CN113087681B - Cyclic polyurea molecule, preparation method and application thereof - Google Patents
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Abstract
The invention relates to a cyclic polyurea molecule, a preparation method and application thereof, belonging to the field of chemical synthesis. The cyclic polyurea molecules take an o-phenyldiurea structure as a basic unit, and form polyurea macrocyclic molecules with different sizes through different bridging groups (aromatic groups or alkyl chains). The method comprises the steps of firstly reacting 4,5-dual R substituted-1,2-o-phenylenediamine with bis (phenyl isocyanate) or bis (carbamate) to obtain a diamine intermediate, and then reacting the diamine intermediate with bis (phenyl isocyanate) or bis (carbamate) to obtain a target product. The method is simple, efficient and universal. The cyclic polyurea molecules are useful for the identification of anions.
Description
Technical Field
The invention relates to a cyclic polyurea molecule, a preparation method and application thereof, belonging to the field of chemical synthesis.
Background
The cyclic polyurea molecule is a functional compound taking a polyurea segment as a main skeleton structure, and has great potential application value in the fields of self-assembly materials, asymmetric catalysis, small molecule recognition, particularly anion recognition. However, due to intermolecular hydrogen bonding between the ureido groups, the solubility of the polyurea macrocyclic molecules is low and purification is difficult, greatly limiting the preparation of related polyurea macrocyclic molecules.
The patent applications PCT WO99/51570 and Xin Wu et al (Gale Chem 2019,5,1210-1222.) respectively adopt 3-step and 5-step reactions to prepare two cyclotetrasurea molecules with different substituents, but the yield is relatively low, the preparation method route is long, and the purification of a target product has certain difficulty. First, both methods require expensive, environmentally hazardous raw materials, intermediates and catalysts (e.g., hydrazine hydrate, metallic nickel, triphosgene and stannous chloride, etc.), which are not conducive to large scale preparation of cyclotetrasurea molecules. Secondly, both methods are methods of preparation of only individual cyclic tetraurea molecules, and are not applicable to other polyurea macrocyclic molecules, which methods have low universality.
Disclosure of Invention
In view of the above, the present invention provides a cyclic polyurea molecule, a method for preparing the same, and applications thereof. The cyclic polyurea molecules take an o-phenyldiurea structure as a basic unit, and form polyurea macrocyclic molecules with different sizes through different bridging groups (aromatic groups or alkyl chains); the method is simple to operate and has universality. The cyclic polyurea molecules are useful in the field of anion recognition.
In order to achieve the above object, the technical solution of the present invention is as follows.
A cyclic polyurea molecule, wherein the cyclic polyurea molecule is a cyclic tetraurea molecule or a cyclic octaurea molecule, and the structural formula of the cyclic tetraurea molecule is shown as a formula I:
wherein R is-H, -F or-CH 3 (ii) a X, Y are each independently-CH 2 -O, -S or-C (CF) 3 ) 2 。
The structural formula of the cyclic octaurea molecule is shown as a formula II:
wherein R is-H, -F or-CH 3 (ii) a X is-CH 2 -O, -S or-C (CF) 3 ) 2 ；。
The preparation method of the cyclic polyurea molecule comprises the following steps:
dissolving 4,5-bis R substituted-1,2-o-phenylenediamine in a solvent I to obtain a solution I under the nitrogen atmosphere, dissolving bis (phenyl isocyanate) or bis (carbamate) in a solvent II to obtain a solution II, dropwise adding the solution II into the solution I to react at the temperature of-20-10 ℃, detecting that bis (phenyl isocyanate) or bis (carbamate) completely reacts through thin-layer chromatography analysis, performing solid-liquid separation, washing the solid with the solvent I or the solvent II, and drying to obtain a target intermediate product, namely a diamine intermediate S;
step two, when the cyclic multi-urea molecule is a cyclic tetraurea molecule, dissolving the diamine intermediate S in a solvent III to obtain a solution III in a nitrogen atmosphere, dissolving bis (phenyl isocyanate) or bis (carbamate) in a solvent IV to obtain a solution IV, adding the solution IV into the solution III, reacting at 70-110 ℃, detecting that bis (phenyl isocyanate) or bis (carbamate) completely reacts through thin-layer chromatography analysis to obtain a reaction solution, evaporating the reaction solution until a precipitate is separated out, adding an anti-solvent until the precipitate is completely separated out, filtering, washing a solid with the anti-solvent, and drying to obtain the cyclic tetraurea molecule;
when the cyclic multi-urea molecule is a cyclic octaurea molecule, dissolving the diamine intermediate S in a solvent III to obtain a solution III in the nitrogen atmosphere, dissolving linear bis (phenyl isocyanate) in a solvent V to obtain a solution V, adding the solution V into the solution III, reacting at 70-110 ℃, detecting the complete reaction of the linear bis (phenyl isocyanate) through thin-layer chromatography analysis to obtain a reaction solution, carrying out rotary evaporation on the reaction solution until precipitation is generated, adding an anti-solvent until the precipitation is generated completely, filtering, washing the solid with the anti-solvent, and drying to obtain the cyclic octaurea molecule;
wherein the structural formula of 4,5-dual R substituted-1,2-o-phenylenediamine in the first step is shown in the specification
R is-H, -F or-CH 3 ；
The structural formula of the bis (phenyl isocyanate) in the step one is shown as
X is-CH 2 -O, -S or-C (CF) 3 ) 2 ；
The structural formula of the bis (carbamate) in the step one is shown in the specification
Y is-CH 2 -O, -S or-C (CF) 3 ) 2 (ii) a R' is
In the first step, the solvent I and the solvent II are mutually soluble;
when bis (carbamate) is dissolved in a solvent II to obtain a solution II, dropwise adding the solution II into the solution I and adding an organic base catalyst;
when the cyclic polyurea molecule is a cyclic tetraurea molecule, dissolving bis (carbamate) in a solvent IV to obtain a solution IV in the step II, adding the solution IV into a solution III, and adding an organic base catalyst;
when the cyclic multi-urea molecule is a cyclic octaurea molecule, the structural formula of the linear bis (phenyl isocyanate) in the second step is shown in the specification
n is a natural number.
Preferably, in step one, the molar ratio of 4,5-bis R substituted-1,2-o-phenylenediamine to bis (isocyanate) or bis (urethane) is 2:1.
Preferably, in the step one, the solvent I and the solvent II are tetrahydrofuran, dichloromethane, trichloromethane, acetonitrile and acetone respectively and independently.
Preferably, when the cyclic polyurea molecule is a cyclic tetraurea molecule, the molar ratio of the diamine intermediate S to bis (isocyanate) or bis (carbamate) in step two is 1:1; when the cyclic polyurea molecule is a cyclic octaurea molecule, the molar ratio of the diamine intermediate S to the linear bis (isocyanate) in step two is 1:1.
Preferably, in the second step, the solvent III is more than one of N, N-dimethylformamide, acetonitrile, acetone and tetrahydrofuran; the anti-solvent is more than one of acetone, diethyl ether, cyclohexane, normal hexane and petroleum ether; when the cyclic multi-urea molecule is a cyclic tetraurea molecule, the solvent IV is more than one of tetrahydrofuran, dichloromethane, trichloromethane, acetonitrile and acetone; and the anti-solvent and the solvent III or the solvent IV are not acetone at the same time; when the cyclic polyureide molecule is a cyclic octaurea molecule, the solvent V in the step two is more than one of tetrahydrofuran, dichloromethane, trichloromethane, acetonitrile and acetone; and the anti-solvent and the solvent III or the solvent V are not acetone at the same time.
Preferably, the organic base catalyst is triethylamine, pyridine, diisopropylethylamine, triethylene diamine, 1,8-diazabicycloundec-7-ene, 4-dimethylpyridine.
Preferably, the molar ratio of the organic base catalyst to bis (carbamate) is 1:1.
Use of a cyclic polyurea molecule as an anion receptor for the recognition of an anion.
Preferably, the cyclic polyurea molecule acts as an anion receptor for the recognition of sulfate ions.
Advantageous effects
(1) The cyclic polyurea molecule takes a typical and repeatable phthalic diurea structure as a basic unit, and polyurea macrocyclic molecules with different sizes are formed by different bridging groups (aromatic groups or alkyl chains).
(2) The raw materials used in the invention are simple and easy to obtain, and the cost is low; the method is simple and efficient, only two steps of reaction are needed, and the target molecule can be prepared without column separation; the method has high universality and can be used for preparing cyclic polyurea molecules with different structures. Furthermore, the total yield of the target molecules can reach more than 80 percent by controlling the dosage of the raw materials.
(3) The cyclic polyurea molecule provided by the invention is used as an anion receptor for identifying anions. When the compound is further used for identifying sulfate ions, single crystal diffraction structure analysis proves that the cyclic polyurea molecules can be combined with the sulfate ions through the strong hydrogen bond donor function of the ureido functional groups to form a complex. Hydrogen bonding between sulfate ions and cyclic polyurea molecules is observed in the crystal structure.
Drawings
FIG. 1 is a structural diagram of a crystal according to example 8;
FIG. 2 is a structural diagram of the crystal described in example 9;
FIG. 3 is a crystal structure diagram of example 10;
FIG. 4 is a structural diagram of the crystal described in example 11;
FIG. 5 is a crystal structure diagram of example 12;
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The following examples:
(1) The structural formula of the compound bis (carbamate) EDC is shown in the specification
The preparation method comprises the following steps:
in a three-necked flask, 4-nitrochloroformate (600 mg) was dissolved in 20mL of tetrahydrofuran under nitrogen atmosphere, stirred, 4,4-diaminodiphenyl ether (200 mg) was added, the reaction solution turned from colorless clear to white turbid, refluxed at 80 ℃ overnight, the reaction solution was spun dry, the product was precipitated with ether, and dried to give a white solid product, bis (carbamate) EDC (504 mg, yield 95%).
The hydrogen and mass spectra of the product are as follows: one dimensional hydrogen nuclear magnetic spectrum (Bruk 400MHz, DMSO-d) 6 Ppm) 10.46 (s, 2H), 8.31 (d, 4H), 7.53-7.50 (m, 8H), 7.01 (d, 4H). Mass spectrum (brueckesi-Q-TOF): [ M + H ]] + :531.2。
(2) The structural formula of the compound bis (carbamate) SDC is shown in the specification
The preparation method comprises the following steps:
in N 2 To a solution of 4-nitrophenylchloroformate (0.51 g) in tetrahydrofuran (10 mL) was added dropwise a solution of 4,4-diaminodiphenylsulfide (0.22 g) in tetrahydrofuran (10 mL) under ambient conditions, the reaction was allowed to warm to 80 ℃ and react for 12 hours, the reaction was cooled to room temperature, the solvent was removed by rotary evaporation, the product was washed with ether and dried to give the product, bis (carbamate) SDC (0.47 g, 85% yield), as a white solid.
Example 1
The method comprises the following steps: in N 2 Weighing 1,2-o-phenylenediamine (0.66 g) and dissolving in 10ml of tetrahydrofuran to obtain solution I, weighing 4,4' -methylene bis (phenyl isocyanate) (MDI) (0.5 g) and dissolving in 10ml of tetrahydrofuran to obtain solution II, dropwise adding the solution II into the solution I, and carrying out ice-water bathAfter 15 minutes of reaction at (0 ℃), MDI was detected by TLC to have reacted to completion, the solid was filtered and washed with tetrahydrofuran and diethyl ether and dried under vacuum to give the desired intermediate (white solid), diamine intermediate S1 (0.91 g, 99% yield).
The hydrogen spectrum and mass spectrum results of the target intermediate product are as follows: one dimensional hydrogen nuclear magnetic spectrum (Bruk 400MHz, DMSO-d 6 δ =8.67 (2H), 7.67 (2H), 7.36-7.32 (6H), 7.09 (4H), 6.81 (2H), 6.72 (2H), 6.58 (2H), 4.72 (4H), 3.80 (2H). Mass spectrum (brueckesi-Q-TOF): [ M + Na ]] + :489.2。
The reaction equation of the first step is as follows:
step two: at N 2 Weighing the diamine intermediate S1 (233 mg) under the atmosphere, dissolving in 10ml of N, N-dimethylformamide and carrying out ultrasonic treatment to completely dissolve the N, N-dimethylformamide to obtain a solution III, transferring the solution III into a three-neck bottle and heating to 100 ℃; weighing 4,4' -methylenebis (phenyl isocyanate) (MDI) (125 mg) and dissolving in 5ml of tetrahydrofuran to obtain a solution IV, adding the solution IV into a three-neck bottle, reacting at 100 ℃ for 1h, detecting that MDI has completely reacted by thin layer chromatography analysis to obtain a reaction liquid, evaporating the reaction liquid in a rotary manner until precipitation is separated out, then adding acetone to force out a white solid until the precipitation is completely separated out, filtering, washing the obtained solid with acetone, and drying in vacuum to obtain a target product (white solid) and a cyclotetrasurea molecule MU (325 mg, yield 92%).
The hydrogen spectrum and mass spectrum results of the target product are as follows: one dimensional hydrogen nuclear magnetic spectrum (Bruk 400MHz, DMSO-d) 6 In ppm, δ =9.01 (2H), 8.02 (2H), 7.57 (2H), 7.36 (4H), 7.10 (4H), 7.04 (2H), 3.80 (2H). Mass spectrum (brueckesi-Q-TOF): [ M + K ]] + :755.3。
The reaction equation of the second step is as follows:
example 2
The method comprises the following steps: same as example 1 step one.
Step two: in N 2 The diamine intermediate S1 (233 mg) was weighed out to dissolve in 10ml of N, N-dimethylformamide under an atmosphere to give a solution III, which was transferred to a three-necked flask and heated to 100 ℃. Weighing compound EDC (265 mg) and dissolving in 10ml of N, N-dimethylformamide to obtain solution IV, slowly adding the solution IV into a three-neck flask, adding triethylamine (0.5 ml), reacting at 100 ℃ for 3h, detecting that EDC has completely reacted through thin layer chromatography analysis to obtain reaction liquid, evaporating the reaction liquid in a rotary manner until precipitation is separated out, then adding acetone to force out white solid till the precipitation is complete, filtering, washing the obtained solid with diethyl ether, and drying in vacuum to obtain a target product (white solid), namely cyclotetraurea molecule MUE (320 mg, yield 89%).
The hydrogen spectrum and mass spectrum results of the target product are as follows: one dimensional hydrogen nuclear magnetic spectrum (Bruk 400MHz, DMSO-d) 6 In ppm, δ =9.04 (4H), 8.02 (4H), 7.59 (4H), 7.46-7.43 (4H), 7.38-7.35 (4H), 7.12-7.08 (4H), 7.07-7.03 (4H), 6.92-6.90 (4H), 3.79 (2H). Mass Spectrometry (BrookESI-Q-TOF): [ M + Na ]] + :741.3。
The reaction equation of the second step is as follows:
example 3
The method comprises the following steps: at N 2 Under the atmosphere, 1,2-o-phenylenediamine (500 mg) is weighed and dissolved in 10ml of tetrahydrofuran to obtain a solution I, compound EDC (1.06 g) is dissolved in 5ml of tetrahydrofuran to obtain a solution II, the solution II is dropwise added into the solution I, 2 ml of triethylamine is added, after reaction for 2 hours under the condition of ice-water bath (0 ℃), EDC is detected to be completely reacted by thin layer chromatography analysis, suction filtration is carried out, the obtained solid is washed with diethyl ether for multiple times, and after vacuum drying, the target intermediate product (white solid) and the diamine intermediate S2 (895 mg, yield 95%) are obtained.
The purpose isThe results of the hydrogen and mass spectra of the target intermediate were as follows: one dimensional hydrogen nuclear magnetic spectrum (Bruk 400MHz, DMSO-d) 6 In ppm, δ =8.72 (2H), 7.68 (2H), 7.43 (4H), 7.32 (2H), 6.91 (4H), 6.82 (2H), 6.73 (2H), 6.57 (2H), 4.77 (4H). Mass spectrum (brueckesi-Q-TOF): [ M + Na ]] + :491.2。
The reaction equation of the first step is as follows:
step two: in N 2 Weighing the diamine intermediate S2 (186 mg) and triethylamine (0.5 ml) to dissolve in 10ml of N, N-dimethylformamide to obtain a solution III, transferring the solution III into a three-neck bottle, heating to 100 ℃, weighing a compound EDC (212 mg) to dissolve in 10ml of N, N-dimethylformamide to obtain a solution IV, dropwise adding the solution IV into the three-neck bottle, stirring at 100 ℃ for reaction for 2 hours, detecting that the EDC has completely reacted by thin layer chromatography to obtain a reaction solution, evaporating the reaction solution until precipitation is generated, then adding acetone to expel solid until precipitation is complete, washing the solid with diethyl ether for multiple times, and drying in vacuum to obtain a target product (EU light yellow solid), and a cyclotetrasurea molecule (273 mg, yield 95%).
The hydrogen spectrum and mass spectrum results of the target product are as follows: one dimensional hydrogen nuclear magnetic spectrum (Bruk 400MHz, DMSO-d) 6 In ppm, δ =9.05 (4H), 8.03 (4H), 7.58 (4H), 7.45 (8H), 7.08 (4H), 6.93 (8H). Mass spectrum (brueckesi-Q-TOF): [ M + Na ]] + :743.2。
The reaction equation of the second step is as follows:
example 4
The method comprises the following steps: same as example 1 step one.
Step two: in N 2 Weighing the diamine intermediate S1 (184 mg) and dissolving in 10ml of N, N-dimethylformamide under the atmosphere to obtain a solution IIIIII is transferred into a three-neck bottle and heated to 100 ℃, hexamethylene Diisocyanate (HDI) (67 mg) is weighed and dissolved in 7ml of dichloromethane to obtain a solution V, the solution V is dropwise added into the three-neck bottle, after stirring and reacting for 1h at 100 ℃, the completion of HDI reaction is detected through thin layer chromatography analysis, a reaction liquid is obtained after the reaction is finished, the reaction liquid is evaporated in a rotary mode until precipitation is completed, then acetone is added to force out a large amount of white solid until precipitation is completed, filtering is carried out, the obtained solid is washed with diethyl ether for multiple times, and vacuum drying is carried out to obtain the target product (white solid), the cyclooctadien molecule MUH (237 mg, yield 94%).
The hydrogen spectrum and mass spectrum results of the target product are as follows: one dimensional hydrogen nuclear magnetic spectrum (Bruk 400MHz, DMSO-d 6 δ =9.00 (4H), 7.96 (4H), 7.79 (4H), 7.54-7.47 (8H), 7.36 (8H), 7.09 (8H), 7.01-6.98 (8H), 6.51 (4H), 3.78 (4H), 3.08 (8H), 1.44 (8H), 1.30 (8H). Mass spectrum (brueckesi-Q-TOF): [ M + K ]] + :1307.5。
The reaction equation of the second step is as follows:
example 5
The method comprises the following steps: same as example 3, step one.
Step two: in N 2 Weighing the diamine intermediate S2 (186 mg) in 10ml of N, N-dimethylformamide to obtain a solution III, transferring the solution III into a three-neck bottle, heating to 100 ℃, weighing Hexamethylene Diisocyanate (HDI) (67 mg) in 2 ml of dichloromethane to obtain a solution V, dropwise adding the solution V into the three-neck bottle, stirring at 100 ℃ for 1h, detecting that the HDI has completely reacted through thin layer chromatography to obtain a reaction solution, evaporating the reaction solution until a precipitate is separated out, adding acetone to force out a large amount of white solid until the precipitate is completely separated out, filtering, washing the obtained solid with diethyl ether for multiple times, and drying in vacuum to obtain the target product (white solid) and the cyclooctadien molecule EUH (234 mg, 92% yield).
The hydrogen spectrum and mass spectrum results of the target product are as follows: aNuclear magnetic resonance of vitamin H spectrum (Bruk 400MHz, DMSO-d) 6 δ =9.06 (H), 7.99 (4H), 7.81 (4H), 7.53-7.49 (8H), 7.43 (8H), 7.04-6.98 (8H), 6.90 (8H), 6.51 (4H), 3.08 (8H), 1.44 (8H), 1.30 (8H). Mass spectrum (brueckesi-Q-TOF): [ M + Na ]] + :1295.5。
The reaction equation of the second step is as follows:
example 6
The method comprises the following steps: at N 2 Under the atmosphere, 1,2-o-phenylenediamine (0.162 g) is dissolved in 10ml of tetrahydrofuran to obtain a solution I, compound SDC (0.273 g) is dissolved in 10ml of tetrahydrofuran to obtain a solution II, the solution II is added into the solution I dropwise, triethylamine (0.5 ml) is added, after the reaction is carried out for 1h under the condition of ice water bath (0 ℃), SDC is detected to be completely reacted through thin layer chromatography analysis, suction filtration is carried out, the obtained solid is washed with diethyl ether and dried to obtain the target intermediate product (white solid), and diamine intermediate S3 (0.25 g, yield 93%).
The hydrogen spectrum and mass spectrum results of the target intermediate product are as follows: one dimensional hydrogen nuclear magnetic spectrum (Bruk 400MHz, DMSO-d) 6 In ppm, δ =8.99 (2H), 7.73 (2H), 7.45 (4H), 7.32 (2H), 7.23 (4H), 6.84 (2H), 6.73 (2H), 6.57 (2H), 4.78 (4H). Mass Spectrometry (BrookESI-Q-TOF): [ M + Na ]] + :507.2。
The reaction equation of the first step is as follows:
step two: in N 2 Weighing the diamine intermediate S3 (145 mg) in 10ml of N, N-dimethylformamide under the atmosphere to obtain a solution III, transferring the solution III into a three-neck flask and heating to 100 ℃, weighing Hexamethylene Diisocyanate (HDI) (50 mg) in 5ml of dichloromethane to obtain a solution V, dropwise adding the solution V into the three-neck flask, stirring and reacting at 100 ℃ for 2 hours, and detecting that HDI is detected by thin layer chromatographyAnd (3) completely reacting to obtain a reaction solution, performing rotary evaporation on the reaction solution until a precipitate is separated out, adding acetone to drive out a large amount of white solid until the precipitate is completely separated out, filtering, washing the solid with diethyl ether, and drying to obtain the target product (Huang Huise solid) and the cyclooctadiurea molecule SUH (178 mg, yield 72%).
The hydrogen spectrum and mass spectrum results of the target product are as follows: one dimensional hydrogen nuclear magnetic spectrum (Bruk 400MHz, acetone-d) 6 δ =11.36 (s, 4H), 11.14 (s, 4H), 10.16 (s, 4H), 8.77 (t, 4H), 8.27 (d, 4H), 7.81 (d, 8H), 7.60 (d, 4H), 7.26 (d, 8H), 6.85 (t, 4H), 6.76 (t, 4H). Mass spectrum (brueck ESI-Q-TOF): [ M + H ]] + :1305.6。
The reaction equation of the second step is as follows:
example 7
The method comprises the following steps: in N 2 Weighing 1,2-o-phenylenediamine (0.66 g) and dissolving in 10ml of tetrahydrofuran to obtain a solution I, weighing 2,2-bis (4-isocyanatophenyl) hexafluoropropane (0.5 g) and dissolving in 10ml of tetrahydrofuran to obtain a solution II, dropwise adding the solution II into the solution I, reacting for 15 minutes in an ice water bath (0 ℃), detecting that 2,2-bis (4-isocyanatophenyl) hexafluoropropane has completely reacted through thin layer chromatography, performing suction filtration, washing the obtained solid with a large amount of tetrahydrofuran and diethyl ether for multiple times, and performing vacuum drying to obtain a target intermediate product, namely a diamine intermediate S4.
Step two: in N 2 The diamine intermediate S4 (210 mg) was weighed out under an atmosphere to obtain a solution iii by dissolving in 10ml of N, N-dimethylformamide, and the solution iii was added to a three-necked flask and heated to 100 ℃. Weighing 2,2-bis (4-isocyanatophenyl) hexafluoropropane (125 mg) and dissolving in 5ml tetrahydrofuran to obtain a solution IV, adding the solution IV into a three-neck bottle, reacting at 100 ℃ for 1h, detecting that 2,2-bis (4-isocyanatophenyl) hexafluoropropane has completely reacted through thin layer chromatography analysis to obtain a reaction solution, carrying out rotary evaporation on the reaction solution until precipitation is generated, then adding acetone to expel solid until precipitation is complete,and filtering, washing the obtained solid with acetone, and drying in vacuum to obtain a target product, wherein the hydrogen spectrum and mass spectrum results of the target product show that the target product is a cyclotetraurea molecule CF3U.
The reaction equation is as follows:
example 8
The cyclic tetraurea molecule MU described in example 1 (20 mg) was weighed into a solution of tetraethylammonium sulfate (20 mg) in acetonitrile (5 mL) and stirred overnight at room temperature. Centrifuging, collecting supernatant, adding the supernatant into a beaker containing acetonitrile, placing the beaker and another beaker containing diethyl ether together in the same closed environment for gas phase diffusion to obtain colorless crystals in the beaker containing acetonitrile, and analyzing the crystals by a single crystal diffraction structure, wherein the structure of the crystals is shown in figure 1, and the result shows that one cyclic tetraurea molecule MU can be combined and coordinated with two sulfate ions.
Example 9
The cyclotetrasurea molecule EU (30 mg) described in example 3 was weighed into a solution of tetraethylammonium sulfate (30 mg) in acetonitrile (7 mL) and stirred at room temperature overnight. Centrifuging, collecting supernatant, adding the supernatant into a beaker containing acetonitrile, placing the beaker and another beaker containing diethyl ether together in the same closed environment for gas phase diffusion to obtain colorless crystals in the beaker containing acetonitrile, and performing single crystal diffraction structure analysis on the crystals, wherein the structure of the crystals is shown in figure 2, and the result shows that one cyclic tetraurea molecule EU can be combined and coordinated with two sulfate ions.
Example 10
The cyclic tetraurea molecule MUE described in example 2 (25 mg) was weighed into a solution of tetraethylammonium sulfate (25 mg) in acetonitrile (10 mL) and stirred overnight at room temperature. Centrifuging, collecting supernatant, adding the supernatant into a beaker containing acetonitrile, placing the beaker and another beaker containing diethyl ether together in the same closed environment for gas phase diffusion to obtain colorless crystals in the beaker containing acetonitrile, and analyzing the crystals by a single crystal diffraction structure, wherein the structure of the crystals is shown in figure 3, and the result shows that one cyclic tetraurea molecule MUE can be combined and coordinated with two sulfate ions.
Example 11
The cyclooctaderea molecule MUH (50 mg) described in example 4 was weighed into a solution of tetraethylammonium sulfate (50 mg) in acetone (6 mL) and N, N-dimethylformamide (1 mL) and stirred at room temperature overnight. Centrifuging, collecting supernatant, adding the supernatant into a beaker containing acetone and N, N-dimethylformamide, placing the beaker and another beaker containing diethyl ether together in the same closed environment for gas phase diffusion to obtain colorless crystals in the beaker containing acetone and N, N-dimethylformamide, and analyzing the crystals by a single crystal diffraction structure, wherein the structure is shown in figure 4, and the result shows that one cyclic octaurea molecule MUH can be combined and coordinated with two sulfate ions.
Example 12
The cycloocta urea molecule EUH (50 mg) described in example 5 was weighed into a solution of tetraethylammonium sulfate (50 mg) in acetone (10 mL) and N, N-dimethylformamide (1 mL) and stirred overnight at room temperature. Centrifuging, collecting supernatant, adding the supernatant into a beaker containing acetone and N, N-dimethylformamide, placing the beaker and another beaker containing diethyl ether together in the same closed environment for gas phase diffusion to obtain colorless crystals in the beaker containing acetone and N, N-dimethylformamide, and analyzing the crystals by a single crystal diffraction structure, wherein the structure is shown in figure 5, and the result shows that one cyclic octaurea molecule EUH can be combined and coordinated with two sulfate ions.
In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.
Claims (9)
1. A cyclic polyurea molecule characterized by: the cyclic polyurea molecule is a cyclic tetraurea molecule or a cyclic octaurea molecule;
wherein the structural formula of the cyclic tetraurea molecule is as follows:
wherein R is-H, -F or-CH 3 (ii) a X, Y are each independently-CH 2 -O, -S or-C (CF) 3 ) 2 ；
The structural formula of the cyclic octaurea molecule is as follows:
wherein R is-H; x is-CH 2 -O or-S; n =4.
2. A method of preparing the cyclic polyurea molecule of claim 1, wherein: the method comprises the following steps:
dissolving 4,5-bis R substituted-1,2-o-phenylenediamine in a solvent I to obtain a solution I under the nitrogen atmosphere, dissolving bis (phenyl isocyanate) or bis (carbamate) in a solvent II to obtain a solution II, dropwise adding the solution II into the solution I to react at the temperature of-20-10 ℃, detecting that bis (phenyl isocyanate) or bis (carbamate) completely reacts through thin-layer chromatography analysis, performing solid-liquid separation, washing the solid with the solvent I or the solvent II, and drying to obtain a target intermediate product, namely a diamine intermediate S;
step two, when the cyclic multi-urea molecule is a cyclic tetraurea molecule, dissolving the diamine intermediate S in a solvent III to obtain a solution III in the nitrogen atmosphere, dissolving bis (phenyl isocyanate) or bis (carbamate) in a solvent IV to obtain a solution IV, adding the solution IV into the solution III, reacting at 70-110 ℃, detecting that bis (phenyl isocyanate) or bis (carbamate) completely reacts through thin-layer chromatography to obtain a reaction liquid, carrying out rotary evaporation on the reaction liquid until precipitation is generated, adding an anti-solvent until precipitation is generated completely, filtering, washing a solid with the anti-solvent, and drying to obtain the cyclic tetraurea molecule;
when the cyclic multi-urea molecule is a cyclic octaurea molecule, dissolving the diamine intermediate S in a solvent III to obtain a solution III in the nitrogen atmosphere, dissolving linear bis (phenyl isocyanate) in a solvent V to obtain a solution V, adding the solution V into the solution III, reacting at 70-110 ℃, detecting the complete reaction of the linear bis (phenyl isocyanate) through thin-layer chromatography analysis to obtain a reaction solution, carrying out rotary evaporation on the reaction solution until precipitation is generated, adding an anti-solvent until the precipitation is generated completely, filtering, washing the solid with the anti-solvent, and drying to obtain the cyclic octaurea molecule;
wherein the structural formula of 4,5-dual R substituted-1,2-o-phenylenediamine in the first step is shown in the specification
R is-H, -F or-CH 3 ；
In the step one, the solvent I and the solvent II are mutually soluble;
when bis (carbamate) is dissolved in a solvent II to obtain a solution II, dropwise adding the solution II into the solution I and adding an organic base catalyst;
when the cyclic multi-urea molecule is a cyclic tetraurea molecule, the structural formula of the bis (phenyl isocyanate) in the step one is shown in the specification
X is-CH 2 -O, -S or-C (CF) 3 ) 2 (ii) a The structural formula of the bis (carbamate) is shown in the specification
Y is-CH 2 -O, -S or-C (CF) 3 ) 2 (ii) a R' is
In the second step, when bis (carbamate) is dissolved in a solvent IV to obtain a solution IV, adding the solution IV into a solution III and adding an organic base catalyst;
when the cyclic polyurea molecule is a cyclic octaurea molecule, the structural formula of the bis (urethane)Is composed of
Y is-O; r' is
The structural formula of the linear bi (phenyl isocyanate) in the step two is shown as
n is 4.
3. The method of claim 2, wherein: in the first step, the molar ratio of 4,5-bis R substituted-1,2-o-phenylenediamine to bis (phenyl isocyanate) or bis (carbamate) is 2:1.
4. The method of claim 2, wherein the cyclic polyurea molecule is prepared by: in the step one, the solvent I and the solvent II are tetrahydrofuran, dichloromethane, trichloromethane, acetonitrile and acetone respectively and independently.
5. The method of claim 2, wherein the cyclic polyurea molecule is prepared by: when the cyclic multi-urea molecule is a cyclic tetraurea molecule, the molar ratio of the diamine intermediate S to the bis (phenyl isocyanate) or the bis (carbamate) in the second step is 1:1; when the cyclic polyurea molecules are cyclic octaurea molecules, the molar ratio of the diamine intermediate S to the linear bis (phenyl isocyanate) in the second step is 1:1.
6. The method of claim 2, wherein the cyclic polyurea molecule is prepared by: in the second step, the solvent III is more than one of N, N-dimethylformamide, acetonitrile, acetone and tetrahydrofuran; the anti-solvent is more than one of acetone, diethyl ether, cyclohexane, normal hexane and petroleum ether; when the cyclic multi-urea molecule is a cyclic tetraurea molecule, the solvent IV is more than one of tetrahydrofuran, dichloromethane, trichloromethane, acetonitrile and acetone; and the anti-solvent and the solvent III or the solvent IV are not acetone at the same time; when the cyclic multi-urea molecule is a cyclic octaurea molecule, the solvent V in the step two is more than one of tetrahydrofuran, dichloromethane, trichloromethane, acetonitrile and acetone; and the anti-solvent and the solvent III or the solvent V are not acetone at the same time.
7. The method of claim 2, wherein: the organic base catalyst is triethylamine, pyridine, diisopropylethylamine, triethylene diamine or 1,8-diazabicycloundec-7-ene.
8. The method of claim 2, wherein: the molar ratio of the organic base catalyst to bis (carbamate) is 1:1.
9. Use of a cyclic polyurea molecule according to claim 1, wherein: the cyclic polyurea molecules act as anion receptors for the recognition of sulfate ions.
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