CN1636422A - 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 PDFInfo
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- CN1636422A CN1636422A CN02826972.1A CN02826972A CN1636422A CN 1636422 A CN1636422 A CN 1636422A CN 02826972 A CN02826972 A CN 02826972A CN 1636422 A CN1636422 A CN 1636422A
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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 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 complex.
Background of invention
As the method for producing inorganic or metallic film, MOCVD has obtained extensive 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 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 neopentanoic acid ethyl ester and pinacoline (3,3-dimethyl-2-butanone, tert-butyl group MIBK) under the Sodamide catalyst, reacts Synthetic 2,2,6,6-tetramethyl-3,5-heptadione, productive rate are 28%.Also described with caustic alcohol making MIBK and ester carry out acylation reaction in this report, it is reported that reactivity reduces when using senior ester.
In the 27th phase of organic chemistry magazine (J.Org.Chem..) the 1036th page (1962), methyl pivalate and pinacoline 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 Sodamide were handled to other similar all being difficult to of metallization sodium of use, thereby had safety problem.And safety measure here is necessary, therefore uses these methods to be difficult to realize industrialization.
Except said method, also reported the synthetic method of the Grignard reaction that utilizes malonyl chloride and t-BuMgCl (t-Bu is the tert-butyl group) 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 beta-diketone compound with following formula (3) representative:
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 compounds and the ketonic 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 pinacoline, 6-tetramethyl-3, the method for 5-heptadione, wherein alkali metal alcoholates can be used as catalyst.
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 complex.
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 pinacoline reaction, wherein do not use other solvent in the reaction beginning but react as solvent or in amide-type 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 slaine can easily obtain 2,2,6,6-tetramethyl-3,5-heptadione metal complex.
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 compounds of following formula (1) representative and the ketonic 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 compounds, 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 pinacoline 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-dimethylacetylamide, N-methyl pyrrolidone and 1, the solvent of 3-dimethyl-2-imidazolidinone.
[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-imidazolidinone.
[8] according to above-mentioned [4] described preparation 2,2,6,6-tetramethyl-3, the method for 5-heptadione, wherein the use amount of solvent is based on pinacoline 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 alkali 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 use amount of alkali metal alkoxide catalyst is based on pinacoline 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 pinacoline 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 solution, 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 separated from what obtain method as described in above-mentioned [12] or [13], 2,6,6-tetramethyl-3 reclaims new pentane acid alkyl ester, pinacoline 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 complex, 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 complex, wherein said slaine is at least a slaine in halide, nitrate, sulfate and the phosphate 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 complex, wherein said slaine 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 complex, the metal in the wherein said slaine 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 complex, the metal in the wherein said slaine 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 complex, wherein hydrophilic solvent is 2,2,6,6-tetramethyl-3, in the reaction of 5-heptadione and slaine as solvent.
[21] according to above-mentioned [20] described preparation 2,2,6,6-tetramethyl-3, the method for 5-heptadione metal complex, 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 complex, 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 complex wherein after reaction is finished, adds entry so that 2,2,6,6-tetramethyl-3,5-heptadione metal complex precipitation is separated this metal complex subsequently.
[24] according to above-mentioned [15] described preparation 2,2,6,6-tetramethyl-3, the method for 5-heptadione metal complex, wherein said 2,2,6,6-tetramethyl-3,5-heptadione metal complex are a kind of wherein 2-4 individual 2,2,6,6-tetramethyl-3, the metal complex of 5-heptadione molecule and 1 metallic atom coordination.
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 ketonic compound prepared in reaction (3) representative of ester compounds 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 pinacoline 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, neopentanoic acid ethyl ester, neopentanoic acid isopropyl ester and neopentanoic acid 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.
