.
[5] according to above-mentioned [3] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione, wherein amide type solvent and urea type solvent are as solvent.
[6] according to above-mentioned [5] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione, wherein said solvent is at least a N of being selected from, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone and 1, the solvent of 3-dimethyl-2-imidazolidone.
[7] according to above-mentioned [6] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione, wherein solvent is N, dinethylformamide and/or 1,3-dimethyl-2-imidazolidone.
[8] according to above-mentioned [4] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione, wherein the usage quantity of solvent is based on Pinacolone 3-30 by mass doubly.
[9] according to above-mentioned [3] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione, wherein the basic metal in the alkali metal alkoxide catalyst is sodium or potassium.
[10] according to above-mentioned [9] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione, wherein the alcohol moiety in the alkali metal alkoxide catalyst is the tertiary alcohol.
[11] according to above-mentioned [3] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione, wherein the usage quantity of alkali metal alkoxide catalyst is based on Pinacolone 1-10 times by mole.
[12] a kind of preparation 2,2,6,6-tetramethyl--3, the method of 5-heptadione, comprise following two steps, step 1 is as described in above-mentioned [3]-[11] any one, by make new pentane acid alkyl ester and Pinacolone reaction Synthetic 2 in the presence of alkali metal alkoxide catalyst, 2,6,6-tetramethyl--3,5-heptadione; Step 2 is to 2,2,6, and 6-tetramethyl--3 adds acid neutralizing in the 5-heptadione reaction soln, and adding entry, that this solution is divided into is two-layer, makes 2,2,6,6-tetramethyl--3, and the 5-heptadione is separated as oil reservoir.
[13] according to above-mentioned [12] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione, wherein said acid is at least a acid that is selected from sulfuric acid, hydrochloric acid and nitric acid.
[14] a kind of preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione is comprising containing 2 by fractionation by distillation from what obtain method as described in above-mentioned [12] or [13], 2,6,6-tetramethyl--3 reclaims new pentane acid alkyl ester, Pinacolone and solvent and is applied to described reaction again in the oil reservoir of 5-heptadione.
[15] a kind of preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes, comprising step 3: make in as above-mentioned [3]-[14], obtain in the method as described in any one 2,2,6,6-tetramethyl--3,5-heptadione and reacting metal salt.
[16] according to above-mentioned [15] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes, wherein said metal-salt is at least a metal-salt in halogenide, nitrate, vitriol and the phosphoric acid salt that is selected from metal.
[17] according to above-mentioned [16] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes, wherein said metal-salt is metal chloride and/or metal nitrate.
[18] according to above-mentioned [15] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes, the metal in the wherein said metal-salt is at least a metal that is selected from transition metal and alkaline-earth metal.
[19] according to above-mentioned [18] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes, the metal in the wherein said metal-salt is at least a metal that is selected from alkaline-earth metal, rare earth metal, Ti, Zr, Hf and Cu.
[20] according to above-mentioned [15] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes, wherein hydrophilic solvent is 2,2,6,6-tetramethyl--3, in the reaction of 5-heptadione and metal-salt as solvent.
[21] according to above-mentioned [20] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes, wherein said hydrophilic solvent is the alcohol of 1-4 carbon atom.
[22] according to above-mentioned [21] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes, wherein said alcohol is methyl alcohol.
[23] according to above-mentioned [15] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes wherein after reaction is finished, adds entry so that 2,2,6,6-tetramethyl--3,5-heptadione metal complexes precipitation is separated this metal complexes subsequently.
[24] according to above-mentioned [15] described preparation 2,2,6,6-tetramethyl--3, the method for 5-heptadione metal complexes, wherein said 2,2,6,6-tetramethyl--3,5-heptadione metal complexes are a kind of wherein 2-4 individual 2,2,6,6-tetramethyl--3,5-heptadione molecule and 1 atoms metal coordinate metal complexes.
Detailed Description Of The Invention
The present invention is described in detail as follows.
