CN114560771A - Method for selective nitration of bromophenol by photocatalysis - Google Patents

Method for selective nitration of bromophenol by photocatalysis Download PDF

Info

Publication number
CN114560771A
CN114560771A CN202210218046.5A CN202210218046A CN114560771A CN 114560771 A CN114560771 A CN 114560771A CN 202210218046 A CN202210218046 A CN 202210218046A CN 114560771 A CN114560771 A CN 114560771A
Authority
CN
China
Prior art keywords
guanidine
silver
nitration
dibromophenol
nitrite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210218046.5A
Other languages
Chinese (zh)
Other versions
CN114560771B (en
Inventor
梁栋
张晓雨
李彦乐
任梦宇
张小悦
李永祥
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
North University of China
Original Assignee
North University of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North University of China filed Critical North University of China
Priority to CN202210218046.5A priority Critical patent/CN114560771B/en
Publication of CN114560771A publication Critical patent/CN114560771A/en
Application granted granted Critical
Publication of CN114560771B publication Critical patent/CN114560771B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/18—Silver
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for selectively nitrifying bromophenol by photocatalysis, and relates to the fields of photocatalytic organic synthesis and fine chemical engineering. Specifically, visible light is used as an energy source, nitrite is used as a nitration reagent, silver-doped guanidino modified carbon nitride is used as a catalyst, and dibromophenol is selectively nitrated in a solvent of acetonitrile and water to prepare a phenol intermediate with both bromo-functional groups and nitro-functional groups. Compared with the traditional nitration process, the invention does not adopt strong acid systems such as nitric acid, sulfuric acid, acetic acid, fluorosulfonic acid and the like, has small environmental responsibility of the production process, does not need heating and is only carried out at normal temperature, can directly utilize common visible light resources in the nature, takes nitrite which is cheap and easy to obtain as a nitration reagent, has mild conditions and high selectivity, and meets the requirements of modern green chemistry.

