CN110590558A - Method for catalyzing selective nitration of 1-methoxynaphthalene by using zeolite molecular sieve - Google Patents
Method for catalyzing selective nitration of 1-methoxynaphthalene by using zeolite molecular sieve Download PDFInfo
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- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 92
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000010457 zeolite Substances 0.000 title claims abstract description 92
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 78
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000006396 nitration reaction Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 112
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- YFJKGPRYPHFGQD-UHFFFAOYSA-N 1-methoxy-4-nitronaphthalene Chemical compound C1=CC=C2C(OC)=CC=C([N+]([O-])=O)C2=C1 YFJKGPRYPHFGQD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 239000012074 organic phase Substances 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- MADSSDZXBDQMAF-UHFFFAOYSA-N 1-methoxy-2-nitronaphthalene Chemical class C1=CC=C2C(OC)=C([N+]([O-])=O)C=CC2=C1 MADSSDZXBDQMAF-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 description 44
- 238000004458 analytical method Methods 0.000 description 20
- 239000011148 porous material Substances 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 230000000802 nitrating effect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 13
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000000758 substrate Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- WUGANDSUVKXMEC-UHFFFAOYSA-N 2-[4-[(4-bromophenyl)sulfonylamino]-1-hydroxynaphthalen-2-yl]sulfanylacetic acid Chemical compound C=12C=CC=CC2=C(O)C(SCC(=O)O)=CC=1NS(=O)(=O)C1=CC=C(Br)C=C1 WUGANDSUVKXMEC-UHFFFAOYSA-N 0.000 description 4
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- JCZMXVGQBBATMY-UHFFFAOYSA-N nitro acetate Chemical compound CC(=O)O[N+]([O-])=O JCZMXVGQBBATMY-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 2
- 101001056180 Homo sapiens Induced myeloid leukemia cell differentiation protein Mcl-1 Proteins 0.000 description 2
- 102100026539 Induced myeloid leukemia cell differentiation protein Mcl-1 Human genes 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 206010061902 Pancreatic neoplasm Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 208000015486 malignant pancreatic neoplasm Diseases 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- -1 nitroxyl cation Chemical class 0.000 description 2
- 201000002528 pancreatic cancer Diseases 0.000 description 2
- 208000008443 pancreatic carcinoma Diseases 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- OKQDLSOSWLNGHR-UHFFFAOYSA-N 1-(naphthalen-1-ylmethoxymethyl)naphthalene Chemical compound C1=CC=C2C(COCC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 OKQDLSOSWLNGHR-UHFFFAOYSA-N 0.000 description 1
- FUZSLHISAMCMOI-UHFFFAOYSA-N 1-(nitromethoxy)naphthalene Chemical compound [O-][N+](=O)COc1cccc2ccccc12 FUZSLHISAMCMOI-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000005775 apoptotic pathway Effects 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- BLNWTAHYTCHDJH-UHFFFAOYSA-O hydroxy(oxo)azanium Chemical compound O[NH+]=O BLNWTAHYTCHDJH-UHFFFAOYSA-O 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000001546 nitrifying effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for catalyzing selective nitration of 1-methoxynaphthalene by using a zeolite molecular sieve, which comprises the following steps: s1: calcining the zeolite molecular sieve catalyst for 6 hours at 550 ℃; s2: putting 6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride into a 50mL single-neck flask, oscillating to completely mix the 1-methoxynaphthalene and the 5mL of acetic anhydride, adding 0.1-1.1 g of zeolite molecular sieve catalyst, slowly adding 2mmol of bismuth nitrate under the stirring state, and stirring in a constant-temperature water bath at 25 ℃ to react for 12 hours; s3: after the reaction is finished, recovering the catalyst, adding 20mL of deionized water, heating to 40 ℃, and continuing the reaction for 1h to fully hydrolyze the acetic anhydride into acetic acid; s4: extracting, washing and drying; s5: and (5) separating and purifying. The invention selects SAPO-11 zeolite molecular sieve, when the dosage is 0.3g, the conversion rate of the raw material reaches 87.79 percent, the yield reaches 78.23 percent, the isomer ratio reaches 8.79, and the yield of 1-methoxy-4-nitronaphthalene is high.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a method for catalyzing selective nitration of 1-methoxynaphthalene by using a zeolite molecular sieve.
Background
The products of the primary nitration of 1-methoxynaphthalene include 1-methoxy-2-nitronaphthalene and 1-methoxy-4-nitronaphthalene, wherein 1-methoxy-4-nitronaphthalene is an important raw material for synthesizing UMI-77 reagent in industry, and UMI-77 can effectively interfere the interaction between cells Mcl-1 and BL-Noxa and the interaction between Mcl-1/Bax protein-protein. UMI-77 inhibited pancreatic cancer cell growth well with IC50 values of 16.1, 12.5, 4.4, 5.5, and 3.4. mu.M for AsPC-1, MiaPaCa-2, Panc-1, Capan-2, and BxPC-3 cells, respectively. UMI-77 induces pancreatic cancer cells to undergo apoptosis by activating Bax conformation change or an inherent apoptosis pathway, and has an important effect in the aspect of cancer medication. With the rapid development of the pharmaceutical and chemical industry in China, the demand of new anticancer materials is gradually increased, and the selective green nitration of 1-methoxynaphthalene is necessary to be realized, which is also a key means for improving the yield of 1-methoxy-4-nitronaphthalene and reducing byproducts.
