CN106008275A - Synthesis method of multi-ureido tripodal type functional monomer molecule with nitrogen as center - Google Patents
Synthesis method of multi-ureido tripodal type functional monomer molecule with nitrogen as center Download PDFInfo
- Publication number
- CN106008275A CN106008275A CN201610467226.1A CN201610467226A CN106008275A CN 106008275 A CN106008275 A CN 106008275A CN 201610467226 A CN201610467226 A CN 201610467226A CN 106008275 A CN106008275 A CN 106008275A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- ureido
- dissolved
- alpha
- tripodal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesis method of a multi-ureido tripodal type functional monomer molecule with nitrogen as a center. According to a method for generating urea through isocyanate at one end of styrene and triamine, 3-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate and tris(2-aminoethyl)amine are subjected to a reaction, the molar ratio of reaction raw materials, the reaction time and a reaction solvent are controlled, and styrene functional monomer molecules containing end polymerizable double bonds and multi-ureido functional groups with a self-aggregation effect are obtained. According to the obtained multi-ureido tripodal type functional monomer molecule with nitrogen as the center, the tripodal functional monomer is formed through connection of a top end nitrogen atom with three ureido functional groups with a specific identification function and the polymerizable double bonds, and stable molecularly imprinted polymers can be formed by three ureido side chains with the strong specific identification function of the tripodal functional monomer and multiple template molecules. The polymers have a special three-dimensional spatial structure and are used for synthesizing novel molecularly imprinted polymers which have application prospect in fields such as bionics, chromatographic separation, solid-phase extraction, membrane separation and the like.
Description
Technical field
The present invention relates to the synthetic method of a kind of tripod-type function monomer molecule of many urea groups centered by nitrogen.
Background technology
1773, Yi Laierluoaier (Hilaire Rouelle) found carbamide (urea), and carbamide is in carbamide compounds
Minimum molecule, carbamide compounds is made up of three parts, is to be connected to form by two kinds of amine by the carbonyl moiety at bridge joint center,
Based on urea groups system, introduce different substituent groups by different synthetic methods, form the ureido derivatives containing different urea groups numbers
, the research of carbamide derivative not only rests on molecular level, urea/ureido functional the interaction between rolling into a ball, urea/ureido functional group and gold
Belonging to cation, the Coordinative Chemistry research with anion is the most progressively goed deep into, the coordination composite obtained or Supramolecular Assembling material
The most all being applied, such as: lubricating oil, hair jelly, contact lens etc., thus by based on urea groups
Molecular recognition and assembling research are extremely important and significant.
The research of tripodal compound and coordination compound thereof be Coordinative Chemistry and supramolecular chemistry field hot research problem it
One [Chinese Journal of Inorganic Chemistry, 2001,17 (4): 478-488].The compound of tripod structure and coordination compound thereof are that a class is with C
, the atom such as N, B, P or a series of special constructions built centered by circulus and the material of character, they are different from one
As symmetry material develop to space two-dimensional direction, but develop to space three-dimensional direction, so having relatively low symmetry.
The coordination compound that tripod ligand is formed with metal ion, its electronic structure, coordination property, biological activity etc. all show with crowd not
With complexity, and some tripodal compound also can with some compounds formed special construction supramolecular system, because of
This, tripodal compound is in catalysis, medicine, biochemistry, fluorescent material, molecular recognition and self assembly and life sciences
Field all has broad application prospects, and design synthesis having the tripodal compound of specific function will be research from now on
Focus.
Centered by nitrogen-atoms, nitrogen-atoms introduces the spider knot of the class that three side chains with special coordination ability are constituted
Structure compound, its side chain is typically made up of Schiff's base, aromatic heterocycle, aliphatic amine, phthalein amine and Open chain cryptand etc..Nitrogen center
Tripodal compound is in application always interested the grinding of people as ionophore, biosimulation and DNA effect etc.
Study carefully problem.The ferrum of amide substituted spider aminated compounds, ketone coordination compound can be as simulations methyl mono-oxygenase (MMO)
And the research [J Am.Chem.Soc., 1992,114:8138-8146] of ketone azurin the system, [J. such as Nath
Organomet.Chem., 2010] synthesize the Schiff's base tripod-type compound centered by nitrogen, synthesize a series of different
The coordination compound of organotin (VI), research finds, the coordination compound ratio three of the metallic tin (VI) formed after coordinating with organotin (VI)
The anti-inflammatory activity of foot rest part itself is compared and is shown more superior anti-inflammatory activity.
