CN105601610A - Preparation method for monobenzalpenlpentaerythritol - Google Patents
Preparation method for monobenzalpenlpentaerythritol Download PDFInfo
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- CN105601610A CN105601610A CN201510836633.0A CN201510836633A CN105601610A CN 105601610 A CN105601610 A CN 105601610A CN 201510836633 A CN201510836633 A CN 201510836633A CN 105601610 A CN105601610 A CN 105601610A
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- benzaldehyde
- pentaerythrite
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- hydrochloric acid
- acetonitrile
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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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Abstract
The invention specifically relates to a preparation method for monobenzalpenlpentaerythritol, which belongs to the technical field of organic synthesis. The method comprises the following steps: (1) adding pentaerythritol, a solvent water and a cosolvent acetonitrile into a container, carrying out stirring and heating to 50 to 80 DEG C, then slowly adding a mixed liquid of benzaldehyde, acetonitrile and a hydrochloric acid solution drop by drop within 0.5 to 1 h, and after completion of dropwise addition, continuing a reaction at a maintained temperature of 2 to 5 h; and (2) cooling a reaction solution to certain temperature under stirring and then successively carrying out pumping filtration, washing and drying. The method provided by the invention is simple, high in reaction yield and high in product purity.
Description
Technical field
The present invention relates to a kind of preparation method of monoacetal, more particularly relate to a kind of system of pentaerythrite list condensing benzaldehydePreparation Method.
Background technology
The condensation reaction of pentaerythrite and benzaldehyde is reversible reaction, and the water generating in reaction adopts benzene, toluene, cyclohexaneRemove in band aqua, reaction is carried out to positive direction. In this reaction system benzene, toluene, cyclohexane be band aqua andSolvent. Because the polarity of pentaerythrite is larger, it is insoluble in most of nonpolar or organic solvents that polarity is less such as benzene,Pentaerythrite and reacting of benzaldehyde are heterogeneous reaction systems like this, and therefore, the reaction time is longer. In addition, seasonPenta tetrol reacts single contracting compound of producing and is generally all dissolved in these organic solvents with benzaldehyde, single like this contracting compound very easily entersOne step and benzaldehyde generation condensation obtain bisacetal compound, and therefore, single contracting compound amount is few, purity is low.
At present, to adopt single solvent (DMF, DMSO) homogeneous phase method and water be solvent to the monoacetal synthetic method of pentaerythriteTwo kinds of heterogeneous methods. Single solvent (DMF, DMSO) homogeneous phase method, because raw material and product are all dissolved in these solvents wellIn, therefore, be difficult to avoid single contracting compound further to generate two contracting compounds with benzaldehyde. In addition, due to this reactionBe acid catalyzed reaction, and acid and DFM are easy to salify, have reduced like this protonated of free acid and ketonic oxygen, and acid is not hadThere is fine performance catalytic action. Water is the heterogeneous method of solvent, because benzaldehyde is insoluble in water, under agitation, reaction systemBe an emulsification system, the reaction speed of itself and pentaerythrite is slower, and single contracting compound of generation is water insoluble,In solution, separate out, when it is separated out, can wrap up some unreacted benzaldehydes, make product purity low.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide one just can obtain high-purity without decompression distillationThe preparation method of the pentaerythrite list condensing benzaldehyde of high yield.
Present inventor, in order to improve yield and the purity of pentaerythrite monoacetal, has invented a solvent pairs homogeneous reaction system,This reaction system makes pentaerythrite react in homogeneous phase with benzaldehyde, but monoacetal product because of be insoluble to this reaction system withThe form of solid is separated out, and greatly reduces so single contracting compound and continues to react the two contracting compounds of generation with benzaldehyde. Meanwhile,In this reaction, increase the consumption of solvent in reaction system, reduced the collision probability of benzaldehyde and single contracting compound, thereby carryThe yield of high single contracting compound (being two hydroxyls in four hydroxyls of pentaerythrite and the condensation product of benzaldehyde) and pureDegree.
