CN115894162B - Method for preparing p-bromotoluene by catalyzing toluene with niobium - Google Patents
Method for preparing p-bromotoluene by catalyzing toluene with niobium Download PDFInfo
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 150
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000010955 niobium Substances 0.000 title claims abstract description 19
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 14
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 148
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 52
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 19
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 12
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 4
- 229930024421 Adenine Natural products 0.000 claims description 4
- 229960000643 adenine Drugs 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 abstract description 35
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 125000001246 bromo group Chemical group Br* 0.000 abstract 1
- 230000009849 deactivation Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 150
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 60
- 239000011259 mixed solution Substances 0.000 description 45
- 238000000605 extraction Methods 0.000 description 30
- 239000012074 organic phase Substances 0.000 description 30
- 229910000027 potassium carbonate Inorganic materials 0.000 description 30
- 239000002904 solvent Substances 0.000 description 30
- 238000011084 recovery Methods 0.000 description 26
- 238000005119 centrifugation Methods 0.000 description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 14
- 229910017604 nitric acid Inorganic materials 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000005893 bromination reaction Methods 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 230000031709 bromination Effects 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 2
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- UVWBADCELNOZAX-UHFFFAOYSA-M [Br+].[OH-] Chemical compound [Br+].[OH-] UVWBADCELNOZAX-UHFFFAOYSA-M 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000002220 antihypertensive agent Substances 0.000 description 1
- 229940127088 antihypertensive drug Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种铌催化甲苯制备对溴甲苯的方法。应用负载氧化铌催化剂，在反应器中加入甲苯，氢溴酸，双氧水，在一定的反应温度下反应得到产物对溴甲苯。该工艺操作简单，溴原子利用率高，污染小。使用的铌催化剂制作方法简单，在强酸中稳定，可多次回收不失活，产物选择性高，催化效果好，具有良好的工业应用前景。The present invention relates to a method for preparing para-bromotoluene by using toluene catalyzed by niobium. A supported niobium oxide catalyst is used, toluene, hydrobromic acid and hydrogen peroxide are added into a reactor, and the product para-bromotoluene is obtained by reaction at a certain reaction temperature. The process is simple to operate, has a high utilization rate of bromine atoms and little pollution. The niobium catalyst used has a simple preparation method, is stable in strong acid, can be recycled multiple times without deactivation, has high product selectivity, good catalytic effect, and has good industrial application prospects.
Description
Technical Field
The invention relates to a method for preparing p-bromotoluene, in particular to a method for oxidizing and brominating p-bromotoluene by using niobium to catalyze toluene.
Background
The niobic acid and the niobium oxide can be used as active components, auxiliary agents or carriers of the catalyst, and have better effects in various reactions, and particularly have excellent stability in the reactions with the participation or the generation of water molecules. For example Xue Jiao et al disclose a preparation and photocatalytic performance [ J ] "(university chemical report, 2018,39 (2): 319-326) of a novel Zn 2+ doped C/Nb 2O5 nano catalyst, wherein a Zn doped C/Nb 2O5 nano catalyst is prepared by adopting a hydrothermal technology, firstly, niobium chloride is dissolved in a mixed solution of ethanol and acetic acid, then zinc acetate is added, after the solution is clear and transparent, the solution is transferred into a polytetrafluoroethylene reaction kettle, then high-temperature crystallization is carried out for 48h, and air calcination is carried out for 2h after drying, thus obtaining the Zn doped Nb 2O5/C material. The preparation of the catalyst has the defect that the preparation is finished by a high-temperature hydrothermal method, and the preparation process is complex. Yuanzhi Hong et al in "Efficient and stable Nb2O5 modified g-C3N4 photocatalyst for removal of antibiotic pollutant[J]"
(Chemical EngineeringJournal,2016,29974-84) A one-step process was used herein to synthesize Nb 2O5/g-C3N4 photocatalysts. Melamine and Nb 2O5 were placed in an agate mortar and ground thoroughly together for 5 minutes. Thereafter, the milled powder was transferred to an alumina crucible and then calcined at 550 ℃ for 4 hours under an air atmosphere. The preparation defects of the catalyst are that the specific surface area of the catalyst is small, the light absorption range is narrow, the yield of melamine after high-temperature calcination is low, and the catalyst is not suitable for mass production and preparation.
