CN105985218A

CN105985218A - Method and application of reaction of carboxylate or carboxylic acid and water for synthesizing acyloin and alcohol (ketone) organics

Info

Publication number: CN105985218A
Application number: CN201510053530.7A
Authority: CN
Inventors: 李坚
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-01-27
Filing date: 2015-01-27
Publication date: 2016-10-05

Abstract

The invention relates to a method for synthesizing acyloin and alcohol (ketone) organics through a chemical catalytic reaction approach with carboxylate or carboxylic acid and water as raw materials, and an application of carboxylate or carboxylic acid as a raw material for carrying out a reaction with water to synthesize the acyloin and alcohol (ketone) organics. For conveniently separate the acyloin and alcohol (ketone) organics from an aqueous alkali solution, the invention also relates to a method for further converting the hydroxyl group in the acyloin and alcohol (ketone) organics into carbonyl group which is to convert the acyloin and alcohol (ketone) organics into ketone and aldehyde organics through a chemical reaction under a high-temperature liquid water condition. The invention also relates to an application of the carboxylate or carboxylic acid as a raw material for carrying out a reaction with water to synthesize the ketone and aldehyde organics.

Description

Carboxylate or carboxylic acid are synthesized acyloin and alcohol (ketone) class with water Organic method and purposes

One, technical field

The present invention relates to a kind of with carboxylate or carboxylic acid and water as raw material, urged by chemistry The approach changing reaction synthesizes acyloin and the method for alcohol (ketone) type organic and carboxylate thereof Or carboxylic acid is synthesized the former of acyloin class and alcohol (ketone) type organic as a kind of and water The purposes of material.And, in order to be conducive to this acyloin and alcohol type organic from aqueous alkali Solution is separated, the invention still further relates to a kind of by high temperature liquid water under the conditions of The approach of chemical reaction, turns the hydroxyl in this acyloin and alcohol type organic further Turn to carbonyl, be i.e. converted into ketone and the organic method of aldehydes and carboxylate thereof or carboxylic acid Ketone and the purposes of aldehydes organic raw material are synthesized with water as a kind of.

Two, background technology

Acyloin and alcohol are synthesized as a kind of with water about selecting carboxylate or carboxylic acid The method of (ketone) type organic and carboxylate thereof or carboxylic acid react with water as a kind of The purposes of raw material, up to now, yet there are no the report of document and data.And having , there is a classical acyloin condensation reaction in chemical machine field, refers to 2 molecules Carboxylate under the effect of metallic sodium simple substance, anhydrous organic at aprotic such as ether In solvent, by condensation or self-coupling reaction, it is converted into corresponding acyloin type organic, Refer to " research that supercritical ultrasonics technology synthesizes the third acyloin ", " 4-hydroxyl-3-hexanone synthesis side The improvement of method ", the paper such as " synthesis of n Butyroin for Using as Flavor ".Contracted by classical keto-alcohol Close reaction, acetoin can be synthesized for raw material, with propanoic acid with ethyl acetate and metallic sodium Ethyl ester and metallic sodium are that raw material can synthesize the third acyloin, with ethyl n-butyrate. and metallic sodium are Raw material can synthesize butyroin.But owing to the method needs to use substantial amounts of metallic sodium Simple substance is raw material, and cost is high, dangerous big, therefore the organic synthesis of this classics Method is unsuitable for the commercial production being applied to large-scale.The present invention is according to recent One new discovery (sees Application No. 201410853085.8, entitled " titanium dioxide Carbon or carbonate are synthesized the organic method such as sugar and sugar alcohol and purposes with water " Patent of invention) identical principle, by the metallic sodium in classical acyloin condensation reaction Reagent be improved to potassium hydroxide or the strong alkaline aqueous solution such as sodium hydroxide or calcium hydroxide with The catalyst of the metal simple-substance combinations such as zinc, most important of which is " KOH/ zinc " catalysis Agent, especially with aprotic such as the ether in the acyloin condensation reaction of water replacement classics Anhydrous organic solvent, make whole preparation process without the discharge of waste water,waste gas and industrial residue, Danger in preparation cost and preparation process is thus greatly reduced, very It is suitable for the application of large-scale industrial production, becomes a kind of typical without " three wastes " row The green chemical synthesis technique put.