The nitration mechanism of 1-methoxy naphthalene is as follows:
1) the reaction mechanism of the nitration of 1-methoxynaphthalene by a nitric acid/acetic anhydride system is as follows: in the reaction process, nitric acid firstly reacts with acetic anhydride to generate nitric acetate, then the nitric acetate is decomposed to generate dinitrogen pentoxide and acetic anhydride, and the dinitrogen pentoxide can generate NO after being activated2 +Ion, NO2 +Ions attack 1-methoxy naphthalene to obtain a nitration product, and the specific reaction process is as follows:
2) the reaction mechanism of the metal nitrate system nitration 1-methoxy naphthalene is as follows: the metal nitrate can decompose nitro radical under certain condition, so that some high-activity substrates such as naphthol, naphthyl methyl ether and the like can be nitrified. Some researchers found Fe (NO)3)3·9H2The O can be decomposed into ferrous nitrate and NO after being heated3Thereby undergoing radical electrophilic substitution with the aromatic compoundThe specific reaction scheme is as follows:
the scheme utilizes a nitrating agent/acetic anhydride system to nitrify 1-methoxynaphthalene, and adopts a controlled variable method to determine that the optimal nitrating agent is bismuth nitrate and NO3 -The optimal mol ratio of the 1-methoxy naphthalene is 1: 1. after the optimal reaction temperature is 25 ℃, influence of different types of zeolite molecular sieve catalysts and the dosage of the catalysts on the selective nitration reaction of the 1-methoxynaphthalene is researched, and influence of the performance and the recovery times of the recovered catalysts on the nitration reaction of the 1-methoxynaphthalene is further researched.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for catalyzing selective nitration of 1-methoxynaphthalene by using a zeolite molecular sieve so as to improve the yield of the 1-methoxy-4-nitronaphthalene and reduce side reactions.
The technical scheme of the invention is summarized as follows:
a method for catalyzing selective nitration of 1-methoxynaphthalene by utilizing a zeolite molecular sieve comprises the following steps:
s1: calcining the zeolite molecular sieve catalyst in a muffle furnace at 550 ℃ for 6 hours, and storing in a dryer;
s2: putting 6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride into a 50mL single-neck flask, oscillating to completely mix the 1-methoxynaphthalene and the 5mL of acetic anhydride, adding 0.1-1.1 g of zeolite molecular sieve catalyst, slowly adding 2mmol of bismuth nitrate under stirring, and controlling NO3 -The dosage ratio of 1-methoxynaphthalene is 1:1, putting a single-neck flask into a 25 ℃ constant-temperature water bath heat collection type heating stirrer for reaction for 12 hours;
s3: after the reaction is finished, recovering the catalyst, adding 20mL of deionized water, heating to 40 ℃, and continuing the reaction for 1h to fully hydrolyze the acetic anhydride into acetic acid;
s4: after the hydrolysis is completed, extracting, washing and drying the solution after the reaction;
s5: and (3) separating and purifying the dried solution, wherein the conversion rate of the raw material reaches 82.22-97.78%, and the ratio of the 1-methoxy-4-nitronaphthalene to the 1-methoxy-2-nitronaphthalene isomer in the product reaches 4.51-8.79.
Preferably, the zeolite molecular sieve catalyst comprises one or more of a beta-25 type zeolite molecular sieve, a beta-60 type zeolite molecular sieve, a SAPO-11 type zeolite molecular sieve, a ZSM-5 type zeolite molecular sieve, a USY type zeolite molecular sieve and a NaY type zeolite molecular sieve.
A method for catalyzing selective nitration of 1-methoxynaphthalene by utilizing a zeolite molecular sieve comprises the following steps:
s1: placing the SAPO-11 type zeolite molecular sieve catalyst in a muffle furnace at 550 ℃ for calcining for 6h, and storing in a dryer;
s2: putting 6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride into a 50mL single-neck flask, oscillating to completely mix, adding 0.3g of zeolite molecular sieve catalyst, slowly adding 2mmol of bismuth nitrate under stirring, and controlling NO3 -The dosage ratio of 1-methoxynaphthalene is 1:1, putting a single-neck flask into a 25 ℃ constant-temperature water bath heat collection type heating stirrer for reaction for 12 hours;
s3: after the reaction is finished, recovering the catalyst, adding 20mL of deionized water, heating to 40 ℃, and continuing the reaction for 1h to fully hydrolyze the acetic anhydride into acetic acid;
s4: after the hydrolysis is completed, extracting, washing and drying the solution after the reaction;
s5: the dried solution is separated and purified, the conversion rate of the raw material reaches 87.79 percent, and the isomer ratio of 1-methoxyl-4-nitronaphthalene to 1-methoxyl-2-nitronaphthalene in the product reaches 8.79.
Preferably, the catalyst recovery method specifically comprises: and (3) standing the solution after the reaction of S2 for 24h, carrying out solid-liquid separation, washing the catalyst at the bottom with water and dichloromethane for 3 times respectively, putting the recovered catalyst into a drying oven for drying for 24h, calcining in a muffle furnace at 550 ℃ for 6h, and repeatedly recovering and recycling for 3 times.
Preferably, the extraction, washing and drying processes are specifically as follows: and after the acetic anhydride is completely hydrolyzed, adding 10mL of dichloromethane, fully oscillating, extracting and separating liquid, retaining a lower organic phase, repeating the operation of the upper aqueous phase with 20mL of dichloromethane, combining the organic phases after liquid separation, washing the obtained organic phase with 20mL of deionized water, washing with 20mL of saturated sodium carbonate solution for 1-2 times, washing with 20mL of deionized water for 3 times, and adding 2g of anhydrous sodium sulfate into the obtained oily organic phase for drying for 24 hours.
Preferably, the separation and purification process specifically comprises: and (3) carrying out coarse purification on the dried solution by using a vacuum rotary evaporator, setting the water bath temperature to be 60 ℃, rotating the speed to be 30r/min, and finishing distillation when no water drops fall below the serpentine condenser pipe.
