CN116283758A - Method for synthesizing N-formyl tetrahydroquinoline from quinoline and product - Google Patents
Method for synthesizing N-formyl tetrahydroquinoline from quinoline and product Download PDFInfo
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- CN116283758A CN116283758A CN202310336143.9A CN202310336143A CN116283758A CN 116283758 A CN116283758 A CN 116283758A CN 202310336143 A CN202310336143 A CN 202310336143A CN 116283758 A CN116283758 A CN 116283758A
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- tetrahydroquinoline
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- CHOVRXRQUYRLHZ-UHFFFAOYSA-N 3,4,4a,5-tetrahydro-2h-quinoline-1-carbaldehyde Chemical compound C1C=CC=C2N(C=O)CCCC21 CHOVRXRQUYRLHZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 229910018936 CoPd Inorganic materials 0.000 claims abstract description 64
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019253 formic acid Nutrition 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 13
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- SIAVMDKGVRXFAX-UHFFFAOYSA-N 4-carboxyphenylboronic acid Chemical compound OB(O)C1=CC=C(C(O)=O)C=C1 SIAVMDKGVRXFAX-UHFFFAOYSA-N 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000010517 secondary reaction Methods 0.000 abstract 1
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 54
- 239000000047 product Substances 0.000 description 45
- 239000006227 byproduct Substances 0.000 description 28
- 238000004458 analytical method Methods 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000006170 formylation reaction Methods 0.000 description 4
- 230000022244 formylation Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- AUVSUPMVIZXUOG-UHFFFAOYSA-N (4-sulfanylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(S)C=C1 AUVSUPMVIZXUOG-UHFFFAOYSA-N 0.000 description 1
- MNABRWLVTSGIMU-FQEVSTJZSA-N 7-[4-[[4-[(5s)-5-(acetamidomethyl)-2-oxo-1,3-oxazolidin-3-yl]-2-fluorophenoxy]methyl]-4-phosphonooxypiperidin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound O=C1O[C@@H](CNC(=O)C)CN1C(C=C1F)=CC=C1OCC1(OP(O)(O)=O)CCN(C=2C(=CC=3C(=O)C(C(O)=O)=CN(C=3C=2)C2CC2)F)CC1 MNABRWLVTSGIMU-FQEVSTJZSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 239000002259 anti human immunodeficiency virus agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 description 1
- 229960001259 diclofenac Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 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
- -1 nomifene Chemical compound 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003530 tetrahydroquinolines Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/08—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms with acylated ring nitrogen atom
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for synthesizing N-formyl tetrahydroquinoline by quinoline and a product thereof, belonging to the technical field of chemistry and chemical engineering. The method comprises the following steps: will N 2 Introducing CoPd/B-g-C 3 N 4 Adding quinoline, formic acid and water into a catalyst to perform secondary reaction, and removing CoPd/B-g-C after the reaction is finished 3 N 4 The catalyst can obtain the N-formyl tetrahydroquinoline. The invention also provides the N-formyl tetrahydroquinoline synthesized by the method. The synthesis method is simple and efficient, can obviously reduce the reaction temperature, does not need high-pressure reaction, realizes the synthesis of high-selectivity N-formyl tetrahydroquinoline under mild conditions, and can be widely applied to industrial application.
Description
Technical Field
The invention belongs to the technical field of chemistry and chemical engineering, and particularly relates to a method for synthesizing N-formyl tetrahydroquinoline and a product thereof.
Background
The selective reduction of N-aromatics in fused aromatic ring systems is a very interesting class of chemical reactions, where hydrogenated N-heterocycles are part of many pharmaceutically important drugs (e.g. diclofenac, nomifene, oxaquin), anti-HIV drugs and lipid controlling compounds (e.g. phenanthroline and quinoxaline) as well as natural alkaloids, and thus research into the selective reduction of N-aromatics is very important. In addition, reduced N-formylated heterocycles are another important class of synthetic intermediates, which are widely used in the pharmaceutical industry.
Quinoline and its derivatives are widely found in coal and oil shale as one of the natural resources, and are also byproducts of petroleum refining processes. And N-formyl tetrahydroquinoline is a very important fine chemical and pharmaceutical intermediate. Thus, the preparation of added-value N-formyl tetrahydroquinolines by supplying more abundant quinolines and derivatives thereof is a very important class of reactions. In the prior art, the most common method for selectively reducing quinolines and derivatives thereof based on the theory of tandem reactions is to use a large amount of gas H 2 Reduction is carried out in which the N-formylation is carried out in H 2 And CO, thereby producing N-formyl tetrahydroquinoline. However, these reactions require high H 2 Pressure and specific reaction settings, and thus, methods for preparing N-formyl tetrahydroquinoline using the above reactions, are rarely used in industrial applications.
Therefore, how to develop a method for synthesizing N-formyl tetrahydroquinoline by selectively reducing quinoline and its derivatives under mild conditions based on the theory of tandem reaction is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for synthesizing N-formyl tetrahydroquinoline by quinoline and a product thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the invention provides a method for synthesizing N-formyl tetrahydroquinoline by quinoline, which comprises the following steps:
will N 2 Introducing CoPd/B-g-C 3 N 4 Adding quinoline, formic acid and water into a catalyst to react, and removing CoPd/B-g-C after the reaction is finished 3 N 4 The catalyst can obtain the N-formyl tetrahydroquinoline.
The beneficial effects are that: in the present invention, N is first added 2 Introducing CoPd/B-g-C 3 N 4 In the catalyst, the air in the reaction vessel is removed, and then CoPd/B-g-C is used 3 N 4 As the catalyst, formic acid is used as a hydrogen source and a formylating agent, the N-formyltetrahydroquinoline can be synthesized by taking quinoline as a raw material under the condition of normal pressure and mild temperature in a liquid phase, and the conversion rate of the reaction for synthesizing the N-formyltetrahydroquinoline and the selectivity of the target product N-formyltetrahydroquinoline are improved.
Further, the N is 2 The inlet amount is 20-30 mL/min, and the inlet time is 80-120 min; the CoPd/B-g-C 3 N 4 The mass ratio of the catalyst to the quinoline to the formic acid to the water is (0.01-0.05) to 1 to 2-5 to 10-20; the reaction is as follows: reacting for 2-5 h at the temperature of 10-50 ℃; the rotational speed of the centrifugation is 8000-14000 rpm, and the time is 2-9 h.
The beneficial effects are that: the invention has the advantages of mild reaction temperature, simple operation and low cost, and can realize the synthesis of the N-formyl tetrahydroquinoline under the condition of adding a small amount of catalyst.
Further, the CoPd/B-g-C 3 N 4 A method for preparing a catalyst comprising the steps of:
(1) Dissolving dicyandiamide in water, adding a source B for hydrothermal reaction, filtering, drying and roasting to obtain B-g-C 3 N 4 ；
(2) Palladium chloride and Co salts are first dissolved in water, followed by the addition of the B-g-C 3 N 4 Then ammonia borane solution is added for reduction reaction, and finally centrifugal drying is carried out, thus obtaining the CoPd/B-g-C 3 N 4 A catalyst.
Further, in the step (1), the mass ratio of the dicyandiamide to the water to the B source is 1:10-16:0.1-0.4.
Still further, the B source includes one or any of boric acid, terephthaloric acid or 4-carboxyphenylboronic acid.
The beneficial effects are that: the invention takes one or more of boric acid, terephthaloyl acid or 4-carboxyphenylboronic acid as a B source, and then carries out hydrothermal self-assembly with dicyandiamide, and the B-g-C is prepared by roasting 3 N 4 The charge distribution of the catalyst can be obviously improved by doping the B source in situ, so that the catalytic activity of the catalyst is improved, and the conversion rate of the reaction is improved.
Further, the hydrothermal reaction in step (1) is: reacting for 18-36 h at 80-140 ℃; the drying is as follows: drying at 70-110 deg.c for 18-24 min; the roasting is as follows: roasting at 520-600 deg.c for 6-12 hr.
The beneficial effects are that: the invention controls the hydrothermal reaction, drying and roasting to be carried out under the conditions, the reaction conditions are milder, and the B-g-C under the milder conditions is realized 3 N 4 Is a controllable synthesis of (2).
Further, the B-g-C in step (2) 3 N 4 The mass ratio of the palladium chloride, the Co salt, the ammonia borane solution and the water is 1:0.1-0.3:0.3-0.5:0.4-0.6:20-60.
Further, the Co salt comprises one or any several of cobalt nitrate, cobalt acetate, cobalt acetylacetonate or cobalt chloride.
The beneficial effects are that: the invention optimizes and controls the synergistic effect among all metal compounds by selecting the precursors and adjusting the proportion, so that the prepared CoPd/B-g-C 3 N 4 The catalyst can more effectively exert the performance and improve the conversion rate of the reaction.
Further, the concentration of the ammonia borane solution in the step (2) is 0.05-0.15 g/L; the temperature of the reduction reaction is-4 ℃ and the time is 3.0-6.0 h.
The beneficial effects are that: the invention uses CoPd/B-g-C 3 N 4 The catalyst is prepared by adjusting the content of a B source, the proportion of a metal component, the concentration of a reducing agent and the reaction condition, so as to change the charge distribution of a metal valence band orbit and adjust the selectivity of catalytic reaction.
The invention also provides the N-formyl tetrahydroquinoline synthesized by the method for synthesizing the N-formyl tetrahydroquinoline by adopting the quinoline.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses CoPd/B-g-C 3 N 4 The catalyst is used for synthesizing N-formyltetrahydroquinoline by taking formic acid as a hydrogen source and a formylating agent, the conversion rate of the reaction reaches more than 99.6%, the selectivity of a target product N-formyltetrahydroquinoline can reach more than 98.9%, the selectivity of a byproduct tetrahydroquinoline is controlled below 1.1%, and the catalyst is far superior to the existing high-pressure formylation process, particularly the formylation is carried out simultaneously by in-situ hydrogen release of formic acid, and the reaction temperature can be obviously reduced. High pressure formylation requires the presence of a catalyst in both CO and H 2 The N-formyl tetrahydroquinoline is synthesized by reaction under the pressure of more than 5MPa, the technology does not need high-pressure reaction, high-selectivity N-formyl tetrahydroquinoline is synthesized under the mild condition, and in addition, the catalyst can still keep good catalytic stability after being recycled for 60 times, so that the sustainable utilization of partial raw materials is realized. The synthesis method of the invention is simple and efficient, and can be widely used for industrial application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 is a TEM image of the CoPd/B-g-C3N4 catalyst prepared in example 1.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the examples of the present invention are all commercially available.
Example 1
A method for synthesizing N-formyl tetrahydroquinoline by quinoline, which comprises the following steps:
(1) 1g of dicyandiamide is dissolved in 10g of water, then 0.1g of boric acid is added, stirred and dissolved, transferred to a hydrothermal synthesis kettle, subjected to hydrothermal reaction at 80 ℃ for 36h, filtered, dried at 70 ℃ for 24h, transferred to a tube furnace, and baked at 520 ℃ for 12h to obtain B-g-C 3 N 4 ；
(2) 0.01g of palladium chloride and 0.03g of cobalt nitrate were dissolved in 2g of water, followed by the addition of 0.1g of the above-mentioned B-g-C 3 N 4 Then 0.04g ammonia borane solution with concentration of 0.05g/L is added to reduce for 6.0h at the temperature of-4 ℃, and the CoPd/B-g-C is obtained after centrifugal drying 3 N 4 Catalyst in which CoPd/B-g-C is prepared 3 N 4 A TEM image of the catalyst is shown in fig. 1, and it can be seen from fig. 1 that the catalyst is uniformly distributed on the support.
(3) 0.1g of the prepared CoPd/B-g-C was reacted with 3 N 4 The catalyst was placed in a three-necked flask and N was introduced at a rate of 20mL/min for 120min 2 Then adding 1g of quinoline, 2g of formic acid and 10g of water into a three-neck flask, uniformly stirring, reacting at 10 ℃ for 5 hours, and finally centrifuging at 10000rpm for 4 hours to remove CoPd/B-g-C 3 N 4 After the catalyst, the N-formyl tetrahydroquinoline can be obtained.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 The catalyst is used for synthesizing N-formyl tetrahydroquinoline, the conversion rate of the reaction is 99.6%, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 98.9%, and the selectivity of the byproduct tetrahydroquinoline is 1.1%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 99.6%, the selectivity of the target product N-formyl tetrahydroquinoline is 98.8%, and the selectivity of the byproduct tetrahydroquinoline is 1.2%.
Example 2
A method for synthesizing N-formyl tetrahydroquinoline by quinoline, which comprises the following steps:
(1) 1g of dicyandiamide is dissolved in 16g of water, then 0.2g of terephthaloyl acid is added, and the mixture is stirred and dissolved and then transferredIn a hydrothermal synthesis kettle, carrying out hydrothermal reaction at 140 ℃ for 18h, filtering, drying at 110 ℃ for 18h, transferring into a tube furnace, and roasting at 600 ℃ for 6h to obtain B-g-C 3 N 4 ；
(2) 0.03g of palladium chloride and 0.05g of cobalt acetate are dissolved in 6g of water, followed by the addition of 0.1g of the abovementioned B-g-C 3 N 4 Then 0.06g ammonia borane solution with the concentration of 0.15g/L is added for reduction for 3.0h at the temperature of 4 ℃, and the CoPd/B-g-C is obtained after centrifugal drying 3 N 4 A catalyst.
(3) 0.1g of the prepared CoPd/B-g-C was reacted with 3 N 4 The catalyst was placed in a three-necked flask and N was introduced at a rate of 30mL/min for 80min 2 Then adding 1g of quinoline, 5g of formic acid and 20g of water into a three-neck flask, uniformly stirring, reacting for 2 hours at 50 ℃, and finally centrifuging for 8 hours at the rotating speed of 8000rpm to remove CoPd/B-g-C 3 N 4 After the catalyst, the N-formyl tetrahydroquinoline can be obtained.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 The catalyst is used for synthesizing N-formyl tetrahydroquinoline, the conversion rate of the reaction is 100%, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 99.9%, and the selectivity of the byproduct tetrahydroquinoline is 0.1%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 100%, the selectivity of the target product N-formyl tetrahydroquinoline is 99.8%, and the selectivity of the byproduct tetrahydroquinoline is 0.2%.
Example 3
A method for synthesizing N-formyl tetrahydroquinoline by quinoline, which comprises the following steps:
(1) Dissolving 1g of dicyandiamide in 14g of water, adding 0.3g of 4-carboxyphenylboronic acid, stirring and dissolving, transferring to a hydrothermal synthesis kettle, performing hydrothermal reaction at 120 ℃ for 28h, filtering, drying at 80 ℃ for 20h, transferring to a tubular furnace, and roasting at 550 ℃ for 8h to obtain B-g-C 3 N 4 ；
(2) 0.02g of palladium chloride and 0.04g of cobalt acetylacetonate are dissolved in 5g of water and then 0.1g of palladium chloride is addedB-g-C as described above 3 N 4 Then 0.05g ammonia borane solution with the concentration of 0.12g/L is added for reduction for 5.0h at the temperature of 2 ℃, and the CoPd/B-g-C is obtained after centrifugal drying 3 N 4 A catalyst.
(3) 0.1g of the prepared CoPd/B-g-C was reacted with 3 N 4 The catalyst was placed in a three-necked flask and N was introduced at a rate of 25mL/min for 100min 2 Then adding 1g of quinoline, 4g of formic acid and 15g of water into a three-neck flask, uniformly stirring, reacting for 3 hours at 40 ℃, and finally centrifuging for 3 hours at the rotating speed of 12000rpm to remove CoPd/B-g-C 3 N 4 After the catalyst, the N-formyl tetrahydroquinoline can be obtained.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 The catalyst is used for synthesizing N-formyl tetrahydroquinoline, the conversion rate of the reaction is 99.8%, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 99.2%, and the selectivity of the byproduct tetrahydroquinoline is 0.8%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 99.8%, the selectivity of the target product N-formyl tetrahydroquinoline is 99.1%, and the selectivity of the byproduct tetrahydroquinoline is 0.9%.
Example 4
A method for synthesizing N-formyl tetrahydroquinoline by quinoline, which comprises the following steps:
(1) 1g of dicyandiamide is dissolved in 12g of water, then 0.4g of 4-carboxyphenylboronic acid is added, stirred and dissolved, transferred to a hydrothermal synthesis kettle, subjected to hydrothermal reaction at 100 ℃ for 32h, filtered, dried at 100 ℃ for 21h, transferred to a tubular furnace, and baked at 570 ℃ for 10h to obtain B-g-C 3 N 4 ；
(2) 0.02g of palladium chloride and 0.05g of cobalt chloride were dissolved in 4g of water, followed by the addition of 0.1g of the above-mentioned B-g-C 3 N 4 Then 0.04g ammonia borane solution with the concentration of 0.10g/L is added for reduction for 5.0h at the temperature of 2 ℃, and the CoPd/B-g-C is obtained after centrifugal drying 3 N 4 A catalyst.
(3) 0.1g of the prepared CoPd/B-g-C was reacted with 3 N 4 The catalyst was placed in a three-necked flask and N was introduced at a rate of 22mL/min for 110min 2 Then adding 1g of quinoline, 3g of formic acid and 12g of water into a three-neck flask, uniformly stirring, reacting for 4 hours at 30 ℃, and finally centrifuging for 2 hours at the speed of 14000rpm to remove CoPd/B-g-C 3 N 4 After the catalyst, the N-formyl tetrahydroquinoline can be obtained.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 The catalyst is used for synthesizing N-formyl tetrahydroquinoline, the conversion rate of the reaction is 99.6%, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 99.1%, and the selectivity of the byproduct tetrahydroquinoline is 0.9%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 99.6%, the selectivity of the target product N-formyl tetrahydroquinoline is 99.0%, and the selectivity of the byproduct tetrahydroquinoline is 1.0%.
Example 5
A method for synthesizing N-formyl tetrahydroquinoline by quinoline, which comprises the following steps:
(1) 1g of dicyandiamide is dissolved in 10g of water, then 0.3g of terephthaloyl acid is added, stirred and dissolved, transferred to a hydrothermal synthesis kettle, subjected to hydrothermal reaction at 130 ℃ for 18h, filtered, dried at 105 ℃ for 19h, transferred to a tubular furnace, and baked at 520 ℃ for 12h to obtain B-g-C 3 N 4 ；
(2) 0.01g of palladium chloride and 0.04g of cobalt acetylacetonate were dissolved in 3g of water, followed by the addition of 0.1g of the above-mentioned B-g-C 3 N 4 Then 0.06g ammonia borane solution with concentration of 0.08g/L is added for reduction for 4.0h at the temperature of 0 ℃, and the CoPd/B-g-C is obtained after centrifugal drying 3 N 4 A catalyst.
(3) 0.1g of the prepared CoPd/B-g-C was reacted with 3 N 4 The catalyst was placed in a three-necked flask and N was introduced at a rate of 24mL/min for 115min 2 Then adding 1g of quinoline, 4g of formic acid and 10g of water into a three-neck flask, uniformly stirring, reacting for 2 hours at 50 ℃, and finally centrifuging for 9 hours at 9000rpm to remove CoPd/B-g-C 3 N 4 After the catalyst, N-methyl can be obtainedAcyl tetrahydroquinolines.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 The catalyst is used for synthesizing N-formyl tetrahydroquinoline, the conversion rate of the reaction is 99.9%, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 99.7%, and the selectivity of the byproduct tetrahydroquinoline is 0.3%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 99.9%, the selectivity of the target product N-formyl tetrahydroquinoline is 99.6%, and the selectivity of the byproduct tetrahydroquinoline is 0.4%.
Example 6
A method for synthesizing N-formyl tetrahydroquinoline by quinoline, which comprises the following steps:
(1) Dissolving 1g of dicyandiamide in 14g of water, adding 0.4g of terephthaloyl ic acid and boric acid, wherein the mass ratio of the terephthaloyl ic acid to the boric acid is 1:2, stirring and dissolving, transferring into a hydrothermal synthesis kettle, carrying out hydrothermal reaction at 120 ℃ for 25h, filtering, drying at 110 ℃ for 19h, transferring into a tubular furnace, and roasting at 580 ℃ for 10h to obtain B-g-C 3 N 4 ；
(2) 0.02g of palladium chloride and 0.05g of cobalt acetate and cobalt chloride are dissolved in 4.5g of water, followed by the addition of 0.1g of B-g-C as described above 3 N 4 Wherein the mass ratio of the cobalt acetate to the cobalt chloride is 1:1, then 0.06g ammonia borane solution with the concentration of 0.08g/L is added for reduction for 5.0h at the temperature of 2 ℃, and the CoPd/B-g-C can be obtained after centrifugal drying 3 N 4 A catalyst.
(3) 0.1g of the prepared CoPd/B-g-C was reacted with 3 N 4 The catalyst was placed in a three-necked flask and N was introduced at a rate of 24mL/min for 115min 2 Then adding 1g of quinoline, 4g of formic acid and 16g of water into a three-neck flask, uniformly stirring, reacting for 4 hours at 30 ℃, and finally centrifuging for 6 hours at 11000rpm to remove CoPd/B-g-C 3 N 4 After the catalyst, the N-formyl tetrahydroquinoline can be obtained.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 Catalyst compositionThe conversion rate of the reaction is 99.9 percent, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 99.4 percent, and the selectivity of the byproduct tetrahydroquinoline is 0.6 percent. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 99.9%, the selectivity of the target product N-formyl tetrahydroquinoline is 99.2%, and the selectivity of the byproduct tetrahydroquinoline is 0.8%.
Comparative example 1
A process for the synthesis of N-formyl tetrahydroquinoline from quinoline differs from example 2 only in that dicyandiamide in step (1) is replaced by melamine. The rest of the procedure is the same as in example 2.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 The catalyst is used for synthesizing N-formyl tetrahydroquinoline, the conversion rate of the reaction is 99.2%, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 97.4%, and the selectivity of the byproduct tetrahydroquinoline is 2.6%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 99.1%, the selectivity of the target product N-formyl tetrahydroquinoline is 97.2%, and the selectivity of the byproduct tetrahydroquinoline is 2.8%.
Comparative example 2
A method for synthesizing N-formyl tetrahydroquinoline by quinoline differs from example 2 only in that the terephthaloboric acid in step (2) is replaced by 4-mercaptophenylboronic acid. The rest of the procedure is the same as in example 2.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 The catalyst is used for synthesizing N-formyl tetrahydroquinoline, the conversion rate of the reaction is 97.4%, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 92.3%, and the selectivity of the byproduct tetrahydroquinoline is 7.7%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 97.3%, the selectivity of the target product N-formyl tetrahydroquinoline is 92.1%, and the selectivity of the byproduct tetrahydroquinoline is 7.9%.
Comparative example 3
A process for the synthesis of N-formyl tetrahydroquinoline from quinoline, which differs from example 2 only in that 0.8g of terephthaloyl acid is added in step (1). The rest of the procedure is the same as in example 2.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 The catalyst is used for synthesizing N-formyl tetrahydroquinoline, the conversion rate of the reaction is 93.4%, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 91.6%, and the selectivity of the byproduct tetrahydroquinoline is 8.4%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 93.2%, the selectivity of the target product N-formyl tetrahydroquinoline is 91.4%, and the selectivity of the byproduct tetrahydroquinoline is 8.6%.
Comparative example 4
A process for the synthesis of N-formyl tetrahydroquinoline from quinoline differs from example 2 only in that palladium chloride in step (2) is replaced by sodium tetrachloropalladate. The rest of the procedure is the same as in example 2.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 The catalyst is used for synthesizing N-formyl tetrahydroquinoline, the conversion rate of the reaction is 97.4%, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 97.6%, and the selectivity of the byproduct tetrahydroquinoline is 2.4%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 97.2%, the selectivity of the target product N-formyl tetrahydroquinoline is 97.5%, and the selectivity of the byproduct tetrahydroquinoline is 2.5%.
Comparative example 5
A process for the synthesis of N-formyl tetrahydroquinoline from quinoline differs from example 2 only in that the ammonia borane solution in step (2) is replaced with hydrogen and then hydrogen is introduced at a rate of 30mL/min for 80 min. The rest of the procedure is the same as in example 2.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 Catalyst compositionThe conversion rate of the reaction is 98.2 percent, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 98.6 percent, and the selectivity of the byproduct tetrahydroquinoline is 1.4 percent. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 98.1%, the selectivity of the target product N-formyl tetrahydroquinoline is 98.5%, and the selectivity of the byproduct tetrahydroquinoline is 1.5%.
Comparative example 6
A process for the synthesis of N-formyl-tetrahydroquinoline from quinoline, which differs from example 2 only in that the formic acid in step (3) is replaced by hydrogen and carbon monoxide at a gas pressure of 5MPa. The rest of the procedure is the same as in example 2.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 The catalyst is used for synthesizing N-formyl tetrahydroquinoline, the conversion rate of the reaction is 99.2%, wherein the selectivity of the target product N-formyl tetrahydroquinoline is 98.6%, and the selectivity of the byproduct tetrahydroquinoline is 1.4%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 99.1%, the selectivity of the target product N-formyl tetrahydroquinoline is 98.4%, and the selectivity of the byproduct tetrahydroquinoline is 1.6%.
Comparative example 7
A method for synthesizing N-formyl tetrahydroquinoline by quinoline, which comprises the following steps:
0.1g of catalyst Pd/C (product No. P116794, palladium on carbon, 5% Pd, shanghai Ala Biochemical technologies Co., ltd.) was placed in a three-necked flask, and N was introduced at a rate of 30mL/min for 80min 2 Then adding 1g of quinoline, 5g of formic acid and 20g of water into a three-neck flask, uniformly stirring, reacting for 2 hours at 50 ℃, and finally centrifuging for 8 hours at the rotating speed of 8000rpm to remove CoPd/B-g-C 3 N 4 After the catalyst, the N-formyl tetrahydroquinoline can be obtained.
Analysis of the product by gas chromatography, showed that CoPd/B-g-C was used 3 N 4 Catalyst for synthesizing N-formyl tetrahydroquinoline and conversion of reactionThe yield was 98.9%, wherein the selectivity of the target product N-formyl tetrahydroquinoline was 98.5%, and the selectivity of the byproduct tetrahydroquinoline was 1.5%. In CoPd/B-g-C 3 N 4 After the catalyst is recycled for 60 times, the catalyst is used for synthesizing N-formyl tetrahydroquinoline again, the conversion rate of the reaction is 98.8%, the selectivity of the target product N-formyl tetrahydroquinoline is 98.4%, and the selectivity of the byproduct tetrahydroquinoline is 1.6%.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. A method for synthesizing N-formyl tetrahydroquinoline by quinoline, which is characterized by comprising the following steps:
will N 2 Introducing CoPd/B-g-C 3 N 4 Adding quinoline, formic acid and water into a catalyst to react, and centrifuging to remove the CoPd/B-g-C after the reaction is finished 3 N 4 The catalyst can obtain the N-formyl tetrahydroquinoline.
2. The method for synthesizing N-formyl tetrahydroquinoline according to claim 1, wherein the N is 2 The flow rate of the air is 20-30 mL/min, and the air inlet time is 80-120 min;
the CoPd/B-g-C 3 N 4 The mass ratio of the catalyst to the quinoline to the formic acid to the water is (0.01-0.05) to 1 to 2-5 to 10-20;
the reaction is as follows: reacting for 2-5 h at the temperature of 10-50 ℃.
3. The method for synthesizing N-formyl tetrahydroquinoline according to claim 1, wherein the CoPd/B-g-C 3 N 4 A method for preparing a catalyst comprising the steps of:
(1) Dissolving dicyandiamide in water, adding a source B for hydrothermal reaction, filtering, drying and roasting to obtain B-g-C 3 N 4 ；
(2) Palladium chloride and Co salts are first dissolved in water, followed by the addition of the B-g-C 3 N 4 Then ammonia borane solution is added for reduction reaction, and finally centrifugal drying is carried out, thus obtaining the CoPd/B-g-C 3 N 4 A catalyst.
4. The method for synthesizing N-formyl tetrahydroquinoline according to claim 3, wherein the mass ratio of dicyandiamide to water to B source in the step (1) is 1:10-16:0.1-0.4.
5. The method for synthesizing N-formyl tetrahydroquinoline according to claim 4, wherein the source B comprises one or more of boric acid, terephthaloric acid or 4-carboxyphenylboronic acid.
6. A method for synthesizing N-formyl tetrahydroquinoline according to claim 3, wherein the hydrothermal reaction in step (1) is: reacting for 18-36 h at 80-140 ℃;
the drying is as follows: drying at 70-110 deg.c for 18-24 hr;
the roasting is as follows: roasting at 520-600 deg.c for 6-12 hr.
7. A process for the synthesis of N-formyl tetrahydroquinoline according to claim 3, wherein in step (2) the B-g-C 3 N 4 The mass ratio of the palladium chloride, the Co salt, the ammonia borane solution and the water is 1:0.1-0.3:0.3-0.5:0.4-0.6:20-60.
8. The method for synthesizing N-formyl tetrahydroquinoline according to claim 7, wherein the Co salt comprises one or any of cobalt nitrate, cobalt acetate, cobalt acetylacetonate or cobalt chloride.
9. A process for the synthesis of N-formyl tetrahydroquinoline according to claim 3, wherein the concentration of the ammonia borane solution in step (2) is from 0.05 to 0.15g/L;
the temperature of the reduction reaction is-4 ℃ and the time is 3.0-6.0 h.
10. An N-formyl tetrahydroquinoline synthesized by the method of synthesizing an N-formyl tetrahydroquinoline according to any one of claims 1 to 9.
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