CN116332803A - Trifunctional aromatic nitrile oxide compound and synthesis method thereof - Google Patents
Trifunctional 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 52
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000006266 etherification reaction Methods 0.000 claims abstract description 7
- 238000006146 oximation reaction Methods 0.000 claims abstract description 7
- 230000032050 esterification Effects 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 42
- 238000001914 filtration Methods 0.000 claims description 32
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 28
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- 239000000706 filtrate Substances 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 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 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 14
- 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
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- 239000001632 sodium acetate Substances 0.000 claims description 14
- 235000017281 sodium acetate Nutrition 0.000 claims description 14
- XXTRGLCPRZQPHJ-UHFFFAOYSA-N 4-hydroxy-2,6-dimethylbenzaldehyde Chemical compound CC1=CC(O)=CC(C)=C1C=O XXTRGLCPRZQPHJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 7
- 238000004440 column chromatography Methods 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
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 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
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000004449 solid propellant Substances 0.000 abstract description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 150000002825 nitriles Chemical class 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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
- 239000003208 petroleum Substances 0.000 description 6
- 239000003480 eluent Substances 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
- 239000000843 powder Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 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
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Classifications
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- 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
- 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
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
-
- 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 tri-functionality aromatic nitrile oxide compound and a synthesis method thereof, wherein the tri-functionality aromatic nitrile oxide compound has a chemical structural formula shown in (I), and the synthesis steps comprise four steps of reaction of sulfonyl esterification, etherification, oximation and dehydrogenation oxidation. The trifunctional 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 three-CNO groups, the applicability of the three-CNO groups in an olefin-based polymer crosslinking system is wider, and the three-CNO groups can undergo cycloaddition reaction with a compound containing unsaturated double bonds, so that the three-CNO can be applied to the field of non-isocyanate room temperature curing molding 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 tri-functionality 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 bond (alkene group) or triple bond (alkyne group, cyano group), 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 its room temperature curability, 2017 (9): 1063-1069, the use of terephthalaldehyde dichloride oxime as a precursor for the immediate synthesis of terephthalonitrile oxide (structure shown as (II)) has been 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 are difunctional nitrile oxides containing two-CNO groups, which have limited applicability in polymer crosslinking systems.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a trifunctional aromatic nitrile oxide compound and a synthesis method thereof, in particular to a trifunctional aromatic nitrile oxide compound which can exist stably at room temperature and contains three-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 trifunctional aromatic nitrile oxide compound having the chemical structural formula shown in (I):
the synthesis method of the tri-functionality aromatic nitrile oxide compound comprises the following steps:
step 1: sulfonyl esterification
Adding 1,1- (trimethylol) ethane, anhydrous triethylamine and 4-dimethylaminopyridine into dry dichloromethane, stirring at room temperature for dissolution, cooling to 0 ℃, then dropwise adding dichloromethane solution containing p-toluenesulfonyl chloride, heating to room temperature for reaction for 24 hours after the addition, diluting the reaction solution with dichloromethane, sequentially performing water washing, drying, filtering and concentrating to obtain a crude product, and separating by column chromatography to obtain trifunctional p-toluenesulfonate;
step 2: etherification reaction
Adding 2, 6-dimethyl-4-hydroxybenzaldehyde and trifunctional para-toluenesulfonate into dry N, N-Dimethylformamide (DMF) under stirring at room temperature, adding anhydrous potassium carbonate and potassium iodide, heating after the addition, refluxing for 24 hours, filtering out precipitate, concentrating filtrate, dissolving the obtained solid with ethyl acetate, washing with water, drying, filtering, concentrating to obtain a crude product, and separating by column chromatography to obtain trifunctional aryl formaldehyde;
step 3: oximation reaction
Adding trifunctional 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 trifunctional aryl formaldehyde oxime;
step 4: oxidative dehydrogenation reaction
Adding the trifunctional 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 trifunctional aromatic nitrile oxide.
The invention also comprises the following technical characteristics:
specifically, in the step 1, the molar ratio of 1,1- (trimethylol) ethane, p-toluenesulfonyl chloride, anhydrous triethylamine and 4-dimethylaminopyridine is 1:6:6:0.6.
Specifically, in the step 2, the molar ratio of the 2, 6-dimethyl-4-hydroxybenzaldehyde, the trifunctional para-toluenesulfonate, the potassium carbonate and the potassium iodide is 3:1:3:0.3-5:1:5:0.5.
