CN110183297A - A kind of preparation method of the general calixarenes intermediate of one's own physical property and its calixarenes intermediate of preparation - Google Patents
A kind of preparation method of the general calixarenes intermediate of one's own physical property and its calixarenes intermediate of preparation Download PDFInfo
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- CN110183297A CN110183297A CN201910606773.7A CN201910606773A CN110183297A CN 110183297 A CN110183297 A CN 110183297A CN 201910606773 A CN201910606773 A CN 201910606773A CN 110183297 A CN110183297 A CN 110183297A
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- calixarenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2076—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)- moiety is eliminated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/92—Systems containing at least three condensed rings with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes
Abstract
The invention discloses a kind of preparation method of one's own general calixarenes intermediate of physical property and its calixarenes intermediate of preparation, preparation method includes catalysis and extraction；The present invention has the advantages that by control formaldehyde and phenol derivatives it is annellated react in reaction temperature, catalyst type and solvent type, the polymer calixarene compound of high-purity, pre-selection determination is obtained, it includes neutral or cationic property content molecule that product, which has,.
Description
Technical field
The present invention relates to a kind of calixarenes intermediate, the system of specifically a kind of general calixarenes intermediate of one's own physical property
Preparation Method and its calixarenes intermediate of preparation, belong to calixarenes intermediate field.
Background technique
With the development of bioscience and medical science, centering is expedited the emergence of out to the research of enzyme and biochemical reaction in mankind's body
The wilderness demand of mesosome.However by becoming increasingly complex now with the biomolecule studied in medicine bioengineering, a variety of enzymes
It interacts more and more cumbersome with mechanism, traditional medicine intermediate is no longer able to provide suitable reaction for macromolecular biological enzyme
Space.Have to the intermediate of the molecule internal cavity with the width for being used to be formed Host-guest complex enough and depth urgent
It cuts and is difficult to the demand substituted.But only have seldom non-peptide type organic to possess at present can suitably to place macromolecular organic
The molecular configuration of the cavity of object, and cost is higher and since structure is complicated, it is more difficult to which nuclear-magnetism or infrared determination its structure are composed by hydrogen
Property.
Summary of the invention
To solve the above-mentioned problems, the present invention devise a kind of general calixarenes intermediate of one's own physical property preparation method and
Its calixarenes intermediate prepared, by control formaldehyde and phenol derivatives it is annellated react in reaction temperature, catalyst kind
Class and solvent type obtain the polymer calixarene compound of high-purity, pre-selection determination.
The technical solution of the present invention is as follows:
A kind of preparation method of the general calixarenes intermediate of one's own physical property, comprising the following steps:
(a) the p- butylphenol for analyzing pure grade or Resorcino or pyrogallol are provided using the skeleton structure as calixarenes, with
And organic solvent or diphenyl ether that the carbon chain lengths quantitative range of the pure grade of analysis is 10-20；
(b) using sodium hydroxide, rubidium hydroxide or potassium hydroxide as catalyst, by p- butylphenol and formaldehyde or acetaldehyde carry out at
Cyclization synthesizes the polymer of the p- butylphenol of 99% purity or more；
(c) it is extracted by a toluene, ethyl alcohol or methanol, ethyl acetate and diphenyl ether, and sieves and diphenyl ether is taken to distill, prepare purity
For 99.9% or more calixarenes intermediate.
Further, the molal quantity ratio of step (2) formaldehyde or acetaldehyde and p- butylphenol is 1-0.5, preferably
, when molal quantity ratio is 0.6, feed stock conversion highest.
Further, in the step (2), the catalyst accounts for the 1-5% of reactant gross mass；Reaction temperature should be 90
DEG C between 300 DEG C, at 150 DEG C of reaction temperature or more, butylphenol tetramer quantity is significantly more than eight aggressiveness of butylphenol, when
When reaction temperature is 270 DEG C, all products are the tetramer.