Description

Method for selective nitration of bromophenol by photocatalysis
Technical Field
The invention belongs to the technical field of photocatalytic organic synthesis and fine chemical engineering, and particularly relates to a method for selectively nitrifying bromophenol by photocatalysis.
Background
The bromophenol intermediate with nitro functional group is converted into several end products with pharmacological activity through etherification, coupling, reduction and other reactions. For example, para-nitrated 2-bromo-4 nitrophenol can be prepared into an insecticide containing fluoroalkyl connected by an ether bond, a diabetic peptidase inhibitor connected with nitrogen heterocycle, a debrominated alkynyl-introduced cytotoxic inhibitor and the like, ortho-nitrated 2-bromo-6 nitrophenol is subjected to reduction, coupling and other reactions to obtain 3-amino-2-hydroxybiphenyl-3-carboxylic acid, which belongs to a key intermediate of a thrombopoietin receptor agonist-eltrombopag, and meta-nitrated 3-bromo-5 nitrophenol is connected with benzyl by an ether bond to obtain 3-bromo-5-nitrophenylbenzyl ether, and the 3-bromo-5-nitrophenylbenzyl ether can be used for synthesizing an anticancer lead compound autolytic mycin.
The nitro functional group is introduced into the bromophenol by the nitration method of other halogenated phenols, and the nitration process of nitric acid is generally adopted. The earliest Nitration of 3-bromophenol with fuming sulfuric acid and sodium nitrate by Herbert Henry Hodgson and Francis Harry Moor in 1926 gave 3-bromo-4-nitrophenol and 3-bromo-6-nitrophenol (Herbert Henry Hodgson and Francis Harry Moor The Nitration of m-Bromophenol. Journal of The Chemical Society, 1926,129, 155-; robin G. Clewley et al nitrify p-bromophenol with nitric acid and trifluoroacetic anhydride and react in chloroform at-40 ℃ to give 4-bromo-2-nitrophenol in only 25% yield (Robin G. Clewley, Gordon G. Cross, Alfred Fischer, George N. Henderson. Format of 4-Halo-4-nitrocyclohexa-2, 5-dienes on mutation of p-halophenols and p-halophenyl acetates [ J ] Tetrahedron, 1989, 45(5): 1299-1310); and the like, namely Zhang ploughing, mixing nitric acid and acetic acid for nitration, and converting p-bromophenol into 4-bromo-2-nitrophenol in an ice-water bath, wherein the yield is improved to 93% (Zhang ploughing, synthetic research on thiophenones and benzoxazine compounds [ D ]. Hunan Tan university 2014). The nitric acid nitration process has short flow and simple principle, but generally adopts strong-corrosion or strong-oxidizing acid, so that certain equipment loss is easily caused during use, and the problem of serious environmental pollution is also caused.
In addition to nitric acid, nitrate is also a commonly used source of nitro groups. For example, sensitize and the like, using ferric nitrate mixed with 65% nitric acid as a nitrating agent, P-bromophenol is converted into 2-nitro-4-bromophenol by reacting in tetrahydrofuran at normal temperature for 10h, the yield is 66%, and byproducts such as 2, 4-dibromo-6-nitrophenol, 2-bromo-4-nitrophenol and the like (sensitize, yiwanpo, nitration method using metal salt to catalyze phenols and phenyl ether compounds [ P ], CN 1709856 a, 2005) are also included; hussni A. Muathen also uses bismuth nitrate and thionyl Chloride as nitrating agents to convert o-bromophenol to 52% 2-bromo-4 nitrophenol and 22% 2-bromo-6 nitrophenol (Hussni A. Muathen. Selective nitration of aromatic compounds with bis subnitrate and thio Chloride [ J ], Molecules, 2003, 8, 593-; v, Anurada and the like preferably nickel nitrate as a nitrating agent, p-Toluenesulfonic acid as a catalyst, and p-bromophenol is reacted in acetone at normal temperature for 1h to obtain 4-bromo-2-nitrophenol with a yield of 78% (V, Anurada, P, V, Srinivas, P, Aparna and J, Madhusudanaraao, p-lutenesulfonic acid catalyzed regiospecific catalysis nitration of olefins with metallic nitrates [ J ]. Tetrahedron Letters, 2006, 47(28): 4933-; K. amani and F.Maleki take heteropoly acid as catalyst, ferric nitrate as nitro source, 2-bromophenol reacts in dichloromethane for 7.5-8.5 h at normal temperature to obtain 60% of 2-bromo-4 nitrophenol and 30% of 2-bromo-6 nitrophenol (K.Amani, F.Maleki. Catalytic effects of sodium key-type phenol and polyoxometalates on selective catalysis of phenols [ J ] phenol of the Iranian Chemical Society, 2007, 4: 238-; the method for nitrating aryl phenol or aryl ether derivative [ P ], CN110590557A, 2019, can convert 46% of P-bromophenol into 4-bromo-2-nitrophenol by nitrating Dunhai and the like with trimethylchlorosilane and the like in acetonitrile solution at normal temperature by using copper sulfate as a catalyst and guanidine nitrate and the like as a nitro source. Essentially, the mechanism of these reactions is still electrophilic substitution reaction which relies on strong acid or strong acid catalyst to obtain nitroxyl positive ion, and the selectivity of the specific position bromo nitrophenol in the reaction process is low.