Characteristics of the present invention are the beta-diketone compounds by the following formula of ketone compound prepared in reaction (3) representative of ester cpds that makes following formula (1) representative in the presence of alkali metal alkoxide catalyst and following formula (2) representative,
CR 1R 2R 3COOR 4(1)
R wherein 1-R 3Be the alkyl of 1-3 carbon atom independently of one another, R 4Be alkyl,
CR 5R 6R 7COCH 2R 8(2)
R wherein 5-R 7Be the alkyl of 1-3 carbon atom independently of one another, R 8Be the alkyl of hydrogen or 1-4 carbon atom,
CR 1R 2R 3COCHR 8COCR 5R 6R 7(3)
R wherein 1-R 3And R 5-R 8Meaning identical with above-mentioned definition.
Below, with useful especially 2,2,6,6-tetramethyl--3, the 5-heptadione elaborates the present invention as the example of beta-diketone compound.
The preferred method of the present invention is to use alkali metal alkoxide catalyst to prepare 2,2,6,6-tetramethyl--3, the method for 5-heptadione by new pentane acid alkyl ester and Pinacolone in organic solvent.Be used for new pentane acid alkyl ester of the present invention and have formula (1) structure, wherein R 1-R 3Be methyl independently of one another, R 4Alcohol moiety for this ester is not particularly limited it, so long as alkyl just can.R 4Be preferably the alkyl of 1-6 carbon atom.The example of this new pentane acid alkyl ester comprises methyl pivalate, PIVALIC ACID CRUDE (25) ethyl ester, PIVALIC ACID CRUDE (25) isopropyl ester and PIVALIC ACID CRUDE (25) butyl ester.
Work as R 4During for phenyl, the activity of described ester itself is enhanced, but because the acidity of the phenol that discharges is stronger, phenol and catalyst reaction form the alkali metal phenolate of low alkalinity, and the result has significantly suppressed described reaction.
Pinacolone as raw material is not particularly limited, any can commercial can using of obtaining.
In the present invention's reaction, bigger variation takes place according to used solvent in reactive behavior, and in the reaction beginning, new pentane acid alkyl ester can be used as solvent by a large amount of uses, needn't use other solvent.
If use other solvent except that new pentane acid alkyl ester, preferably use amide type solvent and urea type solvent, because this two kind solvent can promote described reaction.Amide type solvent be a kind of under reaction conditions for liquid and have a compound of amido linkage, N for example, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc) or N-N-methyl-2-2-pyrrolidone N-(NMP).Urea type solvent be a kind of under reaction conditions for liquid and have a compound of urea key, for example 1,3-dimethyl-2-imidazolidone (DMI).Preferred especially DMF and DMI, this is because hydrogen is not on the α position of carbonyl, and can not produce any carboanion, therefore can suppress the side reaction that is caused by carboanion and ketone or ester condensation reaction.These solvents can use separately also can two or more mixtures form use.Also can be used in combination with other solvent, condition is to produce detrimentally affect (for example, can not use can to the alkali metal alkoxide catalyst generation effect or the solvent of reaction with it) to described reaction.But if only used the solvent that is different from acid amide type and urea type solvent, described reactive behavior will significantly reduce.If the solvent that uses contains water, described reaction will be suppressed, and therefore advantageously described solvent dewaters before use.
Be not particularly limited as the quantity lower limit of the new pentane acid alkyl ester of solvent or the quantity lower limit of amides and urea type solvent, as long as the stirring of reaction system is practical just passable.Though the upper limit of above-mentioned amount is not particularly limited, too Xi Shi reaction system has reduced throughput or activity, is unfavorable.Therefore, be benchmark with the quality, the preferred usage quantity of solvent is based on Pinacolone 0-50 by mass doubly.Preferred use range is in mass 1-40 a times, and preferred especially 3-30 in mass doubly.With the mole is benchmark, and the preferred usage quantity of described solvent is 0-70 a times of Pinacolone molar weight.Preferred use range is in the 0.2-50 of mole doubly, and preferred especially 0.5-20 mole doubly.
