CN115572306A - Synthesis method of novel silane coupling agent trioxy-triethoxy-iminodiacetic acid diethyl ester organosilane - Google Patents
Synthesis method of novel silane coupling agent trioxy-triethoxy-iminodiacetic acid diethyl ester organosilane Download PDFInfo
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- diethyl ester
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- 238000001308 synthesis method Methods 0.000 title claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 title abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- -1 allyloxy triethylene glycol Chemical compound 0.000 claims abstract description 20
- LJDNMOCAQVXVKY-UHFFFAOYSA-N ethyl 2-[(2-ethoxy-2-oxoethyl)amino]acetate Chemical compound CCOC(=O)CNCC(=O)OCC LJDNMOCAQVXVKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims abstract description 17
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 13
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002252 acyl group Chemical group 0.000 claims abstract description 12
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- MFFXVVHUKRKXCI-UHFFFAOYSA-N ethyl iodoacetate Chemical compound CCOC(=O)CI MFFXVVHUKRKXCI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012312 sodium hydride Substances 0.000 claims abstract description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 238000004440 column chromatography Methods 0.000 claims description 20
- 235000019439 ethyl acetate Nutrition 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 11
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 7
- DYHCCCWROHIOFM-UHFFFAOYSA-N 2-iodoethyl acetate Chemical compound CC(=O)OCCI DYHCCCWROHIOFM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- ZHSWSXCDJMIGPF-UHFFFAOYSA-N 1-[2-(2-hydroxyethoxy)ethoxy]-3-(oxiran-2-yl)propan-2-ol Chemical compound OCCOCCOCC(CC1OC1)O ZHSWSXCDJMIGPF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract description 4
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002585 base Substances 0.000 abstract description 3
- ULQQGOGMQRGFFR-UHFFFAOYSA-N 2-chlorobenzenecarboperoxoic acid Chemical compound OOC(=O)C1=CC=CC=C1Cl ULQQGOGMQRGFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 2
- 239000004032 superbase Substances 0.000 abstract description 2
- 150000007525 superbases Chemical class 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- OJCSPXHYDFONPU-UHFFFAOYSA-N etoac etoac Chemical compound CCOC(C)=O.CCOC(C)=O OJCSPXHYDFONPU-UHFFFAOYSA-N 0.000 abstract 1
- 150000001282 organosilanes Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000575 pesticide Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QXTIBZLKQPJVII-UHFFFAOYSA-N triethylsilicon Chemical group CC[Si](CC)CC QXTIBZLKQPJVII-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003124 biologic agent Substances 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003925 brain function Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- IHLAQQPQKRMGSS-UHFFFAOYSA-N oxiracetam Chemical compound NC(=O)CN1CC(O)CC1=O IHLAQQPQKRMGSS-UHFFFAOYSA-N 0.000 description 1
- 229960001227 oxiracetam Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000006916 protein interaction Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to the technical field of chemical synthesis, in particular to a method for synthesizing silane coupling agent trioxy-triethoxy-iminodiacetic acid diethyl ester organosilane. The invention firstly uses ethyl iodoacetate and allyloxy triethylene glycol inN,N-1, 8-diazabicyclo [5.4.0 ] in Dimethylformamide (DMF)]Synthesis of diethyl allyloxytrimethyleneglycolacyliminodiacetate in a series of reactions with undec-7-ene (DBU) as catalyst. This derivative was reacted with chloroperoxybenzoic acid (MCPBA) and triphenylphosphine (Ph) 3 P) are mixed successively in the presence of sodium hydride as a strong base and boron trifluoride etherate (BF) 3• C 2 H 6 O) is used as a catalyst, and the epoxypropyl triethylene glycol acyl iminodiacetic acid diethyl ester is synthesized. Finally, the mixture is mixed with (3-chloropropyl) triethoxysilane under the condition of superbase sodium block, and the target product is prepared by reaction under the catalysis of a phase transfer catalyst benzyltriethylammonium chloride (TEBA). The method of the invention fills the defect that the prior art contains the imidoSynthesis of diethyl diacetate headgroup organosilanes is blank.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthesis method of a novel silane coupling agent of trioxy-triethoxy-iminodiacetic acid diethyl ester organosilane.