Using multiple light sources including ultraviolet light and visible light, with the aid of photon energyThe organic synthesis is driven by the amount, and chemical reactions occurring under some harsh conditions can be converted into mild environments for carrying out, but only few researches are carried out on photocatalytic nitration. For example, Rongzhiming, etc. uses o-methylbenzoic acid as raw material, nitrite such as sodium nitrite and potassium nitrite as nitrating reagent, organic solvent of acetonitrile and dichloroethane and water as mixed reagent, and uses Fe supported by photosensitizer of eosin Y and acridine salt, etc3O4The magnetic nanoparticles are used as a photocatalyst, the 3, 5-dinitro-2-methylbenzoic acid is obtained under the catalysis of visible light with the wavelength ranging from 390 nm to 540nm, and the yield of a nitration product under the optimal condition reaches 98 percent (Wangzhiming, Yankee, Wangyi, Chenrener, Mayongming, a preparation method of the 3, 5-dinitro-2-methylbenzoic acid [ P ]]CN113149845A, 2021); zhong et al used cyclohexane as raw material, 300W high-pressure mercury lamp as light source, concentrated nitric acid as nitrating agent, nitration conversion rate of 22% and selectivity of 87% in cyclohexane/nitric acid biphase system (Wenzhou Zhong, Liqiu Mao, Wenjun Yi, Gouqiiangzou, Yongqiang Li, Dulin yin. highlyfin light-drive HNO)3 nitration–oxidation of cyclohexane to co-product nitrocyclohexane and adipic acid in a biphasic system[J]Research on Chemical Intermediates, 2016, 42: 461-. However, no photocatalytic system capable of selectively synthesizing the nitrated bromophenol with specific positioning has been reported up to now.
Disclosure of Invention
The invention provides a method for nitrifying bromophenol by photocatalysis selectively, which overcomes the defects of the existing bromophenol nitration process, does not contain any strong acid or strong acid additive, only needs normal-temperature illumination reaction, and has the advantages of simple operation, mild condition, novel method and high selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for selectively nitrifying bromophenol by photocatalysis uses dibromophenol as raw material, organic solvent and water as mixed solvent, and silver guanidine/g-C3N4The catalyst is nitrite, the nitrites are nitration reagents, catalytic reaction is carried out under visible light, and after the reaction is finished, post-treatment is carried out to obtain the product bromo-nitrophenol.
The method comprises the following specific steps:
(1) preparation of silver guanidine/g-C3N4：2g g-C3N4Mixing with 150 mL of acetonitrile, carrying out ultrasonic treatment for 0.5-2 h at 80-100 KHz, adding 3.4-4.2 mL of cyanamide, and mixing with g-C3N4Reacting terminal amino to generate guanidino, heating and refluxing for 24-48 h, filtering and drying to obtain guanidine/g-C3N4(ii) a Dissolving 0.4-0.9 g of silver nitrate in 50 mL of absolute ethanol to obtain guanidine/g-C3N4Adding into anhydrous ethanol solution of silver nitrate, using chelation of guanidino and metal, heating and refluxing for 8-12 h in dark, filtering and washing off unreacted Ag+Placing the filter cake under a 150-300W xenon lamp for illumination for 0.5-1 h, filtering and drying to obtain silver guanidine/g-C3N4；
(2) Photocatalytic selective nitration of bromophenol: 0.05 to 0.2g of silver guanidine/g-C3N4Stirring a catalyst and 0.2g of dibromophenol in an acetonitrile solvent for 0.5h, starting a 150-300W xenon lamp light source, dropwise adding 16-32 mL of 0.1mol/L nitrite aqueous solution into the solution, controlling the dropwise adding speed to be 6-10 mL/h, continuously stirring at normal temperature for 3-5 h after the dropwise adding is finished, removing the solvent and water by reduced pressure distillation after the reaction is finished, extracting the obtained product by 10 mL of dichloromethane, and analyzing and calculating the yield of the bromonitrophenol by liquid chromatography.
And (3) in the step (2), the dibromophenol is any one of 2, 4-dibromophenol, 2, 6-dibromophenol or 3, 5-dibromophenol.
And (3) in the step (2), the nitrite is sodium nitrite or potassium nitrite.
The liquid chromatogram adopts a standard ODS C-18 chromatographic column, the column temperature is 35 ℃, the mobile phase is acetonitrile/water with the volume ratio of 25/75, the flow rate is 0.35 ml/min, the ultraviolet detection wavelength is 260nm, and the change of raw materials and products is calculated by a conventional area normalization method.
Dibromophenol retains one bromine when nitrated, is not completely replaced, and the nitro group is introduced at a specific position, which can be referred to as selective nitration. In the conventional nitration reaction of the monobromophenol, the position of introduction of the nitro is uncertain, for example, the nitration of 2-bromophenol can simultaneously obtain 2 bromo-4 nitro and 2 bromo-6 nitrophenol. One bromine of the dibromophenol is positioned and replaced by the nitro, the product is single, and the selectivity is good compared with the prior art. The reaction principle of the invention is as follows:
Figure DEST_PATH_IMAGE002
