CN114671781B - Method for converting arylbenzylamine into arylnitrile compound - Google Patents
Method for converting arylbenzylamine into arylnitrile compound Download PDFInfo
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- CN114671781B CN114671781B CN202210399488.4A CN202210399488A CN114671781B CN 114671781 B CN114671781 B CN 114671781B CN 202210399488 A CN202210399488 A CN 202210399488A CN 114671781 B CN114671781 B CN 114671781B
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- arylbenzylamine
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- arylnitrile
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- -1 aryl benzylamine Chemical compound 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- ZOUPGSMSNQLUNW-UHFFFAOYSA-N 2-(3,4-dichlorophenyl)acetic acid Chemical group OC(=O)CC1=CC=C(Cl)C(Cl)=C1 ZOUPGSMSNQLUNW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007806 chemical reaction intermediate Substances 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 2
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 14
- VPHHJAOJUJHJKD-UHFFFAOYSA-N 3,4-dichlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C(Cl)=C1 VPHHJAOJUJHJKD-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- IXHNFOOSLAWRBQ-UHFFFAOYSA-N (3,4-dichlorophenyl)methanamine Chemical compound NCC1=CC=C(Cl)C(Cl)=C1 IXHNFOOSLAWRBQ-UHFFFAOYSA-N 0.000 description 1
- YMVFJGSXZNNUDW-UHFFFAOYSA-N (4-chlorophenyl)methanamine Chemical compound NCC1=CC=C(Cl)C=C1 YMVFJGSXZNNUDW-UHFFFAOYSA-N 0.000 description 1
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 description 1
- IDPURXSQCKYKIJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 0.000 description 1
- OZRGLPAXIYOWIG-HZPUXBNGSA-N 4-nitrobenzylamine Chemical compound CC(C)C(CC[C@@H](C)[C@H]1CC[C@H]2[C@@H]3CCC4=CCCC[C@]4(C)[C@H]3CC[C@]12C)=O OZRGLPAXIYOWIG-HZPUXBNGSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 238000005609 Rosenmund-von Braun cyanation reaction Methods 0.000 description 1
- 238000000297 Sandmeyer reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for efficiently converting aryl benzylamine into aryl nitrile compounds, which uses a one-pot two-step method, and comprises the steps of activating an amino group by using an activating reagent in the presence of a catalyst to obtain a reaction intermediate, and converting the active reaction intermediate into cyano by alkali treatment. The method can efficiently realize the conversion of the arylbenzylamine to the arylnitrile, does not need to participate in a metal catalyst, has mild conditions, high yield and convenient post-treatment, can realize the amplification of the reaction, and has wide application prospect and practical value.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for converting 3, 4-dichlorobenzyl amine into an aryl nitrile compound under the catalysis of N-chlorosuccinimide.
Background
Aryl nitriles have played an important role in organic synthesis because cyano groups can be conveniently converted into a variety of functional materials including acids, aldehydes, ketones, and the like; meanwhile, the aryl nitrile compound is widely applied to the fields of dyes, medicines and the like, so that the aryl nitrile compound is an important chemical product. Such as the simplest benzonitrile, can be used for synthesizing pesticide molecules and benzomelamine high-grade paint, and can also be used as a key solvent for polymerization reaction.
Traditional methods for synthesizing aryl nitriles include the Sandmeyer reaction, the Rosenmund-von Braun reaction, and the synthesis of aryl nitriles can also be accomplished by functional group conversion and the dehydration oxidation of amines. However, these methods all have different limitations: 1) The use of highly toxic reagents such as cyanide not only has health and safety threat to operators, but also causes serious pollution to the environment; 2) The harsh reaction conditions increase the production requirements, and strict control is required in the production link; 3) Complicated steps and post-treatment processes increase the production cost; 4) Although the use of metal catalysts (Ru, cu, fe, etc.) increases the efficiency of the reaction, the problem of metal residues tends to affect the application of the product, especially in the medical field. Although the use of non-metal catalysts can solve the problem of metal residue, such as the non-metal mesoporous nitrogen doped carbon material disclosed in patent CN 112759533B, the preparation conditions of the catalyst are extremely harsh (calcination at 500-1000 ℃), and the reaction also requires high temperature conditions. While the process reported by Luca et al for the preparation of aromatic nitriles by mixing benzylamine with N-chlorosuccinimide by means of a high kinetic energy collision using a ball mill (eur.j. Org. Chem.2017, 5519-5526), although no catalyst is required, the reaction will have high demands on the production equipment during the scale-up process and will also cause a large energy loss. Therefore, on the basis of fully considering the economic cost and the environmental cost, the method for converting the arylbenzylamine into the arylnitrile compound is designed and developed, and still has high application value.