Pinacoline 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 reactivity, 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 condition for liquid and have a compound of amido link, N for example, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAc) or N-N-methyl-2-2-pyrrolidone N-(NMP).Urea type solvent be a kind of under reaction condition for liquid and have a compound of urea key, for example 1,3-dimethyl-2-imidazolidinone (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 harmful effect (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 reactivity 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 amide-type 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 production capacity or activity, is unfavorable.Therefore, be benchmark with the quality, the preferred use amount of solvent is based on pinacoline 0-50 by mass doubly.The preferred scope of application is in mass 1-40 a times, and preferred especially 3-30 in mass doubly.With the mole is benchmark, and the preferred use amount of described solvent is 0-70 a times of pinacoline mole.The preferred scope of application is in the 0.2-50 of mole doubly, and preferred especially 0.5-20 mole doubly.
The use amount of new pentane acid alkyl ester in described reaction be for based on pinacoline 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 pinacoline is that benchmark is excessive with the new pentane acid alkyl ester, productive rate will reduce owing to the strong influence of pinacoline from condensation so.If the amount of new pentane acid alkyl ester is that benchmark is excessive with the pinacoline, 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 use amount of new pentane acid alkyl ester be based on pinacoline 10-30 by mass times.
Adding method for new pentane acid alkyl ester and pinacoline is not particularly limited, and can add pinacoline earlier and slowly add new pentane acid alkyl ester then, also can add pinacoline and new pentane acid alkyl ester simultaneously.But from condensation, the preferred new pentane acid alkyl ester that adds earlier slowly adds pinacoline then for fear of pinacoline, and in reaction solution, the amount of new pentane acid alkyl ester should surpass the amount of pinacoline like this.New pentane acid alkyl ester and pinacoline can intrinsic form own add, and also can add after being dissolved in solvent for use.
Reaction temperature advantageously in 0-150 ℃ of scope, preferred 20-100 ℃.If reaction temperature is spent low, reactivity variation and reaction time prolong, and the result causes poor efficiency.If reaction temperature 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 alkali metal is sodium or potassium, more preferably potassium.As the alcohol that is used to form alkoxide, usually use monohydric alcohol (wherein alkyl can be a side chain), still also can use polyalcohol (for example ethylene glycol or propylene glycol) or the alkoxyl alcohol (for example monoalky lether of ethylene glycol) that substituted by oxygen atom of the part carbochain of alkyl wherein with 1-6 carbon atom alkyl.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 reactivity 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 pinacoline meter, the amount of alkali is preferably in the 1-10 molar range.
When new pentane acid alkyl ester and pinacoline 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 alkali metal salt.In order to separate 2,2,6,6-tetramethyl-3, the 5-heptadione, 2,2,6,6-tetramethyl-3, the alkali metal salt of 5-heptadione is with the acid neutralization and therefore dissociate out.
Example in the acid of this application comprises inorganic 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 frerrous chloride, ferric trichloride, stannous chloride and aluminium 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 addition 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 solution so that this reaction solution 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, pinacoline and solvent; Water layer contains water, solvent and inorganic salts.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 extractant, 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 the oil reservoir of above-mentioned separation.New pentane acid alkyl ester, pinacoline 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 complex is not particularly limited.For example, described metal complex can prepare by the method that " inorganic synthetic " o. 11th (1968) and " inorganic synthetic " the 31st phase (1997) describe.Usually, described metal complex can be by 2,2,6,6-tetramethyl-3,5-heptadione and slaine prepared in reaction in organic solvent.
To 2,2,6,6-tetramethyl-3, the metal in the 5-heptadione metal complex is not particularly limited, as long as can form the metal of metal complex 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 molecular number of the easy coordination 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 a metallic atom coordination.
Though to being used for 2,2,6,6-tetramethyl-3, the slaine of 5-heptadione reaction is not particularly limited, preferred inorganic salts.The example of this salt comprises halide, nitrate, sulfate, phosphate and perchlorate.Special preferably nitrate and chloride.These salt can use separately or use with form of mixtures.
Slaine and 2,2,6,6-tetramethyl-3, the quantity of 5-heptadione changes than the price with metal in the slaine, 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 slaine.Therefore, preferred polar solvent, particularly hydrophilic solvent, and more preferably have the alcohols solvent of 1-4 carbon atom.The example of this solvent comprises methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, methyl cellosolve and ethoxy ethanol.
Described reaction temperature 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, reaction temperature is preferably in 10-40 ℃ of scope, in 15-30 ℃ of scope.