Three, summary of the invention

An object of the present invention is to provide one carboxylate or carboxylic acid and water Be synthesized acyloin and the method for alcohol (ketone) type organic and carboxylate thereof or carboxylic acid As the purposes of a kind of raw material that acyloin and alcohol (ketone) type organic are synthesized with water, One of present disclosure is just to provide a kind of combination carboxylate or carboxylic acid and water in other words For raw material, prepare acyloin by the approach of chemosynthesis reaction and alcohol (ketone) class is organic The method of thing and to provide one combination carboxylate or carboxylic acid and water be that raw material is as synthesis Acyloin and the purposes of alcohol (ketone) type organic.Such as, it is provided that a kind of with potassium acetate or Acetic acid and water are raw material, by the catalytic reaction of KOH/ zincon, synthesize in aqueous phase The method of the mixture of acetoin and butanediol and diacetyl and potassium acetate or acetic acid thereof are made Purposes for the raw material reacted with water of synthesis acetoin and butanediol and diacetyl.

1, acyloin and alcohol (ketone) type organic are synthesized with carboxylate or carboxylic acid with water Method, including several steps of following sequence:

Select common clearance-type or flow reactor, put into the dense hydrogen-oxygen of amount of calculation Change potassium or concentrated sodium hydroxide or dense calcium hydroxide or the aqueous solution of dense Lithium hydrate or water hangs Supernatant liquid is in this reactor, or puts into the dense tetra-alkyl ammonium hydroxide aqueous solution of amount of calculation Or water slurry is in this reactor, put into again or the zinc of immobilized amount of calculation or ferrum or nickel Or stannum or lead or manganese or all metal simple-substances such as magnesium or copper or the non-gold such as activated carbon or sulfur Genus simple substance is in this reactor, under conditions of uncovered normal pressure, controls temperature 10-140 DEG C, it is slowly added into carboxylate or the carboxylic acid of amount of calculation, when keeping certain catalytic reaction Between, then lower the temperature, stand, filter, the mother solution liquid chromatograph leached and gas phase color Analysis of spectrum is tested, it is known that this mother solution is that the aqueous alkali of acyloin and alcohol (ketone) type organic mixes Compound, if add for carboxylate, then the metallic element in carboxylate is at aqueous solution In be quantitatively converted into corresponding metal hydroxides, such as, if add for second Acid potassium, the potassium element in potassium acetate is converted into equimolar hydroxide the most in aqueous Potassium.The filter cake filtered during Ben is the metal simple-substance powder added, can be with recycled； Then mother solution ethanol or the pyridine solvent of filtration are carried out liquid-liquid extraction, anti-in stirring Answer industrial alcohol and the pyridine adding amount of calculation in device, control temperature 40-90 DEG C, keep Certain stirring extraction time, is then passed through common standing, layering, the list of rectification Unit's process, reclaims ethanol or pyridine solvent, obtains dense acyloin and the alcohol separated with aqueous alkali The mix product of (ketone) type organic.

The two of the purpose of the present invention be to provide a kind of using acyloin and alcohol type organic as A kind of intermediate or raw material, be converted into ketone by the reaction under the conditions of high temperature liquid water The method of (aldehyde) type organic, it may also be said to be to provide a kind of with carboxylate or carboxylic acid It is raw material with water, by the approach of high temperature liquid water catalytic reaction by molecular structure Hydroxyl is converted into the method for oxo process ketone (aldehyde) type organic, and provides carboxylic acid Salt or carboxylic acid are synthesized the former of corresponding ketone (aldehyde) type organic as a kind of with water The purposes of material.Such as, it is provided that one potassium acetate or acetic acid are synthesized fourth two with water Ketone and the method for acetaldehyde and potassium acetate thereof or acetic acid are as a kind of raw material reacted with water Purposes.(note: so-called a kind of " the reacting with water " in this specification, refers to use carboxylic acid Salt or carboxylic acid are the chemical catalysis synthetic reaction that raw material is carried out with water).