The usage quantity of new pentane acid alkyl ester in described reaction be for based on Pinacolone by the 0.5-10 of mole doubly, preferably doubly by the 1-5 of mole, and more preferably doubly by the 1.1-3 of mole.If the amount of Pinacolone is that benchmark is excessive with the new pentane acid alkyl ester, productive rate will reduce owing to the strong influence of Pinacolone from condensation so.If the amount of new pentane acid alkyl ester is that benchmark is excessive with the Pinacolone, must reclaim a large amount of unreacted new pentane acid alkyl esters so.But, when new pentane acid alkyl ester is used as solvent, in described reaction system, there is not difference as the new pentane acid alkyl ester of raw material with as the new pentane acid alkyl ester of solvent, so the usage quantity of new pentane acid alkyl ester be based on Pinacolone 10-30 by mass times.
Adding method for new pentane acid alkyl ester and Pinacolone is not particularly limited, and can add Pinacolone earlier and slowly add new pentane acid alkyl ester then, also can add Pinacolone and new pentane acid alkyl ester simultaneously.But from condensation, the preferred new pentane acid alkyl ester that adds earlier slowly adds Pinacolone then for fear of Pinacolone, and in reaction soln, the amount of new pentane acid alkyl ester should surpass the amount of Pinacolone like this.New pentane acid alkyl ester and Pinacolone can inherent form own add, and also can add after being dissolved in solvent for use.
Temperature of reaction advantageously in 0-150 ℃ of scope, preferred 20-100 ℃.If reaction temperature is spent low, reactive behavior variation and reaction times prolong, and the result causes poor efficiency.If temperature of reaction is too high, productive rate reduces under the influence because of alkaline and the solvolysis that the side reaction development causes.
As the alkali metal alkoxide catalyst that is used for described reaction, can use any compound, but preferred basic metal is sodium or potassium, more preferably potassium.As the alcohol that is used to form alkoxide, usually use monohydroxy-alcohol (wherein alkyl can be a side chain) with 1-6 carbon atom alkyl, still also can use polyvalent alcohol (for example ethylene glycol or propylene glycol) or wherein the part carbochain of alkyl by Sauerstoffatom alternate alkoxyl alcohol (for example monoalky lether of ethylene glycol).The tertiary alcohol that preferably has alkyl.That for example, can mention has a potassium tert.-butoxide.
Above-mentioned alkali metal alkoxide catalyst can use separately or use in two or more modes by the arbitrary proportion combination.If the alkali number that adds is very few, the reactive behavior variation.If their amount is excessive, productive rate will reduce because of the solvolysis that alkali or side reaction cause.Based on 1 mole of Pinacolone meter, the amount of alkali is preferably in the 1-10 molar range.
When new pentane acid alkyl ester and Pinacolone restrain gloomy condensation reaction Synthetic 2 in the presence of alkali metal alkoxide catalyst, 2,6,6-tetramethyl--3, during the 5-heptadione, obtain 2,2,6,6-tetramethyl--3, the 5-heptadione exists with the form of an alkali metal salt.In order to separate 2,2,6,6-tetramethyl--3, the 5-heptadione, 2,2,6,6-tetramethyl--3, an alkali metal salt of 5-heptadione is with the acid neutralization and therefore dissociate out.
Example in the acid of this application comprises mineral acid, for example hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; Organic acid, for example formic acid and acetate; And Lewis acid, for example iron protochloride, iron trichloride, tin protochloride and aluminum chloride.Preferred sulfuric acid, hydrochloric acid and the nitric acid of using.These acid can be used separately also and can two or more be used in combination by arbitrary proportion.The add-on of acid should be enough to reach the equivalents that is no less than the alkali metal alkoxide catalyst that is used for described reaction.Owing to produce heat in the N-process, can cool off in case of necessity.