Disclosure of Invention
The invention aims to: the object of the present invention is to provide a process for converting arylbenzylamines into arylnitriles.
The technical scheme is as follows: the method for converting the arylbenzylamine into the arylnitrile compound provided by the invention uses a one-pot two-step method, in the presence of a catalyst, the arylbenzylamine is activated by an activating reagent to obtain a reaction intermediate, and then the active reaction intermediate is converted into the arylnitrile compound by alkali treatment;
The specific operation steps are as follows: adding arylbenzylamine, an activating reagent, a catalyst and a solvent into a reaction container, stirring at room temperature for reaction, adding alkali into the reaction after proper reaction time, and continuously stirring; after the reaction is finished, removing the solvent, and obtaining the target product aryl nitrile compound through simple separation by column chromatography;
the synthetic method has the following reaction route:
Wherein R 1,R2,R3,R4,R5 is independently selected from hydrogen, alkyl, alkoxy, halogen, nitro, aryl;
The activating reagent is N-halogenated succinimide or 1, 3-dihalo-5, 5-dimethyl hydantoin, wherein X represents Cl, br or I; the structure of the halogenated reagent is as follows:
X＝Cl,Br,I
The solvent is one or a mixture of tetrahydrofuran, acetonitrile, 1, 2-dichloroethane, dichloromethane, N-dimethylformamide and toluene, and preferably the solvent is dichloromethane;
the alkali is any one of 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylene diamine, diisopropylethylamine and triethylamine.
Further, the catalyst is one of carboxylic acid compounds.
Further, the catalyst is 3, 4-dichlorophenylacetic acid.
Further, the reaction process for converting the arylbenzylamine into the arylnitrile is carried out in an air atmosphere.
Further, the molar ratio of the arylbenzylamine to the catalyst is 1:0.01 to 1:0.05, preferably 1:0.05.
Further, the molar ratio of the arylbenzylamine to the activating reagent is 1: 2-1: 2.2, preferably 1:2.05.
Further, the molar ratio of the arylbenzylamine to the alkali is 1: 2-1: 3, preferably 1:2.5.
Further, the concentration of the arylbenzylamine is 0.5 to 2.0M, preferably 1.0M.
Further, the reaction temperature for converting the arylbenzylamine into the arylnitrile is 25-80 ℃, preferably 25 ℃.
Further, the reaction time for converting the arylbenzylamine into the arylnitrile is 0.5-6 hours.
The beneficial effects are that: the invention has the following specific advantages:
1. The invention provides a convenient method for preparing the aryl nitrile compound, and has the advantages of mild reaction condition, simple operation and convenient post-treatment.
2. The catalyst used in the invention has low price, small dosage, simple taking and easy obtaining of the activating reagent.
3. The synthesis method can convert the arylbenzylamine into the arylnitrile compound, can realize amplification of the reaction, and has wide application prospect and practical value.
Detailed Description
The following technical solutions in the embodiments of the present invention will be clearly and completely described so that those skilled in the art can better understand the advantages and features of the present invention, thereby making a clearer definition of the protection scope of the present invention. The described embodiments of the present invention are intended to be only a few, but not all embodiments of the present invention, and all other embodiments that may be made by one of ordinary skill in the art without inventive faculty are intended to be within the scope of the present invention.
Example 1
In a 25mL reaction tube, benzylamine (2 mmol), N-chlorosuccinimide (4.1 mmol), 3, 4-dichlorophenylacetic acid (0.1 mmol) and methylene chloride (2 mL) were added and stirred at 25℃for 0.5 hours. After the completion of the reaction, triethylamine (5 mmol) was added to the reaction system, followed by stirring for 0.5 hours. After the reaction, the reaction system was concentrated and separated by column chromatography to give the objective product (97%). 1 H NMR (400 MHz, chloro form-d) delta 7.68-7.55 (m, 3H), 7.51-7.43 (m, 2H).
Example 2
In a 25mL reaction tube, 4-nitrobenzylamine (2 mmol), N-chlorosuccinimide (4.1 mmol), 3, 4-dichlorobenzoic acid (0.1 mmol) and methylene chloride (2 mL) were added and stirred at 25℃for 0.5 hours. After the completion of the reaction, triethylamine (5 mmol) was added to the reaction system, followed by stirring for 0.5 hours. After the reaction, the reaction system was concentrated and separated by column chromatography to give the objective product (95%). 1 H NMR (400 mhz, chloro-d) δ8.38 (d, j=8.7hz, 2H), 7.92 (d, j=8.7hz, 2H).