Carbamide derivative self has donor and the donor of hydrogen bond, is supermolecule research, especially self assembly and molecular recognition aspect
Extraordinary receptor [Inorg.Chem, 1996 (35)；Chem.Soc, 1987 (109): 6518～6519].Supramolecular chemistry (
Supramolcular Chemistry) it is to study two or more chemical species to be concluded by intermolecular interaction and become tool
The science of the molecule aggregate of ad hoc structure and function, intermolecular interaction is had to include coordinate bond, intermolecular hydrogen bonding, electrostatic
Gravitation, pi-pi accumulation effect, Van der Waals force and hydrophobic interaction etc., wherein hydrogen bond is a kind of very important intermolecular force
, the adhesion of hydrogen bond is relatively strong, and has directivity and selectivity it is considered to be a kind of most important and maximally effective supermolecule structure
Building power or synthon, hydrogen bond can regard a kind of special dipole-dipole interaction as, (such as draws electronics with electronegative atom
Group) dipole of connected hydrogen atom and neighbouring molecule or functional group attracts each other.
Supramolecular chemistry mainly studies the chemistry of weak non-covalent bond synthon aggregation, working in coordination with by weak interaction force
The molecular recognition acted on and carry out and molecule assemble the focus being study now, and a lot of scientists pay special attention to.The pass of self assembly
Key is the collaborative generation of intermolecular multiple weak interaction force, and these active forces are to ensure that the basis of molecular structure stabilized
[Biotechnology Advances,2002,20(5-6):321-339].Azepine aryl tripod ligand and suitable transition gold
Belong to ion and pass through coordinate bond, and the weak force such as hydrogen bond and π-π interaction carries out self assembly, can obtain having uniqueness
The super molecular compound such as caged of topological structure, the labyrinth such as netted, duct, [Angew.Chem.Int.Ed, 1998,
37:1460～1494；Chem.Commun, 2001:509～518], Fujita seminar
[J.Am.Chem.Soc, 1998,120:8561～8562] with triazines rigidity azepine aryl tripod ligand with
Pd(en)(NO3)2Or Pt (en) (NO3)2(en=ethylenediamine) carries out self assembly, has respectively obtained M6L4The octahedral of (M=Pt, Pd) type
Body shape supermolecule cage.
Gelator containing urea groups is particularly effective hydrogen bond module units in Supramolecular Assembling, is obtained by the functionalization of substituent group
To having the function supermolecular gel of multilevel hierarchy, especially many urea groups gelator, its hydrogen bond module units increased can set
Meter and the more diversified gel supermolecule of synthesis.Yamanaka seminar [Tetrahedron Lett.2007,48:8990.
；Supramol.Chem, 2011,23:140.] report and a kind of novel there are the branched three urea groups gels of symmetric three arms of C3
The factor, it forms supermolecule physical gel in polar solvent is such as acetone, and at the chemistry of the halogen ion added or slaine etc.
Under stimulation, there is reversible sol-gel conversion.Yamanaka seminar is further by the branched three urea groups gels of three arms
The peripheral of the factor introduces α-D-glucosides base group modification, obtains can be used as the dodecyl sodium sulfate-supermolecular gel of Separation of Proteins
The brave seminar of electrophoresis (SUGE) [Chem.Commun., 2011,47:10344.] Wang Le [Chem.Commun., 2012,48:
7973.] design has synthesized three ureido derivatives of tribenzylamine tripod structure, find its in the solution or under bulk state, logical
Cross 6 connected head-to-tail urea groups hydrogen bonds and assemble formation dimer；And under ultrasonication, hydrogen bond re-organized drives formation to have
The supermolecular gel of nanofibrous structures.
Molecular recognition is mainly in the supramolecular system that acceptor molecule is combined with substrate molecule by noncovalent interaction power requirement host and guest
Body has matching on energy and space structure.They are by the cooperative effect of the weak interaction force of local, each network made
The structure that compound formation rule is orderly, molecular recognition process needs to follow following two principle: principle of complementarity and pre-organized principle.
Molecular imprinting is exactly a kind of significant process of molecular recognition, its feature exactly target molecule is had specific recognition from
And target molecule is had high adsorption capacity and adsorptive selectivity.Function list based on molecularly imprinted polymer prepared by this technology
Body must simultaneously have containing polymerisable double bond and can be with the functional group of template molecule generation specific recognition, conventional function
Monomer is: 4-vinylphenylboronic acid, 4-vinylbenzaldehyde, 4-vinyl aniline, 4-Vinyl phenol, acrylic acid, second are dilute
Yl benzoic acid vinylpyridine, vinyl imidazole, methyl acrylamide, acrylamide etc., at present about the supermolecule of many urea groups
The application of class is also rarely reported, and about both containing many urea groups identification functional group, contains phenylethylene the most simultaneously
Double bond, it is easy to polymerization, there is not been reported for the novel structure of formation cross linked polymer.
Chinese patent (patent No.: 201010578029) reports with poly-[three (2,3-glycidyl) chlorinated isocyanurates-co-
Three (2-amino-ethyl) amine] it is porous integral material skeleton, use NH3Make epoxide group open loop formed primary amine group, can be used for
Carry out the porous integral material of anion exchange, as chromatography separation media and the rich medium etc. of anion sample.