2, ketone and aldehydes organic method are synthesized with carboxylate or carboxylic acid with water, including Several steps of following sequence:

Select common electric stirring high-pressure reactor, put into the dense hydroxide of amount of calculation Potassium or concentrated sodium hydroxide or dense calcium hydroxide or dense lithium hydroxide aqueous solution or aqueous suspension Liquid, puts into again the zinc powder of amount of calculation or technique of activated ferrous powder with or activity nikel powder or activity copper powder etc. All of metal simple-substance powder or the input non-metal simple-substance such as activated carbon or sulfur, startup is stirred Mix, put into again the carboxylate of amount of calculation or carboxylic acid in this reactor, control and regulate Temperature is 40-300 DEG C, and controlling and regulating pressure is 0-10MPa, and stirring reaction is certain Time after, lower the temperature, stand, filter, filter cake be add metal or nonmetal list Matter powder, filtrate is diones and a ketone and the organic alkaline aqueous mixture of aldehydes, uses This filtrate is extracted by ethanol or acetone, then carries out common layering, the mistake of rectification Journey, reclaims ethanol or acetone solvent, obtain simultaneously the dense diones that separates with aqueous alkali and The mix product of one ketone (aldehyde) type organic.

Four, specific embodiments

Embodiment 1

Selecting common electric stirring reactor, putting into mass content under room temperature is The potassium hydroxide of 40-70% or sodium hydroxide or Lithium hydrate or calcium hydroxide or 25% All alkaline aqueous solutions such as tetra-alkyl ammonium hydroxide or water slurry 100-150 gram In this reactor, put into again 40-70 gram of zinc powder or iron powder or nikel powder or glass putty or lead Powder or all metal simple-substances such as manganese powder or copper powder or the non-metal simple-substance such as activated carbon or sulfur In this reactor, start stirring, under conditions of uncovered normal pressure, slowly heat up, Control temperature 10-140 DEG C, be slowly added into anhydrous acetate or acetic acid simultaneously or add Enter propionate or propanoic acid or add butyrate or butanoic acid each 40-70 gram in this reactor In, stirring reaction 24-48 hour, then lower the temperature, stand, filter, filter cake is for adding Metal powder, reclaim Posterior circle apply mechanically, the mother solution leached is acyloin and alcohol (ketone) The alkaline aqueous mixture of type organic, is carried out this mother solution by liquid chromatograph and gas chromatogram Analyze test, learn therein being mainly composed of acetoin and butanediol and ethanol and fourth The Organic substances such as diketone；Or be mainly composed of the third acyloin and hexanediol and propanol and oneself two The Organic substances such as ketone；Or it is mainly composed of butyroin and ethohexadiol and butanol and acetyl caproyl Organic substance, the gross production rate that various organic mixture add up to respectively more than 82% with On.

Example 2

Selecting common electric stirring reactor, putting into mass content is the hydrogen of 40-70% Potassium oxide or sodium hydroxide or Lithium hydrate or the aqueous solution of calcium hydroxide or aqueous suspension Liquid, or put into all alkaline aqueous solutions such as tetra-alkyl ammonium hydroxide aqueous solution of 25% Or water slurry is in this reactor, put into again zinc powder or technique of activated ferrous powder with or activity nikel powder Or activity copper powder 40-60 gram is in this reactor, starts stirring, at uncovered normal pressure Under the conditions of, control temperature 10-140 DEG C, be slowly added into benzoate or benzoic acid 30-50 Gram, or it is slowly added into furoate or furancarboxylic acid 30-50 gram, stirring reaction 24-48 hour, Then lowering the temperature, stand, filter, the mother solution leached is acyloin and alcohol (ketone) class has The alkaline aqueous mixture of machine thing, is analyzed test by liquid chromatograph and gas chromatogram, Know that primary product is benzoin and hydrobenzoin and benzyl alcohol and diphenylthanedione Deng Organic substance；Or primary product is furoin and difurfuryl ethylene glycol and furfuryl alcohol and two The Organic substances such as furfuryl group second diketone, the gross production rate that various organic mixture add up to respectively More than more than 87%.