The organic bromide is an important intermediate for synthesizing fine chemicals such as medicines, pesticides, dyes and the like, and the high-purity p-bromotoluene is an important intermediate for a mass-market drug-antihypertensive drug Losantan. However, conventional brominating reagents such as bromine and N-bromosuccinimide (NBS) generate hydrogen bromide due to bromination reaction, so that not only are their atom economy low and reaction selectivity poor, but also environmental pollution is caused.
Guo Jianguo et al in patent CN105669364 describe a green bromination process in which p-bromotoluene is prepared with high selectivity using hydrobromic acid, sodium hypochlorite as bromine source and ferric chloride as catalyst. However, the use of metal catalysts makes the cost high and the post-treatment recovery cumbersome.
The method takes toluene as raw material, hydrogen peroxide as oxidant, hydrobromic acid as brominating reagent, and room temperature reaction under illumination of 60W incandescent lamp in toluene oxidizing bromination reaction research [ J ] "(Zhejiang university of Industrial university, 2011,39 (4): 369-371, 398), researches that the oxidizing bromination of toluene has the yield of benzyl bromide of 69.9% and the oxidation product benzaldehyde of 1.3%, and the method has the characteristics of high bromine atom utilization rate, small pollution and the like. The method uses photocatalysis and has lower product yield.
According to the previous method of the same subject group, huang Jun, xu Dandan et al in the invention patent CN114751809a provide a method for preparing bromoanisole by oxidation bromination, oxidizing hydrobromic acid under the action of catalyst and hydrogen peroxide, and brominating anisole to obtain p-bromoanisole. The phosphotungstic acid catalyst can be reused, and has good industrial application prospect. However, phosphotungstic acid is unstable in strong acid and is easily decomposed. And the catalyst preparation cost is high.
Ali Pourjavadi et al at "Gold-Decorated 3D 2,6-Diaminopyridine Network:ARobust Catalyst for the Bromination of Aromatic Compounds[J]"(INDUSTRIAL&ENGINEERING CHEMISTRY RESEARCH,2018,57(37):12314-12322) report the synthesis of magnetic heterogeneous catalysts by modification of gold ions onto crosslinked polymer nanocomposites prepared from 2, 6-diaminopyridine. Then bromination of aromatic compound is carried out, N-bromosuccinimide is used as bromine source, reaction is carried out for 7 hours, and the yield of p-bromotoluene can reach 87%. The catalyst has the advantages of high yield, high gold loading, good stability, easy recycling and the like. However, the bromination reaction produces excessive hydrogen bromide which pollutes the environment.
M. Ghiaci et al in "Regioselective bromination of organic substrates by LDH-CO3 2--Br-promoted by V2O5-H2O2[J]"(APPLIED CATALYSIS A-GENERAL,2010,384(1-2):18-26) designed a novel heterogeneous catalytic system to generate LDH-CO 3 2–-Br3 - in situ for para-selective bromination of aromatic compounds. Magnesium-aluminum layered double hydroxide-CO 3 2--Br(LDH-CO3 2- -Br) is used as a bromide source, V 2O5 is used as an accelerator, and hydrogen peroxide is used as an oxidant to prepare the catalytic system. The phase transfer catalyst reacts for 3 hours at room temperature, and the yield of toluene to bromotoluene can reach 90 percent. And the loss of the catalytic effect is not obvious after four times of recovery. In the method, the preparation method of the layered double hydroxide bromine source is complex, and the in-situ generation takes a long time.
Disclosure of Invention
The invention aims to solve the problems that a phosphotungstic acid and phosphorus vanadium loaded carbon nitrogen material catalyst prepared by the prior art (including the prior art of a subject group) is unstable in strong acid and the preparation cost is high, and discloses a process method for oxidizing and brominating p-bromotoluene by using niobium catalyzed toluene. The method is applied to the preparation process of the p-bromotoluene, has the characteristics of simple reaction operation, high product yield, high bromine atom utilization rate, environmental protection, little pollution and the like.