This method adopts cosolvent water solution system, specifically in reaction flask, adds water, quantitative cosolvent and a small amount ofAqueous hydrochloric acid solution. Adding of cosolvent is to increase the solubility of pentaerythrite in water, the benzene first that also makes postorder add simultaneouslyAldehyde can be dissolved in reaction system well, makes reaction system become homogeneous phase. Then, the solution in reaction system is heated to necessarilyAfter temperature, slowly drip the mixed liquor of benzaldehyde and acetonitrile, the object that acetonitrile adds is in the time dripping benzaldehyde, controlsBenzaldehyde keeps low concentration in reaction system, and benzaldehyde is dispersed in reaction system as early as possible. Along with adding of benzaldehyde,The monoacetal compound that reaction generates is constantly separated out from system. Reason is in this system, and the amount of acetonitrile is less, and (acetonitrile onlyPlay bridge beam action, benzaldehyde and pentaerythrite be dissolved in the aqueous solution), monoacetal compound is at this acetonitrile like thisIn the aqueous solution, solubility is very little, so that separates out with the monoacetal compound that carries out of reaction, has avoided single contracting compound and benzaldehydeContinue reaction and generate bisacetal compound.
Reaction mechanism of the present invention is as follows: the present invention is the reaction mechanism of a nucleophilic addition-dehydration, under acid catalysis, and seasonPenta tetrol carries out addition as the carbonyl in nucleopilic reagent and benzaldehyde, generates hemiacetal, then at the work of inorganic acid (hydrochloric acid)With under, make the hydroxyl proton on hemiacetal, heating under slough water, produce carbonium ion, this carbonium ion is subject to season againOn penta tetrol, another monohydroxy attack, sloughs proton, and finally generates pentaerythrite list condensing benzaldehyde.
Technical solution of the present invention is specific as follows.
The preparation method who the invention provides a kind of pentaerythrite list condensing benzaldehyde, concrete steps are as follows:
(1) in container, add pentaerythrite, water and cosolvent, under stirring, be heated to 50～80 DEG C, then drip benzaldehyde, secondThe mixed liquor of nitrile and hydrochloric acid solution, time for adding 0.5～1h, after dropping finishes, continues insulation reaction 2～5h; Wherein: season pentaThe mol ratio of tetrol and benzaldehyde is 1:1～1:6; The addition of water is 20-40L/mol pentaerythrite; The addition of cosolventIt is 5～20L/mol pentaerythrite; The addition of acetonitrile is 10～20L/mol benzaldehyde; Hydrochloric acid solution is the hydrochloric acid of 8-12wt%Solution, hydrochloric acid solution addition is 5～15L/mol benzaldehyde;
(2) under stirring, reactant liquor is naturally cooled to 20～30 DEG C, suction filtration, washing afterwards, and dry at 60～80 DEG C,To pentaerythrite list condensing benzaldehyde.
In the present invention, in step (1), mixing speed is 100～250r/min.
In the present invention, in step (1), described cosolvent is acetonitrile.
In the present invention, in step (2), mixing speed is 50～100r/min.
Beneficial effect of the present invention is: the present invention has overcome in the past in reaction system, catalyst, pentaerythrite, benzaldehydeIn the existing problem of heterogeneous middle reaction. The present invention has used solvent pairs system (water+water-miscible organic solvent), water-solubleOrganic solvent has played bridge beam action at this, makes the oil phase benzaldehyde system that is soluble in the aqueous phase. By regulating water and water-soluble organicThe ratio of solvent is reacted catalyst, pentaerythrite and benzaldehyde in homogeneous system, has speeded the process of reaction.On the other hand, because pentaerythrite list condensing benzaldehyde solubility in this reaction system is less, with the carrying out of reaction, with solidForm is separated out from reaction system, has reduced pentaerythrite list condensing benzaldehyde and has become the general of two contracting compounds with benzaldehyde againRate, makes the purity of single contracting compound higher.
Detailed description of the invention
Executing example below by concrete enforcement describes in further detail the present invention.
