CN102020542A - Method for producing 2-adamantanone - Google Patents
Method for producing 2-adamantanone Download PDFInfo
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- CN102020542A CN102020542A CN2010106056093A CN201010605609A CN102020542A CN 102020542 A CN102020542 A CN 102020542A CN 2010106056093 A CN2010106056093 A CN 2010106056093A CN 201010605609 A CN201010605609 A CN 201010605609A CN 102020542 A CN102020542 A CN 102020542A
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Abstract
The invention discloses a method for producing 2-adamantanone. In the production method, based on a principle that concentrated sulfuric acid is used to oxidize adamantane so as to produce the 2-adamantanone, oxidizing reaction generates between the phase interfaces of a nonpolar organic phase and an inorganic phase which are mutually non-homogenous; and a nonpolar organic solvent is used to extract esterified products from the inorganic phase so as to carry out the next hydrolysis process. In the method for producing the 2-adamantanone, sulfuric acid phase containing adamantane sulfate is in no need of directly carrying out hydrolysis, thus waste dilute sulphuric acid liquids are not generated in the production process. The sulfuric acid which is subject to reaction and extraction is recycled after impurity removal and thickening, thus effectively solving the problem that a large amount of the waste dilute sulphuric acid liquids generated in producing the adamantanone by using the traditional sulfuric acid oxidation method are difficult to process and reducing the sulfuric acid consumption; in addition, the production technology is more coincident with the environmental requirements, and the product yield can reach over 65%.
Description
Technical field
The present invention relates to a kind of alkane ketone, particularly the production method of 2-diamantane ketone.
Background technology
Diamantane is the symmetric cage compound of a kind of height, and it has the chemical structure similar to adamantine structural unit.The chemistry of diamantane has obtained development rapidly in nearly decades, adamantane derivative is also increasingly extensive in the application of field of medicaments and functional high polymer material field etc., wherein, 2-Buddha's warrior attendant ketone replaces the important initial substance of adamantane derivative as preparation 2-, be the important intermediate of producing multiple medicine, its market demand is also increasing.
At present, 2-Buddha's warrior attendant ketone mainly is to be that starting raw material is prepared with diamantane or 1-adamantanol, and adopts vitriol oil direct oxidation method at present from the industrialized preparing process of diamantane or adamantanol preparation 2-Buddha's warrior attendant ketone.This sulfuric acid direct oxidation method technology is with behind diamantane or the adamantanol usefulness vitriol oil heated oxide, will be hydrolyzed in the entire reaction material input low-temperature cold water, and then by wet distillation 2-diamantane ketone wherein be steamed.This processing method need expend a large amount of sulfuric acid, and 1 ton of 2-diamantane of every production ketone also can produce 50～60 tons of useless dilute sulfuric acid solutions, and the acid concentration of these useless dilute sulfuric acid solutions is lower, contains impurity such as more organic carbide, is difficult to handle and utilize.
Summary of the invention
The object of the invention is to overcome described defective, provides a kind of and prepares the method for 2-diamantane ketone as starting raw material by sulfuric acid oxidation by diamantane, does not produce useless dilute sulfuric acid solution in production process, reduces sulfuric acid consumption.
Technical purpose of the present invention is achieved by the following scheme: the production method of 2-diamantane ketone comprises the steps:
(1) interface oxidation reaction: getting the acid solution that contains the vitriol oil is the first sulfuric acid phase, diamantane is dissolved in the formation first organic solvent phase in back in the organic solvent, with first sulfuric acid second sulfuric acid phase that the interface oxidation reaction obtains second organic solvent phase and contains the diamantane sulfuric ester takes place mutually again, then standing demix isolate above-mentioned second organic solvent mutually with second sulfuric acid mutually, described organic solvent is not react with sulfuric acid and the nonpolar or weakly polar organic solvent little with the mutual solvability of vitriolic;
(2) extraction sulfuric acid phase: polar organic solvent is mixed stirring mutually with above-mentioned second sulfuric acid that obtains that separates, with the diamantane sulfuric ester of second sulfuric acid in mutually be extracted into organic solution mutually in, form the 3rd organic solution mutually and the 3rd sulfuric acid mutually, separate the 3rd organic solution phase and the 3rd sulfuric acid then mutually;
(3) interface hydrolysis: above-mentioned the 3rd organic solution is stirred with alkaline aqueous solution and heat, the having ideals, morality, culture, and discipline machine solution that obtains containing diamantane ketone mutually and contain the water of vitriol;
(4) condensing crystal: clean above-mentioned having ideals, morality, culture, and discipline machine solution phase, remove moisture then, distillation concentrates, crystallisation by cooling, and fractional crystallization is also dry, promptly obtains the coarse crystallization product of 2-diamantane ketone.