The technical scheme includes that a) a niobium oxide loaded carbon-nitrogen material catalyst is prepared by loading and calcining niobium oxalate and a nitrogen source solution, wherein niobium pentoxide accounts for 16% -25% of the total mass of the catalyst, b) the preparation of the p-bromotoluene is carried out by adding toluene, hydrobromic acid, hydrogen peroxide and the niobium oxide loaded carbon-nitrogen material catalyst prepared in the step a) into a reactor, and reacting at a certain temperature to obtain the p-bromotoluene.
The niobium oxide loaded carbon-nitrogen material catalyst in the preferred step a) is prepared by adding a nitrogen source into deionized water, heating until the nitrogen source is dissolved, then adding active carbon into the solution to prepare a solution A, adding niobium oxalate into an aqueous solution, then adding nitric acid to adjust pH=2-3, heating and dissolving the solution A to prepare a solution B, adding the solution B into the solution A under stirring, stirring for 4-5h, drying and calcining at a high temperature to prepare the niobium oxide loaded carbon-nitrogen material catalyst, wherein niobium pentoxide accounts for 16% -25% of the total mass of the catalyst.
Preferably, the mass ratio of the nitrogen source to the activated carbon is (0.168-0.5) 1, and the molar ratio of the niobium oxalate to the nitrogen source reagent is (0.9-2.5).
Preferably, the high-temperature calcination temperature is 500-700 ℃ and the calcination time is 1-2 h.
Preferably, the nitrogen source in step a) is dicyandiamide, adenine or diaminomaleonitrile.
Preferably, the adding amount of hydrobromic acid in the step b) is 0.8-1.2 times of the molar amount of toluene, the adding amount of hydrogen peroxide is 0.9-1.2 times of the molar amount of toluene, and the adding mass of the niobium oxide loaded carbon nitrogen material catalyst is 8.6% -12% of the mass of toluene.
Preferably, the reaction temperature in step b) is 20-30℃and the reaction time is 3-5 hours.
The niobium oxide loaded carbon nitrogen material catalyst prepared by the invention can also be applied to bromination of benzene and naphthalene, and the method comprises the following steps:
(1) Adding a certain amount of substrate benzene into a reactor, sequentially adding hydrobromic acid and hydrogen peroxide, adding the niobium catalyst, and reacting for 5 hours at 50-60 ℃ to obtain the corresponding bromobenzene oxidation and bromination product, wherein the yield is 67-84%.
(2) Adding a certain amount of substrate naphthalene into a reactor, sequentially adding hydrobromic acid and hydrogen peroxide, adding the niobium catalyst, and reacting for 5 hours at 40 ℃ to obtain a corresponding oxidation bromination product 1-bromonaphthalene with the yield of 92%.
The beneficial effects are that:
the invention provides a process for preparing p-bromotoluene by oxidizing and brominating toluene, which has the characteristics of simple reaction operation, high product yield, high bromine atom utilization rate, environmental protection, small pollution and the like. The niobium oxide catalyst is a heterogeneous catalyst, and the preparation method is simple, has high specific surface area, is stable in strong acid, is easy to recycle and recycle, and is easy to produce in large scale.
Detailed Description
Example 1 preparation of niobium oxide catalyst with dicyandiamide as nitrogen source.
33.6G (0.4 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃, 100g of active carbon is added to obtain a mixed solution A, 134g (0.25 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to enable PH to be=2, heating is carried out until the solution is completely dissolved at 60 ℃, a yellowish green transparent solution B is obtained, the solution B is completely dripped into the mixed solution A, stirring is continued for 5 hours, drying is carried out in a vacuum oven, the solution B is put into a muffle furnace for calcination for 2 hours at 600 ℃, 150.7g of niobium oxide catalyst is obtained, and niobium pentoxide accounts for 22% of the total mass of the catalyst.
Examples 2 to 4:
92g (1 mol) of toluene and 162g (0.8 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by 113g (1 mol) of hydrogen peroxide, and 10g of the catalyst prepared in example 1 were reacted at room temperature and 25℃with stirring for 3 hours; 4 hours; 5 hours, unreacted acid was removed by anhydrous potassium carbonate after the reaction was completed, ethyl acetate was added for extraction, and the organic phases were combined, and the solvent was distilled off under reduced pressure to give 115g (0.672 mol) of p-bromotoluene, 84% of 126g (0.736 mol), 92% of 128.6g (0.752 mol) of p-bromotoluene, and 94% of the yield.