The invention has the beneficial effects that:
1. the invention utilizes a nitric acid agent/acetic anhydride system to nitrify 1-methoxynaphthalene, and adopts a controlled variation method to determine that the optimal nitrating agent is bismuth nitrate and NO3 -The optimal mol ratio of the 1-methoxy naphthalene is 1: 1. after the optimal reaction temperature is 25 ℃, the influence of different types of zeolite molecular sieve catalysts and the catalyst dosage on the selective nitration reaction of the 1-methoxynaphthalene is researched, and experiments show that when the catalyst type is an SAPO-11 type zeolite molecular sieve and the dosage is 0.3g, the conversion rate of the raw material reaches 87.79 percent, the yield reaches 78.23 percent, the isomer ratio of the 1-methoxy-4-nitronaphthalene to the 1-methoxy-2-nitronaphthalene in the product reaches 8.79, the optimal nitration yield of the 1-methoxy-4-nitronaphthalene is achieved, the content of byproducts is low, and the reaction nitro product is subjected to post-treatment to obtain the 1-methoxy-4-nitronaphthalene with the purity of 98.9 percent.
2. The zeolite molecular sieve catalyst can be repeatedly recycled for more than three times, and the activity and the surface property of the catalyst are not obviously changed.
Drawings
FIG. 1 is an XRD analysis of a SAPO-11 zeolite molecular sieve catalyst wherein (a) fresh catalyst, (b) recovered catalyst, (c) regenerated catalyst;
FIG. 2 is a FT-IR analysis of a SAPO-11 zeolitic molecular sieve catalyst wherein (a) fresh catalyst, (b) recovered catalyst, (c) regenerated catalyst;
FIG. 3 is N of SAPO-11 zeolite molecular sieve2Adsorption-desorption isotherms;
FIG. 4 is a pore size distribution curve for a SAPO-11 zeolite molecular sieve;
FIG. 5 is a TG diagram of a recovered SAPO-11 zeolite molecular sieve;
FIG. 6 is a surface topography of a SAPO-11 zeolite molecular sieve;
FIG. 7 is a GC-MS spectrum of a 1-methoxynaphthalene nitration product;
FIG. 8 is a retrieval graph of the similarity of the main nitration products of 1-methoxynaphthalene;
FIG. 9 is a FT-IR diagram of 1-methoxy-4-nitronaphthalene;
FIG. 10 is the FT-IR characteristic peak of the pure 1-methoxy-4-nitronaphthalene;
FIG. 11 is a diagram of melting point analysis of a pure 1-methoxy-4-nitronaphthalene;
FIG. 12 is a flow chart of the method of the present invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Examples 1 to 5 study the optimum nitrating agent for nitration of 1-methoxynaphthalene
Under the same other reaction conditions, different kinds of nitrating agents were added to carry out comparative experiments. The nitrating agents corresponding to examples 1-5 were ferric nitrate, aluminum nitrate, bismuth nitrate, magnesium nitrate, and nitric acid in this order, and the test methods were as follows:
weighing 6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride in turn, putting the 1-methoxynaphthalene and the 5mL of acetic anhydride into a 50mL single-neck flask, oscillating to completely mix the 1-methoxynaphthalene and the 5mL of acetic anhydride, slowly adding 2mmol of ferric nitrate/2 mmol of aluminum nitrate/2 mmol of bismuth nitrate/3 mmol of magnesium nitrate/6 mmol of nitric acid into the single-neck flask under the stirring state, and putting the flask into a 25 ℃ constant-temperature water bath heat collection type heating stirrer for reaction for 12 hours.
Product post-treatment:
1) hydrolysis, extraction, washing and drying: after the reaction is finished, adding 20mL of deionized water into the flask, raising the temperature to 40 ℃, and continuing the reaction for 1h to fully hydrolyze the acetic anhydride into acetic acid; adding 10mL of dichloromethane into the flask after complete hydrolysis, fully oscillating, pouring into a separating funnel, extracting and separating, retaining the lower organic phase, repeating the operation on the upper aqueous phase by using 20mL of dichloromethane, and combining the organic phases for 3 times after separating; washing the obtained organic phase with 20mL of deionized water, then washing with 20mL of saturated sodium carbonate solution for 1-2 times, finally washing with 20mL of deionized water for 3 times, placing the obtained oily organic phase in a conical flask, adding 2g of anhydrous sodium sulfate, and drying for 24 h.
2) Gas chromatographic analysis: placing 2mL of dried solution in sample bottles, sequencing the sample bottles, placing the sequenced sample bottles on an automatic sample injector, detecting the sample by using a gas chromatograph provided with CATALOG 19091J-41330m × 0.320mm chromatographic columns, setting the temperature of a sample inlet to be 250 ℃, the split ratio to be 10:1, the temperature of a detector to be 250 ℃, and H2The flow rate is 50.0mL/min, the air flow rate is 250.0mL/min, the sample injection amount is 1 muL, the initial temperature is 140 ℃, the holding time is 1min, the first-stage temperature is 180 ℃, the heating rate is 20 ℃/min, the holding time is 1min, the second-stage temperature is 240 ℃/min, and the holding time is 1 min. And recording the content of each substance in the solution according to the gas chromatogram.
3) Separation and purification: pouring the dried solution into a distillation flask, performing coarse purification by using a vacuum rotary evaporator, setting the water bath temperature at 60 ℃, rotating the rotation speed at 30r/min, finishing distillation when no water drops fall below a serpentine condenser pipe, weighing a coarse product, and calculating the yield;
washing the crude product with anhydrous ether for 3 times, dissolving with anhydrous ethanol at 70 deg.C to saturation, sealing with PC preservative film, crystallizing in a fume hood for 24 hr, filtering to obtain first recrystallized product, oven drying, and measuring content with gas chromatograph; and (4) putting the filtrate into a refrigerator at the temperature of 18 ℃ below zero for continuous crystallization, filtering to obtain a secondary recrystallization product, and performing content determination on the filter residue and the filtrate by using a gas chromatograph respectively.
4) And (3) calculating the yield: calculating the yield of each product according to the content of each component measured in the gas chromatograph by using the following formula:
wherein, ω is1Content of ingredient in the product
m1Actual production
m0Theoretical yield
Table 1 shows the effect of different nitrating agents on the selective nitration of 1-methoxynaphthalene
TABLE 1 Effect of nitrating agent classes on the Selective nitration of 1-methoxynaphthalene
As can be seen from Table 1: under the same other conditions, the conversion rate of the bismuth nitrate nitrated 1-methoxynaphthalene reaches 88.63%, and the proportion of the 4-nitro product to the 2-nitro product is also the highest, so the bismuth nitrate is selected as the nitrating agent. Bismuth nitrate has good conversion rate and selectivity when nitrifying naphthalene and derivatives thereof, and the reaction mechanism of the nitration is as follows:
reacting bismuth nitrate with acetic anhydride in an acetic anhydride system to generate acetyl nitrate and bismuth acetate, wherein the equation is as follows:
and because bismuth nitrate has five crystal waters, acetic anhydride is decomposed into acetic acid in the reaction system in the presence of water, so the general equation of the reaction is as follows:
acetyl nitrate then decomposes into acetate and nitroxyl cation:
wherein the nitroxyl cation is used as an electrophilic attack reagent to attack 1-methoxy naphthalene, so that the 1-methoxy naphthalene is deprotonated to form a nitromethoxy naphthalene product.
Examples 6 to 9 study on the optimum amount of nitrating agent for nitration of 1-methoxynaphthalene
On the basis of obtaining the optimal nitrating agent, the molar ratio of the nitrating agent to the dosage of the 1-methoxynaphthalene is changed. Example 3 corresponding NO3 -NO corresponding to examples 6 to 9, with the amount of 1-methoxynaphthalene in a molar ratio of 1:13 -The molar ratio of the 1-methoxynaphthalene to the 1-methoxynaphthalene is 1.2:1, 1.4:1, 1.6:1 and 1.8:1 in sequence, and the test method comprises the following steps:
6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride are put into a 50mL single-neck flask and shaken to be completely mixed, and NO is slowly added into the single-neck flask under the stirring state3 -Adding bismuth nitrate with the molar ratio of 1.2:1/1.4:1/1.6:1/1.8:1 to 1-methoxynaphthalene into a flask, and reacting for 12h in a water-bath heat-collecting type heating stirrer with the constant temperature of 25 ℃.
The product post-treatment was the same as in examples 1 to 5.
Table 2 shows the effect of different nitrating agent amounts on the selective nitration of 1-methoxynaphthalene
TABLE 2 Effect of nitrating agent dosage on Selective nitration of 1-methoxynaphthalene
As can be seen from Table 2: when NO is present3 -After the dosage ratio of the 1.2:1 to the substrate is reached, the 1-methoxynaphthalene can be regarded as completely reacted, and the isomer ratio of the product is also increased to a certain extent, but in the case of NO3 -When the amount ratio of the product to the substrate is 1.6:1 or more, the isomer ratio of the product begins to decrease, and there is a possibility that a part of dinitro product is formed due to a large amount of the nitrating agent in the reaction. NO because of the great difficulty in subsequent separation and purification due to dinitro product3 -The amount ratio of the substrate to the substrate is selected1:1, namely 2mmol of bismuth nitrate.
Examples 10 to 12 study the optimum reaction temperature for nitration of 1-methoxynaphthalene
The reaction temperature of the system was varied according to the conditions determined above. The reaction temperature for example 3 was 25 ℃, the reaction temperatures for examples 10-12 were 5 ℃, 15 ℃ and 35 ℃ in this order, and the test methods were as follows:
6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride are put into a 50mL single-neck flask, are shaken to be completely mixed, 2mmol of bismuth nitrate is slowly added into the single-neck flask under the stirring state, and then the single-neck flask is respectively put into a constant-temperature water bath heat collection type heating stirrer with the temperature of 5 ℃/15 ℃/35 ℃ to react for 12 hours.
The product post-treatment was the same as in examples 1 to 5.
Table 3 shows the effect of different reaction temperatures on the selective nitration of 1-methoxynaphthalene
TABLE 3 influence of the reaction temperature on the Selective nitration of 1-methoxynaphthalene
As can be seen from Table 3: the optimum reaction temperature is 25 ℃, and the reaction temperature is too low or too high, which is unfavorable for the reaction, probably because the reaction is endothermic, too low temperature can reduce the reaction speed, and too high temperature can lead to the decomposition of the intermediate acetyl nitrate under the heating condition, thereby reducing the conversion rate of the reaction.
Examples 13-18 study on the influence of different zeolite molecular sieve catalysts on the selective nitration of 1-methoxynaphthalene
According to the determined optimal conditions, different kinds of zeolite molecular sieve catalysts are respectively added into the reaction system, and the influence of the different kinds of zeolite molecular sieve catalysts on the reaction is researched. The catalysts corresponding to the embodiments 13-18 are beta-25, beta-60, SAPO-11, ZSM-5, USY and NaY catalysts in sequence, and the test method is as follows:
putting 6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride into a 50mL single-neck flask, oscillating to completely mix the 1-methoxynaphthalene and the 5mL of acetic anhydride, then respectively adding 0.5g of beta-25/beta-60/SAPO-11/ZSM-5/USY/NaY catalyst (all zeolite catalysts are calcined in a muffle furnace at 550 ℃ for 6 hours and stored in a dryer) into the flask, slowly adding 2mmol of bismuth nitrate into the single-neck flask under the stirring state, and then putting all the single-neck flasks into a 25 ℃ constant-temperature water bath heat collection type heating stirrer to react for 12 hours.
The product post-treatment is the same as in examples 1 to 5, except that the catalyst is recovered before hydrolyzing acetic acid, and the recovery method is as follows: after the reaction is finished, standing the solution for 24h, carrying out solid-liquid separation, washing the bottom catalyst with water and dichloromethane for 3 times respectively, putting the recovered catalyst into a drying oven to be dried for 24h, calcining in a muffle furnace at 550 ℃ for 6h, and repeatedly recovering and recycling for 3 times.
Table 4 shows the effect of different zeolite molecular sieve catalysts on the selective nitration of 1-methoxynaphthalene
TABLE 4 Effect of different catalysts on the Selective nitration of 1-Methoxynaphthalene
As can be seen from table 4: after the catalyst is added, the conversion rate and the isomerization ratio of the reaction are changed to some extent. Wherein, the conversion rates of the beta-25, SAPO-11, ZSM-5 and NaY zeolite catalysts are improved to a certain extent, but the isomer ratios of the beta-25, ZSM-5 and NaY are reduced, and the isomer ratio is improved while the conversion rate of the SAPO-11 zeolite is improved. Probably because the crystallinity and acidity of SAPO-11 are more conducive in terms of isomer ratio, the SAPO-11 zeolite catalyst is the best catalyst for the selective nitration of 1-methoxynaphthalene.
Example 19-23 study on the influence of different dosage of SAPO-11 zeolite molecular sieve catalysts on selective nitration of 1-methoxynaphthalene
According to the determined conditions, SAPO-11 catalysts with different masses are added into the reaction system, and the influence of the catalyst dosage on the nitration reaction of the 1-methoxynaphthalene is researched. The catalyst dosage corresponding to the embodiment 15 is 0.5g, and the catalyst dosages corresponding to the embodiments 19 to 23 are 0.1g, 0.3g, 0.7g, 0.9g and 1.1g in sequence, and the test method is as follows:
6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride are put into a 50mL single-neck flask, are shaken to be completely mixed, then are respectively added with 0.1g/0.3g/0.7g/0.9g/1.1g of SAPO-11 zeolite molecular sieve catalyst (which is calcined in a muffle furnace at 550 ℃ for 6h and is stored in a dryer), 2mmol of bismuth nitrate is slowly added into the single-neck flask under the stirring state, and then all the single-neck flasks are put into a 25 ℃ thermostatic waterbath heat collection type heating stirrer to react for 12 h.
The product post-treatment was the same as in examples 15 to 20.
Table 5 shows the effect of different amounts of SAPO-11 zeolite molecular sieve catalyst on the selective nitration of 1-methoxynaphthalene
TABLE 5 influence of the amount of catalyst on the Selective nitration of 1-Methoxynaphthalene
As can be seen from table 5: the conversion rate is not changed greatly by adding catalysts with different mass, and the obvious effect is generated on the isomer ratio. When the amount of catalyst used was 0.3g, the isomer ratio reached the highest value of 8.79. Therefore, 0.3g is preferred.
Comparing the data in Table 5, it can be seen that when the amount of the catalyst is more than 0.7g, not only the isomer ratio begins to decrease, but also the conversion rate of the reaction begins to decrease, probably because the amount of the catalyst adsorbing the substrate is larger and larger as the amount of the catalyst in the reaction system increases, and the substrate adsorbed in the pore diameter of the catalyst cannot completely participate in the reaction, thereby resulting in a decrease in the conversion rate of the reaction.
Example 24-26 study on the influence of the catalyst recovery times on the nitration of 1-methoxynaphthalene
Reuse of SAPO-11 catalyst: 6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride are put into a 50mL single-neck flask, are shaken to be completely mixed, then 0.3g of regenerated 1/2/3 SAPO-11 zeolite molecular sieve catalyst (calcined in a muffle furnace at 550 ℃ for 6 hours) is added into the flask, 2mmol of bismuth nitrate is slowly added into the single-neck flask under stirring, and then all the single-neck flasks are put into a 25 ℃ constant-temperature water bath heat collection type heating stirrer to react for 12 hours. The product post-treatment was the same as in examples 15 to 20.
Table 6 shows the effect of the number of SAPO-11 catalyst recoveries on the selective nitration of 1-methoxynaphthalene
TABLE 6 influence of catalyst regeneration number on 1-methoxynaphthalene Selective nitration
As is clear from the data in Table 6: the SAPO-11 zeolite molecular sieve catalyst has good recycling performance, and the effect of the catalyst on selective nitration of 1-methoxynaphthalene after being recycled for 3 times has no obvious difference with a fresh catalyst. Therefore, the catalyst can be recycled more than 3 times.
Example 27-31 characterization and detection of SAPO-11 Zeolite molecular sieves
Taking SAPO-11 zeolite molecular sieve catalyst as a detection sample, and respectively carrying out XRD analysis, FT-IR analysis and N analysis2Adsorption-desorption analysis, thermogravimetric analysis and SEM characterization are carried out, and the influence of the recovery times on the nitration reaction of the 1-methoxynaphthalene is researched.
Example 27 XRD analysis of SAPO-11 zeolitic molecular sieves
1) XRD analysis method and conditions: an X-ray diffractometer is used for detecting samples of fresh SAPO-11 zeolite molecular sieve catalyst, which are recovered without calcination and regenerated after calcination, the voltage is set to be 20kV, the current is 30mA, DS (SS) (1 degree), RS (0.2 degree), the instrument scanning angle is 5-60 degrees, and the scanning step is 0.02 degree.
2) XRD analysis result: FIG. 1 is an XRD analysis of a SAPO-11 zeolite molecular sieve catalyst wherein (a) fresh catalyst, (b) recovered catalyst, and (c) regenerated catalyst. As can be seen from the figure, the unique structural peaks of the SAPO-11 zeolite molecular sieve catalyst appear at the 2 theta angles of 9.0 degrees, 10.5 degrees, 16.6 degrees, 22.0 degrees and 24.1 degrees; after the recovered catalyst is calcined in a muffle furnace at 550 ℃ for 6 hours, the position and the strength of the peak are not changed compared with those of a fresh catalyst, which shows that the crystal structure and the characteristics of the calcined catalyst are basically unchanged, namely the space structure of the catalyst is not damaged, and the experiment result is also corresponding to the experiment result that the catalyst effect of a regenerated catalyst is similar to that of the fresh catalyst; however, the first diffraction peak of the recovered catalyst is low, which may be caused by that some of the substrate and product enter the catalyst during the reaction to block the pore size, thereby reducing the diffraction intensity.
Example 28 FT-IR analysis of SAPO-11 zeolitic molecular sieves
1) FT-IR analysis method and detection conditions: performing performance analysis on a sample which is fresh, recycled and not calcined and recycled and regenerated by the SAPO-11 zeolite molecular sieve catalyst by using a Fourier transform infrared spectrometer, putting KBr into an infrared oven, baking for 20min, taking out, uniformly mixing with the sample according to the ratio of 100:1, grinding for 10min in an agate mortar, sieving and tabletting. Setting the detection wavelength to 4000cm in the mid-infrared region-1～400cm-1The sample transmittance was measured.
2) FT-IR analysis results: different SAPO-11 zeolite molecular sieve catalysts at 4000cm-1-400cm-1The infrared spectrum in the range is shown in FIG. 2, in which (a) a fresh catalyst, (b) a recovered catalyst, and (c) a regenerated catalyst are shown in the graph at 3600cm-1The nearby peak is an absorption peak generated by the stretching vibration of H-O, 1636cm-1Absorption peaks due to bending vibration of nearby peaks H-O. 1046cm-1、1130cm-1、720cm-1、473cm-1Absorption peaks are respectively external tetrahedral TO4Antisymmetric peak, symmetric stretching vibration, double circular ring and bending vibration peak. The infrared spectrum has the typical characteristics of the SAPO-11 zeolite catalyst. As can be seen by comparison with fresh SAPO-11 zeolite catalyst, the recovered SAPO-11 zeolite catalyst, except for the band with the fresh SAPO-11 zeolite catalyst, was 1510cm-1、1341cm-1、1227cm-1、569cm-1、516cm-1Also has some vibration peaks, which may be catalyst to solvent, 1-methoxy naphthaleneAnd C-H bending vibration peak and stretching vibration peak caused by the absorption of nitration products thereof.
Example 29N treatment of SAPO-11 zeolitic molecular sieves2Adsorption-desorption analysis
1)N2Adsorption-desorption analysis method and detection conditions: respectively taking 0.1g of fresh SAPO-11 zeolite molecular sieve catalyst, recovering the uncalcined zeolite, recovering the calcined zeolite and regenerating the calcined zeolite, putting the samples into a sample tube, degassing the samples in the instrument at 150 ℃ for 12 hours in advance, and then detecting the samples in a specific surface area determinator.
2)N2Adsorption-desorption analysis results: FIG. 3 is N of SAPO-11 zeolite molecular sieve2Adsorption-desorption isotherms, fig. 4 is a pore size distribution curve of the SAPO-11 zeolite molecular sieve, fig. 3 corresponds to fig. 4, and table 7 is a pore size distribution table of the SAPO-11 zeolite molecular sieve.
TABLE 7 pore size distribution Table for SAPO-11 zeolite molecular sieves
As can be seen from the data in Table 7, the specific surface area of the SAPO-11 zeolite catalyst after use was much reduced from the original 210m2·g-1Down to 51.1m2·g-1Pore volume of 0.623cm from the original3·g-1Down to 0.572cm3·g-1The pore diameter is reduced to 1.48nm from the original 2.91nm, and the main reason for analysis is probably that the used catalyst generates adsorption to other substances in a reaction system such as 1-methoxynaphthalene, 1-methoxy-4-nitronaphthalene and the like in the nitration reaction process, and even if the substances enter the pore diameter after being washed by a solvent, the substances cannot be completely desorbed, so that the specific surface area, the pore volume and the pore diameter of the pore channel are reduced; the catalyst returned to essentially its original level after calcination regeneration, a slight decrease, probably due to the acidic species used in the reaction leading to silicon migration and framework collapse of the SAPO-11 catalyst.
Example 30 thermogravimetric analysis of SAPO-11 zeolitic molecular sieves
1) Thermogravimetric analysis method and detection conditions: putting the recovered 15mgSAPO-11 zeolite molecular sieve sample into a corundum crucible, setting the initial temperature to be 25 ℃, the termination temperature to be 600 ℃, heating at the speed of 5 ℃/min, and carrying out thermogravimetric analysis (TGA) by using a microcomputer differential thermal balance.
2) Thermogravimetric analysis results: FIG. 5 is a TG diagram of a recovered SAPO-11 zeolite molecular sieve, and it can be known from the diagram that SAPO-11 zeolite has a certain weight loss in the temperature range of 25-600 ℃, because zeolite has a pore structure and good adsorbability, once exposed in the air, it can adsorb moisture contained in the air, thereby reducing the catalytic performance of the zeolite to nitration reaction, so that the catalyst used before each nitration reaction experiment needs to be dried and calcined and stored in a dryer in time to prevent water absorption from affecting the catalytic effect; meanwhile, because the pore structure of the SAPO-11 enables the SAPO-11 to have certain adsorbability on the 1-methoxynaphthalene and nitration products thereof, a small amount of substances are adsorbed into the pore canal and cannot be desorbed, and impurities in the pore canal cannot be completely washed out by a simple solvent washing liquid. After the temperature reaches 550 ℃, the weight loss rate gradually approaches to equilibrium, which indicates that impurities in the pore diameter of the SAPO-11 are completely calcined, and the performance of the later recovered catalyst is not changed too much and corresponds to the performance of the later recovered catalyst.
Example 31 SEM characterization of SAPO-11 zeolitic molecular sieves
The SAPO-11 zeolite molecular sieve was scanned with a Scanning Electron Microscope (SEM) and a photograph was taken, and fig. 6 is an SEM surface topography of the SAPO-11 zeolite molecular sieve.
EXAMPLE 32 analysis and examination of the selectively nitrated product of 1-methoxynaphthalene in example 20
1) GC-MS analysis of the product
The analysis conditions and methods: placing 2mL of the dried solution (dried solution in the product post-treatment process) in a sample bottle, placing the sample on a SHIMADZU AOC-20i autosampler, performing sample detection by using a gas chromatograph-mass spectrometer equipped with SHIMADZU SH-Rxi-5Sil MS chromatographic column, setting the gas phase injection port temperature at 250 ℃, the split ratio at 10:1, the detector temperature at 250 ℃, and H2Flow rate of 50.0mL/min, air flow rate of 250.0mL/min, sample injection amount of 1 μ L, initial temperature of 140 deg.C, and holding timeThe time is 5min, the first-stage temperature is 180 ℃, the heating rate is 20 ℃/min, the holding time is 10min, the second-stage temperature is 240 ℃/min, and the holding time is 15 min. And then, determining each component in the product according to the similarity retrieval of the mass spectrogram.
And (3) analysis results: FIG. 7 is a GC-MS spectrum of a 1-methoxynaphthalene nitration product; FIG. 8 is a retrieval picture of the similarity of the main nitration products of 1-methoxynaphthalene. As can be seen from FIG. 7, the product of the reaction is 1-methoxy-4-nitronaphthalene, although the similarity is low in the similarity search chart, the reaction substrate is 1-methoxynaphthalene, and only the nitration product can be generated in the reaction system, so that the main product of the reaction can be determined to be 1-methoxy-4-nitronaphthalene.
2) Fourier transform Infrared Spectroscopy (FT-IR) analysis
The analysis conditions and methods: performing performance analysis on the product by using a Fourier transform infrared spectrometer, putting KBr into an infrared oven, baking for 20min, taking out, uniformly mixing with the product according to the ratio of 100:1, grinding in an agate mortar for 10min, sieving and tabletting. Setting the detection wavelength as 4000cm < -1 > to 400cm < -1 > of the mid-infrared region to measure the transmittance of the product.
And (3) analysis results: FIG. 9 is a FT-IR diagram of 1-methoxy-4-nitronaphthalene; FIG. 10 shows FT-IR characteristic peaks of a pure 1-methoxy-4-nitronaphthalene. As can be seen by comparing the spectra, the infrared spectrum has the typical characteristics of 1-methoxy-4-nitronaphthalene.
3) Microcomputer melting point instrument analysis method and condition
The analysis conditions and methods: the melting point of the product is measured by a microcomputer melting point instrument, the product with the height of about 1cm is filled into the capillary, and the capillary is filled into the microcomputer melting point instrument after being filled. Setting the initial temperature to 50 ℃ and the heating rate to 5.0 ℃/min, and recording initial melting and final melting values. FIG. 11 is a graph showing the melting point analysis of a pure 1-methoxy-4-nitronaphthalene.
And (3) analysis results: FIG. 11 is a graph showing the melting point analysis of a pure 1-methoxy-4-nitronaphthalene, and it can be seen that the melting point was measured at 81.1 to 81.6 ℃ and the temperature in the reference was 83 to 85 ℃. The reason for the low melting point may be that the sample is not pure enough and contains a small amount of impurities.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (6)
1. A method for catalyzing selective nitration of 1-methoxynaphthalene by utilizing a zeolite molecular sieve is characterized by comprising the following steps:
s1: calcining the zeolite molecular sieve catalyst in a muffle furnace at 550 ℃ for 6 hours, and storing in a dryer;
s2: putting 6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride into a 50mL single-neck flask, oscillating to completely mix the 1-methoxynaphthalene and the 5mL of acetic anhydride, adding 0.1-1.1 g of zeolite molecular sieve catalyst, slowly adding 2mmol of bismuth nitrate under stirring, and controlling NO3 -The dosage ratio of 1-methoxynaphthalene is 1:1, putting a single-neck flask into a 25 ℃ constant-temperature water bath heat collection type heating stirrer for reaction for 12 hours;
s3: after the reaction is finished, recovering the catalyst, adding 20mL of deionized water, heating to 40 ℃, and continuing the reaction for 1h to fully hydrolyze the acetic anhydride into acetic acid;
s4: after the hydrolysis is completed, extracting, washing and drying the solution after the reaction;
s5: and (3) separating and purifying the dried solution, wherein the conversion rate of the raw material reaches 82.22-97.78%, and the ratio of the 1-methoxy-4-nitronaphthalene to the 1-methoxy-2-nitronaphthalene isomer in the product reaches 4.51-8.79.
2. The method for catalyzing selective nitration of 1-methoxynaphthalene by using zeolite molecular sieve as claimed in claim 1, wherein said zeolite molecular sieve catalyst comprises one or more of zeolite beta-25 type zeolite molecular sieve, zeolite beta-60 type zeolite molecular sieve, zeolite SAPO-11 type zeolite molecular sieve, ZSM-5 type zeolite molecular sieve, zeolite USY type zeolite molecular sieve, and zeolite NaY type zeolite molecular sieve.
3. The method for catalyzing selective nitration of 1-methoxynaphthalene by zeolite molecular sieve according to claim 1, characterized by comprising the steps of:
s1: placing the SAPO-11 type zeolite molecular sieve catalyst in a muffle furnace at 550 ℃ for calcining for 6h, and storing in a dryer;
s2: putting 6mmol of 1-methoxynaphthalene and 5mL of acetic anhydride into a 50mL single-neck flask, oscillating to completely mix, adding 0.3g of zeolite molecular sieve catalyst, slowly adding 2mmol of bismuth nitrate under stirring, and controlling NO3 -The dosage ratio of 1-methoxynaphthalene is 1:1, putting a single-neck flask into a 25 ℃ constant-temperature water bath heat collection type heating stirrer for reaction for 12 hours;
s3: after the reaction is finished, recovering the catalyst, adding 20mL of deionized water, heating to 40 ℃, and continuing the reaction for 1h to fully hydrolyze the acetic anhydride into acetic acid;
s4: after the hydrolysis is completed, extracting, washing and drying the solution after the reaction;
s5: the dried solution is separated and purified, the conversion rate of the raw material reaches 87.79 percent, and the isomer ratio of 1-methoxyl-4-nitronaphthalene to 1-methoxyl-2-nitronaphthalene in the product reaches 8.79.
4. The method for catalyzing selective nitration of 1-methoxynaphthalene by using zeolite molecular sieve according to any one of claims 1 or 3, characterized in that the catalyst recovery method specifically comprises: and (3) standing the solution after the reaction of S2 for 24h, carrying out solid-liquid separation, washing the catalyst at the bottom with water and dichloromethane for 3 times respectively, putting the recovered catalyst into a drying oven for drying for 24h, calcining in a muffle furnace at 550 ℃ for 6h, and repeatedly recovering and recycling for 3 times.
5. The method for catalyzing selective nitration of 1-methoxynaphthalene by using zeolite molecular sieve according to any one of claims 1 or 3, characterized in that the extraction, washing and drying processes are specifically as follows: and after the acetic anhydride is completely hydrolyzed, adding 10mL of dichloromethane, fully oscillating, extracting and separating liquid, retaining a lower organic phase, repeating the operation of the upper aqueous phase with 20mL of dichloromethane, combining the organic phases after liquid separation, washing the obtained organic phase with 20mL of deionized water, washing with 20mL of saturated sodium carbonate solution for 1-2 times, washing with 20mL of deionized water for 3 times, and adding 2g of anhydrous sodium sulfate into the obtained oily organic phase for drying for 24 hours.
6. The method for catalyzing selective nitration of 1-methoxynaphthalene by using zeolite molecular sieve according to any one of claims 1 or 3, characterized in that the separation and purification process specifically comprises: and (3) carrying out coarse purification on the dried solution by using a vacuum rotary evaporator, setting the water bath temperature to be 60 ℃, rotating the speed to be 30r/min, and finishing distillation when no water drops fall below the serpentine condenser pipe.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773201A (en) * | 2022-05-12 | 2022-07-22 | 都创(上海)医药开发有限公司 | Method for rapidly preparing 1-methoxy-4-nitronaphthalene based on micro-channel continuous flow technology |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230718A (en) * | 2014-09-01 | 2014-12-24 | 南京理工大学 | Synthetic method of 4-nitroorhto-xylene |
| CN105175269A (en) * | 2015-08-10 | 2015-12-23 | 合肥师范学院 | Synthesis method of 4-nitro m-xylene by selective nitration of bismuth nitrate |
| CN105859560A (en) * | 2016-05-10 | 2016-08-17 | 蚌埠学院 | Method for increasing nitration nitro product yield of 4,4'-bis(chloromethyl)-1,1'-biphenyl |
| CN106831434A (en) * | 2017-01-20 | 2017-06-13 | 蚌埠学院 | In the method that biphenyl list ethyl ketone nitrification prepares 24 ' acetyl 4 nitrobiphenyls and the nitrobiphenyl of 14 ' acetyl group 2 |
-
2019
- 2019-10-09 CN CN201910953628.6A patent/CN110590558A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230718A (en) * | 2014-09-01 | 2014-12-24 | 南京理工大学 | Synthetic method of 4-nitroorhto-xylene |
| CN105175269A (en) * | 2015-08-10 | 2015-12-23 | 合肥师范学院 | Synthesis method of 4-nitro m-xylene by selective nitration of bismuth nitrate |
| CN105859560A (en) * | 2016-05-10 | 2016-08-17 | 蚌埠学院 | Method for increasing nitration nitro product yield of 4,4'-bis(chloromethyl)-1,1'-biphenyl |
| CN106831434A (en) * | 2017-01-20 | 2017-06-13 | 蚌埠学院 | In the method that biphenyl list ethyl ketone nitrification prepares 24 ' acetyl 4 nitrobiphenyls and the nitrobiphenyl of 14 ' acetyl group 2 |
Non-Patent Citations (1)
| Title |
|---|
| MASAHITO MURAI等: "Regioselective Functionalization of 9,9-Dimethyl-9-silafluorenes by Borylation, Bromination, and Nitration", 《J. ORG. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773201A (en) * | 2022-05-12 | 2022-07-22 | 都创(上海)医药开发有限公司 | Method for rapidly preparing 1-methoxy-4-nitronaphthalene based on micro-channel continuous flow technology |
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