CN113087681A - 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-bis 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, the solubility of the polyurea macrocyclic molecules is low and difficult to purify, limited by intermolecular hydrogen bonding between the ureido groups, greatly limiting the preparation of the relevant 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 target products 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 aims to provide a cyclic polyurea molecule, a preparation method 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-CH3(ii) a X, Y are each independently-CH2-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-CH3(ii) a X is-CH2-O, -S or-C (CF)3)2(ii) a n is a natural number.
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 the complete reaction of bis (phenyl isocyanate) or bis (carbamate) through thin-layer chromatography analysis, carrying out 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 a 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 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 the 4, 5-bi R substituted-1, 2-o-phenylenediamine in the step one is shown in the specification
R is-H, -F or-CH3；
The structural formula of the bis (phenyl isocyanate) in the step one is shown as
X is-CH2-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-CH2-O, -S or-C (CF)3)2(ii) a R' is
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 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, the molar ratio of the 4, 5-bis R-substituted-1, 2-o-phenylenediamine to the bis (isocyanate) or bis (carbamate) in step one 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-diazabicycloundece-7-ene and 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 molecules of the invention are used as anion receptors 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.
In 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 (600mg) was dissolved in 20mL of tetrahydrofuran under nitrogen atmosphere, stirred, and 4, 4-diaminodiphenyl ether (200mg) was added thereto, the reaction solution was changed from colorless to white turbidity, and the mixture was refluxed at 80 ℃ overnight, and the reaction solution was spin-dried to precipitate a product with ether, which was dried to obtain a white solid product, bis (carbamate) EDC (504mg, 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 N2To a solution of 4-nitrophenylchloroformate (0.51g) in tetrahydrofuran (10mL) was added dropwise a solution of 4, 4-diaminodiphenylsulfide (0.22g) in tetrahydrofuran (10mL) under ambient conditions, the reaction was allowed to warm to 80 ℃ and proceed for 12 hours, the reaction was cooled to room temperature, the solvent was removed by rotary evaporation, washed with diethyl ether, and the product was dried to give the product, bis (carbamate) SDC (0.47g, 85% yield), as a white solid.
Example 1
The method comprises the following steps: in N2Weighing 1, 2-o-phenylenediamine (0.66g) in 10ml of tetrahydrofuran under the atmosphere to obtain a solution I, weighing 4, 4' -methylenebis (phenyl isocyanate) (MDI) (0.5g) in 10ml of tetrahydrofuran to obtain a solution II, dropwise adding the solution II into the solution I, reacting for 15 minutes under the condition of ice water bath (0 ℃), detecting that MDI has completely reacted through thin layer chromatography, performing suction filtration, washing the obtained solid with tetrahydrofuran and diethyl ether, and performing vacuum drying to obtain a target intermediate product (white solid) and diamine intermediate S1(0.91g, yield 99%).
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)6In ppm, δ is 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: in N2The diamine intermediate S1(233mg) was weighed out and dissolved in 10ml of N, N under an atmosphere-dimethylformamide and ultrasound to dissolve it completely to give a solution iii, which is transferred to a three-necked flask and heated to 100 ℃; weighing 4, 4' -methylenebis (phenyl isocyanate) (MDI) (125mg) and dissolving in 5ml of tetrahydrofuran to obtain a solution IV, adding the solution IV into a three-neck flask, reacting at 100 ℃ for 1h, detecting that MDI has completely reacted by thin layer chromatography to obtain a reaction solution, carrying out rotary evaporation on the reaction solution until a precipitate is separated out, then adding acetone to force out a white solid until the precipitate is completely precipitated, filtering, washing the obtained solid with acetone, and carrying out vacuum drying to obtain a target product (white solid), namely cyclotetrasurea molecule MU (325mg, 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)6In ppm, δ is 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 N2The diamine intermediate S1(233mg) was weighed out 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 (265mg) 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 reacted completely through thin-layer chromatography analysis to obtain reaction liquid, evaporating the reaction liquid until precipitation is separated out, then adding acetone to drive out white solid until 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 (320mg, yield 89%).
The hydrogen spectrum and mass spectrum results of the target product are as follows: one-dimensionalHydrogen nuclear magnetic spectrum (Bruk 400MHz, DMSO-d)6In ppm, δ is 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 spectrum (brueckesi-Q-TOF): [ M + Na ]]+:741.3。
The reaction equation of the second step is as follows:
example 3
The method comprises the following steps: in N2Weighing 1, 2-o-phenylenediamine (500mg) in 10ml of tetrahydrofuran under the atmosphere to obtain a solution I, dissolving compound EDC (1.06g) in 5ml of tetrahydrofuran to obtain a solution II, dropwise adding the solution II into the solution I, adding 2 ml of triethylamine, reacting for 2 hours under the condition of ice-water bath (0 ℃), detecting that EDC is completely reacted by thin layer chromatography, filtering, washing the obtained solid with diethyl ether for multiple times, and drying in vacuum to obtain a target intermediate product (white solid), namely a diamine intermediate S2(895mg, yield 95%).
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)6In ppm, δ is 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 N2Weighing the diamine intermediate S2(186mg) and triethylamine (0.5 ml) to be dissolved in 10ml of N, N-dimethylformamide under the atmosphere to obtain a solution III, transferring the solution III into a three-neck flask, heating to 100 ℃, weighing a compound EDC (212mg) to be dissolved in 10ml of N, N-dimethylformamide to obtain a solution IV, dropwise adding the solution IV into the three-neck flask, stirring at 100 ℃ for reaction for 2 hours, and reacting byAnd (3) detecting that the EDC has completely reacted by thin-layer chromatography analysis to obtain a reaction solution, evaporating the reaction solution until a precipitate is separated out, adding acetone to expel a solid until the precipitate is completely separated out, washing the solid with diethyl ether for multiple times, and drying in vacuum to obtain a target product (a light yellow solid), namely the cyclotetrasuiea molecule EU (273mg, the yield is 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)6In ppm, δ is 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 N2Weighing the diamine intermediate S1(184mg) 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) (67mg) in 7ml of dichloromethane to obtain a solution V, dropwise adding the solution V into the three-neck bottle, stirring and reacting at 100 ℃ for 1h, detecting that the HDI has completely reacted through thin-layer chromatography, obtaining a reaction solution after the reaction is finished, evaporating the reaction solution until precipitation is generated, then adding acetone to expel a large amount of white solid until the precipitation is complete, filtering, washing the obtained solid with diethyl ether for multiple times, and drying in vacuum to obtain the target product (white solid) cyclooctaurea molecule MUH (237mg, 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)6In ppm, δ is 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: the same procedure as in step one of example 3.
Step two: in N2Weighing the diamine intermediate S2(186mg) 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) (67mg) in 2 ml of dichloromethane to obtain a solution V, dropwise adding the solution V into the three-neck bottle, stirring and reacting for 1h at 100 ℃, detecting that the HDI has completely reacted through thin-layer chromatography to obtain a reaction liquid, evaporating the reaction liquid until precipitation is generated, adding acetone to expel a large amount of white solid until the precipitation is complete, 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 (234mg, 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)6In ppm, δ is 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: in N2Dissolving 1, 2-o-phenylenediamine (0.162g) in 10ml of tetrahydrofuran under atmosphere to obtain a solution I, dissolving a compound SDC (0.273g) in 10ml of tetrahydrofuran to obtain a solution II, dropwise adding the solution II into the solution I, adding triethylamine (0.5 ml), reacting for 1h under the condition of ice-water bath (0 ℃), detecting that the SDC has completely reacted through thin layer chromatography analysis, and performing suction filtrationThe obtained solid was washed with diethyl ether and dried to obtain the objective intermediate (white solid), diamine intermediate S3(0.25g, 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)6In ppm, δ is 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 spectrum (brueckesi-Q-TOF): [ M + Na ]]+:507.2。
The reaction equation of the first step is as follows:
step two: in N2Weighing the diamine intermediate S3(145mg) in 10ml of N, N-dimethylformamide to obtain a solution III, transferring the solution III into a three-neck flask and heating to 100 ℃, weighing Hexamethylene Diisocyanate (HDI) (50mg) in 5ml of dichloromethane to obtain a solution V, dropwise adding the solution V into the three-neck flask, stirring and reacting for 2h at 100 ℃, detecting that the HDI has completely reacted through thin-layer chromatography analysis to obtain a reaction liquid, evaporating the reaction liquid until precipitates are separated out, adding acetone to expel a large amount of white solid until the precipitates are completely separated out, filtering, washing the solid with diethyl ether, and drying to obtain a target product (yellow gray solid), a cyclic octaurea molecule SUH (178mg, 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)6δ ═ 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 N2Weighing 1, 2-o-phenylenediamine (0.66g) in 10ml of tetrahydrofuran to obtain a solution I, weighing 2, 2-bis (4-isocyanatophenyl) hexafluoropropane (0.5g) in 10ml of tetrahydrofuran to obtain a solution II, then dropwise adding the solution II into the solution I, reacting for 15 minutes in an ice water bath (0 ℃), detecting that the 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 N2The diamine intermediate S4(210mg) was weighed out in 10ml of N, N-dimethylformamide under an atmosphere to give solution iii, which was added to a three-necked flask and heated to 100 ℃. Weighing 2, 2-bis (4-isocyanatophenyl) hexafluoropropane (125mg) and dissolving the 2, 2-bis (4-isocyanatophenyl) hexafluoropropane in 5ml of tetrahydrofuran to obtain a solution IV, adding the solution IV into a three-necked bottle, reacting for 1h at 100 ℃, detecting that the 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 a precipitate is separated out, then adding acetone to expel a solid until the precipitate is completely precipitated, filtering, washing the obtained solid with acetone, and carrying out vacuum drying to obtain a target product, wherein hydrogen spectrum and mass spectrum results of the target product show that the target product is a cyclotetrasurea molecule CF 3U.