the invention has the beneficial effects that: compared with the traditional nitration process of the bromophenol, the invention does not adopt strong acid systems such as nitric acid, sulfuric acid, acetic acid, fluorosulfonic acid and the like, has small production process environmental responsibility, does not need heating and is only carried out at normal temperature, can directly utilize common visible light resources in the nature, takes nitrite which is cheap and easy to obtain as a nitration reagent, and obtains the bromonitrophenol which has single product and high selectivity and meets the requirements of modern green chemistry.
Drawings
FIG. 1 shows silver guanidine/g-C obtained in example 13N4SEM-EDX spectrum of (1). The spectrogram can clearly see that silver element particles are dispersed on the folded nano-sheets, which indicates that silver is loaded on guanidyl g-C3N4；
FIG. 2 shows Ag-guanidine/g-C obtained in example 13N4With conventional silver/g-C3N4The metal content measured by ICP-OES, and comparison of the two data revealed that g-C was present under the same conditions3N4Specific guanidino g-C for loading content of silver ions3N4Reduced by about 68%, demonstrating guanidino g-C3N4With general g-C3N4Is significantly different;
FIG. 3 is g-C3N4And silver guanidine/g-C obtained in example 13N4The FT-IR spectrum of (A) shows that the absorption peaks of the two substances are approximately the same, wherein the absorption peak is 806cm-1Bending vibration outside the plane of the triazine ring, and the characteristic absorption peak is 1200-1700 cm-1Belongs to C-N heterocyclic ring stretching vibration, and is 3000-3500 cm-1The absorption peak between the two is the stretching vibration of N-H, compared with pure g-C3N4The N-H stretching vibration is obviously enhanced, which is mainly from silver guanidine/g-C3N4N-H of (A), indicates guanidino and g-C3N4Successfully compounding together;
FIG. 4 shows g-C3N4And silver guanidine/g-C obtained in example 13N4UV-Vis spectrum of (1), from which g-C can be seen3N4And silver guanidine/g-C3N4Silver guanidine/g-C with absorption at 200-450 nm3N4Compared with pure g-C3N4Slightly red-shifted, after calculation, silver guanidine/g-C3N4Band gap value (E) ofg) 2.57eV less than pure g-C3N4Band gap value E ofg(2.69 eV), indicating silver guanidine/g-C3N4More photons can be absorbed, and the utilization rate of visible light is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the disclosures and references cited herein and the materials to which they refer are incorporated by reference.
Those skilled in the art will recognize that equivalents to the specific embodiments described, as may be learned by routine experimentation, are intended to be encompassed by the present application.
The experimental procedures in the following examples are conventional unless otherwise specified. The instruments used in the following examples are, unless otherwise specified, laboratory-standard instruments; the experimental materials used in the following examples were purchased from a general biochemical reagent store unless otherwise specified.
Example 1: a method for selectively nitrifying bromophenol by photocatalysis uses dibromophenol as raw material, organic solvent and water as mixed solvent, and silver guanidine/g-C3N4The catalyst is nitrite, the nitrites are nitration reagents, the catalytic reaction is carried out under visible light, and the product of bromonitrophenol is obtained after the post-treatment after the reaction is finished.
The method comprises the following specific steps:
step (1): weighing 2g g-C3N4And 150 mL of acetonitrile, is subjected to ultrasonic treatment for 0.5h by 90KHz, and 4.2mL of cyanamide and g-C are added3N4Reacting terminal amino to generate guanidino, heating and refluxing for 36h, filtering and drying to obtain guanidine/g-C3N4Adding into 0.9g silver nitrate and 50 mL absolute ethyl alcohol, heating and refluxing for 8h in a dark place by using chelation of guanidyl and metal, filtering and washing off unreacted Ag+Placing the filter cake under a 250W xenon lamp for illumination for 0.5h, filtering and drying to obtain silver guanidine/g-C3N4；
Step (2): 0.2g of silver guanidine/g-C3N4Stirring the catalyst and 0.2g of 2, 6-dibromophenol in an acetonitrile solvent for 0.5h, starting a 250W xenon lamp light source, dropwise adding 24mL of 0.1mol/L potassium nitrite aqueous solution into the solution, controlling the dropwise adding speed to be 10 mL/h by using an injection pump, continuously stirring at normal temperature for 4h after the completion of the reaction, removing the solvent and water by reduced pressure distillation after the reaction is finished, extracting the obtained product by using 10 mL of dichloromethane, analyzing by using liquid chromatography and calculating the yield of the 2-bromo-6 nitrophenol to be 88%. The reaction equation is as follows:
Figure RE-631298DEST_PATH_IMAGE002
。
example 2: step (1): weighing 2g g-C3N4And 150 mL of acetonitrile, performing ultrasonic treatment for 2h by 100KHz, and adding 3.8mL of cyanamide and g-C3N4Reacting terminal amino to generate guanidino, heating and refluxing for 48h, filtering and drying to obtain guanidine/g-C3N4Adding into 0.7g silver nitrate and 50 mL absolute ethyl alcohol, heating and refluxing for 12h in a dark place by using chelation of guanidyl and metal, filtering and washing off unreacted Ag+Placing the filter cake under a 300W xenon lamp for illumination for 1h, filtering and drying to obtain silverguanidine/g-C3N4；