Embodiment 3

Choose the filtrated stock 50 grams of above-described embodiment 1 or embodiment 2, put into general In logical electric stirring reactor, put into industrial alcohol or industry pyridine 100-200 simultaneously Gram in this reactor, start stirring, control temperature 40-90 DEG C, stirring extraction 2-4 Hour, then lower the temperature, stand, be layered, lower floor is saturated aqueous alkali, follows after recovery Ring set use, collects ethanol or the pyridine liquid layer on upper strata, carries out rectification with dephlegmator, steam Going out and reclaim ethanol or pyridine, distillation substrate is the dense acyloin and alcohol separated with aqueous alkali The organic mixture of (ketone) class, composition and above-described embodiment 1 in this mixture Identical with the product of embodiment 2, extracting organic total recovery from aqueous alkali is 77% Above.

Embodiment 4

Select common filler tower reactor, by metal simple-substance zinc or ferrum or copper or nickel Or their alloy preparation becomes screen waviness packings and loads in the reactor, put into 1t mass content be the potassium hydroxide aqueous solution of 50% and with pump by continuous for this aqueous alkali Be circulated through the packing layer of reactor, put into again potassium acetate or acetic acid 20-40 kilogram, Often press control temperature 10-140 DEG C, moves 24-48 with pump by reaction material liquid recycle stream little Time, then lower the temperature, filter, collect the mother solution filtered, put into common electric stirring In reactor, addition 1-2t industrial alcohol or industry pyridine, in this reactor, control Temperature 40-90 DEG C, stirring extraction time 2-4 hour, then lower the temperature, stand, be layered, The lower floor separated is aqueous alkali, capable of circulation after recovery applies mechanically, and the upper strata separated is second Alcohol or pyridine solution, distill with common clearance-type rectifying column and reclaim ethanol or pyridine, Distillation substrate is acetoin and butanediol and ethanol and diacetyl and butanone and hydroxyl is own The organic mix product of ketone, the gross production rate of organic admixture is more than 84%.

Embodiment 5

Select common electric stirring high-pressure reactor, under room temperature, put into mass content For potassium hydroxide or the sodium hydrate aqueous solution 100 grams of 40-70%, put into again zinc powder or Technique of activated ferrous powder with or activity nikel powder or activity copper powder 40 grams, in this reactor, start stirring, Under conditions of uncovered normal pressure, control temperature 10-140 DEG C, be slowly added into acetate or Acetic acid or add propionate or propanoic acid or add butyrate or butanoic acid or add benzene Formates or benzoic acid or add furoate or furancarboxylic acid, each addition is respectively 30-70 Gram, insulated and stirred is reacted 24-48 hour, has generated acetoin and butanediol With ethanol and the mixture of hydroxyl hexanone；Or generated the third acyloin and hexanediol and The mixture of propanol；Or generate the mixture of butyroin and ethohexadiol and capryl alcohol； Or generate the mixture of benzoin and hydrobenzoin and benzyl alcohol；Or Generated furoin and difurfuryl ethylene glycol and the mixture of furfuryl alcohol, then lower the temperature, quiet Put, filter, the mother solution leached is returned in electric stirring high-pressure reactor, again opens Open stirring, regulate and control temperature 160-320 DEG C, control reactor pressure 10MPa Hereinafter, continue stirring reaction 4-12 hour, be then down to room temperature and normal pressure, add Ethanol or the acetone of 100-200 gram extract, and then layering, rectification, steam and return Receiving ethanol or acetone solvent and acetaldehyde or propionic aldehyde or butyraldehyde, distillation substrate is fourth Diketone and butanone and the mixture of hydroxyl hexanone；Or distillation substrate is acetyl butyryl and oneself The mixture of ketone；Or the mixture that distillation substrate is acetyl caproyl and octanone；Or steam Evaporating substrate is diphenylthanedione and diphenylethan and the mixture of benzaldehyde；Or Distillation substrate is the ketone such as the mixture of difurfuryl second diketone and difurfuryl ethyl ketone and furfural The mix product of (aldehyde) type organic, the mixing of various ketone (aldehyde) type organic The gross production rate that thing adds up to respectively reaches more than 75%.

