CN116462612A - Tetrafunctional aromatic nitrile oxide compound and synthesis method thereof - Google Patents
Tetrafunctional aromatic nitrile oxide compound and synthesis method thereof Download PDFInfo
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- -1 aromatic nitrile Chemical class 0.000 title claims abstract description 59
- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 238000001308 synthesis method Methods 0.000 title abstract description 19
- 238000006266 etherification reaction Methods 0.000 claims abstract description 7
- 238000006146 oximation reaction Methods 0.000 claims abstract description 7
- 238000005893 bromination reaction Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 51
- 238000001914 filtration Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000001632 sodium acetate Substances 0.000 claims description 14
- 235000017281 sodium acetate Nutrition 0.000 claims description 14
- OYSVBCSOQFXYHK-UHFFFAOYSA-N 1,3-dibromo-2,2-bis(bromomethyl)propane Chemical compound BrCC(CBr)(CBr)CBr OYSVBCSOQFXYHK-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- XXTRGLCPRZQPHJ-UHFFFAOYSA-N 4-hydroxy-2,6-dimethylbenzaldehyde Chemical compound CC1=CC(O)=CC(C)=C1C=O XXTRGLCPRZQPHJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 7
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 8
- 238000004132 cross linking Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000004449 solid propellant Substances 0.000 abstract description 2
- 230000031709 bromination Effects 0.000 abstract 1
- 238000006356 dehydrogenation reaction Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- REDDCKWAMXYDEQ-UHFFFAOYSA-N 4-oxycyanobenzonitrile Chemical compound [O-][N+]#CC1=CC=C(C#N)C=C1 REDDCKWAMXYDEQ-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002009 alkene group Chemical group 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- KPTPCYVULCSKHA-UHFFFAOYSA-N terephthalaldehyde dihydrochloride Chemical compound Cl.Cl.O=Cc1ccc(C=O)cc1 KPTPCYVULCSKHA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
- C07C291/06—Nitrile oxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
Abstract
The invention discloses a tetrafunctional aromatic nitrile oxide compound and a synthesis method thereof, wherein the compound has a chemical structural formula shown in (I), and the synthesis steps comprise four steps of bromination, etherification, oximation and dehydrogenation oxidation. The tetrafunctional aromatic nitrile oxide compound of the invention can exist stably at room temperature (20-30 ℃), and is easy to store and long-term store. The molecular structure comprises four-CNO groups, the applicability of the molecular structure in an olefin-based polymer crosslinking system is wider, and the molecular structure can carry out cycloaddition reaction with a compound containing unsaturated double bonds, so that the molecular structure can be applied to the field of non-isocyanate room temperature curing and forming of solid propellants.
Description
Technical Field
The invention belongs to the field of organic compounds and preparation thereof, and in particular relates to a stable polyfunctional nitrile oxide and a synthesis method thereof.
Background
Nitrile oxides are a class of organic compounds in which the nitrile oxygen group (-CNO) is directly attached to a carbon atom on the molecule. since-CNO as a generalized 1, 3-dipole can undergo cycloaddition reaction with a dipole-philic compound containing unsaturated double bonds (alkene groups) or four bonds (alkyne groups, cyano groups), and the reaction does not need metal catalysis and no by-product generation, the nitrile oxide is widely applied in the fields of biochemistry, pharmaceutical chemistry and polymer science. The nitrile oxide with two or more-CNO groups in the molecular structure is a common olefin-based polymer cross-linking agent, and the nitrile oxide which is used as a curing agent to participate in the cross-linking reaction has the advantages of mild reaction condition, wide environmental adaptability, no byproduct generation, greenness, no heavy metal pollution and the like. However, most lower aliphatic and aromatic nitrile oxide curing agents are unstable at room temperature and readily dimerize or isomerize.