Specifically, in the step 2, the molar ratio of the 2, 6-dimethyl-4-hydroxybenzaldehyde, the trifunctional para-toluenesulfonate, the potassium carbonate and the potassium iodide is 5:1:5:0.5.
Specifically, in the step 3, the molar ratio of the trifunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:3:3-1:6:6.
Specifically, in the step 3, the molar ratio of the trifunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:6:6.
Specifically, in the step 4, the molar ratio of the trifunctional aryl formaldoxime to the sodium hypochlorite is 1:15.
Compared with the prior art, the invention has the following technical effects:
(1) The trifunctional 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 tri-functional aromatic nitrile oxide compound contains three-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 trifunctional aromatic nitrile oxide compound of the present invention.
FIG. 2 is an infrared spectrum of a trifunctional aromatic nitrile oxide compound of the invention.
Detailed Description
The invention provides a trifunctional aromatic nitrile oxide compound, which has the following structural formula:
the synthetic route of the trifunctional aromatic nitrile oxide compound of the present invention is shown below:
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 trifunctional nitrile oxide is improved based on the steric hindrance effect.
The synthesis method of the trifunctional aromatic nitrile oxide compound comprises the following steps:
step 1: sulfonyl esterification
Adding 1,1- (trimethylol) ethane, anhydrous triethylamine and 4-dimethylaminopyridine into dry dichloromethane, stirring at room temperature for dissolution, cooling to 0 ℃, then dropwise adding dichloromethane solution containing p-toluenesulfonyl chloride, heating to room temperature for reaction for 24 hours after the addition, diluting the reaction solution with dichloromethane, sequentially performing water washing, drying, filtering and concentrating to obtain a crude product, and separating by column chromatography to obtain trifunctional p-toluenesulfonate; the molar ratio of 1,1- (trimethylol) ethane, p-toluenesulfonyl chloride, anhydrous triethylamine and 4-dimethylaminopyridine is 1:6:6:0.6.
Step 2: etherification reaction
Adding 2, 6-dimethyl-4-hydroxybenzaldehyde and trifunctional para-toluenesulfonate into dry DMF under stirring at room temperature, adding anhydrous potassium carbonate and potassium iodide, heating after the addition, refluxing for 24 hours, filtering out precipitate, concentrating filtrate, dissolving the obtained solid with ethyl acetate, washing with water, drying, filtering, concentrating to obtain a crude product, and separating by column chromatography to obtain trifunctional aryl formaldehyde; 2, 6-dimethyl-4-hydroxy benzaldehyde, wherein the molar ratio of the trifunctional para-toluene sulfonate to the potassium carbonate to the potassium iodide is 3:1:3:0.3-5:1:5:0.5; preferably, the molar ratio of the tri-functional p-toluenesulfonate, potassium carbonate and potassium iodide of 2, 6-dimethyl-4-hydroxybenzaldehyde is 5:1:5:0.5
Step 3: oximation reaction
Adding trifunctional 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 trifunctional aryl formaldehyde oxime; the molar ratio of the trifunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:3:3-1:6:6; preferably, the molar ratio of trifunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:6:6.
Step 4: oxidative dehydrogenation reaction
Adding trifunctional 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 trifunctional aromatic nitrile oxide; the molar ratio of trifunctional aryl formaldoxime to sodium hypochlorite is 1:15.
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 trifunctional aromatic nitrile oxide compound and a synthesis method thereof, wherein the synthesis method comprises the following steps:
step 1: sulfonyl esterification
1,1- (Trihydroxymethyl) ethane (10 g,0.083 mol), anhydrous triethylamine (50.4 g,0.498 mol) and 4-dimethylaminopyridine (6.08 g,0.0498 mol) were added to a round-bottomed flask, stirred and dissolved at room temperature, cooled to 0 ℃, then a solution of p-toluenesulfonyl chloride (94.9 g,0.498 mol) in methylene chloride (20 mL) was added dropwise, and after the addition was completed, the reaction was allowed to proceed to room temperature for 24 hours, after the completion of the reaction, the reaction solution was diluted with 100mL of methylene chloride, washed successively with deionized water (150 mL. Times.3) and saturated brine (150 mL. Times.3), the organic phase was collected, dried overnight with anhydrous magnesium sulfate, then the filtrate was collected by filtration, the crude product was concentrated, purified with a column chromatography, the eluent was petroleum ether/ethyl acetate (10/1→1/1) and dried by rotary evaporation to give white powdery trifunctional p-toluenesulfonate 45g in a yield of 92.9%.