Examples 5 to 7:
92g (1 mol) of toluene and 162g (0.8 mol) of hydrobromic acid were added respectively to a 5L round-bottomed flask, followed by 100g (0.9 mol), 124g (1.1 mol), 136g (1.2 mol) of hydrogen peroxide, and 10g of the catalyst prepared in example 1 were stirred at room temperature for 5 hours, unreacted acid was removed by anhydrous potassium carbonate after the completion of the reaction, ethyl acetate was added for extraction, the organic phases were combined, and the solvents were distilled off under reduced pressure to obtain 119g (0.696 mol), yield 87%, 131g (0.768 mol), yield 96%, 131g (0.768 mol) and yield 96% of p-bromotoluene, respectively. And washing the centrifuged catalyst with ethyl acetate for multiple times, and drying for later use.
Embodiment case 8:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 6, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 131g (0.768 mol) of p-bromotoluene in 96% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Embodiment case 9:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 8, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 131g (0.768 mol) of p-bromotoluene in 96% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Embodiment case 10:
92g (1 mol) of toluene and 162g (0.8 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the dried catalyst of example 9, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 128.6g (0.752 mol) of p-bromotoluene in 94% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Embodiment case 11:
92g (1 mol) of toluene and 162g (0.8 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the dried catalyst of example 10, followed by stirring at room temperature and 25℃for reaction for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 128.6g (0.752 mol) of p-bromotoluene in 94% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Embodiment case 12:
92g (1 mol) of toluene and 162g (0.8 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the dried catalyst of example 11, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 128.6g (0.752 mol) of p-bromotoluene in 94% yield.
Examples 13 to 15:
92g (1 mol) of toluene and 162g (0.8 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, 8g;9g;11g of the catalyst prepared in example 1 were added, respectively, stirred at room temperature and 25 ℃ for reaction for 5 hours, unreacted acid was removed by anhydrous potassium carbonate after the reaction was completed, ethyl acetate was added for extraction, and the organic phases were combined, and the solvent was distilled off under reduced pressure to give 123g (0.72 mol) of p-bromotoluene, 90% yield, 126g (0.736 mol), 92% yield, 131g (0.768 mol) and 96% yield, respectively.
Examples 16 to 18:
92g (1 mol) of toluene and 162g (0.8 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the catalyst prepared in example 1 were reacted at 20 ℃;23 ℃;30 ℃ with stirring for 5 hours at 20 ℃ respectively, unreacted acid was removed by anhydrous potassium carbonate after the completion of the reaction, ethyl acetate was added for extraction, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 113g (0.664 mol) of p-bromotoluene, 83% in yield, 120g (0.704 mol), 88% in yield, 131g (0.768 mol) in yield, 96% in yield, respectively.
Example 19 preparation of niobium oxide catalyst with dicyandiamide as nitrogen source.
50G (0.6 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃, 100g of active carbon is added to obtain a mixed solution A, 140g (0.26 mol) of niobium oxalate is added to 400ml of water, nitric acid is added dropwise to enable PH to be=2, heating is carried out until the solution is completely dissolved at 60 ℃, a yellowish green transparent solution B is obtained, the solution B is completely dripped into the mixed solution A, stirring is continued for 5 hours, drying is carried out in a vacuum oven, the solution is put into a muffle furnace at 600 ℃ and calcined for 2 hours, 156g of niobium oxide catalyst is obtained, and niobium pentoxide accounts for 22% of the total mass of the catalyst.
Embodiment case 20:
92g (1 mol) of toluene and 162g (0.8 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the catalyst prepared in example 19, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 131g (0.768 mol) of p-bromotoluene in 96% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Embodiment case 21:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 20, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 131g (0.768 mol) of p-bromotoluene in 96% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Embodiment case 22:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 21, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 131g (0.768 mol) of p-bromotoluene in 96% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Embodiment case 23:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 22, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 131g (0.768 mol) of p-bromotoluene in 96% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Embodiment case 24:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 23, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 128g (0.748 mol) p-bromotoluene in 93.5% yield. The centrifuged catalyst was washed with 5ml of ethyl acetate several times and dried for use.