In order to reclaim 2,2,6 of reaction formation, 6-tetramethyl--3, the 5-heptadione adds reaction soln so that this reaction soln is divided into oil reservoir and water layer with water, and wherein oil reservoir contains 2,2 of the formation that responds, 6,6-tetramethyl--3,5-heptadione, new pentane acid alkyl ester, Pinacolone and solvent; Water layer contains water, solvent and inorganic salt.Because 2,2,6,6-tetramethyl--3,5-heptadione have the bigger hydrophobic group of volume, it is water-soluble hardly, thus even do not use extraction agent, 2,2,6,6-tetramethyl--3, the 5-heptadione also can reclaim with good recovery.But, can add hydrocarbon, ether, aromatic hydrocarbon or similar substance in case of necessity and extract.
In case of necessity, can distill purification to above-mentioned isolating oil reservoir.New pentane acid alkyl ester, Pinacolone and solvent that boiling point is lower than target product can easily reclaim and be used further to described reaction.
To by 2,2,6 of the inventive method preparation, 6-tetramethyl--3, the method that the 5-heptadione prepares metal complexes is not particularly limited.For example, described metal complexes can prepare by the method that " inorganic synthetic " o. 11th (1968) and " inorganic synthetic " the 31st phase (1997) describe.Usually, described metal complexes can be by 2,2,6,6-tetramethyl--3,5-heptadione and metal-salt prepared in reaction in organic solvent.
To 2,2,6,6-tetramethyl--3, the metal in the 5-heptadione metal complexes is not particularly limited, as long as can form the metal of metal complexes with beta-diketone compound.The preferred embodiment of this metal comprises alkaline-earth metal, rare earth metal, Ti, Zr, Hf and Cu.The example of alkaline-earth metal comprises Sr and Ba, and the example of rare earth metal comprises Y, La, Pr, Nd, Sm, Eu, Tm and Tb.
Consider 2,2,6,6-tetramethyl--3, the easy coordinate molecule number of 5-heptadione, described metal is preferably the metal of divalence to quadrivalent ion.When metal ion was the n valency, usually n 2,2,6,6-tetramethyl--3,5-heptadione molecule and an atoms metal coordination.
Though to being used for 2,2,6,6-tetramethyl--3, the metal-salt of 5-heptadione reaction is not particularly limited, preferred inorganic salt.The example of this salt comprises halogenide, nitrate, vitriol, phosphoric acid salt and perchlorate.Special preferably nitrate and muriate.These salt can use separately or use with form of mixtures.
Metal-salt and 2,2,6,6-tetramethyl--3, the quantity of 5-heptadione changes than the price with metal in the metal-salt, but when the price of described metal is n, and 2,2,6,6-tetramethyl--3,5-heptadione are preferably with the amount use mole doubly of n * 0.9 to n * 1.5.
As being used for 2,2,6,6-tetramethyl--3, the solvent of 5-heptadione and reacting metal salt, can not have any with an organic solvent restrictedly.Described solvent preferably can dissolve the solvent of described metal-salt.Therefore, preferred polar solvent, particularly hydrophilic solvent, and more preferably have the alcoholic solvent of 1-4 carbon atom.The example of this solvent comprises methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, methyl cellosolve and ethoxy ethanol.
Described temperature of reaction should be not less than the fusing point of solvent and not be higher than the boiling point of solvent.When carrying out under being reflected near the temperature of room temperature, can not produce any trouble when described.Therefore, temperature of reaction is preferably in 10-40 ℃ of scope, in 15-30 ℃ of scope.
When solvent is hydrophobic nature, by 2,2,6 of described reaction formation, 6-tetramethyl--3,5-heptadione metal complexes can obtain by concentrating.When solvent is normally used hydrophilic solvent, add water so that metal complexes as solid precipitation, and separates this solid by measures such as filtration, centrifugations.According to the type of metal, even metal complexes also can precipitate under the condition of not adding water especially sometimes.