When solvent is hydrophobicity, by 2,2,6 of described reaction formation, 6-tetramethyl-3,5-heptadione metal complex can obtain by concentrating.When solvent is normally used hydrophilic solvent, adds water so that metal complex precipitates as solid, and separate this solid by measures such as filtration, centrifugations.According to the type of metal, even metal complex also can precipitate under the condition of not adding water especially sometimes.
Chemical vapour deposition (CVD) (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 complex can be converted into metal oxide.For example, described 2,2,6,6-tetramethyl-3,5-heptadione metal complex 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, thermal decomposition is to carry out crystal growing near matrix for organo-metallic compound, and this technology is used to form oxide such as compound semiconductor, magnetisable material, ferroelectric thin film and high temperature superconductor crystal at present.Or rather, in vacuum reactor, add earlier hot basal body, near matrix, send into organo-metallic 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 metal film or oxidation film at matrix surface.
As everyone knows, beta-diketon metal complex or derivatives thereof is used as parent material--organo-metallic compound in MOCVD, and the capacity of decomposition of described organo-metallic compound or evaporating 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 WakoJunyaku K.K. to be not less than 95% the reagent standardized product 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 the rate of heat addition then.
Method for quantitatively determining: internal standard 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 agitator, they are heated to 50 ℃.Then, add the 186g methyl pivalate with dropping funel.Afterwards, use dropping funel in 3 hours, to add the mixed solution of 80g pinacoline and 100g DMF, then under heating, stirred again 5 hours.By gas chromatographic analysis confirm to have generated in the solution 76.5g (productive rate: 52% (based on pinacoline)) 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 pinacoline)) 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 pinacoline)) 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 pinacoline)) 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 pinacoline)) 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 caustic alcohol with embodiment 1.By gas chromatographic analysis confirm to have generated in the solution 22.1g (productive rate: 15% (based on pinacoline)) 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 pinacoline)) 2,2,6,6-tetramethyl-3,5-heptadione.
Embodiment 8
React according to the mode identical, but reaction temperature 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 pinacoline)) 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 pinacoline)) 2,2,6,6-tetramethyl-3,5-heptadione.
Reference example 1
React according to the mode identical, but solvent is changed into 1, the 4-diox with embodiment 1.Productive rate is 1% (based on pinacoline) 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 pinacoline) 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 pinacoline) as a result.
Reference example 5
React according to the mode identical, but solvent is changed into the tert-butyl alcohol 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 pinacoline) as a result.
Reference example 7
With the carrene is the operation that solvent carries out embodiment 1.As a result, produced heat, do not carried out the reaction that needs at carrene 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 neopentanoic acid 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 according to the mode identical with embodiment 1 synthetic contain 2,2,6,6-tetramethyl-3 adds 74.3g sulfuric acid, and then adds 1000g water in the reaction solution 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 the crystal of precipitation.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 the crystal of precipitation.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 temperate condition 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 complex.
Claims (24)
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 compounds that makes following formula (1) representative reacts with the ketonic 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.
2. the method for preparing beta-diketone compound as claimed in claim 1, at least a compound of ester compounds, amide type solvent and urea type solvent that wherein is selected from following formula (1) representative be 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. preparation 2,2,6 as claimed in claim 1,6-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 pinacoline 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. preparation 2,2,6 as claimed in claim 3,6-tetramethyl-3, the method for 5-heptadione wherein is reflected at new pentane acid alkyl ester as solvent and do not use under the situation of other solvent and carry out.
5. preparation 2,2,6 as claimed in claim 3,6-tetramethyl-3, the method for 5-heptadione, wherein amide type solvent and urea type solvent are as solvent.
6. preparation 2,2,6 as claimed in claim 5,6-tetramethyl-3, the method for 5-heptadione, wherein said solvent is to be selected from N, dinethylformamide, N, N-dimethylacetylamide, N-methyl pyrrolidone and 1, at least a solvent of 3-dimethyl-2-imidazolidinone.
7. preparation 2,2,6 as claimed in claim 6,6-tetramethyl-3, the method for 5-heptadione, wherein solvent is N, dinethylformamide and/or 1,3-dimethyl-2-imidazolidinone.