Embodiment case 25:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 24, followed by stirring at room temperature of 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 128g (0.748 mol) p-bromotoluene in 93.5% yield.
Example 26 preparation of niobium oxide catalyst with dicyandiamide as the nitrogen source.
16.8G (0.2 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃, 100g of active carbon is added to obtain a mixed solution A, 115g (0.214 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to enable PH to be=2, heating is carried out until the solution is completely dissolved at 60 ℃, a yellowish green transparent solution B is obtained, the solution B is completely dripped into the mixed solution A, stirring is continued for 5 hours, drying is carried out in a vacuum oven, the solution B is put into a muffle furnace for 600 ℃ and calcining for 2 hours, 130g of niobium oxide catalyst is obtained, and niobium pentoxide accounts for 22% of the total mass of the catalyst.
Embodiment case 27:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 26, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to give 117.6g (0.688 mol) p-bromotoluene in 86% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Example 28 preparation of niobium oxide catalyst with dicyandiamide as nitrogen source.
33.6G (0.4 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃,100 g of active carbon is added to obtain a mixed solution A, 90g (0.167 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to ensure PH=2, the mixed solution A is heated to 60 ℃ and stirred until the mixed solution is completely dissolved to obtain a yellowish green transparent solution B, the solution B is completely dripped into the mixed solution A, the mixed solution A is continuously stirred for 5 hours, the mixed solution is dried in a vacuum oven, and calcined for 2 hours at 600 ℃ in a muffle furnace to obtain 138g of niobium oxide catalyst, and niobium pentoxide accounts for 16% of the total mass of the catalyst.
Implementation case 29:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 28, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to give 113g (0.664 mol) p-bromotoluene in 83% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Example 30 preparation of niobium oxide catalyst with dicyandiamide as nitrogen source.
33.6G (0.4 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃, 100g of active carbon is added to obtain a mixed solution A, 107.6g (0.2 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to ensure that PH=2, the mixed solution A is heated to 60 ℃ and stirred until the mixed solution is completely dissolved, a yellowish green transparent solution B is obtained, the solution B is completely dripped into the mixed solution A, the mixed solution A is continuously stirred for 5 hours, the mixed solution A is dried in a vacuum oven, and calcined for 2 hours at 600 ℃ in a muffle furnace, thus obtaining 140g of niobium oxide catalyst, and niobium pentoxide accounts for 19% of the total mass of the catalyst.
Embodiment case 31:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 30, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to give 123g (0.72 mol) p-bromotoluene in a yield of 90%. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Example 32 preparation of niobium oxide catalyst with dicyandiamide as nitrogen source.
33.6G (0.4 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃, 100g of active carbon is added to obtain a mixed solution A, 161.4g (0.3 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to ensure that PH=2, the mixed solution A is heated to 60 ℃ and stirred until the mixed solution is completely dissolved, a yellowish green transparent solution B is obtained, the solution B is completely dripped into the mixed solution A, the mixed solution A is continuously stirred for 5 hours, the mixed solution A is dried in a vacuum oven, and calcined for 2 hours at 600 ℃ in a muffle furnace, 160g of niobium oxide catalyst is obtained, and niobium pentoxide accounts for 25% of the total mass of the catalyst.
Implementation case 33:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 32, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 131g (0.768 mol) of p-bromotoluene in 96% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Example 34 preparation of niobium oxide catalyst with dicyandiamide as nitrogen source.
33.6G (0.4 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃, 100g of active carbon is added to obtain a mixed solution A, 134g (0.25 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to enable PH to be=2, heating is carried out until the solution is completely dissolved at 60 ℃, a yellowish green transparent solution B is obtained, the solution B is completely dripped into the mixed solution A, stirring is continued for 5 hours, drying is carried out in a vacuum oven, the solution B is put into a muffle furnace for calcination for 2 hours at 500 ℃, 150.7g of niobium oxide catalyst is obtained, and niobium pentoxide accounts for 22% of the total mass of the catalyst.
Embodiment case 35:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round bottom flask, followed by 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 34, and the mixture was stirred at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, ethyl acetate was added for extraction, the organic phases were combined, and the solvent was distilled off under reduced pressure to give 124g (0.725 mol) p-bromotoluene in a yield of 90.6%. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Example 36 preparation of niobium oxide catalyst with dicyandiamide as nitrogen source.