Further, carbon chain length quantitative range is 10-20 organic solvent or diphenyl ether etc., which can be used as, prepares cup virtue
The organic solvent of hydrocarbon；The organic solvent that wherein carbon chain length quantity is 10-15 may be used as preparation because its boiling point is lower with p-
Octyl phenol, p- tert-butyl phenol, the eight aggressiveness calixarenes and six aggressiveness calixarenes that p- tert-amyl phenol is raw material；Carbochain long number
Amount be 16-20 or diphenyl ether can as p- octyl phenol, p- tert-butyl phenol, p- tert-amyl phenol, p- hexamethylene phenol,
P- benzylphenol and p- phenylphenol are the preparation of the tetramer, six aggressiveness and eight aggressiveness of raw material.
Preferably, tetramer calixarenes uses potassium hydroxide as catalyst.
Six aggressiveness and eight aggressiveness calixarenes can choose sodium hydroxide, potassium hydroxide or rubidium hydroxide as catalyst.
High-purity calixarenes intermediate and benzene and its derivative generate weak interaction force, to adsorb benzene and its derivative
Object.
High-purity calixarenes intermediate includes being located at by the phenolic molecules and junction of the concatenated journey annular arrangement of methyl
The molecular configuration at the ortho position of hydroxyl, the tetramer, six aggressiveness and eight dimeric structures including similar configuration.Wherein, the tetramer, six
Aggressiveness, eight aggressiveness include: by methyl or the concatenated p- octyl phenol of ethyl, p- tert-butyl phenol, p- tert-amyl phenol, p- hexamethylene
Alkane phenol, p- benzylphenol and p- phenylphenol.Wherein by the concatenated p- octyl phenol of methyl, p- tert-butyl phenol, uncle p- penta
Base phenol molecular shape is the cup type cone in part.
The present invention utilizes formaldehyde, acetaldehyde solution, utilizes molecule different location pole caused by various functional groups
Property variation come control reaction in aldehyde-benzene contraposition replace position, to prepare pure calixarenes；By control temperature,
The reaction conditions such as catalyst, which generate, has the calixarenes intermediate for presetting chain length and aggressiveness quantity.
Calixarenes prepared by the present invention has the characteristics that prepare and have comprising neutral or cationic property content molecule.
Wherein the hydrophobic functional groups of the top edge of molecule can be reacted by Friedel-Crafts and its back reaction is substituted, and be possessed
The potential quality coupled with neutral molecule.And the hydroxyl of lower edge therein is also used to combine or shift organic point with positive electricity
Son or atom.Replace the hydroxyl for falling down edge that can adjust change esters, ketone and amino-compound concatenated by methyl
Phenolic molecules are formed by the shape of calixarenes, are able to the packet that selectivity receives potassium ion or sodium ion to be made
The spherical calixarenes of the functional group containing cation and crown calixarenes.Wherein, spherical calixarenes can be with sodium ion, potassium ion and rubidium
The stable complex of kinetics of ion formation.Possess excellent and not replaceable performance, can be widely applied to medicine and chemical industry
Intermediate.
The molal quantity ratio of formaldehyde or acetaldehyde and phenol type substances is excessive phenol type substances between the range of 1-0.5
It is excessive to may cause final product impurity.
The present invention also provides a kind of one's own general calixarenes intermediates of physical property, are prepared by the above method.
The present invention has the advantages that by control formaldehyde and phenol derivatives it is annellated react in reaction temperature, catalysis
Agent type and solvent type, obtain the determining polymer calixarene compound of high-purity, pre-selection, product have comprising neutral or
Cationic property content molecule.
Below with reference to embodiment, the invention will be further described.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
The percentage sign " % " being related in the present invention refers to mass percent if not specified；But the percentage of solution,
Unless otherwise specified, refer to and contain several grams of solute in solution 100ml；Percentage between liquid, capacity when referring to 20 DEG C
Ratio.