Preferably, the organic solvent described in the step (1) is one or more in sherwood oil, heptane, octane, trimethylpentane, methyl hexane, pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane, ethylcyclohexane, the naphthane;
Preferably, described first organic solvent is 1/9～9/1 with first sulfuric acid volume ratio mutually;
Preferably, described first sulfuric acid also comprises the mixing acid of being made up of halogenated carboxylic acid and halogenosulfonic acid mutually;
Preferably, first sulfuric acid mutually in, the total mass mark of mixing acid is 0～10%, the massfraction of the vitriol oil is 90～100%;
Preferably, the oxidizing reaction described in the step (1) is carried out under heated and stirred, and its temperature of reaction is 30 ℃～120 ℃, and reaction total time is 16 hours～27 hours;
Preferably, second sulfuric acid in the described step (2) is repeatedly extracted with polar organic solvent, until the residual diamantane sulfuric ester quality of gained the 3rd sulfuric acid in mutually be lower than the initial diamantane sulfuric ester total mass of second sulfuric acid in mutually 5% till, then the organic solution of extracting and separating is incorporated in the 3rd organic solution mutually in;
Preferably, described polar organic solvent is methylene dichloride, trichloromethane, 1, one or more in 1-ethylene dichloride, propylene dichloride, chlorohexane, 1-chloro-2-ethyl hexane, N-PROPYLE BROMIDE, caproic acid, 2 Ethylbutanoic acid, the 2 ethyl hexanoic acid;
Preferably, in the step (2), during the single extraction, polar organic solvent is 2/8～8/2 with second sulfuric acid volume ratio mutually;
Preferably, temperature is 20 ℃～80 ℃ during the extraction of described step (2), and the extraction time is 0.5 hour～2 hours;
Preferably, the alkaline aqueous solution in the described step (3) is at least a in sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and the ammoniacal liquor;
Preferably, the quality percentage composition of described alkaline aqueous solution is 0.5%～10%;
Preferably, the 3rd organic solution described in the step (3) is 4/6～9/1 with the volume ratio of alkali aqueous solution;
Preferably, the temperature of described step (3) interface hydrolysis is 30 ℃～80 ℃;
Preferably, in the described concentration crystallization step, clean the 4th machine solution till the pH of washing water value reaches 6-8, remove the moisture content (mass percent)≤0.2% of having ideals, morality, culture, and discipline machine solution phase behind the moisture, the dewatering agent of deviating from moisture is at least a in anhydrous magnesium sulfate, anhydrous sodium sulphate, Calcium Chloride Powder Anhydrous, silica gel and the molecular sieve.
Beneficial effect of the present invention:
The present invention is set out by diamantane and prepares 2-diamantane ketone, its yield can reach more than 65%, the sulfuric acid that no longer will contain the diamantane sulfuric ester among the preparation technology carries out direct hydrolysis mutually, therefore production process can not produce useless dilute sulfuric acid solution, sulfuric acid behind the reaction, extraction is cyclically utilizing after removal of impurities and enrichment processing, solved the problem that produces a large amount of unmanageable useless dilute sulfuric acid solutions in traditional sulfuric acid oxidation legal system diamantane ketone production effectively, reduced sulfuric acid consumption, production technique is compliance with environmental protection requirements more.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in detail.
Technical program of the present invention lies in:
In the step (1), the interface oxidation reaction is that diamantane is dissolved in the formation first organic solvent phase in back in the organic solvent, with first sulfuric acid that contains the vitriol oil the second sulfuric acid phase that the interface oxidation reaction obtains second organic solvent phase and contains the diamantane sulfuric ester takes place mutually again, interface oxidation is reflected under the stirring heating condition and carries out, when reaction proceed to organic solvent mutually in diamantane content reduce to 10% when following of initial content, stop to stir and heating, standing demix isolate above-mentioned second organic solvent mutually with second sulfuric acid mutually, gained second sulfuric acid is proceeded next step reaction mutually, when the next batch products production second organic solvent is used as organic solvent mutually.
Described organic solvent is not react with sulfuric acid and the nonpolar or weakly polar organic solvent little with the mutual solvability of vitriolic, can be in sherwood oil, heptane, octane, trimethylpentane, methyl hexane, pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane, ethylcyclohexane, the naphthane etc. at least a, usually select for use a kind ofly, be convenient to reagent and reclaim;
Because of this nonpolar or weakly polar organic solvent is good to nonpolar diamantane solvability, poorly soluble to having than the sulfuric ester of the sulfuric acid of high polarity and diamantane, and under the temperature condition of surface reaction, do not react with sulfuric acid, under agitation condition, first organic solvent disperses mutually with first sulfuric acid, the diamantane of organic solvent in mutually contacts with sulfuric acid at two-phase interface and reacts, the diamantane sulfuric ester that reaction generates then dissolve in strong polar sulfuric acid mutually in, stirring velocity is big more, dispersity is big more mutually with first sulfuric acid for first organic solvent, two contact abundant more.