33.6G (0.4 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃, 100g of active carbon is added to obtain a mixed solution A, 134g (0.25 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to enable PH to be=2, heating is carried out until the solution is completely dissolved at 60 ℃, a yellowish green transparent solution B is obtained, the solution B is completely dripped into the mixed solution A, stirring is continued for 5 hours, drying is carried out in a vacuum oven, the solution B is put into a muffle furnace for calcination for 1 hour at 700 ℃, 150.7g of niobium oxide catalyst is obtained, and niobium pentoxide accounts for 22% of the total mass of the catalyst.
Implementation case 37:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 36, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 131g (0.768 mol) of p-bromotoluene in 96% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Example 38 preparation of niobium oxide catalyst with dicyandiamide as nitrogen source.
33.6G (0.4 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃, 100g of active carbon is added to obtain a mixed solution A, 134g (0.25 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to enable PH to be=2, heating is carried out until the solution is completely dissolved at 60 ℃, a yellowish green transparent solution B is obtained, the solution B is completely dripped into the mixed solution A, stirring is continued for 5 hours, drying is carried out in a vacuum oven, the solution B is put into a muffle furnace for calcination for 1 hour at 600 ℃, 150.7g of niobium oxide catalyst is obtained, and niobium pentoxide accounts for 22% of the total mass of the catalyst.
Implementation case 39:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 38, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to give 116g (0.68 mol) p-bromotoluene in 85% yield. The catalyst after centrifugation is washed with acetic acid for a plurality of times and dried for standby.
Example 40 preparation of niobium oxide catalyst with adenine as nitrogen source.
33.8G (0.25 mmol) of adenine is dissolved in 200ml of DMF, heated to 60 ℃,100 g of activated carbon is added to obtain a mixed solution A, 134g (0.25 mol) of niobium oxalate is added into 400ml of water, nitric acid is dropwise added to enable PH to be=2, heating is carried out until the mixed solution is completely dissolved, a yellowish green transparent solution B is obtained, all the solution B is dropwise added into the mixed solution A, then the mixed solution is transferred into a 1L polytetrafluoroethylene-lined hydrothermal kettle to be stirred for 5 hours at 150 ℃, the reaction solution is steamed in a rotary mode, a muffle furnace is put at 600 ℃ to be calcined for 2 hours, 150.7g of niobium oxide catalyst is obtained, and niobium pentoxide accounts for 22% of the total mass of the catalyst.
Implementation case 41:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 40, followed by stirring at room temperature of 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 131g (0.768 mol) of p-bromotoluene in 96% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Example 42 preparation of niobium oxide catalyst with diaminomaleonitrile as nitrogen source.
32.4G (0.33 mol) of diaminomaleonitrile is dissolved in 300ml of ethanol, heated to 60 ℃, 100g of activated carbon is added to obtain a mixed solution A, 134g (0.25 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to ensure PH=2, heating is carried out to 60 ℃ and stirring is carried out until the solution is completely dissolved, a yellowish green transparent solution B is obtained, the solution B is completely dripped into the mixed solution A, stirring is continued for 5 hours, drying is carried out in a vacuum oven, and calcination is carried out for 2 hours at 600 ℃ in a muffle furnace, thus obtaining 1.5g of niobium oxide catalyst, and niobium pentoxide accounts for 22% of the total mass of the catalyst. Implementation case 43:
92g (1 mol) toluene and 162g (0.8 mol) hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) hydrogen peroxide, and 10g of the dried catalyst of example 42, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 127g (0.744 mol) p-bromotoluene in 93% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Example 44 preparation of niobium oxide catalyst with dicyandiamide as nitrogen source.
33.6G (0.4 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃, 100g of active carbon is added to obtain a mixed solution A, 134g (0.25 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to enable PH to be=2, heating is carried out until the solution is completely dissolved at 60 ℃, a yellowish green transparent solution B is obtained, the solution B is completely dripped into the mixed solution A, stirring is continued for 4 hours, drying is carried out in a vacuum oven, the solution B is put into a muffle furnace for calcination for 2 hours at 600 ℃, 150.7g of niobium oxide catalyst is obtained, and niobium pentoxide accounts for 22% of the total mass of the catalyst.