Embodiment 1
In 1 liter of flask, add pentaerythrite, the water of 200mL and the acetonitrile of 10mL of 0.8mol, at 120～150r/minUnder stirring, be heated to 60 DEG C, then, drip benzaldehyde, 5mL second eyeball and 10% hydrochloric acid 2mL mixed of 0.2mol with 0.5hClose liquid, after dripping, at this temperature insulation reaction 3h, under stirring with 60r/min, be cooled to 25 DEG C; With 20mL go fromSub-water filtering and washing, dries with 60 DEG C of temperature after draining. Obtain pentaerythrite list condensing benzaldehyde 37.5g, yield 83.0%;134.1～134.8 DEG C of fusing points, high pressure liquid chromatographic analysis, purity is 99.2%.
Embodiment 2
In 1 liter of flask, add pentaerythrite, the water of 200mL and the acetonitrile of 10mL of 0.8mol, at 120～150r/minUnder stirring, be heated to 80 DEG C, then, drip benzaldehyde, 5mL second eyeball and 10% hydrochloric acid 2mL mixed of 0.2mol with 0.5hClose liquid, after dripping, at this temperature insulation reaction 3h, under stirring with 60r/min, be cooled to 25 DEG C; With 20mL go fromSub-water filtering and washing, dries with 60 DEG C of temperature after draining. Obtain product 35.1g, yield 76.5%; Fusing point 128.3～132.8DEG C, high pressure liquid chromatographic analysis, purity is 97.6.%.
Embodiment 3
In 1 liter of flask, add pentaerythrite, the water of 200mL and the acetonitrile of 10mL of 0.8mol, at 120～150r/minUnder stirring, be heated to 60 DEG C, then, drip benzaldehyde, 5mL second eyeball and 10% hydrochloric acid 2mL mixed of 0.3mol with 0.5hClose liquid, after dripping, at this temperature insulation reaction 3h, under stirring with 60r/min, be cooled to 25 DEG C; With 20mL go fromSub-water filtering and washing, dries with 60 DEG C of temperature after draining. Obtain pentaerythrite list condensing benzaldehyde 53.3g, yield 77.5%;132.0～134.5 DEG C of fusing points, high pressure liquid chromatographic analysis, purity is 97.8.%.
Embodiment 4
In 1 liter of flask, add pentaerythrite, the water of 200mL and the acetonitrile of 20mL of 0.8mol, at 120～150r/minUnder stirring, be heated to 80 DEG C, then, drip benzaldehyde, 5mL second eyeball and 10% hydrochloric acid 2mL mixed of 0.2mol with 0.5hClose liquid, after dripping, at this temperature insulation reaction 3h, under stirring with 60r/min, be cooled to 25 DEG C; With 20mL go fromSub-water filtering and washing, dries with 60 DEG C of temperature after draining. Obtain pentaerythrite list condensing benzaldehyde 36.2g, yield 78.4%;126.2～130.5 DEG C of fusing points, high pressure liquid chromatographic analysis, purity is 97.0.%.
Embodiment 5
In 1 liter of flask, add pentaerythrite, the water of 300mL and the acetonitrile of 15mL of 0.8mol, at 120～150r/minUnder stirring, be heated to 60 DEG C, then, drip benzaldehyde, 5mL second eyeball and 10% hydrochloric acid 2mL mixed of 0.2mol with 0.5hClose liquid, after dripping, at this temperature insulation reaction 3h, under stirring with 60r/min, be cooled to 25 DEG C; With 20mL go fromSub-water filtering and washing, dries with 60 DEG C of temperature after draining. Obtain pentaerythrite list condensing benzaldehyde 37.1g, yield 82.3%;134.2～135.0 DEG C of fusing points, high pressure liquid chromatographic analysis, purity is 99.4.%.
Embodiment 6
In 1 liter of flask, add pentaerythrite, the water of 200mL and the acetonitrile of 10mL of 0.6mol, at 120～150r/minUnder stirring, be heated to 60 DEG C, then, drip benzaldehyde, 5mL second eyeball and 10% hydrochloric acid 2mL mixed of 0.2mol with 0.5hClose liquid, after dripping, at this temperature insulation reaction 3h, under stirring with 60r/min, be cooled to 25 DEG C; With 20mL go fromSub-water filtering and washing, dries with 60 DEG C of temperature after draining. Obtain pentaerythrite list condensing benzaldehyde 36.9g, yield 81.2%;131.5～133.8 DEG C of fusing points, high pressure liquid chromatographic analysis, purity is 98.6.%.