In order to overcome the application trouble caused by poor stability of the nitrile oxide, the unstable nitrile oxide is instantly generated in a reaction system, and the in-situ participation reaction is a common solution in the prior art. For example, in fine chemical engineering, synthesis of terephthalonitrile oxide and room temperature curability, 2017 (9): 1063-1069, the instant synthesis of terephthalonitrile oxide (structure shown as (II)) using terephthalaldehyde dichloride as a precursor is reported,in-situ participates in the cross-linking curing reaction of polybutadiene, but ammonium salts are generated while nitrile oxides are generated in the system and remain in cured samples, so that the performance of the cured elastomer is affected. In addition, most nitrile oxide curing agents areDifunctional nitrile oxides containing two-CNO groups are of limited applicability to polymer crosslinking systems.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a tetrafunctional aromatic nitrile oxide compound and a synthesis method thereof, in particular to a tetrafunctional aromatic nitrile oxide compound which can exist stably at room temperature and contains four-CNO groups in a molecular structure and a synthesis method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a tetrafunctional aromatic nitrile oxide compound having the chemical structural formula shown in (I):
the synthesis method of the tetrafunctional aromatic nitrile oxide compound comprises the following steps:
step 1: bromination reaction
Adding pentaerythritol into dry diethyl ether, stirring at room temperature for dissolution, cooling to 0 ℃, then dropwise adding phosphorus tribromide under the protection of nitrogen, heating to room temperature for reaction for 4 hours after the addition, quenching the reaction liquid with ice water, sequentially carrying out the steps of extraction, water washing, drying, filtering and concentration to obtain a crude product, and then recrystallizing to obtain tetrabromoneopentane;
step 2: etherification reaction
Adding 2, 6-dimethyl-4-hydroxybenzaldehyde and tetrabromoneopentane into dry N, N-Dimethylformamide (DMF) under stirring at room temperature, adding anhydrous potassium carbonate, heating to 100 ℃ after the addition, reacting for a period of time t, filtering out precipitate, concentrating filtrate, dissolving the obtained solid with ethyl acetate, sequentially washing with water, drying, filtering, concentrating to obtain a crude product, and separating by column chromatography to obtain tetrafunctional aryl formaldehyde;
step 3: oximation reaction
Adding tetrafunctional aryl formaldehyde into tetrahydrofuran under stirring at room temperature, sequentially adding hydroxylamine hydrochloride and sodium acetate aqueous solution, stirring at room temperature for reaction for 24 hours after the addition, filtering out precipitate, diluting filtrate with ethyl acetate, sequentially washing with water, drying, filtering, and concentrating to obtain tetrafunctional aryl formaldehyde oxime;
step 4: oxidative dehydrogenation reaction
Adding the tetrafunctional aryl formaldoxime into dichloromethane, cooling to 0 ℃, slowly adding sodium hypochlorite aqueous solution, heating to room temperature after the addition, stirring and reacting for 24 hours, diluting the reaction liquid by using dichloromethane, and sequentially performing water washing, drying, filtering and concentrating to obtain the tetrafunctional aromatic nitrile oxide.
The invention also comprises the following technical characteristics:
specifically, in the step 1, the molar ratio of phosphorus tribromide to pentaerythritol is 30:1.
Specifically, in the step 2, the molar ratio of the 2, 6-dimethyl-4-hydroxybenzaldehyde, tetrabromoneopentane and potassium carbonate is 5:1:5.
Specifically, in the step 2, the reaction time t is 24-72 h.
Specifically, in the step 2, the reaction time t is 72h.
Specifically, in the step 3, the molar ratio of the tetrafunctional aryl formaldehyde, the hydroxylamine hydrochloride and the sodium acetate is 1:4:4-1:8:8.
Specifically, in the step 3, the molar ratio of the tetrafunctional aryl formaldehyde, the hydroxylamine hydrochloride and the sodium acetate is 1:8:8.
Specifically, in the step 4, the molar ratio of the tetrafunctional aryl formaldoxime to the sodium hypochlorite is 1:20.