In the interface oxidation reaction, temperature of reaction is 30 ℃～120 ℃, and temperature of reaction will be lower than the boiling point of used organic solvent, to avoid solvent evaporates; Well-knownly be, prepare long reaction time in the technology of diamantane ketone in the diamantane oxidation, the diamantane oxidation is abundant more, but the reaction times is long, the also corresponding increase of by products such as polymeric ether, in present method, getting oxidizing reaction total time is 16 hours～27 hours, and in this reaction time range, the diamantane oxidation is comparatively abundant, the yield height, by product generates few.
In this step, first organic solvent can be 1/9～9/1 with first sulfuric acid volume ratio mutually, and is preferred 3/7～7/3, guarantee that two-phase is fully disperseed under, sulfuric acid is the diamantane of oxidation organic solvent in mutually fully, diamantane transformation efficiency height, efficiency of pcr product is good.
Based on technical scheme of the present invention, described first sulfuric acid can also comprise the mixing acid of being made up of halogenated carboxylic acid and halogenosulfonic acid mutually, the carboxylic acid that halogenated carboxylic acid can select a halogen or many halogen to replace, as Monochloro Acetic Acid, a bromoacetic acid, dichloro acetic acid, dibromoacetic acid, trichoroacetic acid(TCA), a chloropropionic acid, Tripon etc.; Halogenosulfonic acid can be fluosulfonic acid, chlorsulfonic acid; Halogenated carboxylic acid, halogenosulfonic acid mix with the vitriol oil, can reduce the generation of side reaction, and the total mass of mixing acid is 0～10% of the first sulfuric acid phase total mass, and vitriol oil quality is 90～100% the bests of the first sulfuric acid phase total mass.
Step (2) is that second sulfuric acid is extracted mutually, be polar organic solvent is mixed stirring mutually with gained second sulfuric acid, with the diamantane sulfuric ester of second sulfuric acid in mutually be extracted into organic solution mutually in, form the 3rd organic solution mutually and the 3rd sulfuric acid mutually, separate the 3rd organic solution phase and the 3rd sulfuric acid then mutually; Get the 3rd organic solution phase, the 3rd sulfuric acid can loop back recycling in the step (1) after removal of impurities and enrichment processing, also can be used as other purposes.
The selection standard of described polar organic solvent is: polarity is strong and less with water and vitriolic mutual solubility, and is good to polar diamantane sulfuric ester solvability, is convenient to the sulfuric ester of diamantane is extracted mutually from sulfuric acid; Polar organic solvent can be that chloroparaffin is (as methylene dichloride, trichloromethane, 1,1-ethylene dichloride, propylene dichloride, chlorohexane, 1-chloro-2-ethyl hexane, N-PROPYLE BROMIDE), caproic acid, 2 Ethylbutanoic acid, 2 ethyl hexanoic acid etc., usually select wherein a kind of for use, be convenient to reagent and reclaim, can realize purpose of the present invention but select for use the various polarity organic solvent to use with equally.
Polar organic solvent can be 2/8～8/2 with second sulfuric acid volume ratio mutually, and the best is 3/7～6/4.Under agitation condition, two-phase is fully disperseed contact, the diamantane sulfuric ester of second sulfuric acid in mutually by two-phase interface enter polar organic solvent mutually in, finally in two-phase, reach partition equilibrium.
Temperature is controlled at 20 ℃～80 ℃ during extraction, under this temperature condition polar organic solvent not can with sulfuric acid reaction, and guarantee that Buddha's warrior attendant vinic acid ester percentage extraction is better, extraction system is stable, preferred extraction temperature is 30 ℃～60 ℃; Cut down the consumption of energy when percentage extraction is high.
Certainly, extracting operation can carry out several, extract churning time at every turn and be to be advisable in 0.5 hour～2 hours, up to the diamantane sulfuric ester that sulfuric acid contains in mutually have be extracted out more than 95% till.
Step (3) is interface hydrolysis operation, be above-mentioned the 3rd organic solution mixed with alkaline aqueous solution and obtain hydrolysis reaction system, stir and the heating hydrolysis reaction system, treat 99%(massfraction during the 3rd organic solution is mutually) change into till the 2-diamantane ketone more than the above diamantane sulfuric ester, the having ideals, morality, culture, and discipline machine solution phase and the water that contains vitriol that must contain diamantane ketone, usually hydrolysis time is 2 hours～5 hours, gets having ideals, morality, culture, and discipline machine solution and carries out next step operation mutually.
