CN116693543A - Calixarene-derived supermolecule macrocyclic host compound, preparation method and application thereof - Google Patents
Calixarene-derived supermolecule macrocyclic host compound, preparation method and application thereof Download PDFInfo
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- CN116693543A CN116693543A CN202310502457.1A CN202310502457A CN116693543A CN 116693543 A CN116693543 A CN 116693543A CN 202310502457 A CN202310502457 A CN 202310502457A CN 116693543 A CN116693543 A CN 116693543A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 title abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 sodium carboxylate Chemical class 0.000 claims abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 11
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000003419 tautomerization reaction Methods 0.000 claims abstract description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- 150000004985 diamines Chemical class 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 101100327917 Caenorhabditis elegans chup-1 gene Proteins 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 150000001924 cycloalkanes Chemical class 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- GQPLZGRPYWLBPW-UHFFFAOYSA-N calix[4]arene Chemical compound C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 GQPLZGRPYWLBPW-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 238000001212 derivatisation Methods 0.000 abstract description 6
- 239000002775 capsule Substances 0.000 abstract description 4
- 239000007858 starting material Substances 0.000 abstract description 3
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 241001120493 Arene Species 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005710 macrocyclization reaction Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- IQQUSROZGZWBLI-OUKQBFOZSA-N 1-ethyl-4-[(e)-2-(4-methylphenyl)ethenyl]benzene Chemical compound C1=CC(CC)=CC=C1\C=C\C1=CC=C(C)C=C1 IQQUSROZGZWBLI-OUKQBFOZSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 description 1
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/22—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/16—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring
- C07C13/18—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring with a cyclohexane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/24—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a seven-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/26—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with an eight-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/271—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a nine- to ten- membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a supermolecule macrocyclic main body compound derived from calixarene, a preparation method and application thereof, wherein resorcinol derivatives are used as starting materials, sodium carboxylate is introduced at the lower edge through oxidation reaction and hydrolysis reaction to achieve water solubility of the macrocyclic main body molecule, thiourea groups are introduced at the upper edge through condensation with diamine, so that molecular calix cannot stably form hydrogen bond capsules in the aspect of thioketone-thiol tautomerism, and further derivatization at the upper edge is allowed. The method has the advantages of simple route process, easily obtained raw materials, mild reaction conditions, high yield and good repeatability. The molecular cup has better water solubility, and simultaneously provides a hydrophobic cavity capable of containing guest molecules, and can identify straight-chain alkane, carboxylic acid, alcohol, cycloparaffin derivatives and guests with polar functional groups in water, and the conformation of the guests can be pre-organized through the cavity to carry out intramolecular cyclization reaction; has potential application prospect in molecular reaction vessels and biosensing.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a water-soluble benzimidazole mercapto molecular cup, a preparation method and application thereof.
Background
Calixarenes are macrocyclic oligomers formed from a phenol monomer linked via a methylene group at the ortho position to a phenolic hydroxyl group, and are structurally similar to Greek's calix (Calixcrater) and are known as calixarenes, which are commonly referred to as calix [ n ] arenes, where n represents the number of macrocyclic phenol monomers, typically n=4, 6,8, most commonly calix [4] arenes and calix [6] arenes.
In calixarene molecules, the upper edge is composed of para-position substituents of benzene rings, the lower edge is generally composed of phenolic hydroxyl groups which are regularly arranged, the calixarene has hydrophilicity, the middle is a hydrophobic electron-rich cavity composed of benzene rings, and compared with the prior two generations of supermolecule main bodies, the calixarene has the following advantages:
1. the calixarene is convenient and fast to synthesize, the raw materials are cheap and easy to obtain, and the research is convenient to develop;
2. has larger molecular weight, thus having high melting point, good chemical stability and lower toxicity;
3. the derivatization is easy, the structure determines that the para substituent of the upper benzene ring, the lower phenolic hydroxyl and the methylene between the benzene rings can be selectively modified, so that the solubility, the cavity size and other physical and chemical properties of the material can be adjusted;
4. the hydrophobic cavity can be adjusted for different guest molecules, and can complex various small molecular compounds;
5. the conformation is rich, various conformations exist, and the required conformation can be fixed by chemical modification and conditions such as temperature, pH and the like.
