CN115536555B - 1, 2-Bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound - Google Patents
1, 2-Bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound Download PDFInfo
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- -1 ethane compound Chemical class 0.000 title claims abstract description 60
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 title claims abstract description 28
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 42
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 34
- AGYUOJIYYGGHKV-UHFFFAOYSA-N 1,2-bis(2-chloroethoxy)ethane Chemical compound ClCCOCCOCCCl AGYUOJIYYGGHKV-UHFFFAOYSA-N 0.000 claims abstract description 13
- XXTRGLCPRZQPHJ-UHFFFAOYSA-N 4-hydroxy-2,6-dimethylbenzaldehyde Chemical compound CC1=CC(O)=CC(C)=C1C=O XXTRGLCPRZQPHJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 238000001914 filtration Methods 0.000 claims description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 34
- 239000000706 filtrate Substances 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 31
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 14
- 239000001632 sodium acetate Substances 0.000 claims description 14
- 235000017281 sodium acetate Nutrition 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000012074 organic phase Substances 0.000 claims description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 238000007865 diluting Methods 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 9
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000006266 etherification reaction Methods 0.000 abstract description 5
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 abstract description 5
- 238000006146 oximation reaction Methods 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000004449 solid propellant Substances 0.000 abstract description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical group C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 abstract 1
- 125000003172 aldehyde group Chemical group 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- REDDCKWAMXYDEQ-UHFFFAOYSA-N 4-oxycyanobenzonitrile Chemical compound [O-][N+]#CC1=CC=C(C#N)C=C1 REDDCKWAMXYDEQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000003335 steric effect Effects 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 150000004703 alkoxides Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 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
- 150000001336 alkenes 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000006352 cycloaddition reaction Methods 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
- 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
- 238000004895 liquid chromatography mass spectrometry Methods 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001228 spectrum Methods 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a1, 2-bis (2- (3, 5-dimethyl-4-nitrile oxyphenoxy) ethoxy) ethane compound, which has the structural formula:
Description
Technical Field
The invention belongs to an organic compound and a preparation method thereof, and in particular relates to a stable difunctional 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 in the molecular structure. Nitrile oxides are widely used in the fields of pharmaceutical chemistry, biochemistry and polymer science because of their ability to undergo 1, 3-dipolar cycloaddition reactions with dipolar electrophilic compounds containing unsaturated double or triple bonds (olefinic, acetylenic, cyano, etc.), without the need for metal catalysts and without the formation of by-products. The difunctional nitrile oxide containing two-CNO groups in the molecular structure is a common cross-linking agent for polymers containing olefin groups, and has the advantages of mild reaction conditions, wide environmental adaptability, no byproduct generation in the curing process, greenness, no heavy metal pollution and the like. Most lower aliphatic and aromatic difunctional nitrile oxides are unstable at room temperature and readily dimerize or isomerize.
In order to overcome the application trouble caused by poor stability of nitrile oxide, two main solutions exist in the prior art. One method is to use a difunctional nitrile oxide precursor to instantaneously generate a high-activity nitrile oxide, and participate in the reaction in situ, but byproducts are generated in the nitrile oxide generation process, so that the performance of a synthesized sample is affected. 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 reportedIn-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 a cured sample, so that the overall performance of the elastomer is affected. Another approach is to increase the stability of the compound by introducing a large steric hindrance group near the-CNO group of the difunctional nitrile oxide, but steric effects can also result in a decrease in the reactivity of the-CNO group with the dipole-containing compound, resulting in an increase in the reaction temperature. For example, "Rotaxane-based difunctional nitrile N-Oxide crosslinker: Synthesis and direct Introduction of movable crosslinking points into ethylene-propylene-butadiene monomer(EPDM)rubber"Macromol.Rapid Commun.,2021 (42):2000639 reports stable difunctional nitrile oxides (structures shown as (III))/>It can not react with double bond in EPDM rubber at room temperature, and needs to be heated to 60 ℃ for carrying out, and the reaction effect is optimal at 100 ℃.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound, wherein a small steric hindrance group is introduced at the ortho position of an aromatic nitriloxy group, so that the stability of a difunctional nitrile oxide is improved based on a space steric effect, and meanwhile, high reactivity is ensured.