The employed alkali of alkaline aqueous solution can be mineral alkali, and as sodium hydroxide, potassium hydroxide, yellow soda ash, ammoniacal liquor etc., buck concentration is got 0.5%～10%(massfraction), preferred 2%～5%(massfraction), make the hydrolysis degree of diamantane sulfuric ester higher.
The 3rd organic solution is 4/6～9/1 with the volume ratio of alkali aqueous solution, and is preferred 6/4～8/2, guarantees that the hydrolysis of Buddha's warrior attendant vinic acid ester is more abundant.
In this step, the temperature of hydrolysis reaction system can be 30 ℃～80 ℃, preferred 40 ℃～60 ℃.
Step (4) is that having ideals, morality, culture, and discipline machine solution is carried out condensing crystal mutually, comprises cleaning having ideals, morality, culture, and discipline machine solution phase, removes moisture then, and distillation concentrates, crystallisation by cooling, and fractional crystallization is also dry, gets the coarse crystallization product of 2-diamantane ketone.
Clean having ideals, morality, culture, and discipline machine solution phase time, can adopt clear water to stir and wash the mode that once arrives several, stir the clear water volume of washing is 1/10～1/2 of having ideals, morality, culture, and discipline machine solution phase volume amount at every turn, stir at every turn and wash 10 minutes～30 minutes, stir and make the material standing demix after washing, get organic phase and water liquid, get organic phase continuation cleaning next time, reach till 6～8 up to the water liquid pH of washing gained.
Organic phase after the washing is dewatered with dewatering agent, and moisture content is wherein reached below 0.2%.Dewatering agent can be anhydrous magnesium sulfate, anhydrous sodium sulphate, Calcium Chloride Powder Anhydrous, silica gel, molecular sieve etc.
Organic solution after the dehydration concentrates with normal pressure or underpressure distillation, distillates the solvent collection reuse.Organic solution crystallisation by cooling after concentrating goes out crystallization with centrifugation after filtration, again with the crystallization oven dry or dry, obtains the crude product of the target product 2-diamantane ketone of purity more than 95%.
As required, obtain the elaboration of the 2-diamantane ketone of purity more than 99% after the operator also can handle this crude product recrystallization, recrystallization is operated according to a conventional method and is got final product.
Embodiment 1
A, 500ml hexanaphthene and 110g diamantane are dropped in the 1000ml volume glass reaction still, be stirred and heated to 45 ℃, make the diamantane dissolving form the first organic solvent phase, the diamantane mass concentration of first organic solvent in mutually is 22%.
B, get the sulfuric acid of 250ml 98% mass concentration as the first sulfuric acid phase, under agitation condition, will slowly add in the reactor, add strong mixing and make first organic solvent mutually and first sulfuric acid thorough mixing mutually, first temperature control reacted 5 hours at 44-46 ℃, was warmed up to 59-62 ℃ of reaction again and reached 21 hours; The diamantane concentration that detects wherein of organic phase from reaction system sampling has reduced to 1.7% then, stops to stir, reduce below the temperature of reaction system to 40 ℃, standing demix, second organic solvent mutually with second sulfuric acid that contains the diamantane sulfuric ester mutually.
C, get second sulfuric acid and change over to mutually in another 1000ml volumetrical glass reaction still, add the 300ml propylene dichloride, stir extraction 40 minutes down at 30 ℃～33 ℃, behind the standing demix, take off a layer sulfuric acid phase, again with propylene dichloride by this step aforementioned operation re-extract five times, merge each time extraction liquid, the 3rd organic solution phase and the 3rd sulfuric acid mutually.
D, the 3rd organic solution is dropped in the 3000ml volumetrical glass reaction still mutually, the aqueous sodium hydroxide solution that adds 600ml 1% massfraction, at 40 ℃～45 ℃ following stirring reaction 3h, standing demix must contain the having ideals, morality, culture, and discipline machine solution phase of diamantane ketone and the water that vitriol is contained in lower floor in the upper strata then.
E, having ideals, morality, culture, and discipline machine solution stirred with proper amount of clear water wash repeatedly, stir at every turn and wash 10 minutes, stir the clear water volume of washing is 1/10 of having ideals, morality, culture, and discipline machine solution phase volume amount at every turn, stir and make the material standing demix after washing, get organic phase and water liquid, get organic phase continuation cleaning next time, water liquid pH up to the washing gained reaches 7.5, dewater with anhydrous magnesium sulfate then, making the middle mutually moisture content of having ideals, morality, culture, and discipline machine solution is the 1.9%(massfraction), air distillation has small amount of crystalline to separate out to concentrating liquid level again, concentrated solution cooling placement is spent the night, and centrifugation crystallization again obtains crude product crystallization 76.9g, use the GC(gas-chromatography) method detects wherein that 2-diamantane ketone content is 95.4%, and calculated yield is 66.7%.
