CN104327038B - A kind of containing-SO 3the method of acetal (ketone) is prepared in the acid magneticsubstance catalysis of H - Google Patents
A kind of containing-SO 3the method of acetal (ketone) is prepared in the acid magneticsubstance catalysis of H Download PDFInfo
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- CN104327038B CN104327038B CN201410545674.XA CN201410545674A CN104327038B CN 104327038 B CN104327038 B CN 104327038B CN 201410545674 A CN201410545674 A CN 201410545674A CN 104327038 B CN104327038 B CN 104327038B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
- C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/16—Radicals substituted by halogen atoms or nitro radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems
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Abstract
The invention discloses a kind of containing-SO
3the method of acetal (ketone) is prepared in the acid magneticsubstance catalysis of H, belongs to chemical material and preparing technical field thereof.In this preparation method, the mol ratio of aldehydes or ketones used and alcohol is 1:(1 ~ 5), with-SO
3the molar weight that H calculates acid magnetic catalyst used is 8 ~ 10% of aldehydes or ketones used, temperature of reaction is 110 DEG C, reaction times is 0.5 ~ 3h, reaction pressure is a normal atmosphere, room temperature is cooled to after reaction, with magnet sucking-off catalyzer, reaction solution is by the productive rate of the transformation efficiency of gas chromatographic analysis detection reaction raw material, selectivity and acetal (ketone).The present invention is compared with the preparation method of other catalyzer, there is reaction preference high, simply, the advantages such as catalyzer can be recycled without any process and whole preparation process is easy and simple to handle, economic benefit is high, are convenient to industrialization scale operation for catalyzer and product separation.
Description
Technical field
The invention belongs to chemical material and preparing technical field thereof, be specifically related to a kind of containing-SO
3the method of acetal (ketone) is prepared in the acid magneticsubstance catalysis of H.
Background technology
Acetal (ketone) is the important intermediate in chemical industry, is usually used in the protection of aldehydes or ketones, is even used as special reaction solvent.The method that tradition prepares acetal (ketone) is carried out under mineral acid (sulfuric acid, hydrochloric acid, phosphoric acid etc.) catalysis, but this method to there is side reaction many, equipment corrosion is serious, and product purity is not high, and aftertreatment is more loaded down with trivial details, and produces three-waste pollution.Therefore, develop acetal (ketone) green, efficiently, can be recycled and cause the great interest of chemists with the segregative new catalyst of product.
In recent years, acidic ion liquid, particularly bronsted acid ionic liquid owing to having green non-pollution, to organicly there is good solubility, the acidic site be evenly distributed with mineral compound, be easy to product and be separated and can be recycled etc. advantage and being used in the preparation of acetal (ketone).Such as applicant uses the salt acidic ionic liquid of N-methylimidazolium hydrogen sulphate as catalyzer, can nucleophilic addition occur between catalysis aldehydes or ketones and alcohol effectively and then prepare acetal (ketone) under condition of no solvent.Due to catalyzer and acetal (ketone) mutual solubility poor, only need just can realize being separated of product and catalyzer by simple separatory, and the catalyzer after dewatering can recycle.Acidity but due to the salt acidic ionic liquid of N-methylimidazolium hydrogen sulphate is more weak, in preparation process, (method [P] of acetal or ketal is prepared in the catalysis of a kind of N-methylimidazolium hydrogen sulphate ionic liquid to its large usage quantity, Yue Caibo, Yi Tingfeng. application number: 200810243309.8).In order to improve the acidity of acidic ion liquid and then reduce its consumption, old waiting quietly uses containing-SO
3the sulfonic acid funtionalized ionic liquid of H is as catalyzer, preparation process (the research [J] of functionalized ion liquid catalytic performance in acetal (ketone) reaction of acetal (ketone) can be realized when its consumption is only 1%, dragon Venus, Zhao Yingwei, Liu Jianhua, Li Zhen, Chen Jing. Journal of Molecular Catalysis, 2008,22 (3): 199-204).
In addition, in order to reduce the separating difficulty between acetal (ketone) and catalyzer further, thus simplify post-processing operation, simultaneously also in order to reduce the number of dropouts of catalyzer in recycling.Applicant employs a kind of containing-SO
3the metal organic framework compound of H is as heterogeneous catalyst, (method [P] of acetal or ketal is prepared in a kind of metal organic framework compound catalysis to achieve the reaction preparing acetal (ketone) under condition of no solvent, Yue Caibo, Yi Tingfeng. application number: 201310042438.1).