Embodiment 6

Choose above-described embodiment 1 or filtrated stock 50-100 gram of embodiment 2 preparation, Put in common electric stirring reactor, start stirring, slowly heat up, at normal pressure Distillating liquid to fine vacuum, temperature rises to stop distillation when 240 DEG C, passes through The liquid steaming condensation constantly collected by condenser, by gas chromatogram and liquid chromatograph pair This liquid is analyzed test, learns that this liquid is containing of diacetyl and butanone and acetaldehyde Aqueous mixtures；Or it is acetyl butyryl and hexanone and the aqueous mixture of propionic aldehyde；Or it is Acetyl caproyl and octanone and the aqueous mixture of butyraldehyde；Or it is diphenylthanedione and two Phenyl ethyl ketone and the aqueous mixture of benzaldehyde；Or it is difurfuryl second diketone and two brans Base ethyl ketone and the aqueous mixture of furfural, total product that various mixture product add up to respectively Rate is more than 72%.

Embodiment 7

Choosing common electric stirring reactor, putting into mass content is the hydrogen of 30-70% Potassium oxide or sodium hydroxide or calcium hydroxide or the aqueous solution of Lithium hydrate or water slurry 100 grams, or put into the tetraethyl ammonium hydroxide aqueous solution of 25%, put into potassium acetate simultaneously Or sodium acetate or calcium acetate or Quilonorm (SKB) or acetic acid 20-40 gram are in this reactor, again Add activity copper powder or activity nikel powder 40-70 gram, start stirring, at uncovered normal pressure Under the conditions of, control temperature 10-140 DEG C, stirring reaction 12-24 hour, then drip dense Hydrochloric acid, is neutralized to neutrality by reaction feed liquid, then lowers the temperature, and adds 100-200 gram of second Alcohol or pyridine, regulate temperature 40-90 DEG C. stirring extraction 4-8 hour, then lower the temperature, quiet Put, be layered, separate the aqueous alkali layer of lower floor, reclaim Posterior circle and apply mechanically, separate upper strata Ethanol or pyridine layer, distill with common rectifying column, controls vapo(u)rizing temperature 160-240 DEG C, steam and reclaim aqueous ethanol or pyridine solvent and acetaldehyde product, steam Evaporate substrate and be the aqueous mixed of acetoacetic acid and hydroxybutyric acid and acetoin and hydroxyl hexanone Composition powder, the gross production rate that each product adds up to reaches more than 87%, wherein acetoacetic acid and hydroxyl The productivity of two kinds of products of base butanoic acid adds up to 64%.

Embodiment 8

Selecting common electric stirring high-pressure reactor, input mass content is 40-70% Potassium hydroxide or sodium hydroxide or calcium hydroxide or Lithium hydrate etc. all are alkaline Aqueous solution or water slurry 100 grams in this reactor, simultaneously put into activity magnesium powder and Technique of activated ferrous powder with 40-70 gram, puts into 40 grams of Glacial acetic acid potassium the most simultaneously, or puts into nothing Water acetic acid 20 grams, in this reactor, starts stirring, controls temperature 70-200 DEG C, control Below pressing pressure 10Mpa, stirring reaction 12-24 hour, then cooling, blood pressure lowering, Filtering, filter cake is magnesium powder or iron powder, filtrate be diacetyl and acetoin and butanediol and The alkaline aqueous mixture product of butanone, tests with gas chromatogram and liquid-phase chromatographic analysis, fourth What diketone and acetoin and butanediol and butanone added up to gross production rate reaches more than 92%.