The contriver obtains the 2-diamantane ketone crystallization of content 99% after this crude product recrystallization is handled.
Embodiment 2
A, 510ml methylcyclopentane and 125g diamantane are dropped in the 1000ml volume glass reaction still, be stirred and heated to 50 ℃, make the diamantane dissolving form the first organic solvent phase, the diamantane mass concentration of first organic solvent in mutually is 26%.
B, get the sulfuric acid of 300ml 98% mass concentration as the first sulfuric acid phase, under agitation condition, will slowly add in the reactor, add strong mixing and make first organic solvent mutually and first sulfuric acid thorough mixing mutually, first temperature control reacted 8 hours at 39-42 ℃, was warmed up to 55 ℃ of insulation reaction to 26 hour again; The diamantane concentration that detects wherein of organic phase from reaction system sampling has reduced to 2.2% then, stops to stir, reduce below the temperature of reaction system to 40 ℃, standing demix, second organic solvent mutually with second sulfuric acid that contains the diamantane sulfuric ester mutually.
C, get second sulfuric acid and change over to mutually in another 1000ml volumetrical glass reaction still, add the 300ml propylene dichloride, stir extraction 60 minutes down at 38 ℃～40 ℃, behind the standing demix, take off a layer sulfuric acid phase, again with propylene dichloride by this step aforementioned operation re-extract five times, merge each time extraction liquid, the 3rd organic solution phase and the 3rd sulfuric acid mutually.
D, the 3rd organic solution is dropped in the 3000ml volumetrical glass reaction still mutually, the potassium hydroxide aqueous solution that adds 0.5% massfraction of 4/6 times of the 3rd organic solution phase volume, at 30 ℃～33 ℃ following stirring reaction 2h, standing demix must contain the having ideals, morality, culture, and discipline machine solution phase of diamantane ketone and the water that vitriol is contained in lower floor in the upper strata then.
E, having ideals, morality, culture, and discipline machine solution stirred with proper amount of clear water wash repeatedly, stir at every turn and wash 20 minutes, stir the clear water volume of washing is 1/5 of having ideals, morality, culture, and discipline machine solution phase volume amount at every turn, stir and make the material standing demix after washing, get organic phase and water liquid, get organic phase continuation cleaning next time, water liquid pH up to the washing gained reaches 8, and then with the Calcium Chloride Powder Anhydrous dehydration, making the middle mutually moisture content of having ideals, morality, culture, and discipline machine solution is the 1.6%(massfraction), underpressure distillation has small amount of crystalline to separate out to concentrating liquid level again, concentrated solution cooling placement is spent the night, and centrifugation crystallization again obtains crude product crystallization 84.8g, detect wherein with the GC method that 2-diamantane ketone content is 96.2%, calculated yield is 65.3%.
The contriver obtains the 2-diamantane ketone crystallization of content 99% after this crude product recrystallization is handled.
Embodiment 3
Repeat the operation of embodiment 1, difference is:
Among the step a, organic solvent is a sherwood oil, and the stirring heating temperature is 50 ℃.
The sulfuric acid of getting 98% mass concentration among the step b is as the first sulfuric acid phase, first organic solvent is 1/9 with first sulfuric acid volume ratio mutually, first organic solvent mutually and first sulfuric acid mutually behind the thorough mixing first temperature control reacted 7 hours at 52-54 ℃, be warmed up to 65 ℃ of insulation reaction to 27 hour again; The sampling of organic phase from reaction system detects wherein diamantane concentration reduced to 2.0% after, stop to stir cooling and standing demix again.
Among the step c, the polar organic solvent propylene dichloride adopts 1-chloro-2-ethyl hexane to substitute, extraction temperature is 20-22 ℃, the single extraction time is 30min, polar organic solvent is 2/8 with second sulfuric acid volume ratio mutually during the single extraction, re-extract five times, the organic solution liquid that merges extraction gets the 3rd organic solution phase, and adopting the GC method to record the middle mutually diamantane sulfuric ester massfraction of last extraction gained the 3rd sulfuric acid is 3.5% of diamantane sulfuric ester total amount.
In the steps d, alkali aqueous solution is the yellow soda ash of 2% massfraction, and the 3rd organic solution is 3:2 with the volume ratio of alkali aqueous solution, and hydrolysising reacting temperature is 41 ℃～42 ℃, and hydrolysis time is 2.5h.