And (3) structural identification: 1 H NMR(CDCl 3 ,500MHz,ppm),δ:7.71,7.37,3.76,2.47,0.89； 13 C NMR(CDCl 3 ,126MHz,ppm),δ:145.37,132.04,130.09,127.95,69.79,39.45,21.69,16.13.
step 2: etherification reaction
2, 6-dimethyl-4-hydroxybenzaldehyde (5 g,33.3 mmol), trifunctional para-toluenesulfonate (3.88 g,6.66 mmol) and dry DMF (80 mL) were added to a round bottom flask under stirring at room temperature, dissolved under stirring, anhydrous potassium carbonate (4.6 g,33.3 mmol) and potassium iodide (0.55 g,3.33 mmol) were added, the temperature was raised after the addition, the reaction was refluxed for 24 hours, the filtrate was collected by filtration after the reaction was completed, DMF was distilled off under reduced pressure, 100mL of ethyl acetate was added to redissolve the reaction product, poured into a separating funnel, washed with deionized water (60 mL. Times.3) and saturated brine (60 mL. Times.3) in sequence, the organic phase was collected, 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 chromatography column with an eluent of petroleum ether/ethyl acetate (10/1.fwdarw 1/1) and dried by spin distillation to give a white powdery trifunctional arylformaldehyde 2.53g with a yield of 73.5%.
And (3) structural identification: 1 H NMR(CDCl 3 ,500MHz,ppm),δ:10.45,6.61,4.20,2.58,1.39； 13 C NMR(CDCl 3 ,126MHz,ppm),δ:191.42,161.65,144.21,126.03,115.21,70.45,40.31,21.03,16.59.
step 3: oximation reaction
Trifunctional arylformaldehyde (2 g,3.87 mmol) and tetrahydrofuran (20 mL) were added to a round bottom flask, stirred at room temperature for dissolution, then hydroxylamine hydrochloride (1.6 g,23.22 mmol) and an aqueous solution (6 mL) containing sodium acetate (1.9 g,23.22 mmol) were sequentially added, the reaction was stirred for 24 hours, the filtrate was collected by filtration after completion of the reaction, 100mL of ethyl acetate was used for dilution of the filtrate, poured into a separating funnel, washed sequentially with deionized water (60 mL. Times.3) and saturated brine (60 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 trifunctional arylformaldoxime as a white powder (2.03 g) in 93.5% yield.
And (3) structural identification: 1 H NMR(CDCl 3 ,500MHz,ppm),δ:8.38,6.64,4.23,2.40,1.38； 13 C NMR(CDCl 3 ,126MHz,ppm),δ:158.94,149.82,139.62,122.11,114.75,70.51,40.36,21.52,16.62.
step 4: oxidative dehydrogenation reaction
Trifunctional arylformaldoxime (2 g,3.56 mmol) and methylene chloride (40 mL) were added into a round-bottomed flask, stirred and dissolved, then cooled to 0 ℃, slowly added dropwise with an aqueous solution of sodium hypochlorite (53.4 mmol), cooled to room temperature after completion of the dropwise addition, 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×3) and saturated brine (60 ml×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 1.8g of a white powdery trifunctional aromatic nitrile oxide with a yield of 91%.
And (3) structural identification:
1 H NMR(CDCl 3 ,500MHz,ppm),δ:6.65,4.17,2.43,1.39.
13 C NMR(CDCl 3 ,126MHz,ppm),δ:160.21,143.91,115.62,109.74,71.29,41.45,21.06,16.10.
IR(KBr,cm -1 ),ν:2938,2894,2296,1598,1337,1167,1126,1047,887,831,682.
ESI-MS(m/z),[C 32 H 33 N 3 O 6 Cl - ]measured 590.1963, theoretical calculation 590.2058.