The reaction equation is as follows:
example 8
The cyclic tetraurea molecule MU described in example 1 (20mg) was weighed into a solution of tetraethylammonium sulfate (20mg) in acetonitrile (5mL) 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 (30mg) described in example 3 was weighed into a solution of tetraethylammonium sulfate (30mg) in acetonitrile (7mL) 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 (25mg) was weighed into a solution of tetraethylammonium sulfate (25mg) in acetonitrile (10mL) 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 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 (50mg) described in example 4 was weighed out and added to a solution of tetraethylammonium sulfate (50mg) in acetone (6mL) and N, N-dimethylformamide (1mL) 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 cyclooctadiuronium molecule EUH (50mg) described in example 5 was weighed into a solution of tetraethylammonium sulfate (50mg) in acetone (10mL) and N, N-dimethylformamide (1mL) 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 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 (10)
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-CH3(ii) a X, Y are each independently-CH2-O, -S or-C (CF)3)2；
The structural formula of the cyclic octaurea molecule is as follows:
wherein R is-H, -F or-CH3(ii) a X is-CH2-O, -S or-C (CF)3)2(ii) a n is a natural number.
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 the complete reaction of bis (phenyl isocyanate) or bis (carbamate) through thin-layer chromatography analysis, carrying out 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 a 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 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 the 4, 5-bi R substituted-1, 2-o-phenylenediamine in the step one is shown in the specification
R is-H, -F or-CH3；
The structural formula of the bis (phenyl isocyanate) in the step oneIs composed of
X is-CH2-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-CH2-O, -S or-C (CF)3)2(ii) a R' is
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 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.
3. The method of claim 2, wherein the cyclic polyurea molecule is prepared by: in the first step, the molar ratio of the 4, 5-bis R substituted-1, 2-o-phenylenediamine to the bis (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 polyurea molecule is a cyclic tetraurea molecule, the molar ratio of the diamine intermediate S to the bis (isocyanate) or the bis (carbamate) in the second step 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.
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 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.
7. The method of claim 2, wherein the cyclic polyurea molecule is prepared by: the organic base catalyst is triethylamine, pyridine, diisopropylethylamine, triethylene diamine, 1, 8-diazabicycloundece-7-ene and 4-dimethylpyridine.
8. The method of claim 2, wherein the cyclic polyurea molecule is prepared by: 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 anions.
10. 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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| TWI801945B (en) * | 2020-07-30 | 2023-05-11 | 南韓商Ｌｇ化學股份有限公司 | Binder resin, positive-type photosensitive resin composition, insulating film and semiconductor device |
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| CN114685319A (en) * | 2022-03-02 | 2022-07-01 | 北京理工大学 | Tripodal hexaurea neutral ligand, preparation method and application thereof |
| CN114685319B (en) * | 2022-03-02 | 2023-08-11 | 北京理工大学 | Tripodium hexaurea neutral ligand, preparation method and application thereof |
| CN115260970A (en) * | 2022-09-28 | 2022-11-01 | 江苏斯瑞达材料技术股份有限公司 | Acrylic acid composite glue with good weather resistance and humidity resistance and preparation method thereof |
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