In order to solve the technical problems, the invention adopts the following technical scheme:
a1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound having the formula (I):
the invention also comprises the following technical characteristics:
Specifically, the method comprises the following steps:
Step 1, etherification: adding 2, 6-dimethyl-4-hydroxybenzaldehyde and 1, 2-bis (2-chloroethoxy) ethane into dry N, N-dimethylformamide under stirring at room temperature, adding potassium carbonate, heating to 90 ℃ for reaction for 24-48 hours, filtering out precipitate, concentrating filtrate, dissolving the obtained solid by using ethyl acetate, washing, drying, filtering, concentrating to obtain a crude product, and separating by column chromatography to obtain alkoxy chain connected diaryl formaldehyde; wherein the molar ratio of the 2, 6-dimethyl-4-hydroxybenzaldehyde, the 1, 2-bis (2-chloroethoxy) ethane and the potassium carbonate is 2:1:3-3:1:4.5;
step 2, oximation: adding alkoxy chain connected diaryl formaldehyde into tetrahydrofuran or methanol under stirring at room temperature, sequentially adding hydroxylamine hydrochloride and sodium acetate or sodium acetate aqueous solution, stirring at room temperature after the addition is finished for reaction for 24 hours, filtering out precipitate, diluting filtrate with ethyl acetate, sequentially washing with water, drying, filtering and concentrating to obtain alkoxy chain connected diaryl formaldehyde oxime; wherein the molar ratio of the alkoxy chain to the diaryl formaldehyde to the hydroxylamine hydrochloride to the sodium acetate is 1:2:2-1:4:4;
Step 3, oxidative dehydrogenation: adding alkoxy chain-linked diaryl formaldoxime into dichloromethane or DMF, cooling to 0 ℃, slowly adding sodium hypochlorite aqueous solution or sequentially slowly adding N-bromosuccinimide and triethylamine, after the addition, heating to room temperature, stirring for reaction for 24 hours, diluting the reaction solution with dichloromethane, sequentially washing with water, drying, filtering, and concentrating to obtain 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane; wherein the molar ratio of the alkoxy chain to the diaryl aldoxime to the sodium hypochlorite is 1:10 or the molar ratio of the alkoxy chain to the diaryl aldoxime to the N-bromosuccinimide to the triethylamine is 1:2:2.
Specifically, in the step 1, the temperature is raised to 90 ℃ for 48 hours.
Specifically, in the step 1, the molar ratio of the 2, 6-dimethyl-4-hydroxybenzaldehyde, the 1, 2-bis (2-chloroethoxy) ethane and the potassium carbonate is 3:1:4.5.
Specifically, in the step 2, the molar ratio of the alkoxy chain connection diaryl formaldehyde, hydroxylamine hydrochloride and sodium acetate is 1:4:4.
Compared with the prior art, the invention has the following technical effects:
(1) The 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound can be stably stored at room temperature (20-30 ℃), and terephthalonitrile oxide in the comparison literature cannot exist stably at room temperature;
(2) The nitrile oxygen group of the 1, 2-bis (2- (3, 5-dimethyl-4-nitrile oxyphenoxy) ethoxy) ethane compound is stabilized by an ortho-position small-steric hindrance methyl group, has higher reactivity, can rapidly react with a compound containing unsaturated double bonds at room temperature (20-30 ℃), and compared with the difunctional nitrile oxide with stable large steric hindrance groups in the literature, the difunctional nitrile oxide needs to be heated to 60 ℃ for reaction.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound of the invention.
FIG. 2 is an infrared spectrum of a1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound of the invention.
FIG. 3 is a nuclear magnetic resonance spectrum of the product of the reaction of the 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound of the present invention with allyl glycidyl ether at 25 ℃.