Compared with the prior art, the invention has the following technical effects:
(1) The tetrafunctional aromatic nitrile oxide compound of the invention can exist stably at room temperature (20-30 ℃), and is easy to store and long-term store. The terephthalonitrile oxide in the literature is not stable at room temperature.
(2) The four-functional aromatic nitrile oxide compound contains four-CNO groups in the molecular structure, and has wider application in an olefin-based polymer crosslinking system. The terephthalonitrile oxide in the literature contains only two-CNO groups.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a tetrafunctional aromatic nitrile oxide compound of the present invention.
FIG. 2 is an infrared spectrum of a tetrafunctional aromatic nitrile oxide compound of the present invention.
Detailed Description
The structural formula of the tetrafunctional aromatic nitrile oxide compound provided by the invention is as follows:
the synthetic route of the tetrafunctional aromatic nitrile oxide compound of the present invention is shown as follows:
according to the invention, the methyl group is introduced at the ortho-position of the aromatic nitrile oxygen group, so that the stability of the tetrafunctional nitrile oxide is improved based on the steric hindrance effect.
The synthesis method of the tetrafunctional aromatic nitrile oxide compound comprises the following steps:
step 1: bromination reaction
Adding pentaerythritol into dry diethyl ether, stirring at room temperature for dissolution, cooling to 0 ℃, then dropwise adding phosphorus tribromide under the protection of nitrogen, heating to room temperature for reaction for 4 hours after the addition, quenching the reaction liquid with ice water, sequentially carrying out the steps of extraction, water washing, drying, filtering and concentration to obtain a crude product, and then recrystallizing to obtain tetrabromoneopentane; the molar ratio of phosphorus tribromide to pentaerythritol was 30:1.
Step 2: etherification reaction
Adding 2, 6-dimethyl-4-hydroxybenzaldehyde and tetrabromoneopentane into dry N, N-Dimethylformamide (DMF) under stirring at room temperature, adding anhydrous potassium carbonate, heating to 100 ℃ after the addition, reacting for a certain time t, filtering out precipitate, concentrating filtrate, dissolving the obtained solid with ethyl acetate, sequentially washing with water, drying, filtering, concentrating to obtain a crude product, and separating by column chromatography to obtain tetrafunctional aryl formaldehyde; the molar ratio of the 2, 6-dimethyl-4-hydroxybenzaldehyde to the tetrabromoneopentane to the potassium carbonate is 5:1:5, and the reaction time t is 24-72 h; preferably, the reaction time t is 72h.
Step 3: oximation reaction
Adding tetrafunctional aryl formaldehyde into tetrahydrofuran under stirring at room temperature, sequentially adding hydroxylamine hydrochloride and sodium acetate aqueous solution, stirring at room temperature for reaction for 24 hours after the addition, filtering out precipitate, diluting filtrate with ethyl acetate, sequentially washing with water, drying, filtering, and concentrating to obtain tetrafunctional aryl formaldehyde oxime; the molar ratio of the tetrafunctional aryl formaldehyde, the hydroxylamine hydrochloride and the sodium acetate is 1:4:4-1:8:8; preferably, the molar ratio of tetrafunctional aryl formaldehyde, hydroxylamine hydrochloride, and sodium acetate is 1:8:8.
Step 4: oxidative dehydrogenation reaction
Adding tetra-functional aryl formaldoxime into dichloromethane, cooling to 0 ℃, slowly adding sodium hypochlorite aqueous solution, heating to room temperature after the addition, stirring and reacting for 24 hours, diluting the reaction solution with dichloromethane, washing with water, drying, filtering and concentrating to obtain the tetra-functional aromatic nitrile oxide; the molar ratio of tetrafunctional aryl formaldoxime to sodium hypochlorite is 1:20.
The following specific embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present invention.