Chemical vapour deposition (for example, " experimental chemistry teaching materials 13 " (Experimental Chemistry Lectures 13), the 4th edition by common general knowledge, the 46th page), described 2,2,6,6-tetramethyl--3,5-heptadione metal complexes can be converted into metal oxide.For example, described 2,2,6,6-tetramethyl--3,5-heptadione metal complexes produces steam by evaporation, and this steam mixes with oxygen-containing gas and heats to obtain metal oxide.
The representative instance of this method is MOCVD.MOCVD is the general designation of a technology, and in this technology, thermolysis is to carry out crystal growing near matrix for organometallic compound, and this technology is used to form oxide compound such as compound semiconductor, magnetic substance, ferroelectric membranc and high temperature superconductor crystal at present.Or rather, earlier at vacuum reactor internal heating matrix, near matrix, send into organometallic compound gas then and send into oxygen in case of necessity, near matrix surface or matrix, carry out pyrolysis by the induction heating that produces by high frequency electric source or plasma generating, to form metallic membrane or oxide film at matrix surface.
As everyone knows, beta-diketon metal complexes or derivatives thereof is used as parent material--organometallic compound in MOCVD, and the capacity of decomposition of described organometallic compound or vaporization temperature can be controlled as the alkyl of the beta-diketone compound side chain of part by suitable selection.
Embodiment
The present invention further sets forth with reference to the following example, but these embodiment do not constitute any restriction to the present invention.
In the following example, 2,2,6,6-tetramethyl--3, the detection by quantitative of 5-heptadione is determined by gas chromatographic analysis.Analysis condition is as described below.About 2,2,6,6-tetramethyl--3, the 5-heptadione uses the purity of being produced by Wako Junyaku K.K. to be not less than 95% the reagent standard prod as 95% purity.
Analytical conditions for gas chromatography
Instrument: GC-14A is made by Shimadzu Seisakusho K.K.; Disintegrating method (division ratio: 60)
Capillary column: DB-5 is by J﹠amp; W Co. makes diameter 0.25mm * 30mm, inactive liquid thickness: 0.25 μ.
Carrier gas: helium
Injection volume: 1 μ l
INJ. temperature: 250 ℃
DET. temperature (FID): 280 ℃
Temperature program(me): 50 ℃ of down insulations 5 minutes are heated to 250 ℃ with 10 ℃/minute heating rate then.
Method for quantitatively determining: marker method (internal standard material: naphthalene)
Embodiment 1
In one 2 liters four-hole boiling flask, put into 1000g DMF and 135g potassium tert.-butoxide, and under the stirring of mechanical stirrer, they are heated to 50 ℃.Then, add the 186g methyl pivalate with dropping funnel.Afterwards, in 3 hours, adds the mixing solutions of 80g Pinacolone and 100g DMF, followed under heating restir 5 hours with dropping funnel.By gas chromatographic analysis confirm to have generated in the solution 76.5g (productive rate: 52% (based on Pinacolone)) 2,2,6,6-tetramethyl--3,5-heptadione.
Embodiment 2
React according to the mode identical, but solvent is changed into DMAc with embodiment 1.By gas chromatographic analysis confirm to have generated in the solution 47.1g (productive rate: 32% (based on Pinacolone)) 2,2,6,6-tetramethyl--3,5-heptadione.
Embodiment 3
React according to the mode identical, but solvent is changed into DMI with embodiment 1.By gas chromatographic analysis confirm to have generated in the solution 88.3g (productive rate: 60% (based on Pinacolone)) 2,2,6,6-tetramethyl--3,5-heptadione.
Embodiment 4
React according to the mode identical, but solvent is changed into NMP with embodiment 1.By gas chromatographic analysis confirm to have generated in the solution 58.9g (productive rate: 40% (based on Pinacolone)) 2,2,6,6-tetramethyl--3,5-heptadione.
Embodiment 5
React according to the mode identical, but the amount of potassium tert.-butoxide is changed into 270g with embodiment 1.By gas chromatographic analysis confirm to have generated in the solution 103.0g (productive rate: 70% (based on Pinacolone)) 2,2,6,6-tetramethyl--3,5-heptadione.