8. preparation 2,2,6 as claimed in claim 4,6-tetramethyl-3, the method for 5-heptadione, wherein the use amount of solvent is based on pinacoline 3-30 by mass doubly.
9. preparation 2,2,6 as claimed in claim 3,6-tetramethyl-3, the method for 5-heptadione, wherein the alkali metal in the alkali metal alkoxide catalyst is sodium or potassium.
10. preparation 2,2,6 as claimed in claim 9,6-tetramethyl-3, the method for 5-heptadione, wherein the alcohol moiety in the alkali metal alkoxide catalyst is the tertiary alcohol.
11. preparation 2,2,6 as claimed in claim 3,6-tetramethyl-3, the method for 5-heptadione, wherein the use amount of alkali metal alkoxide catalyst is based on pinacoline 1-10 times by mole.
12. one kind prepares 2,2,6,6-tetramethyl-3, the method of 5-heptadione, comprise following two steps, step 1 is as described among the claim 3-11 any one, by make new pentane acid alkyl ester and pinacoline 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 reaction solution 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.
13. preparation 2,2,6 as claimed in claim 12,6-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. one kind prepares 2,2,6,6-tetramethyl-3, the method for 5-heptadione comprises by separated containing 2 from what obtain claim 12 or 13 described methods, 2,6,6-tetramethyl-3 reclaims new pentane acid alkyl ester, pinacoline and solvent and they is applied to described reaction again in the oil reservoir of 5-heptadione.
15. one kind prepares 2,2,6,6-tetramethyl-3, the method for 5-heptadione metal complex comprises step 3: make in as claim 3-14, obtain in the method as described in any one 2,2,6,6-tetramethyl-3,5-heptadione and reacting metal salt.
16. preparation 2,2,6 as claimed in claim 15,6-tetramethyl-3, the method for 5-heptadione metal complex, wherein said slaine is at least a slaine in halide, nitrate, sulfate and the phosphate that is selected from metal.
17. preparation 2,2,6 as claimed in claim 16,6-tetramethyl-3, the method for 5-heptadione metal complex, wherein said slaine is metal chloride and/or metal nitrate.
18. preparation 2,2,6 as claimed in claim 15,6-tetramethyl-3, the method for 5-heptadione metal complex, the metal in the wherein said slaine is at least a metal that is selected from transition metal and alkaline-earth metal.
19. preparation 2,2,6 as claimed in claim 18,6-tetramethyl-3, the method for 5-heptadione metal complex, wherein said metal is at least a metal that is selected from alkaline-earth metal, rare earth metal, Ti, Zr, Hf and Cu.
20. preparation 2,2,6 as claimed in claim 15,6-tetramethyl-3, the method for 5-heptadione metal complex, wherein hydrophilic solvent is 2,2,6,6-tetramethyl-3, in the reaction of 5-heptadione and slaine as solvent.
21. preparation 2,2,6 as claimed in claim 20,6-tetramethyl-3, the method for 5-heptadione metal complex, wherein said hydrophilic solvent is the alcohol of 1-4 carbon atom.
22. preparation 2,2,6 as claimed in claim 21,6-tetramethyl-3, the method for 5-heptadione metal complex, wherein said alcohol is methyl alcohol.
23. preparation 2,2,6 as claimed in claim 15,6-tetramethyl-3, the method for 5-heptadione metal complex wherein after reaction is finished, adds entry so that 2,2,6,6-tetramethyl-3,5-heptadione metal complex precipitation is separated this metal complex subsequently.