Detailed Description
The structural formula of the 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound provided by the invention is as follows:
The synthetic route of the 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound of the invention is shown as follows:
According to the invention, a small steric hindrance group is introduced at the ortho-position of the aromatic nitrile oxygen group, so that the stability of the difunctional nitrile oxide is improved based on a space steric effect, and meanwhile, high reaction activity is ensured; the invention relates to a synthesis method of a1, 2-bis (2- (3, 5-dimethyl-4-nitrile oxyphenoxy) ethoxy) ethane compound, which comprises the following steps:
(1) Etherification: adding 2, 6-dimethyl-4-hydroxybenzaldehyde and 1, 2-bis (2-chloroethoxy) ethane into dry DMF under stirring at room temperature, adding anhydrous potassium carbonate, heating to 90 ℃ after the addition, reacting for 24-48 h, filtering out precipitate, concentrating filtrate, dissolving the obtained solid by using ethyl acetate, sequentially washing, drying, filtering, concentrating to obtain a crude product, and separating by column chromatography to obtain an alkoxy chain connected diaryl formaldehyde, wherein the molar ratio of the 2, 6-dimethyl-4-hydroxybenzaldehyde, the 1, 2-bis (2-chloroethoxy) ethane and the potassium carbonate is 2:1:3-3:1:4.5;
(2) Oximation: adding alkoxy chain connection diaryl formaldehyde into tetrahydrofuran or methanol under stirring at room temperature, sequentially adding hydroxylamine hydrochloride and sodium acetate or sodium acetate aqueous solution, stirring at room temperature after the addition is finished for reaction for 24 hours, filtering out precipitate, diluting filtrate with ethyl acetate, sequentially washing with water, drying, filtering, and concentrating to obtain alkoxy chain connection diaryl formaldehyde oxime, wherein the molar ratio of the alkoxy chain connection diaryl formaldehyde to the hydroxylamine hydrochloride to the sodium acetate is 1:2:2-1:4:4;
(3) Oxidative dehydrogenation: adding alkoxy chain connected diaryl formaldehyde oxime into dichloromethane or DMF, cooling to 0 ℃, slowly adding sodium hypochlorite aqueous solution or sequentially slowly adding N-bromosuccinimide (NBS) and triethylamine, heating to room temperature after the addition is finished, stirring for reaction for 24 hours, diluting the reaction liquid by using dichloromethane, sequentially washing with water, drying, filtering, and concentrating to obtain 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane, wherein the molar ratio of the alkoxy chain connected diaryl formaldehyde oxime to sodium hypochlorite is 1:10 or the molar ratio of the alkoxy chain connected diaryl formaldehyde oxime to NBS and triethylamine is 1:2:2.
Preferably, the synthesis method of the 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound comprises the following steps:
(1) Etherification: adding 2, 6-dimethyl-4-hydroxybenzaldehyde and 1, 2-bis (2-chloroethoxy) ethane into dry DMF under stirring at room temperature, adding anhydrous potassium carbonate, heating to 90 ℃ for reaction for 48 hours after the addition, filtering out precipitates, concentrating filtrate, dissolving the obtained solid by using ethyl acetate, sequentially washing with water, drying, filtering, concentrating to obtain a crude product, and separating by column chromatography to obtain an alkoxy chain connected diaryl formaldehyde, wherein the molar ratio of the 2, 6-dimethyl-4-hydroxybenzaldehyde, the 1, 2-bis (2-chloroethoxy) ethane and the potassium carbonate is 3:1:4.5;
(2) Oximation: adding alkoxy chain connected diaryl formaldehyde into methanol under stirring at room temperature, sequentially adding hydroxylamine hydrochloride and sodium acetate, 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 alkoxy chain connected diaryl formaldehyde oxime, wherein the molar ratio of the alkoxy chain connected diaryl formaldehyde to the hydroxylamine hydrochloride to the sodium acetate is 1:4:4;
(3) Oxidative dehydrogenation: adding the alkoxy chain connected diaryl formaldoxime into dichloromethane, cooling to 0 ℃, slowly adding sodium hypochlorite aqueous solution, heating to room temperature after the addition, stirring for reaction for 24 hours, diluting the reaction liquid by using dichloromethane, sequentially washing with water, drying, filtering, and concentrating to obtain the 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane, wherein the molar ratio of the alkoxy chain connected diaryl formaldoxime to the sodium hypochlorite is 1:10.