Although above-mentioned metal organic framework compound catalyzer catalysis efficiently can prepare acetal (ketone), because its thermostability is poor, structure is easily caved in the reaction, thus affects its catalytic effect and recycle performance.In addition, prepare the raw material of acidic ion liquid and metal organic framework compound costly, be difficult to be used on a large scale in suitability for industrialized production.
Summary of the invention
The object of the invention is to overcome existing catalysis, to prepare catalyzer usage quantity in acetal (ketone) technology large and recycle that middle number of dropouts is large, catalyst preparing price is higher and the shortcoming such as last handling process is complicated, and provide a kind of acidity higher, inexpensive and preparation is simple containing-SO
3the method of acetal (ketone) is prepared in the acid magneticsubstance catalysis of H.
The skeleton symbol of acid magnetic catalyst used in the present invention is:
One of the present invention contains-SO
3the method particular content that acetal (ketone) is prepared in the acid magneticsubstance catalysis of H is as follows: the mol ratio preparing aldehydes or ketones used and alcohol in acetal (ketone) reaction is 1:(1 ~ 5), with-SO
3the molar weight that H calculates acid magnetic catalyst used is 8 ~ 10% of aldehydes or ketones used, temperature of reaction is 110 DEG C, reaction times is 0.5 ~ 3h, reaction pressure is a normal atmosphere, room temperature is cooled to after reaction, with magnet sucking-off catalyzer, reaction solution is by the productive rate of the transformation efficiency of gas chromatographic analysis detection reaction raw material, selectivity and acetal (ketone).The catalyzer of sucking-off is directly used in without the need to any process and reacts next time, and can reuse at least 7 times, its products collection efficiency does not have obvious reduction.
Described aldehydes or ketones is selected from
In one; Wherein: a is the integer between 0 ~ 6, R is the one in alkyl, alkoxyl group, halogen, hydroxyl.
Described alcohol is selected from
In one; Wherein: b is the integer between 1 ~ 5, c is the integer between 0 ~ 4.
The preparation method of acid magnetic catalyst used in the present invention, see pertinent literature (Sulfonicacid-functionalizedsilica-coatedmagneticnanopart iclesasanefficientreusablecatalystforthesynthesisof1-sub stituted1H-tetrazolesundersolvent-freeconditions [J], HosseinNaeimiandSamanehMohamadabadi.DaltonTransactions, 2014,43:12967 ~ 12973).
The present invention, compared with the preparation method of other catalyzer, has the following advantages:
1, catalyst activity is good, and reaction preference is high and environmentally friendly;
2, catalyzer does not need to carry out any process recycling in process;
3, catalyzer and product mutual solubility poor, simple, the convenient and easy handling of sepn process;
4, whole building-up process economy, efficient, is convenient to industrialization scale operation.
Embodiment
Substantive features of the present invention and unusual effect can be embodied from following embodiment; but they do not impose any restrictions the present invention; those skilled in the art's content according to the present invention makes some nonessential improvement and adjustment, all belongs to protection scope of the present invention.
Embodiment 1: by 10mmol butyraldehyde-n, 10mmol1, the acid magneticsubstance of ammediol and 2.72g joins in the 25ml single port bottle with stirrer and prolong.At 110 DEG C, vigorous stirring reaction 0.75h, is cooled to room temperature after reaction, with magnet sucking-off catalyzer.The transformation efficiency that reaction solution gas chromatographic detection obtains butyraldehyde-n is 97%, and the selectivity of product butyraldehyde-n 1,3-PD acetal is 100%, and calculating its productive rate is 97%, and catalyzer uses without cycle for the treatment of.
Embodiment 2: by 10mmol phenyl aldehyde, 15mmol1, the acid magneticsubstance of ammediol and 3.04g joins in the 50ml single port bottle with stirrer and prolong.At 110 DEG C, vigorous stirring reaction 1.5h, is cooled to room temperature after reaction, with magnet sucking-off catalyzer.The transformation efficiency that reaction solution gas chromatographic detection obtains phenyl aldehyde is 93%, and the selectivity of product phenyl aldehyde 1,3-PD acetal is 100%, and calculating its productive rate is 93%, and catalyzer uses without cycle for the treatment of.