24. preparation 2,2,6 as claimed in claim 15,6-tetramethyl-3, the method for 5-heptadione metal complex, wherein said 2,2,6,6-tetramethyl-3,5-heptadione metal complex are a kind of wherein 2-4 individual 2,2,6,6-tetramethyl-3, the metal complex of 5-heptadione molecule and 1 metallic atom coordination.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002002727 | 2002-01-09 | ||
| JP2727/2002 | 2002-01-09 | ||
| JP2002151760A JP4114400B2 (en) | 2002-01-09 | 2002-05-27 | β-diketone compound, metal complex thereof, and method for producing metal compound |
| JP151760/2002 | 2002-05-27 | ||
| PCT/JP2002/013238 WO2003059858A2 (en) | 2002-01-09 | 2002-12-18 | Process for preparing -diketone compound and process for preparing metal complex thereof |
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| Publication Number | Publication Date |
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| CN1636422A true CN1636422A (en) | 2005-07-06 |
| CN1636422B CN1636422B (en) | 2010-10-13 |
Family
ID=29217819
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|---|---|---|---|
| CN02826972.1A Expired - Fee Related CN1636422B (en) | 2002-01-09 | 2002-12-18 | Process for preparing beta-diketone compound and process for preparing metal complex thereof |
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| Country | Link |
|---|---|
| JP (1) | JP4114400B2 (en) |
| CN (1) | CN1636422B (en) |
| TW (1) | TWI269790B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104768911A (en) * | 2012-10-29 | 2015-07-08 | 田中贵金属工业株式会社 | Method for extracting asymmetric [beta]-diketone compound from [beta]-diketone compound |
| CN106397164A (en) * | 2016-08-31 | 2017-02-15 | 安徽省鸿鑫生物科技有限公司 | Synthesis method of 2,2,6,6-tetramethyl-3,5-heptadione |
| CN110304998A (en) * | 2019-08-05 | 2019-10-08 | 盐城工学院 | A kind of purification process of DPM dpm,dipivalomethane |
| CN115260018A (en) * | 2022-10-08 | 2022-11-01 | 苏州源展材料科技有限公司 | Preparation method of tris (2, 6-tetramethyl-3, 5-pimelic acid) bismuth |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4744815B2 (en) * | 2003-06-10 | 2011-08-10 | 昭和電工株式会社 | β-diketone compound, metal complex thereof, and method for producing metal compound |
| JP2006282611A (en) * | 2005-04-01 | 2006-10-19 | Ube Ind Ltd | Method of manufacturing beta-diketone compound having silyl ether group |
| JP4710698B2 (en) * | 2006-04-10 | 2011-06-29 | 宇部興産株式会社 | Process for producing β-diketone compound having silyl ether group |
| KR100741673B1 (en) | 2006-08-04 | 2007-07-25 | 테크노세미켐 주식회사 | Man-ufacturing method of 1-methoxy-2,2,6,6-tetramethyl-heptane-3,5-dione |
| JP6241203B2 (en) * | 2013-10-31 | 2017-12-06 | コニカミノルタ株式会社 | Process for producing bis β-diketone derivative and pyrazole derivative |
-
2002
- 2002-05-27 JP JP2002151760A patent/JP4114400B2/en not_active Expired - Fee Related
- 2002-11-13 TW TW91133277A patent/TWI269790B/en not_active IP Right Cessation
- 2002-12-18 CN CN02826972.1A patent/CN1636422B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104768911A (en) * | 2012-10-29 | 2015-07-08 | 田中贵金属工业株式会社 | Method for extracting asymmetric [beta]-diketone compound from [beta]-diketone compound |
| CN104768911B (en) * | 2012-10-29 | 2016-07-20 | 田中贵金属工业株式会社 | The method extracting asymmetric beta-diketone compound from beta-diketone compound |
| CN106397164A (en) * | 2016-08-31 | 2017-02-15 | 安徽省鸿鑫生物科技有限公司 | Synthesis method of 2,2,6,6-tetramethyl-3,5-heptadione |
| CN110304998A (en) * | 2019-08-05 | 2019-10-08 | 盐城工学院 | A kind of purification process of DPM dpm,dipivalomethane |
| CN115260018A (en) * | 2022-10-08 | 2022-11-01 | 苏州源展材料科技有限公司 | Preparation method of tris (2, 6-tetramethyl-3, 5-pimelic acid) bismuth |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI269790B (en) | 2007-01-01 |
| JP2003267908A (en) | 2003-09-25 |
| JP4114400B2 (en) | 2008-07-09 |
| CN1636422B (en) | 2010-10-13 |
| TW200301757A (en) | 2003-07-16 |
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