Among the step e, stir with proper amount of clear water and to wash having ideals, morality, culture, and discipline machine solution phase time, stir at every turn and wash 10 minutes, single stir when washing clear water and having ideals, morality, culture, and discipline machine solution mutually the body ratio be 1/10, stir to wash repeatedly and reach 6 up to the water liquid pH of washing gained, adopt molecular sieve dehydration, making the middle mutually moisture content of having ideals, morality, culture, and discipline machine solution is the 1.8%(massfraction).
Final crude product crystallization 85.5g detects wherein with the GC method that 2-diamantane ketone content is 96.5%, and calculated yield is 65.4%.
Embodiment 4
Repeat the operation of embodiment 1, difference is:
Among the step a, organic solvent be heptane and naphthane by 1:1 volume ratio blended mixture, the stirring heating temperature is 50 ℃.
The sulfuric acid of getting 98% mass concentration among the step b mixes as first sulfuric acid mutually with the mass ratio of Monochloro Acetic Acid by 9:1, first organic solvent is 3:7 with first sulfuric acid volume ratio mutually, first organic solvent mutually with first sulfuric acid mutually behind the thorough mixing first temperature control at 60-62 ℃ to 16 hours; The sampling of organic phase from reaction system detects wherein diamantane concentration reduced to 2.0% after, stop to stir cooling and standing demix again.
Among the step c, polar organic solvent is that methylene dichloride mixes gained with caproic acid by the 2:1 volume ratio, extraction temperature is 58-60 ℃, the single extraction time is 30min, polar organic solvent is 3:7 with second sulfuric acid volume ratio mutually during the single extraction, re-extract five times, the organic solution liquid that merges extraction gets the 3rd organic solution phase, and adopting the GC method to record the middle mutually diamantane sulfuric ester massfraction of last extraction gained the 3rd sulfuric acid is 4.1% of diamantane sulfuric ester total amount.
In the steps d, alkali aqueous solution is the mixture of sodium hydroxide solution and ammoniacal liquor, in the alkali aqueous solution, sodium hydroxide and ammonium hydroxide total mass mark are the yellow soda ash of 5% massfraction, the 3rd organic solution phase with the alkali aqueous solution volume ratio be 2:1, hydrolysising reacting temperature is 58 ℃～59 ℃, and hydrolysis time is 4h.
Among the step e, stir with proper amount of clear water and to wash having ideals, morality, culture, and discipline machine solution phase time, stir at every turn and wash 30 minutes, single stir when washing clear water and having ideals, morality, culture, and discipline machine solution mutually the body ratio be 1/5, stir to wash repeatedly and reach 7 up to the water liquid pH of washing gained, with the silica gel dehydration, making the middle mutually moisture content of having ideals, morality, culture, and discipline machine solution is the 2%(massfraction).
Final crude product crystallization 84.2g detects wherein with the GC method that 2-diamantane ketone content is 95.7%, and calculated yield is 64.9%.
Embodiment 5
Repeat the operation of embodiment 1, difference is:
Among the step a, organic solvent be trimethylpentane, sherwood oil, ethylcyclohexane by 1:1:1 volume ratio blended mixture, the stirring heating temperature is 75 ℃.
Sulfuric acid, the dibromoacetic acid of getting 98% mass concentration among the step b mix as first sulfuric acid mutually with the mass ratio of fluosulfonic acid by 9:0.5:0.5, first organic solvent is 7:3 with first sulfuric acid volume ratio mutually, first organic solvent mutually with first sulfuric acid mutually behind the thorough mixing first temperature control in 74-75 ℃ reaction to 20 hour; The sampling of organic phase from reaction system detects wherein diamantane concentration reduced to 1.8% after, stop to stir cooling and standing demix again.
Among the step c, polar organic solvent is N-PROPYLE BROMIDE, 2 Ethylbutanoic acid and 1, the 1-ethylene dichloride is pressed the volume ratio of 1:1:1 and is mixed gained, extraction temperature is 77-78 ℃, the single extraction time is 110min, polar organic solvent is 3:2 with second sulfuric acid volume ratio mutually during the single extraction, re-extract three times, the organic solution liquid that merges extraction gets the 3rd organic solution phase, and adopting the GC method to record the middle mutually diamantane sulfuric ester massfraction of last extraction gained the 3rd sulfuric acid is 4.9% of diamantane sulfuric ester total amount.
In the steps d, alkali aqueous solution is the sodium hydroxide solution of 4% massfraction, the 3rd organic solution and alkali aqueous solution and volume ratio be 4:1, hydrolysising reacting temperature is 77 ℃～78 ℃, hydrolysis time is 5h.
Among the step e, stir with proper amount of clear water and to wash having ideals, morality, culture, and discipline machine solution phase time, stir at every turn and wash 10 minutes, single stir when washing clear water and having ideals, morality, culture, and discipline machine solution mutually the body ratio be 1/2, stir to wash repeatedly and reach 7 up to the water liquid pH of washing gained, molecular sieve is adopted in dehydration.