Step (2): 0.1g of silver guanidine/g-C3N4Stirring the catalyst and 0.2g of 2, 4-dibromophenol in an acetonitrile solvent for 0.5h, starting a 300W xenon lamp light source, dropwise adding 32mL of 0.1mol/L potassium nitrite aqueous solution into the solution, controlling the dropwise adding speed to be 6 mL/h by using an injection pump, continuing stirring at normal temperature for 5h after the completion of the reaction, removing the solvent and water by reduced pressure distillation after the reaction is finished, extracting the obtained product by using 10 mL of dichloromethane, analyzing by using liquid chromatography and calculating the yield of the 2-bromo-4 nitrophenol to be 93%. The reaction equation is as follows:
Figure RE-DEST_PATH_IMAGE003
。
example 3: step (1): weighing 2g g-C3N4And 150 mL of acetonitrile, and is subjected to ultrasonic treatment for 1h by 80KHz, and 3.4mL of cyanamide and g-C are added3N4Reacting terminal amino to generate guanidino, heating and refluxing for 24h, filtering and drying to obtain guanidine/g-C3N4Adding into 0.4g silver nitrate and 50 mL absolute ethyl alcohol, heating and refluxing for 10h in a dark place by using chelation of guanidyl and metal, filtering and washing off unreacted Ag+Placing the filter cake under a 150W xenon lamp for illumination for 1h, filtering and drying to obtain silver guanidine/g-C3N4；
Step (2): 0.05g of silver guanidine/g-C3N4Stirring the catalyst and 0.2g of 3, 5-dibromophenol in an acetonitrile solvent for 0.5h, starting a 150W xenon lamp light source, dropwise adding 16mL of 0.1mol/L sodium nitrite aqueous solution into the solution, controlling the dropwise adding speed to be 8mL/h by using an injection pump, continuously stirring at normal temperature for 3h after the completion of the reaction, removing the solvent and water by reduced pressure distillation after the reaction is finished, extracting the obtained product by using 10 mL of dichloromethane, analyzing by using liquid chromatography and calculating the yield of the 3-bromo-5 nitrophenol to be 85%. The reaction equation is as follows:
Figure RE-486122DEST_PATH_IMAGE004
。
the spectrum emitted by a xenon lamp is almost the same as that of sunlight, so that the xenon lamp is generally accepted as a stable light source for simulating visible light such as sunlight in a laboratory. The method selects a xenon lamp as a visible light source to perform the photocatalysis selective nitration bromophenol experiment.
Control runs were made in the absence of light and no catalyst, respectively, according to example 3 above, as follows:
comparative example 1: non-light control experiment
Step (1): weighing 2g g-C3N4And 150 mL of acetonitrile, and is subjected to ultrasonic treatment for 1h by 80KHz, and 3.4mL of cyanamide and g-C are added3N4Reacting the terminal amino group to generate guanidine group, heating and refluxing for 24h, filtering and drying to obtain guanidine/g-C3N4Adding into 0.4g silver nitrate and 50 mL absolute ethyl alcohol, heating and refluxing for 10h in a dark place by using chelation of guanidyl and metal, filtering and washing off unreacted Ag+Placing the filter cake under a 150W xenon lamp for illumination for 1h, filtering and drying to obtain silver guanidine/g-C3N4；
Step (2): 0.05g of silver guanidine/g-C3N4The catalyst and 0.2g3, 5-dibromophenol are stirred in acetonitrile solvent for 0.5h, 16mL of 0.1mol/L sodium nitrite water solution is dropped into the solution in a dark room,by usingControlling the dropping speed by using an injection pump, keeping stirring at normal temperature for 3h after the dropping speed is 8mL/h, removing the solvent and water by reduced pressure distillation after the reaction is finished, extracting the obtained product by using 10 mL dichloromethane, and finding that the product 3-bromo-5 nitrophenol exists by liquid chromatography analysis.
Comparative example 2: no catalyst control experiment
The method comprises the following steps: stirring 0.2g of 3, 5-dibromophenol in an acetonitrile solvent for 0.5h, starting a 150W xenon lamp light source, dropwise adding 16mL of 0.1mol/L sodium nitrite aqueous solution into the solution, controlling the dropwise adding speed to be 8mL/h by using an injection pump, continuously stirring at normal temperature for 3h after the completion of the reaction, removing the solvent and water by reduced pressure distillation after the reaction is finished, extracting the obtained product by using 10 mL of dichloromethane, analyzing by using liquid chromatography and calculating the yield of the 3-bromo-5 nitrophenol to be 19%.
It can be seen from comparative example 1 and comparative example 2 that the yield of the target product is low or even none under the conditions of no light and no catalyst, respectively, which fully illustrates the superiority of the catalyst and the photocatalytic nitration process according to the invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (5)