100 grams of purity are 95% or more by embodiment 1 and are free of the p- tert-butyl phenol of organic acid substance, and 2 milliliters molten
The aqueous solution and 60 milliliter of 37% formalin for having solved the potassium hydroxide that 0.67 gram of purity is 99% or more are placed in stirring
Device in the sealing reaction kettle of electroheat pair, is heated to 110 degree, and revolving speed is adjusted to 50 to 1000rpm, continues 2 hours, until uncle p-
Butylphenol, which is dissolved completely in solvent, generates clear solution.Solution is transferred to non-tight reaction of the non-tight with thermocouple to hold
In device, a large amount of nitrogen are passed through to reaction system and liquid level, are heated to 150 degree, continues 2 hours.Period solution can gradually become
Sticky, reaction kettle wall has drop precipitation, and ultimately forms yellow transparent crystallization.Crystallization is taken out, is placed in comprising blender, electricity
Thermocouple and solution have in the sealing reaction kettle of condenser, are passed through nitrogen, and 1500 milliliters of diphenyl ether revolving speeds are added and adjust to 100rpm-
500rpm, temperature rise to 160 degree, continue 6 hours.Yellow crystal is dissolved in diphenyl ether in reaction process, forms clear solution,
As reaction continuation solution is opaque by the colorless and transparent coffee color that is gradually transformed into, stops reaction at this time, be cooled to room temperature.It is added
2000 milliliters of ethyl acetate extract diphenyl ether, and vacuum filtration obtains light yellow planar product, with 50 milliliter of 20% chlorohydric acid pickling, 100
5% solution of potassium carbonate of milliliter and 100 milliliters of distilled water wash away impurity.Finally obtain pure eight aggressiveness calixarenes of p- tert-butyl.
100 grams of purity are 95% or more by embodiment 2 and are free of the p- tert-butyl phenol of organic acid substance, and 2 milliliters molten
The aqueous solution and 60 milliliter of 37% formalin for having solved the potassium hydroxide that 0.67 gram of purity is 99% or more are placed in stirring
Device is heated to 110 degree, and revolving speed is adjusted to 50 to 1000rpm, continues 2 hours, until p- tert-butyl phenol is dissolved completely in solvent
Generate clear solution.Solution is transferred to non-tight to have in the non-tight reaction vessel of thermocouple, to reaction system and liquid
Face is passed through a large amount of nitrogen, is heated to 150 degree, continues 2 hours.Period solution can gradually become sticky, and reaction kettle wall has drop
It is precipitated, and ultimately forms yellow transparent crystallization.Crystallization is taken out, is placed in comprising blender, electroheat pair and solution has condenser
It seals in reaction kettle, is passed through nitrogen, 1500 milliliters of diphenyl ether revolving speeds are added and adjust to 100rpm-500rpm, temperature rises to 230
Degree, continues 6 hours.Yellow crystal is dissolved in diphenyl ether in reaction process, formed clear solution, with reaction continue solution by
Colorless and transparent to be gradually transformed into coffee-like opaque, continuous heating is opaque to aterrimus, stops reaction at this time, is cooled to room
Temperature.2000 milliliters of ethyl acetate are added and extract diphenyl ether, vacuum filtration obtains white planar product, with 50 milliliter of 20% hydrochloric acid acid
It washes, 100 milliliter of 5% solution of potassium carbonate and 100 milliliters of distilled water wash away impurity.Finally obtain pure six aggressiveness of p- tert-butyl
Calixarenes.