Background
Diethyl iminodiacetate is an important intermediate of medicines, pesticides and materials, can be used for preparing a brain function drug, such as oxiracetam, and is also widely applied to the fields of surfactants, complexing agents, food additives, metal surface treatment in the electroplating industry, polymer material industry, pharmacy and the like.
In nature, many inorganic substances such as glass, quartz, ceramics and the like contain Si-O-Si bonds, so that organic groups are generally lacking, and the compounds belong to inorganic polysiloxanes. However, in the organic silicon chemistry, organic groups need to be connected to silicon atoms to form siloxane compounds, and such organic silicon substances can interact with hydroxyl in inorganic substances and long molecular chains in organic polymers, so that two materials with different properties are coupled, and various properties of biological materials are improved. Therefore, the epoxy resin composition is widely applied to rubber, plastics, filling composite materials, epoxy encapsulating materials, elastomers, coatings, adhesives, sealants and the like.
Triethylsilyl groups are widely present in organic compounds and have important applications in organic synthesis. Silicon heterocyclic compounds are widely used in organic synthetic chemistry, material chemistry, and pharmaceutical chemistry due to their unique physicochemical properties. Therefore, the organic compound containing the triethyl silicon group is directly used for research on synthesis of intermediates of medicines, pesticides and the like, and has important significance. The silicification reaction can protect specific functional groups in a chemical synthesis method so as to reduce the boiling point and increase the volatility of the compound, and the characteristic has important application prospect as an intermediate compound in the fields of medicines, pesticides and the like.
Research shows that the polyethylene glycol (PEG) head group can reduce the interaction between protein and diethyl iminodiacetate in organisms, so that the PEG head group is connected with the diethyl iminodiacetate, the nonspecific adsorption of biological agents before entering targets can be reduced, and the targeting property of the biological agents is improved.
At present, no relevant synthesis reports are found for organosilicon compounds which take iminodiacetic acid diethyl ester as a guiding head group, polyethylene glycol as an intermediate chain and triethylsilicon as a tail mark.
Disclosure of Invention
The invention aims to solve the problem of synthesizing an organic silicon compound which takes iminodiacetic acid diethyl ester as a guiding head group, polyethylene glycol as an intermediate chain and triethylsilicon as a tail mark, provides a method for synthesizing trioxy-triethoxy-iminodiacetic acid diethyl ester silane, solves the problem of building a 'molecular bridge' between interfaces of inorganic substances and organic substances, and has important significance for realizing the function in a biomedical targeted recognition and controlled release system.
By the organosilicon compound synthesized as described above, a "molecular bridge" can be built up between the interfaces of the inorganic substance and the organic substance, connecting two materials having completely different properties together. The target function of the compound in biomedicine, pesticide target identification and controlled release systems can be determined by the reaction groups of triethyl silicon base, diethyl iminodiacetate and organic functional groups of polyethylene glycol.
The triethoxy-diethyl iminodiacetate organosilane has the advantages of excellent activity, stable structure at normal temperature, good stereoselectivity, high stability of the formed coupling system and the like. The synthesis method can be used for synthesizing silane coupling agents such as a series of silicon alkyl chains, variable polyethylene glycol inter-chains and the like, and has an important effect in the field of synthesis research of organic silicon compounds. Therefore, the research on the synthesis method of the triethoxy-iminodiacetic acid diethyl ester organosilane fills the problem that the organic silicon compound explores the effect of a molecular bridge between the interfaces of inorganic substances and organic substances through an inorganic silicon connection technology, and opens up a new research and application path for accurate drug delivery in the fields of medicines and pesticides.