Example 1:
the embodiment provides a tetrafunctional aromatic nitrile oxide compound and a synthesis method thereof, wherein the synthesis method comprises the following steps:
step 1: bromination reaction
Pentaerythritol (5 g,36.7 mmol) and dry diethyl ether (200 mL) were added to a round bottom flask, dissolved under stirring at room temperature, cooled to 0℃and then phosphorus tribromide (298 g,1.1 mol) was added dropwise under nitrogen protection, after the addition was completed, the reaction was allowed to react at room temperature for 4h, the reaction solution was quenched with ice water, then extracted with diethyl ether and the organic phase was collected, washed successively with saturated sodium bicarbonate solution (150 mL. Times.3) and deionized water (150 mL. Times.3), the organic phase was collected, dried overnight with anhydrous magnesium sulfate, then the filtrate was collected by filtration, concentrated to give a crude product, which was recrystallized from acetone to give 6.5g of tetrabromoneopentane as a white powder in 45.7% yield.
And (3) structural identification: 1 H NMR(CDCl 3 ,500MHz,ppm),δ:3.59； 13 C NMR(CDCl 3 ,126MHz,ppm),δ:43.16,34.46.
step 2: etherification reaction
2, 6-dimethyl-4-hydroxybenzaldehyde (3.87 g,25.8 mmol), tetrabromoneopentane (2 g,5.16 mmol) and dry DMF (60 mL) were added to a round bottom flask under stirring at room temperature, dissolved by stirring at room temperature, anhydrous potassium carbonate (3.57 g,25.8 mmol) was added, the temperature was raised to 100℃after completion of the addition, the reaction was carried out for 72 hours, the filtrate was collected by filtration after completion of the reaction, DMF was distilled off under reduced pressure, 100mL of ethyl acetate was added to redissolve the reaction product, poured into a separating funnel, the organic phase was collected by washing with deionized water (60 mL. Times.3) and saturated brine (60 mL. Times.3) in sequence, dried overnight with anhydrous sodium sulfate, then the filtrate was collected by filtration, the solvent was distilled off under reduced pressure, the crude product was collected, purified by a chromatographic column, the eluent was petroleum ether/ethyl acetate (10/1.1.1) and dried by rotary evaporation to obtain a white powdery tetrafunctional arylformaldehyde 2.2g in a yield of 64.1%.
And (3) structural identification: 1 H NMR(CDCl 3 ,500MHz,ppm),δ:10.45,6.61,4.42,2.57； 13 C NMR(CDCl 3 ,126MHz,ppm),δ:191.25,161.32,144.01,125.93,115.03,66.82,44.21,21.07.
step 3: oximation reaction
Four-functionality aryl formaldehyde (2 g,3 mmol) and tetrahydrofuran (20 mL) are added into a round bottom flask, stirred and dissolved at room temperature, hydroxylamine hydrochloride (1.67 g,24 mmol) and aqueous solution (6 mL) containing sodium acetate (1.97 g,24 mmol) are then added sequentially, the reaction is stirred for 24h, the filtrate is collected by filtration after the reaction is finished, 100mL ethyl acetate is used for diluting the filtrate, a separating funnel is poured into the filtrate, deionized water (60 mL multiplied by 3) and saturated saline (60 mL multiplied by 3) are sequentially used for washing, an organic phase is collected, dried overnight with anhydrous sodium sulfate, then the filtrate is collected by filtration, and the solvent is distilled off under reduced pressure to obtain white powdery four-functionality aryl formaldehyde oxime 2g with the yield of 92.2%.
And (3) structural identification: 1 H NMR(CDCl 3 ,500MHz,ppm),δ:8.35,6.63,4.43,2.39； 13 C NMR(CDCl 3 ,126MHz,ppm),δ:158.82,149.76,139.52,122.09,114.63,66.86,44.25,21.51.
step 4: oxidative dehydrogenation reaction
Tetra-functional arylformaldoxime (1 g,1.38 mmol) and methylene chloride (25 mL) were added to a round-bottomed flask, stirred and dissolved, then cooled to 0 ℃, slowly dropwise adding an aqueous solution of sodium hypochlorite (27.6 mmol), after completion of the dropwise addition, warmed to room temperature, stirred for 24 hours, after completion of the reaction, the reaction solution was diluted with 50mL of methylene chloride, poured into a separating funnel, washed with deionized water (60 mL. Times.3) and saturated brine (60 mL. Times.3) in this order, the organic phase was collected, dried overnight with anhydrous sodium sulfate, then the filtrate was collected by filtration, and the solvent was distilled off under reduced pressure to give 880mg of a white powdery tetra-functional aromatic nitrile oxide in 89% yield.