Embodiment 3: acid to 10mmol paranitrobenzaldehyde, 25mmol ethylene glycol and 2.41g magneticsubstance is joined in the 50ml single port bottle with stirrer and prolong.At 110 DEG C, vigorous stirring reaction 2h, is cooled to room temperature after reaction, with magnet sucking-off catalyzer.The transformation efficiency that reaction solution gas chromatographic detection obtains paranitrobenzaldehyde is 96%, and the selectivity of product paranitrobenzaldehyde-Glycol Acetal is 100%, and calculating its productive rate is 96%, and catalyzer uses without cycle for the treatment of.
Embodiment 4: acid to 10mmol pimelinketone, 15mmol2,2-dimethyl propylene glycol and 2.72g magneticsubstance is joined in the 50ml single port bottle with stirrer and prolong.At 110 DEG C, vigorous stirring reaction 2h, is cooled to room temperature after reaction, with magnet sucking-off catalyzer.The transformation efficiency that reaction solution gas chromatographic detection obtains pimelinketone is 90%, and the selectivity of product pimelinketone 2,2-dimethyl propanediol Ketal is 100%, and calculating its productive rate is 90%, and catalyzer uses without cycle for the treatment of.
Embodiment 5: acid to 10mmol n-hexyl aldehyde, 50mmol methyl alcohol and 3.04g magneticsubstance is joined in the 100ml single port bottle with stirrer and prolong.At 110 DEG C, vigorous stirring reaction 3h, is cooled to room temperature after reaction, with magnet sucking-off catalyzer.The transformation efficiency that reaction solution gas chromatographic detection obtains n-hexyl aldehyde is 88%, and the selectivity of product n-hexyl aldehyde-methyl alcohol acetal is 100%, and calculating its productive rate is 88%, and catalyzer uses without cycle for the treatment of.
Embodiment 6: with embodiment 1 for probe reaction, make the active replica test of the acid magneticsubstance of catalysts, catalyzer reuses 7 times, and the transformation efficiency of butyraldehyde-n and the selectivity of product butyraldehyde-n 1,3-PD acetal, yield data are in table 1.
The active revision test result of table 1. catalyzer in butyraldehyde-n and 1,3-PD aldolization
Embodiment 7: with embodiment 4 for probe reaction, make the active replica test of the acid magneticsubstance of catalysts, catalyzer reuses 7 times, and the transformation efficiency of pimelinketone and the selectivity of product pimelinketone 2,2-dimethyl propanediol Ketal, yield data are in table 2.
The active revision test result of table 2. catalyzer in pimelinketone and 2,2-dimethyl propylene glycol ketal reaction
As can be seen from table 1 and 2: in the present invention, this acid magnetic catalyst is recycling in process, and its catalytic capability almost remains unchanged.Can prove that it is prepared in the nucleophilic addition of acetal (ketone) can be reused at least 7 times in catalysis thus.
Claims (2)
1. one kind contains-SO
3the method of acetal or ketal is prepared in the acid magneticsubstance catalysis of H, it is characterized in that, in described preparation method, the mol ratio of aldehydes or ketones used and alcohol is 1:1 ~ 5, with-SO
3the molar weight that H calculates acid magnetic catalyst used is 8 ~ 10% of aldehydes or ketones used, temperature of reaction is 110 DEG C, reaction times is 0.5 ~ 3h, reaction pressure is a normal atmosphere, room temperature is cooled to after reaction, with magnet sucking-off catalyzer, reaction solution is by the productive rate of the transformation efficiency of gas chromatographic analysis detection reaction raw material, selectivity and acetal or ketal;
Described aldehydes or ketones is selected from
In one; Wherein: a is the integer between 0 ~ 6, R is the one in alkyl, alkoxyl group, halogen, hydroxyl;
Described alcohol is selected from
In one; Wherein: b is the integer between 1 ~ 5, c is the integer between 0 ~ 4;
The skeleton symbol of described acid magnetic catalyst is:
2. as claimed in claim 1 a kind of containing-SO
3the method of acetal or ketal is prepared in the acid magneticsubstance catalysis of H, it is characterized in that, the catalyzer after described sucking-off is directly used in without the need to any process and reacts next time, can reuse at least 7 times.
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