Embodiment 6
React according to the mode identical, but replace potassium tert.-butoxide with the 81.6g sodium ethylate with embodiment 1.By gas chromatographic analysis confirm to have generated in the solution 22.1g (productive rate: 15% (based on Pinacolone)) 2,2,6,6-tetramethyl--3,5-heptadione.
Embodiment 7
React according to the mode identical, but replace potassium tert.-butoxide with the 115.2g sodium tert-butoxide with embodiment 1.By gas chromatographic analysis confirm to have generated in the solution 61.8g (productive rate: 42% (based on Pinacolone)) 2,2,6,6-tetramethyl--3,5-heptadione.
Embodiment 8
React according to the mode identical, but temperature of reaction is changed into 90 ℃ with embodiment 1.By gas chromatographic analysis confirm to have generated in the solution 66.2g (productive rate: 45% (based on Pinacolone)) 2,2,6,6-tetramethyl--3,5-heptadione.
Embodiment 9
React according to the mode identical, but do not use any special solvent with embodiment 1, just with the methyl pivalate identical with DMF quantity as solvent.By gas chromatographic analysis confirm to have generated in the solution 44.2g (productive rate: 30% (based on Pinacolone)) 2,2,6,6-tetramethyl--3,5-heptadione.
Reference example 1
React according to the mode identical with embodiment 1, but solvent is changed into 1,4-two
Figure B028269721D00131
Alkane.Productive rate is 1% (based on Pinacolone) as a result.
Reference example 2
React according to the mode identical, but solvent is changed into acetonitrile with embodiment 1.As a result, almost do not have 2,2,6,6-tetramethyl--3, the 5-heptadione generates.
Reference example 3
React according to the mode identical, but solvent is changed t-butyl methyl ether with embodiment 1.Productive rate is 2% (based on Pinacolone) as a result.
Reference example 4
React according to the mode identical, but solvent is changed into toluene with embodiment 1.Productive rate is 4% (based on Pinacolone) as a result.
Reference example 5
React according to the mode identical, but solvent is changed into the trimethyl carbinol with embodiment 1.As a result, almost do not have 2,2,6,6-tetramethyl--3, the 5-heptadione generates.
Reference example 6
React according to the mode identical, but solvent is changed into dimethyl sulfoxide (DMSO) with embodiment 1.Productive rate is 10% (based on Pinacolone) as a result.
Reference example 7
With the methylene dichloride is the operation that solvent carries out embodiment 1.As a result, produced heat, do not carried out the reaction that needs at methylene dichloride and potassium tert.-butoxide mix stages.
Reference example 8
React according to the mode identical, but solvent is changed into dimethylbenzene with embodiment 7.As a result, almost do not have 2,2,6,6-tetramethyl--3, the 5-heptadione generates.
Comparative Examples 1
React according to the mode identical, but replace methyl pivalate with the PIVALIC ACID CRUDE (25) phenyl ester with embodiment 1.As a result, almost do not have 2,2,6,6-tetramethyl--3, the 5-heptadione generates.
Embodiment 10
To containing 2,2,6 according to the mode synthetic identical with embodiment 1,6-tetramethyl--3 adds 74.3g sulfuric acid, and then adds 1000g water in the reaction soln of 5-heptadione, this solution is divided into oil reservoir and water layer.Reclaim oil reservoir and utilize GC (gas-chromatography) to analyze.As a result, 2,2,6,6-tetramethyl--3, the rate of recovery of 5-heptadione reaches 99.5%.
Embodiment 11
Under stirring action, the NaOH of 40.4g (1.01mol) purity 96% is dissolved in the 1155g methyl alcohol, and with the solution cool to room temperature that obtains.Then, add 2,2,6 of 180.3g (0.882mol) purity 90% bit by bit, 6-tetramethyl--3,5-heptadione.Under 25-28 ℃ room temperature, will be in 30 minutes by the Y (NO of 132g (0.294mol) purity 85.6% 3) 36H 2O is dissolved in the solution that 1225g methyl alcohol obtains and adds in this mixture.Reacted 1 hour, and leached sedimentary crystal.In resulting solution, with splashing into 3500g water in 1.5 hours.After described being added dropwise to complete, stirred 1 hour.Take out crystal and the drying that forms by centrifugation.89%) three thus, obtains 166.8g (productive rate: (2,2,6,6-tetramethyl--3, the 5-heptadione closes) yttrium.