Example 2
This example provides a trifunctional aromatic nitrile oxide compound and a method for synthesizing the same as in example 1, steps 1 and 4 of the method for synthesizing this example;
this example differs from example 1 in that in step 2, 6-dimethyl-4-hydroxybenzaldehyde, the molar ratio of trifunctional para-toluene sulfonate, potassium carbonate and potassium iodide is 4:1:4:0.4; in the step 3, the molar ratio of the trifunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:4.5:4.5; specific:
step 2: etherification reaction
2, 6-dimethyl-4-hydroxybenzaldehyde (5 g,33.3 mmol), trifunctional para-toluenesulfonate (4.85 g,8.33 mmol) and dry DMF (80 mL) were added to a round bottom flask under stirring at room temperature, dissolved under stirring, anhydrous potassium carbonate (4.6 g,33.3 mmol) and potassium iodide (0.55 g,3.33 mmol) were added, the temperature was raised after the addition, the reaction was refluxed for 24 hours, the filtrate was collected by filtration after the reaction was completed, DMF was distilled off under reduced pressure, 100mL of ethyl acetate was added to redissolve the reaction product, poured into a separating funnel, washed with deionized water (60 mL. Times.3) and saturated brine (60 mL. Times.3) in sequence, the organic phase was collected, 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 chromatography column with an eluent of petroleum ether/ethyl acetate (10/1- & gt1/1) and dried by spin distillation to give a white powdery trifunctional arylformaldehyde 2.8g with a yield of 65.2%.
Step 3: oximation reaction
Trifunctional arylformaldehyde (2 g,3.87 mmol) and tetrahydrofuran (20 mL) were added to a round bottom flask, stirred at room temperature for dissolution, then hydroxylamine hydrochloride (1.2 g,17.42 mmol) and an aqueous solution (6 mL) containing sodium acetate (1.43 g,17.42 mmol) were sequentially added, the reaction was stirred for 24 hours, the filtrate was collected by filtration after completion of the reaction, 100mL of ethyl acetate was used for dilution of the filtrate, poured into a separating funnel, washed sequentially with deionized water (60 mL. Times.3) and saturated brine (60 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 trifunctional arylformaldoxime as a white powder of 1.96g in 90.2% yield.
Example 3
This example provides a trifunctional aromatic nitrile oxide compound and a method for synthesizing the same as in example 1, steps 1 and 4 of the method for synthesizing this example;
this example differs from example 1 in that in step 2, 6-dimethyl-4-hydroxybenzaldehyde, the molar ratio of trifunctional para-toluene sulfonate, potassium carbonate and potassium iodide is 3:1:3:0.3; in the step 3, the molar ratio of the trifunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:3:3.
Step 2: etherification reaction
2, 6-dimethyl-4-hydroxybenzaldehyde (5 g,33.3 mmol), trifunctional para-toluenesulfonate (6.47 g,11.1 mmol) and dry DMF (80 mL) were added to a round bottom flask under stirring at room temperature, dissolved under stirring, anhydrous potassium carbonate (4.6 g,33.3 mmol) and potassium iodide (0.55 g,3.33 mmol) were added, the temperature was raised after the addition, the reaction was refluxed for 24 hours, the filtrate was collected by filtration after the reaction was completed, DMF was distilled off under reduced pressure, 100mL of ethyl acetate was added to redissolve the reaction product, poured into a separating funnel, washed successively with deionized water (60 mL. Times.3) and saturated brine (60 mL. Times.3), the organic phase was collected, 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 chromatography column with an eluent of petroleum ether/ethyl acetate (10/1.fwdarw.1) and dried by spin distillation to give a white powdery trifunctional arylformaldehyde 2.9g with a yield of 50.6%.
Step 3: oximation reaction
Trifunctional arylformaldehyde (2 g,3.87 mmol) and tetrahydrofuran (20 mL) were added to a round bottom flask, stirred at room temperature for dissolution, then hydroxylamine hydrochloride (0.81 g,11.61 mmol) and an aqueous solution (6 mL) containing sodium acetate (0.95 g,11.61 mmol) were sequentially added, the reaction was stirred for 24 hours, the filtrate was collected by filtration after completion of the reaction, 100mL of ethyl acetate was used for dilution of the filtrate, poured into a separating funnel, deionized water (60 mL. Times.3) and saturated brine (60 mL. Times.3) were sequentially used for washing, the organic phase was collected, dried over night with anhydrous sodium sulfate, the filtrate was collected by filtration, the solvent was distilled off under reduced pressure, purification was performed by a chromatographic column, the eluent was petroleum ether/ethyl acetate (10/1→1/1), and 1.78g of trifunctional arylformaloxime was obtained as a white powder by spin drying, the yield was 82%.