Embodiment 9

Select common electric stirring reactor, under room temperature, put into the hydrogen of 100 gram 50% Potassium oxide aqueous solution, puts into 20 grams of Glacial acetic acids simultaneously, puts into 40 grams of zinc the most simultaneously Powder or put into 50 grams of technique of activated ferrous powder with or put into 70 grams of active copper powders, start stirring, Under conditions of uncovered normal pressure, control reaction temperature and be 40-70 DEG C, stirring reaction 12-24 Hour, then distillation reaction feed liquid under conditions of normal pressure, collect with condenser and to steam Feed liquid, temperature rises to be cooled to when 180 DEG C 90 DEG C, then in the condition of fine vacuum Under start to warm up again and distill, when temperature rises to 180 DEG C, continue the bar in fine vacuum Stirring 1 hour under part, stop stirring, cooling, the feed liquid collected by condensation is second The aqueous mixture product of acyloin and diacetyl, can send into rectification working process and carry out further Separation, the productivity that acetoin and diacetyl add up to is 78%, distills the recyclable set of substrate With.

Embodiment 10

Select common electric stirring high-pressure reactor, start stirring, add anhydrous Butanediol or acetoin 20-30 gram, in this reactor, control temperature 40-300 DEG C, Control pressure 0-10MPa, stirring reaction 4-12 hour, be cooled to room temperature, be depressurized to Normal pressure, adds ethanol or 100-200 gram of acetone is stirred extraction, and 2-4 is little in stirring Time, then stand, be layered, collect upper strata ethanol or acetone liquid layer, divide with common Fractional distillation column carries out rectification separation to this liquid layer, collects the condensed fluid of 70-95% fraction, uses gas Phase chromatograph and liquid-phase chromatographic analysis, this condensed fluid is the aqueous mixing of diacetyl and butanone The gross production rate of thing, diacetyl and butanone is more than 72%.

Embodiment 11

Select common driven high voltage reactor, put into the potassium hydroxide of 40-70% (KOH) or the aqueous solution 100 grams of sodium hydroxide or calcium hydroxide or Lithium hydrate, again Put into zinc powder and technique of activated ferrous powder with or activity copper powder 40 grams in this reactor, startup is stirred Mix, add anhydrous butanediol or acetoin 20-30 gram in this reactor, control temperature Spend 40-300 DEG C, control pressure 0-10MPa, stirring reaction 12-24 hour, lower the temperature, Blood pressure lowering, collects the butane gas overflowed by reactor simultaneously, stands, filters, and filters It is 76% that mother solution is the gross production rate of the aqueous alkali of butanone, butanone and butane.

Claims

1. one kind uses carboxylate or carboxylic acid is that raw material carries out catalytic reaction and synthesizes corresponding with water Acyloin and alcohol and the organic method of ketone, is characterized by that alkaline chemical catalysis reacts Environmental system, i.e. combination potassium hydroxide or sodium hydroxide or Lithium hydrate or calcium hydroxide or The highly basic such as tetra-alkyl ammonium hydroxide and metal simple-substance or non-metal simple-substance become a kind of compound Catalyst, preferred compositions KOH/ zinc composite catalyst, this composite catalyst is put into water Solution carries out the chemical catalysis synthetic reaction of carboxylate or carboxylic acid and water.

2. acyloin and alcohol and ketone organic method are synthesized with carboxylate or carboxylic acid with water, Several steps including following sequence:

Select common clearance-type or flow reactor, put into the dense hydrogen-oxygen of amount of calculation Change potassium or concentrated sodium hydroxide or dense calcium hydroxide or the aqueous solution of dense Lithium hydrate or water hangs Supernatant liquid in this reactor, or put into amount of calculation dense tetra-alkyl ammonium hydroxide aqueous solution or Water slurry, in this reactor, puts into again or the zinc of immobilized amount of calculation or ferrum or nickel or stannum Or lead or manganese or all metal simple-substances such as magnesium or copper or the nonmetal list such as activated carbon or sulfur Matter is in this reactor, under conditions of uncovered normal pressure, controls temperature 10-140 DEG C, It is slowly added into carboxylate or the carboxylic acid of amount of calculation, keeps certain catalytic reaction time, so Rear cooling, standing, filter, the mother solution liquid chromatograph leached and gas chromatographic analysis are surveyed Examination, it is known that this mother solution is acyloin and alcohol and the organic alkaline aqueous mixture of ketone, filtration Filter cake is the metal simple-substance powder added, can be with recycled；Then the mother solution filtered is used Ethanol or pyridine solvent carry out liquid-liquid extraction, add the work of amount of calculation in stirred reactor Industry ethanol and pyridine, control temperature 40-90 DEG C, keep certain stirring extraction time, It is then passed through common standing, layering, the unit process of rectification, reclaims ethanol or pyridine Solvent, obtains the dense acyloin that separates with aqueous alkali and alcohol and ketone organic mixing produce Product.

3. one kind uses carboxylate or carboxylic acid is that raw material carries out catalytic reaction synthesis ketone and aldehyde with water The method of type organic, is characterized in that carboxylate or carboxylic acid to react, with water, the acyloin generated And alcohol type organic is as intermediate or raw material, under conditions of being catalyzed with high temperature liquid water React further, the carboxylic acid thus this intermediate being further converted to and putting into Salt or the corresponding diones of carboxylic acid and a ketone and hydroxyl hexanone class and corresponding aldehydes Organic mix product.

4. ketone and aldehydes organic method are synthesized with carboxylate or carboxylic acid with water, including Several steps of following sequence:

Select common electric stirring high-pressure reactor, put into the dense hydroxide of amount of calculation Potassium or concentrated sodium hydroxide or dense calcium hydroxide or dense lithium hydroxide aqueous solution or water slurry, Put into again the zinc powder of amount of calculation or technique of activated ferrous powder with or activity nikel powder or activity copper powder etc. all Metal simple-substance powder or put into the non-metal simple-substance such as activated carbon or sulfur, start stirring, again Put into the carboxylate of amount of calculation or carboxylic acid in this reactor, control and regulate temperature be 40-300 DEG C, controlling and regulating pressure is 0-10MPa, after the stirring reaction regular hour, Lowering the temperature, stand, filter, filter cake is the metal or non-metal simple-substance powder added, and filtrate is i.e. For diones and a ketone and the corresponding organic alkaline aqueous mixture of aldehydes, with ethanol or third This filtrate is extracted by ketone, then carries out common layering, the process of rectification, reclaims second Alcohol or acetone solvent, obtain the dense diones that separates with aqueous alkali and a ketone and corresponding simultaneously The organic mix product of aldehydes.

5. carboxylate or carboxylic acid as a kind of approach synthesis acyloin class by reacting with water and Corresponding alcohols and ketone and the purposes of the organic raw material of aldehydes.

6. acetate or acetic acid are as a kind of approach synthesis acetoin by reacting with water and fourth The purposes of the raw material of glycol and ethanol and diacetyl and butanone and acetaldehyde and hydroxyl hexanone； Propionate or propanoic acid as a kind of approach by reacting with water synthesize the third acyloin and oneself two The purposes of the raw material of alcohol and propanol and acetyl butyryl and hexanone and propionic aldehyde；Butyrate or butanoic acid As a kind of approach synthesis butyroin by reacting with water and ethohexadiol and capryl alcohol and The purposes of the raw material of acetyl caproyl and octanone；Benzoate or benzoic acid as one by with The approach of water reaction synthesizes benzoin and hydrobenzoin and benzyl alcohol and diphenyl The purposes of the raw material of second diketone and diphenylethan and benzaldehyde；Furoate or furancarboxylic acid conduct A kind of approach synthesis furoin by reacting with water and difurfuryl ethylene glycol and furfuryl alcohol with And the purposes of the raw material of difurfuryl second diketone and furfural.

7. acetate or acetic acid as a kind of approach synthesis of acetyl acetic acid by reacting with water and The purposes of the raw material of hydroxybutyric acid.