100 grams of purity are 95% or more by embodiment 3 and are free of the p- tert-butyl phenol of organic acid substance, and 2 milliliters molten
The aqueous solution and 60 milliliter of 37% formalin for having solved the potassium hydroxide that 0.67 gram of purity is 99% or more are placed in stirring
Device, revolving speed are adjusted to 50 to 1000rpm, continue 2 hours, until p- tert-butyl phenol be dissolved completely in solvent generate it is transparent molten
Liquid.Solution is transferred to non-tight in the non-tight reaction vessel of thermocouple, is passed through largely to reaction system and liquid level
Nitrogen is heated to 150 degree, continues 2 hours.Period solution can gradually become sticky, and reaction kettle wall has drop precipitation, and final
Form yellow transparent crystallization.Crystallization is taken out, is placed in comprising blender, electroheat pair and solution have the sealing reaction kettle of condenser
In, it is passed through nitrogen, 1500 milliliters of diphenyl ether revolving speeds are added and adjust to 100rpm-500rpm, temperature rises to 290 degree, and it is small to continue 24
When.Yellow crystal is dissolved in diphenyl ether in reaction process, formed clear solution, with reaction continue solution by it is colorless and transparent by
Gradually it is transformed into coffee-like opaque, continuous heating to the transparent supernatant liquid of aterrimus, stops reaction at this time, be cooled to room temperature.Add
Enter the product dissolved in 2000 milliliters of acetone extract diphenyl ether, vacuum filtration obtains white crystalline product, with 50 milliliter of 20% salt
Pickling, 100 milliliter of 5% solution of potassium carbonate and 100 milliliters of distilled water wash away impurity.Finally obtain pure p- tert-butyl four
Aggressiveness calixarenes.
176 grams of purity are the p- phenylphenol that organic acid substance is free of in 95% or more and impurity, 2 millis by embodiment 4
Rise the aqueous solution for having dissolved 0.5 gram of sodium hydroxide and 60 milliliter of 37% formalin be placed in blender, electroheat pair it is close
It seals in reaction kettle, is heated to 110 degree, revolving speed is adjusted to 50 to 1000rpm, continues 2 hours, until p- tert-butyl phenol is completely dissolved
Yellow solution is generated in solvent.Solution is transferred to non-tight to have in the non-tight reaction vessel of thermocouple, to reactant
System and liquid level are passed through a large amount of nitrogen, are heated to 150 degree, continue 2 hours.Period solution can gradually become sticky, reaction kettle wall
Drop precipitation is had, and ultimately forms yellow transparent crystallization.Crystallization is taken out, is placed in comprising blender, electroheat pair and solution has
In the sealing reaction kettle of condenser, it is passed through nitrogen, 1500 milliliters of diphenyl ether revolving speeds are added and adjust to 100rpm-500rpm, temperature
290 degree are risen to, continues 96 hours.Yellow crystal is dissolved in diphenyl ether in reaction process, formed clear solution, with reaction after
Continuous solution is gradually transformed into light yellow clear clear solution by colorless and transparent, stops reaction at this time, is cooled to room temperature.It is added 2000
Milliliter ethyl acetate extracts diphenyl ether, and vacuum filtration obtains white crystalline product, with 50 milliliter of 20% chlorohydric acid pickling, 100 milliliter 5%
Solution of potassium carbonate and 100 milliliters of distilled water wash away impurity.Finally obtain pure p- tert-butyl tetramer calixarenes.
Product purpose: in the cyclic structure of calixarenes, bottom has the close and regular hydrophilic hydroxy group official that arranges
It can roll into a ball, may be selected by organic transition metal catalyst and containing halogen organic to replace contraposition functional group, conveniently big point
The modification of sub- organic matter.The hydrophobic functional groups of its underpart also provide the excellent weak molecule with organic solvent or organic molecule
Binding force, facilitate its nonpolarity or human body environment in the combination of molecule to promote to react.Cavity in it, which provides, to be held
The internal environment of larger molecular organics and the physicochemical property due to its cavity are received or fixed, the molecule is made to possess outstanding cation
Transportation function.It is miscellaneous Subjective and Objective molecule class can be formed by hydrogen bond or other weak molecular force with organic neutral molecule or anion
Ring, macrocyclic compound.The cavity size of its molecule can manually be finely tuned by control reaction temperature to adjust phenol molecular amounts.