1. A method for selectively nitrifying bromophenol by photocatalysis is characterized in that: takes dibromophenol as raw material, organic solvent and water as mixed solvent, silver guanidine/g-C3N4The catalyst is nitrite, the nitrites are nitration reagents, the catalytic reaction is carried out under visible light, and the product of bromonitrophenol is obtained after the post-treatment after the reaction is finished.
2. The method for the photocatalytic selective nitration of bromophenols according to claim 1, characterized in that: the method comprises the following specific steps:
(1) preparation of silver guanidine/g-C3N4：2g g-C3N4Mixing with 150 mL of acetonitrile, carrying out ultrasonic treatment for 0.5-2 h at 80-100 KHz, adding 3.4-4.2 mL of cyanamide, and mixing with g-C3N4Reacting terminal amino to generate guanidino, heating and refluxing for 24-48 h, filtering and drying to obtain guanidine/g-C3N4(ii) a Dissolving 0.4-0.9 g of silver nitrate in 50 mL of absolute ethanol to obtain guanidine/g-C3N4Adding into anhydrous ethanol solution of silver nitrate, using chelation of guanidino and metal, heating and refluxing for 8-12 h in dark, filtering and washing off unreacted Ag+Placing the filter cake under a 150-300W xenon lamp for illumination for 0.5-1 h, filtering and drying to obtain silver guanidine/g-C3N4；
(2) Photocatalytic selective nitration of bromophenol: 0.05 to 0.2g of silver guanidine/g-C3N4Stirring the catalyst and 0.2g of dibromophenol in an acetonitrile solvent for 0.5h, starting a 150-300W xenon lamp light source, dropwise adding 16-32 mL of 0.1mol/L nitrite aqueous solution into the solution,and controlling the dropping speed to be 6-10 mL/h, continuously stirring at normal temperature for 3-5 h after the dropping is finished, removing the solvent and water by reduced pressure distillation after the reaction is finished, extracting the obtained product by using 10 mL of dichloromethane, and analyzing and calculating the yield of the bromonitrophenol by using liquid chromatography.
3. The method for the photocatalytic selective nitration of bromophenols according to claim 2, characterized in that: and (3) in the step (2), the dibromophenol is any one of 2, 4-dibromophenol, 2, 6-dibromophenol or 3, 5-dibromophenol.
4. The method for the photocatalytic selective nitration of bromophenols according to claim 2, characterized in that: and (3) in the step (2), the nitrite is sodium nitrite or potassium nitrite.
5. The method for the photocatalytic selective nitration of bromophenols according to claim 2, characterized in that: the liquid chromatogram is a standard ODS C-18 chromatographic column, the column temperature is 35 ℃, the mobile phase is acetonitrile/water with the volume ratio of 25/75, the flow rate is 0.35 ml/min, the ultraviolet detection wavelength is 260nm, and the change of raw materials and products is calculated by a conventional area normalization method.
CN202210218046.5A 2022-03-07 2022-03-07 Method for photocatalytic selective nitration of bromophenol Active CN114560771B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210218046.5A CN114560771B (en) 2022-03-07 2022-03-07 Method for photocatalytic selective nitration of bromophenol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210218046.5A CN114560771B (en) 2022-03-07 2022-03-07 Method for photocatalytic selective nitration of bromophenol