The cavity of the molecular cup can adapt to more types of guest molecules, so that the synthesis of the water-soluble molecular cup is gradually focused by researchers, and the construction of the existing molecular cup cavity is often accompanied by pi-pi stacking, so that the water solubility of host molecules is poor.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a calixarene-derivatized supermolecule macrocyclic host compound, a preparation method and application thereof, wherein the compound has better water solubility and can selectively identify hydrophobic molecules in water. The invention relates to a preparation method of supermolecule with better water solubility, which introduces thiourea group at the upper edge of water-soluble molecular cup, and the thioketone-mercaptan tautomerism allows the further derivatization of the upper edge.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a calixarene-derived supermolecule macrocyclic host compound takes resorcinol calixarene [4] as a core, can be dissolved in water, has a hydrophobic cavity structure capable of containing a guest molecule, has tautomerism of thiourea groups at the upper edge, and has the following molecular calixarene 1 compound structure:
preferably, when the calixarene-derivatized supermolecular macrocyclic host compound of the present invention has the structure of molecular calix 1, the supermolecular macrocyclic host compound has two conformations in water: the device has a C4v symmetrical 'vase' conformation and a C2v symmetrical 'kite' conformation, wherein dynamic balance exists between the two conformations, the 'vase' conformation is provided with a cavity capable of containing a guest, and the guest molecules are wrapped in the cavity of the supermolecular cup.
The invention discloses a preparation method of a calixarene-derived supermolecule macrocyclic main body compound, which takes resorcinol or a derivative thereof as an initial reaction raw material to prepare a water-soluble thiourea molecular calixarene compound, sodium carboxylate is introduced at the lower edge of a compound molecule through oxidation reaction and hydrolysis reaction to achieve the water solubility of the whole compound molecule, and thiourea groups are introduced at the upper edge of the compound molecule through condensation with diamine to obtain the 2-mercaptobenzimidazole molecular calixarene compound.
Preferably, the preparation method of the calixarene-derivatized supermolecule macrocyclic host compound comprises the following synthesis steps:
a. at a low temperature of not higher than 0 ℃, adding the octa-amino hydrochloride precursor of the ester foot into a double-neck round bottom flask in an ice bath, replacing nitrogen for at least 3 times, adding anhydrous tetrahydrofuran, and fully stirring to uniformly disperse the raw materials; replacing nitrogen for at least 3 times again, adding carbon disulfide into the reaction system, and then adding a tetrahydrofuran solution of potassium tert-butoxide; then the reaction system is restored to room temperature, and the temperature is slowly raised to the reflux temperature not lower than 80 ℃, and the reaction system is heated and refluxed for at least 48 hours; then carrying out post-treatment, cooling the reaction mixture to room temperature, slowly adding water and acetic acid, stirring for at least 1 hour, adding a large amount of water to precipitate a product, filtering, washing a filter cake with water for at least 3 times, washing the filter cake with methanol for at least 3 times, refluxing the obtained solid with methanol for at least 24 hours, filtering, collecting the solid, and drying to obtain a solid product;
b. adding the solid product prepared in the step a into another round bottom flask, replacing nitrogen at least 3 times, adding ethanol and tetrahydrofuran mixed solvent, replacing nitrogen at least 3 times again, and then adding sodium hydroxide aqueous solution at the temperature of not higher than 0 ℃; the reaction mixture is then moved to a temperature of not less than 40 ℃ and stirred for at least 12 hours; returning to room temperature, then centrifuging the resulting solid and washing with acetone at least 3 times; the recovered solid was suspended in acetone, then vigorously stirred and heated at 80 ℃ or higher under reflux for at least 1 hour, the suspension was cooled to room temperature, filtered, washed with acetone, and dried under vacuum to give a white solid molecular cup 1 compound.
Preferably, in step a, after the octaamino hydrochloride precursor of the ester foot is added to the two-neck round bottom flask, the vacuum degree of the pumping process of displacing nitrogen is not less than 0.09MPa.
Preferably, in step a, the concentration of potassium tert-butoxide in the tetrahydrofuran solution of potassium tert-butoxide added is not less than 1mol/L.
Preferably, in step a, the equivalent ratio of octaamino hydrochloride precursor of the ester foot, carbon disulphide to potassium tert-butoxide is 1:255:30.
preferably, in step a, the post-treatment of the octaamino hydrochloride precursor per 0.065mol of ester foot requires the addition of at least 0.5mL of water and 2mL of acetic acid.
Preferably, in step b, the solid product prepared in step a and the reactants of sodium hydroxide are mixed in a mass ratio of 1:5-10, wherein the concentration of the aqueous solution of sodium hydroxide is not less than 1mol/L, and the volume ratio of ethanol to tetrahydrofuran is 1:1.
The use of a calixarene-derivatized macrocyclic supramolecular host compound of the invention, having a hydrophobic cavity capable of accommodating a guest molecule, is capable of recognizing linear alkanes, carboxylic acids, alcohols, cycloalkanes, cycloalkane derivatives, and guests bearing polar functional groups, and is capable of performing intramolecular cyclization by pre-organizing the conformation of the guest via the cavity.
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. the molecular cup 1 provided by the invention has a hydrophobic cavity, can identify straight-chain alkane, carboxylic acid, alcohol, cycloparaffin derivative and object with polar functional groups, and can perform cyclization reaction by pre-organizing the conformation of the object through the cavity;
2. the tautomerism of thiourea and mercaptan exists at the upper edge of the molecular cup 1, so that the molecular cup can be further derivatized, and has potential application prospects in the aspects of molecular reaction containers and biosensing.
3. The synthesis route of the invention has simple and convenient process, easily obtained raw materials, mild reaction conditions, high yield and good repeatability.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of benzimidazole sulfhydryl molecular cup precursor.
FIG. 2 is a nuclear magnetic resonance spectrum of benzimidazole thiol molecular cup precursor.
FIG. 3 is a high resolution mass spectrum of benzimidazole thiol molecular cup precursors.
FIG. 4 is a nuclear magnetic resonance diagram of a water-soluble benzimidazole sulfhydryl molecular cup.
FIG. 5 is a nuclear magnetic resonance chart of a water-soluble benzimidazole sulfhydryl molecular cup.
FIG. 6 is a high resolution mass spectrum of a water-soluble benzimidazole thiol molecular cup.
FIG. 7 is a nuclear magnetic resonance spectrum of a linear alkane complexed in molecular cup 1.
FIG. 8 is a nuclear magnetic resonance spectrum of a molecular cup 1 complexed cycloalkane.
FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of a molecular cup 1 complexed stilbene derivative.
FIG. 10 is a nuclear magnetic resonance hydrogen spectrum of a macrocyclization reaction of an alkyl diamine with an NHS ester within molecular cup 1.
Fig. 11 is a schematic molecular structure of the molecular cup 1.
Detailed Description
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
embodiment one:
in this example, a calixarene-derivatized macrocyclic supramolecular host compound. The molecular cup 1 has the following structural formula:
the preparation method of the macrocyclic supermolecule main body compound derivatized by calixarene of the embodiment takes octaamino hydrochloride precursor of ester foot as initial reaction raw material to prepare water-soluble mercaptobenzimidazole molecular calixarene, and introduces sodium carboxylate through hydrolysis reaction at the lower edge to achieve water solubility as a whole, and introduces different thiourea groups through condensation of carbon disulfide and diamine at the upper edge to obtain the 2-mercaptobenzimidazole molecular calixarene. The synthesis method comprises the following steps:
the preparation method of the calixarene-derivatized macrocyclic supermolecule host compound comprises the following synthesis steps:
a. at the low temperature of 0 ℃, adding the octa-amino hydrochloride precursor of the ester foot into a double-neck round bottom flask in an ice bath, replacing nitrogen for three times, adding anhydrous tetrahydrofuran, and fully stirring to uniformly disperse the raw materials; replacing nitrogen for three times again, adding carbon disulfide into the reaction system, and then adding a tetrahydrofuran solution of potassium tert-butoxide; then the reaction system is restored to room temperature, and the temperature is slowly raised to the reflux temperature of 80 ℃, and the reaction system is heated and refluxed for 48 hours; then carrying out post-treatment, cooling the reaction mixture to room temperature, slowly adding water and acetic acid, stirring for 1 hour, adding a large amount of water to precipitate a product, filtering, washing a filter cake with water for 3 times and then methanol for 3 times, refluxing the obtained solid with methanol for 24 hours, filtering, collecting the solid, and drying to obtain a solid product;
the pressure of the pumping process of replacing nitrogen is 0.1 atmosphere;
the concentration of the added potassium tert-butoxide in the tetrahydrofuran solution of the potassium tert-butoxide is 1mol/L;
the equivalent ratio of octaamino hydrochloride precursor of ester foot, carbon disulfide and potassium tert-butoxide is 1:255:30;
post-treatment of the octaamino hydrochloride precursor per 0.065mol of ester foot requires addition of 0.5mL of water and 2mL of acetic acid;
b. adding the solid product prepared in the step a into another round bottom flask, replacing nitrogen for 3 times, adding ethanol and tetrahydrofuran mixed solvent, replacing nitrogen for 3 times again, and then adding sodium hydroxide aqueous solution at 0 ℃; the reaction mixture was then moved to 40 ℃ and stirred for 12 hours; returning to room temperature, then centrifuging the resulting solid and washing with acetone 3 times; suspending the recovered solid in acetone, stirring vigorously and heating at 80deg.C under reflux for 1 hr, cooling the suspension to room temperature, filtering, washing with acetone, and drying under vacuum to obtain white solid molecular cup 1; the molecular cup 1 has the structural formula:
the spatial structure is shown in fig. 11;
the mixing mass ratio of the solid product prepared in the step a to the reactant of sodium hydroxide is 1:10, wherein the concentration of the sodium hydroxide aqueous solution is not lower than 1mol/L, and the volume ratio of ethanol to tetrahydrofuran is 1:1.
In this example, the intermediate product of step a is characterized, 1 H NMR(600MHz,DMSO-d 6 )δ12.04(s,8H),8.09–7.41(m,16H),5.33(s,4H),4.02(q,J＝7.6Hz,7H),2.57(q,8H),2.23(t,8H),1.17(t,12H). 13 C NMR(150MHz,DMSO-d 6 )δ173.26,169.19,155.59,147.95,134.84,129.65,125.15,116.80,105.61,60.62,33.26,32.59,27.32,14.39.HRMS(ESI):Calcd for chemical formula C 76 H 64 N 8 O 16 S 4 :1472.3323,found:1473.3386[M+H] + ；
in this example, the final product molecular cup 1 is characterized, 1 H NMR(600MHz,D 2 O/DMSO-d 6 :10/1)δ7.49(s,4H),7.47(s,4H),7.39(s,8H),5.48(t,J＝8.4Hz,4H),2.45(q,J＝7.8Hz,8H),2.04(t,J＝7.8Hz,8H). 13 C NMR(151MHz,D 2 O/DMSO-d 6 :10/1)δ182.16,166.29,155.48,146.57,135.57,124.21,116.74,106.34,35.82,33.41,30.30,28.25.HRMS(ESI):Calcd for chemical formula C 68 H 48 N 8 O 16 S 4 :1360.2071,found:1361.2157[M+H] + 。
experimental test analysis:
molecular cup 1 (14.48 mg, 10.00. Mu. Mol) was added to a 25mL sample bottle, 10mL of heavy water was added thereto, and the whole was dissolved by sonication to give a clear and transparent colorless solution (1 mmol/L).
Adding 500 mu L of the solution into a nuclear magnetic tube, adding 5 mu L of a 100mmol/L object heavy water solution into the nuclear magnetic tube, mixing the solutions, and measuring 298K nuclear magnetic resonance hydrogen spectrum on a Bruker AVANCE III HD 600M machine, wherein the scanning spectrum width is set to be 20, the center is set to be 4, and the scanning times are set to be 64 times.
FIG. 1 is a nuclear magnetic resonance spectrum of benzimidazole sulfhydryl molecular cup precursor. FIG. 2 is a nuclear magnetic resonance spectrum of benzimidazole thiol molecular cup precursor. FIG. 3 is a high resolution mass spectrum of benzimidazole thiol molecular cup precursors. FIG. 4 shows a nuclear magnetic resonance hydrogen spectrum of the molecular cup 1. FIG. 5 is a nuclear magnetic resonance spectrum of the molecular cup 1. Fig. 6 is a high resolution mass spectrum of the molecular cup 1.