The following specific embodiments of the present application are provided, and it should be noted that the present application is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical scheme of the present application fall within the protection scope of the present application.
(1) Synthesis of Alkoxy chain-linked diarylhydes (etherification reaction)
Example 1:
2, 6-dimethyl-4-hydroxybenzaldehyde (7.51 g,50 mmol), 1, 2-bis (2-chloroethoxy) ethane (4.7 g,25 mmol) and dry DMF (130 mL) were added to a round bottom flask, dissolved by stirring at room temperature, anhydrous potassium carbonate (10.37 g,75 mmol) was added, the reaction flask was placed in an oil bath at 90℃and stirred for 24h, the filtrate was collected by filtration after the reaction was completed, DMF was distilled off under reduced pressure, 200mL 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 (100 mL. Times.3) and saturated brine (100 mL. Times.3) in sequence, dried overnight with anhydrous sodium sulfate, the filtrate was collected by filtration, the solvent was distilled off under reduced pressure, the crude product was collected, purified by a chromatographic column with petroleum ether/ethyl acetate (10/1- > 2/1) as an eluent, and dried by rotary evaporation to give a white powdery alkoxy chain-linked diaryl formaldehyde 6. 6.6 g in a yield of 63.8%.
Example 2:
2, 6-dimethyl-4-hydroxybenzaldehyde (7.51 g,50 mmol), 1, 2-bis (2-chloroethoxy) ethane (4.7 g,25 mmol) and dry DMF (130 mL) were added to a round bottom flask, dissolved by stirring at room temperature, anhydrous potassium carbonate (10.37 g,75 mmol) was added, the reaction flask was placed in an oil bath at 90℃for 36h, the filtrate was collected by filtration after the reaction, DMF was distilled off under reduced pressure, 200mL 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 (100 mL. Times.3) and saturated brine (100 mL. Times.3) in sequence, dried overnight with anhydrous sodium sulfate, the filtrate was collected by filtration, the solvent was distilled off under reduced pressure, the crude product was collected, purified by a chromatographic column with petroleum ether/ethyl acetate (10/1- > 2/1) as eluent, and the white powdery alkoxy chain-linked diaryl formaldehyde 7.4 g% was obtained by spin-drying, yield was 71.5%.
Example 3:
2, 6-dimethyl-4-hydroxybenzaldehyde (9.38 g,62.5 mmol), 1, 2-bis (2-chloroethoxy) ethane (4.7 g,25 mmol) and dry DMF (130 mL) were added to a round bottom flask, stirred at room temperature for dissolution, anhydrous potassium carbonate (13.0 g,93.75 mmol) was added, the flask was placed in an oil bath at 90℃for reaction stirring for 48h, the filtrate was collected by filtration after the reaction was completed, DMF was distilled off under reduced pressure, 200mL 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 (100 mL. Times.3) and saturated brine (100 mL. Times.3) in sequence, dried overnight with anhydrous sodium sulfate, the filtrate was collected by filtration, the solvent was distilled off under reduced pressure, the crude product was collected, purified by a chromatographic column with petroleum ether/ethyl acetate (10/1.2/1) as eluent, and the white powdery alkoxy chain-linked diaryl formaldehyde 8.7g was obtained by spin evaporation drying, the yield was 84.1%.
Example 4:
2, 6-dimethyl-4-hydroxybenzaldehyde (11.26 g,75 mmol), 1, 2-bis (2-chloroethoxy) ethane (4.7 g,25 mmol) and dry DMF (130 mL) were added to a round bottom flask, dissolved by stirring at room temperature, anhydrous potassium carbonate (15.5 g,112.5 mmol) was added, the reaction flask was placed in an oil bath at 90℃for 48h, the filtrate was collected by filtration after the reaction was completed, DMF was distilled off under reduced pressure, 200mL 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 (100 mL. Times.3) and saturated brine (100 mL. Times.3) in sequence, dried overnight with anhydrous sodium sulfate, the filtrate was collected by filtration, the solvent was distilled off under reduced pressure, the crude product was collected, purified by a column chromatography with petroleum ether/ethyl acetate (10/1.2/1) as an eluent, and white powdery alkoxy chain-linked diarylhyde 9.5g was obtained by spin-drying, with a yield of 91.7%.
Structural identification ：1H NMR(CDCl3,500MHz,ppm),δ:10.45,6.58,4.15,3.86,3.74,2.57;13C NMR(CDCl3,125MHz,ppm),δ:191.52,161.86,144.35,126.05,115.35,70.89,69.54,67.31, 21.01.
(2) Synthesis of Alkoxy chain-linked diaryl aldoxime (oximation reaction)
Example 5:
The alkoxy chain-linked diaryl formaldehyde (4 g,9.6 mmol) and tetrahydrofuran (60 mL) were added to a round bottom flask, stirred at room temperature for dissolution, then hydroxylamine hydrochloride (1.34 g,19.2 mmol) and 10mL of aqueous sodium acetate (1.56 g,19.2 mmol) were sequentially added, the reaction was stirred overnight, after the reaction was completed, the reaction solution was diluted with 200mL of ethyl acetate, poured into a separating funnel, washed sequentially with deionized water (100 mL. Times.3) and saturated saline (100 mL. Times.3), 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 with a chromatographic column with petroleum ether/ethyl acetate (10/1- & gt 3/1) as an eluent to give a white powdery alkoxy chain-linked diaryl formaldehyde oxime (3.4 g) with a yield of 79.8%).
Example 6:
Alkoxy chain connected diaryl formaldehyde (4 g,9.6 mmol) and methanol (80 mL) are added into a round bottom flask, stirred and dispersed at room temperature to form a suspension, hydroxylamine hydrochloride (1.34 g,19.2 mmol) and sodium acetate (1.56 g,19.2 mmol) are then sequentially added, the reaction is stirred overnight, filtrate is filtered and collected after the reaction is finished, 200mL ethyl acetate is used for diluting the filtrate, a separating funnel is poured into the filtrate, deionized water (100 mL multiplied by 3) and saturated saline (100 mL multiplied by 3) are sequentially used for washing, an organic phase is collected, anhydrous sodium sulfate is used for drying overnight, then the filtrate is filtered and collected, the solvent is distilled off under reduced pressure, the purification is performed by a chromatographic column, the eluent is petroleum ether/ethyl acetate (10/1- > 3/1), white powdery alkoxy chain connected diaryl formaldehyde oxime 3.6 g is obtained after spin evaporation and drying, and the yield is 84.5%.
Example 7:
alkoxy chain connected diaryl formaldehyde (4 g,9.6 mmol) and methanol (80 mL) are added into a round bottom flask, stirred and dispersed at room temperature to form a suspension, hydroxylamine hydrochloride (1.61 g,23.04 mmol) and sodium acetate (1.87 g,23.04 mmol) are then sequentially added, the reaction is stirred overnight, filtrate is collected by filtration after the reaction is finished, 200mL ethyl acetate is used for diluting the filtrate, a separating funnel is poured into the filtrate, deionized water (100 mL multiplied by 3) and saturated saline (100 mL multiplied by 3) are sequentially used for washing, an organic phase is collected, anhydrous sodium sulfate is used for drying overnight, then the filtrate is collected by filtration, the solvent is distilled off under reduced pressure, the purification is performed by a chromatographic column, the eluent is petroleum ether/ethyl acetate (10/1- > 3/1), white powdery alkoxy chain connected diaryl formaldehyde oxime 3.8 g is obtained by spin evaporation and drying, and the yield is 89.2%.
Example 8:
Alkoxy chain-linked diaryl formaldehyde (4 g,9.6 mmol) and methanol (80 mL) were added to a round bottom flask, stirred and dispersed at room temperature to form a suspension, hydroxylamine hydrochloride (2.67 g,38.4 mmol) and sodium acetate (3.12 g,38.4 mmol) were then added sequentially, the reaction was stirred overnight, the filtrate was collected by filtration after the reaction was completed, the filtrate was diluted with 200mL ethyl acetate, poured into a separating funnel, washed sequentially with deionized water (100 mL. Times.3) and saturated brine (100 mL. Times.3), the organic phase was collected, dried over night with anhydrous sodium sulfate, the filtrate was collected by filtration, and the solvent was distilled off under reduced pressure to give white powdery alkoxy chain-linked diaryl formaldehyde oxime 4.1g in 96.2% yield.
Structural identification ：1H NMR(CDCl3,500MHz,ppm),δ:8.37,6.61,4.12,3.85,3.75,2.37;13C NMR(CDCl3,125MHz,ppm),δ:158.77,149.70,139.46,122.07,114.56,70.90,69.74,67.23, 21.54.
(3) Synthesis (oxidative dehydrogenation) of 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane
Example 9:
the alkoxide chain-linked diaryl formaldoxime (4 g,9.0 mmol) and DMF (40 mL) were added into a round bottom flask, stirred and dissolved, then cooled to 0 ℃, NBS (3.21, 18 mmol) was added in portions, stirred and reacted for 30min, triethylamine (1.82, 18 mmol) was slowly added dropwise, after the addition was completed, warmed to room temperature, the reaction was stirred overnight, after the reaction was completed, the reaction solution was diluted with 50mL of methylene chloride, poured into a separating funnel, washed with deionized water (100 mL. Times.3) and saturated brine (100 mL. Times.3) in sequence, the organic phase was collected, dried over night with anhydrous sodium sulfate, then the filtrate was collected by filtration, the solvent was distilled off under reduced pressure, purified by chromatography column with petroleum ether/ethyl acetate (10/1→2/1) as eluent, and 1.8g of ethyl ethane was obtained as white powder by spin drying in 45.5% yield.
Example 10:
The alkoxide chain-linked diaryl formaldoxime (4 g,9.0 mmol) and methylene chloride (80 mL) were added into a round-bottomed flask, stirred and dissolved, then cooled to 0 ℃, sodium hypochlorite (180 mmol) aqueous solution was slowly added dropwise, after completion of the dropwise addition, the reaction was cooled to room temperature, stirred overnight, after completion of the reaction, the reaction solution was diluted with 50mL methylene chloride, poured into a separating funnel, washed with deionized water (100 mL. Times.3) and saturated saline (100 mL. Times.3) in this order, the organic phase was collected, dried over anhydrous sodium sulfate overnight, and then the filtrate was collected by filtration, and the solvent was distilled off under reduced pressure to give 3.8g of 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane as a white powder, with a yield of 95.9%.
And (3) structural identification:
1H NMR(CDCl3,500MHz,ppm),δ:6.62,4.11,3.84,3.73,2.41；
13C NMR(CDCl3,125MHz,ppm),δ:160.15,143.75,113.80,106.13,70.93,69.60, 67.50,21.12；
IR(KBr,cm-1),ν:2920,2871,2293,1602,1333,1170,1131,1046,859,688.
LC-MS (m/z) [ C 24H28N2O6Na+ ], found 463.1938, theoretical calculation 463.1845.
The nuclear magnetic resonance hydrogen spectrum of the synthesized target compound is shown in figure 1, and the integral ratio of each peak group is consistent with the corresponding hydrogen atom number ratio of the molecular structure of 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane. The infrared spectrum is shown in figure 2, wherein the strong absorption peak 2293cm -1 is the telescopic vibration peak of C.ident.N-, and the target compound is proved to contain stable-CNO groups.