Publications (2)

Publication Number Publication Date
CN114560771A true CN114560771A (en) 2022-05-31
CN114560771B CN114560771B (en) 2023-10-27

Family

ID=81718364

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210218046.5A Active CN114560771B (en) 2022-03-07 2022-03-07 Method for photocatalytic selective nitration of bromophenol

Country Status (1)

Country Link
CN (1) CN114560771B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116444375A (en) * 2023-04-06 2023-07-18 平顶山学院 Method for in-situ nitration of halogenated aromatic hydrocarbon under catalysis of light-induced iridium metal

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0237929A1 (en) * 1986-03-11 1987-09-23 F. Hoffmann-La Roche Ag 3,5-Disubstituted pyrocatechol derivatives
US5250741A (en) * 1992-07-13 1993-10-05 Eastman Kodak Company Process for the preparation of 5-alkoxy-2-nitroso phenols
RU2053223C1 (en) * 1991-11-21 1996-01-27 Московское научно-производственное объединение "НИОПИК" Method for production of 6-brom-2-amino-4-nitrophenol
JPH1067716A (en) * 1996-08-23 1998-03-10 Jiyunsei Kagaku Kk Selective nitration of phenol derivative
US5956657A (en) * 1996-12-27 1999-09-21 Daicel Chemical Industies, Ltd. Method for producing nitro compounds
CN101381311A (en) * 2007-09-07 2009-03-11 上海睿智化学研究有限公司 Preparation method of 5-nitro-2,4-bihalogenated phenols compounds
JP2009062342A (en) * 2007-09-08 2009-03-26 National Institute Of Advanced Industrial & Technology Selection method of solvent for nitration of solid organic compound, and nitration reaction method of substrate organic compound
CN102060717A (en) * 2011-01-07 2011-05-18 大连凯飞精细化工有限公司 Method for synthesizing 3-amino-4-bromophenol
WO2011058162A1 (en) * 2009-11-16 2011-05-19 Ferrer Internacional, S.A. Process for preparing 4-nitro-oxy-methyl-benzoic acid
CN107954878A (en) * 2017-12-01 2018-04-24 苏州艾缇克药物化学有限公司 A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols
CN109320403A (en) * 2018-11-27 2019-02-12 常州大学 A kind of preparation method of 2,5- dibromophenol
CN110698352A (en) * 2019-10-29 2020-01-17 邢台学院 Synthetic method of 3-bromo-5-aminocatechol dimethyl ether

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0237929A1 (en) * 1986-03-11 1987-09-23 F. Hoffmann-La Roche Ag 3,5-Disubstituted pyrocatechol derivatives
RU2053223C1 (en) * 1991-11-21 1996-01-27 Московское научно-производственное объединение "НИОПИК" Method for production of 6-brom-2-amino-4-nitrophenol
US5250741A (en) * 1992-07-13 1993-10-05 Eastman Kodak Company Process for the preparation of 5-alkoxy-2-nitroso phenols
JPH1067716A (en) * 1996-08-23 1998-03-10 Jiyunsei Kagaku Kk Selective nitration of phenol derivative
US5956657A (en) * 1996-12-27 1999-09-21 Daicel Chemical Industies, Ltd. Method for producing nitro compounds
CN101381311A (en) * 2007-09-07 2009-03-11 上海睿智化学研究有限公司 Preparation method of 5-nitro-2,4-bihalogenated phenols compounds
JP2009062342A (en) * 2007-09-08 2009-03-26 National Institute Of Advanced Industrial & Technology Selection method of solvent for nitration of solid organic compound, and nitration reaction method of substrate organic compound
WO2011058162A1 (en) * 2009-11-16 2011-05-19 Ferrer Internacional, S.A. Process for preparing 4-nitro-oxy-methyl-benzoic acid
CN102060717A (en) * 2011-01-07 2011-05-18 大连凯飞精细化工有限公司 Method for synthesizing 3-amino-4-bromophenol
CN107954878A (en) * 2017-12-01 2018-04-24 苏州艾缇克药物化学有限公司 A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols
CN109320403A (en) * 2018-11-27 2019-02-12 常州大学 A kind of preparation method of 2,5- dibromophenol
CN110698352A (en) * 2019-10-29 2020-01-17 邢台学院 Synthetic method of 3-bromo-5-aminocatechol dimethyl ether