FIG. 7 is a nuclear magnetic resonance spectrum of a linear alkane recognition of a guest (excess) complexed by molecular cup 1 (1 mmol/L, 500. Mu.L). The method comprises the following steps from bottom to top:
a) Molecular cup 1 and n-hexane;
b) Molecular cup 1 and n-heptane;
c) Molecular cup 1 and n-octane;
d) Molecular cup 1 and n-nonane;
e) Molecular cup 1 and n-decane.
FIG. 8 is a nuclear magnetic resonance spectrum of molecular cup 1 (1 mmol/L, 500. Mu.L) for recognition of cycloalkanes complexed to a guest (excess). The method comprises the following steps from bottom to top:
a) Molecular cup 1 and cyclohexane;
b) Molecular cup 1 and cycloheptane;
c) Molecular cup 1 and cyclooctane;
d) Molecular cup 1 and cyclononane;
e) Molecular cup 1 and cyclodecane.
FIG. 9 shows nuclear magnetic resonance spectra of molecular cup 1 complexed with stilbene derivative, from bottom to top:
a) Molecular cup 1 and trans-4, 4' -dimethyl stilbene;
b) Molecular cup 1 and trans-4-ethyl-4' -methyl stilbene;
c) Molecular cup 1 and trans-4-isopropyl-4' -methyl stilbene.
The high intensity of the shielding afforded by the host cavity in the structure of the compound, the chemical shift of the guest molecule will shift to a high field in the nuclear magnetic spectrum, which will tend to result in a nuclear magnetic signal of the guest molecule hydrogen after 0ppm, see fig. 7.
FIG. 10 is a nuclear magnetic resonance hydrogen spectrum of a macrocyclization reaction of an alkyl diamine with an NHS ester within molecular cup 1.
According to the preparation method of the molecular cup with good water solubility, the thiourea group is introduced into the upper edge of the water-soluble molecular cup, so that the property of the upper edge of the cavity is changed, the thioketone-mercaptan tautomerism enables the molecular cup to be incapable of stably forming a hydrogen bond capsule, and further derivatization of the upper edge is allowed. In the preparation method of the water-soluble benzimidazole mercapto molecular cup, octaamino hydrochloride precursor of ester footing is taken as a starting material, sodium carboxylate is introduced at the lower edge through hydrolysis reaction to achieve overall water solubility, thiourea groups are introduced at the upper edge through condensation with diamine, so that the molecular cup cannot stably form hydrogen bond capsules in the aspect of thioketone-mercaptan tautomerism, and further derivatization of the upper edge is allowed. The preparation method has the advantages of simple route process, easily obtained raw materials, mild reaction conditions, high yield and good repeatability.
Example two
The use of a calixarene-derivatized macrocyclic supramolecular host compound of the invention, having a hydrophobic cavity capable of accommodating a guest molecule, is capable of recognizing linear alkanes, carboxylic acids, alcohols, cycloalkanes, cycloalkane derivatives, and guests bearing polar functional groups, and is capable of performing intramolecular cyclization by pre-organizing the conformation of the guest via the cavity.
The tautomerism of thiourea and mercaptan exists at the upper edge of the molecular cup 1, so that the molecular cup can be further derivatized, and has potential application prospects in the aspects of molecular reaction containers and biosensing. The molecular cup compound of the embodiment has better water solubility, and simultaneously provides a hydrophobic cavity capable of containing guest molecules, and can recognize straight-chain alkane, carboxylic acid, alcohol, cycloparaffin derivatives and guest with polar functional groups in water, and cyclization reaction can be carried out by pre-organizing the conformation of the guest through the cavity; has potential application prospect in molecular reaction vessels and biosensing.
The above examples introduce sodium carboxylate salts at the lower edge of resorcinol derivatives as starting materials through oxidation and hydrolysis reactions to achieve water solubility of the macrocyclic host molecule, introduce thiourea groups at the upper edge through condensation with diamines, and thus the thioketone-thiol tautomerism does not allow stable formation of hydrogen bond capsules in the molecular cup, and on the other hand, allows further derivatization of the upper edge.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the embodiments described above, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principles of the technical solution of the present invention can be made according to the purpose of the present invention, and all the changes, modifications, substitutions, combinations or simplifications should be equivalent to the substitution, so long as the purpose of the present invention is met, and all the changes are within the scope of the present invention without departing from the technical principles and the inventive concept of the present invention.