The above structural identification data confirm that the material prepared by the present method is 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane.
Performance of 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane:
(1) Solubility of
Is easily dissolved in dichloromethane, chloroform, ethyl acetate, acetone, tetrahydrofuran, etc., slightly dissolved in methanol, insoluble in water, petroleum ether, etc.
(2) Room temperature stability
Is solid powder stable at room temperature (20-30 ℃) and can be stored for a long time.
(3) Reactivity of the reaction
The difunctional nitrile oxide of the present invention can be rapidly cycloaddition reacted with allyl glycidyl ether at 25℃with [3+2] of nitrile oxygen groups and double bonds using chloroform as solvent, and the successful progress of this reaction is confirmed in FIG. 3.
Use of 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane:
The 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane disclosed by the invention has a stable structure, has higher reactivity with a compound containing unsaturated double bonds, and can be applied to the field of non-isocyanate room temperature curing and forming of solid propellants.
Claims (1)
1. A method for synthesizing a1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound is characterized in that the 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane compound has a chemical structural formula shown in (I):
（I）；
the method comprises the following steps:
Adding 11.26 g of 2, 6-dimethyl-4-hydroxybenzaldehyde, 4.7 g g of 1, 2-bis (2-chloroethoxy) ethane and dried DMF 130 mL into a round bottom flask, stirring and dissolving at room temperature, adding 15.5 g of anhydrous potassium carbonate, placing the reaction bottle into an oil bath pot with 90 o ℃ for reacting and stirring for 48 h, filtering and collecting filtrate after the reaction is finished, distilling off DMF under reduced pressure, adding 200 mL ethyl acetate to redissolve reaction products, pouring into a separating funnel, washing with 100 mL X3 deionized water and 100 mL X3 saturated saline water in sequence, collecting an organic phase, drying overnight with anhydrous sodium sulfate, filtering and collecting filtrate, distilling off solvent under reduced pressure, collecting crude product, purifying by using a chromatographic column, obtaining white powdery alkoxy chain-linked diaryl formaldehyde 9.5 g by rotary evaporation and drying, wherein the eluent is petroleum ether/ethyl acetate 10/1- > 2/1, and the yield is 91.7%;
Adding alkoxy chain connected diaryl formaldehyde 4 g and methanol 80 mL into a round bottom flask, stirring and dispersing at room temperature to form a suspension, then sequentially adding hydroxylamine hydrochloride 2.67 g and sodium acetate 3.12g, stirring overnight, filtering and collecting filtrate after the reaction is finished, diluting the filtrate with 200 mL ethyl acetate, pouring into a separating funnel, sequentially washing with deionized water 100mL multiplied by 3 and saturated saline 100mL multiplied by 3, collecting an organic phase, drying overnight with anhydrous sodium sulfate, filtering and collecting filtrate, and evaporating under reduced pressure to remove the solvent to obtain white powdery alkoxy chain connected diaryl formaldehyde oxime 4.1 g with the yield of 96.2%;
Adding an alkoxy chain connected diaryl formaldoxime 4g and methylene dichloride 80mL into a round-bottom flask, stirring and dissolving, then cooling to 0 o ℃, slowly dropwise adding a sodium hypochlorite 180 mmol aqueous solution, after the dropwise adding is completed, heating to room temperature, stirring the reaction overnight, diluting the reaction liquid with 50 mL methylene dichloride after the reaction is completed, pouring into a separating funnel, washing with deionized water 100mL ×3 and saturated saline water 100mL ×3 in sequence, collecting an organic phase, drying overnight with anhydrous sodium sulfate, then filtering and collecting filtrate, and evaporating the solvent under reduced pressure to obtain white powdery 1, 2-bis (2- (3, 5-dimethyl-4-nitriloxyphenoxy) ethoxy) ethane 3.8 g with the yield of 95.9%.
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