Final crude product crystallization 84.2g detects wherein with the GC method that 2-diamantane ketone content is 95.5%, and calculated yield is 64.4%.
Embodiment 6
Repeat the operation of embodiment 1, difference is:
Among the step a, organic solvent is a pentamethylene, and the stirring heating temperature is 30 ℃.
The sulfuric acid of getting 98% mass concentration among the step b is as the first sulfuric acid phase, first organic solvent is 9:1 with first sulfuric acid volume ratio mutually, first organic solvent mutually and first sulfuric acid mutually behind the thorough mixing first temperature control reacted 7 hours at 100 ℃, be warmed up to 120 ℃ of insulation reaction to 25 hour again; The sampling of organic phase from reaction system detects wherein diamantane concentration reduced to 1.8% after, stop to stir cooling and standing demix again.
Among the step c, polar organic solvent is a propylene dichloride, extraction temperature is 45-46 ℃, the single extraction time is 30min, polar organic solvent is 4:1 with second sulfuric acid volume ratio mutually during the single extraction, re-extract four times, the organic solution liquid that merges extraction gets the 3rd organic solution phase, and adopting the GC method to record the middle mutually diamantane sulfuric ester massfraction of last extraction gained the 3rd sulfuric acid is 2.8% of diamantane sulfuric ester total amount.
In the steps d, alkali aqueous solution is the ammoniacal liquor of 10% massfraction, and the 3rd organic solution is 9:1 with the volume ratio of alkali aqueous solution, and hydrolysising reacting temperature is 51 ℃～52 ℃, and hydrolysis time is 5h.
Among the step e, stir with proper amount of clear water and to wash having ideals, morality, culture, and discipline machine solution phase time, stir at every turn and wash 10 minutes, single stir when washing clear water and having ideals, morality, culture, and discipline machine solution mutually the body ratio be 1/3, stir to wash repeatedly and reach 7.5 up to the water liquid pH of washing gained, adopt anhydrous sodium sulfate dehydration, making the middle mutually moisture content of having ideals, morality, culture, and discipline machine solution is the 1.7%(massfraction).
Final crude product crystallization 84.5g detects wherein with the GC method that 2-diamantane ketone content is 96.2%, and calculated yield is 65.1%.
Claims (15)
1. the production method of a 2-diamantane ketone is characterized in that comprising the steps:
(1) interface oxidation reaction: getting the acid solution that contains the vitriol oil is the first sulfuric acid phase, diamantane is dissolved in the formation first organic solvent phase in back in the organic solvent, with first sulfuric acid second sulfuric acid phase that the interface oxidation reaction obtains second organic solvent phase and contains the diamantane sulfuric ester takes place mutually again, then standing demix isolate above-mentioned second organic solvent mutually with second sulfuric acid mutually, described organic solvent is not react with sulfuric acid and the nonpolar or weakly polar organic solvent little with the mutual solvability of vitriolic;
(2) extraction sulfuric acid phase: polar organic solvent is mixed stirring mutually with above-mentioned second sulfuric acid that obtains that separates, with the diamantane sulfuric ester of second sulfuric acid in mutually be extracted into organic solution mutually in, form the 3rd organic solution mutually and the 3rd sulfuric acid mutually, separate the 3rd organic solution phase and the 3rd sulfuric acid then mutually;
(3) interface hydrolysis: above-mentioned the 3rd organic solution is stirred with alkaline aqueous solution and heat, the having ideals, morality, culture, and discipline machine solution that obtains containing diamantane ketone mutually and contain the water of vitriol;
(4) condensing crystal: clean above-mentioned having ideals, morality, culture, and discipline machine solution phase, remove moisture then, distillation concentrates, crystallisation by cooling, and fractional crystallization is also dry, promptly obtains the coarse crystallization product of 2-diamantane ketone.
2. the production method of 2-diamantane ketone according to claim 1 is characterized in that the organic solvent described in the step (1) is one or more in sherwood oil, heptane, octane, trimethylpentane, methyl hexane, pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane, ethylcyclohexane, the naphthane.
3. the production method of 2-diamantane ketone according to claim 1 is characterized in that described first organic solvent is 1/9～9/1 with first sulfuric acid volume ratio mutually.
4. according to the production method of claim 1,3 or 4 described 2-diamantane ketone, it is characterized in that described first sulfuric acid also comprises the mixing acid of being made up of halogenated carboxylic acid and halogenosulfonic acid mutually.
5. the production method of 2-diamantane ketone according to claim 5 is characterized in that first sulfuric acid mutually, and the total mass mark of mixing acid is 0～10%, and the massfraction of the vitriol oil is 90～100%.