Embodiment 7
In 1 liter of flask, add pentaerythrite, the water of 200mL and the acetonitrile of 10mL of 0.4mol, at 120～150r/minUnder stirring, be heated to 60 DEG C, then, drip benzaldehyde, 5mL second eyeball and 10% hydrochloric acid 2mL mixed of 0.2mol with 0.5hClose liquid, after dripping, at this temperature insulation reaction 3h, under stirring with 60r/min, be cooled to 25 DEG C; With 20mL go fromSub-water filtering and washing, dries with 60 DEG C of temperature after draining. Obtain pentaerythrite list condensing benzaldehyde 36.3g, yield 79.2%;131.5～133.8 DEG C of fusing points, high pressure liquid chromatographic analysis purity is 97.7.%.
Above said content is only the basic explanation of the present invention under conceiving, and do according to technical scheme of the present invention any etc.Effect conversion, all should belong to protection scope of the present invention.
Claims (4)
1. a preparation method for pentaerythrite list condensing benzaldehyde, is characterized in that, concrete steps are as follows:
(1) in container, add pentaerythrite, water and cosolvent, under stirring, be heated to 50～80 DEG C, then drip benzaldehyde, secondThe mixed liquor of nitrile and hydrochloric acid solution, time for adding 0.5～1h, after dropping finishes, continues insulation reaction 2～5h; Wherein: season pentaThe mol ratio of tetrol and benzaldehyde is 1:1～1:6; The addition of water is 20-40L/mol pentaerythrite; The addition of cosolventIt is 5～20L/mol pentaerythrite; The addition of acetonitrile is 10～20L/mol benzaldehyde; Hydrochloric acid solution is the hydrochloric acid of 8-12wt%Solution, hydrochloric acid solution addition is 5～15L/mol benzaldehyde;
(2) under stirring, reactant liquor is naturally cooled to 20～30 DEG C, suction filtration, washing afterwards, and dry at 60～80 DEG C,To pentaerythrite list condensing benzaldehyde.
2. preparation method according to claim 1, is characterized in that, in step (1), mixing speed is 100～250r/min.
3. preparation method according to claim 1, is characterized in that, in step (1), described cosolvent is acetonitrile.
4. preparation method according to claim 1, is characterized in that, in step (2), mixing speed is 50～100r/min.
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| CN201510836633.0A CN105601610A (en) | 2015-11-26 | 2015-11-26 | Preparation method for monobenzalpenlpentaerythritol |
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| CN201510836633.0A CN105601610A (en) | 2015-11-26 | 2015-11-26 | Preparation method for monobenzalpenlpentaerythritol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010833A (en) * | 2019-05-29 | 2020-12-01 | 北京化工大学 | Bisphthalonitrile compound containing acetal structure, polymer, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634924A (en) * | 2004-09-27 | 2005-07-06 | 天津理工大学 | Chiral acetal and ketal compounds and their synthesis method and use |
| CN102272116A (en) * | 2009-01-09 | 2011-12-07 | 三菱瓦斯化学株式会社 | Glycol compound having dioxane structure and manufacturing method therefor |
-
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- 2015-11-26 CN CN201510836633.0A patent/CN105601610A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634924A (en) * | 2004-09-27 | 2005-07-06 | 天津理工大学 | Chiral acetal and ketal compounds and their synthesis method and use |
| CN102272116A (en) * | 2009-01-09 | 2011-12-07 | 三菱瓦斯化学株式会社 | Glycol compound having dioxane structure and manufacturing method therefor |
Non-Patent Citations (1)
| Title |
|---|
| 刘芝兰，等，: "环状碳酸酯单体的合成及其聚合", 《武汉大学学报（理学版）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010833A (en) * | 2019-05-29 | 2020-12-01 | 北京化工大学 | Bisphthalonitrile compound containing acetal structure, polymer, preparation method and application thereof |
| CN112010833B (en) * | 2019-05-29 | 2021-12-03 | 北京化工大学 | Bisphthalonitrile compound containing acetal structure, polymer, preparation method and application thereof |
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