The invention is realized by the following technical scheme:
iodoacetic acid ethyl ester with allyloxy triethylene glycol in N, N-Dimethylformamide (DMF) with 1, 8-diazabicyclo [5.4.0 ]]Synthesis of diethyl allyloxytrimethyleneglycolacyliminodiacetate in a series of reactions with undec-7-ene (DBU) as catalyst. The derivative is reacted with chloroperoxybenzoic acid (MCPBA) and triphenylphosphine (Ph) 3 P) are mixed successively in the presence of sodium hydride as a strong base and boron trifluoride etherate (BF) 3· C 2 H 6 O) is used as a catalyst, and the epoxypropyl triethylene glycol acyl iminodiacetic acid diethyl ester is synthesized. Finally, the mixture is mixed with (3-chloropropyl) triethoxysilane under the condition of superbase sodium block, and reacts under the catalysis of a phase transfer catalyst benzyltriethylammonium chloride (TEBA) to prepare the target product triethoxy-iminodiacetic acid diethyl ester organosilane. The structural formula of the trioxy-triethoxy-diethyl iminodiacetate organosilane prepared by the invention is as follows:
the synthesis method of the trioxy-triethoxy-iminodiacetic acid diethyl ester organosilane comprises the following steps:
1) Synthesis of allyloxytrimethylglycol TG-aly
Dissolving triethylene glycol in dry Tetrahydrofuran (THF), stirring at room temperature for 30min, adding pure sodium, quickly stirring for 1h, dropwise adding allyl bromide, and continuously reacting for 6h; dissolving the residue after reduced pressure distillation with dichloromethane, washing with saturated sodium chloride (NaCl) solution, drying with anhydrous magnesium sulfate, filtering, concentrating, and purifying by column chromatography;
2) Synthesis of allyloxytrimethyleneglycol acyliminodiacetic acid diethyl ester
Mixing ethyl iodoacetate and TG-aly, dissolving in dry DMF, stirring at 0 deg.C for 1-2 hr (preferably 1.5 hr), rapidly adding catalytic amount of DBU, stirring at room temperature for 24 hr, adding 95% ethanol solution to decompose excessive DBU, washing with saturated NaCl solution, and adding anhydrous Na 2 SO 4 Drying, filtering, concentrating, and performing column chromatography to obtain eluent of ethyl acetate/petroleum ether.
3) Synthesis of epoxypropyl triethylene glycol acyl imino diethyl diacetate
Allyloxytrimethyleneglycol acyliminodiacetic acid diethyl ester and Ph 3 Mixing P and MCPBA, dissolving in dry dichloromethane, adding appropriate amount of sodium hydride powder, slowly heating to 30-50 deg.C (preferably 40 deg.C), rapidly stirring for 30min, and rapidly adding BF dropwise 3· C 2 H 6 O, continuously stirring for 30 hours at room temperature after the dropwise addition is finished, cooling a reaction product in an ice-water mixture to 0 ℃, and filtering; extracting the concentrated filtrate with mixed organic solvent, and distilling the organic phase under reduced pressure.
4) Synthesis of triethoxy-iminodiacetic acid diethyl ester silane
Dissolving epoxypropyl triethylene glycol acyl iminodiacetic acid diethyl ester and (3-chloropropyl) triethoxysilane in anhydrous DMF, stirring for 2h at 50-80 deg.C (preferably 60 deg.C), adding benzyl triethyl ammonium chloride (TEBA) as catalyst, and stirring for 12h. Washing the reactant with saturated sodium bicarbonate solution, concentrating the organic phase under reduced pressure, filtering, concentrating, separating by column chromatography, and standing in a freezing chamber for 3h to obtain white solid.
Further, in the step 1),
volume ratio of triethylene glycol to allyl bromide 1mL:1.3-2mL; preferably 1mL:1.5mL.
The mass-to-volume ratio of the sodium lumps to the triethylene glycol is 1g:2-3mL; preferably 1g:2.8mL;
the volume ratio of THF to triethylene glycol was 3-3.5mL:1mL; preferably 3mL:1mL.
In column chromatography, silica gel, etOAc and EtOAc were used, wherein the volume ratio v/v of EtOAc and EtOAc was 1.
Further, in the step 2),
the mass ratio of ethyl iodoacetate to TG-aly is 1g:2-3g; preferably 1g:2.5g.
The solvent DMF must be anhydrous;
the volume-mass ratio of DMF to iodoethyl acetate is 1mL:0.02-0.05g; preferably 1mL:0.05g;
the volume-mass ratio of DBU to TG-Allyl is 1 muL: 0.5g-1.30g; preferably 1. Mu.L: 1.25g;
the volume ratio of the 95% ethanol solution to the DBU was 1. Mu.L: 1 mu L of the solution;
in column chromatography, silica gel, etOAc and Petroleum are used, wherein the volume ratio v/v of EtOAc and Petroleum is 1.
Further, in the step 3),
the mass ratio of allyloxytrimethyleneglycol acyl iminodiacetic acid diethyl ester to MCPBA is 1g:0.5-1g, preferably 1g:1g of the total weight of the composition.
Allyloxytrimethyleneglycol acyliminodiacetic acid diethyl ester with Ph 3 The mass ratio of P is 1g:1.5-2g, preferably 1g:2g of the total weight of the composition.
The mixed organic solvent of the extraction filtrate is diethyl ether/ethyl acetate, and the volume ratio v/v is 1.
Further, in the step 4),
the volume ratio of the glycidyl triethylene glycol acyl iminodiacetic acid diethyl ester to the (3-chloropropyl) triethoxysilane is 15:1.
the volume ratio of DMF to diethyl epoxypropyltriglycol acyliminodiacetate is 4-4.5mL:3mL; preferably 4mL:3mL of
The volume-to-mass ratio of (3-chloropropyl) triethoxysilane to TEBA is 1mL:0.1-0.3g, preferably 1mL:0.2g.
Compared with the prior art, the invention has the following beneficial effects:
1) The synthesis method disclosed by the invention is an important raw material for preparing the silicon resin pancreatin-immobilized carrier, can be used for making the immobilized enzyme insoluble in water, and can be used for continuously filtering the inactivated solid-phase enzyme, so that the utilization rate of the biological enzyme is improved, the environmental pollution and the raw material waste are reduced, and the synthesis method fills the blank of synthesizing the coupling agent compound containing diethyl iminodiacetate in the organic silicon in the prior art.
2) The method has the advantages of few steps, simple and convenient operation, high efficiency, more conventional raw materials and catalysts, low toxicity or no toxicity, simple and easily-recovered subsequent treatment and high product yield, and breaks through the limit of complicated, complicated and fussy synthesis method and lower yield of the biomedical organosilicon compounds.
Drawings
FIG. 1 is a NMR spectrum of a final product prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and embodiments, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
(1) Synthesis of allyloxytrimethylglycol TG-aly
10mL of triethylene glycol is dissolved in 30mL of dry THF, stirred at room temperature for 30min, then 3.5g of pure sodium is added, stirred rapidly for 1h, 15mL of allyl bromide is added dropwise, and the reaction is continued for 6h. The residue after distillation under reduced pressure was dissolved in 30mL of dichloromethane, washed with saturated NaCl solution, dried over anhydrous magnesium sulfate, filtered, concentrated and purified by column chromatography to give 4g of a colorless oily product in 80% yield.
In column chromatography, silica gel, etOAc and EtOAc were used, wherein the volume ratio v/v of EtOAc and EtOAc was 1.
(2) Synthesis of allyloxytrimethyleneglycol acyliminodiacetic acid diethyl ester
0.5g of iodoethyl acetate and 1.25g of TG-aly were mixedMixing, dissolving in 10mL dry anhydrous DMF, stirring at 0 deg.C for 1.5 hr, quickly dropwise adding 1 μ L DBU, continuously stirring for 24 hr, adding 1 μ L95% ethanol to dissolve excessive DBU, washing with saturated NaCl solution, and removing anhydrous Na 2 SO 4 Drying, filtering, concentrating and column chromatography to obtain colorless viscous product 0.4g with 75% yield.
In column chromatography, silica gel, etOAc and Petroleum are used, wherein the volume ratio v/v of EtOAc to Petroleum is 1.
(3) Synthesis of epoxypropyl triethylene glycol acyl imino diethyl diacetate
5g of diethyl allyloxytrimethyleneglycol acyliminodiacetate with 5g of MCPBA and 10g of Ph 3 P is mixed successively and dissolved in 30ml dichloromethane, 0.5g sodium hydride powder is added into the solution rapidly, slowly heated to 40 ℃, stirred rapidly for 30min, and then 50 mul BF is dripped 3· C 2 H 6 And O, continuously stirring for 30 hours at room temperature after the dropwise addition is finished. After cooling to 0 ℃ with an ice-water mixture, the mixture was filtered, and the concentrated filtrate was mixed with 20ml of distilled water and extracted with an ether/ethyl acetate mixed solvent (v/v = 1. The aqueous phase was distilled under reduced pressure to obtain 3g of a clear solid product with a yield of 80%.
(4) Synthesis of triethoxy-iminodiacetic acid diethyl ester organosilane
7.5ml of epoxypropyltriglycolyliodiacetidenediacetic acid diethyl ester and 0.5ml of (3-chloropropyl) triethoxysilane are sequentially dissolved in 10ml of anhydrous DMF, stirred for 2h at 60 ℃, then 0.1g of TEBA is slowly added, continuously stirred for 12h, the reactant is washed by saturated sodium bicarbonate solution, the organic phase is concentrated under reduced pressure, filtered, concentrated and separated by column chromatography, and placed in a freezing chamber for 3h to obtain 2g of white solid. The yield was 70%.
1 H NMR(500MHz,CDCl 3 ):δ4.44–4.51(s,2H；H-2)；4.08–4.18(d,J＝12.2Hz,4H；H-1)；3.78–3.88(m,2H；2CH2,ethoxy)；3.32–3.40(m,2H；CH,acetyl),1.50–1.51(m,4H；2OCH2),1.48(m,4H；OCH2CH2)1.26–1.31(brs,12H；CH3),1.18–1.23(t,3J＝6.8Hz,9H；CH3)；0.56–0.60(t,3J＝6.05and 6.8Hz,2H；CH2).
In column chromatography, adoptSilica gel, etOAc and CH 3 OH, wherein EtOAc and CH 3 OH volume ratio v/v of 1 f ＝0.48
From fig. 1 and the above data results, it can be seen that: the final product obtained according to the synthesis method of the invention meets the characteristics of the target substance.
Application example 1 Synthesis of Hexaethoxy-triethoxy-Iminodiacetic acid diethyl ester organosilane
(1) Synthesis of allyloxypolyhexaethylene glycol
10mL of polyhexamethylene glycol are dissolved in 30mL of dry THF, stirred at room temperature for 60min, then 3.5g of pure sodium are added, stirred rapidly for 1h, 15mL of allyl bromide are added dropwise, and the reaction is continued for 6h. The residue after distillation under reduced pressure was dissolved in 30mL of dichloromethane, washed with saturated NaCl solution, dried over anhydrous magnesium sulfate, filtered, concentrated, and purified by recrystallization to obtain 3g of a colorless solid product in 70% yield.
Recrystallization solvent: petroleum ether (30-60 ℃ C.)
(2) Synthesis of allyloxy polyhexamethylene glycol acyl iminodiacetic acid diethyl ester
0.5g of iodoethyl acetate and 1.25g of allyloxypolyhexaethylene glycol were mixed and dissolved in 10mL of dry DMF, and the mixture was stirred at room temperature for 30min and rapidly added dropwise
DBU, continuously stirring for 24h, adding
Dissolving excess DBU in 95% ethanol, washing with saturated NaCl solution, and removing anhydrous Na 2 SO 4 Drying, filtering, concentrating and column chromatography to obtain colorless needle product 0.5g with yield of 80%.
In column chromatography, silica gel, etOAc and Petroleum are used, wherein the volume ratio v/v of EtOAc to Petroleum is 1.
(3) Synthesis of epoxypropyl polyhexamethylene glycol acyl iminodiacetic acid diethyl ester
5g of allyloxypolyhexaethyleneglycolacyliminodiacetic acid diethyl ester with 5g of MCPBA and 10g of Ph 3 P is mixed successively and dissolved in 30ml dichloromethane, 0.5g sodium hydride powder is added into the solution rapidly, slowly heated to 40 ℃, stirred rapidly for 30min, and then 50 mul BF is dripped 3· C 2 H 6 And O, continuously stirring for 30 hours at room temperature after the dropwise addition is finished. After cooling to 0 ℃ with an ice-water mixture, the mixture was filtered, and the concentrated filtrate was mixed with 20ml of distilled water and extracted with an ether/ethyl acetate mixed solvent (v/v = 1. The aqueous phase was distilled under reduced pressure to obtain 2g of a white solid product in the form of flakes in a yield of 60%.
(4) Synthesis of hexa-ethoxy-triethoxy-iminodiacetic acid diethyl ester organosilane
7.5ml of epoxypropyl polyhexamethylene glycol acyl iminodiacetic acid diethyl ester and 0.5ml of (3-chloropropyl) triethoxysilane are sequentially dissolved in 10ml of anhydrous DMF, stirred for 2h at 60 ℃, then 0.1g of TEBA is slowly added, stirring is continuously carried out for 12h, reactants are washed by saturated sodium bicarbonate solution, organic phase is subjected to pressure concentration and then filtration, after concentration, column chromatography separation is carried out, and the mixture is placed in a freezing chamber for 3h, thus obtaining 0.5g of white solid. The yield was 60%.
1 H NMR(500MHz,CDCl 3 ):δ4.50(s,8H；H-2),4.40(12H；H-1),4.13(d,J＝12.2Hz,4H；H-1),3.80–3.83(m,2H；2CH 2 ,ethoxy),3.38–3.40(m,2H；CH,acetyl),1(m,4H；2OCH 2 ),1.50–1.53(m,4H；OCH 2 CH 2 ),1.19–1.22(brs,12H；CH 3 ),0.50(t, 3 J＝6.05and 6.8Hz,2H；CH 2 ).1.20–1.21(t, 3 J＝6.8Hz,9H；CH 3 )
In column chromatography, silica gel, etOAc and CH are used 3 OH, wherein EtOAc and CH 3 OH has a volume ratio v/v of 1, R f ＝0.53.
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or other related fields can be directly or indirectly applied to the present invention, and the same shall be included in the scope of the present invention.
Claims (10)
1. A synthesis method of trioxy-triethoxy-iminodiacetic acid diethyl ester organosilane is characterized in that,
the structural formula of the triethoxy-diethyl iminodiacetate organosilane is shown as follows:
the synthesis method comprises the following steps:
1) Synthesis of allyloxytrimethylglycol TG-aly
Dissolving triethylene glycol in dry Tetrahydrofuran (THF), stirring at room temperature for 30min, adding pure sodium, quickly stirring for 1h, dropwise adding allyl bromide, and continuously reacting for 6h; dissolving the residue after reduced pressure distillation with dichloromethane, washing with saturated sodium chloride NaCl solution, drying with anhydrous magnesium sulfate, filtering, concentrating, and purifying by column chromatography;
2) Synthesis of allyloxytrimethyleneglycol acyliminodiacetic acid diethyl ester
Mixing ethyl iodoacetate and TG-aly, dissolving in dry DMF, stirring at 0 deg.C for 1-2 hr, quickly adding catalytic amount of DBU, stirring at normal temperature for 24 hr, adding 95% ethanol solution to dissolve excessive DBU, washing with saturated NaCl solution, and adding anhydrous Na 2 SO 4 Drying, filtering, concentrating, and performing column chromatography with ethyl acetate/petroleum ether as eluent;
3) Synthesis of epoxypropyl triethylene glycol acyl imino diethyl diacetate
Allyloxytrimethyleneglycol acyliminodiacetic acid diethyl ester with Ph 3 Mixing P and MCPBA, dissolving in dry dichloromethane, adding appropriate amount of sodium hydride powder, slowly heating to 30-50 deg.C, rapidly stirring for 30min, and rapidly adding BF dropwise 3 ·C 2 H 6 O, continuously stirring for 30 hours at room temperature after the dropwise addition is finished, cooling a reaction product in an ice-water mixture to 0 ℃, and filtering; extracting the concentrated filtrate with mixed organic solvent, and distilling the organic phase under reduced pressure;
4) Synthesis of triethoxy-iminodiacetic acid diethyl ester organosilane
Dissolving epoxypropyl triethylene glycol acyl iminodiacetic acid diethyl ester and (3-chloropropyl) triethoxysilane in anhydrous DMF, stirring at 50-80 deg.C for 2h, adding benzyl triethyl ammonium chloride (TEBA) as catalyst, and continuously stirring for 12h; washing the reactant with saturated sodium bicarbonate solution, concentrating the organic phase under reduced pressure, filtering, concentrating, separating by column chromatography, and standing in a freezing chamber for 3h to obtain white solid.
2. The method according to claim 1, wherein in step 1),
volume ratio of triethylene glycol to allyl bromide 1mL:1.3-2mL;
the mass-to-volume ratio of the sodium lumps to the triethylene glycol is 1g:2-3mL;
the volume ratio of THF to triethylene glycol was 3-3.5mL:1mL;
in column chromatography, silica gel and Et are used 2 O and EtOAc, wherein Et 2 The volume ratio v/v of O and EtOAc is 1.
3. The method according to claim 1, wherein in step 2),
the mass ratio of ethyl iodoacetate to TG-aly is 1g:2-3g;
the solvent DMF must be anhydrous;
the volume-mass ratio of DMF to iodoethyl acetate is 1mL:0.02-0.05g;
the volume mass ratio of DBU to TG-aly is 1 mu L:0.5g to 1.30g;
the volume ratio of the 95% ethanol solution to the DBU is 1 mu L:1 mu L of the solution;
in column chromatography, silica gel, etOAc and Petroleum are used, wherein the volume ratio v/v of EtOAc and Petroleum is 1.
4. The method according to claim 1, wherein, in the step 3),
the mass ratio of allyloxytrimethyleneglycol acyl iminodiacetic acid diethyl ester to MCPBA is 1g:0.5-1g;
allyloxy groupTriethylene glycol acyl iminodiacetic acid diethyl ester and Ph 3 The mass ratio of P is 1g:1.5-2g;
the mixed organic solvent of the extraction filtrate is diethyl ether/ethyl acetate, and the volume ratio v/v is 1.
5. The method according to claim 1, wherein, in the step 4),
the volume ratio of the glycidyl triethylene glycol acyl iminodiacetic acid diethyl ester to the (3-chloropropyl) triethoxysilane is 15:1;
the volume ratio of DMF to diethyl epoxypropyltriglycol acyliminodiacetate is 4-4.5mL:3mL;
the volume-to-mass ratio of (3-chloropropyl) triethoxysilane to TEBA is 1mL:0.1-0.3g.
6. The method of claim 1,
in the step 2) of synthesizing allyloxytrimethyleneglycol acyl diethyl iminodiacetate, iodoethyl acetate and allyloxytrimethylene glycol are mixed and then dissolved in dry DMF, and the mixture is stirred for 1.5 hours at the temperature of 0 ℃;
in the step 3), during the synthesis of the glycidyl triethylene glycol acyl diethyl iminodiacetate, adding a proper amount of sodium hydride powder, and slowly heating to 40 ℃;
in the step 4) of synthesizing the triethoxy-iminodiacetic acid diethyl ester organosilane, dissolving epoxypropyl triethylene glycol acyl iminodiacetic acid diethyl ester and (3-chloropropyl) triethoxysilane in anhydrous DMF, and stirring for 2h at 60 ℃.
7. The method according to claim 1, wherein, in the step 1),
the volume ratio of triethylene glycol to allyl bromide is preferably 1mL:1.5mL;
the mass-to-volume ratio of the sodium lumps to the triethylene glycol is preferably 1g:2.8mL;
the volume ratio of THF to triethylene glycol is preferably 3mL:1mL.
8. The method according to claim 1, wherein in step/2),
the mass ratio of ethyl iodoacetate to TG-aly is preferably 1g:2.5g;
the volume-to-mass ratio of DMF to iodoethyl acetate is preferably 1mL:0.05g;
the volume mass ratio of DBU to allyloxytrimethylene glycol is preferably 1 μ L:1.25g.
9. The method according to claim 1, wherein, in the step 3),
the mass ratio of allyloxytrimethyleneglycol acyliminodiacetic acid diethyl ester to MCPBA is preferably 1g:1g of a compound;
allyloxytrimethyleneglycol acyliminodiacetic acid diethyl ester with Ph 3 The mass ratio of P is preferably 1g:2g of the total weight of the composition.
10. The method according to claim 1, wherein, in the step 4),
the volume ratio of DMF to diethyl epoxypropyltriglycol acyliminodiacetate is preferably 4mL:3mL;
the volume-to-mass ratio of (3-chloropropyl) triethoxysilane to TEBA is preferably 1mL:0.2g.
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