Claims (10)
1. A calixarene-derivatized supramolecular macrocyclic host compound characterized by: resorcinol calix [4] arene is taken as a core, can be dissolved in water, has a hydrophobic cavity structure capable of containing guest molecules, and has tautomerism of thiourea groups at the upper edge, and the supermolecule macrocyclic host compound has the following molecular calix 1 compound structure:
2. the calixarene-derivatized supermolecular macrocyclic host compound of claim 1, wherein: when it has the structure of molecular cup 1, the supermolecular macrocyclic host compound has two conformations in water: with C 4v Symmetrical "vase" conformation and C 2v The symmetrical kite conformation has dynamic balance, and the vase conformation has cavity for holding the object and the object molecule is packed inside the cavity of the molecular cup.
3. A process for the preparation of a calixarene-derivatized supermolecular macrocyclic host compound as defined in claim 1, characterized in that: resorcinol or its derivative is used as initial reaction material to prepare water-soluble thiourea molecular cup compound, sodium carboxylate is introduced into the lower edge of compound molecule through oxidation reaction and hydrolysis reaction to obtain water-solubility of the whole compound molecule, and thiourea group is introduced into the upper edge of compound molecule through condensation with diamine to obtain 2-mercaptobenzimidazole molecular cup compound.
4. A process for the preparation of calixarene-derivatized supermolecular macrocyclic host compounds according to claim 3, comprising the following synthetic steps:
a. at a low temperature of not higher than 0 ℃, adding the octa-amino hydrochloride precursor of the ester foot into a double-neck round bottom flask in an ice bath, replacing nitrogen for at least 3 times, adding anhydrous tetrahydrofuran, and fully stirring to uniformly disperse the raw materials; replacing nitrogen for at least 3 times again, adding carbon disulfide into the reaction system, and then adding a tetrahydrofuran solution of potassium tert-butoxide; then the reaction system is restored to room temperature, and the temperature is slowly raised to the reflux temperature not lower than 80 ℃, and the reaction system is heated and refluxed for at least 48 hours; then carrying out post-treatment, cooling the reaction mixture to room temperature, slowly adding water and acetic acid, stirring for at least 1 hour, adding a large amount of water to precipitate a product, filtering, washing a filter cake with water for at least 3 times, washing the filter cake with methanol for at least 3 times, refluxing the obtained solid with methanol for at least 24 hours, filtering, collecting the solid, and drying to obtain a solid product;
b. adding the solid product prepared in the step a into another round bottom flask, replacing nitrogen at least 3 times, adding ethanol and tetrahydrofuran mixed solvent, replacing nitrogen at least 3 times again, and then adding sodium hydroxide aqueous solution at the temperature of not higher than 0 ℃; the reaction mixture is then moved to a temperature of not less than 40 ℃ and stirred for at least 12 hours; returning to room temperature, then centrifuging the resulting solid and washing with acetone at least 3 times; the recovered solid was suspended in acetone, then vigorously stirred and heated at 80 ℃ or higher under reflux for at least 1 hour, the suspension was cooled to room temperature, filtered, washed with acetone, and dried under vacuum to give a white solid molecular cup 1 compound.
5. The method for preparing a calixarene-derivatized supermolecule macrocyclic host compound as claimed in claim 4, wherein: in step a, after the octaamino hydrochloride precursor of the ester foot is added to the two-neck round bottom flask, the pressure of the pumping process of displacing nitrogen is not higher than 0.1 atmosphere.
6. The method for preparing a calixarene-derivatized supermolecule macrocyclic host compound as claimed in claim 4, wherein: in the step a, the concentration of the tetrahydrofuran solution of the added potassium tert-butoxide is not less than 1mol/L.
7. The method for preparing a calixarene-derivatized supermolecule macrocyclic host compound as claimed in claim 4, wherein: in said step a, the equivalent ratio of octaamino hydrochloride precursor of the ester foot, carbon disulphide to potassium tert-butoxide is 1:255:30.
8. the method for preparing a calixarene-derivatized supermolecule macrocyclic host compound as claimed in claim 4, wherein: in said step a, the post-treatment of the octaamino hydrochloride precursor per 0.065mol of ester foot requires the addition of at least 0.5mL of water and 2mL of acetic acid.