Example 3
In a 25mL reaction tube, 4-methoxybenzylamine (2 mmol), N-chlorosuccinimide (4.1 mmol), 3, 4-dichlorobenzoic acid (0.1 mmol) and methylene chloride (2 mL) were added and stirred at 25℃for 0.5 hours. After the completion of the reaction, triethylamine (5 mmol) was added to the reaction system, followed by stirring for 1 hour. After the reaction, the reaction system was concentrated and separated by column chromatography to give the objective product (90%). 1 H NMR (400 MHz, chloroform-d) delta 7.67-7.59 (m, 2H), 6.99-6.89 (m, 2H), 3.90 (s, 3H).
Example 4
In a 25mL reaction tube, 4-methylbenzylamine (2 mmol), N-chlorosuccinimide (4.1 mmol), 3, 4-dichlorobenzoic acid (0.1 mmol) and methylene chloride (2 mL) were added and stirred at 25℃for 0.5 hours. After the completion of the reaction, triethylamine (5 mmol) was added to the reaction system, followed by stirring for 0.5 hours. After the reaction, the reaction system was concentrated and separated by column chromatography to give the objective product (92%). 1 H NMR (400 mhz, chloroform-d) delta 7.53 (d, j=8.0 hz, 2H), 7.27 (d, j=7.5 hz, 2H), 2.40 (s, 3H).
Example 5
In a 25mL reaction tube, 4-chlorobenzylamine (2 mmol), N-chlorosuccinimide (4.1 mmol), 3, 4-dichlorobenzoic acid (0.1 mmol) and methylene chloride (2 mL) were added and stirred at 25℃for 0.5 hours. After the completion of the reaction, triethylamine (5 mmol) was added to the reaction system, followed by stirring for 0.5 hours. After the reaction, the reaction system was concentrated and separated by column chromatography to give the objective product (95%). 1 H NMR (400 mhz, chloro-d) delta 7.62 (d, j=8.5 hz, 2H), 7.49 (d, j=8.5 hz, 2H).
Claims (1)
1. A process for converting arylbenzylamines to arylnitriles, characterized by: in the presence of a catalyst, an activating reagent and a solvent, converting arylbenzylamine into an arylnitrile compound;
The specific operation steps are as follows: adding arylbenzylamine, an activating reagent, a catalyst and a solvent into a reaction container, stirring at room temperature for reaction, adding alkali into the reaction after proper reaction time, and continuously stirring; after the reaction is finished, removing the solvent, and obtaining the target product aryl nitrile compound through simple separation by column chromatography;
The reaction route of the method is as follows:
Wherein R 1,R2,R3,R4,R5 is independently selected from hydrogen, alkyl, alkoxy, halogen, nitro;
the activating reagent is N-halogenated succinimide, wherein X represents Cl, br or I; the structure of the halogenated reagent is as follows:
the solvent is one or a mixture of more of tetrahydrofuran, acetonitrile, 1, 2-dichloroethane, dichloromethane, N-dimethylformamide and toluene;
The alkali is any one of 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylene diamine, diisopropylethylamine and triethylamine;
the catalyst is 3, 4-dichlorophenylacetic acid;
the reaction process for converting the arylbenzylamine into the arylnitrile is carried out in an air atmosphere;
the molar ratio of the arylbenzylamine to the catalyst is 1:0.01 to 1:0.05;
The mole ratio of the arylbenzylamine to the activating reagent is 1: 2-1: 2.2;
The molar ratio of the arylbenzylamine to the alkali is 1: 2-1: 3, a step of;
The concentration of the arylbenzylamine is 0.5-2.0M;
the reaction temperature for converting the arylbenzylamine into the arylnitrile is 25 ℃, and the reaction time is 0.5-6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210399488.4A CN114671781B (en) | 2022-04-15 | 2022-04-15 | Method for converting arylbenzylamine into arylnitrile compound |
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| CN202210399488.4A CN114671781B (en) | 2022-04-15 | 2022-04-15 | Method for converting arylbenzylamine into arylnitrile compound |
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| Publication Number | Publication Date |
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| CN114671781A CN114671781A (en) | 2022-06-28 |
| CN114671781B true CN114671781B (en) | 2024-04-19 |
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2022
- 2022-04-15 CN CN202210399488.4A patent/CN114671781B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| A mechanochemical-assisted oxidation of amines to carbonyl compounds and nitriles;Gaspa Silvia 等;European Journal of Organic Chemistry(第37期);第5519-5526页 * |
| Palladium-catalyzed synthesis of 3-trifluoromethylated 1,3-dienes from acrylate derivatives and BTP;Zhao Qun 等;Tetrahedron;第74卷(第41期);第6033-6040 页 * |
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