Implementation case 45:
92g (1 mol) of toluene and 162g (0.8 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the dried catalyst of example 44, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 127g (0.744 mol) of p-bromotoluene in 93% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Example 46 preparation of niobium oxide catalyst with dicyandiamide as the nitrogen source.
33.6G (0.4 mol) of dicyandiamide is dissolved in 200ml of water, heated to 60 ℃, 100g of active carbon is added to obtain a mixed solution A, 134g (0.25 mol) of niobium oxalate is added into 400ml of water, nitric acid is added dropwise to ensure that PH=3, the mixed solution A is heated to 60 ℃ and stirred until the mixed solution is completely dissolved to obtain a yellowish green transparent solution B, the solution B is completely dripped into the mixed solution A, the mixed solution A is continuously stirred for 5 hours, the mixed solution A is dried in a vacuum oven, and calcined for 2 hours at 600 ℃ in a muffle furnace to obtain 150.7g of niobium oxide catalyst, and niobium pentoxide accounts for 22% of the total mass of the catalyst.
Embodiment case 47:
92g (1 mol) of toluene and 162g (0.8 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the catalyst prepared in example 46, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 131g (0.768 mol) of p-bromotoluene in 96% yield. The catalyst after centrifugation is washed with ethyl acetate for a plurality of times and dried for standby.
Implementation case 48:
92g (1 mol) of toluene and 182g (0.9 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the catalyst prepared in example 1, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 148g (0.864 mol) of p-bromotoluene in 96% yield.
Embodiment case 49:
92g (1 mol) of toluene and 202g (1 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the catalyst prepared in example 1, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to obtain 164g (0.96 mol) of p-bromotoluene in 96% yield.
Embodiment case 50:
92g (1 mol) of toluene and 223g (1.1 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the catalyst prepared in example 1, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to give 166g (0.97 mol) of p-bromotoluene in 97% yield.
Implementation case 51:
92g (1 mol) of toluene and 243g (1.2 mol) of hydrobromic acid were added to a 5L round-bottomed flask, followed by addition of 124g (1.1 mol) of hydrogen peroxide, and 10g of the catalyst prepared in example 1, followed by stirring at room temperature and 25℃for 5 hours, after the completion of the reaction, unreacted acid was removed by anhydrous potassium carbonate, extraction was performed by adding ethyl acetate, the organic phases were combined, and the solvent was distilled off under reduced pressure to give 166g (0.97 mol) of p-bromotoluene in 97% yield.
Table 1:
the catalyst after washing and drying after the reaction in example 6 was reused. The process flow is consistent with example 6, and the catalyst recovery and use conditions are shown in the following table:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 96% |
| 2 | 96% |
| 3 | 94% |
| 4 | 94% |
| 5 | 94% |
| 6 | 94% |
| 7 | 94% |
| 8 | 94% |
| 9 | 93% |
| 10 | 94% |
The catalyst after washing and drying after the reaction in example 20 was reused. The process flow is consistent with the 20 cases of the implementation scheme, and the catalyst recovery and use conditions are shown in the following table:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 96% |
| 2 | 96% |
| 3 | 96% |
| 4 | 93.5% |
| 5 | 93.5% |
| 6 | 93.5% |
| 7 | 93.5% |
| 8 | 93% |
| 9 | 94% |
| 10 | 93% |
The catalyst after washing and drying after the reaction in example 27 was reused. The process flow is consistent with the embodiment 27, and the catalyst recovery and use conditions are shown in the following table:
the catalyst after washing and drying after the reaction in example 29 was reused. The process flow is consistent with the 29 cases of the implementation scheme, and the catalyst recovery and use conditions are shown in the following table:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 83% |
| 2 | 83% |
| 3 | 83% |
| 4 | 82% |
| 5 | 82% |
| 6 | 82% |
| 7 | 82% |
| 8 | 82% |
The catalyst after washing and drying after the reaction in example 31 was reused. The process flow is consistent with the 31 cases of the embodiment, and the catalyst recovery and use conditions are shown in the following table:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 90% |
| 2 | 90% |
| 3 | 88% |
| 4 | 88% |
| 5 | 88% |
| 6 | 88% |
| 7 | 89% |
| 8 | 88% |
The catalyst after washing and drying after the reaction in example 33 was reused. The process flow is consistent with embodiment 33, and the catalyst recovery and use conditions are shown in the following table:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 96% |
| 2 | 96% |
| 3 | 96% |
| 4 | 94% |
| 5 | 94% |
| 6 | 93% |
| 7 | 93% |
| 8 | 94% |
The catalyst after washing and drying after the reaction in example 35 was reused. The process flow is consistent with embodiment 35, and the catalyst recovery and use conditions are shown in the following table:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 90.6% |
| 2 | 90% |
| 3 | 90% |
| 4 | 88% |
| 5 | 88% |
| 6 | 88% |
| 7 | 87% |
| 8 | 88% |
The catalyst after washing and drying after the reaction in example 37 was reused. The process flow is consistent with embodiment 37, and the catalyst recovery and use conditions are shown in the following table:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 96% |
| 2 | 96% |
| 3 | 96% |
| 4 | 94% |
| 5 | 94% |
| 6 | 94% |
| 7 | 94% |
| 8 | 94% |
The catalyst after washing and drying after the reaction in example 39 was reused. The process flow is consistent with example 39, and the catalyst recovery and use conditions are shown in the following table:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 85% |
| 2 | 85% |
| 3 | 83% |
| 4 | 83% |
| 5 | 83% |
| 6 | 84% |
| 7 | 84% |
| 8 | 83% |
The catalyst after washing and drying after the reaction in example 41 was reused. The process flow is consistent with embodiment 41, and the catalyst recovery and use conditions are as follows:
The catalyst after washing and drying after the reaction in example 43 was reused. The process flow is consistent with example 43 and the catalyst recovery is as follows:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 93% |
| 2 | 94% |
| 3 | 94% |
| 4 | 93% |
| 5 | 93% |
| 6 | 93% |
| 7 | 93% |
| 8 | 93% |
The catalyst after washing and drying after the reaction in example 45 was reused. The process flow is consistent with embodiment 45, and the catalyst recovery and use conditions are shown in the following table:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 93% |
| 2 | 93% |
| 3 | 93% |
| 4 | 91% |
| 5 | 92% |
| 6 | 92% |
| 7 | 92.5% |
| 8 | 91% |
The catalyst after washing and drying after the reaction in example 47 was reused. The process flow is consistent with embodiment 47 and catalyst recovery is as follows:
| Number of times of recovery | Para-bromotoluene yield |
| 1 | 96% |
| 2 | 96% |
| 3 | 94% |
| 4 | 94% |
| 5 | 94% |
| 6 | 94% |
| 7 | 94% |
| 8 | 94% |
Claims (5)
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Citations (2)
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|---|---|---|---|---|
| CN103623867A (en) * | 2013-11-18 | 2014-03-12 | 东南大学 | Composite catalyst for selective chlorination of aromatic compounds and application thereof |
| CN110719812A (en) * | 2017-06-06 | 2020-01-21 | 阿科玛法国公司 | Process for changing the fluorine distribution in hydrocarbon compounds |
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| NL132331C (en) * | 1962-06-01 | 1971-04-15 | ||
| EP0829461A1 (en) * | 1996-09-09 | 1998-03-18 | Occidental Chemical Corporation | Selective production of 1,4-dichloro-benzene and 1,2,4-trichlorobenzene |
| JP2005126387A (en) * | 2003-10-27 | 2005-05-19 | Japan Science & Technology Agency | A method for producing an oxidation reaction product, a method for producing an organic compound, an oxidation method, and a method for producing an organic compound. |
| US7863209B2 (en) * | 2004-06-16 | 2011-01-04 | Sabic Innovative Plastics Ip B.V. | Methods for recycling catalyst compositions for aromatic ring halogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103623867A (en) * | 2013-11-18 | 2014-03-12 | 东南大学 | Composite catalyst for selective chlorination of aromatic compounds and application thereof |
| CN110719812A (en) * | 2017-06-06 | 2020-01-21 | 阿科玛法国公司 | Process for changing the fluorine distribution in hydrocarbon compounds |
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