Embodiment 12
In 256g methyl alcohol, dissolve in the methanol solution of sodium methylate of 48.6g (0.252mol) purity 28%, and will obtain the solution cool to room temperature.Then, under agitation with 2,2,6 of 49.3g (0.252mol) purity 94%, 6-tetramethyl--3, the 5-heptadione splashes into.Under 25-28 ℃ room temperature, will be in 30 minutes by the Eu (NO of 45.8g (0.084mol) purity 81.9% 3) 36H 2O is dissolved in the solution that 367g methyl alcohol obtains and adds in this mixture.Reacted 1 hour, and leached sedimentary crystal.In resulting solution, with splashing into 1000g water in 1.5 hours.After described being added dropwise to complete, stirred 1 hour.Take out crystal and the drying that forms by centrifugation.93.6%) three thus, obtains 55.2g (productive rate: (2,2,6,6-tetramethyl--3, the 5-heptadione closes) europium.
Embodiment 13
Obtain three (2,2,6 of 55.2g (productive rate 93.6%) according to the mode identical with embodiment 12,6-tetramethyl--3, the 5-heptadione closes) terbium, still, use 2,2,6 of 49.3g (0.252mol) purity 94%, 6-tetramethyl--3, the 5-heptadione is as 2,2,6,6-tetramethyl--3, the 5-heptadione, and with the Tb (NO of 46.0g (0.084mol) purity 82.7% 3) 36H 2O substitutes Eu (NO 3) 36H 2O.
Embodiment 14
Under stirring action, with 2,2,6 of 43.7g (0.216mol) purity 91%, 6-tetramethyl--3, the 5-heptadione splashes in the 177g methyl alcohol.In about 5 minutes, in resulting solution, add ZrCl then by 12.7g (0.054mol) purity 99% 4Be dissolved in the solution that 218g methyl alcohol and cool to room temperature obtain.Under agitation reacted 1 hour, and in 50 minutes, add 590g water.Then, stirred 1 hour.NaOH solution with 20% is adjusted into 6.6 with the pH of resultant solution.Collect crystal and the drying that forms by centrifugation.98.2%) four obtains 43.9g (productive rate: (2,2,6,6-tetramethyl--3, the 5-heptadione closes) zirconium thus.
Embodiment 15
In 67g methyl alcohol, dissolve in the methanol solution of sodium methylate of 6.6g (0.0366mol) purity 30%, and with the solution cool to room temperature that obtains.Then, under agitation splash into 2,2,6 of 7.41g (0.0366mol) purity 91%, 6-tetramethyl--3,5-heptadione.In this mixture, add Ba (NO by 4.83g (0.0183mol) purity 99% 3) 2Be dissolved in the solution that 38g water obtains.Reacted 1 hour, and dripped 100g water.After described being added dropwise to complete, stirred 1 hour.Take out crystal and the drying that forms by centrifugation.87.6%) two thus, obtains 8.07g (productive rate: (2,2,6,6-tetramethyl--3, the 5-heptadione closes) barium.
Embodiment 16
Obtain 7.28g (productive rate 87.7%) two (2,2,6,6-tetramethyl--3, the 5-heptadione closes) strontium according to the mode identical with embodiment 15, but with the Sr (NO of 3.87g purity 99.5% 3) 2Substitute Ba (NO 3) 2
Embodiment 17
In 53.2g methyl alcohol, dissolve in the methanol solution of sodium methylate of 9.31g (0.0517mol) purity 30%, and with resulting solution cool to room temperature.Then, under agitation splash into 2,2,6 of 10.5g (0.0517mol) purity 91%, 6-tetramethyl--3,5-heptadione.Then, add 6.46g (0.0259mol) Cu (NO 3) 26H 2O.Reacted 1 hour, by filtering the crystal of collecting precipitation.This crystal is dissolved in the 100g ether, with 100g water washing 5 times and be evaporated to drying.78.7%) two thus, obtains 8.74g (productive rate: (2,2,6,6-tetramethyl--3, the 5-heptadione closes) copper.