6. the production method of 2-diamantane ketone according to claim 1 is characterized in that the oxidizing reaction described in the step (1) carries out under heated and stirred, its temperature of reaction is 30 ℃～120 ℃, and reaction total time is 16 hours～27 hours.
7. the production method of 2-diamantane ketone according to claim 1, it is characterized in that second sulfuric acid in the described step (2) is repeatedly extracted with polar organic solvent, until the residual diamantane sulfuric ester quality of gained the 3rd sulfuric acid in mutually be lower than the initial diamantane sulfuric ester total mass of second sulfuric acid in mutually 5% till, then the organic solution of extracting and separating is incorporated in the 3rd organic solution mutually in.
8. the production method of 2-diamantane ketone according to claim 1, it is characterized in that described polar organic solvent is methylene dichloride, trichloromethane, 1, one or more in 1-ethylene dichloride, propylene dichloride, chlorohexane, 1-chloro-2-ethyl hexane, N-PROPYLE BROMIDE, caproic acid, 2 Ethylbutanoic acid, the 2 ethyl hexanoic acid.
9. according to the production method of claim 1 or 8 described 2-diamantane ketone, it is characterized in that in the step (2) that during the single extraction, polar organic solvent is 2/8～8/2 with second sulfuric acid volume ratio mutually.
10. according to the production method of the described 2-diamantane of claim 1 ketone, temperature is 20 ℃～80 ℃ when it is characterized in that the extraction of described step (2), and the extraction time is 0.5 hour～2 hours.
11., it is characterized in that alkaline aqueous solution in the described step (3) is at least a in sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and the ammoniacal liquor according to the production method of the described 2-diamantane of claim 1 ketone.
12. according to the production method of claim 1 or 11 described 2-diamantane ketone, the quality percentage composition that it is characterized in that described alkaline aqueous solution is 0.5%～10%.
13., it is characterized in that the 3rd organic solution described in the step (3) and the volume ratio of alkali aqueous solution are 4/6～9/1 according to the production method of the described 2-diamantane of claim 1 ketone.
14. according to the production method of the described 2-diamantane of claim 1 ketone, the temperature that it is characterized in that described step (3) interface hydrolysis is 30 ℃～80 ℃.
15. production method according to the described 2-diamantane of claim 1 ketone, it is characterized in that in the described concentration crystallization step, clean the 4th machine solution till the pH of washing water value reaches 6-8, remove the moisture content (mass percent)≤0.2% of having ideals, morality, culture, and discipline machine solution phase behind the moisture, the dewatering agent of deviating from moisture is at least a in anhydrous magnesium sulfate, anhydrous sodium sulphate, Calcium Chloride Powder Anhydrous, silica gel and the molecular sieve.
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| CN111233644A (en) * | 2020-03-10 | 2020-06-05 | 四川众邦制药有限公司 | Synthesis and extraction method of adamantanone |
| CN112159309A (en) * | 2020-10-19 | 2021-01-01 | 浙江荣耀生物科技股份有限公司 | Purification method of 2-ethyl-2-adamantanol |
| CN112592262A (en) * | 2020-12-14 | 2021-04-02 | 天津民祥药业有限公司 | Preparation method of adamantanone |
| CN114507124A (en) * | 2022-01-28 | 2022-05-17 | 浙江荣耀生物科技股份有限公司 | Separation method of 2-adamantanone |
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| CN1980877A (en) * | 2004-07-07 | 2007-06-13 | 出光兴产株式会社 | Method for producing 2-adamantanone |
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| CN1980877A (en) * | 2004-07-07 | 2007-06-13 | 出光兴产株式会社 | Method for producing 2-adamantanone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111233644A (en) * | 2020-03-10 | 2020-06-05 | 四川众邦制药有限公司 | Synthesis and extraction method of adamantanone |
| CN111233644B (en) * | 2020-03-10 | 2023-02-17 | 四川众邦新材料股份有限公司 | Synthesis and extraction method of adamantanone |
| CN112159309A (en) * | 2020-10-19 | 2021-01-01 | 浙江荣耀生物科技股份有限公司 | Purification method of 2-ethyl-2-adamantanol |
| CN112159309B (en) * | 2020-10-19 | 2023-05-02 | 浙江荣耀生物科技股份有限公司 | Purification method of 2-ethyl-2-adamantanol |
| CN112592262A (en) * | 2020-12-14 | 2021-04-02 | 天津民祥药业有限公司 | Preparation method of adamantanone |
| CN114507124A (en) * | 2022-01-28 | 2022-05-17 | 浙江荣耀生物科技股份有限公司 | Separation method of 2-adamantanone |
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