9. The method for preparing a calixarene-derivatized supermolecule macrocyclic host compound as claimed in claim 4, wherein: in the step b, the mixing mass ratio of the solid product prepared in the step a to the reactant of sodium hydroxide is 1:5-10, wherein the concentration of the sodium hydroxide aqueous solution is not lower than 1mol/L, and the volume ratio of ethanol to tetrahydrofuran is 1:1.
10. Use of a calixarene-derivatized supermolecular macrocyclic host compound as claimed in claim 1, characterized in that: the calixarene-derivatized supermolecule macrocyclic host compound has a hydrophobic cavity capable of accommodating guest molecules, can recognize linear alkanes, cycloalkanes, cycloalkane derivatives and guests with polar functional groups, and can perform intramolecular cyclization reaction by pre-organizing the conformation of the guest through the cavity.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232614A (en) * | 2018-10-26 | 2019-01-18 | 四川理工学院 | A kind of column [5] aromatic hydrocarbons-bis- cups [4] pyrroles's chirality supermolecule, preparation method and its application |
| CN113461701A (en) * | 2021-06-03 | 2021-10-01 | 上海大学 | Calixarene-derivatized supramolecular macrocyclic host compound, preparation method and application thereof |
| CN113512044A (en) * | 2021-06-03 | 2021-10-19 | 上海大学 | Water-soluble benzotriazole supermolecule cup compound, and preparation method and application thereof |
| CN115504988A (en) * | 2022-07-12 | 2022-12-23 | 上海大学 | Molecular cup macrocyclic host compound based on resorcinol calix [4] arene derivatization, and preparation method and application thereof |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232614A (en) * | 2018-10-26 | 2019-01-18 | 四川理工学院 | A kind of column [5] aromatic hydrocarbons-bis- cups [4] pyrroles's chirality supermolecule, preparation method and its application |
| CN113461701A (en) * | 2021-06-03 | 2021-10-01 | 上海大学 | Calixarene-derivatized supramolecular macrocyclic host compound, preparation method and application thereof |
| CN113512044A (en) * | 2021-06-03 | 2021-10-19 | 上海大学 | Water-soluble benzotriazole supermolecule cup compound, and preparation method and application thereof |
| CN115504988A (en) * | 2022-07-12 | 2022-12-23 | 上海大学 | Molecular cup macrocyclic host compound based on resorcinol calix [4] arene derivatization, and preparation method and application thereof |
Non-Patent Citations (9)
| Title |
|---|
| JI-MIN YANG等: "Rigidified Cavitand Hosts in Water: Bent Guests, Shape Selectivity, and Encapsulation", J. AM. CHEM. SOC., 11 November 2021 (2021-11-11), pages 19517 * |
| JI-MIN YANG等: "Selective Macrocycle Formation in Cavitands", J. AM. CHEM. SOC., 28 January 2021 (2021-01-28), pages 2190 * |
| MICHAEL P. SCHRAMM等: "Guest Recognition with Micelle-Bound Cavitands", J. AM. CHEM. SOC., 31 December 2007 (2007-12-31), pages 9773 - 9779 * |
| MIN-MIN TANG等: "Role of Rim Functions in Recognition and Selectivity of Small- Molecule Guests in Water-Soluble Cavitand Hosts", CHEM ASIAN J., 15 June 2022 (2022-06-15), pages 202200466 * |
| QIXUN SHI等: "Macrocyclization of Folded Diamines in Cavitands", J. AM. CHEM. SOC., 16 August 2016 (2016-08-16), pages 10846 * |
| VENKATACHALAM ANGAMUTHU等: "Binding orientation and reactivity of alkyl α, ω-dibromides in water-soluble cavitands", ORG. BIOMOL. CHEM., 15 May 2019 (2019-05-15), pages 5279 * |
| YUJIE ZHU等: "Water and the Cation−π Interaction", J. AM. CHEM. SOC., 30 July 2021 (2021-07-30), pages 12397 * |
| 万云辉: "水溶性超分子杯的合成及 其应用研究", 上海大学硕士学位论文, 15 March 2022 (2022-03-15), pages 1 - 111 * |
| 关华伟: "吡啶基超分子杯的设计合 成及其在极性分子识别方 面的研究", 上海大学硕士学位论文, 15 March 2022 (2022-03-15), pages 1 - 134 * |
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