And (3) structural identification:
1 H NMR(CDCl 3 ,500MHz,ppm),δ:6.63,4.43,2.43.
13 C NMR(CDCl 3 ,126MHz,ppm),δ:160.29,143.90,114.55,108.94,66.85,44.43,21.09.
IR(KBr,cm -1 ),ν:2895,2295,1600,1339,1167,1127,1047,887,683.
ESI-MS(m/z),[C 41 H 40 N 4 O 8 Cl - ]measured 751.2451, theoretical calculation 751.2535.
Example 2:
the embodiment provides a tetrafunctional aromatic nitrile oxide compound and a synthesis method thereof, wherein the synthesis method comprises the following steps:
step 1: step 1 of the synthesis method of this example is the same as that of example 1;
the synthesis method of this example is different from that of example 1 in that the reaction time t in step 2 is 48h; in the step 3, the molar ratio of the tetrafunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:6:6; specific:
step 2: etherification reaction
2, 6-dimethyl-4-hydroxybenzaldehyde (3.87 g,25.8 mmol), tetrabromoneopentane (2 g,5.16 mmol) and dry DMF (60 mL) were added to a round bottom flask under stirring at room temperature, dissolved by stirring at room temperature, anhydrous potassium carbonate (3.57 g,25.8 mmol) was added, the temperature was raised to 100℃after completion of the addition, the reaction was allowed to proceed for 48 hours, the filtrate was collected by filtration after completion of the reaction, DMF was distilled off under reduced pressure, 100mL of ethyl acetate was added to redissolve the reaction product, poured into a separating funnel, the organic phase was collected by washing with deionized water (60 mL. Times.3) and saturated brine (60 mL. Times.3) in sequence, dried overnight with anhydrous sodium sulfate, then the filtrate was collected by filtration, the solvent was distilled off under reduced pressure, the crude product was collected, purified by a column chromatography, the eluent was petroleum ether/ethyl acetate (10/1.1.1) and dried by rotary evaporation to give a white powdery tetrafunctional arylformaldehyde in a form of 1.8g, yield 52.5%.
Step 3: oximation reaction
Tetra-functional arylformaldehyde (1 g,1.5 mmol) and tetrahydrofuran (10 mL) were added to a round bottom flask, dissolved by stirring at room temperature, then hydroxylamine hydrochloride (625 mg,9 mmol) and an aqueous solution (3 mL) containing sodium acetate (268 mg,9 mmol) were sequentially added, the reaction was stirred for 24 hours, the filtrate was collected by filtration after the completion of the reaction, the filtrate was diluted with 50mL ethyl acetate, poured into a separating funnel, washed sequentially with deionized water (50 mL. Times.3) and saturated brine (50 mL. Times.3), the organic phase was collected, dried overnight with anhydrous sodium sulfate, then the filtrate was collected by filtration, and the solvent was distilled off under reduced pressure to give a white powdery tetra-functional arylformaloxime 950mg in a yield of 87.6%.
Step 4: step 4 of the synthesis method of this example is the same as that of example 1.