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
刘建新等, 《物理化学学报》, vol. 30, no. 4, pages 729 - 737 *
唐天声;王辉;曾卓;廖子英;: "2-溴-4-硝基苯酚合成的新方法", 化学试剂, no. 04, pages 247 - 250 *
米贺, 《优秀硕士学位论文全文数据库（电子期刊）》, no. 01, pages 014 - 733 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116444375A (en) * 2023-04-06 2023-07-18 平顶山学院 Method for in-situ nitration of halogenated aromatic hydrocarbon under catalysis of light-induced iridium metal

Also Published As

Publication number Publication date
CN114560771B (en) 2023-10-27

Similar Documents

Publication Publication Date Title
CN113019414B (en) Hydrogenation catalyst, preparation method and application thereof
CN110102350B (en) Catalyst for oxidative synthesis of 2, 5-furandicarboxylic acid and preparation method and application thereof
Kulal et al. Sol–gel synthesised WO3 nanoparticles supported on mesoporous silica for liquid phase nitration of aromatics
Zolfigol et al. Application of silica vanadic acid as a heterogeneous, selective and highly reusable catalyst for oxidation of sulfides at room temperature
Ning et al. Enhanced catalytic reduction of 4-nitrophenol over titania nanotube supported gold nanoparticles by weak ultraviolet light irradiation: role of gold surface charge
CN114560771A (en) Method for selective nitration of bromophenol by photocatalysis
Yu et al. Hierarchical PS/PANI nanostructure supported Cu (II) complexes: facile synthesis and study of catalytic applications in aerobic oxidation
CN104059001B (en) A kind of adjacent benzoic preparation method of nitro sulfuryl
CN108084050B (en) Method for synthesizing imine by catalyzing with aluminum phosphate molecular sieve
Tamami et al. Polymer supported bromates as new, versatile and efficient oxidizing reagents for various organic compounds
CN101914036A (en) Method for preparing azobenzene derivatives
CN109134368A (en) A method of 3,4- dihydro-isoquinoline is synthesized by half dehydrogenation oxidation of 1,2,3,4- tetrahydroisoquinoline
CN111205238B (en) Method for generating 2-aminophenol oxazine-3-ketone compound by catalyzing oxidation of molecular oxygen in aqueous phase
Mardani et al. Photo-tunable oxidation of toluene and its derivatives catalyzed by TBATB
Kuang et al. Solvent free aerobic oxidation of alcohols with 1-methyl-2-azaadamantane N-oxyl as a recyclable catalyst through phase separation
CN110498772A (en) A kind of Terminal Acetylenes multicomponent synthesis 1,4- replaces the method for 1,2,3- triazole
CN106967019B (en) Method for preparing 2, 5-diformylfuran
CN108314646B (en) Method for preparing drug intermediate for urogenital system from high-dispersion bimetal nano material
CN109942456B (en) Method for synthesizing p-benzoquinone monoimine from p-aminophenol
CN115959997A (en) Method for reducing nitro-substituted aromatic compound
CN102249927B (en) Clean nitration reaction of p-chlorobenzotrifluoride under catalysis of degradable functional ionic liquid
CN115611710B (en) Method for improving oxidation chlorination efficiency of 3, 5-dimethylphenol
CN115583869B (en) Selective oxidation chlorination method for phenolic compound
CN118108584A (en) Continuous production method and continuous production system of parahydroxyben-zaldehyde
CN109020819A (en) The preparation method of halogenated aniline and its derivative

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant