CN117551352A - MOFs composite material and preparation method and application thereof - Google Patents

MOFs composite material and preparation method and application thereof Download PDF

Info

Publication number
CN117551352A
CN117551352A CN202311297502.0A CN202311297502A CN117551352A CN 117551352 A CN117551352 A CN 117551352A CN 202311297502 A CN202311297502 A CN 202311297502A CN 117551352 A CN117551352 A CN 117551352A
Authority
CN
China
Prior art keywords
mofs composite
mof
cysteamine
composite according
reaction
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.)
Pending
Application number
CN202311297502.0A
Other languages
Chinese (zh)
Inventor
刘捷威
赵欣
王海平
邓恩泽
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.)
Wuyi University
Original Assignee
Wuyi University
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 Wuyi University filed Critical Wuyi University
Priority to CN202311297502.0A priority Critical patent/CN117551352A/en
Publication of CN117551352A publication Critical patent/CN117551352A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/36—One oxygen atom
    • C07D263/38—One oxygen atom attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C08K2003/3027—Sulfides of cadmium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a MOFs composite material, a preparation method and application thereof, wherein the MOFs composite material comprises Cd-MOF and CdS; the Cd metal cluster in the Cd-MOF is connected with one end of cysteamine, and the other end of cysteamine is connected with CdS. MOFs composite material pair of the invention catalyzes CO 2 The product has excellent stability and catalytic efficiency performance when being cyclized with propargylamine. This is because of the Cd-MOFIs connected with one end of cysteamine, the other end of cysteamine is connected with CdS, and the synergistic effect of CdS and Cd-MOF greatly improves the catalysis of CO 2 Cyclizing with propargylamine.

Description

MOFs composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of metal organic frame materials, in particular to a MOFs composite material and a preparation method and application thereof.
Background
In recent years, carbon neutralization has attracted considerable attention because of the carbon dioxide (CO 2 ) Environmental and climate problems are caused as greenhouse gases. CO 2 Is also a very promising C in synthetic chemistry 1 A source, which is higher than the conventional C such as CO 1 The source is more environment-friendly and safer. Oxazolidinones have good bactericidal activity and low toxicity to humans and are often used as antibiotics in clinical medicine. By reacting propynylamine with CO 2 Has become an effective method for synthesizing 2-oxazolidinone. However, in CO 2 In the cyclization reaction system with propynylamine, due to CO 2 Dynamic inertness and thermodynamic stability of (C) CO 2 Activation usually requires high temperatures and pressures, which greatly reduces the recovery performance of the catalyst. Therefore, development of a photocatalyst which is mild in condition and does not contain noble metal is urgently required, and green conversion of carbon dioxide and propynylamine is a great challenge under normal temperature and pressure and illumination conditions.
Therefore, it is necessary to develop a catalyst which has high stability and high catalytic efficiency and can be used for photocatalytic reaction of propargylamine and CO at normal temperature and pressure 2 Catalyst for cyclization reaction.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the first aspect of the invention provides a MOFs composite material which has high cycle stability and high catalytic efficiency, and can photo-catalyze propargylamine and CO at normal temperature and pressure 2 Is carried out in the presence of a catalyst.
The second aspect of the invention also provides a preparation method of the MOFs composite material.
The third aspect of the invention also provides an application of the MOFs composite material.
According to a first aspect of the invention, an embodiment provides a MOFs composite material comprising Cd-MOF and CdS; the Cd metal cluster in the Cd-MOF is connected with one end of cysteamine, and the other end of cysteamine is connected with CdS.
The MOFs composite material provided by the embodiment of the invention has at least the following beneficial effects:
MOFs composite material pair of the invention catalyzes CO 2 The product has excellent stability and catalytic efficiency performance when being cyclized with propargylamine. This is because the Cd metal cluster in the Cd-MOF is connected with one end of cysteamine, the other end of cysteamine is connected with CdS, and the synergistic effect of CdS and Cd-MOF greatly improves the catalysis of CO 2 Cyclizing with propargylamine.
According to some embodiments of the invention, the Cd-MOF is prepared from a ligand and a cadmium salt by a solvothermal method;
wherein the structural formula of the ligand is shown as follows:
according to a second aspect of the present invention, there is provided a method for preparing MOFs composite material, comprising the steps of:
s1, heating Cd-MOF, cysteamine and a solvent for reaction; obtaining an intermediate;
s2, adding cadmium salt and thioacetamide in the step S1 for continuous reaction, and obtaining the catalyst.
According to some embodiments of the invention, in step S1, the temperature of the heating reaction is 60 to 100 ℃.
According to some embodiments of the invention, in step S1, the molar ratio of Cd-MOF and cysteamine is (3-6): 1.
according to some embodiments of the invention, in step S2, the molar ratio of cadmium salt to thioacetamide is (0.5 to 2): 1.
according to some embodiments of the invention, the solvent is selected from at least one of ethanol, methanol, ethyl acetate, water, DMF.
According to some embodiments of the invention, the Cd-MOF is prepared by the following method:
and mixing the ligand, cadmium salt and an organic solvent for solvothermal reaction to obtain the Cd-MOF.
According to some embodiments of the invention, the solvothermal reaction temperature is 90-150 ℃.
According to some embodiments of the invention, the solvothermal reaction time is 12-84 hours.
According to some embodiments of the invention, the organic solvent is selected from at least one of dimethylformamide, ethanol, acetonitrile, ethyl acetate.
According to some embodiments of the invention, the cadmium salt includes at least one of cadmium nitrate, cadmium acetate.
The third aspect of the invention provides a MOFs composite material for photocatalytic propargylamine and CO 2 Is used in cyclization reaction.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a graph showing the cycling stability of MOFs composites prepared in example 1 of the present invention in photocatalytic propargylamine and carbon dioxide cyclization reactions.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Example 1
Example 1 provides a MOFs composite material, the preparation method of which is as follows:
synthesis of ligand:the reaction equation is as follows, and the preparation steps are as follows:
step one: a mixture of 2.97g of 3- (methoxycarbonyl) phenylboronic acid (16.5 mmol), 1.42g of 1,3,6, 8-tetrabromopyrene (2.75 mmol), 3.0g of potassium carbonate (22 mmol) and 40mL of dioxane was stirred under nitrogen for 30min at room temperature, followed by the addition of 0.05g of tetrakis (triphenylphosphine) palladium (0.045 mmol). The reaction mixture was refluxed for 3 days. After cooling to room temperature, the reaction mixture was poured into 150mL of aqueous solution containing concentrated hydrochloric acid (3:1). The yellow suspension solution was extracted with chloroform (100 ml×3), the organic phases were combined and dried over anhydrous sodium sulfate. The solvent was removed on a rotary evaporator under vacuum to give 1,3,6, 8-tetrakis (3-methoxycarbonylphenyl) pyrene in 76% yield.
Step two: 2.5g of 1,3,6, 8-tetrakis (3-methoxycarbonylphenyl) pyrene was dissolved with 160mL of THF, and 160mL of an aqueous solution in which 10g of NaOH was dissolved was added with stirring, and the mixture was filtered off with stirring under reflux for 72 hours, to remove the organic solvent in vacuo. The pH of the filtrate was adjusted to 1 with concentrated hydrochloric acid. The yellow solid obtained was collected by filtration, washed with water and methanol, and dried in a vacuum oven to give ligand (H) 4 PTTB), yield: 98%. The hydrogen spectrum data are as follows:
1 H NMR(500MHz,DMSO-d 6 )δ13.14(s,4H),8.24(s,4H),8.17(s,4H),8.11(t,J＝6.2Hz,4H),8.08(s,2H),8.00(d,J＝7.8Hz,4H),7.75(t,J＝7.7Hz,4H).FT-IR(KBr)ν3428(br),3176(br),1709(s),1244(m),1091(m)cm -1 .
synthesis of Cd-MOFs
Will H 4 PTTB(69mg,0.1mmol)、Cd(NO 3 ) 2 ·4H 2 O (206 mg,0.667 mmol), dimethylformamide (DMF, 3.5 mL) and H 2 O (1 mL) was placed in a glass vial, sealed and heated to 100deg.C in an oven. After 72H, orange bulk crystals (82.4 mg, as H) were obtained 4 PTTB base yield 87.6%) and air dried.
MOFs composite material
S1, suspending 120mg of activated Cd-MOFs in 60mL of absolute ethanol. 120mg of cysteamine is added into the suspension, and the mixture is heated and stirred and refluxed for 1h at 80 ℃;
s2, 132.6mg of Cd (CH) was further added 3 COO) 2 ·2H 2 O and 37.2mg thioacetamide, reflux for 12h; the MOFs composite (named CdS@Cd-MOFs) obtained by centrifugation was washed 2 times in deionized water and dried at 60 ℃.
Test example 1
MOFs composite prepared in example 1 was used to catalyze propargylamine with CO 2 The cyclization reaction is specifically as follows:
preparation of propargylamine compounds
The reaction general formula and the preparation steps are as follows:
3-bromopropyne (4 mmol) was added dropwise via a constant pressure dropping funnel to a 25mL glass bottle of an amino compound (20 mmol) under stirring at room temperature for 12 hours under magnetic stirring, and after completion of the reaction, the reaction mixture was stirred magnetically with Et 2 Dilute in O and use saturated NaHCO 3 Aqueous washing (3X 25 mL). The extracted organic phase was concentrated by rotary evaporation and purified by column chromatography on silica gel (PE: ea=10:1) to give the product as a yellow oil.
Propargylamine compounds 1a to 6a were prepared by the above-described preparation methods.
The yellow oil was purified by column chromatography on silica gel (PE/ethyl acetate=10:1, rf=0.5), 1H NMR (500 mhz, cdcl 3) delta 7.42-7.26 (m, 5H), 3.88 (s, 2H), 3.42 (d, j=2.2 hz, 2H), 2.28 (t, j=2.1 hz, 1H), 1.68 (s, 1H).
The yellow oil was purified by column chromatography on silica gel (PE/ethyl acetate=10:1, rf=0.4). 1h NMR (500 mhz, cdcl 3) δ 7.29 (dd, j=6.0, 2.4hz, 2H), 6.89 (d, j=8.6 hz, 2H), 3.84 (d, j=2.2 hz, 2H), 3.81 (d, j=2.6 hz, 3H), 3.43 (t, j=2.5 hz, 2H), 2.28 (d, j=2.4 hz, 1H), 1.75 (d, j=16.0 hz, 1H).
The yellow oil was purified by column chromatography on silica gel (PE/ethyl acetate=10:1, rf=0.6) 1H NMR (500 mhz, cdcl 3) delta 7.33 (dt, j=8.3, 4.2hz, 2H), 7.07-6.94 (m, 2H), 3.87 (s, 2H), 3.43 (t, j=4.1 hz, 2H), 2.29 (t, j=2.4 hz, 1H), 1.70 (s, 1H).
The yellow oil was purified by column chromatography on silica gel (PE/ethyl acetate=10:1, rf=0.6) 1H NMR (500 mhz, cdcl 3) delta 3.40 (d, j=2.4 hz, 2H), 2.50 (d, j=6.7 hz, 2H), 2.19 (s, 1H), 1.70 (d, j=15.5 hz, 5H), 1.44 (dd, j=6.6, 3.3hz, 2H), 1.30-1.09 (m, 3H), 1.01-0.85 (m, 2H).
The yellow oil was purified by column chromatography on silica gel (PE/ethyl acetate=10:1, rf=0.4) 1H NMR (500 mhz, cdcl 3) delta 7.40-7.24 (m, 5H), 4.02 (q, j=6.6 hz, 1H), 3.36 (dd, j=17.1, 2.5hz, 1H), 3.16 (dd, j=17.1, 2.4hz, 1H), 2.22 (t, j=2.4 hz, 1H), 1.37 (d, j=6.6 hz, 3H).
2 Cyclization of propynylamine with CO:
propargylamine compounds 1a to 7a, 1, 3-tetramethylguanidine (TMG, 11.5mg,0.1 mmol), cdS@Cd-MOFs (13.4 mg,0.01 mmol) prepared in example 1, and 2mL of acetonitrile (MeCN) prepared in the above were each prepared under visible light>400 nm) was stirred for 8 hours. Vacuum-treating the glass reactor before light irradiation, and using high-purity CO under a pressure of 1atm 2 Backfilling; the reaction mixture was dried by rotary evaporation, and purified by silica gel column chromatography to give yellow oil (PE/ethyl acetate=10:1) to give compounds 1b to 6b.
Product nuclear magnetism:
purification by silica gel column chromatography (PE/ethyl acetate=10:1, rf=0.4) gave butter (94.9 mg, 99%). 1 H NMR(500MHz,CDCl3)δ7.42–7.26(m,5H),4.78–4.71(m,1H),4.48(s,2H),4.26(dd,J＝5.2,2.2Hz,1H),4.08–3.99(m,2H).
Taking the catalytic preparation of compound 1b as an example, the yield of the photocatalysis by Cd-MOF is 19%; the yield using CdS photocatalysis was 25.2%.
Purification by silica gel column chromatography (PE/ethyl acetate=10:1, rf=0.3) gave butter (94.9 mg, 99%). . 1 H NMR(500MHz,CDCl3)δ7.20–7.12(m,2H),6.88–6.81(m,2H),4.67(dd,J＝5.6,2.7Hz,1H),4.36(s,2H),4.22–4.16(m,1H),3.97(t,J＝2.4Hz,2H),3.76(d,J＝4.9Hz,3H).
Purification by silica gel column chromatography (PE/ethyl acetate=10:1, rf=0.4) gave butter (94.9 mg, 99%). . 1 H NMR(500MHz,CDCl3)δ7.33–7.22(m,2H),7.07–6.97(m,2H),4.72(dd,J＝5.7,2.7Hz,1H),4.43(s,2H),4.25(dt,J＝3.1,2.2Hz,1H),4.02(t,J＝2.4Hz,2H).
Purification by silica gel column chromatography (PE/ethyl acetate=5:1, rf=0.3) gave butter (94.9 mg, 99%). 1 H NMR(500MHz,CDCl3)δ4.73(d,J＝2.9Hz,1H),4.33–4.21(m,1H),4.16(t,J＝2.4Hz,2H),3.12(t,J＝7.0Hz,2H),1.83–1.36(m,5H),1.35–1.11(m,4H),1.07–0.91(m,1H).
Purification by silica gel column chromatography (PE/ethyl acetate=10:1, rf=0.5) gave butter (94.9 mg, 99%). . 1 H NMR(500MHz,CDCl3)δ7.40–7.31(m,5H),5.30–5.22(m,1H),4.71(dd,J＝5.6,2.7Hz,1H),4.21(dt,J＝3.0,2.2Hz,1H),4.10(dt,J＝14.2,2.4Hz,1H),3.77(dt,J＝14.2,2.4Hz,1H),1.60(d,J＝7.1Hz,3H).
Cycling stability experiment
Taking the preparation of compound 1b as an example, after completion of the reaction, the recovered catalyst was washed with acetone (6 ml×3), dried in air, and reused in continuous operation. The results are shown in FIG. 1, and the catalyst has high catalytic efficiency after nine cycles.
The present invention has been described in detail with reference to the above embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (10)

1. MOFs composite material, characterized by comprising Cd-MOF and CdS; the Cd metal cluster in the Cd-MOF is connected with one end of cysteamine, and the other end of cysteamine is connected with CdS.
2. The MOFs composite according to claim 1, wherein the Cd-MOF is prepared from ligands and cadmium salts by solvothermal method;
wherein the structural formula of the ligand is shown as follows:
3. the method for preparing MOFs composite according to claim 1 or 2, comprising the steps of:
s1, heating Cd-MOF, cysteamine and a solvent for reaction; obtaining an intermediate;
s2, adding cadmium salt and thioacetamide in the step S1 for continuous reaction, and obtaining the catalyst.
4. The method for producing MOFs composite according to claim 3, wherein in step S1, the temperature of the heating reaction is 60 to 100 ℃.
5. The method for preparing MOFs composite according to claim 3, wherein in step S1, the molar ratio of Cd-MOF to cysteamine is (3-6): 1.
6. the method for preparing MOFs composite according to claim 3, wherein the solvent is at least one selected from ethanol, methanol, ethyl acetate, water, DMF.
7. The method for preparing MOFs composite according to claim 3, wherein the Cd-MOF is prepared by:
and mixing the ligand, cadmium salt and an organic solvent for solvothermal reaction to obtain the Cd-MOF.
8. The method for preparing MOFs composite according to claim 3, wherein the solvothermal reaction temperature is 90-150 ℃.
9. The method for preparing MOFs composite according to claim 3, wherein the solvothermal reaction time is 12-84 hours.
10. The MOFs composite according to claim 1 or 2, wherein propargylamine and CO are photocatalytic 2 Is used in cyclization reaction.
CN202311297502.0A 2023-10-08 2023-10-08 MOFs composite material and preparation method and application thereof Pending CN117551352A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311297502.0A CN117551352A (en) 2023-10-08 2023-10-08 MOFs composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311297502.0A CN117551352A (en) 2023-10-08 2023-10-08 MOFs composite material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN117551352A true CN117551352A (en) 2024-02-13

Family

ID=89813659

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311297502.0A Pending CN117551352A (en) 2023-10-08 2023-10-08 MOFs composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN117551352A (en)

Similar Documents

Publication Publication Date Title
CN101671365A (en) Chiral spiro aminophosphine ligand compound and synthesis method as well as application thereof
CN103554201B (en) Gamithromycin preparation method
CN109651135B (en) Preparation method and application of chiral Zr-MOF catalyst
CN114920775B (en) Axial chiral bisindole catalyst and synthetic method and application thereof
CN101307015A (en) Process for preparing cilastatin sodium
CN107129444A (en) High-purity (S) -2- t-butoxycarbonyl aminos -3-（4- carbamyl -2,6- 3,5-dimethylphenyls）The preparation method of propionic acid
CN111747923B (en) Crown ether carboxylic acid compound-containing BPDC-12-C-4 and preparation method and application thereof
CN106905254B (en) A kind of preparation method of 5- phenyl -1H- tetrazole
CN117551352A (en) MOFs composite material and preparation method and application thereof
CN114702438B (en) Kumada coupling reaction of heterogeneous catalysis of bimetallic organic framework
CN114644582B (en) Preparation method of phenyl dithiourea compound
CN106636241B (en) Method for preparing esmollin intermediate by enzyme method
CN113754606B (en) Phenoxazine diamine derivative and/or phenothiazine diamine derivative and preparation method thereof
CN113024611A (en) Novel N-heterocyclic carbene cyclic palladium compound and preparation method and application thereof
CN113004248A (en) Method for synthesizing carbazole compound by catalyzing hydrocarbon amination reaction with cobalt
CN113979966A (en) Preparation method of 2-phenylbenzothiazole
CN108948055B (en) 8-methylquinoline gem-diboron compound and preparation method thereof
CN112390696A (en) Method for preparing alpha-aminonitrile, product and application thereof
CN116836107B (en) Carbazol eight-membered ring large conjugated structure OLED material and preparation method thereof
CN113735773B (en) 2, 3-dihydro-1, 2-diazacyclobutene oxynitride and preparation method thereof
CN115304557B (en) Enamine derivative and preparation method thereof
CN104558050B (en) Bimetal Ru supramolecular macrocyclic compound and synthetic method and application thereof
CN113956268B (en) 6-bromo-1-chlorobenzothiophene [2,3-c ] pyridine and synthetic method
CN114805163B (en) Method for synthesizing organic selenium compound
CN111718245B (en) Method for preparing deuterated chemicals through photocatalytic decarboxylation conversion

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