And unique containing functional group in entire molecule, Yi Jinhang chemical modification or modification.Special functional group can pass through displacement
The reaction formings such as substitution have the functional group of most of specific function, and structural property is stablized, and is easy to crystallize to obtain high-purity
Reactant is not necessarily to column separation.
Raw materials used in the present invention is to commonly use raw material in the production of this field, can be obtained from market, and for production
As a result it will not have an impact；Various equipment employed in the present invention are conventional equipment used in the production technology of this field,
And operation, the parameter etc. of each equipment are carried out according to routine operation, have no special feature.
Claims (7)
1. a kind of preparation method of the general calixarenes intermediate of one's own physical property, which comprises the following steps:
(a) p- butylphenol, Resorcino or the pyrogallol of analyzing pure grade are provided using the skeleton structure as calixarenes, and
Analyze the organic solvent or diphenyl ether that the carbon chain lengths quantitative range of pure grade is 10-20；
(b) using sodium hydroxide, rubidium hydroxide or potassium hydroxide as catalyst, by p- butylphenol and formaldehyde or acetaldehyde carry out at
Cyclization synthesizes the polymer of the p- butylphenol of 99% purity or more；
(c) it is extracted by a toluene, ethyl alcohol or methanol and ethyl acetate and diphenyl ether, and sieves and diphenyl ether is taken to distill, prepared pure
The calixarenes intermediate that degree is 99.9% or more.
2. a kind of preparation method of one's own general calixarenes intermediate of physical property according to claim 1, it is characterised in that: institute
The molal quantity ratio for stating step (2) formaldehyde or acetaldehyde and p- butylphenol is 1-0.5.
3. a kind of preparation method of one's own general calixarenes intermediate of physical property according to claim 1, it is characterised in that: institute
It states in step (2), the catalyst accounts for the 1-5% of reactant gross mass；Reaction temperature should be between 90 DEG C to 300 DEG C.
4. a kind of preparation method of one's own general calixarenes intermediate of physical property according to claim 1, it is characterised in that: carbon
The organic solvent or diphenyl ether that chain length quantitative range is 10-20 are as the organic solvent for preparing calixarenes；Wherein carbochain long number
The organic solvent that amount is 10-15 is used as preparation using p- octyl phenol, p- tert-butyl phenol, p- tert-amyl phenol as the eight of raw material
Aggressiveness calixarenes and six aggressiveness calixarenes；Carbon chain length quantity is 16-20 or diphenyl ether is as p- octyl phenol, p- tert-butyl benzene
Phenol, p- tert-amyl phenol, p- hexamethylene phenol, p- benzylphenol and p- phenylphenol be the tetramer of raw material, six aggressiveness and
The preparation of eight aggressiveness.
5. a kind of preparation method of one's own general calixarenes intermediate of physical property according to claim 4, it is characterised in that: four
Aggressiveness calixarenes uses potassium hydroxide as catalyst.
6. a kind of preparation method of one's own general calixarenes intermediate of physical property according to claim 4, it is characterised in that: six
Aggressiveness and eight aggressiveness calixarenes select sodium hydroxide, potassium hydroxide or rubidium hydroxide as catalyst.
7. a kind of general calixarenes intermediate of one's own physical property, it is characterised in that: by preparation as claimed in any one of claims 1 to 6
Method is prepared.
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| FR2795077A1 (en) * | 1999-06-18 | 2000-12-22 | Orapi Socodi | Cation complexing agent comprising optionally O-functionalized p-isopropyl-calix(4-14)arene, useful as anionic or radical polymerization accelerator, especially in cyanoacrylate adhesives |
| TW200905398A (en) * | 2007-04-27 | 2009-02-01 | Idemitsu Kosan Co | Photoresist base material and photoresist composition containing the same |
| JP2013107841A (en) * | 2011-11-18 | 2013-06-06 | Mitsubishi Gas Chemical Co Inc | Cyclic compound, manufacturing method for the same, radiation-sensitive composition and method for forming resist pattern |
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Application publication date: 20190830 |