Effect of the present invention
According to the present invention, by using easy-to-handle alkali metal alkoxide catalyst, make under mild conditions to prepare 2,2,6 with low cost, 6-tetramethyl--3, the 5-heptadione becomes possibility, and needn't drop into substantial contribution aspect plant and equipment.
2,2,6 of the present invention preparation, 6-tetramethyl--3, the 5-heptadione can with the metal-complexing synthetic compound, thereby can provide the raw material 2,2,6 of MOCVD with low cost, 6-tetramethyl--3,5-heptadione metal complexes.

Claims (8)

1. method for preparing the beta-diketone compound of following formula (3) representative comprises step 1: in the presence of alkali metal alkoxide catalyst, the ester cpds that makes following formula (1) representative reacts with the ketone compound that following formula (2) is represented,
CR 1R 2R 3COOR 4(1)
R wherein 1-R 3Be the alkyl of 1-3 carbon atom independently of one another, R 4Be alkyl,
CR 5R 6R 7COCH 2R 8(2)
R wherein 5-R 7Be the alkyl of 1-3 carbon atom independently of one another, R 8Be the alkyl of hydrogen or 1-4 carbon atom,
CR 1R 2R 3COCHR 8COCR 5R 6R 7(3)
R wherein 1-R 3And R 5-R 8Meaning identical with above-mentioned definition,
Wherein, use and not have the amide type solvent of hydrogen on the α position be selected from carbonyl and on the α position of carbonyl, not have at least a compound in the urea type solvent of hydrogen as solvent.
2. the method for preparing beta-diketone compound as claimed in claim 1, wherein solvent is N, dinethylformamide and/or 1,3-dimethyl-2-imidazolidone.
3. the method for preparing beta-diketone compound as claimed in claim 1, the compound of its Chinese style (1) representative are R wherein 1-R 3Respectively the do for oneself new pentane acid alkyl ester of methyl, the compound of formula (2) representative are R wherein 5-R 7Methyl and R respectively do for oneself 8Be the Pinacolone of hydrogen, the compound of formula (3) representative is R wherein 1-R 3And R 5-R 7Methyl and R respectively do for oneself 8Be 2,2,6 of hydrogen, 6-tetramethyl--3,5-heptadione.
4. the method for preparing beta-diketone compound as claimed in claim 3, wherein the usage quantity of solvent is based on Pinacolone 3-30 by mass doubly.
5. the method for preparing beta-diketone compound as claimed in claim 3, wherein the basic metal in the alkali metal alkoxide catalyst is sodium or potassium.
6. the method for preparing beta-diketone compound as claimed in claim 5, wherein the alcohol moiety in the alkali metal alkoxide catalyst is the tertiary alcohol.
7. the method for preparing beta-diketone compound as claimed in claim 3, wherein the usage quantity of alkali metal alkoxide catalyst is based on Pinacolone 1-10 times by molar weight.
8. the method for preparing beta-diketone compound as claimed in claim 3 also comprises the steps 2: to 2,2,6,6-tetramethyl--3 adds acid neutralizing in the reaction soln of 5-heptadione, and adding entry, that this solution is divided into is two-layer, so that 2,2,6,6-tetramethyl--3, the 5-heptadione is separated as oil reservoir, and wherein said acid is at least a acid that is selected from sulfuric acid, hydrochloric acid and nitric acid.
CN02826972.1A 2002-01-09 2002-12-18 Process for preparing beta-diketone compound and process for preparing metal complex thereof Expired - Fee Related CN1636422B (en)

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