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 tri-functionality aromatic nitrile oxide compound. The infrared spectrum is shown in FIG. 2, in which the strong absorption peak 2296cm -1 The target compound was confirmed to contain a stable-CNO group, which was a C.ident.N-stretching vibration peak.
The above structure identification data confirm that the material prepared by the present method is indeed a trifunctional aromatic nitrile oxide.
Performance of trifunctional 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 trifunctional aromatic nitrile oxides:
the trifunctional 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 (8)
1. A trifunctional aromatic nitrile oxide compound characterized by having the chemical structural formula shown in (I):
2. the method for synthesizing a trifunctional aromatic nitrile oxide compound according to claim 1, comprising the steps of:
step 1: sulfonyl esterification
Adding 1,1- (trimethylol) ethane, anhydrous triethylamine and 4-dimethylaminopyridine into dry dichloromethane, stirring at room temperature for dissolution, cooling to 0 ℃, then dropwise adding dichloromethane solution containing p-toluenesulfonyl chloride, heating to room temperature for reaction for 24 hours, diluting the reaction solution with dichloromethane, sequentially performing water washing, drying, filtering and concentrating to obtain a crude product, and separating by column chromatography to obtain trifunctional p-toluenesulfonate;
step 2: etherification reaction
Adding 2, 6-dimethyl-4-hydroxybenzaldehyde and trifunctional para-toluenesulfonate into dry N, N-Dimethylformamide (DMF) under stirring at room temperature, adding anhydrous potassium carbonate and potassium iodide, heating after the addition, refluxing for 24 hours, filtering out precipitate, concentrating filtrate, dissolving the obtained solid with ethyl acetate, washing with water, drying, filtering, concentrating to obtain a crude product, and separating by column chromatography to obtain trifunctional aryl formaldehyde;
step 3: oximation reaction
Adding trifunctional 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 trifunctional aryl formaldehyde oxime;
step 4: oxidative dehydrogenation reaction
Adding the trifunctional 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 with dichloromethane, washing with water, drying, filtering and concentrating to obtain the trifunctional aromatic nitrile oxide.
3. The method for synthesizing a trifunctional aromatic nitrile oxide compound according to claim 2, wherein in step 1, the molar ratio of 1,1- (trimethylol) ethane, p-toluenesulfonyl chloride, anhydrous triethylamine, 4-dimethylaminopyridine is 1:6:6:0.6.
4. The method for synthesizing a trifunctional aromatic nitrile oxide compound according to claim 2, wherein in step 2, the molar ratio of the trifunctional para-toluene sulfonate, potassium carbonate and potassium iodide is 3:1:3:0.3 to 5:1:5:0.5.
5. The method for synthesizing a trifunctional aromatic nitrile oxide compound according to claim 4, wherein in step 2, the molar ratio of 2, 6-dimethyl-4-hydroxybenzaldehyde, trifunctional para-toluenesulfonate, potassium carbonate and potassium iodide is 5:1:5:0.5.
6. The method for synthesizing a trifunctional aromatic nitrile oxide compound according to claim 2, wherein in the step 3, the molar ratio of trifunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:3:3 to 1:6:6.
7. The method for synthesizing a trifunctional aromatic nitrile oxide compound according to claim 6, wherein in said step 3, the molar ratio of trifunctional aryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:6:6.
8. The method for synthesizing a trifunctional aromatic nitrile oxide compound according to claim 2, wherein in said step 4, the molar ratio of trifunctional arylformaldoxime to sodium hypochlorite is 1:15.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997003034A2 (en) * | 1995-07-10 | 1997-01-30 | The Dow Chemical Company | Polynitrile oxides |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997003034A2 (en) * | 1995-07-10 | 1997-01-30 | The Dow Chemical Company | Polynitrile oxides |
| US20110224380A1 (en) * | 2010-03-09 | 2011-09-15 | Toyoda Gosei Co., Ltd. | Crosslinker, crosslinked polymer material, and production method of the crosslinked polymer material |
| JP2011208117A (en) * | 2010-03-09 | 2011-10-20 | Toyoda Gosei Co Ltd | Crosslinking agent, crosslinked polymer material, and method for producing the crosslinked polymer material |
| US20150251995A1 (en) * | 2014-03-07 | 2015-09-10 | Tokyo Institute Of Technology | Multifunctional nitrileoxide compound |
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