Chinese patent (patent No.: 201310690028) discloses the system of a kind of fluorescent rare earth complex modified Nano-aluminum emulsion
Preparation Method, that includes the modified Nano silicon-preparation of aluminum emulsion, the surface modification of modified Nano silicon-aluminum, fluorescent rare earth complex
The preparation of modified Nano silicon-aluminum emulsion, above-mentioned use modifying agent, catalyst, silane coupler are three aminopropyl-triethoxy silicon
Alkane or triuret ethyl triethoxy silicane alkane, prepared coordination compound excitation wavelength 330nm, emission wavelength 612nm, luminous intensity
98a.u。
Chinese patent (patent No.: 201510025566) discloses a kind of damping noise reduction composite and preparation method thereof, this
Bright is by intermolecular hydrogen bond association, polyhydroxy functional groups material and many urea/ureido functionals is rolled into a ball material synthesis and has high crosslinking
The composite of three dimensional network structure, and base oil forms a kind of highly cross-linked oil film, has good anti-attrition characteristic.
The subject matter that molecular imprinting exists at present has, and the function monomer of use, cross-linking agent and polymerization have a foregone conclusion
Sex-limited.Especially can prepare on a large scale and the kind of function monomer cheap and easy to get is very limited to such an extent as to can not meet some mesh
The requirement of mark molecular recognition, this allows for molecular imprinting still can not meet the needs of actual application in some fields.Therefore,
At molecular engram during this, one of difficult point seeks to design and synthesizes different function monomer molecules and matched crosslinking
On the one hand agent, with the synthesis of three (amino-ethyl) amine triuret function monomer as skeleton, introduce different substituents at urea groups end
Acidity can be changed, on the other hand, also widened the scope of application of monomer by the introducing of various functional groups.Spider chemical combination
Thing is a kind of semirigid compound, and it forms sizeable cavity, in addition side substitution by freely overturning of three side chains
The multiformity of base so that it is have the structure of functional groups of abundant changeable specific recognition, spider function monomer is by a top
End atom or group connect three functional groups being at least respectively arranged with a specific recognition and the monomer of polymerizable double bond, its three
The urea groups side chain of strong specific recognition can form stable molecularly imprinted polymer, meanwhile, its three with many template molecules
Strong urea groups side chain can wrap up template molecule from multi-direction and angle, thus improves the specificity to template molecule identification.Therefore,
The tripod structure function monomer molecule of design synthesis novelty is at molecular engram, bionics, chromatographic isolation, Solid-Phase Extraction, film
The aspects such as separation field have extraordinary application prospect.
Summary of the invention
Present invention aim at, it is provided that a kind of many urea groups tripod-type function monomer molecule synthesis method centered by nitrogen, the party
The method that method generates many ureas by one end with cinnamic isocyanates and three replacement amine, employing 3-isopropenyl-α, α-
Dimethyl benzyl isocyanate and the reaction of three (amino-ethyl) amine, by obtaining the optimization of reaction dissolvent and response time
Many urea groups tripod-type function monomer molecule centered by nitrogen.Synthesized many urea groups tripod-type function monomer centered by nitrogen
The advantage of molecule is: spider function monomer be by a top nitrogen-atoms connect the urea/ureido functional group of three specific recognition with
And polymerisable styrene double bond, the urea groups side chain of its three strong specific recognition can be formed stable with many template molecules
Molecularly imprinted polymer, meanwhile, its three strong urea groups side chains can wrap up template molecule from multi-direction and angle, thus improves
Specificity to template molecule identification, for synthesizing new molecularly imprinted polymer, therefore, the spider knot that design synthesis is novel
Structure function monomer molecule is at molecular engram, and the aspect such as bionics, chromatographic isolation, Solid-Phase Extraction, membrance separation field has extraordinary
Application prospect.The method of the present invention is simple to operate, and the response time is short, and post processing is simple.Solve molecularly imprinted polymer limited
Type of crosslinking agent in the limitednumber of function monomer that adapts therewith, and produce substantial amounts of non-specific during molecular engram
The recognition site of property, the problem that identification selection is the highest.
A kind of many urea groups tripod-type function monomer molecule synthesis method centered by nitrogen of the present invention, it is characterised in that press
The following step is carried out:
A, in molar ratio three (2-aminoethyl) amine: 3-isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate=1:3-3.5 weighs instead
Answering raw material, then in round-bottomed flask, by three (2-aminoethyls), amine solvent is in solvent is dichloromethane or acetonitrile, at constant pressure addition
Again 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates being dissolved in solvent in funnel is in dichloromethane or acetonitrile, at ice
Stirring cooling 10min under water bath condition；
B, under the conditions of ice-water bath, be the 3-isopropenyl-α in dichloromethane or acetonitrile by step a is dissolved in solvent,
The solution of α-dimethylbenzyl isocyanates is slowly dropped to and is dissolved in solvent is three (2-aminoethyls) in dichloromethane or acetonitrile
In amine aqueous solution, time for adding is 20min；
After c, dropping, the reaction system in step b at room temperature being reacted, the time is 4h-16h, separates
Purification, steams evaporimeter by reactant liquor rotation and is spin-dried for, the solid with methylene chloride washing of gained, is vacuum dried 6h temperature 40 DEG C,
Obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
A kind of many urea groups tripod-type function monomer molecule synthesis method centered by nitrogen of the present invention, the one of synthesis with
Many urea groups tripod-type function monomer molecular equation centered by nitrogen is:
The present invention provides a kind of tripod-type function monomer molecule synthesis method of many urea groups centered by nitrogen, and the method passes through benzene second
Alkene one end with isocyanates and triamine generate urea method, use 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates
React with three (2-aminoethyl) amine, by controlling the mol ratio of reaction raw materials, response time, reaction dissolvent, obtain both containing end
End polymerizable double bond, contains the phenylethylene function monomer molecule of many urea/ureido functionals group with self aggregation effect the most simultaneously.This
Bright a kind of described many urea groups tripod-type function monomer molecule synthesis method centered by nitrogen, the method is compared with prior art
It has the beneficial effect that the method for the present invention is simple to operate, and the response time is short, and post processing is simple, in synthesized by the present invention with nitrogen being
The advantage of many urea groups tripod-type function monomer molecule of the heart is: function of foot rest monomer is to connect three by a top nitrogen-atoms
The urea/ureido functional group of specific recognition and polymerizable styrene double bond, the urea groups side chain of its three strong specific recognition can be with
Many template molecules form stable molecularly imprinted polymer, and these polymer have special three-D space structure, are used for synthesizing
Novel molecular engram polymer, synthesized novel molecular engram polymer divides at bionics, chromatographic isolation, Solid-Phase Extraction, film
Application prospect from aspects such as fields.
Accompanying drawing explanation
Fig. 1 is the present invention's1H NMR (nucleus magnetic hydrogen spectrum) figure；
Fig. 2 is the present invention13C NMR (nuclear-magnetism carbon spectrum) figure；
Fig. 3 is MS of the present invention (mass spectrum) figure.
Detailed description of the invention
Below in conjunction with executing example, the present invention is described in detail.
Embodiment 1
Three (2-aminoethyl) amine (1mmol, 146mg) are dissolved in acetonitrile solution 10mL, at constant pressure addition by round-bottomed flask
3-isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate (3mmol, 603mg) is dissolved in acetonitrile solution 10mL by funnel again
, magneton stirring cooling 10min under the conditions of ice-water bath；
Under the conditions of ice-water bath, the solution of the 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates being dissolved in acetonitrile delays
Slowly being added drop-wise in three (2-aminoethyl) amine aqueous solution being dissolved in acetonitrile, time for adding is 20min；
After dropping, reaction system is reacted at ambient temperature 4h, after completion of the reaction, carries out isolated and purified, by reactant liquor
Steaming evaporimeter with rotation to remove, i.e. obtain the solid of white, the solid with methylene chloride 20mL of gained washs 3 times, temperature 40 DEG C
6h is dried in vacuum drying, and obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
1H NMR(400MHz,CDCl3)δH 7.44(3H,s),7.30–7.15(9H,m),5.88(6H,s),
5.30(3H,s),5.02(3H,s),2.98(6H,s),2.29(6H,s),2.09(9H,s),1.52(18
H,s).13C NMR(400MHz,CDCl3)δC 158.30(s),148.26(s),143.43(s),140.93(s),
128.02(s),124.16(s),123.43(s),121.84(s),112.25(s),109.89(s),55.61(s),
54.76(s),38.24(s),30.32(s),22.03(s).MS m/z 750(M+)。
Embodiment 2
Three (2-aminoethyl) amine (1mmol, 146mg) are dissolved in acetonitrile solution 10mL, at constant pressure addition by round-bottomed flask
3-isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate (3.2mmol, 643mg) is dissolved in acetonitrile solution 10mL by funnel again
In, magneton stirring cooling 10min under the conditions of ice-water bath；
Under the conditions of ice-water bath, the solution of the 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates being dissolved in acetonitrile delays
Slowly being added drop-wise in three (2-aminoethyl) amine aqueous solution being dissolved in acetonitrile, time for adding is 20min；
After dropping, reaction system is reacted at ambient temperature 4h, after completion of the reaction, carries out isolated and purified, by reactant liquor
Steaming evaporimeter with rotation to remove, i.e. obtain the solid of white, the solid with methylene chloride 20mL of gained washs 3 times, temperature 40 DEG C
6h is dried in vacuum drying, and obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
1H NMR(400MHz,CDCl3)δH 7.44(3H,s),7.30–7.15(9H,m),5.88(6H,s),
5.30(3H,s),5.02(3H,s),2.98(6H,s),2.29(6H,s),2.09(9H,s),1.52(18
H,s).13C NMR(400MHz,CDCl3)δC 158.30(s),148.26(s),143.43(s),140.93(s),
128.02(s),124.16(s),123.43(s),121.84(s),112.25(s),109.89(s),55.61(s),
54.76(s),38.24(s),30.32(s),22.03(s).MS m/z 750(M+)。
Embodiment 3
Three (2-aminoethyl) amine (1mmol, 146mg) are dissolved in acetonitrile solution 10mL, at constant pressure addition by round-bottomed flask
3-isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate (3.5mmol, 703mg) is dissolved in acetonitrile solution 10mL by funnel again
In, magneton stirring cooling 10min under the conditions of ice-water bath；
Under the conditions of ice-water bath, the solution of the 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates being dissolved in acetonitrile delays
Slowly being added drop-wise in three (2-aminoethyl) amine aqueous solution being dissolved in acetonitrile, time for adding is 20min；
After dropping, reaction system is reacted at ambient temperature 4h, after completion of the reaction, carries out isolated and purified, by reactant liquor
Steaming evaporimeter with rotation to remove, i.e. obtain the solid of white, the solid with methylene chloride 20mL of gained washs 3 times, temperature 40 DEG C
6h is dried in vacuum drying, and obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
1H NMR(400MHz,CDCl3)δH 7.44(3H,s),7.30–7.15(9H,m),5.88(6H,s),
5.30(3H,s),5.02(3H,s),2.98(6H,s),2.29(6H,s),2.09(9H,s),1.52(18
H,s).13C NMR(400MHz,CDCl3)δC 158.30(s),148.26(s),143.43(s),140.93(s),
128.02(s),124.16(s),123.43(s),121.84(s),112.25(s),109.89(s),55.61(s),
54.76(s),38.24(s),30.32(s),22.03(s).MS m/z 750(M+)。
Embodiment 4
Three (2-aminoethyl) amine (1mmol, 146mg) are dissolved in acetonitrile solution 10mL, at constant pressure addition by round-bottomed flask
3-isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate (3.5mmol, 703mg) is dissolved in acetonitrile solution 10mL by funnel again
In, magneton stirring cooling 10min under the conditions of ice-water bath；
Under the conditions of ice-water bath, the solution of the 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates being dissolved in acetonitrile delays
Slowly being added drop-wise in three (2-aminoethyl) amine aqueous solution being dissolved in acetonitrile, time for adding is 20min；
After dropping, reaction system is reacted at ambient temperature 6h, after completion of the reaction, carries out isolated and purified, by reactant liquor
Steaming evaporimeter with rotation to remove, i.e. obtain the solid of white, the solid with methylene chloride 20mL of gained washs 3 times, temperature 40 DEG C
6h is dried in vacuum drying, and obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
1H NMR(400MHz,CDCl3)δH 7.44(3H,s),7.30–7.15(9H,m),5.88(6H,s),
5.30(3H,s),5.02(3H,s),2.98(6H,s),2.29(6H,s),2.09(9H,s),1.52(18
H,s).13C NMR(400MHz,CDCl3)δC 158.30(s),148.26(s),143.43(s),140.93(s),
128.02(s),124.16(s),123.43(s),121.84(s),112.25(s),109.89(s),55.61(s),
54.76(s),38.24(s),30.32(s),22.03(s).MS m/z 750(M+)。
Embodiment 5
Three (2-aminoethyl) amine (1mmol, 146mg) are dissolved in acetonitrile solution 10mL, at constant pressure addition by round-bottomed flask
3-isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate (3.5mmol, 703mg) is dissolved in acetonitrile solution 10mL by funnel again
In, magneton stirring cooling 10min under the conditions of ice-water bath；
Under the conditions of ice-water bath, the solution of the 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates being dissolved in acetonitrile delays
Slowly being added drop-wise in three (2-aminoethyl) amine aqueous solution being dissolved in acetonitrile, time for adding is 20min；
After dropping, reaction system is reacted at ambient temperature 8h, after completion of the reaction, carries out isolated and purified, by reactant liquor
Steaming evaporimeter with rotation to remove, i.e. obtain the solid of white, the solid with methylene chloride 20mL of gained washs 3 times, temperature 40 DEG C
6h is dried in vacuum drying, and obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
1H NMR(400MHz,CDCl3)δH 7.44(3H,s),7.30–7.15(9H,m),5.88(6H,s),
5.30(3H,s),5.02(3H,s),2.98(6H,s),2.29(6H,s),2.09(9H,s),1.52(18
H,s).13C NMR(400MHz,CDCl3)δC 158.30(s),148.26(s),143.43(s),140.93(s),
128.02(s),124.16(s),123.43(s),121.84(s),112.25(s),109.89(s),55.61(s),
54.76(s),38.24(s),30.32(s),22.03(s).MS m/z 750(M+)。
Embodiment 6
Three (2-aminoethyl) amine (1mmol, 146mg) are dissolved in dichloromethane solution 10mL, in constant voltage by round-bottomed flask
Again by that 3-isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate (3mmol, 603mg) is dissolved in dichloromethane is molten in Dropping funnel
In liquid 10mL, magneton stirring cooling 10min under the conditions of ice-water bath；
Under the conditions of ice-water bath, the 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates being dissolved in dichloromethane molten
Liquid is slowly dropped in three (2-aminoethyl) amine aqueous solution being dissolved in dichloromethane, and time for adding is 20min；
After dropping, reaction system is reacted at ambient temperature 4h, after completion of the reaction, carries out isolated and purified, by reactant liquor
Steaming evaporimeter with rotation to remove, i.e. obtain the solid of white, the solid with methylene chloride 20mL of gained washs 3 times, temperature 40 DEG C
6h is dried in vacuum drying, and obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
1H NMR(400MHz,CDCl3)δH 7.44(3H,s),7.30–7.15(9H,m),5.88(6H,s),
5.30(3H,s),5.02(3H,s),2.98(6H,s),2.29(6H,s),2.09(9H,s),1.52(18
H,s).13C NMR(400MHz,CDCl3)δC 158.30(s),148.26(s),143.43(s),140.93(s),
128.02(s),124.16(s),123.43(s),121.84(s),112.25(s),109.89(s),55.61(s),
54.76(s),38.24(s),30.32(s),22.03(s).MS m/z 750(M+)。
Embodiment 7
Three (2-aminoethyl) amine (1mmol, 146mg) are dissolved in dichloromethane solution 10mL, in constant voltage by round-bottomed flask
3-isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate (3.2mmol, 643mg) is dissolved in dichloromethane by Dropping funnel again
In solution 10mL, magneton stirring cooling 10min under the conditions of ice-water bath；
Under the conditions of ice-water bath, the 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates being dissolved in dichloromethane molten
Liquid is slowly dropped in three (2-aminoethyl) amine aqueous solution being dissolved in dichloromethane, and time for adding is 20min；
After dropping, reaction system is reacted at ambient temperature 4h, after completion of the reaction, carries out isolated and purified, by reactant liquor
Steaming evaporimeter with rotation to remove, i.e. obtain the solid of white, the solid with methylene chloride 20mL of gained washs 3 times, temperature 40 DEG C
6h is dried in vacuum drying, and obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
1H NMR(400MHz,CDCl3)δH 7.44(3H,s),7.30–7.15(9H,m),5.88(6H,s),
5.30(3H,s),5.02(3H,s),2.98(6H,s),2.29(6H,s),2.09(9H,s),1.52(18
H,s).13C NMR(400MHz,CDCl3)δC 158.30(s),148.26(s),143.43(s),140.93(s),
128.02(s),124.16(s),123.43(s),121.84(s),112.25(s),109.89(s),55.61(s),
54.76(s),38.24(s),30.32(s),22.03(s).MS m/z 750(M+)。
Embodiment 8
Three (2-aminoethyl) amine (1mmol, 146mg) are dissolved in dichloromethane solution 10mL, in constant voltage by round-bottomed flask
3-isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate (3.5mmol, 703mg) is dissolved in dichloromethane by Dropping funnel again
In solution 10mL, magneton stirring cooling 10min under the conditions of ice-water bath；
Under the conditions of ice-water bath, the 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates being dissolved in dichloromethane molten
Liquid is slowly dropped in three (2-aminoethyl) amine aqueous solution being dissolved in dichloromethane, and time for adding is 20min；
After dropping, reaction system is reacted at ambient temperature 4h, after completion of the reaction, carries out isolated and purified, by reactant liquor
Steaming evaporimeter with rotation to remove, i.e. obtain the solid of white, the solid with methylene chloride 20mL of gained washs 3 times, temperature 40 DEG C
6h is dried in vacuum drying, and obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
1H NMR(400MHz,CDCl3)δH 7.44(3H,s),7.30–7.15(9H,m),5.88(6H,s),
5.30(3H,s),5.02(3H,s),2.98(6H,s),2.29(6H,s),2.09(9H,s),1.52(18
H,s).13C NMR(400MHz,CDCl3)δC 158.30(s),148.26(s),143.43(s),140.93(s),
128.02(s),124.16(s),123.43(s),121.84(s),112.25(s),109.89(s),55.61(s),
54.76(s),38.24(s),30.32(s),22.03(s).MS m/z 750(M+)。
Embodiment 9
Three (2-aminoethyl) amine (1mmol, 146mg) are dissolved in dichloromethane solution 10mL, in constant voltage by round-bottomed flask
3-isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate (3.5mmol, 703mg) is dissolved in dichloromethane by Dropping funnel again
In solution 10mL, magneton stirring cooling 10min under the conditions of ice-water bath；
Under the conditions of ice-water bath, the 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanates being dissolved in dichloromethane molten
Liquid is slowly dropped in three (2-aminoethyl) amine aqueous solution being dissolved in dichloromethane, and time for adding is 20min；
After dropping, reaction system is reacted at ambient temperature 8h, after completion of the reaction, carries out isolated and purified, by reactant liquor
Steaming evaporimeter with rotation to remove, i.e. obtain the solid of white, the solid with methylene chloride 20mL of gained washs 3 times, temperature 40 DEG C
6h is dried in vacuum drying, and obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
1H NMR(400MHz,CDCl3)δH 7.44(3H,s),7.30–7.15(9H,m),5.88(6H,s),
5.30(3H,s),5.02(3H,s),2.98(6H,s),2.29(6H,s),2.09(9H,s),1.52(18
H,s).13C NMR(400MHz,CDCl3)δC 158.30(s),148.26(s),143.43(s),140.93(s),
128.02(s),124.16(s),123.43(s),121.84(s),112.25(s),109.89(s),55.61(s),
54.76(s),38.24(s),30.32(s),22.03(s).MS m/z 750(M+)。
Claims (1)
1. the many urea groups tripod-type function monomer molecule synthesis method centered by nitrogen, it is characterised in that follow these steps to carry out:
A, in molar ratio three (2-aminoethyl) amine: 3-isopropenyl-α, α-dimethylbenzyl isocyanates=1:3-3.5 weighs reaction raw materials, then in round-bottomed flask by three (2-aminoethyl) amine solvent in solvent is dichloromethane or acetonitrile, again by 3-isopropenyl-α in constant pressure funnel, it is in dichloromethane or acetonitrile that α-dimethylbenzyl isocyanates is dissolved in solvent, stirring cooling 10min under the conditions of ice-water bath；
B, under the conditions of ice-water bath, it is the 3-isopropenyl-α in dichloromethane or acetonitrile by step a is dissolved in solvent, the solution of α-dimethylbenzyl isocyanates is slowly dropped to and is dissolved in solvent is that in three (2-aminoethyl) amine aqueous solution in dichloromethane or acetonitrile, time for adding is 20min；
After c, dropping, reaction system in step b is at room temperature reacted, time is 4h-8h, carry out isolated and purified, reactant liquor rotation is steamed evaporimeter be spin-dried for, the solid with methylene chloride washing of gained, is vacuum dried 6h temperature 40 DEG C, and obtaining white solid is the many urea groups tripod-type function monomer molecule centered by nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610467226.1A CN106008275A (en) | 2016-06-24 | 2016-06-24 | Synthesis method of multi-ureido tripodal type functional monomer molecule with nitrogen as center |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610467226.1A CN106008275A (en) | 2016-06-24 | 2016-06-24 | Synthesis method of multi-ureido tripodal type functional monomer molecule with nitrogen as center |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106008275A true CN106008275A (en) | 2016-10-12 |
Family
ID=57086753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610467226.1A Pending CN106008275A (en) | 2016-06-24 | 2016-06-24 | Synthesis method of multi-ureido tripodal type functional monomer molecule with nitrogen as center |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106008275A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736140A (en) * | 2022-03-25 | 2022-07-12 | 广西大学 | Ethyl dimethacrylate- (1S,2S) -1, 2-diphenylethylenediamine-based urea and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324909A (en) * | 2000-05-18 | 2001-12-05 | 国家淀粉及化学投资控股公司 | Electronic donor compound capable of solidifying |
| US20080038832A1 (en) * | 2004-10-12 | 2008-02-14 | Mip Technologies Ab | Method for Producing Molecularly Imprinted Polymers for the Recognition of Target Molecules |
| WO2009064245A1 (en) * | 2007-11-12 | 2009-05-22 | Mip Technologies Ab | Imprinted polymers with affinity for phosphorylated peptides and proteins |
| CN103193824A (en) * | 2013-04-08 | 2013-07-10 | 淮海工学院 | Functional monomer and preparation method thereof |
-
2016