Example 3:
the embodiment provides a tetrafunctional aromatic nitrile oxide compound and a synthesis method thereof, wherein the synthesis method comprises the following steps:
step 1: step 1 of the synthesis method of this example is the same as that of example 1;
this example differs from example 1 in that the reaction time t in step 2 is 24h; in the step 3, the molar ratio of the tetrafunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:4:4; specific:
step 2: etherification reaction
2, 6-dimethyl-4-hydroxybenzaldehyde (3.87 g,25.8 mmol), tetrabromoneopentane (2 g,5.16 mmol) and dry DMF (60 mL) were added to a round bottom flask under stirring at room temperature, dissolved by stirring at room temperature, anhydrous potassium carbonate (3.57 g,25.8 mmol) was added, the temperature was raised to 100℃after completion of the addition, the reaction was carried out for 24 hours, the filtrate was collected by filtration after completion of the reaction, DMF was distilled off under reduced pressure, 100mL of ethyl acetate was added to redissolve the reaction product, poured into a separating funnel, the organic phase was collected by washing with deionized water (60 mL. Times.3) and saturated brine (60 mL. Times.3) in sequence, dried overnight with anhydrous sodium sulfate, then the filtrate was collected by filtration, the solvent was distilled off under reduced pressure, the crude product was collected, purified by a column chromatography, the eluent was petroleum ether/ethyl acetate (10/1.1.1) and dried by rotary evaporation to give a white powdery tetrafunctional arylformaldehyde 1.2g in 35% yield.
Step 3: oximation reaction
Four-functionality aryl formaldehyde (1 g,1.5 mmol) and tetrahydrofuran (10 mL) are added into a round bottom flask, stirred and dissolved at room temperature, hydroxylamine hydrochloride (417 mg,6 mmol) and aqueous solution (3 mL) containing sodium acetate (492 mg,6 mmol) are then sequentially added, the reaction is stirred for 24h, the filtrate is collected by filtration after the reaction is finished, the filtrate is diluted with 50mL ethyl acetate, poured into a separating funnel, washed sequentially with deionized water (50 mL multiplied by 3) and saturated saline (50 mL multiplied by 3), the organic phase is collected, dried overnight with anhydrous sodium sulfate, the filtrate is collected by filtration, the solvent is distilled off under reduced pressure, purification is performed by a chromatographic column, the eluent is petroleum ether/ethyl acetate (10/1- > 1/1) and the white powdery four-functionality aryl formaldehyde oxime 881mg is obtained by spin-evaporation and drying, and the yield is 81.2%.
Step 4: step 4 of the synthesis method of this example is the same as that of example 1.
The nuclear magnetic resonance spectrum of the synthesized target compound is shown in figure 1, and each peak group of the nuclear magnetic resonance spectrum is matched with a hydrogen atom in the tetrafunctional aromatic nitrile oxide compound. The infrared spectrum is shown in FIG. 2, in which the strong absorption peak 2295cm -1 Is C.ident.N-The target compound was confirmed to contain a stable-CNO group.
The above structure identification data confirm that the material prepared by the present method is indeed a tetrafunctional aromatic nitrile oxide.
Performance of tetrafunctional aromatic nitrile oxide:
(1) Solubility of
Is soluble in dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, etc., insoluble in water, petroleum ether, etc.
(2) Room temperature stability
Is a white solid powder stable at room temperature (20-30 ℃) and can be stored for a long time.
Use of tetrafunctional aromatic nitrile oxide:
the tetrafunctional aromatic nitrile oxide compound has stable structure, can generate cycloaddition reaction with a compound containing unsaturated double bonds, and can be applied to the field of non-isocyanate room temperature curing molding of solid propellant.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A tetrafunctional aromatic nitrile oxide compound characterized by having the chemical structural formula (I):
2. the method for synthesizing a tetrafunctional aromatic nitrile oxide compound according to claim 1, characterized by comprising the steps of:
step 1: bromination reaction
Adding pentaerythritol into dry diethyl ether, stirring at room temperature for dissolution, cooling to 0 ℃, then dropwise adding phosphorus tribromide under the protection of nitrogen, heating to room temperature for reaction for 4 hours after the addition, quenching the reaction liquid with ice water, sequentially carrying out the steps of extraction, water washing, drying, filtering and concentration to obtain a crude product, and then recrystallizing to obtain tetrabromoneopentane;
step 2: etherification reaction
Adding 2, 6-dimethyl-4-hydroxybenzaldehyde and tetrabromoneopentane into dry N, N-Dimethylformamide (DMF) under stirring at room temperature, adding anhydrous potassium carbonate, heating to 100 ℃ after the addition, reacting for a period of time t, filtering out precipitate, concentrating filtrate, dissolving the obtained solid with ethyl acetate, sequentially washing with water, drying, filtering, concentrating to obtain a crude product, and separating by column chromatography to obtain tetrafunctional aryl formaldehyde;
step 3: oximation reaction
Adding tetrafunctional aryl formaldehyde into tetrahydrofuran under stirring at room temperature, sequentially adding hydroxylamine hydrochloride and sodium acetate aqueous solution, stirring at room temperature for reaction for 24 hours after the addition, filtering out precipitate, diluting filtrate with ethyl acetate, sequentially washing with water, drying, filtering, and concentrating to obtain tetrafunctional aryl formaldehyde oxime;
step 4: oxidative dehydrogenation reaction
Adding the tetrafunctional aryl formaldoxime into dichloromethane, cooling to 0 ℃, slowly adding sodium hypochlorite aqueous solution, heating to room temperature after the addition, stirring and reacting for 24 hours, diluting the reaction liquid by using dichloromethane, and sequentially performing water washing, drying, filtering and concentrating to obtain the tetrafunctional aromatic nitrile oxide.
3. The method for synthesizing a tetrafunctional aromatic nitrile oxide compound according to claim 2, wherein in step 1, the molar ratio of phosphorus tribromide to pentaerythritol is 30:1.
4. The method for synthesizing a tetrafunctional aromatic nitrile oxide compound according to claim 2, wherein in step 2, the molar ratio of 2, 6-dimethyl-4-hydroxybenzaldehyde, tetrabromoneopentane and potassium carbonate is 5:1:5.
5. The method for synthesizing a tetrafunctional aromatic nitrile oxide compound according to claim 2, wherein the reaction time t in step 2 is 24 to 72 hours.
6. The method for synthesizing a tetrafunctional aromatic nitrile oxide compound according to claim 5, wherein in step 2, the reaction time t is 72h.
7. The method for synthesizing a tetrafunctional aromatic nitrile oxide compound according to claim 2, wherein in the step 3, the molar ratio of the tetrafunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:4:4 to 1:8:8.
8. The method for synthesizing a tetrafunctional aromatic nitrile oxide compound according to claim 7, wherein in the step 3, the molar ratio of the tetrafunctional arylformaldehyde, the hydroxylamine hydrochloride, and the sodium acetate is 1:8:8.
9. The method for synthesizing a tetrafunctional aromatic nitrile oxide compound according to claim 2, wherein in step 4, the molar ratio of tetrafunctional aryl formaldoxime to sodium hypochlorite is 1:20.
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| WO1997003034A2 (en) * | 1995-07-10 | 1997-01-30 | The Dow Chemical Company | Polynitrile oxides |
| JP2010037289A (en) * | 2008-08-06 | 2010-02-18 | Air Water Inc | Trifunctional nitrile oxide and method for producing the same |
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| US20150251995A1 (en) * | 2014-03-07 | 2015-09-10 | Tokyo Institute Of Technology | Multifunctional nitrileoxide compound |
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| WO1997003034A2 (en) * | 1995-07-10 | 1997-01-30 | The Dow Chemical Company | Polynitrile oxides |
| JP2010037289A (en) * | 2008-08-06 | 2010-02-18 | Air Water Inc | Trifunctional nitrile oxide and method for producing the same |
| US20110224380A1 (en) * | 2010-03-09 | 2011-09-15 | Toyoda Gosei Co., Ltd. | Crosslinker, crosslinked polymer material, and production method of the crosslinked polymer material |
| US20150251995A1 (en) * | 2014-03-07 | 2015-09-10 | Tokyo Institute Of Technology | Multifunctional nitrileoxide compound |
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