- 2016-06-24 CN CN201610467226.1A patent/CN106008275A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324909A (en) * | 2000-05-18 | 2001-12-05 | 国家淀粉及化学投资控股公司 | Electronic donor compound capable of solidifying |
| US20080038832A1 (en) * | 2004-10-12 | 2008-02-14 | Mip Technologies Ab | Method for Producing Molecularly Imprinted Polymers for the Recognition of Target Molecules |
| WO2009064245A1 (en) * | 2007-11-12 | 2009-05-22 | Mip Technologies Ab | Imprinted polymers with affinity for phosphorylated peptides and proteins |
| CN103193824A (en) * | 2013-04-08 | 2013-07-10 | 淮海工学院 | Functional monomer and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| CHRISTOPHE GOMY等: ""Rational Design of New Polymerizable Oxyanion Receptors"", 《J. ORG. CHEM.》 * |
| GAO HAIFENG等: ""Preparation of a Water‐Soluble Fluorescent Polymer"", 《JOURNAL OF MACROMOLECULAR SCIENCE, PART A》 * |
| WANG JIALU等: ""Templated polymers enable selective capture and release of lysophosphatidic acid in human plasma via optimization of non-covalent binding to functional monomers"", 《ANALYST》 * |
| WU XIANGYANG等: ""Comparison of monofunc tional and multifunc tional monomers in phosphate binding molecularly imprinted polymers"", 《J. MOL. RECOGNIT.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736140A (en) * | 2022-03-25 | 2022-07-12 | 广西大学 | Ethyl dimethacrylate- (1S,2S) -1, 2-diphenylethylenediamine-based urea and preparation method and application thereof |
| CN114736140B (en) * | 2022-03-25 | 2023-05-05 | 广西大学 | Ethyl dimethacrylate- (1S, 2S) -1, 2-diphenyl ethylene diamine urea and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bisson et al. | Synthesis and recognition properties of aromatic amide oligomers: molecular zippers | |
| Kokan et al. | A photoswitchable heteroditopic ion-pair receptor | |
| Zhang et al. | Permanently porous Co (II) porphyrin-based hydrogen bonded framework for gas adsorption and catalysis | |
| Nakamura et al. | A hierarchical self-assembly system built up from preorganized tripodal helical metal complexes | |
| Hu et al. | A1/A2-diamino-substituted pillar [5] arene-based acid–base-responsive host–guest system | |
| Donnelly et al. | Adaptive N-mesoionic ligands anchored to a triazolylidene for ruthenium-mediated (de) hydrogenation catalysis | |
| Carbonell et al. | Silsesquioxane–terpyridine nano building blocks for the design of three-dimensional polymeric networks | |
| JPH04166764A (en) | Packing agent for liquid chromatography and preparation thereof | |
| Li et al. | Construction of hetero [n] rotaxanes by use of polyfunctional rotaxane frameworks | |
| CN101974110A (en) | Preparation method of water-soluble ferrocene supramolecular inclusion compound | |
| Johari et al. | An overview of metal-free sustainable nitrogen-based catalytic knoevenagel condensation reaction | |
| CN107163034A (en) | A kind of thiophene carbazole thiophene derivant and preparation method and application | |
| McConnell et al. | Orthogonal stimuli trigger self-assembly and phase transfer of FeII4L4 cages and cargoes | |
| CN106279442A (en) | The preparation method of a kind of ion liquid functionalization cellulose and cellulose and application | |
| CN110551031A (en) | method for water-phase catalysis Henry asymmetric addition reaction based on polyion liquid type chiral copper amino acid catalyst | |
| CN109160995A (en) | A kind of column [5] aromatic hydrocarbons self assembly elastomeric material and preparation method thereof | |
| Zhang et al. | Synthesis of 2-Aryl-5-alkyl-fulleropyrrolidines: Metal-Free-Mediated Reaction of [60] Fullerene with Aromatic Aldehydes and Inactive Primary Amines | |
| Ren et al. | Thermoresponsive chiral stationary phase functionalized with the copolymer of β-cyclodextrin and N-isopropylacrylamide for high performance liquid chromatography | |
| Mishra et al. | Recent advances on triazolium ionic liquids: synthesis and applications | |
| Park et al. | Different origins of strain-induced chirality inversion of Co2+-triggered supramolecular peptide polymers | |
| CN106008275A (en) | Synthesis method of multi-ureido tripodal type functional monomer molecule with nitrogen as center | |
| CN103193898B (en) | L-Phe derives the synthesis of beta-cyclodextrin bonded silica gel and applies the separation of Alanine enantiomers | |
| CN105330761B (en) | Chitosan two（Aromatic radical carbamate）‑（Urea）, its chiral stationary phase and preparation method thereof | |
| CN102863387B (en) | Novel synthetic method for imidazole onium salts | |
| Umali et al. | Triazine dendrimers with orthogonally protected amines on the periphery. Masking amines with Dde and BOC groups provides an alternative to carrying protected alcohols and disulfides through an iterative synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161012 |
|
| RJ01 | Rejection of invention patent application after publication |